bluuebunny/crossref_metadata_2025 huggingface dataset:
Continuous‐Flow Asymmetric Hydrogenation of an Enol Ester by using Supercritical Carbon Dioxide: Ionic Liquids versus Supported Ionic Liquids as the Catalyst Matrix
Authors: Zhang Ziyun , Franciò Giancarlo , Leitner Walter
Published: June 2015

The continuous‐flow Rh‐catalyzed asymmetric hydrogenation of the enol ester 1‐(trifluoromethyl)vinyl acetate was investigated by using supercritical carbon dioxide (scCO2) as the mobile phase and either ionic liquids (IL) or supported ionic liquids (SILP) as the catalyst matrix. Three molecular catalysts based on chiral ligands were evaluated. The catalyst based on the phosphine‐phosphoramidite ligand (Sa,Rc)‐Xyl‐QUINAPHOS in combination with the SILP/scCO2 immobilization strategy provided the most effective system under continuous‐flow conditions and gave a remarkably stable performance. During 233 h on stream, high single‐pass conversions (90–70 %), slightly increased enantioselectivity (80–84 % ee), and a turnover number of 70 400 were observed; this turnover number shows a six‐fold increase over that achieved in the IL/scCO2 system with the same catalyst.
Work Volition and Job Satisfaction: Examining the Role of Work Meaning and Person–Environment Fit
Authors: Duffy Ryan D. , Autin Kelsey L. , Bott Elizabeth M.
Published: June 2015

Building on core principles within the Psychology‐of‐Working Framework (PWF; Blustein, , ), the authors examined mediators that may explain the link between work volition and job satisfaction among employed adults (135 women, 145 men). A structural equation model was tested hypothesizing that person–environment fit and work meaning would fully mediate the work volition–job satisfaction link. Results suggested that the reason work volition related to job satisfaction was because of stronger perceived fit with one's work environment and greater perceived meaning at work. In total, the predictor variables accounted for 82% of the variance in job satisfaction. Based on these findings, clinicians are encouraged to help clients understand the unique factors that may be limiting their work volition and to specifically target barriers that are amenable to change.
Prepracticum Counseling Students' Perceived Preparedness for Suicide Response
Authors: Binkley Erin E. , Leibert Todd W.
Published: June 2015

The researchers examined how suicide‐response training received before practicum related to degrees of anxiety and confidence for practicum students regarding the treatment of suicidal clients. Results of 113 surveyed practicum students are discussed, along with implications and suggestions for future research.
Familial and Institutional Factors: Job Satisfaction for Female Counselor Educators
Authors: Alexander‐Albritton Carrie , Hill Nicole R.
Published: June 2015

Job satisfaction based on familial and institutional factors was explored for 157 female counselor educators. Results indicate that female associate professors had lower levels of intrinsic rewards domain after controlling for institutional type. Parental responsibility and partnership status were equivocal, with significant interaction effects after controlling for Carnegie Classification.
Quantitative Research Attitudes and Research Training Perceptions Among Master's‐Level Students
Authors: Steele Janeé M. , Rawls Glinda J.
Published: June 2015

This study explored master's‐level counseling students' (N = 804) perceptions of training in the Council for Accreditation of Counseling and Related Educational Programs () Research and Program Evaluation standard, and their attitudes toward quantitative research. Training perceptions and quantitative research attitudes were low to moderate, with no statistical differences across program accreditation or specialty area. Implications and possibilities for future research are discussed.
Bidisperse Shrinking Core Model for Supercritical Fluid Extraction
Authors: Egorov Andrey G. , Salamatin Arthur A.
Published: June 2015

The broken‐and‐intact‐cell model is conventionally used for interpretation of overall extraction curves (OECs) observed in supercritical fluid extraction (SFE) of ground oilseeds. Another possibility, considered here, assumes that the packed beds of the ground material always contain a significant amount of very small particles, i.e., dust, which control the initial extraction rates. The bidisperse representation of particle ensembles allows accurate description of OECs on the basis of the modified shrinking core model. A simple asymptotic solution has been derived for bidisperse granulometric distributions under typical SFE conditions. Special microscopic observations have been performed to reveal and examine the dust fraction in ground seed substrates.
Controlling the Spatial Organization of Liquid Crystalline Nanoparticles by Composition of the Organic Grafting Layer
Authors: Wójcik Michał M. , Olesińska Magdalena , Sawczyk Michał , Mieczkowski Józef , Górecka Ewa
Published: June 2015

Understanding how the spatial ordering of liquid crystalline nanoparticles can be controlled by different factors is of great importance in the further development of their photonic applications. In this paper, we report a new key parameter to control the mesogenic behavior of gold nanoparticles modified by rodlike thiols. An efficient method to control the spatial arrangement of hybrid nanoparticles in a condensed state is developed by changing the composition of the mesogenic grafting layer on the surface of the nanoparticles. The composition can be tuned by different conditions of the ligand exchange reaction. The thermal and optical behavior of the mesogenic and promesogenic ligands were investigated by using differential scanning calorimetry (DSC) and hot‐stage polarized optical microscopy. The chemical structure of the synthesized hybrid nanoparticles was characterized by 1H NMR spectroscopy, thermogravimetric analysis (TGA), XPS, and elemental analysis, whereas the superstructures were examined by small‐angle X‐ray diffraction (SAXSRD) analysis. Structural studies showed that the organic sublayer made of mesogenic ligands is denser with an increasing the average ligand number, thereby separating the nanoparticles in the liquid crystalline phases, which changes the parameters of these phases.
Tetranuclear Uranyl Polyrotaxanes: Preferred Selectivity toward Uranyl Tetramer for Stabilizing a Flexible Polyrotaxane Chain Exhibiting Weakened Supramolecular Inclusion
Authors: Mei Lei , Wang Lin , Liu Cai‐ming , Zhao Yu‐liang , Chai Zhi‐fang , Shi Wei‐qun
Published: June 2015

