Belgium captain Eden Hazard is confident that his side’s “Golden Generation” will fulfil their promised potential unlike that of England’s who failed to deliver on the big stageBelgium enters the World Cup this summer as one of the dark horses to overcome the likes of Germany, Brazil and Spain to claim glory in world football’s biggest stage.Hazard, along with the likes of Kevin De Bruyne, Romelu Lukaku and Thibaut Courtois, is confident that he is part of a new “Golden Generation” and is certain that Belgium can do what England’s previous stars failed to do this summer.Zidane hails ‘quality’ James Rodriguez after Real Madrid’s win Andrew Smyth – September 14, 2019 Zinedine Zidane reserved special praise for James Rodriguez after his starring role in Real Madrid’s 3-2 win over Levante.In the 2000’s, England had the likes of David Beckham, Frank Lampard, Rio Ferdinand, Michael Owen and Steven Gerrard at the peak of their abilities and yet they disappointed by only reaching the quarter-finals in three major tournaments.“The golden generation you had in England, 10 years or 15 years ago, won nothing. Now I think the fans, journalists, all of Belgium, the country just want to win something. We have a golden generation,” said Hazard, according to FirstPost.Hazard and Belgium will begin their World Cup campaign against Panama on June 18, before facing England in their third and final Group G game on June 28.
Sam Allardyce believes that he should still be the England manager and admitted that he is feeling jealous over their recent success in his absenceThe 63-year-old was infamously fired from the role as head coach of the national side in September 2016, despite having only been in charge for one game in a last-gasp 1-0 victory away to Slovakia.Allardyce’s spell of 67 days in charge was the shortest of any England manager.In a BBC documentary called “Managing England: The Impossible Job”, the former Everton boss reflected on his controversial exit from England.“Jealousy is what I feel. Massively disappointed. That should be me there. Unfortunately because of the circumstances that wasn’t the case,” said Allardyce, according to The Sack Race.Crouch: Liverpool could beat Man United to Jadon Sancho Andrew Smyth – September 14, 2019 Peter Crouch wouldn’t be surprised to see Jadon Sancho end up at Liverpool one day instead of his long-term pursuers Manchester United.“One night I was playing golf – next day they said you can’t carry on. And I still don’t know why… because in the cold light of day, there was no substance, nothing behind it.“If a bit more time was taken, a bit more patience, I believe I should still be the England manager.“I’ve bounced back now – and while I will be extremely jealous I will be watching Gareth and the lads and hope they do extremely well.”Despite having guided Everton to a top 10 finish in the Premier League last season, Allardyce was fired by the board and replaced by Marco Silva.
Sadio Mane has revealed why he decided to switch squad jersey numbers this summer and gave insight about his team’s run of fixtures.Mane spent his first two years at Liverpool wearing the number 19 shirt but switched to jersey number 10 after Philippe Coutinho’s departure to Barcelona earlier in the year, and the Senegalese admits he couldn’t wait to swap.“I was very happy to get it because I have always taken the number 10 everywhere I have gone,” added Mane. “When I first came to Liverpool, Philippe (Coutinho) had it, so I was happy with my number 19.“But when he left I thought: it is free, I want to take the number 10 because it has always been my favourite number.“Everywhere I go, I wore number 10, and now I wear it for Liverpool.”Virgil van Dijk praises Roberto Firmino after Liverpool’s win Andrew Smyth – September 14, 2019 Virgil van Dijk hailed team-mate Roberto Firmino after coming off the bench to inspire Liverpool to a 3-1 comeback win against Newcastle United.Liverpool’s are bracing up for the trip to Stamford Bridge which is their fifth game in a run of seven in 23 days.“It’s a very, very tough list,” said Mane, speaking to the official Liverpool matchday programme. “But if you think about it you should be happy because of our strength.“If we are a team at the bottom of the table it would be a lot more difficult, but we are a big team with a big squad so let’s do it.“For us, it is no problem. We will take it game by game, try to win and only then concentrate on the next game.”
