Kinetic features of solvent extraction by N,O-donor ligands of f-elements: a comparative study of diamides based on 1,10-phenanthroline and 2,2'-bipyridine.

A variant of microfluidic setup design for the study of extraction kinetics has been proposed. Mass transfer constants for Am(III) and Eu(III) and observed rate constants were obtained for N-,O-donor ligands featuring phenanthroline and bipyridyl cores. The possibility of determining rate constants for cations independently of each other makes it possible to observe the kinetic effect of separation. The extraction rate was found to be lower for the bipyridyl ligand, compared to phenanthroline. The values of the rotation barriers for the ligands were calculated using the DFT method. The values correlate with the obtained low extraction rate for the bipyridyl ligand. Also, crystallographic data showing anti-conformation for the bipyridyl ligand align with the kinetic data. Surface tension was also determined for the systems with the studied ligands. It is shown that at equal ligand concentrations, the value of surface tension agrees with the extraction rate. Furthermore, it is shown that for the bipyridyl ligand, prior contact of the organic phase with nitric acid significantly affects the surface tension.

Lysozyme binding with amikacin and levofloxacin studied by tritium probe, fluorescence spectroscopy and molecular docking.

Lysozyme complexes with amikacin and levofloxacin were studied by spectroscopy approaches as well as using a tritium probe. Tritium was used as a labeling agent to trace labeled compound concentration in a system of two immiscible liquids and in the atomic form to determine the possible position of the binding site. Co-adsorption of protein and drug at the liquid-liquid interface was analyzed by scintillation phase method that allowed us to directly determine the amount of protein and drug in the mixed adsorption layer. Also, tensiometric measuring of the interfacial tension was used for calculation of binding parameters accordingly to Fainerman model. The treatment of complexes with atomic tritium followed by trypsinolysis and analysis of tritium distribution in the lysozyme peptides reveals the binding sites, binding energies in which were analyzed using molecular docking. Formation of complexes with amikacin and levofloxacin preserves secondar structure of protein. However, the formation of complex with amikacin leads to the almost total loss of the enzymatic activity of lysozyme and the redshift of the maximum on the lysozyme fluorescence band. A slight decrease in the distribution coefficient of lysozyme in the presence of amikacin assumes that the complex has higher hydrophilicity in comparison to lysozyme without additives. The most favorable for binding were the positions of the active centers that included amino acids Asp52 and Glu35, as well as in the vicinity of peptide His15-Arg21, with the participation of amino acids Tyr20, Arg14. In the case of levofloxacin, the formation of lysozyme-ligand complex in aqueous solution is possible without changing the microenvironment of the active center of the protein. Binding of levofloxacin to the active center of the enzyme was the most favorable, but Asp52 and Glu35 that are responsible for the enzymatic activity of lysozyme, were not affected.

Label-Free Imaging of Humic Substance Bioaccumulation by Pump-Probe Microscopy.

Humic substances (HS) are the most abundant forms of natural organic matter on the earth surface. Comprised of decomposed plant and animal materials rich in carbon, oxygen, hydrogen, nitrogen, and sulfur complexes, HS facilitate global carbon and nitrogen cycling and the transport of anthropogenic contaminants. While it is known that HS also interact with organisms at different trophic levels to produce beneficial and harmful effects whether HS exert these biological effects through accumulation remains unknown. Current radiolabeling techniques, which only detect the amount of accumulated radiolabels, cannot visualize the transport and accumulation behavior of HS. Here, using a label-free method based on pump-probe microscopy, we show HS entered the protozoan Tetrahymena thermophila, zebrafish embryos, and human cells and exerted direct effects on these organisms. HS accumulated in the nucleus of T. thermophila, chorion pore canals of zebrafish embryos, and nucleus of intestinal and lung cells in a concentration- and time-dependent way. Epigenetic and transcriptomics assays show HS altered chromatin accessibility and gene transcription in T. thermophila. In zebrafish larvae, HS induced neurotoxicity, altering spontaneous muscle contraction and locomotor activity. Detailed images showing HS accumulation in our study reveal new insights on the ecological and environmental behavior of HS.

