bluuebunny/crossref_metadata_2025 huggingface dataset:
Monofluoroalkenylation of Dimethylamino Compounds through Radical–Radical Cross‐Coupling
Authors: Xie Jin , Yu Jintao , Rudolph Matthias , Rominger Frank , Hashmi A. Stephen K.
Published: June 2016

An unprecedented and challenging radical–radical cross‐coupling of α‐aminoalkyl radicals with monofluoroalkenyl radicals derived from gem‐difluoroalkenes was achieved. This first example of tandem C(sp3)−H and C(sp2)−F bond functionalization through visible‐light photoredox catalysis offers a facile and flexible access to privileged tetrasubstituted monofluoroalkenes under very mild reaction conditions. The striking features of this redox‐neutral method in terms of scope, functional‐group tolerance, and regioselectivity are illustrated by the late‐stage fluoroalkenylation of complex molecular architectures such as bioactive (+)‐diltiazem, rosiglitazone, dihydroartemisinin, oleanic acid, and androsterone derivatives, which represent important new α‐amino C−H monofluoroalkenylations.
Total Synthesis, Structure, and Biological Activity of Adenosylrhodibalamin, the Non‐Natural Rhodium Homologue of Coenzyme B12
Authors: Widner Florian J. , Lawrence Andrew D. , Deery Evelyne , Heldt Dana , Frank Stefanie , Gruber Karl , Wurst Klaus , Warren Martin J. , Kräutler Bernhard
Published: June 2016

B12 is unique among the vitamins as it is biosynthesized only by certain prokaryotes. The complexity of its synthesis relates to its distinctive cobalt corrin structure, which is essential for B12 biochemistry and renders coenzyme B12 (AdoCbl) so intriguingly suitable for enzymatic radical reactions. However, why is cobalt so fit for its role in B12‐dependent enzymes? To address this question, we considered the substitution of cobalt in AdoCbl with rhodium to generate the rhodium analogue 5′‐deoxy‐5′‐adenosylrhodibalamin (AdoRbl). AdoRbl was prepared by de novo total synthesis involving both biological and chemical steps. AdoRbl was found to be inactive in vivo in microbial bioassays for methionine synthase and acted as an in vitro inhibitor of an AdoCbl‐dependent diol dehydratase. Solution NMR studies of AdoRbl revealed a structure similar to that of AdoCbl. However, the crystal structure of AdoRbl revealed a conspicuously better fit of the corrin ligand for RhIII than for CoIII, challenging the current views concerning the evolution of corrins.
Study of molecular weight and chain branching architectures of natural rubber
Authors: Qu Wei , Zhu Yong , Huang Guangsu , Huang Cheng , Luo Ming‐Chao , Zheng Jing
Published: June 2016

The origin of the unique bimodal molecular weight distribution (MWD) of natural rubber (NR) has been controversial up to now. Studying the connection between particle size and molecular weight (MW) might be a key approach to revealing the mystery of NR architectures. In this study, through constructing NR models as objectives and employing gel‐permeation chromatography coupled to a viscosity detector as well as a multiangle laser light scattering detector (GPC‐DP‐MALLS), we have acquired branching parameters for NR from solid experiments and data fitting. It is found that small rubber particles (SRPs) and large rubber particles (LRPs) jointly construct the unique bimodal MWD of NR. SRPs with low branching numbers (Bn) and branching frequency (λ) are believed to be composed of almost linear rubber molecules having no chain‐end groups to be branched. In contrast, LRPs transform their MWD curve into a clear bimodal peak after transesterification and possess high Bn. Meanwhile, the formation of branch points in LRP by hydrogen bonding and ionic linkages has been clearly confirmed. Thus, a clear and exact structure of NR has been revealed for the first time. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci, 2016.
Solvents for thermoporosimetry analysis of natural rubber networks
Authors: Wirtz Marcel , Rommel Robert , López Valentín Juan , Westermann Stephan , Sportelli Franco , Kayser François
Published: June 2016

Thermoporosimetry is known as an analytical method to investigate network structures in swollen elastomers. Despite this interesting potential capability, only few investigations are published in literature which apply different solvents on differently crosslinked natural rubber samples. The choice of the solvent is critical as it strongly influences the separation of confined and bulk solvent transition signal, the confined solvent signal intensity and the peak width representing the pore size resolution. No critical comparison has been done in these investigations regarding the solvent choice related to peak separation, pore size resolution or signal intensity. Furthermore, no critical assessment is available relating thermoporosimetry results to solvent parameters to identify an optimal solvent regarding the mentioned criteria. This argument motivated the present investigation to identify the most appropriate solvents for the analysis of natural rubber compounds by thermoporosimetry. Different types of solvents (aliphatic, aromatic, non‐polar, and polar) were selected and benchmarked against each other. It was concluded that n‐heptane was identified as the best solvent for these investigations. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43998.
Evaluating airlines with slack‐based measures and meta‐frontiers
Authors: Chou Huey‐Wen , Lee Chia‐Yen , Chen Huey‐Kuo , Tsai Mon‐You
Published: June 2016

This study develops a new performance evaluation model, called the meta dynamic network slack‐based measure (MDN‐SBM). This model incorporates the concept of meta‐frontiers to facilitate comparisons of performance of decision making units, while at the same time it generalizes the slack‐based measure (SBM), network SBM, and dynamic SBM. This MDN‐SBM model is capable of dealing with two important special features of the transportation industry: unfavorable accidents and non‐storable goods, i.e. available seat‐kilometers that are wasting assets that lose value completely if unsold before departure. Hence, this generalized model contains higher differentiable capability than all its SBM‐related submodels in the literature. To demonstrate, 35 international airlines with two divisions (production and consumption) in three terms (one‐year time periods from 2007 to 2009) have been analyzed using meta‐performance efficiency measures (ME) for all decision making units and have also been compared by geographical area (Asia‐Pacific, N. America/Europe). The numerical example and comparison validate the proposed MDN‐SBM model and suggest the airlines should put more focus on input resources reduction for productivity improvement. Copyright © 2016 John Wiley & Sons, Ltd.
Intact mirror mechanisms for automatic facial emotions in children and adolescents with autism spectrum disorder
Authors: Schulte‐Rüther Martin , Otte Ellen , Adigüzel Kübra , Firk Christine , Herpertz‐Dahlmann Beate , Koch Iring , Konrad Kerstin
Published: June 2016

