bluuebunny/crossref_metadata_2025_split huggingface dataset:
Nanocrystalline Perovskite Hybrid Photodetectors with High Performance in Almost Every Figure of Merit
Authors: Lin Yuanwei , Lin Guoming , Sun Baoyun , Guo Xuefeng 
Published: December 2017

AbstractConversion of photon into electron is a phenomenon of great importance in nature. Photodetectors based on this principle have immense potential applications at the frontiers of both scientific and industrial communities, thus affecting the daily life. Herein, a novel class of high‐quality organic–inorganic trihalide perovskite nanoscale hybrid photodetectors is presented based on carbon electrode−molecule junctions working at mild conditions. Almost every figure of merit with high performance, such as highest responsivity, highest photogain, high detectivity, high linear dynamic range, and a broad spectral response, could be achieved simultaneously in a single device under different biases. These significant achievements benefit from rational choices of novel energy loss‐prevented hybrid perovskite nanocrystals as active materials and optimized carbon electrode−molecule junctions as device architectures, which leads to a hybridization mechanism of photodiodes and photoconductors. These investigations demonstrate a useful photodetector platform that might lead to many future photoelectric conversion applications in the practical way.
Bio‐Inspired Anisotropic Wettability Surfaces from Dynamic Ferrofluid Assembled Templates
Authors: Shang Luoran , Yu Yunru , Gao Wei , Wang Yuetong , Qu Liangliang , Zhao Ze , Chai Renjie , Zhao Yuanjin 
Published: December 2017

AbstractThe biomimetic principle of harnessing topographical structures to determine liquid motion behavior represents a cutting‐edge direction in constructing green transportation systems without external energy input. Here, inspired by natural Nepenthes peristome, a novel anisotropic wettability surface with characteristic structural features of periodically aligned and overlapped arch‐shaped microcavities, formed by employing ferrofluid assemblies as dynamic templates, is presented. The magnetic strength and orientation are precisely adjustable during the generation process, and thus the size and inclination angle of the ferrofluid droplet templates could be tailored to make the surface morphology of the resultant polymer replica achieve a high degree of similarity to the natural peristome. The resultant anisotropic wettability surface enables autonomous unidirectional water transportation in a fast and continuous way. In addition, it could be tailored into arbitrary shapes to induce water flow along a specific curved path. More importantly, based on the anisotropic wettability surface, novel pump‐free microfluidic devices are constructed to implement multiphase flow reactions, which offer a promising solution to building low‐cost, portable platform for lab‐on‐a‐chip applications.
Local Built‐In Electric Field Enabled in Carbon‐Doped Co3O4 Nanocrystals for Superior Lithium‐Ion Storage
Authors: Yan Chunshuang , Zhu Yue , Li Yutao , Fang Zhiwei , Peng Lele , Zhou Xin , Chen Gang , Yu Guihua 
Published: December 2017

AbstractIn this work, a novel concept of introducing a local built‐in electric field to facilitate lithium‐ion transport and storage within interstitial carbon (C‐) doped nanoarchitectured Co3O4 electrodes for greatly improved lithium‐ion storage properties is demonstrated. The imbalanced charge distribution emerging from the C‐dopant can induce a local electric field, to greatly facilitate charge transfer. Via the mechanism of “surface locking” effect and in situ topotactic conversion, unique sub‐10 nm nanocrystal‐assembled Co3O4 hollow nanotubes (HNTs) are formed, exhibiting excellent structural stability. The resulting C‐doped Co3O4 HNT‐based electrodes demonstrate an excellent reversible capacity ≈950 mA h g−1 after 300 cycles at 0.5 A g−1 and superior rate performance with ≈853 mA h g−1 at 10 A g−1.
Efficacy and safety of rituximab for systemic lupus erythematosus‐associated immune cytopenias: A multicenter retrospective cohort study of 71 adults
Authors: Serris Alexandra , Amoura Zahir , Canouï‐Poitrine Florence , Terrier Benjamin , Hachulla Eric , Costedoat‐Chalumeau Nathalie , Papo Thomas , Lambotte Olivier , Saadoun David , Hié Miguel , Blanche Philippe , Lioger Bertrand , Gottenberg Jacques‐Eric , Godeau Bertrand , Michel Marc 
Published: December 2017

