bluuebunny/crossref_metadata_2025 huggingface dataset:
Harnessing the Oxidation Susceptibility of Deubiquitinases for Inhibition with Small Molecules
Authors: Ohayon Shimrit , Refua Maya , Hendler Adi , Aharoni Amir , Brik Ashraf
Published: October 2014

Deubiquitinases (DUBs) counteract ubiquitination by removing or trimming ubiquitin chains to alter the signal. Their diverse role in biological processes and involvement in diseases have recently attracted great interest with regard to their mechanism and inhibition. It has been shown that some DUBs are regulated by reactive oxygen species (ROS) in which the catalytic Cys residue undergoes reversible oxidation, hence modulating DUBs activity under oxidative stress. Reported herein for the first time, the observation that small molecules, which are capable of generating ROS efficiently, inhibit DUBs by selective and nonreversible oxidation of the catalytic Cys residue. Interestingly, the small molecule beta‐lapachone, which is currently in clinical trials for cancer, is among the potent inhibitors, thus suggesting possible new cellular targets for its therapeutic effects. Our study describes a novel mechanism of DUBs inhibition and opens new opportunities in exploiting them for cancer therapy.
Supramolecular [60]Fullerene Liquid Crystals Formed By Self‐Organized Two‐Dimensional Crystals
Authors: Zhang Xiaoyan , Hsu Chih‐Hao , Ren Xiangkui , Gu Yan , Song Bo , Sun Hao‐Jan , Yang Shuang , Chen Erqiang , Tu Yingfeng , Li Xiaohong , Yang Xiaoming , Li Yaowen , Zhu Xiulin
Published: October 2014

Fullerene‐based liquid crystalline materials have both the excellent optical and electrical properties of fullerene and the self‐organization and external‐field‐responsive properties of liquid crystals (LCs). Herein, we demonstrate a new family of thermotropic [60]fullerene supramolecular LCs with hierarchical structures. The [60]fullerene dyads undergo self‐organization driven by π–π interactions to form triple‐layer two‐dimensional (2D) fullerene crystals sandwiched between layers of alkyl chains. The lamellar packing of 2D crystals gives rise to the formation of supramolecular LCs. This design strategy should be applicable to other molecules and lead to an enlarged family of 2D crystals and supramolecular liquid crystals.
Hydrogenated Anatase: Strong Photocatalytic Dihydrogen Evolution without the Use of a Co‐Catalyst
Authors: Liu Ning , Schneider Christopher , Freitag Detlef , Venkatesan Umamaheswari , Marthala V. R. Reddy , Hartmann Martin , Winter Benjamin , Spiecker Erdmann , Osvet Andres , Zolnhofer Eva M. , Meyer Karsten , Nakajima Tomohiko , Zhou Xuemei , Schmuki Patrik
Published: October 2014

The high‐pressure hydrogenation of commercially available anatase or anatase/rutile TiO2 powder can create a photocatalyst for H2 evolution that is highly effective and stable without the need for any additional co‐catalyst. This activation effect cannot be observed for rutile; however, for anatase/rutile mixtures, a strong synergistic effect can be found (similar to results commonly observed for noble‐metal‐decorated TiO2). EPR and PL measurements indicated the intrinsic co‐catalytic activation of anatase TiO2 to be due to specific defect centers formed during hydrogenation. These active centers can be observed specifically for high‐pressure hydrogenation; other common reduction treatments do not result in this effect.
Catalytic Dinitrogen Reduction at the Molybdenum Center Promoted by a Bulky Tetradentate Phosphine Ligand
Authors: Liao Qian , Saffon‐Merceron Nathalie , Mézailles Nicolas
Published: October 2014

Stoichiometric reduction of N2 at a Mo center stabilized by a bulky tetradentate phosphine ligand (${{\rm PP}{{{\rm Cy}\hfill \atop 3\hfill}}}$) allowed isolation of Mo–imidoamine and Mo–imido complexes. Both complexes as well as the MoII precursor are equally suitable catalysts for the synthesis of NTMS3 (TMS=trimethylsilyl) from N2, TMSCl, and electron sources. Mechanistic studies prove the involvement of a TMS radical at least in one of the catalytic steps.
Tungsten‐Catalyzed Regio‐ and Enantioselective Aminolysis of trans‐2,3‐Epoxy Alcohols: An Entry to Virtually Enantiopure Amino Alcohols
Authors: Wang Chuan , Yamamoto Hisashi
Published: October 2014

The first catalytic enantioselective aminolysis of trans‐2,3‐epoxy alcohols has been accomplished. This stereospecific ring‐opening process was efficiently promoted by a tungsten/bis(hydroxamic acid) catalytic system, furnishing various anti‐3‐amino‐1,2‐diols with excellent regiocontrol and high enantioselectivities (up to 95 % ee). Moreover, virtually enantiopure 3‐amino‐1,2‐diols could be obtained by the sequential combination of two reactions that both involve the use of a chiral catalyst.
A Dehydratase Domain in Ambruticin Biosynthesis Displays Additional Activity as a Pyran‐Forming Cyclase
Authors: Berkhan Gesche , Hahn Frank
Published: October 2014

Hydropyran rings are a common structural motif in reduced polyketides. Information on their biosynthetic formation and particularly the biochemical characterization of the responsible enzymes has only been reported in few cases. The dehydratase domain AmbDH3 from the ambruticin polyketide synthase was investigated. Through in vitro assay of the recombinant domain with synthetically‐derived substrate surrogates, it was shown that it has a second catalytic activity as a cyclase that performs oxa‐conjugate addition. Probing AmbDH3 with synthetic substrate analogues revealed stereoselectivity and substrate tolerance in both substeps. This is the first characterization of a pyran‐forming cyclase from a cis‐AT PKS system and the first report of a polyketide synthase domain with this kind of dual activity. Finally, it was revealed that this domain shows potential for application in chemoenzymatic synthesis.
Three‐Dimensional Geometric Morphometric Analysis of Talar Morphology in Extant Gorilla Taxa from Highland and Lowland Habitats
Authors: Knigge Ryan P. , Tocheri Matthew W. , Orr Caley M. , Mcnulty Kieran P.
Published: October 2014

