bluuebunny/crossref_metadata_2025 huggingface dataset:
Calcium‐Catalyzed Synthesis of Polysubstituted 2‐Alkenylfurans from β‐Keto Esters Tethered to Propargyl Alcohols
Authors: Morcillo Sara P. , Leboeuf David , Bour Christophe , Gandon Vincent
Published: October 2016

An efficient synthesis of polysubstituted 2‐alkenylfurans using Ca(NTf2)2/KPF6 as a catalytic mixture is described. It is based on the cycloelimination of readily available propargyl alcohols tethered to β‐keto esters under dry conditions to avoid competitive Meyer–Schuster rearrangement. The furan can be further functionalized in situ by a calcium‐catalyzed Friedel–Crafts‐type reaction with secondary and tertiary alcohols. The title reaction allows for the high‐yielding preparation of di‐, tri‐, and tetrasubstituted 2‐alkenylfurans, which are important subunits of bioactive compounds.
Intramolecularly Coordinated Gallium Sulfides: Suitable Single Source Precursors for GaS Thin Films
Authors: Řičica Tomáš , Světlík Tomáš , Dostál Libor , Růžička Aleš , Růžička Květoslav , Beneš Ludvík , Němec Petr , Bouška Marek , Jambor Roman
Published: October 2016

Our studies have been focused on the synthesis of N→Ga coordinated organogallium sulfides [L1Ga(μ‐S)]3 (1) and [L2Ga(μ‐S)]2 (2) containing either N,C,N‐ or C,N‐chelating ligands L1 or L2 (L1 is {2,6‐(Me2NCH2)2C6H3}− and L2 is {2‐(Et2NCH2)‐4,6‐tBu2‐C6H2}−). As the result of the different ligands, compounds 1 and 2 differ mutually in their structure. To change the Ga/S ratio, unusually N→Ga coordinated organogallium tetrasulfide L1Ga(κ2‐S4) (3) was prepared and the unprecedented complex [{2‐[CH{(CH2)3CH3}(μ‐OH)]‐6‐CH2NMe2}C6H3]GaS (4) was also isolated as the minor by‐product of the reaction. Compounds 1–3 were further studied as potential single‐source precursors for amorphous GaS thin film deposition by spin‐coating.
Tailorable PC71BM Isomers: Using the Most Prevalent Electron Acceptor to Obtain High‐Performance Polymer Solar Cells
Authors: Zhan Xin‐Xing , Zhang Xin , Dai Si‐Min , Li Shu‐Hui , Lu Xu‐Zhai , Deng Lin‐Long , Xie Su‐Yuan , Huang Rong‐Bin , Zheng Lan‐Sun
Published: October 2016

Despite being widely used as electron acceptor in polymer solar cells, commercially available PC71BM (phenyl‐C71‐butyric acid methyl ester) usually has a “random” composition of mixed regioisomers or stereoisomers. Here PC71BM has been isolated into three typical isomers, α‐, β1‐ and β2‐PC71BM, to establish the isomer‐dependent photovoltaic performance on changing the ternary composition of α‐, β1‐ and β2‐PC71BM. Mixing the isomers in a ratio of α/β1/β2=8:1:1 resulted in the best power conversion efficiency (PCE) of 7.67 % for the polymer solar cells with PTB7:PC71BM as photoactive layer (PTB7=poly[[4,8‐bis[(2‐ethylhexyl)oxy]benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]]). The three typical PC71BM isomers, even though sharing similar LUMO energy levels and light absorption, render starkly different photovoltaic performances with average‐performing PCE of 1.28–7.44 % due to diverse self‐aggregation of individual or mixed PC71BM isomers in the otherwise same polymer solar cells.
Metal Complexes for Two‐Photon Photodynamic Therapy: A Cyclometallated Iridium Complex Induces Two‐Photon Photosensitization of Cancer Cells under Near‐IR Light
Authors: McKenzie Luke K. , Sazanovich Igor V. , Baggaley Elizabeth , Bonneau Mickaële , Guerchais Véronique , Williams J. A. Gareth , Weinstein Julia A. , Bryant Helen E.
Published: October 2016

Photodynamic therapy (PDT) uses photosensitizers (PS) which only become cytotoxic upon light‐irradiation. Transition‐metal complexes are highly promising PS due to long excited‐state lifetimes, and high photo‐stabilities. However, these complexes usually absorb higher‐energy UV/Vis light, whereas the optimal tissue transparency is in the lower‐energy NIR region. Two‐photon excitation (TPE) can overcome this dichotomy, with simultaneous absorption of two lower‐energy NIR‐photons populating the same PS‐active excited state as one higher‐energy photon. We introduce two low‐molecular weight, long‐lived and photo‐stable iridium complexes of the [Ir(N^C)2(N^N)]+ family with high TP‐absorption, which localise to mitochondria and lysosomal structures in live cells. The compounds are efficient PS under 1‐photon irradiation (405 nm) resulting in apoptotic cell death in diverse cancer cell lines at low light doses (3.6 J cm−2), low concentrations, and photo‐indexes greater than 555. Remarkably 1 also displays high PS activity killing cancer cells under NIR two‐photon excitation (760 nm), which along with its photo‐stability indicates potential future clinical application.
2015 American Thyroid Association Management Guidelines for Adult Patients with Thyroid Nodules and Differentiated Thyroid Cancer: What is new and what has changed?
Authors: Haugen Bryan R.
Published: October 2016

