bluuebunny/crossref_metadata_2025 huggingface dataset:
Diffusion of semi‐flexible polyelectrolyte through nanochannels
Authors: Gu Hongyan , Faucher Santiago , Zhu Shiping
Published: November 2009

The diffusion of sodium polystyrene sulfonate through polycarbonate nanochanels was studied in salt‐free dilute aqueous solution. A stronger molecular weight dependence of diffusion was observed compared to free diffusion in dilute solution. Scaling exponentials relating polymer size to diffusivity were between Flory's theory (Deff ∝ N−0.6) and Rouse's model (Deff ∝ N−1), revealing a crossover regime from 3‐D diffusion to 1‐D diffusion. Diffusion was less hindered for the polyelectrolyte (Deff/D0), than for a rigid sphere, when the polymer/channel size ratio exceeded 0.2. This is attributed to elongated chains with reduced frictional hindrance. Simulation of the confined diffusion based on an elongated cigar model gave D ∝ N−1
${R_{\rm t}^{2/3}}$
while the experimental results agree with D ∝ N−0.94${R_{\rm t}^{ 2/3}}$. For charged polyelectrolytes, the transition to 1‐D diffusion therefore begins before the polymer radius of gyration exceeds the channel size contrary to model assumptions. We attribute this to the charged nature of the polyelectrolytes causing extended chain conformations. © 2009 American Institute of Chemical Engineers AIChE J, 2010
Synthesis of PEGylated single wall carbon nanotubes by a photoinitiated graft from polymerization
Authors: Zhang Pu , Henthorn David B.
Published: November 2009

A considerable amount of research has been devoted to carbon nanotubes because of their unique electrical, mechanical, optical, and chemical properties. Here, in this report, we introduce a novel, simple ultraviolet initiated “graft from” polymerization method to synthesize PEGylated carbon nanotubes. This grafting procedure significantly enhanced nanotube aqueous dispersibility and long term stability in solution. Mass of grafted polymer chains was easily modulated by adjusting polymerization reaction time, and nanomaterials containing up to 80% polymer by weight were synthesized. Nanotube morphology was characterized by SEM, TEM before and after the functionalization. In addition, the covalent bonding of polymer chains to the nanotubes structure was elucidated by Raman, ATR‐FTIR, and XPS spectroscopy. © 2009 American Institute of Chemical Engineers AIChE J, 2010
Synthesis of glycidyl methacrylate containing diethanol amine and its binary copolymers with ethyl methacrylate and butyl methacrylate as nano‐size chelating resins for removal of heavy metal ions
Authors: Abd El‐Ghaffar M. A. , El‐Halawany N. R. , Ahmed S. A.
Published: November 2009

One of the most important applications of chelating and functional polymers is their capability to recover metal ions from their solutions. This study concerns the synthesis of a hydrophilic glycidyl methacrylate (GMA) monomer‐bearing diethanol amine (DEA) chelating group from the reaction of GMA and DEA. The formed adduct (A) was characterized via FTIR and mass spectra and subjected to homopolymerization and binary copolymerization with ethyl methacrylate and butyl methacrylate. The copolymerization process was carried out via a semi‐batch emulsion polymerization technique by using potassium persulphate/sodium bisulphite as a redox pair initiation system and sodium dodecyl benzene sulphonate as an emulsifier at 65°C. The obtained polymers were characterized via FTIR, thermal gravimetric analysis, and UV–VIS. Volume‐average diameters (Dv) in nanoscale range for the prepared polymers were confirmed by transmission electron microscope investigation. It was shown that the obtained nano‐size chelating polymers have a powerful adsorption character toward transition metal ions (Cu+2, Cr+3, Ni+2, and Co+2) and efficient selectivity for Cu+2 and Ni+2 ions at normal pH. The effects of pH, time, and different comonomer feed compositions on the uptake of metal ions were studied. The reaction between the obtained chelating resins and different metal ions was confirmed to be a second‐order reaction. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
Biodegradable polyurethane elastomers prepared from isocyanate‐terminated poly(ethylene adipate), castor oil, and glycerol
Authors: Teramoto Naozumi , Saitoh Yuichi , Takahashi Atsuo , Shibata Mitsuhiro
Published: November 2009

The curing reaction of tolylene‐2,4‐diisocyanate‐terminated poly(ethylene adipate) (PEA‐TDI) with a mixture of castor oil (CO) and glycerol (GO) with a NCO/OH ratio of 1.0 at 150°C gave crosslinked polyurethane (CO/GO‐PU). All the polyurethanes were elastomeric materials at room temperature. The glass‐transition temperature of the CO/GO‐PU increased with decreasing CO/GO ratio. All the cured polyurethanes had a higher 5% weight loss temperature than PEA‐TDI. The tensile strength and modulus of the polyurethanes increased with decreasing CO/GO ratio, and tensile residual strain after 300% elongation for all the CO/GO‐PUs was almost 0. All the polyurethanes had biodegradability, when measured by a biochemical oxygen demand method in an aqueous medium using activated sludge. The rate of the biodegradation of the polyurethanes increased with an increase of CO/GO ratio. The crosslinked CO‐PU showed much higher biodegradability than the linear PEA‐TDI. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
Synthesis and characterization of pH‐ and salt‐responsive hydrogels based on etherificated sodium alginate
Authors: Lin Hailin , Zhou Jinjin , Yingde Cui , Gunasekaran Sundaram
Published: November 2009