Introduction of mechanically interlocked components into actinide‐based metal–organic materials such as polyrotaxanes will generate an entirely new type of inorganic–organic hybrid materials showing more supramolecular encapsulation‐based dynamics. In this work, tetranuclear uranyl‐directed polyrotaxanes (UO2)4O2‐C5A3‐CB6 (1) and (UO2)4O2‐C6A3‐CB6 (2), which are the first actinide pseudorotaxanes with high‐nuclearity uranium centers, were obtained through systematic extension of the string spacer in pseudorotaxane ligands from 1,4‐butylene (C4) to 1,5‐pentylene (C5) and 1,6‐hexylene (C6). Both of the as‐synthesized tetranuclear uranyl polyrotaxanes were structurally characterized and analyzed. Considering the structure of UO2‐C4A3‐CB6 and the 1,4‐butylene string spacer, the preference for the uranyl tetramer may be related to the configurational inversion of the pseudorotaxane ligands from trans mode to cis mode on coordination to the uranyl center. Detailed structural analysis suggests that the length of the stretched string molecules for CB6‐encapsulated pseudorotaxanes has remarkable effect on the supramolecular inclusion interactions and the configurations of pseudorotaxanes, and should be responsible for the configurational inversion of pseudorotaxane spacers and subsequent distinct changes of the uranyl building units and geometric structures.
Carbazole‐endcapped Spiro[fluorene‐9,9′‐xanthene] with Large Steric Hindrance as Hole‐transporting Host for Heavily‐doped and High Performance OLEDs
Authors: Zhao Xianghua , Wu Yukun , Shi Nannan , Li Xiaoyu , Zhao Yi , Sun Mingli , Ding Dongxue , Xu Hui , Xie Linghai
Published: June 2015

In this work, we designed and synthesized a novel spirocyclic compound functionalized spiro[fluorene‐9,9′‐xanthene] with carbazole group (2‐carbazolyl‐spiro[fluorene‐9,9′‐xanthene], SFX‐Cz) via Friedel‐Crafts and Ullmann reaction, which is expected to own high thermal and morphological stability, and good carrier injection/transporting properties due to the excellent hole transporting characteristics of carbazole and cruciform structure of spiro[fluorene‐9,9′‐xanthene]. The carbazole end‐capped spiro[fluorene‐9,9′‐xanthene] SFX‐Cz based PhOLEDs with FIrpic as phosphor emitter have been researched by varying dopant concentration, which exhibit the maximum EQEs of 8.9%, 7.4%, 9.1%, and 4.7% with the doping increasing from 10% to 50%. The higher performance PhOLEDs are independent on concentration variation from 10% to 30%, which suggests the bulky steric hindrance of SFX‐Cz might be a potential canditate for high performance and inexpensive device with simplified process.
Chlorine‐Induced Hydrogen‐Bonding Network of A Novel Dimer Based on Nickel and Tridentate Ligand: 3‐Hydrazine‐4‐amino‐1,2,4‐Triazole
Authors: Bi Yangang , Zhao Wenyuan , Li Ying , Zhang Tonglai
Published: June 2015

The reaction of NiCl2 and 3‐hydrazine‐4‐amino‐1,2,4‐triazole (Hatr) in the mixed solvent of EtOH and H2O yielded a dimer compound ([Ni2(Hatr)2(H2O)2(EtOH)2Cl2]Cl2·EtOH) with water and EtOH molecules coordinated to nickle ions. It crystallized in trigonal space group R‐3, a=b=29.67(1) Å, c=8.95(7) Å, β=120(1)°, as determined by single‐crystal X‐ray diffraction. Then, they were fully characterized by the IR spectroscopy, differential scanning calorimetry (DSC), thermogravimetry (TG), and elemental analysis.
Label‐Free DNA Sensors Based on Field‐Effect Transistors with Semiconductor of Carbon Materials
Authors: Zhao Lu , Cao Dapeng , Gao Zhiqiang , Mi Baoxiu , Huang Wei
Published: June 2015

Over one decade, various DNA sensors of carbon material‐based field‐effect transistors (FETs) have been intensively developed into an inspiring area of research and technology to substitute for the traditional method, for instance, fluorescence labeling detection. These FET DNA sensors have advantages of: directly read‐out electrical signal, no need to label DNA molecule with fluorescer, high sensitivity, facility of miniaturization, simple device preparation process, high signal‐to‐noise ratio (SNR) and wide detection range. This review gives a comprehensive description on the state‐of‐the‐art carbon‐based FET DNA sensors from the aspect of both semiconductor material and structure of device. Several essential points in this research field, including sensitivity, selectivity, stability and challenges are addressed. Optimization of sensing performance and application of these devices are also discussed.
Synthesis and Evaluation of Sulfoxide‐Functionalized BODIPYs as Chemosensors for Thiols
Authors: Zhao Chunchang , Jiang Haifeng
Published: June 2015

BODIPY‐based fluorescent chemosensors bearing sulfoxide function were designed and evaluated. Thiols triggered sulfoxide→sulfide transduction in these probes leads to an obvious red‐shift in absorption and dramatic fluorescence enhancement with distinctly ratiometric features, enabling the accurate assay of thiols in living cells.
Synthesis and Absolute Configuration of Two Natural Phenolic Homobenzyl Esters
Authors: Xu Murong , Zhu Shijun , Xu Zejun , Wu Yikang , Gao Po
Published: June 2015

