Elongated tetrahexahedral Au nanocrystals have been grown in high yields using a seed-mediated growth method. Morphological and structural characterizations show that these Au nanocrystals are single-crystalline and enclosed by 24 high-index {037} facets. They are more electrochemically active than octahedral Au nanocrystals that are enclosed by 8 low-index {111} facets. To date, there have been only a few reports of metal nanocrystals that are enclosed exclusively by high-index facets, including trisoctahedral Au nanocrystals enclosed by 24 {122} facets and tetrahexahedral Pt nanocrystals enclosed by 24 {037} facets. Our tetrahexahedral Au nanocrystals will be an important addition to the family of metal nanocrystals that are enclosed exclusively by high-index facets and will also be useful for fundamental catalytic studies on metal nanocrystals.
A sodalite-type porous metal-organic framework with polyoxometalate templates, H(3)[(Cu(4)Cl)(3)(BTC)(8)](2)[PW(12)O(40)]·(C(4)H(12)N)(6)·3H(2)O (NENU-11; BTC = 1,3,5-benzenetricarboxylate), was obtained by a hydrothermal reaction. As a reasonable candidate for eliminating nerve gas, NENU-11 displays good adsorption behavior for dimethyl methylphosphonate (15.5 molecules per formula unit). In virtue of the catalytic activity of polyoxometalate guests, this nerve gas mimic could be facilely decomposed by a hydrolysis reaction.
Ion channels play crucial roles in transport and regulatory functions of living cells. Understanding the gating mechanisms of these channels is important to understanding and treating diseases that have been linked to ion channels. One potential model peptide for studying the mechanism of ion channel gating is alamethicin, which adopts a split alpha/310 helix structure and responds to changes in electric potential. In this study, sum frequency generation vibrational spectroscopy (SFG-VS), supplemented by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), has been applied to characterize interactions between alamethicin (a model for larger channel proteins) and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) lipid bilayers in the presence of an electric potential across the membrane. The membrane potential difference was controlled by changing the pH of the solution in contact with the bilayer, and measured using fluorescence spectroscopy. The orientation angle of alamethicin in POPC lipid bilayers was then determined at different pH values using polarized SFG amide I spectra. Assuming that all molecules adopt the same orientation (a δ distribution), at pH=6.7 the α-helix at the N-terminus and the 310 helix at the C-terminus tilt at about 72° (θ1) and 50° (θ2) versus the surface normal, respectively. When pH increases to 11.9, θ1 and θ2 decrease to 56.5° and 45°, respectively. The δ distribution assumption was verified using a combination of SFG and ATR-FTIR measurements, which showed a quite narrow distribution in the angle of θ1 for both pH conditions. This indicates that all alamethicin molecules at the surface adopt a nearly identical orientation in POPC lipid bilayers. The localized pH change in proximity to the bilayer modulates the membrane potential and thus induces a decrease in both the tilt and bend angles of the two helices in alamethicin. This is the first reported application of SFG to the study of model ion channel gating mechanisms in model cell membranes.
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