Podcasts about dimethyl

Story at-a-glance Sinusitis affects 31 million Americans annually, with many seeking treatments that cause side effects. Natural remedies will address the inflammation and provide relief without the adverse effects of pharmaceuticals Your sinuses are eight cavities located in your head that filter and humidify the air you inhale, removing irritants and providing protection from head impacts Effective home remedies include saline nasal irrigation, steam therapy, staying hydrated, warm compresses, reducing mold exposure, sleeping at an elevated angle, and using humidifiers Anti-inflammatory foods like garlic, onions, ginger, turmeric, pineapple, chili peppers, horseradish, coconut oil, and citrus fruits help manage sinusitis by reducing congestion and fighting infections Dimethyl sulfoxide (DMSO) is another natural solution for treating sinusitis. Research demonstrates it has anti-inflammatory, antibacterial, and antifungal properties that provide significant relief for patients

Story at-a-glance Dimethyl sulfoxide (DMSO) is a potent compound known for treating a wide range of "incurable" musculoskeletal, neurological, infectious, and autoimmune conditions due to its unique properties DMSO properties also transform cancer care as it causes cells to stop being cancerous, significantly increases the potency of many cancer treatments (hence improving their safety and efficacy,) and protects normal tissue from their toxicity Many natural treatments are also dramatically more effective once mixed with DMSO. Hematoxylin, a common pathology dye, when mixed with DMSO is an incredibly potent cancer therapy which has no toxicity to normal tissue Despite promising results and minimal side effects, D-hematoxylin faced significant regulatory barriers, with the FDA and medical establishment effectively marginalizing this potentially breakthrough cancer treatment This article will review the history of this therapy, which cancers it works best against (e.g., leukemias), and the molecular mechanisms that underlie its remarkable effects

Story at-a-glance Sinusitis affects 31 million Americans annually, with many seeking treatments that cause side effects. Natural remedies will address the inflammation and provide relief without the adverse effects of pharmaceuticals Your sinuses are eight cavities located in your head that filter and humidify the air you inhale, removing irritants and providing protection from head impacts Effective home remedies include saline nasal irrigation, steam therapy, staying hydrated, warm compresses, reducing mold exposure, sleeping at an elevated angle, and using humidifiers Anti-inflammatory foods like garlic, onions, ginger, turmeric, pineapple, chili peppers, horseradish, coconut oil, and citrus fruits help manage sinusitis by reducing congestion and fighting infections Dimethyl sulfoxide (DMSO) is another natural solution for treating sinusitis. Research demonstrates it has anti-inflammatory, antibacterial, and antifungal properties that provide significant relief for patients

On this episode, Maui tackles the Pope from Chiraq, Religion, Kanye's new song, Arsenal, U.K. Killer Teens, Podcast regulation, Trump 2028?, and a whole lot more! /Edit More: https://xoroyalty.net℗ 2025 XO LUXURY GOODS

Sponsor Details:Insta360 X5 Camera. To bag a free invisible selfie stick worth US$24.99 with your purchase, head to store.insta360.com and use the promo code "spacenuts", available for the first 30 standard package purchases only.NordVPN: To get the special SpaceNuts discount deal with 4 extra free months, plus a 30 money back guarantee simply visit www.nordvpn.com/spacenuts In this engaging Q&A episode of Space Nuts, host Andrew Dunkley is back alongside the ever-insightful Professor Fred Watson. Together, they tackle a range of intriguing questions from listeners, covering the potential discovery of life on exoplanet K2 18b, the mysteries of gravity and gravitons, and the latest on the Swan Comet.Episode Highlights:- The Buzz Around K2 18b: Andrew and Fred Watson discuss the recent excitement surrounding the detection of dimethyl sulphide on K2 18b, a potential biosignature. They delve into the implications of this discovery and the ongoing debate about the planet's habitability, while also addressing the sensationalist headlines that often accompany such findings.- Gravity and Gravitons: A question from listener James prompts a fascinating discussion on the nature of gravity and the role of the Higgs particle versus the hypothetical graviton. Fred Watson explains the differences between these concepts and the complexities of how gravity operates at a fundamental level.- Observing the Swan Comet: Ted from an undisclosed location shares his experiences of observing the Swan Comet, prompting a conversation about its current visibility and characteristics. Andrew and Fred Watson discuss the comet's colour, tail, and what makes it an interesting object for amateur astronomers.- The Challenge of Fake News in Science: The episode wraps up with a thoughtful examination of how sensationalism in the media can distort scientific discoveries. Andrew and Fred Watson reflect on the responsibility of scientists and journalists alike to convey information accurately and responsibly.For more Space Nuts, including our continually updating newsfeed and to listen to all our episodes, visit our website. Follow us on social media at SpaceNutsPod on Facebook, X, YouTube Music, Tumblr, Instagram, and TikTok. We love engaging with our community, so be sure to drop us a message or comment on your favourite platform.If you'd like to help support Space Nuts and join our growing family of insiders for commercial-free episodes and more, visit spacenutspodcast.com/aboutStay curious, keep looking up, and join us next time for more stellar insights and cosmic wonders. Until then, clear skies and happy stargazing.(00:00) Welcome to Space Nuts with Andrew Dunkley and Fred Watson Watson(01:20) Discussion on the potential discovery of life on K2 18b(15:00) Exploring gravity and the role of gravitons(25:30) Observing the Swan Comet(35:00) The impact of sensationalism in scientific reportingFor commercial-free versions of Space Nuts, join us on Patreon, Supercast, Apple Podcasts, or become a supporter here: https://www.spreaker.com/podcast/space-nuts-astronomy-insights-cosmic-discoveries--2631155/support.

Story at-a-glance Versatile therapeutic benefits — Dimethyl sulfoxide (DMSO) is a potent compound known for treating a wide range of conditions, including chronic pain, stroke recovery, tissue damage, autoimmune disorders, various skin conditions, and complex infections Unique role in cancer care — DMSO's distinctive properties enable it to support the body in combating cancer while safeguarding healthy cells from the harmful effects of chemotherapy and radiation Enhanced chemotherapy delivery — When paired with chemotherapy, DMSO improves the drug's ability to penetrate cancer cells that are typically inaccessible, significantly boosting treatment effectiveness Lower doses, reduced toxicity — By enhancing the potency of chemotherapy, DMSO allows for the use of lower doses, substantially reducing the toxic side effects associated with conventional cancer treatments Synergistic potential — DMSO demonstrates promising results when combined with various pharmaceutical agents, amplifying their cancer-fighting capabilities

On this episode, Maui Usher's Cherries, Crazy Billionaires, Shannon Sharpe, Family, Volodymyr Zelenskyy in South Ahh, Ramaphosa's Legendary run, and a whole lot more! /Edit More: https://xoroyalty.net℗ 2024 XO LUXURY GOODS

Space Nuts Episode 515: K2 18b, Polar Orbits, and the Lucy MissionIn this fascinating episode of Space Nuts, host Heidi Campo takes the helm for her final week as Andrew Dunkley prepares to return. Joined by the ever-knowledgeable Professor Fred Watson, they delve into some of the most exciting recent discoveries in astronomy, including the much-discussed K2 18b, the peculiar polar orbit of a newly discovered planet, and the latest from NASA's Lucy mission.Episode Highlights:- K2 18b's Potential for Life: Heidi and Fred explore the latest findings on K2 18b, a planet in the habitable zone of its star that exhibits chemical signatures potentially linked to life. They discuss the significance of dimethyl sulfide and dimethyldisulfide and the challenges of confirming these findings through the James Webb Space Telescope.- The Mystery of Polar Orbits: The duo shifts gears to discuss the surprising discovery of a planet orbiting in a polar configuration around a binary star system. Fred explains the implications of this unusual orbit and the theories surrounding its formation, raising questions about the nature of planetary systems.- The Lucy Mission: The episode wraps up with an exciting update on NASA's Lucy mission, which aims to explore Trojan asteroids. Heidi and Fred discuss the mission's unique goals, the significance of the asteroid named after paleoanthropologist Donaldjohanson Johanson, and the intriguing connections between the mission's title and its namesake.For more Space Nuts, including our continually updating newsfeed and to listen to all our episodes, visit our website. Follow us on social media at SpaceNutsPod on Facebook, X, YouTube Music Music, Tumblr, Instagram, and TikTok. We love engaging with our community, so be sure to drop us a message or comment on your favorite platform.If you'd like to help support Space Nuts and join our growing family of insiders for commercial-free episodes and more, visit spacenutspodcast.com/aboutStay curious, keep looking up, and join us next time for more stellar insights and cosmic wonders. Until then, clear skies and happy stargazing.(00:00) Welcome to Space Nuts with Heidi Campo and Fred Watson(01:15) Discussion on K2 18b and its potential for life(15:30) The polar orbit discovery around binary stars(25:00) Updates on NASA's Lucy mission and its asteroid flybyFor the commercial-free versions of Space Nuts, join us on Patreon, Supercast, Apple Podcasts, or become a supporter here: https://www.spreaker.com/podcast/space-nuts-astronomy-insights-cosmic-discoveries--2631155/support.

On this episode, Maui tackles Shannon Sharpe, Dimethyl Sufide, the Pope's death, Kanye West & his cousin, Geniuses, Jesus, and a whole lot more! /Edit More: https://xoroyalty.net℗ 2024 XO LUXURY GOODS

Hints of Alien Life, a Galactic Mystery, and Juno's Safe Mode IncidentIn this episode of SpaceTime, we explore groundbreaking revelations suggesting the potential for alien life beyond Earth. Using NASA's Webb Space Telescope, astronomers have detected chemical signatures of dimethyl sulfide and dimethyl disulfide in the atmosphere of the exoplanet K2 18 b, a sub-Neptune world located 124 light years away in the habitable zone of its host star. While these findings are incredibly promising, researchers urge caution as they work to confirm these biosignatures through further observations.A Surprising Spiral Galaxy from the Early UniverseNext, we dive into the discovery of a surprisingly large spiral galaxy dating back 11.4 billion years, which challenges current models of galaxy formation. This massive galaxy, dubbed the "Big Wheel," is three times larger than expected for its time, prompting astronomers to rethink how galaxies can grow and evolve in the early universe. The implications of this finding could reshape our understanding of cosmic structure and formation processes.NASA's Juno Spacecraft in Safe ModeAdditionally, we discuss a recent anomaly that forced NASA's Juno spacecraft to enter safe mode during a close flyby of Jupiter. The spacecraft's precautionary measures allowed it to protect its systems and continue diagnostics, ensuring the mission's ongoing success as it gathers vital data about the gas giant and its moons.00:00 Space Time Series 28 Episode 48 for broadcast on 21 April 202500:49 Potential biosignatures detected on K2 18 b06:30 Implications for the search for extraterrestrial life12:15 Discovery of an ancient spiral galaxy in the early universe18:00 Challenges to current galaxy formation models22:45 Juno spacecraft enters safe mode after anomaly27:00 Summary of recent astronomical discoveries30:15 Science report: Health benefits of sauerkraut and lunar dust solar panelswww.spacetimewithstuartgary.comwww.bitesz.com

Story at-a-glance Dimethyl sulfoxide (DMSO) effectively treats many ailments, including strokes, tissue injuries, autoimmunity, and a myriad of skin diseases and challenging infections DMSO's unique properties also make it highly suited for both eliminating cancers and protecting the normal cells from cancer therapies Hundreds of studies have shown DMSO can transform a wide range of cancerous cells back into normal cells — something very few other agents are capable of DMSO strengthens the immune response to cancer and allows the immune system to recognize and permanently eliminate many different cancers that otherwise evade the immune system DMSO is directly toxic to cancerous cells and greatly increases the potency of a wide range of natural and conventional anticancer agents. This both increases cure rates and allows lower chemotherapy doses, significantly reducing their toxicity

Astronomy Daily | Space News: S04E92In this episode of Astronomy Daily, host Anna takes you on an exhilarating exploration of groundbreaking cosmic discoveries that could change our understanding of life in the universe. From compelling evidence of extraterrestrial life to the complexities surrounding SpaceX's operations, this episode is packed with insights that will ignite your curiosity about the cosmos.Highlights:- Strongest Evidence Yet for Extraterrestrial Life: Join us as we delve into the remarkable findings from the James Webb Space Telescope, which suggest the presence of biological compounds in the atmosphere of the exoplanet K218b. Discover how these observations could mark a pivotal moment in our quest to answer the age-old question: Are we alone in the universe?- SpaceX Landings Suspended in the Bahamas: Learn about the Bahamian government's decision to suspend all SpaceX Falcon 9 rocket landings pending an environmental assessment. We discuss the implications of this sudden halt and the growing regulatory challenges faced by private space companies.- A Planet Orbiting Two Stars: Explore the discovery of an unprecedented exoplanet orbiting a binary brown dwarf system. This unique configuration challenges existing theories of planetary formation and opens new avenues for understanding the diversity of planetary systems.- The Universe May Rotate: Uncover a groundbreaking theory suggesting that the entire universe might be rotating, albeit extremely slowly. This hypothesis could help resolve the Hubble tension and deepen our understanding of cosmic expansion.- Solving the Mystery of Ultra High Energy Cosmic Rays: Discover how scientists may have identified the source of ultra high energy cosmic rays as the mergers of binary neutron stars. This theory provides a new lens through which to study some of the universe's most energetic phenomena.For more cosmic updates, visit our website at astronomydaily.io. Join our community on social media by searching for #AstroDailyPod on Facebook, X, YouTubeMusic, TikTok, and our new Instagram account! Don't forget to subscribe to the podcast on Apple Podcasts, Spotify, iHeartRadio, or wherever you get your podcasts.Thank you for tuning in. This is Anna signing off. Until next time, keep looking up and stay curious about the wonders of our universe.00:00 - Welcome to Astronomy Daily01:05 - Strongest evidence for extraterrestrial life10:30 - SpaceX landings suspended in the Bahamas17:00 - Planet orbiting two stars22:15 - The universe may rotate27:30 - Ultra high energy cosmic rays mystery solved✍️ Episode ReferencesExtraterrestrial Life Findings[University of Cambridge](https://www.cam.ac.uk/)SpaceX Suspension News[Bahamas Government](https://www.bahamas.gov.bs/)Planet Discovery[University of Birmingham](https://www.birmingham.ac.uk/)Universe Rotation Theory[Royal Astronomical Society](https://www.ras.ac.uk/)Ultra High Energy Cosmic Rays Research[New York University](https://www.nyu.edu/)Astronomy Daily[Astronomy Daily](http://www.astronomydaily.io/)Become a supporter of this podcast: https://www.spreaker.com/podcast/astronomy-daily-exciting-space-discoveries-and-news--5648921/support.

