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Direct Glycan Analysis of Biological Samples and Intact Glycoproteins by Integrating Machine Learning-Driven Surface-Enhanced Raman Scattering and Boronic Acid Arrays 通过整合机器学习驱动的表面增强拉曼散射和硼酸阵列直接分析生物样本和完整糖蛋白
Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-05-15 DOI: 10.1021/acsmeasuresciau.4c00014
Qiang Hu,  and , Hung-Jen Wu*, 

Frequent monitoring of glycan patterns is a critical step in studying glycan-mediated cellular processes. However, the current glycan analysis tools are resource-intensive and less suitable for routine use in standard laboratories. We developed a novel glycan detection platform by integrating surface-enhanced Raman spectroscopy (SERS), boronic acid (BA) receptors, and machine learning tools. This sensor monitors the molecular fingerprint spectra of BA binding to cis-diol-containing glycans. Different types of BA receptors could yield different stereoselective reactions toward different glycans and exhibit unique vibrational spectra. By integration of the Raman spectra collected from different BA receptors, the structural information can be enriched, eventually improving the accuracy of glycan classification and quantification. Here, we established a SERS-based sensor incorporating multiple different BA receptors. This sensing platform could directly analyze the biological samples, including whole milk and intact glycoproteins (fetuin and asialofetuin), without tedious glycan release and purification steps. The results demonstrate the platform’s ability to classify milk oligosaccharides with remarkable classification accuracy, despite the presence of other non-glycan constituents in the background. This sensor could also directly quantify sialylation levels of a fetuin/asialofetuin mixture without glycan release procedures. Moreover, by selecting appropriate BA receptors, the sensor exhibits an excellent performance of differentiating between α2,3 and α2,6 linkages of sialic acids. This low-cost, rapid, and highly accessible sensor will provide the scientific community with an invaluable tool for routine glycan screening in standard laboratories.

频繁监测聚糖模式是研究聚糖介导的细胞过程的关键步骤。然而,目前的聚糖分析工具资源密集,不太适合标准实验室的常规使用。我们通过整合表面增强拉曼光谱(SERS)、硼酸(BA)受体和机器学习工具,开发了一种新型聚糖检测平台。这种传感器可监测硼酸与含顺式二醇聚糖结合的分子指纹谱。不同类型的硼酸受体会对不同的聚糖产生不同的立体选择性反应,并表现出独特的振动光谱。通过整合从不同 BA 受体收集到的拉曼光谱,可以丰富结构信息,最终提高聚糖分类和定量的准确性。在这里,我们建立了一种基于 SERS 的传感器,其中包含多种不同的 BA 受体。这种传感平台可以直接分析生物样品,包括全脂牛奶和完整的糖蛋白(胎盘素和asialofetuin),而无需繁琐的聚糖释放和纯化步骤。结果表明,尽管背景中存在其他非糖类成分,该平台仍能对牛奶低聚糖进行分类,且分类准确性极高。这种传感器还能直接量化胎盘素/胎盘素混合物的糖基化水平,而无需糖释放步骤。此外,通过选择适当的 BA 受体,该传感器在区分α2,3 和α2,6 连接的硅烷酸方面表现出色。这种低成本、快速且高度易用的传感器将为科学界提供一种在标准实验室中进行常规聚糖筛选的宝贵工具。
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引用次数: 0
Detection of Uracil-Excising DNA Glycosylases in Cancer Cell Samples Using a Three-Dimensional DNAzyme Walker 利用三维 DNAzyme Walker 检测癌症细胞样本中的尿嘧啶-切除 DNA 糖基化酶
IF 4.6 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-05-08 DOI: 10.1021/acsmeasuresciau.4c0001110.1021/acsmeasuresciau.4c00011
Jeffrey Tao, Hongquan Zhang*, Michael Weinfeld and X. Chris Le*, 

