2024 State of Marketing Report – by HubspotMarius Sescu
https://www.hubspot.com/state-of-marketing
· Scaling relationships and proving ROI
· Social media is the place for search, sales, and service
· Authentic influencer partnerships fuel brand growth
· The strongest connections happen via call, click, chat, and camera.
· Time saved with AI leads to more creative work
· Seeking: A single source of truth
· TLDR; Get on social, try AI, and align your systems.
· More human marketing, powered by robots
ChatGPT is a revolutionary addition to the world since its introduction in 2022. A big shift in the sector of information gathering and processing happened because of this chatbot. What is the story of ChatGPT? How is the bot responding to prompts and generating contents? Swipe through these slides prepared by Expeed Software, a web development company regarding the development and technical intricacies of ChatGPT!
Product Design Trends in 2024 | Teenage EngineeringsPixeldarts
The realm of product design is a constantly changing environment where technology and style intersect. Every year introduces fresh challenges and exciting trends that mold the future of this captivating art form. In this piece, we delve into the significant trends set to influence the look and functionality of product design in the year 2024.
How Race, Age and Gender Shape Attitudes Towards Mental HealthThinkNow
Mental health has been in the news quite a bit lately. Dozens of U.S. states are currently suing Meta for contributing to the youth mental health crisis by inserting addictive features into their products, while the U.S. Surgeon General is touring the nation to bring awareness to the growing epidemic of loneliness and isolation. The country has endured periods of low national morale, such as in the 1970s when high inflation and the energy crisis worsened public sentiment following the Vietnam War. The current mood, however, feels different. Gallup recently reported that national mental health is at an all-time low, with few bright spots to lift spirits.
To better understand how Americans are feeling and their attitudes towards mental health in general, ThinkNow conducted a nationally representative quantitative survey of 1,500 respondents and found some interesting differences among ethnic, age and gender groups.
Technology
For example, 52% agree that technology and social media have a negative impact on mental health, but when broken out by race, 61% of Whites felt technology had a negative effect, and only 48% of Hispanics thought it did.
While technology has helped us keep in touch with friends and family in faraway places, it appears to have degraded our ability to connect in person. Staying connected online is a double-edged sword since the same news feed that brings us pictures of the grandkids and fluffy kittens also feeds us news about the wars in Israel and Ukraine, the dysfunction in Washington, the latest mass shooting and the climate crisis.
Hispanics may have a built-in defense against the isolation technology breeds, owing to their large, multigenerational households, strong social support systems, and tendency to use social media to stay connected with relatives abroad.
Age and Gender
When asked how individuals rate their mental health, men rate it higher than women by 11 percentage points, and Baby Boomers rank it highest at 83%, saying it’s good or excellent vs. 57% of Gen Z saying the same.
Gen Z spends the most amount of time on social media, so the notion that social media negatively affects mental health appears to be correlated. Unfortunately, Gen Z is also the generation that’s least comfortable discussing mental health concerns with healthcare professionals. Only 40% of them state they’re comfortable discussing their issues with a professional compared to 60% of Millennials and 65% of Boomers.
Race Affects Attitudes
As seen in previous research conducted by ThinkNow, Asian Americans lag other groups when it comes to awareness of mental health issues. Twenty-four percent of Asian Americans believe that having a mental health issue is a sign of weakness compared to the 16% average for all groups. Asians are also considerably less likely to be aware of mental health services in their communities (42% vs. 55%) and most likely to seek out information on social media (51% vs. 35%).
AI Trends in Creative Operations 2024 by Artwork Flow.pdfmarketingartwork
This article is all about what AI trends will emerge in the field of creative operations in 2024. All the marketers and brand builders should be aware of these trends for their further use and save themselves some time!
2024 State of Marketing Report – by HubspotMarius Sescu
https://www.hubspot.com/state-of-marketing
· Scaling relationships and proving ROI
· Social media is the place for search, sales, and service
· Authentic influencer partnerships fuel brand growth
· The strongest connections happen via call, click, chat, and camera.
· Time saved with AI leads to more creative work
· Seeking: A single source of truth
· TLDR; Get on social, try AI, and align your systems.
· More human marketing, powered by robots
ChatGPT is a revolutionary addition to the world since its introduction in 2022. A big shift in the sector of information gathering and processing happened because of this chatbot. What is the story of ChatGPT? How is the bot responding to prompts and generating contents? Swipe through these slides prepared by Expeed Software, a web development company regarding the development and technical intricacies of ChatGPT!
