bluuebunny/crossref_metadata_2025 huggingface dataset:
Pairing smoking‐cessation services with lung cancer screening: A clinical guideline from the Association for the Treatment of Tobacco Use and Dependence and the Society for Research on Nicotine and Tobacco
Authors: Fucito Lisa M. , Czabafy Sharon , Hendricks Peter S. , Kotsen Chris , Richardson Donna , Toll Benjamin A. ,   for the Association for the Treatment of Tobacco Use and Dependence (ATTUD)/Society for Research on Nicotine and Tobacco (SRNT) Synergy Committee
Published: February 2016

Smoking cessation is crucial for reducing cancer risk and premature mortality. The US Preventive Services Task Force (USPSTF) has recommended annual lung cancer screening with low‐dose computed tomography (LDCT), and the Center for Medicare and Medicaid Services recently approved lung screening as a benefit for patients ages 55 to 77 years who have a 30 pack‐year history. The Society for Research on Nicotine and Tobacco (SRNT) and the Association for the Treatment of Tobacco Use and Dependence (ATTUD) developed the guideline described in this commentary based on an illustrative literature review to present the evidence for smoking‐cessation health benefits in this high‐risk group and to provide clinical recommendations for integrating evidence‐based smoking‐cessation treatment with lung cancer screening. Unfortunately, extant data on lung cancer screening participants were scarce at the time this guideline was written. However, in this review, the authors summarize the sufficient evidence on the benefits of smoking cessation and the efficacy of smoking‐cessation interventions for smokers ages 55 to 77 years to provide smoking‐cessation interventions for smokers who seek lung cancer screening. It is concluded that smokers who present for lung cancer screening should be encouraged to quit smoking at each visit. Access to evidence‐based smoking‐cessation interventions should be provided to all smokers regardless of scan results, and motivation to quit should not be a necessary precondition for treatment. Follow‐up contacts to support smoking‐cessation efforts should be arranged for smokers. Evidence‐based behavioral strategies should be used at each visit to motivate smokers who are unwilling to try quitting/reducing smoking or to try evidence‐based treatments that may lead to eventual cessation. Cancer 2016;122:1150–9. © 2016 American Cancer Society.
The performance of anal cytology as a screening test for anal HSILs in homosexual men
Authors: Jin Fengyi , Grulich Andrew E. , Poynten I. Mary , Hillman Richard J. , Templeton David J. , Law Carmella L.H. , Farnsworth Annabelle , Garland Suzanne M. , Fairley Christopher K. , Roberts Jennifer M. ,   and on behalf of the SPANC Study Team
Published: February 2016

BACKGROUND

Studies regarding the performance of anal cytology in which both the screening test (cytology) and the diagnostic test (high‐resolution anoscopy [HRA]) are performed in all members of a screening population are rare. The authors evaluated the performance of liquid‐based anal cytology in a cohort of homosexual men in Sydney, New South Wales, Australia.

METHODS

The Study of the Prevention of Anal Cancer (SPANC) is a 3‐year prospective study of the natural history of anal human papillomavirus infection in homosexual men aged ≥35 years. At baseline, all participants underwent a liquid‐based anal cytology test and HRA at the same clinical visit. Biopsies were obtained for histological assessment if lesions suspicious for human papillomavirus infection were visible during HRA. Using any cytological abnormality as the threshold, the sensitivity, specificity, and positive and negative predictive values were calculated against histologically diagnosed high‐grade squamous intraepithelial lesions (HSILs).

RESULTS

Among 617 men recruited, the median age was 49 years (range, 35‐79 years) and 35.7% were positive for the human immunodeficiency virus. Overall, the sensitivity of cytology was 83.2%, the specificity was 52.6%, the positive predictive value was 45.8%, and the negative predictive value was 86.7%. Specificity improved with increasing age (P for trend =.041). Sensitivity was significantly higher in men with >1 anal octant of biopsy‐confirmed HSIL (92.9% vs 77.7%; P = .010), and in those who had ≥10 metaplastic cells present on their cytology slides (87.5% vs 70.2%; P = .007).

CONCLUSIONS

Anal cytology was found to have a higher specificity in older men while maintaining sensitivity. Sensitivity was higher among those with more extensive HSILs and men with metaplastic cells present on cytology. Cancer Cytopathol 2016;124:415–24. © 2016 American Cancer Society.
Transcriptomic analysis of the hippocampus from six inbred strains of mice suggests a basis for sex‐specific susceptibility and severity of neurological disorders
Authors: Vied Cynthia , Ray Surjyendu , Badger Crystal‐Dawn , Bundy Joseph L. , Arbeitman Michelle N. , Nowakowski Richard S.
Published: February 2016

