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1.
Functional zinc(II) phthalocyanines bearing Schiff base complexes as oxidation catalysts for bleaching systems
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Oxidation catalysis is used to increase the performance of hydrogen peroxide in laundry bleach applications. Bleach catalysts provide cost‐effective, energy‐saving and environmentally friendly bleach systems yielding perfect stain removal at lower temperatures. This comparative study is based on the synthesis of bis[bis(salicylhydrazonephenoxy)manganese(III)] phthalocyaninatozinc(II) ( 2 ), bis[bis(salicylhydrazonephenoxy)cobalt(III)] phthalocyaninatozinc(II) ( 3 ) and bis[bis(salicylhydrazonephenoxy)iron(III)] phthalocyaninatozinc(II) ( 4 ) as tri‐nuclear complexes consisting of two Schiff base complexes substituting a zinc phthalocyanine. Complexion on the periphery to obtain complexes 2 , 3 , 4 was performed through the reaction of a Schiff base‐substituted phthalocyanine using MnCl2?4H2O, CoCl2?6H2O or FeCl3?6H2O salts in basic condition in dimethylformamide. Fourier transform infrared, 1H NMR, 13C NMR, UV–visible, inductively coupled plasma optical emission and mass spectra were applied to characterize the prepared compounds. The bleach performances of the three phthalocyanine compounds 2 , 3 , 4 were examined by the degradation of morin as hydrophilic dye. The degradation progress in the presence of catalysts 2 , 3 , 4 /H2O2 combination in aqueous solution was investigated using an online spectrophotometric method. It was found that the catalysts 2 , 3 , 4 exhibited better bleaching performance at 25 °C than tetraactylethylethylenediamine as bleach activator used in powder detergent formulations for stain removal. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
2.
Investigation of suitable digestion methods for the determination of total phosphorus in soils 总被引:1,自引:0,他引:1
Total phosphorus in five soils with different compositions which were obtained from different places were extracted by using Na(2)CO(3) fusion, HClO(4) digestion, HClO(4) + HNO(3) digestion, HF + HClO(4) digestion or NaOBr oxidation methods. In order to test the suitability of the HF + HClO(4) digestion the results obtained by this method were compared with the others above, especially the Na(2)CO(3) fusion which is accepted as a standard method. The phosphorus amount found with the HF + HClO(4) digestion method were almost the same as the phosphorus amount by the Na(2)CO(3) fusion method, while the superiority in extracting phosphorus when compared to other methods were obvious. The methods used in the study were evaluated according to the recovery of total phosphorus, ease of application and rapidity with which they were performed. Orthophosphate in the soil extracts was determined by the molybdenum blue colour method. The relationships between methods are examined statistically. 相似文献
3.
4.
The sorption behavior of a nickel-insolubilized humic acid system in a column arrangement 总被引:2,自引:0,他引:2
The sorption characteristics of insolubilized humic acid (IHA) were investigated for Ni (II) in a column arrangement. The sodium form of the IHA (INaA) was used as a solid phase. Column operations were performed with five steps and all of them were monitored continuously by a flowthrough cell-adapted UV-Vis spectrophotometer. Thus, all solid-phase extraction (SPE) steps were visualized by breakthrough curves and analyses progress were evaluated. However, all calculations and evaluations were focused on the atomic absorption spectrophotometric (AAS) analyses of the solutions collected during the stripping steps. There was a high correlation (r(2), 0.972) between peak area and AAS data of stripping steps. The effect of concentration and pH of the loading solution onto sorption of Ni (II) by INaA was investigated. Sorption characteristics were evaluated by using Freundlich, Langmuir, and Dubinin-Radushkevich (D-R) adsorption isotherms, as well as by Scatchard plot analysis. Multilayer sorption was found to be agreeable for Ni (II). From the D-R isotherm the mean free energy of sorption (E) was calculated (6.65 kJ mol(-1)) and attributed to the multilayer sorption. Finally, the sorption characteristic of the INaA-Ni (II) system was compared with that of the INaA-Cu (II) system, and possible separation of two ions in a binary mixture system is discussed. 相似文献
5.
Gololobov Yu. G. Petrovskii P. V. Ivanova E. M. Linchenko O. A. Schmutzler R. Ernst L. Jones P. G. Karaçar A. Freytag M. Okucu S. 《Russian Chemical Bulletin》2003,52(2):427-436
The reactions of meta—para-substituted aryl isocyanates with phosphorus-containing 1,3-zwitterions, which proceed with the CN migration of the CO2Et group to form the corresponding carbamates, were extended to ortho-substituted aryl isocyanates. The influence of the steric and electronic effects of the ortho substituents in the aromatic rings of aryl isocyanates on the ease of this rearrangement is qualitatively considered. 相似文献
6.
