bluuebunny/crossref_metadata_2025 huggingface dataset:
ITO Breakers: Highly Transparent Conducting Polymer/Metal/Dielectric (P/M/D) Films for Organic Solar Cells
Authors: Ham Juyoung , Lee Jong‐Lam
Published: May 2014

Ormoclear/Ag/WO3 (OAW) films with ultrahigh transparency are designed for application in organic solar cells (OSCs). When the thicknesses of Ag and WO3 are fixed at 8 nm and 30 nm, respectively, excellent transparency that is independent of Ormoclear thickness is successfully achieved by employing soft materials instead of inorganic dielectrics. Oxygen plasma treatment prior to the deposition of Ag introduces the polar functional groups on the Ormoclear surface, which results in increasing the surface hydrophilicity, thereby enhancing the wettability of Ag. From the surface modification, OAW exhibits low sheet resistance (4.8 ohm sq‐1), high transmittance of up to 96.3% at 535 nm, and enhanced efficiency of 7.63% of OSCs. Moreover, nanoimprint lithography is used to prepare a well‐ordered nanopatterned OAW with dimple diameter of 90 nm, leading to further increase in photocurrent density by 17%, compared to that with a planar indium tin oxide (ITO) electrode.
Carbonsäureaktivierung in der asymmetrischen Organokatalyse
Authors: Monaco Mattia Riccardo , Poladura Belén , Diaz de Los Bernardos Miriam , Leutzsch Markus , Goddard Richard , List Benjamin
Published: May 2014

Organokatalyse hat sich zu einem allgemeinen Ansatz für die asymmetrische Katalyse entwickelt und ist sowohl zur Übergangsmetallkatalyse als auch zur Biokatalyse komplementär.1 Ihr Erfolg beruht besonders auf der Einführung neuer und universeller Aktivierungsmodi.2 Bemerkenswerterweise wurden Carbonsäuren zwar als Katalysator oder dirigierende Gruppe in der supramolekularen Übergangsmetallkatalyse verwendet,3 ein genereller und spezifischer Aktivierungsmodus für diese nützliche und weit verbreitete Substanzklasse fehlt aber bisher. Hier stellen wir die Heterodimerbildung von Carbonsäuren und chiralen Phosphorsäuren als neues Aktivierungsprinzip für die Organokatalyse vor. Diese Selbstorganisation erhöht sowohl die Acidität des Phosphorsäurekatalysators als auch die Reaktivität der Carbonsäure. Um dieses Prinzip zu Illustrieren, wenden wir es auf die generelle und hoch enantioselektive katalytische Aziridinöffnung mit Carbonsäuren als Nukleophilen an.
Substrate Profiling of Glutathione S‐transferase with Engineered Enzymes and Matched Glutathione Analogues
Authors: Feng Shan , Zhang Lei , Adilijiang Gulishana , Liu Jieyuan , Luo Minkui , Deng Haiteng
Published: May 2014

The identification of specific substrates of glutathione S‐transferases (GSTs) is important for understanding drug metabolism. A method termed bioorthogonal identification of GST substrates (BIGS) was developed, in which a reduced glutathione (GSH) analogue was developed for recognition by a rationally engineered GST to label the substrates of the corresponding native GST. A K44G‐W40A‐R41A mutant (GST‐KWR) of the mu‐class glutathione S‐transferases GSTM1 was shown to be active with a clickable GSH analogue (GSH‐R1) as the cosubstrate. The GSH‐R1 conjugation products can react with an azido‐based biotin probe for ready enrichment and MS identification. Proof‐of‐principle studies were carried to detect the products of GSH‐R1 conjugation to 1‐chloro‐2,4‐dinitrobenzene (CDNB) and dopamine quinone. The BIGS technology was then used to identify GSTM1 substrates in the Chinese herbal medicine Ganmaocongji.
Simultaneous Arrangement of up to Three Different Molecules on the Pore Surface of a Metal–Macrocycle Framework: Cooperation and Competition
Authors: Tashiro Shohei , Umeki Tsutomu , Kubota Ryou , Shionoya Mitsuhiko
Published: May 2014

Porous crystals are excellent materials with potential spatial functions through molecular encapsulation within the pores. Co‐encapsulation of multiple different molecules further expands their usability and designability. Herein we report the simultaneous arrangement of up to three different guest molecules, TTF (tetrathiafulvalene), ferrocene, and fluorene, on the pore surfaces of a porous crystalline metal–macrocycle framework (MMF). The position and orientation of adsorbed molecules arranged in the pore were determined by single‐crystal X‐ray diffraction analysis. The anchoring effect of hydrogen bonds between the hydroxy groups of the guest molecules and inter‐guest cooperation and competition are significant factors in the adsorption behaviors of the guest molecules. This finding would serve as a design basis of multicomponent functionalized nanospaces for elaborate reactions that are realized in enzymes.
Hydrogenation of Esters to Alcohols with a Well‐Defined Iron Complex
Authors: Werkmeister Svenja , Junge Kathrin , Wendt Bianca , Alberico Elisabetta , Jiao Haijun , Baumann Wolfgang , Junge Henrik , Gallou Fabrice , Beller Matthias
Published: May 2014

We present the first base‐free Fe‐catalyzed ester reduction applying molecular hydrogen. Without any additives, a variety of carboxylic acid esters and lactones were hydrogenated with high efficiency. Computations reveal an outer‐sphere mechanism involving simultaneous hydrogen transfer from the iron center and the ligand. This assumption is supported by NMR experiments.
Helical DNA Origami Tubular Structures with Various Sizes and Arrangements
Authors: Endo Masayuki , Yamamoto Seigi , Emura Tomoko , Hidaka Kumi , Morone Nobuhiro , Heuser John E. , Sugiyama Hiroshi
Published: May 2014

