Analytical Methods
·
2020
·Vol. 12
·期 17
·2221-2227
·
IF 2.596
Junjie Du,Qiwei Zhang,Jianjun Li,Qi Zheng
Sialic acid (Sia) is widespread in vertebrates and humans as well as in some microbes and invertebrates. It is well known that O-acetylation is a common modification for Sia. Also, highly O-acetylated Sias have been reported in humans, bovines, and fish. Derivatization based on 1,2-diamino-4,5-methylenedioxybenzene (DMB) coupled with LC-fluorescence detection or LC-MS analysis has been the routine analytical strategy for O-acetylation profiling of Sias. Unfortunately, DMB offers poor chromatographic resolution for some O-acetylated species. Herein, we report another derivatization reagent, 4,5-dimethylbenzene-1,2-diamine (DMBA), for the LC-MS analysis of Sia isomers. The DMBA method was first evaluated using Sia reference standard, horse serum and carp blood. The results demonstrate that DMBA provides superior chromatographic separation efficiency and comparable MS/MS spectra to DMB. The proposed method was then applied to the analysis of relative abundance of each Sia species in fish tissues, including liver, intestine, muscle and brain. It was found that the relative amounts of Sia species were significantly different among the four tissues. Thus, DMBA derivatization-based LC-MS methods have great potential in investigating the O-acetylation level of Sias in various samples, such as human food and bio-pharmaceutical products.
研究领域:
分析化学
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生物化学
·
药学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF PHARMACEUTICAL AND BIOMEDICAL ANALYSIS
·
2023
·
IF 3.4
Dong Xiang,Tinghui Zhao,Jue Wang,Yang Cao,Qiuxia Yu,Lu Liu,Hengyi Yu,Xiping Li,Ninghong Li,Yang Yi,Xuepeng Gong
A sensitive and robust LC-MS/MS method has been developed and validated for olverembatinib quantification in human plasma and cerebrospinal fluid (CSF). The method involved liquid-liquid extraction with methyl tertiary butyl ether for plasma pretreatment and precipitation enrichment with methanol for CSF pretreatment. Separation was achieved on the C18 column with gradient elutions of 10 mM ammonium formate in water and methanol-acetonitrile (50:50,v/v). Analyte detection was conducted by electrospray ionization (ESI) in a positive ion mode using multiple reaction monitoring (MRM). The m/z transitions were 533.4→433.2 for olverembatinib and m/z 502.4→394.2 for the internal standard (IS, Imatinib-d8). Calibration curves ranged from 0.500 to 50.0 ng/mL for plasma and from 0.0100 to 1.00 ng/mL for CSF. The intra- and inter-day precision and accuracy were < 15% for both plasma and CSF with four different quality control concentrations. The relative matrix effect was < 10% in plasma and artificial CSF. This method was successfully utilized for the measurement of olverembatinib concentrations in plasma and CSF from chronic myeloid leukemia patients.
研究领域:
药理学
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分析化学
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肿瘤学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF PHARMACEUTICAL AND BIOMEDICAL ANALYSIS
·
2013
·
IF 2.947
Jiapeng Leng,Qing Guan,Tuanqi Sun,Yi Wu,Yanjing Cao,Yinlong Guo
Free fatty acids (FFAs) analysis of human tissue is challenging due to the low abundance of tissue lipids and interference from the complex matrix. Based on our previously reported on 2,4-dimethoxy-6-piperazin-1-yl pyrimidine (DMPP) derivatization toward carboxy group, we have further applied DMPP derivatization method in the assay of tissue FFAs in patients with thyroid carcinoma after method optimization including sample pretreatment, and derivatization condition. d 6 -DMPP labeled mixture of FFAs standard was used as the internal standard (IS). The d 0 -DMPP labeled samples (spiked with IS) were subsequently used for lipids profiling by selective reaction monitoring (SRM) detection. The DMPP derivatization combined with SRM not only allowed trace analysis of FFAs in complex matrix due to the extremely high sensitivity, but also minimized the errors in quantitation because of the very similar property between d 0 -DMPP derivatized samples and d 6 -DMPP derivatized IS. Eighteen kinds of FFAs were detected successfully with the increased level in carcinoma tissue compared with the normal tissue, which may be the results of abnormality in the metabolism of fatty acid synthases and lipids. Application of the DMPP based FFAs derivatization is expected to provide a promising tool for the investigation of lipids in vivo , especially for the research of lipid metabolism.
