bluuebunny/crossref_metadata_2025_split huggingface dataset:
Simulation studies of the interfaces of incompatible glycidyl azide polymer/hydroxyl‐terminated polybutadiene blends by dissipative particle dynamics. I. The effect of block copolymers and plasticizers
Authors: Zhou Yang , Long Xin‐Ping , Zeng Qing‐Xuan 
Published: January 2012

AbstractDissipative particle dynamics (DPD) simulations were used to investigate the interfaces of incompatible glycidyl azide polymer (GAP)/hydroxyl‐terminated polybutadiene (HTPB) blends in the presence of block copolymers and plasticizers. They were GAP‐b‐HTPB copolymers and commonly used nitrate ester or inert plasticizers in the formulations of propellants. The results show that there were two abilities that determined the effects of the block copolymers and plasticizers on reducing the interfacial tension (γ). These were the penetrability into each homopolymer phase and the ability for assembling at the interface. The plasticizers mainly depended on the first ability, and the block copolymers depended on the other ability. In addition, block copolymers with the different chain lengths had the different influences on γ of the GAP/HTPB blends. Moreover, this phenomenon could also be explained by the above two abilities. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012
Silicone/silica nanocomposites as culture‐stone protective materials
Authors: Huang Yuewen , Liu Weiqu , Zhou Xuesong 
Published: January 2012

AbstractThe water absorption ratio of the cement‐based material culture stone was reduced obviously by the addition of composite additives of silica AS‐40 with a nanoparticle size, hydroxyl polysiloxane emulsion, and water‐based methyltrimethoxysilane (MTMS); its surface exhibited hydrophobicity and a certain acid resistance. Furthermore, both of the culture stones treated by two hybrid coatings prepared from the sol–gel reaction of tetraethoxysilane (TEOS) with MTMS and TEOS with MTMS and octyltrimethoxysilane (OTMS), respectively, showed excellent water repellence, long‐term contamination resistance, and good acid resistance; particularly, the culture stone treated by the coating from the OTMS precursor displayed better surface hydrophobicity. On the other hand, both the water‐based additives and the two hybrid coatings were characterized by Fourier transform infrared spectroscopy and transmission electron microscopy. The sol–gel reaction coatings of TEOS with MTMS and OTMS were also characterized by 29Si‐NMR. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012
Poly[N‐(2‐hydroxypropyl)methacrylamide] prodrug for metaxalone via a chloroacetyl chloride linker: Synthesis and controlled release evaluation
Authors: Zhang Juan , Liu Yi‐Feng , Liu Lin‐Xue , Zhang Ya‐Zhou , Qiao Chang‐An , Zhou Yong‐Zhu 
Published: January 2012

AbstractPoly[N‐(2‐hydroxypropyl)methacrylamide] (PHPMA) and its drug conjugates are some of the most intensively investigated drug‐delivery systems. Metaxalone (Met) was covalently linked to PHPMA via a spacer, and the procedure of the chemical modification for PHPMA was conducted by a two‐step protocol: (1) synthesis of PHPMA with different molecular weights and (2) synthesis of PHPMA–Met. The Met content in the conjugate could reach 18%. The controlled drug‐release studies were performed in buffer solutions with pH values equal to 1.1, 7.4, and 10.0. The results demonstrate that the rate of hydrolysis for PHPMA–Met was the slowest at pH 1.1, and a greater amount of Met was detected releasing from prodrug matrices in the presence of enzyme in a buffer solution at pH 8.0. It was also found that the novel prodrug effectively improved Met's pharmacokinetics and, furthermore, markedly increased its half‐life period. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012
Unresectable colorectal cancer liver metastases treated by intraoperative radiofrequency ablation with or without resection19
Authors: Evrard S , Rivoire M , Arnaud J-P , Lermite E , Bellera C , Fonck M , Becouarn Y , Lalet C , Pulido M , Mathoulin-Pelissier S 
Published: January 2012

Abstract

Background
Despite neoadjuvant chemotherapy, few patients with colorectal cancer liver metastases (CRLM) are eligible for liver resection. The aim of the present study was to investigate the efficacy of intraoperative radiofrequency ablation (IRFA) in the treatment of unresectable CRLM.

