bluuebunny/crossref_metadata_2025 huggingface dataset:
Selective Functionalization of P4 by Metal‐Mediated CP Bond Formation
Authors: Heinl Sebastian , Reisinger Sabine , Schwarzmaier Christoph , Bodensteiner Michael , Scheer Manfred
Published: May 2014

A new and selective one‐step synthesis was developed for the first activation stage of white phosphorus by organic radicals. The reactions of NaCpR with P4 in the presence of CuX or FeBr3 leads to the clean formation of organic substituted P4 butterfly compounds CpR2P4 (CpR: CpBIG=C5(4‐nBuC6H4)5 (1 a), Cp′′′=C5H2tBu3 (1 b), Cp*=C5Me5 (1 c) und Cp4iPr=C5HiPr4 (1 d)). The reaction proceeds via the activation of P4 by CpR radicals mediated by transition metals. The newly formed organic derivatives of P4 have been comprehensively characterized by NMR spectroscopy and X‐ray crystallography.
Iterative Assembly of Two Separate Polyketide Chains by the Same Single‐Module Bacterial Polyketide Synthase in the Biosynthesis of HSAF
Authors: Li Yaoyao , Chen Haotong , Ding Yanjiao , Xie Yunxuan , Wang Haoxin , Cerny Ronald L. , Shen Yuemao , Du Liangcheng
Published: May 2014

Antifungal HSAF (heat‐stable antifungal factor, dihydromaltophilin) is a polycyclic tetramate macrolactam from the biocontrol agent Lysobacter enzymogenes. Its biosynthetic gene cluster contains only a single‐module polyketide synthase–nonribosomal peptide synthetase (PKS‐NRPS), although two separate hexaketide chains are required to assemble the skeleton. To address the unusual biosynthetic mechanism, we expressed the biosynthetic genes in two “clean” strains of Streptomyces and showed the production of HSAF analogues and a polyene tetramate intermediate. We then expressed the PKS module in Escherichia coli and purified the enzyme. Upon incubation of the enzyme with acyl‐coenzyme A and reduced nicotinamide adenine dinucleotide phosphate (NADPH), a polyene was detected in the tryptic acyl carrier protein (ACP). Finally, we incubated the polyene–PKS with the NRPS module in the presence of ornithine and adenosine triphosphate (ATP), and we detected the same polyene tetramate as that in Streptomyces transformed with the PKS‐NRPS alone. Together, our results provide evidence for an unusual iterative biosynthetic mechanism for bacterial polyketide–peptide natural products.
A Highly Modular One‐Pot Multicomponent Approach to Functionalized Benzo[b]phosphole Derivatives
Authors: Wu Bin , Santra Mithun , Yoshikai Naohiko
Published: May 2014

Benzo[b]phosphole derivatives have attracted significant attention for their unique optoelectronic properties with potential for application in materials science. Herein we report a modular approach to a benzo[b]phosphole derivative based on a one‐pot sequential coupling of an arylzinc reagent, an alkyne, dichlorophenylphosphine (or phosphorus trichloride and a Grignard reagent), and an oxidant (for example H2O2, S, or Se). The approach allows for the construction of a library of previously inaccessible, structurally diverse benzo[b]phosphole derivatives with unprecedented ease.
DNA binding and nuclease activity of cationic iron(IV) and manganese(III) corrole complexes
Authors: Zhang Yang , Wen Jin‐yan , Wang Xiang‐li , Mahmood Mian HR , Liu Ze‐Yu , Wang Hui , Ji Liang‐nian , Liu Hai‐yang
Published: May 2014

Cationic meso(4‐N‐methylpyridyl)‐based metallocorroles, μ‐oxo iron corrole dimer (1b) and manganese corrole monomer (2b), were synthesized and characterized. The interactions of these two metal corrole complexes with CT‐DNA were studied by UV–visible, fluorescence and circular dichroism spectroscopic methods, as well as by viscosity measurements. The results revealed that 1b interacts with CT‐DNA in a difunctional binding mode, i.e. non‐classical intercalation and outside groove binding with H‐aggregation, while 2b can interact with CT‐DNA via an outside groove binding mode only. The binding constants Kb of 1b and 2b were 4.71 × 105 m−1 and 2.17 × 105 m−1, respectively, indicating that 1b can bind more tightly to CT‐DNA than 2b. Furthermore, both complexes may cleave the supercoiled plasmid DNA efficiently in the presence of hydrogen peroxide or tert‐butyl hydroperoxide (TBHP), albeit 1b exhibited a little higher efficiency. The inhibitor tests suggested that singlet oxygen and high‐valent (oxo)iron(VI) corrole or (oxo)manganese(V) corrole might be the active intermediates responsible for the oxidative DNA scission. Copyright © 2014 John Wiley & Sons, Ltd.
A comprehensive review of alkaline–surfactant–polymer (ASP) flooding
Authors: Sheng James J.
Published: May 2014

Alkaline–surfactant–polymer (ASP) flooding is a combination process in which alkali, surfactant, and polymer are injected in the same slug. Because of the synergy of these three components, ASP is the current worldwide focus of research and field trial in chemical enhanced oil recovery (EOR).

This paper is to provide a comprehensive review of the ASP process. The reviewed topics include the following:

ASP synergy and its EOR mechanisms

Screening criteria

Laboratory work

Numerical simulation work

Summary of pilots and large‐scale applications

Project economics

Chemicals used

Water quality

Mobility control requirement

Problems associated with ASP flooding and possible solutions

In addition to the comprehensive review, future developments are also discussed. Data and analyzed results presented in this review will provide the reader with the updated information about ASP and a guide to read relevant papers for those who are new to chemical EOR. The survey data also provide operators with some reference data for their project design and optimization. © 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
Student teachers' perceptions of their role as civic educators: evidence from a large higher education institution in England
Authors: Peterson Andrew , Durrant Ian , Bentley Brendan
Published: June 2014

