bluuebunny/crossref_metadata_2025 huggingface dataset:
ChemInform Abstract: Palladium‐Catalyzed Carbonylative α‐Arylation to β‐Ketonitriles.
Authors: Schranck Johannes , Burhardt Mia , Bornschein Christoph , Neumann Helfried , Skrydstrup Troels , Beller Matthias
Published: January 2015

The procedure can be applied to unactivated nitriles and affords α‐disubstituted β‐ketonitriles as important building blocks in moderate to good yields.
ChemInform Abstract: Direct Palladium‐Catalyzed Desulfitative C—C Coupling of Polyfluoroarenes with Arylsulfinate Salts: Water‐Accelerated Reactions.
Authors: Lin Xiaoxi , You Yi , Weng Zhiqiang
Published: January 2015

Optimum reaction conditions are examined for the palladium‐catalyzed desulfitative C—C coupling of polyfluoroarenes with sodium arylsulfinates.
ChemInform Abstract: Synthesis of Substituted Biarylmethanol via Ferrocenyloxime Palladacycles Catalyzed Suzuki Reaction of Chlorophenylmethanol in Water.
Authors: Li Hong‐Mei , Feng Ai‐Qing , Lou Xin‐Hua
Published: January 2015

The catalyst is air‐ and moisture‐stable, both in solid state and in solution.
ChemInform Abstract: One‐Pot Synthesis of Cinnamylideneacetophenones and Their in vitro Cytotoxicity in Breast Cancer Cells.
Authors: Brantley Eileen , et al. et al.
Published: January 2015

A series of cinnamylidene acetophenones (III) (10 examples) are synthesized via a modified Claisen—Schmidt condensation and evaluated for their cytotoxicity against breast cancer cells.
ChemInform Abstract: Towards High‐Performance Lewis Acid Organocatalysis.
Authors: Ratjen Lars , van Gemmeren Manuel , Pesciaioli Fabio , List Benjamin
Published: January 2015

A new type of catalyst containing (biaryl)methanol side chains in a chiral BINAP‐disulfonamide skeleton is designed and synthesized.
ChemInform Abstract: Discovery and Application of Doubly Quaternized Cinchona‐Alkaloid‐Based Phase‐Transfer Catalysts.
Authors: Xiang Bangping , Belyk Kevin M. , Reamer Robert A. , Yasuda Nobuyoshi
Published: January 2015

Novel N,N′‐dibenzylated cinchona alkaloid‐based phase‐transfer catalysts are designed to provide improved enantioselectivity for the intramolecular spirocyclization of substrates of type (I), (III), and (V) compared to traditional cinchona alkaloid catalysts.
ChemInform Abstract: Copper‐Catalyzed Direct C‐2 Difluoromethylation of Furans and Benzofurans: Access to C‐2 CF2H Derivatives.
Authors: Belhomme Marie‐Charlotte , Poisson Thomas , Pannecoucke Xavier
Published: January 2015

The first Cu‐catalyzed selective difluoromethylation reaction of benzofurans and furans is presented.
ChemInform Abstract: Synthesis of 5‐Alkyl‐5‐aryl‐1‐pyrroline N‐Oxides from 1‐Aryl‐substituted Nitroalkanes and Acrolein via Michael Addition and Nitro Reductive Cyclization.
Authors: Xu Jingjing , Li Xingyao , Wu Jinlong , Dai Wei‐Min
Published: January 2015

A general method for the title synthesis using readily available starting materials is established.
ChemInform Abstract: Facile Synthetic Method for Diverse Polyfunctionalized Imidazoles by Means of Pd‐Catalyzed C—H Bond Arylation of N‐Methyl‐4,5‐dibromoimidazole.
Authors: Yamauchi Takayuki , Shibahara Fumitoshi , Murai Toshiaki
Published: January 2015

The palladium‐phenanthroline catalyst prefers C‐H bonds over C‐Br bonds in arylation of dibromoimidazole.
ChemInform Abstract: Decarboxylative Hydroamination of 3‐Arylpropiolic Acids with N‐Heterocycles under Transition‐Metal‐Free Conditions.
Authors: Pan Xixian , Wan Xiaolong , Yu Xin , Zhang Hui , Xie Weiqing
Published: January 2015

A facile protocol is developed for the synthesis of N‐vinyl heterocycles via base mediated decarboxylation of 2‐arylpropiolic acids and subsequent hydroamination of the resulting arylacetylene intermediates with N‐heterocycles.
ChemInform Abstract: Phase Transfer Agent Assisted Biphasic CuAAC Reaction.
Authors: Kim Jae Hyun , Kim Sanghee
Published: January 2015

The method is applied to the synthesis of an immunostimulating α‐galaytosylceramide analogue.
ChemInform Abstract: Chiral Bifunctional Squaramide‐Catalyzed Highly Enantioselective Michael Addition of Allomaltol to β,γ‐Unsaturated α‐Ketoesters.
Authors: Liu Yunting , Wang Qiaohui , Wang Youming , Song Haibin , Zhou Zhenghong
Published: January 2015

The Michael addition of allomaltol (I), kojic acid (IVa), or its trimethylsilyl ethers (IVb) to unsaturated α‐ketoesters is efficiently catalyzed by a squaramide catalyst to form lactols (III) and (V) with high enantioselectivity.
ChemInform Abstract: Enzyme Catalytic Promiscuity: Lipase Catalyzed Synthesis of Substituted 2H‐Chromenes by a Three‐Component Reaction.
Authors: Yang Fengjuan , Wang Zhi , Wang Haoran , Zhang Hong , Yue Hong , Wang Lei
Published: January 2015

This novel and simple protocol for the synthesis of alkoxy chromene provides a new case of lipase catalytic promiscuity and extends the utility of lipase in organic synthesis.
ChemInform Abstract: Trimethylsilyl Iodide as a Multifunctional Agent in the One‐Pot Synthesis of 9‐(1H‐Indol‐3‐yl)xanthen‐4‐(9H)‐ones from O‐Methyl Protected Salicylaldehydes, Indoles, and β‐Dicarbonyl Compounds.
Authors: Khalafi‐Nezhad Ali , Nourisefat Maryam , Panahi Farhad
Published: January 2015

