Evaluation of the redox properties and anti/pro-oxidant effects of selected flavonoids by means of a DNA-based electrochemical biosensor

Quercetin and rutin as well as catechin and epigallocatechin gallate were investigated, as widely distributed representatives of flavonols and flavanols, respectively, regarding their anti/pro-oxidant properties. The flavonoids are irreversibly oxidized at a dsDNA-modified screen-printed electrode within 0.368 to 0.449 V vs. SHE without binding to DNA. Using the DNA biosensor the detection scheme of a DNA prevention/degradation exploits the [Co(phen)(3)](3+) complex as an electrochemical DNA marker. Antioxidant activity of flavonoids was tested in a model cleavage mixture composed of 5 x 10(-7) mol L(-1) [Cu(phen)(2)](2+) as the catalyst, 1 x 10(-3) mol L(-1) ascorbic acid as the chemical reductant and atmospheric oxygen as the natural oxidant where reactive oxygen radicals are generated. The antioxidant activity increases with the concentration of flavonoids reaching a maximum where pro-oxidative behaviour becomes of importance. The pro-oxidant potency of flavonoids depends on the presence of atmospheric oxygen and follows the order quercetin>rutin>epigallocatechin gallate>catechin.     

The separation of some Bi- and tervalent cations on zirconium phosphate columns

Summary On small columns filled with the inorganic cation-exchanger zirconium phosphate, Zn²⁺-Cd²⁺ were quantitatively and Ni²⁺-Co²⁺ partly separated. The exchanger was in the NH₄+ form, and 0.5–4N NH₄Cl served as eluent. With the exchanger in the H+ form, U0₂ ²⁺ was separated from bivalent cations and ferric iron by stepwise elution with 0.1, 0.5 and 4N HCl solutions.

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Zusammenfassung An kleinen Säulen des anorganischen Kationenaustauschers Zirkoniumphosphat wurden Zn²⁺ und Cd²⁺ quantitativ, Ni²⁺ und Co²⁺ teilweise getrennt. Der Austauscher lag in der NH₄+-Form vor, 0,5-bis 4-n Ammoniumchlorid diente als Eluent. Mit der H+-Form des Austauschers wurde UO₂ ²⁺ von zweiwertigen Kationen und von Fe³⁺ durch schrittweise Elution mit 0,1-, 0,5- und 4-n Salzsäure getrennt.

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Résumé On a séparé Zn²⁺-Cd²⁺ quantitativement et Ni²⁺-Co²⁺ partiellement sur de petites colonnes remplies de phosphate de zirconium comme échangeur minéral cationique. L'échangeur se trouvait sous forme NH₄+ et l'on a pris NH₄Cl 0,5-4N comme éluant. Avec l'échangeur sous forme H⁺, on a séparé UO₂ ²⁺ des cations bivalents et de l'ion ferrique par élution graduelle avec des solutions chlorhydriques 0,1, 0,5 et 4N.

     

DNA interchain cross-links formed by acrolein and crotonaldehyde

Acrolein and higher alpha,beta-unsaturated aldehydes are bifunctional genotoxins. The deoxyguanosine adduct of acrolein, 3-(2-deoxy-beta-d-erythro-pentofuranosyl)-5,6,7,8-tetrahydro-8-hydroxypyrimido[1,2-a]purin-10(3H)-one (8-hydroxy-1,N(2)-propanodeoxyguanosine, 2a), is a major DNA adduct formed by acrolein. The potential for oligodeoxynucleotide duplexes containing 2a to form interchain cross-links was evaluated by HPLC, CZE, MALDI-TOF, and melting phenomena. Interchain cross-links represent one of the most serious types of damage in DNA since they are absolute blocks to replication. In oligodeoxynucleotides containing the sequence 5'-dC-2a, cross-linking occurred in a slow, reversible manner to the extent of approximately 50%. Enzymatic digestion to form 3-(2-deoxy-beta-d-erythro-pentofuranosyl)-5,6,7,8-tetrahydro-8-(N(2)-2'-deoxyguanosinyl)pyrimido[1,2-a]purin-10(3H)one (5a) and reduction with NaCNBH(3) followed by enzymatic digestion to give 1,3-bis(2'-deoxyguanosin-N(2)-yl)propane (6a) established that cross-linking had occurred with the exocyclic amino group of deoxyguanosine. It is concluded that the cross-link is a mixture of imine and carbinolamine structures. With oligodeoxynucleotide duplexes containing the sequence 5'-2a-dC, cross-links were not detected by the techniques enumerated above. In addition, (15)N-(1)H HSQC and HSQC-filtered NOESY spectra carried out with a duplex having (15)N-labeling of the target amino group established unambiguously that a carbinolamine cross-link was not formed. The potential for interchain cross-link formation by the analogous crotonaldehyde adduct (2b) was evaluated in a 5'-dC-2b sequence. Cross-link formation was strongly dependent on the configuration of the methyl group at C6 of 2b. The 6R diastereomer of 2b formed a cross-link to the extent of 38%, whereas the 6S diastereomer cross-linked only 5%.     

