Osmium

  • 文章类型: Journal Article
    羟自由基(·OH)清除能力(HOSC)的估算对于评估抗氧化剂至关重要,天然提取物,或针对临床疾病的药物。虽然纳米酶在相关应用中具有优势,它们仍然面临着活性和选择性的限制。作为回应,这项工作展示了制造的海带蛋白调制的锇(laminarin-Os)纳米簇(1.45±0.05nm),在为合理的HOSC估计量身定制的比色测定中充当过氧化物酶样纳米酶。这项研究验证了海带多糖的表征和显着的稳定性。通过利用海带蛋白Os丰富的表面负电荷和海带蛋白的表面羟基,促进氧化反应,增强laminarin-Os对3,3'的亲和力,5,5'-四甲基联苯胺(TMB)(KM=0.04mM)。这使得基于海带蛋白-Os的比色测定能够比柠檬酸盐更有效地响应·OH,白蛋白-,或其他基于多糖的Os。此外,实验结果还验证了在酸性条件下海带蛋白-Os的选择性过氧化物酶样行为。像抗坏血酸这样的抗氧化剂,谷胱甘肽,鞣酸,和半胱氨酸在比色平台中抑制652nm处的吸光度,使用海带蛋白-Os的过氧化物酶样活性。与商用套件相比,该测定显示出较高的灵敏度(例如,响应抗坏血酸0.01-0.075mM,谷胱甘肽1-15µg/mL,单宁酸0.5-5µM,和甘草酸单铵半胱氨酸1.06-10.63µM)和谷胱甘肽的HOSC测试,鞣酸,和甘草酸单铵半胱氨酸。总的来说,这项研究介绍了一种具有特殊的TMB亲和力和·OH选择性的新型Os纳米酶,为生物医学研究中的HOSC估计铺平了道路,药物分析,药品质量控制,和超越。
    Hydroxyl radical (·OH) scavenging capacity (HOSC) estimation is essential for evaluating antioxidants, natural extracts, or drugs against clinical diseases. While nanozymes offer advantages in related applications, they still face limitations in activity and selectivity. In response, this work showcases the fabrication of laminarin-modulated osmium (laminarin-Os) nanoclusters (1.45 ± 0.05 nm), functioning as peroxidase-like nanozymes within a colorimetric assay tailored for rational HOSC estimation. This study validates both the characterization and remarkable stability of laminarin-Os. By leveraging the abundant surface negative charges of laminarin-Os and the surface hydroxyls of laminarin, oxidation reactions are facilitated, augmenting laminarin-Os\'s affinity for 3,3\',5,5\'-tetramethylbenzidine (TMB) (KM = 0.04 mM). This enables the laminarin-Os-based colorimetric assay to respond to ·OH more effectively than citrate-, albumin-, or other polysaccharides-based Os. In addition, experimental results also validate the selective peroxidase-like behavior of laminarin-Os under acidic conditions. Antioxidants like ascorbic acid, glutathione, tannic acid, and cysteine inhibit absorbance at 652 nm in the colorimetric platform using laminarin-Os\'s peroxidase-like activity. Compared with commercial kits, this assay demonstrates superior sensitivity (e.g., responds to ascorbic acid 0.01-0.075 mM, glutathione 1-15 µg/mL, tannic acid 0.5-5 µM, and monoammonium glycyrrhizinate cysteine 1.06-10.63 µM) and HOSC testing for glutathione, tannic acid, and monoammonium glycyrrhizinate cysteine. Overall, this study introduces a novel Os nanozyme with exceptional TMB affinity and ·OH selectivity, paving the way for HOSC estimation in biomedical research, pharmaceutical analysis, drug quality control, and beyond.
