bluuebunny/crossref_metadata_2025_split huggingface dataset:
Counterion‐Assisted Shaping of Nanocluster Supracrystals
Authors: Yao Qiaofeng , Yu Yue , Yuan Xun , Yu Yong , Zhao Dan , Xie Jianping , Lee Jim Yang 
Published: November 2014

AbstractAg44(p‐MBA)304− (p‐MBA=para‐mercaptobenzoic acid) nanocluster (NC) supracrystals (SCs) with customizable shapes can be obtained by simply altering the type and concentration of the counterions of the p‐MBA ligands in the dimethylsulfoxide (DMSO)/water crystallization system. Changing the counterion of the p‐MBA ligand from H+ to Cs+ eliminates the directional hydrogen bonds in the SCs, resulting in the packing of deprotonated Ag44(p‐MBA)304− NCs into octahedral SCs, which is in stark contrast to the rhombohedral SCs that were formed by the packing of protonated Ag44(p‐MBA)304− NCs in previous studies. Furthermore, the double layer of deprotonated Ag44(p‐MBA)304− NCs is sensitive to charge screening induced by increasing the Cs+ concentration, thereby providing a means to regulate the precipitation kinetics of the Ag44(p‐MBA)304− NCs for SC shape engineering. Slow precipitation kinetics was found to favor over‐growth at the corners and edges of the octahedral SC nuclei, shaping the SCs into concave octahedra.
Impact of Pore Connectivity on the Design of Long‐Lived Zeolite Catalysts
Authors: Milina Maria , Mitchell Sharon , Cooke David , Crivelli Paolo , Pérez‐Ramírez Javier 
Published: November 2014

AbstractWithout techniques sensitive to complex pore architectures, synthetic efforts to enhance molecular transport in zeolite and other porous materials through hierarchical structuring lack descriptors for their rational design. The power of positron annihilation lifetime spectroscopy (PALS) to characterize the pore connectivity in hierarchical MFI zeolites is demonstrated, establishing a direct link with the enhanced catalyst lifetime in the conversion of methanol to valuable hydrocarbons. The unique ability to capture subtleties of the hierarchical structure originates from the dynamic nature of the ortho‐positronium response to the pore network. The findings reveal the strong dependence on the way in which the hierarchical zeolites are manufactured, having direct implications for the practical realization of these advanced catalysts.
Metal‐Free σ‐Bond Metathesis in 1,3,2‐Diazaphospholene‐Catalyzed Hydroboration of Carbonyl Compounds
Authors: Chong Che Chang , Hirao Hajime , Kinjo Rei 
Published: November 2014

AbstractThe first metal‐free catalytic hydroboration of carbonyl derivatives has been developed in which a catalytic amount of 1,3,2‐diazaphospholene effectively promotes a hydroboration reaction of aliphatic and aromatic aldehydes and ketones. The reaction mechanism involves the cleavage of both the PO bond of the alkoxyphosphine intermediate and the BH bond of pinacolborane as well as the formation of PH and BO bonds. Thus, the reaction proceeds through a non‐metal σ‐bond metathesis. Kinetic and computational studies suggest that the σ‐bond metathesis occurred in a stepwise but nearly concerted manner.
Nanoparticle‐Mediated Binning and Profiling of Heterogeneous Circulating Tumor Cell Subpopulations
Authors: Mohamadi Reza M. , Besant Justin D. , Mepham Adam , Green Brenda , Mahmoudian Laili , Gibbs Thaddeus , Ivanov Ivaylo , Malvea Anahita , Stojcic Jessica , Allan Alison L. , Lowes Lori E. , Sargent Edward H. , Nam Robert K. , Kelley Shana O. 
Published: November 2014

