control Controllable tertiary amine-promoted photoactivation metal-free carbonylation of aryl sulfonium salts to aryl carboxylic acid derivatives By pubs.rsc.org Published On :: Green Chem., 2024, Advance ArticleDOI: 10.1039/D4GC04502E, Paper Open Access   This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.Jiajun Zhang, Le-Cheng Wang, Yuanrui Wang, Xiao-Feng WuThis paper describes a new method for the activation of aryl radicals via EDA complexes without metals and photosensitizers for carbonylation with various nucleophilic reagents under visible light.To cite this article before page numbers are assigned, use the DOI form of citation above.The content of this RSS Feed (c) The Royal Society of Chemistry Full Article
control Substrate-controlled regioselective hydrophosphorylation of allenes to enable photocatalytic synthesis of alkenylphosphoryl compounds By pubs.rsc.org Published On :: Green Chem., 2024, 26,11272-11279DOI: 10.1039/D4GC03588G, PaperTian-Ming Yang, Xin-Lu Fan, Wei Shi, Xuefei Zhao, Xu-Hong HuA visible-light-induced hydrophosphorylation of allenes with H-phosphine oxides is demonstrated to give a diverse range of alkenylphosphoryl compounds in a highly stereoselective and regioselective manner.The content of this RSS Feed (c) The Royal Society of Chemistry Full Article
control Shreyas Iyer, Siddhesh Lad smash centuries while 20-year old Angkrish impresses as Mumbai take control against Odisha in Ranji Trophy By indianexpress.com Published On :: Wed, 06 Nov 2024 14:47:10 +0000 Full Article Cricket Sports
control ‘We don’t control the wickets in Australia; it’s their wish, whatever they want to dish out’ – Coach Gambhir By indianexpress.com Published On :: Mon, 11 Nov 2024 07:49:45 +0000 Full Article Cricket Sports
control Thai Super Energy to pick controlling stake in Vietnamese assets for $457m By www.dealstreetasia.com Published On :: Mon, 06 Apr 2020 11:03:16 +0000 The Thai firm expects to generate IRRs of around 17% from these projects over a period of 20 years. The post Thai Super Energy to pick controlling stake in Vietnamese assets for $457m appeared first on DealStreetAsia. Full Article electricity of vietnam Super Energy Corporation
control Controllable structure reconstruction of nickel–iron compounds toward highly efficient oxygen evolution By feeds.rsc.org Published On :: Nanoscale, 2020, Advance ArticleDOI: 10.1039/D0NR02254C, PaperAzhar Mahmood, Qiangmin Yu, Yuting Luo, Zhiyuan Zhang, Chi Zhang, Ling Qiu, Bilu LiuStructure optimized Ni0.8Fe0.2-LDH catalyst and corresponding OER performance.To cite this article before page numbers are assigned, use the DOI form of citation above.The content of this RSS Feed (c) The Royal Society of Chemistry Full Article
control This Guy Has the Best Ball Control Ever By feedproxy.google.com Published On :: Thu, 01 Aug 2013 13:00:00 -0700 Full Article sports soccer funny Video g rated win
control Cell-specific expression of the transcriptional regulator RHAMM provides a timing mechanism that controls appropriate wound re-epithelialization [Glycobiology and Extracellular Matrices] By feedproxy.google.com Published On :: 2020-04-17T00:06:05-07:00 Prevention of aberrant cutaneous wound repair and appropriate regeneration of an intact and functional integument require the coordinated timing of fibroblast and keratinocyte migration. Here, we identified a mechanism whereby opposing cell-specific motogenic functions of a multifunctional intracellular and extracellular protein, the receptor for hyaluronan-mediated motility (RHAMM), coordinates fibroblast and keratinocyte migration speed and ensures appropriate timing of excisional wound closure. We found that, unlike in WT mice, in Rhamm-null mice, keratinocyte migration initiates prematurely in the excisional wounds, resulting in wounds that have re-surfaced before the formation of normal granulation tissue, leading to a defective epidermal architecture. We also noted aberrant keratinocyte and fibroblast migration in the Rhamm-null mice, indicating that RHAMM suppresses keratinocyte motility but increases fibroblast motility. This cell context–dependent effect resulted from cell-specific regulation of extracellular signal-regulated kinase 1/2 (ERK1/2) activation and expression of a RHAMM target gene encoding matrix metalloprotease 9 (MMP-9). In fibroblasts, RHAMM promoted ERK1/2 activation and MMP-9 expression, whereas in keratinocytes, RHAMM suppressed these activities. In keratinocytes, loss of RHAMM function or expression promoted epidermal growth factor receptor–regulated MMP-9 expression via ERK1/2, which resulted in cleavage of the ectodomain of the RHAMM partner protein CD44 and thereby increased keratinocyte motility. These results identify RHAMM as a key factor that integrates the timing of wound repair by controlling cell migration. Full Article
