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Antithrombin deficiency, the most severe thrombophilia, might be underestimated, since it is only investigated in cases with consistent functional deficiency or family history. We have analyzed 444 consecutive, unrelated cases, from 1998 to 2021, with functional results supporting antithrombin deficiency in at least one sample. Plasma antithrombin was evaluated by functional and biochemical methods in at least two samples. SERPINC1 gene was analyzed by sequencing and MPLA. Hypoglycosylation was studied by electrophoresis and high-performance liquid chromatography (HPLC). In 260 of 305 cases (85.2%) with constitutive deficiency (activity < 80% in all samples), a SERPINC1 (N = 250), or N-glycosylation defect (N = 10) was observed, while 45 remained undetermined. The other 139 cases had normal antithrombin activity (≥ 80%) in at least one sample, what we called transient deficiency. Sixty-one of these cases (43.9%) had molecular defects: 48 had SERPINC1 variants, with two recurrent mutations (p.Ala416Ser[Cambridge II], N = 15; p.Val30Glu[Dublin], N = 12), and 13 hypoglycosylation. Thrombotic complications occurred in transient deficiency, but were less frequent, latter-onset, and had a higher proportion of arterial events than in constitutive deficiency. Two mechanisms explained transient deficiency: The limitation of functional methods to detect some variants and the influence of external factors on the pathogenic consequences of these mutations. Our study reveals a molecular defect in a significant proportion of cases with transient antithrombin deficiency, and changes the paradigm of thrombophilia, as the pathogenic effect of some mutations might depend on external factors and be present only at certain timepoints. Antithrombin deficiency is underestimated, and molecular screening might be appropriate in cases with fluctuating laboratory findings.

INTRODUCTION. This research paper presents the authors view on the essence of the problems of modern international law regulation of lethal autonomous weapons systems (LAWS) and international arms circulation. The authors dwell upon various aspects of new technologies in the field of creating LAWS, outline the prospects for the solution of the current challenges, as well as give a legal assessment of the legality of new types of weapons, methods and means of warfare from the perspective of contemporary international law. The system and mechanisms of international law regulation of the military purpose products circulation are also analyzed in this scientific work.MATERIALS AND METHODS. The subject of this study comprises international treaties, international customs, general principles of international law and national legislation of states. The study also includes the analysis of international acts of different nature, reports and other documents of international organizations, national authorities, scientific and educationalliterature. The methodological basis of this study is a wide range of research methods, namely: formal-legal, formal-logical, comparative-legal and historical-legal. In addition, the researchers apply system, structural and functional methods, as well as methods of analysis and generalization.RESEARCH RESULTS. The result of the study is the conclusion about the perspectives of developing auniversal definition of LAWS, as well as a common approach to understanding their characteristics and parameters of human control, and also about the advantages of LAWS in the course of military operations and solving national security problems of states, primarily in terms of compliance with IHL rules, which all military personnel are required to strictly observe. It is also necessary to take into account the crucial role of the issues of secrecy and national security, while Article 36 of Additional Protocol I does not contain criteria for distinguishing new types of weapons from other types of weapons, for example, from those that have undergone multi-stage modernization. It can be stated that at present there are only separate and insuffi ently effective mechanisms of international law regulation due to their voluntary basis. Therefore, national export control mechanisms are of paramount importance for the process of regulating the circulation of military purpose products, which is an essential element of national sovereignty.DISCUSSION AND CONCLUSIONS. The authors come to the following conclusions: the existing provisions of IHL are fully applicable to LAWS; responsibility for the use of LAWS should be borne by the person who manages the robotic complex or «programs» and gives the order to use LAWS, but the specific forms and methods of human control should remain at the discretion of states; Article 36 of Additional Protocol I provides extremely limited opportunities to prevent the creation of new weapons systems, does not require any reporting and control format; research and development of new types ofweapons are secret, and the acquisition or adoption of obviously or presumably indiscriminate weapons systems are not a violation, but rather a preparation for a violation or an activity of a controversial nature; further improvement of the international law regulation of arms circulation should be developed by creating mandatory universal mechanisms of international law regulation that would prevent the uncontrolled circulation and illegal distribution of weapons, including their sale to terrorists.

