bluuebunny/crossref_metadata_2025 huggingface dataset:
ChemInform Abstract: SELECTIVITY AND DIRECTED CHARGE TRANSFER THROUGH AN ELECTROACTIVE METALLOPOLYMER FILM
Authors: ELLIS C. D. , MURPHY W. R. JUN. , MEYER T. J.
Published: April 2016

Die voltammetrischen Eigenschaften der Redoxpaare (I) und (II) werden in Acetonitril an einer Pt‐Elektrode, die chemisch durch Elektropolymerisation von (III) modifiziert ist, untersucht.
ChemInform Abstract: CHELATING 2‐(DIPHENYLPHOSPHINO)PYRIDINE. SYNTHESIS AND STRUCTURE OF DICHLORODICARBONYL(2‐(DIPHENYLPHOSPHINO)PYRIDINE)RUTHENIUM(II)
Authors: OLMSTEAD M. M. , MAISONNAT A. , FARR J. P. , BALCH A. L.
Published: April 2016

Der oktaedrische Titelkomplex (II) wird durch Behandlung des Triruthenium‐Komplexes (I) mit molekularem Chlor synthetisiert.
ChemInform Abstract: STABLE GLUCOPYRANOSYLPALLADIUM COMPOUND WITH A CIS β‐HYDROGEN
Authors: ARAI I. , DAVES G. D. JUN.
Published: April 2016

Der Titelkomplex (IV) mit Pd‐C‐o‐Bindung wurde durch regio‐ und stereospezifische Addition einer in situ aus (I) und (III) erhaltenen Pyrimidindion‐5‐yl‐Pd(II)‐Verbindung an das D‐Glucal (II) dargestellt und durch 1H‐ und 13C‐NMR‐Daten charakterisiert.
ChemInform Abstract: SYNTHESIS AND CRYSTAL STRUCTURE OF BARIUM TETRAKIS(μ‐SQUARATO‐O1,O2)‐DIPLATINATE(II) HEXAHYDRATE
Authors: SIMONSEN O. , TOFTLUND H.
Published: April 2016

Die Titelverbindung (I) entsteht bei Behandlung einer Tetraaquo‐Pt(II)‐ Lösung mit Quadratsäure bei 55°C gemeinsam mit anderen Quadratoplatinaten(II).
ChemInform Abstract: Chemical Synthesis of a (1→2)‐D‐Glucopyranan.
Authors: SHARKEY P. F. , EBY R. , SHUERCH C.
Published: April 2016

1,2‐Anhydro‐3,4,6‐tri‐O‐benzyl‐a‐ D‐glucopyranose (I) wird in Gegenwart von Phosphorpentafluorid zu einem benzy′‐ lierten (l‐2)‐β‐D‐Glucopyranan polymerisiert (Ausb. 60%) und zu (II) entblockiert.
ChemInform Abstract: TOTAL SYNTHESES OF EBURNAMONINE, QUEBRACHAMINE, VINCADINE AND EPIVINCADINE
Authors: WENKERT E. , HALLS T. D. J. , KWART L. D. , MAGNUSSON G. , SHOWALTER H. D. H.
Published: April 2016

Reduktion der isomeren Carbinolaminether (VIII), die entweder ausgehend von (II) über die Stufen (VII) oder ausgehend vom (Ia)‐ Reduktionsprodukt (Ib) über die Stufe (X) zugänglich sind, liefert die Alkohole (IXa) bzw. (IXb), deren Überführung über die Salze (XI) in (i)‐Quebrachamin (XIIa) bekannt ist.
ChemInform Abstract: SYNTHESIS OF DL‐CORIOLIN
Authors: TROST B. M. , CURRAN D. P.
Published: April 2016

Ausgehend von den Endion (I) wird über die Intermediären (II)‐(X) die Schlüsselverbindung (XI) synthetisiert, deren Bis‐trimethylsilylenolether durch Reaktion mit Eschenmoser′s Salz die Mannich‐Base liefert, aus der durch Quaternisierung mit MeI und anschließende Eliminierung das Methylenketon (XIIa) erhalten wird.
ChemInform Abstract: PHEROMONES. PART 37. A STEREOSPECIFIC SYNTHESIS OF THE COMPONENTS OF THE SEX PHEROMONE OF ANTHERAEA POLYPHEMUS, (E,Z)‐6,11‐HEXADECADIENYL ACETATE AND (E,Z)‐HEXADECADIENAL
Authors: BESTMANN H. J. , LI K.
Published: April 2016

Aus dem Ylid (I) und 2‐Hydroxy‐tetrahydropyran (II) entsteht das Carbinol (IIIa), das mit Chromtrioxid/Pyridin zum Aldehyd (IIIb) ‐ oxidiert und dann mit Tetrabromkohlenstoff und Triphenylphosphin im Sinne einer Wittig‐Reaktion zum Dibrommethylenderivat (IV) reagiert.
Numerical simulation of breast reduction with a new knitting condition
Authors: Lopes Diogo , Clain Stéphane , Pereira Rui M. S. , Machado Gaspar J. , Smirnov Georgi , Vasilevskiy Igor
Published: April 2016

Breast reduction is one of the most common procedures in breast surgery. The aim of this work is to develop a computational model allowing one to forecast the final breast geometry according to the incision marking parameters. This model can be used in surgery simulators that provide preoperative planning and training, allowing the study of the origin of the errors in breast reduction. From the mathematical point of view, this is a problem of calculus of variations with unusual boundary conditions, known as knitting conditions. The breast tissue is considered as a hyperelastic material, discretized with three‐dimensional finite elements for the body, whereas the skin is modelled with two‐dimensional finite elements on the curved surface. Although the model is of low precision, we show that it is sufficient for a satisfactory prediction of breast reduction surgery results, allowing an analysis of errors frequently performed during the surgery and giving an understanding of how to avoid or correct them. Copyright © 2016 John Wiley & Sons, Ltd.
Comparative population structure of two dominant species, Shinkaia crosnieri (Munidopsidae: Shinkaia) and Bathymodiolus platifrons (Mytilidae: Bathymodiolus), inhabiting both deep‐sea vent and cold seep inferred from mitochondrial multi‐genes
Authors: Shen Yanjun , Kou Qi , Chen Weitao , He Shunping , Yang Mei , Li Xinzheng , Gan Xiaoni
Published: April 2016