Scotland’s Andrew Robertson has heaped praises on David Bates ahead of his international debut with the team.The Hamburg defender is set to win his first cap in the heart of the Scotland defence, thanks to a large number of withdrawals from the team.Robertson has been impressed by the former Rangers Football Club defender, saying:“You don’t quite know how it will go on your debut but I think David can stand up and be counted,” he said according to Dail Mail.“He’s been really good in training. I remember watching him at Rangers and he’s come on a lot since he made the move to Hamburg.”“It’s up to the manager if he starts or not but, if he does, the more experienced lads will help him out and be positive.”Scotland’s Robertson hopes for a positive result against Belgium Manuel R. Medina – September 7, 2019 Scotland was defeated at home 2-1 by Russia in yesterday’s 2020 European Championship qualifiers, and the team is almost out of the race for a spot at the Euros.“Yes, it will be an inexperienced 11 due to circumstances, but I have confidence in the lads.”“Callum Paterson’s been doing well in the Premier League with Cardiff City and Ryan Fraser has the most assists in that league (with Bournemouth). The Celtic boys are all coming into international duty on a high.”“It can be hard to bring your own individual form from a club into a new team at international level but that’s what we’re aiming to do. Hopefull,y we can get the right result.”Meanwhile, Robertson admits the withdrawals have impacted Scotland’s preparation for UEFA Nations League games against Albania and Israel.“Of course it’s been a bit disruptive but we always plan with different team set-ups, and people are 100 per cent concentrated on what they are doing. These things happen and people will need to step up.”“We have to think that people will react well in adversity. I’m sure that will happen in Albania.”
Facebook0TwitterEmailPrintFriendly分享According to a Soldotna Police Dispatch received on January 27, a Soldotna man was arrested for allegedly assaulting a cab driver. According to Courtview, he was arraigned on January 20 and is currently scheduled for a pre-trial conference on February 15. The incident occured on January 19, at 3:05 a.m., when Soldotna police responded to the Maverick Saloon for an aggressive male threatening to cause bodily harm to a cab driver and refused to pay his cab fare. Story as aired: Audio PlayerJennifer-on-Soldotna-man-threatened-cab-driver.mp3VmJennifer-on-Soldotna-man-threatened-cab-driver.mp300:00RPd Robert Luton, 31, of Soldotna, was arrested for assault in the fourth degree, theft in the fourth degree and violating his conditions of release. Luton was taken to Wildwood and held on $1,000 bail. Luton was arrested in October of 2017, for setting off the fire alarm at Sterling Elementary and causing an evacuation of the school. Luton was arrested for Terroristic Threatening in the 2nd Degree and Criminal Mischief in the 4th Degree.
In addition to the subscription campaigns, Need attributes the revenue spike to a pair of sponsored meet-and-greet events with magazine staff and two topical speaking events featuring Need contributors and members of local organizations. Need also is planning Street Music for Street Kids concert later this month and a “Your Powers for Good” events series.“The idea behind the events was to not only promote Need but to accomplish it through furthering our end mission of assisting humanitarian organizations and those in need,” founder and executive director Kelly Kinnunen said.Need launched the ScrewTheMan, SaveTheWorld intiative—which was inspired by Paste’s Save Paste campaign—in an effort to generate 25,000 new subscribers, which would more than double Need’s current circulation of 19,000. If successful, Need said it would eliminate all commercial advertisingfor one year and replace the allocated advertising pages with storiesof how readers are involved in saving the world.The Who Cares? campaign is intended to drive bulk subscription orders. “The average single order sale is up by $12 from last quarter, so each person is ordering more,” Stephanie Kinnunen said. Despite the revenue boost, though, she said the magazine has secured only “a fraction” of the new subscriptions needed to meet its ambitious goal. Minneapolis, Minnesota-based “humanitarian” magazine Need has seen some positive results from its ScrewTheMan, SaveTheWorld and Who Cares? subscription campaigns. So far—through the June, July and August period—the magazine has seen subscription revenue jump nearly 900 percent from the same period last year.“This has been amazing considering it is summer which is normally bad and we have not had a magazine out since early February,” editor-in-chief Stephanie Kinnunen told FOLIO:. Usually carrying a quarterly frequency, Need hopes to print its next edition by mid- to late-November.