It has been suggested that an early deficit in the human mirror neuron system (MNS) is an important feature of autism. Recent findings related to simple hand and finger movements do not support a general dysfunction of the MNS in autism. Studies investigating facial actions (e.g., emotional expressions) have been more consistent, however, mostly relied on passive observation tasks. We used a new variant of a compatibility task for the assessment of automatic facial mimicry responses that allowed for simultaneous control of attention to facial stimuli. We used facial electromyography in 18 children and adolescents with Autism spectrum disorder (ASD) and 18 typically developing controls (TDCs). We observed a robust compatibility effect in ASD, that is, the execution of a facial expression was facilitated if a congruent facial expression was observed. Time course analysis of RT distributions and comparison to a classic compatibility task (symbolic Simon task) revealed that the facial compatibility effect appeared early and increased with time, suggesting fast and sustained activation of motor codes during observation of facial expressions. We observed a negative correlation of the compatibility effect with age across participants and in ASD, and a positive correlation between self‐rated empathy and congruency for smiling faces in TDC but not in ASD. This pattern of results suggests that basic motor mimicry is intact in ASD, but is not associated with complex social cognitive abilities such as emotion understanding and empathy. Autism Res 2017, 10: 298–310. © 2016 International Society for Autism Research, Wiley Periodicals, Inc.
A review of novel analytical diagnostics for liquid biopsies: spectroscopic and spectrometric serum profiling of primary and secondary brain tumors
Authors: Spalding Katie , Board Ruth , Dawson Timothy , Jenkinson Michael D. , Baker Matthew J.
Published: June 2016

Introduction

Spectroscopic and spectrometric analysis of biological samples is regarded as quick, cost effective, easy to operate, and spectroscopic sample preparation involves minimal sample preparation.

Results

Techniques like infrared (IR) spectroscopy, surface‐enhanced laser desorption/ionization (SELDI)‐mass spectroscopy (MS), and matrix‐assisted laser desorption/ionization (MALDI) ‐MS could enable early diagnosis of cancer, disease monitoring, and assessment of treatment responses allowing refinement, if required.

Discussion

Carrying out analytical testing within outpatient clinics would dramatically cut the time spent by patients attending different appointments, at different locations, save hospital time and resources but importantly would theoretically enable a reduction in mortality and morbidity. While the advantages of such a prospect seem obvious, this review aims to evaluate the use of human serum spectroscopic and spectrometric analysis as a diagnostic tool for brain cancers, creating a platform for the future of cancer diagnostics.
Kinetics of the Interactions between Copper and Amyloid‐β with FAD Mutations and Phosphorylation at the N terminus
Authors: Girvan Paul , Miyake Toru , Teng Xiangyu , Branch Thomas , Ying Liming
Published: June 2016

Mutations and post‐translational modifications of amyloid‐β (Aβ) peptide in its N terminus have been shown to increase fibril formation, yet the molecular mechanism is not clear. Here we investigated the kinetics of the interactions of copper with two Aβ peptides containing Familial Alzheimer's disease (FAD) mutations (English (H6R) and Tottori (D7N)), as well as with Aβ peptide phosphorylated at serine 8 (pS8). All three peptides bind to copper with a similar rate as the wild‐type (wt). The dissociation rates follow the order pS8>H6R>wt>D7N; the interconversion between the two coordinating species occurs 50 % faster for H6R and pS8, whereas D7N had only a negligible effect. Interestingly, the rate of ternary complex (copper‐bridged heterodimer) formation for the modified peptides was significantly faster than that for wt, thus leading us to propose that FAD and sporadic AD might share a kinetic origin for the enhanced oligomerisation of Aβ.
The Outer‐Sphere Mechanism of Nitrene Transfer onto Gold(I) Alkyne Complexes
Authors: Costa Ismael , Marín‐Luna Marta , Comesaña Marta González , Faza Olalla Nieto , Silva López Carlos
Published: June 2016

The recently developed nitrene transfer reaction onto gold‐activated alkynes provides a route to safe and accessible synthons of α‐diazo imides. This reaction is rather unique in that it requires AuI in catalytic amounts; however, this promiscuous metal is only used to activate the alkyne moiety. After such activation is obtained, the nitrene‐transfer process occurs through an outer‐sphere mechanism, in which the metal acts only as a spectator. Density functional theory was applied to elucidate this peculiar reaction and to provide a mechanistic explanation for the experimentally observed isomers at the double bond and imine sites.
Aerogel Architectures Boost Oxygen‐Evolution Performance of NiFe2Ox Spinels to Activity Levels Commensurate with Nickel‐Rich Oxides
Authors: Chervin Christopher N. , DeSario Paul A. , Parker Joseph F. , Nelson Eric S. , Miller Bryan W. , Rolison Debra R. , Long Jeffrey W.
Published: June 2016

Nickel–iron oxides and oxyhydroxides are among the most active oxygen‐evolution reaction (OER) catalysts in alkaline electrolytes. Compositions rich in Ni are reported to show superior activity, but the establishment of competitive OER activity with lower cost, Fe‐rich analogues is more desirable for metal–air batteries and other devices that will see large‐scale production. Herein, we demonstrate that by controlling pore–solid architecture and the degree of crystallinity, we achieve a single‐phase, Fe‐rich NiFe2Ox catalyst that matches the OER performance metrics previously demonstrated for compositions with higher Ni‐to‐Fe ratios. We also show that OER activity linearly tracks increases in the catalyst surface area, whereas the degree of ex situ surface hydroxylation does not play a significant role. To prepare the pore–solid structured forms, NiFe2Ox gels were synthesized by using an epoxide‐initiated sol–gel method and subsequently processed to aerogels or xerogels. The activities of these two sol–gel‐derived nanostructures were compared with a nanoparticulate analogue with lower specific surface area, prepared by using conventional precipitation methods. The higher surface area and larger pore volume expressed by the NiFe2Ox formed as an aerogel result in a performance‐competitive OER overpotential of 356 mV at a current density of 10 mA cm−2, with an approximately 140 mV improvement relative to the low‐surface‐area, precipitated analogue.
Self‐Supporting and Binder‐Free Anode Film Composed of Beaded Stream‐Like Li4Ti5O12 Nanoparticles for High‐Performance Lithium‐Ion Batteries
Authors: Huo Kaifu , Li Xingxing , Gao Biao , Wang Lei , Li Qingwei , Peng Xiang , Zhang Xuming , Fu Jijiang , Chu Paul K.
Published: June 2016

