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1.
(R,R)-Salen-based chiral polymer P-1 was synthesized by the polymerization of 5,5'-((2,5-dibutoxy-1,4-phenylene)bis(ethyne-2,1-diyl))bis(2-hydroxy-3-(piperidin-1-ylmethyl) benzaldehyde (M-1) with (1R,2R)-cyclohexane-1,2-diamine (M-2) via nucleophilic addition- elimination reaction, and (R,R)-salan-based polymer P-2 could be obtained by the reduction reaction of P-1 with NaBH(4). (R,R)-Salen-based chiral polymer P-1 can exhibit greater fluorescence enhancement response toward (l)-α-hydroxyl carboxylic acids, and the value of enantiomeric fluorescence difference ratio (ef) can reach as high as 8.41 for mandelic acid and 6.55 for lactic acid. On the contrary, (R,R)-salan-based chiral polymer P-2 shows obvious fluorescence quenching response toward α-hydroxyl carboxylic acids. Most importantly, (R,R)-salen-based polymer P-1 can display bright blue fluorescence color change in the presence of (l)-α-hydroxyl carboxylic acids under a commercially available UV lamp, which can be clearly observed by the naked eyes. 相似文献
2.
《Journal of Coordination Chemistry》2012,65(2):281-292
In this study, the formation constants of 1?:?1 binary complexes of Cu(II) with L-glutamic acid, L-aspartic acid, glycine, L-alanine, L-valine, and L-leucine and 1?:?2 binary complexes of L-glutamic acid, glycine and the protonation macro- and microconstants of all these amino acids were determined potentiometrically in aqueous solutions at 5.0, 20.0, and 35.0°C at a constant ionic strength of I?=?0.10?mol?L?1 (NaClO4). The thermodynamic parameters ΔG f°, ΔH f°, and ΔS f° were determined for the protonation of all amino acids used in this study and for the complex formation reactions of them with Cu(II). The results were analysed by means of Principle of hard and soft [Lewis] acids and bases. Additionally, in order to confirm the complex formation and determine the stability constants of complexes, UV-Vis spectroscopic studies were carried out. The stability constants obtained by spectrophotometrically are confirmed by those determined potentiometrically. 相似文献
3.
Salvatore Andini Giuseppina Castronuovo Vittorio Elia Amelia Pignone Filomena Velleca 《Journal of solution chemistry》1996,25(9):837-848
Calorimetric and nuclear relaxation time measurements were carried out at 25°C on concentrated aqueous solutions of urea containing the L and D forms of the following -aminoacids: alanine, -aminobutyric acid, norvaline, and norleucine. Glycine was also studied under the same experimental conditions. The enthalpic interaction coefficients were rationalized according to the preferential configuration model. The trends of the homochiral coefficients at increasing concentration of urea underline an interaction mechanism not different from that occurring in water. Chiral recognition is the quantity more affected by the nature of the solvent. Among the amino acids studied, only norleucine presents this effect, which vanishes at the highest concentrations of urea because the attenuated electrostatic interactions cannot impose preferential configurations. 相似文献
4.
There are many examples in the literature of a strict relation between the pathways of decomposition of a drug substance and chemical structure of its molecule. For this reason, a study has now been performed on the relation between thermal decomposition of ??-amino acids and their chemical structure. To achieve this goal, a group of a dozen or so compounds was chosen at random, and the results obtained using the DTA, TG and DTG analyses of their thermal decomposition were interpreted by highly advanced multivariate methods, principal component analysis and cluster analysis. By this statistical analysis, the influence of specific functional groups on thermal decomposition of ??-amino acids was determined. It has been found that first two principal components explain together more than 75?% of variance, and in an exceptional case, about 90?%. The third stage of decomposition was that at which the thermoanalytical data were best correlated with chemical constitution of a compound. It has also been recognized that a better discrimination among the analysed compounds was obtained for the DTA data set. The results can be useful for identification of a relation between the pathway of degradation of a drug substance and chemical structure of its molecule, and for predicting chemical stability of the compounds studied. 相似文献
5.
Marcos Hernández-Rodríguez 《Tetrahedron》2007,63(32):7673-7678
C2-Symmetrical chiral thioureas (S,S)-1 and (S,S)-2 were prepared in good yield by the reaction of 2 equiv of inexpensive (S)-1-phenylethylamine, or the corresponding naphthyl analog, with 1 equiv of thiophosgene in the presence of excess triethylamine. The presence of asymmetric elements in (S,S)-1 and (S,S)-2, and their capacity to act as receptors for anionic species via hydrogen bonding were exploited in the development of 1H NMR spectroscopic enantiodiscrimination of chiral carboxylic acids. In particular, the diastereomeric complexes derived from thioureas (S,S)-1 and (S,S)-2 with ammonium salts of the chiral acids gave rise to well separated signals of the α-hydrogens and simple integration provides the corresponding enantiomeric ratios. Furthermore, it was observed that Cα-H in the (R) enantiomers of the chiral α-hydroxy and α-amino carboxylic acids studied in this work consistently appears downfield relative to the same signals in the (S) enantiomers. 相似文献
6.
