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141.
Angel Clara-Sosa Lydia Prez Mario Snchez Roberto Melgar-Fernndez Eusebio Juaristi Leticia Quintero Cecilia Anaya de Parrodi 《Tetrahedron》2004,60(52):12147-12152
The synthesis of N-benzylsulfinyl derivatives 5a–d from both pairs of enantiomeric hexahydrobenzoxazolidin-2-ones 4a–d is reported. The use of 5a–d as effective chiral sulfinylating reagents in the preparation of enantiopure sulfoxides (e.e.>98%) is also reported. 相似文献
142.
Nandini Savoo Jalal Z. A. Laloo Lydia Rhyman Ponnadurai Ramasami F. Matthias Bickelhaupt Jordi Poater 《Journal of computational chemistry》2020,41(4):317-327
We have computationally studied the bimolecular nucleophilic substitution (SN2) reactions of MnNH2(n−1) + CH3Cl (M+ = Li+, Na+, K+, and MgCl+; n = 0, 1) in the gas phase and in tetrahydrofuran solution at OLYP/6-31++G(d,p) using polarizable continuum model implicit solvation. We wish to explore and understand the effect of the metal counterion M+ and of solvation on the reaction profile and the stereochemical preference, that is, backside (SN2-b) versus frontside attack (SN2-f). The results were compared to the corresponding ion-pair SN2 reactions involving F− and OH− nucleophiles. Our analyses with an extended activation strain model of chemical reactivity uncover and explain various trends in SN2 reactivity along the nucleophiles F−, OH−, and , including solvent and counterion effects. © 2019 Wiley Periodicals, Inc. 相似文献
143.
Rabindra N. Roy Lakshmi N. Roy Bennett J. Tabor Curtis A. Himes Sarah J. Richards Ashley N. Simon Andrew C. Moore Lydia A. Seing Heather D. Craig Kyle T. Robinson 《Journal of solution chemistry》2004,33(10):1199-1211
The values of the second dissociation constant, pK2, and related thermodynamic quantities of 4-(N-morpholino)butanesulfonic acid (MOBS) and N-tris(hydroxymethyl)-4-aminobutanesulfonic acid (TABS) have already been reported over the temperature range 5–55°C including 37{°}C. This paper reports the pH values of twelve equimolal buffer solutions at designated pH (s) with the following compositions: (a) mixtures of MOBS (0.05 mol-kg–1) + NaMOBS (0.05 mol-kg–1); (b) MOBS (0.08 mol-kg–1) + NaMOBS (0.08 mol-kg–1); (c) MOBS (0.08 mol-kg–1) + NaMOBS (0.08 mol-kg–1) + NaCl (0.08 mol-kg–1); (d) TABS (0.05 mol-kg–1) + NaTABS (0.05 mol-kg–1); and (e) TABS (0.08 mol-kg–1) + NaTABS (0.08 mol-kg–1); and (f) TABS (0.08 mol-kg–1) + NaTABS (0.08 mol-kg–1) + NaCl (0.08 mol-kg–1). Two buffer solutions have ionic strengths I= 0.05 mol-kg–1, another two have I=0.08 mol-kg–1, and the remaining two buffer solutions have I= 0.16 mol-kg–1, which is close to that of the clinical fluids (blood serum). These buffers have been recommended as a useful pH standard for the measurements of physiological solutions. Conventional pH values of all six buffer solutions from 5–55°C, as well as those obtained from the liquid junction potential correction at 25 and 37{°}C have been calculated. The flowing-junction calomel cell has been utilized to measure Ej, the liquid junction potential. 相似文献
144.
Rabindra N. Roy Lakshmi N. Roy Ashley N. Simon Andrew C. Moore Lydia A. Seing Sarah J. Richards Heather D. Craig Benjamin A. Childers Bennett J. Tabor Curtis A. Himes Katherine E. Viele 《Journal of solution chemistry》2004,33(4):353-364
N-tris[Hydroxymethyl]-4-aminobutanesulfonic acid (TABS) has been investigated for the determination of the values of the second dissociation constant, pK
2, in water at 12 temperatures in the range 5–55°C, including 37°C. This zwitterionic compound is useful as a secondary pH standard in the range of pH (7–9) for physiological applications. The electromotive force (emf) measurements have been carried out using a hydrogen gas electrode and a silver–silver chloride electrode. The values of pK
2 are fitted as a function of temperature with the following results: pK
2 = 1671.305/T+14.8737–2.04383 ln T, where T is the thermodynamic temperature in Kelvins. The experimental values of pK
2 are 8.834 ± 0.0005 and 8.539 ± 0.0004 at 25 and 37°C, respectively. The related thermodynamic quantities, G°, H°, S°, and C
p
° characterizing the dissociation process have been derived from the pK
2 and its temperature coefficients. 相似文献
145.
Whitehouse CJ Bell SG Tufton HG Kenny RJ Ogilvie LC Wong LL 《Chemical communications (Cambridge, England)》2008,(8):966-968
The evolution of CYP102A1 variants with enhanced activity and altered specificity characteristics. 相似文献
146.
