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Determination of metal-biomolecule interactions by relative mobility shift partial filling affinity capillary electrophoresis 通过相对迁移率偏移部分填充亲和性毛细管电泳测定金属-生物分子相互作用
IF 4.2 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-17 DOI: 10.1039/d4an01176g
Tao Huang, Jinxiang Xu, Chunsu Liang, Liyu Gong, Xiaomei Ling
Metal ions and their interactions with biomolecules play an important role in human health. However, optical detectors commonly used for HPCE cannot directly detect metal ions without UV absorption. To make up the shortcomings of existing HPCE detectors, a new universal HPCE detection system called interface-induced current detector (IICRD) has been constructed previously, with no need of derivatization procedures or complex instrumental modifications. Meanwhile, most of the reported studies on metal-biomolecule interactions only focused on the detection and analysis of biomolecules, commonly causing inaccurate or false-negative results, which was yet to be resolved. Here, the application of HPCE-IICRD realized the determination of metal-biomolecule interactions by directly measuring the electrophoretic parameters of metal ions for the first time, indicating that the interaction intensity can be measured more directly and accurately. Furthermore, an improved affinity capillary electrophoresis (ACE) method called relative mobility shift partial filling ACE-IICRD (rmsPF-ACE-IICRD) was originally developed to quantitatively analyze the binding strength. Binding behaviors between twelve free metal ions and three types of biomolecules (including two blood proteins, two enzyme proteins and two native DNAs) were investigated, and the values of equilibrium dissociation constant (KD) of metal-biomolecule complexes were calculated and evaluated by nonlinear chromatography (NLC) method. The experimental results were basically consistent with the literature values. In particular, heavy metal ions showed stronger interactions with proteins and enzymes, while metal ions tended to show stronger binding with native DNAs than proteins and enzymes, which were in agreement with literature results. The combined use of HPCE-IICRD and rmsPF-ACE showed great advantages such as no need of pretreatment, low operating cost, good repeatability, simple operation and no interference of coexisting substances, which is hopeful to become an efficient metal ion detection method, also to expand the application scope of IICRD in the future.
金属离子及其与生物大分子的相互作用对人类健康起着重要作用。然而,常用于 HPCE 的光学检测器在没有紫外线吸收的情况下无法直接检测金属离子。为了弥补现有 HPCE 检测器的不足,一种新型的通用 HPCE 检测系统--界面诱导电流检测器(IIRRD)应运而生。与此同时,大多数关于金属-生物大分子相互作用的研究仅关注于生物大分子的检测和分析,普遍存在结果不准确或假阴性的问题,这一点尚待解决。在此,应用 HPCE-IICRD 首次实现了直接测量金属离子电泳参数来测定金属-生物大分子相互作用,表明可以更直接、更准确地测量相互作用强度。此外,为了定量分析金属与生物大分子的结合强度,研究人员还开发了一种改进的亲和性毛细管电泳(ACE)方法--相对迁移率偏移部分填充ACE-IICRD(rmsPF-ACE-IICRD)。研究了12种游离金属离子与3种生物大分子(包括2种血液蛋白、2种酶蛋白和2种原生DNA)的结合行为,并利用非线性色谱法(NLC)计算和评价了金属-生物大分子复合物的平衡解离常数(KD)值。实验结果与文献值基本一致。其中,重金属离子与蛋白质和酶的相互作用更强,而金属离子与原生 DNA 的结合力往往强于蛋白质和酶,这与文献结果一致。HPCE-IICRD与rmsPF-ACE的联合使用具有无需前处理、操作成本低、重复性好、操作简单、无共存物质干扰等优点,有望成为一种高效的金属离子检测方法,也将拓展IICRD的应用范围。
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引用次数: 0
A sensitive electrochemical sensor based on CoWO4/multi-walled carbon nanotubes for the selective determination of chlorpromazine hydrochloride 基于 CoWO4/多壁碳纳米管的灵敏电化学传感器用于选择性测定盐酸氯丙嗪
IF 4.2 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-15 DOI: 10.1039/d4an01298d
Si Zeng, Peiyao Zhu, Deyu Liu, Yongmei Hu, Qitong Huang, Haiping Huang
In this work, a novel electrochemical sensor based on cobalt tungstate/multi-walled carbon nanotubes (CoWO4/MWCNTs) nanocomposite has been used to detect chlorpromazine hydrochloride (CPZ). The CoWO4/MWCNTs nanocomposite was obtained by solvothermal technology and ultrasonic method and analyzed via different characterization techniques of scanning electron microscope (SEM), X-ray diffractometer (XRD), energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The electrochemical behavior of CoWO4/MWCNTs/GCE was explored using cyclic voltammetry (CV). Electrochemical experiments have confirmed that CoWO4/MWCNTs/GCE exhibits excellent electrocatalytic activity towards CPZ with good selectivity, reproducibility and stability. The linear dynamic range of CPZ was observed to be 1-2000 µM with a detection limit of 0.33 µM. Moreover, the actual sample was analyzed using lake water with satisfactory results, which endows the sensor as potential candidates for the detection of CPZ.
