bluuebunny/crossref_metadata_2025 huggingface dataset:
Chiral Cationic [Cp′Mo(CO)2(NCMe)]+ Species – Catalyst Precursors for Olefin Epoxidation with H2O2 and tert‐Butyl Hydroperoxide
Authors: Reis Patrícia M. , Gamelas Carla A. , Brito José A. , Saffon Nathalie , Gómez Montserrat , Royo Beatriz
Published: January 2011

A novel cyclopentadienyl ligand bearing a chiral oxazoline pendant group (Cpox) has been prepared. Its coordination to molybdenum and tungsten afforded optically pure (R)‐CpoxM(η3‐C3H5)(CO)2 (M = Mo, W) in which the pendant oxazoline fragment is not coordinated to the metal center. Reaction of (R)‐CpoxMo(η3‐C3H5)(CO)2 with tetrafluoroboric acid gives the bidentate η5‐cyclopentadienyloxazoline complex [CpoxMo(CO)2(NCMe)]BF4 in which the oxazoline is coordinated through the N‐atom to the molybdenum center. Their catalytic performance in the epoxidation of cis‐cyclooctene, (R)‐limonene, and trans‐β‐methylstyrene with H2O2 and tert‐butyl hydroperoxide (TBHP) as oxidants has been studied. (R)‐CpoxW(η3‐C3H5)(CO)2 displayed high catalytic activity achieving quantitative conversion of cyclooctene epoxide in 2 h with H2O2. [CpoxMo(CO)2(NCMe)]+ has been shown to be an efficient catalyst with TBHP and H2O2, reaching quantitative conversions of the corresponding epoxide in 30 min and 11 h, respectively. ESI‐MS studies of the reaction of [CpoxMo(CO)2(NCMe)]+ with H2O2 and TBHP revealed the in situ formation of the corresponding peroxido [CpoxMo(O2)O]+ and dioxido [CpoxMoO2]+ species, respectively. Further oxidation of these complexes resulted in the loss of the cyclopentadienyloxazoline ligand. Based on spin trap experiments, the involvement of both carbon‐ and oxygen‐centred radicals in the olefin epoxidation catalyzed by [CpoxMo(CO)2(NCMe)]+ has been proved.
Convergent Validity of the Eating Disorder Examination and the Eating Disorder Examination‐Questionnaire Among University Women in Norway
Authors: Reas Deborah L. , Wisting Line , Kapstad Hilde , Lask Bryan
Published: January 2011

The present study compared the Eating Disorder Examination (EDE; 16.0) and the Eating Disorder Examination‐Questionnaire (EDE‐Q; 6.0) and investigated the psychometric properties of the Norwegian translation of the EDE. Fifty‐eight university women aged 19–41 years (mean BMI = 23) were assessed with the EDE and EDE‐Q. Satisfactory internal consistency and inter‐rater reliability were demonstrated for the Norwegian translation of the EDE. Generally high convergent validity between the EDE and EDE‐Q was found, with correlations ranging from 0.60 (Eating Concern) to 0.86 (Weight Concern). Agreement for OBEs and vomiting were excellent, while driven exercising generated lower levels of convergence. Consistent with prior studies, the EDE‐Q generated significantly higher levels of psychopathology, although effect sizes were small. Owing to the significantly higher EDE‐Q scores, it is ill advised to administer these two instruments interchangeably, as this may fail to produce meaningful data. Copyright © 2011 John Wiley & Sons, Ltd and Eating Disorders Association.
Disordered eating and suicidal intent: The role of thin ideal internalisation, shame and family criticism
Authors: Unikel C , Von Holle A , Bulik CM , Ocampo R
Published: January 2011

Objective

We explored the effect of thin ideal internalisation, shame proneness and family criticism on disordered eating and suicidal intent in female Mexican adolescents.

Method

We studied a probabilistic sample of 2537 high school students in central Mexico, stratified by marginalisation status and migratory intensity. We used a generalised logistic regression model to estimate the odds of disordered eating and suicidal intent across scores for three predictors: Internalisation of the thin ideal, shame and family criticism.

Results

Disordered eating was reported by 4.2% (95% CI = 0.9–7.5%) and suicidal intent by 13.2% (95% CI = 12.0–14.4%) of girls. The unadjusted odds ratios of any disordered eating for thin ideal internalisation, shame proneness and familial criticism were 1.2, 1.1 and 3.2, respectively. The positive association between thin ideal internalisation and disordered eating remained even after controlling for shame proneness and familial criticism. The association of these variables with suicidal intent was weaker.

Discussion

Results support stronger effects for disordered eating than suicidal intent across the three unadjusted predictors. It also highlights the presence of the relationship of criticism and disordered eating in female adolescents from low and middle socio‐economic backgrounds. Copyright © 2010 John Wiley & Sons, Ltd and Eating Disorders Association.
CHF in a circumferentially non‐uniformly heated tube under low‐pressure and low‐mass‐flux condition (inclined upward flow)
Authors: Ami Takeyuki , Umekawa Hisashi , Ozawa Mamoru , Mishima Kaichiro , Saito Yasushi
Published: January 2011

Most investigations on forced convective boiling have been conducted by using uniformly heated round tubes under a vertical upward flow condition, although the actual system has a non‐uniformly heated condition with several tube orientations. The non‐uniformity of the heat flux and tube inclination causes the liquid film distribution, which in turn affects the critical heat flux. In this investigation, the flow and heat‐transfer characteristics were experimentally investigated under non‐uniformly heated conditions along the circumferential direction with a 45° tube inclination. In the experiment, CHF was measured by using two different heated lengths, i.e., 900 and 1800 mm. The experimental results showed a unique tendency of CHF caused by the interrelationship of the non‐uniform heat flux distribution, the tube inclination, and liquid film redistribution. © 2011 Wiley Periodicals, Inc. Heat Trans Asian Res; Published online in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/htj.20333
Thermal therapy and evaluation by a precise temperature control device
Authors: Maruyama Shigenao , Takashima Shigeru , Okajima Junnosuke , Komiya Atsuki , Seki Takashi , Yambe Tomoyuki
Published: January 2011