Chitosan/hyaluronic acid polyanion bilayer applied from carbon acid as an advanced coating with intelligent antimicrobial properties for improved biological prosthetic heart valves.

The tightly bonded shielding coating on biomatrix significantly enhances the functionality of medical devices, bioprostheses in particular. In our work we have obtained a polyelectrolyte coating on a biomatrix by sequentially depositing chitosan and hyaluronic acid (HA) from solutions in carbonic acid under pressure. This approach makes it possible to obtain hybrid biomatrix with a firmly bonded polymer screen due to the electrostatic bonding of polyions. High-precision analysis using a tritium label shows a 3-fold increase in quantity of HA in carbonic acid under pressure compared to the conventional method. The presence of the chitosan layer increases the HA adsorption by 15-20 % due to electrostatic interaction of differently charged polymers. Antimicrobial results show the possibility of implementing an induced antimicrobial response, due to the lysis of the upper layer of the coating (HA) and the release of antimicrobial agents in the case of growth of pathogens on the bioprosthesis.

Pyridine-di-phosphonates as chelators for trivalent f-elements: kinetics, thermodynamic and interfacial study of Am(III)/Eu(III) solvent extraction.

The fractionation of high-level radioactive waste from nuclear power plants simplifies the handling of its components, and facilitates the reduction of radiotoxic effects on the environment. The search and study of new ligands for solvent extraction, as one of the methods in fractionation, remains a complex and important research task. In this work, four pyridine diphosphonate ligands were synthesized. These ligands are part of the class of the N,O-donor extractants, which are selective towards Am(III). The separation factor SF(Am/Eu) for the best extractant reached values up to 10. The influence of the substituents on the efficiency of extraction and complexation of trivalent f-elements, the kinetics of extraction, and the behavior of the ligand at the interface were described. The effect of nitric acid concentration on the extraction was shown. The stoichiometry of the complexes was determined by slope analysis in solvent extraction experiment and verified by spectrophotometric titration in acetonitrile. Liquid tension experiments with a pendant drop method revealed the interfacial properties of the ligands in "F-3 solvent/H2O" and "F-3 solvent/HNO3" systems. The relationship between the surface activity and the ligand structure was shown. Studies of the extraction kinetics were performed in a modified Lewis cell. The effect of the ligand structure on the extraction rate was shown. The DFT calculation with the B3LYP density functional was used to explain the extraction properties of the ligands, including selectivity. The calculation of the pre-organization energy of the ligands explained the kinetics and extraction patterns for the studied series.

A Use of Tritium-Labeled Peat Fulvic Acids and Polyphenolic Derivatives for Designing Pharmacokinetic Experiments on Mice.

Natural products (e.g., polyphenols) have been used as biologically active compounds for centuries. Still, the mechanisms of biological activity of these multicomponent systems are poorly understood due to a lack of appropriate experimental techniques. The method of tritium thermal bombardment allows for non-selective labeling and tracking of all components of complex natural systems. In this study, we applied it to label two well-characterized polyphenolic compounds, peat fulvic acid (FA-Vi18) and oxidized lignin derivative (BP-Cx-1), of predominantly hydrophilic and hydrophobic character, respectively. The identity of the labeled samples was confirmed using size exclusion chromatography. Using ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT ICR MS), key differences in the molecular composition of BP-Cx-1 and FA-Vi18 were revealed. The labeled samples ([3H]-FA-Vi18 (10 mg/kg) and [3H]-BP-Cx-1 (100 mg/kg)) were administered to female BALB/c mice intravenously (i.v.) and orally. The label distribution was assessed in blood, liver, kidneys, brain, spleen, thymus, ovaries, and heart using liquid scintillation counting. Tritium label was found in all organs studied at different concentrations. For the fulvic acid sample, the largest accumulation was observed in the kidney (Cmax 28.5 mg/kg and 5.6 mg/kg, respectively) for both routes. The organs of preferential accumulation of the lignin derivative were the liver (Cmax accounted for 396.7 and 16.13 mg/kg for i.v. and p.o. routes, respectively) and kidney (Cmax accounted for 343.3 and 17.73 mg/kg for i.v. and p.o. routes, respectively). Our results demonstrate that using the tritium labeling technique enabled successful pharmacokinetic studies on polyphenolic drugs with very different molecular compositions. It proved to be efficient for tissue distribution studies. It was also shown that the dosage of the polyphenolic drug might be lower than 10 mg/kg due to the sensitivity of the 3H detection technique.