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  • 文章类型: Journal Article
    表现出催化作用机制的抗癌剂提供了克服耐药性的独特多靶向策略。尽管如此,开发中的许多细胞内催化剂受到内源性亲核试剂失活的阻碍。我们合成了一种非常有效的,通过在芳烃和螯合二胺配体之间引入永久性共价系链,稳定的基于Os的16电子半三明治(\'钢琴粪便\')催化剂。该催化剂对三阴性乳腺癌细胞表现出与临床药物顺铂相当的抗增殖活性,并且可以克服他莫昔芬耐药性。形态实验显示,Os在细胞外介质中几乎完全与白蛋白结合,虽然细胞积累研究发现了能量依赖性,蛋白质介导的Os积累途径,与白蛋白介导的摄取一致。重要的是,系留的Os复合物对胞内转移加氢催化具有活性,通过共同施用无毒剂量的甲酸钠作为氢化物的来源,表明Os催化剂完整地递送到癌细胞的胞质溶胶中。作用机制涉及活性氧(ROS)的产生,从而利用癌细胞固有的氧化还原脆弱性,伴随着癌细胞相对于非致瘤细胞的选择性。
    Anticancer agents that exhibit catalytic mechanisms of action offer a unique multi-targeting strategy to overcome drug resistance. Nonetheless, many in-cell catalysts in development are hindered by deactivation by endogenous nucleophiles. We have synthesised a highly potent, stable Os-based 16-electron half-sandwich (\'piano stool\') catalyst by introducing a permanent covalent tether between the arene and chelated diamine ligand. This catalyst exhibits antiproliferative activity comparable to the clinical drug cisplatin towards triple-negative breast cancer cells and can overcome tamoxifen resistance. Speciation experiments revealed Os to be almost exclusively albumin-bound in the extracellular medium, while cellular accumulation studies identified an energy-dependent, protein-mediated Os accumulation pathway, consistent with albumin-mediated uptake. Importantly, the tethered Os complex was active for in-cell transfer hydrogenation catalysis, initiated by co-administration of a non-toxic dose of sodium formate as a source of hydride, indicating that the Os catalyst is delivered to the cytosol of cancer cells intact. The mechanism of action involves the generation of reactive oxygen species (ROS), thus exploiting the inherent redox vulnerability of cancer cells, accompanied by selectivity for cancerous cells over non-tumorigenic cells.
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  • 文章类型: Journal Article
    最近已经报道了具有锇纳米颗粒的膜材料用于块状膜和支撑复合膜系统。在本论文中,提出了一种基于分散在正癸醇(nD)或正十二烷醇(nDD)中的锇的催化材料,它也可以作为乳液膜。对硝基苯酚(PNP)的氢化在反应和分离塔中进行,其中酸接收相中的乳液分散在n醇中的锇纳米分散体中。PNP转化过程和对氨基苯酚(PAP)转运的变量如下:膜醇的性质,流动状态,源和接收阶段之间的pH差异以及操作周期数。在所有情况下,nD的转化结果都比nDD好。逆流流动状态优于顺流流动。增加源阶段和接收阶段之间的pH差异会放大该过程。操作周期数限制为五个,之后需要再生膜分散体。基于具有锇纳米颗粒纳米分散的乳液膜(正十二烷醇为0.1×10-3s-1,正癸醇为0.9×10-3s-1)的新型催化材料的表观催化速率常数(kapp)与基于铂金属族催化剂吸附的催化剂相比降低了一个数量级。测试的膜催化材料的优点是它在酸接收相中提取对氨基苯酚。
    Membrane materials with osmium nanoparticles have been recently reported for bulk membranes and supported composite membrane systems. In the present paper, a catalytic material based on osmium dispersed in n-decanol (nD) or n-dodecanol (nDD) is presented, which also works as an emulsion membrane. The hydrogenation of p-nitrophenol (PNP) is carried out in a reaction and separation column in which an emulsion in the acid-receiving phase is dispersed in an osmium nanodispersion in n-alcohols. The variables of the PNP conversion process and p-aminophenol (PAP) transport are as follows: the nature of the membrane alcohol, the flow regime, the pH difference between the source and receiving phases and the number of operating cycles. The conversion results are in all cases better for nD than nDD. The counter-current flow regime is superior to the co-current flow. Increasing the pH difference between the source and receiving phases amplifies the process. The number of operating cycles is limited to five, after which the regeneration of the membrane dispersion is required. The apparent catalytic rate constant (kapp) of the new catalytic material based on the emulsion membrane with the nanodispersion of osmium nanoparticles (0.1 × 10-3 s-1 for n-dodecanol and 0.9 × 10-3 s-1 for n-decanol) is lower by an order of magnitude compared to those based on adsorption on catalysts from the platinum metal group. The advantage of the tested membrane catalytic material is that it extracts p-aminophenol in the acid-receiving phase.
