Hydrogen bonding network dynamics of 1,2-propanediol-water binary solutions by Raman spectroscopy and stimulated Raman scattering.

Raman spectroscopy and stimulated Raman scattering (SRS) were used to investigate the hydrogen bonding (HB) network in 1,2-propanediol (1,2-PD)-water binary solutions. Abnormal changes in hydrogen bonds (HBs) were detected when V1,2-PD (volume fraction of the1,2-PD) was 0.4. In the case of Raman spectroscopy, the HB strength of water is weakened and then strengthened with the increase of 1,2-PD volume fraction. In the case of SRS, two new peaks at 3283 cm-1 and 3319 cm-1 were appeared, which demonstrated the appearance of ice-like structures near the methyl group and the weakening of HBs. Based on these phenomena, the HB structure of this binary system underwent a transition from H2O-H2O to H2O-1,2-PD when the V1,2-PD was 0.4 as V1,2-PD increased. This work serves as a reference value for the study of HB networks in alcohol-water binary solutions.

Efficient frequency conversion and the crossing-pump effect of stimulated Raman scattering in an aqueous sodium sulfate solution.

The cascaded stimulated Raman scattering (SRS) of an aqueous sodium sulfate solution was investigated as well as the generation of the crossing-pump effect. With the introduction of dual sample cells, the first-order Stokes of the O-H stretching vibrational mode was able to act as the pump light to excite the Stokes of the S-O stretching vibrational mode, and a new Raman peak was obtained at 4423 cm-1. The dual sample cell device not only lowered the SRS threshold, but also enhanced the four-wave mixing (FWM) process. Compared to the input laser of 7 ns/pulse, the first-order Stokes of O-H was compressed to a pulse width of 413 ps after passing through the dual sample cells. The SRS of aqueous sodium sulfate solution covered an ultrabroad wavelength ranging from 441 nm to 720 nm (a Raman shift ranging from -3859 cm-1 to 4923 cm-1). The cone-shaped launch ring of the FWM process was also recorded. This work provides a reference for the establishment of laser frequency conversion devices using an aqueous sodium sulfate solution as the Raman medium.

Intramolecular Vibration Energy-Transfer-Driven Cascaded Stimulated Raman Scattering and Four-Wave Mixing in Benzene Series.

Cascaded stimulated Raman scattering (SRS) of benzene, bromobenzene, chlorobenzene, ethylbenzene, and toluene was investigated by a pulsed Nd:YAG laser with 532 nm wavelength. The results showed that the third-order Stokes SRS of the ring skeleton vibration (CC at 3006 cm-1) accompanied by another higher-frequency Stokes SRS of the CH stretching vibration (at 3066 cm-1), which arose only when the third-order Stokes SRS of the ring skeleton was produced, can be attributed to the vibration energy transfer between vibration energy levels of CC and CH. The Stokes and anti-Stokes SRS rings, which originated from the intramolecular energy-transfer-enhanced four-wave mixing (FWM) processes, can be observed only in the forward direction along different angles apart from the pump beam direction. The phenomenon also existed in other derivatives of benzene. We propose the intramolecular energy-transfer-enhanced SRS for the first time, which can be used for a broadband Raman laser.

The main anthocyanin monomer of Lycium ruthenicum Murray induces apoptosis through the ROS/PTEN/PI3K/Akt/caspase 3 signaling pathway in prostate cancer DU-145 cells.

Anthocyanins have been reported to have effective chemopreventive activity. Lycium ruthenicum Murray is rich in anthocyanins and exhibits many biological activities. The purpose of this study was to investigate the effects and possible biological mechanism of the main anthocyanin monomer (Pt3G) of Lycium ruthenicum Murray on prostate cancer DU-145 cells. The cell proliferation was detected by methyl thiazolyl tetrazolium assay. The cell apoptosis rates were assessed by flow cytometric analysis and TUNEL assay. The expressions of apoptosis related proteins were evaluated by western blotting. Our data demonstrated that Pt3G inhibited cell proliferation, induced apoptosis and promoted cell cycle arrest at the S phase in a concentration-dependent manner (0, 100, 200 and 400 µg mL-1). Furthermore, it was shown that Pt3G decreased the mitochondrial membrane permeability through regulating the expressions of Bax and Bcl-2. Western blot analysis indicated that Pt3G significantly increased the expression of PTEN and then activated the PI3K/Akt-mediated caspase 3 pathway. In addition, our results also suggested that Pt3G activated the PTEN gene to induce the apoptosis of DU-145 cells by stimulating the overproduction of ROS. To sum up, these results indicate that Pt3G inhibits cell proliferation and induces apoptosis through the ROS/PTEN/PI3K/Akt/caspase 3 signaling pathway in prostate cancer DU-145 cells. Therefore, Pt3G of Lycium ruthenicum Murray may be a potential anti-proliferative agent for the prevention or treatment of prostate cancer.

