High-Pressure Synthesis of a Pentazolate Salt

The pentazolates, the last all-nitrogen members of the azole series, have been notoriously elusive for the last hundred years despite enormous efforts to make these compounds in either gas or condensed phases. Here we report a successful synthesis of a solid state compound consisting of isolated pentazolate anions N5-, which is achieved by compressing and laser heating cesium azide (CsN3) mixed with N2 cryogenic liquid in a diamond anvil cell. The experiment was guided by theory, which predicted the transformation of the mixture at high pressures to a new compound, cesium pentazolate salt (CsN5). Electron transfer from Cs atoms to N5 rings enables both aromaticity in the pentazolates as well as ionic bonding in the CsN5 crystal. This work provides a critical insight into the role of extreme conditions in exploring unusual bonding routes that ultimately lead to the formation of novel high nitrogen content species

Tetrahymena thermophila and Candida albicans Group I intron-derived ribozymes can catalyze the trans-excision-splicing reaction

Group I intron-derived ribozymes can catalyze a variety of non-native reactions. For the trans-excision-splicing (TES) reaction, an intron-derived ribozyme from the opportunistic pathogen Pneumocystis carinii catalyzes the excision of a predefined region from within an RNA substrate with subsequent ligation of the flanking regions. To establish TES as a general ribozyme-mediated reaction, intron-derived ribozymes from Tetrahymena thermophila and Candida albicans, which are similar to but not the same as that from Pneumocystis, were investigated for their propensity to catalyze the TES reaction. We now report that the Tetrahymena and Candida ribozymes can catalyze the excision of a single nucleotide from within their ribozyme-specific substrates. Under the conditions studied, the Tetrahymena and Candida ribozymes, however, catalyze the TES reaction with lower yields and rates [Tetrahymena (kobs) = 0.14/min and Candida (kobs) = 0.34/min] than the Pneumocystis ribozyme (kobs = 3.2/min). The lower yields are likely partially due to the fact that the Tetrahymena and Candida catalyze additional reactions, separate from TES. The differences in rates are likely partially due to the individual ribozymes ability to effectively bind their 3′ terminal guanosines as intramolecular nucleophiles. Nevertheless, our results demonstrate that group I intron-derived ribozymes are inherently able to catalyze the TES reaction

Vibrational Spectroscopy of Fe(OH)2 at High Pressure: Behavior of the O-H Bond

Infrared and Raman spectra of Fe(OH){sub 2}, ''white rust'', were measured between 7 GPa and 21 GPa at ambient temperature. The frequency of the infrared-active A{sub 2u} and of the Raman-active A1g stretching modes of the O-H group decrease linearly with pressure with slopes of -1.3 {+-} 0.1 cm{sup -1}/GPa and -4.9 {+-} 0.2 cm{sup -1}/GPa, respectively. The peak widths of both the infrared-active and Raman-active modes increase non-linearly with pressure, with a discontinuous increase of in broadening between 10 and 12.5 GPa. The overall broadening of the A{sub 2u} and of the A{sub 1g} stretching modes is approximately four-fold in the examined pressure range. The results of this spectroscopic study are compatible with the trends observed in recent neutron diffraction studies in the isostructural Co(OH){sub 2}. Progressive pressure-induced H disordering could be a viable model to interpret both the broadening of the OH stretching mode and the changes in oxidation state of Fe recently observed by Moessbauer spectroscopy

The Melting Curve and High-Pressure Chemistry of Formic Acid to 8 GPa and 600 K

We have determined the melting temperature of formic acid (HCOOH) to 8.5 GPa using infrared absorption spectroscopy, Raman spectroscopy and visual observation of samples in a resistively heated diamond-anvil cell. The experimentally determined melting curve compares favorably with a two-phase thermodynamic model. Decomposition reactions were observed above the melting temperature up to a pressure of 6.5 GPa, where principal products were CO{sub 2}, H{sub 2}O and CO. At pressures above 6.5 GPa, decomposition led to solid-like reaction products. Infrared and Raman spectra of these recovered products indicate that pressure affects the nature of carbon-carbon bonding

Human telomeres that contain (CTAGGG)n repeats show replication dependent instability in somatic cells and the male germline

A number of different processes that impact on telomere length dynamics have been identified but factors that affect the turnover of repeats located proximally within the telomeric DNA are poorly defined. We have identified a particular repeat type (CTAGGG) that is associated with an extraordinarily high mutation rate (20% per gamete) in the male germline. The mutation rate is affected by the length and sequence homogeneity of the (CTAGGG)n array. This level of instability was not seen with other sequence-variant repeats, including the TCAGGG repeat type that has the same composition. Telomeres carrying a (CTAGGG)n array are also highly unstable in somatic cells with the mutation process resulting in small gains or losses of repeats that also occasionally result in the deletion of the whole (CTAGGG)n array. These sequences are prone to quadruplex formation in vitro but adopt a different topology from (TTAGGG)n (see accompanying article). Interestingly, short (CTAGGG)2 oligonucleotides induce a DNA damage response (γH2AX foci) as efficiently as (TTAGGG)2 oligos in normal fibroblast cells, suggesting they recruit POT1 from the telomere. Moreover, in vitro assays show that (CTAGGG)n repeats bind POT1 more efficiently than (TTAGGG)n or (TCAGGG)n. We estimate that 7% of human telomeres contain (CTAGGG)n repeats and when present, they create additional problems that probably arise during telomere replication