Purpose. To study the preferences of ophthalmologists in the implementation of therapeutic and diagnostic measures in children with myopia and habitually excessive tension of accommodation (HETA) as part of a routine clinical practice. Material and methods. The study was conducted based on outpatient ophthalmologists’ offices. The analysis involved 64 medical questionnaires received from 32 doctors from 23 cities of Russia (2 questionnaires of the same type were filled in, each for 20 patients) and information about 1280 clinical cases of myopia or habitually excessive tension of accommodation, documented in the medical records of children aged 5 to 17 years, diagnosed with myopia (863 children, 67.4% of the surveyed) or habitually excessive tension of accommodation (417 children, 32.6%). Data was sourced from medical treatment records and a survey of doctors’ opinions. Results. In the structure of juvenile myopia, the most commonly observed degrees are mild (49.36%) and moderate (37.31%). The recentness of myopia is proportional to its degree. Most often, for treating juvenile myopia and HETA, doctors combine a drug therapy aimed at improving accommodation (96.5%) with functional methods of treatment. Phenylephrine hydrochloride preparations such as Irifrin® and Irifrin® BK (28.44 and 33.13%, respectively), as well as the combined preparation Midrimax® (36.41%) were most often used as drug therapy. To improve accommodation, ophthalmologists of outpatient clinics more often prescribe a one-month course of drug instillations, and 50% of the respondents undergo it twice a year. However, the number of patients who rated the degree of satisfaction and adherence to therapy as high and very high turned out to be higher in cases when such courses were underwent 4 times a year, compared with the group of patients who underwent them 2 times a year. Conclusion. Convenience of use of Irifrin®, Irifrin® BK and Midrimax® drugs, combined with their availability, make it possible to recommend them for a wide clinical use – treatment of patients with myopia and habitually excessive tension of accommodation.

The purpose of the article is consideration of stylistic and conceptual innovative ideas directed by the modern French avant-garde theater Nanter-Amandier. The methodology consists of the application of empirical, art history, analytical, axiomatic, functional methods of researching the concept of ideas of avant-garde directing of Nanterre-Amandier theater, its innovations, and search for radical reforms of stage skills, phenomenal artistic techniques of theatrical forms. Scientific Novelty. For the first time, empirical analysis and substantiation of the concept of ideas of avant-garde directing of the Nanterre-Amandier Theater, its innovations in the search for original artistic and creative solutions of stage forms. Conclusions. Directors of the modern French avant-garde theater J.-P. Vincent, J.-L. Martinelli and F. Ken successfully embodied innovative artistic techniques by transforming the reality surrounding the modern human and transmitting it to the viewer - this breaks the close relationship of artistic intentions with the socio-cultural environment. The depiction of the world by modern directors of the French avant-garde theater is characterized by a deep and holistic rethinking of it in accordance with the specifics of socio-historical processes, the development of scientific and technological progress, the general philosophical and aesthetic picture of the world, and others.

The article deals with the application of functional methods for the study of the respiratory system, such as spirometry, bronchodilatation test, stress testing to detect bronchial hyperreactivity, provocative test with metacholine, impulse oscillometry, body plethysmography for the diagnosis, following up and prediction of the course of asthma.

This article provides an unsystematic literature review devoted to analyzing the currently existing methods of functional diagnostics for age-related macular degeneration.The essence, advantages and disadvantages, and literature data on the use of such methods asphotostresstest, electrooculography, dark adaptation study, contrast sensitivity function assessment, light and color sensitivity study,electroretinographyand critical flicker fusion frequencyare described.Based on the analysis of literature data, itis shownthat currently, there is a need to searchfor informative and accessible methods of functional diagnostics in age-related macular degeneration, especially for its early diagnosis. The analysis has shown that the existing methods are mainly aimed either at fixing secondary morphological changes in the layer of pigment epithelial cells, at identifying the pathology of the pigment epithelium in conjunction with determining the function of photoreceptor elements, or at a comprehensive assessment of the structures of several layers of the retina. Keywords:age-related macular degeneration; methods of functional diagnostics; photostress test; electrooculography; contrast sensitivity

The purpose of the study is to study the correlation rate of the quality of life, electroneuromyography, doppler and neuro markers BNDF in the blood in patients with a type 2 of type with diabetic foot syndrome. Methods: The following 2 groups of patients were formed: 1 gr. - SDS patients, neuropathic form -37 patients, 2 gr. - SDS patients, neuroichmic form -35 patients, 3 gr. - Control group, these are 20 healthy persons of the appropriate age and gender. Results: In all groups of patients, the quality of life is significantly different in the FSHC questionnaire compared with the control group (p

