bluuebunny/crossref_metadata_2025_split huggingface dataset:
Solar‐Assisted eBiorefinery: Photoelectrochemical Pairing of Oxyfunctionalization and Hydrogenation Reactions
Authors: Choi Da Som , Kim Jinhyun , Hollmann Frank , Park Chan Beum 
Published: June 2020

AbstractInspired by natural photosynthesis, biocatalytic photoelectrochemical (PEC) platforms are gaining prominence for the conversion of solar energy into useful chemicals by combining redox biocatalysis and photoelectrocatalysis. Herein, we report a dual biocatalytic PEC platform consisting of a molybdenum (Mo)‐doped BiVO4 (Mo:BiVO4) photoanode and an inverse opal ITO (IO‐ITO) cathode that gives rise to the coupling of peroxygenase and ene‐reductase‐mediated catalysis, respectively. In the PEC cell, the photoexcited electrons generated from the Mo:BiVO4 are transferred to the IO‐ITO and regenerate reduced flavin mononucleotides to drive ene‐reductase‐catalyzed trans‐hydrogenation of ketoisophrone to (R)‐levodione. Meanwhile, the photoactivated Mo:BiVO4 evolves H2O2 in situ via a two‐electron water‐oxidation process with the aid of an applied bias, which simultaneously supplies peroxygenases to drive selective hydroxylation of ethylbenzene into enantiopure (R)‐1‐phenyl‐1‐hydroxyethane. Thus, the deliberate integration of PEC systems with redox biocatalytic reactions can simultaneously produce valuable chemicals on both electrodes using solar‐powered electrons and water.
Effects of swim‐with‐dolphin tourism on the behaviour of spinner dolphins, at Samadai Reef in the Egyptian Red Sea
Authors: Shawky Ahmed M. , Christiansen Fredrik , Ormond Rupert 
Published: June 2020

Abstract

Spinner dolphins, Stenella longirostris, are the primary target for marine mammal tourism in Egypt. The present study investigated the short‐term effects of tourist presence on the behaviour of spinner dolphins at Sha'ab Samadai (Samadai Reef), in the southern Egyptian Red Sea.
The reef has a large central lagoon where a population of spinner dolphin regularly rest from mid‐morning to mid‐afternoon; visitors are permitted to snorkel in the southern part of the lagoon, but not in the northern closed zone that the dolphins mainly use.
Dolphin behaviour was monitored both on days when tourist boats were present and on days when they were absent. In the presence of tourists the proportion of time that the dolphins spent resting was reduced by two‐thirds, whereas the times spent milling, travelling, and showing avoidance behaviour all increased.
Furthermore, upon using Markov chain modelling to investigate the effect of tourist presence on the transition probabilities between dolphin activity states, significant changes were found in 10 of the 25 possible behavioural transitions, including increased probabilities of transitioning from resting to milling or travelling, from milling to travelling or avoiding, and from travelling to avoiding.
These findings raise concerns that despite the management measures in place, tourist activities affect the dolphins’ behaviour to a greater extent than was previously apparent, with potential long‐term negative effects on their energy budget. The study led to proposals for amending the zoning of the site and for strengthening the regulations for tourist vessels.
Multiple Vacancies on (111) Facets of Single‐Crystal NiFe2O4 Spinel Boost Electrocatalytic Oxygen Evolution Reaction
Authors: Chen Xiaokang , Zhang Xiaohui , Zhuang Linzhou , Zhang Wei , Zhang Naichi , Liu Hongwei , Zhan Tianrong , Zhang Xiaoli , She Xilin , Yang Dongjiang 
Published: June 2020

