Mesoporous Carbons from Polysaccharides and Their Use in Li-O2 Batteries.

Previous studies have demonstrated that the mesoporosity of carbon material obtained by the Starbon® process from starch-formed by amylose and amylopectin can be tuned by controlling this ratio (the higher the amylose, the higher the mesoporosity). This study shows that starch type can also be an important parameter to control this mesoporosity. Carbons with controlled mesoporosity (Vmeso from 0.1-0.7 cm3/g) have been produced by the pre-mixing of different starches using an ionic liquid (IL) followed by a modified Starbon® process. The results show that the use of starch from corn and maize (commercially available Hylon VII with maize, respectively) is the better combination to increase the mesopore volume. Moreover, "low-cost" mesoporous carbons have been obtained by the direct carbonization of the pre-treated starch mixtures with the IL. In all cases, the IL can be recovered and reused, as demonstrated by its recycling up to three times. Furthermore, and as a comparison, chitosan has been also used as a precursor to obtain N-doped mesoporous carbons (5.5 wt% N) with moderate mesoporosity (Vmeso = 0.43 cm3/g). The different mesoporous carbons have been tested as cathode components in Li-O2 batteries and it is shown that a higher carbon mesoporosity, produced from starch precursor, or the N-doping, produced from chitosan precursor, increase the final battery cell performance (specific capacity and cycling).

Self-assembly of a bis(adeninyl)-Cu(I) complex: a cationic nucleobase duplex mimic.

The tetrahedral bis(adeninyl)-Cu(I) complex, , self-associates in polar solvent through complementary hydrogen-bonding interactions and appears to mimic the natural assembly of duplex DNA.

Reactions of Pd(II) with chelate-tethered 2,6-diaminopurine derivatives: N3-coordination and reaction of the purine system.

Alkyldiamine-tethered derivatives of 2,6-diaminopurine, ethylenediamine-N9-propyl-2,6-diaminopurine, L1, and ethylenediamine-N9-ethyl-2,6-diaminopurine, L2, react with Pd(II) to give N3-coordinated complexes. However, the exact nature of the resulting complex is dependent on the reaction conditions. With PdCl(2)(MeCN)(2) in MeCN/H(2)O the expected [PdCl(N3-2,6-DAP-alkyl-en)](+) complex, 1, is formed with L1 chelating the metal center in a tridentate manner through the diamine function and N3 of the purine base. However, under the same conditions the shorter, ethyl-tethered, L2 gives a complex dication, 2, containing a tetradentate ligand forming simultaneously 5-, 6-, and 7-membered chelate rings. This resulting acetamidine, derived by addition to coordinated MeCN, appears to be the first such case involving the 2-amino group of a purine. The ethyl-analogue of 1, [PdCl(N3-2,6-DAP-Et-en)](+) 3, was prepared by reaction of L2 with K(2)PdCl(4) in aqueous media.

Probing metal-ion purine interactions at DNA minor-groove sites.

The effect of the 2-amino group on metal ion binding at the N3-position of a purine base has been investigated using chelate-tethered derivatives. Reactions of diamine-tethered 2,6-diaminopurine (DAP) with divalent d-block metal ions Cu(II) and Cd(II) confirm that binding can occur, but this is much less prevalent than with adenine. In this regard DAP is similar to guanine where we have previously observed a general lack of N3-binding by divalent metal ions compared to adenine (e.g., Houlton et al., Angew. Chem., Int. Ed. 2000, 39, 2360; Chem.-Eur. J. 2000, 6, 4371). For the univalent d-block metals ions, Cu(I) and Ag(I), binding to adenine N3 is not observed in the solid state, as shown by reactions with dithioether-tethered adenine derivatives. Instead, depending on stoichiometry of the reaction, discrete (with metal/ligand ratio 1:2) or polymeric (with metal/ligand ratio 1:1) complexes were isolated and characterized by single crystal X-ray methods. In the former the nucleobases are pendant and involved in base-pair interactions, with both Watson-Crick...Watson-Crick and Hoogsteen...Hoogsteen type pairings present. For the coordination polymers a rather unexpected influence of the tether length on the site of nucleobase binding is found for bridging ligand binding modes involving the chelating diamine and the adeninyl group. Polymer chains derived with the shorter ethyl tether show binding at the N7 site of adeninyl, while binding at N1 is found in the longer propyl chain length.

Multiple metal binding to 6-oxopurine nucleobases as a source of deprotonation. The role of metal ions at N7 and N3.

Simultaneous metal coordination to N7 (Pt(II)) and N3 (Pd(II)) of N9-blocked guanine leads to a 10(4) fold acidification of the guanine-N(1)H position and hence to a virtual complete deprotonation of the N(1)H position at neutral pH. The chelate-tethered nucleobase ethylenediamine-N9-ethylguanine was employed and relevant acid-base equilibria were studied by pD dependent 1H NMR spectroscopy. CH2 resonances of the tether were assigned on the basis of NOESY and COSY experiments. Our findings suggest a plausible method of formation of a previously reported trinuclear Pt(II) complex of 9-ethylguanine with metals coordinated to N1, N3 and N7. According to this, a sequence with the first metal binding to N7, the second one binding to N3, and only the third one binding to N1 with deprotonation of this site is proposed.

Minor groove site coordination of adenine by platinum group metal ions: effects on basicity, base pairing, and electronic structure.

Dithioether- or diamine-tethered adenine derivatives react with Pt(II), Pd(II), and Rh(III) ions to give N3-coordinated complexes of the types [MCl(SSN)](+) (M = Pt or Pd), [RhCl(3)(SSN)], or [RhCl(3)(NNN)] (where SSN = 1-(N9-adenine)-3,6-dithia-heptane or 1-(N9-adenine)-4,7-dithia-octane; NNN = ethylenediamine-N,9-ethyladenine). Single-crystal X-ray analysis confirms the nature of the metal-nucleobase interaction and highlights a conserved intermolecular hydrogen-bonding motif for all the complexes, irrespective of the metal-ion geometry. Coordination significantly reduces the basicity of the adeninyl group, as indicated by a pK(a) value of -0.16 for [PtCl(N3-1-(N9-adenine)-3,6-dithia-heptane)]BF(4), compared to a pK(a) value of 4.2 for 9-ethyladenine. The site of proton binding, N1 or N7, could not be unambiguously assigned from the (1)H NMR data, because of the similar effect on the chemical shifts of the H2 and H8 protons. Density functional calculations at the BP-LACVP level suggest N1 as the site of protonation for this type of complex. This is in contrast to the N7-protonation reported for [Pt(dien)(N3-6,6',9-trimethyladenine)](2+), as reported elsewhere (Meiser et al., Chem.-Eur. J. 1997, 3, 388). However, further electronic structure calculations in the gas phase reveal that the preferred site for protonation for N3-bound complexes is conformationally dependent. N3 coordination was also found to reduce the extent of base pairing between adenine and thymine in dimethylsulfoxide for the self-complementary complex [PtCl(L3)](+) (L3 = 1-(N9-adenine)-3,6-dithia-9-(N1-thymine)nonane), compared to that for the uncomplexed ligand.