共查询到20条相似文献,搜索用时 15 毫秒
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Olsen RA Borchardt D Mink L Agarwal A Mueller LJ Zaera F 《Journal of the American Chemical Society》2006,128(49):15594-15595
The protonation of cinchona alkaloids in solution leads to the severe restriction of their internal rotational degrees of freedom and to the locking of the molecule around a specific conformation held in place by a bridging counterion of the acid used for protonation. For HF, direct interactions were detected by NMR between the fluorine anion and not only with the acidic hydroxo group but also with non-acidic hydrogen atoms in the quinoline ring. 相似文献
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The protonation degree of cresol red (CR) in frozen aqueous solutions at 253 or 77 K, containing various acids (HF, HCl, HNO3, H2SO4, and p-toluenesulfonic acid), sodium hydroxide, NaCl, or NH4Cl, was examined using UV/Vis absorption spectroscopy. CR, a weak organic diacid, has been selected as a model system to study the acid-base interactions at the grain boundaries of ice. The multivariate curve resolution alternating least-squares method was used to determine the number and abundances of chemical species responsible for the overlaying absorption visible spectra measured. The results showed that the extent of CR protonation, enhanced in the solid state by 2-4 orders of magnitude in contrast to the liquid solution, is principally connected to an increase in the local concentration of acids. It was found that this enhancement was not very sensitive to either the freezing rate or the type of acid used and that CR apparently established an acid-base equilibrium prior to solidification. In addition, the presence of inorganic salts, such as NaCl or NH4Cl, is reported to cause a more efficient deprotonation of CR in the former case and an enhanced protonation in the latter case, being well explained by the theory of Bronshteyn and Chernov. CR thus served as an acid-base indicator at the grain boundaries of ice samples. Structural changes in the CR molecule induced by lowering the temperature and a presence of the constraining ice environment were studied by the absorption and 1H NMR spectroscopies. Cryospheric and atmospheric implications concerning the influence of acids and bases on composition and reactivity of ice or snow contaminants were examined. 相似文献
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Tong X Bernard S Dory YL Zhao Y 《Langmuir : the ACS journal of surfaces and colloids》2011,27(7):3867-3871
We report the finding that a chiral cyclopeptide dissolved in a nematic liquid crystal (LC) host could aggregate in a manner that is controlled by the texture (LC director configuration) of a cholesteric phase that is induced by the cyclopeptide itself. On one hand, with the fingerprint texture, where the helical axis formed by rotating LC molecules, that lies in the substrate plane, the cyclopeptide can use the LC texture as a template to aggregate and form long-range-ordered ribbons that mimic the helical configuration of the LC director. On the other hand, with the planar texture, where the helical axis is normal to the substrate plane, the cyclopeptide can migrate into the "oily-streak" defect regions of the cholesteric phase and stabilize a network of defects that dictates the electrooptical response of the LC. This is the first example of a molecular species exhibiting such a structured aggregation and defect stabilization effect in a cholesteric LC, but similar phenomena were previously reported for platinum nanoparticles and silica colloidal particles, respectively, dispersed in a cholesteric LC host. This study provides more evidence for the potential interest of exploring LCs as an anisotropic medium for mediating the aggregation and assembly of cyclopeptides. 相似文献
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Demonstration of isospecific free radical polymerization of acrylate controlled by conformation and chirality of monomer
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Hitoshi Tanaka Yoshitaka Matsubara Katsuhiko Kusunoki Naoki Saito Tatsuya Kibayashi 《Journal of polymer science. Part A, Polymer chemistry》2015,53(17):2007-2016
Radical polymerization of lactic acid‐based chiral and achiral methylene dioxolanones, a model for conformationally s‐cis locked acrylate, was carried out with AIBN to demonstrate an isospecific free radical polymerization controlled by chirality and conformation of monomer. Polymerization of the dioxolanones proceeded smoothly without ring opening to give a polymer with moderate molecular weight and 100% of maximum isotacticity. ESR spectrum indicated a twisted conformation of the growing poly(methylene dioxolanone) radical in contrast to an acyclic analogous radical, suggesting a restriction of the free rotation around main chain Cα? Cβ bond of the growing radical center. Chirality as well as the polarity and bulkiness of monomer affected the polymer tacticity, and chiral alkyl substituent would afford a high isotactic polymer, in which higher the enantiomeric excess of the monomer was, higher the isotacticity of the polymer was. While, achiral or polar substituents including dibenzyl and trichloromethyl groups would afford an atactic polymer. In addition, glass transition temperature (Tg) of the resulting polymers was significantly high, ranging from 172.2 to 229.8 °C, and even for an isotactic polymer Tg was as high as 206.8 °C. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2007–2016 相似文献