Deep‐sea hydrothermal vents and cold seeps, limited environments without sunlight, are two types of extreme habitat for marine organisms. The differences between vents and cold seeps may facilitate genetic isolation and produce population heterogeneity. However, information on such chemosynthetic fauna taxa is rare, especially regarding the population diversity of species inhabiting both vents and cold seeps. In this study, three mitochondrial DNA fragments (the cytochrome c oxidase submit I (COI), cytochrome b gene (Cytb), and 16S) were concatenated as a mitochondrial concatenated dataset (MCD) to examine the genetic diversity, population structure, and demographic history of Shinkaia crosnieri and Bathymodiolus platifrons. The genetic diversity differences between vent and seep populations were statistically significant for S. crosnieri but not for B. platifrons. S. crosnieri showed less gene flow and higher levels of genetic differentiation between the vent and seep populations than B. platifrons. In addition, the results suggest that all the B. platifrons populations, but only the S. crosnieri vent populations, passed through a recent expansion or bottleneck. Therefore, different population distribution patterns for the two dominant species were detected; a pattern of population differentiation for S. crosnieri and a homogeneity pattern for B. platifrons. These different population distribution patterns were related to both extrinsic restrictive factors and intrinsic factors. Based on the fact that the two species were collected in almost identical or adjacent sampling sites, we speculated that the primary factors underlying the differences in the population distribution patterns were intrinsic. The historical demographics, dispersal ability, and the tolerance level of environmental heterogeneity are most likely responsible for the different distribution patterns.
Systematic Synthesis of Di‐, Tri‐, and Tetranuclear Homo‐ and Heterometal Complexes Using a Mononuclear Copper Synthon with a Tetradentate Amino Alcohol Ligand
Authors: Nakajima Takayuki , Yamashiro Chisako , Taya Megumi , Kure Bunsho , Tanase Tomoaki
Published: April 2016

The reaction of Cu(NO3)2·3H2O with an N2O2 tetradentate amino alcohol, N,N‐dibenzyl‐N′,N′‐bis(2‐hydroxyethyl)ethylenediamine (H2L), afforded the mononuclear copper complex [Cu(H2L)(NO3)](NO3) (1), which has been used to construct a series of di‐, tri‐, and tetranuclear homo‐ and heterometallic complexes. Complex 1 dimerized in the presence of NEt3 to form the Cu2 complex [Cu2(HL)2](NO3)2 (2) by the deprotonation of one of the two hydroxy groups in the H2L ligand. The reaction of 1 with Cu(OCOH)2 in the presence of NEt3 afforded the Cu3 complex [Cu3(HL)2(OCOH)2](NO3)2 (5). The metalloligand {Cu(HL)}+ derived from 1 reacted with M(OAc)2 (M = Cu, Co, Zn, Ni) in the absence of NEt3 to form the asymmetric CuM dinuclear complexes [CuM(HL)(OAc)(NO3)2] [M = Cu (3a), Co (3b), Zn (3c), Ni (3d)], whereas in the presence of NEt3 a unit of M(OAc) was captured by two metalloligands to give the bent CuMCu trinuclear complexes [Cu2M(HL)2(OAc)2(NO3)](NO3) [M = Cu (4a), Co (4b), Mn (4c)], which were further transformed into the linear CuMCu trinuclear complexes [Cu3(HL)2{(PhO)2PO2}2](NO3)2 (7a) and [Cu2M(HL)2{(PhO)2PO2}2(MeOH)2](NO3)2 [M = Co (7b), Mn (7c)] with the aid of diphenyl phosphate bridging ligands. When (PhO)PO2(OH) was used as an auxiliary bridging ligand in the reaction of 1 with M(OAc)2 and NEt3, the Cu2M2 tetranuclear complexes [Cu2M2(HL)2{(PhO)PO3}2(NO3)2] [M = Co (8a), Zn (8b)] were synthesized. These results demonstrate that the mononuclear copper synthon with the N2O2 tetradentate amino alcohol ligand {Cu(H2L)}2+ generates the quite useful metalloligand {Cu(HL)}+ by the deprotonation of a hydroxy group, and subsequent reactions lead to the construction of a series of homo‐ and heterometal complexes containing Cu2, CuM (M = Cu, Co, Zn, Ni), bent‐CuMCu (M = Cu, Co, Mn), linear‐CuMCu (M = Cu, Co, Mn), and Cu2M2 (M = Co, Mn) cores in a systematic and selective manner.
Synthesis of Gold(I) Derivatives Bearing Alkylated 1,3,5‐Triaza‐7‐phosphaadamantane as Selective Anticancer Metallodrugs
Authors: Atrián‐Blasco Elena , Gascón Sonia , Rodríguez‐Yoldi M. Jesús , Laguna Mariano , Cerrada Elena
Published: April 2016

The alkylation of one of the nitrogen atoms of the molecule 1,3,5,triaza‐7‐phosphaadamantane (PTA) with para‐substituted benzylic units and the l‐phenylalanine methyl ester moiety are reported. The crystalline structures of the two alkylated PTA species [PTA‐CH2‐p‐COOH‐C6H4]Br (1a) and [PTA‐CH2‐p‐CH2COOH‐C6H4]Br (2) reveal the presence of interactions between the bromide anion and the OH group of the acid moiety. Bis‐phosphane derivatives were prepared by the alkylation of two PTA molecules with a dibromide salt to afford more water‐soluble species. The corresponding mono‐ and dinuclear chloro‐, thiocyanato‐ and pentafluorophenyl gold(I) derivatives are described. Most of the new complexes have been tested as anticancer agents, exhibiting higher cytotoxicity than cisplatin against human colon cancer cell lines. Some of them display low cytotoxicity towards differentiated cells (non‐carcinogenic), as determined from viability studies, thereby demonstrating a significant specificity in this type of cancer.
Synthesis, Characterization and Aerobic Alcohol Oxidation Catalysis of Palladium(II) Complexes with a Bis(imidazolyl)borate Ligand
Authors: Ando Kenta , Nakazawa Jun , Hikichi Shiro
Published: April 2016

