bluuebunny/crossref_metadata_2025 huggingface dataset:
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

Sweet 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.

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Electropolymerizable 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

Copper 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.

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Reaction 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

Chloride 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.

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Binding of Ionic Species: A General Approach To Measuring Binding Constants and Assessing Affinities
Authors: Roelens Stefano , Vacca Alberto , Venturi Chiara
Published: January 2009

Bound 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.

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A 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

A 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).

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The 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

In 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

Veggie‐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.

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Vegetable 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

It 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

Immune 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.
DC contact with HIV‐1‐infected cells leads to high levels of Env‐mediated virion endocytosis coupled with enhanced HIV‐1 Ag presentation
Authors: Muratori Claudia , Bona Roberta , Ruggiero Eliana , D'Ettorre Gabriella , Vullo Vincenzo , Andreotti Mauro , Federico Maurizio
Published: January 2009

In HIV‐infected patients, DC are likely to interact with both cell‐free HIV and HIV‐infected cells. We were interested in investigating the mechanism of virus transmission occurring upon contact between HIV‐1‐infected cells and DC, as well as the consequences for HIV‐1 Ag‐presenting activity. By comparing mixed co‐cultures with trans‐well cultures, we observed that cell‐to‐cell contact strongly increased HIV‐1 Env‐mediated virion endocytosis in target DC. This endocytosis was independent of HIV‐1 tropism, de novo infection, HIV‐1 Env‐CD4‐dependent fusion, and immature DC activation/maturation. We also found that augmentation of HIV‐1 endocytosis was closely correlated with strong, Env‐dependent HIV‐1 Ag presentation by DC. Our results provide a better understanding of the mechanisms underlying the induction of the anti‐HIV adaptive immune response.
DC therapy induces long‐term NK reactivity to tumors via host DC
Authors: Shimizu Kanako , Fujii Shin‐ichiro
Published: January 2009

We vaccinated mice with DC loaded with or without invariant NKT‐cell ligand α‐galactosylceramide and evaluated long‐term resistance against tumor challenge. When mice had been given either DC or DC/galactosylceramide and were challenged with tumor cells even 6–12 months later, both NK and NKT cells were quickly activated to express CD69 and produce IFN‐γ. The NK cells could resist a challenge with several different tumors in vivo. The activated NK and NKT cells could be depleted with anti‐NK1.1 treatment. In spite of this, the activated cells recovered, indicating that tumor‐responsive NK and NKT cells were being generated continuously as a result of vaccination with DC and were not true memory cells. The NK and NKT antitumor response in DC‐vaccinated mice depended on CD4+ T cells, but neither CD8+T cells nor CD4+CD25+ regulatory T cells. However, both vaccine DC and host DC were required for the development of long‐term, tumor reactive innate immunity. These results indicate that DC therapy in mice induces long‐lasting innate NK‐ and NKT‐cell activation through a pathway that requires host DC and CD4+ T cells and that the continued generation of active NK cells resists the establishment of metastases in vivo.
PI3K limits TNF‐α production in CD16‐activated monocytes
Authors: Kramer Phillip R. , Winger Vanessa , Reuben Jayne
Published: January 2009

IgG complexes bind to Fc receptor family members FcγRI (CD64), FcγRII (CD32) and FcγRIII (CD16), activating cell MAPK and PI3K resulting in increased cytokine production from particular leukocytes. The signaling molecules involved in cytokine production after cross‐linking CD16 have not been determined in monocytes. To address this question, TNF‐α, IL‐1β and IL‐6 were measured in activated monocytes after inhibiting MEK1/2, PI3K and glycogen synthase kinase‐β (GSK‐3β). The roles of GSK‐3β and NF‐κB were then determined using reporter assays and siRNA treatment. The data suggested that an MAPK pathway stimulated TNF‐α release but that active PI3K limited TNF‐α, IL‐1β and IL‐6 cytokine production after cross‐linking CD16. PI3K was also shown to limit nuclear translocation of NF‐κB. The limiting effect of PI3K on TNF‐α production from activated monocytes depended on the decrease of GSK‐3β activity, which significantly reduced the transactivation of NF‐κB. Moreover, the TNF‐α production induced by CD16 cross‐linking was reduced in monocytes after treatment with siRNA against NF‐κB, implying that this transcription factor functioned in TNF‐α production. The results suggest that CD16 cross‐linking activated PI3K and that active PI3K limited TNF‐α production by inhibiting GSK‐3β activity, that blocked the action of NF‐κB.
Molecular basis of CD4 repression by the Swi/Snf‐like BAF chromatin remodeling complex
Authors: Wan Mimi , Zhang Jianmin , Lai Dazhi , Jani Anant , Prestone‐Hurlburt Paula , Zhao Lulu , Ramachandran Aruna , Schnitzler Gavin R. , Chi Tian
Published: January 2009