Moxibustion, one of the thermal therapies used in oriental medicine, has several problems, including the fact that temperature distribution over a treatment region is not uniform, the treatment temperature cannot be controlled, and smoke is emitted. To solve these problems, we developed a precise thermal heat transfer control device and applied it to clinical medicine as a substitute for conventional moxibustion. The abdominal heating controller developed in this study has an effect equal to that of moxibustion and can heat the treatment region of human skin uniformly. The treatment effect of the device was evaluated in a clinical experiment, in which we found that these devices can treat ileus, diarrhea, and related disorders. We sought the optimal temperature for thermal therapy with regard to gender, body mass index, and age. We carried out a numerical simulation of temperature distribution inside a human body when the abdominal region is heated. Temperature distribution of the heated abdominal region was calculated using a 2‐D axisymmetric model considering bioheat generation such as blood perfusion and metabolism. The calculation results confirmed that the thermal effect cannot reach the viscera. © 2011 Wiley Periodicals, Inc. Heat Trans Asian Res; Published online in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/htj.20334
Stability of long‐term outcome in bulimia nervosa: a 3‐year follow‐up
Authors: Zeeck Almut , Weber Stephanie , Sandholz Angelika , Joos Andreas , Hartmann Armin
Published: January 2011

We report on the 3‐year course and outcome of patients with bulimia nervosa (BN), initially treated in an inpatient or day clinic setting. Patients were assessed by structured interviews (Structured Clinical Interview for DSM Disorders I and II and Structured Interview for Anorexia and Bulimia Nervosa) and questionnaires (Eating Disorder Inventory‐2, Symptom Checklist‐90‐R, and Social Adjustment Scale) at time points of admission, discharge, and 3‐month, 12‐month and 36‐month follow‐ups. Data of 83.7% of the 43 patients were available. After 3 years, about one third of patients showed complete remission, one third showed partial remission, and one third still fulfilled all the criteria of BN. Most changes occurred during hospitalization. Remission status showed substantial fluctuation over time, with little correlation between time points of assessment (discharge and 3‐month, 12‐month, and 36‐month follow‐ups). A cluster analysis revealed four patterns of longitudinal symptom change. Day clinic and inpatient treatment are overall effective. Longitudinal and repeated assessments are necessary to validly measure outcome in BN. © Wiley Periodicals, Inc. J Clin Psychol 67:1–10, 2011.
SECTORAL GROWTH AND JOB CREATION: EVIDENCE FROM INDONESIA
Authors: Suryadarma Daniel , Suryahadi Asep , Sumarto Sudarno
Published: January 2011

We develop a growth‐employment model that decomposes the Indonesian economy into six components, based on a combination of economic sectors and location, and ascertain the sectors that created the most jobs in Indonesia over the past two decades. We find that urban employment is mostly driven by higher growth in the services sector, especially areas that require skilled personnel. Meanwhile, the agriculture sector growth still drives employment in rural areas, although it appears that the services sector also creates a significant number of jobs. Based on these findings, we provide some policy recommendations. Copyright © 2011 John Wiley & Sons, Ltd.
Ultra‐performance LC‐photodiode array‐eλ‐ESI‐MS/MS screening method for the detection of radical‐scavenging natural antioxidants from Radix et Rhizoma Rhei
Authors: Wang Guo‐Ying , Chen Fang‐Fang , Shi Yan‐Ping
Published: January 2011

A novel ultra‐performance LC‐photodiode array‐eλ‐ESI‐MS/MS screening method was developed for the detection and identification of natural antioxidants from Radix et Rhizoma Rhei. Nine compounds were found to possess a potential antioxidant activity, and their free radical‐scavenging capacities were investigated in detail. The nine compounds were identified as 1‐O‐galloyl‐2‐O‐cinnamoylglucose, 6‐hydroxymusizin‐8‐O‐β‐D‐glucopyranoside, (+)‐catechin, gallic acid 3‐O‐β‐D‐glucopyranoside, trans‐3,5,4′‐trihydroxystilbene‐4′‐O‐β‐D‐(2″‐O‐galloyl)‐glucopyranoside, sennoside A, 4‐(4′‐hydroxyphenyl)‐2‐butanone‐4′‐O‐β‐D‐(2″‐O‐galloyl‐6″‐O‐p‐coumaroyl) glucopyranoside, emodin‐8‐O‐(6′‐O‐malonyl) glucopyranoside, and physcion‐8‐O‐β‐D‐glucopyranoside. The reactivity and SC50 values of those compounds were investigated, respectively. 1‐O‐Galloyl‐2‐O‐cinnamoylglucose showed the strongest capability for scavenging 1,1‐diphenyl‐2‐picrylhydrazyl‐free radical; trans‐3,5,4′‐trihydroxystilbene‐4′‐O‐β‐D‐(2″‐O‐galloyl) glucopyranoside showed the strongest capability for scavenging superoxide radical; 4‐(4′‐hydroxyphenyl)‐2‐butanone‐4′‐O‐2‐D‐(2″‐O‐galloyl‐6″‐O‐p‐coumaroyl) glucopyranoside exhibited the highest reactivity in the lipid peroxidation processes. The use of the analytical screening method based on ultra‐performance LC‐photodiode array‐eλ‐ESI‐MS/MS would provide a new way for rapid detection of radical‐scavenging natural compounds from Radix et Rhizoma Rhei or complex matrices.
H‐Phosphonic Acid Derivatives as Catalysts for Reversible Chain Transfer Catalyzed Polymerization (RTCP) at Ambient and High Pressure
Authors: Wolpers Arne , Ackermann Lutz , Vana Philipp
Published: January 2011

Several H‐phosphonic acid derivatives (PADs) were analyzed regarding their ability to perform as effective catalysts in reversible chain transfer catalyzed polymerization (RTCP), a relatively new type of controlled radical polymerization. Therefore, bulk polymerizations of styrene at 100 °C using different PADs were studied in detail. The obtained number‐average molar masses and polydispersities of the polymeric products showed that a cyclic PAD derived from pinacol was found to be a very well suited catalyst for RTCP under the chosen conditions. In addition, RTCPs at high pressure up to 2000 bar were conducted indicating poor molar mass control compared to the systems at ambient pressure.