control Genetically engineered 'Magneto' protein remotely controls brain and behaviour By www.theguardian.com Published On :: 2016-03-24T14:30:03Z “Badass” new method uses a magnetised protein to activate brain cells rapidly, reversibly, and non-invasivelyResearchers in the United States have developed a new method for controlling the brain circuits associated with complex animal behaviours, using genetic engineering to create a magnetised protein that activates specific groups of nerve cells from a distance.Understanding how the brain generates behaviour is one of the ultimate goals of neuroscience – and one of its most difficult questions. In recent years, researchers have developed a number of methods that enable them to remotely control specified groups of neurons and to probe the workings of neuronal circuits. Related: Remote control of brain activity with heated nanoparticles Related: Researchers read and write brain activity with light Continue reading... Full Article Science Neuroscience
control Nerve terminal nanofilaments control brain signalling By www.theguardian.com Published On :: 2016-04-02T13:25:02Z State-of-the-art electron microscopy reveals the large-scale organization of the proteins that regulate neurotransmitter release This spectacular image – which took the best part of a year to create – shows the fine structure of a nerve terminal at high resolution, revealing, for the very first time, an intricate network of fine filaments that controls the movements of synaptic vesicles.The brain is soft and wet, with the consistency of a lump of jelly. Yet, it is the most complex and highly organized structure that we know of, containing hundreds of billions of neurons and glial cells, and something on the order of one quadrillion synaptic connections, all of which are arranged in a very specific manner. Related: 3D model of a nerve terminal in atomic detail | Mo Costandi Related: Blowing up the brain to reveal its finer details Continue reading... Full Article Science Neuroscience
control [ Elections ] Open Question : See why Boris Johnson will tell public to ‘stay alert, control the virus and save lives’ ? By answers.yahoo.com Published On :: Sun, 10 May 2020 09:08:14 +0000 https://diazhub.com/news/boris-johnson-will-tell-public-to-stay-alert-control-the-virus-and-save-lives/ Full Article
control Singapore: COVID-19 Control Orders Extended to June 1 By www.loc.gov Published On :: Thu, 07 May 2020 19:32:08 +0000 (May 7, 2020) On April 30, 2020, Singapore’s minister for health made an amendment to the COVID‑19 (Temporary Measures) (Control Order) Regulations 2020 to extend the expiration date of the COVID-19 control orders under the regulations to June 1, 2020. The Control Order Regulations, which had been originally issued on April 7, 2020, under the authorization […] Full Article
control After flip-flops, IndiGo clarifies pay cut for senior employees will be for entire 2020-21 – Moneycontrol By rss-newsfeed.india-meets-classic.net Published On :: Sun, 10 May 2020 07:58:28 +0000 After flip-flops, IndiGo clarifies pay cut for senior employees will be for entire 2020-21 MoneycontrolCovid-19: IndiGo's senior employees to face pay cut up to 25% for entire FY21 LivemintAfter Flip-Flops, IndiGo Announces Pay Cu... Full Article IMC News Feed
control Investors may need to take control of Zee Learn from promoters: IiAS By www.financialexpress.com Published On :: 2020-05-05T01:30:00+05:30 A proxy advisory firm has raised objections to the corporate governance structure at Zee Learn, part of the Essel group, expressing concerns over the company’s capital allocation decision, related-party transactions and acquisition of MT Educare. Full Article Industry
control Hackers Build A Skype That's Not Controlled By Microsoft By packetstormsecurity.com Published On :: Tue, 02 Sep 2014 06:15:57 GMT Full Article headline hacker microsoft skype
control Using ShoutBoxes To Control Malicious Software By packetstormsecurity.com Published On :: Tue, 14 Apr 2009 23:17:50 GMT Whitepaper called Using "ShoutBoxes" to control malicious software. Full Article
