bluuebunny/crossref_metadata_2025_split huggingface dataset:
MoS2@HKUST‐1 Flower‐Like Nanohybrids for Efficient Hydrogen Evolution Reactions
Authors: Wang Chengli , Su Yingchun , Zhao Xiaole , Tong Shanshan , Han Xiaojun 
Published: October 2017

AbstractA novel MoS2‐based flower‐like nanohybrid for hydrogen evolution was fabricated through coating the Cu‐containing metal‐organic framework (HKUST‐1) onto MoS2 nanosheets. It is the first time that MoS2@HKUST‐1 nanohybrids have been reported for the enhanced electrochemical performance of HER. The morphologies and components of the MoS2@HKUST‐1 flower‐like nanohybrids were characterized by scanning electron microscopy, X‐ray diffraction analysis and Fourier transform infrared spectroscopy. Compared with pure MoS2, the MoS2@HKUST‐1 hybrids exhibit enhanced performance on hydrogen evolution reaction with an onset potential of −99 mV, a smaller Tafel slope of 69 mV dec−1, and a Faradaic efficiency of nearly 100 %. The MoS2@HKUST‐1 flower‐like nanohybrids exhibit excellent stability in acidic media. This design opens new possibilities to effectively synthesize non‐noble metal catalysts with high performance for the hydrogen evolution reaction (HER).
Naphthyl Thio‐ and Carba‐xylopyranosides for Exploration of the Active Site of β‐1,4‐Galactosyltransferase 7 (β4GalT7)
Authors: Thorsheim Karin , Willén Daniel , Tykesson Emil , Ståhle Jonas , Praly Jean‐Pierre , Vidal Sébastien , Johnson Magnus T. , Widmalm Göran , Manner Sophie , Ellervik Ulf 
Published: October 2017

AbstractXyloside analogues with substitution of the endocyclic oxygen atom by sulfur or carbon were investigated as substrates for β‐1,4‐galactosyltransferase 7 (β4GalT7), a key enzyme in the biosynthesis of glycosaminoglycan chains. The analogues with an endocyclic sulfur atom proved to be excellent substrates for β4GalT7, and were galactosylated approximately fifteen times more efficiently than the corresponding xyloside. The 5a‐carba‐β‐xylopyranoside in the d‐configuration proved to be a good substrate for β4GalT7, whereas the enantiomer in the l‐configuration showed no activity. Further investigations by X‐ray crystallography, NMR spectroscopy, and molecular modeling provided a rationale for the pronounced activity of the sulfur analogues. Favorable π–π interactions between the 2‐naphthyl moiety and a tyrosine side chain of the enzyme were observed for the thio analogues, which open up for the design of efficient GAG primers and inhibitors.
New Insights into the Operating Voltage of Aqueous Supercapacitors
Authors: Yu Minghao , Lu Yongzhuang , Zheng Haibing , Lu Xihong 
Published: October 2017

AbstractThe main limitation of aqueous supercapacitors (SCs) lies in their narrow operating voltages, especially when compared with organic SCs. Fundamental understanding of factors relevant to the operating voltage helps providing guidance for the assembly of high‐voltage aqueous SCs. In this regard, this concept analyzes the deciding factors for the operating voltage of aqueous SCs. Strategies applied to expand the operating voltage are summarized and discussed from the aspects of electrolyte, electrode, and asymmetric structure. Dynamic factors associated with water electrolysis and maximally using the available potential ranges of electrodes are particularly emphasized. Finally, other promising approaches that have not been explored and their challenges are also elaborated, hoping to provide more insights for the design of high‐voltage aqueous SCs.
Structure Determination, Conformational Flexibility, Internal Dynamics, and Chiral Analysis of Pulegone and Its Complex with Water
Authors: Krin Anna , Pérez Cristóbal , Pinacho Pablo , Quesada‐Moreno María Mar , López‐González Juan Jesús , Avilés‐Moreno Juan Ramón , Blanco Susana , López Juan Carlos , Schnell Melanie 
Published: October 2017