《Tetrahedron: Asymmetry》1998,9(8):1441-1444
Through alkylation of ethyl 2-phthalimidoacetate in chiral reverse micelles formed from chiral surfactants, followed by hydrazinolysis and hydrolysis of the resulting products, optically active α-amino acids were synthesized. The highest enantioselectivity was 59.5%. Meanwhile, we have found that the asymmetric induction depends on the reaction temperature, the alkyl chain length of surfactant and the strucure of the surfactants. 相似文献
7.
A new chiral sensor based on an N,N'-dioxide nickel(II) complex was prepared, which could visually recognize a series of chiral α-hydroxycarboxylic acid enantiomers by coordination and self-assembly forming into nanospheres or nanofibers. With the help of various techniques, the morphology structures of the colloid or suspension were obtained and the counterion-displacement assays were also confirmed. In addition, this metal complex could act as a highly enantioselective fluorescence sensor to recognize N-Boc-amino acids and chiral α-hydroxycarboxylic acids. 相似文献
8.
The densities and viscosities of aqueous solution of cetyltrimethylammonium bromide (0.01 mol kg−1) (CTAB) and solutions of CTAB containing amino acids, viz., glycine, l-serine, and l-valine (0.01–0.05 mol kg−1), were determined in the temperature range 298.15—313.15 K. Apparent molar volumes of the amino acids were calculated from
the density and viscosity values. The calculated apparent molar volumes were used to calculate standard partial molar volumes
(-V
20) and standard partial molar volumes of transfer of amino acids from water to an aqueous solution of CTAB. The viscosity values
were used for the calculation of the viscosity coefficients A and B in the Jones—Dole equation. The linear dependences of -V
20 and B on the number of carbon atoms in the alkyl chains of the amino acids were found. The results obtained were used in analysis
of hydrophilic-hydrophilic, hydrophilic-hydrophobic, and hydrophobic-hydrophobic interactions that occur during dissolution
of amino acids in an aqueous solution of CTAB. 相似文献
9.
10.
Jungu Guo Hao Yuan Yuncong Chen Zhongyan Chen Menglong Zhao Liang Zou Yi Liu Zhipeng Liu Qiang Zhao Zijian Guo Weijiang He 《中国科学:化学(英文版)》2019,(4)
A two-photon ratiometric fluorescent sensor for Cu~+ in endoplasmic reticulum(ER), CNSB, was developed via coumarin/ASBD integration based on FRET mechanism. In solution, CNSB shows reversible, highly-specific ratiometric response to Cu~+ .Moreover, CNSB exhibits suitable K_d value, suggesting the possibility of detecting Cu~+ in the living cells. The probe can enter the MCF-7 cells easily and specifically locates in the ER. The highly specific ratiometric response of CNSB toward Cu~+ in MCF-7 cells provides the sensor the capacity to visualize both exogenous and endogenous Cu~+ in the ER via fluorescence imaging.Next, CNSB was utilized to detect the fluctuation and distribution of Cu~+ under ER stress in MCF-7 cells, which confirmed directly the relationship between Cu~+ enhancement and ER stress. Meanwhile, the two-photon ability of coumarin facilitated the sensor to visualize Cu~+ fluctuation via two-photon fluorescence imaging. In addition, the spatial distribution of Cu~+ in the heart slice of the 14-day-old rat was demonstrated using CNSB. This study demonstrates the promising potential of CNSB in clarifying the Cu~+ -dependent signaling in the ER stress-related diseases. 相似文献
11.
Abdelatif Elmarrouni 《Tetrahedron》2010,66(3):612-5977
A simple synthetic method for the preparation of optically active pyrimidinyl α-amino acids is presented. A nucleophilic ipso-substitution reaction between 2-(benzylsulfonyl)-4-isopropoxypyrimidines and a nucleophilic side chain of several protected natural α-amino acids is investigated to obtain new pyrimidin-2-yl α-amino acids. A detailed optimisation study of this reaction is discussed. Moreover, the selective O-alkylation of 2-(benzylsulfanyl)-4(3H)pyrimidinones with a hydroxylic side chain of some natural α-amino acids under Mitsunobu conditions is studied as a method to prepare new pyrimidin-4-yl α-aminoesters. 相似文献
12.