We developed a novel method to design various helical tubular structures using the DNA origami method. The size‐controlled tubular structures which have 192, 256, and 320 base pairs for one turn of the tube were designed and prepared. We observed the formation of the expected short tubes and unexpected long ones. Detailed analyses of the surface patterns of the tubes showed that the short tubes had mainly a left‐handed helical structure. The long tubes mainly formed a right‐handed helical structure and extended to the directions of the double helical axes as structural isomers of the short tubes. The folding pathways of the tubes were estimated by analyzing the proportions of short and long tubes obtained at different annealing conditions. Depending on the number of base pairs involved in one turn of the tube, the population of left‐/right‐handed and short/long tubes changed. The bending stress caused by the stiffness of the bundled double helices and the non‐natural helical pitch determine the structural variety of the tubes.
Deactivation of Cationic CuI and AuI Catalysts for A3 Coupling by CH2Cl2: Mechanistic Implications of the Formation of Neutral CuI and AuI Chlorides
Authors: Grirrane Abdessamad , Álvarez Eleuterio , García Hermenegildo , Corma Avelino
Published: May 2014

Care should be exercised when using CH2Cl2 as a solvent for reactions in which amines are a reagent, since undesirable deactivation of cationic copper(I) and gold(I) catalysts to form the corresponding inactive neutral chloride complexes [LMCl] (M=Cu or Au) can occur as a result of the generation of hydrogen chloride in the medium. CuI and AuI deactivation has been proved for the Mannich three‐component coupling reaction. A series of CuI and AuI complexes with potential mechanistic implications were isolated and characterized by X‐ray crystallography.
Iminophosphine palladium(II) complexes: synthesis, characterization, and application in Heck cross‐coupling reaction of aryl bromides
Authors: Yılmaz Mustafa Kemal , Güzel Bilgehan
Published: May 2014

Palladium(II) complexes containing phosphorus and nitrogen donor atoms (iminophosphine), dichlorido{N‐[2‐(diphenylphosphino)benzylidene]‐2‐trifluoromethylaniline}palladium(II) 1, dichlorido{N‐[2‐(diphenylphosphino)benzylidene]‐3‐trifluoromethylaniline}palladium(II) 2, dichlorido{N‐[2‐(diphenylphosphino)benzylidene]‐2‐methylaniline}palladium(II) 3, dichlorido{N‐[2‐(diphenylphosphino)benzylidene]‐3‐methylaniline}palladium(II) 4 have been successfully synthesized and fully characterized by FT‐IR and NMR (1H, 31P, 19F, and 13C) spectroscopy techniques. These complexes were first step tested in the reaction of bromobenzene and styrene to determine the optimal coupling reaction conditions and then successfully applied as catalysts for Heck cross‐coupling reactions of activated and deactivated aryl bromides with styrene derivatives and several acrylates. Copyright © 2014 John Wiley & Sons, Ltd.
A facile method to prepare high‐purity magnetite nanoparticles by electrooxidation of iron in water using a pulsed direct current
Authors: Setyawan Heru , Fajaroh Fauziatul , Pusfitasari Memik Dian , Yuwana Minta , Affandi Samsudin
Published: May 2014

High‐purity magnetite (Fe3O4) nanoparticles were successfully synthesized via the electrooxidation of iron in an aqueous system using a pulsed direct current (pulsed DC). The pure iron to be electrooxidized was electroplated on a steel plate, which was then used as a sacrificial anode in the electrochemical system. The electrolyte used was demineralized water, either with or without added NaOH, which was used to vary the pH of the solution, between 7 and 10. We showed that the pulsed DC significantly enhanced the purity of the magnetite that was formed. The FeOOH impurities that are typically present when continuous DC is used were not observed. The particles produced using the proposed method were nearly spherical in shape. The size of the particles ranged from 7 to 23 nm depending on the conditions of synthesis, namely, the pulse frequency, duty cycle, and pH. The magnetite nanoparticles exhibited ferromagnetic properties, with values of saturation magnetization ranging from 18 to 55 emu/g. The results obtained from thermal gravimetric/differential thermal analysis revealed that magnetite was converted into maghemite at a temperature of approximately 200 °C and into hematite under further heating to 500 °C. © 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
Chemoenzymatic Synthesis of Functional Sialyl LewisX Mimetics with a Heteroaromatic Core
Authors: Schlemmer Claudine , Wiebe Christine , Ferenc Dorota , Kowalczyk Danuta , Wedepohl Stefanie , Ziegelmüller Patrick , Dernedde Jens , Opatz Till
Published: May 2014

Functional mimetics of the sialyl LewisX tetrasaccharide were prepared by the enzymatic sialylation of a 1,3‐diglycosylated indole and a glycosyl azide, which was subsequently transformed into a 1,4‐diglycosylated 1,2,3‐triazole, by using the trans‐sialidase of Trypanosoma cruzi. These compounds inhibited the binding of E‐, L‐, and P‐selectin‐coated nanoparticles to polyacrylamide‐bound sialyl‐LewisX‐containing neighboring sulfated tyrosine residues (sTyr/sLeX‐PAA) at low or sub‐millimolar concentrations. Except for E‐selectin, the mimetics showed higher activities than the natural tetrasaccharide.
Optimized Plasmid Systems for the Incorporation of Multiple Different Unnatural Amino Acids by Evolved Orthogonal Ribosomes
Authors: Lammers Christoph , Hahn Liljan E. , Neumann Heinz
Published: May 2014

