Biomedical subjects

H A Tajmir-Riahi

Publications and source records attributed to H A Tajmir-Riahi.

At least 55 records · Page 3Linked to original sources

PubMed1995

A quantitative secondary structure analysis of the 33 kDa extrinsic polypeptide of photosystem II by FTIR spectroscopy.

In chloroplast photosystem II, the extrinsic polypeptide of 33 kDa is involved in the stabilization the Mn cluster in charge of water splitting and in the fulfilment of the Ca(2+)-cofactor requirement for oxygen evolution. The conformational analysis of the purified 33 kDa extrinsic polypeptide was carried out using FTIR spectroscopy with its self-deconvolution and second derivative resolution enhancement as well as curve-fitting procedures. The FTIR spectroscopic results showed that the isolated polypeptide is characterized by a major proportion beta-sheet conformation (36%) with 27% alpha-helix, 24% turn, and 13% beta-antiparallel structures.

Calcium↗

PubMed1995

The effect of HCl on the solution structure of calf thymus DNA: a comparative study of DNA denaturation by proton and metal cations using Fourier transform IR difference spectroscopy.

The interaction of HCl with calf thymus DNA was investigated in aqueous solution at pH 7-2 with H+/DNA(P) (P:phosphate) molar ratios (r) of 1/80, 1/40, 1/20, 1/10, 1/4, 1/2, and 1, using Fourier Transform (FTIR) difference spectroscopy. Correlations between spectral changes, proton binding mode, DNA denaturation, and conformational variations are established. A comparison was also made between the ir spectra of denaturated DNA, in the presence of proton and Cu ions with similar cation concentrations. The FTIR difference spectroscopic results have shown that at low proton concentrations of r = 1/80 and 1/40 (pH 7-5), no major spectral changes occur for DNA, and the presence of H+ results in an increased base-stacking interaction and helical stability. At higher proton concentrations of r > 1/40, the proton binding to the cytosine and adenine bases begins with major destabilization of the helical duplex. As base protonation progresses, a B to C conformational conversion occurs with major DNA spectral changes. Protonation of guanine bases occurs at a high cation concentration r > 1/2 (pH < 3) with a major increase in the intensity of several DNA in-plane vibrations. Copper ion complexation with DNA exhibits marked similarities with proton at high cation concentrations (r > 1/10), whereas at low metal ion concentrations, copper-PO2 and copper-guanine N-7 bindings are predominant. No major DNA conformational transition was observed on copper ion complexation.

Animals↗

PubMed1995

A comparative study of ATP and GTP complexation with trivalent Al, Ga and Fe cations. Determination of cation binding site and nucleotide conformation by FTIR difference spectroscopy.

The interactions of adenosine-5'-triphosphate (Na2H2ATP) and guanosine-5'-triphosphate (Na2H2GTP) with trivalent Al, Ga and Fe cations are investigated in aqueous solution at pH = 6-7 with metal/nucleotide ratios (r) 1/10, 1/2, 1 and 4. Fourier Transform infrared (FTIR) difference spectroscopy is used to characterize the nature of metal cation binding and nucleotide conformational variations, in aqueous solution. Spectroscopic evidences show that at low cation concentration (r = 1/10), metal binding is mainly through the -PO2- and -PO3(2-) groups of the nucleotide moiety (outer-sphere), while at r > 1/10, in addition to direct metal-phosphate binding (chelation), minor metal-base complexes are also formed via indirect metal-NH2 or metal-carbonyl interaction (through H2O). At r = 1, metal macrochelate formation occurs, involving direct cation coordination to phosphate groups and imidazol N-7 atom with an indirect metal-NH2 or metal-carbonyl interaction. At r = 4, polymerization of these metal complexes is observed through nucleotide phosphate chain. The amount of cation/phosphate binding is considerably larger than that of metal/base binding. Evidence for metal-phosphate coordination comes from major spectral changes (shifting and intensity variations) of the alpha-, beta- and gamma-PO2- vibrations in the region 1250-900 cm-1, while metal-base binding is characterized by spectral alterations of the bands at 1700 (guanine carbonyl stretch), 1695 (adenine N-1-H+ mode), 1650-1660 (NH2 bending), 1610-1613 (pyrimidine), 1575 (pyrimidine), 1535-1540 (imidazol), 1470-1480 (imidazol) and 1377 cm-1 (imidazol). The ribose moiety shows C2'-endo/anti conformation for the free ATP and its metal-ATP complexes with an infrared marked band at 821 cm-1. A mixture of both C2'-endo/anti and C3'-endo/anti conformations are occurring for the free GTP and its trivalent metal-complexes with marker bands at 820 and 800 cm-1.

