Search Results (17)

This paper presents an overview of the application of Raman spectroscopy (RS) in characterizing carotenoids, which have recently gained attention due to new findings on their health-promoting effects and rising demand in the food, pharmaceutical, and cosmetic industries. The backbone structure in the form of a polyene chain makes carotenoids sensitive to Raman spectroscopy, mainly due to the stretching vibrations of their conjugated double bonds. Raman spectroscopy is increasingly used in agricultural and food sciences and technologies as it is a non-preparative, environmentally friendly, fast and efficient method for characterizing target analytes. The application of RS in the qualitative and quantitative analysis of carotenoids requires the careful selection and adjustment of various instrument parameters (e.g., laser wavelength, laser power, spectral resolution, detector type, etc.) as well as performing complex chemometric modeling to interpret the Raman spectra. Most of the studies covered in this review focus more on qualitative than quantitative analysis. The most frequently used laser wavelengths are 1064, 785, and 532 nm, while 633 nm is the least used. Considering the sensitivity and complexity of RS, the present study focuses on the specific and critical points in the analysis of carotenoids by RS. The main methodological and experimental principles in the study of food carotenoids by RS are discussed and best practices recommended, while the future prospects and expectations for a wider application of RS, especially in food quality assessment, are emphasized. New Raman techniques such as Spatially Offset Raman Spectroscopy (SORS), Coherent Anti-Stokes Raman Spectroscopy (CARS) and Stimulated Raman Scattering Spectroscopy (SRS), as well as the application of artificial intelligence, are also described in the context of carotenoids analysis. Full article

Aceclofenac (ACF), a non-steroidal anti-inflammatory drug, was obtained in its amorphous state by cooling from melt. The glass transition was investigated using dielectric and calorimetric techniques, namely, dielectric relaxation spectroscopy (DRS), thermally stimulated depolarization currents (TSDC), and conventional and temperature-modulated differential scanning calorimetry (DSC and TM-DSC). The dynamic behavior in both the glassy and supercooled liquid states revealed multiple relaxation processes. Well below the glass transition, DRS was able to resolve two secondary relaxations, γ and β, the latter of which was also detectable by TSDC. The kinetic parameters indicated that both processes are associated with localized motions within the molecule. The main (α) relaxation was clearly observed by DRS and TSDC, and results from both techniques confirmed a non-Arrhenian temperature dependence of the relaxation times. However, the glass transition temperature (T_g) extrapolated from DRS data significantly differed from that obtained via TSDC, which in turn showed reasonable agreement with the calorimetric T_g (T_g-DSC = 9.2 °C). The values of the fragility index calculated by the three experimental techniques converged in attributing the character of a moderately fragile glass former to ACF. Above the α relaxation, TSDC showed a well-defined peak. In DRS, after “removing” the high-conductivity contribution using ε’ derivative analysis, a peak with shape parameters α_HN = β_HN = 1 was also detected. The origin of these peaks, found in the full supercooled liquid state, has been discussed in the context of structural and dynamic heterogeneity. This is supported by significant differences observed between the FTIR spectra of the amorphous and crystalline samples, which are likely related to aggregation differences resulting from variations in the hydrogen bonds between the two phases. Additionally, the pronounced decoupling between translational and relaxational motions, as deduced from the low value of the fractional exponent x = 0.72, derived from the fractional Debye–Stokes–Einstein (FDSE) relationship, further supports this interpretation. Full article

The influence of the interference between coherent processes in third-order nonlinear Raman scattering on the spectral shapes of Raman-scattered light waves is numerically modeled and discussed in the cases of commonly used coherent Raman spectroscopy techniques. The effects on the lineshapes depending on the laser intensity are analyzed for the coherent Raman spectroscopy performed via the excitation of molecular systems with focused laser pulses at high intensities. In this case, the interplay between the coherent processes in nonlinear Raman scattering, as well as laser power-induced resonance effects, may be significant and should be taken into account in the spectral lineshape analysis in coherent Raman spectroscopy and its related applications, since the coherent Raman spectra may be considerably modified. Full article

Simultaneous gas phase temperature and water vapor concentration measurement are important to understand reacting flows such as combustion or gas reforming processes. Here, coherent anti-Stokes Raman scattering (CARS) offers the possibility for non-intrusive measurements with a high temporal and spatial resolution. Therefore, this work demonstrates the simultaneous measurement of temperature and relative water vapor–nitrogen concentrations by using dual-pump vibrational coherent anti-Stokes Raman scattering (DPVCARS). A calibration procedure is developed for a temperature range of 473 K to 673 K and a water vapor concentration of 24% to 46% at ambient pressure. This setup is tested with 500 CARS single pulse spectra taken in a gas cell at a known temperature and concentration. Based on these results, information about precision and accuracy can be delivered. Full article