AbstractOxygen evolution reaction (OER) as the rate‐determining reaction of water splitting has been attracting enormous attention. At present, only some noble−metal oxide materials (IrO2 and RuO2) have been reported as efficient OER electrocatalysts for OER. However, the high cost and scarcity of these noble−metal oxide materials greatly hamper their large−scale practical application. Herein, we synthesize 100% (111) faceted NiFe2O4 single crystals with multiple vacancies (cation vacancies and O vacancies). The (111) facets can supply enough platform to break chemical bonds and enhance electrocatalytic activity, due to its high density of atomic steps and kink atoms. Compared to NiFe2O4 (without vacancies), the as‐synthesized NiFe2O4−Ar (with vacancies) exhibits a dramatically improved OER activity. The NiFe2O4−Ar‐30 shows the lowest onset potential (1.45 V vs RHE) and the best electrocatalytic OER activity with the lowest overpotential of 234 mV at 50 mA cm−2. Furthermore, based on the theoretical calculations that the introduction of multiple vacancies can effectively modulate the electronic structure of active centers to accelerate charge transfer and reaction intermediates adsorption, which can reduce the reaction energy barrier and enhance the activity of electrochemical OER.
In‐air self‐reduction synthesis and colour tunable luminescence from SrBPO5:Eu2+–Eu3+ excited using ultraviolet light
Authors: Wu Yuheng , Wu Yuansheng , Yu Lixin , Zou Yingxuan , Gao Zhenyu , Guo Qihuang , Liu Zongjian , Liu Bingfa 
Published: June 2020

AbstractSrBPO5:Eu2+–Eu3+ phosphors were synthesized using a conventional solid self‐reduction reaction in an air atmosphere. Samples were characterized using thermogravimetry analysis (TGA), differential scanning calorimetry (DSC), X‐ray diffraction (XRD), Fourier transform infrared (FTIR) spectra, fluorescence spectra and Commission International de l'Eclairage (CIE) data. The results of TGA and DSC showed that the raw materials could completely react at 1000°C. FTIR spectra and XRD results displayed that europium ions of different concentrations do not effect the structure of the hosts. Fluorescence spectra displayed that europium ions exist in bivalent and trivalent forms, and that the emission peak at 403 nm was attributed to the typical 5d−4f transition for Eu2+; 597 nm and 620 nm emissions were assigned to the characteristic transitions of 5D0−7F1, 2 for Eu3+. CIE results depicted that the colour tone of the phosphors could be macro‐controlled from blue to purple by controlling the doping amount of Eu3+.Therefore, relative luminescence intensity between Eu2+ and Eu3+ could be adjusted by controlling the doping concentration of europium to tune the luminescence colour of SrBPO5.
Liquid chromatography tandem mass spectrometry method for determination of fulvestrant in rat plasma and its application to pharmacokinetic studies of a novel fulvestrant microcrystal
Authors: Leng Guangyi , Zuo Yanhua , Hu Jiahui , Yu Fei , Liu Wanhui 
Published: June 2020

AbstractFulvestrant (‘Faslodex’), an estrogen receptor antagonist, is available for the treatment of advanced breast cancer. The oil‐based vehicle of Faslodex can lead to various adverse effects. A novel fulvestrant microcrystal (aqueous suspension) was developed in this study to eliminate these adverse effects. A sensitive and robust liquid chromatography tandem mass spectrometry method was developed and validated for the determination of fulvestrant in rat plasma using supported‐liquid extraction. The separation of fulvestrant was achieved on an Agilent SB‐C18column (2.1 × 50 mm, 3.5 μm) with isocratic elution using fulvestrant‐d3 as internal standard. Mass spectrometric detection was conducted in negative multiple reaction monitoring mode. Ion transitions were atm/z605.5 → 427.5 for fulvestrant andm/z608.5 → 430.5 for fulvestrant‐d3. The excellent linearity was demonstrated over the range 0.05–100.0 ng/ml (r2 = 0.99). The lower limit of quantitation was 0.05 ng/ml, which was superior to that reported in literature The method validation was evaluated by selectivity, accuracy, precision, recovery and matrix effect in agreement with the US Food and Drug Administration guidance. The method was successfully applied to a pharmacokinetic study of a novel fulvestrant microcrystal in rats after intramuscular administration. It revealed that the rate of absorption increases and the extent of absorption is constant with a decrease in microcrystal diameter.
Dissociated modulations of multivoxel activation patterns in the ventral and dorsal visual pathways by the temporal dynamics of stimuli
Authors: Li Jiaxin , Guo Bingbing , Cui Lin , Huang Hong , Meng Ming 
Published: June 2020