Chloro‐ and hydroxo‐palladium(II) complexes with an imidazole‐based scorpionate ligand bis(1‐methylimidazolyl)methylphenylborate, [B(ImN–Me)2MePh]– (= LPh), have been synthesized. Reaction of a lithium salt of LPh with [PdCl2(NCPh)2] yields a miscellaneous mixture involving a homoleptic complex [Pd(LPh)2]. Replacement of the neutral ligand (benzonitrile) in the starting material with pyridine leads to the desired chloride complex 1. X‐ray crystallographic analysis reveals the formula of 1 to be [PdCl(LPh)(py)] with a square‐planar palladium(II) center supported by the bidentate LPh ligand. Treatment of 1 with NaOH yields non‐pyridine‐containing hydroxo species with LPh such as [Pd(OH)(LPh)(H2O)] and [(PdLPh)2(µ‐OH)2]. The hydroxo species 2 can convert into active species for catalytic secondary alcohol oxidation with O2 in the absence of extra base. The utility of 2 as a catalyst precursor and the inertness of chloride complex 1 suggest that the basic nature of the co‐ligand (i.e. OH–) on the palladium center supported by LPh is essential to the formation of a putative palladium–alkoxide intermediate.
Reactivity of an N‐Heterocyclic Carbene Stabilized Hydrosilylene towards a Ketone and CO2: Experimental and Theoretical Study
Authors: Eisenhut Carsten , Breit Nora C. , Szilvási Tibor , Irran Elisabeth , Inoue Shigeyoshi
Published: April 2016

The reaction of N‐heterocyclic carbene (NHC)‐stabilized hydrosilylene 1, tBu3SiSi(H)←NHC, with one and two equivalents of benzophenone gave rise to bicyclic compounds 2 and 3, tBu3Si(R)[Si‐CH2‐N(CMeCMeNMe)‐CPh2‐O] (R = H, OCHPh2). The NHC plays a crucial role in this reactivity, as it is directly involved in C–C bond formation and supplies the C–H‐activated methyl group. In the formation of 3, the terminal Si–H bond of the hydrosilylene is involved in transition‐metal‐free hydrosilylation. All steps in these mechanisms are based on NHC‐stabilized zwitterionic transition states and intermediates and were investigated by utilizing DFT calculations. In addition, the CO2 activation of 1 to yield cis/trans‐cyclotrisiloxane 4, [(tBu3Si)(H)Si‐O]3, stereoselectively and its mechanistic study are reported.
Microwave‐Assisted C‐2 Direct Alk­enylation of Imidazo[4,5‐b]pyr­idines: Access to Fluorescent Purine Isosteres with Remarkably Large Stokes Shifts
Authors: Baladi Tom , Granzhan Anton , Piguel Sandrine
Published: April 2016

We describe herein the first C‐2 direct alkenylation of the valuable 3H‐imidazo[4,5‐b]pyridine promoted by microwave‐assisted Pd/Cu co‐catalysis. The reaction is rapid and compatible with a wide range of functional groups either on the imidazo[4,5‐b]pyridine ring or on the styryl bromides thereby leading to the isolation of 23 compounds with moderate to good yields. The relevance of this method is demonstrated by its application to the synthesis of new cross‐conjuguated push–pull 2‐vinyl‐ and 2‐alkynylimidazo[4,5‐b]pyridines characterized by satisfactory fluorescence quantum yields and remarkable solvatofluorochromic properties.
(D–π–)2D–π–A‐Type Organic Dyes for Efficient Dye‐Sensitized Solar Cells
Authors: Kaewpuang Terdkait , Prachumrak Narid , Namuangruk Supawadee , Jungsuttiwong Siriporn , Sudyoadsuk Taweesak , Pattanasattayavong Pichaya , Promarak Vinich
Published: April 2016

New (D–π–)2D–π–A‐type dyes (CFTTnA, n = 2, 3) with a triarylamine as electron donor, a cyanoacrylic acid as both electron acceptor and anchoring group, and two π‐conjugated 2‐[7‐(3,6‐di‐tert‐butylcarbazol‐9‐yl)‐9,9‐dihexylfluoren‐2‐yl]thiophenes as N‐aryl substituents on the amine donor as co‐donors have been synthesized and characterized. Compared with a traditional D–π–A‐type dye, these dyes exhibit broader absorption spectra and higher molar extinction coefficients as well as significantly enhanced photovoltaic performances. A power conversion efficiency of 6.64 % was achieved for a dye‐sensitized solar cell (DSSC) based on CFTT3A. Theoretical calculations and electrochemical impedance spectroscopic investigations revealed the mechanism of the enhanced dye properties and cell performances.
Stereoselective Substitution of Configurationally Labile α‐Bromo Aryl­acetates with Amines and Az­lactones by L‐Threonine‐Mediated Crystallization‐Induced Dynamic Resolution
Authors: Yun Soo Choi  , Park SeHee , Park Yong Sun
Published: April 2016

We developed a highly stereoselective C–N and C–C bond‐forming reaction by carrying out a crystallization‐induced dynamic resolution (CIDR) of α‐bromo arylacetates followed by a stereoselective substitution reaction with an amine or azlactone nucleophile. Applications of this synthetic method to the preparation of highly enantioenriched nitrogen‐containing six‐membered heterocycles and α,β‐disubstituted aspartates are also presented.
Syntheses, Structures and Optoelectronic Properties of Spiroconjugated Cyclic Ketones
Authors: Wilbuer Jennifer , Schnakenburg Gregor , Esser Birgit
Published: April 2016