This paper presents the findings of a study concerned with student teachers' perceptions of their role as civic educators. Focusing on student teachers undertaking one‐year, pre‐service programmes within the secondary age range (11‐ to 18‐years‐old) at a large higher education institution in the south of England, the study adopted a mixed methods approach involving a cross‐sectional, whole cohort questionnaire and follow‐up individual interviews with a small sample of the original cohort. Here we explore the expectations and perceptions of students regarding both preparing pupils for responsible and active citizenship as a general curricular aim, and teaching pupils citizenship education as a statutory subject within the English National Curriculum for secondary schools. The research is presented in the context of a mixed picture (in terms of both policy and practice) in English secondary schools, with evidence suggesting that education for citizenship is often taught by non‐specialists and that practice is inconsistent across schools. The findings of our research show that the student teachers perceived their role as civic educators to be important, believed that this was a key part of their role as teachers, and that the strength of both perceptions increased over the course of their programmes. The findings also suggest, however, that the student teachers conceptualised education for citizenship in varied and contrasting ways.
A novel role for protein arginine deiminase 4 in pluripotency: The emerging role of citrullinated histone H1 in cellular programming
Authors: Slade Daniel J. , Horibata Sachi , Coonrod Scott A. , Thompson Paul R.
Published: May 2014

Histone post‐translational modifications (PTMs) alter the chromatin architecture, generating “open” and “closed” states, and these structural changes can modulate gene expression under specific cellular conditions. While methylation and acetylation are the best‐characterized histone PTMs, citrullination by the protein arginine deiminases (PADs) represents another important player in this process. In addition to “fine tuning” chromatin structure at specific loci, histone citrullination can also promote rapid global chromatin decondensation during the formation of extracellular traps (ETs) in immune cells. Recent studies now show that PAD4‐mediated citrullination of histone H1 at promoter elements can also promote localized chromatin decondensation in stem cells, thus regulating the pluripotent state. These observations suggest that PAD‐mediated histone deimination profoundly affects chromatin structure, possibly above and beyond that of other PTMs. Additionally, these recent findings further enhance our understanding of PAD biology and the important contributions that these enzymes play in development, health, and disease.
Electrogenerated chemiluminescence of tris(2‐phenylpyridine)iridium(III) in water, acetonitrile and trifluorethanol
Authors: Robinson Wesley D. , Richter Mark M.
Published: May 2014

The spectroscopic, electrochemical and coreactant electrogenerated chemiluminescence (ECL) properties of Ir(ppy)3 (where ppy = 2‐phenylpyridine) have been obtained in aqueous buffered (KH2PO4), 50 : 50 (v/v) acetonitrile–aqueous buffered (MeCN–KH2PO4) and 30% trifluoroethanol (TFE) solutions. Tri‐n‐propylamine was used as the oxidative‐reductive ECL coreactant. The photoluminescence (PL) efficiency (ϕem) of Ir(ppy)3 in TFE (ϕem ≈ 0.029) was slightly higher than in 50 : 50 MeCN–KH2PO4 (ϕem ≈ 0.0021) and water (ϕem ≈ 0.00016) compared to a Ru(bpy)32+ standard solution in water (Φem ≈ 0.042). PL and ECL emission spectra were nearly identical in all three solvents, with dual emission maxima at 510 and 530 nm. The similarity between the ECL and PL spectra indicate that the same excited state is probably formed in both experiments. ECL efficiencies (ϕecl) in 30% TFE solution (ϕecl = 0.0098) were higher than aqueous solution (ϕecl = 0.00092) system yet lower than a 50% MeCN–KH2PO4 solution (ϕecl = 0.0091). Copyright © 2014 John Wiley & Sons, Ltd.
T‐DM1, a novel antibody–drug conjugate, is highly effective against primary HER2 overexpressing uterine serous carcinoma in vitro and in vivo
Authors: English Diana P. , Bellone Stefania , Schwab Carlton L. , Bortolomai Ileana , Bonazzoli Elena , Cocco Emiliano , Buza Natalia , Hui Pei , Lopez Salvatore , Ratner Elena , Silasi Dan‐Arin , Azodi Masoud , Schwartz Peter E. , Rutherford Thomas J. , Santin Alessandro D.
Published: June 2014

Amplification of c‐erbB2 has been reported in over 30% of uterine serous carcinoma (USC) and found to confer poor survival because of high proliferation and increased resistance to therapy. In this study, we evaluated for the first time Trastuzumab emtansine (T‐DM1), a novel antibody–drug conjugate, against multiple epidermal growth factor receptor‐2 (HER2)‐positive USC cells in vitro followed by developing a supportive in vivo model. Fifteen primary USC cell lines were assessed by immunohistochemistry (IHC) and flow cytometry for HER2 protein expression. C‐erbB2 gene amplification was evaluated using fluorescent in situ hybridization. Sensitivity to T‐DM1 and trastuzumab (T)‐induced antibody‐dependent cell‐mediated cytotoxicity was evaluated in 5‐h chromium release assays. T‐DM1 and T cytostatic and apoptotic activities were evaluated using flow‐cytometry‐based proliferation assays. In vivo activity of T‐DM1 versus T in USC xenografts in SCID mice was also evaluated. High levels of HER2 protein overexpression and HER2 gene amplification were detected in 33% of USC cell lines. T‐DM1 was considerably more effective than trastuzumab in inhibiting cell proliferation and in causing apoptosis (P = 0.004) of USC showing HER2 overexpression. Importantly, T‐DM1 was highly active at reducing tumor formation in vivo in USC xenografts overexpressing HER2 (P = 0.04) and mice treated with TDM‐1 had significantly longer survival when compared to T‐treated mice and control mice (P ≤ 0.0001). T‐DM1 shows promising antitumor effect in HER2‐positive USC cell lines and USC xenografts and its activity is significantly higher when compared to T. T‐DM1 may represent a novel treatment option for HER2‐positive USC patients with disease refractory to trastuzumab and traditional chemotherapy.
Immune and Anticancer Responses Elicited by Fully Synthetic Aberrantly Glycosylated MUC1 Tripartite Vaccines Modified by a TLR2 or TLR9 Agonist
Authors: Abdel‐Aal Abu‐Baker M. , Lakshminarayanan Vani , Thompson Pamela , Supekar Nitin , Bradley Judy M. , Wolfert Margreet A. , Cohen Peter A. , Gendler Sandra J. , Boons Geert‐Jan
Published: May 2014