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Formation of Thermosets via Molecular Pockets in Thermoplastic Chains: A Simple and Direct Way to Nanospherical Thermosets
Authors: Rungswang Wonchalerm , Chirachanchai Suwabun
Published: January 2011

By curing bisphenol A‐based benzoxazine in a thermoplastic polystyrene‐block‐poly (ethylene‐co‐1‐butene)‐block‐polystyrene (SEBS) block copolymer, nanospherical polybenzoxazines as small as 150 nm with narrow size distribution are obtained in high yield. This specific condition allows simple and direct formation of nano‐ or microspherical thermoset resins. A model of how the thermoplastic block copolymer chains act as a molecular pocket where the thermoset curing proceeds is presented. It is demonstrated that this mechanism requires (i) a particular block of thermoplastic copolymer which allows specific interaction with monomeric thermoset molecules, and (ii) the curing of thermosets in a molecular assembly structure to confine the phase separation of thermoset prepolymer during curing.

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Spherical fractional and hypersingular integrals of variable order in generalized Hölder spaces with variable characteristic
Authors: Samko Natasha , Vakulov Boris
Published: January 2011

We consider non‐standard generalized Hölder spaces of functionsfon the unit sphere\documentclass{article}\usepackage{amssymb}\pagestyle{empty}\begin{document}${\mathbb S}^{n-1} $\end{document}in\documentclass{article}\usepackage{amssymb}\pagestyle{empty}\begin{document}${\mathbb R}^n $\end{document}, whose local continuity modulus Ω(f,x,h) at a point\documentclass{article}\usepackage{amssymb}\pagestyle{empty}\begin{document}$x\in {\mathbb S}^{n-1} $\end{document}has a dominant ω(x,h) which may vary from point to point. We establish theorems on the mapping properties of spherical potential operators of variable order α(x), from such a variable generalized Hölder space to another one with a “better” dominant ωα(x,h) =hℜα(x)ω(x,h), and similar mapping properties of spherical hypersingular integrals of variable order α(x) from such a space into the space with “worse” dominant ω−α(x,h) =h−ℜα(x)ω(x,h). We admit variable complex valued orders α(x) which may vanish at a set of measure zero. To cover this case, we consider the action of potential operators to weighted generalized Hölder spaces with the weight α(x). © 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim
One Decade of Microwave‐Assisted Polymerizations: Quo vadis?
Authors: Ebner Clemens , Bodner Thomas , Stelzer Franz , Wiesbrock Frank
Published: January 2011

The application of microwave irradiation in polymer syntheses and modifications is of continuously growing interest and has received significant international interest since the beginning of the millennium. Preceded by a review that was published 6 years ago, the present paper summarizes the most recent trends in this research area. Radical as well as step‐growth and ring‐opening polymerizations will be addressed; furthermore, the evolution from microwave‐assisted polymerizations to microwave‐assisted material fabrication will be described on the examples of polymeranalogous reactions, polymer/metal composites and bio‐based materials.

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Glaucasides A–C, three saikosaponins from Atriplex glauca L. var. ifiniensis (Caball) Maire
Authors: Jabrane Aymen , Ben Jannet Hichem , Miyamoto Tomofumi , Tanaka Chiaki , Mirjolet Jean‐François , Duchamp Olivier , Harzallah‐Skhiri Féthia , Lacaille‐Dubois Marie‐Aleth
Published: January 2011

From the roots of Atriplex glauca L. var. ifiniensis (Caball) Maire (syn. of Atriplex parvifolia Lowe var. genuina Maire), three new saikosaponins designated as glaucasides A–C (1–3) were isolated together with the known 3‐O‐$\bf{\beta}$‐D‐glucopyranosyl‐(1 → 2)‐$\bf{\beta}$‐D‐galactopyranosyl‐saikogenin F (4). The structures of the new compounds were elucidated by extensive analysis of one‐dimensional and two‐dimensional NMR spectroscopy, FABMS, HR‐ESIMS and chemical evidence as 13$\bf{\beta}$,28‐epoxy‐16$\bf{\beta}$,21$\bf{\beta}$‐dihydroxyolean‐11‐en‐3$\bf{\beta}$‐yl O‐$\bf{\beta}$‐D‐[2‐O‐sulfate]‐glucopyranosyl‐(1 → 2)‐$\bf{\alpha}$‐L‐arabinopyranoside (1), 13$\bf{\beta}$,28‐epoxy‐16$\bf{\beta}$,21$\bf{\beta}$‐dihydroxyolean‐11‐en‐3$\bf{\beta}$‐yl O‐$\bf{\beta}$‐D‐[2‐O‐sulfate]‐glucopyranosyl‐(1 → 2)‐$\bf{\alpha}$‐L‐arabinopyranosyl 21‐O‐{4‐(secbutylamido)‐butanoyl ester} (2) and 3‐O‐$\bf{\beta}$‐D‐glucopyranosyl‐(1 → 2)‐$\bf{\beta}$‐D‐galactopyranosyl saikogenin G (3). The cytotoxic activities of these compounds were evaluated against the HT‐29 and HCT 116 human colon cancer cell lines. Copyright © 2011 John Wiley & Sons, Ltd.
1H, 13C, 195Pt and 15N NMR structural correlations in Pd(II) and Pt(II) chloride complexes with various alkyl and aryl derivatives of 2,2′‐bipyridine and 1,10‐phenanthroline
Authors: Pawlak Tomasz , Pazderski Leszek , Sitkowski Jerzy , Kozerski Lech , Szłyk Edward
Published: January 2011

