bluuebunny/crossref_metadata_2025_split huggingface dataset:
Selective CO2 Photoreduction to CH4 via Pdδ+‐Assisted Hydrodeoxygenation over CeO2 Nanosheets
Authors: Wang Zhiqiang , Zhu Juncheng , Zu Xiaolong , Wu Yang , Shang Shu , Ling Peiquan , Qiao Panzhe , Liu Chengyuan , Hu Jun , Pan Yang , Zhu Junfa , Sun Yongfu , Xie Yi 
Published: May 2022

AbstractHere, noble‐metal‐doped two‐dimensional metal oxide nanosheets are designed to realize selective CO2 photoreduction to CH4. As a prototype, Pd‐doped CeO2 nanosheets are fabricated, where the active sites of Pdδ+ (2<δ<4) and Ce3+−Ov are revealed by quasi in situ X‐ray photoelectron spectra and in situ electron paramagnetic resonance spectra. Moreover, in situ Fourier‐transform infrared spectra of D2O photodissociation and desorption verify the existence of the Pd−OD bond, implying that Pdδ+ sites can participate in water oxidation to deliver H* species for facilitating the protonation of the intermediates. Furthermore, theoretical calculations suggest the Pd doping could regulate the formation energy barrier of the key intermediates CO* and CH3O*, thus making CO2 reduction to CH4 become the favorable process. Accordingly, Pd‐doped CeO2 nanosheets achieve nearly 100 % CH4 selectivity of CO2 photoreduction, with the raising CH4 evolution rate of 41.6 μmol g−1 h−1.
Regioselective Fluoroalkylphosphorylation of Unactivated Alkenes by Radical‐Mediated Alkoxyphosphine Rearrangement**
Authors: Xie Dong‐Tai , Chen Hong‐Lei , Wei Dian , Wei Bang‐Yi , Li Zheng‐Hu , Zhang Jian‐Wu , Yu Wei , Han Bing 
Published: May 2022

AbstractA novel distal radical rearrangement of alkoxyphosphine is developed for the first time and applied to the regioselective radical fluoroalkylphosphorylation of unactivated olefins. By employing a one‐pot two‐step reaction of (bis)homoallylic alcohols, organophosphine chlorides, and fluoroalkyl iodides under CFL (compact fluorescence light) irradiation, a series of fluoroalkylphosphorylated alkyl iodides and alcohols are easily synthesized by regiospecific installing a phosphonyl onto the inner carbon of terminal olefins and further iodination/hydroxylation. Mechanism studies reveal that the migration undergoes a distinctive radical cyclization/β‐scission on the lone electron pair of phosphorus, resulting in C−P bond formation and C−O bond cleavage.
Directing the Morphology, Packing, and Properties of Chiral Metal–Organic Frameworks by Cation Exchange**
Authors: Nasi Hadar , Chiara di Gregorio Maria , Wen Qiang , Shimon Linda J. W. , Kaplan‐Ashiri Ifat , Bendikov Tatyana , Leitus Gregory , Kazes Miri , Oron Dan , Lahav Michal , van der Boom Milko E. 
Published: May 2022

AbstractWe show that metal–organic frameworks, based on tetrahedral pyridyl ligands, can be used as a morphological and structural template to form a series of isostructural crystals having different metal ions and properties. An iterative crystal‐to‐crystal conversion has been demonstrated by consecutive cation exchanges. The primary manganese‐based crystals are characterized by an uncommon space group (P622). The packing includes chiral channels that can mediate the cation exchange, as indicated by energy‐dispersive X‐ray spectroscopy on microtome‐sectioned crystals. The observed cation exchange is in excellent agreement with the Irving–Williams series (Mn<Fe<Co<Ni< Cu>Zn) associated with the relative stability of the resulting coordination nodes. Furthermore, we demonstrate how the metal cation controls the optical and magnetic properties. The crystals maintain their morphology, allowing a quantitative comparison of their properties at both the ensemble and single‐crystal level.
Silicon‐Stereogenic Monohydrosilane: Synthesis and Applications
Authors: Wu Yichen , Wang Peng 
Published: May 2022

AbstractOptically active organosilanes have been demonstrated to be versatile chiral reagents in synthetic chemistry since the early seminal contributions by Sommer and Corriu. Among these silicon‐containing chiral architectures, monohydrosilanes, which bear a Si−H bond, hold a unique position because of their facile transformations through stereospecific Si–carbon or Si–heteroatom bond‐formation reactions. In addition, those compounds have also been leveraged as chiral reagents for alcohol resolution, chiral auxiliaries, mechanistic probes, as well as potential optoelectronic materials. This Minireview comprehensively summarizes the synthesis and synthetic applications of silicon‐stereogenic monohydrosilanes, particularly the advances in the transition‐metal‐catalyzed asymmetric synthesis of this class of functional molecules.
Ein planarer aromatischer Fünfring stabilisiert durch nur zwei π‐Elektronen
Authors: Kysliak Oleksandr , Schreiner Simon H. F. , Grabicki Niklas , Liebing Phil , Weigend Florian , Dumele Oliver , Kretschmer Robert 
Published: May 2022

