Synthesis, structure and properties of delocalized transition metal chelates: Diazoketiminato chelates of Co(III) and Pt(II)

The reactions of HL 1 [where HL is 1N-(2-pyridyl-2-methyl)-2-arylazoaniline and is formulated as ArN = NC₆H₄N(H)(CH₂C₅H₄N); Ar = C₆H₅ (for HL¹) or p-MeC₆H₄ (for HL²) or p-ClC₆H₄ (for HL³)] with K₂PtCl₄ and Co(ClO₄)₃ · 6H₂O afforded the (L)PtCl and [(L)₂Co]ClO₄ complexes, respectively. The HL ligands bind the platinum(II) and cobalt(III) centres in a tridentate (N,N,N) fashion, forming new diazoketiminato chelates upon dissociating the amino proton. The X-ray structures of (L³)PtCl and [(L³)₂Co]ClO₄ were determined. Redox properties of the new complexes have been examined.     

Low coordinate germanium and tin compounds (ArO)2ME and (ArO)2MM′Ln M=Ge, Sn; E=S, Se, –NSiMe3 M′=Cr, W, Fe, Pt [Ar=2,4,6-tris((dimethylamino)methyl)phenyl-]

The reactions of the divalent species (ArO)₂M (Ar=2,4,6-[(CH₃)₂NCH₂]₃C₆H₂; M=Ge, Sn) with either Me₃SiN₃, elemental S₈, Se or transition metal complexes M′(CO)_n+1 (M′=Fe, n=4; M′=Cr, W; n=5) (Ph₃P)₂Pt·C₂H₄ have resulted in the isolation of either the new stable formal metallanimines (ArO)₂M=N–SiMe₃, germanethione, -selone (ArO)₂Ge=E (E=S, Se) (the expected formations of the stannanethione and -selone were not observed), or the (ArO)₂M=M′(CO)_n, (ArO)₂M=Pt(PPh₃)₂ complexes, respectively. The direct oxidation of the (ArO)₂M species with various oxidizing agents led to the formation of the corresponding metalloxanes [(ArO)₂M–O–]₂. All of the chalcogenido- and transition metal–metal 14 complexes have been physicochemically and chemically characterized. The reactions of the (ArO)₂Ge=E (E=S, Se) compounds with 3,5-di-tert-butyl-1,2-benzoquinone produced, by extrusion of sulfur or selenium, the dioxametalloles corresponding to the formal addition of the divalent species (ArO)₂M to the benzoquinone. A substitution reaction of chalcogen (S/Se) has been observed permitting to go from germaneselone to germanethione.     

Distribution of Platinum and Palladium between Dissolved,Nanoparticulate, and Microparticulate Fractions of Road Dust

Ageing processes of vehicle catalytic converters inevitably lead to the release of Pt and Pd into the environment, road dust being the main sink. Though Pt and Pd are contained in catalytic converters in nanoparticulate metallic form, under environmental conditions, they can be transformed into toxic dissolved species. In the present work, the distribution of Pt and Pd between dissolved, nanoparticulate, and microparticulate fractions of Moscow road dust is assessed. The total concentrations of Pt and Pd in dust vary in the ranges 9–142 ng (mean 35) and 155–456 (mean 235) ng g⁻¹, respectively. The nanoparticulate and dissolved species of Pt and Pd in dust were studied using single particle inductively coupled plasma mass spectrometry. The median sizes of nanoparticulate Pt and Pd were 7 and 13 nm, respectively. The nanoparticulate fraction of Pt and Pd in Moscow dust is only about 1.6–1.8%. The average contents of dissolved fraction of Pt and Pd are 10.4% and 4.1%, respectively. The major fractions of Pt and Pd (88–94%) in road dust are associated with microparticles. Although the microparticulate fractions of Pt and Pd are relatively stable, they may become dissolved under changing environmental conditions and, hence, transformed into toxic species.     

