Thermal investigations on γ-radiation processed natural medicinal products (Ashwagandha,Amla and Hartiki)

DSC and TG studies were carried out on -radiation processed Indian natural products of medicinal importance, namely Ashwagandha (Withania Somnifera), Amla (Emblica Officinalis) and Hartiki (Terminalia chebula). DSC thermoanalytical curves were recorded from 35 to 400°C in air and nitrogen atmosphere. Similarly, TG thermoanalytical curves were taken from 35 to 700°C in air and nitrogen atmosphere. Irradiated products gave significantly different thermoanalytical profiles in comparison to non-irradiated samples. The differences were observed above decomposition temperature of 200°C and were non-linear with respect to radiation dose. Partial oxidation of the products during irradiation in air could be responsible for the observed differences.     

Metallophthalocyanines with rod-shaped substituents

4-(4′-Dioctylaminocarbonylbiphenyloxy) phthalonitrile was synthesized from 4-(4′-carboxybiphenyloxy)phthalonitrile and dioctylamine in the presence of Et₃N. Metallophthalocyanines (Zn, Co and Cu) substituted with four dioctylaminocarbonyl biphenyloxy groups on the peripheral positions were prepared from 4-(4′-dioctylaminocarbonylbiphenyloxy)phthalonitrile and the corresponding divalent metal salts (Zn(CH₃COO)₂, CoCl₂ and CuCl₂). The new phthalocyanines are soluble in common organic solvents. These compounds were characterised by ¹H-NMR, ¹³C-NMR, FT-IR, UV-Vis and mass spectroscopies.     

New liquid chromatographic-chemometric approach for the determination of sunset yellow and tartrazine in commercial preparation

A new liquid chromatographic (LC)-chemometric approach was developed for the determination of sunset yellow (SUN) and tartrazine (TAR) in commercial preparations. This approach uses LC and chemometric calibration methods, i.e., classical least-squares (CLS), principal component regression (PCR), and partial-least squares (PLS), simultaneously. The combined LC-chemometric approaches, denoted as LC-CLS, LC-PCR, and LC-PLS, are based on photodiode array (PDA) detection at multiple wavelengths. Optimum chromatographic separation of SUN and TAR with allura red as the internal standard (IS) was obtained by using a Waters Symmetry C18 column, 5 microm, 4.6 x 250 mm, and 0.2 M acetate buffer (pH 5)-acetonitrile-methano-bidistilled water (55 + 20 + 15 + 10, v/v) as the mobile phase at a flow rate of 1.9 mL/min. The LC data sets consisting of the ratios of analyte peak areas to the IS peak area were obtained by using PDA detection at 5 wavelengths (465, 470, 475, 480, and 485 nm). LC-chemometric calibrations for SUN and TAR were separately constructed by using the relationship between the peak-area ratio and the training sets for each colorant. LC-chemometric approaches were tested for different synthetic mixtures containing SUN and TAR in the presence of the IS. These LC-chemometric calibrations were applied to a commercial preparation of the 2 colorants. The experimental results of the LC-chemometric approaches were compared with those obtained by a developed classical LC method using single-wavelength detection.     

Behavior of rifampicin in association with<Emphasis Type="Italic"> β</Emphasis>-cyclodextrin in aqueous media: a spectroscopic and conductometric study

The behavior of rifampicin (D) with -cyclodextrin (-CyD) in aqueous media (W) has been examined by means of UV-vis spectroscopy and conductivity measurements over the temperature range 15–30 °C. The UV-vis study has been used to characterize the systems. The estimated molar absorption coefficient for D/CyD/W system was 10757±280 M^–1 cm^–1 in comparison to the value of 6133±99 M^–1 cm^–1 for D/W system. The conductivity was measured (i) as a function of [D] for binary D/W systems, (ii) as a function of [CyD], keeping the concentration of drug constant, for D/CyD/W system, and (iii) as a function of [D] in the presence of a constant cyclodextrin concentration. Two transition points were observed for D/CyD/W system at constant [CyD], which were assigned as cac-1 and cac-2. The stoichiometry of the association was estimated from the conductivity data. This was obtained from [drug] value at which the change in slope of occurs. The standard free energy change, of aggregation was also calculated from the critical concentration data. An attempt has also been made to estimate the stoichiometry of -cyclodextrin:rifampicin association.     

