Jiro Manio arrested for stabbing man in Marikina Carpio hits red carpet treatment for China Coast Guard PLAY LIST 02:14Carpio hits red carpet treatment for China Coast Guard02:56NCRPO pledges to donate P3.5 million to victims of Taal eruption00:56Heavy rain brings some relief in Australia02:37Calm moments allow Taal folks some respite03:23Negosyo sa Tagaytay City, bagsak sa pag-aalboroto ng Bulkang Taal01:13Christian Standhardinger wins PBA Best Player award LATEST STORIES Brian Heruela arrival bolsters Phoenix backcourt, defense MOST READ Salvador seizes early lead at Eagle ridge Steam emission over Taal’s main crater ‘steady’ for past 24 hours Don’t miss out on the latest news and information. Meralco ‘never the same’ after Almazan injury in PBA Finals Lights inside SMX hall flicker as Duterte rants vs Ayala, Pangilinan anew Scottie Thompson also worthy of Finals MVP, thinks Cone “I’d rather wait when the 30 days are over,” Marcial told sportswriters on Wednesday during the first Philippine Sportswriters Association (PSA) Forum for the year at Tapa King-Farmers Market in Cubao.“I don’t know whether it (PBA commissioner) will be given to me. What are their expectations (from me), and also my expectations from them. That’s why I can’t say anything.”FEATURED STORIESSPORTSTim Cone, Ginebra set their sights on elusive All-Filipino crownSPORTSGinebra beats Meralco again to capture PBA Governors’ Cup titleSPORTSAfter winning title, time for LA Tenorio to give back to Batangas folkMarcial was appointed OIC after the resignation of former Commissioner Chito Narvasa became effective at the start of the year. OSG plea to revoke ABS-CBN franchise ’a duplicitous move’ – Lacson OSG plea to revoke ABS-CBN franchise ’a duplicitous move’ – Lacson Willie MarcialWillie Marcial said he would wait for his appointment as PBA officer-in-charge to lapse before making plans amid reports that several parties were pushing for him to be formally named league commissioner.Marcial was given 30 days as league caretaker and has already put in place noteworthy projects that the league could pursue if it awards him a tenured post as commissioner.ADVERTISEMENT Redemption is sweet for Ginebra, Scottie Thompson View comments Sports Related Videospowered by AdSparcRead Next
Facebook Twitter Google+LinkedInPinterestWhatsApp Facebook Twitter Google+LinkedInPinterestWhatsAppUnited States, July 20, 2017 – Miami, FL – Caribbean viewers will have a front row seat to watch the best young athletes from the across the Commonwealth in action at the 2017 Commonwealth Youth Games, as Flow Sports, the Home of Sports in the Caribbean, airs 8 hours of live coverage each day, from July 19 to 23rd.The largest-ever edition of the Commonwealth Youth Games will be hosted this year in The Bahamas and presented by the Bahamas Telecommunications Company (BTC).Flow Sports will once again deliver anytime, anywhere access so ‘on-the-go’ viewers can have the option of watching the coverage on the Flow Sports App or via the website, www.flowsports.co.According to Sean Riley, Managing Director of Flow Sports, “We are pleased to announce that Flow Sports has worldwide distribution rights to broadcast the Commonwealth Youth Games. We are truly proud of this development as it gives our talented young regional athletes significantly more exposure while allowing their families, friends and fans the opportunity to see them in action as they compete on the world stage. This will no doubt delight Caribbean people in the diaspora who wish to catch up on the action of our up and coming star athletes.” As with the highly successful coverage of the 2017 Flow CARIFTA Games in Curacao this past Easter, the Flow Sports team of well-known Caribbean sports media personalities will cover a variety of disciplines such as aquatics, boxing, beach volleyball, beach soccer and judo, anchored in the highly anticipated track-and-field events.The Commonwealth Youth Games is the largest sporting competition to ever take place in The Bahamas and at the official press conference to announce the Games, BTC Interim CEO Dexter Cartwright said, “Today is a very special day for BTC, our sister company Flow Sports l, as we open our arms here in The Bahamas to welcome hundreds of young athletes from almost 70 countries. Continuing our mission to invest heavily in sports, we are proud to officially announce our $250,000 investment in the sixth edition of the Commonwealth Youth Games – and we’re confident it’s going to be the best yet. Good luck to all the competitors!”For a full listing of the daily times for live event broadcasts, please visit the Flow Sports website at www.flowsports.co/tv-guide/.This is the first time the event has been held in the Caribbean in over 50 years – the last being the 1966 Commonwealth Games in Kingston, Jamaica.Press Release: FLOW Related Items:
Aston Martin Aston Martin’s DBX SUV throws snow all over the place More From Roadshow 2020 Hyundai Palisade review: Posh enough to make Genesis jealous Now playing: Watch this: Preview • 2019 Aston Martin DB11 Volante: A good reason for sunburn 2020 BMW M340i review: A dash of M makes everything better Share your voice 10 Photos This December, Aston Martin will welcome its first SUV into the world known as the DBX. The British luxury brand delivered the news in a teaser video (embedded above) for the DBX SUV on Monday without providing a more specific date. Previously, we knew the luxury SUV was coming in the final quarter of this year, but Aston Martin is going to wait until the very last month to unveil its SUV. Not only that, but the brand wants us to know that just because this is an SUV, it doesn’t mean it’s not a true part of the DB family. The designation dates back decades and sits as a prefix to some of the most iconic Aston Martin models.This teaser focuses specifically on the grille, which takes a familiar shape from the DB line of cars. Today, that encompasses the DBS Superleggera and DB11. As is all too familiar a story, people dig utility vehicles these days, which has led to an insurgence of ultraluxurious SUVs. The Rolls-Royce Cullinan, Bentley Bentayga, Lamborghini Urus and more have recently cropped up. The DBX will do its best to capture the same market, though more than likely, owners will park it next to another Aston Martin in the garage.Aside from the small shot of the grille, we do get a rough look at the headlights and daytime-running lights as the teaser closes. However, prototype photos already give us a good idea as to what the SUV will look like when we see it later this year. The biggest mystery remains the rear end, which we don’t see at all in the teaser. Even in the previously released prototype photos (see the gallery below), the DBX’s back end was pretty well camouflaged. Do expect a Vantage-esque look with the taillights.While the original idea was to make the DBX an electric vehicle, Aston Martin scrapped that plan as the Lagonda came back into the picture. As for powertrains, it’ll likely stick to V8 and V12 engines, but we’ll know for sure in a few months. The Rapide AMR has the last-ever naturally aspirated… 2020 Hyundai Sonata first drive: An attractive and compelling midsize sedan Post a comment More about 2019 Aston Martin DB11 Volante 4:39 Tags 0 SUVs Luxury cars Aston Martin
Bradley Cooper (R) and his partner Russian model Irina ShaykGetty imagesBradley Cooper and Irina Shayk have been in a committed relationship from a very long time but as per a recent claim, things are not going too well between them. Fans are now speculating if Lady Gaga is reportedly the reason behind the ongoing friction between the couple or is there something else going on between Cooper and Shayk.As per a recent claim by PageSix, the 44-year-old Bradley Cooper and his longtime girlfriend Irina Shayk are reportedly doing their best to make everything work for the sake of their daughter, Lea De Seine. However, their long-time relationship is “hanging by a thread.”Bradley Cooper and Lady Gaga shared the screen space in the Academy Award-nominee movie, A Star Is Born. Ever since then, fans are rooting for them to become a couple in real life as well.Things started to go south after Bradley Cooper and his A Star Is Born co-star Lady Gaga performed a highly intimate duet at the 91st Academy Awards. During the Oscars, Gaga and Cooper amazed everyone by singing “Shallow” and several reports surfaced around that time suggesting that there is something going on between these two. Lady Gaga, however, has already debunked these absurd claims and stated that they are actors and they were merely acting on the stage.That being said, another insider previously revealed to PageSix that Bradley Cooper and Irina Shayk are reportedly miserable together as the acclaimed actor does not drink but his long-time partner wishes to go out. Lady Gaga and Bradley Cooper in A Star is BornLady Gaga (@ladygaga/Instagram)”They were not looking happy … They barely spoke to each other at the start of the meal,” another source revealed. “They couldn’t break up when he was doing promotion for ‘A Star Is Born,’ but who knows what will happen now?”Bradley Cooper and Irina Shayk began dating in 2015. Apparently, this is not for the first time when such bogus reports have surfaced online. But the couple has remained strong than ever. Even Lady Gaga has made it clear that she is a very good friend of Bradley and nothing is going on between both of them. It should be noted that Bradley Cooper and Lady Gaga are not dating, and he is still in a very loving relationship with Irina Shayk, despite the claims.
