bluuebunny/crossref_metadata_2025_split huggingface dataset:
Biodegradable Supramolecular Materials Based on Cationic Polyaspartamides and Pillar[5]arene for Targeting Gram‐Positive Bacteria and Mitigating Antimicrobial Resistance
Authors: Yan Shuzhen , Chen Shuai , Gou Xiangbo , Yang Jie , An Jinxia , Jin Xiaoyu , Yang Ying‐Wei , Chen Li , Gao Hui 
Published: July 2019

AbstractThe increasing number of infections caused by pathogenic bacteria has severely affected human society, for instance, numerous deaths are from Gram‐positive methicillin‐resistant Staphylococcus aureus (MRSA) each year. In this work, four biodegradable antibacterial polymer materials based on cationic polyaspartamide derivatives with different lengths of side chains are synthesized through the ring‐opening polymerization of β‐benzyl‐l‐aspartate N‐carboxy anhydride, followed by an aminolysis reaction and subsequent methylation reaction. The cationic quaternary ammonium groups contribute to the insertion of the catiomers into the negatively charged bacterial membranes, which leads to membranolysis, the leakage of bacterial content, and the death of pathogens. Except for wiping out MRSA readily, the biodegradable polymers possessing alterable antibacterial potency can minimize the possibility of microbial resistance and mitigate drug accumulation by virtue of their cleavable backbone. To manipulate the poor biocompatibility of these polycations, carboxylatopillar[5]arene (CP[5]A) is introduced to the polymeric antibacterial catiomers through the supramolecular host–guest approach to obtain novel antibacterial materials with pH‐sensitive characteristics (with CP[5]A departure from cationic quaternary ammonium compounds under acid conditions) and selective targeting of Gram‐positive bacteria. Finally, the facile and robust antibacterial system is successfully applied to in vivo MRSA‐infected wound healing, providing a significant reference for the construction of advanced antibacterial biomaterials.
Light‐Driven Active Proton Transport through Photoacid‐ and Photobase‐Doped Janus Graphene Oxide Membranes
Authors: Wang Lili , Wen Qi , Jia Pan , Jia Meijuan , Lu Diannan , Sun Xiaoming , Jiang Lei , Guo Wei 
Published: July 2019

AbstractBiological electrogenic systems use protein‐based ionic pumps to move salt ions uphill across a cell membrane to accumulate an ion concentration gradient from the equilibrium physiological environment. Toward high‐performance and robust artificial electric organs, attaining an antigradient ion transport mode by fully abiotic materials remains a great challenge. Herein, a light‐driven proton pump transport phenomenon through a Janus graphene oxide membrane (JGOM) is reported. The JGOM is fabricated by sequential deposition of graphene oxide (GO) nanosheets modified with photobase (BOH) and photoacid (HA) molecules. Upon ultraviolet light illumination, the generation of a net protonic photocurrent through the JGOM, from the HA‐GO to the BOH‐GO side, is observed. The directional proton flow can thus establish a transmembrane proton concentration gradient of up to 0.8 pH units mm−2 membrane area at a proton transport rate of 3.0 mol h−1 m−2. Against a concentration gradient, antigradient proton transport can be achieved. The working principle is explained in terms of asymmetric surface charge polarization on HA‐GO and BOH‐GO multilayers triggered by photoisomerization reactions, and the consequent intramembrane proton concentration gradient. The implementation of membrane‐scale light‐harvesting 2D nanofluidic system that mimics the charge process of the bioelectric organs makes a straightforward step toward artificial electrogenic and photosynthetic applications.
Self‐Confined Growth of Ultrathin 2D Nonlayered Wide‐Bandgap Semiconductor CuBr Flakes
Authors: Gong Chuanhui , Chu Junwei , Yin Chujun , Yan Chaoyi , Hu Xiaozong , Qian Shifeng , Hu Yin , Hu Kai , Huang Jianwen , Wang Hongbo , Wang Yang , Wangyang Peihua , Lei Tianyu , Dai Liping , Wu Chunyang , Chen Bo , Li Chaobo , Liao Min , Zhai Tianyou , Xiong Jie 
Published: July 2019