The mucin MUC1 is overexpressed and aberrantly glycosylated by many epithelial cancer cells manifested by truncated O‐linked saccharides. Although tumor‐associated MUC1 has generated considerable attention because of its potential for the development of a therapeutic cancer vaccine, it has been difficult to design constructs that consistently induce cytotoxic T‐lymphocytes (CTLs) and ADCC‐mediating antibodies specific for the tumor form of MUC1. We have designed, chemically synthesized, and immunologically examined vaccine candidates each composed of a glycopeptide derived from MUC1, a promiscuous Thelper peptide, and a TLR2 (Pam3CysSK4) or TLR9 (CpG‐ODN 1826) agonist. It was found that the Pam3CysSK4‐containing compound elicits more potent antigenic and cellular immune responses, resulting in a therapeutic effect in a mouse model of mammary cancer. It is thus shown, for the first time, that the nature of an inbuilt adjuvant of a tripartite vaccine can significantly impact the quality of immune responses elicited against a tumor‐associated glycopeptide. The unique adjuvant properties of Pam3CysSK4, which can reduce the suppressive function of regulatory T cells and enhance the cytotoxicity of tumor‐specific CTLs, are likely responsible for the superior properties of the vaccine candidate 1.
Exploring the Substrate Range of Wild‐Type Aminoacyl‐tRNA Synthetases
Authors: Fan Chenguang , Ho Joanne M. L. , Chirathivat Napon , Söll Dieter , Wang Yane‐Shih
Published: May 2014

We tested the substrate range of four wild‐type E. coli aminoacyl‐tRNA synthetases (AARSs) with a library of nonstandard amino acids (nsAAs). Although these AARSs could discriminate efficiently against the other canonical amino acids, they were able to use many nsAAs as substrates. Our results also show that E. coli tryptophanyl‐tRNA synthetase (TrpRS) and tyrosyl‐tRNA synthetase have overlapping substrate ranges. In addition, we found that the nature of the anticodon sequence of tRNATrp altered the nsAA substrate range of TrpRS; this implies that the sequence of the anticodon affects the TrpRS amino acid binding pocket. These results highlight again that inherent AARS polyspecificity will be a major challenge in the aim of incorporating multiple different amino acids site‐specifically into proteins.
Comparison of VEGF gene silencing efficiencies of chitosan and protamine complexes containing shRNA
Authors: Erdem‐Çakmak Fulden , Özbaş‐Turan Suna , Şalva Emine , Akbuğa Jülide
Published: May 2014

VEGF is an angiogenic factor promoting the proliferation and migration of endothelial cells. Inhibition of VEGF by RNAi mechanism is one of the novel and the most important strategies in antiangiogenesis therapy. In this study, the tumor silencing efficiency of ternary complexes after addition of protamine to chitosan complexes containing VEGF targeting shRNA was investigated. Besides chitosan, protamine is an effective gene delivery material. Binary and ternary complexes consisting of chitosan, protamine, and shRNA were prepared to target VEGF, their morphology, size, and zeta potential of the complexes being measured. The average size of the complexes was between 173 and 284 nm and zeta potential was between +10 and 16 mV. In the ternary complexes, size decreased as the chitosan ratio increased; however, its molecular weight had no effect on the size of complexes. HeLa, HEK293, and MCF‐7 cell lines were used for in vitro transfection. VEGF was assayed by ELISA. A higher silencing effect was obtained using ternary complexes. Transgene expression was increased by adding protamine to chitosan complexes. Gene inhibition values in cell lines followed the rank HEK293>HeLa>MCF‐7. The addition of protamine to the chitosan/shRNA (VEGF) complexes increased the knockdown of VEGF genes in the cell lines, and no cytotoxicity was found after the complexes had been incorporated into the cells.
Response surface methodology for optimization of cyanamide analysis by in situ derivatization and dispersive liquid–liquid microextraction
Authors: Neves Junior Augusto C. V. , Melo Armindo , Pinho Carina , Coneglian Regina C. C. , Soares Antônio G. , Ferreira Isabel M. P. L. V. O.
Published: May 2014

Cyanamide is widely used for agricultural purposes; therefore, its residues can be found in water. A new method was developed for its quantification using in situ derivatization with 2,6‐dimethyl‐4‐quinolinecarboxylic acid N‐hydroxysuccinimide ester followed by dispersive liquid–liquid microextraction (DLLME) and high‐performance liquid chromatography/fluorescence analysis. Multivariate chemometric techniques were successfully used to obtain the optimum conditions for direct derivatization and DLLME extraction. Derivatization parameters and DLLME extraction conditions were optimized by a two‐step design, 2k factorial design for screening, and central composite design for optimization. Best derivatization conditions were addition of 600 μL of derivatizing reagent, a temperature of 4 ºC, and pH 8.5, whereas for optimum extraction 800 μL of solvent, 30% NaCl conc. w/v, and pH 3.8 were chosen.

The analytical performance of the method for routine analysis was evaluated. Excellent linearity was achieved from 10 to 200 µg L−1 with a correlation factor of 0.9996. Precision ranged from 3.5% to 5.5% for intraday assays and 8.5% to 8.6% for interday assays. The mean recoveries performed on water from different origins (ground, river, sea, tap, and mineral) at three levels of concentration (20, 75, and 200 µg L−1) ranged from 90.2% to 110.2%. Copyright © 2014 John Wiley & Sons, Ltd.
Azaphosphatrane Organocatalysts in Confined Space: Cage Effect in CO2 Conversion
Authors: Chatelet Bastien , Joucla Lionel , Dutasta Jean‐Pierre , Martinez Alexandre , Dufaud Véronique
Published: May 2014

The endohedral functionalization of a molecular cage by an azaphosphatrane unit has allowed for the creation of highly engineered catalytic cavities for efficient conversion of CO2 into cyclic carbonates. Strong structure/activity/stability correlations have been demonstrated by careful adjustment of the size, shape, and electronic properties of the hemicryptophane host.
Photochemistry of RuII 4,4′‐Bi‐1,2,3‐triazolyl (btz) Complexes: Crystallographic Characterization of the Photoreactive Ligand‐Loss Intermediate trans‐[Ru(bpy)(κ2‐btz)(κ1‐btz)(NCMe)]2+
Authors: Welby Christine E. , Armitage Georgina K. , Bartley Harry , Wilkinson Aaron , Sinopoli Alessandro , Uppal Baljinder S. , Rice Craig R. , Elliott Paul I. P.
Published: May 2014