DNA glycosylase dysregulation is implicated in carcinogenesis and therapeutic resistance of cancers. Thus, various DNA-based detection platforms have been developed by leveraging the base excision activity of DNA glycosylases. However, the efficacy of DNA-based methods is hampered due to nonspecific degradation by nucleases commonly present in cancer cells and during preparations of cell lysates. In this report, we describe a fluorescence-based assay using a specific and nuclease-resistant three-dimensional DNAzyme walker to investigate the activity of DNA glycosylases from cancer cell lysates. We focus on DNA glycosylases that excise uracil from deoxyuridine (dU) lesions, namely, uracil DNA glycosylase (UDG) and single-stranded monofunctional uracil DNA glycosylase (SMUG1). The limits of detection for detecting UDG and SMUG1 in the buffer were 3.2 and 3.0 pM, respectively. The DNAzyme walker detected uracil excision activity in diluted cancer cell lysate from as few as 48 A549 cells. The results of the UDG inhibitor experiments demonstrate that UDG is the predominant uracil-excising glycosylase in A549 cells. Approximately 500 nM of UDG is present in each A549 cell on average. No fluorescence was generated in the samples lacking DNAzyme activation, indicating that there was no nonspecific nuclease interference. The ability of the DNAzyme walker to respond to glycosylase activity illustrates the potential use of DNAzyme walker technology to monitor and study biochemical processes involving glycosylases.

DNA 糖基化酶失调与癌症的发生和抗药性有关。因此,人们利用 DNA 糖基化酶的碱基切除活性,开发了各种基于 DNA 的检测平台。然而,由于癌细胞中常见的核酸酶以及细胞裂解液制备过程中的非特异性降解,基于 DNA 的方法的有效性受到了影响。在本报告中,我们介绍了一种基于荧光的检测方法,利用特异性和抗核酸酶的三维 DNA 酶步行器来研究癌细胞裂解液中 DNA 糖基化酶的活性。我们重点研究了从脱氧尿苷(dU)病变中切除尿嘧啶的 DNA 糖基化酶,即尿嘧啶 DNA 糖基化酶(UDG)和单链单功能尿嘧啶 DNA 糖基化酶(SMUG1)。在缓冲液中检测 UDG 和 SMUG1 的检测限分别为 3.2 和 3.0 pM。DNAzyme walker 在稀释的 A549 癌细胞裂解物中检测到了尿嘧啶切除活性。UDG 抑制剂实验的结果表明,UDG 是 A549 细胞中最主要的尿嘧啶切除糖基化酶。每个 A549 细胞中平均存在约 500 nM 的 UDG。缺乏 DNA 酶活化的样本不会产生荧光,这表明没有非特异性核酸酶干扰。DNA 酶步行器对糖基化酶活性的反应能力说明了 DNA 酶步行器技术在监测和研究涉及糖基化酶的生化过程方面的潜在用途。
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引用次数: 0
Combating Prozone Effects and Predicting the Dynamic Range of Naked-Eye Nanoplasmonic Biosensors through Capture Bioentity Optimization 通过捕获生物特性优化消除原区效应并预测裸眼纳米光电生物传感器的动态范围
Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-05-08 DOI: 10.1021/acsmeasuresciau.4c00010
Zoe Bradley, Nikhil Bhalla
Accurately quantifying high analyte concentrations poses a challenge due to the common occurrence of the prozone or hook effect within sandwich assays utilized in plasmonic nanoparticle-based lateral flow devices (LFDs). As a result, LFDs are often underestimated compared to other biosensors with concerns surrounding their specificity and sensitivity toward the target analyte. To address this limitation, here we develop an analytical model capable of predicting the prozone effect and subsequently the dynamic range of the biosensor based on the concentration of the capture antibody. To support our model, we conduct a sandwich immunoassay to detect C-reactive protein (CRP) in a phosphate-buffered saline (PBS) buffer using an LFD. Within the experiment, we investigate the relationship between the CRP dynamic range and the prozone effect as a function of the capture antibody concentration, which is increased from 0.1 to 2 mg/mL. The experimental results, while supporting the developed analytical model, show that increasing the capture antibody concentration increases the dynamic range. The developed model therefore holds the potential to expand the measurable range and reduce costs associated with quantifying biomarkers in diverse diagnostic assays. This will ultimately allow LFDs to have better clinical significance before the prozone effect becomes dominant.