Adenosine Triphosphate↗

PubMed1995

DNA-drug interaction. The effects of vitamin C on the solution structure of Calf-thymus DNA studied by FTIR and laser Raman difference spectroscopy.

The interaction of calf-thymus DNA with L-ascorbic acid was investigated in aqueous solution at pH=7.6 with drug/DNA(P)(P=phosphate) molar ratios (r) of 1/40, 1/20, 1/10, 1/5, 1/2, 1 and 2. Fourier Transform infrared (FTIR) and laser Raman difference spectroscopic techniques were used to establish correlations between spectral modifications and drug binding mode, sequence specificity, DNA melting and conformational changes, as well as structural variations of drug-DNA complexes in aqueous solution. Infrared and Raman spectroscopic results showed that at low drug concentration (r = 1/40), a B to A-type conformational conversion occurs with minor drug-DNA interaction through A-T bases. At r=1/20, drug-PO2 binding was also observed with reduced intensity of DNA inplane vibrational frequencies, due to the increased base-stacking interaction and duplex stability. At r> 1/20, major perturbations of DNA bases were observed for both A-T and G-C base pairs in the major and minor grooves of the duplex. Evidence for this comes form the shift of the infrared and Raman vibrations of the A-T and G-C bases on drug interaction. At r>1/5, a minor helix destabilization occurred with participation of several DNA donor sites in drug complexation. The ascorbate anion interaction occurred mainly through H-bonding of the acid OH and C-O groups with DNA phosphate, bases and doxyribose donor atoms.

Animals↗

PubMed1994

Light-induced Fourier transform infrared spectrum of the cation radical P680+.

The structure of the primary electron donor of photosystem II, P680, is still under debate. It is not decided if it is composed of a chlorophyll (Chl) monomer or dimer. In this study, Fourier transform infrared (FTIR) spectroscopy was used to analyze the changes in the vibration modes occurring upon photooxidation of P680 in a Mn-depleted PS II preparation. It is demonstrated that illumination of the above in the presence of artificial electron acceptors results in a light-minus-dark absorbance change typical of the formation of P680+. The light-minus-dark difference FTIR spectrum obtained under similar conditions is characterized by two negative peaks located at 1694 and 1652 or 1626 cm-1 that can be assigned to the 9-keto groups of the P680 Chl, the latter band being indicative of a strongly associated group. These vibrations are shifted to 1714 and 1676 cm-1, respectively, in the positive features of the difference spectrum attributed to P680+. The occurrence of two pairs of bands attributed to 9-keto groups is discussed in terms of P680 being formed of a Chl dimer.

Chlorophyll↗

PubMed1994

DNA-carbohydrate interaction. The effects of mono- and disaccharides on the solution structure of calf-thymus DNA.

We report the interaction of calf-thymus DNA with D-glucose, D-fructose, D-galactose and sucrose in aqueous solution at physiological pH with sugar/DNA(P)(P = phosphate) molar ratios (r) of 1/10, 1/5, 1, 5 and 10. FTIR difference spectroscopy was used to characterize the nature of sugar-DNA interaction and correlations between spectral changes and structural variations for both sugar and DNA complexes have been established.

Animals↗

PubMed1993

The effects of Cu2+ and Pb2+ on the solution structure of calf thymus DNA: DNA condensation and denaturation studied by Fourier transform ir difference spectroscopy.

The interaction of calf thymus DNA with Cu2+ and Pb2+ was studied in aqueous solution at pH 6.5 with metal/DNA (P) (P = phosphate) molar ratios (r) 1/80, 1/40, 1/20, 1/10, 1/4, 1/2, and 1, using Fourier Transform ir (FTIR) spectroscopy. Correlations between the ir spectral changes, metal ion binding mode, DNA condensation, and denaturation, as well as conformational features, were established. Spectroscopic evidence has shown that at low metal/DNA (P) molar ratios 1/80 and 1/40, copper and lead ions bind mainly to the PO2- of the backbone, resulting in increased base-stacking interaction and duplex stability. The major copper ion base binding via G-C base pairs begins at r > 1/40, while the lead ion base binding occurs at r > 1/20 with the A-T base pairs. The denaturation of DNA begins at r = 1/10 and continues up to r = 1/2 in the presence of copper ions, whereas a partial destabilization of the helical structure was observed for the lead ion at high metal ion concentration (r = 1/2). Metal-DNA binding also results in DNA condensation. No major departure from the B-family structure was observed, upon DNA interaction with these metal ions.