Hydrogels composed of etherificated sodium alginate (ESA), sodium acrylic acid (NaAA), and poly (vinyl alcohol) (PVA) were synthesized by aqueous solution polymerization. The effects of reaction variables such as terminal pH, ions, and ionic strength on hydrogel swelling ratio (SR) were determined and compared. SR was influenced strongly by pH and ionic strength. SR increased with increasing pH but tended to decrease with PVA content. At a given ionic strength, SR of ESA/NaAA/PVA hydrogel was dependent on the valence of anion; SR was higher in multivalent anion salt solution than in monovalent anion salt solution, i.e., SRK2SO4 > SRKCl and SRNa2SO4 > SRNaCl. The swelling kinetic of the hydrogels showed Fickian kinetic diffusion in acidic media and non‐Fickian behavior in alkaline media. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
Reactivity ratios and copolymer composition evolution during styrene/dimethacrylate free‐radical crosslinking copolymerization
Authors: Schroeder Walter F. , Aranguren Mirta I. , Borrajo Julio
Published: November 2009

In this article, experimental and simulated results are presented for the evolution of the copolymer composition as unsaturations are consumed in the free‐radical cross‐linking copolymerization of Styrene(St) and BisphenolA glycerolate dimethacrylate (BDMA). Real time FTIR measurements were performed to monitor the depletion of each comonomer double bond during the isothermal curing reaction at 80°C. From the experimental data corresponding to different feed compositions, the initial reactivity ratios and their evolution with conversion were determined via a nonlinear least squares optimization of the integrated form of the copolymerization equation. The reactivity ratio of St increases continuously and exponentially with the overall reaction conversion, while that of BDMA decreases linearly. A modified terminal copolymerization model including the dependence of the reactivity ratios with the overall conversion was proposed. The application of this model provides a consistent fitting for the conversion of each comonomer during all reaction stages, even at high conversion values where large diffusion and topological restrictions for chain movements are present. Simulations show that the concentration of styrene units added to the copolymer increases with the overall reaction conversion, while that for the BDMA double bonds diminishes. Structures rich in homopolymerized styrene are predicted at later stages of the reaction.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
Highly crosslinked micron‐sized, monodispersed polystyrene particles by semicontinuous dispersion polymerization. II. Semicontinuous, delayed addition and seeded semicontinuous processes
Authors: Lee Ki‐Chang , Wi Han‐Ah
Published: November 2009

A highly crosslinked, monodispersed polystyrene (PS) particle was prepared by the seeded semicontinuous dispersion polymerization using ready‐made monodispersed PS seed particles. The effects of Styrene (in 2nd stage)/Styrene (in PS seed) ratio, addition point and feeding time of divinylbenzene (DVB), concentration of DVB and polymerization temperature on the particle size, size distribution and morphology of the resulting particles were investigated. Monodispersed PS particles with 15 wt % of the DVB were prepared at 1/1 in St/St ratio, In comparison, highly crosslinked monodispersed and smooth‐surfaced PS particles containing up to 70 wt % of the DVB were effectively prepared at 0/1. 5% weight loss of the PS particles determined by TGA occurred from 353.3 to 389.6°C and the degree of swellability in toluene decreased from 113 to 101% as the DVB concentration increased from 10 to 70 wt %, implying increased thermal stability and solvent resistance due to the increase of the crosslink density. This study demonstrates that the seeded semicontinuous process, primarily with the starved condition at the second stage, is an efficient way to obtain highly crosslinked, monodispersed PS particles. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
Influence of structural feature of aluminum coatings on mechanical and water barrier properties of metallized PET films
Authors: Garnier Géraldine , Yrieix Bernard , Brechet Yves , Flandin Lionel
Published: November 2009

This article focuses on description and evaluation of multilayer films, which are used for vacuum insulation panels (VIP). The materials investigated include a neat polyethylene terephthalate (PET) and PET films coated by chemical vapor deposition with different aluminum thicknesses. The aim of these investigations was to evaluate the influence of structural features on the physical properties of Al/PET systems. The morphological analyzes associated to water vapor permeability measurements showed that the metallized surface exhibited defects through which a small amount of water vapor can permeate. It is shown that the permeance varies linearly with the surface fraction occupied by pinholes which in turn changes linearly with the aluminum thickness. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
Study of the biodegradable poly(ε‐caprolactone)/clay nanocomposite foams
Authors: Liu Hao , Han Changyu , Dong Lisong
Published: November 2009

In this article, biodegradable poly(ε‐caprolactone)/layered silicate nanocomposites were prepared and characterized. The dispersion state of modified clay in PCL matrix and its effect on thermal, rheological and mechanical properties of PCL were studied. The PCL/clay nanocomposites were then foamed using chemical foaming method. Cellular parameters such as mean cell size, cell wall thickness and cell densities of nanocomposite foams with different clay loading were collected. Effect of layered silicate on the structure and mechanical properties of PCL foams were evaluated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
The influence of electrospinning parameters on the structural morphology and diameter of electrospun nanofibers
Authors: Jacobs Valencia , Anandjiwala Rajesh D. , Maaza Malik
Published: November 2009

Electrospinning is a simple method of producing nanofibers by introducing electric field into the polymer solutions. We report an experimental investigation on the influence of processing parameters and solution properties on the structural morphology and average fiber diameter of electrospun poly ethylene oxide (PEO) polymer solution. Experimental trials have been conducted to investigate the effect of solution parameters, such as concentration, molecular weight, addition of polyelectrolyte in PEO solution, solvent effect, as well as governing parameter, such as applied voltage. The concentration of the aqueous PEO solution has shown noteworthy influence on the fiber diameter and structural morphology of electrospun nanofibers. At lower concentrations of PEO polymer solution, the fibers showed irregular morphology with large variations in fiber diameter, whereas at higher concentrations, the nanofibers with regular morphology and on average uniform fiber diameter were obtained. We find that the addition of polyelectrolytes, such as sodium salt of Poly acrylic acid (PAA) and Poly allylamine hydrochloride (PAH), increases the conductivity of PEO solutions and thereby decreases the bead formation in electrospun nanofibers. The increase in applied voltage has been found to affect the structural morphology of nanofiber while the addition of ethanol in PEO solution diminishes the bead defects. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
New sets of solubility parameters of linear and crosslinked aromatic polyamides
Authors: Fiori Stefano , Monticelli Orietta , Alzari Valeria , Mariani Alberto
Published: November 2009

