bluuebunny/crossref_metadata_2025 huggingface dataset:
Constructing Progress Maps of Digital Technology for Diagnosing Mathematical Proficiency
Authors: Junpeng Putcharee , Krotha Jenrop , Chanayota Kanokphon , Tang KeowNgang , Wilson Mark
Published: October 2019

This research aims to construct and validate progress maps of digital technology for diagnosing the multidimensional mathematical proficiency (MP) in Number and Algebra for Grade 7 students utilizing the Construct Modeling Approach. Researchers employed four building blocks as follows. Firstly, researchers developed the progress maps as an assessment framework of multidimensional MP. This is followed by creating the test for diagnosing MP. Next, researchers assigned scoring criteria and created the transition points of students’ MP levels. Finally, researchers validated the quality of the progress maps through empirical evidence. A total sample 1,500 Grade 7 students was used to support the validity and reliability evidence of the progress maps through the Wright Map using Multidimensional Random Coefficients Multinomial Logit Model. Results revealed that there were two dimensions of progress maps, namely mathematical procedures (MAP) and structure of learning outcome (SLO), and the researchers investigated three strands of validity evidence, namely test content, response processes, and internal structure. The reliability values in the MAP and SLO were 0.84 and 0.80 respectively. Finally, the Grade 7 students were mainly found to be at level-2 in the MAP dimension (44.95%) and the SLO dimension (61.57%). The experts’ evaluation results showed that the digital technology that was developed at the “most appropriate” quality levels in terms of usefulness, suitability, and accuracy, and at the “very appropriate” for the feasibility aspect, and hence is successfully contributing to the clarification of learning goals, to support for student-centered instruction, and that it is helpful in improving in teacher professional development.
Improving Efficiency of Asset Management in the Context of Ensuring Competitiveness of Mechanical Engineering Enterprises in Developing Countries
Authors: Yepifanova Irina M.
Published: October 2019

The research paper deals with the formation of new scientific solutions regarding increasing the efficiency of asset management in the context of ensuring the competitiveness of mechanical engineering enterprises in developing countries. The study noted the disparity in the development of economically developed and developing countries. It is revealed that one of the main aspects of such disparity is the competitiveness of both the economies of the countries as a whole, and of individual industries and enterprises. At the same time, the importance of ensuring the competitiveness of mechanical engineering enterprises in developing countries was noted, taking into account their potential and opportunities for stimulating GDP and employment growth in these countries. The relationship between the competitiveness of mechanical engineering enterprises and their asset management is established. The main problems of asset management at the mechanical engineering enterprises in the developing countries are localized, and the ways of their elimination are proposed taking into account the division of enterprises into those operating as part of the transnational and foreign corporations, large enterprises with national capital, medium and small enterprises with national capital. A considerable range of problems regarding the asset management in small and medium enterprises was noted. Directions of further scientific researchers are suggested.
The investigation of copper-ion coordination to amyloid-beta and potential chelation materials for the treatment of Alzheimer’s disease
Authors: Pavuluru Neha , Luo Xuan
Published: October 2019

Alzheimer's disease is a neurodegenerative disorder that results in the death of neurons and impaired cognitive function. One of the pathological hallmarks of Alzheimer's is the formation of senile plaques which originate from the aggregation of the Amyloid-beta protein. Recent research has found a correlation between the overabundance of copper-ions in the brain and this problem. They have hypothesized that chelation therapy may be an effective tool to solve it. In this study, we conducted Density Functional Theory calculations to investigate the interaction of the copper-ion to the truncated Amyloid-beta protein, as well as the adsorption of the copper-ion by potential chelation materials. Binding energy and charge transfer calculations were evaluated for copper's interaction with potential chelators: monolayer boron nitride, monolayer molybdenum disulfide, and monolayer silicene. Silicene produced the highest binding energies to copper, and the evidence of charge transfer between copper and the monolayer proves that there is a strong ionic bond present. Although our three monolayers did not directly present chelation potential, the absolute differences between the binding energies of the silicene binding sites and the Amyloid-beta binding sites were minimal proving that further research in silicene chelators may be useful for therapy in Alzheimer's disease.
‘Extimacy’ (Extimité): From Structural Theory of Language to Affective Theory of ‘Ex-Centric’ Subject*
Authors: Lubowicz Hanna
Published: October 2019

The following exposure of the RSI topological complexities, orienting all the possible (inter)subjectivity, plays on the following two pairs of polarities: external/internal and linguistic/affective (it may be added: structure and topology). Lacan introduces the third possibility of human experience: “extimacy”, linking what is both excluded and intimate. The concept is the lacking link leading from structuralist approaches to language to thoroughly affective subjectivity of any speaking being. Spinosa’s geometrical, highly dynamic system and his “differential calculus of affects” may account for the part that the vicissitudes of drive play in human existence as rooted in the deeply “extimate” sources.
Influence Factors of People Purchasing on Social Commerce Sites
Authors: Chiang I Ping , Lin Kai Chieh , Huang Chih Hui , Yang Wan-Ling
Published: October 2019

With the growing use of social media in the world, a wide variety of social media applications and services have been produced. Popular social media platforms leverage their unique functions to persuade their users to adopt such applications and services, and many enterprises have begun to consider social media operations as a crucial aspect. Thus, since the gradual influence of social media on consumer behavior, a new social commerce model has begun to develop. This research examined both business and social aspects of social commerce sites to establish an evaluation model for measuring their quality and effectiveness. We collected 468 valid samples of online users who had used social commerce site to browse or purchase products and were willing to use again. We used EFA and CFA to confirm the model we constructed, and Partial least squares regression was used to analyze the relationship among the antecedents and consequences of quality evaluation in social commerce sites. According to the result, the consumers’ behaviors were most likely affected by functionality, enjoyment, process, reliability, presence, and identity with a social commerce site. This study not only provided a credible social commerce quality measurement for other scholars to conduct relevant research but also provide conclusions for the marketing strategy of social commerce sites and products as a reference.