The Brg1/Brm‐associated factor (BAF) chromatin remodeling complex directly binds the CD4 silencer and is essential for CD4 repression during T‐cell development, because deletion of the ATPase subunit Brg1 or a dominant negative mutant of BAF57 each impairs CD4 repression in early thymocytes. Paradoxically, BAF57 is dispensable for remodeling nucleosomes in vitro or for binding of the BAF complex to the CD4 silencer in vivo. Thus, it is unclear whether BAF57‐dependent CD4 repression involves chromatin remodeling and, if so, how the remodeling translates into CD4 repression. Here we show that nucleosomes at the CD4 silencer occupy multiple translational frames. BAF57 dominant negative mutant does not alter these frames, but reduces the accessibility of the entire silencer without affecting the flanking regions, concomitant with localized accumulation of linker histone H1 and eviction of Runx1, a key repressor of CD4 transcription that directly binds the CD4 silencer. Our data indicate that precise nucleosome positioning is not critical for the CD4 silencer function and that BAF57 participates in remodeling H1‐containing chromatin at the CD4 silencer, which enables Runx1 to access the silencer and repress CD4. In addition to BAF57, multiple other subunits in the BAF complex are also dispensable for chromatin remodelling in vitro. Our data suggest that these subunits could also help remodel chromatin at a step after the recruitment of the BAF complex to target genes.
Selective Crystallization of Dimeric vs. Monomeric Dimethyltin‐Containing Tungstoarsenates(III) and ‐antimonates(III) with the Guanidinium Cation
Authors: Reinoso Santiago , Dickman Michael H. , Kortz Ulrich
Published: January 2009

The use of guanidinium cations [C(NH2)3]+ as crystallizing agents allowed us to selectively isolate the dimeric [{(CH3)2Sn(H2O)}4{(CH3)2Sn}(B‐β‐XW9O33)2]8– (1, X = AsIII; 2, X = SbIII) polyanions from the reaction of (CH3)2SnCl2 with Na9[B‐α‐XW9O33] (3:1 ratio) in water at pH 3. This reaction is known to give the monomeric [{(CH3)2Sn(H2O)2}3(B‐β‐XW9O33)]3– polyanions as the major species. Polyanions 1 and 2 are composed of one octahedral trans‐(CH3)2SnO4 moiety that bridges two trilacunary [B‐β‐XW9O33]9– Keggin subunits further decorated by two structurally nonequivalent {(CH3)2Sn}2+ functionalities each: one distorted octahedral trans‐(CH3)2SnO4 linking moiety and one trigonal‐bipyramidal cis‐(CH3)2SnO3 pendant group. This results in a dimeric, centrosymmetric assembly where each [B‐β‐XW9O33]9– subunit is connected to three {(CH3)2Sn}2+ functionalities through two Sn–O(W) bonds. Polyanions 1 and 2 polymerize upon crystallization by forming intermolecular Sn–O–W bridges resulting in the isostructural hybrid materials [C(NH2)3]8[{(CH3)2Sn(H2O)}4{(CH3)2Sn}(B‐β‐XW9O33)2]·10H2O (1a, X = AsIII; 2a, X = SbIII). Compounds 1a and 2a were characterized in the solid state by elemental analysis, infrared spectroscopy, thermal analysis, and single‐crystal X‐ray diffraction. The crystal packing shows a 2D arrangement of the polyanions connected by the trans‐(CH3)2SnO4 linking moieties, resulting in corrugated hybrid layers parallel to the (101) plane with the cis‐(CH3)2SnO3 pendant groups acting as interlamellar spacers.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Synthesis, Crystal Structures and Redox Properties of Mixed‐Sandwich Complexes of Ruthenium(II) with Cyclopentadienyl and Tris(pyrazolyl)methane Ligands
Authors: Kuzu Istemi , Nied Dominik , Breher Frank
Published: January 2009