AbstractThe aim of the study was to assess the efficacy and safety of rituximab (RTX) for treating systemic lupus erythematosus (SLE)‐associated immune cytopenias. This multicenter retrospective cohort study of adults from French referral centers and networks for adult immune cytopenias and SLE involved patients ≥18 years old with a definite diagnosis of SLE treated with RTX specifically for SLE‐associated immune cytopenia from 2005 to 2015. Response assessment was based on standard definitions. In total, 71 patients, 61 women (85.9%), with median age 36 years [interquartile range 31‐48], were included. The median duration of SLE at the time of the first RTX administration was 6.1 years [2.6‐11.6] and the reason for using RTX was immune thrombocytopenia (ITP) for 44 patients (62.0%), autoimmune hemolytic anemia (AIHA) for 16 (22.5%), Evans syndrome for 10 (14.1%), and pure red cell aplasia for one patient. Before receiving RTX, patients had received a mean of 3.1 ± 1.3 treatments that included corticosteroids (100%), and hydroxychloroquine (88.5%). The overall initial response rate to RTX was 86% (91% with ITP, 87.5% with AIHA, and 60% with Evans syndrome), including 60.5% with complete response. Median follow‐up after the first injection of RTX was 26.4 months [14.3‐71.2]. Among 61 initial responders, relapse occurred in 24 (39.3%); for 18, RTX retreatment was successful in 16 (88.8%). Severe infections occurred after RTX in three patients, with no fatal outcome. No cases of RTX‐induced neutropenia were observed. In conclusion, RTX seems effective and relatively safe for treating SLE‐associated immune cytopenias.
Photochromie jenseits des Sichtbaren: Direkte, im biologischen Fenster addressierbare Einphotonen‐NIR‐Photoschalter
Authors: Klaue Kristin , Garmshausen Yves , Hecht Stefan 
Published: December 2017

AbstractDer Erfolg der Photopharmakologie ist eng mit der Verfügbarkeit geeigneter Photoschalter verknüpft, die innerhalb des biologischen Fensters (λ=650–1450 nm) adressierbar sind, um eine maximale Eindringtiefe ins Gewebe zu ermöglichen. Mithilfe einer generellen Designstrategie wurde ein Dihydropyren‐Derivat entwickelt, das negative T‐Typ‐Photochromie aufweist und ein effizientes sowie nahezu quantitatives (95 %) Schalten unter Einwirkung von NIR‐Licht mit λ>800 nm ermöglicht. Die thermische Halbwertzeit des entfärbten, offenen meta‐Cyclophandien‐Isomers variiert zwischen Minuten und Stunden je nach Lösungsmittelpolarität und kann als Sonde für die lokale Umgebung wirken. Durch die eher geringen Strukturunterschiede zwischen den beiden Isomeren wären entsprechend modifizierte NIR‐Photoschalter mögliche Kandidaten für das Schalten im aktiven Zentrum eines biologischen Targets und ermöglichen prinzipiell eine reversible, lichtinduzierte Inhibitor‐Deaktivierung als einen alternativen Ansatz zur externen Regulation biologischer Funktionen.
Development of a validated liquid chromatographic method for quantification of sorafenib tosylate in the presence of stress‐induced degradation products and in biological matrix employing analytical quality by design approach
Authors: Sharma Teenu , Khurana Rajneet Kaur , Jain Atul , Katare O.P. , Singh Bhupinder 
Published: December 2017

AbstractThe current research work envisages an analytical quality by design‐enabled development of a simple, rapid, sensitive, specific, robust and cost‐effective stability‐indicating reversed‐phase high‐performance liquid chromatographic method for determining stress‐induced forced‐degradation products of sorafenib tosylate (SFN). An Ishikawa fishbone diagram was constructed to embark upon analytical target profile and critical analytical attributes, i.e. peak area, theoretical plates, retention time and peak tailing. Factor screening using Taguchi orthogonal arrays and quality risk assessment studies carried out using failure mode effect analysis aided the selection of critical method parameters, i.e. mobile phase ratio and flow rate potentially affecting the chosen critical analytical attributes. Systematic optimization using response surface methodology of the chosen critical method parameters was carried out employing a two‐factor–three‐level–13‐run, face‐centered cubic design. A method operable design region was earmarked providing optimum method performance using numerical and graphical optimization. The optimum method employed a mobile phase composition consisting of acetonitrile and water (containing orthophosphoric acid, pH 4.1) at 65:35 v/v at a flow rate of 0.8 mL/min with UV detection at 265 nm using a C18 column. Response surface methodology validation studies confirmed good efficiency and sensitivity of the developed method for analysis of SFN in mobile phase as well as in human plasma matrix. The forced degradation studies were conducted under different recommended stress conditions as per ICH Q1A (R2). Mass spectroscopy studies showed that SFN degrades in strongly acidic, alkaline and oxidative hydrolytic conditions at elevated temperature, while the drug was per se found to be photostable. Oxidative hydrolysis using 30% H2O2 showed maximum degradation with products at retention times of 3.35, 3.65, 4.20 and 5.67 min. The absence of any significant change in the retention time of SFN and degradation products, formed under different stress conditions, ratified selectivity and specificity of the systematically developed method.
First in human evaluation of the vascular biocompatibility and biomechanical performance of a novel ultra high molecular weight amorphous PLLA bioresorbable scaffold in the absence of anti‐proliferative drugs: Two‐year imaging results in humans
Authors: Moncada Miguel , Delgado Juan A. , Colombo Antonio , Gasior Pawel , Ramzipoor Kamal , Estrada Alex , Lee Chang , Dokko Danny , Granada Juan F. 
Published: December 2017