Synthetic investigations towards spiroconjugated ketones and derivatives thereof are presented. These studies led to the development of a short procedure for the synthesis of spiroconjugated tetraketone 1 in two steps with 10 % overall yield and the first‐time synthesis of spirocyclic trindone 2. The optoelectronic properties of these compounds based on spectroscopic and electrochemical measurements in combination with DFT calculations as well as their molecular structures in the solid state are presented and discussed.
Diastereo‐ and Enantioselective Synthesis of Spiro‐Pyrrolidine‐Pyr­azolones by Squaramide‐Catalyzed Cascade Aza‐Michael/Michael Reactions
Authors: Li Jun‐Hua , Wen Hongliang , Liu Lei , Du Da‐Ming
Published: April 2016

A new method was developed to rapidly generate a series of spiro‐pyrrolidine‐pyrazolones by using a squaramide‐catalyzed cascade aza‐Michael/Michael addition of either tosylaminomethyl enones or enoates to unsaturated pyrazolones. This tandem reaction sequence proceeded well by using 5 mol‐% of a chiral bifunctional tertiary amine squaramide catalyst to afford the desired products in good to excellent yields (up to 98 %) with excellent diastereoselectivities [up to >20:1 diastereomeric ratio (dr)] and high to excellent enantioselectivities (up to 98 % ee).
Small Donor–Acceptor Molecules Based on a Quinoline–Fluorene System with Promising Photovoltaic Properties
Authors: Slodek Aneta , Matussek Marek , Filapek Michal , Szafraniec‐Gorol Grazyna , Szlapa Agata , Grudzka‐Flak Iwona , Szczurek Magdalena , Malecki Jan Grzegorz , Maron Anna , Schab‐Balcerzak Ewa , Nowak Elzbieta M. , Sanetra Jerzy , Olejnik Marian , Danikiewicz Witold , Krompiec Stanislaw
Published: April 2016

A series of small donor–acceptor (D–A) systems based on quinoline derivatives bearing a fluorenyl motif were synthesized through Ru‐catalyzed reactions. Their photophysical, electrochemical, and structural properties were investigated deeply. The photoluminescence spectra of most of the compounds were characterized by an intense band at λ ≈ 400 nm, whereas a redshifted band occurred at λ = 560 nm if the substituent of the quinoline was changed to the strongly electron‐withdrawing NO2 group. Most of the synthesized compounds exhibited appealing luminescence and electrical properties, which might make them useful materials for photovoltaics. Preliminary electrical conductivity measurements of indium tin oxide/compound/Al devices showed that the current is enhanced as the applied voltage increases and, therefore, proved the semiconducting properties of the investigated compounds. Moreover, one of the synthesized compound was tested as a component of the active layer in a bulk heterojunction (BHJ) solar cell, and a power conversion efficiency (PCE) of 0.25 % was obtained.
Performance loss of Corynebacterium glutamicum cultivations under scale‐down conditions using complex media
Authors: Lemoine Anja , Limberg Michael H. , Kästner Steffen , Oldiges Marco , Neubauer Peter , Junne Stefan
Published: April 2016

Substrate and oxygen gradients appear in industrial‐scale fed‐batch processes due to limitations in the achievable power input and concomitantly increased mixing times. In order to mimic these gradients at lab scale, scale‐down reactors are applied. Previous studies in such reactor systems suggest that Corynebacterium glutamicum is robust against oscillatory oxygen and substrate availability in relation to growth and side product accumulation. Usually, defined mineral salt media are applied contrary to the industrial case, in which complex media containing different carbon sources are used. Therefore, this study investigated the cultivation performance using complex medium based on sucrose, molasses, and corn steep liquor in a three‐compartment scale‐down reactor. The reactor consisted of a stirred tank and two plug flow reactor modules. This approach was applied based on assumptions of gradient distributions in bottom‐fed bioreactors. A drastic reduction of growth and volumetric product yield of a cadaverine producing strain was observed while several short chain fatty acids accumulated, among them l‐lactate and acetate. Growth was depleted after several hours of cultivation, while the substrate uptake rate was reduced by 20%. Hence, the main carbon source sucrose accumulated after 10 h of fed‐batch cultivation. Despite growth cessation, neither reduction of cell vitality nor increased cell lysis were observed.
Analytical modelling of multi‐mass flexible rocking structures
Authors: Acikgoz Sinan , DeJong Matthew J.
Published: April 2016

This paper presents a new analytical model for describing the large rocking response of an elastic multi‐mass structure resting on ideally rigid ground. Using the experimental results from a rocking steel column, the ability of the proposed analytical model to estimate the rocking and translational acceleration response under free vibration, pulse and earthquake excitations is evaluated. It is observed that the classical treatment of impact may result in an unrealistically large transfer of energy to vibrations. Therefore a new Dirac‐delta type impact model that spreads the effects of impact over time and space is proposed. The use of a Dirac‐delta model and accurate restitution factors play a pivotal role in prediction of rocking and acceleration responses. In order to characterize the nonlinear response better, a modal analysis of the linearized system is proposed. With this approach, the vibration mode frequencies and shapes during rocking action were determined. A comparison of analytical and experimental modal estimations suggests good agreement. The results emphasize that the vibration characteristics of several vibration modes are affected by rocking action, and these modes may be excited at impact. Copyright © 2016 John Wiley & Sons, Ltd.
Building a minimum frustration framework for brain functions over long time scales
Authors: Tozzi Arturo , Flå Tor , Peters James F.
Published: April 2016

