bluuebunny/crossref_metadata_2025 huggingface dataset:
Core‐Modified Analogues of Expanded Porphyrins Containing Rigid β,β′‐Linked o‐Phenylene Bridges
Authors: Shetti Vijayendra S. , Kee Se‐Young , Lee Chang‐Hee
Published: December 2013

Structural modifications that lead to the creation of π‐extended aromatic macrocyles involving a heterocyclic ring other than pyrrole and rigid β‐β′ linkages have not been well studied up to date. The rigidity caused by the conformational restriction would change the spectroscopic properties of the system as compared with those of the normal congeners. With these considerations, we have synthesized and fully characterized π‐extended, core modified expanded porphyrins bearing rigid bipyrrole units. Core‐modified naphthorubyrins were synthesized by the Lewis acid‐catalyzed condensation of naphthobipyrrole with thiophene/furan diols, whereas naphthosapphyrins were obtained by reacting 2,9‐diformyl‐naphthobipyrrole with 16‐thia/oxatripyrranes under mild reaction conditions. The core‐modified analogues of both naphthorubyrin and naphthosapphyrin displayed the aromatic character. The dithiarubyrin analogues showed a lack of conformational change as expected and displayed well‐resolved 1H NMR resonances at room temperature. On the other hand, the oxasapphyrin analogue adopts a furan‐inverted geometry, and the ring inversion is independent of the protonation state. The oxanaphthosapphyrin also exhibited a weak fluorescence emission at 613 nm.
Robust Practical Stabilization of Nonholonomic Mobile Robots Based on Visual Servoing Feedback with Inputs Saturation
Authors: Chen Hua , Wang Chaoli , Liang Zhenying , Zhang Dongkai , Zhang Hengjun
Published: December 2013

In this paper, the saturated practical stabilization problem is addressed for a class of nonholonomic mobile robots based on visual servoing feedback with uncertain camera parameters. The new switching control design method to be proposed is directly based on the original system, which can avoid the problem of singularity arising from state or input transformation. A saturated discontinuous controller is presented by applying the multi‐step switching control strategy and the theory of finite‐time stability. The closed‐loop system can be stabilized to a prescribed arbitrarily small neighborhood of the zero equilibrium point in a finite time. Finally, the simulation results show the effectiveness of the proposed controller design approach.
Rhamsan gum production by Sphingomonas sp. CGMCC 6833 using a two‐stage agitation speed control strategy
Authors: Xu Xiao Ying , Zhu Ping , Li Sha , Chen Xiao Ye , Jiang Xing Huan , Xu Hong
Published: December 2013

Varying the agitation speed could greatly affect rhamsan gum production by Sphingomonas sp. CGMCC 6833. Batch fermentations at agitation speeds of 400, 600, 800, and 1,000 rpm were therefore carried out. The time course of specific cell growth rate, specific glucose consumption rate, and specific rhamsan gum formation rate was subsequently determined. Based on the results, a novel two‐stage agitation speed control strategy was developed. From 0 to 13 H, the high specific cell growth and glucose consumption rates were achieved by setting the agitation speed of the fermenter at 800 rpm. From 13 H onward to the end of fermentation, the glucose consumption rate and specific cell growth rate were high at the agitation speed of 600 rpm. Using this method, the maximum concentration and productivity of rhamsan gum reached 21.63 ± 1.76 g L−1 and 0.338 ± 0.028 g L−1 H−1, respectively, which were both higher than the optimum results obtained at constant agitation speeds.
Simultaneous determination of imperatorin and its metabolites in vitro and in vivo by a GC‐MS method: application to a bioavailability and protein binding ability study in rat plasma
Authors: Zhao Gang , Peng Cheng , Du Wei , Wang Sicen
Published: December 2013

In this study, a simple and sensitive gas chromatography–mass spectrometry method was developed for the study of bioavailability and protein binding and the metabolism of imperatorin in rat. The results showed that the pharmacokinetics of imperatorin after intravenous and oral administration in rats exhibited linear characteristics. The absolute bioavailability of imperatorin was calculated as ~3.85, ~33.51 and ~34.76% for 6.25, 12.5 and 25 mg/kg, respectively. The low bioavailability of imperatorin may be attributed to the poor absorption or extensive metabolism. The phase I metabolites of imperatorin formed in vitro by rat liver microsomes were studied, and two metabolites were isolated and identified as xanthotoxol and heraclenin. Following oral administration of imperatorin, one metabolite (heraclenin) was detected in rat plasma, and two potential metabolites (xanthotoxol and heraclenin) were detected in rat urine. However, none of potential metabolites was detected in rat feces and bile. The results showed that the metabolites of imperatorin were excreted by kidney, and heraclenin was associated with an active component. Demethylation and oxygenization were the main metabolic pathways. In vitro plasma protein binding of imperatorin was 90.1 and 92.6% for the spiked rat plasma concentrations of 1.0 and 50.0 µg/mL, respectively, indicating that imperatorin showed slow distribution into the intra‐ and extracellular space. Copyright © 2013 John Wiley & Sons, Ltd.
High‐level expression of Aspergillus niger β‐galactosidase in Ashbya gossypii
Authors: Magalhães Frederico , Aguiar Tatiana Q. , Oliveira Carla , Domingues Lucília
Published: December 2013