Identifying sex differences in gene expression within the brain is critical for determining why multiple neurological and behavioral disorders differentially affect males and females. Several disorders are more common or severe in males (e.g., autism and schizophrenia) or in females (e.g., Alzheimer's disease and depression). We analyzed transcriptomic data from the mouse hippocampus of six inbred strains (129S1/SvImJ, A/J, C57BL/6J, DBA/1J, DBA/2J, and PWD/Ph) to provide a perspective on differences between male and female gene expression. Our data show that 1) gene expression differences in males vs. females varies substantially across the strains, 2) only a few genes are differentially expressed across all of the strains (termed core genes), and 3) >2,600 genes differ in the individual strain comparisons (termed noncore genes). We found that DBA/2J uniquely has a substantial majority (89%) of differentially expressed genes (DEGs) that are more highly expressed in females than in males (female‐biased); 129/SvImJ has a majority (69%) of DEGs that are more highly expressed in males. To gain insight into the function of the DEGs, we examined gene ontology and pathway and phenotype enrichment and found significant enrichment in phenotypes related to abnormal nervous system morphology and physiology, among others. In addition, several pathways are enriched significantly, including Alzheimer's disease (AD), with 32 genes implicated in AD, eight of which are male‐biased. Three of the male‐biased genes have been implicated in a neuroprotective role in AD. Our transcriptomic data provide new insight into the possible genetic bases for sex‐specific susceptibility and severity of brain disorders. J. Comp. Neurol. 524:2696–2710, 2016. © 2016 Wiley Periodicals, Inc.
Identification of the mechanical parameters for the human uterus in vivo using intrauterine pressure measurements
Authors: Sharifimajd Babak , Ölvander Johan , Stålhand Jonas
Published: February 2016

There are limited experimental data to characterize the mechanical response of human myometrium. A method is presented in this work to identify mechanical parameters describing the active response of human myometrium from the in vivo intrauterine pressure measurements. The human uterine contraction during labor is simulated by implementing a coupled model in a finite element scheme, and the intrauterine pressure is evaluated as the outcome. A meta‐model is developed to approximate the finite element simulation response with a lower computational cost and used to identify model parameters through fitting its prediction to the in vivo measurements. Copyright © 2016 John Wiley & Sons, Ltd.
Performance evaluation of job schedulers on Hadoop YARN
Authors: Lin Jia‐Chun , Lee Ming‐Chang
Published: February 2016

To solve the limitation of Hadoop on scalability, resource sharing, and application support, the open‐source community proposes the next generation of Hadoop's compute platform called Yet Another Resource Negotiator (YARN) by separating resource management functions from the programming model. This separation enables various application types to run on YARN in parallel. To achieve fair resource sharing and high resource utilization, YARN provides the capacity scheduler and the fair scheduler. However, the performance impacts of the two schedulers are not clear when mixed applications run on a YARN cluster. Therefore, in this paper, we study four scheduling‐policy combinations (SPCs for short) derived from the two schedulers and then evaluate the four SPCs in extensive scenarios, which consider not only four application types, but also three different queue structures for organizing applications. The experimental results enable YARN managers to comprehend the influences of different SPCs and different queue structures on mixed applications. The results also help them to select a proper SPC and an appropriate queue structure to achieve better application execution performance. Copyright © 2016 John Wiley & Sons, Ltd.
Optimizing hadoop parameter settings with gene expression programming guided PSO
Authors: Khan Mukhtaj , Huang Zhengwen , Li Maozhen , Taylor Gareth A. , Khan Mushtaq
Published: February 2016

Hadoop MapReduce has become a major computing technology in support of big data analytics. The Hadoop framework has over 190 configuration parameters, and some of them can have a significant effect on the performance of a Hadoop job. Manually tuning the optimum or near optimum values of these parameters is a challenging task and also a time consuming process. This paper optimizes the performance of Hadoop by automatically tuning its configuration parameter settings. The proposed work first employs gene expression programming technique to build an objective function based on historical job running records, which represents a correlation among the Hadoop configuration parameters. It then employs particle swarm optimization technique, which makes use of the objective function to search for optimal or near optimal parameter settings. Experimental results show that the proposed work enhances the performance of Hadoop significantly compared with the default settings. Moreover, it outperforms both rule‐of‐thumb settings and the Starfish model in Hadoop performance optimization. © 2016 The Authors. Concurrency and Computation: Practice and Experience Published by John Wiley & Sons Ltd.
Knowledge diffusion in complex networks
Authors: Zhang Yichao , Li Xing , Aziz‐alaoui M. A. , Bertelle Cyrille , Guan Jihong , Zhou Shuigeng
Published: February 2016

Modern communication networks and social networks are the main tunnels of knowledge diffusion. Knowledge diffusion in complex networks is different from the epidemic‐like information spreading, because individuals are willing to learn and spread knowledge to their friends and the learning process can hardly be achieved in a few conversations. In this paper, we investigate the important issue as what topological structure is suitable for knowledge diffusion. We propose a new knowledge diffusion model, where both learning and forgetting mechanisms are considered. In this model, individuals can play imparter and learner simultaneously. Comparing knowledge diffusion on a series of complex topologies, we observe that the individuals with a large degree can quickly learn more knowledge, who are beneficial to knowledge diffusion. Our results surprisingly reveal that the networks with high degree‐heterogeneity are likely to be suitable for knowledge diffusion. Our finding suggests that enhancing the degree heterogeneity of existing social networks may help to improve the performance of knowledge diffusion. This result is well confirmed by our extensive simulation results. Our model therefore provides a theoretical framework for understanding knowledge diffusion in complex topologies. Copyright © 2016 John Wiley & Sons, Ltd.
Multiple multicast group key management for the Internet of People
Authors: Zhong Hong , Luo Weiya , Cui Jie
Published: February 2016

