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1.
Nature ; 603(7900): 271-275, 2022 03.
Artigo em Inglês | MEDLINE | ID: mdl-35038718

RESUMO

In oxidation reactions catalysed by supported metal nanoparticles with oxygen as the terminal oxidant, the rate of the oxygen reduction can be a limiting factor. This is exemplified by the oxidative dehydrogenation of alcohols, an important class of reactions with modern commercial applications1-3. Supported gold nanoparticles are highly active for the dehydrogenation of the alcohol to an aldehyde4 but are less effective for oxygen reduction5,6. By contrast, supported palladium nanoparticles offer high efficacy for oxygen reduction5,6. This imbalance can be overcome by alloying gold with palladium, which gives enhanced activity to both reactions7,8,9; however, the electrochemical potential of the alloy is a compromise between that of the two metals, meaning that although the oxygen reduction can be improved in the alloy, the dehydrogenation activity is often limited. Here we show that by separating the gold and palladium components in bimetallic carbon-supported catalysts, we can almost double the reaction rate compared with that achieved with the corresponding alloy catalyst. We demonstrate this using physical mixtures of carbon-supported monometallic gold and palladium catalysts and a bimetallic catalyst comprising separated gold and palladium regions. Furthermore, we demonstrate electrochemically that this enhancement is attributable to the coupling of separate redox processes occurring at isolated gold and palladium sites. The discovery of this catalytic effect-a cooperative redox enhancement-offers an approach to the design of multicomponent heterogeneous catalysts.


Assuntos
Ouro , Nanopartículas Metálicas , Álcoois , Ligas , Carbono , Catálise , Oxirredução , Oxigênio , Paládio
2.
PLoS Genet ; 20(6): e1011302, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38829899

RESUMO

Cryptococcus neoformans is an opportunistic, human fungal pathogen which undergoes fascinating switches in cell cycle control and ploidy when it encounters stressful environments such as the human lung. Here we carry out a mechanistic analysis of the spindle checkpoint which regulates the metaphase to anaphase transition, focusing on Mps1 kinase and the downstream checkpoint components Mad1 and Mad2. We demonstrate that Cryptococcus mad1Δ or mad2Δ strains are unable to respond to microtubule perturbations, continuing to re-bud and divide, and die as a consequence. Fluorescent tagging of Chromosome 3, using a lacO array and mNeonGreen-lacI fusion protein, demonstrates that mad mutants are unable to maintain sister-chromatid cohesion in the absence of microtubule polymers. Thus, the classic checkpoint functions of the SAC are conserved in Cryptococcus. In interphase, GFP-Mad1 is enriched at the nuclear periphery, and it is recruited to unattached kinetochores in mitosis. Purification of GFP-Mad1 followed by mass spectrometric analysis of associated proteins show that it forms a complex with Mad2 and that it interacts with other checkpoint signalling components (Bub1) and effectors (Cdc20 and APC/C sub-units) in mitosis. We also demonstrate that overexpression of Mps1 kinase is sufficient to arrest Cryptococcus cells in mitosis, and show that this arrest is dependent on both Mad1 and Mad2. We find that a C-terminal fragment of Mad1 is an effective in vitro substrate for Mps1 kinase and map several Mad1 phosphorylation sites. Some sites are highly conserved within the C-terminal Mad1 structure and we demonstrate that mutation of threonine 667 (T667A) leads to loss of checkpoint signalling and abrogation of the GAL-MPS1 arrest. Thus Mps1-dependent phosphorylation of C-terminal Mad1 residues is a critical step in Cryptococcus spindle checkpoint signalling. We conclude that CnMps1 protein kinase, Mad1 and Mad2 proteins have all conserved their important, spindle checkpoint signalling roles helping ensure high fidelity chromosome segregation.


