bluuebunny/crossref_metadata_2025 huggingface dataset:
Facilitated Electron Hopping in Nanolayer Oxygen‐Insensitive Glucose Biosensor for Application in a Complex Matrix
Authors: Grattieri Matteo , Tucci Matteo , Bestetti Massimiliano , Trasatti Stefano , Cristiani Pierangela
Published: August 2016

Electrochemical experimental evidence of facilitated electron transfer in a sub‐micrometer biosensor is presented. Layer‐by‐layer self‐assembled deposition provides the unique advantage to specifically control the thickness of the biosensors, allowing an oxygen‐insensitive device with a film thickness of 70 nanometers to be obtained. The biosensor is based on a poly(allylamine) osmium redox mediator and glucose 1‐oxidase. The immobilized enzyme contributes to the signal generation through the full biosensor thickness, with no loss of “active enzyme” in the outer layer of the biosensor through reaction with oxygen, as reported in the case of thick redox hydrogels. The application of the biosensor in complex matrices was approached with tests in wastewater. Encapsulation of the biosensor with Nafion® membrane ensured the protection of the enzyme molecules from the external environment, allowing the successful application of the sensor in a complex matrix.
Modulation by Amino Acids: Toward Superior Control in the Synthesis of Zirconium Metal–Organic Frameworks
Authors: Gutov Oleksii V. , Molina Sonia , Escudero‐Adán Eduardo C. , Shafir Alexandr
Published: August 2016

The synthesis of zirconium metal–organic frameworks (Zr MOFs) modulated by various amino acids, including l‐proline, glycine, and l‐phenylalanine, is shown to be a straightforward approach toward functional‐group incorporation and particle‐size control. High yields in Zr‐MOF synthesis are achieved by employing 5 equivalents of the modulator at 120 °C. At lower temperatures, the method provides a series of Zr MOFs with increased particle size, including many suitable for single‐crystal X‐ray diffraction studies. Furthermore, amino acid modulators can be incorporated at defect sites in Zr MOFs with an amino acid/ligand ratio of up to 1:1, depending on the ligand structure and reaction conditions. The MOFs obtained through amino acid modulation exhibit an improved CO2‐capture capacity relative to nonfunctionalized materials.
Synthesis, Structure and Catalytic Activity of NHC–AgI Carboxylate Complexes
Authors: Wong Valerie H. L. , Vummaleti Sai V. C. , Cavallo Luigi , White Andrew J. P. , Nolan Steven P. , Hii King Kuok (Mimi)
Published: August 2016

A general synthetic route was used to prepare 15 new N‐heterocyclic carbene (NHC)–AgI complexes bearing anionic carboxylate ligands [Ag(NHC)(O2CR)], including a homologous series of complexes of sterically flexible ITent ligands, which permit a systematic spectroscopic and theoretical study of the structural and electronic features of these compounds. The complexes displayed a significant ligand‐accelerated effect in the intramolecular cyclisation of propargylic amides to oxazolidines. The substrate scope is highly complementary to that previously achieved by NHC–Au and pyridyl–AgI complexes.
A Sequential Method to Prepare Polymorphs and Solvatomorphs of [Fe(1,3‐bpp)2](ClO4)2⋅nH2O (n=0, 1, 2) with Varying Spin‐Crossover Behaviour
Authors: Bartual‐Murgui Carlos , Codina Carlota , Roubeau Olivier , Aromí Guillem
Published: August 2016

Two polymorphs of the spin crossover (SCO) compound [Fe(1,3‐bpp)2](ClO4)2 (1 and 2; 1,3‐bpp=2‐(pyrazol‐1‐yl)‐6‐(pyrazol‐3‐yl)pyridine) were prepared using a novel, stepwise procedure. Crystals of 1 deposit from dry solvents, while 2 is obtained from a solid‐state procedure, by sequentially removing lattice H2O molecules from the solvatomorph [Fe(1,3‐bpp)2](ClO4)2⋅2 H2O (2⋅2 H2O), using single‐crystal‐to‐single‐crystal (SCSC) transformations. Hydrate 2⋅2 H2O is obtained through the same reaction as 1, now with 2.5 % of water added. Compounds 2 and 2⋅2 H2O are unstable in the atmosphere and absorb or lose one equivalent of water, respectively, to both yield the stable solvatomorph [Fe(1,3‐bpp)2](ClO4)2⋅H2O (2⋅H2O), also following SCSC processes. The four derivatives have been characterised by single‐crystal X‐ray diffraction (SCXRD). Furthermore, the homogeneity of the various compounds as well as their SCSC interconversions have been confirmed by powder X‐ray diffraction (PXRD). Polymorphs 1 and 2 exhibit abrupt SCO behaviour near room temperature with T1/2↑=279/316 K and T1/2↓=276/314 K (near 40 K of shift) and different cooperativity.
Communication between Discrete Nanostructures Triggered by Fine Tuning of an External Stimulus
Authors: Schilirò Matteo , Contino Annalinda , Millesi Salvatrice , Maccarrone Giuseppe , Gulino Antonino
Published: August 2016

The design of molecular architectures able to transfer mass to each other is a field of extreme importance. In the present study it is shown that two especially designed covalently assembled nanostructures can interchange Cu2+ ions upon an external OH− trigger. The obtained solid interfaces are of interest for signaling, communication, memory storage and optical devices.
Synthesis of an Open‐Cage Structure POSS Containing Various Functional Groups and Their Effect on the Formation and Properties of Langmuir Monolayers
Authors: Dutkiewicz Michał , Karasiewicz Joanna , Rojewska Monika , Skrzypiec Marta , Dopierała Katarzyna , Prochaska Krystyna , Maciejewski Hieronim
Published: August 2016