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  • 文章类型: Journal Article
    在植物和活体切片上的细胞培养物中的次生代谢物定位的研究受到难以获得的阻碍,正确定向的部分。用于将组织固定在树脂中的技术允许克服这些困难。适当选择的组织固定技术允许使用不同的染料来鉴定感兴趣的化合物。此外,组织固定的某些成分可以用作固定剂和鉴定次级代谢产物的染料。例如,四氧化锇,将脂质固定在组织中,将酚类化合物染成黑色。本文介绍了使用四氧化锇检测荞麦形态发生愈伤组织培养物中酚类化合物的方法。甲苯胺蓝O染料,和氯化铁作为染料在环氧树脂包埋的细胞培养中进行双重固定,并将材料固定在Karnovsky的固定剂中。
    The study of the localization of secondary metabolites in both plants and the cell cultures on the intravital sections is hampered by the difficulty of obtaining thin, correctly oriented sections. Techniques for fixing tissues in resins allow these difficulties to be overcome. Properly selected tissue fixation techniques allow using different dyes to identify the compound of interest. In addition, some components of tissue fixation can act as fixatives and as a dye for identifying secondary metabolites. For example, osmium tetroxide, which fixes lipids in tissues, stains phenolic compounds black. This paper describes methods for the detection of phenolic compounds in morphogenic callus culture of buckwheat using osmium tetroxide, Toluidine Blue O dye, and ferric chloride as dyes in epoxy resin-embedded cell culture with double fixation of the material and when material fixed in Karnovsky\'s fixative.
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  • 文章类型: Journal Article
    糖尿病伤口容易受到细菌感染,在很大程度上与高血糖(高血糖)有关。为了治疗这样的伤口,例如葡萄糖氧化酶(GOx)的酶可以与纳米酶(纳米材料模拟酶)组合以有效地使用葡萄糖用于目的。然而,这些系统仍有改进的空间,特别是在过程简化方面,酶活性调节,和治疗效果。在这里,我们的方法利用GOx直接促进锇(Os)纳米酶(GOx-OsNC)的生物矿化生长,导致双重活性中心和显着的三重酶活性。最初,GOx-OsNC采用邻位双活动中心,启用自级联机制,与逐步反应相比,显着增强葡萄糖传感性能,超越其他金属来源如金和铂的能力。此外,GOx-OsNC已整合到葡萄糖感应凝胶中,实现瞬时视觉反馈。在感染的糖尿病伤口的治疗中,GOx-OsNC通过降低血糖水平并通过产生羟基自由基而表现出抗菌性能,从而表现出多方面的益处,从而通过培育有利的微环境来加速愈合。此外,GOx-OsNC的过氧化氢酶样活性有助于减少氧化应激,炎症,缺氧,最终改善愈合结果。总的来说,这种协同酶-纳米酶混合物是用户友好的,并具有广泛的应用前景。本文受版权保护。保留所有权利。
    Diabetic wounds are susceptible to bacterial infections, largely linked to high blood glucose levels (hyperglycemia). To treat such wounds, enzymes like glucose oxidase (GOx) can be combined with nanozymes (nanomaterials mimic enzymes) to use glucose effectively for purposes. However, there is still room for improvement in these systems, particularly in terms of process simplification, enzyme activity regulation, and treatment effects. Herein, the approach utilizes GOx to directly facilitate the biomineralized growth of osmium (Os) nanozyme (GOx-OsNCs), leading to dual-active centers and remarkable triple enzyme activities. Initially, GOx-OsNCs use vicinal dual-active centers, enabling a self-cascaded mechanism that significantly enhances glucose sensing performance compared to step-by-step reactions, surpassing the capabilities of other metal sources such as gold and platinum. In addition, GOx-OsNCs are integrated into a glucose-sensing gel, enabling instantaneous visual feedback. In the treatment of infected diabetic wounds, GOx-OsNCs exhibit multifaceted benefits by lowering blood glucose levels and exhibiting antibacterial properties through the generation of hydroxyl free radicals, thereby expediting healing by fostering a favorable microenvironment. Furthermore, the catalase-like activity of GOx-OsNCs aids in reducing oxidative stress, inflammation, and hypoxia, culminating in improved healing outcomes. Overall, this synergistic enzyme-nanozyme blend is user-friendly and holds considerable promise for diverse applications.