As generally accepted, also in the case of polyamides linear and crosslinked polymeric materials are believed to be characterized by the same solution properties and, consequently, by the same solubility parameters. However, despite their great practical importance, a thorough study aimed to determine the best solvent media able to dissolve linear aromatic polyamides has not been performed yet or, at least, has not been published. In this study, we report on our study on the solubility parameters of linear and crosslinked aromatic polyamides. We demonstrate that the assumption of considering these two classes as having the same solubility properties can lead to dramatically erroneous results. Two new different sets for linear and crosslinked aromatic polyamides are proposed. Namely, linear poly(p‐phenylene terephthalamide) is characterized by δp, δd, and δH equal to 8.6, 18.4, and 11.3, respectively; by contrast, the corresponding values of the crosslinked aromatic polyamides taken into consideration are: 11.5, 16.8, and 10.2. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
Synthesis and characterization of copolymers based on poly(butylene terephthalate) and ethylene oxide‐poly(dimethylsiloxane)‐ethylene oxide
Authors: Vučković Marija V. , Antić Vesna V. , Govedarica Milutin N. , Djonlagić Jasna
Published: November 2009

A series of thermoplastic elastomers based on ethylene oxide‐poly(dimethylsiloxane)‐ethylene oxide (EO‐PDMS‐EO), as the soft segment, and poly(butylene terephthalate) (PBT), as the hard segment, were synthesized by catalyzed two‐step, melt transesterification reaction of dimethyl terephthalate (DMT) with 1,4‐butanediol (BD) and α,ω‐dihydroxy‐(EO‐PDMS‐EO). Copolymers with a content of hard PBT segments between 40 and 90 mass % and a constant length of the soft EO‐PDMS‐EO segments were prepared. The siloxane prepolymer with hydrophilic terminal EO units was used to improve the miscibility between the polar comonomers, DMT and BD, and the nonpolar PDMS. The molecular structure and composition of the copolymers were determined by 1H‐NMR spectroscopy, whereas the effectiveness of the incorporation of α,ω‐dihydroxy‐(EO‐PDMS‐EO) into the copolymer chains was verified by chloroform extraction. The effects of the structure and composition of the copolymers on the melting temperatures and the degree of crystallinity, as well as on the thermal degradation stability and some rheological properties, were studied. It was demonstrated that the degree of crystallinity, the melting and crystallization temperatures of the copolymers increased with increasing mass fraction of the PBT segments. The thermal stability of the copolymers was lower than that of PBT homopolymer, because of the presence of thermoliable ether bonds in the soft segments. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
Self synthesize of silver nanoparticles in/on polyurethane nanofibers: Nano‐biotechnological approach
Authors: Sheikh Faheem A. , Barakat Nasser A. M. , Kanjwal Muzafar A. , Jeon Seol‐Hee , Kang Hyung‐Sub , Kim Hak‐Yong
Published: November 2009

In this study, we are introducing a new class of Polyurethane (PU) nanofibers containing silver nanoparticles (NPs) by electrospinning. A simple method not depending on the addition of foreign chemicals has been used to self‐synthesize of silver NPs in/on PU nanofibers. Typically, a sol−gel consisting of AgNO3/PU/N,N‐dimethylformamide (DMF) has been electrospun and aged for a week, so silver NPs have been created in/on PU nanofibers. Syntheses of silver NPs were carried out by exploiting the reduction ability of the DMF solvent which is the main constituent to obtain PU electrospun nanofibers in decomposition of silver nitrate precursor into silver NPs. Physiochemical characterizations confirmed well oriented nanofibers and good dispersing of pure silver NPs. Various parameters affecting utilizing of the prepared nanofibers on various nano‐biotechnological fields have been studied. For instance, the obtained nanofiber mats were checked for mechanical properties which showed the improvement of the tensile strength upon increase in silver NPs content. Moreover, the nanofibers were subjected to 10 times successive washing experiments with using solid to liquid ratio of 3 : 5000 for 25 h, UV spectroscopy analysis reveals no losses of silver NPs from the PU nanofibers. 3T3‐L1 fibroblasts were cultured in presence of the designed nanofibers. The morphological features of the cells attached on nanofibers were examined by BIO‐SEM, which showed well attachment of cells to fibrous mats. The cytotoxicity results indicated absence of toxic effect on the 3T3‐L1 cells after cell culturing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
A comprehensive volumetric analysis of the cerebellum in children and adolescents with autism spectrum disorder
Authors: Scott Julia A. , Schumann Cynthia Mills , Goodlin‐Jones Beth L. , Amaral David G.
Published: November 2009

