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SYNTHETIC METALS · 2018 · IF 2.526

Chiral recognition of dihydroxyphenylalanine enantiomers with (R)/(S)-2-Phenylpropionic acid grafted PProDOT electrochemical sensors

Junlong Niu,Liangmei Rao,Ping Liu,Wenwen Zhang,Wenna Zhang,Yinxiu Zuo,Keke Chai,Shuai Chen,Jingkun Xu,Xuemin Duan

Two novel chiral 3,4-dihydro-2 H -thieno[3,4- b ][1,4]dioxepine (ProDOT)-based electrochemical sensor , employing a pair of glassy carbon electrodes modified with chiral poly(2-Phenyl-propionic acid 3,4-dihydro-2 H -thieno[3,4- b ][1,4]dioxepin-3-ylmethyl ester) (PProDTM-PP), were utilized for the enantioselective detection of chiral 3,4-dihydroxyphenylalanine (DOPA). The enantioselective recognition between chiral PProDTM-PP modified glassy carbon electrodes and chiral DOPA was studied by using different electrochemical technologies. The redox activity and electrochemical stability of chiral PProDTM-PP was good. ( R )-PProDTM-PP and ( S )-PProDTM-PP showed higher peak current responses toward D -DOPA and L -DOPA, respectively. Furthermore, the recognition efficiencies of chiral PProDTM-PP are between 1.48 and 1.89, which is higher than chiral PEDOT-based electrochemical sensors (around 1.10). The chiral PProDTM-PP provides an alternative to chiral recognition.

研究领域: 生物化学 · 材料科学 · 分析化学
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JOURNAL OF MOLECULAR STRUCTURE · 2025 · IF 4.7

Terahertz absorption spectra of (S)-(+)-2-phenylpropanoic acid, (R)-(-)-2-phenylpropanoic acid and their racemic mixtures

Yusong Zhang,Wei Shi,Huanlin Li,Lei Yang,Lei Hou,Cheng Ma

Enantiomers often exhibit significant differences or even diametrically opposed effects in pharmacological activity, toxicological properties, and metabolic behavior. Single-enantiomer drugs frequently demonstrate distinct advantages over the racemate. Therefore, accurately distinguishing between enantiomers and racemate is particularly crucial in the fields of chemistry and biomedicine. Racemates, as mixtures of equal amounts of the enantiomers (levorotating and dextrorotating), exist in two forms: racemic mixtures and racemic compounds. Racemic compounds exhibit differences from their enantiomers in absorption spectra, whereas racemic mixtures do not. This study investigates the absorption spectra of ( S )-(+)-2-phenylpropionic acid, ( R )-(-)-2-phenylpropionic acid, and their racemates using terahertz time-domain spectroscopy technology. Experimental results indicate that the enantiomer exhibits absorption peaks similar to those of the racemic mixture, but with a significant difference in absorption intensity. Further combined with density functional theory (DFT), theoretical spectral calculations were performed on the solid state and solution enantiomers based on single molecule and unit cell models respectively. It was found that the enantiomeric simulation spectra were highly consistent. After the sample transitioned from solid to solution state, changes in hydrogen bonds would change its molecular vibration characteristics and intermolecular interaction patterns.

CAS / MDL: 7782-24-3 7782-26-5
研究领域: 物理化学 · 光谱学 · 手性化学 · 药学 · 计算化学
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Bioresources and Bioprocessing · 2019 ·Vol. 6 ·期 1 ·1-12 · IF 0

Production of enantiopure (R)- or (S)-2-hydroxy-4-(methylthio)butanoic acid by multi-enzyme cascades

