Fast, copper-free click chemistry: a convenient solid-phase approach to oligonucleotide conjugation

Solid-phase oligonucleotide conjugation by nitrile oxide-alkyne click cycloaddition chemistry has been successfully demonstrated; the reaction, compatible with all nucleobases, requires no metal catalyst and proceeds under physiological conditions.

Carbon chemistry in Galactic bulge planetary nebulae

Galactic bulge planetary nebulae show evidence of mixed chemistry with emission from both silicate dust and polycyclic aromatic hydrocarbons (PAHs). This mixed chemistry is unlikely to be related to carbon dredge-up, as third dredge-up is not expected to occur in the low-mass bulge stars. We show that the phenomenon is widespread and is seen in 30 nebulae out of 40 of our sample, selected on the basis of their infrared flux. Hubble Space Telescope (HST) images and Ultraviolet and Visual Echelle Spectrograph (UVES) spectra show that the mixed chemistry is not related to the presence of emission-line stars, as it is in the Galactic disc population. We also rule out interaction with the interstellar medium (ISM) as origin of the PAHs. Instead, a strong correlation is found with morphology and the presence of a dense torus. A chemical model is presented which shows that hydrocarbon chains can form within oxygen-rich gas through gas-phase chemical reactions. The model predicts two layers, one at A_V~ 1.5, where small hydrocarbons form from reactions with C+, and one at A_V~ 4, where larger chains (and by implication, PAHs) form from reactions with neutral, atomic carbon. These reactions take place in a mini-photon-dominated region (PDR). We conclude that the mixed-chemistry phenomenon occurring in the Galactic bulge planetary nebulae is best explained through hydrocarbon chemistry in an ultraviolet (UV)-irradiated, dense torus.

A click chemistry approach to C3 symmetric, G-quadruplex stabilising ligands.

Described is the structure-based design and synthesis of a series of tris-triazole G-quadruplex binding ligands utilising the copper catalysed azide–alkyne ‘click’ reaction. The results of G-quadruplex stabilisation by the ligands are reported and discussed.

Targeting telomerase and telomeres: a click chemistry approach towards highly selective G-quadruplex ligands.

Maintenance of telomeres—specialized complexes that protect the ends of chromosomes, is undertaken by the enzyme complex telomerase, which is a key factor that is activated in more than 80% of cancer cells, but is absent in most normal cells. Targeting telomere maintenance mechanisms could potentially halt tumour growth across a broad spectrum of cancer types, with little cytotoxic effect outside cancer cells. Here, we describe in detail a new class of G-quadruplex binding ligands synthesized using a click chemistry approach. These ligands comprise a 1,3-di(1,2,3-triazol-4-yl)benzene pharmacophore, and display high levels of selectivity for interaction with G-quadruplex DNA vs. duplex DNA. The ability of these ligands to inhibit the enzymatic activity of telomerase correlates with their ability to stabilize quadruplex DNA, and with estimates of affinity calculated by molecular modeling.

Gas and grain chemistry in a protoplanetary disk

The chemistry in a protoplanetary accretion disk is modelled between a radius of 100 and 0.1 AU of the central object. We find that interaction of the gas with the dust grains is very important, both by removing a large fraction of the material from the gas in the outer regions and through the chemical reactions which can occur on the dust grain surfaces. In addition, collision with grains neutralises gaseous ions effectively and keeps the ionization fraction low. This results in a chemistry which is dominated by neutral-neutral reactions, even if ionization is provided by cosmic rays or by the decay of radioactive isotopes. We model the effects of two desorption processes with very different efficiencies and find that while these produce similar results over much of the disk for many species, some molecules are extremely sensitive to the nature of the desorption and may one day be used as an observational test for the desorption process.

Sulphur chemistry and evolution in hot cores

We compare the results of our JCMT spectral line survey of molecular gas towards ultracompact HII regions with the predictions of models of sulphur chemistry in hot cores. We investigate the range of evolutionary models that are consistent with the observed physical conditions and chemical abundances, and see to what extent it is possible to constrain core ages by comparing abundances with the predictions of chemical models. The observed abundance ratios vary little from source to source, suggesting that all the sources are at a similar evolutionary stage. The models are capable of predicting the observed abundances of H2S, SO, SO2, and CS. The models fail to predict the amount of OCS observed, suggesting that an alternative formation route is required. An initial H2S abundance from grain mantle evaporation of similar to 10(-7) is preferred.