Animals↗

PubMed1993

Interaction of calf-thymus DNA with trivalent La, Eu, and Tb ions. Metal ion binding, DNA condensation and structural features.

The interaction of calf-thymus DNA with La3+, Eu3+ and Tb3+ has been investigated in aqueous solution at pH 6.5, using metal/DNA(P) molar ratios(r) 1/80, 1/40, 1/20, 1/10, 1/4 and 1/2. Correlations between FTIR spectral changes and DNA structural properties have been established. At low metal/DNA(P) (r) 1/80, the metal ions bind mainly to the PO2- groups of the backbone, resulting in increased base-stacking interaction and duplex stability. At (r) 1/40 and 1/20, metal ion binding to the PO2- and the guanine N-7 site (chelation) predominates with minor perturbations of the A-T base pairs. Evidence for this comes from the displacement of the band at 1712 cm-1 (T,G) towards a lower frequency and the PO2- antisymmetric band at 1222 cm-1 towards a higher frequency. At higher metal/DNA(P) ratio, r > 1/20, DNA begins to condensate and drastic structural changes occur, which are accompanied by the shift and intensity changes of several G-C and A-T absorption bands. No major departure from B-DNA conformation was observed before and after DNA condensation even though some local structural modifications were observed. A comparison with the Cu-DNA complexes (denaturated DNA) shows some degree of helical destabilization of the biopolymer in the presence of lanthanide ions.

Animals↗

PubMed1993

The effects of cobalt-hexammine and cobalt-pentammine cations on the solution structure of calf-thymus DNA. DNA condensation and structural features studied by FTIR difference spectroscopy.

The interaction of calf-thymus DNA with cobalt-hexammine and cobalt-pentammine cations was investigated, in aqueous solution at pH 6-7 with cation/DNA(phosphate) molar ratios r = 1/80, 1/40, 1/20, 1/10, 1/4, 1/2 and 1, using Fourier Transform infrared (FTIR) difference spectroscopy. Correlations between spectral changes, DNA condensation and helical stabilization due to the cation interaction as well as conformational features are established. At a very low cation concentration (r = 1/80), the binding of cobalt-hexammine cation with DNA is through the H-bond formation between cation NH3 groups and the PO2 groups of the backbone, resulting in duplex stability. As the cation concentration increases, hydrogen bonding expands towards guanine N-7 and O-6 atoms. At r > 1/20, DNA condensation occurs with major reduction in the intensity of several DNA in-plane vibrations and that of the phosphate group. The cobalt-pentammine cation binding is via the PO2 groups (directly) at very low metal cation concentration (r = 1/80) and the guanine N-7 and the O-6 groups (indirectly) at higher ratios. At r > 1/10, DNA condensation begins with some degree of direct cation-base binding. No major conformational changes from the B-family structure were observed before and after DNA collapse, in the presence of cobalt-ammine cations.

Animals↗

PubMed1992

The effects of monovalent cations Li+, Na+, K+, NH4+, Rb+ and Cs+ on the solid and solution structures of the nucleic acid components. Metal ion binding and sugar conformation.

