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The mitochondrion is known as the "powerhouse" of eukaryotic cells since it is the main site of adenosine 5'-triphosphate (ATP) production. Using a temperature-sensitive fluorescent probe, it has recently been suggested that the stray free energy, not captured into ATP, is potentially sufficient to sustain mitochondrial temperatures higher than the cellular environment, possibly reaching up to 50 °C. By 50 °C, some DNA and mitochondrial proteins may reach their melting temperatures; how then do these biomolecules maintain their structure and function? Further, the production of reactive oxygen species (ROS) accelerates with temperature, implying higher oxidative stresses in the mitochondrion than generally appreciated. Herein, it is proposed that mitochondrial heat shock proteins (particularly Hsp70), in addition to their roles in protein transport and folding, protect mitochondrial proteins and DNA from thermal and ROS damage. Other thermoprotectant mechanisms are also discussed.
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Proteínas de Choque Térmico/metabolismo , Mitocôndrias/metabolismo , DNA Mitocondrial/metabolismo , Proteínas de Choque Térmico/genética , Mitocôndrias/genética , Proteínas Mitocondriais/genética , Proteínas Mitocondriais/metabolismo , Espécies Reativas de Oxigênio/metabolismo , Simbiose , Temperatura , Regulação para CimaRESUMO
The possibility of the efficient preparation of graphene-like 1H-WS2 by the primary solventless nanostructuration of bulk 2H-WS2 by means of its mechanochemical treatment in the presence of a chemically inert agent (NaCl) and the subsequent liquid exfoliation of the nanostructured 2H-WS2 in an organic solvent is shown for the first time. The shear stresses generated during the grinding of the WS2/NaCl mixture caused the formation of WS2 particles with a reduced number of layers, while the stresses normal to their surface led to their cracking and a significant reduction in lateral size. The graphene-like morphology of the 1H-WS2 nanoparticles in the prepared dispersions is confirmed by atomic force microscopy and Raman spectroscopy. The semiconducting character of 1Ð-WS2 is supported by electron absorption and x-ray photoelectron spectroscopy data.
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Tremendous deposits of disposable medical facemask waste after the COVID-19 pandemic require improvement of waste management practice according to WHO report 2022, moreover facemasks are still in use around the world to protect against numerous airborne infections. Here, water-suspended smoke preparations from the combustion of disposable medical facemasks (polypropylene fibers) were collected; size, zeta potential, surface groups of smoke particulate matter were determined by dynamic light scattering, FTIR and Raman spectroscopy, and their optical properties were characterized. Neurochemical study using nerve terminals isolated from rat cortex revealed a significant decrease in the initial rate of the uptake/accumulation of excitatory and inhibitory neurotransmitters, L-[14C]glutamate and [3H]GABA, and exocytotic release, and also an increase in the extracellular level of these neurotransmitters. Fluorescent measurements revealed that ROS generation induced by hydrogen peroxide and glutamate receptor agonist kainate decreased in nerve terminals. A decrease in the membrane potential of nerve terminals and isolated neurons, the mitochondrial potential and synaptic vesicle acidification was also shown. Therefore, accidental or intentional utilization of disposable medical facemask waste by combustion results in the release of neuroactive ultrafine particulate matter to the environment, thereby contributing to plastic-associated pollution of air and water resources and neuropathology development and expansion.
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COVID-19 , Fumaça , Animais , Humanos , Ratos , Máscaras , Neurotransmissores , Pandemias , Material ParticuladoRESUMO
Here, water-suspended smoke aerosol preparation was synthesized from biomass-based fuel, i.e., a widespread product for residential heating, wood sawdust (WP) (pine, poplar, and birch mixture), and its properties were compared in parallel experiments with the smoke preparation from plastics (PP). Molecular groups in the PM preparations were analyzed using Raman and Fourier-transform infrared spectroscopy. WP was assessed in neurotoxicity studies using rat cortex nerve terminals (synaptosomes). Generation of spontaneous and H2O2-evoked reactive oxygen species (ROS) detected using fluorescent dye 2',7'-dichlorofluorescein in nerve terminals was decreased by WP. In comparison with PP, WP demonstrated more pronounced reduction of spontaneous and H2O2-evoked ROS production. WP completely inhibited glutamate receptor agonist kainate-induced ROS production, thereby affecting the glutamate receptor-mediated signaling pathways. WP decreased the synaptosomal membrane potential in fluorimetric experiments and the synaptosomal transporter-mediated uptake of excitatory and inhibitory neurotransmitters, L-[14C]glutamate and [3H] γ-aminobutyric acid (GABA), respectively. PP decreased the ambient synaptosomal level of [3H]GABA, whereas it did not change that of L-[14C]glutamate. Principal difference between WP and PP was found in their ability to influence the ambient synaptosomal level of [3H]GABA (an increase and decrease, respectively), thereby showing riskiness in mitigation of synaptic inhibition by PP and triggering development of neuropathology.