Western gorillas (Gorilla gorilla) are known to climb significantly more often than eastern gorillas (Gorilla beringei), a behavioral distinction attributable to major differences in their respective habitats (i.e., highland vs. lowland). Genetic evidence suggests that the lineages leading to these taxa began diverging from one another between approximately 1 and 3 million years ago. Thus, gorillas offer a special opportunity to examine the degree to which morphology of recently diverged taxa may be “fine‐tuned” to differing ecological requirements. Using three‐dimensional (3D) geometric morphometrics, we compared talar morphology in a sample of 87 specimens including western (lowland), mountain (highland), and grauer gorillas (lowland and highland populations). Talar shape was captured with a series of landmarks and semilandmarks superimposed by generalized Procrustes analysis. A between‐group principal components analysis of overall talar shape separates gorillas by ecological habitat and by taxon. An analysis of only the trochlea and lateral malleolar facet identifies subtle variations in trochlear shape between western lowland and lowland grauer gorillas, potentially indicative of convergent evolution of arboreal adaptations in the talus. Lastly, talar shape scales differently with centroid size for highland and lowland gorillas, suggesting that ankle morphology may track body‐size mediated variation in arboreal behaviors differently depending on ecological setting. Several of the observed shape differences are linked biomechanically to the facilitation of climbing in lowland gorillas and to stability and load‐bearing on terrestrial substrates in the highland taxa, providing an important comparative model for studying morphological variation in groups known only from fossils (e.g., early hominins). Anat Rec, 298:277–290, 2015. © 2014 Wiley Periodicals, Inc.
The h‐Difference Approach to Controllability and Observability of Fractional Linear Systems with Caputo–Type Operator
Authors: Mozyrska Dorota , Pawłuszewicz Ewa , Wyrwas Małgorzata
Published: October 2014

In the paper a class of h‐difference linear control systems with n fractional orders is studied. The Caputo‐type h‐difference operator is used. The formula of the solution to the stated initial value problem of the given system is proved. The problems of controllability and observability in a finite number of steps of h‐difference linear control systems with n fractional orders are studied.
Transgenic switchgrass (Panicum virgatum L.) biomass is increased by overexpression of switchgrass sucrose synthase (PvSUS1)
Authors: Poovaiah Charleson R. , Mazarei Mitra , Decker Stephen R. , Turner Geoffrey B. , Sykes Robert W. , Davis Mark F. , Stewart C. Neal
Published: October 2014

Sucrose synthase (SUS) converts sucrose and uridine di‐phosphate (UDP) into UDP‐glucose and fructose. UDP‐glucose is used by the cellulose synthase to produce cellulose for cell wall biosynthesis. For lignocellulosic feedstocks such as switchgrass, the manipulation of cell walls to decrease lignin content is needed to reduce recalcitrance of conversion of biomass into biofuels. Of perhaps equal importance for bioenergy feedstocks is increasing biomass. Four SUS genes were identified in switchgrass. Each gene contained 14 or 15 introns. PvSUS1 was expressed ubiquitously in the tissues tested. PvSUS2 and PvSUS6 were highly expressed in internodes and roots, respectively. PvSUS4 was expressed in low levels in the tissues tested. Transgenic switchgrass plants overexpressing PvSUS1 had increases in plant height by up to 37%, biomass by up to 13.6%, and tiller number by up to 79% compared to control plants. The lignin content was increased in all lines, while the sugar release efficiency was decreased in PvSUS1‐overexpressing transgenic switchgrass plants. For switchgrass and other bioenergy feedstocks, the overexpression of SUS1 genes might be a feasible strategy to increase both plant biomass and cellulose content, and to stack with other genes to increase biofuel production per land area cultivated.
Photocatalytic Hydrogen Evolution from Silica‐Templated Polymeric Graphitic Carbon Nitride–Is the Surface Area Important?
Authors: Li Xiaobo , Masters Anthony F. , Maschmeyer Thomas
Published: October 2014

Low‐surface‐area, mesoporous silica‐templated polymeric graphitic carbon nitride (SBA–g‐C3N4), when irradiated with visible light, exhibits a greatly improved photocatalytic hydrogen evolution rate as compared to that of conventional bulk g‐C3N4 synthesized directly from the condensation of dicyandiamide. It also performs very similarly to high‐surface‐area mesoporous g‐C3N4 on a per‐unit mass basis. However, on the per‐unit area basis it greatly outperforms the other materials. The intrinsically high surface activity of SBA–g‐C3N4 was confirmed by using two different co‐catalysts, in situ photodeposited Pt and a structurally well‐defined molecular cobaloxime. Instead of the magnitude of the surface area as the dominant feature that determines activity, it was established that the high activity of SBA–g‐C3N4 results from a much higher number of delocalized electrons present and a suppressed recombination probability of photogenerated electron–hole pairs.
Eco‐Friendly Catalytic Systems Based on Carbon‐Supported Magnesium Oxide Materials for the Friedländer Condensation
Authors: Godino‐Ojer Marina , López‐Peinado Antonio J. , Martín‐Aranda Rosa M. , Przepiórski Jacek , Pérez‐Mayoral Elena , Soriano Elena
Published: October 2014

Carbon‐supported MgO materials are excellent and sustainable catalysts for the synthesis of N‐containing heterocyclic compounds by the Friedländer condensation under mild, solvent‐free conditions. The results reported herein indicate that MgO is the most active catalytic species that accelerates the reaction compared with the catalytic behavior observed for the carbon material Norit RX3. On the basis of DFT calculations, a reaction mechanism that involves dual activation of the reacting structures by the catalyst is proposed.
Exploring the Reactivity of Nickel Pincer Complexes in the Decomposition of Formic Acid to CO2/H2 and the Hydrogenation of NaHCO3 to HCOONa
Authors: Enthaler Stephan , Brück Andreas , Kammer Anja , Junge Henrik , Irran Elisabeth , Gülak Samet
Published: October 2014