A self‐supporting film composed of arrays of Li4Ti5O12 (LTO) nanoparticles (NPs) prepared through chemical lithiation of anodic TiO2 nanotube arrays and calcination in air is used as a high‐performance binder‐free anode in lithium‐ion batteries (LIBs). The LTO nanoparticles formed in situ are closely connected along the axial direction of the pristine TiO2 nanotubes, forming a beaded stream‐like structure. The self‐supporting NPs film has a large tap density and overall packing factor, and the three‐dimensional (3D) network of NPs increases the electroactive interface, facilitating transfer of Li+ and enhancing the intercalation kinetics during charging/discharging. The LTO electrode with excellent mechanical flexibility and robustness has a volumetric capacity of 304 mAh cm−3 at a current density of 50 mA cm−3 as well as a high rate capability of 208 mAh cm−3 at 5000 mA cm−3. After undergoing 500 cycles at a high current density of 1250 mA cm−3, 91.4 % of the capacity is retained, demonstrating high reversibility and cycling stability of the binder‐free LTO NPs film electrode in LIBs.
Diamondoid Structure in a Metal–Organic Framework of Fe4 Single‐Molecule Magnets
Authors: Rigamonti Luca , Cotton Carri , Nava Andrea , Lang Heinrich , Rüffer Tobias , Perfetti Mauro , Sorace Lorenzo , Barra Anne‐Laure , Lan Yanhua , Wernsdorfer Wolfgang , Sessoli Roberta , Cornia Andrea
Published: June 2016

A 3D metal–organic framework (MOF) having single‐molecule magnet (SMM) linkers was prepared in crystalline form by using a tetrairon(III) complex functionalised with two divergent pyridyl groups, namely [Fe4(pPy)2(dpm)6] (1; H3pPy=2‐(hydroxymethyl)‐2‐(pyridin‐4‐yl)propane‐1,3‐diol, Hdpm=dipivaloylmethane). Reaction of 1 with silver(I) perchlorate afforded {[Fe4(pPy)2(dpm)6]2Ag}ClO4 (2), which crystallises in a cubic face‐centred lattice and exhibits two interlocked diamondoid networks. In 2, the SMMs act as linear ditopic synthons, and silver(I) ions as tetrahedral nodes coordinated by four pyridyl nitrogen atoms. The magnetic properties of 1 (S=5 and D≈−0.4 cm−1 in the ground spin state) are largely preserved in 2, which shows slow magnetic relaxation with an anisotropy barrier of Ueff/kB=11.46(10) K in zero field and 14.25(8) K in an applied field of 1 kOe. However, crystal symmetry triggers highly noncollinear magnetic anisotropy contributions oriented at 109.47° from each other along the threefold axes of AgN4 tetrahedra, a unique scenario fully confirmed by a single‐crystal cantilever torque magnetometry investigation. Magnetisation curves down to 0.03 K demonstrated the occurrence of a wide hysteresis loop when the magnetic field was swept along one of the four Ag−N bonds. By symmetry, the crystalline compound can then be persistently magnetised parallel or antiparallel to the four main diagonals of the unit cell, although the crystals have no overall second‐order anisotropy.
An Ethylene‐Bridged Phosphane/Borane Frustrated Lewis Pair Featuring the ‐B(Fxyl)2 Lewis Acid Component
Authors: Wang Long , Samigullin Kamil , Wagner Matthias , McQuilken Alison C. , Warren Timothy H. , Daniliuc Constantin G. , Kehr Gerald , Erker Gerhard
Published: June 2016

Hydroboration of dimesitylvinylphosphane with bis[3,5‐bis(trifluoromethyl)phenyl]borane [HB(Fxyl)2] gave the intramolecular ethylene‐bridged P/B frustrated Lewis pair (FLP) Mes2PCH2CH2B(Fxyl)2. The new compound underwent a variety of typical FLP reactions such as P/B‐addition to the carbonyl group of p‐chloro‐benzaldehyde. Cooperative N,N‐addition to nitric oxide gave the respective persistent P/B FLPNO. radical, which readily reacted with 1,4‐cyclohexadiene by H‐atom abstraction to yield the corresponding P/B FLPNOH product. The B(Fxyl)2‐containing FLP reacted as a template for the HB(C6F5)2 reduction of carbon monoxide to the formyl stage to give the respective FLP(η2‐formylborane) product. Most products were characterized by single‐crystal X‐ray crystal structure analysis.
Surprisingly Different Reaction Behavior of Alkali and Alkaline Earth Metal Bis(trimethylsilyl)amides toward Bulky N‐(2‐Pyridylethyl)‐N′‐(2,6‐diisopropylphenyl)pivalamidine
Authors: Kalden Diana , Oberheide Ansgar , Loh Claas , Görls Helmar , Krieck Sven , Westerhausen Matthias
Published: June 2016