Enhanced Stimulated Raman Scattering by a Pressure-Controlled Shock Wave in Liquid Water.

Stimulated Raman scattering (SRS) is observed using a Nd:YAG laser in liquid water at both forward and backward directions under different pressures. The spectra at atmospheric pressure and high pressure exhibit different characteristic features. For high pressure, the main SRS peak (about 3400 cm-1) of liquid water shifts to low frequency. Interestingly, a new peak is observed in both directions. The position of the new peak is lower than that at atmospheric pressure, which belongs to strong hydrogen bonds. Especially, a low peak is obtained at around 3140 cm-1 in the backward direction at 400 MPa, indicating the formation of an ice-like structure. In addition, the normalized SRS intensity of high pressure is higher than that of atmospheric pressure. These results indicate that high pressure can significantly enhance the SRS of water molecules. The enhancement mechanism is attributed to the long duration and slightly slow velocity of the shock wave induced by high pressure.

Si quantum dots enhanced hydrogen bonds networks of liquid water in a stimulated Raman scattering process.

Stimulated Raman scattering (SRS) of silicon quantum dots (Si QD) water solutions of different sizes (2 and 5 nm) are investigated using Nd:YAG laser. Since strong and weak hydrogen bonds are formed by the charge transfer between water molecules and Si QDs, two SRS peaks of OH stretching vibrations of Si QDs solutions are observed in the forward direction. Simultaneously, characteristic feature peaks related to the interaction between OH groups and excess electrons are obtained in the backward SRS of 2 nm Si QDs solutions. The excess electrons induce a strong electrostatic field, leading to the transformation from water to an ice-VIII structure.

Raman spectra study hydrogen bonds network in ice Ih with cooling.

The Raman spectra of ice Ih (H2O and HDO) in the temperatures range from 253 to 83 K are measured. The results show that Raman peaks shift to low- or high-wavenumber due to the influence of temperature on hydrogen bonds dynamics. Importantly, Raman shifts are linear relationship with temperatures and its slope fully reflects the change of hydrogen bonds length. Finally, Raman intensity of ice Ih dependent on temperatures are also discussed.

A Raman spectroscopy study on the effects of intermolecular hydrogen bonding on water molecules absorbed by borosilicate glass surface.

The structural forms of water/deuterated water molecules located on the surface of borosilicate capillaries have been first investigated in this study on the basis of the Raman spectral data obtained at different temperatures and under atmospheric pressure for molecules in bulk and also for molecules absorbed by borosilicate glass surface. The strongest two fundamental bands locating at 3063cm-1 (2438cm-1) in the recorded Raman spectra are assigned here to the OH (OD) bond stretching vibrations and they are compared with the corresponding bands observed at 3124cm-1 (2325cm-1) in the Raman spectrum of ice Ih. Our spectroscopic observations have indicated that the structure of water and deuterated water molecules on borosilicate surface is similar to that of ice Ih (hexagonal phase of ice). These observations have also indicated that water molecules locate on the borosilicate surface so as to construct a bilayer structure and that strong and weak intermolecular hydrogen bonds are formed between water/deuterated molecules and silanol groups on borosilicate surface. In accordance with these findings, water and deuterated water molecules at the interface of capillary have a higher melting temperature.

Influence of the hydrogen bond quantum nature in liquid water and heavy water on stimulated Raman scattering.

