Confocal Raman micro-spectroscopy (CRM) has developed into a versatile tool that is frequently used to determine skin penetration of various compounds. Topically applied optical clearing agents decrease skin scattering, improving CRM imaging abilities. The use of magnetic resonance (MR) and X-ray contrast agents to increase transparency of biological objects has attracted more attention recently. By analysing Raman bands at 1003 and 1663 cm-1 and applying Fick's second law model, we calculated the diffusion coefficients of 3.51 × 10-8 cm2/s for Gadovist and 3.20 × 10-7 cm2/s for Omnipaque, with a slower diffusion regime for Dotarem. These diffusion kinetics directly governed penetration depth profiles across the investigated 0-240 µm dermal region and dictated optical clearing efficiency. Gadovist yielded the strongest short-term (30 min, up to 52% signal increase), whereas Omnipaque reached the highest and most depth-uniform optical clearing (60 min), consistent with its one-order-of-magnitude higher diffusivity. In contrast, Dotarem exhibited limited penetration and negligible optical clearing. Autofluorescence enhancement scaled with diffusion-driven refractive index matching, confirming that optical clearing is mechanistically coupled to molecular transport; it may also arise from protein structural modifications, oxidative stress, or increased protein density following contrast agent interaction. Together, these findings establish a quantitative link between contrast-agent diffusivity, dermal penetration depth, optical transparency, and tissue autofluorescence, providing a framework for integrating Raman, MR, and X-ray modalities in multimodal depth-resolved skin imaging.
Cardiomyopathies are often characterized by significant fibrotic remodelling of the heart, marked by an abnormal accumulation of collagen type I. Label free Raman spectroscopy, a non-invasive diagnostic technique, holds promise for monitoring biochemical changes throughout the initiation and progression of different diseases, including cardiomyopathies. This study demonstrates the effectiveness of 70% glycerol as a hyperosmotic immersion liquid for in-depth controlling the optical properties of ex vivo myocardium tissue during deep-UV Raman spectroscopy with 244 nm excitation. The results revealed a considerable enhancement in the intensities of Raman peak, particularly the amide I region after glycerol treatment. This occurred across all depths (0-120 & micro;m) and glycerol treatment durations (30 and 60 min). A noticeable enhancement of the Raman peak at 1647 cm-1 was also observed that is attributable to structural transformations of the collagen due to the dehydration induced by glycerol. This finding suggest that deep-UV Raman can be employed as a specific probe of the collagen environment. As the amide I region reflects structural changes in collagen type I, these findings propose the potential of deep-UV Raman spectroscopy in combination with glycerol as optical clearing agent for monitoring collagen modifications.
The ex vivo porcine lung tissue exposure to nicotine-flavour free e-liquid was examined in-depth using confocal Raman micro-spectroscopy. It was found that the lung-related Raman bands and autofluorescence intensities were enhanced after exposure to e-liquid for all depths and treatment time (first and second treatments) due to the optical clearing effect of glycerol and propylene glycol as an OC agent. The nicotine-flavour free e-liquids that contain glycerol and propylene glycol could potentially be used in clinical protocols for lung disease discrimination in-depth using Raman-based in vivo bronchoscopy due to light scattering reduction as an optical clearing agent.
The effect of laser irradiation in the energy range from 20 mW to 200 mW was investigated in 109 nm thick Fe _51 Rh _49 film deposited on an MgO (100) substrate. The initial, A1 structure with fully paramagnetic magnetic ordering was achieved after irradiating the samples with 120 keV Ne ^+ ions with a fluence of 1 × 10 ^16 ion cm ^−2 , as it was confirmed by conversion-electron Mössbauer spectroscopy. At higher powers physical damage of the layer was observed, while in the lowest power case, magnetic force microscopy revealed a well-defined magnetic structure reflecting the laser irradiation pattern. The presented results have the potential to be employed for laser ablation or allows the fabrication of arbitrary ferromagnetic pattern within a homogeneous paramagnetic FeRh thin films.
