Interaction of metal ions with 6-oxopurine nucleotides. Part 1. X-Ray structures of ternary cobalt(III) complexes with inosine 5'-monophosphate or guanosine 5'-monophosphate

The crystal structures of two ternary metal nucleotide complexes of cobalt, [Co(en)2(H2O)2]-[Co(5?-IMP)2(H2O)4]Cl2·4H2O (1) and [Co(en)2(H2O)2][Co(5?-GMP)2(H2O)4]Cl2·4H2O (2), have been analysed by X-ray diffraction (en = ethylenediamine, 5?-IMP = inosine 5?-monophosphate, and 5?-GMP = guanosine 5?-monophosphate). Both complexes crystallize in the orthorhombic space group C2221 with a= 8.725(1), b= 25.891(5), c= 21.212(5)Å, Z= 4 for (1) and a= 8.733(2), b= 26.169(4), c= 21.288(4)Å, Z= 4 for (2). The structure of (1) was solved by the heavy-atom method, while that of (2) was deduced from (1). The structures were refined to R values of 0.09 and 0.10 for 1 546 and 1 572 reflections for (1) and (2) respectively. The two structures are isomorphous. A novel feature is that the chelate ligand en and the nucleotide are not co-ordinated to the same metal ion. One of the metal ions lying on the two-fold a axis is octahedrally co-ordinated by two chelating en molecules and two water oxygens, while the other on the two-fold b axis is octahedrally co-ordinated by two N(7) atoms of symmetry-related nucleotides in a cis position and four water oxygens. The conformations of the nucleotides are C(2?)-endo, anti, and gauche�gauche. In both (1) and (2) the charge-neutralising chloride ions are disordered in the vacant space between the molecules. These structures bear similarities to the mode of nucleotide co-ordination to PtII complexes of 6-oxopurine nucleotides, which are the proposed models for intrastrand cross-linking in DNA by a metal complex.

Interaction of metal ions with 6-oxopurine nucleotides. Part 2. X-Ray structures of ternary nickel(II) complexes with 2'-deoxyguanosine 5'-monophosphate or guanosine 5'-monophosphate

The ternary metal nucleotide complexes [Ni(en)1.3(H2O)1.4(H2O)2][Ni(5?-dGMP)2(en)0.7-(H2O)0.6(H2O)2]·7H2O (1) and [Ni(en)2(H2O)2][Ni(5?-GMP)2(H2O)4]·6H2O (2)(en = ethylenediamine, 5?-dGMP = 2?-deoxyguanosine 5?-monophosphate, 5?-GMP = guanosine 5?-monophosphate) have been prepared and their structures analyzed by X-ray diffraction methods. Both compounds crystallise in the space group C2221 with a= 8.810(1), b= 25.090(4), c= 21.084(1)Å, and Z= 4 for (1) and a= 8.730(1), b= 25.691(4), c= 21.313(5)Å, and Z= 4 for (2). The structures were deduced from the analogous CoIII complexes and refined by full-matrix least-squares methods to final R values of 0.087 and 0.131 for 1 211 and 954 reflections for (1) and (2) respectively. An interesting feature of the deoxyribonucleotide complex (1) is that en is not totally labilized from the metal centre on nucleotide co-ordination, as observed in corresponding ribonucleotide complexes. Apart from extensive intra- and inter-molecular hydrogen bonding, the structures are stabilized by significant intracomplex base�base and base�sugar interactions. The nucleotides in both complexes have an anti base, C(2?)-endo sugar pucker, and gauche�gauche conformation about the C(4?)�C(5?) bond.

