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SCIENCE OF THE TOTAL ENVIRONMENT · 2024 · IF 8.2

Unveiling responses and mechanisms of spice crop chive exposure to three typical pesticides using metabolomics combined with transcriptomics, physiology and biochemistry

Yibo Dong,Jiaohong Li,Zhenxiang Guo,Lei Han,Jing Zhao,Xiaomao Wu,Xiangsheng Chen

Pesticides are frequently used to control target pests in the production of spice crops such as chives ( Allium ascalonicum ). However, little information is available on the responses and underlying mechanisms of pesticide exposure in this crop. Our findings revealed that the uptake, transportation, and subcellular distribution of three typical pesticides—the fungicide pyraclostrobin (PAL), insecticide acetamiprid (ATP), and herbicide pendimethalin (PND) in chives, as well as their physiological, biochemical, metabolic, and transcriptomic responses—were dependent on pesticide properties, especially hydrophobicity. The distribution of PAL and PND in chives decreased in the order root > stem > leaf, but the distribution order of ATP was the opposite. The proportion of PAL and PND in the solid phase of the root cells gradually increased, but ATP mainly existed in the cell-soluble component, indicating that the latter had an upward translocation ability and thus mainly accumulated in the leaves. Malondialdehyde levels in chive leaves were not significantly affected by exposure to these pesticides; however, the activities of superoxide dismutase (SOD) and catalase (CAT) in chive leaves increased significantly. Moreover, these pesticides exhibited critical differences in chive responses through the interaction of metabolites and regulation of differentially expressed genes. PAL dramatically influenced five carbohydrate metabolic pathways (34.35 %), disturbing the starch-to-sucrose balance. ATP strongly affected five amino acid (AC) metabolic pathways (33.38 %), enhancing four free amino acid levels. PND notably affected eight fatty acid (FA) metabolic pathways (25.38 %), increasing two unsaturated and decreasing one saturated FA. Simultaneously, PND, ATP, and PND accumulated in the chives could be detoxified through metabolic pathways mediated by cytochrome P450 (P450) and glycosyltransferase (GT)/glutathione S-transferase (GST), producing phase I (7, 4, and 5) and II (11, 13, and 10) metabolites, respectively. This study provides important molecular insights into the responses and underlying mechanisms of spice crop exposure to pesticides.

研究领域: 植物科学 · 环境毒理学 · 分子生物学
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MICROCHEMICAL JOURNAL · 2022 · IF 5.304

Derivatization reaction-based multi-spectroscopic techniques for ultrasensitive and rapid detection of phosphate in food using Nile blue A as probe

Zhichen Deng,Jiahua Zhang,Zhengquan Su,Yan Bai,Jincan He

Herein, a multi-spectroscopic assay based on a derivatization reaction was proposed for phosphate detection. In this assay, the phosphate with weak spectral signals was transformed to a large ion-association complex via a derivatization reaction. The operation procedure of the assay was easily performed by physically mixing sulfuric acid, derivatization reagent, phosphate (or sample solution), and dye probe (Nile blue A) for 10 min. Considerable changes in three types of spectral signals, i.e., resonance Rayleigh scattering (RRS), fluorescence, and ultraviolet-visible absorption, could be achieved. Under certain conditions, good linear relationship was obtained between each of the three signal variations and the phosphate concentration. The assay shows good selectivity and high sensitivity with limits of detection (LOD) of 4.8, 4.9 and 5.2 ng/mL for the RRS method, fluorophotometry and spectrophotometry, respectively. The multi-spectroscopic assay was applied to detect phosphate in real food samples, achieving recoveries of 93.3 %–109.6 % and relative standard divisions of 1.8 %–7.1 %. Owing to its speediness, easy operation, high sensitivity, good selectivity, self-comparison function, the multi-spectroscopic assay exhibits great potential for determination of phosphate in complex samples and provides an instructive strategy for detecting analytes with no or weak spectral signal.