研究领域:
分析化学
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肿瘤学
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代谢组学
✓ 已验证
DOI
PubMed
高影响因子
ANALYTICA CHIMICA ACTA
·
2023
·
IF 6.2
Jie Chen,Pei Zhang,Siyuan Qin,Bei Tan,Siqi Li,Shaoran Tang,Chuyao Liao,Ying Zhang,Zunjian Zhang,Fengguo Xu
The metabolome and lipidome are critical components in illustrating biological processes and pathological mechanisms. Generally, two or more independent methods are required to analyze the two compound panels due to their distinct chemical properties and polarity differences. Here, a novel strategy integrating stepwise solid-phase extraction (SPE) and dansyl chemical derivatization was proposed for all-in-one injection LC-MS/MS analysis of serum metabolome and lipidome. In this workflow, a stepwise elution procedure was firstly optimized to separate the metabolome and lipidome fractions using an Ostro plate. Dansyl chemical derivatization was then applied to label amine/phenol, carboxyl, and carbonyl-containing sub-metabolomes. Our results demonstrated that the dansyl labeling could significantly improve chromatographic separation, enhance the MS response, and overcome the matrix effect of co-eluting lipids . Ultimately, an all-in-one injection LC-MS/MS method measuring 256 lipids (covering 20 subclasses) and 212 metabolites (including amino acids , bile acids , fatty acids , acylcarnitines, indole derivatives, ketones and aldehydes, nucleic acid metabolism, polyamines , etc.) was established. This method was applied to investigate the metabolic changes in cisplatin-induced nephrotoxicity in rats and the results were compared with previous untargeted metabolomics . The presented strategy could predominantly improve the analytical coverage and throughput and can be of great use in discovering reliable potential biomarkers in various applications.
研究领域:
分析化学
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生物化学
·
医学
✓ 已验证
DOI
PubMed
高影响因子
TALANTA
·
2021
·
IF 6.057
Mengyuan Qu,Shanshan Ma,Yanjie Huang,Hang Yuan,Shusheng Zhang,Gangfeng Ouyang,Yufen Zhao
Investigation into monosaccharides is critical for studies of oligosaccharides structure and function in biological processes. However, monosaccharides quantification is still challenge due to their isomeric structure and high hydrophilic properties . Besides, it was difficult to obtain isotopic internal standards (IS) of each monosaccharide in complex matrixes. Herein, we developed a novel strategy for the qualification and quantification of monosaccharides in urine using two structure analogs 1-(4-methylphenyl)-3-methyl-5-pyrazolone (MPMP) and1-phenyl-3-methyl-5-pyrazolone (PMP) as non-isotopically paired labeling (NIPL) reagents by liquid chromatograph-tandem mass spectrometry (LC-MS/MS). The derivatized monosaccharides by NIPL method not only had sufficient retention time differences on reversed-phase column, but also exhibited predominant product ion pairs ( m/z 189 & m/z 175) in the multiple reaction monitoring (MRM) mode. In this method, PMP labeled standards were adopted as one-to-one internal standards (ISs). 12 urinary monosaccharides were successfully determined and the linear ranges expanded five orders of magnitude with limit of quantification (LOQ) varied from 0.09 ng mL −1 to 0.36 ng mL −1 as well as the accuracy higher than 98.15% and the relative standard derivation (RSD) lower than 7.92%. With assistance of multivariate analysis, the targeted monosaccharide biomarkers were firstly obtained for the diagnosis of bladder cancer. By the inexpensive NIPL reagents—MPMP/PMP, the developed strategy possessed the specific advantages of low cost, simple operation, high sensitivity and high accuracy for the qualification and quantitation of monosaccharides. As expected, this method will provide an alternative application potential for targeted metabolomics analysis.