在这项研究中,一种基于钨酸钴/多壁碳纳米管(CoWO4/MWCNTs)纳米复合材料的新型电化学传感器被用于检测盐酸氯丙嗪(CPZ)。CoWO4/MWCNTs 纳米复合材料是通过溶热技术和超声波法获得的,并通过扫描电子显微镜(SEM)、X 射线衍射仪(XRD)、能量色散光谱(EDS)和 X 射线光电子能谱(XPS)等不同的表征技术进行了分析。使用循环伏安法 (CV) 探索了 CoWO4/MWCNTs/GCE 的电化学行为。电化学实验证实,CoWO4/MWCNTs/GCE 对 CPZ 具有优异的电催化活性,并具有良好的选择性、重现性和稳定性。CPZ 的线性动态范围为 1-2000 µM,检测限为 0.33 µM。此外,还使用湖水对实际样品进行了分析,结果令人满意。
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引用次数: 0
Fluorogenic detection of cyanide ions in pure aqueous media through intramolecular crossed-benzoin reaction: limitations unveiled and possible solutions 通过分子内交叉安息香反应荧光检测纯水介质中的氰离子:揭示的局限性和可能的解决方案
IF 4.2 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-15 DOI: 10.1039/d4an01368a
Vincent Gaumerd, Yoan Capello, Quentin Bonnin, Pierre-Yves Renard, Anthony Romieu
Reaction-based fluorogenic sensing of lethal cyanide anion in aqueous matrices remains a big challenge. We have revisited the reported approach about intramolecular crossed-benzoin reaction leading to the release of a phenol-based fluorophore. Fluorescence assays and RP-HPLC-MS analyses have helped us to highlight its limitations related to poor aqueous stability of probes and impossibility to achieve molecular amplification despite the assumed catalytic activation mechanism. Traceless cleavable linker strategies were considered to obtain usable cyanide-responsive chemodosimeters and statistical analyses of fluorescence data have been deepened to accurately delineate their sensing performances, especially limit of detection (LOD).