Abstract2D planar structures of nonlayered wide‐bandgap semiconductors enable distinguished electronic properties, desirable short wavelength emission, and facile construction of 2D heterojunction without lattice match. However, the growth of ultrathin 2D nonlayered materials is limited by their strong covalent bonded nature. Herein, the synthesis of ultrathin 2D nonlayered CuBr nanosheets with a thickness of about 0.91 nm and an edge size of 45 µm via a controllable self‐confined chemical vapor deposition method is described. The enhanced spin‐triplet exciton (Zf, 2.98 eV) luminescence and polarization‐enhanced second‐harmonic generation based on the 2D CuBr flakes demonstrate the potential of short‐wavelength luminescent applications. Solar‐blind and self‐driven ultraviolet (UV) photodetectors based on the as‐synthesized 2D CuBr flakes exhibit a high photoresponsivity of 3.17 A W−1, an external quantum efficiency of 1126%, and a detectivity (D*) of 1.4 × 1011 Jones, accompanied by a fast rise time of 32 ms and a decay time of 48 ms. The unique nonlayered structure and novel optical properties of the 2D CuBr flakes, together with their controllable growth, make them a highly promising candidate for future applications in short‐wavelength light‐emitting devices, nonlinear optical devices, and UV photodetectors.
Novel Stable 3D Stainless Steel‐Based Electrodes for Efficient Water Splitting
Authors: Zhang Haojie , de Souza e Silva Juliana Martins , Lu Xubin , de Oliveira Cristine Santos , Cui Bin , Li Xiaopeng , Lin Chao , Schweizer Stefan L. , Maijenburg A. Wouter , Bron Michael , Wehrspohn Ralf B. 
Published: July 2019

AbstractThe stability of electrocatalysts grown on substrates is a significant challenge for the construction of 3‐dimensional (3D) stainless‐steel (SS)‐based electrodes for highly efficient water splitting. This paper presents an efficient and universal process to enhance the interfacial interaction between SS and highly active electrocatalysts for the preparation of 3D electrodes through the formation of an interfacial network of carbon nanotubes (CNTs) on the SS. Nanoscale X‐ray computed tomography and focused ion beam are used to visualize the interface between CNTs and SS, and 3D structure of CNT/SS electrodes. The strongly interconnected CNTs network increases the surface area of the SS support that benefits the modification of highly active electrocatalysts and also serves as an electron/charge‐conductive highway between electrocatalysts and support. The electrocatalysts on CNT/SS further improve hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performances, respectively, of the 3D electrodes. While compared to the SS‐based electrodes reported recently, Pt/OxCNT/SS shows the best HER activity over wide pH range and RuO2/OxCNT/SS exhibits a comparable OER performance in neutral and alkaline electrolyte. An efficient approach is reported to combine highly active electrocatalysts with SS for the preparation of active and stable 3D electrodes that can be further explored in various areas.
Impact of Nonfullerene Acceptor Side Chain Variation on Transistor Mobility
Authors: Bristow Helen , Thorley Karl J. , White Andrew J. P. , Wadsworth Andrew , Babics Maxime , Hamid Zeinab , Zhang Weimin , Paterson Alexandra F. , Kosco Jan , Panidi Julianna , Anthopoulos Thomas D. , McCulloch Iain 
Published: July 2019

AbstractOrganic photovoltaic power conversion efficiencies exceeding 14% can largely be attributed to the development of nonfullerene acceptors (NFAs). Many of these molecules are structural derivatives of IDTBR and ITIC, two common NFAs. By modifying the chemical structure of the acceptor, the optical absorption, energy levels, and bulk heterojunction morphology can be tuned. However, the effect of structural modifications on NFA charge transport properties has not yet been fully explored. In this work, the relationship between chemical structure, molecular packing, and charge transport, as measured in organic thin‐film transistors (OTFTs), is investigated for two high performance NFAs, namely O‐IDTBR and ITIC, along with their structural derivatives EH‐IDTBR and ITIC‐Th. O‐IDTBR exhibits a higher n‐type saturation field effect mobility of 0.12 cm2 V−1 s−1 compared with the other acceptors investigated. This can be attributed to the linear side chains of O‐IDTBR which direct an interdigitated columnar packing motif. The study provides insight into the transport properties and molecular packing of NFAs, thereby contributing to understanding the relationship between chemical structure, material properties, and device performance for these materials. The high electron mobility achieved by O‐IDTBR also suggests its applications can be extended to use as an n‐type semiconductor in OTFTs.
Marked Cofuel Tuning of Combustion Synthesis Pathways for Metal Oxide Semiconductor Films
Authors: Wang Binghao , Leonardi Matthew J. , Huang Wei , Chen Yao , Zeng Li , Eckstein Brian J. , Marks Tobin J. , Facchetti Antonio 
Published: July 2019