Assuntos
Proteínas de Ciclo Celular , Cryptococcus neoformans , Proteínas Mad2 , Fuso Acromático , Cryptococcus neoformans/genética , Cryptococcus neoformans/metabolismo , Proteínas de Ciclo Celular/metabolismo , Proteínas de Ciclo Celular/genética , Proteínas Mad2/metabolismo , Proteínas Mad2/genética , Fuso Acromático/metabolismo , Fuso Acromático/genética , Transdução de Sinais , Proteínas Fúngicas/metabolismo , Proteínas Fúngicas/genética , Humanos , Proteínas Serina-Treonina Quinases/metabolismo , Proteínas Serina-Treonina Quinases/genética , Pontos de Checagem da Fase M do Ciclo Celular/genética , Mitose/genética , Cinetocoros/metabolismo , Segregação de Cromossomos/genética , Microtúbulos/metabolismo , Microtúbulos/genética , Proteínas Nucleares/metabolismo , Proteínas Nucleares/genética
3.
Proc Natl Acad Sci U S A ; 119(28): e2111212119, 2022 07 12.
Artigo em Inglês | MEDLINE | ID: mdl-35787044

RESUMO

The origins of Homo, as well as the diversity and biogeographic distribution of early Homo species, remain critical outstanding issues in paleoanthropology. Debates about the recognition of early Homo, first appearance dates, and taxonomic diversity within Homo are particularly important for determining the role that southern African taxa may have played in the origins of the genus. The correct identification of Homo remains also has implications for reconstructing phylogenetic relationships between species of Australopithecus and Paranthropus, and the links between early Homo species and Homo erectus. We use microcomputed tomography and landmark-free deformation-based three-dimensional geometric morphometrics to extract taxonomically informative data from the internal structure of postcanine teeth attributed to Early Pleistocene Homo in the southern African hominin-bearing sites of Sterkfontein, Swartkrans, Drimolen, and Kromdraai B. Our results indicate that, from our sample of 23 specimens, only 4 are unambiguously attributed to Homo, 3 of them coming from Swartkrans member 1 (SK 27, SK 847, and SKX 21204) and 1 from Sterkfontein (Sts 9). Three other specimens from Sterkfontein (StW 80 and 81, SE 1508, and StW 669) approximate the Homo condition in terms of overall enamel-dentine junction shape, but retain Australopithecus-like dental traits, and their generic status remains unclear. The other specimens, including SK 15, present a dominant australopith dental signature. In light of these results, previous dietary and ecological interpretations can be reevaluated, showing that the geochemical signal of one tooth from Kromdraai (KB 5223) and two from Swartkrans (SK 96 and SKX 268) is consistent with that of australopiths.


Assuntos
Hominidae , Dente , Animais , Fósseis , Filogenia , Dente/diagnóstico por imagem , Microtomografia por Raio-X
4.
Br J Anaesth ; 133(3): 538-549, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-38688799

RESUMO

INTRODUCTION: Persistent inflammation, immunosuppression, and catabolism syndrome (PICS) has been proposed as an endotype of chronic critical illness (CCI). The aim of this systematic review is to synthesise the available evidence of risk factors, biomarkers, and biological mechanisms underlying PICS. METHODS: MEDLINE, CENTRAL, and EMBASE were searched on June 2, 2023. Our population of interest was adult intensive care unit survivors. The exposure group was patients with PICS and the comparator group was patients with no PICS, CCI, or rapid recovery. Mean differences were pooled for each biomarker using a random effects DerSimonian-Laird method. Risk of bias assessment was done using the Newcastle-Ottawa Scale. RESULTS: Six papers were included. Five were single-centre retrospective cohort studies, and one was a prospective cohort study, with sample sizes ranging from 22 to 391 patients. Two studies showed an increased incidence of PICS with age, and two studies showed an association between PICS and Charlson Comorbidity Index scores. PICS was associated with requiring mechanical ventilation in four studies. Meta-analysis showed a 34.4 mg L-1 higher C-reactive protein (95% confidence interval [CI] 12.7-56.2 mg L-1; P<0.01), a 4.4 g L-1 lower albumin (95% CI 0.5-8.3 g L-1; P<0.01), and a 0.36×109 L-1 lower lymphocyte count (95% CI 0.25-0.47×109 L-1; P=0.01) in the PICS compared with the non-PICS group. There are a large variety of other potential biomarkers but limited validation studies. The overall quality of evidence is limited, and these results should be interpreted accordingly. CONCLUSIONS: While older patients and those with co-morbidities could be at greater risk for PICS, acquired risk factors, such as injury severity, are potentially more predictive of PICS than intrinsic patient characteristics. There are many potential biomarkers for PICS, but limited validation studies have been conducted. Persistent myeloid-derived suppressor cell expansion, the continual release of danger-associated molecular patterns and pathogen-associated molecular patterns propagating inflammation, and bioenergetic failure are all mechanisms underlying PICS that could offer potential for novel biomarkers and therapeutic interventions. CLINICAL TRIAL REGISTRATION: International Prospective Register of Systematic Reviews (PROSPERO; CRD42023427749).


