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The approaches to analysis of medical personnel of stomatological service continue to be based on principles formed in relation to state health care system that makes it difficult to objectively assess situation due to increasing proportion of specialists employed in its private sector. The study, targeted to comprehensive comparative analysis of stomatological medical personnel of state and private medical organizations in the Irkutsk Oblast, for the first time made it possible to assess provision of population of large region and its municipalities with stomatologists, considering specialists employed in private medical organizations, in dynamics and in context of separate specialties. The decrease in provision of population with stomatologists in state medical organizations by 12.3% in 2019-2023 against the background of its increase in private ones by 14.5% was revealed. In 2023, 50.5% of stomatologists were concentrated in private sector of stomatological service and 30.8% in state sector. Yet another 18.7% combined their work in medical organizations of both types. The stomatologists employed in private sector of stomatological service were mainly concentrated in metropolises, especially in regional center, where their provision exceeds average regional level by 2.6 times.

Ultrafast all-optical modulation with optically resonant nanostructures is an essential technology for high-speed signal processing on a compact optical chip. Key challenges that exist in this field are relatively low and slow modulations in the visible range as well as the use of expensive materials. Here we develop an ultrafast all-optical modulator based on MAPbBr 3 perovskite metasurface supporting exciton-polariton states with exceptional points. The additional angular and spectral filtering of the modulated light transmitted through the designed metasurface allows us to achieve 2500% optical signal modulation with the shortest modulation time of 440 fs at the pump fluence of ∼40 μJ/cm 2 . Such a value of the modulation depth is record-high among the existing modulators in the visible range, while the main physical effect behind it is polariton condensation. Scalable and cheap metasurface fabrication via nanoimprint lithography along with the simplicity of perovskite synthesis and deposition make the developed approach promising for real-life applications.

Optical data storage, information encryption, and security labeling technologies require materials that exhibit local, pronounced, and diverse modifications of their structure-dependent optical properties under external excitation. Herein, we propose and develop a novel platform relying on lead halide Ruddlesden-Popper phases that undergo a light-induced transition toward bulk perovskite and employ this phenomenon for the direct optical writing of multicolor patterns. This transition causes the weakening of quantum confinement and hence a reduction in the band gap. To extend the color gamut of photoluminescence, we use mixed-halide compositions that exhibit photoinduced halide segregation. The emission of the films can be tuned across the range of 450-600 nm. Laser irradiation provides high-resolution direct writing, whereas continuous-wave ultraviolet exposure is suitable for recording on larger scales. The luminescent images created on such films can be erased during the visualization process. This makes the proposed writing/erasing platform suitable for the manufacturing of optical data storage devices and light-erasable security labels.

Cyanocobalamin (CNCbl), a medicinal form of vitamin B 12 , is resistant to glutathione (GSH), and undergoes intracellular processing via reductive decyanation producing the Co(II)-form of Cbl (Cbl(II)) mediated by the CblC-protein. Alteration of the CblC-protein structure might inhibit CNCbl processing. Here, we showed that introducing a bromine atom to the C10-position of the CNCbl corrin ring facilitates its reaction with GSH leading to the formation of Cbl(II) and cyanide dissociation. In a neutral medium, the reaction between C10-Br-CNCbl and GSH proceeds via the complexation of the reactants further leading to dimethylbenzimidazole (DMBI) substitution and electron transfer from GSH to the Co(III)-ion. The reaction is accelerated upon the GSH thiol group deprotonation. The key factors explaining the higher reactivity of C10-Br-CNCbl compared with unmodified CNCbl towards GSH are increasing the electrode potential of CNCbl two-electron reduction upon meso-bromination and the substantial labilization of DMBI, which was shown by comparing their reactions with cyanide and the pK a values of DMBI protonation (pK a base-off ). Aquacobalamin (H 2 OCbl) brominated at the C10-position of the corrin reacts with GSH to give Cbl(II) via GSH complexation and subsequent reaction of this complex with a second GSH molecule, whereas unmodified H 2 OCbl generates glutathionyl-Cbl, which is resistant to further reduction by GSH., (© 2023. The Author(s), under exclusive licence to Society for Biological Inorganic Chemistry (SBIC).)

The task of increasing staffing of physicians in primary health care level is resolving by accreditation of medical workers. The sociological assessment of motives of employment and professional adaptation of graduates of medical university who started to work as district therapists and pediatricians after undergoing primary accreditation was carried out. Only about 7% of graduates initially wished to work as district physicians. The most frequent reasons of employment were to get additional points for admission to residency (18%) and need in financial resources (18%). The analysis of professional plans of respondents testifies intention of every second to leave primary medical care to work in specialty received in residency. The seven out of ten respondents noted insufficient scope of necessary clinical knowledge and practical skills, lacking of effective measures for professional adaptation, including internship and supervision.

Nowadays, development of organizational structures coordinating personnel policy in health care of the Subjects of the Russian Federation is relevant. The purpose of the study was to investigate feasibility, scientifically substantiate and implement at the level of the subject of the Russian Federation measures developing organizational structures to coordinate participants of personnel policy in health care. According to 88.5% of interrogated experts, insufficient interaction between participants of personnel policy in health care is a significant cause of problems of medical personnel in the Irkutsk Oblast. About 81.1% of respondents consider overall efficiency of interaction between participants as low. The survey permitted to study main directions and degree of interaction between participants of personnel policy in Oblast health care. At that, 82.8% of respondents indicated that intensification of low interaction requires development of special organizational structure. The obtained results permitted to formulate proposals concerning organization in the Irkutsk Oblast of Medical Council under the Governor and in its structure working group on personnel policy in health care. The corresponding methodological support was developed.

