首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到10条相似文献,搜索用时 203 毫秒
1.
A facile avenue to fabricate micrometer‐sized chiral (L ‐, D ‐) and meso‐like (dl ‐) SiO2 materials with unique structures by using crystalline complexes (cPEI/tart), composed of comblike polyethyleneimine (cPEI) and L ‐, D ‐, or dl ‐tartaric acid, respectively, as catalytic templates is reported. Interestingly, both chiral crystalline complexes appeared as regularly left‐ and right‐twisted bundle structures about 10 μm in length and about 5 μm in diameter, whereas the dl ‐form occurred as circular structures with about 10 μm diameter. Subsequently, SiO2@cPEI/tart hybrids with high silica content (>55.0 wt %) were prepared by stirring a mixture containing tetramethoxysilane (TMOS) and the aggregates of the crystalline complexes in water. The chiral SiO2 hybrids and calcined chiral SiO2 showed very strong CD signals and a nanofiber‐based morphology on their surface, whereas dl ‐SiO2 showed no CD activity and a nanosheet‐packed disklike shape. Furthermore, metallic silver nanoparticles (Ag NPs) were encapsulated in each silica hybrid to obtain chiral (D and L forms) and meso‐like (dl form) Ag@SiO2 composites. Also, the reaction between L ‐cysteine (Lcys) and these Ag@SiO2 composites was preliminarily investigated. Only chiral L ‐ and D ‐Ag@SiO2 composites promoted the reaction between Lcys and Ag NPs to produce a molecular [Ag–Lcys]n complex with remarkable exciton chirality, whereas the reaction hardly occurred in the case of meso‐like (dl ‐) Ag@SiO2 composite.  相似文献   

2.
3‐Phenyllactic acid is an antimicrobial compound with broad‐spectrum activity against various bacteria and fungus. The observed difference in pharmacological activity between optical isomeric 3‐phenyllactic acid necessitates a method for enantioseparation. Chiral ligand exchange countercurrent chromatography was investigated for the enantioseparation of 3‐phenyllactic acid with a synthesized chiral ligand. A two‐phase solvent system was composed of n‐butanol/hexane/water (0.4:0.6:1, v/v/v) to which Nn‐dodecyl‐l ‐hydroxyproline was added to the organic phase as chiral ligand and cupric acetate was added in the aqueous phase as a transitional metal ion. The influence factors were optimized by enantioselective liquid–liquid extraction. Baseline enantioseparation of racemic 3‐phenyllactic acid by analytical high‐speed countercurrent chromatography was achieved. The optical purities of enantiomeric 3‐phenyllactic acid reached 99.0%, as determined by chiral high‐performance liquid chromatography.  相似文献   

3.
A computational protein design method is extended to allow Monte Carlo simulations where two ligands are titrated into a protein binding pocket, yielding binding free energy differences. These provide a stringent test of the physical model, including the energy surface and sidechain rotamer definition. As a test, we consider tyrosyl‐tRNA synthetase (TyrRS), which has been extensively redesigned experimentally. We consider its specificity for its substrate l ‐tyrosine (l ‐Tyr), compared to the analogs d ‐Tyr, p‐acetyl‐, and p‐azido‐phenylalanine (ac‐Phe, az‐Phe). We simulate l ‐ and d ‐Tyr binding to TyrRS and six mutants, and compare the structures and binding free energies to a more rigorous “MD/GBSA” procedure: molecular dynamics with explicit solvent for structures and a Generalized Born + Surface Area model for binding free energies. Next, we consider l ‐Tyr, ac‐ and az‐Phe binding to six other TyrRS variants. The titration results are sensitive to the precise rotamer definition, which involves a short energy minimization for each sidechain pair to help relax bad contacts induced by the discrete rotamer set. However, when designed mutant structures are rescored with a standard GBSA energy model, results agree well with the more rigorous MD/GBSA. As a third test, we redesign three amino acid positions in the substrate coordination sphere, with either l ‐Tyr or d ‐Tyr as the ligand. For two, we obtain good agreement with experiment, recovering the wildtype residue when l ‐Tyr is the ligand and a d ‐Tyr specific mutant when d ‐Tyr is the ligand. For the third, we recover His with either ligand, instead of wildtype Gln. © 2015 Wiley Periodicals, Inc.  相似文献   