The ground states of the neutral and anionic tetrafluoride and hexafluoride series of 3d-metal atoms from Sc to Zn were assigned by using a double-check approach in which the pure and hybrid density functional methods were interchangeably used. It was confirmed that all these neutral fluorides are superhalogens except for TiF4. The electron affinities of the hexafluorides were shown to be consistently higher than those of the tetrafluorides in accordance with the superhalogen conception of the extra electron delocalization over a larger number of the electronegative ligands. In the search for mononuclear fluorides possessing higher electron affinities, we considered the M(F2)6- and M(F3)6- series where M = Sc-Zn. We found that the optimized geometrical structures in both series may be described as MF6-- k(F2), k = 3 and 6, of which the geometry of the MF6- core mimics that of the corresponding hexafluoride anion and the F2 dimers are kept in a bound state by polarizing forces. In these cases, the electron affinity is decreased by tenths of eV with respect to the electron affinity of the core hexafluorides due to a confinement of the extra electron by the F2 environment.

Microvascular dysfunction is one of the hallmarks of systemic sclerosis (SSc). The presence of pulmonary-arterial-hypertension (PAH) in SSc-patients is associated with poor prognosis. This is a systematic review and meta-analysis of studies assessing microvascular and endothelial injury with functional techniques in SSc-patients with PAH (SSc–PAH) compared to those without PAH (SSc–non-PAH) (PROSPERO: CRD42021236212). Literature search involved PubMed, the-Cochrane-Library, Web-of-Science, Scopus and manual search of article references. Studies assessing microvascular function by all available functional methods were considered eligible. Preclinical studies and studies using structural nailfold-videocapillaroscopy or biomarkers were excluded. Newcastle–Ottawa-Scale (NOS) was applied to evaluate the quality of retrieved studies. From a total of 602 retrieved articles, four studies (n = 159 participants) were included in meta-analysis; three studies were of high quality (NOS ≥ 7). In pooled analysis, a marginally significant impaired microvascular function was observed in SSc–PAH compared to SSc–non-PAH patients [SMD − 0.71, 95% CI (− 1.53, 0.12)], with significant between-study heterogeneity (I2 = 80%, p = 0.002). Among the studies examining endothelium-dependent and -independent vasodilation with LDF-iontophoresis, SSc–PAH subjects had significantly impaired endothelium-dependent-vasodilation [Ach-stimulated %change WMD − 216.79, 95% CI (− 337.87, − 95.71), I2 = 0%, p = 0.40], but no significant differences in endothelium-independent-vasodilation [SNP-stimulated %change WMD 90.84, 95% CI (− 82.52, 264.19), I2 = 44%, p = 0.18] compared with SSc–non-PAH subjects. In sensitivity analysis including only studies where SSc–PAH patients were diagnosed by right-heart-catheterization, a borderline difference between the two groups was noted [SMD − 1.09, 95% CI (− 2.30, 0.13), I2 = 82%, p = 0.004]. SSc–PAH patients showed marginally impaired microvascular function in the pooled analysis, as well as impaired endothelium-dependent-vasodilation in subgroup analysis compared with SSc–non-PAH patients. Vascular endothelial dysfunction could be involved in high cardiovascular risk of patients with SSc and PAH.

Topicality. All over the world, there is an increased interest in mental retardation issue in various aspects. The role of physical therapy for mentally retarded children is to correct the motor skills, to increase the level of health and physical training, and to have a positive effect on the psycho-emotional status. The aim of the research was to analyze the effect of physical therapy on the morphofunctional status and fine motor skills of 7–8 year old boys with mild mental retardation. Stuff and research methods. The study, by agreement of the parents, involved 8 boys aged 7–8 years with a diagnosis of ICD-10 – retardation, F70 – mild mental retardation. The study used theoretical research methods, clinical examination, questionnaires, survey, anthropometric methods, functional methods, and motor function diagnostics. The research results. During the experiment, which lasted 8 months, the indicators of physical development and functional status of 7–8 year old boys underwent positive changes. A comparative analysis of the indicators of boys’ fine motor skills development after the experiment has showed a significant improvement of test results. Thus, when performing the test “Make a mosaic” the difference in indicators before and after the experiment was 2 points, at p