N‐(2,6‐Diisopropylphenyl)‐N′‐(2‐pyridylethyl)pivalamidine (Dipp‐N=C(tBu)‐N(H)‐C2H4‐Py) (1), reacts with metalation reagents of lithium, magnesium, calcium, and strontium to give the corresponding pivalamidinates [(tmeda)Li{Dipp‐N=C(tBu)‐N‐C2H4‐Py}] (6), [Mg{Dipp‐N=C(tBu)‐N‐C2H4‐Py}2] (3), and heteroleptic [{(Me3Si)2N}Ae{Dipp‐N=C(tBu)‐N‐C2H4‐Py}], with Ae being Ca (2 a) and Sr (2 b). In contrast to this straightforward deprotonation of the amidine units, the reaction of 1 with the bis(trimethylsilyl)amides of sodium or potassium unexpectedly leads to a β‐metalation and an immediate deamidation reaction yielding [(thf)2Na{Dipp‐N=C(tBu)‐N(H)}] (4 a) or [(thf)2K{Dipp‐N=C(tBu)‐N(H)}] (4 b), respectively, as well as 2‐vinylpyridine in both cases. The lithium derivative shows a similar reaction behavior to the alkaline earth metal congeners, underlining the diagonal relationship in the periodic table. Protonation of 4 a or the metathesis reaction of 4 b with CaI2 in tetrahydrofuran yields N‐(2,6‐diisopropylphenyl)pivalamidine (Dipp‐N=C(tBu)‐NH2) (5), or [(thf)4Ca{Dipp‐N=C(tBu)‐N(H)}2] (7), respectively. The reaction of AN(SiMe3)2 (A=Na, K) with less bulky formamidine Dipp‐N=C(H)‐N(H)‐C2H4‐Py (8) leads to deprotonation of the amidine functionality, and [(thf)Na{Dipp‐N=C(H)‐N‐C2H4‐Py}]2 (9 a) or [(thf)K{Dipp‐N=C(H)‐N‐C2H4‐Py}]2 (9 b), respectively, are isolated as dinuclear complexes. From these experiments it is obvious, that β‐metalation/deamidation of N‐(2‐pyridylethyl)amidines requires bases with soft metal ions and also steric pressure. The isomeric forms of all compounds are verified by single‐crystal X‐ray structure analysis and are maintained in solution.
Rational Molecular Design and Synthesis of Highly Thermo‐ and Photostable Near‐Infrared‐Absorbing Heptamethine Cyanine Dyes with the Use of Fluorine Atoms
Authors: Funabiki Kazumasa , Yagi Kazutaka , Ueta Masato , Nakajima Mitsuru , Horiuchi Masako , Kubota Yasuhiro , Mastui Masaki
Published: June 2016

Highly thermo‐ and photostable, near‐infrared‐absorbing heptamethine cyanine dyes were achieved with the use of fluorine‐containing components. In particular, one prepared heptamethine cyanine dye, bearing a tetrakis(pentafluorophenyl)borate as a counter anion and an N‐ethyl‐2,2,2‐trifluoroacetamido group at the meso position, showed not only a high decomposition temperature (Tdt), but also very high photostability toward white LED irradiation.
ChemInform Abstract: Preparation of the Monoacylates of 2‐Substituted (Z)‐But‐2‐ene‐1,4‐diols Using Porcine Pancreas Lipase.
Authors: Kawashima Yuya , Ezawa Tetsuya , Harada Taisuke , Noguchi Takuya , Kawasaki Masashi , Kirihara Masayuki , Imai Nobuyuki
Published: June 2016

Regioselective acylations of (Z)‐but‐2‐ene‐1,4‐diols can be performed with 10 equivalents of vinyl acetate in the presence of porcine pancreas lipase.
ChemInform Abstract: Unknown Camphor: Regioselective Rearrangement under Acylation in a CF3SO3H/(CF3CO)2O System.
Authors: Kovalev Vladimir , Shokova Elvira , Chertkov Vyacheslav , Tafeenko Victor
Published: June 2016

Camphor (I) is regio‐ and diastereoselectively acylated and rearranged to give isoborneols (IV) with carvenone (V) as byproduct (5‐8%).
ChemInform Abstract: Carboxylate‐Assisted Iridium‐Catalyzed C—H Amination of Arenes with Biologically Relevant Alkyl Azides.
Authors: Zhang Tao , Hu Xuejiao , Wang Zhen , Yang Tiantian , Sun Hao , Li Guigen , Lu Hongjian
Published: June 2016

Optimized conditions including the molar ratio of the reactants are elaborated and applied to a broad spectrum of benzamides and azides.
ChemInform Abstract: Asymmetric Alkylation of N‐Sulfonylbenzamides with Vinyl Ethers via C—H Bond Activation Catalyzed by Hydroxoiridium/Chiral Diene Complexes.
Authors: Hatano Miyuki , Ebe Yusuke , Nishimura Takahiro , Yorimitsu Hideki
Published: June 2016

This method uses an iridium diene catalyst for the alkylation of benzamides with vinyl ethers giving the branched products in good yields and with excellent enantioselectivities.
ChemInform Abstract: Metal‐Free Oxidative Deamination Cross‐Coupling of Imidazo‐Heterocycles with 2‐Aminobenzothiazoles.
Authors: Ji Xiao‐Ming , Xu Li , Yan Yun , Chen Fan , Tang Ri‐Yuan
Published: June 2016

For the first time, a mild and environmentally friendly method of the title reaction using tert‐butyl nitrite as mediator is presented.
ChemInform Abstract: Rapid and Straightforward Transesterification of Sulfonyl Carbamates.
Authors: Isaksson Rebecka , Kumpina Ilze , Larhed Mats , Wannberg Johan
Published: June 2016

A new method for the rapid and simple transesterification of alkyl alcohols with alkyl (arylsulfonyl)carbamates is developed.
ChemInform Abstract: D‐Xylonic Acid: A Solvent and an Effective Biocatalyst for a Three‐Component Reaction.
Authors: Ma Jiliang , Zhong Linxin , Peng Xinwen , Sun Runcang
Published: June 2016

D‐xylonic acid is proved to be both an effective biocatalyst and a green reaction medium for the one‐pot three‐component Biginelli condensation reaction to give pyrimidinone and ‐thione derivatives.
ChemInform Abstract: Aerobic Linear Allylic C—H Amination: Overcoming Benzoquinone Inhibition.
Authors: Pattillo Christopher C. , Strambeanu Iulia I. , Calleja Pilar , Vermeulen Nicolaas A. , Mizuno Tomokazu , White M. Christina
Published: June 2016

Aerobic linear allylic amination reactions of terminal olefins using an O2/Co/catalytic dihydroquinone redox relay in combination with a Pd/bis‐sulfoxide catalyst are investigated.
ChemInform Abstract: Activation of Chiral (Salen)AlCl Complex by Phosphorane for Highly Enantioselective Cyanosilylation of Ketones and Enones.
Authors: Zeng Xing‐Ping , Cao Zhong‐Yan , Wang Xin , Chen Long , Zhou Feng , Zhu Feng , Wang Cui‐Hong , Zhou Jian
Published: June 2016