Group key management (GKM) is an important research topic in mobile multicast communication nowadays. With the development of multiple services based on groups, it may be a very common phenomenon that multiple multicast groups coexist under a single network, and mobile subscribers can subscribe a variety of these services. Nevertheless, the current GKM schemes are focused on the communication in only a single group, which do not fit for multiple multicast group scenarios because of inefficient use of keys. In this paper, we propose a novel GKM scheme for multiple multicast groups in the Internet of People, called the area based multiple GKM (AMGKM) scheme. AMGKM can be implemented in wireless mobile network environments such as VANETs, and supports users to move across the wireless networks in the Internet of People while users subscribing to multiple multicast services with minimized communication overheads. AMGKM can also effectively mitigate the investment pressure of signaling load, and satisfy both the forward and the backward security and support membership changes. Our proposed method exploits the master key encryption (MKE) algorithm for efficiently reducing the rekeying overheads while providing intense security. Copyright © 2016 John Wiley & Sons, Ltd.
Efficient Blue‐Colored Solid‐State Dye‐Sensitized Solar Cells: Enhanced Charge Collection by Using an in Situ Photoelectrochemically Generated Conducting Polymer Hole Conductor
Authors: Zhang Jinbao , Vlachopoulos Nick , Hao Yan , Holcombe Thomas W. , Boschloo Gerrit , Johansson Erik M. J. , Grätzel Michael , Hagfeldt Anders
Published: February 2016

A high power conversion efficiency (PCE) of 5.5 % was achieved by efficiently incorporating a diketopyrrolopyrrole‐based dye with a conducting polymer poly(3,4‐ethylenediothiophene) (PEDOT) hole‐transporting material (HTM) that was formed in situ, compared with a PCE of 2.9 % for small molecular spiro‐OMeTAD‐based solid‐state dye solar cells (sDSCs). The high PCE for PEDOT‐based sDSCs is mainly attributed to the significantly enhanced charge‐collection efficiency, as a result of the three‐order‐of‐magnitude higher hole conductivity (0.53 S cm−1) compared with that of the widely used low molecular weight HTM spiro‐OMeTAD (3.5×10−4 S cm−1).
Implications of Programmed Cell Death 1 Ligand 1 Heterogeneity in the Selection of Patients With Non‐Small Cell Lung Cancer to Receive Immunotherapy
Authors: Mansfield AS , Dong H
Published: February 2016

The use of programmed cell death 1 ligand 1 (PD‐L1) as a predictive biomarker to select patients to receive programmed cell death 1 (PD‐1) or PD‐L1 inhibitors in non‐small cell lung cancer (NSCLC) is limited by the definitions of positivity, interassay agreement, and intra‐ and intertumoral heterogeneity of expression. Although PD‐L1 expression enriches for responses, the lack of expression does not exclude clinical benefit.
Hydrogenolysis of Glycerol to 1,3‐propanediol under Low Hydrogen Pressure over WOx‐Supported Single/Pseudo‐Single Atom Pt Catalyst
Authors: Wang Jia , Zhao Xiaochen , Lei Nian , Li Lin , Zhang Leilei , Xu Shutao , Miao Shu , Pan Xiaoli , Wang Aiqin , Zhang Tao
Published: February 2016

Single/pseudo‐single atom Pt catalyst was prepared on mesoporous WOx. The large surface area and abundant oxygen vacancies of WOx improve the Pt dispersion and stabilize the Pt isolation. This newly prepared catalyst exhibited outstanding hydrogenolysis activity under 1 MPa H2 pressure with a very high space–time yield towards 1,3‐propanediol (3.78 g gPt−1 h−1) in Pt–W catalysts. The highly isolated Pt structure is thought to contribute to the excellent H2 dissociation capacity over Pt/WOx. The high selectivity towards 1,3‐propanediol is attributed to the heterolytic dissociation of H2 at the interface of Pt and WOx (providing specific Brønsted acid sites and the concerted dehydration–hydrogenation reaction) and the bond formation between glycerol and WOx, which favors/stabilizes the formation of a secondary carbocation intermediate as well as triggers the redox cycle of the W species (W6+⇄W5+).
The Thermophysical Properties of Iron Plasma
Authors: Apfelbaum E. M.
Published: February 2016

The pressure, internal energy, conductivity, thermal conductivity and thermal power of Iron plasma have been calculated at temperatures 10–100 kK and densities less than 2 g/cm3. The plasma composition has been obtained by means of corresponding system of coupled mass action laws. We have considered the atom ionization up to +6. The transport coefficients have been obtained within the relaxation time approximation. The comparison of our results with available measurement and calculation data has shown very good agreement for the pressure and less good agreement for the conductivity. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
The Dynamics of Dust Structures under Magnetic Field in Stratified Glow Discharge
Authors: Karasev V. Yu. , Dzlieva E. S. , Pavlov S. I. , Ermolenko M. A. , Novikov L. A. , Maiorov S. A.
Published: February 2016

A detailed research of mechanisms causing the rotation of dust structures formed in striations of the glow discharge in longitudinal magnetic field is presented. Literary data speak about sign‐variable dependence of angular velocity of dust structure on the magnetic field. The first done experiment proves that ion drag force is the reason of rotation with the negative projection of angular velocity on magnetic induction in small magnetic fields. The method of a variation of an ion flux in mixes of gases was used for the research. In the second experiment the gas rotation arising because of eddy electron current in the magnetic field was revealed by the method of probing of the discharge by dust particles. Estimates show that a prevalence of the mechanism of rotation of dust structures and correspondingly the direction of rotation depends both on discharge conditions and on the size of dust particles. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
A Dusty Plasma in a Non‐Self‐Sustained Gas Discharge at Atmospheric Pressure
Authors: Fiippov A. V. , Babichev V. N. , Pal' A. F. , Starostin A. N. , Cherkovets V. E.
Published: February 2016