由于在基于等离子纳米粒子的横向流动装置(LFD)中使用的夹心检测法中经常出现前区或钩状效应,因此准确量化高浓度分析物是一项挑战。因此,与其他生物传感器相比,LFD 经常被低估,人们担心其对目标分析物的特异性和灵敏度。为了解决这一局限性,我们在此建立了一个分析模型,该模型能够根据捕获抗体的浓度预测原区效应以及生物传感器的动态范围。为了支持我们的模型,我们使用 LFD 进行了夹心免疫测定,以检测磷酸盐缓冲盐水 (PBS) 缓冲液中的 C 反应蛋白 (CRP)。在实验中,我们研究了 CRP 动态范围和原区效应与捕获抗体浓度(从 0.1 毫克/毫升增加到 2 毫克/毫升)之间的关系。实验结果支持所开发的分析模型,同时表明提高捕获抗体浓度会增加动态范围。因此,所开发的模型有可能扩大可测量范围,降低在各种诊断检测中量化生物标记物的相关成本。这最终将使 LFD 在原区效应占主导地位之前具有更好的临床意义。
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引用次数: 0
Combating Prozone Effects and Predicting the Dynamic Range of Naked-Eye Nanoplasmonic Biosensors through Capture Bioentity Optimization 通过捕获生物特性优化消除原区效应并预测裸眼纳米光电生物传感器的动态范围
IF 4.6 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-05-08 DOI: 10.1021/acsmeasuresciau.4c0001010.1021/acsmeasuresciau.4c00010
Zoe Bradley,  and , Nikhil Bhalla*, 

Accurately quantifying high analyte concentrations poses a challenge due to the common occurrence of the prozone or hook effect within sandwich assays utilized in plasmonic nanoparticle-based lateral flow devices (LFDs). As a result, LFDs are often underestimated compared to other biosensors with concerns surrounding their specificity and sensitivity toward the target analyte. To address this limitation, here we develop an analytical model capable of predicting the prozone effect and subsequently the dynamic range of the biosensor based on the concentration of the capture antibody. To support our model, we conduct a sandwich immunoassay to detect C-reactive protein (CRP) in a phosphate-buffered saline (PBS) buffer using an LFD. Within the experiment, we investigate the relationship between the CRP dynamic range and the prozone effect as a function of the capture antibody concentration, which is increased from 0.1 to 2 mg/mL. The experimental results, while supporting the developed analytical model, show that increasing the capture antibody concentration increases the dynamic range. The developed model therefore holds the potential to expand the measurable range and reduce costs associated with quantifying biomarkers in diverse diagnostic assays. This will ultimately allow LFDs to have better clinical significance before the prozone effect becomes dominant.

