bluuebunny/crossref_metadata_2025_split huggingface dataset:
Low‐Toxicity ZnSe/ZnS Quantum Dots as Potent Photoreductants and Triplet Sensitizers for Organic Transformations
Authors: Nie Chengming , Lin Xuyang , Zhao Guohui , Wu Kaifeng 
Published: October 2022

AbstractColloidal quantum dots (QDs) can photocatalyze diverse organic reactions. However, reported QD‐photocatalysts often contain highly‐toxic elements Cd or Pb, and have not surpassed prototypical transition‐metal complexes in terms of their photoredox power or excited‐state energy. Here we report low‐toxicity ZnSe/ZnS core/shell QDs as potent visible photocatalysts to drive challenging organic transformations. To overcome the limitation of short excited‐state lifetime of the QDs, we functionalize their surfaces with benzophenone ligands which can rapidly extract electrons from photoexcited QDs and sustain long‐lived charge‐separated states. The benzophenone anions function as potent electron relay to drive dehalogenation of aryl chlorides and additive‐free polymerization of acrylates. Alternatively, the QDs are functionalized with biphenyl ligands to store energy in long‐lived, energetic triplets, enabling [2+2] homo‐cycloaddition of styrene and cycloaddition of carbonyls with alkenes.
Stereochemie steuert die Stärke der Diwasserstoffbrücken‐Bindungen in chiralen Amin‐Boran‐Addukten
Authors: Kemper Michael , Drost Deborah A. , Engelage Elric , Merten Christian 
Published: October 2022

AbstractDas wachsende Interesse an der Nutzung neuartiger Konzepte nicht‐kovalenter Wechselwirkungen in Katalysatoren und in der supramolekularen Chemie hat uns veranlasst, eine besondere Art von Wasserstoffbrückenbindungen erneut aufzugreifen: die Diwasserstoffbrückenbindung (dihydrogen bond, DHB), die zwischen einem klassischen Wasserstoffbrückenbindungs‐Donor und einem hydridischen Wasserstoff als Akzeptor gebildet wird. In diesem Beitrag wird durch Vergleich der Strukturen und Bindungsenthalpien verschiedener chiraler Amin‐Boran‐Addukte untersucht wie die Stärke der N−Hδ+⋅⋅⋅δ−H−B‐Wechselwirkung und damit eine durch DHB‐getriebene Selbstaggregation von sterischen Effekte bestimmt wird. Für ein Amin‐Boran Diastereomerenpaar, das aus einem chiralen sekundären Amin hergestellt wurde, wird gezeigt, dass die Stereochemie am Stickstoff einen signifikanten Einfluss auf die Wechselwirkungsenthalpie hat. Basierend auf dieser Erkenntnis können N‐chirale Amin‐Borane als interessante, supramolekulare Bausteine zur Feinabstimmung der Bildungsdynamiken von Assemblierungen betrachtet werden.
Spatially Directed Biosynthesis of Quantum Dots via Spidroin Templating in Escherichia coli
Authors: Chen Meng‐Ting , Hu Chun‐Fei , Huang Hai‐Bo , Qian Zhi‐Gang , Xia Xiao‐Xia 
Published: October 2022

AbstractSpatially directed synthesis of quantum dots (QDs) is intriguing yet challenging in organisms, due to the dispersed feature of templating biomolecules and precursors. Whether this task could be accomplished by biomolecular condensates, an emerging type of membraneless compartments in cells remains unknown. Here we report synthetic protein condensates for templated synthesis of QDs in bacterium Escherichia coli. This was realized by overexpression of spider silk protein to bind precursor ions and recruit other necessary components, which induced the spidroin to form more β‐sheet structures for assembly and maturation of the protein condensates. This in turn enabled formation and co‐localization of the fluorescent QDs to “light up” the condensates, and alleviated cytotoxicity of the precursor heavy metal ions and resulting QDs. Thus, our results suggest a new strategy for nanostructure synthesis and deposition in subcellular compartments with great potential for in situ applications.
Arylboration of Enecarbamates for the Synthesis of Borylated Saturated N‐Heterocycles
Authors: Trammel Grace L. , Kannangara Prashansa B. , Vasko Dmytro , Datsenko Oleksandr , Mykhailiuk Pavel , Brown M. Kevin 
Published: October 2022

