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71.
Peptide nucleic acid (PNA) is a synthetic analogue of DNA, which has the same nucleobases as DNA but typically has a backbone based on aminoethyl glycine (Aeg). PNA forms duplexes by Watson Crick hybridization. The Aeg-based PNA duplexes adopt a chiral helical structure but do not have a preferred handedness because they do not contain a chiral center. An L-lysine situated at the C-end of one or both strands of a PNA duplex causes the duplex to preferably adopt a left-handed structure. We have introduced into the PNA duplexes both a C-terminal L-lysine and one or two PNA monomers that have a γ-(S)-methyl-aminoethyl glycine backbone, which is known to induce a preference for a right-handed structure. Indeed, we found that in these duplexes the γ-methyl monomer exerts the dominant chiral induction effect causing the duplexes to adopt a right-handed structure. The chiral PNA monomer had a 2,2':6',2'-terpyridine (Tpy) ligand instead of a nucleobase and PNA duplexes that contained one or two Tpys formed [Cu(Tpy)(2)](2+) complexes in the presence of Cu(2+). The CD spectroscopy studies showed that these metal-coordinated duplexes were right-handed due to the chiral induction effect exerted by the S-Tpy PNA monomer(s) except for the cases when the [Cu(Tpy)(2)](2+) complex was formed with Tpy ligands from two different PNA duplexes. In the latter case, the metal complex bridged the two PNA duplexes and the duplexes were left-handed. The results of this study show that the preferred handedness of a ligand-modified PNA can be switched as a consequence of metal coordination to the ligand. This finding could be used as a tool in the design of functional nucleic-acid based nanostructures. 相似文献
72.
Eremchev IY Vainer YG Naumov AV Kador L 《Physical chemistry chemical physics : PCCP》2011,13(5):1843-1848
Numerous experiments have shown that the low-temperature dynamics of a wide variety of disordered solids is qualitatively universal. However, most of these results were obtained with ensemble-averaging techniques which hide the local parameters of the dynamic processes. We used single-molecule (SM) spectroscopy for direct observation of the dynamic processes in disordered solids with different internal structure and chemical composition. The surprising result is that the dynamics of low-molecular-weight glasses and short-chain polymers does not follow, on a microscopic level, the current concept of low-temperature glass dynamics. An extra contribution to the dynamics was detected causing irreproducible jumps and drifts of the SM spectra on timescales between milliseconds and minutes. In most matrices consisting of small molecules and oligomers, the spectral dynamics was so fast that SM spectra could hardly or not at all be recorded and only irregular fluorescence flares were observed. These results provide new mechanistic insight into the behavior of glasses in general: At low temperatures, the local dynamics of disordered solids is not universal but depends on the structure and chemical composition of the material. 相似文献
73.
A novel asymptotic approach to the theory of non-homogeneous anisotropic plates is suggested. For the problem of linear static deformations we consider solutions, which are slowly varying in the plane of the plate in comparison to the thickness direction. A small parameter is introduced in the general equations of the theory of elasticity. According to the procedure of asymptotic splitting, the principal terms of the series expansion of the solution are determined from the conditions of solvability for the minor terms. Three-dimensional conditions of compatibility make the analysis more efficient and straightforward. We obtain the system of equations of classical Kirchhoff's plate theory, including the balance equations, compatibility conditions, elastic relations and kinematic relations between the displacements and strain measures. Subsequent analysis of the edge layer near the contour of the plate is required in order to satisfy the remaining boundary conditions of the three-dimensional problem. Matching of the asymptotic expansions of the solution in the edge layer and inside the domain provides four classical plate boundary conditions. Additional effects, like electromechanical coupling for piezoelectric plates, can easily be incorporated into the model due to the modular structure of the analysis. The results of the paper constitute a sound basis to the equations of the theory of classical plates with piezoelectric effects, and provide a trustworthy algorithm for computation of the stressed state in the three-dimensional problem. Numerical and analytical studies of a sample electromechanical problem demonstrate the asymptotic nature of the present theory. 相似文献
74.
