The molybdenum complexes of Schiff base ligands viz. [MoO2LH2O] where L1 = tris(hydroxymethyl)(salicylide-neamino)methane, L2 = tris(hydroxymethyl)(2,3-dihydroxybenzylideneamino)methane and L3 = tris(hydroxymethyl)(2,3,4-trihydroxybenzylideneamino)methane have been synthesized and characterized by spectroscopic and electrochemical techniques. The X-ray crystal structure of the complex [MoO2L1H2O] reveals a distorted octahedral geometry with one ligand and a water molecule coordinated to the MoO2 center. No previous complex of this type contains a coordinated water molecule. The complex undergoes an oxotransfer in the presence of Bu3P to form a -oxobridged molybdenum(V,V) dimer. This rules out Mo—S coordination as a prerequisite for oxotransfer in such molybdenum(VI) complexes. 相似文献
Optical methods are appropriate tools to detect organic micro-pollutants in fluids. A new technique is introduced which uses the decay of interaction processes like fluorescence and elastically scattered radiation by a fluid. Principally two different parameters are determined:
1. (i) the decay-time of the conventional interaction τC, which occurs at relatively short path-lengths of the incidence beam in the fluid, and
2. (ii) the decay-time τMP of the multi-path-saturation interaction originating at long path-lengths, e.g. in multi-path-reflection cuvettes, where the incidence beam is fully absorbed by the fluid.
A relation between the decay-time and the absorption coefficient of a fluid is theoretically derived. A simple preliminary experiment is performed considering distilled water polluted with non-fluorescent azobenzene and fluorescent quinine-sulphate. A nitrogen laser has been used to generate the fluorescence and scattering signals. The reciprocal value of the difference between the decay-time of the multi-path and conventional signals, 1/(τMP − τC), yields the total absorption coefficient directly. In comparison to the conventional absorption technique the decay-time method is characterized by a higher sensitivity. 相似文献
Positively charged zinc containing or metal free phthalocyanines 6a-c and 7a-c were prepared via a three step procedure starting from 4-nitrophthalonitrile. The phthalocyanines contain alkyl chains of different length in order to influence the hydrophilic vs lipophilic character of the compounds. The partition between a hydrophilic (water) and lipophilic (octanol-1) phase was determined, and the photoredox activities were investigated. Initial results on the photodynamic activity of these compounds were compared with those of Dougherty's Photofrin II on different malignant and non-malignant cell lines (XP 29MAmal, CX1, HeLa, S180 and NO17). Positively charged phthalocyanines in vitro showed a higher photodynamic activity than Photofrin II. 相似文献
A planar, polycyclic and aromatic hydrocarbon ligand, namely 9,10-phenanthrenequinone semicarbazone, and its transition metal complexes have been synthesized and structurally characterized. The in vitro antiproliferative activity of these compounds against five human cancer cell lines revealed that they were effective against androgen receptor-positive/negative prostate cancer cells as well as COX-positive pancreatic BxPC-3 cancer cell line. The driving force behind such antiproliferative activity seems to be the up-regulated COX expression in these cells, which was amenable for targeting through metal complexation. These structural motifs can, therefore, serve as a starting point for developing novel cytotoxic agents against the growing number of prostate and pancreatic cancers. 相似文献
Methylaluminoxane prepared from trimethylaluminium on a surface of ice mainly can be described as [Al4O3(CH3)6]4. This is shown through analysis, phase separation experiments with diethyl ether and molecular weight determinations in benzene, 1, 4-dioxane, tetrahydrofuran and trimethylaluminium. It is discussed that the reason for forming this ball-like structure is the saturation of four coordinated Al4O3(CH3)6. This molecule has a cavern which contains a solvent molecule or a molecule of trimethylaluminium. The consequences for the formation of the catalytically active structure together with metallocene are discussed. 相似文献
ZnO single crystals were prepared by means of two methods:i slow cooling of ZnO/PbF2 (PbO) high temperature solution, (ii) flux reaction technique, hydrolysis of ZnF2 in PbF2 as a solvent. At cooling rate ≥ 0.9 K/h the known plates, hexagonal prisms, and hollow crystals were obtained. At the cooling rate 0.6 K/h compact crystals have grown. This habit was also formed with the flux reaction technique. An estimation of the deposition rates of both methods has shown approximative agreement between the cooling runs with 0.6 K/h and the flux reaction technique under the chosen conditions. The deposition rate appears to be a relevant parameter for forming compact ZnO crystals in these systems. 相似文献
Two new fluorescein-based chemosensors for Cu2+ were designed with highly selective “off-on” behavior, one of them working in both absorption and emission, the other only in absorption. Binding to Cu2+ binding is reversible, as indicated by the bleaching of the color when the metal is extracted. The compounds form the basis for rapid, selective and sensitive Cu2+ chemosensors in aqueous media. 相似文献
Fluorescence-detected circular dichroism (FDCD) spectroscopy is applied for the first time to supramolecular host–guest and host–protein systems and compared to the more known electronic circular dichroism (ECD). We find that FDCD can be an excellent choice for common supramolecular applications, e.g. for the detection and chirality sensing of chiral organic analytes, as well as for reaction monitoring. Our comprehensive investigations demonstrate that FDCD can be conducted in favorable circumstances at much lower concentrations than ECD measurements, even in chromophoric and auto-emissive biofluids such as blood serum, overcoming the sensitivity limitation of absorbance-based chiroptical spectroscopy. Besides, the combined use of FDCD and ECD can provide additional valuable information about the system, e.g. the chemical identity of an analyte or hidden aggregation phenomena. We believe that simultaneous FDCD- and ECD-based chiroptical characterization of emissive supramolecular systems will be of general benefit for characterizing fluorescent, chiral supramolecular systems due to the higher information content obtained by their combined use.Fluorescence-detected circular dichroism (FDCD) spectroscopy is applied for the first time to supramolecular host–guest and host–protein systems and compared to the more known electronic circular dichroism (ECD).相似文献