bluuebunny/crossref_metadata_2025_split huggingface dataset:
Visible‐Light‐Mediated Synthesis of β‐Chloro Ketones from Aryl Cyclopropanes
Authors: Petzold Daniel , Singh Pardeep , Almqvist Fredrik , König Burkhard 
Published: March 2019

AbstractWe report the visible‐light‐mediated synthesis of β‐chloro ketones from aryl cyclopropanes, oxygen, hydrochloric acid, and nitric acid. The operationally simple and catalyst‐free method uses cheap standard laboratory reagents and displays broad functional‐group tolerance. Moreover, scale up of the reaction and late‐stage functionalization of bioactive compounds is possible, providing the opportunity to utilize the cyclopropane ring as a masked β‐chloro ketone in a reaction sequence. We propose a light‐driven radical chain reaction initiated by the reaction of diluted hydrochloric and nitric acid to produce small quantities of molecular chlorine. The mechanistic hypothesis is supported by 18O labelling and UV/Vis experiments, cyclovoltammetry, and several control reactions.
Preparation of epoxidized acrylonitrile butadiene rubber and its compatibilization effect on water‐swellable rubber composites
Authors: Lv Guozheng , Cen Lan , Tan Xinwen , Wu Qihao 
Published: March 2019

ABSTRACTIn this research, water‐swellable rubbers (WSRs) were prepared by the blending of acrylonitrile butadiene rubber (NBR) with epoxidized acrylonitrile butadiene rubber (ENBR), precipitated silica, vulcanizing agents, and polyacrylic acid sodium (PAAS) as superabsorbent polymers (SAPs). ENBR was prepared with a molybdenum trioxide catalyst and a tert‐butyl hydroperoxide oxidant through a free‐radical reaction under specific conditions and was used as a compatibilizer to improve the interfacial adhesion of the NBR matrix and hydrophilic components of the WSRs. Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy were used to analyze the structure and properties of ENBR. The dispersion of silica and SAPs in the rubber matrix was investigated by transmission electron microscopy. The presence of ENBR enhanced the water‐absorption properties of the WSRs. The NBR–ENBR composites exhibited a higher mechanical performance after water absorption than that without ENBR. Both the swelling ratio and the absorption rate increased with the ENBR content. When the weight ratio of NBR–ENBR was 25/75, an equilibrium swelling ratio of 172% (13% higher than that of the sample without ENBR) was obtained. Scanning electron microscopy analysis revealed that the addition of ENBR improved the compatibility between the SAPs and the NBR matrix. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47694.
Improved energy dissipation control of overhead cranes
Authors: Zhang Shengzeng , He Xiongxiong , Chen Qiang , Feng Yuanjing 
Published: March 2019

AbstractIn this paper, an improved energy dissipation controller is presented for overhead cranes. Our main contribution is the characterization of overhead cranes for which energy shaping method yields a significant storage function, where a nonlinear coupling controller is delivered that drastically increases the damping of the control system. Additional terms are fabricated to assure a soft start and a limited overshoot. In the frame of the Lyapunov theory, we apply LaSalle's invariance principle to illustrate the corresponding stability. Such a controller is experimented and some results are reported.
Exonic variants of genes related to the vitamin D signaling pathway in the families of familial multiple sclerosis using whole‐exome next generation sequencing
Authors: Pytel Vanesa , Matías‐Guiu Jordi A. , Torre‐Fuentes Laura , Montero‐Escribano Paloma , Maietta Paolo , Botet Javier , Álvarez Sara , Gómez‐Pinedo Ulises , Matías‐Guiu Jorge 
Published: March 2019

