Photochemistry of Transition Metal Complexes Induced by Outer-Sphere Charge Transfer Excitation

The intermolecular (outer sphere, OS) interaction of a reducing and an oxidizing metal complex generates a new optical transition involving charge transfer (CT) from the electron donor to the acceptor. OS CT transitions are classified according to the redox site (metal or ligand). Generally, the interaction between donor and acceptor is facilitated by ion pairs consisting of an oxidizing complex cation and a reducing complex anion. There are also ion pairs which are composed of a metal complex and an organic counter ion as electron donor or acceptor. In addition, the review includes examples of OS CT interaction which do not involve ion pairs at all. — A short introduction into the theory is followed by the discussion of the spectroscopy of OS CT of transition metal complexes. Finally, photoreactions induced by OS CT transitions are reviewed. The optical transfer is frequently followed by a rapid back electron transfer which regenerates the starting complexes. In many cases the primary products are kinetically labile and substitution reactions compete successfully with back electron transfer. As a result stable redox products may be formed. As an alternative, the substitution can be followed by back electron transfer. Product formation appears then as a substitution of the starting complexes. The various possibilities are illustrated by appropriate examples

Lymphocyte Activation Dynamics Is Shaped by Hereditary Components at Chromosome Region 17q12-q21

Single nucleotide polymorphisms (SNPs) located in the chromosome region 17q12-q21 are risk factors for asthma. Particularly, there are cis-regulatory haplotypes within this region that regulate differentially the expression levels of ORMDL3, GSDMB and ZPBP2 genes. Remarkably, ORMDL3 has been shown to modulate lymphocyte activation parameters in a heterologous expression system. In this context, it has been shown that Th2 and Th17 cytokine production is affected by SNPs in this region. Therefore, we aim to assess the impact of hereditary components within region 17q12-q21 on the activation profile of human T lymphocytes, focusing on the haplotype formed by allelic variants of SNPs rs7216389 and rs12936231. We measured calcium influx and activation markers, as well as the proliferation rate upon T cell activation. Haplotype-dependent differences in mRNA expression levels of IL-2 and INF-γ were observed at early times after activation. In addition, the allelic variants of these SNPs impacted on the extent of calcium influx in resting lymphocytes and altered proliferation rates in a dose dependent manner. As a result, the asthma risk haplotype carriers showed a lower threshold of saturation during activation. Finally, we confirmed differences in activation marker expression by flow cytometry using phytohemagglutinin, a strong polyclonal stimulus. Altogether, our data suggest that the genetic component of pro-inflammatory pathologies present in this chromosome region could be explained by different T lymphocyte activation dynamics depending on individual allelic heredity.This work was supported by grants from the Spanish Ministry of Economy and Competitiveness (SAF2010-16725, SAF2013-46077-R, SAF2014-52228-R, BES-2011-043839), Fondo de Investigación Sanitaria (Red HERACLES RD12/0042/0014), Fundació la Marató de TV3 (20134030) and Fondo Nacional de Desarrollo Científico y Tecnológico (FONDECYT 3150113). The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript