Photoinitiated Rearrangement of Aromatic Azides to 2-Aminonicotinates.

This study describes a one-pot photoinduced method for azepine synthesis and their subsequent rearrangement into pyridines. The rearrangement of the azepine, formed during photolysis, occurs due to both thermal and photochemical activation of the reaction. This requires an electron-donating substituent at the second position of the azepine and an electron-withdrawing substituent at the third position of the azepine. A reaction mechanism has been proposed to explain the role of water and the nature of the azepine substituents.

Year-Round Presence of Microcystins and Toxin-Producing Microcystis in the Water Column and Ice Cover of a Eutrophic Lake Located in the Continuous Permafrost Zone (Yakutia, Russia).

This study aimed to test the hypothesis of the year-round presence of toxigenic Microcystis and cyanotoxins in the water and ice of the shallow eutrophic Lake Ytyk-Kyuyol located in the continuous permafrost zone. Three independent approaches-mass-spectrometry, molecular methods and light microscopy-were applied in the study. The cyanobacterial biomass ranged from 1.0 × 10-4 to 4.8 mg L-1. Microcystis flos-aquae and M. aeruginosa were the dominant morphospecies in plankton throughout the observation. In environmental DNA, the presence of M. aeruginosa was supported and mcy gene regions responsible for microcystin biosynthesis were detected through a BLAST (Basic Local Alignment Search Tool) search and phylogenetic estimation based on newly obtained 16S rRNA, 16S-23S ITS rRNA, mcyA and mcyE nucleotide sequences. The intracellular microcystin concentration ranged from <0.1 to 803 ng L-1, and the microcystin quota in the Microcystis biomass was extremely low. For the first time, it was shown that Microcystis cells containing mcy genes and microcystins presented permanently in the water column, both during the ice-free period and under ice, as well as inside thick ice covers within 7 months of severe winter. We hypothesized that minor pelagic and ice populations of Microcystis could participate in increasing cell density in the spring. However, further studies are needed to confirm the viability of the overwintering Microcystis colonies in the water and inside the ice of Lake Ytyk-Kyuyol.

Monitoring the skin structure during edema in vivo with spatially resolved diffuse reflectance spectroscopy.

Significance: Edema occurs in the course of various skin diseases. It manifests itself in changes in water concentrations in skin layers: dermis and hypodermis and their thicknesses. In medicine and cosmetology, objective tools are required to assess the skin's physiological parameters. The dynamics of edema and the skin of healthy volunteers were studied using spatially resolved diffuse reflectance spectroscopy (DRS) in conjunction with ultrasound (US). Aim: In this work, we have developed a method based on DRS with a spatial resolution (SR DRS), allowing us to simultaneously assess water content in the dermis, dermal thickness, and hypodermal thickness. Approach: An experimental investigation of histamine included edema using SR DRS under the control of US was conducted. An approach for skin parameter determination was studied and confirmed using Monte-Carlo simulation of diffuse reflectance spectra for a three-layered system with the varying dermis and hypodermis parameters. Results: It was shown that an interfiber distance of 1 mm yields a minimal relative error of water content determination in the dermis equal to 9.3%. The lowest error of hypodermal thickness estimation was achieved with the interfiber distance of 10 mm. Dermal thickness for a group of volunteers (7 participants, 21 measurement sites) was determined using SR DRS technique with an 8.3% error using machine learning approaches, taking measurements at multiple interfiber distances into account. Hypodermis thickness was determined with root mean squared error of 0.56 mm for the same group. Conclusions: This study demonstrates that measurement of the skin diffuse reflectance response at multiple distances makes it possible to determine the main parameters of the skin and will serve as the basis for the development and verification of an approach that works in a wide range of skin structure parameters.

Grading cartilage damage with diffuse reflectance spectroscopy: Optical markers and mechanical properties.

Osteoarthritis (OA) is one of the most common joint diseases worldwide. Unfortunately, clinical methods lack the ability to detect OA in the early stages. Timely detection of the knee joint degradation at the level of tissue changes can prevent its progressive damage. Here, diffuse reflectance spectroscopy (DRS) in the NIR range was used to obtain optical markers of the cartilage damage grades and to assess its mechanical properties. It was observed that the water content obtained by DRS strongly correlates with the cartilage thickness (R = .82) and viscoelastic relaxation time (R = .7). Moreover, the spectral parameters, including water content (OH-band), protein content (CH-band), and scattering parameters allowed for discrimination between the cartilage damage grades (10-4 < P ≤ 10-3 ). The developed approach may become a valuable addition to arthroscopy, helping to identify lesions at the microscopic level in the early stages of OA and complement the surgical analysis.

In vivo sensing of cutaneous edema: A comparative study of diffuse reflectance, Raman spectroscopy and multispectral imaging.

Quantitative noninvasive assessment of water content in tissues is important for biomedicine. Optical spectroscopy is potentially capable of solving this problem; however, its applicability for clinical diagnostics remains questionable. The presented study compares diffuse reflectance spectroscopy, Raman spectroscopy and multispectral imaging in the characterization of cutaneous edema. The source-detector geometries for each method are selected based on Monte Carlo simulations results to detect the signal from the dermis. Then, the kinetics of the edema development is studied for two models. All methods demonstrate synchronous trends for histamine-induced edema: The water content reaches a maximum of 1 hour after histamine application and then gradually decreases. For the venous occlusion, a 51% increase in water content is observed with Raman spectroscopy. The differences in water content estimation by three methods are explained based on the light propagation model. The obtained results are essential for introducing quantitative optical water measurement technology to the clinics.

Pericapillary Edema Assessment by Means of the Nailfold Capillaroscopy and Laser Scanning Microscopy.

Edema, i.e., fluid accumulation in the interstitial space, accompanies numerous pathological states of the human organism, including heart failure (HF), inflammatory response, and lymphedema. Nevertheless, techniques for quantitative assessment of the edema's severity and dynamics are absent in clinical practice, and the analysis is mainly limited to physical examination. This fact stimulates the development of novel methods for fast and reliable diagnostics of fluid retention in tissues. In this work, we focused on the possibilities of two microscopic techniques, nailfold video capillaroscopy (NVC) and confocal laser scanning microscopy (CLSM), in the assessment of the short-term and long-term cutaneous edema. We showed that for the patients with HF, morphological parameters obtained by NVC-namely, the apical diameter of capillaries and the size of the perivascular zone-indicate long-term edema. On the other hand, for healthy volunteers, the application of two models of short-term edema, venous occlusion, and histamine treatment of the skin, did not reveal notable changes in the capillary parameters. However, a significant reduction of the NVC image sharpness was observed in this case, which was suggested to be due to water accumulation in the epidermis. To verify these findings, we made use of CLSM, which provides the skin structure with cellular resolution. It was observed that for the histamine-treated skin, the areas of the dermal papillae become hyporefractive, leading to the loss of contrast and the lower visibility of capillaries. Similar effect was observed for patients undergoing infusion therapy. Collectively, our results reveal the parameters can be used for pericapillary edema assessment using the NVC and CLSM, and paves the way for their application in a clinical set-up.