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Homogeneous Catalysts for Hydrogenative PHIP Used in Biomedical Applications 生物医学应用氢化PHIP均相催化剂
IF 2.9 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-08-15 DOI: 10.1002/anse.202400044
Dr. Mai T. Huynh, Prof. Zoltan Kovacs

At present, two competing hyperpolarization (HP) techniques, dissolution dynamic nuclear polarization (DNP) and parahydrogen (para-H2) induced polarization (PHIP), can generate sufficiently high liquid state 13C signal enhancement for in vivo studies. PHIP utilizes the singlet spin state of para-H2 to create non-equilibrium spin populations. In hydrogenative PHIP, para-H2 is irreversibly added to unsaturated precursors, typically in the presence of a homogeneous catalyst. The hydrogenation catalyst plays a crucial role in converting the singlet spin order of para-H2 into detectable nuclear polarization. Currently, rhodium(I) bisphosphine complexes are the most widely employed catalysts for PHIP, capable of catalyzing the addition of para-H2 to unsaturated precursors in organic solvents or aqueous media, depending on the ligand. Chiral catalysts enable the stereoselective production of hyperpolarized substrates. Ruthenium(II) piano stool complexes are capable of trans addition and are used to generate hyperpolarized fumarate. However, these catalysts systems are not optimal, and the greatest source of nuclear spin polarization loss is attributed to the mixing of singlet and triplet states of the protons derived from the para-H2 during the hydrogenation process. Hence, future efforts should focus on enhancing the efficiency and kinetics of these catalysts.

目前,两种相互竞争的超极化(HP)技术,溶解动态核极化(DNP)和对氢诱导极化(PHIP),可以产生足够高的液态13C信号增强,用于体内研究。PHIP利用para-H2的单线态自旋产生非平衡自旋居群。在氢化PHIP中,通常在均相催化剂的存在下,对h2被不可逆地添加到不饱和前体中。氢化催化剂在将对h2的单重态自旋顺序转化为可探测的核极化过程中起着至关重要的作用。目前,铑(I)双膦配合物是应用最广泛的PHIP催化剂,根据配体的不同,它能够在有机溶剂或水介质中催化对h2向不饱和前体的加成。手性催化剂使立体选择性生产超极化底物成为可能。钌(II)钢琴凳配合物具有反式加成的能力,用于生成超极化富马酸盐。然而,这些催化剂体系并不是最优的,核自旋极化损失的最大来源是氢化过程中来自对h2的质子的单线态和三重态的混合。因此,未来的工作应集中在提高这些催化剂的效率和动力学。
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引用次数: 0
The Promise of Carbon Nano-Onions: Preparation, Characterization and Their Application in Electrochemical Sensing 碳纳米洋葱的前景:制备、表征及其在电化学传感中的应用
IF 2.9 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-08-14 DOI: 10.1002/anse.202400035
Hector Daniel Almeida Gonzalez, Janser Hernandez Ojeda, Angel Luis Corcho-Valdés, Ivan Padron-Ramirez, Marina Perez Cruz, Claudia Iriarte-Mesa, Luis Felipe Desdin-Garcia, Pierangelo Gobbo, Manuel Antuch

Carbon nano-onions (CNOs) promise to improve the range of applications of carbon materials for electroanalytical applications. In this review, we explore the synthesis, characterization, and electrochemical applications of CNOs. CNO-based sensors present impressive features, including low detection limits in the femtogram per milliliter range, a broad linear detection range spanning up to 7 orders of magnitude, exceptional selectivity, reproducibility, and stability. Synthetic methods and characterization techniques for CNOs were thoroughly examined, shedding light on their pivotal role in biosensing technologies. Comparative analyses with other carbon materials underscore CNOs′ competitive performance, either surpassing or matching many counterparts. Despite their relatively recent integration in biosensing applications, CNOs exhibit comparable or superior results concerning other carbon-based materials. Indeed, the incorporation of CNOs into hybrid nanocomposites has shown promising outcomes, indicating a synergistic potential for future advancements in biosensing technologies. Our review provides a broad approach to the application of CNOs to the field, with emphasis on breakthroughs of the last 5 years.

