bluuebunny/crossref_metadata_2025 huggingface dataset:
ChemInform Abstract: Expedient Synthesis of Fused Azepine Derivatives Using a Sequential Rhodium(II)‐Catalyzed Cyclopropanation/1‐Aza‐Cope Rearrangement of Dienyltriazoles.
Authors: Schultz Erica E. , Lindsay Vincent N. G. , Sarpong Richmond
Published: February 2015

A general process for the cyclization of 1,2,3‐triazoles of type (I) and (III) having a tethered dienyl side chain is developed to provide the synthesis of fused dihydroazepines through a Rh‐catalyzed cyclopropanation/1‐aza‐Cope rearrangement.
ChemInform Abstract: Synthesis of Methyl 7,9‐Dimethyl‐5‐oxo‐2,3,4,5‐tetrahydro‐1H‐benzo[b]azepine‐1‐carboxylate and Its Analogues.
Authors: Vaid Radhe K. , Boini Sathish K. , Alt Charles A. , Spitler Jeremy T. , Hadden Chad E. , Frank Scott A. , Moher Eric D.
Published: February 2015

The synthesis of (Ia) on an industrial scale is elaborated and applied to the preparation of (Ib,c) and (II).
ChemInform Abstract: Short Synthesis of Enantiopure Thieno[2,3‐f]triazolo[1,5‐a][1,4]diazepines and Thieno[2,3‐f][1,4]diazepin‐5‐ones.
Authors: Molteni Giorgio
Published: February 2015

The title compounds (IV) and (VII) are obtained in two steps starting from 2‐carboxy‐3‐thenylazide (I) and enantiopure amines as chiral building blocks involving an intramolecular azide cycloaddition as the key step.
ChemInform Abstract: Phosphine‐Catalyzed anti‐Carboboration of Alkynoates with Alkyl‐, Alkenyl‐, and Arylboranes.
Authors: Nagao Kazunori , Ohmiya Hirohisa , Sawamura Masaya
Published: February 2015

The transformation of the 2‐tolyl substituted analogue of the phenyl alkynoate (III) requires 100 °C to provide a moderate yield of the corresponding sterically congested alkylborane.
ChemInform Abstract: Copper(I)‐Catalyzed Highly Regio‐ and Stereoselective Hydrosilylation of Terminal Alkynes with Boryldisiloxane.
Authors: Zhou Hui , Wang Yan‐Bo
Published: February 2015

Terminal alkynes regio‐ and stereoselectively undergo hydrosilylation with 1,3‐(pinacolboryl)disiloxane (I) as a novel silicon source.
ChemInform Abstract: Two New Acidic Diterpenoids from the Heartwood of Pinus massoniana Lamb.
Authors: Abd. Mohamed H. , Hsieh Chin‐Lin , Hsu Chin , Kuo Ching‐Chuan , Chang Hsuan‐Shuo , Lee Ching‐Kuo , Lee Tzon‐Huei , Wu Jin‐Bin , Chang Chi‐I , Kuo Yueh‐Hsiung
Published: February 2015

isolation and structure determination of a new abietane diterpene, named abietopinoic acid (I), and a new podocarpane diterpene, podopinoic acid (II)
ChemInform Abstract: Interaction of 16‐Hydroxymethylidene Derivatives of Androstane and Estrone with Thiohydrazides of Oxamic Acids.
Authors: Zavarzin I. V. , Antonov Ya. S. , Chernoburova E. I. , Shchetinina M. A. , Kolotyrkina N. G. , Shashkov A. S.
Published: February 2015

The title reaction leads to thiohydrazones which cyclize in situ in refluxing AcOH furnishing thiadiazole derivatives (IV) and (V) in good yield.
ChemInform Abstract: FeCl3·6H2O/C: An Efficient and Recyclable Catalyst for the Synthesis of 2,3‐Unsaturated O‐and S‐Glycosides.
Authors: Zhou Jiafen , Chen Heshan , Shan Junjie , Li Juan , Yang Guofang , Chen Xuan , Xin Kunyun , Zhang Jianbo , Tang Jie
Published: February 2015

FeCl3·6H2O/C is used as catalyst for the synthesis of 35 2,3‐unsaturated O‐and S‐glycosides.
ChemInform Abstract: Brocaeloids A—C, 4‐Oxoquinoline and Indole Alkaloids with C‐2 Reversed Prenylation from the Mangrove‐Derived Endophytic Fungus Penicillium brocae.
Authors: Zhang Peng , Meng Ling‐Hong , Mandi Attila , Kurtan Tibor , Li Xiao‐Ming , Liu Yang , Li Xin , Li Chun‐Shun , Wang Bin‐Gui
Published: February 2015

The three new brocaeloids (I)‐(III) are isolated from the cultures of penicillium brocae MA‐192.
ChemInform Abstract: New Lignans from the Leaves and Stems of Schisandra chinensis and Their anti‐HIV‐1 Activities.
Authors: Shi Yiming , Zhong Weimao , Chen Huan , Wang Ruirui , Shang Shanzhai , Liang Chengqin , Gao Zhonghua , Zheng Yongtang , Xiao Weilie , Sun Handong
Published: February 2015

Six new lignans (I), (II), (III), and (IV) are isolated along with five known ones from the leaves and stems of Schisandra chinensis.
ChemInform Abstract: NMR Studies of Actinide Oxides ‐ A Review
Authors: Walstedt Russell E. , Tokunaga Yo , Kambe Shinsaku
Published: February 2015

Review: 40 refs.
ChemInform Abstract: Recent Advances of Desymmetrization Protocol Applied in Natural Product Total Synthesis
Authors: Wang Ming , Feng Minghao , Tang Bingqing , Jiang Xuefeng
Published: February 2015

Review: [66 refs.
ChemInform Abstract: Thiyl Radicals: From Simple Radical Additions to Asymmetric Catalysis
Authors: Subramanian Hariharaputhiran , Moorthy Ramkumar , Sibi Mukund P.
Published: February 2015