研究领域:
分析化学
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代谢组学
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医学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
BIOMEDICAL CHROMATOGRAPHY
·
2025
·Vol. 39
·期 2
·e6067
·
IF 1.7
Jiale Liu,Rongfei Yuan,Qi Wang,Hai Qiao,Yuling Yang,Siyu Yang,Hua Zhang,Chang Chen
High-intensity focused ultrasound (HIFU) is a noninvasive soft tissue ablation technique, which utilizes ultrasound energy to induce thermal coagulation necrosis in targeted tissues. Whether this high energy causes side effects in vivo, such as the formation of peptide bonds, has not been fully investigated. Glycylglycine is the simplest dipeptide and hence is often used as a model compound for peptide studies. In this study, we developed and validated a sensitive quantification method based on ion-exchange solid-phase extraction, liquid chromatography, and tandem mass spectrometry (SPE-LC-MS/MS) for the analysis of glycylglycine without derivatization, and then used it to evaluate whether HIFU promoted peptide bond formation in aqueous solution (without enzymes) and plasma (with enzymes). The results showed that strong cation exchange SPE significantly reduced the matrix effect and improved the sensitivity of the LC-MS/MS method. No formation of glycylglycine in the aqueous solution or plasma was observed following HIFU irradiation.
研究领域:
生物化学
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医学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
FOOD CHEMISTRY
·
2025
·
IF 9.8
Lei Ye,Xuezhen Yang,Zhenzhu Huang,Bo Zhang,Qing Tian,Yu Huang,Wei Tan,Mingjun Feng,Xiaolin Li,Hongbin Xu
Driven by the need for sustainable agriculture, using Lycium barbarum (goji) sawdust as a substrate for mushroom cultivation increases productivity while reducing environmental impact. This study evaluates the effects of different proportions of goji sawdust on the growth, yield, and metabolic profiles of pink A. cornea . Six substrate formulations were tested, with 16 % goji sawdust supporting optimal yield and quality. LC-MS/MS-based metabolomics identified 1335 metabolites, mainly organic acids and derivatives, lipids and lipid-like molecules, organoheterocyclic compounds, and benzenoids. Biomarker analysis revealed twenty to thirty-five metabolites associated with substrate variations. KEGG enrichment highlighted key metabolic pathways, including ABC transporters, amino acid biosynthesis, D-amino acid metabolism, and aminoacyl-tRNA biosynthesis, contributing to substrate adaptation. While this study offers insights into the metabolic responses of pink A. cornea to goji sawdust, future research should incorporate absolute biomarkers quantification to further validate these results and optimize substrate compositions.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
FOOD CHEMISTRY
·
2017
·
IF 4.529
Ruyan Hou,Mengmeng Tong,Wanjun Gao,Lei Wang,Tianxi Yang,Lili He
To investigate the degradation and penetration behaviors of the organophosphate insecticide dimethoate applied on spinach leaves, in situ SERS and LC-MS methods were used to detect dimethoate residue on&in spinach leaves picked on different days after treatment (DAT). The SERS and LC-MS methods determined that the dimethoate degradation rate followed first-order kinetics, with a half-life of 3.56 or 4.13 days, depending on the respective method. The correlation coefficient of quantification value of these two methods was 0.9562. With the SERS method, we detected most of the penetrated dimethoate in the depth of 60–110 μm. With the LC-MS method, we detected dimethoate up to 0.17 ng in leaves and that the dimethoate on:in ratio of spinach leaves ranged from 562.25 on 0 DAT to 5.23 on 14 DAT. The combination of these two methods facilitated a better understanding of the behavior and biological fate of pesticides in a complex biological system.