碳纳米洋葱(CNOs)有望改善碳材料在电分析中的应用范围。本文综述了CNOs的合成、表征及其电化学应用。基于cnos的传感器具有令人印象深刻的特点,包括在每毫升飞图范围内的低检测限,宽线性检测范围可达7个数量级,卓越的选择性,可重复性和稳定性。深入研究了CNOs的合成方法和表征技术,揭示了其在生物传感技术中的关键作用。与其他碳材料的比较分析强调了CNOs的竞争性能,超越或与许多同行相匹配。尽管它们在生物传感应用中的整合相对较晚,但在其他碳基材料中,CNOs表现出相当或更好的结果。事实上,将CNOs加入到混合纳米复合材料中已经显示出有希望的结果,这表明了生物传感技术未来发展的协同潜力。我们的综述为CNOs在油田的应用提供了一个广泛的方法,重点介绍了过去5年的突破。
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引用次数: 0
Pioneering Sensing Technologies Using Borophene-Based Composite/Hybrid Electrochemical Biosensors for Health Monitoring: A Perspective 利用硼吩基复合/混合电化学生物传感器进行健康监测的先锋传感技术:透视
IF 2.9 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-08-07 DOI: 10.1002/anse.202400034
Shahzad Ahmed, Arshiya Ansari, Syed Kashif Ali, Bhagyashree R. Patil, Farhana Riyaz, Afzal Khan, Pranay Ranjan

Biosensors are analytical tools that integrate a biological element with a physicochemical detector in order to quantify the existence or concentration of chemicals, biomolecules, or other biological elements for human health monitoring purposes. Electrochemical techniques for biological analyte detection include the use of electrochemical sensors to identify and quantify the existence and concentration of biological molecules. These techniques are often used because of their high sensitivity, specificity, quick reaction time, and the possibility of being made smaller in size, but still, the research problem in electrochemical-based biosensing largely revolves around improving biosensors′ sensitivity, selectivity, stability, and response time. Borophene, an intriguing and novel substance within the domain of two-dimensional (2D) materials, emerges as a highly promising protagonist in the continuous and dynamic history of nanoscience and nanotechnology. Borophene, characterized by its distinctive electronic, mechanical, and thermal properties, enthralls scientists due to its atomic structure consisting exclusively of boron atoms organized in a honeycomb lattice. In recent years, borophene hybrids and composites have emerged as potentially fruitful avenues for expanding their utility in numerous fields and improving their properties. In addition, borophene and its hybrid systems hold significant potential to overcome the limitations of current electrochemical-based biosensors. By leveraging their unique properties—such as high surface area, chemical versatility, and mechanical strength—these materials can improve biosensors′ limitations. Moreover, the integration of borophene with other materials can further optimize performance, paving the way for advanced and practical biosensing solutions. This perspective presents a synopsis of recent developments in biosensing composites and hybrids based on borophene, including polymers and other nanomaterials. In addition, we emphasized the remarkable characteristics of borophene hybrids, which permit the detection of biological analytes such as proteins, nucleic acids, and small molecules in a sensitive and selective manner. Additionally, a summary of the computational investigations into analyte detection utilizing borophene-based systems has been provided. In a nutshell, we discussed the challenges and future directions in the field, outlining opportunities for further innovation and optimization of borophene-based biosensing platforms.

