bluuebunny/crossref_metadata_2025_split huggingface dataset:
Time to diagnosis in systemic sclerosis: Is sex a factor?
Authors: Hudson Marie , Thombs Brett , Baron Murray ,   The Canadian Scleroderma Research Group
Published: January 2009

AbstractObjectiveTo determine whether sex plays a role in the time to diagnosis of systemic sclerosis (SSc).MethodsIn the Canadian Scleroderma Research Group registry, dates of onset of Raynaud's phenomenon, the first non–Raynaud's disease symptom, and diagnosis were recorded based on patient reports. Association between sex and time to diagnosis was assessed for the group as a whole and stratified based on extent of skin involvement, either limited or diffuse.ResultsOf the 408 patients studied (347 women, 61 men, 44% with diffuse cutaneous SSc), the time to diagnosis after the onset of Raynaud's phenomenon was significantly longer for women than men (log rank P = 0.001), but not significantly different after the onset of the first non–Raynaud's disease manifestation. In an analysis stratified by limited or diffuse status, the time to diagnosis from onset of Raynaud's phenomenon was also significantly longer for women than men with diffuse cutaneous SSc (log rank P = 0.008). A trend toward a longer period between onset of Raynaud's phenomenon and SSc diagnosis was observed in women compared with men with limited cutaneous SSc (median 4.6 years in women versus 2.1 years in men; P = 0.085), and there was no sex difference in time to diagnosis after the onset of the first non–Raynaud's disease manifestation.ConclusionIn SSc, the time to diagnosis is longer for women than men after the onset of Raynaud's phenomenon, suggesting that there may be possible biologic differences in the progression of disease or in the health care trajectories of men and women with early SSc.
Role of placenta growth factor and its receptor flt‐1 in rheumatoid inflammation: A link between angiogenesis and inflammation
Authors: Yoo Seung‐Ah , Yoon Hyung‐Ju , Kim Hyun‐Sook , Chae Chi‐Bom , De Falco Sandro , Cho Chul‐Soo , Kim Wan‐Uk 
Published: January 2009

AbstractObjectiveTo investigate the direct effects of placenta growth factor (PlGF) and its specific receptor, flt‐1, which are known to mediate angiogenesis, on the inflammatory process of rheumatoid arthritis (RA).MethodsExpression of PlGF and flt‐1 in the synovial tissue of RA patients was examined using immunohistochemistry. Enzyme‐linked immunosorbent assay was used to determine the concentrations of PlGF, tumor necrosis factor α (TNFα), and interleukin‐6 (IL‐6) in culture supernatants of either mononuclear cells or synoviocytes. The flt‐1 expression level in mononuclear cells was analyzed by flow cytometry. Experimental arthritis was induced in mice either by immunization with type II collagen (CII) or by injection of anti‐CII antibody.ResultsPlGF was highly expressed in the synovium of RA patients, and its primary source was fibroblast‐like synoviocytes (FLS). When stimulated with IL‐1β, FLS from RA patients produced higher amounts of PlGF than did FLS from patients with osteoarthritis. Exogenous PlGF specifically increased the production of TNFα and IL‐6 in mononuclear cells from RA patients (but not those from healthy controls) via a calcineurin‐dependent pathway. The response to PlGF was associated with increased expression of flt‐1 on RA monocytes, which could be induced by IL‐1β and TNFα. A novel anti–flt‐1 hexapeptide, GNQWFI, abrogated the PlGF‐induced increase in TNFα and IL‐6 production, and also suppressed CII‐induced arthritis and serum IL‐6 concentrations in mice. Moreover, genetic ablation of PlGF prevented the development of anti‐CII antibody–induced arthritis in mice.ConclusionOur data suggest that enhanced expression of PlGF and flt‐1 may contribute to rheumatoid inflammation by triggering production of proinflammatory cytokines. The use of the novel anti–flt‐1 peptide, GNQWFI, may be an effective strategy for the treatment of RA.
Land‐based versus water‐based rehabilitation following total knee replacement: A randomized, single‐blind trial
Authors: Harmer Alison R. , Naylor Justine M. , Crosbie Jack , Russell Tyson 
Published: January 2009

