bluuebunny/crossref_metadata_2025_split huggingface dataset:
Gene expression profile in the salivary glands of primary Sjögren's syndrome patients before and after treatment with rituximab
Authors: Devauchelle‐Pensec Valérie , Cagnard Nicolas , Pers Jacques‐Olivier , Youinou Pierre , Saraux Alain , Chiocchia Gilles 
Published: April 2010

AbstractObjectivePrimary Sjögren's syndrome (SS) is a complex disorder, in part due to B cell abnormalities. Although anti–B cell therapy is promising in primary SS, no treatment has yet been demonstrated to modify the disease course. This open‐label study was undertaken to evaluate the efficacy of rituximab in primary SS and to investigate whether expression of specific genes is associated with efficacy of this treatment.MethodsFifteen patients with primary SS were treated in an open‐label trial. Salivary gland biopsy specimens were obtained, and total RNA was extracted and amplified. Microarray analysis with the Affymetrix Human Genome U133 Plus 2.0 Array was used to analyze >54,000 transcripts, and potential pathways were identified.ResultsWith gene expression data obtained before treatment, patients could be correctly classified in terms of whether they would be responders or nonresponders to rituximab. Gene pathway analysis demonstrated that the B cell signaling pathway was the most profoundly differentially expressed before treatment in the responders compared with nonresponders. Subclassification of patients based on the level of infiltration also demonstrated differential expression of genes belonging to the interferon (IFN) pathway between responders and nonresponders. Furthermore, unsupervised analysis based on gene expression modification before and after treatment allowed identification of 8 genes that were differentially expressed between responders and nonresponders, with the difference remaining significant after Bonferroni correction.ConclusionOur results demonstrate the ability to elaborate a set of genes predictive of rituximab efficacy and highlight the importance of studying the differential expression of B cell and IFN pathway signaling molecules in relation to the response to anti‐CD20 treatment. A randomized controlled study is currently ongoing to confirm these results.
A grid service‐based Distributed Network Simulation Environment for computer networks education
Authors: Bote‐Lorenzo Miguel L. , Asensio‐Pérez Juan I. , Gómez‐Sánchez Eduardo , Vega‐Gorgojo Guillermo , Alario‐Hoyos Carlos 
Published: April 2010

AbstractThis paper presents a Distributed Network Simulation Environment (DNSE) based on grid technology that, unlike the well‐known ns‐2 simulator, provides two important features that facilitate the study of network scenarios that require running multiple simulations. First, the DNSE is capable of automatically handling the realization of multiple distributed simulations with the aim of completing all simulations in a reasonable amount of time. Second, the DNSE integrates the realization of simulations with the analysis of their results in an intuitive GUI in order to relieve students from the burden of launching multiple simulations and handling the many output files that may be generated to study the results. The performance analysis of the DNSE shows that it can significantly reduce the time required to complete multiple simulations. Furthermore, the assessment of an experience with students evidence that the DNSE can successfully support a real learning scenario and that students prefer using the DNSE over the ns‐2. © 2010 Wiley Periodicals, Inc. Comput Appl Eng Educ 20: 654–665, 2012
Too cheap to chug: frugality as a buffer against college‐student drinking
Authors: Rose Paul , Smith Shannon Toney , Segrist Daniel J. 
Published: April 2010

Abstract
Beyond its probable effect on preventing financial problems, frugality may contribute to consumer well‐being in other ways. Using survey data collected from American undergraduates, in this paper we demonstrate that frugality is negatively associated with several types of alcohol use. These relationships hold even when sex and impulsivity are controlled. To further substantiate the link between frugality and college‐student drinking, we confirmed that typical amount spent on alcohol mediates the relations between frugality and each type of drinking we assessed. These results are consistent with suggestions that young adults' drinking‐related choices are subject to price considerations and that policy makers may be able to leverage such considerations to prevent excessive drinking.
Copyright © 2010 John Wiley & Sons, Ltd.
Wiki based management of chemometric research projects
Authors: Alsberg Bjørn K. , Clare Amanda 
Published: April 2010

