Remarkable enhancement in photocytotoxicity and hydrolytic stability of curcumin on binding to an oxovanadium(IV) moiety

Oxovanadium(IV) complexes of polypyridyl and curcumin-based ligands, viz. VO(cur)(L)Cl] (1, 2) and VO(scur)(L)Cl] (3, 4), where L is 1,10-phenanthroline (phen in 1 and 3), dipyrido3,2-a:2',3'-c]phenazine (dppz in 2 and 4), Hcur is curcumin and Hscur is diglucosylcurcumin, were synthesized and characterized and their cellular uptake, photocytotoxicity, intracellular localization, DNA binding, and DNA photo-cleavage activity studied. Complex VO(cur)(phen)Cl] (1) has (VN2O3Cl)-N-IV distorted octahedral geometry as evidenced from its crystal structure. The sugar appended complexes show significantly higher uptake into the cancer cells compared to their normal analogues. The complexes are remarkably photocytotoxic in visible light (400-700 nm) giving an IC50 value of <5 mu M in HeLa, HaCaT and MCF-7 cells with no significant dark toxicity. The green emission of the complexes was used for cellular imaging. Predominant cytosolic localization of the complexes 1-4 to a lesser extent into the nucleus was evidenced from confocal imaging. The complexes as strong binders of calf thymus DNA displayed photocleavage of supercoiled pUC19 DNA in red light by generating (OH)-O-center dot radicals as the ROS. The cell death is via an apoptotic pathway involving the ROS. Binding to the VO2+ moiety has resulted in stability against any hydrolytic degradation of curcumin along with an enhancement of its photocytotoxicity.

Conformational Stability and Intramolecular Hydrogen Bonding in 1,2-Ethanediol and 1,4-Butanediol

The gas-phase infrared spectra of 1,2-ED and 1,4-BD have been, recorded at three different temperatures using a multipass gas cell of 6 m optical path length. DFT calculation has also been carried out using 6-311++G** and aug-cc-pVDZ basis sets to look for the existence of intramolecular hydrogen bonding, in them from the red shift and infrared absorption intensity enhancement of the bonded O-H band compared to that of the free O-H hand. Equilibrium population analysis With 10 conformers of 1,2-ED and 1,4-BD at experimental temperatures were-carried out for the reconstruction of the Observed vibrational spectra at that temperature,using standard statistical relationships. The most abundant conformer at experimental temperatures, was identified. In 1,2-ED a red shift of 45 cm(-1) in the intramolecularly interacting O-H stretching vibrational band position and no significant intensity enhancement compared to that of-the free O-H have been observed. On the contrary, in one of the hydrogen bonded conformers of 1,4-BD, a 124 cm(-1) red shift in the O-H stretching frequency and 8.5 times-intensity enhancement for the ``bonded'' O-H compared to that of the ``free'' O-H is seen. On the basis of this comparative study, we have concluded that strong intramolecular hydrogen bonding exists in 1,4-BD. But there appears, to be weak intramolecular hydrogen bonding in 1,2-ED at temperatures of 303, 313, and 323 Km the gas phase We have found that most stable hydrogen-bonded conformers of 1,4-BD are less populated than some of the non-hydrogen-bonded conformers. Even for the 1,4-BD, the relative population of the g'GG'Gt conformer, which has a strong intramolecular,hydrogen bond, is less than what is predicted. Perhaps the intramolecular hydrogen bond plays a less Significant role in the relative stability,of the various Conformers than what has been predicted from calculations and prevails in the literature.

Influences of Hydration Force and Elastic Strain Energy on the Stability of Solid Film in a Very Thin Solid-on-Liquid Structure

Since hydration forces become very strong at short range and are particularly important for determining the magnitude of the adhesion between two surfaces or interaction energy, the influences of the hydration force and elastic strain energy due to hydration-induced layering of liquid molecules close to a solid film surface on the stability of a solid film in a solid-on-liquid (SOL) nanostructure are studied in this paper. The liquid of this thin SOL structure is a kind of water solution. Since the surface forces play an important role in the structure, the total free energy change of SOL structures consists of the changes in the bulk elastic energy within the solid film, the surface energy at the solid-liquid interface and the solid-air interface, and highly nonlinear volumetric component associated with interfacial forces. The critical wavelength of one-dimensional undulation, the critical thickness of the solid film, and the critical thickness of the liquid layer are studied, and the stability regions of the solid film have been determined. Emphasis is placed on calculation of critical values, which are the basis of analyzing the stability of the very thin solid film.