Methods
Patients with unresectable metastases confined to the liver were eligible for this prospective, multicentre phase II study conducted between 2003 and 2008. They received IRFA treatment either with or without parenchymal resection, and underwent clinical and pathological examinations. The primary endpoint was complete hepatic response at 3 months. Overall, event-free and local progression-free survival, morbidity and quality of life were also examined.

Results
Fifty-two patients were included, all of whom received neoadjuvant chemotherapy. They had a median of 5 (range 1–13) metastases, mostly bilateral or recurrent. A complete hepatic response was observed in 39 patients (75 (95 per cent confidence interval (c.i.) 61 to 86) per cent). Of ten patients with hepatic recurrence at 3 months, two relapses were at the site of ablation. Median follow-up was 2·9 (95 per cent c.i. 2·5 to 3·6) years. The 1-year local progression-free survival rate was 46 (95 per cent c.i. 32 to 59) per cent, the 3-year event-free survival rate was 10 (95 per cent c.i. 4 to 21) per cent and the 5-year overall survival rate was 43 (95 per cent c.i. 21 to 64) per cent. Twenty patients had postoperative complications, including one death. Quality of life increased over time for patients without disease progression.

Conclusion
IRFA, either with or without resection, is a promising treatment option for patients with unresectable CRLM. Registration number: NTC00210106 (http://www.clinicaltrials.gov).
‘Playing with Fire and Getting Burned’: The Case of the Naïve Action Researcher
Authors: Estacio Emee Vida 
Published: January 2012

ABSTRACTThe value of community‐based research as a useful mechanism for social change is gaining recognition in the psychological literature. While this kind of work has the potential to impact upon the lives of individuals and communities we engage with, it can also leave researchers facilitating the process with a lasting impression on both their academic and personal lives. This article is a case‐based reflection on the dilemmas surrounding community‐based research and how it can impact upon the experiences of both the community and the researchers facilitating the project. This case study is based upon the author's experiences of facilitating a participatory action research (PAR) project with a small indigenous community in the Philippines. Written more than five years since the project commenced, some of the challenges encountered are presented and reflected upon. This includes the dynamic nature of PAR, inter‐organisational conflicts, and lack of personal distance in action research. Sensitive issues specific to this case study are also discussed, i.e. land grabbing and violence against indigenous communities. Reflections are contextualized within discussions from various academic orientations within the psychological and social science literature, including community and critical psychology, Sikolohiyang Pilipino, and human rights. Copyright © 2012 John Wiley & Sons, Ltd.
Study of the Chemical Mechanism Involved in the Formation of Tungstite in Benzyl Alcohol by the Advanced QEXAFS Technique
Authors: Olliges‐Stadler Inga , Stötzel Jan , Koziej Dorota , Rossell Marta D. , Grunwaldt Jan‐Dierk , Nachtegaal Maarten , Frahm Ronald , Niederberger Markus 
Published: January 2012

AbstractInsight into the complex chemical mechanism for the formation of tungstite nanoparticles obtained by the reaction of tungsten hexachloride with benzyl alcohol is presented herein. The organic and inorganic species involved in the formation of the nanoparticles were studied by time‐dependent gas chromatography and X‐ray diffraction as well as by time‐resolved in situ X‐ray absorption near‐edge structure and extended X‐ray absorption fine structure spectroscopy. Principal component analysis revealed two intermediates, which were identified as WCl4 and WOCl4 by using linear combination analysis. Quick‐scanning extended X‐ray absorption fine structure spectroscopy enabled the time‐dependent evolution of the starting compound, the intermediates and the product to be monitored over the full reaction period. The reaction starts with fast chlorine substitution and partial reduction during the dissolution of the tungsten hexachloride in benzyl alcohol followed by the generation of intermediates with WO double bonds and finally the construction of the WOW network of the tungstite structure.
Calcium–Amidoborane–Ammine Complexes: Thermal Decomposition of Model Systems
Authors: Harder Sjoerd , Spielmann Jan , Tobey Briac 
Published: January 2012