生物传感器是一种分析工具,它将生物元素与理化检测器结合在一起,以量化化学品、生物分子或其他生物元素的存在或浓度,从而达到监测人类健康的目的。用于生物分析物检测的电化学技术包括使用电化学传感器来识别和量化生物分子的存在和浓度。这些技术因其灵敏度高、特异性强、反应时间快以及体积可以做得更小而经常被使用,但基于电化学的生物传感的研究问题仍主要围绕提高生物传感器的灵敏度、选择性、稳定性和反应时间展开。硼吩是二维(2D)材料领域中一种引人入胜的新型物质,是纳米科学和纳米技术发展史上极具潜力的主角。硼铼具有独特的电子、机械和热特性,其原子结构完全由蜂窝晶格中的硼原子组成,这使科学家们为之着迷。近年来,硼吩混 合物和复合材料的出现为扩大其在众多领域的应用和改善其性能提供了潜在的富有成效的途径。此外,硼吩和其混合系统在克服目前基于电化学的生物传感器的局限性方面具有巨大潜力。这些材料利用其独特的性能,如高比表面积、化学多功能性和机械强度,可以改善生物传感器的局限性。此外,硼吩与其他材料的整合可以进一步优化性能,为先进实用的生物传感解决方案铺平道路。本视角概述了基于硼吩的生物传感复合材料和混合材料(包括聚合物和其他纳米材料)的最新发展。此外,我们还强调了硼吩混合物的显著特点,它可以灵敏、选择性地检测蛋白质、核酸和小分子等生物分析物。此外,我们还总结了利用硼吩基系统检测分析物的计算研究。总之,我们讨论了该领域的挑战和未来方向,概述了进一步创新和优化基于硼吩的生物传感平台的机会。
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引用次数: 0
Robust G-Quadruplex Dimer-Guided Transmembrane DNA Nanovehicles for Targeted Payload Delivery 稳健的g -四重二聚体引导的跨膜DNA纳米载体靶向有效载荷递送
IF 2.9 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-08-06 DOI: 10.1002/anse.202400048
Chengbin Liu, Qiwei Wang, Prof. Lili Shi, Prof. Tao Li

Here we report a robust G-quadruplex (G4) dimer-guided transmembrane DNA nanovehicle for targeted payload delivery, based on dimeric G4-proximized aptamers that efficiently target transferrin receptors (TfR) over-expressed on cancer cell surface. It enables the cancer-specific delivery of fluorescent G4 ligands and therapeutic drugs for cellular imaging and treatment.

在这里,我们报道了一种强大的g -四重体(G4)二聚体引导的跨膜DNA纳米载体,用于靶向有效载荷递送,基于二聚体G4-近端适配体,有效靶向癌细胞表面过表达的转铁蛋白受体(TfR)。它使荧光G4配体和用于细胞成像和治疗的治疗药物的癌症特异性递送成为可能。
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引用次数: 0
Signal Amplification by Reversible Exchange and its Translation to Hyperpolarized Magnetic Resonance Imaging in Biomedicine 可逆交换的信号放大及其在生物医学超极化磁共振成像中的应用
IF 2.9 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-08-05 DOI: 10.1002/anse.202400039
Dr. Andreas B. Schmidt, Prof. Dr. Eduard Y. Chekmenev, Henri de Maissin, Philipp R. Groß, Stefan Petersen, Luca Nagel, Prof. Dr. Franz Schilling, Dr. Ilai Schwartz, Prof. Dr. Thomas Reinheckel, Prof. Dr. Jan-Bernd Hövener, Dr. Stephan Knecht

Hyperpolarized magnetic resonance imaging (HP-MRI) has emerged as a powerful tool in molecular imaging, providing in vivo, real-time insights into metabolic pathways without ionizing radiation. Signal Amplification by Reversible Exchange (SABRE) represents a promising hyperpolarization technique, leveraging parahydrogen to enhance MRI signals. In this concept, we delineate the evolution of SABRE and landmark papers that have enabled us recently to produce biocompatible and low-cost hyperpolarized pyruvate within minutes for in vivo metabolic imaging, showcasing SABRE′s potential for preclinical and near-future clinical settings. Looking ahead, with ongoing efforts focused on optimizing polarizer technology and expanding applications beyond pyruvate, we envision SABRE as a key player in the research and application of HP-MRI due to its simplicity and throughput.

