Low frequency four-wave mixing spectroscopy of biopolymer hydration layers in aqueous solutions

Four-wave mixing (FWM) spectroscopy has been applied to detection of H₂O₂ molecules rotational resonances in both DNA and denatured DNA aqueous solutions in the range ±100 cm⁻¹. A considerable growth of rotational lines intensity of H₂O and H₂O₂ has been observed in comparison with distilled water. This fact was interpreted as an exhibition of specific property of a hydration layer formation at DNA/water and denatured DNA/water interfaces. The fitting of four-wave mixing spectra shows the increasing of the H₂O₂ rotational line’s amplitude by a factor of ∼3 in DNA solutions due to denaturizing. The shifting of FWM Brillouin resonances in opposite way in protein solution and SWNT (single wall carbon nanotube) suspension to comparison with water was observed and discussed.     

Coherent laser spectroscopy of RF resonances in liquid

Four-photon polarization spectra of double distilled water subjected to a special treatment in a cavitation chamber and 20% aqueous solution of hydrogen peroxide were recorded in the range ±8 cm⁻¹. All recorded spectra contain narrow (< 0.3 cm⁻¹) resonances corresponding to the frequencies of the rotational spectrum of ortho and para spin isomers of the H₂O molecule. Numerical simulation of the spectra obtained made it possible to quantitatively estimate the contribution of the rotational spectrum to the coherent scattering signal. It was found that the contribution of the para spin isomer of the H₂O molecule to the rotational line spectrum decreases in an aqueous solution of the α-chymotrypsin protein. Apparently, this decrease indicates the selectivity of interaction of biopolymer molecules with different spin isomers.     

Four-photon polarization spectroscopy of the rotational resonances in liquids in the range 0–3 THz

The spectra of the coherent molecular rotation that coincide with the rotational spectra of the corresponding molecules in the gas phase are measured for the first time using four-photon coherent laser spectroscopy in the range 0–100 cm^?1 in several liquids (CCl₄, H₂O₂, D₂O, and H₂O). The measured spectra make it possible to separate the spectral contributions of the slow rotational molecular motions about the equilibrium and the fast rotations. The selectivity of the action of the microwave radiation on biological objects can be increased using the results obtained.     

Laser-field-induced coherent molecular librations in liquid

The temperature evolution of rotational spectra is demonstrated for four-photon scattering in water in the interval 0.1–8 cm^?1 (3–240 THz). A detailed numerical simulation of the spectra is performed. The best agreement is reached using the frequencies of the rotational resonances of free molecules. It is demonstrated that the contribution of coherent librations into the measured signal increases proportionally to the decrease in the shear viscosity of water. The four-photon-scattering spectra of water corresponding to an increase in the temperature and dilution with H₂O₂ are compared.     

Raman‐induced Kerr effect spectroscopy of single‐wall carbon nanotubes aqueous suspensions in the range 0.1–10 and 100–250 cm−1

Here, we study a low (less than 0.1 µg/ml) concentration aqueous suspension of single‐wall carbon nanotubes (SWNTs) by Raman‐induced Kerr effect spectroscopy (RIKES) in the spectral bands 0.1–10 and 100–250 cm⁻¹. This method is capable of carrying out direct investigation of SWNT hydration layers. A comparison of RIKES spectra of SWNT aqueous suspension and that of milli‐Q water shows a considerable growth in the intensity of low wavenumber Raman modes. These modes in the 0.1–10 cm⁻¹ range are attributed to the rotational transitions of H₂O₂ and H₂O molecules. We explain the observed intensity increase as due to the production of hydrogen peroxide and the formation of a low‐density depletion layer on the water–nanotube interface. A few SWNT radial breathing modes (RBM)are observed (ω_RBM = 118.5, 164.7 and 233.5 cm⁻¹) in aqueous suspension, which allows us to estimate the SWNT diameters (∼2.0, 1.5, and 1 nm, respectively). Copyright © 2011 John Wiley & Sons, Ltd.     