对水基质中致命的氰阴离子进行基于反应的荧光传感仍然是一个巨大的挑战。我们重新研究了已报道的分子内交叉安息香反应导致苯酚基荧光团释放的方法。荧光测定和 RP-HPLC-MS 分析帮助我们强调了该方法的局限性,即探针的水稳定性差,以及尽管假定了催化活化机制,但却无法实现分子放大。我们考虑了无痕可裂解链接策略,以获得可用的氰化物响应化学剂量计,并深化了荧光数据的统计分析,以准确界定其传感性能,尤其是检测限(LOD)。
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引用次数: 0
Prussian blue-doped CaCO3 nanoparticle-labeled secondary antibodies for electrochemical immunoassay of interleukin-6 with migraine patients 用于偏头痛患者白细胞介素-6 电化学免疫测定的普鲁士蓝掺杂 CaCO3 纳米粒子标记二抗
IF 4.2 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-15 DOI: 10.1039/d4an01357c
Zhong Chen, Wenhui He, Renhe Lin, Dongzhi Wu, Xiaoling Jiang, Yunfan Cheng
Sensitive and accurate identification of interleukin-6 (IL-6) in biological fluids is very essential for judging migraine due to its role in different physiological and pathological processes. In this study, we designed a simple and feasible electrochemical immunosensing method for the voltammetric measurement of IL-6. The electrochemical immunosensor was fabricated through covalent conjugation of anti-IL-6 capture antibodies on the glassy carbon electrode with a typical carbodiimide coupling method. Anti-IL-6 secondary antibodies were labeled on the surface of Prussian blue-doped CaCO3 nanoparticle (PBCaNP) via the epoxy-amino reaction. The assay was carried out with a sandwich-type immunoreaction. In the presence of target IL-6, the analyst was sandwiched between capture antibody and detection antibody. Thereafter, the carried PBCaNP accompanying the secondary antibody could be determined by using square wave voltammetry (SWV). The voltammetric peak current was dependant on the concentration of target IL-6. Under optimum conditions, the electrochemical immunosensor exhibited good analytical properties, and allowed detection of IL-6 within a wide linear range from 0.1 to 1000 pg mL-1. The limit of detection was estimated to 0.078 pg mL-1 IL-6 at the 3sB criterion. An intermediate reproducibility of ≤10.59% was accomplished with batch-to-batch identification, and good anti-interferring capacity against other biomolecules was achieved. Importantly, clinical human serum samples obtained from 15 migraine patients were analyzed with the developed electrochemical immunosensors, giving well-matched results obtained from the referenced enzyme-linked immunosorbent assay (ELISA) method.
由于白细胞介素-6(IL-6)在不同的生理和病理过程中发挥作用,因此灵敏、准确地鉴定生物液体中的白细胞介素-6对判断偏头痛非常重要。在这项研究中,我们设计了一种简单可行的电化学免疫传感方法,用于伏安法测定 IL-6。该电化学免疫传感器是通过典型的碳二亚胺偶联法将抗 IL-6 捕获抗体共价键合在玻璃碳电极上制成的。抗 IL-6 二抗通过环氧氨基反应被标记在掺杂普鲁士蓝的 CaCO3 纳米粒子(PBCaNP)表面。检测采用夹心型免疫反应。在目标 IL-6 存在的情况下,将分析物夹在捕获抗体和检测抗体之间。然后,利用方波伏安法(SWV)测定二抗所携带的 PBCaNP。伏安峰值电流取决于目标 IL-6 的浓度。在最佳条件下,电化学免疫传感器具有良好的分析性能,可在 0.1 至 1000 pg mL-1 的宽线性范围内检测 IL-6。在 3sB 标准下,IL-6 的检测限估计为 0.078 pg mL-1。批次间鉴定的重现性≤10.59%,对其他生物大分子具有良好的抗干扰能力。重要的是,用所开发的电化学免疫传感器分析了 15 位偏头痛患者的临床人体血清样本,结果与参考的酶联免疫吸附测定法(ELISA)结果完全吻合。
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引用次数: 0
Recent Advances and Future Prospects of Oxidative-Reduction Low-Triggering-Potential Electrochemiluminescence Strategy Based on Nanoparticle Luminophores 基于纳米粒子发光体的氧化还原低触发电位电化学发光策略的最新进展和未来展望
IF 4.2 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-14 DOI: 10.1039/d4an01314j
Li Fu, Tianyuan Song, Qi Li, Guizheng Zou, Fuwei Zhang, Zongchao Li, Haotian Guan, Yingshu Guo
he oxidative-reduction electrochemiluminescence (ECL) potential of luminophore is one of the most significant indexes during the light generation processes to satisfy the growing demand for anti-interference analysis techniques, electrode compatibility and biological molecules damaging for the excessive excitation potential. The nanoparticle luminophores including quantum dots (QDs) and metal nanoclusters (NCs) processes tremendous potential for forming various ECL sensors due to their adjustable surface state. However, there are a few reviews focused on the nanoparticle luminophores based ECL system for low-triggering-potential (LTP) oxidative-reduction ECL to avoid the possible interference and oxidative damage of biological molecules. This review summarizes the recent advances of LTP oxidative-reduction ECL potential strategy of nanoparticle luminophores as ECL emitters, including matching efficient coreactant and nanoparticle luminophores, doping of nanoparticle luminophores, construction donor-acceptor system, choosing suitable working electrode, combining multiplex nanoparticle luminophores, and surface-engineering strategy. According to the different LTP ECL system, potential-lowing strategies and bio-related applications are discussed in detail. Moreover, the future trends and challenges of lowering ECL-triggering-potential strategies are discussed.