Halide perovskites belong to an important family of semiconducting materials with electronic properties that enable a myriad of applications, especially in photovoltaics and optoelectronics. Their optical properties, including photoluminescence quantum yield, are affected and notably enhanced at crystal imperfections where the symmetry is broken and the density of states increases. These lattice distortions can be introduced through structural phase transitions, allowing charge gradients to appear near the interfaces between phase structures. In this work, we demonstrate controlled multiphase structuring in a single perovskite crystal. The concept uses cesium lead bromine (CsPbBr 3 ) placed on a thermoplasmonic TiN/Si metasurface and enables single-, double-, and triple-phase structures to form on demand above room temperature. This approach promises application horizons of dynamically controlled heterostructures with distinctive electronic and enhanced optical properties.

Ligand-free methods for the synthesis of halide perovskite nanocrystals are of great interest because of their excellent performance in optoelectronics and photonics. In addition, template-assisted synthesis methods have become a powerful tool for the fabrication of environmentally stable and bright nanocrystals. Here we develop a novel approach for the facile ligand-free template-assisted fabrication of perovskite nanocrystals with a near-unity absolute quantum yield, which involves CaCO 3 vaterite micro- and submicrospheres as templates. We show that the optical properties of the obtained nanocrystals are affected not mainly by the template morphology, but strongly depend on the concentration of precursor solutions, anion and cation ratio, as well as on adding defect-passivating rare-earth dopants. The optimized samples are further tested as infrared radiation visualizers exhibiting promising characteristics comparable to those that are commercially available.

We demonstrate that the power conversion efficiency (PCE), photocurrent, and fill factor (FF) of perovskite solar cells (PSC) can be significantly improved by the photoinduced self-gating in ionic liquids (ILs) via n-doping of the carbon nanotube (CNT) top electrode on the fullerene electron transport layer (ETL). CNTs, graphene, and other carbon electrodes have been proven to be stable electrodes for PSC, but efficiency was not high. We have previously shown that the performance of PSCs with CNT electrodes can be improved by IL gating with gate voltage ( V g ) applied from an external power source. Here we demonstrate that effective self-gating in ILs is possible by a photoinduced process, without an external source. The open circuit voltage ( V oc ) generated by the PSC itself can be applied to the CNT/C60 electrode as V g leading to photogating. This self-gating with V oc is compared to photocharging of CNTs in ILs without any gating for two types of fullerene ETLs: C 60 and C 70 , Two types of ILs, DEME-TFSI and BMIM-BF 4 , are tested for two types of nanotubes electrodes: single wall (SWCNT), and multiwall (MWCNT). The resulting improvements are analyzed using the effective diode-circuit (DC) and the drift-diffusion (DD) models. Self-gating allows the PCE improvement from 3-5% to 10-11% for PSCs with a thick ETL, while for optimal combination of a thin SWCNT/ETL with added layers for improved stability, the PCE reached 13.2% in DEME-TFSI IL., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

During the last years, giant optical anisotropy has demonstrated its paramount importance for light manipulation. In spite of recent advances in the field, the achievement of continuous tunability of optical anisotropy remains an outstanding challenge. Here, we present a solution to the problem through the chemical alteration of halogen atoms in single-crystal halide perovskites. As a result, we manage to continually modify the optical anisotropy by 0.14. We also discover that the halide perovskite can demonstrate optical anisotropy up to 0.6 in the visible range─the largest value among non-van der Waals materials. Moreover, our results reveal that this anisotropy could be in-plane and out-of-plane depending on perovskite shape─rectangular and square. As a practical demonstration, we have created perovskite anisotropic nanowaveguides and shown a significant impact of anisotropy on high-order guiding modes. These findings pave the way for halide perovskites as a next-generation platform for tunable anisotropic photonics.

A novel series of cyclometalated platinum(II) complexes bearing acyclic diaminocarbene (ADC) ancillary ligands were designed and prepared. Their photophysical properties were systematically studied through experimental and theoretical investigations. All complexes exhibit green phosphorescence with a quantum efficiency of up to 45% in 2 wt% doped PMMA film at room temperature. The complexes are used as light-emitting dopants for organic light-emitting diode (OLED) fabrication. The devices displayed a green emission with a maximum current efficiency of 2.9 cd A -1 and a luminance of 2700 cd m -2 . These results show that these cyclometalated platinum(II) complexes can be used as efficient green emitting components of OLED devices.

Halide perovskite nano- and microlasers have become a very convenient tool for many applications from sensing to reconfigurable optical chips. Indeed, they exhibit outstanding emission robustness to crystalline defects due to so-called "defect tolerance" allowing for their simple chemical synthesis and further integration with various photonic designs. Here we demonstrate that such robust microlasers can be combined with another class of resilient photonic components, namely, with topological metasurfaces supporting topological guided boundary modes. We show that this approach allows to outcouple and deliver the generated coherent light over tens of microns despite the presence of defects of different nature in the structure: sharp corners in the waveguide, random location of the microlaser, and defects in the microlaser caused by mechanical pressure applied during its transfer to the metasurface. As a result, the developed platform provides a strategy to attain robust integrated lasing-waveguiding designs resilient to a broad range of structural imperfections, both for electrons in a laser and for pseudo-spin-polarized photons in a waveguide.