AbstractAs research projects grow in size, there is a tendency for the number of management tasks to increase even faster. There are many different data objects and relations which need to be managed as part of the whole project: raw data, script files, function files, results, plots, tables etc.Here it is suggested that a combination of wiki and version control software can be used as very effective and efficient tools in the management of chemometric research projects. A wiki provides a system for editing, viewing and navigating hyperlinked documents using web browsers. Easy syntax allows fast construction of web pages and hyperlinks without having to write HTML. Version control systems provide shared storage for source code and data (such as m‐files, Python and Perl scripts, plot and diagram source files, LaTeX files etc). Items stored in version control are given version numbers and can be retrieved, worked upon and updated by multiple users in different locations without conflict.At the top level of a project wiki the main ideas and goals are described whereas at the bottom level there are scripts, tables and raw data. The structure suggested by the different levels supports a common understanding of the need to record information and of which information to record. All levels can rapidly be accessed by following hyperlinks in the wiki. Combining information into new wiki pages is also very easy in this framework. Copyright © 2010 John Wiley & Sons, Ltd.
Ruthenium‐Catalyzed Alkylation of Indoles with Tertiary Amines by Oxidation of a sp3 CH Bond and Lewis Acid Catalysis
Authors: Wang Ming‐Zhong , Zhou Cong‐Ying , Wong Man‐Kin , Che Chi‐Ming 
Published: April 2010

AbstractRuthenium porphyrins (particularly [Ru(2,6‐Cl2tpp)CO]; tpp=tetraphenylporphinato) and RuCl3 can act as oxidation and/or Lewis acid catalysts for direct C‐3 alkylation of indoles, giving the desired products in high yields (up to 82 % based on 60–95 % substrate conversions). These ruthenium compounds catalyze oxidative coupling reactions of a wide variety of anilines and indoles bearing electron‐withdrawing or electron‐donating substituents with high regioselectivity when using tBuOOH as an oxidant, resulting in the alkylation of N‐arylindoles to 3‐{[(N‐aryl‐N‐alkyl)amino]methyl}indoles (yield: up to 82 %, conversion: up to 95 %) and the alkylation of N‐alkyl or N‐H indoles to 3‐[p‐(dialkylamino)benzyl]indoles (yield: up to 73 %, conversion: up to 92 %). A tentative reaction mechanism involving two pathways is proposed: an iminium ion intermediate may be generated by oxidation of an sp3 CH bond of the alkylated aniline by an oxoruthenium species; this iminium ion could then either be trapped by an N‐arylindole (pathway A) or converted to formaldehyde, allowing a subsequent three‐component coupling reaction of the in situ generated formaldehyde with an N‐alkylindole and an aniline in the presence of a Lewis acid catalyst (pathway B). The results of deuterium‐labeling experiments are consistent with the alkylation of N‐alkylindoles via pathway B. The relative reaction rates of [Ru(2,6‐Cl2tpp)CO]‐catalyzed oxidative coupling reactions of 4‐X‐substituted N,N‐dimethylanilines with N‐phenylindole (using tBuOOH as oxidant), determined through competition experiments, correlate linearly with the substituent constants σ (R2=0.989), giving a ρ value of −1.09. This ρ value and the magnitudes of the intra‐ and intermolecular deuterium isotope effects (kH/kD) suggest that electron transfer most likely occurs during the initial stage of the oxidation of 4‐X‐substituted N,N‐dimethylanilines. Ruthenium‐catalyzed three‐component reaction of N‐alkyl/N‐H indoles, paraformaldehyde, and anilines gave 3‐[p‐(dialkylamino)benzyl]indoles in up to 82 % yield (conversion: up to 95 %).
Nitrocyanamide‐Based Ionic Liquids and Their Potential Applications as Hypergolic Fuels
Authors: He Ling , Tao Guo‐Hong , Parrish Damon A. , Shreeve Jean'ne M. 
Published: April 2010