Trimethylsilyl iodide is introduced as an efficient reagent for the one‐pot synthesis of various xathenone derivatives.
ChemInform Abstract: Lewis Base Catalyzed, Enantioselective, Intramolecular Sulfenoamination of Olefins.
Authors: Denmark Scott E. , Chi Hyung Min
Published: January 2015

Exo‐/endo‐selectivity strongly depends on the steric effects of the substituents at the double bond.
ChemInform Abstract: Rhodium‐Catalyzed Asymmetric Hydrogenation of Unprotected NH Imines Assisted by a Thiourea.
Authors: Zhao Qingyang , Wen Jialin , Tan Renchang , Huang Kexuan , Metola Pedro , Wang Rui , Anslyn Eric V. , Zhang Xumu
Published: January 2015

The hydrogenation provides chiral amines in high yields and enantioselectivities up to 95% ee.
ChemInform Abstract: Diastereoselective Construction of Tetrahydropyridine Fused Bicyclic Structures via Three‐Component Domino Reaction.
Authors: Wan Jie‐Ping , Lin Yunfang , Huang Qing , Liu Yunyun
Published: January 2015

A three‐component reaction of aminoalcohols, propiolic esters, and α,β‐unsaturated aldehydes is developed to permit the highly diastereoselective synthesis of a range of tetrahydropyridine fused heterocycles.
ChemInform Abstract: DBU: An Efficient Base Catalyst for Synthesis of the New Oxazolo[5,4‐d]pyrimidine Derivatives.
Authors: Nikseresht Ahmad , Bakavoli Mehdi , Bayraq Samad Shoghpour
Published: January 2015

via heteroannulation of 2‐substituted 5‐amino‐4‐cyano‐1,3‐oxazoles (III) with isothiocyanates (IV)
ChemInform Abstract: One‐Pot Synthesis of 1,3,5‐Triazine Derivatives via Controlled Cross‐Cyclotrimerization of Nitriles: A Mechanism Approach.
Authors: Herrera Antonio , Riano Alberto , Moreno Ramon , Caso Barbara , Pardo Zulay D. , Fernandez Israel , Saez Elena , Molero Dolores , Sanchez‐Vazquez Angel , Martinez‐Alvarez Roberto
Published: January 2015

Treatment of the starting nitrile with equimolar amounts of Tf2O or TfOH produces a nitrilium salt which reacts with 2 equiv.
ChemInform Abstract: Microwave‐Promoted Synthesis of Bicyclic Azocine‐β‐Lactams from Bis(allenes).
Authors: Alcaide Benito , Almendros Pedro , Aragoncillo Cristina , Fernandez Israel , Gomez‐Campillos Gonzalo
Published: January 2015

A metal and catalyst free process is developed to construct azocine‐β‐lactams by microwave promoted cyclization of bis‐allenyl tethered azetidinones (I) and (III).
ChemInform Abstract: Synthesis of (S)‐ and (R)‐Harmicine from Proline: An Approach Toward Tetrahydro‐β‐carbolines.
Authors: Lood Lood
Published: January 2015

The target compound is synthesized in 9 steps and 19% overall yield.
ChemInform Abstract: Cyclopentane‐Condensed Chromones from Marine‐Derived Fungus Penicillium oxalicum.
Authors: Bao Jie , Zhang Xiao‐Yong , Dong Jie‐jie , Xu Xin‐ya , Nong Xu‐Hua , Qi Shu‐Hua
Published: January 2015

Five new cyclopentane‐condensed chromones, coniochaetones G‐K (I) ‐ (III), are isolated together with four known compounds from the crude extract of marine‐derived fungus Penicillium oxalicum.
ChemInform Abstract: Combustion Synthesis of TiFe by Utilizing Magnesiothermic Reduction.
Authors: Deguchi Masaya , Yasuda Naoto , Zhu Chunyu , Okinaka Noriyuki , Akiyama Tomohiro
Published: January 2015

The TiFe hydrogen storage alloy is prepared by combustion synthesis via magnesiothermic reduction of a mixture of TiO2 and Fe with Mg in a molar ratio of 1:1:4, which is pressed into cylinders and placed in a graphite crucible of a stainless steel reactor (heating to the combustion temp.
ChemInform Abstract: Neutron Scattering Studies on URu2Si2
Authors: Bourdarot Frederic , Raymond Stephane , Regnault Louis‐Pierre
Published: January 2015

Review: 60 refs.
ChemInform Abstract: Itinerant Multipolar Order in URuSi and Its Signature in Magnetic and Lattice Properties
Authors: Thalmeier Peter , Takimoto Tetsuya , Ikeda Hiroaki
Published: January 2015

Review: 30 refs.
ChemInform Abstract: Interacting Magnetic Cluster‐Spin Glasses and Strain Glasses in Ni—Mn Based Heusler Structured Intermetallics
Authors: Entel Peter , Gruner Markus E. , Comtesse Denis , Sokolovskiy Vladimir V. , Buchelnikov Vasiliy D.
Published: January 2015

Review: 78 refs.
ChemInform Abstract: Electroanalytical Chemistry of Lanthanides and Actinides
Authors: Schumacher Paul D. , Doyle Jamie L. , Schenk James O. , Clark Sue B.
Published: January 2015

Review: 83 refs.
ChemInform Abstract: Recent Advances in Asymmetric Fluorination and Fluoroalkylation Reactions via Organocatalysis
Authors: Lin Jin‐Hong , Xiao Ji‐Chang
Published: January 2015

Review: [41 refs.
ChemInform Abstract: Chiral Sulfinamides as Highly Enantioselective Organocatalysts
Authors: Diner Peter , Sadhukhan Arghya , Blomkvist Bjoern
Published: January 2015

Review: 30 refs.
ChemInform Abstract: Recent Advances and Applications of Reductive Desulfurization in Organic Synthesis
Authors: Rentner Jana , Kljajic Marko , Offner Lisa , Breinbauer Rolf
Published: January 2015

Review: 170 refs.
ChemInform Abstract: Limonene: A Versatile Chemical of the Bioeconomy
Authors: Ciriminna Rosaria , Lomeli‐Rodriguez Monica , Demma Cara Piera , Lopez‐Sanchez Jose A. , Pagliaro Mario
Published: January 2015

Review: 62 refs.
ChemInform Abstract: Furans and Singlet Oxygen — Why There is More to Come from This Powerful Partnership
Authors: Montagnon Tamsyn , Kalaitzakis Dimitris , Triantafyllakis Myron , Stratakis Manolis , Vassilikogiannakis Georgios
Published: January 2015