Assuntos
Biomarcadores , Estado Terminal , Inflamação , Humanos , Biomarcadores/sangue , Fatores de Risco , Inflamação/sangue , Síndrome , Tolerância Imunológica
5.
Br J Anaesth ; 2024 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-39389833

RESUMO

BACKGROUND: Nitrous oxide (N2O) is a potent greenhouse gas that contributes significantly to the healthcare sector's carbon footprint. Pre-utilisation losses of N2O are up to 95%. Decommissioning manifolds can reduce these losses. METHODS: Hospitals in our Greater London research network with at least one active N2O manifold were included in the Nitrous Oxide Manifold and Other Reduction of Emissions (NoMoreGas) study. N2O utilisation data were collected continuously over 5 days and extrapolated over a year, in addition to collecting procurement records from the preceding financial year. The primary outcome was the discrepancy between clinically utilised N2O and the quantity procured by hospitals, referred to as the 'N2O gap'. Secondary outcomes included anaesthetists' self-reported utilisation of N2O and their opinions on manifold decommissioning. RESULTS: Eighteen of 53 hospitals were included. In total, 6 487 200 L of N2O were procured with a median (IQR) of 304 200 (183 600-473 400) L per site. During the 5-day data collection period, sites utilised a median (IQR) of 501 (42-1409) L of N2O. Extrapolating over a year resulted in a median (IQR) annual utilisation of 36 573 (3066-102 857) L per site and a total of 1 175 348 L. This represented an estimated 18% of the N2O procured, suggesting pre-utilisation losses of 5 311 852 L. Among surveyed anaesthetists, 70% (n=309) reported using N2O within the previous year, with one-third (n=97) using it once a week or more. There was widespread support for decommissioning manifolds. CONCLUSIONS: Consistent with other reports, the data demonstrate a substantial discrepancy between the quantities of N2O procured and utilised clinically, indicative of significant pre-utilisation losses. Our findings support the decommissioning of N2O manifolds for environmental and economic benefits.

6.
Curr Opin Crit Care ; 29(2): 108-113, 2023 04 01.
Artigo em Inglês | MEDLINE | ID: mdl-36762680

RESUMO

PURPOSE OF REVIEW: Muscle wasting in critical illness has proven to be refractory to physical rehabilitation, and to conventional nutritional strategies. This presents one of the central challenges to critical care medicine in the 21st century. Novel strategies are needed that facilitate nutritional interventions, identify patients that will benefit and have measurable, relevant benefits. RECENT FINDINGS: Drug repurposing was demonstrated to be a powerful technique in the coronavirus disease 2019 pandemic, and may have similar applications to address the metabolic derangements of critical illness. Newer biological signatures may aid the application of these techniques and the association between changes in urea:creatinine ratio and the development of skeletal muscle wasting is increasing. A core outcome set for nutrition interventions in critical illness, supported by multiple international societies, was published earlier this year should be adopted by future nutrition trials aiming to attenuate muscle wasting. SUMMARY: The evidence base for the lack of efficacy for conventional nutritional strategies in preventing muscle wasting in critically ill patients continues to grow. Novel strategies such as metabolic modulators, patient level biological signatures of nutritional response and standardized outcome for measurements of efficacy will be central to future research and clinical care of the critically ill patient.


