bluuebunny/crossref_metadata_2025 huggingface dataset:
ChemInform Abstract: Double γ‐Alkylation of Allylic Phosphorus Ylides: A Unique Access to Oxa‐Bicyclic[3.3.0] Diene Skeletons.
Authors: Wang Peng , Liao Saihu , Zhu Jian‐Bo , Tang Yong
Published: April 2014

A new ylide‐initiated tandem cyclization reaction based on γ‐dialkylation of allylic ylides (I) is reported affording a series of bicyclic compounds (III) in high yields with perfect diastereoselectivity.
ChemInform Abstract: Synthesis of Dihydrobenzo[b]furans by Diastereoselective Acyloxyarylation.
Authors: Hata Kazuhiro , He Zhiheng , Daniliuc Constantin Gabriel , Itami Kenichiro , Studer Armido
Published: April 2014

A highly regio‐ and diastereoselective dearomatizing 2,3‐difunctionalization of benzofurans (I) is reported.
ChemInform Abstract: Synthesis of 3‐Iodothiophenes via Iodocyclization of (Z)‐Thiobutenynes.
Authors: Baroni Adriano C. M. , et al. et al.
Published: April 2014

Various 3‐iodothiophenes are synthesized in good to excellent yields and the formation of diiodobutadiene as by‐product can be suppressed.
ChemInform Abstract: Solvent‐Mediated One‐Pot Synthesis of Cyclic N‐Substituted Imides.
Authors: Patil Sambhaji V. , Mahale Keshao A. , Gosavi Kirankumar S. , Deshmukh Ganesh B. , Patil Nilesh S.
Published: April 2014

The yields of the products are not given.
ChemInform Abstract: Nickel‐Catalyzed Direct Addition of Diorganozinc Reagents to Phthalimides: Selective Formation of Gamma‐Hydroxylactams.
Authors: Dennis Joseph M. , Calyore Catherine M. , Sjoholm Jessica S. , Lutz J. Patrick , Gair Joseph J. , Johnson Jeffrey B.
Published: April 2014

This nickel‐catalyzed protocol allows the selective mono‐addition of diorganozinc reagents to various phthalimides to give 3‐hydroxyisoindolinones.
ChemInform Abstract: Organocatalytic Conjugate Addition of Nitroalkanes to 3‐Ylidene Oxindoles: A Stereocontrolled Diversity Oriented Route to Oxindole Derivatives.
Authors: Quintavalla Arianna , Lanza Francesco , Montroni Elisa , Lombardo Marco , Trombini Claudio
Published: April 2014

The asymmetric Michael addition affords various substituted oxindole derivatives by using a thiourea‐based organocatalyst.
ChemInform Abstract: Copper‐Catalyzed Trifluoromethylation of N‐Arylacrylamides “on Water” at Room Temperature.
Authors: Yang Fang , Klumphu Piyatida , Liang Yong‐Min , Lipshutz Bruce H.
Published: April 2014

The intramolecular trifluoromethylation of arylacrylamides (I) and (IV) with Langlois′ reagent leads to the formation of oxindole derivatives (III) and (V)/(VI) via a radical process.
ChemInform Abstract: Synthesis and Diels—Alder Reactions of Pyrrolo[3,4‐b]indoles. A Synthesis of 4‐Acetamidocarbazoles and an Approach to the Antiostatins.
Authors: Peky Erin T. , Jiang Jun , Gribble Gordon W.
Published: April 2014

An efficient and potentially general method for the synthesis of stable 3‐alkyl‐2‐acylpyrrolo[3,4‐b]indoles from skatole is developed.
ChemInform Abstract: Asymmetric Synthesis of 3,4‐Annulated Indoles Through an Organocatalytic Cascade Approach.
Authors: Caruana Lorenzo , Fochi Mariafrancesca , Comes Franchini Mauro , Ranieri Silvia , Mazzanti Andrea , Bernardi Luca
Published: April 2014

Indoles (II) and (V) bearing Michael acceptors at the 4‐position are used in enantioselective organocatalytic cascade reactions with enals (III) and (VI).
ChemInform Abstract: Designing and Synthesis of Novel Antimicrobial Heterocyclic Analogues of Fatty Acids.
Authors: Ahmad Aiman , Ahmad Anis , Varshney Himani , Rauf Abdul , Rehan Mohd , Subbarao Naidu , Khan Asad U.
Published: April 2014

Isoxazole (III) and 4 dihydroisoxazoles of type (V) are prepared and tested for their antimicrobial activities.
ChemInform Abstract: Synthesis and Biological Evaluation of 3‐(Trimethoxyphenyl)‐2(3H)‐thiazole Thiones as Combretastatin Analogues.
Authors: Banimustafa Mandana , Kheirollahi Asma , Safavi Maliheh , Kabudanian Ardestani Sussan , Aryapour Hassan , Foroumadi Alireza , Emami Saeed
Published: April 2014

A series of thiazole thione derivatives of type (III) and (VI) are prepared and among them, it is shown that (IIIb) exhibits the highest activity against human cancer cell lines T47D, MCF‐7 and MDA‐MB‐231.
ChemInform Abstract: A Tandem Isomerization/Prins Strategy: Iridium(III)/Broensted Acid Cooperative Catalysis.
Authors: Lombardo Vince M. , Thomas Christopher D. , Scheidt Karl A.
Published: April 2014

Different types of indoles containing aliphatic allyl ether side chains are investigated as substrates in a tandem isomerization/Prins‐cyclization sequence to give pyran fused indoles in good yields.
ChemInform Abstract: Guanidine‐Catalyzed γ‐Selective Morita—Baylis—Hillman Reactions on α,γ‐Dialkyl‐allenoates: Access to Densely Substituted Heterocycles.
Authors: Selig Philipp , Turockin Aleksej , Raven William
Published: April 2014

The bicyclic guanidine MTBD is shown to be an efficient catalyst for the Morita—Baylis—Hillman reaction of allenoates (I) with aldehydes (II).
ChemInform Abstract: Hydroxylated Polyfunctionalized Benzo[c]coumarins by an Organocatalyzed Tandem 1,4‐Conjugate Addition, Decarboxylation and Aromatization Reaction.
Authors: Talhi Oualid , Makhloufi‐Chebli Malika , Pinto Diana C. G. A. , Hamdi Maamar , Silva Artur M. S.
Published: April 2014

