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JOURNAL OF MOLECULAR LIQUIDS · 2020 · IF 5.065

Solid-liquid equilibrium and dissolution thermodynamics of 4-Methylumbelliferon in different solvents

Jinbo Ouyang,Jian Chen,Haiqing Huang,Limin Zhou,Xin Huang

Solubility of 4-Methylumbelliferon in different pure solvents, including polar and apolar solvents, were firstly measured at varied temperatures under 0.1 MPa by a gravimetric method. Results showed that solubility in all solvents increase with rising of temperature, and 4-Methylumbelliferon is most soluble in acetone, followed by 1-butanol, isopropanol, 1-propanol, isobutanol , ethyl acetate , ethanol, methanol, methyl acetate , acetonitrile , butyl acetate and water. The experimental solubility data were correlated by several thermodynamic models, including modified Apelblat model, NRTL model and Wilson model. The accuracy of these models is determined by calculation of mean relative deviation ( MRD ). Moreover, dissolution thermodynamics i.e. dissolution enthalpy, dissolution Gibbs energy and dissolution entropy, were calculated by using Wilson equations.

CAS / MDL: 90-33-5
研究领域: 化学工程 · 物理化学
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APPLIED BIOCHEMISTRY AND MICROBIOLOGY · 2017 ·Vol. 53 ·期 1 ·85-93 · IF 0.659

Glycosylation and sulfation of 4-methylumbelliferone by Gliocladium deliquescens NRRL 1086

Fan N.,Du C. H.,Xu J. Q.,Xu Y. X.,Yu B. Y.,Zhang J.

The aim of the study was to expand the substrate scope of Gliocladium deliquescens NRRL 1086 and generate coumarin glycosides using 4-methylumbelliferone (4-MU) as a substrate. The obtained results indicated that 4-MU can be metabolized to its glucoside (M1) and sulfate conjugate (M2), and the structures of the metabolites were elucidated by spectroscopic or enzymatic methods. Time course experiments detected that nearly 90% of 4-MU could be metabolized within 24 h, and the maximum yield of M1 could reach as high as 32%. Further tests revealed that the glucose concentration in the medium had little effect on the yield of M1 but time of 4-MU-adding could markedly affect the glycosylation procedure, and the favorable time to accumulate M1 was in the 12 or 24 h-old stage II culture, while in the 36 h-old or even older stage II culture, the substrate was almost metabolized to M2. The attempts to alter the ratio between M1 and M2 were performed by addition of quercetin and S-tetrahydroberberrubine or reduction of the sulfate concentration in the culture medium. Herein we describe, to the best of our knowledge, the first example of simultaneously microbial glycosylation and sulfation of coumarins.

研究领域: 微生物学 · 有机化学 · 药理学
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2016 · IF 2.653

Simultaneous determination of umbelliferone and scopoletin in Tibetan medicine Saussurea laniceps and traditional Chinese medicine Radix angelicae pubescentis using excitation-emission matrix fluorescence coupled with second-order calibration method

Li Wang,Hai-Long Wu,Xiao-Li Yin,Yong Hu,Hui-Wen Gu,Ru-Qin Yu

A chemometrics-assisted excitation-emission matrix (EEM) fluorescence method is presented for simultaneous determination of umbelliferone and scopoletin in Tibetan medicine Saussurea laniceps (SL) and traditional Chinese medicine Radix angelicae pubescentis (RAP). Using the strategy of combining EEM fluorescence data with second-order calibration method based on the alternating trilinear decomposition (ATLD) algorithm, the simultaneous quantification of umbelliferone and scopoletin in the two different complex systems was achieved successfully, even in the presence of potential interferents. The pretreatment is simple due to the “second-order advantage” and the use of “mathematical separation” instead of awkward “physical or chemical separation”. Satisfactory results have been achieved with the limits of detection (LODs) of umbelliferone and scopoletin being 0.06   ng   mL −   1 and 0.16   ng   mL −   1 , respectively. The average spike recoveries of umbelliferone and scopoletin are 98.8   ±   4.3% and 102.5   ±   3.3%, respectively. Besides, HPLC-DAD method was used to further validate the presented strategy, and t- test indicates that prediction results of the two methods have no significant differences. Satisfactory experimental results imply that our method is fast, low-cost and sensitive when compared with HPLC-DAD method.