The high efficiency of this reaction relies on orthogonal activation of the AlCl(salen) complex and Tms—CN by the phosphorane and POPh3, respectively.
ChemInform Abstract: anti‐Selective Aldol Reactions of Pentafluorosulfanylacetic Acid Esters with Aldehydes Mediated by Dicyclohexylchloroborane.
Authors: Friese Florian W. , Dreier Anna‐Lena , Matsnev Andrej V. , Daniliuc Constantin G. , Thrasher Joseph S. , Haufe Guenter
Published: June 2016

The title reaction tolerates aryl and alkyl aldehydes.
ChemInform Abstract: Aromatic Ring Hydrogenation Catalyzed by Nanoporous Montmorillonite Supported Ir(0)‐Nanoparticle Composites under Solvent Free Conditions.
Authors: Das Prabin , Sarmah Podma Pollov , Borah Bibek Jyoti , Saikia Lakshi , Dutta Dipak Kumar
Published: June 2016

The aromatic ring hydrogenation of a range of aryl compounds is efficiently accomplished with hydrogen under catalysis of iridium nanoparticles supported by an activated montmorillonite matrix.
ChemInform Abstract: Stable and Reusable Platinum Nanocatalyst: An Efficient Chemoselective Reduction of Nitroarenes in Water.
Authors: Kotha Surya Srinivas , Sharma Nidhi , Sekar Govindasamy
Published: June 2016

Binaphthyl stabilized highly stable Pt nanoparticles are prepared and used as an efficient catalyst for chemoselective hydrogenation of nitroarenes in water at room temperature under hydrogen atmosphere.
ChemInform Abstract: A General Approach to Substituted Diphenyldiazenes.
Authors: Lutz Toni A. , Spanner Patrick , Wanner Klaus T.
Published: June 2016

The diazonium salts (I) and (V) are freshly prepared from the corresponding iodoanilines and treated with diallylated anilines (II) to produce the desired unsymmetrically substituted diphenyl diazenes which are of high synthetical interest.
ChemInform Abstract: Palladium‐Catalyzed Oxidative Synthesis of Unsymmetrical Azophenols.
Authors: Nguyen Thi Hong Long , Gigant Nicolas , Delarue‐Cochin Sandrine , Joseph Delphine
Published: June 2016

A new method for the ortho‐directed hydroxylation of both symmetrical and unsymmetrical azobenzenes is developed.
ChemInform Abstract: Metal‐Free CH—CH‐Type Cross‐Coupling of Arenes and Alkynes Directed by a Multifunctional Sulfoxide Group.
Authors: Fernandez‐Salas Jose A. , Eberhart Andrew J. , Procter David J.
Published: June 2016

The title process is mediated by a multifunctional sulfoxide directing group which captures and activates the alkyne coupling partner before delivery to the arene and C—C bond formation.
ChemInform Abstract: Silica Microparticles Supported Gold and Copper Ferrite Nanoparticles: A Magnetically Recyclable Bimetallic Catalyst for Sonogashira Reaction.
Authors: Gholinejad Mohammad , Ahmadi Jahantab , Najera Carmen
Published: June 2016

A magnetic bimetallic catalyst is prepared, characterized and used in the Sonogashira reaction of aromatic halides with acetylenes.
ChemInform Abstract: Construction of Turmerone Motif‐Fused Spiropyrrolidine Oxindoles and Their Biological Evaluation for Anticancer Activities.
Authors: Liu Xiong‐Li , Yang Chao , Zhang Wen‐Hui , Zhou Gen , Ma Xi‐Tao , Lin Bing , Zhang Min , Zhou Ying , Feng Ting‐Ting
Published: June 2016

Facile and efficient methodology for the synthesis of novel turmerone motif‐fused spiropyrrolidine oxindoles via a multicomponent 1,3‐dipolar cycloaddition reaction of dienones with azomethine ylides is reported.
ChemInform Abstract: Ambient Temperature Synthesis of Spiro[indoline‐3,2′‐thiazolidinones] by a DBSA‐Catalyzed Sequential Reaction in Water.
Authors: Preetam Amreeta , Nath Mahendra
Published: June 2016

This new methodology demonstrates several key advantages including green reaction conditions, use of aqueous media, and good to excellent yields of desired products.
ChemInform Abstract: Convenient and Efficient Synthesis of 2‐Methyl‐5‐nitrobenzo[b]thiophene and Its Derivatives.
Authors: Migulin Vasily A.
Published: June 2016

The previously unknown title compound (V) is synthesized in four steps with an overall yield of 87%.
ChemInform Abstract: Opening the Way to Catalytic Aminopalladation/Proxicyclic Dehydropalladation: Access to Methylidene γ‐Lactams.
Authors: Lorion Melanie M. , Duarte Filipe J. S. , Calhorda Maria Jose , Oble Julie , Poli Giovanni
Published: June 2016

Various N‐sulfonyl protected pent‐4‐enoic acids are efficiently cyclized to methylidene γ‐lactams, whereas a corresponding transformation of hex‐5‐enoic acids provides mixtures of methylidene piperidones and vinylpyrrolidones.
ChemInform Abstract: Tandem Copper‐Catalyzed Propargylation/Alkyne Azacyclization/Isomerization Reaction under Microwave Irradiation: Synthesis of Fully Substituted Pyrroles.
Authors: Zhang Xiao‐Yan , Yang Zhi‐Wei , Chen Zhongzhu , Wang Jun , Yang Dong‐Lin , Shen Ze , Hu Li‐Li , Xie Jian‐Wu , Zhang Jin , Cui Hai‐Lei
Published: June 2016

Pentasubstituted pyrroles, including α‐arylpyrroles are prepared from readily available β‐enamino compounds and propargyl acetates.
ChemInform Abstract: Aza‐Conjugate Addition Methodology for the Synthesis of N‐Hydroxy‐isoindolin‐1‐ones.
Authors: Royo Santiago , Chapman Robert S. L. , Sim Alisia M. , Peacock Lucy R. , Bull Steven D.
Published: June 2016

Aryl aldehydes containing an ortho‐propiolate or propiolamide moiety are efficiently cyclized to N‐hydroxyisoindoline‐1‐ones, which are subsequently converted into the parent isoindoline‐1‐ones.
ChemInform Abstract: Stereoselective Synthesis of 1,3‐Disubstituted Isoindolines via Rh(III)‐Catalyzed Tandem Oxidative Olefination—Cyclization of 4‐Aryl Cyclic Sulfamidates.
Authors: Son Se‐Mi , Seo Yeon Ji , Lee Hyeon‐Kyu
Published: June 2016

