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排序方式: 共有501条查询结果,搜索用时 15 毫秒
81.
Bitton R Berglin M Elwing H Colin C Delage L Potin P Bianco-Peled H 《Macromolecular bioscience》2007,7(12):1280-1289
Adhesive materials extracted from the brown algae Fucus Serratus were studied. These adhesives are composed of cross-linked alginate and polyphenols oxidized in the presence of KI or KBr. All formulations were capable of adhering to a variety of surfaces, however the adhesion properties were influenced by the halide used. SAXS and TEM experiments revealed that oxidized polyphenols self-assemble into chain-like objects, irrespective of the oxidation conditions. Yet, slight differences in the aggregate size were detected. QCM-D results showed that the kinetics of the oxidation was faster with iodide than with bromide. Moreover, oxidation with iodide generates stiffer networks, suggesting that the interaction between the alginate and the polyphenol could be the cause of the reduced adhesion. 相似文献
82.
Foltz C Stecker B Marconi G Bellemin-Laponnaz S Wadepohl H Gade LH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(35):9912-9923
The underlying conceptual differences in exploiting two- and threefold rotational symmetry in the design of chiral ligands for asymmetric catalysis have been addressed in a comparative study of the catalytic performance of bisoxazoline (BOX) and tris(oxazolinyl)ethanes (trisox) containing copper(II) Lewis acid catalysts. The differences become apparent in constructing new catalysts by systematically "deforming" the stereodirecting ligand by inverting chiral centres or replacing chiral by achiral oxazolines. The catalytic alpha-amination of ethyl 2-methylacetoacetate with dibenzyl azodicaboxylate, which occurs with high enantioselectivity for both Ph(2)-BOX and Ph(3)-trisox copper catalysts, has been employed as the test reaction. In the trisox-copper complex [Cu(II)(iPr(3)-trisox)(kappa(2)-O,O'-MeCOCHCOOEt)](+)[BF(4)](-) (1), which was characterised by X-ray diffraction, two of the oxazoline groups are coordinated to the central copper atom, whilst the third oxazoline unit is dangling with the N-donor pointing away from the metal centre. A similar arrangement is found for the stereochemically "mixed" C(1)-trisox complex [Cu(II){(Ph(3)-trisox(R,S,S)}(kappa(2)-O,O'-MeCOCHCOOEt)(H(2)O)](+)[ClO(4)](-) (2), in which the phenyl substituents adopt a first coordination sphere meso arrangement. The almost identical selectivity of the Ph(3)-trisox(R,R,R)- and Ph(2)-BOX(R,R)-derived catalysts is as expected from the proposed model of the active catalyst based on a partially decoordinated podand. The behaviour of the "desymmetrised" trisox-Cu catalysts may be rationalised in terms of a general steady-state kinetic model for the three possible active bisoxazoline-copper species, which are expected to be in rapid exchange with each other in solution. This applies to both the trisox derivatives with stereochemically inverted and achiral oxazoline rings. The study underscores previous observations of superior performance of the catalysts bearing C(3)-chiral stereodirecting ligands as compared to systems of lower symmetry. 相似文献
83.
Baffert C Feldberg SW Bond AM Long DL Cronin L 《Dalton transactions (Cambridge, England : 2003)》2007,(40):4599-4607
The electrochemistry of the Dawson-like sulfite polyoxometalate anion alpha-[Mo18O54(SO3)2]6-, derived from the TEAH6{alpha-[Mo18O54(SO3)2]} salt (TEAH+ is the triethanolammonium cation; pKa=7.8), has been investigated in aqueous media using cyclic and rotated disk voltammetry at glassy carbon electrodes and bulk electrolysis, with a focus on the pH-dependence for oxidation to alpha-[Mo18O54(SO3)2]4-. In buffered media at pH>or=4, the cyclic voltammetric response for alpha-[Mo18O54(SO3)2]6- reveals two partially resolved one-electron oxidation processes corresponding to the sequential generation of alpha-[Mo18O54(SO3)2]5- and alpha-[Mo18O54(SO3)2]4-. At lower pH, using electrolytes containing sulfuric acid, the two waves coalesce but the individual apparent E0' reversible formal potential values for the two processes can be extracted down to pH 2 by assuming that reversible protonation accompanies fast electron transfer. The results for 2相似文献
84.
Carole T. Ferrand 《Journal of voice》2000,14(1):17-21
This study examined harmonics-to-noise ratios (HNR) in 4 groups of normally speaking children. HNRs were calculated for the vowels /ai/ and /inverted v/, selected from conversational speech samples of 80 children aged 4, 6, 8, and 10 years (10 boys and 10 girls at each age level). HNR values for /inverted v/ were significantly higher than those for /ai/. Significant age differences emerged for /ai/ between ages 4 and 8, and ages 8 and 10. Girls obtained significantly higher HNRs than boys for the /ai/ vowel. Overall, the HNR values for these normally speaking children were lower than those reported for normally speaking adults. These findings suggest that acoustic values for children cannot be validly compared to those for adults, and that the child's gender and age should be taken into account when applying spectral analyses to research and/or clinical situations. 相似文献
85.
