bluuebunny/crossref_metadata_2025 huggingface dataset:
La guerra de Irak como campo de prueba para el desarrollo de las imágenes digitales domésticas
Authors: Quintana Àngel
Published: January 2012

La guerra del Golfo de 1991 fue diseñada como la gran guerra en directo de un tiempo en que la televisión ocupaba un espacio central dentro de la esfera mediática. La promesa fracasó y se convirtió en una guerra espectral en la que se vislumbraron las grandes estrategias informáticas de imagen y simulación. La guerra de Irak de 2003 debía ser la revalida de las cadenas de televisión, pero durante los doce años que separan las dos guerras se habían producido una serie de cambios en el paradigma informativo. El directo televisivo debía competir con el directo de al red, la cadena CNN debía competir con la cadena Al Jazeera y las cámaras profesionales con las cámaras domésticas. El artículo analiza el impacto que los sistemas no profesionales de filmación, generados en plena era digital ha tenido en los procesos de visibilidad de la guerra de Irak. La guerra real se ha convertido en banco de pruebas de una guerra de las imágenes que ha servido para afianzar algunos de los recursos de la web 2.0. También ha servido para demostrar de qué modo la gran utopía de la objetividad informativa se ha visto amenazada por la irrupción de nuevas subjetividades. El reto fundamental que plantea el futuro reside en la concepción del archivo, en vislumbrar hasta que punto la historia se escribirá a partir del uso como documento de las imágenes profesionales de las cadenas de televisión o de las imágenes amateur que se han depositado en YouTube.
Immunoglobulin light chain amyloidosis: 2012 update on diagnosis, prognosis, and treatment
Authors: Gertz Morie A.
Published: January 2012

Disease Overview: Immunoglobulin (Ig) light chain amyloidosis is a clonal but nonproliferative plasma cell disorder in which fragments of an Ig light chain are deposited in tissues. The clinical features depend on the organs involved but can include restrictive cardiomyopathy, nephrotic syndrome, hepatic failure, and peripheral/autonomic neuropathy.

Diagnosis: Tissue biopsy stained with Congo red demonstrating amyloid deposits with apple‐green birefringence is required for diagnosis. Invasive organ biopsy is not required because amyloid deposits can be found in bone marrow biopsy or subcutaneous fat aspirate in 85% of patients. Prognosis: N‐terminal pro–brain natriuretic peptide and serum troponin T values are used to classify patients into three groups of approximately equal size; median survivals are 26.4, 10.5, and 3.5 months, respectively. Therapy: All patients with a visceral amyloid syndrome require therapy to prevent deposition of amyloid in other viscera and to prevent progressive organ failure of involved sites. Stem cell transplant (SCT) is a preferred technique, but only 20% of patients are eligible. Requirements for safe SCT include mild or no cardiac involvement, troponin T value <0.06 ng/mL, age <70 years, <3 organs involved, and serum creatinine value ≤1.7 mg/dL. Nontransplant candidates can be offered melphalan–dexamethasone. Pomalidomide appears to have activity, as do other combinations of chemotherapy with agents such as cyclophosphamide–thalidomide–dexamethasone, bortezomib–dexamethasone, and melphalan–prednisone–lenalidomide. Future Challenges: Late diagnosis remains a major obstacle to initiating effective therapy when organ dysfunction is still recoverable. Recognizing the presenting syndromes is necessary for improvement in survival. Am. J. Hematol., 2011. © 2011 Wiley Periodicals, Inc.
Gamma‐induced polymerization and grafting of a novel phosphorous‐, nitrogen‐, and sulfur‐containing monomer on cotton fabric to impart flame retardancy
Authors: Verma Sanjeev K. , Kaur Inderjeet
Published: January 2012