New mixed‐sandwich ruthenium(II) complexes have been prepared by treatment of either [RuCp(acn)3][PF6] or [RuCp*(acn)3][PF6] (Cp = η5‐cyclopentadienyl; Cp* = η5‐pentamethylcyclopentadienyl, acn = CH3CN) with tris(pyrazolyl)methane (HTpm) and tris(3,5‐dimethylpyrazolyl)methane (MeTpm), respectively. [RuCp(HTpm)][PF6] (1), [RuCp*(HTpm)][PF6] (2) and [RuCp(MeTpm)][PF6] (3) have been examined by single‐crystal X‐ray diffraction (1, 2) and 2D NMR experiments, which reveal discrete units of cationic mixed‐sandwich complexes of the composition [RuCp(*)(RTpm)]+ featuring η5‐cyclopentadienyl and κ3N‐coordinated RTpm ligands. The air‐sensitive salt [RuCp*(acn)(MeTpm)][PF6] (4) exhibits a κ2N‐coordinated MeTpm and one remaining acetonitrile ligand, presumably due to steric interactions between the sterically more bulky Cp* and MeTpm ligands. Cyclic voltammetric studies of the symmetric mixed‐sandwich complexes 1–3 in acetonitrile show quasi‐reversible oxidation processes centred at E01/2 = +0.38 (1), +0.15 V (2) and +0.35 V (3) vs. Fc/Fc+. These values are mainly affected by the different nature of the Cp ligands; the differently substituted RTpm entities have very little influence.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Mixed Valency at the Nearly Delocalized Limit: Fundamentals and Forecast (Eur. J. Inorg. Chem. 5/2009)
Authors: Glover Starla D. , Goeltz John C. , Lear Benjamin J. , Kubiak Clifford P.
Published: January 2009

The cover picture shows a Class II/III mixed‐valence system, {[Ru3O(OAc)6(CO)(pyridine)]2–pyrazine}–1, which undergoes picosecond intramolecular electron transfer (right). In nearly delocalized mixed‐valence complexes, rates of ET depend highly on solvent dynamics. Freezing of the solution causes a localized‐to‐delocalized transition, and rates of ET increase. We find that, for Class II/III mixed‐valence complexes, solvent dynamical parameters control rates of ET and tend to localize otherwise delocalized electronic states. Details are presented in the Microreview by C. P. Kubiak et al. on p. 585 ff.
Omphalotins E–I, Five Oxidatively Modified Nematicidal Cyclopeptides from Omphalotus olearius
Authors: Liermann Johannes C. , Opatz Till , Kolshorn Heinz , Antelo Luis , Hof Carolin , Anke Heidrun
Published: January 2009

Omphalotins E–I, oxidatively modified cyclic dodecapeptides, were isolated from mycelial extracts of the basidiomycete Omphalotus olearius, and their structures were determined by NMR spectroscopic and MS methods. Four of the five omphalotins contained an unprecedented N‐hydroxylated tricyclic tryptophan derivative. All compounds exhibited strong and selective nematicidal activity against the plant pathogen Meloidogyne incognita with LD90 values between 2 and 5 μg mL–1. Cytotoxic activities were not detected up to 50 μg mL–1. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Analysis of aliphatic amines using head‐column field‐enhanced sample stacking in MEKC with LIF detection
Authors: Zhang Jianhua , Cui Huimin , Xu Liangjun , Zhang Lan , Chen Guonan
Published: January 2009