At the present time, about 20% of graduates of medical universities after initial accreditation are employed as district physicians. The purpose of the study was to investigate readiness of graduates of medical university to work as district physicians after primary accreditation. The analysis was based on results of sociological survey of immediate supervisors of graduates. The interviewed heads of departments assess as relatively low level of practical training of graduates (3.8 points out of 5) and their readiness to independent work as district physicians (41.2%). The scarcity of implementation of the most effective measures for professional adaptation of novice district physicians, including paid mentoring (5.0%) and internship (1.7%) is established too. According to survey results, for training of district physicians, the most appropriate is to revive such previous forms of training in national system of higher medical education as internship (21.2%) and subordination (50.6%).

An approach to increase the efficiency of europium-based OLEDs was proposed through the formation of a mixed-ligand complex. The design of a series of europium complexes, together with an optimization of the solution deposition, including the host selection, as well as the variation of the solvent and deposition parameters, resulted in a noticeable increase in OLED luminance. As a result, the maximum luminance of the Eu-based OLED reached up to 700 cd/m 2 , which is one of the highest values for an Eu-based solution-processed OLED. Finally, its stability was investigated.

Detection of hazardous volatile organic and inorganic species is a crucial task for addressing human safety in the chemical industry. Among these species, there are hydrogen halides (HX, X = Cl, Br, I) vastly exploited in numerous technological processes. Therefore, the development of a cost-effective, highly sensitive detector selective to any HX gas is of particular interest. Herein, we demonstrate the optical detection of hydrogen chloride gas with solution-processed halide perovskite nanowire lasers grown on a nanostructured alumina substrate. An anion exchange reaction between a CsPbBr 3 nanowire and vaporized HCl molecules results in the formation of a structure consisting of a bromide core and thin mixed-halide CsPb(Cl,Br) 3 shell. The shell has a lower refractive index than the core does. Therefore, the formation and further expansion of the shell reduce the field confinement for experimentally observed laser modes and provokes an increase in their frequency. This phenomenon is confirmed by the coherency of the data derived from XPS spectroscopy, EDX analysis, in situ XRD experiments, HRTEM images, and fluorescent microspectroscopy, as well as numerical modeling for Cl - ion diffusion and the shell-thickness-dependent spectral position of eigenmodes in a core-shell perovskite nanowire. The revealed optical response allows the detection of HCl molecules in the 5-500 ppm range. The observed spectral tunability of the perovskite nanowire lasers can be employed not only for sensing but also for their precise spectral tuning.

Exciton-polaritons offer a versatile platform for realization of all-optical integrated logic gates due to the strong effective optical nonlinearity resulting from the exciton-exciton interactions. In most of the current excitonic materials there exists a direct connection between the exciton robustness to thermal fluctuations and the strength of the exciton-exciton interaction, making materials with the highest levels of exciton nonlinearity applicable at cryogenic temperatures only. Here, we show that strong polaronic effects, characteristic for perovskite materials, allow overcoming this limitation. Namely, we demonstrate a record-high value of the nonlinear optical response in the nanostructured organic-inorganic halide perovskite MAPbI 3 , experimentally detected as a 19.7 meV blueshift of the polariton branch under femtosecond laser irradiation. This is substantially higher than characteristic values for the samples based on conventional semiconductors and monolayers of transition-metal dichalcogenides. The observed strong polaron-enhanced nonlinearity exists for both tetragonal and orthorhombic phases of MAPbI 3 and remains stable at elevated temperatures.

Silicon nanophotonics has become a versatile platform for optics and optoelectronics. For example, strong light localization at the nanoscale and lack of parasitic losses in infrared and visible spectral ranges make resonant silicon nanoparticles a prospect for improvement in such rapidly developing fields as photovoltaics. Here, we employed optically resonant silicon nanoparticles produced by laser ablation for boosting the power conversion efficiency of organic solar cells. Namely, we created colloidal solutions of spherical nanoparticles with a range of diameters (80-240 nm) in different solvents. We tested how the nanoparticles' position in the device, their concentration, silicon doping, and method of deposition affected the final device efficiency. The best conditions optimization resulted in an efficiency improvement from 6% up to 7.5%, which correlated with numerical simulations of nanoparticles' optical properties. The developed low-cost approach paves the way toward highly efficient and stable solution-processable solar cells.

Perovskite solar cells (PSCs) currently reach high efficiencies, while their insufficient stability remains an obstacle to their technological commercialization. The introduction of hole-transport materials (HTMs) into the device structure is a key approach for enhancing the efficiency and stability of devices. However, currently, the influence of the HTM structure or properties on the characteristics and operational stability of PSCs remains insufficiently studied. Herein, we present four novel push-pull small molecules, H1-4 , with alternating thiophene and benzothiadiazole or fluorine-loaded benzothiadiazole units, which contain branched and linear alkyl chains in the different positions of terminal thiophenes to evaluate the impact of HTM structure on PSC performance. It is demonstrated that minor changes in the structure of HTMs significantly influence their behavior in thin films. In particular, H3 organizes into highly ordered lamellar structures in thin films, which proves to be crucial in boosting the efficiency and stability of PSCs. The presented results shed light on the crucial role of the HTM structure and the morphology of films in the performance of PSCs.