Recently, silsesquioxanes have been recognized as a new group of film‐forming materials. This study has been aimed at determining the effect of the kind of functional groups present in two different open‐cage structure POSS molecules on the possibility of the formation of Langmuir monolayers and their properties. To achieve this goal, two new POSS derivatives (of open‐cage structures) containing polyether and fluoroalkyl functional groups have been synthesized on the basis of a hydrosilylation process. An optimization of the process was performed, which makes it possible to obtain the above‐mentioned derivatives with high yields. In the next step, the Langmuir technique was applied to measurements of the surface pressure (π) − the mean molecular area (A) isotherms during the compression of monolayers formed by molecules of the two POSS derivatives considered. Subsequently, the monolayers were transferred onto quartz plates according to the Langmuir–Blodgett technique. Both derivatives are able to form insoluble Langmuir films at the air–water interface, which can be transferred onto a solid substrate and effectively change its wetting properties.
Palladium‐Catalyzed N‐Arylation of Iminodibenzyls and Iminostilbenes with Aryl‐ and Heteroaryl Halides
Authors: Huang Wenliang , Buchwald Stephen L.
Published: August 2016

Compounds containing the iminodibenzyl and iminostilbene ring systems are prevalent in medicinal targets and functional materials. Herein, we report palladium‐catalyzed conditions for the N‐arylation of these ring systems. This protocol could be applied to a variety of (hetero)aryl chloride and bromide substrates, including ones, which are sterically hindered or those containing a variety of functional groups. Use of the fourth‐generation palladacycle precatalyst gave good to excellent yields by using low palladium‐catalyst loadings (0.1 to 1 mol %).
Pd‐PEPPSI‐IHeptCl: A General‐Purpose, Highly Reactive Catalyst for the Selective Coupling of Secondary Alkyl Organozincs
Authors: Atwater Bruce , Chandrasoma Nalin , Mitchell David , Rodriguez Michael J. , Organ Michael G.
Published: August 2016

Dichloro[1,3‐bis(2,6‐di‐4‐heptylphenyl)imidazol‐2‐ylidene](3‐chloropyridyl)palladium(II) (Pd‐PEPPSI‐IHeptCl), a new, very bulky yet flexible Pd–N‐heterocyclic carbene (NHC) complex has been evaluated in the cross‐coupling of secondary alkylzinc reactants with a wide variety of oxidative addition partners in high yields and excellent selectivity. The desired, direct reductive elimination branched products were obtained with no sign of migratory insertion across electron‐rich and electron‐poor aromatics and all forms of heteroaromatics (five and six membered). Impressively, there is no impact of substituents at the site of reductive elimination (i.e., ortho or even di‐ortho), which has not yet been demonstrated by another catalyst system to date.
Identification of Highly Potent Protein Kinase C‐Related Kinase 1 Inhibitors by Virtual Screening, Binding Free Energy Rescoring, and in vitro Testing
Authors: Slynko Inna , Schmidtkunz Karin , Rumpf Tobias , Klaeger Susan , Heinzlmeir Stephanie , Najar Abdulkarim , Metzger Eric , Kuster Bernhard , Schüle Roland , Jung Manfred , Sippl Wolfgang
Published: August 2016

Despite the considerable interest in protein kinase C‐related kinase 1 (PRK1) as a target in cancer research, there is still a lack of PRK1 inhibitors with suitable selectivity profiles and physicochemical properties. To identify new PRK1 inhibitors we applied a virtual screening approach, which combines ensemble docking, minimization of the protein–ligand complex, binding free energy calculations, and application of quantitative structure–activity relationship (QSAR) models for predicting in vitro activity. The developed approach was then applied in a prospective manner to screen available libraries of kinase inhibitors from Selleck and GlaxoSmithKline (GSK). Compounds that showed favorable prediction were then tested in vitro for PRK1 inhibition. Some of the hits were found to inhibit PRK1 in the low‐nanomolar range. Three in vitro hits were additionally tested in a mass‐spectrometry‐based cellular kinase profiling assay to examine selectivity. Our findings show that nanomolar and drug‐like inhibitors can be identified by the virtual screening approach presented herein. The identified inhibitors are valuable tools for gaining a better understanding of PRK1 inhibition, and the identified hits can serve as starting points for further chemical optimization.
Frequency of psycho‐oncologic and social service counseling in cancer centers relative to center site and hospital characteristics: Findings from 879 center sites in Germany, Austria, Switzerland, and Italy
Authors: Kowalski Christoph , Ferencz Julia , Singer Susanne , Weis Ilse , Wesselmann Simone
Published: August 2016

BACKGROUND

There is extensive evidence that patients with cancer and cancer survivors have a strong need for expert support in relation to the psychological and social consequences of the disease. The requirements set out in the German Cancer Society's cancer center certification system include the routine provision of psycho‐oncologic care (POC) and social service counseling for every patient. The current study investigated which organizational and structural characteristics in hospitals account for variations in psychosocial care provision in these centers.

METHODS

Data routinely collected during the certification process regarding the percentages of psychosocial care provision and characteristics of center sites and hospitals were matched with data with regard to size of the municipality, teaching hospital status, and institutional ownership. Linear multilevel regression analyses were performed to identify the characteristics of hospitals and center sites that were related to psychosocial care provision.

RESULTS

Substantial differences were found for different types of cancer (eg, a greater provision of psychosocial care in centers specializing in breast rather than prostate cancer). There was more POC provision in longer‐certified centers and less in rural areas and university hospitals. Much of the variation between hospitals remains unexplained.