Herein, we investigate the performance of single- and multiparametric luminescence thermometry founded on the temperature-dependent spectral features of Ca₆BaP₄O₁₇:Mn⁵⁺ near-infrared emission. The material was prepared by a conventional steady-state synthesis, and its photoluminescence emission was measured from 7500 to 10,000 cm⁻¹ over the 293–373 K temperature range in 5 K increments. The spectra are composed of the emissions from ¹E → ³A₂ and ³T₂ → ³A₂ electronic transitions and Stokes and anti-Stokes vibronic sidebands at 320 cm⁻¹ and 800 cm⁻¹ from the maximum of ¹E → ³A₂ emission. Upon temperature increase, the ³T₂ and Stokes bands gained in intensity while the maximum of ¹E emission band is redshifted. We introduced the procedure for the linearization and feature scaling of input variables for linear multiparametric regression. Then, we experimentally determined accuracies and precisions of the luminescence thermometry based on luminescence intensity ratios between emissions from the ¹E and ³T₂ states, between Stokes and anti-Stokes emission sidebands, and at the ¹E energy maximum. The multiparametric luminescence thermometry involving the same spectral features showed similar performance, comparable to the best single-parameter thermometry. Full article

Searching for new low-dimensional organic–inorganic hybrid phosphors is of great significance due to their unique optical properties and wide applications in the optoelectronic field. In this work, we report a Mn⁴⁺ doped zero-dimensional organic–inorganic hybrid phosphor [N(CH₃)₄]₂ZrF₆, which was synthesized by a wet chemical method. The crystal structure, thermal stability, and optical properties were systemically investigated by means of XRD, SEM, TG-DTA, FTIR, DRS, emission spectra, excitation spectra, as well as decay curves. Narrow red emission with high color purity can be observed from [N(CH₃)₄]₂ZrF₆:Mn⁴⁺ phosphor, which maintains effective emission intensity even at room temperature, indicating its potential practical application in WLEDs. In the temperature range of 13–295 K, anti-Stokes and Stokes sidebands of Mn⁴⁺ ions exhibit different temperature responses. By applying the emission intensity ratio of anti-Stokes vs. Stokes sidebands as temperature readout, an optical thermometer with a maximum absolute sensitivity of 2.13% K⁻¹ and relative sensitivity of 2.47% K⁻¹ can be obtained. Meanwhile, the lifetime Mn⁴⁺ ions can also be used for temperature sensing with a maximum relative sensitivity of 0.41% K⁻¹, demonstrating its potential application in optical thermometry. Full article

Anti-Stokes photoluminescence (ASPL), which is an up-conversion phonon-assisted process of the radiative recombination of photoexcited charge carriers, was investigated in methylammonium lead bromide (MALB) perovskite nanocrystals (NCs) with mean sizes that varied from about 6 to 120 nm. The structure properties of the MALB NCs were investigated by means of the scanning and transmission electron microscopy, X-ray diffraction and Raman spectroscopy. ASPL spectra of MALB NCs were measured under near-resonant laser excitation with a photon energy of 2.33 eV and they were compared with the results of the photoluminescence (PL) measurements under non-resonant excitation at 3.06 eV to reveal a contribution of phonon-assisted processes in ASPL. MALB NCs with a mean size of about 6 nm were found to demonstrate the most efficient ASPL, which is explained by an enhanced contribution of the phonon absorption process during the photoexcitation of small NCs. The obtained results can be useful for the application of nanocrystalline organometal perovskites in optoelectronic and all-optical solid-state cooling devices. Full article

Two water-soluble single-benzene-based chromophores, 2,5-di(azetidine-1-yl)-tereph- thalic acid (DAPA) and its disodium carboxylate (DAP-Na), were conveniently obtained. Both chromophores preserved moderate quantum yields in a wide range of polar and protonic solvents. Spectroscopic studies demonstrated that DAPA exhibited red luminescence as well as large Stokes shift (>200 nm) in aqueous solutions. Femtosecond transient absorption spectra illustrated quadrupolar DAPA usually involved the formation of an intramolecular charge transfer state. Its Frank–Condon state could be rapidly relaxed to a slight symmetry-breaking state upon light excitation following the solvent relaxation, then the slight charge separation may occur and the charge localization became partially asymmetrical in polar environments. Density functional theory (DFT) calculation results were supported well with the experimental measurements. Unique pH-dependent fluorescent properties endows the two chromophores with rapid, highly selective, and sensitive responses to the amino acids in aqueous media. In detail, DAPA served as a fluorescence turn-on probe with a detection limit (DL) of 0.50 μM for Arg and with that of 0.41 μM for Lys. In contrast, DAP-Na featured bright green luminescence and showed fluorescence turn-off responses to Asp and Glu with the DLs of 0.12 μM and 0.16 μM, respectively. Meanwhile, these two simple-structure probes exhibited strong anti-interference ability towards other natural amino acids and realized visual identification of specific analytes. The present work helps to understand the photophysic–structure relationship of these kinds of compounds and render their fluorescent detection applications. Full article

