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81.
Photoreactive surfaces derived from a new photocleavable surface modification agent and with photosensitivity in the Vis and IR region are described. A ruthenium(II) caged aminosilane, [Ru(bpy)(2)(PMe(3))(APTS)](PF(6))(2), was synthesized and attached to silica surfaces. Light irradiation removed the cage and generated surface patterns with reactive amine groups. The photosensitivity of this compound under single (460 nm) and two-photon (900) excitation is demonstrated. Functional patterns with site-selective attachment of other molecular species are described.  相似文献   
82.
The inhibition of the model enzyme, haloalkane dehalogenase from Sphingomonas paucimobilis, was investigated by a combination of electrophoretically mediated microanalysis with a partial filling technique, followed by indirect or direct detection. In this setup, part of the capillary is filled with a buffer suitable for the enzymatic reaction (20 mM glycine buffer, pH 8.6) whereas the rest of the capillary is filled with the background electrolyte optimal for separation of substrates and products. Two different background electrolytes and corresponding detection approaches were used to show the versatility of the developed method. The inhibition effect of 1,2-dichloroethane on the dehalogenation of brominated substrate 1-bromobutane was studied by means of 10 mM chromate - 0.1 mM cetyltrimethylammonium bromide (pH 9.2) in combination with indirect detection or 20 mM beta-alanine - hydrochloric acid (pH 3.5) in combination with direct detection. The method was used to estimate the inhibition constant K(I) (0.44 mM by indirect detection and 0.63 mM by of direct detection) and to determine the inhibition type. Compared to spectrophotometric and other discontinuous assays, the method is rapid, can be automated, and requires only small amount of reagents that is especially important in the case of enzymes and inhibitors.  相似文献   
83.
The first direct NMR determination of the conformation of a conformationally flexible heparin-like hexasaccharide bound to a key receptor, FGF-1, is described. The determination has been based on the use of a 13C-labeled protein and a regular 12C sugar. FGF-1 recognizes several conformations of the iduronic moieties of the hexasaccharide. Therefore, this case is different than that described for the controversial recognition of heparin-like saccharides by AT-III, which seems to recognize just one conformation of the iduronic acid residues.  相似文献   
84.

Differential scanning calorimetry (DSC) technique has been applied for the experimental determination of temperature and heat of phase transition of pure silicon (7 N) during heating and cooling cycles at the rate of 10 K min?1. The measurements were carried out in the temperature range of 25–1450 °C in a flow gas atmosphere (Ar, 99.9992%) using three types of crucibles made of alumina, h-BN and alumina covered with h-BN coating. The following characteristics were estimated from DSC curves: melting point of silicon—1414 °C, the heat of fusion—1826 J g?1 and the heat of solidification—1654 J g?1. It was found that the silicon evaporation phenomenon accompanying the tests had no effect on the measurements of temperature during solid-to-liquid and liquid-to-solid transformations and on the measurement of the latent heat of fusion. The effect of crucible type on the DSC measurements is discussed.

  相似文献   
85.
The first asymmetric version of intermolecular Pauson-Khand reactions of unstrained alkenes is described. Generally simple acyclic alkenes exhibit low reactivity and regioselectivity in intermolecular Pauson-Khand reactions; however, o-(dimethylamino)phenyl vinyl sulfoxide reacts under very mild conditions with a wide variety of terminal alkynes in a completely regioselective and highly stereoselective manner. The utility of the resulting 5-sulfinyl-2-cyclopentenones in asymmetric synthesis is illustrated by a very short enantioselective synthesis of the antibiotic (-)-pentenomycin I.  相似文献   
86.
Electrospray ionization mass spectrometry (MS) has been widely used to detect noncovalent interactions in supramolecular compounds, especially in biological systems. In our work, we present the application of the electrospray ionization MS technique to characterize the metallamacrocycles, known as metallacrowns. This project involves investigations of the aminohydroxamic acids structure and chirality influence on formation of ternary 12‐metallacrown‐4 complexes. For our experiments, we used a series of β‐aminohydroxamic acids and derivatives of histidinehydroxamic acid. A high stability of the studied supramolecular systems in the gas phase was confirmed by MS/MS experiments. We also proposed the fragmentation pathways for the studied compounds. Obtained results reveal that the ternary 12‐metallacrown‐4 formation process is not selective, and ligands of various structures and chiralities can be incorporated into these systems. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   
87.
Propyl gallate (PG) adsolubilisation in the cationic, anionic and nonionic surfactant micelles formed in the bulk solution and at the silica/solution interface has been investigated. It was found that in the absence of surfactant, propyl gallate does not adsorb on the silica surface from aqueous solution. However, in the presence of hexyltrimethylammonium bromide (CTAB), its uptake by silica significantly increases. Alumina is quite an effective adsorbent for SDS and propyl gallate and does not adsorb nonionic TX-100. The addition of PG promotes adsorption of SDS and TX-100.  相似文献   
88.
We report on a convenient synthesis of the ligand precursor, diethylethylene-1,2-bis(oxamate), (Et2H2oeo, 1), and show how a partial and preferential hydrolysis of the ester group can give rise to the dianionic ligand, (H2oeo)2−. Reaction of this ligand with Cu(II) affords the neutral dimeric species, [Cu2(H2oeo)2], which has a low aqueous solubility. We describe the crystal structure of the hydrate Cu2(H2oeo)2(H2O)4 (2) and report magnetic studies that show a weak exchange interaction in the solid. Under more basic conditions and in the presence of Cu(II) ions, we are able to avoid amide cleavage and yet deprotonate the amide group, resulting in the formation of the highly soluble [Cu(Hoeo)2]4− complex anion. The structure of (NBu4)4[Cu(Hoeo)2](H2O)4 (3) is described and compared with the recently reported anhydrous phase.  相似文献   
89.
This paper presents the effect of insecticides on the composition of the surface compounds of one of the most harmful insects, Tenebrio molitor, by analysis using GC–MS. As a result of the use of insecticides, the composition of the chemical compounds on the surface of insects changes, depending on the insecticides used. The most numerous groups of the marked compounds were fatty acids, alkanes, esters and sterols. The content of the identified compounds in the larvae increased at both 24 and 48 h after the application of insecticides, in comparison with the control samples. The content of identified compounds in the samples taken from the females increased 24, 48 and 72 h after the application of insecticides in comparison with the control samples. By contrast, in samples prepared from males, the content of identified compounds decreased 24 h after the application of insecticides, compared with the control samples. The highest content of chemical compounds was for fatty acids and alkanes after the use of insecticides. The content of fatty acids after the application of the insecticide with deltamethrin was 62.1 ± 3.3–466.9 ± 5.9 μg/g, and after the application of the insecticide with cyfluthrin was 49.9 ± 1.9–458.3 ± 4.2 μg/g. However, the content of alkanes after the use of deltamethrin was 115.6 ± 4.2–4672.0 ± 32.1 μg/g, and after the use of cyfluthrin was 189.4 ± 3.8–3975.0 ± 10.2 μg/g.  相似文献   
90.
Chromatographia - Nucleobases, nucleosides and nucleotides can act as chemical markers and immunnostimulants. Ultra-high-performance liquid chromatography with electrospray ionization and...  相似文献   
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