bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Effective Conjugation Length Is Responsible for the Red/Green Spectral Tuning in the Cyanobacteriochrome Slr1393g3
Authors: Wiebeler Christian , Rao Aditya G. , Gärtner Wolfgang , Schapiro Igor 
Published: December 2018

AbstractThe origin of the spectral shift from a red‐ to a green‐absorbing form in a cyanobacteriochrome, Slr1393g3, was identified by combined quantum mechanics/molecular mechanics simulations. This protein, related to classical phytochromes, carries the open‐chain tetrapyrrole chromophore phycocyanobilin. Our calculations reveal that the effective conjugation length in the chromophore becomes shorter upon conversion from the red to the green form. This is related to the planarity of the entire chromophore. A large distortion was found for the terminal pyrrole rings A and D; however, the D ring contributes more strongly to the photoproduct tuning, despite a larger change in the twist of the A ring. Our findings implicate that the D ring twist can be exploited to regulate the absorption of the photoproduct. Hence, mutations that affect the D ring twist can lead to rational tuning of the photoproduct absorption, allowing the tailoring of cyanobacteriochromes for biotechnological applications such as optogenetics and bioimaging.
Base‐Free Iron Catalyzed Transfer Hydrogenation of Esters Using EtOH as Hydrogen Source
Authors: Farrar‐Tobar Ronald A. , Wozniak Bartosz , Savini Arianna , Hinze Sandra , Tin Sergey , de Vries Johannes G. 
Published: December 2018

AbstractHerein, we report on the use of the iron pincer complex Iron‐MACHO‐BH, in the base‐free transfer hydrogenation of esters with EtOH as a hydrogen source. More than 20 substrates including aromatic and aliphatic esters and lactones were reduced affording the desired primary alcohols and diols with moderate to excellent isolated yields. It is also possible to reduce polyesters to the diols with this method, enabling a novel way of plastic recycling. Reduction of the renewable substrate methyl levulinate proceeds to form 1,4‐pentanediol directly. The yields are largely governed by the equilibrium between the alcohol and the ethyl ester.
Engineering Multifunctional DNA Hybrid Nanospheres through Coordination‐Driven Self‐Assembly
Authors: Li Mengyuan , Wang Congli , Di Zhenghan , Li Hui , Zhang Jingfang , Xue Wenting , Zhao Meiping , Zhang Ke , Zhao Yuliang , Li Lele 
Published: December 2018

AbstractDeveloping simple and general approaches for the synthesis of nanometer‐sized DNA materials with specific morphologies and functionalities is important for various applications. Herein, a novel approach for the synthesis of a new set of DNA‐based nanoarchitectures through coordination‐driven self‐assembly of FeII ions and DNA molecules is reported. By fine‐tuning the assembly, Fe–DNA nanospheres of precise sizes and controlled compositions can be produced. The hybrid nanoparticles can be tailored for delivery of functional DNA to cells in vitro and in vivo with enhanced biological function. This highlights the potential of metal ion coordination as a tool for directing the assembly of DNA architectures, which conceptualizes a new pathway to expand the repertoire of DNA‐based nanomaterials. This methodology will advance both the fields of DNA nanobiotechnology and metal–ligand coordination chemistry.
Towards Unveiling the Exact Molecular Structure of Amorphous Red Phosphorus by Single‐Molecule Studies
Authors: Zhang Song , Qian Hu‐jun , Liu Zhonghua , Ju Hongyu , Lu Zhong‐yuan , Zhang Haiming , Chi Lifeng , Cui Shuxun 
Published: December 2018

AbstractSince the discovery of amorphous red phosphorus (a‐red P) in 1847, many possible structures have been proposed. However, the exact molecular structure has not yet been determined because of its amorphous nature. Herein several methods are used to investigate basic properties of a‐red P. Data from scanning tunneling microscopy (STM) and gel permeation chromatography (GPC) confirm that a‐red P is a linear inorganic polymer with a broad molecular weight distribution. The theoretical single‐molecule elasticities of the possible a‐red P structures are obtained by quantum mechanical (QM) calculations. The experimental single‐molecule elasticity of a‐red P measured by single‐molecule AFM matches with the theoretical result of the zig‐zag ladder structure, indicating that a‐red P may adopt this structure. Although this conclusion needs further validation, this fundamental study represents progress towards solving the structure of a‐red P. It is expected that the strategy utilized in this work can be applied to study other inorganic polymers.
Association of Baseline Peptidylarginine Deiminase 4 Autoantibodies With Favorable Response to Treatment Escalation in Rheumatoid Arthritis
Authors: Darrah Erika , Yu Fang , Cappelli Laura C. , Rosen Antony , O'Dell James R. , Mikuls Ted R. 
Published: December 2018

