Spectrophotometric studies of molecular complex formation between water-soluble cobalt(II) Schiff base complex and nucleotides in mixed solvent systems

The formation constants for 1:1 molecular complex formation between water-soluble cobalt(II) tetradentate Schiff base complex, disodium[{bis(4-methoxy-5-sulfo-salicylaldehyde)-4,5-dimethyl-o-phenylenediiminato}cobalt(II)], Na2[Co(SO3-4-meosal-4,5-dmophen)], and nucleotides, adenosine-5'-triphosphate (ATP) and cytidine-5'-triphosphate (CTP), in mixed solvent systems of ethanol and water with different volume fractions of ethanol and water have been determined spectrophotometrically at constant ionic strength (I = 0.2 mol dm(-3) NaClO4) and temperature 278 K. Trends in the values of formation constants according to the volume fractions of ethanol and water in ethanol and water mixed solvent systems, suggest that the trend of molecular complex formation increases with increasing the volume fraction of ethanol in mixed solvent systems.     

Interaction of copper(II) complex of compartmental Schiff base ligand N,N'-bis(3-hydroxysalicylidene)ethylenediamine with bovine serum albumin

Circular dichroism (CD) spectroscopy, cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to investigate the interaction between copper(II) complex of compartmental Schiff base ligand (L), N,N'-bis(3-hydroxysalicylidene)ethylenediamine, and bovine serum albumin (BSA) in 0.1 mol dm(-3) phosphate buffer solution adjusted to physiological pH 7.0 containing 20% (w/w) dimethylsulfoxide at room temperature. CD spectra show that the interaction of the copper(II) complex with BSA leads to changes in the alpha-helical content of BSA and therefore changes in secondary structure of the protein with the slight red shift (2 nm) in CD spectra. From the voltammetric data, i.e. changes in limiting current with addition of BSA, the binding constant (K) of the interaction of copper(II) complex with BSA was found to be 1.96 x 10(4)dm(3)mol(-1). From the shifts in potential with the addition of BSA, the equilibrium constant ratio (K(2)/K(1)) for the binding of the oxidized Cu(II)L (K(1)) and reduced Cu(I)L (K(2)) species to BSA was found to be 3.77, which shows that the reduced form Cu(I)L is bound more strongly to BSA than the oxidized form Cu(II)L.     

Influence of calcination temperature on structural and magnetic properties of nanocomposites formed by Co-ferrite dispersed in sol-gel silica matrix using tetrakis(2-hydroxyethyl) orthosilicate as precursor

Effects of calcination temperatures varying from 400 to 1000°C on structural and magnetic properties of nanocomposites formed by Co-ferrite dispersed in the sol-gel silica matrix using tetrakis(2-hydroxyethyl) orthosilicate (THEOS) as water-soluble silica precursor have been investigated. Studies carried out using XRD, FT-IR, TEM, STA (TG-DTG-DTA) and VSM techniques. Results indicated that magnetic properties of samples such as superparamagnetism and ferromagnetism showed great dependence on the variation of the crystallinity and particle size caused by the calcination temperature. The crystallization, saturation magnetization M_s and remenant magnetization M_r increased as the calcination temperature increased. But the variation of coercivity H_c was not in accordance with that of M_s and M_r, indicating that H_c is not determined only by the crystallinity and size of CoFe₂O₄ nanoparticles. TEM images showed spherical nanoparticles dispersed in the silica network with sizes of 10-30 nm. Results showed that the well-established silica network provided nucleation locations for CoFe₂O₄ nanoparticles to confinement the coarsening and aggregation of nanoparticles. THEOS as silica matrix network provides an ideal nucleation environment to disperse CoFe₂O₄ nanoparticles and thus to confine them to aggregate and coarsen. By using THEOS as water-soluble silica precursor over the currently used TEOS and TMOS, the organic solvents are not needed owing to the complete solubility of THEOS in water. Synthesized nanocomposites with adjustable particle sizes and controllable magnetic properties make the applicability of Co-ferrite even more versatile.     