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The hypothesis is introduced, that nonrigid drug molecules interact with biological receptors in a well-defined but unknown conformation that need not belong to an energy minimum. A verification of this assumption has to include a match of conformation and chirality. Even the different action of pairs of nonrigid enantiomers allow one to recognize uniquely the important role of conformations because flexible molecules are partially able to avoid wrong attachment to the receptor. According to a simple model, a monotonic relation between biological activity and rotational barriers (and/or torque constants) can be expected and, by means of rank correlation analysis of adrenergic activities, has been found, too. In order to apply the latter method, particularities concerning quantitative structure–activity analyses of nonrigid and/or chiral molecules are worked out. We optimized conformations by means of analytically calculated first partials of the energy and a quasi-Newton method. Using a convenient numerical method, it was shown that coplanar conformations of catecholamines are generally unstable. Moreover, CNDO /2 proved to be a reliable method for conformational studies, in which rotations about conjugated bonds [1] are not considered. 相似文献
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《Acta Crystallographica. Section C, Structural Chemistry》2018,74(3):274-282
Naltrexone [systematic name: (4R,4aS,7aR,12bS)‐3‐cyclopropylmethyl‐4a,9‐dihydroxy‐2,4,5,6,7a,13‐hexahydro‐1H‐4,12‐methanobenzofuro[3,2‐e]isoquinolin‐7‐one] is an important morphine‐related drug used for combating alcoholism and opioid dependence. Of the eight crystal forms of naltrexone known thus far, only one exists in the neutral form and it crystallizes as a monohydrate. We have isolated the naltrexone free base as two new solvate forms, i.e. the ethyl acetate 0.33‐solvate, C20H23NO4·0.33C4H8O2, (I), and the diethyl ether hemisolvate, C20H23NO4·0.5C4H10O, (II). While just one solvent molecule is present in the asymmetric unit of each solvate, there are three drug molecules (Z′ = 3) in ethyl acetate solvate (I) and two (Z′ = 2) in diethyl ether solvate (II). In (I), one of the three crystallographically independent drug molecules is present with its cyclopropyl group disordered over two sets of positions, as is the whole diethyl ether solvent molecule in (II). In all known forms, including the title forms, the naltrexone molecule exhibits the same conformation of the fused rings. The only conformational variability of naltrexone is in the cyclopropylmethyl group. Two conformations can be found around the bond connecting this group to the N‐heterocycle, which is directly related to drug protonation. We have calculated, at the B3LYP/6‐31G** level of theory, the minimum energy conformations of protonated and neutral naltrexone molecules for a chosen torsion angle about this bond. The lowest energy conformers depend on the protonation state and are in agreement with those found in the solid state. Within the cyclopropylmethyl group, the bond joining the methylene C atom to the cyclopropyl fragment also evidences conformational variability. In the literature, there are two well defined conformations around this bond. A third cyclopropyl conformation around this second bond is observed in the title solvates. Concerning the supramolecular features of the previously reported crystal structures, only one classical hydrogen bond between naltrexone molecules and one C(8) homosynthon is known, pointing to the robustness of this synthon and the difficulty in disrupting it. New R22(7) and C22(10) homosynthons are found in both (I) and (II), suggesting that their occurrence derives from crystallization of the neutral drug from nonpolar solvents. 相似文献
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A new cyclodextrin-polythiophene conjugate (CDPT) has been prepared by attaching permethyl-α-cyclodextrins to polythiophene (PT) through a hexamethylene tether. Circular dichroism spectral examination of CDPT revealed that only a weak positive Cotton effect (Δε=0.1?M(-1) cm(-1) ) was induced at the main band of the PT in dimethyl sulfoxide and similarly weak bisignate signals in pure and aqueous methanol solutions, which indicates that the α-cyclodextrins appended to PT with a long tether are ineffective in inducing a homochiral structure in the PT backbone. Nevertheless, enantiomeric amino acids and dipeptides added to an aqueous methanolic solution of CDPT caused chirality-dependent hypochromic changes in the UV/Vis spectra, which enabled us to sense these species and quantitatively determine the enantioselectivity by observing the difference in absorbance upon interaction with pairs of enantiomers. Enantiomeric d,d/l,l-dipeptide pairs rather than D/L-amino acid pairs were better differentiated in general, the highest dd/ll selectivity of 13.7 being observed for Phe-Phe. 相似文献
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New 30-membered achiral and chiral polyaza macrocyclic ligands, L1 and L2 were synthesized directly from [3 + 3] condensation of phthalic dicarboxaldehyde with cis- and (1R,2R)-diaminocyclohexane, respectively. The trimeric macrocyclic structures were confirmed by electrospray ionization mass spectrometry (ESI-MS), 1H NMR, 13C NMR spectroscopy and elemental analysis. Potentiometry was used to determine the protonation constants of the ligands. UV-vis spectrophotometric titration was employed to investigate the coordination and conformational properties of the chiral ligand (L2). Direct enantioselective aldol reaction has been successfully performed using 4-nitrobenzaldehyde and acetone in the presence of the chiral macrocycle and its zinc(II) complexes as catalysts. 相似文献
