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In this study, we investigate the structural changes, electronic properties, and charge redistribution within azo-bithiophene (Azo-BT)-chemisorbed monolayers under different light stimuli using the density functional theory and molecular dynamics simulations. We consider two types of switches, Azo-BT and BT-Azo, with different arrangements of the Azo and BT blocks counting from the anchor thiol group. The chemisorbed monolayers of pure cis- and trans-isomers with a surface concentration of approximately 2.7 molecules per nm 2 are modeled on a gold surface using the classical all-atom molecular dynamics. Our results reveal a significant shrinkage of the BT-Azo layer under UV illumination, whereas the thicknesses of the Azo-BT layer remain comparable for both isomers. This difference in behavior is attributed to the ordering of the trans-molecules in the layers, which is more pronounced for Azo-BT, leading to a narrow distribution of the inclination angle to the gold surface. Conversely, both layers consisting of cis-switches exhibit disorder, resulting in similar brush heights. To study charge transfer within the immobilized layers, we analyze each snapshot of the layer and calculate the mean charge transfer integrals using Nelsen's algorithm for a number of interacting neighboring molecules. Combining these integrals with reorganization energies defined for the isolated molecules, we evaluate the charge transfer rates and mobilities for electron and hole hopping within the layers at room temperature based on Marcus' theory. This research offers new perspectives for the innovative design of electrode surface modifications and provides insights into controlling charge transfer within immobilized layers using light triggers. Additionally, we identify molecular properties that are enhanced via specific molecular design, which contributes to the development of more efficient molecular switches for various electronic applications. [ABSTRACT FROM AUTHOR]

In this article, we report on experimental studies of the influence of several laser radiation parameters, such as the duration of the laser pulse, the radiation wavelength, and the pulse energy, on the efficiency of the destruction of urinary calculi. The study used a laser lithotripter based on a fiber Tm laser generating at a wavelength of 1940 nm with pulses with a duration of about 1800 μs and pulse energy of up to 6 J, as well as a femtosecond solid-state Yb laser generating at a wavelength of 1032 nm with a pulse duration of about 250 fs and pulse energy of up to 400 μJ. A comparative analysis was carried out according to such criteria as the productivity of lasers when removing a unit mass of images and the amount of sample displacement resulting from the retropulsion effect. The results obtained in this work demonstrated that the femtosecond laser loses approximately two times its efficiency in terms of sample material removal. However, this shows the absolute advantage of the photoionization mechanism of femtosecond laser ablation in the study of retropulsion and thermal heating, which were completely absent in this case. [ABSTRACT FROM AUTHOR]

Nanosecond lasers have recently been widely involved in human activity. However, high-intensity laser radiation can cause severe damage to organs of vision and expensive photonic devices. Radiation in the near UV range is especially dangerous for human eyes, since it is strongly absorbed by biological media and is also invisible, i.e., the reaction time of the eye to such radiation is much lower than that of visible light. Passive limiters have high transmission (>70%) at a low light intensity and begin to "darken" only when the threshold value of the laser radiation intensity is reached. In this work, we studied liquid nanodispersed nonlinear optical limiters based on hybrids of single-walled carbon nanotubes (SWCNTs) with metal-free tetra(hydroxy)phthalocyanine (OH)4PcHH). The value of the hydrodynamic radius of separate particles after (OH)4PcHH binding increased from 288 ± 55 nm to 350 ± 60 nm, which confirms the attachment of phthalocyanine complexes to nanotubes. The third harmonic of a Nd:YAG nanosecond laser (355 nm, 20 ns) was used to study the nonlinear optical response. Based on a Z-scan with open-aperture and input-output dependence curves, third-order nonlinear optical absorption coefficients of 149, 236, and 229 cm/GW were obtained for dispersions of composites of SWCNTs and (OH)4PcHH in water, dimethylformamide (DMF), and dimethylsulfoxide (DMSO), respectively. Threshold values did not exceed 100 mJ/cm2. The Z-scan showed a gradual decrease in the duration of the laser pulse by 53%; however, near the focus, there was a sharp increase in the duration of the transmitted pulse, reaching a value of 29 ns in z = 0. This phenomenon confirms the occurrence of reverse saturable absorption in the investigated media and can be used in photonic devices to control the temporal characteristics of the signal. Thus, the possibility of protection of sensitive photonic devices and human eyes from nanosecond laser pulses in the near UV range by nanodispersed liquid media based on composites of SWCNTs with (OH)4PcHH has been discussed in this paper. [ABSTRACT FROM AUTHOR]

