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A ZnO-nanorod/PEDOT:PSS nanocomposite functionalized bridge-like membrane type nanomechanical sensing device for ultrasensitive blood lead detection 用于超灵敏血铅检测的 ZnO-nanorod/PEDOT:PSS 纳米复合材料功能化桥式膜纳米机械传感装置
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-09 DOI: 10.1016/j.aca.2024.343317
Yi-Kuang Yen , Chia-Ming Yang , Chen-Ting Kao , Tzung-Hai Yen , Ragurethinam Shanmugam , Yan-Lin Chen , Hwai-En Lin
Lead (Pb) ion detection poses a critical problem, particularly in environmental monitoring, industrial operations, and public health, especially for young children and expecting women. Determining lead levels in blood early on is essential to minimizing the long-term consequences of lead exposure. Several sophisticated detection instruments, such as mass spectrometers which perform with high sensitivity, specificity and accuracy, but require a lab-based setting, multi-step sample preparation, expensive payment and professional operation. It is evident that a highly sensitive, portable, low-cost, quick sample-to-result, blood lead detection device that can be tested at the point-of-care is necessary. Consequently, we developed a unique ZnO/PEDOT:PSS nanocomposite layer integrated with a CMOS MEMS-based bridge-like membrane-type (BM) nanomechanical sensor for detecting lead levels in blood. PEDOT:PSS was combined with ZnO nanorods to increase lead ion binding. The sensor responds seven times better to lead ions using nanorods in the detecting layer. A linear resistance change rate response was found from 0.005 to 10 ppm, with the limit of detection (LOD) of 0.12 ppb. Similarly, our BM nanomechanical sensor can correctly assess Pb2+ in human serum with recovery rates of 86.25–150 %. Measurements of human blood samples from patients with varying lead ion concentrations validated by the standard AAS show a good linear connection with the BM nanomechanical sensors' concentration, with a regression coefficient of 0.92. This describes the first micromachined nanoachanical sensing system for detection of Pb2+ in only 5 μL of human serum sample. The device achieves a time-to-result of less than 10 min. The system is designed to be very sensitive and offers affordable, disposable sensing chips together with a portable signal acquisition platform.
铅(Pb)离子检测是一个关键问题,尤其是在环境监测、工业运行和公共卫生方面,特别是对幼儿和孕妇而言。及早确定血液中的铅含量对于最大限度地减少铅暴露的长期后果至关重要。一些先进的检测仪器,如质谱仪,具有高灵敏度、特异性和准确性,但需要实验室环境、多步骤的样品制备、昂贵的费用和专业的操作。显然,我们需要一种高灵敏度、便携式、低成本、快速采样出结果、可在医疗点进行检测的血铅检测设备。因此,我们开发了一种独特的 ZnO/PEDOT:PSS 纳米复合层,与基于 CMOS MEMS 的桥式膜(BM)纳米机械传感器集成,用于检测血液中的铅含量。PEDOT:PSS 与 ZnO 纳米棒相结合,增加了铅离子的结合力。在检测层中使用纳米棒,传感器对铅离子的响应速度提高了七倍。从 0.005 到 10 ppm 的线性电阻变化率响应,检测限 (LOD) 为 0.12 ppb。同样,我们的 BM 纳米机械传感器也能正确评估人体血清中的 Pb2+,回收率为 86.25-150%。通过标准 AAS 验证的不同铅离子浓度的人体血样测量结果表明,BM 纳米机械传感器的浓度与人体血样的浓度呈良好的线性关系,回归系数为 0.92。这描述了首个用于检测仅 5 μL 人体血清样本中 Pb2+ 的微型机械纳米传感系统。该装置的检测时间小于 10 分钟。该系统设计得非常灵敏,提供经济实惠的一次性传感芯片和便携式信号采集平台。
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引用次数: 0
Characterization of monoclonal antibody charge variants under near-native separation conditions using nanoflow sheath liquid capillary electrophoresis-mass spectrometry 利用纳流式鞘液毛细管电泳-质谱法表征近原生分离条件下的单克隆抗体电荷变体
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-09 DOI: 10.1016/j.aca.2024.343287
Annika A.M. van der Zon , Alisa Höchsmann , Tijmen S. Bos , Christian Neusüß , Govert W. Somsen , Kevin Jooß , Rob Haselberg , Andrea F.G. Gargano

Background

Monoclonal antibodies (mAbs) undergo multiple post-translational modifications (PTMs) during production and storage, resulting for instance in charge and oxidized variants. PTMs need to be assessed as critical quality attributes to assure protein quality and safety. Capillary zone electrophoresis (CZE) enables efficient charge-based separation. The CZE method developed by He et al. (2011) is currently applied routinely in the pharmaceutical industry for profiling charge heterogeneity of mAbs. However, as the method relies on a non-volatile background electrolyte (BGE), it cannot be directly hyphenated with mass spectrometry (MS), hampering the identification of separated charge variants.