AbstractNitrocyanamide ionic liquids with substituted imidazolium, guanidinium, and tetrazolium cations have been synthesized and fully characterized. Aminoguanidinium nitrocyanamide (7) crystallizes in the triclinic system P$\bar 1$. The results obtained from theoretical calculations based on 7 are consistent with the single‐crystal structure data. These ionic liquids exhibit desirable physicochemical properties, such as low melting points and good thermal stabilities. Furthermore, they are all impact insensitive materials. Their energetic performances, including heats of formation, detonation pressures, and detonation velocities, were studied by a combination of theoretical and empirical calculations. The ionic liquids 1–4 have large liquid ranges and low viscosities. They were shown to be promising candidates as hypergolic ionic liquids through the combustion tests with 100 % HNO3.
Kinetic Control in the Chiral Recognition of Three‐Bladed Propellers
Authors: Bonnot Clément , Aubert Emmanuel , Banerji Natalie , Lacour Jérôme , Espinosa Enrique , Chambron Jean‐Claude 
Published: April 2010

AbstractThe ion pair of the stereolabile C3‐symmetric, i+o proton complex [1⋅H]+ of diaza‐macropentacycle 1 and the configurationally stable Δ‐TRISPHAT ([Δ‐3]−) anion exists in the form of two diastereomers, namely, [Δ‐(1⋅H)][Δ‐3] and [Λ‐(1⋅H)][Δ‐3], the ratio of which, in terms of diastereomeric excess (de) decreases in the order [D8]THF (28 %)>CD2Cl2 (22 %)>CDCl3 (20 %)>[D8]toluene (16 %)>C6D6 (7 %)>[D6]acetone (0 %) at thermodynamic equilibrium. Except in the case of [D6]acetone, the latter is reached after a period of time that increases from 1 h ([D8]THF) to 24 h (CDCl3). Moreover, the initial value of the de of [1⋅H][Δ‐3] in CDCl3, before the thermodynamic equilibrium is reached, depends on the solvent in which the sample has been previously equilibrated (sample “history”). This property has been used to show that the crystals of [1⋅H][Δ‐3] formed by slow evaporation of CH2Cl2/CH3OH mixtures had 100 % de, which indicates that [1⋅H][Δ‐3] has enjoyed a crystallization‐induced asymmetric transformation. Structural studies in solution (NMR spectroscopy) and in the gas phase by calculations at the semiempirical PM6 level of theory suggest that the optically active anion is docked on the i+ (endo) external side of the proton complex such that one of the aromatic rings of [Δ‐3]− is inserted into a groove of [1⋅H]+, a second aromatic ring being placed astride the outside i+ pocket. Solvent polarity controls the thermodynamics of inversion of the [1⋅H]+ propeller. However, both polarity and basicity control its kinetics. Therefore, the rate‐limiting steps correspond to the ion‐pair separation/recombination and [1⋅H]+/1 deprotonation/protonation processes, rather than the inversion of [1⋅H]+, the latter being likely to take place in the deprotonated form (1).
Metal Ions Drive Thermodynamics and Photochemistry of the Bis(styryl) Macrocyclic Tweezer
Authors: Tulyakova Elena V. , Vermeersch Gaston , Gulakova Elena N. , Fedorova Olga A. , Fedorov Yuri V. , Micheau Jean Claude , Delbaere Stéphanie 
Published: April 2010