The configurational integrity of the stereogenic center in the starting cyclic sulfamidate is completely retained.
ChemInform Abstract: Synthesis and Antiproliferative Efficiency of Novel Bis(imidazol‐1‐yl)vinyl‐1,2,4‐oxadiazoles.
Authors: Nandeesh Kebballi N. , Swarup Hassan A. , Sandhya Nagarakere C. , Mohan Chakrabhavi D. , Pavan Kumar Chottanahalli S. , Kumara Manikyanahalli N. , Mantelingu Kempegowda , Ananda Sannaiah , Rangappa Kanchugarakoppal S.
Published: June 2016

The title oxadiazoles are efficiently synthesized by a one‐pot reaction between N,N′‐carbonyldiimidazole, trifluoropropionic acid and various amidoximes.
ChemInform Abstract: Easy Access to 1‐Amino and 1‐Carbon Substituted Isoquinolines via Cobalt‐Catalyzed C—H/N—O Bond Activation.
Authors: Muralirajan Krishnamoorthy , Kuppusamy Ramajayam , Prakash Sekar , Cheng Chien‐Hong
Published: June 2016

This atom‐economical method for preparation of isoquinolines uses a =N‐OH functionality both as directing group and internal oxidant.
ChemInform Abstract: Catalyst‐Free Microwave‐Assisted Arylglyoxal‐Based Multicomponent Reactions for the Synthesis of Fused Pyrans.
Authors: Mishra Richa , Choudhury Lokman H.
Published: June 2016

A microwave‐enhanced three‐component reaction of arylglyoxal monohydrates, malononitrile, and cyclic 1,3‐dicarbonyls affords quinolone‐, naphthoquinone‐, coumarin‐, and pyrone‐fused pyrans.
ChemInform Abstract: Planar Chiral Phosphoramidites with a Paracyclophane Scaffold: Synthesis, Gold(I) Complexes, and Enantioselective Cycloisomerization of Dienynes.
Authors: Wu Zhiyong , Isaac Kevin , Retailleau Pascal , Betzer Jean‐Francois , Voituriez Arnaud , Marinetti Angela
Published: June 2016

Key structural feature of the new phosphoramidites is a paracyclophane scaffold in which two aryl rings are tethered by both a 1,8‐biphenylene unit and a O—P—O bridge.
ChemInform Abstract: A Convenient ′NOSE′ Approach Used Towards the Synthesis of 6‐Amino‐1,3‐dimethyl‐5‐indolyl‐1H‐pyrimidine‐2,4‐dione Derivatives Catalyzed by Nano‐Ag.
Authors: Das Vijay Kumar , Bharali Pranjal , Konwar Bolin Kumar , Mikkola Jyri‐Pekka , Shchukarev Andrey , Thakur Ashim Jyoti
Published: June 2016

Uracil‐based compounds are efficiently synthesized in good to high yields under aerobic conditions using moisture‐stable and recyclable nano‐Ag as catalyst.
ChemInform Abstract: Copper‐Catalyzed Divergent Trifluoromethylation/Cyclization of Unactivated Alkenes.
Authors: Zheng Jing , Deng Ziyang , Zhang Yan , Cui Sunliang
Published: June 2016

This trifluoromethylation protocol works for both unactivated terminal and internal alkenes and enables divergent late stage cyclization reactions.
ChemInform Abstract: Potassium Carbonate‐Mediated Tandem C—S and C—N Coupling Reaction for the Synthesis of Phenothiazines under Transition‐Metal‐Free and Ligand‐Free Conditions.
Authors: Wu San , Hu Wei‐Ye , Zhang Song‐Lin
Published: June 2016

A cyclization of N‐(2‐iodophenyl)acetamides and 2‐halobenzenethiols affords phenothiazines.
ChemInform Abstract: Isopimarane Diterpenoids from Kaempferia pulchra Rhizomes Collected in Myanmar and Their Vpr Inhibitory Activity.
Authors: Win Nwet Nwet , et al.
Published: June 2016

23 Kaempulchraols are isolated along with 7 isopimarane diterpenoids from the active CHCl3‐soluble extract of Kaempferia pulchra rhizomes.
ChemInform Abstract: Four Cytotoxic Spongian Diterpenes from the Sponge Dysidea cf. arenaria.
Authors: Shingaki Mika , Wauke Tsuyoshi , Ahmadi Peni , Tanaka Junichi
Published: June 2016

Four new diterpenes are isolated and evaluated for their cytotoxicity.
ChemInform Abstract: α‐Amino Acid‐Isosteric α‐Amino Tetrazoles.
Authors: Zhao Ting , Kurpiewska Katarzyna , Kalinowska‐Tluscik Justyna , Herdtweck Eberhardt , Doemling Alexander
Published: June 2016

A concise and rapid approach is evaluated for all 20 natural proteinogenic α‐amino acids and 4 analogues.
ChemInform Abstract: Indium Salts‐Catalyzed O and S‐Glycosylation of Bromo Sugar with Benzyl Glycolate: An Unprecedented Hydrogenolysis.
Authors: Chandra Sunena , Yadav Ram N. , Paniagua Armando , Banik Bimal K.
Published: June 2016

Various O and S‐glycosyl esters and their corresponding acids are synthesized through a reaction of bromo sugar and benzyl glycolate in the presence of indium trichloride and indium tribromide as promoter.
ChemInform Abstract: Fluorinated Radicamine A and B: Synthesis and Glycosidase Inhibition.
Authors: Li Yi‐Xian , Iwaki Ren , Kato Atsushi , Jia Yue‐Mei , Fleet George W. J. , Zhao Xuan , Xiao Min , Yu Chu‐Yi
Published: June 2016

Fluorinated derivatives of radicamine A (Ia‐d) and radicamine B (Ie,f) are synthesized from a D‐arabinose‐derived cyclic nitrone using established methods.
ChemInform Abstract: Dinuclear PdI Complexes with Bridging Allyl and Related Ligands
Authors: Hazari Nilay , Hruszkewycz Damian P.
Published: June 2016