Thyroid nodules are very common, and thyroid cancer is currently the fifth leading cancer diagnosis in women. The American Thyroid Association has led the development and revision of guidelines for the management of patients with thyroid nodules and differentiated thyroid cancer (DTC). The most current revision was published in the January 2016 issue of the journal Thyroid. The current guidelines have 101 recommendations, with 8 figures and 17 tables that are hopefully helpful to those treating patients with thyroid nodules and cancer. The primary goals of the American Thyroid Association Guidelines Task Force were to use the current evidence to guide recommendations and yet be as helpful and practical as possible within the scope and strength of the evidence. The current review focuses on new and significantly revised recommendations that may very well change clinical practice. The author notes 3 new basic principles that have emerged in this guidelines revision: 1) the management of thyroid nodules, including the decision to perform a fine‐needle aspiration biopsy as well as follow‐up decision making, will be heavily influenced by the newly developed sonographic risk pattern; 2) the long‐term management of DTC along with thyroid‐stimulating hormone target goals will be heavily influenced by the 4 categories of “response to therapy”; and 3) the management of patients with radioactive iodine‐refractory DTC will be divided into 4 basic decision‐making groups: patients who should undergo monitoring, patients who should undergo directed therapies, patients who should undergo systemic therapies, and patients who should be offered entry into clinical trials. Cancer 2017;123:372–381. © 2016 American Cancer Society.
Insights into the Ring‐Opening of Biomass‐Derived Furanics over Carbon‐Supported Ruthenium
Authors: Gilkey Matthew J. , Mironenko Alexander V. , Yang Leerang , Vlachos Dionisios G. , Xu Bingjun
Published: October 2016

The selective ring‐opening of cellulose‐derived furanic molecules is a promising pathway for the production of industrially relevant linear oxygenates, such as 1,6‐hexanediol. 2,5‐Dimethylfuran (DMF) is employed as a model compound in a combined experimental and computational investigation to provide insights into the metal‐catalyzed ring‐opening. Ring‐opening to 2‐hexanol and 2‐hexanone and ring‐saturation to 2,5‐dimethyltetrahydrofuran (DMTHF) are identified as two main parallel pathways. DFT calculations and microkinetic modeling indicate that DMF adsorbs on Ru in an open‐ring configuration, which is potentially a common surface intermediate that leads to both ring‐opening and ring‐saturation products. Although the activation barriers for the two pathways are comparable, the formation of DMTHF is more thermodynamically favorable. In addition, steric interactions with co‐adsorbed 2‐propoxyl, derived from the solvent, and the oxophilic nature of Ru play key roles to determine the product distribution: the former favors less bulky, that is, ring‐closed, intermediates, and the latter retards O−H bond formation. Finally, we show that the hydrodeoxygenation of oxygenated furanics, such as 5‐methylfurfural and (5‐methyl‐2‐furyl)methanol, on Ru occurs preferentially at oxygen‐containing side groups to form DMF, followed by either ring‐opening or ring‐saturation.
Marmoset vocal communication: Behavior and neurobiology
Authors: Eliades Steven J. , Miller Cory T.
Published: October 2016

There has been recent increasing interest in the use of marmosets, a New World primate species, as a model in biomedical research. One of the principal advantages of marmosets as a research model is their rich vocal repertoire and communicative vocal behaviors displayed both in the wild and in captivity. Studies of this species' vocal communication system have the potential to reveal the evolutionary underpinnings of human speech, and therefore are of interest to the neuroscience and biology research communities. Here a recent research into the behavioral and neurobiological basis of marmoset vocal communication was reviewed and they argued for their broader value as a neuroscientific model. They discuss potential avenues for future research including developmental neurobiology and the application of modern molecular tools to the study of primate communication. © 2016 Wiley Periodicals, Inc. Develop Neurobiol 77: 286–299, 2017
The Effects of Visual Attention Span and Phonological Decoding in Reading Comprehension in Dyslexia: A Path Analysis
Authors: Chen Chen , Schneps Matthew H. , Masyn Katherine E. , Thomson Jennifer M.
Published: October 2016

Increasing evidence has shown visual attention span to be a factor, distinct from phonological skills, that explains single‐word identification (pseudo‐word/word reading) performance in dyslexia. Yet, little is known about how well visual attention span explains text comprehension. Observing reading comprehension in a sample of 105 high school students with dyslexia, we used a pathway analysis to examine the direct and indirect path between visual attention span and reading comprehension while controlling for other factors such as phonological awareness, letter identification, short‐term memory, IQ and age. Integrating phonemic decoding efficiency skills in the analytic model, this study aimed to disentangle how visual attention span and phonological skills work together in reading comprehension for readers with dyslexia. We found visual attention span to have a significant direct effect on more difficult reading comprehension but not on an easier level. It also had a significant direct effect on pseudo‐word identification but not on word identification. In addition, we found that visual attention span indirectly explains reading comprehension through pseudo‐word reading and word reading skills. This study supports the hypothesis that at least part of the dyslexic profile can be explained by visual attention abilities. Copyright © 2016 John Wiley & Sons, Ltd.
Weight, shape, and muscularity concerns in male and female adolescents: Predictors of change and influences on eating concern
Authors: Hoffmann Svenja , Warschburger Petra
Published: October 2016

Objective

The purpose of this study was to examine the impact of age and weight status on adolescents' body dissatisfaction and its change over 20 months in a gender‐comparing design. The influence of body image concern on eating concern was also investigated.