Review: 8 refs.
ChemInform Abstract: Natural Products with anti‐Bredt and Bridgehead Double Bonds
Authors: Mak Jeffrey Y. W. , Pouwer Rebecca H. , Williams Craig M.
Published: February 2015

Review: [172 refs.
ChemInform Abstract: Increasing the Reactivity of Amides Towards Organometallic Reagents: An Overview
Authors: Pace Vittorio , Holzer Wolfgang , Olofsson Berit
Published: February 2015

Review: 151 refs.
ChemInform Abstract: The Synthesis of Enantioenriched α‐Hydroxy Esters
Authors: Gu Xin , Wang Lan , Gao Yong‐fei , Ma Wei , Li Ya‐ming , Gong Pin
Published: February 2015

Review: 35 refs.
ChemInform Abstract: Recent Advances in the Synthesis of 2‐Substituted Benzothiazoles: A Review
Authors: Prajapati Neelam P. , Vekariya Rajesh H. , Borad Mayuri A. , Patel Hitesh D.
Published: February 2015

Review: 184 refs.
ChemInform Abstract: The Chemistry and Biological Activities of Natural Products from Northern African Plant Families: From Aloaceae to Cupressaceae
Authors: Ntie‐Kang Fidele , Yong Joseph N.
Published: February 2015

Review: 113 refs.
ChemInform Abstract: Siloxy Alkynes in Annulation Reactions
Authors: Qian Hui , Zhao Wanxiang , Sun Jianwei
Published: February 2015

Review: [29 refs.
ChemInform Abstract: A Journey to the Total Synthesis of Daptomycin
Authors: Lam Hiu Yung , Gaarden Rannveig Ingebrigtsen , Li Xuechen
Published: February 2015

Review: [30 refs.
ChemInform Abstract: Antitubercular Natural Terpenoids: Recent Developments and Syntheses
Authors: Sansinenea Estibaliz , Ortiz Aurelio
Published: February 2015

Review: 119 refs.
ChemInform Abstract: The Ever‐expanding Role of Asymmetric Covalent Organocatalysis in Scalable, Natural Product Synthesis
Authors: Abbasov Mikail E. , Romo Daniel
Published: February 2015

Review: 155 refs.
ChemInform Abstract: Recent Developments Towards the Synthesis of Varitriol: An Antitumour Agent from Marine Derived Fungus Emericella Variecolor
Authors: Majik Mahesh S. , Tilvi Supriya , Parvatkar Prakash T.
Published: February 2015

Review: 59 refs.
ChemInform Abstract: Natural Dibenzo‐α‐pyrones and Their Bioactivities
Authors: Mao Ziling , Sun Weibo , Fu Linyun , Luo Haiyu , Lai Daowan , Zhou Ligang
Published: February 2015

Review: 101 refs.
ChemInform Abstract: Combining the ′Two Worlds′ of Chemocatalysis and Biocatalysis Towards Multi‐Step One‐Pot Processes in Aqueous Media
Authors: Groeger Harald , Hummel Werner
Published: February 2015

Review: 30 refs.
ChemInform Abstract: Microwave Irradiation and Phase Transfer Catalysis in C‐, O‐ and N‐Alkylation Reactions
Authors: Keglevich Gyorgy , Grun Alajos , Balint Erika
Published: February 2015

Review: 78 refs.
ChemInform Abstract: Privileged Structures: Efficient Chemical “Navigators” Toward Unexplored Biologically Relevant Chemical Spaces
Authors: Kim Jonghoon , Kim Heejun , Park Seung Bum
Published: February 2015

Review: 104 refs.
ChemInform Abstract: Two‐Dimensional Soft Nanomaterials: A Fascinating World of Materials
Authors: Zhuang Xiaodong , Mai Yiyong , Wu Dongqing , Zhang Fan , Feng Xinliang
Published: February 2015

Review: 211 refs.
ChemInform Abstract: Metal Oxides and Polysaccharides: An Efficient Hybrid Association for Materials Chemistry
Authors: Boury B. , Plumejeau S.
Published: February 2015

Review: 270 refs.
ChemInform Abstract: Recent Progress on Supported Polyoxometalates for Biodiesel Synthesis via Esterification and Transesterification
Authors: Narkhede Nilesh , Singh Sukriti , Patel Anjali
Published: February 2015

Review: 110 refs.
ChemInform Abstract: Rules and Benefits of Life Cycle Assessment in Green Chemical Process and Synthesis Design: A Tutorial Review
Authors: Kralisch Dana , Ott Denise , Gericke Doerthe
Published: February 2015

Review: 133 refs.
ChemInform Abstract: Transiting from Adipic Acid to Bioadipic Acid. 1, Petroleum‐Based Processes
Authors: Bart Jan C. J. , Cavallaro Stefano
Published: February 2015

Review: 444 refs.
ChemInform Abstract: Novel Aromatic and Antiaromatic Systems
Authors: Breslow Ronald
Published: February 2015

Review: 48 refs.
Atomistic Modeling of IR Action Spectra Under Circularly Polarized Electromagnetic Fields: Toward Action VCD Spectra
Authors: Calvo Florent
Published: February 2015

The nonlinear response and dissociation propensity of an isolated chiral molecule, camphor, to a circularly polarized infrared laser pulse was simulated by molecular dynamics as a function of the excitation wavelength. The results indicate similarities with linear absorption spectra, but also differences that are ascribable to dynamical anharmonic effects. Comparing the responses between left‐ and right‐circularly polarized pulses in terms of dissociation probabilities, or equivalently between R‐ and S‐camphor to a similarly polarized pulse, we find significant differences for the fingerprint C = O amide mode, with a sensitivity that could be sufficient to possibly enable vibrational circular dichroism as an action technique for probing molecular chirality and absolute conformations in the gas phase. Chirality 27:253–261, 2015. © 2015 Wiley Periodicals, Inc.
Increased anxiety‐like behavior and selective learning impairments are concomitant to loss of hippocampal interneurons in the presymptomatic SOD1(G93A) ALS mouse model
Authors: Quarta Eros , Bravi Riccardo , Scambi Ilaria , Mariotti Raffaella , Minciacchi Diego
Published: February 2015

