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91.
Giordano Lesma 《Tetrahedron》2007,63(25):5567-5578
New peptidomimetics containing the Tic moiety were synthesized in enantiomerically pure form and their conformational features were studied by NMR, IR, and molecular modeling techniques. The presence of a reverse turn conformation was observed in all the structures, suggesting the key role of the scaffold as reverse turn inducer. In particular, all the analyses led to the conclusion that a β-turn conformation is mostly stabilized in tetrapeptide mimetic 4b and in hexapeptide mimetics 5a,b. In the case of 5a,b, the C1 stereochemistry plays a central role in determining stable conformations, supporting the formation of a β-hairpin arrangement with a 14-membered intramolecular hydrogen bond ring only in 5b. 相似文献
92.
The fine-tuning of the enzymatic hydrolysis of proteins may provide a pool of peptides with predefined molar mass distributions. However, the complex mixture of molecules (peptides and amino acids) that results after the proteolysis of cheese whey turns unfeasible the assessment of individual species. In this work, a hybrid kinetic model for the proteolysis of whey by alcalase, multipoint-immobilized on agarose, is presented, which takes into account the influence of pH (8.0-10.4) and temperature (40-55 degrees C) on the activity of the enzyme. Five ranges of peptides' molar mass have their reaction rates predicted by neural networks (NNs). The output of NNs trained for constant pH and temperatures was interpolated, instead of including these variables in the input vector of a larger NN. Thus, the model complexity was reduced. Coupled to differential mass balances, this hybrid model can be employed for the online inference of peptides' molar mass distributions. Experimental kinetic assays were carried out using a pH-stat, in a laboratory-scale (0.03 L) batch reactor. The neural-kinetic model was integrated to a supervisory system of a bench-scale continually stirred tank reactor (0.5 L), providing accurate predictions during validation tests. 相似文献
93.
New pyrroloisoquinoline-based tetrapeptides were synthesized in enantiomerically pure form, and their conformational features were studied by NMR, IR, and molecular-modeling techniques. The presence of a reverse turn was observed in both structures, with the C1 stereochemistry playing a central role in determining stable conformations. In particular, all of the analyses led to the conclusion that a type II' beta-turn is mostly stabilized in tetrapeptide mimic 3a, while a typical inverse gamma-turn geometry is revealed for the diastereoisomer 3b. 相似文献
94.
S. Bollanti P. Di Lazzaro F. Flora G. Giordano T. Letardi D. Murra G. Schina C.E. Zheng 《Applied physics. B, Lasers and optics》1999,68(4):683-688
6 shots, the X-ray dose, uniformity, and ionisation rate values guarantee an effective preionisation of excimer laser discharges.
Owing to both the long lifetime and the substantial absence of maintenance, this X-ray diode seems suitable to preionise commercial
gas lasers, such as excimer and TEA CO2 lasers.
Received: 28 August 1998 / Revised version: 16 November 1998 / Published online: 24 February 1999 相似文献
95.
96.
Bruno Danieli Giordano Lesma Daniele Passarella Davide Prosperi Alessandra Silvani Ezio Bombardelli 《Helvetica chimica acta》1999,82(9):1502-1508
In an attempt to use 3,5-di(tert-butyl)-1,2-benzoquinone for the oxidative deamination of N-deacetylcolchicine ( 4 ) and N-deacetylthiocolchicine (=N-deacetyl-10-demethoxy-10-(methylthio)colchicine; 5 ) to give the corresponding ketones 2 and 3 , the 2H-1,4-benzoxazine-type adducts 8 / 9 and 11 / 12 , respectively, were formed instead, showing a new and unexpected behavior of Corey's reagent. The adducts were separated and spectroscopically characterized, and a plausible scheme of formation is reported. 相似文献
97.
A. Laricchiuta D. Bruno M. Capitelli C. Catalfamo R. Celiberto G. Colonna P. Diomede D. Giordano C. Gorse S. Longo D. Pagano F. Pirani 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2009,54(3):607-612
In the perspective of higher approximations of the Chapman-Enskog theory for transport property calculations, existing transport
cross sections databases for interactions involving Earth atmosphere species have been updated and extended to Mars atmosphere
components, proposing a phenomenological approach for the derivation of the relevant elastic collision integrals in neutral-neutral
and neutral-ion interactions. Inelastic collision integrals terms, due to resonant charge exchange channels, have been considered
and the asymptotic approach extended to the estimation of charge transfer cross section of multiple resonant processes.