Magnetic resonance imaging (MRI) and postmortem neuropathological studies have implicated the cerebellum in the pathophysiology of autism. Controversy remains, however, concerning the nature and the consistency of cerebellar alterations. MRI studies of the cross‐sectional area of the vermis have found both decreases and no difference in autism groups. Volumetric analysis of the vermis, which is less prone to “plane of section artifacts” may provide a more reliable assessment of size differences but few such studies exist in the literature. Here we present the results of a volumetric analysis of the structure of the whole cerebellum and its components in children and adolescents with autism spectrum disorders. Structural MRI's were acquired from 62 male participants (7.5 to 18.5 years‐old) who met criteria for the following age‐matched diagnostic groups: low functioning autism, high functioning autism (HFA), Asperger syndrome, and typically developing children. When compared to controls, the midsagittal area of the vermis, or of subgroups of lobules, was not reduced in any of the autism groups. However, we did find that total vermis volume was decreased in the combined autism group. When examined separately, the vermis of only the HFA group was significantly reduced compared to typically developing controls. Neither IQ nor age predicted the size of the vermis within the autism groups. There were no differences in the volume of individual vermal lobules or cerebellar hemispheres. These findings are discussed in relation to the pathology of autism and to the fairly common alterations of vermal morphology in various neurodevelopmental disorders.
Does EMDR reduce post‐traumatic stress disorder symptomatology in combat veterans?
Authors: Albright David L. , Thyer Bruce
Published: November 2009

Prior meta‐analyses have suggested that eye‐movement desensitization and reprocessing (EMDR) may be effective in alleviating the symptoms of post‐traumatic stress disorder (PTSD). EMDR is now being recommended as a treatment for military combat veterans who suffer from PTSD. We provide a review of published outcome studies that appeared in print from 1987 – April, 2008 which examined the specific effects of EMDR on PTSD among military combat veterans. Studies were identified through electronic bibliographic databases, web sites, and manual searches of article reference lists. A total of six randomized controlled trials (RCTs) and three quasi‐experimental studies met our inclusionary criteria and are reviewed. The evidence supporting the use of EMDR to treat combat veterans suffering from PTSD is sparse and equivocal, and does not rise to the threshold of labeling the therapy as an empirically supported treatment. It is premature to incorporate EMDR into routine care for veterans to alleviate combat‐related PTSD. EMDR needs a considerably stronger evidentiary foundation which includes large‐scale RCTs involving credible placebo controlled treatment conditions. Copyright © 2009 John Wiley & Sons, Ltd.
Importance of the spatial display of charged residues in heparin–peptide interactions
Authors: Rullo Anthony , Nitz Mark
Published: November 2009

Many studies have examined consensus sequences required for protein‐glycosaminoglycan interactions. Through the synthesis of helical heparin binding peptides, this study probes the relationship between spatial arrangement of positive charge and heparin binding affinity. Peptides with a linear distribution of positive charge along one face of the α‐helix had the highest affinity for heparin. Moving the basic residues away from a single face resulted in drastic changes in heparin binding affinity of up to three orders of magnitude. These findings demonstrate that amino acid sequences, different from the known heparin binding consensus sequences, will form high affinity protein‐heparin binding interactions when the charged residues are aligned linearly. © 2009 Wiley Periodicals, Inc. Biopolymers 93: 290–298, 2010.

This article was originally published online as an accepted preprint. The “Published Online” date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com
Development of a liquid chromatography–isotope dilution mass spectrometry method for quantification of fentanyl in human plasma
Authors: Lu Chuan , Jia Jing‐ying , Gui Yu‐zhou , Liu Gang‐yi , Shi Xiao‐jin , Li Shui‐jun , Yu Chen
Published: November 2009

Fentanyl is a potent analgesic drug in relieving chronic pain in patients. In this report, we present a simple, reliable and sensitive LC–ID/MS method for the quantification of fentanyl in human plasma. LC‐ID/MS analysis was carried out on a triple quadrupole mass spectrometer operated in positive electrospray ionization multiple‐reaction‐monitoring using the transitions m/z 337.6 → 187.9 for fentanyl and m/z 342.6 → 187.9 for the internal standard (D5‐fentanyl). The calibration curve covered the range 0.02–10 ng/mL. The intra‐ and inter‐batch precision were less than 6.739 and 3.126% for fentanyl and IS, with accuracy from 94.16 to 102.0%. The lower limit of quantification was identifiable and reproducible at 0.02 ng/mL. The validated method offered increased sensitivity and wide linear concentration range. This method was successfully adopted for the evaluation of bioequivalence of two fentanyl transdermal preparations after single dose administration to 20 Chinese pain‐patients. Copyright © 2009 John Wiley & Sons, Ltd.
Isothiocyanates as derivatization reagents for amines in liquid chromatography/electrospray ionization–tandem mass spectrometry
Authors: Santa Tomofumi
Published: November 2009

The applicability of 3‐pyridyl isothiocyanate, p‐(dimethylamino)phenyl isothiocyanate and m‐nitrophenyl isothiocyanate as the derivatization reagents for amines in high‐performance liquid chromatography/electrospray ionization–tandem mass spectrometry (LC/ESI‐MS/MS) was examined. The generated derivatives of amines with these reagents were favorably separated on the reversed‐phase column and detected by ESI‐MS/MS. The C–N bond of the generated thiourea structure was efficiently cleaved by collision‐induced dissociation and gave the single and intense product ion. Among the three reagents, 3‐pyridyl isothiocyanate was the most suitable as the derivatization reagent with regard to the reactivity to amines and the detection sensitivity. Copyright © 2009 John Wiley & Sons, Ltd.
A sensitive and specific liquid chromatography/tandem mass spectrometry method for quantification of nevirapine and its five metabolites and their pharmacokinetics in baboons
Authors: Ren Chen , Fan‐Havard Patty , Schlabritz‐Loutsevitch Natalia , Ling Yonghua , Chan Kenneth K. , Liu Zhongfa
Published: November 2009

