bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Pyrene‐Linked Cavity within a β‐Barrel Protein Promotes an Asymmetric Diels–Alder Reaction
Authors: Himiyama Tomoki , Taniguchi Naomasa , Kato Shunsuke , Onoda Akira , Hayashi Takashi 
Published: August 2017

AbstractA unique π‐expanded reaction cavity tethering a polycyclic moiety which provides a platform for substrate binding was constructed within the robust β‐barrel structure of nitrobindin (NB). NB variants with cavities of different sizes and shapes are coupled with N‐(1‐pyrenyl)maleimide (Pyr) to prepare a series of NB‐Pyr conjugates. The orientation of the pyrene moiety is fixed within the cavity by the coupling reaction. The fluorescent quenching analysis of NB‐Pyr indicates that azachalcone (aza), which is a dienophile for a Diels–Alder (DA) reaction, is efficiently incorporated within the pyrene‐linked reaction cavity by the aromatic interaction. The DA reaction between aza and cyclopentadiene proceeds within the reaction cavity of NB‐Pyr in the presence of CuII ion in high yield and high enantio‐ and regioselectivity.
Aryloxide‐Facilitated Catalyst Turnover in Enantioselective α,β‐Unsaturated Acyl Ammonium Catalysis
Authors: Matviitsuk Anastassia , Greenhalgh Mark D. , Antúnez Diego‐Javier Barrios , Slawin Alexandra M. Z. , Smith Andrew D. 
Published: August 2017

AbstractA new general concept for α,β‐unsaturated acyl ammonium catalysis is reported that uses p‐nitrophenoxide release from an α,β‐unsaturated p‐nitrophenyl ester substrate to facilitate catalyst turnover. This method was used for the enantioselective isothiourea‐catalyzed Michael addition of nitroalkanes to α,β‐unsaturated p‐nitrophenyl esters in generally good yield and with excellent enantioselectivity (27 examples, up to 79 % yield, 99:1 er). Mechanistic studies identified rapid and reversible catalyst acylation by the α,β‐unsaturated p‐nitrophenyl ester, and a recently reported variable‐time normalization kinetic analysis method was used to delineate the complex reaction kinetics.
Photochemical Intramolecular C−H Addition of Dimesityl(hetero)arylboranes through a [1,6]‐Sigmatropic Rearrangement
Authors: Ando Naoki , Fukazawa Aiko , Kushida Tomokatsu , Shiota Yoshihito , Itoyama Shuhei , Yoshizawa Kazunari , Matsui Yasunori , Kuramoto Yutaro , Ikeda Hiroshi , Yamaguchi Shigehiro 
Published: August 2017

AbstractA new reaction mode for triarylboranes under photochemical conditions was discovered. Photoirradiation of dimesitylboryl‐substituted (hetero)arenes produced spirocyclic boraindanes, where one of the C−H bonds in the ortho‐methyl groups of the mesityl substituents was formally added in a syn fashion to a C−C double bond of the (hetero)aryl group. Quantum chemical calculations and laser flash photolysis measurements indicated that the reaction proceeds through a [1,6]‐sigmatropic rearrangement. This behavior is reminiscent of the photochemical reaction mode of arylalkenylketones, thus demonstrating the isosteric relation between tricoordinate organoboron compounds and the corresponding pseudo‐carbocationic species in terms of pericyclic reactions. Despite the disrupted π‐conjugation, the resulting spirocyclic boraindanes exhibited a characteristic absorption band at relatively long wavelengths (λ=370—400 nm).
Silica–polyaniline hybrid materials prepared by inverse emulsion polymerization for epoxy‐based anticorrosive coating
Authors: Caldas Camila M. , Calheiros Loan F. , G. Soares Bluma 
Published: August 2017

ABSTRACTPolyaniline doped with dodecylbenzene sulfonic acid (PAni.DBSA) was prepared by inverse emulsion polymerization of aniline in toluene medium in the presence of silica (SiO2) nanoparticles. The presence of cetyltrimethylammonium bromide (CTAB) during the aniline polymerization results in hybrid material with smaller particle size, as indicated by dynamic light scattering analysis and scanning electron microscopy. Also the electrical conductivity of such hybrid is one order higher, as compared with that prepared without CTAB. Moreover, more ordered PAni chain is obtained as indicated by the red shift of the π–polaron transition band observed by UV–vis spectroscopy and higher crystallinity observed by X‐ray diffraction analysis. Anti‐corrosive properties of carbon steel substrate coated with epoxy resin containing 5 wt % of PAni.DBSA and the corresponding SiO2‐based hybrid materials were evaluated in 3.5% NaCl solution by electrochemical impedance spectroscopy. The coating resistance increases by one order for the epoxy system containing PAni.DBSA/SiO2 hybrid prepared in the presence of CTAB, thus confirming the anticorrosion efficiency of this hybrid. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45505.
Analytical interpretations of static and dynamic mechanical properties of thermoplastic elastomer toughened PLA blends
Authors: Nehra Ranjana , Maiti Saurindra Nath , Jacob Josemon 
Published: August 2017

