Chelsea winger Christian Pulisic eyeing loan move awayby Paul Vegas19 days agoSend to a friendShare the loveChelsea winger Christian Pulisic is eyeing a loan move away in January.The Daily Mailsays he is said to be considering asking for a loan move away from Chelsea if he is not given more opportunities soon.Pulisic has found himself falling down the pecking order at Stamford Bridge just three months after completing his £58million move from Borussia Dortmund.The 21-year-old has been an unused sub in the last three Premier League matches – and hasn’t been seen in top flight action since August.Now the American is open to the prospect of moving elsewhere in January if Frank Lampard continues to overlook him in his Chelsea plans. TagsTransfersAbout the authorPaul VegasShare the loveHave your say
“As a Government we want to see more youth accessing tertiary education, and this is a policy directive at the SLB,” he said. The Students’ Loan Bureau (SLB) is reporting that for the 2017-2018 academic year it received 13,679 applications. for which more than $3.09 billion was disbursed, with an approval rate of 99 per cent. Addressing a Jamaica Information Service (JIS) ‘Think Tank’ on March 14, State Minister in the Ministry of Education, Youth and Information, Hon. Floyd Green, assured students that the Government is working to ensure that all persons who qualify to access tertiary education will be able to pursue their goal. Story Highlights The Students’ Loan Bureau (SLB) is reporting that for the 2017-2018 academic year it received 13,679 applications. for which more than $3.09 billion was disbursed, with an approval rate of 99 per cent.The SLB provides loans as well as grants to help with non-tuition expenses to students pursuing tertiary studies.Addressing a Jamaica Information Service (JIS) ‘Think Tank’ on March 14, State Minister in the Ministry of Education, Youth and Information, Hon. Floyd Green, assured students that the Government is working to ensure that all persons who qualify to access tertiary education will be able to pursue their goal.“As a Government we want to see more youth accessing tertiary education, and this is a policy directive at the SLB,” he said.There are three types of loans that students may access – Targeted; Pay as you Study and Postgraduate.Executive Director of the SLB, Monica Brown, who also addressed the ‘Think Tank’, said that under the Targeted loan type, where a majority of the students would access tertiary financing, they are required to repay the loan on completion of their studies.The loan repayment period has been adjusted from 10 years to 15 or 20 years, depending on the programme of study.Ms. Brown said that although students accessing Targeted loans are not required to make repayments during the in-school years, the SLB encourages those who are able to make payments during the moratorium period to do so, as this reduces the amount that will be left to repay on completion of their studies.She pointed out that effective April 2016, the Bureau switched from using the ‘add on method’ to using the reducing balance method to calculate the interest rate on repayment, and this has resulted in significant savings for those who borrow from the SLB.The applicable interest rate using the reducing balance is 7.8 per cent during the in-school years and 9.5 per cent when the loan enters repayment stage. Ms. Brown noted that there are areas given priority for the allocation of funds, particularly where the contributions to national development are greatest. They are agricultural studies, engineering, information technology and maritime and logistics studies. The interest rate repayment is six per cent on the reducing balance.Applications, which are now open for persons who wish to access loans for the 2018-2019 academic year, will close on Thursday, May 31.
CARACAS, Venezuela — Venezuela will hold onto its U.S.-based Citgo refineries, settling a lawsuit that threw ownership of the struggling country’s prized assets into peril.Court papers show that Venezuela on Friday began paying off $1.4 billion that a panel said was owed to the Canadian mining firm Crystallex, following a disputed takeover of the company by the late-President Hugo Chavez.To recoup its losses, Crystallex had targeted Citgo refineries, potentially forcing Venezuela to sell off its most valuable foreign asset.Papers filed in a Canadian court say Venezuela recently paid Crystallex $425 million, while agreeing to make good on the rest by 2021. That enables them to hold onto their refineries.Russ Dallen of Miami-based Caracas Capital Markets says the payment shows Venezuela’s changing tactics — from fighting creditors to striking deals.The Associated Press
If you are interested in knowing more about the changes happening in the Senate, Senator Woo will shed light on how Senate reform has led the Senate in a direction that is less partisan; more diverse in background, gender, and qualifications. FORT ST. JOHN, B.C. – The Comunity Development Institute is hosting their Leaders Lab Series with guest speaker Senator Yuen Pau Woo.On Wednesday, July, 17th, 2019 at the Northern Lights College, Room 202, at 7 pm join in this free talk by Senator Yuen Pau Woo an independent Senator representing British Columbia.