A highly sensitive and specific LC‐MS/MS assay was developed and validated to quantify nevirapine (NVP) and its five metabolites [2‐, 3‐, 8‐, 12‐hydroxyl NVP (OHNVP) and 4‐carboxyl NVP (CANVP)] simultaneously in baboon serum and the assay was used to characterize their pharmacokinetic studies of an oral‐dose escalation study in baboon. The lower limit of quantification (LLOQ) for NVP and its four hydroxyl nevirapine metabolites was 1.0 ng/mL and for 4‐CANVP was 5.0 ng/mL. The between‐run and within‐run precisions and accuracies at four quality control concentrations (1, 5, 50 and 500 ng/mL) were evaluated in baboon serum with less than 14% variation and 93–114% accuracies (n= 6), except for the LLOQ for 2‐OHNVP, which had an accuracy of 115.8% for between‐run validation. The pharmacokinetics of NVP and its five metabolites in non‐pregnant baboons by a single‐dose escalation study were also profiled. The major metabolites detected were 4‐CANVP and 12‐OHNVP. 3‐OHNVP and 2‐OHNVP were the minor metabolites with only a trace amount of 2‐OHNVP detected in some pharmacokinetic samples. No 8‐OHNVP was observed in all of the pharmacokinetic samples. In addition, the fragmentation for the four hydroxyl metabolite isomers is also discussed. Copyright © 2009 John Wiley & Sons, Ltd.
Development and validation of an analytical method for the quantification of cytochrome c in skin transport studies
Authors: Bachhav Yogeshwar G. , Kalia Yogeshvar N.
Published: November 2009

A simple isocratic HPLC method for the quantification of Cytochrome c in skin permeation samples was developed and validated. The mobile phase comprised a 41 : 59 mixture of an organic phase A (0.1% trifluoroacetic acid in a 90 : 10 mixture of MeCN–H2O) and an aqueous phase B (0.1% trifluoroacetic acid in H2O). The Cytochrome c retention and run times were 2.62 and 8.0 min, respectively—much shorter than those for existing gradient methods. The response was accurate, precise and linear from 2.5 to 25 μg/mL. The mean recoveries for intra‐day and inter‐day analysis ranged from 88.5 to 103.8% and the RSD varied from 0.05 to 1.55%. The assay was used to quantify transport of Cytochrome c across intact and laser‐microporated porcine skin in vitro. Cytochrome c permeation and the amount of protein retained within the membrane over 24 h were quantified as a function of the number of micropores. Although no Cytochrome c permeation was observed across intact skin, laser microporation enabled delivery of 22.9 ± 3.3 and 56.0 ± 15.9 μg/cm2 of the protein across skin samples with 300 and 1800 micropores, respectively. In conclusion, the HPLC method provided a fast, efficient means to quantify Cytochrome c in samples from skin transport studies. Copyright © 2009 John Wiley & Sons, Ltd.
Profiles of adult survivors of severe sexual, physical and emotional institutional abuse in Ireland
Authors: Fitzpatrick Mark , Carr Alan , Dooley Barbara , Flanagan‐Howard Roisín , Flanagan Edel , Tierney Kevin , White Megan , Daly Margaret , Shevlin Mark , Egan Jonathan
Published: November 2009

Adult survivors of institutional abuse were interviewed with a comprehensive assessment protocol which included the Childhood Trauma Questionnaire, the Institutional Child Abuse Processes and Coping Inventory, the Structured Clinical Interviews for Disorders of the Diagnostic and Statistical Manual of Mental Disorders IV axis I disorders and personality disorders, the Trauma Symptoms Inventory, a Life Problems Checklist, the Experiences in Close Relationships Inventory and the Kansas Marital Satisfaction Scale. Profiles were identified for subgroups that described severe sexual (N = 60), physical (N = 102), or emotional (N = 85) abuse as their worst forms of maltreatment. Survivors of severe sexual abuse had the most abnormal profile, which was characterised by higher rates of all forms of child maltreatment and higher rates of post‐traumatic stress disorder, alcohol and substance abuse, antisocial personality disorder, trauma symptoms and life problems. Survivors of severe emotional abuse were better adjusted than the other two groups. The profile of survivors of severe physical abuse occupied an intermediate position between the other two groups. A thorough assessment of abuse history and current functioning should be conducted when providing services to adult survivors of institutional abuse, since this may have important implications for the intensity of services required. Survivors of severe sexual abuse may require more intensive services. Copyright © 2009 John Wiley & Sons, Ltd.
The harms of pornography exposure among children and young people
Authors: Flood Michael
Published: November 2009

Exposure to pornography is routine among children and young people, with a range of notable and often troubling effects. Particularly among younger children, exposure to pornography may be disturbing or upsetting. Exposure to pornography helps to sustain young people's adherence to sexist and unhealthy notions of sex and relationships. And, especially among boys and young men who are frequent consumers of pornography, including of more violent materials, consumption intensifies attitudes supportive of sexual coercion and increases their likelihood of perpetrating assault. While children and young people are sexual beings and deserve age‐appropriate materials on sex and sexuality, pornography is a poor, and indeed dangerous, sex educator. Copyright © 2009 John Wiley & Sons, Ltd.
Transcriptional regulation of IER3IP1 gene by tumor necrosis factor‐α and Sp family proteins
Authors: Yiu Wai Han , Yeung Tsz Lun , Poon Jodie Wing Ming , Tsui Stephen Kwok Wing , Fung Kwok Pui , Waye Mary Miu Yee
Published: November 2009