John K. Gallos Vassiliki C. Sarli Zoe S. Massen Anastassia C. Varvogli Constantina Z. Papadoyanni Sofia D. Papaspyrou Nicolaos G. Argyropoulos 《Tetrahedron》2005,61(3):565-574
A new method for the synthesis of racemic non-proteinogenic α-amino acids has been developed, which involves (i) hetero-Diels-Alder addition of ethyl 2-nitrosoacrylate to electron rich alkenes such as enol ethers, enamines and allylsilanes, (ii) NaCNBH3 reduction of the CN bond in the oxazines thus generated, the stereochemistry of the products being controlled by epimerisation of the thermodynamically less stable isomer to the more stable one, (iii) protection of the N-H group as N-Boc and (iv) finally, N-O bond cleavage of both free and protected products to give proline or bis-homoserine derivatives, respectively. An example with concomitant reduction of the carboxylate group, resulting in the formation of the respective amino alcohol is reported. Applying this methodology to a homochiral enol ether, the protected parent d-proline was prepared in enantiomerically pure form, whereas the asymmetric synthesis of the respective bis-homoserine was unsuccessful. 相似文献
13.
Christopher I. Harding 《Tetrahedron》2004,60(35):7679-7692
A benzyloxycarbonyl protected glycine equivalent 2 has been prepared in enantiopure form and has been used in the synthesis of both α-substituted amino acids and α,α-disubstituted amino acids. The process involved deprotonation to form the corresponding enolates which underwent stereoselective alkylation with various electrophiles and upon hydrolysis gave the corresponding amino acid derivatives as enantiomerically pure products. 相似文献
14.
《Tetrahedron: Asymmetry》2000,11(6):1411-1423
The novel, chiral glycinamides (S,S)-3 and (S,S)-4 were prepared in good yields from C2-symmetric chiral amines (S,S)-1 and (S,S)-2, respectively. Enolate formation and addition to methyl iodide and benzyl bromide proceeded in good yield and high diastereoselectivity, especially in the presence of LiCl or DMPU. Removal of the phthaloyl protecting group with hydrazine, followed by hydrolysis with 6N HCl, converted the benzylated product (S,S,S)-7 to enantiopure (S)-phenylalanine. 相似文献
15.
Positron emission tomography (PET) utilises positron emitting radiopharmaceuticals in the study of metabolic and physiological processes. FDG-PET is a useful technique for tumour detection; however FDG has disadvantages. The incorporation of labelled amino acids into brain tumours and into some other organs with high physiological consumption of glucose is a superior diagnostic method due to its much higher selectivity compared to FDG. A Ni(II) complex with a Schiff base of BPB and glycine was one of the first glycine synthons used for asymmetric synthesis of carbon-11 and fluorine-18 labelled α-amino acids. A similar complex was employed for routine preparation of [(18)F]FET. Physico-chemical investigations allowed us to design modified complexes with much stronger stereodiscriminative power including stereospecific ones. Chiral nickel complexes are also used for the preparation of tailored amino acids for the incorporation into peptides followed by labelling the peptides with fluorine-18 labelled "click" reagents. This review covers PET applications of Ni(II) complexes of Schiff base of BPB and α-amino acids from 1989 to date. 相似文献
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18.
Summary A method is proposed for determining the monomer in the polycondensation of esters of-amino acids. The accuracy of the method was to within 1–1.5%. 相似文献
19.
Dilution enthalpies of aqueous solutions of 3-amino propanoic acid, 4-amino butanoic acid, 5-amino pentanoic acid, and 6-amino hexanoic acid were determined at T = (293.15, 298.15, 303.15, and 308.15) K using an LKB flow microcalorimeter. The homotactic interaction coefficients were obtained according to the McMillan–Mayer theory from the experimental data. For all the systems studied, the dilution of α,ω-amino acids in water is an exothermic process; the pair coefficients have positive values which increases with chain length. The obtained values of the interaction coefficients are interpreted in terms of solute–solvent and solute–solute interactions and are used as indicative of hydrophobic behavior of the amino acid studied. 相似文献
20.
M. Angeles Díaz-Díez Fernando J. García-Barros Francisco J. Higes-Rolando Alvaro Bernalte-García Cristóbal Valenzuela-Calahorro 《Transition Metal Chemistry》1995,20(4):402-405
Summary Complexes of CuII with 2-(benzylamino)-2-deoxy-d-glycero-d-talo heptonic acid (BnMa) and 2-(benzylamino)-2-deoxy-d-glycero-l-gluco heptonic acid (BnGa) were prepared and characterized by elemental analysis, thermal data, i.r., electronic and e.s.r. spectra, magnetic susceptibility measurements, and X-ray powder diffraction. The metal:ligand stoichiometry of these complexes is 12 and coordination around CuII seems to be octahedral, with the ligands bound through the N atom of the amino group and O atoms of the bridging carboxylate group. 相似文献