More From Roadshow 2019 GMC Sierra Denali review: So close to greatness Car Culture Car Games and Apps Honda RidgelineAgain keeping the status quo, the Honda Ridgeline maintains third place on the American Made Index. This crossover-that-looks-like-a-truck provides a better ride than a traditional pickup and gets an awesome lockable trunk right in the floor of the bed. And it doesn’t do the truck stuff too badly, either, as it’s able to carry 1,860 pounds of payload and tow 3,500 pounds.The Ridgeline is powered by a 3.5-liter V6 good for 280 horsepower and 262 pound-feet of torque. That is channeled through a six-speed automatic transmission with available all-wheel drive. It’s built in Lincoln, Alabama. Now playing: Watch this: 68 Photos 2019 Jeep Cherokee can handle the rough stuff Chevrolet ColoradoMaking its debut in the top 10 is the Chevrolet Colorado. Shown here in the tough ZR2 Bison off-road spec, the Chevy Colorado is an excellent truck and one of the two midsize pickups you can get with a diesel engine. Adding to the ZR2’s two-inch lift and front and rear locking differentials, the Bison gets beefier skid plates (trust me, that’s a good thing), steel bumpers and integrated recovery points. Heck, you can even get a snorkel.Base models get a 2.5-liter four-cylinder engine with a six-speed manual transmission, but a more popular choice is the 3.6-liter V6 gas engine with 308 horsepower and 275 pound-feet of torque, mated to an eight-speed automatic transmission. Meanwhile, the 2.8-liter diesel pumps out 186 horsepower and a delicious 369 pound-feet of twist and is mated to a six-speed automatic. The Chevy Colorado is built in Wentzville, Missouri. Honda OdysseyThe feature-rich Honda Odyssey minivan also retains its number-two slot from last year’s list. While the 2019 model doesn’t see any changes from last, it’s still a darn good choice for families on the go with reconfigurable seats, Wi-Fi and an excellent rear-seat entertainment system. The Cabin Watch video system lets parents keep an eye on their little darlings without turning around in their seats, while Cabin Talk amplifies their voice so no yelling is required.The Odyssey is powered by a 3.5-liter V6 rated for 280 horsepower and 262 pound-feet of torque. Most trims get a nine-speed automatic but the top Touring and Elite trims now use a 10-speed automatic with stop-start technology. The Honda Odyssey is made in Lincoln, Alabama. 2019 Acura MDX adds new features and an A-Spec model Share your voice The Ford GT MkII shows what a race car can be when you… Chevrolet CorvetteMoving up from the 10th-place slot last year is the 2019 Chevrolet Corvette. While we’ve all been ogling the new mid-engine Corvette, it’s easy to forget what a performance bargain the current-generation ‘Vette is. From the base trim to the Grand Sport to the bonkers ZR1, the Corvette is an American icon.My preference is for the Grand Sport, which strikes a perfect balance between everyday drivability and canyon-carving performance. The 6.2-liter V8 puts out 460 horsepower and 465 pound-feet of torque. You can get it with a seven-speed manual or eight-speed automatic transmission, but the kicker is the borrowed chassis and aero parts from the beefier Z06. Like I said, perfect balance. The Corvette is made in Bowling Green, Kentucky. Tags Gamescom Ford 2020 Porsche 718 Cayman GT4 first drive: A standout track star Esports Ford,Enlarge ImageIt’s all in a day’s work for the Jeep Cherokee, the most American-made car in 2019. Jeep With high trade tensions looming and increasing talk of tariffs, more and more consumers are looking to buy American. Cars.com has released its annual American Made Index, showcasing companies that use the most American-sourced parts and labor in their vehicles. The results may surprise you.Cars.com analyzed more than 100 US-built vehicles for five key data points: manufacturing location, parts sourcing, US employment, engine sourcing and transmission sourcing. You might think something like the Ford F-150 would top the list, but it drops from its No. 5 spot for 2018 and out of the top 10 completely. Even the first-place holder, the Jeep Cherokee, is a pretty global product. It’s a Jeep, sure, but that brand is part of Fiat Chrysler Automobiles, an Italian-owned business.Cars.com surveyed 1,000 people and found that half are concerned about automotive import tariffs, with 41% saying they are unsure if tariffs would make them more likely to buy American. Either way, we’re big fans of all the vehicles on this list. These days, buying American doesn’t necessarily mean sticking with a US-based automaker. Tags 2019 GMC Canyon: A fancier Colorado General Motors Chevrolet Honda Jeep Acura 71 Photos 12 Photos 2020 BMW M340i review: A dash of M makes everything better 2019 Honda Pilot Elite: A smoother, tech-rich crossover SUV 81 Photos 2019 Chevy Colorado ZR2 Bison: An off-road animal 52 Photos 26 Photos 2020 Hyundai Palisade review: Posh enough to make Genesis jealous 63 Photos 69 Photos 18 Photos 2019 Honda Ridgeline review: Light duty, heavy punch 2019 Chevrolet