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71.
The chiral resolving ability of a novel single-isomer cationic β-cyclodextrin (CD), mono-6A-propylammonium-6A-deoxy-β-cyclodextrin chloride (PrAMCD), as a chiral selector in capillary electrophoresis (CE) is reported in this work for the enantioseparation of hydroxy, carboxylic acids and amphoteric analytes. The effect of chiral selector concentration on the resolution was studied. Good resolutions were achieved for hydroxy acids. Optimum resolutions were obtained even at 3.5 mM CD concentration for carboxylic acids. The electrophoretic method showed good linearity and reproducibility in terms of migration times and peak areas, which should make it suitable for routine analysis. In addition, baseline chiral separation of a six-acid mixture was achieved within 20 min. PrAMCD proved to be an effective chiral selector for acidic analytes. 相似文献
72.
The direct reactions of (C5H5)2LnCl with LiN=C(NMe2)2 proceeded at room temperature in THF under pure nitrogen to yield the lanthanocene guanidinate complexes [(C5H5)2Ln(mu-eta1:eta2-N=C(NMe2)2)]2 (Ln = Gd (1), Er (2)). Treatment of phenyl isocyanate with complexes 1 and 2 results in monoinsertion of phenyl isocyanate into the Ln-N(mu-Gua) bond to yield the corresponding insertion products [(C5H5)2Ln(mu-eta1:eta2-OC(N=C(NMe2)2)NPh)]2 (Ln = Gd (3), Er (4)), presenting the first example of unsaturated organic small molecule insertion into the metal-guanidinate ligand bond. Further investigations indicate that N,N'-diisopropylcarbodiimide does not react with complexes 1 and 2 under the same conditions; however, it readily inserts into the lithium-guanidinate ligand bond of LiN=C(NMe2)2. As a synthon of the insertion product Li[(iPrN)2C(N=C(NMe2)2)], its reaction with (C5H5)2LnCl gives the novel organolanthanide complexes containing the guanidinoacetamidinate ligand, (C5H5)2Ln[(iPrN)2C(N=C(NMe2)2)] (Ln = Yb (5), Er (6), Dy (7)). All complexes were characterized by elemental analysis and spectroscopic properties. The structures of complexes 1, 3, 5 and 7 were determined through X-ray single-crystal diffraction analysis. 相似文献
73.
Ebrahim Kianmehr Maryam Fardpour Ali Darvish Ali Nemati Kharat Seik Weng Ng 《Tetrahedron letters》2019,60(10):699-702
Synthesis of substituted phthalides through a ruthenium-catalyzed reaction of phthalic anhydrides with acrylates is described. The reaction proceeds via CH bond activation and leads to the formation of vinylated phthalides through a successive double vinylation accompanied by decarboxylation and annulation reactions. 相似文献
74.
Applied Biochemistry and Biotechnology - The model describes the anaerobiosis of 2-ethylhexanoic acid (2-EHA), which is a persistent and inhibitory organic waste. Model development was based on a... 相似文献
75.
Wen Weng Qing Le Zeng Bi Xia Yao Wen Shi Lin Qing Hua Wang Xiu Li You 《Chromatographia》2006,64(7-8):463-467
Five structurally related amino acid derivatives were enantioseparated by HPLC with a commercially available chiral stationary phase, Chiralcel OD-H. The chromatographic experiments were performed in the normal phase mode. n-Hexane/polar alcohol was used as mobile phase. Excellent baseline enantioseparations could be obtained for all these solutes. The effects of the concentration of polar alcohol and the column temperature on the retentions and enantioseparations were studied in detail. From the van't Hoff plots the corresponding apparent thermodynamic parameters were derived. Mechanism aspects of chiral recognition were discussed based on the relationship between the thermodynamic parameters and the structures of the solutes. It was found that the substituent of the phenyl group on the residual group of the amino acid derivatives was close relevant to thermodynamic origin of enantioseparation. Much better enthalpy–entropy compensation effect was obtained by plotting the differential, rather than the original, thermodynamic parameters. 相似文献
76.
Seven structurally related amino acid derivatives were successfully enantioseparated by HPLC with a commercially available column containing a chiral immobilized network polymer derived from L-tartaric acid. The experiments were carried out under normal-phase conditions. All the solutes could be baseline separated using n-hexane/2-propanol (95/5) as eluent at a flow rate of 1 ml/min at 25 degrees C, with reasonable retention time (<12 min). The effects of the polar alcohol modifier (type and content) in the mobile phase and the column temperature on the enantioseparation were studied. Apparent thermodynamic parameters were also calculated from the plots of ln alpha or ln k' versus 1/T. Some mechanistic aspects of chiral recognition were discussed with respect to the structures of the solutes. It was found that the enantioseparations are all enthalpy driven, and the N-acyl groups of the solutes have significant influence on the chiral recognition. 相似文献
77.
水/AOT/正庚烷微乳体系中磺酸根水化作用的FT—IR研究 总被引:1,自引:0,他引:1
运用傅立叶变换红外光谱(FT-IR)对水/琥珀酸(乙基已基)磺酸钠(AOT)/正庚烷微乳体系中磺酸根的水化作用进行了研究.由于微乳体系中水分子与表面活性剂分子的相互作用,S=O对称伸缩振动的红外吸收峰向低频方向移动.体系中的加水量W0(水与AOT的摩尔比)由0.5增大至25时,磺酸根对称伸缩振动的红外吸收峰由1051.39cm-1向低频移动至1046.15cm-1.同时,由于Na 的不对称作用,AOT分子中磺酸根反对称伸缩振动分裂成两个吸收峰,分别位于正215cm-1及1245cm-1附近,两个劈裂峰的距离及各自的峰面积均随体系中加水量的变化而变化,应用二阶导数、傅立叶退卷积及曲线拟会等分辨率增强技术可更清楚地反映出这个二重峰的变化情况.固体AOT分子中碳酸根反对称伸缩振动分裂的两个峰之间频率的差值约为42cm-1,形成微乳液以后,这两个峰的差值变小,W0为20时,这两个峰频率的差值逐渐减小到29cm-1,这些变化与磺酸根的水化程度直接相关 相似文献
78.
Campos LM Dang H Ng D Yang Z Martinez HL Garcia-Garibay MA 《The Journal of organic chemistry》2002,67(11):3749-3754
A detailed thermochemical analysis of the alpha-cleavage and decarbonylation reactions of acetone and several ketodiesters was carried out with the B3LYP/6-31G* density functional method. The heats of formation of several ground-state ketones and radicals were calculated at 298 K to determine bond dissociation energies (BDE) and radical stabilization energies (RSE) as a function of substituents. Results show that the radical-stabilizing abilities of the ketone substituents play a very important role on the thermodynamics of the alpha-cleavage and decarbonylation steps. An excellent correlation between calculated values and previous experimental observations suggests that photochemical alpha-cleavage and decarbonylation in crystals should be predictable from knowledge of excitation energies and the RSE of the substituent. 相似文献
79.
We are dealing with a numerical method for solving the problem of minimizing a difference of two convex functions (a d.c. function) over a closed convex set in
n
. This algorithm combines a new prismatic branch and bound technique with polyhedral outer approximation in such a way that only linear programming problems have to be solved.Parts of this research were accomplished while the third author was visiting the University of Trier, Germany, as a fellow of the Alexander von Humboldt foundation. 相似文献
80.