control Windows NT/2K/XP/2K3/VISTA/2K8/7 NtVdmControl()- By packetstormsecurity.com Published On :: Thu, 21 Jan 2010 00:12:04 GMT Microsoft Windows NT/2K/XP/2K3/VISTA/2K8/7 NtVdmControl()->KiTrap0d local ring0 exploit. Google flags this as malware so only use this if you know what you are doing. The password to unarchive this zip is the word "infected". Full Article
control Disease Control Bill: Some people are working on voodoo theory — Rep Igbakpa By www.vanguardngr.com Published On :: Sun, 10 May 2020 07:58:07 +0000 Ben Igbakpa, a member of the House of Representatives, representing Ethiope East and Ethiope West Federal Constituency of Delta State, in this interview, speaks on the intendment of the controversial Infectious Disease Control Bill, saying sponsors mean well for Nigeria. The post Disease Control Bill: Some people are working on voodoo theory — Rep Igbakpa appeared first on Vanguard News. Full Article News Disease Control Bil Rep Igbakpa
control Australian Children to Gradually Return to School As COVID-19 Controls Ease By www.voanews.com Published On :: Sun, 10 May 2020 04:12:08 -0400 Parents frustrated at mixed COVID-19 school messages Full Article
control SHC directs food secretary to appoint district food controllers within a month By feedproxy.google.com Published On :: Sun, 10 May 2020 06:00:00 +0500 The Sindh High Court on Friday directed the food secretary to appoint the district food controllers within a month in accordance with the law.The direction came on a petition of Ali Ashgar who impugned the appointments of assistant food controllers to look after the work of district food... Full Article
control Trump Wants to Let Your Boss Take Away Your Birth Control By www.motherjones.com Published On :: Wed, 31 May 2017 18:14:09 +0000 The Trump administration is considering a broad exemption to Obamacare's mandate on contraceptive coverage, according to a leaked draft of the proposed rule published by Vox on Wednesday. Since 2011, the Obamacare provision has required that most employers provide insurance that covers birth control, without any cost to the patient. The rule has been the target of a number of lawsuits by religious employers who felt that the requirement violated their religious beliefs. Showing sensitivity to such concerns, in 2014 the Supreme Court ruled in Burwell v. Hobby Lobby that some religious employers could opt out of the coverage. But the court required them to file paperwork indicating their objection, in turn triggering separate contraceptive coverage for employees provided directly by the insurance company. That ruling, though, didn't settle the issue for religious groups. In a follow-up 2016 Supreme Court case, Zubik v. Burwell, a number of religious organizations said that even this accommodation required them to violate their beliefs, as the paperwork made them complicit in providing birth control coverage. The Supreme Court sent the case down to the lower courts, where it has still not been resolved. Now, the Trump administration seems ready to extend the birth control exemption beyond just religious employers. According to the leaked draft, dated May 23, the new rule would allow virtually any organization to opt out of the mandate if they feel contraception coverage violates "their religious beliefs and moral convictions." "This rule would mean women across the country could be denied insurance coverage for birth control on a whim from their employer or university," said Dana Singiser, vice president for public policy and government relations of Planned Parenthood Federation of America, in a statement. "It would expand the Supreme Court’s Hobby Lobby ruling to allow any employer—including huge, publicly traded companies—to deny birth control coverage to their employees. Think about it: Under this rule, bosses will be able to impose their personal beliefs on their female employees' private medical decisions." What's more, this draft doesn't require employers opting out of the mandate to notify the government they are doing so; they're only required to notify employees of a change in their insurance plans. Insurance companies could also themselves refuse to cover contraception if it violates their religious or moral beliefs. This appears to provide an even broader exemption than what team Trump has previously signaled it would enact. Throughout the campaign, Trump assured religious leaders their organizations would not have to comply with the contraception mandate: "I will make absolutely certain religious orders like the Little Sisters of the Poor are not bullied by the federal government