Review: [121 refs.
ChemInform Abstract: Polycyclic Six‐Membered N‐Heterocycles: Microwave‐Assisted Synthesis
Authors: Kaur Navjeet
Published: January 2015

Review: 134 refs.
ChemInform Abstract: Present and Future of Cyclopropanations in Fragrance Chemistry
Authors: Schroeder Fridtjof
Published: January 2015

Review: 48 refs.
ChemInform Abstract: Applications of Acidic and Basic TSIL in Multikomponent Reactions
Authors: Chaudhary Ankita , Saluja Pooja , Aggarwal Komal , Khurana Jitender M.
Published: January 2015

Review: [36 refs.
ChemInform Abstract: Synthetic Approaches to Asymmetric Phthalocyanines and Their Analogues
Authors: Nemykin Victor N. , Dudkin Semyon V. , Dumoulin Fabienne , Hirel Catherine , Gurek Ayse Gul , Ahsen Vefa
Published: January 2015

Review: 283 refs.
ChemInform Abstract: C‐Ethynylpyrroles: Synthesis and Reactivity
Authors: Sobenina L. N. , Tomilin D. N. , Trofimov B. A.
Published: January 2015

Review: 131 refs.
ChemInform Abstract: Chemistry of Silybin
Authors: Biedermann D. , Vavrikova E. , Cvak L. , Kren V.
Published: January 2015

Review: data form 1959 to 2013; 94 refs.
ChemInform Abstract: Characterization of Biomass and Its Derived Char Using 13C‐Solid State Nuclear Magnetic Resonance
Authors: Baccile Niki , Falco Camillo , Titirici Maria‐Magdalena
Published: January 2015

Review: [171 refs.
ChemInform Abstract: Nanosafety Research — Are We on the Right Track?
Authors: Krug Harald F.
Published: January 2015

Review: 84 refs.
ChemInform Abstract: Mitochondria as a Target in the Therapeutic Properties of Curcumin
Authors: Trujillo Joyce , Granados‐Castro Luis Fernando , Zazueta Cecilia , Anderica‐Romero Ana Cristina , Chirino Yolanda Irasema , Pedraza‐Chaverri Jose
Published: January 2015

Review: 8 refs.
ChemInform Abstract: Effective Use of Heterologous Hosts for Characterization of Biosynthetic Enzymes Allows Production of Natural Products and Promotes New Natural Product Discovery
Authors: Watanabe Kenji
Published: January 2015

Review: 91 refs.
Thyroid FNA: International perspectives from the European Congress of Cytopathology—Can we cross the bridge of classifications?
Authors: Rossi Esther Diana , Pusztaszeri Marc , Schmitt Fernando , Bongiovanni Massimo , Chandra Ashish , Faquin William C.
Published: January 2015

The 38th European Congress of Cytology 2014, held in Geneva, Switzerland, offered a specific symposium concerning the Bethesda thyroid classification scheme. What emerged in that thyroid symposium, which was attended by all of the authors of this commentary, was the persistent need for a universally adopted thyroid fine‐needle aspiration reporting system that can diagnose the same thyroid nodule in the same way anywhere in the world. Herein, the authors critically outline the advantages and limits of thyroid fine‐needle aspiration classification schemes that were discussed at the symposium.
Synthesis and Electrochromic Properties of Conducting Polymers Based on Highly Planar 2,7‐Disubstituted Xanthene Derivatives
Authors: Olech Kamila , Gutkowski Ramona , Kuznetsov Volodymyr , Roszak Szczepan , Sołoducho Jadwiga , Schuhmann Wolfgang
Published: January 2015

On the basis of preliminary DFT calculations, p‐type semiconducting polymers based on 2,7‐substituted xanthene building blocks that show a high degree of planarity were designed. The synthesis, electrochemical characterization, and theoretical modeling of 2,7‐bis(thiophen‐2‐yl)‐9,9‐dimethylxanthene (1) and 2,7‐bis(3‐hexylthiophen‐2‐yl)‐9,9‐dimethylxanthene (2) is described. The synthetic procedure is based on the incorporation of thiophene rings by means of Pd‐catalyzed cross‐coupling reactions, which lead to monomers 1 and 2. Copolymers P1 and P2 obtained by means of anodic polymerization have been characterized by spectroscopic and electrochemical methods. Electrochromism was observed for both polymers. The experimental data supported by density functional theory modeling explain the influence of alkyl chain substitution on the properties of the investigated copolymers.
Iron Oxide Supported Sulfhydryl‐Functionalized Multiwalled Carbon Nanotubes for Removal of Arsenite from Aqueous Solution
Authors: Chen Bo , Zhu Zhiliang , Ma Jie , Qiu Yanling , Chen Junhong
Published: January 2015

Magnetic iron oxide/carbon nanotube (MI–CNT) hybrids have been successfully synthesized through a simple solid‐phase method by using as‐prepared CNTs (APCNTs). To further enhance the adsorption capacity for AsIII, MI–CNTs were subsequently functionalized by using an amino acid derivative (glutathione (GSH)) through a facile chemical route. CNTs not only act as a support for iron oxide but also significantly contribute to arsenic removal. The resulting GMI–CNTs possess simultaneously a high adsorption capacity and desirable magnetic properties, thus making them promising for use as an adsorbent to remove AsIII with significantly enhanced adsorption capacity (19.12 mg g−1) and desired magnetic separation properties (Ms=27.3 emu g−1). Adsorption studies indicated that the active sites on the surface of GMI–CNTs for AsIII are heterogeneous owing to the multiphase of Fe and the GSH functionalization. Therefore GMI–CNTs can potentially be used as a practical adsorbent for the decontamination of AsIII in water. The results of this study are highly important for practical applications of as‐prepared CNTs that contain catalyst nanoparticles.
Controlled Synthesis of Monodispersed Sub‐50 nm Nanoporous In2O3 Spheres and Their Photoelectrochemical Performance
Authors: Liu Qi , Zhang Wen , Liu Rongmei , Mao Guobing
Published: January 2015