This paper describes the use of head‐column field‐enhanced sample stacking for on‐line sample concentration in MEKC; the method has been applied to the determination of C1∼C9 aliphatic amines after their pre‐capillary derivatization with 3‐(4‐carboxybenzoyl) quinoline‐2‐carboxaldehyde (CBQCA). The optimum derivatization, on‐line concentration and separation conditions for these aliphatic amines were investigated in detail. The optimized molar ratio of CBQCA to amines was found to be 120:1, and 50 mmol/L borate buffer (pH 9.5) was used for derivatization in order to achieve high efficiency. Nine imidazole aliphatic amines were baseline separated within 12 min by using 50 mmol/L of sodium borate (pH 9.5) and 15 mmol/L of SDS as running buffer. Under the optimum conditions, the detection limits of these nine aliphatic amines ranged from 1.2 to 3.8 pmol/L. S/N=3, which was about 49∼173‐fold lower than those of conventional sample injections. After validation, the developed method was applied to the determination of C1∼C9 aliphatic amines in river water with the average recoveries of 86.7∼105%.
Field‐amplified sample injection for the determination of albumin and transferrin in human urines by MEKC
Authors: Wu Yi‐Wei , Liu Jun‐Feng , Xiao Tang‐Xin , Han De‐Yan , Zhang Hai‐Li , Pan Ji‐Cheng
Published: January 2009

An MEKC method combining field‐amplified sample injection (FASI) has been developed for the analysis of albumin (Alb) and transferrin (TRF) in human urines. Various parameters affecting FASI preconcentration were optimized systematically. Under the optimum conditions, using electrokinetic sample injection for 90 s, the sensitivity was improved 77.6‐ and 45.3‐fold for TRF and Alb, respectively, without loss of separation efficiency when compared with hydrodynamical sample injection for 5 s (0.5 psi). The detection limits of TRF and Alb were found to be 0.31 and 0.14 mg/L, respectively. The proposed method has been successfully applied to the determination of TRF and Alb in desalted urines from patients with kidney diseases, and the recoveries of TRF and Alb were 91.1–101.7%.
Three New Dicoumarins from Daphne feddei
Authors: Liang Shuang , Shen Yun‐Heng , Tian Jun‐Mian , Wu Zhi‐Jun , Jin Hui‐Zi , Zhang Wei‐Dong , Yan Shi‐Kai
Published: January 2009

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A novel dicoumarinolignoid, feddeiticin (1), the first example with a dicoumarinolignoid skeleton, along with the two new dicoumarin glucosides 2 and 3, were isolated from the stem barks of Daphne feddei. The structures were elucidated on the basis of spectral analyses.
Synthesis of 4‐(Methoxycarbonyl)phenyl β‐Lactoside Derivatives Modified at C(6) or C(6′), and Evaluation of Their Inhibitory Activity on Erythrina cristagalli Lectin‐Mediated Hemagglutination
Authors: Butera Anna Paola , de Souza Filho José Dias , Prado Maria Auxiliadôra Fontes , Lisboa Marilda Pereira , Alves Ricardo José
Published: January 2009

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We report herein the synthesis of 4‐(methoxycarbonyl)phenyl β‐lactoside and eight derivatives modified at C(6) or C(6′). These compounds were evaluated in hemagglutination inhibition assay using the lectin from Erythrina cristagalli. None of the compounds showed enhanced activity as compared to lactose.
The Absolute Configuration of the (+)‐ and (−)‐cis‐ and (+)‐ and (−)‐trans‐1‐Benzyl‐4‐hydroxypiperidine‐3‐methanols: An Unusual Application of the 1H‐NMR‐Mosher Method
Authors: Clerc Christian , Matarazzo Igor , Rüedi Peter
Published: January 2009