Amyotrophic lateral sclerosis (ALS), a fatal neurodegenerative disease primarily characterized by motor neuron death, causes damages beyond motor‐related areas. In particular, cognitive impairments and hippocampal damage have been reported in ALS patients. We investigated spatial navigation learning and hippocampal interneurons in a mutant SOD1(G93A) mouse (mSOD1) model of ALS. Behavioral tests were performed by using presymptomatic mSOD1 mice. General motor activity was comparable to that of wild‐type mice in the open‐field test, in which, however mSOD1 exhibited increased anxiety‐like behavior. In the Barnes maze test, mSOD1 mice displayed a delay in learning, outperformed wild‐type mice during the first probe trial, and exhibited impaired long‐term memory. Stereological counts of parvalbumin‐positive interneurons, which are crucial for hippocampal physiology and known to be altered in other central nervous system regions of mSOD1 mice, were also performed. At postnatal day (P) 56, the population of parvalbumin‐positive interneurons in mSOD1 mice was already reduced in CA1 and in CA3, and at P90 the reduction extended to the dentate gyrus. Loss of parvalbumin‐positive hippocampal interneurons occurred mostly during the presymptomatic stage. Western blot analysis showed that hippocampal parvalbumin expression levels were already reduced in mSOD1 mice at P56. The hippocampal alterations in mSOD1 mice could at least partly account for the increased anxiety‐like behavior and deficits in spatial navigation learning. Our study provides evidence for cognitive alterations and damage to the γ‐aminobutyric acid (GABA)ergic system in the hippocampus of murine ALS, thereby revealing selective deficits antecedent to the onset of motor symptoms. J. Comp. Neurol. 523:1622–1638, 2015. © 2015 Wiley Periodicals, Inc.
Density Functional Theory and Hydrogen Bonds: Are We There Yet?
Authors: Boese A. Daniel
Published: February 2015

Density functional theory (DFT) has become more successful at introducing dispersion interactions, and can be thus applied to a wide range of systems. Amongst these are systems that contain hydrogen bonds, which are extremely important for the biological regime. Here, the description of hydrogen‐bonded interactions by DFT with and without dispersion corrections is investigated. For small complexes, for which electrostatics are the determining factor in the intermolecular interactions, the inclusion of dispersion with most functionals yields large errors. Only for larger systems, in which van der Waals interactions are more important, do dispersion corrections improve the performance of DFT for hydrogen‐bonded systems. None of the studied functionals, including double hybrid functionals (with the exception of DSD‐PBEP86 without dispersion corrections), are more accurate than MP2 for the investigated species.
Enantioselective Epoxidation of Styrene by Manganese Chiral Schiff Base Complexes Immobilized on MCM‐41
Authors: Mandal Moon , Nagaraju Vemu , Sarma Bipul , Karunakar G. V. , Bania Kusum K.
Published: February 2015

Two chiral MnIII complexes synthesized and characterized by single‐crystal X‐ray diffraction were grafted onto mesoporous silica MCM‐41. The MCM‐41‐immobilized solid chiral catalysts were characterized by various spectrochemical and physicochemical methods (XRD, FTIR, 29Si NMR, TGA, UV/Vis/DRS, EPR, cyclic voltammetry, SEM, BET). Both the homogeneous and heterogeneous MnIII chiral complexes are found to be effective catalysts for epoxidation of styrene. MCM‐41‐supported chiral catalysts are found to retain their catalytic activity up to five cycles. When an ionic liquid was implemented to enhance the catalytic recyclability of the homogeneous catalysts, they can be recycled up to three times. However, after the third cycle the catalytic activities of the complexes were found to decrease due to rupturing of the chiral catalyst.
Service‐oriented 5G network architecture: an end‐to‐end software defining approach
Authors: Yang Mao , Li Yong , Li Bo , Jin Depeng , Chen Sheng
Published: February 2015

With the ever‐increasing mobile demands and proliferation of mobile services, mobile Internet has penetrated into every aspect of human life. Although the 4G mobile communication system is now being deployed worldwide, simply evolving or incrementally improving the current mobile networks can no longer keep the pace with the proliferation of mobile services. Against this background, aiming to achieve service‐oriented 5G mobile networks, this article proposes an end‐to‐end software defining architecture, which introduces a logically centralized control plane and dramatically simplifies the data‐plane. The control plane decomposes the diversified mobile service requirements and, correspondingly, controls the functions and behaviors of data‐plane devices. Consequently, the network directly orients towards services, and the devices are dynamically operated according to the service requirements. Therefore, the proposed architecture efficiently guarantees the end‐to‐end QoS and quality of experience. The challenges and key technologies of our architecture are also discussed in this article. Real traces‐based simulations validate the performance advantages of proposed architecture, including energy efficiency and the whole performance. Copyright © 2015 John Wiley & Sons, Ltd.
Support students with disabilities who transfer, both into and out of your institution
Authors: Gaddy Stephanie
Published: February 2015

While transfer rates vary across institutions, as many as one‐third of all college students may transfer from one institution to another within their college careers. Often, transfer students — whether they are coming into or leaving your institution — miss orientations for new students and information designed to get them acquainted with the disability services office. But all institutions are different. Offices serving students with disabilities can have different names, and their policies and procedures for securing services can vary widely.
Learn the ABCs of effective leadership
Authors: Hope Joan
Published: February 2015

As leader of your disability services department, it's imperative that your staff members see you as such. But being seen as a true leader is about more than simply a title. It's about how you behave.
Make sure your campus offers some accessible on‐street parking
Authors: Gomez Cynthia
Published: February 2015

Many colleges and universities situated in busy metropolitan areas have a limited number of parking lots, so students, faculty and staff may at times need to use on‐street parking.
Coordinative Flexibility of a Thiophenolate Oxazoline Ligand in Nickel(II), Palladium(II), and Platinum(II) Complexes
Authors: Peschel Lydia M. , Holzer Christof , Mihajlović‐Lalić Ljiljana , Belaj Ferdinand , Mösch‐Zanetti Nadia C.
Published: February 2015

