Podcasts about MP2

#373Puzzle SystemsInterview2024.11.15Releasing 2019's "Baba is You" after more than a decade of making puzzle games was a milestone for this week's guest, but it was also just the beginning of his design journey. Arvi "Hempuli" Teikari talks to your nice hosts about the balance between giving players freedom and constraining their expression, the pacing and sequencing of individual puzzles, what happens when a "cool" design annoys players, and more.Arvi's cats make a spirited apperance in the back half of the episode. Here they are basking in the Finnish sun.Puzzle SystemsGame DesignToolsMultimedia Fusion 2 - ClickteamClickteam Fusion 2.5 - ClickteamConstruct - Scirra LtdMP2MP2 Chowdren EngineBring the ice cube to the goal without exposing it to heat. - IncreparePuzzleScript - IncrepareCovechrome - Hempuli, itch.ioYou nice hosts previously discussed what happens to players who become developers in:"Numbers go up."Arvi "Hempuli" TeikariGuestExternal linkHempuli - social media linksHempuli on Itch.io

Releasing 2019's "Baba is You" after more than a decade of making puzzle games was a milestone for this week's guest, but it was also just the beginning of his design journey. Arvi "Hempuli" Teikari talks to your nice hosts about the balance between giving players freedom and constraining their expression, the pacing and sequencing of individual puzzles, what happens when a "cool" design annoys players, and more.Arvi's cats make a spirited apperance in the back half of the episode. Here they are basking in the Finnish sun.Puzzle SystemsGame DesignToolsMultimedia Fusion 2 - ClickteamClickteam Fusion 2.5 - ClickteamConstruct - Scirra LtdMP2MP2 Chowdren EngineBring the ice cube to the goal without exposing it to heat. - IncreparePuzzleScript - IncrepareCovechrome - Hempuli, itch.ioYou nice hosts previously discussed what happens to players who become developers in:"Numbers go up."Arvi "Hempuli" TeikariGuestExternal linkHempuli - social media linksHempuli on Itch.io

In this episode: We discuss the basics of Pagibig MP2 Savings, its dividend payout rate the last 5 years, and how to open an MP2 account online.

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Olá, bio-ouvintes! Poluição do ar e resistência a antibióticos: Já se sabe que exposições ao ar poluído diminuem a expectativa de vida e têm associação com doenças cardíacas, asma e até câncer de pulmão. E recentemente, um estudo encontrou correlações significativas entre a resistência a antibióticos e a concentração de MP2.5 (material particulado 30 vezes mais fino que um cabelo humano), que pode carregar genes de resistência a antibióticos por aí. Estação de pesquisas poluindo a Antártida: Os programas de pesquisa antárticos de todos os países estão tendo que lidar com lixo e contaminação, graças principalmente às estações mais antigas. Foram encontradas altas concetrações de hidrocarbonetos e metais pesados, além de bifenilos policlorados (compostos altamente carcinogênicos) nas águas antárticas.   CONTATOS cartinhas@biologiainsitu.com.br Instagram, Facebook e LinkedIn: @biologiainsitu Twitter e TikTok: @bioinsitu   APOIO Apoio recorrente na Orelo! Ou no Padrim! Pix: cartinhas@biologiainsitu.com.br Também no PicPay!   CRÉDITOS Coordenação por Bruna Canellas, Cristianne Santos, Heloá Caramuru, Ricardo Gomes e Vitor Lopes. Pesquisa e roteiro: Natã Rahhal. Locução: Ricardo Gomes. Edição e mixagem de áudio: Marina Milito. Arte de capa: Larissa Castro.   CITAÇÃO DO EPISÓDIO (ABNT) Biologia In Situ 118: 118 - Bionews - Poluição no ar e na Antártida. Coordenação: Bruna Garcia da Cruz Canellas, Cristianne Santana Santos, Heloá Caramuru Carlos, Ricardo da Silva Gomes e Vitor Estanislau de Almeida Souza Lopes. Pesquisa e roteiro: Natã Dutra Fernandes Rahhal. Locução: Ricardo da Silva Gomes. Edição e mixagem de áudio: Marina Milito Góes. Arte de capa: Larissa Araguaia Monteiro de Castro. [S. l.] Canal Biologia In Situ, 05 de outubro de 2023. Podcast. Disponível em: .

In this episode, Sir Vince tackles on how we can use PAGIBIG MP2 as a way to save up for emergencies. In this episode, he shares some tips on how we can utilize MP2 and the steps to be done in making it a viable option to save our emergency fund. ——————————————————————————— Join the USAPANG PERA GROUP

FEATURING GOSHEN PUBLISHER'S AUTHORS: Peoples, Rogers, Hayes, & Maple Maharold Peoples Jr https://www.goshenpublishers.com/maharold-peoples-jr “MP2” is a licensed minister, published author, and gospel artist. He is also a songwriter and producer. In his What To Do series, he is writing for you to be encouraged and strengthened in the Lord and in the power of His might. Nathan Rogers, PhD: https://www.goshenpublishers.com/dr-nathan-rogers Dr. Nathan Rogers is an entrepreneur, a veteran, and an academic and social scientist. Driven by the need to help others with their hidden talents, he has written a book to empower you to take control of your own learning. Kimberly Hayes, D.Min https://www.goshenpublishers.com/dr-kimberly-hayes Dr. Hayes is fascinated by the way people function in their relationships and how those relationships affect community. There is so much to gain when you investigate why people do the things they do. Uche Maple https://www.goshenpublishers.com/uche-maple Ucheonye Maple is the owner of Aghaeze-Maple Enterprises, LLC, a leadership and personal development training company. She has held various leadership roles within Fortune 500 companies in the field of engineering from systems engineering to program management. --- Support this podcast: https://anchor.fm/dr-angelia-griffin/support

A urgente demanda pelas Academias da Mente - As Academias da Mente terão a função de desenvolver e manter ativas as Camadas mais Abstratas da Mente 2.0. - Quanto mais abstrata é a função da mente, mais ela exige um tipo diferente de preparação. - Basicamente, os Personal Trainers da Mente terão a função de “muscular e alongar” a MP2, MP3 e a MP4. - Precisamos desenvolver, de forma cada vez melhor, a nossa habilidade de Auto-Reformatação das camadas mais básicas da mente. - A Mente do Sapiens 2.0 tem que ter uma Formatação Primária muito mais flexível do que a do 1.0. - O Sapiens 2.0 terá que praticar uma “musculação” constante das Camadas mais Reformatadoras da Mente. - Mudou a Civilização é preciso criar um processo consciente e planejado de readaptação das mentes. - As Mentes 1.0 foram formatadas para viver em um mundo MENOS mutante, inovador, competitivo, horizontalizado, informado e criativo. https://bit.ly/artigobimodal090922a É isso, que dizes? Venha conhecer a Visão de Futuro para Disruptores da Bimodais! Me manda um Zap: 21-996086422 (Nepô, chega de MIMIMI!) Compre meu livro Administração 3.0, autografado:https://bit.ly/adm30autografado

#2 - Hábitos Atômicos - James Clear - Não podemos afirmar que o processo de Inovação Pessoal é de autoconhecimento, mas da Auto-reformatação. - Inovar é, em qualquer nível, um processo de Auto-Reformatação. - Quanto mais disruptiva é a mudança, mais e mais precisamos ativar as nossas mentes mais abstratas. - Como temos dito aqui dentro da visão filosófica da Ciência da Inovação Bimodal, o Sapiens é a espécie mais artificial do planeta. - Boa parte de nossa Identidade Inicial é muito mais construída de forma para dentro do que de dentro para fora. - Quanto mais Filosófica é a demanda pela Reformatação Individual, mais precisamos nos utilizar de funções mais abstratas da mente. - Auto-Reformatações mais operacionais são feitas pela MP2 e as mais Filosóficas demandam a atividade da MP3. - A chegada da Civilização 2.0 nos obriga que haja um Processo Mais Continuado de Auto-Reformatação Pessoal. https://bit.ly/artigobimodal080922a É isso, que dizes? Venha conhecer a Visão de Futuro para Disruptores da Bimodais! Me manda um Zap: 21-996086422 (Nepô, chega de MIMIMI!) Compre meu livro Administração 3.0, autografado:https://bit.ly/adm30autografado

Alam mo ba kung paano gawin ang MP2? In this episode, Sir Vince and Sir Ed discusses the ways on how you can maximize your approach in investing in PAG-IBIG MP2. They discuss the personal MP2 hacks that they do for MP2 and why it remains one of their favorite investment vehicles. How to invest: https://m.me/vincerapisura?ref=w13160758 Join the USAPANG PERA GROUP

Alam nyo ba na the Pag-IBIG Board of Trustees has approved dividends for their members' savings in the amount of P31.79 billion – the highest declared amount in the history of PagIBIG! The final dividend rates for 2021 are now 5.5% for the Pag-IBIG Regular Savings and 6% for MP2. Pero ano ba talaga ang MP2 or Modified Pagibig 2 savings program? Paano tayo pwedeng kumita or mawalan ng pera dito? At ito nga ba ang best investment vehicle for us Filipinos? Yan ang tatalakayin natin today dahil I've researched the most asked questions sa investment vehicle na to kaya make sure na you finish this episode until the end! What You'll Learn: - Why consider Pag-Ibig MP2? - What exactly is MP2? - How MP2 works - How you make and lose money from MP2 - How much you need to start - What happens to your dividends if you withdraw early - How to renew - How to open an account - How to fund your MP2 account - Who should invest in it Resources: MP2 Savings Enrollment: https://www.pagibigfundservices.com/MP2Enrollment/ Online Membership Registration: https://www.pagibigfundservices.com/PubReg/NewReg_Page.aspx?88D64A1E7CDAFB6882DDFEB76443D811 Pay MP2: https://www.pagibigfundservices.com/virtualpagibig/OPF.aspx?PT=M2 Pag-IBIG MEMBERSHIP ID (MID) NUMBER INQUIRY: https://www.pagibigfundservices.com/virtualpagibig/MIDInquiry.aspx MP2 FAQ & SAMPLE COMPUTATIONS: https://www.pagibigfund.gov.ph/Membership_ModifiedPagIBIG2.html EMail Template for MID Number: https://docs.google.com/document/d/1hNEzsSjBhbmysmcAmGwT3zq4jFHRZIGvL59TJqDFAJU/edit?usp=sharing —

Paralelo 20 (26/9/2021) [00:00:00] 9:00 am - Paralelo 20 [00:57:59] DYRA1312000 [00:58:30] PROMO WACHAP GEN 06 2021SQLXFRAME1AUDIO25_00_00 PROMOS 2017PROMO WACHAP GEN 06 2021.MP2 [00:59:26] 12/04/21BOMBAI JINGLE MARCA ok (Copia)BOMBAI JINGLE MARCA okSQLXFRAME1AUDIO25_00_00 PROMOS 2017BOMBAI JINGLE MARCA OK.MP2 [00:59:57] GOLPE RM 1SQLXFRAME1AUDIO25_00_00 PROMOS 2017 GOLPE RM 1.MP2 See omnystudio.com/listener for privacy information.

Paralelo 20 (19/9/2021) [00:00:00] 9:00 am - Paralelo 20 [00:00:07] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 [00:57:58] SKTZ-FM San Francisco-Oak-San Jose [00:58:28] PRIB0353000_PCL_WestCoast_SF_30 [00:58:58] ONG Plan InternacionalSQLXFRAME1AUDIO25_00_00 PROMOS 2017ONG PLAN INTERNACIONAL.MP2 [00:59:29] L-DPROMO FAD CHALLENGESQLXFRAME1AUDIO25_00_00 PROMOS 2017PROMO FAD CHALLENGE.MP2 [00:59:49] RAFAGA RM 2020 3 SQLXFRAME1AUDIO25_00_00 PROMOS 2017RAFAGA RM 2020 3 .MP2 [00:59:58] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 See omnystudio.com/listener for privacy information.

Paralelo 20 (12/9/2021) [00:00:00] 9:00 am - Paralelo 20 [00:00:07] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 [00:56:15] Q4-Menthol-Implementation-Audio-Racist-30-Eng [00:56:46] EUCC0251000 [00:57:16] ORNTL21952 (1) [00:57:46] GPN_Orange_Bike_Tag01_FULLMIX [00:58:17] PROMO ONG RAIS DIC 19SQLXFRAME1AUDIO25_00_00 PROMOS 2017PROMO ONG RAIS DIC 19.MP2 [00:58:53] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 See omnystudio.com/listener for privacy information.

