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Preparation and application of Cu-doped antimony electrode to improve the performance of pH measurement in seawater 制备和应用掺铜锑电极以提高海水 pH 值测量性能
IF 4.2 3区 化学 Q1 Chemistry Pub Date : 2024-05-23 DOI: 10.1039/d4an00606b
Zhen Li, Li Zong, Tao Xu, Caiyun Zhang, Chao Liu
Antimony-based electrodes are widely used in various fields for pH detection due to their low cost. However, their application in the marine environment is significantly hampered by the significant potential drift observed in seawater pH measurements. This study focuses on enhancing the stability of the pure antimony electrode by doping various amounts of copper without compromising its pH response. A series of electrochemical tests demonstrated that the fabricated alloy electrodes exhibited excellent pH response characteristics, including sensitivity, ion selectivity, response time, reversibility, and temperature coefficient. Moreover, the alloy electrodes were more resistant to corrosion than the pure antimony electrode, thereby guaranteeing the stability. Notably, the alloy electrodes containing the 63 at% and 70 at% antimony exhibited the superior electrochemical characteristics. The surface analysis elucidated that the alloy electrode had reduced oxidation, surface cracks and antimony peeling compared to the pure antimony electrode. Furthermore, the prepared alloy electrodes exhibited excellent pH response and stability in simulated high-salinity seawater and real seawater. The above results highlight that doping cheap copper into antimony can improve the electrode stability by enhancing the corrosion resistance and slowing down the oxidation rate, thus enabling reliable long-time operation in a relatively stable state. These findings provide experimental support for developing novel pH electrodes based on the non-noble metals for use in challenging environments such as seawater.
锑基电极由于成本低廉,被广泛应用于各种领域的 pH 值检测。然而,在海水 pH 值测量中观察到的明显电位漂移严重阻碍了它们在海洋环境中的应用。本研究的重点是通过掺杂不同数量的铜来增强纯锑电极的稳定性,同时不影响其 pH 响应。一系列电化学测试表明,制备的合金电极具有优异的 pH 响应特性,包括灵敏度、离子选择性、响应时间、可逆性和温度系数。此外,合金电极比纯锑电极更耐腐蚀,从而保证了其稳定性。值得注意的是,含锑 63% 和 70% 的合金电极表现出更优越的电化学特性。表面分析表明,与纯锑电极相比,合金电极减少了氧化、表面裂纹和锑剥落。此外,制备的合金电极在模拟高盐度海水和真实海水中均表现出优异的 pH 响应和稳定性。上述结果表明,在锑中掺入廉价的铜可以通过增强抗腐蚀性和减缓氧化速率来提高电极的稳定性,从而使电极在相对稳定的状态下可靠地长时间工作。这些发现为开发基于非贵金属的新型 pH 电极提供了实验支持,以便在海水等挑战性环境中使用。
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引用次数: 0
Ultrasensitive detection of dopamine using Au microelectrodes integrated with mesoporous silica thin films 使用与介孔二氧化硅薄膜集成的金微电极超灵敏检测多巴胺
IF 4.2 3区 化学 Q1 Chemistry Pub Date : 2024-05-22 DOI: 10.1039/d4an00398e
Juan Huang, Huaxu Zhou, Yanqi Zou, Huiqing Liu, Qianjin Chen
An electrochemical method was developed for ultrasensitive and selective detection of dopamine in human serum using mesoporous silica thin film modified gold microelectrodes. Vertically aligned mesoporous silica thin films were deposited onto Au microelectrodes by electrochemically assisted self-assembly (EASA). The mesochannel has uniform pore size of 2.1 nm in diameter and a negatively charged wall surface. Cyclic voltammetry reveals effective charge permselectivity through the negatively charged mesoporous channels. By using differential pulse voltammetry, the mesoporous silica thin films modified Au microelectrode can be employed for the ultrasensitive detection of dopamine with a detection limit as low as 0.084 μM. In addition, thanks to the electrostatic and steric effects of the silica mesochannels, excellent anti-Interference and anti-fouling properties of the electrochemical sensors are demonstrated.