because of their religious beliefs," he wrote in a letter to Catholic leaders last year, referring to the order of nuns that were party to the Zubik Supreme Court case. And on May 4, Trump, flanked by the Little Sisters of the Poor, signed an executive order about religious liberty, which encourages several agencies to address religious employers' objections to Obamacare's preventive care requirements, including contraception. It is unclear what changes may have been made to this draft since May 23, but what is clear is that the rule is in an advanced stage of the process; the Office of Management and Budget announced that it is currently reviewing it, the penultimate step before the rule is enacted via posting in the Federal Register. You can read the full draft, obtained by Vox, below: Preventive Services Final Rule (PDF) Preventive Services Final Rule (Text) Full Article Politics Reproductive Rights
control Trump WH: Birth Control Mandate Is Unnecessary Because of Planned Parenthood, Which We’ll Also Defund By www.motherjones.com Published On :: Thu, 01 Jun 2017 21:13:41 +0000 The Trump administration's argument for letting lots of employers opt out of covering birth control is…not exactly bulletproof. Yesterday, Vox reported that the Trump administration is considering a broad exemption to Obamacare's mandate on contraceptive coverage, according to a leaked draft of the proposed rule. If passed, the rule would allow virtually any employer, not just a religious one, to remove birth control coverage from its insurance plan if contraception violates the organization's religious beliefs or "moral convictions"—a broad and murky standard. But, in a curious twist, part of the Trump administration's justification for the move hinges on the existence of hundreds of Planned Parenthood clinics, many of which the White House is actively trying to close by "defunding" Planned Parenthood. As the draft text explains, the administration believes the past rationale for Obamacare's contraception mandate is insufficient. The document lists several reasons why this is the case. Here's one of them: "There are multiple Federal, state, and local programs that provide free or subsidized contraceptives for low-income women, including Medicaid (with a 90% Federal match for family planning services), Title X, health center grants, and Temporary Assistance for Needy Families. According to the Guttmacher Institute, government-subsidized family planning services are provided at 8,409 health centers overall. Various state programs supplement Federal programs, and 28 states have their own mandates of contraceptive coverage as a matter of state law. For example, the Title X program, administered by the HHS Office of Population Affairs (OPA), provides voluntary family planning information and services for clients based on their ability to pay. ... "The availability of such programs to serve the most at-risk women identified by IOM [Institute of Medicine, now known as the National Academy of Medicine] diminishes the Government's interest in applying the Mandate to objecting employers." The implication here is that since there are already programs like Medicaid and Title X to help low-income women afford contraception, the requirement that most employers provide no-cost birth control is less pressing. But there are a couple of glaring contradictions here: First of all, of the 8,409 health centers that provide Medicaid and Title X family planning services, as cited in the rule, 817 of them are run by Planned Parenthood—the very group that Congress and the administration are trying to exclude from using Title X and Medicaid funds to provide health care. Trump has already signed a bill into law allowing states to exclude Planned Parenthood and other providers who offer abortions from receiving Title X family planning funding—never mind that Title X funding is used exclusively for nonabortion services. Beyond that, there are several more proposals moving through government—including in the House's American Health Care Act and in the Trump budget proposal—to withhold Medicaid and other federal dollars, including Title X, specifically from Planned Parenthood. The problem with the White House's logic boils down to this: As the nation's largest provider of federal Title X-funded care, in 2015 Planned Parenthood centers served more than 40 percent of women nationwide using Title X-funded family planning care—a whopping 1.58 million patients. But if Planned Parenthood can no longer receive a single federal dollar to provide contraception and other family planning care—an oft-repeated goal of the Trump administration—then these nearly 1.6 million low-income patients will suddenly lose their family planning care. And now their employers may not cover that care either. Full Article Politics Reproductive Rights