Mike Wikan is a Game Designer who has worked on Duke Nukem, Donkey Kong and DOOM. He is most well known for being Lead Designer on the Metroid Prime Trilogy during his tenure at Retro Studios. He is now Creative Director at Booz Allen Hamilton WEBSITE - https://www.boozallen.com   #metroid #metroidprime #gamedesign     TIMESTAMPS   00:00 - Intro 01:27 - How Metroid Prime Was Developed/Techniques That Were Used 07:06 - Working With Nintendo/Language Difficulties/Translators 08:11 - How Nintendo Operates 09:09 - Shigeru Miyamoto Story From Donkey Kong Country Returns 11:12 - Tanabe Was The Reason For Spider Ball & Boost Ball Guardians Difficulty 12:17 - Fixing Things In Metroid Prime Trilogy 13:14 - Nintendo Analysed Every Bit Of Text In Metroid Prime Trilogy 14:03 - Who Was Responsible For The Lore/Luminoth Language 15:56 - Sketching Background /How Mike Learned Coding, 3D Models, Design etc. 19:45 - Growing Up In The Military/Taking Military Experiences Into Metroid Prime Development 22:16 - Mike Had To Do Non Detailed Sketches Before Handing Them To Artists 24:10 - How Quadraxis Boss Was Designed/Gameplay Ramping/Game Engine Camera System 30:28 - MP2 and MP3 Didn't Have Crunch 31:09 - The True Story Behind Metroid Prime 2's Initial Development 32:20 - Metroid Prime 1 Crunch/Management Of Retro Studios Changed After Metroid Prime 1 34:00 - How Booz Allen Hamilton Gaming Development Works/Avoiding Crunch For Creatives 36:35 - How To Manage Creative Staff Properly 39:05 - How To Prepare For Curve Balls In Game Design/The Pillars Of Game Design 40:52 - Meta Ridley Boss Fight In MP3 Inspired By Lord Of The Rings/Original Meta Ridley Design Fight In MP1 42:26 - Mike Wikan Loves Lord Of The Rings 43:15 - Mike Is Very Introverted/How He Breaks Through It  46:35 - Being A Lifetime Learner 47:18 - The Problem With AAA Game Studios & Lack Of Leadership 49:01 - Breakdown Of Gaming Studios Profits From Game Sales 51:28 - How Nintendo Operates In Terms Of Managing Staff 52:03 - Eastern Game Design Vs Western Game Design 52:53 - Gameplay Trumps Graphics/Story Never Sells A Game 54:22 - AAA Games Designs Flaws/How Mike Guides Game Designers 57:10 - How Management Works Once You Have More Than 45 Staff 57:47 - No Excuse For Western Developers Not Adapting To Eastern Game Methodology 58:58 - Mike's Managing Style At Boon Allen Hamilton 1:02:35 - What Games Mike Wikan Plays/Bullet Echo 1:05:31 - Mike Will Play Metroid Dread & Prime 4 1:06:40 - Where To Keep Up With What Mike Wikan Is Working On 1:07:44 - What Was Being Fine-tuned With Metroid Primes Audio/Clark Wen 1:09:45 - Mike Is Extremely Thankful To All The Metroid Prime Fans To This Day

Paralelo 20 (22/8/2021) [00:00:00] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 [00:57:57] H2F_SHIFT [00:58:29] ORNTL21952 (1) [00:58:59] DYRA1300000 [00:59:29] THRE0001000 See omnystudio.com/listener for privacy information.

Paralelo 20 (15/8/2021) [00:00:00] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:00:01] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 [00:57:59] AMZ_PAY20 [00:58:29] ORNTL21952 (1) [00:58:59] DYRA1300000 [00:59:30] Q2-Flavors2020-Audio-Nicotine-Flavors-30-Eng See omnystudio.com/listener for privacy information.

Paralelo 20 (25/7/2021) [00:00:00] 9:00 am - Paralelo 20 [00:00:03] RAFAGA RM 2020 1SQLXFRAME1AUDIO25_00_00 PROMOS 2017RAFAGA RM 2020 1(1).MP2 [00:00:11] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:00:12] Advertisement [00:00:42] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 [00:59:12] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:59:13] 12/02PROMO ONG SOÑAR DESPIERTOSQLXFRAME1AUDIO25_00_00 PROMOS 2017PROMO ONG SOÑAR DESPIERTO.MP2 See omnystudio.com/listener for privacy information.

MARCA Gaming Show Podcast - 2021-7-24 [00:00:00] 4:00 pm - MARCA Gaming Show [00:18:30] Advertisement [00:19:00] 60db438889cd4459add423fd [00:19:30] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 [00:49:35] 3DTMF (5-D) SOLO RADIO AEQ PROMO SQLXFRAME1AUDIOPUBLICIDADDTMF (5-D) SOLO RADIO AEQ PROMO.MP2 [00:49:37] 12/07/20F-PROMO MARCADOR 2020SQLXFRAME1AUDIO25_00_00 PROMOS 2017F-PROMO MARCADOR 2020.MP2 [00:50:09] 60db438889cd4459add423fd [00:50:40] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 See omnystudio.com/listener for privacy information.

Paralelo 20 (18/7/2021) [00:00:00] 9:00 am - Paralelo 20 [00:57:58] 60db438889cd4459add423fd [00:58:29] Audio [00:58:43] 12/02PROMO ONG SOÑAR DESPIERTOSQLXFRAME1AUDIO25_00_00 PROMOS 2017PROMO ONG SOÑAR DESPIERTO.MP2 [00:59:32] L-DF-PROMO WASAP FRIKISQLXFRAME1AUDIO25_00_00 PROMOS 2017F-PROMO WASAP FRIKI.MP2 See omnystudio.com/listener for privacy information.

Paralelo 20 (2/5/2021) [00:00:00] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 [00:57:06] THRE0001000 [00:57:37] 12/02PROMO ONG SOÑAR DESPIERTOSQLXFRAME1AUDIO25_00_00 PROMOS 2017PROMO ONG SOÑAR DESPIERTO.MP2 [00:58:26] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:58:27] L-DF-PROMO WASAP FRIKISQLXFRAME1AUDIO25_00_00 PROMOS 2017F-PROMO WASAP FRIKI.MP2 [00:59:01] GOLPE RM 1SQLXFRAME1AUDIO25_00_00 PROMOS 2017 GOLPE RM 1.MP2 [00:59:05] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:59:06] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 See omnystudio.com/listener for privacy information.

Paralelo 20 (25/4/2021) [00:00:00] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 [00:57:46] XGGA9400100. [00:58:16] L-DG-PROMO PODCAST RAQUELSQLXFRAME1AUDIO25_00_00 PROMOS 2017G-PROMO PODCAST .MP2 [00:58:44] PROMO CORRILLO NUEVACORRILLO ASTERIXROBINAUDIOSQLXFRAME1AUDIO25_00_00 PROMOS 2017PROMO CORRILLO NUEVA.MP2 [00:59:13] PROMO WACHAP 2SQLXFRAME1AUDIO25_00_00 PROMOS 2017PROMO WACHAP 22.MP2 [00:59:51] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 See omnystudio.com/listener for privacy information.

Paralelo 20 (18/4/2021) [00:00:00] 9:00 am - Paralelo 20 [00:00:04] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 [00:57:47] XGGA9400100. [00:58:17] DG3MFT20561H_MF_EVRGRN_RAP_3001G_Num1Reatil_LTTSl_30R FULL MIX [00:58:47] EnergyTransfer-Petroleum-Female-15-Vers2 [00:59:03] EUCC0206000 [00:59:33] 12/07/20F-PROMO MARCADOR 2020SQLXFRAME1AUDIO25_00_00 PROMOS 2017F-PROMO MARCADOR 2020.MP2 See omnystudio.com/listener for privacy information.

Paralelo 20 (11/4/2021) [00:00:00] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 [00:58:00] XGGA9400100. [00:58:30] QMAY2439OS1 GO EM [00:59:01] 3/29-4/11 DYRA1281000 [00:59:31] L-DF-PROMO WASAP FRIKISQLXFRAME1AUDIO25_00_00 PROMOS 2017F-PROMO WASAP FRIKI.MP2 See omnystudio.com/listener for privacy information.

Paralelo 20 (21/3/2021) [00:00:00] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:00:01] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:00:02] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 [00:57:57] FWRS2112000 [00:58:27] Q121 TMO Magenta Max Radio 30 WWVS9968 (1) [00:58:58] 3/1 - 3/28 EUCC0245000_Clean_Energy_Anthem_30_EN_Radio (1) (2) (3) [00:59:27] L-DF-PROMO WASAP FRIKISQLXFRAME1AUDIO25_00_00 PROMOS 2017F-PROMO WASAP FRIKI.MP2 See omnystudio.com/listener for privacy information.

Paralelo 20 (14/3/2021) [00:00:00] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:00:01] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 [00:58:02] DYRA1275000 [00:58:33] Q1-Cessation-COVID-DigitalAudio-Donald-30-Eng [00:59:03] 12/02PROMO ONG SOÑAR DESPIERTOSQLXFRAME1AUDIO25_00_00 PROMOS 2017PROMO ONG SOÑAR DESPIERTO.MP2 [00:59:52] L-DF-PROMO WASAP FRIKISQLXFRAME1AUDIO25_00_00 PROMOS 2017F-PROMO WASAP FRIKI.MP2 See omnystudio.com/listener for privacy information.

Paralelo 20 (7/3/2021) [00:00:00] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:00:01] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:00:02] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 [00:57:17] DYRA1275000 [00:57:47] 3/1 - 3/28 EUCC0251000_Cleaner_Laundry_Cleaner_California_EN_Radio (1) (2) (3) [00:58:17] THRE0001000 (9) [00:58:48] PROMO WACHAP 22SQLXFRAME1AUDIO25_00_00 PROMOS 2017PROMO WACHAP 22.MP2 [00:59:25] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 See omnystudio.com/listener for privacy information.

Paralelo 20 (28/2/2021) [00:00:00] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 [00:58:00] Audio [00:58:30] YALM0126000 [00:59:00] ORNTL20816 (19) [00:59:30] QMTPZ10675 (42) See omnystudio.com/listener for privacy information.

Paralelo 20 (21/2/2021) [00:00:00] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 [00:58:05] 3DTMF (5-D) SOLO RADIO AEQ PROMO SQLXFRAME1AUDIOPUBLICIDADDTMF (5-D) SOLO RADIO AEQ PROMO.MP2 [00:58:07] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:58:08] PROMO ONG RAIS DIC 19SQLXFRAME1AUDIO25_00_00 PROMOS 2017PROMO ONG RAIS DIC 19.MP2 [00:58:44] Audio [00:59:15] QMTPZ10675 (42) [00:59:45] PLZL0672000 (2) See omnystudio.com/listener for privacy information.

Paralelo 20 (14/2/2021) [00:00:00] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 [00:57:57] QMTPZ10675 (42) [00:58:27] TUBK0706000 [00:58:57] LSRA0021000_BookAppt_Masked_Founders_150Bundle_Radio_30 [00:59:28] Total_Wine_DonRoberto_Radio_30 (3) See omnystudio.com/listener for privacy information.

Paralelo 20 (7/2/2021) [00:00:00] 9:00 am - Paralelo 20 [00:57:55] 3DTMF (5-D) SOLO RADIO AEQ PROMO SQLXFRAME1AUDIOPUBLICIDADDTMF (5-D) SOLO RADIO AEQ PROMO.MP2 [00:57:56] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:57:57] 12/07/20F-PROMO PODCAST 2020SQLXFRAME1AUDIO25_00_00 PROMOS 2017F-PROMO PODCAST 2020.MP2 [00:58:21] ONG FUNDACIO GAEM FALCASQLXFRAME1AUDIO25_00_00 PROMOS 2017ONG FUNDACIO GAEM FALCA.MP2 [00:58:42] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:58:43] PROMO Seriadictos NACIONAL 2020Seriadictos NACIONAL 2020SQLXFRAME1AUDIO25_00_00 PROMOS 2017PROMO SERIADICTOS NACIONAL 2020.MP2 [00:59:15] L-SF-PROMO BAJO PAR 2 2019FERNANDOSQLXFRAME1AUDIO25_00_00 PROMOS 2017F-PROMO BAJO PAR 2 2019.MP2 [00:59:48] GOLPE RM 3 SQLXFRAME1AUDIO25_00_00 PROMOS 2017 GOLPE RM 3 .MP2 [00:59:50] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:59:52] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:59:53] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 See omnystudio.com/listener for privacy information.

Paralelo 20 (31/1/2021) [00:00:00] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:00:01] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 [00:58:02] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:58:03] 3DTMF (5-D) SOLO RADIO AEQ PROMO SQLXFRAME1AUDIOPUBLICIDADDTMF (5-D) SOLO RADIO AEQ PROMO.MP2 [00:58:05] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:58:06] L-DA-PROMO RM GOLLA VIDA ES COMO UN GOL OKROBINAUDIOSQLXFRAME1AUDIO25_00_00 PROMOS 2017A-PROMO RM GOL.MP2 [00:58:37] ONG FUNDACIO GAEM FALCASQLXFRAME1AUDIO25_00_00 PROMOS 2017ONG FUNDACIO GAEM FALCA.MP2 [00:58:57] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:58:58] 12/07/20F-PROMO PODCAST 2020SQLXFRAME1AUDIO25_00_00 PROMOS 2017F-PROMO PODCAST 2020.MP2 [00:59:22] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:59:23] PROMO ONG RAIS DIC 19SQLXFRAME1AUDIO25_00_00 PROMOS 2017PROMO ONG RAIS DIC 19.MP2 See omnystudio.com/listener for privacy information.

Paralelo 20 (24/1/2021) [00:00:00] 9:00 am - Paralelo 20 [00:57:59] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:58:00] 3DTMF (5-D) SOLO RADIO AEQ PROMO SQLXFRAME1AUDIOPUBLICIDADDTMF (5-D) SOLO RADIO AEQ PROMO.MP2 [00:58:02] 12/07/20F-PROMO PARALELO 20 2020SQLXFRAME1AUDIO25_00_00 PROMOS 2017F-PROMO PARALELO 20 2020.MP2 [00:58:35] RAFAGA RM 2020 1SQLXFRAME1AUDIO25_00_00 PROMOS 2017RAFAGA RM 2020 1.MP2 [00:58:43] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:58:44] 14/09/20PROMO 3 PQPSQLXFRAME1AUDIO25_00_00 PROMOS 2017PROMO 3 PQP.MP2 [00:59:11] X-VF-PROMO LA DEPORTECA OCT 20SQLXFRAME1AUDIO25_00_00 PROMOS 2017F-PROMO LA DEPORTECA OCT 20.MP2 [00:59:43] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:59:44] RAFAGA RM 2020 5SQLXFRAME1AUDIO25_00_00 PROMOS 2017ZZZ RMARCA DESCON1 A PROMO.MP2 [00:59:55] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:59:57] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:59:58] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 See omnystudio.com/listener for privacy information.

