Preparation of controlled porosity carbon-aerogels for energy storage in rechargeable lithium oxygen batteries

Porous carbon aerogels are prepared by polycondensation of resorcinol and formaldehyde catalyzed by sodium carbonate followed by carbonization of the resultant aerogels in an inert atmosphere. Pore structure of carbon aerogels is adjusted by changing the molar ratio of resorcinol to catalyst during gel preparation and also pyrolysis under Ar and activation under CO2 atmosphere at different temperatures. The prepared carbons are used as active materials in fabrication of composite carbon electrodes. The electrochemical performance of the electrodes has been tested in a Li/O2 cell. Through the galvanostatic charge/discharge measurements, it is found that the cell performance (i.e. discharge capacity and discharge voltage) depends on the morphology of carbon and a combined effect of pore volume, pore size and surface area of carbon affects the storage capacity. A Li/O2 cell using the carbon with the largest pore volume (2.195cm3/g) and a wide pore size (14.23 nm) showed a specific capacity of 1290mAh g-1.

Preparation of Aqueous Core/Polymer Shell Microcapsules by Internal Phase Separation

Aqueous core/polymer shell microcapsules with mommuclear and polynuclear core morphologies have been formed by internal phase separation from water-in-oil emulsions. The water-in-oil emulsions were prepared with the shell polymer dissolved in the aqueous phase by adding a low boiling point cosolvent. Subsequent removal of this cosolvent (by evaporation) leads to phase separation of the polymer and, if the spreading conditions are correct, formation of a polymer shell encapsulating the aqueous core. Poly(tetrahydrofuran) (PTHF) shell/aqueous core microcapsules, with a single (mononuclear) core, have been prepared, but the low T-g (-84 degreesC) of PTHF makes characterization of the particles more difficult. Poly(methyl methacrylate) and poly(isobutyl methacrylate) have higher T-g values (105 and 55 degreesC, respectively) and can be dissolved in water at sufficiently high acetone concentrations, but evaporation of the acetone from the emulsion droplets in these cases mostly resulted in polynuclear capsules, that is, having cores with many very small water droplets contained within the polymer matrix. Microcapsules with fewer, larger aqueous droplets in the core could be produced by reducing the rate of evaporation of the acetone. A possible mechanism for the formation of these polynuclear cores is suggested. These microcapsules were prepared dispersed in an oil-continuous phase. They could, however, be successfully transferred to a water-continuous phase, using a simple centrifugation technique. In this way, microcapsules with aqueous cores, dispersed in an aqueous medium, could be made. It would appear that a real challenge with the water-core systems, compared to the previous oil-core systems, is to obtain the correct order of magnitude of the three interfacial tensions, between the polymer, the aqueous phase, and the continuous oil phase; these control the spreading conditions necessary to produce shells rather than "acorns".

Synthesis of N3- and 2-NH2-substituted 6,7-diphenylpterins and their use as intermediates for the preparation of oligonucleotide conjugates designed to target photooxidative damage on single-stranded DNA representing the bcr-abl chimeric gene

Two 17-mer oligodeoxynucleotide-5'-linked-(6,7-diphenylpterin) conjugates, 2 and 3, were prepared as photosensitisers for targeting photooxidative damage to a 34-mer DNA oligodeoxynucleotide (ODN) fragment 1 representing the chimeric bcr-abl gene that is implicated in the pathogenesis of chronic myeloid leukaemia (CML). The base sequence in the 17-mer was 3'G G T A G T T A T T C C T T C T T5'. In the first of these ODN conjugates (2) the pterin was attached at its N3 atom, via a -(CH2)3OPO(OH)- linker, to the 5'-OH group of the ODN. Conjugate 2 was prepared from 2-amino-3-(3-hydroxypropyl)-6,7-diphenyl-4(3H)-pteridinone 10, using phosphoramidite methodology. Starting material 10 was prepared from 5-amino-7-methylthiofurazano[3,4-d]pyrimidine 4 via an unusual highly resonance stabilised cation 8, incorporating the rare 2H,6H-pyrimido[6,1-b][1,3]oxazine ring system. In the characterisation of 10 two pteridine phosphazenes, 15 and 29, were obtained, as well as new products containing two uncommon tricyclic ring systems, namely pyrimido[2,1-b]pteridine (20 and 24) and pyrimido[1,2-c]pteridine (27). In the second ODN conjugate the linker was -(CH2)5CONH(CH2)6OPO(OH)- and was attached to the 2-amino group of the pterin. In the preparation of 3, the N-hydroxysuccinimide ester 37 of 2-(5-carboxypentylamino)-6,7-diphenyl-4(3H)-pteridinone was condensed with the hexylamino-modified 17-mer. Excitation of 36 with near UV light in the presence of the single-stranded target 34-mer, 5'T G A C C A T C A A T A A G14 G A A G18 A A G21 C C C T T C A G C G G C C3' 1 caused oxidative damage at guanine bases, leading to alkali-labile sites which were monitored by polyacrylamide gel electrophoresis. Cleavage was observed at all guanine sites with a marked preference for cleavage at G14. In contrast, excitation of ODN-pteridine conjugate 2 in the presence of 1 caused oxidation of the latter predominantly at G18, with a smaller extent of cleavage at G15 and G14 (in the double-stranded portion) and G21. These results contrast with our previous observation of specific cleavage at G21 with ruthenium polypyridyl sensitisers, and suggest that a different mechanism, probably one involving Type 1 photochemical electron transfer, is operative. Much lower yields were found with the ODN-pteridine conjugate 3, perhaps as a consequence of the longer linker between the ODN and the pteridine in this case.