ABSTRACTPoly(lactic acid) (PLA) was melt blended with thermoplastic elastomer (TPE) styrene–ethylene–butylene–styrene‐g‐maleic anhydride (SEBS‐g‐MA) copolymer using a micro compounder which used melt recirculation approach for efficient dispersion of SEBS‐g‐MA in PLA. The SEBS‐g‐MA volume fraction (Φd) was varied between 0.07 and 0.48. Dynamic mechanical analysis showed 10.4 °C decrease in glass transition temperature at Φd = 0.48. Differential scanning calorimetry results exhibited shift in cold crystallization temperature to a higher temperature in the presence of SEBS‐g‐MA. Thermogravimetric analysis presented enhanced thermal stability of PLA/SEBS‐g‐MA blends. Tensile strength and modulus decreased while elongation‐at‐break and Izod impact strength increased in the blends. Theoretical models were employed to analyze the tensile properties of the blends in order to evaluate the blend structure. The microstructural attributes were characterized by wide‐angle X‐ray diffraction, Fourier‐transform infrared spectroscopy, and scanning electron microscopy of cryofractured, impact fractured, and tensile fractured surfaces. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45644.
Novel 3D Semiconducting Open‐Frameworks based on Cuprous Bromides with Visible Light Driven Photocatalytic Properties
Authors: Lei Xiao‐Wu , Yue Cheng‐Yang , Wei Jun‐Chao , Li Rui‐Qing , Mi Fu‐Qi , Li Yan , Gao Lu , Liu Quan‐Xiu 
Published: August 2017

AbstractVisible light driven photocatalysts based on crystalline microporous metal halogenides received much less attention compared with dense or composite oxide semiconductors. Using the well‐known photosensitive transition metal‐complexes [TM(2,2‐bipy)3]2+ (TM=Fe, Co, Ni, Ru) as templates, a special three‐dimensional (3D) metal halogenide framework of [TM(2,2‐bipy)3]Cu4Br6 was designed with [Cu4Br4] cluster as 4‐connected node. These microporous materials feature narrow band gaps and stable visible light driven photocatalytic properties including water reduction to provide H2 and photodegradation of organic pollutants. The study of electronic band structure shows that the TM complexes effectively prevent the recombination of photo‐induced electron/hole pairs leading to excellent photocatalytic activity and photochemical stability. This work represents the first 3D microporous metal halogenides used as visible light driven photocatalyst to provide hydrogen energy.
Utility of DNA barcoding to identify rare endemic vascular plant species in Trinidad
Authors: Hosein Fazeeda N. , Austin Nigel , Maharaj Shobha , Johnson Winston , Rostant Luke , Ramdass Amanda C. , Rampersad Sephra N. 
Published: August 2017

AbstractThe islands of the Caribbean are considered to be a “biodiversity hotspot.” Collectively, a high level of endemism for several plant groups has been reported for this region. Biodiversity conservation should, in part, be informed by taxonomy, population status, and distribution of flora. One taxonomic impediment to species inventory and management is correct identification as conventional morphology‐based assessment is subject to several caveats. DNA barcoding can be a useful tool to quickly and accurately identify species and has the potential to prompt the discovery of new species. In this study, the ability of DNA barcoding to confirm the identities of 14 endangered endemic vascular plant species in Trinidad was assessed using three DNA barcodes (matK, rbcL, and rpoC1). Herbarium identifications were previously made for all species under study. matK, rbcL, and rpoC1 markers were successful in amplifying target regions for seven of the 14 species. rpoC1 sequences required extensive editing and were unusable. rbcL primers resulted in cleanest reads, however, matK appeared to be superior to rbcL based on a number of parameters assessed including level of DNA polymorphism in the sequences, genetic distance, reference library coverage based on BLASTN statistics, direct sequence comparisons within “best match” and “best close match” criteria, and finally, degree of clustering with moderate to strong bootstrap support (>60%) in neighbor‐joining tree‐based comparisons. The performance of both markers seemed to be species‐specific based on the parameters examined. Overall, the Trinidad sequences were accurately identified to the genus level for all endemic plant species successfully amplified and sequenced using both matK and rbcL markers. DNA barcoding can contribute to taxonomic and biodiversity research and will complement efforts to select taxa for various molecular ecology and population genetics studies.
Progression of regional atrophy in the left hemisphere contributes to clinical and cognitive deterioration in multiple sclerosis: A 5‐year study
Authors: Preziosa Paolo , Pagani Elisabetta , Mesaros Sarlota , Riccitelli Gianna C. , Dackovic Jelena , Drulovic Jelena , Filippi Massimo , Rocca Maria A. 
Published: August 2017