A simple one‐pot protocol for the title reaction sequence starting from coumarin derivatives (I) and (II) is presented.
ChemInform Abstract: Novel and Cleaner Synthesis of Pyridinium Salts from Pyridoxal Oxime and Substituted Phenacyl Bromides
Authors: Busic Valentina , Gaso‐Sokac Dajana , Kovac Spomenka
Published: April 2014

using a liquid‐assisted grinding methodology
ChemInform Abstract: Iron(II)‐Catalyzed [2 + 2 + 2] Cycloaddition for Pyridine Ring Construction.
Authors: Richard Vincent , Ipouck Melinda , Merel Delphine S. , Gaillard Sylvain , Whitby Richard J. , Witulski Bernhard , Renaud Jean‐Luc
Published: April 2014

The products are obtained in lower yields when aromatic nitriles are applied.
ChemInform Abstract: Regioselective Synthesis of 3‐Benzyl Substituted Pyrimidino Chromen‐2‐ones and Evaluation of anti‐Microbial and anti‐Biofilm Activities.
Authors: Emmadi Narender Reddy , Atmakur Krishnaiah , Bingi Chiranjeevi , Godumagadda Narender Reddy , Kumar Chityal Ganesh , Nanubolu Jagadeesh Babu
Published: April 2014

A variety of highly functionalized pyrimidinylmethylchromene derivatives (IV) (22 examples) are synthesized via a one‐pot three‐component reaction.
ChemInform Abstract: Iminophosphoranes in Heterocyclic Synthesis: Synthesis of Pyrazolo[1,5‐a]pyrimidines, Imidazo[1,2‐b]pyrazole and Pyrazolo[1,5‐b][1,2,4]triazine Derivatives via Intermolecular Aza‐Wittig Reactions.
Authors: Raslan Mohamed , Khalil Mohamed , Sayed Samia Mohamed
Published: April 2014

Iminophosphoranes are used as building blocks in the synthesis of pyrazolopyrimidines [e.g. (III), (XIII)], imidazopyrazole (VII) and pyrazolotriazines (XV).
ChemInform Abstract: Chiral Phosphoric Acid‐Catalyzed Asymmetric Aza‐Friedel—Crafts Reaction of Indoles with Cyclic N‐Acylketimines: Enantioselective Synthesis of Trifluoromethyldihydroquinazolines.
Authors: Zhang Ke‐Feng , Nie Jing , Guo Ran , Zheng Yan , Ma Jun‐An
Published: April 2014

An enantioselective aza‐Friedel—Crafts reaction of cyclic N‐acylketimines with electron‐rich arenes is developed.
ChemInform Abstract: Unexpected Ring Enlargement of 2‐Hydrazono‐2,3‐dihydro‐1,3‐thiazoles to 1,3,4‐Thiadiazines.
Authors: Pfeiffer Wolf‐Diethard , Ahlers Klaus‐Dieter , Saghyan Ashot S. , Villinger Alexander , Langer Peter
Published: April 2014

4‐Methyl‐ and 4‐ethylthiosemicarbazides are investigated as dinucleophilic building blocks in the cyclization reaction with α‐bromoacetophenones.
ChemInform Abstract: Regioselective Synthesis of 2,3‐Dihydrobenzodioxepinones from Epoxides and 2‐Bromophenols via Palladium‐Catalyzed Carbonylation.
Authors: Li Haoquan , Spannenberg Anke , Neumann Helfried , Beller Matthias , Wu Xiao‐Feng
Published: April 2014

Ethyl 3‐phenyloxirane‐2‐carboxylate does not react to the desired 2,3‐disubstituted product.
ChemInform Abstract: Iridium‐ and Rhodium‐Catalyzed Dehydrogenative Silylations of C(sp3)—H Bonds Adjacent to a Nitrogen Atom Using Hydrosilanes.
Authors: Mita Tsuyoshi , Michigami Kenichi , Sato Yoshihiro
Published: April 2014

In the presence of iridium or rhodium catalysts, C(sp3)—H bonds adjacent to a nitrogen atom are silylated by the aid of a pyridine‐directing group.
ChemInform Abstract: Synthesis and Biological Evaluations of a Series of Novel Azolyl, Azinyl, Pyranyl, Chromonyl and Azepinyl Phosphonates.
Authors: Ali Tarik E. , Abdel‐Aziz Salah A. , El‐Edfawy Somaya M. , Mohamed El‐Hossain A. , Abdel‐Kariem Somaia M.
Published: April 2014

Among the tested compounds, derivative (XVIIa) is most effective against Staphylococcus aureus and Bacillus subtilis and derivative (XVIIb) shows the best activities against Candida albicans and Aspergillus fumigatus.
ChemInform Abstract: An Approach to Benzophosphole Oxides Through Silver‐ or Manganese‐Mediated Dehydrogenative Annulation Involving C—C and C—P Bond Formation.
Authors: Unoh Yuto , Hirano Koji , Satoh Tetsuya , Miura Masahiro
Published: April 2014

It is demonstrated that Ag‐mediated dehydrogenative coupling of arylphosphine oxides with internal alkynes produces benzophosphole oxides in good yields.
ChemInform Abstract: Synthesis of Photochromic Bis‐1,3‐diazabicyclo[3.1.0]hex‐3‐ene Derivatives Having a Bisindole Linkage.
Authors: Mahmoodi N. O. , Ghavidast A.
Published: April 2014

New photochromic bis‐1,3‐diazabicyclo[3.1.0]hex‐3‐ene derivatives (III) (6 examples) are synthesized which form deeply colored, relatively stable ylides under UV irradiation.
ChemInform Abstract: New Antiinflammatory Cembranoid Diterpenoids from the Vietnamese Soft Coral Lobophytum crassum.
Authors: Thao Nguyen Phuong , Luyen Bui Thi Thuy , Ngan Nguyen Thi Thanh , Song Seok Bean , Cuong Nguyen Xuan , Nam Nguyen Hoai , Kiem Phan Van , Kim Young Ho , Minh Chau Van
Published: April 2014