Story at-a-glance Dimethyl sulfoxide (DMSO), a forgotten gem from the 1960s, effectively treats a broad spectrum of conditions, including strokes, tissue injuries, autoimmune inflammation, a myriad of skin diseases, and many challenging infections One of the least-known benefits of DMSO is that it also eliminates cancers (especially when combined with another therapy) and protects the body from damage created by conventional cancer therapies In dozens of experiments, DMSO has been shown to prevent the damage radiation does to cells, animals, and humans and to heal existing radiation injuries — something relevant not only to cancer patients but also to those receiving CT scans DMSO effectively prevents many of the illnesses and complications that follow chemotherapy. Likewise, it also protects patients from accidental chemotherapy injuries where the medication leaks into the tissue DMSO heals surgical wounds (which prevents many complications from cancer surgeries) and significantly extends the survival of patients whose tumors were surgically removed

Today's podcast comes from four blog posts: DMSO: For Pain, Inflammation, Tissue Healing and Protection DMSO for Vascular and Circulatory Disorders DMSO for Nerves and the Nervous System DMSO for Skin and Connective Tissues Discover more Christian podcasts at lifeaudio.com and inquire about advertising opportunities at lifeaudio.com/contact-us.

Today on Health & Longevity, Dr. John Westerdahl's featured guest is Archie Scott, a DMSO expert, chemist, and author. Archie Scott is recognized as a leading expert and educator on the topic of Dimethyl sulfoxide, commonly known as DMSO. DMSO is a popular compound used both externally and internally as a treatment for numerous health conditions. It has been used for relief of arthritis, pain, burns and injuries. Mr. Scott discusses DMSO and its possible medical applications. He is author of the book, The DMSO Handbook for Doctors.

Welcome to the NeurologyLive® Mind Moments® podcast. Tune in to hear leaders in neurology sound off on topics that impact your clinical practice. In this episode, Francesco Saccà, MD, PhD, an associate professor of neurology at the University of Naples, discussed an ongoing study assessing the use of dimethyl fumarate, an approved therapy for relapsing multiple sclerosis, in patients with Friedreich ataxia (FA). He spoke on the mechanism of action of the agent and why it can be beneficial in this patient population, as well as how it differs from omaveloxolone (Skyclarys; Biogen), the first approved treatment for FA. In addition, he outlined the study design, the primary end point of frataxin decrease, and what would be considered a "successful" study. Furthermore, he spoke on the reasons behind the trial and what led investigators to this point. Looking for more ataxia discussion? Check out the NeurologyLive® ataxia clinical focus page. Episode Breakdown: 1:05 – Origin of the study 3:00 – Conduct of the study, end points, goals  5:10 – Promising mechanism of action of dimethyl fumarate to treat Friedreich ataxia 7:30 – Questions in clinical impact of changes in frataxin 10:00 – Neurology News Minute 12:40 – What is considered a successful study? 14:55 – Patient inclusion, demographic makeup of the study 16:35 – Timeline of the trial and data readout The stories featured in this week's Neurology News Minute, which will give you quick updates on the following developments in neurology, are further detailed here: FDA Approves Alexion's Ravulizumab-cwvz for Neuromyelitis Optica Spectrum Disorder Epilepsy Agent STK-001 Demonstrates Disease-Modifying Effects in Early Phase Studies of Dravet Syndrome Eisai Submits sBLA for Monthly Intravenous Maintenance Dosing of Alzheimer Therapy Lecanemab Thanks for listening to the NeurologyLive® Mind Moments® podcast. To support the show, be sure to rate, review, and subscribe wherever you listen to podcasts. For more neurology news and expert-driven content, visit neurologylive.com.

Dr. Martin answers questions sent in by our listeners. Some of today's topics include: Rising cancer rates Eye drop antibiotics Dark circles under eyes Tremors and stuttering in jawline Dimethyl sulfoxide (DMSO) Estrogen & protective benefits against heart disease Supplements Dr. Martin takes  

In this King Hero interview with ADV (Amandha Vollmer), we will be exploring the healing properties of DMSO - Dimethyl Sulfoxide.  The author of "Healing with DMSO" and healing practitioner of many years of experience, Amandha will be talking about the history of how this substance was discovered to be a healing force, why it is actually safe and effective, where to be cautious, what conditions are best addressed with it, when not to use it, and how to know if it is working. Social Media  Linktree: https://linktr.ee/Yummy.doctor Instagram: @Yummy.Doctor, @amandh.a.v and @yumnaturals Facebook: Amanda Vollmer and @yumnaturalsTwitter: @yummy_doctor Telegram Groups  ADV's Main Channel: https://t.me/amandhavollmer    ADV's Group: https://t.me/healthydoseoftruth ADV's Legal/Lawful Templates Group: https://t.me/HDoT_Templates  ADV's Local Ontario Group: https://t.me/ontarioawake  *** MORE FROM BETH Apply to become a member of the House of Free Will Ministry Find the other 260+ King Hero's Journey interviews and Personal Rants Donate by PayPal if you're inspired King Hero Telegram Channel King Hero Telegram Chat Apply for archetype, de-programming or business coaching and trainingor email beth at bethmartens.com Sign up to do a King Hero's Journey archetype quiz Order a copy of my book, ‘Journey: A Map of Archetypes to Find Lost Purpose in a Sea of Meaninglessness' Join me on the uncensored Rokfin Canadian Court Procedure Study Group sign up Affiliates: Take Dr. Frederick Graves' Jurisdictionary online course (with my link)Get a Brown's gas AquaCure with $125 US savings by using the code: FREEWILL at www.eagle-research.life Being free is not a spectator sport - Hal Anthony, “Behind the Woodshed” ***ABOUT BETH MARTENS For archetype, purpose and business coach, author, coach trainer, and founder of the House of Free Will in the Private Domain, Beth Martens, her calling is a life or death thing. After a decade as a corporate VP in her family's firm, 8 trips to India, and a 3-year battle with cancer 20 years ago, she used archetypes to save her life.  Today she helps truth lovers find their sacred purpose, be valued for their life's work, and survive the ordeals of their Hero's Journey. As a recovering feminist, she helps strong men to survive their missions, and hosts the King Hero's Journey podcast to highlight important leaders, entrepreneurs, movement makers, law experts, and purveyors of the truth.   Visit her at www.bethmartens.com to do a free ‘King Hero' Archetype Quiz to learn where you are on the path of purpose. Find her book, “Journey: A Map of Archetypes to Find Lost Purpose in a Sea of Meaninglessness” is available at www.bethmartens.com. Apply to become a member in the House of Free Will Ministry at www.freewillministry.live. --- Send in a voice message: https://podcasters.spotify.com/pod/show/beth-martens/message

In this episode of “How Do You Say That?!” sponsored by britishvoiceover.co.uk, Katy Maw joins Sam and Mark to talk about finding our quiz show personas, how to voice successfully despite personal tragedies, and making sure you approach a script with conviction because "If you hold back people hear it".Our VO question this week is all about whether it's worth taking a travel kit away with you on holiday.We'd love you to join in and send us your version of one of the reads in today's show – just pop it onto an mp3 and send it to podcast@britishvoiceover.co.ukScript 1·Welcome contestant! Have you got what it takes to take on our quiz?·Hello there! Are you ready for a quizzing good time?·Let's welcome our next contestant!·It's time, to GET QUIZZY!!!·It's time to give the wheel another spin.·Round it goes, round it goes. Where it stops, nobody knows!·Let's hope you get a better category this time.·Oooh, the anticipation is killing me!Script 2There are 6 primary gases that have the most significant impact on the distinctive odour of a decaying body. These are:Cadaverine (rotting fish odour)Putrescine (faeces odour)Indole (sticky sweet odour)Hydrogen sulphide (rotten egg odour)Methanethiol (rotting cabbage odour)Dimethyl disulphide & Trisulphide (foul garlic odour)By far the most common gases that contribute to the putrid smell of a cadaver are cadaverine & putrescine.**Listen to all of our podcasts here - you can also watch on YouTube, or say "Alexa, Play How Do You Say That?!"About our guest: Katy has been voicing for 24 years now after becoming a classically trained actor in London. She works daily, predominantly on corporate & commercial scripts & has voiced literally thousands of local & National radio ads over the years and she works across all other mediums of voicing, like e-learning and IVR, narration and dubbing/ADR. She has been seen & heard on television and film sporadically over the years (Sherlock, Eastenders) and has, in more recent years, started voicing video games and audio drama as she gets back into her dramatic acting.Her clients include Amazon, Blizzard, Warhammer, ASDA, T K Maxx, Global, Bauer, ITV & the BBC, but that is just the tip of the Blue Chip iceberg. A natural RP speaker but equally at home using accents particular when she gets to use her Bristolian home town accent! Katy's Website @katy.maw on Instagram Katy's Facebook page @KatyMawMedia on TwitterResources: Howjasay Mark's demos & contact details: https://linktr.ee/britishvoiceovermarkSam's demos & contact details:

00:00 - Introduction01:03 - Types of algaecides01:52 - Copper sulfate04:54 - Quat and Polyquat (quaternary ammonia)08:11 - Enzymes conflict with polyquat algaecide too09:53 - Sodium bromide13:35 - Mineral systems and ionized metals16:09 - Ammonium sulfate and Dimethyl ammonium chloride19:14 - Polymers20:13 - Wrap up ------------------------------------Connect with Orenda TechnologiesWebsite: https://www.orendatech.comHelp Center: https://ask.orendatech.comBlog: https://blog.orendatech.comYouTube: https://www.youtube.com/user/OrendaTechnologiesFacebook: https://www.facebook.com/orendatech/Instagram: https://www.instagram.com/orendatechnologies/Swim Across America | Team Orenda: https://www.swimacrossamerica.org/goto/orenda

In this week's episode, we'll learn more about the treatment of relapsed and refractory cutaneous T-cell lymphoma with dimethyl fumarate, discuss the use of lipid nanoparticles for ex vivo editing of human hematopoietic cells, and learn more about racial and geographic disparities in lymphoma clinical trials.

#96 Decarbonizing with DME (Dimethyl Ether) Renewable DME (dimethyl ether) is a sustainable fuel that The post #96 Decarbonizing with DME (Dimethyl Ether) appeared first on Transport Energy Strategies.

#96 Decarbonizing with DME (Dimethyl Ether) Renewable DME (dimethyl ether) is a sustainable fuel that The post #96 Decarbonizing with DME (Dimethyl Ether) appeared first on Transport Energy Strategies.

Welcome to the NeurologyLive® Mind Moments® podcast. Tune in to hear leaders in neurology sound off on topics that impact your clinical practice. In this episode, we spoke with Darin Okuda, MD, director of Neuroinnovation and Multiple Sclerosis & Neuroimmunology Imaging Program at UT Southwestern Medical Center. He spoke about the phase 2 ARISE study assessing dimethyl fumarate (Tecfidera; Biogen) in patients with radiologically isolated syndrome, the significance of the findings, next steps in validating this therapy, and more.  Looking for more multiple sclerosis discussion? Check out the NeurologyLive® multiple sclerosis clinical focus page. Episode Breakdown: 1:20 – Overview of ARISE and conduct of study 4:20 – Potential subgroup responders to dimethyl fumarate 8:10 – Efforts to improve the detection of radiologically isolated syndrome 10:05 – Neurology News Minute 11:55 – Next steps of research following ARISE 16:50 – Closing thoughts on significance of the study This episode is brought to you by Medical World News, a streaming channel from MJH Life Sciences®. Check out new content and shows every day, only at medicalworldnews.com. The stories featured in this week's Neurology News Minute, which will give you quick updates on the following developments in neurology, are further detailed here: CNM-Au8 Shows Positive Findings on MS-Related Biomarkers of Whole Brain, White Matter Aducanumab's Label Updated to Include Risks on Brain Bleeding Primary Care Physicians Show Greater Confidence in Diagnosing Alzheimer Disease Through DISCERN Skin Test FDA Approves Extended-Release Deutetrabenazine for Huntington Disease Chorea, Tardive Dyskinesia Thanks for listening to the NeurologyLive® Mind Moments® podcast. To support the show, be sure to rate, review, and subscribe wherever you listen to podcasts. For more neurology news and expert-driven content, visit neurologylive.com. REFERENCE Okuda DT, Kantarci O, Lebrun-Frenay C, et al. Dimethyl fumarate delays multiple sclerosis radiologically isolated syndrome. Ann Neurol. 2023;93(3):604-614. doi:10.1002/ana.26555

Dimethyl sulfoxide (DMSO) is an amazing substance the potential of which few people are aware. It is an analgesic, anti-inflammatory, antioxidant, anti-fungal, and so much more. Listen to today's Solutions Talk to find out more about this substance.Links to my book Autism Wellbeing Plan: How to Get Your Child Healthy:US Amazon: https://www.amazon.com/Autism-Wellbeing-Plan-Child-Healthy/dp/1916393004UK Amazon: https://www.amazon.co.uk/Autism-Wellbeing-Plan-Child-Healthy-ebook/dp/B084GBBDL9My podcast, Autism and Children's Health: https://podcasts.apple.com/us/podcast/autism-and-childrens-health-lab-testing-diet/id1512380225Video courses:The Healthy Gluten-Free, Casein-Free Diet for Autism & ADHD:https://www.udemy.com/course/gluten-free-casein-free-diet-for-children-autism-adhd-gut-dysfunction/?referralCode=F232BBF8D4DABBBF6110Sign up to my mailing list to get the below course on nutrient supplementation for your child for free: https://christianyordanov.com/autism-wellbeing-plan-resources/Nutrient Supplements for Autism, ADHD, and Children's Health:https://www.udemy.com/course/nutrient-supplementation-for-childrens-health/?referralCode=6269D58AC095B1D4039CWebsite: https://christianyordanov.com/