4.
Chiral quantum dots (QDs), differing in their core or shell size and, consequently, in their optical properties, were synthesized by the treatment of commercially available amine‐capped quantum dots with methyl ester N‐acetyl‐L ‐cysteine (CysP). Interestingly, their colloidal methanol solutions remain stable for several months. Their NMR and IR spectra were in accordance with CysP binding to the QD surface through two anchoring groups; its thiolate (strongly bound) and the carbonyl group of its ester (weaker bound) group, whereas their circular dichroism (CD) spectra showed a new broad redshifted band, suggesting that the attachment to the QD surface modified the conformational equilibrium towards conformer(s) with optical activity in this region. These QDs were sufficiently fluorescent to perform studies of the chiral recognition of drugs, in particular the aryl propionic acids (APAs) ketoprofen (KP), naproxen (NP), flurbiprofen (FP), and ibuprofen (IP). We used different drug concentration ranges, depending on the QD solubility. All the assayed drugs quenched the QD emission in a concentration‐dependent mode. Quenching fluorescence assays with the chiral QDs (CS@CysP) showed their extraordinary capacity for the chiral recognition of KP, NP, and FP, and particularly in the case of KP and FP, a remarkable positive allosteric effect was detected for the R enantiomer. By using a drug/CS@CysP molar ratio of 5000:1 and 2500:1, the changes of intensity and the sign of the CD spectrum of the drug evidenced the dissociation of the drug carboxylic group in the presence of the QD.  相似文献   

5.
Novel polyamide with chiral environment was obtained from aromatic diamine, 4,4′‐diaminodiphenylmethane (DADPM), and N‐α‐protected L ‐glutamic acid, N‐α‐benzoyl‐L ‐glutamic acid (Benzoyl‐L ‐Glu‐OH). The optical rotation ([α]D ) of the polyamide was determined to be 3.6° (c = 1.00 g/dL in DMF), implying that the optically active polyamide was obtained. The present polyamide gave a durable self‐standing membrane. The membrane selectively incorporated the D ‐isomer of Ac‐Trp from racemic mixture of Ac‐Trp. The adsorption selectivity toward Ac‐D ‐Trp was determined to be 1.95. It showed chiral separation ability by adopting potential difference as a driving force for membrane transport. The permselectivity was dependent on the potential difference, and at the applied potential difference of 3.0 V, the membrane selectively transported Ac‐D ‐Trp and the permselectivity toward Ac‐D ‐Trp was determined to be 1.84, which was close to the adsorption selectivity of 1.95. Contrary to this, the membrane showed opposite permselectivity at the applied potential difference of 2.0 V and the permselectivity toward the L ‐isomer reached 2.48. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2530–2538, 2009  相似文献   

6.
The accumulation and deposition of β‐amyloid (Aβ) plaques in the brain is considered a potential pathogenic mechanism underlying Alzheimer's disease (AD). Chiral l/d ‐FexCuySe nanoparticles (NPs) were fabricated that interfer with the self‐assembly of Aβ42 monomers and trigger the Aβ42 fibrils in dense structures to become looser monomers under 808 nm near‐infrared (NIR) illumination. d ‐FexCuySe NPs have a much higher affinity for Aβ42 fibrils than l ‐FexCuySe NPs and chiral Cu2?xSe NPs. The chiral FexCuySe NPs also generate more reactive oxygen species (ROS) than chiral Cu2?xSe NPs under NIR‐light irradiation. In living MN9D cells, d ‐NPs attenuate the adhesion of Aβ42 to membranes and neuron loss after NIR treatment within 10 min without the photothermal effect. In‐vivo experiments showed that d ‐FexCuySe NPs provide an efficient protection against neuronal damage induced by the deposition of Aβ42 and alleviate symptoms in a mouse model of AD, leading to the recovery of cognitive competence.  相似文献   