Results

This study presents a CZE-UV/MS method using a neutral static capillary coating of hydroxypropyl methylcellulose combined with a volatile BGE at pH 5.0 to allow for MS-compatible mAb charge variant separations. The effect of several parameters, including pH and concentration of the BGE, applied voltage, and injected mAb concentrations on separation performance was investigated using a panel of commercially available mAbs. The optimized method was evaluated with IgG1 and IgG4 mAbs of varying pI (7.4–9.2) and degrees of heterogeneity. Basic and acidic variants were separated from the parent mAb using a BGE of 50 mM acetic acid adjusted to pH 5.0 with ammonium hydroxide. The relative abundances of charge variants determined with the new method showed a good correlation with the corresponding relative levels obtained with the method of He et al. CZE-MS coupling was accomplished using the nanoCEasy, a low-flow sheath liquid interface, which enabled the identification and quantitation of basic, acidic, and incomplete pyroglutamate variants, and glycoforms of the tested mAbs.

Significance

This manuscript describes a new CZE-MS method that permits heterogeneity assessment of mAbs under MS-compatible conditions, providing charge variant separation.
背景单克隆抗体(mAbs)在生产和储存过程中会发生多种翻译后修饰(PTMs),例如产生电荷和氧化变体。为确保蛋白质的质量和安全性,需要将 PTM 作为关键质量属性进行评估。毛细管区带电泳(CZE)可实现高效的电荷分离。He 等人(2011 年)开发的 CZE 方法目前已在制药行业常规应用,用于分析 mAbs 的电荷异质性。结果本研究提出了一种 CZE-UV/MS 方法,该方法使用羟丙基甲基纤维素的中性静态毛细管涂层,结合 pH 值为 5.0 的挥发性 BGE,实现了与 MS 兼容的 mAb 电荷变体分离。使用一组市售 mAb 研究了多个参数对分离性能的影响,包括 pH 值和 BGE 浓度、外加电压和注入的 mAb 浓度。使用不同 pI(7.4-9.2)和异质性程度的 IgG1 和 IgG4 mAb 对优化方法进行了评估。碱性和酸性变体用氢氧化铵调节 pH 值为 5.0 的 50 mM 乙酸 BGE 从母体 mAb 中分离出来。用新方法测定的电荷变体的相对丰度与用 He 等人的方法测定的相对丰度有很好的相关性。CZE-MS 耦合是用 nanoCEasy(一种低流量鞘液界面)完成的,它可以鉴定和定量检测 mAb 的碱性、酸性和不完全焦谷氨酸变体以及糖型。
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引用次数: 0
Metal–to–particle charge transfer invoked photoelectrochemistry on ferroelectric SrTiO3 for split–mode and high–throughput aptasensing 铁电 SrTiO3 上的金属-粒子电荷转移引发的光电化学,用于分模式和高通量灵敏度检测
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-09 DOI: 10.1016/j.aca.2024.343318
Qi Zhang, Mengmeng Gu, Lan Zhang, Xiuming Wu, Guang-Li Wang
Split–mode aptasensing is highly desirable in photoelectrochemistry because of its distinctive advantages of high-throughput, avoided damage to biomolecules, and increased sensitivity and selectivity. However, the currently available photoelectrochemical (PEC) strategy conducible to split–mode aptasensing is still limited to the bioreaction mediated generation of photoactive species, in which a low photocurrent was usually attained, rending this strategy