The minimum frustration principle (MFP) is a computational approach stating that, over the long time scales of evolution, proteins' free energy decreases more than expected by thermodynamical constraints as their amino acids assume conformations progressively closer to the lowest energetic state. This Review shows that this general principle, borrowed from protein folding dynamics, can also be fruitfully applied to nervous function. Highlighting the foremost role of energetic requirements, macromolecular dynamics, and above all intertwined time scales in brain activity, the MFP elucidates a wide range of mental processes from sensations to memory retrieval. Brain functions are compared with trajectories that, over long nervous time scales, are attracted toward the low‐energy bottom of funnel‐like structures characterized by both robustness and plasticity. We discuss how the principle, derived explicitly from evolution and selection of a funneling structure from microdynamics of contacts, is unlike other brain models equipped with energy landscapes, such as the Bayesian and free energy principles and the Hopfield networks. In summary, we make available a novel approach to brain function cast in a biologically informed fashion, with the potential to be operationalized and assessed empirically. © 2016 Wiley Periodicals, Inc.
Role of regulatory b cells in neuroimmunologic disorders
Authors: Han Jinming , Sun Li , Fan Xueli , Wang Zhongkun , Cheng Yun , Zhu Jie , Jin Tao
Published: April 2016

B lymphocytes augment the immune response by producing antibodies and activating T cells by antigen presentation. Recent studies have highlighted a specific and functionally significant B‐cell subset that could downregulate excessive immune and inflammatory responses through a vast array of inhibitory cytokines, such as interleukin (IL)‐10 and transforming growth factor‐β (TGF‐β). This subset of B cells is generally referred to as regulatory B cells (Bregs). In addition, recent studies have shown that IL‐35‐producing Bregs also play a role in downregulation of immunity. Diverse phenotypes of Bregs have been proposed to underlie human disorders and their animal models. Most studies have focused on the role of different subsets of Bregs and Bregs‐associated molecules such as IL‐10, TGF‐β, and IL‐35 in the pathogenesis of neuroimmunologic disorders. Furthermore, Bregs exert regulatory function mainly through suppressing the differentiation of Th1/Th17 cells and promoting regulatory T‐cell expansion. Reduced presence of Bregs is reportedly associated with progression of several neuroimmunologic disorders. This Review summarizes the current knowledge on the role of Bregs in neuroimmunologic disorders, including multiple sclerosis, neuromyelitis optica, and myasthenia gravis. © 2016 The Authors. Journal of Neuroscience Research Published by Wiley Periodicals, Inc.
Trend analysis of temperature and precipitation extremes in major grain producing area of China
Authors: Tian Jiyang , Liu Jia , Wang Jianhua , Li Chuanzhe , Nie Hanjiang , Yu Fuliang
Published: April 2016

To identify whether the spatial and temporal distribution of temperature extremes and precipitation extremes has changed in central and eastern China including Henan, Shandong, Anhui and Jiangsu provinces, the spatial and temporal distributions of extreme temperature and precipitation indices trends during 1961–2011 were investigated and analysed. To guarantee the accuracy of trend analysis, daily maximum and minimum surface temperature and daily precipitation from 299 meteorological stations were used. Eight extreme temperature indices and seven extreme precipitation indices were chosen. Mann–Kendall method was used to check the statistical significance of trends, while Sen's nonparametric method was used to calculate the trend magnitudes. The analyses of extreme temperature indices detected significant and stable trends in the majority of the stations, especially for the most part of southern Anhui and southern Jiangsu provinces. The strongly stable downward trends in cold extremes and the strongly stable upward trends in hot extremes were recorded in most of the regions. In contrast, significant and stable positive trends were insignificantly recorded for precipitation extremes in the study area, which predominantly occurred in the southern part of the region. Furthermore, the positive trends were more frequent than the negative trends in most extreme precipitation indices. The results may provide a reference for a more particular knowledge of the climate change in this region and provide guidance for agriculture development.
Quality‐control of an hourly rainfall dataset and climatology of extremes for the UK
Authors: Blenkinsop Stephen , Lewis Elizabeth , Chan Steven C. , Fowler Hayley J.
Published: April 2016

Sub‐daily rainfall extremes may be associated with flash flooding, particularly in urban areas but, compared with extremes on daily timescales, have been relatively little studied in many regions. This paper describes a new, hourly rainfall dataset for the UK based on ∼1600 rain gauges from three different data sources. This includes tipping bucket rain gauge data from the UK Environment Agency (EA), which has been collected for operational purposes, principally flood forecasting. Significant problems in the use of such data for the analysis of extreme events include the recording of accumulated totals, high frequency bucket tips, rain gauge recording errors and the non‐operation of gauges. Given the prospect of an intensification of short‐duration rainfall in a warming climate, the identification of such errors is essential if sub‐daily datasets are to be used to better understand extreme events. We therefore first describe a series of procedures developed to quality control this new dataset. We then analyse ∼380 gauges with near‐complete hourly records for 1992–2011 and map the seasonal climatology of intense rainfall based on UK hourly extremes using annual maxima, n‐largest events and fixed threshold approaches. We find that the highest frequencies and intensities of hourly extreme rainfall occur during summer when the usual orographically defined pattern of extreme rainfall is replaced by a weaker, north–south pattern. A strong diurnal cycle in hourly extremes, peaking in late afternoon to early evening, is also identified in summer and, for some areas, in spring. This likely reflects the different mechanisms that generate sub‐daily rainfall, with convection dominating during summer. The resulting quality‐controlled hourly rainfall dataset will provide considerable value in several contexts, including the development of standard, globally applicable quality‐control procedures for sub‐daily data, the validation of the new generation of very high‐resolution climate models and improved understanding of the drivers of extreme rainfall.
Computational design and fabrication of core–shell magnetic molecularly imprinted polymer for dispersive micro‐solid‐phase extraction coupled with high‐performance liquid chromatography for the determination of rhodamine 6G
Authors: Xie Jin , Xie Jie , Deng Jian , Fang Xiangfang , Zhao Haiqing , Qian Duo , Wang Hongjuan
Published: April 2016