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The enantiomerically pure title compounds were prepared and the absolute configurations assigned by the high‐field 1H‐NMR application of the Mosher method on the bis‐MTPA derivatives (MTPA=α‐methoxy‐α‐(trifluoromethyl)benzeneacetic acid). The final evidence for the adaptability of the procedure was effected by X‐ray crystallographic analyses. The absolute configurations of the cis‐ and trans‐1‐benzyl‐4‐hydroxypiperidine‐3‐methanols are as follows: (+)‐(3S,4S) and (−)‐(3R,4R) (cis), and (+)‐(3R,4S) and (−)‐(3S,4R) (trans), respectively (Scheme 2). Nonfermenting bakers' yeast reduction of methyl 1‐benzyl‐4‐oxopiperidine‐3‐carboxylate afforded (+)‐methyl (3R,4S)‐1‐benzyl‐4‐hydroxypiperidine‐3‐carboxylate (de>97%, ee>99%) which was further reduced to the (+)‐(3S,4S)‐diol (Scheme 3). The result confirms the stereochemical outcome of the biological reduction with re‐face selectivity and cis‐diastereoselectivity as predicted for bakers' yeast. The 4‐hydroxypiperidine‐3‐methanols are the key starting compounds for the synthesis of the enantiomerically pure P(3)‐axially and P(3)‐equatorially substituted cis‐ and trans‐configurated 8‐benzyl‐2,4‐dioxa‐8‐aza‐3‐phosphadecalin 3‐oxides (=8‐benzyl‐2,4‐dioxa‐8‐aza‐3‐phospha‐bicyclo[4.4.0]decane 3‐oxides) representing γ‐homo‐acetylcholine mimetics.
5‐Benzyl‐3‐methylimidazolidin‐4‐one‐Derived Reactive Intermediates of Organocatalysis – A Comforting Resemblance of X‐Ray, NMR, and DFT Solid‐Phase, Liquid‐Phase, and Gas‐Phase Structures
Authors: Grošelj Uroš , Schweizer W. Bernd , Ebert Marc‐Olivier , Seebach Dieter
Published: January 2009

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The X‐ray crystal structures of three (E)‐1‐cinnamoylidene iminium PF6 salts of 5‐benzyl‐3‐methylimidazolidin‐4‐ones (2,2‐dimethyl‐, cis‐2‐(tert‐butyl)‐, and cis‐2‐styryl‐substituted; 2–4, resp.) are reported (Figs. 3–5). In the 2,2‐dimethyl and in the cis‐2‐styryl derivative, 2 and 4, respectively, a CH bond of the cis‐substituent in 2‐position points to the center of the benzene ring of the benzyl group above the five‐membered ring (Fig. 6, a and b). NMR Measurements (Fig. 8) provide evidence that the same structure is present in solution, and that a fourth derivative of this type, 5 (Scheme), has (Z)‐ instead of (E)‐configuration around the CN bond. In the cis‐2‐(tert‐butyl) derivative 3, the benzyl group is located over the iminium π‐system (Figs. 4 and 6, c). Overlays with DFT‐calculated crotonylidene analogs, A and B, show that the theoretical and experimental structures are almost superimposable (Fig. 9 and Table). The structures are discussed in view of their role as reactive intermediates in organocatalysis and in view of the help synthetic organic chemists may experience from theory.
Isotopic approach to understanding the groundwater flow system within an andesitic stratovolcano in a temperate humid region: case study of Ontake volcano, central Japan
Authors: Asai Kazuyoshi , Satake Hiroshi , Tsujimura Maki
Published: January 2009

We used isotope tracer methods to clarify the groundwater flow system within Mt Ontake: a stratovolcano consisting of andesite lava and pyroclastic rock, located within a temperate humid region. Precipitation was collected monthly at 11 sites on the south, east, north, and west slopes of the volcano for a period of 26 months. The weighted mean δ‐value in precipitation shows a clear decrease with increasing elevation (altitude effect) on all slopes and is relatively low on the leeward slope (rain‐shadowing effect). The springs collected over the entire area of the volcano show δ‐values that are controlled by the altitude effect and the rain‐shadowing effect on precipitation. The average recharge elevations of the individual springs were calculated from their δ18O‐values and the equation of the altitude effect of groundwater for corresponding slope. The average recharge elevation and tritium concentration in springs indicate that the large‐scale groundwater flow systems (vertical drop: ca 800 m) with a relatively long residence time are maintained along the lava flow in the younger volcano north zone, whereas relatively small‐scale groundwater flow systems (vertical drop: ca 400 m) are distributed across a wide range of elevations in the younger volcano south zone. In the older volcano zone at the foot of the volcano body, it is inferred that local groundwater flow systems (vertical drop: less than 200 m) dominate and that these flow systems are not connected to those in the younger volcano zone. Consequently, the scale of the groundwater flow system decreases with increasing age of the volcano body. This contraction of the flow system with time might reflect the progressive erosion of the volcano body, especially within the younger volcano zone. Copyright © 2009 John Wiley & Sons, Ltd.
Preparation of hydroxyapatite‐titania hybrid coatings on titanium alloy
Authors: Ün Serhat , Durucan Caner
Published: January 2009