impotent for attaining high sensitivity. As a result, to explore new strategies that are amendable to highly efficient, split-mode PEC aptasensing are still challenging but demanding. Herein, ferrocyanide mediated metal–to–particle charge transition (MPCT) on ferroelectric strontium titanate (SrTiO3) was explored as an innovative signal transduction strategy and was validated for high-performance aptasensing. By taking the 17β–Estradiol (E2) as a model analyte, the recognition between the target (E2) and its aptamer anchored on the Fe3O4@Au (named as Fe3O4@Au/Apt) destroyed the beforehand formed assembly between the Fe3O4@Au/Apt and the ssDNA labeled liposome encapsulated with [Fe(CN)6]4- (named as DLL–FeCN), which resulted in the release of the beforehand encapsulated [Fe(CN)6]4- into solution. The released [Fe(CN)6]4- then coordinated onto the surface of SrTiO3 nanoparticles consisted photoelectrode, forming the MPCT process from metal ion (iron (II) in [Fe(CN)6]4-) to the conduction band (CB) of SrTiO3 for anodic photocurrent signal output. The detection achieved linear range of 1.0 pM–100 nM, with a detection limit of 0.3 pM for E2. Benefiting from the cooperative effects of the MPCT process and the ferroelectric polarization in bulk SrTiO3 for achieving highly efficient photocurrent generation capability, the developed split–type detection had the advantage of high sensitivity/selectivity and high throughput. This work not only opens up the MPCT process for innovative PEC sensing strategy but also blazes a new road for high performance PEC aptasensing.
分离模式灵敏传感具有高通量、避免对生物分子造成损害、提高灵敏度和选择性等独特优势,因此在光电化学中非常受欢迎。然而,目前可用于分模灵敏传感的光电化学(PEC)策略仍局限于生物反应介导的光活性物种的生成,通常只能获得较低的光电流,因而无法实现高灵敏度。因此,探索可实现高效、分模式 PEC 光敏传感的新策略仍然具有挑战性,但要求很高。本文探索了铁电钛酸锶(SrTiO3)上铁氰化物介导的金属-粒子电荷转移(MPCT),将其作为一种创新的信号转导策略,并在高性能灵敏传感中得到了验证。以 17β-雌二醇(E2)为模型分析物,目标物(E2)与其锚定在 Fe3O4@Au 上的适配体(命名为 Fe3O4@Au/Apt)之间的识别破坏了 Fe3O4@Au/Apt 与用 [Fe(CN)6]4- 包封的 ssDNA 标记脂质体(命名为 DLL-FeCN)之间事先形成的组装、这导致事先封装的[Fe(CN)6]4-释放到溶液中。释放出的[Fe(CN)6]4-随后配位到组成光电极的 SrTiO3 纳米粒子表面,形成从金属离子([Fe(CN)6]4-中的铁(II))到 SrTiO3 传导带(CB)的 MPCT 过程,从而输出阳极光电流信号。检测的线性范围为 1.0 pM 至 100 nM,E2 的检测限为 0.3 pM。得益于 MPCT 工艺和块状 SrTiO3 中铁电极化的协同效应,所开发的分体式检测器实现了高效的光电流生成能力,具有高灵敏度/选择性和高通量的优点。这项工作不仅为创新型 PEC 传感策略开辟了 MPCT 工艺,还为高性能 PEC 光传感开辟了一条新路。
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引用次数: 0
Analysis of deliquescent chloride salt by laser-induced breakdown spectroscopy with controlled uniform precipitation 用激光诱导击穿光谱法分析受控均匀沉淀的潮解氯化盐
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-09 DOI: 10.1016/j.aca.2024.343315
Lizhu Kang , Ji Chen , Zhijie Huang , Zhanjian Lin , Rui Zhang , Bing Lu , Xiangyou Li

