bluuebunny/crossref_metadata_2025_split huggingface dataset:
Insight into the Transition‐Metal Hydroxide Cover Layer for Enhancing Photoelectrochemical Water Oxidation
Authors: Ning Xingming , Du Peiyao , Han Zhengang , Chen Jing , Lu Xiaoquan 
Published: October 2020

AbstractDepositing a transition‐metal hydroxide (TMH) layer on a photoanode has been demonstrated to enhance photoelectrochemical (PEC) water oxidation. However, the controversial understanding for the improvement origin remains a key challenge to unlock the PEC performance. Herein, by taking BiVO4/iron‐nickel hydroxide (BVO/FxN4−x‐H) as a prototype, we decoupled the PEC process into two processes including charge transfer and surface catalytic reaction. The kinetic information at the BVO/FxN4−x‐H and FxN4−x‐H/electrolyte interfaces was systematically evaluated by employing scanning photoelectrochemical microscopy (SPECM), intensity modulated photocurrent spectroscopy (IMPS) and oxygen evolution reaction (OER) model. It was found that FxN4−x‐H acts as a charge transporter rather than a sole electrocatalyst. PEC performance improvement is mainly ascribed to the efficient suppression of charge recombination by fast hole transfer kinetics at BVO/FxN4−x‐H interface.
An Iminophosphonamido‐Chlorosilylene as a Strong σ‐Donating NHSi Ligand: Synthesis and Coordination Chemistry
Authors: Takahashi Shintaro , Sekiguchi Jueri , Ishii Akihiko , Nakata Norio 
Published: October 2020

AbstractTheN‐heterocyclic silylene (NHSi) [Ph2P(tBuN)2]SiCl (1), supported by an iminophosphonamide ligand, was obtained from the dehydrochlorination of [Ph2P(tBuN)2]SiHCl2(2) with LiN(SiMe3)2. NHSi1contains an extremely high‐energy HOMO level and consequently displays unique coordination behavior toward RhIcomplexes. When1was treated with 1/4 of an equivalent of [RhCl(cod)]2(cod=1,5‐cyclooctadiene), the 14‐electron Y‐shaped bis(chlorosilylene) RhIcomplex5was obtained as dark purple crystals. The reaction of1with 1/6 of an equivalent of [RhCl(cod)]2yielded the cationic tris(silylene)‐RhIcomplex [6]+⋅Cl−as red crystals, wherein a two‐coordinated silylene ligand engages in a Si=Rh double bond. A structural analysis of5and [6]+⋅Cl−revealed that the central rhodium atoms adopt trigonal and square‐planar coordination geometries, respectively, with considerably shortened Si‐Rh bonds [5: 2.1605(5) Å; [6]+: 2.133(1) Å].
Surface Coordination of Multiple Ligands Endows N‐Heterocyclic Carbene‐Stabilized Gold Nanoclusters with High Robustness and Surface Reactivity
Authors: Shen Hui , Xu Zhen , Hazer Maryam Sabooni Asre , Wu Qingyuan , Peng Jian , Qin Ruixuan , Malola Sami , Teo Boon K. , Häkkinen Hannu , Zheng Nanfeng 
Published: October 2020

AbstractDeciphering the molecular pictures of the multi‐component and non‐periodic organic‐inorganic interlayer is a grand technical challenge. Here we show that the atomic arrangement of hybrid surface ligands on metal nanoparticles can be precisely quantified through comprehensive characterization of a novel gold cluster, Au44(iPr2‐bimy)9(PA)6Br8 (1), which features three types of ligands, namely, carbene (1,3‐diisopropylbenzimidazolin‐2‐ylidene, iPr2‐bimy), alkynyl (phenylacetylide, PA), and halide (Br), respectively. The delicately balanced stereochemical effects and bonding capabilities of the three ligands give rise to peculiar geometrical and electronic structures. Remarkably, despite its complex and highly distorted surface structure, cluster 1 exhibits unusual catalytic properties and yet it is highly stable, both chemically and thermally. Moreover, rich reactive sites on the cluster surface raise the prospect of bio‐compatibility (as it can be functionalized to yield water‐soluble derivatives) and bio‐applications.
Adrenergic Modulation With Photochromic Ligands
Authors: Prischich Davia , Gomila Alexandre M. J. , Milla‐Navarro Santiago , Sangüesa Gemma , Diez‐Alarcia Rebeca , Preda Beatrice , Matera Carlo , Batlle Montserrat , Ramírez Laura , Giralt Ernest , Hernando Jordi , Guasch Eduard , Meana J. Javier , de la Villa Pedro , Gorostiza Pau 
Published: October 2020