Two recently identified natural phenolic homobenzyl esters, isolated from Phragmipedium calurum (an orchid) and Eupatorium fortunei TURCZ (a perennial herb in the Asteraceae family), respectively, were synthesized in enantiopure forms. By comparison of the optical rotations for the synthetic and the natural samples, the absolute configurations for the natural products were reliably assigned. The synthesis also enables establishment of the absolute configuration of a closely related natural homobenzyl alcohol and provided for the first time complete physical and spectroscopic data for two other natural homobenzyl esters.
Prognostic factors and immunobiologic insights into Merkel cell carcinoma
Authors: Han Dale , Iyer Jayasri G.
Published: June 2015

Merkel cell carcinoma is an aggressive cutaneous neuroendocrine cancer, and although the current staging system takes into account several prognostic features, further study is needed to better determine whether other clinicopathologic features are also predictive of survival. The discovery of the Merkel cell polyomavirus with persistently expressed viral epitopes and an understanding of the various immune evasion mechanisms in Merkel cell carcinoma tumors provide an exciting and unique opportunity for the development of rational immune therapies to improve patient outcomes for this biologically unique, virus‐associated cancer.
Estrogen and colorectal cancer incidence and mortality
Authors: Lavasani Sayeh , Chlebowski Rowan T. , Prentice Ross L. , Kato Ikuko , Wactawski‐Wende Jean , Johnson Karen C. , Young Alicia , Rodabough Rebecca , Hubbell F. Allan , Mahinbakht Ali , Simon Michael S.
Published: June 2015

BACKGROUND

The preponderance of observational studies describe an association between the use of estrogen alone and a lower incidence of colorectal cancer. In contrast, no difference in the incidence of colorectal cancer was seen in the Women's Health Initiative (WHI) randomized, placebo‐controlled trial with estrogen alone after a mean intervention of 7.1 years and cumulative follow‐up of 13.2 years. This study extends these findings by providing detailed analyses of the effects of estrogen alone on the histology, grade, and stage of colorectal cancer, relevant subgroups, and deaths from and after colorectal cancer.

METHODS

The WHI study was a randomized, double‐blind, placebo‐controlled trial involving 10,739 postmenopausal women with prior hysterectomy. Participants were assigned to conjugated equine estrogen at 0.625 mg/d (n = 5279) or a matching placebo (n = 5409). Rates of colorectal cancer diagnoses and deaths from and after colorectal cancer were assessed throughout the study.

RESULTS

Colorectal cancer rates in the estrogen‐alone and placebo groups were comparable: 0.14% and 0.12% per year, respectively (hazard ratio [HR], 1.13; 95% confidence interval [CI], 0.83‐1.58; P = .43). Bowel screening examinations were comparable between the 2 groups throughout the study. The grade, stage, and location of colorectal cancer did not differ between the randomization groups. There were more colorectal cancer deaths in the estrogen‐alone group (34 [0.05%] vs 24 [0.03%]; HR, 1.46, 95% CI, 0.86‐2.46; P = .16), but the difference was not statistically significant. The colorectal cancer incidence was higher for participants with a history of colon polyp removal in the estrogen‐alone group (0.23% vs 0.02%; HR, 13.47; nominal 95% CI, 1.76‐103.0; P < .001).

CONCLUSIONS

The use of estrogen alone in postmenopausal women with prior hysterectomy does not influence the incidence of colorectal cancer or deaths from or after colorectal cancer. A possibly higher risk of colorectal cancer in women with prior colon polyp removal who use estrogen alone requires confirmation. Cancer 2015;121:3261–3271. © 2015 American Cancer Society.
Heart rate variability analysis by chaotic global techniques in children with attention deficit hyperactivity disorder
Authors: Wajnsztejn Rubens , De Carvalho Tatiana Dias , Garner David M. , Vanderlei Luiz Carlos Marques , Godoy Moacir Fernandes , Raimundo Rodrigo Daminello , Ferreira Celso , Valenti Vitor E. , De Abreu Luiz Carlos
Published: June 2015

Attention deficit hyperactivity disorder (ADHD) is characterized by decreased attention span, impulsiveness, and hyperactivity. Autonomic nervous system imbalance was previously described in this population. We aim to compare the autonomic function of children with ADHD and controls by analyzing heart rate variability (HRV). Children with ADHD (22 boys, mean age 9.964 years) and 28 controls (15 boys, mean age 9.857 years) rested in supine position with spontaneous breathing for 20 min. Heart rate was recorded beat by beat. HRV analysis was performed by use of chaotic global techniques. ADHD promoted an increase in the chaotic forward parameter. The algorithm which applied all three chaotic global parameters was only the second optimum statistically measured by Kruskal–Wallis (P  < 0.0001) and low standard deviations. It was also highly influential by principal component analysis with almost all variation covered by the first two components. The third algorithm which lacked the (high spectral Detrended Fluctuation Analysis) parameter performed best statistically. However, we chose the algorithm which applied all three chaotic globals due to previous studies mentioned in the text—forward and inverse problems. Comparison of the autonomic function by analyzing HRV with chaotic global techniques suggests an increase in chaotic activity in children with ADHD in relation to the control group. © 2015 Wiley Periodicals, Inc. Complexity 21: 412–419, 2016
Capacitive Deionization using Biomass‐based Microporous Salt‐Templated Heteroatom‐Doped Carbons
Authors: Porada Slawomir , Schipper Florian , Aslan Mesut , Antonietti Markus , Presser Volker , Fellinger Tim‐Patrick
Published: June 2015