AbstractViele der heute bekannten Chemikalien sind teilweise oder vollständig aromatisch, da ein Ringgerüst durch die Delokalisierung von π‐Elektronen eine zusätzliche Stabilisierung erfährt. Während aromatische Ringe mit gleicher Anzahl an π‐Elektronen und Ringatomen wie beispielsweise Benzol besonders stabil sind, sind solche mit den mindestens erforderlichen zwei π‐Elektronen sehr selten und blieben bislang auf drei‐ und viergliedrige Ringe beschränkt, sofern sie nicht in der Koordinationssphäre von Schwermetallen stabilisiert wurden. Hier berichten wir über die einfache Synthese eines Dikaliumcyclopentagallens, ein einzigartiges Beispiel für einen fünfgliedrigen aromatischen Ring, der durch nur zwei π‐Elektronen stabilisiert wird. Einkristall‐Röntgenstrukturanalyse ergab einen planaren Ga5‐Ring mit nahezu gleichen Gallium–Gallium‐Bindungslängen, was zusammen mit spektroskopischen und theoretischen Daten dessen aromatischen Charakter untermauert. Unsere Ergebnisse belegen, dass die aromatische Stabilisierung weit über das hinausgeht, was bisher als minimale π‐Elektronenzahl für fünfatomige Ringfragmente angenommen wurde.
Exploring the Influence of Inter‐ and Intra‐crystal Diversity of Surface Barriers in Zeolites on Mass Transport by Using Super‐Resolution Microimaging of Time‐Resolved Guest Profiles
Authors: Peng Shichao , Xie Yiwei , Wang Linying , Liu Wenjuan , Li Hua , Xu Zhaochao , Ye Mao , Liu Zhongmin 
Published: May 2022

AbstractThe applications of nanoporous crystalline materials are closely related to the mass transfer of guest molecules. However, the fundamental knowledge of mass transfer, and in particular the surface barriers controlled by the permeation of guest molecules through the external surfaces of materials, is still incomplete. The diversity of surface permeability at the single‐crystal level, caused by the varying origins of surface transport resistance, hinders the rational materials design and needs better understanding. Herein, we probe the molecular transport in single zeolite crystals with fluorescent 4‐(4‐diethylaminostyryl‐1‐methylpyridinium iodide) (DAMPI) using super‐resolution structured illumination microscopy (SIM). It showed that both the inter‐ and intra‐crystal diversity of surface barriers could be monitored by detecting the diffusion behaviors on the center and surface planes in single crystals. This adds a new perspective for studying the origins of the surface barriers as well as the molecular transport mechanisms in nanoporous materials.
Synthesis of a new adsorbent poly(allylisothiocyanate‐co‐hydroxyethylmethacrylate‐co‐vinylimidazole) via photopolymerization: Characterization and investigation of heavy metal adsorption capacity
Authors: Saltan Fehmi , Saltan Gözde Murat 
Published: May 2022

AbstractWe report the copolymerization synthesis of novel poly(allylisothiocyanate‐co‐hydroxyethylmethacrylate‐co‐vinylimidazole) (PAHV) adsorbents for potential applications in the heavy metal removals. In the present study, the copolymerization reaction was introduced by photopolymerization using benzophenone as the photoinitiator. The chemical structure in the PAHV adsorbents was monitored and evaluated by Fourier transform infrared spectroscopy, 1H‐nuclear magnetic resonance, andX‐ray photoelectron spectroscopy measurements. Surface analysis and molecular weight distribution of PAHV adsorbents were performed by scanning electron microscopy and gel permeation chromatography analysis, respectively. The adsorption method, which is one of the most effective techniques, was used for the elimination of heavy metal ions from aqueous solutions in this study. In order to understand the adsorption capacity and removal efficiency of heavy metal ions by PAHV, the effects of pH value and monomer ratio in the adsorbents were investigated. Inductively coupled plasma mass spectrometry device was used for these analyses. The optimum pH values for adsorption capacity and removal efficiency of heavy metal ions have been 6–8. The removal efficiency of heavy metal ions by the various PAHV adsorbents decreased in the order: Cd2+ > Pb2+ > Co3+ > Cr3+ > Ni2+ > Cu2+.
Recent progress of mechanism of mineralization process induced by Ta2O5/PCL scaffolds
Authors: Gao Chen , Jiang Junbo , Wang Juan , Wang Yutong , Zhang Yangyang , Rao Caihua , Cheng Yue , Chen Zhongrong , Yang Runhuai , Zhao Gang 
Published: May 2022