Charge transfer complexes of adenosine-5'-monophosphate and cytidine-5'-monophosphate with water-soluble cobalt(II) Schiff base complexes in aqueous solution

Water-soluble cobalt(II) tetradentate Schiff base complexes have been shown to form charge transfer (CT) complexes with a series of nucleoside monophosphates including adenosine-5'-monophosphate (AMP) and cytidine-5'-monophosphate (CMP). The investigated water-soluble cobalt(II) Schiff base complexes are (i) disodium[{bis(5-sulfo-salicylaldehyde)-o-phenylenediiminato}cobalt(II)], Na2[Co(SO3-salophen)] (1); (ii) disodium[{bis(5-sulfo-salicylaldehyde)-4,5-dimethyl-o-phenylenediiminato}cobalt(II)], Na2[Co(SO3-sal-4,5-dmophen)] (2) and (iii) disodium[{bis(4-methoxy-5-sulfo-salicylaldehyde)-4,5-dimethyl-o-phenylenediiminato}cobalt(II)], Na(2)[Co(SO3-4-meosal-4,5-dmophen)] (3). The formation constant and thermodynamic parameters for charge transfer complex formation of water-soluble cobalt(II) Schiff base complexes with nucleoside monophosphates were determined spectrophotometrically in aqueous solution at constant ionic strength (I = 0.2 mol dm(-3) KNO3) under physiological condition (pH 7.0) and at various temperatures between 288 and 308 K. The stoichiometry has been found to be 1:1 (water-soluble cobalt(II) Schiff base complex: nucleoside monophosphate) in each case. Our spectroscopic and thermodynamic results show that the interaction of water-soluble cobalt(II) Schiff base complexes with the investigated nucleoside monophosphates occurs mainly through the phosphate group. The trend of the interaction according to the cobalt(II) Schiff base complexes due to electronic and steric factors is as follows: Na2[Co(SO3-salophen)] > Na2[Co(SO3-sal-4,5-dmophen)] > Na2[Co(SO3-4-meosal-4,5-dmophen)]. Also the trend of the interaction of a given cobalt(II) Schiff base complex according to the nucleoside monophosphate is as follows: CMP > AMP.     

Ultrafast electrokinetics

The influence of a high electric field applied on both fluid flow and particle velocities is quantified at large Peclet numbers. The experiments involved simultaneous particle image velocimetry and flow rate measurements. These are conducted in polydimethylsiloxane channels with spherical nonconducting polystyrene particles and DI water as the background flow. The high electric field tests produced up to three orders of magnitude higher electrokinetic velocities than any previous reports. The maximum electroosmotic velocity and electrophoretic velocity measured were 3.55 and 2.3 m/s. Electrophoretic velocities are measured over the range of 100 V/cm < E < 250 000 V/cm. The results are separated according to the different nonlinear theoretical models, including low and high Peclet numbers, and weak and strong concentration polarization. They show good agreement with the models. Such fast velocities could be used for flow separation, mixing, transport, control, and manipulation of suspended particles as well as microthrust generation among other applications.     

Study on elastic modulus of crosslinked polyurethane/organoclay nanocomposites

In this paper, two polyurethane/clay nanocomposite systems with crosslinked structure were synthesized via in situ polymerization of a polyether‐ as well as a polyester‐based prepolymer with methylene‐bis‐ortho‐chloroanilline (MOCA). Two types of modified clays with different organic modifiers were used in order to see the effect of compatibility between polymer matrix and clays on elastic modulus of nanocomposites. The morphology and the dispersion of clay layers in polyurethanes have been characterized by X‐ray diffraction (XRD) and microscopic techniques. The changes of elastic modulus of nanocomposites with clay content were examined and compared with those predicted by some conventional composite models. The results showed a reasonable fitting of experimental and theoretical values only at very low clay contents. As the clay content exceeds 1.5 wt% in this system, a reduction in elastic modulus was experimentally observed due to insufficient dispersion degree of silicate layers throughout the crosslinked matrix. This behavior was not predicted with the conventional composite theories. A new model on the basis of Wu model was then developed in order to predict the reduction of elastic modulus at various clay contents in crosslinked PU matrix. This model fitted reasonably the experimental results. Copyright © 2010 John Wiley & Sons, Ltd.     

Crisp and soft multivariate methods visualize individual cell nuclei in Raman images of liver tissue sections

Raman and infrared spectroscopy have been recognized to be promising tools in clinical diagnostics because they provide molecular contrast without external stains. Here, vertex component analysis (VCA) was applied to Raman and Fourier transform infrared (FTIR) images of liver tissue sections and the results were compared with K-means cluster analysis, fuzzy C-means cluster analysis and principal component analysis. The main components of VCA from three Raman images were assigned to the central vein, periportal vein, cell nuclei, liver parenchyma and bile duct. After resonant Mie scattering correction, VCA of FTIR images identified veins, liver parenchyma, cracks, but no cell nuclei. The advantages of VCA in the context of tissue characterization by vibrational spectroscopic imaging are that the tissue architecture is visualized and the spectral information is reconstructed. Composite images were constructed that revealed a high molecular contrast and that can be interpreted in a similar way like hematoxylin and eosin stained tissue sections.