We report the unprecedented observation and unequivocal crystallographic characterization of the meta‐stable ligand loss intermediate solvento complex trans‐[Ru(bpy)(κ2‐btz)(κ1‐btz)(NCMe)]2+ (1 a) that contains a monodentate chelate ligand. This and analogous complexes can be observed during the photolysis reactions of a family of complexes of the form [Ru($\widehat{NN}$)(btz)2]2+ (1 a–d: btz=1,1′‐dibenzyl‐4,4′‐bi‐1,2,3‐triazolyl; $\widehat{NN}$=a) 2,2′‐bipyridyl (bpy), b) 4,4′‐dimethyl‐2,2′‐bipyridyl (dmbpy), c) 4,4′‐dimethoxy‐2,2′‐bipyridyl (dmeobpy), d) 1,10‐phenanthroline (phen)). In acetonitrile solutions, 1 a–d eventually convert to the bis‐solvento complexes trans‐[Ru($\widehat{NN}$)(btz)(NCMe)2]2+ (3 a–d) along with one equivalent of free btz, in a process in which the remaining coordinated bidentate ligands undergo a new rearrangement such that they become coplanar. X‐ray crystal structure of 3 a and 3 d confirmed the co‐planar arrangement of the $\widehat{NN}$ and btz ligands and the trans coordination of two solvent molecules. These conversions proceed via the observed intermediate complexes 2 a–d, which are formed quantitatively from 1 a–d in a matter of minutes and to which they slowly revert back on being left to stand in the dark over several days. The remarkably long lifetime of the intermediate complexes (>12 h at 40 °C) allowed the isolation of 2 a in the solid state, and the complex to be crystallographically characterized. Similarly to the structures adopted by complexes 3 a and d, the bpy and κ2‐btz ligands in 2 a coordinate in a square‐planar fashion with the second monodentate btz ligand coordinated trans to an acetonitrile ligand.
α‐Cationic Phosphines: Synthesis and Applications
Authors: Alcarazo Manuel
Published: May 2014

In coordination chemistry, typical ancillary ligands are anionic or neutral species. Cationic ones are exceptions and, when used, the positively charged groups are normally attached to the periphery and not close to the donating atom. However, this concept article highlights a series of recent experimental, as well as theoretical results, suggesting that the utility in catalysis of cationic phosphines with no spacer between the phosphorus atom and the positively charged group(s) has been largely overlooked. In fact, a growing number of studies indicate that, because of their specific architecture, these cationic ligands depict excellent π‐acceptor character that can exceed that of phosphites or polyfluorinated phosphines. This property has been used to increase the Lewis acidity of the metals they coordinate. Specifically, new extreme π‐acid catalysts, mainly based on PtIIand AuI, have been recently prepared and their superior performance demonstrated along several mechanistically distinct transformations. In this concept article the current state of the art is critically assessed and possible future directions of the topic discussed.
Copper‐Catalyzed One‐Pot Denitrogenative–Dehydrogenative–Decarboxylative Coupling of β‐Ketoacids with Trifluorodiazoethane: Facile Access to Trifluoromethylated Aldol Products
Authors: Xiong Heng‐Ying , Yang Zhen‐Yan , Chen Zhen , Zeng Jun‐Liang , Nie Jing , Ma Jun‐An
Published: May 2014

A novel copper‐catalyzed one‐pot cross‐coupling of β‐ketoacids with in situ generated trifluorodiazoethane has been developed. This reaction provides a direct and efficient method, in which one CC bond and one CO bond were formed in a carbenoid center with concomitant denitrogenation–dehydrogenation–decarboxylation, to afford trifluoromethylated aldol products. In several preliminary experiments, good to high enantioselectivities were also obtained.
Total Synthesis of 7‐ and 8‐Oxygenated Pyrano[3,2‐a]carbazole and Pyrano[2,3‐a]carbazole Alkaloids via Boronic Acid‐Catalyzed Annulation of the Pyran Ring
Authors: Julich‐Gruner Konstanze K. , Kataeva Olga , Schmidt Arndt W. , Knölker Hans‐Joachim
Published: May 2014

The boronic acid‐catalyzed annulation of citral opens up a short route to oxygenated cyclized monoterpenoid pyranocarbazole alkaloids. Thus, murrayamine‐D is available in only three steps and 55% overall yield from the corresponding carbazole precursor.
ChemInform Abstract: Giant Dielectric Response and Enhanced Thermal Stability of Multiferroic BiFeO3.
Authors: Lin Peng , Cui Simin , Zeng Xierong , Huang Haitao , Ke Shanming
Published: June 2014

Large‐scale fabrication of multiferroic BiFeO3 nanoparticles under ambient pressure is performed by precipitation of BiFe(CN)6·4H2O from an aq.
ChemInform Abstract: Porous Co3O4 Nanorods as Anode for Lithium‐Ion Battery with Excellent Electrochemical Performance.
Authors: Guo Jinxue , Chen Lei , Zhang Xiao , Chen Haoxin
Published: June 2014

Mesoporous Co3O4 nanorods as high performance anode for Li‐ion batteries are prepared by a two‐step approach comprising hydrothermal processing of CoCl2 and urea (autoclave, 100 °C, 12 h) followed by calcination in air (300 °C, 2 h).
ChemInform Abstract: KSbB2O6 and BaSb2B4O12: Novel Boroantimonates with 3D Anionic Architectures Composed of 1D Chains of SbO6 Octahedra and B2O5 Groups.
Authors: Huang Chao , Zhang Jian‐Han , Hu Chun‐Li , Xu Xiang , Kong Fang , Mao Jiang‐Gao
Published: June 2014