I read from dime store to diminutive.     Dimethyl Sulfoxide https://en.wikipedia.org/wiki/Dimethyl_sulfoxide     Dimethyltryptamine (AKA: DMT) https://en.wikipedia.org/wiki/N,N-Dimethyltryptamine     The word of the episode is "diminished".     Theme music from Tom Maslowski https://zestysol.com/     Merchandising! https://www.teepublic.com/user/spejampar     "The Dictionary - Letter A" on YouTube   "The Dictionary - Letter B" on YouTube   "The Dictionary - Letter C" on YouTube   "The Dictionary - Letter D" on YouTube     Featured in a Top 10 Dictionary Podcasts list! https://blog.feedspot.com/dictionary_podcasts/     Backwards Talking on YouTube: https://www.youtube.com/playlist?list=PLmIujMwEDbgZUexyR90jaTEEVmAYcCzuq     dictionarypod@gmail.com https://www.facebook.com/thedictionarypod/ https://twitter.com/dictionarypod https://www.instagram.com/dictionarypod/ https://www.patreon.com/spejampar https://www.tiktok.com/@spejampar 917-727-5757

On March 8, the ESO announced in their Press Release (https://www.eso.org/public/news/eso2205/?lang) that a team of researchers from Leiden University, The Netherlands, had detected the largest molecule to date within a planetary disc. At 9-atoms, dimethyl ether is considered a precursor of larger organic molecules that can lead to the emergence of life. Tonight we are pleased to air Fraser's prerecorded interview with two members of the team that detected the molecule, Nashanty Brunken and Dr. Alice Booth, who will tell us more about this amazing detection. Nashanty Brunken is an Astronomy Masters student at Leiden University with experience in Astrochemistry research. She is a writer at Leiden Science Magazine and De Universum. Previously, Nashanty was an astronomy Student Ambassador with experience in Public Relations and Communications. Dr. Alice Booth is an Astrochemistry PostDoc at Leiden Observatory. She earned her PhD from the School of Physics and Astronomy at the University of Leeds, and her BS in Physics from the University of Aberdeen, her hometown, in 2016. She is interested in the formation, composition and detection of (exo)planets, and her current research centers around the structure and composition of protoplanetary disks. In addition to her research, Alice is passionate about science communication, has been involved with the organisation Pint of Science for a number of years, and coordinated Leeds Pint of Science 2019. Be sure to follow Nashanty on LinkedIn (https://www.linkedin.com/in/nashanty-brunken-026514212/). You can learn more about Alice on her personal website (https://aliceboothastronomy.wordpress.com/), her professional website (https://www.universiteitleiden.nl/en/staffmembers/alice-booth#tab-1), and be sure to follow her on Twitter (https://twitter.com/Alice_Centauri). **************************************** The Weekly Space Hangout is a production of CosmoQuest. Want to support CosmoQuest? Here are some specific ways you can help: Subscribe FREE to our YouTube channel at https://www.youtube.com/c/cosmoquest Subscribe to our podcasts Astronomy Cast and Daily Space where ever you get your podcasts! Watch our streams over on Twitch at https://www.twitch.tv/cosmoquestx – follow and subscribe! Become a Patreon of CosmoQuest https://www.patreon.com/cosmoquestx Become a Patreon of Astronomy Cast https://www.patreon.com/astronomycast Buy stuff from our Redbubble https://www.redbubble.com/people/cosmoquestx Join our Discord server for CosmoQuest - https://discord.gg/X8rw4vv Join the Weekly Space Hangout Crew! - http://www.wshcrew.space/ Don't forget to like and subscribe! Plus we love being shared out to new people, so tweet, comment, review us... all the free things you can do to help bring science into people's lives.

https://youtu.be/8xFQGQsGurs Host: Fraser Cain ( @fcain )Special Guest: On March 8, the ESO announced in their Press Release ( https://www.eso.org/public/news/eso2205/?lang ) that a team of researchers from Leiden University, The Netherlands, had detected the largest molecule to date within a planetary disc. At 9-atoms, dimethyl ether is considered a precursor of larger organic molecules that can lead to the emergence of life. Tonight we are pleased to air Fraser's prerecorded interview with two members of the team that detected the molecule, Nashanty Brunken and Dr. Alice Booth, who will tell us more about this amazing detection.   Nashanty Brunken is an Astronomy Masters student at Leiden University with experience in Astrochemistry research. She is a writer at Leiden Science Magazine and De Universum. Previously, Nashanty was an astronomy Student Ambassador with experience in Public Relations and Communications.   Dr. Alice Booth is an Astrochemistry PostDoc at Leiden Observatory. She earned her PhD from the School of Physics and Astronomy at the University of Leeds, and her BS in Physics from the University of Aberdeen, her hometown, in 2016. She is interested in the formation, composition and detection of exoplanets, and her current research centers around the structure and composition of protoplanetary disks. In addition to her research, Alice is passionate about science communication, has been involved with the organization Pint of Science for a number of years, and coordinated Leeds Pint of Science 2019.   Be sure to follow Nashanty on LinkedIn (https://www.linkedin.com/in/nashanty-...). You can learn more about Alice on her personal website:  https://aliceboothastronomy.wordpress...  … her professional website: https://www.universiteitleiden.nl/en/... … and be sure to follow her on Twitter: https://twitter.com/Alice_Centauri   Regular Guests: Dr. Kimberly Cartier ( http://KimberlyCartier.org & @AstroKimCartier ) Dr. Nick Castle ( @PlanetaryGeoDoc / https://wanderingsci.com/ )  Dave Dickinson ( http://astroguyz.com/ & @Astroguyz ) This week's stories: - Apollo 17, Artemis & SLS. Internal volumes: Apollo: 210 cu ft, Orion: 316 cu ft, Crew Dragon: 328 cu ft. - JWST is focused! - Ingenuity extended! - Hot spots on magnetars. - How would a Mars sample return mission work?   We've added a new way to donate to 365 Days of Astronomy to support editing, hosting, and production costs.  Just visit: https://www.patreon.com/365DaysOfAstronomy and donate as much as you can! Share the podcast with your friends and send the Patreon link to them too!  Every bit helps! Thank you! ------------------------------------ Do go visit http://www.redbubble.com/people/CosmoQuestX/shop for cool Astronomy Cast and CosmoQuest t-shirts, coffee mugs and other awesomeness! http://cosmoquest.org/Donate This show is made possible through your donations.  Thank you! (Haven't donated? It's not too late! Just click!) ------------------------------------ The 365 Days of Astronomy Podcast is produced by the Planetary Science Institute. http://www.psi.edu Visit us on the web at 365DaysOfAstronomy.org or email us at info@365DaysOfAstronomy.org.

Dr. Jason Crowell talks with 46brooklyn Research CEO Antonio Ciaccia about how Medicare Part D has hidden the benefits of generic competition for Tecfidera, a disease-modifying therapy for multiple sclerosis. Read the full article at 46brooklyn.com. To hear the full podcast: https://www.neurology.org/podcast

Dr. Jason Crowell talks with 46brooklyn Research CEO Antonio Ciaccia about how Medicare Part D has hidden the benefits of generic competition for Tecfidera, a disease-modifying therapy for multiple sclerosis. Read the full article at 46brooklyn.com.