研究领域: 分析化学 · 食品科学
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ANALYTICAL CHEMISTRY · 2022 · IF 8.008

Rapid Derivatization of Phenolic and Oxime Hydroxyl with Isonicotinoyl Chloride under Aqueous Conditions and Its Application in LC–MS/MS Profiling Multiclass Steroids

Hui-Yang Liao,Xuan Xiao,Rui Peng,Juan Le,Hai-Bo Wang,Shao-Ting Wang

Quantification of steroids possesses a crucial clinical value in early diagnosis and prognosis evaluation of various endocrine diseases. However, it is still challenging to realize feasible analysis of estrogens, androgens, progestogens, and corticoids within one single workflow. In this study, two derivatization reactions were newly designed for improvement: (1) acylation of phenolic hydroxyl on estrogens with isonicotinoyl chloride (INC) under the catalysis of 4-dimethylaminopyridine and (2) post-modification of oxime hydroxyl on hydroxylamine-pretreated ketosteroids with INC. Both reactions could conduct instantaneously at room temperature under aqueous conditions. Moreover, the resulting phenolic-INC and oxime-INC esters exhibited favorable MS responses. Through integrating these derivatization strategies with cold-induced phase separation technology, a feasible LC–MS/MS method was developed for simultaneous quantification of 15 multiclass steroids with proper sample consumption (50 μL serum), satisfying sensitivity (lower limit of quantitation at 0.01–5.00 ng/mL) and high throughput (40 min for sample-preparation). The practical applicability was tested by detecting 30 real samples from pregnant and non-pregnant women. The obtained results showed a good agreement with a previous validated methodology.

研究领域: 临床医学 · 分析化学
✓ 已验证 DOI PubMed 高影响因子
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TALANTA · 2021 · IF 6.057

Sensitive detection of trace 4-methylimidazole utilizing a derivatization reaction-based ratiometric surface-enhanced Raman scattering platform

Lichen Gou,Xiaoliang Zeng,Huan Du,Ling Li,Yunfei Tian,Xiandeng Hou,Li Wu

Herein, a facile and fast surface-enhanced Raman scattering (SERS) method with ratiometric strategy was developed for detection of 4-methylimidazole (4-MI). Via a chemical derivatization reaction with 3-amino-5-mercapto-1,2,4-triazole (AMTA) diazonium salts, 4-MI could be converted to SERS-sensitive species. The SERS intensity ratio between the peaks at 1243 cm −1 and 1110 cm −1 (I 1243 /I 1110 ) was used for the quantification of 4-MI. In addition, the method sensitivity was further improved by the aggregation of beta-cyclodextrin-modified Ag nanoparticles (beta-CD-AgNPs). Under the optimal conditions, the limit of detection (LOD) and the limit of quantification (LOQ) for 4-MI were 1.7 nM (S/N = 3) and 5.7 nM (S/N = 10), respectively. The relative standard deviation (RSD) for 0.5 μM 4-MI was 8.2% (n = 20). This method was successfully used for the determination of 4-MI in cola samples with recoveries ranging from 92% to 106%. The present method is convenient, sensitive, selective, reliable and may have a promising application in determination of the compounds with an imidazole ring containing active hydrogen atoms .

研究领域: 分析化学 · 食品安全检测
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TALANTA · 2016 · IF 4.035

Derivatization reaction-based surface-enhanced Raman scattering (SERS) for detection of trace acetone

Ying Zheng,Zhuo Chen,Chengbin Zheng,Yong-Ill Lee,Xiandeng Hou,Li Wu,Yunfei Tian

A facile method was developed for determination of trace volatile acetone by coupling a derivatization reaction to surface-enhanced Raman scattering (SERS). With iodide modified Ag nanoparticles (Ag IMNPs) as the SERS substrate, acetone without obvious Raman signal could be converted to SERS-sensitive species via a chemical derivatization reaction with 2,4-dinitrophenylhydrazine (2,4-DNPH). In addition, acetone can be effectively separated from liquid phase with a purge-sampling device and then any serious interference from sample matrices can be significantly reduced. The optimal conditions for the derivatization reaction and the SERS analysis were investigated in detail, and the selectivity and reproducibility of this method were also evaluated. Under the optimal conditions, the limit of detection (LOD) for acetone was 5   mg   L −1 or 0.09   mM (3σ). The relative standard deviation (RSD) for 80   mg   L −1 acetone (n=9) was 1.7%. This method was successfully used for the determination of acetone in artificial urine and human urine samples with spiked recoveries ranging from 92% to 110%. The present method is convenient, sensitive, selective, reliable and suitable for analysis of trace acetone, and it could have a promising clinical application in early diabetes diagnosis.