Ashbya gossypii has been recently considered as a host for the expression of recombinant proteins. The production levels achieved thus far were similar to those obtained with Saccharomyces cerevisiae for the same proteins. Here, the β‐galactosidase from Aspergillus niger was successfully expressed and secreted by A. gossypii from 2‐µm plasmids carrying the native signal sequence at higher levels than those secreted by S. cerevisiae laboratorial strains. Four different constitutive promoters were used to regulate the expression of β‐galactosidase: A. gossypii AgTEF and AgGPD promoters, and S. cerevisiae ScADH1 and ScPGK1 promoters. The native AgTEF promoter drove the highest expression levels of recombinant β‐galactosidase in A. gossypii, leading to 2‐ and 8‐fold higher extracellular activity than the AgGPD promoter and the heterologous promoters, respectively. In similar production conditions, the levels of active β‐galactosidase secreted by A. gossypii were up to 37 times higher than those secreted by recombinant S. cerevisiae and ∼2.5 times higher than those previously reported for the β‐galactosidase‐high producing S. cerevisiae NCYC869‐A3/pVK1.1. The substitution of glucose by glycerol in the production medium led to a 1.5‐fold increase in the secretion of active β‐galactosidase by A. gossypii. Recombinant β‐galactosidase secreted by A. gossypii was extensively glycosylated, as are the native A. niger β‐galactosidase and recombinant β‐galactosidase produced by yeast. These results highlight the potential of A. gossypii as a recombinant protein producer and open new perspectives to further optimize recombinant protein secretion in this fungus. © 2013 American Institute of Chemical Engineers Biotechnol. Prog., 30:261–268, 2014
Development of at‐line assay to monitor charge variants of MAbs during production
Authors: St. Amand M. M. , Ogunnaike B. A. , Robinson A.S.
Published: December 2013

One major challenge currently facing the biopharmaceutical industry is to understand how MAb microheterogeneity affects therapeutic efficacy, potency, immunogenicity, and clearance. MAb micro‐heterogeneity can result from post‐translational modifications such as sialylation, galactosylation, C‐terminal lysine cleavage, glycine amidation, and tryptophan oxidation, each of which can generate MAb charge variants; such heterogeneity can affect pharmacokinetics (PK) considerably. Implementation of appropriate on‐line quality control strategies may help to regulate bioprocesses, thus enabling more homogenous material with desired post‐translational modifications and PK behavior. However, one major restriction to implementation of quality control strategies is the availability of techniques for obtaining on‐line or at‐line measurements of these attributes. In this work, we describe the development of an at‐line assay to separate MAb charge variants in near real‐time, which could ultimately be used to implement on‐line quality control strategies for MAb production. The assay consists of a 2D‐HPLC method with sequential in‐line Protein A and WCX‐10 HPLC column steps. To perform the 2D‐HPLC assay at‐line, the two columns steps were integrated into a single method using a novel system configuration that allowed parallel flow over column 1 or column 2 or sequential flow from column 1 to column 2. A bioreactor system was also developed such that media samples could be removed automatically from bioreactor vessels during production and delivered to the 2D‐HPLC for analysis. With this at‐line HPLC assay, we have demonstrated that MAb microheterogeneity occurs throughout the cell cycle whether the host cell line is grown under different or the same nominal culture conditions. © 2013 American Institute of Chemical Engineers Biotechnol. Prog., 30:249–255, 2014
Phospholipase C ε‐1 inhibits p53 expression in lung cancer
Authors: Luo Xue‐ping
Published: December 2013

The pathogenesis of lung cancer is to be further investigated. Recent reports indicate that phospholipase C ε‐1 (PLCE1) is a critical molecule involved in tumour growth. This study aims to investigate the role of PLCE1 in the regulation of apoptosis in lung cancer cells. In this study, the surgically removed non‐small‐cell lung cancer (NSCLC) tissue was collected from 36 patients. Single NSCLC cells were prepared from the tissue, in which immune cells of CD3+, CD11c+, CD19+, CD68+ and CD14+ were eliminated by magnetic cell sorting. The expression of PLCE1 and p53 was assessed by quantitative real‐time polymerase chain reaction and Western blotting. Apoptosis of NSCLC cells was analysed by flow cytometry. The results showed that, in cultured NSCLC cells, high levels of PLCE1 and low levels p53 were detected; the two molecules showed a negative correlation (p < 0.01). The addition of anti‐PLCE1 antibody increased the expression of p53 in NSCLC cells, which increased the frequency of apoptotic NSCLC cells. We conclude that NSCLC cells express high levels of PLCE1, which suppresses the expression of p53 in NSCLC cells. PLCE1 can be a therapeutic target of NSCLC. Copyright © 2013 John Wiley & Sons, Ltd.
A Systematic Investigation of Iminosugar Click Clusters as Pharmacological Chaperones for the Treatment of Gaucher Disease
Authors: Joosten Antoine , Decroocq Camille , de Sousa Julien , Schneider Jérémy P. , Etamé Emile , Bodlenner Anne , Butters Terry D. , Compain Philippe
Published: December 2013

A series of 18 mono‐ to 14‐valent iminosugars with different ligands, scaffolds, and alkyl spacer lengths have been synthesized and evaluated as inhibitors and pharmacological chaperones of β‐glucocerebrosidase (GCase). Small but significant multivalent effects in GCase inhibition have been observed for two iminosugar clusters. Our study provides strong confirmation that compounds that display the best affinity for GCase are not necessarily the best chaperones. The best chaperoning effect observed for a deprotected iminosugar cluster has been obtained with a tetravalent 1‐deoxynojirimycin (DNJ) analogue (3.3‐fold increase at 10 μM). In addition, our study provides the first evidence of the high potential of prodrugs for the development of potent pharmacological chaperones. Acetylation of a trivalent DNJ derivative, to give the corresponding acetate prodrug, leads to a pharmacological chaperone that produces higher enzyme activity increases (3.0‐fold instead of 2.4‐fold) at a cellular concentration (1 μM) reduced by one order of magnitude.
First‐in‐Man Study of the Low‐Dose Paclitaxel Using the COBRA‐P Drug‐Eluting Coronary Stent System With a Novel Biodegradable Coating in De Novo Coronary Lesions
Authors: Nakatani Daisaku , Waseda Katsuhisa , Ako Junya , Calderas Carlos , Condado Jose A. , Condado Jose F. , Honda Yasuhiro , Fitzgerald Peter J.
Published: December 2013

Objective

The aim of this first‐in‐man trial was to evaluate vessel response of two doses of the balloon expandable Cobra‐P drug‐eluting coronary stent (DES).

Background

The Cobra‐P DES system consists of a cobalt chromium alloy with bioabsorbable siloxane sol–gel matrix coating that elutes low dose paclitaxel.