Paralelo 20 (17/1/2021) [00:00:00] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:57:57] 3DTMF (5-D) SOLO RADIO AEQ PROMO SQLXFRAME1AUDIOPUBLICIDADDTMF (5-D) SOLO RADIO AEQ PROMO.MP2 [00:57:58] 12/07/20F-PROMO PARALELO 20 2020SQLXFRAME1AUDIO25_00_00 PROMOS 2017F-PROMO PARALELO 20 2020.MP2 [00:58:32] RAFAGA RM 2020 1SQLXFRAME1AUDIO25_00_00 PROMOS 2017RAFAGA RM 2020 1.MP2 [00:58:40] 14/09/20PROMO 3 PQPSQLXFRAME1AUDIO25_00_00 PROMOS 2017PROMO 3 PQP.MP2 [00:59:07] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:59:08] X-VF-PROMO LA DEPORTECA OCT 20SQLXFRAME1AUDIO25_00_00 PROMOS 2017F-PROMO LA DEPORTECA OCT 20.MP2 [00:59:40] RAFAGA RM 2020 5SQLXFRAME1AUDIO25_00_00 PROMOS 2017ZZZ RMARCA DESCON1 A PROMO.MP2 [00:59:52] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:59:53] BLANCO 1## PROMO SQLXFRAME1AUDIO25_00_00 PROMOS 2017 BLANCO 1## PROMO.S48 [00:59:54] FINDESCOSQLXFRAME1AUDIO25_00_00 PROMOS 2017FINDESCO.MP2 See omnystudio.com/listener for privacy information.

Let’s learn some interesting inventions of Germany in this new episode of “Inventions”. We have to refill our car engines with diesel, right? But who made these diesel engines? It was made by Rudolf Diesel in 1868. One day he got an idea of creating a high compression igniting engine for cars. After a lot of experimentations, he finally made a fuel-based engine. The outlook of the diesel engine might have changed and modified today but the basic characteristics and technological science date back to the 1896 model. Every science lab has an electron microscope. Microscopes magnify small particles and give us a wider view. In 1931, German physicist Ernst Ruska and Max Knoll created the first working electron microscope which is a super useful invention in the world of science. You might have seen your parents wearing a contact lens in their eyes. Do you know what are those for? Contact lens corrects the problem of focus in our eyes and provides us with good vision. In 1888, a German ophthalmologist Adolf Gaston Eugen Fick used a blown glass to create the lens that would protect the cornea, the transparent part of our eye. The tape recorder is a kind of mixed invention. Fritz Pfleumer in 1928 invented magnetic tape and following this invention, later tape recorder was created. The 1st tape recorder was demonstrated in 1935. An audio engineer, John Mulein created the tape recorder all by himself in his studio. We all know about MP3 right? The audio format is used to compress large audio files without losing their original quality. Mp3 stands for MPEG. Mp1 appeared in 1992 but had low bandwidth. Then with a lot of modifications, MP2 was made which was ideally played for DVDs. The came MP3 which turned out to be a major hit all across the globe.Let’s learn about all these great German inventions in this short kids podcast.www.chimesradio.com http://onelink.to/8uzr4g https://www.facebook.com/chimesradio/ https://www.instagram.com/vrchimesradio/ Support the show: https://www.patreon.com/chimesradioSee omnystudio.com/listener for privacy information.

On this episode of Smart Energy Voices, Jeff Colvin, Executive VP of Sales at MP2 Energy, joins John Failla of Smart Energy Decisions to discuss his career as a leader in the energy industry and his role at MP2 and its relationship with Shell Energy North America. With the growing interest that international oil companies have in the energy transition and the role that MP2 Energy is specifically playing for Shell Energy North America, this conversation provides tremendous insights.  You will want to hear this episode if you are interested in... Jeff and his role with MP2 Energy [1:38] Shell's interest in renewables [3:12] Advantages of being an early mover in developing an integrated power business [5:24] The role MP2 Energy is playing in Shell's North American strategy [8:07] Important considerations for shifting to renewables and sustainability goals [11:19] How MP2 is positioned to meet expanding customer needs [13:09] Some specific customer deployments MP2 has had success with [15:17] How large company announcements are bringing small renewable initiatives [18:31] How Shell's reach has allowed MP2 to adapt and move with the company [20:23] Where the industry is heading in terms of evolving customer requirements [22:30] What led Jeff to start a career in the energy industry [25:10] The pivotal point that propelled Jeff into seeking leadership positions [27:27] How Jeff's career has evolved and his proudest accomplishments [29:28] Jeff's biggest challenges [33:48] Integration and acquisition challenges and solutions [36:29] Jeff's legacy in the energy industry [39:25] The focus is electricity Shell sees electricity as the fastest-growing part of the energy industry and a huge opportunity as companies focus more on renewables to mitigate their greenhouse gas emissions. Shell Energy North America (SENA) is a leader of power traders and wholesale suppliers in North America and abroad. MP2 Energy,  which was acquired by Shell in September of 2017, works with companies like Wells Fargo to meet renewable energy goals.  How larger company initiatives are impacting Scope 3 emissions As large corporations like Facebook, Google, and Amazon set science-based targets, companies like Shell are beginning to communicate with companies that provide their supply chain and scope 3 emissions. Companies that supply these large corporations are influenced by these conglomerates to live up to their sustainability initiatives and goals alike. It is encouraging to see smaller companies in the supply chain see value in the message that larger corporations are sending worldwide when it comes to sustainability.  Leaving a legacy...how Jeff would like to be remembered In Jeff's words, “I'd like to know that our customers are in a better place with their budget and with their sustainability targets and that they're smarter about how they use their power than they were before they came to us or before we met them. I'd like to know that our brokers and consultants trust us to do what's right for them and for our mutual customers, day in and day out. I'd like to know that MP2 and Shell are better, maybe just a bit, but better because I and my team were here, and that the team we built made a difference. I know, those are lofty goals considering the size of Royal Dutch Shell, but it remains. If I walk away in 20 years and the customers and the brokers and the organization as a whole are better because of what our teams delivered, then I'm a happy and a proud man and I walk away knowing that I did good.” Resources & People Mentioned MP2 Energy a Shell Energy North America Subsidiary Connect with Jeff Colvin On Linkedin Jeff Colvin, Executive Vice President Sales, MP2 Energy At MP2 Energy, Jeff Colvin, EVP, Sales, has built up both the Pricing and Sales teams, improved training and coaching efforts, deployed a CRM solution, built and released a scalable Renewable Energy platform, and has been critical in leading a Sales Team that increased sales year over year every year that he has been in the organization.  Most recently Jeff onboarded a new channel, a Large C&I National Direct Sales Team, something very different for MP2 historically, a business built on the backs of its Retail Brokers and Consultants.  Jeff joined MP2 Energy in 2016; in April 2020, he was promoted to EVP, Sales to help guide, direct, and lead the commercial C&I business and the overarching strategy of MP2 within Shell.  Connect With Smart Energy Decisions https://smartenergydecisions.com   Follow them on Facebook Follow them on Twitter Follow them on LinkedIn   Subscribe to Smart Energy Voices If you're interested in participating in the next edition of the SED Renewable Energy Sourcing Forum taking place on December 7-11, visit smartenergydecisions.com or email our Event Operations Director, Lisa Carroll at lisa@smartenergydecisions.com"

Ang Modified Pag-IBIG Savings II o MP2 ay isang savings program na open para sa lahat ng members ng Pag-IBIG. Kinakailangan lang na more than PhP5,000 ang kinikita kada buwan para mag-qualify dito. Paano ba magbukas ng MP2 account at anu-ano ba ang mga benepisyo nito? Pag-usapan natin ito sa ating #UsapangPera. #PagIBIG #MP2 Read more about Pag-IBIG MP2 at http://bit.ly/pag-ibig-mp2 Join the USAPANG PERA GROUP

Ang Pag-IBIG ay ang national savings and housing program ng gobyerno. Lingid sa kaalaman ng marami, nagbibigay ng mataas na kita sa savings natin, 100% government-guaranteed at tax free pa. Magandang gamitin ang Modified Savings Pag-IBIG 2 (MP2) para sa pag-iipon sa mahahalagang financial goals na long term in nature tulad ng pagpapaaral sa anak. Alamin sa episode na ito ng #UsapangPera with Sir Vince and guest Atom Araullo. #UsapangPera More details here: https://bit.ly/2QfRD2J Join the USAPANG PERA GROUP

Henry Jennings from Marcus Today and Claude Walker from A Rich Life go in-depth and stock-specific. Stocks: NEA, TGR, OPY, ADH, TRS, OCL, HM1, SYD, MP2, VRS. The stock of the day is Domino's Pizza Enterprises Ltd (DMP). See acast.com/privacy for privacy and opt-out information.

Inizia a suonare il basso da autodidatta all'età di 16 anni e due anni dopo ne fa una professione entrando a far parte della band di Elisa. Ha suonato in gran parte della discografia e in tutti i tour della cantante friulana e dal 2006 ha ricoperto per lei anche il ruolo di direttore musicale, dando vita a tour spettacolari e tecnologici. In oltre vent'anni di carriera ha collaborato in studio e live con artisti del calibro di: Vasco Rossi, Gianna Nannini, Ivano Fossati, Mauro Pagani, Tiromancino, Tiziano Ferro, Carl Palmer, Alberto Fortis, 883, Arisa, Bobby Solo, Serena Abrami, Mp2, Maurizio Solieri, Massimo Ranieri, Francesca Michielin, Bugo e moltri altri. Facciamo quattro chiacchiere online con... Max Gelsi!Vai al Video

* Tutti i guadagni pubblicitari di Marzo, Aprile e Maggio 2020 di questo canale verrano devoluti alla protezione civile.Tutti i CORSI di CHITARRA: https://chitarrafacile.com/corsiMax Gelsi diventato famoso per essere stato il bassista do Elisa ed in alcuni casi anche il suo produttore e direttore musicale della band, ma ha collaborato (live o studio) anche con Vasco Rossi, Gianna Nannini, Ivano Fossati, Mauro Pagani, Tiromancino, Tiziano Ferro, Carl Palmer, Alberto Fortis, 883, Arisa, Bobby Solo, Serena Abrami, Mp2, Maurizio Solieri, Massimo Ranieri, Francesca Michielin e molti altri…In questa puntata del podcast Chitarra da Bar (quarantena version), è con noi uno dei migliori bassisti e musicisti in Italia.TUTTI i PODCAST: https://www.youtube.com/playlist?list=PLCLqIdUojsVpmMhqwGWILcVJO2DmbSQfpContatti di Max Gelsi:Facebook: https://www.facebook.com/max.gelsi#MaxGelsi #Podcast #Intervista #ElisaAUDIO PODCAST:iTunes: https://itunes.apple.com/it/podcast/chitarra-da-bar/id1182987992?mt=2Spotify: https://open.spotify.com/show/5sA0nKRZCxNVvCtXqrfjLTSpreaker: https://www.spreaker.com/show/chitarradabarATTREZZATURA:Microfoni: https://amzn.to/2RzrZqHMixer: https://amzn.to/2J776QWCavi per Microfoni: https://amzn.to/2RR4wBFAsta piegevole: https://amzn.to/2Xlh452ARREDAMENTO:Tazza: https://www.moteefe.com/chitarra-da-bar?color=black&product=black-mug&size=11ozLampada nel retro: https://amzn.to/2Ysv2naQuadri: http://stilechitarra.comPupazzetti dei Chitarristi: https://amzn.to/2RR5vll

¿Y si pudiéramos captar la contaminación del aire que nos rodea y convertirla en algo útil? El inventor Anirudh Sharma nos cuenta como creó AIR-INK, una tinta negra hecha a partir de la contaminación por material particulado fino (MP2,5). Aprendamos cómo estos materiales basados en el carbón pueden alterar procesos anticuados en industrias como la moda, las imprentas y los embalajes, y hacer que el mundo sea un poco más limpio al mismo tiempo.

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 Our Masked Podcasters take on an entire multiverse when they confront the Mandela Effect, MP2 encoders, and WELCOME DATACOMP. Just by posting this episode they are now one of the most long-lived podcasts in Internet history!