Background

The electrolytic efficiency in magnesium (Mg) production by molten salt electrolysis is mainly affected by the chloride content, which is determined by the metal content in the cooled molten salt. Laser-induced breakdown spectroscopy (LIBS) is a potential element detection method in cooled molten salt element detection. However, the cooled molten chloride salt is easily deliquescent, which greatly affects the LIBS detection results.

Results

To solve the problem, a liquid-phase precipitation method based on the addition of a dispersant named as controlled uniform precipitation (CUP) method was proposed to pretreat the samples. Compared with the conventional powder compacting method and precipitation method, the CUP obtained the highest spectral stability and detection accuracy. The average relative standard deviation (ARSD) of Mg, Ca, and Na decreased from the 51.80%, 77.04%, and 44.01% to 6.77%, 6.27%, and 29.97%, the determination coefficient of the calibration curve (R2) increased from 0.044, 0.084, and -0.109 to 0.974, 0.954, and 0.802, and the average relative error (ARE) decreased from 58.49%, 52.46%, and 99.78% to 8.58%, 11.28%, and 29.38%, respectively, compared with the powder compacting method. Further investigation showed that the CUP method suppressed the sample deliquescence and the coffee ring effect, leading to the performance improvement of LIBS quantitative detection.

Significance

The CUP provided an effective method of detecting metal elements for deliquescent samples and showed applied potential for other precipitable elements detection.
背景熔盐电解法生产镁(Mg)的电解效率主要受氯化物含量的影响,而氯化物含量则由冷却熔盐中的金属含量决定。激光诱导击穿光谱(LIBS)是一种潜在的冷却熔盐元素检测方法。为了解决这个问题,我们提出了一种基于添加分散剂的液相沉淀方法,即受控均匀沉淀法(CUP)来预处理样品。与传统的粉末压制法和沉淀法相比,CUP 法获得了最高的光谱稳定性和检测准确度。Mg、Ca和Na的平均相对标准偏差(ARSD)从51.80%、77.04%和44.01%下降到6.77%、6.27%和29.97%,校正曲线的确定系数(R2)从0.与粉末压实法相比,平均相对误差(ARE)分别从 58.49%、52.46% 和 99.78%下降到 8.58%、11.28% 和 29.38%。进一步的研究表明,CUP 方法抑制了样品潮解和咖啡环效应,从而提高了 LIBS 定量检测的性能。
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引用次数: 0
Oriental covalent immobilization of N-glycan binding protein via N-terminal selective modification 通过 N 端选择性修饰实现 N-聚糖结合蛋白的东方共价固定化
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-09 DOI: 10.1016/j.aca.2024.343311
Wenhui Wang , Liang Zhang , Yuanyuan Liu , Xiang Liu , Xin Liu
Lectin affinity chromatography is one of powerful tools for the study of protein glycosylation. Different lectin proteins can recognize different structures of monosaccharides or oligosaccharide units, allowing for the selective separation of glycopeptides or glycoproteins containing different polysaccharide structures. However, the N-glycans were only partially captured by most of common lectins, reducing the coverage rate of identifying N-glycoconjugates. Recently, it has been reported that the engineering variant of glycan binding protein Fbs1 has a high affinity for innermost Man3GlcNAc2 structure and is able to bind diverse types of N-glycans, which can be suitable for the analysis of protein N-glycosylation. However, efficient immobilization of protein to separation matrix is particularly challenging as it requires the functionality and integrity of the protein to be preserved. Herein, we describe a simple and robust strategy for oriental covalent immobilization of proteins on magnetic nanoparticles by N-terminal selective labeling techniques. We inserted the enterokinase cleavage site to produce the specific N- terminal glycine of protein. Under physiological conditions, the protein was immobilized on the surface of the MNPs by this glycine tag, and the enrichment process could be completed within 30 min. A whole enrichment and purification of glycan and glycopeptides were completed and analyzed by MALDI TOF-MS. The functional materials achieved stable enrichment of glycan structure in different enzyme digestion systems or complex samples, showing excellent anti-interference and applicability.
凝集素亲和层析是研究蛋白质糖基化的有力工具之一。不同的凝集素蛋白可以识别不同结构的单糖或寡糖单位,从而选择性地分离含有不同多糖结构的糖肽或糖蛋白。然而,大多数普通凝集素只能捕获部分 N-聚糖,从而降低了鉴定 N-聚糖共轭物的覆盖率。最近有报道称,糖结合蛋白 Fbs1 的工程变体对最内层的 Man3GlcNAc2 结构具有很高的亲和力,能够结合多种类型的 N-聚糖,适用于蛋白质 N-糖基化的分析。然而,将蛋白质高效固定到分离基质上是一项特别具有挑战性的工作,因为这需要保持蛋白质的功能性和完整性。在本文中,我们介绍了一种通过 N 端选择性标记技术将蛋白质共价固定在磁性纳米粒子上的简单而稳健的东方策略。我们插入了肠激酶的裂解位点,以产生特定的蛋白质 N 端甘氨酸。在生理条件下,蛋白质被甘氨酸标签固定在磁性纳米粒子表面,富集过程可在 30 分钟内完成。完成了整个聚糖和聚糖肽的富集和纯化过程,并通过 MALDI TOF-MS 进行了分析。该功能材料在不同的酶解体系或复杂样品中都能实现对聚糖结构的稳定富集,具有良好的抗干扰性和适用性。
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引用次数: 0
Towards the non-invasive determination of estradiol levels: Development and validation of an LC-MS/MS assay for quantification of salivary estradiol at sub-pg/mL level 实现雌二醇水平的无创测定:开发和验证用于定量唾液中亚克/毫升水平雌二醇的 LC-MS/MS 检测方法
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-09 DOI: 10.1016/j.aca.2024.343313
David Fabregat-Safont , Élida Alechaga , Noemí Haro , Àlex Gomez-Gomez , Eric R. Velasco , Jaime F. Nabás , Raül Andero , Oscar J. Pozo

Background

Estradiol (E2) is a female sex hormone involved in several biological processes. Although E2 levels are commonly measured in blood samples, the use of non-invasive techniques (e.g. determination of salivary E2) would allow for the collection of repeated samples and the inclusion of a greater number of participants. Immunoassay-based techniques to measure salivary E2 failed to accurately mirror the variations observed in the plasmatic concentrations of E2 during the menstrual cycle probably due to the high sensitivity required (in the sub-pg/mL range). Therefore, sensitive and rugged analytical methods for the determination of salivary E2 are required. For this, we developed and validated an analytical methodology for the accurate determination of salivary E2.

