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11.
The kinetics and the equilibrium constant of the chlorine transfer reaction between monochloramine NH2Cl and the amines: C2H5NH2, (CH3)2CHNH2, (CH3)2NH, and (C2H5)2NH are investigated by spectrophotometry in aqueous medium at 25°C, in the pH range from 8 to 13 and for an ionic strength equal to 1.03 ± 0.05M. For a concentration of total ammonia equal to 1M, the observed rate constant is pH independent below 8 and above 12.8 and reaches a maximum located between the pKas of NH4+ and RR'NH2+. From these results and those obtained earlier for NH2Cl and CH3NH2, the reaction is shown to involve an interaction between neutral molecules NH2Cl and RR'NH, subject to general acid catalysis. The ability of an interaction corresponding to a specific catalysis and involving NH3Cl+ and RR'NH rather than NH2Cl and RR'NH2+ is also discussed. The activation parameters are given for each reaction. 相似文献
12.
13.
Namita Singh Sana Ahmed Aliyah Fakim Somayah Qutub Othman Alahmed Omar El Tall Osama Shekhah Mohamed Eddaoudi Niveen M. Khashab 《Chemical science》2020,11(41):11280
Assembling well-defined MOF superstructures remains challenging as it requires easily removable hard templates or readily available immiscible solutions for an emulsion-based soft-template approach. In this work, a single-step emulsion-free soft templating approach is reported to spontaneously prepare hollow ZIF-8 and ZIF-67 colloidosomes with no further purification. These superstructures can load different enzymes regardless of the size and charge with a high encapsulation efficiency of 99%. We envisage that this work will expand the repertoires of MOF superstructures by the judicious selection of precursors and the reaction medium.An emulsion-free approach for the preparation of hollow ZIF-8 superstructures in a single step is established based on metal sulfate hydrates in methanol. 相似文献
14.
Top S Vessières A Leclercq G Quivy J Tang J Vaissermann J Huché M Jaouen G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(21):5223-5236
A series of ferrocene derivatives based upon the structure of the antiestrogenic drug tamoxifen or of its active metabolite hydroxytamoxifen has been prepared and named by analogy ferrocifens and hydroxyferrocifens. This series includes 1-[4-(O(CH(2))(n)NMe(2))phenyl]-1-phenyl-2-ferrocenyl-but-1-ene and 1-[4-(-O(CH(2))(n)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenyl-but-1-ene, with n=2, 3, 5 and 8, and 1-[4-(-O(CH(2))(2)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenylethene. Most of these molecules have been synthesised by McMurry cross-coupling of the appropriate ketones, except for the ethene complexes, which were prepared by a four-step reaction sequence starting from the ferrocenylacetic acid. All these compounds were obtained as mixtures of Z and E isomers. The isomers were separated in the cases of the ferrocenyl derivatives of tamoxifen and hydroxytamoxifen (n=2). No isomerisation of the Z and E isomers occurred in DMSO after one day, while a 50:50 mixture of the isomers was obtained within one hour in chloroform. The X-ray structure of (E)-1-[4-(-O(CH(2))(2)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenyl-but-1-ene has been determined. The relative binding affinity (RBA) values of the hydroxyferrocifens for the estrogen receptor alpha (ERalpha) was good to moderate, with values decreasing progressively with the length of the basic chain. The RBA values found for the estrogen receptor beta (ERbeta) are equal to or slightly less than those found for the alpha form. The lipophilicity of the hydroxyferrocifens are superior to the values found for estradiol and increase with lengthening of the chain. The antiproliferative effects of the four hydroxyferrocifens with n=2, 3, 5 and 8 were studied on four breast cancer cell lines (MCF7, MDA-MB231, RTx6 and TD5) possessing different levels of ERalpha. On MCF7 cells containing high levels of ERalpha, hydroxyferrocifens behave as antiestrogens. At a molarity of 1 microM the effect is close to that of hydroxytamoxifen (used for reference) when n=2 or 5, more marked when n=3, and weaker when n=8. Ferrocene alone has no effect. For the MDA-MB231 cells, classed as a hormone-independent breast cancer cell line, on the other hand, the hydroxyferrocifens show remarkable antiproliferative behaviour while the hydroxytamoxifen is completely inactive. Hydroxyferrocifens therefore show the unique property of being active both on hormone-dependent and on hormone-independent breast cancer cell lines. The molecular modelling study provides some clues for understanding of the antagonist effect of these molecules, while an additional cytotoxic effect due to the vectorised ferrocenyl unit is revealed in some occasions. 相似文献
15.