Methods

A total of 60 lesions (54 patients) were sequentially assigned to extremely low‐dose (group A: 3.7 µg/18 mm; n = 30, 1/33 dose of the TAXUS Liberte) or low‐dose (group B: 8 µg/18 mm; n = 30) arm. Intravascular ultrasound images were obtained at post‐procedure and at 4 months.

Results

Patient and lesion characteristics were matched between the two groups except for the higher prevalence of men in group B. At 4 months, there were no significant differences in neointimal obstruction (13.5 ± 9.5% vs. 10.9 ± 7.8%, P = 0.276), and maximum cross‐sectional narrowing (31.2 ± 14.3% vs. 28.6 ± 16.1%, P = 0.523) between the two groups. Late‐acquired incomplete stent apposition occurred in four cases in each arm (P = 1.000). Although the volume of late‐acquired incomplete stent apposition did not differ between the two groups (1.0 ± 0.6 mm3 vs. 8.6 ± 10.9 mm3, P = 0.200), maximum late‐acquired incomplete stent apposition area was significantly smaller in group A than in group B (1.1 ± 0.3 mm2 vs. 2.5 ± 1.4 mm2, P = 0.029).

Conclusions

In the first‐in‐man study of the Cobra‐P DES, neointimal hyperplasia at 4 months appears to be similar between extremely low‐dose and low‐dose groups. Although the incidence of late‐acquired incomplete stent apposition was similar, the magnitude of the late‐acquired gap between the stent and vessel was greater in the low‐dose group compared with the extremely low‐dose group. © 2013 Wiley Periodicals, Inc.
Whole‐Cell One‐Pot Biosynthesis of Azelaic Acid
Authors: Otte Konrad B. , Kittelberger Jens , Kirtz Marko , Nestl Bettina M. , Hauer Bernhard
Published: December 2013

Polymers benefit from the use of biogenic resources such as fatty acids. They enable easy access to valuable monomeric building blocks, which, in comparison to their exclusively fossil counterparts, lead to products with improved physicochemical properties. Monomers of special interest are medium‐chain dicarboxylic acids, which are not easy to obtain by traditional chemical means. Previously, we established an in vitro pathway that combined a 9‐lipoxygenase and a 9/13‐hydroperoxide lyase, which enabled the conversion of linoleic acid via a hydroperoxy intermediate into 9‐oxononanoic acid, the precursor of azelaic acid. Herein, we aimed for the further development of the multi‐enzyme cascade, which included the oxidation of 9‐oxononanoic acid and the establishment of a suitable whole‐cell catalyst. A detailed investigation of the simultaneous in vitro reaction setup revealed that both lipoxygenase activation and the subsequent hydroperoxide lyase reaction depend on the hydroperoxide reaction intermediate. For the activation of lipoxygenase, the hydroperoxide lyase activity, therefore, has to be significantly reduced. In accordance with these observations, we established a suitable dual‐expression system and we further demonstrated that endogenous E. coli redox enzymes are feasible to oxidize 9‐oxononanoic acid to azelaic acid. The resulting whole‐cell catalyst is, therefore, able to perform the direct bioconversion of linoleic acid into azelaic acid. The use of organic solvent as the second phase improved the overall performance of the E. coli host strain. The developed one‐pot, single‐step process afforded 29 mg L−1 of azelaic acid within 8 h with a substrate conversion of 34 % and a selectivity of 47 %.
New Insight into Platinum Dissolution from Nanoparticulate Platinum‐Based Electrocatalysts Using Highly Sensitive In Situ Concentration Measurements
Authors: Jovanovič Primož , Pavlišič Andraž , Šelih Vid Simon , Šala Martin , Hodnik Nejc , Bele Marjan , Hočevar Samo , Gaberšček Miran
Published: December 2013

Time‐ and potential‐resolved electrochemical Pt dissolution from commercial Pt and prepared PtCu alloy nanoparticulate catalysts have been studied under potentiodynamic conditions in 0.1 M HClO4 by using on‐line inductively coupled plasma mass spectrometry (ICP‐MS). For the first time the exact amount of dissolved Pt per cycle has been measured on real electrocatalysts. Results show clearly that Pt dissolution depends on the particle size: approximately seven times as much Pt is released into the solution from commercial 3 nm Pt particles as from a commercial 30 nm Pt sample. The stability of our prepared PtCu electrocatalyst is higher than that of a commercial 3 nm electrocatalyst, which is, however, still slightly lower than that of a commercial 30 nm Pt electrocatalyst.
Monitoring of a Pharmaceuticals Freeze‐Drying Process by Model‐Based Process Analytical Technology Tools
Authors: Bosca Serena , Fissore Davide
Published: December 2013

Pharmaceuticals freeze‐drying requires a careful monitoring to preserve product quality. This is a challenging task as it is not possible to measure inline the variables of interest, i.e., temperature and residual amount of ice in the product in the primary drying stage and residual unfrozen water in the secondary drying stage. Various sensors are available to estimate the state of the product, coupling experimental measures and a model of the process. Methods based on the measure of product temperature and on the pressure rise test are discussed and compared by means of experimental investigations. The former is a local intrusive method, as it requires placing thermocouples in various vials, but allows monitoring the batch taking into account its non‐uniformity, while the latter is a global and non‐intrusive method which permits a partial insight into process dynamics.
Oxidative Addition to Palladium(0) Diphosphine Complexes: Observations of Mechanistic Complexity with Iodobenzene as Reactant
Authors: Kurbangalieva Almira , Carmichael Duncan , Hii K. K. (Mimi) , Jutand Anny , Brown John M.
Published: December 2013