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Material Particulado , Fumaça , Animais , Ácido Glutâmico/metabolismo , Peróxido de Hidrogênio/farmacologia , Estresse Oxidativo , Material Particulado/metabolismo , Plásticos/metabolismo , Ratos , Espécies Reativas de Oxigênio/metabolismo , Receptores de Glutamato/metabolismo , Análise Espectral , Madeira/metabolismo , Ácido gama-Aminobutírico/metabolismoRESUMO
Remdesivir is a novel antiviral drug, which is active against the SARS-CoV-2 virus. Remdesivir is known to accumulate in the brain but it is not clear whether it influences the neurotransmission. Here we report diverse and pronounced effects of remdesivir on transportation and release of excitatory and inhibitory neurotransmitters in rat cortex nerve terminals (synaptosomes) in vitro. Direct incorporation of remdesivir molecules into the cellular membranes was shown by FTIR spectroscopy, planar phospholipid bilayer membranes and computational techniques. Remdesivir decreases depolarization-induced exocytotic release of L-[14C] glutamate and [3H] GABA, and also [3H] GABA uptake and extracellular level in synaptosomes in a dose-dependent manner. Fluorimetric studies confirmed remdesivir-induced impairment of exocytosis in nerve terminals and revealed a decrease in synaptic vesicle acidification. Our data suggest that remdesivir dosing during antiviral therapy should be precisely controlled to prevent possible neuromodulatory action at the presynaptic level. Further studies of neurotropic and membranotropic effects of remdesivir are necessary.
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Tratamento Farmacológico da COVID-19 , SARS-CoV-2 , Monofosfato de Adenosina/análogos & derivados , Alanina/análogos & derivados , Animais , Bicamadas Lipídicas , Ratos , Ratos Wistar , Transmissão Sináptica , Ácido gama-Aminobutírico/metabolismoRESUMO
Adsorption of guest molecules on host surfaces can lead to dramatic changes in the spectral properties of the guest. One such effect is surface-enhanced infrared absorption (SEIRA), observed when the guest is adsorbed on, for example, thin films, metal surfaces, or nanotubes. p-Nitrobenzoic acid (p-NBA) exhibits a SEIRA effect when adsorbed on Ag and Au. Herein, the IR spectra of p-NBA adsorbed on a homemade rough Au surface, recorded in reflection mode with an angle of incidence of 16.5°, are reported. This SEIRA experiment reveals more bands than found by previous SEIRA studies. The intensities of both symmetric and asymmetric COO(-) and NO(2) stretching, in-plane CH, and C=C ring stretching modes are enhanced. Theoretical models constructed on the basis of density functional theory reveal the binding mode of p-NBA to gold "particles". The p-NBA anion binds to gold much more strongly than the neutral form, and interaction via the carboxylic oxygen atoms is preferred over the nitro group-gold contact. A significant charge transfer during chemisorption is found, which is considered to be crucial in leading to a high SEIRA enhancement factor.
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The shape of coherent anti-Stokes Raman scattering (CARS) spectral line depends on the ratio of the vibrational and electronic contributions to the third-order susceptibility of the material. The G-mode (1590 cm-1) of graphene and carbon nanotubes (CNTs) exhibits opposite features in the CARS spectrum, showing "dip" and "peak," respectively. Here, we consider the CARS spectra of graphene and carbon nanotubes in terms of Fano formalism describing the line shapes of CARS resonances. We show that imaging at only 1590 cm-1 is not sufficient to separate the constituents of a composite material consisting of both graphene and CNTs. We propose an algorithm to map the graphene and CNTs in a composite material.
