bluuebunny/crossref_metadata_2025_split huggingface dataset:
Rapid Assembly of Saturated Nitrogen Heterocycles in One‐Pot: Diazo‐Heterocycle “Stitching” by N–H Insertion and Cyclization
Authors: Boddy Alexander J. , Affron Dominic P. , Cordier Christopher J. , Rivers Emma L. , Spivey Alan C. , Bull James A. 
Published: December 2018

AbstractMethods that provide rapid access to new heterocyclic structures in biologically relevant chemical space provide important opportunities in drug discovery. Here, a strategy is described for the preparation of 2,2‐disubstituted azetidines, pyrrolidines, piperidines, and azepanes bearing ester and diverse aryl substituents. A one‐pot rhodium catalyzed N–H insertion and cyclization sequence uses diazo compounds to stitch together linear 1,m‐haloamines (m=2–5) to rapidly assemble 4 ‐, 5 ‐, 6 ‐, and 7 ‐membered saturated nitrogen heterocycles in excellent yields. Over fifty examples are demonstrated, including examples with diazo compounds derived from biologically active compounds. The products can be functionalized to afford α,α‐disubstituted amino acids and applied to fragment synthesis.
Access to N‐Substituted 2‐Pyridones by Catalytic Intermolecular Dearomatization and 1,4‐Acyl Transfer
Authors: Xu Guangyang , Chen Ping , Liu Pei , Tang Shengbiao , Zhang Xinhao , Sun Jiangtao 
Published: December 2018

AbstractA novel rhodium‐catalyzed dearomatization of O‐substituted pyridines to access N‐substituted 2‐pyridones has been developed. A computational study suggests a mechanism involving the formation of a pyridinium ylide followed by an unprecedented 1,4‐acyl migratory rearrangement from O to C. Furthermore, the chiral dirhodium complexes serve as the catalyst for the asymmetric transformation with excellent enantioselective control. DFT calculations indicate the chirality is transferred from axial chirality to the central stereogenic centre. The stronger π–π interaction and CH–π interaction account for the high enantioselectivity.
Divergent Synthesis of 3‐Deoxy‐d‐manno‐oct‐2‐ulosonic Acid (Kdo) Glycosides Containing α‐(2→4)‐Linked Kdo‐Kdo Unit
Authors: Zhou Xian‐Yang , Yang Pan , Luo Sheng , Yang Jin‐Song 
Published: December 2018

AbstractA convenient and divergent approach was developed to prepare diverse bacterial 3‐deoxy‐d‐manno‐oct‐2‐ulosonic acid (Kdo) oligosaccharides containing a Kdo‐α‐(2→4)‐Kdo fragment. The orthogonal protected α‐(2→4) linked Kdo‐Kdo disaccharide 3, serving as a common precursor, was divergently transformed into the corresponding 8‐, 8′‐, and 4′‐hydroxy disaccharides 5, 7, and 14, respectively. Then, these alcohols were glycosylated, respectively, with the 5,7‐O‐di‐tert‐butylsilylene (DTBS) protected Kdo thioglycoside donors 1 or 2 in an α‐stereoselective and high‐yielding manner to afford a range of Kdo oligosaccharides. Finally, removal of all protecting groups of the newly formed glycosides resulted in the desired free Kdo oligomer.
Recent advances in biosensors for diagnosis of celiac disease: A review
Authors: Gupta Shagun , Kaushal Ankur , Kumar Ashok , Kumar Dinesh 
Published: December 2018

AbstractCeliac disease (CD) is an intestinal issue activated by the inappropriate immune reaction towards gluten protein of wheat, rye, barley, oats, and autoantigen, tissue transglutaminase. Regardless of the accessibility of immunochemical conventions for research facility analysis of CD, there is as yet a need of speedier, less expensive, and simpler devices for diagnosing CD. This review concentrates on progresses in biosensors for diagnosing CD in perspective of the scaled down hardware, multianalyte discovery and low sample volume necessity. Various recently developed biosensors in this field are presented.
Objective and subjective measures of prior sleep–wake behavior predict functional connectivity in the default mode network during NREM sleep
Authors: Wilson Rebecca S. , Mayhew Stephen D. , Rollings David T. , Goldstone Aimee , Hale Joanne R. , Bagshaw Andrew P. 
Published: December 2018