AbstractAdrenoceptors are ubiquitous and mediate important autonomic functions as well as modulating arousal, cognition, and pain on a central level. Understanding these physiological processes and their underlying neural circuits requires manipulating adrenergic neurotransmission with high spatio‐temporal precision. Here we present a first generation of photochromic ligands (adrenoswitches) obtained via azologization of a class of cyclic amidines related to the known ligand clonidine. Their pharmacology, photochromism, bioavailability, and lack of toxicity allow for broad biological applications, as demonstrated by controlling locomotion in zebrafish and pupillary responses in mice.
Discovery and Supramolecular Interactions of Neutral Palladium‐Oxo Clusters Pd16and Pd24
Authors: Bhattacharya Saurav , Basu Uttara , Haouas Mohamed , Su Pei , Espenship Michael Forrester , Wang Fei , Solé‐Daura Albert , Taffa Dereje H. , Wark Michael , Poblet Josep M. , Laskin Julia , Cadot Emmanuel , Kortz Ulrich 
Published: October 2020

AbstractWe report on the synthesis, structure, and physicochemical characterization of the first three examples of neutral palladium‐oxo clusters (POCs). The 16‐palladium(II)‐oxo cluster [Pd16O24(OH)8((CH3)2As)8] (Pd16) comprises a cyclic palladium‐oxo unit capped by eight dimethylarsinate groups. The chloro‐derivative [Pd16Na2O26(OH)3 Cl3 ((CH3)2 As)8] (Pd16Cl) was also prepared, which forms a highly stable 3D supramolecular lattice via strong intermolecular interactions. The 24‐palladium(II)‐oxo cluster [Pd24O44(OH)8((CH3)2As)16] (Pd24) can be considered as a bicapped derivative ofPd16with a tetra‐palladium‐oxo unit grafted on either side. The three compounds were fully characterized 1) in the solid state by single‐crystal and powder XRD, IR, TGA, and solid‐state1H and13C NMR spectroscopy, 2) in solution by1H,13C NMR and1H DOSY spectroscopic methods, and 3) in the gas phase by electrospray ionization mass spectrometry (ESI‐MS).
Nickel‐ and Palladium‐Catalyzed Cross‐Coupling Reactions of Organostibines with Organoboronic Acids
Authors: Zhang Dejiang , Le Liyuan , Qiu Renhua , Wong Wai‐Yeung , Kambe Nobuaki 
Published: October 2020

AbstractA strategy for the formation of antimony‐carbon bond was developed by nickel‐catalyzed cross‐coupling of halostibines. This method has been applied to the synthesis of various triaryl‐ and diarylalkylstibines from the corresponding cyclic and acyclic halostibines. This protocol showed a wide substrate scope (72 examples) and was compatible to a wide range of functional groups such as aldehyde, ketone, alkene, alkyne, haloarenes (F, Cl, Br, I), and heteroarenes. A successful synthesis of arylated stibine 3 a in a scale of 34.77 g demonstrates high synthetic potential of this transformation. The formed stibines (R3Sb) were then used for the palladium‐catalyzed carbon–carbon bond forming reaction with aryl boronic acids [R−B(OH)2], giving biaryls with high selectivity, even the structures of two organomoieties (R and R′) are very similar. Plausible catalytic pathways were proposed based on control experiments.
Synergy between Metallic and Oxidized Pt Sites Unravelled during Room Temperature CO Oxidation on Pt/Ceria
Authors: Meunier Frederic C. , Cardenas Luis , Kaper Helena , Šmíd Břetislav , Vorokhta Mykhailo , Grosjean Rémi , Aubert Daniel , Dembélé Kassiogé , Lunkenbein Thomas 
Published: October 2020