AbstractThe analysis of circulating tumor cells (CTCs) is an important capability that may lead to new approaches for cancer management. CTC capture devices developed to date isolate a bulk population of CTCs and do not differentiate subpopulations that may have varying phenotypes with different levels of clinical relevance. Here, we present a new device for CTC spatial sorting and profiling that sequesters blood‐borne tumor cells with different phenotypes into discrete spatial bins. Validation data are presented showing that cancer cell lines with varying surface expression generate different binning profiles within the device. Working with patient blood samples, we obtain profiles that elucidate the heterogeneity of CTC populations present in cancer patients and also report on the status of CTCs within the epithelial‐to‐mesenchymal transition (EMT).
High Performance Regulator for Fractional Order Systems: A Soft Variable Structure Control Approach
Authors: Kamal Shyam , Bandyopadhyay Bijnan 
Published: November 2014

AbstractIn this paper, soft variable structure control of fractional order systems is proposed for achieving high regulation rates and short settling times. Using the appropriate fractional order Lyapunov approach, a controller based on continuous fractional switch are designed to achieve high control performance. Due to the alleviation of chattering phenomenon soft VSC that is proposed for fractional order systems are quite useful in future for the practical systems.
Membrane potential depolarization causes alterations in neuron arrangement and connectivity in cocultures
Authors: Özkucur Nurdan , Quinn Kyle P. , Pang Jin C. , Du Chuang , Georgakoudi Irene , Miller Eric , Levin Michael , Kaplan David L. 
Published: November 2014

AbstractBackgroundThe disruption of neuron arrangement is associated with several pathologies. In contrast to action potentials, the role of resting potential (Vmem) in regulating connectivity remains unknown.MethodsNeuron assemblies were quantified when their Vmem was depolarized using ivermectin (Ivm), a drug that opens chloride channels, for 24 h in cocultures with astrocytes. Cell aggregation was analyzed using automated cluster analysis methods. Neural connectivity was quantified based on the identification of isolated somas in phase‐contrast images using image processing. Vmem was measured using voltage‐sensitive dyes and whole‐cell patch clamping. Immunocytochemistry and Western blotting were used to detect changes in the distribution and production of the proteins.ResultsData show that Vmem regulates cortical tissue shape and connectivity. Automated cluster analysis methods revealed that the degree of neural aggregation was significantly increased (0.26 clustering factor vs. 0.21 in controls, P ≤ 0.01). The number of beta‐tubulin III positive neural projections was also significantly increased in the neural aggregates in cocultures with Ivm. Hyperpolarized neuron cells formed fewer connections (33% at 24 h, P ≤ 0.05) compared to control cells in 1‐day cultures. Glia cell densities increased (33.3%, P ≤ 0.05) under depolarizing conditions.ConclusionVmem can be a useful tool to probe neuronal cells, disease tissues models, and cortical tissue arrangements.
A Kinetic Study of Sunflower Oil Methanolysis Catalyzed by Barium Hydroxide
Authors: Stamenković Olivera S. , Todorović Zoran B. , Veljković Vlada B. 
Published: November 2014

AbstractMethanolysis of sunflower oil was investigated in the presence of barium hydroxide as a catalyst. It was observed that the methanolysis reaction was both heterogeneously and homogeneously catalyzed. The heterogeneously catalyzed reaction is faster than the homogeneously catalyzed one and determines the overall reaction rate. Under optimum reaction conditions, a very high fatty acid methyl ester content was obtained within a few minutes. The barium hydroxide‐catalyzed methanolysis is faster than the methanolysis catalyzed by calcium oxide and calcium hydroxide and comparable to the potassium hydroxide‐catalyzed methanolysis.
Cu/Ni‐Loaded CeO2‐ZrO2 Catalyst for the Water‐Gas Shift Reaction: Effects of Loaded Metals and CeO2 Addition
Authors: Chamnankid Busaya , Föttinger Karin , Rupprechter Günther , Kongkachuichay Paisan 
Published: November 2014

AbstractTwo different types of metals (Cu and Ni) and the effect of CeO2 addition to produce a CeO2‐ZrO2 co‐supporter were investigated through the water‐gas shift (WGS) reaction. It was found that the WGS activity could be enhanced with CeO2 addition. At relatively high temperature, Ni‐loaded catalysts exhibited higher CO conversion while Cu‐loaded catalysts demonstrated better performance at low temperatures. The stability and yield of the CO2 and H2 products of the Cu catalysts were higher than those of the Ni catalysts. These results may be caused by an irreversible adsorption of CO on Ni and the reverse WGS reaction occurring on the Ni catalysts. In situ diffuse‐reflection infrared Fourier transform spectroscopy data suggests that the WGS mechanism likely proceeded via formate species.
The syn/anti‐Dichotomy in the Palladium‐Catalyzed Addition of Nucleophiles to Alkenes
Authors: Kočovský Pavel , Bäckvall Jan‐E. 
Published: November 2014