In this episode, Ryan and I go down various wormholes. We talk about the anomalies at The Skinwalker Ranch and other parts of the U.S., the UFO phenomenon, aliens, portals, DMT, society, and more! I hope you enjoy it.  Check out Ryan's work at ryanpatrickburns.com and spacewolfresearch.com Twitter: twitter.com/HERO_Paranormal Podcast: heroparanormal.com Please don't forget to shoot us a comment, rating, and follow us on social media! Check out our website at www.thejuanonjuanpodcast.com IG: @thejuanonjuanpodcast TIKTOK: @thejuanonjuanpodcast YT: "The Juan on Juan Podcast" Stake your Cardano with us at FIGHT POOL at fightpool.io! Thank you for tuning in! Full transcript: 00:00:13Welcome back to another episode of the 101 podcast. I'm your host is always one. And today we are joined by the one and only Ryan Burns. What's up bro? To be back with you talking about important stuff. Yeah, I when I texted you the other sent you a message on Instagram the other day. I was like what's up didn't really notice just watching the world burn just like everybody else and I'm like 00:01:06Yeah, so we can get into that while before we get started. Can you show me where people can find your work, social media website, whatever it is. You want to plug? Sure. You can find it on sea hero, paranormal.com. You can also find my books, the Utah UFO Ranch, and shapeshifter territory on Amazon and a little science project I have going on at space Wolf research.com., What's been the latest with that dude? Are you writing? Any new books? Did you ever write that book on consciousness? 00:01:42So not really I started it. I'm about a hundred pages in. I've got a couple of books that it it's really weird man cuz 00:01:54You know, I'm scared to release them basically, but it was a bad idea on the Vegas shooting. I mean as near as I can tell. That's a lawsuit waiting to happen and 00:02:06The other one like you said his unconsciousness. I'm kind of waiting to do that because I think I think In Our Lifetime we're going to crack we're going to we're going to kind of crack the nut to this whole Matrix Consciousness question. And I think it's dangerously close. So, you know, maybe I'm wrong but I'm just kind of waiting on that and I'm getting input from other people and working with people they have more more to offer to the big picture and and I've been having some really strange but yeah, a lot of strange things happening on all fronts, for sure. I think we're getting closer to answering this whole Matrix deconstruction. We're picking away at it like literally picking away at the nuts and bolts of it. And you can tell when you start doing that bad. 00:02:55It's aware whatever the universal Consciousness is, or the program or the alien, artificial intelligence. Whatever you want to call it. You know, the higher power, there's many names for the same. 00:03:08Mystery and it's it is it becomes aware when you start pulling at the threads of reality? Absolutely. 00:03:19That concept of threads, I just did an episode. 00:03:25With a friend of mine, Jeffrey from the functionally dysfunctional, show. And yeah, we talked, he was an ex evangelist and he talked about how they would all about thread and eventually gets the point where they keep pulling at the thread and it's all gone and they figure out it's all bullshit and I can't imagine the feeling of putting everything you've had until 1. 00:03:53Until one thing, whatever, that may be a hobby career, whatever it is, and then figuring out that in the end, it's all bulshit. Right? And right, you're talkin about. 00:04:07Do you think they said the same thing in the seventies and in the 50s and in the twenties? You think where they were? Hey, I think we're going to crack this. I think the other you think people were as open to that back then and then especially well maybe in the fifties I would say. Cuz of all the Roswell and all that bush that was going on. Then you think they were saying the same thing. Like maybe we're going to crack this code. Oh for sure. And I think we probably have cracked the code multiple times throughout human existence and then there's another great reset, you know, and everybody's left scrambling in the Dust trying to find 00:04:47Tidbits of information to start over. It's just the Human Experience. And you know to give you an idea like this is just a, for instance, an example. My my wife is a very, very skeptical, reasonable. Not. Woo, woo, person at all. Come to the club, bro. That's a good litmus test to have a mate or a partner like that. The kind of, you know, checks you and caress you and keeps you grounded. And, you know, I had a, I had a call from a caretaker at this science project, I have going on and and he, he told me a situation where he woke up in the middle of the night. He heard, you know, what the voice. 00:05:35Say hey and he woke up and then he hurt his car. Alarm, go on outside. He went outside. There's nothing out there. 00:05:43Needless to say he's in an area of a lot more High strangeness than I am at my home. And the caretaker went outside turned off, his car alarm came back inside. 00:05:54Again, same thing happened again. He went out again. No, Critters around the car. Nothing. So something was trying to engage with him. I told my wife the story. She was like that. That there's a lot of thinking this would be just south of it within a golf swing is the way I like to explain it to throw a rock at it. You can pretty much there's no part of that Rance. You can't virtually see from this property. So 00:06:24It's it. Pops close enough and it functions. Anyway, what went down as well. Fast forward, just a little while and she was sitting, this is just a couple days ago. She was sitting in the kitchen with my two children, and I was coming down the stairs and I heard it as well. 00:06:50And it sounded like a loudspeaker in the kitchen and it was a woman's voice. And she said, hey. 00:06:57Oh, okay. 00:06:59And then it went off. What the heck was that? Knowing? You think maybe I'm getting chills right now, bro. Yeah, it freaked me out so hard because nothing we have would do that and it it you know, it got everybody's attention. It was loud enough. It sounded like the p a in a school and it just sounded like, you know, The Truman Show like, oh my gosh, all sudden, you know, it was through the glitch of some sort. And you know what you think it is and it's a fine point where you don't have an explanation much like Ariel unidentified phenomena and you know things you see it in the in the trees like cryptozoological variants, when you don't have, when there's not a readily-available real explanation for something, you start to question reality, when you start questioning reality. I think you open yourself up to these like matrix-like issues and 00:07:58And open to navigate, you know, they Pete be unclear Waters of what our existence really means. 00:08:08You like that clip? I posted it today. I said the DNA some NPCs are glitching out. There's been videos going around of people. Just acting strange is very strange. Where 00:08:20Maybe some people or entities or whatever. It is. Our non-player characters are just here to fill in the void to have some sort of interaction which is kind of scary. Because are you an NPC, Ryan? Are you here? How we are? We were conducting Witchcraft and I were talking through a screen through this thing and it's being transmitted to you on some other place at it. There's a different time zone over there. This is fucking wild, right? We're literally on. Scrying mirrors, utilizing Technologies. We don't understand. That's the thing fully engaged as if, as if ya. Are you real or are we in a 00:09:11Black Mirror episode. 00:09:13Are we in because it seems like it, right? And in, and right now, I'm in a group chat where we're having. 00:09:21An argument about the reality of Statistics, right? You know what I'm getting at a different numbers and things that are going on in the world right now that I'm honestly I'm tired of talking about it. I like talking about other things, other topics that are cool like aliens and shit right in in in Bigfoot, but people are so sucked up into the thing that's going on right now. Everything and it just makes me think what else is going, on. They're distracting us from because anything that happens. The number one thing is a what's the what's the distraction from what's actually going on that? They don't want us to see that? Hey, this is just a asiop type of thing and 00:10:02I have a friend of mine was very passionate about the Awakening of humanity as a as a conscious. And so it's, it's happening, is happening right now. It's about to happen. Is it really? You know what I mean? Is it would you, would you be okay with it? Not happening during your lifetime. 00:10:19Oh, totally. I just think we're that unlucky Bundt or lucky Bunch depending on how you see it that. 00:10:27It's happening. I agree with your friend, at least in some view because, you know, you talk to people on that Consciousness to who have had near-death experiences and they, you know, it's real is our reality scenes without question. They almost always 00:10:49Relay, their experiences being more real than this one. This is a blurry. 00:10:56Blurry. Muddy comparison to what they experienced when when they have. 00:11:04These out-of-body near-death experiences. So what we are experiencing now, is it as real as it is seems very blurry muddied? And not as authentic as the experiences which are encountered in that particular Consciousness and 00:11:27Getting bits and pieces here, and there will have like you do, you know those moments of deja vu or it seems again more real than it's a nebula in space and time. They totally and I don't know if I've ever asked you, but have you ever done. Give me a second. Dimethyl. Trip to me. Her done DMT. 00:11:47Very interesting, you know? No, I've never done the actual drug. Now, that being said that being said that the little science experiment experiment that myself and others are engaged with. I sold a portion and I don't know how much to tell her because we're dealing with some pretty major. 00:12:11Stuff we're doing out there and I hate when I have you on the show you talk about it cuz you can't talk about it. Yeah, man, I'll just say it. I'll just say it a, a partner of mine and I only stayed partner Lexus. I can blur whatever whatever you want out. After the fact, I'll say it in the correct format. I sold the Western portion of space Wolf research, which used to be twice the size. It is now to a silent partner who does not want to be named. He doesn't want to be a part of 00:12:45Anything yet. Just screams reptilian to me just right now. He's a great guy and we have very similar Mutual shared interest and I wouldn't have sold it to anybody who did not have the same feelings about the land and what its meaning is to humanity and he has, for lack of a better word been bringing Consciousness technology to the area. 00:13:14Which is. 00:13:18Able to reconstruct the DMT experience without the use of drugs. So I'm right here on Tusk by any chance know, but he's definitely a musketeer as I am in that sense that he 00:13:37This. This Consciousness technology dude. That's a wild man. Yeah, it's a lamp of sorts and I've heard about that on Joe Rogan with a strap you in and they were able to put pulses of Light. Have you tried that? I don't want to get into that. But my experience is not as important as it's very important on this podcast Ryan. Well, I've I've delved into other areas like 00:14:07When I, when I will go to the property and yeah, so so there's there's stuff going on. But when I've gone to the property, I typically will. 00:14:19Try to commune with the land or engage with with the land itself and do so on a very. 00:14:30Empty, I guess level not coming in with any precognition or expectations or anything along that just kind of shift to just a receptor. Just neurological receptor. That's taking it all in and it's hard to keep your mind empty. It's almost like a meditation, but it's hard to keep your mind empty without you know, that human loaded precognition. Where you get all this is good. This is bad that I don't know. It's like, who cares what we think? And I try to go in with that more and more like I just in intelligence and Observe and Report idea and and it when you go with that, observe and report, 00:15:14Mindset, I feel that it goes a lot better or like Oriental cultures will often, you know, call it turning your mind into an empty bowl and then it is filled with the rice or the whatever comes out of that instead of instead of optioning to command our own. 00:15:35Feelings on what happens. And so the Observer when I can say is the Observer Super T, in areas of high strangeness and what you bring to the table is super important. So it's important to like literally show up at the table with nothing in your hands and 00:15:54Just be open to what it wants to send you and do they know for example, if I was to go out there would they know I have a podcast about this year? 00:16:05It is yeah, man, it's whatever this intelligence is. It is like what scientist before me have called it, namely a precognitive. 00:16:20Intelligence. So it 00:16:23knows ahead of time. What you are going to think. 00:16:31bro, this shit balls on my ended because 00:16:38that is scary as hell. That is very scary and Ryan why you think and correct me if I'm wrong, but this 00:16:51Collective Consciousness or entity, or architect program, or whatever it may be. 00:16:58Why is it that my whole thing is why is it so strong and concentrated there? I know that there's certain minerals and rocks and different things that are only found in that area in the entire world. But are there other places such as the Skinwalker Ranch, with the same aspects may be in Australia or in China or in Japan or around the world. Does that have to do with the ley-lines? You think is this word? These people, I mean, and they can correct me if I'm wrong. This is where these people build their sacred temples and establishments for religious. 00:17:38For religious activities. Know who am? I am I wrong in that term? Because a lot of these places that they tear down and they build churches on top of, you know, maybe ancient Pagan sites, they build churches or even establishments on these places. Like, what's his name that that one that one guy who, who the super billing? I forget his name. Is it something Bloomberg or something like that? Whatever his last name is where he restored an old Temple of Jupiter or Venus and he made it like this crazy technologically advanced building and he's a super billionaire, but he restored a a temple to I believe it to its in Baalbek or Lebanon some place over there. He rebuilt this Temple. 00:18:22And just checked it all out. And it's like, what could you possibly want with this sort of thing? A, my whole obviously, Skinwalker Ranch is famous, but are there other places that you're aware of that are on par with the quality of encounters? 00:18:43Such a Skinwalker Ranch where you able to be like, hey, there is a correlation between these two. 00:18:51Yeah, I think that there are multiple sites and locations that are similar For Me, The Fray. I mean, homemade Skinwalker to me. So for me, The Fray is that location, but I've gone to other locations that have similar phrase or bales that seem to be glitchy Sedona what parts of Nevada and the desert here. There's multiple locations. Now obviously Skinwalker is very close to the 37th parallel. And like you said, people that will argue that ley-line. 00:19:37Theory. It it's it's pretty obvious to me that there is some legitimate background to that. When you went when you really start to look at, as you said, we're both indigenous and even more. Modern Lee people seem to see this High strangeness, I mean back in 1776 when father Escalante and Dominguez, we're coming through mapping Trails for the Spanish. They were encountering the same stuff but our government and twos is priest under him which they were booked Roman Catholic. Priests Dominguez, his priests under him. They were they were a pair of priests that the Spanish sent to Matt. Basically. Yeah, well, 00:20:30The theory was that the priest had a better chance of making it alive and they did they would basically make map these routes that the Spanish would later use for gold and it's known as The Old Spanish Trail now, but yeah, when they went through the Basin, they reported very similar things in the sky and the ground and absolutely unearthly. 00:21:03apparitions, so, 00:21:06It's not it's not something that is new. But it the definitely they were communing with the same type of thing that our current intelligence, both government military through, you know, many Freedom of Information Act requests and and and actually be the New York Times coming out and straight up saying it. The advanced Aviation threat identification program as well as he Advanced Aerospace weapon system, application program, a tip and off app. We're both strategically held for lack of a better word. A tip for sure was held right there at Skinwalker. So it's, you know, that is the program that Lou Elizondo claims to have been in charge of and 00:21:53It it was investigating something for a reason, something that seemed to be a threat and that they could not pinpoint. So it's a, it's a very, you know, top scientists with the Bearcats are very interesting and intriguing mystery that continues. They have, since disbanded the program, renamed it, but it is still very much alive and the same players other than Lou. Some of the same players I should say, are still at the Forefront of investigating things that are able to Traverse for lack of a better word, portals wormholes. You know, they have, they definitely have a monopoly on whatever these intelligences are seem to have a monopoly on being able to 00:22:46Blink in and out of our reality. 00:22:51woman, blow my fucking mind with this stuff where 00:22:56Is that is that the one that Bob Lazar was talking to a being being a part of? Or is that a different program? That's a different area. I know, dude. It's so interesting. You mention Bob Lazar because 00:23:09Okay, you just leave him by the way. I'm sure you. Do you believe him 100% do? Now I wouldn't. But I have some friends close friends who are in communication with him. 00:23:22And it's a great example of how the government can come in and change your history and make the public believe anything they want about you. 00:23:31He very much worked at the places. He said he worked and interesting Lee enough where the streams cross with with the Uintah Basin is how can I put this? Okay, I'll just I'll just tell you what I'm told by very inside in, I just want for me. I love myself. I would never kill myself and I love the United States of America and Giovanni Patriot. I'm a patriot exactly. 00:24:08A scientific expert who has very credible information. 00:24:17Told me recently that one of the element 115 spent fuel rods that were found were found 500 feet from a property boundary from my property. Boundary do, what these purported fuel cells. They were appear to be metal rods and they are what the national about mids Bigelow scientific team, the National Institute for Discovery Science. Their scientists deemed that these were reportedly 00:24:58fuel rods, for 00:25:01Flying saucers or reverse-engineered craft, which Falls completely in line with what Bob Lazar said? Years ago, that this element 115 was, in fact, an element that just because it was not on our periodic table, then it is now. But at the time, it was not on our periodic table and had not been proven to be stable enough to be on the periodic table ever. Since then it has been proven to be stable, at least in a temporary sense enough to be on our periodic table. And that these reversed engineered crap or saucers for lack of a better word were using these fuel rods as fuel. So they would somehow convert that into energy that could 00:25:50Make them not only anti-gravitational but you know go forward backward up down any way they want and and and the element and in discussion as a Muscovy mm, chemical element with the symbol m, c and atomic number 115. Is that the right one element 115? It is it's, it's been named a few things. And Bob, Lazar first came out with this information. Everybody scoffed at him and laughed at him and they have since sort of retracted that when it was proven to exist. So either the guys talking out his butt or his butts really smart because it figured out this element existed long before it existed and he he is very smart. He's a very knowledgeable individual, he's not talking out his but unfortunately there is such it's almost like a movement lately that is just out to the bunk anything that has to do with going against the 00:26:50Armand reality that we know exists. And you know, that's always sort of been the case, you know, when 00:26:58People were saying the Earth was round and the status quo was saying, it was flat. They would kill you. So, a lot of things have not changed, and it seems that time is the factor that changes it. Because if you just wait long enough, these things come to fruition and then everybody back steps and Rio, you okay? Well, we accept it now, but I can do at that time. If you, you know, this is centuries ago. If you claimed the world was round, you know, you were a heretic and you were burned at the stake, whether you were right or not. It's like that. That part of, I'm reading Tom hatches book LSD, the Wonder child and it talks about when they exposed. 00:27:45Chimpanzees tile SD there, wouldn't show any discomfort and they would release them back into their society and the other chimps would ostracize them. And because they were following, the hierarchy of of pretty much their simulation, their world. He was going against the grain, and he would be punished almost like what's happening right now, right? Where if you don't follow certain Norms, your outcasted, this is happened before. And I looked into something, dude, that blew my fucking mind yesterday, and I couldn't believe it. I couldn't believe. I had to look deeper into it. 00:28:24I posted the clip on my Tik-Tok and Instagram and it was about the Third Reich and the end of the nurses that they had their, they would literally kill babies. They would hold the babies, that would put them outside to get frostbite. They would kill babies. These people doing these horrible experiments and 00:28:43The idea of eugenics which is presented in Plato's The Republic Wright. Plato was one of the first people to come up with this idea of selective. Breeding only the higher-ups could read, you know, it and keep the bloodline pure. 00:28:59The book, The Republic was looked upon by a Martin Luther King Jr. And the Nazis write two separate movements. They both looked at the same piece of work of of of 00:29:13A literature which comes to show you the what Plato talks about, in that work, the Arts speak to people on a deeper level than just, that's why he wanted to limit certain frequencies, right? That's very important. Wanted to limit for certain frequencies from from that because he thought that it would give a person hope they would have rebelled against the system and break out of potatoes to the cave right? Break out of the cage. When you come back to tell them. Hey, there's another world out there. They fight you. No, no shut the fuck up. Going to sit back down. 00:29:46And when it comes to this sort of thing. 00:29:51I also my my, my breakthrough was that apparently the idea of eugenics actually came from the US and the Nazis adopted a law trying to compete with the US. And if you look into it and then early 1900, the US was sterilizing. 00:30:12Mentally handicapped, people over 400,000, people were sterilized, who were mentally handicapped, or whatever. It may be, some sort of disorder that they had disabled such as the Nazis did with the gypsies, the polka polish, all these different groups of people, ultimately that the Jews as well. And that's how they start you with it. They started with hey, these people are sick. We're going to take him to these camps, to make them feel better. We're going to take what's happening in Australia right now. They got fucking concentration camps out there. And guess what? They can't do anything. They have no guns. They can't stand up to their tyrannical. Government. Why? Because they gave their guns up, back in the 90s and this is what happens. And I don't feel like this is going to come knocking on our doorstep, but it's just something to keep open because well, never say, never right? I saw your face Never Say Never 00:31:06It is scary. And when we talk about the world burning, we see this but it blew my mind. Dude. I was like all the Nazis weren't at the Forefront of this. I said, wait a minute then who was all the US? 00:31:17And in night in the 1970 that passed laws and everything in regards to this and I said, there's no fucking way and there would be articles that would come on and pay. The Nazis are beating us or hey, the Nazi was saying we have to compete with the US. 00:31:33That is disgusting because I talk to, I talk to somebody recently about this about how not too long ago. 00:31:40We were racist as fuck for as black people. Right towards people of color, that we were super only a person's lifetime or away. 1940s 1950s. We just came out of of doing that. And there still racism in this world today that we have where that's why I feel that. 00:32:02I don't, I don't know if if 00:32:06That there needs to be some sort of cleansing, right. Of like this this and I want to be careful the way I word it not but some sort of 00:32:17Consciousness cleanse, I don't know, you know what I mean, like maybe knocked out all the bullshit because my whole thing is if people was weird open up their eyes and realize, hey, this is all bulshit this reality that what is all bulshit. Right? If we're able to break out of that thinking and break free of the chains of the of the materialism and in consumerism and all this other bullshit that's taking a hold of everybody. I think we'll be able to move up that next level of being able to live in harmony, but the powers-that-be these reptilian us. 00:32:53people, these overlords 00:32:56They feed off that energy, right? They feed off that negativity in that lower vibrational vibrational energy. And that's why I talked about the Saturn time Cube about how Saturn is ruling, is the demiurges rule in this reality, right? And in The Matrix, these all that they're coming out with a new Matrix movie. 00:33:17I love it. I love it. I can't wait to see it. Cuz I wonder what they're going to do is lie,. I was having these dreams and speaking of Dreams the other day. I went to Coral Castle at Wild Place. Dude. I don't know how this guy did it. It makes you wonder these people who who its technology. But when you see the things that they're able to do, how you how you mentioned before, and have references numerous times on my podcast, how you said, when you put certain stones in certain positions, in certain ways, you are able to send a message. What was that place you were at? That was like a spiral. What was that? 00:33:55It's a pic. It's a location known as rhyolite Nevada. It's an abandoned. It's actually at open-air Art Museum. Now, however it is and it is basically a ghost town that used to be very functional and the artwork there and like you saw the the spiral very interesting energy out in the middle of nowhere. I mean it it literally took me an entire day just to get to the location and but that's like what I like to do, but it's very real of these repeat these areas function in ways that and I agree with you 100% like Coral Castle in 00:34:42These Elemental Technologies. 00:34:45By the way, I'll a line runs through there, too. By the way. 00:34:52Run. Are you cut out? I can't hear your audio, dude. 00:34:57Did you meet yourself? 00:35:04I can't hear you. Your likes is the archons at work, dude. 00:35:11Are you go? Yeah. Yeah. There we go. 00:35:14The archons at work. Did you go? That was weird? 00:35:20To my point. I think a Ley line runs through the Coral Castle. By the way, just saying that out, Elemental Technologies, like you said, running placing stones and Elemental Technologies and certain 00:35:40designs. 00:35:42They continue to work whether the Wi-Fi goes down or not. So we're other forms of technology can glitch out and just couldn't be completely erased from history. I honestly believe that there is an elemental technology that can be utilized, that will continue to both receive and 00:36:05Put out energies and the dysfunction regardless of your temporary technology. Like the ones were using. The, the interesting thing is 00:36:19There are. 00:36:23How can I put the scissors? It seems to me that there's always been entities that act as these? 00:36:32They just kind of hold hold stuff together. Hold the Matrix together, like almost like a Metatron, like a Metatron, like a Baphomet, something coagulating, at dissolving or Metatron, just basically making sure the program is working and functioning because the last thing that the in the lizard tank because I'm half wizard. I mean, we all, we all live within the confines of this reality, which is based on a monetary fiat currency and just buy that very engagement with the system. We're all pretty much half lizard. Anyway, you have to worry about, you know, paying your bills and stuff, you know supporting your family and things of that nature which are not very human Tendencies. These are these are, these are things that have been imposed upon us and not necessarily go with the core of our being. So, 00:37:23When, you know, and I know when I see people that are wealthy Elites, I call them lizards and yet, do I wish I was a lizard. I wish I had more money in the bank. I wish I had more stock on you and I know a few lizards to, but when you hang out with them, door, like normal people aware in touch and conscious of this. 00:37:51Financial gain, which is not a bad thing. However, I think it can become a bad thing. It's, it's like it and, you know, there's wealthy Elites and then there's worth wealthy Elites. I remember guiding Tiger Woods down the river and he was the first billionaire I ever met. 00:38:12It might be, I don't know if it is or not. I may have left that out. But, you know, he was the first billionaire that I ever met, and you just a normal guy, but you can tell that it gets to you and I've met billionaire since, and they definitely have something that we don't have, which is a lot of money on a paper. A lot of pieces of paper and with that literally comes an air of 00:38:43Entitlement and it's not a bad thing. But, you know, much, you know, much like the guy that has to work 9 to 5, and then you see the guy that drives by in the 00:38:54Limo who hasn't worked a day in his life. There is, it's not arrogance, but there is a superiority complex that comes with it. Whether you want it to or not. It's the same feeling we get, you know, when you see these these videos online of like send a dollar a day and you'll feed three children in Africa. You see this stuff and I'll send you like, holy crap. Have it ready. Yeah, it speaks to you and Kyle. Thankful. Yeah. Yeah, you're very thankful for your position or just living in those countries. I mean fathomable to most of the world. So 00:39:34You know, it it's one of those things that I can see how that power would propagate and evolutionary in an evolutionary sense, propagate along Bloodlines and exponentially recreate itself to bigger and bigger proportions. And you would end up with these extremely unfathomably, wealthy Elites who only operate on that particular system of power. And I think that's what people mean when they're talking about lizards, but, you know, everybody goes down the super like, where's their tail? If you are cold-blooded enough, no punishment upon intended, I guess cold-blooded enough, to only concentrate on the absorption of power like, a sponge. It's pretty amazing. I'm sure how far you could get in life, and 00:40:29I mean, you probably would not care about those around you. Look no further. Dude. Is it, is it me? Or does it feel like Jeff Bezos came out of nowhere? 00:40:40I would totally like, where's his family, who, who was under him before him? You know what I mean? Is like this, dude just popped out of nowhere and you're saying, while the sky's the limit for the literal sky is the limit for these people that they're launching their. It's almost like a pissing match now. It's how long can I be in space now? How long, how much longer can I be than you or how much higher can I go in you when they were launching the new? The SpaceX, the first crude then they're like, hey were were well past a hundred kilometers at this point almost like doing that job over at at these other guys. The guy from Virgin Galactic nnn Jeff Bezos where they only went up to space for two minutes, but these guys 00:41:23I've always said it where they know when you know, you're in a game. 00:41:29You're going to play differently.

