Engineering hydrogen bonding at tyrosine-201 in the orange carotenoid protein using halogenated analogues.

The Orange Carotenoid Protein (OCP) is a unique water-soluble photoactive protein that plays a critical role in regulating the balance between light harvesting and photoprotective responses in cyanobacteria. The challenge in understanding OCP´s photoactivation mechanism stems from the heterogeneity of the initial configurations of its embedded ketocarotenoid, which in the dark-adapted state can form up to two hydrogen bonds to critical amino acids in the protein's C-terminal domain, and the extremely low quantum yield of primary photoproduct formation. While a series of experiments involving point mutations within these contacts helped us to identify these challenges, they did not resolve them.

Pallidal Spike-Train Variability and Randomness Are the Most Important Signatures to Classify Parkinson's Disease and Cervical Dystonia.

Movement disorders such as Parkinson's disease (PD) and cervical dystonia (CD) are associated with abnormal neuronal activity in the globus pallidus internus (GPi). Reduced firing rate and presence of spiking bursts are typical for CD, whereas PD is characterized by high frequency tonic activity. This research aims to identify the most important pallidal spiking parameters to classify these conditions.

Whisker-free lithium electrodeposition by tuning electrode microstructure.

Growth of lithium whiskers or dendrites is the major obstacle towards safe and stable utilization of lithium metal anodes in rechargeable batteries. In this study, we look deeper into the mechanism of lithium electrodeposition. We find that before lithium whisker or dendrite nucleation occurs, lithium is deposited into the grain boundaries of the metal electrode, which we directly observed in the focused ion beam cross-sections of the lithium electrode.

Redox-Active Water-Soluble Low-Weight and Polymer-Based Anolytes Containing Tetrazine Groups: Synthesis and Electrochemical Characterization.

Polymer-based aqueous redox flow batteries (RFBs) are attracting increasing attention as a promising next-generation energy storage technology due to their potential for low cost and environmental friendliness. The search for new redox-active organic compounds for incorporation into polymer materials is ongoing, with anolyte-type compounds in high demand. In response to this need, we have synthesized and tested a range of new water-soluble redox-active s-tetrazine derivatives, including both low molecular weight compounds and polymers with different architectures.

Detonation Nanodiamond Soot-A Structurally Tailorable Hybrid Graphite/Nanodiamond Carbon-Based Material.

The results of a comprehensive investigation into the structure and properties of nanodiamond soot (NDS), obtained from the detonation of various explosive precursors (trinitrotoluene, a trinitrotoluene/hexogen mixture, and tetryl), are presented. The colloidal behavior of the NDS particles in different liquid media was studied. The results of the scanning electron microscopy, dynamic light scattering, zeta potential measurements, and laser diffraction analysis suggested a similarity in the morphology of the NDS particle aggregates and agglomerates.

Periodic and Aperiodic Components of Subthalamic Nucleus Activity Reflect Different Aspects of Motor Impairment in Parkinson's Disease.

Excessive beta oscillations in the subthalamic nucleus are established as a primary electrophysiological biomarker for motor impairment in Parkinson's disease and are currently used as feedback signals in adaptive deep brain stimulation systems. However, there is still a need for optimization of stimulation parameters and the identification of optimal biomarkers that can accommodate varying patient conditions, such as ON and OFF levodopa medication. The precise boundaries of 'pathological' oscillatory ranges, associated with different aspects of motor impairment, are still not fully clarified.

Characterization and Evaluation of Zero-Order Release System Comprising Glycero-(9,10-trioxolane)-trialeate and PLA: Opportunity for Packaging and Biomedicine Applications.

Glycerol-(9,10-trioxolane) trioleate (OTOA) is a promising material that combines good plasticizing properties for PLA with profound antimicrobial activity, which makes it suitable for application in state-of-the-art biomedical and packaging materials with added functionality. On the other hand, application of OTOA in PLA-based antibacterial materials is hindered by a lack of knowledge on kinetics of the OTOA release. In this work, the release of glycero-(9,10-trioxolane) trioleate (OTOA) from PLA films with 50% OTOA content was studied during incubation in normal saline solution, and for the first time, the kinetics of OTOA release from PLA film was evaluated.