Single-shot interferometric measurement of pulse-to-pulse stability of absolute phase using a time-stretch technique.

Measurement of the absolute phase of ultrashort optical pulses in real-time is crucial for various applications, including frequency comb and high-field physics. Modern single-shot techniques, such as dispersive Fourier transform and time-lens, make it possible to investigate non-repetitive spectral dynamics of ultrashort pulses yet do not provide the information on absolute phase. In this work, we demonstrate a novel approach to characterise single-shot pulse-to-pulse stability of the absolute phase with the acquisition rate of 15 MHz. The acquisition rate, limited by the repetition rate of the used free-running mode-locked Erbium-doped fibre laser, substantially exceeds one of the traditional techniques. The method is based on the time-stretch technique. It exploits a simple all-fibre Mach-Zehnder interferometric setup with a remarkable resolution of ∼7.3 mrad. Using the proposed method, we observed phase oscillations in the output pulses governed by fluctuations in the pulse intensity due to Kerr-induced self-phase modulation at frequencies peaked at 4.6 kHz. As a proof-of-concept application of the demonstrated interferometric methodology, we evaluated phase behaviour during vibration exposure on the laser platform. The results propose a new view on the phase measurements that provide a novel avenue for numerous sensing applications with MHz data frequencies.

Rotation Active Sensors Based on Ultrafast Fibre Lasers.

Gyroscopes merit an undeniable role in inertial navigation systems, geodesy and seismology. By employing the optical Sagnac effect, ring laser gyroscopes provide exceptionally accurate measurements of even ultraslow angular velocity with a resolution up to 10-11 rad/s. With the recent advancement of ultrafast fibre lasers and, particularly, enabling effective bidirectional generation, their applications have been expanded to the areas of dual-comb spectroscopy and gyroscopy. Exceptional compactness, maintenance-free operation and rather low cost make ultrafast fibre lasers attractive for sensing applications. Remarkably, laser gyroscope operation in the ultrashort pulse generation regime presents a promising approach for eliminating sensing limitations caused by the synchronisation of counter-propagating channels, the most critical of which is frequency lock-in. In this work, we overview the fundamentals of gyroscopic sensing and ultrafast fibre lasers to bridge the gap between tools development and their real-world applications. This article provides a historical outline, highlights the most recent advancements and discusses perspectives for the expanding field of ultrafast fibre laser gyroscopes. We acknowledge the bottlenecks and deficiencies of the presented ultrafast laser gyroscope concepts due to intrinsic physical effects or currently available measurement methodology. Finally, the current work outlines solutions for further ultrafast laser technology development to translate to future commercial gyroscopes.

First-order fiber Bragg grating inscription in indium fluoride fiber using a UV/Vis femtosecond laser and two-beam interferometry.