AbstractTwo catalytic systems have been developed for the arylboration of endocyclic enecarbamates to deliver synthetically versatile borylated saturated N‐heterocycles in good regio‐ and diastereoselectivities. A Cu/Pd dual catalytic reaction enables the synthesis of borylated, α‐arylated azetidines, while a Ni‐catalysed arylboration reaction efficiently functionalizes 5‐, 6‐, and 7‐membered enecarbamates. In the case of the Cu/Pd‐system, a remarkable additive effect was identified that allowed for broader scope. The products are synthetically useful, as demonstrated by manipulations of the boronic ester to access biologically active compounds.
Hydrogen Drives Part of the Reverse Krebs Cycle under Metal or Meteorite Catalysis
Authors: Rauscher Sophia A. , Moran Joseph 
Published: October 2022

AbstractHydrogen (H2) is a geological source of reducing electrons that is thought to have powered the metabolism of the last universal common ancestor to all extant life, and that is still metabolized by various modern organisms. It has been suggested that H2drove a geochemical analogue of some or all of the reverse Krebs cycle at the emergence of the metabolic network, catalyzed by metals, but this has yet to be demonstrated experimentally. Herein, we show that three consecutive steps of the reverse Krebs cycle, converting oxaloacetate into succinate, can be driven without enzymes and in one‐pot by H2as the reducing agent under mild conditions compatible with biological chemistry. Low catalytic amounts of nickel (10–20 mol %) or platinum group metals (0.1–1 mol %) or even small amounts of ground meteorites were found to promote the reductive chemistry at temperatures between 5 and 60 °C and over a wide pH range, including pH 7. These results lend additional support to the hypothesis that geologically produced hydrogen and metal catalysts could have initiated early metabolic networks.
One‐dimensional metal–organic frameworks built by coordinating 2,4,6‐tris(4‐pyridyl)‐1,3,5‐triazine linker with copper nodes: CO2 adsorption properties
Authors: Portolés‐Gil Núria , Vallcorba Oriol , Fraile‐Sainz Julio , López‐Periago Ana M. , Domingo Concepción , Ayllón José A. 
Published: October 2022

The reaction between 2,4,6‐tris(4‐pyridyl)‐1,3,5‐triazine (4‐tpt) and copper(II) hexafluoroacetylacetone (Cu(hfa)2) yields two different 1D metal–organic frameworks (MOFs), [(Cu(hfa)2)2(4‐tpt)]n (1) and [Cu(hfa)2(4‐tpt)]n (2). The Cu:4‐tpt ratio in the new MOFs is determined by the reaction medium, particularly, the solvent used. The two compounds have been fully characterized, including crystal structure elucidation. [(Cu(hfa)2)2(4‐tpt)]n (1), with a 2:1 Cu:4‐tpt ratio, could be precipitated in either 1,1,2‐trichloroethane or supercritical CO2. In (1), 4‐tpt shows a tritopic coordination mode, but only half of the Cu(hfa)2 subunits act as a node, thus connecting two 4‐tpt and giving a 1D network. The other half of Cu(hfa)2 subunits are connected only to one pyridine and thus protrude along the chains. The later Cu(hfa)2 fragments show a labile character and can be dissolved in diethyl ether to give the second MOF [Cu(hfa)2(4‐tpt)]n (2), with a 1:1 Cu:4‐tpt ratio. The compound (2) has also a 1D structure, with all the incorporated copper atoms acting as nodes. In this case, the packing of the chains defines accessible channels, which are perpendicular to the chain axis. After activation, N2 adsorption/desorption measurements at 77 K confirm the microporous character of (2) with an apparent surface area of 190 m2 g−1. Besides, at 273 K this material clearly shows a significant adsorption of CO2 prompted by noncoordinated nitrogen in the triazine linker.
An efficient new method for electrospinning chitosan and heparin for the preparation of pro‐angiogenic nanofibrous membranes for wound healing applications
Authors: Shahzadi Lubna , Ramzan Amna , Anjum Awais , Jabbar Faiza , Khan Ather Farooq , Manzoor Faisal , Shahzad Sohail Anjum , Chaudhry Aqif Anwar , Rehman Ihtesham ur , Yar Muhammad 
Published: October 2022