Future technologies underpinning multifunctional physical and chemical systems and compact biological sensors will rely on densely packed transformative and tunable circuitry employing nanophotonics . For many years, plasmonics was considered as the only available platform for subwavelength optics, but the recently emerged field of resonant metaphotonics may provide a versatile practical platform for nanoscale science by employing resonances in high-index dielectric nanoparticles and metasurfaces. Here, we discuss the recently emerged field of metaphotonics and describe its connection to material science and chemistry. For tunabilty, metaphotonics employs a variety of the recently highlighted materials such as polymers, perovskites, transition metal dichalcogenides, and phase change materials. This allows to achieve diverse functionalities of metasystems and metasurfaces for efficient spatial and temporal control of light by employing multipolar resonances and the physics of bound states in the continuum. We anticipate expanding applications of these concepts in nanolasers, tunable metadevices, metachemistry, as well as a design of a new generation of chemical and biological ultracompact sensing devices.

Besides its use in medicine, vitamin B 12 (cobalamin) and its derivatives have found in numerous applications as catalysts. However, studies related to the activation of oxidants via cobalamin are scant. In this work, we showed how the addition of aquacobalamin (H 2 OCbl) accelerates the destruction of azo-dye Orange II by peroxymonosulfate (HSO 5 - ) in aqueous solutions. In neutral and weakly alkaline media, the process is initiated by the modification of the corrin macrocycle with HSO 5 - , which requires the preliminary deprotonation of the aqua-ligand in H 2 OCbl to give hydroxocobalamin, producing 5,6-dioxo-5,6-secocobalamin or its isomer (14,15-dioxo-14,15-secocobalamin). In acidic solutions, where the concentration of hydroxocobalamin is negligible, the formation of dioxo-seco-species is not observed, and the reaction between H 2 OCbl and HSO 5 - results in slow chromophore bleaching. Using terephthalic acid, we demonstrated the formation of hydroxyl radicals in the mixture of H 2 OCbl with HSO 5 - , whereas the generation of sulfate radicals was proved by comparing the effects of ethanol and nitrobenzene on Orange II destruction using the H 2 OCbl/HSO 5 - system. The reaction mechanism includes the binding of HSO 5 - to the Co(III) ion of dioxo-secocobalamin, which results in its deprotonation and the labilization of the O-O bond, leading to the formation of sulfate and hydroxyl radicals which further react with Orange II.

Antireflection and light-trapping coatings are important parts of photovoltaic architectures, which enable the reduction of parasitic optical losses, and therefore increase the power conversion efficiency (PCE). Here, we propose a novel approach to enhance the efficiency of perovskite solar cells using a light-trapping electrode (LTE) with non-reciprocal optical transmission, consisting of a perforated metal film covered with a densely packed array of nanospheres. Our LTE combines charge collection and light trapping, and it can replace classical transparent conducting oxides (TCOs) such as ITO or FTO, providing better optical transmission and conductivity. One of the most promising applications of our original LTE is the optimization of efficient bifacial perovskite solar cells. We demonstrate that with our LTE, the short-circuit current density and fill factor are improved for both front and back illumination of the solar cells. Thus, we observe an 11% improvement in the light absorption for the monofacial PSCs, and a 15% for the bifacial PSCs. The best theoretical results of efficiency for our PSCs are 27.9% (monofacial) and 33.4% (bifacial). Our study opens new prospects for the further efficiency enhancement for perovskite solar cells.

Nutritional deficiency and genetic errors that impair the transport, absorption, and utilization of vitamin B 12 (B 12 ) lead to hematological and neurological manifestations. The cblC disease (cobalamin complementation type C) is an autosomal recessive disorder caused by mutations and epi-mutations in the MMACHC gene and the most common inborn error of B 12 metabolism. Pathogenic mutations in MMACHC disrupt enzymatic processing of B 12 , an indispensable step before micronutrient utilization by the two B 12 -dependent enzymes methionine synthase (MS) and methylmalonyl-CoA mutase (MUT). As a result, patients with cblC disease exhibit plasma elevation of homocysteine (Hcy, substrate of MS) and methylmalonic acid (MMA, degradation product of methylmalonyl-CoA, substrate of MUT). The cblC disorder manifests early in childhood or in late adulthood with heterogeneous multi-organ involvement. This review covers current knowledge on the cblC disease, structure-function relationships of the MMACHC protein, the genotypic and phenotypic spectra in humans, experimental disease models, and promising therapies., Competing Interests: The authors declare no competing interests., (© 2022.)

The outstanding optical properties and multiphoton absorption of lead halide perovskites make them promising for use as fluorescence tags in bioimaging applications. However, their poor stability in aqueous media and biological fluids significantly limits their further use for in vitro and in vivo applications. In this work, we have developed a universal approach for the encapsulation of lead halide perovskite nanocrystals (PNCs) (CsPbBr 3 and CsPbI 3 ) as water-resistant fluorescent markers, which are suitable for fluorescence bioimaging. The obtained encapsulated PNCs demonstrate bright green emission at 510 nm (CsPbBr 3 ) and red emission at 688 nm (CsPbI 3 ) under one- and two-photon excitation, and they possess an enhanced stability in water and biological fluids (PBS, human serum) for a prolonged period of time (1 week). Further in vitro and in vivo experiments revealed enhanced stability of PNCs even after their introduction directly into the biological microenvironment (CT26 cells and DBA mice). The developed approach allows making a step toward stable, low-cost, and highly efficient bioimaging platforms that are spectrally tunable and have narrow emission.