Perturbation of the stability of amyloid fibrils through alteration of electrostatic interactions.

The self-assembly of proteins and peptides into polymeric amyloid fibrils is a process that has important implications ranging from the understanding of protein misfolding disorders to the discovery of novel nanobiomaterials. In this study, we probe the stability of fibrils prepared at pH 2.0 and composed of the protein insulin by manipulating electrostatic interactions within the fibril architecture. We demonstrate that strong electrostatic repulsion is sufficient to disrupt the hydrogen-bonded, cross-β network that links insulin molecules and ultimately results in fibril dissociation. The extent of this dissociation correlates well with predictions for colloidal models considering the net global charge of the polypeptide chain, although the kinetics of the process is regulated by the charge state of a single amino acid. We found the fibrils to be maximally stable under their formation conditions. Partial disruption of the cross-β network under conditions where the fibrils remain intact leads to a reduction in their stability. Together, these results support the contention that a major determinant of amyloid stability stems from the interactions in the structured core, and show how the control of electrostatic interactions can be used to characterize the factors that modulate fibril stability.

Sidewall flow stability in the MHD channel flows

The velocity distribution between two sidewalls is; M-shaped for the MHD channel flows with rectangular cross section and thin conducting walls in a strong transverse magnetic field. Assume that the dimensionless numbers R(m) much less than 1, M, N much greater than 1, and sigma

Effects of wall temperature on boundary layer stability over a blunt cone at Mach 7.99

Effects of wall temperature on stabilities of hypersonic boundary layer over a 7-degree half-cone-angle blunt cone are studied by using both direct numerical simulation (DNS) and linear stability theory (LST) analysis. Four isothermal wall cases with Tw/T0= 0.5, 0.7, 0.8 and 0.9, as well as an adiabatic wall case are considered. Results of both DNS and LST indicate that wall temperature has significant effects on the growth of disturbance waves. Cooling the surface accelerates unstable Mack II mode waves and decelerates the first mode (Tollmien–Schlichting mode) waves. LST results show that growth rate of the most unstable Mack II mode waves for the cases of cold wall Tw/T0=0.5 and 0.7 are about 45% and 25% larger than that for the adiabatic wall, respectively. Numerical results show that surface cooling modifies the profiles of rdut/dyn and temperature in the boundary layers, and thus changes the stability haracteristic of the boundary layers, and then effects on the growth of unstable waves. The results of DNS indicate that the disturbances with the frequency range from about 119.4 to 179.1 kHz, including the most unstable Mack modes, produce strong mode competition in the downstream region from about 11 to 100 nose radii. And adiabatic wall enhances the amplitudes of disturbance according to the results of DNS, although the LST indicates that the growth rate of the disturbance of cold wall is larger. That because the growth of the disturbance does not only depend on the development of the second unstable mode.

Efficiency vs. Stability in a Mixed Network Formation Model

Documentos de Trabajo

The intensity distribution and thermal stability of InnoSlab laser

Partially end-pumped slab laser is an innovative solid state laser, namely InnoSlab. Combining the hybrid resonator with partially end-pumping, the output power can be scaled with high beam quality. In this paper, the output intensity distributions are simulated by coordinate transformation fast Fourier transform (FFT) algorithm, comparing the thermal lens influence. As the simulated curves showed, the output mode is still good when the thermal lens effect is strong, indicating the good thermal stability of InnoSlab laser. Such a new kind of laser can be designed and optimized on the base of this simulation.

Effect of alkali and alkaline earth fluoride introduction on thermal stability and structure of fluorophosphate glasses

The thermal stability and structure of RF-RF2-AIF(3)-Al(PO3)(3) fluorophosphate glasses were investigated. Analyses of infrared absorbance spectra and Raman spectra reveal that with increasing number of alkali and alkaline earth fluoride components, the sum of P-O-P bond and O-P-O bond increases and glass network is strengthened. Consequently, the inhibition to nucleation and crystallization processes is improved, which is proved by the increment of thermal stability factors AT and S determined by differential scanning calorimetry. In addition, it was found that LiF has poor ability to form glass in univalent alkali fluorides and MgF2 has comparative strong ability to form glass in bivalent alkaline earth fluorides. (c) 2006 Published by Elsevier B.V.