keywords: Social commerce, Internet marketing, Online shopping, E-commerce

To cite this document: Chiang, I.-P., Lin, K.-C., Huang, C.-H., Yang, W.-L. (2019). Influence factors of people purchasing on social commerce sites. Contemporary Management Research, 15(2), 69-87. https://doi.org/10.7903/cmr.18575
Semen exosomes inhibit HIV infection and HIV‐induced proinflammatory cytokine production independent of the activation state of primary lymphocytes
Authors: Welch Jennifer L. , Kaufman Thomas M. , Stapleton Jack T. , Okeoma Chioma M.
Published: October 2019

Semen exosomes (SE) inhibit HIV infection. However, the effect of SE on cell activation and inflammation remains unknown. We characterized the response of peripheral blood mononuclear cells (PBMCs) from HIV‐uninfected and antiretroviral therapy‐suppressed HIV‐infected (HIV+) subjects to SE. Quiescent PBMCs or T‐cell receptor (TCR)‐activated PBMCs from HIV− and HIV+ donors were stimulated with SE in the presence/absence of ex vivo HIV infection. In HIV‐infected PBMCs, SE did not reactivate HIV, did not induce lymphoblast development, nor increase CD69+/CD25+ numbers. Furthermore, SE inhibited de novo HIV infection without altering cell activation. SE also asynchronously downregulated HIV‐inducible IL1β, IL8, and TNFα and upregulated CXCL10. These data suggest that SE inhibits HIV infection and production of HIV‐induced proinflammatory cytokines while preserving lymphocyte activation.
A Redox‐Triggered Bispecific Supramolecular Nanomedicine Based on Peptide Self‐Assembly for High‐Efficacy and Low‐Toxic Cancer Therapy
Authors: Yang Da‐Song , Yang Yin‐He , Zhou Yunjiang , Yu Li‐Li , Wang Rui‐Han , Di Bin , Niu Miao‐Miao
Published: October 2019

Polo‐like kinase 1 (PLK1) and polo‐like kinase 4 (PLK4) are closely associated with the progression of several cancers, and their bispecific inhibitors can kill tumor cells effectively. Herein, a redox‐responsive bispecific supramolecular nanomedicine based on the self‐assembly of a cyclic peptide, termed as C‐1, targeting both PLK1 and PLK4 as a potent anticancer agent is reported. C‐1 is a cyclic peptide in response to reducing agents such as glutathione (GSH), which is constructed by a combined approach of pharmacophore modeling, molecular docking, and reversible cyclization. After entering the cytosol of cancer cell, the disulfide linkage is reduced by intracellular GSH, with the resulting linear conformation self‐assembling into bispecific nanofibers. C‐1 can lead to apoptotic cell death by inducing caspase‐3 activation and PARP cleavage in HeLa cells. Moreover, it suppresses the growth of HeLa cells in cell assays, and inhibits the progression of HeLa cells‐induced xenografts in nude mice without inducing notable side effects. This work provides a successful example of developing the redox‐responsive bispecific nanomedicine for high‐efficacy and low‐toxic cancer therapy.
Metal Boride‐Based Catalysts for Electrochemical Water‐Splitting: A Review
Authors: Gupta Suraj , Patel Maulik K. , Miotello Antonio , Patel Nainesh
Published: October 2019

Electrocatalytic water‐splitting has gained a firm hold in the area of renewable hydrogen production owing to its integrative compatibility with intermittent energy sources. However, wide‐scale implementation of this technology demands discovery of new electrode materials that strike a good balance between efficiency, stability, and cost. In the pool of inexpensive electrodes capable of catalyzing hydrogen and oxygen evolution reactions, metal borides/borates have made a big splash in the last decade. However, the research in this family of electrocatalysts remains unorganized owing to the diversity of reports. This review summarizes the past and present research progress in metal borides/borates for electrocatalytic water‐splitting. The fundamental reasons for electrochemical behavior in different metal borides/borates are highlighted here, also including some comments regarding erroneous practices in the performance evaluation of metal borides/borates. Various strategies used to enhance the electrocatalytic performance of metal borides/borates are discussed in detail. Different methods evolved over the years for the synthesis of metal borides/borates are also discussed. Finally, an assessment of the commercial viability of metal borides/borates is made and future research directions are suggested.
3D Printed Microheater Sensor‐Integrated, Drug‐Encapsulated Microneedle Patch System for Pain Management
Authors: Yin Mengtian , Xiao Li , Liu Qingchang , Kwon Sung‐Yun , Zhang Yi , Sharma Poonam R. , Jin Li , Li Xudong , Xu Baoxing
Published: October 2019