Uranyl coordination environment in hydrophobic ionic liquids: an in situ investigation

Different inner-sphere coordination environments are observed for the uranyl nitrate complexes formed with octyl-phenyl-N,N-diisobutylcarbamoylmethylphosphine oxide and tributyl phosphate in dodecane and in the hydrophobic ionic liquids (ILs) [C(4)mim][PF(6)] and [C(8)mim][N(SO(2)CF(3))(2)]. Qualitative differences in the coordination environment of the extracted uranyl species are implied by changes in peak intensity patterns and locations for uranyl UV-visible spectral bands when the solvent is changed. EXAFS data for uranyl complexes in dodecane solutions is consistent with hexagonal bipyramidal coordination and the existence of UO(2)(NO(3))(2)(CMPO)(2). In contrast, the complexes formed when uranyl is transferred from aqueous nitric acid solutions into the ILs exhibit an average equatorial coordination number of approximately 4.5. Liquid/liquid extraction results for uranyl in both ILs indicate a net stoichiometry of UO(2)(NO(3))(CMPO)(+). The concentration of the IL cation in the aqueous phase increases in proportion to the amount of UO(2)(NO(3))(CMPO)(+) in the IL phase, supporting a predominantly cation exchange mechanism for partitioning in the IL systems.     

The phenomenon of conglomerate crystallization. XX. Spontaneous resolution in coordination compounds. XVIII.

The title compound, [cis-Co(en)₂(NO₂)₂](NO₂) (1), crystallizes in the polar, nonenantiomorphic, monoclinic space group, Cc, with lattice constants:a=9.198(2) Å,b=12.444(2),c=9.963(3), and=96.76(2)°;V=1132.39 ų andd(calc;Z=4) =1.860 g cm^–3. Thus, with NO_2– as the counteranion, [cis-Co(en)₂(NO₂)₂] crystallizes in a heterochiral lattice containing racemic pairs of cations. A total of 2699 data were collected over the range of 4°270°; of these, 1859 (independent and withI3(I)) were used in the structural analysis. Data were corrected for absorption (=15.465 cm^–1) and the relative transmission coefficients ranged from 0.9934 to 0.7112. Refinement was carried out for both lattice polarities and the finalR(F) andR _w (F) residuals were, respectively, 0.0242 and 0.0202 for (–––) and 0.0264 and 0.0243 for (+++). Thus, the former was selected as correct for our specimen.Unlike all previous X-ray diffraction studies of the structural properties of the cation [cis-Co(en)₂(NO₂)₂]⁺, which are found to have a pair of oppositely configured en rings [i.e., () or ()], we find that in1 the cations are in the lowest energy conformation and configuration; i.e., () or (). We attribute this change in configuration to the formation of strong interionic hydrogen bonds between nitrite anion oxygens and the axial—NH₂ hydrogens, which markedly weaken the intermolecular and intramolecular hydrogen bonds between ligand—NO₂ oxygens and the hydrogens of those same amine moieties. Thus, the nitrite anions behave exactly as nitrate anions, except that the hydrogen bonds found here are stronger than those formed by the latter. This is as expected since the negative charge is delocalized over two, instead of three, oxygens.     

Formation of two isomeric closo-[(eta5-C5H5)FePC2B8H10] phosphadicarbaborane analogues of ferrocene via isolable eta1-bonded complexes of the [7-[(eta5-C5H5)Fe(CO)2]-(eta1-nido-PC2B8H10)] type

The reaction of nido-[7,8,9-PC(2)B(8)H(11)] (1) with [[CpFe(CO)(2)](2)] (Cp=eta(5)-C(5)H(5) (-)) in benzene (reflux, 3 days) gave an eta(1)-bonded complex [7-Fp-(eta(1)-nido-7,8,9,-PC(2)B(8)H(10))] (2; Fp=CpFe(CO)(2); yield 38 %). A similar reaction at elevated temperatures (xylene, reflux 24 h) gave the isomeric complex [7-Fp-(eta(1)-nido-7,9,10-PC(2)B(8)H(10))] (3; yield 28 %) together with the fully sandwiched complexes [1-Cp-closo-1,2,4,5-FePC(2)B(8)H(10)] 4 a (yield 30%) and [1-Cp-closo-1,2,4,8-FePC(2)B(8)H(10)] 4 b (yield 5%). Compounds 2 and 3 are isolable intermediates along the full eta(5)-complexation pathway of the phosphadicarbaborane cage; their heating (xylene, reflux, 24 h) leads finally to the isolation of compounds 4 a (yields 46 and 52%, respectively) and 4 b (yields 4 and 5%, respectively). Moreover, compound 3 is isolated as a side product from the heating of 2 (yield 10%). The structure of compound 4 a was determined by an X-ray structural analysis and the constitution of all compounds is consistent with the results of mass spectrometry and IR spectroscopy. Multinuclear ((1)H, (11)B, (31)P, and (13)C), two-dimensional [(11)B-(11)B]-COSY, and (1)H[(11)B(selective)] magnetic resonance measurements led to complete assignments of all resonances and are in excellent agreement with the structures proposed.     