A non‐self‐sustained (NSS) discharge at atmospheric gas pressure containing dust particles is studied. The NSS discharge was controlled by a stationary electron beam with energy up to 120 keV. A numerical model of the NSS discharge is based on the drift‐diffusion approach for electrons and ions and self‐consistently takes into account effects of the dust particles on the electron and ion densities. The dusty component is described by the number balance equation and the equation of motion for dust particles with allowance for the Stokes force, gravity force and electric force in the cathode sheath. Interaction between dust particles is described in the self‐consistent field approximation. It is established that, at a given gas ionization rate and given applied voltage, there is a critical dust particle size above which the levitation condition in the cathode sheath cannot be satisfied. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
CD4 results with a bias larger than hundred cells per microliter can have a significant impact on the clinical decision during treatment initiation of HIV patients
Authors: Daneau Géraldine , Buyze Jozefien , Wade Djibril , Diaw Papa Alassane , Dieye Tandakha Ndeye , Sopheak Thai , Florence Eric , Lynen Lutgarde , Kestens Luc
Published: February 2016

Background

CD4 counts are currently used to assess HIV patients for treatment eligibility and to monitor antiretroviral response to treatment. The emerging point‐of‐care devices could fill an important gap in resource‐limited settings. However, the accuracy of CD4‐counting instruments is diverse and data on how CD4 measurement errors have an impact on clinical decisions are lacking.

Methods

Clinicians were queried on the use of CD4 results in their clinical setting. Subsequently, the effect of CD4 measurement errors on treatment initiation was put in a statistical model. Based on clinical CD4 databases from Belgium, Cambodia, and Senegal, the percentage of unchanged clinical decisions was calculated (treatment initiation should start within a 3‐month delay [one visit]) for escalating CD4 measurement errors, taking into account the strict or preventive application of CD4 thresholds at 350 or 500 cells/µl used by clinicians.

Results

To ensure that the treatment was initiated appropriately for at least 95% of patients, an error of 5 − 10 cells/µl was allowed. This is significantly smaller than the bias of ±50 cells/µl most clinicians considered acceptable. For limits of agreement (LOA, 1.96 x error) of 100 cells/µl, corresponding to most CD4 instrument evaluations, the misclassification rate of patients was found to be 3 − 28% at the threshold of 350 cells/µl (strict or flexible), and 13 − 20% at 500 cells/µl.

Conclusions

The maximum allowed CD4 bias on results from new CD4 technologies should not exceed 50 cells/µl (LOA 100 cells/µl) when applied for treatment initiation, to ensure at least 72% of correct clinical decisions. © 2016 International Clinical Cytometry Society
Dynamic switch migration towards a scalable SDN control plane
Authors: Cheng Guozhen , Chen Hongchang , Hu Hongchao , Lan Julong
Published: February 2016

Distributed control plane is a promising approach to scalable software‐defined networking (SDN). Live migration of switches from controllers that are overloaded to those that are underutilized may be a solution to handle peak switch traffic using available control resource. However, such migration has to be performed with a well‐designed mechanism to fully utilize available resources in all three resource dimensions: CPU, bandwidth, and memory. In this article, we first provide a resource model for SDN and reduce the switch migration decision to a centralized resource utilization maximization problem under constraints of CPU, bandwidth, and memory. Second, we show that the problem of maximizing resource utilization in an SDN is equivalent to that of maximizing game players' profits in the context of non‐cooperative game theory. Taking controllers and switches as game players and commodities respectively, the player policy is how to migrate switches among the control plane. Finally, we implement a proof of concept, called GAME‐Switch Migration (GAME‐SM). The numerical experiments using Mininet emulator validate nice properties of our game model in enhancing the performance of control plane in SDN. Copyright © 2016 John Wiley & Sons, Ltd.
Multilevel space–time trellis coded cooperation with channel state information at transmitter
Authors: Aneja Sakshi , Sharma Sanjay
Published: February 2016

In this paper, the authors propose a system where a number of cooperating mobile nodes transmit information to a common destination node. Each cooperating node has a set of decoders to detect the information of other nodes and a set of encoders to further encode the decoded information as well as its own information using multilevel space–time trellis coding (MLSTTC) scheme. The coded information is mapped using multi‐resolution modulation partitioning to M‐ary quadrature amplitude modulation constellation. The mapped symbols are weighted based on the available channel state information at transmitting nodes. The weighting of transmitting symbols provides beamforming resulting in receive signal‐to‐noise ratio gain. The weighted symbols are sent to destination node through two transmit antennas. If the information of other nodes has been correctly decoded at the cooperating node, then the destination node receives the information of each node as many times as there are number of transmitting nodes, thus achieving full diversity order. A multistage Viterbi decoder is used at the destination node to extract information of each mobile node. The results indicate that the performance of proposed cooperative MLSTTC system is superior to non‐cooperative MLSTTC system. Copyright © 2016 John Wiley & Sons, Ltd.
Facilitate transfer, degree completion with concurrent enrollment program
Authors: Hope Joan
Published: February 2016

Whether students start at two‐ or four‐year institutions, most of them share the same goal: graduation. Many students who start at community colleges plan to earn bachelor's degrees. But often, not all their credits transfer. Or they learn they did not take the right courses to be on track to graduation for their chosen major.
The extent of shifts in vegetation phenology between rural and urban areas within a human‐dominated region
Authors: Dallimer Martin , Tang Zhiyao , Gaston Kevin J. , Davies Zoe G.
Published: February 2016