Fluid and mineral inclusions in metamorphic rocks allow the understanding of fluid-involved processes in subduction-zones providing essential contributions to the nature of geochemical processes and element cycling in present day subduction zones. In this work, we studied ultramafic granulite from the high-pressure (HP) and high-temperature (HT) metamorphic series of the Cabo Ortegal Complex, Spain, combining quartz-in-garnet and zircon-in-garnet Raman spectroscopy-based elastic geothermobarometry with Ti-in-quartz trace element ther-mometry. The studied quartz and zircon inclusions occur within garnet, together with rutile and multiphase fluid inclusions (MFI). Textural evidence, like occurrence in the same 3D cluster and common intergrowth of mineral inclusions, shows that both crystal inclusions and MFI were likely entrapped simultaneously. Hence, the appli-cation of elastic thermobarometry to quartz and zircon inclusions in these rocks provides excellent opportunity to define P-T environment of entrapment. Results from Raman spectroscopy on multiple quartz and zircon in-clusions showed that the remnant elastic inclusion pressure (Pinc) at room conditions for both (on average 0.51 +/- 0.04 GPa and 0.72 +/- 0.05 GPa for the quartz and zircon inclusions, respectively) fall within the range of 2 sigma uncertainty confirming the crystallization within the same growth-stage of garnet. Intersection of the entrapment isomekes is at a P-T of 1.8 +/- 0.2 GPa and 880 +/- 70 degrees C. Electron microprobe measurements on quartz inclusions from the same garnet zone show uniform Ti concentrations (45-59 ppm). Isopleths calculated from Ti-in-quartz thermometer intersect the average quartz-in-garnet isomeke within the P-T range indicated by the intersection of quartz and zircon entrapment isomekes, which is P = 1.8 +/- 0.2 GPa and T = 860 +/- 70 degrees C. Besides, we made a comparison of different reference materials applied for zircon-in-garnet elastic thermo-barometry verified by independent Ti-in-quartz trace element thermometry. Our findings indicate that elastic thermobarometry on mineral inclusions provide a reliable constraint on the entrapment P-T conditions of coexisting fluid inclusions.
Ex vivo porcine lung immersed in e-liquid was investigated in-depth using confocal Raman micro-spectroscopy to assess the e-liquid influence on the lung. It was found that lung-related Raman band intensities at 1002, 1548, 1618 and 1655 cm(-1) increased after first and second treatments except the surface, which was attributed to the well-known optical clearing (OC) effect due to alveoli filling with e-liquid resulting in light scattering reduction. The autofluorescence enhancement was explained by oxidative stress induced in lung during exposure to e-liquid. Moreover, e-liquid induced collagen dehydration was revealed by the I-937/I-926 Raman band intensity ratio change. The effect was enhanced after the second treatment of the same lung tissue that indicates the possibility of multi-step OC treatment. We hypothesize that the nicotine-flavour-free e-liquids containing glycerol and propylene glycol could potentially be used in clinical protocols as OC agent for enhanced in-depth Raman-guided bronchoscopy.
AbstractStimulated Raman Scattering (SRS) microscopy is a light-based non-linear imaging method for visualizing a molecule based on its chemical properties, i.e., the vibrational energy states reflecting the molecule’s structure and its environment. This technique, relying on the specificity of the molecule’s spectral fingerprint, enables label-free, high-sensitivity, and high-resolution 3D reconstruction of the distribution and the properties of a molecule within a tissue. Despite its tremendous potentials, the application of SRS is still not frequent in the field of life science, where it could be applied over an extremely broad investigation range, from the study of the molecular interactions at subcellular level to the characterization of tissue alterations in clinical studies. Trying to fill this gap, here, after describing the general principles of SRS, we present the materials and the methods to integrate spectrally focused Stimulated Raman Spectroscopy (sf-SRS) on commercial multiphoton microscopes and highlight the critical aspects to consider.