研究领域: 分析化学 · 医学诊断 · 纳米技术
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ANALYST · 2014 ·Vol. 139 ·期 14 ·3614-3621 · IF 3.906

Rapid analysis of trace volatile formaldehyde in aquatic products by derivatization reaction-based surface enhanced Raman spectroscopy

Zhuomin Zhang,Cheng Zhao,Yunjian Ma,Gongke Li

Toxic formaldehyde is sometimes used illegally as a food preservative, however, on-site rapid analysis of trace formaldehyde in aquatic products remains a challenge. In this work, a simple on-site rapid quantification method for trace volatile formaldehyde in aquatic products was developed by a derivative reaction-based surface enhanced Raman spectroscopy (SERS) technique coupled with a homemade portable purge-sampling device. Trace formaldehyde separated from complicated aquatic matrices via a purge-sampling procedure was reacted with a derivative reagent to produce a Raman-active analyte for consequent SERS analysis. Au/SiO2 nanoparticles (NPs) were employed as the enhancement substrate to achieve significant enhancement of Raman signal intensity. Conditions of derivative reaction and SERS detection were optimized in detail, and the selectivity of this analytical method was also evaluated based on related analogs. Under optimal conditions, an extremely low detection limit of 0.17 μg L−1 was achieved. Trace volatile formaldehyde can be found in fresh squid and shrimp samples without obvious matrix interference, and this was quantified to be 0.13–0.21 mg kg−1 using the described method. The recoveries of spiked aquatic product samples were found to be 70.0–89.1% with RSDs of 2.3–7.2% (n = 3). The results suggest that the proposed method is reliable and suitable for on-site rapid analysis of trace formaldehyde in aquatic products.

研究领域: 分析化学 · 食品安全 · 光谱学 · 环境毒理学 · 食品质量控制
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BIOTECHNOLOGY AND APPLIED BIOCHEMISTRY · 2023 ·Vol. 70 ·期 6 ·1806-1816 · IF 2.8

Quantitative determination of rhamnolipid using HPLC-UV through carboxyl labeling

Jing Zhou,Si-Jia Miao,Shi-Zhong Yang,Jin-Feng Liu,Hong-Ze Gang,Bo-Zhong Mu

Rhamnolipid, as a low-toxic, biodegradable and environmentally friendly biosurfactant, has broad application prospects in many industries. However, the quantitative determination of rhamnolipid is still a challenging task. Here, a new sensitive method for the quantitative analysis of rhamnolipid based on a simple derivatization reaction was developed. In this study, 3-[3′-( l -rhamnopyranosyloxy) decanoyloxy] decanoic acid (Rha-C10-C10) and 3-[3′-(2′- O -α- l -rhamnopyranosyloxy) decanoyloxy] decanoic acid (Rha-Rha-C10-C10) were utilized as the representative rhamnolipids. Liquid chromatography–mass spectrometry and high-performance liquid chromatography-ultra violet results showed that these two compounds were successfully labeled with 1 N1-(4-nitrophenyl)-1,2-ethylenediamine. There was an excellent linear relationship between rhamnolipid concentration and peak area of labeled rhamnolipid. The detection limits of the Rha-C10-C10 and Rha-Rha-C10-C10 were 0.018 mg/L (36 nmol/L) and 0.014 mg/L (22 nmol/L), respectively. The established amidation method was suitable for the accurate analysis of rhamnolipids in the biotechnological process. The method had good reproducibility with the relative standard deviation of 0.96% and 0.79%, respectively, and sufficient accuracy with a recovery of 96%–100%. This method was applied to quantitative analysis of 10 rhamnolipid homologs metabolized by Pseudomonas aeruginosa LJ-8. The single labeling method was used for the quantitative analysis of multiple components, which provided an effective method for the quality evaluation of other glycolipids with carboxyl groups.

