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The stratum corneum of the outermost skin is an important barrier impeding transdermal permeation, and permeation enhancers can reduce the barrier resistance of the stratum corneum and enhance the permeation of drugs in tissues. The optical imaging depth, signal intensity, and scattering coefficient variation rules of skin tissues in time dimension are obtained by using optical coherence tomography (OCT). The effect of optical clearing agents (OCAs) on OCT imaging is obtained by quantitatively analyzing the changes in the optical properties of tissues. D-fructose, one of the monosaccharides, and sucrose, one of the disaccharides, were selected for the ex vivo optical clearing experiments on pig skin tissues utilizing the dimethyl sulfoxide (DMSO) carrier effect. We find that DMSO synergized with sugars applied to skin tissue has a more significant increase in the optical imaging depth and signal intensity, and a reduction in the scattering coefficient with an increasing concentration of DMSO. DMSO with a high concentration and D-fructose with saturated concentration (10:1; v/v) effectively reduce light attenuation in OCT imaging and improve the image quality. This operation will also shorten the application time to minimize skin damage from hyperosmotic agents.
Assuntos
Açúcares , Tomografia de Coerência Óptica , Animais , Suínos , Dimetil Sulfóxido/farmacologia , Pele , FrutoseRESUMO
Despite a great deal of effort spanning for decades, it remains yet puzzling concerning how alcohol molecules functionalize the hydrogen bond (H-bond) networks of water. We employed an isotopic substitution method (using alcohol-heavy water system) to avoid spectral overlap between the alcohol hydroxyl groups and water hydrogen bonds. We showed spectrometrically that under the strong pulse laser, the low mixing ratio (VA < 20%) of alcohol can strengthen the H-bond network structure of D2O through :ÖC2H6â D2Ö: compression. But when VA > 20%, H-bond network of D2O will deform via the self-association between alcohol molecules. Our experiments not only reveal the H-bond kinetics of heavy water-alcohol interactions but also provide important reference for understanding the distinctive properties of H-bond in water-organic system.
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The microstructural, electrical, and optical properties of crystals are critical to laser device performance, and the temperature-dependence effect of crystals has gained a great deal of attention in research. The linewidth, stimulated Raman scattering (SRS) shift, and intensity of the characteristic peak at 890â cm-1 of YVO4 crystal have been investigated between 148 and 448â K. As the crystal temperature increases, the bond length increases and the crystal force constant decreases, and the phonon softening process arises in the crystal at high temperature. The temperature effect on Raman shift and full width at half maximum is explained in detail in terms of the phonon anharmonic effect. The temperature dependence of SRS can be well demonstrated by an empirical equation. This work can provide new insights into the further understanding of lattice anharmonicity and contribute to the discovery of new optoelectronic materials.
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A method of energy-transfer resonance of lycopene used to enhance stimulated Raman scattering (SRS) of a weak vibration C-O mode in tetrahydrofuran (THF) was developed in this study. Only C-H SRS was observed in pure THF at high energies. When lycopene was added, the C-O SRS located at 915â cm-1 of the weak vibration mode in THF was observed. The maximum SRS enhancement of the C-O mode was achieved when the concentration was 3.72 × 10-6â mol/L because of the resonance enhancement of the solute, which transferred the excess vibrational energy to the solvent. Moreover, the pulse width compression phenomenon of the C-H vibration in the presence of C-O SRS was obtained.
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Ring skeleton vibrations of aromatic series are dominant in Raman spectroscopy compared with the C-H stretching vibrations. When a laser-induced plasma (LIP) was generated in a mixed solution of naphthalene and benzene, an anomalous enhancement was observed in stimulated Raman scattering (SRS) of aromatic C-H stretching vibrations of naphthalene (3055â cm-1). However, SRS of C-H stretching vibrations of benzene at 3060â cm-1 disappeared. The LIP produced electrons and cations, and the transient production of ionized material contributed to the enhancement of SRS of C-H vibrations of naphthalene. Density functional theory calculations showed that the C-H Raman activity of the naphthalene molecules in (naphthalene-benzene)+ heterodimer was significantly enhanced compared with neutral naphthalene. In addition, SRS pulse durations were better compressed in pure benzene and naphthalene due to the self-focusing effect.