CONCLUSIONS

Although the implementation of mandatory psychosocial services generally provides patients with access to POC and social service counseling, the wide differences in the provision of counseling indicate that additional measures are needed to avoid inequalities resulting from the center at which a patient receives cancer treatment. Cancer 2016;122:3538–3545. © 2016 American Cancer Society
Expression of homeobox genes in the mouse olfactory epithelium
Authors: Parrilla Marta , Chang Isabelle , Degl'Innocenti Andrea , Omura Masayo
Published: August 2016

Homeobox genes constitute a large family of genes widely studied because of their role in the establishment of the body pattern. However, they are also involved in many other events during development and adulthood. The main olfactory epithelium (MOE) is an excellent model to study neurogenesis in the adult nervous system. Analyses of homeobox genes during development show that some of these genes are involved in the formation and establishment of cell diversity in the MOE. Moreover, the mechanisms of expression of odorant receptors (ORs) constitute one of the biggest enigmas in the field. Analyses of OR promoters revealed the presence of homeodomain binding sites in their sequences. Here we characterize the expression patterns of a set of 49 homeobox genes in the MOE with in situ hybridization. We found that seven of them (Dlx3, Dlx5, Dlx6, Msx1, Meis1, Isl1, and Pitx1) are zonally expressed. The homeobox gene Emx1 is expressed in three guanylate cyclase+ populations, two located in the MOE and the third one in an olfactory subsystem known as Grüneberg ganglion located at the entrance of the nasal cavity. The homeobox gene Tshz1 is expressed in a unique patchy pattern across the MOE. Our findings provide new insights to guide functional studies that aim to understand the complexity of transcription factor expression and gene regulation in the MOE. J. Comp. Neurol. 524:2713–2739, 2016. © 2016 Wiley Periodicals, Inc.
Rhodium and Iridium Fluorido and Bifluorido Complexes Derived from Peroxido Precursors
Authors: Baumgarth Hanna , Meier Gregor , Braun Thomas , Braun‐Cula Beatrice
Published: August 2016

The rhodium and iridium fluorido bifluorido complexes trans‐[Rh(4‐C5F4N)(F)(FHF)(CNtBu)(PEt3)2] (1) and trans‐[Ir(4‐C5F4N)(F)(FHF)(CNtBu)(PiPr3)2] (2) have been synthesized by protonation of the peroxido complexes trans‐[M(4‐C5F4N)(O2)(CNtBu)(PR3)2] with an HF source (M = Rh, R = Et; M = Ir, R = iPr). Abstraction of the coordinated HF resulted in the formation of the difluorido compounds trans‐[M(4‐C5F4N)(F)2(CNtBu)(PR3)2] (4: M = Rh, R = Et; 5: M = Ir, R = iPr).
Effect of Anionic Electrolytes and Precursor Concentrations on the Electrodeposited Pt Structures
Authors: Kim Dajeong , Kim Jongwon
Published: August 2016

Electrodeposition of functional metal surfaces has received great attention because of their useful applications. Recently, interesting electrodeposition behavior of Pt at −0.8 V (vs. Ag/AgCl) was reported, where underpotential deposited H (Hupd) layers played a unique role in the electrodeposition. Here, we report the effect of anionic electrolytes and precursor concentrations on the electrochemical deposition behavior of Pt. Depending on these two experimental parameters, two distinct Pt structures, monolayer Pt films and Pt spheres, were electrodeposited at −0.8 V. In addition to the underpotential deposited H (Hupd) layers formed at −0.8 V, the adsorption of Cl− also plays a significant role in determining the electrodeposited Pt structures. When the PtCl42− concentration was low and the Cl− concentration was high enough for the adsorption of PtCl42− to be blocked by the Hupd and Cl− layers, monolayer Pt films were electrodeposited. Otherwise, further electrodeposition of Pt spheres over the monolayer Pt films occurred. The effect of other halide ion adsorption and the controlled growth of Pt spheres during the Pt electrodeposition were also investigated. The electrochemical deposition behavior of Pt demonstrated in this work provides insight into the fabrication of functional Pt surfaces.
Separation of high‐purity syringol and acetosyringone from rice straw‐derived bio‐oil by combining the basification‐acidification process and column chromatography
Authors: Hao Shilai , Chen Kaifei , Cao Leichang , Zhu Xiangdong , Luo Gang , Zhang Shicheng , Chen Jianmin
Published: August 2016

Numerous technologies have been used to reclaim valuable chemicals from bio‐oil. In this study, a combination of the basification‐acidification process and column chromatography was employed for the separation of high‐purity syringol and acetosyringone from rice straw‐derived bio‐oil. The optimal conditions for the basification‐acidification process and the possible precipitation mechanism of the basification were explored. The results showed the following as the optimal conditions for the basification process: mass ratio of calcium hydroxide (Ca(OH)2) to bio‐oil, 2.0; reaction temperature, 70°C; and reaction time, 30 min. The results also showed that 1.6 mol of hydrochloric acid (HCl) per gram of bio‐oil was optimal for the acidification. The precipitation was found to proceed via a possible mechanism involving the reaction of the phenolic compounds in the bio‐oil with Ca(OH)2 to produce a precipitate. After further separation by column chromatography, purities of 91.4 and 96.2% (from gas chromatography‐mass spectrometry) were obtained for syringol and acetosyringone, respectively. Their recoveries for the whole process were 73.0 and 39.3%, respectively.
Ultra‐sensitive, rapid gold nanoparticle‐quantum dot plexcitonic self‐assembled aptamer‐based nanobiosensor for the detection of human cardiac troponin I
Authors: Rezaei Zahra , Ranjbar Bijan
Published: August 2016