Zhang Can,Song Wei,Liu Jia,Chen Xiulai,Liu Liming

( R )- or ( S )-2-Hydroxy-4-(methylthio)butanoic acid (HMTBA) is used as a poultry nutritional supplement and to treat renal failure disease. Herein, we report an artificially designed biocatalytic cascade process, which uses l -methionine to synthesize ( R )- or ( S )-HMTBA. This biocatalysis cascade comprises a basic module and two different extender modules and operates in a modular assembly manner. The basic module responsible for the transformation of l -methionine to α-keto-γ-methylthiobutyric acid (KMTB) is comprised of the l -amino acid deaminase. Two different extender modules responsible for the transformation of KMTB to ( R )- or ( S )-HMTBA are comprised of the R/S-specific lactate dehydrogenase in combination with the formate dehydrogenase, respectively. Engineered Escherichia coli catalysts, one containing the basic module, the other containing the one of two different extender modules, produced 97.6 g L −1 ( R )-HMTBA and 96.4 g L −1 ( S )-HMTBA with a yield of 96.9% and 95.8% at the large scale (1 L) using a two-stage strategy in one pot, respectively. Therefore, this biocatalytic process lays the foundation for the industrial-scale conversion of low-cost l -amino acids to corresponding high-value enantiopure chiral 2-hydroxy acids.

研究领域: 生物技术 · 酶工程 · 代谢工程 · 合成生物学
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GREEN CHEMISTRY · 2026 · IF 9.2

A simple self-corrosion method constructs the Ni 3 S 2 @FeOOH heterostructure enables industrialized seawater oxidation

Yujie Yuan,Ziyu Yang,Hao Wang,Tong Wu,Xiaoyi Zhang,Lin Chen,Zhaohuan Wei,Rui Wang,C. Venkata Reddy,Jaesool Shim,Hui Tang

Electrocatalytic seawater splitting holds immense promise as a green hydrogen production technology; however, the anodic oxygen evolution reaction (OER) confronts formidable challenges arising from the high concentration of chloride ions (Cl -) and other impurities in seawater. Herein, we develop a facile two-step immersion corrosion strategy to successfully construct a Ni 3 S 2 @FeOOH heterojunction electrocatalyst on nickel foam (NF) tailored for industrial alkaline seawater oxidation. Integrating density functional theory (DFT) calculations and experimental characterizations, we demonstrate that Ni 3 S 2 @FeOOH selectively enriches OH -while repelling Cl -during OER in alkaline seawater electrolytes. Notably, in situ leaching of SO 4 2-from the electrode triggers efficient self-reconstruction, facilitating the generation of high-valence metal active sites. The asfabricated catalyst exhibits remarkable OER performance with a low overpotential of 390.5 mV at an ultrahigh current density of 1000 mA cm -2 in alkaline seawater. Moreover, it maintains exceptional electrochemical stability for over 1000 hours at the industrial current density of 1000 mA cm -2 . This work provides a scalable strategy for constructing self-reconstructing electrocatalysts that promote highvalence metal site formation and efficient Cl -repulsion in alkaline seawater oxidation.

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ACS Omega · 2023 · IF 4.1

Synthesis of a Lignin-Enhanced Graphene Aerogel for Lipase Immobilization

Hong Zhang,Xin Zhang,Lei Wang,Bo Wang,Xu Zeng,Bo Ren,Xiaodong Yang

A novel lignin-enhanced graphene aerogel (LGA) was prepared by one-step hydrothermal synthesis, and lipase from Pseudomonas sp. (PSL) was immobilized on LGA successfully by interfacial activation. The catalytic activity and enantioselectivity of LGA-PSL for the preparation of (S)-2-octanol by an enantioselective transesterification were improved obviously. The characterization of LGA and LGA-PSL was performed. X-ray diffraction and Fourier transform infrared spectroscopy demonstrated the formation of numerous electrostatic and hydrogen bonds between lignin and graphene in the aerogel structure. In addition, the specific surface area pore size analyzer (BET) test proved that the introduction of lignin significantly increased the specific surface area and pore size of the aerogel material, which improved the immobilization efficiency of lipase in the aerogel. The introduction of lignin has changed the original lamellar structure of the graphene oxide (GO) aerogels. The lignin cross-linked with the GO lamellae through hydrogen bonding, causing a porous structure to form between the original lamellae, thus increasing their specific surface area. The immobilized lipase (LGA-PSL) was used for the preparation of (S)-2-octanol by an enantioselective transesterification, and the reaction conditions for this enzymatic transesterification had been optimized. LGA-PSL exhibited a high catalytic performance and could be reused four times in this reaction. Based on these results, LGA as an immobilization carrier had potential applications in the industrial application of lipase.

