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111.
Immobilized sulfhydryl groups were prepared by partial thiolation of NH2-glass beads. The microenvironment of the immobilized SH groups was varied by different chemical modifications of neighboring
NH2 groups. Introduction of a strong charge in the surroundings of immobilized sulfhydryls results in their dramatic stabilization
against autooxidation. This effect is due to the salting of O2 from the surface microlayer of the thiolated beads. 相似文献
112.
Conditions for the determination of electrophoretic mobilities of bacteria by capillary electrophoresis (CE) were explored. Most precise values are obtained using fused silica capillaries of 1–3 m length (0.25 mm inner diameter), a background buffer with an ionic strength of 0.0015 mol/L and a pH value of 7–10 at a field strength of 120 V/cm. Capillary electrophoretic separation of three different bacteria populations on the basis of their mobility differences could be realized. Electrophoretic band widths of all bacteria populations investigated are relatively large compared to molecule bands. It finds its explanation in the different distribution of surface charge density to cross-sectional area of each single cell of a population. 相似文献
113.
Alexander R. Giaquinto Richard E. Lindstrom James Swarbrick Antonio LoSurdo 《Journal of solution chemistry》1977,6(10):687-701
Solubility and apparent molar volume data are used to demonstrate effects of amide alkylation on amide-water interactions at 25° C. Precise measurements were made of the apparent molar volumes of the amides in binary amide-water mixtures using a dilatometric technique. The results show that the apparent molar volumes of alkyl-substituted amides in water pass through a minimum at an amide concentration which varies inversely with the degree of alkylation. Further studies showed that the solubilities of methyl paraben (methyl-p-hydroxybenzoate) and naphthalene in various amide-water solvent systems increased in characteristic fashion with amide alkylation. 相似文献
114.
Yuri A. Berlin Alexander L. Burin Vitalii V. Goldanskii 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1996,37(4):333-339
The “paradox of optical isomers” revealed by Hund in 1927 is re-examined taking into account the interaction of a chiral molecule with phonons of optically inactive solids below the Debye temperature θD. It has been shown, that in the strong coupling limit, where the dephasing rate is much higher than the energy splitting frequency, the interaction can lead to a complete loss of coherence between mirror-antipodal states of the molecule due to the phonon-induced dephasing. This, in turn, suppresses tunnelling oscillations between them, so that transitions, which are reversible in time for an isolated chiral molecule become irreversible for the same molecule placed in a low-temperature matrix. In order to propose a particular mechanism of such stabilization, contributions of a single- and multi-phonon processes in the dephasing rate have been evaluated. It has been established that only the two-phonon scattering provides the sufficiently strong dephasing in low-temperature solids. Such a two-phonon mechanism is responsible for the stabilization of molecular chiral states as long as the temperature of the medium is lower θD, but exceeds a few Kelvin degrees. These findings are discussed in the context of the evolutionary concept known as “the cold prehistory of life”. 相似文献
115.
Liquid-liquid cloud point diagrams of solutions of nearly monodisperse samples of polystyrene (PS), and binary mixtures of nearly monodisperse PS’s, both in methylcyclohexane (MCH), were determined for several polymer molecular weights (Mw) at 0.1 MPa. The bimodal mixtures (PS[Mw(1),ρ(1)] + PS[Mw(2),ρ(2)], Mw(1)=90×103 g/mol, Mw(2)=13×103 g/mol, 5.78 × 103 g/mol, and 2.2 × 103 g/mol, ρ=1.06) were prepared constraining 〈Mw〉=38.6×103 g/mol, ρ=Mw/Mn is the polydispersity index. In each case the cloud point curves (CPC’s) for the bimodal mixtures are strongly skewed, lying well above CPC for 〈Mw〉 when φ<φCRITICAL, and below CPC for 〈Mw〉 when φ>φCRITICAL; φ is volume fraction polymer in the polymer/solvent mixture. The experimental results are discussed in the context of empirical and mean-field representations. 相似文献
116.
Alexander Kaiser Klaus K. Mayer Andreas Sellmer Wolfgang Wiegrebe 《Monatshefte für Chemie / Chemical Monthly》2003,43(11):343-354
The molecular ion 1 of N-(n-propoxy)benzaldimine I rearranges by an 1,5-H-shift to the δ-distonic ion 2 which subsequently cyclizes to the α-distonic ion 3. Homolytic cleavage of the N–O bond in 3 results in the δ-distonic ion 4 which expels CH2O leading to the β-distonic ion 5. Ion 5 is also formed from the molecular ions of tetrahydrooxazines II and III and from M+• of phenylazetidine IVa. In a subsequent step, ion 5 cyclizes to the N-protonated 3,4-dihydroisoquinolinium ion 6. The syntheses of II–IV and their derivatives are described. 相似文献
117.
Varughese M. Alexander 《Tetrahedron letters》2005,46(40):6957-6959
Bismuth(III) nitrate pentahydrate is found to be an efficient catalyst for the Pechmann condensation reaction of phenols and β-ketoesters under solvent-free conditions. The reaction protocol is simple and is followed by aqueous work-up leading to the formation of the corresponding coumarin derivatives in good yield and high purity. 相似文献
118.
Nanogel nanosecond photonic crystal optical switching 总被引:3,自引:0,他引:3
Reese CE Mikhonin AV Kamenjicki M Tikhonov A Asher SA 《Journal of the American Chemical Society》2004,126(5):1493-1496
We developed a robust nanosecond photonic crystal switching material by using poly(N-isopropylacrylamide) (PNIPAM) nanogel colloidal particles that self-assemble into crystalline colloidal arrays (CCAs). The CCA was polymerized into a loose-knit hydrogel which permits the individual embedded nanogel PNIPAM particles to coherently and synchronously undergo their thermally induced volume phase transitions. A laser T-jump from 30 to 35 degrees C actuates the nanogel particle shrinkage; the resulting increased diffraction decreases light transmission within 900 ns. Additional transmission decreases occur with characteristic times of 19 and 130 ns. Individual NIPAM sphere volume switching occurs in the approximately 100 ns time regime. These nanogel nanosecond phenomena may be useful in the design of fast photonic crystal switches and optical limiting materials. Smaller nanogels will show even faster volume phase transitions. 相似文献
119.
120.
A simple, accurate and reproducible reversed-phase high-performance liquid chromatography (HPLC) method was developed for the separation and characterisation of alkylphenols (APs) and alkylphenol polyethoxylates (APEOs), using a C18 octadecyl silica (ODS) column. APs and each APEO oligomer were separated successfully within a reasonable time without gradient elution. An excellent resolution was obtained, even for mixtures of APs and low EO number APEOs, which are otherwise difficult to separate using conventional normal-phase HPLC methods. This method, combined with solid-phase extraction, was highly applicable for the simultaneous determination of alkylphenols and alkylphenol ethoxylates in real samples. 相似文献