Incorporation of multiple different unnatural amino acids into the same polypeptide remains a significant challenge. Orthogonal ribosomes, which are evolvable as they direct the translation of a single dedicated orthogonal mRNA, can provide an avenue to produce such polypeptides routinely. Recent advances in engineering orthogonal ribosomes have created a prototype system to enable genetically encoded introduction of two different functional groups, albeit with limited efficiency. Here, we systematically investigated the limiting factors of this system by using assays to measure the levels and activities of individual components; we identified Methanosarcina barkeri PylRS as a limiting factor for protein yield. Balancing the expression levels of individual components significantly improved growth rate and protein yield. This optimization of the system is likely to increase the scope of evolved orthogonal ribosome‐mediated incorporation of multiple different unnatural amino acids.
Activation of protease‐activated receptor‐2 disrupts vaginal epithelial barrier function
Authors: Li Yan , Feng Chong , Wei Xing , Zhang Jiyuan , Zan Ronghua , Zheng Guizhi , Yang Xiaoying , Zhai Jianjun
Published: May 2014

The epithelial cell barrier function is a critical factor in the maintenance of the homeostasis of the vaginal mucosa. This study elucidates one of the mast cell‐derived chemical mediators, tryptase, on compromising the vaginal epithelial barrier function. The results showed that human vaginal cell line, VK2, express PAR2. Activation of PAR2 increases the expression of ADAM10 in VK2 cells, interferes with the endosome/lysosome fusion, and compromises the epithelial barrier function. We conclude that the activation of PAR2 on VK2 cells increases the expression of ADAM10, and compromises the VK2 monolayer barrier function.
Development block of golden hamster ICSI embryos is associated with decreased expression of HDAC1, HSPA1A and MYC
Authors: Pan Xiaoyan , Kong Delong , Liu Limei , Gao Fei , Zhang Xueming , Tang Bo , Li Ziyi
Published: May 2014

We have investigated the mechanism for embryo development block in vitro and to improve the development rate of golden hamster embryos in vitro. Intracytoplasmic sperm injection (ICSI) technique was used to produce golden hamster ICSI embryos. The changes in the histone acetylation and the expression of histone deacetylase and related genes were analyzed by immunocytochemical staining and real‐time PCR both in golden hamster in vivo embryos and in ICSI embryos. Aged oocytes significantly increased the oocyte spontaneous activation rate. In vitro cultured ICSI embryos suffered from severe development block in M199TE medium. Expression of histone deacetylase 1 (HDAC1) was significantly decreased in the nuclei of the arrested ICSI 2‐cell embryos, and its nuclear and cytoplasmic expression pattern was also markedly altered. The acetylation level of H4K5, however, was not significantly changed between golden hamster in vivo embryos and ICSI embryos. HSPA1A and MYC, the marker genes for zygotic genome activation (ZGA), were transcriptionally decreased in arrested ICSI 2‐cell embryos. Transcription of HDAC1 was also downregulated in these embryos, whereas the mRNA expression of the proapoptotic gene, BAX, was not changed. These results indicate that the golden hamster ICSI embryo development block during ZGA is associated with decreased nuclear expression and altered expression of HDAC1. HSPA1A, MYC, and HDAC1 mRNA levels, which decrease, resulting in ZGA failure.
CYP3A4‐dependent cellular response does not relate to CYP3A4‐catalysed metabolites of C‐1748 and C‐1305 acridine antitumor agents in HepG2 cells
Authors: Augustin Ewa , Niemira Magdalena , Hołownia Adam , Mazerska Zofia
Published: May 2014

High CYP3A4 expression sensitizes tumor cells to certain antitumor agents while for others it can lower their therapeutic efficacy. We have elucidated the influence of CYP3A4 overexpression on the cellular response induced by antitumor acridine derivatives, C‐1305 and C‐1748, in two hepatocellular carcinoma (HepG2) cell lines, Hep3A4 stably transfected with CYP3A4 isoenzyme, and HepC34 expressing empty vector. The compounds were selected considering their different chemical structures and different metabolic pathways seen earlier in human and rat liver microsomes C‐1748 was transformed to several metabolites at a higher rate in Hep3A4 than in HepC34 cells. In contrast, C‐1305 metabolism in Hep3A4 cells was unchanged compared to HepC34 cells, with each cell line producing a single metabolite of comparable concentration. C‐1748 resulted in a progressive appearance of sub‐G1 population to its high level in both cell lines. In turn, the sub‐G1 fraction was dominated in CYP3A4‐overexpressing cells following C‐1305 exposure. Both compounds induced necrosis and to a lesser extent apoptosis, which were more pronounced in Hep3A4 than in wild‐type cells. In conclusion, CYP3A4‐overexpressing cells produce higher levels of C‐1748 metabolites, but they do not affect the cellular responses to the drug. Conversely, cellular response was modulated following C‐1305 treatment in CYP3A4‐overexpressing cells, although metabolism of this drug was unaltered.
The Effect of Water on the Heterogeneously Catalyzed Selective Oxidation of Acrolein: An Isotope Study
Authors: Petzold Tina , Blickhan Nina , Drochner Alfons , Vogel Herbert
Published: May 2014

The effect of water on the selective gas phase oxidation of acrolein to acrylic acid on a Mo/V/W mixed oxide catalyst was studied by performing steady‐state isotopic transient kinetic analysis experiments with H218O. Experiments were performed in the temperature range of 90–345 °C at ambient pressure. It could be shown that acrolein exchanges its carbonylic oxygen with oxygen from water even at low temperatures (<200 °C), at which no acrolein oxidation occurs. At higher temperatures (>200 °C), the oxygen atoms of the water molecules incorporate into all oxidation products such as acrylic acid, carbon monoxide, and carbon dioxide.
Mn Oxide‐Silver Composite Nanowires for Improved Thermal Stability, SERS and Electrical Conductivity
Authors: Pradhan Mukul , Sinha Arun Kumar , Pal Tarasankar
Published: May 2014