CAS / MDL: 93-35-6 92-61-5
研究领域: 中药分析 · 化学计量学 · 药物分析
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Molecular Medicine Reports · 2025 ·Vol. 32 ·期 1 ·1-12 · IF 3.5

Inhibitory effects of umbelliferone on carbon tetrachloride-induced hepatic fibrosis in rats through the TGF‑β1‑Smad signaling pathway

Lijuan Liang,Zhiheng Dong,Ziqing Shen,Yifan Zang,Wenlong Yang,Lan Wu,Lidao Bao

Hepatic fibrosis (HF) is a critical marker of advanced‑stage chronic liver disease and involves pivotal contributions from hepatic stellate cells (HSCs). Currently, there are no effective treatments for HF. Umbelliferone (7‑hydroxycoumarin; UMB) is a natural compound with significant anti‑inflammatory, antioxidant and anti‑tumor activities. However, its potential efficacy in treating HF has not been studied. The present study explored the protective effects of UMB against HF, targeting the TGF‑β1‑Smad signaling pathway to explore the underlying mechanisms of UMB. Carbon tetrachloride (CCl4) was injected intraperitoneally to induce HF in rats and primary HSCs were treated in vitro with UMB to investigate the improvement effect of UMB on HF. The levels of fibrosis markers, inflammation, oxidative stress and TGF‑β1‑Smad signaling pathway in the rat liver tissue and HSCs were detected using hematoxylin and eosin staining, enzyme‑linked immunosorbent assay, reverse transcription‑quantitative PCR, Cell Counting Kit‑8 and western blotting. The improvement in liver histopathology, liver function indexes and fibrosis markers demonstrated that UMB markedly inhibited the CCl4‑induced HF and inflammation in the rats. Additionally, UMB prominently reduced the pro‑inflammatory factors and oxidative stress levels. In vitro, UMB markedly inhibited primary HSC activation and decreased alpha‑smooth muscle actin and collagen I expression. The mechanism experiment proved that UMB inhibited the TGF‑β1‑Smad signaling pathway and ameliorated HF. The present study was the first to demonstrate, to the best of the authors' knowledge, that UMB might be a promising natural active compound for treating HF. Its therapeutic effect is associated with its modulation of the TGF‑β1‑Smad signaling pathway.

CAS / MDL: 56-23-5
研究领域: 药理学 · 肝脏病学
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DYES AND PIGMENTS · 2022 · IF 5.122

Dual-emitting ZIF-8⊃4-MU@Zn2GeO4:Mn2+ nanocomposites for ratiomertic luminescent thermometer and information encryption

Zishuo Yi,Weiling Huang,Yan Xu

Dual-emitting ratiometric optical thermometers with the advantages of excellent self-calibration and high-sensitivity have become a research hot spot. Herein, a dual-emissive 4-methylumbelliferone encapsulated ZIF-8 (ZIF-8⊃4-MU) modified Zn 2 GeO 4 :Mn 2+ nanocomposite was simply prepared by adding Zn 2 GeO 4 :Mn 2+ nanorods into a methanol solution containing 4-methylumbelliferone (4-MU), zinc (II) nitrate hexahydrate, and 2-methylimidazole. Accompanying with the self-assembly of ZIF-8⊃4-MU, the binding affinity of Zn 2+ ions to the surface of Zn 2 GeO 4 :Mn 2+ nanorods enables the formation of ZIF-8⊃4-MU@Zn 2 GeO 4 :Mn 2+ nanocomposite. The photoluminescence violet-blue (420 nm) and green emissions (531 nm) of the nanocomposite can be ascribed to the two independent luminescent centers of 4-MU dyes confined in ZIF-8 and the characteristic transition of 4 T 1 - 6 A 1 for Mn 2+ ions doped in Zn 2 GeO 4 , respectively. The fluorescent intensity ratios (FIRs) of 4-MU to Mn 2+ (I 420 nm /I 531 nm ) showed excellent self-calibrating temperature monitoring functions with a maximum relative sensitivity (S r ) of 1.82%· o C −1 and stable reusability in the temperature range of 20–100 °C. Also, the ZIF-8⊃4-MU@Zn 2 GeO 4 :Mn 2+ hybridized polyvinyl alcohol (PVA) transparent film showed a similar multi-emitting behavior, as well as good processability and tensile properties . Benefiting from the excitation-dependent emitting property of ZIF-8⊃4-MU@Zn 2 GeO 4 :Mn 2+ , a multiple optical encryption of digital information was successfully realized based on a two-dimensional code, achieving an enhanced security level for preventing counterfeiting. This proof-of-concept study offers a feasible assembled way in fabricating multi-mode luminescent nanocomposites for ratiometric temperature sensing and information encryption .