AbstractObjectiveTo compare outcomes between land‐based and water‐based exercise programs delivered in the early subacute phase up to 6 months after total knee replacement (TKR).MethodsTwo weeks after surgery (baseline), 102 patients were randomized to participate in either land‐based (n = 49) or water‐based (n = 53) exercise classes. Treatment parameters were guided by current clinical practice protocols. Therefore, each study arm involved 1‐hour sessions twice a week for 6 weeks, with patient‐determined exercise intensity. Session attendance was recorded. Outcomes were measured at baseline and at 8 and 26 weeks postsurgery. Outcomes included distance on the 6‐Minute Walk test, stair climbing power (SCP), the Western Ontario and McMaster Universities (WOMAC) Osteoarthritis Index (n = 85 English‐proficient patients), visual analog scale for joint pain, passive knee range of motion, and knee edema (circumference). Planned orthogonal contrasts, with an intent‐to‐treat approach, were used to analyze the effects of time and time‐group interactions.ResultsCompliance in both groups was excellent with 81% attending 8 or more sessions. Loss to followup was 5%. Significant improvements were observed across time in all outcomes at 8 weeks, with further improvements evident in all variables (except WOMAC pain) at 26 weeks. Minor between‐group differences were evident for 4 outcomes (SCP, WOMAC stiffness, WOMAC function, and edema) but these appear clinically insignificant.ConclusionA short‐term, clinically pragmatic program of either land‐based or water‐based rehabilitation delivered in the early phase after TKR was associated with comparable outcomes at the end of the program and up to 26 weeks postsurgery.
Synthesis, Characterization, and DNA‐Binding Studies of Mononuclear Copper(II)–Phenanthroline–Tyrosine Complex
Authors: Reddy Pulimamidi R. , Manjula Pallerla 
Published: January 2009

Abstractmagnified imageThe mononuclear complex [CuII(phen)(L‐Tyr)(H2O)] was synthesized and structurally characterized by elemental analysis, magnetic susceptibility, UV/VIS, IR, and EPR spectroscopy, and ESI mass spectrometry. The electronic and EPR spectral data suggest a square‐pyramidal geometry around CuII. Absorption spectra, thermal denaturation, and fluorescence‐spectroscopic studies were conducted to assess the interaction of the CuII complex with calf thymus DNA (CT DNA). The intrinsic binding constant for CT DNA/complex (Kb=3750 M−1) and Stern–Volmer quenching constant (K=0.39) were determined.
Nitration of Alkyl Benzoates with Mixed Acid
Authors: Klais O. , Hoffmann H. , Kyaw Naing E. 
Published: January 2009

AbstractThe nitration of (substituted) benzoic acid esters is usually performed in fed‐batch operation. The ester is solved in sulfuric acid charged first. The nitric acid dosed keeps the reaction temperature under control. The safety regarding uncontrolled reaction conditions was investigated under variation of the ratio of nitric acid to charged aromatic compound. A significant decrease in thermal stability of the reaction mixture was observed with excess of nitric acid. Safe operation cannot be assumed in general when the acid is close to or exceeds 10 % molar ratio. The investigation was restricted to aromatic carboxylic acid alkyl esters which form homogeneous mixtures with sulfuric acid. The thermal stability was investigated by differential thermal analysis (closed systems), adiabatic storage tests, and dynamic calorimeters. The reaction products were analyzed by means of NMR and mass spectrometry. The experiments showed that the formation of dinitro compounds cannot cause the thermal instability alone. The formation of dinitro compounds starts at temperatures above the reaction conditions. Another component is responsible for the thermal instability which accumulates in the presence of an ester group at excess nitric acid. It could be deduced that the decomposition reaction is primarily caused by the reaction of surplus nitryl cation (NO2+ ion) with the nitrated carboxylic acid ester in the presence of sulfuric acid. The decomposition temperature of the reaction mixture depends on the nature of the ester group and the type and number of further substituents on the aromatic ring.
Stereo‐ and Regioselectivity in an Intramolecular Nitrone–Alkene Cycloaddition of Hept‐6‐enoses with a trans‐Acetonide Blocking Group
Authors: Shing Tony K. M. , Wong Wai F. , Ikeno Taketo , Yamada Tohru 
Published: January 2009