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  • 文章类型: Journal Article
    一系列新的螯合双齿(SS)烷基咪唑-2-硫酮-Ru(II)/Os(II)配合物(3ai,3aii,3aiii,3bii/4aii,4bi,4bii),和三齿(SNS)吡啶-2,6-二基咪唑-2-硫酮-Ru(II)/Os(II)配合物(5bi,5civ/6bi,6ci,6civ)形式为[MII(cym)(L)Cl]PF6和[MII(cym)(L)]PF6(M=Ru或Os,Cym=η6-对异丙基苯,和L=硫脲的杂环衍生物),成功合成。光谱和分析方法用于表征配合物及其配体。固态单晶X射线衍射分析显示,在各个配合物中的Ru(II)或Os(II)中心周围呈“钢琴凳”几何形状。使用MTT测定法研究了复合物对人宫颈癌(HeLa)和非癌细胞系(Hek293)的体外化疗活性。化合物3aii,5civ,5bi,4aiii,6ci,6civ,和参考药物,发现5-氟尿嘧啶对肿瘤细胞具有选择性;化合物3ai,3aiii,3bii,4bi,4bii,6bi,发现在正常和肿瘤细胞系之间没有选择性。三齿半夹心复合物5bi的IC50值(86±9μM)显示出与参考的商业抗癌药物相当的抗增殖活性,5-氟尿嘧啶(87±15μM)。在各自的剂量浓度下,钳形(SNS)锇络合物6ci(36±10μM)和6civ(40±4μM)的有效性是参考药物5-氟尿嘧啶的两倍。然而,类似的夹式(SNS)钌络合物5civ是无效的,没有显示抗增殖活性,甚至在147±1μM的较高浓度下。这些发现暗示,络合物中的螯合(SS)和钳(SNS)配体结构的较高稳定性通过减少在生理条件下配体解离的机会来改善络合物的生物(抗增殖)活性。总的来说,夹式(SNS)锇配合物被发现比它们的钌类似物更具细胞毒性,表明咪唑-2-硫酮-Ru/Os配合物的抗增殖活性取决于配体的空间配位,金属中心的性质,和金属络合物离子的电荷。
    A series of new chelating bidentate (SS) alkylimidazole-2-thione-Ru(II)/Os(II) complexes (3ai, 3aii, 3aiii, 3bii/4aiii, 4bi, 4bii), and the tridentate (SNS) pyridine-2,6-diylimidazole-2-thione-Ru(II)/Os(II) complexes (5bi, 5civ/6bi, 6ci, 6civ) in the forms [MII(cym)(L)Cl]PF6 and [MII(cym)(L)]PF6 (M = Ru or Os, cym = η6-p-cymene, and L = heterocyclic derivatives of thiourea) respectively, were successfully synthesized. Spectroscopic and analytical methods were used to characterize the complexes and their ligands. Solid-state single-crystal X-ray diffraction analyses revealed a \"piano-stool\" geometry around the Ru(II) or Os(II) centers in the respective complexes. The complexes were investigated for in vitro chemotherapeutic activities against human cervical carcinoma (HeLa) and the non-cancerous cell line (Hek293) using the MTT assay. The compounds 3aii, 5civ, 5bi, 4aiii, 6ci, 6civ, and the reference drug, 5-fluorouracil were found to be selective toward the tumor cells; the compounds 3ai, 3aiii, 3bii, 4bi, 4bii, and 6bi, which were found not to be selective between normal and tumor cell lines. The IC50 value of the tridentate half-sandwich complex 5bi (86 ± 9 μM) showed comparable anti-proliferative activity with the referenced commercial anti-cancer drug, 5-fluorouracil (87 ± 15 μM). The pincer (SNS) osmium complexes 6ci (36 ± 10 μM) and 6civ (40 ± 4 μM) were twice as effective as the reference drug 5-fluorouracil at the respective dose concentrations. However, the analogous pincer (SNS) ruthenium complex 5civ was ineffective and did not show anti-proliferative activity, even at a higher concentration of 147 ± 1 μM. These findings imply that the higher stability of the chelating (SS) and the pincer (SNS) ligand architectures in the complexes improves the biological (anti-proliferative) activity of the complexes by reducing the chance of ligand dissociation under physiological conditions. In general, the pincer (SNS) osmium complexes were found to be more cytotoxic than their ruthenium analogues, suggesting that the anti-proliferative activity of the imidazole-2-thione-Ru/Os complexes depends on the ligand\'s spatial coordination, the nature of the metal center, and the charge of the metal complex ions.