86.
Laia Josa-Culler Thomas J. Cogswell Irene Georgiou Morgan Jay-Smith Thomas R. Jackson Carole J. R. Bataille Stephen G. Davies Paresh Vyas Thomas A. Milne Graham M. Wynne Angela J. Russell 《Molecules (Basel, Switzerland)》2021,26(21)
Acute myeloid leukemia (AML) is the most aggressive type of blood cancer, and there is a continued need for new treatments that are well tolerated and improve long-term survival rates in patients. Induction of differentiation has emerged as a promising alternative to conventional cytotoxic chemotherapy, but known agents lack efficacy in genetically distinct patient populations. Previously, we established a phenotypic screen to identify small molecules that could stimulate differentiation in a range of AML cell lines. Utilising this strategy, a 1,5-dihydrobenzo[e][1,4]oxazepin-2(3H)-one hit compound was identified. Herein, we report the hit validation in vitro, structure-activity relationship (SAR) studies and the pharmacokinetic profiles for selected compounds. 相似文献
87.
88.
89.
Guilhem Arrachart Dr. Carole Carcel Dr. Philippe Trens Prof. Jöel J. E. Moreau Prof. Michel Wong Chi Man Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(25):6279-6288
Imprinted materials : Monosilylated derivatives of melamine and cyanuric acid are used in the preparation of hybrid silica. The assembly of the melamine and cyanuric acid moieties through molecular recognition properties is the key factor in building a bridged silsesquioxane and an imprinted hybrid silica (see picture).
90.
Mialane P Duboc C Marrot J Rivière E Dolbecq A Sécheresse F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(7):1950-1959
Two new azido-bridged polyoxometalate compounds were synthesized in acetonitrile/methanol media and their molecular structures have been determined by X-ray crystallography. The [[(gamma-SiW10O36)Mn2(OH)2(N3)(0.5)(H2O)(0.5)]2(mu-1,3-N3)](10-) (1 a) tetranuclear Mn(III) complex, in which an end-to-end N3- ligand acts as a linker between two [(gamma-SiW10O36)Mn2(OH)2]4- units, represents the first manganese-azido polyoxometalate. The magnetic properties have been studied considering the spin Hamiltonian H = -J1(S1S2+S1*S2*)-J2(S1S1*), showing that antiferromagnetic interactions between the paramagnetic centers (g = 1.98) occur both through the di-(mu-OH) bridge (J1 = -25.5 cm(-1)) and the mu-1,3-azido bridge (J2 = -19.6 cm(-1)). The [(gamma-SiW10O36)2Cu4(mu-1,1,1-N3)2(mu-1,1-N3)2]12- (2 a) tetranuclear Cu(II) complex consists of two [gamma-SiW10O36Cu2(N3)2]6- subunits connected through the two mu-1,1,1-azido ligands, the four paramagnetic centers forming a lozenge. The magnetic susceptibility data have been fitted. This reveals ferromagnetic interactions between the four Cu(II) centers, leading to an S=2 ground state (H = -J1(S1S2+S1*S2*)-J2(S2S2*), J1 = +294.5 cm(-1), J2 = +1.6 cm(-1), g = 2.085). The ferromagnetic coupling between the Cu(II) centers in each subunit is the strongest ever observed either in a polyoxometalate compound or in a diazido-bridged Cu(II) complex. Considering complex 2 a and the previously reported basal-basal di-(mu-1,1-N3)-bridged Cu(II) complexes in which the metallic centers are not connected by other magnetically coupling ligands, the linear correlation J1 = 2639.5-24.95*theta(av) between the theta(av) bridging angle and the J1 coupling parameter has been proposed. The electronic structure of complex 2 a has also been investigated by using multifrequency high-field electron paramagnetic resonance (HF-EPR) spectroscopy between 95 and 285 GHz. The spin Hamiltonian parameters of the S = 2 ground state (D = -0.135(2) cm(-1), E = -0.003(2) cm(-1), g(x) = 2.290(5), g(y) = 2.135(10), g(z) = 2.158(5)) as well as of the first excited spin state S = 1 (D = -0.960(4) cm(-1), E = -0.080(5) cm(-1), g(x) = 2.042(5), g(y) = 2.335(5), g(z) = 2.095(5)) have been determined, since the energy gap between these two spin states is very small (1.6 cm(-1)). 相似文献