AbstractFrom sugar to cycloadduct: The effect of the trans‐acetonide blocking group and the stereochemistry of the substituents on the regio‐ and stereoselectivity in the intramolecular nitrone–alkene cycloaddition (INAC) reaction of hept‐6‐enoses (see scheme) is reported and studied by using theoretical analysis.magnified imageThe positional effect of the trans‐acetonide blocking group and the effect of the stereochemistry of the substituents on the regio‐ and stereoselectivity in intramolecular nitrone–alkene cycloaddition (INAC) reactions of hept‐6‐enoses are reported. Hept‐6‐enoses with a 2,3‐trans‐acetonide group were reacted with N‐alkyl hydroxylamine to give a mixture of exo and endo cycloadducts (cyclohexanols and cycloheptanols, respectively). Complete formation of endo cycloadducts (cycloheptanols) was realized for the INAC reaction of hept‐6‐enoses containing a 3,4‐trans‐O‐isopropylidene ring. Similarly, reaction of a hept‐6‐enose possessing a 4,5‐trans‐acetonide group surprisingly afforded exo cycloadducts (cyclohexanols) exclusively. The regio‐ and stereochemical outcomes of these reactions were rationalized on the basis of transition‐state energies obtained by computation.
Integrated Oligoaniline‐Cross‐Linked Composites of Au Nanoparticles/Glucose Oxidase Electrodes: A Generic Paradigm for Electrically Contacted Enzyme Systems
Authors: Yehezkeli Omer , Yan Yi‐Ming , Baravik Ilina , Tel‐Vered Ran , Willner Itamar 
Published: January 2009

AbstractSweet sensor: A bis‐aniline‐cross‐linked Au nanoparticles (NPs)/glucose oxidase composite has been electropolymerized on a Au electrode (see picture). The integrated Au NPs/enzyme electrode provides an effective matrix for making electrical contact with the enzyme, and this yields a specific amperometric glucose biosensor.magnified imageElectropolymerizable glucose oxidase (GOx) was synthesized by the tethering of thioaniline units to the protein. The electropolymerization of the thioaniline‐modified GOx in the presence of thioaniline‐functionalized Au nanoparticles (NPs) yielded a three‐dimensional bis‐aniline‐cross‐linked Au NPs/GOx network. The bis‐aniline bridging units are redox active and mediate the electron transfer between the enzyme redox sites and the electrode, and the Au NPs provide the three‐dimensional conductivity for transporting the electrons to the electrode. The covalently linked GOx displays an effective electrical contact with the electrode (turnover rate of ca. 500 s−1), which results in a sensitive and selective glucose‐sensing electrode. The preparation of the electrode by means of electropolymerization, and the bioelectrocatalytic features of the electrode, suggest its feasibility as a miniaturized electrode with a sensing matrix and as an implantable glucose sensor in future applications.
Self‐Assembly of High‐Nuclearity Copper Cages: Tricorne Cu21 and Saddlelike Cyclic Cu16
Authors: Bai Yue‐Ling , Tangoulis Vassilis , Huang Rong‐Bin , Zheng Lan‐Sun , Tao Jun 
Published: January 2009

AbstractCopper clusters: Two high‐nuclearity copper cages, tricorne Cu21 and saddlelike cyclic Cu16 (see pictures), were synthesized. Magnetic studies and Monte Carlo calculations were also performed to show the overall antiferromagnetic properties of the two compounds.magnified imageReaction of cupric salts with H2Rppz (R=H, Me; H2ppz=3‐(2‐hydroxyphenyl)pyrazole; H2Meppz=3‐(2‐hydroxy‐5‐methylphenyl)pyrazole) in the presence of sodium azide and triethylamine as bases gave two high‐nuclearity copper cage compounds [HNEt3]2⋅[Cu21(CH3CN)2(H2O)(μ2‐N3)6(μ3‐N3)2(ppz)18]⋅(H2O)3⋅(EtOH)2 (1) and [Cu16(EtOH)2(H2O)2(Meppz)16]⋅9.5 H2O (2), respectively. X‐ray crystallographic studies revealed that molecular skeletons of 1 and 2 are unique tricorne Cu21 and saddlelike cyclic Cu16 aggregates, respectively. The magnetic properties studies showed overall antiferromagnetic interactions in 1 and 2. Quantum Monte Carlo simulations by using a 3‐J model for 1 and a 2‐J model for 2 were performed, which indicated that the magnetic couplings within the triangular copper units in 1 are ferromagnetic and those between other copper ions are antiferromagnetic, whereas in 2 all magnetic couplings between adjacent copper ions are exclusively antiferromagnetic.
Chloride‐Free Method to Synthesise New Ionic Liquids with Mixed Borate Anions
Authors: Schreiner Christian , Amereller Marius , Gores Heiner J. 
Published: January 2009