Results

The method is based on chemical derivatization with 1,2-dimethyl-1H-imidazole-5-sulphonyl chloride and liquid chromatography-tandem mass spectrometry analysis by summing highly-specific SRM transitions. This strategy allowed for increasing the sensitivity of the method. The validation of the method showed an accurate and precise quantification of E2 in 1 mL of saliva even at 250 fg/mL (97 % accuracy and 15 % RSD intra-day, and 104 % accuracy and 18 % RSD inter-day). In order to evaluate its efficacy, we analysed saliva samples from 5 healthy female volunteers collected during a whole menstrual cycle. Our analyses showed that the variations in the concentration of E2 in the measured samples mirrored those expected during a complete menstrual cycle. Additionally, we validated the suitability of our method for determining salivary E2 levels during pregnancy.

Significance

To the best of our knowledge, this is the first method that allows to precisely and accurately measuring E2 in saliva samples along the whole menstrual cycle of healthy females. It is also suitable for the determination of estradiol during pregnancy. Its high sensitivity makes this strategy ideal for the evaluation of the role of hormone production in women's health.
背景雌二醇(E2)是一种女性性激素,参与多种生物过程。尽管雌二醇水平通常通过血液样本进行测量,但使用非侵入性技术(如测定唾液中的雌二醇)可重复采集样本,并纳入更多的参与者。测量唾液 E2 的免疫测定技术无法准确反映月经周期中观察到的 E2 血浆浓度变化,这可能是由于所需的灵敏度较高(在亚皮克/毫升范围内)。因此,我们需要灵敏、耐用的分析方法来测定唾液中的 E2。结果该方法基于 1,2-二甲基-1H-咪唑-5-磺酰氯的化学衍生和液相色谱-串联质谱分析,通过对高特异性 SRM 过渡进行求和。这种方法提高了灵敏度。该方法的验证结果表明,即使在 250 fg/mL 的浓度下,1 mL 唾液中 E2 的定量也是准确和精确的(日内准确度为 97%,RSD 为 15%;日间准确度为 104%,RSD 为 18%)。为了评估其功效,我们分析了 5 名健康女性志愿者在整个月经周期中采集的唾液样本。分析结果表明,测量样本中 E2 浓度的变化反映了完整月经周期中的预期变化。据我们所知,这是第一种可以精确测量健康女性整个月经周期唾液样本中 E2 含量的方法。它也适用于孕期雌二醇的测定。它的高灵敏度使其成为评估激素分泌在女性健康中的作用的理想方法。
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引用次数: 0
Development of an accurate synchronous transport signal hand-held sensing platform for fluorescence-based berberine on-site detection 开发精确的同步传输信号手持传感平台,用于基于荧光的小檗碱现场检测
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-05 DOI: 10.1016/j.aca.2024.343304
Liucheng Guo , Liyue Du , Yan Zhang , Jie Gao , Fengling Cui

Background

Berberine is widely used in clinical treatment because of its wide antibacterial spectrum and low toxic side effects. However, its abuse could lead to bacterial resistance and several other adverse effects. In addition, measuring the content of berberine in environmental water samples helps to monitor its accumulation and metabolism in ecosystems. Traditional detection methods usually need to be carried out in the laboratory, involving complex processing procedures, which are not only time-consuming, but also unfavorable for rapid response and decision-making. Therefore, it is necessary to develop portable instruments to provide reasonable guidance on the addition and intake of berberine to reduce the harm caused by its abuse.

Results

In this work, an accurate synchronous transport signal hand-held sensing platform (STSHSP) with a low-cost, easy-to-manufacture, independent use was developed by using photoelectric conversion technology, Bluetooth technology, remote synchronous signal technology, electrical technology, and 3D printing technology. To verify the performance of STSHSP, a 5-oxo-2,3-dihydro-5H-thiazolo [3,2-a] pyridine-3,7-dicarboxylic acid (TPDCA) with ultra-high quantum yield was designed and synthesized as a probe. TPDCA exhibited bright blue fluorescence under the ultraviolet light of 365 nm which could be quenched by berberine through the inner filter effect. In the range of 0.1–80 μg/mL, the voltage displayed by the prepared STSHSP has a good linearity with the berberine concentration (R2 = 0.9997) with a detection limit of 28.32 ng/mL. The portable sensor demonstrated good stability, accuracy, and reliability in detecting actual river water, urine, traditional Chinese medicine, and its preparation samples.