Uniform nanoporous In2O3 nanospheres with high surface areas were synthesized through a simple solvothermal route with ethylenediamine (en) as the solvent. The prepared In2O3 nanospheres with diameters about 50 nm are composed of many nanoparticles with average sizes of ca. 5 nm. The unique nanospheres inherit both the large surface areas of the nanoparticles and the high crystallinity of bulky materials. The introduction of water or some other solvents into the reaction solution results in the formation of InOOH and In(OH)3 particles indicating that en is indispensable for synthesis of In2O3 with a nanoporous nanosphere structure. UV/Vis spectroscopy reveals that the band‐gap of synthesized In2O3 nanospheres is about 2.95 eV, mostly close to that of the single‐crystalline bcc‐In2O3. The PL spectrum of the In2O3 nanospheres shows two emission peaks located at 470 nm and 483 nm. The photocurrent of the prepared In2O3 electrodes by electrophoretic deposition strongly depends on the calcination temperature. The highest photocurrent density up to 1.9 mA cm–2 at 0.65 V (vs. Ag/AgCl) in 0.1 M Na2SO4 aqueous solution was recorded in the sample annealed at 550 °C. The high photocatalytic activity of the In2O3 nanospheres can be attributed to the high surface area, and the large number of nanopores in the In2O3 nanospheres.
Dicationic μ‐Diborolyl Arene Triple‐Decker Complexes [CpCo(μ‐1,3‐C3B2Me5)M(arene)]2+ (M = Rh, Ir; Cp = Cyclopentadienyl): Synthesis, Structures, Electrochemistry and Bonding
Authors: Muratov Dmitry V. , Romanov Alexander S. , Loginov Dmitry A. , Corsini Maddalena , Fabrizi de Biani Fabrizia , Kudinov Alexander R.
Published: January 2015

The reaction of the bromide complexes [CpCo(μ‐1,3‐C3B2Me5)MBr2]2 [M = Rh (1), Ir (2); Cp = cyclopentadienyl] with AgBF4 in acetonitrile affords the tris(acetonitrile) μ‐diborolyl triple‐decker complexes [CpCo(μ‐1,3‐C3B2Me5)M(MeCN)3]2+ [Rh (3), Ir (4)]. The labile nitromethane solvates [CpCo(μ‐1,3‐C3B2Me5)M(MeNO2)3]2+, generated in a similar way, react with benzene and its methylated derivatives to give the arene triple‐decker complexes [CpCo(μ‐1,3‐C3B2Me5)M(arene)]2+ [M = Rh (5), Ir (6); arene = C6H6 (a), 1,2,4,5‐Me4C6H2 (b), C6Me6 (c)]. The structures of 5b(BF4)2, 5c(BF4)2, 6b(BF4)2 and 6c(BF4)2 were determined by X‐ray diffraction. The electron‐transfer ability of the arene complexes was ascertained by electrochemical techniques. In general, they are able to undergo two separate one‐electron reductions reversibly. DFT calculations revealed structural changes caused by redox processes and satisfactorily predicted the redox potentials. The second reduction is accompanied by a η6 → η4 hapticity change of the arene ligand. Energy decomposition analysis revealed that the Rh–benzene bond in cation 5a is weaker than in cyclopentadienyl analogues [(C5R5)Rh(C6H6)]2+; however, 5a proved to be the least reactive in benzene replacement with acetonitrile and mesitylene.
The Unexpected Isolation of Bismuth Tris(carboxylate) Hydrates: Syntheses and Structures of [Bi(Hsal)3(H2O)] and [Bi(Hanth)3(H2O)] (H2sal = 2‐OH‐C6H4CO2H, Hanth = 2‐NH2‐C6H4CO2H)
Authors: Kumar Ish , Andrews Phil , Whitmire Kenton H.
Published: January 2015

A complex of the composition [Bi(2‐OH‐C6H4CO2)3(H2O)] (1) was isolated from the 1:3 reaction of BiPh3 with H2sal (H2sal = salicylic acid = 2‐OH‐C6H4CO2H) in wet xylene, and the analogous anthranilate compound [Bi(2‐NH2‐C6H4CO2)3(H2O)] (2) was obtained from the 1:3 reaction of Bi(OtBu)3 with Hanth (Hanth = anthranilic acid = 2‐NH2‐C6H4CO2H) in tetrahydrofuran. Compounds 1 and 2 were fully characterized spectroscopically and by single‐crystal X‐ray diffraction. Compounds 1 and 2 crystallize in the triclinic space group and display the η2‐(O,O′) binding mode for the oxygen atoms of the carboxylate ligands. There are two independent molecules in the asymmetric units of 1 and 2 that are connected by a weak bridging interaction of the OH or NH2 group to an adjacent molecule. Both bismuth atoms are bound to a H2O molecule, but the distances are highly asymmetric, long Bi···O lengths ranging from 2.74 to 2.89 Å.
Transition Metal Complexes with 1‐Adamantoyl Hydrazones – Cytotoxic Copper(II) Complexes of Tri‐ and Tetradentate Pyridine Chelators Containing an Adamantane Ring System
Authors: Leovac Vukadin M. , Rodić Marko V. , Jovanović Ljiljana S. , Joksović Milan D. , Stanojković Tatjana , Vujčić Miroslava , Sladić Dušan , Marković Violeta , Vojinović‐Ješić Ljiljana S.
Published: January 2015

Five pentacoordinate copper(II) complexes with 2‐acetylpyridine or di(2‐pyridyl) ketone 1‐adamantoyl hydrazone ligands (Adpy and Addpy, respectively) of the formulae [CuCl2(Adpy)] (1), [Cu2(μ‐Cl)2(Adpy‐H)2] (2), [Cu(NCS)2(Adpy)] (3), [Cu2(μ‐Cl)2(Addpy‐H)2] (4), and [Cu2(NCS)2(μ‐Addpy‐H)2] (5) were synthesized and characterized by spectral, electrochemical, and X‐ray structural analysis. Flow cytometry and morphological analysis confirmed that the copper(II) complexes 2 and 5 induced accumulation of a sub‐G1 phase population, and fluorescence microscopy indicated the presence of large cells in apoptosis. The interaction of the copper(II) complexes with calf thymus DNA (CT‐DNA) was monitored by changes in their UV/Vis spectra. The observed intrinsic binding constants for 2 and 5 (Kb = 1.77 × 106 and 3.58 × 106 M–1, respectively) together with ethidium displacement fluorescence experiments indicate intercalative binding. Complexes 2 and 5 showed nuclease activity against pUC19 plasmid DNA.
Synthesis and Structure–Activity Relationships of Gadolinium Complexes of DO3A–Benzothiazole Conjugates as Potential Theranostic Agents
Authors: Jung Ki‐Hye , Kang Sun‐Hee , Kang Min‐Kyoung , Kim Soyeon , Kim Hee‐Kyung , Kim Yeoun‐Hee , Ho Lee Gang , Shim Gyu‐Bo , Jung Jae‐Chang , Chang Yongmin , Kim Tae‐Jeong
Published: January 2015