由于在基于等离子纳米粒子的横向流动装置(LFD)中使用的夹心检测法中经常出现前区或钩状效应,因此准确量化高浓度分析物是一项挑战。因此,与其他生物传感器相比,LFD 经常被低估,人们担心其对目标分析物的特异性和灵敏度。为了解决这一局限性,我们在此建立了一个分析模型,该模型能够根据捕获抗体的浓度预测原区效应以及生物传感器的动态范围。为了支持我们的模型,我们使用 LFD 进行了夹心免疫测定,以检测磷酸盐缓冲盐水 (PBS) 缓冲液中的 C 反应蛋白 (CRP)。在实验中,我们研究了 CRP 动态范围和原区效应与捕获抗体浓度(从 0.1 毫克/毫升增加到 2 毫克/毫升)之间的关系。实验结果支持所开发的分析模型,同时表明提高捕获抗体浓度会增加动态范围。因此,所开发的模型有可能扩大可测量范围,降低在各种诊断检测中量化生物标记物的相关成本。这最终将使 LFD 在原区效应占主导地位之前具有更好的临床意义。
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引用次数: 0
Detection of Uracil-Excising DNA Glycosylases in Cancer Cell Samples Using a Three-Dimensional DNAzyme Walker 利用三维 DNAzyme Walker 检测癌症细胞样本中的尿嘧啶-切除 DNA 糖基化酶
Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-05-08 DOI: 10.1021/acsmeasuresciau.4c00011
Jeffrey Tao, Hongquan Zhang, Michael Weinfeld, X. Chris Le
DNA glycosylase dysregulation is implicated in carcinogenesis and therapeutic resistance of cancers. Thus, various DNA-based detection platforms have been developed by leveraging the base excision activity of DNA glycosylases. However, the efficacy of DNA-based methods is hampered due to nonspecific degradation by nucleases commonly present in cancer cells and during preparations of cell lysates. In this report, we describe a fluorescence-based assay using a specific and nuclease-resistant three-dimensional DNAzyme walker to investigate the activity of DNA glycosylases from cancer cell lysates. We focus on DNA glycosylases that excise uracil from deoxyuridine (dU) lesions, namely, uracil DNA glycosylase (UDG) and single-stranded monofunctional uracil DNA glycosylase (SMUG1). The limits of detection for detecting UDG and SMUG1 in the buffer were 3.2 and 3.0 pM, respectively. The DNAzyme walker detected uracil excision activity in diluted cancer cell lysate from as few as 48 A549 cells. The results of the UDG inhibitor experiments demonstrate that UDG is the predominant uracil-excising glycosylase in A549 cells. Approximately 500 nM of UDG is present in each A549 cell on average. No fluorescence was generated in the samples lacking DNAzyme activation, indicating that there was no nonspecific nuclease interference. The ability of the DNAzyme walker to respond to glycosylase activity illustrates the potential use of DNAzyme walker technology to monitor and study biochemical processes involving glycosylases.
DNA 糖基化酶失调与癌症的发生和抗药性有关。因此,人们利用 DNA 糖基化酶的碱基切除活性,开发了各种基于 DNA 的检测平台。然而,由于癌细胞中常见的核酸酶以及细胞裂解液制备过程中的非特异性降解,基于 DNA 的方法的有效性受到了影响。在本报告中,我们介绍了一种基于荧光的检测方法,利用特异性和抗核酸酶的三维 DNA 酶步行器来研究癌细胞裂解液中 DNA 糖基化酶的活性。我们重点研究了从脱氧尿苷(dU)病变中切除尿嘧啶的 DNA 糖基化酶,即尿嘧啶 DNA 糖基化酶(UDG)和单链单功能尿嘧啶 DNA 糖基化酶(SMUG1)。在缓冲液中检测 UDG 和 SMUG1 的检测限分别为 3.2 和 3.0 pM。DNAzyme walker 在稀释的 A549 癌细胞裂解物中检测到了尿嘧啶切除活性。UDG 抑制剂实验的结果表明,UDG 是 A549 细胞中最主要的尿嘧啶切除糖基化酶。每个 A549 细胞中平均存在约 500 nM 的 UDG。缺乏 DNA 酶活化的样本不会产生荧光,这表明没有非特异性核酸酶干扰。DNA 酶步行器对糖基化酶活性的反应能力说明了 DNA 酶步行器技术在监测和研究涉及糖基化酶的生化过程方面的潜在用途。
{"title":"Detection of Uracil-Excising DNA Glycosylases in Cancer Cell Samples Using a Three-Dimensional DNAzyme Walker","authors":"Jeffrey Tao, Hongquan Zhang, Michael Weinfeld, X. Chris Le","doi":"10.1021/acsmeasuresciau.4c00011","DOIUrl":"https://doi.org/10.1021/acsmeasuresciau.4c00011","url":null,"abstract":"DNA glycosylase dysregulation is implicated in carcinogenesis and therapeutic resistance of cancers. Thus, various DNA-based detection platforms have been developed by leveraging the base excision activity of DNA glycosylases. However, the efficacy of DNA-based methods is hampered due to nonspecific degradation by