A novel core–shell magnetic nano‐adsorbent with surface molecularly imprinted polymer coating was fabricated and then applied to dispersive micro‐solid‐phase extraction followed by determination of rhodamine 6G using high‐performance liquid chromatography. The molecularly imprinted polymer coating was prepared by copolymerization of dopamine and m‐aminophenylboronic acid (functional monomers), in the presence of rhodamine 6G (template). The selection of the suitable functional monomers was based on the interaction between different monomers and the template using the density functional theory. The ratios of the monomers to template were further optimized by an OA9 (34) orthogonal array design. The binding performances of the adsorbent were evaluated by static, kinetic, and selective adsorption experiments. The results reveal that the adsorbent possesses remarkable affinity and binding specificity for rhodamine 6G because of the enhanced Lewis acid‐base interaction between the B(Ш) embedded in the imprinted cavities and the template. The nano‐adsorbent was successfully applied to dispersive micro‐solid‐phase extraction coupled to high‐performance liquid chromatography for the trace determination of rhodamine 6G in samples with a detection limit of 2.7 nmol/L. Spiked recoveries ranged from 93.0–99.1, 89.5–92.7, and 86.9–105% in river water, matrimony vine and paprika samples, respectively, with relative standard deviations of less than 4.3%.
The Importance of Relative Reaction Rates in the Optimization of Detailed Kinetic Models
Authors: Manion Jeffrey A. , McGivern W. Sean
Published: April 2016

Numerous mathematical tools intended to adjust rate constants employed in complex detailed kinetic models to make them consistent with multiple sets of experimental data have been reported in the literature. Application of such model optimization methods typically begins with the assignment of uncertainties in the absolute rate constants in a starting model, followed by variation of the rate constants within these uncertainty bounds to tune rate parameters to match model outputs to experimental observations. The present work examines the impact of including information on relative reaction rates in the optimization strategy, which is not typically done in current implementations. It is shown that where such rate constant data are available, the available parameter space changes dramatically due to the correlations inherent in such measurements. Relative rate constants are typically measured with greater relative accuracy than corresponding absolute rate constant measurements. This greater accuracy further reduces the available parameter space, which significantly affects the uncertainty in the model outcomes as a result of kinetic parameter uncertainties. We demonstrate this effect by considering a simple example case emulating an ignition event and show that use of relative rate measurements leads to a significantly smaller uncertainty in the output ignition delay time in comparison with results based on absolute measurements. This is true even though the same range of absolute rate constants is sampled in each case. Implications of the results with respect to the maintenance of physically realistic kinetics in optimized models are discussed, and suggestions are made for the path forward in the refinement of detailed kinetic models.
Posterior cricoarytenoid muscle electrophysiologic changes are predictive of vocal cord paralysis with recurrent laryngeal nerve compressive injury in a canine model
Authors: Puram Sidharth V. , Chow Harold , Wu Che‐Wei , Heaton James T. , Kamani Dipti , Gorti Gautham , Chiang Feng Yu , Dionigi Gianlorenzo , Barczynski Marcin , Schneider Rick , Dralle Henning , Lorenz Kerstin , Randolph Gregory W.
Published: April 2016

Objectives/Hypothesis

Injury to the recurrent laryngeal nerve (RLN) is a dreaded complication of endocrine surgery. Intraoperative neural monitoring (IONM) has been increasingly utilized to assess the functional status of the RLN. Although the posterior cricoarytenoid muscle (PCA) is innervated by the RLN as the abductor of the larynx, PCA electromyography (EMG) is infrequently recorded during IONM and PCA activity after RLN compressive injury remains poorly characterized.

Study Design

Single‐subject prospective animal study.

Methods

We employed a canine model to identify postcricoid EMG correlates of postoperative vocal cord paralysis (VCP). Postcricoid electrode recordings were obtained before and after compressive RLN injury associated with VCP.

Results

Normative postcricoid recordings revealed mean amplitude of 1288 microvolt (μV) and latency of 8.2 millisecond (ms) with maximum (1 milliamp [mA]) vagal stimulation, and mean amplitude of 1807 μV and latency of 3.5 ms with maximum (1 mA) RLN stimulation. Following injury that was associated with VCP, there was 62.1% decrement in postcricoid EMG amplitude with maximum vagal stimulation and 80% decrement with maximum RLN stimulation. Threshold stimulation of the vagus increased by 23%, and there was a corresponding 42% decrease in amplitude. For RLN stimulation, latency increased by 17.3% following injury, whereas threshold stimulation increased by 61% with 35.5% decrement in EMG amplitude. Thus, if RLN amplitude decreases by ≥ 80%, with absolute amplitude of ≤ 300 μV or less and latency increase of ≥ 10%, RLN injury is likely associated with VCP.

Conclusion

Our results predict postoperative VCP based on postcricoid electromyographic IONM and may guide surgical decision making.

Level of Evidence

NA Laryngoscope, 126:2744–2751, 2016
Polymeric Nanohybrids as a New Class of Therapeutic Biotransporters
Authors: Whitlow Jonathan , Pacelli Settimio , Paul Arghya
Published: April 2016

A possible solution to enhance existing drug and gene therapies is to develop hybrid nanocarriers capable of delivering therapeutic agents in a controlled and targeted manner. This goal can be achieved by designing nanohybrid systems, which combine organic or inorganic nanomaterials with biomacromolecules into a single composite. The unique combination of properties along with their facile fabrication enables the design of smart carriers for both drug and gene delivery. These hybrids can be further modified with cell targeting motifs to enhance their biological interactivity. In this Talents and Trends article, an overview of emerging nanohybrid‐based technologies will be provided to highlight their potential use as innovative platforms for improved cancer therapies and new strategies in regenerative medicine. The clinical relevance of these systems will be reviewed to define the current challenges which still need to be addressed to allow these therapies to move from bench to bedside.