利用介孔二氧化硅薄膜修饰的金微电极,开发了一种超灵敏和选择性检测人血清中多巴胺的电化学方法。通过电化学辅助自组装(EASA)将垂直排列的介孔二氧化硅薄膜沉积到金微电极上。介孔通道具有直径为 2.1 nm 的均匀孔径和带负电的壁面。循环伏安法显示了通过带负电的介孔通道的有效电荷选择性。利用差分脉冲伏安法,介孔二氧化硅薄膜修饰的金微电极可用于多巴胺的超灵敏检测,检测限低至 0.084 μM。此外,由于二氧化硅介孔的静电和立体效应,电化学传感器还具有出色的抗干扰和防污性能。
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引用次数: 0
Rapid Analysis of Bioactive Compounds from Citrus Samples by Direct Analysis in Real-Time Mass Spectrometry Combined with Chemometrics 通过实时质谱直接分析结合化学计量学快速分析柑橘样品中的生物活性化合物
IF 4.2 3区 化学 Q1 Chemistry Pub Date : 2024-05-22 DOI: 10.1039/d4an00316k
Xingyu Wang, Yilin Chen, Yanqiao Xie, Yamin Liu, Linhong Fan, Linnan Li, Zhengtao Wang, Li Yang
Renowned for their nutritional benefits, citrus fruits are harvested at various stages in China for functional food production. This study introduces an innovative analytical method, DART-MS, enabling direct qualitative analysis of citrus samples without the need for preprocessing. Simultaneously, the combination of chemometrics can be applied for distinguishing between three different citrus samples: Citri Reticulatae Pericarpium, Citri Reticulatae Pericarpium Viride, and Citri reticulatae "Chachi". Notably, given international regulatory concerns surrounding synephrine, a precise quantitative analysis method for synephrine has been developed. The limit of detection (LOD) and the limit of quantification (LOQ) were 39 ng/mL and 156 ng/mL, respectively. And the recovery rates obtained varied from 98.46% to 100.71%. Furthermore, the intra-day and inter-day precision demonstrated robust consistency, with values spanning 5.0–6.1% and 5.03–6.08%, respectively. Offering quicker results compared to HPLC-MS, promising safer assessment of herbal and food products.
柑橘类水果以其营养价值而闻名,在中国,柑橘类水果在不同阶段都会被采收用于功能性食品的生产。本研究引入了一种创新的分析方法--DART-MS,无需预处理即可直接对柑橘样品进行定性分析。同时,结合化学计量学可用于区分三种不同的柑橘样品:Citri Reticulatae Pericarpium、Citri Reticulatae Pericarpium Viride 和 Citri reticulatae "Chachi"。值得注意的是,考虑到国际法规对脱氧肾上腺素的关注,我们开发了一种精确的脱氧肾上腺素定量分析方法。该方法的检出限(LOD)和定量限(LOQ)分别为 39 纳克/毫升和 156 纳克/毫升。回收率为 98.46% 至 100.71%。此外,日内精密度和日间精密度表现出很强的一致性,分别为 5.0-6.1% 和 5.03-6.08%。与 HPLC-MS 相比,该方法能更快地得出结果,有望对草药和食品进行更安全的评估。
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引用次数: 0
Immobilising an acid-cleavable dimeric phthalocyanine on gold nanobipyramids for intracellular pH detection and photodynamic elimination of cancer cells† 在金纳米双锥体上固定可酸解的二聚酞菁,用于细胞内 pH 值检测和光动力消除癌细胞
IF 4.2 3区 化学 Q1 Chemistry Pub Date : 2024-05-22 DOI: 10.1039/D4AN00420E
Yue Cao, Roy C. H. Wong, Evelyn Y. Xue, Han Zhang, Jie Wang, Yan Ding, Lei Zhang, Feng Chen, Jianfang Wang and Dennis K. P. Ng

An acetal-linked dimeric phthalocyanine has been synthesised and immobilised on the surface of gold nanobipyramids. The resulting nanocomposite serves as a highly sensitive probe for intracellular pH through its acid-responsive fluorescence and surface-enhanced Raman scattering signals. The phthalocyanine units released in the acidic intracellular environment can also effectively eliminate the cancer cells upon light irradiation, rendering this simple fabricated nanosystem a bimodal and bifunctional theranostic agent.