AbstractThin‐film combustion synthesis (CS), driven by the exothermic reaction of liquid fuel+oxidizer+metal precursors is an important methodology for growing smooth, transparent, amorphous, and polycrystalline metal oxide (MO) films at low temperatures. In optimized MO CS precursors, the fuel combines a primary coordinating ligand [e.g., acetylacetone (AcAcH)] with an additional cofuel. Several studies suggest a structure–property relationship between the resulting MO film composition/microstructure and macroscopic charge transport characteristics. However, the structural and compositional details of solution‐phase precursors remain poorly defined. Here a diverse series of cofuels (urea, glycine, sorbitol, L‐ascorbic acid) are selected and mechanistic details of the fuel‐assisted CS process are provided, focusing on technologically relevant indium gallium zinc oxide (IGZO). Thermal analysis, proton nuclear magnetic resonance, mass spectrometry, and X‐ray diffraction are used to probe how the cofuel affects AcAcH‐metal ion binding and how it influences the MO precursor response. The charge transport characteristics of cofuel‐derived IGZO films stimulate additional cofuel studies and the results support the primary cofuel role of enhancing CS heat generation, hence IGZO film microstructure densification and carrier mobility. These results provide new insight into precursor design and its relationship to thin‐film CS processes, yielding guidance for more efficient, environmentally benign (co)fuels for high‐performance solution‐processed MO electronics.
Infant loss during and after male replacement in gibbons
Authors: Ma Chang‐Yong , Brockelman Warren Y. , Light Lydia E. O. , Bartlett Thad Q. , Fan Peng‐Fei 
Published: July 2019

AbstractAccording to the sexual selection hypothesis, infanticide during resident male replacement is an adaptive strategy that has evolved because the killing of unweaned offspring sired by previous males shortens the inter‐birth intervals of the mothers whose infants are targeted and thereby increases the reproductive fitness of the perpetrator. To test this hypothesis, we describe previously unreported cases of primary male replacement for two gibbon species (Hylobates lar and Nomascus nasutus), and review all other reported cases of primary male replacement in gibbons. Overall, infants were present in nearly half of all cases (16/33, 48%) and of the 18 infants present during replacement, 50% (N = 9) disappeared within 2 months of the event. In four of the five cases where there was sufficient demographic information to identify the likely sire of the subsequent offspring of females that lost infants, the new male was believed to be the sire. Infants were also less likely to die or disappear if the new male and original resident male were possible kin. However, there was no significant difference in the age of infants between those that died or disappeared following replacement and those that survived to weaning (p = .630). Our review of takeover‐related infant loss in gibbons confirms that periods of male instability are risky for unweaned infants and that replacing males benefit from infant loss. Nevertheless, variability in the context of infant loss and difficulties related to data collection in the field make it difficult to test competing hypotheses concerning the mechanisms and functions of infanticide in the small apes.
Subicular pyramidal neurons gate drug resistance in temporal lobe epilepsy
Authors: Xu Cenglin , Wang Yi , Zhang Shuo , Nao Jiazhen , Liu Yao , Wang Ying , Ding Fang , Zhong Kai , Chen Liying , Ying Xiaoying , Wang Shuang , Zhou Yudong , Duan Shumin , Chen Zhong 
Published: July 2019

ObjectiveDrug‐resistant epilepsy causes great clinical danger and still lacks effective treatments.MethodsHere, we used multifaceted approaches combining electrophysiology, optogenetics, and chemogenetics in a classic phenytoin‐resistant epilepsy model to reveal the key target of subicular pyramidal neurons in phenytoin resistance.ResultsIn vivo neural recording showed that the firing rate of pyramidal neurons in the subiculum, but not other hippocampal subregions, could not be inhibited by phenytoin in phenytoin‐resistant rats. Selective inhibition of subicular pyramidal neurons by optogenetics or chemogenetics reversed phenytoin resistance, whereas selective activation of subicular pyramidal neurons induced phenytoin resistance. Moreover, long‐term low‐frequency stimulation at the subiculum, which is clinically feasible, significantly inhibited the subicular pyramidal neurons and reversed phenytoin resistance. Furthermore, in vitro electrophysiology revealed that off‐target use of phenytoin on sodium channels of subicular pyramidal neurons was involved in the phenytoin resistance, and clinical neuroimaging data suggested the volume of the subiculum in drug‐resistant patients was related to the usage of sodium channel inhibitors.InterpretationThese results highlight that the subicular pyramidal neurons may be a key switch control of drug‐resistant epilepsy and represent a new potential target for precise treatments. ANN NEUROL 2019;86:626–640
Cyclotris(paraquat‐p‐phenylenes)
Authors: Anamimoghadam Ommid , Cooper James A. , Nguyen Minh T. , Guo Qing‐Hui , Mosca Lorenzo , Roy Indranil , Sun Junling , Stern Charlotte L. , Redfern Louis , Farha Omar K. , Stoddart J. Fraser 
Published: July 2019