Hydroxypapatite‐titania hybrid films on Ti6Al4V alloys were prepared by sol–gel technique by incorporating presynthesized hydroxypapatite (Ca10(PO4)6(OH)2 or HAp) powders into a titanium‐alkoxide dip coating solution. Titania network was formed by the hydrolysis and condensation of Ti‐isopropoxide Ti[OCH(CH3)2]4‐based sols. The effect of titania sol formulation, specifically the effect of organic solvents on the microstructure of the dip coated films calcined at 500°C has been investigated. The coatings exhibit higher tendency for cracking when a high vapor pressure solvent, such as ethanol (C2H5OH) is used causing development of higher macroscopic stresses during evaporation of the sol. Titania sol formulations replacing the solvent with n‐proponal (CH3(CH2)2OH) and acetly‐acetone (C5H8O) combinations enhanced the microstructural integrity of the coating during evaporation and calcination treatments. Sol–gel processing parameters, such as multilayer coating application and withdrawal rate, can be employed to change the titania thickness in the range of 0.120–1.1 μm and to control the microstructure of HAp‐titania hybrid coatings. A high‐calcination temperature in the range of 400–600°C does not cause a distinct change in crystals nature of the titania matrix or HAp, but results in more cracking due to the combined effect of densification originated stresses and thermal stresses upon cooling. Slower withdraw rates and multilayer dip coating lead to coatings more vulnerable to microcracking. © 2009 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2009
Development of a biomimetic collagen‐hydroxyapatite scaffold for bone tissue engineering using a SBF immersion technique
Authors: Al‐Munajjed Amir A. , Plunkett Niamh A. , Gleeson John P. , Weber Tim , Jungreuthmayer Christian , Levingstone Tanya , Hammer Joachim , O'Brien Fergal J.
Published: January 2009

The objective of this study was to develop a biomimetic, highly porous collagen‐hydroxyapatite (HA) composite scaffold for bone tissue engineering (TE), combining the biological performance and the high porosity of a collagen scaffold with the high mechanical stiffness of a HA scaffold. Pure collagen scaffolds were produced using a lyophilization process and immersed in simulated body fluid (SBF) to provide a biomimetic coating. Pure collagen scaffolds served as a control. The mechanical, material, and structural properties of the scaffolds were analyzed and the biological performance of the scaffolds was evaluated by monitoring the cellular metabolic activity and cell number at 1, 2, and 7 days post seeding. The SBF‐treated scaffolds exhibited a significantly increased stiffness compared to the pure collagen group (4‐fold increase), while a highly interconnected structure (95%) was retained. FTIR indicated that the SBF coating exhibited similar characteristics to pure HA. Micro‐CT showed a homogeneous distribution of HA. Scanning electron microscopy also indicated a mineralization of the collagen combined with a precipitation of HA onto the collagen. The excellent biological performance of the collagen scaffolds was maintained in the collagen‐HA scaffolds as demonstrated from cellular metabolic activity and total cell number. This investigation has successfully developed a biomimetic collagen‐HA composite scaffold. An increase in the mechanical properties combined with an excellent biological performance in vitro was observed, indicating the high potential of the scaffold for bone TE. © 2009 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2009
The effect of nucleus implant parameters on the compressive mechanics of the lumbar intervertebral disc: A finite element study
Authors: Joshi Abhijeet , Massey Christopher J. , Karduna Andrew , Vresilovic Edward , Marcolongo Michele
Published: January 2009