超极化磁共振成像(HP-MRI)已成为分子成像领域的一种强大工具,可在不产生电离辐射的情况下实时深入了解体内代谢途径。可逆交换信号放大技术(SABRE)是一种前景广阔的超极化技术,它利用对氢增强磁共振成像信号。在这一概念中,我们描述了 SABRE 的演变过程和具有里程碑意义的论文,这些论文使我们最近能够在几分钟内生产出生物相容性和低成本的超极化丙酮酸,用于体内代谢成像,展示了 SABRE 在临床前和不久的将来临床应用中的潜力。展望未来,SABRE 将继续致力于优化偏振片技术,并将应用扩展到丙酮酸盐以外的领域。
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引用次数: 0
Front Cover: (Anal. Sens. 4/2024) 封面:(Anal. Sens. 4/2024)
IF 2.9 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-07-16 DOI: 10.1002/anse.202480401

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引用次数: 0
Analysis of 5-Methyl Cytosine Containing Oligomers Via Reduction of Tetracationic Di-Viologen Derivatives Using Square Wave Voltammetry 利用方波伏安法分析通过还原四阳离子二缩二脲衍生物获得的含 5-甲基胞嘧啶的低聚物
IF 2.9 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-07-12 DOI: 10.1002/anse.202400011
Victoria G. Preston, Eli G. Hvastkovs

5-Methylcytosine (5 mC) is an epigenetic modification that plays several important roles ranging from development to disease progression. Local cytosine methylation is still detected and quantified utilizing bisulfite cytosine to uracil conversion and methylated base counting following PCR. Electrochemical approaches may offer more rapid means to provide this output. Here, small oligomeric DNA sequences from the CD8+ T-cell reporter gene featuring between 0 and 4 5 mC sites were immobilized on Au electrodes via self-assembly. 5 mC content was assayed via square wave voltametric reduction of a di-viologen molecule (C12H25V2+C6H12V2+C12H25, V2+=4,4’-bipyridyl or viologen) bound to the DNA. 5 mC presence induced subtle structural changes in the oligomers, which could be detected monitoring di-viologen reduction current changes at −0.39 V vs. SCE after exposure to higher ionic strength conditions. Solution phase CD spectroscopy was employed to validate the DNA structural changes occurring at the electrode surface and provide insight into the structural perturbations resulting from 5 mC presence. Overall, this method provides a relatively simple electrochemical 5 mC monitoring approach for small gene sequences based on helical structure.

5-甲基胞嘧啶(5mC)是一种表观遗传修饰,在发育和疾病进展等方面发挥着多种重要作用。目前仍利用亚硫酸氢盐胞嘧啶到尿嘧啶的转化以及 PCR 之后的甲基化碱基计数来检测和量化局部胞嘧啶甲基化。 电化学方法可以更快速地提供这种结果。在这里,来自 CD8+ T 细胞报告基因、具有 0 至 4 个 5mC 位点的小寡聚 DNA 序列通过自组装被固定在金电极上。通过方波伏安法还原与 DNA 结合的双紫精烯分子(C12H25V2+C6H12V2+C12H25,V2+ = 4,4'- 联吡啶或紫精烯)来检测 5mC 含量。5mC 的存在诱导了低聚物结构的微妙变化,在暴露于较高离子强度条件下后,通过监测二紫罗兰还原电流在 -0.39 V 与 SCE 的对比变化,可以检测到这种变化。利用溶液相 CD 光谱验证了电极表面发生的 DNA 结构变化,并深入了解了 5mC 的存在所导致的结构扰动。总之,这种方法为基于螺旋结构的小基因序列提供了一种相对简单的电化学 5mC 监测方法。
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引用次数: 0
Biomarker Multiplexing with Rational Design of Nucleic Acid Probe Complex 通过合理设计核酸探针复合物实现生物标记多重化
IF 2.9 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-07-10 DOI: 10.1002/anse.202400009
Yu Zhao, Hui Xin, Chunyan Wang