Product Design Trends in 2024 | Teenage EngineeringsPixeldarts
The realm of product design is a constantly changing environment where technology and style intersect. Every year introduces fresh challenges and exciting trends that mold the future of this captivating art form. In this piece, we delve into the significant trends set to influence the look and functionality of product design in the year 2024.
How Race, Age and Gender Shape Attitudes Towards Mental HealthThinkNow
Mental health has been in the news quite a bit lately. Dozens of U.S. states are currently suing Meta for contributing to the youth mental health crisis by inserting addictive features into their products, while the U.S. Surgeon General is touring the nation to bring awareness to the growing epidemic of loneliness and isolation. The country has endured periods of low national morale, such as in the 1970s when high inflation and the energy crisis worsened public sentiment following the Vietnam War. The current mood, however, feels different. Gallup recently reported that national mental health is at an all-time low, with few bright spots to lift spirits.
To better understand how Americans are feeling and their attitudes towards mental health in general, ThinkNow conducted a nationally representative quantitative survey of 1,500 respondents and found some interesting differences among ethnic, age and gender groups.
Technology
For example, 52% agree that technology and social media have a negative impact on mental health, but when broken out by race, 61% of Whites felt technology had a negative effect, and only 48% of Hispanics thought it did.
While technology has helped us keep in touch with friends and family in faraway places, it appears to have degraded our ability to connect in person. Staying connected online is a double-edged sword since the same news feed that brings us pictures of the grandkids and fluffy kittens also feeds us news about the wars in Israel and Ukraine, the dysfunction in Washington, the latest mass shooting and the climate crisis.
Hispanics may have a built-in defense against the isolation technology breeds, owing to their large, multigenerational households, strong social support systems, and tendency to use social media to stay connected with relatives abroad.
Age and Gender
When asked how individuals rate their mental health, men rate it higher than women by 11 percentage points, and Baby Boomers rank it highest at 83%, saying it’s good or excellent vs. 57% of Gen Z saying the same.
Gen Z spends the most amount of time on social media, so the notion that social media negatively affects mental health appears to be correlated. Unfortunately, Gen Z is also the generation that’s least comfortable discussing mental health concerns with healthcare professionals. Only 40% of them state they’re comfortable discussing their issues with a professional compared to 60% of Millennials and 65% of Boomers.
Race Affects Attitudes
As seen in previous research conducted by ThinkNow, Asian Americans lag other groups when it comes to awareness of mental health issues. Twenty-four percent of Asian Americans believe that having a mental health issue is a sign of weakness compared to the 16% average for all groups. Asians are also considerably less likely to be aware of mental health services in their communities (42% vs. 55%) and most likely to seek out information on social media (51% vs. 35%).
AI Trends in Creative Operations 2024 by Artwork Flow.pdfmarketingartwork
This article is all about what AI trends will emerge in the field of creative operations in 2024. All the marketers and brand builders should be aware of these trends for their further use and save themselves some time!
A report by thenetworkone and Kurio.
The contributing experts and agencies are (in an alphabetical order): Sylwia Rytel, Social Media Supervisor, 180heartbeats + JUNG v MATT (PL), Sharlene Jenner, Vice President - Director of Engagement Strategy, Abelson Taylor (USA), Alex Casanovas, Digital Director, Atrevia (ES), Dora Beilin, Senior Social Strategist, Barrett Hoffher (USA), Min Seo, Campaign Director, Brand New Agency (KR), Deshé M. Gully, Associate Strategist, Day One Agency (USA), Francesca Trevisan, Strategist, Different (IT), Trevor Crossman, CX and Digital Transformation Director; Olivia Hussey, Strategic Planner; Simi Srinarula, Social Media Manager, The Hallway (AUS), James Hebbert, Managing Director, Hylink (CN / UK), Mundy Álvarez, Planning Director; Pedro Rojas, Social Media Manager; Pancho González, CCO, Inbrax (CH), Oana Oprea, Head of Digital Planning, Jam Session Agency (RO), Amy Bottrill, Social Account Director, Launch (UK), Gaby Arriaga, Founder, Leonardo1452 (MX), Shantesh S Row, Creative Director, Liwa (UAE), Rajesh Mehta, Chief Strategy Officer; Dhruv Gaur, Digital Planning Lead; Leonie Mergulhao, Account Supervisor - Social Media & PR, Medulla (IN), Aurelija Plioplytė, Head of Digital & Social, Not Perfect (LI), Daiana Khaidargaliyeva, Account Manager, Osaka Labs (UK / USA), Stefanie Söhnchen, Vice President Digital, PIABO Communications (DE), Elisabeth Winiartati, Managing Consultant, Head of Global Integrated Communications; Lydia Aprina, Account Manager, Integrated Marketing and Communications; Nita Prabowo, Account Manager, Integrated Marketing and Communications; Okhi, Web Developer, PNTR Group (ID), Kei Obusan, Insights Director; Daffi Ranandi, Insights Manager, Radarr (SG), Gautam Reghunath, Co-founder & CEO, Talented (IN), Donagh Humphreys, Head of Social and Digital Innovation, THINKHOUSE (IRE), Sarah Yim, Strategy Director, Zulu Alpha Kilo (CA).