AbstractIn the current work we present a detailed analysis of the chiral molecule pulegone, which is a constituent of essential oils, using broadband rotational spectroscopy. Two conformers are observed under the cold conditions of a molecular jet. We report an accurate experimentally determined structure for the lowest energy conformer. For both conformers, a characteristic splitting pattern is observed in the spectrum, resulting from the internal rotation of the two non‐equivalent methyl groups situated in the isopropylidene side chain. The determined energy barriers are 1.961911(46) kJ mol−1and 6.3617(12) kJ mol−1for one conformer, and 1.96094(74) kJ mol−1and 6.705(44) kJ mol−1for the other one. Moreover, a cluster of the lowest energy conformer with one water molecule is reported. The water molecule locks one of the methyl groups by means of a hydrogen bond and some secondary interactions, so that we only observe internal rotation splittings from the other methyl group with an internal rotation barrier of 2.01013(38) kJ mol−1. Additionally, the chirality‐sensitive microwave three‐wave mixing technique is applied for the differentiation between the enantiomers, which can become of further use for the analysis of essential oils.
The Structure of Diphenyl Ether–Methanol in the Electronically Excited and Ionic Ground States: A Combined IR/UV Spectroscopic and Theoretical Study
Authors: Bernhard Dominic , Holzer Christof , Dietrich Fabian , Stamm Anke , Klopper Wim , Gerhards Markus 
Published: October 2017

AbstractDiphenyl ether offers competing docking sites for methanol: the ether oxygen acts as a common hydrogen‐bond acceptor and the π system of each phenyl ring allows for OH–π interactions driven by electrostatic, induction, and dispersion forces. Based on investigations in the electronic ground state (S0), we present a detailed study of the electronically excited state (S1) and the ionic ground state (D0), in which an impact on the structural preference is expected compared with the S0 state. Dispersion forces in the electronically excited state were analyzed by comparing the computed binding energies at the coupled‐cluster‐singles (CCS) and approximate coupled‐cluster‐singles‐doubles levels of theory (CC2 approximation). By applying UV/IR/UV spectroscopy, we found a more strongly bound OH–π structure in the S1 state compared with the S0 state, in agreement with spin‐component‐scaled CC2 calculations. A structural rearrangement into a non‐hydrogen‐bonded structure takes places upon ionization in the D0 state, which was revealed by using IR photodissociation spectroscopy and confirmed by theory.
Ultrafast Dynamics of a Fluorescent Tetrazolium Compound in Solution
Authors: Bolze Tom , Wree Jan‐Lucas , Kanal Florian , Schleier Domenik , Nuernberger Patrick 
Published: October 2017

AbstractTetrazolium salts are exploited in various fields of research by virtue of their low reduction potentials. Increasingly, associated applications also attend to the photochemical and luminescence properties of these systems. Here, we investigate the photoinduced dynamics of phenyl‐benzo[c]tetrazolo‐cinnolinium chloride (PTC), one of the very few known fluorescent tetrazolium compounds, by using time‐correlated single‐photon counting, femtosecond fluorescence upconversion, and ultrafast transient absorption spectroscopy. PTC is generated photochemically by ultraviolet illumination of 2,3,5‐triphenyl‐tetrazolium chloride (TTC) in various alcohols. Time‐resolved fluorescence measurements on PTC with different excitation wavelengths disclose biphasic solvation and vibrational relaxation dynamics. Depending on the solvent, the emission behavior of PTC is characterized by quantum yields on the order of several tens of percent and corresponding excited‐state lifetimes of several hundreds of picoseconds. The radiative rate is basically constant for the studied alcohols, whereas the rate of the competing non‐radiative process is sensitive to the solvent polarity. Hence, we discuss the possible involvement of intermediate radicals and further presumptive reaction pathways pursued after photoexcitation of PTC.
Continuity between DSM‐5 Section II and Section III personality traits for obsessive–compulsive personality disorder
Authors: Liggett Jacqueline , Sellbom Martin , Bach Bo 
Published: October 2017

AbstractObjectiveObsessive–compulsive personality disorder (OCPD) is formally operationalized in Section II of the DSM‐5 by a heterogeneous collection of 8 categorical criteria. Section III contains an alternative model operationalizing personality disorders via dimensional personality traits and associated impairment. The extent to which the personality traits used to define OCPD in Section III correspond with the Section II operationalization of the disorder is contested. The current study aims to contribute to the evidence base necessary to solidify the optimal trait profile for this disorder via a more fine‐tuned examination of OCPD.MethodThe research questions were examined using a clinical sample of 142 Danish adults who completed the Structured Clinical Interview for DSM‐IV Axis II Disorders and the Personality Inventory for DSM‐5 to index both the Sections II and III (personality traits) operationalizations of OCPD, respectively.ResultsBivariate correlations supported Rigid Perfectionism and Perseveration as traits relevant to OCPD; however, hierarchical regression analyses indicated that of the 4 traits used in the Section III operationalization of OCPD, only Rigid Perfectionism uniquely predicted OCPD (p < .05). In addition to Rigid Perfectionism, the conceptually relevant traits of Submissiveness, Suspiciousness, and (low) Impulsivity were also found to uniquely predict OCPD and its specific symptoms in a regression model.ConclusionsThese findings indicate that the traits proposed in Section III are only partially aligned with the traditional, Section II conceptualization of OCPD, and may be augmented by incorporating Submissiveness, Suspiciousness, and (low) Impulsivity. In light of the current findings and existing literature, a modified constellation of traits to operationalize OCPD is likely justified.
Different expression about induced sputum cell sorting in the two main types of chronic obstructive pulmonary disease
Authors: Song Huifang , Yun Chunmei , Xu Maoye , Sun Dejun 
Published: October 2017