The enhancement and selective excitation of coherent anti-Stokes Raman scattering (CARS) and the suppression of background noise are very important problems for real-time detection at the single-molecule level. Optimizing the plasmonic substrate to ensure that all the hot spots of the pump, probe, Stokes, and anti-Stokes light are at the same position is the key to increasing the CARS signal to reach the level of single-molecule detection. The selective excitation of the target CARS peak and the suppression of the other peaks are the key to improving the signal-to-noise ratio. In this paper, we present a theoretical study to control the selective excitation and enhancement of any one of the three CARS peaks using the Fano resonance of a disk-ring structure. By optimizing the modulation of the pump, Stokes, and probe pulse, one CARS peak is maximized, while the other two are suppressed to zero. Fano resonance is applied to simultaneously enhance the four surface plasmon modes of the pump, probe, Stokes, and anti-Stokes light and to ensure that all the hot spots are located at the same position by adjusting the size of the disk-ring structure. The hot spots of the four pulses are concentrated in the disk-ring gap with a deviation distance of less than 2 nm, and the intensity of the CARS is enhanced by 1.43 × 10¹² times, which is much higher than the requirement of single-molecule detection. The time, frequency, and phase distribution of the input and the response of the four pulses are studied in detail. It was found that the selective excitation and the spectra of CARS are both well preserved. Full article

Here, the experimental and numerical results provide evidence of strong coupling between an Au layer and an azo-dye. Strong coupling between the Au and a dye is not easy to observe, so a deep analysis for understanding the physics of the system is carried on. After an accurate analysis of the reflectivity of the plain Au layer as well as after the chromophore adsorption, a hypothesis of strong coupling was advanced. The reflectivity dispersion of system polariton-exciton is characterized by an anti-crossing and two polaritons with a distance that raises with the concentration of the molecules until reaching a condition of saturation, as proof of a non-weak coupling. However, from one side the low-quality factor Q, from the other the optical characteristics of the dye, the strong coupling seems to contradict the achieved results. Then, a possible explanation of these results is that the collective vibrational level structure of the molecules plays a crucial role, and despite the poor conditions of coupling, the matching between the phonons and the excitons reaches an outstanding strength. The emission spectra permitted to characterize the vibrational status of the molecules coupled to the polaritons. Due to the dye adsorption, the surface plasmon frequency shifts, and the Stokes peak splits into two peaks, having a distance bigger than their line width. The strong effect of the collective mechanism of the molecules was described by a hybrid model. Finally, after proving and characterizing the strong coupling, the Raman scattering from such hybridized light-matter states was studied. The coherent nature of the vibro-polariton states increases the Raman scattering cross-section and indicates an enhancement mechanism due to the intrinsic properties of the molecules (e.g., polarizability). Since the light-matter interaction permits the property modulation of materials by confining to small volumes the light field for forming exciton-polariton states, these results provide insight into molecular science. Full article

Hot-band absorption (HBA)-induced anti-Stokes fluorescence (ASF) with longer-wavelength excitation is one effective pathway to deep penetration and low autofluorescence in intravital fluorescence imaging, raising demands for fluorophores with broad spectra, high absorption, and strong emission. However, typical fluorescent dyes display some emission quenching when their concentration is increased in order to obtain brighter fluorescence. In this work, the HBA-induced ASF of aggregation-induced emission (AIE) dots is reported. BPN-BBTD dots were synthesized and confirmed with a fluorescence enhancement and a considerable ASF intensity. In addition, the mechanism of ASF and the HBA process of BPN-BBTD dots were carefully validated and discussed. To obtain the full advantages of the long-wavelength excitation and the short fluorescence lifetime in deep-tissue bioimaging, a large-depth ASF confocal microscopic imaging of in vivo cerebral vasculature was conducted under the excitation of a 980 nm continuous wave laser after intravenous injection of BPN-BBTD dots. Meanwhile, the 3D structure of the cerebrovascular network was successfully reconstructed. Full article

