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111.
A capillary zone electrophoresis (CZE) method, optimised chemometrically, underwent a complete in-house validation protocol for the qualification and quantification of sucralose in various foodstuffs. Separation from matrix components was obtained in a dinitrobenzoic acid (3 mM)/sodium hydroxide (20 mM) background electrolyte with a pH of 12.1, a potential of 0.11 kV cm–1 and a temperature of 22 °C. Detection was achieved at 238 nm by indirect UV. Screening, optimisation and robustness testing were all carried out with the aid of experimental design. Using standard addition calibration, the CZE method has been applied to still, carbonated and alcoholic beverages, yoghurts and hard-boiled candy. The method allows the detection of sucralose at >30 mg kg–1, with a linearity range of 50–500 mg kg–1, making it suitable for implementation of the recently amended Sweeteners for use in foodstuffs Directive (European Parliament and Council (2003) Off J L237:3–12), which set maximum usable doses of sucralose for many foodstuffs, most ranging from 200 mg kg–1 to 450 mg kg–1. 相似文献
112.
Biosynthesis and structure of aeruginoside 126A and 126B, cyanobacterial peptide glycosides bearing a 2-carboxy-6-hydroxyoctahydroindole moiety 总被引:1,自引:0,他引:1
Ishida K Christiansen G Yoshida WY Kurmayer R Welker M Valls N Bonjoch J Hertweck C Börner T Hemscheidt T Dittmann E 《Chemistry & biology》2007,14(5):565-576
Aeruginosins represent a group of peptide metabolites isolated from various cyanobacterial genera and from marine sponges that potently inhibit different types of serine proteases. Members of this family are characterized by the presence of a 2-carboxy-6-hydroxyoctahydroindole (Choi) moiety. We have identified and fully sequenced a NRPS gene cluster in the genome of the cyanobacterium Planktothrix agardhii CYA126/8. Insertional mutagenesis of a NRPS component led to the discovery and structural elucidation of two glycopeptides that were designated aeruginoside 126A and aeruginoside 126B. One variant of the aglycone contains a 1-amino-2-(N-amidino-Delta(3)-pyrrolinyl)ethyl moiety at the C terminus, the other bears an agmatine residue. In silico analyses of the aeruginoside biosynthetic genes aerA-aerI as well as additional mutagenesis and feeding studies allowed the prediction of enzymatic steps leading to the formation of aeruginosides and the unusual Choi moiety. 相似文献
113.
Prof. Dr. Peter Schwerdtfeger Dr. Ralf Tonner Dr. Gloria E. Moyano Dr. Elke Pahl 《Angewandte Chemie (International ed. in English)》2016,55(40):12200-12205
The cohesive energies of argon in its cubic and hexagonal closed packed structures are computed with an unprecedented accuracy of about 5 J mol?1 (corresponding to 0.05 % of the total cohesive energy). The same relative accuracy with respect to experimental data is also found for the face‐centered cubic lattice constant deviating by ca. 0.003 Å. This level of accuracy was enabled by using high‐level theoretical, wave‐function‐based methods within a many‐body decomposition of the interaction energy. Static contributions of two‐, three‐, and four‐body fragments of the crystal are all individually converged to sub‐J mol?1 accuracy and complemented by harmonic and anharmonic vibrational corrections. Computational chemistry is thus achieving or even surpassing experimental accuracy for the solid‐state rare gases. 相似文献
114.
Armand Blaschette Elke Wieland Gerlinde Seurig Dietrich Koch Firouz Safari 《无机化学与普通化学杂志》1983,506(11):75-86
Investigations on Bis(methylsulfonyl)-amine (Dimesylamine). III. Onium Salts of Dimesylamine Thirty-five salts of the strong acid HN(SO2Me)2 containing onium cations are reported. These include higher quaternary ammonium salts which show excellent solubility in solvents of low polarity, thus being particularly useful for preparing solutions of “naked” (MeSO2)2N? or corresponding ion-pairs. Pyrolysis of the quaternary ammonium salts at temperatures of 200—250°C produces tertiary amines and N-alkyl-dimesylamines by (N → N′)-alkyl transfer. Alkene formation is not observed. 相似文献
115.
Elke Marten Rolf-Joachim Müller Wolf-Dieter Deckwer 《Polymer Degradation and Stability》2003,80(3):485-501
The bio-catalysed cleavage of ester bonds in low molecular mass model esters and aliphatic polyesters was studied in detail with the aim to gain improved information about the underlying mechanism and the parameters controlling polyester degradation. Among various hydrolytic enzymes the lipase of Pseudomonas species (PsL) was chosen for the investigations. In the heterogeneous phase system the specific hydrolysis rate of the esters was constant as long as free substrate surface was available. In addition to aliphatic low molecular mass model esters, also cycloaliphatic and aromatic esters were cleaved by PsL, indicating that a steric hindrance of the enzymatic ester cleavage is not the predominant controlling factor in polyester degradation. However, the cleavage rates of the aliphatic model esters are larger by more than an order of magnitude. For aliphatic polyesters the temperature difference between the melting point of the polymer and the temperature where degradation takes place (ΔTmt), turned out to be the primary controlling parameter for polyester degradation with the lipase. Only if ΔTmt<30 °C, a measurable enzymatic degradation rate is found. ΔTmt can be regarded as a measure of the mobility of the polyesters chains in the crystalline domains, necessary for the access of the esters to the active site of the lipase. Though aliphatic homopolyesters are seemingly very similar with regard to their chemical structure and reactivity of the ester bonds, their enzymatic degradation rates still differ significantly even at the same ΔTmt. These differences have obviously to be attributed to small changes in the chemical structure, as, for instance, the C number of the aliphatic diacid. 相似文献
116.
