bluuebunny/crossref_metadata_2025_split huggingface dataset:
Incidence and predictive score for delayed hemolytic transfusion reaction in adult patients with sickle cell disease
Authors: Narbey David , Habibi Anoosha , Chadebech Philippe , Mekontso‐Dessap Armand , Khellaf Mehdi , Lelièvre Jean‐Daniel , Godeau Bertrand , Michel Marc , Galactéros Frédéric , Djoudi Rachid , Bartolucci Pablo , Pirenne France 
Published: September 2017

AbstractDelayed hemolytic transfusion reaction (DHTR) is a life‐threatening complication of transfusion in sickle cell disease (SCD). The frequency of DHTR is underestimated because its symptoms mimic those of vaso‐occlusive crisis and antibodies (Abs) are often not detectable. No predictive factors for identifying patients likely to develop DHTR have yet been defined. We conducted a prospective single‐center observational study over 30 months in adult sickle cell patients. We included 694 transfusion episodes (TEs) in 311 patients, divided into occasional TEs (OTEs: 360) and chronic transfusion program (CTEs: 334). During follow‐up, 15 cases of DHTR were recorded, exclusively after OTEs. DHTR incidence was 4.2% per OTE (95% CI [2.6; 6.9]) and 6.8% per patient during the 30 months of the study (95% CI [4.2; 11.3]). We studied 11 additional DHTR cases, to construct a predictive score for DHTR. The DHTR mortality is high, 3 (11.5%) of the 26 DHTR patients died. The variables retained in the multivariate model were history of DHTR, number of units previously transfused and immunization status before transfusion. The resulting DHTR‐predictive score had an area under the ROC curve of 0.850 [95% CI: 0.780‐0.930], a negative‐predictive value of 98.4% and a positive‐predictive value of 50%. We report in our study population, for the first time, the incidence of DHTR, and, its occurrence exclusively in occasionally transfused patients. We also describe a simple score for predicting DHTR in patients undergoing occasional transfusion, to facilitate the management of blood transfusion in SCD patients.
Solution Structure and Reactivity with Metallocenes of AlMe2F: Mimicking Cation–Anion Interactions in Metallocenium–Methylalumoxane Inner‐Sphere Ion Pairs
Authors: Oliva Leone , Oliva Patrizia , Galdi Nunzia , Pellecchia Claudio , Sian Leonardo , Macchioni Alceo , Zuccaccia Cristiano 
Published: September 2017

AbstractThe solution structure of AlMe2F and its reactivity with a prototypical ansa‐metallocene have been investigated by advanced NMR techniques, in an attempt to indirectly shed some light on the structure and working principles of methylalumoxane (MAO) mixtures in olefin polymerization. In solution, AlMe2F gives rise to a complex equilibrium of oligomeric species, including a heterocubane [(Me2Al)4F4] tetramer, resembling the behavior of MAO. This complex mixture reacts with (ETH)ZrMe2 (ETH=rac‐[ethylenebis(4,5,6,7‐tetrahydro‐1‐indenyl)]) to afford [(ETH)ZrMeδ+(μ‐F)(AlMe2F)nAlMe3δ−] inner‐sphere ion pairs through successive insertions/deinsertions of AlMe2F units into the Zr⋅⋅⋅(μ‐F) bond.
Hydrogen‐Transfer‐Mediated α‐Functionalization of 1,8‐Naphthyridines by a Strategy Overcoming the Over‐Hydrogenation Barrier
Authors: Chen Xiu‐Wen , Zhao He , Chen Chun‐Lian , Jiang Huan‐Feng , Zhang Min 
Published: September 2017