The nickel‐catalyzed decomposition of formic acid to yield molecular hydrogen and the nickel‐catalyzed hydrogenation of bicarbonate as a carbon dioxide mimic have been examined. Well‐defined nickel complexes modified by a PCP‐pincer ligand, especially nickel hydride and nickel formate complexes, revealed catalytic activity with turnover numbers of up to 626 (decomposition) and 3000 (hydrogenation). Thus, a formal hydrogen storage and release cycle performed by a well‐defined nickel catalyst was accomplished.
Luminescence Color Tuning of PtII Complexes and a Kinetic Study of Trimer Formation in the Photoexcited State
Authors: Kayano T. , Takayasu S. , Sato K. , Shinozaki K.
Published: October 2014

We investigated the luminescence properties and color tuning of [Pt(dpb)Cl] (dpbH=1,3‐di(2‐pyridyl)benzene) and its analogues. An almost blue emission was obtained for the complex [Pt(Fmdpb)CN] (FmdpbH=4‐fluoro‐1,3‐di(4‐methyl‐2‐pyridyl)benzene), modified by the introduction of F and CH3 groups to the dpb ligand and the substitution of Cl by CN. As the concentration of the solution was increased, the color of the emission varied from blue to white to orange. The color change resulted from a monomer–excimer equilibrium in the excited state. A broad emission spectrum around 620 nm was clearly detected along with a structured monomer emission around 500 nm. Upon further increases in concentration, another broad peak appeared in the longer wavelength region of the spectrum. We assigned the near‐infrared band to the emission from an excited trimer generated by the reaction of the excimer with the ground‐state monomer. The emission lifetimes of the monomer, dimer, and trimer were evaluated as τM=12.8 μs, τD=2.13 μs, and τT=0.68 μs, respectively, which were sufficiently long to allow association with another PtII complex and dissociation into a lower order aggregate. Based on equilibrium constants determined from a kinetic study, the formation of the excimer and the excited trimer were concluded to be exothermic processes, with ΔG*D=−24.5 kJ mol−1 and ΔG*T=−20.4 kJ mol−1 respectively, at 300 K.
Metal‐Free Oxidative Radical Addition of Carbonyl Compounds to α,α‐Diaryl Allylic Alcohols: Synthesis of Highly Functionalized Ketones
Authors: Chu Xue‐Qiang , Meng Hua , Zi You , Xu Xiao‐Ping , Ji Shun‐Jun
Published: October 2014

A metal‐free direct alkylation of simple carbonyl compounds (ketones, esters, and amides) with α,α‐diaryl allylic alcohols is described. The protocol provides facile access to highly functionalized dicarbonyl ketones by a radical addition/1,2‐aryl migration cascade. The regioselectivity of the reaction was precisely controlled by the nature of the carbonyl compound.
Copper‐Catalyzed Propargylic Substitution of Dichloro Substrates: Enantioselective Synthesis of Trisubstituted Allenes and Formation of Propargylic Quaternary Stereogenic Centers
Authors: Li Hailing , Grassi David , Guénée Laure , Bürgi Thomas , Alexakis Alexandre
Published: October 2014

An easy and versatile Cu‐catalyzed propargylic substitution process is presented. Using easily prepared prochiral dichloro substrates, readily available Grignard reagents together with catalytic amount of copper salt and chiral ligand, we accessed a range of synthetically interesting trisubstituted chloroallenes. Substrate scope and nucleophile scope are broad, providing generally high enantioselectivity for the desired 1,3‐substitution products. The enantioenriched chloroallenes could be further transformed into the corresponding trisubstituted allenes or terminal alkynes bearing all‐carbon quaternary stereogenic centers, through the copper‐catalyzed enantiospecific 1,1/1,3‐substitutions. The two successive copper‐catalyzed reactions could be eventually combined into a one‐pot procedure and different desired allenes or alkynes were obtained respectively with high enantiomeric excesses.
Hydroarylations of Heterobicyclic Alkenes through Rhodium‐Catalyzed Directed CH Functionalizations of S‐Aryl Sulfoximines
Authors: Dong Wanrong , Parthasarathy Kanniyappan , Cheng Ying , Pan Fangfang , Bolm Carsten
Published: October 2014

Rhodium‐catalyzed directed CH‐functionalizations have been used in hydroarylations of heterobicyclic alkenes with NH‐sulfoximines. Unexpectedly, the bicyclic framework is retained, resulting in the formation of addition products being attractive intermediates for functionalized molecules that are difficult to prepare by other means.
ChemInform Abstract: New Insight into Self‐Irradiation Effects on Local and Long‐Range Structure of Uranium—Americium Mixed Oxides (Through XAS and XRD).
Authors: Lebreton Florent , Martin Philippe M. , Horlait Denis , Bes Rene , Scheinost Andreas C. , Rossberg Andre , Delahaye Thibaud , Blanchart Philippe
Published: October 2014

The effects of self‐irradiation on the structure of U1‐xAmxO2.+‐.δ solid solutions (x = 0.15, 0.20) aged 3 to 4 years are studied by XRD and X‐ray absorption spectroscopy.
ChemInform Abstract: Crystal Growth and Characterization of the Narrow‐Band‐Gap Semiconductors OsPn2 (Pn: P, As, Sb).
Authors: Bugaris Daniel E. , Malliakas Christos D. , Shoemaker Daniel P. , Do Dat T. , Chung Duck Young , Mahanti Subhendra D. , Kanatzidis Mercouri G.
Published: October 2014