Single crystals of the title compounds are prepared by solid state reaction of K2CO3 or Ba(OH)2, Sb2O3, and H3BO3 (Pt crucibles, 850 °C, 33 h).
ChemInform Abstract: K2S6, a Potassium Polysulfide with Long Sulfur Chain.
Authors: Getzschmann Juergen , Kaskel Stefan
Published: June 2014

K2S6 is prepared in high purity by reacting potassium dissolved in liq.
ChemInform Abstract: Na2Y3Cl3[TeO3]4: Synthesis, Crystal Structure and Spectroscopic Properties of the Bulk Material and Its Luminescent Eu3+‐Doped Samples.
Authors: Zitzer Sabine , Schleifenbaum Frank , Schleid Thomas
Published: June 2014

Colorless single crystals of the title compound are prepared by solid state reaction of Y2O3 and TeO2 in a molar ratio of 3:8 with an excess of NaCl as flux and reactant (silica ampule, Ar, 775 °C, 5 d).
ChemInform Abstract: Enantioselective Fluorination Reaction of β‐Ketoester‐Catalyzed Chiral Primary Amine‐Based Multifunctional Catalyst Systems.
Authors: Shang Jun‐Yan , Li Li , Lu Yixin , Yang Ke‐Fang , Xu Li‐Wen
Published: June 2014

Combination of a cinchona alkaloid‐derived primary amine with L‐leucine gives a dual amine system with promising catalytic activity in enantioselective fluorination reactions of indanone‐2‐carboxylates (I).
ChemInform Abstract: Chiral Lewis Acid Catalyzed Asymmetric Cycloadditions of Disubstituted Ketenes for the Synthesis of β‐Lactones and δ‐Lactones.
Authors: Hao Xiaoyu , Liu Xiaohua , Li Wei , Tan Fei , Chu Yangyang , Zhao Xiaohu , Lin Lili , Feng Xiaoming
Published: June 2014

All reaction products are isolated with 98% diastereoisomeric excess.
ChemInform Abstract: Rare Earth Triflates/Chlorotrimethylsilane‐Promoted One‐Pot Synthesis of Enals.
Authors: Toyota Masahiro , Kagawa Natsuko , Sasaki Yoshiko , Sakaguchi Shoko , Nagatomo Ayumi , Kojima Hideo
Published: June 2014

Et3N can be doubly activated by Tms‐Cl and various rare earth lanthanide triflates to become a protected acetaldehyde anion equivalent, which reacts with various heteroaromatic aldehydes to furnish the corresponding enals in moderate yields.
ChemInform Abstract: Studies Towards 1,3‐Diol Units Starting from syn β‐Hydroxy Acylsilanes.
Authors: PavanKumar Reddy Gangireddy , Srirama Murthy Akondi , Satyanarayana Reddy J. , Das Saibal , Roisnel Thierry , Yadav Jhillu S. , Chandrasekhar Srivari , Gree Rene
Published: June 2014

Syn β‐hydroxy acylsilanes migrate to 1,3‐diols in the presence of fluoride anions.
ChemInform Abstract: Synthesis of Novel Zerumbone Derivatives via Regioselective Palladium Catalyzed Decarboxylative Coupling Reaction: A New Class of α‐Glucosidase Inhibitors.
Authors: Ajish K. R. , Dhanya B. P. , Joseph Nayana , Rani M. Priya , Raghu K. G. , Vineetha V. P. , Radhakrishnan K. V.
Published: June 2014

A strategy for the synthesis of novel zerumbone derivatives via a regioselective palladium catalyzed decarboxylative coupling reaction using arene carboxylic acids is described.
ChemInform Abstract: A Chiral Sulfoxide‐Ligated Ruthenium Complex for Asymmetric Catalysis: Enantio‐ and Regioselective Allylic Substitution.
Authors: Trost Barry M. , Rao Meera , Dieskau Andre P.
Published: June 2014

This reaction proceeds with good regio‐ and enantioselectivity yielding preferably the branched products.
ChemInform Abstract: A Convenient Synthesis of Bisamides with BF3 Etherate as Catalyst.
Authors: Zhang Yi , Zhong Zhihao , Han Yingmei , Han Ruirui , Cheng Xu
Published: June 2014

BF3‐catalyzed reaction of carboxylic amides with a variety of aldehydes allows the synthesis of bisamides under very mild reaction conditions.
ChemInform Abstract: Oxidation of Benzaldehydes to Benzoate Esters Using Household Bleach and Sodium Iodide in Alcohol Solvents.
Authors: Hathaway Bruce A. , DeKastle Christopher A. D. , Arnett Brianna A.
Published: June 2014

Performing the reaction in EtOH provides esters in yields comparable to those obtained in MeOH.
ChemInform Abstract: Diverse Modifications of the 4‐Methylphenyl Moiety of TAK‐779 by Late‐Stage Suzuki—Miyaura Cross‐Coupling.
Authors: Junker Anna , Schepmann Dirk , Yamaguchi Junichiro , Itami Kenichiro , Faust Andreas , Kopka Klaus , Wagner Stefan , Wuensch Bernhard
Published: June 2014

A variety of new analogues of the potent and selective CCRS receptor antagonist TAK‐779 with increased oral bioavailability are synthesized.
ChemInform Abstract: Synthesis and Acylation of 3‐Aryl‐5‐(2‐phenylethynyl)‐4,5‐dihydro‐1H‐pyrazoles.
Authors: Odin I. S. , Golovanov A. A. , Bekin V. V. , Pisareva V. S.
Published: June 2014

Hydrazinolysis of ketones (I) in EtOH gives the title pyrazoles (II), which form stable N‐acyl derivatives (IV) with expected activity against mycobacteria.
ChemInform Abstract: CuI‐Catalyzed Cycloisomerization of Propargyl Amides.
Authors: Alhalib Ali , Moran Wesley J.
Published: June 2014

The synthesis of substituted dihydrooxazoles (II) and (IV) by a CuI‐catalyzed cycloisomerization of terminal propargyl amides (I) is reported.
ChemInform Abstract: Synthesis of New 1‐Substituted‐1H‐1,2,3,4‐tetrazoles from L‐α‐Amino Acids and Their Biological Assays.
Authors: Habibi Davood , Rahmani Payam , Ahmadi Fatemeh , Bokharaei Hanieh , Kaboudvand Zahra
Published: June 2014