Acid-base characteristics (acidity, pKa, and hydricity, ΔG°H− or kH−) of metal hydride complexes could be a helpful value for forecasting their activity in various catalytic reactions. Polarity of the M–H bond may change radically at the stage of formation of a non-covalent adduct with an acidic/basic partner. This stage is responsible for subsequent hydrogen ion (hydride or proton) transfer. Here, the reaction of tricarbonyl manganese hydrides mer,trans–[L2Mn(CO)3H] (1; L = P(OPh)3, 2; L = PPh3) and fac–[(L–L′)Mn(CO)3H] (3, L–L′ = Ph2PCH2PPh2 (dppm); 4, L–L′ = Ph2PCH2–NHC) with organic bases and Lewis acid (B(C6F5)3) was explored by spectroscopic (IR, NMR) methods to find the conditions for the Mn–H bond repolarization. Complex 1, bearing phosphite ligands, features acidic properties (pKa 21.3) but can serve also as a hydride donor (ΔG≠298K = 19.8 kcal/mol). Complex 3 with pronounced hydride character can be deprotonated with KHMDS at the CH2–bridge position in THF and at the Mn–H position in MeCN. The kinetic hydricity of manganese complexes 1–4 increases in the order mer,trans–[(P(OPh)3)2Mn(CO)3H] (1) < mer,trans–[(PPh3)2Mn(CO)3H] (2) ≈ fac–[(dppm)Mn(CO)3H] (3) < fac–[(Ph2PCH2NHC)Mn(CO)3H] (4), corresponding to the gain of the phosphorus ligand electron-donor properties. [ABSTRACT FROM AUTHOR]

The present study aimed to improve the optical sensing performance of tapered optical fiber sensors toward aqueous Rhodamine B solution of different concentrations by applying single-walled carbon nanotubes (SWCNTs). The functional coating was formed on the surface of the tapered optical fiber sensor using an aerosol layer-by-layer deposition method. Before deposition, the SWCNTs were processed with multistage liquid-phase treatment in order to form a stable dispersion. The effect of SWCNT treatment was investigated through Raman spectroscopy. The deposition of 220 layers caused a reduction of up to 60% of the initial optical power of radiation propagating through the optical fiber core. The optical fiber sensor coated with SWCNTs demonstrated significantly higher sensitivity compared to a non-coated sensor in the range of 2–32 mg/L of Rhodamine B concentration in an aqueous solution. The experimental results demonstrated that the sensitivity was increased 10 times from 32 (mg/L)−1, for the non-coated sensor, up to 317 (mg/L)−1 after SWCNT coating deposition. Moreover, the SWCNT-coated sensor demonstrated high repeatability that allowed for the evaluation of the concentration regardless of the previously analyzed dye concentration. [ABSTRACT FROM AUTHOR]

The long-term storage of the genetic resources of fruit crops for breeding needs can be freely developed by cryopreservation cuttings with dormant buds in liquid nitrogen vapor, but so far, this method has not been practically used for peach. Cuttings with dormant buds of five peach varieties growing in the field gene bank at Krymsk Experiment and Breeding Station of VIR were collected for cryopreservation in 2019–2021. The three-factor analysis of variance showed that the viability of peach cuttings was significantly affected by the year (p < 0.001) and variety (p < 0.001). According to the three-year average characteristics of the cultivars, the analysis of variance showed a significant difference in the viability of the cultivars after cryopreservation (p = 0.004). According to the results of the three years of study, cvs. 'Podarok Kryma' (43.3%) and 'Lucky 24 B' (44.4%) showed the lowest viability after cryopreservation, significantly lower than cvs. 'Baby Gold' (54.4%) and 'Ustojchivy 90′ (55.6%). Cv. 'Lyubimets Krasnodara' (48.9%) occupied an intermediate position. These viability values exceeded the minimum requirement for samples subjected to long-term cryogenic storage in a cryobank. Low-temperature storage of peach cuttings at –5 °C can be used for short-term preservation. After low-temperature storage, the viability of peach cutting amounted to an average of 67.1%. [ABSTRACT FROM AUTHOR]