The synthesis of two bifunctional chelates, 1,4,7,10‐tetraazacyclododecane‐1,4,7‐triacetic acid (DO3A) conjugates of benzothiazoles (H3L3a and H3L3b), and the corresponding gadolinium complexes (GdL3a and GdL3b) was achieved. The intracellular and tumor‐specific nature of GdL3a and GdL3b were confirmed by magnetic resonance images of the cytosols and nuclei of various cell lines. The two complexes displayed antitumor activities with varying degrees of growth‐inhibition and total‐growth‐inhibition values depending on the types of tumor cells. They caused morphological changes in tumor cell lines at much lower concentrations of gadolinium ([Gd] ≥ 50 μM) than their predecessors, DO3A–(p‐aniline benzothiazole) conjugates (H3L1), and its GdIII complex (GdL1) required concentrations that were almost four times as high ([Gd] ≥ 200 μM).
Drying temperature and extraction method influence physicochemical and sensory characteristics of pistachio oils
Authors: Sena‐Moreno Estela , Pardo José Emilio , Catalán Luis , Gómez Ricardo , Pardo‐Giménez Arturo , Alvarez‐Ortí Manuel
Published: January 2015

Drying is an important operation in pistachio processing to ensure good quality. Study of drying parameters is important since they affect the quality, mainly in color, flavor and nutritional value. Hence, drying parameters could also affect pistachio oils. Pistachios of variety Larnaka were dried at different temperatures (room, 30, 50, and 70°C). Changes in physicochemical quality parameters, stability, and chemical composition of the extracted oils were evaluated. Sensory evaluation was also performed. An increase in the peroxide value was observed when pistachios were dried at 70°C or when screw press was used to extract the oil, remaining low in the rest of oils extracted with the hydraulic press. A similar pattern was observed for K270 extinction coefficient. In addition, the oils from pistachios dried at higher temperatures (50°C, 70°C) showed an increase in polyphenol content and a decrease in stigmasterol. The oxidative stability was slightly higher when screw press was used. Changes in drying temperature and extraction system had no significant effects on fatty acid composition. Color sensory tests indicated a consumer preference for oils from pistachios dried at 70°C, which produced greenish oils. Pistachio oils with different characteristics are obtained depending on the drying temperature used, both of them acceptable by consumers.

Practical applications

Pistachios are considered nuts with the most nutritional value and a rich source of natural antioxidants. Drying is an important stage during pistachio processing, as it affects their oil fraction. The extraction system may also influence the characteristics of the final product. The combination of the drying temperature and extraction system may produce oils with different characteristics, which could be an interesting alternative in order to fit any consumer preferences.

Physicochemical parameters and chemical composition of pistachio oils obtained by means of two pressure systems were analysed. The effect of drying temperature of the pistachios was mitigated in the oils extracted with the screw press, whereas it was clearly visible in the oils obtained with the hydraulic press. The combination of drying temperature and extraction system produces oils with different characteristics.
Linker‐Length‐Dependent Complexation of a Triptycene‐Derived Macrotricyclic Polyether with π‐Extended Viologens
Authors: Han Ying , Gu Ya‐Kun , Guo Jia‐Bin , Chen Chuan‐Feng
Published: January 2015

Complexation between a triptycene‐derived macrotricyclic polyether and π‐extended viologens with different linker lengths in both the solution and the solid state was investigated in detail. No changes in complexation modes were observed with the host and guests of different linker length bearing methyl terminal functional groups, whereas different complexation modes were found with the host and guests of different linker length bearing methoxyethyl terminal functional groups. It was also found that two different complexation modes could exist in the same unit cell. Furthermore, we found that the binding and release of the guest in the complex could easily be controlled by addition and removal of K+ ions.
Picomolar Detection of Melamine Using Molecularly Imprinted Polymer‐Based Electrochemical Sensors Prepared by UV‐Graft Photopolymerization
Authors: Bakas Idriss , Salmi Zakaria , Jouini Mohamed , Geneste Florence , Mazerie Isabelle , Floner Didier , Carbonnier Benjamin , Yagci Yusuf , Chehimi Mohamed M.
Published: January 2015

Molecularly imprinted polymer (MIP) films of melamine were prepared by photopolymerization of vinylic monomers on diazonium‐modified gold electrodes. The gold‐grafted MIPs are specific and selective for melamine in either organic or aqueous media. The interferent molecules cyromazine and cyanuric acid were not recognized by the MIPs. The limit of detection was as low as 1.75×10−12 mol L−1 at S/N=3. Efficiency of melamine rebinding is related to the solubility parameter of the organic solvent or pH and ionic strength of the aqueous medium. It is concluded that diazonium salts permit to design robust electrochemical MIP sensors.
A Ruthenium Based Organometallic Complex for Biosensing that is both a Stable Redox Label and a Homobifunctional Linker
Authors: Lee Yeng Ying , Parker Stephen G. , Barfidokht Abbas , Alam Muhammad Tanzirul , Walker D. Barney , Messerle Barbara A. , Gooding J. Justin
Published: January 2015

A stable ruthenium‐based redox label, Ru(acetylacetonate)2(bipyridine‐NH2), has been synthesized with the target of circumventing the problem associated with the use of ferrocene for biosensing in solutions containing chloride ions. The redox species was shown to be highly stable with repeated cycling in biological buffers as well as being amenable to surface coupling reactions. To demonstrate the latter, the redox label was anchored onto a self‐assembled monolayer of 6‐mercaptohexanoic acid, using carbodiimide coupling, followed by binding of a pentapeptide to the redox label.
Lovastatin and (+)‐geodin production by Aspergillus terreus from crude glycerol
Authors: Abd Rahim Muhamad Hafiz , Hasan Hanan , Montoya Alejandro , Abbas Ali
Published: January 2015