Four new cembranoid diterpenes lobocrasols A (Ia), B (Ib), C (IIa), and D (IIb) are isolated.
ChemInform Abstract: Rubescins A (I), B (II) and C (III): New Havanensin Type Limonoids from Root Bark of Trichilia rubescens (Meliaceae).
Authors: Tsamo Tontsa Armelle , Mkounga Pierre , Njayou Frederic Nico , Manautou Jose , Kirk Marat , Hultin Philip Gregory , Nkengfack Augustin Ephrem
Published: April 2014

Title compounds are isolated from the root bark of Trichilia rubescens (Meliaceae) together with 3 known compounds.
ChemInform Abstract: Non‐terpenoidal Constituents of Azadirachta indica Root Bark
Authors: Siddiqui Bina Shaheen , Ara Iffat , Faizi Shaheen
Published: April 2014

isolation and structure of the new steroid margocidin (I)
ChemInform Abstract: Nucleophilic Catalysis of MeON‐Neoglycoside Formation by Aniline Derivatives.
Authors: Loskot Steven A. , Zhang Jianjun , Langenhan Joseph M.
Published: April 2014

A kinetic study of the formation of MeON‐Neoglycosides of various carbohydrates by deployment of different aniline catalysts is described.
ChemInform Abstract: Organocatalyzed Cascade Reactions of Carbohydrates — A Direct Access to C‐Glycosides.
Authors: Voigt Benjamin , Mahrwald Rainer
Published: April 2014

An organocatalytic transformation to elongate carbohydrates is reported.
ChemInform Abstract: Indole Diterpene Alkaloids as Novel Inhibitors of the Wnt/β‐Catenin Pathway in Breast Cancer Cells.
Authors: Sallam Asmaa A. , Ayoub Nehad M. , Foudah Ahmed I. , Gissendanner Chris R. , Meyer Sharon A. , El Sayed Khalid A.
Published: April 2014

Nine new penitrem analogs (Ia)‐(Ig), (IIa), and (IIb) are semisynthetically prepared in an attempt to identify pharmacophores correlated with BK channel inhibition and tremorgenicity of penitrems and decrease their toxicity.
ChemInform Abstract: Anisotropic Gold Nanoparticles: Synthesis, Properties, Applications, and Toxicity
Authors: Li Na , Zhao Pengxiang , Astruc Didier
Published: April 2014

Review: 429 refs.
ChemInform Abstract: Controlling Nanomaterial Synthesis, Chemical Reactions and Self Assembly in Dynamic Thin Films
Authors: Chen Xianjue , Smith Nicole M. , Iyer K. Swaminathan , Raston Colin L.
Published: April 2014

Review: emphasis on the application of spinning disc processors and rotating tube processors; 80 refs.
ChemInform Abstract: Electrochemical Engineering of Hollow Nanoarchitectures: Pulse/Step Anodization (Si, Al, Ti) and Their Applications
Authors: Wang Kaiying , Liu Guohua , Hoivik Nils , Johannessen Erik , Jakobsen Henrik
Published: April 2014

Review: 252 refs.
ChemInform Abstract: Fluorocarbons Modulate the Coordination Sphere of f‐Element Complexes
Authors: Alvarez Santiago , Menjon Babil
Published: April 2014

Review: 13 refs.
ChemInform Abstract: Hydrogen‐Bonding in Aminocatalysis: From Proline and Beyond
Authors: Albrecht Lukasz , Jiang Hao , Joergensen Karl Anker
Published: April 2014

Review: 29 refs.
ChemInform Abstract: Towards Ideal Synthesis: Alkenylation of Aryl C—H Bonds by a Fujiwara—Moritani Reaction
Authors: Zhou Lihong , Lu Wenjun
Published: April 2014

Review: 11 refs.
ChemInform Abstract: Organic Electron Donors as Powerful Single‐Electron Reducing Agents in Organic Synthesis
Authors: Broggi Julie , Terme Thierry , Vanelle Patrice
Published: April 2014

Review: [177 refs.
ChemInform Abstract: New Site‐Selective Organoradical Based on Hypervalent Iodine Reagent for Controlled Alkane sp3 C—H Oxidations
Authors: Dohi Toshifumi , Kita Yasuyuki
Published: April 2014

Review: 38 refs.
ChemInform Abstract: Iron(III) Chloride Promoted Cyclization: A Facile Approach to Polycyclic Aromatics for Functional Materials
Authors: Cao Yue , Wang Xiao‐Ye , Wang Jie‐Yu , Pei Jian
Published: April 2014

Review: [32 refs.
ChemInform Abstract: Chemical Constituents of the Plants from the Genus Oplopanax
Authors: Huang Wei‐Hua , Zhang Qing‐Wen , Yuan Chun‐Su , Wang Chong‐Zhi , Li Shao‐Ping , Zhou Hong‐Hao
Published: April 2014

Review: 86 refs.
ChemInform Abstract: Synthesis of D‐Galactofuranose‐Containing Molecules: Design of Galactofuranosyl Acceptors
Authors: Marino Carla , Baldoni Luciana
Published: April 2014

Review: 102 refs.
ChemInform Abstract: Hydroformylation in the Realm of Scents
Authors: Gusevskaya Elena V. , Jimenez‐Pinto Jhonny , Boerner Armin
Published: April 2014

Review: 200 refs.
ChemInform Abstract: Piperylene — A Versatile Basic Chemical in Catalysis
Authors: Behr Arno , Neubert Peter
Published: April 2014

Review: 165 refs.
ChemInform Abstract: Poly(ethylene glycol)‐Based Ionic Liquids: Properties and Uses as Alternative Solvents in Organic Synthesis and Catalysis
Authors: Cecchini Martina Maya , Charnay Clarence , De Angelis Francesco , Lamaty Frederic , Martinez Jean , Colacino Evelina
Published: April 2014

Review: 83 refs.
ChemInform Abstract: Environmentally Benign Syntheses of α‐Substituted Phosphonates: Preparation of α‐Amino‐ and α‐Hydroxyphosphonates in Water, in Ionic Liquids, and under Solvent‐Free Conditions
Authors: Olszewski Tomasz K.
Published: April 2014