AbstractMineralization of hydroxyapatite mineralized by acidic metal oxides has attracted substantial research interest in the research and development of orthopedic substitutes. In this study, Polycaprolactone (PCL) nanofibers with nano‐tantalum oxide (Ta2O5) were successfully fabricated through electrospinning. The scaffold simulates the mineralization process of hydroxyapatite in simulated body fluid. However, in the process of mineralization, there is a chemical reaction between hydrophobic scaffolds and acid oxides, which is believed to have a significant impact on the biological effects of the scaffolds. The results of SEM, EDS, XRD, Mapping, FTIR, GPC, 13CNMR, and 1HNMR explain the principle of hydroxyapatite mineralization by Ta2O5 and the reason why the composite scaffold is blurred, that is, the carbonyl carbon of PCL attacked by the surface hydroxyl groups of Ta2O5 to catalyze its ring‐opening polymerization to synthesize PCL/Ta2O5 nanocomposites in one step. In order to accurately explore the effect of this reaction on the metabolism of biological macromolecules in the future, we provide a detailed route of Ag Nanoparticles ‐Dimercaptosuccinic acid@Transcription activator (AgNPs‐DMSA@TAT) probe synthesis. The results provide a reference for the sedimentation of hydroxyapatite induced by acid oxides and its effect on traditional electrospun fiber scaffolds.
Reducing dynamic heat build‐up of styrene butadiene rubber/carbon black by filling aramid pulp coated with natural rubber latex
Authors: Wang Xingyu , Ji Yongchun , Luo Zhu , Zhang Hao , Zhong Jincheng , Liang Jiuming 
Published: May 2022

AbstractThe manufacture of green tires with low heat build‐up has attracted extensive attention. Furthermore, the trouble to solve the problem of rubber failure caused by tires dynamic heat build‐up is a great challenge faced by the automotive tire industry. In this article, a method of preparing styrene butadiene rubber/carbon black/aramid pulp‐natural rubber latex (SBR/CB/AP‐NRL) composites was described in detail, which used AP coated with NRL to fill SBR/CB. A flexible interface layer was constructed between fibers and rubber matrix, making for forming a large specific surface area of the NRL. The mechanism of reducing heat build‐up of the rubber composite through “deforming transformation” in the flexible interface layer was discussed. In addition, the NRL interface layer contributed to the dispersion of the AP in the rubber matrix and the good interfacial bonding between AP and the rubber matrix. In the experiment of replacing a part of CB with a certain content of AP‐NRL, it was found that the temperature rise of the rubber composites decreased by 8.33% with 1 phr modified AP replacing 5 phr CB. The strategy of reducing dynamic heat build‐up of rubber composite provides a new idea for the development of green tire.
Novel isoxazoline‐linked 1,3,4‐thiadiazole hybrids as anticancer agents: Design, synthesis, biological evaluation, molecular docking, and molecular dynamics simulation
Authors: Oubella Ali , Byadi Said , Bimoussa Abdoullah , Fawzi Mourad , Auhmani Aziz , Podlipnik Crtomir , Morjani Hamid , Riahi Abdelkhalek , Robert Anthony , Itto My Youssef A. 
Published: May 2022

AbstractIn the current study, natural (R)‐carvone was utilized as a starting material for the efficient synthesis of two series of isoxazoline derivatives bearing the 1,3,4‐thiadiazole moiety. The new compounds were obtained in good yields and were characterized by 1H and 13C NMR and HRMS analysis. The newly synthesized monoterpenic isoxazoline 1,3,4‐thiadiazole and their thiosemicarbazone intermediate derivatives were evaluated for their anticancer activity in four cancer cell lines (HT‐1080, A‐549, MCF‐7, and MDA‐MB‐231). Most of the synthesized compounds exhibited moderate to high anticancer effects. Compound 13c showed the highest anticancer activity with IC50 values ranging from 19.33 ± 1.81 to 34.81 ± 3.03 µM. Further investigation revealed that compounds 12e and 13c could inhibit the cell growth of HT‐1080 and MCF‐7 cells by inducing apoptosis through caspase‐3/7 activation. The apoptotic effect was accompanied by an S phase and G2/M cell cycle arrest for 13c and 12e, respectively. Compounds 12e and 13c were assessed in silico using molecular docking and molecular dynamics. We found that compound 13c is moderately active against the caspase‐3 protein, which triggers apoptosis via intrinsic and extrinsic routes, making compound 13c a promising candidate to activate the proapoptotic protein (caspase‐3).
At the crossroads of logics: Automating newswork with artificial intelligence—(Re)defining journalistic logics from the perspective of technologists
Authors: Sirén‐Heikel Stefanie , Kjellman Martin , Lindén Carl‐Gustav 
Published: May 2022

