共振二胺结构的鳌合树脂对铂、钯把吸附性的研究

具有共振二胺结构的螯合树脂,在pH1—2时能对铂、钯离子进行定量吸附,而且在Fe,Cu,Ni,Zn,Cd离子共存下有很好的选择性,该树脂吸附Pt,Pd的容量分别为374.3毫克/克、233.4毫克/克.从树脂含氮量分析及螯合容量算得螯合比均为2:1     

博莱霉素切割DNA反应的定量测定及其影响因素

用硫代巴比妥酸反应分析了博莱霉素 Ａ５ （ Ｂ Ｌ Ｍ Ａ５ ）对 Ｄ Ｎ Ａ 的断裂作用在 Ｆｅ２＋ 和 Ｏ２存在下, Ｂ Ｌ Ｍ Ａ５能导致 Ｄ Ｎ Ａ 链断裂研究了一些因素对 Ｂ Ｌ Ｍ Ａ５ 催化 Ｄ Ｎ Ａ 断链反应的影响,设计并建立了 Ｂ Ｌ Ｍ Ａ５ 切割 Ｄ Ｎ Ａ 反应的定量测定方法,并测得 Ｋｍ 约为１５３ μｍ ｏｌ· Ｌ－ １, Ｖｍ ａｘ 约为００４６ Ａ５３２ｎｍ Ｕｎｉｔ·ｓ－ １      

A Bis-Chelating / Ligand for the Synthesis of Heterobimetallic Platinum(II)/Rhenium(I) Complexes: Tools for the Optimization of a New Class of Platinum(II) Anticancer Agents

The two independent and coordination sites of a newly synthesized bis[2-(hydroxyphenyl)-1,2,4-triazole] platform have been exploited to prepare four monometallic neutral ()Pt^II complexes carrying DMSO, pyridine, triphenylphosphine, or N-heterocyclic carbene as the fourth ligand. Then, the second coordination site was used to introduce an IR-active rhenium tricarbonyl entity, affording the four corresponding heterobimetallic neutral Pt^II/Re^I complexes, as well as a cationic Pt^II/Re^I derivative. X-ray crystallographic studies showed that distortion of the organic platform occurred to accommodate the coordination geometry of both metal centers. No ligand exchange or transchelation occurred upon incubation of the Pt^II complexes in aqueous environment or in the presence of Fe^III, respectively. The antiproliferative activity of the ligand and complexes was first screened on the triple-negative breast cancer cell line MDA-MB-231. Then, the IC₅₀ values of the most active candidates were determined on a wider panel of human cancer cells (MDA-MB-231, MCF-7, and A2780), as well as on a nontumorigenic cell line (MCF-10A). Low micromolar activities were reached for the complexes carrying a DMSO ligand, making them the first examples of highly active, but hydrolytically stable, Pt^II complexes. Finally, the characteristic mid-IR signature of the {Re(CO)₃} fragment in the Pt/Re heterobimetallic complexes was used to quantify their uptake in breast cancer cells.     

Adsorption of azacrown ethers at solid–liquid interface. Contact angle and neutron reflectivity study

Adsorption of two alkylated N,N′-diaza-18-crown-6 ethers (decyl- and hexadecyl-derivatives, ACE-10 and ACE-16, respectively) on solid surfaces was studied by using contact angle and neutron reflectivity measurements. The solid substrates used were (a) Si covered with a native oxide layer (Si/SiO₂) and (b) Si with sputtered Pt layer (Si/Pt). The sensitivity of neutron reflectivity was drastically improved by applying the intermediate Pt layer of 150 Å, which gave rise to several Kiessig fringes in the experimentally accessible q-range. The position of the fringes is very sensitive to slight changes of the interfacial composition induced by adsorption of a thin monolayer, otherwise very difficult to detect. Unfortunately, in the studied case this sensitivity is immediately lost due to undesired adsorption of a protonated material on the Pt surface exposed to the lab air. A decrease of surface energy (increase of contact angle) of both Si/SiO₂ and Si/Pt upon exposure to toluene solutions of ACEs suggests that the latter are attached to the surface via the hydrophilic azacrown ether head with alkyl chains standing upright towards the liquid phase.     

