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R1
Kinds of R1 Terms modified by R1 Selected AbstractsStudy of the MR relaxation of microglia cells labeled with Gd-DTPA-bearing nanoparticlesCONTRAST MEDIA & MOLECULAR IMAGING, Issue 3 2009Emeline Julie Ribot Abstract Therapies involving cells as vehicles need to visualize in situ the trafficking of the cells concerned. This cellular imaging can be driven by cell contrast agent-based nanoparticle internalization and non-invasive MRI (magnetic resonance imaging) detection. Here, microglial cells, that would transport a suicide gene to a glioma, were incubated for different times, with various concentrations of silica nanoparticles on which numerous Gd-DTPA were grafted. The goal of this study was to investigate the repartition of cell-associated particles. MRI was used to quantitatively follow the particle uptake process. Fluorescence microscopy images showed that, although most of the nanoparticles were internalized, some remained adsorbed on the extracellular membrane surface. The cells were then submitted to various treatments: glycine to release bound nanoparticles and/or ultrasound to destroy the cell membranes. The R1 relaxation rates were measured at 4.7 T. R1 was maximal for 4,h of incubation, decreased after 8,h and remained stable for the 24 following hours. The magnetic resonance signal of ultrasonicated and glycine-treated cells made it possible to quantify the loss of bound nanoparticles after 8,h. Nevertheless, this release did not prevent cell detection since the internalized nanoparticles are enough concentrated to visualize the labeled cells even after 4 days of cell growth. These results highlight the compartmentalization of nanoparticles in microglia and the evolution of the MR signal of the labeled cells. This study could be of importance to interpret in vivo the MR signal changes that could occur after administration of such nanoparticle-labeled cells in therapeutic strategies. Copyright © 2009 John Wiley & Sons, Ltd. [source] Imidazolium based ionic liquid crystals: structure, photophysical and thermal behaviour of [Cnmim]Br·xH2O (n = 12, 14; x=0, 1)CRYSTAL RESEARCH AND TECHNOLOGY, Issue 11 2008A. Getsis Abstract The long chain imidazolium halides [Cnmim]Br·xH2O (n = 10, 12; x = 0, 1) have been synthesized and their structural and thermal behaviour together with their photophysical properties characterized. X-ray structure analyses of the monohydrates ([C12mim]Br·H2O: triclinic, P1, no. 2, Z = 2, Pearson code aP112, a = 550.0(5) pm, b = 779.4(5) pm, c = 2296.1(5) pm, , = 81.89(5)°, , = 83.76(5)°, , = 78.102(5)°, 3523 unique reflections with Io > 2,(Io), R1 = 0.0263, wR2 = 0.0652, GooF = 1.037, T = 263(2) K; [C14mim]Br,H2O: triclinic, P1, no. 2, Z = 12, Pearson code aP11, a = 549.86(8) pm, 782.09(13) pm, c = 2511.3(4) pm, , = 94.86(2)°, , = 94.39(2)°, , = 101.83(2)°, 2063 unique reflections with Io > 2,(Io), R1 = 0.0429, wR2 = 0.0690, GooF = 0.770, T = 293(2) K) show for both compounds similar bilayered structures. Sheets composed of hydrophilic structure regions constituted by positively charged imidazolium head groups, bromide anions and hydrogen bonded water alternate with hydrophobic areas formed by interdigitated long alkyl chains belonging to imidazolium cations with different orientation. Combined differential scanning calorimetry and polarizing optical microscopy shows that the monohydrates as well as the anhydrous imidazolium salts are thermotropic liquid crystals which adopt smectic mesophases. The mesophase region is larger in case of the monohydrates when compared to the anhydrous compounds indicating that water obviously stabilizes the mesophase. All compounds show an intense whitish photoluminescence with short lived (1,,1,*) and long lived (1,,3,*) transitions. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Crystal structure of a tetrazole derivativeCRYSTAL RESEARCH AND TECHNOLOGY, Issue 3 2006H. S. Yathirajan Abstract 5-(4'-Methyl-1,1'-biphenyl-2-yl)-1H-tetrazole(MBT), C28H24N8, CCDC: 223082, F.W.=472.55, triclinic, P1, a=4.99(1)Å, b=14.25(4)Å, c=16.63(5)Å, , = 90.27(5)°, , = 91.19(5)°, , = 90.64(5)°, V = 1182(6)Å3, Z = 4, Dcal = 1.327 Mgm -3, , = 0.084mm -1, F000 = 496, , (MoK,) = 0.71073Å, final R1 and wR2 are 0.0924 and 0.2309, respectively. There are two crystallographically independent molecules in the asymmetric unit. The dihedral angles between the two phenyl rings of the biphenyl ring system are 44.2(2)° and 44.3(2)° for the two molecules respectively. The molecules are stabilized by N-H,N and C-H,N types of intermolecular hydrogen bonds in the unit cell in addition to van der Waals forces. © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [source] Synthesis and X-ray structure of two conformational isomers of [Zn(medpt)(SCN)2], medpt = bis (3 , aminopropyl)methylamineCRYSTAL RESEARCH AND TECHNOLOGY, Issue 2 2006S. Guha Abstract Two conformational isomers of [Zn (medpt)(NCS)2], medpt=bis(3-aminopropyl) methylamine, (1) and (2) have been synthesised and the crystal structures are determined using single crystal X-ray diffraction. The structures of the complexes have been solved by Patterson method and refined by full-matrix least- squares techniques to R1 = 0.0524 for (1) and R1 = 0.0506 for (2), respectively. The geometry around the Zn(II) centre in both isomers is distorted trigonal bipyramidal. The two pendent thiocyanate moieties in (1), with Zn,N,C angles 167.9(4),173.9(4)º, coordinate the mental centre almost linearly while the corresponding coordinations in (2) are significantly bent [Zn,N,C