AbstractPt‐based materials are widely used as heterogeneous catalysts, in particular for pollutant removal applications. The state of Pt has often been proposed to differ depending on experimental conditions, for example, metallic Pt poisoned with CO being present at lower temperature before light‐off, while an oxidized Pt surface prevails above light‐off temperature. In stark contrast to all previous reports, we show herein that both metallic and oxidized Pt are present in similar proportions under reaction conditions at the surface of ca. 1 nm nanoparticles showing high activity at 30 °C. The simultaneous presence of metallic and oxidized Pt enables a synergy between these phases. The main role of the metallic Pt phase is to provide strong adsorption sites for CO, while that of oxidized Pt supposedly supplies reactive oxygen. Our results emphasize the complex dual oxidic–metallic nature of supported Pt catalysts and platinum's evolving nature under reaction conditions.
Exploiting Ru‐Induced Lattice Strain in CoRu Nanoalloys for Robust Bifunctional Hydrogen Production
Authors: Li Weidong , Zhao Yunxuan , Liu Yuan , Sun Mingzi , Waterhouse Geoffrey I. N. , Huang Bolong , Zhang Kan , Zhang Tierui , Lu Siyu 
Published: October 2020

AbstractDesigning bifunctional catalysts capable of driving the electrochemical hydrogen evolution reaction (HER) and also H2 evolution via the hydrolysis of hydrogen storage materials such as ammonia borane (AB) is of considerable practical importance for future hydrogen economies. Herein, we systematically examined the effect of tensile lattice strain in CoRu nanoalloys supported on carbon quantum dots (CoRu/CQDs) on hydrogen generation by HER and AB hydrolysis. By varying the Ru content, the lattice parameters and Ru‐induced lattice strain in the CoRu nanoalloys could be tuned. The CoRu0.5/CQDs catalyst with an ultra‐low Ru content (1.33 wt.%) exhibited excellent catalytic activity for HER (η=18 mV at 10 mA cm−2 in 1 M KOH) and extraordinary activity for the hydrolysis of AB with a turnover frequency of 3255.4 mol
mol−1(Ru) min−1 or 814.7 mol
mol−1(cat) min−1 at 298 K, respectively, representing one of the best activities yet reported for AB hydrolysis over a ruthenium alloy catalyst. Moreover, the CoRu0.5/CQDs catalyst displayed excellent stability during each reaction, including seven alternating cycles of HER and AB hydrolysis. Theoretical calculations revealed that the remarkable catalytic performance of CoRu0.5/CQDs resulted from the optimal alloy electronic structure realized by incorporating small amounts of Ru, which enabled fast interfacial electron transfer to intermediates, thus benefitting H2 evolution kinetics. Results support the development of new and improved catalysts HER and AB hydrolysis.
Multiple imputation methods for handling missing values in longitudinal studies with sampling weights: Comparison of methods implemented in Stata
Authors: De Silva Anurika P. , De Livera Alysha M. , Lee Katherine J. , Moreno‐Betancur Margarita , Simpson Julie A. 
Published: October 2020

