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91.
Avian eggshell matrix proteins were studied by two analytical approaches. Peptide mapping was done by trypsin and pepsin followed by collagenase cleavage; analyses were carried out by capillary electrophoresis and reversed-phase high-performance liquid chromatography (HPLC). Comparison of peptide maps obtained by both methods revealed a complex mixture of peptides in the insoluble layers of the eggshell; it was concluded that there are at least three different insoluble protein/peptide layers in the avian eggshell (cuticle, palisade, and mammillary layer). Partial characterization of peptides in each layer was made by HPLC-mass spectrometry analysis. There is an evidence that the eggshell insoluble proteins contain species susceptible to collagenase cleavage, however, the sequences split by this enzyme probably are not those typical for the main triple-helical core of collagenous proteins. It is proposed that the action of collagenase upon eggshell proteins is caused by the side effect of collagenase described previously with synthetic peptides. Some of the proteins present are probably glycosylated. Fatty acid content in the insoluble eggshell layers (after decalcification) was in the range of 2-4% (which reflected both lipid and lipoproteins bound fatty acids). Porphyrin pigments are dominant in the cuticle layer. 相似文献
92.
James D. Korp Ivan Bernal Nikolaus H. Fischer Charles Leonard Ihl-Young Lee Ngo LeVan 《Journal of heterocyclic chemistry》1982,19(1):181-187
The isolation and structure determination of two new guaianolides, pumilin and its 2,3-epoxide, from Berlandiera pumila and B. texana are reported. The structure of pumilin was determined from nmr and mass spectral data, and from an X-ray single crystal study; the structure of the epoxide was found by comparison of nmr spectra. Pumilin is shown to be a Δ1(10)-cis-guaianolide with a cyclopentenone ring attached to C1 and C5, and an α-methylene-γ-lactone ring trans-fused to C6 and C7. The absolute configuration was inferred from spectral considerations and knowledge of previous structural determinations. The cd spectrum of pumilin exhibits a negative Cotton effect, and the lactone chromophore has left-handed chirality. The cyclo-heptene ring is in the chair configuration, with the lactone a half-chair and the cyclopentenone essentially planar. Crystals are orthorhombic, a = 7.065, b = 13.652, c = 19.586 Å, space group P212121, Z = 4, and the final R value is 3.9%. The crystal structure is strengthened by an O···O hydrogen bond linking the molecules into infinite chains. 相似文献
93.
Djordje Vlaović Gordana Ćetković Ivan Juranić Jelica Balaž Stevan Lajšić Dejan Djoković 《Monatshefte für Chemie / Chemical Monthly》1990,121(11):931-939
Summary The syntheses andin vitro antibacterial and antifungal evaluation of certain (5-nitro-2-furyl)azomethines with different heterocyclic nuclei are described.
Die Anwendung von Lävulinsäure und 5-Nitro-2-furylmethylendiacetat in der Totalsynthese einiger neuer biologisch aktiver (5-Nitro-2-furyl)azomethine
Zusammenfassung Es wird die Synthese und diein-vitro-antibakterielle und antifungale Wirksamkeit für bestimmte (5-Nitro-2-furyl)azomethine mit verschiedenen heterocyclischen Kernen beschrieben.相似文献
94.
Beech sawdust (S) and samples containing 1% of H3PO4 (SP), (NaPO3)n (PS), P2O5 (POS), NaOH/P2O5 (SPS), NaOH (SS) or Na2CO3 (CS) were analysed using dynamic and isothermal thermogravimetry (TG) in nitrogen and oxygen environments. According to the results of dynamic experiments in nitrogen, the thermal resistance at 275 °C decreased in the order: S > SS > CS > SP> SPS > PS > POS, while in oxygen the order was: S > POS > SPS=CS=PS > SP > SS. The difference in residues obtained in nitrogen in comparison to oxygen environment reaches its maximum at temperatures from 300 to 325 °C and according to the decreasing values the following order could be listed: SS (300 °C/27%) > SP (325 °C/25%) > CS (300 °C/24%) > S (325 °C/23%) > SPS (300 °C/19%) > PS (300 °C/11%) > POS (275 °C/4%). This indicates that with a decreasing difference in residues formed in oxidative and inert environments the flame-retardant effect of the sample is increasing. The calculated initial rate constants of residue formation and gasification and the corresponding activation energies of the processes in nitrogen and oxygen from the isothermal experiments gave smaller values of rate constants for SPS than for S. For the SPS sample in comparison with S the activation energy of residue formation in nitrogen decreased while the three remaining values increased. The Er* of PS in the oxygen is the biggest from all studied samples under the conditions used, while SPS gave the biggest Eg* in the oxygen environment. The phosphorus could be washed out with water from SP and SPS, while it remained in PS and POS. These last two samples also have the best flame-retarding properties according to TG analysis. 相似文献
95.