The synthesis, full characterization, and molecular structures of seven new coordination compounds that feature the 2‐(4′,4′‐dimethyloxazolin‐2′‐yl)thiophenolate ligand (S‐Phoz) with group 10 metals Ni, Pd, and Pt in the +II oxidation state are presented. The ML2 complexes [Pt(S‐Phoz)2] (1a), [Pd(S‐Phoz)2] (1b), and [Ni(S‐Phoz)2] (2) were prepared starting from MCl2. Compound 1a was obtained isomerically pure in a trans arrangement, whereas its Pd analogue 1b exhibits a dynamic, solvent‐dependent cis/trans equilibrium, and 2 adopts a tetrahedral arrangement. The reaction of LiS‐Phoz with [cis‐MCl2(PPh3)2] precursors resulted in full replacement of the PPh3 for M = Ni and in partial substitution for M = Pt, Pd to yield [Ni(S‐Phoz)2] (2), [Pt(κ2‐S‐Phoz)(κ1‐S‐Phoz)(PPh3)] (3a), and [Pd(κ2‐S‐Phoz)(κ1‐S‐Phoz)(PPh3)] (3b). The Pd compound 3b exhibits an interesting solvent‐dependent equilibrium with 1b and PPh3 as demonstrated by 1H and 31P NMR spectroscopy. Compounds [{PdCl(S‐Phoz)}2] (4) and [PdCl(S‐Phoz)(PPh3)] (5) were synthesized from [PdCl2(NCMe)2]. Molecular structures of compounds trans‐1a, trans‐1b, 2, 3a, 3b, 4, and 5 were determined by single‐crystal X‐ray diffraction studies. With the exception of the Ni complex 2, all compounds exhibit distorted square‐planar geometries.
Electronic Structures of “Low‐Valent” Neutral Complexes [NiL2]0 (S = 0; L = bpy, phen, tpy) – An Experimental and DFT Computational Study
Authors: Wang Mei , England Jason , Weyhermüller Thomas , Wieghardt Karl
Published: February 2015

The electronic structures of the neutral complexes [Ni(bpy)2]0, [Ni(tpy)2]0, and [Ni(phen)2]0 (bpy = 2,2′‐bipyridine; tpy = 2,2′:6′,2″‐terpyridine; phen = 1,10‐phenanthroline) have been investigated by a combination of UV/Vis spectroscopy, magnetochemistry, and X‐ray crystallography {the structures of [Ni(bpy)2]0, [Ni(tpy)Cl]0, [Cu(bpy)2](PF6)2 (reinvestigation), and [(bpy)2Cu(μ2‐NO3)Cu(bpy)2](PF6)3 are reported herein}. To further clarify the electronic structures of the title compounds and elucidate those of the electron transfer series produced by their reduction and oxidation, broken‐symmetry (BS) density functional theory (DFT) calculations were performed for [Ni(bpy)2]m (m = 2+, 1+, 0, 1–, 2–), [Ni(bpy)3]m (m = 3+, 2+, 1+, 0, 1–, 2–), [Ni(tpy)2]m (m = 3+, 2+, 1+, 0), and, for calibration purposes, [Zn(phen)(NH3)xCl(2–x)]0 (x = 2, 1, 0). Through the aforementioned studies, it was shown that none of the so called “low‐valent” Ni complexes contain zero‐valent Ni. Instead, they each contain at least one (bpy·)1–, (tpy·)1–, or (phen·)1– π‐radical monoanionic ligand. More specifically, they are all four‐coordinate and possess the following electronic structures: [NiI(bpy·)(bpy0)] (delocalized), [NiI(tpy·)(tpy0)] (delocalized), and [NiII(Mephen·)2] (Mephen = 2,9‐dimethyl‐1,10‐phenanthroline). In addition, all members of the series [Ni(bpy)2]m with m ≤ 1+ contain a NiI ion (d9, SNi = 1/2), and the redox processes that link them are ligand‐centered. A similar finding was made for six‐coordinate [Ni(bpy)3]m and [Ni(tpy)2]m, but in this case complexes with m ≤ 2+ contain Ni ions posessing an invariant +II oxidation state (d8, SNi = 1).
Suzuki Coupling Reactions Catalyzed with Palladacycles and Palladium(II) Complexes of 2‐Thiophenemethylamine‐Based Schiff Bases: Examples of Divergent Pathways for the Same Ligand
Authors: Joshi Hemant , Prakash Om , Sharma Alpesh K. , Sharma Kamal Nayan , Singh Ajai K.
Published: February 2015

Activation of Suzuki coupling with a complex of palladium varies with the mode of coordination of its ligand. The moisture‐/air‐insensitive palladacycles and palladium complexes designed using the same ligand (Schiff base, coordinating as an N,C– and N,O– ligand, respectively) have been found to follow different pathways. Palladacycles are more efficient, as their 0.001 mol‐% loading gives good conversion (yield > 90 %) in several cases. Higher loading than this is required for Pd complexes to obtain a similar yield. Activation with palladacycles involves the role of nanosized Pd‐containing species generated in situ during catalysis, in which, as with PdII complexes, no such particle is formed and Pd0 probably remains protected by the sulfur of the thienyl group. The Schiff bases used here were designed by the reaction of 2‐thiophenemethylamine with 2‐hydroxybenzophenone/2‐hydroxy‐4‐methoxybenzophenone/2‐hydroxyacetophenone (L1/L2/L3). Upon treatment with [PdCl2(CH3CN)2] and [Na2PdCl4] they gave palladacycles [PdL1/L2(CH3CN)Cl] (1/3) and palladium(II) complexes [Pd(L1/L2/L3)2] (2/4/5), respectively. Compounds L1–L3 and their complexes 1–5 were authenticated with 1H and 13C{1H} NMR spectroscopy, and HRMS. Single crystal structures of 1, 2, 4, and 5 reveal nearly square‐planar geometry around Pd in each case. The PPh3/Hg poisoning and two‐phase tests indicate that the catalysis is homogeneous for both the palladacycle and palladium complexes, probably through leaching of Pd0 from NPs in the case of the former.
Synthesis of the First Example of Selenium‐Containing Platinum(II)–Alkenylarylalkynyl Complexes
Authors: Rahman Md. Mostafizur , Younus Muhammad , Ogawa Akiya
Published: February 2015