Diethyl (acryloyloxy) ethylthiophosphoramidate (DEAETPN), a novel phosphorus‐, nitrogen‐, and sulfur‐containing monomer, was synthesized in a two‐step reaction. The monomer was polymerized and grafted onto cotton fabric by gamma radiation method. Effect of methyl methacrylate (MMA) on percentage grafting (Pg) of DEAETPN on cotton fabric was studied, and it was found that small amount of MMA increases Pg on cotton fabric. The monomer, polymer, and the grafted cotton fabric were characterized by spectroscopic and thermogravimetric techniques. Flame retardant property of the modified cotton fabric was studied by the Shirley Manual Flammability Tester. The flame retardancy of cotton‐g‐DEAETPN by gamma radiation method and living radical polymerization method was compared. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012
Clay modification and its effect on the physical properties of silicone rubber/clay composites
Authors: Kim Eung‐Soo , Kim Eun Jeong , Lee Tae Hwa , Yoon Jin‐San
Published: January 2012

Sodium montmorillonite (MMT) was modified with benzyldimethyltetradecylammonium* chloride (B13) to prepare M‐MMT. Treatment of MMT and M‐MMT with bis(3‐triethoxy silylpropyl) tetra sulfide (TEPTS) introduced tetra sulfide groups (TS) on the surface of the clays and yielded MMT‐TS and M‐MMT‐TS, respectively. A high temperature vulcanization silicone rubber (HTV) was compounded with MMT, MMT‐TS, M‐MMT, and M‐MMT‐TS, and the morphology of the resulting HTV/clay composites was analyzed by using the corresponding TEM images. The degree of swelling of the HTV composites in the toluene solution was measured to gauge their crosslinking density and thus to exclude the possibility that the enhanced mechanical properties came from increase in the crosslinking density. The greatly improved mechanical properties, as a result of the incorporation of the TEPTS‐modified clay into HTV, were attributed to the enhanced interaction owing to the plausible chemical reaction between the TEPTS‐modified clay and the HTV matrix. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012
Highly refractive and organo‐soluble poly(amide imide)s based on 5,5′‐thiobis(2‐amino‐4‐methyl‐thiazole): Synthesis and characterization
Authors: Shockravi Abbas , Javadi Ali , Kamali Mahmood , Hajavi Saeideh
Published: January 2012

A new thioether‐bridged diimide‐diacid (DIDA) monomer was synthesized from the condensation of 5,5′‐thiobis(2‐amino‐4‐methyl‐thiazole) (DA) and trimellitic anhydride at 1 : 2 molar ratio. A series of novel organic‐soluble poly(amide imide)s (PAIs) bearing flexible thioether linkages and heteroaromatic thiazole groups were synthesized from DIDA with various commercially available aromatic diamines (1–5) via a direct polycondensation method with triphenyl phosphite and pyridine. The resulting polymers were obtained in high yields and possessed inherent viscosities in the range of 0.47–0.91 dL g–1. All of the polymers were amorphous in nature, showed good solubility and could be easily dissolved in amide‐type polar aprotic solvents (e.g., N‐methyl‐2‐pyrrolidone, dimethyl sulfoxide, and N,N‐dimethylacetamide), and even dissolved in less polar solvents (e.g., pyridine and tetrahydrofuran). They showed excellent thermal stability with glass transition temperatures between 233–269°C and 10% weight loss temperatures in excess of 480°C in nitrogen and 450°C in air atmosphere. The flexible structure endowed the PAI films with good optical transparency. The optical transmittances of the PAI films at 450 nm were higher than 80% for the thickness of approximately 10 μm. Moreover, the thiazole moieties and flexible thioether linkages in the molecular chains of the PAIs provided them with high refractive indices of 1.7329–1.7509 and low birefringences of 0.0065–0.0098. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012
Influence of the silane grafting of polyethylene on the morphology, barrier, thermal, and rheological properties of high‐density polyethylene/organoclay nanocomposites
Authors: Sharif‐Pakdaman Ali , Morshedian Jalil , Jahani Yousef
Published: January 2012