Microneedle patch devices have been widely utilized for transdermal drug delivery in pain management, but is challenged by accurate control of drug release and subsequent diffusion to human body. The recent emerging wearable electronics that could be integrated with microneedle devices offer a facile approach to address such a challenge. Here a 3D‐printed microheater integrated drug‐encapsulated microneedle patch system for drug delivery is presented. The ink solution comprised polydimethylsiloxane (PDMS) and multiwalled carbon nanotubes (MWCNTs) with a mass concentration of up to 45% (≈10 times higher of existing ones) is prepared and used to print crack‐free stretchable microheaters on substrates with a broad range of materials and geometric curves. The adhesion strength of the printed microheater on the microneedle patch in elevated temperatures is measured to evaluate their integration performance. Assessments of encapsulated drug release into rat's skin are confirmed by examining degradation of microneedles, skin morphologies, and released fluorescent signals. Results and demonstrations established here creates a new opportunity for developing sensor controlled smart microneedle patch systems by integrating with wearable electronics, potentially useful in clinical and biomedical research.
CRISPR/Cas13a‐Powered Electrochemical Microfluidic Biosensor for Nucleic Acid Amplification‐Free miRNA Diagnostics
Authors: Bruch Richard , Baaske Julia , Chatelle Claire , Meirich Mailin , Madlener Sibylle , Weber Wilfried , Dincer Can , Urban Gerald Anton
Published: October 2019

Noncoding small RNAs, such as microRNAs, are becoming the biomarkers of choice for multiple diseases in clinical diagnostics. A dysregulation of these microRNAs can be associated with many different diseases, such as cancer, dementia, and cardiovascular conditions. The key for effective treatment is an accurate initial diagnosis at an early stage, improving the patient's survival chances. In this work, the first clustered regularly interspaced short palindromic repeats (CRISPR)/Cas13a‐powered microfluidic, integrated electrochemical biosensor for the on‐site detection of microRNAs is introduced. Through this unique combination, the quantification of the potential tumor markers microRNA miR‐19b and miR‐20a is realized without any nucleic acid amplification. With a readout time of 9 min and an overall process time of less than 4 h, a limit of detection of 10 pm is achieved, using a measuring volume of less than 0.6 µL. Furthermore, the feasibility of the biosensor platform to detect miR‐19b in serum samples of children, suffering from brain cancer, is demonstrated. The validation of the obtained results with a standard quantitative real‐time polymerase chain reaction method shows the ability of the electrochemical CRISPR‐powered system to be a low‐cost, easily scalable, and target amplification‐free tool for nucleic acid based diagnostics.
3D Printable and Reconfigurable Liquid Crystal Elastomers with Light‐Induced Shape Memory via Dynamic Bond Exchange
Authors: Davidson Emily C. , Kotikian Arda , Li Shucong , Aizenberg Joanna , Lewis Jennifer A.
Published: October 2019

3D printable and reconfigurable liquid crystal elastomers (LCEs) that reversibly shape‐morph when cycled above and below their nematic‐to‐isotropic transition temperature (TNI) are created, whose actuated shape can be locked‐in via high‐temperature UV exposure. By synthesizing LCE‐based inks with light‐triggerable dynamic bonds, printing can be harnessed to locally program their director alignment and UV light can be used to enable controlled network reconfiguration without requiring an imposed mechanical field. Using this integrated approach, 3D LCEs are constructed in both monolithic and heterogenous layouts that exhibit complex shape changes, and whose transformed shapes could be locked‐in on demand.
CV‐driven Optimization: Cobalt‐Catalyzed Electrochemical Expedient Oxychlorination of Alkenes via ORR
Authors: Tian Siyu , Lv Shide , Jia Xiaofei , Ma Li , Li Baoying , Zhang Guofeng , Gao Wei , Wei Yingqin , Chen Jianbin
Published: October 2019

Instead of screening reaction conditions by yield‐based chemical trial‐and‐error, potential‐based cyclic voltammetry was alternatively employed for optimization of electrochemical oxychlorination of alkenes. With this unconventional screening method, the catalyst system including catalysts, molar ratio of chloride sources and solvents were identified in a rational, time‐ and energy‐efficient manner. The optimal catalytic system in combination with oxygen reduction reaction enabled broad substrate scopes for the desired transformation by taking advantages of persistent radical effect. UV‐vis and CV titration experiments confirmed the in‐situ formed catalytic species [CoCl5]. Moreover, cyclic voltammetry was applied to obtain mechanistic insights in our reaction system.

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Composite Thermoresponsive Hydrogel with Auranofin‐Loaded Nanoparticles for Topical Treatment of Vaginal Trichomonad Infection
Authors: Zhang Yue , Miyamoto Yukiko , Ihara Sozaburo , Yang Justin Z. , Zuill Douglas E. , Angsantikul Pavimol , Zhang Qiangzhe , Gao Weiwei , Zhang Liangfang , Eckmann Lars
Published: October 2019

Trichomonas vaginalisis responsible for the most common non‐viral sexually transmitted disease worldwide. Standard treatment is with oral metronidazole or tinidazole, but resistance is emerging and adverse effects can be problematic. Topical treatment offers potential benefits for increasing local drug concentrations while reducing systemic exposure, but none are currently approved for trichomoniasis. The anti‐rheumatic drug, auranofin (AF), was recently discovered to have significant trichomonacidal activity, but has a long plasma half‐life and significant adverse effects. Here, this drug is used as a model to develop a novel topical formulation composed of AF‐loaded nanoparticles (NP) embedded in a thermoresponsive hydrogel for intravaginal administration. The AF‐NP composite gel shows sustained drug release for at least 12 h, and underwent sol–gel transition with increased viscoelasticity within a minute. Intravaginal administration in mice shows excellent NP retention for >6 h and markedly increases local AF levels, but reduces plasma and liver levels compared to oral treatment with a much higher dose. Furthermore, intravaginal AF‐NP gel greatly outperforms oral AF in eliminating vaginal trichomonad infection in mice, while causing no systemic or local toxicity. These results show the potential of the AF‐NP hydrogel formulation for effective topical therapy of vaginal infections.
Droplets as Carriers for Flexible Electronic Devices
Authors: Zhou Mingxing , Wu Ziyue , Zhao Yicong , Yang Qing , Ling Wei , Li Ya , Xu Hang , Wang Cheng , Huang Xian
Published: October 2019