AbstractChronic skin wounds and surgical sutures need critical care and fast recovery, robust connection of blood vessels and effective restoration of circulation is necessary in progressive wound healing. Heparin is well known for its' anticoagulant properties, VEGF activation and antithrombosis action. Chitosan aid in the development of the vascular grafts due to its ECM like properties of blood vessels. For electrospinning of Heparin negatively charged and low molecular weight positively charges chitosan, the homogenous solution is required, they precipitate out during mixing due to opposite charges. In the current study, a an efficient strategy is developed for the electrospinning of chitosan and heparin in the presence of lysozyme. The insolubility/non‐homogenous solution formation for electrospinning from charged chitosan and heparin fast acting was solved by using a small amount of N‐cetyl‐N,N,N‐trimethyl ammonium bromide (CTAB) and the resulting solution produced very smooth nanofibers. Polycaprolactone (PCL) was found to be a suitable polymer for the electrospinning of chitosan and heparin using organic and inorganic solvents. Surface morphology of the synthesized fibers was investigated by scanning electron microscopy (SEM) and the presence of functional groups was investigated by FTIR. Degradation studies were performed which revealed that lysozyme loaded materials were degraded much faster as compared to other materials. The angiogenic and biocompatible potential of heparin with 1 mg/ml and 4 mg/ml lysozyme concentration was demonstrated by chorionic allantoic membrane (CAM) assay and it was estimated that 1 mg/ml (lysozyme) loaded CS/HA material was found to be an efficient biomaterial to stimulate angiogenesis.
Bond strength and bond mechanism of injection over‐molded woven carbon fiber/PEEK‐short carbon fiber/PEEK composite components
Authors: Deng Tianzhengxiong , Huang Zhigao , Zheng Bing , Jiang Wei , Chen Lu , Chen Cheng , Zhou Helezi , Zhou Huamin 
Published: October 2022

AbstractA weak interface is formed between injected plastic and substrate during the injection over‐molding process. This study investigated the effects of mold temperature and melt temperature on the bond strength of injection over‐molded components, which were produced by injecting short carbon fiber reinforced polyether‐ether‐ketone (SCF/PEEK) onto the surface of woven carbon fiber reinforced PEEK (WCF/PEEK) laminate substrate. The results show that the interfacial laminar shear strength (ILSS) increases significantly from 15.8 to 50.0 MPa as the mold temperature raises from 190 to 260°C. The ILSS increases first and then decreases with melt temperature raises from 380 to 420°C, achieving a maximum value of 44.4 MPa at 410°C melt temperature. Crystallinity analysis and microscopic observations indicate different bonding modes are formed at the interface. The matrix tangling appears in the matrix enrichment area, interlocking, and tangling appear in the pits and weak tangling and cracks occur on the fiber surface. The mold temperature affects the ILSS by changing the crystallization property and the connection mode in the interface, while the melt temperature affects the ILSS by changing the area of the matrix entanglement. The relationship between the process conditions—interfacial microstructure—interfacial mechanical performance was discussed.
Photovoltaic performance of mixed cation K0.005MA0.995PbI3‐based perovskite solar module
Authors: Singh Harpreet , Dhakla Shweta , Deendyal Parvesh K. , Kumar Anand , Kumar Sarvesh , Kashyap Manish K. 
Published: October 2022

AbstractHybrid halide perovskites (HHPs) are attracting large attention due to their excellent photovoltaic characteristics. MAPbI3 (MA = CH3NH3) based solar cells are widely studied both on experimental and theoretical fronts. Alkali metal ion doping in the absorbing layer material (MAPbI3) of HHP solar cells is helpful for enhancing the photovoltaic performance and stability of the complete solar module. In present work, a complete perovskite solar module with K‐doped MAPbI3 absorbing layer has been simulated numerically. The effect of various parameters such as thickness, defect density, series, and shunt resistances on device performance has been studied. After optimizing these parameters, a device with the maximum possible efficiency (20.69%) has been reported. The reproducibility of solar cells before and after optimization has also been compared with respect to the variation in carrier mobilities in absorber layer material. Higher reproducibility of the optimized device has been obtained as compared to the pristine device. This present work contains adequate information to run an experimental trial for designing solar module containing K‐doped MAPbI3 absorbing layer.
Reset of Inflammatory Priming of Joint Tissue and Reduction of the Severity of Arthritis Flares by Bromodomain Inhibition
Authors: Friščić Jasna , Reinwald Christiane , Böttcher Martin , Houtman Miranda , Euler Maximilien , Chen Xi , Walker Kellie I. , Kirchner Philipp , Zhu Honglin , Wirth Benjamin , Weidner Daniela , Krüger René , Trajkovic Vladimir , Ekici Arif B. , Klein Kerstin , Mougiakakos Dimitrios , Ospelt Caroline , Schett Georg , Hoffmann Markus H. 
Published: October 2022