AbstractIntroductionPrevious studies suggested temporal limitations of visual object identification in the ventral pathway. Moreover, multivoxel pattern analyses (MVPA) of fMRI activation have shown reliable encoding of various object categories including faces and tools in the ventral pathway. By contrast, the dorsal pathway is involved in reaching a target and grasping a tool, and quicker in processing the temporal dynamics of stimulus change. However, little is known about how activation patterns in both pathways may change according to the temporal dynamics of stimulus change.MethodsHere, we measured fMRI responses of two consecutive stimuli with varying interstimulus intervals (ISIs), and we compared how the two visual pathways respond to the dynamics of stimuli by using MVPA and information‐based searchlight mapping.ResultsWe found that the temporal dynamics of stimuli modulate responses of the two visual pathways in opposite directions. Specifically, slower temporal dynamics (longer ISIs) led to greater activity and better MVPA results in the ventral pathway. However, faster temporal dynamics (shorter ISIs) led to greater activity and better MVPA results in the dorsal pathway.ConclusionsThese results are the first to show how temporal dynamics of stimulus change modulated multivoxel fMRI activation pattern change. And such temporal dynamic response function in different ROIs along the two visual pathways may shed lights on understanding functional relationship and organization of these ROIs.
Synthesis, Characterization, Molecular Docking, and Biological Activities of Some Natural and Synthetic Urolithin Analogs
Authors: Noshadi Bahareh , Ercetin Tugba , Luise Chiara , Yuksel Mine Yarim , Sippl Wolfgang , Sahin Mustafa Fethi , Gazi Mustafa , Gulcan Hayrettin Ozan 
Published: June 2020

AbstractUrolithins (that is, hydroxy substituted benzo[c]chromen‐6‐one derivatives) are formed within the gastrointestinal tract following to the exposure to various ellagitannin rich diet, particularly involving pomegranate, nuts, and berries. Regarding the bioavailability deficiency of ellagitannins, the biological activities obtained through the extracts of these dietaries are attributed to the urolithin compounds, since they are bioavailable. Particularly, there are studies indicating the importance of ellagitannin‐rich food for protective and alternative treatment of Alzheimer's Disease (AD). From this perspective, within this study, the major urolithins (that is, urolithins A and B), their methyl ether metabolites, as well as some synthetic urolithin analogs have been synthesized and screened for their biological activities in various enzyme inhibition (acetylcholinesterase, butyrylcholinesterase, monoamine oxidase B, cyclooxygenase 1, and cyclooxygenase 2) and antioxidant (DPPH radical scavenging) assay systems. The results pointed out the potential of urolithins to act as inhibitors on these receptors. Docking studies were also performed to investigate the possible interactions.
Transcatheter aortic valve replacement in patients with a history of cancer: Periprocedural and long‐term outcomes
Authors: Murphy Alexandra C. , Koshy Anoop N. , Cameron William , Horrigan Mark , Kearney Leighton , Yeo Belinda , Farouque Omar , Yudi Matias B. 
Published: June 2020