The use of pure substrate represents a significant proportion of the cost of manufacturing a drug such as lovastatin. This study explores the production of lovastatin and (+)‐geodin by Aspergillus terreus ATCC 20542 using biodiesel‐derived crude glycerol (CG) as a feedstock. Shake flask experiments showed reduced lovastatin production and glycerol consumption in the presence of 10–50 g/L CG with respect to pure glycerol controls. At 50 g/L, lovastatin and (+)‐geodin production was significantly reduced by 82 and 73%, respectively. The lowest lovastatin inhibition was detected in 30 g/L of CG (48%), which was accompanied by a significant rise in (+)‐geodin production (338%). Further investigation was performed on three major impurities found in CG, namely methanol (MeOH), sodium chloride (NaCl), and fatty acids (oleic acid and palmitic acid (PA), soap). None was particularly inhibitory for lovastatin, except soap and PAs, which reduced its production by more than 50% at all concentrations tested. In contrast, (+)‐geodin was inhibited in the presence of MeOH and PA by up to 46 and 91%, respectively. These observations indicate that partial purification of CG would be potentially useful in improving production of lovastatin and (+)‐geodin by A. terreus.
Power law statistics of cliff failures, scaling and percolation
Authors: Baldassarri Andrea , Sapoval Bernard
Published: January 2015

Large cliff failures have often been characterized by their size in terms of the horizontal eroded area at the cliff top, and the maximum local retreat of the coastline. Field studies suggest that the frequencies of these two quantities decrease as power laws of their respective magnitudes, defining two different decay exponents. Moreover, the horizontal area increases as a power law of the maximum local retreat, identifying a third exponent. This observation indicates that the geometry of cliff failures are similar for different magnitudes. It is shown that, under a ‘scaling hypothesis’, the exponents satisfy a precise mathematical relation that relates the exponent of the distributions of magnitudes of events and their geometry – a relation that could be useful to validate the analysis of field catalogs. In order to understand the observed scenario, a numerical model of rocky coast erosion is developed. Despite its minimal character, it reproduces the observed cliff failure statistics. Strikingly, the model precisely reproduces the geometric similarity of cliff failures observed in the field. These results suggest that the theory of percolation, which underlies the erosion model, can possibly be used as a guide to decipher the physics of rocky coast erosion and could provide precise predictions of the statistics of cliff collapses. Copyright © 2015 John Wiley & Sons, Ltd.
A compressible two‐fluid multiphase model for CO2 leakage through a wellbore
Authors: Musivand Arzanfudi Mehdi , Al‐Khoury Rafid
Published: January 2015

This paper introduces an effectively mesh‐independent and computationally efficient model for CO2 leakage through wellbores. A one‐dimensional compressible two‐fluid domain, representing a homogeneous air gas and a multiphase CO2 with a jump at the interface between them, is modeled.

The physical domain is modeled using the drift‐flux model, and the governing equations are solved using a mixed finite‐element discretization scheme. The standard Galerkin FEM, the partition of unity method, and the level‐set method are integrated to solve the problem. All important physical phenomena and processes occurring along the wellbore path, including fluid dynamics, buoyancy, phase change, compressibility, thermal interaction, wall friction, and slip between phases, together with the jump in density and enthalpy between air and CO2, are considered. Two numerical examples illustrating the computational capability and efficiency of the model are presented. Copyright © 2015 John Wiley & Sons, Ltd.
Clastic sedimentation in the Late Oligocene Southalpine Foredeep: from tectonically controlled melting to tectonically driven erosion
Authors: Di Capua Andrea , Vezzoli Giovanni , Cavallo Alessandro , Groppelli Gianluca
Published: January 2015

The Villa Olmo Conglomerate (lower member of the Como Conglomerate Formation, Gonfolite Lombarda Group, Southern Alps, Italy) represents the first coarse clastic inputs into the Oligocene Southalpine Foredeep. A number of techniques including sedimentary lithofacies analyses, clast counts on turbidite conglomerate bodies, sandstone petrography through Gazzi–Dickinson point‐count method and XRF analyses, and optical and minero‐chemical analyses on single clasts have been performed, in order to better define the sediment source area and geodynamic conditions which promoted sedimentation in the Southalpine Foredeep at the end of the Oligocene. The Villa Olmo Conglomerate interdigitates with the upper part of the Chiasso Formation, and gradually passes upward into the overlying Como Conglomerate Formation. Provenance analyses (conglomerate clast counts and sandstone petrography) reveal a strong metamorphic provenance signal, likely sourced from eroded Southalpine basement. An increase in igneous plutonic clasts reflects sediment supply from the Southern Steep Belt and a decrease of volcano‐sedimentary Mesozoic cover sequences. Optical and minero‐chemical analyses on volcanic detritus detect the presence of sub‐intrusive to effusive, andesite to rhyolite products, ascribable to the Varese‐Lugano Permian volcanoclastic suite, as well as Oligocene andesite products. Plutonic clasts document the presence of tonalites, granites, and brittle deformed granodiorites (with two micas), being likely sourced from the tonalite tail of the Bergell Pluton and the plutonic units of the Bellinzona‐Dascio Zone. The identification of this provenance suite implies palaeo‐drainage from the region between Varese (Southern Alps) and the Bellinzona‐Dascio Zone (Central Alps). The Villa Olmo Conglomerate is the first depositional record of the onset of tectonically driven erosion in the Alpine belt. We infer that the previous low sediment budget regime (Eocene–Middle Oligocene) was a consequence of a tectonically controlled melting phase, during which tectonic events promoted magmatic production in the middle crust of the Central Alps at rates higher than those of crustal deformation, so inhibiting sediment production. We conclude that changes in the deep structures of the Alpine Orogenic chain have controlled the main geodynamic processes during Oligocene–Neogene times, and have controlled sediment composition and supply into the Southalpine Foredeep. Copyright © 2015 John Wiley & Sons, Ltd.
Copper(I)‐Catalyzed Amination of Halogenopyridines with Polyamines
Authors: Anokhin Maksim V. , Averin Alexei D. , Panchenko Svetlana P. , Maloshitskaya Olga A. , Buryak Alexei K. , Beletskaya Irina P.
Published: January 2015