ObjectiveTo determine if the baseline presence of autoantibodies to peptidylarginine deiminase 4 (PAD4) predicts therapeutic response to biologic and conventional disease‐modifying antirheumatic drugs (DMARDs) in patients with rheumatoid arthritis (RA) in whom methotrexate (MTX) monotherapy was unsuccessful.MethodsBaseline serum from 282 RA patients in whom MTX monotherapy was unsuccessful was screened for the presence of anti‐PAD4 antibodies by immunoprecipitation. Clinical response to either triple DMARD (MTX, sulfasalazine, and hydroxychloroquine) or MTX/etanercept combination therapy was determined at 24 and 48 weeks post–treatment initiation. Disease activity was measured using the Disease Activity Score 28‐joint assessment (DAS28), and erosive disease was quantified using the Sharp/van der Heijde scoring method. Generalized estimating equations (GEEs) were used to model the clinical responses to treatment in patients with and those without baseline anti‐PAD4 antibodies.ResultsAnti‐PAD4 antibody positivity was associated with male sex, a history of never smoking, and anti–citrullinated protein antibodies. At baseline, patients with anti‐PAD4 antibodies had longer disease duration and significantly more radiographic joint damage than anti‐PAD4–negative patients, but did not differ in disease activity according to the DAS28. In unadjusted analyses and multivariable GEE models, patients with anti‐PAD4 antibodies exhibited greater improvements in DAS28 (adjusted P = 0.02 and P = 0.008, respectively) and less radiographic progression (adjusted P = 0.01 and P = 0.002, respectively) compared to anti‐PAD antibody–negative patients, independent of treatment received.ConclusionAlthough anti‐PAD4 antibodies were associated with worse baseline radiographic joint damage, suggesting a history of active or undiagnosed disease, treatment escalation therapy was more effective in reducing disease activity and slowing the progression of joint damage in this patient subset.
Employment of fucosidases for the synthesis of fucosylated oligosaccharides with biological potential
Authors: Guzmán‐Rodríguez Francisco , Alatorre‐Santamaría Sergio , Gómez‐Ruiz Lorena , Rodríguez‐Serrano Gabriela , García‐Garibay Mariano , Cruz‐Guerrero Alma 
Published: December 2018

AbstractFucosylated oligosaccharides play important physiological roles in humans, including in the immune response, transduction of signals, early embryogenesis and development, growth regulation, apoptosis, pathogen adhesion, and so on. Efforts have been made to synthesize fucosylated oligosaccharides, as it is difficult to purify them from their natural sources, such as human milk, epithelial tissue, blood, and so on. Within the strategies for itsin vitrosynthesis, it is remarkable the employment of fucosidases, enzymes that normally cleave the fucosyl residue from the non‐reducing end of fucosylated compounds, as these enzymes are also capable of synthesizing them by means of a transfucosylation reaction. This review summarizes the progress in the use of fucosidases for the synthesis of compounds that have potential for industrial and commercial applications.
Multiset sparse redundancy analysis for high‐dimensional omics data
Authors: Csala Attila , Hof Michel H. , Zwinderman Aeilko H. 
Published: December 2018

AbstractRedundancy Analysis (RDA) is a well‐known method used to describe the directional relationship between related data sets. Recently, we proposed sparse Redundancy Analysis (sRDA) for high‐dimensional genomic data analysis to find explanatory variables that explain the most variance of the response variables. As more and more biomolecular data become available from different biological levels, such as genotypic and phenotypic data from different omics domains, a natural research direction is to apply an integrated analysis approach in order to explore the underlying biological mechanism of certain phenotypes of the given organism. We show that the multiset sparse Redundancy Analysis (multi‐sRDA) framework is a prominent candidate for high‐dimensional omics data analysis since it accounts for the directional information transfer between omics sets, and, through its sparse solutions, the interpretability of the result is improved. In this paper, we also describe a software implementation for multi‐sRDA, based on the Partial Least Squares Path Modeling algorithm. We test our method through simulation and real omics data analysis with data sets of 364,134 methylation markers, 18,424 gene expression markers, and 47 cytokine markers measured on 37 patients with Marfan syndrome.
A novel EMD mutation in a Chinese family with initial diagnosis of conduction cardiomyopathy
Authors: Zhou Junfeng , Li Hui , Li Xiangping , Li Yonggui , Yang Mei , Shi Gaoxing , Xu Danyan , Shi Xiaoliu 
Published: December 2018