Review: synthesis, structure, and reactivity of dinuclear PdI complexes containing bridging allyl or related bridging cyclopentadienyl and/or indenyl ligands;134 refs.
ChemInform Abstract: Comparison of Ionic Liquids to Conventional Organic Solvents for Extraction of Aromatics from Aliphatics
Authors: Canales Roberto I. , Brennecke Joan F.
Published: June 2016

Review: 209 refs.
ChemInform Abstract: Late‐Stage Annulative Convergency in Natural Product Synthesis
Authors: Hill Nicholas , Paruch Kamil , Svenda Jakub
Published: June 2016

Review: [147 refs.
ChemInform Abstract: Strategies and Methods for the Synthesis of Pyridinocrownophanes (Microreview)
Authors: Le Anh Tuan , Soldatenkov Anatoly T.
Published: June 2016

Review: [16 refs.
ChemInform Abstract: C‐Linked 8‐Aryl Guanine Nucleobase Adducts: Biological Outcomes and Utility as Fluorescent Probes
Authors: Manderville Richard A. , Wetmore Stacey D.
Published: June 2016

Review: 102 refs.
ChemInform Abstract: Medicinal Uses, Phytochemistry, and Pharmacology of Origanum onites (L.): A Review
Authors: Tepe Bektas , Cakir Ahmet , Tepe Arzuhan Sihoglu
Published: June 2016

Review: 103 refs.
Stereochemical Properties of Multidentate Nitrogen Donor Ligands and Their Copper Complexes by Electronic CD and DFT
Authors: Poopari Mohammad Reza , Dezhahang Zahra , Xu Yunjie
Published: June 2016

UV–Vis and electronic circular dichroism (ECD) spectroscopy, complemented with Density Functional Theory (DFT) calculations, were used to elucidate the structural diversities of three multidentate nitrogen donor ligands and two associated copper complexes in solution directly. The three chiral salen ligands all consist of trans‐cyclohexane‐1,2‐diamine as a chiral scaffold and also of pyridine rings as chromophores, differing only in the linking groups between the two functional groups mentioned above. Very different ECD intensities and somewhat different ECD patterns were observed for these ligands and satisfactorily interpreted theoretically. For the geometry optimization and spectral simulation of the open‐shell metal complexes, the LANL2DZ basis set with effective core potential for the Cu and Cl atoms and pure cc‐pVTZ for the rest of the atoms was utilized. The performance of the same calculations with the polarization functions (f,g) from the cc‐pVTZ basis added to the LANL2DZ basis was compared. While the three ligands exhibit different conformational flexibility, the associated copper complexes show great rigidity imposed by the metal–ligand coordination, taking on a single structure in each case. In addition, dispersion interactions were shown to change the conformational stability ordering of the ligands noticeably and to exert considerable influence on the simulated UV–Vis and ECD spectra. Chirality 28:545–555, 2016. © 2016 Wiley Periodicals, Inc.
High‐Throughput Chiral LC–MS/MS Method Using Overlapping Injection Mode for the Determination of Pantoprazole Enantiomers in Human Plasma with Application to Pharmacokinetic Study
Authors: Li Shengni , Jiang Huafang , Wang Yiya , Liu Yinli , Shen Xiaohang , Liang Wenzhong , Hong Zhanying
Published: June 2016

A sensitive and high‐throughput chiral liquid chromatography–tandem mass spectrometry method was developed and validated for the quantification of R‐pantoprazole and S‐pantoprazole in human plasma. Sample extraction was carried out by using ethyl acetate liquid–liquid extraction in 96‐well plate format. The separation of pantoprazole enantiomers was performed on a CHIRALCEL OJ‐RH column and an overlapping injection mode was used to achieve a run time of 5.0 min/sample. The mobile phase consisted of 1) 10 mM ammonium acetate in methanol: acetonitrile (1:1, v/v) and 2) 20 mM ammonium acetate in water. Isocratic elution was used with flow rate at 500 μL/min. The enantiomers were quantified on a triple‐quadrupole mass spectrometer under multiple reaction monitoring (MRM) mode with m/z 382.1/230.0 for pantoprazole and m/z 388.4/230.1 for pantoprazole‐d7. Linearity from 20.0 to 5000 ng/mL was established for each enantiomer (r2 > 0.99). Extraction recovery ranged from 91.7% to 96.4% for R‐pantoprazole and from 92.5% to 96.5% for S‐pantoprazole and the IS‐normalized matrix factor was 0.98 to 1.07 for R‐pantoprazole and S‐pantoprazole, respectively. The method was demonstrated with acceptable accuracy, precision, selectivity, and stability and the method was applied to support a pharmacokinetic study of a phase I clinical trial of racemic pantoprazole in healthy Chinese subjects. Chirality 28:569–575, 2016. © 2016 Wiley Periodicals, Inc.
Seasonal and Temporal Dynamics of Physicochemical and Biological Properties of Chronosequence Coal Mine Spoil Soils
Authors: Tapadar Sufian A. , Jha Dhruva Kumar
Published: June 2016

Open cast coal mining cause severe damage to soil physicochemical and biological properties. The present study, therefore, was carried out to evaluate the effect of open cast coal mining on the seasonal and temporal dynamics of soil properties. Soil samples were collected from chronosequence spoil soils and one undisturbed forest in two seasons for 2 consecutive years. Most of the studied soil properties deviated from the forest soil. The dumping soils were highly acidic as compared to the forest soil. Soil acidity decreased with increase in soil age. Significant negative correlation of soil pH and nickel (Ni), zinc (Zn), copper (Cu), nitrogen (N), phosphorus (P) (p < 0.01), indicated that increase in spoil soil acidity increased the solubility/availability of these heavy metals, while decrease in soil acidity increased the availability of N and P. High soil acidity and higher concentration of heavy metals reduced the bacterial population number and activity of soil enzymes. Soil enzymes and bacterial population number significantly correlated with each other indicating their interdependence. Seasonal dynamics was observed in soil temperature. While, temporal dynamics was exhibited by soil pH, N, P, Ni, Zn, Cu, and dehydrogenase activity. Soil moisture content, arsenic, bacterial population number, urease, and phosphatase activity exhibited both seasonal and temporal dynamics. Ordination diagram of principal component analysis showed strong relationship of soil biological properties with undisturbed forest and heavy metals with disturbed spoil soils.
Recent Progress in 1D Air Electrode Nanomaterials for Enhancing the Performance of Nonaqueous Lithium–Oxygen Batteries
Authors: Yoon Ki Ro , Jung Ji‐Won , Kim Il‐Doo
Published: June 2016