Coupling soft bodies and dynamic motions with multifunctional flexible electronics is challenging, but is essential in satisfying the urgent and soaring demands of fully soft and comprehensive robotic systems that can perform tasks in spite of rigorous spatial constraints. Here, the mobility and adaptability of liquid droplets with the functionality of flexible electronics, and techniques to use droplets as carriers for flexible devices are combined. The resulting active droplets (ADs) with volumes ranging from 150 to 600 µL can conduct programmable functions, such as sensing, actuation, and energy harvesting defined by the carried flexible devices and move under the excitation of gravitational force or magnetic force. They work in both dry and wet environments, and adapt to the surrounding environment through reversible shape shifting. These ADs can achieve controllable motions at a maximum velocity of 226 cm min−1 on a dry surface and 32 cm min−1 in a liquid environment. The conceptual system may eventually lead to individually addressable ADs that offer sophisticated functions for high‐throughput molecule analysis, drug assessment, chemical synthesis, and information collection.
The Spacer Cations Interplay for Efficient and Stable Layered 2D Perovskite Solar Cells
Authors: Zhou Ning , Huang Bolong , Sun Mingzi , Zhang Yu , Li Liang , Lun Yingzhuo , Wang Xueyun , Hong Jiawang , Chen Qi , Zhou Huanping
Published: October 2019

Organic spacer cations in layered 2D (A1)2(A2)n−1BnX3n+1 (where A1 is an organic cation acting as a spacer between the perovskite layers, A2 is a monovalent cation, e.g., Cs+,CH3NH3+, CH(NH2)2+) perovskite materials improve the long‐term stability of the resulting solar cells, but hamper their power conversion efficiency due to poor carrier generation/transportation. Rational guidelines are thus required to enable the design of organic spacer cations. Herein, mixed A1 cations are employed in layered 2D perovskites to investigate the interplay between alkylamine cations and unsaturated alkylamine cations. It is revealed that alkylamine spacer cations are able to facilitate precursor assembly, which results in the orientated growth of perovskite crystals. Unsaturated alkylamine cations further lead to reduced exciton binding energy, which improves carrier pathway in the 2D perovskites. By mixing both cations, substantially improved open circuit voltage is observed in the resultant photovoltaic cells with the efficiency of 15.46%, one of the highest one based on (A1)2(A2)3Pb4I13 layered 2D perovskites. The generality of the design principle is further extended to other cation combinations.
Cyanomethylation of β‐Alkoxyaldehydes: Toward a Short Synthesis of Atorvastatin
Authors: Tak Raj Kumar , Noda Hidetoshi , Shibasaki Masakatsu
Published: October 2019

The cyanomethylation of β‐alkoxyaldehydes is described. These elimination‐prone substrates pose a chemoselectivity issue due to the competing elimination and addition pathways. While many commonly used strong Brønsted bases favor elimination,nBuLi effectively promotes the addition of an α‐cyanocarbanion and suppresses the undesired elimination. The cyanomethylated product can be converted to a known intermediate for the synthesis of atorvastatin, an active pharmaceutical ingredient of Lipitor, showcasing the synthetic potential of the current transformation.
Synthesis of Polyampholyte Janus‐like Microgels by Coacervation of Reactive Precursors in Precipitation Polymerization
Authors: Xu Wenjing , Rudov Andrey , Oppermann Alex , Wypysek Sarah , Kather Michael , Schroeder Ricarda , Richtering Walter , Potemkin Igor I. , Wöll Dominik , Pich Andrij
Published: October 2019

Controlling the distribution of ionizable groups of opposite charge in microgels is an extremely challenging task, which could open new pathways to design a new generation of stimuli‐responsive colloids. Herein, we report a straightforward approach for the synthesis of polyampholyte Janus‐like microgels, where ionizable groups of opposite charge are located on different sides of the colloidal network. This synthesis approach is based on the controlled self‐assembly of growing polyelectrolyte microgel precursors during the precipitation polymerization process. We confirmed the morphology of polyampholyte Janus‐like microgels and demonstrate that they are capable of responding quickly to changes in both pH and temperature in aqueous solutions.
Organocatalytic Enantioselective Synthesis of Tetrasubstituted α‐Amino Allenoates by Dearomative γ‐Addition of 2,3‐Disubstituted Indoles to β,γ‐Alkynyl‐α‐imino Esters
Authors: Yang Junxian , Wang Zheng , He Zeyuan , Li Guofeng , Hong Liang , Sun Wangsheng , Wang Rui
Published: October 2019

The first asymmetric synthesis of tetrasubstituted α‐amino allenoates by a chiral phosphoric acid catalyzed dearomative γ‐addition reaction of 2,3‐disubstituted indoles to β,γ‐alkynyl‐α‐imino esters is reported. This method provides access to a series of highly functionalized tetrasubstituted allenes featuring quaternary stereocenters in high yields, and with excellent regio‐, diastereo‐, and enantioselectivities under mild conditions without by‐product formation. Representative large‐scale reactions and diverse transformations of the products into various scaffolds with potential biological activities render are also disclosed. The mechanism of the reaction was elucidated by control reactions and DFT calculations.
Cellulose Nanocrystal Elastomers with Reversible Visible Color
Authors: Boott Charlotte E. , Tran Andy , Hamad Wadood Y. , MacLachlan Mark J.
Published: October 2019