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  • 文章类型: Journal Article
    急性肾损伤(AKI)是化疗患者常见的不良事件。AKI伴随着活性氧(ROS)和炎症的产生。因此,ROS和炎症的管理是缓解AKI的潜在策略.在这里,聚乙二醇涂层的基于纳米酶的解毒剂(Os)被开发用于成像引导的光热疗法(PTT)与顺铂(Pt)联合使用,同时避免了高剂量Pt引起的AKI。Os纳米解毒剂可以提高PTT和化疗联合治疗肿瘤的效率,并通过改善缺氧和炎性肿瘤微环境来抑制肿瘤转移。Os纳米解毒剂由于其2nm的大小分布而优先在肾脏中积累,然后通过清除ROS和产生氧气来调节炎症以减轻Pt诱导的AKI。Os纳米解毒剂可以通过尿液排泄从肾脏清除,但可以在过氧化氢刺激下降解,减少这些化合物的生物滞留。通过整合PTT与炎症调节,Os纳米解毒剂有可能减少化疗的副作用,为化疗诱导的AKI癌症患者的临床治疗提供替代途径。本文受版权保护。保留所有权利。
    Acute kidney injury (AKI) is a common adverse event in chemotherapy patients. AKI is accompanied by the generation of reactive oxygen species (ROS) and inflammation. Therefore, the management of ROS and inflammation is a potential strategy for AKI mitigation. Herein, polyethylene glycol-coated osmium nanozyme-based antidotes (Os) are developed for imaging-guided photothermal therapy (PTT) in combination with cisplatin (Pt); while, avoiding AKI induced by high-dose Pt. Os nanoantidotes can enhance the efficiency of tumor treatment during combined PTT and chemotherapy and inhibit tumor metastasis by improving the hypoxic and inflammatory tumor microenvironment. Os nanoantidotes preferentially accumulate in the kidney because of their 2-nm size distribution; and then, regulate inflammation by scavenging ROS and generating oxygen to alleviate Pt-induced AKI. Os nanoantidotes can be cleared from the kidneys by urine excretion but can be degraded under hydrogen peroxide stimulation, reducing the bio-retention of these compounds. By integrating PTT with inflammatory regulation, Os nanoantidotes have the potential to reduce the side effects of chemotherapy, offering an alternative route for the clinical management of cancer patients with chemotherapy-induced AKI.
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  • 文章类型: Case Reports
    四氧化锇是一种强氧化剂。皮肤接触四氧化锇后,皮肤变色和红色丘疹可能发生。我们描述了由于四氧化锇而导致皮肤变色的患者。
    一名25岁的研究生在实验室工作时无意中将手暴露于四氧化锇。立即清洗后,他因左中指变色而寻求医疗护理。他报告患处没有不适。继续进行彻底的水冲洗,并应用皮质类固醇软膏。
    我们的患者在左中指的腹侧出现深棕色色素沉着。一周后色素消失。
    四氧化锇可引起深棕色皮肤变色。
    UNASSIGNED: Osmium tetroxide is a strong oxidizing agent. After dermal exposure to osmium tetroxide, skin discoloration and red papules can occur. We describe a patient with skin discoloration due to osmium tetroxide.
    UNASSIGNED: A 25-year-old postgraduate student unintentionally exposed his hand to osmium tetroxide while working in a laboratory setting. After immediate washing, he sought medical care due to left middle finger discoloration. He reported no discomfort in the affected area. Thorough water rinsing was continued, and corticosteroid ointment was applied.
    UNASSIGNED: Our patient developed dark brown pigmentation on the ventral side of the left middle finger. The pigmentation disappeared one week later.