Redox transformation reaction between aqueous AgNO3 and Mn(CH3COO)2 at low temperature (∼80 °C) has been adopted for industrial‐scale production of uniform Ag–MnOOH composite nanowires for the first time. Varying amounts of incorporated Ag in the composite retain the 1D morphology of the composite. Nanowires upon annealing evolve Ag–MnO2 nanocomposites, once again with the retention of the parental morphology. Just 4 % of silver incorporation in the composite demonstrates metal‐like conducting performance from the corresponding semiconducting material. Transition of MnO2 to Mn2O3 to Mn3O4 takes place upon heat treatment in relation to successive increase in Ag concentrations in the nanowires. The composites offer resistance to the observed oxide transformation. This is evidenced from the progressive increase in transition temperature. In situ Raman, ex situ thermal and XRD analysis corroborate the fact. The composite with 12 % Ag offers resistance to the transformation of MnO2, which is also verified from laser heating. Importantly, Ag nanoparticle incorporation is proved to offer a thermally stable and better surface enhanced Raman scattering (SERS) platform than the individual components. Both the Ag–MnOOH and Ag–MnO2 nanocomposites with 8 atomic % Ag show the best SERS enhancement (enhancement factor ∼1010). The observed enhancement relates to charge transfer as well as electromagnetic effects.
A Supramolecular Tubular Nanoreactor
Authors: Li Zhi‐Qiang , Zhang Ying‐Ming , Chen Yong , Liu Yu
Published: May 2014

The extremely strong noncovalent complexation between the rigid host of phthalocyanine‐bridged β‐cyclodextrins and the amphiphilic guest carboxylated porphyrin is employed to construct a hollow tubular structure as a supramolecular nanoreactor. A representative coupling reaction occurs in the hydrophobic interlayers of the tubular walls in pure water at room temperature, leading to an enhancement of ten times higher reaction rate without any adverse effect on catalytic activity and conversion.
Halogen‐ and Hydrogen‐Bonding Catenanes for Halide‐Anion Recognition
Authors: Gilday Lydia C. , Beer Paul D.
Published: May 2014

Halogen‐bonding (XB) interactions were exploited in the solution‐phase assembly of anion‐templated pseudorotaxanes between an isophthalamide‐containing macrocycle and bromo‐ or iodo‐functionalised pyridinium threading components. 1H NMR spectroscopic titration investigations demonstrated that such XB interpenetrated assemblies are more stable than analogous hydrogen bonding (HB) pseudorotaxanes. The stability of the anion‐templated halogen‐bonded pseudorotaxane architectures was exploited in the preparation of new halogen‐bonding interlocked catenane species through a Grubbs’ ring‐closing metathesis (RCM) clipping methodology. The catenanes’ anion recognition properties in the competitive CDCl3/CD3OD 1:1 solvent mixture revealed selectivity for the heavier halides iodide and bromide over chloride and acetate.
A New Strategy for Storage and Transportation of Sensitive High‐Energy Materials: Guest‐Dependent Energy and Sensitivity of 3D Metal–Organic‐Framework‐Based Energetic Compounds
Authors: Zhang Sheng , Liu Xiangyu , Yang Qi , Su Zhiyong , Gao Wenjuan , Wei Qing , Xie Gang , Chen Sanping , Gao Shengli
Published: May 2014

Reaction of Co(II) with the nitrogen‐rich ligand N,N‐bis(1H‐tetrazole‐5‐yl)‐amine (H2bta) leads to a mixed‐valence, 3D, porous, metal–organic framework (MOF)‐based, energetic material with the nitrogen content of 51.78%, [Co9(bta)10(Hbta)2(H2O)10]n⋅(22 H2O)n (1). Compound 1 was thermohydrated to produce a new, stable, energetic material with the nitrogen content of 59.85% and heat of denotation of 4.537 kcal cm−3, [Co9(bta)10(Hbta)2(H2O)10]n (2). Sensitivity tests show that 2 is more sensitivity to external stimuli than 1, reflecting guest‐dependent energy and sensitivity of 3D, MOF‐based, energetic materials. Less‐sensitive 1 can be regarded as a more safe form for storage and transformation to sensitive 2.
Two‐Step Synthesis of Multi‐Substituted Amines by Using an N‐Methoxy Group as a Reactivity Control Element
Authors: Yoritate Makoto , Meguro Tatsuhiko , Matsuo Naoya , Shirokane Kenji , Sato Takaaki , Chida Noritaka
Published: May 2014

Invited for the cover of this issue is the group of Prof. Noritaka Chida and Dr. Takaaki Sato at Keio University, Japan. The cover illustrates the­ N‐methoxy group as the reactivity control element to allow for beautiful chemical transformations to blossom in organic synthesis. Read the full text of the article at 10.1002/chem.201402231.
Model‐Based Determination of the Optimal Reaction Route for Integrated Multiphase Processes
Authors: Hentschel Benjamin , Freund Hannsjörg , Sundmacher Kai
Published: May 2014

Grundlage für eine optimale Reaktorauslegung ist die Kenntnis der optimalen Reaktionsführung. Modellbasierte Methoden sind dabei von besonderem Wert, da bei komplexen Systemen eine intuitive Erarbeitung der optimalen Reaktionsführung nicht mehr möglich ist. Am Beispiel der Hydroformulierung langkettiger Alkene wird hier eine auf modellbasierter Optimalsteuerung beruhende Methode beschrieben, die mögliche Stoffrückführungen bereits in einer frühen Phase der Prozessentwicklung berücksichtigt und damit neben der optimalen Reaktionsführung auch auf Anforderungen an die Trennoperationen schließen lässt.
Regulating the Interactions of Adsorbates on Surfaces by Scanning Tunneling Microscopy Manipulation
Authors: Sun Qiang , Xu Wei
Published: May 2014