Method

In a prospective study, 675 male and female adolescents aged 12–16 were assessed using self‐report questionnaires on weight, shape, muscularity, and eating concerns. Height and weight measurements were taken by trained personnel. Data were analyzed using structural equation modeling.

Results

Analyses of latent means revealed more pronounced weight/shape concern in females than males and more pronounced muscularity concern in males than females. Weight/shape concern increased in females over time, whereas muscularity concern remained stable in both genders. Baseline levels of weight/shape concern could be predicted by age and weight status in females and by weight status in males. The only predictor of change in weight/shape concern was weight status in males. Baseline levels of muscularity concern could be predicted by age in females and by weight status in males. Similar effects were found for changes in muscularity concern in both genders. Increases in weight/shape and muscularity concern were associated with more pronounced eating concern.

Discussion

The results confirm gender differences in distinctive facets of body image concern and its prediction. The relevance of increase in body image concern in adolescents is underlined by its association with eating concern in both genders. Further explanatory variables for change in body dissatisfaction should be examined in future studies. © 2016 Wiley Periodicals, Inc.(Int J Eat Disord 2017; 50:139–147)
Microbial community responses to soil tillage and crop rotation in a corn/soybean agroecosystem
Authors: Smith Chris R. , Blair Peter L. , Boyd Charlie , Cody Brianne , Hazel Alexander , Hedrick Ashley , Kathuria Hitesh , Khurana Parul , Kramer Brent , Muterspaw Kristin , Peck Charles , Sells Emily , Skinner Jessica , Tegeler Cara , Wolfe Zoe
Published: October 2016

The acreage planted in corn and soybean crops is vast, and these crops contribute substantially to the world economy. The agricultural practices employed for farming these crops have major effects on ecosystem health at a worldwide scale. The microbial communities living in agricultural soils significantly contribute to nutrient uptake and cycling and can have both positive and negative impacts on the crops growing with them. In this study, we examined the impact of the crop planted and soil tillage on nutrient levels, microbial communities, and the biochemical pathways present in the soil. We found that farming practice, that is conventional tillage versus no‐till, had a much greater impact on nearly everything measured compared to the crop planted. No‐till fields tended to have higher nutrient levels and distinct microbial communities. Moreover, no‐till fields had more DNA sequences associated with key nitrogen cycle processes, suggesting that the microbial communities were more active in cycling nitrogen. Our results indicate that tilling of agricultural soil may magnify the degree of nutrient waste and runoff by altering nutrient cycles through changes to microbial communities. Currently, a minority of acreage is maintained without tillage despite clear benefits to soil nutrient levels, and a decrease in nutrient runoff—both of which have ecosystem‐level effects and both direct and indirect effects on humans and other organisms.
Nitrogen cycling and export in California chaparral: the role of climate in shaping ecosystem responses to fire
Authors: Hanan Erin J. , Tague Christina (Naomi) , Schimel Joshua P.
Published: October 2016

Climate change models predict that interannual rainfall variability will increase in California over the next several decades; these changes will likely influence how frequently California ecosystems burn and how they respond to fire. Fires uncouple N mobilization from uptake by destroying plant biomass and increasing nitrification. Following fire, autumn and winter rains can leach N into streams from slopes that have been denuded. The amount of N exported depends on how rapidly soil microbes metabolize it into mobile forms such as , and the rate that recovering plants take up available N. However, the long‐term effects of a changing climate on postfire N dynamics remain unknown. We used the ecohydrologic model RHESSys (regional hydro‐ecologic simulation system) to evaluate how interannual climate variability may affect the magnitude of N mineralization, nitrification, N export, and plant recovery following fire. N export was highest when fire was followed by drought; even though there was less water moving through the system, dry conditions prolonged the period during which N mobilization was decoupled from plant uptake. We also found that the effects of drought on N export were magnified in stands dominated by obligate seeders, which initially recovered more slowly than resprouters. These findings suggest that climate may regulate N balance most powerfully by influencing how quickly plants “turn on” and begin to immobilize N.
Spatial and environmental processes show temporal variation in the structuring of waterbird metacommunities
Authors: Henry Dominic A. W. , Cumming Graeme S.
Published: October 2016

Metacommunity theory provides a framework for assessing the role of spatial and environmental processes in structuring ecological communities and places emphasis on the role of dispersal. Four metacommunity perspectives have been proposed: species‐sorting, patch dynamics, mass effects, and a neutral model. Metacommunity analysis decomposes the variance in communities into regional and local dynamics and ascribes it to one of these perspectives, although they are not always mutually exclusive. Although birds are a well‐studied taxon, consensus around processes structuring freshwater avian metacommunities is lacking and few studies have repeated samples through time. We used variance partitioning to analyze waterbird community data collected over seven sampling periods at 60 wetland sites in KwaZulu‐Natal, South Africa, to distinguish the processes driving beta‐diversity and identify which metacommunity perspective(s) best explained these patterns. We addressed two focal questions: (1) how do environmental, spatial, and spatially structured environmental components contribute to variance in the waterbird community; and (2) given a significant contribution, which environmental variables were most important in explaining metacommunity structure? We also investigated the role of temporal variation in community processes by comparing results across sampling periods. The underlying landscape was characterized by four groups of environmental variables: vegetation structure, water quality, rainfall, and land cover. Moran's eigenvector maps were used to generate a set of multiscale spatial predictor variables. Our results showed that the spatially structured environmental component was dominant through the sampling periods. Purely spatial and environmental components contributed a significant proportion of variance, but their magnitudes showed considerable temporal variation. Environmental processes were more pronounced in winter periods while purely spatial processes were augmented in the summer months. Our results suggest that species‐sorting is the primary structuring forces in waterbird communities. The presence of spatial effects, especially in summer, does however suggest that species‐sorting does not operate in isolation. Future efforts also need to address the causes and consequences of temporal variation in metacommunity processes.
Management of forest regeneration in boreal and temperate deer–forest systems: challenges, guidelines, and research gaps
Authors: Beguin Julien , Tremblay Jean‐Pierre , Thiffault Nelson , Pothier David , Côté Steeve D.
Published: October 2016