AbstractMany analyses of longitudinal cohorts require incorporating sampling weights to account for unequal sampling probabilities of participants, as well as the use of multiple imputation (MI) for dealing with missing data. However, there is no guidance on how MI and sampling weights should be implemented together. We simulated a target population based on the Australian Bureau of Statistics Estimated Resident Population and drew 1000 random samples dependent on three design variables to mimic the Longitudinal Study of Australian Children. The target analysis was the weighted prevalence of overweight/obesity over childhood. We evaluated the performance of several MI approaches available in Stata, based on multivariate normal imputation (MVNI), fully conditional specification (FCS) and twofold FCS: a weighted imputation model, imputing missing data separately for each quintile sampling weight grouping, including the design stratum indicator in the imputation model, and using sampling weights as a covariate in the imputation model. Approaches based on available cases and inverse probability weighting (IPW), with time‐varying weights, were also compared. We observed severe issues of convergence with FCS and twofold FCS. All MVNI‐based approaches performed similarly, producing minimal bias and nominal coverage, except for when imputation was conducted separately for each quintile sampling weight group. IPW performed equally as well as MVNI‐based approaches in terms of bias, however, was less precise. In similar longitudinal studies, we recommend using MVNI with the design stratum as a covariate in the imputation model. If this is unknown, including the sampling weight as a covariate is an appropriate alternative.
Preclinical Evaluation of a Novel TALEN Targeting CCR5 Confirms Efficacy and Safety in Conferring Resistance to HIV‐1 Infection
Authors: Romito Marianna , Juillerat Alexandre , Kok Yik Lim , Hildenbeutel Markus , Rhiel Manuel , Andrieux Geoffroy , Geiger Johannes , Rudolph Carsten , Mussolino Claudio , Duclert Aymeric , Metzner Karin J. , Duchateau Philippe , Cathomen Toni , Cornu Tatjana I. 
Published: October 2020

AbstractTherapies to treat patients infected with human immunodeficiency virus (HIV) aim at preventing viral replication but fail to eliminate the virus. Although transplantation of allogeneic CCR5Δ32 homozygous stem cell grafts provided a cure for a few patients, this approach is not considered a general therapeutic strategy because of potential side effects. Conversely, gene editing to disrupt the C‐C chemokine receptor type 5 (CCR5) locus, which encodes the major HIV coreceptor, has shown to confer resistance to CCR5‐tropic HIV strains. Here, an engineered transcription activator‐like effector nuclease (TALEN) that enables efficient CCR5 editing in hematopoietic cells is presented. After transferring TALEN‐encoding mRNA into primary CD4+ T cells, up to 89% of CCR5 alleles are disrupted. Genotyping confirms the genetic stability of the CCR5‐edited cells, and genome‐wide off‐target analyses established the absence of relevant mutagenic events. When challenging the edited T cells with CCR5‐tropic HIV, protection in a dose‐dependent manner is observed. Functional assessments reveal no significant differences between edited and control cells in terms of proliferation and their ability to secrete cytokines upon exogenous stimuli. In conclusion, a highly active and specific TALEN to disrupt CCR5 is successfully engineered, paving the way for its clinical application in hematopoietic stem cell grafts.
Low serum 25‐hydroxyvitamin D3 levels and late delayed radiation‐induced brain injury in patients with nasopharyngeal carcinoma: A case–control study
Authors: Deng Zhezhi , Li Minping , Guo Junjie , Zhou Dongxiao , Huang Xurui , Huang Yongxin , Huang Haiwei 
Published: October 2020

AbstractBackground and PurposeInflammatory reaction plays a critical role in the pathogenesis of late delayed radiation‐induced brain injury (RBI). Low vitamin D levels are closely associated with various immuno‐inflammatory diseases, but the relationship with late delayed RBI remains unknown. Here, we aimed to determine the association of serum vitamin D levels with clinical parameters in late delayed RBI patients with nasopharyngeal carcinoma.Methods25‐Hydroxyvitamin D3 levels and clinical and cerebrospinal fluid parameters were evaluated in 21 patients with RBI and compared with 90 age‐, sex‐, and season‐matched healthy controls.Results25‐(OH)D3 levels were lower in patients with RBI compared to controls (40.39 ± 22.11 vs. 64.54 ± 19.89 nmol/L, p < .001), especially for aged ≥60 years (vs. <60 years, p = .038), females (vs. males, p = .012), short latency (<5 years) (vs. ≥5 years, p = .015), and severe impairment (LENT/SOMA score ≥3) (vs. LENT/SOMA score <3, p = .010). Serum 25‐(OH)D3 levels were associated with age (r = −.464, p = .015), Latency of RBI (r = .416, p = .031) and LENT/SOMA Scale (r = −.488, p = .010).ConclusionsOur data showed that serum 25‐(OH)D3 levels were reduced in late delayed RBI patients with nasopharyngeal carcinoma.
Charting a New Path Towards Degrading Every Protein
Authors: Nabet Behnam 
Published: October 2020