nucleases commonly present in cancer cells and during preparations of cell lysates. In this report, we describe a fluorescence-based assay using a specific and nuclease-resistant three-dimensional DNAzyme walker to investigate the activity of DNA glycosylases from cancer cell lysates. We focus on DNA glycosylases that excise uracil from deoxyuridine (dU) lesions, namely, uracil DNA glycosylase (UDG) and single-stranded monofunctional uracil DNA glycosylase (SMUG1). The limits of detection for detecting UDG and SMUG1 in the buffer were 3.2 and 3.0 pM, respectively. The DNAzyme walker detected uracil excision activity in diluted cancer cell lysate from as few as 48 A549 cells. The results of the UDG inhibitor experiments demonstrate that UDG is the predominant uracil-excising glycosylase in A549 cells. Approximately 500 nM of UDG is present in each A549 cell on average. No fluorescence was generated in the samples lacking DNAzyme activation, indicating that there was no nonspecific nuclease interference. The ability of the DNAzyme walker to respond to glycosylase activity illustrates the potential use of DNAzyme walker technology to monitor and study biochemical processes involving glycosylases.","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":"2015 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140935699","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Practical Guide to Large Amplitude Fourier-Transformed Alternating Current Voltammetry─What, How, and Why 大振幅傅立叶变换交流伏安法实用指南--内容、方法和原因
IF 4.6 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-05-07 DOI: 10.1021/acsmeasuresciau.4c0000810.1021/acsmeasuresciau.4c00008
Natalia G. Baranska, Bryn Jones, Mark R. Dowsett, Chris Rhodes, Darrell M. Elton, Jie Zhang, Alan M. Bond, David Gavaghan, Henry O. Lloyd-Laney* and Alison Parkin*, 

Fourier-transformed alternating current voltammetry (FTacV) is a technique utilizing a combination of a periodic (frequently sinusoidal) oscillation superimposed onto a staircase or linear potential ramp. The advanced utilization of a large amplitude sine wave induces substantial nonlinear current responses. Subsequent filter processing (via Fourier-transformation, band selection, followed by inverse Fourier-transformation) generates a series of harmonics in which rapid electron transfer processes may be separated from non-Faradaic and competing electron transfer processes with slower kinetics. Thus, FTacV enables the isolation of current associated with redox processes under experimental conditions that would not generate meaningful data using direct current voltammetry (dcV). In this study, the enhanced experimental sensitivity and selectivity of FTacV versus dcV are illustrated in measurements that (i) separate the Faradaic current from background current contributions, (ii) use a low (5 μM) concentration of analyte (exemplified with ferrocene), and (iii) enable discrimination of the reversible [Ru(NH3)6]3+/2+ electron-transfer process from the irreversible reduction of oxygen under a standard atmosphere, negating the requirement for inert gas conditions. The simple, homebuilt check-cell described ensures that modern instruments can be checked for their ability to perform valid FTacV experiments. Detailed analysis methods and open-source data sets that accompany this work are intended to facilitate other researchers in the integration of FTacV into their everyday electrochemical methodological toolkit.