7.
Chiral optical metamaterials with delicate structures are in high demand in various fields because of their strong light–matter interactions. Recently, a scalable strategy for the synthesis of chiral plasmonic nanoparticles (NPs) using amino acids and peptides has been reported. Reported herein, 3D chiral gold NPs were synthesized using dipeptide γ‐Glu‐Cys and Cys‐Gly and analyzed crystallographically. The γ‐Glu‐Cys‐directed NPs present a cube‐like outline with a protruding chiral wing. In comparison, the NPs synthesized with Cys‐Gly exhibited a rhombic dodecahedron‐like outline with curved edges and elliptical cavities on each face. Morphology analysis of intermediates indicated that γ‐Glu‐Cys generated an intermediate concave hexoctahedron morphology, while Cys‐Gly formed a concave rhombic dodecahedron. NPs synthesized with Cys‐Gly are named 432 helicoid V because of their unique morphology and growth pathway.  相似文献   

8.
Recently, amino acid ionic liquids (AAILs) have attracted much research interest. In this paper, we present the first application of AAILs in chiral separation based on the chiral ligand exchange principle. By using 1‐alkyl‐3‐methylimidazolium L ‐proline (L ‐Pro) as a chiral ligand coordinated with copper(II), four pairs of underivatized amino acid enantiomers—dl ‐phenylalanine (dl ‐Phe), dl ‐histidine (dl ‐His), dl ‐tryptophane (dl ‐Trp), and dl ‐tyrosine (dl ‐Tyr)—were successfully separated in two major chiral separation techniques, HPLC and capillary electrophoresis (CE), with higher enantioselectivity than conventionally used amino acid ligands (resolution (Rs)=3.26–10.81 for HPLC; Rs=1.34–4.27 for CE). Interestingly, increasing the alkyl chain length of the AAIL cation remarkably enhanced the enantioselectivity. It was inferred that the alkylmethylimidazolium cations and L ‐Pro form ion pairs on the surface of the stationary phase or on the inner surface of the capillary. The ternary copper complexes with L ‐Pro are consequently attached to the support surface, thus inducing an ion‐exchange type of retention for the dl ‐enantiomers. Therefore, the AAIL cation plays an essential role in the separation. This work demonstrates that AAILs are good alternatives to conventional amino acid ligands for ligand‐exchange‐based chiral separation. It also reveals the tremendous application potential of this new type of task‐specific ILs.  相似文献   

9.
The chromatographic retention mechanism describing relationship between retention factor and concentration of Cu2+(l ‐phenylalanine)2 using chiral ligand mobile phase was investigated and eight mandelic acid derivatives were enantioseparated by chiral ligand exchange chromatography. The relationship between retention factor and concentration of the Cu2+(l ‐phenylalanine)2 complex was proven to be in conformity with chromatographic retention mechanism in which chiral discrimination occurred both in mobile and stationary phase. Different copper(II) salts, chiral ligands, organic modifier, pH of aqueous phase, and conventional temperature on retention behavior were optimized. Eight racemates were successfully enantioseparated on a common reversed‐phase column with an optimized mobile phase composed of 6 mmol/L of l ‐phenylalanine or N,N‐dimethyl‐l ‐phenylalanine and 3 mmol/Lof copper(II) acetate or copper(II) sulfate aqueous solution and methanol.  相似文献   

10.
Au nanoparticles (NPs) functionalized with thioaniline and cysteine are used to assemble bis‐aniline‐bridged Au‐NP composites on Au surfaces using an electropolymerization process. During the polymerization of the functionalized Au NPs in the presence of different amino acids, for example, L ‐glutamic acid, L ‐aspartic acid, L ‐histidine, and L ‐phenylalanine, zwitterionic interactions between the amino acids and the cysteine units linked to the particles lead to the formation of molecularly imprinted sites in the electropolymerized Au‐NP composites. Following the elimination of the template amino acid molecules, the electropolymerized matrices reveal selective recognition and binding capabilities toward the imprinted amino acid. Furthermore, by imprinting of L ‐glutamic or D ‐glutamic acids, chiroselective imprinted sites are generated in the Au‐NP composites. The binding of amino acids to the imprinted recognition sites was followed by surface plasmon resonance spectroscopy. The refractive index changes occurring upon the binding of the amino acids to the imprinted sites are amplified by the coupling between the localized plasmon associated with the Au NPs and the surface plasmon wave.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号