AbstractIntroductionVitamin D (VD) deficiency has been associated with multiple sclerosis (MS) and other autoimmune diseases (AIDs). However, the effect of the genetics of VD on the risk of MS is subject to debate. This study focuses on genes linked to the VD signaling pathway in families with MS. The evaluation of gene variants in all the members of families could contribute to an additional knowledge on the information obtained from case‐control studies that use nonrelated healthy people.Material and MethodsWe studied 94 individuals from 15 families including at least two patients with MS. We performed whole‐exome next generation sequencing on all individuals and analyzed variants of the DHCR7, CYP2R1, CYP3A4, CYP27A1, GC, CYP27B1, LRP2, CUBN, DAB2, FCGR, RXR, VDR, CYP24A1, and PDIA3 genes. We also studied PTH, FGF23, METTL1, METTL21B, and the role of the linkage disequilibrium block on the long arm of chromosome 12, through analysis of the CDK4, TSFM, AGAP2, and AVIL genes. We compared patients with MS, other AIDs and unaffected members from different family types.ResultsThe study described the variants in the VD signaling pathway that appear in families with at least two patients with MS. Some infrequent variants were detected in these families, but no significant difference was observed between patients with MS and/or other AIDs and unaffected family members in the frequency of these variants. Variants previously associated with MS in the literature were not observed in these families or were distributed similarly in patients and unaffected family members.ConclusionThe study of genes involved in the VD signaling pathway in families that include more than one patient with MS did not identify any variants that could explain the presence of the disease, suggesting that VD metabolism could probably play a role in MS more as an environmental factor rather than as a genetic factor. Our study also supports the analysis of cases and unaffected individuals within families in order to determine the influence of genetic factors.
Symbolic reactions or substantive pro‐environmental behaviour? An empirical study of corporate environmental performance under the government's environmental subsidy scheme
Authors: Ren Shenggang , He Duojun , Zhang Tao , Chen Xiaohong 
Published: March 2019

AbstractDo firms substantively improve their corporate environmental performance (CEP), or do they just react symbolically under the government's environmental subsidy (ENS) scheme? There is little empirical research into this business ethical problem in the literature. To understand how firms respond to the government's ENS scheme, in this study, we empirically examine the relationship between ENS and CEP. Specifically, we distinguish two types of CEP, that is, environmental management performance (EMP) and environmental operational performance (EOP), and then test the effects of ENS on EMP and EOP and the moderating role of environmental enforcement intensity (EEI) in both effects. We collect 5‐year panel data of Chinese listed companies operating in heavily polluting industries for the empirical analysis and find that (a) China's ENS significantly improves EMP, but its effect on EOP is not significant. Subsidized firms mainly respond to the government's ENS scheme through the process‐oriented pro‐environmental behaviour such as implementing the ISO14001 certification to improve EMP rather than the outcome‐oriented pro‐environmental behaviour such as investing on environment‐related R&D projects and energy conservation and emission reduction to improve EOP. This sort of firm pro‐environmental behaviour under the Chinese government's ENS scheme is symbolic rather than substantive. (b) China's EEI positively moderates the effect of ENS on EMP, but its moderating role in the effect of ENS on EOP is not significant. Therefore, the power of the current environmental regulation enforcement mechanism in China is insufficient to push firms to engage in real pro‐environmental activities to improve EOP. Relevant policy implications are discussed in the paper.
Applied conversation analysis for counselling and psychotherapy researchers
Authors: O'Reilly Michelle , Lester Jessica 
Published: March 2019

AbstractApplied Conversation Analysis (CA) is broadly accepted to be a qualitative methodological approach associated with the discursive turn. Although some argue for a distinct observational science paradigm, the current methodological dichotomy positions this work under the qualitative rubric. Applied CA focuses on the sequential design of social interaction, examining language and meaning within institutional settings. It emphasises informing practice and provides a useful form of evidence for therapists and counsellors, as the work is grounded in real‐world therapeutic practices. In therapy, language and talk are fundamental to the process and outcomes. Studying therapeutic social interaction through Applied CA can illuminate processes, improve practice, and utilise best practice to inform care. The focus of this article is our perspective on the value of Applied CA as a form of evidence in counselling and psychotherapy, and to encourage partnership working between academics and clinicians working in the field.
Can Predictive Algorithms Assist Decision‐Making in Social Work with Children and Families?
Authors: Gillingham Philip 
Published: March 2019

Decision support systems (DSS) which incorporate algorithms trained using administrative data have been promoted as the next promising development in initiatives to improve and assist decision‐making in social work with children and families. In this article, research and grey literature about DSS designed, and in some cases implemented, in the USA, the Netherlands, Australia and New Zealand are analysed to assess the extent to which they are currently able to meet this promise. The challenges of developing DSS for social work are identified and ideas are suggested to overcome them. © 2019 John Wiley & Sons, Ltd.Key Practitioner Messages

