Titanium dioxide (TiO2) is considered to be a nontoxic material and is widely used in a number of everyday products, such as sunscreen. TiO2 nanoparticles (NP) are also considered as prospective agents for photodynamic therapy and drug delivery. These applications require an understanding of the potential effects of TiO2 on the blood system and its components upon administration. In the presented work, we analyze the interaction of TiO2 nanoparticles of different crystal phases (anatase and rutile) with individual rat Red Blood Cells (RBC) and the TiO2 influence on the oxygenation state and functionality of RBC, estimated via analysis of Raman spectra of Hemoglobin (Hb) and their distribution along individual RBC. Raman spectral signals also allow localization of the TiO2 NP on the RBC. No penetration of the NP inside RBC was observed; however, both kinds of TiO2 NP adsorbed on the RBC membrane can affect the Hb state. Mechanisms involving the NP–membrane–Hb interaction, resulting in partial deoxygenation of Hb and TiO2 photothermal effect on Hb under Raman laser excitation, are suggested. The possible influence on the safety of TiO2 use in advanced medical application, especially on the safety and efficiency of photothermal therapy, is discussed.
This article presents materials that highlight the bioengineering potential of polymeric systems of natural origin based on biodegradable polysaccharides, with applications in creating modern products for localized wound healing. Exploring the unique biological and physicochemical properties of polysaccharides offers a promising avenue for the atraumatic, controlled restoration of damaged tissues in extensive wounds. The study focused on alginate, pectin, and a hydrogel composed of their mixture in a 1:1 ratio. Atomic force microscopy data revealed that the two-component gel exhibits greater cohesion and is characterized by the presence of filament-like elements. The dynamic light scattering method indicated that this structural change results in a reduction in the damping of acoustic modes in the gel mixture compared to the component gels. Raman spectroscopy research on these gels revealed the emergence of new bonds between the components’ molecules, contributing to the observed effects. The biocompatibility of the gels was evaluated using dental pulp stem cells, demonstrating that all the gels exhibit biocompatibility.
In this work, several optical-spectroscopic methods have been used to visualize and investigate the penetration of diamond nanoparticles (NPs) of various sizes (3–150 nm), surface structures and fluorescence properties into the animal skin in vitro. Murine skin samples have been treated with nanodiamond (ND) water suspensions and studied using optical coherence tomography (OCT), confocal and two-photon fluorescence microscopy and fluorescence lifetime imaging (FLIM). An analysis of the optical properties of the used nanodiamonds (NDs) enables the selection of optimal optical methods or their combination for the study of nanodiamond–skin interaction. Among studied NDs, particles of 100 nm in nominal size were shown to be appropriate for multimodal imaging using all three methods. All the applied NDs were able to cross the skin barrier and penetrate the different layers of the epidermis to finally arrive in the hair follicle niches. The results suggest that NDs have the potential for multifunctional applications utilizing multimodal imaging.
Raman microspectroscopy has become an effective method for analyzing the molecular appearance of biomarkers in skin tissue. For the first time, we acquired in vitro Raman spectra of healthy and malignant skin tissues, including basal cell carcinoma (BCC) and squamous cell carcinoma (SCC), at 532 and 785 nm laser excitation wavelengths in the wavenumber ranges of 900–1800 cm−1 and 2800–3100 cm−1 and analyzed them to find spectral features for differentiation between the three classes of the samples. The intensity ratios of the bands at 1268, 1336, and 1445 cm−1 appeared to be the most reliable criteria for the three-class differentiation at 532 nm excitation, whereas the bands from the higher wavenumber region (2850, 2880, and 2930 cm−1) were a robust measure of the increased protein/lipid ratio in the tumors at both excitation wavelengths. Selecting ratios of the three bands from the merged (532 + 785) dataset made it possible to increase the accuracy to 87% for the three classes and reach the specificities for BCC + SCC equal to 87% and 81% for the sensitivities of 95% and 99%, respectively. Development of multi-wavelength excitation Raman spectroscopic techniques provides a versatile non-invasive tool for research of the processes in malignant skin tumors, as well as other forms of cancer.
Confocal scanning Raman and photoluminescence (PL) microspectroscopy is a structure-sensitive optical method that allows the non-invasive analysis of biomarkers in the skin tissue. We used it to perform in vitro diagnostics of different malignant skin neoplasms at several excitation wavelengths (532, 785 and 1064 nm). Distinct spectral differences were noticed in the Raman spectra of basal cell carcinoma (BCC) and squamous cell carcinoma (SCC), compared with healthy skin. Our analysis of Raman/PL spectra at the different excitation wavelengths enabled us to propose two novel wavelength-independent spectral criteria (intensity ratios for 1302 cm−1 and 1445 cm−1 bands, 1745 cm−1 and 1445 cm−1 bands), related to the different vibrational “fingerprints” of cell membrane lipids as biomarkers, which was confirmed by the multivariate curve resolution (MCR) technique. These criteria allowed us to differentiate healthy skin from BCC and SCC with sensitivity and specificity higher than 95%, demonstrating high clinical importance in the differential diagnostics of skin tumors.
An amorphous carbon film with embedded detonation nanodiamond (DND) particles (a-C:ND) was produced by magnetron sputtering of nanodiamond powder. An Ag film was deposited on the carbon structure by radiofrequency magnetron sputtering. The silver film was irradiated with a 150 eV Ar+ to form plasmonic-active nanoparticles (NP) on the surface of the a-C:ND. The structure of the obtained a-C:ND and a-C:ND/Ag structures were studied by scanning and transmission electron microscopy, electron energy-loss spectroscopy, UV–Visible absorption spectroscopy, Raman spectroscopy, and fluorescence lifetime imaging at two-photon excitation. The analysis revealed 76% of sp3-carbon and a good dispersion of diamond nanoparticles in the a-C. Surface-enhanced Raman scattering (SERS) was applied to investigate the a-C:ND/Ag structure, allowing for the observation of SERS from the sp2-carbon species and the absence of significant a-C:ND damage after Ar+ irradiation of the Ag overlayer. A plasmonic-metal-enhanced luminescence was observed at one- and two-photon excitations, revealing a two- to five-fold intensity increase. The activity of the used DNDs was tested using the agar diffusion method and observed against the bacteria of Bacillus subtilis, Staphylococcus aureus, and Escherichia coli and the fungi of Aspergillus niger, Aspergillus fumigatus, and the yeast of Candida albicans, showing DND activity against all the test strains of fungi.