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61.
Interaction between the guanine-cytosine base pair and the episulfonium form of sulfur mustard (HD+) or the aziridinium form of nitrogen mustard (HN2+) was studied using the ab initio LCAO-MO method at the HF/6-31G level. The alkylation mechanism on the guanine N7 was analyzed by using a supermolecular modeling. Our stereostructural results associated with the molecular electrostatic potentials and highest occupied/lowest unoccupied molecular orbital (HOMO(SINGLEBOND)LUMO) properties show that in vacuum the alkylation of the N7 of guanine by HD+ in the agressive episulfonium form is a direct process without a transition state and of which the pathway is determined. Our study shows that interaction of guanine with the aziridinium form of HN2+ necessitates a transition state for the N7 alkylation route. When the N7 guanine alkylation by HD+ or HN2+ is achieved, about half of a positive charge moves from the alkylator toward the guanine in both cases. © 1996 John Wiley & Sons, Inc. 相似文献
62.
Ana Maria Titoiu Roxana Porumb Pablo Fanjul‐Bolado Petru Epure Medana Zamfir Alina Vasilescu 《Electroanalysis》2019,31(11):2262-2273
In this work we investigate the performance of a simple, disposable electrochemical aptasensor for lysozyme and its usefulness for monitoring the allergen risk along wine production. The sensor relies on screen‐printed gold electrodes modified with gold nanoparticles as the electrochemical transducer, with detection by cyclic voltammetry. This simple method is characterized by a detection limit of 0.32 μg.mL?1 lysozyme and a linear range of 1–10 μg.mL?1, being appropriate for the analysis of lysozyme‐treated wines. Several white wines where sulphur dioxide was partially replaced by lysozyme were produced and analyzed with the aptasensor at critical stages during wine production. The results obtained with the aptasensor were moreover compared with those recorded in parallel by a standard method, high performance liquid chromatography (HPLC). The specific advantages brought by the use of nanomaterial and the limitations of the sensor are discussed. The sensor allowed evaluating the effect of various technological steps along wine production on the content of lysozyme. 相似文献
63.
The effect of Antipyrin upon the antioxidant activity of the riboflavin has been evidenced using chemiluminescent system luminol–hydrogen
peroxide, in Tris–HCl buffer, pH 8.5. It was found that riboflavin antioxidant activity depends on the reaction time and the
Antipyrin concentration. Using ESR spectroscopy the hydroxyl radical generation, in the mentioned chemiluminescent system,
was evidenced. The interaction between reactants was also investigated by UV-VIS and fluorescence spectroscopy. The effect
of Antipyrin concentration upon the riboflavin fluorescence has also been investigated. The fluorescence quenching by Antipyrin
is not significant and subsequently the riboflavin fluorescence quenching doesn’t indicate an electron transfer process through
diffusion-controlled mechanism. The results are discussed with relevance to the redox processes of riboflavin. 相似文献
64.
为了低成本有效制备人参稀有皂苷C-K或F2, 将A. niger g.848菌酶用于转化含有人参皂苷(质量分数)分别为49.6% Rb1, 25.9% Rd, 19.3% Rc和5.23% Rb2的西洋参二醇混合皂苷. 霉菌发酵时, 采用人参二醇皂苷诱导物比人参提取液诱导物的产酶总活力提高10%~15%. 所产的2种诱导酶均能水解人参二醇皂苷的3-O-和20-O-多种糖基, 均为人参皂苷酶Ⅰ型; 但是人参二醇皂苷诱导物所产酶几乎全部转化人参二醇皂苷为C-K, 而人参提取液诱导物所产酶则残留中间产物. 使用黑曲霉人参二醇皂苷诱导所产酶, 在转化西洋参二醇皂苷的动态研究中发现, 酶反应1.5~2.5 h, 主要为产物F2; 酶反应12 h后, 主要产物为C-K皂苷. 基于此, 40 g人参二醇类皂苷在45 ℃粗酶反应24 h, 经处理得到含C-K质量分数为87%的23 g酶反应产物, C-K转化率达85%(摩尔分数). 用40 g西洋参二醇皂苷在45 ℃粗酶反应2.5 h, 经处理得到含有质量分数为58%的F2和27%的C-K的26 g酶反应产物, F2转化率为50.4%, C-K转化率为29.5%. 通过人参二醇皂苷诱导的黑曲霉粗酶转化人参二醇类皂苷动态研究, 建立了C-K转化率为85%, F2转化率为50%的制备方法, 为大批量制备提供了基础依据. 相似文献
65.