Using a combination of electrochemical and NMR techniques, the oxidative addition of PhX to three closely related bis‐diphosphine P2Pd0 complexes, where the steric bulk of just one substituent was varied, has been analysed quantitatively. For the complex derived from MetBu2P, a rapid reaction ensued with PhI following an associative mechanism, and data was also obtained by cyclic voltammetry for PhOTs, PhBr and PhCl, revealing distinct relative reactivities from the related (PCx3)2Pd complex (Cx=cyclohexyl) previously studied. The corresponding EttBu2P complex reacted more slowly with PhI and was studied by NMR spectroscopy. The reaction course indicated a mixture of pathways, with contribution from a component that was [PhI] independent. For the CxtBu2P complex, reaction was again monitored by NMR spectroscopy, and was even slower. At high PhI concentrations reaction was predominantly linear in [PhI], but at lower concentrations the [PhI] independent pathway was again observed, and an accelerating influence of the reaction product was observed over the concentration range. The NMR spectra of the EttBu2P and CxtBu2P complexes conducted in C6D6 shows some line broadening that was augmented on addition of PhI. NMR experiments carried out in parallel show that there is rapid ligand exchange between free phosphine and the Pd2Pd complex and also a slow ligand crossover between different P2Pd complexes. DFT calculations were carried out to further test the feasibility of C6D6 involvement in the oxidative addition process, and located Van der Waals complexes for association of the P2Pd0 complexes with either PhI or benzene. PhI or solvent‐assisted pathways for ligand loss are both lower in energy than direct ligand dissociation. Taken all together, these results provide a consistent explanation for the surprising complexity of an apparently simple reaction step. The clear dividing line between reactions that give a di‐ or monophosphine palladium complex after oxidative addition clarifies the participation of the ligand in coupling catalysis.
Hexanuclear Gold(I) Phosphide Complexes as Platforms for Multiple Redox‐Active Ferrocenyl Units
Authors: Lee Terence Kwok‐Ming , Cheng Eddie Chung‐Chin , Zhu Nianyong , Yam Vivian Wing‐Wah
Published: December 2013

The synthesis, X‐ray crystal structures, electrochemical, and spectroscopic studies of a series of hexanuclear gold(I) μ3‐ferrocenylmethylphosphido complexes stabilized by bridging phosphine ligands, [Au6(PP)n(Fc‐CH2‐P)2][PF6]2 (n=3, PP=dppm (bis(diphenylphosphino)methane) (1), dppe (1,2‐bis(diphenylphosphino)ethane) (2), dppp (1,3‐bis(diphenylphosphino)propane) (3), Ph2PN(C3H7)‐PPh2 (4), Ph2PN(Ph‐CH3‐p)PPh2 (5), dppf (1,1′‐bis(diphenylphosphino)ferrocene) (6); n=2, PP=dpepp (bis(2‐diphenylphosphinoethyl)phenylphosphine) (7)), as platforms for multiple redox‐active ferrocenyl units, are reported. The investigation of the structural changes of the clusters has been probed by introducing different bridging phosphine ligands. This class of gold(I) μ3‐ferrocenylmethylphosphido complexes has been found to exhibit one reversible oxidation couple, suggestive of the absence of electronic communication between the ferrocene units through the Au6P2 cluster core, providing an understanding of the electronic properties of the hexanuclear AuI cluster linkage. The present complexes also serve as an ideal system for the design of multi‐electron reservoir and molecular battery systems.
Isomerization‐ and Temperature‐Jump‐Induced Dynamics of a Photoswitchable β‐Hairpin
Authors: Deeg Andreas A. , Rampp Michael S. , Popp Alexander , Pilles Bert M. , Schrader Tobias E. , Moroder Luis , Hauser Karin , Zinth Wolfgang
Published: December 2013

Conformational changes in proteins and peptides can be initiated by diverse processes. This raises the question how the variation of initiation mechanisms is connected to differences in folding or unfolding processes. In this work structural dynamics of a photoswitchable β‐hairpin model peptide were initiated by two different mechanisms: temperature jump (T‐jump) and isomerization of a backbone element. In both experiments the structural changes were followed by time‐resolved IR spectroscopy in the nanosecond to microsecond range. When the photoisomerization of the azobenzene backbone switch initiated the folding reaction, pronounced absorption changes related to folding into the hairpin structure were found with a time constant of about 16 μs. In the T‐jump experiment kinetics with the same time constant were observed. For both initiation processes the reaction dynamics revealed the same strong dependence of the reaction time on temperature. The highly similar transients in the microsecond range show that the peptide dynamics induced by T‐jump and isomerization are both determined by the same mechanism and exclude a downhill‐folding process. Furthermore, the combination of the two techniques allows a detailed model for folding and unfolding to be presented: The isomerization‐induced folding process ends in a transition‐state reaction scheme, in which a high energetic barrier of 48 kJ mol−1 separates unfolded and folded structures.
Synthesis of Polycyclic Indole Skeletons by a Gold(I)‐Catalyzed Cascade Reaction
Authors: Wang Tao , Shi Shuai , Pflästerer Daniel , Rettenmeier Eva , Rudolph Matthias , Rominger Frank , Hashmi A. Stephen K.
Published: December 2013

The conversion of simple, easily available urea‐substituted 3‐phenylpropargyl alcohols catalyzed by a simple IPr–gold(I) catalyst in a gold(I)‐catalyzed cascade reaction composing of a gold‐catalyzed nucleophilic addition and a subsequent gold‐catalyzed substitution reaction delivers 1H‐imidazo[1, 5−a]indol‐3(2 H)‐ones. Other gold(I) catalysts or silver catalysts gave lower yields and often gave other side products. Gold(III) and copper(II) catalysts decomposed the starting material. Twelve examples, including donor and acceptor substituents on the distal nitrogen of the urea substructure, are provided. An X‐ray crystal structure analysis confirmed the structural assignment. The mechanistic investigation including isolation and further conversion of intermediates and reactions with enantiopure starting materials indicated that after the nucleophilic‐addition step, the substrate undergoes an SN1‐type benzylic substitution reaction at the indolyl alcohol intermediate or an intramolecular hydroamination reaction of the 2‐vinylindole intermediate.
Boryl‐Functionalized σ‐Alkynyl and Vinylidene Rhodium Complexes: Synthesis and Electronic Properties
Authors: Braunschweig Holger , Brown Christopher K. L. , Dewhurst Rian D. , Jimenez‐Halla J. Oscar C. , Kramer Thomas , Krummenacher Ivo , Pfaffinger Bernd
Published: December 2013