Invited for this month′s cover are the groups of Tim‐Patrick Fellinger (MPI Potsdam) and Volker Presser (INM Saarbrücken and Saarland University). The image shows the dynamic process of ion electrosorption: anions are attracted and cations repelled from electrically charged electrodes based on carbons with heteroatoms. This process of capacitive deionization is particularly attractive for facile low‐energy water treatment applications. The Full Paper itself is available at 10.1002/cssc.201500166.
Fatty acid binding protein 7 and n‐3 poly unsaturated fatty acid supply in early rat brain development
Authors: Maximin Elise , Langelier Bénédicte , Aïoun Josiane , Al‐Gubory Kaïs H. , Bordat Christian , Lavialle Monique , Heberden Christine
Published: June 2015

Fatty acid binding protein 7 (FABP7), abundant in the embryonic brain, binds with the highest affinity to docosahexaenoic acid (DHA) and is expressed in the early stages of embryogenesis. Here, we have examined the consequences of the exposure to different DHA levels and of the in utero depletion of FABP7 on early rat brain development. Neurodevelopment was evaluated through the contents of two proteins, connexin 43 (Cx43) and cyclin‐dependent kinase 5 (CDK5), both involved in neuroblast proliferation, differentiation, and migration. The dams were fed with diets presenting different DHA contents, from deficiency to supplementation. DHA brain embryos contents already differed at embryonic day 11.5 and the differences kept increasing with time. Cx43 and CDK5 contents were positively associated with the brain DHA levels. When FABP7 was depleted in vivo by injections of siRNA in the telencephalon, the enhancement of the contents of both proteins was lost in supplemented animals, but FABP7 depletion did not modify phospholipid compositions regardless of the diets. Thus, FABP7 is a necessary mediator of the effect of DHA on these proteins synthesis, but its role in DHA uptake is not critical, although FABP7 is localized in phospholipid‐rich areas. Our study shows that high contents of DHA associated with FABP7 are necessary to promote early brain development, which prompted us to recommend DHA supplementation early in pregnancy. © 2015 Wiley Periodicals, Inc. Develop Neurobiol 76: 287–297, 2016
Structural and Magnetic Analysis of Retrosynthetically Designed Architectures Built from a Triply Bridged Heterometallic (CuL)2Co Node and Benzenedicarboxylates
Authors: Ghosh Soumavo , Aromí Guillem , Gamez Patrick , Ghosh Ashutosh
Published: June 2015

The flexible trinuclear metallatecton {(CuL)2Co}2+ [H2L = N,N′‐bis(salicylidene)‐1,3‐propanediamine] has been used as a building block, and its coordinative interaction with ortho‐, meta‐, and para‐benzenedicarboxylates (BDCs) has been investigated to evaluate the positional isomeric effect of these carboxylate ligands on the resulting compounds. Structural characterization reveals that o‐H2BDC produces a discrete trinuclear complex, namely [(CuL)2Co(o‐HBDC)2]·H2O (1). As expected from the retrosynthetic design, one‐dimensional (1D) coordination polymers, i.e., [{(CuL)2Co(m‐BDC)}·CH3OH]∞ (2) and [{(CuL)2Co(p‐BDC)}·2CH3OH]∞ (3), are obtained with m‐BDC and p‐BDC linkers, respectively. In all three complexes, the triply bridged bimetallic trinuclear coordination clusters are linear and solely a syn‐syn bridging mode is observed for the carboxylates. In 2, the nodes are connected sidewise and are inclined toward each other to be accommodated by the 120°‐angular m‐BDC units, whereas in 3, the linear p‐BDC linkers connect the parallel nodes diagonally. These differences in connectivity give rise to one‐dimensional “great wall”‐like chains for 2 and to quasi‐linear coordination chains for 3. These distinct one‐dimensional propagations induced by the different BDC isomers influence the three‐dimensional columnar packing of 2 and 3. Magnetic susceptibility measurements and fitting of the results confirm that these three compounds are made by analogous magnetic building blocks, with very similar antiferromagnetic intramolecular magnetic exchange (with J in the –16.96 to –11.80 cm–1 range, using the –2JS1S2 convention). The structural homogeneity of the magnetic fragment within this family of compounds has allowed magnetostructural correlations to be explored, which has not previously been attempted.
Synthesis of Thorium(IV) and Uranium(IV) Salicylaldiminate Pseudo‐Halide Complexes
Authors: Dame Ashley N. , Bharara Mohan S. , Barnes Charles L. , Walensky Justin R.
Published: June 2015

To explore the coordination chemistry of salicylaldiminate ligands as a non‐cyclopentadienyl ligand framework, we report the synthesis of their ThIV and UIV complexes. Deprotonation of (NC5H4)N=C(H)(3,5‐tBu2C6H2)OH (1), (NC9H6)N=C(H)(3,5‐tBu2C6H2)OH (2), and (CH3SC6H4)N=C(H)(3,5‐tBu2C6H2)OH (3) with sodium hydride and the subsequent addition of 0.5 equivalents of [UI4(1,4‐dioxane)2] yielded [{(NC5H4)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,N′)}2UI2] (4), [{(NC9H6)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,N′)}2UI2] (5), and [{(CH3SC6H4)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,S)}2UI2] (6), respectively. The reaction of 3 equivalents of the sodium salt of 1 afforded [{(NC5H4)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,N′)}3U]I3 (7). By using [ThCl4(dme)2], [{(NC5H4)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,N′)}2ThCl2] (8) and [{(NC9H6)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,N′)}2ThCl2] (9) were isolated. The metathesis of both chloride ligands in 9 with NaN3 led to a rare thorium azide product, [{(NC9H6)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,N′)}2Th(N3)2] (10). The reaction of 5 with AgOTf (OTf = O3SCF3) afforded [{(NC9H6)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,N′)}2U(OTf)2] (11), and the subsequent reaction of 11 with 2 equivalents of NaN3 provided [{(NC9H6)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,N′)}2U(N3)2] (12). The reaction of 5 with 2 equivalents of AgNO3 produced [{(NC9H6)N=C(H)(3,5‐tBu2C6H2)O‐κ3(O,N,N′)}2U{NO3‐κ2(O,O)}2] (13). Each complex was characterized by 1H NMR and IR spectroscopy and, with the exception of 11, their structures were determined by X‐ray crystallographic analysis.
The Syntheses and Crystal Structures of the First Disiloxane‐1,3‐dithiol and Its Cadmium Complex
Authors: Ciborska Anna , Conterosito Eleonora , Milanesio Marco , Kazimierczuk Katarzyna , Rzymowska Katarzyna , Brzozowski Krzysztof , Dołęga Anna
Published: June 2015