Cleavage of the peptide bond of beta-alanyl-L-histidine (carnosine) induced by a Co(III)-amine complexes: reaction, structure and mechanism

Cleavage of the peptide bond occurs when beta]-alanyl-L-histidine (carnosine) reacts with [Co(tren)Cl2]+ (tren = tris(2-aminoethyl)amine) to give [Co(tren)(histidine)](2+) 1 and [Co(tren)(beta-alanine)](2+) 2. [Co(tren)(histidine)](2+) 1 crystallizes in the enantiomorphic space group P2(1)2(1)2(1) and 2 crystallizes in the P2(1)/c space group. The mechanism of the cleavage reactions were studied in detail for the precursor [Co(tren)Cl2]+ and [Co(trien)Cl2]+, which convert into [Co(tren)(OH)2]+/[Co(tren)(OH)(OH2)]2+ and [Co(trien)(OH)2]+/[Co(trien)(OH)(OH2)]2+ in water at basic pH (trien = 1,4,7,10-tetraazadecane). At a slightly basic pH, the initial coordination of the substrate (beta-alanyl-L-histidine) is by the carboxylate group for the reaction with [Co(tren)Cl2]+. This is followed by a rate-limiting nucleophilic attack of the hydroxide group at the beta-alanyl-L-histidine carbonyl group. In a strongly basic reaction medium substrate, binding of the metal was through carboxylate and amine terminals. On the other hand, for the reaction between [cis-beta-Co(trien)Cl2]+ and beta-alanyl-L-histidine, the initial coordination of the substrate takes place via an imidazole ring nitrogen, independently, and followed by a nucleophilic attack of the hydroxide group at the beta-alanyl-L-histidine carbonyl group. The circular dichroism spectrum for 1 suggests that a very small extent of racemization of the amino acid (L-histidine) takes place during the cleavage reaction between [Co(tren)Cl2]+ and beta-alanyl-L-histidine. Reaction between [cis-beta-Co(trien)Cl2]+ and beta-alanyl-L-histidine also causes cleavage of the peptide bond, producing a free beta-alanyl molecule and a cationic fragment [cis-alpha-Co(trien)(histidine)](2+) 3 that crystallizes in the optically active space group P2(1)2(1)2(1). Unlike the previous case an appreciable degree of racemization of the L-histidine takes place during the reaction between [cis-beta-Co(trien)Cl2]+ and beta-alanyl-L-histidine. Crystals containing L-histidine and D-histidine fragments in the [cis-alpha-Co(trien)(histidine)]2+ moiety were crystallographically documented by mounting a number of randomly selected crystals.     

Capillary gas chromatographic separation of C10–C12 secondary phenylalkanes on modified cyclodextrin stationary phases

The separation of isomers and enantiomers of branched C₁₀-C₁₂ phenylalkanes by gas chromatography on fused silica capillary columns coated with some modified β- and γ-cyclodextrins was studied. It was shown that the separation of positional isomers of C₁₀-C₁₂ phynylalkanes on modified cyclodextrin capillary columns is not better than that on a column coated with modified polyethylene glycol. Differences were found in the enantioselectivity of modified β- and γ-cyclodextrins for the separation of C₁₀-C₁₂ secondary phenylalkane enantiomers. While alkylderivatives of β-CDs resolve enantiomers of 3-phenylalkanes, alkyl derivatives of γ-CD resolve enantiomers of 2-phenylalkanes. Since shape selectivity factors of modified cyclodextrins have indicated no inclusion of the considered solutes in cyclodextrin cavities, enantioselective interactions most probably occur on the outer sphere of cyclodextrins.     

The dynamics of vortex sources in a deformation flow

This paper is concerned with the dynamics of vortex sources in a deformation flow. The case of two vortex sources is shown to be integrable by quadratures. In addition, the relative equilibria (of the reduced system) are examined in detail and it is shown that in this case the trajectory of vortex sources is an ellipse.     

Control of Protonated Schiff Base Excited State Decay within Visual Protein Mimics: A Unified Model for Retinal Chromophores

Artificial biomimetic chromophore-protein complexes inspired by natural visual pigments can feature color tunability across the full visible spectrum. However, control of excited state dynamics of the retinal chromophore, which is of paramount importance for technological applications, is lacking due to its complex and subtle photophysics/photochemistry. Here, ultrafast transient absorption spectroscopy and quantum mechanics/molecular mechanics simulations are combined for the study of highly tunable rhodopsin mimics, as compared to retinal chromophores in solution. Conical intersections and transient fluorescent intermediates are identified with atomistic resolution, providing unambiguous assignment of their ultrafast excited state absorption features. The results point out that the electrostatic environment of the chromophore, modified by protein point mutations, affects its excited state properties allowing control of its photophysics with same power of chemical modifications of the chromophore. The complex nature of such fine control is a fundamental knowledge for the design of bio-mimetic opto-electronic and photonic devices.