Mixed Azide and 5-(Pyrimidyl)tetrazole Bridged Co(II)/Mn(II) Polymers: Synthesis, Crystal Structures, Ferroelectric and Magnetic Behavior

The reaction of pyrimidine-2-carbonitrile, NaN3 in the presence of Co(NO3)(2)center dot 6H(2)O or MnCl2 center dot 4H(2)O leads to the formation of complexes Co(pmtz)(mu(1,3)-N-3)(H2O)](n) (1) and Mn(pmtz)(mu(1,3)-N-3)(H2O)](n) (2) respectively, under hydrothermal condition pmtz =5-(pyrimidyl)tetrazolate]. These two complexes have been fully characterized by single crystal X-ray diffraction. Complex 1 crystallizes in a non-centrosymmetric space group Aba2 in the orthorhombic system and is found to exhibit ferroelectric behavior, whereas complex 2 crystallizes in the P2(1)/c space group in the monoclinic system. Variable temperature magnetic characterizations in the temperature range of 2-300 K indicate that complex 1 is a canted antiferromagnet (weak ferromagnet) with T-c = 15.9 K. Complex 1 represents a unique example of a multiferroic coordination polymer containing tetrazole as a co-ligand. Complex 2 is a one-dimensional chain of Mn(II) bridged by a well-known antiferromagnetic coupler end-to-end azido ligand. In contrast to the role played by the end-to-end azido pathway in most of the transition metal complexes, complex 2 showed unusual ferromagnetic behavior below 40 K because of spin canting.

5-Benzyl-1-(4-fluorophenyl)-2-phenyl-4,5,6,7-tetrahydro-1H-pyrrolo3,2 -c] pyridine

In the title compound, C26H23FN2, the dihedral angle between the 4-fluorophenyl ring and the adjacent phenyl ring is 62.3 (1)degrees. The crystal structure is stabilized by C-H center dot center dot center dot pi interactions.

Synthesis, structure and magnetic properties of the polyoxovanadate cluster Zn-2(NH2(CH2)(2)NH2)(5)]{Zn(NH2(CH2)(2)NH2)(2)}(2){V18O42(H2O)\ ]center dot xH(2)O (x similar to 12), possessing a layered structure

A hydrothermal reaction of a mixture of ZnCl2, V2O5, ethylenediamine and water gave rise to a layered poly oxovanadate material. clusters. These clusters, with all the vanadium ions in the +4 state, are connected together through Zn(NH2(CH2)(2)NH2)(2) linkers forming a two-dimensional structure. The layers are also separated by distorted trigonal bipyramidal [Zn-2(NH2(CH2)(2)NH2)(5)] complexes. The Structure, thus, presents a dual role for the Zn-ethylenediamine complex. The magnetic susceptibility studies indicate that the interactions between the V centres in I are predominantly antiferromagnetic in nature and the compound shows highly frustrated behaviour. The magnetic properties are compared to the theoretical calculations based oil the Heisenberg model, in addition to correlating to the structure. Crystal data for the complexes are presented.

Structure of 1,2,4-oxadiazolidine-3,5-dione monohydrate

C2H2N203.H20, Mr= 120.07, monoclinic,P21/c, a= 5.011 (1), b= 11.796(2), c= 7.689 (2)A,fl= 95.22 (2) ° , V= 452.61 A 3, Z= 4, Dx= 1.76, D m = 1.75 gcm -3, /].(Cu Ks) = 1.5418 A, g = 14-0 cm -l,F(000) = 248, T = 293 K, crystal quality was poor and the final R =0.107, wR =0.090 for 881 observed reflections. The compound is derived from a novel form of the monopropellant oxalohydroxamic acid. The two exocyclic C-O bond lengths of 1.240 (3) and 1.228 (4)A indicate double bonds. The C-N bond lengths of 1.334 (4), 1.390 (4) and 1.359 (4) A are characteristic of the amide bond. The N atom covalently bonded to the two carbonyl C atoms acts as a proton donor in an intermolecular hydrogen bond to the ring O atom: N1...O3i = 2.854 ]k (i =x-- 1,y, z), H...O = 2.15 A, N-H...O = 159 °.