Review: [82 refs.
ChemInform Abstract: Synthesis and Biological Applications of Selenoureas
Authors: Hussain Raja Azadar , Badshah Amin , Shah Afzal
Published: April 2014

Review: 101 refs.
ChemInform Abstract: Hosts for High‐Performance Phosphorescent Organic Light‐Emitting Diodes Based on Carbazole Derivatives
Authors: Jiang Hongji
Published: April 2014

Review: up‐to‐date methods for chemical modifications to obtain hosts for high‐performance PHOLEDs based on carbazole derivatives; 66 refs.
ChemInform Abstract: Processes to Separate Enantiomers
Authors: Lorenz Heike , Seidel‐Morgenstern Andreas
Published: April 2014

Review: [enantioselective crystallization, preparative chromatography or a combination of both processes; 315 refs.
ChemInform Abstract: Synthesis of the C18‐Norditerpenoid Alkaloid Neofinaconitine: A Lesson in Convergent Synthesis Planning
Authors: Liu Xiao‐Yu , Chen David Y.‐K.
Published: April 2014

Review: 20 refs.
ChemInform Abstract: Nanoparticles in the Supramolecular Order of Discotic Liquid Crystals
Authors: Kumar Sandeep
Published: April 2014

Review: 115 refs.
ChemInform Abstract: Chirality‐Driven Wettability Switching and Mass Transfer
Authors: Qing Guangyan , Sun Taolei
Published: April 2014

Review: [16 refs.
ChemInform Abstract: Recent Progress in Quantifying Substituent Effects
Authors: Cao ChenZhong , Wu YaXin
Published: April 2014

Review: 152 refs.
ChemInform Abstract: Heteronuclear Spin Decoupling in Solid‐State Nuclear Magnetic Resonance: Overview and Outlook
Authors: Madhu P. K.
Published: April 2014

Review: 52 refs.
Getting to the Source: Selective Drug Targeting of Cancer Stem Cells
Authors: Ismail Fatima , Winkler David A.
Published: April 2014

Cancers are among the most important and most difficult to treat diseases of the 21st century. Conventional therapies include surgery, immunotherapy, and radiotherapy, as well many forms of drug treatments such as tamoxifen and Gleevec. However, these forms of treatment often do not eradicate the cancer stem cells, only managing to decrease the size of the tumor, allowing the cancer to return. The cancer stem cell hypothesis stipulates that malignancy is maintained through self‐renewal of cancer stem cells (CSCs), which generate rapidly dividing progeny that comprise the tumors, and that are largely untouched by conventional therapies. Evidence for the central role of CSCs in many tumors has provided a paradigm shift in the way cancer chemotherapy may be addressed. Recent discoveries regarding the nature of the stem cell niche, and the key signaling pathways involved in stem cell self‐renewal and differentiation from regenerative medicine, have provided key information that facilitates selective targeting of CSCs by small‐molecule drugs. The growing body of biochemical knowledge on the nature of CSCs, and differences between them and normal adult stem cells essential for maintaining organisms, has augmented the increasing number of small molecules shown to control normal and aberrant stem cells. Here, we review small‐molecule approaches to the selective targeting of CSCs.
Photodelivery of CO by Designed PhotoCORMs: Correlation between Absorption in the Visible Region and Metal–CO Bond Labilization in Carbonyl Complexes
Authors: Chakraborty Indranil , Carrington Samantha J. , Mascharak Pradip K.
Published: April 2014

The therapeutic potential of photoactive CO‐releasing molecules (photoCORMs) have called for close examination of the roles of the ligand(s) and the central metal atoms on the overall photochemical labilization of the metal–CO bonds. Along this line, we have synthesized four metal complexes, namely, [MnBr(azpy)(CO)3] (1), [Mn(azpy)(CO)3(PPh3)]ClO4 (2), [ReBr(azpy)(CO)3] (3), and [Re(azpy)(CO)3(PPh3)]ClO4 (4), derived from 2‐phenylazopyridine. These complexes were characterized by spectroscopic and crystallographic studies. Although both 1 and 3 exhibit strong metal‐to‐ligand charge‐transfer bands in the 500–600 nm region, only 1 photoreleases CO upon illumination with visible light. Results of theoretical studies were used to gain insight into this surprising difference. Strong spin‐orbit coupling (prominent in heavy metals) appears to promote intersystem crossing to a triplet state in 3, a step that discourages CO release upon illumination with visible light. Slow release of CO from 2 and 4 also indicates that strong σ‐donating ligands, such as Br−, accelerate the rate of CO photorelease relative to π‐acid ligands, such as PPh3.
Potential for cell therapy in Parkinson's disease using genetically programmed human embryonic stem cell–derived neural progenitor cells
Authors: Ambasudhan Rajesh , Dolatabadi Nima , Nutter Anthony , Masliah Eliezer , Mckercher Scott R. , Lipton Stuart A.
Published: April 2014

Neural transplantation is a promising strategy for restoring dopaminergic dysfunction and modifying disease progression in Parkinson's disease (PD). Human embryonic stem cells (hESCs) are a potential resource in this regard because of their ability to provide a virtually limitless supply of homogenous dopaminergic progenitors and neurons of appropriate lineage. The recent advances in developing robust cell culture protocols for directed differentiation of hESCs to near pure populations of ventral mesencephalic (A9‐type) dopaminergic neurons has heightened the prospects for PD cell therapy. Here, we focus our review on current state‐of‐the‐art techniques for harnessing hESC‐based strategies toward development of a stem cell therapeutic for PD. Importantly, we also briefly describe a novel genetic‐programming approach that may address many of the key challenges that remain in the field and that may hasten clinical translation. J. Comp. Neurol. 522:2845–2856, 2014. © 2014 Wiley Periodicals, Inc.
Thermodynamics of Micellization from Heat‐Capacity Measurements
Authors: Šarac Bojan , Bešter‐Rogač Marija , Lah Jurij
Published: April 2014