AbstractStrategies to directly alter protein abundance such as small‐molecule‐induced targeted protein degradation (TPD) are innovative pharmacological modalities with promising clinical potential. Herein, I describe my experience with the development of the degradation tag (dTAG) system, which is a chemical biology strategy to induce rapid and precise degradation of any target protein. Open‐source collaborative discovery has been critical for advancing the versatility and accessibility of the dTAG system and will be necessary to understand the benefits and limits of TPD‐based strategies in the clinic.
A FRET‐Based Fluorescent Probe to Screen Anticancer Drugs, Inhibiting p73 Binding to MDM2
Authors: Han A. Ro , Durgannavar Trishaladevi , Ahn Dohee , Chung Sang J. 
Published: October 2020

AbstractThe protein p73 acts as a transcription factor, resulting in tumour suppression. MDM2, an oncogenic protein, can negatively influence p73‐mediated apoptosis by binding to p73 transactivation domains (TAD). Inhibition of the protein‐protein interaction between p73 and oncogenic proteins is an attractive strategy for promoting p73‐mediated apoptosis. Herein, we describe the use of a modified p73‐TAD peptide for the FRET‐based assay of the binding of p73‐TAD to MDM2. The FRET probe, equipped with 1‐naphthylamine (λex=330 nm, λem=445 nm), serves as a FRET acceptor, and the tryptophan of the protein acts as FRET donor (λex=280 nm, λem=340 nm). Sensitized emission from the FRET probe was observed upon excitation of the protein‐FRET‐probe complex at the excitation wavelength of Trp. Furthermore, addition of the MDM2 inhibitor Nutiln‐3 drastically reduced the FRET signal, thus indicating that the FRET probe competes with Nutiln‐3 for MDM2 binding. The developed FRET binding assay might be applicable in high‐throughput screening of novel drugs that inhibit interactions between p73 and MDM2.
A case of laparoscopic resection of leiomyosarcoma arising in the mesentery of descending colon: a case report and review of the literature
Authors: Koyama Ryota , Maeda Yoshiaki , Minagawa Nozomi , Shinohara Toshiki 
Published: October 2020

AbstractLeiomyosarcoma of mesenteric origin is rare and may be managed by laparoscopic surgery as a less invasive procedure, on the condition that the tumor can be resected with a safe margin.
Spontaneous disruption of the dividing membrane in monochorionic diamniotic twin pregnancy
Authors: Yokoyama Nobuko , Sagawa Kei , Miyazaki Miwa , Suzuki Shunji 
Published: October 2020

AbstractSpontaneous disruption of the dividing membrane in MD twins is rare and be associated with a higher incidence of prematurity and neonatal morbidity. In the present case, a spontaneous disrupted dividing membrane could be noted by ultrasonography.
Photoswitchable Catalysis Mediated by Nanoparticles
Authors: Sobczak Grzegorz , Sashuk Volodymyr 
Published: October 2020

AbstractPhotoswitchable catalysis utilizes spatiotemporal light delivery to provide control over reaction rate and selectivity. The inception and further development of this field was related to bulk solutions. This minireview describes the recent evolution of nanoparticle‐based colloidal systems and explains the principles ruling therein. Subsequently, examples of such systems are reported with thorough analysis and comparison. Finally, we provide an outlook on possible new directions in this field.
Cellulose‐Based Reduced Nanographene Oxide on Gold Nanoparticle Supports for CO2 Electrocatalysis
Authors: Koyejo Adefunke O. , Kesavan Lokesh , Damlin Pia , Salomäki Mikko , Yao Jenevieve G. , Hakkarainen Minna , Kvarnström Carita 
Published: October 2020