Heavy browsing pressure from large ungulates is a multicontinent phenomenon that causes regeneration failure of many palatable tree species and induces important socioeconomic and ecological impacts in forest ecosystems. The development of forest management practices that address adequately this issue, however, remains scarce and challenging because (1) large herbivores are both a resource and a source of disturbance; (2) the management of forests and ungulate populations remains largely disconnected in practice; and (3) we still lack a good understanding of the role of critical factors, especially deer densities, vegetation attributes, and their interactions, on the magnitude of browsing damages on forest regeneration. We bring new insights into these challenging issues by critically reviewing the current methods used by managers and conservationists to mitigate deer impacts on forest regeneration, emphasizing the spatial scale at which these methods are undertaken. Specifically, we review management actions at multiple scales on both deer populations (e.g., hunting) and vegetation (e.g., silvicultural treatments) that are common to most deer–forest systems and, for that reason, deserve priority investigation. We identify strengths and limitations of current management actions and highlight the main research gaps. Based on this review, we propose a new integrated management scheme that explicitly addresses: (1) the integration and prioritization of management actions, (2) the development of adaptive management plans, and (3) the participation of stakeholders. Conflicting demands by different stakeholders have challenged the effectiveness of management strategies in deer–forest systems. To reverse this situation, we advocate for a shift of paradigm and the development of integrated strategies that (1) bridge the gap between management actions and the design of in situ experiments and (2) coordinate actions at multiple spatial scales on both deer populations and forests. We propose a new framework informed by key objectives and grounded in the adaptive management paradigm to support this transition, and suggest a research agenda for the next decade(s).
An invasive ant reduces diversity but does not disrupt a key ecosystem function in an African savanna
Authors: Milligan Patrick D. , Prior Kirsten M. , Palmer Todd M.
Published: October 2016

Understanding the consequences of anthropogenic biodiversity decline has become an increasingly urgent priority for ecologists. Biological invasions are a common result of anthropogenic habitat change, and numerous studies have established the negative impact of invasions on the diversity and abundance of native species. But fewer studies have directly examined the effect of biological invasions on ecosystem functions and services. We leveraged a recent invasion by the big‐headed ant (Pheidole megacephala) in an East African savanna to evaluate the impact of invasion on arthropod diversity, and on dung decomposition, an ecosystem function provided by a subset of these arthropods. We found that invaded sites had lower overall arthropod diversity, but these diversity changes did not extend to a functional group of detritivorous insects (e.g., dung beetles and termites), which play key roles in dung decomposition. In a manipulative experiment, we found that rates of dung pile decomposition did not differ significantly in invaded vs. non‐invaded sites. Our study provides evidence that these invaded savannas are undergoing large changes in arthropod diversity, while maintaining resilience in decomposition function, suggesting that diversity alone may be an insufficient impact assessment tool. By monitoring functional guilds and their attendant services, we may better understand the broader structural and functional consequences of invasion.
Another Example of Organo‐Click Reactions: TEMPO‐Promoted Oxidative Azide–Olefin Cycloaddition for the Synthesis of 1,2,3‐Triazoles in Water
Authors: Gangaprasad Dasari , Paul Raj John , Kiranmye Tayyala , Karthikeyan Kesavan , Elangovan Jebamalai
Published: October 2016

The water‐mediated, metal‐free, 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) promoted oxidative [3+2] cycloaddition of organic azides with electron‐deficient terminal and internal olefins was explored. A library of 1,4‐disubstituted and 1,4,5‐trisubstituted‐1,2,3‐triazoles were synthesized in moderate to excellent yields. This method was also found to be compatible not only with open‐chain olefins but also with cyclic olefins.
Applying causal mediation methods to clinical trial data: What can we learn about why our interventions (don't) work?
Authors: Whittle R. , Mansell G. , Jellema P. , van der Windt D.
Published: October 2016

Background

Many randomized controlled trials (RCTs) of psychosocial interventions for low back pain (LBP) have been found to have only small effects on disability outcomes. Investigations of the specific mechanisms that may lead to an improvement in outcome have therefore been called for.

Methods

We present an application of the causal inference approach to mediation analysis using the example of a cluster RCT in a primary care population with (sub)acute LBP randomized to either usual GP care (n = 171) or a minimal psychosocial intervention (n = 143). Mediation analysis explored the causal pathway between treatment allocation and disability at 3 months by considering pain catastrophizing, fear‐avoidance beliefs, distress and receiving and following advice as potential mediators, all measured at 6 weeks. We have attempted to explain this approach to mediation analysis in a step‐by‐step manner to help clinical researchers apply this method more easily.

