bluuebunny/crossref_metadata_2025 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

The 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

Biological 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

2D 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

The 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

Organic 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

Thin‐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

According 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

Objective

Drug‐resistant epilepsy causes great clinical danger and still lacks effective treatments.

Methods

Here, 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.

Results

In 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.

Interpretation

These 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

Reported 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

Die 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

Glycidyl 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

The 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

A 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.
Intermittent pulsed electromagnetic field stimulation activates the mTOR pathway and stimulates the proliferation of osteoblast‐like cells
Authors: Miyamoto Hironori , Sawaji Yasunobu , Iwaki Takahiro , Masaoka Toshinori , Fukada Eiichi , Date Munehiro , Yamamoto Kengo
Published: July 2019

Pulsed electromagnetic fields (PEMFs) have been shown to be a noninvasive physical stimulant for bone fracture healing. However, PEMF stimulation requires a relatively long period of time and its mechanism of action has not yet been fully clarified. Recently, the mammalian target of rapamycin (mTOR) pathway has been shown to be involved in bone formation. This study aimed to investigate the effects of PEMFs on osteoblastic MC3T3‐E1 cells by examining various cellular responses including changes in the mTOR pathway. Continuous PEMF stimulation induced a transient phosphorylation of the mTOR pathway, whereas intermittent PEMF stimulation (1 cycle of 10 min stimulation followed by 20 min of stimulation pause) revitalized the reduced phosphorylation. Moreover, PEMF stimulation stimulated cell proliferation (bromodeoxyuridine incorporation) rather than differentiation (alkaline phosphatase activity), with a more notable effect in the intermittently stimulated cells. These results suggest that intermittent PEMF stimulation may be effective in promoting bone fracture healing by accelerating cell proliferation, and in shortening stimulation time. Bioelectromagnetics. 2019;40:412–421. © 2019 Bioelectromagnetics Society.
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

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

Objective

This study investigates the expression of mRNA encoding vasopressin in the hypothalamus of autopsy brains of individuals diagnosed with schizophrenia.

Methods

Ten 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.

Results

The 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).

Conclusions

Our 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.
Design, Synthesis and in Vitro Tumor Cytotoxicity Evaluation of 3,5‐Diamino‐N‐substituted Benzamide Derivatives as Novel GSK‐3β Small Molecule Inhibitors
Authors: Zhou Yanping , Zhang Lijuan , Fu Xiujuan , Jiang Zhongliang , Tong Rongsheng , Shi Jianyou , Li Jian , Zhong Lei
Published: July 2019

Glycogen synthase kinase‐3 (GSK‐3) plays an important regulatory role in various signaling pathways; such as PI3 K/AKT, which is closely related to the occurrence and development of tumors. At present, the most reported active GSK‐3 inhibitors have the same structure: lactam ring or amide structure. To find out the GSK‐3β small molecule inhibitor with novel, safe, efficient and more uncomplicated synthesis method, we analyzed in‐depth reported crystal‐binding patterns of GSK‐3β small molecule inhibitor with GSK‐3β protein, and designed and synthesized 17 non‐reported 3,5‐diamino‐N‐substituted benzamide compounds. Their structures were confirmed by 1H‐NMR, 13C‐NMR, and HR‐MS. The preliminary screening of tumor cytotoxicity of compounds in vitro was detected by MTT, and their structure–activity relationships were illustrated. The results have shown that 3,5‐diamino‐N‐[3‐(trifluoromethyl)phenyl]benzamide (4d) exhibited significant tumor cytotoxicity against human colon cancer cells (HCT‐116) with IC50 of 8.3 μm and showed commendable selectivity to GSK‐3β. In addition, Compound 4d induced apoptosis to some extent and possessed modest PK properties.
Comparative outcomes for a national cohort of persons convicted of murder, with and without serious mental illness, and those found not guilty by reason of insanity on a murder charge: A 25‐year follow‐up study
Authors: Skipworth Jeremy , Bevin Wendy , McKenna Brian , Simpson Alexander I.F. , Brinded Phil , Pearson Janet
Published: July 2019

Background

Serious mental illness (SMI) is common among persons sentenced to life imprisonment for murder, yet little is known about how this affects rehabilitation, prospects of parole, or risk to the community.

Aim

The aim of this study is to compare outcomes for a national cohort of offenders charged with murder who were either convicted and sentenced to life in prison or placed on a forensic hospital order.