control PM to unveil Covid-19 alert system with new message to ‘control the virus’ By www.itv.com Published On :: Sat, 09 May 2020 23:16:23 +0100 On Monday, the Government will publish a 50-page document outlining the full plan to cautiously re-start the economy to MPs. Full Article
control Control your thoughts By feedproxy.google.com Published On :: Most of our thoughts are negatives ones and no wonder why. When thoughts are negative in nature (thoughts of worry, anxiety, stress, lack, resentment, guilt etc) they produce resistance to the movement of your life, and this resistance is... Full Article
control GST: States Adamant On Sole Control Over Small Businesses By feedproxy.google.com Published On :: With states and Centre set to meet this week to chalk out jurisdiction over assessees under goods and services tax (GST). Full Article
control Regulatory Transparency in Multilateral Agreements Controlling Exports of Tropical Timber, E-Waste and Conflict Diamonds By www.oecd-ilibrary.org Published On :: Tue, 11 Dec 2012 09:50:00 GMT This paper examines how three multilateral environmental agreements (MEAs) incorporate transparency into their regulatory regimes: CITES (endangered species, especially tropical timber), the Basel Convention (hazardous e-waste), and the Kimberley Process (conflict diamonds) Full Article
control The OECD Control System for waste recovery By www.oecd.org Published On :: Tue, 05 Feb 2019 17:17:00 GMT An update of the OECD database on transboundary movements of wastes is now available for download. Since 1992, transboundary movements of recyclable wastes between OECD countries are regulated by the Council Decision C(2001)107, which was established by the OECD Council, and designed as an agreement under Article 11 of the Basel Convention. Full Article
control After flip-flops, IndiGo clarifies pay cut for senior employees will be for entire 2020-21 - Moneycontrol By news.google.com Published On :: Sun, 10 May 2020 07:38:23 GMT After flip-flops, IndiGo clarifies pay cut for senior employees will be for entire 2020-21 MoneycontrolCovid-19: IndiGo's senior employees to face pay cut up to 25% for entire FY21 LivemintAfter Flip-Flops, IndiGo Announces Pay Cut For Senior Employees For Entire 2020-21 NDTV ProfitIndiGos pay cuts for senior employees to remain effective through FY21 Business StandardIndiGo To Cut Pay And Send Some Staff On Unpaid Leave Simple FlyingView Full coverage on Google News Full Article
control China flexes its military muscle: Beijing exploits Covid crisis to assert control of South China Sea By Published On :: Sun, 10 May 2020 00:51:58 +0100 Deeply worried about Beijing's insatiable desire for land and the way its military has occupied areas by stealth, Washington has sent three warships to the region. Full Article
control Boris Johnson will tell public to 'stay alert, control the virus and save lives' By Published On :: Sun, 10 May 2020 08:25:51 +0100 Boris Johnson is expected to drop the 'stay at home' slogan during a televised address to Britain on Sunday at 7pm in an effort to reopen parts of the economy damaged during the coronavirus crisis. Full Article
control Boris Johnson will tell public to 'stay alert, control the virus and save lives' By www.dailymail.co.uk Published On :: Sun, 10 May 2020 07:45:58 GMT Boris Johnson is expected to drop the 'stay at home' slogan during a televised address to Britain on Sunday at 7pm in an effort to reopen parts of the economy damaged during the coronavirus crisis. Full Article
control Facebook's Sheryl Sandberg responds to 'control freak' claims By www.dailymail.co.uk Published On :: Thu, 27 Feb 2020 16:03:24 GMT Sheryl Sandberg, who is Facebook's chief operating officer, has defended herself against claims she is a control freak obsessed with her public image. Full Article
control China flexes its military muscle: Beijing exploits Covid crisis to assert control of South China Sea By www.dailymail.co.uk Published On :: Sat, 09 May 2020 23:51:58 GMT Deeply worried about Beijing's insatiable desire for land and the way its military has occupied areas by stealth, Washington has sent three warships to the region. Full Article