If you enjoy this podcast, consider buying me a coffee: https://adamstoner.com/support ‘Defying Conventions: Is Beats 1 Redefining Radio?' was originally submitted as part of a University of Gloucestershire Radio Production module. With the exception of two small typographical changes, this essay is posted exactly as it was submitted. Appendices have been redacted but bibliography and in-line references remain – get in touch if you need to chase anything. Apple's annual World Wide Developer Conference is a showcase of the company's latest software and technology. Described by CEO Tim Cook as the ‘epicentre of change', 2015 marked their ‘most global conference ever' (Apple, 2015), a fitting stage to announce their new ‘worldwide' and ‘always on' internet radio station, Beats 1. The announcement of Beats 1 came as a footnote to an addendum. The presentation mainly dealt with Apple's latest technological offering, ‘Apple Music' – a streaming service and social network combined, of which the radio station is merely a subsidiary – rather than with Beats 1 Radio directly. Nevertheless, speaker, record producer, and entrepreneur Jimmy Iovine painted it as a nod to the company's history; the minds behind the iPod and media software iTunes were returning to the grassroots of music sharing: radio. This essay will look at the early success and criticisms of Beats 1. It will do this by examining how the station defies established radio theory and is helping to evolve the medium both technologically and stylistically. It will contextualise these findings in the form of current industry practice, as well as what pressures the station may put on commercial and public service radio broadcasting in the United Kingdom. The essay aims to explore the timing and reasons behind the inception of the station and will raise questions behind its ideology. It will draw on a range of practitioner, academic and secondary sources as well as personal listening and theorisation in order to explore whether Apple's Beats 1 is ‘redefining radio'. Defining Radio From the offset, a couple of basic but important distinctions need to be made. As the Radio Advertising Bureau reflect in their 2014 report Audio Now (p.10), new forms of audio are continually emerging. The report highlights three main forms of consumer-level audio, with the latest — ‘on-demand' — being less than ten years old: ‘Owned audio': Here, the consumer owns the physical or digital audio format. This may include digital downloads, gathered legally or otherwise, or physical copies of the sound, such as CD, cassette or vinyl. ‘Live audio': This is the oldest of the three forms. The report refers to it as ‘live radio' but for the purposes of this essay we shall expand its definition to all audio consumed in real-time, as it is performed or transmitted. ‘On-demand': The newest of the three and the most complex to define due to its multifaceted nature. This encapsulates audio where the consumer does not have the original file and listens in isolation. Examples cited in Audio Now include streaming services, podcasts and YouTube videos. This notion of ‘owned audio' can be entirely discounted when discussing Apple Music as a standalone product; the user never gets physical access to the music files, just the right to stream them in exchange for a monthly membership fee of £9.99. The second and third definitions – ‘live audio' and ‘on-demand' respectively – are vital when addressing Beats 1 and Apple Music's other ‘radio'-esqué offerings, the definition of which has been somewhat corrupted by modern-day ‘on-demand' music streaming services. ‘Radio', as understood by the likes of Spotify, Deezer, Pandora, or similar, is intrinsically different from the traditional and well-established institution of radio broadcasting. This is not to say traditional radio is out-dated – far from it – but that ‘on-demand' services have appropriated the name of the medium and have used it incorrectly. There are multiple differences between the two, with the most notable being that the more traditional notion of radio broadcasting features human presence. Chignell (2009, p.33) explains people ‘add meaning' and context, and also provide a sense of co-presence. This is the complete antithesis of so-called ‘radio stations' on streaming services which strip broadcasting of its ‘essential element' (Priestman, 2006, p.36): human-to-human contact. As Corderio (2011, p.499) highlights, there is a long line of radio theorists who contend ‘music playlists, without human interaction, should not be confused with radio', and that radio can be easily defined as public, point-to-point_s_ broadcasting. Priestman describes the aforementioned, human-bare stations as ‘automated web “jukebox[es]”' and for the purposes of this essay, these on-demand web-jukeboxes will be called exactly that. iTunes Radio – the 2013 predecessor of Apple Music – was one such service. Allowing users to create ‘stations' around a single artist or band, algorithms mixed content from one band with similar material by similar artists. As Baldwin (2013) reports, iTunes Radio let users ‘rate the songs (…) as they stream[ed]', thereby learning individual preference in order to modify the output to better suit taste. While iTunes Radio was by no means a failure, algorithms, as Iovine himself admits, ‘can't do it alone' (Dredge, 2015). While movements in the realm of acoustic and computer science are moving in the right direction, machines currently fail to recognise mood, thus playing inappropriate or mismatched tracks sequentially, and cannot provide all important context. Enter Apple Music. While the newer service still contains web-jukeboxes, Apple makes a clear point of distinguishing Beats 1 Radio from them. In the native Music application on iOS, a graphic inviting people to ‘Listen Now' takes centre stage (appendix; a), occupying well over 50% of the screen space. Not only does this force automated-jukebox stations to exist several swipes away but it also separates Beats 1 from these lesser-refined services. The Beats 1 landing page on the Apple website makes a further point of highlighting this distinction by defining the true meaning of radio itself: ‘No matter where you are or when you tune in, you'll hear the same great programming as every other listener' (2015b). This reinforces a concept Chignell (2009, p.74) writes about, co-presence, a theory Scannell and Cardiff (1991) highlight, imagined community, and Marshal McLuhan's Global Village, ‘one world connected by an electronic nervous system' (Stewart, n.d.). Irrespective of scale, collective listening is precisely what radio is all about. As a technology company, there are technological considerations to take in to account when defining what ‘radio' means to Apple. As the smartphone market leader (Forbes, 2015), it is fitting of Apple to create a station that is marketed at, and primarily received on, mobile devices. According to a 2015 report from the International Federation of the Phonographic Industry, the digital music industry is worth $6.85 billion worldwide per annum (IFPI, p.6), with ‘music subscription services' accounting for 22.75% of revenue. On the other hand, ‘radio is a massive $20 billion industry' (Truong, 2015). At a time where physical format sales are declining (IFPI, 2015b), where the revenue share of music streaming is growing exponentially, and where radio is still ‘able to command the largest share of the listening ear' (Lloyd, 2015, p.293), Apple wants in. Moreover, there are some strong statistics to suggest mobile listening is quick becoming a force to be reckoned with. ‘31 minutes a day is the average amount of time spent listening to music on a phone', Global (2015) claims, and ‘65% of “digital audio” streamers' – both live audio and on-demand consumers – ‘listen with head[/ear]phones'. Undoubtedly, radio is an intimate and personal medium, esteemed by consumers (McLeish, 2016, pp.3 to 6). To further emphasise this, by interacting through earphones, listeners are choosing to place broadcasters in their ears, to make the broadcast a part of their body, a sacred trust and one only radio could garner. Global also claim ‘44% of 35-44 year-olds' stream music over tablet devices. Logically, what with early adoption rates and increased technological competence in younger generations who have grown up with this hardware from an early age, this number will only be higher in the 15 to 24 and 25 to 34 demographics, precisely the age of consumer Apple is attempting to capture with Beats 1 Radio. Defying Radio In the words of both Finer (2003, p.32) and Castelles (2003, p.17), the internet is the world's first international radio frequency. Apple not only advertise Beats 1 as being ‘worldwide', but as ‘a truly global listening experience', letting audience members discover ‘what's going on in the world of music'. While parts of this statement are correct – the station can be received in 100 countries around the world (Apple, 2015c), although that is only 51% of the planet – the overall sentiment could not be further from the truth. At present, the BBC World Service is the world's largest international broadcaster (House of Commons, 2010, ev.11) serving over 188 million people per week (BBC, 2009). Whilst the on-air content of each station cannot be compared – the BBC World Service is primarily a news and informational platform, while Beats 1 is purely a music station – there are, in terms of scale, many similarities. Evident from its marketing decisions and branding, Apple's goal is for Beats 1 to adopt an audience of ‘World Service' magnitude – ‘truly global', ‘worldwide'. However, in the same way Beats 1 broadcasts from exclusively Western locations – New York City, London, and Los Angeles – yet claims it is a ‘global' voice, the BBC World Service soldiers in a similar vein. The Operating Agreement of the World Service (BBC Trust, 2012, p.6) sets out English language services as their ‘core offer' and designates 75% of overall output worldwide to English language programming each week. Even the name of the BBC World Service contains a jarring juxtaposition, seating ‘British' and ‘World' two words apart. On the other hand, ‘beats' – acoustically speaking – know no borders and are not unique to any specific genre of music. Here, Beats 1's lack of cultural identity, as far as the name of the station and the simplistic graphical signifiers and branding it uses, allows the station to be transient in nature. However, as O'Malley (2015) reflects, this ‘ill-defined genre remit' hasn't come without criticism – He goes on to state ‘if you make content so broad, it becomes meaningless'. Beats 1 contradicts Priestman's (2006, p.233) argument that ‘web radio works best as a narrow-cast or niche medium' and Nyre's argument (2008, p.192) that music radio stations attempt ‘to attract niche audiences'. Roy Martin, managing editor of Radio Today, claims Beats 1 threatens ‘specialist music stations such as 1Xtra, Kiss [and BBC Radio] 6 Music' (2015). The breadth of music these stations play is replicated on Beats 1 without advertisements or pressures to fill remit goals. Contrasting Martin's sentiment, BBC Radio 1's controller Ben Cooper – who has lost two talents: Head of Music George Ergatoudis to Spotify (Lunden, 2015) and Lowe to Apple – claims ‘a rising tide lifts all boats' (Griffiths, 2015). Martin continues, ‘the likes of Radio Plymouth, The Bee [Lancashire] and Clyde 1 [Glasgow]' need not feel at risk, despite Beats 1 being billed as ‘the world's local station' (Quartz, 2015). Although Beats 1 can attempt to masquerade as local radio, when it comes to discussing truly local news and events, even at its closest level of inspection Beats 1 has to take a national view for fear of alienating other listeners. Locality is what makes radio work and Beats 1, with its syndicated, single, linear programming which never once breaks out in to local titbits, cannot possibly achieve the same effect on its desired scale. The on-air content of Apple's Beats 1 behaves as a BBC Radio 1Xtra and Radio 6 Music hybrid. The station is clearly attempting to promote ‘challenging, innovative' (BBC Trust, 2012b, p.2) music, with a distinctive focus on ‘contemporary black music (…) rarely heard elsewhere' (BBC Trust, 2015, pp.2 to 4), as the aforementioned BBC stations also reflect in their respective remits. Introducing challenging music comes with the need to reason track selection and explain why the creation deserves respect. BBC Radio 6 Music achieves this through interviews and technical discussions, many of which deconstruct musical theory, and through detailed back-announcements that may include the name of record labels, similar musicians, and artist influences. BBC Radio 1 Xtra achieves the same effect by discussing the artists' potential influence in relation to black British culture. This form of education, required by remit, is evident in the plays-per-day of each station, with BBC Radio 6 Music totaling an average of 172 plays per day and 1Xtra averaging 159 (Last FM, 2016, 2016b). The breaks are filled with news, documentaries and interviews. This is a stark contrast to Beats 1, a station that plays an average of 300 songs per weekday, peaking to 600 on weekends due in part to ‘high-track-turnover DJ mix shows that play during prime party hours' (Quartz, 2015). The on-air schedule of Apple's Beats 1 Radio is unlike any other station. Those familiar with radio will be aware of dayparting, ‘the practice of segmenting the broadcast schedule in to blocks (…) programmed for unique audience demographics and listeners' daily habits' (Piasek, 1998). Dayparting helps broadcasters provide more of that all-important context Chignell (2009, p.33) discusses. Nielsen Audio (2015, p.23), one of several U.S. audience rating services, divides a weekday into five such parts. Having slightly adjusted the times for an audience based in the United Kingdom, those dayparts are as follows: 0600 to 9000: Breakfast 0900 to 1600: Daytime 1600 to 1900: Evening Drive Time 1900 to 2300: Late Night 2300 to 0600: Overnight (colloquially known as the ‘graveyard slot') James Cridland believes (2015) ‘it makes no sense putting the money into a great breakfast show (…) because the timezones mean it's always breakfast somewhere'. Beats 1 replays its three flagship programmes – Zane Lowe, Ebro Darden, and Julie Adenuga – on a twelve-hour loop, thus hitting both eastern and western-based audiences with all three shows in any given 24-hour period. The rest of the schedule is comprised of irregular and one-off programmes fronted by musicians from Elton John to HAIM, and organisations like Noisey and Pitchfork. This pre-recorded content, masquerading ‘as live', is broadcast at times relevant to the market Apple is attempting to target. For example, St. Vincent's programme is played at 3 a.m. GMT, 7 p.m. PST (American East-Coast) and 11 a.m. CST (Mainland China), evidently targeting listeners in the Americas and Asia rather than the United Kingdom. Whilst this may seem a strange idea, it works. One of radio's early strengths, the art of ephemeral broadcasting, is being eroded in the age of podcasting, ‘owned audio' and ‘on-demand'. With this comes a pressure for more refined content – producers now must craft sound not only for initial impact, but also for replay value. Transmitting great content once then losing it to the ether is neither cost effective nor clever. LBC – a commercial, London-based news and talk station – is one of the first in the United Kingdom to implement pay-for catch-up services. Subscription services on a rolling monthly