AbstractIntroductionPrior sleep behavior has been shown to correlate with waking resting‐state functional connectivity (FC) in the default mode network (DMN). However, the impact of sleep history on FC during sleep has not been investigated. The aim of this study was to establish whether there is an association between intersubject variability in habitual sleep behaviors and the strength of FC within the regions of the DMN during non‐rapid eye movement (NREM) sleep.MethodsWrist actigraphy and sleep questionnaires were used as objective and subjective measures of habitual sleep behavior, and EEG‐functional MRI during NREM sleep was used to quantify sleep.ResultsThere was a significant, regionally specific association between the interindividual variability in objective (total sleep time on the night before scanning) and subjective (Insomnia Severity Index) measures of prior sleep–wake behavior and the strength of DMN FC during subsequent wakefulness and NREM sleep. In several cases, FC was related to sleep measures independently of sleep stage, suggesting that previous sleep history effects sleep FC globally across the stages.ConclusionsThis work highlights the need to consider a subject's prior sleep history in studies utilizing FC analysis during wakefulness and sleep, and indicates the complexity of the impact of sleep on the brain both in the short and long term.
ZnO Nanoclusters Supported on Dealuminated Zeolite β as a Novel Catalyst for Direct Dehydrogenation of Propane to Propylene
Authors: Chen Chong , Hu Zhongpan , Ren Jintao , Zhang Shoumin , Wang Zheng , Yuan Zhong‐Yong 
Published: December 2018

AbstractSmall ZnO nanoclusters supported on dealuminated β zeolite were prepared and evaluated for catalyzing direct dehydrogenation of propane to propylene (PDH), exhibiting high catalytic performance. N2 sorption, XRD, TEM, 27Al and 28Si MAS NMR, IR, XRF, DR UV‐vis, XPS, and NH3‐TPD techniques were employed to characterize the physicochemical properties of this novel catalyst system. It is found that the Zn species can be accommodated in the vacant T‐atom sites of dealuminated β zeolite due to the reaction of aqueous zinc acetate solution with silanol groups, and thus, producing massive small ZnO nanoclusters as active phases in PDH. Additionally, dealuminated β zeolite can greatly depress side reactions attributable to the absence of strong acid sites, thereby guaranteeing high catalytic activity, propylene selectivity and stability. As a result, the optimal catalyst of 10 wt% Zn loaded on dealuminated β zeolite exhibits a high initial propane conversion of around 53 % and a superior propylene selectivity of about 93 % at a space velocity of 4000 cm3 gcat−1 h−1, together with the high stability and satisfactory reusability. This study may open a new way to design and synthesize highly active PDH catalysts with high selectivity and stability.
Peculiar Photoinduced Electron Transfer in Porphyrin–Fullerene Akamptisomers
Authors: Stasyuk Antony J. , Stasyuk Olga A. , Solà Miquel , Voityuk Alexander A. 
Published: December 2018

AbstractPorphyrin–fullerene dyads are promising candidates for organic photovoltaic devices. The electron‐transfer (ET) properties of the molecular devices depend significantly on the mutual position of the donor and acceptor. Recently, a new type of molecular isomerism (akamptisomerism) has been discovered. In the present study, we explore how photoinduced ET can be modulated by passing from one akamptisomer to another. To this aim, four akamptisomers of the quinoxalinoporphyrin–[60]fullerene complex are selected for computational study. The most striking finding is that, depending on the isomer, the porphyrin unit in the dyad can act as either electron donor or electron acceptor. Thus, the stereoisomeric diversity allows one to change the direction of ET between the porphyrin and fullerene moieties. To understand the effect of akamptisomerism on the photoinduced ET processes, a detailed analysis of initial and final states involved in the ET is performed. The computed rate for charge separation is estimated to be in the region of 1–10 ns−1. The formation of a long‐living quinoxalinoporphyrin anion radical species is predicted.
The Origin of the Reproduction of Different Nitrogen Uptakes in Covalent Organic Frameworks (COFs)
Authors: Guan Yiran , Li Wenliang , Wang Hailong , Zhang Jingping 
Published: December 2018