1H, 13C, 195Pt and 15N NMR studies of platinide(II) (M = Pd, Pt) chloride complexes with such alkyl and aryl derivatives of 2,2′‐bipyridine and 1,10‐phenanthroline as LL = 6,6′‐dimethyl‐bpy, 5,5′‐dimethyl‐bpy, 4,4′‐di‐tert‐butyl‐bpy, 2,9‐dimethyl‐phen, 2,9‐dimethyl‐4,7‐diphenyl‐phen, 3,4,7,8‐tetramethyl‐phen, having the general [M(LL)Cl2] formula were performed and the respective chemical shifts (δ1H, δ13C, δ195Pt, δ15N) reported. 1H high‐frequency coordination shifts ($\Delta_{\rm {coord}}^{\rm {1H}} = \delta_{\rm {complex}}^{\rm {1H}} - \delta_{\rm {ligand}}^{\rm {1H}}$) mostly pronounced for nitrogen‐adjacent protons and methyl groups in the nearest adjacency of nitrogen, as well as 15N low‐frequency coordination shifts ($\Delta_{\rm {coord}}^{\rm {15N}} = \delta_{\rm {complex}}^{\rm {15N}} - \delta_{\rm {ligand}}^{\rm {15N}}$) were discussed in relation to the molecular structures. Copyright © 2011 John Wiley & Sons, Ltd.
Solid‐state NMR detection of 14N13C dipolar couplings between amino acid side groups provides constraints on amyloid fibril architecture
Authors: Middleton David A.
Published: January 2011

Solid‐state nuclear magnetic resonance (SSNMR) is a powerful technique for the structural analysis of amyloid fibrils. With suitable isotope labelling patterns, SSNMR can provide constraints on the secondary structure, alignment and registration of β‐strands within amyloid fibrils and identify the tertiary and quaternary contacts defining the packing of the β‐sheet layers. Detection of 14N13C dipolar couplings may provide potentially useful additional structural constraints on β‐sheet packing within amyloid fibrils but has not until now been exploited for this purpose. Here a frequency‐selective, transfer of population in double resonance SSNMR experiment is used to detect a weak 14N13C dipolar coupling in amyloid‐like fibrils of the peptide H2N‐SNNFGAILSS‐COOH, which was uniformly 13C and 15N labelled across the four C‐terminal amino acids. The 14N13C interatomic distance between leucine and asparagine side groups is constrained between 2.4 and 3.8 Å, which allows current structural models of the β‐spine arrangement within the fibrils to be refined. This procedure could be useful for the general structural analysis of other proteins in condensed phases and environments, such as biological membranes. Copyright © 2011 John Wiley & Sons, Ltd.
Theoretical prediction and assignment of vicinal 1H–1H coupling constants of diastereomeric 3‐alkoxy‐6,7‐epoxy‐2‐oxabicyclo[3.3.0]octanes
Authors: Aav Riina , Pehk Tõnis , Tamp Sven , Tamm Toomas , Kudrjašova Marina , Parve Omar , Lopp Margus
Published: January 2011

Spin–spin coupling constants between nuclei in NMR spectroscopy reflect their spatial arrangement. A number of calculation methods, applying different levels of theory, have been developed to support the stereochemical assignment of novel compounds. Nevertheless, revisions of the assignment of structures in the literature are not rare. In the present work, the reliability of the calculation methods amenable for a theoretical prediction of spin–spin coupling constants of vicinal protons to support correct stereochemical assignment of substitution at five‐membered rings of 3‐alkoxy‐6,7‐epoxy‐2‐oxabicyclo[3.3.0]octanes was studied. Experimental 3J(H,H) coupling constants were compared with the coupling constants calculated for all possible diastereomers. The fully quantum chemical approach provided theoretical 3J(H,H) coupling constants with an absolute deviation of no more than 1.1 Hz for 91% of the experimentally studied coupled spins, whereas the methods without quantum chemical geometry optimization resulted in completely unreliable predictions. Consequently, for a reliable stereochemical assignment of small and medium size molecules, the protocol for calculating the coupling constants based on the results of the quantum chemical geometry optimization is recommended. Copyright © 2011 John Wiley & Sons, Ltd.
Demonstration of anipi‐diode photovoltaic
Authors: Cress Cory D. , Polly Stephen J. , Hubbard Seth M. , Raffaelle Ryne P. , Walters Robert J.
Published: January 2011

The simulation, growth, processing, and characterization of a three‐period GaAs n‐type/intrinsic/p‐type/intrinsic … (nipi) doping solar cell is demonstrated. A V‐groove etching process is characterized and used to expose the multiple n‐type and p‐type layers for electrical connection made by interdigitated grid‐finger electrodes. A five‐layer photolithographic process flow is developed and used to make 1 × 1 cm2devices with varying grid‐finger separation. Device simulations of the structure indicate that strong rectification can be achieved in the parallel‐connected three periodnipiGaAs solar cell structure provided the necessary semiconductor doping compensation is achieved in the region near the metal‐semiconductor interfaces. Experimentally, the improvements observed in the open circuit voltage, short circuit current, and ideality of the devices following thermal annealing suggests the formation of barriers near the contacts, which support the simulation results. A comparison of the short circuit current and series resistance under illumination indicate a tradeoff between shadowing and series resistance, which may be overcome with modification to the device structure. Ultimately, these results show promise towards the development of high efficiency solar cells or radioisotope batteries, and offer a novel device structure for the incorporation of nano‐structures such as quantum wells or quantum dots. Copyright © 2010 John Wiley & Sons, Ltd.
The home for histrionism
Authors: Gore Whitney L. , Tomiatti Michele , Widiger Thomas A.
Published: January 2011