angles 150.8(3),153.1(2)°]. Intermolecular N,H,S hydrogen bonds stabilise the crystal packing in the complexes forming infinite chains parallel to the [100] direction. The combinations of molecular chains generate three/two dimensional supramolecular framework in complexes (1) and (2). (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] In humans the adiponectin receptor R2 is expressed predominantly in adipose tissue and linked to the adipose tissue expression of MMIF-1DIABETES OBESITY & METABOLISM, Issue 4 2010K. Kos In this study, the regional adipose tissue-adiponectin (AT-ADN) and adiponectin receptor (R1 and R2) expression and their relation with metabolic parameters, circulating and AT-derived cytokine expressions were compared. Paired subcutaneous adipose tissue (SCAT) and visceral adipose tissue (VAT) were taken from 18 lean and 39 obese humans, AT-mRNA expression of adipokines analysed by RT-PCR and corresponding serum levels by enzyme-linked immunosorbent assay (ELISA). R1 and R2 adipocyte expression was compared with 17 other human tissues. ADN-gene expression was lower in VAT than SCAT [mean (SD) 1.54 (1.1) vs. 2.84 (0.87); p < 0.001], and lower in obese subjects (VAT : p = 0.01;SCAT : p < 0.001). SCAT-ADN correlated positively with serum ADN (r = 0.33;p = 0.036) but not VAT-ADN. AT expressions of ADN and macrophage migration inhibiting factor (MMIF), IL18 and cluster of differentiation factor 14 (CD14) in both depots showed inverse correlations. R1 and R2 were expressed ubiquitously and R2 highest in SCAT, and this is much higher (×100) than R1 (×100). R expression was similar in lean and obese subjects and unrelated to the metabolic syndrome, however, receptors correlated with VAT-MMIF (R 1: r = 0.4;p = 0.008;R 2: r = 0.35,p = 0.02) and SCAT-MMIF expression (R 2: r = 0.43;p = 0.004). Unlike ADN, its receptors are expressed in many human tissues. Human R2 expression is not highest in the liver but in AT where it is associated with MMIF expression. The adiponectin-dependent insulin-sensitizing action of thiazolidinediones is thus probably to differ amongst species with weaker effects on the human liver. [source] Synthesis and calcium channel modulating effects of modified Hantzsch nitrooxyalkyl 1,4-dihydro-2,6-dimethyl-3-nitro-4-(pyridinyl or 2-trifluoromethylphenyl)-5-pyridinecarboxylatesDRUG DEVELOPMENT RESEARCH, Issue 4 2000Ramin Miri Abstract A group of racemic nitrooxyalkyl 1,4-dihydro-2,6-dimethyl-3-nitro-4-(pyridinyl or 2-trifluoromethylphenyl)-5-pyridinecarboxylates 8a,o were synthesized using modified Hantzsch reactions. In vitro calcium channel antagonist activities, determined using a guinea pig ileum longitudinal smooth muscle (GPILSM) assay, showed that compounds 8a,o exhibited weaker calcium antagonist activity (10,5 to 10,7 M range) than the reference drug nifedipine (IC50 = 1.43 × 10,8 M). Compounds 8 possessing a C-4 R1 = 2-pyridyl substituent were always more potent than the approximately equiactive analogs having an R1 = 3-pyridyl, 4-pyridyl or 2-CF3 -C6H4 -substituent, within each subgroup of nitrooxyalkyl compounds [R2 = , (CH2)nONO2 (n = 2, 3, 4) or ,CH(CH2ONO2)2]. Although the length of the R2 = ,(CH2)nONO2 substituent (n = 2,4) was not a determinant of smooth muscle calcium antagonist activity when the C-4 R1 -substituent was 2-pyridyl, when R1 was a 3-pyridyl, 4-pyridyl, or 2-CF3 -C6H4 -substituent, the relative potency order with respect to the R2 = ,(CH2)nONO2 substituent was n = 3 and 4 > n = 2. Replacement of the isopropyl substituent of the ester moiety of the calcium antagonist (±)-2-pyridyl 3a by a ,(CH2)nONO2 (n = 2,4) moiety increased calcium antagonist activity on GPILSM by 8-fold. In contrast, replacement of the isopropyl substituent of the ester moiety of the calcium agonists (±)-3-pyridyl 3b, (±)-4-pyridyl 3c or the methyl substituent of the ester moiety of Bay K8644 by a R2 nitrooxyalkyl substituent resulted in abolition of their calcium agonist effects on GPILSM that is replaced by a smooth muscle calcium antagonist effect. These calcium antagonist data support the concept that incorporation of a nitrooxyalkyl ester substituent constitutes a valuable drug design strategy to enhance Hantzsch 1,4-dihydropyridine calcium antagonist and/or abolish calcium agonist effects on smooth muscle. Replacement of the isopropyl (8b,c), or the methyl (8d) group by a ,CH2CH2ONO2 moiety resulted in retention of the cardiac positive inotropic effect where the relative potency order with respect to the C-4 substituent was 2-CF3 -C6H6 - (8d) > 3-pyridyl (8b) , 4-pyridyl (8c). Model hybrid (calcium channel modulation, ·NO release) compounds, that exhibit dual cardioselective agonist / smooth muscle selective antagonist activities, represent a novel type of 1,4-dihydropyridine CC modulator that offers a potential approach to drug discovery targeted toward the treatment of congestive heart failure and for use as probes to study the structure,function relationship of calcium channels. Drug Dev. Res. 51:225,232, 2000. © 2001 Wiley-Liss, Inc. [source] Improved treatment outcome in Chinese children and adolescents with Burkitt's lymphoma and large cell lymphoma by using the modified B-non-Hodgkin's lymphoma-Berlin-Frankfurt-Münster-90 protocolEUROPEAN JOURNAL OF HAEMATOLOGY, Issue 5 2006Xiao-Fei Sun Abstract:,Objectives:,This study was designed to evaluate the efficacy and toxicity of the modified B-Non-Hodgkin's Lymphoma (NHL)-Berlin-Frankfurt-Münster (BFM)-90-based protocol in Chinese children and adolescents with Burkitt's lymphoma and large cell lymphoma. Methods:,From September 