Scanning tunneling microscopy (STM) manipulation has received wide attention in the surface science community since the pioneering work of Eigler to construct surface nanostructures in an atom by atom fashion. Lots of scientists have been inspired and devoted to study the surface issues with the help of STM manipulations and great achievements have been obtained. In this Minireview, we mainly describe the recent progress in applying STM manipulations to regulate the inter‐adsorbate and adsorbate–substrate interactions on solid surfaces. It was shown that this technique could not only differentiate intermolecular interactions but also construct molecular nanostructures by regulating different kinds of inter‐adsorbate interactions or adsorbate–substrate interactions.
Organic Nonlinear Optical Materials: The Mechanism of Intermolecular Covalent Bonding Interactions of Kekulé Hydrocarbons with Significant Singlet Biradical Character
Authors: Liu Jing , Xia Jiarui , Song Peng , Ding Yong , Cui Yanling , Liu Xuemei , Dai Yumei , Ma Fengcai
Published: May 2014

The ground‐ and excited‐state properties of benzene‐linked bisphenalenyl (B‐LBP), naphthaline‐linked bisphenalenyl (N‐LBP), and anthracene‐linked bisphenalenyl (A‐LBP) Kekulé molecules and their respective one‐dimensional (1D) stacks are investigated using time‐dependent density functional theory (TD‐DFT) and a range of extensive multidimensional visualization techniques. The results reveal a covalent π–π bonding interaction between overlapping phenalenyl radicals whose bond length is shorter than the van der Waals distance between carbon atoms. Increasing the linker length and/or number of molecules involved in the 1D stack decreases the HOMO–LUMO energy gap and increases the wavelength of the systems. The charge‐transfer mechanism and electron coherence both differ with changes in the linker length and/or number of molecules involved in the 1D stack.
Discrete Dipole Approximation Analysis of Plasmonic Core/Alloy Nanoparticles
Authors: Wu Wenjie , Maye Mathew M.
Published: May 2014

The surface plasmon resonance (SPR) properties of Au/AuxAg1−x core/alloy nanoparticles (NPs) have been investigated by means of the discrete dipole approximation. The core/alloy microstructure was varied by changing the shell alloy composition x, its thickness tS, and the shell thickness to core radius ratio (tS/rC) in the range of 0.05–1.0. These changes resulted in a novel tuning of SPR shape, frequency, and extinction. These models were compared with experimental results for Au/AuxAg1−x NPs prepared by a microwave‐mediated hydrothermal processing method, which produces core/alloy NPs with SPR signatures closely resembling those of the models.
Effectiveness of Psychotherapy in Personality Disorders Not Otherwise Specified: A Comparison of Different Treatment Modalities
Authors: Horn Eva K. , Bartak Anna , Meerman Anke M. M. A. , Rossum Bert V. , Ziegler Uli M. , Thunnissen Moniek , Soons Mirjam , Andrea Helene , Hamers Elisabeth F. M. , Emmelkamp Paul M. G. , Stijnen Theo , Busschbach Jan J. V. , Verheul Roel
Published: May 2014

Objective

Although personality disorder not otherwise specified (PDNOS) is highly prevalent and associated with a high burden of disease, only a few treatment studies in this patient group exist. This study is the first to investigate the effectiveness of different modalities of psychotherapy in patients with PDNOS, i.e., short‐term (up to 6 months) and long‐term (more than 6 months) outpatient, day hospital, and inpatient psychotherapy.

Method

A total of 205 patients with PDNOS were assigned to one of six treatment modalities. Effectiveness was assessed over 60 months after baseline. The primary outcome measure was symptom severity, and the secondary outcome measures included psychosocial functioning and quality of life. The study design was quasi‐experimental, and the multiple propensity score was used to control for initial differences between treatment groups.

Results

All treatment modalities showed positive outcomes, especially in terms of improvements of symptom severity and social role functioning. At 12‐month follow‐up, after adjustment for initial differences between the treatment groups, short‐term outpatient psychotherapy and short‐term inpatient psychotherapy showed most improvement and generally outperformed the other modalities concerning symptom severity. At 60 months after baseline, effectiveness remained but observed differences between modalities mostly diminished.

Conclusion

Patients with PDNOS benefit from psychotherapy both at short‐term and long‐term follow‐up. Short‐term outpatient psychotherapy and short‐term inpatient psychotherapy seem to be superior to the other treatment modalities at 12‐month follow‐up. At 60‐month follow‐up, treatments showed mostly comparable effectiveness. Copyright © 2014 John Wiley & Sons, Ltd.

Key Practitioner Messages

The effectiveness of different modalities of psychotherapy in patients with PDNOS (i.e., short‐term vs long‐term; outpatient versus day hospital versus inpatient psychotherapy) has not yet been compared.

Different modalities of psychotherapy are effective for patients with PDNOS, and positive effects remain after 5 years.

In patients with PDNOS short‐term (less than 6 months) outpatient psychotherapy and short‐term inpatient psychotherapy seem to be superior to the four other treatment modalities at 12‐month follow‐up.

At 60‐month follow‐up, treatments showed mostly comparable effectiveness.
Design and Functionalization of Photocatalytic Systems within Mesoporous Silica
Authors: Qian Xufang , Fuku Kojirou , Kuwahara Yasutaka , Kamegawa Takashi , Mori Kohsuke , Yamashita Hiromi
Published: May 2014

The Front Cover artwork is provided by the group of Prof. Hiromi Yamashita from Osaka University. The image shows four photocatalytic systems assembled on transparent mesoporous silica materials with the background of environmental remedy and solar energy utilization. The Minireview itself is available at 10.1002/cssc.201400111
Investigating dynamic pain sensitivity in the context of the fear‐avoidance model
Authors: Gay C.W. , Horn M.E. , Bishop M.D. , Robinson M.E. , Bialosky J.E.
Published: May 2014

Background

Although nearly everyone at some point in their lives experiences back pain; the amount of interference with routine activity varies significantly. The fear‐avoidance (FA) model of chronic pain explains how psychological variables, such as fear, act as mediating factors influencing the relationship between clinical pain intensity and the amount of interference with daily activities. What remains less clear is how other mediating factors fit within this model. The primary objective of this report was to examine the extent to which a dynamic measure of pain sensitivity provides additional information within the context of the FA model.