AbstractBackgroundA history of cancer is incorporated into the surgical risk assessment of patients undergoing surgical aortic valve replacement through the Society for Thoracic Surgeons score. However, the prognostic significance of cancer in patients treated with transcatheter aortic valve replacement (TAVR) is unclear. As the cancer survivorship population increases, it is imperative to establish the efficacy and safety of TAVR in patients with severe symptomatic aortic stenosis (AS) and a history of malignancy.ObjectivesThe primary goal of this study was to assess the periprocedural outcomes and long‐term mortality in patients with a history of cancer undergoing TAVR.MethodsA systematic review of PubMed, MEDLINE, and EMBASE was conducted to identify studies reporting outcomes in patients with a history of malignancy undergoing TAVR. A meta‐analysis was performed using a random‐effects model with a primary outcome of all‐cause mortality and cardiac mortality at the longest follow‐up. On secondary analyses, procedural safety was assessed.ResultsA total of 13 observational studies with 10,916 patients were identified in the systematic review. Seven studies including 6,323 patients were included in the quantitative analysis. Short‐term mortality (relative risk [RR] 0.61, 95%CI 0.36–1.01; p = .06) and long‐term all‐cause mortality (RR 1.24, 95%CI 0.95–1.63; p = .11) were not significantly different when comparing patients with and without a history of cancer. No significant difference in the rate of periprocedural complications including stroke, bleeding, acute kidney injury, and pacemaker implantation was noted.ConclusionIn patients with severe AS undergoing TAVR, a history of cancer was not associated with adverse short or long‐term survival. Based on these findings, TAVR should be considered in all patients with severe symptomatic AS, irrespective of their history of malignancy.
Signet‐ring cell large B‐cell lymphoma: A potential diagnostic pitfall with signet‐ring cell carcinoma
Authors: Patel Vijay , Pina‐Oviedo Sergio 
Published: June 2020

Key Clinical MessageThis study reveals the importance of recognizing uncommon histologic variants in diffuse large B‐cell lymphoma, such as the signet‐ring cell variant, which may result in an erroneous or delayed diagnosis with potential impact in patient treatment.
Two‐Dimensional Mesoporous Carbon Materials Derived from Fullerene Microsheets for Energy Applications
Authors: Xu Ting , Yu Danyang , Du Zhiling , Huang Wenhuan , Lu Xing 
Published: June 2020

AbstractPorous carbon materials rich in defects are promising candidates in energy storage and conversion applications. Herein, a facile template‐free approach is reported for the synthesis of a two‐dimensional (2 D) mesoporous carbon material derived from fullerene (C60) microsheets (FMSs) through simple heat treatment. The sample obtained at 1000 °C (FMS1000) shows a large surface area of 1507.6 m2 g−1 owing to the presence of mesopores and rich defects, which promote electron and mass transfer in the electrocatalytic process of the oxygen reduction reaction (ORR), showing an excellent performance with an onset potential of 0.95 V, a half‐wave potential of 0.85 V, and long‐term durability of 2000 cycles, comparable to the performance of commercial Pt/C. Moreover, FMS1000 displays a remarkable supercapacitive property with a specific capacitance of 330.7 F g−1 at 0.2 A g−1 and good long‐term stability with a capacitance retention of 97 % over 50 000 cycles. Thus, a practical strategy for the production of mesoporous carbon materials with different morphological structures and porous defects as high‐performance energy materials is advanced.
Ligand‐Enabled Palladium‐Catalyzed Through‐Space C−H Bond Activation via a Carbopalladation/1,4‐Pd Migration/C−H Functionalization Sequence
Authors: Chen Su , Ranjan Prabhat , Ramkumar Nagarajan , Van Meervelt Luc , Van der Eycken Erik V. , Sharma Upendra K. 
Published: June 2020

AbstractWe report, herein, a palladium‐catalyzed cascade comprising carbopalladation, 1,4‐Pd‐migration and C(sp2)−C(sp2) bond formation to construct a variety of bis‐heterocyclic frameworks in a single operational step. The methodology provides a direct approach to introduce an oxadiazole core at a remote location without any functional group obligation, with moderate to good yields.
Nanoisozymes: The Origin behind Pristine CeO2 as Enzyme Mimetics
Authors: Tan Zicong , Chen Yu‐Cheng , Zhang Jieru , Chou Jyh‐Pin , Hu Alice , Peng Yung‐Kang 
Published: June 2020