AbstractObjectivesIn this first‐in‐human study, we prospectively studied the vascular compatibility and mechanical performance of a novel bare ultra‐high molecular weight amorphous PLLA bioresorbable scaffold (BRS, FORTITUDE®, Amaranth Medical, Mountain View, California) up to two years after implantation using multimodality imaging techniques.BackgroundThe vascular biocompatibility of polymers used in BRS has not been fully characterized in the absence of anti‐proliferative drugs.MethodsA total of 10 patients undergoing single scaffold implantation were included in the final analysis and were followed up using optical coherence tomography (OCT) at 2‐years. All devices were implanted under angiographic and intravascular ultrasound (IVUS) guidance. Angiographic and IVUS follow up was performed at 6 months. Additionally, angiography and OCT imaging were performed at 2‐years.ResultsAt 6 months, mean intra‐scaffold angiographic MLD slightly decreased from baseline procedural values. However, at 2 years, mean angiographic MLD increased (post procedure; 2.9 [2.7, 3.1] mm vs. 6 months; 2.1 [1.6, 2.5] vs. 2 years; 2.4 [2.1, 2.6], P = .001). Also, angiographic percent diameter stenosis decreased and late lumen gain increased between 6 months and 2 years follow up. Mean neointimal hyperplasia volume assessed by IVUS at 6 months was 26% [15.2, 29.3]. At 2 years OCT follow up neointimal hyperplasia volume was 24.2% [19.4, 28.9]. No presence of neoatherosclerosis was identified in any of the analyzed cases.ConclusionAt 2 years, this novel PLLA‐based BRS induced expansive vascular remodeling from 6 to 24 months, a biological phenomenon that appears to be independent of the presence of anti‐proliferative drugs.
A Self‐Repairing Cathode Material for Lithium–Selenium Batteries: Se−C Chemically Bonded Selenium–Graphene Composite
Authors: Sha Linna , Gao Peng , Ren Xiaochen , Chi Qianqian , Chen Yujin , Yang Piaoping 
Published: December 2017

AbstractLithium–selenium batteries, employing selenium as a cathode material, exhibit some notable advantages, such as high discharge rates and good cycling performance, due to their high electrical conductivity, high output voltages, and high volumetric capacity density. However, an important problem, termed the “shuttle effect”, can lead to capacity decay in Li‐Se cells (and in Li‐S cells), which arises from aggregation and the loss of Se or S from the cathode into the electrolyte. In this work, in order to solve this problem, a new self‐repairing system has been devised, in which some Se atoms are chemically bonded to the carbon atoms of graphene and act as reclaiming points for dissociated Se atoms through the establishment of ‐Se‐Se‐Se‐ chains. Se‐decorated graphene (Se‐GE) was first constructed through a facile high‐energy ball‐milling process. Its formation was confirmed by XRD, SEM, HRTEM, XPS, and Raman analyses. As we anticipated, in examining cell properties, the as‐prepared Se‐GE composite underwent an initial capacity decay in the first 20 cycles (from 1050 mAh g−1 to 750 mAh g−1, ca. 29 % loss), but the capacity then reverted to 970 mAh g−1 (ca. 92 % of the initial value). Other measurements were also consistent with the recapture of dissociated Se atoms.
Bis(dioxaborine) Dyes with Variable π‐Bridges: Towards Two‐Photon Absorbing Fluorophores with Very High Brightness
Authors: Marín Á. Moneo , Telo João P. , Collado Daniel , Nájera Francisco , Pérez‐Inestrosa Ezequiel , Pischel Uwe 
Published: December 2017