ObjectiveWe have recently shown that priming of synovial fibroblasts (SFs) drives arthritis flares. Pathogenic priming of SFs is essentially mediated by epigenetic reprogramming. Bromodomain and extraterminal motif (BET) proteins translate epigenetic changes into transcription. Here, we used a BET inhibitor (I‐BET151) to target inflammatory tissue priming and to reduce flare severity in a murine experimental arthritis model.MethodsBALB/c mice were treated by intraperitoneal injection or by local injection in the paw with I‐BET151, which blocks the interaction of BET proteins with acetylated histones. We assessed the effects of I‐BET151 on acute arthritis and/or inflammatory tissue priming in a model of repeated injections of monosodium urate crystals or zymosan into the mouse paw. I‐BET151 was given before arthritis induction, at peak inflammation, or after healing of the first arthritis bout. We performed transcriptomic (RNA‐Seq), epigenomic (ATAC‐Seq), and functional (invasion, cytokine production, migration, senescence, metabolic flux) analyses of murine and human SFs treated with I‐BET151 in vitro or in vivo.ResultsSystemic I‐BET151 administration did not affect acute inflammation but abolished inflammatory tissue priming and diminished flare severity in both preventive and therapeutic treatment settings. I‐BET151 was also effective when applied locally in the joint. BET inhibition also inhibited osteoclast differentiation, while macrophage activation in the joint was not affected. Flare reduction after BET inhibition was mediated, at least in part, by rolling back the primed transcriptional, metabolic, and pathogenic phenotype of SFs.ConclusionInflammatory tissue priming is dependent on transcriptional regulation by BET proteins, making them promising therapeutic targets for prevention of arthritis flares in previously affected joints.
The highest percentage of Gleason Pattern 4 is a predictor in intermediate‐risk prostate cancer
Authors: Sato Shun , Kimura Takahiro , Onuma Hajime , Egawa Shin , Shimoda Masayuki , Takahashi Hiroyuki 
Published: October 2022

AbstractObjectivesThis study aims to clarify the clinicopathological significance of several novel pathological markers, including the percentage of Gleason pattern 4 and small/non‐small cribriform pattern, in intermediate‐risk Gleason score 3 + 4 = 7 prostate cancer.Subjects and MethodsTwo‐hundred and twenty‐eight patients with Gleason score 3 + 4 = 7 intermediate‐risk prostate cancer who underwent radical prostatectomy between 2009 and 2019 at our institute were selected. Preoperative clinicopathological characteristics, including serum prostate‐specific antigen level, clinical T stage, percentage of cancer‐positive cores at biopsy, small/non‐small cribriform pattern, the highest percentage of Gleason pattern 4, the total length of Gleason pattern 4 and percentage of Gleason score 7 cores were examined in univariate/multivariate logistic regression analysis to determine their predictive value for postoperative adverse pathological findings, defined as an upgrade to Gleason score 4 + 3 = 7 or higher, pN1 or pT3b disease.ResultsFifty‐four cases (23.7%) showed adverse pathological findings. Although a non‐small cribriform pattern, highest Gleason pattern 4 percentage and total length of Gleason pattern 4 were predictive of adverse pathological findings in univariate analysis, only the highest Gleason pattern 4 percentage was an independent predictive factor in multivariate analysis (odds ratio: 1.610; 95% confidence interval: 1.260–2.070; P = 0.0002).ConclusionThe highest Gleason pattern 4 percentage was a potent predictive parameter for Gleason score 3 + 4 = 7 intermediate‐risk prostate cancer and should be considered in the risk classification scheme for prostate cancer.
The agony of choice: Impact of the host animal species on the enzyme‐linked immunosorbent assay performance for host cell protein quantification
Authors: Seisenberger Christina , Graf Tobias , Sticht Sarah , Haindl Markus , Mohn Ulrich , Wegele Harald , Wiedmann Michael , Wohlrab Stefanie 
Published: October 2022

AbstractHost cell proteins (HCPs) are inevitable process‐related impurities in biotherapeutics commonly monitored by enzyme‐linked immunosorbent assays (ELISAs). Of particular importance for their reliable detection are the anti‐HCP polyclonal antibodies (pAbs), supposed to detect a broad range of HCPs. The present study focuses on the identification of suitable host animal species for the development of high‐performance CHO‐HCP ELISAs, assuming the generation of pAbs with adequate coverage and specificity. Hence, antibodies derived from immunization of sheep, goats, donkeys, rabbits, and chickens were compared concerning their amount of HCP‐specific antibodies, coverage, and performance in a sandwich ELISA. Immunization of sheep, goats, donkeys, and rabbits met all test criteria, whereas the antibodies from chickens cannot be recommended based on the results of this study. Additionally, a mixture of antibodies from the five host species was prepared to assess if coverage and ELISA performance can be improved by a multispecies approach. Comparable results were obtained for the single‐ and multispecies ELISAs in different in‐process samples, indicating no substantial improvement for the latter in ELISA performance while raising ethical and financial concerns.
An empirical study on the evaluation system of innovation and entrepreneurship education in applied universities
Authors: Wang Wenhao , Qiu Dong , Chen Xiaobing , Yu Zhenyang 
Published: October 2022