Trends In Paid Search: Navigating The Digital Landscape In 2024Search Engine Journal
The search marketing landscape is evolving rapidly with new technologies, and professionals, like you, rely on innovative paid search strategies to meet changing demands.
It’s important that you’re ready to implement new strategies in 2024.
Check this out and learn the top trends in paid search advertising that are expected to gain traction, so you can drive higher ROI more efficiently in 2024.
You’ll learn:
- The latest trends in AI and automation, and what this means for an evolving paid search ecosystem.
- New developments in privacy and data regulation.
- Emerging ad formats that are expected to make an impact next year.
Watch Sreekant Lanka from iQuanti and Irina Klein from OneMain Financial as they dive into the future of paid search and explore the trends, strategies, and technologies that will shape the search marketing landscape.
If you’re looking to assess your paid search strategy and design an industry-aligned plan for 2024, then this webinar is for you.
5 Public speaking tips from TED - Visualized summarySpeakerHub
From their humble beginnings in 1984, TED has grown into the world’s most powerful amplifier for speakers and thought-leaders to share their ideas. They have over 2,400 filmed talks (not including the 30,000+ TEDx videos) freely available online, and have hosted over 17,500 events around the world.
With over one billion views in a year, it’s no wonder that so many speakers are looking to TED for ideas on how to share their message more effectively.
The article “5 Public-Speaking Tips TED Gives Its Speakers”, by Carmine Gallo for Forbes, gives speakers five practical ways to connect with their audience, and effectively share their ideas on stage.
Whether you are gearing up to get on a TED stage yourself, or just want to master the skills that so many of their speakers possess, these tips and quotes from Chris Anderson, the TED Talks Curator, will encourage you to make the most impactful impression on your audience.
See the full article and more summaries like this on SpeakerHub here: https://speakerhub.com/blog/5-presentation-tips-ted-gives-its-speakers
See the original article on Forbes here:
http://www.forbes.com/forbes/welcome/?toURL=http://www.forbes.com/sites/carminegallo/2016/05/06/5-public-speaking-tips-ted-gives-its-speakers/&refURL=&referrer=#5c07a8221d9b
ChatGPT and the Future of Work - Clark Boyd Clark Boyd
Everyone is in agreement that ChatGPT (and other generative AI tools) will shape the future of work. Yet there is little consensus on exactly how, when, and to what extent this technology will change our world.
Businesses that extract maximum value from ChatGPT will use it as a collaborative tool for everything from brainstorming to technical maintenance.
For individuals, now is the time to pinpoint the skills the future professional will need to thrive in the AI age.
Check out this presentation to understand what ChatGPT is, how it will shape the future of work, and how you can prepare to take advantage.
A brief introduction to DataScience with explaining of the concepts, algorithms, machine learning, supervised and unsupervised learning, clustering, statistics, data preprocessing, real-world applications etc.
It's part of a Data Science Corner Campaign where I will be discussing the fundamentals of DataScience, AIML, Statistics etc.
Time Management & Productivity - Best PracticesVit Horky
Here's my presentation on by proven best practices how to manage your work time effectively and how to improve your productivity. It includes practical tips and how to use tools such as Slack, Google Apps, Hubspot, Google Calendar, Gmail and others.
The six step guide to practical project managementMindGenius
The six step guide to practical project management
If you think managing projects is too difficult, think again.
We’ve stripped back project management processes to the
basics – to make it quicker and easier, without sacrificing
the vital ingredients for success.
