CRYSTAL GROWTH & DESIGN
·
2023
·
IF 3.8
Yaoguo Wang,Genpei Shi,Kuo Wang,Weiwei Tang,Junbo Gong
Crystallization of chiral compounds is dictated by chiral recognition and molecular self-assembly in solution. However, their interplay remains elusive. The reason for the considerably reduced polymorphism in chiral molecules than that of nonchiral molecules remains unclear. Herein, we use a combination of experimental and computational techniques to show that excessive enantiomer functioning, as a native crystallization inhibitor, selectively suppresses the crystallization of racemic polymorphs, affording preferential crystallization of the metastable α polymorph of dl-methionine. Bulk crystallization assays show concomitant crystallization of the α and β polymorphs of racemic dl-methionine in the solution with no enantiomeric excess. However, when the solution contains excessive d-/l-methionine enantiomer, only the metastable α form can be crystallized. Crystal growth experiments, fluoresce confocal microscopy, and atomic force microscope surface topology measurements reveal the growth inhibition of both polymorphs with preferential suppression of the β form by excess native enantiomer. Binding energy calculations and molecular dynamic simulations further demonstrate the preferential adsorption of excessive enantiomers on the (0 0 2) facet of the β form over the α form. Overall, our results uncover a unique chiral self-positioning mechanism where the excess enantiomer solutes serve as a native growth inhibitor to disrupt the kinetics of racemic polymorphic crystallization, affording selective crystallization of only one polymorph of dl-methionine. Our results highlight the important effect of excess enantiomer in a solution on the polymorph occurrence of chiral molecules.
研究领域:
化学
·
材料科学
·
计算化学
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产品关联
DOI
高影响因子
OPTIK
·
2022
·
IF 2.84
Xiang-Lin Fang,Rui-Tong Zhao,Na Chen,Xin Wang,Peng Wang,Zhi-Wei He,Shao-Xin Li,Yang Xu,Yong-Hong He
As one of important optical properties of chiral molecules, the real-time monitoring of the optical rotation is of great significance to study the reaction characteristics of chiral molecules. In this study, we have built an optical frequency domain weak measurement system with linear common-path method for chiral sensing, in which the response between optical rotation and central wavelength shift can reach more than 1200 nm/rad. The high-precision measurement of the optical rotation of chiral molecules and the high-sensitivity real-time monitoring of the decomposition rate in the acidic hydrolysis of sucrose under different concentrations of catalysts are realized using this system. The experimental results are basically consistent with the theoretical prediction. This study shows that optical weak measurement chiral sensing can monitor the hydrolysis degree of chiral molecules in real time without separating and labeling molecules. It has great application potential in the production and research of chiral compounds, especially chiral medicine.
研究领域:
化学
·
光学
·
药物研究
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产品关联
DOI
高影响因子
MOLECULES
·
2022
·Vol. 27
·期 3
·1098
·
IF 4.927
Zhe Liu,Hong Wang,Zhu Chen,Ying Ye,Yuwei Wang
Chiral cholesteric molecular tweezer 7d was synthesized and its influences on changes in the ultraviolet (UV) and fluorescence spectra of various anions were investigated. The results displayed that molecular tweezer 7d selectively recognized F−ions in dimethyl sulfoxide with a detection limit of 5.14 μmol/L, while other anions had little interference. On this basis, a method for the rapid detection of F−ions by host molecular tweezer 7d was established, and the naked-eye detection of F−was realized through the unique yellow color of the complex solution. According to the determination of F−ions in real food samples, it was proved that the established method had good application prospects in F−ion detection.Keywords:cholesteric molecular tweezer;fluoride ions;naked-eye detection;specific recognition;food samples
研究领域:
分析化学
·
食品安全
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DOI
PubMed
高影响因子
MOLECULES
·
2024
·Vol. 29
·期 24
·5887
·
IF 4.2
Jiaxiang Liu,Yongwen Zhang,Ruijuan Yao,Haitao Ren,Weijie Wang,Haohao Feng,Wentao Li,Zongcheng Miao
Achieving superior circularly polarized luminescence brightness (BCPL) is an important subject and continuous challenge for chiroptical materials. Herein, by applying a binary molecular design for the synthesis of chiral organo-Tb3+molecules, a novel pair of mononuclear chiraltris-pyrazolate-Tb3+enantiomers, [Tb(PMIP)3(R,R-Ph-PyBox)] (2) and [Tb(PMIP)3(S,S-Ph-PyBox)] (5), have been synthesized and characterized. The three 1-phenyl-3-methyl-4-(isobutyryl)-5-pyrazolone (HPMIP) ligands play the role of efficient luminescence sensitizers and strong light-harvesting antennas, while the enantiopure 2,6-bis(4-phenyl-2-oxazolin-2-yl) pyridine ligand (R,R/S,S-Ph-PyBox) is employed as the strong point-chiral inducer. With the proper combination of theHPMIPandChiral-Ph-PyBoxwithin the Tb3+enantiomers, strong (PMIP)−-centered π-π*electronic absorption (ε263 nm= 38,400–39,500 M−1cm−1) and brilliant high-purity ligand-sensitized Tb3+-centered green luminescence (ΦPL= 47–48%) were observed. In addition, a clear circularly polarized luminescence (CPL) activity (|glum| = 0.096–0.103) was also observed, resulting in a strongBCPL(610–623 M−1cm−1) for the two Tb3+enantiomers from the hypersensitive transitions. Our results offer an effective path to develop high-performance chiroptical organo-Tb3+luminophores.