AbstractIn this review the stereochemistry of palladium‐catalyzed addition of nucleophiles to alkenes is discussed, and examples of these reactions in organic synthesis are given. Most of the reactions discussed involve oxygen and nitrogen nucleophiles; the Wacker oxidation of ethylene has been reviewed in detail. An anti‐hydroxypalladation in the Wacker oxidation has strong support from both experimental and computational studies. From the reviewed material it is clear that anti‐addition of oxygen and nitrogen nucleophiles is strongly favored in intermolecular addition to olefin–palladium complexes even if the nucleophile is coordinated to the metal. On the other hand, syn‐addition is common in the case of intramolecular oxy‐ and amidopalladation as a result of the initial coordination of the internal nucleophile to the metal.
Hydrothermal Combination of Trilacunary Dawson Phosphotungstates and Hexanickel Clusters: From an Isolated Cluster to a 3D Framework
Authors: Li Xin‐Xiong , Fang Wei‐Hui , Zhao Jun‐Wei , Yang Guo‐Yu 
Published: November 2014

AbstractThree novel hexa‐Ni‐substituted Dawson phosphortungstates [Ni6(en)3(H2O)6(μ3‐OH)3(H3P2W15O56)]⋅14 H2O (1), [Ni(enMe)2(H2O)][Ni6(enMe)3(μ3‐OH)3(H2O)6(HP2W15O56)]⋅ 10 H2O (2), and [Ni(enMe)2]3[Ni(enMe)2(H2O)][Ni(enMe)(H2O)2][Ni6(enMe)3(μ3‐OH)3(Ac)2(H2O)(P2W15O56)]2⋅6 H2O (3) (en=ethylenediamine, enMe=1, 2‐diaminopropane, Ac=CH3COO−) have been made under hydrothermal conditions and were characterized by IR spectroscopy, elemental analysis, diffuse reflectance spectroscopy, thermogravimetric analysis, powder X‐ray diffraction, and single‐crystal X‐ray diffraction. The common structural features of compounds 1–3 contain the similar hexa‐Ni‐substituted Dawson polyoxometalate (POM) units that can be viewed as a [Ni6(μ3‐OH)3]9+ cluster capping on a [P2W15O56]12− fragment. Compounds 1 and 2 are two isolated clusters, whereas compound 3 is the first 3D POM framework constructed from hexa‐Ni‐substituted Dawson POM units and Ni(enMe) complex bridges. The preparations of compounds 1–3 not only indicate that triangle coplanar Ni6 clusters are very stable fragments in both trivacant Keggin and trivacant Dawson POM systems, but also offer that the hydrothermal technique can act as an effective strategy for making novel Dawson‐type high‐nuclear transition‐metal cluster substituted POMs by combination of lacunary Dawson precusors with transition‐metal cations in the tunable role of organic ligands. In addition, magnetic measurements illustrate that there exist overall ferromagnetic interactions in compound 3.
Combining [Arene–Ru] with Azocarboxamide to Generate a Complex with Cytotoxic Properties
Authors: Sommer Michael G. , Kureljak Petra , Urankar Damijana , Schweinfurth David , Stojanović Nikolina , Bubrin Martina , Gazvoda Martin , Osmak Maja , Sarkar Biprajit , Košmrlj Janez 
Published: November 2014