AbstractIn order to quantitatively examine the activation level for covalent‐organic frameworks (COFs) on gas adsorption, the effect of impurities on nitrogen uptakes in a series of boron‐based COFs was investigated by grand canonical Monte Carlo simulation (GCMC), based on accurate force fields derived from high‐level B2PLYP‐D3/def2‐TZVPP calculation. The conformations and the type of impurities were found to have little effect on the gas uptakes, but the quantity of impurities plays a crucial role on N2 loadings. More important, the terms of “activation mass ratio” and “activation volume ratio” were defined to estimate the realistic pore volume ratio for DBA‐COFs (DBA=π‐conjugated dehydro‐benzoannulene), and predict the potential of gas uptakes in DBA‐COFs. Our approach for DBA‐COFs materials could also be adopted for high‐throughput screening of a much vaster number of porous materials, to evaluate their impurities content and predict their adsorption potential.
Strength in Numbers: Development of a Fluorescence Sensor Array for Secondary Structures of DNA
Authors: Zuffo Michela , Xie Xiao , Granzhan Anton 
Published: December 2018

AbstractThe high‐throughput assessment of the secondary structures adopted by DNA oligonucleotides is currently hampered by the lack of suitable biophysical methods. Fluorescent sensors hold great potential in this respect; however, the moderate selectivity that they display for one DNA conformation over the others constitutes a major drawback to the development of accurate assays. Moreover, the use of single sensors impedes a comprehensive classification of the tested sequences. Herein, we propose to overcome these limitations through the development of a fluorescence sensor array constituted by easily accessible, commercial dyes. Multivariate analysis of the emission data matrix produced by the array allows the conformational preferences of DNA sequences of interest to be explored, either by calculating the probability of group membership in the six predefined structural categories (three G‐quadruplex groups, double‐stranded, and two groups of single‐stranded forms) or by revealing their particular structural features. The assay enables rapid screening of synthetic DNA oligonucleotides in a 96‐well plate format.
Multivalent Thiosialosides and Their Synergistic Interaction with Pathogenic Sialidases
Authors: Brissonnet Yoan , Assailly Coralie , Saumonneau Amélie , Bouckaert Julie , Maillasson Mike , Petitot Clémence , Roubinet Benoit , Didak Blanka , Landemarre Ludovic , Bridot Clarisse , Blossey Ralf , Deniaud David , Yan Xibo , Bernard Julien , Tellier Charles , Grandjean Cyrille , Daligault Franck , Gouin Sébastien G. 
Published: December 2018

AbstractSialidases (SAs) hydrolyze sialyl residues from glycoconjugates of the eukaryotic cell surface and are virulence factors expressed by pathogenic bacteria, viruses, and parasites. The catalytic domains of SAs are often flanked with carbohydrate‐binding module(s) previously shown to bind sialosides and to enhance enzymatic catalytic efficiency. Herein, non‐hydrolyzable multivalent thiosialosides were designed as probes and inhibitors of V. cholerae, T. cruzi, and S. pneumoniae (NanA) sialidases. NanA was truncated from the catalytic and lectinic domains (NanA‐L and NanA‐C) to probe their respective roles upon interacting with sialylated surfaces and the synthetically designed di‐ and polymeric thiosialosides. The NanA‐L domain was shown to fully drive NanA binding, improving affinity for the thiosialylated surface and compounds by more than two orders of magnitude. Importantly, each thiosialoside grafted onto the polymer was also shown to reduce NanA and NanA‐C catalytic activity with efficiency that was 3000‐fold higher than that of the monovalent thiosialoside reference. These results extend the concept of multivalency for designing potent bacterial and parasitic sialidase inhibitors.
Stereoselective Insertion of Benzynes into Lawsones: Synthesis of Biologically Important Benzannulated Bicyclo[3.3.0]octanes
Authors: Kumar A. Suresh , Thirupathi Guguloth , Reddy G. Surendra , Ramachary Dhevalapally B. 
Published: December 2018

AbstractAn ideal stereoselective insertion of in situ generated benzynes into lawsones through domino formal [2+2]‐cycloaddition followed by rearrangement is disclosed. The reaction allowed for the preparation of biologically important benzannulated bicyclo[3.3.0]octanes in good yields and with excellent selectivities by using simple substrates and conditions.
Combination of chemical and biological processes to enhance the treatment of hardly biodegradable matter in industrial wastewater: Selection parameters and performances
Authors: Minière Marine , Boutin Olivier , Soric Audrey 
Published: December 2018