Assuntos
COVID-19 , Estado Terminal , Humanos , Estado Terminal/terapia , Atrofia Muscular/prevenção & controle , Atrofia Muscular/metabolismo , Estado Nutricional , Músculos , Músculo Esquelético/metabolismo
7.
J Am Chem Soc ; 144(41): 18817-18822, 2022 10 19.
Artigo em Inglês | MEDLINE | ID: mdl-36194199

RESUMO

The nickel catalyzed reductive coupling of aldehydes with sorbate esters and related electron-deficient 1,3-dienes are known in the literature to occur at the π-bond proximal to the ester to afford aldol-type products. In stark contrast to this established path, a VAPOL-derived phosphoramidite ligand in combination with a bench-stable nickel precatalyst brokers a regiocomplementary course in that C-C bond formation proceeds exclusively at the distal alkene site to give deoxypropionate type products carrying an acrylate handle; they can be made in either anti- or syn-configured form. In addition to this enabling reverse pathway, the reaction is distinguished by excellent levels of chemo-, diastereo-, and enantioselectivity; moreover, it can be extended to the catalytic formation of F3C-substituted stereogenic centers. The use of a dienyl pinacolboronate instead of a sorbate ester is also possible, which opens access to valuable chiral borylated building blocks in optically active form.


Assuntos
Elétrons , Níquel , Níquel/química , Estereoisomerismo , Ligantes , Aldeídos/química , Catálise , Alcenos/química , Ésteres , Polienos , Acrilatos
8.
J Am Chem Soc ; 144(34): 15431-15436, 2022 08 31.
Artigo em Inglês | MEDLINE | ID: mdl-35976628

RESUMO

Heterogeneous palladium catalysts modified by N-heterocyclic carbenes (NHCs) are shown to be highly effective toward the direct synthesis of hydrogen peroxide (H2O2), in the absence of the promoters which are typically required to enhance both activity and selectivity. Catalytic evaluation in a batch regime demonstrated that through careful selection of the N-substituent of the NHC it is possible to greatly enhance catalytic performance when compared to the unmodified analogue and reach concentrations of H2O2 rivaling that obtained by state-of-the-art catalysts. The enhanced performance of the modified catalyst, which is retained upon reuse, is attributed to the ability of the NHC to electronically modify Pd speciation.


Assuntos
Compostos Heterocíclicos , Paládio , Catálise , Peróxido de Hidrogênio , Metano/análogos & derivados
9.
Glob Chang Biol ; 28(18): 5346-5367, 2022 09.
Artigo em Inglês | MEDLINE | ID: mdl-35583661

RESUMO

The globally widespread adoption of Artificial Light at Night (ALAN) began in the mid-20th century. Yet, it is only in the last decade that a renewed research focus has emerged into its impacts on ecological and biological processes in the marine environment that are guided by natural intensities, moon phase, natural light and dark cycles and daily light spectra alterations. The field has diversified rapidly from one restricted to impacts on a handful of vertebrates, to one in which impacts have been quantified across a broad array of marine and coastal habitats and species. Here, we review the current understanding of ALAN impacts in diverse marine ecosystems. The review presents the current state of knowledge across key marine and coastal ecosystems (sandy and rocky shores, coral reefs and pelagic) and taxa (birds and sea turtles), introducing how ALAN can mask seabird and sea turtle navigation, cause changes in animals predation patterns and failure of coral spawning synchronization, as well as inhibition of zooplankton Diel Vertical Migration. Mitigation measures are recommended, however, while strategies for mitigation were easily identified, barriers to implementation are poorly understood. Finally, we point out knowledge gaps that if addressed would aid in the prediction and mitigation of ALAN impacts in the marine realm.