研究领域:
化学
·
材料科学
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产品关联
DOI
PubMed
高影响因子
MICROCHIMICA ACTA
·
2020
·Vol. 187
·期 7
·1-8
·
IF 6.232
Li Shuhuai,Pang Chaohai,Ma Xionghui,Zhao Min,Li Haibo,Wang Mingyue,Li Jianping,Luo Jinhui
A luminescent double recognition nanoprobe is described as a new strategy for the selective determination of chiral molecules. C-dots/Ir/Au fluorescent nanoparticles, synthesised under hydrothermal conditions, are used as a high-performance probe in combination with a molecularly imprinted polymer (MIP) and calix[6]arene as a double recognition element. Thiolated calix[6]arene is grafted on C-dots/Ir/Au as the first recognition element, which then forms a host–guest complex with the target molecule levodopa (L-DOPA). Subsequently, an MIP is prepared on the C-dots/Ir/Au (MIP/C-dots/Ir/Au) by chemical polymerisation. After the removal of L-DOPA, double recognition imprinting cavities are formed. The fluorescence intensity at 478 nm of the nanoprobe is effectively quenched by adsorption of L-DOPA on MIP/C-dots/Ir/Au, which provides a method for L-DOPA determination. Owing to the double recognition strategy, this method has excellent selectivity which can effectively avoid interference from enantiomer D-DOPA, and a imprinting factor of 7.1 is obtained for L-DOPA. This accurate and reliable method, with a wide linear range (5 × 10 −10 to 1.2 × 10 −7 mol L −1 ) and a low limit of detection (1.45 × 10 −10 mol L −1 ), was successfully applied to the determination of L-DOPA in real samples, giving standard recoveries of 89.7–110.0%. Thus, the proposed sensing method provides a viable approach for the determination of a single enantiomer.
Schematic presentation of the MIP/C-dots/Ir/Au for L-DOPA detection. A fluorescence double chiral recognition nanoprobe is prepared of C-dots/Ir/Au nanoparticles as signal probe, and a molecularly imprinted polymer (MIP) and calix[6]arene as a double recognition element. Owing to the double recognition strategy, this method has strong specificity and can effectively avoid interference from enantiomers and racemates.
研究领域:
分析化学
·
药物化学
·
材料科学
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产品关联
DOI
PubMed
高影响因子
CHEMISTRY OF MATERIALS
·
2022
·
IF 10.508
Han Lin,Hideyuki Mitomo,Yusuke Yonamine,Zhiyong Guo,Kuniharu Ijiro
The emerging concept of tunable plasmonic chirality is mostly observed as a reconfigurable behavior or a feature of complex chiral plasmonic assemblies. For discrete colloidal particles, it is challenging to achieve reversible tunability or a transient response with regard to chiroptical activities, particularly in the visible or near-infrared region. Herein, we demonstrate a stimulus-responsive system based on chiral molecule–achiral plasmonic nanoparticles coated with polyaniline (PANI) as a variable dielectric layer, in which l-/d-cysteine molecules are introduced between the gold core and the shell as a static chiral source, allowing the chiral transfer effect to be greatly amplified by the hotspot gap of sub-monomolecular thickness. By taking advantage of the responsive properties to either pH or the electric potential dual stimuli of PANI, which also provides a stable and real-time switchable dielectric environment for the whole system, dynamic tuning of the plasmon and its induced chiroptical activities of core–gap–shell nanoparticles@PANI were precisely obtained. This well-defined design provides an open platform for flexible and rational tailoring of plasmonic cores, chiral molecules, and variable dielectrics to chiroptical needs, which is important for realizing applications in chemical sensing, chiral nanocatalysis, enantioselective separations, and novel optical devices.