Electronic supplementary material Supplementary Online Material 相似文献
98.
Joubert Trovati Roberto C. Giordano Raquel L. C. Giordano 《Applied biochemistry and biotechnology》2009,156(1-3):76-90
In a previous work, a continuous simultaneous saccharification and fermentation process to produce ethanol from cassava starch was studied, using a set of fixed-bed reactors. The biocatalyst consisted of glucoamylase immobilized in silica particles and co-immobilized with S. cerevisiae in pectin gel. Using 3.8 U mL?1 reactor and 0.05 gwet yeast mL?1 reactor at start-up, starch hydrolysis was the rate-limiting step. Maximum ethanol productivity was 5.8 gethanol L?1 h?1, with 94.0% conversion of total reducing sugars (TRS) and 83.0% of the ethanol theoretical yield. In this work, the molar mass of the substrate and the biocatalyst particle size were reduced in an attempt to improve the bioreactor performance. The diameters of silica and pectin gel particles were reduced from 100 μm and 3–4 mm, respectively, to 60 μm and 1–1.5 mm, and the degree of substrate prehydrolysis by α-amylase was increased. The bioreactor performance was assessed for different loads of immobilized glucoamylase (2.1, 2.8, and 3.8 U mL?1 reactor), for the same initial cell concentration (0.05 gwet yeast.mL?1 reactor). Feeding with 154.0 g L?1 of TRS and using 3.8 U mL?1 reactor, fermentation became the rate-limiting step. Productivity reached 11.7 g L?1 h?1, with 97.0% of TRS conversion and 92.0% of the ethanol theoretical yield. The reactor was operated during 275 h without any indication of destabilization. 相似文献
99.
The interaction of Pd and Au atoms with a silica surface and SiO2Mo(112) ultrathin films has been studied with periodic density-functional theory-generalized gradient approximation calculations. On both unsupported and supported silica, Pd and Au are weakly bound. No charge transfer occurs to the empty Pd and Au orbitals. Differently from Au, Pd can easily penetrate with virtually no barrier into the hexagonal rings of the supported silica film and binds strongly at the SiO2-Mo interface. The same process for Au implies overcoming a barrier of 0.9 eV. Completely different is the behavior of Ti-doped silica films. Au forms a direct covalent bond with substitutional Ti at the expense of the Ti...O-Mo interface bond which breaks. The global process is exothermic by 1 eV and nonactivated, showing that Ti doping results in solid anchoring points for the adsorbed Au atoms and for nucleation and growth of small gold particles. The effect of Ti doping is less pronounced for Pd but still visible with substantial enhancement of the Pd adsorption strength. 相似文献
100.
Dyes and pigments are extensively used in polymer materials to confer colour-changing properties. However, these additives can significantly affect polymer stability against degradation. While the mechanism of stabilization of polymers by some pigments, such as carbon black, has been studied and is well known, the action of chromatic colorants, mainly in the sensitization of the degradation process, remains unclear. Cu-phthalocyanine dye can stabilize polymers against degradation as well as accelerate degradation in other situations. Cu-phthalocyanine incorporated into polycarbonate resulted in an acceleration of the degradation when the material was submitted to photochemical aging. The possible mechanism to explain the photodegradative behavior of PC containing Cu-phthalocyanine is based on the hypothesis that specific interactions among excited states of PC and Cu-phthalocyanine take place and enhance the formation of reactive species in polycarbonate. Excited states of Cu-phthalocyanine may abstract hydrogen atoms from methyl groups in polycarbonate, increasing the formation of free radicals P, which are the starting points for the sequential photo-oxidation reactions that lead to the degradation of the polycarbonate. Electron transfer sensitization is also a possible mechanism: the excited state of Cu-Ph abstracts an electron from PC to form the Cu-Ph radical anion and the PC radical cation. These reactive species in the presence of oxygen can cause oxidation of the aromatic ring. 相似文献