Stimulated Raman scattering (SRS) of liquid water and heavy water have been investigated using Nd:YAG laser. The SRS spectra of liquid heavy water indicate that ice-VII and ice-VIII structures are formed by shock-induced compression (SIC) in forward and backward directions, respectively. Simultaneously, the SRS spectra reveal of liquid water that only ice-VII structure is formed in the backward direction. The difference in ice structures formed by SIC in liquid water and heavy water could be attributed to the effect of the hydrogen bond quantum nature with H+. SRS spectra of 2M NaOH water solution with ice-VII and ice-VIII structures have been successfully obtained in forward and backward, respectively, as OH- greatly reduce the quantum nature of hydrogen bonds by neutralizing H+ in water. The hydrogen bond quantum nature is important for understanding isotope calibration test structure and isotopic effect.

Study of hydrogen bonding in ethanol-water binary solutions by Raman spectroscopy.

Raman spectra of ethanol-water binary solutions have been observed at room temperature and atmospheric pressure. We find that with increasing ethanol concentration, the symmetric and asymmetric OH stretching vibrational mode (3286 and 3434cm-1) of water are shifted to lower frequency and the weak shoulder peak at 3615cm-1 (free OH) disappears. These results indicate that ethanol strengthens hydrogen bonds in water. Simultaneously, our experiment shows that Raman shifts of ethanol reverses when the volume ratio of ethanol and the overall solution is 0.2, which demonstrates that ethanol-water structure undergoes a phase transition.

Dynamic high pressure induced strong and weak hydrogen bonds enhanced by pre-resonance stimulated Raman scattering in liquid water.

355 nm pulsed laser is employed to excite pre-resonance forward stimulated Raman scattering (FSRS) of liquid water at ambient temperature. Due to the shockwave induced dynamic high pressure, the obtained Raman spectra begin to exhibit double peaks distribution at 3318 and 3373 cm-1 with the input energy of 17 mJ,which correspond with OH stretching vibration with strong and weak hydrogen (H) bonds. With laser energy rising from 17 to 27 mJ, the Stokes line at 3318 cm-1 shifts to 3255 and 3230 cm-1 because of the high pressure being enlarged. When the energy is up to 32 mJ, only 3373 cm-1 peak exists. The strong and weak H bond exhibit quite different energy dependent behaviors.

Structure of water molecules from Raman measurements of cooling different concentrations of NaOH solutions.

The Raman spectra of different concentrations of NaOH solutions have been successfully obtained at normal pressure by cooling. The results indicate that the icing point and the ice phase transition temperature of NaOH solutions decrease with increasing concentrations. Particularly, the different concentrations (2, 4, 6 or 8 and 12M) take place the liquid- III- Ih, liquid- V- Ih, liquid- VI- XV and liquid- IX- VI phase transition, respectively. In addition, the three peaks of around 3524, 3580 and 3624cm-1 appear spectra of the NaOH solutions at low temperature.

Study of the transient "free" OH radical generated in H2O-H2O2 mixtures by stimulated Raman scattering.

Forward and backward stimulated Raman scattering (SRS) were studied in the H2O2-H2O mixtures by a strong excitation laser with 532nm. Only the backward SRS (BSRS) of the H2O2-H2O system shows an unexpected SRS shoulder peak at around 3600cm-1, which is similar to the characteristic peak of "free" OH radical. The generation of the "free" OH radical is mainly attributed to the dissociation of hydrogen peroxide (HP) molecules. Simultaneously, the ionization of HP-water clusters generates a part of "free" OH radical under the Laser-induced breakdown (LIB). The interaction of water and HP is also discussed.

Influence of strong and weak hydrogen bonds in ices on stimulated Raman scattering.

Stimulated Raman scattering (SRS) in liquid water and ice Ih using Nd:YAG laser is investigated. The spectrum of backward SRS (BSRS) in water is acquired. The spectrum shows an unexpected SRS peak at around 3453 cm(-1) besides the normal peak, which is similar to the spontaneous Raman spectrum of ice VII. The ice VII phase will be formed by laser-induced shock compression in liquid water. Simultaneously, unlike the spontaneous Raman spectrum, the pre-resonance SRS of ice Ih at around 3110 and 3210 cm(-1) is observed. The Raman peaks appeared in liquid water and ice Ih are attributed to the effect of strong and weak hydrogen bonds (H bonds), which should be ubiquitous in other ice phases.