Immediate early response 3 interacting protein 1 (IER3IP1) is an endoplasmic reticulum protein with its potential cellular function involved in cell differentiation and cell death processes. In this report, we investigated the molecular mechanism by which the expression of IER3IP1 gene is regulated by cloning the 5′ flanking region of the human IER3IP1 gene for various promoter studies. Deletion analysis was used to identify the basal promoter activity retained at −298/−59 region and mutation analysis proved that Sp1 is a transcriptional activator of this gene expression. As an early response gene, IER3IP1 showed an increase in transcription in response to tumor necrosis factor α (TNF‐α) in a time‐ and dose‐dependent manner. This inducible response to TNF‐α is mediated by the demonstration of nuclear factor κB (NF‐κB) responsive element on IER3IP1 promoter sequence. From our results, we suggest that IER3IP1 gene is involved in TNF‐α‐mediated cellular response to stressful conditions. Copyright © 2009 John Wiley & Sons, Ltd.
Increased resistance to hydrogen peroxide‐induced cardiac contracture is associated with decreased myocardial oxidative stress in hypothyroid rats
Authors: da Rosa Araujo Alex Sander , Silva de Miranda Madalena Freitas , de Oliveira Ubirajara Oliveira , Fernandes Tânia , Llesuy Susana , Rios Kucharski Luiz Carlos , Khaper Neelam , Belló‐Klein Adriane
Published: November 2009

The purpose of this study was to determine whether decreased oxidative stress would increase the resistance to cardiac contracture induced by H2O2 in hypothyroid rats. Male Wistar rats were divided into two groups: control and hypothyroid. Hypothyroidism was induced via thyroidectomy. Four weeks post surgery, blood samples were collected to perform thyroid hormone assessments, and excised hearts were perfused at a constant flow with or without H2O2 (1 mmol/L), being divided into two sub‐groups: control, hypothyroid, control + H2O2, hypothyroid + H2O2. Lipid peroxidation (LPO) was evaluated by chemiluminescence (CL) and thiobarbituric acid reactive substances (TBARS) methods, and protein oxidation by carbonyls assay in heart homogenates. Cardiac tissue was also screened for superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx) activities, and for total radical‐trapping antioxidant potential (TRAP). Analyses of SOD and glutathione‐S‐transferase (GST) protein expression were also performed in heart homogenates. Hypothyroid hearts were found to be more resistant to H2O2‐induced contracture (60% elevation in LVEDP) as compared to control. CL, TBARS, carbonyl, as well as SOD, CAT, GPx activities and TRAP levels were reduced (35, 30, 40, 30, 16, 25, and 33%, respectively) in the cardiac homogenates of the hypothyroid group as compared to controls. A decrease in SOD and GST protein levels by 20 and 16%, respectively, was also observed in the hypothyroid group. These results suggest that a hypometabolic state caused by thyroid hormone deficiency can lead to an improved response to H2O2 challenge and is associated with decreased oxidative myocardial damage. Copyright © 2009 John Wiley & Sons, Ltd.
Diarylpropane‐1,3‐dione Derivatives as TetR‐Inducing Tetracycline Mimetics: Synthesis and Biological Investigations
Authors: Kormann Christian , Pimenta Irina , Löber Stefan , Wimmer Cornelius , Lanig Harald , Clark Timothy , Hillen Wolfgang , Gmeiner Peter
Published: November 2009

Synthesis, biological investigations and molecular docking studies of nonantibiotic and nontetracyclic inducers that feature a minimal key motif of the natural lead tetracycline are presented. The diarylpropane‐1,3‐dione motif was identified as the minimal substructure responsible for TetR induction by tetracyclines. The first nontetracyclic surrogates of the natural tetracyclines displayed significant inducing effects for TetR(BD)S135L, whereby the chlorohydroxyphenyl‐substituted β‐diketone 31 displayed the highest activity. Interestingly, antibiotic activity could not be detected for 31. Homology modeling based on the X‐ray structure of 7‐chlorotetracycline bound to TetR indicated analogous binding modes for the natural inducer and the synthetic diarylpropane‐1,3‐dione derivatives.
γ‐Alumina‐Supported Silver Cluster for N‐Benzylation of Anilines with Alcohols
Authors: Shimizu Kenichi , Nishimura Masanari , Satsuma Atsushi
Published: November 2009

An alumina‐supported silver cluster with a Lewis acidic cocatalyst (polyvalent metal salts, such as FeCl3⋅6 H2O) acts as a heterogeneous and recyclable catalyst for the direct N‐alkylation of anilines with benzyl alcohols, which is driven by the borrowing hydrogen mechanism. Systematic studies on the effects of metal (Pt, Pd, Au, and Ag), silver particle size, support oxides (CeO2, ZrO2, Al2O3, SiO2), and Lewis acidic additives show four important factors required to achieve selective N‐alkylation of anilines: 1) metal with a weak metal–hydrogen bond energy (i.e., Ag), 2) smaller size of the silver cluster, 3) the support having both acidic and basic sites (i.e., Al2O3), and 4) additives with high Lewis acidity (i.e., FeIII salt). Fundamental information will be useful for the rational design of platinum‐group metal‐free heterogeneous catalysts for environmentally benign CN bond forming reactions.
Supramolecular Assemblies of Polyaniline through Cooperative Bundling by a Palladium‐Complex‐Appended Synthetic Cross‐Linker
Authors: Kaseyama Takahiro , Takebayashi Shinji , Wakabayashi Rie , Shinkai Seiji , Kaneko Kenji , Takeuchi Masayuki
Published: November 2009

