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NF-κB is recognized as a redox-sensitive transcription factor and has been implicated in cellular response to oxidative stress. The study was designed to correlate the changes in antioxidant status with the levels of nuclear factor-κB (NF-κB) p65 subunit DNA-binding activity in relation to lymph node involvement, tumor size, and staging in breast carcinoma patients. Case control study comprised of 40 breast carcinoma patients along with 40 age- and sex-matched healthy subjects as controls. Levels of enzymatic/nonenzymatic antioxidants along with the trace elements were measured to study the antioxidant status in the study subjects. Levels of NF-κB p65 subunit DNA-binding activity was estimated by ELISA assay. The levels of enzymatic, nonenzymatic antioxidants, and trace elements were found to be significantly depleted in breast carcinoma patients in comparison to healthy controls suggesting significantly decreased levels of antioxidant activity in the breast carcinoma patients. Also, these results indicate that antioxidant levels decrease progressively with the advancement of stage and subsequent progression of disease. DNA-binding activity of NF-κB p65 subunit was higher in breast cancer patients in comparison to normal healthy controls, and the activity was found to increase with the advancement of disease. Significant correlation was observed between the DNA-binding activity of NF-κB p65 subunit and antioxidant status in the patients. The logistic regression analysis revealed decreased levels of antioxidants and increased level of DNA-binding activity of NF-κB p65 subunit were significantly associated with incidence of breast carcinoma. Depleted antioxidant status and increased level of DNA-binding activity of NF-κB p65 subunit thus point clearly of an association in relation to disease progression, clinical stage, and cytological grade in the pathophysiology of breast carcinoma. [ABSTRACT FROM AUTHOR]

The present paper deals with the kinetics and mechanism of Ru(III)-catalyzed oxidation of paracetamol by chloramine-T (CAT) in aqueous perchloric acid medium at 303 K. The experimental result shows a first order dependence on paracetamol at its low concentrations, but tending towards zeroth order at its higher concentrations. The reactions follow a first order rate dependence with respect to oxidant [CAT] and [Ru(III)]. The reaction showed negative fractional-order dependence on the rate for [H+] and p-toluenesulphonamide. Variation in [Cl−] and ionic strength of the medium did not bring about any significant change on the rate of reaction. The decrease in the reaction rate with decrease in the dielectric constant of the medium was observed in the oxidation of paracetamol. Kinetic and equivalence studies together with product analysis, observed effect of dielectric constant of the medium on the rate of reaction and activation parameters furnished a basis for the formation of a common reaction mechanism for the Ru(III)-catalyzed oxidation of paracetamol by CAT in the acidic medium. [ABSTRACT FROM AUTHOR]

Kinetics of Ruthenium(III) [Ru(III)] chloride catalyzed oxidation of valine (Val) has been studied by N-bromophthalimide (NBP) in the acidic medium at 35 °C. The reaction rate follows first-order and zero-order dependence with respect to [NBP] and [Val]. First-order kinetics was observed for Ru(III) chloride at low range of concentrations and tending towards zero-order at higher concentrations. A negative effect was observed for [H+] and [phthalimide], while a positive effect was observed for [Cl−] on the reaction rate. Hg(OAc)2, ionic strength (I), and dielectric constant ( D) of the medium did not change significantly the reaction rate. The rate constants as a function of temperature (298–318 K) were used to calculate activation parameters of the oxidation of Val by NBP. A plausible mechanism was proposed to explain the results of kinetic studies, reaction stoichiometry and product analysis. [ABSTRACT FROM AUTHOR]

Kinetic studies in homogenous Ru(III) catalyzed oxidation of l-leucine (Leu), by N-bromophthalimide (NBP) in the presence of perchloric acid have been made at 303 K using mercuric acetate as Br ion scavenger. The reaction follows first-order kinetics with respect to [NBP]. In the lower concentration range of Leu and Ru(III) chloride, the reaction follows first-order kinetics but tends to zero at higher concentration. A positive effect of [Cl] was observed in the oxidation of Leu. An increase in the rate of reaction with the decrease in dielectric constant of the medium was observed while negative effect was observed for [H]. The rate of oxidation is unaffected by the change in [phthalimide (NHP)]. Rate of reaction decreased with increase in ionic strength of the medium. The main oxidation products of the reactions were identified as aldehyde, ammonia and CO for the oxidation of Leu. From the effect of temperature (298-318 K) on the reaction rate, various activation parameters have been calculated and on the basis of these parameters, a suitable explanation for the reaction mechanism has been given. [ABSTRACT FROM AUTHOR]