The interactions of the monovalent ions Li+, Na+, K+, NH4+, Rb+ and Cs+ with adenosine-5'-monophosphoric acid (H2-AMP), guanosine-5'-monophosphoric acid (H2-GMP) and deoxyguanosine-5'-monophosphoric acid (H2-dGMP) were investigated in aqueous solution at physiological pH. The crystalline salts M2-nucleotide.nH2O, where M = Li+, Na+, K+ NH4+, Rb+ and Cs+, nucleotide = AMP, GMP and dGMP anions and n = 2-4 were isolated and characterized by Fourier Transform infrared (FTIR) and 1H-NMR spectroscopy. Spectroscopic evidence showed that these ions are in the form of M(H2O)n+ with no direct metal-nucleotide interaction, in aqueous solution. In the solid state, Li+ ions bind to the base N-7 site and the phosphate group (inner-sphere), while the NH4+ cations are in the vicinity of the N-7 position and the phosphate group, through hydrogen bonding systems. The Na-nucleotides and K-nucleotides are structurally similar. The Na+ ions bind to the phosphate group of the AMP through metal hydration shell (outer-sphere), whereas in the Na2-GMP, the hydrated metal ions bind to the base N-7 or the ribose hydroxyl groups (inner-sphere). The Na2-dGMP contains hydrated metal-carbonyl and metal-phosphate bindings (inner-sphere). The Rb+ and Cs+ ions are directly bonded to the phosphate groups and indirectly to the base moieties (via H2O). The ribose moiety shows C2'-endo/anti conformation for the free AMP acid and its alkali metal ion salts. In the free GMP acid, the ribose ring exhibits C3'-endo/anti conformer, while a C2'-endo/anti sugar pucker was found in the Na2-GMP and K2-GMP salts and a C3'-endo/anti conformation for the Li+, NH4+, Rb+ and Cs+ salts. The deoxyribose has C3'-endo/anti conformation in the free dGMP acid and O4'-endo/anti in the Na2-dGMP, K2-dGMP and a C3'-endo/anti for the Li+, NH4+, Rb+ and Cs+ salts. An equilibrium mixture of the C2'-endo/anti and C3'-endo/anti sugar puckers was found for these metal-nucleotide salts in aqueous solution.

Adenosine Monophosphate↗

PubMed1991

Interaction of guanylic acid with the Mg(II), Ca(II), Sr(II), and Ba(II) ions in the crystalline solid and aqueous solution: evidence for the ribose C2'-endo/anti and C3'-endo/anti conformational changes.

The interaction of guanosine-5'-monophosphoric acid (H2-GMP) with the alkaline earth metal ions has been studied in aqueous solution at neutral pH. The crystalline salts of the type Mg-GMP.5H2O, Ca-GMP.6H2O, Sr-GMP.7H2O, and Ba-GMP.7H2O were isolated and characterized by Fourier transform ir, 1H-nmr and x-ray powder diffraction measurements. Two types of macrochelate complexes have been identified: (a) The direct metalbase and indirect metal-phosphate bindings (inner and outer sphere interaction) for the Mg(II), Ca(II), and Sr(II), ions; and (b) the indirect metal-base and direct metal-phosphate bindings (outer and inner sphere interaction) for the Ba(II) ion. In aqueous solution, an equilibrium exists between the base-metal-H2O...PO3 and base...H2O-M-PO3 interactions. The ribose moiety shows C3'-endo/anti conformation in the free acid; C2'-endo/anti in the Na2-GMP salt; C3'-endo/anti in the Mg(II)-, Ca(II)-, and Sr(II)-GMP salts; and C2'-endo/anti, in the Ba(II)-GMP salt.

Barium↗

PubMed1991

Interaction of La (III) and Tb (III) ions with purine nucleotides: evidence for metal chelation (N-7-M-PO3) and the effect of macrochelate formation on the nucleotide sugar conformation.

The interaction of the La (III) and Tb (III) ions with adenosine-5'-monophosphate (5'-AMP), guanosine-5'-monophosphate (5'-GMP), and 2'-deoxyguanosine-5'-monophosphate (5'-dGMP) anions with metal/nucleotide ratios of 1 and 2 has been studied in aqueous solution in acidic and neutral pHs. The solid complexes were isolated and characterized by Fourier transform ir and 1H-nmr spectroscopy. The lanthanide (III)-nucleotide complexes are polymeric in nature both in the solid and aqueous solutions. In the metal-nucleotide complexes isolated from acidic solution, the nucleotide binding is via the phosphate group (inner sphere) and an indirect metal-N-7 interaction (outer-sphere) with the adenine N-1 site protonated. In the complexes obtained from neutral solution, metal chelation through the N-7 and the PO3(2-) group is prevailing. In aqueous solution, an equilibrium between the inner and outer sphere metal-nucleotide interaction has been observed. The ribose moiety shows C2'-endo/anti pucker in the free AMP anion and in the lanthanide (III)-AMP complexes, whereas the GMP anion with C2'-endo/anti sugar conformation exhibits a mixture of the C2'-endo/anti and C3'-endo/anti sugar puckers in the lanthanide (III)-GMP salts. The deoxyribose has O4'-endo/anti sugar pucker in the free dGMP anion and a C3'-endo/anti, in the lanthanide (III)-dGMP complexes.