Structure of 6,5'-anhydro-6-hydroxy-2',3' O-isopropylideneuridine

CI2HI4N206, Mr=282"3, orthorhombic,P21212 t, a = 10.412 (2), b = 14.936 (2), c =16.651(3),/k, V=2589.46A 3, Z--8, Din= 1.450, D x = 1.447 Mg m -3, 2(Cu Kct) = 1.5418/~, # =0.902mm -~, F(000)-- 1184.00, T= 293 K, R = 0.039, wR--0.038 for 2548 unique reflections with F > 3a(F). The two crystallographically independent molecules in the asymmetric unit have similar geome-tries with the ribose ring having an O(4')-exo, C(4')-endo pucker and the uracil base in the anti conformation.The geometry about the exocyclic C(4')-C(5') bond in both molecules is gauche-gauche. The dioxolane ring assumes twist conformations in both molecules.

Temperature and thiol-induced desensitization of a Ca2+-sensitive cyclic-3',5'-nucleotide phosphodiesterase from sheep lung

Ca2+-sensitivity of sheep lung cyclic-3',5'-nucleotide phosphodiesterase is provided by endogenous tightly bound calmodulin. The calcium sensitivity of a highly purified enzyme was desensitized by increasing the assay temperature. It could also be desensitized to Ca2+-activation by thiols such as dithiothreitol. The thiol-induced desensitization could be partially reversed by dialysis and almost completely reversed by dilution. The results presented in this paper indicate that thiols are possibly involved in the interaction of calmodulin with cyclic-3',5'-nucleotide phosphodiesterase. This is the first report on temperature and thiol-induced desensitization of Ca2+-sensitivity of a cyclic-3',5'-nucleotide phosphodiesterase.

The structure of 3[beta],20[alpha]-bis(dimethylamino)pregn-5-en-18-ol

Abstract. C25H44N20 , M r= 388.6, orthorhombic, P21212 I, a = 6.185 (2), b = 18.123 (2), c = 20.852 (2) A, U= 2337.2 A 3, Z = 4, D x = 1.104 Mg m -a, 2(Cu Ka) = 1.5418 A,/~ = 0.47 mm -~, F(000) = 864, T= 293 K. Final R - 0.038 for 1791 reflections with I >_ 3a(I). Rings A and C are in chair conformation. Ring B is in an 8fl,9a-half-chair conformation. Ring D adopts a conformation in between 13fl,14a-half-chair and 13t-envelope. There is a quasitrans fusion of rings A and B, whilst ring systems B/C and C/D are trans fused about the bonds C(8)-C(9)and C(13)-C(14).

Mass analyser optics for wide-beam ion sources in ion implantation systems

Ion implantation systems, used for producing high-current ion beams, employ wide-beam ion sources which are rotated through 90 degrees . These sources need mass analyser optics which are different from the conventional design. The authors present results of calculation of the image distance as a function of entrance and exit angles of a sector magnet mass analyser having such a source. These computations have been performed for the magnetic deflection angles 45 degrees , 60 degrees and 90 degrees . The details of the computations carried out using the computer program MODBEAM, developed for this purpose, are also discussed.

Effect of grain size and texture on the mechanical properties of warm worked cadmium-1.5 Pct zinc alloy

The structural changes occurring during warm working of Cd-1.5 pct Zn alloy and their effect on the subsequent mechanical properties are studied. It is observed that changes in grain size and preferred orientation are important to a large extent in controlling the mechanical strength. The Hall-Petch slope,R decreases in the warm worked material while the friction stress, σo increases. The lowerR values are attributed to the development of a (101l) texture and the higher σo values are interpreted on the basis of changes in the basal texture.

Effect of phenyl and phenolic acids on mevalonate-5-Phosphate decarboxylase if the brain

Phenyl and phenolic acids are known to inhibit metabolism of mevalonate in rat brain. The site of inhibition has been found to be mevalonate-5-pyrophosphate decarboxylase. Phenolic acids also inhibited mevalonate-5-phosphate kinase on preincubation. The kinetics showed that p-coumaric acid and isoferulic acid were competing with substrates, mevalonate-5-phosphate or mevalonate-5-pyre phosphate, whereas others showed an uncompetitive type of inhibition. Chlorophenoxyisobutyrate, a hypocholesterolaemic drug, had no effect on these enzymes. An improved method for the synthesis of mevalonate-5-phosphate and mevalonate-5-pyrophosphate, labeled at carbon-1, is described.