Four-wave mixing spectroscopy of aqueous suspensions of single-wall carbon nanotubes in the ranges of 0.1–10 and 100–250 cm<Superscript>−1</Superscript>

Distinctive optical properties of single-wall carbon nanotubes (SWNT) are highly sensitive to variations in the environment. Here, we have studied SWNT in aqueous suspensions at a low (less than 0.1 μg ml⁻¹) concentration by four-wave mixing (FWM) spectroscopy in the spectral bands of 0.1 to 10 cm⁻¹ (≈300 GHz) and 100 to 250 cm⁻¹ (3 to 7.5 THz). We directly investigated the hydration layers around SWNT. A comparison of the FWM spectra of an SWNT aqueous suspension and Milli-Q water shows a considerable increase in the intensity of low-frequency Raman modes, which are attributed to the rotational transitions of H₂O₂ and H₂O molecules. We explain the observed phenomenon by the hydrogen peroxide production and formation of a low-density depletion layer at the water-nanotube interface. We have observed several SWNT radial breathing modes ω _RBM =118.5, 164.7, and 233.5 cm⁻¹ in an SWNT aqueous suspension and estimated the corresponding SWNT diameters as ≈2.0, 1.5, and 1 nm.     

H<Subscript>3</Subscript>O<Stack><Subscript>2</Subscript><Superscript>-</Superscript></Stack> ions with a strong quasi-symmetrical H-bond and their hydration in aqueous solutions of NaOH and KOH

Ion-molecular interactions in aqueous solutions of NaOH (0–47.8%) and KOH (0–51.95%) are studied by multiple frustrated total internal reflection IR spectroscopy. Interpretation of the spectra and analysis of the spectral data are performed based on the results of DFT calculations (B3LYP/6-31++G(d, p)) of the characteristics of the free and double hydrated H₃O ₂ ^- ion. It is established that the changes in the IR spectra of NaOH and KOH aqueous solutions caused by increasing alkali concentration are due to the formation of H₃O ₂ ^- ions with a strong quasi-symmetrical hydrogen bond and their subsequent hydration by one or two water molecules. The influence of the cation nature on the degree of hydration of H₃O ₂ ^- ions is demonstrated. The equilibrium concentrations of monohydrate (H₃O ₂ ^- ? H₂O) and dihydrate (H₃O ₂ ^- ? 2H₂O) are calculated and their IR continuous absorption spectra are isolated.     

Water enrichment by hydroxyl and hydrogen peroxide due to cavitation treatment: GHz four-wave mixing spectroscopy

Four-waves mixing spectroscopy has been applied to detection of H₂O₂ and OH molecules in water after different treatments in a cavitation jet. The considerable growth of the ortho-H₂O, OH, and H₂O₂ rotational lines amplitude in cavitation water relatively to distilled water and 1% hydrogen peroxide aqueous solution have been found. This fact was interpreted as the exhibition of H₂O molecules dissociation onto atoms and recombination into OH and H₂O₂. Four-waves mixing spectra fitting gives the evaluation of H₂O₂ rotational line’s amplitude increasing in cavitation water by factor of ～3 in comparison to 1% H₂O₂ aqueous solution.     

Lyman transitions of high rovibrationally excited H2, HD and D2 molecules

Energies and probabilities of Lyman transitions of high rovibrationally excited H₂, HD and D₂ molecules have been measured and compared with calculations. The experimental results are obtained from laser-induced fluorescence spectra that have been recorded in the spectral range from 60 500 to 83 500 cm⁻¹, covering 2/3 of the hydrogen Lyman band system. The necessary vacuum-UV radiation is produced by stimulated anti-Stokes Raman scattering, providing a widely tunable radiation source with narrow spectral bandwidth to resolve single Lyman transitions. The highest internal energies of detected hydrogen isotopologues are close to the dissociation limit. This extends the available data base of Lyman transitions from and to higher rotational states (J > 10) of HD and D₂.     

Infrared Spectra of Water in Aqueous Solutions Using Internal Reflection Spectroscopy

Abstract

There has been a continuing interest in the structure of water and of aqueous solutions, and many studies have employed spectroscopic techniques. These have frequently involved absorption spectroscopy in the near-IR range, and Raman scattering. In general, however, the normal IR range has been but little used except for studies of HDO-containing solutions, and the region near 3500 cm^?1 of the intense H₂O absorption has been almost completely avoided. Transmission techniques have been exclusively employed with absorption spectroscopy. Internal reflection spectroscopy (IRS) techniques have been employed to examine aqueous solutions, but the emphasis was placed on studying the solute rather than the solvent. Also, the solute concentrations which had been employed in transmission studies have been rather high. We now suggest the feasibility of carrying out structural studies of aqueous solutions by using IRS techniques to record spectra in the IR range, employing solutions of relatively low concentrations. For example, the lowest concentration of aqueous HCl solution examined by Ackermann¹ was 2.5 M by transmission techniques in the 4000-1100 cm^?1 range; in contrast, using IRS, the perturbations of the O-H stretching and deformation bands of H₂O could be observed with 0.1 M HCl.     