The mercury dihalides show a remarkable diversity in the structural preferences in their minimum energy structure types, spanning molecular to strongly bound ionic solids. A challenge in the development of density functional methods for extended systems is to arrive at strategies that serve equally well such a broad range of bonding modes or structural preferences. The chemical bonding and the stabilities of mercury dihalides and the general utility and reliability of the van der Waals density functional with C09 exchange (vdW-DF-C09) in predicting or describing the energetics and structural preferences in these metal dihalides is examined. We show that, in contrast with the uncorrected generalized gradient approximation of the Perdew-Burke-Erzenhoff (PBE) exchange-correlation functional, qualitative and quantitative patterns in the bonding of the mercury dihalide solids are well reproduced with vdW-DF-C09 for the full series of HgX2 systems for X = F, Cl, Br, and I. The possible existence of a low-temperature cotunnite polymorph for HgF2 and PbF2 is posited.

Quantum chemical calculations using density functional methods were performed for complexes of type L2C2 with L = NHCMe (1), SNHCMe (2) (S = saturated), cAACMe (3), and diamidocarbene (DACMe) (4). ...

Background Occlusal interference causes instability in temporomandibular joint and hyperactivity of mastication muscles which eventually leads to temporomandibular joint dysfunction. Therefore, achieving stable occlusion is important in young patients. It is key factor in optimizing functional occlusion in adulthood. Aim Application of «The ABO Model Grading System» and Mandibular Position Indicator as an additional diagnostic method in children undergoing orthodontic treatment using braces. Methods Thirty-two patients aged 14 to 18 diagnosed with teeth crowding on the upper and lower jaws were examined, then separated in two groups of 16 people each. All patients underwent orthodontic treatment using braces. Results In group 2, due to application the anthropometrical system of quantitative evaluation ABO with re-fixing the incorrectly arranged braces by indirect bonding method, occlusal interferences were eliminated. MPI analysis showed discrepancy between the central occlusion and the central relation which was not as relevant as in the group 1 (p > 0.05). Conclusion Using the anthropometric system of quantitative assessment of ABO with subsequent re-fixation of incorrectly placed braces by indirect bonding, effectively improves the MPI. This determines the unity of position between articular condyles on the lower jaw in the centric occlusion and in the centric relation, which allows to get a stable result of orthodontic treatment.

Tri-coordinated Fe single sites on the (111)n surface of γ-alumina have been investigated by the carefully calibrated density functional methods (M12-L/SV) using periodic boundary conditions. For a...

Subject. The current level of development of dentistry requires the use of an algorithm for diagnosis, monitoring and quality control of orthopedic treatment of patients using functional research methods, planning and manufacturing of dental prosthesis designs based on digital technologies. The goal is to develop an algorithm for orthopedic treatment of patients with defects in the hard tissues of teeth and dentitions using digital functional examination methods. Methodology. Clinical data are based on the results of orthopedic treatment of two groups of patients with defects in the hard tissues of teeth and dentitions. The main group consisted of 129 people, whose diagnostic and treatment complex had an extended instrumental clinical and functional analysis of static and dynamic ratios of teeth and jaws, and orthopedic treatment was carried out according to an improved CAD/CAM protocol. Comparison group ― 147 people, comprehensive dental diagnostics and prosthetic treatment carried out using the standard CAD/CAM technique. Results. Using in-depth functional diagnostics of the dento-jaw system based on digital technologies, a comprehensive assessment of the status of the dental status of the examined patients is given, an algorithm for their comprehensive diagnosis and treatment is developed, indications for their prosthetics in the usual occlusion or in the central ratio of the jaws are specified. The production of fixed anatomical structures of dentures has been optimized by improving the methodology for modeling their masticatory surfaces using the Hint-Els CAD/CAM system. Conclusions. Analysis of the examination results and monitoring of the stages of orthopedic treatment of patients testifies to the effectiveness of the proposed algorithm and advanced CAD/CAM technology. The developed indications for the replacement of defects in the hard tissues of teeth and dentitions are determined as the result of many years of research that can achieve practical results ― increasing the effectiveness of their treatment using digital functional diagnostic methods and orthopedic treatment.