The silicon–sulfur compound bis‐1,3‐[di(2,6‐diisopropylphenoxy)]disiloxane‐1,3‐dithiol was obtained from silicon disulfide and 2,6‐diisopropylphenol in a reaction catalyzed by imidazole or 4‐(dimethylamino)pyridine (DMAP). The disiloxane‐1,3‐dithiol is produced in a low yield but in a repeatable manner and can be isolated as colorless crystals. The X‐ray crystal structure of the compound reveals a linear or close‐to‐linear Si–O–Si angle and a mutual trans position of the two hydrosulfido groups. The compound forms a chelating mononuclear complex with cadmium ions. In the complex, the sulfido groups adopt a cis conformation, and the Si–O–Siangle deviates from linearity. The molecular structure of the compound is discussed on the basis of DFT calculations.
Hafnium Trifluoromethanesulfonate [Hf(OTf)4] as a Unique Lewis Acid in Organic Synthesis
Authors: Ishitani Haruro , Suzuki Hirotsugu , Saito Yuki , Yamashita Yasuhiro , Kobayashi Shū
Published: June 2015

This microreview summarizes examples of Hf(OTf)4‐mediated or ‐catalyzed organic reactions. Hafnium triflate possesses four strongly electron‐withdrawing OTf groups, together with an ionic radius of intermediate range (Al < Ti < Hf, Zr < Sc < Ln), and has an oxophilic hard character typical of group IV metals. This Lewis acid shows outstanding performance in catalytic Friedel–Crafts acylation reactions and Mannich‐type reactions of imines, hydrazones, and N,O‐acetals. Several natural products have also been synthesized by use of Hf(OTf)4‐mediated or ‐catalyzed reactions. Moreover, Hf(OTf)4 has a number of potent features in carbohydrate syntheses. Hf(OTf)4 possesses many unique characteristics that distinguish it from other Lewis acids. The unique characteristics of Hf(OTf)4 should make this compound a major candidate for selection as a Lewis acid in the future.
Rhodium‐Catalyzed Hydrosilylation Reaction of N‐Sulfonyl‐1,2,3‐triazoles with Triphenylsilane: Access to Diverse Compounds
Authors: Wang Hui , Qiao Hongwei , Zhang Hao , Yang Haijun , Zhao Yufen , Fu Hua
Published: June 2015

A highly efficient rhodium‐catalyzed hydrosilylation of N‐sulfonyl‐1,2,3‐triazoles has been developed. The protocol uses readily available N‐sulfonyl‐1,2,3‐triazoles and triphenylsilane as starting materials, and the reactions first gave 2‐(triphenylsilyl)‐2‐aryl‐N‐(arylsulfonyl)ethanimines, the isomerization of which provided (E)‐2‐(triphenylsilyl)‐2‐aryl‐N‐(arylsulfonyl)ethenamines in the presence of triethylamine; the reduction of which with LiAlH4 led to 2‐(triphenylsilyl)‐2‐aryl‐N‐(arylsulfonyl)ethanamines. It is worthwhile to note that the obtained products could be converted into indole and arylethylamine derivatives. Therefore, the highly efficient rhodium‐catalyzed hydrosilylation method is a valuable strategy for synthesis of diverse compounds.
Access to Substituted Carbazoles in Water by a One‐Pot Sequential Reaction of α,β‐Substituted Nitro Olefins with 2‐(3‐Formyl‐1H‐indol‐2‐yl)acetates
Authors: Biswas Soumen , Dagar Anuradha , Srivastava Anvita , Samanta Sampak
Published: June 2015

A series of interesting new multifunctional carbazole scaffolds have been prepared in good to excellent yields by an organocatalytic one‐pot two‐step sequential reaction between α‐alkyl‐β‐substituted nitro olefins or α‐alkyl‐δ‐substituted nitro‐dienes and 2‐(3‐formyl‐1H‐indol‐2‐yl)acetates in water at room temperature followed by treatment with 2 n HCl under mild conditions. This one‐pot, organocatalytic, oxidant‐free, mild, and eco‐friendly process may provide a powerful alternative synthetic protocol to rapidly access 3‐alkyl‐substituted carbazole frameworks that have a close structural resemblance to biologically active natural carbazoles. Moreover, biologically significant cyclic imide‐ and quinolinone‐fused carbazoles have been efficiently prepared by using this synthetic method.
The Synthesis of Desepoxy‐Isotedanolide – A Potential Biosynthetic Precursor of Tedanolide
Authors: Naini Arun , Fohrer Jörg , Kalesse Markus
Published: June 2015