1997 to August 2005, 55 untreated patients (age less than 20 yr) from a single institution were enrolled. The patients were stratified by risk factors (stage, LDH level and chemotherapy response). All patients were treated with a modified B-NHL-BFM 90 protocol. Results:,The median age of the patients was 8 yr (range 1.5,20 yr). Of these patients, 22 (40%) had Burkitt's lymphoma (BKL), 22 (40%) had diffuse large B-cell lymphoma (DLBL) and 11 (20%) had anaplastic large T-cell lymphoma (ALCL). Complete remission (CR) occurred in 45 patients (83%), partial remission (PR) in eight patients (14.5%), and progressive disease (PD) in one patient (1.8%). At a median follow up of 24 months, the event free survival (EFS) for all patients was 85% ± 5% with 100% for group R1, 84% ± 7% for group R2 and 72% ± 13% for group R3, and most notably, 80% ± 6% for stage III/IV at diagnosis. There was no statistically significant difference (P = 0.96) in EFS among BKL and DLBL and ALCL. The major toxicity complications were myelosuppression and mucositis, but these conditions were tolerated and manageable. Conclusions:,This modified NHL-BFM-90 protocol is very effective for Chinese children and adolescents with BKL and large cell lymphomas, and represented an increase in the cure rates in childhood NHL in China. [source] Ba6Si6N10O2(CN2) , A Nitridosilicate with a NPO-Zeolite Structure Type Containing Carbodiimide IonsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2009Sandro Pagano Abstract A new precursor approach leading to NPO-zeolite analogous nitridosilicates with cavities containing carbodiimide ions is presented. The reaction of amorphous "Si(CN2)2" and barium in liquid sodium afforded Ba6Si6N10O2(CN2) as yellow crystals. The structure is a rare example of the NPO-zeolite framework type and the first nitridosilicate incorporating carbodiimide ions. The partially ordered integration of carbodiimide moieties in the channels leads to the formation of a superstructure (P, no. 174, a = 16.255(2), c = 5.4690(11) Å, Z = 3, R1 = 0.0299, 2139 data, 100 parameters) and merohedral twinning. A comprehensive structure solution is presented, taking all possible ordering variants and twin laws into account.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Nickel Complexes of N/O -Functionalized N-Heterocyclic Carbenes as Precatalysts for Michael Reactions in Air at Room Temperature Under the Much Preferred Base-Free ConditionsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2009Sriparna Ray Abstract A series of several new nickel precatalysts supported overN/O -functionalized N-heterocyclic carbenes (NHC) for the Michael reactions of ,-dicarbonyl, ,-keto ester, ,-diester, and ,-cyano ester compounds with ,,,-unsaturated carbonyl compounds in air at ambient temperature under the much preferred base-free conditions are reported. Specifically, the nickel complexes, [1-(R1 -aminocarbonylmethyl)-3-R2 -imidazol-2-ylidene]2Ni [R1 = 2-C6H4(OMe); R2 = Me (1b), iPr (2b), CH2Ph (3b) and R1 = 2-CH2C4H3O; R2 = Me (4b), CH2Ph (5b)] carried out the highly convenient base-free Michael addition of the activated C,H compounds across ,,,-unsaturated carbonyl compounds in air at room temperature. The complexes 1b,5b were synthesized by the direct reaction of the respective imidazolium chloride salt with NiCl2·6H2O in CH3CN in the presence of K2CO3 as a base. The exceptional stability of 1b,5b has been attributed to the deeply buried nickel,NHC ,-bonding molecular orbitals as evidenced from the density functional theory (DFT) studies. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Fragmentation of Alkoxo(catecholato)vanadium(V) Complexes[(C6H4O2)V(OR1)(OR2)]+ in the Gas PhaseEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 14 2005Malgorzata Kaczorowska Abstract Electrospray ionization (ESI) mass spectrometry is used to investigate the gas-phase dissociation behavior of vanadium(V) complexes [(C6H4O2)V(OR1)(OR2)]+ containing two identical or different alkoxy groups (R1, R2 = CH3, C2H5, n -C3H7, i -C3H7 and t -C4H9) and a catecholato ligand (C6H4O2). The fragmentation reactions of the complexes are studied by collision-induced dissociation (CID) and labeling experiments. For [(C6H4O2)V(OR1)(OR2)]+ cations with alkoxo groups larger than methyl, a trend for preferential evaporation of hydrocarbon fragments is observed, followed by expulsion of neutral alcohols. Further, the CID spectra of all complexes show a signal which can be assigned to the complex [(C6H4O2)VO]+. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] A Theoretical Investigation of Substituent Effects on the Absorption and Emission Properties of a Series of Terpyridylplatinum(II) Acetylide ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 10 2005Xiao-Juan Liu Abstract A comprehensive calculational investigation has been carried out on a series of complexes of the type [(terpyridyl-R1)Pt(C,C-R2)], where terpyridyl-R1 is a series of substituted 2,2':6',2"-terpyridyl ligands and C,C-R2 is a series of substituted acetylide ligands. In one series of complexes (I), the energy of the electronic excited state is varied by changing the substituents on the terpyridyl ligand (R1). In a second series of complexes (II), this electronic structure variation is obtained by changing the para substituents (R2) of the acetylide ligand. The effect of varying the substituents on the lowest-energy excited states of the complexes has been assessed by calculating their electronic structures and excitation energies. We anticipated that introduction of electron-withdrawing substituents on