In situ U–Pb analyses were performed on SEM-BSE, SEM-CL and Raman mapped zircons from the Variscan granitoids exposed in the Mórágy pluton, Hungary. However, the routinely used LA-ICP-MS could result only in reliable age constraints if the system was not overprinted by multiple geological processes that affect the isotope system of zircons. To overcome the ambiguities the new zircon U–Pb age data were evaluated carefully, first using simple statistical models, then a zircon internal texture related complex approach was applied. This method demonstrates that the U–Pb age in overprinted systems correlates with the structural state; the worse structural state zones showing younger, but still concordant ages. Individual zircon internal texture and structural state based evaluation made it possible to select the least overprinted age components of the system and identify five steps in the evolution of the studied intrusive rock. The two melts (granitoid and mafic) passed the zircon U–Pb isotope closure temperature 355 ± 3 Ma ago during their cooling. Crystallization of the two mingled magmas overarched the 350–340 Ma period, including two intense zircon crystallization peaks ( 347 Ma, 333 Ma). The cessation of melt crystallization ( 650 °C) happened 334 ± 4 Ma ago, as indicated by the age of the “normal and long prismatic” zircons. Further confirming this statement, they are embedding in their rims the eutectic mineral assemblage. A Cretaceous post-magmatic event was identified according to slightly discordant U–Pb ages for the Mórágy pluton.
Gold nanoparticle assisted thermally initiated chemical vapor deposition was used to synthesize nanostructured As-S films. The nanostructures were grown on heated Si substrates covered by spherical gold nanoparticles of different (5, 20, 40 and 60 nm) sizes. In contrast to polycrystalline As-S films prepared by ordinary thermal evaporation and chemical vapor deposition of As2S3 glass without the use of gold nanoparticles, the gold nanoparticle assisted synthesis leads to growth of particular type of crystal-like As-S nanostructures. The As-S micro-crystallites with well-defined size and shape were obtained with 43.9 and 56.1 at% As and S atomic content, respectively. The local structure of the As-S microcrystallites was investigated by Raman and/or surface-enhanced Raman spectroscopy. To assist the interpretation of the experimental Raman spectra and to identify the structure of the crystallites, the vibrational spectra of different cage-like nanocluster models were also calculated by using the density functional theory. Results show that at specific deposition conditions a stimulated formation of As4S5 molecules occurs which activates the growth of micro-crystallites on the gold nanoparticle coated Si surface with well distinguished shape. The structure and properties of nanostructured As-S films synthesized with and without the use of gold nanoparticles were investigated and the gold nanoparticle assisted selective growth of a new type of As-S microcrystallite is discussed. (C) 2021 Elsevier B.V. All rights reserved.
The middle Anisian extensional tectonics of the Neotethyan realm developed a small, isolated carbonate platform in the middle part of the Balaton Highland (western Hungary), resulted in the deposition of uranium-bearing seamount phosphorite on the top of the drowned platform and produced some epigenetic fluorite veins in the Middle Triassic sequence. The stable C-O isotope data of carbonates are shifted from the typical Triassic carbonate ranges, confirming the epigenetic-hydrothermal origin of veining. Primary fluid inclusions in fluorite indicate that these veins were formed from low temperature (85–169 °C) and high salinity NaCl + CaCl2 + H2O type (apparent total salinity: 15.91–22.46 NaCl wt%) hydrothermal fluids, similar to parent fluids of the Alpine-type Pb-Zn deposits. These findings indicate that the Triassic regional fluid circulation systems in the Alpine platform carbonates also affected the area of the Balaton Highland. This is also in agreement with the previously established palinspatic tectonic reconstructions indicating that the Triassic carbonate and basement units in the Balaton Highland area were a part of the Southern Alpine. Similar fluorite veining in phosphorite deposits is also known in the Southern Alpine areas (e.g., Monte San Giorgi, Italy). Raman spectroscopic analyses detected H2 gas in the vapor phase of the fluid inclusions and a defect-rich fluorite structure in violet to black colored growth zones. This unique phenomenon is assumed to be the result of interaction between the uranium-rich phosphorite and the parent fluids of the epigenetic fluorite veins.