CuI‐Catalyzed amination of 2‐bromo‐, and 2‐, 3‐, and 4‐iodopyridines with tri‐ and tetraamines aimed at the synthesis of N,N′‐diheteroaryl derivatives was studied. A strong dependence of the product yields on the nature of starting compounds and the ligand used was observed. The increase in the number of ethene‐1,2‐diamine fragments in the polyamine structure led to the increase in the yields of polyheteroarylated compounds, whereas propane‐1,3‐diamine fragments favored the formation of monopyridinyl derivatives and promoted the heteroarylation of the secondary amino groups. 2‐Iodopyridine, as a more reactive compound, readily formed N,N‐diarylated products. The best yields of the target N,N′‐dipyridin‐2‐yl derivatives were 76% in the case of the triamine and 68% in the case of the tetraamine. A comparison of CuI‐ and Pd0‐mediated heteroarylation of polyamines was also presented.
New Route for the Synthesis of Four‐Membered Cyclic Ketene Dithioacetals
Authors: Habibi Azizollah , Valizadeh Yousef , Alizadeh Abdolali
Published: January 2015

Novel ketene dithioacetals have been synthesized by a one‐pot condensation reaction of active methylene compounds with CS2 in the presence of alkyl acetylenecarboxylates. This reaction proceeds in a regioselective manner and provides products in good yields. The structures of the ketene dithioacetals were characterized by IR, 1H‐ and 13C‐NMR, and MS data, and elemental analyses.
Steroidal Alkaloids from Veratrum dahuricum (Turcz.) Loes. f. with Genotoxicity on Brain Cell DNA in Mice
Authors: Cong Yue , Li Jing , Zhang Qing‐Chun , Guo Jing‐Gong , Li Sha‐Sha
Published: January 2015

Two new steroidal alkaloids, 2β‐hydroxyverdine (1) and tomatillidine 3‐O‐β‐D‐glucopyranoside (2), were isolated from the root and rhizome of Veratrum dahuricum (Turcz.) Loes. f., together with four known compounds, i.e., 16‐O‐(2‐methylbutyroyl)germine (3), veramitaline (4), jervine (5), and veratroylzygadenine (6). Their structures were established by extensive spectroscopic analysis, as well as by comparison with data in literature. Compounds 1–6 exhibited genotoxicity on brain cell DNA of the cerebellum and cerebral cortex in mice, evaluated by using single‐cell gel electrophoresis (comet assay).
New Flavanol Glucosides from Abacopteris aspera (Presl) Ching
Authors: Fan Zhen , Jin Jing , Lin Chaozhan , Zhu Chenchen , Yang Tao , Yang Bao , Zhu Jinping , Zhao Zhongxiang
Published: January 2015

Three new flavanol glycosides, 1–3, and eight known compounds, 4–11, were isolated from a MeOH extract of the fern Abacopteris aspera (Presl) Ching. Their structures were elucidated on the basis of extensive spectroscopic analysis, including HSQC, HMBC, 1H,1H‐COSY, and NOESY experiments, acid hydrolysis, and by the comparison of their NMR data with those of related compounds.
Tandem Benzylic Oxidation/Dihydroxylation of α‐Vinyl‐ and α‐Alkenylbenzyl Alcohols
Authors: Fernandes Rodney A. , Kattanguru Pullaiah
Published: January 2015

A de novo tandem benzylic oxidative dihydroxylation of α‐vinyl‐ and α‐alkenylbenzyl alcohols has been developed to give α,β‐dihydroxypropiophenones (=2,3‐dihydroxy‐1‐phenylpropan‐1‐ones) and α,β‐dihydroxyalkyl phenones. This method was shown to be substrate‐selective and specific for the oxidation of benzylic alcohols.
Absolute Configuration of Resveratrol Oligomers Isolated from Hopea utilis
Authors: Ito Tetsuro , Hoshino Ryosuke , Iinuma Munekazu
Published: January 2015

Phytochemical studies on a stem of Hopea utilis (Dipterocarpaceae) resulted in the isolation of two new resveratrol derivatives, namely hopeaside E (1; resveratrol trimer) and hopeaside F (2; resveratrol pentamer), together with ten known resveratrol derivatives, 3–12. The structures of the new compounds were elucidated by spectroscopic analyses, including NMR experiments, and their absolute configurations were determined on the basis of a comparative configurational analysis using the β‐D‐glucopyranosyl group and chiroptical data. The absolute configuration of (+)‐balanocarpol (3) was also determined by acid‐catalyzed skeletal conversion.
Palladium‐Catalyzed Arylation of Olefins by Triarylphosphines via CP Bond Cleavage
Authors: Lu Dapeng , Xu Yu , Liu Wenjing , Guo Lijuan , Sun Xingxia
Published: January 2015

CH Arylation of olefins by triarylphosphines via CP bond cleavage has been achieved with either Pd0 or PdII catalysts. A variety of olefins and triarylphosphines are tolerated, and we inferred that both Pd0 and PdII could function directly without pre‐oxidation or pre‐reduction.
First Stereoselective Synthesis of the Cytotoxic Polyketide (4R)‐1‐(3,5‐Dihydroxyphenyl)‐4‐hydroxypentan‐2‐one
Authors: Rajendra Prasad Kothakonda , Purushotham Reddy Sudina , Suresh Babu Katragadda , Madhusudana Rao Janaswamy
Published: January 2015

The first stereoselective synthesis of the cytotoxic polyketide (4R)‐1‐(3,5‐dihydroxyphenyl)‐4‐hydroxypentan‐2‐one (1) was achieved from readily available propylene oxide and 3,5‐dimethoxybenzyl alcohol. The synthesis involves Jacobsen's hydrolytic kinetic resolution (HKR) and Grignard reaction as key steps.
Synthesis of a Regioisomer of β‐Lapachone and Analogs as Potent Antitumor Agents
Authors: Ding Qunshan , Zhang Yan , Shen Zhenhua , Song Chuanjun , Chang Junbiao
Published: January 2015

A regioisomer of β‐lapachone and two analogs were synthesized and evaluated for their antitumor activities. All three compounds tested were found to exhibit promising activities against PC‐3, HepG2, and Raji cancer cell lines in μM range.
Lithium Enolates: ‘Capricious’ Structures – Reliable Reagents for Synthesis
Authors: Braun Manfred
Published: January 2015