Results

In unadjusted mediation analyses, fear‐avoidance beliefs were identified as a mediator of treatment on disability, with an indirect effect of −0.30 (95% CI: −0.86, −0.03), although this relationship was found to be non‐significant after adjusting for age, gender and baseline scores. This finding supports the trial authors’ hypothesis that while fear‐avoidance beliefs are important, this intervention may not have targeted them strongly enough to lead to change.

Conclusion

The use of mediation analysis to identify what factors may be part of the causal pathway between intervention and outcome, regardless of whether the intervention was successful, can provide useful information and insight into how to improve future interventions.

Significance

This study presents a step‐by‐step approach to mediation analysis using the causal inference framework to investigate why a psychosocial intervention for LBP was unsuccessful. Fear‐avoidance beliefs were found to mediate the relationship between treatment and disability, although not when controlling for baseline scores.
Modified Electrodes Based on Poly[(2E)‐2‐(Azulen‐1‐ylmethylidene)hydrazinecarbothioamide] for Heavy Metal Ions Complexation
Authors: Buica George‐Octavian , Birzan Liviu , Tecuceanu Victorita , Razus Alexandru C. , Arnold Georgiana‐Luiza , Ungureanu Eleonora‐Mihaela
Published: October 2016

The synthesis and electrochemical characterization of a new azulene‐thiourea like complexing monomer namely, (2E)‐2‐(azulen‐1‐ylmethylidene) hydrazinecarbothioamide (L) is reported. The electropolymerization of L in acetonitrile on glassy carbon electrodes, put in evidence by EQCM and ferrocene redox assay probe, led to the immobilization of the complexing monomer on the electrode surface. The polyL modified electrodes were electrochemically characterized and their morphology was evaluated using scanning electron microscopy. The complexing abilities of L and polyL towards heavy metal ions were highlighted.
Dynamic double coating, electrophoretic method with indirect detection for the simultaneous quantification of mono‐ and divalent cations in various water samples
Authors: Kowalski Piotr , Olędzka Ilona , Plenis Alina , Bączek Tomasz
Published: October 2016

An indirect UV detection method based on CE was developed and validated to determinate 12 metal cations, including alkali, alkaline earth, transition metal, and ammonium. In this paper, a new electrolyte system (pH 4.22) contained 20 mM benzimidazole (as co‐ion), 75 mM acetic acid (as a counter‐ion) as well as 0.6 mM 18‐crown‐6 ether was applied. The metal ions were completely separated within 8 min under hydrodynamic mode injection with a running voltage of 20 kV at 25 ± 0.1°C. Additional use of the dynamic double coating method enabled to get an excellent repeatability of migration times and quantitative parameters for all analytes. The repeatability of migration times for analytes were less than 0.9% and peak areas and peak heights ranged from 3.7 to 7.2 and 3.9 to 7.7%, respectively (n = 6). The proposed technique proved to be definitely faster and less expensive in comparison to currently employed methods. In this work, we discuss also the linear range, method detection limits as well as precision and accuracy. The applicability of the elaborated method was authenticated by the quantification of metal ions in commercially available mineral water, tap water, and selected medical injection samples.
A hydrophobic ionic liquid compartmentalized sampling/labeling and its separation techniques in polydimethylsiloxane microchip capillary electrophoresis
Authors: Quan Hong Hua , Li Ming , Huang Yan , Hahn Jong Hoon
Published: October 2016

This paper demonstrates a novel compartmentalized sampling/labeling method and its separation techniques using a hydrophobic ionic liquid (IL)—1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)‐imidate (BmimNTf2)—as the immiscible phase, which is capable of minimizing signal losses during microchip capillary electrophoresis (MCE). The MCE device consists of a silica tube connected to a straight polydimethylsiloxane (PDMS) separation channel. Poly(diallyldimethylammonium chloride) (PDDAC) was coated on the inner surface of channel to ease the introduction of IL plugs and enhance the IL wetting on the PDMS surface for sample releasing. Electroosmotic flow (EOF)‐based sample compartmentalization was carried out through a sequenced injection into sampling tubes with the following order: leading IL plug/sample segment/terminal IL plug. The movement of the sample segment was easily controlled by applying an electrical voltage across both ends of the chip without a sample volume change. This approach effectively prevented analyte diffusion before injection into MCE channels. When the sample segment was manipulated to the PDDAC‐modified PDMS channel, the sample plug then was released from isolation under EOF while IL plugs adsorbed onto channel surfaces owing to strong adhesion. A mixture of flavin adenine nucleotides (FAD) and flavin mononucleotides (FMN) was successfully separated on a 2.5 cm long separation channel, for which the theoretical numbers of plates were 15 000 and 17 000, respectively. The obtained peak intensity was increased 6.3‐fold over the corresponding value from conventional electrokinetic injection with the same sampling time. Furthermore, based on the compartmented sample segment serving as an interim reactor, an on‐chip fluorescence labeling is demonstrated.
Evaluation of protein separation mechanism and pore size distribution in colloidal self‐assembled nanoparticle sieves for on‐chip protein sizing
Authors: Azim Mohammad , Malekpourkoupaei Ali , Ye Wenmin , Jemere Abebaw B. , Harrison D. Jed
Published: October 2016