Spectrothermal studies of 1,10-phenanthroline complexes of Co(II), NI(II), Cu(II) and Cd(II) orotates

The 1,10-phenanthroline (phen) complexes of Co(II), Ni(II), Cu(II) and Cd(II) orotates were synthesized and characterized by elemental analysis, magnetic susceptibility, spectral methods (UV-vis and FTIR) and thermal analysis techniques (TG, DTG and DTA). The Co(II), Ni(II), Cu(II) and Cd(II) ions in diaquabis(1,10-phenanthroline)metal(II) diorotate octahedral complexes [M(H₂O)₂(phen)₂](H₂Or)₂·nH₂O (M=Co(II), n=2.25; Ni(II), n=3; Cu(II) and Cd(II), n=2) are coordinated by two aqua ligands and two moles of phen molecules as chelating ligands through their two nitrogen atoms. The monoanionic orotate behaves as a counter ion in the complexes. On the basis of the first DTG_max, the thermal stability of the hydrated complexes follows the order: Cd(II), 68°C 68°C     

New Copper（Ⅱ） and Nickel（Ⅱ） Complexes of 4-Morpholinoacetophenone Thiosemicarbazone： Structural, Electrochemical and Antimicrobial Studies

4-Morpholinoacetophenone thiosemicarbazone, MAPT, and its nickel（Ⅱ） and copper（Ⅱ） complexes have been prepared and characterized by elemental analysis, magnetic susceptibility, spectral methods （FT-IR, ^1H NMR） and cyclic voltammetry. Electrochemical behaviors of the complexes have been studied by cyclic voltammetry in DMF media showing metal centered reduction processes for both of them. The redox properties, nature of the electrode processes and the stability of the complexes were discussed. [Cu（MAPT）2]Cl2 complex shows Cu（Ⅱ）/Cu（Ⅰ） couple and quasi-reversible wave associated with the Cu（Ⅲ）/Cu（Ⅱ） process. The reduction/oxidation potential values depend on the structures of complexes. Also, the antimicrobial activities of these complexes were determined against S. aureus, E. coli and B. subtilis.     

Spin crossover studies in tris(N,N′-dialkyldithiocarbamato)iron(III) complexes

A series of fifteen complexes of the type [Fe(RRNCS₂)₃] with symmetric (R=R=n- C₆H₁₃, n-C₈H₁₇, CH₂–CH=;CH₂, C₆H₅, C₆H₁₁ and C₆H₅CH₂), unsymmetric (R = CH₃; R = n-C₄H₉, C₆H₁₁, C₆H₅ and R = C₂H₅; R = n-C₄H₉, C₆H₁₁, C₆H₅ and i-C₃H₇) and ring substituents (RNR=pyrrolidyl and piperidyl) have been synthesized and their magnetic moments and Mössbauer spectra recorded from room temperature (RT) to liquid nitrogen temperature (LNT). Room temperature Mössbauer spectra of all the complexes exhibit an asymmetric doublet, which could be resolved into two doublets, each corresponding to low and high spin states in equilibrium. The crystal structure of tris(N, N-diallyldithiocarbamato)iron(III) shows it to be monoclinic with trigonally distorted octahedral geometry and space group C2/c. Fe–S stretching vibrations in the far i.r. region also show equilibria, HS LS. Depending on the nature of the alkyl group substituent, variable temperature magnetic moment and Mössbauer spectral studies, all the complexes may be divided into three groups; high spin complexes exhibiting spin-crossover (⁶A_1g ²T_2g), high spin complexes exhibiting spin transition (⁶A_1g ⁴T_1g) and intermediate spin complexes showing spin transition (⁴A_1g ²T_2g). On the basis of areas of the two doublets corresponding to high and low spin states, their percent contributions were calculated. Furthermore, magnetic moments of the equilibrium mixture calculated on the basis of respective areas compare well with the experimentally determined _eff values. E_Q values for both high and low spin states show linear decrease with increasing temperature.     

Solvent extraction behaviour of iodine and bromine in aqueous-organic systems,analogy with radioactive decay

The extraction of iodine and bromine under various conditions from their saturated aqueous solutions by CCl₄, C₆H₆ and o-xylene has been studied. The data obtained from the experiments carried out at various temperatures, for H₂O(I₂)−CCl₄ and H₂O(I₂)−C₆H₆ systems, exhibit an Arrhenius behaviour. The overall activation energy calculated for the extraction in the H₂O(I₂)−CCl₄ system, 650±50 cal·mol⁻¹ is lower than that of H₂O(I₂)−C₆H₆, 3600±300 cal·mol⁻¹. The use of the solubility parameter for the interpretation of the data in the extraction of iodine is investigated. The data obtained in multiple extractions are treated by using the analogy between extraction and radioactive decay. The half number of extraction for each system is determined. The complex curves obtained in the H₂O(I₂)−CCl₄ and H₂O(I₂) −Br₂)−CCl₄ systems are resolved into two components.     