Due to the increase in the average age of humans, Alzheimer’s disease (AD) has become one of the disorders with the highest incidence worldwide. Abnormal amyloid β protein (Aβ) accumulation is believed to be the most common cause of AD. Therefore, distinguishing the lesion areas can provide clues for AD diagnosis. Here, we present an optical spectroscopy and imaging approach based on coherent anti-Stokes Raman scattering (CARS). Label-free vibrational imaging of Aβ in a mouse model of AD was performed to distinguish the lesion areas by studying the spectra of regions with and without Aβ plaques. Raman spectra in Aβ and non-Aβ regions exhibited a specific difference in the intensity ratio of the wave peaks detected at 2850 and 2930 cm⁻¹. In the non-Aβ region, the ratio of the peak intensity at 2850 cm⁻¹ to that at 2930 cm⁻¹ was approximately 1, whereas that in the Aβ region was 0.8. This label-free vibrational imaging may provide a new method for the clinical diagnosis and basic research of AD. Full article

Fluorescence spectra of graphitic (g-C₃N₄) and spherical (s-C₃N₄) modifications of carbon nitride were measured as a function of green pulsed (6 ns-pulse) laser intensity. It was found that the intensity of the laser increases the maximum of the fluorescence shifts towards the anti-Stokes side of the fluorescence for s-C₃N₄ spherical nanoparticles. This phenomenon was not observed for g-C₃N₄ particles. The maximum of the anti-Stokes fluorescence in s-C₃N₄ nanoparticles was observed at 480 nm. The ratio of the intensity of the anti-Stokes peak (centered at 480 nm) to that of the Stokes peak (centered at 582 nm) was measured to be I_484/582 = 6.4 × 10⁻³ at a low level of intensity (5 mW) of a green pulsed laser, whereas it rose to I_484/582 = 2.27 with a high level of laser intensity (1500 mW). Full article

The determination of local temperature at the nanoscale is a key point to govern physical, chemical and biological processes, strongly influenced by temperature. Since a wide range of applications, from nanomedicine to nano- or micro-electronics, requires a precise determination of the local temperature, significant efforts have to be devoted to nanothermometry. The identification of efficient materials and the implementation of detection techniques are still a hot topic in nanothermometry. Many strategies have been already investigated and applied to real cases, but there is an urgent need to develop new protocols allowing for accurate and sensitive temperature determination. The focus of this work is the investigation of efficient optical thermometers, with potential applications in the biological field. Among the different optical techniques, Raman spectroscopy is currently emerging as a very interesting tool. Its main advantages rely on the possibility of carrying out non-destructive and non-contact measurements with high spatial resolution, reaching even the nanoscale. Temperature variations can be determined by following the changes in intensity, frequency position and width of one or more bands. Concerning the materials, Titanium dioxide has been chosen as Raman active material because of its intense cross-section and its biocompatibility, as already demonstrated in literature. Raman measurements have been performed on commercial anatase powder, with a crystallite dimension of hundreds of nm, using 488.0, 514.5, 568.2 and 647.1 nm excitation lines of the CW Ar⁺/Kr⁺ ion laser. The laser beam was focalized through a microscope on the sample, kept at defined temperature using a temperature controller, and the temperature was varied in the range of 283–323 K. The Stokes and anti-Stokes scattered light was analyzed through a triple monochromator and detected by a liquid nitrogen-cooled CCD camera. Raw data have been analyzed with Matlab, and Raman spectrum parameters—such as area, intensity, frequency position and width of the peak—have been calculated using a Lorentz fitting curve. Results obtained, calculating the anti-Stokes/Stokes area ratio, demonstrate that the Raman modes of anatase, in particular the E_g one at 143 cm⁻¹, are excellent candidates for the local temperature detection in the visible range. Full article

The backscattering spectra of a 500 nm thick gold film, which was excited near the 525 nm transverse localized plasmon resonance of its constituent, self-organized, vertically-aligned nanorods by normally incident 515 nm, 300 fs laser pulses with linear, radial, azimuthal and circular polarizations, revealed a few-percent conversion into Stokes and anti-Stokes side-band peaks. The investigation of these spectral features based on the nanoscale characterization of the oligomeric structure and numerical simulations of its backscattering response indicated nonlinear Fano-like plasmonic interactions, particularly the partially degenerate four-wave mixing comprised by the visible-range transverse plasmon resonance of the individual nanorods and an IR-range collective mode of the oligomeric structure. Such oligomeric structures in plasmonic films may greatly enhance inner nonlinear electromagnetic interactions and inner near-IR hotspots, paving the way for their engineered IR tunability for broad applications in chemosensing and biosensing. Full article