AbstractIn this longitudinal study, we investigated the regional patterns of focal lesions accumulation, and gray (GM) and white matter (WM) atrophy progression over a five‐year follow‐up (FU) in multiple sclerosis (MS) patients and their association with clinical and cognitive deterioration. Neurological, neuropsychological and brain MRI (dual‐echo and 3D T1‐weighted sequences) assessments were prospectively performed at baseline (T0) and after a median FU of 4.9 years from 66 MS patients (including relapse‐onset and primary progressive MS) and 16 matched controls. Lesion probability maps were obtained. Longitudinal changes of GM and WM volumes and their association with clinical and cognitive deterioration were assessed using tensor‐based morphometry and SPM12. At FU, 36/66 (54.5%) MS patients showed a significant disability worsening, 14/66 (21.2%) evolved to a worse clinical phenotype, and 18/63 (28.6%) developed cognitive deterioration. At T0, compared to controls, MS patients showed a widespread pattern of GM atrophy, involving cortex, deep GM and cerebellum, and atrophy of the majority of WM tracts, which further progressed at FU (P < 0.001, uncorrected). Compared to stable patients, those with clinical and cognitive worsening showed a left‐lateralized pattern of GM and WM atrophy, involving deep GM, fronto‐temporo‐parieto‐occipital regions, cerebellum, and several WM tracts (P < 0.001, uncorrected).GM and WM atrophy of relevant brain regions occur in MS after 5 years. A different vulnerability of the two brain hemispheres to irreversible structural damage may be among the factors contributing to clinical and cognitive worsening in these patients. Hum Brain Mapp 38:5648–5665, 2017. © 2017 Wiley Periodicals, Inc.
Intrinsic functional connectivity variance and state‐specific under‐connectivity in autism
Authors: Chen Heng , Nomi Jason S. , Uddin Lucina Q. , Duan Xujun , Chen Huafu 
Published: August 2017

AbstractAutism spectrum disorder (ASD) is a neurodevelopmental condition associated with altered brain connectivity. Previous neuroimaging research demonstrates inconsistent results, particularly in studies of functional connectivity in ASD. Typically, these inconsistent findings are results of studies using static measures of resting‐state functional connectivity. Recent work has demonstrated that functional brain connections are dynamic, suggesting that static connectivity metrics fail to capture nuanced time‐varying properties of functional connections in the brain. Here we used a dynamic functional connectivity approach to examine the differences in the strength and variance of dynamic functional connections between individuals with ASD and healthy controls (HCs). The variance of dynamic functional connections was defined as the respective standard deviations of the dynamic functional connectivity strength across time. We utilized a large multicenter dataset of 507 male subjects (209 with ASD and 298 HC, from 6 to 36 years old) from the Autism Brain Imaging Data Exchange (ABIDE) to identify six distinct whole‐brain dynamic functional connectivity states. Analyses demonstrated greater variance of widespread long‐range dynamic functional connections in ASD (P < 0.05, NBS method) and weaker dynamic functional connections in ASD (P < 0.05, NBS method) within specific whole‐brain connectivity states. Hypervariant dynamic connections were also characterized by weaker connectivity strength in ASD compared with HC. Increased variance of dynamic functional connections was also related to ASD symptom severity (ADOS total score) (P < 0.05), and was most prominent in connections related to the medial superior frontal gyrus and temporal pole. These results demonstrate that greater intraindividual dynamic variance is a potential biomarker of ASD. Hum Brain Mapp 38:5740–5755, 2017. © 2017 Wiley Periodicals, Inc.
Dorsal and palmar aspect dimensions of hand anthropometry for designing hand tools and protections
Authors: Vergara M. , Agost M. J. , Gracia‐Ibáñez V. 
Published: August 2017