Colorado ZR2 Bison: A tougher off-roader 2019 Honda Ridgeline: The commuter’s pickup truck GMC CanyonIf you’re looking for a slightly fancier version of the Colorado that’s more focused on luxe than dirt, check out the GMC Canyon. The top Denali trim gets standard heated and ventilated front seats as well as a heated steering wheel. Maximum payload capability is 1,665 pounds while max towing is a fairly healthy 7,600 pounds.The Canyon is available with the same 2.5-liter four-cylinder engine, 3.6-liter V6 or 2.8-liter diesel as the Chevrolet Colorado. It’s also built in Wentzville, Missouri. Car Industry Comment 10 Photos 4:41 49 Photos Team Fordzilla is looking for star video game drivers in Europe. Ford The annual Gamescom video game conference in Germany isn’t just about gaming. Ford Europe took the opportunity to announce it wants to be more involved in the virtual world, launching its Fordzilla esports racing team at the conference. The team will focus on “highest level” of racing on the virtual stage and recruitment began this week at Gamescom. The automaker plans to recruit national teams for France, Germany, the UK and Spain. From there, Ford will create a European team with a star player from each country.While Fordzilla will likely tackle multiple racing games in the future, the team will begin with a presence in “Forza Motorsport 7,” the latest driving simulator game for the Xbox One console. Ford has a good relationship with Turn 10, the studio behind the Forza Motorsport franchise. It worked with Turn 10 to make the second-generation Ford GT the “Forza Motorsport 6” cover car back in 2015.Like other companies that are increasingly turning to the virtual sport, Ford eyes a piece of the growing revenue stream esports brings in. According to data Ford cited, esports is expected to generate over $1 billion in revenue this year — a 26.7% jump over 2018. The automaker also said the synergies between gaming and future mobility solutions intrigues the company.Ford isn’t alone in esports involvement. Earlier this month, Honda expanded its involvement to become the official partner of the Riot Games League of Legends Championship Series. The Japanese automaker also serves as the official partner of Team Liquid in the series. Acura MDXMoving up one slot to sixth place on the American Made Index is the non-hybrid variant of the Acura MDX. With its SH-AWD system, the MDX is one of the better handling midsize luxury crossovers, and for 2019 the company gives us the A-Spec treatment with a new front fascia and side skirts, 20-inch wheels, wider exhaust tips, unique gauges, a new steering wheel, carbon fiber trim and various Alcantara interior touches.However, both the standard and A-Spec models get a 3.5-liter V6 engine, rated for 290 horsepower and 267 pound-feet of torque going through a nine-speed automatic transmission. The Acura MDX is made in East Liberty, Ohio. 2019 Acura RDX A-Spec: Sharp handling, sharper looks 3 Comments More From Roadshow Acura RDXThe third-generation Acura RDX squeaks into the top ten list with larger proportions, plenty of interior space and better handling than its predecessor. Forward collision warning with collision mitigation braking, adaptive cruise control that works even in low-speed traffic, lane-keeping steering assist and road departure mitigation are all standard across the board. Like its MDX counterpart, the RDX is available with the A-Spec styling package.The RDX sports a 2.0-liter, turbocharged, four-cylinder engine. Output is stated at 273 horsepower and 280 pound-feet of torque, and it’s mated to a 10-speed automatic transmission. The new RDX is built in East Liberty, Ohio. 2019 Honda Passport: A well-rounded midsize offering Jeep CherokeeKeeping its top-of-the-list placement, the Jeep Cherokee is 2019’s most American-made car. Refreshed for 2019, the compact crossover now features more tech, better cargo space and a slightly tweaked look. It’s available in no fewer the nine trims, including the off-road specific Trailhawk and a fancy-pants Trailhawk Elite.For 2019, the Cherokee gets a new 2.0-liter, turbocharged, four-cylinder engine with 270 horsepower and 295 pound-feet of torque, though naturally aspirated I4 and V6 choices are also available. Regardless of engine, a nine-speed automatic transmission gets the power to the pavement — or dirt as the case may be. The Cherokee is made in Belvidere, Illinois. 2019 Ford Mustang Shelby GT350: A friendlier track animal Share your voice Honda PassportThe Honda Passport is a new (well, reborn) entry to both the Honda lineup and the American Made Index. This midsize crossover comes to the fray with great driving dynamics and plenty of tech like the standard Honda Sensing suite of active safety features. An available 8-inch touchscreen gets Apple CarPlay and Android Auto as well as a Wi-Fi hotspot.Under the hood is the stalwart 3.5-liter V6 producing 280 horsepower and 262 pound-feet of torque. However unlike the Ridgeline, the Passport sends that power through a nine-speed automatic transmission. Having said that, just like the Ridgeline, this is the only powertrain available. The Honda Passport is built in Lincoln, Alabama. 