control The people's airwaves, but controlled By indiatogether.org Published On :: Sun, 26 Aug 2012 00:00:00 +0000 Seventeen years after the Supreme Court ruled that the government cannot restrict content on radio, it remains impossible for independent news to be aired on radio channels. Navya P K reports. Full Article
control Vizag gas leak situation under control: TDP MLA By www.newkerala.com Published On :: Sat, 09 May 2020 12:12:02 +0530 Full Article
control Situation at Vizag plant under control: LG Polymers By www.newkerala.com Published On :: Sat, 09 May 2020 17:22:01 +0530 Full Article
control Delhi's UP Bhawan Control Room gets over 2,000 calls every day By www.newkerala.com Published On :: Sun, 10 May 2020 04:18:02 +0530 Full Article
control Now, automatic water-level control system mandatory By www.thehindu.com Published On :: Sat, 09 May 2020 21:12:25 +0530 Amendments to the Bangalore Water Supply Sewerage Act, 1964, have made installation of automatic water level control system and provision of internal Full Article Bengaluru
control Punjab CM forms 13-member control room to coordinate wheat harvesting By www.newkerala.com Published On :: Wed, 08 Apr 2020 02:52:01 +0530 Full Article
control Punjab govt sets up control room for wheat harvesting season By www.newkerala.com Published On :: Wed, 08 Apr 2020 04:52:01 +0530 Full Article
control Coherent Bragg imaging of 60 nm Au nanoparticles under electrochemical control at the NanoMAX beamline By scripts.iucr.org Published On :: 2019-08-27 Nanoparticles are essential electrocatalysts in chemical production, water treatment and energy conversion, but engineering efficient and specific catalysts requires understanding complex structure–reactivity relations. Recent experiments have shown that Bragg coherent diffraction imaging might be a powerful tool in this regard. The technique provides three-dimensional lattice strain fields from which surface reactivity maps can be inferred. However, all experiments published so far have investigated particles an order of magnitude larger than those used in practical applications. Studying smaller particles quickly becomes demanding as the diffracted intensity falls. Here, in situ nanodiffraction data from 60 nm Au nanoparticles under electrochemical control collected at the hard X-ray nanoprobe beamline of MAX IV, NanoMAX, are presented. Two-dimensional image reconstructions of these particles are produced, and it is estimated that NanoMAX, which is now open for general users, has the requisites for three-dimensional imaging of particles of a size relevant for catalytic applications. This represents the first demonstration of coherent X-ray diffraction experiments performed at a diffraction-limited storage ring, and illustrates the importance of these new sources for experiments where coherence properties become crucial. Full Article text
control Optimization of crystallization of biological macromolecules using dialysis combined with temperature control By scripts.iucr.org Published On :: 2020-05-05 A rational way to find the appropriate conditions to grow crystal samples for bio-crystallography is to determine the crystallization phase diagram, which allows precise control of the parameters affecting the crystal growth process. First, the nucleation is induced at supersaturated conditions close to the solubility boundary between the nucleation and metastable regions. Then, crystal growth is further achieved in the metastable zone – which is the optimal location for slow and ordered crystal expansion – by modulation of specific physical parameters. Recently, a prototype of an integrated apparatus for the rational optimization of crystal growth by mapping and manipulating temperature–precipitant–concentration phase diagrams has been constructed. Here, it is demonstrated that a thorough knowledge of the phase diagram is vital in any crystallization experiment. The relevance of the selection of the starting position and the kinetic pathway undertaken in controlling most of the final properties of the synthesized crystals is shown. The rational crystallization optimization strategies developed and presented here allow tailoring of crystal size and diffraction quality, significantly reducing the time, effort and amount of expensive protein material required for structure determination. Full Article text