研究领域:
纳米材料
·
光学
·
化学
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DOI
高影响因子
GREEN CHEMISTRY
·
2021
·Vol. 23
·期 21
·8685-8693
·
IF 10.182
Zhenqing Dai,Junli Guo,Tiantian Su,Jinfeng Wang,Zhida Gao,Yan-Yan Song
The artificial solid-state nanopore/nanochannel based electrochemical sensing technique has demonstrated great advantages such as high sensitivity and minimalized equipment. However, its application is largely hindered by complex routes and high expense for fabrication. Here, we develop low-cost and easily accessible channels based on natural wood and present a pathway to utilize the wood membrane for local electrochemistry applications. Inspired by the natural mineralization of wood, Prussian blue (PB), an artificial peroxidase (POD)-like mimetic, is mineralized in wood channels via a contra-diffusion technique. Using glucose enantiomers (L/D-Glu) as model analysts, a target-activated strategy is used for chiral molecule recognition by combining glucose oxidase (GOx) with PB-modified wood channels. In the as-proposed hybrid channels, GOx catalyzes the oxidation of only D-Glu to gluconic acid and H2O2. These products dramatically activate the POD-like activity of PB and further trigger the oxidation of the uncharged substrate 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) to cationic species (ABTS˙+) in the channels. More importantly, benefitting from the confinement effect of the channel and the asymmetrical mineralization of PB, a significantly selective and sensitive identification of D-Glu is achieved. This study provides a promising way to use natural wood as a novel channel membrane to replace artificial channels for constructing electrochemical sensing platforms.
研究领域:
材料科学
·
生物医学工程
·
分析化学
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DOI
高影响因子
INTERNATIONAL JOURNAL OF PHARMACEUTICS
·
2021
·
IF 5.875
Liping Wang,Xuhui She,Zhi Chen,Sisi Quan,Yingtao Liu,Xiaoman Mai,Tiefeng Yuan,Huajun Fan
A novel molecularly imprinted polymer (MIP) with chiral recognition affinity to S-sulpiride (S-SUL) enantiomer was prepared by using newly synthesized N-acryloyl-tryptophan (ATrp) as function monomer , S-SUL as the template molecule, and ethyleneglycol dimethacrylate (EGDMA) as the cross linker. Under the optimized synthesis conditions, the MIP was synthesized by bulk polymerization according to the molar ratio of 1:4 of S-SUL to ATrp, and structurally characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM) and laser particle analysis. The results illustrated that the MIP offered uniform, loose and porous structure. The adsorption performance of the MIP was evaluated by the isotherm and kinetic models, and the adsorption isotherm conformed to the Freundlich model. The maximum adsorption capacity, selectivity factor and enantioselectivity coefficient to S-SUL were respectively 226.2389 µmol/g, 2.34 and 11.66. Based on the chiral recognition specificity, the drug release experiments demonstrated that the MIP as controlled and sustained release carrier could inhibit the release rate of S-enantiomer compared to the tablet without the MIP, exhibiting the potential of the MIP synthesized in chiral drug delivery.
研究领域:
药物化学
·
材料科学
·
制药工程
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产品关联
DOI
PubMed
高影响因子
ANALYTICAL CHEMISTRY
·
2025
·
IF 6.7
Xiaohui Niu,Yuewei Wang,Xing Yang,Yongqi Liu,Mei Yuan,Jianying Zhang,Hongxia Li,Kunjie Wang
Introducing chiral molecules into metal–organic frameworks (MOFs) to obtain chiral MOFs (CMOFs), the tunability of their structures makes them a highly anticipated class of chiral materials for electrochemical sensing. However, the structure of CMOFs is often limited by synthesis challenges, and introducing chiral molecules into MOFs often leads to a decrease in their internal space. This study introduces a defect engineering strategy into the synthesis of CMOFs to obtain CMOFs with defects, which is an efficient synthesis method. The two CMOFs constructed with different structures not only have more chiral recognition sites but also greatly increase the substrate capacity due to the defects, making them have a wide range of substrates and enhancing the enantioselective recognition effect of the two defective CMOFs. In addition, using MOF as a chiral carrier greatly overcomes the problem of low conductivity of chiral molecules. Based on the advantages of defective CMOFs, we have designed a novel chiral electrochemical sensor with an excellent enantiomer recognition performance. This study provides a simple and scalable synthetic method for constructing CMOFs with defects and high stability.