AbstractBis(dioxaborine) dyes of the A‐π‐A format (A: acceptor, π: conjugated bridge) were prepared and photophysically characterized. The best performing dyes feature (a) visible‐light absorption (>400 nm), (b) high molar absorption coefficients (up to 70000 m−1 cm−1), (c) Stokes shifts in the range of ca. 2500–5800 cm−1, and (d) strong fluorescence emission with quantum yields of up to 0.74. This yields very bright‐emitting dyes for one‐photon excitation. However, the most intriguing feature of the dyes is their strong two‐photon absorption. This was achieved by means of increased π‐conjugation in the phenylene or phenylene‐thiophene bridges through the variation of the conjugation length and rigidity. This provided two‐photon absorption cross sections of up to 2800 GM (1 Goeppert‐Mayer (GM)=10−50 cm4 s photon−1). Considering the mentioned high fluorescence quantum yields, exceptionally bright‐emitting A‐π‐A two‐photon absorbing dyes with low molecular mass are obtained. Time‐dependent density‐functional theory calculations corroborated the experimental results.
Synthesis and Dimerization Studies of a Lipophilic Photoresponsive Aryl‐Extended Tetraurea‐Calix[4]pyrrole
Authors: Sekiya Ryo , Díaz‐Moscoso Alejandro , Ballester Pablo 
Published: December 2017

AbstractWe describe the syntheses of the lipophilic aryl‐extended α,α,α,α‐tetraurea‐phenyl‐calix[4]pyrrole 1, featuring four appended azo‐phenyl groups with two tert‐butoxy carbonyl meta‐substituents and its photo‐inactive counterpart 2. In CD2Cl2 solutions, both tetraurea‐calix[4]pyrroles self‐assemble into dimeric capsules by encapsulating one molecule of a suitable bis‐N‐oxide or two molecules of a mono‐N‐oxide. The dimeric capsules are mainly stabilized by a cyclic array of sixteen hydrogen bonds established between the eight unidirectionally oriented urea groups. Photoirradiation experiments demonstrated the trans‐to‐cis isomerization of the azo‐phenyl groups and the formation of a plethora of stereo isomeric cis‐azo‐enriched capsular assemblies. The highly cis‐azo enriched capsular assemblies seem to show a reduced stability and their involvement in equilibria with non‐capsular counterparts that also bind the N‐oxides. The thermally induced cis‐to‐trans interconversion processes demonstrated the reversibility of the photoisomerization and the photostability of most binding partners. An equimolar mixture of the two tetraureas produced two homodimeric capsules and the heterodimeric counterpart in a ratio close to statistical distribution.
Mechanistic Studies on NaHCO3 Hydrogenation and HCOOH Dehydrogenation Reactions Catalysed by a FeII Linear Tetraphosphine Complex
Authors: Marcos Rocío , Bertini Federica , Rinkevicius Zilvinas , Peruzzini Maurizio , Gonsalvi Luca , Ahlquist Mårten S. G. 
Published: December 2017

AbstractWe present a theoretical extension of the previously published bicarbonate hydrogenation to formate and formic acid dehydrogenation catalysed by FeII complexes bearing the linear tetraphosphine ligand tetraphos‐1. The hydrogenation reaction was found to proceed at the singlet surface with two competing pathways: A) H2 association to the Fe−H species followed by deprotonation to give a Fe(H)2 intermediate, which then reacts with CO2 to give formate. B) CO2 insertion into the Fe−H bond, followed by H2 association and subsequent deprotonation. B was found to be slightly preferred with an activation energy of 22.8 kcal mol−1, compared to 25.3 for A. Further we have reassigned the Fe−H complex, as a Fe(H)(H2), which undergoes extremely rapid hydrogen exchange.
Structural Origin of Metal Specificity in Isatin Hydrolase from Labrenzia aggregata Investigated by Computer Simulations
Authors: Uribe Lalita , Diezemann Gregor , Gauss Jürgen , Morth Jens Preben , Cascella Michele 
Published: December 2017

AbstractWe performed quantum‐chemical calculations, ab initio molecular dynamics, hybrid quantum mechanics/molecular mechanics (QM/MM) and enhanced sampling metadynamics simulations to investigate the origin of metal specificity in isatin hydrolase from Labrenzia aggregata. The peculiar octahedral binding geometry of the Mn2+ ion in the Michaelis complex includes both the isatin substrate and the catalytic water within the first coordination shell of the cation. Our calculations show that the same arrangement of the ligands cannot be efficiently achieved in the presence of other small divalent metal cations such as Zn2+ or Cu2+. On the contrary, bulkier alkaline‐earth cations such as Mg2+, which allow octahedral coordination, are not able to activate the catalytic water into the stronger OH− nucleophile required to attack the stable N‐aryl‐amide moiety of isatin.
Pyro‐Phyllobilins: Elusive Chlorophyll Catabolites Lacking a Critical Carboxylate Function of the Natural Chlorophylls
Authors: Li Chengjie , Wurst Klaus , Berghold Joachim , Podewitz Maren , Liedl Klaus R. , Kräutler Bernhard 
Published: December 2017