我们合成了一种乙缩醛连接的二聚酞菁,并将其固定在金纳米双锥体表面。由此产生的纳米复合材料通过其酸响应荧光和表面增强拉曼散射信号成为细胞内 pH 值的高灵敏度探针。在酸性细胞内环境中释放的酞菁单元还能在光照射下有效消除癌细胞,从而使这种简单的纳米系统成为一种双功能和双模治疗剂。
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引用次数: 0
A facile fluorescence method for the effective detection of ampicillin using antioxidant carbon dots with specific fluorescent response to ˙OH† 利用对 ∙OH 具有特异性荧光响应的抗氧化碳点有效检测氨苄西林的简便荧光方法
IF 3.6 3区 化学 Q1 Chemistry Pub Date : 2024-05-21 DOI: 10.1039/D4AN00561A
Xiaoqin Deng, Menghan Zhang, Yao Wang, Chenfang Miao, Yanjie Zheng, Jiyue Huang, Yongzhong Chen and Shaohuang Weng

Monitoring methods for beta-lactam (β-lactam) antibiotics, especially for ampicillin (AMP), with simple operation and sensitivity for realtime applications are highly required. To address this need, antioxidant carbon dots (E-CDs) with excellent fluorescence properties were synthesized using citric acid and ethylenediamine as raw materials. With a quantum yield of 81.97%, E-CDs exhibited a specific and sensitive response to ˙OH. The quenched fluorescence of E-CDs by the formed ˙OH could be restored through a competition reaction with AMP. Leveraging the signal-quenching strategy of E-CDs, H2O2, and Fe2+, a fluorescence signal-on strategy was developed using AMP as the fluorescence recovery agent for the sensitive detection of AMP. The mechanism of the quenching of E-CDs by ˙OH was attributed to the damaging effect of ˙OH on E-CDs. Under optimal conditions, the detection limit of this method for AMP was determined to be 0.38 μg mL−1. This method was successful in drug quality control and the spiked detection of AMP in lake water, milk, and sea cucumber, presenting a viable option for convenient and rapid antibiotic monitoring methods.

β-内酰胺类(β-lactam)抗生素,尤其是氨苄西林(AMP)的监测方法非常需要操作简单、灵敏度高的实际应用。针对这一需求,研究人员以柠檬酸和乙二胺为原料,合成了具有优异荧光特性的抗氧化碳点(E-CDs)。E-CDs 的量子产率为 81.97%,对-OH 具有特异性和敏感性。E-CDs的荧光被形成的-OH淬灭后,可通过与AMP的竞争反应恢复。利用 E-CDs、H2O2 和 Fe2+ 的信号淬灭策略,开发了一种以 AMP 为荧光恢复剂的荧光信号开启策略,用于灵敏检测 AMP。-OH淬灭E-CDs的机制是由于-OH对E-CDs的破坏作用。在最佳条件下,该方法对AMP的检测限为0.38 μg/mL。该方法可用于药物质量控制和湖水、牛奶和海参中AMP的添加检测,为方便快捷的抗生素监测方法提供了一种可行的选择。
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引用次数: 0
Ultrafast protein digestion using immobilized enzyme reactor following high-resolution mass spectrometry analysis for rapid identification of abrin toxin. 利用固定酶反应器进行超快蛋白质消化,然后进行高分辨率质谱分析,以快速鉴定abrin毒素。
IF 4.2 3区 化学 Q1 Chemistry Pub Date : 2024-05-21 DOI: 10.1039/d4an00406j
Meng Chen, baoqiang Li, Wenlu Wei, Zhongyao Zhang, Lin Zhang, Cuiping Li, Qibin Huang
Abrin toxin, highly dangerous with an estimated human lethal dose of 0.1–1 μg/kg body weight, has attracted much attention regarding criminal and terroristic misuse over the past decade. Therefore, developing a rapid detection method for abrin toxin is of great significance in the field of biosecurity. In this study, based on the specific dissociation method of immobilized enzyme reactor, trypsin immobilized reactor Fe3O4@CTS-GA-Try was prepared to replace free trypsin, and the immobilized enzyme digestion process was systematically investigated and optimized by using bovine serum albumin as the simulant of abrin. After 5 min one-step denaturation and reduction, satisfactory peptide number and coverage were yielded with only 15 s assisted by ultrasound probe to identify model proteins. Subsequently, abrin was rapidly digested using the established method, resulting in stable and highly reproducible characteristic peptide numbers of 39, which can be analyzed by nanoelectrospray ionization coupled with high-resolution mass spectrometry. With the acquisition mode of full MS scan coupled with PRM, not only MS spectra of total abrin peptides but also the corresponding MS/MS spectra of specific abrin peptides can achieve characteristic detection of abrin toxin and its different isoforms in less than 10 minutes, with high repeatability. This assay provides a universal platform and has great potential for the development of on-site detection and rapid mass spectrometric analysis techniques for macromolecular protein toxins and can further be applied to the integrated detection of chemical and biological agents.
