bluuebunny/crossref_metadata_2025_split huggingface dataset:
Preventing Teen Relationship Abuse and Sexual Assault through Bystander Training: Intervention Outcomes for School Personnel
Authors: Edwards Katie M. , Sessarego Stephanie N. , Mitchell Kimberly J. , Chang Hong , Waterman Emily A. , Banyard Victoria L. 
Published: August 2019

AbstractThe purpose of the current study was to examine the impact of exposure to Bringing in the Bystander—High School Curriculum (BITB‐HSC) on school personnel, which included a seven session classroom curriculum for ninth through twelfth graders (student curriculum), a bystander training workshop for school personnel (school personnel workshop), and reading materials (handout). We examined how exposure to these various BITB‐HSC intervention components was associated with school personnel's knowledge and bystander efficacy, intentions, and barriers specific to student relationship abuse (RA) and sexual assault (SA). Participants were 488 school personnel from 12 high schools in upper New England who completed the 4‐month follow‐up survey that assessed for intervention exposure (284 participants completed both the baseline and follow‐up survey). Whereas 53% of participants were exposed to no intervention components, the other half of the sample were exposed to a combination of intervention components. Higher baseline knowledge and reactive bystander intentions were associated with subsequent exposure to both the student curriculum and the handout, and fewer barriers to bystander action predicted exposure to the school personnel workshop. Exposure to the school personnel workshop, student curriculum, and handout was associated with subsequent greater knowledge, exposure to the student curriculum predicted reactive bystander intentions, and exposure to the handout predicted higher reactive bystander intentions and bystander efficacy. Findings suggest that despite challenges with engagement, exposure to the BITB‐HSC components may be a useful tool in improving school personnel's responses to RA and SA among high school students.
Effects of endoscopic sinus surgery on objective and subjective measures of cognitive dysfunction in chronic rhinosinusitis
Authors: Yoo Frederick , Schlosser Rodney J. , Storck Kristina A. , Ganjaei Kimia G. , Rowan Nicholas R. , Soler Zachary M. 
Published: August 2019

BackgroundChronic rhinosinusitis (CRS) is a common condition that has been associated with cognitive dysfunction. The purpose of this study was to evaluate the effect of endoscopic sinus surgery (ESS) on the subjective and objective measures of cognitive dysfunction and related quality‐of‐life measures in CRS.MethodsThirty‐five adults with CRS refractory to medical therapy were prospectively enrolled. Preoperatively and postoperatively (≥4 months), subjects completed objective neurocognitive evaluation with the Automated Neuropsychological Assessment Metrics (ANAM) platform and multiple questionnaires, including the Cognitive Failures Questionnaire (CFQ), a modified World Health Organization Health and Work Performance Questionnaire (ctHPQ), 22‐item Sino‐Nasal Outcomes Test (SNOT‐22), Sinus Control Test (SCT), Questionnaire of Olfactory Disorders (QOD), Beck Depression Inventory―second edition (BDI‐II), Pittsburgh Sleep Quality Index (PSQI), and Fatigue Severity Scale (FSS).ResultsThirty‐three of 35 patients satisfactorily completed the study. Postsurgical improvement in the CFQ was 46.7 ± 18.4 to 31.9 ± 17.8 (p < 0.001). Neurocognitive testing revealed significant improvements in mathematical processing (p = 0.003) and matching to sample (p = 0.023), as well as a significant decline in simple reaction time (p = 0.026). In addition, improvements were noted for SNOT‐22 (54.8 ± 21.4 to 24.8 ± 21.1, p < 0.001), SCT (9.3 ± 2.6 to 3.9 ± 3.8, p < 0.001), PSQI (10.7 ± 4.5 to 6.9 ± 4.0, p < 0.001), BDI‐II (14.0 ± 9.9 to 8.9 ± 9.0, p < 0.001), QOD (17.6 ± 13.4 to 9.9 ± 12.3, p = 0.001), and FSS (4.6 ± 1.4 to 3.1 ± 1.5, p < 0.001). There was significant improvement in overall presenteeism (7.3 ± 1.4 to 8.4 ± 1.3, p = 0.029). Analysis by polyp status revealed significant improvement in mathematical processing and matching to sample in only CRS patients without polyps.ConclusionESS is associated with improvement in subjective and some aspects of objective cognition.
Spontaneous pancreatic undifferentiated pleomorphic sarcoma in a laboratory rat: A case report
Authors: Ypsilantis Petros , Meditskou Soultana , Lambropoulou Maria , Papamitsou Theodora , Simopoulos Constantinos 
Published: August 2019