AbstractUV/Vis and NMR spectroscopy were used for the structural elucidation and thermodynamic and photochemical studies of the metal‐coordinated crown‐containing macrocyclic tweezer (E,E)‐1. The bis(styryl) tweezer (E,E)‐1 formed two types of complexes with magnesium(II): a 1:1 intramolecular asymmetric sandwich complex [(E,E)‐1]⋅Mg2+ and a 1:2 complex [(E,E)‐1]⋅(Mg2+)2. In the former case, there is direct cation intramolecular exchange (0.299 s−1, ΔG≠=69.4 kJ mol−1) between two parts of the bis(styryl) tweezer (E,E)‐1. Addition of barium(II) to the bis(styryl) tweezer (E,E)‐1 led to an intramolecular centrosymmetric sandwich 1:1 complex [(E,E)‐1]⋅Ba2+. Irradiation of [(E,E)‐1]⋅Ba2+ afforded reversible intramolecular [2π+2π] photocyclization with excellent stereoselectivity and quantitative yield. In contrast, irradiation of [(E,E)‐1]⋅(Mg2+)2 resulted in reversible stepwise E,Z‐isomerization.
Chemoselectivity as a Delineator of Cuprate Structure in Catalytic 1,4‐Addition of Diorganozinc Reagents to Michael Acceptors
Authors: Welker Matthias , Woodward Simon , Veiros Luis F. , Calhorda Maria José 
Published: April 2010

AbstractReaction of the cyclic thioacetal (RS)2CHCHO [R=1/2×(CH2)3] with HCCCOMe, followed by treatment with TsCl/DABCO (Ts=tosyl, DABCO=1,4‐diazabicyclo[2.2.2]octane) affords the mono‐protected 1,4‐benzoquinone dithioacetal. The reactivity of this SR‐protected 1,4‐benzoquinone has been compared with the behavior of the analogous OR‐protected acetal in copper‐catalyzed additions of ZnMe2 by using chiral phosphoramidite ligands. The activation energy for 1,4‐methylation of the latter OR‐acetals with ZnMe2 (>95 % ee) has been determined for two CuX2 pre‐catalysts (X=OAc, 12.2 kcal mol−1; X=OTf, 6.7 kcal mol−1; Tf=triflate). The dithioacetal SR aromatizes in the presence of CuI/ZnMe2 giving 1,4‐HOC6H4S(CH2)3SMe through CS bond formation. The disparate behavior of these two very closely related substrates is in accordance with the formation of closely related cuprate intermediates that were optimized by DFT calculations, supporting the synthetic and kinetic studies and thus defining the mechanisms of both pathways.
Complex–Surfactant‐Assisted Hydrothermal Synthesis and Properties of Hierarchical Worm‐Like Cobalt Sulfide Microtubes Assembled by Hexagonal Nanoplates
Authors: Liu Bo , Wei Shuang , Xing Yan , Liu Dan , Shi Zhan , Liu Xianchun , Sun Xiujuan , Hou Suying , Su Zhongmin 
Published: April 2010

AbstractThe preparation of exquisite hierarchical worm‐like Co1−xS (x=0.75) microtubes by a one‐pot complex–surfactant‐assisted hydrothermal method is successfully achieved for the first time. The hierarchical structures of the microtube wall are assembled from numerous interleaving hexagonal nanoplates. X‐ray diffraction, X‐ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, and high‐resolution transmission electron microscopy were used to characterize the samples. The experimental results indicate that the “soft template” surfactant cetyltrimethylammonium bromide and the chelating ethylenediamine both play important roles for the formation of hierarchical Co1−xS microtubes. A possible formation mechanism for the growth processes is proposed. Additionally, the electrochemical and magnetic properties of Co1−xS microtubes were systematically studied.
Reaction of 1,1′‐Divinyl Ferrocene with One‐Electron Oxidants: Entry into Functionalised [4]Ferrocenophanes and Observation of an Isotope‐Dependent Chemoselectivity Effect
Authors: Gleixner Renate M. , Joly Kévin M. , Tremayne MaryJane , Kariuki Benson M. , Male Louise , Coe Diane M. , Cox Liam R. 
Published: April 2010