AbstractAzocarboxamide (azcH) has been combined for the first time with [Ru–Cym] to generate metal complexes with N,N‐ and N,O‐coordination mode, [(Cym)Ru(azc)Cl] and [(Cym)Ru(azcH)Cl]+[PF6]−. Geometric and electronic structures of the complexes are reported along with their in vitro activities against different tumour cell lines and preliminary results on solution chemistry. Compound [(Cym)Ru(azc)Cl] exhibited remarkable cytotoxic properties. It was cell‐type specific and had comparable IC50 values towards both cancer cells and their drug‐resistant subline. A tenfold increase in the sensitivity towards [(Cym)Ru(azc)Cl] was noted for the tumour cells with depleted intracellular glutathione (GSH) level, suggesting the essential role of GSH in cell response to this compound.
Multivalency as a Key Factor for High Activity of Selective Supported Organocatalysts for the Baylis–Hillman Reaction
Authors: Goren Kerem , Karabline‐Kuks Jeny , Shiloni Yael , Barak‐Kulbak Einav , Miller Scott J. , Portnoy Moshe 
Published: November 2014

AbstractThe polystyrene‐supported N‐alkylimidazole‐based dendritic catalysts for the Baylis–Hillman reaction exhibit one of the strongest beneficial effects of multivalent architecture ever reported for an organocatalyst. The yields in the model reaction of methyl vinyl ketone with p‐nitrobenzaldehyde are more than tripled when a non‐dendritic catalyst is replaced by a second‐ or third‐generation analogue. Moreover, the reaction of the less active substrates will not occur with the non‐dendritic catalyst and will proceed to a significant extent only with the analogous catalysts of higher generations. A substantial additional enhancement of the reaction yield could be achieved by increasing the content of water in the reaction solvent. The plausible cause of the dendritic effect is the assistance of the second, nearby imidazole moiety in the presumably rate‐determining proton transfer in the intermediate adduct, after the first imidazole unit induced the formation of the new carbon–carbon bond.
Titanium cis‐1,2‐Diaminocyclohexane (cis‐DACH) Salalen Catalysts for the Asymmetric Epoxidation of Terminal Non‐Conjugated Olefins with Hydrogen Peroxide
Authors: Wang Qifang , Neudörfl Jörg‐M. , Berkessel Albrecht 
Published: November 2014

AbstractChiral Ti salalen complexes catalyze the asymmetric epoxidation of terminal non‐conjugated olefins with hydrogen peroxide. Modular ligands based on cis‐1,2‐diamino‐cyclohexane (cis‐DACH) were developed, giving high yields and enantiomeric excesses (ee, up to 96 %) at catalyst loadings as low as 0.1–0.5 mol %, and even under solvent‐free conditions.
Synthesis of a Pentasaccharide and Neoglycoconjugates Related to Fungal α‐(1→3)‐Glucan and Their Use in the Generation of Antibodies to Trace Aspergillus fumigatus Cell Wall
Authors: Komarova Bozhena S. , Orekhova Maria V. , Tsvetkov Yury E. , Beau Remi , Aimanianda Vishukumar , Latgé Jean‐Paul , Nifantiev Nikolay E. 
Published: November 2014

Abstract3‐Aminopropyl α‐(1→3)‐pentaglucoside, a fragment of α‐(1→3)‐glucan of the cell wall of Aspergillus fumigatus, has been synthesized in a blockwise approach. The application of mono‐ and disaccharide N‐phenyltrifluoroacetimidates bearing a stereodirecting 6‐O‐benzoyl group was essential for stereoselective α‐glucosylations. In the products, p‐methoxyphenyl and levulinoyl groups served as orthogonal protecting groups for the anomeric position and 3‐OH group, respectively. Their removal from shared blocks led to donors and acceptors that were used for the synthesis of pentasaccharides. Coupling of free α‐(1→3)‐pentaglucoside with biotin and bovine serum albumin (BSA) gave glycoconjugate tools for mycological studies. Immunization of mice with the BSA conjugate induced the generation of antibodies that recognize α‐(1→3)‐glucan on A. fumigatus cell wall and distinguish its morphotypes. This discovery represents a first step to the development of a diagnostic test system and a vaccine to detect and fight this life‐threatening pathogen.
Controlled Zn‐Mediated Grafting of Thin Layers of Bipodal Diazonium Salt on Gold and Carbon Substrates
Authors: Torréns Mabel , Ortiz Mayreli , Turner Anthony P. F. , Beni Valerio , O'Sullivan Ciara K. 
Published: November 2014