Differential scanning calorimetry (DSC), the most important technique for studying the thermodynamics of structural transitions of biological macromolecules, is seldom used in quantitative thermodynamic studies of surfactant micellization/demicellization. The reason for this could be ascribed to an insufficient understanding of the temperature dependence of the heat capacity of surfactant solutions (DSC data) in terms of thermodynamics, which leads to problems with the design of experiments and interpretation of the output signals. We address these issues by careful design of DSC experiments performed with solutions of ionic and nonionic surfactants at various surfactant concentrations, and individual and global mass‐action model analysis of the obtained DSC data. Our approach leads to reliable thermodynamic parameters of micellization for all types of surfactants, comparable with those obtained by using isothermal titration calorimetry (ITC). In summary, we demonstrate that DSC can be successfully used as an independent method to obtain temperature‐dependent thermodynamic parameters for micellization.
Probing the Influence of the Ligands on the Magnetism of Dinuclear Manganese, Iron, and Chromium Complexes Supported by Aroylhydrazone
Authors: Domingo Alex , Specklin David , Rosa Vitor , Mameri Samir , Robert Vincent , Welter Richard
Published: April 2014

The influence of aroylhydrazone and bridging ligands on the exchange coupling constant (J) of five dinuclear metal complexes is analyzed through ab initio calculations. The complete active space second‐order perturbation theory with localized orbitals offers not only estimates of J but also detailed information about the contributions of the molecular regions to the overall magnetism. This computational strategy is first validated for two previously reported ferromagnetic MnIII/MnIII and antiferromagnetic FeIII/FeIII complexes. Such calculations are extended to three new dinuclear complexes of MnIV, FeIII and CrIII constructed with a chemically simpler ligand (HL). We provide the synthesis and structural characterization (X‐ray diffraction crystallography) of these three new compounds. The HL ligand exhibits little electronic influence over the J value, but it directs the magnetic properties of the compound by conditioning the relative arrangement of the metal centres.
Selective Synthesis of Unsymmetrical Diboryl PtII and Diaminoboryl CuI Complexes by B–B Activation of Unsymmetrical Diboranes(4) {pinB–B[(NR)2C6H4]}
Authors: Borner Corinna , Kleeberg Christian
Published: April 2014

Diaminoboryl ligands are currently intensively investigated because of their unique coordination chemical properties, for example, as part of pincer ligands. Owing to synthetic restrictions, however, access to diaminoboryl complexes is limited. Unsymmetrical diborane(4) derivatives comprising a dialkoxy‐ and a diaminoboron moiety provide efficient access to diaminoboryl complexes either by oxidative addition or by σ‐bond metathesis reactions. Especially, the latter is complementary to existing methods and overcomes the existing limitations. This is illustrated by the modular synthesis of four unsymmetrical diborane(4) derivatives and their application in the selective preparation of unprecedented unsymmetrical diboryl PtII complexes as well as sterically little encumbered diaminoboryl CuI complexes.
Highly Stereoselective aza‐Baylis–Hillman Reactions of CF3‐Sulfinylimines: Straightforward Access to α‐Methylene β‐CF3 β‐Amino Acids
Authors: Milcent Thierry , Hao Jing , Kawada Kosuke , Soloshonok Vadim A. , Ongeri Sandrine , Crousse Benoit
Published: April 2014

1,4‐Diazabicyclo[2.2.2]octane‐catalyzed asymmetric aza‐Baylis–Hillman (ABH) reaction of (R)‐N‐tert‐butanesulfinyl‐(3,3,3)‐trifluoroacetaldimine with various Michael acceptors proceeds with exceptionally high rates and stereochemical outcome. This ABH approach provides convenient and practical access to previously unknown enantiomerically pure α‐methylene β‐CF3 β‐amino esters/acids, forthright useable for peptide synthesis.
Resveratrol reduces morphine tolerance by inhibiting microglial activation via AMPK signalling
Authors: Han Y. , Jiang C. , Tang J. , Wang C. , Wu P. , Zhang G. , Liu W. , Jamangulova N. , Wu X. , Song X.
Published: April 2014

Background

Evidence has accumulated indicating that microglia within the spinal cord play a critical role in morphine tolerance. The present study investigated the effects and possible mechanisms of 5′ adenosine monophosphate‐activated protein kinase (AMPK) activator resveratrol and AICAR to inhibit microglial activation and to limit the decrease in antinociceptive effects of morphine.

Methods

The microglial cell line BV‐2 was used. Cytokine expression was measured using quantitative polymerase chain reaction. Cell signalling was assayed by Western blot and immunohistochemistry. The antinociception and morphine tolerance were assessed in CD‐1 mice using the hot plate and tail‐flick tests.

Results

(1) Morphine induces robust BV‐2 cell activation, as evidenced by increased p38 mitogen‐activated protein kinase phosphorylation, nuclear factor‐κB translocation and mRNA expression of pro‐inflammatory cytokines [including interleukin‐1β (IL‐1β), IL‐6 and tumour necrosis factor‐α], inducible nitric oxide synthase and Toll‐like receptor‐4, and these changes are inhibited by resveratrol. (2) Resveratrol activates AMPK to suppress morphine‐induced BV‐2 cell activation. AICAR, another AMPK activator, can mimic the effects of resveratrol, whereas compound C, an AMPK inhibitor, reverses the inhibitory effects of resveratrol treatment. (3) Systemic or spinal administration of resveratrol with morphine significantly blocks microglial activation in the spinal cord and then attenuates the development of acute and chronic morphine tolerance in both male and female mice.

Conclusion

Resveratrol directly suppresses morphine‐induced microglial activation through activating AMPK, resulting in significant attenuation of morphine antinociceptive tolerance.
Intrathecal administration of botulinum toxin type A improves urinary bladder function and reduces pain in rats with cystitis
Authors: Coelho A. , Oliveira R. , Rossetto O. , Cruz C.D. , Cruz F. , Avelino A.
Published: April 2014

Background

Botulinum toxin A (Onabot/A) has been shown to have an antinociceptive effect. This might be due to an impairment of sensory nerves not only in the peripheral but also in the central nervous system. In this work, we analysed both systems by studying the effect of intrathecal (i.t.) administration of botulinum toxin A in an animal model of bladder pain and hyperactivity induced by cyclophosphamide (CYP).