A simplified finite element model of the human lumbar intervertebral disc was utilized for understanding nucleus pulposus implant mechanics. The model was used to assess the effect of nucleus implant parameter variations on the resulting compressive biomechanics of the lumbar anterior column unit. The effects of nucleus implant material (modulus and Poisson's ratio) and geometrical (height and diameter) parameters on the mechanical behavior of the disc were investigated. The model predicted that variations in implant modulus contribute less to the compressive disc mechanics compared to the implant geometrical parameters, for the ranges examined. It was concluded that some threshold exists for the nucleus implant modulus, below which little variations in load–displacement behavior were shown. Compressive biomechanics were highly affected by implant volume (under‐filling the nucleus cavity, line‐to‐line fit, or over‐filling the nucleus cavity) with a greater restoration of compressive mechanics observed with the over‐filled implant design. This work indicated the effect of nucleus implant parameter variations on the compressive mechanics of the human lumbar intervertebral disc and importance of the “fit and fill” effect of the nuclear cavity in the restoration of the human intervertebral disc mechanics in compression. These findings may have clinical significance for nucleus implant design. © 2009 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2009
Ecomorphology of morpho‐functional relationships in the family of sparidae: A quantitative statistic approach
Authors: Antonucci Francesca , Costa Corrado , Aguzzi, Jacopo , Cataudella Stefano
Published: January 2009

In many fish species, morphological similarity can be considered as a proxy for similarities in habitat use. The Sparidae family includes species that are recognized for common morphological features such as structure and positioning of the fins and specialized dentition. The aim of this study was to quantitatively describe the relationship of body shape morphology with habitat use, trophic level, and systematics in the majority of known Sparidae species (N = 92). This ecomorphological comparison was performed with a geometric morphometric approach considering as variables the Trophic Index (TROPH), the habitat (i.e., classified as demersal, benthopelagic and reef associated) and the phylogenetic relationship of species at the subfamily level. The analysis by the TROPH variable showed a positive relation with shape because the morphological features of all the species are strongly correlated with their trophic behavior (e.g., herbivore species have a smaller mouth gap that make them able to feed upon sessile resources). The morphological analysis according to the Habitat variable was used to classify species according to a feeding‐habitat niche in terms of portion of the water column and seabed space where species mostly perform their behavioral activities. We described three kinds of morphological designs in relation to a benthopelagic, demersal and reef‐associated habit. The six subfamily groups were morphologically well distinguishable and the cladogram relative to Mahalanobis' morphological distances was compared with those proposed by other authors. We also quantified the phylogenetic relationship among the different subfamilies based on the analysis of shape in relation to trophic ecology, confirming the observations of the authors. J. Morphol., 2009. © 2009 Wiley‐Liss, Inc.
The role of positive‐based research in building the science of organizational behavior
Authors: Wright Thomas A. , Quick James Campbell
Published: January 2009

The role of the positive organizational movement continues to garner significant attention in the applied sciences. Using Kipling's “six honest serving men” framework (What, Why, When, How, Where, and Who), we discuss six potential challenges and opportunities facing the positive organizational movement. First, we review what constitutes the realm of positive behavior. Next, we discuss why an awareness of the holistic model is highly germane to any discussion of the positive organizational movement. Third, and addressing a key methodological issue confronting the positive movement, we examine when a “trait” is really a trait. Fourth, how we study what we study is examined. Fifth, where the positive movement can best contribute to employee betterment is introduced. Finally, we close with a discussion of just who really benefit from our research. Copyright © 2009 John Wiley & Sons, Ltd.
The emerging positive agenda in organizations: greater than a trickle, but not yet a deluge
Authors: Wright Thomas A. , Quick James Campbell
Published: January 2009

The evidence is clear regarding applied science's longstanding fascination with the negative aspects of organizational life. The purpose of this special issue of theJournal of Organizational Behavioris to tangibly demonstrate that the concept of a “positive psychology” is gaining importance in both psychology and organizational behavior. To that end, our lead article focuses on five topic areas. First, we provide a limited historical backdrop of positive organizational research. Second, we suggest the theoretical basis forwhythe current overwhelming emphasis on the negative. Next, we introduce the seven peer refereed articles contained in this special issue which, when considered together, highlight the varied application and potentially widespread benefits of studying the positive in organizational research. Fourth, incorporating the “point/counterpoint”JOBframework, we offer two varying, but insightful, perspectives on positive organizational research by Luthans and Avolio and Hackman. Finally, the article concludes with a discussion ofhowemerging research on the positive can be used to help build a stronger science of organizational behavior. Copyright © 2009 John Wiley & Sons, Ltd.
Psychological ownership: theoretical extensions, measurement and relation to work outcomes
Authors: Avey James B. , Avolio Bruce J. , Crossley Craig D. , Luthans Fred
Published: January 2009