Nature has provided the binuclear zinc based active site of bovine lens leucine aminopeptidase (blLAP) with two water channels: one for substrate docking and a much smaller one (function unknown) above Zn1. In addition, Zn1 possesses an unusual pentacoordinate geometry with a loosely bound carbonyl ligand (Ala333). Extensive DFT calculations on a model of the active site provide first mechanistic implications for these structural features. The weakly bound carbonyl ligand is capable of functioning as a "traffic cop" to direct water molecules coming from the small channel into the heart of the active site. A water sluice is thus generated that is capable of repeatedly providing a series of nucleophilic active "Zn-OH" functionalities. 相似文献
117.
Calorimetric and dielectric results for crystallizable poly(n-alkyl methacrylates) (PnAMA) with C=12, 16 and 18 alkyl carbons per side chain are presented. Degree of crystallization Dcal and melting peak temperature TM are estimated from conventional DSC measurements. For poly(n-hexadecyl methacrylate) (C=16) the influence of isothermal crystallization is studied by DSC as well as TMDSC. Changes in dielectric relaxation strength Δε and α peak shape during crystallization are investigated. Effects of side chain crystallization on the complex dynamics of PnAMA are discussed. The results are related to the relaxation behavior of lower nanophase-separated PnAMA with two co-existing glass transitions, the conventional glass transition (a or α) and the polyethylene-like glass transition (αPE) within alkyl nanodomains formed by aggregated alkyl rests. It is shown that amorphous as well as semicrystalline PnAMA can be understood as nanophase-separated polymers with alkyl nanodomains having a typical dimension of 1-2 nm. The results are compared with the predictions of simple morphological pictures for side chain polymers. X-ray scattering data for the amorphous and semicrystalline PnAMA are included in the discussion. Common aspects of nanophase-separated systems in both states as well as differences caused by crystallization are discussed. Indications for the existence of rigid amorphous regions are compiled. Different approaches to explain a similar increase of Tg(αPE)—the glass temperature of the amorphous alkyl nanodomains—and TM—the melting temperature of crystalline alkyl nanodomains—with side chain length are considered. Pros and cons of both approaches, based on increasing order within the alkyl nanodomains and confinement effects in nanophase-separated systems, are discussed. Main trends concerning crystallization and cooperative dynamics are compared with those in other systems with self-assembled nanometer confinements like microphase-separated blockcopolymers or semicrystalline main chain polymers. 相似文献
118.
The dependency of EOF on the H+-concentration and the related so called pH* value of methanolic electrolytes has been examined with poly(ethylene glycol) (PEG), poly(vinyl alcohol) (PVA) and uncoated capillaries. These results were compared with the pH dependency of EOF of these capillaries using aqueous buffers. In uncoated capillaries the dependency of EOF on the pH(*)-value is very similar for aqueous and methanolic electrolytes. The EOF increases with increasing H+-concentration and pH-hysteresis is observed. In PVA coated capillaries the EOF is strongly reduced over wide pH* or pH ranges for both methanolic electrolytes and aqueous buffers. The EOF in PEG coated capillaries is surprisingly directed to the anode with methanolic electrolytes whereas a reduced cathodic EOF is observed in aqueous electrolytes. The anodic EOF of PEG-coated capillaries in methanolic electrolytes is independent of the pH*-value. The usefulness of PEG- and PVA-coated capillaries for adjusting the EOF in non-aqueous electrolytes for the analysis of isomeric organic acids was demonstrated. 相似文献
119.
Determination of siloxanes,silicon, and platinum in tissues of women with silicone gel-filled implants 总被引:4,自引:0,他引:4
Flassbeck D Pfleiderer B Klemens P Heumann KG Eltze E Hirner AV 《Analytical and bioanalytical chemistry》2003,375(3):356-362
Silicone [poly(dimethylsiloxane)] gel used in breast implants has been known to migrate through intact silicone elastomer shells, resulting in the clinically observable "gel bleed" on the implant surface. Although silicon concentrations in capsular tissues of women with silicone prostheses have been measured with element-specific silicon analyses, no silicone-specific investigation of these tissues has been performed as yet.A combination of element-specific inductively coupled plasma high-resolution isotope dilution mass spectrometry (ICP-HR-IDMS) and species-specific gas chromatography coupled mass spectrometry (GC-MS) was used to analyze silicon, platinum, and siloxanes in prosthesis capsule, muscle, and fat tissues of women (n=3) who had silicone gel-filled breast implants and in breast tissue of non-augmented women (n=3) as controls.In all tissues of augmented women, siloxanes, in particular octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were identified. Depending on the siloxane species and type of tissue analyzed, siloxane levels in the range of about 10-1,400 ng g(-1) were detected; total silicon was found in all tissue samples in the range of about 8,900-85,000 ng g(-1). Higher platinum levels ranging from 25-90 ng g(-1 )were detected in fibrin layer and fat tissue of two patients with prostheses. No siloxanes were detected in control breast tissue samples.This investigation of human tissues by a combination of element-specific and species-specific analytical techniques clearly demonstrates for the first time that platinum and siloxanes leak from prostheses and accumulate in their surrounding tissues. 相似文献
120.
Hans-Joachim Knlker Elke Baum Regina Graf Peter G. Jones Oliver Spieß 《Angewandte Chemie (International ed. in English)》1999,38(17):2583-2585
A stereoselective synthesis of the disilyl derivatives 3 is achieved by the title reaction, an unprecedented Lewis acid promoted domino reaction, between the cross-conjugated dienone 1 and the allylsilanes 2 . The configurations of the five stereogenic centers of this novel ring system are established in the first step of the reaction sequence, the double [3+2] cycloaddition. 相似文献