CAS / MDL: 9005-53-2
研究领域: 材料科学 · 生物催化 · 酶工程
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MICROCHIMICA ACTA · 2026 ·Vol. 193 ·期 10 ·676 · IF 5.4

Chiral metal-organic cage core-shell composite UMOP-S-2- Ppa@SiO2 used as stationary phase for HPLC enantioseparation

He Yi-Juan,Zhu Yu-Lan,Zhao Yun-Qiao,He Ren-Xiu,Xie Sheng-Ming,Wang Bang-Jin,Zhang Jun-Hui,Yuan Li-Ming

A facile one-pot strategy was developed to construct a core-shell UMOP-S-2-Ppa@SiO 2 composite using (S)-2-phenylpropionic acid as chiral selector. The prepared UMOP-S-2-Ppa@SiO 2 composite was utilized as a novel chiral stationary phase (CSP) for HPLC enantioseparation. Under normal-phase HPLC conditions, the packed column afforded effective enantioseparation for 18 racemates including alcohols, aldehydes, esters, ketones, amines, and epoxy compounds, among which 11 pairs of enantiomers achieved baseline resolution. Compared with the widely used Chiralpak AD-H and Chiralcel OD-H columns, the developed chiral column exhibited good chiral separation complementarity. It can efficiently resolve some racemates that fail to be separated by the above commercial columns. The column also demonstrated satisfactory repeatability and stability, and the relative standard deviations of retention time and peak area remained below 1.0% after 250 consecutive injections. These results demonstrate that chiral metal-organic cages(MOC)@SiO 2 core-shell composites prepared via a post-synthetic modification strategy hold great promise for HPLC enantioseparation, offering new insights into the development of MOC-based materials for chromatographic applications. Graphical

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ENZYME AND MICROBIAL TECHNOLOGY · 2014 · IF 2.966

Immobilized Candida antarctica lipase B on ZnO nanowires/macroporous silica composites for catalyzing chiral resolution of (R,S)-2-octanol

Chuan-Yang Shang,Wei-Xun Li,Rui-Feng Zhang

ZnO nanowires were successfully introduced into a macroporous SiO 2 by in situ hydrothermal growth in 3D pores. The obtained composites were characterized by SEM and XRD, and used as supports to immobilize Candida antarctica lipase B (CALB) through adsorption. The high specific surface area (233   m 2 /g) and strong electrostatic interaction resulted that the average loading amount of the composite supports (196.8   mg/g) was 3–4 times of that of macroporous SiO 2 and approximate to that of a silica-based mesoporous material. Both adsorption capacity and the activity of the CALB immobilized on the composite supports almost kept unchanged as the samples were soaked in buffer solution for 48   h. The chiral resolution of 2-octanol was catalyzed by immobilized CALB. A maximum molar conversion of 49.1% was achieved with 99% enantiomeric excess of ( R )-2-octanol acetate under the optimal condition: a reaction using 1.0   mol/L ( R , S )-2-octanol, 2.0   mol/L vinyl acetate and 4.0   wt.% water content at 60   °C for 8   h. After fifteen recycles the immobilized lipase could retain 96.9% of relative activity and 93.8% of relative enantioselectivity .