Welcome to The Hydrogen Podcast!In episode 025, Could Mexico be the next hotbed for green hydrogen? A joint project between Los Alamos National Laboratory and Oberon fuels receives Department of Energy funding to produce renewable hydrogen from renewable DME. And just what is this, RDME anyway? All of this on today's hydrogen podcast. Thank you for listening and I hope you enjoy the podcast. Please feel free to email me at info@thehydrogenpodcast.com with any questions. Also, if you wouldn't mind subscribing to my podcast using your preferred platform... I would greatly appreciate it. Respectfully,Paul RoddenVISIT THE HYDROGEN PODCAST WEBSITEhttps://thehydrogenpodcast.comCHECK OUT OUR BLOGhttps://thehydrogenpodcast.com/blog/WANT TO SPONSOR THE PODCAST? Send us an email to: info@thehydrogenpodcast.com

This week, Drewby and Yergy review the mysterious case of Gloria Ramirez, a cervical cancer victim, whose brief but dramatic emergency room stay  in Riverside, California and untimely death baffled the medical community in the mid 90's due to medical workers falling very ill just by being in the presence of her and her body, prompting concern that her body had turned into a chemical weapon, and this was further highlighted as a possibility due to her alleged self-administration of Dimethyl sulfoxide (DMSO). Later the county health department attempted to make the claim that the whole thing was simply a case of mass hysteria, as many of the workers who fell ill were women. The case was further complicated due to multiple autopsies with the majority done after her body had already badly decomposed. Several conspiracy theories have since arisen. We also discuss the need for continued funding to clinics that specialize in reproductive health in order to detect, treat, and eradicate diseases such as cervical cancer and HPV, the leading cause of this fairly preventable disease.  Join Our Facebook Group to Request a Topic: https://t.co/DeSZIIMgXs?amp=1 Support Our Patreon For More Unreleased Content: https://www.patreon.com/themiserymachine PayPal: https://www.paypal.me/themiserymachine Instagram: miserymachinepodcast Twitter: misery_podcast Discord: https://discord.gg/kCCzjZM #podcast #documentary #truecrime  Source Material: https://www.rxlist.com/dmso_dimethylsulfoxide/supplements.htm https://en.wikipedia.org/wiki/Cheyne-Stokes_respiration https://en.wikipedia.org/wiki/Death_of_Gloria_Ramirez https://www.discovermagazine.com/health/analysis-of-a-toxic-death

Welcome to The Best 5 Minute Wine Podcast. I'm your host Forrest Kelly from the seed to the glass. Wine has a past. Our aim at The Best 5 Minute Wine Podcast is to look for adventure at wineries around the globe. After all grape minds think alike. Let's start the adventure. We go on a different journey. We don't drop into a specific winery. We are speaking with Todd White, founder, and CEO of https://www.dryfarmwines.com/ (Dry Farm Wines). There are 76 additives approved by the https://en.wikipedia.org/wiki/Food_and_Drug_Administration (FDA) for use in winemaking. Four of them are quite https://en.wikipedia.org/wiki/Toxicity (toxic). The most toxic is https://en.wikipedia.org/wiki/Dimethyl_dicarbonate (Dimethyl dicarbonate) marketed under the brand name https://velcorin.com/ (Velcorin). And it's used to treat https://en.wikipedia.org/wiki/Brettanomyces (Brettanomyces), which is the most common bacterial fault and why it's highly toxic. If you go to Dimethyl dicarbonate on Wikipedia, you'll see how toxic it is. Okay, I did look it up on https://en.wikipedia.org/wiki/Main_Page (Wikipedia) Dimethyl dicarbonate. It is classified as toxic. The first warning is harmful if swallowed. It's also toxic by inhalation. It causes burns. Well, that's not really something that you want to be ingesting, especially if you're going to be drinking it over a lifetime. Now, the public doesn't know about these additives some and in fairness some are natural. Many are not. The wine industry spends millions of dollars a year and lobby money to keep content labeling and nutritional information off of wine labels. So you don't have any idea how much sugar is in the wine you're drinking. To people who care about their health sugar is a very important thing they want to know about. So our job is education. The wine sells itself. Now, that brings up the question. Dryfarmwines.com because of these strict guidelines. Why don't you carry any domestic wines? The reason being is that there are not really any U.S. wines that meet our criteria. And so you talk about U.S. wines. There are a number of difficult criteria for them to meet. And they're in the order of dry farming. So almost all domestic vineyards are irrigated. Number two, alcohol. We don't accept any alcohol over twelve and a half percent. And that's lab tested by us. Alcohol stated on a wine bottle is not required by law to be accurate. So we did lab testing for alcohol. So there are virtually no U.S. wines made that are twelve and a half percent or lower in alcohol. Virtually none. And then the third most prevalent reason that a U.S. wine wouldn't qualify for our program is cost. So all of our wines sell for exactly the same amount. They're $22.00 a bottle. There are no U.S. wines that meet our criteria of organic or biodynamic dry farming and alcohol that cost anywhere close to $22.00. The primary driver on a domestic wine price is going to be the cost of the land. All of U. S. vineyard costs are just so much higher than the capital cost of land in Europe and places like https://en.wikipedia.org/wiki/Beaujolais (Beaujolais), where anywhere across Europe where most of these small family farms that produce natural wines that we buy wine from, most of them are multigenerational landowners, that they don't have any capital costs. We're constantly being told to hydrate, drink more water. That philosophy does not transfer to grapevines. There are a lot of reasons not to irrigate a grapevine. And in most of Europe, it's against the law to irrigate grapevines. Europeans have been making wine for over 3000 years. Now what we know, the moment you irrigate a great vine, you fundamentally change the physiology of how the fruit ripens. It also makes for a lazy vine and the fruit is actually less healthy. So the https://en.wikipedia.org/wiki/Phenolic_content_in_wine (polyphenols), https://en.wikipedia.org/wiki/Flavonoid (flavonoids), native https://en.wikipedia.org/wiki/Flavonoid (flavonoids), and other...

Crankiness from being overheated and thirsty or dehydrated may be bad for health, and for a good night's sleep - which might be part of the cause of the health risks. Our brain is cleared of toxins during sleep hours. During normal sleep the body and brain are cooler than during awake hours, and the brain is smaller in size which allows more fluid movement and white blood cell activity. The white blood cells' autophagy and apoptosis functions are more active in the brain during sleep hours. Autophagy and brain health was a topic discussed in the Hangry and Hanxious Part Two episodes. Insomnia tips - cooling the forehead with a reusable freezer gel pack wrapped in fabric may help if insomnia is a problem. The body normally cools down before sleep and it doesn't happen as well with insomnia. Dimethyl-glycine (DMG) is an amino acid that has inhibitory effects in the brain. Taking a 1/2 teaspoon of the powder supplement DMG in a glass of water before bed might help slow down the brain activity and temperature to a point where relaxing and falling asleep might be easier. This episode is in three parts. The Trailer includes an overview and hormones that may cause crankiness. The Main section gets into more detail about the potential negative effects for brain health of being chronically overheated, dehydrated, and unable to sleep well. The final Bonus section includes a few tips that might help you get to sleep if insomnia is a problem. Image quote: "Be patient where you sit in the dark, the dawn is coming." - Rumi Email - jen@peace-is-happy.org Twitter - @denutrients Webpage - peace-is-happy.org/how are you feeling Transcript/Reference list Additional information and references about sleep, and the cooling strategies mentioned in this episode are included in two posts: Glymphatic system – yes- sleep helps protect against Alzheimer’s dementia Sleep and Health. Disclaimer: This information is provided for educational purposes within the guidelines of Fair Use. It is not intended to provide individual guidance. Please seek a health care provider for individualized health care guidance.

In the first segment, Dr. Stacey Clardy talks with Dr. Mathias Buron about his paper addressing the comparative effectiveness of teriflunomide and dimethyl fumarate. In the second part of the podcast, Dr. Jason Crowell focuses his interview with Dr. Joanna Hellmuth on the rise of pseudomedicine for dementia and brain health.

Dr. Mathias Buron discusses the takeaways from his paper the comparative effectiveness of teriflunomide and dimethyl fumarate.