Methods

The 386 cases of murder charges in New Zealand between 1988 and 2000 were divided into three groups: perpetrators without SMI sentenced to life imprisonment (n = 313), perpetrators with SMI but sentenced to life imprisonment (n = 32), or those with such illness and found not guilty by reason of insanity (NGRI) who received a forensic hospital order (n = 41). Access to rehabilitative interventions, time to release, reoffending, and recall to prison or hospital were examined.

Results

Being in prison but having severe mental illness delayed release on parole but did not increase the risk of criminal recidivism or recall to prison. Hospital order patients were a demographically different group; they were released to the community earlier and had a lower rate of criminal recidivism.

Conclusions

This study provides some evidence that incarceration periods for life‐sentenced homicide perpetrators with SMI may be reduced without increasing community risk if hospital transfer and/or more targeted interventions are provided in prison. It also provides further evidence that persons found NGRI after a charge of murder have a relatively low risk of criminal recidivism. The stigma that may sometimes attach to such offenders is unwarranted, if it relies on concerns about risk of reoffending.
Mechanism of Oxidative Activation of Fluorinated Aromatic Compounds by N‐Bridged Diiron‐Phthalocyanine: What Determines the Reactivity?
Authors: Colomban Cédric , Tobing Anthonio H. , Mukherjee Gourab , Sastri Chivukula V. , Sorokin Alexander B. , de Visser Sam P.
Published: July 2019

The biodegradation of compounds with C−F bonds is challenging due to the fact that these bonds are stronger than the C−H bond in methane. In this work, results on the unprecedented reactivity of a biomimetic model complex that contains an N‐bridged diiron‐phthalocyanine are presented; this model complex is shown to react with perfluorinated arenes under addition of H2O2 effectively. To get mechanistic insight into this unusual reactivity, detailed density functional theory calculations on the mechanism of C6F6 activation by an iron(IV)‐oxo active species of the N‐bridged diiron phthalocyanine system were performed. Our studies show that the reaction proceeds through a rate‐determining electrophilic C−O addition reaction followed by a 1,2‐fluoride shift to give the ketone product, which can further rearrange to the phenol. A thermochemical analysis shows that the weakest C−F bond is the aliphatic C−F bond in the ketone intermediate. The oxidative defluorination of perfluoroaromatics is demonstrated to proceed through a completely different mechanism compared to that of aromatic C−H hydroxylation by iron(IV)‐oxo intermediates such as cytochrome P450 Compound I.
Catalyst‐Free Arylation of Tertiary Phosphines with Diaryliodonium Salts Enabled by Visible Light
Authors: Bugaenko Dmitry I. , Volkov Alexey A. , Livantsov Mikhail V. , Yurovskaya Marina A. , Karchava Alexander V.
Published: July 2019

The visible‐light‐induced arylation of tertiary phosphines with aryl(mesityl)iodonium triflates to produce the quaternary phosphonium salts occurs under mild, metal, and catalyst‐free conditions. Photo‐excited EDA complexes between diaryliodonium salts and phosphines supposedly enable this transformation, which is difficult to achieve through the traditional ground‐state reactions. Demonstrating high functional group tolerance, broad scope, and complete selectivity of the aryl group transfer, the method is particularly compatible with sterically congested phosphines, which are challenging under metal‐based catalytic methods.
From p‐Xylene to Ibuprofen in Flow: Three‐Step Synthesis by a Unified Sequence of Chemoselective C−H Metalations
Authors: Lee Hyune‐Jea , Kim Heejin , Kim Dong‐Pyo
Published: July 2019

Ibuprofen was prepared from an inactive and inexpensive p‐xylene by three‐step flow functionalizations through chemoselective metalations of benzyl positions in sequence using an in situ generated LICKOR‐type superbase. The flow approach in the microreactor facilitated the comprehensive exploration of over 100 conditions in the first‐step reaction by varying concentrations, temperatures, solvents, and equivalents of reagents, enabling optimal conditions to be found with 95 % yield by significantly suppressing the formation of byproducts, followed by the second C−H metalation step in 95 % yield. Moreover, gram‐scale synthesis of ibuprofen in the final step was achieved by biphasic flow reaction of solution‐phase intermediate with CO2, isolating 2.3 g for 10 min of operation time.
Quantitatively immunological characterization of mogamulizumab skin disorders in ATL patients
Authors: Ito Asahi , Suzuki Yui , Masaki Ayako , Yoshida Shinichiro , Suzushima Hitoshi , Takemoto Shigeki , Utsunomiya Atae , Ishii Toshihiko , Hiura Masanori , Takahashi Takeshi , Yurimoto Satoshi , Inagaki Hiroshi , Morita Akimichi , Iida Shinsuke , Ishida Takashi
Published: July 2019

Purpose

Skin disorders demonstrate highly variable phenotypical and histopathological features. Mogamulizumab, a humanized anti‐CC chemokine receptor 4 monoclonal antibody indicated for the treatment of adult T‐cell leukemia‐lymphoma, has been shown to induce skin‐related adverse events in some patients, including rare cases of Stevens‐Johnson syndrome. Hence, we aimed to elucidate immunological primary reactions in skins of mogamulizumab by quantitatively comparing any patterns of other skin disorders.