The Norsesquiterpene Glycoside Ptaquiloside as a Poisonous,Carcinogenic Component of Certain Ferns

Previous studies related to the ptaquiloside molecule, a carcinogenic secondary metabolite known from the world of ferns, are summarised. Ptaquiloside (PTA) belongs to the group of norsesquiterpenes of the illudane type. The name illudane refers to the fungal taxa from which the first representatives of the molecular group were identified. Ptaquiloside occurs mainly in Pteridium fern species, although it is also known in other fern taxa. The species of the genus Pteridium are common, frequent invasive species on all continents, and PTA is formed in smaller or larger amounts in all organs of the affected species. The effects of PTA and of their derivatives on animals and humans are of great toxicological significance. Its basic chemical property is that the molecule can be transformed. First, with the loss of sugar moiety, ptaquilosine is formed, and then, under certain conditions, a dienone derivative (pteridienone) may arise. The latter can alkylate (through its cyclopropane groups) certain molecules, including DNA, in animal or human organisms. In this case, DNA adducts are formed, which can later have a carcinogenic effect through point mutations. The scope of the PTA is interdisciplinary in nature since, for example, molecules from plant biomass can enter the body of animals or humans in several ways (directly and indirectly). Due to its physico-chemical properties (excellent water solubility), PTA can get from the plant into the soil and then into different water layers. PTA molecules that enter the soil, but mainly water, undergo degradation (hydrolytic) processes, so it is very important to clarify the toxicological conditions of a given ecosystem and to estimate the possible risks caused by PTA. The toxicoses and diseases of the animal world (mainly for ruminant farm animals) caused by PTA are briefly described. The intake of PTA-containing plants as a feed source causes not only various syndromes but can also enter the milk (and meat) of animals. In connection with the toxicological safety of the food chain, it is important to investigate the transport of carcinogenic PTA metabolites between organisms in a reassuring manner and in detail. This is a global, interdisciplinary task. The present review aims to contribute to this.     

Research Progress of Antioxidant Nanomaterials for Acute Pancreatitis

Acute pancreatitis (AP) is a complex inflammatory disease caused by multiple etiologies, the pathogenesis of which has not been fully elucidated. Oxidative stress is important for the regulation of inflammation-related signaling pathways, the recruitment of inflammatory cells, the release of inflammatory factors, and other processes, and plays a key role in the occurrence and development of AP. In recent years, antioxidant therapy that suppresses oxidative stress by scavenging reactive oxygen species has become a research highlight of AP. However, traditional antioxidant drugs have problems such as poor drug stability and low delivery efficiency, which limit their clinical translation and applications. Nanomaterials bring a brand-new opportunity for the antioxidant treatment of AP. This review focuses on the multiple advantages of nanomaterials, including small size, good stability, high permeability, and long retention effect, which can be used not only as effective carriers of traditional antioxidant drugs but also directly as antioxidants. In this review, after first discussing the association between oxidative stress and AP, we focused on summarizing the literature related to antioxidant nanomaterials for the treatment of AP and highlighting the effects of these nanomaterials on the indicators related to oxidative stress in pathological states, aiming to provide references for follow-up research and promote clinical application.     

WWOX Modulates ROS-Dependent Senescence in Bladder Cancer

The tumor-suppressor gene, WW domain-containing oxidoreductase (WWOX), has been found to be lost in various types of cancers. ROS result as a tightly regulated signaling process for the induction of cell senescence. The aim of this study was to investigate the role of WWOX in the regulation of ROS and cell senescence, which is intriguing in terms of the possible mechanism of WWOX contributing to bladder cancer. In this study, we used the AY-27 rat bladder tumor cell line and F344 orthotopic bladder tumor models to reveal the pro-senescence effects of WWOX and the corresponding underlying mechanism in bladder cancer. WWOX-overexpressing lentivirus (LV-WWOX) remarkably stimulated cellular senescence, including increased senescence-associated secretory phenotype (SASP) formation, enlarged cellular morphology, and induced SA-β-Gal-positive staining. A further mechanism study revealed that the pro-senescence effect of LV-WWOX was dependent on increased intercellular reactive oxygen species (ROS) generation, which subsequently triggered p21/p27. Moreover, LV-WWOX significantly inhibited the tumor size by 30.49% in the F344/AY-27 rat orthotopic model (p < 0.05) by activating cellular senescence. The expression of p21 was significantly enhanced in the orthotopic bladder tumors under WWOX treatment. The orthotopic bladder tumors in the groups of rats verified the effect in vivo. Our study suggests that WWOX, an ROS-dependent senescence-induced gene, could be further studied for its therapeutic implications in bladder cancer.     