A synthetic method has been developed to construct a new series of selenium‐containing trans‐platinum(II)–bis(alkenylarylalkynyl) complexes with general formula trans‐[(PR3)2Pt{C≡C–Ar–C(SePh)=CH(SePh)}2] (R = ethyl, phenyl, and Ar = phenylene, biphenylene), having two phenylseleno moieties on each alkenyl backbone. Reaction of the diterminal alkynyl ligand of trans‐platinum(II)–bis(alkynylarylalkynyl) complex 1 with an amount slightly in excess of two equivalents of diphenyl diselenide in chloroform readily affords trans‐platinum(II) complex 2 upon irradiation, in good to excellent yields with good regioselectivity. As compared to the absorption band of platinum(II) complexes 1, it was found that the position of the lowest energy absorption bands of platinum(II) complexes 2 are redshifted.
Asymmetric Base‐Free Michael Addition at Room Temperature with Nickel‐Based Bifunctional Amido‐Functionalized N‐Heterocyclic Carbene Catalysts
Authors: Rao Mitta Nageswar , Haridas Meera , Gangwar Manoj Kumar , Rajakannu Palanisamy , Kalita Alok Ch. , Ghosh Prasenjit
Published: February 2015

A series of nickel‐based chiral bifunctional catalysts (1d–3d) with N‐heterocyclic carbene (NHC) ligands derived from (1R)‐(–)‐menthol, (1S)‐(–)pinene, and (1R)‐(+)‐camphor have been successfully designed for asymmetric Michael addition reactions under base‐free conditions. The NHC complexes, namely, [1‐R‐3‐{N‐(phenylacetamido)}imidazol‐2‐ylidene]2Ni [R = (1S)‐menthyl (1d), (1S)‐pinane (2d), and (1R)‐isobornyl (3d)], bearing chiral ancillaries on the amido‐functionalized side arms of the NHC ligands, performed the bifunctional catalysis of the asymmetric base‐free Michael addition reaction of the α‐methyl cyano ester substrates ethyl 2‐cyanopropanoate (4), isopropyl 2‐cyanopropanoate (5), and tert‐butyl 2‐cyanopropanoate (6) with the activated olefinic substrates methyl vinyl ketone (7) and acrylonitrile (8) in 63–98 % yields with enantiomeric excess (ee) values of 2–75 % at room temperature in 8 h. More interestingly, only the longest of the three catalysts, the menthol derivative 1d, showed significant chiral induction of up to 75 % ee; this has been attributed to the reduction of the steric influence owing to the relatively distant dispositions of the chiral ancillaries from the catalytically active metal center that arise as a consequence of the cis geometries of 1d–3d.
Synthesis of 2‐Acylphenol and Flavene Derivatives from the Ruthenium‐Catalyzed Oxidative C–H Acylation of Phenols with Aldehydes
Authors: Lee Hanbin , Yi Chae S.
Published: February 2015

The cationic ruthenium hydride complex [(C6H6)(PCy3)(CO)RuH]+BF4– has been found to be an effective catalyst for the oxidative C–H coupling reaction of phenols with aldehydes to give 2‐acylphenol compounds. The coupling of phenols with α,β‐unsaturated aldehydes selectively gives the flavene derivatives. The catalytic method mediates direct oxidative C–H coupling of phenol and aldehyde substrates without using any metal oxidants or forming wasteful byproducts.
Superhard, Antireflective Texturized Coatings Based on Hyperbranched Polymer Composite Hybrids for Thin‐Film Solar Cell Encapsulation
Authors: González Lazo Marina A. , Schüler Andreas , Haug Franz‐Josef , Ballif Christophe , Månson Jan‐Anders E. , Leterrier Yves
Published: February 2015

In this study, we demonstrate by simulation and experiment the antireflective (AR) performance of hyperbranched polymer (HBP) nanocomposites textures replicated from a moth‐eye pattern using ultraviolet (UV) nanoimprint lithography. A UV‐curable acrylated HBP and a hybrid composite of the HBP with silica nanoparticles with an organometal precursor were used. Using effective medium theory (EMT) simulations, optimal patterns were found to be arrays of paraboloids with stable AR performance over a large range of geometries. A good agreement was found between the simulated and measured optical behavior of such AR arrays with a normal reflectance within the visible range of approximately 4 % for the use of a glass substrate. The photocurrent of AR‐coated a‐Si:H solar cells was found to be 2 % higher than the reference value of an uncoated cell whereas, for AR‐coated tandem thin film Si cells, the increase was 3 % for the top a‐Si:H cell and 2 % for the bottom microcrystalline Si cell.
Lowest‐density MDS array codes for reliable Smart Meter networks
Authors: Sandell Magnus , Tosato Filippo
Published: February 2015

In this paper, we introduce a lowest‐density maximum‐distance separable (MDS) array code, which is applied to a Smart Meter network to introduce reliability. By treating the network as distributed storage with multiple sources, information can be exchanged between the nodes in the network allowing each node to store parity symbols relating to data from other nodes. A lowest‐density MDS array code is then applied to make the network robust against outages, ensuring low overhead and data transfers. We show the minimum amount of overhead required to be able to recover from r node erasures in an n node network and explicitly design an optimal array code with lowest density. In contrast to existing codes, this one has no restrictions on the number of nodes or erasures it can correct. Furthermore, we consider incomplete networks where all nodes are not connected to each other. This limits the exchange of data for purposes of redundancy, and we derive conditions on the minimum node degree that allow lowest‐density MDS codes to exist. We also present an explicit code design for incomplete networks that is capable of correcting two node failures. Copyright © 2015 John Wiley & Sons, Ltd.
A rich locality in South Kensington: the fossil hominin collection of the Natural History Museum, London
Authors: Buck Laura T. , Stringer Christopher B.
Published: February 2015