2,4-dinitrophenol as an activating reagent in a facile preparation of cyclic phosphate trimesters

Abstract 2,4-Dinitrophenol was employed with benzyloxy-bis-(diisopropylamino)phosphine to synthesise the cyclic phosphate derivatives of a series of alkane diols (HO–(CH2)n–OH, n=2–6) in good isolated yields. Tetrazole and DNP were compared by 31P NMR spectroscopy for their ability to catalyse the cyclisation at the P(III) stage. Investigation of the phosphate triester stability under various oxidation and chromatographic conditions resulted in the optimisation of the isolation procedures of the chemically unstable cyclic compounds. Conditions for debenzylation were developed to yield the corresponding cyclic phosphodiesters quantitatively. The methodology was further applied to the preparation and isolation of the cyclic phosphate derivative of a carbohydrate.

Enantiocomplementary preparation of (S)- and (R)-1-pyridylalkanols via ketone reduction and alkane hydroxylation using whole cells of Pseudomonas putida UV4

A previously unreported alcohol dehydrogenase enzyme in the mutant soil bacterium Pseudomonas putida UV4 catalyses the reduction of 2-, 3- and 4-acylpyridines to afford the corresponding (S)-1-pyridyl alkanols, with moderate to high e.e., whilst under the same conditions 2,6-diacetylpyridine is readily converted to the corresponding enantiopure C2-symmetric (S,S)-diol in one step. In contrast, the toluene dioxygenase enzyme in the same organism catalyses the hydroxylation of 2- and 3-alkylpyridines to (R)-1-(2-pyridyl) and (R)-1-(3-pyridyl)alkanols. This combination of oxidative and reductive biotransformations thus provides a method for preparing both enantiomers of chiral 1-pyridyl alkanols using one biocatalyst.

Preparation of Potential Cell-Permeant Nucleoside-2',3'-Cyclic Phosphate Precursors

Uridine-3'-phosphorothiolate triesters bearing lipophilic moieties were prepared via Michaelis-Arbuzov chemistry. Subsequent deprotection of the S-cholesteryl phosphorothiolate triester afforded the corresponding diester which underwent spontaneous Cyclization to cleanly afford uridine 2',3'-cyclic phosphate. This transesterification reaction could be expedited by treatment with iodine under mild, neutral conditions.

A simple method for the preparation of 3-hydroxyiminodehydroquinate, a potent inhibitor of type II dehydroquinase

A number of routes to hydroxyiminodehydroquinate, one of the most potent inhibitors of type II dehydroquinase that is currently known, have been investigated. Methods based on the existing literature synthesis, i.e. oxime formation of a suitably C-4 and C-5 protected methyl 3-dehydroquinate derivative were initially studied. Benzoyl protection did give the desired product but in low overall yield. An alternative BBA protection strategy starting with a protected dehydroquinate was successful in generating a C4/C5 analogue of the desired oxime in high yield. Further investigation revealed that it was unecessary to protect the dehydroquinate precursor, hence the potassium salt corresponding to the desired oxime was simply synthesised as a single isomer from methyl dehydroquinate.