Microorganisms and plants can be important sources of many compounds with potential pharmaceutical applications. Extraction of these matrices is one of the ways of identifying the presence of inhibitory active substances against enzymes whose high activity leads to serious human diseases including cancer, Parkinson's or Crohn's diseases. The isolation and purification of inhibitors are time-consuming and expensive steps in the analysis of the crude extract and therefore, it is necessary to find a fast, efficient, and inexpensive method for screening extracts of interest. TLC-Bioautography combines the separation of the extract on a thin layer with its subsequent biological analysis. TLC-Bioautography methods have been developed for several classes of enzymes including oxidoreductases, hydrolases and isomerases, and there is a potential for developing functional methods for other classes of enzymes. This review summarizes known TLC-Bioautography methods and their applications for determining the presence of enzyme inhibitors in extracts and compares the effectiveness of different methodological approaches. It also indicates the current state and perspective of the development of TLC-Bioautography and its possible future applications.

The purpose of the study was to assess the prevalence of sarcopenia in people over 65 years of age, to analyze instrumental and functional methods for studying skeletal muscle in the elderly. A case-control study of 230 participants 65 years of age and older, the average age of 74±6,5 years. Patients were divided into three age groups: 1st - 65-74 years old, 2nd - 75-84 years old, 3rd - 85 years and older. The calculation of muscle mass was carried out according to the index of appendicular muscle mass (AMM/m2) using dual-energy x-ray absorptiometry (DXA) with correction of patient growth. Muscle strength was measured with a «Jamar» hand dynamometer, muscle function was determined using a short set of physical activity tests (SPPB tests). The prevalence of sarcopenia was 30% in the presented sample and increased with increasing age of patients. There were no significant differences in the incidence of the most common chronic diseases, with the exception of obesity, which was less common in sarcopenic patients than in non-sarcopenic patients (p

In the article, we solve the inverse problems to recover unknown space-time dependent functions of heat conductivity and heat source for a nonlinear convective-diffusive equation, without needing o...

1) To elucidate the role of collector channels in the aqueous humor outflow pathway 2) To suggest anatomic and functional methods of imaging collector channels in-vitro and in-vivo and 3) To discuss the role of such imaging modalities in the surgical management of glaucoma.A thorough literature search was conducted on databases for studies published in English regarding the available methods to determine the role of collecting channels in normal and glaucomatous patients and to assess their patency.Intraocular pressure (IOP) exists as a balance between aqueous humor production and aqueous humor outflow. Collector channels are an essential anatomical constituent of the distal portion of the conventional aqueous humor outflow pathway. There are different surgical options for glaucoma management and with the recent advances in Schlemm's canal-based surgeries, collector channel's patency became a key factor in determining the optimum management for the glaucomatous eye. The advent of anatomic imaging methods has improved the ability to visualize collector channel morphology in-vitro, including swept-source optical coherence tomography (SS-OCT), spectral domain optical coherence tomography (SD-OCT), micro-computed tomography (micro CT), new immunohistochemistry techniques and scanning electron microscopy. The recent advent of real-time assessment of collector channel patency (including evaluation of episcleral venous outflow, observation of episcleral venous fluid wave, and tracer studies utilizing fluorescein, indocyanine green, and trypan blue) has been validated by the aforementioned anatomic imaging modalities.New modalities of in-vitro and in-vivo studies of collector channels provide promise to aid in the assessment of collector channel patency and individualization of surgical management for glaucoma patients.

A transformation is introduced in momentum representation to keep a covariant description at every stage of a loop computation in gravity. The procedure treats on equal footing local internal and space-time symmetries althought the complete transformation is known for the former [1] whereas in gravity we solve for the first few orders in an expansion. As an explicit application the one loop UV divergences of Hilbert-Einstein gravity with a cosmological constant and spin 0, 1/2 and 1 matter are computed with functional methods and in a field-covariant formalism.