AbstractReported here is the synthesis, solid‐state characterization, and redox properties of new triangular, threefold symmetric, viologen‐containing macrocycles. Cyclotris(paraquat‐p‐phenylene) (CTPQT6+) and cyclotris(paraquat‐p‐1,4‐dimethoxyphenylene) (MCTPQT6+) were prepared and their X‐ray single‐crystal (super)structures reveal intricate three‐dimensional packing. MCTPQT6+ results in nanometer‐sized channels, in contrast with its parent counterpart CTPQT6+ which crystallizes as a couple of polymorphs in the form of intercalated assemblies. In the solid state, MCTPQT3(.+) exhibits stacks between the 1,4‐dimethoxyphenylene and bipyridinium radical cations, providing new opportunities for the manipulation and control of the recognition motif associated with viologen radical cations. These redox‐active cyclophanes demonstrate that geometry‐matching and weak intermolecular interactions are of paramount importance in dictating the formation of their intricate solid‐state superstructures.
Unkonventionelle Metall‐Netzwerk‐Wechselwirkungen in MgSi5
Authors: Hübner Julia‐Maria , Carrillo‐Cabrera Wilder , Prots Yurii , Bobnar Matej , Schwarz Ulrich , Grin Yuri 
Published: July 2019

AbstractDie siliciumreiche Käfigverbindung MgSi5 wird durch Hochdruck‐Hochtemperatur‐Synthese erhalten. Die erste Bestimmung der Kristallstruktur durch Elektronendiffraktionstomographie schaffte die Basis für Phasenanalysen und damit für den Optimierungsprozess der Synthesebedingungen. Dieser Prozess ermöglichte letztendlich die Herstellung von Einkristallen, die für Röntgendiffraktionsexperimente geeignet waren. Die Kristallstruktur von MgSi5 (Raumgruppe Cmme, oS24, a=4.4868(2) Å, b=10.1066(5) Å und c=9.0753(4) Å) stellt eine neue Art eines Netzwerks dar, in dem vierbindige Siliciumatome die Magnesiumatome umschließende Si15‐Käfige bilden. Zwei Arten kleinerer Si8‐Käfige bleiben leer. Die atomaren Wechselwirkungen sind durch zwei‐Zentren‐zwei‐Elektronen Bindungen innerhalb des Siliciumnetzwerks gekennzeichnet. Zusätzlich gibt es Hinweise auf Mehrzentren‐Bindungen zwischen Mg und Si in den großen Hohlräumen des Netzwerks und auf Interaktionen in den kleineren leeren Lücken, die denen zwischen freien Elektronenpaaren ähneln.
Glycidyl Tosylate: Polymerization of a “Non‐Polymerizable” Monomer permits Universal Post‐Functionalization of Polyethers
Authors: Jung Philipp , Ziegler Arthur D. , Blankenburg Jan , Frey Holger 
Published: July 2019

AbstractGlycidyl tosylate appears to be a non‐polymerizable epoxide when nucleophilic initiators are used because of the excellent leaving group properties of the tosylate. However, using the monomer‐activated mechanism, this unusual monomer can be copolymerized with ethylene oxide (EO) and propylene oxide (PO), respectively, yielding copolymers with 7–25 % incorporated tosylate‐moieties. The microstructure of the copolymers was investigated via in situ 1H NMR spectroscopy, and the reactivity ratios of the copolymerizations have been determined. Quantitative nucleophilic substitution of the tosylate‐moiety is demonstrated for several examples. This new structure provides access to a library of functionalized polyethers that cannot be synthesized by conventional oxyanionic polymerization.
Unconventional Metal–Framework Interaction in MgSi5
Authors: Hübner Julia‐Maria , Carrillo‐Cabrera Wilder , Prots Yurii , Bobnar Matej , Schwarz Ulrich , Grin Yuri 
Published: July 2019

AbstractThe silicon‐rich cage compound MgSi5 was obtained by high‐pressure high‐temperature synthesis. Initial crystal structure determination by electron diffraction tomography provided the basis for phase analyses in the process of synthesis optimization, finally facilitating the growth of single crystals suitable for X‐ray diffraction experiments. The crystal structure of MgSi5 (space group Cmme, Pearson notation oS24, a=4.4868(2) Å, b=10.1066(5) Å, and c=9.0753(4) Å) constitutes a new type of framework of four‐bonded silicon atoms forming Si15 cages enclosing the Mg atoms. Two types of smaller Si8 cages remain empty. The atomic interactions are characterized by two‐center two‐electron bonds within the silicon framework. In addition, there is evidence for multi‐center Mg−Si bonding in the large cavities of the framework and for lone‐pair‐like interactions in the smaller empty voids.
Bifunctional Gyroidal MOFs: Highly Efficient Lewis Base and Lewis Acid Catalysts
Authors: Li Yan Yan , He Tian‐Ya , Dai Rui‐Rong , Huang Yong‐Liang , Zhou Xiao‐Ping , Chen Tianfeng , Li Dan 
Published: July 2019