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Carotenoids are a class of natural pigments that play a fundamental role in photosynthesis and optoelectronics. However, the complexity of their energy level structure and electronic states has prevented a clear interpretation of their photophysics and photochemistry. The mediating nonradiative decay of the bright S2 state to the dark S1 state of carotenoids involves a population of bridging intermediate state. Herein, time-dependent DFT was used to study the energy level and electronic excitation process of ß-carotene. A π-π* transition and π electron delocalization of electron excitation could be inferred based on the difference in the electron cloud distribution of the HOMO and LUMO orbitals. Through the electronic transition contribution in the UV-vis spectra and the electron density difference between the ground state and the excited state, the electronic energy level structure and possible dark state were analyzed. On this basis, the electronic excitation process of ß-carotene was theoretically studied by combining electron-hole analysis and transition density matrix (TDM). There was a charge transfer from the ß-ionone ring to the long-chain in the (S0) â (S2), (S0) â (S4) and (S0) â (S5).
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Supercontinuum radiation has found numerous applications in diverse fields encompassing spectroscopy, pulse compression, and tunable laser sources. Anomalous enhanced stimulated Raman scattering (SRS) of cyclohexane-benzene mixtures was obtained in this study. SRS of the pure solvent, the multi-order Stokes of the strongest fundamental vibration modes, and energy transfer in intra-molecular modes were observed. SRS of the mixture revealed that the cross-pumping effect was generated between the C-H stretching (v2) mode of cyclohexane and the C=C ring skeleton (v1) mode of benzene, thereby producing the intermolecular secondary stimulated Raman emission and the appearance of two super-broadband radiations at 664.36-673.9 nm and 704.62-729.22 nm. The results suggest that the energy transfer of intermolecular vibrational modes, where the strongest vibrational mode excites other vibrational modes, is a simple approach for generating supercontinuum coherent radiation.
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The hydrogen bond (HB) network structure and kinetics of the acetone-water mixed solutions were investigated by the spontaneous Raman and stimulated Raman scattering (SRS) spectra. The HB network of water molecules was enhanced when the volume fraction of acetone ranged from 0 to 0.25. Two new SRS peaks of water at 3272 and 3380 cm-1 were obtained, resulting from the cooperation of the polar carbonyl (C = O)-enhanced HB and the ice-like structure formed around the methyl groups. However, when the volume fraction went beyond 0.25, the spontaneous Raman main peak at 3445 cm-1 showed a significant blue-shift, and the corresponding SRS signal disappeared, indicating that the HB of water was weakened, which originated from the self-association of acetone. In the meantime, the fully tetrahedral HB structure among water molecules was destroyed at the higher volume fraction (≥ 0.8). Hopefully, our study here would advance the study of HB network structures and kinetics in other aqueous solutions.
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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.
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The cascaded stimulated Raman scattering (SRS) of 30% H2O2 aqueous solutions was investigated using a pulsed Nd: YAG laser with a wavelength of 532â nm. The transfer of excess electrons between H2O2 and H2O molecules enhanced the SRS. Together, the decomposition of H2O2 and the intense SRS Stokes led to the generation of the crossing-pump effect of H2O2 aqueous solutions and the appearance of a new peak at 4229â cm-1 that is excited by Stokes as the pump source. Crossing-pump not only reduced the threshold but also generated the broadband-coherent Raman comb, defined as a coherent radiation wavelength ranging from 434 to 831â nm (i.e., a Raman shift ranging from -4225 to 6756â cm-1). The anti-Stokes SRS was attributed to the four-wave mixing (FWM) process.
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Stimulated Raman scattering (SRS) in a liquid has been a major focus of nonlinear optics. Traditional SRS generates single or cascaded Stokes components arising from spontaneous Raman noise. Herein, we report the formation mechanism of a specific spectrum-continuous spectroscopy technique based on SRS of mixed liquids. SRS of a mixed acetone and carbon disulfide solution is investigated by a pulsed Nd:YAG laser with a wavelength of 532â nm. Two remarkably asymmetric broadened SRS lines are obtained. When the volume ratio is 7:3, the broadened spectral bands are optimized. The supercontinuum spectroscopy phenomenon is explained by hydrogen bond formation, adjacent vibrational modes coupling, and laser-induced plasma generation. This technique has the potential to contribute to the development of a supercontinuum Raman laser.