FORT ST. JOHN, B.C. – The Fort St. John RCMP are currently searching for a wanted person following an incident of flight from police.According to RCMP, on the afternoon of August 14 at around 3:00 p.m., officers attempted to conduct a traffic stop on a dark coloured pickup, where the alleged driver, 30-year-old Gavin Davis who is well known to police, refused to stop and fled at a high rate of speed.As a result of this incident, RCMP have issued five arrest warrants for Davis varying from Dangerous operation of a motor vehicle to Driving without a valid driver’s licence. Davis is described as:Indigenous man5’8’’ tall, weighing 230 poundsblack hairbrown eyesThe RCMP say Davis is considered armed and dangerous, and should not be approached.If you see Davis, you are being asked to call 9-1-1 immediately.
New Delhi: A light bout of rain and windy conditions Friday provided much-needed respite from the scorching dry heat in the national capital, officials said. The weatherman said a number of areas in the city recorded light rainfall accompanied by cool breeze. The city has been witnessing temperatures soaring to mid-40s over the last few days. On Tuesday, Palam recorded a sizzling high of 45.3 degrees Celsius, equalling the record high of April 25, 1970. Also Read – India gets first tranche of Swiss account details under automatic exchange frameworkOn Friday, the city recorded a high of 39.5 degrees Celsius and a low of 24.8 degrees Celsius. The humidity level oscillated between 37 and 64 per cent. The relative humidity recorded at 8.30 am was 54 per cent. The Met office has predicted partly cloudy skies for Saturday. The maximum and minimum temperatures are likely to hover around 40 and 24 degrees Celsius. On Thursday, the minimum temperature was 25.8 degrees Celsius and the maximum temperature settled at 41 degrees Celsius.
Bayern Munich’s Thiago Alcantara wants to leave the club and is keen on a move to Real Madrid this summer, according to Don Balon.The Spain international wants to return to Spain to continue his club career and has set his sights on a move to the Santiago Bernabeu.The midfielder has been linked a move away from the Allianz Arena all summer long with Manchester City and Real Madrid reportedly interested in his services.However, with the close of the transfer window in England, any chance of the Premier League champions signing him this summer have disappeared leaving European champions, Madrid as the sole destination should he leave Munich this summer.Thiago reveals that Bayern Munich still use Pep Guardiola’s philosophies Andrew Smyth – April 24, 2019 Thiago Alcantara admits Pep Guardiola’s coaching philosophies are still used at Bayern Munich, despite the Catalan leaving nearly three years ago.He has a good relationship with Julen Lopetegui, who he worked wine during their time together in the Spanish national team and the former Spain head coach wants to sign another midfielder, but President Florentino Perez is hesitant to meet Bayern’s asking price.Thiago moved to Bayern five years ago when former Barcelona manager Pep Guardiola who gave his debut at the Camp Nou, decided to sign him for the Bavarians.His potential move to Barcelona rivals Real Madrid wouldn’t go well with the hardcore fans of the Catalan club as the player is a graduate of the famous La Masia academy.
Former Juventus midfielder Edgar Davids is not “convinced” at all by Paul Pogba and has urged the Frenchman to showcase more of his talentThe 25-year-old played a pivotal role in France’s World Cup-winning campaign at Russia this summer.However, Pogba has again reverted to the patchy form that he often had last season with Manchester United.Manager Jose Mourinho had handed the French midfielder the captain’s armband in the hope that it would inspire improved performances at United.But the Red Devils’ recent results have suggested otherwise after losing two of their opening four Premier League of the 2018/19 campaign.Davids himself is disappointed to see Pogba’s continued struggles at United.Although the Dutchman knows that Pogba has what it takes to be one of the world’s best central midfielders.Vidic: “Ronaldo is the most professional footballer I’ve seen” Andrew Smyth – September 14, 2019 Nemanja Vidic opened up on how a 21-year-old Cristiano Ronaldo’s professionalism left him stunned at Manchester United.He told Canale 5: “I am not at all convinced by Paul Pogba.“He plays a lot in England, it’s true, but I expected a lot more from him.”Recent reports suggest that Pogba may be on the verge of a sensational return to Juventus as part of an exchange deal with Argentine striker Paolo Dybala.But Davids feels that there is still more to come from Dybala and urged him to “work harder”.“Dybala is a great talent, but he has to work harder,” he continued.“It is not always the fault of the coach or the game system, even the player must look in the mirror and do more.”Davids spent the majority of his career at Juventus and won three Serie A titles along with two Italian Supercups.