Assuntos
Antozoários , Ecossistema , Animais , Recifes de Corais , Luz , Poluição Luminosa
10.
Chemistry ; 28(56): e202201575, 2022 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-35801389

RESUMO

N-heterocyclic carbenes (NHCs) have become attractive ligands for functionalizing gold nanoparticle surfaces with applications ranging from catalysis to biomedicine. Despite their great potential, NHC stabilized gold colloids (NHC@AuNPs) are still scarcely explored and further efforts should be conducted to improve their design and functionalization. Here, the 'bottom-up' synthesis of two water-soluble gold nanoparticles (AuNP-1 and AuNP-2) stabilized by hydrophilic mono- and bidentate NHC ligands is reported together with their characterization by various spectroscopic and analytical methods. The NPs showed key differences likely to be due to the selected NHC ligand systems. Transmission electron microscopy (TEM) images showed small quasi-spherical and faceted NHC@AuNPs of similar particle size (ca. 2.3-2.6 nm) and narrow particle size distribution, but the colloids featured different ratios of Au(I)/Au(0) by X-ray photoelectron spectroscopy (XPS). Furthermore, the NHC@AuNPs were supported on titania and fully characterized. The new NPs were studied for their catalytic activity towards the reduction of nitrophenol substrates, the reduction of resazurin and for their photothermal efficiency. Initial results on their application in photothermal therapy (PTT) were obtained in human cancer cells in vitro. The aforementioned reactions represent important model reactions towards wastewater remediation, bioorthogonal transformations and cancer treatment.


Assuntos
Ouro , Nanopartículas Metálicas , Coloides , Ouro/química , Humanos , Ligantes , Nanopartículas Metálicas/química , Metano/análogos & derivados , Nitrofenóis , Águas Residuárias , Água
11.
Biol Lett ; 18(7): 20220110, 2022 07.
Artigo em Inglês | MEDLINE | ID: mdl-35892207

RESUMO

Mounting evidence shows that artificial light at night (ALAN) alters biological processes across levels of organization, from cells to communities. Yet, the combined impacts of ALAN and natural sources of night-time illumination remain little explored. This is in part due the lack of accurate simulations of the complex changes moonlight intensity, timing and spectra throughout a single night and lunar cycles in laboratory experiments. We custom-built a novel system to simulate natural patterns of moonlight to test how different ALAN intensities affect predator-prey relationships over the full lunar cycle. Exposure to high intensity ALAN (10 and 50 lx) reversed the natural lunar-guided foraging pattern by the gastropod mesopredator Nucella lapillus on its prey Semibalanus balanoides. Foraging decreased during brighter moonlight in naturally lit conditions. When exposed to high intensity ALAN, foraging increased with brighter moonlight. Low intensity ALAN (0.1 and 0.5 lx) had no impact on foraging. Our results show that ALAN alters the foraging pattern guided by changes in moonlight brightness. ALAN impacts on ecosystems can depend on lunar light cycles. Accurate simulations of night-time light cycle will warrant more realistic insights into ALAN impacts and also facilitate advances in fundamental night-time ecology and chronobiology.


Assuntos
Ecossistema , Gastrópodes , Animais , Luz , Poluição Luminosa , Iluminação , Fotoperíodo
12.
Nature ; 531(7592): 83-7, 2016 Mar 03.
Artigo em Inglês | MEDLINE | ID: mdl-26878237

RESUMO

Copper and zinc form an important group of hydroxycarbonate minerals that include zincian malachite, aurichalcite, rosasite and the exceptionally rare and unstable--and hence little known and largely ignored--georgeite. The first three of these minerals are widely used as catalyst precursors for the industrially important methanol-synthesis and low-temperature water-gas shift (LTS) reactions, with the choice of precursor phase strongly influencing the activity of the final catalyst. The preferred phase is usually zincian malachite. This is prepared by a co-precipitation method that involves the transient formation of georgeite; with few exceptions it uses sodium carbonate as the carbonate source, but this also introduces sodium ions--a potential catalyst poison. Here we show that supercritical antisolvent (SAS) precipitation using carbon dioxide (refs 13, 14), a process that exploits the high diffusion rates and solvation power of supercritical carbon dioxide to rapidly expand and supersaturate solutions, can be used to prepare copper/zinc hydroxycarbonate precursors with low sodium content. These include stable georgeite, which we find to be a precursor to highly active methanol-synthesis and superior LTS catalysts. Our findings highlight the value of advanced synthesis methods in accessing unusual mineral phases, and show that there is room for exploring improvements to established industrial catalysts.

