Fixation of atmospheric carbon dioxide by a cadmium(II) macrocyclic complex

A crystal structure showing an unusual trinuclear Cd(II) cluster bridged in mu3 fashion by a carbonate ligand is reported. The carbonate ion is formed by fixation of atmospheric carbon dioxide from the corresponding cadmium mononuclear complex containing an aza crown ether.     

Functional expression, targeting and Ca2+ signaling of a mouse melanopsin-eYFP fusion protein in a retinal pigment epithelium cell line

Melanopsin, first discovered in Xenopus melanophores, is now established as a functional sensory photopigment of the intrinsically photosensitive retinal ganglion cells. These ganglion cells drive circadian rhythm and pupillary adjustments through projection to the brain. Melanopsin shares structural similarities with all known opsins. Comprehensive characterization of melanopsin with respect to its spectral properties, photochemical cascade and signaling partners requires a suitable recombinant system and high expression levels. This combination has not yet been described. To address this issue, we have expressed recombinant mouse melanopsin in several cell lines. Using enhanced yellow fluorescent protein (eYFP) as a visualization tag, expression was observed in all cell lines. Confocal microscopy revealed that melanopsin was properly routed to the plasma membrane only in retinal pigment epithelium (RPE)-derived D407 cells and in human embryonic kidney (HEK) cells. Further, we performed intracellular calcium measurements in order to probe the melanopsin signaling activity of this fusion protein. Transfected cells were loaded with the calcium indicator Fura2-AM. Upon illumination, an immediate but transient calcium response was observed in HEK as well as in D407 cells, while mock-transfected cells showed no calcium response under identical conditions. Supplementation with 11-cis retinal or all-trans retinal enhanced the response. After prolonged illumination the cells became desensitized. Thus, RPE-derived cells expressing recombinant melanopsin may constitute a suitable system for the study of the structural and functional characteristics of melanopsin.     

Small-scale structure in fluid cholesterol–lipid bilayers

Cholesterol is the single most abundant molecule in animal plasma membranes, in the range of 20–30 mol%, where it is known to modulate the lipid-bilayer component of the membrane and lead to increased mechanical stability, lower permeability, larger thickness, and a distinct lateral organization. The phase equilibria of membranes with cholesterol and the associated large- and small-scale structure have turned out to be a particularly elusive problem. With the proposal that lipid domains and so-called ‘rafts’, characterized by high local levels of cholesterol in a liquid-ordered phase, are important for a wide range of cellular functions, an understanding and a quantitative assessment of the nature of these cholesterol-induced structures and their types of ordering have become urgent. Recent progress in neutron diffraction studies of lipid–cholesterol model membranes has now revealed details of the lateral ordering, and combined with earlier molecular model studies a picture emerges of the membrane as a locally structured liquid with small ordered ‘domains’ of a highly dynamic nature.     

A Photoswitchable Agonist for the Histamine H3 Receptor,a Prototypic Family A G‐Protein‐Coupled Receptor

Spatiotemporal control over biochemical signaling processes involving G protein‐coupled receptors (GPCRs) is highly desired for dissecting their complex intracellular signaling. We developed sixteen photoswitchable ligands for the human histamine H₃ receptor (hH₃R). Upon illumination, key compound 65 decreases its affinity for the hH₃R by 8.5‐fold and its potency in hH₃R‐mediated G_i protein activation by over 20‐fold, with the trans and cis isomer both acting as full agonist. In real‐time two‐electrode voltage clamp experiments in Xenopus oocytes, 65 shows rapid light‐induced modulation of hH₃R activity. Ligand 65 shows good binding selectivity amongst the histamine receptor subfamily and has good photolytic stability. In all, 65 (VUF15000) is the first photoswitchable GPCR agonist confirmed to be modulated through its affinity and potency upon photoswitching while maintaining its intrinsic activity, rendering it a new chemical biology tool for spatiotemporal control of GPCR activation.     

Dispersion relation of lipid membrane shape fluctuations by neutron spin-echo spectrometry

We have studied the mesoscopic shape fluctuations in aligned multilamellar stacks of 1,2-dimyristoyl-sn-glycero-3-phoshatidylcholine bilayers using the neutron spin-echo technique. The corresponding in plane dispersion relation tau-1(q//) at different temperatures in the gel (ripple, Pbeta') and the fluid (Lalpha) phase of this model system has been determined. Two relaxation processes, one at about 10 ns and a second, slower process at about 100 ns can be quantified. The dispersion relation in the fluid phase is fitted to a smectic hydrodynamic theory, with a correction for finite qz resolution. We extract values for the bilayer bending rigidity kappa, the compressional modulus of the stacks B, and the effective sliding viscosity eta3. The softening of a mode which can be associated with the formation of the ripple structure is observed close to the main phase transition.     

CASPT2 study of the potential energy surface of the HSO2 system

The importance of the HSO(2) system in atmospheric and combustion chemistry has motivated several works dedicated to the study of associated structures and chemical reactions. Nevertheless controversy still exists in connection with the reaction SH + O(2)→ H + SO(2) and also related to the role of the HSOO isomers in the potential energy surface (PES). Here we report high-level ab initio calculation for the electronic ground state of the HSO(2) system. Energetic, geometric, and frequency properties for the major stationary states of the PES are reported at the same level of calculations: CASPT2/aug-cc-pV(T+d)Z. This study introduces three new stationary points (two saddle points and one minimum). These structures allow the connection of the skewed HSOO(s) and the HSO(2) minima defining new reaction paths for SH + O(2) → H + SO(2) and SH + O(2) → OH + SO. In addition, the location of the HSOO isomers in the reaction pathways have been clarified.     

Controlled methyl chloride synthesis at mild conditions using ultrasound irradiation

A new route for the chlorination of methane is described using ultrasound irradiation, which allows for an intrinsically safe process at ambient pressure and temperature. By tuning the gas feed composition methyl chloride yields of up to 19% have been obtained.