研究领域: 材料科学 · 光学
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ANALYTICAL BIOCHEMISTRY · 2018 · IF 2.275

Fluorescent microplate assay method for high-throughput detection of lipase transesterification activity

Jianyong Zheng,Wei Wei,Xing Lan,Yinjun Zhang,Zhao Wang

This study describes a sensitive and fluorescent microplate assay method to detect lipase transesterification activity. Lipase-catalyzed transesterification between butyryl 4-methyl umbelliferone (Bu-4-Mu) and methanol in tert -butanol was selected as the model reaction. The release of 4-methylumbelliferone (4-Mu) in the reaction was determined by detecting the fluorescence intensity at λ ex 330 nm and λ em 390 nm. Several lipases were used to investigate the accuracy and efficiency of the proposed method. Apparent Michaelis constant ( K m) was calculated for transesterification between Bu-4-Mu and methanol by the lipases. The main advantages of the assay method include high sensitivity, inexpensive reagents, and simple detection process.

研究领域: 生物化学 · 酶学
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INDUSTRIAL CROPS AND PRODUCTS · 2023 · IF 5.9

Comprehensive multi-omics analysis reveals the importance of CtCOSY in the energy metabolism and coumarin biosynthesis in Clematis terniflora DC

Minglei Tao,Shengzhi Liu,Yaohan Li,Amin Liu,Zijian Sun,Vinesh Maharaj,Shouxin Li,Jingkui Tian,Wei Zhu

Coumarin synthase (COSY) is the key enzyme involved in the coumarin biosynthesis. Although it has been identified firstly in Arabidopisis thaliana , there is little known about the COSY gene function in Clematis terniflora DC. Our previous study indicated that the contents of coumarins in C. terniflora leaf were increased under ultraviolet-B radiation and dark treatments (UV-D). To reveal the function of COSY in C. terniflora and its role in response to UV-D stress, the functional characterization of CtCOSY which was identified as a BADH acyltransferase was performed. The results showed that coupled reaction of CtCOSY with 4-coumarinyl CoA-ligase in vitro to produce umbelliferone . Moreover, the functions of CtCOSY in response to UV-D stress was studied using proteomic and metabolomic techniques. Multi-omics analyses of CtCOSY -silenced C. terniflora indicated that as well as a limitation of coumarin synthesis, aspects of the energy metabolism, such as the TCA cycle, were disturbed in these plants. Under UV-D stress, CtCOSY affected the biosynthesis of phenylpropanoids in C. terniflora , resulting in the improvement of coumarin biosynthesis and affecting purine metabolism. This study provides the evidences of CtCOSY responsible for the biosynthesis of coumarin in C. terniflora and the resistance to UV-D stress.

研究领域: 植物生物化学 · 分子生物学 · 胁迫生理学
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2024 · IF 7.7

Biomimetic immobilization of α-glucosidase inspired by antibody-antigen specific recognition for catalytic preparation of 4-methylumbelliferone

Shuang Guo,Shuo Liu,Chang Liu,Yi Wang,Dongyu Gu,Jing Tian,Yi Yang

Immobilization technology plays an important role in enhancing enzyme stability and environmental adaptability. Despite its rapid development, this technology still encounters many challenges such as enzyme leakage, difficulties in large-scale implementation, and limited reusability. Drawing inspiration from natural paired molecules, this study aimed to establish a method for immobilized α-glucosidase using artificial antibody-antigen interaction. The proposed method consists of three main parts: synthesis of artificial antibodies, synthesis of artificial antigens, and assembly of the artificial antibody-antigen complex. The critical step in this method involves selecting a pair of structurally similar compounds: catechol as a template for preparing artificial antibodies and protocatechualdehyde for modifying the enzyme to create the artificial antigens. By utilizing the same functional groups in these compounds, specific recognition of the antigen by the artificial antibody can be achieved, thereby immobilizing the enzymes. The results demonstrated that the immobilization amount, specific activity, and enzyme activity of the immobilized α-glucosidase were 25.09 ± 0.10 mg/g, 5.71 ± 0.17 U/mg protein and 143.25 ± 1.71 U/g carrier , respectively. The immobilized α-glucosidase not only exhibited excellent reusability but also demonstrated remarkable performance in catalyzing the hydrolysis of 4-methylumbelliferyl-α-D-glucopyranoside.

