Vibrational spectra and rotational isomerism of allyl amine

The infrared spectra of allyl amine in the vapour, liquid and solid phases have been measured from 250 to 4000 cm⁻¹. The laser-Raman spectrum in the liquid state has also been recorded photoelectrically and qualitative depolarization measurements have been made. The interpretation of the spectral data suggests the presence of two rotational isomers (‘cis and trans”, and ‘ganche and trans’) in the vapour and liquid phases whereas the form having asymmetrical structure (‘gauche and trans’, C₁ symmetry) gets stabilized in the solid state at low temperature.     

Vibrational spectra and rotational isomerism of tripropargyl amine

The infrared spectra of tripropargyl amine were recorded from 250 to 4000 cm⁻¹ in the vapor, liquid and solid phases. The Raman spectrum of the liquid at room temperature was photoelectrically recorded and qualitative depolarization measurements were made. A comparative study of the infrared spectra in the fluid phase and in various solvents with that in solid phase reveals the existence of rotational isomers in the liquid and vapor phases. Various possibilities for rotational isomers with different point group symmetries are discussed.     

Microwave spectrum and rotational isomerism in isopropyl mercaptan

A microwave investigation of isopropyl mercaptan has established the existence of both trans and gauche conformers, the trans being more stable by 57 cal mole^?1. Stark effect measurements give the dipole moments as 1.61 ± 0.2 D for the trans and 1.53 ± 0.2 D for the gauche species. The spectra of the isotopic species (CH₃)₂CH³²SD, (CH₃)₂CH³⁴SH, and (CH₃)₂CH³⁴SD of the trans form have also been analyzed, providing a limited amount of structural data.The rotational spectrum of the gauche isomer is noticeably influenced by inversion. Interactions between energy levels in the two lowest inversion states have been satisfactorily accounted for in terms of rotational constants, coupling parameters (G_a and G_c), and ΔE₀, the inversion level splitting. ΔE₀ is found to be 562.4 MHz for the ground state of (CH₃)₂CHSH and 10.0 MHz for (CH₃)₂CHSD. A value of 1.98 kcal mole^?1 has been calculated for the barrier to internal rotation of the -SH group in terms of a V₃ potential.     

Skeletal deformation vibrations and rotational isomerism of ethylenediamine and monoethanolamine

The infrared and Raman spectra of ethylenediamine hydrochloride, sulfate crystals, their N-deuterated compounds and ethylenediamine in the liquid and gaseous states and in cyclohexane solution were studied.The skeletal deformation vibration frequencies were found to be conformation sensitive and showed that the ethylenediamine molecule takes the trans and gauche forms in the liquid state and the gauche form in the gaseous state and in cyclohexane solution.The infrared and Raman spectra of monoethanolamine were studied in the liquid state. The spectra in the region for which the skeletal deformation vibration bands appear showed that the monoethanolamine molecule takes the trans and gauche form in the liquid state.     

Fluorescence spectra of anthracene and pyrene in water and in aqueous surfactant solution

The fluorescence and excitation spectra of anthracene and pyrene have been measured in water and in aqueous solution of sodium dodecyl sulfate (SDS), and compared with the spectra in ethanol, for microcrystals and in a solution by the dilution method. The molecular spectra observed in water exhibit large broadenings and red-shifts due to the specific solvent effects of water. In aqueous SDS solution the spectra of anthracene are considerably broadened and red-shifted, suggesting the existence of the molecules near the micellar surface, while in the emission spectrum of pyrene remarkable intensity reductions of the vibronic bands have been observed, indicating a weak polarity of the environment in the SDS micelles.     

Microwave spectrum and rotational isomerism of n-propyl isocyanide

The microwave spectrum of n-propyl isocyanide has revealed the existence of two rotational isomers, trans (methyl trans to the isocyanide substituent), and gauche. Plausible structures have been fitted to the data, giving the gauche dihedral angle as 119° ± 2° from the trans position. Stark effect measurements have yielded dipole moments for the two rotamers: μ_trans = 4.16 ± 0.02 D and μ_gauche = 4.10 ± 0.09 D. The rotational constants of the trans form are A = 23 700 ± 100, B = 2407.632 ± 0.020, and C = 2278.853 ± 0.030 MHz, and those of the gauche form are A = 10 208.983 ± 0.030, B = 3479.219 ± 0.015, and C = 2859.981 ± 0.015 MHz. It has been found from relative intensity measurements that the gauche ground state is slightly more stable than the trans ground state, with an energy difference of 99 ± 45 cm^?1. Several vibrationally excited states have been assigned to the torsional motion around the central carbon-carbon bond, the CNC bending motion, and the methyl internal rotation. The torsional vibration frequency is 114 ± 20 cm^?1 in the trans form and 123 ± 20 cm^?1 in the gauche form. A four-term potential function for internal rotation about the central CC bond has been determined.     