The synthesis, reactivity, and properties of boryl‐functionalized σ‐alkynyl and vinylidene rhodium complexes such as trans‐[RhCl(CCHBMes2)(PiPr3)2] and trans‐[Rh(CCBMes2)(IMe)(PiPr3)2] are reported. An equilibrium was found to exist between rhodium vinylidene complexes and the corresponding hydrido σ‐alkynyl complexes in solution. The complex trans‐[Rh(CCBMes2)(IMe)(PiPr3)2] (IMe=1,3‐dimethylimidazol‐2‐ylidene) was found to exhibit solvatochromism and can be quasireversibly oxidized and reduced electrochemically. Density functional calculations were performed to determine the reaction mechanism and to help rationalize the photophysical properties of trans‐[Rh(CCBMes2)(IMe)(PiPr3)2].
Electrophile‐Induced Nucleophilic Substitution of the nido‐Dicarbaundecaborate Anion nido‐7,8‐C2B9H12− by Conjugated Heterodienes
Authors: Frank René , Adhikari Anup Kumar , Auer Henry , Hey‐Hawkins Evamarie
Published: December 2013

Substitution of the dicarbaundecaborate anion nido‐7,8‐C2B9H12− (1) by precise hydride abstraction followed by nucleophilic attack usually leads to symmetric products 10‐R‐nido‐7,8‐C2B9H11. However, thioacetamide (MeC(S)NH2) as nucleophile and acetone/AlCl3 as hydride abstractor gave asymmetric 9‐[MeC(NHiPr)S]‐nido‐7,8‐C2B9H11 (2), whereas N,N‐dimethylthioacetamide (MeC(S)NMe2) gave the expected symmetric 10‐[MeC(NMe2)S]‐nido‐7,8‐C2B9H11 (4). For the formation of 2, acetone and thioacetamide are assumed to give the intermediate MeC(S)N(CMe2) (3), which then attacks 1 with formation of 2. Similarly, reaction of acetyliminium chloride [MeC(O)NH(CPh2)]Cl (5) with 1 in THF gave a mixture of 9‐ and 10‐substituted [MeC(NHCHPh2)O]‐nido‐7,8‐C2B9H11 (6 and 7, respectively). These reactions are the first examples in which compounds (here heterodienes) that unite the functionalities of both hydride acceptor and nucleophilic site react with 1 in a bimolecular fashion. Furthermore, the analogous reaction of 1 and 5 (in an equilibrium mixture with acetyl chloride and benzophenone imine) in MeCN afforded 10‐[MeC(NCPh2)NH]‐nido‐7,8‐C2B9H11 (8) and MeC(O)NHCHPh2 (9).
Tripod Immobilization of Triphenylphosphane on a Silica‐Gel Surface to Enable Selective Mono‐Ligation to Palladium: Application to Suzuki–Miyaura Cross‐Coupling Reactions with Chloroarenes
Authors: Iwai Tomohiro , Tanaka Ryotaro , Harada Tomoya , Sawamura Masaya
Published: December 2013

A silica‐supported triphenylphosphane (Silica‐3p‐TPP) with a Ph3P‐type core, immobilized on a silica surface, was synthesized and characterized by nitrogen‐absorption measurements and solid‐state NMR spectroscopy. The tripodal immobilization constrains the mobility of the phosphane molecule and causes the lone pair on the phosphorus atom to face in the direction perpendicular to the support, resulting in the selective formation of a 1:1 metal–phosphane species that is free from unfavorable steric repulsions caused by the silica surface. Heterogeneous Pd catalysts created in this manner enabled room‐temperature Suzuki–Miyaura cross‐coupling reactions with unactivated chloroarenes, despite the moderate electronic and steric nature of the Ph3P‐based ligands. These catalysts also showed potential in reactions with more challenging substrates under mild conditions. Tripodally immobilized and well‐dispersed phosphanes on the silica surface were crucial for high catalytic activity.
ChemInform Abstract: Measurement of the Md3+/Md2+ Reduction Potential Studied with Flow Electrolytic Chromatography.
Authors: Toyoshima Atsushi , et al. et al.
Published: December 2013

The electrochemical reduction behavior of mendelevium is studied using a flow electrolytic chromatography apparatus employing C fibers modified with Nafion perfluorinated ion exchange resin as the working electrode.
ChemInform Abstract: Simultaneous Presence of (Si3O10)8‐ and (Si2O7)6‐ Groups in New Synthetic Mixed Sorosilicates: BaY4(Si2O7)(Si3O10) and Isotypic Compounds, Studied by Single‐Crystal X‐Ray Diffraction, Raman Spectroscopy and DFT Calculations.
Authors: Wierzbicka‐Wieczorek Maria , Toebbens Daniel M. , Kolitsch Uwe , Tillmanns Ekkehart
Published: December 2013

The new isotypic compounds BaY4(Si2O7)(Si3O10), SrYb4(Si2O7)(Si3O10), and SrSc4(Si2O7)(Si3O10) are synthesized by a high‐temperature flux growth method from mixtures of M2O3 (M: Y, Yb, Sc), BaCO3 or Sr(OH)2, an alkali metal carbonate, and MoO3 as a flux (Pt crucibles, 1150 °C, 3 h).
ChemInform Abstract: Synthesis and Properties of Charge‐Ordered Thallium Halide Perovskites, CsTI+0.5TI3+0.5X3 (X: F or Cl): Theoretical Precursors for Superconductivity?
Authors: Greenblatt M. , et al. et al.
Published: December 2013

CsTlCl3 (I) is prepared via the precursor Cs2TlCl5·H2O (II) which is obtained by precipitation from a HCl solution of CsCl and Tl2O3 using H2O.
ChemInform Abstract: Two New Quaternary Selenostannates Synthesized under Solvothermal Conditions: Crystal Structure and Reflectance Spectra of (1,4‐dabH)2MnSnSe4 and (1,4‐dabH2) Cu2SnSe4.
Authors: Baiyin Menghe , Naren Jiruga , Gang Gang , Wang Xiaojing , Xu Xiaoqing
Published: December 2013