The healing efficiency in self-healing materials is bound by the ability to form blends between the prepolymer and curing agent. One of the problems in the development of self-healing polymers is the reduced affinity of the bismaleimide curing agent for the elastomeric furan-containing matrix. Even when stoichiometric amounts of both components are applied, incompatibility of components can significantly reduce the effectiveness of self-healing, and lead to undesirable side effects, such as crystallization of the curing agent, in the thickness and on the surface. This is exactly what we have seen in the development of linear and cross-linked PUs using BMI as a hardener. In this work, we present a new series of the di- and tetrafuranic isocyanate-related ureas—promising curing agents for the development of polyurethanes-like self-healing materials via the Diels–Alder reaction. The commonly used isocyanates (4,4′-Methylene diphenyl diisocyanate, MDI; 2,4-Tolylene diisocyanate, TDI; and Hexamethylene diisocyanate, HDI) and furfurylamine, difurfurylamine, and furfuryl alcohol (derived from biorenewables) as furanic compounds were utilized for synthesis. The remendable polyurethane for testing was synthesized from a maleimide-terminated prepolymer and one of the T-series urea. Self-healing properties were investigated by thermal analysis. Molecular mass was determined by gel permeation chromatography. The properties of the new polymer were compared with polyurethane from a furan-terminated analog. Visual tests showed that the obtained material has thermally induced self-healing abilities. Resulting polyurethane (PU) has a rather low fusing point and thus may be used as potential material for Fused Deposition Modeling (FDM) 3D printing. [ABSTRACT FROM AUTHOR]

A technology for the formation and bonding with a substrate of hybrid carbon nanostructures from single-walled carbon nanotubes (SWCNT) and reduced graphene oxide (rGO) by laser radiation is proposed. Molecular dynamics modeling by the real-time time-dependent density functional tight-binding (TD-DFTB) method made it possible to reveal the mechanism of field emission centers formation in carbon nanostructures layers. Laser radiation stimulates the formation of graphene-nanotube covalent contacts and also induces a dipole moment of hybrid nanostructures, which ensures their orientation along the force lines of the radiation field. The main mechanical and emission characteristics of the formed hybrid nanostructures were determined. By Raman spectroscopy, the effect of laser radiation energy on the defectiveness of all types of layers formed from nanostructures was determined. Laser exposure increased the hardness of all samples more than twice. Maximum hardness was obtained for hybrid nanostructure with a buffer layer (bl) of rGO and the main layer of SWCNT—rGO(bl)-SWCNT and was 54.4 GPa. In addition, the adhesion of rGO to the substrate and electron transport between the substrate and rGO(bl)-SWCNT increased. The rGO(bl)-SWCNT cathode with an area of ~1 mm2 showed a field emission current density of 562 mA/cm2 and stability for 9 h at a current of 1 mA. The developed technology for the formation of hybrid nanostructures can be used both to create high-performance and stable field emission cathodes and in other applications where nanomaterials coating with good adhesion, strength, and electrical conductivity is required. [ABSTRACT FROM AUTHOR]

Recently, Ti-Ni based intermetallic alloys with shape memory effect (SME) have attracted much attention as promising functional materials for the development of record small nanomechanical tools, such as nanotweezers, for 3D manipulation of the real nano-objects. The problem of the fundamental restrictions on the minimal size of the nanomechanical device with SME for manipulation is connected with size effects which are observed in small samples of Ti-Ni based intermetallic alloys with thermoplastic structural phase transition from austenitic high symmetrical phase to low symmetrical martensitic phase. In the present work, by combining density functional theory and molecular dynamics modelling, austenite has been shown to be more stable than martensite in nanometer-sized TiNi wafers. In this case, the temperature of the martensitic transition asymptotically decreases with a decrease in the plate thickness h, and the complete suppression of the phase transition occurs for a plate with a thickness of 2 nm, which is in qualitative agreement with the experimental data. Moreover, the theoretical values obtained indicate the potential for even greater minimization of nanomechanical devices based on SME in TiNi. [ABSTRACT FROM AUTHOR]

Here we report a series of 1-phenyl-5-substituted 2,6-di(pyrazol-3-yl)pyridine complexes with iron(II) ion found in a high spin state in solids (according to magnetochemistry) and in solution (according to NMR spectroscopy), providing experimental evidence for it being an intramolecular effect induced by the phenyl groups. According to X-ray diffraction, the high spin locking of the metal ion is a result of its highly distorted coordination environment (with a very low 'twist' angle atypical of 2,6-di(pyrazol-3-yl)pyridine complexes), which remains this way in complexes with different substituents and counterions, in a diamagnetic zinc(II) analogue and in their solutions. Three possible reasons behind it, including additional coordination with the phenyl group, energy penalty incurred by its rotation or intramolecular stacking interactions, are addressed experimentally. [ABSTRACT FROM AUTHOR]