“If you’re looking for some real-world guidance, then The Six Step Guide to Practical Project Management will help.”
Dr Andrew Makar, Tactical Project Management
Unlocking the Power of ChatGPT and AI in Testing - A Real-World Look, present...Applitools
During this webinar, Anand Bagmar demonstrates how AI tools such as ChatGPT can be applied to various stages of the software development life cycle (SDLC) using an eCommerce application case study. Find the on-demand recording and more info at https://applitools.info/b59
Key takeaways:
• Learn how to use ChatGPT to add AI power to your testing and test automation
• Understand the limitations of the technology and where human expertise is crucial
• Gain insight into different AI-based tools
• Adopt AI-based tools to stay relevant and optimize work for developers and testers
* ChatGPT and OpenAI belong to OpenAI, L.L.C.
More than Just Lines on a Map: Best Practices for U.S Bike Routes
This session highlights best practices and lessons learned for U.S. Bike Route System designation, as well as how and why these routes should be integrated into bicycle planning at the local and regional level.
Presenters:
Presenter: Kevin Luecke Toole Design Group
Co-Presenter: Virginia Sullivan Adventure Cycling Association
Ride the Storm: Navigating Through Unstable Periods / Katerina Rudko (Belka G...DevGAMM Conference
Has your project been caught in a storm of deadlines, clashing requirements, and the need to change course halfway through? If yes, then check out how the administration team navigated through all of this, relocating 160 people from 3 countries and opening 2 offices during the most turbulent time in the last 20 years. Belka Games’ Chief Administrative Officer, Katerina Rudko, will share universal approaches and life hacks that can help your project survive unstable periods when there seem to be too many tasks and a lack of time and people.
This presentation was designed to provide strategic recommendations for a brand in decline. The deck also incorporates a situational assessment, including a brand identity, positioning, architecture, and portfolio strategy for the Brand.
Presentation originally created for NYU Stern's Brand Strategy course. Design by Erica Santiago & Chris Alexander.
A report by thenetworkone and Kurio.
The contributing experts and agencies are (in an alphabetical order): Sylwia Rytel, Social Media Supervisor, 180heartbeats + JUNG v MATT (PL), Sharlene Jenner, Vice President - Director of Engagement Strategy, Abelson Taylor (USA), Alex Casanovas, Digital Director, Atrevia (ES), Dora Beilin, Senior Social Strategist, Barrett Hoffher (USA), Min Seo, Campaign Director, Brand New Agency (KR), Deshé M. Gully, Associate Strategist, Day One Agency (USA), Francesca Trevisan, Strategist, Different (IT), Trevor Crossman, CX and Digital Transformation Director; Olivia Hussey, Strategic Planner; Simi Srinarula, Social Media Manager, The Hallway (AUS), James Hebbert, Managing Director, Hylink (CN / UK), Mundy Álvarez, Planning Director; Pedro Rojas, Social Media Manager; Pancho González, CCO, Inbrax (CH), Oana Oprea, Head of Digital Planning, Jam Session Agency (RO), Amy Bottrill, Social Account Director, Launch (UK), Gaby Arriaga, Founder, Leonardo1452 (MX), Shantesh S Row, Creative Director, Liwa (UAE), Rajesh Mehta, Chief Strategy Officer; Dhruv Gaur, Digital Planning Lead; Leonie Mergulhao, Account Supervisor - Social Media & PR, Medulla (IN), Aurelija Plioplytė, Head of Digital & Social, Not Perfect (LI), Daiana Khaidargaliyeva, Account Manager, Osaka Labs (UK / USA), Stefanie Söhnchen, Vice President Digital, PIABO Communications (DE), Elisabeth Winiartati, Managing Consultant, Head of Global Integrated Communications; Lydia Aprina, Account Manager, Integrated Marketing and Communications; Nita Prabowo, Account Manager, Integrated Marketing and Communications; Okhi, Web Developer, PNTR Group (ID), Kei Obusan, Insights Director; Daffi Ranandi, Insights Manager, Radarr (SG), Gautam Reghunath, Co-founder & CEO, Talented (IN), Donagh Humphreys, Head of Social and Digital Innovation, THINKHOUSE (IRE), Sarah Yim, Strategy Director, Zulu Alpha Kilo (CA).