Acetic acid catalyzes the reaction between L‐α amino‐acids, triethyl orthoformate and sodium azide giving tetrazole products (III) in good yields.
ChemInform Abstract: Immobilization of 1,4‐Diazabicyclo[2.2.2]octane (DABCO) over Mesoporous Silica SBA‐15: An Efficient Approach for the Synthesis of Functionalized Spirochromenes.
Authors: Baharfar Robabeh , Azimi Razieh
Published: June 2014

Immobilized DABCO appears to be an efficient heterogeneous catalyst for the synthesis of biologically active functionalized spirochromene derivatives via three‐component reaction of isatins/acenaphthoquinone with activated methylene reagents and 1,3‐dicarbonyl compounds in water.
ChemInform Abstract: Palladium‐Catalyzed Domino Protodecarboxylation/Oxidative Heck Reaction: Regioselective Arylation of Coumarin‐3‐carboxylic Acids.
Authors: Khoobi Mehdi , Molaverdi Fatemeh , Alipour Masoumeh , Jafarpour Farnaz , Foroumadi Alireza , Shafiee Abbas
Published: June 2014

A simple catalyst system consisting of Pd(OAc)2 and 1,10‐phenanthroline is applied to give a wide range of different substituted coumarins without the need of a base or co‐catalyst.
ChemInform Abstract: A Multicomponent Reaction of Acetals for the Preparation of Quinolines.
Authors: Zhang Xue‐Lin , Wu Qin‐Pei , Zhang Qing‐Shan
Published: June 2014

No products are obtained when an internal alkyne diphenylacetylene or unsubstituted dimethoxymethane are used as substrates.
ChemInform Abstract: A Facile Access to Polyfunctional Oxygen‐Containing Heterocycles via Intramolecularly Formed Protic Oxonium Ylide Trapping Processes.
Authors: Guo Xin , Liu Wei , Hu Wenhao
Published: June 2014

Intramolecular trapping of oxonium ylides, generated by Cu‐catalyzed decomposition of diazoesters (I), with electron‐deficient aldehydes and isatins yields 3‐substituted 1,4‐dioxan‐2‐ones with high diastereoselectivity.
ChemInform Abstract: Synthesis of Thianthrene Derivatives Linked by Carbon Chains.
Authors: Sheikh Md. Chanmiya , Iwasawa Takasi , Nakajima Akitaka , Kitao Atsutaka , Tsubaki Noritatsu , Miyatake Ryuta , Yoshimura Toshiaki , Morita Hiroyuki
Published: June 2014

This describes the syntheses of several carbon‐chain‐linked thianthrene derivatives, e.
ChemInform Abstract: Structural Proof of Tetrazolo[1,5‐a]quinazoline Derivatives and Their Application in the Synthesis of 4‐Amino‐2‐(1,2,3‐triazol‐1‐yl)quinazolines.
Authors: Kalnina A. , Bizdena E. , Kiselovs G. , Mishnev A. , Turks M.
Published: June 2014

2,4‐Diazidoquinazoline (I), which exists as an equilibrium mixture of azide and tetrazoles, reacts with amines (II) to furnish tetrazoloquinazolines (III).
ChemInform Abstract: 25th Anniversary Article: Semiconductor Nanowires — Synthesis, Characterization, and Applications
Authors: Dasgupta Neil P. , Sun Jianwei , Liu Chong , Brittman Sarah , Andrews Sean C. , Lim Jongwoo , Gao Hanwei , Yan Ruoxue , Yang Peidong
Published: June 2014

Review: 350 refs.
ChemInform Abstract: Phase Diagram of the Iridium—Rhenium System
Authors: Yusenko Kirill V.
Published: June 2014

Review: 35 refs.
ChemInform Abstract: Chemical Expansion of Solid Oxide Fuel Cell Materials: A Brief Overview
Authors: Bishop S. R.
Published: June 2014

Review: 62 refs.
ChemInform Abstract: Molecular CuII‐O‐CuIIComplexes: Still Waters Run Deep
Authors: Haack Peter , Limberg Christian
Published: June 2014

Review: [70 refs.
ChemInform Abstract: Development of π‐Electron Systems Based on [M(dmit)2] (M: Ni and Pd; dmit: 1,3‐Dithiole‐2‐thione‐4,5‐dithiolate) Anion Radicals
Authors: Kato Reizo
Published: June 2014

Review: 91 refs.
ChemInform Abstract: Generation and Reactivity of O‐Carborynes
Authors: Qiu Zaozao , Xie Zuowei
Published: June 2014

Review: 51 refs.
ChemInform Abstract: Strategies Towards Challenging Fluorination Reactions
Authors: Hollingworth Charlotte , Gouverneur Veronique
Published: June 2014

Review: 131 refs.
ChemInform Abstract: Synthesis of Phthalocyanines with an Extended System of π‐Electron Conjugation
Authors: Dubinina T. V. , Tomilova L. G. , Zefirov N. S.
Published: June 2014

Review: 112 refs.
ChemInform Abstract: Molecular Tools for the Construction of Peptide‐Based Materials
Authors: Ramakers B. E. I. , van Hest J. C. M. , Loewik D. W. P. M.
Published: June 2014

Review: 90 refs.
ChemInform Abstract: Doped Graphene for Metal‐Free Catalysis
Authors: Kong Xiang‐Kai , Chen Chang‐Le , Chen Qian‐Wang
Published: June 2014

Review: 125 refs.
ChemInform Abstract: Transition Metal‐Catalyzed Direct Arylation of Unactivated Arenes with Aryl Halides
Authors: Lei Aiwen , Zhang Hua
Published: June 2014

Review: 48 refs.
ChemInform Abstract: Crystallographic Evidence for the Host‐Guest Interaction of Metallamacromolecules
Authors: Lee Cheng‐Hua , Huang Chia‐Yuan , Thanasekaran Pounraj
Published: June 2014

Review: [30 refs.
ChemInform Abstract: Hetero‐Cycloreversions Mediated by Photoinduced Electron Transfer
Authors: Perez‐Ruiz Raul , Jimenez M. Consuelo , Miranda Miguel A.
Published: June 2014