傅立叶变换交流伏安法(FTacV)是一种将周期性(通常为正弦波)振荡叠加到阶梯或线性电位斜坡上的技术。对大振幅正弦波的先进利用会诱发大量非线性电流响应。随后的滤波处理(通过傅立叶变换、波段选择和反傅立叶变换)会产生一系列谐波,在这些谐波中,快速电子传递过程可以与非法拉第电子传递过程和动力学较慢的竞争电子传递过程区分开来。因此,FTacV 能够在使用直流伏安法(dcV)无法产生有意义数据的实验条件下,分离出与氧化还原过程相关的电流。在本研究中,FTacV 相对于 dcV 的更高实验灵敏度和选择性体现在以下测量中:(i) 将法拉第电流从背景电流贡献中分离出来;(ii) 使用低(5 μM)浓度的分析物(以二茂铁为例);(iii) 在标准大气环境下将可逆的[Ru(NH3)6]3+/2+ 电子转移过程与不可逆的氧气还原过程区分开来,从而消除了对惰性气体条件的要求。所述简单的自制检查电池可确保检查现代仪器是否能够进行有效的 FTacV 实验。这项工作所附带的详细分析方法和开源数据集旨在帮助其他研究人员将 FTacV 纳入他们的日常电化学方法工具包。
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引用次数: 0
Practical Guide to Large Amplitude Fourier-Transformed Alternating Current Voltammetry─What, How, and Why 大振幅傅立叶变换交流伏安法实用指南--内容、方法和原因
Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-05-07 DOI: 10.1021/acsmeasuresciau.4c00008
Natalia G. Baranska, Bryn Jones, Mark R. Dowsett, Chris Rhodes, Darrell M. Elton, Jie Zhang, Alan M. Bond, David Gavaghan, Henry O. Lloyd-Laney, Alison Parkin
Fourier-transformed alternating current voltammetry (FTacV) is a technique utilizing a combination of a periodic (frequently sinusoidal) oscillation superimposed onto a staircase or linear potential ramp. The advanced utilization of a large amplitude sine wave induces substantial nonlinear current responses. Subsequent filter processing (via Fourier-transformation, band selection, followed by inverse Fourier-transformation) generates a series of harmonics in which rapid electron transfer processes may be separated from non-Faradaic and competing electron transfer processes with slower kinetics. Thus, FTacV enables the isolation of current associated with redox processes under experimental conditions that would not generate meaningful data using direct current voltammetry (dcV). In this study, the enhanced experimental sensitivity and selectivity of FTacV versus dcV are illustrated in measurements that (i) separate the Faradaic current from background current contributions, (ii) use a low (5 μM) concentration of analyte (exemplified with ferrocene), and (iii) enable discrimination of the reversible [Ru(NH3)6]3+/2+ electron-transfer process from the irreversible reduction of oxygen under a standard atmosphere, negating the requirement for inert gas conditions. The simple, homebuilt check-cell described ensures that modern instruments can be checked for their ability to perform valid FTacV experiments. Detailed analysis methods and open-source data sets that accompany this work are intended to facilitate other researchers in the integration of FTacV into their everyday electrochemical methodological toolkit.
傅立叶变换交流伏安法(FTacV)是一种将周期性(通常为正弦波)振荡叠加到阶梯或线性电位斜坡上的技术。对大振幅正弦波的先进利用会诱发大量非线性电流响应。随后的滤波处理(通过傅立叶变换、波段选择和反傅立叶变换)会产生一系列谐波,在这些谐波中,快速电子传递过程可以与非法拉第电子传递过程和动力学较慢的竞争电子传递过程区分开来。因此,FTacV 能够在使用直流伏安法(dcV)无法产生有意义数据的实验条件下,分离出与氧化还原过程相关的电流。在本研究中,FTacV 相对于 dcV 的更高实验灵敏度和选择性体现在以下测量中:(i) 将法拉第电流从背景电流贡献中分离出来;(ii) 使用低(5 μM)浓度的分析物(以二茂铁为例);(iii) 在标准大气环境下将可逆的[Ru(NH3)6]3+/2+ 电子转移过程与不可逆的氧气还原过程区分开来,从而消除了对惰性气体条件的要求。所述简单的自制检查电池可确保检查现代仪器是否能够进行有效的 FTacV 实验。这项工作所附带的详细分析方法和开源数据集旨在帮助其他研究人员将 FTacV 纳入他们的日常电化学方法工具包。
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引用次数: 0
Establishing Quality Control Metrics for Large-Scale Plasma Proteomic Sample Preparation 建立大规模血浆蛋白质组样品制备的质量控制指标
IF 4.6 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-04-29 DOI: 10.1021/acsmeasuresciau.3c0007010.1021/acsmeasuresciau.3c00070
Nekesa C. Oliver, Min Ji Choi, Albert B. Arul, Marsalas D. Whitaker and Renã A. S. Robinson*, 