AbstractAs artificial intelligence (AI) technologies become more ubiquitous for streamlining and optimizing work, they are entering fields representing organizational logics at odds with the efficiency logic of automation. One such field is journalism, an industry defined by a logic enacted through professional norms, practices, and values. This paper examines the experience of technologists developing and employing natural language generation (NLG) in news organizations, looking at how they situate themselves and their technology in relation to newswork. Drawing on institutional logics, a theoretical framework from organizational theory, we show how technologists shape their logic for building these emerging technologies based on a theory of rationalizing news organizations, a frame of optimizing newswork, and a narrative of news organizations misinterpreting the technology. Our interviews reveal technologists mitigating tensions with journalistic logic and newswork by labeling stories generated by their systems as nonjournalistic content, seeing their technology as a solution for improving journalism, enabling newswork to move away from routine tasks. We also find that as technologists interact with news organizations, they assimilate elements from journalistic logic beneficial for benchmarking their technology for more lucrative industries.
Downregulation of TGIF2 is possibly correlated with neuronal apoptosis and autism‐like symptoms in mice
Authors: Lei Jing , Deng Yijue , Ma Songdong 
Published: May 2022

AbstractBackgroundTGFB‐induced factor homeobox 2 (TGIF2) has been reported to exert essential functions in brain development. This study aimed to elucidate the correlation of TGIF2 with autism, a neurodevelopmental condition which presents with severe communication problems.MethodsAn autism‐related gene expression dataset GSE36315 was used to analyze aberrantly expressed genes in autistic brain tissues. Maternal mice were treated with valproate (VPA), and their offspring were selected as model mice with autism. The functions of TGIF2 in autism‐like symptoms in mice were examined by behavioral tests and histological examination of their hippocampal tissues. Mouse hippocampal neurons were extracted for in vitro studies. A gene set enrichment analysis was performed to analyze the signaling pathways involved, and the upstream factors influencing TGIF2 expression were explored in the ENCODE database and validated by ChIP‐qPCR assays.ResultsTGIF2 was poorly expressed in autistic patients in the GSE36315 dataset as well as in the temporal cortex tissues of autistic mice. Adenovirus‐mediated overexpression of TGIF2 suppressed autism‐like symptoms and neuronal apoptosis in autistic mice. TGIF2 activated the Wnt/β‐catenin signaling pathway. TGIF2 could be regulated by monomethylation of histone H3 Lys4 (H3K4me1). The histone demethylase LSD1 was highly expressed in the tissues of autistic mice and bound to TGIF2 promoter, which was possibly responsible for TGIF2 downregulation.ConclusionThis research suggests that the downregulation of TGIF2, possibly regulated by LSD1/H3K4me1, is correlated with neuronal apoptosis and development of autism in mice through the inactivation of the Wnt/β‐catenin pathway.
Cell‐Free Protein Synthesis for the Screening of Novel Azoreductases and Their Preferred Electron Donor
Authors: Rolf Jascha , Ngo Anna Christina Reyes , Lütz Stephan , Tischler Dirk , Rosenthal Katrin 
Published: May 2022

AbstractAzoreductases are potent biocatalysts for the cleavage of azo bonds. Various gene sequences coding for potential azoreductases are available in databases, but many of their gene products are still uncharacterized. To avoid the laborious heterologous expression in a host organism, we developed a screening approach involving cell‐free protein synthesis (CFPS) combined with a colorimetric activity assay, which allows the parallel screening of putative azoreductases in a short time. First, we evaluated different CFPS systems and optimized the synthesis conditions of a model azoreductase. With the findings obtained, 10 azoreductases, half of them undescribed so far, were screened for their ability to degrade the azo dye methyl red. All novel enzymes catalyzed the degradation of methyl red and can therefore be referred to as azoreductases. In addition, all enzymes degraded the more complex and bulkier azo dye Brilliant Black and four of them also showed the ability to reduce p‐benzoquinone. NADH was the preferred electron donor for the most enzymes, although the synthetic nicotinamide co‐substrate analogue 1‐benzyl‐1,4‐dihydronicotinamide (BNAH) was also accepted by all active azoreductases. This screening approach allows accelerated identification of potential biocatalysts for various applications.
Supporting young people's cognition and communication in the courtroom: A scoping review of current practices
Authors: Turner Kim , Hughes Nathan 
Published: May 2022