Nanoshock wave resonance enhancement on stimulated Raman scattering of H(2)O(2) in liquid water.

This study investigates the stimulated Raman scattering (SRS) of H(2)O(2)-H(2)O mixtures. The laser-induced plasma nanoshock wave is formed by focusing an intense pulsed 532 nm laser beam on the mixtures. An enhancement at the low-frequency 1715 cm(-1) SRS line of the bending mode of H(2)O(2) is observed. The mechanism of enhancement was attributed to nanoshock wave resonance with the bending mode, which would preferentially excite phonon and lower energy molecular vibrations.

Pre-resonance-stimulated Raman scattering for water bilayer structure on laser-induced plasma bubble surface.

Pre-resonance-stimulated Raman scattering (PSRS) from water molecules in the air/water interfacial regions was studied when the laser-induced plasma bubble was generated at the interfaces. A characteristically lower Raman shift of OH-stretching vibrational modes of water molecules at around 3000 cm(-1) (370 meV) was observed, in which the mechanisms were possibly attributed to the strong hydrogen bond in a well-ordered water bilayer structure that was formed on a laser-induced plasma bubble surface. Simultaneously, the PSRS of ice Ih at about 3100 cm(-1) was obtained, which also belonged to the strong hydrogen bond effect in ice Ih structure.

Hydrated-electron resonance enhancement O-H stretching vibration of water hexamer at air-water interface.

Raman scattering of the O-H stretching vibration mode inside water, as well as near and at the air-water interface, was investigated by laser-induced breakdown (LIB). An intense and characteristic higher wavenumber Raman shift of the O-H vibration was observed at the air-water interface, which was attributed to the hydrated-electron resonance enhancement of the O-H stretching vibration mode of water hexamer. The hydrated electron in the water hexamer structure was formed by excess electrons injected into the gas-like phase with low hydrogen bond order under LIB. The electron-phonon coupled mechanism was discussed.

Anharmonic coupling between fundamental modes in tetramethylurea.

In situ high pressure Raman spectra of tetramethylurea have been measured up to 25 GPa, liquid-solid and solid-solid phase transitions were detected at 0.2 GPa and 7.4 GPa, respectively. An unprecedented spectral phenomenon is the observation of a Fermi resonance between the fundamental modes. An exponential relationship between the intensity and the frequency difference was concluded. Pressure provides us a new way to study the correlation between Fermi resonance parameters.

Raman spectra from symmetric hydrogen bonds in water by high-intensity laser-induced breakdown.

Raman spectra of ice VII and X were investigated using strong plasma shockwave generated by laser-induced breakdown (LIB) in liquid water. Simultaneously, the occurrence of the hydrogen emission lines of 656 nm (Hα), 486 nm (Hß), 434 nm (Hγ) and 410 nm (Hδ) was observed. At 5 × 10(12) W/cm(2) optical power density, the O-H symmetric stretching, translational and librational modes of ice VII and a single peak at 785 cm(-1) appeared in the spectra. The band was assigned to the Raman-active O-O mode of the monomolecular phase, which was the symmetric hydrogen bond of cuprite ice X. The spectra indicated that ice VII and X structure were formed, as the trajectory of the strong plasma shockwave passes through the stable Pressure-Temperature range of ice VII and X. The shockwave temperature and pressure were calculated by the Grüneisen model.

[Enhancing stimulated Raman scattering of water and heavy water lattice vibration by laser induced plasma].

Stimulated Raman scattering was studied in water and heavy water using pulse laser at the wavelength of 532nm, not only obtaining the stimulated Raman of O-H and O-D stretching vibration, but also obtaining the stimulated Raman lattice vibration. When the laser energy was 130 mJ, the low frequency Stokes and anti-Stokes 313 cm(-1) line of water could be observed; When the laser energy was 160 mJ, the low frequnecy Stokes and anti-Stokes 280 cm(-1) line of heavy water could be observed. The results were explained by physics mechanism of laser induced plasma.