The local and global stability of confined planar wakes at intermediate Reynolds number

At high Reynolds numbers, wake flows become more globally unstable when they are confined within a duct or between two flat plates. At Reynolds numbers around 100, however, global analyses suggest that such flows become more stable when confined, while local analyses suggest that they become more unstable. The aim of this paper is to resolve this apparent contradiction by examining a set of obstacle-free wakes. In this theoretical and numerical study, we combine global and local stability analyses of planar wake flows at $\mathit{Re}= 100$ to determine the effect of confinement. We find that confinement acts in three ways: it modifies the length of the recirculation zone if one exists, it brings the boundary layers closer to the shear layers, and it can make the flow more locally absolutely unstable. Depending on the flow parameters, these effects work with or against each other to destabilize or stabilize the flow. In wake flows at $\mathit{Re}= 100$ with free-slip boundaries, flows are most globally unstable when the outer flows are 50 % wider than the half-width of the inner flow because the first and third effects work together. In wake flows at $\mathit{Re}= 100$ with no-slip boundaries, confinement has little overall effect when the flows are weakly confined because the first two effects work against the third. Confinement has a strong stabilizing effect, however, when the flows are strongly confined because all three effects work together. By combining local and global analyses, we have been able to isolate these three effects and resolve the apparent contradictions in previous work.

The influence of stoichiometry on the structural stability and on the optical emission of erbium silicate thin films

We report the effects of thermal annealing performed in N2 or O2 ambient at 1200 °C on the structural and optical properties of Er silicate films having different compositions (Er2Si O 5,Er2 Si2 O7, and their mixture). We demonstrate that the chemical composition of the stoichiometric films is preserved after the thermal treatments. All different crystalline structures formed after the thermal annealing are identified. Thermal treatments in O 2 lead to a strong enhancement of the photoluminescence intensity, owing to the efficient reduction of defect density. In particular the highest optical efficiency is associated to Er ions in the α phase of Er 2 Si2 O7. © 2008 American Institute of Physics.

STATISTICAL THERMODYNAMICS OF POLYDISPERSE POLYMER BLENDS WITH STRONG INTERACTION

A statistical thermodynamics theory of polydisperse polymer mixtures with strong interaction between dissimilar components based on a lattice fluid model is formulated. Expressions for the free energy, equation of state, phase stability and spinodal for a polydisperse, binary polymer mixture with strong interaction are derived.

Effect of variations in acid properties of HZSM-5 on the coking behavior and reaction stability in butene aromatization

In order to investigate the effect of acid properties on the coke behavior and stability of butene aromatization, we prepared the AHZSM-5 samples with various acid properties by the methods of hydrothernial treatment and K addition. The reaction of butene aromatization was carried out at 350 degrees C and 0.5 MPa in a continuous flow fixed bed. The characterization of the fresh/coked catalysts with NH3-TPD, N-2 adsorption-desorption measurement, and TG techniques has shown that a large amount of acid sites (high acid density) of the AHZMS-5 catalyst can cause a large quantity of coke deposit and serious channel blockage, and so result in a rapid loss of aromatization activity. On the contrary, after a great reduction in strong acid sites of AHZSM-5 catalyst resulting from some K-modification, the presence of only many weak acid sites also could not lessen the formation of coke nor improve the reaction stability of butene aromatization. Interestingly, the simultaneous reduction in the strong and weak acid sites to a desirable level by hydrothermal treating the AHZSM-5 catalyst at a proper temperature can effectively suppress the coke formation and channel blockage, and thus improve its olefin aromatization stability. (c) 2005 Elsevier B.V. All rights reserved.

An improved result of exponential stability of stochastic semilinear evolution equations

Sufficient conditions for the exponential stability of a class ofnonlinear, non-autonomous stochastic differential equations in infinitedimensions are studied. The analysis consists of introducing a suitableapproximating solution systems and using a limiting argument to pass onstability of strong solutions to mild ones. As a consequence, the classicalcriteriaof stability in A. Ichikawa [8] are improved and extended to cover a class ofnon-autonomous stochastic evolution equations.Two examples are investigated to illustrate our theory.

Ergodicity and stability of generalised Markov branching processes with resurrection

This paper concentrates on investigating ergodicity and stability for generalised Markov branching processes with resurrection. Easy checking criteria including several clear-cut corollaries are established for ordinary and strong ergodicity of such processes. The equilibrium distribution is given in an elegant closed form for the ergodic case. The probabilistic interpretation of the results is clear and thus explained.