Anbalagan K Lydia IS 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2008,69(3):964-970
The effect of solvent participation on the ligand-to-metal charge transfer (LMCT, L-->Co(III)) reduction of the of Co(III)(en)(2)Br(RC(6)H(4)NH(2))(2+) where R=m-OCH(3), p-F, H, m-CH(3), p-CH(3,)p-OC(2)H(5) and p-OCH(3) were examined in aqueous 2-methyl-2-propanol (Bu(t)OH) solutions. The change in the reduction behavior of Co(III) centre was also examined through cyclic voltammetric studies. The observed reduction in quantum yield due to LMCT excitation can mainly be accounted using linear solvation energy relationship (LSER) comprising model correlation equations. These consist of empirical parameters such as Grunwald-Winstein's solvent ionizing power, Y, Dimroth-Richardt's solvent micro-polarity parameter, E(T)(N), Gutmann's donor number, DN(N), along with Kamlet-Taft's solvatochromic parameters (hydrogen bond acceptor acidity/basicity alpha/beta and solvent dipolarity/polarizability, pi*). The origin of solvent effect is found to be due to microscopic interaction between the solvent donor and the nitrogen-bound hydrogen of the ligand. Cyclic voltammograms show an irreversible reduction of Co(III) in DMF using Glassy Carbon Electrode, GCE, the redox peaks for the aniline complexes appear at -0.20 and 0.525V. Irradiation of the complexes with UV light (lambda=254nm) in binary mixtures produce Co(II)(aq) and the concentration of this species are highly dependent on x(alc) (x(alc)=mole fraction of alcohol). The observed quantum yield (logPhi(Co(II))) is found to be linearly related to mole fraction of organic co-solvent added in the mixture, therefore, logPhi(Co(II))=26.41 x 10(-2) when x(2)=0.0094 and 43.75 x 10(-2) when x(2)=0.076 for a typical complex Co(III)(en)(2)Br(p-OCH(3)C(6)H(4)NH(2))(2+) in aqueous 2-methyl-2-propanol at 300K. Cyclic voltammetry and LSER analyses illustrate the variation of reduction property of Co(III) by the aryl ligand and homogeneous solvation of the excited state of the complex Co(III)(en)(2)Br(RC(6)H(4)NH(2))(2+) in H(2)O/Bu(t)OH mixtures. 相似文献
147.
The directed migration of endothelial cells is an early and critical step in angiogenesis, or new blood vessel formation. In this study, the polarization and chemotaxis of human umbilical vein endothelial cells (HUVEC) in response to quantified gradients of vascular endothelial growth factor (VEGF) were examined. To accomplish this, a microfluidic device was designed and fabricated to generate stable concentration gradients of biomolecules in a cell culture chamber while minimizing the fluid shear stress experienced by the cells. Finite element simulation of the device geometry produced excellent agreement with the observed VEGF concentration distribution, which was found to be stable across multiple hours. This device is expected to have wide applicability in the study of shear-sensitive cells such as HUVEC and non-adherent cell types as well as in the study of migration through three-dimensional matrices. HUVEC were observed to chemotax towards higher VEGF concentrations across the entire range of concentrations studied (18-32 ng mL(-1)) when the concentration gradient was 14 ng mL(-1) mm(-1). In contrast, shallow gradients (2 ng mL(-1) mm(-1)) across the same concentration range were unable to induce HUVEC chemotaxis. Furthermore, while all HUVEC exposed to elevated VEGF levels (both in steep and shallow gradients) displayed an increased number of filopodia, only chemotaxing HUVEC displayed an asymmetric distribution of filopodia, with enhanced numbers of protrusions present along the leading edge. These results suggest a two-part requirement to induce VEGF chemotaxis: the VEGF absolute concentration enhances the total number of filopodia extended while the VEGF gradient steepness induces filopodia localization, cell polarization, and subsequent directed migration. 相似文献
148.
Roy S Bossers LC Meeldijk HJ Kuipers BW Kegel WK 《Langmuir : the ACS journal of surfaces and colloids》2008,24(3):666-669
Polyoxometalates or POMs, a class of inorganic transition metal-oxide based clusters, have gained significant interest owing to their catalytic, magnetic, and material science applications. All such applications require high surface area POM based materials. However, chemically synthesized POMs are still at most in the range of a few nanometers, with their size and morphology being difficult to control. Hence, there is an immediate need to develop design principles that allow easy control of POM morphology and size on mesoscopic (50-500 nm) length scales. Here, we report a design strategy to meet this need. Our method reported here avoids a complex chemical labyrinth by using a prefabricated cationic 1,2-dioleol-3-trimethylammonium-propane (DOTAP) vesicle as a scaffold/structure directing agent and gluing simple anionic heptamolybdates by electrostatic interaction and hydrogen bonds to form large POM spheres. By this method, complexity in the resulting structure can be deliberately induced either via the scaffold or via the oxometalate. The high degree of control in the matter of the size and morphology of the resulting POM superstructures renders this method attractive from a synthetic standpoint. 相似文献
149.
HS-SPME-GC-MS in combination with PCA was employed to discriminate different arabica/robusta blends having different geographical origins. HS-SPME confirmed to be an effective and reproducible sampling technique for routine characterization of coffees. In addition, the chemometric approach permitted to find parameters suitable for the differentiation of the different blends and the determination of the real quality of the products. Finally, the proposed methods have been successfully applied to some commercial coffee blends. 相似文献
150.
Lydia Killer 《Fresenius' Journal of Analytical Chemistry》1960,174(2):148
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