研究领域:
材料科学
·
分析化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ADVANCED MATERIALS
·
2022
·Vol. 34
·期 37
·2203956
·
IF 32.086
Mengjia Cen,Jiawei Wang,Jianxun Liu,Huilin He,Ke Li,Wenfeng Cai,Tun Cao,Yan Jun Liu
Chiral metasurfaces can exhibit a strong circular dichroism, but it is limited by the complicated fabrication procedure and alignment errors. Here, a new type of self-aligned suspended chiral bilayer metasurface with only one-step electron beam lithography exposure is demonstrated. A significant optical chirality of 221° µm −1 can be realized using suspended metasurfaces with a thickness of 100 nm. Furthermore, this study experimentally demonstrates that such a structure is capable of label-free discrimination of the chiral molecules at zeptomole level, exhibiting a much higher sensitivity (orders of magnitude) compared to the conventional circular dichroism spectroscopy. The fundamental principles for chiral sensing using molecules–metasurfaces interactions are explored. Benefiting from the giant chiroptical response, the proposed metadevice may offer promising applications for ultrathin circular polarizers, chiral molecular detectors, and asymmetry information processing.
研究领域:
光学
·
材料科学
·
纳米技术
·
分析化学
✓ 已验证
DOI
PubMed
高影响因子
LIQUID CRYSTALS
·
2025
·
IF 2.2
Yutong Liu,Mengqi Xie,Yue Cao,Zhidong Liu,Dong Wang,Zhou Yang,Wanli He,Hui Cao,Yinjie Chen
In this paper, we propose a method to fabricate bilayer reflective broadband up to 1336 nm for PSCLC films. Unlike previous multilayer films, instead of using the polymeric network as the main diffusion channel for molecules between the upper and lower layers, the coverage of reflective bands in the partially visible and near-infrared regions is realised by the superposition of the upper and lower layers in conjunction with a small amount of diffusion of chiral molecules. We add the polymerisable chiral compounds and non-polymerisable chiral compounds with the same rotation direction into the liquid crystal mixing system of the upper and lower films respectively. Due to the presence of photoinitiators, when UV light irradiates the polymerisation, the polymerisable monomers including the polymerisable chiral compounds are rapidly polymerised in the near-light side, and the non-polymerisable monomers do diffusion movement to the near-light side, and the bilayer thin film forms the large-small-large pitch, thus realising broadband reflection. The bilayer PSCLC films reported in this study are expected to be promising candidates for a number of applications such as shielding infrared devices, energy-efficient windows for automobiles, and modern building facades.
研究领域:
材料科学
·
光学工程
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DOI
高影响因子
MICROCHIMICA ACTA
·
2023
·Vol. 190
·期 7
·1-11
·
IF 5.7
Li Yuchen,Xu Guangfu,Chen Jiaquan,Yu Tao,Miao Pandeng,Du Yingxiang
A novel chiral molecularly imprinted polymer TiO 2 nanoparticle was synthesized in one step for the enantioseparation of phenylalanine in coated capillary electrochromatography. To the author’s knowledge, the chiral molecularly imprinted nanomaterials have still not been reported, to date. Chiral molecularly imprinted TiO 2 nanomaterials (L-PHE@MIP(APTES-TEOS)@TiO 2 ) were used as a chiral stationary phase to separate the phenylalanine enantiomers in coated capillary electrochromatography (CEC). The imprinted coating was prepared from L-phenylalanine (L-PHE) as the template, TiO 2 nanoparticles (NPs) as the support substrate, 3-aminopropyltriethoxysilane (APTES) as the functional monomer, and tetraethyl silicate (TEOS) as the cross-linker. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were used for the characterization of the L-PHE@MIP(APTES-TEOS)@TiO 2 @capillary. Fourier transform infrared spectra (FT-IR), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA) were employed for the characterization of the L-PHE@MIP(APTES-TEOS)@TiO 2 . The effects of the applied voltage, pH value, buffer concentration, and acetonitrile content were investigated experimentally to determine the optimum conditions for CEC. The best resolution for phenylalanine enantiomers by CEC reached a value of 3.48. In addition, the specific recognition effect of L-PHE@MIP(APTES-TEOS)@TiO 2 on PHE enantiomers was studied by selective experiment. Finally, adsorption kinetic research, adsorption equilibrium isotherm study, and adsorption thermodynamic experiment were carried out to investigate the separation mechanism of PHE enantiomers with the L-PHE@MIP (APTES-TEOS)@TiO 2 @capillary, and the results were consistent with those of CEC experiments. Graphical Abstract
研究领域:
分析化学
·
材料科学
·
分离科学
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产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）