Methods

We quantitatively analyzed Foxp3+, CD8+, CD4+, granzyme B+, CD56+, and macrophage‐derived chemokine‐positive cells, and compared the results with trends observed in other inflammatory skin disorders such as psoriasis vulgaris, atopic dermatitis, and lichen planus. The analysis was separately performed in dermis, basement membrane, or epidermis of skins.

Results

Foxp3+/CD8+ cell ratio in dermis and basement membrane of mogamulizumab‐emergent skin disorders was significantly lower compared with those of the other skin disorders. In inflammatory skins, the more the number of CD8+ cells were infiltrated, the more the number of Foxp3+ cells were prone to be infiltrated, but not in mogamulizumab‐emergent skin disorders. No significant difference between all of the other skin disorders was observed in other immunological markers.

Conclusion

The low Foxp3+/CD8+ cell ratio of skins is the underlying reason for mogamulizumab‐emergent skin disorders.
Hydrogen Diffusion Guided Design of Pt‐Based Alloys for Inhibition of Butadiene Over‐Hydrogenation
Authors: Hu Chaoquan , Sun Jiahan , Wang Dongjie , Peng Mi , Shao Mingyuan , Zhu Qingshan , Ma Ding
Published: July 2019

The front cover artwork is provided by the groups of Dr. Chaoquan Hu, Prof. Qingshan Zhu (Institute of Process Engineering, Chinese Academy of Sciences), and Prof. Ding Ma (Peking University, P.R. China). The image shows the inhibition of C=C bond hydrogenation by increasing the barrier for H atom diffusion to the site, on which the H atom shares two Pt atoms with the C=C bond. Read the full text of the Article at 10.1002/cphc.201900380.
PlantNE: a global database of plant biomass from nitrogen‐addition experiments
Authors: Xu Xiaoni , Lu Ruiling , Yan Liming , Xia Jianyang
Published: July 2019

The growth of terrestrial plants and the production of terrestrial ecosystems are highly dependent on the availability of nitrogen (N). During the past decades, the rate of global atmospheric N deposition has shown an increasing trend, greatly relieving N limitation on terrestrial plant growth. Thus, whether and how plant biomass will respond to increasing N deposition in the future is particularly important with regard to the function of terrestrial ecosystems. The N‐addition experiment is a major approach to study the ecological responses of plant species occurring in natural terrestrial ecosystems under N enrichment. In recent decades, many N‐addition experiments have been conducted across various plant functional types and terrestrial ecosystems, but their data on plant biomass have yet to be synthesized into a single database. Here, we present an open‐access database of measured plant biomass in N‐addition experiments (PlantNE) collected from available publications in Web of Science. The reported mean, standard deviation, and sample size of plant biomass in both control and treatment plots were collected in each publication. As a result, the PlantNE database records 519 plant species from 4,599 observations in 348 published studies. It covers a wide geographical range (54.75° S–69.66° N; 157.80° W–175.30°E) and a broad natural climate zone (−10°C to 27.6°C; 94–7,000 mm) over the past three decades (1982–2018). Information related to the experimental site (i.e., latitude, longitude, country, ecosystem, experimental condition, temperature, and precipitation), biotic factors (i.e., species, plant category, plant age, planting pattern, and plant part), and N treatment (i.e., N dose, treatment interval and duration, and N addition with other treatments) is included in this database. We expect that the PlantNE database can contribute to the understanding of ecosystem productivity and biodiversity under increasing atmospheric N deposition and provide empirical data for model studies. There are no copyright restrictions; personal or noncommercial use of this database by researchers and teachers is encouraged. Researchers are requested to cite this paper if using all or part of the database. As we intend to keep this database up to date on GitHub (see Metadata S1 for details) and Zenodo (https://doi.org/10.5281/zenodo.3359810), researchers are encouraged to inform us of the applications of this database.
Severe drought limits trees in a semi‐arid savanna
Authors: Case Madelon F. , Wigley‐Coetsee Corli , Nzima Noel , Scogings Peter F. , Staver A. Carla
Published: July 2019