AbstractIntroductionEmery–Dreifuss muscular dystrophy (EDMD) is a hereditary myopathy characterized as triad of muscular dystrophy, joint contractures, and conduction cardiomyopathy. In this study, we diagnosed a X‐linked recessive EDMD patient with severe conduction cardiomyopathy while noteless muscular and joint disorders.MethodsA Chinese cardiomyopathy family spanning four generations was enrolled in the study. Targeted next‐generation sequencing (NGS) was performed to identify the underlying mutation in the proband and validated by Sanger sequencing. Segregation analysis was applied to all 13 participants.ResultsA novel frameshift mutation (c.253_254insT, p.Y85Lfs*8) of emerin gene (EMD) was found and co‐segregated with family members. Other than the typical manifestations of X‐linked EDMD, this patient presented inconspicuous muscular disorders which were later diagnosed after the mutation been identified.ConclusionsThis study enriches the EMD gene mutation database and reminds us of the possibility of EDMD while encountering patients with severe heart rhythm defects or dilated cardiomyopathy of unknown etiology, even if they have neither obvious skeletal muscle disorder nor joint involvement.
Total MRI burden of cerebral vessel disease correlates with the progression in patients with acute single small subcortical strokes
Authors: Jiang Jingwen , Huang Xiaojun , Zhang Yu , Deng Weiping , Shen Fanxia , Liu Jianrong 
Published: December 2018

AbstractBackgroundThe patients of single small subcortical strokes (SS) commonly have neurological worsening with risk factors, and mechanisms remain unclear. Asymptomatic lacunes, white matter lesions, cerebral microbleeds, and enlarged perivascular spaces are MRI markers of cerebral small vessel disease (cSVD). Previous studies mostly explored the association between the neurological deterioration and presence of above markers separately. The relationship between progressive single small SS and the simultaneous presence of multiple markers of cSVD has not been fully identified. We aimed to investigate whether total burden of cSVD detected with MRI was associated with progressive small SS in this study.MethodsPatients with single small SS (2.0 cm in diameter) were prospectively recruited during January 2016 and May 2018. Progression was defined as worsening by ≥1 point in National Institutes Health Stroke Scale (NIHSS) motor score within 72 hr from onset. The presence and burden of cSVD were determined by brain MRI, producing a score between 0 and 4. Besides, the patients' characteristics, clinical data, medical treatments during hospitalization stay were collected and statistically analyzed. Associations with progression were tested with forward stepwise regression analyses.ResultsFifty‐seven (35.6%) patients underwent progression. No significant difference was observed in the distribution of any single vascular risk factor and its related laboratory data among these patients. After adjustment for age, sex, NIHSS score at admission, and time from stroke to MRI in separate models, severe WMHs (OR = 4.892; 95% CI = 2.011–11.904, p = 0.016), moderate‐ and high‐grade basal ganglia EPVS (OR = 2.970; 95% CI = 1.861–6.121, p = 0.009), and total cSVD score (OR = 3.359; 95% CI = 2.016–5.599, p = 0.010) were associated with progression.ConclusionThis study demonstrated that total MRI cSVD burden was independently associated with progression after single small subcortical strokes.
Anesthesia for endovascular treatment in anterior circulation stroke: A systematic review and meta‐analysis
Authors: Li Xuefei , Hu Zheng , Li Qian , Guo Yinping , Xu Shabei , Wang Wei , He Dan , Luo Xiang 
Published: December 2018