AbstractChloride avoided! A new chloride‐free method to synthesise ionic liquids (ILs) with mixed borate anions, starting from tetrafluoroborate compounds, has been developed and a number of examples including some new ILs are presented (see scheme; [CAT]+=cation). It is widely applicable and allows access to mixed borates with various types of ligands in a straightforward manner.magnified image
Binding of Ionic Species: A General Approach To Measuring Binding Constants and Assessing Affinities
Authors: Roelens Stefano , Vacca Alberto , Venturi Chiara 
Published: January 2009

AbstractBound together: The association of receptors with ionic species cannot be assimilated to the binding of neutral guests. When dealing with salts, both ion pairing and binding to the free and the ion‐paired ionic guest determine the actual association pattern (see figure). The general issue of measuring association constants and assessing affinities for ions is addressed and validated in two cases of anion binding.magnified imageA general approach to the largely underestimated issue of measuring binding constants and assessing affinities in the binding of ionic species is described. The approach is based on a rigorous, nongraphical determination of binding constants in multiequilibrium systems by nonlinear regression of chemical shift data from NMR titrations and on the use of the BC50 descriptor for assessing affinities and ranking the binding ability of receptors on a common scale. The approach has been validated with two tripodal anion‐binding receptors, namely, a ureidic (1) and a pyrrolic (2) receptor, binding to tetramethylammonium chloride in CDCl3/CD3CN (80:20). A set of five and six formation constants could be measured for 1 and 2, respectively, including, in addition to the ion pair, complexes of the free and the ion‐paired anion. The BC50 values calculated from the measured constants allowed a quantitative assessment of each receptor's binding affinity towards the chloride anion, the pyrrolic receptor showing a 15‐fold larger affinity over the ureidic receptor, a figure that quantifies the improvement obtained by replacing the amido‐pyrrolic for ureidic binding groups on the tripodal scaffold of the receptor. The results have shown that, in contrast to common practice, neither of the two systems could be appropriately described by a 1:1 association with the anion only, but required the ion‐pairing and ion‐pair binding equilibria to be taken into account because these contribute substantially to the complexation process. The BC50 descriptor has also been shown to be a useful and general tool for the assessment of affinities of systems involving ionic species. The required extension of the BC50 binding descriptor to include the treatment of ion‐binding has been described in detail.
Highly Diastereoselective Addition of Allyltitanocenes to Ketones
Authors: Yatsumonji Yasutaka , Nishimura Takuya , Tsubouchi Akira , Noguchi Keiichi , Takeda Takeshi 
Published: January 2009

AbstractA route with less congestion: A practical method for the highly diastereoselective preparation of anti tertiary homoallylic alcohols has been developed. The reaction of allyltitanocenes, generated by the reductive titanation of various allylic substrates with a titanocene(II) species, with a variety of ketones produced the anti tertiary homoallylic alcohols in good diastereoselectivity, even when using sterically less congested ketones (see scheme; Cp: cyclopentadienyl; Piv: pivaloyl).magnified imageThe reaction of allyltitanocenes, generated by the reductive titanation of allylic sulfides or allylic alcohol derivatives with a titanocene(II) species, with phenyl and sterically hindered alkyl methyl ketones produced anti tertiary homoallylic alcohols with complete diastereoselectivity. Even when sterically less congested methyl ethyl ketone and methyl vinyl ketone were employed, the anti homoallylic alcohols were obtained with unprecedented high diastereoselectivity. The observed anti selectivity suggests that the reaction proceeds by the addition of primary (E)‐σ‐allyltitanocenes to ketones through chairlike cyclic transition states.
The Personality Structure Questionnaire (PSQ): a cross‐validation with a large clinical sample
Authors: Bedford Alan , Davies Felix , Tibbles Jennifer 
Published: January 2009

AbstractIn a large sample of adult National Health Service (NHS) patients (initially n = 1296) referred for psychological therapy, the Personality Structure Questionnaire (PSQ) items were found to constitute a unidimensional scale according to maximum likelihood and principal component analyses, and by Cronbach's alpha criteria. The PSQ scores showed a significant small negative association with age, where higher scores indicate pathology; but no sex difference was found. Scores remain stable during time spent on the waiting list, but were reduced significantly following therapy of an equivalent length of time (median = 15 weeks). The intercorrelations between the three clusters of items (sub‐concepts, as proposed by the test authors) comprising the full PSQ varied, but were all sizeable and highly statistically significant. Additional information to that of the test authors is provided on convergent and discriminant validity through its correlations with psychological tests and clinicians' ratings. Suggestions are made for the possible further improvement and refinement of the questionnaire. Copyright © 2009 John Wiley & Sons, Ltd.
Novel Polymeric Materials from Vegetable Oils and Vinyl Monomers: Preparation, Properties, and Applications
Authors: Lu Yongshang , Larock Richard C. 
Published: January 2009