Increasingly frequent and severe droughts under climate change are expected to have major impacts on vegetation worldwide. However, research to date has focused on tree vulnerability to drought in forests. Less is known about trees and drought in savannas, where a sparse tree layer coexists with grass. These tree–grass interactions (often mediated by fire and herbivory) shape savanna tree ecology, and confound predictions of how strongly drought might affect trees. On the one hand, drought is physiologically stressful, which could harm trees and be exacerbated by herbivore impacts; on the other hand, trees adapted to semiarid savannas might be relatively drought tolerant, and the considerable impacts of drought on grass could even benefit trees via reduced grass competition and fire risk, especially in the year following a drought. Here, we sought to understand the net effects of severe drought on the savanna tree layer, and how fire and herbivory mediate these effects. We monitored tree growth, mortality, and community structure for 2 yr within existing long‐term fire and herbivory experiments across a drought‐severity contrast, following a major drought in Kruger National Park, South Africa. Overall, severe drought was a major stressor for trees. Tree mortality rates in most species increased by an order of magnitude in the year following drought, and slower growth rates for some persisted for 2 yr. At the community level, this translated into substantial decreases in tree densities. Herbivory and fire did little either to mitigate or exacerbate drought effects on trees, and overall, drought swamped effects of herbivory and fire that have otherwise been observed. However, species differed in their responses to drought, with some dominant encroaching species especially vulnerable. We suggest that increasing drought frequency and severity could drastically alter savanna vegetation by repeatedly killing off trees.
A Copper Metal–Organic Hydrogel as a Catalyst for SO2 and CO2 Fixation under Ambient Conditions
Authors: Karan Chandane Kumar , Bhattacharjee Manish
Published: July 2019

A copper metal–organic hydrogel (MOG) has been synthesized using an amino acid‐based ligand, Na2HL {H3L = 2‐{(3,5‐di‐tert‐butyl‐2‐hydroxybenzyl)amino succinic acid} as a gelator. The metallohydrogel exhibits pH‐responsive nature as well as chemical responsiveness. Besides, it shows rapid thixotropic behavior when external mechanical forces are applied. The metal–organic hydrogel can be used as a heterogeneous catalyst for the reaction of SO2 and CO2 with epoxides to produce cyclic 1,3,2‐dioxathiolane‐2‐oxides and carbonates, respectively. The conversions were found to be dependent on the size and type of the side chain of the epoxides.
Catalyst‐Free Synthesis of Novel Dimeric Tetrahydroisoquinoline Derivatives through [2+2+2] Annulation
Authors: Cui Hai‐Lei , Liu Si , Jiang Lu
Published: July 2019

A simple, straightforward, and atom economic catalyst‐free [2+2+2] annulation of dihydroisoquinolines and allenoates has been developed. A diverse range of novel dimeric tetrahydroisoquinoline derivatives can be prepared in moderate to good yields (37–87 %) from readily available material. Dihydro‐β‐carboline can also be used in this reaction system delivering corresponding dimeric dihydro‐β‐carboline derivatives. Notably, the reaction could be easily scaled up to gram scale. The easy scale‐up of this process may provide structurally diversified natural product‐like molecules possessing privileged scaffold for potential application in biomedical research and other research fields. Interestingly, in contrast to the α,β‐selectivity observed in our previous study, β,γ‐selective [2+2+2] annulation was preferred in this work.
An efficient Benzannulation protocol for the synthesis of 9,9‐Diphenyl‐9H‐fluorenols using Intramolecular Allene Friedel–Crafts Annulation
Authors: Yaragorla Srinivasarao , Rajesh P.
Published: July 2019

Herein we report a one‐pot cascade benzannulation protocol for the synthesis 9,9‐diaryl‐9H‐fluorenol, a key structure of many important natural products which exhibit the significant biological activities particularly phosphodiesterase‐4 (PDE4) inhibitory activity. This approach proceeds through the annulation of tert‐propargyl alcohols with 2‐methyl acetylacetone through an intramolecular allene Friedel–Crafts reaction using Ca(OTf)2 as the environmentally benign catalyst. Synthetic transformations of these compounds to useful materials are also presented here with the aid of cross‐coupling and RCM reactions.
How does culture shape our moral identity? Moral foundations in Saudi Arabia and Britain
Authors: AlSheddi Mona , Russell Sophie , Hegarty Peter
Published: July 2019