basis cost £3.99 (AudioAgain, 2014). In comparison, Beats 1 offers the same catch-up method: pay to become an Apple Music member. ‘While it doesn't quite provide the experience of listening to the show live, (…) every DJ will post a set playlist for their show a few hours after it ends' (iMore, 2015). Most commercial radio stations are yet to offer on-demand catch-up services at all, but some, like Fun Kids – the UK's only radio station aimed at under-12s – have in excess of 80 podcast channels (Think Fun Kids, n.d.). It is as-of-yet unclear whether the pay-for catch-up model works well enough to warrant the long-term investment required by commercial radio stations in order to develop distribution platforms. However, empowering the consumer through this medium provides another point-of-entry to the station and rewards active consumers with the opportunity to replay their favourite moments from past programmes, or to store the show for posterity. Given the high profile musicians Beats 1 has access to and the respective fan-bases of those musicians, Apple's move is clearly another call to subscribe. Once an interview or programme has been broadcast, the only way for dedicated fans to hear that content again – or catch-up, if they missed it first time around – is to pay. Apple know many fans have a fear of missing out, desperate to hear content from their favourite creators, therefore can reasonably assure themselves a select number of subscribers by providing exclusive content hidden behind paywalls. Redefining Radio Being owned by a multinational, technological giant has its advantages. While the equipment Beats 1 uses to broadcast is the same as any other digital radio station, the techniques are certainly groundbreaking. Beats 1 is available in two stream formats, 64 kbps and 256 kbps (Painter, 2015) AAC, superior to DAB's MP2 streams which vary from 64 kbps – for stations including Absolute Radio, Amazing Radio and BBC Radio 5 Live – to 192 kbps – used exclusively by BBC Radio 3 (Laird, 2015). With concern to mobile devices, where the vast majority of stations stream second-by-second, Beats 1 utilises the new HLS streaming format. HLS is HTTP Live Streaming, a new communications protocol developed and implemented by Apple (2014). Designed to be adaptive, devices request stream information in packets of varying quality, and, if at any point diminished bandwidth or download speed causes stress to the stream, devices will request the next packet in a lower quality. This creates the effect of zero buffering, allowing for a smooth and more dynamic listening experience. The highly customisable nature of mobile phones makes this next statistic hard to measure but assuming a couple of reasonable conditions – that a user has biometric Touch ID enabled and has not moved the Music application from the factory default setting in their iPhone's docking bar – an ordinary mobile user can become a Beats 1 listener in only four taps. If Siri's newer hands-free function – ‘Hey Siri' – is enabled, a user can become a listener without even having to touch their device (appendix; b). In stark contrast to popular radio streaming applications such as TuneIn or RadioPlayer – two of numerous for desktop and smartphone – Apple forces consumers to use their dedicated Music application in order to hear Beats 1. The reason behind this decision is simple: Apple is a lover of control; proven by the fact Beats 1 audio steams are encrypted. The keys to decrypt the audio streams lay within the Music application itself. When addressing Apple's design decisions, the company has previously been accused of attempting to create a ‘totalitarian monoculture' (Bissell, 2008), a statement that is hard to defend Apple against. Indeed, in order for a listener to switch from Apple's Beats 1 to a potential rival – say, BBC Radio 1 or Capital FM – they would have to conduct at least eighteen further interactions with their device, first by launching a non-native iPhone application, then by having to search for the station before launching it, an overwhelming contrast in user-friendliness from the potential hands-free starting of Beats 1. Matt Deegan – radio practitioner and Creative Director of Folder Media – emphasised this, explaining the inception of Beats 1 is a move to ‘keep people in the Apple Music ecosystem' (University of Gloucestershire, 2015). On December 29th 2015 it was reported (RadioToday) Beats Electronics LLC., a division of Apple and the owners of the Beats brand, had put in a bid to internationally trademark the names of four potential new stations, Beats 2 through 5 and respective station logos ‘B2' through ‘B5'. Whilst Apple has made their intention to expand its radio arm clear (Billboard, 2015), it is unknown whether the filings are just a protective measure to prevent others piggybacking the Beats Radio brand. In the United Kingdom, the government-approved communications and competition regulator Ofcom, can step-in to ensure monopolies of broadcasting remain fair. If a station like Beats 1 wanted to broadcast on FM, AM, or even DAB, there's a high likelihood that Apple – with their marketing budget in excess of $1 billion USD (United States Securities and Exchange Commission, 2012) and end-goal of creating several ‘Beats'-branded stations – would not be in receipt of an license. This is where broadcasting solely online has measureable advantages, namely in the lack of regulation. Under the sole condition Apple pays for the rights to stream music in the 100 countries Beats 1 is playable from, there are no further restrictions. Although indecency regulations do not apply to its online streams, Apple still chooses to play non-explicit, clean, radio-edited versions of tracks 24/7. ‘[C]ensoring explicit language could be a matter of playing it safe rather than hoping the content flies everywhere it's played,' Kastrenakes (2015) believes, ‘it's likely a way to stay in advertisers' good graces — and it's certainly possible that ads will show up on Beats 1 eventually, especially since it's available for free', he adds. Where a track has a particularly high number of expletives, presenters signpost the non-censored version as ‘now streaming on Apple Music', a call to subscribe to the service for uncensored content ‘as the artist intended'. As Priestman (2006, p.3) reminds us, ‘[r]adio was supposed to mean the end of newspapers [and] television was supposed to mean the end of radio', but as is now evident, newer mediums change their predecessors but do not replace them. Criticism aside, Apple has made some logical additions to the visual and multimedia assets accompanying radio. Beats 1's metadata – ‘data that provides information about other data' (Merriam Webster, n.d.) such as what is playing on the station – is visualised on the iPhone lock-screen (appendix; c, d). If users are Apple Music subscribers they can ‘favourite' tracks, add them to personal playlists for offline ‘on-demand' streaming, and share the station via social media channels. Moreover, the synergy Apple's Beats 1 manages to achieve by embedding its content within the native Music application is unrivalled. Presenters regularly direct listeners to their ‘Connect' pages – the social networking arm of Apple Music – to see content complimentary to on-air discussions. Apple's monopolistic attitude over its content pays-off here, where the dynamo and fluidity of content publishing aids the sense of liveness. While it is clear to see Apple have brought many innovations to the worlds of technology and of music – and is continuing to experiment, along with on-demand streaming services, with the power of radio – I am unconvinced Beats 1 poses a threat to traditional notions of radio broadcasting. I believe Apple has missed a trick by failing to make the station more revolutionary. The stream is ‘live' but its DJs are not, the station is ‘global' but radio works best locally. It is entirely within Apple's capabilities to syndicate international programming with local break-offs, in the same way Heart FM syndicates a national breakfast show with regional news and travel. Similarly, Apple could easily syndicate its presenters across several genres of station, unifying links but playing different tracks, thus narrowcasting to niche audiences while still maintaining an overall brand identity. Absolute Radio's ‘Project Banana', piloted during Christian O'Connell's breakfast show, adopts this method, handing consumers the power to ‘choose the music to suit their tastes, while enjoying and interacting with the show's hosts' live (MediaWeek, 2014). While the station certainly has had success in marketing itself as a ‘breakthrough', in the words of James Cridland (2015) ‘I'm not sure it'll set the world on fire'. Moreover, the move to launch a radio station has attracted many critics, one of which stated it was ‘a terribly exclusive vanity project' (O'Malley, 2015), a statement I'm inclined to agree with. Matt Deegan is correct; Beats 1 is an advertising space for Apple Music, and contains measureable disadvantages for non-subscribers. Nevertheless, Beats 1 does pose serious questions for Station Managers and Radio Futurologists alike, namely around sharing multimedia content, ideas of exclusivity and privilege, and scheduling for maximum impact. Where Beats 1 excels, such as in technological competence and innovation, it is my opinion more traditional stations fall far behind. Here, they really are ‘redefining radio'. In this digital age, stations need to strive for technological excellence and Beats 1 is a prime example. This is not shocking, as the biggest and most valuable technology company in the world owns Beats 1. It is just a shame that, as far as content is concerned, where other stations excel, Beats 1 misses the boat. It comes across clumsy and mismatched, alienating and lazy, rather than the inclusive, ‘worldwide', gritty and new-age aesthetic it needs to succeed. – Bibliography Apple (2014) ‘HTTP Live Streaming Overview' On: iOS Developer Library [Accessed 01 January 2016] Apple (2015) Apple – WWDC 2015. [Online Video], 15 June. [Accessed 01 October 2015] Apple (2015b) Music: Radio [Online] [Accessed 01 October 2015] Apple (2015c) Availability of Apple Music, Apple Music Radio, and iTunes Match [online] [Accessed 01 October 2015] AudioAgain (2014) LBC Podcasts [online] [Accessed 21 January 2016] Baldwin, R. (2013) ‘Apple Dials in iTunes Radio, a New Streaming Music Service'; Wired. [online] [Accessed 24 November 2015] BBC (2009) ‘BBC's international news services attract record global audience of 238 million' On: BBC Press Office. [online] [Accessed 05 January 2015] BBC Trust (2012) Operating Agreement: BBC World Service [online PDF] [Accessed 08 December 2015] BBC Trust (2012b) BBC 6 Music Service Licence [online PDF] [Accessed 30 December 2015] BBC Trust (2015) 1Xtra Service Licence [online PDF] [Accessed 15 January 2015] Billboard (2015) Apple Could Launch Five More Beats Radio Stations, According to Report [online][Accessed 10 December 2015] Bissell, M. (2008) ‘The Totalitarian Regime of Apple' On: Michael Bissell [online] [Accessed 04 January 2016] Castells, M. (2003) The Rise Of The Network Society, The Information Age: Economy, Society And Culture, 2nd edn. Blackwell: Oxford. Chignell, H. (2009) Key Concepts in Radio Studies. Sage: London Cordeiro, P. (2012) ‘Radio becoming r@dio: Convergence, interactivity and broadcasting trends in perspective' In: Participations; Journal of Audience & Reception Studies; Vol. 9, Iss. 2, pp. 492 to 510. Cridland, J. (2015) ‘What We Can Learn From Beats 1' On: RadioInfo [Online][Accessed 24 Oct 2015] Cridland, J. (2015b) ‘What People Are Saying About Apple Music and Beats 1' On: RadioInfo [Online] [Accessed 24 Oct 2015] Dredge, S. (2015) ‘Apple Music intervieiw: ‘Algorithms can't do it alone – you need a human touch'; The Guardian [online] [Accessed 24 November 2015] Finer, J. (2003) Longplayer. Artangel: London. Forbes (2015) Apple Surpassed Samsung As Global Phone Market Leader, Says Report [online] [Accessed 15 December 2015] Global (2015) ‘An Audio Revolution' [online PDF] [Accessed 23 December 2015] Griffiths, S. (2015) ‘Apple Beats 1: Why is Apple bothering with radio?' On: BBC News [online] [Accessed December 29 2015] House of Commons [Foreign Affairs Committee] (2010) The Work of the BBC World Service 2008–09 – Third Report of Session 2009–10 [online PDF] [Accessed 08 January 2016] IFPI (2015) ‘IFPI Digital Music Report 2015: Charting the Path to Sustainable Growth' On: IFPI [online PDF] [Accessed 19 January 2016] IFPI (2015b) IFPI Global Statistics [online] Available at: [Accessed 19 January 2016] iMore (2015) ‘How to listen to Beats 1 shows you've missed' On: iMore. [online] [Accessed 21 January 2016] Kastrenakes, J. (2015) ‘Apple is playing censored songs on Beats 1' On: The Verge.[Accessed 21 January 2015] Laird, J. (2015) ‘Why DAB radio in the UK is broken, and how to fix it' On: TechRadar [online] Available at: [Accessed 30 December 2015] Last FM (2016) ‘BBC Radio 6 Music Scrobble Library' On: Last FM [online] [Accessed 18 January 2016] Last FM (2016b) ‘BBC Radio 1 Xtra Music Scrobble Library' On: Last FM [online] [Accessed 18 January 2016] Lloyd, D. (2015) How To Make Great Radio. Biteback Publishing: London. Lunden, I. (2015) ‘Spotify Poaches BBC Radio Exec In Push For Localised, Curated And Undiscovered Content' On: TechCrunch [online] [Accessed 02 January 2016] Martin, R., On: RadioToday (2015) Trademarks made for more Beats radio stations On: RadioToday [online] [Accessed 28 December 2015] MediaWeek (2014) ‘Absolute Radio launches UK's first tailored music service, dubbed ‘Project Banana'' On: MediaWeek [online] [Accessed 20 January 2016] Merriam Webster (n.d.) Definition: ‘Metadata' [online] [Accessed 21 January 2016] Nielson Audio (2015) Nielsen Monitor-Plus™ Methodology by Medium [online PDF] [Accessed 01 January 2016] Nyre, L. (2008) Sound Media, From Live Journalism To Musical Recording. Routledge: London. O'Malley, J. (2015) ‘Apple Music's Beats 1 Radio Station is Just a Terrible Executive Vanity Project' On: Gizmondo [Online] [Accessed 24 October 2015] Painter, L (2015) ‘Apple Music FAQ: How to set up Apple Music, cancel your subscription, share an account, find tracks you've played in Apple Music' On: MacWorld [online] [Accessed 20 December 2015] Piasek, J., In: Godfrey, D. and Leigh, F. (1998) Historical Dictionary of American Radio. Greenwood Publishing: Portsmouth, US. Priestman, C. (2006) Web Radio: Radio Production for Internet Streaming. Focal Press: Oxford. Radio Advertising Bureau [RAB] (2014) Audio Now. [online] [Accessed 01 December 2015; PDF hard copy retained and available on request] Scannell, P., and, Cardiff, D. (1991) A Social History of British Broadcasting, vol. 1: 1992-1939. Blackwell: Oxford. Stewart, W. (n.d.) ‘Marshall McLuhan Predicts The Global Village' On: Living Internet [online] [Accessed 20 January 2016] Think Fun Kids (n.d.) ‘Podcasts' [online] [Accessed 19 January 2016] Truong, A. (2015) ‘Radio is a massive $20 billion industry, and Apple wants in' On: Quartz [online] [Accessed 20 December 2015] United States Securities and Exchange Commission (2012) Form 10-K, Apple Inc. ANNUAL REPORT PURSUANT TO SECTION 13 OR 15(d) OF THE SECURITIES EXCHANGE ACT OF 1934. [online] Published at Washington D.C.: United States. University of Gloucestershire (2015) Media Festival Lecture: Matt Deegan of Folder Media. [Digital hard copy retained and available upon request] Quartz (2015) ‘We analyzed a month of Beats 1 tracks to figure out Apple's taste in music' On: Quartz [online] [Accessed 12 January 2016]