Four-photon laser spectroscopy of liquid water and aqueous solutions of α-chymotrypsin in the range ±5 cm<Superscript>−1</Superscript>

The resonances located at 1.2, 1.6, 2.0, and 2.3 cm^?1 with a width of ～0.2 cm^?1 were observed for the first time in the range ±5 cm^?1 of the four-photon Rayleigh wing spectra of distilled water and aqueous solutions of the protein α-chymotrypsin. The line at 2.3 cm^?1 belongs to the rotational transition 3(2, 1)–4(1, 4) of the ground vibrational state of water. In the presence of the protein, the spectrum is modified by the appearance of new lines, located at 0.74, 2.8, and 3.2 cm^?1. The modification of the spectrum observed is interpreted as a manifestation of low-frequency vibrations of large molecular fragments in aqueous protein solutions and as a result of the structuring of water in the vicinity of protein molecules.     

High resolution pulsed cars spectroscopy of the Q-branches of some simple gases

Coherent anti-Stokes Raman spectra of the Q-branches of N₂, O₂ and of v₁ of C₂H₂ have been measured with fairly high resolution (≈ 0.30 cm^-1) by means of a pulsed dye laser system. Calculated CARS spectra show very good agreement with the observed rotational Q-branch structure.     

The ground state of molecular hydrogen

The v = 0?0 quadrupole spectrum of H₂ has been recorded using a 0.005-cm^?1 resolution Fourier transform spectrometer. The rotational lines S(1) through S(5) are observable in the spectra, in the region 587 to 1447 cm^?1. The spectral position for S(0) was also obtained from its v = 1-0 ground-state combination difference. The high accuracy of the H₂ measurements has permitted a determination of four rotational constants. These are (in cm^?1) B₀ = 59.33455(6); D₀ = 0.045682(4); H₀ = 4.854(12) × 10^?5; L₀ = ?5.41(12) × 10^?8. The hydrogen line positions will facilitate studies of structure and dynamics in astrophysical objects exhibiting infrared H₂ spectra. The absolute accuracy of frequency calibration over wide spectral ranges was verified using 10-μm CO₂ and 3.39-μm CH₄ laser frequencies. Standard frequencies for 5-μm CO were found to be high by 12 MHz (3.9 × 10^?4 cm^?1).     

Far infrared emission spectra from stratospheric hydrogen peroxide

Synthetic emission spectra from two stratospheric altitude observations have been analyzed for the presence of H₂O₂ in the far infrared region. The calculations are made with a high spectral resolution (10^–3 cm^–1 or 10^–4 cm^–1) greater than those in experimental measurements which are in the region of 3.10^–3 cm^–1. Spectra cover a spectral interval between 40 and 120 cm^–1 showing the best features of H₂O₂ susceptible to observation in a stratospheric spectrum. The optimum conditions for identification have been considered. Using the variations in H₂O₂ abundance in the measurement data and photochemical models, the H₂O₂ features detection limits have been studied.     

CARS investigation of collisional shift of the hydrogen Q‐branch transitions by water at high temperatures

A high‐resolution (∼0.1 cm⁻¹) spectroscopic method based on the application of a Fabry–Pérot interferometer to the spectral analysis of the coherent anti‐Stokes Raman scattering (CARS) signal from an individual Raman transition was used to obtain single‐shot spectra of hydrogen Q‐branch transitions directly in the flame of a pulsed, high‐pressure H₂/O₂ combustion chamber. Simultaneously with the Fabry–Pérot pattern, a broadband CARS spectrum of the complete H₂Q ‐branch structure was recorded in order to measure the temperature of the probe volume. During every cycle of the combustion chamber, a pressure pulse together with single‐shot CARS spectra, providing information on individual line shapes and medium temperature, was recorded. On the basis of the experimental data, the temperature dependences of lineshift coefficients for several Q‐branch lines of hydrogen molecules under collisions with water molecules were determined in the temperature range 2100 < T < 3500 K, and an empirical ‘fitting law’ for H₂ H₂O lineshift coefficients is proposed. Copyright © 2010 John Wiley & Sons, Ltd.     