Acute myocardial infarction (AMI) is one of the leading causes of death throughout the world. Usual methods for detecting AMI are expensive, time‐consuming and using blood samples as biological samples. Therefore, creating an ultra‐fast, sensitive and non‐invasive diagnostic test is necessary. Herein, a novel ultra‐sensitive, fluorescent, plasmon‐exciton coupling hybrid of a gold nanoparticle‐quantum dot (PQ)‐based aptamer nanobiosensor is presented for the detection of human cardiac troponin I (cTnI), the golden biomarker of AMI, and a preclinical test is performed within saliva. The binding of the cTnI protein to aptamer leads to a fluorescence enhancement of the plexcitonic hybrid system. The response range of this nanobiosensor is 0.4–2500 fM and the limit of detection is 0.3 fM. It seems that this novel design of nanobiosensor in the form of the PQ plexcitonic hybrid system can presents new opportunities for nanobiosensor progress.
Prospective study of guideline‐tailored therapy with direct‐acting antivirals for hepatitis C virus‐associated mixed cryoglobulinemia
Authors: Gragnani Laura , Visentini Marcella , Fognani Elisa , Urraro Teresa , De Santis Adriano , Petraccia Luisa , Perez Marie , Ceccotti Giorgia , Colantuono Stefania , Mitrevski Milica , Stasi Cristina , Del Padre Martina , Monti Monica , Gianni Elena , Pulsoni Alessandro , Fiorilli Massimo , Casato Milvia , Zignego Anna Linda
Published: August 2016

Hepatitis C virus (HCV)‐associated mixed cryoglobulinemia (MC) vasculitis commonly regresses upon virus eradication, but conventional therapy with pegylated interferon and ribavirin yields approximately 40% sustained virologic responses (SVR). We prospectively evaluated the efficacy and safety of sofosbuvir‐based direct‐acting antiviral therapy, individually tailored according to the latest guidelines, in a cohort of 44 consecutive patients with HCV‐associated MC. In two patients MC had evolved into an indolent lymphoma with monoclonal B‐cell lymphocytosis. All patients had negative HCV viremia at week 12 (SVR12) and at week 24 (SVR24) posttreatment, at which time all had a clinical response of vasculitis. The mean (±standard deviation) Birmingham Vasculitis Activity Score decreased from 5.41 (±3.53) at baseline to 2.35 (±2.25) (P < 0.001) at week 4 on treatment to 1.39 (±1.48) (P < 0.001) at SVR12 and to 1.27 (±1.68) (P < 0.001) at SVR24. The mean cryocrit value fell from 7.2 (±15.4)% at baseline to 2.9 (±7.4)% (P < 0.01) at SVR12 and to 1.8 (±5.1)% (P < 0.001) at SVR24. Intriguingly, in the 2 patients with MC and lymphoma there was a partial clinical response of vasculitis and ∼50% decrease of cryocrit, although none experienced a significant decrease of monoclonal B‐cell lymphocytosis. Adverse events occurred in 59% of patients and were generally mild, with the exception of 1 patient with ribavirin‐related anemia requiring blood transfusion. Conclusion: Interferon‐free, guideline‐tailored therapy with direct‐acting antivirals is highly effective and safe for HCV‐associated MC patients; the overall 100% rate of clinical response of vasculitis, on an intention‐to‐treat basis, opens the perspective for curing the large majority of these so far difficult‐to‐treat patients. (Hepatology 2016;64:1473‐1482)
Worse quality of life in young and recently diagnosed breast cancer survivors compared with female survivors of other cancers: A cross‐sectional study
Authors: Li Jingmei , Humphreys Keith , Eriksson Mikael , Dar Huma , Brandberg Yvonne , Hall Per , Czene Kamila
Published: August 2016

Literature focusing on health‐related quality of life (HRQoL) by cancer site among women only is scarce. This study examines HRQoL of breast cancer (BC) survivors compared with female survivors of other cancers, and to understand which subgroups of BC survivors were particularly at risk of reduced HRQoL. We placed emphasis on young (<50 years) and recently diagnosed (≤5 years) survivors, where the deficits in HRQoL were most pronounced. The cross‐sectional study consisted of 2,224 BC survivors, 8,504 non‐cancer controls and 2,205 other cancer survivors in the Karma study. We examined HRQoL differences using linear regression analyses in the whole cohort and in a subset of young and recently diagnosed BC survivors (n = 242) and female survivors of other cancers (n = 140) with comparable ages at diagnosis (43.6 vs 43.6, p = 0.917) and time since diagnosis (2.3 vs 2.8 years, p < 0.001). HRQoL was assessed using the EORTC QLQ‐C30 questionnaire. While only cognitive functioning was significantly compromised in BC survivors compared with survivors of other cancers when women of all ages were included, young BC survivors reported significantly lower HRQoL on multiple functional scales (global quality of life, emotional, role, social and cognitive functioning) and experienced more fatigue and insomnia. BC survivors with any prior medical history of mental disorders reported poorer HRQoL than those without such a history. We also observed a close–knit relationship between tumor and treatment characteristics. BC survivors perform poorly in HRQoL in comparison with female survivors of other cancers. Our results emphasize the importance of age‐ and gender‐appropriate comparison groups.
Redox Signaling through DNA
Authors: O'Brien Elizabeth , Silva Rebekah M. B. , Barton Jacqueline K.
Published: August 2016