AbstractWe present a case of spontaneous undifferentiated/unclassified sarcoma, of a pleomorphic subtype formerly known as malignant fibrous histiocytoma (UPS/MFH), arising from the pancreas of a laboratory rat. The mass was excised after laparotomy from a 6‐month‐old female laboratory Wistar rat. It presented a giant multilobulated mass of irregular shape, which had arisen from the pancreas and occupied almost the entire peritoneal cavity. Histologically the tumor was characterized by a highly variable morphological pattern, with frequent transitions from storiform to pleomorphic areas. An extensive immunohistochemical examination revealed no specific lines of differentiation. Immunohistochemical positivity was observed only to MIB‐1 (high Ki‐67 proliferation index), vimentin and CD68 antibodies. The diagnosis was compatible with UPS/MFH. To the best of our knowledge, the present case is the first report of a spontaneous primary UPS/MFH arising from the pancreas of a laboratory rat.
Intrinsic Self‐Trapped Emission in 0D Lead‐Free (C4H14N2)2In2Br10 Single Crystal
Authors: Zhou Lei , Liao Jin‐Feng , Huang Zeng‐Guang , Wei Jun‐Hua , Wang Xu‐Dong , Chen Hong‐Yan , Kuang Dai‐Bin 
Published: August 2019

AbstractLow‐dimensional lead halide perovskite materials recently have drawn much attention owing to the intriguing broadband emissions; however, the toxicity of lead will hinder their future development. Now, a lead‐free (C4H14N2)2In2Br10 single crystal with a unique zero‐dimensional (0D) structure constituted by [InBr6]3− octahedral and [InBr4]− tetrahedral units is described. The single crystal exhibits broadband photoluminescence (PL) that spans almost the whole visible spectrum with a lifetime of 3.2 μs. Computational and experimental studies unveil that an excited‐state structural distortion in [InBr6]3− octahedral units enables the formation of intrinsic self‐trapped excitons (STEs) and thus contributing the broad emission. Furthermore, femtosecond transient absorption (fs‐TA) measurement reveals that the ultrafast STEs formation together with an efficient intersystem crossing has made a significant contribution to the long‐lived and broad STE‐based emission behavior.
Observation and Kinetic Characterization of Transient Schiff Base Intermediates by CEST NMR Spectroscopy
Authors: Ramanujam Venkatraman , Charlier Cyril , Bax Ad 
Published: August 2019

AbstractIn aqueous solution, many biochemical reaction pathways involve reaction of an aldehyde with an amine, which progresses through generally unstable, hydrated and dehydrated, Schiff base intermediates that often are unobservable by conventional NMR. There are 4 states in the relevant equilibrium: 1) gem‐diol, 2) aldehyde, 3) hemiaminal, and 4) Schiff base. For the reaction between protein amino groups and DOPAL, a highly toxic metabolite of dopamine, the 1H resonances of both the hemiaminal and the dehydrated Schiff base can be observed by CEST NMR, even when their populations fall below 0.1 %. CEST NMR reveals the quantitative exchange kinetics between reactants and Schiff base intermediates, explaining why the Schiff base NMR signals are rarely observed. The reactivity of DOPAL with Nα‐amino groups is greater than with lysine Nϵ‐amines and, in the presence of O2, both types of Schiff base DOPAL–peptide intermediates rapidly react with free DOPAL to irreversibly form dicatechol pyrrole adducts.
Molybdenum Alkylidyne Complexes with Tripodal Silanolate Ligands: The Next Generation of Alkyne Metathesis Catalysts
Authors: Hillenbrand Julius , Leutzsch Markus , Fürstner Alois 
Published: August 2019

AbstractA new type of molybdenum alkylidyne catalysts for alkyne metathesis is described, which is distinguished by an unconventional podand topology. These structurally well‐defined complexes are easy to make on scale and proved to be tolerant toward numerous functional groups; even certain protic substituents were found to be compatible. The new catalysts were characterized by X‐ray crystallography and by spectroscopic means, including 95Mo NMR.
Modification of Enzyme Activity by Vibrational Strong Coupling of Water
Authors: Vergauwe Robrecht M. A. , Thomas Anoop , Nagarajan Kalaivanan , Shalabney Atef , George Jino , Chervy Thibault , Seidel Marcus , Devaux Eloïse , Torbeev Vladimir , Ebbesen Thomas W. 
Published: August 2019