In this work, silane‐grafted high‐density polyethylene was prepared by reactive extrusion. This product and neat high‐density polyethylene were then melt‐compounded with organically modified montmorillonite to form nanocomposites. A series of tests, including Fourier transform infrared spectroscopy, small‐angle X‐ray diffraction, and transmission electron microscopy, were done on the specimens to investigate the grafting efficiency and its compatibilizing effect and the microstructure of the samples. In addition, the thermal, rheological, and barrier properties were examined to study of the grafting effects and nanocomposite characteristics. The results indicate that an intercalated structure could be easily obtained in the nanocomposites with a grafted matrix. A significant reduction in the degree of crystallinity and an increased crystallization temperature with grafting and the incorporation of nanoclay were proven by thermal analysis (differential scanning calorimetry), whereas the melting temperature did not change noticeably. Dynamic rheological testing indicated the disappearance of the Newtonian plateau and solidlike behavior of the nanocomposites based on grafted polyethylene in lower frequencies. Furthermore, the oxygen transfer rate of the samples decreased significantly with the incorporation of nanoclay in the grafted matrix and the moisture crosslinking of the samples. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012
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

Dissipative 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

The 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

Poly[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

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

The 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

Insight 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

Hydrocarbon‐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

A 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

Room‐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

The 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

A 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

Excess‐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

Business‐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

We 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

Ecteinascidin 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

The 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

A 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.
Molecular Dynamics Simulation of Diffusion of Vitamin C in Water Solution
Authors: Zeng Jianping , Wang Aimin , Gong Xuedong , Chen Jingwen , Chen Song , Xue Feng
Published: January 2012

Under different temperatures and concentrations, the diffusion of Vitamin C (VC) in water solution was examined by molecular dynamics simulation. The diffusion coefficients were calculated based on the Einstein equation. The influences of temperature, concentration, and simulation time on the diffusion coefficient were discussed. The results showed that at higher temperature and lower concentration the normal diffusions appear relatively late, but the linear range of mean square displacement curves continues longer than that at lower temperature and higher concentration. At the same temperature, the normal diffusion time increases and the diffusion coefficient decreases as the simulation concentration increases. These simulation results are in good agreement with experiments. Analyses of the pair correlation functions of the simulation systems showed that hydrogen bonds are mainly formed between the hydrogen atoms of VC molecules and oxygen atoms of H2O molecules, rather than between the O atoms of VC molecules and H atoms of H2O molecules. The diffusion coefficient is higher as the interaction between water molecules and VC molecules is stronger when VC concentration is lower. The water in the model systems affects the diffusion of VC molecules by the short‐range repulsion of O(H2O)‐O(H2O) pairs and the non‐bond interaction of H(H2O)‐H(H2O) pairs. The short‐range repulsion of O(H2O)‐O(H2O) pairs is greater when VC concentration is higher, the diffusion of VC is weaker. The greater the non‐bond interaction of H(H2O)‐H(H2O) pairs is, the higher the VC diffusion is. It is expected that this study can provide a theoretical direction for the experiments on the mass transfer of VC in water solution.
A Novel Sandwich‐type Dinuclear Complex for High‐capacity Hydrogen Storage
Authors: Zhu Haiyan , Chen Yuanzhen , Li Sai , Cao Xiuzhen , Liu Yongning
Published: January 2012

From density functional theory (DFT) calculations, we predicted that the sandwich‐type dinuclear organometallic compounds Cp2Ti2 and Cp2Sc2 can adsorb up to eight hydrogen molecules respectively, corresponding to a high gravimetric storage capacity of 6.7% and 6.8% (w), respectively. These sandwich‐type organometallocenes proposed in this work are favorable for reversible adsorption and desorption of hydrogen at ambient conditions.
Preparation of Mesoporous 1,4‐Phenylene‐silica Nanorings through a Dual‐templating Approach
Authors: Zhu Weike , Li Baozong , Bi Lifeng , Wang Sibing , Zhuang Wei , Li Yi , Yang Yonggang
Published: January 2012