Viewing psychological ownership as a positive resource for impacting human performance in organizations, the present study investigated the components of an expanded view of psychological ownership. Confirmatory factor analyses on a proposed measure of psychological ownership provided support for a positively‐oriented, “promotion‐focused” aspect of psychological ownership comprised of four dimensions: self‐efficacy, accountability, sense of belongingness and self‐identity. In addition, territoriality was examined as a unique and more “prevention‐focused” form of ownership. Practical implications and suggestions for future research on psychological ownership and positive organizational behavior conclude the article. Copyright © 2009 John Wiley & Sons, Ltd.
Zest and work
Authors: Peterson Christopher , Park Nansook , Hall Nicholas , Seligman Martin E. P.
Published: January 2009

Zest is a positive trait reflecting a person's approach to life with anticipation, energy, and excitement. In the present study, 9803 currently employed adult respondents to an Internet site completed measures of dispositional zest, orientation to work as a calling, and satisfaction with work and life in general. Across all occupations, zest predicted the stance that work was a calling (r = .39), as well as work satisfaction (r = .46) and general life satisfaction (r = .53). Zest deserves further attention from organizational scholars, especially how it can be encouraged in the workplace. Copyright © 2009 John Wiley & Sons, Ltd.
Team level positivity: investigating positive psychological capacities and team level outcomes
Authors: West Bradley J. , Patera Jaime L. , Carsten Melissa K.
Published: January 2009

The movement toward positive psychology has uncovered the important role that positivity plays in both individual and organizational success. Given that work teams are becoming increasingly embedded in organizational structures, it is surprising that few researchers have investigated positivity at the team level. The present study examines the emergence of team level positive psychological capacities and their relationship with team outcomes (e.g., cohesion, cooperation, coordination, and conflict and team satisfaction) during two team sessions. Results from 101 teams suggest that team optimism is an important predictor of team outcomes when teams are newly formed, whereas team resilience and team efficacy show greater explanatory power after several team interactions. Implications of the findings are discussed, as well as possible avenues for additional research. Copyright © 2009 John Wiley & Sons, Ltd.
Thoracic cytoreductive surgery and intraoperative hyperthermic intrathoracic chemotherapy for pseudomyxoma peritonei
Authors: Chua Terence C. , Yan Tristan D. , Yap Zhu L. , Horton Matthew D. , Fermanis Gary G. , Morris David L.
Published: January 2009

Background

Pleural dissemination of pseudomyxoma peritonei (PMP) is considered an advanced/terminal disease. We review our experience with thoracic cytoreductive surgery (CRS) and intraoperative hyperthermic intrathoracic chemotherapy (HITHOC) for the treatment of pleural recurrence of PMP following previous intraabdominal surgery.

Patients and Methods

An observational study of five patients with pleural dissemination from PMP treated with thoracic CRS and intraoperative HITHOC with mitomycin C for 90 min at 41.5°C.

Results

There were three men. The mean age was 46.5 (10.5) years. Postoperatively, one patient developed Grade I, one patient developed Grade III and one patient developed Grade IV postoperative complication. Two patients had an unremarkable postoperative recovery. Only one patient has died 38 months since treatment from abdominal complication of this disease with no evidence of thoracic disease. The four surviving patients are still alive 4.6–47.4 months after treatment. Two patients have evidence of an intraabdominal recurrence.

Conclusions

Thoracic CRS and intraoperative HITHOC is a safe and effective procedure to treat pleural dissemination from PMP. Long‐term disease‐free survival can be achieved from this treatment for which no other potentially curative therapy has been described. J. Surg. Oncol. 2009;99:292–295. © 2009 Wiley‐Liss, Inc.