DMS is a commonly cited off-flavor that many claim tastes like cooked vegetables and, while appropriate in small doses in certain styles, is typically avoided by brewers. In this episode, contributor Malcolm Frazer joins Marshall to take a closer look at this curiously corny compound and discuss some interesting exBEERiments they've performed on the topic! | Relevant Articles | Lid On vs. Lid Off During The Boil xBmt: http://brulosophy.com/2016/10/31/the-boil-lid-on-vs-lid-off-exbeeriment-results/ DMS Off-Flavor xBmt: http://brulosophy.com/2016/09/05/off-flavor-series-pt-1-dimethyl-sulfide-dms-exbeeriment-results/

Injury is inevitable, unfortunately. It is part of the human condition. If you train properly, using body weight, perfectly paleo types of exercise, you won’t become injured from that. UNLESS you overdo it, which can always happen. Overuse is the number one cause of injuries- just look at me! A few weeks back I posted about being injured from an overuse injury, painting a barn of a garage for just too many hours, and inflaming the bursa in my shoulder. I also did other jobs that overworked that same joint, and the result has been a few weeks of rehab. I used the occasion to research what worked and what didn’t, so here we go my paleo friends! First of all, remember that it is not the end of the world. If you work out each and every day as I do, (and as I recommend for all creatures that exist on this earth), it is really irksome to have one part of your body that just…hurts. But, you just work around it- you exercise other parts of your body, and only work the hurting part through a limited range of motion (if you can) that doesn’t hurt! Of course, sometimes you can’t work, say, one arm at all for awhile. Don’t sweat it- just rest it. But, there are some other things that will help dramatically as well. Putting a cold pack on the injured part (in my case this time- my right shoulder) is great. To alternate that with a warm, moist pack is ideal- this promotes blood flow. I would alternate cold with hot- in the shower is one great place to easily do this. But what about later, as you relax in your easy chair? A bag of frozen vegetables is great to rest on your shoulder for awhile, but you can also get a re-freezable cold pack inexpensively, some even have straps to attach them to your body part. But how to alternate with hot? I have the perfect, although somewhat embarrassing answer- Get a disposable diaper! That’s right, you can get about 30 for a few dollars. (Luckily, I have a new grandson who could use the rest!) I just took off the cold pack, and moistened the diaper from the faucet. Then, I microwaved it for a minute… hot and moist- perfect! And it attaches easily to any part of your body!! Just don’t forget, and answer the door with a diaper attached to your shoulder- very embarrassing. But the best solution of all, besides gently stretching and alternating heat and cold?? DMSO, or Dimethyl sulfoxide, is almost a miracle. Anti-inflammatory, it penetrated the skin and goes right into the tissues beneath, immediately relieving pain. It’s not really a drug, it is a solvent byproduct of the paper industry that has been known of since the 1950’s. The fact that it cannot be patented pinpoints why the pharmaceutical companies are uninterested. It can’t be patented. There is no big money to be made here! Sad but true… It is also a potent source of sulphur, which is a substance that is wonderful for any musculoskeletal ache or pain. Think of sulphur-rich hot baths, that people go to to rejuvenate their bodies. DMSO is a hot springs bath on steroids, that you just rub onto your body! Anyway, for arthritis, bursitis, and any ache, strain, or pain- it is a miracle! Cheap, too- it is one of the veterinarians’ main tools for treating animals, mainly race horses that have been injured. Remember: even though the FDA might say that the effects from DMSO are a “placebo”- well, placebos don’t work on horses, do they? So, get yourself some DMSO- 70% concentration is best, I like it in a cream form for easy application. Under $20 for a miracle drug! Just like white willow bark, this is something you should always have in your medicine cabinet!  

We all know what it’s like when all is going great- morning workout, great breakfast with a green paleo smoothie and coffee with coconut oil and cinnamon, cloves and chocolate powder- and then off to a productive day! Life can be wonderful… But, it can also be quite stressful, as we all know. I know personally, because I got injured! While not the end of the world, injuries can be very stressful, both mentally and physically. Just know that injuries are, periodically, a real part of leading an authentic, athletic life. Just sequestering yourself and perpetually “being careful” about your body is a fast track to the nursing home- our bodies expect, and need to be stressed, and to do hard things at the very edge of our abilities! In my case, I just overworked. This is the same as overtraining, which I have seen time and again- someone gets good results with strength training, and thinks “Hey- if I just do even more I’ll be awesome!” Well, then they wind up with black and blue bruises on their triceps, or wherever, and become weaker, not stronger than before- and also injured in many cases, which is even worse. I know the dangers of overtraining- in fact, my podcast and blog are kind of a mantra against such overtraining- forget the heavy weights, do bodyweight training, train your tendons and ligaments before your muscles exclusively- be cautious yet train very hard! I know this so well, in my training… But, when I get caught up in physical work, well, I get too caught up and forget. I just want to get the job completed! And so, when I painted my barn of a garage, I just kept going, and going, and going! Then, I wanted to construct a playhouse for my grandson, and kept working on it, in very confined spaces, with a big power drill that contorted my body (and shoulders) into uncomfortable angles. These two activities took up 4 whole days, on which of course I did my workouts before starting work! And then, my mower deck needed repair- I crawled underneath, and spent most of another day, doing that… My right shoulder was fried! Dark bruises formed around the perimeter, and I could not really lift my right arm above my head. Me! PaleoJay, exercise nut and functional fitness espouser- victim of my own cautionary tales. Ah, such is humility. It happens. We are all only all too human, and afterwards we need to get up and start to repair the damage. And, it is a learning experience: I learned about DMSO, which is Dimethyl sulfoxide. You can get it in a cream form, or liquid, and I have been rubbing the cream on my shoulder a couple of times per day. It is anti-inflammatory, and enhances circulation dramatically- in addition, it relieves pain really quickly as well. DMSO has been used by veterinarians and horse race trainers for decades, along with some enlightened medical practitioners. I plan to continue to use it, and explore its possibilities. Of course, the FDA disapproves, as they disapprove of anything that can’t be patented by drug companies for huge profit potential. DMSO has been known of for so long, that no one can claim the patent. In addition to that? Train cautiously. For a few days, all I did was to stretch out in the mornings. Also, I did do isometric full body holds for multiple reps, with my arms at my sides… Then, I added in straight legged setups and hindu squats for multiple sets, since they did not aggravate my upper body. My shoulder mobility improved dramatically, and this morning, about a week later, I did some pushups and other exercises using my gymnastic rings in the basement! Hallelujah!! If you do not yet have rings in your house or garage, consider getting them- the most useful apparatus for training ever. I was doing pushups in the almost standing position, and flies as well- no strain. Went back and lower, still fine- I just made sure to not go into the “pain zone”. I could do pistol squats as well, no problem, and even chins on t

What? Another full-length show this week? Yep! We recently acquired a BJCP-curated sensory kit from the Siebel Institute, and decided to record and share our mostly horrible tasting experiences with all of you. Ethyl hexanoateAniseed, apple or licoriceCommon sources: Fermentation product, wort composition or yeast health GeraniolFloral, geranium flowersCommon sources: Hop addition and variety IndoleFarm, barnyardCommon sources: Bacterial infection during fermentation Spicy (Eugenol)Cloves, all spiceCommon sources: Microbial contamination, wild yeast or aging Earthy (2-Ethyl fenchol)Geosmin, soil-likeCommon sources: Packaging or water-derived contamination Papery (Trans-2-nonenal)Cardboard, oxidizedCommon sources: Product of oxidation, staling Isovaleric acidCheesy, old hops, sweaty socksCommon sources: Use of old, degraded hops AcetaldehydeGreen Apple, cut grassCommon Sources: Fermentation Product, staling, or contamination Butyric acidPutrid, baby vomitCommon Sources: Bacterial contamination D.M.S. (Dimethyl sulfide)Cooked corn, cooked vegetablesCommon sources: Wort boil, wort cooling or contamination Diacetyl (2,3-Butanedione)Butter, butterscotchCommon sources: Microbial contamination or improper maturation Ethyl acetateSolvent-like, nail polish removerCommon sources: Wort composition and yeast growth The Beerists are: John Rubio, Anastacia Kelly, Grant Davis and Mike Lambert. Photo courtesy of Shane Wilder. See more from his shoot with us here. Subscribe!Point your podcatcher to our RSS feed: feed://feeds.feedburner.com/thebeerists Or, subscribe via iTunes (Give us a review and a rating!) twitter.com/thebeeristsfacebook.com/thebeeristsor email us at info@thebeerists.com

Dimethyl sulfide podcast from Chemistry World - the magazine of the Royal Society of Chemistry

Quantenchemische Berechnungen von Carbokationen-Stabilitäten und Elektrophilieparametern E Die Strukturen von zwölf Benzhydrylkationen (XC6H4)2CH+ und ihrer Additionsprodukte mit dem Methylanion (XC6H4)2CH-CH3 wurden auf B3LYP/6-31G(d,p)-Niveau optimiert. Struktur und Reaktivität wurden diskutiert. ClClMeMeMeMeOOOOONMe2Me2NNNNNtol(Ph)CH+(tol)2CH+(ani)2CH+(pcp)2CH+ani(Ph)CH+ani(tol)CH+(fur)2CH+(mfa)2CH+(dma)2CH+(jul)2CH+(lil)2CH+Ph2CH+NNCF3MeMeF3COH3CH3CCH3H3C Abbildung 0-1: Zwölf Benzhydrylkationen; dargestellt ist jeweils das optimierte Konformere.Der Einfluss des Basissatzes wurde bis zum B3LYP/6-311++G(3df,2pd)//B3LYP/6-31g(d,p)-Niveau untersucht. Eine ausgezeichnete lineare Korrelation wurde zwischen dem experimentellen Elektrophilieparameter E (aus der Beziehung lg k = s (N + E)[1]) und den berechneten Methylanion-Affinitäten bereits auf B3LYP/6-31g(d,p)-Niveau gefunden.Abbildung 0-2: Korrelation zwischen den Elektrophilieparametern E verschiedener Benzhydrylkationen mit berechneten Methylanion Affinitäten [∆E0 = E0(Ar2CH–CH3) – E0(Ar2CH+) – E0(CH3–)] auf B3LYP/6-31G(d,p) Niveau (r = 0.9976). Hydrid- und Hydroxidanionaffinitäten von fünf Benzhydrylkationen wurden auf B3LYP/6-31G(d,p)-Niveau berechnet. Diese korrelieren mit den berechneten Methylanion-Affinitäten mit einer Steigung von 1.00; dies zeigt an, dass die relativen Anion-Affinitäten von Benzhydrylkationen von der Lewis-Base unabhängig sind. Um Solvatationseffekte zu berücksichtigen, wurden Hydroxidanionaffinitäten in der Gasphase mit entsprechenden experimentellen Affinitäten in Lösung (d.h. pKR+) verglichen. Dabei ergab sich, dass sich die Stabilitätsunterschiede derCarbokationen in Lösung verkleinern. Zum gleichen Ergebnis gelangt man durch Korrelation von experimentellen Chloridanion-Affinitäten in Lösung mit den berechneten Methylanion-Affinitäten in der Gasphase. Mit Hilfe der Marcus-Gleichung konnte gezeigt werden, dass die intrinsische Barriere konstant bleibt, wenn ein Nucleophil mit dem Steigungsparameter s = 0.67 mit einer Serie von Benzhydrylkationen umgesetzt wird. Größere bzw. kleinere Werte von s als 0.67 zeigen ein Absinken bzw. Ansteigen der intrinsischen Barriere mit zunehmender thermodynamischen Triebkraft der Reaktion an. Diels-Alder-Reaktionen von 1,3-Diarylallylkationen Die Allylkationen 41 und 42 wurden als Tetrafluoroborat-Salze synthetisiert. BF4NMe2Me2NBF4OMeMeO4142 Abbildung 0-3: Allylkationen 41 und 42. Bei den Umsetzungen von 41 und 42 mit one-bond-Nucleophilen (Allylsilane, Allylstannane, Silylenolether, Heteroarene und Hydriddonoren) wurden die erwarteten Produkte erhalten (Schema 0-1).BF4XXXXNuNuX = OMe, NMe241 / 42 Schema 0-1: Umsetzung von 41 und 42 mit one-bond Nucleophilen. 41 reagierte mit den Dienen 61-63 zu Sechsringen (Schema 0-2). Entsprechende Reaktionen mit 42 konnten auch mit elektronenreicheren Dienen nicht beobachtet werden. MeOMeOMeR1R2ZnCl2OMeMeMeOMeOMeOR1R261 62 6364 65 6641MeMeOMeOR1R2ZnCl2OMe68 Me HH HR1 R2H Me61, 6462, 6563, 66 Schema 0-2: Bildung von Cycloaddukten ausgehend von 41. Die Kinetik der Reaktionen von 41 und 42 mit one-bond Nucleophilen wurde UV-spektroskopisch untersucht. Dadurch konnten die Elektrophilieparameter der beiden Allylkationen 41 und 42 bestimmt werden.Aus diesen E-Parametern und bereits bekannten s- und N-Parametern der Diene konnten Geschwindigkeitskonstanten für die Reaktion von 41 und 42 mit Dienen für den Fall vorhergesagt werden, dass nur eine neue Bindung im geschwindigkeitsbestimmenden Schritt geknüpft wird. Entsprechend berechnete Werte stimmen mit den gemessenen Geschwindigkeitskonstanten überein. Übergangszustände mit hohem Grad an Konzertiertheit können daher ausgeschlossen werden. Quantenchemische Untersuchung der Reaktionspfade der Reaktion von Methyl-substituierten Allylkationen mit 1,3-Dienen Die Reaktion des 1,1-Dimethylallykations mit s-cis-1,3-Butadien[2] wurde auf B3LYP/6-311++G(3df,2pd)//B3LYP/6-311G(d,p)-Niveau studiert. Da die Reaktion keine Barriere bezüglich Etot besitzt, wurden drei Reaktionspfade (lineare-, exo- und endo-Annäherung) vorgegeben und an Strukturen entlang dieser Pfade Frequenzrechnungen durchgeführt. linexoendoHHHHHHHHH Abbildung 0-4: Untersuchte Reaktionspfade der Reaktions des 1,1-Dimethylallykations mit s-cis-1,3-Butadien. Auf diese Weise wurden Barrieren der freien Enthalpie (∆G ‡) zwischen 2 und 3 kcal mol-1 erhalten. Die Reaktion des 1,1,3-Trimethylallylkations mit 1,3-Butadien wurde auf B3LYP/6-311++G(3df,2pd)//B3LYP/6-311G(d,p)-Niveau untersucht. Die Strukturen der Edukte, von vier π-Komplexen, von fünf Übergangszuständen und von vier möglichen Produkten wurden auf B3LYP/6-311G(d,p)-Niveau durch Geometrieoptimierung ermittelt. Die Übergangsstrukturen zeigen ein hohes Maß an Unsymmetrie. Die durchgeführten IRC-Rechnungen (intrinsic reaction coordinate) belegen eine große Asynchronizität der [2++4]-Cycloadditionen. Berechnung der Übergangsstrukturen der Diels-Alder-Reaktion des Kations 41 mit 2,3-Dimethyl-1,3-butadien und Isopren zeigen in Übereinstimmung mit den experimentellen Ergebnissen keine Mehrzentrenbeteiligung. Experimentelle und theoretische Untersuchungen der Reaktion des N-Methyl-4-vinylpyridinium-Ions mit Cyclopentadien und Diazoessigester N-Methyl-4-vinylpyridiniumtriflat (103) wurde nach Literaturvorschrift synthetisiert. NOTf103 Abbildung 0-5: N-Methyl-4-vinylpyridiniumtriflat (103). Die Reaktionen von 103 mit Morpholinocyclohexen (72), Diazoessigester (89) sowie Cyclopentadien (86) lieferten die Cycloaddukte 105, 109 und 106.OTfNNHNCO2EtNOTfOTfNNO109106105 Abbildung 0-6: Cycloaddukte105, 109 und 106. Die Elektrophilie von 103 wurde aufgrund eigener kinetischer Untersuchungen und literaturbekannter Geschwindigkeitskonstanten ermittelt. Mit Hilfe der Gleichung lg k = s (N + E) wurden Geschwindigkeitskonstanten für die Reaktionen von 103 mit Nucleophilen berechnet, die Mehrzentrenreaktionen eingehen können. Der Vergleich dieser berechneten Geschwindigkeitskonstanten mit experimentellen Werten ergab große Abweichungen für die Reaktionen von 103 mit Cyclopentadien und Diazoessigester. Dies ermöglichte die Berechnung der „free enthalpy of concert“, den Energiebetrag um den die konzertierte (und real ablaufende) Reaktion gegenüber der (hypothetischen) stufenweisen Reaktion bevorzugt ist. Während man für die Diels-Alder-Reaktion des N-Methyl-4-vinylpyridinium-Ions 103 mit Cyclopentadien eine free enthalpy of concert von ca. 11 kcal mol-1 ermittelt, ergibt sich für die 1,3-dipolare Cycloaddition von 103 mit Diazoessigester ein Konzertiertheitsgrad von ca. 4 kcal mol-1. Berechnungen der Reaktion von 103 mit Cyclopentadien auf B3LYP/6-311++G(3df,2pd)//B3LYP/6-31G(d,p) wurden durchgeführt Die endo-Übergangsstruktur ist um 2.9 kcal mol-1 (∆G) gegenüber der Übergangsstruktur des linearen Angriffs von Cyclopentadien bevorzugt.