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Study of the composition and morphology of new modifications of titanium‐magnesium catalysts with improved properties in ethylene polymerization
Authors: Mikenas Tatiana B. , Koshevoy Evgeny I. , Cherepanova Svetlana V. , Zakharov Vladimir A.
Published: April 2016

Data on new modifications of supported titanium‐magnesium catalysts (TMCs) with improved performance in ethylene polymerization are reported. These catalysts possess a high and stable activity, an enhanced ability to regulate molecular weight of the polymer by hydrogen, a controllable particle size at a narrow particle size distribution, and the ability to produce the polymer with an increased bulk density. Various physicochemical methods were used to obtain data on the chemical composition of novel supports and catalysts, their phase composition and crystal structure as well as the pore structure. The results obtained were used to discuss possible correlations between composition and structure of TMCs and their catalytic properties. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2545–2558
Sensitivity of resolved and parametrized surface drag to changes in resolution and parametrization
Authors: van Niekerk Annelize , Shepherd Theodore G. , Vosper Simon B. , Webster Stuart
Published: April 2016

The relative contributions of resolved and parametrized surface drag towards balancing the atmospheric angular momentum flux convergence (AMFC) and their sensitivity to horizontal resolution and parametrization are investigated in an atmospheric model. This sensitivity can be difficult to elucidate in free‐running climate models, in which the AMFC varies with changing climatologies and, as a result, the relative contributions of surface terms balancing the AMFC also vary. While the sensitivity question has previously been addressed using short‐range forecasts, we demonstrate that a nudging framework is an effective method for constraining the AMFC. The Met Office Unified Model is integrated at three horizontal resolutions ranging from 130 (N96) to 25 km (N512), while relaxing the model's wind and temperature fields towards the ERA‐Interim reanalysis within the altitude regions of maximum AMFC. This method is validated against short‐range forecasts and good agreement is found. These experiments are then used to assess the fidelity of the exchange between parametrized and resolved orographic torques with changes in horizontal resolution. Although the parametrized orographic torque reduces substantially with increasing horizontal resolution, there is little change in resolved orographic torque over 20–50°N. The tendencies produced by the nudging routine indicate that the additional drag at lower horizontal resolution is excessive. When parametrized orographic blocking is removed at the coarsest of these resolutions, there is a lack of compensation, and even compensation of the opposite sense, by the boundary layer and resolved torques, which is particularly pronounced over 20–50°N. This study demonstrates that there is strong sensitivity in the behaviour of the resolved and parametrized surface drag over this region.
Crowdsourced Seismology
Authors: Deatrick Elizabeth
Published: April 2016

The seismologists of the world want to turn you into an earthquake detector.
LIMK Regulates Tumor-Cell Invasion and Matrix Degradation Through Tyrosine Phosphorylation of MT1-MMP
Authors: Lagoutte Emilie , Villeneuve Clémentine , Lafanechère Laurence , Wells Claire M. , Jones Gareth E. , Chavrier Philippe , Rossé Carine
Published: April 2016

During their metastatic spread, cancer cells need to remodel the extracellular matrix in order to migrate through stromal compartments adjacent to the primary tumor. Dissemination of breast carcinoma cells is mediated by membrane type 1-matrix metalloproteinase (MT1-MMP/MMP14), the main invadopodial matrix degradative component. Here, we identify MT1-MMP as a novel interacting partner of dual-specificity LIM Kinase-1 and -2 (LIMK1/2) and provide several evidence for phosphorylation of tyrosine Y573 in the cytoplasmic domain of MT1-MMP by LIMK. Phosphorylation of Y573 influences association of F-actin binding protein cortactin to MT1-MMP-positive endosomes and invadopodia formation and matrix degradation. Moreover, we show that LIMK1 regulates cortactin association to MT1-MMP-positive endosomes, while LIMK2 controls invadopodia-associated cortactin. In turn, LIMK1 and LIMK2 are required for MT1-MMP-dependent matrix degradation and cell invasion in a three-dimensional type I collagen environment. This novel link between LIMK1/2 and MT1-MMP may have important consequences for therapeutic control of breast cancer cell invasion.
Logical operations with single x-ray photons via dynamically-controlled nuclear resonances
Authors: Gunst Jonas , Keitel Christoph H. , Pálffy Adriana
Published: April 2016

Photonic qubits lie at the heart of quantum information technology, often encoding information in their polarization state. So far, only low-frequency optical and infrared photons have been employed as flying qubits, as the resources that are at present easiest to control. With their essentially different way of interacting with matter, x-ray qubits would bear however relevant advantages: they are extremely robust, penetrate deep through materials and can be focused down to few-nm waveguides, allowing unprecedented miniaturization. Also, x-rays are resonant to nuclear transitions, which are very well isolated from the environment and present long coherence times. Here, we show theoretically that x-ray polarization qubits can be dynamically controlled by nuclear Mössbauer resonances. The control knob is played by nuclear hyperfine magnetic fields, that allow via fast rotations precise processing of single x-ray quanta polarization. With such rotations, single-qubit and binary logical operations such as a destructive C-NOT gate can be implemented.
A lanthanide complex-based molecularly imprinted luminescence probe for rapid and selective determination of λ-cyhalothrin in the environment
Authors: Zheng Xudong , Zhang Fusheng , Liu Enli , Shi Weidong , Yan Yongsheng
Published: April 2016

Molecularly imprinted polymers cladded lanthanide complexes were synthesized via precipitation polymerization.
Unveiling the electrochemical mechanisms of Li2Fe(SO4)2 polymorphs by neutron diffraction and density functional theory calculations
Authors: Lander Laura , Reynaud Marine , Carrasco Javier , Katcho Nebil A. , Bellin Christophe , Polian Alain , Baptiste Benoît , Rousse Gwenaëlle , Tarascon Jean-Marie
Published: April 2016

The structure of electrochemically active Li1.5Fe(SO4)2 with difference Fourier maps highlighting the two lithium positions, which are also represented in the unit cell.
Petal-like graphene–Ag composites with highly exposed active edge sites were designed and constructed for electrochemical determination of metronidazole
Authors: Li Cong , Zheng Bo , Zhang Tingting , Zhao Jingyu , Gu Yue , Yan Xiaoyi , Li Yaru , Liu Weilu , Feng Guodong , Zhang Zhiquan
Published: April 2016

The petal-like graphene–Ag composites with highly exposed active edge sites were constructed, which served as both the electrocatalyst and the current amplifier for electrochemical detection of metronidazole.
Saponin-enhanced biomass accumulation and demulsification capability of the demulsifying bacteria Alcaligenes sp. S-XJ-1
Authors: Huang Xiangfeng , Zhang Yuyan , Wei Yansong , Liu Jia , Lu Lijun , Peng Kaiming
Published: April 2016