AbstractA controlled, rapid, and potentiostat‐free method has been developed for grafting the diazonium salt (3,5‐bis(4‐diazophenoxy)benzoic acid tetrafluoroborate (DCOOH)) on gold and carbon substrates, based on a Zn‐mediated chemical dediazonation. The highly stable thin layer organic platforms obtained were characterized by cyclic voltammetry, AFM, impedance, XP, and Raman spectroscopies. A dediazonation mechanism based on radical formation is proposed. Finally, DCOOH was proved as a linker to an aminated electroactive probe.
Platinum(II) Olefin Hydroarylation Catalysts: Tuning Selectivity for the anti‐Markovnikov Product
Authors: Clement Marie L. , Grice Kyle A. , Luedtke Avery T. , Kaminsky Werner , Goldberg Karen I. 
Published: November 2014

AbstractPtII complexes containing unsymmetrical (pyridyl)pyrrolide ligands are shown to catalyze the hydroarylation of unactivated alkenes with selectivity for the anti‐Markovnikov product. Substitution on the pyrrolide portion of the ligand allows effective tuning of the selectivity to anti‐Markovnikov alkylarene products, whereas substitution on the pyridyl portion can promote competitive alkenylarene production.
CuII/TEMPO‐Promoted One‐Pot Synthesis of Highly Substituted Pyrimidines from Amino Acid Esters
Authors: Zhou Nini , Xie Tao , Li Zhongle , Xie Zhixiang 
Published: November 2014

AbstractA novel, Cu(OAc)2/TEMPO promoted one‐step approach for the preparation of fully substituted pyrimidines from readily available amino acid esters has been described. In this reaction, the amino acid esters act as the only NC sources for the construction of corresponding pyrimidines. The mechanism of this process includes oxidative dehydrogenation, the generation of an imine radical, and a formal [3+3] cycloaddition. This methodology proves to be a high atom‐economic and straightforward strategy for the synthesis of pyrimidines and diverse substrates which are substituted by various functional groups have been afforded in moderate to good yield.
Biotechnologie und Bioverfahrenstechnik – Vom ersten Ullmanns Artikel bis hin zu aktuellen Forschungsthemen
Authors: Al‐Kaidy Huschyar , Duwe Anna , Huster Manuel , Muffler Kai , Schlegel Christin , Sieker Tim , Stadtmüller Ralf , Tippkötter Nils , Ulber Roland 
Published: November 2014

AbstractBiotechnologie und die mit ihr verbundenen technischen Prozesse prägen seit Jahrtausenden die Entwicklung der Menschheit. Ausgehend von empirischen Verfahren, insbesondere zur Herstellung von Lebensmitteln und täglichen Gebrauchsgütern, haben sich diese Disziplinen zu einem der innovativsten Zukunftsfelder entwickelt. Durch das immer detailliertere Verständnis zellulärer Vorgänge können mittlerweile Produktionsstämme gezielt optimiert werden. Im Zusammenspiel mit moderner Prozesstechnik können so eine Vielzahl von Bulk‐ und Feinchemikalien sowie Pharmazeutika effizient hergestellt werden. In diesem Artikel werden exemplarisch einige der aktuellen Trends vorgestellt.
Development of Second‐Generation Small‐Molecule RhoA Inhibitors with Enhanced Water Solubility, Tissue Potency, and Significant in vivo Efficacy
Authors: Ma Sheng , Deng Jing , Li Baoli , Li Xiujiang , Yan Zhaowei , Zhu Jin , Chen Gang , Wang Zhong , Jiang Hualiang , Miao Liyan , Li Jian 
Published: November 2014