In FrequencyCast Show 37, Carl and Pete look at the latest sat nav developments. We look at the latest Digital TV news - Sky HD boxes are being recalled, more on Freeview HD, plus the football rights scores. Also, your questions on cricket, BT Vision, routers and MP2 recordings.

In this exciting episode, MP2 promises to tell us of the adventures of the Chronic Argonauts, then utterly fails to do so. Then they chatter about Season 1 of Lost. Will MP1 go on another skeptical rant? There's only one way to find out!Well, a bunch of ways, actually. You could just write and ask us.  We don't mind.

Click Here This is my final project called, "The Idea Process."

The molecular structures of all silver halide monomers, Ag2X, AgX, AgX2 and AgX3, (X = F, Cl, Br, I), have been calculated at the B3LYP, MP2 and CCSD(T) levels of theory by using quasirelativistic pseudopotentials for all atoms except fluorine and chlorine. All silver monohalides are stable molecules, while the relative stabilities of the subhalides, dihalides and trihalides considerably decrease toward the larger halogens. The ground-state structure of all Ag2X silver subhalides has C2v symmetry, and the molecules can be best described as [Ag2]+X-. Silver dihalides are linear molecules; AgF2 has a 2Sg ground state, while all of the other silver dihalides have a ground state of 2Pg symmetry. The potential energy surface (PES) of all silver trihalides has been investigated. Neither of these molecules has a D3h symmetric trigonal planar geometry, due to their Jahn-Teller distortion. The minimum energy structure of AgF3 is a T-shaped structure with C2v symmetry. For AgCl3, AgBr3 and AgI3, the global minimum is an L-shaped structure, which lies outside the Jahn-Teller PES. This structure can be considered as a donor-acceptor system, with X2 acting as donor and AgX as acceptor. Thus, except for AgF3, in the other three silver trihalides, silver is not present in the formal oxidation state 3. Hybrid density functional theory methods have been used to examine the reactivity of hexafluoro- and hexachlorocyclotriphosphazene with respect to single, multiple and complete substitution with water, ammonia, phosphoric and sulfuric acid. Geometries of both educts and all substitution products habe been optimized and their thermodynamic properties are discussed. Based on these results the thermodynamically most favorable reaction pathways have been determined. Starting from a basic unit, which consists of two phosphazene rings that are geminally linked by two hydrazine bridges, several possibilities to form double-stranded chains or helices containing cyclotriphosphazenes were examined by PM3 calculations.