研究领域: 生物化学 · 材料科学 · 催化工程
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Progress in Natural Science-Materials International · 2021 · IF 3.607

Immobilization of cross-linked In-doped Mo(O,S)2 on cellulose nanofiber for effective organic-compound degradation under visible light illumination

Hairus Abdullah,Chi-Ning Hsu,Hardy Shuwanto,Noto Susanto Gultom,Worku Lakew Kebede,Chang-Mou Wu,Chiu-Chun Lai,Ri-Ichi Murakami,Masayuki Hirota,Antonio Norio Nakagaito,Dong-Hau Kuo

Relatively small amounts of In-doped Mo(O,S) 2 (IMS) catalysts (10%, 20%, and 30%) were deposited on cellulose nanofiber (CNF) by cross-linking them with functional groups of siloxane and epoxy to form CNF-IMS hybrid composites. The as-prepared hybrid composites were characterized and tested their performances toward the photo degradations of cationic (MB and RhB) and anionic (MO) dyes. As indium was doped into Mo(O,S) 2 lattice to form solid-solution, the charge transfer and photocarrier separation during the catalytic reaction were simultaneously enhanced as probed with electrochemical impedance spectroscopy and photoluminescence measurements, respectively. To ensure the catalyst on CNF was well deposited and recyclable, the hybrid composite was evaluated with a reusability experiment to show the stability performance in degrading organic dyes. It was found the environmentally friendly CNF-IMS hybrid composite was relatively stable during the reusability experiment, indicating no catalyst powder was leached out during the photocatalytic reaction. The photoreaction mechanism was convinced by radical-scavenging experiments to show that hydroxyl and superoxide played essential roles for the organic dye degradations in visible-light illuminated conditions. The cross-linked organic/inorganic hybrid catalyst showed a prospective visible light active material not only to solve the environmental issue due to the leaching of nanoparticles but also to lower the post-treatment/recycling cost of photocatalyst in industrial application.

研究领域: 材料科学 · 环境科学
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MOLECULAR PHARMACEUTICS · 2023 · IF 4.9

Naphthyl-Poly(S-((2-carboxyethyl)thio)-l-cysteine) Peptide Amphiphiles with Different Degrees of Polymerization: Synthesis, Self-Assembly, pH/Reduction-Triggered Drug Release, and Cytotoxicity

Qinming Xu,Xing Li,Jingang Yang,Yan Zhang,Xiaocui Deng,Gang Li,Qingmei Yuan

Four peptide amphiphiles (PA1-4) with different degrees of polymerization (DP = 40, 15, 10, and 6) were synthesized by Fuchs-Farthing and ring-opening polymerization followed by post-polymerization modification, as fully characterized by 1H NMR, FT-IR, gel permeation chromatography, and circular dichroism (CD) spectroscopy. It was found that PAs could self-assemble to form regular spherical micelles in low-concentration (about 1 mg/mL) aqueous solution, which had different contents of secondary structures and mainly adopted random coil conformations. The water solubility of PAs increases with the increase of DP, the polypeptide chain stretches randomly in water, the β-sheets decrease, and the random coil conformations dominate. When the pH of PA solution decreases or increases, intramolecular hydrogen bonds break, and molecular chains stretch, leading to a decrease of α-helix, turn conformations, and an increase of β-sheets. Meanwhile, the particle size of micelles increases. At around 0.4 mg/mL, the hemolysis ability of PA2 is negligible at pH 7.4 and 6.5 and about 33% at pH 5.5. Cisplatin (CDDP) was linked to micelles by coordination bonds to explore their potential as drug carriers, exhibiting controlled pH and reduction in dual drug release effects. MTT assay showed that the HeLa cell viability was 78% when cultured in the 13.5 μg/mL PA2 blank micelles for 2 days, while the cell viability was 60% in the CDDP-loaded micelles. Furthermore, a high concentration of PA2 (about 100 mg/mL) could self-assemble into a fibrous hydrogel at pH 5.5, which self-healed 2 h after incision and self-degraded 71% within 14 days. The CDDP-loaded fiber hydrogel exhibited a sustained release effect similar to the CDDP-loaded micelles. The cytotoxicity of CDDP-loaded fibers at 48 h was detected to be the same as that of the same amount of CDDP, and the cell viability was 7%. Therefore, we provide a new strategy for the synthesis of amphiphilic peptides with potential applications in nano-drug carriers and cancer therapy.