NMR spectroscopy has become a vital tool for studies of protein conformational changes and dynamics. Oxidized Fe(III)cytochromes c are a particularly attractive target for NMR analysis because their paramagnetism (S = (1)/(2)) leads to high (1)H chemical shift dispersion, even for unfolded or otherwise disordered states. In addition, analysis of shifts induced by the hyperfine interaction reveals details of the structure of the heme and its ligands for native and nonnative protein conformational states. The use of NMR spectroscopy to investigate the folding and dynamics of paramagnetic cytochromes c is reviewed here. Studies of nonnative conformations formed by denaturation and by anomalous in vivo maturation (heme attachment) are facilitated by the paramagnetic, low-spin nature of native and nonnative forms of cytochromes c. Investigation of the dynamics of folded cytochromes c also are aided by their paramagnetism. As an example of this analysis, the expression in Escherichia coli of cytochrome c(552) from Nitrosomonas europaea is reported here, along with analysis of its unusual heme hyperfine shifts. The results are suggestive of heme axial methionine fluxion in N. europaea ferricytochrome c(552). The application of NMR spectroscopy to investigate paramagnetic cytochrome c folding and dynamics has advanced our understanding of the structure and dynamics of both native and nonnative states of heme proteins. 相似文献
7.
Szefczyk B Mulholland AJ Ranaghan KE Sokalski WA 《Journal of the American Chemical Society》2004,126(49):16148-16159
Chorismate mutase is a key model system in the development of theories of enzyme catalysis. To analyze the physical nature of catalytic interactions within the enzyme active site and to estimate the stabilization of the transition state (TS) relative to the substrate (differential transition state stabilization, DTSS), we have carried out nonempirical variation-perturbation analysis of the electrostatic, exchange, delocalization, and correlation interactions of the enzyme-bound substrate and transition-state structures derived from ab initio QM/MM modeling of Bacillus subtilis chorismate mutase. Significant TS stabilization by approximately -23 kcal/mol [MP2/6-31G(d)] relative to the bound substrate is in agreement with that of previous QM/MM modeling and contrasts with suggestions that catalysis by this enzyme arises purely from conformational selection effects. The most important contributions to DTSS come from the residues, Arg90, Arg7, Glu78, a crystallographic water molecule, Arg116, and Arg63, and are dominated by electrostatic effects. Analysis of the differential electrostatic potential of the TS and substrate allows calculation of the catalytic field, predicting the optimal location of charged groups to achieve maximal DTSS. Comparison with the active site of the enzyme from those of several species shows that the positions of charged active site residues correspond closely to the optimal catalytic field, showing that the enzyme has evolved specifically to stabilize the TS relative to the substrate. 相似文献
8.
A new Schiff base, N,N′-bis-(2-hydroxy-5-bromobenzyl)-2-hydroxy-1,3-diiminopropane, has been synthesized for the very sensitive
determination of iron(III) and iron(II) in natural water samples. It enabled a very selective and rapid method for iron determination
to be developed. The method has also been applied to total iron determination in sediment samples. In the preconcentration
system, the Schiff base reagent is mixed with the samples and chelates containing iron(III). The complexes are then adsorbed
on silica gel within a column system. Elution of the adsorbed chelate from the silica gel was performed with a small volume
of acetone containing 2.5% nitric acid. The iron is measured off-line by flame atomic absorption spectrometry. The method
can be applied to the preconcentration, separation and speciation of iron. The effects of parameters such as pH, sample flow
rate, eluent flow rate, foreign ions and ligand concentration have been investigated. The effect of humic acid that can produce
complexes with metal ions in natural systems has also been investigated. The results obtained indicate that the method is
not affected by the presence of up to 10 ppm humic acid, which would be a very high concentration to be present in natural
systems. The solid phase extraction method developed has been applied to the determination of iron in both natural water samples
and sediment samples. The LOD was found to be 0.17 mg L−1 when no preconcentration was used, although preconcentration factors of 100 could be achieved. The recovery values for spiked
samples were between 100 and 104%. The results were compared statistically with those from the standard 1,10 phenanthroline
method used for iron speciation in water systems. A Student’s t-test indicated no significant difference between the two methods. In addition, this method was applied to the analysis of
a certified sediment sample, LGC 6156. Generally, a 10-fold preconcentration factor was required for the analysis of natural
water samples. 相似文献
9.
Kati Finzel 《International journal of quantum chemistry》2014,114(9):568-576
The electronic stress tensor is not uniquely defined. Possible bonding indicators originating from the quantum stress tensor may inherit this ambiguity. Based on a general formula of the stress tensor this ambiguity can be described by an external parameter λ for indicators derived from the scaled trace of the stress tensor (whereby the scaling function is proportional to the Thomas–Fermi kinetic energy density). The influence of λ is analyzed and the consequences for the representation of chemical bonding are discussed in detail. It is found that the scaled trace of the stress tensor may serve as suitable bonding indicator over a wide range of λ values, excluding the value range between ?0.15 and ?0.48. Focusing on the eigenvalues of the stress tensor, it is found that the sign of the eigenvalues heavily depends on the chosen representation of the stress tensor. Therefore, chemical bonding analyses which are based on the interpretation of the eigenvalue sign (e.g., the spindle structure) are strongly dependent on the chosen form of the stress tensor. © 2014 Wiley Periodicals, Inc. 相似文献
10.