the terpyridyl ligand will benefit the LLCT (or MLCT) and prohibit the nonradiative pathways via d-d transitions in these complexes; introduction of electron-donating substituents on the acetylide ligand can also prohibit the nonradiative pathways by increasing the energy gaps between the HOMO,LUMO and d-d transitions. The results also reveal that the lowest-energy excitations of all complexes of series I and IIa,b complexes are dominated by a ,(C,C),,,,*(terp) (LLCT) transition mixed with some energetically d,(Pt),,,terpyridyl (MLCT) transition. However, for the complexes IIc,IId, in which phenyl rings are introduced on the acetylide ligand, the lowest-lying absorptions of IIc and IId are predominately LLCT in character, with less MLCT mixture, due to a lower contribution of the Pt(d) orbital to the HOMO, while for IIe, with a stronger donor on the acetylide, the lowest-lying absorption is completely LLCT in character. The absorption and emission calculations using the TDDFT method are based on the optimized geometries obtained at the B3LYP/LanL2DZ and CIS/LanL2DZ levels, respectively. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Structural and Electrochemical Studies of Dimerization and Rotational Isomerization in Multi-Iron SilicotungstatesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2005Travis M. Anderson Abstract A structural and electrochemical investigation of dimerization and Baker,Figgis (rotational) isomerization in the tri-ferric-substituted silicotungstates has been undertaken because these phenomena are important in a large number of polyoxometalates. A single-crystal X-ray diffraction analysis of K4Na7[(,-SiFe3W9(OH)3O34)2(OH)3] (,1) has been carried out [a = 12.9709(7) Å, b = 38.720(2) Å, c = 21.4221(12) Å, orthorhombic, Pbcm, R1 = 8.48,%, based on 13809 independent reflections]. The complex is isostructural with [(,-SiFe3W9(OH)3O34)2(OH)3]11, (,1) except that the edge-shared W3O13 caps in each [SiFe3W9(OH)3O34]4, unit are rotated by 60°. Electrochemical measurements, performed in a pH 5 acetate buffer, indicate a positive shift in the FeIII -based peak potential (and no change for the WVI -based potential) upon going from ,1 to its monomeric derivative [(,-Si(FeOH2)3W9(OH)3O34)]4, (,2) (,0.484,±,0.005 V and ,0.474,±,0.005 V, respectively). In contrast, the peak potentials of the FeIII - and WVI -based redox processes of ,1 are both found at more negative values than its rotational isomer ,1. The absolute values of the reduction peak potential differences are 0.022 V for FeIII and 0.162 V for WVI. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Carboxy Ester Hydrolysis Promoted by a Dicopper(II) Macrocyclic Polyamine Complex with Hydroxypropyl Pendant GroupsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2004Jin Huang Abstract A dinuclear CuII complex containing a hexaaza macrocyclic ligand bearing two 2-hydroxypropyl pendants, 3,6,9,16,19,22-hexaaza-6,19-bis(2-hydroxypropyl)tricyclo[22.2.2.211,14]triaconta-1,11,13,24,27,29-hexaene (L), was synthesized. The title complex [Cu2(H,2L)Cl2]·6.5H2O was isolated as a blue crystal, orthorhombic, space group Fddd, with a = 16.4581(12), b = 32.248(2), c = 35.830(2) Å, V = 19017(2) Å3, Z = 16, R1 = 0.0690, and wR2 = 0.1546 [I > 2,(I)]. The protonation constants of Cu2L were determined by potentiometric titration, and it was found that the alcoholic hydroxypropyl group of the complex Cu2L exhibits low pKa values of pKa1 = 7.31, pKa2 = 7.83 at 25 °C. The hydrolysis kinetics of 4-nitrophenyl acetate (NA) promoted by the title complex have also been studied. The pH-rate profile for Cu2L gave a sigmoidal curve and showed a second-order rate constant of 0.39 ± 0.02 M,1 s,1 in 10% CH3CN/H2O(v/v), which is greater than that of the dinuclear CuII complex formed by a hexaaza macrocycle without pendants. The reason for the higher catalytic activity of the title complex is discussed. We found that the volume of nucleophile RO, can effect the hydrolysis of the carboxy ester, the nucleophilicity of RO, and the Lewis acidity of the metal macrocycle also affect the carboxy ester hydrolysis. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Synthesis and Dynamic Features of (Chloro)zirconocene Cations Stabilised by Pendant (Diarylphosphanyl)alkyl and (Dimethylamino)alkyl Substituents at Their Cyclopentadienyl Ring SystemsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2003Steve Döring Abstract Treatment of the substituted (diarylphosphanyl)methyl group-4 metallocene complexes [(C5H4,CR1R2,PAr2)2ZrCl2] (2: R1/R2 = CH3/CH3, H/CH3, H/aryl) with Li[B(C6F5)4] in dichloromethane solution results in chloride ligand abstraction (with LiCl precipitation) to yield the complexes [(C5H4,CR1R2,PAr2)2Zr,Cl+] (5), with both phosphanyl groups internally coordinated to the metal centre. Three possible diastereoisomers are observed in the case of 5c (R1 = H; R2 = CH3), while bulkier R2 substituents give higher selectivities. The thermally induced (reversible) cleavage of the Zr,phosphane linkage results in dynamic NMR behaviour. Gibbs activation energies of ,G,(298 K) = 14.8 ± 0.5 and 14.5 ± 0.5 kcal/mol were obtained for these intramolecular equilibration processes in the complexes trans - 5d (R1 = H; R2 = Ph) and trans - 5e (R1 = H; R2 = ferrocenyl), respectively. Treatment of the substituted (dimethylamino)methyl metallocene complexes [(C5H4,CR1R2,NMe2)2ZrCl2] (6a, 6b) with Li[B(C6F5)4] proceeds analogously to yield the cation systems [{C5H4,C(CH3)2,NMe2}2ZrCl+] (12a) and [{C5H4,CH(CH3),NMe2}2ZrCl+] (12b, three possible diastereoisomers). Both complexes