Ziele dieser Arbeit waren zunächst die Optimierung der Synthese der razemischen 2- Hydroxy-2,3,3-trimethyl-butansäure (4) sowie die Entwicklung einer effizienten Razematspaltung dieser Säure. Nach dem Aufbau des Glycinäquivalents sollte dieses für den stereoselektiven Aufbau 2-substituierter 1-Aminocyclobutancarbonsäuren verwendet werden. Dabei sollte zum einen auf bereits bestehende Synthesemethoden zurückgegriffen, als auch ggf. neue Synthesewege entwickelt werden. Die 1-Aminocyclobutancarbonsäuren sollten anschließend auf ihre biologische Aktivität hin untersucht werden. Razemische 2-Hydroxy-2,3,3-trimethyl-butansäure (4) konnte in einer zweistufigen Synthese dargestellt werden, indem zunächst in Anlehnung an eine literaturbekannte Methode Pinakolon (5) mit KMnO4 zur 3,3-Dimethyl-2-oxobutansäure (13) oxidiert und diese dann mit einem Überschuß MeMgCl zur gewünschten razemischen Carbonsäure 4 umgesetzt wurde (Abb. 112). Für die Razematspaltung der razemischen α-Hydroxycarbonsäure 4 erwies sich Phenylalaninol (22) als am günstigsten. Damit konnte in zwei Schritten, durch Ausfällen und Umkristallisation, die enantiomerenreinen Carbonsäuren (S)-4 und (R)-4 nach Ansäuern in einer Enantiomerenreinheit von ≥ 99.5:0.5 erhalten werden. (S)-4 wurde durch Ausfällung mit (R)-Phenylalaninol ((R)-22, Abb. 112) und (R)-4 mit (S)-22 erhalten und dies in Ausbeuten von größer 70%. Nach der Synthese des chiralen Glycinäquivalents 2 in beiden enantiomeren Formen – (S)-2 und (R)-2 – nach einem Verfahren von A. Grandl wurde als Modellreaktion für die Synthese von Cyclobutylderivaten zunächst mit 1,3-Diiodpropan (41) als 1,3-Biselektrophil umgesetzt. Als Deprotonierungsreagenz diente Phosphazenbase (tBu-P4). Dabei entstand die spiro- Verbindung (R)-42 ohne erkennbare Nebenprodukte in einer Ausbeute von 35%. Nach Hydrolyse und Elution über einen Ionenaustauscher, konnte die freie Aminocyclobutancarbonsäure 48 in Ausbeuten bis zu 92% isoliert werden (Abb. 113). Anschließend wurden weitere Biselektrophile eingesetzt, welche mit dem Glycinäquivalent 2 2-substituierte spiro-Cyclobutanderivate liefern sollten. Zunächst wurden die mit einer geschützten Hydroxymethylenseitenkette versehenen 1,3-Biselektrophile (RS)-54 und (RS)- 65 eingesetzt. Diese waren aus 1,2,4-Butantriol ((RS)-49) in Synthesen von je 6 Stufen und in Ausbeuten von 32% ((RS)-65) und 25% ((RS)-54) zugänglich (Abb. 114). Trotz ausführlicher Variation der Versuchsbedingungen ließen sich diese mit 2 nicht zu den gewünschten spiro- Cyclobutanderivaten (ent)-64a/b umsetzen (Abb. 114). Als weiteres Biselektrophil kam trans-1,4-Dichlorbut-2-en (68) zum Einsatz. Anstelle der erwünschten diastereomeren Monoalkylierungsprodukte (ent)-69a/b wurden jedoch die vier diastereomeren spiro-Cyclopropylverbindungen (ent)-71a/b/c/d in einer Gesamtausbeute um 32% und in einem Isomerenverhältnis von 60:35:4:1 erhalten (Abb. 115). Da der Einsatz von Biselektrophilen nicht zu den gewünschten Verbindungen führte, wurde im Weiteren mit funktionalisierten Monoelektrophilen alkyliert. Der Ringschluß hatte dann in einem Folgeschritt zu erfolgen. Als Modell diente das allylierte Glycinderivat 83. Dieses wurde mit mCPBA zu den diastereomeren Epoxiden 84 und 85 umgesetzt (Ausbeuten >80%). Die anschließende Cyclisierung führte jedoch nicht zu den spiro-Cyclobutylverbindungen, was nicht unerwartet war, sondern zu den bereits bekannten spiro-Cyclopropylverbindungen 88 und 89 (Abb. 116). Aufgrund dieser Ergebnisse wurden vergleichbare Versuche mit dem homologen Alken (ent)- 135a/b durchgeführt. Das dafür erforderliche butenylsubstituierte Glycinderivat (ent)-135a/b ließ sich mit Phosphazenbase tBu-P4 als Deprotonierungsreagenz und Butenylbromid (134) in 60% Ausbeute darstellen, wobei jedoch das Auftreten des doppelt alkylierten Produktes (ent)- 82 nicht vermieden werden konnte. Mit Butentriflat (136) als Elektrophil – unter Verwendung von sBuLi als Base – ließ sich dieses Nebenprodukt vermeiden und die Ausbeute an (ent)- 135a/b betrug 69% (Abb. 117). Die Verbindung (ent)-135a ließ sich mit mCPBA in einer Ausbeute von 86% in ein Gemisch der isomeren Epoxide (ent)-97a/b überführen, wobei die Diastereoselektivität etwa 1:1 betrug (Abb. 118). Alle Versuche, die Verbindungen (ent)-97a/b zu den spiro- Cyclobutylverbindungen (ent)-139a/b zu cyclisieren blieben aber erfolglos (Abb. 118). Eine Umsetzung des monobutenylierten chiralen Glycinäquivalents (ent)-135a mit Iod, in der Absicht, das Diiodaddukt des Alkens zu erhalten, führte zu den diastereomeren monoiodierten Bicyclen (ent)-145a/b in Ausbeuten von etwa 70 % und Diastereoselektivitäten von etwa 65:35 ds (Abb. 119). Bei einer weiteren Route wurden (R)-2 und (S)-2 zunächst mit Iodessigsäureethylester alkyliert, was in sehr guten Ausbeuten (85% und 83%) gelang (Abb. 120, nur Alkylierung an (R)-2 dargestellt). Versuche, (ent)-98a/b mit 1,2-Dibromethan als Biselektrophil zur spiro- Cyclobutylverbindung (ent)-100 umzusetzen, blieben trotz Variation der Reaktionsbedingungen erfolglos (Abb. 120). In Analogie zur Arbeit von O. Achatz ließ sich jedoch der Syntheseweg zu den spiro- Cyclobutylphenylsulfonylverbindungen 133a/b erfolgreich nachvollziehen. Das Glycinäquivalent (S)-2 wurde dazu zunächst mit den silylgeschützten Iodethanolderivaten 108 und 109, und anschließend mit Iodmethylphenylsulfid (116) alkyliert und die Produkte anschließend zu den entsprechenden Sulfonen 119 und 120 oxidiert. Abspaltung der Silylschutzgruppe lieferte dann das Derivat 121 (Abb. 121). 121 war jedoch noch über eine weitere Syntheseroute zugänglich. Dazu wurde das allylierte chirale Glycinäquivalent 83 zunächst ebenfalls mit Iodmethylphenylsulfid (116) alkyliert. Anschließend wurde die dann vorliegende Verbindung 123 oxidiert und damit die Sulfidfunktion in ein Sulfon überführt und die Doppelbindung zum Aldehyd gespalten. Nach Reduktion des Produktes 128 gelangte man zum oben beschriebenen Derivat 121 mit Sulfonund OH-Funktion. Diese wurde anschließend in das Iodid 132 überführt, welches nach Behandlung mit Base (tBu-P4) in guten Ausbeuten zu den gewünschten diastereomeren spiro- Cyclobutylverbindungen 133a/b cyclisiert werden konnte. Die Hydrolyse zu den freien 1- Amino-2-phenylsulfonylcyclobutylcarbonsäuren 102a/b steht noch aus (Abb. 121). Schließlich wurde noch eine weitere Syntheseroute entwickelt, welche letztendlich zu den gewünschten diastereomeren 1-Amino-2-hydroxymethylencyclobutancarbonsäuren 150, (ent)-150, 151 und (ent)-151 führte. Für diese Route wurde von den diastereomeren butenylsubstituierten Verbindungen 135a/b, bzw. (ent)-135a/b ausgegangen und diese zunächst mit OsO4 und Trimethylamin-N-oxid behandelt, wodurch die Doppelbindung bishydroxyliert wurde. Die dabei gebildeten vicinalen Diole entstanden in einer Gesamtausbeute bis zu 90% und in einem Verhältnis von etwa 4:4:1:1. Im nächsten Schritt wurde das Isomerengemisch 146a/b/c/d, bzw. (ent)-146a/b/c/d, ohne sie zu trennen, selektiv an der primären Hydroxyfunktion mit einem Silylrest geschützt (90% Ausbeute). Die sekundäre Hydroxyfunktion wurde dann in ein Iodid überführt. Die Ausbeute des Isomerengemisches 148a/b/c/d, bzw. (ent)-148a/b/c/d lag bei 90% und das Isomerenverhältnis bei etwa 4:4:1:1. Die Produkte wurden dann mit der Phosphazenbase tBu- P4 zu den gewünschten spiro-Cyclobutylverbindungen 149a/b/c/d, bzw. (ent)-149a/b/c/d cyclisiert (Ausbeute über 80%, Isomerenverhältnis etwa 45:35:15:5). Nach Desilylierung wurden in 90%iger Ausbeute Isomerengemische der freien Alkohole 139a/b/c/d, bzw. (ent)- 139a/b/c/d erhalten, die durch präparative HPLC in ihre Einzelkomponenten getrennt wurden (Isomerenverhältnis: 48:31:18:3 , Abb. 122, die Synthesesequenz ausgehend von (S)-2 ist dargestellt). Da die beiden Nebendiastereomere 139c/d, bzw. (ent)-139c/d nur in einem Anteil von zusammen 21% anfielen, wurden diese nicht für die Generierung der freien Aminosäuren verwendet. Hydrolyse der Hauptdiastereomere 139a und 139b lieferte die freien Aminosäuren 150 und 151. Zur Darstellung der spiegelbildlichen Aminosäuren (ent)-150 und (ent)-151 wurden die für diesen Zweck dargestellten Enantiomere (ent)-139a und (ent)-139b der vorgenannten Hauptisomere hydrolysiert. Die Ausbeuten für die freien Aminosäuren lagen bei über 70% (Abb. 123). Zudem wurde noch versucht, die Cyclobutaneinheit über eine thermische [2+2]-Cycloaddition aufzubauen. Angewendet wurde dabei eine Methode von Ghosez. Dabei wurde die Ethylidenverbindung (R)-154, die durch eine Aldolkondensation von (R)-2 mit Acetaldehyd (153) zugänglich war (78%), mit dem Keteniminiumsalz des N-Propionylpyrrolidins, das in situ erzeugt wurde, umgesetzt. Es entstand jedoch nur ein Produktgemisch der verschiedenen möglichen Diastereomere und dies auch nur in einer Gesamtausbeute von etwa 10%. Deshalb wurden keine weiteren Versuche in dieser Richtung unternommen (Abb. 124).