Mesoporous 1,4‐phenylene‐silica nanorings were prepared using cetyltrimethylammonium bromide (CTAB) and (S)‐2‐methyl‐1‐butanol as a chiral dopant in concentrated aqueous NH3 solutions. Transmission electron microscopy images of the samples indicated that the nanorings were formed by bending nanorods 360°. With increasing the stirring speed or the (S)‐2‐methyl‐1‐butanol/CTAB molar ratio, the morphologies of mesoporous 1,4‐phenylene‐silicas changed from helical nanofibers to nanorings, and then to nano‐saddles. Circular dichroism spectra of these hybrid silicas indicated that they were chiral.
Spectrofluorimetric and Spectrophotometric Stability‐Indicating Methods for the Analysis of Veralipride in Presence of Its Degradants and in Spiked Human Plasma
Authors: Salama Nahla Nour El Din Ahmed , Salem Maissa Yacoub , Abd El Halim Lobna Mohammed , Abdel Fattah Laila El‐Sayed
Published: January 2012

Spectrofluorimetric and spectrophotometric stability‐indicating methods were developed and validated for analysis of veralipride (Ver) in presence of its hydrolytic and oxidative degradants. The spectrofluorimetric method was based on direct measurement of the intrinsic fluorescence of Ver at 366 nm after excitation at 299 nm using sodium lauryl sulfate (SLS) as micelle enhancer. The fluorescence intensity plot was linear over the concentration range 1.0–10.0 µg·mL−1. The high sensitivity of the method allowed its successful application to the analysis of Ver in spiked human plasma. Two other methods were developed. They are based on the oxidative coupling reaction of Ver with 3‐methyl benzothiazolin‐2‐one hydrazone (MBTH) hydrochloride in presence of ceric ammonium sulphate in an acidic medium. The first method depends on spectrophotometric measurement of the stable green colored oxidative coupling product at 660 nm. The different experimental parameters affecting the reaction were optimized. Linearity range is 10.0–100.0 µg·mL−1. The second method depends on a fluorescence quenching effect of Ver on the fluorescence of Ce3+. The difference in fluorescence intensity was measured at 380 nm after excitation at 300 nm. This method is applicable over the concentration ranges 0.25–2.50 µg·mL−1. The methods were validated according to the ICH guidelines. They were successfully applied for the analysis of Ver in drug substance, drug product and in laboratory prepared mixtures containing different percentages of hydrolytic and oxidative degradants.
Kinetics of the Reaction of 2‐Chloro‐3,5‐dinitrobenzotriflouride with Aniline in Toluene and Methanol‐Toluene Mixed Solvents
Authors: Fathalla Magda F.
Published: January 2012

Kinetics of the reaction of 2‐chloro‐3,5‐dinitrobenzotriflouride with aniline were studied in toluene, methanol‐toluene binary solvents, benzene and chloroform. The reaction in toluene exhibits third‐order kinetics consistent with aggregates of aniline. Thermodynamic parameters (H#, (S# and (G#are calculated and discussed for the reaction of 2‐chloro‐3,5‐dinitrobenzotriflouride with aniline in methanol‐toluene. Molecular complexes between aniline and the substrate are rejected spectrophotometricaly. The mechanism is studied and compared with the reaction in presence of pyridine. It shows an amine dependence and formation of homo and/or hetero mixed aggregates between aniline and pyridine i.e. dimer mechanism.
Environmental and Health Impacts of Successive Mineral Fertilization in Egypt
Authors: Abdelhafez Ahmed A. , Abbas Hassan H. , Abd‐El‐Aal Rafat S. , Kandil Nabil F. , Li Jianhua , Mahmoud Wahballah
Published: January 2012