Nickel nanoparticles are gaining increasing attention in catalysis due to their versatile catalytic action. A novel, low-cost and facile method was developed in this work to synthesize carbon microsphere-supported metallic nickel nanoparticles (Ni-NP/C) for heterogeneous catalysis. The synthesis was based on carbonizing a polystyrene-based cation exchange resin loaded with nickel ions at temperatures between 500 and 1000 °C. The decomposition of the nickel-organic framework resulted in both Ni-NP and carbon microsphere formation. The phase composition, morphology and surface area of these Ni-NP/C microspheres were characterized by powder X-ray diffraction, Raman spectroscopy, scanning electron microscopy and BET analysis. Elemental nickel was found to be the only metal containing phase; fcc-Ni coexisted with hcp-Ni at carbonization temperatures between 500 and 700 °C, and fcc-Ni was the only metallic phase at 800–1000 °C. Graphitization and carbon nanotube formation were observed at high temperatures. The catalytic activity of Ni-NP/C was tested in the reduction of 4-nitrophenol to 4-aminophenol by sodium borohydride, and Ni-NP/C was proved to be an efficient catalyst in this reaction. The relatively easy and scalable synthetic method, as well as the easy separation and catalytic activity of Ni-NP/C, provide a viable alternative to existing nickel nanocatalysts in future applications.
In this work, the degree of conversion and polymerization kinetics of diethylene glycol dimethacrylate (DEGDMA) monomer in different solvents upon gamma irradiation with different doses have been studied by Raman spectroscopy and mass difference measurements. Density functional theory calculations were performed on the monomer and the crosslinked structure to obtain the assignment of Raman peaks to specific bonds. The evolution of the bonding configuration of the structure with dose and the composition of the monomer mixture was investigated. The dependence of the polymerization rate on the solvent type was explained by the mechanism of the polymerization affected by the relative solubility of the components of the monomer mixture. Raman measurements revealed also that there are not fully crosslinked monomer molecules in the polymer matrix.
Confocal Raman microspectroscopy (CRM) with 633- and 785-nm excitation wavelengths combined with optical clearing (OC) technique was used for ex-vivo study of porcine skin in the Raman fingerprint region. The optical clearing has been performed on the skin samples by applying a mixture of glycerol and distilled water and a mixture of glycerol, distilled water and chemical penetration enhancer dimethyl sulfoxide (DMSO) during 30[Formula: see text]min and 60[Formula: see text]min of treatment. It was shown that the combined use of the optical clearing technique and CRM at 633[Formula: see text]nm allowed one to preserve the high probing depth, signal-to-noise ratio and spectral resolution simultaneously. Comparing the effect of different optical clearing agents on porcine skin showed that an optical clearing agent containing chemical penetration enhancer provides higher optical clearing efficiency. Also, an increase in treatment time allows to improve the optical clearing efficiency of both optical clearing agents. As a result of optical clearing, the detection of the amide-III spectral region indicating well-distinguishable structural differences between the type-I and type-IV collagens has been improved.
Composition and bonding configuration of silicate glasses with different lithium content was studied by laser induced breakdown spectroscopy and Raman spectroscopy. The lithium content of the formed glass matrix has been determined by using laser induced breakdown spectroscopy with high precision. Analysis of the Raman spectra implied on the complex character of lithium incorporation into the glassy matrix with lithium content. It was found that the addition of lithium results in more depolymerized SiO4 structures and, in general, increases the disorder of the structure. However, at certain concentrations lithium has an ordering effect due to more homogeneous size distribution of structural units of the glass matrix.