The tedanolides are biologically active polyketides that exhibit a characteristic feature of an 18‐membered macrolactone generated from a primary hydroxyl group. In the realm of polyketides only secondary alcohols are generated by polyketidal transformations. With this knowledge, Taylor hypothesized that the observed macrolactone might arise from an intramolecular transesterification. To investigate this hypothetical transesterification, we completed the synthesis of desepoxy‐isotedanolide as tedanolide's putative biosynthetic precursor. This synthesis required a modified protecting group strategy, which proved to be non‐trivial. Unfortunately, it was not possible to accomplish the envisioned transesterification under laboratory conditions.
Gold(I)‐Catalyzed 1,3‐O‐Transposition Reactions: Ynesulfonamides to Ynamides
Authors: Li De‐Yao , Wei Yin , Shi Min
Published: June 2015

The gold‐catalyzed 1,3‐O‐transposition reaction of ynesulfonamides provides a practical synthetic protocol for the synthesis of ynamides under mild conditions. This is the first 1,3‐O‐transposition example of ynesulfonamides in which a heteroatom is attached to the alkynyl terminal. A plausible mechanism is been proposed on the basis of 18O‐labeling and control experiments as well as DFT calculation. By simple treatment, the obtained ynamides can easily be transformed into useful products.
When immigrant groups “misbehave”: The influence of perceived deviant behavior on increased threat and discriminatory intentions and the moderating role of right‐wing authoritarianism
Authors: Kauff Mathias , Asbrock Frank , Issmer Christian , Thörner Stefan , Wagner Ulrich
Published: June 2015

In two studies, we tested the relationship between non‐immigrant individuals' perceptions of deviant behavior carried out by Muslims and foreigners and discriminatory intentions towards these outgroups. Based on a longitudinal and a representative cross‐sectional sample, we showed that two different types of perceived deviant behavior (Study 1, Muslims' unwillingness to integrate; and Study 2, foreigners' hostility towards the non‐immigrant majority group) are related to increased intergroup threat, which in turn is related to increased intentions to show passive discrimination (i.e., avoidance) towards these outgroups. In line with theorizing about an increased sensitivity for threat in authoritarian individuals, the relationship between perceptions of deviant behavior and threat was especially strong among high authoritarian individuals. Theoretical and practical implications of our results are discussed.
Reconstruction of a destructive debris‐flow event via numerical modeling: the role of valley geometry on flow dynamics
Authors: Schilirò Luca , De Blasio Fabio V. , Esposito Carlo , Scarascia Mugnozza Gabriele
Published: June 2015

Debris‐flows are widespread natural phenomena characterized by high mobility (high velocity and long runout distance) and impact forces, which frequently cause human casualties and significant damage to infrastructure. To better understand the dynamics of such events, analyzing in particular the effect induced by the valley geometry on flow velocity, runout and mobilized volumes, in this work we reconstruct a real debris‐flow event through numerical modeling. Specifically, we used a modified version of the BING model, a fluid‐dynamic depth‐integrated numerical model for debris flows, which has been properly modified to account for width changes along the valley. The studied event, which occurred in Scaletta Zanclea (Messina, north‐eastern Sicily, Italy) on October 1, 2009, is exceptionally well constrained by field and topographic information. In this respect the flow velocity, estimated from two specific locations on the basis of field evidence, the distribution of erosional and depositional areas along the Racinazzo valley, based on the comparison of pre‐ and post‐event digital elevation models (DEMs), and the runout distance were used as constraints to calibrate the model. Furthermore, we report a detailed description of the main event characteristics based on hydrological records and witness reports. The numerical modeling results are consistent with witness reports and the severe damage recorded in the Scaletta Marina village, and highlight the effect of the valley geometry on both the debris flow velocity and the erosion/deposition processes. The effect of changing valley width has been also quantified, resulting in accelerations of the debris in correspondence of the valley narrowing and stagnations at the plateaus. Copyright © 2015 John Wiley & Sons, Ltd.
Application of passive sampling for measuring dissolved concentrations of organic contaminants in the water column at three marine superfund sites
Authors: Burgess Robert M. , Lohmann Rainer , Schubauer-Berigan Joseph P. , Reitsma Pamela , Perron Monique M. , Lefkovitz Lisa , Cantwell Mark G.
Published: June 2015

Currently, there is an effort under way to encourage remedial project managers at contaminated sites to use passive sampling to collect freely dissolved concentrations (Cfree) of hydrophobic organic contaminants to improve site assessments. The objective of the present study was to evaluate the use of passive sampling for measuring water column Cfree for several hydrophobic organic contaminants at 3 US Environmental Protection Agency Superfund sites. Sites investigated included New Bedford Harbor (New Bedford, MA, USA), Palos Verdes Shelf (Los Angeles, CA, USA), and Naval Station Newport (Newport, RI, USA); and the passive samplers evaluated were polyethylene, polydimethylsiloxane-coated solid-phase microextraction fibers, semipermeable membrane devices, and polyoxymethylene. In general, the different passive samplers demonstrated good agreement, with Cfree values varying by a factor of 2 to 3. Further, at New Bedford Harbor, where conventional water sample concentrations were also measured (i.e., grab samples), passive sampler–based Cfree values agreed within a factor of 2. These findings suggest that all of the samplers were experiencing and measuring similar Cfree during their respective deployments. Also, at New Bedford Harbor, a strong log-linear, correlative, and predictive relationship was found between polyethylene passive sampler accumulation and lipid-normalized blue mussel bioaccumulation of polychlorinated biphenyls (r2 = 0.92, p < 0.05). The present study demonstrates the utility of passive sampling for generating scientifically accurate water column Cfree values, which is critical for making informed environmental management decisions at contaminated sediment sites. Environ Toxicol Chem 2015;34:1720–1733. Published 2015 SETAC. This article is a US Government work and is in the public domain in the USA.
Heating Process Simulation of Steel Coil in Bell‐Type Annealing Furnace
Authors: Yang Peipei , Wen Zhi , Dou Ruifeng
Published: June 2015