Significance

The sensor with its compact structure, portability, and simple operation was suitable for in-situ detection with accurate, reliable, and feasible results, which is beneficial for improving drug quality and ensuring human health. Fortunately, the device could transmit the information to the control center and/or a third-party supervision institution in real-time, which could effectively eliminate the trust crisis. The sensor has broad application prospects in the field of environmental water quality detection and drug safety.
背景小檗碱的抗菌谱广,毒副作用小,因此被广泛用于临床治疗。然而,滥用小檗碱可能会导致细菌耐药性和其他一些不良影响。此外,测定环境水样中的小檗碱含量有助于监测其在生态系统中的积累和代谢。传统的检测方法通常需要在实验室进行,涉及复杂的处理程序,不仅耗时,而且不利于快速反应和决策。因此,有必要开发便携式仪器,为小檗碱的添加和摄入提供合理的指导,以减少其滥用带来的危害。结果在这项工作中,利用光电转换技术、蓝牙技术、远程同步信号技术、电学技术和3D打印技术,开发了一种低成本、易制造、可独立使用的精确同步传输信号手持传感平台(STSHSP)。为了验证 STSHSP 的性能,设计并合成了一种具有超高量子产率的 5-oxo-2,3-dihydro-5H-thiazolo [3,2-a] pyridine-3,7-dicarboxylic acid(TPDCA)作为探针。TPDCA 在 365 纳米紫外光下发出明亮的蓝色荧光,小檗碱可通过内滤光片效应将其淬灭。在 0.1 - 80 μg/mL 范围内,所制备的 STSHSP 显示的电压与小檗碱浓度具有良好的线性关系(R2 = 0.9997),检测限为 28.32 ng/mL。该便携式传感器在检测实际河水、尿液、中药及其制剂样品时表现出良好的稳定性、准确性和可靠性。值得庆幸的是,该设备能将信息实时传输到控制中心和/或第三方监管机构,有效消除了信任危机。该传感器在环境水质检测和药品安全领域具有广阔的应用前景。
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引用次数: 0
Intensity- and time-based strategies for micro/nano-sizing via single-particle ICP-mass spectrometry: A comparative assessment using Au and SiO2 as model particles 基于强度和时间的单颗粒 ICP 质谱仪微/纳米尺寸测定策略:以金和二氧化硅为模型颗粒的比较评估
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-05 DOI: 10.1016/j.aca.2024.343305
Antonio Bazo, Eduardo Bolea-Fernandez, Ana Rua-Ibarz, Maite Aramendía, Martín Resano

Background

Single-particle ICP-mass spectrometry (SP-ICP-MS) is a powerful method for micro/nano-particle (MNP) sizing. Despite the outstanding evolution of the technique in the last decade, most studies still rely on traditional approaches based on (1) the use of integrated intensity as the analytical signal and (2) the calculation of the transport efficiency (TE). However, the increasing availability of MNP standards and advancements in hardware and software have unveiled new venues for MNP sizing, including TE-independent and time-based approaches. This work systematically examines these different methodologies to identify and summarize their strengths and weaknesses, thus helping to determine their preferred application areas.

Results

Different SP-ICP-MS methods for MNP sizing were assessed using AuNPs (20–70 nm) and SiO2MNPs (100–1000 nm). Among TE-dependent approaches, the particle frequency method was characterized by larger uncertainties than the particle size method. The results of the latter were dependent on the appropriate selection of the reference MNP, making the use of multiple reference MNPs recommended. TE-independent methods were based on external (linear and polynomial) calibrations and a relative approach. These methods exhibited the lowest uncertainties of all the strategies evaluated. External calibrations benefited from simpler calculations, but their application could be hindered by a lack of reference MNPs within the desired size range or by the need for interpolations outside the calibration range. Finally, transit time signals are directly proportional to the MNP size rather than its mass. The time-based method demonstrated adequate performance for sizing AuNPs but failed when sizing the largest SiO2MNPs (1000 nm).