The expression profiles of intracellular biomarkers hold significance for understanding cellular biological functions and tracking pathological activities. Due to its programmability and biocompatibility, extensive efforts have been devoted to design various kinds of nucleic acid probes for biomarker detection. However, pinpointing a single biomarker could end up in a false positive signal, delaying diagnosis. In this review, we present an overview of current advances in biomarker detection and signal amplification techniques. We highlight strategies for biomarker multiplexing and signal amplification with combination of isothermal approaches. High specificity and sensitivity are the two criteria for a desired probe, as are the challenges encountered by a probe that operates efficiently in biological systems. With higher biomarker identification accuracy, we may be able to move one step closer to precision medicine.

细胞内生物标记物的表达谱对于了解细胞生物功能和追踪病理活动具有重要意义。由于核酸探针具有可编程性和生物相容性,人们一直致力于设计各种核酸探针来检测生物标志物。然而,精确定位单一生物标记物可能会出现假阳性信号,从而延误诊断。在这篇综述中,我们概述了生物标记物检测和信号放大技术的最新进展。我们重点介绍了结合等温方法进行生物标志物复用和信号放大的策略。高特异性和高灵敏度是理想探针的两个标准,也是探针在生物系统中高效运行所面临的挑战。有了更高的生物标记物识别准确度,我们或许就能向精准医疗更进一步。
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引用次数: 0
High Selectivity MEMS C2H2 Sensor for Transformer Fault Characteristic Gas Detection** 用于变压器故障特征气体检测的高选择性 MEMS C2H2 传感器**
IF 2.9 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-06-26 DOI: 10.1002/anse.202400032
Yifeng Xu, Haixia Mei, Yu Bing, Fuyun Zhang, Ning Sui, Assoc. Prof. Tingting Zhou, Xiaopeng Fan, Lijie Wang, Prof. Tong Zhang

Acetylene (C2H2), as an important characteristic gas in transformer fault diagnosis, should be accurately detected and effectively distinguished from other dissolved gases (H2, CH4, C2H6, C2H4, CO, CO2), which is crucial to determine whether the fault occurs and the fault type, but also faces challenges now. The rational design and employment of rare earth and noble metals are expected to address this issue. In this work, SnO2-3 at% Sm2O3-1 at% PdO based MEMS gas sensor was prepared to achieve high performance detection of C2H2 which has a response value of 56 to 50 ppm C2H2, response/recovery time of 2 s/136 s, lower detection limit of 1 ppm, power consumption of 15.5 mW, and weak cross sensitivity to other transformer fault characteristic gases. Lewis acids and bases theory was used to explain the reason why rare earth Sm is a benefit element to improve selectivity to C2H2. The formation of oxygen vacancies and hetero junctions was used to explain the increased sensitivity of the material. This study proved the feasibility of rare earth and noble metals as potential additives to enable advanced gas-sensitive materials for highly selective transformer fault characteristic gas C2H2 detection.