Chemistry in oxygen-rich circumstellar envelopes

We have considered the chemistry occuring in the circumstellar envelope surrounding an oxygen-rich AGE star and have specifically modelled 4 sources; R Dor, TX Cam, OH231.8+4.2 and IK Tau. Methane has been assumed to be a parent molecule and the resulting carbon chemistry is investigated. We find that carbon chain molecules up to C2H4 can be abundant as can CH3CN and CH3OH. Our model extends previous work by including the chemistry of silicon, chlorine and phosphorus. The presence of CH4 as a parent and hence its daughter species CH3 and CH3+ leads to other carbon-bearing species such as H2CS, SiCH2, H2CN and CCl.

Chemistry in anisotropic asymptotic giant branch winds

We have constructed a model for chemistry in the outflow of an asymptotic giant branch (AGB) star, using a spheroidal anisotropy in density, after that used by Jura. The predicted distributions of a selection of representative species are shown, and it is suggested that the abundance distributions observed by interferometry in IRC + 10216 may be the result of directional variation in outflow velocity.

The chemistry of deuterium in hot molecular cores

This paper presents the results of a model of the chemistry of deuterium-bearing molecules in hot molecular cores. It is found that because hydrogen- and deuterium-bearing molecules are destroyed by the same reactions at about the same rates, the initial fractionation present in ice mantles persists for over 10(4) yr. This is the case for a wide range of physical conditions, so it is safe to infer the fractionation on grain surfaces from observations of deuterated molecules in hot cores. The implications of the observed abundances of deuterium-bearing species in Orion are then discussed.

THE CHEMISTRY OF COMPLEX-MOLECULES IN INTERSTELLAR CLOUDS

This paper is concerned with the chemical evolution of large molecules in interstellar clouds. We consider the chemistry and ionisation balance of large polycyclic aromatic hydrocarbon (PAH) type molecules in diffuse clouds and show that certain PAH molecules can be doubly ionised by the interstellar ultraviolet radiation field. If recombination of the dications so produced with electrons is dissociative rather than radiative, then PAHs are rapidly destroyed. PAHs which can only be singly ionised have much smaller recombination energies and can be long lasting in these regions. This type of property may be very important in selecting the PAH species which can populate the general interstellar medium and account for certain of the diffuse bands observed in optical spectra. Destruction of PAH molecules via formation of dications may be responsible for the weakening of the diffuse bands observed in regions of high UV flux.

THE CHEMISTRY OF PHOSPHORUS IN HOT MOLECULAR CORES

Hot molecular cores in star-forming regions are known to have gas-phase chemical compositions determined by the material evaporated from the icy mantles of interstellar grains, followed by subsequent reactions in the gas phase. Current models suggest that the evaporated material is rich in hydrogenated species. In this paper, we consider the chemistry induced in a hot core by the release of phosphine, PH3 from interstellar grains. We find that PH3 is rapidly destroyed by a series of reactions with atomic hydrogen and is converted, within 10(4) yr, into atomic P, and PO and PN, with P atoms being the most abundant species. Other P-bearing molecules can be formed in the hot gas, but on time-scales that are long compared to those of the hot cores.

THE EFFECT OF VARYING COSMIC-RAY IONIZATION RATES ON DARK CLOUD CHEMISTRY

We investigate the effects of varying the cosmic ray ionization rate in chemical models of dense interstellar clouds. In the absence of such ionization, a scenario which may be applicable to dark cloud cores, we find that chemi-ionization is able to drive a limited ion-neutral chemistry. Models of clouds in starburst galaxies, which may have enhanced cosmic ray fluxes, are also investigated and enable an upper limit to be derived for the cosmic ray ionization rate in M82. The derived value, which is about 700 times the typical value for Galactic molecular clouds, is in good agreement with that necessary to explain the recent observations of C I in this galaxy.