AbstractA general catalytic hydrogen transfer‐mediated α‐functionalization of 1,8‐naphthyridines is reported for the first time that benefits from a hydrogen transfer‐mediated activation mode for non‐activated pyridyl cores. The pyridyl α‐site selectively couples with the C8‐site of various tetrahydroquinolines (THQs) to afford novel α‐functionalized tetrahydro 1,8‐naphthyridines, a class of synthetically useful building blocks and potential candidates for the discovery of therapeutic and bio‐active products. The utilization of THQs as inactive hydrogen donors (HDs) appears to be a key strategy to overcome the over‐hydrogenation barrier and address the chemoselectivity issue. The developed chemistry features operational simplicity, readily available catalyst and good functional group tolerance, and offers a significant basis for further development of new protocols to directly transform or functionalize inert N‐heterocycles.
Stereospezifische Reaktion von Donor‐Akzeptor‐Cyclopropanen mit Thioketonen: ein Zugang zu hoch substituierten Tetrahydrothiophenen
Authors: Augustin André U. , Sensse Maximilian , Jones Peter G. , Werz Daniel B. 
Published: September 2017

AbstractLewis‐Säure‐katalysierte Reaktionen von 2‐substituierten Cyclopropandicarboxylaten mit Thioketonen werden beschrieben. In einem stereospezifischen Prozess wurden unter milden Bedingungen und der Verwendung von AlCl3 als Lewis‐Säure hoch substituierte Tetrahydrothiophene mit zwei benachbarten quartären Kohlenstoffatomen in hohen Ausbeuten erhalten. Ferner konnte eine intramolekulare Version verwirklicht werden, die den Zugang zu Schwefel‐überbrückten [n.2.1]bicyclischen Ringsystemen ermöglicht. Die Umsetzung von Selenoketonen, den höheren Analoga der Thioketone, unter ähnlichen Bedingungen führt zur Bildung verschiedener Tetrahydroselenophene.
Synthesis of a Metallo‐Iminosilane via a Silanone–Metal π‐Complex
Authors: Hadlington Terrance J. , Szilvási Tibor , Driess Matthias 
Published: September 2017

AbstractFacile oxygenation of the acyclic amido‐chlorosilylene bis(N‐heterocyclic carbene) Ni0 complex [{N(Dipp)(SiMe3)ClSi:→Ni(NHC)2] (1; Dipp=2,6‐iPr2C6H4; N‐heterocyclic carbene=C[(iPr)NC(Me)]2) with N2O furnishes the first Si‐metalated iminosilane, [DippN=Si(OSiMe3)Ni(Cl)(NHC)2] (3), in a rearrangement cascade. Markedly, the formation of 3 proceeds via the silanone (Si=O)–Ni π‐complex 2 as the initial product, which was predicted by DFT calculations and observed spectroscopically. The Si=O and Si=N moieties in 2 and 3, respectively, show remarkable hydroboration reactivity towards H−B bonds of boranes, in the former case corroborating the proposed formation of a (Si=O)–Ni π‐complex at low temperature.
Polyamine‐Mediated Stoichiometric Assembly of Ribonucleoproteins for Enhanced mRNA Delivery
Authors: Li Jiahe , He Yanpu , Wang Wade , Wu Connie , Hong Celestine , Hammond Paula T. 
Published: September 2017

AbstractMessenger RNA (mRNA) represents a promising class of nucleic acid drugs. Although numerous carriers have been developed for mRNA delivery, the inefficient mRNA expression inside cells remains a major challenge. Inspired by the dependence of mRNA on 3′‐terminal polyadenosine nucleotides (poly A) and poly A binding proteins (PABPs) for optimal expression, we complexed synthetic mRNA containing a poly A tail with PABPs in a stoichiometric manner and stabilized the ribonucleoproteins (RNPs) with a family of polypeptides bearing different arrangements of cationic side groups. We found that the molecular structure of these polypeptides modulates the degree of PABP‐mediated enhancement of mRNA expression. This strategy elicits an up to 20‐fold increase in mRNA expression in vitro and an approximately fourfold increase in mice. These findings suggest a set of new design principles for gene delivery by the synergistic co‐assembly of mRNA with helper proteins.
Organocatalytic Enantioselective Protonation for Photoreduction of Activated Ketones and Ketimines Induced by Visible Light
Authors: Lin Lu , Bai Xiangbin , Ye Xinyi , Zhao Xiaowei , Tan Choon‐Hong , Jiang Zhiyong 
Published: September 2017