AbstractBackgroundEndovascular treatment in patients with acute anterior circulation stroke could be performed under either conscious sedation (CS) or general anesthesia (GA). Although several studies have investigated the association between the clinical outcomes and the two anesthesia methods, consensus is lacking.MethodsPubMed and EMBASE searches were used to select full‐text articles comparing the effects of GA and CS on functional outcome and complications in patients with anterior circulation ischemic stroke. Enrolled patients were assigned to receive endovascular treatment with CS or GA, with a primary outcome of functional independency within 90 days. Secondary outcomes included intracranial hemorrhage, all‐cause mortality at 90 days, pneumonia, and intraprocedural complications.ResultsThirteen studies (3 RCTs and 10 observational studies), which included 3,857 patients (CS = 2,129, GA = 1,728), were eligible for the analysis. The overall analysis including the RCTs and observational studies demonstrated that the functional independence within 90 days occurred more frequently among patients with CS compared with GA (OR, 1.42; 95% CI, 1.05–1.92, p = 0.02); and the risk of mortality was higher with GA compared with CS; furthermore, CS was associated with lower rate of intracranial hemorrhage. In RCTs, GA was associated with increased functional independence (OR, 0.55; 95% CI, 0.34–0.89, p = 0.01) and successful reperfusion (OR, 0.51; 95% CI, 0.30–0.89, p = 0.02).ConclusionsIn the overall analysis and observational studies, CS was associated with improved functional outcomes and relatively safe for anterior ischemic stroke compared with GA. While the pooled data from RCTs suggested that GA was associated with improved outcomes. The inconsistency indicated that more large‐scale RCTs are required to evaluate what factors influenced the effect of the anesthesia methods on clinical outcomes.
Macromolecular Crowding Tunes Protein Stability by Manipulating Solvent Accessibility
Authors: Köhn Birgit , Kovermann Michael 
Published: December 2018

AbstractIn all intracellular processes, protein structure and dynamics are subject to the influence of macromolecular crowding (MC). Here, the impact of MC agents of different types and sizes on the model protein Bacillus subtilis Cold shock protein B (BsCspB) during both thermal and chemical denaturation have been comprehensively investigated. We consistently reveal a distinct stabilization of BsCspB in a manner dependent on the MC concentration but not on viscosity, polarity, or size of the MC agent used. This general stabilization has been decoded by use of NMR spectroscopy, through monitoring of chemical shift (CS) perturbations and the intramolecular hydrogen‐bonding networks, as well as local protection of amide protons against exchange with solvent protons. Whereas CSs and hydrogen‐bonding networks are not systematically affected in the presence of MC, we detected a pronounced reduction in exchange in loop regions of BsCspB. We conclude that this reduced accessibility of solvent protons is a key parameter for the increases in protein stability seen under MC.
Myocardial fibrosis predicts adverse outcome after MitraClip implantation
Authors: Velu Juliëtte F. , Hirsch Alexander , Boekholdt S. M. , Koch Karel T. , Marije Vis M. , Nils Planken R. , Piek Jan J. , Baan Jan , Bouma Berto J. 
Published: December 2018

AbstractBackgroundHigh‐risk patients with mitral regurgitation (MR) may be treated by a percutaneous mitral valve repair with the MitraClip, but identification of patients who may benefit remains difficult. We aimed to determine whether myocardial fibrosis predicts outcome in MR patients undergoing MitraClip implantation and is beneficial in clinical decision making.MethodsPreprocedural to the MitraClip implantation, myocardial fibrosis was analyzed with cardiovascular magnetic resonance (CMR) through late gadolinium enhancement. The CMR data were core‐lab adjudicated measured before the MitraClip implantation. Adverse outcome was defined as New York Heart Association (NYHA) class III or IV after 1 month or death within 1 month after the MitraClip implantation.ResultsIn total, 23 patients underwent preprocedural CMR, mean age 80 ± 9 years, 45% male, 64% atrial fibrillation and 73% NYHA class III or IV at baseline. Myocardial fibrosis was present in 55% of the patients with degenerative MR and in 64% of the patients with functional MR. An adverse outcome occurred in 69% of the patients with myocardial fibrosis and in 11% of the patients without myocardial fibrosis (P = 0.01).ConclusionsOur hypothesis‐generating study showed that the presence of myocardial fibrosis predicts adverse outcome in patients undergoing MitraClip implantation. After confirmation with larger sample size, identification of myocardial fibrosis might contribute to assess prognosis and to clinical decision making.
Bench‐Stable Cobalt Pre‐Catalysts for Mild Hydrosilative Reduction of Tertiary Amides to Amines and Beyond
Authors: Nurseiit Alibek , Janabel Jaysan , Gudun Kristina A. , Kassymbek Aishabibi , Segizbayev Medet , Seilkhanov Tulegen M. , Khalimon Andrey Y. 
Published: December 2018