Trends In Paid Search: Navigating The Digital Landscape In 2024Search Engine Journal
The search marketing landscape is evolving rapidly with new technologies, and professionals, like you, rely on innovative paid search strategies to meet changing demands.
It’s important that you’re ready to implement new strategies in 2024.
Check this out and learn the top trends in paid search advertising that are expected to gain traction, so you can drive higher ROI more efficiently in 2024.
You’ll learn:
- The latest trends in AI and automation, and what this means for an evolving paid search ecosystem.
- New developments in privacy and data regulation.
- Emerging ad formats that are expected to make an impact next year.
Watch Sreekant Lanka from iQuanti and Irina Klein from OneMain Financial as they dive into the future of paid search and explore the trends, strategies, and technologies that will shape the search marketing landscape.
If you’re looking to assess your paid search strategy and design an industry-aligned plan for 2024, then this webinar is for you.
5 Public speaking tips from TED - Visualized summarySpeakerHub
From their humble beginnings in 1984, TED has grown into the world’s most powerful amplifier for speakers and thought-leaders to share their ideas. They have over 2,400 filmed talks (not including the 30,000+ TEDx videos) freely available online, and have hosted over 17,500 events around the world.
With over one billion views in a year, it’s no wonder that so many speakers are looking to TED for ideas on how to share their message more effectively.
The article “5 Public-Speaking Tips TED Gives Its Speakers”, by Carmine Gallo for Forbes, gives speakers five practical ways to connect with their audience, and effectively share their ideas on stage.
Whether you are gearing up to get on a TED stage yourself, or just want to master the skills that so many of their speakers possess, these tips and quotes from Chris Anderson, the TED Talks Curator, will encourage you to make the most impactful impression on your audience.
See the full article and more summaries like this on SpeakerHub here: https://speakerhub.com/blog/5-presentation-tips-ted-gives-its-speakers
See the original article on Forbes here:
http://www.forbes.com/forbes/welcome/?toURL=http://www.forbes.com/sites/carminegallo/2016/05/06/5-public-speaking-tips-ted-gives-its-speakers/&refURL=&referrer=#5c07a8221d9b
ChatGPT and the Future of Work - Clark Boyd Clark Boyd
Everyone is in agreement that ChatGPT (and other generative AI tools) will shape the future of work. Yet there is little consensus on exactly how, when, and to what extent this technology will change our world.
Businesses that extract maximum value from ChatGPT will use it as a collaborative tool for everything from brainstorming to technical maintenance.
For individuals, now is the time to pinpoint the skills the future professional will need to thrive in the AI age.
Check out this presentation to understand what ChatGPT is, how it will shape the future of work, and how you can prepare to take advantage.
A brief introduction to DataScience with explaining of the concepts, algorithms, machine learning, supervised and unsupervised learning, clustering, statistics, data preprocessing, real-world applications etc.
It's part of a Data Science Corner Campaign where I will be discussing the fundamentals of DataScience, AIML, Statistics etc.
Time Management & Productivity - Best PracticesVit Horky
Here's my presentation on by proven best practices how to manage your work time effectively and how to improve your productivity. It includes practical tips and how to use tools such as Slack, Google Apps, Hubspot, Google Calendar, Gmail and others.
The six step guide to practical project managementMindGenius
The six step guide to practical project management
If you think managing projects is too difficult, think again.
We’ve stripped back project management processes to the
basics – to make it quicker and easier, without sacrificing
the vital ingredients for success.
“If you’re looking for some real-world guidance, then The Six Step Guide to Practical Project Management will help.”
Dr Andrew Makar, Tactical Project Management
Unlocking the Power of ChatGPT and AI in Testing - A Real-World Look, present...Applitools
During this webinar, Anand Bagmar demonstrates how AI tools such as ChatGPT can be applied to various stages of the software development life cycle (SDLC) using an eCommerce application case study. Find the on-demand recording and more info at https://applitools.info/b59
Key takeaways:
• Learn how to use ChatGPT to add AI power to your testing and test automation
• Understand the limitations of the technology and where human expertise is crucial
• Gain insight into different AI-based tools
• Adopt AI-based tools to stay relevant and optimize work for developers and testers
* ChatGPT and OpenAI belong to OpenAI, L.L.C.
More than Just Lines on a Map: Best Practices for U.S Bike Routes
This session highlights best practices and lessons learned for U.S. Bike Route System designation, as well as how and why these routes should be integrated into bicycle planning at the local and regional level.