AbstractThe first catalytic asymmetric photoreduction of 1,2‐diketones and α‐keto ketimines under visible light irradiation is reported. A transition‐metal‐free synergistic catalysis platform harnessing dicyanopyrazine‐derived chromophore (DPZ) as the photoredox catalyst and a non‐covalent chiral organocatalyst is effective for these transformations. With the flexible use of a chiral Brønsted acid or base in H+ transfer interchange to control the elusive enantioselective protonation, a variety of chiral α‐hydroxy ketones and α‐amino ketones were obtained with high yields and enantioselectivities.
A Simple and Broadly Applicable C−N Bond Forming Dearomatization Protocol Enabled by Bifunctional Amino Reagents
Authors: Ma Xiaofeng , Farndon Joshua J. , Young Tom A. , Fey Natalie , Bower John F. 
Published: September 2017

AbstractA C−N bond forming dearomatization protocol with broad scope is outlined. Specifically, bifunctional amino reagents are used for sequential nucleophilic and electrophilic C−N bond formations, with the latter effecting the key dearomatization step. Using this approach, γ‐arylated alcohols are converted to a wide range of differentially protected spirocyclic pyrrolidines in just two or three steps.
Differences in protein expression among five species of stream stonefly (Plecoptera) along a latitudinal gradient in Japan
Authors: Gamboa Maribet , Tsuchiya Maria Claret , Matsumoto Suguru , Iwata Hisato , Watanabe Kozo 
Published: September 2017

AbstractProteome variation among natural populations along an environmental gradient may provide insights into how the biological functions of species are related to their local adaptation. We investigated protein expression in five stream stonefly species from four geographic regions along a latitudinal gradient in Japan with varying climatic conditions. The extracted proteins were separated by two‐dimensional gel electrophoresis and identified by matrix‐assisted laser desorption/ionization of time‐of‐flight (MALDI TOF/TOF), yielding 446 proteins. Low interspecies variation in the proteome profiles was observed among five species within geographical regions, presumably due to the co‐occurring species sharing the environments. However, large spatial variations in protein expression were found among four geographic regions, suggesting strong regulation of protein expression in heterogeneous environments, where the spatial variations were positively correlated with water temperature. We identified 21 unique proteins expressed specifically in a geographical region and six common proteins expressed throughout all regions. In warmer regions, metabolic proteins were upregulated, whereas proteins related to cold stress, the photoperiod, and mating were downregulated. Oxygen‐related and energy‐production proteins were upregulated in colder regions with higher altitudes. Thus, our proteomic approach is useful for identifying and understanding important biological functions related to local adaptations by populations of stoneflies.
Thermal melt circular dichroism spectroscopic studies for identifying stabilising amphipathic molecules for the voltage‐gated sodium channel NavMs
Authors: Ireland Sam M. , Sula Altin , Wallace B.A. 
Published: September 2017

AbstractPurified integral membrane proteins require amphipathic molecules to maintain their solubility in aqueous solutions. These complexes, in turn, are used in studies to characterise the protein structures by a variety of biophysical and structural techniques, including spectroscopy, crystallography, and cryo‐electron microscopy. Typically the amphilphiles used have been detergent molecules, but more recently they have included amphipols, which are polymers of different sizes and compositions designed to create smaller, more well‐defined solubilised forms of the membrane proteins. In this study we used circular dichroism spectroscopy to compare the secondary structures and thermal stabilities of the NavMs voltage‐gated sodium channel in different amphipols and detergents as a means of identifying amphipathic environments that maximally maintain the protein structure whilst providing a stabilising environment. These types of characterisations also have potential as means of screening for sample types that may be more suitable for crystallisation and/or cryo‐electron microscopy structure determinations.
Characterizing community courts
Authors: Gal Tali , Dancig‐Rosenberg Hadar 
Published: September 2017