Adenosine Monophosphate↗

PubMed1991

Coordination chemistry of vitamin C. Part II. Interaction of L-ascorbic acid with Zn(II), Cd(II), Hg(II), and Mn(II) ions in the solid state and in aqueous solution.

The reaction of L-ascorbic acid with the zinc group and manganese ions has been investigated in aqueous solution at pH 6-7. The solid salts of the type M (L-ascorbate)2.2H2O, where M = Zn(II), Cd(II) and Mn(II) were isolated and characterized by 13C NMR and Fourier Transform infrared (FT-IR) spectroscopy. Spectroscopic evidence showed that in aqueous solution, the bindings of the Zn(II) and Mn(II) ions are through the ascorbate anion O-3 and O(2)-H groups (chelation), while the Cd(II) ion binding is via the O-3 atom only. In the solid state, the binding of these metal ions would be through two acid anions via O-3, O-2 of the first and O-1, O-3 of the second anion as well as to two H2O molecules, resulting in a six-coordinated metal ion. The Hg(II) ion interaction leads to the oxidation of the ascorbic acid in aqueous solution.

Antiviral Agents↗

PubMed1991

Interaction of purine nucleotides with cobalt-hexammine, cobalt-pentammine and cobalt-tetrammine cations. Evidence for the rigidity of adenosine and flexibility of guanosine and deoxyguanosine sugar conformations.

The interaction of adenosine-5'-monophosphate (5'-AMP), guanosine-5'-monophosphate (5'-GMP) and 2'-deoxyguanosine-5'-monophosphate (5'-dGMP) with the [Co(NH3)6]3+, [Co(NH3)5Cl]2+ and [Co(NH3)4Cl2]+ cations has been investigated in aqueous solution with metal/nucleotide ratios (r) of 1/2, 1 and 2 at neutral pH. The solid complexes have been isolated and characterized by FT-IR and 1H-NMR spectroscopy. The complexes are polymeric in nature both in the crystalline solid and aqueous solution. The binding of the cobalt-hexammine cation is indirectly (via NH3) through the N-7 and the PO3(2-) groups of the AMP and via O-6, N-7 and the PO3(2-) of the GMP and dGMP anions (outer-sphere). The cobalt-pentammine and cobalt-tetrammine bindings are through the phosphate groups (inner-sphere) and the N-7 site (outer-sphere) of these nucleotide anions. The ribose moiety shows C2'-endo/anti conformation, in the free AMP and GMP anions as well as in the cobalt-ammine-AMP complexes, whereas a mixture of teh C2'-endo/anti and C3'-endo/anti sugar puckers were observed for the Co(NH3)6-GMP, Co(NH3)5-GMP and a C3'-endo/anti conformer for the Co(NH3)4-GMP complexes. The deoxyribose showed an O4'-endo/anti conformation for the free dGMP anion and a C3'-endo/anti for the Co(NH3)6-dGMP, Co(NH3)5-dGMP and Co(NH3)4-dGMP complexes.

Adenosine↗

PubMed1990

Interaction of adenylic acid with alkaline earth metal ions in the crystalline solid and aqueous solution. Evidence for the sugar C'2-endo/anti, C'3-endo/anti and C'4-exon/anti conformational changes.

The reaction of adenosine 5'-monophosphoric acid (H2-AMP) with the alkaline earth metal ions has been investigated in aqueous solution at neutral pH. The solid salts of Mg-AMP.5H2O, Ca-AMP.6H2O, Sr-AMP.7H2O and Ba-AMP.7H2O were isolated and characterized by Fourier transform infrared, 1H-NMR spectroscopy and X-ray powder diffraction measurements. Spectroscopic and other evidence showed that the Sr-AMP.7H2O and Ba-AMP.7H2O are isomorphous, whereas the Mg-AMP.5H2O and Ca-AMP.6H2O are not similar. The Mg2+ binding is through the N-7 (inner-sphere) and the phosphate group (outer-sphere via H2O), while the Ca2+ binds to the phosphate group (inner-sphere) and to the base N-7 site (outer-sphere through H2O). The Sr2+ and Ba2+ bind to H2O molecules, H-bonding to the N-7, N-1 and the phosphate group (outer-sphere). In aqueous solution, an equilibrium between the inner- and outer-sphere metal ion bindings can be established. The sugar moiety exhibited C'2-endo/anti conformation, in the free H2-AMP acid and the magnesium salt, C'3-endo/anti in the calcium salt and unusual C'4-exo/anti, in the strontium and barium salts.

