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61.
A novel solid-phase strategy allows the efficient preparation of "traceless" sulfahydantoins. A total of 28 derivatives, with crude purity generally higher than 85%, were prepared by parallel synthesis. Through reductive alkylations, Mitsunobu reactions, and sulfamoylation reactions on oxime resin, the synthetic strategy affords sulfahydantoin derivatives selectively substituted at N(2), N(5) and N(2), N(5) positions, although yields of disubstituted compounds are lower. The mild reaction conditions involved lead to sulfahydantoins without racemization. 相似文献
62.
The rapid parallel synthesis and characterization of diverse chirally defined 1,3-oxazolidines is reported. Three diversity elements were incorporated in a 6 x 4 x 4 block approach to generate a 96-member 1,3-oxazolidine library. The synthetic route involved initial attachment of six nonracemic phenylglycidols, (2S,3S)1A-C and (2R,3R)-2A-C, to 2% cross-linked polystyrene resin via a chlorodiethylsilane linker (PS-DES), followed by regio- and stereoselective oxirane ring opening with four primary amines (3a-d). The key condensation reaction between the resulting polymer-bound beta-amino alcohols and four aldehydes (4a-d) was found to occur optimally in warm benzene (60 degrees C) in the presence of anhydrous magnesium sulfate. Cleavage of the oxazolidines from the resin support was achieved with TBAF to give the individual members (2R,4R,5R)-5Aaa-Cdd and (2S,4S,5S)-6Aaa-Cdd in good to excellent yields (51-99%) based on mass recovery. Purities of all these crude products was generally >85% (as measured by LCMS). 1H, 13C NMR, and 1D difference nOe of the library members confirmed the structural and stereochemical integrity of the substituents around the 1,3-oxazolidine core. The asymmetric induction at C-2 (cis or trans to the C-4 substituent) ratio ranged from 4 to I to 49 to 1 across the library. This report highlights the versatility of the 1,3-oxazolidine heterocycle as a scaffold for concise parallel library construction and opens the way for high-throughput screening of such compounds in the biological sphere. 相似文献
63.
[reaction: see text] A new fluorogenic transformation based on a quinone reduction/lactonization sequence has been developed and evaluated as a tool for probing redox phenomena in a biochemical context. The probe presented herein is an irreversible redox probe and is reduced selectively by biologically relevant quinols such as ubiquinol but is inert to reduced nicotinamides (e.g., NADH). The ensuing cyclization is fast and quantitative and provides a measurable optical response. 相似文献
64.
Vincent Denavit Jacob St-Gelais Thomas Tremblay Prof. Denis Giguère 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(39):9272-9279
There is a growing interest in the preparation of polyfluorinated carbohydrates. A limited number of fluorohexopyranosides have been used in biological investigations because of the synthetic challenge they present. Hence, we report the synthesis of fluorinated homodimer, fluorodisaccharides, C-terminal fluoroglycopeptides, lipoic acid fluoroglycoconjugate and trifluoroallopyranoside derivatives functionalized at C-6. Our strategy uses levoglucosan as inexpensive starting material and facilitates an approach to complex carbohydrate analogues with multiple C−F bonds. The challenge of our synthetic route centered around an efficient preparation of crucial 1,6-anhydro-2,4-dideoxy-difluoroglucopyranose and focused on achieving a difficult glycosylation of the trifluoroallopyranose donor. The results clearly highlight challenges related to the preparation of polyhalogenated complex organic molecules and pave the way to access novel medically relevant tools. 相似文献
65.
Yi Zhao Luc Tremblay Yue Zhao 《Journal of polymer science. Part A, Polymer chemistry》2010,48(18):4055-4066
We report the synthesis and investigation of a new type of photoresponsive block copolymers (BCPs). They were designed to comprise two water‐soluble polymers containing two different photoisomerizable moieties (either azobenzene and spiropyran or two different azobenzenes), with the two constituting blocks that, when separated, exhibit a lower critical solution temperature (LCST) in water and can shift their LCST in opposite directions upon photoisomerization (decrease of LCST for one polymer and increase for the other). A variety of such doubly photoresponsive BCPs were synthesized using either azobenzene‐ or spiropyran‐containing poly(N,N‐dimethylacrylamide) (PDMA), poly(N‐isopropylacrylamide) (PNIPAM) and poly[methoxydi(ethylene glycol) methacrylate] (PDEGMMA). Their thermal phase transition behaviors in aqueous solution before and after simultaneous photoreactions on the two blocks were investigated in comparison with their constituting blocks, by means of solution transmittance (turbidity) and variable‐temperature 1H NMR measurements. The results show that BCPs displayed a single LCST whose shift upon two photoisomerizations appeared to be determined by the competing and opposing photoinduced effects on the two blocks. Moreover, optically controlling the relative photoisomerization degrees of trans azobenzene‐to‐cis azobenzene and spiropyran‐to‐merocyanine could be used to tune the LCST of BCP solution. This study demonstrates the potential of exploring a more complex photoreaction scheme to optically control the solution properties of water‐soluble thermosensitive BCPs. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4055–4066, 2010 相似文献
66.