AbstractHydrocarbon‐soluble model systems for the calcium–amidoborane–ammine complex Ca(NH2BH3)2⋅(NH3)2 were prepared and structurally characterized. The following complexes were obtained by the reaction of RNH2BH3 (R=H, Me, iPr, DIPP; DIPP=2,6‐diisopropylphenyl) with Ca(DIPP‐nacnac)(NH2)⋅(NH3)2 (DIPP‐nacnac=DIPPNC(Me)CHC(Me)NDIPP): Ca(DIPP‐nacnac)(NH2BH3)⋅(NH3)2, Ca(DIPP‐nacnac)(NH2BH3)⋅(NH3)3, Ca(DIPP‐nacnac)[NH(Me)BH3]⋅ (NH3)2, Ca(DIPP‐nacnac)[NH(iPr)BH3]⋅(NH3)2, and Ca(DIPP‐nacnac)[NH(DIPP)BH3]⋅NH3. The crystal structure of Ca(DIPP‐nacnac)(NH2BH3)⋅(NH3)3 showed a NH2BH3− unit that was fully embedded in a network of BH⋅⋅⋅HN interactions (range: 1.97(4)–2.39(4) Å) that were mainly found between NH3 ligands and BH3 groups. In addition, there were NH⋅⋅⋅C interactions between NH3 ligands and the central carbon atom in the ligand. Solutions of these calcium–amidoborane–ammine complexes in benzene were heated stepwise to 60 °C and thermally decomposed. The following main conclusions can be drawn: 1) Competing protonation of the DIPP‐nacnac anion by NH3 was observed; 2) The NH3 ligands were bound loosely to the Ca2+ ions and were partially eliminated upon heating. Crystal structures of [Ca(DIPP‐nacnac)(NH2BH3)⋅(NH3)]∞, Ca(DIPP‐nacnac)(NH2BH3)⋅(NH3)⋅(THF), and [Ca(DIPP‐nacnac){NH(iPr)BH3}]2 were obtained. 3) Independent of the nature of the substituent R in NH(R)BH3, the formation of H2 was observed at around 50 °C. 4) In all cases, the complex [Ca(DIPP‐nacnac)(NH2)]2 was formed as a major product of thermal decomposition, and its dimeric nature was confirmed by single‐crystal analysis. We proposed that thermal decomposition of calcium–amidoborane–ammine complexes goes through an intermediate calcium–hydride–ammine complex which eliminates hydrogen and [Ca(DIPP‐nacnac)(NH2)]2. It is likely that the formation of metal amides is also an important reaction pathway for the decomposition of metal–amidoborane–ammine complexes in the solid state.
Catalytic Four‐Electron Oxidation of Water by Intramolecular Coupling of the Oxo Ligands of a Bis(ruthenium–bipyridine) Complex
Authors: Wada Tohru , Ohtsu Hideki , Tanaka Koji 
Published: January 2012

