Studies on the mechanism of the peroxyoxalate chemiluminescence reaction Part 1. Confirmation of 1,2-dioxetanedione as an intermediate using 13C nuclear magnetic resonance spectroscopy

A simple model peroxyoxalate chemiluminescence system was monitored directly across a range of temperatures (from −80 to +20 °C) using 13C nuclear magnetic resonance spectroscopy. These experiments were made possible by the utilisation of 13C doubly labelled oxalyl chloride, which was reacted with anhydrous hydrogen peroxide in dry tetrahydrofuran. Ab initio quantum calculations were also performed to estimate the 13C nuclear magnetic resonance (NMR) shift of the most commonly postulated key intermediate 1,2-dioxetanedione and this data, in concert with the spectroscopic evidence, confirmed its presence during the reaction

Green chemiluminescence from a bis-cyclometalated iridium(III) complex with an ancillary bathophenanthroline disulfonate ligand

The reaction of a fluorinated iridium complex with cerium(IV) and organic reducing agents generates an intense emission with a significant hypsochromic shift compared to contemporary chemically-initiated luminescence from metal complexes

How to move ionized gas: an introduction to the dynamics of HII regions

This review covers the dynamic processes that are important in the evolution and structure of galactic HII regions, concentrating on an elementary presentation of the physical concepts and recent numerical simulations of HII region evolution in a non-uniform medium. The contents are as follows: (1) The equations (Euler equations; Radiative transfer; Rate equations; How to avoid the dynamics; How to avoid the atomic physics). (2) Physical concepts (Static photoionization equilibrium; Ionization front propagation; Structure of a D-type front; Photoablation flows; Other ingredients - Stellar winds, Radiation pressure, Magnetic fields, Instabilities). (3) HII region evolution (Early phases: hypercompact and ultracompact regions; Later phases: compact and extended regions; Clumps and turbulence).Comment: To be published as a chapter in 'Diffuse Matter from Star Forming Regions to Active Galaxies' - A volume Honouring John Dyson. Eds. T. W. Harquist, J. M. Pittard and S. A. E. G. Falle. 25 pages, 7 figures. Some figures degraded to meet size restriction. Full-resolution version available at http://www.ifront.org/wiki/Dyson_Festschrift_Chapte

31st Annual Meeting and Associated Programs of the Society for Immunotherapy of Cancer (SITC 2016) : part two

Background The immunological escape of tumors represents one of the main ob- stacles to the treatment of malignancies. The blockade of PD-1 or CTLA-4 receptors represented a milestone in the history of immunotherapy. However, immune checkpoint inhibitors seem to be effective in specific cohorts of patients. It has been proposed that their efficacy relies on the presence of an immunological response. Thus, we hypothesized that disruption of the PD-L1/PD-1 axis would synergize with our oncolytic vaccine platform PeptiCRAd. Methods We used murine B16OVA in vivo tumor models and flow cytometry analysis to investigate the immunological background. Results First, we found that high-burden B16OVA tumors were refractory to combination immunotherapy. However, with a more aggressive schedule, tumors with a lower burden were more susceptible to the combination of PeptiCRAd and PD-L1 blockade. The therapy signifi- cantly increased the median survival of mice (Fig. 7). Interestingly, the reduced growth of contralaterally injected B16F10 cells sug- gested the presence of a long lasting immunological memory also against non-targeted antigens. Concerning the functional state of tumor infiltrating lymphocytes (TILs), we found that all the immune therapies would enhance the percentage of activated (PD-1pos TIM- 3neg) T lymphocytes and reduce the amount of exhausted (PD-1pos TIM-3pos) cells compared to placebo. As expected, we found that PeptiCRAd monotherapy could increase the number of antigen spe- cific CD8+ T cells compared to other treatments. However, only the combination with PD-L1 blockade could significantly increase the ra- tio between activated and exhausted pentamer positive cells (p= 0.0058), suggesting that by disrupting the PD-1/PD-L1 axis we could decrease the amount of dysfunctional antigen specific T cells. We ob- served that the anatomical location deeply influenced the state of CD4+ and CD8+ T lymphocytes. In fact, TIM-3 expression was in- creased by 2 fold on TILs compared to splenic and lymphoid T cells. In the CD8+ compartment, the expression of PD-1 on the surface seemed to be restricted to the tumor micro-environment, while CD4 + T cells had a high expression of PD-1 also in lymphoid organs. Interestingly, we found that the levels of PD-1 were significantly higher on CD8+ T cells than on CD4+ T cells into the tumor micro- environment (p < 0.0001). Conclusions In conclusion, we demonstrated that the efficacy of immune check- point inhibitors might be strongly enhanced by their combination with cancer vaccines. PeptiCRAd was able to increase the number of antigen-specific T cells and PD-L1 blockade prevented their exhaus- tion, resulting in long-lasting immunological memory and increased median survival

Characterisation of a synthesised fluorescent ligand (4-acridinol-1-sulphonic acid) using nuclear magnetic resonance spectroscopy

The synthesis and complete characterisation of the fluorescent ligand, 4-acridinol-1-sulphonic acid (the acridine analogue of 8-quinolinol-5-sulfonic acid) is described. Using a judicious array of nuclear magnetic resonance spectroscopy experiments, the structural elucidation and full assignment of all proton and carbon chemical shifts were afforded. The 4-acridinol-1-sulphonic acid was found to behave in a similar manner to 8-quinolinol-5-sulphonic acid, forming fluorescent complexes with magnesium(II) and zinc(II). The uncorrected emission maxima for the metal&ndash;acridinol complexes were found to be at around 620 nm compared to 505 nm for the respective quinolinol complexes. Unfortunately, preliminary spectrofluorimetric analytical figures of merit revealed that the detection limits of the new acridinol metal complexes were one and a half orders of magnitude poorer than those attained with the corresponding quinolinol ligand. However, in contrast to 8-quinolinol-5-sulphonic acid, the 4-acridinol-1-sulphonic acid ligand showed considerable selectivity for magnesium(II) and zinc(II) over aluminium(III)

Factors influencing anion binding stoichiometry : the subtle influence of electronic effects

Six new, charge-neutral norbornene-based receptors 1a,1b&ndash; 3a,3b were prepared, and their ability to interact with simple anions in DMSO was investigated using 1H NMR and UV/ Vis spectroscopy. Binding of dihydrogenphosphate by the six receptors appeared to be based solely on steric constraints. In contrast, the binding stoichiometry of 3a and 3b to acetate was controlled by subtle electronic factors.<br /