AbstractVeggie‐based products: Vegetable‐oil‐based polymeric materials, prepared by free radical, cationic, and olefin metathesis polymerizations, range from soft rubbers to ductile or rigid plastics, and to high‐performance biocomposites and nanocomposites. They display a wide range of thermophysical and mechanical properties and may find promising applications as alternatives to petroleum‐based polymers.magnified imageVegetable oils are considered to be among the most promising renewable raw materials for polymers, because of their ready availability, inherent biodegradability, and their many versatile applications. Research on and development of vegetable oil based polymeric materials, including thermosetting resins, biocomposites, and nanocomposites, have attracted increasing attention in recent years. This Minireview focuses on the latest developments in the preparation, properties, and applications of vegetable oil based polymeric materials obtained by free radical, cationic, and olefin metathesis polymerizations. The novel vegetable oil based polymeric materials obtained range from soft rubbery materials to ductile or rigid plastics and to high‐performance biocomposites and nanocomposites. These vegetable oil based polymeric materials display a wide range of thermophysical and mechanical properties and should find useful applications as alternatives to their petroleum‐based counterparts.
Imprinted DC mediate the immune‐educating effect of early‐life microbial exposure
Authors: Jiao Lei , Han Xiaobing , Wang Shuhe , Fan Yijun , Yang Megan , Qiu Hongyu , Yang Xi 
Published: January 2009

AbstractIt has been long proposed that exposure to environmental factors early in life may have an educating effect on the development of immune regulatory functions. However, experimental studies on this issue are limited and the related molecular and cellular basis remains unclear. Here we report that neonatal exposure to killed bacteria (Chlamydia muridarum, originally called Chlamydia trachomatis mouse pneumonitis (MoPn)) changed the pattern of the hosts' immune responses to a model allergen (OVA) in adulthood. This was associated with altered phenotype and function of DC. We found that DC from adult mice treated neonatally with UV‐killed MoPn exhibited distinct patterns of surface marker and TLR expression and cytokine production from control mice (DC from adult mice neonatally treated with vehicle, (Sham‐DC)). More importantly, DC from adult mice treated neonatally with UV‐killed MoPn induced significantly lower type‐2 antigen‐specific T‐cell responses than Sham‐DC shown in DC:T co‐culture experiments in vitro and in adoptive transfer experiments in vivo. In addition, depletion of T cells in vivo largely abolished the phenotypic and functional alterations of DC caused by bacterial exposure, suggesting the involvement of T cell in this process. Our study demonstrates a central role of DC in linking the early‐life exposure to microbial products and the balanced development of immune regulatory functions and the involvement of T cells in imprinting of the DC function.
A novel IL‐17‐dependent mechanism of cross protection: Respiratory infection with mycoplasma protects against a secondary listeria infection
Authors: Sieve Amy N. , Meeks Karen D. , Bodhankar Sheetal , Lee Suheung , Kolls Jay K. , Simecka Jerry W. , Berg Rance E. 
Published: January 2009

AbstractImmune responses to pathogens occur within the context of current and previous infections. Cross protection refers to the phenomena where infection with a particular pathogen provides enhanced resistance to a subsequent unrelated pathogen in an antigen‐independent manner. Proposed mechanisms of antigen‐independent cross protection have involved the secretion of IFN‐γ, which activates macrophages, thus providing enhanced innate immunity against the secondary viral or bacterial pathogen. Here we provide evidence that a primary infection with the chronic respiratory pathogen, Mycoplasma pulmonis, provides a novel form of cross protection against a secondary infection with Listeria monocytogenes that is not mediated by IFN‐γ, but instead relies upon IL‐17 and mobilization of neutrophils. Mice infected with M. pulmonis have enhanced clearance of L. monocytogenes from the spleen and liver, which is associated with increased numbers of Gr‐1+CD11b+ cells and higher levels of IL‐17. This enhanced clearance of L. monocytogenes was absent in mice depleted of Gr‐1+ cells or in mice deficient in the IL‐17 receptor. Additionally, both the IL‐17 receptor and neutrophils were essential for optimal clearance of M. pulmonis. Thus, a natural component of the immune response directed against M. pulmonis was able to enhance clearance of L. monocytogenes.