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Identification of chemically homologous microcrystals in a polycrystal sample is a big challenge and requires developing specific highly sensitive tools. Second harmonic (SHG) and coherent anti-Stokes Raman scattering (CARS) spectroscopy can be used to reveal arrangement of thymine molecules, one of the DNA bases, in microcrystalline sample. Strong dependence of CARS and SHG intensity on the orientation of the linear polarization of the excitation light allows to obtain high resolution images of thymine microcrystals by additionally utilizing the scanning microscopy technique. Experimental findings and theoretical interpretation of the results are compared. Presented experimental data together with quantum chemistry-based theoretical interpretation allowed us to determine the most probable organization of the thymine molecules.
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The naturally occurring modified nucleotide queuosine 5'-monophosphate (QMP) related to biochemical regulatory pathways in the cell was investigated using quantum chemical approaches. The relative stability of biologically relevant conformations of QMP in solvent under a pH change was predicted at the BVP86/TZVP and MP2/TZVP levels of theory. Hydrogen bonding in QMP was studied using Bader's approach. The acidity constants of QMP were estimated using the COSMO-RS theory. It has been found that the neutral and anionic forms of QMP are the most stable in the physiological pH range. These forms correspond to the anti/north conformation and exist as zwitterionic tautomers having a negatively charged phosphate group (-1 for neutral and -2 for anionic) and a positively charged secondary amine group in the side chain. It was also found that QMP possesses the syn conformation in the cationic state at pH < 5.0 and undergoes syn to anti conformation transition when the pH increases, remaining in the anti conformation at the higher pH values. The marker IR bands specific for the anionic and neutral QMP forms in the 2300-2700 cm(-1) region were assigned to H-bonded NH groups of the QMP side chain. The bands between 800 and 1300 cm(-1) of the "fingerprint" (400-1500 cm(-1)) region were assigned to the vibrations of the ribose ring, the phosphate group and the side chain of QMP. The predicted IR spectra can be useful for the assignment of vibration bands in the experiential spectra of QMP or identification of the QMP forms. The revealed peculiarities of the QMP conformation sensitivity to a pH change as well as additional formed H-bonds could be responsible for specific nucleotide interactions with enzymes.
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Guanosina Monofosfato/análogos & derivados , Guanosina Monofosfato/química , Ligação de Hidrogênio , Concentração de Íons de Hidrogênio , Modelos Moleculares , Conformação Molecular , Prótons , Soluções , Espectrofotometria Infravermelho , Termodinâmica , Água/químicaRESUMO
Metal-carbon nanocomposites possess attractive physical-chemical properties compared to their macroscopic counterparts. They are important and unique nanosystems with applications including in the future development of nanomaterial enabled sensors, polymer fillers for electromagnetic radiation shields, and catalysts for various chemical reactions. However, synthesis of these nanocomposites typically employs toxic solvents and hazardous precursors, leading to environmental and health concerns. Together with the complexity of the synthetic processes involved, it is clear that a new synthesis route is required. Herein, Cu/C, Ni/C and Co/C nanocomposites were synthesized using a two-step method including mechanochemical treatment of polyethylene glycol and acetates of copper, nickel and cobalt, followed by pyrolysis of the mixtures in an argon flow at 700 °C. Morphological and structural analysis of the synthesized nanocomposites show their core-shell nature with average crystallite sizes of 50 (Cu/C), 18 (Co/C) and 20 nm (Ni/C) respectively. The carbon shell originates from disordered sp2 carbon (5.2-17.2 wt.%) with a low graphitization degree. The stability and prolonged resistance of composites to oxidation in air arise from the complete embedding of the metal core into the carbon shell together with the presence of surface oxide layer of metal nanoparticles. This approach demonstrates an environmentally friendly method of mechanochemistry for controllable synthesis of metal-carbon nanocomposites.
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SUMMARY: Regeneration of the dura mater following duraplasty using a collagen film, a chitosan film, or a combination of both with gelatin, was studied in a craniotomy and penetrating brain injury model in rats. Collagen autofluorescence in the regenerated dura mater was evaluated using confocal microscopy with excitation at λem = 488 nm and λem = 543 nm. An increase in regeneration of the extracellular matrix of connective tissue and an increase in matrix fluorescence were detected at 6 weeks after duraplasty. The major contributors to dura mater regeneration were collagen films, chitosan plus gelatin-based films, and, to a much lesser extent, chitosan-based films. By using autofluorescence densitometry of extracellular matrix, the authors were able to quantify the degree of connective tissue regeneration in the dura mater following duraplasty.