Significance and novelty

This work provides further insights into the application of different SP-ICP-MS methodologies for MNP sizing. Both TE-independent approaches and the monitoring of the transit time as the analytical signal are underused strategies; in this context, a Python script was developed for accurate transit time measurement. After 20 years of development, a quantitative comparison of the different methodologies, including the most novel approaches, is deemed necessary for further growth on solid theoretical ground.
背景单粒子 ICP 质谱法(SP-ICP-MS)是一种强大的微/纳米粒子(MNP)测定方法。尽管该技术在过去十年中取得了长足发展,但大多数研究仍依赖于基于以下两点的传统方法:(1) 使用积分强度作为分析信号;(2) 计算传输效率 (TE)。然而,随着 MNP 标准的不断增加以及硬件和软件的进步,为 MNP 的尺寸确定提供了新的途径,包括与 TE 无关的方法和基于时间的方法。结果使用 AuNPs(20 - 70 nm)和 SiO2MNPs(100 - 1000 nm)对不同的 SP-ICP-MS 方法进行了评估。在依赖 TE 的方法中,粒子频率法的不确定性大于粒度法。后者的结果取决于参考 MNP 的适当选择,因此建议使用多个参考 MNP。与 TE 无关的方法基于外部(线性和多项式)校准和相对方法。在所有评估方法中,这些方法的不确定性最低。外部校准的优点是计算简单,但由于缺乏所需尺寸范围内的参考 MNP 或需要在校准范围外进行内插,因此其应用可能会受到阻碍。最后,传输时间信号与 MNP 大小而非其质量成正比。基于时间的方法在测定 AuNPs 尺寸时表现出了足够的性能,但在测定最大的 SiO2MNPs(1000 nm)时却失败了。独立于 TE 的方法和监测作为分析信号的通过时间都是未充分利用的策略;在此背景下,我们开发了一个 Python 脚本,用于精确测量通过时间。经过 20 年的发展,我们认为有必要对不同的方法(包括最新颖的方法)进行定量比较,以便在坚实的理论基础上进一步发展。
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引用次数: 0
Optimization of complexing membranes for platinum analysis in water at part per trillion levels by X-ray fluorescence 通过 X 射线荧光法优化用于万亿分之一级水中铂分析的络合膜
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-05 DOI: 10.1016/j.aca.2024.343306
Georgia P. Vlamaki, Nikolaos G. Kallithrakas-Kontos

Background

Platinum is a critical metal, especially in medicine and catalysis. Its concentration in aquatic ecosystems may gradually affect aquatic animals due to its ability to bioaccumulate. Additionally, the recycling of platinum has become crucial, so new extraction methods are needed. In recent years, there has been increasing interest in environmental studies based on X-Ray Fluorescence, due to the requirements of green chemistry. Complexing membranes have been used for platinum analysis in combination with X-ray Fluorescence, although with a relatively high detection limit.

Results

Several optimizations were introduced to achieve a significantly improved detection limit and repeatability. Self-supported membranes were used for the first time and proved to be highly effective in binding platinum from aqueous solutions. An extensive search was conducted to identify an appropriate chemical element to serve as an internal standard; osmium met many of the necessary criteria and was successfully used as an internal standard, leading to a remarkable improvement in the method's precision. The effect of various elements present in natural waters was examined, and no interferences were observed. The method gave equally reliable results in all types of water, including seawater. Through substantial optimization procedures, a minimum detection limit up of 37 ng L−1 was achieved with a 1000 s irradiation time. The potential aging of the membrane was investigated, showing that the membrane does not deteriorate for at least one month when stored at refrigeration temperature.

Significance

The newly introduced self-supported complexing membranes improved the platinum detection limit by more than 100-fold, enabling, for the first time, platinum analysis at low ng L−1 concentration levels using X-ray Fluorescence. This method can be used to various types of natural waters, including seawater with near-complete recovery from the aquatic matrix. This research may also contribute to improving the minimum detection limits of the method for other trace elements besides platinum.
背景铂是一种重要的金属,尤其是在医药和催化领域。由于铂具有生物蓄积性,其在水生生态系统中的浓度可能会逐渐影响水生动物。此外,铂金的回收利用已变得至关重要,因此需要新的提取方法。近年来,由于绿色化学的要求,人们对基于 X 射线荧光的环境研究越来越感兴趣。络合膜已被用于结合 X 射线荧光进行铂金分析,但检测限相对较高。首次使用了自支撑膜,并证明它能非常有效地从水溶液中结合铂。为了找到一种合适的化学元素作为内标,进行了广泛的搜索;锇符合许多必要的标准,并成功地被用作内标,从而显著提高了该方法的精确度。对天然水中存在的各种元素的影响进行了研究,没有发现任何干扰。该方法在包括海水在内的所有类型的水中都能得出同样可靠的结果。通过大量的优化程序,在照射时间为 1000 秒的情况下,最低检测限可达到 37 纳克/升。新推出的自支撑络合膜将铂金检测限提高了 100 多倍,首次实现了利用 X 射线荧光法在低纳克/升浓度水平下分析铂金。这种方法可用于各种类型的自然水体,包括海水,几乎能从水生基质中完全回收。这项研究还有助于提高该方法对铂以外的其他微量元素的最低检测限。
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引用次数: 0
A novel dual-ligand copper-based nanoflower for the colorimetric and fluorescence detection of 2,4-dichlorophenol, epinephrine and hydrogen peroxide 一种新型双配体铜基纳米花,用于比色和荧光检测 2,4-二氯苯酚、肾上腺素和过氧化氢
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-05 DOI: 10.1016/j.aca.2024.343298
Jia-Xin Li , Tong-Qing Chai , Guo-Ying Chen , Mao-Ling Luo , Jian-Bo Wan , Feng-Qing Yang