The separation behavior of 6.5–66 kDa proteins in silica particle array‐based sieves formed by colloidal self‐assembly in microchips is reported across a pore size range of 22–103 nm. The protein separation and resolution improves markedly with decreasing pore size. The variation of electrophoretic mobility with molecular weight of SDS–protein complexes and with particle size was evaluated using the Ogston sieving equation for a random pore gel structure, and using the modified Giddings equation developed by Wirth for uniform pore structures. The Wirth/Giddings equation provides the best fit for estimation of molecular weight of proteins, and demonstrates that even though experimental evidence shows there is some dispersion in measured pore sizes, these structures can best be described as having a uniform pore size.
Anti‐Fas conjugated hyaluronic acid microsphere gels for neural stem cell delivery
Authors: Shendi Dalia , Albrecht Dirk R. , Jain Anjana
Published: October 2016

Central nervous system (CNS) injuries and diseases result in neuronal damage and loss of function. Transplantation of neural stem cells (NSCs) has been shown to improve locomotor function after transplantation. However, due to the immune and inflammatory response at the injury site, the survival rate of the engrafted cells is low. Engrafted cell viability has been shown to increase when transplanted within a hydrogel. Hyaluronic acid (HA) hydrogels have natural anti‐inflammatory properties and the backbone can be modified to introduce bioactive agents, such as anti‐Fas, which we have previously shown to promote NSC survival while suppressing immune cell activity in bulk hydrogels in vitro. Although bulk HA hydrogels have shown to promote stem cell survival, microsphere gels for NSC encapsulation and delivery may have additional advantages. In this study, a flow‐focusing microfluidic device was used to fabricate either vinyl sulfone‐modified HA (VS‐HA) or anti‐Fas‐conjugated HA (anti‐Fas HA) microsphere gels encapsulated with NSCs. The majority of encapsulated NSCs remained viable for at least 24 h in the VS‐HA and anti‐Fas HA microsphere gels. Moreover, T‐cells cultured in suspension with the anti‐Fas HA microsphere gels had reduced viability after contact with the microsphere gels compared to the media control and soluble anti‐Fas conditions. This approach can be adapted to encapsulate various cell types for therapeutic strategies in other physiological systems in order to increase survival by reducing the immune response. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 608–618, 2017.
Sarcopenic Obesity and Its Temporal Associations With Changes in Bone Mineral Density, Incident Falls, and Fractures in Older Men: The Concord Health and Ageing in Men Project
Authors: Scott David , Seibel Markus , Cumming Robert , Naganathan Vasi , Blyth Fiona , Le Couteur David G , Handelsman David J , Waite Louise M , Hirani Vasant
Published: October 2016

Body composition and muscle function have important implications for falls and fractures in older adults. We aimed to investigate longitudinal associations between sarcopenic obesity and its components with bone mineral density (BMD) and incident falls and fractures in Australian community-dwelling older men. A total of 1486 men aged ≥70 years from the Concord Health and Ageing in Men Project (CHAMP) study were assessed at baseline (2005–2007), 2-year follow-up (2007–2009; n = 1238), and 5-year follow-up (2010–2013; n = 861). At all three time points, measurements included appendicular lean mass (ALM), body fat percentage and total hip BMD, hand-grip strength, and gait speed. Participants were contacted every 4 months for 6.1 ± 2.1 years to ascertain incident falls and fractures, the latter being confirmed by radiographic reports. Sarcopenic obesity was defined using sarcopenia algorithms of the European Working Group on Sarcopenia (EWGSOP) and the Foundation for the National Institutes of Health (FNIH) and total body fat ≥30% of total mass. Sarcopenic obese men did not have significantly different total hip BMD over 5 years compared with non-sarcopenic non-obese men (p > 0.05). EWGSOP-defined sarcopenic obesity at baseline was associated with significantly higher 2-year fall rates (incidence rate ratio [IRR] 1.66; 95% confidence interval [CI] 1.16–2.37), as were non-sarcopenic obesity (1.30; 1.04–1.62) and sarcopenic non-obesity (1.58; 1.14–2.17), compared with non-sarcopenic non-obese. No association with falls was found for sarcopenic obesity using the FNIH definition (1.01; 0.63–1.60), but after multivariable adjustment, the FNIH-defined non-sarcopenic obese group had a reduced hazard for any 6-year fracture compared with sarcopenic obese men (hazard ratio 0.44; 95% CI 0.23–0.86). In older men, EWGSOP-defined sarcopenic obesity is associated with increased fall rates over 2 years, and FNIH-defined sarcopenic obese men have increased fracture risk over 6 years compared with non-sarcopenic obese men. © 2016 American Society for Bone and Mineral Research.
Comparative Safety and Effectiveness of Denosumab Versus Zoledronic Acid in Patients With Osteoporosis: A Cohort Study
Authors: Choi Nam-Kyong , Solomon Daniel H , Tsacogianis Theodore N , Landon Joan E , Song Hong Ji , Kim Seoyoung C
Published: October 2016