Adenosine Monophosphate↗

PubMed1990

Raman spectroscopic study of the effects of Ca2+, Mg2+, Zn2+, and Cd2+ ions on calf thymus DNA: binding sites and conformational changes.

The interaction of Mg2+, Ca2+, Zn2+, and Cd2+ with calf thymus DNA has been investigated by Raman spectroscopy. These spectra reveal that all of these ions, and particularly Zn2+, bind to phosphate groups of DNA, causing a slight structural change in the polynucleotide at very small metal: DNA (P) concentration ratio (ca. 1:30). This results in increased base-stacking interactions, with negligible change of the B conformation of DNA. Contrary to Zn2+ and Cd2+, which interact extensively with the nucleic bases (particularly at the N7 position of guanine), the alkaline-earth metal ions are bound almost exclusively to the phosphate groups. The affinity of both the Zn2+ and Cd2+ ions for G.C base pairs is comparable, but the Cd2+ ions interact more extensively with A.T pairs than Zn2+ ions. Interstrand cross-linking through the N3 atom of cytosine is suggested in the presence of Zn2+, but not Cd2+.

Animals↗

PubMed1990

Coordination chemistry of vitamin C. Part I. Interaction of L-ascorbic acid with alkaline earth metal ions in the crystalline solid and aqueous solution.

The interaction of L-ascorbic acid with alkaline earth metal ions has been investigated in aqueous solution at pH 6-7. The solid salts of the type Mg(L-ascorbate)2.4H2O, Ca(L-ascorbate)2.2H2O, Sr(L-ascorbate)2.2H2O and Ba(L-ascorbate)2.2H2O were isolated and characterized by means of 13C NMR and FT-IR spectroscopy. Spectroscopic and other evidence suggested that in aqueous solution, the binding of the alkaline earth metal ions is through the O-3 atom of the ascorbate anion, while in the solid state the binding of the Mg(II) is different from those of the other alkaline earth metal ion salts. The Mg(II) ion binds to the O-3, O-1 atom of the two ascorbate anions and to two H2O molecules, while the eight-coordination around the Ca(II), Sr(II), and Ba(II) ions would be completed by the coordination of three acid anions, through O-5, O-6 of the first, O-3, O-5, O-6 of the second and O-1 of the third anion as well as to two H2O molecules. The structural properties of the alkaline earth metal-ascorbate salts are different in the solid and aqueous solution.

Ascorbic Acid↗

PubMed1990

Interaction of deoxyguanylic acid with alkaline earth metal ions. Evidence for the deoxyribose C3'-endo/anti, O4'-endo/anti and C2'-endo/anti conformational transitions.

The interaction of 2'-deoxyguanosine-5'-monophosphoric acid (H2-dGMP) with the alkaline earth metal ions has been investigated in aqueous solution at neutral pH. The solid salts of the type Mg-dGMP.5H2O Ca-dGMP.6H2O, Sr-dGMP.7H2O and Ba-dGMP.7H2O were isolated and characterized by FT-IR, proton-NMR and X-ray powder diffraction measurements. Two types of metal-nucleotide interactions have been identified: (a) the indirect metal-base and the direct metal-phosphate bindings (outer- and inner-sphere interaction), for the Mg(II) and Sr(II) ions and (b) the direct metal-base and direct metal-phosphate bindings (inner-sphere interaction), for the Ca(II) and Ba(II) ions. In aqueous solution, a dynamic equilibrium of the type base-metal-H2O. . .PO3 in equilibrium base. . .H2O-metal-PO3 is present. The deoxyribose moiety exhibits C3'-endo/anti conformation, in the Mg(II)-, Ca(II)-, Sr(II)- and Ba(II)-dGMP salts.

Biomarkers↗