© 2015 Phys.org Citation: Synthesis and characterization of an important intermediate for biocatalysts (2015, March 19) retrieved 18 August 2019 from https://phys.org/news/2015-03-synthesis-characterization-important-intermediate-biocatalysts.html Cytochrome P450 Oxidase (CYP2C9). Credit: Wikipedia/CC BY-SA 3.0 (Phys.org)—Cytochrome P450 (CYP) is sometimes referred to as the “Rosetta Stone” of iron-containing oxygenases, because of its ubiquity as a biocatalyst for various reactions, including drug metabolism and synthesis of biological molecules. Importantly, CYP catalyzes carbon-hydrogen hydroxylation reactions, cleaving some of the most difficult carbon-hydrogen bonding structures. While CYP is well studied, scientists are eager to understand the ferryl intermediates formed during hydroxylation in an effort to fine-tune catalytic reactions as well as seek out other biocatalysts to react with carbon-hydrogen bonds that are typically unreactive. Apolipoprotein(a): A natural regulator of inflammation More information: “Heme-thiolate ferryl of aromatic peroxygenase is basic and reactive” Xiaoshi Wang, Rene Ullrich, Marticn Hofrichter, and John T. Groves, www.pnas.org/cgi/doi/10.1073/pnas.1503340112AbstractA kinetic and spectroscopic characterization of the ferryl intermediate (APO-II) from APO, the heme-thiolate peroxygenase from Agrocybe aegerita, is described. APO-II was generated by reaction of the ferric enzyme with metachloroperoxybenzoic acid in the presence of nitroxyl radicals and detected with the use of rapid-mixing stopped-flow UV-visible (UV-vis) spectroscopy. The nitroxyl radicals served as selective reductants of APO-I, reacting only slowly with APO-II. APO-II displayed a split Soret UV-vis spectrum (370 nm and 428 nm) characteristic of thiolate ligation. Rapid-mixing, pH-jump spectrophotometry revealed a basic pKa of 10.0 for the FeIV−O−H of APO-II, indicating that APO-II is protonated under typical turnover conditions. Kinetic characterization showed that APO-II is unusually reactive toward a panel of benzylic C−H and phenolic substrates, with second-order rate constants for C−H and O−H bond scission in the range of 10–107 M−1⋅s−1. Our results demonstrate the important role of the axial cysteine ligand in increasing the proton affinity of the ferryl oxygen of APO intermediates, thus providing additional driving force for C−H and O−H bond scission. 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. Researchers have recently found that aromatic peroxygenases (APO), a fungus-based heme thiolate protein, can catalyze the oxygenation of aliphatic and aromatic hydrocarbons. Based on the products from these reactions, APO seems to behave similarly to CYP, although it apparently is more stable over a larger range of pH. This provides an opportunity to study the hydroxylation reaction mechanism of an analogous molecule to CYP that could serve as another potential biocatalyst. Xiaoshi Wang and John T. Groves from the Department of Chemistry at Princeton University report the isolation and characterization of APO-II, an important intermediate in hydroxylation, in the Proceedings of the National Academy of Sciences.Previous work by Groves’ group has shown that APO, derived from Agrocybe aegerita forms an oxoiron (IV) porphyrin radical cation (APO-I) that can be detected by UV-visible spectroscopy. The current work, isolates APO-II, a reduced form of APO-I. APO has an OH2 group coordinated to the central iron atom. Oxidation, using mCPBA yields an oxidized, Fe=O, interaction. Wang and Groves sought to isolate APO-II, which has an OH group coordinated to iron, via a one electron reduction reaction.Wang and Groves began by oxidizing APO using mCPBA, and then determined that the reduction of APO-I using a nitroxyl radical would provide APO-II. They tested their nitroxyl radical candidates using a model system, ensuring that they would get complete conversion from the oxidized to the reduced intermediate, and landed on 3-carboxy-PROXYL as the best reducing agent.UV-visible spectroscopy confirmed that they made APO-II