Responsive photonic crystals have potential applications in mechanical sensors and soft displays; however, new materials are constantly desired to provide new innovations and improve on existing technologies. To address this, we report stretchable chiral nematic cellulose nanocrystal (CNC) elastomer composites that exhibit reversible visible color upon the application of mechanical stress. When stretched (or compressed) the colorless materials maintain their chiral nematic structure but the helical pitch is reduced into the visible region, resulting in coloration of the CNC‐elastomer composite. By increasing the percentage elongation of the material (ca. 50–300 %), the structural color can be tuned from red to blue. The color of the materials was characterized by reflectance optical microscopy and reflectance circular dichroism to confirm the wavelength and polarization of the reflected light. We also probed the mechanism of the structural color using 2D‐X‐ray diffraction. Finally, by either water‐patterning the starting CNC film, or by forming a CNC film with gradient color, through masked evaporation, we were able to prepare encoded stretchable chiral nematic CNC‐elastomers.
Microporosity of a Guanidinium Organodisulfonate Hydrogen‐Bonded Framework
Authors: Brekalo Ivana , Deliz David E. , Barbour Leonard J. , Ward Michael D. , Friščić Tomislav , Holman K. Travis
Published: October 2019

Guanidinium organosulfonates (GSs) are a large and well‐explored archetypal family of hydrogen‐bonded organic host frameworks that have, over the past 25 years, been regarded as nonporous. Reported here is the only example to date of a conventionally microporous GS host phase, namely guanidinium 1,4‐benzenedisulfonate (p‐G2BDS). p‐G2BDS is obtained from its acetone solvate, AcMe@G2BDS, by single‐crystal‐to‐single‐crystal (SC‐SC) desolvation, and exhibits a Type I low‐temperature/pressure N2 sorption isotherm (SABET=408.7(2) m2 g−1, 77 K). SC‐SC sorption of N2, CO2, Xe, and AcMe by p‐G2BDS is explored under various conditions and X‐ray diffraction provides a measurement of the high‐pressure, room temperature Xe and CO2 sorption isotherms. Though p‐G2BDS is formally metastable relative to the “collapsed”, nonporous polymorph, np‐G2BDS, a sample of p‐G2BDS survived for almost two decades under ambient conditions. np‐G2BDS reverts to zCO2@p‐G2BDS or yXe@p‐G2BDS (y,z=variable) when pressure of CO2 or Xe, respectively, is applied.
Construction of Chiral 2,3‐Allenols through a Copper(I)‐Catalyzed Asymmetric Direct Alkynylogous Aldol Reaction
Authors: Zhong Feng , Xue Qi‐Yan , Yin Liang
Published: October 2019

Chiral 2,3‐allenols were constructed through copper(I)‐catalyzed asymmetric direct alkynylogous aldol reaction. With aromatic and heteroaromatic aldehydes, the alkynylogous aldol reaction with (R)‐DTBM‐SEGPHOS as the ligand proceeded smoothly to furnish the products in excellent regioselectivity with good to high diastereoselectivity and excellent enantioselectivity. In the cases of aliphatic aldehydes, esters of but‐2‐yn‐1‐ol as the substrates and (R,R)‐Ph‐BPE as the ligand were found to be crucial to get good to high regio‐ and diastereoselectivity. The produced chiral 2,3‐allenols are easily transformed into synthetically useful 2‐furanones through cyclization. Finally, the developed method was successfully applied in the rapid synthesis of two chiral intermediates toward the synthesis of two pharmaceutically active compounds that have been proposed for the treatment of neurological disorders.
Designing Sub‐2 nm Organosilica Nanohybrids for Far‐Field Super‐Resolution Imaging
Authors: Liang Liangliang , Yan Wei , Qin Xian , Peng Xiao , Feng Han , Wang Yu , Zhu Ziyu , Liu Lingmei , Han Yu , Xu Qinghua , Qu Junle , Liu Xiaogang
Published: October 2019

Stimulated emission depletion (STED) microscopy enables ultrastructural imaging of biological samples with high spatiotemporal resolution. STED nanoprobes based on fluorescent organosilica nanohybrids featuring sub‐2 nm size and near‐unity quantum yield are presented. The spin–orbit coupling (SOC) of heavy‐atom‐rich organic fluorophores is mitigated through a silane‐molecule‐mediated condensation/dehalogenation process, resulting in bright fluorescent organosilica nanohybrids with multiple emitters in one hybrid nanodot. When harnessed as STED nanoprobes, these fluorescent nanohybrids show intense photoluminescence, high biocompatibility, and long‐term photostability. Taking advantage of the low‐power excitation (0.5 μW), prolonged singlet‐state lifetime, and negligible depletion‐induced re‐excitation, these STED nanohybrids present high depletion efficiency (>96 %), extremely low saturation intensity (0.54 mW, ca. 0.188 MW cm−2), and ultra‐high lateral resolution (ca. λem/28).
2D Oligosilyl Metal–Organic Frameworks as Multi‐state Switchable Materials
Authors: Burns David A. , Press Eric M. , Siegler M. A. , Klausen Rebekka S. , Thoi V. Sara
Published: October 2019

We report the synthesis of a set of 2D metal–organic frameworks (MOFs) constructed with organosilicon‐based linkers. These oligosilyl MOFs feature linear SinMe2n(C6H4CO2H)2 ligands (lin‐Sin, n=2, 4) connected by Cu paddlewheels. The stacking arrangement of the 2D sheets is dictated by van der Waals interactions and is tunable by solvent exchange, leading to reversible structural transformations between many crystalline and amorphous phases.
Unconventional Route to Oxygen‐Vacancy‐Enabled Highly Efficient Electron Extraction and Transport in Perovskite Solar Cells
Authors: Wang Bing , Zhang Meng , Cui Xun , Wang Zewei , Rager Matthew , Yang Yingkui , Zou Zhigang , Wang Zhong Lin , Lin Zhiqun
Published: October 2019