2019 Honda Odyssey offers plenty of room and features for families 1 2019 Chevrolet Corvette Grand Sport loves to hustle Honda PilotDropping down to seventh place for 2019 is the Honda Pilot. Like its two-row Passport sibling, the three-row Pilot offers parent-focused technology like Cabin Talk as well as myriad standard driver-assistance features through the Honda Sensing tech suite. Honda’s largest crossover offers up nearly 84 cubic feet of cargo space. Honda’s 3.5-liter V6 engine shows up again, making a serviceable 280 horsepower and 262 pound-feet of torque. Touring and Elite trims get a nine-speed automatic transmission while lower trims have to make do with a six-speed auto. The Honda Pilot is made in Lincoln, Alabama.
The Supreme Court on Tuesday dismissed a petition filed by the Board of Control for Cricket in India (BCCI) to review the apex court’s order, in which it agreed with the recommendations of the Justice (retd) RM Lodha Committee. The recommendations, when implemented, would bring more transparency to the cricketing body.The BCCI, led by president Anurag Thakur, has said that implementing the recommendations could spell more problems for the cricketing body, including its expulsion from the International Cricket Council (ICC).In an affidavit filed with the apex court on Monday, Thakur had said of his conversation with ICC President Shashank Manohar: “When he was president of BCCI, he had taken a view that the Lodha panel recommendations of appointing a nominee of the CAG on the board’s Apex Council would amount to governmental interference and might invoke an action of suspension from ICC,” Thakur had said.The Lodha panel recommendations, it may be noted, include barring ministers and civil servants as well as those above 70 years of age from becoming BCCI office bearers. If implemented, this could end political presence in the BCCI.The current BCCI president, Anurag Thakur, is a Bharatiya Janata Party (BJP) leader. Former BCCI chief Sharad Pawar is the founder of Nationalist Congress Party. He is a former Union Cabinet minister and the former chief minister of Maharashtra.The BCCI has also contested the one-state-one-vote proposal, which limits the voting power of traditionally more influential states and their selectors; and a cooling off period in its review petition in the Supreme Court.If and when the recommendations are implemented, Thakur and many others could be on their way out of the BCCI. However, Thakur could land a role in the ICC, with sources saying that the world cricketing body is keen on giving Thakur the chairmanship role in its development committee. He will succeed Manohar.
Prime minister Sheikh Hasina. File PhotoPrime minister Sheikh Hasina on Monday urged the public representatives to work for the welfare of the people saying that victory in polls is not enough, rather they (public representatives) must win the hearts of the masses.“Being elected public representatives once means not an end of a chapter, rather they will have to win hearts and minds of the people of their locality,” she said.The premier added: “So, you’ll have to work for the welfare of the people irrespective of the party affiliations and uphold the trust and confidence that the people reposed on you.”The prime minister was addressing the oath-taking ceremony of newly- elected mayor and councillors of the Mymensingh City Corporation (MCC) at her office here this morning.Sheikh Hasina said public representatives will have to work for the development of their respective areas to earn satisfaction of the people.In this regard, she reminded them about their responsibilities saying the politics for the personal interest never sustains and can’t bring any welfare to the people.Referring to the steps of her government for decentralisation and strengthening of the local government bodies, the prime minister said new divisions and city corporations have been created in the country to attain the goal.Sheikh Hasina said her government has been implementing Taka one lakh 73 thousand crore ADP this year and public representatives will have to appropriately spend hard-earned money of the people.About the national budget to be placed on 13 June next, the prime minister said over Taka five lakh crore budget is being prepared, of which Taka two lakh crore will be spent for implementation of the ADP.She called upon the public representatives to oversee the development programmes being implemented in their localities to ensure proper use of public money.Sheikh Hasina said her government wants to ensure that Bangladesh as an independent country can advance in the world stage with its independent existence.Pointing out her government’s massive uplift efforts, she said all measures have been taken to develop the country from very grassroots level. “We’re working not only to develop the urban areas, we’re also working to develop the rural areas,” she said. Earlier, the premier administered the oath of office to MCC Mayor Ekramul