AbstractVibrational strong coupling (VSC) has recently emerged as a completely new tool for influencing chemical reactivity. It harnesses electromagnetic vacuum fluctuations through the creation of hybrid states of light and matter, called polaritonic states, in an optical cavity resonant to a molecular absorption band. Here, we investigate the effect of vibrational strong coupling of water on the enzymatic activity of pepsin, where a water molecule is directly involved in the enzyme's chemical mechanism. We observe an approximately 4.5‐fold decrease of the apparent second‐order rate constant kcat/Km when coupling the water stretching vibration, whereas no effect was detected for the strong coupling of the bending vibration. The possibility of modifying enzymatic activity by coupling water demonstrates the potential of VSC as a new tool to study biochemical reactivity.
A Diruthenium‐Based Mixed Spin Complex Ru25+(S=1/2)‐CN‐Ru25+(S=3/2)
Authors: Su Shao‐Dong , Zhu Xiao‐Quan , Wen Yue‐Hong , Zhang Lin‐Tao , Yang Yu‐Ying , Lin Chen‐Sheng , Wu Xin‐Tao , Sheng Tian‐Lu 
Published: August 2019

AbstractAn unusual tetra‐nuclear linear cyanido‐bridged complex [Ru2(μ‐ap)4‐CN‐Ru2(μ‐ap)4](BPh4) (1) (ap=2‐anilinopyridinate) has been synthesized and well characterized. The crystallographic data, magnetic measurement, IR, EPR and theoretical calculation results demonstrate that complex 1 is the first example of mixed spin Ru25+‐based complex with uncommon electronic configurations of S=1/2 for the cyanido‐C bound Ru25+ and S=3/2 for the cyanido‐N bound Ru25+. This phenomenon can be understood by the theoretical calculation results that from the precursor Ru2(μ‐ap)4(CN) (S=3/2) to complex 1 the energy gap between π* and δ* orbitals of the cyanido‐C bound Ru25+ core increases from 0.57 to 1.61 eV due to the enhancement of asymmetrical π back‐bonding effect, but that of the cyanido‐N bound Ru25+ core is essential identical (0.56 eV). Besides, the analysis of UV/Vis‐NIR spectra suggests that there exists metal to metal charge transfer (MMCT) from the cyanido‐N bound Ru25+ (S=3/2) to the cyanido‐C bound Ru25+ (S=1/2), supported by the TDDFT calculations.
Safe, Low‐Cost, Fast‐Kinetics and Low‐Strain Inorganic‐Open‐Framework Anode for Potassium‐Ion Batteries
Authors: Zhang Ruding , Huang Jiajia , Deng Wenzhuo , Bao Jingze , Pan Yilong , Huang Shuping , Sun Chuan‐Fu 
Published: August 2019

AbstractA key challenge for potassium‐ion batteries is to explore low‐cost electrode materials that allow fast and reversible insertion of large‐ionic‐size K+. Here, we report an inorganic‐open‐framework anode (KTiOPO4), which achieves a reversible capacity of up to 102 mAh g−1 (307 mAh cm−3), flat voltage plateaus at a safe average potential of 0.82 V (vs. K/K+), a long lifespan of over 200 cycles, and K+‐transport kinetics ≈10 times faster than those of Na‐superionic conductors. Combined experimental analysis and first‐principles calculations reveal a charge storage mechanism involving biphasic and solid solution reactions and a cell volume change (9.5 %) even smaller than that for Li+‐insertion into graphite (≈10 %). KTiOPO4 exhibits quasi‐3D lattice expansion on K+ intercalation, enabling the disintegration of small lattice strain and thus high structural stability. The inorganic open‐frameworks may open a new avenue for exploring low‐cost, stable and fast‐kinetic battery chemistry.
Synthesis, molecular docking studies, and biological evaluation of novel alkyl bis(4‐amino‐5‐cyanopyrimidine) derivatives
Authors: Boualia Imen , Derabli Chamseddine , Boulcina Raouf , Bensouici Chawki , Yildirim Muhammet , Birinci Yildirim Arzu , Mokrani El Hassen , Debache Abdelmadjid 
Published: August 2019