Urbanization is one of the major environmental challenges facing the world today. One of its particularly pressing effects is alterations to local and regional climate through, for example, the Urban Heat Island. Such changes in conditions are likely to have an impact on the phenology of urban vegetation, which will have knock‐on implications for the role that urban green infrastructure can play in delivering multiple ecosystem services. Here, in a human‐dominated region, we undertake an explicit comparison of vegetation phenology between urban and rural zones. Using satellite‐derived MODIS‐EVI data from the first decade of the 20th century, we extract metrics of vegetation phenology (date of start of growing season, date of end of growing season, and length of season) for Britain's 15 largest cities and their rural surrounds. On average, urban areas experienced a growing season 8.8 days longer than surrounding rural zones. As would be expected, there was a significant decline in growing season length with latitude (by 3.4 and 2.4 days/degree latitude in rural and urban areas respectively). Although there is considerable variability in how phenology in urban and rural areas differs across our study cities, we found no evidence that built urban form influences the start, end, or length of the growing season. However, the difference in the length of the growing season between rural and urban areas was significantly negatively associated with the mean disposable household income for a city. Vegetation in urban areas deliver many ecosystem services such as temperature mitigation, pollution removal, carbon uptake and storage, the provision of amenity value for humans and habitat for biodiversity. Given the rapid pace of urbanization and ongoing climate change, understanding how vegetation phenology will alter in the future is important if we wish to be able to manage urban greenspaces effectively.
Responses of ground‐dwelling arthropods to surface flow drying in channels and adjacent habitats along Mediterranean streams
Authors: Sánchez‐Montoya María del Mar , von Schiller Daniel , Ruhí Albert , Pechar Giuliano Sting , Proia Lorenzo , Miñano Jesús , Vidal‐Abarca María Rosario , Suárez María Luisa , Tockner Klement
Published: February 2016

Intermittent streams are dynamic ecosystems that alternate between dry and wet states. Despite their global dominance, we have scant information about the effects of surface flow drying on terrestrial arthropods in channel and adjacent terrestrial habitats. In the present study, we used pitfall traps to characterise the terrestrial arthropod assemblages along lateral gradients (channel, riparian, and upland habitats) in perennial and intermittent reaches of two contrasting Mediterranean intermittent streams (Rogativa and Fuirosos streams). Simultaneously, we assessed changes in assemblage composition and structure on five sampling occasions over the entire drying period (i.e. 29 days). The composition of arthropod assemblages differed among streams, flow regimes, habitat types, and sampling dates. In contrast, depending on the stream, taxonomic richness and total abundance were similar between perennial and intermittent reaches, but differed among habitat types. Formicidae, Araneae, Collembola, and Coleoptera explained most of the differences between flow regimes and habitat types in both streams. In Rogativa stream, arthropod abundances peaked in the dry channel and increased with drying time, while abundances decreased in riparian and upland habitats. It implies that the dry channel may be colonized by riparian and upland arthropods to a greater or lesser extent depending on the stream and the specific landscape context. Our results emphasize the importance of dry channels as temporary habitats for terrestrial arthropod assemblages. Thus, the dry period should be considered explicitly when assessing biodiversity of and establishing management strategies for intermittent streams and their fringing riparian and upland areas. Copyright © 2016 John Wiley & Sons, Ltd.
Synthesis, Characterization, Reactivity, Catalytic Activity, and Antiamoebic Activity of Vanadium(V) Complexes of ICL670 (Deferasirox) and a Related Ligand
Authors: Maurya Mannar R. , Sarkar Bithika , Avecilla Fernando , Tariq Saba , Azam Amir , Correia Isabel
Published: February 2016

The reactions of [VIVO(acac)2] (acac = acetylacetonato) with two ONO tridentate ligands, 4‐[3,5‐bis(2‐hydroxyphenyl)‐1,2,4‐triazol‐1‐yl]benzoic acid (H2L1, I) and 3,5‐bis(2‐hydroxyphenyl)‐1‐phenyl‐1,2,4‐triazole (H2L2, II) in methanol lead to the formation of the oxidovanadium(V) complexes [VVO(µ‐L1)(OMe)]2 (1) and [VVO(µ‐L2)(OMe)]2 (2). In the presence of KOH/CsOH, they give the corresponding dioxidovanadium(V) complexes. The isolated complexes K(H2O)[VVO2(L1)] (3), K(H2O)[VVO2(L2)] (4), Cs(H2O)[VVO2(L1)] (5), and Cs(H2O)[VVO2(L2)] (6) along with 1 and 2 have been characterized by various spectroscopic techniques (FTIR; UV/Vis; 1H, 13C, and 51V NMR), elemental analysis, thermal studies, MALDI‐TOF MS analysis, and single‐crystal analysis of 1a (complex 1 grown together with 4,4′‐bipyridyl). The oxidative bromination of thymol, catalyzed by these complexes, in the presence of KBr and HClO4 with H2O2 as an oxidant, gives 2‐bromothymol, 4‐bromothymol, and 2,4‐dibromothymol. The amounts of the catalyst, oxidant, KBr, HClO4, and the solvent were optimized for the maximum conversion of thymol. Both ligands and all complexes were tested in vitro for antiamoebic activity against the HM1:IMSS strain of Entamoeba histolytica by a microdilution method. The complexes are more potent amoebicidal agents than the standard drug metronidazole. Toxicity studies against a human cervical cancer cell line (HeLa) also confirm that these compounds are less cytotoxic than metronidazole.
Synthesis and Properties of Organic Hexahalocerate(III) Salts
Authors: Pohako‐Esko Kaija , Wehner Tobias , Schulz Peter S. , Heinemann Frank W. , Müller‐Buschbaum Klaus , Wasserscheid Peter
Published: February 2016

