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81.
The synthesis of hydroxyethyl celluloses with regioselective functionalization in position 2 and 3 starting from triphenylmethyl (trityl) cellulose is described. The effects of reaction conditions upon both the degree of substitution and the distribution of the hydroxyethyl moieties were investigated in detail. The interest was not only focused on regioselective functionalization within the anhydroglucose unit but also on the formation of oxyethylene side chains. To avoid the formation of oxyethylene side chains, 2-(2-bromoethoxy)tetrahydropyran was used as etherifying agent in comparison with 2-bromoethanol. By acidic hydrolysis, both protecting groups – trityl at 6 position and tetrahydropyran at the hydroxyethyl substituent – can be simultaneously cleaved off. The hydroxyethyl celluloses were characterized by one- and two-dimensional NMR spectroscopy in order to determine the substitution pattern.  相似文献   
82.
The interactions of ionic liquids (IL) with solvents usually used in liquid-state nuclear magnetic resonance (NMR) spectroscopy are studied. The 1H- and 13C-NMR chemical shift values of 1-n-butyl-3-methyl (BM)- and 1-ethyl-3-methyl (EM)-substituted imidazolium (IM) -chlorides (Cl) and -acetates (Ac) are determined before and after diluting with deuterated solvents (DMSO-d6, D2O, CD3OD, and CDCl3). The dilution offers structural modifications of the IL due to the solvents capacity to ionization. For further investigation of highly viscous cellulose dopes made of imidazolium-based IL, solid-state NMR spectroscopy enables the reproducibility of liquid-state NMR data of pure IL. The correlation of liquid- and solid-state NMR is shown on EMIM-Ac and cellulose/EMIM-Ac dope (10 wt %).  相似文献   
83.
Dinuclear Pt-containing compounds might be used to overcome the intrinsic and acquired cell resistance of widely used anticancer drugs such as cisplatin. Recently, the complexes [[cis-Pt(NH3)2]2(mu-OH)(mu-pz)](NO3)2 (with pz = pyrazolate) (1), [[cis-Pt(NH3)2]2(mu-OH)(mu-1,2,3-ta-N(1),N(2))](NO3)2 (with ta = 1,2,3-triazolate) (2), and the binding of 1 to d(CpTpCpTpG*pG*pTpCpTpCp) have been characterized. Here we provide the structural and electronic properties of the free drugs, of the intermediates of binding to guanine bases, and of the products, by performing DFT calculations. Our results show that in 2 an isomerization of the Pt-coordination sphere from N(2) to N(3) of the triazolate unit determines a thermodynamic stabilization of approximately 20 kcal/mol as a consequence of the formation of an allylic structure. In addition, hybrid quantum-classical molecular dynamics simulations of 1 and 2 DNA adducts have shed light on the structural distortions that the drugs induce to the DNA duplex. Our calculations show that the rise and the tilt of the two adjacent guanines are identical in the presence of 1 and 2, but they markedly increase when 2 binds in the N(1),N(3) fashion. In addition, the drugs do not provoke any kink upon binding to the double-stranded DNA, suggesting that they may act with a mechanism different than that of cisplatin. The accuracy of our calculations is established by a comparison with the NMR data for the corresponding complex with 1.  相似文献   
84.
GivenanergodicmeasurewithpositiveentropyandonlypositiveLyapunov exponents, its dynamical quantifiers can be approximated by means of quantifiers of some family of uniformly expanding repellers. Here non-uniformly expanding maps are studied that are C 1+β smooth outside a set of possibly critical or singular points.  相似文献   
85.
In contrast to classical optimization problems, in multiobjective optimization several objective functions are considered at the same time. For these problems, the solution is not a single optimum but a set of optimal compromises, the so-called Pareto set. In this work, we consider multiobjective optimization problems that additionally depend on an external parameter ${\lambda \in \mathbb{R}}$ , so-called parametric multiobjective optimization problems. The solution of such a problem is given by the λ-dependent Pareto set. In this work we give a new definition that allows to characterize λ-robust Pareto points, meaning points which hardly vary under the variation of the parameter λ. To describe this task mathematically, we make use of the classical calculus of variations. A system of differential algebraic equations will turn out to describe λ-robust solutions. For the numerical solution of these equations concepts of the discrete calculus of variations are used. The new robustness concept is illustrated by numerical examples.  相似文献   
86.
The generation of a nonheme oxoiron(IV) intermediate, [(cyclam)FeIV(O)(CH3CN)]2+ ( 2 ; cyclam=1,4,8,11‐tetraazacyclotetradecane), is reported in the reactions of [(cyclam)FeII]2+ with aqueous hydrogen peroxide (H2O2) or a soluble iodosylbenzene (sPhIO) as a rare example of an oxoiron(IV) species that shows a preference for epoxidation over allylic oxidation in the oxidation of cyclohexene. Complex 2 is kinetically and catalytically competent to perform the epoxidation of olefins with high stereo‐ and regioselectivity. More importantly, 2 is likely to be the reactive intermediate involved in the catalytic epoxidation of olefins by [(cyclam)FeII]2+ and H2O2. In spite of the predominance of the oxoiron(IV) cores in biology, the present study is a rare example of high‐yield isolation and spectroscopic characterization of a catalytically relevant oxoiron(IV) intermediate in chemical oxidation reactions.  相似文献   
87.
88.
The absorption of a resonant coupling laser driving a closed degenerate two-level system in an atomic cesium beam was investigated as a function of the detuning of a second laser probing the same transition. The measurements were performed for four different polarization combinations of the two laser beams. Except for the beams of counterrotating polarizations all coupling-laser absorption profiles showed "absorption within transparency," i.e., the absorption in the region around the two-photon resonance was smaller than the absorption corresponding to the one-photon transition induced by the coupling laser, and an extra absorption peak was observed on this curve at the two-photon resonance. With regard to the beams of counterrotating polarizations we observed a switch from absorption within transparency to "transparency within transparency" when the probe-laser power exceeded the constant coupling-laser power. In other words, the cesium ensemble became mostly transparent to the coupling-laser beam at the two-photon resonance.  相似文献   
89.
90.
We study isometric embeddings of a Euclidean space or a Heisenberg group into a higher dimensional Heisenberg group, where both the source and target space are equipped with an arbitrary left-invariant homogeneous distance that is not necessarily sub-Riemannian. We show that if all infinite geodesics in the target are straight lines, then such an embedding must be a homogeneous homomorphism. We discuss a necessary and certain sufficient conditions for the target space to have this ‘geodesic linearity property’, and we provide various examples.  相似文献   
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