研究领域: 生物技术 · 分析化学 · 环境科学
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2020 ·Vol. 412 ·期 5 ·1087-1096 · IF 3.637

Redox-derivatization reaction-based rapid and sensitive determination of nitrite using resonance Rayleigh scattering method

He Jincan,Zhong Zihui,Tan Shiying,Wu Fuhai,Bai Yan

It remains a problem for direct detection of small inorganic nitrite ions using resonance Rayleigh scattering (RRS) method based on the direct dye-binding reaction. In the present study, a redox-derivatization reaction taking only 5 min was introduced prior to nitrite detection. In the redox-derivatization reaction, nitrite ions were reduced by excess iodine ions to generate triiodide ions (I 3 − ), which were further derivatized with a cationic dye (basic violet 1, BV1) to form the ion associates of I 3 − -BV1. Therefore, the RRS signal was significantly enhanced, resulting from the increase of particle size and resonance-enhanced scattering effect. The analytical procedure was performed by just mixing nitrite, oxidant, acid, and dye all-in-one, avoiding the tediousness of a multi-step process or the preparation of nanoparticles. The whole detection process including the redox-derivatization reaction was less than 6 min. The reaction conditions such as concentration of hydrochloric acid, potassium iodide, and BV1, reaction time, and temperature were investigated. Under optimum conditions, the concentration of nitrite was linear with an RRS signal of I 3 − -BV1 ion associates at 320 nm in the range of 0.015–1.2 mg/L. The limit of detection (LOD) was calculated to be 3.0 μg/L. The RRS method was applied to the determination of nitrite in real samples such as pork sausage, milk powder, and water with recovery of 95.2–112%. With advantages of rapidness, high sensitivity, and high selectivity, the method indicates potential applicability for detection of nitrite in complex samples. The method also provides an instructive protocol for detection of analytes that generate no/weak RRS enhancement after the direct dye-binding reaction. Graphical abstract

CAS / MDL: 7681-11-0
研究领域: 分析化学 · 环境科学
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FOOD CHEMISTRY · 2018 · IF 4.946

Highly selective colorimetric detection of putrescine in fish products using o-phthalaldehyde derivatization reaction

Xuan Qi,Wei-Feng Wang,Jun Wang,Jun-Li Yang,Yan-Ping Shi

A highly selective colorimetric detection method for putrescine on the basis of an optimized derivatization reaction was established. With the aids of o -phthalaldehyde (OPA) and thioglycolic acid (TGA), putrescine was derived to become red derivatives (PUT-RD), the form that can be detected qualitatively and quantitatively by visual inspection and UV-vis spectrophotometer at λ max of 490 nm, respectively. Key parameters affecting the experiment were investigated by one-factor-at-a-time and response surface analysis. At the optimal condition, this colorimetric method achieved good linearity at putrescine concentrations ranging from 0.8 to 200 μM with detection limit of 0.44 µM. The method also has good selectivity when common amino acids and inorganic ions, as well as ethylenediamine, 1,3-propanediamine, 1,5-pentanediamine, and 1,6-hexanediamine were used as interferences. The established colorimetric method was successfully employed for the detection of putrescine in 10 commercial fish products.

研究领域: 食品科学 · 分析化学
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LAB ON A CHIP · 2024 ·Vol. 24 ·期 14 ·3412-3421 · IF 6.1