The first part of this review article deals with the structures of enolates. The development of research in this field during the last half century will be illustrated by highlightening seminal contributions, while, by no means, an attempt of comprehensiveness is made: the choice of spotlights has, admittedly, a personal touch. Aside from derivatization of lithium enolates and their crystal structures that meanwhile are classics, more recent solution studies are presented. In the second part, it will be shown by contributions of our laboratory that, despite their complicated structures, lithium enolates are reliable ‘workhorses’ in synthesis with emphasis being given to stereoselective CC bond forming reactions due to the Pd‐catalyzed allylic alkylation of non‐stabilized, preformed enolates.
Sculpting Metal‐binding Environments in De Novo Designed Three‐helix Bundles
Authors: Plegaria Jefferson S. , Pecoraro Vincent L.
Published: January 2015

De novo protein design is a biologically relevant approach used to study the active centers of native metalloproteins. In this review, we will first discuss the design process in achieving α3D, a de novo designed three‐helix bundle peptide with a well‐defined fold. We will then cover our recent work in functionalizing the α3D framework by incorporating a tris(cysteine) and tris(histidine) motif. Our first design contains the thiol‐rich sites found in metalloregulatory proteins that control the levels of toxic metal ions (Hg, Cd, and Pb). The latter design recapitulates the catalytic site and activity of a natural metalloenzyme carbonic anhydrase. The review will conclude with future design goals aimed at introducing an asymmetric metal‐binding site in the α3D framework.
Second Morning ACR Could Be the Alternative to First Morning ACR to Assess Albuminuria in Elderly Population
Authors: Wang Hua‐Bin , Li Rong , Liu Rui , Cui Xiao‐Fan , Pan Wen‐Jie , Sun Ao
Published: January 2015

Background

Albumin/creatinine ratio (ACR) from a first morning urine is recommended as a early indicator for diabetic nephropathy. However, it is not always feasible to collect the first morning urine for outpatients. We aimed to explore whether ACR from a second morning urine had a good consistency with that from a first morning urine to predict albuminuria in Chinese elderly citizens.

Method

One hundred and ninety‐one elderly citizens (≧60 years old) from Junliangcheng community, Dongli district, Tianjin, China were included. A first and second morning urine was collected from each participants, successfully and detected the urinary albumin and creatinine of each urine sample. Albumin to creatinine ratio from a first morning urine (ACR1) was compared with that from a second morning urine (ACR2), and the ability of ACR1 and ACR2 to predict albuminuria was assessed. Result: ACR1 and ACR2 were highly correlated (r = 0.901), especially in male and hypertension group (r = 0.938 and 0.904). The slope and intercept were 0.93 and 0.11 after log‐transformed. And there was no statistical difference between values of ACR1 and ACR2 (P = 0.271). Overall, 26.2% participants were detected with albuminuria when judged by ACR1 and 28.3% by ACR2. A good concordance of ACR category (normal or albuminuria) was found between ACR1 and ACR2 (Kappa value = 0.815 in overall; in male and hypertension group were 0.900 and 0.850).

Conclusion

A second morning urine ACR could be the alternative to a first morning urine ACR for albuminuria detection in elderly population.
Dietary protein influences the life‐history characteristics across generations in the African striped mouse Rhabdomys
Authors: Nel Kerith , Rimbach Rebecca , Pillay Neville
Published: January 2015

The level of dietary protein determines the onset of reproduction, affects offspring growth and maturation, and hence influences life‐history traits and fitness. However, to date, the long‐term life‐history consequences of protein deficiency are not well understood. We studied the transgenerational effects of different levels of dietary protein on the life‐history and level of maternal behavior of the striped mouse Rhabdomys dilectus chakae in captivity. Breeding pairs were assigned to three treatments based on the percentage of dietary protein: baseline (BP; 19%); high protein (HP; 24%); and low protein (LP; 10%). Reproductive output and offspring ontogeny was diminished in the LP treatment compared to the other treatments. Transgenerational effects were studied by breeding F2 females raised on the LP or HP diets on the same (HP–HP, LP–LP) or altered diets (HP–LP, LP–HP). The LP–LP treatment had no reproductive success, while reproductive capacity in the remaining treatments was determined mainly by the diet of mothers at breeding. Pups from protein‐restricted females (LP, HP–LP) showed post‐weaning compensatory growth. Timing of sexual maturity was age‐dependent in female and mass‐dependent in male offspring. Females fed low protein diets during breeding (LP, HP–LP) displayed lower levels of maternal behavior than females from the other treatments. This study demonstrates that the level of dietary protein influences the life‐history of R. d. chakae in predictable ways. The taxon responds to changes in dietary protein at breeding, largely regardless of its nutrition during rearing. Such phenotypic flexibility in life‐history parameters allows Rhabdomys to adaptively respond to unpredictable environmental changes. J. Exp. Zool. 323A: 97–108, 2015. © 2015 Wiley Periodicals, Inc.
Do turtles follow the rules? Latitudinal gradients in species richness, body size, and geographic range area of the world's turtles
Authors: Angielczyk Kenneth D. , Burroughs Robert W. , Feldman Chris. R.
Published: January 2015

Understanding how and why biodiversity is structured across the globe has been central to ecology, evolution, and biogeography even before those disciplines took their modern forms. Three global‐scale patterns in particular have been the focus of research and debate for decades: latitudinal gradients in species richness (richness decreases with increasing latitude), body size (body size increases with increasing latitude in endotherms; Bergmann's rule), and geographic range size (range size increases with increasing latitude; Rapoport's rule). Despite decades of study, the generality and robustness of these trends have been debated, as have their underlying causes. Here we investigate latitudinal gradients in species richness, body size, and range size in the world's turtles (Testudines), and add more evidence that these rules do not seem to apply across all taxa. We show that turtle diversity actually peaks at 25° north, a highly unusual global pattern. Turtles also fail to follow Bergmann's Rule, and may show the converse (larger at lower latitudes), though trends are weak. Turtles also show a complex relationship between latitude and range size that does not directly follow Rapoport's rule. Body size and geographic range size are significantly correlated, and multiple abiotic and biotic variables help explain the relationships between latitude and species diversity, body size, and range size. Although we show that turtles do not strictly follow some classic biogeographical rules, we also call for further in‐depth research to investigate potential causal mechanisms for these atypical patterns.J. Exp. Zool. (Mol. Dev. Evol.) 324B: 270–294, 2015. © 2015 Wiley Periodicals, Inc.