Characterization and Rheological Properties of Ultra-High Molecular Weight Polyethylenes.

The molecular characteristics and rheological properties of three UHMWPE samples were investigated. The high-temperature GPC method was used for characterizing UHMWPE samples used. The interpretation of the measurement results was based on calibration using the PS standard and the approximation of the PS data by linear and cubic polynomials, as well as on the data for linear PE.

Blood plasma proteomic markers of Alzheimer's disease, current status and application prospects.

Introduction: Identifying early risks of developing Alzheimer's disease (AD) is a major challenge as the number of patients with AD steadily increases and requires innovative solutions. Current molecular diagnostic modalities, such as cerebrospinal fluid (CSF) testing and positron emission tomography (PET) imaging, exhibit limitations in their applicability for large-scale screening. In recent years, there has been a marked shift toward the development of blood plasma-based diagnostic tests, which offer a more accessible and clinically viable alternative for widespread use.

Dose threshold for residual γH2AX, 53BP1, pATM and p-p53 (Ser-15) foci in X-ray irradiated human fibroblasts.

Background: Enumeration of residual DNA repair foci 24 hours or more after exposure to ionizing radiation (IR) is often used to assess the efficiency of DNA double-strand break repair. However, the relationship between the number of residual foci in irradiated cells and the radiation dose is still poorly understood. The aim of this work was to investigate the dose responses for residual DNA repair foci in normal human fibroblasts after X-ray exposure in the absorbed dose range from 0.

Effect of Macromolecular Architecture on Adhesion.

The behavior of single linear chains on a substrate is a well-studied area of polymer science. Herein, one of the most essential issues is the interaction of the chains with the substrate, which determines both macromolecular conformations near the substrate and adhesive properties of polymer materials. However, very little is known about the effect of macromolecular architecture on adhesion.

Effect of Drug-to-Protein Reaction Kinetics on the Results of Thermal Proteome Profiling.

In this Letter, a two-term formalism for constructing protein solubility curves in thermal proteome profiling (TPP) is considered, which takes into account the efficiency of the drug-protein binding reaction. When the reaction is incomplete, this results in distortion of the otherwise sigmoidal shape of the curve after drug treatment, which is often observed in experiments. This distortion may be significant enough to disqualify the corresponding protein from the list of drug target candidates, thus negatively affecting the results of TPP data analysis.

FLASH Radiotherapy: Benefits, Mechanisms, and Obstacles to Its Clinical Application.

Radiotherapy (RT) has been shown to be a cornerstone of both palliative and curative tumor care. RT has generally been reported to be sharply limited by ionizing radiation (IR)-induced toxicity, thereby constraining the control effect of RT on tumor growth. FLASH-RT is the delivery of ultra-high dose rate (UHDR) several orders of magnitude higher than what is presently used in conventional RT (CONV-RT).

Second harmonic generation and broad-band photoluminescence in mesoporous Si/SiO nanoparticles.

Efficient second harmonic generation and broad-band photoluminescence from deeply subwavelength and nontoxic nanoparticles is essential for nanophotonic applications. Here, we explore nonlinear optical response from mesoporous Si/SiO, SiO, and Si nanoparticles, considering various fabrication and treatment procedures. We show that thermal annealing (including femtosecond laser treatment) of mesoporous Si/SiO nanoparticles provides the transformation of Si phase from amorphous to crystalline, enhancing the second harmonic and nonlinear photoluminescent response.

Unraveling the neural signatures: Distinct pallidal patterns in dystonia subtypes.