AbstractA bis(ruthenium–bipyridine) complex bridged by 1,8‐bis(2,2′:6′,2′′‐terpyrid‐4′‐yl)anthracene (btpyan), [Ru2(μ‐Cl)(bpy)2(btpyan)](BF4)3 ([1](BF4)3; bpy=2,2′‐bipyridine), was prepared. The cyclic voltammogram of [1](BF4)3 in water at pH 1.0 displayed two reversible [RuII,RuII]3+/[RuII,RuIII]4+ and [RuII,RuIII]4+/[RuIII,RuIII]5+ redox couples at E1/2(1)=+0.61 and E1/2(2)=+0.80 V (vs. Ag/AgCl), respectively, and an irreversible anodic peak at around E=+1.2 V followed by a strong anodic currents as a result of the oxidation of water. The controlled potential electrolysis of [1]3+ ions at E=+1.60 V in water at pH 2.6 (buffered with H3PO4/NaH2PO4) catalytically evolved dioxygen. Immediately after the electrolysis of the [1]3+ ion in H216O at E=+1.40 V, the resultant solution displayed two resonance Raman bands at $\tilde \nu $=442 and 824 cm‐1. These bands shifted to $\tilde \nu $=426 and 780 cm−1, respectively, when the same electrolysis was conducted in H218O. The chemical oxidation of the [1]3+ ion by using a CeIV species in H216O and H218O also exhibited the same resonance Raman spectra. The observed isotope frequency shifts (Δ$\tilde \nu $=16 and 44 cm−1) fully fit the calculated ones based on the RuO and OO stretching modes, respectively. The first successful identification of the metalOOmetal stretching band in the oxidation of water indicates that the oxygen–oxygen bond at the stage prior to the evolution of O2 is formed through the intramolecular coupling of two Ru–oxo groups derived from the [1]3+ ion.
Long‐Lived Room‐Temperature Near‐IR Phosphorescence of BODIPY in a Visible‐Light‐Harvesting N^C^N PtII–Acetylide Complex with a Directly Metalated BODIPY Chromophore
Authors: Wu Wanhua , Zhao Jianzhang , Guo Huimin , Sun Jifu , Ji Shaomin , Wang Zilong 
Published: January 2012

AbstractRoom‐temperature long‐lived near‐IR phosphorescence of boron‐dipyrromethene (BODIPY) was observed (λem=770 nm, ΦP=3.5 %, τP=128.4 μs). Our molecular‐design strategy is to attach PtII coordination centers directly onto the BODIPY π‐core using acetylide bonds, rather than on the periphery of the BODIPY core, thus maximizing the heavy‐atom effect of PtII. In this case, the intersystem crossing (ISC) is facilitated and the radiative decay of the T1 excited state of BODIPY is observed, that is, the phosphorescence of BODIPY. The complex shows strong absorption in the visible range (ε=53800 M−1 cm−1 at 574 nm), which is rare for PtII–acetylide complexes. The complex is dual emissive with 3MLCT emission at 660 nm and the 3IL emission at 770 nm. The T1 excited state of the complex is mainly localized on the BODIPY moiety (i.e. 3IL state, as determined by steady‐state and time‐resolved spectroscopy, 77 K emission spectra, and spin‐density analysis). The strong visible‐light‐harvesting ability and long‐lived T1 excite state of the complex were used for triplet‐triplet annihilation based upconversion and an upconversion quantum yield of 5.2 % was observed. The overall upconversion capability (η=ε×ΦUC) of this complex is remarkable considering its strong absorption. The model complex, without the BODIPY moiety, gives no upconversion under the same experimental conditions. Our work paves the way for access to transition‐metal complexes that show strong absorption of visible light and long‐lived 3IL excited states, which are important for applications in photovoltaics, photocatalysis, and upconversions, etc.
Designing Fluorinated Cinchona Alkaloids for Enantioselective Catalysis: Controlling Internal Rotation by a Fluorine‐Ammonium Ion gauche Effect (φNCCF)
Authors: Tanzer Eva‐Maria , Schweizer W. Bernd , Ebert Marc‐Olivier , Gilmour Ryan 
Published: January 2012