DNA-binding studies of mixed ligand cobalt(III) complexes

The DNA binding characteristics of mixed ligand complexes of the type [Co(en)₂(L)]Br₃ where en = N,N′-ethylenediamine and L = 1,10-phenanthroline (phen), 2,2′-bipyridine (bpy), 1,10-phenanthroline-5,6-dione (phendione), dipyrido[3,2-a:2′,3′-c]phenazine (dppz) have been investigated by absorption titration, competitive binding fluorescence spectroscopy and viscosity measurements. The order of intercalative ability of the coordinated ligands is dppz > phen > phendione > bpy in this series of complexes.     

Single-site mutation and secondary structure stability: an isodesmic reaction approach. The case of unnatural amino acid mutagenesis Ala-->Lac

A method is described to evaluate backbone interactions in proteins via computational unnatural amino acid mutagenesis. Several N-acetyl polyalanyl amides (AcA(n)NH(2)) were optimized in the representative helical (3(10)-, 4(13)-, and a "hybrid" kappa-helix, n = 7, 9, 10, 14) and hairpin (two- and three-stranded antiparallel beta-sheets with type I turns betaalphaalphaepsilon, n = 6, 9, 10) conformations, and extended conformers of N-acetyl polyalanyl methylamides (n = 2, 3) were used to derive multistranded beta-sheet fragments. Subsequently, each residue of every model structure was substituted, one at a time, with l-lactic acid. The resulting mutant structures were again optimized, and group-transfer energies DeltaE(GT) were obtained as heats of the isodesmic reactions: AcA(n)NHR + AcOMe --> AcA(x)LacA(y)NHR + AcNHMe (R = H, CH(3)). These group-transfer energies correlate with the degree of charge polarization of the substituted peptide linkages as measured by the difference Deltae in H and O Mulliken populations in HN-C=O and with the H-bond distances in the "wild-type" structures. A good correlation obtains for the HF/3-21G and B3LYP/6-31G* group-transfer energies. The destabilization effects are interpreted in terms of loss of interstrand and intrastrand H-bonds, decrease in Lewis basicity of the C=O group, and O...O repulsion. On the basis of several comparisons of Ala --> Lac DeltaE(GT)'s with heats of the NH --> CH(2) substitutions, the latter contribution is estimated (B3LYP/6-31G*) to range between 1.5 and 2.4 kcal mol(-1), a figure close to the recent experimental DeltaDeltaG(o) value of 2.6 kcal mol(-1) (McComas, C. C.; Crowley, B. M.; Boger, D. L. J. Am.Chem. Soc. 2003, 125, 9314). The partitioning yields the following maximum values of the electronic association energy of H-bonds in the examined sample of model structures (B3LYP/6-31G* estimates): 3(10)-helix D(e) = -1.7 kcal mol(-1), alpha-helix D(e) = -3.8 kcal mol(-1), beta-sheet D(e) = -6.1 kcal mol(-1). The premise of experimental evaluations of the backbone-backbone H-bonding that Ala --> Lac substitution in proteins is isosteric (e.g., Koh, J. T.; Cornish, V. W.; Schultz, P. G. Biochemistry 1997, 36, 11314) is often but not always corroborated. Examination of the integrity of H-bonding pattern and phi(i), psi(i) distribution identified several mutants with significant distortions of the "wild-type" structure resulting inter alia from the transitions between i, i + 3 and i, i + 4 H-bonding in helices, observed previously in the crystallographic studies of depsipeptides (Ohyama, T.; Oku, H.; Hiroki, A.; Maekawa, Y.; Yoshida, M.; Katakai, R. Biopolymers 2000, 54, 375; Karle, I. L.; Das, C.; Balaram, P. Biopolymers 2001, 59, 276). Thus, the isodesmic reaction approach provides a simple way to gauge how conformation of the polypeptide chain and dimensions of the H-bonding network affect the strength of backbone-backbone C=O...HN bonds. The results indicate that the stabilization provided by such interactions increases on going from 3(10)-helix to alpha-helix to beta-sheet.