AbstractMost hand anthropometric studies are performed on the palmar aspect, while dimensions of the dorsal aspect are also useful in ergonomics and hand modeling. A survey of hand anthropometrics for a Spanish population (69 females, 70 males) is presented. Landmarks were selected to compare lengths from the dorsal and palmar aspects and to be useful for hand modeling and ergonomics design. Ninety‐nine dimensions of fingers and thumb of the right hand (41 lengths, 32 depths, 26 breadths) were collected, including thumb breadths and depths. Descriptive statistics of all the dimensions are presented. Lengths were measured from both dorsal and palmar aspects and paired lengths compared through t‐tests. Significant differences were found in almost all the lengths, showing that databases should explicitly state the aspect (dorsal or palmar) where dimensions have been measured. The data provided are useful for designing tools and hand protections and developing hand models more accurately.
Identification of expression quantitative trait loci (eQTLs) in human peripheral blood mononuclear cells (PBMCs) and shared with liver and brain
Authors: He Pei , Xia Wei , Wang Lan , Wu Jian , Guo Yu‐Fan , Zeng Ke‐Qin , Wang Ming‐Jun , Bing Peng‐Fei , Xie Fang‐Fei , Lu Xin , Zhang Yong‐Hong , Lei Shu‐Feng , Deng Fei‐Yan 
Published: August 2017

AbstractPBMCs are essential for immunity and involved in various diseases. To identify genetic variations contributing to PBMCs transcriptome‐wide gene expression, we performed a genome‐wide eQTL analysis by using genome‐wide SNPs data and transcriptome‐wide mRNA expression data. To assess whether there are common regulation patterns shared among different tissues/organs, public datasets were utilized to identify common eQTLs shared with PBMCs in lymphoblastoid, monocytes, liver, and brain. Allelic expression imbalance (AEI) assay was employed to validate representative eQTLs identified. We identified 443 cis‐ and 2386 trans‐eSNPs (FDR <0.05), which regulated 128 and 635 target genes, respectively. A transcriptome‐wide expression regulation network was constructed, highlighting the importance of 28 pleiotropic eSNPs and 18 dually (cis‐ and trans‐) regulated genes. Three genes, that is, TIPRL, HSPB8, and EGLN3, were commonly regulated by hundreds of eSNPs and constituted a very complex interaction network. Strikingly, the missense SNP rs371513 trans‐ regulated 25 target genes, which were functionally related to poly(A) RNA binding. Among 8904 eQTLs (P < 0.001) identified herein in PBMCs, a minority (163) was overlapped with lymphoblastoid, monocytes, liver, and/or brain. Besides, two cis‐eSNPs in PBMC were confirmed by AEI. The present results demonstrated a comprehensive expression regulation network for human PBMCs and may provide novel insights into the pathogenesis of immunological diseases related to PBMCs.
Applications of optogenetic and chemogenetic methods to seizure circuits: Where to go next?
Authors: Forcelli Patrick A. 
Published: August 2017

AbstractEpilepsy is the quintessential circuit disorder, with seizure activity propagating through anatomically constrained pathways. These pathways, necessary for normal sensory, motor, and cognitive function, are hijacked during seizures. Understanding the network architecture at the level of both local microcircuits and distributed macrocircuits may provide new therapeutic avenues for the treatment of epilepsy. Over the past decade, optogenetic and chemogenetic tools have enabled previously impossible levels of functional circuit mapping in neuroscience. In this review, examples of the application of optogenetics and chemogenetics to epilepsy are raised, the comparative strengths and weaknesses of these approaches are discussed for both preclinical and translational applications, and recent applications of these approaches in other areas of neuroscience are highlighted. These points are raised in an effort to highlight the potential of these methods to address additional unanswered questions in epilepsy.
Ultra high performance liquid chromatography coupled with electrospray ionization/quadrupole time‐of‐flight mass spectrometry for the rapid analysis of constituents in the traditional Chinese medicine formula Wu Ji Bai Feng Pill
Authors: Duan Shengnan , Qi Wen , Zhang Siwen , Huang Kunkun , Yuan Dan 
Published: August 2017