AbstractThe C9 position of cinchona alkaloids functions as a molecular hinge, with internal rotations around the C8C9 (τ1) and C9C4′ (τ2) bonds giving rise to four low energy conformers (1; anti‐closed, anti‐open, syn‐closed, and syn‐open). By substituting the C9 carbinol centre by a configurationally defined fluorine substituent, a fluorine‐ammonium ion gauche effect (σC−H→σC−F*; Fδ−⋅⋅⋅N+) encodes for two out of the four possible conformers (2). This constitutes a partial solution to the long‐standing problem of governing internal rotations in cinchonium‐based catalysts relying solely on a fluorine conformational effect.
One‐Pot Organocatalytic Tandem Aldol/Polycyclization Reactions between 1,3‐Dicarbonyl Compounds and α,β,γ,δ‐Unsaturated Aldehydes for the Straightforward Assembly of Cyclopenta[b]furan‐Type Derivatives: New Insight into the Knoevenagel Reaction
Authors: Riveira Martín J. , Mischne Mirta P. 
Published: January 2012

AbstractA new cascade pathway viable for Knoevenagel chemistry that involves the coupling between 1,3‐dicarbonyl systems and α,β,γ,δ‐unsaturated aldehydes has been developed. The process comprises the combination of a classic aldol‐type condensation and a rare spontaneous metal‐free cycloisomerization, representing a convergent and innovative approach for the stereoselective synthesis of cyclopenta[b]furan‐type derivatives. The scope and limitations with respect to both reaction partners and mechanistic features were investigated. Meaningfully, our study provides valuable guidance concerning the structural and electronic effects controlling the reactivity of conjugated polyene carbonyl systems.
Excess‐Electron Injection and Transfer in Terthiophene‐Modified DNA: Terthiophene as a Photosensitizing Electron Donor for Thymine, Cytosine, and Adenine
Authors: Park Man Jae , Fujitsuka Mamoru , Kawai Kiyohiko , Majima Tetsuro 
Published: January 2012

AbstractExcess‐electron transfer (EET) in DNA has attracted wide attention owing to its close relation to DNA repair and nanowires. To clarify the dynamics of EET in DNA, a photosensitizing electron donor that can donate an excess electron to a variety of DNA sequences has to be developed. Herein, a terthiophene (3T) derivative was used as the photosensitizing electron donor. From the dyad systems in which 3T was connected to a single nucleobase, it was revealed that 13T* donates an excess electron efficiently to thymine, cytosine, and adenine, despite adenine being a well‐known hole conductor. The free‐energy dependence of the electron‐transfer rate was explained on the basis of the Marcus theory. From the DNA hairpins, it became clear that 13T* can donate an excess electron not only to the adjacent nucleobase but also to the neighbor one nucleobase further along and so on. From the charge‐injection rate, the possibilities of smaller β value and/or charge delocalization were discussed. In addition, EET through consecutive cytosine nucleobases was suggested.
Business‐to‐Business Branding: A Review and Assessment of the Impact of Non‐Attribute‐Based Brand Beliefs on Buyer's Attitudinal Loyalty
Authors: Cassia Fabio , Magno Francesca 
Published: January 2012

AbstractBusiness‐to‐business branding has received increasing attention from researchers in the last few years. Nonetheless, there is no agreement on the relative contribution of a brand versus an offering's functional attributes to the industrial buyer's preferences. Drawing on models from the business‐to‐consumer context, this paper demonstrates that non‐attribute‒based brand beliefs are predictors of hedonic outcomes as measured by industrial buyers' attitudinal loyalty, while attribute‐based brand beliefs are not. Moreover, the moderating role of the buyer's level of knowledge for the value‐generating process is identified, suggesting that the impact of non‐attribute‒based brand beliefs on attitudinal loyalty is greater for buyers with a low level of knowledge. Copyright © 2012 ASAC. Published by John Wiley & Sons, Ltd.
CuCl‐Catalyzed Aerobic Oxidation of Allylic and Propargylic Alcohols to Aldehydes or Ketones with 1:1 Combination of Phenanthroline and Bipyridine as the Ligands
Authors: Liu Yu , Ma Shengming 
Published: January 2012