Ein Ziel dieser Arbeit war es, die Zugänglichkeit von geminalen Bis(alkylzink)imiden zu untersuchen. Verbindungen des Typs (RZn)2NR´ wurden bereits in der Literatur[33][34] als Polymerisationskatalysator erwähnt, jedoch nicht strukturell erfasst. In Kapitel 2.1 ist die Zinkierung primärer Amine mit Dimethyl- und Diethylzink beschrieben. Sowohl in Lösung als auch im Feststoff erhält man nach Gleichung 37 dimere Alkylzinkamide des Typs [RZnN(H)R´]2. Während [MeZnN(H)SiiPr3]2 1 und [EtZnN(H)SiiPr3]2 2 solvensfrei mit seltenen, dreifach koordinierten Zinkatomen isoliert werden konnten, ist an das zentrale [MeZnN(H)Ad]2-Fragment bei Verbindung 4 ein Molekül Adamantylamin sowie ein Molekül THF mit einer außergewöhnlich langen Zn-O-Bindung (240 pm) angelagert. Daraus ergibt sich eine unterschiedliche koordinative Umgebung der beiden Zinkatome bei 4. 2 R´NH2 + R´ 2 ZnR2 - 2 CH4 R´= iPr3Si R = Me (1), Et (2) Zn NH NH Zn R R R´ R´= Adamantyl R = Me (4); *AdNH2; *THF Gleichung 37. Zinkierung primärer Amine zu dimeren Alkylzink-amiden des Typs [RZnN(H)R´]2. Vor allem Komplex 4 zeigt, dass Dimethylzink weder in der Lage ist, den Adamantylamidsubstituenten noch den koordinierten Adamantylaminliganden, selbst unter drastischen Bedingungen wie hoher Temperatur, zu metallieren. Die bis heute noch nicht strukturell charakterisierten Bis(alkylzink)imide lassen sich nach unseren Untersuchungen nicht durch Zinkierung primärer Amine erhalten und stehen somit nicht im Einklang mit dem in der Literatur beschriebenen Polymerisationskatalysator N,N-Bis(ethylzink)-tert-butylimid[33] oder mit den Bis(alkylzink)-trialkylsilylimiden.[34] Mit Zink-bis[κ2-N,N´-chlorzink-N-trimethylsilylamino-diphenylphosphoranyl]methandiid 5 konnte das erste Bis(halogenzink)methandiid strukturell charakterisiert werden. Im Gegensatz zu dem bisher als einzigen über Röntgenstruktur untersuchten, tetrameren Bis(alkylzink)- methandiid [(2-Pyridyl)(SiMe3)CZn]4 [50] kann man 5 auch als Zink-silylamid auffassen, da eine Umlagerung die Koordination zweier Zinkatome an das Methandiidkohlenstoffatom verhindert. In Kapitel 2.2 sind Synthese, Struktur und Reaktivität der 2-Aminomethylpyridinzinkdihalogenide beschrieben. Da Zinkhalogenide oft als Katalysatoren in der organischen Synthese eingesetzt werden, sind deren koordinative Umgebung und Eigenschaften von besonderem Interesse. Durch Addition von Zink(II)chlorid an Aminomethylpyridin erhält man nach Gleichung 38 Aminomethylpyridinzinkchlorid 6, während die schwereren Zinkhalogenide in Form von Bis(aminomethylpyridin)zinkbromid 7 bzw. –iodid 8 anfallen und als getrennte Ionenpaare [(AMP)2ZnX]+ X- (X = Br (7), I (8)) beschrieben werden können. Durch Abspaltung eines Liganden erhält man im Fall des Bromids 2-Aminomethylpyridinzinkbromid 9. Die Verbindungen 6 bis 9 reagieren mit Aceton unter Wasserabspaltung und hohen Ausbeuten leicht zu den entsprechenden Propylidenkomplexen 10 bis 12. Um den linearen Zusammenhang zwischen Zn-N-Bindungslängen und R-Zn-R´- Bindungswinkeln in Verbindungen des Typs (L)2ZnRR´ zu untersuchen, wurden die Molekülstrukturen von 9, 10 und 12 bestimmt. Die Verbindungen weisen die kleinsten bis heute bestimmten Winkel (115°) auf und fügen sich mit ihren sehr kurzen Zn-N-Bindungslängen von 205 pm in die genannte Beziehung ein. Die dargestellten TMEDAKomplexe von ClZnCH2SiMe3 14 und ClZntBu 15 reihen sich ebenso ein. Die Reaktion von 10 mit Lithium-methanid ergibt Methylzink-2-azabenzylidenaminopropan-2- id 13 und zeigt, dass der Aminomethylpyridinligand leicht durch eine Base in α-Stellung zum Ring deprotoniert werden kann. In Kapitel 2.3 wird eine neuartige, oxidative Kohlenstoff-Kohlenstoff-Kupplung bei der Umsetzung von (Trialkylsilyl)(2-pyridylmethyl)aminen mit Dialkylzinkverbindungen beschrieben (Gleichung 39). Es gelang den Reaktionsmechanismus dieser ungewöhnlichen metallorganischen Reaktion aufzuklären und die Zwischenstufen strukturell zu charakterisieren. Im Gegensatz zur Reaktion von 1,4-Di(tert-butyl)-1,4-diazabutadien (DAB) mit Dialkylzink,[89][90][91][92] bei der ebenfalls eine C-C-Kupplung zu beobachten ist, lässt sich ein radikalischer Reaktionsweg von uns ausschließen. Bei der Umsetzung von (Trialkylsilyl)(2-pyridylmethyl)aminen 16 mit Dialkylzink erhält man bei R.T. zunächst dimeres Alkylzink-2-pyridylmethyl(tert-butyldimethylsilyl)amid 17, das beim Erhitzen mit einem Überschuss R´2Zn zu dem C-C-Kupplungsprodukt 18 weiterreagiert. Im Verlauf dieser Reaktion beobachtet man die äquimolare Abscheidung von elementarem Zink und die Abspaltung von Methangas. Die C-C-gekuppelte Spezies weist einen sehr kurzen, nicht bindenden Zn⋅⋅⋅Zn-Abstand (272 pm) sowie eine neue, relativ lange C-C-Bindung (157 bzw. 160 pm, abhängig vom sterischen Anspruch der Reste) auf. Durch die Knüpfung der neuen Bindung ergeben sich zwei chirale Zentren im Molekül, wobei ausschließlich ein Gemisch der (S,S)- und (R,R)-Enantiomeren erhalten wird und nie die meso-Form. Beide Zinkatome sind tetraedrisch umgeben. Zur Aufklärung des Mechanismus wurden die entsprechenden Benzylderivate (E = CH, Gleichung 39) dargestellt. Dies gelang bis auf Typ O und P, die C-C-gekuppelte Spezies. Die Notwendigkeit des Pyridylstickstoffs bei der C-C-Kupplung kann mit Zwischenverbindung O aus Gleichung 39 erklärt werden, denn nur über das Zink-bisamid kann es zur oxidativen Kupplung der Kohlenstoffatome kommen. Untersucht man den Zusammenhang der Größe der Reste in Bezug auf die Kupplungsreaktion, so kann man keinen Einfluss bei Variation der Alkylgruppen (R) am Siliciumatom erkennen. Eine Vergrößerung der am Zink gebundenen Gruppen (R´) zeigt dagegen eine Abnahme der Reaktionsgeschwindigkeit bis hin zum Ausbleiben der C-C-Kupplung bei R´ = C(SiMe3)3. Bis(methylzink)-1,2-dipyridyl-1,2-bis(tert-butyldimethylsilylamido)ethan 18 ist ein in jeder Hinsicht ungewöhnlicher, binuclearer Komplex. Bei Reaktionen mit Verbindungen des Typs R´EH2, beschrieben in Kapitel 2.4, zeigen sich in Abhängigkeit der Acidität der Protonen unterschiedliche Reaktionsarten. Mit Triisopropylsilylphosphan und –arsan wird das Gruppe-15 Atom durch ein Methylzinkfragment unter Abgabe von Methan zinkiert (Gleichung 40). Da überraschenderweise zusätzlich die vierzähnige Aminobase vom Phosphan protoniert wird, erhält man den dreikernigen Komplex 25, bei dem zwei Zn-Atome vierfach und eines zweifach koordiniert ist. Dieser Komplex stellt das erste Beispiel für ein zweifach koordiniertes Zinkatom in einem Phosphandiid dar. Der P-Zn-P-Winkel weicht mit 154° stark von der, bei Koordinationszahl 2 zu erwartenden Linearität, wie bei den Bisamiden und Bismethaniden[99][101][133][134] ab. Wie auch bei Ausgangsverbindung 18 erhält man ein Gemisch der (S,S)- und (R,R)-Enantiomeren, jedoch nicht die meso-Form. Durch die eingeschränkte freie Drehbarkeit der großen Reste und einer unterschiedlichen magnetischen Umgebung zeigt sich für die Chemischen Verschiebungen der beiden Methylgruppen am Silicium ein bemerkenswert großer Unterschied von 20 ppm im 13C{1H}-NMR-Spektrum. Setzt man 18 mit Methanol, Isopropanol oder Acetamid um, kann man die Protolyse zu dem metallfreien Liganden 27 beobachten. Allerdings werden die N-Si-Bindungen durch MeOH und iPrOH ebenfalls angegriffen, so dass die Protolyse mit Acetamid vorzuziehen ist. Das entstandene Enantiomerengemisch aus (S,S)- und (R,R)-Form kann durch Belichten teilweise in die meso-Form 29 überführt werden. Da es sich bei den Verbindungen um AA´XX´-Systeme handelt, erhält man für die Protonen des Brückenkopfs ein Signal höherer Ordnung im 1HNMR- Spektrum. Die Bindung zwischen den chiralen Zentren ist bei den beiden Diastereomeren sowie dem H2O-Addukt der (S,S)-Form mit ca. 156 pm relativ lang. Lässt man die meso-Form 29 mit Dimethylzink reagieren, so gelangt man wieder zu der (S,S)- und (R,R)- Form von 18. Eine Darstellung der meso-Form des binuklearen Komplexes ist nicht möglich. Mit dem in der Reihe am wenigsten sauren Anilin (PhNH2) führt eine ungewöhnliche C-NAktivierung zu einem Austausch der [NSiMe2 tBu]2-- gegen eine [NPh]2--Gruppe. Mittels Isotopenmarkierung konnte gezeigt werden, dass nicht die Si-N-, sondern die C-N-Bindung aktiviert und der Anilinstickstoff quantitativ über eine nukleophile Substitutionsreaktion in die neu entstehende Verbindung Bis(methylzink)-1,2-dipyridyl-1,2-bis(phenylamido)ethan 30 eingebaut wird. Der Komplex 30 weist mit 8,2 Hz eine bemerkenswert große 3J(15N15N)- Kopplung auf. Durch einen Deuterierungsversuch kann ein Eliminierungs-Additions- Mechanismus ausgeschlossen werden. Die Protolyse von 30 mit Acetamid führt zu isotopenmarkiertem, metallfreiem 1,2-Dipyridyl-1,2-di(phenylamino)ethan 31. In Kapitel 2.5 wird die Reaktion von 2-Aminomethylpyridin mit Dimethylzink beschrieben. Während bei R.T. nur die Metallierung zu 2-(Amidomethyl)pyridyl-zinkmethanid 32 beobachtet wird, kommt es bei höherer Temperatur oder langen Reaktionszeiten unter Abscheidung von Zinkmetall zur oxidativen C-C-Kupplung und anschließender C-NAktivierung nach Gleichung 41. Bei dem entstandenem Diazacyclohexanderivat 34 wurden zwei C-C- und zwei C-N-Bindungen neu geknüpft. Durch Protolyse des Reaktionsgemisches gelang mit (Z)-1-Amino-1,2-di(2-pyridyl)ethen 33 die Isolierung eines durch Eliminierungsreaktion entstandenen primären Enamins. Bei allen drei Derivaten konnte die Struktur durch Röntgenstrukturanalyse aufgeklärt werden. Während 32 als Trimeres kristallisiert, in Lösung jedoch sowohl dimer als auch trimer vorliegt, handelt es sich bei 33 um ein primäres Enamin und somit um eine strukturell kaum charakterisierte Verbindungsklasse. Die neue C=C-Bindung ist extrem kurz (130 pm), der Abstand zwischen dem C- und dem N-Atom des Amins mit 138 pm etwas länger als eine gewöhnliche C=N-Doppelbindung. Die Planarität des Moleküls wird durch die ausgebildeten Wasserstoffbrücken der Enaminform erzwungen. Ein Gleichgewicht mit dem Imin wird nicht beobachtet. Das sesselförmige Diazayclohexanderivat 34 kristallisiert als vierkerniger Komplex mit vier- und fünffach koordinierten Zinkatomen. Die gefundene, koordinative Zn- N(py)-Bindung zählt mit 246 pm zu den längsten ihrer Art. Die neu geknüpften C-NBindungen entsprechen mit 147 pm den Erwartungen, während die gekuppelte C-C-Bindung mit 157 pm wiederum etwas länger als eine normale C-C-Einfachbindung ist.

A mixture of solid KOH in dimethyl sulfoxide has a strong basicity, but only a low nucleophilicity and is used for methylation of ketones. With this simple and inexpensive reagent complete methylation with yields up to 90% can be achieved.

The incorporation of [Me-14C] from SAM-[Me-14C] into precursors indicates the following sequence of tocopherol synthesis in spinach: 2-methyl-6-phytylquinol (6-phytyltoluquinol) (1a) → 2,3-dimethyl-5-phytylquinol (phytylplastoquinol) (2a)→,γ-tocopherol (5a)→-tocopherol (6). 1a is particularly preferred to 2-methyl-5-phytylquinol (1b) and 2-methyl-3-phytylquinol (1c). 1a only forms 2a. 2a is converted to 6 via 5a and, to a lesser extent, 2,5-dimethyl-6-phylquinol (2b) to 6 via β-tocopherol (5b). Trimethylphytylquinol (3) is not an intermediate in the formation of 6. All reactions are independent of light.

Sun, 1 Jan 1978 12:00:00 +0100 http://epub.ub.uni-muenchen.de/3818/ http://epub.ub.uni-muenchen.de/3818/1/013.pdf Olah, George A.; Donovan, Daniel J.; Lin, Henry C.; Mayr, Herbert; Andreozzi, Patricia; Klopman, Gilles Olah, George A.; Donovan, Daniel J.; Lin, Henry C.; Mayr, Herbert; Andreozzi, Patricia und Klopman, Gilles (1978): Onium ions. 18. Static protonated and exchanging diprotonated ambivalent heteroorganic systems. hydroxylamines, acetone oxime, and dimethyl sulfoxide. In: Journal of Organic Chemistry, Vol. 43, Nr. 1