(1,4‐dabH)2MnSnSe4 (I) (1,4‐dab: 1,4‐diaminobutane) and (1,4‐dabH2)Cu2SnSe4 (II) are prepared by solvothermal reaction of the elements in diaminobutane (autoclave, 160 °C, 7 d).
ChemInform Abstract: CrVI→CrV Transition in Uranyl Chromium Compounds: Synthesis and High‐Temperature X‐Ray Diffraction Study of Cs2[(UO2)2(CrO4)3].
Authors: Siidra Oleg I. , Nazarchuk Evgeny V. , Kayukov Roman A. , Bubnova Rimma S. , Krivovichev Sergey V.
Published: December 2013

Single crystals of Cs2[(UO2)2(CrO4)3] are hydrothermally synthesized from aqueous mixtures of (UO2)(NO3)2, CsNO3, and CrO3 (autoclave, 100 °C, 7 d, 92% yield).
ChemInform Abstract: Highly Efficient Synthesis of Heterocyclic and Alicyclic β2‐Amino Acid Derivatives by Catalytic Asymmetric Hydrogenation.
Authors: Li Lanning , Chen Bin , Ke Yuanyuan , Li Qing , Zhuang Yue , Duan Kun , Huang Yichun , Pang Jiyan , Qiu Liqin
Published: December 2013

The novel β2‐amino acid derivatives bearing heterocyclic or alicyclic groups are prepared with excellent enantioselectivities and high yields by catalytic asymmetric hydrogenation under mild conditions.
ChemInform Abstract: Polymer‐Supported Siloxane Transfer Agents for Pd‐Catalyzed Cross‐Coupling Reactions.
Authors: Nguyen Minh H. , Smith Amos B. III
Published: December 2013

A novel polymer‐supported siloxan transfer reagent is developed and efficiently used in Pd‐catalyzed cross‐coupling reactions.
ChemInform Abstract: Cu‐Catalyzed Formal Methylative and Hydrogenative Carboxylation of Alkynes with Carbon Dioxide: Efficient Synthesis of α,β‐Unsaturated Carboxylic Acids.
Authors: Takimoto Masanori , Hou Zhaomin
Published: December 2013

The formal carboxylation of alkynes by a carboalumination (or hydroalumination)/carboxylation cascade is described.
ChemInform Abstract: Stereoselective Synthesis of β‐Alkylated α‐Amino Acids via Palladium‐Catalyzed Alkylation of Unactivated Methylene C(sp3)—H Bonds with Primary Alkyl Halides.
Authors: Zhang Shu‐Yu , Li Qiong , He Gang , Nack William A. , Chen Gong
Published: December 2013

This is a versatile method for the Pd‐catalyzed β‐alkylation of amides.
ChemInform Abstract: A Bifunctional Palladium/Acid Solid Catalyst Performs the Direct Synthesis of Cyclohexylanilines and Dicyclohexylamines from Nitrobenzenes.
Authors: Rubio‐Marques Paula , Leyva‐Perez Antonio , Corma Avelino
Published: December 2013

One‐pot formation of cyclohexylanilines and dicyclohexylamines is described with the degree of hydrogenation determined by the reaction temperature.
ChemInform Abstract: Gram‐Scale Ketone Synthesis by Direct Reductive Coupling of Alkyl Iodides with Acid Chlorides.
Authors: Lu Wenbin , Liang Zhuye , Zhang Yuwei , Wu Fan , Qian Qun , Gong Hegui
Published: December 2013

This procedure is also compatible with the application of crude acid chlorides generated in situ by reaction of the corresponding acids with SOCl2.
ChemInform Abstract: Synthesis of Aryl Sulfonamides via Palladium‐Catalyzed Chlorosulfonylation of Arylboronic Acids.
Authors: DeBergh J. Robb , Niljianskul Nootaree , Buchwald Stephen L.
Published: December 2013

A novel, mild palladium‐catalyzed chlorosulfonylation of boronic acids is developed.
ChemInform Abstract: Pd(0)‐Catalyzed Sequential C—N Bond Formation via Allylic and Aromatic C—H Amination of α‐Methylstyrenes with Diaziridinone.
Authors: Ramirez Thomas A. , Wang Qian , Zhu Yingguang , Zheng Huaiji , Peng Xingao , Cornwall Richard G. , Shi Yian
Published: December 2013

The title method allows the conversion of various substituted α‐methylstyrenes into spirocyclic indolines.
ChemInform Abstract: Synthesis of N‐Methylcarbazoles from N‐(2‐Iodoaryl)‐N‐methylanilines in the Presence of Potassium tert‐Butoxide and Iron(II) Bromide.
Authors: Melnika I. , Bringis K. , Katkevics M.
Published: December 2013

The preparation of N‐methylcarbazoles is achieved from N‐iodoaryl‐N‐methylanilines (V) and (XI) without the use of toxic transition metals or special techniques for generation of radicals.
ChemInform Abstract: Stereoselective Rhodium‐Catalyzed [(3 + 2) + 2] Carbocyclization Reaction of Trialkoxysilyl‐Substituted Alkenylidenecyclopropanes with Monosubstituted Alkynes.
Authors: Evans P. Andrew , Baikstis Tomass , Inglesby Phillip A.
Published: December 2013

All compounds are isolated in high diastereopurity of at least 96% d.e.
ChemInform Abstract: Synthesis of Monospiro‐2‐amino‐4H‐pyran Derivatives Catalyzed by Propane‐1‐sulfonic Acid‐Modified Magnetic Hydroxyapatite Nanoparticles.
Authors: Jalili‐Baleh Leili , Mohammadi Narges , Khoobi Mehdi , Ma'mani Leila , Foroumadi Alireza , Shafiee Abbas
Published: December 2013

A variety of monospiro‐2‐aminopyran derivatives such as (IV), (VII), and (X) (24 examples) are synthesized via three‐component coupling of isatin (I) or ninhydrin (VIII) with malononitrile (II) and 1,3‐dicarbonyl compounds.
ChemInform Abstract: Au‐Catalyzed Formation of Functionalized Quinolines from 2‐Alkynyl Arylazide Derivatives.
Authors: Gronnier Colombe , Boissonnat Guillaume , Gagosz Fabien
Published: December 2013