Decision support systems (DSS) are being developed for social work with children and families and they may transform how decisions are made with important consequences for both service users and the profession.
Current DSS are mostly not very accurate in their predictions and further work is required in their development and on the data used to train the algorithms.
The next stage in the development of DSS will require long‐term commitment by social workers to work in collaboration with data scientists and researchers. It will also be expensive. Social workers need to lead the debate about whether DSS are worth the investment.
‘Decision support systems are being developed for social work with children and families and they may transform how decisions are made’
Genetically Encoded Biotin Analogues: Incorporation and Application in Bacterial and Mammalian Cells
Authors: Hohl Adrian , Mideksa Yonatan G. , Karan Ram , Akal Anastassja , Vogler Malvina , Groll Michael , Rueping Magnus , Lang Kathrin , Feige Matthias J. , Eppinger Jörg 
Published: March 2019

AbstractThe biotin–streptavidin interaction is among the strongest known in nature. Herein, the site‐directed incorporation of biotin and 2‐iminobiotin composed of noncanonical amino acids (ncAAs) into proteins is reported. 2‐Iminobiotin lysine was employed for protein purification based on the pH‐dependent dissociation constant to streptavidin. By using the high‐affinity binding of biotin lysine, the bacterial protein RecA could be specifically isolated and its interaction partners analyzed. Furthermore, the biotinylation approach was successfully transferred to mammalian cells. Stringent control over the biotinylation site and the tunable affinity between ncAAs and streptavidin of the different biotin analogues make this approach an attractive tool for protein interaction studies, protein immobilization, and the generation of well‐defined protein–drug conjugates.
Heterogeneous lupus‐specific lesions and treatment outcome, in a single patient, over a period of time
Authors: Fernandes Melissa , Taulaigo Anna V. , Vidal Carolina , Agostini Patrick , Riso Nuno , Moraes‐Fontes Maria Francisca 
Published: March 2019

Key Clinical MessageThe report highlights the importance of strict clinico‐histological correlations when skin biopsies are performed in diagnostic doubt in systemic lupus erythematosus. Furthermore, PUVA is never indicated in autoimmune conditions involving photosensitivity, due to high potential for internal and cutaneous aggravation of the disease, as the authors observed in this case.
Multidisciplinary clinical approach by sharing oral examination information to treat a diabetes patient with dysgeusia
Authors: Matsunaga Kazuyuki , Yoshida Yasuko , Takemaru Makoto , Yamashiro Keisuke , Monden Ikuko , Inohara Ken , Nakagawa Saki , Maeda Eriko , Nakahama Kanako , Kohriyama Tatsuo , Takashiba Shogo 
Published: March 2019

Key Clinical MessageTaste alteration is one of the complications of severe diabetes. It is important in diabetes treatment to assess taste alteration and perform dietary counseling, therapeutic exercise, and oral care. In this case, multidisciplinary clinical approach by medical staff was successful for a severely diabetic patient with dysgeusia.
Selective One‐Step Aerobic Oxidation of Cyclohexane to ϵ‐Caprolactone Mediated by N‐Hydroxyphthalimide (NHPI)
Authors: Wang Lingyao , Zhang Yuanbin , Du Renfeng , Yuan Haoran , Wang Yongtao , Yao Jia , Li Haoran 
Published: March 2019

AbstractThe selective one‐step aerobic oxidation of cyclohexane to ϵ‐caprolactone was achieved in the presence of N‐hydroxyphthalimide (NHPI) and aldehyde under mild conditions. Remarkably, 12 % of cyclohexane was converted with a selectivity of 77 % of ϵ‐caprolactone and 15 % of KA oil. Control experiments indicated that NHPI accelerated the oxidation of aldehydes and peroxy radicals generated from aldehydes in situ were the key intermediates in the period of CH bond activation. 2,2,6,6‐Tetramethylpiperidine 1‐oxyl (TEMPO) addition and a series of m‐chloroperoxybenzoic acid (m‐CPBA) oxidation experiments showed that the oxidation proceeded via a complex radical chain mechanism.
Green Oxidation of n‐Octanol on Supported Nanogold Catalysts: Formation of Gold Active Sites under Combined Effect of Gold Content, Additive Nature and Redox Pretreatment
Authors: Pakrieva E. , Kolobova E. , Mamontov G. , Bogdanchikova N. , Farias M. H. , Pascual L. , Cortés Corberán V. , Martinez Gonzalez S. , Carabineiro S. A. C. , Pestryakov A. 
Published: March 2019