Single crystals of the title compounds are prepared from mixtures of Os, P or As, and Sn (1050 °C, 24 h), or Os and Sb (1150 °C, 48 h).
ChemInform Abstract: Synthesis, Crystal Structure and Optical Properties of Two New Layered Cadmium Iodates: Cd(IO3)X (X: Cl, OH).
Authors: Yang Bing‐Ping , Mao Jiang‐Gao
Published: October 2014

The layered iodate Cd(IO3)Cl (I) is prepared by hydrothermal reaction of CdCl2 and I2O5 (H2O, autoclave, 200 °C, 4 d, 82% yield).
ChemInform Abstract: Ionic Liquid Coated Sulfonated Carbon/Silica Composites: Novel Heterogeneous Catalysts for Organic Syntheses in Water.
Authors: Gupta Princy , Kour Manmeet , Paul Satya , Clark James H.
Published: October 2014

According to a recently reported procedure carbon/silica composites are prepared from mixtures of starch and glucose (3:1) and coated with ionic liquid such as [bmim]Br.
ChemInform Abstract: Asymmetric Synthesis of Chloroisothreonine Derivatives via syn‐Stereoselective Mannich‐Type Additions Across N‐Sulfinyl‐α‐chloroimines.
Authors: Callebaut Gert , Colpaert Filip , Nonn Melinda , Kiss Lorand , Sillanpaeae Reijo , Toernroos Karl W. , Fueloep Ferenc , De Kimpe Norbert , Mangelinckx Sven
Published: October 2014

The synthesized chloroisothreonine derivatives [(III) and (VII)] are further converted to aziridines (IV) and biologically relevant oxazolidinones (V).
ChemInform Abstract: Stereoselective Lewis Acid Mediated [3 + 2] Cycloadditions of N‐H‐ and N‐Sulfonylaziridines with Heterocumulenes.
Authors: Craig Robert A. II , O'Connor Nicholas R. , Goldberg Alexander F. G. , Stoltz Brian M.
Published: October 2014

Evidence is given for an intimate ion‐pair mechanism operating in these reactions.
ChemInform Abstract: Cooperative N‐Heterocyclic Carbene/Broensted Acid Catalysis for the Tail‐to‐Tail (Co)dimerization of Methacrylonitrile.
Authors: Kato Terumasa , Matsuoka Shin‐ichi , Suzuki Masato
Published: October 2014

For the first time, the tail‐to‐tail dimerization of methacrylonitrile (I) is realized.
ChemInform Abstract: Microwave‐Promoted Regio‐ and Stereoselective Vinylation of Heterocyclic Thiols.
Authors: Rajesh Nimmakuri , Sarma Rupam , Prajapati Dipak
Published: October 2014

Microwave promoted hydrothiolation of activated terminal alkyne (II) with hetaryl and aryl sulfides offers a convenient synthesis of vinyl sulfides in short reaction times.
ChemInform Abstract: Organocatalytic Asymmetric Condensation/Keto—Enol Tautomerization Tandem Reaction: Access to Cyclobutanone α‐Amino Acid Ester Derivatives.
Authors: Frongia Angelo , Melis Nicola , Serra Ilaria , Secci Francesco , Piras Pier Paolo , Caboni Pierluigi
Published: October 2014

No configurational assignments given for the cyclobutanone α‐carbon.
ChemInform Abstract: Deuterodehalogenation — A Mild Method for Synthesising Deuterated Heterocycles.
Authors: Donald Craig S. , Moss Thomas A. , Noonan Gary M. , Roberts Bryan , Durham Emma C.
Published: October 2014

Optimized reaction conditions including 2‐propanol‐d8 as the deuterium source are developed for the deuterodehalogenation of various bromo‐ and chloro‐substituted heterocycles.
ChemInform Abstract: Copper‐Catalyzed Oxidative α‐Alkylation of α‐Amino Carbonyl Compounds with Ethers via Dual C(sp3)—H Oxidative Cross‐Coupling.
Authors: Wei Wen‐Ting , Song Ren‐Jie , Li Jin‐Heng
Published: October 2014

The tertiary amine N‐methyl piperidine does not react with (I).
ChemInform Abstract: Mechanosynthesis of Pharmaceutically Relevant Sulfonyl‐(thio)ureas.
Authors: Tan Davin , Strukil Vjekoslav , Mottillo Cristina , Friscic Tomislav
Published: October 2014

The first application of mechanochemistry to conduct the synthesis of sulfonyl‐(thio)ureas (III), (VI), and (X), including antidiabetic drugs tolbutamide, chlorpropamide (VIa) and glibenclamide (X) by either stoichiometric base‐assisted or Cu‐catalyzed coupling of sulfonamides and iso(thio)cyanates, is reported.
ChemInform Abstract: An Efficient Palladium N‐Heterocyclic Carbene Catalyst Allowing the Suzuki—Miyaura Cross‐Coupling of Aryl Chlorides and Arylboronic Acids at Room Temperature in Aqueous Solution.
Authors: Rajabi Fatemeh , Thiel Werner R.
Published: October 2014

This method gives the coupling products in high yields even at low catalyst loadings.
ChemInform Abstract: O‐Aryloxime Ether Analogues as Novel and Efficient Ligands for Palladium‐Catalyzed Suzuki—Miyaura Coupling in Water.
Authors: Mondal Manoj , Bora Utpal
Published: October 2014

A simple combination consisting of PdCl2 and O‐aryl oxime ethers is found to catalyze the Suzuki—Miyaura coupling of aryl bromides with arylboronic acids in water at room temperature (27°C).
ChemInform Abstract: Access to Functionalized Bicyclo[4,3,0]nonenes via Palladium‐Catalyzed Oxidative Cyclization of 2‐Allylcyclohexyl Oximes.
Authors: Zhu Jia‐Liang , Wu Sih‐Ting , Shie Jr‐Yun
Published: October 2014