using a single-mixing stopped flow experiment. They were also able to confirm that APO-II was formed via the direct reduction of APO-I using a double-mixing step. Kinetic studies indicated that APO-II remained in solution for 0.5 seconds and has an approximate decay rate of 1 sec-1, making it an intermediate that is stable enough to allow for further study.Because APO is stable at a wide range of pH values, pH 7.0 to pH 12, Wang and Groves were able to determine the pKa value of the proton on the hydroxyl group of APO-II using titration with buffer solutions and characterization with UV-visible spectroscopy. They found that the pKa for the hydroxyl proton was approximately 10, indicating that the molecule was protonated at a pH below 10. They also determined that the sulfur remained bound to the iron upon deprotonation at high pH.Finally, Wang and Groves investigated the reactivity of various substrates in an APO-II catalyzed hydroxylation reaction. They found that APO-II has a surprisingly high reactivity toward phenols and substrates with relatively weak benzylic carbon-hydrogen bonds. The high reactivity with phenols was unexpected because analogous peroxidases typically do not react as quickly. Additionally, according to the kinetic data, APO-II seems to be a milder oxidant compared to APO-I, which was expected based on other systems.This research provides insight into CYP-like reactivity by investigating a key intermediate in the hydroxylation reaction. According to Dr. Groves, “The surprisingly high reactivity of APO-II toward weak C-H bonds may facilitate the development of more selective biocatalysts.” Journal information: Proceedings of the National Academy of Sciences Explore further
Kolkata: Congratulating Prime Minister Narendra Modi a day before the swearing-in ceremony which is scheduled to be held on Thursday, Chief Minister Mamata Banerjee has requested the former to excuse her for not attending the function.Earlier, Banerjee had decided to attend the function in Delhi and was scheduled to leave for the national Capital on Wednesday afternoon. Meanwhile, the Bengal BJP has decided to take the members of 54 people whom they termed as “martyrs” to attend the swearing-in ceremony. Also Read – Rs 13,000 crore investment to provide 2 lakh jobs: MamataReacting sharply, Banerjee said the BJP’s claim that 54 people died in political violence is “completely untrue.” There have been no political murders in Bengal and the persons might have died due to family feud or personal enmity or other disputes. She remarked that the swearing-in ceremony is “an august occasion to celebrate democracy” and should not be devalued by any political party that wants to use it as an opportunity “to score political points.” Also Read – Lightning kills 8, injures 16 in stateShortly after cancelling the trip to Delhi, she tweeted: “Congratulations, new Prime Minister Narendra Modi ji. It was my plan to accept the “Constitutional Invitation” and attend the oath-taking ceremony. However, in the last one hour, I am seeing media reports that the BJP are claiming 54 people have been murdered in political violence in Bengal. This is completely untrue. There have been no political murders in Bengal. These deaths may have occurred due to personal enmity, family quarrels and other disputes, nothing related to politics. There is no such record with us. So I am sorry Narendra Modi ji, this has compelled me not to attend the ceremony.” She further mentioned: “The ceremony is an august occasion to celebrate democracy, not one that should be devalued by any political party which uses it as an opportunity to score political points. Please excuse me.” Political experts felt that as the administrative head of the state, Banerjee has taken the right decision. It is an insult to her to share the same dais with the family members of the deceased as to accept it will mean a stamp on BJP’s tall claims. The saffron party claims that 46 party workers had died during the Panchayats election held in 2018 and five during the recently-concluded Lok Sabha election.