Abstract1,1′‐Divinyl ferrocene (2) reacts with K3[Fe(CN)6] under basic biphasic conditions to give a [4]ferrocenophane (4) in good yield. Incorporating deuterium labels into the internal positions of the vinyl groups of 2 affects the chemoselectivity of the reaction; thus under identical reaction conditions, [D2]‐2 reacts to provide a diol‐functionalised [4]ferrocenophane, [D2]‐D/L‐6 in addition to the expected keto‐alcohol, [D1]‐4. Variants on this one‐electron oxidative cyclisation methodology can be used to give other [4]ferrocenophanes; thus, the reaction of 2 with CuCl2 in MeOH or iPrOH leads to dialkoxy [4]ferrocenophanes 19 and 20, respectively, whereas the reaction of 2 with benzyl carbamate in the presence of tBuOCl gives a bis(carbamate)[4]ferrocenophane, 21. Mechanisms to account for the formation of the products, the stereoselectivity, and the unusual isotope‐dependent chemoselectivity in the reaction of 2 and [D2]‐2 with K3[Fe(CN)6] are proposed.
Polymer Covalent Functionalization of Carbon Nanohorns Using Bulk Free Radical Polymerization
Authors: Mountrichas Grigoris , Pispas Stergios , Ichihasi Toshinari , Yudasaka Masako , Iijima Sumio , Tagmatarchis Nikos 
Published: April 2010

AbstractHerein, we report on a facile approach for the covalent functionalization of carbon nanohorns, using in situ bulk free radical polymerization of methacrylic acid. The obtained material is soluble in aqueous media, facilitating its processability and has been fully characterized by means of complementary spectroscopic techniques, electron microscopy, thermogravimetric analysis, and light scattering. Simultaneously, the material has been used as a template for the synthesis of gold nanoparticles on the surface of the polymer‐decorated carbon nanohorns.
Photochromic Organometallics with a Dithienylethene (DTE) Bridge, [YCCDTECCY] (Y={MCp*(dppe)}): Photoswitchable Molecular Wire (M=Fe) versus Dual Photo‐ and Electrochromism (M=Ru)
Authors: Tanaka Yuya , Ishisaka Takuya , Inagaki Akiko , Koike Takashi , Lapinte Claude , Akita Munetaka 
Published: April 2010

AbstractDinuclear acetylide‐type complexes bridged by a photochromic dithienylethene unit (DTE), [YCCDTECCY] 1 (Y={MCp*(dppe)}; Cp*=pentamethylcyclopentadienyl, M=Fe (1Fe), Ru (1Ru)), have been prepared, and their wirelike and switching behavior, as well as their oxidation chemistry has been investigated. The DTE complexes 1 exhibit photochromic behavior in a manner similar to organic DTE derivatives; UV irradiation causes ring closure of the open isomer 1O to form the closed isomer 1C and visible‐light irradiation of the resultant 1C causes reverse ring opening to regenerate 1O. But the performance is dependent on the metals. With respect to the interconversion rates and the 1C content at the photostationary state under UV irradiation, the ruthenium complex 1Ru is superior to the iron analogue 1Fe. The wirelike performance is associated with the photochromic processes, and the efficient switching performance has been verified for 1Fe as characterized by the Vab values [Vab is the electronic coupling derived from intervalence charge‐transfer (IVCT) bands: Vab(1FeC; ON)=0.047 eV versus Vab(1FeO; OFF)=0 eV], and are also supported by the large switching factor (SF=KC(C; ON)/KC(O; OFF)=39; KC=comproportionation constant). SF for 1Ru is determined to be 4.2. The remarkable switching behavior arises from the different π‐conjugated systems in the two isomeric forms, that is, cross‐conjugated (1O) and fully conjugated π‐systems (1C). It was also found that, in contrast to the reversible redox behavior of the iron complex 1Fe, the ruthenium complex 1RuO undergoes oxidative ring closure to form the dicationic species of the closed isomer 1RuC2+ and, thus, the ruthenium system 1Ru shows dual photo‐ and electrochromism. The distinct oxidation behavior of 1Fe and 1Ru can be ascribed to the spin distribution on the diradical intermediates 1FeO2+ and 1RuO2+, as supported by DFT calculations.
Sterically Less‐Hindered Half‐Titanocene(IV) Phenoxides: Ancillary‐Ligand Effect on Mono‐, Bis‐, and Tris(2‐Alkyl‐/arylphenoxy) Titanium(IV) Chloride Complexes
Authors: Kim Tae‐Jin , Kim Sung‐Kwan , Kim Beom‐Jun , Son Ho‐Jin , Hahn Jong Sok , Cheong Minserk , Mitoraj Mariusz , Srebro Monika , Piękoś Łukasz , Michalak Artur , Kang Sang Ook 
Published: April 2010