13.
JAMA ; 327(18): 1795-1805, 2022 05 10.
Artigo em Inglês | MEDLINE | ID: mdl-35510389

RESUMO

Importance: The benefit of endovascular thrombectomy (EVT) for acute ischemic stroke is highly time-dependent, and it is challenging to expedite treatment for patients in remote areas. Objective: To determine whether deployment of a flying intervention team, compared with patient interhospital transfer, is associated with a shorter time to endovascular thrombectomy and improved clinical outcomes for patients with acute ischemic stroke. Design, Setting, and Participants: This was a nonrandomized controlled intervention study comparing 2 systems of care in alternating weeks. The study was conducted in a nonurban region in Germany including 13 primary telemedicine-assisted stroke centers within a telestroke network. A total of 157 patients with acute ischemic stroke for whom decision to pursue thrombectomy had been made and deployment of flying intervention team or patient interhospital transfer was initiated were enrolled between February 1, 2018, and October 24, 2019. The date of final follow-up was January 31, 2020. Exposures: Deployment of a flying intervention team for EVT in a primary stroke center vs patient interhospital transfer for EVT to a referral center. Main Outcomes and Measures: The primary outcome was time delay from decision to pursue thrombectomy to start of the procedure in minutes. Secondary outcomes included functional outcome after 3 months, determined by the distribution of the modified Rankin Scale score (a disability score ranging from 0 [no deficit] to 6 [death]). Results: Among the 157 patients included (median [IQR] age, 75 [66-80] y; 80 [51%] women), 72 received flying team care and 85 were transferred. EVT was performed in 60 patients (83%) in the flying team group vs 57 (67%) in the transfer group. Median (IQR) time from decision to pursue EVT to start of the procedure was 58 (51-71) minutes in the flying team group and 148 (124-177) minutes in the transfer group (difference, 90 minutes [95% CI, 75-103]; P < .001). There was no significant difference in modified Rankin Scale score after 3 months between patients in the flying team (n = 59) and transfer (n = 57) groups who received EVT (median [IQR] score, 3 [2-6] vs 3 [2-5]; adjusted common odds ratio for less disability, 1.91 [95% CI, 0.96-3.88]; P = .07). Conclusions and Relevance: In a nonurban stroke network in Germany, deployment of a flying intervention team to local stroke centers, compared with patient interhospital transfer to referral centers, was significantly associated with shorter time to EVT for patients with acute ischemic stroke. The findings may support consideration of a flying intervention team for some stroke systems of care, although further research is needed to confirm long-term clinical outcomes and to understand applicability to other geographic settings.


Assuntos
Isquemia Encefálica , Procedimentos Endovasculares , AVC Isquêmico , Transferência de Pacientes , Trombectomia , Idoso , Idoso de 80 Anos ou mais , Isquemia Encefálica/cirurgia , Procedimentos Endovasculares/métodos , Feminino , Alemanha , Humanos , AVC Isquêmico/cirurgia , Masculino , Acidente Vascular Cerebral/cirurgia , Trombectomia/métodos , Fatores de Tempo , Resultado do Tratamento , População Urbana
14.
Biophys J ; 120(17): 3831-3840, 2021 09 07.
Artigo em Inglês | MEDLINE | ID: mdl-34214523

RESUMO

A "permanent" bent shape can be imposed on a straight human hair by a two-stage reduction/oxidation (perm-waving) process. The process relies on the molecular level on sulfhydryl/disulfide interchange as bond exchange reaction (BER). We expected a well-documented transition temperature around 60°C to be the trigger for the shape memory (SM) process of perm-waved hair. We confirm the existence of the SM process as such and investigate its time and temperature dependence. The results show a two-stage SM behavior, implying two distinct variations of the BER. The model to fit the data contains two fractional, normalized, elastic bending rigidities, which are strictly compensatory. They show Arrhenius-type temperature dependence and a common activation energy (EA) of ∼-12 kJ/mol. The characteristic relaxation time for the first SM process shows little, if any, temperature dependence (EA = -4 ± 2.7 kJ/mol). This is in contrast to the second process (EA = -58 ± 5.5 kJ/mol) but in line with the expected properties of the suggested BERs. None of the parameters shows any sign of the expected trigger transition (∼60°C). We hypothesize that this specific transition occurs only for large tensile deformations, when specific SS bonds in the intermediate filaments of hair are activated. There is thus no specific "trigger" transition for the SM behavior of bent, perm-waved hair.