have their pairs of amino groups coordinated to the metal centre. The complexes exhibit dynamic NMR spectra. Selective equilibration of the diastereotopic N(CH3)A(CH3)B resonances of complex 12a is observed [,G,(233 K) = 11.5 ± 0.2 kcal/mol], whereas the adjacent C(CH3)A(CH3)B methyl groups remain diastereotopic. The dynamic equilibration of the latter was observed at a markedly higher temperature [,G,(333 K) = 17.3 ± 0.2 kcal/mol]. Treatment of [{C5H4,C(CH3)2,NMe2}CpZrCl2] (10) with Li[B(C6F5)4] resulted in the formation of complex [{C5H4,C(CH3)2,NMe2}CpZr,Cl+] (11), which shows the internal ,N(CH3)A(CH)B equilibration proceeding with a markedly higher activation barrier [,G,(333 K) = 17.6 ± 0.2 kcal/mol] than in 12a, and a stereochemical memory effect indicative of solvent coordination to the metal centre of the resulting highly electrophilic chlorozirconocene cation intermediate. Complex 11 was characterised by an X-ray crystal structure analysis, which shows the internal Zr,amine coordination. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Rapid and long-term alterations of hippocampal GABAB receptors in a mouse model of temporal lobe epilepsyEUROPEAN JOURNAL OF NEUROSCIENCE, Issue 8 2003Andrea Straessle Abstract Alterations of ,-aminobutyric acid (GABA)B receptor expression have been reported in human temporal lobe epilepsy (TLE). Here, changes in regional and cellular expression of the GABAB receptor subunits R1 (GBR1) and R2 (GBR2) were investigated in a mouse model that replicates major functional and histopathological features of TLE. Adult mice received a single, unilateral injection of kainic acid (KA) into the dorsal hippocampus, and GABAB receptor immunoreactivity was analysed between 1 day and 3 months thereafter. In control mice, GBR1 and GBR2 were distributed uniformly across the dendritic layers of CA1,CA3 and dentate gyrus. In addition, some interneurons were labelled selectively for GBR1. At 1 day post-KA, staining for both GBR1 and GBR2 was profoundly reduced in CA1, CA3c and the hilus, and no interneurons were visible anymore. At later stages, the loss of GABAB receptors persisted in CA1 and CA3, whereas staining increased gradually in dentate gyrus granule cells, which become dispersed in this model. Most strikingly, a subpopulation of strongly labelled interneurons reappeared, mainly in the hilus and CA3 starting at 1 week post-KA. In double-staining experiments, these cells were selectively labelled for neuropeptide Y. The number of GBR1-positive interneurons also increased contralaterally in the hilus. The rapid KA-induced loss of GABAB receptors might contribute to epileptogenesis because of a reduction in both presynaptic control of transmitter release and postsynaptic inhibition. In turn, the long-term increase in GABAB receptors in granule cells and specific subtypes of interneurons may represent a compensatory response to recurrent seizures. [source] Dentine sealing provided by smear layer/smear plugs vs. adhesive resins/resin tagsEUROPEAN JOURNAL OF ORAL SCIENCES, Issue 4 2007Marcela R. Carrilho The aim of this study was to evaluate the ability of five experimental resins, which ranged from hydrophobic to hydrophilic blends, to seal acid-etched dentine saturated with water or ethanol. The experimental resins (R1, R2, R3, R4, and R5) were evaluated as neat bonding agents (100% resin) or as solutions solvated with absolute ethanol (70% resin/30% ethanol). Fluid conductance was measured at 20 cm H2O hydrostatic pressure after sound dentine surfaces were: (i) covered with a smear layer; (ii) acid-etched; or (iii) bonded with neat or solvated resins, which were applied to acid-etched dentine saturated with water or ethanol. In general, the fluid conductance of resin-bonded dentine was significantly higher than that of smear layer-covered dentine. However, when the most hydrophobic neat resins (R1 and R2) were applied to acid-etched dentine saturated with ethanol, the fluid conductance was as low as that produced by smear layers. The fluid conductance of resin-bonded dentine saturated with ethanol was significantly lower than for resin bonded to water-saturated dentine, except for resin R4. Application of more hydrophobic resins may provide better sealing of acid-etched dentine if the substrate is saturated with ethanol instead of with water. [source] Activation Parameters for the Epoxidation of Substituted cis/trans Pairs of 1,2-Dialkylalkenes by DimethyldioxiraneEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 20 2006Brian S. Crow Abstract The first activation parameter data for the reaction of dimethyldioxirane (1) with five cis/trans pairs of alkenes are reported. The epoxidation of cis -1,2-dialkylalkenes (2cis: R1 = Me, R2 = iPr; 3cis: R1 = Me, R2 = tBu; 4cis: R1 = R2 = Et; 5cis: R1 = Et, R2 = iPr; 6cis: R1 = Et, R2 = tBu) and trans -1,2-dialkylalkenes (2trans: R1 = Me, R2 = iPr; 3trans: R1 = Me, R2 = tBu; 4trans: R1 = R2 = Et; 5trans: R1 = Et, R2 = iPr; 6trans: R1 = Et, R2 = tBu) by 1 produced the corresponding epoxides, quantitatively and stereospecifically, as the sole observable products. Activation parameters of the epoxidation of the five pairs of alkenes, 2cis,6cis and 2trans,6trans, by 1 were determined using the Arrhenius method. Enhanced selectivity for cis - vs. trans -alkene epoxidation was observed at lower temperatures. In general, the ,G, terms were larger and showed more variability for the reaction of 1 with trans -alkenes as compared to those for the corresponding cis isomers. The ,H, terms mirrored trends observed in ,G, because ,S, terms for all ten of the compounds were roughly identical. The ,,G, values, a comparison of the trans to the cis isomer data, yielded positive values of 1.2 to 1.8 kcal/mol for the five sets of data and appeared to be dependent on relative steric interactions. The experimental activation parameter data, consistent with predictions from ab initio calculations based on a spiro transition-state model, showed that the lower reactivity of trans -alkenes is due to enthalpy factors. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] A mutagenic analysis of the RNase mechanism of the bacterial Kid toxin by mass spectrometryFEBS JOURNAL, Issue 17 2009Elizabeth Diago-Navarro Kid, the toxin of the parD (kis, kid) maintenance system of plasmid R1, is an endoribonuclease that preferentially cleaves RNA at the 5, of A in the core sequence 5,-UA(A/C)-3,. A model of the Kid toxin interacting with the uncleavable mimetic 5,-AdUACA-3, is available. To evaluate this model, a significant collection of mutants in some of the key residues proposed to be involved in RNA binding (T46, A55, T69 and R85) or RNA cleavage (R73, D75 and H17) were analysed by mass spectrometry in RNA binding and cleavage assays. A pair of substrates, 5,-AUACA-3,, and its uncleavable mimetic 5,-AdUACA-3,, used to establish the model and structure of the Kid,RNA complex, were used in both the RNA cleavage and binding assays. A second RNA substrate, 5,-UUACU-3, efficiently cleaved by Kid both in vivo and in vitro, was also used in the cleavage assays. Compared with the wild-type protein, mutations in the residues of the catalytic site abolished RNA cleavage without substantially altering RNA binding. Mutations in residues proposed to be involved in RNA binding show reduced binding efficiency and a corresponding decrease in RNA cleavage efficiency. The cleavage profiles of the different mutants were similar with the two substrates used, but RNA cleavage required much lower protein concentrations when the 5,-UUACU-3, substrate was used. Protein synthesis and growth assays are consistent with there being a correlation between the RNase activity of Kid and its inhibitory potential. These results give important support to the available models of Kid RNase and the Kid,RNA complex. [source] Porous Polymersomes with Encapsulated Gd-Labeled Dendrimers as Highly Efficient MRI Contrast AgentsADVANCED FUNCTIONAL MATERIALS, Issue 23 2009Zhiliang Cheng Abstract The use of nanovesicles with encapsulated Gd as magnetic resonance (MR) contrast agents has largely been ignored due to the detrimental effects of the slow water exchange rate through the vesicle bilayer on the relaxivity of encapsulated Gd. Here, the facile synthesis of a composite MR contrast platform is described; it consists of dendrimer conjugates encapsulated in porous polymersomes. These nanoparticles exhibit improved permeability to water flux and a large capacity to store chelated Gd within the aqueous lumen, resulting in enhanced longitudinal relaxivity. The porous polymersomes, ,130,nm in diameter, are produced through the aqueous assembly of the polymers, polyethylene oxide- b -polybutadiene (PBdEO), and polyethylene oxide- b -polycaprolactone (PEOCL). Subsequent hydrolysis of the caprolactone (CL) block resulted in a highly permeable outer membrane. To prevent the leakage of small Gd-chelate through the pores, Gd was conjugated to polyamidoamine (PAMAM) dendrimers via diethylenetriaminepentaacetic acid dianhydride (DTPA dianhydride) prior to encapsulation. As a result of the slower rotational correlation time of Gd-labeled dendrimers, the porous outer membrane of the nanovesicle, and the high Gd payload, these functional nanoparticles are found to exhibit a relaxivity (R1) of 292 109,mM,1,s,1 per particle. The polymersomes are also found to exhibit unique pharmacokinetics with a circulation half-life of >3.5,h and predominantly renal clearance. [source] Competition between the replication initiator DnaA and the sequestration factor SeqA for binding to the hemimethylated chromosomal origin of E. coli in vitroGENES TO CELLS, Issue 11 2000Aziz Taghbalout Following replication initiation, the replication origin (oriC) in Escherichia coli enters a hemimethylated state at Dam methylation sites which are recognized by the SeqA protein. SeqA binds preferentially to hemimethylated GATC sequences of DNA in vitro. SeqA is essential for the synchronous initiation of chromosome replication from oriC copies in vivo. We show that: (i) purified SeqA binds AT-rich and 13-mers regions and two DnaA boxes, R1 and M, of hemimethylated oriC. (ii) SeqA inhibits the in vitro replication of a hemimethylated oriC plasmid more efficiently than the fully methylated, (iii) SeqA inhibits competitive binding of DnaA protein to the regions of the hemimethylated oriC plasmid, explaining the mechanism of its inhibitory effect. The inhibition of DnaA binding by SeqA also occurs efficiently on a small hemimethylated oriC fragment containing both R1 and M DnaA boxes, but not the 13-mer region. SeqA binds strongly the long region from the AT-rich region to the M DnaA box of the hemimethylated oriC DNA and releases DnaA molecules from the long region. [source] High-Performance Solution-Processable Poly(p -phenylene vinylene)s for Air-Stable Organic Field-Effect TransistorsADVANCED FUNCTIONAL MATERIALS, Issue 5 2005Abstract The influence of the substitution pattern (unsymmetrical or symmetrical), the nature of the side chain (linear or branched), and the processing of several solution processable alkoxy-substituted poly(p -phenylene vinylene)s (PPVs) on the charge-carrier mobility in organic field-effect transistors (OFETs) is investigated. We have found the highest mobilities in a class of symmetrically substituted PPVs with linear alkyl chains (e.g., R1, R2,=,n -C11H23, R3,=,n -C18H37). We have shown that the mobility of these PPVs can be improved significantly up to values of 10,2,cm2,V,1,s,1 by annealing at 110,°C. In addition, these devices display an excellent stability in air and dark conditions. No change in the electrical performance is observed, even after storage for thirty days in humid air. [source] Reaction of tellurium tetraiodide with 2,3-dihydro-1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene,HETEROATOM CHEMISTRY, Issue 5 2005Norbert Kuhn 2,3-Dihydro-1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene 1 (Carb, R1 = iPr, R2 = Me) reacts with TeI4 to give the carbene adduct CarbTeI2 (3). The crystal structure of 3 consists of T-shaped monomeric fragments linked by weak Te. I interactions to form infinite helical chains. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:316,319, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20090 [source] Planarity of acetamides, thioacetamides, and selenoacetamides: Crystal structure of N,N -dimethylselenoacetamideHETEROATOM CHEMISTRY, Issue 4 2002Shuqiang Niu The planarity of acetamides 1a,3a, thioacetamides 4a,6a, and selenoacetamides 7a,9a, R1R2NC(=E)CH3 where E = O, S, Se, and R1, R2 = H or CH3, was investigated using theoretical calculations at the density functional theory (DFT) level. The calculations showed that the methyl substitution on nitrogen and the change from the amide moiety (NCO) to NCS or NCSe group increased the double bond character of the NC bond. In other words, the planarity of these compounds (1a,9a) increases in the order NH2 < NHCH3 < N(CH3)2 and O < S < Se. The calculations of bending energy suggest that the planar geometry represents the lowest energy conformation for all compounds investigated in this work. N,N-Dimethyl-selenoacetamide (9a), (CH3)2NC(Se) CH3, has the largest bending energy of 10.37 kcal/mol, which suggests that it possesses the greatest planarity among the compounds 1a,9a. However, the solid phase molecular structure of 9a was found to be slightly nonplanar by X-ray crystallography. The slight nonplanarity observed experimentally is very likely the consequence of intermolecular interactions arising within the crystal packing. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:380,386, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10056 [source] Resection margins and R1 rates in pancreatic cancer , are we there yet?HISTOPATHOLOGY, Issue 7 2008C S Verbeke The prognosis of pancreatic cancer is poor, even for those patients who undergo surgical resection. The rate of local recurrence is high, despite the fact that in most series complete (,R0') resection is reported to be achieved in the majority of patients. The discrepancy between pathological assessment and clinical outcome indicates that microscopic margin involvement (R1) is frequently underreported, and potential causes for this are discussed in this review. Special emphasis is given to the variation that exists between currently used dissection techniques and their impact on the assessment of the resection margins in pancreatoduodenectomy specimens. [source] Redefining resection margin status in pancreatic cancerHPB, Issue 4 2009Caroline S. Verbeke Abstract Curative resection is crucial to survival in pancreatic cancer; however, despite optimization and standardization of surgical procedures, this is not always achieved. This review highlights that the rates of microscopic margin involvement (R1) vary markedly between studies and, although resection margin status is believed to be a key prognostic factor, the rates of margin involvement and local tumour recurrence or overall survival of pancreatic cancer patients are often incongruent. Recent studies indicate that the discrepancy between margin status and clinical outcome is caused by frequent underreporting of microscopic margin involvement. Lack of standardization of pathological examination, confusing nomenclature and controversy regarding the definition of microscopic margin involvement have resulted in the wide variation of reported R1 rates that precludes meaningful comparison of data and clinicopathological correlation. [source] Maternal representations during pregnancy and early motherhoodINFANT MENTAL HEALTH JOURNAL, Issue 1 2004Ebru Taskin Ilicali The aim of the present study was to study the maternal representations of pregnant women and mothers in their early postpartum period, by beginning the process of validating the maternal representations questionnaire L'entretien R1 and by developing a means to assess the content-free aspects of the representations. Participants were 23 primiparous (first-time mothers) pregnant women in their fourth to seventh month of pregnancy and 22 primiparous mothers in their early (zero to six months) postpartum period. It was found that the four subscales of L'entretien (self-as-mother, self-as-person, own-mother, and partner) produced meaningful results for Turkish subjects. The results were compatible with the idea of integrated representations of self-as-person and self-as-mother even in the second trimester of their pregnancy and also showed that they could differentiate themselves from their mothers as early as that period. The results revealed no significant differences in the content and content-free dimensions of the representations of pregnant women and mothers. ©2004 