Methods

Rats were implanted with an i.t. catheter at the L6 segment. Bladder pain was induced by intraperitoneal (i.p.) injection of CYP. Five experimental groups were created: (1) Saline i.p. + i.t.; (2) Onabot/A i.t.; (3) CYP i.p. + saline i.t.; (4) CYP i.p. + Onabot/A i.t. 48 h after CYP; and (5) Onabot/A i.t. 30 days. Mechanical sensitivity was assessed in the abdomen and hindpaws. Motor activity was observed in an open‐field arena. Bladder reflex activity was evaluated by cystometry. At the end, bladders and spinal cord were immunoreacted (IR) against cleaved SNAP‐25 (cSNAP‐25), c‐Fos, p‐ERK, calcitonin gene‐related peptide (CGRP) and GAP43.

Results

The toxin reduced pain symptoms, bladder hyperactivity, expression of neuronal activation markers and CGRP, typically up‐regulated in this inflammatory model. The presence of cSNAP‐25 was detected in the spinal cord and bladder fibres from animals treated with Onabot/A. No somatic or visceral motor impairments were observed.

Conclusions

Our findings suggest that i.t. Onabot/A has a strong analgesic effect in a model of severe bladder pain. This route of administration can be further explored to treat intractable forms of pain.
Longitudinal effects of intravenous immunoglobulin on Alzheimer's cerebrospinal fluid proteome
Authors: Shayan Gilda , Adamiak Basia , Choe Leila H. , Relkin Norman , Lee Kelvin H.
Published: April 2014

Intravenous immunoglobulin (IVIg) therapy has shown promise in the treatment of Alzheimer's disease (AD). In this study, serial cerebrospinal fluid (CSF) samples from a group of subjects with AD undergoing IVIg immunotherapy are analyzed to identify IVIg‐related changes. CSF samples from eight subjects were collected before therapy, after 6 months of therapy, and after a 3‐month drug washout period. Samples were analyzed using a gel‐based proteomics strategy and IVIg‐related changes were determined by gel spot percent volumes. An initial assessment of the data revealed consistent and considerable change in 69 spots. A statistical analysis revealed 79 protein spots with a significant change after 6 months; furthermore, in a subset of these (25), the percent volume change was either maintained or reversed in the washout samples. The proteins that showed a significant change during IVIg therapy, including Ig molecules, gelsolin, transferrin, and transthyretin, have been previously implicated in AD. This study provides preliminary findings regarding a group of CSF proteins that may be associated with the treatment of AD, as well as the potential use of IVIg as an AD immunotherapy.
The erosive growth of hillside gullies
Authors: Rose Calvin W. , Yu Bofu , Ward Douglas P. , Saxton Nina E. , Olley Jon M. , Tews Errol K.
Published: April 2014

The rate of erosion of hillside gullies depends both on gully flow characteristics and the resistance offered by the gully soil profile to erosion. This paper describes a method for quantifying a physically‐based resistance measure, illustrated by application to a gully feeding sediment into the Bremer River, southeast Queensland, Australia. The dynamics of discharge down the gully during runoff events is the driver of erosion, but this was unknown. A new method is described whereby this unmeasured flow can be estimated using data on rainfall rate and river gauge monitoring.

The data collected on the gully was the increase in dimensions and volume (and so soil loss) over a two year period. This information was obtained from a digital elevation model (DEM) of the catchment, derived from Light Detection and Ranging (LiDAR) observations made at either end of the two year period. The soil profile resistance characteristic evaluated is the energy required to erode a unit mass of soil from the gully walls, a physically‐defined parameter, J, present in flow‐driven erosion theory, which was adapted and applied to predict soil loss from the Bremer River gully. The value of J was evaluated by equating predicted to measured gully soil loss over the two year period using two alternative descriptions of gully cross‐section. Firstly a realistic gully shape description was used, made possible by LiDAR data, yielding J = 405.5 J/kg. Secondly, in order to allow use of more widely‐available aerial photography for such studies, the simplifying assumption of a semi‐circular gully shape was made, yielding J = 455 J/kg. Allowing a ±30% error in estimated effective runoff rate for this ungauged gully, the estimated J value would have an uncertainty of +1%/−7% using the actual gully geometry. The assumptions made in estimating J are discussed, and possible applications of this information listed. Copyright © 2014 John Wiley & Sons, Ltd.
Cortisol administration increases hippocampal activation to infant crying in males depending on childhood neglect
Authors: Bos Peter A. , Montoya Estrella R. , Terburg David , van Honk Jack
Published: April 2014

Animal studies show that exposure to parental neglect alters stress regulation and can lead to neural hyposensitivity or hypersensitivity in response to cortisol, most pronounced in the hippocampus. Cortisol, the end product of the hypothalamic‐pituitary‐adrenal (HPA) axis, has also been related to parenting more directly, for example, in both sexes, cortisol levels increase when listening to infants crying, possibly to activate and facilitate effective care behavior. Severe trauma is known to negatively affect the HPA‐axis in humans; however, it is unknown whether normal variation in parental care in the healthy population can alter sensitivity of the hippocampus to cortisol. Here, we investigate whether variation in experienced neglect changes neural sensitivity to cortisol when humans listen to infant crying, which is an unequivocal signal relevant for care behavior. In a placebo‐controlled, within‐subject neuroimaging study, we administered 40 mg cortisol to 21 healthy young males without children and used a validated task for measuring neural responses to infant crying. The Dutch version of the Childhood Trauma Questionnaire was used to index participants' early exposure to abuse and neglect. The data show that cortisol markedly increased hippocampal activation toward crying infants, and this effect varied significantly with parental neglect, even in our nonclinical subject sample. Without exposure to severe trauma or neglect, reduced self‐experienced quality of parental care in the normal range already substantially increased hippocampal responsivity to cortisol. Altered hippocampal sensitivity to cortisol might be a cross‐species marker for the risk of developing later life psychopathology. Hum Brain Mapp 35:5116–5126, 2014. © 2014 Wiley Periodicals, Inc.
Human OX40 tunes the function of regulatory T cells in tumor and nontumor areas of hepatitis C virus–infected liver tissue
Authors: Piconese Silvia , Timperi Eleonora , Pacella Ilenia , Schinzari Valeria , Tripodo Claudio , Rossi Massimo , Guglielmo Nicola , Mennini Gianluca , Grazi Gian Luca , Di Filippo Simona , Brozzetti Stefania , Fazzi Katia , Antonelli Guido , Lozzi Maria Antonietta , Sanchez Massimo , Barnaba Vincenzo
Published: April 2014