乙炔(C2H2)作为变压器故障诊断中的重要特征气体,需要准确检测并与其他溶解气体(H2、CH4、C2H6、C2H4、CO、CO2)有效区分,这对于判断是否发生故障以及故障类型至关重要,但目前也面临着挑战。稀土和贵金属的合理设计和使用有望解决这一问题。在这项工作中,制备了基于 SnO2-3 at% Sm2O3-1 at% PdO 的 MEMS 气体传感器,实现了对 C2H2 的高性能检测,其响应值为 56 至 50 ppm C2H2,响应/恢复时间为 2 s/136 s,检测下限为 1 ppm,功耗为 15.5 mW,对其他变压器故障特征气体的交叉敏感性较弱。路易斯酸和碱理论被用来解释稀土钐为何是提高对 C2H2 选择性的有利元素。氧空位和异质结的形成被用来解释材料灵敏度提高的原因。这项研究证明了稀土和贵金属作为潜在添加剂的可行性,从而使先进的气敏材料能够用于高选择性变压器故障特征气体 C2H2 的检测。
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引用次数: 0
Solvent Effects in Hyperpolarization of 15N Nuclei in [15N3]Metronidazole and [15N3]Nimorazole Antibiotics via SABRE-SHEATH** 通过 SABRE-SHEATH** 使[15N3]甲硝唑和[15N3]硝咪唑抗生素中的 15N 核超极化的溶剂效应
IF 2.9 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-06-20 DOI: 10.1002/anse.202400045
Anna P. Yi, Dr. Oleg G. Salnikov, Dr. Dudari B. Burueva, Dr. Nikita V. Chukanov, Prof. Eduard Y. Chekmenev, Prof. Igor V. Koptyug

Metronidazole and nimorazole are antibiotics of a nitroimidazole group which also may be potentially utilized as hypoxia radiosensitizers for the treatment of cancerous tumors. Hyperpolarization of 15N nuclei in these compounds using SABRE-SHEATH (Signal Amplification By Reversible Exchange in SHield Enables Alignment Transfer to Heteronuclei) approach provides dramatic enhancement of detection sensitivity of these analytes using magnetic resonance spectroscopy and imaging. Methanol-d4 is conventionally employed as a solvent in SABRE hyperpolarization process. Herein, we investigate SABRE-SHEATH hyperpolarization of isotopically labeled [15N3]metronidazole and [15N3]nimorazole in nondeuterated methanol and ethanol solvents. Optimization of such hyperpolarization parameters as polarization transfer magnetic field, temperature, parahydrogen flow rate and pressure allowed us to obtain an average 15N polarization of up to 7.2–7.4 % for both substrates. The highest 15N polarizations were observed in methanol-d4 for [15N3]metronidazole and in ethanol for [15N3]nimorazole. At a clinically relevant magnetic field of 1.4 T the 15N nuclei of these substrates possess long characteristic hyperpolarization lifetimes (T1) of ca. 1 to ca. 7 min. This study represents a major step toward SABRE in more biocompatible solvents, such as ethanol, and also paves the way for future utilization of these hyperpolarized nitroimidazoles as molecular contrast agents for MRI visualization of tumors.

甲硝唑和尼莫拉唑是硝基咪唑类抗生素,也可用作治疗癌症肿瘤的缺氧放射增敏剂。利用 SABRE-SHEATH(Signal Amplification By Reversible Exchange in SHield Enables Alignment Transfer to Heteronuclei)方法对这些化合物中的 15N 核进行超极化,可显著提高磁共振光谱和成像对这些分析物的检测灵敏度。在 SABRE 超极化过程中,甲醇-d4 通常被用作溶剂。在此,我们研究了同位素标记的[15N3]甲硝唑和[15N3]尼莫拉唑在非氚代甲醇和乙醇溶剂中的 SABRE-SHEATH 超极化过程。对极化传递磁场、温度、对氢流速和压力等超极化参数进行优化后,两种基质的平均 15N 极化率可达 7.2-7.4%。在甲醇-d4 中,[15N3]甲硝唑的 15N 极化率最高,在乙醇中,[15N3]尼莫拉唑的 15N 极化率最高。在 1.4 T 的临床相关磁场中,这些底物的 15N 核具有较长的特征超极化寿命(T1),约为 1 至 7 分钟。这项研究标志着在乙醇等生物相容性更强的溶剂中进行 SABRE 迈出了重要一步,同时也为将来利用这些超极化硝基咪唑作为分子对比剂进行肿瘤核磁共振成像铺平了道路。
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引用次数: 0
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