Invitro impact of a combination of red and infrared LEDs, infrared laser and magnetic field on biomarkers of oxidative stress and hemolysis of erythrocytes sampled from healthy individuals and diabetes patients.

AIMS: Low-intensity infrared laser irradiation with output emissions of the laser and LED for in vitro irradiation of plasma and erythrocyte samples collected from healthy individuals and diabetes mellitus (DM) patients was used in the current study. METHODS: The generated emission was in the range 0.85-0.89 nm with pulse duration near 130 ns and repetition rates of pulses 50, 150, 600, and 1500 Hz, average power 0, 50, or 100 mW, in the range of 1-9 min for different 30 variants of irradiation. The levels of 2-thiobarbituric-acid reactive substances (TBARS), aldehydic and ketonic derivatives of oxidatively modified proteins (OMP), total antioxidant capacity (TAC), acid-induced resistance of erythrocytes, and activities of the main antioxidant enzymes were assessed in erythrocyte and plasma samples after irradiation. RESULTS: The low-intensity infrared laser irradiation and low-intensity light emitted by a red LED decreased the lipid peroxidation levels in the erythrocytes of both healthy individuals and DM patients. A statistically significant decrease in TBARS and OMP levels and an increase in the TAC level were observed at the irradiation energy of 34.39 and 68.79 J/cm2 for samples collected from both healthy individuals and DM patients. The effects of the irradiation were accompanied by a statistically significant decrease in catalase activity of both healthy individuals and DM patients. CONCLUSIONS: In many variants of the laser irradiation and low-intensity light emitted by a red LED used in our study, a decrease in the percent of hemolyzed erythrocytes was observed, suggesting that laser therapy protocols should take into account fluencies, frequencies, and wavelengths of the laser before the beginning of treatment, especially in DM patients.

Changes in energetic metabolism and lysosomal destruction in the skeletal muscle and cardiac tissues of pigeons (Columba livia f. urbana) from urban areas of the northern Pomeranian region (Poland).

The aim of the present study was to evaluate the biochemical responses of the skeletal muscle and cardiac tissues of the urban pigeon as a bioindicator organism tested in diverse environments (Szpegawa as a rural environment and Slupsk as an urban environment, Pomeranian Voivodeship, northern Poland), resulting in changes in the level of lipid peroxidation at the initial and final stages of this process and the activities of Krebs cycle enzymes (succinate dehydrogenase, pyruvate dehydrogenase, isocitrate dehydrogenase, and alfa-ketoglutarate dehydrogenase). Szpegawa village was chosen due to the intensive use of the European motorway A1 with significant traffic and pollution levels. The concentration of Pb was higher in the soil and feathers of pigeons nesting in the polluted areas (Szpegawa). Our studies have shown that the presence of lead in soil and feathers of the pigeons resulted in the activation of lipid peroxidation, destabilization and increased activity of lysosomal membranes, and activation of mitochondrial enzymes of the Krebs cycle with energy deficiency (reduction of ATP levels) in cardiac and skeletal muscle tissues simultaneously.

Profile of Heavy Metals and Antioxidant Defense in the Muscle Tissues of Pigeons (Columba livia f. urbana) from Anthropogenically Transformed Areas in the Pomeranian Region (Northern Poland).

Pigeons can be successfully used as bioindicators of a contaminated environment. We studied the relationship between the functioning of the pro/antioxidant balance in muscle tissues (skeletal muscle and cardiac tissues) of pigeons (Columba livia f. urbana) living in areas with different levels of pollution (Pomeranian Voivodeship, Northern Poland). The current study demonstrated the impact of the environment with preferential high Pb contamination in soil and feathers of pigeons on the formation of adaptive redox mechanisms in muscle tissues. An increase in the intensity of lipid peroxidation (estimated by the TBARS level) accompanied by enhancement of the oxidative modification of proteins (aldehydic and ketonic derivatives) and an important decrease in the activity of antioxidant enzymes (SOD, CAT, and GR) in pigeon muscle tissue was observed. These changes in enzyme activities were dependent on the type of muscle tissue (skeletal muscle and cardiac tissues). Our results confirm the concept of the recalculation of the De Ritis ratio (AsAT/AlAT) in both types of muscles indicating the tendency to cardio- and hepatocellular damage and toxicity caused by heavy metals from the polluted environment.

Direct excitation of higher excited state and kinetics of photoreactions.

Excited-state reactions (ESR) play an essential role in chemical, physical, and biological processes. The mathematical models are usually used to study ESR in kinetics and steady-state regimes. In these models, the excitation pulse populates the first excited state (the first singlet level) of the primary molecular form. Recently, researchers' paid growing attention to the reactions excited via the higher energy levels. We modeled these reactions using the system of linear differential equations. Exact analytical expressions of the kinetics of N* and P* populations were derived for the general case when excitation performed via the higher Sn singlet state by the delta pulse. The graphical forms of these expressions were N and P time-dependent pulses. We detected the changes of the pulses' shapes, their maxima locations, the time behavior of the populations, and the total yield of the P* population. The changes occur due to the populating of the product excited state in the kinetic and thermodynamic reaction regimes. Numerical analysis performed for different ESR parameters revealed peculiarities of the N* and P* populations. Kinetics properties of these population characterize systems with varying rates of reversible ESR and various contributions of anti-Kasha (AK) reaction (from the Sn state) to P* population. Modeling data presented in graphical form, allowed to understand better (a) the impact of the AK reaction on the kinetic properties of the excited states of the molecular systems operating in various mode of ESR (kinetic, reversible and intermediate); (b) the photochemical processes' mechanisms. Also, this modeling allowed establishing the criteria for revealing the effect of the AK reaction for improving the efficiency of anti-Kasha processes.

Spectroscopic methods for the study of energetic characteristics of the normal and photoproduct forms of 3-hydroxyflavones.

We report spectroscopic properties of 3-hydroxyflavone (3-HF) and 4'-N,N-dimethylamino-3-hydroxyflavone (DMA3HF) in acetonitrile and ethyl acetate at different temperatures in the range from 10 °C to about 67 °C. These compounds are characterized by excited-state intramolecular proton transfer (ESIPT) which leads to occurrence of two forms of these molecules. For this reason their fluorescence spectra have two bands which correspond to emission of normal and photoproduct (tautomer) forms. The correlation between ratio of integrated intensity of these two bands and inverse absolute temperature (the Arrhenius plot) have been applied to estimate energetic properties, such as difference between energy levels of excited states as well ground states for normal and tautomer forms for each molecule.

Breaking the Kasha Rule for More Efficient Photochemistry.

This paper provides a systematic review and analysis of different phenomena that violate a basic principle, Kasha's rule, when applied to photochemical reactions. In contrast to the classical route of ultrafast transition to the lowest energy excited state and photochemical reaction starting therein, in some cases, these reactions proceed directly from high-energy excited states. Nowadays, this phenomenon can be observed for a number of major types of excited-state reactions: harvesting product via intersystem crossing; photoisomerizations; bond-breaking; and electron, proton, and energy transfers. We show that specific conditions for their observation are determined by kinetic factors. They should be among the fastest reactions in studied systems, competing with vibrational relaxation and radiative or nonradiative processes occurring in upper excited states. The anti-Kasha effects, which provide an important element that sheds light on the mechanisms of excited-state transformations, open new possibilities of selective control of these reactions for a variety of practical applications. Efficient utilization of excess electronic energy should enhance performance in the systems of artificial photosynthesis and photovoltaic devices. The modulation of the reporting signal by the energy of excitation of light should lead to new technologies in optical sensing and imaging.