Starting from the chiral title substrates the synthesis of either bicyclic hydroxyaldehydes or enones bearing aliphatic substituents can be achieved by variation of the catalytic system.
ChemInform Abstract: Novel Method of Tetramic Acid Synthesis: Silver‐Catalyzed Carbon Dioxide Incorporation into Propargylic Amine and Intramolecular Rearrangement.
Authors: Ishida Tomonobu , Kobayashi Ryo , Yamada Tohru
Published: October 2014

A new strategy for the synthesis of tetramic acids from propargylic amines and carbon dioxide under mild reaction conditions is presented.
ChemInform Abstract: 1,2‐Alkylarylation of Activated Alkenes with Two C—H Bonds by Using Visible‐Light Catalysis.
Authors: Zhang Jia‐Ling , Liu Yu , Song Ren‐Jie , Jiang Guo‐Fang , Li Jin‐Heng
Published: October 2014

A new visible‐light catalysis strategy for the synthesis of functionalized oxindoles by reaction of various N‐arylacrylamides with acetonitrile or acetone.
ChemInform Abstract: Regioselective Synthesis of 1,3‐Oxathiolane‐2‐imine Derivatives.
Authors: Samzadeh‐Kermani Alireza
Published: October 2014

An efficient one‐pot synthesis of functionalized 1,3‐oxathiolanes (III) (18 examples) by reaction of various aryl isothiocyanates and oxiranes in the presence of a catalytic amount of methoxide is presented.
ChemInform Abstract: Highly Convergent One‐Pot Four‐Component Regioselective Synthesis of Spiro‐pyranopyrazoles and Oxa‐aza‐[3.3.3]propellanes.
Authors: Alizadeh Abdolali , Bayat Fahimeh
Published: October 2014

The title compounds are efficiently obtained by a simple, regioselective multicomponent reaction of ninhydrin, malononitrile, hydrazine derivatives, and β‐ketoesters or dimethyl acetylenedicarboxylate.
ChemInform Abstract: One‐Pot Tandem Palladium‐Catalyzed Decarboxylative Cross‐Coupling and C—H Activation Route to Thienoisoquinolines.
Authors: Chen Fei , Wong Nicholas W. Y. , Forgione Pat
Published: October 2014

The reaction yields strongly depend on the electronic nature of the aryl sulfonamide as well as of the aryl bromides employed.
ChemInform Abstract: Oxone‐Mediated Oxidative Carbon‐Heteroatom Bond Cleavage: Synthesis of Benzoxazinones from Benzoxazoles with α‐Oxocarboxylic Acids.
Authors: Wang Hua , Yang Hua , Li Yiping , Duan Xin‐Hua
Published: October 2014

Tandem oxidative cleavage/coupling of benzoxazoles with α‐oxocarboxylic acids allows the synthesis of benzoxazinones via in situ generated ortho‐aminophenol derivatives.
ChemInform Abstract: An Efficient Ligand‐Free Ferric Chloride Catalyzed Synthesis of Annulated 1,4‐Thiazine‐3‐one Derivatives.
Authors: Majumdar K. C. , Ghosh Debankan
Published: October 2014

The FeCl3‐catalyzed reaction of 2‐chloro‐N‐methylacetamide derivatives with sodium sulfide provides an easy access to a variety of annulated 1,4‐thiazin‐3‐ones.
ChemInform Abstract: Asymmetric Synthesis of Protected α‐Amino Boronic Acid Derivatives with an Air‐and Moisture‐Stable Cu(II) Catalyst.
Authors: Buesking Andrew W. , Bacauanu Vlad , Cai Irene , Ellman Jonathan A.
Published: October 2014

The enantioselective synthesis of the title compounds from aldimines uses a low catalyst loading.
ChemInform Abstract: Cs2CO3‐Promoted One‐Pot Synthesis of Alkynylphosphonates, ‐phosphinates, and ‐phosphine Oxides.
Authors: Wang Yulei , Gan Jiepeng , Liu Liu , Yuan Hang , Gao Yuxing , Liu Yan , Zhao Yufen
Published: October 2014

The preparation of the title compound classes from readily available 1,1‐dibromo‐1‐alkenes is presented in an operational simple process without transition‐metal containing promoters.
ChemInform Abstract: Hypervalent Iodine Mediated Synthesis of C‐2 Deoxy Glycosides and Amino Acid Glycoconjugates.
Authors: Islam Maidul , Tirukoti Nishanth D. , Nandi Shyamapada , Hotha Srinivas
Published: October 2014

The synthesis of amino acid glycoconjugates (VI) is achieved by the synthesis of C‐2 deoxy glycosides (III) and a subsequent intramolecularly aglycon delivery (V) followed by a dehalogenation reaction.
ChemInform Abstract: Recent Advances in Trivalent F‐Element Borate Chemistry
Authors: Polinski Matthew J. , Alekseev Evgeny V. , Depmeier Wulf , Albrecht‐Schmitt Thomas E.
Published: October 2014

Review: 41 refs.
ChemInform Abstract: Helicene‐Based Transition Metal Complexes: Synthesis, Properties and Applications
Authors: Saleh Nidal , Shen Chengshuo , Crassous Jeanne
Published: October 2014

Review: 96 refs.
ChemInform Abstract: The Elusive Cyanoformate: An Unusual Cyanide Shuttle
Authors: Hering Christian , von Langermann Jan , Schulz Axel
Published: October 2014

Review: 21 refs.
ChemInform Abstract: Microwave‐Assisted Synthesis of Six‐Membered O,O‐Heterocycles
Authors: Kaur Navjeet , Kishore Dharma
Published: October 2014

Review: 98 refs.
ChemInform Abstract: Block Copolymer Self‐Assembly Controlled by the “Green” Gas Stimulus of Carbon Dioxide
Authors: Yan Qiang , Zhao Yue
Published: October 2014

Review: 84 refs.
ChemInform Abstract: Noncovalent Interaction‐Assisted Polymeric Micelles for Controlled Drug Delivery
Authors: Ding Jianxun , Chen Linghui , Xiao Chunsheng , Chen Li , Zhuang Xiuli , Chen Xuesi
Published: October 2014