Assuntos
Cabelo , Filamentos Intermediários , Dissulfetos , Humanos , Cinética , Oxirredução , Temperatura
15.
Biophys J ; 120(15): 3091-3102, 2021 08 03.
Artigo em Inglês | MEDLINE | ID: mdl-34214527

RESUMO

In green plants, light harvesting complex of Photosystem II (LHCII) absorbs and transports excitation energy toward the photosynthetic reaction centers and serves as a site for energy-dependent nonphotochemical quenching (qE), the photoprotective dissipation of energy as heat. LHCII is thought to activate dissipation through conformational changes that change the photophysical behaviors. Understanding this balance requires a characterization of how the conformations of LHCII, and thus its photophysics, are influenced by individual factors within the membrane environment. Here, we used ensemble and single-molecule fluorescence to characterize the excited-state lifetimes and switching kinetics of LHCII embedded in nanodisc- and liposome-based model membranes of various sizes and lipid compositions. As the membrane area decreased, the quenched population and the rate of conformational dynamics both increased because of interactions with other proteins, the aqueous solution, and/or disordered lipids. Although the conformational states and dynamics were similar in both thylakoid and asolectin lipids, photodegradation increased with thylakoid lipids, likely because of their charge and pressure properties. Collectively, these findings demonstrate the ability of membrane environments to tune the conformations and photophysics of LHCII.


Assuntos
Complexos de Proteínas Captadores de Luz , Tilacoides , Cinética , Complexos de Proteínas Captadores de Luz/metabolismo , Complexo de Proteína do Fotossistema II , Imagem Individual de Molécula , Tilacoides/metabolismo
16.
J Am Chem Soc ; 143(34): 13489-13494, 2021 09 01.
Artigo em Inglês | MEDLINE | ID: mdl-34410708

RESUMO

Nickel catalysis allied with cyclodiphosphazane or VAPOL-derived phosphoramidite ligands provides selective access to monoprotected vicinal diols by reductive coupling of dienol ethers and aldehydes. The observed regioselectivity is unprecedented, in that the diene reacts at the least nucleophilic and most hindered C atom that is attached to the oxygen substituent rather than at the terminal position. Notably, both syn and anti diastereomers of the products can be accessed depending on the configuration of the diene partner with usually excellent diastereo- and enantioselectivity.

17.
Small ; 17(16): e2007221, 2021 04.
Artigo em Inglês | MEDLINE | ID: mdl-33629821

RESUMO

The formation of highly active and stable acetylene hydrochlorination catalysts is of great industrial importance. The successful replacement of the highly toxic mercuric chloride catalyst with gold has led to a flurry of research in this area. One key aspect, which led to the commercialization of the gold catalyst is the use of thiosulphate as a stabilizing ligand. This study investigates the use of a range of sulfur containing compounds as promoters for production of highly active Au/C catalysts. Promotion is observed across a range of metal sulfates, non-metal sulfates, and sulfuric acid treatments. This observed enhancement can be optimized by careful consideration of either pre- or post-treatments, concentration of dopants used, and modification of washing steps. Pre-treatment of the carbon support with sulfuric acid (0.76 m) resulted in the most active Au/C in this series with an acetylene conversion of ≈70% at 200 °C.


Assuntos
Acetileno , Ouro , Carbono , Catálise , Enxofre
18.
Chemistry ; 27(35): 8918-8927, 2021 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-33857343

RESUMO

Sulfinylamines (R-N=S=O), monoaza analogues of sulfur dioxide, have been known for well over a century, and their reactivity as sulfur electrophiles and in Diels-Alder reactions is well-established. However, they have only rarely been used in organic synthesis in recent decades despite the increasing prominence of compounds containing N=S=O functionality, such as sulfoximines and sulfonimidamides. This Minireview aims to bring wider visibility to the unique chemistry enabled by this class of compounds. We focus on advances from the last 10 years, including the first examples of their use in the one-pot syntheses of sulfoximines and sulfonimidamides. Also covered are the reactions of sulfinylamines with carbon-centred radicals, their use for formation of heterocycles through cycloadditions, and catalytic enantioselective allylic oxidation of alkenes via a hetero-ene reaction. These examples highlight the different reactivity modes of sulfinylamines and their underappreciated potential for forming molecules which contain high- or low-valent sulfur, or even no sulfur at all.