control Full reciprocal-space mapping up to 2000 K under controlled atmosphere: the multipurpose QMAX furnace By scripts.iucr.org Published On :: 2020-04-23 A furnace that covers the temperature range from room temperature up to 2000 K has been designed, built and implemented on the D2AM beamline at the ESRF. The QMAX furnace is devoted to the full exploration of the reciprocal hemispace located above the sample surface. It is well suited for symmetric and asymmetric 3D reciprocal space mapping. Owing to the hemispherical design of the furnace, 3D grazing-incidence small- and wide-angle scattering and diffraction measurements are possible. Inert and reactive experiments can be performed at atmospheric pressure under controlled gas flux. It is demonstrated that the QMAX furnace allows monitoring of structural phase transitions as well as microstructural evolution at the nanoscale, such as self-organization processes, crystal growth and strain relaxation. A time-resolved in situ oxidation experiment illustrates the capability to probe the high-temperature reactivity of materials. Full Article text
control The flavin mononucleotide cofactor in α-hydroxyacid oxidases exerts its electrophilic/nucleophilic duality in control of the substrate-oxidation level By scripts.iucr.org Published On :: 2019-09-24 The Y128F single mutant of p-hydroxymandelate oxidase (Hmo) is capable of oxidizing mandelate to benzoate via a four-electron oxidative decarboxylation reaction. When benzoylformate (the product of the first two-electron oxidation) and hydrogen peroxide (an oxidant) were used as substrates the reaction did not proceed, suggesting that free hydrogen peroxide is not the committed oxidant in the second two-electron oxidation. How the flavin mononucleotide (FMN)-dependent four-electron oxidation reaction takes place remains elusive. Structural and biochemical explorations have shed new light on this issue. 15 high-resolution crystal structures of Hmo and its mutants liganded with or without a substrate reveal that oxidized FMN (FMNox) possesses a previously unknown electrophilic/nucleophilic duality. In the Y128F mutant the active-site perturbation ensemble facilitates the polarization of FMNox to a nucleophilic ylide, which is in a position to act on an α-ketoacid, forming an N5-acyl-FMNred dead-end adduct. In four-electron oxidation, an intramolecular disproportionation reaction via an N5-alkanol-FMNred C'α carbanion intermediate may account for the ThDP/PLP/NADPH-independent oxidative decarboxylation reaction. A synthetic 5-deaza-FMNox cofactor in combination with an α-hydroxyamide or α-ketoamide biochemically and structurally supports the proposed mechanism. Full Article text
control Controlled dehydration, structural flexibility and gadolinium MRI contrast compound binding in the human plasma glycoprotein afamin By scripts.iucr.org Published On :: 2019-11-19 Afamin, which is a human blood plasma glycoprotein, a putative multifunctional transporter of hydrophobic molecules and a marker for metabolic syndrome, poses multiple challenges for crystallographic structure determination, both practically and in analysis of the models. Several hundred crystals were analysed, and an unusual variability in cell volume and difficulty in solving the structure despite an ∼34% sequence identity with nonglycosylated human serum albumin indicated that the molecule exhibits variable and context-sensitive packing, despite the simplified glycosylation in insect cell-expressed recombinant afamin. Controlled dehydration of the crystals was able to stabilize the orthorhombic crystal form, reducing the number of molecules in the asymmetric unit from the monoclinic form and changing the conformational state of the protein. An iterative strategy using fully automatic experiments available on MASSIF-1 was used to quickly determine the optimal protocol to achieve the phase transition, which should be readily applicable to many types of sample. The study also highlights the drawback of using a single crystallographic structure model for computational modelling purposes given that the conformational state of the binding sites and the electron density in the binding site, which is likely to result from PEGs, greatly varies between models. This also holds for the analysis of nonspecific low-affinity ligands, where often a variety of fragments with similar uncertainty can be modelled, inviting interpretative bias. As a promiscuous transporter, afamin also seems to bind gadoteridol, a magnetic resonance imaging contrast compound, in at least two sites. One pair of gadoteridol molecules is located near the human albumin Sudlow site, and a second gadoteridol molecule is located at an intermolecular site in proximity to domain IA. The data from the co-crystals support modern metrics of data quality in the context of the information that can be gleaned from data sets that would be abandoned on classical measures. Full Article text