The ability to effectively transfer photoexcited electrons and holes is an important endeavor toward achieving high‐efficiency solar energy conversion. Now, a simple yet robust acid‐treatment strategy is used to judiciously create an amorphous TiO2 buffer layer intimately situated on the anatase TiO2 surface as an electron‐transport layer (ETL) for efficient electron transport. The facile acid treatment is capable of weakening the bonding of zigzag octahedral chains in anatase TiO2, thereby shortening staggered octahedron chains to form an amorphous buffer layer on the anatase TiO2 surface. Such amorphous TiO2‐coated ETL possesses an increased electron density owing to the presence of oxygen vacancies, leading to efficient electron transfer from perovskite to TiO2. Compared to pristine TiO2‐based devices, the perovskite solar cells (PSCs) with acid‐treated TiO2 ETL exhibit an enhanced short‐circuit current and power conversion efficiency.
Reversible Thermochromism and Strong Ferromagnetism in Two‐Dimensional Hybrid Perovskites
Authors: Sun Bing , Liu Xiao‐Fei , Li Xiang‐Yang , Cao Yang , Yan Ze , Fu Lin , Tang Nujiang , Wang Qiang , Shao Xiangfeng , Yang Dezheng , Zhang Hao‐Li
Published: October 2019

Two‐dimensional (2D) hybrid perovskites have shown many attractive properties associated with their soft lattices and multiple quantum well structure. Herein, we report the synthesis and characterization of two new multifunctional 2D hybrid perovskites, (PED)CuCl4 and (BED)2CuCl6, which show reversible thermochromic behavior, dramatic temperature‐dependent conductivity change, and strong ferromagnetism. Upon temperature change, the (PED)CuCl4 and (BED)2CuCl6 crystals exhibit a reversible color change between yellow and red‐brown. The associated structural changes were monitored by in situ temperature‐dependent powder X‐ray diffraction (PXRD). The (BED)2CuCl6 exhibits superior thermal stability, with a thermochromic working temperature up to 443 K. The conductivity of (BED)2CuCl6 changes over six orders of magnitude upon temperature change. The 2D perovskites exhibit ferromagnetic properties with Curie temperatures around 13 K.
A [001]‐Oriented Hittorf's Phosphorus Nanorods/Polymeric Carbon Nitride Heterostructure for Boosting Wide‐Spectrum‐Responsive Photocatalytic Hydrogen Evolution from Pure Water
Authors: Zhu Yukun , Lv Chunxiao , Yin Zhuocheng , Ren Jun , Yang Xianfeng , Dong Chung‐Li , Liu Hongwei , Cai Rongsheng , Huang Yu‐Cheng , Theis Wolfgang , Shen Shaohua , Yang Dongjiang
Published: October 2019

Red phosphorus is a promising photocatalyst with wide visible‐light absorption up to 700 nm, but the fast charge recombination limits its photocatalytic hydrogen evolution reaction (HER) activity. Now, [001]‐oriented Hittorf's phosphorus (HP) nanorods were successfully grown on polymeric carbon nitride (PCN) by a chemical vapor deposition strategy. Compared with the bare PCN and HP, the optimized PCN@HP hybrid exhibited a significantly enhanced photocatalytic activity, with HER rates reaching 33.2 and 17.5 μmol h−1 from pure water under simulated solar light and visible light irradiation, respectively. It was theoretically and experimentally indicated that the strong electronic coupling between PCN and [001]‐oriented HP nanorods gave rise to the enhanced visible light absorption and the greatly accelerated photoinduced electron–hole separation and transfer, which benefited the photocatalytic HER performance.
An Unprecedented Kernel Growth Mode and Layer‐Number‐Odevity‐Dependent Properties in Gold Nanoclusters
Authors: Liao Lingwen , Wang Chengming , Zhuang Shengli , Yan Nan , Zhao Yan , Yang Ying , Li Jin , Deng Haiteng , Wu Zhikun
Published: October 2019

Kernel atoms of Au nanoclusters are packed layer‐by‐layer along the [001] direction with every full (001) monolayer composed of 8 Au atoms (Au8 unit) in nanoclusters with formula of Au8n+4(TBBT)4n+8 (n is the number of Au8 units; TBBTH=4‐tert‐butylbenzenelthiol). It is unclear whether the kernel atoms can be stacked in a defective‐layer way along the [001] direction during growth of the series of nanoclusters and how the kernel layer number affects properties. Now, a nanocluster is synthesized that is precisely characterized by mass spectrometry and single‐crystal X‐ray crystallography, revealing a layer stacking mode in which a half monolayer composed of 4 atoms (Au4 unit) is stacked on the full monolayer along the [001] direction. The size and the odevity of the kernel layer number influence the properties (polarity, photoluminescence) of gold nanoclusters. The obtained nanocluster extends the previous formula from Au8n+4(TBBT)4n+8 to Au4n+4(TBBT)2n+8 (n is the number of Au4 units).
Highly Selective Electrochemical Reduction of CO2 to Alcohols on an FeP Nanoarray
Authors: Ji Lei , Li Lei , Ji Xuqiang , Zhang Ya , Mou Shiyong , Wu Tongwei , Liu Qian , Li Baihai , Zhu Xiaojuan , Luo Yonglan , Shi Xifeng , Asiri Abdullah M. , Sun Xuping
Published: October 2019