AbstractA series of mono‐, bis‐, and tris(phenoxy)–titanium(IV) chlorides of the type [Cp*Ti(2‐RPhO)nCl3−n] (n=1–3; Cp*=pentamethylcyclopentadienyl) was prepared, in which R=Me, iPr, tBu, and Ph. The formation of each mono‐, bis‐, and tris(2‐alkyl‐/arylphenoxy) series was authenticated by structural studies on representative examples of the phenyl series including [Cp*Ti(2‐PhPhO)Cl2] (1 PhCl2), [Cp*Ti(2‐PhPhO)2Cl] (2 PhCl), and [Cp*Ti(2‐PhPhO)3] (3 Ph). The metal‐coordination geometry of each compound is best described as pseudotetrahedral with the Cp* ring and the 2‐PhPhO and chloride ligands occupying three leg positions in a piano‐stool geometry. The mean TiO distances, observed with an increasing number of 2‐PhPhO groups, are 1.784(3), 1.802(4), and 1.799(3) Å for 1 PhCl2, 2 PhCl, and 3 Ph, respectively. All four alkyl/aryl series with Me, iPr, tBu, and Ph substituents were tested for ethylene homopolymerization after activation with Ph3C+[B(C6F5)4]− and modified methyaluminoxane (7% aluminum in isopar E; mMAO‐7) at 140 °C. The phenyl series showed much higher catalytic activity, which ranged from 43.2 and 65.4 kg (mmol of Ti⋅h)−1, than the Me, iPr, and tBu series (19.2 and 36.6 kg (mmol of Ti⋅h)−1). Among the phenyl series, the bis(phenoxide) complex of 2 PhCl showed the highest activity of 65.4 kg (mmol of Ti⋅h)−1. Therefore, the catalyst precursors of the phenyl series were examined by treating them with a variety of alkylating reagents, such as trimethylaluminum (TMA), triisobutylaluminum (TIBA), and methylaluminoxane (MAO). In all cases, 2 PhCl produced the most catalytically active alkylated species, [Cp*Ti(2‐PhPhO)MeCl]. This enhancement was further supported by DFT calculations based on the simplified model with TMA.
Photochemistry in Photonic Crystal Fiber Nanoreactors
Authors: Chen Jocelyn S. Y. , Euser Tijmen G. , Farrer Nicola J. , Sadler Peter J. , Scharrer Michael , Russell Philip St. J. 
Published: April 2010

AbstractWe report the use of a liquid‐filled hollow‐core photonic crystal fiber (PCF) as a highly controlled photochemical reactor. Hollow‐core PCFs have several major advantages over conventional sample cells: the sample volume per optical path length is very small (2.8 nL cm−1 in the fiber used), long optical path lengths are possible as a result of very low intrinsic waveguide loss, and furthermore the light travels in a diffractionless single mode with a constant transverse intensity profile. As a proof of principle, the (very low) quantum yield of the photochemical conversion of vitamin B12, cyanocobalamin (CNCbl) to hydroxocobalamin ([H2OCbl]+) in aqueous solution was measured for several pH values from 2.5 to 7.5. The dynamics of the actively induced reaction were monitored in real‐time by broadband absorption spectroscopy. The PCF nanoreactor required ten thousand times less sample volume compared to conventional techniques. Furthermore, the enhanced sensitivity and optical pump intensity implied that even systems with very small quantum yields can be measured very quickly—in our experiments one thousand times faster than in a conventional cuvette.