RESUMEN: Se estudió la regeneración de la duramadre después de una duraplastía utilizando una lámina de colágeno, una lamina de quitosano o una combinación de ambas con gelatina en un modelo de craneotomía y lesión cerebral en ratas. La autofluorescencia del colágeno en la duramadre regenerada se evaluó mediante microscopía confocal con excitación a λem = 488 nm y λem = 543 nm. Se observó un aumento en la regeneración de la matriz extracelular del tejido conectivo y un aumento en la fluorescencia de la matriz a las 6 semanas después de la duraplastía. Se observe un efecto significativo en la regeneración de la duramadre con las láminas de colágeno, las láminas en base de quitosano más gelatina y, en un menor grado, las láminas a base de quitosano. Mediante el uso de densitometría de autofluorescencia de la matriz extracelular, los autores lograron cuantificar el grado de regenera- ción del tejido conectivo en la duramadre después de la duraplastía.
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Animais , Masculino , Ratos , Dura-Máter/anatomia & histologia , Dura-Máter/cirurgia , Dura-Máter/fisiologia , Craniectomia Descompressiva , Regeneração , Densitometria , Quitosana , Modelos Animais de Doenças , FluorescênciaRESUMO
Despite the fact that non-covalent interactions between various aromatic compounds and carbon nanotubes are being extensively investigated now, there is still a lack of understanding about the nature of such interactions. The present paper sheds light on one of the possible mechanisms of interaction between the typical aromatic dye proflavine and the carbon nanotube surface, namely, π-stacking between aromatic rings of these compounds. To investigate such a complexation, a qualitative analysis was performed by means of ultraviolet visible, infrared, and nuclear magnetic resonance spectroscopy. The data obtained suggest that π-stacking brings the major contribution to the stabilization of the complex between proflavine and the carbon nanotube.
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Espectroscopia de Ressonância Magnética/métodos , Nanotubos de Carbono/química , Proflavina/química , Espectrofotometria Ultravioleta/métodos , Adsorção , Modelos MolecularesRESUMO
Oxovanadium compounds exert preventive effects against chemical carcinogenesis in animals and form complexes with DNA and RNA in vivo. This study was designed to examine the interaction of transfer RNA (tRNA) with VO(2+) and VO3â» ions in aqueous solution at physiological pH, with constant a tRNA concentration of 12.5 mM and different vanadium/RNA (P) (P = phosphate) molar ratios (r) of 1:60 to 1:2. Affinity capillary electrophoresis and Fourier transform infrared spectroscopy were used to determine the ion-binding site, the binding constant, and tRNA conformation in oxovanadium-RNA complexes. Structural analysis showed that VO(2+) binds tRNA through guanine, adenine N7, and uracil O2 as well as to the backbone PO(2) group with apparent binding constants of K(G) = 8.9 (+/-1.2) x 10(4) M(-1) and K(U) = 3.4 (+/-0.85) x 10(4) M(-1). VO3â» shows weaker binding through guanine and adenine bases with K = 4.6 (+/-0.95) x 10(4) M(-1) and no interaction with the backbone phosphate group. No tRNA conformational transition was observed upon vanadium complexation, whereas biopolymer aggregation occurred at high oxovanadium concentrations.
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RNA de Transferência/química , Vanadatos/química , Íons/química , Saccharomyces cerevisiae/química , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
The DNA from Carcinoma Guerina resistant and sensitive cells of Wistar line rats and their interaction with anti-cancer drugs--cis-platin and doxorubicin (DOX)--have been studied in in vivo experiments. Surface enhanced infrared absorption (SEIRA) in reflectance absorption spectroscopy (RAS) mode was applied for registration of conformational change of the DNA induced by cancer process and anti-cancer drugs. We have registered numerous minor changes in infrared spectra of the DNA from sensitive and resistant cells that could reflect essential changes in molecular structure of DNA from cancer cells. The most significant transformation was undergone by the sugar phosphate backbone of the DNA from cancer cells. The DNA from resistant cancer cells could be characterized as rigid structures and look like the canonical helix form of DNA being practically unchangeable after anti-cancer drug application. The structure of DNA from sensitive cancer cells seems to be flexible and after application of anti-cancer drugs drastically changes and approaches to structure of helix form. It has been shown that doxorubicin strongly influences the DNA structure, leading to DNA stabilization and formation of new H-bonds in DNA doxorubicin complex. We have registered slight cis-platin influence on the DNA structure in in vivo experiment. Principal component analysis of SEIRA spectra can select the DNA from cancer cells.