AbstractRhoA, a member of the Rho GTPases, is involved in a variety of cellular functions and could be a suitable therapeutic target for the treatment of cardiovascular diseases. However, few small‐molecule RhoA inhibitors have been reported. Based on our previously reported lead compounds, 32 new 2‐substituted quinoline (or quinoxaline) derivatives were synthesized and tested in biological assays. Six compounds showed high RhoA inhibitory activities, with IC50 values of 1.17–1.84 μM. Among these, (E)‐3‐(3‐(ethyl(quinolin‐2‐yl)amino)phenyl)acrylic acid (26 b) and (E)‐3‐(3‐(butyl(quinolin‐2‐yl)amino)phenyl)acrylic acid (26 d) demonstrated noticeable vasorelaxation effects against phenylephrine‐induced contraction in thoracic aorta artery rings, and compound 26 b had good water solubility and showed significant in vivo efficacy, which was similar to that of 5‐(1,4‐diazepane‐1‐sulfonyl)isoquinoline (fasudil) in a subarachnoid hemorrhage–cardiovascular model. To the best of our knowledge, compound 26 b is the first example of a small‐ molecule RhoA inhibitor with potent in vivo efficacy, which could serve as a good lead for designing cardiovascular agents.
Single‐ and multiple‐dose pharmacokinetic studies of tramadol immediate‐release tablets in children and adolescents
Authors: Vandenbossche J. , Richards H. , Solanki B. , Van Peer A. 
Published: November 2014

AbstractIn these combined analyzes from 3 open‐label, phase‐1 studies, the pharmacokinetic profile of tramadol and its metabolite (M1) following administration of tramadol immediate‐release (IR) tablets in children and adolescents, 7–16 years old (studies 1 and 2: n = 38; study 3: n = 21) with painful conditions following single oral dose of tramadol IR (25–100 mg) (studies 1 and 2) or multiple oral doses of tramadol IR tablets every 6 hours for 3 days (study 3) were compared with that of healthy adults following similar treatment. Area under the curve of tramadol and its metabolite M1 in children and adolescents was lower compared with adults (Dose‐normalized [DN] AUC, h ng/mL: tramadol: 1316.87 [children]; 1418.02 [adolescents];1838.29 [adults]; M1: 342.56 [children]; 475.4 [adolescents]; 636.13 [adults]) while the Cmax remained similar (DN Cmax, ng/mL: tramadol: 203.75 [children]; 165.35 [adolescents]; 226.92 [adults]; M1: 34.93 [children]; 38.42 [adolescents]; 52.14 [adults]). The DN AUC was further lower in children and adolescents with a lower body weight (<50 kg). The weight normalized oral clearance of tramadol was higher in children and adolescents compared with adults (CL/F, mL/min/kg: 12.66 [children]; 11.75 [adolescents]; 9.06 [adults]). No new safety findings emerged. Tramadol was generally safe and well‐tolerated by children and adolescents with painful conditions.
Quantitation of the impact of CYP3A5 A6986G polymorphism on quetiapine pharmacokinetics by simulation of target attainment
Authors: Shilbayeh Sireen A.R. , Sy Sherwin K.B. , Melhem Murad , Zmeili Rawan , Derendorf Hartmut 
Published: November 2014

AbstractThe aim of this study was to evaluate whether genetic polymorphisms in CYP3A5 and ABCB1 are responsible for the interindividual variability observed in quetiapine pharmacokinetics. Pharmacokinetic data from a randomized crossover study evaluating 2 quetiapine 25 mg immediate‐release tablets after single oral dose were used to develop a population pharmacokinetic model. The single nucleotide polymorphisms (SNPs) evaluated for the genotype effects of quetiapine pharmacokinetics were CYP3A5 A6986G and ABCB1 C3435T, along with other demographic variables and formulations. A one‐compartment distribution model with linear elimination plus four transit compartments for the delayed absorption adequately described quetiapine disposition. CYP3A5 *1/*1 individuals (n = 3) had 29% increased clearance compared to *1/*3 and *3/*3 individuals. The impact of an increased clearance was evaluated by simulations. By computing the probability of target attainment (PTA) of steady‐state therapeutic goal at 1‐hour and 12‐hour time points after 50–400 mg twice‐daily regimens, the results indicated that CYP3A5 genotype has minimal impact on the PTA of the 1‐hour concentrations but a significant impact on the 12‐hour concentrations. The interpretation based on the simulations does not call for a genotype‐based dosing scheme and is consistent with consensus guidelines for quetiapine that therapeutic drug monitoring is considered useful. Clinical Pharmacology in Drug Development