Two new cryptic 3,4-dihydronaphthalen-(2H)-1-one (1-tetralone) derivatives, aspvanicin A (1) and its epimer aspvanicin B (2), as well as several known cryptic metabolites (3–8), were obtained from the ethyl acetate extract of the co-culture of the endophytic fungus Aspergillus versicolor KU258497 with the bacterium Bacillus subtilis 168 trpC2 on solid rice medium. When A. versicolor was cultured axenically in liquid Wickerham medium supplemented with 3.5% DMSO, an additional three known secondary metabolites (9–11) were isolated that were lacking when the fungus was fermented on rice medium. The structures of the new compounds were elucidated using one- and two-dimensional NMR spectroscopy as well as HRESIMS. The relative and absolute configurations of 1 and 2 were determined by the combination of NMR and electronic circular dichroism (ECD) analysis aided by DFT conformational analysis and TDDFT-ECD calculations. The ECD calculations revealed that although the sign of the blue-shifted overlapping n-π1 ECD transition follows the helicity rule of cyclic aryl ketones, the calculation of low-energy conformers and ECD spectra was necessary to determine the stereochemistry. All metabolites were assessed for their antibacterial and cytotoxic activities; one of the new diastereomers, compound 2, showed moderate cytotoxic activity against the mouse lymphoma cell line L5178Y. 相似文献
In this work, an electromembrane extraction (EME) technique was used for the extraction and determination of gold from water samples prior to UV-Vis spectrophotometry. An artificial neural network (ANN) combined with imperialist competitive algorithm (ICA) has been applied to optimize the EME. The effective parameters including pH of acceptor phase, extraction time (t), volume of sample solution (V), stirring rate (S), and voltage (E) were chosen as input variables and the extraction recovery of gold was considered as output variable. The mean of squared error (i.e., 0.0009) and determination coefficient (i.e., 0.9821) were applied to estimate the performance of the ANN model. The limit of detection was 4.5?µg L?1 (S/N?=?3) on the optimized variables. The intra- and interday precisions (%) were found to be 6.7% and 2.6%, respectively. This technique was then applied for analysis of gold from environment water samples. 相似文献
The authors describe a method for functionalization of gold nanoparticles (AuNPs) with the supramolecular host molecule, curcubit[7]uril (CB[7]) which can bind rhodamine B (RhB). The fluorescence of RhB is quenched by the AuNPs via surface energy transfer. On addition of ATP, a dimeric RhB-ATP complex is formed and RhB is pushed out of CB[7]. Hence, fluorescence increases by a factor of 8. This fluorescence recovery effect has been utilized to develop a new detection scheme for ATP. The assay, measured at fluorescence excitation and emission wavelengths of 500 nm and 574 nm respectively, works in the 0.5–10 μM concentration range and has a 100 nM detection limit. The method is not interfered by UTP, GTP, CTP, TTP, ascorbic acid and glutathione.
Graphical abstract Schematic of a method for determination of ATP in the 500 nM to 10 μM concentration range by using fluorescence recovery after surface energy transfer (SET) between rhodamine B (RhB) and gold nanoparticles capped with curcubit[7]uril (CB[7]).
In the present work, catecholase activity is presented. The complexes were prepared by condensation of the organic ligand pyrazolyl L1–L4 and copper(II) ion in situ. The pyrazolyl compounds L1–L4 used in this study are: L1 is (3,5-dimethyl-pyrazol-1-ylmethyl)-(4-methyl-pyridin-2-yl)-pyrazol-1-ylmethyl-amine; L2 is 1-{4-[(3,5-dimethyl-pyrazol-1-ylmethyl)-pyrazol-1-ylmethyl-amino]-phenyl}-ethanone; L3 is 1-{4-[(3,5-dimethyl-pyrazol-1-ylmethyl)-[1,2,4]triazol-1-ylmethyl-amino]-phenyl}-ethanone, and L4 is 2-[(3,5-dimethyl-pyrazol-1-ylmethyl)-[1,2,4]triazol-1-ylmethyl-amino]-6-methyl-pyrimidin-4-ol, and copper ions salts Cu(II) are (Cu(CH3COO)2, CuCl2, Cu(NO3)2 and CuSO4). In order to determine factors influencing the catecholase activity of these complexes, the effect of ligand nature, ligand concentration, nature of solvent and nature of counter anion has been studied. The best activity of catechol oxidation is given by the combination formed by one equivalent of ligand L2 and one equivalent of Cu(CH3COO)2 in methanol solvent which is equal to 9.09 µmol L?1 min?1. The Michaelis–Menten model is applied for the best combination, to obtain the kinetic parameters, and we proposed the mechanism for oxidation reaction of catecholase. 相似文献
The efficient, 12–14 step (LLS) total synthesis of (?)‐halenaquinone has been achieved. Key steps in the synthetic sequence include: (a) proline sulfonamide‐catalyzed, Yamada–Otani reaction to establish the C6 all‐carbon quaternary stereocenter, (b) multiple, novel palladium‐mediated oxidative cyclizations to introduce the furan moiety, and (c) oxidative Bergman cyclization to form the final quinone ring. 相似文献