Review: 176 refs.
ChemInform Abstract: Present Status of Quinoxaline Motifs: Excellent Pathfinders in Therapeutic Medicine
Authors: Ajani Olayinka Oyewale
Published: October 2014

Review: [205 refs.
ChemInform Abstract: Band Excitation in Scanning Probe Microscopy: Recognition and Functional Imaging
Authors: Jesse S. , Vasudevan R. K. , Collins L. , Strelcov E. , Okatan M. B. , Belianinov A. , Baddorf A. P. , Proksch R. , Kalinin S. V.
Published: October 2014

Review: 97 refs.
Regio‐ and Enantioselective Friedel–Crafts Reactions of Indoles to Epoxides Catalyzed by Graphene Oxide: A Green Approach
Authors: Acocella Maria Rosaria , Mauro Marco , Guerra Gaetano
Published: October 2014

Graphene oxide efficiently promotes high regio‐ and enantioselective ring opening reactions of aromatic epoxides by indoles addition, in solvent‐ and metal‐free conditions. The Friedel–Crafts products were obtained with enantioselectivity up to 99 % ee. The complete inversion of stereochemistry indicates the occurrence of SN2‐type reaction, which assures high level of enantioselectivity.
Silanediol‐Catalyzed Carbon Dioxide Fixation
Authors: Hardman‐Baldwin Andrea M. , Mattson Anita E.
Published: October 2014

Carbon dioxide is an abundant and renewable C1 source. However, mild transformations with carbon dioxide at atmospheric pressure are difficult to accomplish. Silanediols have been discovered to operate as effective hydrogen‐bond donor organocatalysts for the atom‐efficient conversion of epoxides to cyclic carbonates under environmentally friendly conditions. The reaction system is tolerant of a variety of epoxides and the desired cyclic carbonates are isolated in excellent yields.
The Ugi–Smiles and Passerini–Smiles Couplings: A Story About Phenols in Isocyanide‐Based Multicomponent Reactions
Authors: El Kaïm Laurent , Grimaud Laurence
Published: October 2014

The Ugi–Smiles and Passerini–Smiles couplings are extensions of Ugi and Passerini reactions involving the use of acidic phenols in place of the traditional carboxylic acid partners. A Smiles rearrangement is in each case responsible for the final N‐aryl carboxamide formation. All the available data on the mechanisms and the scope of these reactions are presented. To demonstrate the interest of Ugi–Smiles and Passerini–Smiles couplings, these reactions have been further applied to the preparation of various fused heterocyclic systems. These “post‐condensation” studies are also covered in this review.
Transformation of Glycals into α,β,γ,δ‐Conjugated Chirons under Metal‐Free Conditions
Authors: Madhubabu Tatina , Yousuf Syed Khalid , Kusunuru Anil Kumar , Mukherjee Debaraj
Published: October 2014

A diastereoselective, metal‐free, one‐pot domino synthetic strategy was developed for the transformation of glycals into new chiral scaffolds. Optimization of the reaction conditions to exclude normal Ferrier products, characterization of the new entities, and a plausible mechanism were investigated.
An Improved Protocol for the Synthesis of α‐Trifluoromethylthio‐Substituted Ketones by Copper‐Mediated Trifluoromethylthiolation of α‐Bromo Ketones
Authors: Huang Yangjie , He Xing , Li Haohong , Weng Zhiqiang
Published: October 2014

An efficient and practical approach to α‐trifluoromethylthio‐substituted ketones was developed. The trifluoromethylthiolation of (bpy)Cu(SCF3) (bpy = 2,2′‐bipyridyl) with various α‐bromo ketones afforded the desired α‐trifluoromethylthio‐substituted ketones in good yields. The reaction tolerates more functionally than previously reported methods and demonstrates efficient scalability and practicality.
The impact of pro‐glacial lakes on downstream sediment delivery in Norway
Authors: Bogen Jim , Xu Mengzhen , Kennie Patricia
Published: October 2014

Glacier recessions caused by climate change may uncover pro‐glacial lakes that form important sedimentation basins regulating the downstream sediment delivery. The impact of modern pro‐glacial lakes on fluvial sediment transport from three different Norwegian glaciers: Nigardsbreen, Engabreen and Tunsbergdalsbreen, and their long‐term development has been studied. All of these lakes developed in modern times in overdeepened bedrock basins.

The recession of Nigardsbreen uncovered a 1.8 km long and on average 15 m deep pro‐glacial lake basin during 1937 to 1968. Since then the glacier front has been situated entirely on land, and the sediment input and output of the lake has been measured. The suspended sediment transport into and out of the lake averaged 11 730 t yr−1 and 2340 t yr−1 respectively. Thus, 20% remained in suspension at the outlet. The measured mean annual bedload supplied to the lake was 11 800 t yr−1, giving a total transport of 23 530 t yr−1 which corresponds to a specific sediment yield of 561 t km−2 yr−1.

A 1.9 km long and up to 90 m deep pro‐glacial lake basin downstream from Engabreen glacier was uncovered during 1890 to 1944. The average suspended sediment load delivered from the glacier during the years 1970–1981 amounted to 12 375 t yr−1and the transport out of the lake was 2021 t yr−1, giving an average of 16% remaining in suspension. The mean annual bedload was 8000 t yr−1, thus the total transport was 20 375 t yr−1, giving a specific sediment yield of 566 t km−2 yr−1.