The Emirati club is playing for the first time in the FIFA Club World Cup and they hope to get far in the tournamentUnited Arab Emirates’ club Al Ain is celebrating its 50th anniversary this year, and they want to do it with style.The team will take part in the 2018 FIFA Club World Cup which starts on Wednesday, December 12.Known as The Boss, this team is based in the city of Al-Ain in the United Arab Emirates.The club was founded in 1968 and is celebrating its 50 anniversary this year.With 34 official championships, Al-Ain is one of the biggest clubs in the Emirates, having won the local tournament 13 times.OFFICIAL: Qatar will host the next two Club World Cups Manuel R. Medina – June 3, 2019 FIFA has announced today that the next two competitions will be played as planned, after meeting today in Paris.They have only won the AFC Champions League once.Being the local team, they will surely be well-supported during their 2018 FIFA Club World Cup participation.Like all hosts, they will battle for a ticket to the Quarter-Finals in the Playoff match against New Zealand’s Team Wellington on December 12th.#CWC18: Get to know @alainfcae_en – The Emirati club is playing for the first time in the @ClubWorldCups and they hope to get far in the tournament. pic.twitter.com/YCrwaKfNvc— Ronaldo.com (@ronaldocomint) December 8, 2018
Facebook Twitter Google+LinkedInPinterestWhatsAppThe Fast & the Furious fans worldwide have being mourning the death of one of the franchise’s stars, Paul Walker who plays “Brian O’Conner ” in the movies. In a sort of twisted irony, the actor and his friend died in a movie-like car crash in California while he was on his way to a charity event to aid Filipino victims of Typhoon Haiyan. Reports are that the Porsche GT Walker was driving flew off the road, slammed into a tree then burst into flames. Officials say speed is a factor. The final Fast & Furious sequel will open in June 2014. Walker was 40 years old. Also passing away over the weekend, another Paul… founder of TBN, Trinity Broadcasting Network Paul Crouch. Crouch had been suffering a degenerative heart disease for years now and was known for his love of shouting praise the lord. TBN is the world’s largest Christian television network. Paul Couch was 79 years old. Facebook Twitter Google+LinkedInPinterestWhatsApp Related Items:
Women and children are at greater risk than men.ReutersThe Innovation for Clean Air (IfCA) was launched in Bengaluru on Wednesday. The two-year UK-India joint initiative provides Indian and UK stakeholders opportunities to test interventions related to air quality and EV integration. Speaking at the IfCA launch on Wednesday, British Deputy High Commissioner Dominic McAllister said: “I am delighted to launch this joint programme. Such collaborative initiatives are an example of how the UK and India can work as a joint force for good on innovative solutions and can bring the best of our research communities, academia and businesses together to address shared challenges, such as clean air.”The initiative provides a unique measurement system for air quality by integrating satellite and sensor data and helping to support India’s transition to electric vehicles. The programme is led by Innovate UK, part of UK Research and Innovation (UKRI), and is funded by the Newton Fund with matched resources from various partners in Karnataka and India. Speaking at the IfCA launch, British Deputy High Commissioner Dominic McAllister said: “The UK and India can work as a joint force to bring the best of our research communities, academia and businesses together to address shared challenges, such as clean air.”UK Research and Innovation India (UKRI) Director Rebecca Fairbairn said: “This is a really exciting initiative. UKRI has been working with India for over a decade, focussing on excellent research that makes a difference to society and to our economies but this is the first time the UK Catapult network, which drives innovation in highly targeted industries has been implemented here and it demonstrates the creativity possible through India-UK partnership.”The key partners for