Presenters:
Presenter: Kevin Luecke Toole Design Group
Co-Presenter: Virginia Sullivan Adventure Cycling Association
Ride the Storm: Navigating Through Unstable Periods / Katerina Rudko (Belka G...DevGAMM Conference
Has your project been caught in a storm of deadlines, clashing requirements, and the need to change course halfway through? If yes, then check out how the administration team navigated through all of this, relocating 160 people from 3 countries and opening 2 offices during the most turbulent time in the last 20 years. Belka Games’ Chief Administrative Officer, Katerina Rudko, will share universal approaches and life hacks that can help your project survive unstable periods when there seem to be too many tasks and a lack of time and people.
This presentation was designed to provide strategic recommendations for a brand in decline. The deck also incorporates a situational assessment, including a brand identity, positioning, architecture, and portfolio strategy for the Brand.
Presentation originally created for NYU Stern's Brand Strategy course. Design by Erica Santiago & Chris Alexander.
1. Argumentace
Následující publikace je upravenou verzí dokumentu, který posloužil k ohodnocení mé
průběžné práce a projektů během mého bakalářského a magisterského studia v předmětu
C8855 Počítačová chemie a molekulové modelování II. Název publikace napovídá, že hl.
objektem studia je molekula Bambus[6]uril a jaké metodiky byly při studiu této molekuly
použity.
Anotace
Tato práce předkládá studii nově syntetizované supramolekulární sloučeniny nazvané
bambus[6]uril pomocí metod výpočetní chemie. Sloučenina je derivátem glykolurilu a svými
vlastnostmi spojuje chemické chování cucurbit[n]urilů a hemicucurbit[n]urilů. Práce
podrobně popisuje stavební strukturu a z ní vyplývající vlastnosti především afinitu aniontů
k makrocyklu.
Bambus[6]uril byl studován metodami molekulové dynamiky (MD) a kvantově
mechanickým přístupem(QM). Pomocí QM je vypočítána vazebná energie odlišných druhů
aniontů do bambus[6]urilu. Získané energie byly uspořádány dle velikosti a porovnány
s výsledky experimentu.
Klíčová slova
Bambus[6]uril, glykoluril, výpočetní chemie, počítačové modelování, supramolekulární
chemie
Studium nové makromolekuly Bambus[6]urilu pomocí
výpočetní chemie a modelování
1. Úvod
Tato práce se soustřeďuje na nedávno nově syntetizovanou makromolekulární
sloučeninou nazvanou Bambus[6]uril [BU6] (viz Obrázek 1.). Na jejím vývoji se především
podílel Jan Švec pod odborným vedením Vladimíra Šindeláře na organické sekci Masarykovy
univerzity. Tato sloučenina svým prostorovým uspořádáním připomíná skupinu molekul typu
cucurbiturilů složených z glykolurilových strukturních jednotek. BU6 se skládá z 6 jednotek
glykolurilu propojených methylovými skupinami, které svou kompozicí lze připodobnit
k dutému válci bez spodní a horní podstavy (jeden článek bambusu). Molekula BU6 je
schopná interakce s různými typy aniontů vyplývající z atomové konstituce a rozložení
1
Mgr. Jan Slavík – publikace pro předmět Kurz práce s informacemi vyučovaný na Masarykově univerzitě v Brně dne 1.6.2013
2. parciálních nábojů. Utvářejí se tak komplexy BU6/Xz-, kde X je interagující anion např.
halogenidy, NO3 -, NO2-, PF6- a další a z je odpovídající náboj aniontu. S přihlédnutím
k velikosti aniontu lze říci, že anionty jsou v komplexu s BU6 lokalizovány v dutině BU6.
Jako vhodným rozpouštědlem pro BU6 se ukázala být ekvimolární směs ethanolu a
chloroformu.1
Obrázek 1. Bambus[6]uril – pohled z boku (vlevo) a shora (vpravo)
Především je tato práce částečným shrnutím mé bakalářské práce2. Podává přehled
metod, které byly použity pro vytvoření modelu BU6 a při chemických výpočtech. Na časové
ose lze najít, jak bylo postupováno při tvorbě mé bakalářské práce (Obrázek 2.)
