The Ground And Excited States Of Aromatic Oxide Radicals Via Anion Photoelectron Spectroscopy

Aromatic oxide free radicals play an important role in atmospheric and combustion chemistry, where they are involved in the formation of secondary organic aerosols and soot. The oxygen atom lone pairs can readily mix with the aromatic system giving rise to extensive electronic delocalization and influencing molecular reactivity. The oxygen atom also imparts a significant dipole moment to the radical system, which supports low-lying resonance and dipole bound states. We probed three cryogenically cooled aromatic oxide radicals (phenoxy, 1-naphthoxy, 2-naphthoxy) via Slow Electron Velocity Map Imaging (SEVI) to unravel their electronic and vibrational structure. We determined electron affinities and excited state energies for the three systems, and observed numerous active vibrational modes. Resonant photoexcitation to the dipole bound state was found to drastically alter the observed vibrational structure, and care was taken to avoid these resonances during direct photodetachment studies

Alkali metal-glucose interaction probed with infrared pre-dissociation spectroscopy

The efficient extraction of cellulose from biomass and its subsequent conversion to glucose derivatives is an attractive goal in the field of energy science. However, current industrial methods require high ionic strength and harsh conditions. Ionic liquids (IL�s) are a class of �green� compounds that have been shown to dissolve cellulose in concentrations of up to 25 wt%. In order to understand IL�s extraordinary cellulose dissolving power, a molecular level understanding of the IL-cellulose interaction is needed. Toward that end, we have acquired infrared pre-dissociation spectra of M$^{+}$-glucose, where M$^{+}$=Li$^{+}$, Na$^{+}$, or K$^{+}$. Through comparisons with density functional theory calculations, we have determined the relative abundances of various M$^{+}$-glucose binding motifs in both the thermodynamic and kinetic limits. These results provide insight on the hydrogen bonding dynamics of glucose and are a step towards a fuller understanding of cellulose interactions with ionic liquids

The lncRNA landscape of breast cancer reveals a role for DSCAM-AS1 in breast cancer progression.

Molecular classification of cancers into subtypes has resulted in an advance in our understanding of tumour biology and treatment response across multiple tumour types. However, to date, cancer profiling has largely focused on protein-coding genes, which comprise <1% of the genome. Here we leverage a compendium of 58,648 long noncoding RNAs (lncRNAs) to subtype 947 breast cancer samples. We show that lncRNA-based profiling categorizes breast tumours by their known molecular subtypes in breast cancer. We identify a cohort of breast cancer-associated and oestrogen-regulated lncRNAs, and investigate the role of the top prioritized oestrogen receptor (ER)-regulated lncRNA, DSCAM-AS1. We demonstrate that DSCAM-AS1 mediates tumour progression and tamoxifen resistance and identify hnRNPL as an interacting protein involved in the mechanism of DSCAM-AS1 action. By highlighting the role of DSCAM-AS1 in breast cancer biology and treatment resistance, this study provides insight into the potential clinical implications of lncRNAs in breast cancer

Gas Phase Spectra And Structural Determination Of Glucose 6 Phosphate Using Cryogenic Ion Vibrational Spectroscopy

Glucose-6-Phosphate (G6P) is one member of a class of simple phosphorylated sugars that are relevant in biological processes. We have acquired a gas phase infrared spectrum of G6P$^{-}$ using cryogenic ion vibrational spectroscopy (CIVS) in a home-built spectrometer. The experimental spectrum was compared with calculated vibrational spectra from a systematic conformer search. For both of the $\alpha$ and $\beta$ anomers, results show that only the lowest energy conformers are present in the gas phase. If spectral signatures for similar sugars could be cataloged, it would allow for conformer-specific determination of mixture composition, for example, for glycolyzation processes