A series of hexahalocerate(III) salts with the general formula [cation]3[CeHal6] have been prepared by dissolving anhydrous cerium trihalides in imidazolium halide ionic liquids. Complexes with different anions, [CeCl6]3–, [CeBr6]3– and [CeBr3Cl3]3–, were synthesized and their cationic alkyl chains were varied. To confirm the structures of the prepared salts, X‐ray crystallography was used to characterize [BMIM]3[CeCl6]. Two different crystal structures were found: [BMIM]3[CeCl6] and the linear coordination polymer [BMIM]x[Ce(µ‐Cl)2Cl2(EtOH)2]x containing coordinated solvent. All the synthesized compounds were characterized by DSC and TGA. The influence of the cationic and anionic structures on the melting points and decomposition temperatures is discussed. Furthermore, the Ce‐containing salts [BMIM]3[CeHal6] show interesting photoluminescence properties: intense Ce3+‐based 5d–4f‐centred emission from the soft UV‐B region to the border of visible light is observed that is driven both by direct excitation of Ce3+ as well as by a sensitizer effect of the [BMIM]+ cation.
Methoxyphenyl Substituted Bis(picolyl)phosphines and Phosphine Oxides
Authors: Hettstedt Christina , Unglert Martin , Mayer Robert J. , Frank Anna , Karaghiosoff Konstantin
Published: February 2016

Three new derivatives of methoxyphenyl‐substituted bis(picolyl)phosphines 3–5, the CH2TMS substituted bis(picolyl)phosphine (6) and related phosphine oxides 2b–5b have been synthesized. Syntheses were accomplished by reacting the corresponding dichlorophosphines with picolylTMS (7). An improved synthesis of most of the starting materials is also presented and enables increased ligand yields in all cases. The new bis(picolyl)phosphines and phosphine oxides are extensively characterized by 1H, 13C and 31P NMR spectroscopy and, in the case of the literature known tris(picolyl)phosphine (2) and its new phosphine oxide derivative, single‐crystal X‐ray analysis was applied to structure elucidation efforts. The determination of the molecular structure of (o‐methoxyphenyl)dichlorophosphine (3a) was achieved by X‐ray analysis of a co‐crystal consisting of 3a and its rare phosphonic anhydride derivative 8.
Dihydrogen Bonding and Proton Transfer from MH and OH Acids to Group 10 Metal Hydrides [(tBuPCP)MH] [tBuPCP = κ3‐2,6‐(tBu2PCH2)2C6H3; M = Ni, Pd]
Authors: Osipova Elena S. , Belkova Natalia V. , Epstein Lina M. , Filippov Oleg A. , Kirkina Vladislava A. , Titova Ekaterina M. , Rossin Andrea , Peruzzini Maurizio , Shubina Elena S.
Published: February 2016

The interactions of HA acids {indole, fluorinated alcohols, phenols, and [CpW(CO)3H] (2)]} with the title hydrides [(tBuPCP)MH] [M = Ni (1a), Pd (1b)] have been studied by a combination of spectroscopic (variable‐temperature IR, NMR, UV/Vis) and computational (DFT/M06, AIM) methods in THF and toluene. The formation of the dihydrogen bond (DHB) 1···HA is the first step in a process leading to proton transfer and H2 evolution. The DHBs of 1 with 2 are much weaker than those of 1 with NH or OH acids, but the former complexes are more reactive. Kinetic studies of the reactions of 4‐(4′‐nitrophenylazo)phenol and [CpWH(CO)3] with 1b in THF gave activation enthalpies ΔH≠ = 9.2 ± 0.4 and 6.5 ± 1.5 kcal mol–1 and activation entropies ΔS≠ = –30 ± 1 and –35 ± 6 cal mol–1 K–1, respectively. Calculations revealed the (η2‐H2)‐like TS (ΔE≠ = 9.3 kcal mol–1) for the reaction of 1b with p‐nitrophenol and the [Pd(η2‐H2)]+OAr– complex as a local minimum at around 5 kcal mol–1 above the DHB adduct. In the reaction of 1b with 2, both the acidic WH and hydridic NiH or PdH bonds undergo heterolytic cleavage (ΔE≠ = 7.4 kcal mol–1) to yield the unusual µ,η1:1‐H2 end‐on complex. The µ,η1:1‐H2 molecule transforms easily into the more stable η2‐H2 side‐on tautomer, which eventually gives the bimetallic product after H2 evolution.
A rapid in‐house validated GC‐FID method for simultaneous determination of lipophilic bioactives in olive oil: Squalene, α‐tocopherol, and β‐sitosterol
Authors: Seçmeler Özge , Güçlü Üstündağ Özlem
Published: February 2016

The analytical methodologies utilizing HPLC or GC techniques for the determination of predominant lipophilic bioactives in olive oil (β‐sitosterol, squalene, and α‐tocopherol) may include a number of sample pre‐treatment steps (such as clean up (using TLC and SPE), saponification, and derivatization) making them rather lengthy and impractical. The objective of this study was to develop a rapid and in‐house validated GC‐FID method for the simultaneous determination of these bioactives using response surface methodology for optimization of critical parameters (time and temperature of saponification and derivatization). In‐house method validation based on method performance parameters (linearity, limit of detection (LOD), limit of quantification (LOQ), repeatability, and recovery) was carried out using optimized method parameters (10 min derivatization time for 30°C derivatization temperature, 56°C saponification temperature, and 10 min saponification time). The linear range of β‐sitosterol, squalene, and α‐tocopherol was determined to be between LOQ value (8.4; 16.0; 12.5 mg/100 g, respectively) and upper end (500; 700 mg/100 g for β‐sitosterol; squalene, respectively) with acceptable accuracy, recovery (92–97%; 93–95%; 93–110%) and repeatability.

Practical applications: The in‐house GC‐FID method developed in this study offers a rapid, accurate and validated method alternative to current official methods and simultaneous methods recently published in the literature. Time of analysis was reduced to ∼5 h for every six samples compared to ∼20 h specified in official methods. The developed method was fully validated covering all parameters; linearity, LOQ, LOD, recovery, and repeatability. This method can be incorporated into quality control programs for olive oil and its application areas can be expanded to include other plant oils after further validation studies.

A new rapid multicomponent in‐house validated method was developed to determine predominant lipophilics of olive oil.
N‐Rich Fused Heterocyclic Systems: Synthesis, Structure, Optical and Electrochemical Characterization
Authors: Fusco Sandra , Maglione Cira , Velardo Amalia , Piccialli Vincenzo , Liguori Rosalba , Peluso Andrea , Rubino Alfredo , Centore Roberto
Published: February 2016

A new class of N‐rich fused heterocyclic compounds containing the triazolo‐triazine moiety was synthesized and studied by cyclic voltammetry, UV/Vis spectroscopy, X‐ray diffraction, and first principle computations. All the compounds show reversible or quasi‐reversible reduction processes, with reduction potentials easily tunable within the class. LUMO energies as low as –3.95 eV have been measured. The UV/Vis spectra show highly structured absorptions, indicative of rigid molecular skeletons. The solid‐state packing is dominated by π–π stacking interactions, which are promoted by weak CAr–H···N interactions, whereas face‐to‐edge contacts (T contacts), typical of many fused hydrocarbons, are largely absent.
Titanium Enolate Chemistry at the Beginning of the 21st Century
Authors: Cież Dariusz , Pałasz Aleksandra , Trzewik Bartosz
Published: February 2016

The aim of the microreview is to summarize the current state of knowledge in the field of titanium enolate chemistry. The authors focus on stereoselective organic syntheses promoted by titanium enolates and analyze developments in the synthetic methodology observed in this area during the last fifteen years.
Social functioning in adulthood: Understanding long‐term outcomes of adolescents with chronic pain/fatigue treated at inpatient rehabilitation programs
Authors: Westendorp T. , Verbunt J.A. , Remerie S.C. , de Blécourt A.C.E. , van Baalen B. , Smeets R.J.E.M.
Published: February 2016

Background

Chronic pain and fatigue are both common complaints in childhood and adolescence and often persist over time. The aim of the study was to investigate whether chronic pain/fatigue persists during adulthood and how former patients function and participate in society as adults.

Methods

This historical cohort study used questionnaires to gather the data. Predictors for social participation in adulthood were also identified. Differences in functioning and health care use between young adults with current pain/fatigue complaints and those without were also discussed.

Results

Ninety‐four young adults responded; their mean age was 26.6 years and 91.5% were women. The average time since treatment was 10.2 years. 63.4% reported ongoing or new pain/fatigue complaints. 72.0% had a paid job; of those who worked, 22.1% reported taking sick leave in the past month. 78.7% of them reported having one or more chronic diseases.

A higher level of pain/fatigue measured pre‐treatment was identified as a predictor for more impaired social participation in adulthood. Young adults with current pain/fatigue complaints reported more healthcare utilization, lower levels of physical functioning and limitations in daily activities due to physical problems.

Conclusions

A considerable number of these young adults still have pain/fatigue complaints in adulthood. More pain/fatigue pre‐treatment during adolescence predict impaired functioning in the work‐educational domain in young adulthood.

What does this study add?

This study examines the social participation of young adults who suffered from severe chronic pain/fatigue during adolescence.

Predictors for social participation are reported, as are the differences between young adults with and without persistent pain/fatigue complaints.
Analgesia by telemedically supported paramedics compared with physician‐administered analgesia: A prospective, interventional, multicentre trial
Authors: Brokmann J.C. , Rossaint R. , Hirsch F. , Beckers S.K. , Czaplik M. , Chowanetz M. , Tamm M. , Bergrath S.
Published: February 2016

Background

In German emergency medical services (EMS), the analgesia is restricted to physicians. In this prospective, interventional, multicentre trial, complications with and quality of telemedically delegated analgesia were evaluated.

Methods

If prehospital analgesia was necessary, five telemedically equipped paramedic ambulances from four different districts could consult a telemedicine centre. Analgesics were delegated based on a predefined algorithm. Telemedically assisted cases were compared with local historical regular EMS missions using matched pairs. The primary outcome was the frequency of therapeutic complications (respiratory/circulatory insufficiency, allergic reactions). Secondary outcomes were quality of analgesia (11‐point numerical rating scale, NRS) and the frequency of nausea/vomiting.

