铬的形态分析研究与进展

综述了Cr(Ⅲ)、Cr(Ⅵ)形态分析的发展。内容包括概述、样品分离富集、光谱分析、色谱分析等。引用文献43篇。     

Thermodynamics of Ion-Association of NaClO4 in Aqueous-Methanol and Aqueous-Glycerol Using Conductance Measurements

The conductance of NaClO₄ at (25–45)°C in methanol-H₂O, and glycerol-H₂O mixtures in a concentration range up to 10^?2 M has been measured. The association constant, K_A, values have been determined, where the conductometric data were analysed by a M S X computer using the Fuoss-Aprano method. The K_A values for NaClO₄ in methanol-H₂O are higher than in glycerel-H₂O mixtures, Also K_A values increase as the proportional of methanol or glycerol increases in mixture. The thermodynamic parameters ΔH°, ΔG°, and ΔS° were also calculated. It is obvious that the entire process of the ionic association in those systems are endothermic ones. The Walden products, Λ_oη were calculated for all systems investigated.     

An Ab Initio Study of N_2O Decomposition on MgO Catalyst

Nl0isalwaysusedasoxidantinalotofoxidativecatalyticprocesses,suchastheoxidativecouplingofmethane(0CM),oxidativedehydr0genationofalkanesands0on,becauseitdecomPosestoprovideOadspeciesonmetal0xidecatalystsandleadstothespecificoxidativeselectivity.Forexample,itwasf0undthatf0rOCMreacti0nonMgOandLougOcatalystS,thereactiontemPeraturerequiredislowerwhenoneusesN20asoxidantthanusing0,'.TheunderstandingofN20dec0mposihon0nmetal0xidecatalystsandthepropertiesofthereIevant0adspeciesshouldbeagoodstarting…     

Malformin-A1 (MA1) Sensitizes Chemoresistant Ovarian Cancer Cells to Cisplatin-Induced Apoptosis

High-grade epithelial ovarian cancer is a fatal disease in women frequently associated with drug resistance and poor outcomes. We previously demonstrated that a marine-derived compound MalforminA1 (MA1) was cytotoxic for the breast cancer cell line MCF-7. In this study, we aimed to examine the effect of MA1 on human ovarian cancer cells. The potential cytotoxicity of MA1was tested on cisplatin-sensitive (A2780S) and cisplatin-resistant (A2780CP) ovarian cancer cell lines using AlamarBlue assay, Hoechst dye, flow cytometry, Western blot, and RT-qPCR. MA1 had higher cytotoxic activity on A2780S (IC50 = 0.23 µM) and A2780CP (IC50 = 0.34 µM) cell lines when compared to cisplatin (IC50 = 31.4 µM and 76.9 µM, respectively). Flow cytometry analysis confirmed the cytotoxic effect of MA1. The synergistic effect of the two drugs was obvious, since only 13% of A2780S and 7% of A2780CP cells remained alive after 24 h of treatment with both MA1 and cisplatin. Moreover, we examined the expression of bcl2, p53, caspase3/9 genes at RNA and protein levels using RT-qPCR and Western blot, respectively, to figure out the cell death mechanism induced by MA1. A significant down-regulation in bcl2 and p53 genes was observed in treated cells compared to non-treated cells (p < 0.05), suggesting that MA1 may not follow the canonical pathway to induce apoptosis in ovarian cancer cell lines. MalforminA1 showed promising anticancer activity by inducing cytotoxicity in cisplatin-sensitive and cisplatin-resistant cancer cell lines. Interestingly, a synergistic effect was observed when MA1 was combined with cisplatin, leading to it overcoming its resistance to cisplatin.     

Saffron Pre-Treatment Promotes Reduction in Tissue Inflammatory Profiles and Alters Microbiome Composition in Experimental Colitis Mice

Inflammatory bowel disease (IBD) is a chronic inflammatory condition of the gastrointestinal tract with an incompletely understood pathogenesis. Long-standing colitis is associated with increased risk of colon cancer. Despite the availability of various anti-inflammatory and immunomodulatory drugs, many patients fail to respond to pharmacologic therapy and some experience drug-induced adverse events. Dietary supplements, particularly saffron (Crocus sativus), have recently gained an appreciable attention in alleviating some symptoms of digestive diseases. In our study, we investigated whether saffron may have a prophylactic effect in a murine colitis model. Saffron pre-treatment improved the gross and histopathological characteristics of the colonic mucosa in murine experimental colitis. Treatment with saffron showed a significant amelioration of colitis when compared to the vehicle-treated mice group. Saffron treatment significantly decreased secretion of serotonin and pro-inflammatory cytokines, such as TNF-α, IL-1β, and IL-6, in the colon tissues by suppressing the nuclear translocation of NF-κB. The gut microbiome analysis revealed distinct clusters in the saffron-treated and untreated mice in dextran sulfate sodium (DSS)-induced colitis by visualization of the Bray–Curtis diversity by principal coordinates analysis (PCoA). Furthermore, we observed that, at the operational taxonomic unit (OTU) level, Cyanobacteria were depleted, while short-chain fatty acids (SCFAs), such as isobutyric acid, acetic acid, and propionic acid, were increased in saffron-treated mice. Our data suggest that pre-treatment with saffron inhibits DSS-induced pro-inflammatory cytokine secretion, modulates gut microbiota composition, prevents the depletion of SCFAs, and reduces the susceptibility to colitis.     