Review: 62 refs.
ChemInform Abstract: Metal—Carbon Bonds in Biopolymer Conjugates: Bioorganometallic Nucleic Acid Chemistry
Authors: Duprey Jean‐Louis H. A. , Tucker James H. R.
Published: June 2014

Review: [74 refs.
ChemInform Abstract: A Fresh Look at an Old Nano‐Technology: Catalysis
Authors: Freund H.‐J. , Nilius N. , Risse T. , Schauermann S.
Published: June 2014

Review: 116 refs.
ChemInform Abstract: The Concept, Reality and Utility of Single‐Site Heterogeneous Catalysts (SSHCs)
Authors: Thomas John Meurig
Published: June 2014

Review: 107 refs.
Inhibitory Effects of Carvone Isomers on the GABAA Receptor in Primary Cultures of Rat Cortical Neurons
Authors: Sánchez‐Borzone Mariela , Delgado‐Marín Leticia , García Daniel A.
Published: May 2014

Carvone is a natural terpene which can be purified as R‐(−) or S‐(+) enantiomers. There are many reports about its antibacterial, antifungal, and insecticide activities, and also of some effects on the nervous system, where both enantiomers showed different potencies. Considering that the GABAA receptor is a major insecticide target, we studied the pharmacological activity of both carvone enantiomers, and of thujone as a reference compound acting on the receptor, on native GABAA by determining their effects on benzodiazepine recognition sites using primary neuronal cultures. Both isomers were able to inhibit the GABA‐induced stimulation of [3H]flunitrazepam binding, suggesting their interaction with the GABAA receptor as negative allosteric modulators. Their activity was comparable to that described for thujone in the present article, with the R‐(−)‐carvone being the more similar and potent stereoisomer. The different configuration of the isopropenyl group in position 5 thus seems to be significant for receptor interaction and the bicycle structure not to be critical for receptor recognition. The concentrations necessary to induce negative modulation of the receptor were not cytotoxic in a murine neuron culture system. These results confirm that, at least partially, the reported insecticidal activity of carvones may be explained by their interaction with the GABAA receptor at its noncompetitive blocker site. Chirality 26:368–372, 2014. © 2014 Wiley Periodicals, Inc.
Recent Advances in Chemical Process Optimization
Authors: Biegler Lorenz T.
Published: May 2014

Systematic optimization strategies are essential in process design, operations and control. This study provides a concise overview of recent advances in process optimization, with a particular focus on nonlinear programming. Here, derivative‐free, SQP, reduced gradient, and interior point methods are described. Moreover, state of the art problem formulations and modeling environments are described, and contrasted with popular process simulation tools. Finally research directions are identified for future trends in multi‐scale optimization within large‐scale equation‐oriented optimization environments.
A fast path planning approach for unmanned aerial vehicles
Authors: Li Shidong , Zhou Huihua , Hu Jia , Ai Qing , Cai Chao
Published: May 2014

In unmanned aerial vehicles navigation, path planning is aimed at obtaining the optimal safety path between start and destination locations. The efficiency and optimality criterion depend on the environment and planning method adopted. In this paper, a general fast path planning framework is proposed for unmanned aerial vehicles navigation. Standard A* search is performed online on the roadmap, which consists of path segments that are pre‐computed offline with the aid of a multi‐resolution grid and terminate at somewhere along the boundary between adjacent cells. Fast marching method (FMM) was employed for two aspects of the roadmap pre‐computation: the location of segment termination points is determined by FMM propagation from the center of a given cell at the highest resolution grid, and the actual segments are computed using FMM between all pairs of nodes belonging to a given cell at all resolutions. Environment dynamics are taken into account by replanning from scratch after modifying the costs associated with the path segments that intersect ‘threat’ or ‘no‐fly’ zones. The altitude along the planned path is determined in a post‐processing step by inspecting the elevation profile along the path and using Sparse A*searching method. The experimental results show that planning speed can be improved significantly with the proposed method, especially, fast online path planning can be achieved to adapt to environmental changes. Copyright © 2014 John Wiley & Sons, Ltd.
Controlling fairness and task granularity in distributed, online, non‐clairvoyant workflow executions
Authors: Ferreira da Silva Rafael , Glatard Tristan , Desprez Frédéric
Published: May 2014

Distributed computing infrastructures are commonly used for scientific computing, and science gateways provide complete middleware stacks to allow their transparent exploitation by end users. However, administrating such systems manually is time consuming and sub‐optimal because of the complexity of the execution conditions. Algorithms and frameworks aiming at automating system administration must deal with online and non‐clairvoyant conditions, where most parameters are unknown and evolve over time. We consider the problem of controlling task granularity and fairness among scientific workflows executed in these conditions. We present two self‐managing loops monitoring the fineness, coarseness, and fairness of workflow executions, comparing these metrics with thresholds extracted from knowledge acquired in previous executions and planning appropriate actions to maintain these metrics to appropriate ranges. Experiments on the European Grid Infrastructure show that our task granularity control can speed up executions up to a factor of 2 and that our fairness control reduces slowdown variability by 3–7 compared with first‐come, first‐served. We also study the interaction between granularity control and fairness control: our experiments demonstrate that controlling task granularity degrades fairness but that our fairness control algorithm can compensate this degradation. Copyright © 2014 John Wiley & Sons, Ltd.
Tuning Photoluminescence Emission of a Cadmium–Organic Framework by Excitation
Authors: Wang Lin , Yang E , Zhang Huabin , Zhang Jian
Published: May 2014

A novel three‐dimensional metal–organic framework with primitive cubic (pcu) topology exhibits interesting tunable photoluminescent emission based on the variation of excitation light at room temperature. By judicious choice of two different conjugated organic linkers incorporating in a certain framework, the contributions of distinct emission bands may be finely controlled. This work may provide a new route to explore functional luminescent materials with tunable photoluminescence.
Consensus protocol design for discrete‐time networks of multiagent with time‐varying delay via logarithmic quantizer
Authors: Park Myeong Jin , Kwon Oh Min , Choi Seong Gon , Cha Eun Jong
Published: May 2014