Saponin significantly enhanced biomass accumulation and demulsification capability of the demulsifying bacteria.
Insights into the nitridation of zero-valent iron nanoparticles for the facile synthesis of iron nitride nanoparticles
Authors: Rohith Vinod K. , Saravanan P. , Sakar M. , Balakumar S.
Published: April 2016

The process of nitridation of zero-valent iron nanoparticles (ZVINPs) is investigated by employing two different synthesis strategies such as solvothermal method and gas diffusion using N2 and NH3.
Transformation and bioaccessibility of lead during physiologically based extraction test: effects of phosphate amendment and extract fluid components
Authors: Sima Jingke , Zhao Ling , Xu Xiaoyun , Luo Qishi , Cao Xinde
Published: April 2016

Pb bioaccessibility decreased continuously with phosphate amendment due to the formation and transformation of insoluble Pb phosphate precipitates during PBET.
A band-gap-graded CZTSSe solar cell with 12.3% efficiency
Authors: Yang Kee-Jeong , Son Dae-Ho , Sung Shi-Joon , Sim Jun-Hyoung , Kim Young-Ill , Park Si-Nae , Jeon Dong-Hwan , Kim JungSik , Hwang Dae-Kue , Jeon Chan-Wook , Nam Dahyun , Cheong Hyeonsik , Kang Jin-Kyu , Kim Dae-Hwan
Published: April 2016

Using an appropriate SeS2/Se weight ratio, band gap grading was realized. By increasing the value ofVOCthrough band gap grading in the depletion region, a recordVOCdeficit of 0.576 V and an efficiency of 12.3% were obtained.
Facile strategy for controllable synthesis of stable mesoporous black TiO2hollow spheres with efficient solar-driven photocatalytic hydrogen evolution
Authors: Hu Weiyao , Zhou Wei , Zhang Kaifu , Zhang Xiangcheng , Wang Lei , Jiang Baojiang , Tian Guohui , Zhao Dongyuan , Fu Honggang
Published: April 2016

Stable mesoporous black TiO2hollow spheres with controllable diameter, wall thickness and narrow bandgap are fabricatedviaa small amine molecules encircling strategy, showing high solar-driven photocatalytic hydrogen evolution.
An ultrasound-assisted wet-chemistry approach towards uniform Mg(BH4)2·6NH3nanoparticles with improved dehydrogenation properties
Authors: Li You , Liu Yongfeng , Zhang Xin , Zhou Di , Lu Yunhao , Gao Mingxia , Pan Hongge
Published: April 2016

Mg(BH4)2·6NH3nanoparticles measuring 20–40 nm in diameter were successfully synthesized by an ultrasound-assisted wet-chemistry approach, which exhibit significantly improved dehydrogenation properties.
Impact of TNF and IL-1β on capillary networks within engineered human adipose tissues
Authors: Proulx Maryse , Safoine Meryem , Mayrand Dominique , Aubin Kim , Maux Amandine , Fradette Julie
Published: April 2016

Inflammatory cytokines lead to capillary network disorganization and secreted factor modulation within human microvascularized engineered adipose tissues.
Macrophage TCF-4 co-activates p65 to potentiate chronic inflammation and insulin resistance in mice
Authors: Kang Xia , Hou Along , Wang Rui , Liu Da , Xiang Wei , Xie Qingyun , Zhang Bo , Gan Lixia , Zheng Wei , Miao Hongming
Published: April 2016

Transcription factor 4 (TCF-4) was recently identified as a candidate gene for the cause of type 2 diabetes, although the mechanisms have not been fully elucidated. In the present study, we demonstrated that the TCF-4 transgene in macrophages aggravated high-fat diet (HFD)-induced insulin resistance and chronic inflammation, characterized by the elevation of proinflammatory cytokines in the blood, liver and white adipose tissue, as well as a proinflammatory profile of immune cells in visceral fats in mice. Mechanistically, TCF-4 functioned as a co-activator of p65 to amplify the saturated free fatty acid (FFA)-stimulated promoter activity, mRNA transcription and secretion of proinflammatory cytokines in primary macrophages. Blockage of p65 with a specific interfering RNA or inhibitor could prevent TCF-4-enhanced expression of proinflammatory cytokines in FFA/lipopolysaccharide-treated primary macrophages. The p65 inhibitor could abolish macrophage TCF-4 transgene-aggravated systemic inflammation, glucose intolerance and insulin resistance in HFD-treated mice. In addition, we demonstrated that the mRNA expression of TCF-4 in the peripheral blood monocytes from humans was positively correlated to the levels of interleukin (IL)-1β, tumour necrosis factor α, IL-6 and fasting plasma glucose. In summary, we identified TCF-4 as a co-activator of p65 in the potentiation of proinflammatory cytokine production in macrophages and aggravation of HFD-induced chronic inflammation and insulin resistance in mice.
Code-Switching as a Communicative Resource Within Routine, Bilingual Family Interactions for a Child on the Autism Spectrum
Authors: Yu Betty
Published: April 2016

In today's global society, bilingualism is increasingly regarded as an asset. Bilingual competencies have been associated, for example, with cognitive benefits, increased ethnolinguistic pride, and access to more expansive sociocultural experiences. Currently, there is a convergence of research findings showing that bilingual children with autism spectrum disorders (ASD) perform comparably to monolingual children with ASD across measures of social-interactional, linguistic, and cognitive performance. In other words, bilingualism has not been shown to put children with ASD at a disadvantage. We have not yet, however, begun to examine bilingualism as a benefit for children with ASD. We currently have no information on how bilingual abilities are displayed by children with ASD and how the children draw on those competencies to navigate the demands of bilingual social interactions. This study is a conversation analysis (CA) of the code-switching behaviors of a bilingual child on the autism spectrum as he engaged in routine interactions with family members. The findings reveal that code-switching was used by this child strategically and systematically as a unique pragmatic resource.