Farnesol Protects against Cardiotoxicity Caused by Doxorubicin-Induced Stress,Inflammation, and Cell Death: An In Vivo Study in Wistar Rats

Doxorubicin (DOXO) is an antineoplastic drug that is used extensively in managing multiple cancer types. However, DOXO-induced cardiotoxicity is a limiting factor for its widespread use and considerably affects patients’ quality of life. Farnesol (FSN) is a sesquiterpene with antioxidant, anti-inflammatory, and anti-tumor properties. Thus, the current study explored the cardioprotective effect of FSN against DOXO-induced cardiotoxicity. In this study, male Wistar rats were randomly divided into five groups (n = 7) and treated for 14 days. Group I (Control): normal saline, p.o. daily for 14 days; Group II (TOXIC): DOXO 2.4 mg/kg, i.p, thrice weekly for 14 days; Group III: FSN 100 mg/kg, p.o. daily for 14 days + DOXO similar to Group II; Group IV: FSN 200 mg/kg, p.o. daily for 14 days + DOXO similar to Group II; Group V (Standard): nifedipine 10 mg/kg, p.o. daily for 14 days + DOXO similar to Group II. At the end of the study, animals were weighed, blood was collected, and heart-weight was measured. The cardiac tissue was used to estimate biochemical markers and for histopathological studies. The observed results revealed that the FSN-treated group rats showed decrease in heart weight and heart weight/body weight ratio, reversed the oxidative stress, cardiac-specific injury markers, proinflammatory and proapoptotic markers and histopathological aberrations towards normal, and showed cardioprotection. In summary, the FSN reduces cardiac injuries caused by DOXO via its antioxidant, anti-inflammatory, and anti-apoptotic potential. However, more detailed mechanism-based studies are needed to bring this drug into clinical use.     

表面等离子共振(SPR)——一种新型化学检测方法的原理

近年来,表面等离子共振(SPR)现象、由于在金属纳米材料研究以及在作为灵敏检测不同化学和生化物种信号的报告器方面有着特殊的应用价值,因而受到广泛的关注.本文较详细的介绍了表面等离子共振现象的形成机制,特别对如何利用本方法作为一种新型的物种检测报告器的有关问题做了较系统的讨论.     

Biological Risk Assessment of Three Dental Composite Materials following Gas Plasma Exposure

Gas plasma is an approved technology that generates a plethora of reactive oxygen species, which are actively applied for chronic wound healing. Its particular antimicrobial action has spurred interest in other medical fields, such as periodontitis in dentistry. Recent work has indicated the possibility of performing gas plasma-mediated biofilm removal on teeth. Teeth frequently contain restoration materials for filling cavities, e.g., resin-based composites. However, it is unknown if such materials are altered upon gas plasma exposure. To this end, we generated a new in-house workflow for three commonly used resin-based composites following gas plasma treatment and incubated the material with human HaCaT keratinocytes in vitro. Cytotoxicity was investigated by metabolic activity analysis, flow cytometry, and quantitative high-content fluorescence imaging. The inflammatory consequences were assessed using quantitative analysis of 13 different chemokines and cytokines in the culture supernatants. Hydrogen peroxide served as the control condition. A modest but significant cytotoxic effect was observed in the metabolic activity and viability after plasma treatment for all three composites. This was only partially treatment time-dependent and the composites alone affected the cells to some extent, as evident by differential secretion profiles of VEGF, for example. Gas plasma composite modification markedly elevated the secretion of IL6, IL8, IL18, and CCL2, with the latter showing the highest correlation with treatment time (Pearson’s r > 0.95). Cell culture media incubated with gas plasma-treated composite chips and added to cells thereafter could not replicate the effects, pointing to the potential that surface modifications elicited the findings. In conclusion, our data suggest that gas plasma treatment modifies composite material surfaces to a certain extent, leading to measurable but overall modest biological effects.     

X射线光谱在生命起源和全球气候变化等若干重大科学问题中的研究进展

生命起源、全球气候变化等是关系到人类未来命运的重大科学问题, X射线光谱(XRS)可原位测定物质组成与元素形态,在解决重大科学问题、揭示自然规律中发挥了重要作用:(1)在生命起源探索中,通过RNA结构和海洋热液自养体系元素形态分析,揭示了RNA形成机制和生物地球化学规律;(2)在地球早期生命研究中,通过沉积纹层、细胞组构测定,发现了远古生物保存机制与证据;(3)在全球碳循环研究中,通过物相与元素形态分析,揭示了铁源生物有效性与碳汇机制。利用XRS从微纳米尺度原位测定元素三维空间分布与形态,实现活体分析蛋白质信息传递与生物响应过程,探索元素与有机质构效关系,揭示生命起源与生物代谢机制及全球气候变化规律,是XRS未来发展中的重要领域;作为冶金、材料、地质、文物、工矿、生态、环境、医学与生命科学等领域中的重要分析手段, XRS所特有的无损、原位与活体分析特性,已呈现了巨大应用价值,在未来探索重大科学问题、解决关键技术难点的研究中, X射线光谱分析技术必将发挥更大作用。