研究领域:
植物学
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农药科学
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分析化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHROMATOGRAPHIA
·
2023
·Vol. 86
·期 8
·595-603
·
IF 1.7
Huang Dan,Tian Yufei,Zheng Yili,Li Mengyu,Xu Xia,Chen Hongyuan,Rui Wen
Forced degradation studies aim to systemically characterize the degradation products of an active pharmaceutical ingredient (API) and its formulations under harsh conditions that accelerate degradation. These studies are especially valuable for sustained-release products in selecting appropriate packaging materials and storage conditions in the field of pharmaceutics. To demonstrate the degradation pathways and degradation products of the API and products, mass spectrometry is used for further characterization of the degradation products. Goserelin acetate sustained-release implant, which is prepared by hot melt extrusion using biodegradable material polylactic acid-glycolic acid copolymer as a carrier, is used for the treatment of early breast cancer in premenopausal and perimenopausal women. In this study, a simple and sensitive high-performance chromatography method was established following the ICH guidance. We conducted forced degradation experiments to determine the conditions of the product. The forced degradation studies of the goserelin acetate sustained-release implant showed the presence of a single impurity during thermal degradation, as observed in the HPLC analysis. To elucidate the structure of the impurity and characterize its degradation pathway, we performed further characterization using LC–MS.
研究领域:
药学
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分析化学
✓ 已验证
产品关联
DOI
高影响因子
BIOMEDICAL CHROMATOGRAPHY
·
2023
·Vol. 37
·期 12
·e5751
·
IF 1.8
Feng Chen,Xiaoxia Yang,Huanhuan Li,Xiaodan Zeng,Ziwei Deng,Hongqiang Wang,Yuanxiang Jin,Chengfeng Qiu,Zhihua Shi
In order to facilitate therapeutic drug monitoring of tacrolimus and cyclosporine A in clinical practice, a simple, rapid, robust, sensitive and specific LC–MS/MS assay was developed and validated for the simultaneous determination of tacrolimus and cyclosporine A in human whole blood. Erythrocytes were destroyed using internal standard solution with 10% (w/v) zinc sulfate in water. The analytes were extracted from 100 μl of whole blood by protein precipitation with acetonitrile. Chromatographic separation was conducted on a Kinetex PFP column (60°C) by a gradient elution with a flow rate of 0.450 ml/min in 2.5 min. Quantitative analysis was performed using electrospray ionization and multiple reaction monitoring in positive ionization mode. The method was fully validated as per current guidelines on bioanalytical methodologies of the US Food and Drug Administration and European Medicines Agency. The method developed was applied successfully in analyzing clinical samples from patients administered tacrolimus or cyclosporine A. The sample treatment procedure was rationalized and improved to fulfill the complete target extraction. The chromatography conditions were optimized to achieve rapid and accurate quantification of both analytes. This method may be beneficial as a constructive input for the therapeutic drug monitoring of tacrolimus and cyclosporine A in obtaining individualized therapy.