A novel gold‐catalyzed method to convert 2‐alkynyl arylazides into polysubstituted quinolines is developed.
ChemInform Abstract: Catalytic Asymmetric exo‐Selective [6 + 3] Cycloaddition of Iminoesters with Fulvenes.
Authors: Potowski Marco , Antonchick Andrey P. , Waldmann Herbert
Published: December 2013

The title reaction proceeds with high diastereo‐ and enantioselectivity and allows the selective formation of piperidine derivatives.
ChemInform Abstract: Synthesis and Biological Evaluation of Amino Analogues of Ludartin: Potent and Selective Cytotoxic Agents.
Authors: Lone Shabir H. , Bhat Khursheed A. , Shakeel‐u‐Rehman Shakeel‐u‐Rehman , Majeed Rabiya , Hamid Abid , Khuroo Mohd A.
Published: December 2013

Various amino‐analogues of the cytotoxic guaianolide ludartin are synthesized by Michael type addition of amines at the highly active α‐methylene‐γ‐lactone motif.
ChemInform Abstract: Cyclic Sulfoxides Garlicnins B2, B3, B4, C2, and C3 from Allium sativum.
Authors: Nohara Toshihiro , Fujiwara Yukio , Ikeda Tsuyoshi , Murakami Kohtaro , Ono Masateru , Nakano Daisuke , Kinjo Junei
Published: December 2013

The isolation of five novel natural sulfoxides as well as the elucidation of their relative structures are reported.
ChemInform Abstract: Recent Advances in Free‐Standing Two‐Dimensional Crystals with Atomic Thickness: Design, Assembly and Transfer Strategies
Authors: Zhang Xiaodong , Xie Yi
Published: December 2013

Review: 56 refs.
ChemInform Abstract: K—O (Potassium—Oxygen) System
Authors: Sangster James
Published: December 2013

Review: 131 refs.
ChemInform Abstract: Functional 3‐Arylisoxazoles and 3‐Aryl‐2‐isoxazolines from Reaction of Aryl Nitrile Oxides and Enolates: Synthesis and Reactivity
Authors: Vitale Paola , Scilimati Antonio
Published: December 2013

Review: 47 refs.
ChemInform Abstract: Catalysis by Gold: New Insights into the Support Effect
Authors: Liu Xiao Yan , Wang Aiqin , Zhang Tao , Mou Chung‐Yuan
Published: December 2013

Review: 186 refs.
ChemInform Abstract: Synthesis and Chemical Properties of Adamantylated Nucleic Bases and Related Compounds
Authors: Shokova E. A. , Kovalev V. V.
Published: December 2013

Review: 57 refs.
ChemInform Abstract: Catalytic Cascade Reactions Involving Metal Carbene Migratory Insertion
Authors: Xia Ying , Zhang Yan , Wang Jianbo
Published: December 2013

Review: 61 refs.
ChemInform Abstract: Coordination Polymers Constructed from Oligonuclear Nodes
Authors: Andruh Marius
Published: December 2013

Review: 44 refs.
ChemInform Abstract: Solution Phase Thermodynamics of Strong Electrolytes Based on Ionic Concentrations, Hydration Numbers and Volumes of Dissolved Entities
Authors: Heyrovska Raji
Published: December 2013

Review: 54 refs.
ChemInform Abstract: New Modelling Approach to Liquid‐Solid Reaction Kinetics: From Ideal Particles to Real Particles
Authors: Salmi Tapio , Grenman Henrik , Warna Johan , Murzin Dmitry Yu.
Published: December 2013

Review: 41 refs.
An Update on Lysine Deacylases Targeting the Expanding “Acylome”
Authors: Olsen Christian A.
Published: December 2013

Lysine ε‐amino acetylation has long been recognized as an epigenetically relevant post‐translational modification of multiple residues in histone proteins. However, it has become clear that lysine acetylation is not restricted to histones, and therefore, it may be involved in the regulation of a wide variety of proteins, some of which have been identified and studied in detail. More recently, post‐translational modifications of lysine side chains by additional acyl groups have also been identified, and some of these appear to be regulated by histone deacetylases (HDACs) and/or sirtuins. In this Concept, new developments are discussed with emphasis on the enzymes that have been shown to catalyze the cleavage of these novel marks, including new assays and inhibitors. Ultimately, a deeper understand of these mechanisms should facilitate the development of ligands with therapeutic potential.
Selective expression of CSPG receptors PTPσ and LAR in poorly regenerating reticulospinal neurons of lamprey
Authors: Zhang Guixin , Hu Jianli , Li Shuxin , Huang Lisa , Selzer Michael E.
Published: December 2013

Disability following spinal cord injury is due to failure of axon regeneration, which has been ascribed to environmental factors in the central nervous system and a developmental loss of intrinsic growth capacity in neurons. Recently, the receptor‐like protein tyrosine phosphatases, protein tyrosine phosphatase σ (PTPσ) and leukocyte common antigen‐related phosphatase (LAR), have been identified as specific receptors for the regeneration‐inhibiting matrix molecules chondroitin sulfate proteoglycans (CSPGs). After spinal cord transection in lampreys, axons of the large, identified reticulospinal neurons have heterogeneous regenerative abilities. The bad‐regenerating neurons also undergo a delayed form of axotomy‐induced apoptosis. In the present study, a lamprey genomic database was used to identify homologs of CSPGs, clone PTPσ and LAR, and examine their mRNA expression. CSPG immunoreactivity was increased significantly near the lesion at 2 weeks post transection, and decreased thereafter. Both receptors were expressed selectively in the bad‐regenerating neurons and had overlapping cellular distributions. PTPσ was upregulated with age (LAR was not evaluated). By 2 weeks post transection, neurons expressing PTPσ also showed caspase activation, suggesting apoptosis. The probability of axon regeneration for individual identified neurons was negatively correlated with the expression level of PTPσ in both control and spinal cord–transected lampreys. In an animal 7 weeks post transection, regenerated axons were labeled retrogradely from beyond the transection. PTPσ expression and caspase labeling was seen only in neurons whose axon had not regenerated. These results are consistent with a possible role for PTPσ (and LAR) in both retrograde neuronal death and the poor intrinsic regenerative ability of bad‐regenerating neurons. J. Comp. Neurol. 522:2209–2229, 2014. © 2013 Wiley Periodicals, Inc.
Psychophysical models of consumer expectations and colour harmony in the context of juice packaging
Authors: Wei Shuo-Ting , Ou Li‐Chen , Ronnier Luo M. , Hutchings John
Published: December 2013