Results

Analgesia was necessary in 106 telemedically assisted missions. In 23 cases, the telemedical procedure was used until an EMS physician arrived. Of the remaining 83 cases, 80 could be matched to comparable controls. Complications did not occur in either the study group or the control group (0 vs. 0; p = N/A). Complete NRS documentation was noted in 65/80 (study group) and 32/80 (control group) cases (p < 0.0001). Adequate initial pain reduction (quality indicator: reduction of NRS ≥ 2 points or NRS < 5 at end of mission) occurred in 61/65 versus 31/32 cases (p = 1.0); NRS reduction during mission was 3.78 ± 2.0 versus 4.38 ± 2.2 points (p = 0.0159). Nausea and vomiting occurred with equal frequency in both groups.

Conclusions

Telemedical delegation of analgesics to paramedics was safe and led to a pain reduction superior to the published minimum standard in both groups. The documentation quality was better in the telemedicine group.

What does this study add?

Little is known about the safety and quality of prehospital analgesia carried out by emergency medical services (EMS). Beside potential quality problems, in some countries meaningful pain reduction is limited by legal regulations that allow only physicians to administer analgesics.

This first multicentre prospective trial for telemedically delegated analgesia demonstrates that remote analgesia is possible and safe and retains equivalent analgesic quality compared with that administered by onsite EMS physicians.
Pain‐catastrophizing and fear‐avoidance beliefs as mediators between post‐traumatic stress symptoms and pain following whiplash injury – A prospective cohort study
Authors: Andersen T.E. , Karstoft K‐I. , Brink O. , Elklit A.
Published: February 2016

Background

Knowledge about the course of recovery after whiplash injury is important. Most valuable is identification of prognostic factors that may be reversed by intervention. The mutual maintenance model outlines how post‐traumatic stress symptoms (PTSS) and pain may be mutually maintained by attention bias, fear, negative affect and avoidance behaviours. In a similar vein, the fear‐avoidance model describes how pain‐catastrophizing (PCS), fear‐avoidance beliefs (FA) and depression may result in persistent pain. These mechanisms still need to be investigated longitudinally in a whiplash cohort.

Methods

A longitudinal cohort design was used to assess patients for pain intensity and psychological distress after whiplash injury. Consecutive patients were all contacted within 3 weeks after their whiplash injury (n = 198). Follow‐up questionnaires were sent 3 and 6 months post‐injury. Latent Growth Mixture Modelling was used to identify distinct trajectories of recovery from pain.

Results

Five distinct trajectories were identified. Six months post‐injury, 64.6% could be classified as recovered and 35.4% as non‐recovered. The non‐recovered (the medium stable, high stable and very high stable trajectories) displayed significantly higher levels of PTSS, PCS, FA and depression at all time points compared to the recovered trajectories. Importantly, PCS and FA mediated the effect of PTSS on pain intensity.

Conclusions

The present study adds important knowledge about the development of psychological distress and pain after whiplash injury. The finding, that PCS and FA mediated the effect of PTSS on pain intensity is a novel finding with important implications for prevention and management of whiplash‐associated disorders.

What does this study add?

The study confirms the mechanisms as outlined in the fear‐avoidance model and the mutual maintenance model.

The study adds important knowledge of pain‐catastrophizing and fear‐avoidance beliefs as mediating mechanisms in the effect of post‐traumatic stress on pain intensity. Hence, cognitive behavioural techniques targeting avoidance behaviour and catastrophizing may be beneficial preventing the development of chronic pain.
Resilience moderates the association between chronic pain and depressive symptoms in the elderly
Authors: Bauer H. , Emeny R. T. , Baumert J. , Ladwig K.‐H.
Published: February 2016

Background

Chronic pain is frequent in elderly people and, especially if widespread, associated with poor mental health. We investigated whether a resilient personality protects older adults against the adverse effects of chronic pain.

Methods

Pain status [no pain, chronic local pain (CLP) and chronic widespread pain (CWP)] was determined using the American College of Rheumatologists' criteria for widespread pain in a cross‐sectional sample of 724 participants aged 68–92 years drawn from the population‐based KORA‐Age study in Southern Germany. Depressive symptoms and resilience were assessed via the scales GDS‐15 and RS‐5. The relation between pain, resilience and depressive symptoms was modelled using logistic and quantile regression.

Results

CLP prevalence and CWP prevalence were 57.5% and 12.3%, respectively. Confounder‐adjusted logistic regression indicated a fourfold risk of depressed mood (GDS‐15 ≥ 5) in CWP, vs. no pain (OR = 4.08, 95% CI 1.90–8.74). However, in quantile regression, the adverse effect of CWP was significantly attenuated by resilience when looking at the GDS‐15 score lower quartile (p = 0.011) and median (p = 0.011). This effect appeared to be mainly driven by participants aged 75–84 years. Confounder adjustment reduced the effect of CLP on depressive symptoms to non‐significance, and effect modification by resilience was undetectable in regression models of CLP.

Conclusions

Resilience was protective in the association of CWP with depressive symptoms in this analysis. Older adults with CWP may potentially benefit from interventions supporting resilience. Prospective research should investigate the protective role of resilience in the potentially self‐perpetuating relation between chronic pain and depressed affect.

What does this study add?

The association of chronic widespread pain with depressive symptoms in the elderly population is attenuated by resilience.