the programme are the Indian Institute of Science (IISc), Enzen, Project Lithium, Confederation of Indian Industries, C40 Cities and Clean Air Platform. Other partners include Citizens for Sustainability, World Resources Institute, Indian Institute for Information Technology Bangalore (IIIT-B), Shakti Foundation, Shell Technology Centre, Global Business Inroads and India Smart Grid Forum. A current UK partner is Earthsense working in collaboration with the Catapults.Air quality & EV innovation: Bengaluru and London share challenges and opportunities in relation to improving air quality. The two cities are founding partners of the C40 Air Quality Network. The programme will identify innovations that have the potential to improve air quality and provide an environment to test and refine ideas. In parallel, the programme will contribute to a more detailed localised map of the air quality of Bengaluru through the unique combination of satellite and sensor data, including both on-the-ground and mobile data. The programme will identify relevant challenges around EV charging infrastructure, grid management and integrating renewable energy to ensure a sufficient, reliable and clean source power and facilitate opportunities for Indian and UK innovators to collaborate in developing long-lasting relationships to address these challenges.Innovate UK is funding the UK Catapult network in executing this programme. The UK Catapults network established by the UK government is a network of world-leading organisations focused on driving innovation in specific industrial sectors. They bring together the best businesses, scientists and engineers to work side by side on late-stage research and development. Representatives from the UK Energy Systems, Connected Places and Satellite Applications Catapults are in Bengaluru, Karnataka this week to launch the UK-India Innovating for Clean Air programme. They met stakeholders in Bengaluru, including the state government. Due to the enthusiasm of stakeholders such as the success of Lithium Taxis and BMTC’s plan to launch electric buses, the Catapult network has decided to focus on Bengaluru to enhance the progress already made in air quality and electric vehicle transition in Bengaluru.
Hilsa fish file photoFishermen in coastal districts are preparing to net hilsa as the 22-day government ban on fishing the delicious fish comes to an end on Monday, reports news agency UNB.Earlier, the government imposed a ban on catching, selling, hoarding and transportation of hilsa in different rivers for 22 days from October 12 in 27 districts to boost Hilsa output through protection of the mother fish during its peak breeding season.During a visit to the KB Bazar Ghat in Bagerhat on Saturday, the UNB correspondent saw the fishermen preparing their trawlers and fishing nets to go to the Bay of Bengal to catch hilsa.Trawlers were being towed to rivers from the dockyard. Fishing nets, fuel and daily essentials were being loaded in the trawlers. Thousands of fishermen are waiting to start their journeys to the sea.Locals alleged that fishermen from India enter Bangladesh water territories illegally to catch Hilsa. They demanded government steps so that the Indian fishermen cannot enter Bangladesh territory.Officials at the Fisheries Department, Bangladesh Navy, Coast Guard, Air Force, district and upazila administration, police, Rapid Action Battalion (RAB) conducted drives to prevent Hilsa fishing during the period.Besides, executive magistrates conducted mobile courts and punished a good number of fishermen who violated the ban.Sheikh Idris Sheikh, president of Bagerhat Coastal Fishermen Association, also alleged Indian fishermen enter Bangladesh territory and catch fish during the restricted period.Zia Haider Chowdhury, district fisheries officer, said: “Now we’ve to save Hilsa fry (under 10 inches). The authorities will impose a ban on catching Hilsa fry from November 1 to June 30 in coastal areas.”“If jatka (hilsa fry) can get the chance to get mature, around five and a half lakh tonnes of hisa could be netted next year,” the official added.