A synthetic cross‐linker (1) bearing two binding sites for imine moieties in polyaniline has been used to organize polyaniline emeraldine base (EB) or polyaniline emeraldine salt (ES) into aligned assemblies. Complex 1 exhibited highly cooperative binding toward mEB (a repeating unit analogue of EB), for which the association constants K1 and K2 were evaluated to be 2.2×104 and 9.4×105 M‐1, respectively. 1H NMR studies revealed that the diimine moieties in mEB are recognized cooperatively in anti‐conformation by 1. The ordered structures organized from 1 and EB or ES were efficiently formed through supramolecular bundling. These ordered assemblies have a periodicity of 2.5 nm that was confirmed by means of transmittance electron microscopy (TEM) and high‐resolution TEM (HRTEM). The cooperative binding would be important for the bundling and alignment of the polymers, as evidenced by the fact that neither reference compounds 2 nor 3 were capable of producing similar assemblies. The electric conductivity of the samples was measured and the results were discussed.
HPLC‐method for determination of permethrin enantiomers using chiral β‐cyclodextrin‐based stationary phase
Authors: Shishovska Maja , Trajkovska Vera
Published: November 2009

The liquid chromatographic separation of permethrin enantiomers on chiral β‐cyclodextrin‐based stationary phase has been investigated. All four enantiomers are obtained by using simple methanol and water mobile phase, under gradient mode. The method was optimized and validated. The relationship between temperature and chromatographic parameters: k′ (capacity factor), α (separation factor) and Rs (resolution factor) was studied. Van't Hoff's curves for each enantiomer were plotted for temperature range 288–318 K. It was noticed that the response factor ratio of permethrin isomers differ and calculated value is found to be 1.66 (cis/trans, for n = 5). This method has been used for determining permethrin enantiomer ratio for a few samples of working standards and one formulation. Chirality 2010. © 2009 Wiley‐Liss, Inc.
New applications and challenges for computational ROA spectroscopy
Authors: Pecul Magdalena
Published: November 2009

In this article, applications of quantum chemical methods in calculations of the vibrational Raman optical activity (ROA) spectra are reviewed and new developements are discussed. Modeling of ROA spectra of amino acids and peptides and applications for establishing absolute configuration are briefly outlined. Particular attention is paid to the modeling of solvent effects on ROA spectra, anharmonicity in ROA, resonance and pre‐resonance ROA spectra, and ROA spectra of molecules adsorbed on metal surfaces or metal nanoparticles (surface‐enhanced Raman optical activity, SEROA). Remaining challenges in computational ROA spectroscopy are also pointed out. Chirality 21:E98–E104, 2009. © 2009 Wiley‐Liss, Inc.
Channel‐like crystal structure of cinchoninium L‐O‐phosphoserine salt dihydrate
Authors: Wesełucha‐Birczyńska Aleksandra , Oleksyn Barbara J. , Wątroba Joanna
Published: November 2009

Studies on the interactions between L‐O‐ phosphoserine, as one of the simplest fragments of membrane components, and the Cinchona alkaloid cinchonine, in the crystalline state were performed. Cinchoninium L‐O‐phosposerine salt dihydrate (PhSerCin) crystallizes in a monoclinic crystal system, space group P21, with unit cell parameters: a = 8.45400(10) Å, b = 7.17100(10) Å, c = 20.7760(4) Å, α = 90°, β = 98.7830(10)°, γ = 90°, Z = 2. The asymmetric unit consists of the cinchoninium cation linked by hydrogen bonds to a phosphoserine anion and two water molecules. Intermolecular hydrogen bonds connecting phosphoserine anions via water molecules form chains extended along the b axis. Two such chains symmetrically related by twofold screw axis create a “channel.” On both sides of this channel cinchonine cations are attached by hydrogen bonds in which the atoms N1, O12, and water molecules participate. This arrangement mimics the system of bilayer biological membrane. Chirality 2010. © 2009 Wiley‐Liss, Inc.
Factors influencing the interconversion of a new class of dibenzodiazepine sulfonamide atropisomers
Authors: Welch Christopher J. , Gong Xiaoyi , Schafer Wes , Chobanian Harry , Lin Linus , Biba Mirlinda , Liu Ping , Guo Yan , Beard Adam
Published: November 2009

A novel family of atropisomers based on a conformationally constrained seven membered ring system is investigated using a combination of preparative chiral chromatography, circular dichroism, and other analytical techniques. The influence of structure on the rate of atropisomer interconversion was explored with a series of analogs showing a range of interconversion rates ranging from very fast (undetectable on the HPLC timescale) to very slow (half life of many days). Chirality 21:E105–E109, 2009. © 2009 Wiley‐Liss, Inc.
„Ich rieche was, was du nicht riechst”︁:
Authors: Waitz Thomas , Tiemann Michael
Published: November 2009

Halbleitende Metalloxid‐Gassensoren werden sowohl im industriellen Bereich als auch im Haushalt zur Luftüberwachung verwendet. Die Funktionsweise basiert auf einer reversiblen Änderung des Sensorwiderstandes in Anwesenheit sowohl oxidierender als auch reduzierender Gase, die mit einfachen Mitteln gemessen werden kann. In diesem Artikel wird vorgestellt, wie sich die bei der Gasdetektion ablaufenden Vorgänge mit Hilfe des Ionosorptionsmodells in Kombination mit einem einfachen Festkörperbändermodell deuten lassen. Abschließend werden einfache, im Chemieunterricht zu realisierende Experimente mit Gassensoren präsentiert.
Grundchemikalien aus Kohlenhydraten
Authors: Eissen Marco , Kammler Maren
Published: November 2009

