Cantrell Landry (africadonna92)

We report the first total synthesis of the polyunsaturated fatty acid 7-hydroxydocosahexaenoic acid (7-HDHA) in racemic form and the enantioselective synthesis of 7-(S)-HDHA. Both syntheses follow a convergent approach that unites the C1-C9 and C10-C22 fragments using Sonogashira coupling and Boland reduction as key steps. These syntheses enabled the unambiguous characterization of this natural product for the first time and helped establish 7(S)-HDHA as a possible endogenous ligand for peroxisome proliferator-activated receptor alpha.In cryogenic ion vibrational predissociation (CIVP) spectroscopy, the influence of the tag on the spectrum is an important consideration. Whereas for small ions several studies have shown that the tag effects can be significant, these effects are less understood for large ions or for large numbers of tags. Nevertheless, it is commonly assumed that if the investigated molecular ion is large enough, the perturbations arising from the tag are small and can therefore be neglected in the interpretation. In addition, it is generally assumed that the more weakly bound the tag is, the less it perturbs the CIVP spectrum. Under these assumptions, CIVP spectra are claimed to be effectively IR absorption spectra of the free molecular ion. Having observed unexpected splittings in otherwise unproblematic CIVP spectra of some tagged ions, we report Born-Oppenheimer molecular dynamics (BOMD) simulations that strongly indicate that mobility among the more weakly bound tags leads to the surprising splittings. We compared the behavior of two tags commonly used in CIVP spectroscopy (H2 and N2) with a large pyridinium cation. Our experimental results surprisingly show that under the appropriate circumstances, the more weakly bound tag can perturb the CIVP spectra more than the more strongly bound tag by not just shifting but also splitting the observed bands. The more weakly bound tag had significant residence times at several spectroscopically distinct sites on the molecular ion. This indicates that the weakly bound tag is likely to sample several binding sites in the experiment, some of which involve interaction with the reporter chromophore.The metabotropic glutamate receptor (mGluR) 2 plays a key role in the central nervous system. mGluR2 has been shown to be regulated by its surrounding lipid environment, especially by cholesterol, by an unknown mechanism. Here, using a combination of biochemical approaches, photo-cross-linking experiments, and molecular dynamics simulations we show the interaction of cholesterol with at least two, but potentially five more, preferential sites on the mGluR2 transmembrane domain. Our simulations demonstrate that surface matching, rather than electrostatic interactions with specific amino acids, is the main factor defining cholesterol localization. Moreover, the cholesterol localization observed here is similar to the sterol-binding pattern previously described in silico for other members of the mGluR family. Biochemical assays suggest little influence of cholesterol on trafficking or dimerization of mGluR2. Nevertheless, simulations revealed a significant reduction of residue-residue contacts together with an alteration in the internal mechanical stress at the cytoplasmic side of the helical bundle when cholesterol was present in the membrane. These alterations may be related to destabilization of the basal state of mGluR2. Due to the high sequence conservation of the transmembrane domains of mGluRs, the molecular interaction of cholesterol and mGluR2 described here is also likely to be relevant for other members of the mGLuR family.Silica nanoparticles (SiO2-NPs) are promising in nanoenabled agriculture due to their large surface area and biocompatible properties. Understanding the fundamental interaction between SiO2-NPs and plants is important for their sustainable use. Here, 3 week-old pakchoi (Brassica chinensis L.) plants were sprayed with SiO2-NPs every 3 days for 15 day