AbstractCommunity courts (CCs) provide a therapeutic diversion for repeat low‐level offenders. This article explores the characteristics of two Israeli CCs using the Criminal Law Taxonomy (CLT), an instrument developed by the authors for assessing process‐, stakeholder‐, substance‐, and outcomes‐related characteristics of criminal justice mechanisms. Through court‐hearing observations and a process of multi‐rater coding of cases, the article analyzes the courtroom dynamics according to a set of 13 measurable parameters. The process was conceived as a vehicle for promoting the model goals: it was highly offender‐oriented and involved a needs‐based terminology while allowing for restrained expression of emotion. However, the process included no victim–offender dialogue and offender supporters and community representatives were only partially involved. The findings provide information about the program's implementation integrity; they also offer a basis for comparison with the characteristics of other justice mechanisms. While focusing on an Israeli program, the issues the article addresses reflect practices and controversies that are salient in many jurisdictions worldwide.
Biosynthetic Machinery of Diterpene Pleuromutilin Isolated from Basidiomycete Fungi
Authors: Yamane Momoka , Minami Atsushi , Liu Chengwei , Ozaki Taro , Takeuchi Ichiro , Tsukagoshi Tae , Tokiwano Tetsuo , Gomi Katsuya , Oikawa Hideaki 
Published: September 2017

AbstractThe diterpene pleuromutilin is a ribosome‐targeting antibiotic isolated from basidiomycete fungi, such as Clitopilus pseudo‐pinsitus. The functional characterization of all biosynthetic enzymes involved in pleuromutilin biosynthesis is reported and a biosynthetic pathway proposed. In vitro enzymatic reactions and mutational analysis revealed that a labdane‐related diterpene synthase, Ple3, catalyzed two rounds of cyclization from geranylgeranyl diphosphate to premutilin possessing a characteristic 5–6–8‐tricyclic carbon skeleton. Biotransformation experiments utilizing Aspergillus oryzae transformants possessing modification enzyme genes allowed the biosynthetic pathway from premutilin to pleuromutilin to be proposed. The present study sets the stage for the enzymatic synthesis of natural products isolated from basidiomycete fungi, which are a prolific source of structurally diverse and biologically active terpenoids.
Multistage Li1.2Ni0.2Mn0.6O2 Micro‐architecture towards High‐Performance Cathode Materials for Lithium‐Ion Batteries
Authors: He Wei , Zheng Hongfei , Ju Xiaokang , Li Shengyang , Ma Yating , Xie Qingshui , Wang Laisen , Qu Baihua , Peng Dong‐Liang 
Published: September 2017

AbstractConstructing hierarchical‐architecture primary nanoparticles that assemble with secondary micro‐architectures is very effective to achieve high‐performance cathode materials for lithium‐ion batteries (LIBs). In this work, well‐crystallized lithium‐rich layered oxide cathode materials Li1.2Ni0.2Mn0.6O2 (LNMO) with a micro‐architecture was successfully synthesized. The preparation process is divided into two steps: the solvothermal process synthesizes the precursor Ni0.25Mn0.75CO3 (NMCO) and gradient temperature calcination is used to prepare the primary nanoparticles that agglomerate into hierarchical microspheres for final‐product LNMO. The as‐prepared material was used as cathode materials for LIBs, which exhibit good cycle life and excellent rate performances. The material retains a fairly high discharge capacity of approximately 180 mAh g−1 after 180 cycles at the 2C rate (1C=200 mA g−1). Even after a 50‐fold (5C/0.1C) increase, a discharge capacity 61.4 %  (153.8 mAh g−1) of the capacity at 0.1C (ca. 249.1 mAh g−1) could be retained. This superior cycle life and rate performance are attributed to the merits of the hierarchical nano‐/microsphere structures.
Structural‐Defect‐Controlled Electrochemical Performance of Sodium Ion Batteries with NaCrO2 Cathodes
Authors: Sawicki Monica , Ortiz Angel L. , Luo Mei , Shaw Leon L. 
Published: September 2017