The primacy of fossils in the Natural History Museum (NHM) goes back to the very origins of the Museum, but the first fossil hominins in the collections were probably the Upper Palaeolithic remains from Bruniquel, which were accessioned in 1864. This founded a collection which has continued to expand into this century. While there have been many compilations and descriptions of the fossil hominin collection at the NHM over its long history, to our knowledge no‐one has prepared a review of the collection itself. The intention of the current paper is to synthesize earlier sources with accounts of new finds, revised chronologies and rediscovered treasures in order to illustrate the breadth and continuing importance of the fossil hominins curated at the NHM. We list and discuss all the hominin material known or thought to pre‐date the Holocene. These form a collection of great importance, both in terms of their research value and history of science. With the application of new investigative techniques such as aDNA and microCT, the material remains central to palaeoanthropological research in the 21st Century. Copyright © 2015 John Wiley & Sons, Ltd.
New insights into the neural network mediating reading processes provided by cortico‐subcortical electrical mapping
Authors: Zemmoura Ilyess , Herbet Guillaume , Moritz‐Gasser Sylvie , Duffau Hugues
Published: February 2015

Objectives

To ascertain the neural network mediating reading using intraoperative electrostimulation.

Experimental design

A cortical and axonal intraoperative electrical mapping of reading processes was achieved in seven patients who underwent awake surgery for a left occipitotemporal glioma. We performed resection cavity overlapping and superimposition with a diffusion tensor imaging‐based white matter atlas. We assessed the relationship between the location of resection cavities and the occurrence of reading impairments of regular, irregular, and pseudowords.

Principal observations

Intraoperative stimulation of the left posterior inferior temporal cortex (ITCp) elicited reading disturbances. Subcortical stimulation at the anterior portion of the visual word form area (VWFA) induced addressed phonology (irregular words reading) disturbances. Subcortical stimulation of the connection between VWFA and the posterior segment of the arcuate fascicle (AFp) induced both addressed and assembled phonology (irregular and pseudowords reading) disturbances. Postoperative assessment showed that resection of the posterior portion of the inferior longitudinal fascicle (ILFp), connecting the visual cortex to VWFA, induced long‐term and global reading impairment. Resection of the terminations of left AFp in the ITCp‐induced irregular and pseudowords reading disturbances with no impairment of regular words reading. Resection of the anterior portion of ILF did not induce reading impairment.

Conclusions

Our data support an inner posterior‐to‐anterior hierarchical coding of letter strings in the VWFA and a crucial role of the left ILFp to provide visual inputs to the VWFA. Furthermore, we suggest that the AFp is involved in an interactive feedback system between visual and nonvisual information, recruited when reading irregular and pseudowords. Hum Brain Mapp 36:2215–2230, 2015. © 2015 Wiley Periodicals, Inc.
A cortical–subcortical syntax pathway linking Broca's area and the striatum
Authors: Teichmann Marc , Rosso Charlotte , Martini Jean‐Baptiste , Bloch Isabelle , Brugières Pierre , Duffau Hugues , Lehéricy Stéphane , Bachoud‐Lévi Anne‐Catherine
Published: February 2015

Combinatorial syntax has been shown to be underpinned by cortical key regions such as Broca's area and temporal cortices, and by subcortical structures such as the striatum. The cortical regions are connected via several cortico‐to‐cortical tracts impacting syntactic processing (e.g., the arcuate) but it remains unclear whether and how the striatum can be integrated into this cortex‐centered syntax network. Here, we used a systematic stepwise approach to investigate the existence and syntactic function of an additional deep Broca‐striatum pathway. We first asked 15 healthy controls and 12 patients with frontal/striatal lesions to perform three syntax tests. The results obtained were subjected to voxel‐based lesion‐symptom mapping (VLSM) to provide an anatomo‐functional approximation of the pathway. The significant VLSM clusters were then overlapped with the probability maps of four cortico‐cortical language tracts generated for 12 healthy participants (arcuate, extreme capsule fiber system, uncinate, aslant), including a probabilistic Broca‐striatum tract. Finally, we carried out quantitative analyses of the relationship between the lesion load along the tracts and syntactic processing, by calculating tract‐lesion overlap for each patient and analyzing the correlation with syntactic data. Our findings revealed a Broca‐striatum tract linking BA45 with the left caudate head and overlapping with VLSM voxel clusters relating to complex syntax. The lesion load values for this tract were correlated with complex syntax scores, whereas no such correlation was observed for the other tracts. These results extend current syntax‐network models, by adding a deep “Broca‐caudate pathway,” and are consistent with functional accounts of frontostriatal circuits. Hum Brain Mapp 36:2270–2283, 2015. © 2015 Wiley Periodicals, Inc.
The effects of work‐reinforcer schedules on performance and preference in students with autism
Authors: Bukala Magdalena , Hu Meng Yao , Lee Ronald , Ward‐Horner John C. , Fienup Daniel M.
Published: February 2015

This study investigated performance under and preference for continuous and discontinuous work‐reinforcer schedules in 3 students who had been diagnosed with autism. Under continuous schedules, participants completed all work and consumed all reinforcers in contiguous units. Under discontinuous schedules, work and reinforcer access were broken up into smaller units. During the alternating‐schedules phase, session duration was shorter in the continuous schedule for 2 participants. During free choice, all 3 participants preferred the continuous work schedule.
Teaching children with autism to discriminate the reinforced and nonreinforced responses of others: Implications for observational learning
Authors: DeQuinzio Jaime Ann , Taylor Bridget A.
Published: February 2015