In this communication we propose a novel application for prefluorescent probes in the detection of free carbon-centered radicals in enzymatic processes. Prefluorescent probes combine a fluorescent moiety tethered to a paramagnetic nitroxide that acts as a fluorescence quencher. Trapping of a radical by the nitroxide group restores the fluorescence properties. The increase in fluorescence intensity with time reflects the formation and quenching of carbon-centered radicals and can be used for the quantitative evaluation of yields and kinetics. As a test system we used horseradish peroxidase, an oxidoreductase that is widely accepted to operate by a radical-mediated mechanism. We used the prefluorescent probe (quinoline-TEMPO), where a quinoline moiety has been tethered to 2,2,6,6-tetramethylpiperidin-1-oxyl. 相似文献
96.
Ivan Němec Zorka Machá?ková Ivana Císa?ová Zdeněk Mi?ka 《Journal of solid state chemistry》2004,177(12):4655-4664
Aminoguanidinium(1+) dihydrogen phosphate was prepared by crystallization from aqueous solution. On the basis of the results of DSC measurements, X-ray structural analysis was carried out at temperatures of 160, 215 and 293 K for three aminoguanidinium(1+) dihydrogen phosphate phases ( |Z=2|non-ferroic |melting point 408 K; II |201-222 K|(2) |Z=2|non-ferroic|-; III |<201 K|(2)|Z=4|non-ferroic|-). The triclinic unit cell dimensions (a=6.8220(2), b=7.1000(2), c=7.4500(2) Å, α=86.925(2)°, β=80.731(2)°, γ=79.630(2)°, V=350.21(2) Å3—phase I) are similar for all three structural phases with the exception of phase III, where doubling of the c-axis length leads to an increase in the volume to 692.34(3) Å3. The crystal structure of all three modifications consists of parallel layers of dihydrogen phosphate anions that are interconnected by aminoguanidinium(1+) cations through hydrogen bonds of the N-H…O type. The planar aminoguanidinium(1+) cations are oriented almost parallel to each other and are perpendicular to the anion layers. The primary differences amongst phases I, II and III lie in the location of the H atom in the short O-H…O bonds connecting the dihydrogen phosphate anions in layers. The FTIR and FT Raman spectra of natural and deuterated compounds were recorded and interpreted. The FTIR spectra were studied down to a temperature of 90 K. 相似文献
97.
Quantitative investigation of the reaction of the ferri-heme model compound Fe(III)(TPPS)(H(2)O)(2) (1) to give Fe(II)(TPPS)(NO) (2) (TPPS = tetra(4-sulfonato-phenyl)porphinato) in buffered aqueous solution demonstrates a slow pH-independent reductive nitrosylation pathway in the pH range 4-6. The rate of this reaction is subject to modest general base catalysis. In the course of this study, a surprising catalytic pathway whereby nitrite ion (NO(2)(-)) strongly catalyzes the reduction of 1 to 2 under reductive nitrosylation conditions was demonstrated. 相似文献
98.
Klika KD Imrich J Danihel I Böhm S Kristian P Hamul'aková S Pihlaja K Koch A Kleinpeter E 《Magnetic resonance in chemistry : MRC》2005,43(5):380-388
The configuration and dynamic behavior of O-allyl-S-methyl-N-(acridin-9-yl)iminothiocarbonate (1) and its S-allyl-O-methyl regioisomer (2) were studied using quantum chemical calculations and by applying a novel graphical method to scatter maps obtained from MD simulations for evaluation of an NOE-weighted internuclear distance (r(NOE)). Energy calculations indicated that the Z configuration was predominant for each compound and, further, this was supported both by the calculated chemical shifts and the r(NOE). Both N-inversion- and rotation-type transition-state structures were also calculated for the E/Z isomerization process, the results indicating that the preferred interconversion mechanism for 1 is N-inversion, but contrastingly, interconversion via rotation is equally as probable as N-inversion for 2. This supports the notion that one or the other or both pathways can be active and each system needs to be assessed on a case-by-case basis. 相似文献
99.
Evaluated in the present investigation are possible synthetic approaches to vinigrol based on the involvement of lactone rings as tools for the conformational rigidification of functionalized cis-octalins. Emphasis was placed on the structural arrangements resident in 3 and 5. The first of these systems proved to be highly strained and inaccessible. Especially notable was the finding that hydroxy ketenes 14 and 21 could be isolated and shown not to be amenable to cyclization when heated. The stereo-controlled assembly of 5 was successfully accomplished through exploitation of a related synthetic pathway. However, neither this attractive intermediate nor its close relative 33 could be processed in a manner that delivered the vinigrol framework. Nonetheless, several features of the routes deployed offer the prospect of wider application in other contexts. 相似文献
100.
The method is based on the oxidation of ethanol in the presence of alcohol oxidase, followed by oxidation of 2,2'-azino-di(3-ethylbenzthiazoline-6-sulfonate) in the presence of peroxidase. 相似文献