NMR and EPR structural delineation of copper(II) complexes formed by kanamycin A in water

The complexes formed by kanamycin A at three different pH values (5.5, 7.4 and 12.0) were investigated by NMR and EPR spectroscopy. Paramagnetic relaxation contributions to proton relaxation rates were measured using a combination of the TOCSY sequence with the inversion recovery experiment in order to gain signal resolution in the bulk region. Measured contributions were converted into distances and used for structural determination by restrained simulated annealing where all possible chair and boat conformations of the rings were taken into account. The interaction of the Cu(II) ion with the nitrogen of the C ring is apparent at all pH values. At higher pH also the amino group of ring A starts to be involved in the metal coordination sphere. This is accompanied by a switch in conformation of ring C. Structures are consistent with the involvement in the coordination sphere either of the 2' or 4' hydroxyl oxygens at pH 5.5 and the 5 and the 6' hydroxyl oxygens (or the ring oxygen) at pH 12.0.     

Electrochemical study of quercetin-DNA interactions: part I. Analysis in incubated solutions

The present study aims to investigate the quercetin-deoxyribonucleic acid (DNA) interaction occurring in bulk solution either electrochemically using differential pulse voltammetry or spectrophotometrically, in order to explain the possible DNA-damaging activity of quercetin. A very weak interaction between quercetin and DNA in solution was found to take place. However, since extensive quercetin-induced DNA damage via reaction with Cu(II) has been reported, an electrochemical study of the DNA-Cu(II)-quercetin system in solution was undertaken. The product of DNA interaction with quercetin-Cu(II) complex was observed. Damages to DNA were electrochemically recognized via the increasing of the anodic peaks corresponding to the oxidation of guanosine and adenosine bases and spectrophotometrically via increasing of the 260 nm adsorption band. It was also observed that dsDNA damage produced by the quercetin-Cu(II) complex occurred with time. Control experiments with different mixtures of Cu(II), quercetin, ssDNA, dsDNA or poly[A] were carried out in order to establish a possible mechanism of interaction between DNA and quercetin via Cu(II).     

Monolithic columns with a gradient of functionalities prepared via photoinitiated grafting for separations using capillary electrochromatography

Stationary phases for capillary electrochromatography with a longitudinal gradient of functionalities have been prepared via photoinitiated grafting of polymer chains onto the pore surface of a porous polymer monolith. In order to achieve the desired retention and electroosmotic flow, the hydrophobic poly(butyl methacrylate-co-ethylene dimethacrylate) monolith with optimized porous properties was grafted with a layer of ionizable polymer, poly(2-acrylamido-2-methyl-1-propanesulfonic acid). A moving shutter and a neutral density filter were used to control the dose of UV light received at different locations along the monolith in order to create the longitudinal gradient of functionalities. Formation of the desired gradients was confirmed using electron probe microanalysis of different locations along the column. The preparation technique significantly affects performance in the CEC mode as demonstrated on the separations of a model mixture using columns both with homogeneous distribution of grafts and with a gradient of functionality. Columns grafted with the gradient of functionalities were found superior to those functionalized uniformly. A comparison of the performance of the gradient column with another containing evenly distributed functionalities showed the performance benefits of the "gradient" column.     

Development of a capillary zone electrophoretic method to determine six antidepressants in their pharmaceutical preparations. Experimental design for evaluating the ruggedness of method

A capillary zone electrophoresis method is proposed for the separation of six of the antidepressants most used for the treatment of mental illness (clomipramine, paroxetine, fluoxetine, citalopram, fluvoxamine, and trazodone). Optimum conditions for their separation were investigated. A background electrolyte solution consisting of 50 mM phosphate buffer adjusted to pH 2.0, hydrodynamic injection, and 25 kV as separation voltage were used. Relative standard deviations (RSD) were <0.38% and <2.93% for migration time and corrected peak area (n = 24), respectively. Detection limits obtained for the six antidepressants ranged from 0.03 to 0.11 mg L(-1). Stability of the solutions, linear concentration range, accuracy, and precision were examined during validation of the method. A ruggedness test of this method was performed using the fractional factorial model of Plackett-Burman, requiring in our case design of a matrix of 15 experiments, in which the influence of seven factors at three different levels was tested on different electrophoretic results: efficiency; resolution; and corrected peak area. Statistical evaluation of electrophoretic results was achieved by Youden and Steiner's method. The described method is rapid, sensitive, and rugged and it was tested for the pharmaceutical formulation analysis, giving recoveries between 95.6 and 99.1% with respect to the nominal content.     

On a Question of Haskell P. Rosenthal Concerning a Characterization of c0 and lp

The following property of a normalized basis in a Banach spaceis considered: any normalized block sequence of the basis hasa subsequence equivalent to the basis. Under uniformity or othernatural assumptions, a basis with this property is equivalentto the unit vector basis of c₀ or l_p. An analogous problem concerningspreading models is also addressed. 2000 Mathematics SubjectClassification 46B20 (primary), 46B15 (secondary).     

On the Almost Intersections of Transient Brownian Motions

Let {B ₁ ^d (t)} and {B ^d ₂(t)} be independent Brownian motions in R ^d starting from 0 and nx respectively, and let w ^d _i (a,b) ={xR ^d : B ^d _i (t)=x for some t(a,b)}, i=1,2. Asymptotic expressions as n for the probability of dist(w ^d ₁(n ² t ₁, n ² t ₂), w ₂ ^d (0,n ² t ₃))1 with d4, respectively for the probability of dist(w ₁ ⁴(n ² t ₁,n ² t ₂),w ₂ ⁴(0,n ² t ₃))1 are obtained. As an application, an improvement of a result due to M. Aizenman concerning the intersections of Wiener sausages in R ⁴ is presented.     

Domains of Holomorphy of Generating Functions of Pólya Frequency Sequences of Finite Order*

A domain is the domain of holomorphy of the generating function of a Pólya frequency sequence of order r if and only if it satisfies the following conditions: (A) G contains the point z = 0, (B) G is symmetric with respect to the real axis, (C) T = dist(0,G)G.     

Investigation of metabolic changes in irradiated rat brain tissue by means of 1H NMR in vitro relaxation study

The effect of irradiation on concentrations and relaxation behaviour of brain metabolites was studied by means of high-resolution 1H NMR in vitro. The studies were performed on rat brains irradiated with the doses of 20 Gy applied in fractions of 2 Gy. Standard procedures were used to obtain HClO4 extracts of rat brains. The 1H NMR studies of the extracts solutions in D2O were performed using a Varian Inova-300 NMR spectrometer. The integral intensities of the metabolite signals were found to change during the irradiation cycle and after it. These changes are accompanied by the variations in the T1 relaxation times. N-acetylaspartate, glycerophosphocholine, phosphocholine, choline, creatine and phosphocreatine, myoinositol and taurine were analysed as potential markers of irradiation injury.     

Soliton-based Y-branch in photorefractive crystals induced through dispersion-shifted optical fiber

We experimentally demonstrate for what is believed to be the first time that a dispersion-shifted fiber can be used to electro-optically induce a soliton Y-branch structure in a photorefractive centrosymmetric paraelectric crystal (potassium lithium tantalate niobate). The application of a nonstationary external bias field enables us to stabilize the spatially partially coherent behavior of the optical beam at the fiber output. Furthermore, we show the switching capabilities of this soliton-based device in the optical communication field guiding a probe beam at a nonphotorefractive wavelength (1557 nm).