Obrázek 2. Posloupnost progresu bakalářské práce
2
Mgr. Jan Slavík – publikace pro předmět Kurz práce s informacemi vyučovaný na Masarykově univerzitě v Brně dne 1.6.2013
3. 2. Metody
2.1 Příprava systému
Struktura studovaného bambus[6]urilu byla uměle vytvořena pomocí softwaru
Spartan ’023 a geometrie byla porovnána s dostupnou krystalovou strukturou. Následná
optimalizace struktury byla provedena za použití Hartree-Fockovi metody a báze 6-31G*
v programu Gaussian 034. Atomové náboje byly získány standardní RESP postupem na
úrovni HF/6-31*.
2.2 Molekulární dynamika (MD)
Vstupní struktura pro MD simulace byla vygenerována v programu Leap
z softwarového balíku Amber 105, za použití silového pole GAFF6. Provedené simulace
vedly nejen k získání dynamického chování studovaného systému, ale také k vysvětlení
důležitých trendů – jako rozpustnost a stabilita BU6. Pro spuštěné simulace bylo
navrženo pět různých prostředí (vakuum, voda, metanol, chloroform a ekvimolární směs
methanolu a chloroformu). Systém v rozpouštědle vody byl připraven za využití
programu Solvate s TIP3P modelem pro molekuly vody a tvar boxu odpovídal truncated
octahedral s nastaveným poloměrem na 22Å. Parametry pro organická rozpouštědla byly
získány dodatečně a systémy byly solvatovány programem Leap. Velikost jednotlivých
boxů byla ovlivněna rozměry použitých molekul rozpouštědel, aby simulace probíhaly
v přítomnosti podobného počtu atomů. Proto velikost boxu pro menší molekuly metanolu
byla 21Å a pro chloroform 31Å. Veškeré simulace byly provedeny pro dva stavy, zaprvé
pro samotný BU6 a zadruhé za přítomnosti chloridového aniontu v jeho dutině.
V potřebných případech byly k zajištění elektroneutrality přidány sodné kationty. Sodné a
chloridové ionty byly popsány silovým polem parm99SB.
Vytvořené systémy byly první optimalizovány a pak pomalu zahřívány z 1 na 300K
během 100ps dlouhé simulace za konstantního obejmu systému. Počáteční rychlosti při
teplotě 1K byly generovány pro odpovídající Maxwell-Boltzmanově distribuci.
Integrační krok byl nastaven na 1fs a pro zafixování délky vazeb obsahujících vodíkový
atom bylo použito SHAKE algoritmu. Teplota byla regulována Langevinovým
termostatem. Následná relaxace systému proběhla při 300K a konstantního tlaku 1 bar
3
Mgr. Jan Slavík – publikace pro předmět Kurz práce s informacemi vyučovaný na Masarykově univerzitě v Brně dne 1.6.2013
4. v délce trvání 200ps. Daleko-dosahové interakce byly popsaný metodou Particle Mesh
Ewald s nastaveným cut-off na 9.0Å.
Postup popsaný výše byl aplikován pro všechny prostředí a jak pro samotný BU6,
tak pro komplex s chloridovým aniontem v dutině. Jednotlivé simulace trvaly shodně
10ns a provedeny byly za konstantního tlaku.
2.3 Kvantová mechanika (QM)
Z hlediska experimentálního pozorování vyplývá, že Bambus[6]uril vykazuje
vysokou afinitu k aniontům, které je schopen vázat. Pro hodnocení trendů a výpočet
komplexačních energií pro různé druhy aniontů bylo využito kvantově chemických
metod. Získané výsledky byly porovnány (pokud bylo možno) s experimentem. Hlavní
zájem výpočtů byl kladen na skupinu halogenidových aniontů a díky zvláštním
vlastnostem také atomu xenonu.
Vstupní geometrie pro všechny zkoumané komplexy byly připraveny podobně jako
pro samotnou molekulu bambus[6]urilu. Střed hmoty aniontů byl uměle umístěn
do dutiny, tedy do těžiště BU6. Jednotlivé komplexy byly nejprve optimalizovány
v Gaussianu 03, HF/6-31G*. Takto optimalizované souřadnice sloužily jako vstup pro
následnou sofistikovanější BP DFT optimalizaci, zahrnující RI korekci (resolution of
identity). S ohledem na požadovanou přesnost výsledků byla vybrána def2-TZVVP báze.