Biological electron transfer reactions between metal cofactors are critical to many essential processes within the cell. Duplex DNA is, moreover, capable of mediating the transport of charge through its π‐stacked nitrogenous bases. Increasingly, [4Fe4S] clusters, generally redox‐active cofactors, have been found to be associated with enzymes involved in DNA processing. DNA‐binding enzymes containing [4Fe4S] clusters can thus utilize DNA charge transport (DNA CT) for redox signaling to coordinate reactions over long molecular distances. In particular, DNA CT signaling may represent the first step in the search for DNA lesions by proteins containing [4Fe4S] clusters that are involved in DNA repair. Here we describe research carried out to examine the chemical characteristics and biological consequences of DNA CT. We are finding that DNA CT among metalloproteins represents powerful chemistry for redox signaling at long range within the cell.
Metalloneurochemistry and the Pierian Spring: ‘Shallow Draughts Intoxicate the Brain’
Authors: Goldberg Jacob M. , Loas Andrei , Lippard Stephen J.
Published: August 2016

Metal ions perform critical and diverse functions in nervous system physiology and pathology. The field of metalloneurochemistry aims to understand the mechanistic bases for these varied roles at the molecular level. Here, we review research that illustrates progress toward achieving this ambitious goal and identify key challenges for the future. We examine the use of lithium as a mood stabilizer, the roles of mobile zinc and copper in the synapse, the interplay of nitric oxide and metals in retrograde signaling, and the regulation of iron homeostasis in the brain. We are beginning to uncover the principles by which receptors and transmitters utilize metal ions to modulate neurotransmission. These advances have revealed exciting new insights into the intricate mechanisms that give rise to learning, memory, and sensory perception, while opening many new avenues for further exploration.
Cross‐validation of cultural tightness and looseness measures
Authors: Uz Irem
Published: August 2016

The goal of the present study was to cross‐validate two measures of cultural tightness and looseness, CTL: one used in a comparison within the United States, and the other used in a cross‐country comparison. The former was based mainly on aggregation of state laws on controversial issues and religiosity and the latter on assessment of homogeneity in moral values among representative samples across countries. To cross‐validate these two measures, both were recomputed at the US divisional level. Despite the differences in their methods of computation, the two measures of CTL correlated highly with each other, r = .92, and with theoretical variables of interest. Further, when the two measures of CTL were used simultaneously to predict theoretical variables of interest, neither remained significant suggesting that they were substitutable with each other. Convergence of results with measures computed via maximally different methods increases the confidence in the validity of these two CTL measures.
Novel Electrochemically Treated Graphite Pencil Electrode Surfaces for the Determination of Traceα‐Naphthol in Water Samples
Authors: Rana Azeem , Kawde Abdel‐Nasser
Published: August 2016

An electrochemically treated graphite pencil electrode (PGPE) has been simply prepared for trace level determination of α‐naphthol. The pretreatment of GPE surfaces is conducted in 0.8 M NaOH by cycling the potential between +1.3 and +1.9 V for 50 CV segments at a scan rate of 100 mV s−1. The influence of the pretreatment is studied extensively, and optimum conditions are obtained. Linear sweep anodic stripping voltammetry (LSASV) is used for the determination of α‐naphthol. Based on the constructed calibration curve, a linear range of 0.01 μM to 2.0 μM with a detection limit of 1.5 nM (S/N=3) is obtained. The results reveal that the electrochemical treatment of the GPE surface improves its electrochemical catalytic activity with reference to surfaces of the non‐treated GPE. The present method is applied for the determination of trace α‐naphthol in real water samples.
Maternal PTSD and Children's Adjustment: Parenting Stress and Emotional Availability as Proposed Mediators
Authors: Samuelson Kristin W. , Wilson Christina K. , Padrón Elena , Lee Suellen , Gavron Lauren
Published: August 2016

Objectives

Maternal posttraumatic stress disorder (PTSD) is a risk factor for negative child adjustment, but it is unclear whether this association is direct (e.g., a mother's PTSD symptoms are observed, learned, and internalized by children which results in behavioral and emotional problems) or indirect, through parent–child relationship difficulties or parenting stress. We hypothesized that parenting stress and maternal emotional availability would exhibit indirect effects on relationships between maternal PTSD and children's functioning.

Method

Participants were 52 trauma‐exposed mothers and their children (aged 7–12 years). Mothers completed measures of PTSD and parenting stress and reported on their children's functioning. Emotional availability was assessed through observer‐rated mother–child interactions.

Results

Emotional availability was not related to PTSD or child outcomes. Parenting stress had a substantial indirect effect on the relationships between maternal PTSD and child emotion regulation, internalizing, and externalizing behaviors.

Conclusions

Results highlight the need to target parenting stress in interventions with trauma‐exposed families.
Changes in nail keratin observed by Raman spectroscopy after Nd:YAG laser treatment
Authors: Shin Min Kyung , Kim Tae In , Kim Wan Sun , Park Hun‐Kuk , Kim Kyung Sook
Published: August 2016

Lasers and photodynamic therapy have been considered a convergence treatment for onychomycosis, which is a fungal infection on the nail bed and nail plate. Laser therapies have shown satisfactory results without significant complications for onychomycosis; however, the mechanism of clearing remains unknown. In this work, we investigated changes in the chemical structure of nail keratin induced by Nd:YAG laser using Raman spectroscopy. Toe nails with onychomycosis were treated with 1064 nm Nd:YAG laser. After laser treatment, the disulfide band (490–590 cm−1) of nail keratin was rarely observed or was reduced in intensity. The amide I band (1500–1700 cm−1) also showed changes induced by the laser. The α‐helical (1652 cm−1) structures dominated the β‐sheet (1673 cm−1) in nontreated nail, but the opposite phenomenon was observed after laser treatment.
Determination of haloacetic acids in water using layered double hydroxides as a sorbent in dispersive solid‐phase extraction followed by liquid chromatography with tandem mass spectrometry
Authors: Alsharaa Abdulnaser , Sajid Muhammad , Basheer Chanbasha , Alhooshani Khalid , Lee Hian Kee
Published: August 2016