One of the official proposals for the fifth edition of the American Psychiatric Association's diagnostic manual (DSM‐5) is to provide a dimensional model in which 37 traits are included within six broad domains. One of the more important traits within this model is ‘histrionism’ because another proposal for DSM‐5 is to delete the histrionic diagnostic category. The only way to recover histrionic traits in DSM‐5 will be through the dimensional model. Histrionism, though, is included within the domain of antagonism of this dimensional model, despite the fact that previous research has consistently placed histrionic personality disorder within extraversion. The current study tests empirically whether histrionic personality traits are optimally placed within the domain of extraversion or antagonism through tests involving seven alternative measures of histrionic personality disorder, five scales to assess the DSM‐5 components of histrionism, 10 measures of various histrionic personality traits and two alternative measures of extraversion. The results of the study provide support for placing histrionism within antagonism and clarify the inconsistency of the DSM‐5 placement with the existing research, but also indicate that a more complete and accurate understanding of histrionism would include extraversion. The implications of the findings for DSM‐5 and future research are discussed. Copyright © 2010 John Wiley & Sons, Ltd.
Investigation of solubilization and digestion methods for microsomal membrane proteome analysis using data‐independent LC‐MSE
Authors: Mbeunkui Flaubert , Goshe Michael B.
Published: January 2011

To evaluate the implementation of various denaturants and their efficacy in bottom‐up membrane proteomic methods using LC‐MS analysis, microsomes isolated from tomato roots were treated with MS‐compatible surfactants (RapiGest SF Surfactant from Waters and PPS Silent Surfactant from Protein Discovery), a chaotropic reagent (guanidine hydrochloride), and an organic solvent (methanol). Peptides were analyzed in triplicate sample and technical replicates by data‐independent LC‐MSE analysis. Overall, 2333 unique peptides matching to 662 unique proteins were detected with the order of denaturant method efficacy being RapiGest SF Surfactant, PPS Silent Surfactant, guanidine hydrochloride, and methanol. Using bioinformatic analysis, 103 proteins were determined to be integral membrane proteins. When normalizing the data as a percentage of the overall number of peptides and proteins identified for each method, the order for integral membrane protein identification efficacy was methanol, guanidine hydrochloride, RapiGest SF Surfactant, and PPS Silent Surfactant. Interestingly, only 8% of the proteins were identified in all four methods with the silent surfactants having the greatest overlap at 17%. GRAVY analysis at the protein and peptide level indicated that methanol and guanidine hydrochloride promoted detection of hydrophobic proteins and peptides, respectively; however, trypsin activity in the presence of each denaturant was determined as a major factor contributing to peptide identification by LC‐MSE. These results reveal the complementary nature of each denaturant method, which can be used in an integrated approach to provide a more effective bottom‐up analysis of membrane proteomes than can be achieved using only a single denaturant.
Proteome analysis of wheat leaf rust fungus, Puccinia triticina, infection structures enriched for haustoria
Authors: Song Xiao , Rampitsch Christof , Soltani Bahram , Mauthe Wayne , Linning Rob , Banks Travis , McCallum Brent , Bakkeren Guus
Published: January 2011

Puccinia triticina (Pt) is a representative of several cereal‐infecting rust fungal pathogens of major economic importance world wide. Upon entry through leaf stomata, these fungi establish intracellular haustoria, crucial feeding structures. We report the first proteome of infection structures from parasitized wheat leaves, enriched for haustoria through filtration and sucrose density centrifugation. 2‐D PAGE MS/MS and gel‐based LC‐MS (GeLC‐MS) were used to separate proteins. Generated spectra were compared with a partial proteome predicted from a preliminary Pt genome and generated ESTs, to a comprehensive genome‐predicted protein complement from the related wheat stem rust fungus, Puccinia graminis f. sp. tritici (Pgt) and to various plant resources. We identified over 260 fungal proteins, 16 of which matched peptides from Pgt. Based on bioinformatic analyses and/or the presence of a signal peptide, at least 50 proteins were predicted to be secreted. Among those, six have effector protein signatures, some are related and the respective genes of several seem to belong to clusters. Many ribosomal structural proteins, proteins involved in energy, general metabolism and transport were detected. Measuring gene expression over several life cycle stages of ten representative candidates using quantitative RT‐PCR, all were shown to be strongly upregulated and four expressed solely upon infection.
A combined free‐flow electrophoresis and DIGE approach to identify proteins regulated by butyrate in HT29 cells
Authors: Fung Kim Y. C. , Cursaro Chris , Lewanowitsch Tanya , Brierley Gemma V. , McColl Shaun R. , Lockett Trevor , Head Richard , Hoffmann Peter , Cosgrove Leah
Published: January 2011

Many biologically active agents exert a pleiotropic response in cells and tissues. This presents challenges in descriptive and comparative analysis of the proteome in response to these agents. Although free‐flow electrophoresis has been applied in a number of proteomic studies as a protein separation technique, the combination of free‐flow electrophoresis and DIGE has not yet been investigated for comparative proteomic analysis. In this study, we have compared the effects of butyrate on HT29 colorectal cancer cells with a particular focus on apoptosis and describe the utility of a novel approach combining free‐flow electrophoresis with DIGE to identify differentially expressed proteins. We verify the results obtained by the combined free‐flow electrophoresis and DIGE approach with Western blot analysis of selected proteins. We also report for the first time the regulation of a number of proteins by butyrate in HT29 colorectal cells including peptidyl‐prolyl cis‐trans isomerase A (cyclophilin A) and profilin‐1.
The suzuki–heck polymerization as a tool for the straightforward obtainment of poly(fluorenylene‐vinylene) sensitizers for dye‐sensitized solar cells
Authors: Grisorio Roberto , Mastrorilli Piero , Suranna Gian Paolo , Cosma Pinalysa , De Marco Luisa , Manca Michele , Gigli Giuseppe
Published: January 2011