发光体的氧化还原电化学发光(ECL)电位是光产生过程中最重要的指标之一,可满足日益增长的抗干扰分析技术、电极兼容性和对过高激发电位有破坏作用的生物分子的需求。包括量子点(QDs)和金属纳米团簇(NCs)在内的纳米粒子发光体因其表面状态可调,在形成各种 ECL 传感器方面具有巨大潜力。然而,很少有综述关注基于纳米颗粒发光体的低触发电位(LTP)氧化还原 ECL 系统,以避免生物分子可能受到的干扰和氧化损伤。本综述总结了纳米颗粒发光体作为ECL发射体的低触发电位氧化还原ECL策略的最新进展,包括高效核心反应物与纳米颗粒发光体的匹配、纳米颗粒发光体的掺杂、供体-受体系统的构建、合适工作电极的选择、复用纳米颗粒发光体的组合以及表面工程策略等。针对不同的 LTP ECL 系统,详细讨论了降低潜能的策略和生物相关应用。此外,还讨论了降低 ECL 触发电位策略的未来趋势和挑战。
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引用次数: 0
Tuning the electro-catalytic activity of the Zn-Cu MOF/rGO nanocomposite as a novel enzyme-free electrochemical sensor for the detection of Oxytocin hormone 调节 Zn-Cu MOF/rGO 纳米复合材料的电催化活性,将其作为检测催产素激素的新型无酶电化学传感器
IF 4.2 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-14 DOI: 10.1039/d4an01157k
Md Zainul Abedeen, Manish Sharma, Himmat Singh Kushwaha, Ragini Gupta
Oxytocin (OXY), a peptide hormone and neurotransmitter essential to biological processes with nine distinct amino acid residues, has significantly received attention due to illegal use in food adulteration and stimulating milk ejection in cattle. Herein, for the first time, the electrochemical detection of Oxytocin (OXY) is reported using a novel nanocomposite consisting of a Zn-Cu metal-organic framework (Zn-Cu MOF) decorated on the reduced graphene oxide (rGO). An octahedral surface morphology with a crystalline structure of the size 45 nm, formation of a metal-oxygen bond, an enhanced pore diameter of 6.8 nm, a specific surface area of 70.8 m2/g, and pore volume of 0.08 cm3/g, revealed from the different characterization technique. The electro-catalytic behavior of Zn-Cu MOF/rGO nanocomposite has been increased substantially attributed to the synergistic effect, evident from the cyclic voltammetry (CV) when compared to Zn MOF, Cu MOF, Zn MOF/rGO, Cu MOF/rGO, Zn-Cu MOF keeping other parameters same. Moreover, the electrochemical impedance spectroscopy (EIS) spectra reveal the excellent conductivity of nanocomposite. The experimental parameters, viz. electrolyte pH (5), supporting electrolyte (0.1 M ABS), and volume of coating (12 µL), were optimized. The differential pulse voltammetry (DPV) technique was adopted to determine the OXY with the lowest limit of detection (LOD) to be 1.1 nM (S/N=3) with a linear range of 40 - 400 nM. The analytical application of the modified electrode was examined by spiking the OXY in pasteurized toned milk, skimmed powder milk, animal milk, and RO water, with a good recovery range of 95-106%.
