Template synthesiS: Geometrical and electronic structures of the Fe nitrosyl complex formed by bis(S-methylisothiosemicarbazone)-2,4-pentandione

Sodium acetylacetonate reacts with S-metliylisothiosemicarbazidium nitrate and Fe(NO₃)₃ · 9H₂O in ethanol to make [Fe(HL)NO]NO₃, in which H₃L is bis(S-methyl-isothiosemicarbazone)-2,4-puntandione. The [Fe(HL)NO]⁺ cation has a square pyramidal structure with the HL^2- arranged around the central ion in the basal plane and the nitrogen atom of the NO group in the apical position, with the iron atom diverging from the plane of the base of the pyramid by 0.477 Å. The FeN0 moiety has a linear structure (FeNO = l72.7°). XRD, IR, and Mössbauer spectroscopy have been combined with calculations on the electronic structure to demonstrate that the Fe-NO bond is covalent.Chemical Institute, Academy of Sciences of Moldavian SSR. Applied Physics Institute, Academy of Sciences of the Moldavian SSR. Kishinev. Institute of Crystallography, Academy of Sciences of the USSR. Kurnakov Institute for General and Inorganic Chemistry, Academy of Sciences of the USSR, Moscow. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 27, No, 3, pp. 376–381, May–June, 1991. Original article submitted February 18, 1991.     

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.     

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     

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.     

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.     

Structure of starch-bentonite gels

Mixed gels of starch and bentonite are investigated in the interval 0.056–0.089 of total solids/water ratio and 0-100% starch in the solids. The bentonite was a sodium calcium bentonite with a Na/Ca ratio of 1.76. In water it forms gels consisting of a network of band-type structures. Starch forms gels through hydrogen bonds between granules and/or amylose and amylopectin present on the external surfaces of granules and/or in fully stretched form. Mixed gels of bentonite and starch were obtained by adding corn starch granules to the already formed bentonite gels and heating the mixture above the Kofler gelatinization temperature. Amylose and amylopectin were adsorbed on strands of band-type structures of mont-morillonite lamellae. Starch gellation, e.g. diffusion of amylose out of the granule, was facilitated in the presence of bentonite. On the other hand, the presence of starch favored delamination of the montmorillonite particle into thinner lamellae. Maximum gelatinization and polymer adsorption were observed for gels with 20% starch and 80% bentonite. Montmorillonite networks formed the continuous phase for 0-80% starch. At higher starch concentrations, montmorillonite flakes were dispersed within the polymer network. Increase in the water content of the gels caused segregation of the bentonite and starch.     

The first bis(orotato–N,O) complex: Synthesis,crystal structure,spectroscopic and thermal characterization of (chaH)2[Cu(HOr–N,O)2(cha)] · 2H2O (cha = cyclohexylamine and HOr = orotate(2−))

The novel bis(cyclohexylaminium) cyclohexylaminebis(orotate–N,O)cuprate(II) dihydrate, (C₆H₁₅N)₂[Cu(C₅H₂N₂O₄)₂(C₆H₁₄N)] · 2H₂O, has been prepared and characterized by elemental analysis, magnetic measurements, FT-IR and UV–Vis spectroscopy, thermal analysis and X-ray diffraction. The Cu(II) complex crystallizes in the monoclinic space group P2₁/c. The copper atom in the five-coordinated (chaH)₂[Cu(HOr–N,O)₂(cha)] · 2H₂O is chelated by a deprotonated pyrimidine nitrogen atom and carboxylate oxygen atom as a bis(bidentate) ligand and the cyclohexylamine ligand completes the square-pyramidal coordination. The thermal decomposition of the complex has been predicted by the help of thermal analysis (TG, DTG and DTA).     

A survey of 222Rn concentrations in dwellings of Turkey

As part of a national program to determine public exposure to natural radiation, indoor air ²²²Rn concentrations were determined in dwellings of Turkey. The ²²²Rn concentrations were measured with time-integrating passive nuclear etched track detectors in 27 provincial centers. The indoor radon concentrations were found to be in the range of 10-380 Bq^.m^-3. This revised version was published online in August 2006 with corrections to the Cover Date.