One of the most important tasks in transition to primary accreditation of health care professionals is increasing manning of primary health care section. It is achievable at the expense of opportunity for graduates of medical universities to find employment as district physicians and pediatricians without residency training. The purpose of the study was to assess impact on increasing of number of physicians of primary health care section of their admission to professional activities after primary accreditation. The study was carried out in the Irkutsk State Medical University provided objective quantitative evaluation of this occurrence. It was revealed that only every fifth graduate in specialty "General Medicine" and "Pediatrics" is employed as district physician, in half of cases combining this work with residency training, that subsequently results in leaving primary health care section. Only one out of ten continues to work in this position during 3-5 years.

Halide perovskite nanowire-based lasers have become a powerful tool for modern nanophotonics, being deeply subwavelength in cross-section and demonstrating low-threshold lasing within the whole visible spectral range owing to the huge gain of material even at room temperature. However, their emission directivity remains poorly controlled because of the efficient outcoupling of radiation through their subwavelength facets working as pointlike light sources. Here, we achieve directional lasing from a single perovskite CsPbBr 3 nanowire by imprinting a nanograting on its surface, which provides stimulated emission outcoupling to its vertical direction with a divergence angle around 2°. The nanopatterning is carried out by the high-throughput laser ablation method, which preserves the luminescent properties of the material that is typically deteriorated after processing via conventional lithographic approaches. Moreover, nanopatterning of the perovskite nanowire is found to decrease the number of the lasing modes with a 2-fold increase of the quality factor of the remaining modes.

The architecture of transparent contacts is of utmost importance for creation of efficient flexible light-emitting devices (LEDs) and other deformable electronic devices. We successfully combined the newly synthesized transparent and durable silicone rubbers and the semiconductor materials with original fabrication methods to design LEDs and demonstrate their significant flexibility. We developed electrodes based on a composite GaP nanowire-phenylethyl-functionalized silicone rubber membrane, improved with single-walled carbon nanotube films for a hybrid poly(ethylene oxide)-metal-halide perovskite (CsPbBr 3 ) flexible green LED. The proposed approach provides a novel platform for fabrication of flexible hybrid optoelectronic devices.

Halide perovskite nanomaterials are widely used in optoelectronics and photonics due to their outstanding luminescent properties, whereas their strong multiphoton absorption makes them prospective for bioimaging. Nonetheless, instability of perovskites in aqueous solutions is an important limitation that prevents their application in biology and medicine. Here, we demonstrate fluorescence and upconversion imaging in living cells by employing CsPbBr 3 nanocrystals (NCs) that show an improved water-resistance (at least for 24 h) after their coating as individual particles with various silica-based shells. The obtained phTEOS-TMOS@CsPbBr 3 NCs possess high quality, which we confirm with high-resolution transmission and scanning transmission electron microscopy, X-ray diffraction analysis, Fourier-transform infrared and energy-dispersive X-ray spectroscopies, as well as with fluorescence optical microscopy. The developed platform can make the halide perovskite NCs suitable for various bioimaging applications.

Multiphoton absorption and luminescence are fundamentally important nonlinear processes for utilizing efficient light-matter interaction. Resonant enhancement of nonlinear processes has been demonstrated for many nanostructures; however, it is believed that all higher-order processes are always much weaker than their corresponding linear processes. Here, we study multiphoton luminescence from structured surfaces and, combining multiple advantages of perovskites with the concept of metasurfaces, we demonstrate that the efficiency of nonlinear multiphoton processes can become comparable to the efficiency of the linear process. We reveal that the perovskite metasurface can enhance substantially two-photon stimulated emission with the threshold being comparable with that of the one-photon process. Our modeling of free-carrier dynamics and exciton recombination upon nonlinear photoexcitation uncovers that this effect can be attributed to the local field enhancement in structured media, a substantial increase of the mode overlap, and the selection rules of two-photon absorption in perovskites.

Aquacobalamin binds hydrogen peroxide reversibly to form a cobalt(III) hydroperoxo adduct with a 0.25 mM dissociation constant, as evidenced by UV-vis absorption spectroscopy and corroborated by NMR, Raman spectroscopy, stopped-flow UV-vis measurements, and density functional theory calculations.

The level of development of human resources in health care is determined by a number of factors, among which an important place belongs to turnover of medical staff. The turnover, or the process of unscheduled dismissal of staff, negatively affects functioning of the organization in any field, including health care. Although the analysis of staff turnover is widely applied in various fields of activity, relatively few studies are related to problems of assessing causes of this phenomenon in health care. The purpose of the study was to assess the characteristics and causes of turnover of medical staff in state medical organizations of the Irkutsk Oblast. The detailed information about the respondents obtained in the study made it possible to get a concept of intensity and characteristics of turnover of physicians and medical nurses, and to study causes of dismissal of respondents from their previous employment as well as causes that influenced current employment and to assess content and effectiveness of measures of professional adaptation and social support of hired specialists.

We study active dielectric metasurfaces composed of two-dimensional arrays of split-nanodisk resonators fabricated in InGaAsP membranes with embedded quantum wells. Depending on the geometric parameters, such split-nanodisk resonators can operate in the optical anapole regime originating from an overlap of the electric dipole and toroidal dipole Mie-resonant optical modes, thus supporting strongly localized fields and high- Q resonances. We demonstrate room-temperature lasing from the anapole lattices of engineered active metasurfaces with low threshold and high coherence.