North American measures of moral identity (MI) assume that caring and fairness are the most prototypical features of morality. Moral foundations theory describes such individualising foundations of morality as dominant in individualist cultures and binding foundations of morality as more particular to collectivist cultures. We weighed the criticism that moral identity scales are guilty of “liberal ethnocentrism” in two studies drawing on participants in the UK and Saudi Arabia. Only individualising traits were prototypical of concepts of moral people in Britain, while individualising and binding traits were both prototypical of such concepts in Saudi Arabia (Study 1, N = 160). In Study 2 (N = 539), participants completed the moral identity scale following typical instructions that referred to the prototypical traits of one of five moral foundations. Overall MI scores were lower in Britain than in Saudi Arabia, particularly when instructions described binding traits as characteristics of a moral person. Cross‐cultural differences were mediated by the perceived cultural importance attributed to these traits, particularly binding traits. These results justify concerns that existing moral identity scales underestimate important cultural variation in conceptualising moral identity, but justice and caring concerns remain the best single candidates for a universal foundation of human morality.
A new numerical method for evaluating the variation of casing inner diameter after strike‐slip fault sliding during multistage fracturing in shale gas wells
Authors: Xi Yan , Li Jun , Liu Gonghui , Zha Chunqing , Zeng Xiamao , Zhong Wenli
Published: July 2019

Casing shear deformation has become a prominent problem in the process of completion in shale gas wells. It was believed that the slide of strike‐slip fault induced by multistage fracturing was the main reason. This paper presented a new numerical investigation for evaluating the casing inner diameter after strike‐slip fault sliding based on the microseismic data. A 3D finite element model, considering the mechanical anisotropy of shale and heat‐fluid‐solid coupling effect during multistage fracturing, was developed to calculate the variation of casing inner diameter after fault sliding under different engineering and geological conditions. The calculation result was verified by comparison with the measurement result of the multi‐finger caliper survey. Sensitivity analysis was carried out and the results showed that decreasing the sliding distance, maintaining high pressure, increasing the casing thickness, and increasing the elasticity modulus and decreasing the Poisson ratio of cement sheath were beneficial to protect the casing integrity. Finally, the engineering verification demonstrated that the numerical method has an accuracy up to 85.9%. Numerical model in this study was expected to provide a better understanding of casing shear deformation and an evaluation method of casing inner diameter after fault sliding during multistage fracturing in shale gas wells.
Sedimentary characteristics of hyperpycnites in a shallow lacustrine environment: A case study from the Lower Cretaceous Xiguayuan Formation, Luanping Basin, Northeast China
Authors: Dou Luxing , Hou Jiagen , Song Suihong , Zhang Li , Liu Yuming , Sun Shuang , Li Yongqiang , Wang Xixin , Ren Xiaoxu , Tang Ying , Tian Heng , Yang Yuhua
Published: July 2019

Hyperpycnites are extrabasinal turbidites related to hyperpycnal flows which form during river floods. Compared to intrabasinal turbidite systems in deep marine or lacustrine settings, hyperpycnites in shallow lakes settings are not understood. In this work, we studied the typical sedimentary characteristics of shallow lacustrine hyperpycnal flow deposits in outcrops of the Luanping Basin, Northeast China. Based on the sedimentary architecture and analysis of the facies associations in these outcrops, the hyperpycnites can be classified into the following three types: (a) bedload‐dominated erosional channel deposits, (b) bedload‐ and suspended‐load‐dominated channel‐to‐lobe transitional deposits, and (c) suspended‐load‐dominated lobe deposits. The erosional channels in proximal locations are filled by mud clasts, parallel‐laminated sandstones, massive sandstones, cross‐bedded sandstones, massive siltstones, and mudstones. The channel‐to‐lobe transitional deposits in a middle location are composed of parallel‐laminated sandstones, cross‐bedded sandstones, mud clasts near internal erosional surfaces, ripple cross‐bedded sandstones, massive siltstones, and mudstones. The lobe deposits in distal locations are composed of ripple cross‐bedded sandstones, massive siltstones, and mudstones. The sedimentary process of the shallow lacustrine hyperpycnal flows shows obvious response to periodic flood energy fluctuations. Gentle slope, small capacity of flood discharges and semiarid paleoclimate may be the possible reason for the observed sedimentary architecture of the shallow lacustrine hyperpycnal flow deposits. Therefore, this study offers new insights into the sedimentology of shallow lacustrine deposits in rift basins.