研究领域:
临床药理学
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分析化学
·
医学检验
✓ 已验证
产品关联
DOI
PubMed
高影响因子
MICROCHIMICA ACTA
·
2020
·Vol. 187
·期 7
·1-8
·
IF 6.232
Li Nianlu,Li Ruohan,Song Yinshuang,Ma Long,Gao Cuiling,Li Lili,Cheng Shi-Bo,Zhang Xiaoli,Chen Jing,Zhan Jinhua
Carbonaceous shell-coated γ-Fe 2 O 3 nanoparticles (γ-Fe 2 O 3 @CNM) were synthesized from glucose caramelization and used as a novel magnetic solid-phase extraction medium for malachite green and crystal violet in environmental water. Malachite green and crystal violet were absorbed on to γ-Fe 2 O 3 @CNM by electrostatic and π-interactions. The morphologies, pore structures, surface functional groups, and magnetic properties of γ-Fe 2 O 3 @CNM were characterized by TEM, FTIR, hysteresis regression, Brunauer-Emmet-Teller analysis, zeta potential, XPS, and XRD. The magnetic solid-phase extraction procedure was optimized by extraction pH, absorption time, desorption solvent, and desorption time. The absorption capacities (q max values) for malachite green and crystal violet were 34.2 and 27.9 mg g −1 , respectively. After magnetic solid-phase extraction, malachite green and crystal violet were determined by LC-MS/MS. The analytical method was validated with a linear range of 0.02–20 ng mL −1 , enrichment factor of 25.8 and 25.4, method detection limit of 0.004 ng mL −1 , and intra-day precisions of 2.1% and 2.6% for malachite green and crystal violet, respectively. The relative recovery was found to be 73.4–101.5% for malachite green and 83.1–102.7% for crystal violet upon the application of the magnetic solid-phase extraction method to real water samples from lake, spring, sea, fishpond, and industrial waste.
Caramelized-carbon-coated magnetic nanoparticles are used as novel extraction medium based on electrostatic and π-interactions. It is porous, amphiphilic, electronegative, magnetically strong, and features abundant absorption site. These characteristics stimulate mass transfer and result in a useful MSPE method in environmental analysis.
研究领域:
分析化学
·
环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Frontiers in Pharmacology
·
2024
·
IF 4.4
Chen Li,Zhu Ruiqin,Ma Yaxing,Huang Chuixiu,Shen Xiantao
Objective: LC-MS/MS-based metabolomics is an important tool for studying disease-related biomarkers. Conventionally, different strategies have been used to screen biomarkers. However, many studies for biomarker screening by different strategies have ignored the dose-response relationship between the biomarker level and exposure level, and no relevant studies have described and compared different strategies in detail. Phenobarbital (PHB) which belongs to the barbiturates, was selected as the typical representative of neurotoxins. Acylcarnitines have been promising candidates for diagnostic biomarkers for several neurological disorders and neurotoxicity. In this work, we aimed to use an acute PHB poisoning animal model to clarify PHB poisoning effects on plasma and brain acylcarnitine changes and how to rationally analyze data from LC-MS/MS.Methods: The acylcarnitine profiles in plasma and brain regions in an actuate PHB poisoning animal model were utilized. The dose-response relationship between plasma PHB and carnitine and acylcarnitines (CARs) in plasma and brain were assessed by the variance analysis trend test and Spearman’s rank correlation test. In different strategies, principal component analysis (PCA) and partial least squares discriminant analysis (OPLS-DA) screened the differential CARs, variable importance plots (VIPs) were utilized to select putative biomarkers for PHB-induced toxicity, and receiver operating characteristic (ROC) curve analysis then illustrated the reliability of biomarkers.Results: Under the first strategy, 14 potential toxicity biomarkers were obtained including eight downregulated CARs with AUC >0.8. Under the second strategy, 11 potential toxicity biomarkers were obtained containing five downregulated CARs with AUC >0.8. Only when the dose-response relationship was fully considered, different strategies screen for the same biomarkers (plasma acetyl-carnitine (C2) and plasma decanoyl-carnitine (C10)), which indicated plasma acylcarnitines might serve as toxicity biomarkers. In addition, the plasma CAR level changes showed differences from brain CAR level changes, and correlations between plasma CARs and their brain counterparts were weak.Conclusion: We found that plasma C2 and C10 might serve as toxicity biomarkers for PHB poisoning disorders, and PHB poisoning effects on changes in plasma CARs may not be fully representative of changes in brain CARs.
研究领域:
代谢组学
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神经毒理学
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医学
✓ 已验证
DOI
PubMed
高影响因子
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