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Nanosecond laser-induced breakdown (LIB) in liquids (e.g., water) can produce dynamic high pressure and high temperature. However, since high pressure needs to negate the effect of high temperature to some degree, it is only partially effective. As a result, it is difficult to directly measure the effective pressure due to the transient and complex LIB process. Here, we presented a simple method based on Raman spectroscopy to indirectly determine the effective pressure caused by LIB in liquid pure H2O and low concentration H2O-H2O2 mixtures. By comparing the Raman shifts of the ice-VII mode for pure H2O and H2O-H2O2 mixtures under laser pumping and static high pressure, the LIB effective pressure can be first estimated. The empirical equation was then derived base on the correlation of the LIB effective pressure to ice-VII-point stimulated Raman scattering thresholds for pure and mixture water solutions, which can be used to estimate the LIB effective pressures for other different mixture water solutions with the uncertainty of 0.14-0.25 Gpa. Hopefully, our study here would advance the measurements of effective pressure in the LIB process.
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Acetonitrile (AN), as an organic solvent, has a wide range of applications. The C≡N stretching vibration mode (ν2) and the combination mode (ν3 + ν4) are coupled by Fermi resonance (FR). In this work, the phase transition and the interaction mechanism of the 60% AN-water binary solution (AN-Water) were analyzed by calculating FR parameters and two-dimensional correlation Raman spectroscopy (2DCRS). The change in the ν2 band and the base bands ν3 and ν4 caused energy transfer by anharmonic interaction, which led to a change in FR parameters. With a reduced temperature, the energy transfer was caused by microheterogeneity and the energy transfer effect (293-273 K), the phase separation (263-233 K), and the phase transition of AN (223-173 K). The 2DCRS and Gaussian deconvolution provided more information on FR, which revealed the interaction mechanism of the Fermi doublet. The polarity and binding modes of molecules provided a new perspective for analyzing the transmission of electrons and ions in the electrolyte at different temperatures.
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Stimulated Raman scattering (SRS) of liquid and ice-Ih D2O was investigated using a pulsed Nd:YAG laser with a wavelength of 532 nm. The high-order Stokes peaks and corresponding anti-Stokes SRS [Coherent Anti-Stokes Raman Spectroscopy (CARS)] peaks were obtained. Two symmetric and antisymmetric Raman modes of stretching vibrations were observed in liquid D2O, while only a symmetric stretching vibration mode was observed in ice-Ih D2O. Pure Stokes SRS is always collinear with the pump beam along the axial direction. Some ring-like Stokes SRS and CARS shifts, which originate from four-wave mixing processes, can also be observed only in the forward direction along with different angles meeting the phase-matching criteria, respectively. Simultaneously, the temporal behavior of SRS in liquid and ice-Ih D2O was examined, and the temporal waveforms of the pump laser pulse, transmitted pump pulse, and the forward SRS pulse were measured. In both cases, SRS was the dominant contributor to stimulated scattering. However, the efficiency values drastically decreased due to the self-termination behavior of SRS in liquid D2O, which arose from the thermal self-defocusing of both the pump beam and the SRS beam, owing to the Stokes shift-related opto-heating effect. In contrast, for the SRS process in ice-Ih D2O, the thermal self-defocusing influence was negligible, benefitting from a much greater thermal conductivity and a higher conversion efficiency of SRS generation retained under both of the conditions.
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Cascaded stimulated Raman scattering (SRS) of carbon disulfide (CS2) was investigated by a pulsed Nd:YAG laser with a wavelength of 532 nm. The fourth-order Stokes and second-order anti-Stokes lines were generated when the pump laser energy was about 1.909 mJ in one sample cell (C1) only. However, the same result was obtained in the second sample cell (C2) with a pump energy of 0.883 mJ. At the same time, the fifth-order Stokes line was produced in C2 when the pump energy increased to 1.208 mJ, and the coherent radiation wavelength ranged from 498 to 644 nm. The result was attributed to the resonance enhancement effect, where the frequency difference between the pump laser and the Stokes light emitted from the working medium (CS2) self-matched with the vibrational energy level of C=S, which resulted in the generation of the cascaded broadband SRS. The anti-Stokes SRS was attributed to four-wave mixing. Simultaneously, the pulse durations of the Stokes and anti-Stokes were compressed to about 380 ps by SRS and laser-induced breakdown. The resonance effect not only reduced the threshold, but it also generated broadband and short-pulse SRS.