AbstractIt is known that the interplay between molecules and active sites on the topmost surface of a solid catalyst determines its activity in heterogeneous catalysis. The electron density of the active site is believed to affect both adsorption and activation of reactant molecules at the surface. Unfortunately, commercial X‐ray photoelectron spectroscopy, which is often adopted for such characterization, is not sensitive enough to analyze the topmost surface of a catalyst. Most researchers fail to acknowledge this point during their catalytic correlation, leading to different interpretations in the literature in recent decades. Recent studies on pristine Cu2O [Nat. Catal. 2019, 2, 889; Nat. Energy 2019, 4, 957] have clearly suggested that the electron density of surface Cu is facet dependent and plays a key role in CO2 reduction. Herein, it is shown that pristine CeO2 can reach 2506/1133 % increase in phosphatase‐/peroxidase‐like activity if the exposed surface is wisely selected. By using NMR spectroscopy with a surface probe, the electron density of the surface Ce (i.e., the active site) is found to be facet dependent and the key factor dictating their enzyme‐mimicking activities. Most importantly, the surface area of the CeO2 morphologies is demonstrated to become a factor only if surface Ce can activate the adsorbed reactant molecules.
Journey from Small‐Molecule Diyne Structures to 2D Graphdiyne: Synthetic Strategies
Authors: Li Yongjun , He Jingyi , Shen Han 
Published: June 2020

AbstractGraphdiyne (GDY) exhibits unique characteristics of a highly conjugated π system, evenly distributed nanopores, and a direct band gap. This has encouraged multidisciplinary research groups to investigate its application in energy conversion and storage, catalysts, electronic devices, sensing, and separation. Herein, the achievements of synthetic strategies for preparing small‐molecule diyne structures (GDY substructure), 1D nanoribbons, and 2D GDY are presented. These studies may help future investigations into the basic structure‐related properties of GDY and synthetic methodology for the future developments of GDY‐related 2D carbon materials.
Chemoselective Electrochemical Hydrogenation of Ketones and Aldehydes with a Well‐Defined Base‐Metal Catalyst
Authors: Fokin Igor , Siewert Inke 
Published: June 2020

AbstractHydrogenation reactions are fundamental functional group transformations in chemical synthesis. Here, we introduce an electrochemical method for the hydrogenation of ketones and aldehydes by in situ formation of a Mn‐H species. We utilise protons and electric current as surrogate for H2 and a base‐metal complex to form selectively the alcohols. The method is chemoselective for the hydrogenation of C=O bonds over C=C bonds. Mechanistic studies revealed initial 3 e− reduction of the catalyst forming the steady state species [Mn2(H−1L)(CO)6]−. Subsequently, we assume protonation, reduction and internal proton shift forming the hydride species. Finally, the transfer of the hydride and a proton to the ketone yields the alcohol and the steady state species is regenerated via reduction. The interplay of two manganese centres and the internal proton relay represent the key features for ketone and aldehyde reduction as the respective mononuclear complex and the complex without the proton relay are barely active.
Linkage Isomerism Leading to Contrasting Carboboration Chemistry: Access to Three Constitutional Isomers of a Borylated Phosphaalkene
Authors: Wilson Daniel W. N. , Mehta Meera , Franco Mauricio P. , McGrady John E. , Goicoechea Jose M. 
Published: June 2020