蓖麻毒素具有高度危险性,估计人体致死剂量为 0.1-1 μg/kg 体重,在过去十年中,蓖麻毒素在犯罪和恐怖滥用方面引起了广泛关注。因此,开发一种快速检测蓖麻毒素的方法在生物安全领域具有重要意义。本研究基于固定化酶反应器的特异性解离方法,制备了胰蛋白酶固定化反应器Fe3O4@CTS-GA-Try以替代游离胰蛋白酶,并以牛血清白蛋白作为阿布林蛋白的模拟物,对固定化酶消化过程进行了系统研究和优化。经过 5 分钟的一步变性和还原后,在超声探头的辅助下,仅用 15 秒就能获得令人满意的肽数和覆盖率,从而鉴定出模型蛋白质。随后,使用既定方法对 abrin 进行快速消化,得到了稳定且重现性高的 39 个特征肽段,并可通过纳米电喷雾离子化和高分辨率质谱进行分析。采用全质谱扫描结合PRM的采集模式,不仅可以获得胰蛋白酶总肽段的质谱图,还可以获得特异性胰蛋白酶肽段相应的质谱/质谱图,从而在10分钟内实现对胰蛋白酶毒素及其不同异构体的特征性检测,且重复性高。该检测方法提供了一个通用平台,在开发大分子蛋白质毒素的现场检测和快速质谱分析技术方面具有巨大潜力,并可进一步应用于化学和生物制剂的综合检测。
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引用次数: 0
Analytical applications of droplet deposition Raman spectroscopy 液滴沉积拉曼光谱的分析应用。
IF 4.2 3区 化学 Q1 Chemistry Pub Date : 2024-05-21 DOI: 10.1039/D4AN00336E
Eva Kočišová, Alžbeta Kuižová and Marek Procházka

The droplet deposition methods in Raman spectroscopy have received considerable attention in the field of analytical sensing focusing on effective pre-concentration of the studied analyte (coffee-ring effect or small spots). This review covers different analytical applications of drop-coating deposition Raman scattering (DCDRS) and droplet deposition surface-enhanced Raman scattering (SERS) spectroscopy. Two main advantages of droplet deposition Raman techniques are considered: the drying-induced segregation of the components from the mixtures (such as body fluids) and the sensitivity of detection of various analytically important molecules. Some recent advanced applications, including clinical cancer diagnosis, are discussed and summarized. Finally, the potential and further perspectives of the droplet deposition Raman methods for analytical studies are introduced.

