2 research outputs found
Tuning the Surface Chemistry of Chiral Cu(531)<sup><i>S</i></sup> for Enhanced Enantiospecific Adsorption of Amino Acids
Amino
acids are important bioorganic compounds composed of amine
and carboxylic acid because they are the main
building blocks of many biomolecules. All of them are chiral except
glycine. Thus, they have two enantiomers which provide dramatically
different biological effects, thereby requiring their separation.
High Miller index metal surfaces often define intrinsically chiral
structures. A number of previous studies have proved the enantiospecific
adsorption difference of chiral molecules on those surfaces. To further
enhance the enantiospecificity, step decoration, which is doping the
kink site of chiral metal surface with a second metal, can be one
route. It may induce one enantiomer adsorbed on the surface to become
more stable than the other, inducing the larger enantiospecific energy
difference. In this study, we performed density functional theory
(DFT) calculations to systemically examine the adsorption geometries
and energetics of each enantiomer of alanine, serine, and cysteine,
and their enantiospecific energy differences on pure, Pd-, Pt-, and
Au-decorated Cu(531)<sup><i>S</i></sup>, respectively. By
decorating the kinked site with an Au atom, the enantiospecificity
of adsorbed cysteine was meaningfully enhanced by 0.08 eV, in the
case when the side chain has a high affinity with the surface. Our
results provide useful insight of how to tune chiral metal surfaces
to enlarge the enantiospecificity of chiral molecules
Aerosol Cross-Linked Crown Ether Diols Melded with Poly(vinyl alcohol) as Specialized Microfibrous Li<sup>+</sup> Adsorbents
Crown
ether (CE)-based Li<sup>+</sup> adsorbent microfibers (MFs) were successfully fabricated through a combined
use of CE diols, electrospinning, and aerosol cross-linking. The 14-
to 16-membered CEs, with varied ring subunits and cavity dimensions,
have two hydroxyl groups for covalent attachments to polyÂ(vinyl alcohol)
(PVA) as the chosen matrix. The CE diols were blended with PVA and
transformed into microfibers via electrospinning, a highly effective
technique in minimizing CE loss during MF fabrication. Subsequent
aerosol glutaraldehyde (GA) cross-linking of the electrospun CE/PVA
MFs stabilized the adsorbents in water. The aerosol technique is highly
effective in cross-linking the MFs at short time (5 h) with minimal
volume requirement of GA solution (2.4 mL g<sup>–1</sup> MF).
GA cross-linking alleviated CE leakage from the fibers as the CEs
were securely attached with PVA through covalent CE–GA–PVA
linkages. Three types of CE/PVA MFs were fabricated and characterized
through Fourier transform infrared-attenuated total reflection, <sup>13</sup>C cross-polarization magic angle spinning NMR, field emission
scanning electron microscope, N<sub>2</sub> adsorption/desorption,
and universal testing machine. The MFs exhibited pseudo-second-order
rate and Langmuir-type Li<sup>+</sup> adsorption. At their saturated
states, the MFs were able to use 90–99% CEs for 1:1 Li<sup>+</sup> complexation, suggesting favorability of their microfibrous
structures for CE accessibility to Li<sup>+</sup>. The MFs were highly
Li<sup>+</sup>-selective in seawater. Neopentyl-bearing CE was most
effective in blocking larger monovalents Na<sup>+</sup> and K<sup>+</sup>, whereas the dibenzo CE was best in discriminating divalents
Mg<sup>2+</sup> and Ca<sup>2+</sup>. Experimental selectivity trends
concur with the reaction enthalpies from density functional theory
calculations, confirming the influence of CE structures and cavity
dimensions in their “size-match” Li<sup>+</sup> selectivity