AbstractThe front cover artwork for Issue 06/2019 is provided by researchers from Tomsk Polytechnic University (Russia), Tomsk State University (Russia), UNAM (México), CSIC (Spain) and Universidade do Porto (Portugal). The image shows the oxidation of n‐octanol over supported nanogold catalysts. See the Full Paper itself at https://doi.org/10.1002/cctc.201801566.
Mahkota Dewa Subcritical Water Extraction Process: Experimental and Molecular Dynamics Simulation Study
Authors: Hashim Nurmaryam Aini , Mudalip Siti Kholijah Abdul , Harun Noorlisa , Man Rohaida Che , Sulaiman Siti Zubaidah , Arshad Zatul Iffah Mohd , Shaarani Shalyda M. , Azmir Jannatul 
Published: March 2019

AbstractSubcritical water extraction and molecular dynamics simulation were performed to investigate mangiferin and antioxidant extraction from Mahkota Dewa fruits at different operating temperatures. The mangiferin yield and antioxidant activity were analyzed using high‐performance liquid chromatography and 2‐diphenyl‐1‐picrylhydrazyl assay method, respectively. The diffusivity and intermolecular interactions were determined by mean squared displacement (MSD) and radial distribution function (RDF) analysis, respectively. The temperature exerts a momentous effect on mangiferin yield and antioxidant activity of the extract. TheMSDresult showed an increment in diffusivity coefficient of mangiferin with temperature. The RDF analysis revealed hydrogen bonding formations between mangiferin and water through OH2O••HMR4(OH1)interaction that plays a role in the extraction process.
Designation of a Nano‐Fe3O4 Based Composite Electrode with Long Cycle Life for Lithium‐Ion Batteries
Authors: Wu Pengfei , Dong Xichao , Gu Chong , Ge Shuaipeng , Su Zhiming , Lu Yingxi , Guo Changqing , Shao Guangyu , Zhong Yunwang , Liu Anhua 
Published: March 2019

AbstractIn order to address the issue of large volume expansion and poor electrical conductivity of Fe3O4‐based anodes for lithium‐ion batteries, carbon and SiOx/SiC heterojunction double‐shell coated Fe3O4(FexSiy) nanocomposites were synthesized by crosslinking, pyrolysis and decarbonization of sol particles. The particles were produced by the reaction of iron carbonyl with liquid polycarbosilane using pitch as isolator, which is a low cost and easy to scale up preparation method. It is found that the double‐shell structure of the nanoparticles not only solves the problem of comminution of Fe3O4 during cycling, but also ensures stable cycling and superior rate performance. The FeOSiC‐30 anode delivers a high reversible capacity (1357.2 mAh g−1 for 550 cycles at 1 A g−1 and 1060.7 mAh g−1 for 2500 cycles at 5 A g−1). The excellent electrochemical performance can be contributed to the novel structure: 1) the uniform carbon layer can improve the electrical conductivity and ensure the formation of a stable SEI; 2) different active materials can relieve the stress caused by volume variation and also contribute additional capacity; 3) the small particle size can offer a strong kinetic of electrochemical reactions and lithium ion transfer. These results can strongly support the improvement of the capacity of Fe3O4‐based anodes by the unique multi‐function structural design, also providing new pathways for the design of other electrode materials.
Fully sp2‐Carbon‐Linked Crystalline Two‐Dimensional Conjugated Polymers: Insight into 2D Poly(phenylenecyanovinylene) Formation and its Optoelectronic Properties
Authors: Becker Daniel , Biswal Bishnu P. , Kaleńczuk Paula , Chandrasekhar Naisa , Giebeler Lars , Addicoat Matthew , Paasch Silvia , Brunner Eike , Leo Karl , Dianat Arezoo , Cuniberti Gianaurelio , Berger Reinhard , Feng Xinliang 
Published: March 2019