Trimesitylblei(IV)bromid und Dimesitylblei(IV)dibromid, Mes3PbBr und Mes2PbBr2 Bei der äquimolaren Umsetzung von Mesityllithium mit Blei(II)chlorid in THF bei Raumtemperatur konnten Mes3PbBr und als Nebenprodukt Mes2PbBr2 isoliert und charakterisiert werden. Die Plumbylene Mes2Pb, MesPbCl oder MesPbBr, können als Intermediate postuliert werden, die mit Mesityllithium weiter zu Mes3PbBr bzw. zu Mes2PbBr2 reagieren können. Die Bildung der Blei−Brom-Bindung ist vermutlich auf einen Austausch von Chlor gegen Brom zurückzuführen, welches sich durch die Synthese von MesLi im Reaktionssystem befindet. Eine Grignard-Umsetzung führte nicht zu einer Ausbeuteverbesserung, sondern die Ausbeute an Mes3PbBr sinkt von 44% aus der Reaktionsgleichung a auf 2% von Gleichung b. Besonders aussagekräftig sind die 207Pb-NMR Spektren der beiden Mesityl-Blei- Verbindungen. Die Spektren zeigen jeweils ein scharfes Signal für die Blei-Resonanz, welches von 13C-Satelliten umgeben ist. Auch alle 1H- und 13C-Resonanzen weisen aufgrund der Kopplung mit 207Pb Bleisatelliten auf. Ein besonders auffallendes Merkmal beim Vergleich der NMR-Daten von Mes3PbBr mit Mes2PbBr2 ist der signifikante Anstieg (~40- 60%) der Werte für die Kopplungskonstanten nJH-Pb (n = 4,6) und nJC-Pb (n = 1-5) vom Bromid zum Dibromid. Die Übereinstimmungen zwischen experimentell ermittelten (Röntgenstrukturanalyse) und quantenchemisch berechneten (PM3) Strukturparametern ist recht gut, was zeigt, dass die PM3 Parameter sogar für die Vorhersage der Eigenschaften von schwermetallorganischen Verbindungen wie Mes3PbBr und Mes2PbBr2 geeignet sind. Die besonders interessanten strukturellen Merkmale sind die Bindungswinkel am zentralen Bleiatom, welche wesentlich von den idealen Tetraederwinkeln (109.5°) abweichen. Die C−Pb−C-Winkel liegen sowohl experimentell, als auch rechnerisch bei 115-123°. Die C−Pb−Br- und Br−Pb−Br-Winkel liegen zwischen 96 und 115°. Diese Tatsachen stimmen hervorragend mit der Bent'schen Regel überein, welche besagt, dass elektronegativere Substituenten Hybridorbitale mit geringerem s-Charakter und elektropositivere Substituenten Hybridorbitale mit höherem s- Charakter bevorzugen [100-102]. Bei Trimesitylblei(IV)bromid handelt es sich um eine sehr stabile Verbindung, die sowohl hydrolyse- als auch luftbeständig ist. Ein Austausch des Halogens gegen eine Azid- Gruppierung konnte nicht zweifelsfrei nachgewiesen werden. Zwar sind in den IR- und Raman-Spektren der erhaltenen Substanzen die symmetrischen und antisymmetrischen Azid- Schwingungen erkennbar, doch sind die gefundenen Stickstoffgehalte zu gering, was zu der Vermutung führt, dass nur ein teilweiser Halogen-Azid-Austausch stattgefunden hat. Leider war bisher jede Trennung eines Mes3PbBr/Mes3PbN3-Gemisches unmöglich, ebenso waren Kristallzüchtungsversuche bislang erfolglos. Tetraphenylphosphonium(arsonium)octabromoplumbat(II), [Ph4E]2[Pb3Br8] mit E = P, As Neue anionische Blei-Halogensysteme wurden hergestellt, z.B. Tetraphenylphosphoniumoctabromoplumbat. Um [Ph4P]2[Pb3Br8] zu erhalten, wurde [Ph4P]Br mit PbBr2 bei 75°C in CH3CN umgesetzt. Das Anion bildet Ketten, in denen zwei verschiedene Arten an Blei-Atomen existieren; das eine besitzt eine oktaedrische Koordinationssphäre, ist somit von sechs Brom-Atomen umgeben, während das zweite Blei-Atom eine mehrfach verzerrt tetraedrische Koordination aufweist (Abbildung A). Das 207Pb-NMR Spektrum einer frisch hergestellten Lösung von [Ph4P]2[Pb3Br8] in DMSOD6 zeigt mit 323 ppm eine andere chemische Verschiebung als eine um ca. 4 Monate gealterte Probenlösung mit 208 ppm. Zu erklären ist dies wahrscheinlich durch einen zunehmenden Einfluss einer DMSO-Koordination über die Sauerstoffatome zum Blei-Atom. Das Anion [Pb3Br8]2− kann auch mit dem Kation [Ph4As]+ durch die Reaktion von [Ph4As]Cl mit PbBr2 bei 75°C in CH3CN isoliert werden. Hierbei konnte kein Chlorid- Transfer zum Blei hin beobachtet werden, so dass kein gemischtes Halogenoplumbat-Anion gebildet wurde. Die Struktur der Verbindung wurde mit Hilfe der Einkristall- Röntgenstrukturanalyse bestimmt. Die Struktur des Anions [Pb3Br8]2− entspricht hierbei dem in der Verbindung [Ph4P]2[Pb3Br8]. Das von einer frisch hergestellten Lösung von [Ph4As]2[Pb3Br8] in DMSO-D6 aufgenommene 207Pb-NMR-Spektrum zeigt eine chemische Verschiebung von 386 ppm. Der wenn auch nur geringe Unterschied im 207Pb-Shift von [Ph4As]2[Pb3Br8] (386 ppm) zu [Ph4P]2[Pb3Br8] (323 ppm), lässt sich durch den unterschiedlichen Einfluss der Kationen, die sich in ihrer Grösse unterscheiden und somit die Umgebung der Blei-Atome verändern, erklären. Wie schon bei [Ph4P]2[Pb3Br8] können die beiden unterschiedlichen Blei-Atome des Anions im 207Pb-Spektrum nicht unterschieden werden. Tetraphenylphosphoniumbromodichloroplumbat(II), [Ph4P][PbBrCl2]·CH3CN Gemischte Halogenoplumbate sind bisher nicht sonderlich gut charakterisiert worden. Setzt man [Ph4P]Br mit PbCl2 bei 70°C in CH3CN um (Gleichung c), so erhält man das gemischte Bromodichloroplumbat [Ph4P][PbBrCl2]·CH3CN. Das in der Verbindung koordinierte Acetonitril kann auch durch ein längeres Erwärmen der Substanz im Vakuum nicht entfernt werden. Die chemische Verschiebung im 207Pb-NMR Spektrum einer frisch hergestellten Lösung von [Ph4P][PbBrCl2]·CH3CN in DMSO-D6 beträgt 466 ppm. Vermisst man diese Probe nach ca. 4 Wochen erneut, so verändert sich der Shift von δ = 466 auf 361 ppm. Da dieses Phänomen auch u.a. bei der Verbindung [Ph4P]2[Pb3Br8] zu beobachten ist, kann ein möglicher Halogenaustausch im [PbBrCl2]−- Anion ausgeschlossen werden. Im Kristall sind die Anionen fehlgeordnet, und es werden keine Blei-Brom-Ketten gebildet, wie es z.B. im [Pb3Br8]2−-Anion der Fall ist, sondern diskrete [PbBrCl2]−-Einheiten. Die experimentell beobachteten und berechneten (MP2 und CCSD) Struktur- und Schwingungsdaten wurden miteinander verglichen. Die Übereinstimmung zwischen berechneten Raman-Daten und den beobachteten Raman-Frequenzen ist sehr gut. Die durch Röntgenstrukturanalyse gemessenen Pb−Cl- und Pb−Br-Bindungslängen liegen ebenfalls im Rahmen der auf MP2-Niveau kalkulierten Werte. Die kürzere Rechenzeiten benötigende und somit billigere MP2-Methode in Kombination mit einem "double-zeta"-Basissatz hat sich dabei als zuverlässige Methode erwiesen, um gute Strukturresultate und Schwingungsfrequenzen zu erhalten. Tetraphenylphosphoniumchlorodibromoplumbat(II), [Ph4P][PbBr2Cl]·CH3CN Dieses weitere, gemischte Halogenoplumbat wurde durch die Umsetzung von [Ph4P]Cl mit PbBr2 bei 70°C in CH3CN erhalten (Gleichung d). Hierbei erfolgt ein Chlorid-Transfer auf das Blei. Wie schon bei [Ph4P][PbBrCl2]·CH3CN lässt sich auch hier das koordinierte Acetonitril nicht aus der Verbindung entfernen. [Ph4P]Cl     →  CN CH PbBr 3 2 , [Ph4P][PbBr2Cl]·CH3CN (d) Die chemische Verschiebung von einer frisch hergestellten Lösung von [Ph4P][PbBr2Cl]·CH3CN in DMSO-D6 im 207Pb-NMR Spektrum liegt mit 439 ppm zwischen den Werten von [Ph4P][PbCl3] mit 430 ppm und [Ph4P][PbBrCl2]·CH3CN mit 466 ppm. Die durchgeführten quantenchemischen Rechnungen auf HF-, BLYP- und B3LYP-Niveaus konnten aufgrund dessen, dass keine experimentell ermittelten Strukturdaten zur Verfügung stehen, nicht verglichen werden. Nur die auf B3LYP/LANL2DZ-Niveau berechnete Schwingungsfrequenz bei 249.4 cm−1 findet sich im gemessenen Raman-Spektrum bei 249 cm−1 als Deformationsschwingung von Br−Pb−Cl wieder. Tetraphenylarsoniumtrichloroplumbat(II), [Ph4As][PbCl3] Die Verbindung wird aus [Ph4As]Cl und PbCl2 in CH3CN gewonnen (Gleichung e). [Ph4As]Cl     →  CN CH PbCl 3 2 , [Ph4As][PbCl3] (e) Der im Vakuum gut getrocknete Feststoff enthält kein gebundenes Acetonitril, während aus CH3CN gewonnene Kristalle ein Äquivalent des Lösungsmittels eingebaut haben. Dieses geht aus den Werten der Elementaranalyse eindeutig hervor. Im von einer in DMSO-D6 gelösten Probe aufgenommenen 207Pb-NMR Spektrum ist nur eine Resonanz bei 450 ppm sichtbar. Der Unterschied zwischen [Ph4P]+ und [Ph4As]+ ist nicht sonderlich gross, sodass die bei diesem Versuch gewonnene Verbindung [Ph4As][PbCl3] die gleichen Strukturmerkmale aufweisen sollte wie das analoge Phosphonium-Salz. Tetrakis(pentafluorphenyl)blei(IV), (C6F5)4Pb (C6F5)4Pb wurde als potentielle Ausgangsverbindung zur Darstellung von (C6F5)nPb-Aziden synthetisiert. Die Darstellung der Verbindung (C6F5)4Pb, die bisher nicht vollständig charakterisiert wurde, erfolgte durch zwei Methoden (Gleichungen f und g), wobei aufgrund der höheren Ausbeute, der beschriebene Syntheseweg in Gleichung f bevorzugt wurde. Die NMR-Studien dieser Verbindung sind sehr aussagekräftig. In den 13C-NMR und 19FNMR Spektren von Tetrakis(pentafluorphenyl)blei(IV) sind die Signale des magnetisch aktiven Blei-Isotops (207Pb, I = ½, 22.6%) teilweise mit denen der nicht magnetisch aktiven Blei-Isotopomere überlagert. Im 207Pb-NMR Spektrum wurde ein Signal bei δ = −391 beobachtet, welches sich in ein komplexes aber gut aufgelöstes Multiplett aufspaltet. Dieses 21-Spinsystem wurde hervorgerufen durch die Kopplung des Pb-Kerns mit allen 19F-Kernen (8 ortho, 8 meta und 4 para). Eine Spektrensimulation mit der PERCH NMR-Software führt zu einem praktisch deckungsgleichen Spektrum. 4 C6F5MgBr + PbCl2 + Br2        →  − − MgBrCl 2 / MgBr 2 2 (f) Ein Vergleich zwischen den experimentell ermittelten (Röntgenstrukturanalyse) und auf semiempirischen PM3-Niveau berechneten Strukturdaten zeigt eine gute Übereinstimmung der Pb−C-Bindungslängen. Wie erwartet, wird auch gezeigt, dass die positive Ladung auf dem Metall mit steigender Substitution durch Fluor von +1.33 für (C6H5)4Pb auf +1.70 für (C6F5)4Pb steigt [107]. Ein Ansteigen der positiven Ladung am Blei, welches auf die elektronegativen Substituenten zurückzuführen ist, steigert die Grössenunterschiede zwischen den 6s- und 6p-Orbitalen und favorisiert somit die effiziente sp-Hybridisierung weniger stark. Es kann erwartet werden, dass (C6F5)4Pb stärkere Hybridisierungseffekte erleidet als (C6H5)4Pb und somit alle Pb−C-Bindungen durch die Substitution von elektronegativen Gruppen verkürzt werden. Deshalb sind die Pb−C-Bindungen in (C6F5)4Pb erwartungsgemäss kürzer als in (C6H5)4Pb. Versuchte Darstellungen von perfluorierten Blei-Verbindungen Die Verbindung (C6F5)2Cd·Diglyme ist als C6F5-Transferreagenz bekannt. Ph2Pb(N3)2 + (C6F5)2Cd·Diglyme →  Ph2Pb(N3)2 / (C6F5)2Pb(N3)2 /... (h) Ph2Pb(NO3)2 + (C6F5)2Cd·Diglyme →  Ph2Pb(NO3)2 / (C6F5)2Pb(NO3)2 /... (i) Die unter Gleichung h beschriebene Reaktion wurde durch die Verwendung verschiedener Lösungsmittel und verschiedener Mengenverhältnisse variiert. Aufgrund der gemessenen IR- und Raman-Spektren, sowie der Elementaranalysen konnte jeweils nur eine Teilumsetzung erkannt werden. Da Kristallisationsversuche bisher fehlschlugen, war eine genaue Charakterisierung der entstehenden Produkte bisher nicht möglich. Dieselben Argumente gelten für die in Gleichung i beschriebene Reaktion. Auch hier konnten nur Teilumsetzungen beobachtet werden. Die Verbindung (C6F5)4Pb ist extrem stabil. Behandelt man sie mit Salpetersäure (65% oder 100%), so findet keine Reaktion statt. Als Schlussfolgerung aus den gesamten Versuchen, neue (C6F5)nPb-Verbindungen darzustellen, lässt sich zusammenfassend sagen, dass es auf den beschrittenen Synthesewegen nicht möglich scheint, die gewünschten Produkte zu isolieren. Die C6F5-Reste lassen sich nicht bzw. nur geringfügig auf Blei-Verbindungen übertragen; ebenso ist (C6F5)4Pb so extrem stabil, dass auch von dieser Seite keine erfolgreiche Route beschritten werden kann. Azido(triphenylphosphan)gold(I), Ph3PAuN3 Kristalle dieser Verbindung konnten aus CH2Cl2 unter Zusatz geringer Mengen an Pentan bei einer Temperatur von 5°C gewonnen werden. Ein Kristall besteht aus diskreten Ph3PAuN3-Molekülen. Besonders interessant sind die Bindungslängen in der Azid-Einheit. Hier ist die Bindungslänge von N1−N2 mit einem Wert von 0.995(7) Å geringer als die von N2−N3 mit 1.294(8) Å. Dieses ist sehr erstaunlich und vermutlich falsch, da die Verhältnisse genau umgekehrt sein sollten. Eine kristallographische Erklärung dieser "verdrehten" Bindungsverhältnisse ist bislang noch nicht gefunden worden. Ausserdem ist der Wert von 0.995(7) Å für einen N−N-Abstand extrem gering. Im Gegensatz zu den durch Einkristall-Röntgenstrukturanalyse bestimmten N1−N2- und N2−N3-Bindungsabständen befinden sich die auf B3LYP-Niveau berechneten Werte in Übereinstimmung mit den Erwartungen, d.h. die Bindungslänge N1−N2 ist grösser, als die von N2−N3. Beide verwendeten Methoden, B3LYP/LANL2DZ und B3LYP/SDD, liefern sehr ähnliche Ergebnisse. Bis auf den P−Au−N1-Bindungswinkel von 164.1 bzw. 176.4° sind alle anderen theoretisch errechneten Abstände und Winkel nahezu gleich. Die Übereinstimmung mit den experimentell gefundenen Daten ist recht gut, mit Aussnahme der N−N-Abstände, wobei hier den quantenmechanisch berechneten Werten grösseres Vertrauen geschenkt werden sollte. Tetraphenylarsoniumtetraazidoaurat(III), [Ph4As][Au(N3)4] Kristalle dieser Verbindung konnten aus CH2Cl2 unter Zusatz geringer Mengen an Pentan bei einer Temperatur von 5°C gewonnen werden. Entgegen einer früheren Röntgenstrukturanalyse, bei welcher ein tetragonales System mit der Raumgruppe P4/n gefunden wurde, konnte nun bei dieser Bestimmung ein monoklines System mit der Raumgruppe C2/c ermittelt werden. Das Gold-Atom ist praktisch quadratischplanar von vier Stickstoff-Atomen umgeben. Die Bindungslänge von N1−N2 ist wie erwartet länger als die Distanz zwischen N2−N3. Die auf B3LYP- und MP2-Niveau theoretisch berechneten Strukturwerte stimmen im Vergleich zu den experimentell ermittelten recht gut überein. Die Bindungsabstände sind bei den Rechnungen länger als in den Röntgenstrukturen, was sich durch Packungseffekte im Kristall erklären lässt. Die Bindungswinkel sind nahezu identisch. Versuche zur Darstellung weiterer Gold-Azide Bei der Gold-Azid-Chemie handelt es sich um ein sehr diffiziles Thema. Die Verbindungen sind extrem explosionsgefährlich. So kam es mehrfach vor, dass bei einer zweiten Elementaranalyse ein und der selben Verbindung, diese explodierte, obwohl bei davor durchgeführten Tests kein explosives Verhalten festzustellen war. Die durchgeführten Versuche werden in der folgenden Übersicht tabellarisch zusammengefasst. Leider konnten bisher keine Kristalle der Verbindungen erhalten werden, so dass sich keine strukturellen Voraussagen treffen lassen. Da die Azid-Gruppe gegenüber Ag+ dasselbe Verhalten zeigt wie auch Cl−, kann man Chlorid-Ionen nicht ohne Probleme nachweisen. Anhand der Schwingungs- und 14N-NMR Spektroskopie lässt sich aber für alle in der Tabelle aufgeführten Reaktionen eindeutig sagen, dass es sich bei den entstandenen Produkten um kovalent-gebundene Gold-Azide handelt. Fallhammer-Explosionsteststand Der konstruierte Fallhammer hat sich als ein nützliches Werkzeug für Forschungszwecke herausgestellt. Die gemessenen Werte der maximalen absoluten Schallpegel ergeben eine wertvolle halb-quantitative Skala über die Explosionsfähigkeit und Schlagempfindlichkeit von potentiellen Explosivstoffen. Alle getesteten Substanzen waren Feststoffe und enthielten mindestens eine Azidgruppe: Silber(I)azid, Blei(II)azid, Cyanurazid, 1,3,5-Trinitro-2,4,6- triazidobenzen (TNTA), 1,3-Dinitro-2,4,6-triazidobenzen (DNTA) und 1,3,5-Trinitro-2- monoazidobenzen (TNMA). Cyanurazid ist ein noch stärkerer Explosivstoff als Silber- und Bleiazid. Eine Explosion von 20 mg Cyanurazid hat fast die gleiche Lautstärke wie eine durch 40 mg Pb(N3)2 oder durch 35 mg AgN3 verursachte Detonation. Neben den anorganischen Verbindungen, wurden einige organische Nitroazidsubstanzen getestet. Selbst die schwächste dieser organischen Explosivstoffe ist kraftvoller als AgN3 oder Pb(N3)2. Die Reihenfolge des Schallpegels ist TNMA < DNTA < TNTA, aber die Werte für DNTA und TNTA sind sehr ähnlich.