BNP joint secretary general Syed Moazzem Hossain Alal at Nirbachan Bhaban in city. Photo: Tanvir AhmedJatiya Oikya Front on Thursday demanded the withdrawal of more 92 higher public and police officials from election duty before the upcoming 11th parliamentary polls, reports UNB.The opposition alliance made the demand by submitting a list of the officials to Election Commission (EC) secretary at Nirbachan Bhaban in the afternoon.On behalf of Oikya Front, BNP joint secretary general Syed Moazzem Hossain Alal submitted the list and 13 letters signed by party secretary general Mirza Fakhrul Islam Alamgir on their various demands and observations to create a level-playing field.Of the 92 officials, 70 are from police administration while 22 from public administration, including deputy commissioners and EC secretary Helal Uddin Ahmed.The alliance urged the EC not to engage police officials who are the followers of any particular political party in the election duties.Talking to newsmen, Alal said, “We’ve demanded the withdrawal of over 60 officers of different ranks of police, including DIG, additional DIG and police superintendent, who are busy creating obstacles towards ensuring level-playing field.”He said they also submitted detailed information to the EC about the police officials they are seeking to be pulled out from the electoral responsibilities.The BNP leader said the chief election commissioner today (Thursday) called upon the police officials to remain neutral, but the commission has the authorities to give them order.He claimed that some government and EC officials have been carrying out activities that go against the electoral code of conduct after the announcement of the election schedule. “We’ve presented some documents in this regard and sought preventive measures.”Alal alleged that some ‘controversial’ officials at National Telecom Monitoring Centre (NTMC) and Bangladesh Telecommunication Regulatory Commission (BTRC) had blocked Skype and internet services around their chairperson’s Gulshan office as their leader Tarique Rahman was interviewing the party’s nomination seekers. “It’s also a violation of the election code of conduct.”He said police kept arresting BNP leaders and activists, including the nomination hopefuls.Alal said the EC instructed all to remove the election campaign materials, including posters and billboards, but many city areas are still replete with posters of Boat and Plough. “We’ve placed enough documents before the EC in this regard and demanded necessary actions.”He said different city corporations and other government organisations are still carrying out campaigns in favour of Awami League in the name of development. “We demanded the commission stop it immediately.
For Black History Month, the AFRO presents a series of articles highlighting important local heroes from the paper’s archives. We start off this week with Lillian Nutter, an expert watch repairer.In 1940, Lillian Nutter was nominated for the AFRO’s Hall of Fame. (AFRO File Photo)Because she is one of the few women in this country who are expert watch-repairers, Mrs. Lillian Nutter of 1719 Harlem Avenue is this week’s nominee for the AFRO’s Hall of Fame.For more than five years, Mrs. Nutter has worked daily alongside of Colvin R. Nutter, her husband, helping to repair watches and clocks, at their store in the 1200 block of Pennsylvania Avenue.Has Charming MannerMrs. Nutter is not the type of woman you would expect to see sitting at a work bench in a jewelry store – that is, if you would expect to see any woman handling that type of work. Small, pleasant-faced, and the possessor of a charming manner, she has the appearance, instead, of a woman whose interest rarely go beyond her home.Bearing the maiden name of Gray, Mrs. Nutter is a native of Calvert County, Md., and is one of a family of seven children. Before her marriage, she supported herself by her work as a seamstress.‘Twas Love at First SightApproximately seven years ago, she met Mr. Nutter, one Sunday afternoon, when her sister invited him to her house for dinner. It was love at first sight, and, shortly afterwards, they were married.Right away, Mrs. Nutter began to take an active interest in her husband’s jewelry business. Beginning in his store as a clerk and secretary, later she began studying the art of repairing timepieces under his guidance, and, in a year’s time, she was far enough advanced to handle the simple repair work.Now, she is fully capable of handling a watch repairing establishment by herself, and, according to Mr. Nutter, is an expert on both the theory and practice of watch repairing.Aside from all of this, Mr. Nutter declares that Mrs. Nutter is positively the best cook in the city, and is the only person he has ever known who could cook a turkey to suit his taste.Loves to CookMrs. Nutter readily admitted that she loved to cook, and also liked to read and play tennis. Not caring for fiction, her reading is generally confined to biographies, books on metaphysics, and other non-fiction works.Having been coached by her husband, who is himself a player of no mean ability, Mrs. Nutter has made such rapid strides in her tennis that she is now thinking seriously of entering one or two of larger tournaments this year.She’s a Bit ModestAlong with her husband, she has been a member of Metropolitan Methodist Church for a number of years. There are no children.Although she is a rather frank person, Mrs. Nutter is just a little modest when there is any mention of the fact that her advancement in her chosen profession has made her an outstanding character. Yet, her explanation of it all is that she thinks every woman should interest herself in her husband’s business, and help him as much as possible to make is successful.