This article describes the synthesis and properties of the first poly(arylene‐vinylene)‐based sensitizers for application in dye‐sensitized solar cells (DSSC). The polymers were prepared by the Suzuki–Heck copolymerization of potassium vinyltrifluoroborate (PVTB) with a mixture of dibromoaryl comonomers designed to obtain macromolecules able to bind onto the photoelectrode by means of carboxyphenylene units. The copolymerization reactions were carried out in the presence of an excess of PVTB to lower the molecular weights of the polymers, which were obtained as soluble materials. The polymers poly[(9,9‐didodecyl‐2,7‐fluorenylene)‐vinylene‐co‐(carboxy‐2,5‐phenylene)‐vinylene] (P1), poly[(9,9‐didodecyl‐2,7‐fluorenylene)‐vinylene‐co‐(carboxy‐2,5‐phenylene)‐vinylene‐co‐(4,7‐benzothiadiazolylene)‐vinylene] (P2), and poly[(9,9‐didodecyl‐2,7‐fluorenylene)‐vinylene‐co‐(carboxy‐2,5‐phenylene)‐vinylene‐co‐2,5‐thienylene‐vinylene] (P3) were used in DSSC devices, obtaining conversion efficiencies up to 0.88% (P3). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011
Oxidation of sec‐alcohols with Ru(II)‐bearing microgel star polymer catalysts via hydrogen transfer reaction: Unique microgel‐core catalysis
Authors: Terashima Takaya , Ouchi Makoto , Ando Tsuyoshi , Sawamoto Mitsuo
Published: January 2011

Oxidation of sec‐alcohols was investigated with ruthenium‐bearing microgel core star polymer catalysts [Ru(II)‐Star]. The star polymer catalysts were directly prepared via RuCl2(PPh3)3‐catalyzed living radical polymerization of methyl methacrylate (MMA), followed by the arm‐linking reaction with ethylene glycol dimethacrylate (1) in the presence of diphenylphosphinostyrene (2). The Ru(II)‐Star efficiently and homogeneously catalyzed the oxidation of 1‐phenylethanol (S1) to give a corresponding ketone (acetophenone) in higher yield (92%) than the analogs of polymer‐supported ruthenium complexes. Importantly, the star catalyst afforded high recycling efficiency in the oxidation. They held catalytic activity against three times catalysis even though they were recovered under air‐exposure, whereas the conventional RuCl2(PPh3)3 lost the activity for same recycling procedure due to the deactivation by oxygen. The stability of the star catalysts during the recycle experiment was confirmed by detailed spectroscopic characterization. The star polymers also catalyzed oxidation for a wide range of sec‐alcohols with aromatic and aliphatic groups. The substrate affinity was different from that with RuCl2(PPh3)3, suggesting the unique selectivity caused by the specific structure. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.
Synthesis of polyethylene‐grafted multiwalled carbon nanotubes via a peroxide‐initiating radical coupling reaction and by using well‐defined TEMPO and thiol end‐functionalized polyethylenes
Authors: Akbar Sohaib , Beyou Emmanuel , Chaumont Philippe , Mazzolini Jérôme , Espinosa Edgar , D'agosto Franck , Boisson Christophe
Published: January 2011

Polyethylene (PE), alkoxyamine‐ and thiol‐terminated PEs (PE‐TEMPO and PE‐SH, respectively) can be converted to macroradicals using a peroxide, a thermal cleavage of the alkoxyamine and a hydrogen transfer reaction of the thiol, respectively. The addition of these macroradicals to multiwalled carbon nanotubes (MWCNTs) were compared by performing grafting reactions at 160 °C in 1,3‐dichlorobenzene as solvent. Raman spectroscopy was utilized to follow the introduction of PE on the MWCNTs' surface while thermogravimetric and elemental analysis indicated the extent of this grafting. The grafting ratio was found to be in the range of 19–36 wt %. PE‐functionalized MWCNTs were imaged by transmission electronic microscopy showing a PE layer with various thicknesses covering the surface of nanotubes. It was found that higher levels of grafting were obtained using PE‐2,2,6,6‐tetramethylpiperidinyl‐1‐oxy and PE‐SH rather than a radical grafting reaction in which dicumyl peroxide, PE, and MWCNTs were reacted. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011
Synthesis and properties of bio‐based polyurethanes bearing hydroxy groups derived from alditols
Authors: Hashimoto Kazuhiko , Hashimoto Naoya , Kamaya Takehiko , Yoshioka Junya , Okawa Haruki
Published: January 2011

Four kinds of bio‐based polyurethanes bearing hydroxy groups in the pendants were synthesized by the polyaddition of D‐mannitol‐ and D,L‐erythritol‐derived diols (1,2:5,6‐di‐O‐isopropylidene‐D‐mannitol and 1,2‐O‐isopropylidene‐D,L‐erythritol) with hexamethylene diisocyanate and methyl (S)‐2,6‐diisocyanatohexanoate and the subsequent deprotection of the isopropylidene groups. They were hydrolyzed much more quickly than the corresponding protected polyurethanes at 50 °C and pH 7.0, although their hydrolytic degradation rate was lower than that of polyurethanes with saccharic and glucuronic lactone groups, which had been reported in our previous articles. The introduction of D‐mannitol units to the polyether‐polyurethanes containing poly(oxytetramethylene) glycol units also enhanced their hydrolyzibility. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011
Synthesis of a variety of star‐shaped polybenzamides via chain‐growth condensation polymerization with tetrafunctional porphyrin initiator
Authors: Yoshino Kazuo , Yokoyama Akihiro , Yokozawa Tsutomu
Published: January 2011