Yury G. Galyametdinov Larisa V. Malykhina Wolfgang Haase Kris Driesen Koen Binnemans 《Liquid crystals》2002,29(12):1581-1584
Lewis-base adducts of tris( β-diketonato)lanthanide(III) complexes were prepared, where the β-diketone is para -alkoxy-substituted 1,3-diphenyl-1,3-propanedione. These compounds are the first examples of liquid crystalline lanthanide complexes in which the mesomorphism is introduced via a β-diketonate ligand. Depending on the type of the Lewis base, the metallomesogens exhibit a monotropic smectic A or a monotropic highly ordered smectic phase. Intense photoluminescence was observed for the europium(III) complexes at room temperature. 相似文献
75.
Ildar Bikchantaev Yury G. Galyametdinov Olga Kharitonova Igor V. Ovchinnikov Duncan W. Bruce David A. Dunmur Daniel Guillon Benoî t Heinrich 《Liquid crystals》1996,20(4):489-492
Reaction of β-enaminoketones with lanthanide salts leads to mesomorphic complexes displaying an SA mesophase. The mesophase was characterized using X-ray scattering, EPR and magnetic susceptibility. A very high magnetic anisotropy was deduced for a complex containing dysprosium. 相似文献
76.
I. A. Luchko P. A. Parshukov A. G. Smirnov 《Journal of Applied Mechanics and Technical Physics》1974,15(4):507-510
Experimental results are given on the parameters of cylindrical blast waves in water-impregnated sandy loam as a function of the charge depth, the distance from the charge, and the free porosity of the soil.Translated from Zhurnal Prikladnoi Mekhaniki i Tekhnicheskoi Fiziki, No. 4, pp. 88–93, July–August, 1974. 相似文献
77.
Mixed mode stationary phases with ion-pairing reagent (acidic or basic) as integral part of hydrophobic chain offers unique selectivity, and hence, are ideal for multidimensional separations. The retention of hydrophobic components is a function of organic content, whereas that of charged species is a function of organic content, ionogenic modifier and its level in the mobile phase. Hence, by controlling the parameters influencing component retention (stationary phase and mobile phase), the selectivity of chemical components in the two-dimensional plane can be manipulated to improve the separation. A two-dimensional liquid chromatograph has been developed by coupling similar and dissimilar mixed mode stationary phases in the two dimensions. This technique has immense potential in resolving co-eluting components as the retention mechanism in the two-dimensions are complementary. However, with only part of the primary column eluent sampled into the secondary column, the technique is limited to qualitative analysis. 相似文献
78.
We introduce a recursive construction of regular Handamard matrices with row sum 2h for h=±3n. Whenever q=(2h – 1)2 is a prime power, we construct, for every positive integer m, a symmetric designs with parameters (4h2(qm+1 – 1)/(q – 1), (2h2 – h)qm, (h2 – h)qm). 相似文献
79.
Skazov RS Nekrasov YS Kuklin SA Simenel AA 《European journal of mass spectrometry (Chichester, England)》2006,12(2):137-142
Influence of experimental conditions on electrospray/ionization (ESI) mass spectra of ferrocene derivatives FcCHRAz (Fc = eta5-C5H5-Fe-eta5- C5H4; R = H, Az = benzimidazole; R = Ph, Az = 2-methylimidazole) has been investigated. The spectra of all the compounds revealed [M]+*, product of its fragmentation [FcCHR]+ as well as products of ion/molecular interactions (protonated molecule [MH]+, binuclear ion [(FcCHR)2 Az]+, dimeric ion [M2]+* and its protonated form [M2H]+). Relative abundances of these ions appreciably (more than one order) depend on experimental conditions: analyte concentration, temperature of heated capillary, spray voltage, flow rate of mobile phase and polarity of solvents. Established correlations allow the selection of optimum experimental conditions for registration of ESI mass spectra, as required by the application. If an unknown compound is to be identified, it is necessary to operate by using polar solvents, small concentration, low temperature of heated capillary, high spray voltage and flow rates. There are high-intensity binuclear and protonated dimeric ions in mass spectra under other conditions. It can give rise to wrong interpretation of the structure of investigated compound. At the same time, for study of ion-molecular processes by ESI-MS it is necessary to use concentrated samples in non-polar solvents. In this case the dependence of reaction products yields on temperature and flow rate of mobile phase must be investigated. 相似文献
80.
We describe degenerations of four-dimensional binary Lie algebras, and five- and six-dimensional nilpotent Malcev algebras over ?. In particular, we describe all irreducible components of these varieties. 相似文献