A pulsed excimer-pumped dye laser was used to excite atomic flourescence in graphite tube electrothermal atomizer. A 60-Hz ac magnitude field was applied around the atomizer and parallel to the excitation beam, for Zeeman background correction. The correction system was found to degrade the detection limits for silver, cobalt, indium, manganese, lead, and thallium by a factor of between 1 and 10. An increase in magnetic field strength, or a decrease in laser linewidth, should improve the detection limits, but was not possible here. For copper, the application of Zeeman background correction was unsuccessfull because the instrumentation was unable to resolve the sigma components from the laser emission profile sufficiently during the background correction measurement. For elements that exhibit sufficient Zeeman splitting, the linear dynamic range was the same with or without background correction Zeeman background correction was used to correct for scatter, in the resonance flourescence determination of manganese in a zinc chloride matrix and in mouse brain tissue. 相似文献
16.
Designs, Codes and Cryptography - The problem of classifying linear systems of conics in projective planes dates back at least to Jordan, who classified pencils (one-dimensional systems) of conics... 相似文献
17.
Harel Michel Ngatchou-Wandji Joseph Andriamampionona Livasoa Harison Victor 《Statistical Inference for Stochastic Processes》2022,25(3):485-504
Statistical Inference for Stochastic Processes - This paper deals with the weak convergence of nonparametric estimators of the multidimensional and multidimensional-multivariate renewal functions... 相似文献
18.
Bertrand Pierre Broniatowski Michel Marcotorchino Jean-François 《Advances in Data Analysis and Classification》2022,16(4):1069-1093
Advances in Data Analysis and Classification - This paper aims at comparing two coupling approaches as basic layers for building clustering criteria, suited for modularizing and clustering very... 相似文献
19.
Michel Cibils Yvan Cuche Gerhard Müller 《Zeitschrift für Physik B Condensed Matter》1995,97(4):565-572
The peculiar spectral properties of the spinboson model make it suitable for an investigation of quantum nonintegrability effects and level statistics from a new perspective. For fixed spin quantum numbers, its energy spectrum consists of 2s+1 sequences of levels with no upper bound. These sequences are identified and labelled consecutively by means of a quantum invariant calculated from the time average of a non-stationary operator. For integrable cases, level repulsion (on the energy axis) is limited to states within each sequence. From the observed spectral properties, we infer a series ofs-dependent level-spacing distributions. They converge towards a Poisson distribution fors. For nonintegrable cases, level repulsion becomes a universal phenomenon, but the amount of repulsion between two states decreases with increasing separation (in label) of the two sequences to which they belong. For smalls, the quantum nonintegrability effects are compelling but not at all chaotic. Nevertheless, they contain all the ingredients necessary to produce the symptoms commonly described as indicators of quantum chaos. In this model, we can observe quantum chaos in the making under very controllable conditions. 相似文献
20.
Michel Weber 《Journal of Theoretical Probability》1996,9(1):105-112
Let (Y,,,T) be an ergodic dynamical system. LetA be an nonempty subset ofL
2() such that
, whereA=sup{||sȒt||2
,s, tA} andN(A, u) is the smallest number ofL
2()-open balls of radiusu, centered inA, enough to coverA. Let
. We prove as a consequence of a more general result, thatC(A) is aGB subset ofL
2(). 相似文献