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Resonance Raman scattering can be used to investigate the ground and excited state information of carotenoid. It is known that the Dushinsky rotation can significantly influence the resonant Raman intensity of ß-carotene (ß-car). The excited state geometry revealed by the double components feature of the C = C stretching vibrational modes and the environmental dependence of the Raman intensity for each component remain unknown. We explore the influence of environmental factors on the relative intensity of these two C = C stretching vibration modes and perform two-dimensional resonance Raman correlation analysis to reveal the changes on ß-car excited state geometry. The results show that the relative wavelength difference between the 0-0 absorption and the excitation is the key factor that decides the intensity ratio of the two components and that the intensity of each mode is modulated by environmental factors. This modulation is closely related to the excited state geometry and dynamics, effective conjugation length, and electron-phonon coupling constant. It also shows that the asynchronous cross-peaks in the two-dimensional resonance Raman correlation spectrum (2DRRCOS) can effectively characterize the degree of the varied electron-phonon coupling with the changing conditions. These results are not only complementary to the research on the excited states of carotenoids but also applicable to investigate the environmental dependence of Raman intensity for a lot of π-conjugated molecules.
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Stimulated Raman scattering (SRS) of water and a 1 M KOH-H2O solution are investigated using a Nd:YAG laser in both forward and backward directions. An obvious enhanced SRS signal is realized by dissolving KOH in liquid water. Compared with pure water, the performance improvements include the appearance of low-wavenumber Raman peaks, higher Raman intensity, an increased Raman gain, and an enhanced hydrogen bonding network. In this paper, the SRS enhancement phenomenon is explained from both the hydrogen bonding structure and the mechanism of stimulated Raman scattering. We consider it to be a very important SRS enhancement technique, which is low cost, simple, but reliable. Meanwhile, it can easily be extended to other alkali hydroxides.
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Stimulated Raman scattering (SRS) and spontaneous Raman spectra are both used here to study the hydrogen bond (HB) structure and kinetics of methanol (MeOH)-water mixtures in different volume ratios. We have found that when the volume fraction of MeOH ranges from 0 to 0.27, the HB structure of water molecules is enhanced, originating from the cooperation of the hydroxyl-enhanced HBs in liquid water and the formation of an ice-like structure around the methyl groups. However, when the volume fraction of MeOH goes beyond 0.27, the main Raman peak of water becomes very weak and even disappeared, which reveals that the HB structure of liquid water is weakened. This weakening can be attributed to the H-H repulsion introduced by MeOH salvation derives. Furthermore, some HBs among water molecules are destroyed at a high MeOH volume fraction ([gt-or-equal]0.7) based on the change of C-H vibrations.
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Halogen bonding, an attractive interaction that is analogous to hydrogen bonding, has been widely investigated by computational methods. However, halogen bonding in solution is hard to study by spectroscopic techniques since the intermolecular interaction often gives overlapping bands and may be difficult to interpret. The traditional interpretation of iodomethane-ethanol mixtures considered only hydrogen bonding effects and the experimental investigation was limited. Here, we employed near-infrared (NIR) spectroscopy, Raman, density functional theory calculation, and two-dimensional (2D) correlation analysis to find evidence of the halogen bonding in iodomethane-ethanol mixtures. Our results suggest that the blue-shifting C-I stretching band is probably due to the cooperative influence from halogen bonding, hydrogen bonding, and the solvent effect, while the O-H band is a cumulative band from three dimer complexes. The 2D correlation spectra further validate the hypothesis above and reveal the interaction evolution from the ethanol-rich region to the iodomethane region. These results indicate that the unique nature of the iodomethane-ethanol mixture and the larger σ-hole strengthen the halogen bond, leading to particular spectroscopic results which are different from those of the other halogenated alkanes.
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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.