AbstractA family of gyroidal metal–organic frameworks (STUs) composited with transition metal ions and bi‐imidazolate ligands (BIm) were prepared and applied as both Lewis base and acid catalysts. Benefiting from the intrinsic basicity of the ligands and the Lewis acidic sites of the open metal centres, the STUs materials show excellent catalytic activities as Lewis base for the Knoevenagel condensation reaction between various aldehydes and malononitrile, and as Lewis acid for cyanosilylation reactions. Among these STUs, STU‐4 (Ni(BIm)) shows the best catalytic efficiency (conversions >99 %) in both Knoevenagel condensation and cyanosilylation reactions under mild conditions, providing thus an advanced material for both Lewis base and Lewis acid catalysis.
Prognostic factors and patterns of failure after surgery for T4 rectal cancer in the beyond total mesorectal excision era
Authors: Peacock O , Waters P S , Bressel M , Lynch A C , Wakeman C , Eglinton T , Koh C E , Lee P J , Austin K K , Warrier S K , Solomon M J , Frizelle F A , Heriot A G 
Published: July 2019

Abstract

Background
Despite advances in the rates of total mesorectal excision (TME) for rectal cancer surgery, decreased local recurrence rates and increased 5-year survival, there still exists large variation in the quality of treatment received. Up to 30 per cent of rectal cancers are locally advanced at presentation and approximately 5–10 per cent still breach the mesorectal plane and invade adjacent structures despite neoadjuvant therapy. With the evolution of extended resections for rectal cancers beyond the TME plane, proponents advocate that these resections should be performed only in specialist centres. The aim was to assess the prognostic factors and patterns of failure after beyond TME surgery for T4 rectal cancers.

Methods
Data were collected from prospective databases at three high-volume institutions specializing in beyond TME surgery for T4 rectal cancers between 1990 and 2013. The primary outcome measures were overall survival, local recurrence and patterns of first failure.

Results
Three hundred and sixty patients were identified. The negative resection margin (R0) rate was 82·8 per cent (298 patients) and the local recurrence rate was 12·5 per cent (45 patients). The type of surgical procedure (Hartmann's: hazard ratio (HR) 4·49, 95 per cent c.i. 1·99 to 10·14; P = 0·002) and lymphovascular invasion (HR 2·02, 1·08 to 3·77; P = 0·032) were independent predictors of local recurrence. The 5-year overall survival rate for all patients was 61 (95 per cent c.i. 55 to 67) per cent. The 5-year cumulative incidence of first failure was 8 per cent for local recurrence, 6 per cent for local and distant disease, and 18 per cent for distant disease.

Conclusion
This study has demonstrated that a coordinated approach in specialist centres for beyond TME surgery can offer good oncological and long-term survival in patients with T4 rectal cancers.
Expression of vasopressin mRNA in the hypothalamus of individuals with a diagnosis of schizophrenia
Authors: Busch Johannes R. , Jacobsen Christina , Lynnerup Niels , Banner Jytte , Møller Morten 
Published: July 2019

AbstractObjectiveThis study investigates the expression of mRNA encoding vasopressin in the hypothalamus of autopsy brains of individuals diagnosed with schizophrenia.MethodsTen brains of individuals with schizophrenia and 10 brains from individuals without any disease were examined during autopsy. The hypothalamic block was dissected and immersion fixed in paraformaldehyde, sucrose substituted, frozen, and cut into 20‐µm‐thick coronal cryostat sections. The sections were hybridized with an S‐35‐labeled DNA antisense oligo probe and after washing covered by an X‐ray film. The hybridization signals on the films were transferred to a computer and densitometrically quantified.ResultsThe densitometry signals showed a statistically significant lower mRNA expression (53% decrease; p = 0.014) in the paraventricular nucleus of the individuals with schizophrenia compared to the controls. In the supraoptic nucleus, the decrease in the group with schizophrenia was 39% compared to the controls, but this decrease was not statistically significant (p = 0.194).ConclusionsOur results show a low expression of mRNA encoding vasopressin in the paraventricular nucleus of the individuals with schizophrenia. We suggest that vasopressin is not directly involved in the pathogenesis of schizophrenia, but might influence schizophrenic symptoms via vasopressin receptors located in the social behavioral neural network in the forebrain.