Novel approach to synthesizing hydrophobically associating copolymer using template copolymerization: the synthesis and behaviors of acrylamide and 4-(omega-propenoyloxyethoxy) benzoic acid copolymer

Hydrophobically associating copolymers of acrylamide (AM) with a small amount of 4-(omega-propenoyloxyethoxy) benzoic acid (PEBA, <2.5%) were synthesized by template copolymerization in the presence of poly(allylammonium chloride) (PAAC) as a template in an aqueous medium. These template copolymers exhibited remarkable thickening properties due to the effective hydrophobic association, which were similar to those copolymers with a multiblock structure obtained by the micellar process. The pH of the reaction medium and the molecular weight of the template strongly influenced the thickening properties of the products. In the experimental range, the higher the PEBA content, the larger the thickening capacity of these hydrophobic copolymers. The aggregate behaviors of these copolymers were studied by fluorescence, transmission electron microscopy (TEM), and light scattering techniques. The apparent critical interpolymer aggregate concentration (cac) of the copolymer solution was about 0.5 g/dL. As the concentration of the copolymer became higher than the cac, the aggregates changed their morphology from small hollow spheres to big flower-shaped aggregates. All the above results indicated that the template copolymerization gave access to a very simple and powerful means for the preparation of hydrophobically associating copolymers and other functional polymer materials.     

Reduction Reaction of the Copper(II) Complex Bearing 1,3-Di(pyridine-2-carboxaldimino)propane (pitn) by Decamethylferrocene in Acetonitrile

The reduction reaction of the Cu(II)–pitn complex (pitn = 1,3-di(pyridine-2-carboxaldimino)propane) by decamethylferrocene [Fe(Cp*)₂] was examined in acetonitrile. The observed pseudo-first-order rate constants exhibited saturation kinetics with increasing excess amount of [Fe(Cp*)₂]. Detailed analyses revealed that the reaction is controlled by a structural change prior to the electron transfer step, rather than a conventional bimolecular electron transfer process preceded by ion pair (encounter complex) formation. The rate constant for the structural change was estimated to be 275 ± 13 s^?1 at 298 K (?H* = 33.3 ± 1.0 kJ·mol^?1, ?S* = 86 ± 5 J·mol^?1·K^?1), which is the fastest among gated reactions involving CuN₄ complexes. It was confirmed by EPR measurement and Conflex calculations that the dihedral angle between the two N–N planes is significantly large (40°) in solution whereas it is merely 17.14° in the crystal.     

N-Protection of amines using pyridinium 2, 2, 2-trifluoroacetate ionic liquid as an efficient and reusable catalyst

A simple, green, and efficient method for the N-tert-butoxycarbonylation of amines by pyridinium 2,2,2- trifluoroacetate （[Py][OTf]） as an efficient and reusable catalyst is reported. In general, electron donating groups on aryl group give rise to the higher yields than electron withdrawing groups. Clean reaction, short reaction times, high yields, reusability of catalyst, and easy preparation of it are some advantages of this work.     

Development of an ion-exchange method for separation of radioiodine from tellurium and antimony and its application to the production of 124I via the 121Sb(α,n)-process

A novel anion-exchange chromatographic method for separation of radioiodine from an antimony target irradiated with ³He- or α-particles was developed, with separation yield of radioiodine amounting to 90 ± 5 % and its decontamination factor from the Te and Sb radionuclides to ~10⁴. The optimized separation method developed was then applied to the production of ¹²⁴I via the ¹²¹Sb(α,n)¹²⁴I process using a highly enriched ¹²¹Sb target. Quality control tests showed that the separated ¹²⁴I occurred >99 % as iodide and the longer lived impurities ¹²⁶I and ¹²⁵I amounted to 0.16 % and <0.05 %, respectively. The trace level of inactive Sb impurity was determined by ICP–OES.     

Synthesis and in vitro anticancer activity of pyrazolo[1,5-a]pyrimidines and pyrazolo[3,4-d][1,2,3]triazines

A novel series of pyrazolo[1,5-a]pyrimidines 14a–j and pyrazolo[1,5-a]quinazolines 18a, b were synthesized via condensation of 5-amino-1H-pyrazoles 10a, b with 3-(dimethylamino)-1-aryl-prop-2-en-1-ones 11a–e and 2-((dimethylamino)methylene)-5,5-dimethylcyclohexane-1,3-dione (15), respectively, in glacial acetic acid. Finally, treatment of 10a, b with sodium nitrite (NaNO₂) afforded pyrazolo[3,4-d]triazines 20a, b. Structures of compounds were confirmed by their spectral data. These compounds were screened for their in vitro cytotoxic activities against human cancer cell lines (HepG-2 and MCF-7) using 3-[4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay. The results reveal that, the compounds 14b and 14h were the most potent in comparison with doxorubicin. The structure–activity relationship was discussed.