In the present study, highly efficient and simple dispersive solid‐phase extraction procedure for the determination of haloacetic acids in water samples has been established. Three different types of layered double hydroxides were synthesized and used as a sorbent in dispersive solid‐phase extraction. Due to the interesting behavior of layered double hydroxides in an acidic medium (pH˂4), the analyte elution step was not needed; the layered double hydroxides are simply dissolved in acid immediately after extraction to release the analytes which are then directly introduced into a liquid chromatography with tandem mass spectrometry system for analysis. Several dispersive solid‐phase extraction parameters were optimized to increase the extraction efficiency of haloacetic acids such as temperature, extraction time and pH. Under optimum conditions, good linearity was achieved over the concentration range of 0.05–100 μg/L with detection limits in the range of 0.006–0.05 μg/L. The relative standard deviations were 0.33–3.64% (n = 6). The proposed method was applied to different water samples collected from a drinking water plant to determine the concentrations of haloacetic acids.
Molecular Dynamics of Poly(ethylene‐2,5‐furanoate) (PEF) as a Function of the Degree of Crystallinity by Dielectric Spectroscopy and Calorimetry
Authors: Dimitriadis Theodoros , Bikiaris Dimitrios N. , Papageorgiou George Z. , Floudas George
Published: August 2016

The segmental and local dynamics of the bio‐based polyester poly(ethylene‐2,5‐furanoate) (PEF) are investigated by dielectric spectroscopy (DS) at atmospheric pressure as a function of temperature and frequency for samples prepared with different degrees of crystallinity. Crystallization significantly alters the segmental process as this is manifested in the dielectric strength and the distribution of relaxation times. Enhanced crystallinity by the different annealing protocols increases the glass temperature of the mobile amorphous fraction. A two‐phase model is adequate in describing the dynamics associated with the β‐process within the glassy state. However, the same model fails in describing the segmental dynamics at and above the glass temperature. The combined differential scanning calorimetry and DS results provide evidence that for samples with a degree of crystallinity of ≈40%, approximately a third of segments are located within the restricted amorphous fraction.

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Adjunctive Role of Glucagon‐Like Peptide‐1 Receptor Agonists in the Management of Type 1 Diabetes Mellitus
Authors: Harris Kira B. , Boland Cassie L.
Published: August 2016

Glucagon‐like peptide‐1 receptor agonists (GLP‐1 RAs) are commonly used in combination with insulin to manage type 2 diabetes mellitus, and four agents are currently approved for this indication: exenatide, liraglutide, dulaglutide, and albiglutide. The distinctive properties of GLP‐1 RAs—potential hemoglobin A1c (A1C) reduction, weight loss, potential to reduce insulin doses, and lower hypoglycemia risk—have made these agents potential treatment options for patients with type 1 diabetes mellitus (T1DM) as well. These positive effects are due to glucose‐dependent insulin secretion, reduced glucagon secretion, increased satiety, and delayed gastric emptying. Patients with T1DM are unable to suppress glucagon during meals, which contributes to postprandial hyperglycemia and may be improved with GLP‐1 therapy. In this review, we evaluated the available literature on the clinical efficacy and safety of GLP‐1 RAs in patients with T1DM. We conducted a search of the PubMed (1966–May 2016) and Ovid (1946–May 2016) databases. Abstracts presented at the scientific and clinical sessions of the American Diabetes Association and the American Association of Clinical Endocrinologists were also searched. The references of the published articles were also reviewed to identify additional studies appropriate for inclusion. All identified articles published in English were evaluated. Studies were included if they evaluated the clinical use or safety of GLP‐1 RAs in patients with T1DM. Twelve studies were included, with four evaluating exenatide, one evaluating exenatide extended release, and seven evaluating liraglutide. Both exenatide and liraglutide showed significant reductions in hemoglobin A1C, plasma glucose concentration, body weight, and insulin doses when administered to patients with T1DM already receiving insulin therapy, without increasing the occurrence of hypoglycemia. Adverse effects were mostly gastrointestinal in nature but were mild and transient. Patients who may benefit most are those experiencing adverse effects from insulin, those not at their A1C goal but hypoglycemia prevents insulin titration, and those who may benefit from weight loss.
Phase separation of polymer mixtures driven by photochemical reactions: current status and perspectives
Authors: Tran‐Cong‐Miyata Qui , Nakanishi Hideyuki
Published: August 2016

Phase separation of polymer mixtures induced by photo‐crosslinking and photopolymerization is summarized from the viewpoint of competing interactions in polymeric systems. First, the kinetics of photo‐crosslinking and photopolymerization are reviewed with particular emphasis on the Trommsdorff − Norrish effect in polymerization, which leads to the formation of a bimodal distribution of molecular weight at long irradiation time. The emergence of a very large molecular weight and the characteristic time for this effect to set in are utilized as a tool to control the temporal development of the resulting morphology. The shrinkage associated with the reaction and particularly its effect on the phase separation and the morphology are discussed together with the influence of the Trommsdorff − Norrish effect. Experiments on polymerization‐induced phase separation extended from binary to ternary mixtures are described where the interfacial interactions give rise to a wide variety of morphologies. Taking advantages of light, experiments using spatial and temporal modulation have been performed to control and manipulate the phase separation. These experimental results are summarized and briefly discussed in relation to the elastic deformation induced by polymerization. Finally, an overview of theoretical studies and numerical simulation of reaction‐induced phase separation is given with some comments on the complexity of the phenomena. © 2016 Society of Chemical Industry
Removal of the 5‐nitro‐2‐pyridine‐sulfenyl protecting group from selenocysteine and cysteine by ascorbolysis
Authors: Ste. Marie Emma J. , Ruggles Erik L. , Hondal Robert J.
Published: August 2016