研究领域: 生物化学 · 药学 · 纳米医学 · 肿瘤学
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY · 2024 ·Vol. 60 ·期 10 ·1999-2003 · IF 0.8

Synthesis of (S)-2-{(R)-Hydroxy[2-(trifluoromethyl)phenyl]­methyl}cyclohexan-1-one Using (1R,2R)-2-(Piperidin-1-yl)­cyclohexan-1-amine as a Catalyst

Li C. L.,Wang S. Y.,Zhan M. R.,Chen C. C.,Wang Z. X.

Chiral monosubstituted cyclohexanediamine catalyst, namely (1 R ,2 R )-2-(piperidin-1-yl)cyclo­hexan-1-amine ( Cat1 ) has been efficiently synthesized and used to catalyze the aldol reaction of cyclohexanone and 2-(trifluoromethyl)benzaldehyde to obtain ( R )-2-{( S )-hydroxy[2-(trifluoromethyl)phenyl]methyl}cyclo­hexan-1-one. The catalyst (20 mol %) provided high yield (up to 85%) and excellent enantioselectivity (95.6% ee ) in water solution in three parallel tests.

研究领域: 有机化学 · 催化化学
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JOURNAL OF CHROMATOGRAPHY A · 2021 · IF 4.759

Highly sensitive novel fluorescent chiral probe possessing (S)-2-methylproline structures for the determination of chiral amino compounds by ultra-performance liquid chromatography with fluorescence: An application in the saliva of healthy volunteer

Xi-Ling Li,Yu Han,Yuan Huang,Xiaoqi Sun,Shuyun Xiao,Jun Zhe Min

We developed a novel fluorescent chiral probe, DBD-trans-2-methyl-L-proline (DBD-M-Pro), which can be used to target recognition of amino functional groups using chiral resolution. To investigate the chiral resolution efficiency, 20 chiral amino enantiomers (19 DL-amino acids and phenylethylamine) were labeled using ultra-performance liquid chromatography (UPLC) with a fluorescence (FL) system. Diastereomers were formed by the reactions of DBD-M-Pro with enantiomers of amino functional groups at 60 °C for 60 min and detected on a BEH C18 column (100 × 2.1 mm, 1.7 μm). Gradient elution of 10 mM ammonium acetate with 0.05% formic acid (FA) aqueous solution and 0.1% FA acetonitrile or 0.1% FA methanol solution was performed at an excitation wavelength (Ex) 460 nm and emission wavelength (Em) 550 nm. Each resulting derivative of D- and L- type was effectively separated. The results showed that the resolution (Rs) of 17 amino acids and phenylethylamine (PEA) in the range of 1.59–24.11, except for histidine (His) (Rs = 1.32) and serine (Ser) (Rs = 1.47), achieved completely separation. The DBD-M-Pro chiral probe has a robust chiral selectivity for D-amino acids. Furthermore, a new method for the simultaneous determination of six DL-amino acids (Pro, Val, Trp, Phe, Leu, Lys) in human saliva was developed. The proposed method showed resolution values of 1.78–16.38, and an excellent linear relationship was obtained in the range of 2.5–500 pmol ( R 2  ≥ 0.9990). The limit of detection (S/ N  = 3) ranged from 0.5 to 3.75 pmol. The intra-day and inter-day coefficient of variation (CV) were within the range of 1.75–11.73%. The average addition recoveries in saliva ranged from 95.99 to 106.97%. The methodology was used to determine the content of DL-amino acids and the D/L-amino acid ratio in the saliva of 40 healthy volunteers (15 males and 25 females), as well as evaluating the differences between men and women. Our study suggests that the DBD-M-Pro chiral probe could be an effective tool for screening potential D-amino acid biomarkers in disease.

研究领域: 分析化学 · 生物化学 · 医学诊断
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