Haque Titu, while 44 councillors — 33 male councillors and 11 women councillors — took oath from Local Government Minister Md Tazul Islam.Local Government Division Senior Secretary SM Golam Faruk conducted the oath-taking ceremony, while Road Transport and Bridges Minister ObaidulQuader was present on the dais.Agriculture Minister Dr Abdur Razzaque, Deputy Opposition Leader in Parliament Begum Raushon Ershad and PM’s Adviser Dr Tawfiq-e-Elahi Chowdhurywere present, among others, at the function.The first-ever election to the MCC was held on May 5 in a festive mood.Awami League mayoral contender Ekramul Haque Titu was elected uncontested as there was no rival candidate against him after the withdrawal of candidature by Jatiya Party mayoral contestant Jahangir Ahmed.Some 242 candidates contested for the general councillor posts in 33 wards, while 70 women candidates vied for 11 reserved women councillor postsin the polls.The government upgraded Mymensingh to Bangladesh’s 12th city corporation on 15 Oct of last year.Sheikh Hasina, also the president of Bangladesh Awami League, expressed her profound gratitude to the countrymen for reelecting her party and giving her chance to serve them again.She said that the aim of the government is to materialize the dream of Father of the Nation Bangabandhu Sheikh Mujibur Rahman to turn the country into a Sonar Bangla (golden Bengal).The prime minister said that the government has already announced 2020-21 as “Mujib Barsho” and decided to celebrate the year by reducing poverty further.She mentioned that the government has adopted Delta Plan 2100 for the future generation of the country and signed an agreement with the Netherlands government to this end.Sheikh Hasina said that the government is setting up 100 economic zones across the county and already earmarked places for 80 economic zones.“The aim of this move is to restrict setting up industries indiscriminately on the cropland,” she said.The AL chief said that after setting up these economic zones, the country will move towards industrialization further with employment generation.The prime minister said if the country could manage 90 percent of its development budget with internal resources, then there will be mo need for begging for help from others.“We’ll live with our own dignity and this was the dream of the Father of the Nation … we’ll materialize that dream,” she added.She said that people under the leadership of Bangabandhu had liberated this country through the liberation war. “So the thinking and spirit of the people of this land should be like that,” she said.Vowing to build a corruption-free Bangladesh, the premier asked the public representatives to stay alert to terrorism, militancy and drugs as these social menaces destroy a family, society and country.
Single-Walled Carbon Nanotube (SWNT). Source: Christian Thielemann More information: Reactions of the inner surface of carbon nanotubes and nanoprotrusion processes imaged at the atomic scale, Nature Chemistry (2011), doi:10.1038/nchem.1115, Published online 14 August 2011Related: Self-assembly of a sulfur-terminated graphene nanoribbon within a single-walled carbon nanotube, Nature Materials 10, 687–692 (2011), doi:10.1038/nmat3082 , Published online 07 August 2011 Carbon nanotube structures changed by ‘attack’ from within, researchers discover (PhysOrg.com) — Historically, the interior surface of single-walled carbon nanotubes (SWNTs) has not been considered to be chemically reactive. Recently, however, researchers at the University of Nottingham School of Chemistry in the UK and the Ulm University Transmission Electron Microscopy Group in Germany demonstrated sidewall (inner surface) chemical reactions when they inserted catalytically active atoms of rhenium metal (Re) into these atomically thin cylinders of carbon. These reactions formed nanometer-sized hollow protrusions in three distinct phases (sidewall deformation and rupture, open nanoprotrusion formation, and stable closed nanoprotrusion) which the researchers imaged at the atomic level – in real time at room temperature – using Aberration-Corrected High-Resolution Transmission Electron Microscopy (AC-HRTEM). Explore further Prof. Andrei N. Khlobystov conceived of the initial idea, proposed the general mechanism and wrote the original manuscript; Thomas W. Chamberlain designed the experiments, synthesized the materials and analyzed the microscopy data; Ute Kaiser contributed to the development of the experimental methodology and discussion of the results; Elena Bichoutskaia, Nicholas A. Besley and Adriano Santana performed the theoretical modeling and explained the details of the reaction mechanisms; and Johannes Biskupek analyzed the images, carried out TEM image simulations, and – with Jannik C. Meyer and Jens Leschner – recorded the AC-HRTEM images and contributed to the initial explanation of the observations.The main experimental challenge the team faced was to devise a method for delivering single atoms of catalytically active metal into very narrow carbon nanotubes with a diameter of 1.5 nm – about 