We previously reported on a method for the facile removal of 4‐methoxybenzyl and acetamidomethyl protecting groups from cysteine (Cys) and selenocysteine (Sec) using 2,2′‐dithiobis‐5‐nitropyridine dissolved in trifluoroacetic acid, with or without thioanisole. The use of this reaction mixture removes the protecting group and replaces it with a 2‐thio(5‐nitropyridyl) (5‐Npys) group. This results in either a mixed selenosulfide bond or disulfide bond (depending on the use of Sec or Cys), which can subsequently be reduced by thiolysis. A major disadvantage of thiolysis is that excess thiol must be used to drive the reaction to completion and then removed before using the Cys‐containing or Sec‐containing peptide in further applications. Here, we report a further advancement of this method as we have found that ascorbate at pH 4.5 and 25 °C will reduce the selenosulfide to the selenol. Ascorbolysis of the mixed disulfide between Cys and 5‐Npys is much less efficient but can be accomplished at higher concentrations of ascorbate at pH 7 and 37 °C with extended reaction times. We envision that our improved method will allow for in situ reactions with alkylating agents and electrophiles without the need for further purification, as well as a number of other applications. Copyright © 2016 European Peptide Society and John Wiley & Sons, Ltd.
F2 dimer: Improved intermolecular potential energy surface using ab initio calculations
Authors: Tashakor Saeedeh , Noorbala Mohammad R. , Namazian Mansoor
Published: August 2016

A computational study on the intermolecular potential energy of 44 different orientations of F2 dimers is presented. Basis set superposition error (BSSE) corrected potential energy surface is calculated using the supermolecular approach at CCSD(T) and QCISD(T) levels of theory. The interaction energies obtained using the aug‐cc‐pVDZ and aug‐cc‐pVTZ basis sets are extrapolated to the complete basis set limit using the latest extrapolation scheme. The basis set effect is checked and it is found that the extrapolated intermolecular energies provide the best compromise between the accuracy and computational cost. Among 1320 energy points of F2–F2 system covering more relative orientations, the most stable structure of the dimers was obtained with a well depth of −146.62 cm−1 that related to cross configuration, and the most unstable structure is related to linear orientation with a well depth of −52.63 cm−1. The calculated second virial coefficients are in good agreement with experimental data. The latest extrapolation scheme of the complete basis set limit at the CCSD(T) level of theory is used to determine the intermolecular potential energy surface of the F2 dimer. Comparing the results obtained by the latest scheme with those by older schemes show that the new approach provides the best compromise between accuracy and computational cost.
Adult‐onset Pompe's disease presenting with insidious hypercapnic respiratory failure
Authors: O'Callaghan Cara , Henderson Robert , Masel Philip , Tay George , Tsang Benjamin
Published: August 2016

Orthopnoea is commonly attributed to heart failure but can be caused by diaphragm weakness, which, when severe, is often associated with hypercapnic respiratory failure. Bilateral diaphragm weakness is generally due to systemic nerve or muscle disease and usually occurs in the setting of severe generalized muscle weakness, but the diaphragm can be the initial or only muscle involved. Here, we report the case of a 39‐year‐old female who presented with slowly progressive orthopnoea and daytime somnolence. Pulmonary function studies and polysomnogram confirmed bilateral diaphragm weakness complicated by nocturnal hypoventilation and she was subsequently diagnosed with adult‐onset Pompe's disease, a rare metabolic myopathy.
Distributed model predictive control for multi‐agent flocking via neighbor screening optimization
Authors: Zhou Lifeng , Li Shaoyuan
Published: August 2016

This study presents a distributed model predictive control (MPC) strategy to achieve flocking of multi‐agent systems. Based on the relative motion between each pair of neighboring agents, we introduce a neighbor screening protocol, by which each agent only focuses on its neighbors, which have the relative motion that violates the formation of flocks. Then, a truly distributed MPC flocking algorithm (Algorithm 1) is designed with consideration of neighbor screening mechanism. Specifically, at each sampling instant, each agent monitors the information in the networked system, finds its neighbors to form its subsystem, determines the screened neighbor set, and optimizes its plan by collecting the position states within the screened subsystem. And geometric properties of the optimal path are used to guarantee the formation of the flock without inter‐agent collision. Finally, the performance and advantage of the proposed distributed MPC flocking strategy are vividly verified by the simulation results. Copyright © 2016 John Wiley & Sons, Ltd.
The asymptotic distribution of symbols on diagonals of random weighted staircase tableaux
Authors: Lohss Amanda
Published: August 2016

Staircase tableaux are combinatorial objects that were first introduced due to a connection with the asymmetric simple exclusion process (ASEP) and Askey‐Wilson polynomials. Since their introduction, staircase tableaux have been the object of study in many recent papers. Relevant to this paper, Hitczenko and Janson proved that distribution of parameters on the first diagonal is asymptotically normal. In addition, they conjectured that other diagonals would be asymptotically Poisson. Since then, only the second and the third diagonal were proven to follow the conjecture. This paper builds upon those results to prove the conjecture for the kth diagonal where k is fixed. In particular, we prove that the distribution of the number of α's (β's) on the kth diagonal, k > 1, is asymptotically Poisson with parameter 1/2. In addition, we prove that symbols on the kth diagonal are asymptotically independent and thus, collectively follow the Poisson distribution with parameter 1. © 2016 Wiley Periodicals, Inc. Random Struct. Alg., 49, 795–818, 2016
Edge‐disorder effects on electric transport in metallic graphene nanoribbons at finite temperature
Authors: Takashima Kengo , Konabe Satoru , Yamamoto Takahiro
Published: August 2016