Fiber gratings are among key components in fiber-based photonics systems and, particularly, laser cavities. In the latter, they can play multiple roles, such as those of mirrors, polarizers, filters, or dispersion compensators. In this Letter, we present the inscription of highly reflective first-order fiber Bragg gratings (FBGs) in soft indium fluoride-based (InF3) fibers using a two-beam phase-mask interferometer and a femtosecond laser. We demonstrate an enhanced response of InF3-based fiber to a visible (400 nm) inscription wavelength compared to ultraviolet irradiation at 266 nm. In this way, FBGs with a reflectivity >99.7% were inscribed at around 1.9 µm with the bandwidth of 2.68 nm. After thermal annealing at 393K, the Bragg wavelength demonstrates stable thermal shift of 20 pm/K in the temperature range 293-373K. These observations suggest a potential extension of InF3 fiber-based laser components to an operational range of up to 5 µm.

Lysozyme-dalargin self-organization at the aqueous-air and liquid-liquid interfaces.

An experimental study of protein-peptide binding was performed by means of radiochemical and spectroscopic methods. Lysozyme and dalargin were chosen due to their biological and physiological importance. By means of tensiometry and radiochemical assays, it was found that dalargin possesses rather high surface activity at the aqueous-air and aqueous-p-xylene interfaces to be substituted by protein. Dalargin forms a hydrophobic complex with lysozyme in which the secondary structure of lysozyme is preserved. When lysozyme forms a mixed adsorption layer with dalargin at the aqueous-air surface, the peptide prevents protein from concentrating in the subsurface monolayer. In the presence of p-xylene protein in the interface, reorganization occurs quickly, so there is no lag in the interfacial tension time dependence. The interfacial tension in this case is controlled by protein and/or protein-peptide complexes. An increase in the enzymatic activity of lysozyme in the presence of dalargin was confirmed by a docking model that suggests the formation of hydrogen bonds between dalargin and amino acid residues in the active site.

Tritium labelling to study humic substance-nanodiamond composites.

Nanodiamonds produced by the detonation method are used as lubricants, polishing compositions, polymer composites, etc. To reveal how nanodiamonds differ in terms of surface properties and interact with natural organic matter, we used tritium-labelled humic substances to quantitively describe their adsorption onto the nanodiamond surface. It was shown that the adsorption of humic substances onto nanodiamonds resulted in fractionation of humic substances that was strongly dependent on the zeta potential of nanodiamonds in water but did not significantly affect the uptake of nanodiamonds by wheat seedlings. The uptake of nanodiamond particles by plants was determined by the functional composition of the particle surface.

Autofluorescence guided welding of heart tissue by laser pulse bursts at 1550 nm.

Wound healing and other surgical technologies traditionally solved by suturing and stapling have recently been enhanced by the application of laser tissue welding. The usage of high energy laser radiation to anastomose tissues eliminates a foreign body reaction, reduces scar formation, and allows for the creation of watertight closure. In the current work, we show that an ultrafast pulsed fibre laser beam with 183 µJ·cm-2 energy fluence at 1550 nm provides successful welding of dissected chicken heart walls with the tensile strength of 1.03±0.12 kg·cm-2 equal to that of native tissue. The welding process was monitored employing fluorescence spectroscopy that detects the biochemical composition of tissues. We believe that fluorescence spectroscopy guided laser tissue welding is a promising approach for decreasing wound healing times and the avoiding risks of postoperative complications.

Structural peculiarities of lysozyme - PLURONIC complexes at the aqueous-air and liquid-liquid interfaces and in the bulk of aqueous solution.

Interaction between proteins and synthetic polymers that represent a perspective potential in drug delivery or/and already used in medicine plays a key role in biological functioning of both molecules along with a system as a whole. In present study association between hen egg white lysozyme and Pluronic triblock-copolymers (L121, P123 and F127) in the bulk of the solution as well as at the aqueous-air and liquid-liquid interfaces was analyzed by means of spectroscopic and radiochemical assay. In protein-Pluronic complexes lysozyme keeps the secondary structure (CD and SAXS data results), while fluorescence and UV-analysis indicates changes in the local surrounding of fluorophoric amino acid residues. Radiochemical assay in combination with molecular docking reveals the formation of the complexes, in which proline residues turned to the interface between water and hydrophobic medium.