AbstractAn ultra high performance liquid chromatography coupled with electrospray ionization quadrupole time‐of‐flight mass spectrometry method in both positive and negative ion modes was established in order to comprehensively investigate the major constituents in Wu Ji Bai Feng Pill. Briefly, a Waters ACQUITY UPLC HSS C18 column was used to separate the aqueous extract of Wu Ji Bai Feng Pill. A total of 0.1% formic acid in acetonitrile and 0.1% aqueous formic acid v/v were used as the mobile phase. All analytes were determined using quadrupole time‐of‐flight mass spectrometry with electrospray ionization source in positive and negative ion modes. At length, a total of 173 components including flavones and their glycosides, monoterpene glycosides, triterpene saponins, phenethylalchohol glycosides, iridoid glycosides, phthalides, tanshinones, phenolic acids, sesquiterpenoids and cyclopeptides were identified or tentatively characterized in Wu Ji Bai Feng Pill in an analysis of 16.0 min based on the accurate mass and tandem mass spectrometry behaviors. The developed method is rapid and highly sensitive to characterize the chemical constituents of Wu Ji Bai Feng Pill, which could not only be used for chemical standardization and quality control of Wu Ji Bai Feng Pill, but also be helpful for further study in vivo metabolism of Wu Ji Bai Feng Pill.
Comprehensive headspace gas chromatographic analysis of denaturants in denatured ethanol
Authors: van Boxtel Niels , Wolfs Kris , Guillén Palacín Marta , Van Schepdael Ann , Adams Erwin 
Published: August 2017

AbstractTo discourage consumption, ethanol is often denatured using both volatile (e.g., methyl ethyl ketone and isopropanol) and nonvolatile (e.g., denatonium benzoate) chemical substances. As a result, the analysis of denatured ethanol samples is usually performed by multiple techniques such as gas chromatography for the volatile denaturants and liquid chromatography for the nonvolatile ones. However, the need for multiple techniques increases the cost of analysis and forms a severe obstruction for on‐site product control. Using the full evaporation technique combined with gas chromatography and flame ionization detection, only one analytical methodology has to be used here to determine both volatile and nonvolatile denaturants in denatured ethanol. Denatonium benzoate is determined as benzyl chloride following an in‐vial reaction. Compared to conventional techniques, the novel method performs equally well, but it is simpler to apply. At the same time, drawbacks of alternative methods are circumvented such as equilibration issues and alterations to the stationary phase when using liquid chromatography with ion pairing agents or matrix effects when applying static headspace gas chromatography. The developed method showed good linearity, repeatability, and recovery toward all analytes and was applied to the analysis of commercial denatured ethanol for disinfection and ethanol‐based windscreen washer fluids.
Heterogeneity in reporting on urinary outcome and cure after surgical interventions for stress urinary incontinence in adult neuro‐urological patients: A systematic review
Authors: Reuvers Sarah H.M. , Groen Jan , Scheepe Jeroen R. , ‘t Hoen Lisette A. , Castro‐Diaz David , Padilla‐Fernández Bárbara , Del Popolo Giulio , Musco Stefania , Pannek Jürgen , Kessler Thomas M. , Schneider Marc P. , Karsenty Gilles , Phé Veronique , Hamid Rizwan , Ecclestone Hazel , Blok Bertil F.M. 
Published: August 2017

AimsTo describe all outcome parameters and definitions of cure used to report on outcome of surgical interventions for stress urinary incontinence (SUI) in neuro‐urological (NU) patients.MethodsThis systematic review was performed and reported according to the Preferred Reporting Items for Systematic Reviews and Meta‐Analyses (PRISMA) statement. The study protocol was registered and published (CRD42016033303; http://www.crd.york.ac.uk/PROSPERO). Medline, Embase, Cochrane controlled trials databases, and clinicaltrial.gov were systematically searched for relevant publications until February 2017.ResultsA total of 3168 abstracts were screened. Seventeen studies reporting on SUI surgeries in NU patients were included. Sixteen different outcome parameters and nine definitions of cure were used. Six studies reported on objective outcome parameters mainly derived from urodynamic investigations. All studies reported on one or more subjective outcome parameters. Patient‐reported pad use (reported during interview) was the most commonly used outcome parameter. Only three of 17 studies used standardized questionnaires (two on impact of incontinence and one on quality of life). Overall, a high risk of bias was found.ConclusionsWe found a considerable heterogeneity in outcome parameters and definitions of cure used to report on outcome of surgical interventions for SUI in NU patients. The results of this systematic review may begin the dialogue to a future consensus on this topic. Standardization of outcome parameters and definitions of cure would enable researchers and clinicians to consistently compare outcomes of different studies and therapies.