AbstractThe increasing complexity of industrial effluents, combined with the increase in discharge constraints, leads to the necessity to improve processes treatment. Apart from new processes, the combination and optimization of existing processes could be the answer to these questions. Regarding coupling processes, the purifying potential has been demonstrated for a large range of processes, pollutants, and effluents. However, there has been a lack of studies integrating a biological process, although this has increased since 2000. The objective of this review is to focus on the combination of chemical and biological treatments for industrial applications and to provide recommendations based on different examples from the literature.
Levels and patterns of self‐reported and objectively‐measured free‐living physical activity among prostate cancer survivors: A prospective cohort study
Authors: Smith Lee , Lee Jung Ae , Mun Junbae , Pakpahan Ratna , Imm Kellie R. , Izadi Sonya , Kibel Adam S. , Colditz Graham A. , Grubb Robert L. , Wolin Kathleen Y. , Sutcliffe Siobhan , Yang Lin 
Published: December 2018

BackgroundNo prior study has measured or compared self‐reported and objectively measured physical activity trajectories in prostate cancer survivors before and after treatment.MethodsClinically localized prostate cancer patients treated with radical prostatectomy were recruited between 2011 and 2014. Of the 350 participants enrolled at the main site, 310 provided self‐reported physical activity at baseline before radical prostatectomy, and 5 weeks, 6 months, and 12 months after radical prostatectomy. A subset of participants (n = 81) provided objectively measured physical activity at all study time points by wearing an accelerometer for 7 days each. Changes in activity over time were compared using Friedman’s test. Agreement between self‐reported and objective measures was evaluated using Spearman’s rank correlation coefficient.ResultsSelf‐reported moderate‐to‐vigorous physical activity was high at baseline (median, 32.1 min/day), followed by a decline at 5 weeks (median, 15.0 min/day) and a recovery at 6 and 12 months (median, 32.1‐47.1 min/day). In contrast, objectively measured moderate‐to‐vigorous physical activity was low at all 4 time points (median, 0.0‐5.2 min/day), with no overall change across study assessments (global P = .29). Self‐reported moderate‐to‐vigorous physical activity tended to be more closely related to objectively measured light‐intensity physical activity (ρ = 0.29‐0.42) than to objectively measured moderate‐to‐vigorous physical activity (ρ = 0.07‐0.27, P = .009‐.32).ConclusionsIn our population of prostate cancer survivors with critically low moderate‐to‐vigorous physical activity levels, self‐reported measures greatly overestimated moderate‐to‐vigorous physical activity and may have been more reflective of light‐intensity physical activity. Because cancer survivor guidelines are derived from self‐reported data, our findings may imply that intensities of physical activity below moderate, such as light intensity, still have health benefits.
A study on the construction of evaluative system of Smart City based on entropy‐weighted matter‐element model method
Authors: Yong Xiang , Yan Cui , Weiyao  , Qiang Xu 
Published: December 2018

SummarySince our country has started to build the pilot project of a smart city in 2013, its effect has already appeared tentatively promoted by policies. However, its evaluation system is not yet mature. Therefore, this technical paper first considered the construction of evaluation index system according to the concept and construction situation of Smart City, adopted the five‐year statistics of Sichuan Province as empirical data, and this paper applied modeling calculation to draw the objective state of current Smart City construction. It also included the construction of evaluation index system with the introduction of a matter‐element extension method and entropy method to assign the weights, discussed the changes in the maximum relational degree of the six rule hierarchy indicators, and analyzed the key index that influences its development in the soft urban environment and information service to point out the direction for the next phase of the development.
In Situ Synthesis of Dicarboxylic Acid Functionalized Upconversion Nanoparticles for Bioimaging Applications
Authors: Wang Meifeng , Zhang Tao , Hu Yongjun , Qin Yiru , Wei Wei 
Published: December 2018

AbstractWe report a one‐step strategy to synthesize, in situ, highly water‐dispersible NaYF4 : Yb/Er upconversion nanoparticles (UCNPs) by employing dicarboxylic acids. The dicarboxylic acids serve as a type of dual‐purpose surface ligand for both controlling the growth and enabling the water dispersibility of the NaYF4 : Yb/Er UCNPs. It is found that the carbon chain length of the dicarboxylic acids has a marked effect on the size and morphology of the UCNPs. Among the dicarboxylic acids studied, adipic acid shows a superior performance. The UCNPs functionalized with adipic acid exhibit comparatively uniform size and morphology, as well as excellent water dispersibility. Our results also demonstrate their minimal toxicity and great potential for bioimaging applications.
Pharmacogenetics of type 2 diabetes mellitus, the route toward tailored medicine
Authors: Mannino Gaia Chiara , Andreozzi Francesco , Sesti Giorgio 
Published: December 2018