For Tunsbergdalsbreen glacier, measurements in the early 1970s indicated that the suspended sediment transport was on average 44 000 t yr−1. From 1987 to 1993 the recession of the glacier uncovered a small pro‐glacial lake, 0.3 km long and around 9 m deep. Downstream from this, the suspended sediment load measured in 2009 was 28 000 t yr−1, indicating that as much as 64% remained in suspension. Flow velocity, grain size of sediment, and morphology of the lake are important factors controlling the sedimentation rate in the pro‐glacial lakes. A survey of the sub‐glacial morphology of Tunsbergdalsbreen revealed that there are several overdeepened basins beneath the glacier. The largest is 4 km long and 100 m deep. When the glacier melts back they will become lakes and act as sedimentation basins. Despite an expected increase in sediment yield from the glacier, little sediment will pass these lakes and downstream sediment delivery will be reduced markedly. Beneath Nigardsbreen there was only a small depression that may form a lake and the sediment delivery will not be significantly affected. © 2014 The Authors. Earth Surface Processes and Landforms published by John Wiley & Sons Ltd.
Fracking: Fix It or Forget It?
Authors: Klein Daniel E.
Published: October 2014

For decades, US energy policy has been dominated by two daunting challenges.
Slip Length Measurements Using µPIV and TIRF‐Based Velocimetry
Authors: Li Zhenzhen , D'eramo Loic , Monti Fabrice , Vayssade Anne‐Laure , Chollet Benjamin , Bresson Bruno , Tran Yvette , Cloitre Michel , Tabeling Patrick
Published: October 2014

The goal of this paper is to review progress (mostly recent) made in micro and nanovelocimetry, focusing on two techniques: µPIV (microparticle image velocimetry) and nanoPTV (nanoparticle tracking velocimetry). The paper focuses on the measurement of slippage (taken as a benchmark for these techniques), concentrating on work done in our group. We review the developments of µPIV that led, in the last ten years, to the achievement of 100 nm accuracy in the measurement of slip lengths. Later, this approach was complemented by nanoPTV, which recently obtained ±5 nm precision. Here, we also mention recent application of these techniques toward better characterization of microgel and polymer flows. As a whole, the two techniques have conveyed valuable information on flow behavior within and close to the boundaries of microchannels, on the importance of wetting, and on the role of surface heterogeneities. µPIV is commercially available but nanoPTV is not mature. Interesting instrumental developments are expected in the future for the latter technique.
Validity and Efficacy of Screening Algorithms for Assessing Deep Brain Stimulation Candidacy in Parkinson's Disease
Authors: Coleman Robert R. , Kotagal Vikas , Patil Parag G. , Chou Kelvin L.
Published: October 2014

DBS for Parkinson's disease (PD) may be underutilized because of limited access to care (most DBS surgeries are performed at specialized centers) or over‐referral of poor candidates, leading to inequitable utilization of limited evaluative resources. There is a pressing need for a widely employable screening algorithm to aid in the evaluation of PD candidates for DBS. The aim of this study was to compare the validity and efficacy of two published screening algorithms, the Florida Surgical Questionnaire for PD and Stimulus, to predict candidacy for DBS. We reviewed the clinical data at our DBS center for 147 consecutive PD DBS referrals between 1 September 2007 and 31 December 2011. Florida Surgical Questionnaire and Stimulus scores were applied retrospectively through a chart review of the movement disorder neurologist's initial clinical evaluation. The validity and accuracy of these two algorithms in predicting candidacy for DBS was compared to the decision to offer DBS surgery by our multidisciplinary DBS team. Of the 130 consecutive PD referrals who presented for initial evaluation, 50 were offered DBS after a standardized multidisciplinary evaluation. The Stimulus scale was a superior screening tool for predicting PD DBS candidacy in these referrals (area under the receiver operating curve [AUROC] = 0.8088), compared to the Florida Surgical Questionnaire for PD (AUROC = 0.6285). In this single‐center study, Stimulus was a more appropriate screening measure than the Florida Surgical Questionnaire for PD to assess DBS candidacy for PD.
Monitoring of River Contamination Derived From Acid Mine Drainage Using Airborne Imaging Spectroscopy (HyMap Data, South‐West Spain)
Authors: Buzzi J. , Riaza A. , García‐Meléndez E. , Carrère V. , Holzwarth S.
Published: October 2014

Imaging spectroscopy is used in this work as an essential mapping tool to monitor changes in contaminated river sediments. Multidate hyperspectral image data (HyMap) are utilized to identify spatial mineral patterns, to detect temporal changes in mineralogy and to link these changes with geochemical processes and short‐term climate characteristics.

River sediments contaminated by acid mine drainage are covered by crusts with variably hydrated iron sulphate. The mineralogy of the crusts and the grain size of the underlying fluvial sediments overlap. The spectra used to build up maps from HyMap data are diagnosed mineralogically with archive spectral libraries from pyrite oxidation minerals from well‐known sequences of minerals.

The maps compiled from hyperspectral imagery display generalized oxidation shown by the coatings over river sediments following warm and dry periods with low water level. After the wet periods, the area covered by oxidized mineralogical phases recedes in favour of hydrated sulphate.

The iteration of image processing algorithms and the mineralogical and potential contamination in a geological context are described. Change detection of the mineral crusts on the river sediments by mapping using hyperspectral remote sensing data may thus enable a quantitative and qualitative environmental evaluation by the regulators. Copyright © 2014 John Wiley & Sons, Ltd.
Ecosystem Management Along Ephemeral Rivers: Trading Off Socio‐Economic Water Supply and Vegetation Conservation under Flood Regime Uncertainty
Authors: Arnold S. , Attinger S. , Frank K. , Baxter P. , Possingham H. , Hildebrandt A.
Published: October 2014