Camelia Albu Ramona Penu Ioana Vasilescu Simona Carmen Litescu Gabriel-Lucian Radu 《Analytical letters》2017,50(4):591-606
The goal of the present work was to study the influence of winemaking procedures and the effect of bottle-aging on the antioxidant activity and on the variation of low molecular weight phenolics of Feteasca Neagra and Negru Aromat red wine from the Valea Calugareasca vineyard, Romania. The free radical-scavenging activity was measured using the 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) radical from bottles sampled every 3 months up to the 9th month. The results indicated that Negru Aromat obtained by classical maceration had the highest activity at 6th month. The high-performance liquid chromatography results showed that the most abundant low molecular weight phenolic compounds were catechin, (?)-epicatechin, gallic acid, malvidin, and peonidin 3-O-glucoside. For the phenolics, Feteasca Neagra prepared by classical maceration and Negru Aromat by run-off juice were the richest. For anthocyanidins, the Feteasca Neagra and Negru Aromat wine by classical maceration had the highest concentrations. These results suggest that classical maceration is the winemaking procedure of choice to obtain the highest quality wine from the Valea Calugareasca vineyard. 相似文献
66.
Electrochemistry provides an array of methods to investigate protein aggregation and determine biomarkers of neurodenenerative diseases. Biosensors detecting monomeric or oligomeric biomarkers of Alzheimer's disease and Parkinson's disease evolved toward femtomolar, multiplexed detection in blood and biological fluids for less invasive diagnosis. The biosensors also serve as complementary tools in studies investigating putative biomarkers for the assessment of patient's cognitive decline. The study of protein aggregation via the direct electrochemical oxidation focused recently on enhanced sensitivity and on establishing correlations between protein structure and aggregation propensity. Departing from classic approaches, nanopore resistive pulse sensing and single-particle collision electrochemistry enable studying aggregates in solution. Growing applications converge toward accurate evaluation of aggregate populations and method adoption beyond proof of principle. 相似文献
67.
Molecular modeling of melatonin was conducted using AM1 and ab initio quantum computations. Our study shows that four minimal energy conformations (noted I to IV) with a folded ethylamido side-chain are possible. These conformations are in correspondance (form I with form II, and form III with form IV) and are characterized by equivalent orbital frontiers and electrostatic properties. Conformations II and IV are in good agreement with pharmacophore models proposed by Jansen et al. [Bioorganic Med. Chem. 4 (1996) 1321] or by Sicsic et al. [J. Med. Chem. 40 (1997) 739].
The localization of molecular electrostatic potential and of the H and L onto the indole may explain a dominant role of this ring in the free radical scavenging mechanism. 相似文献
68.
Cristina Stere Mihaela Iovu Adrian Boborodea Dan Sorin Vasilescu Iosif Sorin Fazakas-Anca 《先进技术聚合物》1998,9(6):322-325
The potassium naphthalenide complex with 18-crown-6 is able to initiate anionic polymerization of L -lactide at 20°C. This type of anionic initiator does not have to be removed from the polymer as it does not affect metabolic processes. The ionic polymerization of L -lactide with an initiator based on Zn(II) acetyl acetonate, which is fairly stable, has been investigated. It has been found that this process leads to the corresponding polyesters, at high yields. © 1998 John Wiley & Sons, Ltd. 相似文献
69.
The formation of an intramolecular excimer of 1,10-bis(1-pyrene)decane in sodium dodecyl sulfate (SDS)/bovine serum albumin (BSA) and SDS/poly(ethylene oxide) (PEO) solutions was studied by steady-state and time-resolved fluorescence methods to determine the effect of viscosity. The viscosity-dependent ratio between intramolecular excimer and monomer fluorescence intensities of 1,10-bis(1-pyrene)decane was obtained by steady-state fluorescence measurements. The results show that in micelle-like clusters formed in SDS/BSA and SDS/PEO systems, the microviscosity is higher than in free micelles. It was found that Birks' kinetic model was not valid in this case, and the monomer and excimer fluorescence decays had to be fitted by a sum of three exponentials. The excimer formation kinetics in constrained systems is more complex than in homogeneous solutions, but it is possible to find an empirical parameter depending on viscosity. 相似文献
70.