Hydrogen sulfide (H 2 S) is a gasotransmitter and the smallest signaling thiol metabolite with important roles in human health. The turnover of H 2 S in humans is mainly governed by enzymes of sulfur amino acid metabolism and also by the microbiome. As is the case with other small signaling molecules, disease-promoting effects of H 2 S largely depend on its concentration and compartmentalization. Genetic defects that impair the biogenesis and catabolism of H 2 S have been described; however, a gap in knowledge remains concerning physiological steady-state concentrations of H 2 S and their direct clinical implications. The small size and considerable reactivity of H 2 S renders its quantification in biological samples an experimental challenge. A compilation of methods currently employed to quantify H 2 S in biological specimens is provided in this review. Substantial discrepancy exists in the concentrations of H 2 S determined by different techniques. Available methodologies permit end-point measurement of H 2 S concentration, yet no definitive protocol exists for the continuous, real-time measurement of H 2 S produced by its enzymatic sources. We present a summary of available animal models, monogenic diseases that impair H 2 S metabolism in humans including structure-function relationships of pathogenic mutations, and discuss possible approaches to overcome current limitations of study.

Hypochlorous acid (HOCl) is a strong oxidant produced by myeloperoxidase. Previous work suggested that HOCl modifies the corrin ring of cobalamins to yield chlorinated species via mechanisms that are incompletely understood. Herein, we report a mechanistic study on the reaction between cyanocobalamin (CNCbl, vitamin B 12 ) and HOCl. Under weakly acidic, neutral and weakly alkaline conditions, the reaction produces the c-lactone derivative of CNCbl chlorinated at the C10-position of corrin ring (C10-Cl-CNCbl-c-lactone). Formation of C10-Cl-CNCbl-c-lactone was not observed at pH ≥ 9.9. The chlorination of CNCbl by HOCl proceeds via two pathways involving one and two HOCl molecules: the reaction is initiated by the very fast formation of a complex between CNCbl and HOCl, which either undergoes slow transformation to chlorinated species, or rapidly reacts with a second HOCl molecule to produce C10-Cl-CNCbl. Subsequent reaction of C10-Cl-CNCbl with HOCl proceeds rapidly toward lactone ring formation by H-atom abstraction at position C8. This work uncovered mechanisms and products of the reaction of a biologically active and therapeutically used cobalamin, CNCbl and the endogenous oxidant HOCl. Binding and reactivity studies of C10-Cl-CNCbl and C10-Cl-CNCbl-c-lactone with relevant proteins of the cobalamin pathway and with cultured cells are necessary to elucidate the potential physiological effects of these species.

The medical personnel reallocation is the most important resource to ensure sustainable functioning and development of medical organizations and health care system as a whole. The purpose of the study was to assess reallocation of medical personnel of state medical organizations in the subject of the Russian Federation exemplified by the Irkutsk Oblast in 2015-2019. The study permitted to test approaches to application of methods for analysis of reallocation of medical personnel in respect of physicians. The results contribute to development of measures targeted to prevent and to reduce the medical personnel turnover and to increase efficiency of human resources management in health care.

Thiolatocobalamins are a class of cobalamins comprised of naturally occurring and synthetic ligands. Glutathionylcobalamin (GSCbl) occurs naturally in mammalian cells, and also as an intermediate in the glutathione-dependent dealkylation of methylcobalamin (MeCbl) to form cob(I)alamin by pure recombinant CblC from C. elegans. Glutathione-driven deglutathionylation of GSCbl was demonstrated both in mammalian as well as in C. elegans CblC. Dethiolation is orders of magnitude faster than dealkylation of Co-C bonded cobalamins, which motivated us to investigate two synthetic thiolatocobalamins as substrates to repair the enzymatic activity of pathogenic CblC variants in humans. We report the synthesis and kinetic characterization of cysteaminylcobalamin (CyaCbl) and 2-mercaptopropionylglycinocobalamin (MpgCbl). Both CyaCbl and MpgCbl were obtained in high purity (90-95%) and yield (78-85%). UV-visible spectral properties agreed with those reported for other thiolatocobalamins with absorbance maxima observed at 372 nm and 532 nm. Both CyaCbl and MpgCbl bound to wild type human recombinant CblC inducing spectral blue-shifts characteristic of the respective base-on to base-off transitions. Addition of excess glutathione (GSH) resulted in rapid elimination of the β-ligand to give aquacobalamin (H 2 OCbl) as the reaction product under aerobic conditions. Further, CyaCbl and MpgCbl underwent spontaneous dethiolation thereby repairing the loss of activity of pathogenic variants of human CblC, namely R161G and R161Q. We posit that thiolatocobalamins could be exploited therapeutically for the treatment of inborn errors of metabolism that impair processing of dietary and supplemental cobalamin forms. While these disorders are targets for newborn screening in some countries, there is currently no effective treatment available to patients., Competing Interests: Declaration of competing interest The authors declare no conflicts of interest., (Copyright © 2020 Elsevier B.V. and Société Française de Biochimie et Biologie Moléculaire (SFBBM). All rights reserved.)

Inorganic halides perovskite CsPbX 3 (X = Cl, Br, and I or mixed halide systems Cl/Br and Br/I) nanoparticles are efficient light-conversion objects that have attracted significant attention due to their broadband tunability over the entire visible spectral range of 410-700 nm and high quantum yield of up to 95%. Here, we demonstrate a new method of recrystallization of CsPbBr 3 nanoparticles inside the electrospun fluoropolymer fibers. We have synthesized nonwoven tetrafluoroethylene mats embedding CsPbBr 3 nanoparticles using inexpensive commercial precursors and syringe electrospinning equipment. The fabricated nonwoven mat samples demonstrated both down-conversion of UV light to 506 nm and up-conversion of IR femtosecond laser radiation to 513 nm green photoluminescence characterized by narrow emission line-widths of 35 nm. Nanoparticle formation inside nonwoven fibers was confirmed by TEM imaging and water stability tests controlled by fluorimetry measurements. The combination of enhanced optical properties of CsPbBr 3 nanoparticles and mechanical stability and environmental robustness of highly deformable nonwoven fluoropolymer mats is appealing for flexible optoelectronic applications, while the industry-friendly fabrication method is attractive for commercial implementations.