Method

To address our primary objective, classic mediation and moderated mediation analyses were conducted on baseline clinical, psychological and quantitative sensory measures obtained on 67 subjects with back pain (mean age, 31.4 ± 12.1 years; 70% female).

Results

There was a moderately strong relationship (r = 0.52; p < 0.01) between clinical pain intensity and interference, explaining about 27% of the variance in the outcome. Mediation analyses confirmed fear partially mediated the total effect of clinical pain intensity on interference (Δβ = 0.27; p < 0.01), and accounted for an additional 16% of the variance. In our FA model, pain sensitivity did not demonstrate additional indirect effects; however, it did moderate the strength of indirect effects of fear.

Conclusion

This preliminary modelling suggests complex interactions exist between pain‐related fear and pain sensitivity measures that further explain individual differences in behaviour.
Out of sight, but not out of mind? Greater reported pain in patients who spontaneously look away during venepuncture
Authors: Vijayan R. , Scott G. , Brownlie W.
Published: May 2014

Background

Various external factors can influence patients’ experiences of noxious stimuli, but little is known of how patients’ natural behaviour may be relevant. We ascertained how often patients spontaneously look or look away during venepuncture and associated reports of pain during a previously reported experimental randomized study. The study was conducted in the outpatient department of a UK district general hospital.

Methods

Patients were randomized to hearing ‘sharp scratch’ or the verbal cue ‘ready?’ immediately before venepuncture. Whether patients looked or looked away during needle insertion was recorded. Patients were asked to rate their pain using a verbal numerical rating score (VNRS) and verbal response scale (VRS).

Results

One hundred ninety‐two patients were included; mean age 51.7 years, 55% male. During needle insertion, 73% spontaneously looked away, whereas 27% looked. There was no significant difference in the proportion of these patients assigned to the ‘sharp scratch’ or ‘ready?’ groups, nor was there any difference in mean age or gender. For the group that looked, mean VNRS was 0.48 and VRS was 1.27, significantly less than the group that looked away (mean VNRS 0.94, p = 0.014; VRS 1.61, p = 0.002). As previously reported, pain ratings between ‘sharp scratch’ and ‘ready?’ groups were not significantly different.

Conclusions

Almost three quarters of patients spontaneously look away during venepuncture, but their pain ratings are almost twice that of the quarter of patients who look. It is unclear why this may be, but previous experimental studies indicate that observing the body when a noxious stimulus is applied can have an analgesic effect.
Replacement of sugar in the product formulation of “Bomboyson” by jaggery
Authors: Gartaula Ghanendra , Bhattarai Mahendra
Published: May 2014

“Bomboyson” is a traditional heat desiccated dairy product of eastern Nepal, prepared using khoa, sugar, and ghee, and has a great commercial potential. This study was carried out to standardize the product and study its nutritive value and storage life for the organized production. The formulation was based on survey and the best product was selected using 9‐point hedonic rating scale method. The sugar in the best product was replaced by jaggery, and both were compared with the most popular market product for sensory and nutritional qualities. The products were stored at ambient (25°C) and refrigerated (5°C) temperatures to study the microbiological qualities. Bomboyson prepared from 100 parts khoa, 40 parts sugar, and 20 parts ghee was found to be superior (P < 0.05) in terms of overall sensory attributes. The proximate composition of sugar‐added bomboyson was found to be 8.98 ± 0.04% moisture, 28.66 ± 1.16% fat, 16.42 ± 0.56% protein, 1.08 ± 0.12% total ash, 44.86 ± 0.86% carbohydrate, and 91.02 ± 0.04% total solids. The proximate composition of control and sugar‐added product were same (P > 0.05) while both the product had lower contents (P < 0.05) of moisture and total ash than the jaggery‐added product. The microbiological study confirmed that the products were acceptable throughout the storage period of 28 days at 5°C and 21 days at 25°C.
Transcriptional profiling predicts overwhelming homology of schwann cells, olfactory ensheathing cells, and schwann cell‐like glia
Authors: Ulrich Reiner , Imbschweiler Ilka , Kalkuhl Arno , Lehmbecker Annika , Ziege Susanne , Kegler Kristel , Becker Kathrin , Deschl Ulrich , Wewetzer Konstantin , Baumgärtner Wolfgang
Published: May 2014

Schwann cells (SCs), olfactory ensheathing cells (OECs), and central nervous system Schwann cell‐like glia (SG) represent a group of nerve growth factor receptor p75 (NGFR)‐positive cells, originating from different tissues. Because of their pro‐regenerative capacities, these cells are subjects in experimental transplantation‐based therapies of spinal cord trauma. The objective of this study was to compare the transcriptomes of uninfected and canine distemper virus‐infected OECs, SCs, SG and fibroblasts (FBs) derived from four beagle dogs and cultured under identical conditions in vitro, employing canine genome 2.0 arrays (Affymetrix). Here, we observed a complete lack of transcriptional differerences between OECs and SG, a high similarity of OECs/SG to SCs, and a marked difference of SCs and OECs/SG towards FBs. Differentially expressed genes possibly involved in the maintenance of cell type‐specific identity included an up‐regulation of HOXD8 and HOXC4 in SCs, and an up‐regulation of CNTNAP2 and EFEMP1 in OECs/SG. We identified cell type‐specific biomarkers employing supervised clustering with a K‐nearest‐neighbors algorithm and correlation‐based feature selection. Thereby AQP1 and SCRG1 were predicted to be the most powerful biomarkers distinguishing SCs from OECs/SG. Immunofluorescence confirmed a higher expression of SCRG1 in OECs and SG, and conversely a higher expression of AQP1 in SCs in vitro. Furthermore, canine and murine olfactory nerves showed SCRG1‐positive, AQP1‐negative OECs and/or axons, whereas sciatic nerves displayed multifocal non‐myelinated, AQP1‐positive, SCRG1‐negative cells. Conclusively, OECs/SG are suggested to be a uniform cell type differing only in the tissue of origin and highly related to SCs. GLIA 2014;62:1559–1581
American society for apheresis guidelines on the use of apheresis in clinical practice: Practical, concise, evidence‐based recommendations for the apheresis practitioner
Authors: Winters Jeffrey L.
Published: May 2014