We taught 4 participants with autism to discriminate between the reinforced and nonreinforced responses of an adult model and evaluated the effectiveness of this intervention using a multiple baseline design. During baseline, participants were simply exposed to adult models' correct and incorrect responses and the respective consequences of each. During discrimination training, in the presence of target pictures, we taught participants to imitate the reinforced responses of an adult model and to say “I don't know” when an adult model's response was not reinforced. Test sessions were conducted after baseline, discrimination training, and generalization sessions to measure responding to target pictures in the absence of the model, prompts, and reinforcement. All 4 participants showed acquisition in the discrimination of reinforced and nonreinforced responses of the adult model during test sessions. Generalization to stimuli not associated with training was variable across the 4 participants. Implications for teaching observational learning responses to children with autism are discussed.
The multieffects of DMF and DBU on the [5 + 1] benzannulation of nitroethane and α‐alkenoyl ketene‐(S,S)‐acetals: Hydrogen bonding and electrostatic interactions
Authors: Yuan Haiyan , Zheng Yiying , Li Bo , Li Wenliang , Zhang Jingping
Published: February 2015

A density functional theory (DFT) study was performed to elucidate the mechanism for the [5 + 1] benzannulation of nitroethane and α‐alkenoyl ketene‐(S,S)‐acetals. The calculation results are consistent with experimental findings, showing that the reaction proceeds via deprotonation of nitroethane, nucleophilic addition, intramolecular cyclization, elimination of HNO2, and the keto‐enol tautomerization sequence. It was disclosed that N,N‐dimethylformamide (DMF) and 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) act as not only solvent and nonnucleophilic base, respectively, but also catalysts in the reaction by stabilizing the transition states (TSs) and intermediates via intermolecular hydrogen bonds and electrostatic interactions. Besides, the effective orbital interaction of the reaction site in TS also contributes to the intramolecular cyclization step. The new mechanistic insights obtained by DFT calculations highlight that the hydrogen bonds and electrostatic interactions are key factors for the [5 + 1] benzannulation of nitroethane and α‐alkenoyl ketene‐(S,S)‐acetals. © 2015 Wiley Periodicals, Inc.
Unitary group adapted state specific multireference perturbation theory: Formulation and pilot applications
Authors: Sen Avijit , Sen Sangita , Samanta Pradipta Kumar , Mukherjee Debashis
Published: February 2015

We present here a comprehensive account of the formulation and pilot applications of the second‐order perturbative analogue of the recently proposed unitary group adapted state‐specific multireference coupled cluster theory (UGA‐SSMRCC), which we call as the UGA‐SSMRPT2. We also discuss the essential similarities and differences between the UGA‐SSMRPT2 and the allied SA‐SSMRPT2. Our theory, like its parent UGA‐SSMRCC formalism, is size‐extensive. However, because of the noninvariance of the theory with respect to the transformation among the active orbitals, it requires the use of localized orbitals to ensure size‐consistency. We have demonstrated the performance of the formalism with a set of pilot applications, exploring (a) the accuracy of the potential energy surface (PES) of a set of small prototypical difficult molecules in their various low‐lying states, using natural, pseudocanonical and localized orbitals and compared the respective nonparallelity errors (NPE) and the mean average deviations (MAD) vis‐a‐vis the full CI results with the same basis; (b) the efficacy of localized active orbitals to ensure and demonstrate manifest size‐consistency with respect to fragmentation. We found that natural orbitals lead to the best overall PES, as evidenced by the NPE and MAD values. The MRMP2 results for individual states and of the MCQDPT2 for multiple states displaying avoided curve crossings are uniformly poorer as compared with the UGA‐SSMRPT2 results. The striking aspect of the size‐consistency check is the complete insensitivity of the sum of fragment energies with given fragment spin‐multiplicities, which are obtained as the asymptotic limit of super‐molecules with different coupled spins. © 2015 Wiley Periodicals, Inc.
Serum Adenosine Deaminase (ADA) Activity: A Novel Screening Test to Differentiate HIV Monoinfection From HIV‐HBV and HIV‐HCV Coinfections
Authors: Abdi Mohammad , Rahbari Rizgar , Khatooni Zahed , Naseri Nima , Najafi Adel , Khodadadi Iraj
Published: February 2015

Background

CD4+ cell count, the common HIV infection screening test, is costly and unable to differentiate HIV monoinfection from its concurrent infection with hepatitis B or C virus. We aimed to ascertain diagnostic value of serum adenosine deaminase (ADA) activity as a useful tool to differentiate HIV mono‐ and co‐infection.

Methods

Blood samples were collected from 30 HIV‐HBV and 30 HIV‐HCV coinfected patients, 33 HIV positive subjects, and 72 controls. CD4+ cell count, serum total ADA (tADA), and ADA1, and ADA2 isoenzyme activities were determined and their sensitivity and specificity were computed.

Results

tADA and ADA2 activities were significantly higher and CD4+ counts were markedly lower in all patients compared with controls. Strong inverse agreements between CD4+ cell counts and both tADA and ADA2 activities were observed. Serum tADA and ADA1 activities showed the highest specificity and the highest sensitivity, respectively, for differentiating HIV monoinfection from HIV‐HBV and HIV‐HCV coinfections.

Conclusions

We showed strong agreement and correlation between CD4+ cell count and ADA enzyme activity. Based on high ADA sensitivity and specificity, it is concluded that determination of ADA activity might be a novel diagnostic tool to distinguish of HIV monoinfection from its coinfection with HBV or HCV.
[11C]Carbon monoxide in labeling chemistry and positron emission tomography tracer development: scope and limitations
Authors: Rahman Obaidur
Published: February 2015