Excessive amounts of mineral fertilizers are unnecessarily applied to agricultural soils in Egypt to increase crop yield. The current study aims at assessing the impacts of fertilization with different mineral fertilizers for different cultivation periods on the accumulation of heavy metals in soils and plants grown thereon. In addition, human risks resulted due to the exposure to these metal ions through ingestion, and dermal routes were evaluated. Soil and plant samples were collected from several locations in El‐Behira Governorate, Egypt and their heavy metal contents were measured. The result indicated that there is a continuous accumulation of heavy metals in the soils and the plants grown thereon. Calculation of the hazard index (HI) revealed that humans, especially children, have a potential health risk for both Pb and Cd, which have levels greater than the safe level (1). Finally, the obtained results showed that the continuous application of mineral fertilizers containing high levels of heavy metals pose a potential health threat.
Study of the Interaction Mechanism in the Biosorption of Copper(II) Ions onto Posidonia oceanica and Peat
Authors: Izquierdo Marta , Marzal Paula , Gabaldón Carmen , Silvetti Margherita , Castaldi Paola
Published: January 2012

A systematic approach was used to characterize the biosorption of copper(II) onto two biosorbents, Posidonia oceanica and peat, focusing on the interaction mechanisms, the copper(II) sorption–desorption process and the thermal behavior of the biosorbents. Sorption isotherms at pH 4–6 were obtained and the experimental data were fitted to the Langmuir model with a maximum uptake (qmax) at pH 6 of 85.78 and 49.69 mg g−1, for P. oceanica and peat, respectively. A sequential desorption (SD) with water, Ca(NO3)2, and EDTA was applied to copper‐saturated biosorbents. Around 65–70% copper(II) were desorbed with EDTA, indicating that this heavy metal was strongly bound. The reversibility of copper(II) sorption was obtained by desorption with HCl and SD. Fourier transform IR spectroscopy (FTIR) analysis detected the presence of peaks associated with OH groups in aromatic and aliphatic structures, CH, CH2, and CH3 in aliphatic structures, COO− and COOH groups and unsaturated aromatic structures on the surface of both biosorbents, as well as peaks corresponding to SiO groups on the surface of peat. The results of SEM‐EDX and FTIR analysis of copper‐saturated samples demonstrated that ion exchange was one of the mechanisms involved in copper(II) retention. Thermal analysis of biosorbent samples showed that copper(II) sorption–desorption processes affected the thermal stability of the biosorbents.
Brainstem origins of glutamatergic innervation of the rat hypothalamic paraventricular nucleus
Authors: Ziegler Dana R. , Edwards Monica R. , Ulrich‐Lai Yvonne M. , Herman James P. , Cullinan William E.
Published: January 2012

Multiple lines of evidence document a role for glutamatergic input to the hypothalamic paraventricular nucleus (PVH) in stress‐induced activation of the hypothalamic‐pituitary‐adrenocortical (HPA) axis. However, the neuroanatomical origins of the glutamatergic input have yet to be definitively determined. We have previously shown that vesicular glutamate transporter 2 (VGLUT2) is the predominant VGLUT isoform expressed in the basal forebrain and brainstem, including PVH‐projecting regions, and that the PVH is preferentially innervated by VGLUT2‐immunoreactive terminals/boutons. The present study employed a dual‐labeling approach, combining immunolabeling for a retrograde tract tracer, Fluoro‐Gold (FG), with in situ hybridization for VGLUT2 mRNA, to map the brainstem and caudal forebrain distribution of glutamatergic PVH‐projecting neurons. The present report presents evidence for substantial dual labeling in the periaqueductal gray, caudal portions of the zona incerta and subparafascicular nucleus, and the lateral parabrachial nucleus. The current data also suggest that relatively few PVH‐projecting neurons in ascending raphe nuclei, nucleus of the solitary tract, or ventrolateral medulla are VGLUT2 positive. The data reveal multiple brainstem origins of glutamatergic input to PVH that are positioned to play a role in transducing a diverse range of stressful stimuli. J. Comp. Neurol. 520:2369–2394, 2012. © 2012 Wiley Periodicals Inc.
The Clean Development Mechanism in China: Institutional Perspectives on Governance
Authors: Buhr Katarina , Thörn Philip , Hjerpe Mattias
Published: January 2012