Assuntos
Alcenos , Catálise , Técnicas de Química Sintética , Reação de Cicloadição , Indicadores e Reagentes
19.
J Hum Evol ; 152: 102939, 2021 03.
Artigo em Inglês | MEDLINE | ID: mdl-33517134

RESUMO

Thirteen permanent fully erupted teeth were excavated at the Paleolithic site of La Cotte de St Brelade in Jersey in 1910 and 1911. These were all found in the same location, on a ledge behind a hearth in a Mousterian occupation level. They were originally identified as being Neanderthal. A fragment of occipital bone was found in a separate locality in a later season. Recent dating of adjacent sediments gives a probable age of <48 ka. The purpose of this article is to provide an updated description of the morphology of this material and consider its likely taxonomic assignment from comparison with Neanderthal and Homo sapiens samples. One of the original teeth has been lost, and we identify one as nonhominin. At least two adult individuals are represented. Cervix shape and the absence of common Neanderthal traits in several teeth suggest affinities with H. sapiens in both individuals, while crown and root dimensions and root morphology of all the teeth are entirely consistent with a Neanderthal attribution, pointing toward a possible shared Neanderthal and H. sapiens ancestry (the likely date of this material corresponds with the time in which both Neanderthals and H. sapiens were present in Europe). The occipital fragment is stratigraphically more recent and does not exhibit any diagnostic Neanderthal features.


Assuntos
Fósseis/anatomia & histologia , Homem de Neandertal/anatomia & histologia , Dente/anatomia & histologia , Animais , Evolução Biológica , Ilhas Anglo-Normandas , Feminino , Paleodontologia
20.
Cerebrovasc Dis ; 50(4): 375-382, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-33849042

RESUMO

BACKGROUND: Endovascular treatment of large vessel occlusion in acute ischemic stroke patients is difficult to establish in remote areas, and time dependency of treatment effect increases the urge to develop health care concepts for this population. SUMMARY: Current strategies include direct transportation of patients to a comprehensive stroke center (CSC) ("mothership model") or transportation to the nearest primary stroke center (PSC) and secondary transfer to the CSC ("drip-and-ship model"). Both have disadvantages. We propose the model "flying intervention team." Patients will be transported to the nearest PSC; if telemedically identified as eligible for thrombectomy, an intervention team will be acutely transported via helicopter to the PSC and endovascular treatment will be performed on site. Patients stay at the PSC for further stroke unit care. This model was implemented at a telestroke network in Germany. Fifteen remote hospitals participated in the project, covering 14,000 km2 and a population of 2 million. All have well established telemedically supported stroke units, an angiography suite, and a helicopter pad. Processes were defined individually for each hospital and training sessions were implemented for all stroke teams. An exclusive project helicopter was installed to be available from 8 a.m. to 10 p.m. during 26 weeks per year. Key Messages: The model of the flying intervention team is likely to reduce time delays since processes will be performed in parallel, rather than consecutively, and since it is quicker to move a medical team rather than a patient. This project is currently under evaluation (clinicaltrials NCT04270513).


Assuntos
Resgate Aéreo/organização & administração , Prestação Integrada de Cuidados de Saúde/organização & administração , Procedimentos Endovasculares , AVC Isquêmico/terapia , Serviços de Saúde Rural/organização & administração , Telemedicina/organização & administração , Trombectomia , Terapia Trombolítica , Área Programática de Saúde , Procedimentos Endovasculares/efeitos adversos , Humanos , AVC Isquêmico/diagnóstico , Trombectomia/efeitos adversos , Terapia Trombolítica/efeitos adversos , Fatores de Tempo , Tempo para o Tratamento/organização & administração , Resultado do Tratamento
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