AbstractA β‐keto ester grouping is a characteristic of ring E of the chlorophylls (Chls). Its presence has also reinforced the original identification of nonfluorescent Chl catabolites (NCCs) as colorless, amphiphilic phyllobilins (PBs). Polar NCCs were also detected in higher plants, in which a free carboxyl group replaced the ring E ester group. Such NCCs are surprisingly resistant to loss of this carboxyl unit, and NCCs lacking the latter, that is, pyro‐NCCs (pyNCCs), have not been reported. Intrigued by the question of the natural occurrence of pyro‐phyllobilins (pyPBs), we have prepared a representative pyNCC by decarboxylation of a natural NCC. We also converted the pyNCC into its yellow oxidation product, a pyro‐YCC (pyYCC). The solution structures of pyNCC and of pyYCC, and a crystal structure of the pyYCC methyl ester (pyYCC‐Me) were obtained. pyYCC‐Me features the same remarkable H‐bonded and π‐stacked dimer structure as the corresponding natural yellow Chl catabolite (YCC) with the ring E methyl ester group. Indeed, the latter substituent has little effect on the structure, as well as on the unique self‐assembly and photoswitch behavior of yellow PBs.
Direct, Metal‐free C(sp2)−H Chalcogenation of Indoles and Imidazopyridines with Dichalcogenides Catalysed by KIO3
Authors: Rafique Jamal , Saba Sumbal , Franco Marcelo S. , Bettanin Luana , Schneider Alex R. , Silva Lais T. , Braga Antonio L. 
Published: December 2017

AbstractHerein, we report a greener protocol for the synthesis of 3‐Se/S‐indoles and imidazo[1,2‐a]pyridines through direct C(sp2)−H bond chalcogenation of heteroarenes with half molar equivalents of different dichalcogenides, using KIO3 as a non‐toxic, easy‐to‐handle catalyst and a stoichiometric amount of glycerol. The reaction features are high yields, based on atom economy, easy performance on gram‐scale, metal‐ and solvent‐free conditions as well as applicability to different types of N‐heteroarenes.
Total Synthesis of Sarpagine‐Related Bioactive Indole Alkaloids
Authors: Rahman M. Toufiqur , Deschamps Jeffrey R. , Imler Gregory H. , Cook James M. 
Published: December 2017

AbstractExtension of the asymmetric Pictet–Spengler reaction to bulkier Nb‐alkylated tryptophan derivatives resulted in an improved stereospecific access to the key bicyclo[3.3.1]nonane core of bioactive C‐19 methyl substituted sarpagine/macroline/ajmaline indole alkaloids with excellent diastereoselectivity by internal asymmetric induction. Complete stereocontrol of the C‐19 methyl function in either the α‐ or β‐configuration was achieved, which enables the total synthesis of any member from this group of thirty alkaloids. We report herein, the total synthesis of macrocarpines (A‐C) 1–3, talcarpine 4, N(4)‐methyl‐N(4),21‐secotalpinine 5, dihydroperaksine 8 and deoxyperaksine 9.
Closing the Gap: Structural Evidence for the Missing Hexabromide Dianion [Br6]2−
Authors: Sonnenberg Karsten , Pröhm Patrick , Müller Carsten , Beckers Helmut , Steinhauer Simon , Lentz Dieter , Riedel Sebastian 
Published: December 2017

AbstractThe formation and experimental characterization of the first hexabromide dianion is presented. This dianion fills the last remaining gap in the series of polybromides from the tribromide [Br3]− to the undecabromide [Br11]−. The experimental results are compared to quantum‐chemical calculations. These calculations predict—based on electrostatic interactions—a T‐structure for the hexabromide dianion, while halogen–halogen bonding favors the hockey‐stick‐like structure experimentally found in the crystal structure. The hexabromide is built of two tribromide moieties, one of which is highly asymmetric. The classification of this unique anion as hexabromide dianion is discussed. The counter ion [C5H10N2Br]+ stabilizes the hexabromide dianion by additional σ‐hole interactions. The compound is fully characterized by mass spectrometry, NMR‐, IR and single crystal Raman spectroscopies as well as single‐crystal X‐ray diffraction.