拉曼光谱中的液滴沉积方法在分析传感领域受到广泛关注,其重点是有效预浓缩所研究的分析物(咖啡环效应或小光斑)。本综述涉及液滴涂敷沉积拉曼散射(DCDRS)和液滴沉积表面增强拉曼散射(SERS)光谱的不同分析应用。研究考虑了液滴沉积拉曼技术的两大优势:干燥引起的混合物(如体液)成分分离和各种重要分析分子的检测灵敏度。还讨论并总结了最近的一些先进应用,包括临床癌症诊断。最后,介绍了用于分析研究的液滴沉积拉曼方法的潜力和前景。
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引用次数: 0
Study of nusinersen metabolites in cerebrospinal fluid of children with spinal muscular atrophy using ultra-high-performance liquid chromatography coupled with quadrupole-time-of-flight mass spectrometry 利用超高效液相色谱-四极杆飞行时间质谱法研究脊髓性肌萎缩症患儿脑脊液中的奴西那生代谢物
IF 4.2 3区 化学 Q1 Chemistry Pub Date : 2024-05-20 DOI: 10.1039/d4an00436a
Sylwia Studzińska, Oliwia Błachowicz, Szymon Bocian, Oktawia Kalisz, Aleksandra Jaworska, Jakub Szymarek, Maria Mazurkiewicz-Bełdzińska
The study aimed to analyze nusinersen metabolites in the cerebrospinal fluid samples using ion-pair reversed-phase ultrahigh-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry. Three different sample preparation methods were tested for extraction and purification, but solid phase extraction appeared to be the most suitable, allowing a significant sample enrichment (40-fold). This step was necessary to detect and identify metabolites of nusinersen in the cerebrospinal fluid. The developed and applied analytical procedure enabled the identification of nusinersen metabolites: sequences shorter by several nucleotides from the 3' end; shorter by several nucleotides from both the 3' and 5' ends; and some depurination products. To the best of our knowledge, this is the first report on the analysis and identification of nusinersen metabolites in cerebrospinal fluid samples taken from children with spinal muscular atrophy treated with Spinraza.
该研究旨在利用离子对反相超高效液相色谱法和四极杆飞行时间质谱法分析脑脊液样本中的奴西那生代谢物。对三种不同的样品制备方法进行了提取和纯化测试,但固相萃取似乎是最合适的方法,可以显著富集样品(40 倍)。这一步骤对于检测和鉴定脑脊液中的奴西那生代谢物十分必要。所开发和应用的分析程序能够鉴定出努西奈森代谢物:3'末端短几个核苷酸的序列;3'和5'末端均短几个核苷酸的序列;以及一些去嘌呤产物。据我们所知,这是第一份关于分析和鉴定使用 Spinraza 治疗脊髓性肌萎缩症患儿脑脊液样本中努西奈森代谢物的报告。
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引用次数: 0
Development of in vitro microfluidic models to study endothelial responses to pulsatility with different mechanical circulatory support devices† 开发体外微流控模型,研究内皮对不同机械循环支持装置脉动的反应
IF 3.6 3区 化学 Q1 Chemistry Pub Date : 2024-05-20 DOI: 10.1039/D4AN00507D
Xueying Wang, Lixue Liang, Guruprasad A. Giridharan, Palaniappan Sethu, Yanxia Wang, Kai-rong Qin, Peng Qu and Yu Wang

Continuous-flow ventricular assist devices (CFVAD) and counterpulsation devices (CPD) are used to treat heart failure (HF). CFVAD can diminish pulsatility, but pulsatile modes have been implemented to increase vascular pulsatility. The effects of CFVAD in a pulsatile mode and CPD support on the function of endothelial cells (ECs) are yet to be investigated. In this study, two in vitro microfluidic models for culturing ECs are proposed to reproduce blood pressure (BP) and wall shear stress (WSS) on the arterial endothelium while using these medical devices. The layout and parameters of the two microfluidic systems were optimized based on the principle of hemodynamic similarity to efficiently simulate physiological conditions. Moreover, the unique design of the double-pump and double afterload systems could successfully reproduce the working mode of CPDs in an in vitro microfluidic system. The performance of the two systems was verified by numerical simulations and in vitro experiments. BP and WSS under HF, CFVAD in pulsatile modes, and CPD were reproduced accurately in the systems, and these induced signals improved the expression of Ca2+, NO, and reactive oxygen species in ECs, proving that CPD may be effective in normalizing endothelial function and replacing CFVAD to a certain extent to treat non-severe HF. This method offers an important tool for the study of cell mechanobiology and a key experimental basis for exploring the potential value of mechanical circulatory support devices in reducing adverse events and improving outcomes in the treatment of HF in the future.