Lithium–oxygen (Li–O2) batteries are considered as the most promising candidates owing to their higher theoretical energy density than other energy storage devices. However, the unfavorable structure of the air cathode has become a major cause of low performance for Li–O2 batteries, limiting their use in practical applications. To deal with this issue, the rational construction of porous air electrodes, where crucial reactions take place, is in high demand. Among the various dimensional materials, 1D nanomaterials have been frequently applied for air electrodes in several different forms, owing to their fascinating morphologies and unique characteristics. We present a focus review on the recent research relating to 1D nanomaterials adopted as air electrodes in Li–O2 cells. This paper gives the current issues surrounding Li–O2 cells, which are analyzed in terms of the efforts to apply the advantages of 1D nanomaterial electrodes for enhancing the electrochemical performance of the given cells.
On a Class of Fully Nonlinear Elliptic Equations on Closed Hermitian Manifolds II: L∞ Estimate
Authors: Sun Wei
Published: June 2016

We study a class of fully nonlinear elliptic equations on closed Hermitian manifolds. Under the assumption of the cone condition, we derive the L∞ estimate directly. As an application, we solve the complex quotient equations on closed Kähler manifolds. © 2016 Wiley Periodicals, Inc.
Stopping of Deuterium in Warm Dense Deuterium from Ehrenfest Time‐Dependent Density Functional Theory
Authors: Magyar R. J. , Shulenburger L. , Baczewski A. D.
Published: June 2016

In these proceedings, we show that time‐dependent density functional theory is capable of stopping calculations at the extreme conditions of temperature and pressure seen in warm dense matter. The accuracy of the stopping curves tends to be up to about 20% lower than empirical models that are in use. However, TDDFT calculations are free from fitting parameters and assumptions about the model form of the dielectric function. This work allows the simulation of ion stopping in many materials that are difficult to study experimentally. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Spectral diversity area relationships for assessing biodiversity in a wildland–agriculture matrix
Authors: Dahlin Kyla Marie
Published: June 2016

Species–area relationships have long been used to assess patterns of species diversity across scales. Here, this concept is extended to spectral diversity using hyperspectral data collected by NASA's Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) over western Michigan. This mixture of mesic forest and agricultural lands offers two end‐points on the local‐scale diversity continuum; one set of well‐mixed forest patches and one set of highly homogeneous agricultural patches. Using the sum of the first three principal component values and the principal components' convex hull volume, spectral diversity was compared within and among these plots and to null expectations for perfectly random and perfectly patchy landscapes. Overall, the spectral diversity–area relationship confirms the patterns that would be expected for this landscape, but this application suggests that this approach could be extended to less well‐understood landscapes and could reveal key insights about the relative importance of different drivers of community assembly, even in the absence of additional data about plant functional traits or species' identities.
Land use changes in an afrotropical biodiversity hotspot affect stream alpha and beta diversity
Authors: Fugère V. , Kasangaki A. , Chapman L. J.
Published: June 2016

Land use changes such as deforestation and agricultural expansion strongly affect stream biodiversity, with several studies demonstrating negative impacts on stream alpha diversity. Effects of forest conversion on stream beta diversity are much harder to predict, both because empirical studies are few and because competing theories suggest opposite responses. Moreover, almost no data exist for tropical Africa, a region that is paradoxically a hotspot of both current deforestation and freshwater biodiversity. Here, we compared environmental variables, invertebrate community composition, and alpha and beta diversity of forested and deforested (agricultural) streams in and around Kibale National Park, Uganda. We found that forest conversion strongly influenced stream environmental variables and invertebrate community composition, and that agricultural land use reduced stream alpha diversity. However, among‐stream beta diversity was greater across the agricultural landscape than inside the forest. Decomposing beta diversity into taxa replacement and richness differences demonstrated that replacement contributed a similar proportion to total beta diversity in both land use classes. Because of this greater beta diversity, the agricultural landscape had similar gamma diversity as the forested landscape despite its lower alpha diversity. We discuss conservation implications of these land use‐associated biodiversity changes in a highly diverse yet little‐studied deforestation hotspot.
Forecasting the relative influence of environmental and anthropogenic stressors on polar bears
Authors: Atwood Todd C. , Marcot Bruce G. , Douglas David C. , Amstrup Steven C. , Rode Karyn D. , Durner George M. , Bromaghin Jeffrey F.
Published: June 2016

Effective conservation planning requires understanding and ranking threats to wildlife populations. We developed a Bayesian network model to evaluate the relative influence of environmental and anthropogenic stressors, and their mitigation, on the persistence of polar bears (Ursus maritimus). Overall sea ice conditions, affected by rising global temperatures, were the most influential determinant of population outcomes. Accordingly, unabated rise in atmospheric greenhouse gas (GHG) concentrations was the dominant influence leading to worsened population outcomes, with polar bears in three of four ecoregions reaching a dominant probability of decreased or greatly decreased by the latter part of this century. Stabilization of atmospheric GHG concentrations by mid‐century delayed the greatly reduced state by ≈25 yr in two ecoregions. Prompt and aggressive mitigation of emissions reduced the probability of any regional population becoming greatly reduced by up to 25%. Marine prey availability, linked closely to sea ice trend, had slightly less influence on outcome state than sea ice availability itself. Reduced mortality from hunting and defense of life and property interactions resulted in modest declines in the probability of a decreased or greatly decreased population outcome. Minimizing other stressors such as trans‐Arctic shipping, oil and gas exploration, and contaminants had a negligible effect on polar bear outcomes, although the model was not well‐informed with respect to the potential influence of these stressors. Adverse consequences of loss of sea ice habitat became more pronounced as the summer ice‐free period lengthened beyond four months, which could occur in most of the Arctic basin after mid‐century if GHG emissions are not promptly reduced. Long‐term conservation of polar bears would be best supported by holding global mean temperature to ≤ 2°C above preindustrial levels. Until further sea ice loss is stopped, management of other stressors may serve to slow the transition of populations to progressively worsened outcomes, and improve the prospects for their long‐term persistence.