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Solutions of CoII salts of organic acids in primary amines absorb molecular oxygen rapidly and irreversibly forming μ-dioxygen—cobalt complexes. Thermolysis leads to a homopolar cleavage of the OO bond with subsequent radical reactions involving ligand amine. After thermolysis the capacity of oxygen uptake is reestablished (catalysis).  相似文献   
124.
A liquid chromatographic-mass spectrometric assay with atmospheric pressure chemical ionization (LC-APCI-MS) is presented for screening for, library-assisted identification (both in scan mode) and quantification (selected-ion mode) of the beta-blockers acebutolol, diacetolol, alprenolol, atenolol, betaxolol, bisoprolol, bupranolol, carazolol, carteolol, carvedilol, celiprolol, esmolol, labetalol, metoprolol, nadolol, nebivolol, oxprenolol, penbutolol, propranolol, sotalol, talinolol and timolol in blood plasma after mixed-mode (HCX) solid-phase extraction (SPE) and separation by reverse-phase liquid chromatography with gradient elution. The validation data were within the required limits. The assay was successfully applied to authentic plasma samples allowing confirmation of diagnosis of overdose situations as well as monitoring of patients' compliance.  相似文献   
125.
The synthesis, characterization, and optical properties of a series of new 2,6‐disubstituted naphthalene‐bisimide dyes as molecular rods comprising terminal AcS groups is reported. The first series of dyes ( 1 – 3 ), comprising phenylhetero (Ph‐X) core substituents, cover a broad range of the VIS spectrum, ranging from yellow ( 2 ) over red ( 3 ) to blue ( 1 ). The second series of dyes contains benzylhetero (Bn‐X) core substituents ( 4 – 7 ). For the same heteroatom connecting the substituent to the naphthalene core, both series were found to display comparable colors. For the second series, the colors were blue ( 4 ), red ( 5 ), and violet ( 6, 7 ). The Ph‐X‐substituted dyes 1 – 3 are nonfluorescent, in contrast to the Bn‐X‐substituted compounds 4 – 7 . This rich variety of optical features that can be adjusted by rather small alterations of the core substituents makes these structurally very comparable molecular rods ideal candidates for optically triggered molecular‐transport investigations. Also, thanks to the terminal AcS groups, these compounds can be placed between nobel‐metal electrodes for optically triggered transport experiments.  相似文献   
126.
The synthesis and binding properties of a new tricationic guanidiniocarbonyl pyrrole receptor 7 are described. Receptor 7 binds citrate 9 and other tricarboxylates such as trimesic acid tricarboxylate 8 with unprecedented high association constants of K(assoc) > 10(5) M(-1) in water as determined by UV and fluorescence tritration studies. According to NOESY experiments and molecular modeling calculations, the tricarboxylates are bound within the inner cavity of receptor 7 by ion pairing between the carboxylate groups and the guanidiniocarbonyl pyrrole moieties, favored by the nonpolar microenvironment of the cavity. Hence, receptor 7 can be regarded as a molecular flytrap. In the case of the aromatic tricarboxylate 8, additional aromatic interactions further strengthen the complex. The complexes with the tricarboxylates are so strong that even the presence of a large excess of competing anions or buffer salts does not significantly affect the association constant. For example, the association constant for citrate changes only from K(assoc) = 1.6 x 10(5) M(-1) in pure water to K(assoc) = 8.6 x 10(4) M(-1) in the presence of a 170-fold excess of bis-tris buffer and a 1000-fold excess of chloride. This makes 7 one of the most efficient receptors for the binding of citrate in aqueous solvents reported thus far.  相似文献   
127.
High resolution gas chromatography, with mass selective detection, has been used for the analysis of PCB on methyl 50 % octyl polysiloxane (SB 50 Octyl), methyl octadecyl polysiloxane, and a smectic polysiloxane (SB Smectic); and for the analysis of polychlorodibenzodioxins and polychlorodibenzofurans with 1 to 8 chlorine substituents on 100 % cyanopropyl siloxane (SP 2331), smectic polysiloxane (SB Smectic), a new polar stationary phase (DB-Dioxin). The analysis has also been performed by column coupling.  相似文献   
128.
The aim of the present study was to provide the official wine control authorities with an internationally validated method for the determination of 3-methoxy-1,2-propanediol (3-MPD) and cyclic diglycerols (CycDs)-both of which are recognized as impurities of technical glycerol-in different types of wine. Because glycerol gives a sweet flavor to wine and contributes to its full-body taste, an economic incentive is to add glycerol to a wine to mask its poor quality. Furthermore, it is known that glycerol, depending on whether it is produced from triglycerides or petrochemicals, may contain considerable amounts of 3-MPD in the first case or CycDs in the second. However, because these compounds are not natural wine components, it is possible to detect glycerol added to wine illegally by determining the above-mentioned by-products. To this end, one of the published methods was adopted, modified, and tested in a collaborative study. The method is based on gas chromatographic/mass spectrometric analysis of diethyl ether extracts after salting out with potassium carbonate. The interlaboratory study for the determination of 3-MPD and CycDs in wine was performed in 11 laboratories in 4 countries. Wine samples were prepared and sent to participants as 5 blind duplicate test materials and 1 single test material. The concentrations covered ranges of 0.1-0.8 mg/L for 3-MPD and 0.5-1.5 mg/L for CycDs. The precision of the method was within the range predicted by the Horwitz equation. HORRAT values obtained for 3-MPD ranged from 0.8 to 1.7, and those obtained for CycDs ranged from 0.9 to 1.3. Average recoveries were 104 and 109%, respectively.  相似文献   
129.
A dimethylsiloxane diluted polysiloxane side chain co-polymer with non-chiral banana-shaped mesogenic units shows an optically isotropic ferroelectric switching polar smectic C phase (SmCPF) consisting of a conglomerate of homogeneously chiral domains with opposite handedness.  相似文献   
130.
The oligosaccharide antibiotic avilamycin A is composed of a polyketide-derived dichloroisoeverninic acid moiety attached to a heptasaccharide chain consisting of six hexoses and one unusual pentose moiety. We describe the generation of mutant strains of the avilamycin producer defective in different sugar biosynthetic genes. Inactivation of two genes (aviD and aviE2) resulted in the breakdown of the avilamycin biosynthesis. In contrast, avilamycin production was not influenced in an aviP mutant. Inactivation of aviGT4 resulted in a mutant that accumulated a novel avilamycin derivative lacking the terminal eurekanate residue. Finally, AviE2 was expressed in Escherichia coli and the gene product was characterized biochemically. AviE2 was shown to convert UDP-D-glucuronic acid to UDP-D-xylose, indicating that the pentose residue of avilamycin A is derived from D-glucose and not from D-ribose. Here we report a UDP-D-glucuronic acid decarboxylase in actinomycetes.  相似文献   
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