80,000 times smaller than the thickness of human hair. “The presence of such metal atoms within the nanotube is important not just for investigating the chemical reactivity of the inner sidewall, but also for creating new nanostructures from the nanotube,” notes Khlobystov. The second major challenge, he adds, “was to study the delicate molecules, reactive atoms and their chemical transformation inside nanotubes in real-time at the atomic level.” To address these challenges, the team exploited the remarkable affinity of carbon nanotube with fullerenes – carbon nanostructures, which look like nanometer-sized cages and can be considered as structurally related to nanotubes. “The fullerenes are known to be attracted strongly into the nanotube cavity by van der Waals forces. We tagged each fullerene with a single atom of rhenium metal, so that each molecule brings a catalytically active metal atom into the nanotube,” Khlobystov explains. “It appears that such modified fullerenes are excellent vehicles for delivery of metal atoms into nanotubes, as they enter in nanotube spontaneously and irreversibly.”The second challenge, he continues, was solved by the researchers in Ulm, who applied a specially designed electron microscope that utilizes low energy electrons for imaging molecules and atoms. “They have succeeded at imaging the delicate molecules with atomic resolution and, most importantly, at capturing them in action – i.e., in chemical processes within the carbon nanotube in real time.” This document is subject to copyright. Apart from any fair dealing for the purpose of private study or research, no part may be reproduced without the written permission. The content is provided for information purposes only. Copyright 2011 PhysOrg.com. All rights reserved. This material may not be published, broadcast, rewritten or redistributed in whole or part without the express written permission of PhysOrg.com. Citation: Inside story: Chemical reactivity on the inner surface of single-walled carbon nanotubes (2011, September 15) retrieved 18 August 2019 from https://phys.org/news/2011-09-story-chemical-reactivity-surface-single-walled.html Kaiser comments that “Our aim is use low voltage TEM – which is now possible after the introduction of hardware aberration correction by Harald Rose, Max Haider and Knut Urban – to study in detail the atom-by-atom level influence of electron-beam interacting with low-Z matter,” which is matter with a low atomic number. “To accomplish this we developed the real-time imaging and data acquisition technology to reveal carbon nanotubes and their interior in high contrast and atomic resolution. “In order to provide a comprehensive description of a possible mechanism for nanoprotrusion formation on carbon nanotube walls,” adds Bichoutskaia, “we used a multi-scale modeling approach that combined accurate quantum chemical methods with semi-empirical molecular dynamics simulations.”Going forward, there are a number of innovations that might be developed and applied to the current experimental design – for example, catalysts other than rhenium, carbon sources other than the fullerene cage wall, nanotubes produced or grown using an alternative method, nanotubes using different fullerene, or variations in the e-beam. “Our next steps include implementing catalysts and more complex molecules into carbon nanotubes,” Kaiser confirms. “We’re also working on varying the e-beam energy and detection efficiency in our Sub-Angström Low-Voltage Electron (SALVE) microscopy project at Ulm University.”Khlobystov points out that there are dozens of different metals in the Periodic Table of elements, and each of them has a distinct set of useful physicochemical properties that could be harnessed at the single-atom level. “Our method of transport and encapsulation of metals into nanotubes is quite universal, as it can be adapted for any of the transition metals, many of which have outstanding chemical, optical and magnetic properties,” he explains. “For example, introduction of photoactive atoms into carbon nanotubes, such as ruthenium or platinum, may enable initiation and control of chemical reactions within nanotubes using pulses of light, which would be more useful than an electron beam for practical applications.”Furthermore, transition metals with well-defined catalytic properties different from those of rhenium, such as palladium, platinum, rhodium, and nickel, could trigger entirely different reactions in nanotubes, leading to different products that are difficult to anticipate at this stage – but Khlobystov is confident that within the next 12 months the team will be able to tell exactly what can be achieved with other types of metals. “Even now,” he stresses, “we know that addition of non-metallic elements other, such as sulfur, into nanotubes can drastically change the course of chemical reactions inside the nanotube.” Recently, the team published a paper showing that when sulfur and carbon are present in nanotube together, we can form unique nanoribbon structures with remarkable properties.”In terms of how