Výpočty proběhly v balíku Turbomole verze 6.3. Veškeré komplexační energie aniontů
byly počítány v prostředí vakuu a při zahrnutí implicitního solventu COSMO. Jelikož
experimenty byly vedeny v kapalné ekvimolární směsi metanolu a chloroformu, byla
nastavena pro COSMO relativní permitivita 19. Odpovídá průměrné hodnotě obou
permitivit pro metanol a chloroform. Všechny výpočty také zahrnovaly korekce na Basis
Set Superposition Error (BSSE) a na disperzi použitím metody DFT-D3.
Získané výsledky jsou shrnuty v tabulce 1., která je seřazena dle klesající afinity
aniontu k BU6 a tedy lepší schopnosti tvořit komplex s BU6 (čím zápornější hodnota, tím
stabilnější komplex). Výsledky porovnané s experimentem se shodují v pozorovaném
trendu pro halogenidové anionty. Avšak pořadí v tabulce pro další typy aniontů poskytuje
jisté odchylky a získané výsledky je nutno hodnotit kriticky. Problém a zároveň
vysvětlení, proč nehalogenidové komplexační vypočtené energie neodpovídají trendům
z experimentů, můžeme nalézt v použití implicitního solventu při simulaci, který se
chová jako homogenní kontinuum. Nemusí tak odpovídat reálnému rozmístění molekul
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Mgr. Jan Slavík – publikace pro předmět Kurz práce s informacemi vyučovaný na Masarykově univerzitě v Brně dne 1.6.2013
5. metanolu a chloroformu okolo a uvnitř. Molekuly jednotlivých rozpouštědel mohou
jistou mírou také přispívat ke stabilizaci komplexu. Tato stabilizace se, však nemůže
v plné míře projevit při využití COSMO modelu. Využitím metod výpočtu volných
energií (FEC) lze zapojit i explicitní molekuly rozpouštědla a tím získat přesnější
hodnoty celkové afinity iontů k BU6. FEC jsou součástí navazující magisterské práce7.
dEtotal
BU6/BF4- -25,12
BU6/PF6- -24,32
-
BU6/CH3COO -22,37
BU6/OCN- -20,84
-
BU6/HCO3 -20,80
-
BU6/HCOO -19,46
-
BU6/I -19,44
-
BU6/NO3 -18,25
-
BU6/Br -16,74
BU6/SCN- -16,08
-
BU6/Cl -13,18
-
BU6/F -10,29
BU6/Xe -6,88
2-
BU6/NO 8,74
Tabulka 1. Asociační energie komplexu BU6 s anionty seřazeny dle
stoupající afinitní energie (žlutě zvýrazněny halogenidové anionty)
3. Reference
(1) Svec, J.; Necas, M.; Sindelar, V. Bambus[6]uril. Angew. Chem. Int. Ed. 2010,
(2) Slavík, J. Bakalářská práce; Masarykova univerzita, 2010.
(3) Spartan ’02; Wavefunction, Inc.: Irvine, CA.
(4) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J.
A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.;
Cossi, M.; Scalmani, Y.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda,
R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.;
Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev,
O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador,
P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.;
Rabuck, A. D.; Raghavachari, J.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski,
J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-
Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong,
M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, Revision E.1; Gaussian, Inc.: Wallingford, CT, 2003.
(5) Case, D. A.; Darden, T. A.; Cheatham, T. E.; Simmerling, C. L.; Wang, J.; Duke, R. E.; Luo, R.; Crowley, M.;
Ross C. Walker; Zhang, W.; Merz, K. M.; Wang, B.; Hayik, S.; Roitberg, A.; Seabra, G.; Kolossváry, I.; Wong,
K. F.; Paesani, F.; Vanicek, J.; Wu, X.; Brozell, S. R.; Steinbrecher, T.; Gohlke, H.; Yang, L.; Tan, C.; Mongan,
J.; Hornak, V.; Cui, G.; Mathews, D. H.; Seetin, M. G.; Sagui, C.; Babin, V.; Kollman, P. A. Amber 10;
University of California, San Francisco, 2008.
(6) Wang, J. M.; Wolf, R. M.; Caldwell, J. W.; Kollman, P. A.; Case, D. A. Development and Testing of a
General Amber Force Field. J. Comput. Chem. 2004, 25, 1157–1174.
(7) Slavík, J. Diplomová práce; Masarykova univerzita, 2012.
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Mgr. Jan Slavík – publikace pro předmět Kurz práce s informacemi vyučovaný na Masarykově univerzitě v Brně dne 1.6.2013