Introduction: Dystonia manifests as slow twisting movements (pure dystonia) or repetitive, jerky motions (jerky dystonia). Dystonia can coexist with myoclonus (myoclonus dystonia) or tremor (tremor dystonia). Each of these presentations can have distinct etiology, can involve discrete sensorimotor networks, and may have characteristic neurophysiological signature.

Effect of Hyaluronic Acid on the Activity of Methylene Blue in Photogeneration of O.

The effect of a natural polysaccharide (hyaluronic acid (HA)) on the photocatalytic activity of methylene blue (MB) was studied both under model conditions (a tryptophan photooxidation reaction in water) and with in vitro experiments on and bacterial cultures. It was shown spectrophotometrically that, in the presence of HA, an increase in the optical density of the absorption bands λ = 665 nm and 620 nm-which correspond to the monomeric and dimeric forms of the dye, respectively-was observed in the EAS of the dye, while the ratio of the optical density of these bands remained practically unchanged. When adding HA to MB, the intensity of singlet oxygen O photoluminescence and the degree of fluorescence polarization of MB increase.

A comprehensive guide for accurate conformational energies of microsolvated Li clusters with organic carbonates.

Organic carbonates and their mixtures are frequently used in electrolyte solutions in lithium-ion batteries. Rationalization and tuning of the related Li solvation processes are rooted in the proper identification of the representative low-energy spatial structures of the microsolvated Li(S) clusters. In this study, we introduce an automatically generated database of conformational energies (CEs), LICARBCONF806, comprising 806 diverse conformers of Li clusters with 7 common organic carbonates.

Kinetics of Electron Transfer between Redox Cofactors in Photosystem I Measured by High-Frequency EPR Spectroscopy.

The kinetics of the primary electron donor P and the quinone acceptor A redox transitions were simultaneously studied for the first time in the time range of 200 μs-10 ms using high-frequency pulse Q-band EPR spectroscopy at cryogenic temperatures in various complexes of photosystem I (PSI) from the cyanobacterium PCC 6803. In the A-core PSI complexes that lack 4Fe4S clusters, the kinetics of the A and P signals disappearance at 100 K were similar and had a characteristic time of τ ≈ 500 μs, caused by charge recombination in the PA ion-radical pair in the branch of redox cofactors. The kinetics of the backward electron transfer from A to P in the branch of redox cofactors with τ < 100 μs could not be resolved due to time limitations of the method.

Comparative study of various molecular feature representations for solvation free energy predictions of neutral species.

Predicting molecular properties with the help of Neural Networks is a common way to substitute or enhance comprehensive quantum-chemical calculations. One of the problems facing researchers is the choice of vectorization approach to representing the solvent and the solute for the estimator model. In this work, 10 different approaches have been investigated for both organic solute and solvent including vectorizers that relied on macroscopic parameters, functional groups classification, molecular graphs, or atomic coordinates.

Methylene Blue Solid Alginate Gels for Photodynamic Therapy: The Peculiarities of Production and Controlled Release of the Dye.

The purpose of this work is to establish the influence of the nature of solid alginate gels (alginic acid, AAG; calcium alginate, CAG) and the conditions of methylene blue (MB) introduction to alginate matrices upon its release into aqueous media. MB is an active photosensitizer, which is used in the photodynamic therapy of tumors and purulent wounds. Solid alginate gels based on AAG and CAG were obtained by adding hydrochloric acid and calcium chloride to sodium alginate.

Cu-Methylsilsesquioxane Cage Decorated with Cu(dppe) Moieties for Mild Oxidative Functionalization of Alkanes.

We report a high nuclear (Cu) complex synthesized via the self-assembly of copper-methylsilsesquioxane induced by the complexation with 1,2-bis(diphenylphosphino)ethane (dppe). The structure includes two cationic Cu(dppe) moieties and an anionic silsesquioxane cage of an unprecedented Cu structural type. The Cu cage fragment exhibits a unique () combination of Si-cyclic/Si-acyclic silsesquioxane ligands and () encapsulation of two different chloride and carbonate species.