Synthesis and structural, spectroscopic and magnetic studies of two new polymorphs of Mn(SeO3)·H2O

Two new manganese(II) selenite polymorphs with formula Mn(SeO₃)·H₂O have been synthesized by slow evaporation from an aqueous solution. The crystal structure of both compounds (1) and (2) have been solved from X-ray diffraction data. The structure of (1) was determined from single-crystal X-ray diffraction techniques. The compound crystallizes in the Ama2 space group, with a=5.817(1), b=13.449(3), and Z=4. The structure of (2) has been solved from X-ray powder diffraction data. This phase crystallizes in the P2₁/n space group with unit-cell parameters of a=4.921(3), b=13.121(7), , β=90.03(2)° and Z=4. Both polymorphs exhibit a layered structure formed by isolated sheets of MnO₆ octahedra and (SeO₃)²⁻ trigonal pyramids in the (010) plane. These layers, which contain one manganese and selenium atom crystallographically independent, are formed by octahedra linked between them through the selenite oxoanions. The difference of both compounds consists in the stacking of the layers along the b-axis. The IR spectra show the characteristic bands of the selenite anion. Studies of luminescence performed at 6 K and diffuse reflectance spectroscopy have been carried out for both phases. The Dq and Racah (B and C) parameters, from luminescence and diffuse reflectance spectroscopy, are Dq=705, B=750, for (1) and Dq=720, B=745, for (2). The ESR spectra of both compounds are isotropic with g-values of 1.99(1). Magnetic measurements indicate the presence of antiferromagnetic couplings in both phases. The J-exchange parameters have been estimated by fitting the experimental magnetic data to a model for square-planar lattice. The values obtained are J/k=-0.83, −0.91 K and J^′/k=-0.97, −1.20 K, for polymorphs (1) and (2), respectively.     

Toward efficient Zn(II)-based artificial nucleases

A series of cis-cis-triaminocyclohexane Zn(II) complex-anthraquinone intercalator conjugates, designed in such a way to allow their easy synthesis and modification, have been investigated as hydrolytic cleaving agents for plasmid DNA. The ligand structure comprises a triaminocyclohexane platform linked by means of alkyl spacers of different length (from C(4) to C(8)) to the anthraquinone group which may intercalate the DNA. At a concentration of 5 microM, the complex of the derivative with a C(8) alkyl spacer induces the hydrolytic stand scission of supercoiled DNA with a rate of 4.6 x 10(-6) s(-1) at pH 7 and 37 degrees C. The conjugation of the metal complex with the anthraquinone group leads to a 15-fold increase of the cleavage efficiency when compared with the anthraquinone lacking Zn-triaminocyclohexane complex. The straightforward synthetic procedure employed, allowing a systematic change of the spacer length, made possible to gain more insight on the role of the intercalating group in determining the reactivity of the systems. Comparison of the reactivity of the different complexes shows a remarkable increase of the DNA cleaving efficiency with the length of the spacer. In the case of too-short spacers, the advantages due to the increased DNA affinity are canceled due to the incorrect positioning of the reactive group, thus leading to cleavage inhibition.     

Stereochemical analysis of 3,4-methylenedioxymethamphetamine and its main metabolites by gas chromatography/mass spectrometry

3,4-Methylenedioxymethamphetamine (MDMA, ecstasy) is consumed as the racemate but some metabolic steps are enantioselective. In addition, chiral properties are preserved during MDMA biotransformation. A quantitative analytical methodology using gas chromatography/mass spectrometry (GC/MS) to determine enantioselective disposition in the body of MDMA and its main metabolites including 3,4-methylenedioxyamphetamine (MDA), 4-hydroxy-3-methoxymethamphetamine (HMMA), and 4-hydroxy-3-methoxyamphetamine (HMA) was developed. Plasma and urine samples were collected from a male volunteer. The analysis of MDMA, MDA, and 4-hydroxy-3-methoxy metabolites by GC/MS required a two-step derivatization procedure. The first step consisted of derivatization of the amine with enantiomerically pure Mosher's reagent ((R)-MTPCl). Triethylamine was used as a base to neutralize hydrochloric acid formed during the reaction allowing quantitative derivatization, which resulted in a substantial improvement in the sensitivity of the method compared with other previously described techniques. Further treatment with ammonium hydroxide was required since both amine and hydroxyl groups underwent derivatization in the reaction. Ammonium hydroxide breaks bonds formed with hydroxyl groups without affecting amine derivatives. The second derivatization step using hexamethyldisilazane was needed for metabolites containing phenol residues. This derivatization method permitted the stereochemically specific study of MDMA and its main monohydroxylated metabolites by GC/MS. A detailed study of the chemical reactions involved in the derivatization steps was indispensable to develop a straightforward, sensitive, and reproducible method for the analysis of the parent drug compound and its metabolites.     