持续流心室辅助装置(CFVAD)和反搏器(CPD)已被用于治疗心力衰竭(HF)。CFVAD 可降低搏动性,但脉冲模式可增加血管搏动性。脉动方式的 CFVAD 和 CPD 支持对内皮细胞(ECs)功能的影响有待研究。本研究提出了两种用于培养 ECs 的体外微流控模型,以重现这些医疗设备引起的动脉内皮的血压(BP)和壁剪应力(WSS)。根据血流动力学相似性原理对这两种微流控系统进行了优化,使此类系统的开发和布局更具可重复性。此外,双泵和双后载系统的独特设计可以在体外微流控系统中成功再现 CPD 的工作模式。两种系统的性能通过数值模拟和体外实验得到了验证。HF、脉冲模式的CFVAD和CPD均能准确再现BP和WSS,这些诱导信号改善了EC中Ca2+、NO和活性氧的表达,证明CPD可有效恢复内皮功能,并在一定程度上替代CFVAD治疗非重度HF。该方法为研究细胞机械生物学提供了重要工具,也为探索机械循环支持装置的潜在价值和减少不良事件以改善未来治疗高血压的预后提供了重要的实验基础。
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引用次数: 0
An effective urobilin clearance strategy based on paramagnetic beads facilitates microscale proteomic analysis of urine† 基于顺磁珠的有效尿蛋白清除策略有助于对尿液进行微尺度蛋白质组分析
IF 3.6 3区 化学 Q1 Chemistry Pub Date : 2024-05-20 DOI: 10.1039/D4AN00312H
Kemiao Zhen, Wenhao Hou, Lu Bai, Mingchao Wang, Zhan Yue, Zanxin Xu, Deyun Xiong, Li Gao and Wantao Ying

Urine provides an ideal source for disease biomarker discovery. High-adhesion contaminants such as urobilin, which are difficult to remove from urine, can severely interfere with urinary proteomic analysis. Here, we aimed to establish a strategy based on single-pot, solid-phase-enhanced sample preparation (SP3) technology to prepare samples for urinary proteomics analysis that almost completely eliminates the impact of urobilin. A systematic evaluation of the effects of two urinary protein precipitation methods, two types of protein lysis buffers, and different ratios of magnetic digestion beads on the identification and quantification of the microscale urinary proteome was conducted. Our results indicate that methanol–chloroform precipitation, coupled with efficient lysis facilitated by urea, and subsequent enzymatic digestion using a mix of hydrophilic and hydrophobic magnetic beads offers the best performance. Further applying this strategy to the urine of patients with benign prostatic hyperplasia, prostate cancer and healthy individuals, combined with a narrow window of data-independent acquisition, FGFR4, MYLK, ORM2, GOLM1, SPP1, CD55, CSF1, DLD and TIMP3 were identified as potential biomarkers to discriminate benign prostatic hyperplasia and prostate cancer patients.

尿液是发现疾病生物标记物的理想来源。尿蛋白等高附着性污染物很难从尿液中去除,会严重干扰尿液蛋白质组分析。在此,我们旨在建立一种基于单锅固相增强样品制备(SP3)技术的策略,以制备用于尿液蛋白质组学分析的样品,从而几乎完全消除尿蛋白的影响。我们系统地评估了两种尿液蛋白质沉淀方法、两种蛋白质裂解缓冲液和不同比例的磁性消化珠对微量尿液蛋白质组的鉴定和定量的影响。我们的研究结果表明,甲醇-氯仿沉淀法加上尿素促进的高效裂解,以及随后使用亲水性和疏水性混合磁珠进行酶消化的方法性能最佳。将这一策略进一步应用于良性前列腺增生患者、前列腺癌患者和健康人的尿液,并结合窄窗口数据无关性采集,结果发现 FGFR4、MYLK、ORM2、GOLM1、SPP1、CD55、CSF1、DLD 和 TIMP3 是区分良性前列腺增生和前列腺癌患者的潜在生物标记物。
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引用次数: 0
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