This article considers the problem of consensus for discrete‐time networks of multiagent with time‐varying delays and quantization. It is assumed that the logarithmic quantizer is utilized between the information flow through the sensor of each agent, and its quantization error is included in the proposed method. By constructing a suitable Lyapunov‐Krasovskii functional and utilizing matrix theory, a new consensus criterion for the concerned systems is established in terms of linear matrix inequalities (LMIs) which can be easily solved by various effective optimization algorithms. Based on the consensus criterion, a designing method of consensus protocol is introduced. One numerical example is given to illustrate the effectiveness of the proposed method. © 2014 Wiley Periodicals, Inc. Complexity 21: 163–176, 2015
Multisignal histogram‐based islanding detection using neuro‐fuzzy algorithm
Authors: Hagh Mehrdad Tarafdar , Ghadimi Noradin
Published: May 2014

Islanding is an important concern for grid‐connected distributed resources due to personnel and equipment safety issues. Several techniques based on passive and active detection schemes have been proposed previously. Although passive schemes have a large nondetection zone (NDZ), concerns have been raised about active methods because of their degrading effect on power quality. Reliably detecting this condition is regarded by many as an ongoing challenge because existing methods are not entirely satisfactory. This article proposes a new integrated histogram analysis method using a neuro‐fuzzy approach for islanding detection in grid‐connected wind turbines. The main objective of the proposed approach is to reduce the NDZ to as close as possible to zero and to maintain the output power quality unchanged. In addition, this technique can also overcome the problem of setting detection thresholds which is inherent in existing techniques. The method proposed in this study has a small NDZ and is capable of detecting islanding accurately within the minimum standard time. Moreover, for those regions which require better visualization, the proposed approach can serve as an efficient aid for better detecting grid‐power disconnection. © 2014 Wiley Periodicals, Inc. Complexity 21: 195–205, 2015
Facile solvothermal synthesis, growth mechanism and thermoelectric property of flower‐like Bi2Te3
Authors: Jin Rencheng , Liu Junshen , Li Guihua
Published: May 2014

Hierarchical flower‐like Bi2Te3 was synthesized through a facile solvothermal method. The crystal structure and morphology of the as‐prepared samples were characterized by X‐ray diffraction (XRD), filed emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and high resolution TEM. The reaction parameters such as reaction time, the amount of glucose, concentration of NaOH and the reaction temperature were systematically investigated. Based on the FESEM observations, a possible mechanism defined as a self‐assembly process accompanied by anisotropic growth mechanism was proposed. Moreover, the thermoelectric properties were measured at the temperature range of 300–600 K. The hierarchical flower‐like Bi2Te3 presented good thermoelectrical properties. The maximum ZT value reached up to 0.6 at 600 K, which was higher than that of Bi2Te3 nanoparticles.
A Synthetic Biotinylated Peptide, BP21, Inhibits the Induction of mRNA Expression of Inflammatory Substances by Oxidized‐ and Lyso‐Phosphatidylcholine
Authors: Sato Akira , Kumagai Takeshi , Ebina Keiichi
Published: May 2014

Preclinical Research

Oxidized low‐density lipoprotein (ox‐LDL) is implicated in many inflammatory diseases, e.g., type 2 diabetes, obesity, atherosclerosis, and metabolic syndrome. We previously reported that a synthetic biotinylated peptide, BP21, inhibits the bioactivity of ox‐LDL via direct binding to ox‐LDL. Here, we investigated the effect of BP21 on the mRNA expression of proinflammatory mediators induced by two major components of ox‐LDL, oxidized‐ and lyso‐phosphatidylcholine (ox‐PC and LPC), in monocytes/macrophages (THP‐1 cells) and adipocytes (3T3‐L1 cells). In THP‐1 cells, BP21 markedly reduced the mRNA expression of interleukin (IL)‐6, adipocyte fatty acid‐binding protein (aP2), tumor necrosis factor‐α, and mitogen‐activated protein kinase phosphatase‐1, which are induced by one of the major bioactive components of ox‐PC, 1‐palmitoyl‐2‐(5′‐oxo‐valeroyl)‐sn‐glycero‐3‐phosphocholine (POVPC), and reduced the mRNA expression of IL‐6, the ox‐LDL‐specific scavenger receptor CD36, and aP2 induced by LPC. In adipocytes, the mRNA expression of IL‐1β as an adipokine and aP2 is highly induced by ox‐PC and LPC, and BP21 markedly reduced the mRNA expression of IL‐1β and aP2 induced by POVPC and LPC. Furthermore, BP21 specifically bound to LPC and POVPC in a dose‐dependent manner. These results suggest that BP21 may be useful lead for the potential treatment and prevention of inflammatory diseases caused by ox‐PC and LPC.
Does the increase of deodorisation temperature improve the oxidative stability of refined olive oils?
Authors: Gomes Tommaso , Caponio Francesco , Paradiso Vito Michele , Durante Viviana , Summo Carmine , Pasqualone Antonella
Published: May 2014

One sample of lampante olive oil, neutralised and bleached by a laboratory‐scale refining plant, was deodorised at the two most frequently adopted temperatures in olive oil refining (220°C and 230°C). The samples of deodorised oil were subjected to oven test at 60°C for 25 days. Aliquots of the oils were sampled at fixed times for analytical determinations, and the oxidative stability was evaluated by measuring the time needed to reach the peroxide value of 20 meq O2/kg. The sample that showed the highest oxidative stability was the oil deodorised at the highest temperature. This oil presented a higher level of TAG oligopolymers (TAGP) and lower amounts of oxidised TAGs (ox‐TAG) respect to the oil deodorised at lower temperature. These findings could be explained by the greater pro‐oxidant effect of ox‐TAG respect to TAGP.

Practical applications: The results of this paper can help to choose the right deodorisation temperature for an oil. In fact, increasing the deodorisation temperature – other parameters being equal – leads to an increase in the oxidative stability of the refined oil. Therefore it could be an option when refining oils with potentially low stability. Nevertheless, it should be preferred submitting to refining slightly oxidized oils, with lower deodorisation temperatures, in order to obtain oils with low amounts of both ox‐TAG and TAGP.

Effect of different deodorisation temperatures on the oxidative stability of an olive oil.