The aim of this study was to develop psychophysical models that predict the influence of pack colours on consumers' psychological responses of fruit juices, such as visually perceived expectations of freshness, quality, liking, and colour harmony. Two existing colour harmony models derived from experiments involving only uniform colour plaques were tested using the juice packaging experimental data. Both models failed to predict the visual results obtained. Nevertheless, two parameters relevant to chromatic difference and hue difference were somewhat associated with the visual results. This suggested that, among all colour harmony principles for uniform colours, only the equal‐hue and the equal‐chroma principles can be adopted to describe colour harmony of packaging used for juice. This has the implication that the principles of colour harmony may vary according to the context in which the colours are used. A new colour harmony model was developed for juice packaging, and a predictive model of freshness was derived. Both models adopted CIELAB colour attributes of the package colour and the fruit image colour to predict viewers' responses. Expected liking and juice quality can be predicted using the colour harmony model while expected freshness can be predicted using the predictive model of freshness. © 2013 Wiley Periodicals, Inc. Col Res Appl, 40, 157–168, 2015
Chiral Isotropic Sponge Phase of Hexatic Smectic Layers of Achiral Molecules
Authors: Chen Dong , Shen Yongqiang , Aguero Jose , Korblova Eva , Walba David M. , Kapernaum Nadia , Giesselmann Frank , Watanabe Junji , Maclennan Joseph E. , Glaser Matthew A. , Clark Noel A.
Published: December 2013

Smectic layers of tilted, bent‐core liquid crystals have a tendency to exhibit spontaneous saddle‐splay curvature, a mechanical response that relieves the internal strain of the layers. When this tendency is strong enough, the smectic layers form complex, equilibrium, non‐planar structures such as the helical nanofilaments in the B4 phase and the disordered focal conics in the chiral dark conglomerate (DC) phase. The DC phase is usually observed on cooling directly from the isotropic phase, with the disordered focal conics analogous to the disordered sponge phase found in lyotropic systems. We report a DC phase observed below a B2 phase that is stable down to room temperature. In mixtures with the calamitic liquid crystal 8CB, the low‐temperature DC phase forms a more ordered, bicontinuous structure, resembling the cubic phase observed in the lyotropic systems, which is attributed to the enhanced intralayer ordering of the bent‐core molecules in the mixtures.
A novel emergency management platform for smart public safety
Authors: Bartoli G. , Fantacci R. , Gei F. , Marabissi D. , Micciullo L.
Published: December 2013

This paper proposes an efficient architecture of a smart public safety platform that involves public professional operators as well as citizens. The proposed system is compliant with the emerging paradigm of a smart city. Its main features are that of monitoring, forecasting and managing emergency situations, arising from environmental disasters or crimes. The proposed platform performs a smart and functional integration of heterogeneous components as a smart data gathering and analysis system, a novel professional communication system, wireless sensor networks and social networks. Each element acts not only as an information collector but has autonomous capabilities to cooperate with the others in order to increase the system efficiency and to reduce the need of human interactions. Finally, the paper highlights some open research issues that represent critical aspects and require additional investigations in order to further improve the performance of the proposed platform. Copyright © 2013 John Wiley & Sons, Ltd.
Analysis of capacity and coverage region for Rayleigh fading MIMO relay channel
Authors: Alizadeh Alireza , Hodtani Ghosheh Abed
Published: December 2013

In this paper, we consider Rayleigh fading MIMO relay channel with channel state information at the receivers. First, we extend the previously obtained results for the ergodic capacity of uncorrelated and semi‐correlated MIMO channels and derive closed‐form expressions for the capacity bounds of MIMO relay channel. Next, we study this channel from a new point of view, maximizing coverage region for a desired transmission rate, and investigate the optimal relay location in the sense of maximizing coverage region. However, in order to overcome the mathematical complexity in desired transmission rate analysis, because of the randomness of the multiple antenna channel matrices, we evaluate this rate by using an existing exact formula and also by an approximation we find in the high signal‐to‐noise ratio regime. Numerical results show a perfect match between the Monte Carlo simulations and the obtained analytical closed‐form expressions and also confirm the effectiveness of our approach in cooperative vehicular communication for determining optimal relay location at which the coverage region is maximum. Copyright © 2013 John Wiley & Sons, Ltd.
Benefits of caloric restriction for cardiometabolic health, including type 2 diabetes mellitus risk
Authors: Soare Andreea , Weiss Edward P. , Pozzilli Paolo
Published: December 2013

In the United States, life expectancy has markedly increased during the past century, and population ageing is expected to double within the next 25 years. The process of ageing in a population is associated with the development of chronic diseases, such as type 2 diabetes mellitus, that can be prevented, and even reversed, with the implementation of healthy lifestyle interventions. The evidence to date, consolidated by the numerous epidemiological studies and clinical trials conducted, suggests that caloric restriction is an effective nutritional intervention for preventing most of these age‐related conditions. At a metabolic level, caloric restriction with adequate nutrition has been shown to improve insulin sensitivity, reduce fasting glucose and insulin concentration and prevent obesity, type 2 diabetes, hypertension and chronic inflammation. The purpose of this article is to review current knowledge of the metabolic and clinical implications of caloric restriction with adequate nutrition for the prevention of type 2 diabetes and cardiovascular disease. Copyright © 2013 John Wiley & Sons, Ltd.