催产素(OXY)是一种肽类激素和神经递质,对生物过程至关重要,具有九个不同的氨基酸残基,因被非法用于食品掺假和刺激牛产奶而备受关注。本文首次报道了一种新型纳米复合材料对催产素(OXY)的电化学检测,该复合材料由装饰在还原氧化石墨烯(rGO)上的锌-铜金属有机框架(Zn-Cu MOF)组成。通过不同的表征技术发现,Zn-Cu MOF 具有八面体表面形态,晶体结构尺寸为 45 nm,形成了金属氧键,孔径增大至 6.8 nm,比表面积为 70.8 m2/g,孔体积为 0.08 cm3/g。与 Zn MOF、Cu MOF、Zn MOF/rGO、Cu MOF/rGO、Zn-Cu MOF 相比,在其他参数不变的情况下,Zn-Cu MOF/rGO 纳米复合材料的电催化行为因协同效应而大幅提高。此外,电化学阻抗谱(EIS)光谱显示纳米复合材料具有优异的导电性。实验参数,即电解质 pH 值(5)、支持电解质(0.1 M ABS)和涂层体积(12 µL)均已优化。采用微分脉冲伏安法(DPV)测定 OXY,最低检测限(LOD)为 1.1 nM(S/N=3),线性范围为 40 - 400 nM。通过在巴氏杀菌调制奶、脱脂奶粉、动物奶和 RO 水中添加 OXY,考察了改良电极的分析应用,回收率范围为 95-106%。
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引用次数: 0
Real-time monitoring of vancomycin using split-aptamer surface plasmon resonance biosensor 利用分裂aptamer表面等离子体共振生物传感器实时监测万古霉素
IF 4.2 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-14 DOI: 10.1039/d4an01226g
Cátia Santa, Soohyun Park, Artur Gejt, Heather A Clark, Bastian Hengerer, Khulan Sergelen
Real-time monitoring of therapeutic drugs is crucial for treatment management and pharmacokinetic studies. We present the optimization and affinity tuning of split-aptamer sandwich assay for real-time monitoring of the narrow therapeutic window drug vancomycin, using surface plasmon resonance (SPR). To achieve reversible, label-free sensing of small molecules by SPR, we adapted the vancomycin binding aptamer in a sandwich assay format through split-aptamer approach. By evaluating multiple split sites within the secondary structure of the original aptamer, we identified position 27 (P27) as optimal for preserving target affinity, ensuring reversibility, and maximizing sensitivity. The assay demonstrated robust performance under physiologically relevant ranges of pH and divalent cations and the specific ternary complex formation of the aptamer split segments with the analyte was confirmed by circular dichroism spectroscopy. Subsequently, we engineered a series of split-aptamer pairs with increasing complementarity in the stem regions, improving both the affinity and limit of detection up to 10-fold, as compared to the primary P27 pair. The kinetics of the engineered split-aptamer pairs were evaluated, revealing fast association and dissociation rates, confirming improved affinity and detection limits across variants. Most importantly, the reversibility of the assay, essential for real-time monitoring, was maintained in all pairs. Finally, the assay was further validated in complex biological matrices, including cerebrospinal fluid from dog and diluted plasma from rat, demonstrating functionality in biological environments, and stability exceeding 9 hours. Our study paves the way for applications of split-aptamers in real-time monitoring of small molecules, with potential implications for in vivo therapeutic drug monitoring and pharmacokinetic studies.
实时监测治疗药物对于治疗管理和药代动力学研究至关重要。我们利用表面等离子体共振(SPR)技术,对用于实时监测治疗窗口期较窄的药物万古霉素的分离式吸附剂夹心检测法进行了优化和亲和力调谐。为了通过 SPR 实现对小分子的可逆、无标记传感,我们将万古霉素结合适配体通过分裂适配体方法改装成夹心测定格式。通过评估原始适配体二级结构中的多个分裂位点,我们确定第 27 位(P27)是保持目标亲和力、确保可逆性和最大灵敏度的最佳位置。该检测方法在生理相关的 pH 值和二价阳离子范围内表现出了强大的性能,并且通过圆二色性光谱证实了合体分裂片段与分析物形成的特异性三元复合物。随后,我们又设计了一系列拆分适配体对,其干区的互补性不断增加,与原始的 P27 对相比,亲和力和检测限均提高了 10 倍。对工程化拆分aptamer对的动力学进行了评估,发现其结合和解离速率很快,证实了不同变体的亲和力和检测限均有所提高。最重要的是,所有配对都保持了检测的可逆性,这对实时监测至关重要。最后,该检测方法在复杂的生物基质中得到了进一步验证,包括狗的脑脊液和大鼠的稀释血浆,证明了其在生物环境中的功能性和超过 9 小时的稳定性。我们的研究为在小分子实时监测中应用拆分触媒铺平了道路,对体内治疗药物监测和药代动力学研究具有潜在的意义。
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引用次数: 0
Green One-step Pyrolytic Synthesis of Folic Acid-Derived Carbon Dots for Sensitive Turn-on Fluorescence Detection of Cysteine 一步绿色热解合成叶酸衍生碳点,用于半胱氨酸的灵敏荧光检测