The 6th Guidelines on the use of therapeutic apheresis in clinical practice published by the American Society of Apheresis provide practical, concise, and evidence based guidance for the apheresis medicine practitioner. The overall format of the Guidelines has remained unchanged with the 6th edition, compared to the 5th edition, with enhancements in the committee process of creating the guidelines. Because of changes in the writing committee structure, a number of changes have occurred in the ASFA category and recommendation grade for the use of apheresis in the treatment for a number of previously categorized clinical indications. In addition, eight new indications for apheresis, twenty three new clinical situations for previously categorized diseases, and ten new apheresis treatments for previously categorized disorders have been added. The 6th Guidelines continue to be an invaluable resource for those involved in apheresis medicine. J. Clin. Apheresis 29:191–193, 2014. © 2014 Wiley Periodicals, Inc.
Trends in the use of evidence‐based therapy for resectable gastric cancer
Authors: Snyder Rebecca A. , Penson David F. , Ni Shenghua , Koyama Tatsuki , Merchant Nipun B.
Published: May 2014

Background and Objectives

Two pivotal randomized controlled trials (RCTs), the Intergroup (INT‐0116) and Medical Research Council Adjuvant Gastric Infusional Chemotherapy (MAGIC) trials, demonstrated a survival benefit of multimodality therapy in patients with resectable gastric cancer. The purpose of this study was to determine utilization rates of these treatment regimens in the United States and to identify factors associated with receipt of evidence‐based care.

Methods

We performed a retrospective cohort study of patients with Stage IB–IV (M0) gastric adenocarcinoma who underwent resection from 1991 to 2009 using the linked SEER–Medicare database.

Results

Only 19.1% of patients received post‐operative chemoradiation therapy (CRT), and 1.9% received peri‐operative chemotherapy; most patients underwent surgery alone (60.9%). Patients with more advanced stage, younger age, and fewer comorbidities were more likely to receive evidence‐based care. We found no association between National Cancer Institute (NCI) designation and delivery of multimodality therapy. However, patients who underwent medical oncology consultation were much more likely to receive evidence‐based treatment (OR 3.10, 95% CI 2.35–4.09).

Conclusions

Rates of peri‐operative chemotherapy and post‐operative CRT in patients with resected gastric cancer remain remarkably low, despite high‐quality RCT evidence demonstrating their benefit. Furthermore, NCI designation does not appear to be associated with administration of evidence‐based treatment. J. Surg. Oncol. 2014 110:285–290. © 2014 Wiley Periodicals, Inc.
Fractional laser for vitiligo treated by 10 600 nm ablative fractional carbon dioxide laser followed by sun exposure
Authors: Hélou J. , Maatouk I. , Obeid G. , Moutran R. , Stéphan F. , Tomb R.
Published: May 2014

Background

Vitiligo is an acquired disorder of the skin and mucous membranes. Many patients with vitiligo remain in the refractory state despite the availability of numerous potential treatments. To the best of our knowledge, only one trial considers ablative fractional CO2 laser in the treatment of vitiligo.

Objective

To investigate the effects of fractional CO2 laser followed by systemic sun exposure on non‐segmental vitiligo (NSV).

Methods

Ten patients presenting refractory NSV were enrolled in this study. The patients underwent three sessions, one month apart, of fractional CO2 laser therapy on the affected areas of the skin (L‐group). Five days after each laser treatment, patients were asked to expose themselves to the sun for 2 hours on a daily basis. Objective and subjective clinical assessments were performed at the beginning and at the end of the treatment. The L‐group was then compared to a control group (C‐group) that consisted of vitiligo lesions in the same patients but with sun exposure as the exclusive therapy.

Results

Compared to the C‐group, the L‐group showed better improvement in both objective and subjective assessments. There were no noticeable adverse events in terms of scarring and Koebner phenomenon among others.

Conclusions

All patients treated with both, laser sessions and sun exposure, improved their chronic NSV lesions. Improvement was less significant in patients who exhibited vitiligo lesions over articular surfaces such as elbows and underarms. The best results were observed in vitiligo plaques located on the face, neck and legs. Consequently, fractional CO2 laser followed by sun exposure could be considered as an alternative modality for the treatment of refractory vitiligo, especially in sunny regions. Lasers Surg. Med. 46:443–448, 2014. © 2014 Wiley Periodicals, Inc.
Collaboration in the Shadow of the Technology Frontier: Evidence from the Flat Panel Display Industry
Authors: Wang I. Kim , Yang Hsiao‐shan , Miller Douglas J.
Published: May 2014

The literature on competition through innovation tends to emphasize the benefits of technological leadership. However, we explain why a capable firm might prefer to shadow the technology leader—remaining slightly behind rather than competing directly at the frontier. On the basis of a formal model and the competitive dynamics literature, we propose that the more benefits a firm gains from collaboration with a technological leader through licensing and supply agreements, the more likely the firm is to take a shadowing position. Our hypotheses, particularly regarding licensing from a technological leader, receive support from a large sample in the flat panel display industry. Copyright © 2014 John Wiley & Sons, Ltd.
Preparation and characterization of POSS‐SiO2/cyanate ester composites with high performance
Authors: Zhang Mengmeng , Yan Hongxia , Liu Chao , Zhang Junping
Published: May 2014