AbstractIn this study, we report the effects of structural defects on the electrochemical cycle stability of Na‐ion batteries made of NaCrO2 cathodes. Three processing conditions are used to create NaCrO2 with different structural defects. One condition entails high‐energy ball milling of reactants before the solid‐state reaction at 900 °C, the second one has no high‐energy ball milling but simple mixing of reactants before the solid‐state reaction, and the last one has high‐energy ball milling after the solid‐state reaction. The NaCrO2 crystals derived from the process with high‐energy ball milling of reactants before the solid‐state reaction exhibit the best bulk conductivity and highest specific capacity with little capacity decay over 46 charge/discharge cycles. In contrast, the NaCrO2 crystals derived from the process without high‐energy ball milling have significant capacity decay, whereas the NaCrO2 crystals obtained from the process with high‐energy ball milling after the solid‐state reaction exhibits the lowest bulk conductivity and very low specific capacities. The different electrochemical properties exhibited by these NaCrO2 crystals have been ascribed to different extents of structural defects present in these crystals. This study unambiguously demonstrates that structural defects in NaCrO2 crystals are critical in achieving NaCrO2 electrodes with high specific capacity and excellent capacity retention.
Rational Design of a Bifunctional, Two‐Fold Interpenetrated ZnII‐Metal–Organic Framework for Selective Adsorption of CO2 and Efficient Aqueous Phase Sensing of 2,4,6‐Trinitrophenol
Authors: Singh Dhankhar Sandeep , Sharma Nayuesh , Kumar Sandeep , Dhilip Kumar T. J. , Nagaraja C. M. 
Published: September 2017

AbstractA bifunctional, microporous ZnII metal–organic framework, [Zn2(NH2BDC)2(dpNDI)]n (MOF1) (where, NH2BDC=2‐aminoterephthalic acid, dpNDI=N,N′‐di(4‐pyridyl)‐1,4,5,8‐naphthalenediimide) has been synthesized solvothermally. MOF1 shows an interesting two‐fold interpenetrated, 3D pillar‐layered framework structure composed of two types of 1D channels with dimensions of approximately 2.99×3.58 Å and 4.58×5.38 Å decorated with pendent −NH2 groups. Owing to the presence of a basic functionalized pore surface, MOF1 exhibits selective adsorption of CO2 with high value of heat of adsorption (Qst=46.5 kJ mol−1) which is further supported by theoretically calculated binding energy of 48.4 kJ mol−1. Interestingly, the value of Qst observed for MOF1 is about 10 kJ mol−1 higher than that of analogues MOF with the benzene‐1,4‐dicarboxylic acid (BDC) ligand, which establishes the critical role of the −NH2 group for CO2 capture. Moreover, MOF1 exhibits highly selective and sensitive sensing of the nitroaromatic compound (NAC), 2,4,6‐trinitrophenol (TNP) over other competing NACs through a luminescence quenching mechanism. The observed selectivity for TNP over other nitrophenols has been correlated to stronger hydrogen bonding interaction of TNP with the basic −NH2 group of MOF1, which is revealed from DFT calculations. To the best of our knowledge, MOF1 is the first example of an interpenetrated ZnII‐MOF exhibiting selective adsorption of CO2 as well as efficient aqueous‐phase sensing of TNP; investigated through combined experimental and theoretical studies.
Quasi‐Emulsion Confined Synthesis of Edge‐Rich Ultrathin MoS2 Nanosheets/Graphene Hybrid for Enhanced Hydrogen Evolution
Authors: Yin Xuying , Yan Ya , Miao Mao , Zhan Ke , Li Pingwei , Yang Junhe , Zhao Bin , Xia Bao Yu 
Published: September 2017

AbstractHigh‐purity hydrogen produced by water splitting is considered as one of the most promising fuels to replace traditional fossil fuels. Developing highly efficient electrocatalysts toward hydrogen evolution is vital for the realization of large‐scale H2 generation. Glycerol is used herein in a facile solvothermal process to synthesize edge‐rich ultrathin MoS2/reduced graphene oxide (RGO) composites. The introduction of glycerol plays an important role in the formation of such interesting structures. The MoS2/RGO electrocatalyst exhibits excellent hydrogen evolution reaction (HER) activity and remarkable stability, owing to the rich active edges and improved electrical conductivity of the catalyst composites. This work provides new insights to engineer the structures of MoSx‐based composites and thus achieves more active and efficient electrocatalysts.
One‐Pot Synthesis of Size‐Controllable Core–Shell CdS and Derived CdS@ZnxCd1−xS Structures for Photocatalytic Hydrogen Production
Authors: Kai Shuangshuang , Xi Baojuan , Wang Yifeng , Xiong Shenglin 
Published: September 2017