This study examines two important parameters: the convective heat‐transfer coefficient and radiative heat‐transfer coefficient, which have a significant impact on coil temperature in a furnace. A new three‐dimensional model is proposed for convective heat transfer, and the factors affecting the Nusselt number (Nu) are studied using the orthogonal test method. Finally, the relationship between the Nu number and flow rate is determined. Considering the complex geometric structure of a furnace, this study uses the Monte Carlo method to calculate the angle factor and obtains the radiant heat flux using a radiation network diagram. The calculated values are applied to steel coil temperatures for accurate boundary conditions. The results show that the temperature simulated by using the mathematical model is in good agreement with the experimental data obtained with the thermocouple insert experiment.
Novel porous soy protein‐based blend structures for biomedical applications: Microstructure, mechanical, and physical properties
Authors: Barkay‐Olami Hilla , Zilberman Meital
Published: June 2015

Use of naturally derived materials for biomedical applications is steadily increasing. Soy protein has advantages over various types of natural proteins employed for biomedical applications due to its low price, nonanimal origin, and relatively long storage time and stability. In the current study, blends of soy protein with other polymers (gelatin, alginate, pectin, polyvinyl alcohol, and polyethylene glycol) were developed and studied. The mechanical tensile properties of dense films were studied in order to select the best secondary polymer for porous three‐dimensional structures. The porous soy–gelatin and soy–alginate structures were then studied for physical properties, degradation behavior, and microstructure. The results show that these blends can be assembled into porous three‐dimensional structures by combining chemical crosslinking with freeze‐drying. The soy–alginate blends are advantageous over soy–gelatin blends, demonstrated better stability, and degradation time along with controlled swelling behavior due to more effective crosslinking and higher water uptake than soy–gelatin blends. Water vapor transmission rate experiments showed that all porous blend structures were in the desired range for burn treatment [2000–2500 g/(m2 d)] and can be controlled by the crosslinking process. We conclude that these novel porous three‐dimensional structures have a high potential for use as scaffolds for tissue engineering, especially for skin regeneration applications. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 1109–1120, 2016.
Gender Self‐Confidence and Social Influence: Impact on Working Alliance
Authors: Anderson Ruthann Smith , Levitt Dana Heller
Published: June 2015

The authors investigated the relationships between the counselor's gender self‐confidence, the counselor's use of social influence within the counseling session, and the counselor's sex in relation to the counseling relationship. These attributes were studied with regard to how deeply a therapeutic working alliance developed between the counselor and the client. Results support the importance of counselor characteristics on the counselor–client alliance. Implications for teaching, research, and practice are presented.
Perceptions of Wellness From Adults With Mobility Impairments
Authors: Snook Joy‐Del , Oliver Marvarene
Published: June 2015

The purpose of this study was to describe the perceptions of wellness from adults with mobility impairments by using phenomenological‐heuristic inquiry. The primary research question was, how do adults with mobility impairments perceive wellness? Eight participants were interviewed, and 6 core themes emerged: overcoming barriers, pain management, psychological wellness, physical activity and nutrition, social connectedness and family support, and spirituality. Implications for counselors and counselor educators and suggestions for future research are presented.
School Counselors' Ways of Knowing and Social Orientation in Relationship to Poverty Beliefs
Authors: Bray Susan Stewart , Schommer‐Aikins Marlene
Published: June 2015

The beliefs about poverty, ways of knowing, and social relationship orientation of 513 American School Counselor Association members were evaluated using canonical correlation analysis. Results indicated a relationship between the beliefs that poverty is caused by individuals' internal characteristics, connected knowing, and social hierarchies. A relationship also exists for school counselors who believe that poverty is caused by external factors, use a combination of connected and separate knowing, and embrace social equality.
Addressing Clients' Experiences of Racism: A Model for Clinical Practice
Authors: Malott Krista M. , Schaefle Scott
Published: June 2015

This article synthesizes the literature relevant to coping with racism to provide a 4‐stage model for addressing clients' discriminatory experiences. Major suggestions drawn from the literature include applying frameworks with a contextual lens, using broaching and eliciting skills to promote client exploration of racism and the effects of racism on persons of color, enhancing client racial and ethnic identities, and tailoring interventions to the clients' culture and preferred coping strategies.
A hierarchical algorithm for molecular similarity (H‐FORMS)
Authors: Ramirez‐Manzanares Alonso , Peña Joaquin , Azpiroz Jon M. , Merino Gabriel
Published: June 2015

A new hierarchical method to determine molecular similarity is introduced. The goal of this method is to detect if a pair of molecules has the same structure by estimating a rigid transformation that aligns the molecules and a correspondence function that matches their atoms. The algorithm firstly detect similarity based on the global spatial structure. If this analysis is not sufficient, the algorithm computes novel local structural rotation‐invariant descriptors for the atom neighborhood and uses this information to match atoms. Two strategies (deterministic and stochastic) on the matching based alignment computation are tested. As a result, the atom‐matching based on local similarity indexes decreases the number of testing trials and significantly reduces the dimensionality of the Hungarian assignation problem. The experiments on well‐known datasets show that our proposal outperforms state‐of‐the‐art methods in terms of the required computational time and accuracy. © 2015 Wiley Periodicals, Inc.
Animal Models for Progressive Multifocal Leukoencephalopathy
Authors: White Martyn K. , Gordon Jennifer , Berger Joseph R. , Khalili Kamel
Published: June 2015