Maryland Gov. Larry Hogan this week signed legislation that strengthens the state’s equal pay law.The bill increases transparency, shining a light on possible pay disparities by prohibiting businesses from penalizing employees who disclose or discuss their salary.The measure also buttresses anti-discrimination statutes in the existing Equal Pay for Equal Work law by also barring discrimination on the basis of gender identity.Civil, women’s and LGBT rights advocates praise Maryland’s efforts, which mirror efforts nationwide such as the federal Lilly Ledbetter Fair Pay Act, which makes it easier for workers to challenge unequal pay.“All workers in Maryland and across the United States deserve to be paid fairly for their work, and this commonsense measure represents welcome progress on that front,” said Center for American Progress Senior Fellow Jocelyn Frye in a statement. “These provisions will provide a critical protection to vulnerable communities, particularly transgender individuals who face significant wage disparities and workplace discrimination, and foster more understanding and openness in pay practices.”Despite advocacy effort at the federal, state and local level, the gender wage gap continues to be a pervasive problem in the United States, which activists say undermines the economic stability of women and their families.In Maryland, for example, men who work full-time positions on average earn about $8,604 more annually than women on average. Put another way: women in Maryland are paid 85 cents for every dollar paid to men, according to an analysis of U.S. Census Bureau data. Nationally, women are paid 79 cents for every dollar paid to men.Among women of color the inequity is even worse. Among Maryland women who hold full-time, year-round jobs, African-American women are paid 69 cents, Latinas are paid 47 cents and Asian women are paid 82 cents for every dollar paid to White men. Nationally, African-American women earning 60 cents for every dollar earned by White men and Native-American women and Latinas earning only 59 cents and 55 cents, respectively.“Equal pay is by no means just a women’s issue – it’s a family issue. It’s about parents who find themselves with less money for tuition or child care; couples who wind up with less to retire on; households where, when one breadwinner is paid less than she deserves, that’s the difference between affording the mortgage – or not; between keeping the heat on, or paying the doctor’s bills – or not,” said President Barack Obama at the signing of the Lilly Ledbetter Fair Pay Restoration Act. “In signing this bill today, I intend to send a clear message: That making our economy work means making sure it works for everyone. That there are no second class citizens in our workplaces, and that it’s not just unfair and illegal – but bad for business – to pay someone less because of their gender, age, race, ethnicity, religion or disability.”
PausePlay% buffered00:0000:00UnmuteMuteDisable captionsEnable captionsSettingsCaptionsDisabledQuality0SpeedNormalCaptionsGo back to previous menuQualityGo back to previous menuSpeedGo back to previous menu0.5×0.75×Normal1.25×1.5×1.75×2×Exit fullscreenEnter fullscreen Tailored chemistry links nanoparticles in stable monolayers Research groups from Westfälische Wilhelms-Universität in Münster led by Professors Harald Fuchs and Frank Glorius, used scanning-tunneling microscopy analyses combined with first principles calculations of representative NHC monolayers on gold surfaces to determine how the monolayers can be both chemically robust and highly mobile. They found that the NHC bound to gold forms an adatom that then traverses the gold surface in a ballbot-type motion. Their report appeared in a recent issue of Nature Chemistry.NHCs form a particularly strong bond with gold because of the sp2 hybridized lone pair of electrons on the carbon atom (See figure of NHCs above). Studies have shown that NHCs can be used to form particularly stable self-assembled monolayers (SAMs) on gold surfaces and can even be modified after formation of the monolayer, but these studies are difficult to compare with each other because they do not have similar R groups.The nitrogen-substituted R groups play a significant role in the behavior of the NHCs. Bulky R groups prohibit dimerization but may affect the stability of monolayer formation. Also because the nitrogen atoms are part of an aromatic ring, they serve as electron donors to the substituents. The type of substituent affects the electronics of the molecule.In this study, Wang et al. used three different NHCs that were synthesized in the Glorius group, each of which had R groups that had previously been studied and represented a range of steric and electronic properties. These groups include IMes which has 2,4,6 trimethyl phenyl rings as the N-substituents; IPr which has 2,6-diisopropylphenyl