AbstractA series of bis(4‐amino‐5‐cyano‐pyrimidines) was synthesized and evaluated as dual inhibitors of acetylcholinesterase (AChE) and butyrylcholinesterase (BChE). To further explore the multifunctional properties of the new derivatives, their antioxidant and antibacterial activities were also tested. The results showed that most of these compounds could effectively inhibit AChE and BChE. Particularly, compound 7c exhibited the best AChE inhibitory activity (IC50 = 5.72 ± 1.53 μM), whereas compound 7h was identified as the most potent BChE inhibitor (IC50 = 12.19 ± 0.57 μM). Molecular modeling study revealed that compounds 7c, 7f, and 7b showed a higher inhibitory activity than that of galantamine against both AChE and BChE. Anticholinesterase activity of compounds 7h, 7b, and 7c was significant in vitro and in silico for both enzymes, since these compounds have hydrophobic rings (Br‐phenyl, dimethyl, and methoxyphenyl), which bind very well in both sites. In addition to cholinesterase inhibitory activities, these compounds showed different levels of antioxidant activities. Indeed, in the superoxide–dimethyl sulfoxide alkaline assay, compound 7j showed very high inhibition (IC50 = 0.37 ± 0.28 μM). Also, compound 7l exhibited strong and good antibacterial activity against Staphylococcus epidermidis and Staphylococcus aureus, respectively. Taking into account the results of biological evaluation, further modifications will be designed to increase potency on different targets. In this study, the obtained results can be a new starting point for further development of multifunctional agents for the treatment of Alzheimer's disease.
Conditional Markov Chain Design for Accrual Clinical Trials
Authors: Matts J. P. , McHugh R. B. 
Published: August 2019

Randomization in a comparative experiment has, as one aim, the control of bias in the initial selection of experimental units. When the experiment is a clinical trial employing the accrual of patients, two additional aims are the control of admission bias and control of chronologic bias. This can be accomplished by using a method of randomization, such as the “biased coin design” of Efron, which sequentially forces balance.As an extension of Efron's design, this paper develops a class of conditional Markov chain designs. The detailed randomization employed utilizes the sequential imbalances in the treatment allocation as states in a Markov process. Through the use of appropriate transition probabilities, a range of possible designs can be attained.An additional objective of physical randomization is to provide a model for data analysis. Such a randomization theoretic analysis is presented for the current designs. In addition, Monte Carlo sampling results are given to support the proposed normal theory approximation to the exact randomization distribution.
A Clustering Method for the States of a Markov Chain with an Application to Primate Communication
Authors: Pruscha H. 
Published: August 2019

In some applications clustering problems in stochastic processes arise when the experimenter wants to improve the insight into the structure of the observed system by lumping its states into clusters. As measure of goodness of a cluster solution we choose the rate of predictability of the forthcoming events which can be quantified by means of the entropy of the lumped process. The entropy in turn can be estimated by making use of a Shannon‐McMillan‐type theorem. We will establish some asymptotic results for the estimate of entropy in the case where the underlying stochastic process is a Markov chain. Our main tool will be a representation of functions of Markov chains which is due to Blackwell (1957).The method proposed here is applied to data on communication processes in monkeys. The object of our analysis will be to find a subgroup structure in the animal group.
Pilot randomised controlled trial of counselling in a community mental health setting: Pitfalls and learnings
Authors: Farr Joanna , Di Malta Gina , Cooper Mick 
Published: August 2019

AbstractThe establishment of counselling and psychotherapy as “evidence‐based” interventions is contingent on the effective implementation of randomised controlled trials (RCTs) in real‐world clinical settings. This paper identifies some of the pitfalls that led to the termination of a practical RCT in a community mental health setting. It reflects upon the significance of the lessons learned by drawing on similar challenges that are documented in the wider literature. Issues surrounding staff turnover, counsellor engagement and procedural clarity are discussed, as is the conflict between the time required for research procedures and counsellors’ clinical time constraints. In our recommendations, we recognise the decisive role of collaboration and counsellor motivation in research partnerships, and the significance of clinical relevance, communication, training and research co‐production in achieving them. Time commitment is identified as the pivotal challenge in the formation and maintenance of collaborative research, but one that also must be overcome for the advancement of the counselling and psychotherapy field.
Chemoenzymatic Total Synthesis of Sorbicatechol Structural Analogues and Evaluation of Their Antiviral Potential
Authors: Sib Anna , Milzarek Tobias M. , Herrmann Alexander , Oubraham Lila , Müller Jonas I. , Pichlmair Andreas , Brack‐Werner Ruth , Gulder Tobias A. M. 
Published: August 2019