In this article, a hybrid filler based on polyhedral oligomeric silsesquioxane and silica, coded as POSS‐SiO2, has been successfully synthesized. The structure of POSS‐SiO2 was studied by Fourier‐transform infrared spectra, X‐ray diffraction, and scanning electron microscopy. Then the POSS‐SiO2 was compounded with dicyclopentadiene bisphenol dicyanate ester (DCPDCE) resin to prepare composites. The effects of POSS‐SiO2 on the curing reaction, mechanical, thermal, dielectric and tribological properties of DCPDCE resin were investigated systematically. Results of differential scanning calorimetry show that the addition of POSS‐SiO2 can facilitate the curing reaction of DCPDCE and decrease the curing temperature of DCPDCE. Compared with pure DCPDCE resin, the impact and flexural strengths of the composites materials are improved markedly with up to 72 and 52% increasing magnitude, respectively. Meanwhile, the POSS‐SiO2/DCPDCE systems exhibit lower dielectric constant and loss than pure DCPDCE resin over the testing frequency from 10 to 60 MHz. In addition, the thermal stability and tribological properties of POSS‐SiO2/DCPDCE composites are also superior to that of pure DCPDCE resin. POLYM. COMPOS., 36:1840–1848, 2015. © 2014 Society of Plastics Engineers
Enhanced Photocatalytic Property of Reduced Graphene Oxide/TiO2 Nanobelt Surface Heterostructures Constructed by an In Situ Photochemical Reduction Method
Authors: Sang Yuanhua , Zhao Zhenhuan , Tian Jian , Hao Pin , Jiang Huaidong , Liu Hong , Claverie Jerome P.
Published: May 2014

A facile method is proposed to assemble graphene oxide (GO) on the surface of a TiO2 nanobelt followed by an in situ photocatalytic reduction to form reduced graphene oxide (rGO)/TiO2 nanobelt surface heterostructures. The special colloidal properties of GO and TiO2 nanobelt are exploited as well as the photocatalytic properties of TiO2. Using water–ethanol solvent mixtures, GO nanosheets are tightly wrapped around the surface of the TiO2 nanobelts through an aggregation process and are then reduced in situ under UV‐light irradiation to form rGO/TiO2 nanobelt surface heterostructures. The heterostructures enhance the separation of the photoinduced carriers, which results in a higher photocurrent due to the special electronic characteristics of rGO. Compared to TiO2 nanobelts, the rGO/TiO2 nanobelt surface heterostructures possess higher photocatalytic activity for the degradation of methyl orange and for the production of hydrogen from water, as well as excellent recyclability, with no loss of activity over five cycles.
Continuous Flow Photochemistry
Authors: Gilmore Kerry , Seeberger Peter H.
Published: May 2014

Due to the narrow width of tubing/reactors used, photochemistry performed in micro‐ and mesoflow systems is significantly more efficient than when performed in batch due to the Beer‐Lambert Law. Owing to the constant removal of product and facility of flow chemical scalability, the degree of degradation observed is generally decreased and the productivity of photochemical processes is increased. In this Personal Account, we describe a wide range of photochemical transformations we have examined using both visible and UV light, covering cyclizations, intermolecular couplings, radical polymerizations, as well as singlet oxygen oxygenations.
Production of kaempferol 3-O-rhamnoside from glucose using engineered Escherichia coli
Authors: Yang So-Mi , Han So Hyun , Kim Bong-Gyu , Ahn Joong-Hoon
Published: May 2014

Flavonoids are ubiquitous phenolic compounds and at least 9,000 have been isolated from plants. Most flavonoids have been isolated and assessed in terms of their biological activities. Microorganisms such as Escherichia coli and Saccharomyces cerevisiae are efficient systems for the synthesis of flavonoids. Kaempferol 3-O-rhamnoside has notable biological activities such as the inhibition of the proliferation of breast cancer cells, the absorption of glucose in the intestines, and the inhibition of the self-assembly of beta amyloids. We attempted to synthesize kaempferol 3-O-rhamnoside from glucose in E. coli. Five flavonoid biosynthetic genes [tyrosine ammonia lyase (TAL), 4-coumaroyl CoA ligase (4CL), chalcone synthase (CHS), flavonol synthase (FLS), and flavonol 3-O-rhamnosyltransferase (UGT78D1)] from tyrosine were introduced into E. coli that was engineered to increase tyrosine production. By using this approach, the production of kaempferol 3-O-rhamnoside increased to 57 mg/L.
Antioxidant Activity of Soybean Oil Containing 4‐Vinylsyringol Obtained from Decarboxylated Sinapic Acid
Authors: Wang Xiang‐Yu , Yang Dan , Zhang Hua , Jia Cai‐Hua , Shin Jung‐Ah , Hong Soon Taek , Lee Yong‐Hwa , Jang Young‐Seok , Lee Ki‐Teak
Published: May 2014

4‐Vinylsyringol was produced by decarboxylation from sinapic acid. To evaluate the antioxidant activity of 4‐vinylsyringol, 500 ppm of 4‐vinylsyringol, sinapic acid, or α‐tocopherol was added to soybean oil and the oxidation processes were monitored by the peroxide value (PV), the thiobarbituric acid reactive substances value (TBARS) assay, and 1H‐NMR spectroscopy. The results obtained by PV and TBARS indicated that soybean oil containing 4‐vinylsyringol (SBO‐VS) showed the highest oxidative stability. 1H‐NMR analysis also showed concurring results. After 19 days of oxidation, the degradation rates of linoleic acid (4.2 %) and linolenic acid (4.4 %) in SBO‐VS were significantly lower than those in other oils. Secondary oxidation products (i.e. aldehydes) were undetectable in SBO‐VS by 1H NMR, whereas concentrations of such compounds in soybean oils containing α‐tocopherol or sinapic acid were 38.0 ± 0.4 and 2.75 ± 0.2 mM oil, respectively. In addition, synergistic antioxidant effect between any two antioxidants was not observed.