Quantum-chemical calculations of electronic-absorption spectra of aromatic amino acids in aqueous solution

Quantum-chemical methods are used to calculate electronic-absorption spectra, dipole moments, and atomic-charge distributions of aromatic amino acids in aqueous solutions at various concentrations. The electronic-absorption spectra are analyzed and compared with the spectra that are calculated for gas phase. The bathochromic shift of the spectral position is shown for the long-wavelength absorption peak of the singlet-singlet transition for aqueous solutions of amino acids.     

Modified polypropylene fabrics and their metal ion sorption role in aqueous solution

Polypropylene non-woven fabrics were grafted with glycidyl methacrylate by the electron beam irradiation method and the introduced epoxide rings were chemically conversed to hydroxyl and thiol groups. The modified polypropylene fabrics showed sufficient hydrophilicity to adsorb the metal ions from the aqueous solutions. The modified fibers were examined as adsorbents for metal ions dissolved in seawater and its model solutions at various conditions. The amount of ions adsorbed on the fabrics was determined by a sequential plasma spectrometry. The modified polypropylene fabrics adsorbed extremely high amount of Au(III) and Hg(II) ions. The equilibrium adsorption of Au(III) was almost not disturbed, even if Cu(II), Cd(II), Pb(II) and the other ions coexisted in the same aqueous solution. Nowadays, the most widely advantages of this technique are the recovery of metal ions dissolved in water and the treatment of industrial wastewater systems.     

Influence of surfactants on the fluorescence and absorption spectra of erythrosin in aqueous solution

The effect of certain non-ionic, anionic and cationic surfactants on the fluorescence and absorption spectra of erythrosin has been studied. Shifts towards longer wavelengths in absorption and fluorescence peaks have been observed. Also, there appears to be a marked enhancement in the fluorescence intensity of erythrosin on adding small amounts of surfactants. The shift in the absorption peak wavelength appears to be due to the binding of the surfactant with dye molecules. The enhancement in the fluorescence intensity is attributed to the disaggregation of erythrosin dye dimer and multimer forms into the monomeric form. The change in the geometry of dye molecules in the presence of cationic surfactants has also been discussed. Enhancement in the fluorescence intensity on the addition of ethanol has been observed.     

The effect of nitrobenzene on the Raman spectra of ribonuclease in aqueous solution

The Raman spectra of the native ribonuclease treated with nitrobenzene in aqueous solution have been obtianed. The conformation of the main chain and the side chain in ribonuclease were studied. Among the amide Ⅰ and amide Ⅲ bands, the characters of β-sheet and random coil structures are clear. The disulfide bridges assume the gauche-gauche-gauche conformation. The parts of tyrosine residue are buried. It indicates that nitrobenzene treatment on protein aqueous solution is an efficient means for obtaining better Raman spectra.     

Influence of rotational isomerism on two-photon absorption properties of FTC chromophores

The influence of rotational isomerism on the two-photon absorption(TPA) of FTC chromophores has been investigated using the quadratic response theory with the B3LYP functional.Eight rotamers induced by three rotatable single bonds in the molecule are fully optimized,and it is found that their conformational energies are nearly degenerate.Our calculations demonstrate that rotational isomerism has an important effect on the TPA cross sections.For a certain rotamer,the maximum TPA cross section is enhanced significantly.In addition,in the longer wavelength region,the rotational isomerism could lead to a large shift of the TPA position.     

Specific ion adsorption and short-range interactions at the air aqueous solution interface

We have investigated the surface composition of alkali-halide aqueous solutions using grazing incidence x-ray fluorescence. Using mixtures of salts as a means to enhance the short-range effects, small differences in concentration over a few angstrom could be resolved, with, for example I- or Br- > Cl-. In order to explain our data, we need to include an effective potential accounting for the short-range (A) solvent mediated couplings, responsible for specific effects together with dispersion forces. This attractive potential (few k{B}T for halides) leads to concentration profiles which are in good agreement with recent numerical simulations.     

Infrared spectra of CdSb

We present new measurements of infrared reflectivity of CdSb crystals. Phonons were detected for the three crystallographic axes and fitted with the factorized oscillator model. Fourteen out of the fifteen predicted phonons were detected.