SummaryType 2 diabetes mellitus (T2DM) is a chronic disease that has reached the levels of a global epidemic. In order to achieve optimal glucose control, it is often necessary to rely on combination therapy of multiple drugs or insulin because uncontrolled glucose levels result in T2DM progression and enhanced risk of complications and mortality. Several antihyperglycemic agents have been developed over time, and T2DM pharmacotherapy should be prescribed based on suitability for the individual patient's characteristics. Pharmacogenetics is the branch of genetics that investigates how our genome influences individual responses to drugs, therapeutic outcomes, and incidence of adverse effects. In this review, we evaluated the pharmacogenetic evidences currently available in the literature, and we identified the top informative genetic variants associated with response to the most common anti‐diabetic drugs: metformin, DPP‐4 inhibitors/GLP1R agonists, thiazolidinediones, and sulfonylureas/meglitinides. Overall, we found 40 polymorphisms for each drug class in a total of 71 loci, and we examined the possibility of encouraging genetic screening of these variants/loci in order to critically implement decision‐making about the therapeutic approach through precision medicine strategies. It is possible then to anticipate that when the clinical practice will take advantage of the genetic information of the diabetic patients, this will provide a useful resource for the prevention of T2DM progression, enabling the identification of the precise drug that is most likely to be effective and safe for each patient and the reduction of the economic impact on a global scale.
Semiarid ecosystem sensitivity to precipitation extremes: weak evidence for vegetation constraints
Authors: Felton Andrew J. , Zavislan‐Pullaro Sam , Smith Melinda D. 
Published: December 2018

AbstractIn semiarid regions, vegetation constraints on plant growth responses to precipitation (PPT) are hypothesized to place an upper limit on net primary productivity (NPP), leading to predictions of future shifts from currently defined linear to saturating NPP–PPT relationships as increases in both dry and wet PPT extremes occur. We experimentally tested this prediction by imposing a replicated gradient of growing season PPT (GSP, n = 11 levels, n = 4 replicates), ranging from the driest to wettest conditions in the 75‐yr climate record, within a semiarid grassland. We focused on responses of two key ecosystem processes: aboveground NPP (ANPP) and soil respiration (Rs). ANPP and Rs both exhibited greater relative responses to wet vs. dry GSP extremes, with a linear relationship consistently best explaining the response of both processes to GSP. However, this responsiveness to GSP peaked at moderate levels of extremity for both processes, and declined at the most extreme GSP levels, suggesting that greater sensitivity of ANPP and Rs to wet vs. dry conditions may diminish under increased magnitudes of GSP extremes. Underlying these responses was rapid plant compositional change driven by increased forb production and cover as GSP transitioned to extreme wet conditions. This compositional shift increased the magnitude of ANPP responses to wet GSP extremes, as well as the slope and variability explained in the ANPP–GSP relationship. Our findings suggest that rapid plant compositional change may act as a mediator of semiarid ecosystem responses to predicted changes in GSP extremes.
Temporal clustering of extreme climate events drives a regime shift in rocky intertidal biofilms
Authors: Dal Bello Martina , Rindi Luca , Benedetti‐Cecchi Lisandro 
Published: December 2018

AbstractResearch on regime shifts has focused primarily on how changes in the intensity and duration of press disturbances precipitate natural systems into undesirable, alternative states. By contrast, the role of recurrent pulse perturbations, such as extreme climatic events, has been largely neglected, hindering our understanding of how historical processes regulate the onset of a regime shift. We performed field manipulations to evaluate whether combinations of extreme events of temperature and sediment deposition that differed in their degree of temporal clustering generated alternative states in rocky intertidal epilithic microphytobenthos (biofilms) on rocky shores. The likelihood of biofilms to shift from a vegetated to a bare state depended on the degree of temporal clustering of events, with biofilm biomass showing both states under a regime of non‐clustered (60 d apart) perturbations while collapsing in the clustered (15 d apart) scenario. Our results indicate that time since the last perturbation can be an important predictor of collapse in systems exhibiting alternative states and that consideration of historical effects in studies of regime shifts may largely improve our understanding of ecosystem dynamics under climate change.