Hybrid organic-inorganic perovskites, while well examined for photovoltaic applications, remain almost completely unexplored in the terahertz (THz) range. These low-cost hybrid materials are extremely attractive for THz applications because their optoelectronic properties can be chemically engineered with relative ease. Here, we experimentally demonstrate the first attempt to apply solution-processed polycrystalline films of hybrid perovskites for the development of photoconductive terahertz emitters. By using the widely studied methylammonium-based perovskites MAPbI 3 and MAPbBr 3 , we fabricate and characterize large-aperture photoconductive antennas. The work presented here examines polycrystalline perovskite films excited both above and below the bandgap, as well as the scaling of THz emission with the applied bias field and the optical excitation fluence. The combination of ultrafast time-resolved spectroscopy and terahertz emission experiments allows us to determine the still-debated room temperature carrier lifetime and mobility of charge carriers in halide perovskites using an alternative noninvasive method. Our results demonstrate the applicability of hybrid perovskites for the development of scalable THz photoconductive devices, making these materials competitive with conventional semiconductors for THz emission.

The integration of nanoparticles (NPs) into functional materials is a powerful tool for the smart engineering of their physical properties. If properly designed and optimized, NPs possess unique optical, electrical, quantum, and other effects that will improve the efficiency of optoelectronic devices. Here, we propose a novel approach for the enhancement of perovskite light-emitting diodes (PeLEDs) based on electronic band structure deformation by core-shell NPs forming a metal-oxide-semiconductor (MOS) structure with an Au core and SiO2 shell located in the perovskite layer. The presence of the MOS interface enables favorable charge distribution in the active layer through the formation of hole transporting channels. For the PeLED design, we consider integration of the core-shell NPs in the realistic numerical model. Using our verified model, we show that, compared with the bare structure, the incorporation of NPs increases the radiative recombination rate of PeLED by several orders of magnitude. It is intended that this study will open new perspectives for further efficiency enhancement of perovskite-based optoelectronic devices with NPs.

The full control of the fundamental photophysics of nanosystems at frequencies as high as few THz is key for tunable and ultrafast nanophotonic devices and metamaterials. Here we combine geometrical and ultrafast control of the optical properties of halide perovskite nanoparticles, which constitute a prominent platform for nanophotonics. The pulsed photoinjection of free carriers across the semiconducting gap leads to a subpicosecond modification of the far-field electromagnetic properties that is fully controlled by the geometry of the system. When the nanoparticle size is tuned so as to achieve the overlap between the narrowband excitons and the geometry-controlled Mie resonances, the ultrafast modulation of the transmittivity is completely reversed with respect to what is usually observed in nanoparticles with different sizes, in bulk systems, and in thin films. The interplay between chemical, geometrical, and ultrafast tuning offers an additional control parameter with impact on nanoantennas and ultrafast optical switches.

Inexpensive perovskite light-emitting devices fabricated by a simple wet chemical approach have recently demonstrated very prospective characteristics such as narrowband emission, low turn-on bias, high brightness, and high external quantum efficiency of electroluminescence, and have presented a good alternative to well-established technology of epitaxially grown III-V semiconducting alloys. Engineering of highly efficient perovskite light-emitting devices emitting green, red, and near-infrared light has been demonstrated in numerous reports and has faced no major fundamental limitations. On the contrary, the devices emitting blue light, in particular, based on 3D mixed-halide perovskites, suffer from electric field-induced phase separation (segregation). This crystal lattice defect-mediated phenomenon results in an undesirable color change of electroluminescence. Here we report a novel approach towards the suppression of the segregation in single-layer perovskite light-emitting electrochemical cells. Co-crystallization of direct band gap CsPb(Cl,Br)3 and indirect band gap Cs4Pb(Cl,Br)6 phases in the presence of poly(ethylene oxide) during a thin film deposition affords passivation of surface defect states and an increase in the density of photoexcited charge carriers in CsPb(Cl,Br)3 grains. Furthermore, the hexahalide phase prevents the dissociation of the emissive grains in the strong electric field during the device operation. Entirely resistant to 5.7 × 106 V·m-1 electric field-driven segregation light-emitting electrochemical cell exhibits stable emission at wavelength 479 nm with maximum external quantum efficiency 0.7%, maximum brightness 47 cd·m-2, and turn-on bias of 2.5 V.

The personnel policy is one of priority areas of developing national health care. Its effective implementation requires evidence-based development of relevant program documents, the most important of which is the Concept of health care personnel policy that currently exists only in a number of regions of the Russian Federation. In this regard, the purpose of the study was to develop approaches to scientific justification and development of the Concept of health care personnel policy at the level of region of the Russian Federation, as exemplified in the Irkutsk oblast. The article describes progress of this large-scale and lengthy study, its main results included. The developed approaches resulted in comprehensive organizational technology of development corresponding Concept. The results of this experience can be implemented in other regions of the Russian Federation. Therefore, it is of scientific and practical interest for all potential developers of similar program documents and wide range of specialists in health care organization.

