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91.
The new 3-hydroxychromone derivative 2-(6-diethylaminobenzo[b]furan-2-yl)-3-hydroxychromone (FA) displays a dramatic solvent-dependent transformation of fluorescence spectra in the range of low-polarity solvents. The two well-separated emission bands change their relative intensities so that the short-wavelength band being of a very low intensity in hexane becomes dominant in the more polar ethyl acetate and trichloromethane. We suggest the participation in this effect of excited-state intramolecular proton transfer, which is characteristic for other 3-hydroxychromone and 3-hydroxyflavone derivatives, in the range of solvents of much higher polarities. Because of these unique properties, a number of spectroscopic parameters (positions of absorption and two fluorescence maxima, the ratio of their intensities and the fluorescence quantum yield) can be measured in this solvent range with multiparametric analysis of the data. In terms of solvent polarity, the shifts in both emission bands and their intensity ratio demonstrate a good correlation with empirical polarity scales ETN, Py and SPP, while the absorption spectra reveal some deviations for the tested oxygen-containing solvent molecules. A good cross-correlation is observed between fluorescence spectral shifts and the ratio of band intensities. The latter provides the means for a dramatic amplification of solvent response. Thus, a new approach for ultrasensitive scaling and probing the solvent polarity in the low-polararity range can be suggested. It involves very simple ratiometric measurements at two emission bands and can be posed for a variety of applications. We present examples of these applications for distinguishing of polarities between methylated benzene derivatives, for quantitative assay of polar impurities in low-polar solvents and for detection of the changes of solvent polarity as a function of temperature. 相似文献
92.
New 2D graphical representation of DNA sequences 总被引:5,自引:0,他引:5
We consider a 2D graphical representations of DNA sequences, which avoids loss of information associated with crossing and overlapping of the corresponding curve. We outline an approach, which is based on the construction of a three-component vector whose components are the normalized leading eigenvalues of the L/L matrices associated with DNA. The examination of similarities/dissimilarities among the coding sequences of the first exon of beta-globin gene of different species illustrates the utility of the approach. 相似文献
93.
A new dual‐amplification strategy of electrochemical signaling from antigen–antibody interactions was proposed via backfilling gold nanoparticles on (3‐mercaptopropyl) trimethoxysilane sol‐gel (MPTS) functionalized interface. The MPTS was employed not only as a building block for the electrode surface modification but also as a matrix for ligand functionalization with first amplification. The second signal amplification strategy introduced in this study was based on the backfilling immobilization of nanogold particles to the immunosensor surface. Several coupling techniques, such as with nanogold but not MPTS or with MPTS but not nanogold, were investigated for the determination of carcinoembryonic antigen (CEA) as a model, and a very good result was obtained with nanogold and MPTS coupling immunosensor. With the noncompetitive format, the formation of the antigen–antibody complex by a simple one‐step immunoreaction between the immobilized anti‐CEA and CEA in sample solution introduced membrane potential change before and after the antigen–antibody interaction. Under optimal conditions, the proposed immunosensor exhibited a good electrochemical behavior to CEA in a dynamic concentration range of 4.4 to 85.7 ng/mL with a detection limit of 1.2 ng/mL (at 3 δ). Moreover, the precision, reproducibility and stability of the as‐prepared immunosensor were acceptable. Importantly, the proposed methodology would be valuable for diagnosis and monitoring of carcinoma and its metastasis. 相似文献
94.
The aza-Michael reaction of a variety of chalcones with weaker nucleophilic carbamates catalyzed by InCl3 in the presence of TMSCl via the entry of dual activation of both hard nucleophiles (carbamates) and soft electrophiles (enones) to provide the corresponding adducts in good yields. The first example of enantioselective aza-Michael reaction of chalcones with carbamates was also investigated in the presence of the present catalyst system. 相似文献
95.