Recycling of plastic waste, in particular polypropylene, represents one of the most pressing challenges facing humanity. Despite the promise of chemical methods for recycling polypropylene, they usually require a high temperature and are energy-intensive. In this work, we investigated the oxidative thermolysis of polypropylene in aqueous media. This approach rendered it possible to carry out the decomposition of the polymer at a comparatively low temperature (150 °C). It was shown that among the tested, the most promising aqueous medium for the decomposition of polypropylene is water saturated with gaseous oxygen at an elevated pressure (14 bar) and at a temperature of 150 °C. In such an environment, polypropylene was converted mostly to acetic acid (up to 1.3 g/g acetic acid to starting polypropylene mass ratio). Moreover, methanol, formic acid, and propionic acid were also detected as the products. Finally, the applicability of the proposed recycling method to real polypropylene waste was shown. [ABSTRACT FROM AUTHOR]

A technology for the formation of electrically conductive nanostructures from single-walled carbon nanotubes (SWCNT), multi-walled carbon nanotubes (MWCNT), and their hybrids with reduced graphene oxide (rGO) on Si substrate has been developed. Under the action of single pulses of laser irradiation, nanowelding of SWCNT and MWCNT nanotubes with graphene sheets was obtained. Dependences of electromagnetic wave absorption by films of short and long nanotubes with subnanometer and nanometer diameters on wavelength are calculated. It was determined from dependences that absorption maxima of various types of nanotubes are in the wavelength region of about 266 nm. It was found that contact between nanotube and graphene was formed in time up to 400 fs. Formation of networks of SWCNT/MWCNT and their hybrids with rGO at threshold energy densities of 0.3/0.5 J/cm2 is shown. With an increase in energy density above the threshold value, formation of amorphous carbon nanoinclusions on the surface of nanotubes was demonstrated. For all films, except the MWCNT film, an increase in defectiveness after laser irradiation was obtained, which is associated with appearance of C–C bonds with neighboring nanotubes or graphene sheets. CNTs played the role of bridges connecting graphene sheets. Laser-synthesized hybrid nanostructures demonstrated the highest hardness compared to pure nanotubes. Maximum hardness (52.7 GPa) was obtained for MWCNT/rGO topology. Regularity of an increase in electrical conductivity of nanostructures after laser irradiation has been established for films made of all nanomaterials. Hybrid structures of nanotubes and graphene sheets have the highest electrical conductivity compared to networks of pure nanotubes. Maximum electrical conductivity was obtained for MWCNT/rGO hybrid structure (~22.6 kS/m). Networks of nanotubes and CNT/rGO hybrids can be used to form strong electrically conductive interconnections in nanoelectronics, as well as to create components for flexible electronics and bioelectronics, including intelligent wearable devices (IWDs). [ABSTRACT FROM AUTHOR]

We prepared a series of thermally remendable and recyclable polyurethanes crosslinked via reversible furan-maleimide Diels–Alder reaction based on TDI end-caped branched Voranol 3138 terminated with difurfurylamine and 4,4′-bis(maleimido)diphenylmethane (BMI). We showed that Young modulus strongly depends on BMI content (from 8 to 250 MPa) that allows us to obtain materials of different elasticity as simple as varying BMI content. The ability of DA and retro-DA reactions between furan and maleimide to reversibly bind material components was investigated by NMR spectroscopy, differential scanning calorimetry, and recycle testing. All polymers obtained demonstrated high strengths and could be recovering without significant loss in mechanical properties for at least five reprocessing cycles. [ABSTRACT FROM AUTHOR]

The blades of modern gas turbine engines are complex structures made of heat-resistant nickel alloys with a complex system of internal cavities. The article describes a method of strengthening samples of a heat-resistant Ni-Cr alloy by applying a composite coating (Cr-Al-Co + ZrO2-Y2O3). The alloy prototypes were fabricated by vacuum melting. An ion-plasma technology of a two-layer coating with an inner metal and an outer ceramic layer on the prepared surface of the heat-resistant alloy matrix was developed. The morphology and structure of the alloy prototypes and the investigated composite coating were studied by scanning electron spectroscopy. The total thickness of the two-layer wear-resistant coating was 17–18 μm. The thickness of the inner layer (Cr/Al/Co) is 10–11 μm and the thickness of the outer ceramic coating (ZrO2-Y2O3) is 6–7 μm. To improve the operational characteristics of the material, an electron-beam surface treatment was proposed. The research results showed a sevenfold increase in surface resistance compared with the initial state. [ABSTRACT FROM AUTHOR]