Background

Nanozymes have the advantages of cost effective, simple synthesis, high durability and stability, and have been widely used in various fields. However, only a few nanomaterials with multiple enzyme-like activity have been reported, and most of the currently developed nanozymes are usually used in colorimetric or fluorescence analysis depending on a single colorimetric or fluorescence signal output. In this study, a copper-based dual-ligand biomimetic nanoflower (Cu-MN) was constructed, which demonstrated potential multiple enzyme-like activity, and was applied to the multi-mode detection of 2,4-dichlorophenol (2,4-DP), epinephrine (EP), and H2O2.

Results

The laccase-like activity of Cu-MN can catalyze the conversion of 2,4-DP and EP, resulting in the formation of red and yellow-brown oxidation products with distinct UV absorption peaks at 510 nm and 485 nm, respectively. Furthermore, the fluorescence emission peak at 426 nm of Cu-MN can be dynamic quenched during substrate oxidation due to the fluorescence internal filtration effect (IFE). Therefore, a dual-mode analysis method was constructed to detect 2,4-DP and EP by fluorescence and ultraviolet colorimetry, which was successfully applied in natural lake water and rabbit plasma analysis, respectively. Furthermore, a colorimetric sensing strategy based on the peroxidase-like activity of Cu-MN was developed and successfully applied to the monitoring of H2O2 in hydrogen peroxide disinfectant. Additionally, the visualization analysis method was also established by RGB reading of the smartphone.

Significance and novelty

In brief, inspired by the fluorescence characteristics of 2-aminoterephthallc acid and the imidazole group of 2-methylimidazole, a novel copper-based dual-ligand biomimetic nanoflower (Cu-MN) was prepared and used to establish multi-mode method for the detection of 2,4-DP, EP, and H2O2, which opens up new avenues for its applications in bioanalysis and environmental monitoring.
背景纳米酶具有成本低、合成简单、耐久性和稳定性高等优点,已被广泛应用于各个领域。然而,目前仅有少数具有类似多种酶活性的纳米材料被报道,而且目前开发的大多数纳米酶通常用于比色或荧光分析,依赖于单一的比色或荧光信号输出。本研究构建了一种铜基双配体仿生纳米花(Cu-MN),该纳米花具有潜在的类似多种酶的活性,并将其应用于 2,4-二氯苯酚(2,4-DP)、肾上腺素(EP)和 H2O2 的多模式检测。结果 Cu-MN 的类漆酶活性可催化 2,4-DP 和 EP 的转化,形成红色和黄棕色的氧化产物,紫外吸收峰分别在 510 纳米和 485 纳米。此外,在底物氧化过程中,由于荧光内滤效应(IFE),Cu-MN 在 426 纳米处的荧光发射峰会被动态淬灭。因此,构建了一种双模式分析方法,利用荧光和紫外比色法检测 2,4-DP 和 EP,并分别成功应用于天然湖水和兔血浆分析。此外,还开发了一种基于 Cu-MN 过氧化物酶样活性的比色传感策略,并成功应用于过氧化氢消毒剂中 H2O2 的监测。简而言之,受 2-aminoterephallc acid 的荧光特性和 2-methylimidazole 的咪唑基团的启发,制备了一种新型铜基双配体仿生纳米花(Cu-MN),并利用它建立了检测 2,4-DP、EP 和 H2O2 的多模式方法,为其在生物分析和环境监测领域的应用开辟了新途径。
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引用次数: 0
期刊
Analytica Chimica Acta
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