Spectrochim Acta A Mol Biomol Spectrosc
March 2018
Dimer formation with dipole neutralization produces species such as low polarity water (LPW) compatible with hydrophobic surfaces (Phys. Chem. Chem.
View Article and Find Full Text PDFPhys Chem Chem Phys
October 2015
The bridge between water repelling and water-attracting regions is recognized here as low polarity water, a novel "neutral" form of water; its identity as a dipole-dipole water dimer is supported by spectroscopic evidence of its presence in thin films of water on a polyethylene surface. High resolution (0.5 cm(-1)), low signal energies (Sg 100) and short scans (0.
View Article and Find Full Text PDFThe simplest (minimal) peptide model is HCONHCH3. An increase in the π-helix content with increased substitution in the acyl portion suggested the examination of N-methyl-trimethylacetamide) (NMT). NMT displays spectra, in which there is evolution of a set of helices defined by their amide I maxima near 1686 (3(10)), 1655 (first π), and, most importantly, at 1637 cm(-1) (π).
View Article and Find Full Text PDFA peptide model is a physical system containing a CONH group, the simplest being HCONHCH3 , N-methylformamide (NMF). We have discovered that NMF and N-methylacetamide (NMA), which form hydrogen-bonded oligomers in thin films on a planar AgX fiber, display infrared (IR) spectra with peaks like those of polypeptide helices. Structures can be assigned by their amide I maxima near 1672 (3(10)), 1655 (3(10)), 1653 (α), 1655 (π), and 1635 cm(-1) (π), which are the first IR data for the π-helix.
View Article and Find Full Text PDFEvaporation of water on a planar AgX surface leads to a strongly bound monolayer for which IR spectra display the marker peaks for modest numbers of oligomers. From 700-1800 spectra for each isotopomer, H(2)O(16) and H(2)O(18), a pair was selected with moderate intensity at 1616 cm(-1) (a peak reported for the cyclic trimer of water) from the monolayer portion of the experiment. Every selected spectrum had lesser peaks for other oligomers.
View Article and Find Full Text PDFN-methylformamide (NMF), the simplest model for peptides, exhibits hyperplectic (both simple and complex) behavior as revealed by thin film infrared spectroscopy on planar AgX [AgCl:AgBr] fiber. IR spectra (0.1 s scans) of 10 microg NMF/dichloromethane(DCM) under N(2) flow first show NMF monomer, dimers, and trimers, which then form surface-organized NMF oligomers as pseudocrystals (P(n)) of increasing length and intensity to P(12).
View Article and Find Full Text PDFAcetonitrile and [D3]acetonitrile in the vicinal region of a planar AgX fiber contain linear dipole-dipole linked oligomers as shown by 1) comparison of infrared band intensity ratios in the gaseous and condensed phases and 2) remarkable plots of absorbance (C--N stretch) versus time during evaporation from an AgX planar fiber element. The plots (CH3CN 2252 cm(-1), CD3CN 2262 cm(-1)) reveal the presence of octamers, hexamers, tetramers, and dimers along with some heptamer, trimer, and monomer structures. A novel isotope effect arises from the somewhat smaller size of the CD3CN resulting in an increase in the CN band intensity.
View Article and Find Full Text PDFSurface-enhanced infrared absorption spectroscopy (SEIRA) of methanol, ethanol, 1-propanol, and 2-propanol in thin films on planar silver halide (AgX) fibers under slow N(2) flow using 1 sec scans reveals structure in absorbance-time plots. The absorption intensities show extra enhancements (3x) in the absorbance (O--H stretch) ascribed to oligomers present at the AgX surface (molecule enhanced, thus MOSEIRA). This is above those due to amplification (40x, 20 reflections) and enhancement (30x, image dipoles or surface phonon polaritons).
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