substituents; and IMe which just has methyl groups as the N-substituents. Play Credit: (c) Nature Chemistry (2016) doi:10.1038/nchem.2622 Beginning with carboxylate versions of IMes, IPr, and IMe, they deposited the NHCs onto the gold surfaces via ultrahigh vacuum vapor deposition. XPS confirmed that the NHC, not the carboxylate version, was bound to the gold surface. Scanning tunneling microscopy (STM) showed that IPr and IMe made neat, controlled surfaces, while IMes molecules were less ordered. Citation: Self-assembled monolayers of NHCs on gold have ballbot-type motion (2016, October 20) retrieved 18 August 2019 from https://phys.org/news/2016-10-self-assembled-monolayers-nhcs-gold-ballbot-type.html Journal information: Nature (Phys.org)—Self-assembled monolayers are molecules anchored to a surface. These molecules have been used to advance the fields of molecular sensors and electronics. Monolayers on gold surfaces are typically anchored by a thiol. One alternative to thiols are N-heterocyclic carbenes (NHCs). First isolated in 1991, NHCs have proved an important molecule for practical uses because it can serve as a ligand for transition metals as well as some main group elements. NHCs have also been used for organocatalysis, cross-coupling reactions, and pharmaceuticals. 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. Explore further © 2016 Phys.org , Nature Chemistry a, Schematic illustration of the procedure used to install NHCs on gold by physical vapour deposition. b, The investigated NHCs. c, The STM image (V = −2.2 V, I = 34 pA) shows IMes directly bonded to a Au(111) surface. d, The STM image (V = 2.73 V, I = 25 pA) of IPr on Au(111) shows a highly ordered and dense hexagonally packed full monolayer. Credit: (c) Nature Chemistry (2016) doi:10.1038/nchem.2622 At various surface coverage densities, the IPr surface would form islands that broke apart and recombined. This indicated that the surface was mobile, but there was no change to morphology of the gold surface. Despite this mobility, the bond between the NHC and the gold surface proved to be highly stable at high temperatures.This behavior may be explained by the formation of adatoms, or the interaction of one NHC molecule with one gold atom. This adatom then moves around the surface as one entity, which the authors liken to ballbot movement. They confirmed this structure by looking at the height of the IPr monolayers.DFT calculations helped to explain how exactly these adatoms formed and moved. IPr and IMe likely bound to a gold atom that was pulled from the surface. Simultaneously, a gold atom from the second layer moves into the vacant hole. The gold atom that was pulled from the surface was bound irreversibly to the NHC to form an adatom that then readily moved across the surface. Additional free energy calculations looked at the effects of bulky R groups, specifically comparing IPr with IMes. Wang et al. found that the pi interactions between the phenyl rings and the surface play a role in adatom formation and mobility. They reasoned that there is a balance between steric hindrance, as with IPr, and pi interactions, as displayed with IMes. And, indeed, the non-bulky IMe compound, which was more mobile than IPr and IMes, was able to form dimeric and trimeric complexes with one gold atom.This study provides important insights into how NHC-Au monolayers form and behave. They seem to form a stronger bond than thiols with gold, but they also display mobility that is influence by the identity of the nitrogen substituents. The NHCs that tend to have weaker pi interacts with the gold surface readily forming adatoms that then move across the surface like a ballbot. More information: Gaoqiang Wang et al, Ballbot-type motion of N-heterocyclic carbenes on gold surfaces, Nature Chemistry (2016). DOI: 10.1038/NCHEM.2622AbstractRecently, N-heterocyclic carbenes (NHCs) were introduced as alternative anchors for surface modifications and so offered many attractive features, which might render them superior to thiol-based systems. However, little effort has been made to investigate the self-organization process of NHCs on surfaces, an important aspect for the formation of self-assembled monolayers (SAMs), which requires molecular mobility. Based on investigations with scanning tunnelling microscopy and first-principles calculations, we provide an understanding of the microscopic mechanism behind the high mobility observed for NHCs. These NHCs extract a gold atom from the surface, which leads to the formation of an NHC–gold adatom complex that displays a high surface mobility by a ballbot-type motion. Together with their high desorption barrier this enables the formation of ordered and strongly bound SAMs. In addition, this mechanism allows a complementary surface-assisted synthesis of dimeric and hitherto unknown trimeric NHC gold complexes on the surface.