A new and simple method is developed to synthesize carbon microspheres decorated with iron sulfide nanoparticles for mercury ion removal from water. The synthesis is based on carbonizing polystyrene–divinylbenzene-based and iron(III) sulfate-loaded cation exchange resins between 500 and 1000 °C. The phase composition, surface area, and morphology of these materials are characterized by various spectroscopic and diffraction techniques, including Mössbauer spectroscopy, powder X-ray diffraction, Raman and scanning electron microscopy, and BET analysis. Pyrrhotite is found to be the dominant iron-containing phase. The adsorption performance of microspheres for mercury ion removal from water is studied as a function of adsorbent load and contact time at pH 6.5 using a solution of 40 mg dm −3 mercury ion. Pyrrhotite nanoparticles played a key role in mercury ion removal amounting to 70–90% of the extracted amount. A high adsorption capacity of 104 mg of mercury/g of adsorbent at an adsorbent load of 0.33 g dm −3 is achieved, and the removal kinetics could be well fitted with a pseudo-second-order kinetic model, indicating chemical sorption. The synthetic method is easy to scale up for large-scale production and materials are easy to handle, which is significant for large-scale environmental applications.
Rudabanyaite was found in cavities of siliceous sphaerosiderite and limonite rocks at the Adolf mine area of the Rudabanya ore deposit (North-East Hungary). The new mineral forms small crystals up to 0.6 mm and aggregates of a few mm across. Usually they have a xenomorphic shape, only occasionally cubic symmetry is morphologically discernible; the crystal forms {110} and {100} were recognized. The crystals are transparent, have yellowish-orange to brownish-yellow colour and a lemonyellow streak, the lustre is adamantine. The Mohs' hardness is 3-4. No cleavage was observed. Rudabanyaite is optically isotropic. The density could not be measured due to lack of material; rho(calc.) = 8.04 g/cm(3). Electron-microprobe analyses gave the average composition (in wt%) Ag2O 29.39, Hg2O 52.62, As2O5 13.69, Cl 4.62, SO3 0.19, O= Cl - 1.04, sum 99.47. The empirical formula based on four oxygen atoms is (Ag2.06Hg2.05)(Sigma)= 4.11(As0.97S0.02)(Sigma= 0.99)O4Cl1.06; the idealized formula as derived from chemical analyses and crystal-structure investigation is [Ag2Hg2][AsO4] Cl. The crystal-structure investigation was performed on single-crystal X-ray data; the refinements on F-2 converged at wR2(F-2) = 0.068 and R1(F) = 0.031 for all 972 unique data and 53 variable parameters. Rudabanyaite crystallizes in space group F (4) over bar 3c, a = 17.360(3) angstrom, V = 5231.8 angstrom(3), Z = 32. The crystal structure is characterised by two crystallographically different [M-4](4+) cluster cations forming tetrahedra; M = (Ag, Hg) with a ratio Ag:Hg similar to 1:1. There is not any evidence for an order between the Ag and Hg atoms. Small amounts of the M atoms are displaced by similar to 0.5 angstrom. Topologically, the barycentres of the [M-4](4+) clusters and the As atom positions of the crystal structure of rudabanyaite form a cubic primitive lattice with a' = 1/2 a = 8.68 angstrom; half of the voids are occupied by Cl atoms.
A gold-coated array of flow-through inverse pyramids applicable as substrate for entrapment and immobilization of micro-objects and for surface enhanced Raman spectroscopic measurements was fabricated using bulk micromachining techniques from silicon. Surface morphology, optical reflectance, immobilization properties, and surface enhanced Raman amplification of the array were modelled and characterized. It was found that the special perforated periodic 3D structure can be used for parallel particle and cell trapping and highly sensitive molecular analysis of the immobilized objects.
Gold coated patterned silicon substrates of different morphology, pattern size and period were prepared by photolithography and subsequent etching. Their performance in surface enhanced Raman scattering (SERS) was tested using an organic model compound. The highest enhancement was obtained for an array of inverse pyramids, followed by inverse hemispheres and rounded-edge inverse pyramids. The SERS performance of the substrates was demonstrated with silicon-carbide nanoparticles.