Shinsaku Fujita 《Journal of mathematical chemistry》2007,42(2):215-263
The concepts of double coset representations and sphericities of double cosets are proposed to characterize stereoisomerism, where double cosets are classified into three types, i.e., homospheric double cosets, enantiospheric double cosets, or hemispheric double cosets. They determine modes of substitutions (i.e., chirality fittingness), where homospheric double cosets permit
achiral ligands only; enantiospheric ones permit achiral ligands or enantiomeric pairs; and hemispheric ones permit achiral
and chiral ligands. The sphericities of double cosets are linked to the sphericities of cycles which are ascribed to right
coset representations. Thus, each cycle is assigned to the corresponding sphericity index (a
d
, c
d
, or b
d
) so as to construct a cycle indices with chirality fittingness (CI-CFs). The resulting CI-CFs are proved to be identical
with CI-CFs introduced in Fujita’s proligand method (S. Fujita, Theor. Chem. Acc. 113 (2005) 73–79 and 80–86). The versatility
of the CI-CFs in combinatorial enumeration of stereoisomers is demonstrated by using methane derivatives as examples, where
the numbers of achiral plus chiral stereoisomers, those of achiral stereoisomers, and those of chiral stereoisomers are calculated
separately by means of respective generating functions. 相似文献
96.
双光束流动注射光度法测定生活用水中氯离子 总被引:12,自引:0,他引:12
将流动注射分析技术应用到双光束分光光度法中,对其理论和实验技术进行了研究,采用自行组装的流动注射系统进行了生活用水中氯离子的测定,获得满意结果。 相似文献
97.
98.
Designing proteins with novel protein/protein binding properties can be achieved by combining the tools that have been developed independently for protein docking and protein design. We describe here the sequence-independent generation of protein dimer orientations by protein docking for use as scaffolds in protein sequence design algorithms. To dock monomers into sequence-independent dimer conformations, we use a reduced representation in which the side chains are approximated by spheres with atomic radii derived from known C2 symmetry-related homodimers. The interfaces of C2-related homodimers are usually more hydrophobic and protein core-like than the interfaces of heterodimers; we parameterize the radii for docking against this feature to capture and recreate the spatial characteristics of a hydrophobic interface. A fast Fourier transform-based geometric recognition algorithm is used for docking the reduced representation protein models. The resulting docking algorithm successfully predicted the wild-type homodimer orientations in 65 out of 121 dimer test cases. The success rate increases to approximately 70% for the subset of molecules with large surface area burial in the interface relative to their chain length. Forty-five of the predictions exhibited less than 1 A C(alpha) RMSD compared to the native X-ray structures. The reduced protein representation therefore appears to be a reasonable approximation and can be used to position protein backbones in plausible orientations for homodimer design. 相似文献
99.
Shinsaku Fujita 《Theoretical chemistry accounts》1990,78(1):45-63
Summary A coset representation (G(/G
i
)), which is defined algebraically by a coset decomposition of a finite groupG by its subgroupG
i
, is shown to be a method for the decomposition of a regular body into its point group orbits. This proof also shows that each member of theG(/G
i
) orbit belongs to theG
i
site-symmetry. In addition, a general equation concerning the multiplicities of such coset representations is derived and shown to involve Brester's equations and thek-value equations of framework groups as special cases. The relationship of the coset representation and the site-symmetry affords a general procedure for obtaining symmetry adapted functions. 相似文献
100.
Christian Borgs Roman Kotecký Salvador Miracle-Solé 《Journal of statistical physics》1991,62(3-4):529-551
Recently, Borgs and Kotecký developed a rigorous theory of finite-size effects near first-order phase transitions. Here we apply this theory to the ferromagneticq-state Potts model, which (forq large andd2) undergoes a first-order phase transition as the inverse temperature is varied. We prove a formula for the internal energy in a periodic cube of side lengthL which describes the rounding of the infinite-volume jumpE in terms of a hyperbolic tangent, and show that the position of the maximum of the specific heat is shifted by
m
(L)=(Inq/E)L
–d
+O(L
–2d
) with respect to the infinite-volume transition point
t
. We also propose an alternative definition of the finite-volume transition temperature
t
(L) which might be useful for numerical calculations because it differs only by exponentially small corrections from
t
. 相似文献