AbstractBackgroundThe difference in expression of sputum cells types between the two main types of chronic obstructive pulmonary disease (COPD) is largely unknown. This study aims to investigate the difference and then wants to depend on sputum cells sorting to direct the treatment of COPD.MethodsA total of 218 patients with stable COPD (FEV1 < 80%) were selected. Stable COPD patients (n = 218) were classified as eosinophilic (A phenotype) or noneosinophilic (B phenotype); sometimes, the subjects were separated into cough group (C phenotype) and dyspnea group (D phenotype). Cross‐sectional analysis was conducted comparing demographics and clinical characteristics. Receiver‐operating characteristic curve was used to assess predictive ability of sputum eosinophils for D phenotype.ResultsThe A phenotype showed a higher correlation with the patients complaining of presenting with dyspnea on exertion, the dyspnea group (D phenotype). The B phenotype showed a higher prevalence of those who cough and product sputum, this was cough group (C phenotype). Sputum eosinophil and macrophages counts were significantly higher in patients with dyspnea (n = 95) compared to those with cough (P < .05), and neutrophils were significantly lower in patients with dyspnea (n = 95) compared to those with cough (P < .05). Percentage sputum eosinophil count was predictive of dyspnea (D phenotype) COPD with area under curve (AUC) of 0.831 (95% confidence interval (CI) 0.77‐0.89; P ≤ .001). Neutrophils were also predictive of dyspnea (D phenotype) COPD with AUC of 0.276 (95% CI 0.204–0.347; P ≤ .001).ConclusionThese findings suggest that the morphological phenotypes of COPD show several clinical characteristics and different sputum cell sorting.
Squamous cell carcinoma in serous effusions: Avoiding pitfalls in this rare encounter
Authors: LePhong Christopher , Hubbard Elizabeth W. , Van Meter Stuart , Nodit Laurentia 
Published: October 2017

BackgroundWith advent of personalized medicine, precise classification of malignant tumors becomes essential. Squamous cell carcinoma (SCC) is rarely found in serous effusions and has morphologic and immunohistochemical (IHC) overlap with other neoplasms.Methods17‐year review identified 49 fluids from 26 patients where SCC was recognized.ResultsSCC was more frequent in pleural fluid (84%) and rare in other effusions. Lung SCC was common (65%), followed by head and neck (16%), with other origins less represented. 19 samples were diagnosed positive for SCC, 12 were reported as non‐small cell carcinoma and 13 were atypical/suspicious. Two were false negative (on hypocellular smears) and one was false positive (smear with small orangeophilic squamous‐like cells). Two fluids were diagnosed as adenocarcinoma on smears and SCC on cellblocks after IHC. A chi‐square test showed the correct diagnosis more often on cellblocks than smears (P‐value = .0005) and all false positive, negative or misclassifications were done on cytology smears. Ber EP4 and MOC 31 immunostains were positive in most cases when performed, and the most specific immunostains for SCC were p63 and p40. Negative mucin stains were helpful. Cytology smears are imperfect tools in evaluation of body fluids and SCC can be misclassified as adenocarcinoma on smears alone. Orangeophilic cytoplasm can lead to false positive results. The most useful stains for identification were p40, p63, and mucicarmine.ConclusionThe combination of clinical history with cellblock preparation and appropriate IHCs is the best method to ensure a correct diagnosis.
Range of therapeutic prothipendyl and prothipendyl sulfoxide concentrations in clinical blood samples
Authors: Krämer Michael , Heese Peter , Banger Markus , Madea Burkhard , Hess Cornelius 
Published: October 2017