Kinetics and Mechanism of the Photosensitized Oxidation of Furosemide*

Detection of O2(1δg) phosphorescence emission, γmax = 1270 nm, following laser excitation and steady-state competitive methods was employed to measure total rate constants, kT, for the reactions of the diuretic furosemide, 2-methylfurane and furfurylamine with singlet oxygen in several solvents. Correlation of kT values with solvent parameters and product identification shows that the reaction mechanism is strongly solvent dependent. In aliphatic alcohols, the dependence of kT on solvent parameters is similar to the one observed for triethylamine, suggesting a reaction mechanism involving partial charge transfer from the amino group to the singlet oxygen. In nonprotic solvents, the dependence of kT on solvent parameters resembles the behavior found for 2-methylfur-ane and furfurylamine, implying that mostly a 2 + 4 cy-cloaddition mechanism of singlet oxygen to furane ring of furosemide occurs in these solvents. These mechanistic differences are explained in terms of hydrogen-bonding interactions between the carboxylic group in the aromatic ring and the amino group of furosemide. Furthermore, direct generation of C2(1δg) by furosemide was detected. Quantum yields of 0.047 ± 0.003 and 0.078 ± 0.004 were determined in acetonitrile and benzene, respectively. This last result may be related, at least partially, to the photodynamic effects of this diuretic drug.     

Spectroscopic study of the light-harvesting protein C-phycocyanin associated with colorless linker peptides

C-Phycocyanin (PC) trimers associated with linker polypeptides were isolated from the phycobilisome (PBS) rods of Synechococcus sp. PCC 7002. LXY refers to a linker polypeptide (L) having an apparent mass of Y kDa, located at position X in the phycobilisome where X can be R (rod), C (core) or RC (rod-core junction). Measurements of the absorption, fluorescence and excitation anisotropy of PC trimer, PC.LR32.3 and PC.LRC28.5 complexes document the spectroscopic modulation of each linker polypeptide on the PC chromophores. The difference spectra between the PC trimer and the PC-linker complexes show that although the effect induced by the linker polypeptides is qualitatively similar in behavior, the extent of the modulation is greater in PC.LRC28.5. Measurements taken at 77 K show that a red-wavelength component of the PC trimer absorption-fluorescence spectra is the target of the linker's influence and that this component is altered to a greater extent by LRC28.5. In addition the 77 K absorbance of the PC trimer resolves band features that are consistent with an excitonic coupling interaction between neighboring alpha 84 and beta 84 chromophores. These band features are also evident in the absorbance of PC.LR32.3 but are absent in PC.LRC28.5 indicating that LRC28.5 may be perturbing the coupling interaction established in the PC trimer alpha 84-beta 84 chromophore pairs. Structurally, the linker polypeptide should disrupt the C3 symmetry in the central cavity of the associated phycobiliprotein and this asymmetric interaction should serve to guide the transfer of excitation energy along PBS rods toward the core elements.     

Diffusion coefficients of 2-fluoroanisole, 2-bromoanisole, allylbenzene and 1,3-divinylbenzene at infinite dilution in supercritical carbon dioxide

The Taylor–Aris chromatographic technique was employed for the determination of diffusion coefficients of 2-fluoroanisole, 2-bromoanisole, allylbenzene and 1,3-divinylbenzene at infinite dilution in supercritical carbon dioxide from 313.16 to 333.16 K and pressures between 15 and 35 MPa. As expected, the diffusivities rise when temperature increases and pressure decreases. Numerous predictive equations are compared with experimental data: Lai–Tan, Liu–Ruckenstein cluster formula, Woerlee, Hippler–Schubert–Troe, Catchpole–King, Eaton–Akgerman, He, He–Yu, Liu–Silva–Macedo, Funazukuri and coworkers, Dariva–Coelho–Oliveira, Zhu–Lu–Zhou–Wang–Shi and the Liu–Ruckenstein RHS formula. The equations of He, He–Yu and Catchpole–King are the best of all, but cannot be used in the whole range of temperatures and solvent densities.     

Holo- and hemidirected lead(II) in the polymeric [Pb(4)(mu-3,4-TDTA)2(H2O)2]*4H2O complex. N,N,N',N'-tetraacetate ligands derived from o-phenylenediamines as sequestering agents for lead(II)

The coordinating ability of the ligands 3,4-toluenediamine-N,N,N',N'-tetraacetate (3,4-TDTA), o-phenylenediamine-N,N,N',N'-tetraacetate (o-PhDTA), and 4-chloro-1,2-phenylenediamine-N,N,N',N'-tetraacetate (4-Cl-o-PhDTA) (H4L acids) toward lead(II) is studied by potentiometry (25 degrees C, I = 0.5 mol x dm(-3) in NaClO4), UV-vis spectrophotometry, and 207Pb NMR spectrometry. The stability constants of the complex species formed were determined. X-ray diffraction structural analysis of the complex [Pb4(mu-3,4-TDTA)4(H2O)2]*4H2O (1) revealed that 1 has a 2-D structure. The layers are built up by the polymerization of centrosymmetric [Pb4L2(H2O)2] tetranuclear units. The neutral layers have the aromatic rings of the ligands pointing to the periphery, whereas the metallic ions are located in the central part of the layers. In compound 1, two types of six-coordinate lead(II) environments are produced. The Pb(1) is coordinated to two nitrogen atoms and four carboxylate oxygens from the ligand, whereas Pb(2) has an O6 trigonally distorted octahedral surrounding. The lead(II) ion is surrounded by five carboxylate oxygens and a water molecule. The carboxylate oxygens belong to four different ligands that are also joined to four other Pb(1) ions. The selective uptake of lead(II) was analyzed by means of chemical speciation diagrams as well as the so-called conditional or effective formation constants K(Pb)eff. The results indicate that, in competition with other ligands that are strong complexing agents for lead(II), our ligands are better sequestering agents in acidic media.     

Opportunities for the valorization of industrial glycerol via biotransformations

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