Go back to the e-newsletter Go back to the e-newsletterLooking for that amazing honeymoon getaway or just an excuse to reignite the flame with a loved one? The Berkeley River Lodge‘s ‘Romancing the Berkeley’ package allows couples to experience one of Australia’s most spectacular and beautiful retreats – complete with cruises along the Berkeley River exploring river gorges and swims in the crystal-clear pools of nearby waterfalls along with wilderness picnics.This all-inclusive package includes accommodation in a private Honeymoon Ocean View Villa, return scenic transfers daily from Kununurra and Darwin, His and Hers Romance Pack and a bottle of Veuve Clicquot champagne in villa on arrival, all gourmet meals and beverages, incredible tours including a stunning river cruise, coastal tours, treks and more.Couples will have something special to remember with an inclusive Sunset Helicopter excursion while watching the sun set over the Berkeley River as they feast on a gourmet wine and cheese platter.Opened in 2012, The Berkeley River Lodge is located in the heart of one of the last wilderness areas on Earth, located right in between the Timor Sea sunrise and Berkeley River sunset where the ultimate Kimberley adventure awaits. The unique and iconic venue offers the essential qualities of a remote location – only being accessible by air.The lodge is one of seven properties Australia-wide that is a member of the exclusive Small Luxury Hotels of the World.
Liberty Global-owned cable operator UPC Poland has extended its public WiFi network rollout to Krakow.UPC Poland previously launched public WiFi in the Baltic Sea resort of Sopot. The operator has rolled out a WiFi hotspot network based on the partitioning of residential WiFi routers.The network is free to all UPC subscribers who have signed up for broadband at 30Mbps or above.
Pay TV operator Canal+ has secured the African rights to key international and French football competitions for the next few seasons in a move that bolsters its pay TV offering in the French-speaking parts of the continent.Canal+ said it had now struck deals to acquire the African rights to the UEFA Champions League for three seasons from this year, along with rights to the FIFA World Cup in Russia later this year.Canal+ also has the rights to French Ligue 1 football for the next six seasons, along with Ligue 2 rights, the Coupe de la Ligue and the Trophée des Champions. African Canal+ subscribers will also be able to view the Coupe de France de Football tournament from 2018-22.In addition to non-African football, Canal+ also has the rights to the bi-annual Africa Cup of Nations, kicking off with the 2019 tournament in Cameroon.In addition to these recent acquisitions, Canal+ en Afrique also offers coverage of other national leagues such as the English Premier League and Spain’s La Liga.“We are delighted to strengthen the international and African football offering for our subscribers, this sport being one of the most popular programmes at the heart of our bouquets,” said Jacqued du Puy, president of Canal+ Overseas.“Canal+ today is incontestably the greatest sports arena in Africa, and the totality of these acquisitions allows us to offer to our viewrs a unique quality spectacle all year long.”In Africa, Canal+ offers four Canal+ Sport channels and the recently-launched A+ Sport channel.
Canal+ has secured the rights to English Premier League football in France for three seasons from next year and has renewed its existing contract for the Premier League in Poland.Winning back the Premier League, currently held by Altice’s RMC Sport, is a significant coup for the embattled pay TV broadcaster, which saw its grip on France’s top tier Ligue 1 rights removed by Spanish broadcaster Mediapro earlier this year when it outbid the pay TV operator to secure these from 2020. Canal+ also lost the UEFA Champions League and Europa League rights from this year to Altice.Canal+ said that winning back the rights “reflects the Group’s drive to invest in premium content over time and to offer an unparalleled football offering, primarily on its own channels”.The acquisition of Premier League rights means that in France, Canal+ will be able to offer a selction of French football games including the top three Ligue 1 games, the Premier league and Top14 French rugby, Formula 1, Moto GP, WRC, Golf and the 2020 Olympics.In Poland, the Premier League will join Polish national league Lotto Ekstraklasa, 50% of Spanish La Liga, selected German Bundesliga matches, NBA, the best speedway league in the world PGE Ekstraliga and Speedway Grand Prix, CEV Volleyball Champions League, EHF Champions League, Polish handball Superliga, Rugby Six Nations Cup, and PGA golfThe reversion of French Premier League rights to Canal+ is a blow for Altice and RMC Sport. SFR said it would work with Canal+, in “the spirit of” an existing agreement giving Canal+ access to Champions League, to provide RMC Sport subscribers access to the Premier League from next year. The operator was referring to an offer launched in September providing Canal+, BeIN Sports and RMC Sport to its subscribers for €40 a month.SFR said that RMC Sport remained “the most complete sports platform” but said that, in terms of exclusive rights, it would now focus on “premium events” like the Champions League.