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Sakamoto M Iwamoto T Nono N Ando M Arai W Mino T Fujita T 《The Journal of organic chemistry》2003,68(3):942-946
Asymmetric synthesis using frozen chirality generated by spontaneous crystallization was performed. Achiral asymmetrically substituted imide with a tetrahydronaphthyl group on the nitrogen atom crystallized in a chiral fashion, with space group P2(1)2(1)2(1). The molecular chirality generated by spontaneous crystallization was retained in cold THF. The half-life determined on the basis of decreasing optical activity followed by CD spectrometer was 7.8, 33.1, and 150.0 min at -20, -30, -40 degrees C, respectively. The energy barrier (DeltaG()) of racemization was calculated with the temperature dependence of the kinetic constant to be 18.24-18.36 kcal mol(-)(1) at 233-253 K. The memorized frozen chirality was transferred to permanent optically active alcohols by nucleophilic addition with n-buthyllithium. 相似文献
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A 2.2.2 cryptand-based anion exchanger was recently introduced as a commercial product. This new technology relies on a covalently bonded 2.2.2 cryptand, which allows one to selectively control the capacity of the column simply by the choice of eluent. This provides the analyst with more flexibility over conventional anion exchangers to suit the needs of the sample matrix. Since that time, a 2.2.1 version has also been developed and studied. In this paper we will compare the two types of columns and choose the best one for analyzing several environmental samples. 相似文献
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A unique feature of synthetic helical polymers for the detection and amplification of chirality is briefly described in this article. In sharp contrast to host-guest and supramolecular systems that use small synthetic receptor molecules, chirality can be significantly amplified in a helical polymer, such as poly(phenylacetylene)s with functional pendants, which enable the detection of a tiny imbalance in biologically important chiral molecules through a noncovalent bonding interaction with high cooperativity. The rational design of polymeric receptors can be possible by using chromophoric helical polymers combined with functional groups as the pendants, which target particular chiral guest molecules for developing a highly efficient chirality-sensing system. The chirality sensing of other small molecular and supramolecular systems is also briefly described for comparison. 相似文献
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A pair of copper(II) complexes 1 and 2 exhibit an enantiomeric chiral center at the oxygen atom that coordinates to the metal center. The configurations of the oxygen atom chirality and the chelate ring conformation are simply controlled by protected/free hydroxyl groups of the sugar moiety, yielding mirror image CD spectra. In this system, repulsive and attractive forces are used to regulate chirality on the copper-coordinated oxygen atom both in the solid state and in solution. 相似文献
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A series of coordination compounds has been prepared comprising manganese, iron, nickel, and zinc bound by a hexaanionic cryptand where carboxamides are anionic N-donors. The metal complexes have been investigated by X-ray crystallography, and possess metal centers in trigonal monopyramidal geometries with intermetallic distances spanning d(Mn,avg) = 6.080 ? to d(Ni,avg) = 6.495 ?. All complexes featuring trigonal monopyramidal metal(II) ions crystallize in Cc, and feature extended three-dimensional networks composed of cryptate anions linked by bridging potassium countercations. We also report the first solid state structure of the free cryptand ligand, which features no guest in its cavity and which possesses an extended hydrogen-bonding network. SQuID magnetometry data of the metal complexes reveal weak antiferromagnetic coupling of the metal centers. Only the diiron(II) complex exhibits reversible electrochemistry, and correspondingly, its chemical oxidation yields a powder formulated as the diiron(III) congener. The insertion of cyanide into the intermetallic cleft of the diiron(II) complex has been achieved, and comparisons of its solid state structure to the recently reported dicobalt(II) analogue are made. The antiferromagnetic coupling between the diiron(II) and the dicobalt(II) centers when bridged by cyanide does not increase significantly relative to the unbridged congeners. A one-site model satisfactorily fits Mo?ssbauer spectra of unbridged diiron(II) and diiron(III) complexes whereas a two site fit was needed to model the iron(II) centers that are bridged by cyanide. 相似文献
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Harry Adams Neil A. Bailey David E. Fenton Choki Fukuhara Masatoshi Kanesato 《Supramolecular chemistry》2013,25(4):325-330
Abstract The synthesis and crystal structure of the diprotonated cryptand derived from the reaction of tren and 2,6-diacetyl pyridine is reported. The imino nitrogens of the Schiff base linkages are directed so that the dicarbimine functions are in trans, trans geometry relative to the pyridine C-N bond. This configuration has not previously been reported in related pyridine-derived Schiff base macrocycles. 相似文献