Michigan Association for Infant Mental Health. [source] An optimized kinetics model for OH chemiluminescence at high temperatures and atmospheric pressuresINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 12 2006Joel M. Hall Chemiluminescence from the OH(A , X) transition near 307 nm is a commonly used diagnostic in combustion applications such as flame chemistry, shock-tube experiments, and reacting-flow visualization. Although absolute measurements of OH(X) concentrations are well defined, there is no elementary relation between emission from the electronically excited state (OH*) and its absolute concentration. Thus, to enable quantitative emission measurements, a kinetics model has been assembled and optimized to predict OH* formation and quenching at combustion conditions. Shock-tube experiments were conducted in mixtures of H2/O2/Ar, CH4/O2/Ar, and CH4/H2/O2/Ar with high levels of argon dilution (>98%). Elementary reactions to model OH*, along with initial estimates of their rate coefficients, were taken from the literature. The important formation steps follow: (R0) (R1) Sensitivity analyses were performed to identify experimental conditions under which the shape of the measured OH* profiles and the magnitude of the OH* emission would be sensitive to the formation reactions. A fitting routine was developed to express the formation rate parameters as a function of a single rate, k1 at the reference temperature (1490 K). With all rates so expressed, H2/CH4 mixtures were designed to uniquely determine the value of k1 at the reference temperature, from which the remaining rate parameters were calculated. Quenching rates were fixed at their literature values. The new model predicts the experimental data over the range of conditions studied and can be used to calibrate the emission diagnostic for other applications, such as measurements in real combustion environments, containing higher order hydrocarbon fuels and lower levels of dilution in air. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 714,724, 2006 [source] A shock tube study of the reaction NH2 + CH4 , NH3 + CH3 and comparison with transition state theoryINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 7 2003Soonho Song The rate coefficient for NH2 + CH4 , NH3 + CH3 (R1) has been measured in a shock tube in the temperature range 1591,2084 K using FM spectroscopy to monitor NH2 radicals. The measurements are combined with a calculation of the potential energy surface and canonical transition state theory with WKB tunneling to obtain an expression for k1 = 1.47 × 103T3.01e,5001/T(K) cm3 mol,1 s,1 that describes available data in the temperature range 300 ,2100 K. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 304,309, 2003 [source] OH concentration time histories in n -alkane oxidationINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 12 2001D. F. Davidson OH radical concentration time histories were measured behind reflected shocks in the oxidation of four n -alkanes: propane, n -butane, n -heptane, and n -decane. Initial reflected shock conditions of these measurements were 1357,1784 K, 2.02,3.80 atm, with fuel concentrations of 300,2000 ppm, and equivalence ratios from 0.8 to 1.2. OH concentrations were measured using narrow-linewidth ring-dye laser absorption of the R1(5) line of the A,X (0,0) transition at 306.5 nm. These concentration time-history measurements were compared to the modeled predictions of eight large n -alkane oxidation mechanisms currently available in the literature and the kinetic implications of these measurements are discussed. These data, in conjunction with recent measurements of n -alkane ignition times and ethylene yields in n -alkane pyrolysis experiments, also performed in this laboratory, provide a unique database of species concentration time histories for n -alkane mechanism validation. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 775,783, 2001 [source] Prophylactic control of post-operative nausea and vomiting using ondansetron and ramosetron after cardiac surgeryACTA ANAESTHESIOLOGICA SCANDINAVICA, Issue 8 2010D. K. CHOI Background: The aim of this study was to evaluate the efficacy of ondansetron and ramosetron in the reduction of post-operative nausea and vomiting (PONV) associated with patient-controlled analgesia (PCA) after cardiac surgery. Methods: A total of 320 patients scheduled for elective cardiac surgery were enrolled. Patients were randomly assigned to one of four treatment regimens (n=80 in each group): no prophylactic antiemetics (group P); intravenous (i.v.) ondansetron 4 mg at the end of surgery and 12 mg added to PCA (group O); i.v. ramosetron 0.3 mg at the end of surgery and no antiemetics added to PCA (group R1); and i.v. ramosetron 0.3 mg at the end of surgery and 0.6 mg added to PCA (group R2). Results: The incidence of PONV during the 48-h post-operative period was lower in groups O (46%), R1 (54%), and R2 (35%) compared with group P (71%, P<0.001). The incidence and severity of nausea were lower in groups O, R1, and R2 than in group P during the 24-h post-operative period, whereas the incidence and severity of nausea during 24,48 h after surgery were lower in groups O and R2, but not in group R1, than in group P. Compared with group P (53%), the frequency of rescue antiemetic usage was significantly lower in groups O (34%) and R2 (29%), but not in group R1 (43%). Conclusion: The addition of either ondansetron or ramosetron to PCA can reduce the incidence of PONV during 48 h after cardiac surgery. [source] | ||||||||||||||||||||||||||||||||||||||||||||||