Behavior of humic substances in the liquid-liquid system directly measured using tritium label.

Humic substances (HS) in the aqueous solutions can be considered as colloidal particles formed by amphiphilic units. HS form micelles-like structures at concentrations close to 5 g/L. However colloidal behavior of HS at concentrations below 100 mg/L is unknown. Using radiotracer assay we have shown that in this concentration range HS form rare adsorption layers at the liquid/liquid interface and penetrate into the organic phase with the distribution ratio close to 10-3. We found that pH and HS molecular weight strongly influence on the distribution ratio but do not significantly change the adsorption. Furthermore, colloidal properties of HS are strongly depending on its origin: the highest surface activity was shown for HS separated from peat and the least was observed for HS separated from soils. We anticipate our assay to be a helpful tool for detailed analysis and modeling HS and humic-like materials colloidal behavior in the environment.

Surface characterization of the thermal remodeling helical plant virus.

Previously, we have reported that spherical particles (SPs) are formed by the thermal remodeling of rigid helical virions of native tobacco mosaic virus (TMV) at 94°C. SPs have remarkable features: stability, unique adsorption properties and immunostimulation potential. Here we performed a comparative study of the amino acid composition of the SPs and virions surface to characterize their properties and take an important step to understanding the structure of SPs. The results of tritium planigraphy showed that thermal transformation of TMV leads to a significant increase in tritium label incorporation into the following sites of SPs protein: 41-71 а.a. and 93-122 a.a. At the same time, there was a decrease in tritium label incorporation into the N- and C- terminal region (1-15 a.a., 142-158 a.a). The use of complementary physico-chemical methods allowed us to carry out a detailed structural analysis of the surface and to determine the most likely surface areas of SPs. The obtained data make it possible to consider viral protein thermal rearrangements, and to open new opportunities for biologically active complex design using information about SPs surface amino acid composition and methods of non-specific adsorption and bioconjugation.

High-density multi-fiber photometry for studying large-scale brain circuit dynamics.

Animal behavior originates from neuronal activity distributed across brain-wide networks. However, techniques available to assess large-scale neural dynamics in behaving animals remain limited. Here we present compact, chronically implantable, high-density arrays of optical fibers that enable multi-fiber photometry and optogenetic perturbations across many regions in the mammalian brain. In mice engaged in a texture discrimination task, we achieved simultaneous photometric calcium recordings from networks of 12-48 brain regions, including striatal, thalamic, hippocampal and cortical areas. Furthermore, we optically perturbed subsets of regions in VGAT-ChR2 mice by targeting specific fiber channels with a spatial light modulator. Perturbation of ventral thalamic nuclei caused distributed network modulation and behavioral deficits. Finally, we demonstrate multi-fiber photometry in freely moving animals, including simultaneous recordings from two mice during social interaction. High-density multi-fiber arrays are versatile tools for the investigation of large-scale brain dynamics during behavior.

Structural and mechanical characteristics of collagen tissue coated with chitosan in a liquid CO2/water system at different pressures.

Chitosan coatings of biological heart-valve prostheses enhance their biocompatibility, resistance to pathogenic microflora and lifetime. Collagen tissues can be coated with chitosan in aqueous solution acidified, to make chitosan soluble, with H2CO3 formed from a coexisting liquid CO2 phase under pressure. The advantage of H2CO3 is that it can be easily removed after the coating procedure. This study assessed the effects of 6-50 MPa CO2 pressure during the coating procedure on the structure and mechanical properties of the resulting biocomposite matrices. The dependence of chitosan adsorption on CO2 pressure was bell-shaped, reaching a maximum adsorption of 0.8 mass % at 40 MPa. Tissue surface became highly porous upon pressure treatment. At 50 MPa, the pores merged to form furrows with lengths of several hundred micrometers, accompanied by collagen fibril reorganisation. Chitosan coating did not affect tissue tensile strength in the axial direction, but increased it by 75% in the radial direction in the tissue coated at 50 MPa pressure. Strain at break, a measure of elasticity, increased in both directions by up to 100% upon coating with chitosan. CO2 pressure of 30-50 MPa seems thus optimal in terms of chitosan incorporation and tissue mechanical properties.