Droplet drinking in constrictions

Shi Feng,Chundong Xue,Cunliang Pan,Shengyang Tao

Droplets generated through microfluidics serve as a common platform for assembling artificial cells, which are feasibly tailored using microfluidic methodology. The ability of natural cells to undergo shape changes, such as phagocytosis, is a typical characteristic that researchers aim to mimic in artificial cells. However, simulating the deformation behavior of natural cells within droplets is exceptionally challenging. Here, this study reports a pinocytosis-like phenomenon observed in droplets, termed “droplet drinking”. When droplets traverse a capillary with constrictions, the shear force from the continuous-phase fluid induces relative motion within the droplets, creating concave regions at the rear. These regions facilitate engulfing of the continuous-phase fluid, resulting in the formation of multiple emulsions. This behavior is influenced by the capillary number, and the size of the ingested droplets is governed by the interfacial tension between the two phases. The production of multicore or multi-shell emulsions can be easily accomplished by making slight adjustments to the constrictions. Furthermore, this method demonstrates the integration of reactants into pre-existing droplets, facilitating biochemical reactions. This study presents a convenient approach for generating complex emulsions and an innovative strategy for studying deformation behavior in droplet-based artificial cells.

研究领域: 微流控技术 · 生物物理学 · 化学工程 · 细胞生物学
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Small Methods · 2025 · IF 9.1

Elucidating Local Confinement in Crowded Polymer Solutions Within Giant Unilamellar Vesicles (GUVs) Through Single Particle Tracking Toward Deeper Understanding of Cells

Yingming Zhao,Shubin Li,Yanhao Liu,Chao Li,Yongshuo Ren,Xiangxiang Zhang,Zhao Wang,Mingdong Dong,Xiaojun Han

In a crowded environment, macromolecules occupy a significant proportion volume of cells to repulse other molecules in H 2 O-rich phase domains. These H 2 O-rich phase domains have been found to significantly influence material transportation and biochemical reactions. However, the accurate quantification of the size of these domains remains a challenge. Here, formulas are set up to calculate the anomalous diffusion exponent ( α ), the concentration threshold ( c p ), and the radius of the H 2 O-rich phase domain ( r 0 ) to characterize the crowded solutions. Fitting coefficient ( R 2 ) of the r 0 fitted curves are 0.9989 for PEG-8k Da and 0.9901 for PEG-20k Da, respectively, which confirms the formulas to be suitable for quantifying the crowding degree. The values of α , r 0 , and c p of three different cell lysates is are calculated using these formulas. The r 0 values of the cytosol from eukaryotic cells are 1.22 µm for HEK-293T and 1.46 µm for S. Cerevisiae , respectively, which are smaller than that (2.13 µm) from prokaryotic cells ( E. coli ). This may be due to the more complex components, with higher molecular weight but lower concentration in the eukaryotic cells. This method for quantifying the H 2 O-rich phase in a crowded solution helps to have a deeper understanding of the biochemical mechanism inside cells.

研究领域: 生物物理学 · 细胞生物学 · 软物质物理学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

Thermally-resilient, phase-invertible, ultra-stable all-aqueous compartments by pH-modulated protein colloidal particles

Tao Zhou,Zhou Liu,Xudong Ma,Chaofeng Cen,Zhangwei Huang,Yi Lu,Tiantian Kong,Cheng Qi

The essence of compartmentalization in cells is the inspiration behind the engineering of synthetic counterparts, which has emerged as a significant engineering theme. Here, we report the formation of ultra-stable water-in-water (W/W) emulsion droplets. These W/W droplets demonstrate previously unattained stability across a broad pH spectrum and exhibit resilience at temperatures up to 80℃, overcoming the challenge of insufficient robustness in dispersed droplets of aqueous two-phase systems (ATPS). The exceptional robustness is attributed to the strong anchoring of micelle-like casein colloidal particles at the PEO/DEX interface, which maintains stability under varying environmental conditions. The increased surface hydrophobicity of these particles at high temperatures contributes to the formation of thermally-stable droplets, enduring temperatures as high as 80℃. Furthermore, our study illustrates the adaptable affinity of micelle-like casein colloidal particles towards the PEO/DEX-rich phase, enabling the formation of stable DEX-in-PEO emulsions at lower pH levels, and PEO-in-DEX emulsions as the pH rises above the isoelectric point. The robust nature of these W/W emulsions unlocks new possibilities for exploring various biochemical reactions within synthetic subcellular modules and lays a solid foundation for the development of novel biomimetic materials.

CAS / MDL: 55965-84-9 9005-46-3
研究领域: 材料科学 · 生物技术 · 化学工程 · 胶体科学 · 生物材料
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