AbstractChalcogenide micro/nanocomposite structures have been attracting worldwide attention due to prospective applications in photocatalytic hydrogen production. Well‐defined micro/nanostructures with pronounced properties are of extraordinary importance. Herein, a facile one‐pot method for the synthesis of monodisperse, size‐controllable CdS core–shell and CdS@ZnxCd1−xS core–double shell submicrospheres, which were engineered with respect to structure and size, is reported. CdS core–shell submicrospheres with different sizes were selectively prepared for the first time. The growth mechanism was investigated in detail by monitoring the time‐dependent morphology of intermediates by TEM. By introduction of a zinc precursor in the synthetic system, CdS@ZnxCd1−xS core–double shell submicrospheres were obtained by cation exchange of CdS with zinc ions, with a process of diffusion of CdS towards the outside and transformation of ZnxCd1−xS crystallites. The H2 evolution rate over CdS@CdxZn1−xS (5.17 mmol h−1 g−1) is 12.3 times that of CdS core–shell structures (0.42 mmol h−1 g−1) under visible light, owing to the efficient charge separation, as demonstrated by electrochemical impedance and transient‐state time‐resolved photoluminescence spectroscopy. Furthermore, CdS@ZnxCd1−xS core–double shell structures exhibited excellent stability over 20 h of hydrogen production.
Co3O4 Nanowire Arrays toward Superior Water Oxidation Electrocatalysis in Alkaline Media by Surface Amorphization
Authors: Zhou Dan , He Liangbo , Zhang Rong , Hao Shuai , Hou Xiandeng , Liu Zhiang , Du Gu , Asiri Abdullah M. , Zheng Chengbin , Sun Xuping 
Published: September 2017

AbstractIt is highly desirable to develop a simple, fast and straightforward method to boost the alkaline water oxidation of metal oxide catalysts. In this communication, we report our recent finding that the generation of amorphous Co‐borate layer on Co3O4 nanowire arrays supported on Ti mesh (Co3O4@Co‐Bi NA/TM) leads to significantly boosted OER activity. The as‐prepared Co3O4@Co‐Bi NA/TM demands overpotential of 304 mV to drive a geometrical current density of 20 mA cm‐2 in 1.0 M KOH, which is 109 mV less than that for Co3O4 NA/TM, with its catalytic activity being preserved for at least 20 h. It suggests that the existence of amorphous Co‐Bi layer promotes more CoOx(OH)y generation on Co3O4 surface.
Synergistic Configuration of Diols as Brønsted Bases
Authors: Kim Ye‐Jin , Rakshit Surajit , Jin Geun Young , Ghosh Prasun , Lee Young Min , Park Won‐Woo , Kim Yung Sam , Kwon Oh‐Hoon 
Published: September 2017

AbstractAs viscous hydroxylic organic compounds, diols are of interest for their functional molecular conformation, which is based on inter‐ and intramolecular hydrogen (H)‐bonds. By utilising steady‐state electronic and vibrational spectroscopy, time‐resolved fluorescence spectroscopy, and computational analyses, we report the association of the hydroxyl groups of diols via intra‐ or intermolecular H‐bonds to enhance their reactivity as a base. Whereas the formation of an intermolecularly H‐bonded dimer is requisite for diols of weak intramolecular H‐bond to extract a proton from a model strong photoacid, a well‐configured single diol molecule with an optimised intramolecular H‐bond is revealed to serve as an effective Brønsted base with increased basicity. This observation highlights the collective role of H‐bonding in acid–base reactions, and provides mechanistic backgrounds to understand the reactivity of polyols in the acid‐catalysed dehydration for the synthesis of cyclic ethers at the molecular level.