AbstractDue to a lack of reference blood concentrations in the literature, the forensic evaluation of prothipendyl findings in blood samples is difficult. Interpretations with regard to the assessment of blood concentrations as well as an estimation of the ingested prothipendyl amounts were often vague. To describe a concentration range in clinical samples, prothipendyl and prothipendyl sulfoxide concentrations were determined in serum samples of 50 psychiatric patients receiving 40 mg, 80 mg, or 160 mg doses of prothipendyl. The analyses of prothipendyl and prothipendyl sulfoxide were carried out using validated methods of high performance liquid chromatography coupled to triple quadrupole mass spectrometry (LC–QQQ–MS), respectively. 40 mg doses caused average prothipendyl serum concentrations of 18.0 ng/mL (1 hour after intake) and 7.9 ng/mL (10.5 hours after intake), while 80 mg doses caused averages of 42.6 ng/mL and 15.2 ng/mL at the mentioned times of sampling. Irrespective of the given dose, prothipendyl concentrations below 30 ng/mL were observed in 80% of the patient samples taken 1 hour after ingestion as well as in 90% of the samples collected 10.5 hours after administration. Serum concentrations of the Phase I metabolite prothipendyl sulfoxide averaged 4.3 ng/mL (1 hour after intake) and 3.6 ng/mL (10.5 hours after intake). Possible drug‐drug interactions regarding absorption and metabolism of prothipendyl are discussed. Results of the herein presented study are useful for the interpretation of analytical prothipendyl findings in forensic toxicology. The utility of the described concentration range is demonstrated by discussing two death cases involving prothipendyl findings.
Fungi reduce preference and performance of insect herbivores on challenged plants
Authors: Fernandez‐Conradi Pilar , Jactel Hervé , Robin Cécile , Tack Ayco J. M. , Castagneyrol Bastien 
Published: October 2017

AbstractAlthough insect herbivores and fungal pathogens frequently share the same individual host plant, we lack general insights in how fungal infection affects insect preference and performance. We addressed this question in a meta‐analysis of 1,113 case studies gathered from 101 primary papers that compared preference or performance of insect herbivores on control vs. fungus challenged plants. Generally, insects preferred, and performed better on, not challenged plants, regardless of experimental conditions. Insect response to fungus infection significantly differed according to fungus lifestyle, insect feeding guild, and the spatial scale of the interaction (local/distant). Insect performance was reduced on plants challenged by biotrophic pathogens or endophytes but not by necrotrophic pathogens. For both chewing and piercing‐sucking insects, performance was reduced on challenged plants when interactions occurred locally but not distantly. In plants challenged by biotrophic pathogens, both preference and performance of herbivores were negatively impacted, whereas infection by necrotrophic pathogens reduced herbivore preference more than performance and endophyte infection reduced only herbivore performance. Our study demonstrates that fungi could be important but hitherto overlooked drivers of plant‐herbivore interactions, suggesting both direct and plant‐mediated effects of fungi on insect's behavior and development.
Duration of chronic heart failure affects outcomes with preserved effects of heart rate reduction with ivabradine: findings from SHIFT
Authors: Böhm Michael , Komajda Michel , Borer Jeffrey S. , Ford Ian , Maack Christoph , Tavazzi Luigi , Moyne Aurélie , Swedberg Karl ,   on behalf of the SHIFT Investigators
Published: October 2017

AimsIn heart failure (HF) with reduced ejection fraction and sinus rhythm, heart rate reduction with ivabradine reduces the composite incidence of cardiovascular death and HF hospitalization.Methods and resultsIt is unclear whether the duration of HF prior to therapy independently affects outcomes and whether it modifies the effect of heart rate reduction. In SHIFT, 6505 patients with chronic HF (left ventricular ejection fraction of ≤35%), in sinus rhythm, heart rate of ≥70 b.p.m., treated with guideline‐recommended therapies, were randomized to placebo or ivabradine. Outcomes and the treatment effect of ivabradine in patients with different durations of HF were examined. Prior to randomization, 1416 ivabradine and 1459 placebo patients had HF duration of ≥4 weeks and <1.5 years; 836 ivabradine and 806 placebo patients had HF duration of 1.5 years to <4 years, and 989 ivabradine and 999 placebo patients had HF duration of ≥4 years. Patients with longer duration of HF were older (62.5 years vs. 59.0 years; P < 0.0001), had more severe disease (New York Heart Association classes III/IV in 56% vs. 44.9%; P < 0.0001) and greater incidences of co‐morbidities [myocardial infarction: 62.9% vs. 49.4% (P < 0.0001); renal dysfunction: 31.5% vs. 21.5% (P < 0.0001); peripheral artery disease: 7.0% vs. 4.8% (P < 0.0001)] compared with patients with a more recent diagnosis. After adjustments, longer HF duration was independently associated with poorer outcome. Effects of ivabradine were independent of HF duration.ConclusionsDuration of HF predicts outcome independently of risk indicators such as higher age, greater severity and more co‐morbidities. Heart rate reduction with ivabradine improved outcomes independently of HF duration. Thus, HF treatments should be initiated early and it is important to characterize HF populations according to the chronicity of HF in future trials.
Circulating microRNA‐132 levels improve risk prediction for heart failure hospitalization in patients with chronic heart failure
Authors: Masson Serge , Batkai Sandor , Beermann Julia , Bär Christian , Pfanne Angelika , Thum Sabrina , Magnoli Michela , Balconi Giovanna , Nicolosi Gian Luigi , Tavazzi Luigi , Latini Roberto , Thum Thomas 
Published: October 2017