Electrochemical reduction of CO2 into various chemicals and fuels provides an attractive pathway for environmental and energy sustainability. It is now shown that a FeP nanoarray on Ti mesh (FeP NA/TM) acts as an efficient 3D catalyst electrode for the CO2 reduction reaction to convert CO2 into alcohols with high selectivity. In 0.5 m KHCO3, such FeP NA/TM is capable of achieving a high Faradaic efficiency (FE
) up to 80.2 %, with a total FE
of 94.3 % at −0.20 V vs. reversible hydrogen electrode. Density functional theory calculations reveal that the FeP(211) surface significantly promotes the adsorption and reduction of CO2 toward CH3OH owing to the synergistic effect of two adjacent Fe atoms, and the potential‐determining step is the hydrogenation process of *CO.
Efficient Electrosynthesis of Syngas with Tunable CO/H2Ratios over ZnxCd1−xS‐Amine Inorganic–Organic Hybrids
Authors: Meng Nannan , Liu Cuibo , Liu Yang , Yu Yifu , Zhang Bin
Published: October 2019

Efficient electrochemical reduction of CO2and H2O into industrial syngas with tunable CO/H2ratios, especially integrated with anodic organic synthesis to replace the low‐value oxygen evolution reaction (OER), is highly desirable. Here, integration of controllable partial substitution of zinc (Zn) with amine incorporation into CdS‐amine inorganic‐organic hybrids is used to generate highly efficient electrocatalysts for synthesizing syngas with tunable CO/H2ratios (0–19.7), which are important feedstocks for the Fischer–Tropsch process. Diethylenetriamine could enhance the adsorption and accelerate the activation of CO2to form the key intermediate COOH* for CO formation. Zn substitution promoted the hydrogen evolution reaction (HER), leading to tunable CO/H2ratios. Importantly, syngas and dihydroisoquinoline can be simultaneously synthesized by pairing with anodic semi‐oxidation of tetrahydroisoquinoline in a ZnxCd1−xS‐Amine ∥ Ni2P two‐electrode electrolyzer.
Game‐Based Learning in Virtual Worlds: A Multiuser Online Game for Medical Undergraduate Radiology Education within Second Life
Authors: Lorenzo‐Alvarez Rocio , Rudolphi‐Solero Teodoro , Ruiz‐Gomez Miguel J. , Sendra‐Portero Francisco
Published: October 2019

Game‐based learning can have a positive impact on medical education, and virtual worlds have great potential for supporting immersive online games. It is necessary to reinforce current medical students' knowledge about radiological anatomy and radiological signs. To meet this need, the objectives of this study were: to design a competition‐based game in the virtual world, Second Life and to analyze the students' perceptions of Second Life and the game, as well as to analyze the medium‐term retention of knowledge and the potential impact on the final grades. Ninety out of 197 (45.6%) third‐year medical students voluntarily participated in an online game based on self‐guided presentations and multiple‐choice tests over six 6‐day stages. Participants and non‐participants were invited to perform an evaluation questionnaire about the experience and a post‐exposure knowledge test. Participants rated the experience with mean scores equal to or higher than 8.1 on a 10‐point scale, highlighting the professor (9.5 ± 1.1; mean ± SD) and the virtual environment (8.9 ± 1.1). Participants had better results in the post‐exposure test than non‐participants (59.0 ± 13.5 versus 45.3 ± 11.5; P < 0.001) and a lower percentage of answers left blank (6.7 ± 8.4 versus 13.1 ± 12.9; P = 0.014). Competitive game‐based learning within Second Life is an effective and well‐accepted means of teaching core radiological anatomy and radiological signs content to medical students. The higher medium‐term outcomes obtained by participants may indicate effective learning with the game. Additionally, valuable positive perceptions about the game, the educational contents, and the potential benefit for their education were discovered among non‐participants.
Phosphine‐Activated Lysine Analogues for Fast Chemical Control of Protein Subcellular Localization and Protein SUMOylation
Authors: Wesalo Joshua S. , Luo Ji , Morihiro Kunihiko , Liu Jihe , Deiters Alexander
Published: October 2019

The Staudinger reduction and its variants have exceptional compatibility with live cells but can be limited by slow kinetics. Herein we report new small‐molecule triggers that turn on proteins through a Staudinger reduction/self‐immolation cascade with substantially improved kinetics and yields. We achieved this through site‐specific incorporation of a new set of azidobenzyloxycarbonyl lysine derivatives in mammalian cells. This approach allowed us to activate proteins by adding a nontoxic, bioorthogonal phosphine trigger. We applied this methodology to control a post‐translational modification (SUMOylation) in live cells, using native modification machinery. This work significantly improves the rate, yield, and tunability of the Staudinger reduction‐based activation, paving the way for its application in other proteins and organisms.
Isolated unilateral absence of the pulmonary artery
Authors: Kanno Kenji , Maehara Takamitsu , Yamamoto Taketsugu , Nemoto Daiji , Kigoshi Hironori , Masuda Munetaka
Published: October 2019

Isolated unilateral absence of the pulmonary artery (UAPA) is a rare malformation. It is associated with respiratory symptoms, such as dyspnea or hemoptysis. We suggest that surgical treatment should be positively considered in patients with UAPA who are severely symptomatic and who have no other cardiovascular or respiratory comorbidities.
Selective Deposition of Cobalt and Copper Oxides on BiVO4 Facets for Enhancement of CO2 Photocatalytic Reduction to Hydrocarbons
Authors: Yu Xiang , Ordomsky Vitaly V. , Khodakov Andrei Y.
Published: October 2019