High resolution molecular spectroscopy in the submillimeter region

Fourier Transform laboratory measurements have been carried out, for the first time in the 8–85 cm^–1 spectral region, with an unapodized resolution of 3.3. 10^–3 cm^–1 and a frequency accuracy of 2. 10^–4 cm^–1. Samples from spectra of several molecules namely: CO, O₃, H₂O₂, NO, NO₂, HNO₃, SO₂, H₂S, HOCL, NOCL, HNCO, ND₃ and AsH₃ are presented to show both the quality of the measurements and the type of information supplied by high resolution spectroscopy in the submillimeter region.     

Conversion of ortho-para H2O isomers in water and a jump in erythrocyte fluidity through a microcapillary at a temperature of 36.6±0.3°C

A mechanism is proposed for the previously observed [1] jump in erythrocyte fluidity through a microcapillary 1.3 μm in diameter at a temperature of 36.6±0.3°C. Our interpretation is based on the experimental evidence both for existence of ortho and para H₂O isomers in water and on spin-selective interaction of proteins with para H₂O isomers as hydration shells of biomolecules are being formed [2]. It is important that the formation of hydration shells of proteins and DNA in aqueous solutions is accompanied by an increase in the Brillouin shift to 0.4 cm⁻1 (≃0.25 cm⁻¹ in water), which points to the formation of icelike structures. We believe that the coincidence of the translational energy kT of the Brownian motion and the energy of the rotational quanta for the 3₁₃–2₀₂ transition of para H₂O isomers at the temperature 36.6°C increases the probability for excitation of para H₂O isomers in collisions. Collisions mix quantum states of closely spaced levels in para H₂O (3₁₃, 285.2 cm⁻¹) and ortho H₂O (3₃₀, 285.4 cm⁻¹) and induce conversion of para isomers to ortho H₂O. It is assumed that this conversion in the icelike hydration shell of hemoglobin (Hb) is accelerated under the catalyzing effect of oxygen and iron present in Hb and triggers a chain reaction: release of ortho H₂O isomers through the erythrocyte membrane→compaction of Hb molecules and increase in concentration of catalysts→acceleration of conversion→structural gel-sol transition. It is the sequence of these processes that provides a jump in fluidity of erythrocytes through a microcapillary and the anomalous increase in fluidity of the aqueous solution of hemoglobin by almost an order of magnitude at temperatures close to 36.6°C and an increase in the solution concentration by a factor of 1.7.     

Raman Spectra of Nitrogen,Carbon Dioxide,and Hydrogen in a Methane Environment

Changes in the Raman spectra of N₂, H₂, and CO₂ are studied in the range of 200–3800 cm^–1 depending on the concentration of surrounding CH₄ molecules at a fixed medium pressure of 25 atm and temperature of 300 K. It has been found that changes in the spectral characteristics of purely rotational H₂ lines in a CH₄ medium are negligible, while the Q-branches of the v₁/2v₂ Fermi dyad in СO₂ become narrower and wavenumbers of its high-frequency component and v₁ band of N₂ decrease. In addition, under these conditions, the ratio of intensities of the CO₂ Fermi dyad Q-branch varies in proportion to the concentration of surrounding molecules of CH₄. The obtained data will be used in diagnosing the composition of natural gas using Raman spectroscopy.     

Far infrared spectral lines and absorptance calculation of NO

The positions and intensities of pure rotation lines of ¹⁴N¹⁶O have been calculated between 10–200 cm^-1 and are tabulated. The line by line absorption spectrum has been computed using tabulated parameters, and compared with experimental spectra measured by other authors. The spectral emission of atmospheric NO has been calculated for an altitude of 14.5 km, where some measurements have been carried out. After comparing the NO and the background H₂O+O₂+O₃ spectra, it is shown that the NO emission in the far i.r. spectrum of the lower stratosphere is negligible.     

Spectral least squares quantification of several atmospheric gases from high resolution infrared solar spectra obtained at the South Pole

Spectral least squares fitting has been used to analyze high resolution (0.02 cm^-1) i.r. solar spectra obtained at the South Pole in 1980. The spectral regions analyzed allow the simultaneous quantification of CO₂, H₂O, N₂O, CH₄, and O₃. Information is obtained on the column amount and on the vertical distribution.