AimsNon‐coding microRNAs (miRNAs) are critically involved in cardiovascular pathophysiology. Since they are measurable in most body fluids, they have been proposed as circulating biomarkers. We examined the prognostic value of a specific candidate miRNA in a large cohort of patients with chronic heart failure (HF) enrolled in a multicentre clinical trial.Methods and resultsPlasma levels of miR‐132 were measured using miRNA‐specific PCR‐based technologies at randomization in 953 patients with chronic, symptomatic HF from the GISSI‐Heart Failure trial. The association with fatal (all‐cause and cardiovascular death) and non‐fatal events (time to first admission to hospital for cardiovascular reasons or worsening of HF) and the incremental risk prediction were estimated in adjusted models. Higher circulating miR‐132 levels were independently associated with younger age, better renal filtration, ischaemic aetiology of HF, more severe HF symptoms, higher diastolic blood pressure, higher cholesterol, and male sex. After extensive adjustment for demographic, clinical, and echocardiographic risk factors and baseline NT‐proBNP concentrations, miR‐132 remained associated only with HF hospitalizations (hazard ratio 0.79, 95% confidence interval 0.66–0.95, P = 0.01) and improved its risk prediction with the continuous net reclassification index (cNRI 0.205, P = 0.001).ConclusionIn well characterized patients with chronic HF, circulating miR‐132 levels rise with the severity of HF. Lower circulating miR‐132 levels improved risk prediction for HF readmission beyond traditional risk factors, but not for mortality. MiR‐132 may be helpful to intensify strategies aimed at reducing re‐hospitalization, which has a substantial health and economic burden in HF.
Immunization with α‐synuclein/Grp94 reshapes peripheral immunity and suppresses microgliosis in a chronic Parkinsonism model
Authors: Villadiego Javier , Labrador‐Garrido Adahir , Franco Jaime M. , Leal‐Lasarte Magdalena , De Genst Erwin J. , Dobson Christopher M. , Pozo David , Toledo‐Aral Juan J. , Roodveldt Cintia 
Published: October 2017

AbstractNeuroinflammation mediated by chronically activated microglia, largely caused by abnormal accumulation of misfolded α‐synuclein (αSyn) protein, is known to contribute to the pathophysiology of Parkinson's disease (PD). In this work, based on the immunomodulatory activities displayed by particular heat‐shock proteins (HSPs), we tested a novel vaccination strategy that used a combination of αSyn and Grp94 (HSPC4 or Gp96) chaperone and a murine PD model. We used two different procedures, first, the adoptive transfer of splenocytes from αSyn/Grp94‐immunized mice to recipient animals, and second, direct immunization with αSyn/Grp94, to study the effects in a chronic mouse MPTP‐model of parkinsonism. We found that both approaches promoted a distinct profile in the peripheral system—supported by humoral and cellular immunity—consisting of a Th1‐shifted αSyn‐specific response accompanied by an immune‐regulatory/Th2‐skewed general phenotype. Remarkably, this mixed profile sustained by αSyn/Grp94 immunization led to strong suppression of microglial activation in the substantia nigra and striatum, pointing to a newly described positive effect of anti‐αSyn Th1‐responses in the context of PD. This strategy is the first to target αSyn and report the suppression of PD‐associated microgliosis. Overall, we show that the αSyn/Grp94 combination supports a distinct and long‐lasting immune profile in the peripheral system, which has an impact at the CNS level by suppressing chronic microglial activation in an MPTP model of PD. Furthermore, our study demonstrates that reshaping peripheral immunity by vaccination with appropriate misfolding protein/HSP combinations could be highly beneficial as a treatment for neurodegenerative misfolding diseases.