Revealing the nature of morphological changes in carbon nanotube-polymer saturable absorber under high-power laser irradiation.

Composites of single-walled carbon nanotubes (SWNTs) and water-soluble polymers (WSP) are the focus of significant worldwide research due to a number of applications in biotechnology and photonics, particularly for ultrashort pulse generation. Despite the unique possibility of constructing non-linear optical SWNT-WSP composites with controlled optical properties, their thermal degradation threshold and limit of operational power remain unexplored. In this study, we discover the nature of the SWNT-polyvinyl alcohol (PVA) film thermal degradation and evaluate the modification of the composite properties under continuous high-power ultrashort pulse laser operation. Using high-precision optical microscopy and micro-Raman spectroscopy, we have examined SWNT-PVA films before and after continuous laser radiation exposure (up to 40 hours) with a maximum optical fluence of 2.3 mJ·cm-2. We demonstrate that high-intensity laser radiation results in measurable changes in the composition and morphology of the SWNT-PVA film due to efficient heat transfer from SWNTs to the polymer matrix. The saturable absorber modification does not affect the laser operational performance. We anticipate our work to be a starting point for more sophisticated research aimed at the enhancement of SWNT-PVA films fabrication for their operation as reliable saturable absorbers in high-power ultrafast lasers.

Chitosan coatings with enhanced biostability in vivo.

In this article, we study the stability of chitosan coatings applied on glutaraldehyde-stabilized bovine pericardium when exposed to biodegradation in vivo in the course of model subcutaneous tests on rats. The coatings were deposited from carbonic acid solutions, that is, H2 O saturated with CO2 at high pressure. Histological sections of treated pericardium samples demonstrated that the structure of pericardial connective tissues was not significantly altered by the coating application method. It was revealed that the dynamics of biodegradation depended on the total mass of chitosan applied as well as on the DDA of chitosan used. As long as the amount of chitosan did not exceed a certain threshold limit, no detectable degradation occurred within the time of the tests (12 weeks for the rat model). For higher chitosan amounts, we detected a ∼20% reduction of the mass after the in vivo exposition. The presumed mechanism of such behavior is discussed. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 270-277, 2018.

Double-Wall Carbon Nanotube Hybrid Mode-Locker in Tm-doped Fibre Laser: A Novel Mechanism for Robust Bound-State Solitons Generation.

The complex nonlinear dynamics of mode-locked fibre lasers, including a broad variety of dissipative structures and self-organization effects, have drawn significant research interest. Around the 2 µm band, conventional saturable absorbers (SAs) possess small modulation depth and slow relaxation time and, therefore, are incapable of ensuring complex inter-pulse dynamics and bound-state soliton generation. We present observation of multi-soliton complex generation in mode-locked thulium (Tm)-doped fibre laser, using double-wall carbon nanotubes (DWNT-SA) and nonlinear polarisation evolution (NPE). The rigid structure of DWNTs ensures high modulation depth (64%), fast relaxation (1.25 ps) and high thermal damage threshold. This enables formation of 560-fs soliton pulses; two-soliton bound-state with 560 fs pulse duration and 1.37 ps separation; and singlet+doublet soliton structures with 1.8 ps duration and 6 ps separation. Numerical simulations based on the vectorial nonlinear Schr¨odinger equation demonstrate a transition from single-pulse to two-soliton bound-states generation. The results imply that DWNTs are an excellent SA for the formation of steady single- and multi-soliton structures around 2 µm region, which could not be supported by single-wall carbon nanotubes (SWNTs). The combination of the potential bandwidth resource around 2 µm with the soliton molecule concept for encoding two bits of data per clock period opens exciting opportunities for data-carrying capacity enhancement.