AbstractWe developed a modified protocol for the oxidation of 2,3‐allenyl alcohols using CuCl with 1:1 combination of phenanthroline and bipyridine as the catalyst. To further investigate the applicability of this system, other types of alcohols such as allylic and propargylic alcohols have been tested: we found that both allylic and propargylic alcohols may be oxidized to the corresponding aldehydes or ketones using molecular oxygen in air as the oxidant with moderate to excellent yields.
Molecularly Imprinted Polymer for Solid‐Phase Extraction of Ecteinascidin 743 from Sea Squirt
Authors: Tian Minglei , Li Shengnan , Row Kyungho 
Published: January 2012

AbstractEcteinascidin 743 from sea squirt is one of the most original anti‐tumoral activity compounds, as proven by the Natural Cancer Institute. Ecteinascidin 743 could be obtained with traditional liquid extraction, but it should be purified and separated from the extract. A molecularly imprinted solid‐phase extraction procedure was developed for the selective separation. Ecteinascidin 743 was used as the template and the polymer was synthesized in a methanol environment. Water and n‐hexane as the washing solvents can eliminate most of the interference. Good linearity and low relative standard deviations (less than 4.39%) justify its continuing development.
Molecular and Mesoscopic Dynamics Simulations on the Compatibility of PLA/Plasticizer Blends
Authors: Jing Jie , Qiao Qing'an , Jin Yueqing , Ma Cuihua , Cai Honglan , Meng Yanfeng , Cai Zhengting , Feng Dacheng 
Published: January 2012

AbstractThe compatibility of the blend systems for olyactic acid (PLA)/tributyl citrate (TBC) and PLA/glycerol has been studied by molecule and mesoscopic dynamics methods. The results from glass transition temperature simulations showed that the compatibility of PLA/TBC system was better than that of PLA/glycerol, which were consistent with the conclusion obtained from the pair correlation functions. Besides, the behaviors of phase state distribution and evolution process were investigated by mesoscopic dynamics method as well. The results indicated that citrate ester was a better plasticizer than glycerol for PLA.
Nanoporous Pt Catalyst Modified by Sn Electrodeposition for Electrochemical Oxidation of Formaldehyde
Authors: Yi Qingfeng , Zuo Gekunkun 
Published: January 2012

AbstractA nanoporous Pt particles‐modified Ti (nanoPt/Ti) electrode was prepared through a simple hydrothermal method using aqueous H2PtCl6 as a precursor and formaldehyde as a reduction agent. The nanoPt/Ti electrode was then modified with limited amounts of tin particles generated by cyclic potential scans in the range of −0.20 to 0.50 V in a 0.01 mol·L−1 SnCl2 solution, to synthesize a Sn‐modified nanoporous Pt catalyst (Sn/nanoPt/Ti). Electroactivity of the nanoPt/Ti and Sn/nanoPt/Ti electrodes towards formaldehyde oxidation in a 0.5 mol·L−1 H2SO4 solution was evaluated by cyclic voltammetry and chronoamperometry. Electrooxidation of formaldehyde on the nanoPt/Ti electrode takes place at a potential of 0.45 V and then presents high anodic current densities due to the large real surface area of the nanoPt/Ti electrode. The formaldehyde oxidation rate is dramatically increased on the Sn/nanoPt/Ti electrode at the most negative potentials, where anodic formaldehyde oxidation is completely suppressed on the nanoPt/Ti electrode. Chronoamperogramms (CA) of the Sn/nanoPt/Ti electrode display stable and large quasi‐steady state current densities at more negative potential steps. Amperometric data obtained at a potential step of 100 mV show a linear dependence of the current density for formaldehyde oxidation upon formaldehyde concentration in the range of 0.003 to 0.1 mol·L−1 with a sensitivity of 59.29 mA·cm−2 (mol·L−1)−1. A detection limit of 0.506 mmol·L−1 formaldehyde was found. The superior electroactivity of the Sn/nanoPt/Ti electrode for formaldehyde oxidation can be illustrated by a so‐called bifunctional mechanism which is involved in the oxidation of poisoning adsorbed CO species via the surface reaction with OH adsorbed on neighboring Sn sites.