AbstractBackgroundA recent meta‐analysis suggested that the majority of young people in contact with the criminal justice system have cognitive and/or communication impairments. Over the past 20 years, recognition of these complex needs has resulted in support measures being put in place in courtrooms across the globe. It is therefore timely to review evidence for the efficacy of these measures.AimsThis scoping review evaluates evidence on support measures employed to facilitate access to court proceedings for individuals with cognition and communication impairments, and considers how this evidence might inform future research and practice.MethodsResearch databases were searched for studies that: directly or indirectly involved a population with a form of functional impairment and/or diagnosed neurodevelopmental disorder; and refer to support delivered to remove barriers or support access to courtroom processes.ResultsSearches identified 3,318 distinct articles. Following review, 37 papers were identified for inclusion. The papers were published between 1993 and 2019, with the majority being published since 2010 (n = 23). The majority of papers were from the United Kingdom (n = 26); other countries represented were Australia (n = 1), Canada (n = 3), New Zealand (n = 2), UK papers don't necessarily state which countries involved (n = 2) Scotland specifically state Scotland only and the United States (n = 3). No papers met the criteria for an experimental research design.ConclusionsWhilst the high level of need in this population is well established, which support measures are most effective in enabling engagement in court processes is not currently clear. More robust evaluative research is therefore required to establish the most effective methods of support. Despite this lack of evidence regarding outcomes, both young people and professionals generally view support measures favourably. There is an increasing onus on professionals to adapt their practice rather than to support/enhance the cognition and communication skills of young people.
Detection and Treatment of Persistent Pollutants in Water: General Review of Pharmaceutical Products
Authors: Bustos Bustos Erika , Sandoval‐González Antonia , Martínez‐Sánchez Carolina 
Published: May 2022

AbstractEnvironmental problems of great complexity arise from the enormous number of toxic substances that are generated by anthropogenic activities. Seemingly, society encounters new issues every day thus these problems seem to be endless. Now in the face of the COVID‐19 pandemic and the SARS‐CoV‐2 crisis, a large number of emerging treatment compounds generated by pharmaceutical companies worldwide makes future issues even more treacherous. For this reason, there is an increasing need to detect and treat emerging compounds to prevent them from becoming persistent pollutants. This review describes the advances in the use of electrochemical sensors with modified carbon‐based electrodes among other issues, to determine antibiotics, anti‐inflammatories and antidepressants levels in the environment. It further explores technologies suggested for cleaning wastewater polluted by pharmaceutical products using biological or advanced oxidation processes including photolysis, photocatalysis, microwave heating, ultrasound, Fenton, electro‐Fenton, photoelectro‐Fenton and various combined treatments.
Fluid structure interaction versus rigid‐wall approach in the study of the symptomatic stenosed carotid artery: Importance of wall compliance and resilience of loose connective tissue
Authors: Jodko Daniel , Jeckowski Mateusz , Tyfa Zbigniew 
Published: May 2022

AbstractThe purpose of this paper is to demonstrate the importance of a compliant wall approach in modeling of non‐Newtonian and non‐physiological blood flows. A case study of a stenosed and symptomatic carotid bifurcation was considered to show the influence of the wall‐resilience assumption on the flow parameters obtained with numerical simulations. Patient‐specific data concerning the geometry and flow conditions were collected and used to carry out two‐way coupled fluid structure interaction simulations of the pulsatile blood flow through carotid artery. The wall compliance was considered separately as related to the wall‐elasticity and as associated with the reaction of the loose connective tissue surrounding the carotid bifurcation. The obtained hemodynamic parameters were compared to those which were found in rigid‐wall simulations. The difference between the results obtained for rigid‐wall and compliant‐wall approaches for the peak‐systolic area‐averaged wall shear stress achieved 35%, whereas the difference between the time‐averaged local vorticity and shear strain reached, respectively, 42% and 43%. The influence of the highly resilient wall on the monitored hemodynamic parameters was significant even if time‐averaged values are compared, which suggests that these metrics are considerably overestimated if the wall compliance is not considered. Moreover, the findings show that the mechanical response of the loose connective tissue cannot be neglected in blood flow simulations. Additionally, this study indicates that stiffening of the arterial wall due to atherosclerosis significantly rises hemodynamic parameters. This explains the therapeutic benefits of surgical removal of plaque lesions formed in the carotid bifurcation (endarterectomy).