AbstractCellulose‐based reduced graphene oxide materials (r‐nGO) were fabricated and anchored onto polyvinyl alcohol stabilized gold nanoparticles. Their potential in applications in the electrocatalytic reduction of CO2 (ER‐CO2) is demonstrated. The nGO was synthesized by microwave‐assisted cellulose carbonization followed by two different reduction methods, that is, with super‐heated water (i) or caffeic acid (ii). These materials, denoted as r‐nGO (i) r‐nGO‐CA (ii), were utilized to immobilize colloidal gold nanoparticles (Au NPs) in an aqueous environment. The two r‐nGO‐supported Au NP materials were deposited on glassy carbon electrode surfaces and studied as catalysts for ER‐CO2. ER‐CO2 was investigated at room temperature and pressure (RTP) using ionic liquids (RTILs) or an aprotic solvent acetonitrile (ACN). Tetrabutylammonium hexafluoroborate (TBAPF6) was used as an electrolyte salt in the case of ACN. The current response resulting from ER‐CO2 was measured under cyclic voltammetric conditions using a one‐compartment three‐electrode cell. Results showed that, r‐nGO‐supported gold nanoparticles catalyze ER‐CO2 and they significantly reduce the overpotential of CO2 reduction from −1.9 V to −1.6 V vs. Ag/AgCl. Moreover, of all the materials studied, Au/r‐nGO was superior in reducing CO2 in both RTILs and TBAPF6/ACN. These outcomes serve as grounds for the further development of electrocatalysts from bio‐based reduced graphene oxides.
7‐Hydroxycoumarin as a Novel Film‐Forming Additive for LiNi0.5Mn1.5O4 Cathode at Elevated Temperature
Authors: Shang Huimin , Jiang Jinjin , Zhang Huan , Niu Wenchao , Qiao Yingjun , Zhou Hanxiao , Li Tianhui , Qu Meizhen , Peng Gongchang , Xie Zhengwei 
Published: October 2020

AbstractA novel additive, 7‐hydroxycoumarin (7‐HC), is employed to construct a stable interface film on the LiNi0.5Mn1.5O4 cathode to improve the cyclic stability of Li/LiNi0.5Mn1.5O4 cells at elevated temperature (ca. 55 °C). In the 0.01 wt% 7‐hydroxycoumarin‐containing electrolyte, the capacity retention of Li/LiNi0.5Mn1.5O4 cell increases from 78.15 % to 95.64 % at elevated temperature after 100 cycles at 1 C rate. Through theoretical calculations and ex‐situ analysis, it suggests that 7‐HC is susceptible to oxidation than other components of the electrolyte to form a thin and stable film on the surface of LiNi0.5Mn1.5O4 cathode. The thin and stable film can effectively reduce the interface oxidation reaction and the “cross‐talk” between the positive electrode and negative electrode and effectively inhibit the structural changes of LiNi0.5Mn1.5O4 caused by dissolved transition metals in subsequent cycles, thereby improving the cyclic stability of the cell at elevated temperature.
Sodium Cyclopentadienide as a New Type of Electrolyte for Sodium Batteries
Authors: Binder Markus , Mandl Magdalena , Zaubitzer Steve , Wohlfahrt‐Mehrens Margret , Passerini Stefano , Böse Olaf , Danzer Michael A. , Marinaro Mario 
Published: October 2020

AbstractOwing to the low cost and high abundance of sodium, sodium‐based batteries, especially those employing metallic sodium anodes, are considered for post‐lithium energy storage. In order to develop high‐performance and long‐lasting sodium‐metal batteries, however, the reversible Na‐metal stripping and plating challenge must be addressed. Most organic electrolytes suffer from non‐uniform and continuous formation of the solid electrolyte interphase as well as unfavorable dendritic growth. The use of sodium cyclopentadienide dissolved in tetrahydrofuran as the electrolyte reveals an improved reversibility of sodium dissolution and electrodeposition combined with an electrochemical stability window of around 2.2 V vs. Na/Na+ and an ionic conductivity of 1.36 mS cm−1 at 25 °C. Furthermore, the plated electrodes showed a remarkable morphology of the Na deposits, that is, no dendrite formation, whereby the above‐mentioned electrolyte could overcome the aforementioned cycling issues, thus suggesting suitability for further studies.