Using polymer hydrogels and nanocomposites hydrogels still promising materials for many applications. Polyvinyl pyrrolidone (PVP) has been used with various polymers synthetic and natural for different applications. In this study PVP and hydroxyl ethyl methacrylate (HEMA) copolymer hydrogels were prepared by the aid of gamma radiation and the PVP/HEMA nanocomposite hydrogels were obtained by in situ adsorption and reduction method of iron salts and silver nitrates (AgNO3) to form PVP/HEMA-Fe3O4 and PVP/HEMA-Ag nanocomposites. The prepared hydrogels and the formed nanoparticles were studied by various techniques; FTIR, TEM, SEM and also the gel content and swelling behavior were evaluated. The prepared hydrogels and nanocomposites hydrogels were examined as drug delivery systems for Ciprofloxacin HCl as model drug. The PVP/HEMA-Fe3O4 nanocomposite gave the suitable load and release behavior towards Ciprofloxacin HCl. 相似文献
Shewanella oneidensis MR‐1 gains energy by extracellular electron transfer to solid surfaces. They employ c‐type cytochromes in two Mtr transmembrane complexes, forming a multiheme wire for electron transport across the cellular outer membrane. We investigated electron‐ and hole‐transfer mechanisms in the external terminal of the two complexes, MtrC and MtrF. Comparison of computed redox potentials with previous voltammetry experiments in distinct environments (isolated and electrode‐bound conditions of PFV or in vivo) suggests that these systems function in different regimes depending on the environment. Analysis of redox potential shifts in different regimes indicates strong coupling between the hemes via an interplay between direct Coulomb and indirect interactions through local structural reorganization. The latter results in the screening of Coulomb interactions and explains poor correlation of the strength of the heme‐to‐heme interactions with the distance between the hemes. 相似文献
Normetanephrine is a marker for pheochromocytoma, a rare catecholamine-secreting and neuroendocrine tumor, that arises from sympathetic and parasympathetic paraganglia. In this work, a novel carbon/chitosan electrode paste was used for sensitive voltammetric determination of normetanephrine and dopamine in the presence of ascorbic acid and uric acid. The modified electrode has shown an increase in the effective area of up to 68%, well-separated oxidation peaks, and an excellent electrocatalytic activity. The electrochemical response characteristics were investigated by cyclic and differential pulse voltammetry. Interestingly, high sensitivity and selectivity in the linear range of normetanephrine, dopamine, ascorbic acid, and uric acid concentrations were observed. The present method was applied in the urine sample and satisfactory results were obtained showing that this electrode is very suitable in pharmaceutical and clinical preparations. 相似文献
The Fe–Er phase diagram and thermodynamic properties of all its phases are assessed by means of self-consistent analysis. To refine the data on phase equilibria in the Fe–Er system, an investigation is performed in the 10–40 at % range of Er concentrations. The temperature–concentration dependences of the thermodynamic properties of a melt are presented using the model of ideal associated solutions. Thermodynamic parameters of each phase are obtained, and the calculated results are in agreement with available experimental data. The correlation between the thermodynamic properties of liquid Fe–Er alloys and their tendency toward amorphization are studied. It is shown that compositions of amorphous alloys prepared by melt quenching coincide with the ranges of concentration with the predominance of Fe3Er and FeEr2 associative groups that have large negative entropies of formation. 相似文献
In this work, a triblock copolymer polytetrahydrofuran–block-poly(glycidyl azide)–block-polytetrahydrofuran was synthesized through ring-opening polymerization of epichlorohydrin and tetrahydrofuran catalyzed by BF3-diethyl ether at 30°C, and further modification. The structure of the polymer was verified by IR, 1H and 13C NMR spectroscopy. The decomposition and kinetic parameters of the block copolymer such as its activation energy and frequency factor were determined using the differential scanning calorimetry and thermo-gravimetric analysis. The results revealed that the main thermal degradation for the copolymer occurs in the temperature range of 220–250°C. Finally, the effect of polytetrahydrofuran content on the thermal stability and decomposition temperature of the overall copolymer was investigated. 相似文献