We theoretically study electric transport in edge‐disordered armchair graphene nanoribbons (ED‐AGNRs) using an extended Hückel model combined with the non‐equilibrium Green's function formulation. We find that ED‐AGNRs exhibit the Anderson localization even at the Fermi energy (i.e., charge neutral point) originating from broken chiral symmetry of the system. Moreover, the localization length increases with temperature at low‐density edge disorder, whereas it is almost independent of temperature at high‐density one. Copyright © 2016 John Wiley & Sons, Ltd.
Chitosan‐konjac glucomannan‐cassava starch‐nanosilver composite films with moisture resistant and antimicrobial properties for food‐packaging applications
Authors: Nair Soumya B. , Alummoottil N Jyothi , Moothandasserry S. Sajeev
Published: August 2016

For the past few decades, there has been a considerable research interest in the area of food packaging using biopolymer‐based materials. Unfortunately, the water barrier property of biopolymer films is very poor. In this study, konjac glucomannan (KGM)‐chitosan films incorporated with granular cassava starch (GST) and nanosilver were prepared and characterized by FTIR, SEM, XRD, TG, and DSC analysis. Incorporation of GST has significantly improved the physicochemical properties, especially the moisture barrier properties of KGM‐chitosan films. Compared to neat KGM‐chitosan films, the water solubility and swelling capacity of GST incorporated films decreased with increase in starch content. The moisture absorbability, water vapor transmission rate, as well as oxygen transmission rate also reduced significantly in GST‐incorporated films. Contact angle measurements revealed improved hydrophobicity of GST‐incorporated KGM‐chitosan films. Incorporation of nanosilver particles further improved the thermal stability, tensile strength, and antimicrobial properties. Food‐contact tests showed that the migration of silver was significantly lower than the permitted level of migrating quantity of silver (10 mg/L) into stored bread samples, which suggests that these KGM‐chitosan‐GST‐nanosilver films would be safe to be used as food‐packaging materials. Moreover, compared to conventional food‐packaging films, these nanocomposite films also exhibited better antimicrobial activity.
Modeling and performance analysis of dynamic spectrum sharing between DSRC and Wi‐Fi systems
Authors: Wang Jian , Wu Tao , Liu Yanheng , Deng Weiwen , Oh Heekuck
Published: August 2016

The Notice of Proposed Rulemaking 13‐22 released by Federal Communications Commission unlocks the Dedicated Short Range Communication (DSRC) spectrum for Wi‐Fi availability, which undoubtedly brings unpredictable effects to the new‐emerging vehicular applications and services. To efficiently harmonize the spectrum operation between DSRC and Wi‐Fi networks, several dynamic spectrum‐sharing schemes are already proposed to improve the spectral efficiency over a limited bandwidth situation and as well to satisfy the ever‐increasing demand for bandwidth resource. Different from most previous literature that mainly focused on the performance analysis of cellular‐network‐centric spectrum sharing, we aim to analyze the performance of the mainstream dynamic spectrum‐sharing schemes specially designed for the coexistence of DSRC and Wi‐Fi networks against various combinations of network parameters through a hybrid network model and performance indicators. We employ the Poisson point process to model a hybrid network where DSRC vehicles and Wi‐Fi devices coexist, and introduce the performance indicators of spectrum efficiency and data rate to assess the utility of different spectrum sharing candidates. Through the presented hybrid model and performance indicators, we collect extensive numerical and simulation results to investigate four typical spectrum allocation schemes for DSRC and Wi‐Fi coexistence, that is non‐sharing scheme, original sharing scheme, and Qualcomm's and Cisco's proposals, respectively. The results show that the dynamic spectrum sharing in the 5.9‐GHz band can significantly raise the performance of Wi‐Fi network without excessively degrading the DSRC system, and especially the Cisco's proposal prefers to protect the DSRC profit while the Qualcomm's draft favors Wi‐Fi exclusively. Copyright © 2016 John Wiley & Sons, Ltd.
Tuning of Cloud Point by the Nature of Surfactant Headgroup: Influence of Counterion and Additives
Authors: Yadav Sanjay Kumar , Yadav Ran Bahadur , Kumar Sanjeev
Published: August 2016

Work was performed to distinguish the role of sulfonate (–SO3−) and sulfate (–OSO3−) with respect to the micellization and clouding phenomenon in ionic surfactant solutions. The clouding phenomenon is a recent addition to the conventional one observed with nonionic surfactants. Three ionic surfactants [sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), and sodium dodecylsulfonate (SDSo)] are chosen and the effects of added tetra‐n‐pentylammonium bromide (TPeAB) and benzyl tributylammonium bromide (BTAC) have been studied on micellization and clouding behaviors in aqueous solution. Based on critical micelle concentration (CMC) and cloud point (CP) measurements, the following order has been observed: SDBS < SDS < SDSo. Though both SDBS and SDSo contain sulfonate groups, they are found at the two ends of the ordering. Therefore, the role of the phenyl ring is also having importance in clouding phenomena. For a typical surfactant, TPeAB was found to be more effective than BTAC. Based on the CP studies, two compositions of SDSo + TPeAB/BTAC were chosen and the effects of different additives (carbohydrate, amino acid, and l‐ascorbic acid) on the CP were investigated. Additive may either decrease or increase CP, depending on the structure of the counterion or additive. The present work shows a few novelties: (1) headgroup/counterion dependence of CP and (2) hydrophobicity of counterion/surfactant has an important bearing on the phenomenon. The data can be utilised in improving cloud point extraction methodologies (CPEMs).