AbstractRegarding the difficulties in the assessment of innovation and entrepreneurship teaching capability currently like biased qualitative assessment and less nonlinear quantitative assessment and insufficient assessment efficiency, an assessment model of innovation and entrepreneurship education targeted at local University students on the foundation of the Back Propagation (BP) neural network is designed. First, the contents of the questionnaire are carefully designed, on whose basis the assessment index system is built. Then, a BP neural network model is utilized for the purpose of comprehensively evaluating the collected data. Lastly, we carry out a demonstration study on innovation and entrepreneurship education, whose results reveal the students' professional knowledge and skills, participation in national competitions, and centralized entrepreneurship training camp play a key role and have a profound effect on innovation and entrepreneurship capability. The evaluation system is able to effectively assess the actual effects of innovation and entrepreneurship education, direct teachers' instructional activity, as well as motivate students to learn and practice.
Biosensor Characterization from Cratylia mollis Seed Lectin (Cramoll)‐MOF and Specific Carbohydrate Interactions in an Electrochemical Model
Authors: de Carvalho Maryana Hermínio , de Araújo Hallysson Douglas Andrade , da Silva Renata Pereira , dos Santos Correia Maria Tereza , de Freitas Katia Cristina Silva , de Souza Sandra Rodrigues , Barroso Coelho Luana Cassandra Breitenbach 
Published: October 2022

AbstractBiosensors are small devices known for their selectivity, high specificity and sensitivity to the respective analyte, at low concentrations. We developed an electrochemical biosensor using the crystalline polymer MOF‐[Cu3(BTC)2(H2O)2]n to characterize Cratylia mollis seed lectin (Cramoll) and its interaction with free carbohydrate (glucose) and carbohydrates on the surface of rabbit erythrocytes. The electrochemical potentials presented by the exponential curves that vary from 96 to 142 mV in relation to concentrations of 10 to 20 mM of glucose are decisive for the use of the system containing gold electrode/MOF/Cramoll for the characterization of biological models due to its high sensitivity. As well as the kinetic behavior presented in the cyclic voltammograms, with a cathodic current response of 0.000 3 A for a glucose concentration of 15 mM. These results were due to the high specificity of Cramoll under these conditions, promoting stability of surface charges at the Cramoll/electrode interface. This phenomenon facilitates the monitoring of the interaction with free glucose present in the electrolyte medium by potentiometric and amperometric methods and with carbohydrates present on the surface of rabbit erythrocytes through the potentiometric method. Through scanning electron microscopy (SEM) it was possible to observe Cramoll immobilized on the MOF surface, proving the specificity of the ligand (glucose‐lectin) through the morphological lectin changes in this process. This electrochemical model, Cramoll/MOF biosensor, is effective for evaluating free lectin/carbohydrate or in the erythrocyte membrane.
The Mechanism of Crocetin Targeting Cardiovascular Disease Based on Network Pharmacology Constrained by Spectral Experiments
Authors: Geng Zhaoming , Guo Ming , Zhou Qingteng , Pan Lanying 
Published: October 2022

AbstractThe network pharmacology under conditions is a recent development trend. We use network pharmacology methods to analyze the mechanism of crocetin (CRO) that regulates cardiovascular diseases. In this work, the spectral experimental data of CRO‐Protein interaction is first time combined with constraint conditions to solve the problems of targeting redundancy and lack of verification. CRO targets and cardiovascular disease targets were obtained by the target database. The STRING platform was used for PPI analysis. The GO and KEGG pathways of the target were analyzed using the Metascape platform; The core functional targets of CRO were screened by molecular docking techniques and the spectra of CRO and human serum albumin (HSA). Under the collaborative constraint conditions, the core targets of CRO that regulate cardiovascular diseases are ADRA1A, ADRA1B, CHRM1, CHRM2, GABRA1, and PTGS2; This study incorporates spectroscopy and molecular docking as constraints into the network pharmacological analysis, which significantly improves the credibility of network pharmacological analysis compared with unconstrained conditions. This method provides theoretical references for the in‐depth study of the mechanism between active substances and protein targets for other medicines in network pharmacology.