Limited head-to-head comparative safety and effectiveness data exist between denosumab and zoledronic acid in real-world healthcare. We aimed to examine the safety and effectiveness of denosumab compared to zoledronic acid with regard to risk of serious infection and cardiovascular disease (CVD) and osteoporotic fracture. We conducted a cohort study using claims data (2009–2013) from a US commercial insurance plan database. We included patients aged ≥50 years who were newly initiated on denosumab or zoledronic acid. The primary outcomes were (1) hospitalization for serious infection; (2) composite CVD endpoint including myocardial infarction, stroke, coronary revascularization, and heart failure; and (3) nonvertebral osteoporotic fracture including hip, wrist, forearm, and pelvic fracture. To control for potential confounders, we used 1:1 propensity score (PS) matching. Cox proportional hazards models compared the risk of serious infection, CVD, and osteoporotic fracture within 365 days after initiation of denosumab versus zoledronic acid. After PS matching, a total of 2467 pairs of denosumab and zoledronic acid initiators were selected with a mean age of 63 years and 96% were female. When compared with zoledronic acid, denosumab was not associated with an increased risk of serious infection (HR 0.81; 95% confidence interval [CI], 0.55 to 1.21) or CVD (HR 1.11; 95% CI, 0.60 to 2.03). Similar results were obtained for each component of CVD. The risk of osteoporotic fracture was also similar between groups (HR 1.21; 95% CI, 0.84 to 1.73). This large population-based cohort study shows that denosumab and zoledronic acid have comparable clinical safety and effectiveness with regard to the risk of serious infection, CVD, and osteoporosis fracture within 365 days after initiation of medications. © 2016 American Society for Bone and Mineral Research.
Impact of Competing Risk of Mortality on Association of Weight Loss With Risk of Central Body Fractures in Older Men: A Prospective Cohort Study
Authors: Ensrud Kristine E , Harrison Stephanie L , Cauley Jane A , Langsetmo Lisa , Schousboe John T , Kado Deborah M , Gourlay Margaret L , Lyons Jennifer G , Fredman Lisa , Napoli Nicolas , Crandall Carolyn J , Lewis Cora E , Orwoll Eric S , Stefanick Marcia L , Cawthon Peggy M ,   for the Osteoporotic Fractures in Men (MrOS) Research Group
Published: October 2016

To determine the association of weight loss with risk of clinical fractures at the hip, spine, and pelvis (central body fractures [CBFs]) in older men with and without accounting for the competing risk of mortality, we used data from 4523 men (mean age 77.5 years). Weight change between baseline and follow-up (mean 4.5 years between examinations) was categorized as moderate loss (loss ≥10%), mild loss (loss 5% to <10%), stable (<5% change) or gain (gain ≥5%). Participants were contacted every 4 months after the follow-up examination to ascertain vital status (deaths verified by death certificates) and ask about fractures (confirmed by radiographic reports). Absolute probability of CBF by weight change category was estimated using traditional Kaplan-Meier method and cumulative incidence function accounting for competing mortality risk. Risk of CBF by weight change category was determined using conventional Cox proportional hazards regression and subdistribution hazards models with death as a competing risk. During an average of 8 years, 337 men (7.5%) experienced CBF and 1569 (34.7%) died before experiencing this outcome. Among men with moderate weight loss, CBF probability was 6.8% at 5 years and 16.9% at 10 years using Kaplan-Meier versus 5.7% at 5 years and 10.2% at 10 years using a competing risk approach. Men with moderate weight loss compared with those with stable weight had a 1.6-fold higher adjusted risk of CBF (HR 1.59; 95% CI, 1.06 to 2.38) using Cox models that was substantially attenuated in models accounting for competing mortality risk and no longer significant (subdistribution HR 1.16; 95% CI, 0.77 to 1.75). Results were similar in analyses substituting hip fracture for CBF. Older men with weight loss who survive are at increased risk of CBF, including hip fracture. However, ignoring the competing mortality risk among men with weight loss substantially overestimates their long-term fracture probability and relative fracture risk. © 2016 American Society for Bone and Mineral Research.
Modulation of the specific immune response in Balb/c mice by intranasal application of recombinant H1D2 chimera
Authors: Mrkić Ivan , Minić Rajna , Bulat Tanja , Aradska Jana , Atanasković‐Marković Marina , Drakulić Branko , Gavrović‐Jankulović Marija
Published: October 2016

BACKGROUND

Group 1 and group 2 allergens from house dust mite are the major elicitors of respiratory allergic diseases and the main candidates for immunotherapy.

RESULTS

The potential therapeutic role of a chimera composed of recombinant Der p 2 (D2) linked to Influenza A virus hemagglutinin 1 (H1) for intranasal application was created, expressed and tested in a mouse model. H1D2 and D2 were produced by genetic engineering in Escherichia coli and their primary structure was confirmed by mass fingerprint. Both antigens preserved IgE reactivity in immunoblot with serum from seven house dust mite allergic persons. Balb/c mice were sensitized with D2 allergen in alum and subsequently received H1D2 or D2, intranasally. The reduced levels of serum D2 specific IgE, together with the increased serum specific IgG and IgA were detected in both groups which received H1D2 and D2 intranasally. A higher level of effector CD4+CD25+ spleen lymphocytes was found only in the group of mice which received i.n. H1D2.