AbstractSorbicillinoids are fungal polyketides characterized by highly complex and diverse molecular structures, with considerable stereochemical intricacy combined with a high degree of oxygenation. Many sorbicillinoids possess promising biological activities. An interesting member of this natural product family is sorbicatechol A, which is reported to have antiviral activity, particularly against influenza A virus (H1N1). Through a straightforward, one‐pot chemoenzymatic approach with recently developed oxidoreductase SorbC, the characteristic bicyclo[2.2.2]octane core of sorbicatechol is structurally diversified by variation of its natural 2‐methoxyphenol substituent. This facilitates the preparation of a focused library of structural analogues bearing substituted aromatic systems, alkanes, heterocycles, and ethers. Fast access to this structural diversity provides an opportunity to explore the antiviral potential of the sorbicatechol family.
Triplet‐State Position and Crystal‐Field Tuning in Opto‐Magnetic Lanthanide Complexes: Two Sides of the Same Coin
Authors: Gálico Diogo A. , Marin Riccardo , Brunet Gabriel , Errulat Dylan , Hemmer Eva , Sigoli Fernando A. , Moilanen Jani O. , Murugesu Muralee 
Published: August 2019

AbstractLanthanide‐complex‐based luminescence thermometry and single‐molecule magnetism are two effervescent fields of research, owing to the great promise they hold from an application standpoint. The high thermal sensitivity achievable, their contactless nature, along with sub‐micrometric spatial resolution make these luminescent thermometers appealing for accurate temperature probing in miniaturised electronics. To that end, single‐molecule magnets (SMMs) are expected to revolutionise the field of spintronics, thanks to the improvements made in terms of their working temperature—now surpassing that of liquid nitrogen—and manipulation of their spin state. Hence, the combination of such opto‐magnetic properties in a single molecule is desirable in the aim of overcoming, among others, addressability issues. Yet, improvements must be made through design strategies for the realisation of the aforementioned goal. Moving forward from these considerations, we present a thorough investigation of the effect that changes in the ligand scaffold of a family of terbium complexes have on their performance as luminescent thermometers and SMMs. In particular, an increased number of electron‐withdrawing groups yields modifications of the metal coordination environment and a lowering of the triplet state of the ligands. These effects are tightly intertwined, thus, resulting in concomitant variations of the SMM and the luminescence thermometry behaviour of the complexes. Supported by ab initio calculations, we can rationally interpret the observed trends and provide solid foundations for the development of opto‐magnetic lanthanide complexes.
Asymmetric Synthesis of α‐Amino Phosphonic Acids using Stable Imino Phosphonate as a Universal Precursor
Authors: Inokuma Tsubasa , Sakakibara Takuya , Someno Takatoshi , Masui Kana , Shigenaga Akira , Otaka Akira , Yamada Ken‐ichi 
Published: August 2019

AbstractA practical method for synthesizing chiral α‐amino phosphonic acid derivatives was developed. Readily available and stable N‐o‐nitrophenylsulfenyl (Nps) imino phosphonate was utilized as a substrate for a highly enantioselective Friedel–Crafts‐type addition of indole or pyrrole nucleophiles catalyzed by chiral phosphoric acid. The resulting adduct was easily converted into N‐9‐fluorenylmethyloxycarbonyl (Fmoc) amino phosphonic acid, which is useful for synthesizing peptides containing an amino phosphonic acid.
Die Chemikalien‐verordnung REACH
Authors: Herrmann Andrea , Maeß Christian 
Published: August 2019

ZusammenfassungDie europäische Chemikalienverordnung REACH führt derzeit zu einem Umbruch in der chemischen Industrie. Das Ziel von REACH ist es, ein hohes Schutzniveau für die menschliche Gesundheit und für die Umwelt sicherzustellen. Die Hersteller müssen daher neue Chemikalien, die in der EU hergestellt oder gehandelt werden sollen, bei der Europäischen Chemikalienbehörde registrieren, dazu müssen sie umfassende Daten zur Umweltverträglichkeit liefern. Zusätzlich müssen für alle Substanzen, die vor 1981 in Verkehr gebracht wurden, die Daten nachgereicht werden. Die letzte Frist für die Registrierung dieser Altstoffe endete im Mai 2018. Als besonders gefährlich eingestufte Stoffe können in ihrer Verwendung beschränkt oder verboten werden.