Sharif Digital Repository

In the present research, a new tweezer T bearing azobenzene linker 1 was prepared, characterized by applying FT-IR spectroscopy, fluorescence spectroscopy, UV–visible spectroscopy, and elemental analysis 1H and 13C{1H} NMR. T crystals were obtained by reaction of 1 with ZnTPP in CHCl3/acetone. Under irradiation with a mercury lamp to achieve the trans-to-cis isomerization, a dramatic color change from violet to green in chloroform was observed. The X-ray crystallography of T revealed an observable macroring deformation of the ZnTPP for the trans isomer. We observed a deviation of 0.11 Å from planarity for the least-squares plane of ZnTPP owing to the axial coordination by the pyridine... 

Under experimental conditions in which the self-association of the adenine phosphates (AP), that is, of adenosine 5′-monophosphate (AMP2-) and adenosine 5′-diphosphate (ADP3-), is negligible, potentiometric pH titrations were carried out to determine the stabilities of the M(H;AP) and M(AP) complexes where M2+=Mg2+, Ca2+, Sr2+, Ba2+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+, or Cd2+ (25°C; I = 0.1m, NaNO3). It is concluded that in the M(H;AMP)+ species M2+ is bound at the adenine moiety and in the M(H;ADP) complexes at the diphosphate unit; however, the proton resides in both types of monoprotonated complexes at the phosphate residue. The stabilities of nearly all the M(AMP) and M(ADP)- complexes are... 

The isomerization of D-glucose to D-fructose using the immobilized glucose isomerase, as a typical model system of solid-liquid enzyme reactions has been carried out in a novel type of two-impinging-jets reactor (TIJR), which is characterized by a rotating inner cylinder in a stationary one. Because of the impinging process, turbulence, and complex trajectory of the solid particles within the reactor, the fractional conversion of glucose obtained in the TIJR increased dramatically compared to that obtained by conventional reaction systems. A compartment model was considered to describe the pattern of flow [residence time distribution (RTD) of solid particles] within the TIJR. Considering... 

We present the kinetic parameters and equilibrium constant of the enzymatic glucose-fructose isomerization reaction with an immobilized glucose isomerase (IGI), Sweetzyme IT, using a batch stirred-tank reactor following the procedure developed by Dehkordi et al. (AIChE J. 2008, 54, 1333). The model predictions were compared with the experimental data and fair agreements were found. The influence of temperature on the equilibrium constant and kinetic parameters of glucose to fructose isomerization reaction was investigated. In addition, the frequency factors and the activation energies were determined by using Arrhenius-like expressions. Furthermore, correlations were found for the maximum... 

A simple and green route to synthesis of (4 or 5)-aryl-2-aryloyl-(1H)-imidazoles is described. Two isomers can tautomerize to each other by the heat absorption. The tauto-isomerization process was studied by NMR technique. Acidity and stability of products were studied using B3LYP method. © 2009 Elsevier Ltd. All rights reserved  

Calcineurin is an essential calcium-activated serine/threonine phosphatase. The six NMR-observable methionine methyl groups in the catalytic domain of human calcineurin Aα (CNA) were assigned and used as reporters of the presence of potential cis-trans isomers in solution. Proline 84 is found in the cis conformation in most calcineurin X-ray structures, and proline 309, which is part of a highly conserved motif in phosphoprotein phosphatases, was modeled with a cis peptide bond in one of the two molecules present in the asymmetric unit of CNA. We mutated each of the two prolines to alanine to force the trans conformation. Solution NMR shows that the P84A CNA mutant exists in two forms,... 

In this report, the synthesis of a new bi-macrocycle tweezer linked through an azobenzene moiety, L was undertaken. The characterization of the tweezer was accomplished by employing IR, 1H and 13C NMR, UV–vis, fluorescence spectroscopy and CHN microanalysis while the UV–visible spectroscopy illustrated a trans ⇆ cis photo-isomerization for L. According to our preliminary fluorescence observations, a metal-ion chemosensing behavior was established for trans-L isomer towards Cr(III) ion among the library metal ions. The quenching of the respective trans ⇆ cis isomerization in the presence of Cr(III) ion suggested the preference of a strong interaction between Cr(III) ion with L, leading to... 

In this paper, the performance of immobilized packed bed glucose isomerase enzyme was mathematically modeled. A modified Michaelis-Menten type relation was used to describe the enzyme kinetics. Mass transfer inside the biocatalyst particle and through the bed column was analyzed simultaneously. Using measured data, physicochemical properties including diffusivity, viscosity and density of sugar solutions were correlated with its concentrations and were used to provide precision in solving the set of model equations. Model equations were solved using the Runge-Kutta and Gauss-Seidel algorithms and finite difference numerical method in MATLAB environment. Model output was used to demonstrate... 

N,N′,N″-triethylenethiophosphoramide (Thiotepa) and its oxo analogue (Tepa) as the major metabolite are trifunctional alkylating agents with a broad spectrum of antitumor activity. In vivo and vitro studies show alkylation of DNA by Thiotepa and Tepa can follow two pathways, but it remains unclear which pathway represents the precise mechanism of action. In pathway 1, these agents are capable of forming cross-links with DNA molecules via two different mechanisms. In the first mechanism, the ring opening reaction is initiated by protonating the aziridine, which then becomes the primary target of nucleophilic attack by the N7-Guanine. The second one is a direct nucleophilic ring opening of... 

An unusual heterobimetallic bis(triphenylphosphane)(NO2)AgI–CoIII(dimethyl-glyoximate)(NO2) coordination compound with both bridging and terminal –NO2 (nitro) coordination modes has been isolated and characterized from the reaction of [CoCl(DMGH)2(PPh3)] (DMGH2 is dimethylglyoxime or N,N′-di-hydroxybutane-2,3-diimine) with excess AgNO2. In the title compound, namely bis(dimethylglyoximato-1κ2O,O′)(μ-nitro-1κN:2κ2O,O′)(nitro-1κN)bis(triphenyl-phosphane-2κP)cobalt(III)silver(I), [AgCo(C4H7N2O2)2(NO2)2(C18H15P)2], one of the ambidentate –NO2 ligands, in a bridging mode, chelates the AgI atom in an isobidentate κ2O,O′-manner and its N atom is coordinated to the CoIII atom. The other –NO2 ligand... 

The interaction of n-dodecyl trimethylammonium bromide (DTAB) with oxyhemoglobin A and oxyhemoglobin S is investigated using UV-visible absorption spectra and chemometric resolution techniques. Oxyhemoglobins (A and S) induced to partial oxidized form (ferrihemoglobin) by DTAB and finally transform to fully oxidized hemichrome. Hemichrome mole fractions of HbS are more than HbA because of more hydrophobic interaction of DTAB-HbS in second set of binding site relative to DTAB-HbA. The visible spectra between 500 and 650 nm are used for identifying the present components in solution because each species of hemoglobin has a specific spectrum in this region. The number of components and mole...