Biomasse wird in absehbarer Zukunft Erdöl als Energielieferant und Rohstoffgrundlage ersetzen. Den größten Anteil der Biomasse stellen Kohlenhydrate dar, aus denen sich Grundchemikalien gewinnen lassen. Während Milchsäure (2‐Hydroxypropansäure) bereits in kommerziell nennenswerten Mengen hergestellt wird, warten andere Produkte wie z. B. 5‐Hydroxymethylfurfural noch auf ihren Durchbruch. Die Arbeitsblätter (mit Musterlösungen) sind als online‐Ergänzung zugänglich und zeigen beispielhaft auf, inwiefern sich Alltagsprodukte aus Kohlenhydraten bereits herstellen lassen und wo sich gegenwärtig noch Potentiale verbergen. Übungsaufgaben decken ein breites Spektrum dessen ab, was Schüler mit dem Thema ‚Kohlenhydrate’︁ lernen.
Genistein reverses hypermethylation and induces active histone modifications in tumor suppressor gene B‐Cell translocation gene 3 in prostate cancer
Authors: Majid Shahana , Dar Altaf A. , Shahryari Varahram , Hirata Hiroshi , Ahmad Ardalan , Saini Sharanjot , Tanaka Yuichiro , Dahiya Angela V. , Dahiya Rajvir
Published: November 2009

BACKGROUND:

B‐cell translocation gene 3 (BTG3/ANA/APRO4) is a candidate tumor suppressor gene in some malignancies. We report here that B‐cell translocation gene 3 (BTG3) is transcriptionally down‐regulated in prostate cancer and the mechanism of inactivation is through promoter hypermethylation.

METHODS:

Prostate cancer and normal cell lines were treated with different doses of genistein and 5‐aza‐2′‐deoxycytidine (5Aza‐C). BTG3 messenger ribonucleic acid (mRNA) expression was determined by quantitative real‐time polymerase chain reaction in tissues and cell lines. Bisulfate‐modified polymerase chain reaction, cloning and sequencing were used to examine promoter methylation in tumor samples and cell lines. Enzyme activity/inhibition assays were done to check the effect of genistein and 5Aza‐C on DNA methyltransferases. ChIP assay was performed to analyze chromatin modifications caused by genistein treatment.

RESULTS:

BTG3 mRNA expression was down‐regulated in cancer tissues and cells. Genistein and 5Aza‐C induced BTG3 mRNA expression in all PC cell lines. Complete methylation of BTG3 promoter in tumor samples and cancer cell lines was observed. Genistein and 5Aza‐C treatment significantly decreased promoter methylation, reactivating BTG3 expression. Genistein and 5Aza‐C increased levels of acetylated histones 3, 4, histone 3 dimethylated at lysine 4, histone 3 trimethylated at lysine 4, and RNA polymerase II, decreased DNA methyl transferase and methyl‐binding domain protein 2 activity, and increased histone acetyl transferase (HAT) activity.

CONCLUSIONS:

This is the first report to show that BTG3 is silenced in prostate cancer and can be reactivated by genistein‐induced promoter demethylation and active histone modification. Genistein showed similar effects to that of 5Aza‐C, which is currently undergoing phase 2 clinical trials as a treatment for prostate cancer. Because genistein is a natural, nontoxic, and dietary isoflavone, these results indicate that genistein is a novel, advantageous therapeutic agent for treating prostate cancer. Cancer 2010. © 2010 American Cancer Society.
Combination of cladribine plus topotecan for recurrent or refractory pediatric acute myeloid leukemia
Authors: Inaba Hiroto , Stewart Clinton F. , Crews Kristine R. , Yang Shengping , Pounds Stanley , Pui Ching‐Hon , Rubnitz Jeffrey E. , Razzouk Bassem I. , Ribeiro Raul C.
Published: November 2009

BACKGROUND:

The prognosis after recurrence of pediatric acute myeloid leukemia (AML) is poor, and effective salvage regimens are urgently needed.

METHODS:

In phase 1 and pilot studies, the authors evaluated the maximum tolerated dose (MTD) and dose‐limiting toxicities (DLTs) of a 5‐day course of cladribine followed by topotecan in pediatric patients with recurrent/refractory AML. The cladribine dose was escalated as follows: 9.1, 13.6, 16.3, and 19.5 mg/m2 per day (8.9 mg/m2 per day in the pilot study). Outcome was analyzed according to the absence (Stratum 1) versus presence (Stratum 2) of previous allogeneic hematopoietic stem cell transplantation. Twenty‐six patients (20 in Stratum 1 and 6 in Stratum 2) were treated.

RESULTS:

The MTD was not reached in Stratum 1, but a DLT occurred at the lowest cladribine dosage (9.1 mg/m2 per day) in Stratum 2. Febrile neutropenia was common in both strata. Nine (34.6%) of 26 patients experienced a complete response, and 7 (30.4%) achieved a partial response; 5 (19.2%) were long‐term survivors at the time of last follow‒up. Clinical outcome was not associated with cladribine or topotecan systemic exposure.

CONCLUSIONS:

The combination was well tolerated in Sratum 1, and the response rate was encouraging. This regimen offers a postrecurrence treatment alternative for patients, especially those who have received anthracycline‐containing chemotherapy. Cancer 2010. © 2010 American Cancer Society.
Porous Carbohydrate‐Based Materials via Hard Templating
Authors: Kubo Shiori , Demir‐Cakan Rezan , Zhao Li , White Robin J. , Titirici Maria‐Magdalena
Published: November 2009

Among various techniques, the hydrothermal carbonization (HTC) of biomass (either isolated carbohydrates or crude plants) is a promising candidate for the synthesis of novel carbon‐based materials with a wide variety of potential applications. In this Minireview, we discuss various synthetic routes towards such porous carbon‐based materials or composites through the HTC process, using the nanocasting procedure. We focus on the synthesis of carbon materials with different pore systems and morphologies directed by the presence of various nanostructured inorganic sacrificial templates. This method allows tailoring of the final structure via the tools of colloid and polymer science, leading to selectable material morphology for a wide range of applications.