In ecosystems driven by water availability, plant community dynamics depend on complex interactions between vegetation, hydrology, and human water resources use. Along ephemeral rivers—where water availability is erratic—vegetation and people are particularly vulnerable to changes in each other's water use. Sensible management requires that water supply be maintained for people, while preserving ecosystem health. Meeting such requirements is challenging because of the unpredictable water availability. We applied information gap decision theory to an ecohydrological system model of the Kuiseb River environment in Namibia. Our aim was to identify the robustness of ecosystem and water management strategies to uncertainties in future flood regimes along ephemeral rivers. We evaluated the trade‐offs between alternative performance criteria and their robustness to uncertainty to account for both (i) human demands for water supply and (ii) reducing the risk of species extinction caused by water mining. Increasing uncertainty of flood regime parameters reduced the performance under both objectives. Remarkably, the ecological objective (species coexistence) was more sensitive to uncertainty than the water supply objective. However, within each objective, the relative performance of different management strategies was insensitive to uncertainty. The ‘best’ management strategy was one that is tuned to the competitive species interactions in the Kuiseb environment. It regulates the biomass of the strongest competitor and, thus, at the same time decreases transpiration, thereby increasing groundwater storage and reducing pressure on less dominant species. This robust mutually acceptable strategy enables species persistence without markedly reducing the water supply for humans. This study emphasises the utility of ecohydrological models for resource management of water‐controlled ecosystems. Although trade‐offs were identified between alternative performance criteria and their robustness to uncertain future flood regimes, management strategies were identified that help to secure an ecologically sustainable water supply. Copyright © 2014 John Wiley & Sons, Ltd.
Eco‐friendly Trifoliate Stable Energetic Zinc Nitrate Co­ordination Compounds: Synthesis, Structures, Thermal and Explosive Properties
Authors: Tong Wen‐Chao , Liu Jian‐Chao , Wang Qian‐You , Yang Li , Zhang Tong‐Lai
Published: October 2014

Three trifoliate environmental friendly coordination compounds, [Zn(SCZ)3](NO3)2 (1) (SCZ = semicarbazide), [Zn(CHZ)3](NO3)2 (2) (CHZ = carbohydrazide), and [Zn(MCZ)3](NO3)2·H2O (3) (MCZ = methyl carbazate), were synthesized by the reaction of zinc nitrate with its corresponding ligands. The products were characterized by elemental analysis and FT‐IR spectroscopy. Furthermore, compound 1 and 2 were characterized by X‐ray single crystal diffraction. The crystal structures of both 1 and 2 belong to the monoclinic P21/c space group. Remarkably, in all the three compounds, the central zinc cations are six‐coordinated with three oxygen atoms of carbonyl groups and three terminal nitrogen atoms of the hydrazine groups from three SCZ / CHZ / MCZ molecules, which can form three five‐member (Zn–O–C–N–N) rings and exhibit a distorted octahedron. Thermal stabilities of 1 to 3 were studied by differential scanning calorimetry (DSC) and showed that they are all thermostable. The non‐isothermal kinetics parameters were calculated by the Kissinger's method and Ozawa's method, respectively. The energies of combustion, enthalpies of formation, critical temperature of thermal explosion, entropies of activation (ΔS≠), enthalpies of activation (ΔH≠), and free energies of activation (ΔG≠) were measured and calculated. Sensitivity tests revealed that 1–3 are insensitive to mechanical stimuli. The studies of all these three zinc compounds showed that they have potential applications as heat‐stable insensitive energetic materials, especially the semicarbazide coordination compound 1, which has higher crystal density.
Synthesis and Characterization of the Ternary Telluroargentate K4[Ag18Te11]
Authors: Davaasuren Bambar , Dashjav Enkhtsetseg , Rothenberger Alexander
Published: October 2014

The ternary potassium telluroargentate(I), K4[Ag18Te11], was prepared by solvothermal synthesis in ethylenediamine at 160 °C. It crystallizes in the cubic space group Fm$\bar{3}$m (no. 225) with the cell parameter a = 18.6589(6) Å. The crystal structure can be described as a [Ag18Te11]4– three‐dimensional anionic framework with the voids accommodating potassium cations. Chemical bonding analysis reveals polar covalent Ag–Te bonds and considerable Ag–Ag interactions, which support the complex anionic character of the structure. The compound is thermally stable up to 450 °C in an inert atmosphere.
Living Supramolecular Compounds: Influence of Multiple Hydrogen Bond Connection on Molecular Configuration of Monophosphate or Pyrophosphate Thiamine with Anions or Coordination Anions
Authors: Zhang Xiao Xi , Zhang Rui , Sun Qiao , Wei Si Yue , Xu Xue Ting , Wang Ji Xiao , Bai Feng Ying , Xing Yong Heng
Published: October 2014

Three supramolecular compounds with monophosphate or pyrophosphate esters of thiamine, namely, [TPPH+·CF3SO3·H2O] (1), [TMPH+·(CdCl4)0.5·2H2O] (2), and [TMPH+·NO3·2.5H2O] (3) (TPP = thiamine pyrophosphate, TMP = thiamine monophosphate) were synthesized in methanol or water systems at room temperature. They were characterized by elemental analysis, IR spectrocopy, and single X‐ray diffraction. Structural analysis shows that they are all supramolecular compounds and there are abundant interhydrogen and intrahydrogen bonds in the molecules. In addition, combined with the quantum mechanical calculations, their potential reaction activity and molecular electronic configuration were discussed.
Four pH‐Dependent 1D CoII/NiII Coordination Polymers Based on a Terphenyl‐2,2′,4,4′‐Tetracarboxylic Acid: Syntheses, Structures, and Magnetic Properties
Authors: Xia Wei , Zhao Jun , Wang Ye‐Nan , Guo Sha‐Sha , Tang Ping
Published: October 2014

Four CoII/NiII coordination polymers, namely, [M(H3L)2(H2O)2]n (1, 2) and [M(H2L)(H2O)3]n (3, 4), (M = Co for 1 and 3, M = Ni for 2 and 4, H4L = terphenyl‐2,2′,4,4′‐tetracarboxylic acid) were synthesized through hydrothermal reactions at different pH values and structurally characterized. Single crystal X‐ray crystallographic analysis reveals that compounds 1 and 2 are isostructural and exhibit a 1D [M2(H3L)2]n loop‐like infinite chain, whereas compounds 3 and 4 are also isostructural and show a 1D pendant H2L attached [M(H2O)]n chain motif. Additionally, variable‐temperature magnetic susceptibility measurement shows weak antiferromagnetic coupling among the adjacent central CoII atoms in 1 and 3.