A selection of kernel functions is given to be used in a new integral constitutive equation proposed by Piau whereby the deviatoric stress is calculated from the integral of the history of the past intrinsic rate of rotation and rate of deformation tensors through a representation theorem. Piau has demonstrated the objectivity of a frame moving with a given particle whose axis are directed along the eigenvectors of the rate of deformation tensor. The use of such a framework provides a new approach in the attempt to reduce the computational difficulties associated with conventional constitutive equations written in co-deformational or co-rotational reference frames.The shear and primary normal-stress material functions and the extensional (elongational) stress growth function are defined for the proposed integral constitutive equation. These material functions are used to calculate the kernel functions using steady state, stress relaxation and stress growth data of Attané in simple shear flow for monodisperse polystyrene solutions. The shear and extensional stress growth data of Meissner for a polyethylene melt are also used to show the flexibility of the rheological model.The material functions are first written in terms of five monotonically decreasing functions of the time lag between the past and the present time. Then kernel functions are chosen such that when substituted in the new integral constitutive equation they yield the functions used to describe the data. A further condition imposed on the normalized kernel functions is that they be decreasing functions of time lag. 相似文献
67.
Crystal M. Schneck Adam J. Poncheri John T. Jennings Deanna L. Snyder Jill L. Worlinsky Swarna Basu 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2010,75(2):624-628
The interaction between 9-fluorenone, various indoles and solvents has been studied using steady-state fluorescence spectroscopy and quantum chemical calculations. It was determined that polar protic solvents such as methanol and ethanol significantly quenched the fluorescence of 9-fluorenone but various indoles reversed the solvent quenching. The effect of various solvents on the 9-fluorenone carbonyl vibration was investigated using infrared spectroscopy. Ab initio calculations using Gaussian03 were also carried out in order to determine the minimum energy conformations of these systems along with binding energies. 相似文献
68.
Donohoue DL Bauer D Cossairt B Hynes AJ 《The journal of physical chemistry. A》2006,110(21):6623-6632
A pulsed laser photolysis-pulsed laser induced fluorescence technique has been employed to study the recombination of mercury and bromine atoms, Hg + Br + M --> HgBr + M (1) and the self-reaction of bromine atoms, Br + Br + M --> Br2 + M (2). Rate coefficients were determined as a function of pressure (200-600 Torr) and temperature (243-293 K) in nitrogen buffer gas and as a function of pressure (200-600 Torr) in helium buffer gas at room temperature. For reaction 1, kinetic measurements were performed under conditions in which bromine atoms were the reactant in excess concentration while simultaneously monitoring the concentration of both mercury and bromine. A temperature dependent expression of (1.46 +/- 0.34) x 10(-32) x (T/298)(-(1.86+/-1.49)) cm6 molecule(-2) s(-1) was determined for the third-order recombination rate coefficient in nitrogen buffer gas. The effective second-order rate coefficient for reaction 1 under atmospheric conditions is a factor of 9 smaller than previously determined in a recently published relative rate study. For reaction 2 we obtain a temperature dependent expression of (4.31 +/- 0.21) x 10(-33) x (T/298)(-(2.77+/-0.30)) cm6 molecule(-2) s(-1) for the third-order recombination rate coefficient in nitrogen buffer gas. The rate coefficients are reported with a 2sigma error of precision only; however, due to the uncertainty in the determination of absolute bromine atom concentrations and other unidentified systematic errors we conservatively estimate an uncertainty of +/-50% in the rate coefficients. For both reactions the observed pressure, temperature and buffer gas dependencies are consistent with the expected behavior for three-body recombination. 相似文献
69.
A modular synthetic method for the differential incorporation of two lanthanide ions into a single molecular scaffold is reported; the mixed bimetallic Tb/Eu complex displays an interesting solvent polarity-dependent ratiometric luminescence. 相似文献
70.
Using the bicomplex numbers
which is a commutative ring with zero divisors defined by
where i12 = − 1, i22 = − 1, j2 = 1 and i1i2 = j = i2i1, we construct hyperbolic and bicomplex Hilbert spaces. Linear functionals and dual spaces are considered on these spaces
and properties of linear operators are obtained; in particular it is established that the eigenvalues of a bicomplex self-adjoint
operator are in the set of hyperbolic numbers. 相似文献