One of the prospective ways to safely preserve the genetic resources of red and black currant for breeding needs is the cryopreservation of cuttings with dormant buds. Vegetative cuttings of 12 varieties of red and 11 varieties of black currant were harvested in various regions of Russia: North, Northwest, and Central. Their viability after cryopreservation in nitrogen vapors (about −184 °C) under field conditions was studied. For red currant samples, it ranged from 61.2 ± 1.2% to 72.3 ± 3.0%, black currant—from 58.9 ± 1.1% to 73.5 ± 1.9%. In the group of red currant varieties, there were no significant differences in viability between varieties after cryopreservation. In the group of black currant varieties, "Chereshneva" and "Georgiy" had lower viability after storage in liquid nitrogen vapors than the others, 61.1% and 58.9%, respectively. On red currant, dry growing conditions of the experiment year significantly decreased the viability after cryopreservation. Neither black nor red currants revealed the influence of the place of harvesting on the survival of cuttings after cryopreservation. These results indicate the possibility of using cryopreservation to preserve cuttings of red and black currant with dormant buds collected in regions with different climatic environments. [ABSTRACT FROM AUTHOR]

The coating formation technique for artificial knee ligaments was proposed, which provided tight fixation of ligaments of polyethylene terephthalate (PET) fibers as a result of the healing of the bone channel in the short-term period after implantation. The coating is a frame structure of single-walled carbon nanotubes (SWCNT) in a collagen matrix, which is formed by layer-by-layer solidification of an aqueous dispersion of SWCNT with collagen during spin coating and controlled irradiation with IR radiation. Quantum mechanical method SCC DFTB, with a self-consistent charge, was used. It is based on the density functional theory and the tight-binding approximation. The method established the optimal temperature and time for the formation of the equilibrium configurations of the SWCNT/collagen type II complexes to ensure maximum binding energies between the nanotube and the collagen. The highest binding energies were observed in complexes with SWCNT nanometer diameter in comparison with subnanometer SWCNT. The coating had a porous structure—pore size was 0.5—6 μm. The process of reducing the mass and volume of the coating with the initial biodegradation of collagen after contact with blood plasma was demonstrated. This is proved by exceeding the intensity of the SWCNT peaks G and D after contact with the blood serum in the Raman spectrum and by decreasing the intensity of the main collagen bands in the SWCNT/collagen complex frame coating. The number of pores and their size increased to 20 μm. The modification of the PET tape with the SWCNT/collagen coating allowed to increase its hydrophilicity by 1.7 times compared to the original PET fibers and by 1.3 times compared to the collagen coating. A reduced hemolysis level of the PET tape coated with SWCNT/collagen was achieved. The SWCNT/collagen coating provided 2.2 times less hemolysis than an uncoated PET implant. MicroCT showed the effective formation of new bone and dense connective tissue around the implant. A decrease in channel diameter from 2.5 to 1.7 mm was detected at three and, especially, six months after implantation of a PET tape with SWCNT/collagen coating. MicroCT allowed us to identify areas for histological sections, which demonstrated the favorable interaction of the PET tape with the surrounding tissues. In the case of using the PET tape coated with SWCNT/collagen, more active growth of connective tissue with mature collagen fibers in the area of implantation was observed than in the case of only collagen coating. The stimulating effect of SWCNT/collagen on the formation of bone trabeculae around and inside the PET tape was evident in three and six months after implantation. Thus, a PET tape with SWCNT/collagen coating has osteoconductivity as well as a high level of hydrophilicity and hemocompatibility. [ABSTRACT FROM AUTHOR]

The effect of anomalous diffusion of lithium on the discharge curves and impedance spectra of lithium-ion batteries (LIB) is studied within the fractional differential generalization of the single-particle model. The distribution of lithium ions in electrolyte and electrode particles is expressed through the Mittag–Leffler function and the Lévy stable density. Using the new model, we generalize the equivalent circuit of LIB. The slope of the low-frequency rectilinear part of the Nyquist diagram does not always unambiguously determine the subdiffusion index and can be either larger or smaller than the slope corresponding to normal diffusion. The new aspect of capacity degradation related to a change in the type of ion diffusion in LIB components is discussed. [ABSTRACT FROM AUTHOR]