Regulatory T cells (Tregs) can be considered as a mixed population of distinct subsets, endowed with a diverse extent and quality of adaptation to microenvironmental signals. Here, we uncovered an opposite distribution of Treg expansion, phenotype, and plasticity in different microenvironments in the same organ (liver) derived from patients with chronic hepatitis C: On the one side, cirrhotic and tumor fragments were moderately and highly infiltrated by Tregs, respectively, expressing OX40 and a T-bethighIFN-γ– “T-helper (Th)1-suppressing” phenotype; on the other side, noncirrhotic liver specimens contained low frequencies of Tregs that expressed low levels of OX40 and highly produced interferon-gamma (IFN-γ; T-bet+IFN-γ+), thus becoming “Th1-like” cells. OX40-expressing and Th1-suppressing Tregs were enriched in the Helios-positive subset, carrying highly demethylated Treg cell-specific demethylated region that configures committed Tregs stably expressing forkhead box protein 3. OX40 ligand, mostly expressed by M2-like monocytes and macrophages, boosted OX40+ Treg proliferation and antagonized the differentiation of Th1-like Tregs. However, this signal is counteracted in noncirrhotic liver tissue (showing various levels of inflammation) by high availability of interleukin-12 and IFN-γ, ultimately leading to complete, full Th1-like Treg differentiation.

Conclusion

: Our data demonstrate that Tregs can finely adapt, or even subvert, their classical inhibitory machinery in distinct microenvironments within the same organ. (Hepatology 2014;60:1494–1507)
Inter‐annual variation in the topographic controls on catchment‐scale snow distribution in a maritime alpine catchment, New Zealand
Authors: Webster Clare S. , Kingston Daniel G. , Kerr Tim
Published: April 2014

Seasonal snow is a globally important water resource that contributes substantially to upland and lowland water resources. As such, there is a need to understand the controls on the spatial and temporal variation in snow distribution. This study meets this research need by investigating the topographic controls on snow depth distribution in the upper Jollie catchment in the Southern Alps of New Zealand. Furthermore, inter‐annual variation in the importance of the topographic controls is examined and linked to variation in the dominant synoptic‐scale weather patterns over a 4‐year period (2007–2010). Through the use of regression trees, the relative importance of the topographic controls on snow depth was shown to vary between the four study years. In particular, elevation explained the greatest amount of variance in 2007 and 2008 and east‐exposure explained the greatest variance in 2009 and 2010. The other wind exposure variables also had a large effect on the snow depth distribution in 2009 and 2010. Differences in the frequency and duration of synoptic weather patterns were physically consistent with the changing importance of these variables. In particular, a higher frequency of troughing events in 2009 and 2010 is thought to be associated with a reduced importance of elevation and greater influence of wind exposure on snow depth in these years. These findings demonstrate the importance of using multi‐year data sets, and of considering topographic and climatic influences, when attempting to model alpine snow distribution. Copyright © 2014 John Wiley & Sons, Ltd.
Air‐stream temperature correlation in forested and urban headwater streams in the Southern Appalachians
Authors: Gu Chuanhui , Anderson William P. , Colby Jeffrey D. , Coffey Christopher L.
Published: April 2014

Air temperature can be an effective predictor of stream temperature. However, little work has been done in studying urban impacts on air‐stream relationships in groundwater‐fed headwater streams in mountainous watersheds. We applied wavelet coherence analysis to two 13‐month continuous (1 hr interval) stream and air temperature datasets collected at Boone Creek, an urban stream, and Winkler Creek, a forest stream, in northwestern North Carolina. The main advantage of a wavelet coherence analysis approach is the ability to analyse non‐stationary dynamics for the temporal covariance between air and stream temperature over time and at multiple temporal scales (e.g. hours, days, weeks and months). The coherence is both time and scale‐dependent. Our research indicated that air temperature generally co‐varied with stream temperature at time scales greater than 0.5 day. The correlation was poor during the winter at the scales of 1 to 64 days and summer at the scales of 1.5 to 4 days, respectively. The empirical models that relate air temperature to stream temperature failed at these scales and during these periods. Finally, urbanization altered the air‐stream temperature correlation at intermediate time scales ranging from 2 to 12 days. The correlation at the urban creek increased at the 12‐day scale, whereas it decreased at scales of 2 to 7 days as compared with the forested stream, which is probably due to heated surface runoff during summer thunderstorms or leaking stormwater or wastewater collection systems. Our results provide insights into air‐stream temperature relationships over both time and scale domains. Identifying controls over time and scales are needed to predict water temperature to understand the future impacts that interacting climate and land use changes will have on aquatic ecosystem in river networks. Copyright © 2014 John Wiley & Sons, Ltd.
Novel Target Genes of RUNX2 Transcription Factor and 1,25‐Dihydroxyvitamin D3
Authors: Stephens Alexandre S. , Morrison Nigel A.
Published: April 2014

The RUNX2 transcription factor is indispensable for skeletal development and controls bone formation by acting as a signaling hub and transcriptional regulator to coordinate target gene expression. A signaling partner of RUNX2 is the nuclear vitamin D receptor (VDR) that becomes active when bound by its ligand 1,25‐dihydroxyvitamin D3 (VD3). RUNX2 and VDR unite to cooperatively regulate the expression of numerous genes. In this study, we overexpressed RUNX2 in NIH3T3 fibroblasts concomitantly treated with VD3 and show that RUNX2 alone, or in combination with VD3, failed to promote an osteoblastic phenotype in NIH3T3 cells. However, the expression of numerous osteoblast‐related genes was up‐regulated by RUNX2 and large‐scale gene expression profiling using microarrays identified over 800 transcripts that displayed a twofold of greater change in expression in response to RUNX2 overexpression or VD3 treatment. Functional analysis using gene ontology (GO) revealed GO terms for ossification, cellular motility, biological adhesion, and chromosome organization were enriched in the pool of genes regulated by RUNX2. For the set of genes whose expression was modulated by VD3, the GO terms response to hormone stimulus, chemotaxis, and metalloendopeptidase activity where overrepresented. Our study provides a functional insight into the consequences of RUNX2 overexpression and VD3 treatment in NIH3T3 cells in addition to identifying candidate genes whose expression is controlled by either factor individually or through their functional cooperation. J. Cell. Biochem. 115: 1594–1608, 2014. © 2014 Wiley Periodicals, Inc.
NaBH4/Ac2O/DOWEX(R)50WX4: A Convenient System for Fast Preparation of gem‐Diacetates from Aldehydes
Authors: Asl Parisa Azizi , Setamdideh Davood
Published: April 2014