1 Hydraziniumazide In dieser Arbeit wurde untersucht, ob die Eigenschaften von Hydraziniumazid durch Einführung organischer Substituenten verbessert werden können. Die Hydraziniumazidderivate wurden aus den jeweiligen wasserfreien, substituierten Hydrazinen und einer wasserfreien Lösung von HN3 in Ether dargestellt, die aus der Reaktion von Tetrafluoroborsäureetherat mit Natriumazid gewonnen wurde. Hydraziniumazid ist ein Addukt der schwachen Säure HN3 (pKs = 4.92) mit Hydrazin. Zwischen den Hydrazinium- und Azidionen treten starke Wasserstoffbrückenbindungen auf. Die Stärke der Wasserstoffbrückenbindungen ist entscheidend für die Eigenschaften der jeweiligen Verbindungen. Die Leichtflüchtigkeit sowie die Hygroskopie von Hydraziniumazid und seinen Derivaten lassen sich auf die Stärke und Zahl der Wasserstoffbrückenbindungen zurückführen. Die Einführung organischer Substituenten schwächt die Bindung zwischen Azidionen und Hydraziniumionen bereits dadurch, dass weniger NH Wasserstoffatome, die Wasserstoffbrückenbindungen bilden können, vorhanden sind. Je mehr Substituenten vorhanden sind, desto schwächer ist somit die Bindung zwischen Hydrazin und HN3. Der Schmelzpunkt der Hydraziniumazide ist eine gute Beschreibungsgröße für die Stärke der Wasserstoffbrückenbindungen und damit die Stärke des Hydrazin-HN3 Addukts. Dies kann an den sinkenden Schmelzpunkten der methylierten Verbindungen Methylhydraziniumazid (3), N,N-Dimethylhydraziniumazid (4), N,N´- Dimethylhydraziniumazid (5), und N,N,N´-Trimethylhydraziniumazid (6) überprüft werden. Die organischen Substituenten lieferten während der Explosion keine Energiebeiträge, da sie entweder zum Kohlenwasserstoff oder zum organylsubstituierten Amin reagierten. Daher sinkt der Anteil an aktiver Masse mit zunehmendem Substitutionsgrad. Erstaunlicherweise explodierten aber die flüssigen di-, tri- und tetramethylierten Verbindungen 4-7 bei Erwärmung heftiger als das monomethylierte 3. Dies ist auf die schwache Bindung von HN3 in diesen Verbindungen zurückzuführen. Es wurde zuerst HN3 abgespalten, das dann explodierte. Es wurde versucht, die Bindung zwischen Hydrazinium- und Azidionen durch zusätzliche Wasserstoffbrückenbindungen mit weiteren NH und OH Protonen in 2-Hydroxyethylhydrazin und Ethylendihydrazin zu stärken. Aus der Reaktion dieser Hydrazinderivate mit HN3 wurden keine Feststoffe, sondern zähflüssige Produkte, die nicht die stöchiometrische Menge HN3 enthielten, isoliert.Der Einbau eines Hydrazinstickstoffatoms in Ringsysteme führt zur Erhöhung der Basizität des Stickstoffatoms. Stärkere Hydrazin-HN3 Addukte sollten sich ergeben. Dies wird dadurch belegt, dass der Schmelzpunkt der N,N-dimethylierten Verbindungen N,NDimethylhydraziniumazid (4) und N-Amino-1-azoniacyclohexanazid (18) im Sechsringsystem 18 um 50 °C höher ist. Das Siebenringsystem N-Amino-1- azoniacycloheptanazid (19) zeigt ebenfalls eine Erhöhung des Schmelzpunktes von 18 °C gegenüber 4. Die Erhöhung ist geringer als bei 18, da in Siebenringsystemen die Basizitätserhöhung des Ringstickstoffatoms niedriger ist als in Sechsringsystemen. Das bei N-Amino-1-azonia-4-oxacylcohexanazid (20) im Ringsystem vorhandene Sauerstoffatom zeigt keine Auswirkungen auf den Schmelzpunkt. 20 spaltete jedoch während längerer Lagerung eine NH2-Gruppe ab, Morpholiniumazid (21) wurde erhalten. Auch bei den N,N´-dimethylierten Verbindungen N,N´-Dimethylhydraziniumazid 5, N,N´-Diethylhydraziniumazid (22), Pyrazolidiniumazid (23) und Hexahydropyridaziniumazid (24) wurde eine Erhöhung des Schmelzpunktes durch Einbinden des Hydrazinmoleküls in ein Ringssystem festgestellt. Während die offenkettigen Azide 5 und 22 erst unterhalb Raumtemperatur fest wurden, waren die Ringsysteme 23 und 24 bei Raumtemperatur fest. Diorganylsubstituierte Hydraziniumazide sind nicht praktisch anwendbar, da zu viele organische Substituenten vorhanden sind, die die Explosion hemmen. Während der Explosion entstanden große Mengen an organischen Nebenprodukten, vor allem Organylamine. Ein weiterer Nachteil ist die Oxidationsempfindlichkeit der Alkylhydrazine, die sich in den Azidderivaten wiederfindet. Die Verbindungen N,N,N´,N´-Tetramethylhydraziniumazid-tetramethylhydrazinat (7) und Phenylhydraziniumazid-phenylhydrazinat (14) sind Grenzfälle. Bei der Reaktion mit HN3 bildeten sich Dimere der Hydrazine, an die das Azidion über Wasserstoffbrückenbindungen gebunden ist. Es war nicht möglich, aus einem festen, substituierten Hydrazin das Addukt mit HN3 zu bilden, da bei der Entfernung des Lösungsmittels immer das substituierte Hydrazin ausfiel. Substituierte Hydrazine mit einem permethylierten Stickstoffatom ergaben Hydraziniumazidderivate, die nicht mehr flüchtig, aber sehr hygroskopisch sind. Sie wurden aus der Umsetzung der jeweiligen Hydraziniumiodide mit Silberazid erhalten. N,N,NTrimethylhydraziniumazid (8), N,N,N,N´-Tetramethylhydraziniumazid (9) und Pentamethylhydraziniumazid (10) haben Schmelzpunkte um 180 °C. Die Anzahl der Methylgruppen wirkt sich hier nicht auf den Schmelzpunkt aus. 8-10 explodierten aufgrund der vielen organischen Substituenten nur schwach, bei der Explosion entstanden größere Mengen Trimethylamin. Günstige Auswirkung auf die Eigenschaften von Hydraziniumazid hat die Adduktbildung mit einem weiteren Molekül Hydrazin. Hydraziniumazidhydrazinat (2) ist nicht mehr hygroskopisch, wesentlich weniger flüchtig und die Empfindlichlichkeit gegenüber Schlag, Reibung und Temperaturerhöhung sinkt. Der Schmelzpunkt ist mit 65 °C allerdings noch niedriger als der Schmelzpunkt von Hydraziniumazid mit 75 °C. Ein weiterer Nachteil ist, dass bei der Explosion mehr Ammoniak entsteht als bei Hydraziniumazid. Als Beispiel ist hier die Struktur von Hydraziniumazidhydrazinat (2) abgebildet, die Strukturen vieler anderer Hydraziniumazide finden sich in Kapitel 1. 2 Methylierte Hydraziniumnitrate In Raketentriebwerken werden Methylhydrazin oder N,N-Dimethylhydrazin und N2O4 eingesetzt. Bei der unvollständigen Verbrennung können Ablagerungen der jeweiligen Ammonium- und Hydraziniumnitrate gebildet werden. Die mono- und N,N-dimethylierten Ammonium- und Hydraziniumnitrate wurden hergestellt und ihre Eigenschaften überprüft. Sowohl Methylhydrazinium- (27) als auch N,N-Dimethylhydraziniumnitrat (28) sind sehr hygroskopische Substanzen. Wasser konnte aus den Hydraziniumnitraten nicht im Vakuum entfernt werden. Daher wurden 27 und 28 aus den wasserfreien, methylierten Hydrazinen und wasserfreier Salpetersäure bei –78 °C hergestellt. Die Hydraziniumnitrate zersetzten sich bei leicht erhöhter Temperatur (60 °C) bereits langsam zu den jeweiligen Ammoniumnitraten. Die Strukturen von Methylhydraziniumnitrat (27) und Dimethylhydraziniumnitrat (28) wurden bestimmt, die Struktur von Methylhydraziniumnitrat (27) ist hier als Beispiel angegeben. Die Zersetzung der Ammonium- und Hydraziniumnitrate bei hoher Temperatur erfolgte nicht vollständig. Während die Ammoniumnitrate größere Mengen NO2 ergaben, wurden bei den Hydraziniumnitraten nur Produkte einer weiter fortgeschrittenen Zersetzung, z.B. NO, nachgewiesen. Auch kleine Mengen Methylazid wurden gefunden. Während der durchgeführten Test ist es nicht gelungen, die Nitrate zur Explosion zu bringen. Beim starken Erhitzen der Hydraziniumnitrate 27 und 28 fand nur eine Zersetzung, keine Explosion statt. 3 Reaktionen mit cis-Hyponitrit Die in der Literatur erwähnten Verbindungen mit cis-Hyponitritanionen wurden entweder durch Kupplung von zwei NO Molekülen an einem Metallzentrum oder durch Reaktion von N2O mit Natriumoxid erhalten. In dieser Arbeit ist es nicht gelungen, aus Reaktionen des cis-Hyponitritions neue Verbindungen zu isolieren, es wurde immer die Bildung von N2O beobachtet. Die theoretische Untersuchung der Zersetzung der einfach protonierten Verbindung cis-HN2O2 – ergab eine niedrige Aktivierungsbarriere von 11.9 kcal/mol (MP2/6-31+G(d,p)) für die Bildung von N2O und OH– in der Gasphase. Zusätzlich muss berücksichtigt werden, dass vor allem das OH–-Ion in einem Lösungsmittel gegenüber der Gasphase beträchtlich stabilisiert wird, so dass die Aktivierungsenergie in Lösung noch niedriger liegen dürfte. Dies erklärt die Bildung von N2O, die bei allen durchgeführten Experimenten, selbst bei sehr tiefen Temperaturen beobachtet wurde. Eine Isolierung der cis-hyposalpetrigen Säure kann daher wahrscheinlich nicht aus Lösung erfolgen, da sich die einfach protonierte Verbindung sofort zu N2O und OH– zersetzt. Ein Stickstoffoxid N6O4, das aus der Reaktion von Natrium-cis-hyponitrit mit Tetrafluorhydrazin entstehen kann, hat nur bei der Berechnung auf PM3 und HF Niveau ein Miniumum. Bei stärkerer Berücksichtigung der Elektronenkorrelation auf B3LYP oder MP2 Niveau wurden keine Minima auf der Energiehyperfläche gefunden. 4 Verbindungen mit 5,5´-Azotetrazolat Das 5,5´-Azotetrazolation enthält bereits 5 Mol Stickstoff. Durch Kombination mit Kationen von Stickstoffbasen, vor allen Hydraziniumkationen, können Verbindungen erhalten werden, die pro Formeleinheit viele Mole Gas erzeugen. Der Hauptbestandteil der Explosionsgase ist Stickstoff. Hydraziniumverbindungen bilden zusätzlich Wasserstoff, was für hohe Detonationsgeschwindigkeiten sorgt. Verbindungen, die große Mengen Stickstoff erzeugen, werden für Gasgeneratoren in automatischen Feuerlöschsystemen, Airbags und Rettungswesten gesucht. Ein Vorteil der Salze von 5,5´-Azotetrazolat mit Stickstoffbasen ist, dass sie gegenüber Schlag und Reibung relativ unempfindlich sind, was für eine Anwendung wichtig ist. Das empfindlichste Salz ist das Ammoniumsalz, das im Fallhammertest in der Literatur bei 4.4 kg bei einer Fallhöhe von 50 cm explodierte. [130] 5,5´-Azotetrazol ist im Gegensatz zu HN3 eine starke Säure und zerfiel bei Raumtemperatur innerhalb einer Minute vollständig zu Tetrazolhydrazin. Die freie Säure kann bei –30 °C hergestellt und bei –80 °C mehrere Wochen gelagert werden. Aus Methanol kristallisierte 5,5´-Azotetrazol mit zwei Molekülen Kristallwasser (70). 5,5´-Azotetrazolatsalze sind jedoch stabil. Die Synthese von 5,5´-Azotetrazolatsalzen erfolgte durch Umsetzung von Sulfaten der entsprechenden Kationen mit Barium-5,5´-azotetrazolat. Die Stabilität von 5,5´-Azotetrazolatsalzen mit protonierten Stickstoffbasen ist davon abhängig, wie leicht das Proton von der Stickstoffbase auf das 5,5´-Azotetrazolation übertragen werden kann. Dies kann an den Ammmoniumsalzen Diammonium-5,5´- azotetrazolat (45), Bis-methylammonium-5,5´-azotetrazolat (46), Bis-dimethylammonium- 5,5´-azotetrazolat (47), Bis-trimethylammonium-5,5´-azotetrazolat (48) und den Hydraziniumsalzen Hydrazinium(2+)-5,5´-azotetrazolat (51), Dihydrazinium-5,5´- azotetrazolat (53), Bis-methylhydrazinium-5,5´-azotetrazolat (54), Bis-N,Ndimethylhydrazinium- 5,5´azotetrazolat (55) und Bis-N,N´-dimethylhydrazinium-5,5´- azotetrazolat (56) abgelesen werden. Je mehr Methylgruppen vorhanden waren, desto tiefer waren die Zersetzungstemperatur der Salze. Waren keine NH+ Gruppen in den Kationen vorhanden, z.B. in Bis-tetramethylammonium-5,5´-azotetrazolat (49) und Bis-N,N,Ntrimethylhydrazinium- 5,5´-azotetrazolat (57), so erfolgte die Zersetzung über einen anderen Mechanismus, der wahrscheinlich umgekehrt zur Bildung der Tetrazolringe verläuft und erst bei höheren Temperaturen stattfindet. Die Synthese von 5,5´-Azotetrazolatsalzen mit protonierten Stickstoffbasen kann bei Raumtemperatur nur in Wasser als Lösungsmittel stattfinden. In organischen Lösungsmitteln erfolgte eine Zersetzung des Azotetrazolations. Dihydrazinium-5,5´-azotetrazolat (53) ist eine neue hochenergetische Verbindung, die alle Anforderungen für einen modernen Sprengstoff erfüllt. Die hohe Standardbildungsenthalpie von 264 kcal/mol (ber.), die bei der Detonation freigesetzt wird sowie die bei der Detonation gebildeten großen Mengen Wasserstoff sorgen für ein gute Detonationsgeschwindigkeit von 6330 m/s. Der größte Nachteil von 53 ist die niedrigen Dichte. Bei einer vergleichbaren Dichte würde die Verbindung die Werte der kommerziellen Sprengstoffe RDX und HMX übertreffen. Die bereits bekannten Guanidinium- (66) und Triaminoguanidiniumverbindungen (68), deren Kristallstrukturen in dieser Arbeit bestimmt wurden, haben höhere Dichten und sind thermisch stabiler. Vor allem das Guanidiniumsalz wird wahrscheinlich in den nächsten Jahren in Gasgeneratoren zum Einsatz kommen. Die niedrigen Dichten der Hydraziniumsalze im Vergleich zu den Guanidiuniumsalzen sind geometrisch begründet. Die Guanidiuniumderivate sind flach. Dadurch können sich sowohl die 5,5´-Azotetrazolationen als auch die Kationen platzsparend übereinander anordnen. Hydraziniumionen haben Wasserstoffatome, die nach allen Raumrichtungen ausgerichtet sind. Da diese Wasserstoffatome in Wasserstoffbrückenbindungen einbezogen werden, entstehen Lücken zwischen den 5,5´-Azotetrazolationen in der Kristallpackung. Das Hydraziniumsalz 53 kann zwei Einheiten Wasser oder Hydrazin über Wasserstoffbrücken binden. Sowohl das Ammoniumsalz 45, als auch Hydroxylammonium- 5,5´-azotetrazolat (50) und die methylierten Ammonium- 46-49 und Hydraziniumverbindungen 54-57 können keine zusätzlichen Stickstoffbasen über Wasserstoffbrückenbindungen binden. Die Alkali- und Erdalkalisalze 29-37 von 5,5´-Azotetrazolat binden große Mengen Kristallwasser. Die Wassermoleküle sind sowohl an die Kationen koordiniert als auch über Wasserstoffbrückenbindungen im Kristall gebunden. Daraus ergeben sich verschiedene Bedingungen für die Entfernung des Kristallwassers. Während nur über Wasserstoffbrückenbindungen gebundenes Kristallwasser beim Aufheizen bereits bei Temperaturen um 100 °C entwichen ist, liessen sich die koordierten Wassermoleküle erst bei Temperaturen von 120-150 °C entfernen. Bei der Entfernung der letzten Wassermoleküle wurden im DSC jeweils große Energiemengen festgestellt, die für eine Strukturänderung nach der Entfernung der letzten Wassermoleküle sprechen. Die Temperaturstabilität der Alkali- und Erdalkalimetallsalze sinkt mit zunehmender Größe des Kations. Während die Lithiumverbindung (29) erst bei 335 °C explodierte, explodierte die Bariumverbindung (37) bereits bei 211 °C. Bei der Entfernung von Wasser bei Temperaturen um 100 °C im Ölpumpenvakuum fanden Explosionen statt. Daher kann Wasser praktisch nur durch lange Lagerung der Salze im Exsikkator über P2O5 entfernt werden. Die wasserfreien Alkali- und Erdalkalimetallsalze sind schlag- und reibungsempfindlich, was sie zu potentiellen Primärexplosivstoffen macht Die Kristallstrukturen von Lithium-5,5´-azotetrazolat-hexahydrat (29), Natrium-5,5´- azotetrazolat-pentahydrat (30), Rubidium-5,5´-azotetrazolat-hydrat (32) und Barium-5,5´- azotetrazolat-pentahydrat (37) zeigen eine Koordination von 5,5´-Azotetrazolat– stickstoffatomen an das jeweilige Metallion. In Calcium-5,5´-azotetrazolat-octahydrat (35) und Yttrium-5,5´-azotetrazolat-docosahydrat (39) sind die 5,5´-Azotetrazolatstickstoffatome nicht mehr an die Metallionen koordiniert, die Metallionen sind von einer Hydrathülle umgeben. Auch Magnesium-5,5´-azotetrazolat-octahydrat (34) und die Salze der dreiwertigen Kationen Aluminium 38, Lanthan 40, Cer 41 und Neodym 42 sind im Einklang mit dem HSAB-Prinzip wahrscheinlich nur von einer Hydrathülle umgeben. Das Magnesiumsalz 34 sowie die Salze der dreiwertigen Kationen sind nur solange stabil, wie das Kation von der Hydrathülle umgeben ist. Verlieren die Verbindungen Wasser, z. B. beim Erhitzen, so werden farblose Zersetzungsprodukte erhalten. Bei der Reaktion von [Ce]4+[SO4]2– 2 mit Barium-5,5´-azotetrazolat kommt es sofort zu einer Gasentwicklung, Ce+4 ist in wässriger Lösung zu sauer. Nach Auflösen von Barium-5,5´-azotetrazolat in Hydrazin entfärbte sich die Reaktionslösung innerhalb von zwei Stunden. Farbloses Barium-N,N´-ditetrazolatohydrazintrihydrazin (44) wurde erhalten. 5 Reaktion von Tetrazoldiazoniumchlorid mit Lithiumazid Aus der Reaktion von Benzoldiazoniumchlorid mit Lithiumazid konnte Phenylpentazol isoliert werden. Analoge Reaktionen mit verschiedenen Phenylderivaten ergaben substituierte Phenylpentazole. Die Reaktion von Tetrazoldiazoniumchlorid mit Lithiumazid ergibt Tetrazolazid. Daher wurde auch in dieser Reaktion eine Pentazolzwischenstufe vermutet. Theoretische Berechnungen ergaben, dass die Aktivierungsenergie für den Zerfall verschiedener Tetrazolpentazolisomere in der Gasphase zu Tetrazolazid und Stickstoff mindestens 14.8 kcal/mol beträgt. Daher erschien es möglich, Tetrazolpentazol im Experiment zu beobachten. Bei der 15N-NMR spektroskopischen Verfolgung der Reaktion von Tetrazoldiazoniumchlorid (71) mit Lithium-15Nα-azid wurden zwei Signale bei δ = –29.7 und δ = 7.7 beobachtet, die bei Erwärmung auf –50 °C an Intensität abnahmen und bei –30 °C vollständig verschwunden waren. Gleichzeitig nahm das Signal von Stickstoff an Intensität zu und ein Signal von Nβ markiertem Tetrazolazid erschien. Die bereits bei tiefen Temperaturen wieder verschwindende Zwischenstufe der Reaktion von Tetrazoldiazoniumchlorid mit Lithiumazid entspricht daher sowohl ihrem chemischen Verhalten, als auch in den beobachteten Signalen dem Verhalten, das von Tetrazolpentazol erwartet wird.