The Clean Development Mechanism (CDM) has grown into a central feature of the global carbon market. Besides a range of normative and evaluative research into the CDM, scholars have applied international relations perspectives in which the CDM has been analysed as an example of global governance, engaging multiple actors across administrative levels. This paper focuses on a national government and how its activities affect the CDM market. We draw on an empirical case study of China to demonstrate how governmental action can be understood in light of national institutional factors, defined as normative, cognitive or regulative elements. The paper describes and explains the extensiveness of Chinese government action regarding the CDM and discusses its consequences for the market. Copyright © 2012 John Wiley & Sons, Ltd and ERP Environment.
Fabrication of a 3D Hierarchical Flower‐Like MgO Microsphere and Its Application as Heterogeneous Catalyst
Authors: Qu Yang , Zhou Wei , Ren Zhiyu , Pan Kai , Tian Chungui , Liu Yang , Feng Shanshan , Dong Youzhen , Fu Honggang
Published: January 2012

A 3D hierarchical flower‐like MgO microsphere was successfully obtained by pyrolysis of the flower‐like Mg5(CO3)4(OH)2·4H2O microsphere precursor which was itself synthesised by means of a facile and environmentally friendly hydrothermal route from MgCl2·6H2O. The possible formation process of the microsphere precursor was systematically investigated and considered to result from the following steps: (i) forming the 1D pillar‐like MgCO3; (ii) cracking to a 2D flake structure; (iii) assembling to the 3D flower‐like Mg5(CO3)4(OH)2·4H2O microsphere. The obtained close‐packed 3D flower‐like MgO microsphere has cubic symmetry and high crystallinity assembled by nanoflake particles with a mean diameter of 10 μm. Moreover, the heterogeneous catalysis of the Claisen–Schmidt condensation reaction between benzaldehyde and acetophenone to synthesise chalcones was also studied. The 3D flower‐like MgO microsphere exhibited better catalytic performance than that of commercial MgO and this was attributed to the especially 3D hierarchical flower‐like structure and the large surface area.
Zinc and nickel determination in liquid edible oils by FAAS after the extraction
Authors: Baran Eda Köse , Yaşar Sema Bağdat
Published: January 2012

A new method has been developed for the extraction and determination of zinc and nickel in liquid edible oils by using the complexation of these metals with [N,N′‐bis(salicylidene)‐2,2′‐dimethyl‐1,3‐propanediaminato]. Zn(II) and Ni(II) complexes with a tetradentate Schiff base have been investigated spectrophotometrically. Experimental extraction conditions for these metals from liquid oil standards were optimized using central composite design. Optimum conditions for Zn(II) and Ni(II) extractions from oil have been found close to each other. The ratio of the volume of used Schiff base solution to the amount of oil (VLDM/moil; mL/g), the stirring time and the temperature were round about 1.00 mL/g, 55 min, 32°C, respectively, for simultaneous determination of both metals in same sample. The recovery percentages at the optimum experimental conditions were found 98.9 ± 2.8 and 101.8 ± 4.7 for Zn(II) and Ni(II), respectively. The proposed method was applied on the raw and spiked samples such as olive oil, sunflower oil, corn oil, canola oil and obtained recovery values were between 93.7–107.2 and 93.1–101.1% for Zn(II) and Ni(II), respectively.

Practical applications: There is interest in the determination of metals in liquid edible oils because of their catalytic effect on the oxidation reaction of oils. A new method for the determination of Zn(II) and Ni(II) in liquid edible oils which does not require any digestion or decomposition was developed. This study offeres a cheap, rapid, accurate, sensitive, risk‐free, and practical metal determination method after the extraction.