control Fast continuous measurement of synchrotron powder diffraction synchronized with controlling gas and vapour pressures at beamline BL02B2 of SPring-8 By scripts.iucr.org Published On :: 2020-03-16 A gas- and vapour-pressure control system synchronized with the continuous data acquisition of millisecond high-resolution powder diffraction measurements was developed to study structural change processes in gas storage and reaction materials such as metal organic framework compounds, zeolite and layered double hydroxide. The apparatus, which can be set up on beamline BL02B2 at SPring-8, mainly comprises a pressure control system of gases and vapour, a gas cell for a capillary sample, and six one-dimensional solid-state (MYTHEN) detectors. The pressure control system can be remotely controlled via developed software connected to a diffraction measurement system and can be operated in the closed gas and vapour line system. By using the temperature-control system on the sample, high-resolution powder diffraction data can be obtained under gas and vapour pressures ranging from 1 Pa to 130 kPa in temperatures ranging from 30 to 1473 K. This system enables one to perform automatic and high-throughput in situ X-ray powder diffraction experiments even at extremely low pressures. Furthermore, this developed system is useful for studying crystal structures during the adsorption/desorption processes, as acquired by millisecond and continuous powder diffraction measurements. The acquisition of diffraction data can be synchronized with the control of the pressure with a high frame rate of up to 100 Hz. In situ and time-resolved powder diffraction measurements are demonstrated for nanoporous Cu coordination polymer in various gas and vapour atmospheres. Full Article text
control A temperature-controlled cold-gas humidifier and its application to protein crystals with the humid-air and glue-coating method By scripts.iucr.org Published On :: 2019-06-14 The room-temperature experiment has been revisited for macromolecular crystallography. Despite being limited by radiation damage, such experiments reveal structural differences depending on temperature, and it is expected that they will be able to probe structures that are physiologically alive. For such experiments, the humid-air and glue-coating (HAG) method for humidity-controlled experiments is proposed. The HAG method improves the stability of most crystals in capillary-free experiments and is applicable at both cryogenic and ambient temperatures. To expand the thermal versatility of the HAG method, a new humidifier and a protein-crystal-handling workbench have been developed. The devices provide temperatures down to 4°C and successfully maintain growth at that temperature of bovine cytochrome c oxidase crystals, which are highly sensitive to temperature variation. Hence, the humidifier and protein-crystal-handling workbench have proved useful for temperature-sensitive samples and will help reveal temperature-dependent variations in protein structures. Full Article text
control A temperature-controlled cold-gas humidifier and its application to protein crystals with the humid-air and glue-coating method By journals.iucr.org Published On :: A new temperature-controllable humidifier for X-ray diffraction has been developed. It is shown that the humidifier can successfully maintain protein crystal growth at a temperature lower than room temperature. Full Article text
control Unit-cell response of tetragonal hen egg white lysozyme upon controlled relative humidity variation By journals.iucr.org Published On :: The effects of relative humidity on a tetragonal crystal form of hen egg white lysozyme are studied via in situ laboratory X-ray powder diffraction. Full Article text
control Optimization of crystallization of biological macromolecules using dialysis combined with temperature control By journals.iucr.org Published On :: This article describes rational strategies for the optimization of crystal growth using precise in situ control of the temperature and chemical composition of the crystallization solution through dialysis, to generate crystals of the specific sizes required for different downstream structure determination approaches. Full Article text