Engineering of nonlinear optical response in nanostructures is one of the key topics in nanophotonics, as it allows for broad frequency conversion at the nanoscale. Nevertheless, the application of the developed designs is limited by either high cost of their manufacturing or low conversion efficiencies. This paper reports on the efficient second-harmonic generation in a free-standing GaP nanowire array encapsulated in a polymer membrane. Light coupling with optical resonances and field confinement in the nanowires together with high nonlinearity of GaP material yield a strong second-harmonic signal and efficient near-infrared (800-1200 nm) to visible upconversion. The fabricated nanowire-based membranes demonstrate high flexibility and semitransparency for the incident infrared radiation, allowing utilizing them for infrared imaging, which can be easily integrated into different optical schemes without disturbing the visualized beam.

Resonant dielectric structures have emerged recently as a new platform for subwavelength nonplasmonic photonics. It was suggested and demonstrated that magnetic and electric Mie resonances can enhance substantially many effects at the nanoscale including spontaneous Raman scattering. Here, we demonstrate stimulated Raman scattering (SRS) for isolated crystalline silicon (c-Si) nanoparticles and observe experimentally a transition from spontaneous to stimulated scattering manifested in a nonlinear growth of the signal intensity above a certain pump threshold. At the Mie resonance, the light gets confined into a low volume of the resonant mode with enhanced electromagnetic fields inside the c-Si nanoparticle due to its high refractive index, which leads to an overall strong SRS signal at low pump intensities. Our finding paves the way for the development of efficient Raman nanolasers for multifunctional photonic metadevices.

Reduction of the wavelength in on-chip light circuitry is critically important not only for the sake of keeping up with Moore's law for photonics but also for reaching toward the spectral ranges of operation of emerging materials, such as atomically thin semiconductors, vacancy-based single-photon emitters, and quantum dots. This requires efficient and tunable light sources as well as compatible waveguide networks. For the first challenge, halide perovskites are prospective materials that enable cost-efficient fabrication of micro- and nanolasers. On the other hand, III-V semiconductor nanowires are optimal for guiding of visible light as they exhibit a high refractive index as well as excellent shape and crystalline quality beneficial for strong light confinement and long-range waveguiding. Here, we develop an integrated platform for visible light that comprises gallium phosphide (GaP) nanowires directly embedded into compact CsPbBr 3 -based light sources. In our devices, perovskite microcrystals support stable room-temperature lasing and broadband chemical tuning of the emission wavelength in the range of 530-680 nm, whereas GaP nanowaveguides support efficient outcoupling of light, its subwavelength (<200 nm) confinement, and long-range guiding over distances more than 20 μm. As a highlight of our approach, we demonstrate sequential transfer and conversion of light using an intermediate perovskite nanoparticle in a chain of GaP nanowaveguides.

Subwavelength particles supporting Mie resonances underpin a strategy in nanophotonics for efficient control and manipulation of light by employing both an electric and a magnetic optically induced multipolar resonant response. Here, we demonstrate that monolithic dielectric nanoparticles made of CsPbBr 3 halide perovskites can exhibit both efficient Mie-resonant lasing and structural coloring in the visible and near-IR frequency ranges. We employ a simple chemical synthesis with nearly epitaxial quality for fabricating subwavelength cubes with high optical gain and demonstrate single-mode lasing governed by the Mie resonances from nanocubes as small as 310 nm by the side length. These active nanoantennas represent the most compact room-temperature nonplasmonic nanolasers demonstrated until now.

Nanophotonics based on resonant nanostructures and metasurfaces made of halide perovskites have become a prospective direction for efficient light manipulation at the subwavelength scale in advanced photonic designs. One of the main challenges in this field is the lack of large-scale low-cost technique for subwavelength perovskite structures fabrication preserving highly efficient luminescence. Here, unique properties of halide perovskites addressed to their extremely low thermal conductivity (lower than that of silica glass) and high defect tolerance to apply projection femtosecond laser lithography for nanofabrication with precise spatial control in all three dimensions preserving the material luminescence efficiency are employed. Namely, with CH 3 NH 3 PbI 3 perovskite highly ordered nanoholes and nanostripes of width as small as 250 nm, metasurfaces with periods less than 400 nm, and nanowire lasers as thin as 500 nm, corresponding to the state-of-the-art in multistage expensive lithographical methods are created. Remarkable performance of the developed approach allows to demonstrate a number of advanced optical applications, including morphology-controlled photoluminescence yield, structural coloring, optical- information encryption, and lasing., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Nowadays, in Russia number of problems is present in effective personnel policy in health care. The National Concept of personnel policy in health care (2002) expired in 2010 and no new one was developed. However, corresponding program documents were adopted at the level of subjects of the Russian Federation. The purpose of study was to compare evaluation of program documents of subjects of the Russian Federation related to issues of personnel policy in health care. The continuous sampling technique was applied to study these documents, which were valid in the territories of all subjects of the Russian Federation in 2002-2019. The comparative assessment was performed. It is demonstrated that the most informative document in this area is only the corresponding specialized Concept. However, this document was adopted only in 8.2% of the subjects of the Russian Federation, and they were valid only in two subjects. The concepts of health care development in the subjects of the Russian Federation, addressing medical personnel policy were adopted in 44.7% of the subjects of the Russian Federation. However, these legal documents operate only in 15.3% of territories. At the same time, the availability of appropriate specialized program document is a prerequisite of development of coherent and effective medical personnel policy in health care at all its levels.