A variety of well‐defined tetra‐armed star‐shaped poly(N‐substituted p‐benzamide)s, including block poly(p‐benzamide)s with different N‐substituents, and poly(N‐substituted m‐benzamide)s, were synthesized by using porphyrin‐cored tetra‐functional initiator 2 under optimized polymerization conditions. The initiator 2 allowed discrimination of the target star polymer from concomitantly formed linear polymer by‐products by means of GPC with UV detection, and the polymerization conditions were easily optimized for selective synthesis of the star polybenzamides. Star‐shaped poly(p‐benzamide) with tri(ethylene glycol) monomethyl ether (TEG) side chain was selectively obtained by polymerization of phenyl 4‐{2‐[2‐(2‐methoxyethoxy)ethoxy]ethylamino}benzoate (1b′) with 2 at −10 °C in the case of [1b′]0/[2]0 = 40 and at 0 °C in the case of [1b′]0/[2]0 = 80. Star‐shaped poly(p‐benzamide) with 4‐(octyloxy)benzyl (OOB) substituent was obtained only when methyl 4‐[4‐(octyloxy)benzylamino]benzoate (1c) was polymerized at 25 °C at [1c]0/[2]0 = 20. On the other hand, star‐shaped poly(m‐benzamide)s with N‐butyl, N‐octyl, and N‐TEG side chains were able to be synthesized by polymerization of the corresponding meta‐substituted aminobenzoic acid alkyl ester monomers 3 at 0 °C until the ratio of [3]0/[2]0 reached 80. However, star‐shaped poly(m‐benzamide)s with the OOB group were contaminated with linear polymer even when the feed ratio of the monomer 3d to 2 was 20. The UV–visible spectrum of an aqueous solution of star‐shaped poly(p‐benzamide) with TEG side chain indicated that the hydrophobic porphyrin core was aggregated. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011
Syntheses of random PET‐co‐PTTs and some related copolyesters by entropically‐driven ring‐opening polymerizations and by melt blending: Thermal properties and crystallinity
Authors: Conzatti Lucia , Alessi Matteo , Stagnaro Paola , Hodge Philip
Published: January 2011

A library of random poly(ethylene terephthalate) (PET), poly(trimethylene terephthalate) (PTT), and seven PET–PTT copolymers has been prepared in a high throughput manner by entropically‐driven ring‐opening polymerizations of the corresponding macrocyclic oligomers. The products have been investigated by differential scanning calorimetry and wide angle X‐ray diffraction. They show that the 50:50 copolymer displays a crystalline phase. The same phase can be formed by in situ transesterification when a 50:50 mixture of PET and PTT is melt blended. Poly(butylene terephthalate) (PBT)–PET and PTT–PBT 50:50 copolymers also show crystal phases. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011
Low molecular weight aromatic compounds possessing a nonflammable characteristic in fluoroalkyl end‐capped acrylic acid oligomer/silica nanocomposite matrices after calcination at 800 °C under atmospheric conditions
Authors: Sawada Hideo , Kikuchi Mieko , Nishida Masakazu
Published: January 2011

Fluoroalkyl end‐capped acrylic acid oligomer [RF‐(ACA)n‐RF] reacted with tetraethoxysilane and silica nanoparticles in the presence of low molecular weight aromatic compounds [Ar‐H] such as cetylpyridinium chloride (CPC) and bisphenol AF under alkaline conditions to afford RF‐(ACA)n‐RF/SiO2 nanocomposites‐encapsulated Ar‐H in 47–94% isolated yields. These fluorinated silica nanocomposites‐encapsulated Ar‐H can exhibit no weight loss behavior corresponding to the contents of Ar‐H after calcination at 800 °C under atmospheric conditions, although fluoroalkyl end‐capped acrylic acid oligomer in the nanocomposites decomposed completely under similar conditions. UV‐vis spectra of well‐dispersed methanol solutions of RF‐(ACA)n‐RF/SiO2/CPC nanocomposites before calcination show that CPC can be encapsulated into fluorinated silica nanocomposites with encapsulated ratios: 23–43%. The fluorinated nanocomposites after calcination was found to exhibit a higher antibacterial activity related to the presence of CPC in the composites. Encapsulated bisphenol AF into RF‐(ACA)n‐RF/SiO2 nanocomposites before and after calcination at 800 °C can exhibit a good releasing ability toward methanol with released ratios: 48 and 26%, respectively. 1H MAS NMR, HPLC analysis, and LC‐MS spectra of RF‐(ACA)n‐RF/silica nanocomposites‐encapsulated bisphenol AF also showed the presence of bisphenol AF in the nanocomposites even after calcination at 800 °C under atmospheric conditions. These findings suggest that CPC and bisphenol AF can exhibit a nonflammable characteristic in the fluorinated silica nanocomposites. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011
Multi‐functional initiator and poly(carboxybetaine methacrylamides) for building biocompatible surfaces using “nitroxide mediated free radical polymerization” strategies
Authors: Abraham Sinoj , Unsworth Larry D.
Published: January 2011

Biomaterials generally suffer from rapid nonspecific protein adsorption, which initiates many deleterious host responses, and complex chemistries that are employed to facilitate cellular interactions. A chemical approach that, based upon current literature, combines a nonfouling architecture with a biomemtic cell‐adhesive end‐group, is presented. Namely, surface‐initiated polymerization of zwitterionic [poly (carboxybetaine methacrylamide)] brushes, with controlled charge densities and phosphonate head groups. Nitroxide mediated free radical polymerization (NMFRP) was employed for various reasons: reduces presence of potentially cytotoxic organometallic catalysts common in atom transfer radical polymerization (ATRP); and it allows a phosphonate end‐group instead of the common brominated end‐group. Thermally oxidized silicon wafers were covalently functionalized with diethyl‐(1‐(N‐(1‐(3‐(trimethoxysilyl)propylcarbamoyl)ethoxy)‐N‐tert‐butylamino)ethyl)phosphonate. NMFRP was used to graft zwitterionic carboxybetaine methacrylamide monomers of varying inter‐charge separation. The resulting thin films were characterized using Attenuated Total Reflectance‐Fourier Transform Infrared (ATR‐FTIR) and X‐ray photoelectron (XPS) spectroscopy, ellipsometry, water contact angle analysis, and thermo gravimetric analysis (TGA). The effect of spacer group on the surface charge density was determined using zeta potential techniques. It is thought that this stratagem will facilitate the ability to tailor systematically both the interior and terminal polymer properties, providing a platform for further understanding how these conditions affect protein adsorption as well as cell‐surface interactions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011
Preparation of poly(p‐oxybenzoyl) crystals using direct polymerization of p‐hydroxybenzoic acid in the presence of boronic anhydrides
Authors: Kihara Masahiro , Kohama Shin‐Ichiro , Umezono Shota , Wakabayashi Kanji , Yamazaki Shinichi , Kimura Kunio
Published: January 2011