Large-scale plasma proteomics studies have been transformed due to the multiplexing and automation of sample preparation workflows. However, these workflows can suffer from reproducibility issues, a lack of standardized quality control (QC) metrics, and the assessment of variation before liquid chromatography–tandem mass spectrometry (LC–MS/MS) analysis. The incorporation of robust QC metrics in sample preparation workflows ensures better reproducibility, lower assay variation, and better-informed decisions for troubleshooting. Our laboratory conducted a plasma proteomics study of a cohort of patient samples (N = 808) using tandem mass tag (TMT) 16-plex batches (N = 58). The proteomic workflow consisted of protein depletion, protein digestion, TMT labeling, and fractionation. Five QC sample types (QCstd, QCdig, QCpool, QCTMT, and QCBSA) were created to measure the performance of sample preparation prior to the final LC–MS/MS analysis. We measured <10% CV for individual sample preparation steps in the proteomic workflow based on data from various QC sample steps. The establishment of robust measures for QC of sample preparation steps allowed for greater confidence in prepared samples for subsequent LC–MS/MS analysis. This study also provides recommendations for standardized QC metrics that can assist with future large-scale cohort sample preparation workflows.

由于样品制备工作流程的多重化和自动化,大规模血浆蛋白质组学研究已经发生了转变。然而,这些工作流程可能存在可重复性问题、缺乏标准化的质量控制(QC)指标,以及在液相色谱-串联质谱(LC-MS/MS)分析前评估变异等问题。在样品制备工作流程中纳入可靠的质量控制指标可确保更好的重现性、更低的检测变异以及更明智的故障排除决策。我们实验室使用串联质量标签(TMT)16-plex 批次(N = 58)对一组患者样本(N = 808)进行了血浆蛋白质组学研究。蛋白质组学工作流程包括蛋白质去除、蛋白质消化、TMT 标记和分馏。我们创建了五种质控样品类型(QCstd、QCdig、QCpool、QCTMT 和 QCBSA),用于测量最终 LC-MS/MS 分析前样品制备的性能。我们根据不同质控样品步骤的数据,测量了蛋白质组工作流程中各个样品制备步骤的 <10% CV。为样品制备步骤的质量控制建立了可靠的衡量标准,从而提高了后续 LC-MS/MS 分析中制备样品的可信度。这项研究还为标准化质量控制指标提供了建议,有助于未来大规模队列样品制备工作流程的开展。
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引用次数: 0
Establishing Quality Control Metrics for Large-Scale Plasma Proteomic Sample Preparation 建立大规模血浆蛋白质组样品制备的质量控制指标
Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-04-29 DOI: 10.1021/acsmeasuresciau.3c00070
Nekesa C. Oliver, Min Ji Choi, Albert B. Arul, Marsalas D. Whitaker, Renã A. S. Robinson
Large-scale plasma proteomics studies have been transformed due to the multiplexing and automation of sample preparation workflows. However, these workflows can suffer from reproducibility issues, a lack of standardized quality control (QC) metrics, and the assessment of variation before liquid chromatography–tandem mass spectrometry (LC–MS/MS) analysis. The incorporation of robust QC metrics in sample preparation workflows ensures better reproducibility, lower assay variation, and better-informed decisions for troubleshooting. Our laboratory conducted a plasma proteomics study of a cohort of patient samples (N = 808) using tandem mass tag (TMT) 16-plex batches (N = 58). The proteomic workflow consisted of protein depletion, protein digestion, TMT labeling, and fractionation. Five QC sample types (QCstd, QCdig, QCpool, QCTMT, and QCBSA) were created to measure the performance of sample preparation prior to the final LC–MS/MS analysis. We measured <10% CV for individual sample preparation steps in the proteomic workflow based on data from various QC sample steps. The establishment of robust measures for QC of sample preparation steps allowed for greater confidence in prepared samples for subsequent LC–MS/MS analysis. This study also provides recommendations for standardized QC metrics that can assist with future large-scale cohort sample preparation workflows.