    UNASSIGNED: Osmium tetroxide may induce dark brown skin discoloration.
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  • 文章类型: Journal Article
    树脂包埋标本的超薄切片的二维观察对膜性细胞器的三维(3D)形态信息的理解不足。锇浸渍法,由田中教授的小组开发>40年前,是唯一允许使用扫描电子显微镜(SEM)直接观察膜系统的3D超微结构的技术,不需要任何重建过程。使用这种方法,可溶性细胞质蛋白从冻裂的细胞表面去除,同时保持膜细胞器的完整性,通过将组织浸入稀释的锇溶液中几天来实现。通过采用浸渍法,研究人员使用SEM揭示了诸如高尔基体等细胞器的3D超微结构,各种细胞类型的线粒体和内质网。最近,我们开发了基于浸渍方法的新SEM技术,以探索该方法的进一步可能性。这些措施包括:(i)一种快速的锇浸渍方法,该方法可以减少该程序的反应持续时间,(ii)将琼脂糖包埋与锇浸渍相结合的组合方法,以阐明游离和培养细胞中细胞器的3D超微结构,以及(iii)将冷冻切片与锇浸渍方法相结合的相关免疫荧光和SEM技术,使分子的免疫细胞化学定位与细胞器的3D超微结构相关。在本文中,我们回顾了前面描述的新型锇浸渍方法,并讨论了它们在生物学和生物医学研究领域的潜力和未来方向。
    The two-dimensional observation of ultrathin sections from resin-embedded specimens provides an insufficient understanding of the three-dimensional (3D) morphological information of membranous organelles. The osmium maceration method, developed by Professor Tanaka\'s group >40 years ago, is the only technique that allows direct observation of the 3D ultrastructure of membrane systems using scanning electron microscopy (SEM), without the need for any reconstruction process. With this method, the soluble cytoplasmic proteins are removed from the freeze-cracked surface of cells while preserving the integrity of membranous organelles, achieved by immersing tissues in a diluted osmium solution for several days. By employing the maceration method, researchers using SEM have revealed the 3D ultrastructure of organelles such as the Golgi apparatus, mitochondria and endoplasmic reticulum in various cell types. Recently, we have developed new SEM techniques based on the maceration method to explore further possibilities of this method. These include: (i) a rapid osmium maceration method that reduces the reaction duration of the procedure, (ii) a combination method that combines agarose embedding with osmium maceration to elucidate the 3D ultrastructure of organelles in free and cultured cells and (iii) a correlative immunofluorescence and SEM technique that combines cryosectioning with the osmium maceration method, enabling the correlation of the immunocytochemical localization of molecules with the 3D ultrastructure of organelles. In this paper, we review the novel osmium maceration methods described earlier and discuss their potential and future directions in the field of biology and biomedical research.
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  • 文章类型: Journal Article
    贵金属纳米颗粒是从催化和传感到医学的一系列应用的关键。虽然黄金(Au),银(Ag),铂(Pt),钯(Pd)或钌(Ru)纳米粒子已被广泛研究,其他贵金属研究较少。锇(Os)是研究最少的贵金属之一。然而,Os纳米粒子是有趣的材料,因为它们与其他贵金属相比具有独特的功能,Os纳米材料已被报道可用于一系列应用。例如催化或传感。随着先进表征技术的日益普及,研究相对较小的Os纳米粒子和簇的性质变得更加容易,可以预见,我们对Os纳米材料的了解将在未来几年增加。本文旨在概述Os和Os氧化物材料的合成和应用。
    Precious metal nanoparticles are key for a range of applications ranging from catalysis and sensing to medicine. While gold (Au), silver (Ag), platinum (Pt), palladium (Pd) or ruthenium (Ru) nanoparticles have been widely studied, other precious metals are less investigated. Osmium (Os) is one of the least studied of the precious metals. However, Os nanoparticles are interesting materials since they present unique features compared to other precious metals and Os nanomaterials have been reported to be useful for a range of applications, catalysis or sensing for instance. With the increasing availability of advanced characterization techniques, investigating the properties of relatively small Os nanoparticles and clusters has become easier and it can be expected that our knowledge on Os nanomaterials will increase in the coming years. This review aims to give an overview on Os and Os oxide materials syntheses and applications.
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