CONCLUSION

H1D2 chimera can have therapeutic potential in Der p 2 allergic persons as dual vaccine which, beside protective allergen specific, can provide protective antibodies against Influenza A virus hemagglutinin 1. © 2016 Society of Chemical Industry
The influence of the Fe2O3 content on the Raman spectra of sapphires
Authors: Phan D. T. M. , Häger T. , Hofmeister W.
Published: October 2016

In this paper, we study the influence of the Fe2O3 content on the Raman spectra of sapphires by confocal micro Raman spectroscopy and Electron Probe Micro Analysis (EPMA) on a wide variety of sapphire samples collected from 18 different mining regions. Almost all of the samples have a basaltic origin, which is often characterized by a high Fe2O3 content. The Raman peak positions of the two peaks at 418.3 cm−1 and 577.7 cm−1 shift in the investigated area linearly with the Fe2O3 content. This correlation can be applied in, for example, estimating the Fe2O3 content in sapphire or corundum in general and contributes in distinguishing sapphires from different origins. Copyright © 2016 John Wiley & Sons, Ltd.
Extraction and identification of mixed pesticides' Raman signal and establishment of their prediction models
Authors: Zhai Chen , Peng Yankun , Li Yongyu , Chao Kuanglin
Published: October 2016

A nondestructive and sensitive method is developed to determine mixed pesticides of acetamiprid, chlorpyrifos and carbendazim in apple samples by surface‐enhanced Raman spectroscopy (SERS). Self‐modeling mixture analysis (SMA) was used to identify and extract the Raman signals of each pesticide from the spectra of apples contaminated with mixed pesticides. Results indicate that the obtained SERS signal intensities of each pesticide in their mixture have no obvious difference to the signal intensities of the corresponding pure pesticide at a low concentration. The lowest detectable level of acetamiprid, chlorpyrifos and carbendazim in apple are 0.0054 mg/kg, 0.064 mg/kg and 0.014 mg/kg, respectively, which are sensitive enough for identifying apple contaminated with pesticides above the maximum residue limit. The predicted values of each pesticide in their mixture are obtained using the prediction model based on the Raman signal of the single pesticide. The correlation coefficients of predicted values and actual values are 0.893 for acetamiprid, 0.926 for chlorpyrifos and 0.938 for carbendazim, respectively. The method presents the ultrasensitive SERS performance for quantifying residual pesticides in apple samples without sample pre‐treatment, showing great potential to serve as a useful means for monitoring pesticide residues used in mixed state. Copyright © 2016 John Wiley & Sons, Ltd.
Laser Beam Welding of Copper
Authors: Reisgen Uwe , Olschok Simon , Turner Christoph
Published: October 2016

Laser beam welding of copper, especially for comparatively high plate thicknesses and low welding speeds, is very challenging critical welding defects are very likely to occur. By reducing the ambient pressure, it becomes possible to increase the process capability in a huge amount. The so called laser beam welding in vacuum (LaVa) process variant allows high quality welding of copper at welding speeds below 2 m/min and thereby a high penetration depth with a comparatively low laser power.
Laser Processing of Sapphire: Application Know‐How Matters
Authors: Berndt Michael , Danner Markus
Published: October 2016

We demonstrate how lasers can be applied for processing of sapphire. Due to its hardness, sapphire is difficult to process with mechanical tools and laser processing is the tool of choice. Based on this example, we show how novel laser material processes are being qualified and how different material qualities as well as process requirements regarding speed and accuracy define an applicative solution consisting of a combination of laser source and processing optics. Thus, one thing becomes particularly apparent: application know‐how matters.
Cutting Plastic Film
Authors: Brandt Thorsten
Published: October 2016

In our daily lives, everywhere we look, we encounter plastic film. It has become such an integral part of our lives, that we take it for granted. In some cases, only professionals can even tell that certain product components started out as plastic film. It is one more reason to take a closer look at the topic of film and its applications and processing methods. We would like to present a few main areas and products, show you which materials are typically used and how the film is processed. In this context, we're going to examine the possibilities of using laser technology in particular.
Transmission Laser Welding of Large Plastic Components
Authors: Borges Malte
Published: October 2016

More efficient drives, more complex controls and lightweight constructions: these components are becoming increasingly important to cut down energy consumption in the automotive world. Modern joining technologies also make it possible now to optimize large components for car making applications. Laser technologies make a crucial contribution here.
Enhanced Bioactivity of α‐Tocopheryl Succinate Based Block Copolymer Nanoparticles by Reduced Hydrophobicity
Authors: Palao‐Suay Raquel , Aguilar María Rosa , Parra‐Ruiz Francisco J. , Maji Samarendra , Hoogenboom Richard , Rohner Nathan A. , Thomas Susan N. , Román Julio San
Published: October 2016

Well‐structured amphiphilic copolymers are necessary to obtain self‐assembled nanoparticles (NPs) based on synthetic polymers. Highly homogeneous and monodispersed macromolecules obtained by controlled polymerization have successfully been used for this purpose. However, disaggregation of the organized macromolecules is desired when a bioactive element, such as α‐tocopheryl succinate, is introduced in self‐assembled NPs and this element must be exposed or released to exert its action. The aim of this work is to demonstrate that the bioactivity of synthetic NPs based on defined reversible addition‐fragmentation chain transfer polymerization copolymers can be enhanced by the introduction of hydrophilic comonomers in the hydrophobic segment. The amphiphilic terpolymers are based on poly(ethylene glycol) (PEG) as hydrophilic block, and a hydrophobic block based on a methacrylic derivative of α‐tocopheryl succinate (MTOS) and small amounts of 2‐hydroxyethyl methacrylate (HEMA) (PEG‐b‐poly(MTOS‐co‐HEMA)). The introduction of HEMA reduces hydrophobicity and introduces “disorder” both in the homogeneous blocks and the compact core of the corresponding NPs. These NPs are able to encapsulate additional α‐tocopheryl succinate (α‐TOS) with high efficiency and their biological activity is much higher than that described for the unmodified copolymers, proposedly due to more efficient degradation and release of α‐TOS, demonstrating the importance of the hydrophilic–hydrophobic balance.

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