Progressive multifocal leukoencephalopathy (PML) is a severe demyelinating disease of the CNS caused by the human polyomavirus JC (JCV). JCV replication occurs only in human cells and investigation of PML has been severely hampered by the lack of an animal model. The common feature of PML is impairment of the immune system. The key to understanding PML is working out the complex mechanisms that underlie viral entry and replication within the CNS and the immunosurveillance that suppresses the virus or allows it to reactivate. Early models involved the simple inoculation of JCV into animals such as monkeys, hamsters, and mice. More recently, mouse models transgenic for the gene encoding the JCV early protein, T‐antigen, a protein thought to be involved in the disruption of myelin seen in PML, have been employed. These animal models resulted in tumorigenesis rather than demyelination. Another approach is to use animal polyomaviruses that are closely related to JCV but able to replicate in the animal such as mouse polyomavirus and SV40. More recently, novel models have been developed that involve the engraftment of human cells into the animal. Here, we review progress that has been made to establish an animal model for PML, the advances and limitations of different models and weigh future prospects. J. Cell. Physiol. 230: 2869–2874, 2015. © 2015 Wiley Periodicals, Inc.
Mechanisms and Consequences of Double‐Strand DNA Break Formation in Chromatin
Authors: Cannan Wendy J. , Pederson David S.
Published: June 2015

All organisms suffer double‐strand breaks (DSBs) in their DNA as a result of exposure to ionizing radiation. DSBs can also form when replication forks encounter DNA lesions or repair intermediates. The processing and repair of DSBs can lead to mutations, loss of heterozygosity, and chromosome rearrangements that result in cell death or cancer. The most common pathway used to repair DSBs in metazoans (non‐homologous DNA end joining) is more commonly mutagenic than the alternative pathway (homologous recombination mediated repair). Thus, factors that influence the choice of pathways used DSB repair can affect an individual's mutation burden and risk of cancer. This review describes radiological, chemical, and biological mechanisms that generate DSBs, and discusses the impact of such variables as DSB etiology, cell type, cell cycle, and chromatin structure on the yield, distribution, and processing of DSBs. The final section focuses on nucleosome‐specific mechanisms that influence DSB production, and the possible relationship between higher order chromosome coiling and chromosome shattering (chromothripsis). J. Cell. Physiol. 230: 3–14, 2016. © 2015 Wiley Periodicals, Inc.
Changes in the concentrations of four maternal steroids during embryonic development in the threespined stickleback (Gasterosteus aculeatus)
Authors: Paitz Ryan Thomas , Mommer Brett Christian , Suhr Elissa , Bell Alison Marie
Published: June 2015

Embryonic exposure to steroids often leads to long‐term phenotypic effects. It has been hypothesized that mothers may be able to create a steroid environment that adjusts the phenotypes of offspring to current environmental conditions. Complicating this hypothesis is the potential for developing embryos to modulate their early endocrine environment. This study utilized the threespined stickleback (Gasterosteus aculeatus) to characterize the early endocrine environment within eggs by measuring four steroids (progesterone, testosterone, estradiol, and cortisol) of maternal origin. We then examined how the concentrations of these four steroids changed over the first 12 days post fertilization (dpf). Progesterone, testosterone, estradiol, and cortisol of maternal origin could be detected within unfertilized eggs and levels of all four steroids declined in the first 3 days following fertilization. While levels of progesterone, testosterone, and estradiol remained low after the initial decline, levels of cortisol rose again by 8 dpf. These results demonstrate thatG. aculeatusembryos begin development in the presence of a number of maternal steroids but levels begin to change quickly following fertilization. This suggests that embryonic processes change the early endocrine environment and hence influence the ability of maternal steroids to affect development. With these findings,G. aculeatusbecomes an intriguing system in which to study how selection may act on both maternal and embryonic processes to shape the evolutionary consequence of steroid‐mediated maternal effects.J. Exp. Zool. 323A: 422–429, 2015. © 2015 Wiley Periodicals, Inc.
Molecular and transcriptional characterization of GTHs and mPRα during ovarian maturation in rock bream Oplegnathus fasciatus
Authors: Shi Bao , Liu Xuezhou , Xu Yongjiang , Sun Zhongzhi , Chen Shengyi , Zang Kun
Published: June 2015

The membrane progestin receptor α (mPRα) plays an important role in the regulation of oocyte meiotic maturation in fish. However, the endocrine regulation of multiple spawning in fish with asynchronous ovarian development remains to be determined. We identified four genes (FSHβ, LHβ, CGα and mPRα) that are widely expressed in both the reproductive and non‐reproductive tissues of rock bream Oplegnathus fasciatus and examined their expression during ovarian maturation. The level of FSHβ transcripts in the pituitary remained high during vitellogenic stages, when the plasma levels of estradiol‐17β reached maximum levels and oocyte development was stimulated. LHβ expression in the pituitary and ovary reached maximum levels during oocyte maturation when the plasma levels of testosterone also reached a maximum. A significant correlation between mPRα transcript levels and the gonadosomatic index was observed during vitellogenesis and final maturation. Brain gonadotropin (FSHβ and LHβ) and mPRα were continuously expressed at different stages of ovarian development. The dynamic and diverse nature of gonadotropins and mPRα gene expression patterns suggests that these genes might jointly regulate ovarian development and maturation through the brain–pituitary–ovary axis in the rock bream endocrine system. J. Exp. Zool. 323A: 430–444, 2015. © 2015 Wiley Periodicals, Inc.