AbstractCyano‐substituted polyphenylene vinylenes (PPVs) have been the focus of research for several decades owing to their interesting optoelectronic properties and potential applications in organic electronics. With the advent of organic two‐dimensional (2D) crystals, the question arose as to how the chemical and optoelectronic advantages of PPVs evolve in 2D compared with their linear counterparts. In this work, we present the efficient synthesis of two novel 2D fully sp2‐carbon‐linked crystalline PPVs and investigate the essentiality of inorganic bases for their catalytic formation. Notably, among all bases screened, cesium carbonate (Cs2CO3) plays a crucial role and enables reversibility in the first step with subsequent structure locking by formation of a C=C double bond to maintain crystallinity, which is supported by density functional theory (DFT) calculations. A quantifiable energy diagram of a “quasi‐reversible reaction” is proposed, which allows the identification of further suitable C−C bond formation reactions for 2D polymerizations. Moreover, the narrowing of the HOMO–LUMO gap is delineated by expanding the conjugation into two dimensions. To enable environmentally benign processing, the post‐modification of 2D PPVs is further performed, which renders stable dispersions in the aqueous phase.
Donor and Ring‐Fusing Engineering for Far‐Red to Near‐Infrared Triphenylpyrylium Fluorophores with Enhanced Fluorescence Performance for Sensing and Imaging
Authors: Wen Si‐Yu , Zhang Wei , Ren Tian‐Bing , Zhang Qian‐Ling , Liu Yu‐Peng , Shi Ling , Hu Rongfeng , Zhang Xiao‐Bing , Yuan Lin 
Published: March 2019

AbstractFluorescent probes have become an indispensable tool in the detection and imaging of biological and disease‐related analytes due to their sensitivity and technical simplicity. In particular, fluorescent probes with far‐red to near‐infrared (FR‐NIR) emissions are very attractive for biomedical applications. However, many available FR‐NIR fluorophores suffer from small Stokes shifts and sometimes low quantum yields, resulting in self‐quenching and low contrast. In this work, we describe the rational design and engineering of FR‐NIR 2,4,6‐triphenylpyrylium‐based fluorophores (TPP‐Fluors) with the help of theoretical calculations. Our strategy is based on the appending of electron‐donating substituents and fusing groups onto 2,4,6‐triphenylpyrylium. In contrast to the parent TPP with short emission wavelength, weak quantum yields, and low chemical stability, the obtained novel TPP‐Fluors display some favorable properties, such as long‐wavelength emission, large Stokes shifts, moderate to high quantum yields, and chemical stability. TPP‐Fluors demonstrate their biological value as mitochondria‐specific labeling reagents due to their inherently positive nature. In addition, TPP‐Fluors can also be applied to develop ratiometric fluorescent probes, as the electron‐donating ability of the 2,6‐phenyl substituents is closely correlated with their emission wavelength. A proof‐of‐concept ratiometric probe has been developed by derivatizing the amino groups of TPP‐Fluor for the detection and imaging of nitroreductase in vitro and in hypoxic cells.
The Influence of Chemical Change on Protein Dynamics: A Case Study with Pyruvate Formate‐Lyase
Authors: Hanževački Marko , Čondić‐Jurkić Karmen , Banhatti Radha Dilip , Smith Ana‐Sunčana , Smith David M. 
Published: March 2019

AbstractPyruvate formate‐lyase (PFL) catalyzes the reversible conversion of pyruvate and coenzyme A (CoA) into formate and acetyl‐CoA in two half‐reactions. For the second half‐reaction to take place, the S−H group of CoA must enter the active site of the enzyme to retrieve a protein‐bound acetyl group. However, CoA is bound at the protein surface, whereas the active site is buried in the protein interior, some 20–30 Å away. The PFL system was therefore subjected to a series of extensive molecular dynamics simulations (in the μs range) and a host of advanced analysis procedures. Models representing PFL before and after the first half‐reaction were used to examine the possible effect of enzyme acetylation. All simulated structures were found to be relatively stable compared to the initial crystal structure. Although the adenine portion of CoA remained predominantly bound at the protein surface, the binding of the S−H group was significantly more labile. A potential entry channel for CoA, which would allow the S−H group to reach the active site, was identified and characterized. The channel was found to be associated with accentuated fluctuations and a higher probability of being in an open state in acetylated systems. This result suggests that the acetylation of the enzyme assumes a prominent functional role, whereby the formation of the acyl intermediate serves to initiate a subtle signaling cascade that influences the protein dynamics and facilitates the entry of the second substrate.