[11C]Carbon monoxide is an attractive precursor for labeling carbonyl position in a wide range of organic compounds. The use of [11C]carbon monoxide in transition metal‐mediated coupling reactions has been explored by several groups during the last 15 years, and an impressive number of the synthesis of [carbonyl‐11C]compounds have been published to date. The application of radical‐mediated [11C]carbonylation has also been explored in some extent. However, the main limitations to apply this potential precursor in 11C‐labeling chemistry are low concentration, poor solubility in commonly used organic solvents, and low reactivity. A couple of technical solutions such as high‐pressure reactor system, microfluidic system, and different approaches to confine [11C]CO to the reaction media at ambient pressure have been developed over the years. Although considerable advances in [11C]carbon monoxide chemistry have been reported in recent years, its application in positron emission tomography tracer development is still an area of work in progress. This review summarizes all contributions to the area of radiolabeling using [11C]carbon monoxide published between 1995 and 2014 and discusses the scope and limitations of this method in clinical positron emission tomography tracer development.
Molecular dissection of the interactions of an antitumor interleukin‐2‐derived mutein on a phage display‐based platform
Authors: Rojas Gertrudis , Carmenate Tania , Leon Kalet
Published: February 2015

A mutein with stronger antitumor activity and lower toxicity than wild‐type human interleukin‐2 (IL‐2) has been recently described. The rationale behind its design was to reinforce the immunostimulatory potential through the introduction of four mutations that would selectively disrupt the interaction with the IL‐2 receptor alpha chain (thought to be critical for both IL‐2‐driven expansion of T regulatory cells and IL‐2‐mediated toxic effects). Despite the successful results of the mutein in several tumor models, characterization of its interactions was still to be performed. The current work, based on phage display of IL‐2‐derived variants, showed the individual contribution of each mutation to the impairment of alpha chain binding. A more sensitive assay, based on the ability of phage‐displayed IL‐2 variants to induce proliferation of the IL‐2‐dependent CTLL‐2 cell line, revealed differences between the mutated variants. The results validated the mutein design, highlighting the importance of the combined effects of the four mutations. The developed phage display‐based platform is robust and sensitive, allows a fast comparative evaluation of multiple variants, and could be broadly used to engineer IL‐2 and related cytokines, accelerating the development of cytokine‐derived therapeutics. Copyright © 2015 John Wiley & Sons, Ltd.
Economic impact of considering El Niño‐Southern Oscillation on the representation of streamflow in an electric system simulator
Authors: Maciel Fernanda , Terra Rafael , Chaer Ruben
Published: February 2015

The Electric Power System Simulator (SimSEE) is a model that optimizes and simulates the operation of an electric system and has been widely used to analyze the integrated power system in Uruguay. Among the stochastic processes that SimSEE needs to represent are the streamflow inputs to the hydroelectric dams, which constitute a key factor for both energy dispatches and mid‐term planning. A dominant feature of streamflow time series is that they show very high interannual variability, which represents a major uncertainty for energy operation in Uruguay. Part of this variability is associated with El Niño‐Southern Oscillation (ENSO) phenomena. In this work, a climate index associated with ENSO is incorporated to the stochastic generator of streamflow series used by the SimSEE. Forty six‐month‐long simulations are performed with and without such modifications. We find that the system operator can take advantage of the ENSO‐related information incorporated to SinSEE in 65% of the cases (semesters) considered, reducing the total costs of operation. This result still holds in a scenario with larger firm capacity. The amounts saved, however, are reduced as the firm capacity increases. The enhanced generation options associated with a larger firm capacity diminish the overall costs of generation, especially in times of low streamflow, rendering the savings associated with a more efficient management of the reservoir less significant.
Climatology of global lightning classified by stroke energy using WWLLN data
Authors: Iwasaki Hiroyuki
Published: February 2015

Climatological features of lightning, based on stroke energy, were studied by considering the hourly detection efficiency of the World Wide Lightning Location Network (WWLLN) data set from April 2009 to April 2014. Five regions were found in which the ratio of strong lightning (>90th percentile of stroke energy) to overall lightning exceeded 30% (high S‐ratio regions), and one region was determined in which the ratio of weak lightning (<10th percentile) to overall lightning exceeded 30% (high W‐ratio region). One region of high S‐ratio was the Tibetan Plateau. Lightning activity and the S‐ratio in this region increased during summer afternoons as rainfall increased; however, the large S‐ratio was observed in the grid where lightning activity was very weak. The four other areas of high S‐ratio were located over the ocean in the sub‐polar climatic zones of the Northern and Southern Hemispheres. In cold seasons of the two hemispheres, when rainfall amount increased, both the lightning activity and the S‐ratio increased, displaying nocturnal maxima; however, the amount of rainfall did not exhibit diurnal variation. Here, a large S‐ratio was also observed in the grid where lightning activity was very weak. Weak lightning activity dominated in the East Pacific. The activity of weak lightning and the W‐ratio showed a tendency to increase during daytime in the cold season. The seasonal variation of the W‐ratio was almost in accordance with rainfall amount; however, diurnal variation of the W‐ratio was not. A large value of the W‐ratio was also observed in the grid where the lightning activity was very weak.
Infrared Spectroscopic Evidence for a Heterogeneous Reaction between Ozone and Sodium Oleate at the Gas–Aerosol Interface: Effect of Relative Humidity
Authors: Nájera Juan J. , Percival Carl J. , Horn Andrew B.
Published: February 2015

The heterogeneous ozonolysis of sodium oleate aerosols in an aerosol flow tube is reported under different relative humidity (RH%) conditions. Submicron sodium oleate particles were exposed to a known ozone concentration and the consumption of sodium oleate was monitored by infrared spectroscopy. When the experimental results are treated as a surface‐mediated reaction (i.e., following a Langmuir–Hinshelwood type mechanism), the following parameters are obtained: at low RH%, = (3 ± 1) × 10−16 cm3 molecule−1 and = (0.046 ± 0.006) s−1; at high RH%, = (6 ± 2) × 10−16 cm3 molecule−1 and = (0.21 ± 0.05) s−1. From these pseudo–first‐order coefficients, the reactive uptake coefficients for dry and aqueous sodium oleate aerosols are calculated as (1.5 − 0.5) × 10−7 and (1.7 − 0.7) × 10−6, respectively. Hydrated oleate aerosols display both an increase in the ozone trapping ability and an increase in the effective rate reaction at the droplet surface compared to dry aerosol surfaces. These observations may provide an explanation for some of the variability observed between lab studies of dry ozonolysis and real‐world, atmospheric lifetimes of oleic acid–related species.