their research might impact the design and/or development of electronic, medical, sensor or other nanoscale devices, Khlobystov notes that since carbon nanotubes are ideal containers for molecules and atoms, “With one macroscopic dimension,” being length, “and two nanoscopic dimensions, they can serve as a bridge between the molecular and the macroscopic worlds. Magnetically active molecules embedded in nanotubes, for example, could be integrated in miniature data storage and spintronic devices, and nanotubes could be used as a capsule for delivery of medicinal molecules directly into diseased cells in human body.” Moreover, Khlobystov notes that the electronic properties of the nanotube itself, such as band gap and charge carrier concentrations and mobility, are greatly affected by interactions with the guest molecules inside the nanotube, which forms a basis for sensors and detectors. “Furthermore,” he adds, “development of nanotubes as chemical reactors is a very promising direction, as pathways and rates of chemical reactions confined in nanotubes are drastically affected by the nanotube. Chemical synthesis in nanotubes is a new way of making molecules that will enable us to make new products that are not possible to prepare otherwise. Catalysis by transition metals is essential in this context, and understanding direct reactions of metals with nanotubes is the first step.”Kaiser believes that besides chemists and physicists working on basic research, nanotechnologists devoted to topics such as energy storage, catalysis and medical drug delivery both on hard-, soft- and combined hard-soft matter will benefit from the team’s research. “New technologies in TEM control, efficiency that allows us to detect every scattered electron, and goniometer design that is not disturbed by drift issues during TEM data acquisition will strongly enhance the new applications.” (A goniometer allows a specimen to be rotated to a precise angular position.)Kaiser agrees that carbon nanotube spontaneous self-assembly and interior nanoprotrusion formation, which all may open new avenues for nanoscale molecular synthesis. She also cites the effect of confinement within carbon nanotubes as well as the newly shaped CNT with nanoprotrusions as potentially providing a new mechanism for tuning the electronic properties of graphene nanoribbons. “The spectacular rotational and translational motion of helical nanoribbons within the nanotube, she adds, “as well as the possible regular formation of nanoprotrusions may inspire the exploration and harnessing of new electromechanical effects in nanodevices.”In the short-term, Khlobystov points out, the team is rapidly expanding the range of transition metals inserted into nanotubes to broaden the scope of chemical reactions studied under conditions of extreme confinement and, at the same time, to see whether the nanotube sidewall could be engaged in further, perhaps even more spectacular chemical transformations. “So far, our experiments have been carried out on a small scale, so our process would also need to be scaled up to test and explore real applications of these materials,” he acknowledges.For Kaiser, next steps include imaging more complex structures at the present 80kV aberration-corrected TEM and at 20kV with our new SALVE prototype microscope. “We will explore the electron-beam specimen interaction further and will probably discover further surprises,” she adds.The potential for an in vivo application remains uncertain. “At the moment,” Khlobystov opines, “I can’t really see how our process can be transferred to an in vivo protocol. The conditions required to spark chemical transformations in nanotubes are still very harsh. However, if a living system would possess some sort of super-enzyme that is able to crack carbon-carbon bonds of the nanotube sidewall, in principle, we could adopt our nanoreactors for a biological system.”Kaiser admits that this is rather speculative, noting the additional limitation that in vivo atomic resolution is not obtainable today. “However,” she opines, “with our SALVE initiative a new low-voltage TEM will be finalized in two years through our collaborations with partners CEOS and Carl Zeiss, we will be a step closer to image beam-sensitive biological materials.”Khlobystov emphasizes that these exciting applications rely on a well-defined and reliable interface between the nanotube container and the contained molecules and atoms. “Because a pristine nanotube has an atomically smooth surface, the molecules shuttle randomly from one position to another within the nanotube in almost frictionless motion. Nanoprotrusions formed on nanotubes in our experiments create hollow pockets on the nanotube inner surface, which can effectively trap desired molecules and atoms in a specific location, thus giving a mechanism for controlling their positions and orientations. A greater degree of control over the dynamic behavior of encapsulated molecules is essential,” he concludes, “for successfully harnessing the full potential of their optical, magnetic and chemical properties.”