The nanostructure of a semiconductor is a crucial parameter for efficient photocatalytic performance. Hereby, we have synthesized monoclinic bismuth vanadate (BiVO4) crystals with controlled ratio of {010} and {110} facets. The selective deposition of CuOx and CoOx over {010} and {110} facets has been performed using photo‐reduction and photo‐oxidation methods, respectively. It resulted in a highly efficient charge separation of photogenerated electrons and holes and enhancement of the photocatalytic reduction of CO2 by H2O into hydrocarbons, including CH4, C2H6 and C3H8. The controlled co‐catalyst deposition over different semiconductor facets provides a strategy for the synthesis of hydrocarbons from CO2 and H2O by efficient charge separation.
Photoionization Mass Spectrometry for Online Detection of Reactive and Unstable Gas‐Phase Intermediates in Heterogeneous Catalytic Reactions
Authors: You Rui , Huang Weixin
Published: October 2019

Heterogeneous catalytic reactions always involve surface intermediates on catalyst surfaces, and some of them also involve reactive and unstable gas‐phase intermediates such as radicals and alkyl hydroperoxides. Online detection of these gas‐phase intermediates is of great importance for fundamentally understanding reaction mechanisms of relevant heterogeneous catalytic reactions, designing structures of efficient catalysts and optimizing reactors. However, it has remained a long‐time challenge due to the lack of routine characterization techniques. Herein we review recent progress on applications of photoionization mass spectrometry in online detection of reactive and unstable gas‐phase intermediates in heterogeneous catalytic reactions. The development and advantages of photoionization mass spectrometry and the relevant equipment setup for heterogeneous catalysis studies are also described. Finally, a future perspective is given.
Enhancement of the Yield of Ammonia by Hydrogen‐Sink Effect during Plasma Catalysis
Authors: Shah Javishk , Gorky Fnu , Psarras Peter , Seong Bomsaerah , Gómez‐Gualdrón Diego A. , Carreon Maria L.
Published: October 2019

Plasma‐catalytic ammonia synthesis has been known since the early 1900s, but only until now efforts to optimize catalysts for this purpose are emerging. Here, we investigate various transition metals, low‐melting‐point metals, and gallium‐rich alloy catalysts for their activity towards ammonia production under a plasma environment. The best three pure metal catalysts were Ni, Sn and Au, which are not traditional catalysts for the current industrial ammonia synthesis. The ammonia yields for these catalysts were 34 %, 29 %, and 19 %, respectively. Synergistic effects were detected when employing alloys, as some alloys presented ∼25–50 % higher yields than their constituent metals. The employed metals were classified into two categories. Category I metals (Cu, Ag, Au and Fe), which are nitrophobic (excluding Fe, the Haber‐Bosch catalyst) and poor hydrogen sinks. For these metals, the measured concentration of Hα in the gas phase tended to correlate inversely with ammonia yield and directly with the H binding strength on the catalyst surface. Category II metals (Ga, In, Sn and Ni), which are good hydrogen sinks, tend to have a lower concentration of Hα in the gas phase than that of category I metals, which is consistent with their expected sink behavior. For these metals, the concentration of Hα correlates with ammonia yield. Plasma characterization experiments and DFT calculations suggest that the higher performance of Ni and Sn is related to the benefit of dissolving hydrogen to slow down H recombination, which is a feature that could be potentially optimized in future studies by rationally altering the catalyst composition.
Ruthenium(II)‐Catalyzed Hydrogen Isotope Exchange of Pharmaceutical Drugs by C−H Deuteration and C−H Tritiation
Authors: Müller Valentin , Weck Remo , Derdau Volker , Ackermann Lutz
Published: October 2019

Well‐defined ruthenium(II) biscarboxylate complexes enabled selective ortho‐deuteration with weakly‐coordinating, synthetically useful carboxylic acid with outstanding levels of isotopic labeling. The robust nature of the catalytic system was reflected by a broad functional group tolerance in an operationally‐simple manner, allowing the isotope labeling of challenging pharmaceuticals and bioactive heterocyclic motifs. The synthetic power of our method was highlighted by the selective tritium‐labeling of repaglinide, an antidiabetic drug, providing access to defined tritium labeled therapeutics.
Fabrication of Core‐Shell Ni2P@N, P−Co‐Doped Carbon/Reduced Graphene Oxide Composite as Anode Material for Lithium‐ and Sodium‐Ion Batteries
Authors: Li Yongsheng , Zhang Jianmin , Li Dan , Ding Jie , Liu Yushan , Cai Qiang
Published: October 2019

Commonly, carbon layer was a suitable choice to enhance the conductivity and reduce the large volume effect of Ni2P nanoparticles (NPs) in electrochemical applications. The doped nitrogen (N) and phosphorous (P) atoms in carbon could further improve its performance. In this paper, core‐shell structure Ni2P@N, P‐co‐doped carbon (Ni2P@N, P−C) NPs were loaded onto reduced graphene oxide nanosheets (GN) to form new composite serial Ni2P@N, P−C/GN, which was designed for the combination of these merits and successfully obtained by two‐step method (firstly hydrothermal process and secondly phosphorization process). As anodes for LIBs and SIBs, the responding electrochemical studies showed the Ni2P@N, P−C/GN‐0.4 electrode exhibited an outstanding specific capacity of 450 mA h g−1 at 5 A g−1 after 2000 cycles in lithium‐ion batteries (LIBs) and maintained 110 mA h g−1 at 2 A g−1 after 3000 cycles in sodium‐ion batteries (SIBs), respectively. These results showed that Ni2P@N, P−C/GN material could be an excellent candidate for energy storage area.