IF 4.2 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-13 DOI: 10.1039/d4an01144a
Jie Huang, Ruicheng Xu, Qiaoting Yang, kang Tao, Dan Shan
This study introduces a straightforward one-step pyrolytic method for synthesizing carbon dots derived from folic acid (FACDs). This green and cost-effective approach simplifies the production of fluorescent carbon nanomaterials, which exhibit strong and stable fluorescence properties. These properties make FACDs particularly suitable for the sensitive and selective detection of cysteine (Cys) through a "turn-on" fluorescence mechanism. The FACDs demonstrate a low detection limit of 1.7 × 10⁻⁷ M and a broad linear range from 5.0 × 10⁻⁷ to 8.0 × 10⁻ 5M, effectively restoring quenched fluorescence in the presence of Cys. These results underscore the potential of FACDs as reliable, high-performance sensors for various biological and environmental applications, paving the way for the development of versatile and efficient fluorescence-based detection platforms.
本研究介绍了一种简单的一步热解法合成叶酸衍生碳点(FACDs)。这种绿色环保、经济高效的方法简化了荧光碳纳米材料的生产过程,这种材料具有强烈而稳定的荧光特性。这些特性使 FACDs 特别适合通过 "开启 "荧光机制对半胱氨酸(Cys)进行灵敏和选择性检测。FACD 的检测限低至 1.7 × 10-⁷ M,线性范围从 5.0 × 10-⁷ 到 8.0 × 10- 5M,能有效恢复 Cys 存在时淬灭的荧光。这些结果凸显了 FACD 作为可靠、高性能传感器在各种生物和环境应用中的潜力,为开发多功能、高效的荧光检测平台铺平了道路。
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引用次数: 0
Towards high-resolution water isotope analysis in ice cores using laser ablation – cavity ring-down spectroscopy 利用激光烧蚀-空腔环向下光谱技术实现冰芯中水同位素的高分辨率分析
IF 4.2 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-12 DOI: 10.1039/d4an01054j
Eirini Malegiannaki, Pascal Bohleber, Daniele Zannoni, Ciprian Stremtan, Agnese Petteni, Barbara Stenni, Carlo Barbante, Bo M. Vinther, Vasileios Gkinis
A new micro-destructive technique for high-resolution water isotope analysis of ice samples using a Laser Ablation (LA) system coupled with a Cavity Ring Down Spectrometer (CRDS) is presented. This method marks the first time water isotope analysis is conducted directly on the ice, bypassing the traditional steps of melting and vaporizing the ice sample, thanks to the direct transition of ice into water vapour through the laser ablation process. A nanosecond ArF laser ablation system (193 nm) with an integrated two-volume ablation chamber was successfully coupled to a CRDS analyzer, utilizing nitrogen as the carrier gas. The application goal is the use of LA-CRDS for ice core studies, so a method for preparing ice standard samples using liquid water isotope standards, widely used for ice core analysis, is introduced. The measurements were conducted in a discrete mode, by performing laser ablation raster scans of 4 mm × 4 mm areas, establishing a sampling resolution of 4 mm along an ice core's depth. The water vapour concentration reaching the CRDS analyzer as well as the quality of the water isotopic measurements of δ18O and δD were influenced by laser parameters, such as laser spot size, repetition rate, laser fluence, ablation time as well as by the flow rates of the carrier gas. After optimizing the experimental conditions for water vapour formation, three ice standards samples were analyzed for calibration purposes on the VSMOW-SLAP scale and a section of an ice core sample was also tested. Critical parameters influencing the precision and accuracy of water isotopic measurements were investigated, and isotopic fractionation phenomena were identified, pointing to essential considerations for the technique's further development.