Determination of trace metals by voltamperometry in zebra mussel (Dreissena polymorpha) employed as environmental bio-indicator

Abstract

In the present work, metals (cadmium, lead, copper, nickel, tin, selenium, and mercury) have been estimated in the Ebro River (Spain) using the zebra mussel (Dreissena polymorpha) as an environmental bio-indicator. In two sequential studies, in 2006 and 2008, concentrations of metals were calculated in water as well as in the shells and fleshes of the zebra mussels. Samples were collected from assorted locations of the river. Metals were determined successfully at trace levels through voltamperometry, a sensitive technique. It has been noted that analysis of bioaccumulators like zebra mussels can be helpful in evaluating metal pollution in water.     

Chiral bidiaziridines by a two-step domino aziridination of meso-α-diimines

Chiral racemic α-diimines, tested in aziridination reactions with NsONHCO₂Et, for the first time led to the synthesis of (±)-bidiaziridines, stereoselectively derived from the corresponding meso (E-s-trans-E)-α-diimines. Moreover, a minor bidiaziridine isomer, probably a meso form that was lost under classical work-up conditions, can be obtained by adding water to the crude mixtures at the end of amination reactions. The results definitively prove that the imine aziridination by carbamates is a two-step domino process. The structures of the compounds were determined using 2D NMR on purified bidiaziridines.     

Cathode catalysts degradation mechanism from liquid electrolyte to membrane electrode assembly

Single-cell and half-cell degradation test procedures were evaluated for carbon-supported Pt/C, PtCo/C and PtNi/C catalysts. Half-cell analyses were employed to understand the effect of the number of cycles and of the scan rate over the cathode catalysts degradation under potential cycling from 0.6 to 1.2 V. The data suggested a time-dependent degradation for all three catalytic systems. Single-cell measurements were used to evaluate the impact of catalyst degradation on fuel cell performance. The measurements in both setups showed similar ECSA and ORR mass activity losses. Specific degradation mechanisms related to Pt dissolution, Pt agglomeration, and transitional metal leaching were quantified and correlated with performance losses.     

Investigation of Coenzyme Q10 by Voltammetry

A simple, accurate and rapid voltammetric method has been developed for the quantitative determination of coenzyme Q₁₀. Studies with direct current voltammetry were carried out using a glassy carbon electrode (GCE) in a phosphate buffer solution (pH 6.86). A well-defined oxidation peak of CoQ₁₀ was obtained at -0.600 V vs Ag/AgCl. The magnitude of the oxidation peak current has been found to be related to the concentration of the coenzyme over the range of (2.010^-5 to 2.010^-4 M) (r = 0,991). Antioxidant activity of CoQ₁₀ was investigated.     

Chiral Modification of Platinum by Co‐Adsorbed Cinchonidine and Trifluoroacetic Acid: Origin of Enhanced Stereocontrol in the Hydrogenation of Trifluoroacetophenone

Cinchonidine (CD) adsorbed onto a platinum metal catalyst leads to rate acceleration and induces strong stereocontrol in the asymmetric hydrogenation of trifluoroacetophenone. Addition of catalytic amounts of trifluoroacetic acid (TFA) significantly enhances the enantiomeric excess from 50 to 92 %. The origin of the enantioselectivity bestowed by co‐adsorbed CD and TFA is investigated by using in situ attenuated total reflection infrared spectroscopy and modulation excitation spectroscopy. Molecular interactions between the chiral modifier (CD), acid additive (TFA) and the trifluoro‐activated substrate at the solid–liquid interface are elucidated under conditions relevant to catalytic hydrogenations, that is, on a technical Pt/Al₂O₃ catalyst in the presence of H₂ and solvent. Monitoring of the unmodified and modified surface during the hydrogenation provides an insight into the phenomenon of rate enhancement and the crucial interactions of CD with the ketone, corresponding product alcohol, and TFA. Comparison of the diastereomeric interactions occurring on the modified surface and in the liquid solution shows a striking difference for the chiral preferences of CD. The spectroscopic data, in combination with calculations of molecular structures and energies, sheds light on the reaction mechanism of the heterogeneous asymmetric hydrogenation of trifluoromethyl ketones and the involvement of TFA in the diastereomeric intermediate surface complex: the quinuclidine N atom of the adsorbed CD forms an N?H?O‐type hydrogen‐bonding interaction not only with the trifluoro‐activated ketone but also with the corresponding alcohol and the acid additive. Strong evidence is provided that it is a monodentate acid/base adduct in which the carboxylate of TFA resides at the quinuclidine N‐atom of CD, which imparts a better stereochemical control.