AbstractWe describe the reactivity of two linkage isomers of a boryl‐phosphaethynolate, [B]OCP and [B]PCO (where [B]=N,N’‐bis(2,6‐diisopropylphenyl)‐2,3‐dihydro‐1H‐1,3,2‐diazaboryl), towards tris‐ (pentafluorophenyl)borane (BCF). These reactions afforded three constitutional isomers all of which contain a phosphaalkene core. [B]OCP reacts with BCF through a 1,2 carboboration reaction to afford a novel phosphaalkene, E‐[B]O{(C6F5)2B}C=P(C6F5), which subsequently undergoes a rearrangement process involving migration of both the boryloxy and pentafluorophenyl substituents to afford Z‐{(C6F5)2B}(C6F5)C=PO[B]. By contrast, [B]PCO undergoes a 1,3‐carboboration process accompanied by migration of the N,N’‐bis(2,6‐diisopropylphenyl)‐2,3‐dihydro‐1H‐1,3,2‐diazaboryl to the carbon centre.
The Earlier the Better: Structural Analysis and Separation of Lanthanides with Pyrroloquinoline Quinone
Authors: Lumpe Henning , Menke Annika , Haisch Christoph , Mayer Peter , Kabelitz Anke , Yusenko Kirill V. , Guilherme Buzanich Ana , Block Theresa , Pöttgen Rainer , Emmerling Franziska , Daumann Lena J. 
Published: June 2020

AbstractLanthanides (Ln) are critical raw materials, however, their mining and purification have a considerable negative environmental impact and sustainable recycling and separation strategies for these elements are needed. In this study, the precipitation and solubility behavior of Ln complexes with pyrroloquinoline quinone (PQQ), the cofactor of recently discovered lanthanide (Ln) dependent methanol dehydrogenase (MDH) enzymes, is presented. In this context, the molecular structure of a biorelevant europium PQQ complex was for the first time elucidated outside a protein environment. The complex crystallizes as an inversion symmetric dimer, Eu2PQQ2, with binding of Eu in the biologically relevant pocket of PQQ. LnPQQ and Ln1Ln2PQQ complexes were characterized by using inductively coupled plasma mass spectrometry (ICP‐MS), infrared (IR) spectroscopy, 151Eu‐Mössbauer spectroscopy, X‐ray total scattering, and extended X‐ray absorption fine structure (EXAFS). It is shown that a natural enzymatic cofactor is capable to achieve separation by precipitation of the notoriously similar, and thus difficult to separate, lanthanides to some extent.
Bioprosthetic vs mechanical mitral valve replacement for infective endocarditis in patients aged 50 to 69 years
Authors: Hu Xingjian , Jiang Weiwei , Xie Minghui , Guo Ruikang , Yim Wai Yen , Dong Nianguo , Wang Yin 
Published: June 2020

AbstractBackgroundThe optimal choice of the valve prosthesis in mitral valve replacement (MVR) for infective endocarditis (IE) is controversial and challenging, particularly for younger patients.HypothesisThe postoperative outcomes of mechanical and biological MVR in IE patients aged 50 to 69 years are different.MethodsAll IE patients aged 50 to 69 years with primary MVR in Hubei province hospitals from 2002 to 2018 were retrospectively reviewed. The median duration of follow‐up was 8.7 years (IQR, 6.8‐10.9 years). Propensity score matching (1:3 ratio) was used to yield 492 patients with comparable baseline features between bioprostheses and mechanical prosthetic valve groups. Outcomes were postoperative mid‐ to long‐ term survival, mitral valve reoperation, prosthetic valve endocarditis (PVE), stroke, and major bleeding events.ResultsFifteen‐year survival after MVR was 80.6% in the mechanical valve group and 69.3% in the bioprostheses group (HR 0.545, P = .040). The cumulative incidence of mitral valve reoperation was 8.8% with mechanical valves and 21.4% with bioprostheses (HR 0.260, P = .002). The cumulative incidence of PVE was 5.6% with mechanical valves and 7.2% with bioprostheses (HR 0.629, P = .435). The cumulative incidence of stroke was 12.9% with mechanical valves and 10.5% with bioprostheses (HR 1.217, P = .647). The cumulative incidence of major bleeding was 12.0% with mechanical valves and 6.75% with bioprostheses (HR 1.579, P = .268).ConclusionsMechanical valve prostheses were associated with better survival, lower rates of reoperation compared with bioprostheses within 15 years after MVR in IE patients aged 50 to 69. These findings suggest mechanical valve prostheses may be a more reasonable alternative to bioprostheses in this patient group.