Reductive‐acylalation of aldehydes has been carried out by NaBH4/Ac2O/DOWEX(R)50WX4 system. A variety of aldehydes (1 mmol) have been reacted with Ac2O (0.5 mL) and NaBH4 (1 mmol) in the presence of DOWEX(R)50WX4 (0.5 g) for the preparation of their corresponding acylals within 1 min at room temperature with excellent yields of the products (90‐95%). Ketones do not react with this system.
Green Photochemical Processes and Technologies for Research & Development, Scale‐up and Chemical Production
Authors: Oelgemöller Michael
Published: April 2014

Photochemistry is often viewed as a green chemical method since photons are regarded as a ‘clean and traceless reagent’. Despite this, photochemical transformations generally suffer from a variety of ‘non‐green’ drawbacks that have prevented their widespread adaptation in chemical manufacturing. These include the necessity for hazardous solvents, low quantum yields of photochemical transformations, high energy demands of traditional lamps and the need for high dilution due to the low penetration of light into the reaction mixture. As a result, photochemical operations generate large volumes of hazardous solvent waste, demand prolonged irradiation times and require high energy inputs. This highlight article shows recent examples of green photochemical processes and technologies that overcome these limitations. These include photodecarboxylations in water matrices with high quantum yields in an advanced 308‐nm excimer falling film reactor, solar photooxygenations utilizing concentrated sunlight generated in a parabolic trough loop and photosensitized additions in resource‐efficient microreactors under continuous flow conditions. The results show that photochemistry can be implemented as a truly green methodology across the entire chemical process spectrum from early R&D to scale‐up and subsequently production.
Note on the blow‐lamp method of detecting organic halogen compounds in the air
Authors: Timmis L. B.
Published: April 2014

An ordinary petrol blow lamp burning light petroleum serves to detect, by the coloration of the flame, low concentrations of organic halogen vapours in the surrounding air, and for this purpose it may be used instead (if the special alcohol lamp standardised by D.S.I.R. Within certain ranges the concentration may be roughly estimated, and figures are given for trichloroethylene, carbon tetrachloride, and “Freon.”
The determination of aniline in alkylanilines
Authors: Spencer G. , Brimley J. E.
Published: April 2014

The picryl chloride method for the determination of aniline in some alkylanilines has been investigated in detail and a very rapid and satisfactory method evolved. Picryl chloride and aniline react with elimination of a molecule of hydrochloric acid, which can lie determined by titration with caustic soda, and satisfactory procedures for varying amounts of undine in Home of the commoner alkylanilines have been worked out.
Dried egg. The relationship of analysis to flavour
Authors: Fryd C. F. M. , Hanson S. W. F.
Published: April 2014

The methods used by the Government Laboratory in the examination of dried egg during the period from 1942 to the present day are described, including the use of physical and chemical properties for calculating a numerical equivalent of the flavour score, A revised equation is given, which brings all known forms of deterioration in spray‐dried egg within the scope of this calculation.
Simplified procedure for estimation of total carotenoids in carrots
Authors: Booth V. H.
Published: April 2014

Two simple methods for the removal of small representative samples from carrots are described: (a) in the sector method narrow sectors are out and weighed; (b) in the cylinder method small rods are bored out and measured. The latter method is suitable for sampling in the field; the roots survive and may be replanted and grown on for seed production. A simplified and rapid procedure for the estimation of total carotenoids in the samples is described. The pigments are extracted with cold light petroleum‐acetone, and colorimetric determinations made directly on this solution. Carotene averages M% of the total carotenoids in mature carrots.
Vitamin‐C content of vegetables. Part II. Effect of storage on raw vegetables
Authors: Lampitt L. H. , Baker L. C. , Parkinson T. L.
Published: April 2014

The storage of lettuce, broccoli, cabbage and spinach at room temperature resulted in loss of vitamin‐C at different rates. These rates were greatly reduced by lowering the storage temperature to 3°c., in fact at 3°c. increases in the amount of vitamin‐C present in lettuce, broccoli and cabbage were actually observed during the first 2 days of the storage period. There appeared to be some correlation between the loss of vitamin‐C on storing and the general withering and deterioration in the appearance of the vegetable.
Hydroxybenzyl alcohols from phenol form‐aldehyde resins
Authors: Ruderman I. W.
Published: April 2014

Crystalline deposits were found to have sublimed in the exhaust stacks of tunnel dryers when paper or cloth impregnated with a commercial phenol‐formaldehyde ammonia‐catalysed resin was dried. Analysis of these deposits led to the isolation and identification of o‐ and p‐hydroxy‐benzyl alcohol. The isolation of those intermediates by sublimation from resins has not been reported before.
The use of low‐temperature crystallisation in the determination of component acids of liquid fats. I. fats in which oleic and linoleic acids are major components
Authors: Hilditch T. P. , Riley J. P.
Published: April 2014

Preliminary separation of mixed fatty acids by crystallisation from solvents at low temperatures, according to the technique of J. B. Brown1 and his colleagues, is preferable to lead salt separation in the cases of fats which contain only small proportions of saturated acids. The procedure, coupled with subsequent ester‐fractionation, has been applied to the acids of sunflower seed, sesame, and groundnut oils (all of which have oleic and linoleic acids as their major components). The results agree well with earlier analyses in which lead salt separation had been employed. To some extent, acid fractions in which linoleic and oleic acids are respectively concentrated can also be obtained by the low‐temperature crystallisation procedure.