Poly(p‐oxybenzoyl) (POB) crystals were prepared by reaction‐induced crystallization during direct polymerization of p‐hydroxybenzoic acid in the presence of boronic anhydrides. Polymerizations were carried out at 300 °C in dibenzyltoluene at a concentration of 1% with three kinds of anhydrides of boronic acid such as 3,4,5‐trifluorophenylboronic acid (TFB), 4‐methoxyphenylboronic acid (MPB) and 4‐biphenylboronic acid (BPB). The POB crystals were formed as precipitates in the solution and the morphology was considerably influenced by both the structure of the boronic anhydride and its concentration (cB). Needle‐like crystals were firmed in the presence of TFB anhydride (TFBA) at cBs of 5 and 10 mol % by the spiral growth of lamellae. Spherical aggregates of slab‐like crystals were formed at cBs from 50 to 100 mol %. The polymerization with MPB anhydride and BPB anhydride (BPBA) also yielded the needle‐like crystals at cBs of 50 and 5 mol %, respectively. The polymerization with TFBA at lower cB was favorable to prepare the needle‐like crystal. Molecular weight was also influenced by the structure of the boronic anhydride and cB. Mn increased generally with cB and BPBA gave the highest Mn of 14.7 × 103 at cB of 100 mol %. The loose packing of the molecules in the crystal caused by the bulkiness of the end‐groups made the polymerization in the crystals more efficiently. Morphology and molecular weight of the POB crystals could be controlled by the chemical structure and the content of boronic anhydride. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.
Development of a new conjugated polymer containing dialkoxynaphthalene for efficient polymer solar cells and organic thin film transistors
Authors: Kwon Jun Ho , An Ji‐Young , Jang Hanmae , Choi Solji , Chung Dae Sung , Lee Min‐Jung , Cha Hyo‐Jung , Park Jin‐Hee , Park Chan‐Eon , Kim Yun‐Hi
Published: January 2011

A new semiconducting polymer, poly((5,5‐E‐α‐((2‐thienyl)methylene)‐2‐thiopheneacetonitrile)‐alt‐2,6‐[(1,5‐didecyloxy)naphthalene])) (PBTADN), an alternating copolymer of 2,3‐bis‐(thiophene‐2‐yl)‐acrylronitrile and didecyloxy naphthalene, is synthesized and used as an active material for organic thin film transistors (OTFTs) and organic solar cells. The incorporation of 2,3‐bis‐(thiophene‐2‐yl)‐acrylronitrile as an electron deficient group and didecyloxy naphthalene as an electron rich group resulted in a relatively low bandgap, high charge carrier mobility, and finally good photovoltaic performances of PBTADN solar cells. Because of the excellent miscibility of PBTADN and PC71BM, as confirmed by Grazing Incident X‐ray Scattering (GIXS) measurements and Transmission Electron Microscopy (TEM), homogeneous film morphology was achieved. The maximum power conversion efficiency of the PBTADN:PC71BM solar cell reached 2.9% with a Voc of 0.88 V, a short circuit current density (Jsc) of 5.6 mA/cm2, and a fill factor of 59.1%. The solution processed thin film transistor with PBTADN revealed a highest saturation mobility of 0.025 cm2/Vs with an on/off ratio of 104. The molecular weight dependence of the morphology, charge carrier mobility, and finally the photovoltaic performances were also studied and it was found that high molecular weight PBTADN has better self assembly characteristics, showing enhanced performance. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011
Synthesis and characterization of fluorene‐based oligomers and polymers incorporating N‐arylphenothiazine‐S,S‐dioxide units
Authors: Kamtekar Kiran T. , Dahms Katja , Batsanov Andrei S. , Jankus Vygintas , Vaughan Helen L. , Monkman Andrew P. , Bryce Martin R.
Published: January 2011

A series of 3,7‐bis(9,9‐di‐n‐hexylfluoren‐2‐yl)‐N‐arylphenothiazine‐S,S‐dioxide trimers and (9,9‐di‐n‐octylfluorene‐2,7‐diyl‐co‐N‐arylphenothiazine‐S,S‐dioxide) co‐polymers, with varying ratios of phenothiazine‐S,S‐dioxide units, have been prepared in good yields by palladium‐catalyzed cross‐coupling reactions. The materials are deep blue emitters and show no solvatochromism or evidence for an intramolecular charge‐transfer state. The photoluminescence quantum yields of the trimers are ϕPL 15–30% in solution and 14–25% in films. The polymers demonstrated very high values in solution (ϕPL 74–84%) and ϕPL values in films of 28–47%. The estimated HOMO energy levels are between −5.64 and −5.62 eV for the polymers with 15% incorporation of the phenothiazine‐S,S‐dioxide units. An analogous N‐arylphenothiazine co‐polymer shows significantly red shifted absorption and emission. Solution electrochemical data and density functional theory calculations are also presented. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011
L‐arabinitol‐based functional polyurethanes
Authors: Ferris Cristina , de Paz M. Violante , Galbis Juan A.
Published: January 2011

Three new polymerizable diols, based on mono‐, di‐, and tri‐O‐allyl‐L‐arabinitol derivatives, were prepared from L‐arabinitol as versatile materials for the preparation of tailor‐made polyurethanes with varied degrees of functionalization. Their allyl functional groups can take part in thiol‐ene reactions, to obtain greatly diverse materials. This “click” reaction with 2‐mercaptoethanol was firstly studied on the highly hindered sugar precursor 2,3,4‐tri‐O‐allyl‐1,5‐di‐O‐trityl‐L‐arabinitol, to apply it later to macromolecules. A polyurethane with multiple pendant allyl groups was synthesized by polyaddition reaction of 2,3,4‐tri‐O‐allyl‐L‐arabinitol with 1,6‐hexamethylene diisocyanate, and then functionalized by thiol‐ene reaction. The coupling reaction took place in every allyl group, as confirmed by standard techniques. The thermal stability of the novel polyurethanes was investigated by thermogravimetric analysis and differential scanning calorimetry (DSC). This strategy provides a simple and versatile platform for the design of new materials whose functionality can be easily modified. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011