AbstractThe readily synthesized and bench‐stable cobalt dichloride complex (dpephos)CoCl2is employed as a pre‐catalyst for a diversity of silane additions to unsaturated organic molecules, including the normally challenging reduction of amides to amines. With regard to hydrosilative reduction of amides even more effective and activator free catalytic systems can be generated from the bench‐stable, commercially available Co(acac)2and Co(OAc)2with dpephos and PPh3ligands. These systems operate under mild conditions (<100 °C), with many examples of room temperature transformations, presenting a first example of mild cobalt‐catalyzed hydrosilylation of amides.
Reactive Oxygen Species Produced by Mutated Mitochondrial Respiratory Chains of Entire Cells Monitored Using Modified Microelectrodes
Authors: Malferrari Marco , Ghelli Anna , Roggiani Francesco , Valenti Giovanni , Paolucci Francesco , Rugolo Michela , Rapino Stefania 
Published: December 2018

AbstractGenetic alterations affecting subunits of the mitochondrial respiratory chain complexes often impair their catalytic activities and result in enhanced production of reactive oxygen species (ROS). An electrochemical setup was employed to quantify mitochondrial ROS production in plasma membrane‐permeabilized cellular models of two genetic diseases: the Δcytb cell line bearing a microdeletion in the mitochondrial MT‐CYB gene causing a severe encephalomyopathy and the RJ206 cell line, harbouring a pathogenic mutation associated with Leber's hereditary optic neuropathy. The responses of black platinum modified microelectrodes to the most common cellular redox buffers, namely, NADH and glutathione, as well as substrates deriving from the oxidative metabolism of glucose, were investigated; a relatively high sensitivity, although lower than that for ROS, was shown for NADH. Time‐resolved amperometric measurements of ROS production upon respiratory chain activation at high NADH/NAD+ ratio revealed a 50 % and 100 % increase of ROS in cells bearing defective complex I and complex III, respectively, as compared to wild type cells.
Phosphorus‐Doped Nanocrystalline Diamond for Supercapacitor Application
Authors: Yu Siyu , Xu Jing , Kato Hiromitsu , Yang Nianjun , Schulte Anna , Schönherr Holger , Jiang Xin 
Published: December 2018

AbstractHeavily phosphorus‐doped nanocrystalline diamond (P‐NCD) has been grown by using a plasma‐enhanced chemical vapor deposition technique and further applied as an electrode for the construction of supercapacitors. This P‐NCD electrode shows a capacitance of 11.40 μF cm−2 in 1.0 M Na2SO4 at a scan rate of 10 mV s−1 and behaves as a n‐type semiconductor electrode in redox‐active electrolyte of 0.05 M Fe(CN)63−/4−+1.0 M Na2SO4. The post‐thermal treatment of as‐grown P‐NCD films in vacuum at high temperatures for several hours leads to the achievement of much higher capacitances. At the scan rates of 10 and 20 mV s−1, the capacitances are up to 2.01 and 63.56 mF cm−2 for an electrical double layer capacitor and a pseudocapacitor, respectively. Such high capacitances originate from the improved electrical conductivity, varied surface state and surface functional groups, and changed content of non‐carbon diamond inside the P‐NCD films during the annealing treatment. Therefore, P‐NCD films are quite promising as an electrode material for supercapacitor applications.
MnO2‐Mediated Synthesis of Mn3O4@CaMn7O12 Core@Shell Nanorods for Electrocatalytic Oxygen Reduction Reaction
Authors: Ma Aijing , Chang Ailiu , Zhang Jingfang , Gui Jianzhou , Liu Dan , Yu Yifu , Zhang Bin 
Published: December 2018

AbstractThe rational design of low‐cost and earth‐abundant perovskite oxide alternatives as highly efficient and robust electrocatalysts for the oxygen reduction reaction (ORR) is desirable but remains a great challenge. Herein, we developed a simple MnO2‐mediated synthetic approach to Mn3O4@CaMn7O12 core@shell nanorods by impregnating MnO2 nanorods with a certain amount of Ca(NO3)2 solution (Mn : Ca=15 : 1), followed by a calcination process at 850 °C in air. By adjusting the Mn : Ca molar ratios, Ca−Mn oxides with different structures can also be prepared. Benefiting from the intrinsic characteristics of CaMn7O12 perovskite oxides and the structural advantage of nanorods, Mn3O4@CaMn7O12 core@shell nanorods exhibit high ORR activity with a positive onset potential of 0.90 V and half‐wave potential of 0.75 V. Also, they have an excellent tolerance ability to methanol. More importantly, the work may pave a new avenue to design other novel electrocatalysts with high performance and stability towards energy conversion and storage applications.