介绍了一种利用激光烧蚀(LA)系统和腔环向下光谱仪(CRDS)对冰样品进行高分辨率水同位素分析的新型微破坏技术。这种方法是首次直接在冰上进行水同位素分析,绕过了传统的冰样融化和汽化步骤,通过激光烧蚀过程将冰直接转化为水蒸气。纳秒 ArF 激光烧蚀系统(193 纳米)集成了两个烧蚀室,利用氮气作为载气,成功地与 CRDS 分析仪耦合。应用目标是将 LA-CRDS 用于冰芯研究,因此介绍了一种利用广泛用于冰芯分析的液态水同位素标准制备冰标准样品的方法。测量以离散模式进行,对 4 毫米×4 毫米的区域进行激光烧蚀光栅扫描,沿冰芯深度建立 4 毫米的采样分辨率。到达 CRDS 分析仪的水蒸气浓度以及 δ18O 和 δD 水同位素测量的质量受到激光参数的影响,如激光光斑大小、重复率、激光通量、烧蚀时间以及载气流速。在对水蒸气形成的实验条件进行优化后,对三个冰标准样品进行了分析,以便在 VSMOW-SLAP 标尺上进行校准,同时还对冰芯样品的一个部分进行了测试。对影响水同位素测量精度和准确性的关键参数进行了研究,并确定了同位素分馏现象,为该技术的进一步发展提供了重要依据。
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引用次数: 0
Rapid lung ventilation MRI using parahydrogen-induced polarization of propane gas 利用丙烷气体的对氢诱导极化实现快速肺通气磁共振成像
IF 4.2 3区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-12 DOI: 10.1039/d4an01029a
Md Raduanul H. Chowdhury, Clementinah Oladun, Nuwandi M. Ariyasingha, Anna Samoilenko, Tarek Bawardi, Dudari B. Burueva, Oleg G. Salnikov, Larisa M. Kovtunova, Valerii I. Bukhtiyarov, Zhongjie Shi, Kehuan Luo, Sidhartha Tan, Juri G. Gelovani, Igor V. Koptyug, Boyd M. Goodson, Eduard Y. Chekmenev
Proton-hyperpolarized contrast agents are attractive because they can be imaged on virtually any clinical MRI scanner, which is typically equipped to scan only protons rather than heteronuclei (i.e., anything besides protons, e.g., 13C, 15N, 129Xe, 23Na, etc.). Even though the lifetime of the proton spin hyperpolarization is only a few seconds, it is sufficient for inhalation and scanning of proton-hyperpolarized gas media. We demonstrate the utility of producing hyperpolarized propane gas via heterogeneous parahydrogen-induced polarization for the purpose of ventilation imaging in an excised rabbit lung model. The magnetization of protons in hyperpolarized propane gas is similar to that of tissue water protons, making it possible to rapidly perform lung ventilation imaging with a 0.35 T clinical MRI scanner. Here, we demonstrate the feasibility of rapid (2 s) lung ventilation MRI in excised rabbit lungs using hyperpolarized propane gas with a 1 × 1 mm2 pixel size using a 50 mm slice thickness, and a 1.7 × 1.7 mm2 pixel size using a 9 mm slice thickness.
质子超极化造影剂之所以具有吸引力,是因为它们几乎可以在任何临床核磁共振成像扫描仪上成像,而这种扫描仪通常只扫描质子而不是异核(即除质子以外的任何物质,如 13C、15N、129Xe、23Na 等)。尽管质子自旋超极化的寿命只有几秒钟,但它足以用于质子超极化气体介质的吸入和扫描。我们展示了通过异质副氢诱导极化产生超极化丙烷气体的实用性,以便在切除的兔肺模型中进行通气成像。超极化丙烷气体中质子的磁化率与组织水质子的磁化率相似,这使得使用 0.35 T 临床磁共振成像扫描仪快速进行肺通气成像成为可能。在这里,我们展示了使用超极化丙烷气体在切除的兔肺中进行快速(2 秒)肺通气磁共振成像的可行性,使用 50 毫米切片厚度时像素大小为 1 × 1 平方毫米,使用 9 毫米切片厚度时像素大小为 1.7 × 1.7 平方毫米。
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引用次数: 0
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