由于样品制备工作流程的多重化和自动化,大规模血浆蛋白质组学研究已经发生了转变。然而,这些工作流程可能存在可重复性问题、缺乏标准化的质量控制(QC)指标,以及在液相色谱-串联质谱(LC-MS/MS)分析前评估变异等问题。在样品制备工作流程中纳入可靠的质量控制指标可确保更好的重现性、更低的检测变异以及更明智的故障排除决策。我们实验室使用串联质量标签(TMT)16-plex 批次(N = 58)对一组患者样本(N = 808)进行了血浆蛋白质组学研究。蛋白质组学工作流程包括蛋白质去除、蛋白质消化、TMT 标记和分馏。我们创建了五种质控样品类型(QCstd、QCdig、QCpool、QCTMT 和 QCBSA),用于测量最终 LC-MS/MS 分析前样品制备的性能。我们根据不同质控样品步骤的数据,测量了蛋白质组工作流程中各个样品制备步骤的 <10% CV。为样品制备步骤的质量控制建立了可靠的衡量标准,从而提高了后续 LC-MS/MS 分析中制备样品的可信度。这项研究还为标准化质量控制指标提供了建议,有助于未来大规模队列样品制备工作流程的开展。
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引用次数: 0
Paired Electrosynthesis at Interdigitated Microband Electrodes: Exploring Diffusion and Reaction Zones in the Absence of a Supporting Electrolyte 交织微带电极上的配对电合成:探索无支撑电解质时的扩散和反应区
Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-04-17 DOI: 10.1021/acsmeasuresciau.4c00009
Tingran Liu, Evaldo Batista Carneiro-Neto, Ernesto Pereira, James E. Taylor, Philip J. Fletcher and Frank Marken*, 

Electrosynthesis traditionally requires dedicated reactor systems and an added electrolyte, although some paired electrosynthesis processes are possible at interdigitated microband electrodes simply immersed in solution and without an intentionally added electrolyte. Here, 1,1′-ferrocenedimethanol oxidation and activated olefin electro-hydrogenation reactions are investigated as model processes at a Pt–Pt interdigitated microband array electrode with 5 μm width and with 5 μm interelectrode gap. Voltammetric responses for electro-hydrogenation are discussed, and product yields are determined in methanol (MeOH) in the presence/absence of an added electrolyte (LiClO4). An isotope effect is observed in CH3OD solvent, leading to olefin monodeuteration linked to a fast EC-type process close to the cathode surface (in the cathode reaction zone) rather than to charge annihilation in the interelectrode zone. A finite element simulation is employed to visualize/discuss reaction zones and to contrast the rate of charge annihilation processes with/without a supporting electrolyte.

电合成传统上需要专用的反应器系统和添加的电解液,但在仅仅浸入溶液中而不刻意添加电解液的交错微带电极上也可以进行一些成对的电合成过程。本文以 1,1′-二茂铁甲醇氧化反应和活化烯烃电加氢反应为模型,研究了在宽度为 5 μm、电极间隙为 5 μm 的铂-铂交错微带阵列电极上的反应过程。讨论了电加氢的伏安反应,并测定了在有/无添加电解质(LiClO4)的甲醇(MeOH)中的产物产率。在 CH3OD 溶剂中观察到同位素效应,导致烯烃单脱氢与靠近阴极表面(阴极反应区)的快速 EC 型过程有关,而不是与电极内区的电荷湮灭有关。采用有限元模拟来直观显示/讨论反应区,并对比有/无支撑电解质的电荷湮灭过程的速率。
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ACS Measurement Science Au
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