CAS / MDL: 609-99-4
研究领域: 生物技术 · 酶学 · 催化 · 材料科学
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RSC Advances · 2019 ·Vol. 9 ·期 41 ·23658-23665 · IF 3.049

A spherical poly(acrylic acid) brush–enzyme block with high catalytic capacity for signal amplification in digital biological assays

Yibei Wang,Zehang Gao,Jingwei Yi,Hongbo Zhou,Xiaoxia Fang,Hong Xu,Jianlong Zhao,Hongchen Gu

Ultrasensitive determination of some ultra-low abundance biological molecules closely related to diseases is currently a wide concern and urgent issue to be addressed. Here, a spherical poly(acrylic acid)–alkaline phosphatase (SP–AKP) signal amplification block using spherical poly(acrylic acid) brush nanoparticles (SP) as the immobilized carriers was designed and synthesized optimally first. The results show that a single SP–AKP with high enzyme binding capacity and high catalytic ability (up to about 4800 effective free AKP per SP–AKP) has much greater fluorescence signal amplification ability than a single free AKP or SiO2–COOH–AKP. Then, a droplet generation microfluidic chip was prepared successfully, and the SP–AKP was loaded and confined in a 14 pL droplet by adjusting its concentration to ensure at most one SP–AKP was encapsulated in each droplet according to Poisson's theory. Finally, the fluorescence signals produced by 4-methylumbelliferyl phosphate (4-MUP) catalyzed via SP–AKP within 6 min were sufficient to be detected by a fluorescence microscope. Thus, the digital signal distribution of “1/0” (signal/background) was obtained, making this SP–AKP signal amplification block a promising enzyme label for potential high sensitivity digital biological detection applications.

CAS / MDL: 107-06-2
研究领域: 分析化学 · 生物化学 · 纳米技术 · 生物医学工程
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MICROCHEMICAL JOURNAL · 2025 · IF 5.1

A novel Eu(III)-based nano-aggregation for ratiometric fluorescence sensing of tetracycline

Zhen-Wen Zhang,Ao-Jun Qiu,Geng-Jin-Sheng Cheng,Yu Fan,Yu Xiao,Yan-Zhu Liu,Qian-Yong Cao

Tetracycline detection remains an important research topic in the bioenvironmental field today. This paper reports a novel amphiphilic Eu(III) complex DO 3 AC 12 -Eu for single signal and ratiometric fluorescence detection of tetracycline (TC) in aqueous solution. DO 3 AC 12 -Eu can self-assemble micelle-like nano-aggregation in aqueous solution with no fluorescence. After addition of TC, the Eu(III)-based emission was observed for the effective antenna effect from TC to Eu(III) center. In addition, DO 3 AC 12 -Eu can load 4-methylumbelliferone sodium (MU) as a fluorescence reference to form DO 3 AC 12 -Eu/MU co-assembly nano-aggregation with a blue emission at 450 nm. Based on the TC-induced antenna effect and inner filter effect mechanism between TC and MU, DO 3 AC 12 -Eu/MU exhibits a ratiometrically fluorescent response toward TC, with increasing Eu(III)-based emission at 615 nm, and decreasing MU-based emission at 450 nm. Importantly, DO 3 AC 12 -Eu/MU exhibits superior sensitivity and selectivity over DO 3 AC 12 -Eu . The detection limit of DO 3 AC 12 -Eu/MU toward TC is 0.82 nM, far lower than that of DO 3 AC 12 -Eu (9.5 nM). Furthermore, DO 3 AC 12 -Eu/MU assembly has been successfully used for on-site and real-time detection of TC in food samples by using the smartphone-based visualization method and test gel.

研究领域: 分析化学 · 环境监测 · 生物环境科学 · 荧光传感技术 · 纳米科技 · 配位化学 · 食品安全检测
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