Relevance. The subject of the research is to compare different functional methods for determining the optimal position of the mandible.Purpose. To find the advantages and disadvantages of using various functional diagnostic methods to determine the optimal position of the mandible.Materials and methods. We conducted a literature review of the functional methods for determining the optimal position of the mandible in the treatment of patients with temporomandibular disorders. Nowadays different methods are used, such as anatomical and physiological method, bilateral manipulation, front deprogrammer, graphic method, aksiography, kineziography, TENS et al.Results. The method of bimanual manipulation and frontal deprogrammer determine the central relation when TMJ pathology is not expressed and the load test is negative. The graphic method evaluates the function of the temporomandibular joint, determines the optimal position of the mandible. TENS moves the lower jaw to a position of physiological rest. Kinesiography and Axiography determine the temporomandibular disorders and we can use them to dynamically monitor patients at all stages of treatment, monitor the determination of the optimal position of the mandible.Conclusion. From the results of this study, we can conclude that there are a lot of methods of functional diagnostics of TMJ, which help to determine the optimal position of the mandible. Everybody can choose their own set of methods, that let reduce the number of non-examined patients with temporomandibular disorders.

Background Despite of many attempts to determine or correct hip and knee joint parameters via non-invasive techniques such as regression or functional methods, in conventional gait models the position of the ankle joint center still is assumed at the center point between malleoli. Research question The aim of this study was to estimate the ankle joint parameters using a functional approach. Methods To this aim, we used data of 23 typically developed adults performing two different calibration motions. Subsequently, we applied functional approaches to determine the functional joint center and axis. Results The results show significant differences for ankle joint parameters in all directions for both calibration motions applied with respect to the malleoli line. Most prominently, we find a shift of the ankle joint center of 7 % of the foot length anteriorly to the malleoli mid-point when applying functional calibration. Conclusion These significant alterations of the ankle joint center and axis indicate the importance of accurate determination of ankle joint parameters and consequently their influence on the clinical outcome.

Two methods to calculate negative electron affinities systematically from ground-state density functional methods are presented. One makes use of the lowest unoccupied molecular orbital energy shift provided by approximate inclusion of derivative discontinuity in the nearly correct asymptotic potential (NCAP) nonempirical, constraint-based generalized gradient approximation exchange functional. The other uses a second-order perturbation calculation of the derivative discontinuity based on the NCAP exchange-correlation potential. On a set of thirty-eight molecules, NCAP leads to a rather accurate description that is improved further through the perturbation correction. The results presented show the importance of the asymptotic behavior of the exchange-correlation potential in the calculation of negative electron affinities as well as demonstrating the versatility of the NCAP functional.

International activity of modern states has the multi-layered nature comprising regions and municipalities (local communities). Switzerland is a federal state where cantons have broad powers. Cantons’ international activity is a matter of academic interest. Firstly, they develop cooperation with the constituent entities of the Russian Federation. Secondly, they have much experience in international activity. Thirdly, that issue hasn’t been sufficiently researched in Russia. The subject of the study is an analysis of legal regulation and the mechanism of public administration in the field of the Swiss cantons’ international links. The formal legal, comparative and functional methods are used. The source base includes Swiss legislation, cantons’ constitutions and their international treaties. Special attention is paid to the practical aspect of the cantons’ participation in the international relations, particularly with the subjects of the Russian Federation. The resources of the data are the Ministry of Foreign Affairs and the Ministry of Industry and Trade of the Russian Federation. The novelty of the analysis is the determination of forms of cantons’ international activity, as well as the analysis of the institutional mechanism of public administration in that area. The findings can be used to improve the practice of the public administration and the coordination of the international and foreign economic links of the constituent entities of the Russian Federation.

Outlier detection techniques play a vital role in exploring unusual data of extreme events that have a critical effect considerably in the modeling and forecasting of functional data. The functional methods have an effective way of identifying outliers graphically, which might not be visible through the original data plot in classical analysis. This study’s main objective is to detect the extreme rainfall events using functional outliers detection methods depending on the depth and density functions. In order to identify the unusual events of rainfall variation over long time intervals, this work conducts based on the average monthly rainfall of the Taiz region from 1998 to 2019. Data were extracted from the Tropical Rainfall Measuring Mission and the analysis has been processed by R software. The approaches applied in this study involve rainbow plots, functional highest density region box-plot as well as functional bag-plot. According to the current results, the functional density box-plot method has proven effective in detecting outlier compared to the functional depth bag-plot method. In conclusion, the results of the current study showed that the rainfall over the Taiz region during the last two decades was influenced by the extreme events of years 1999, 2004, 2005, and 2009.

Fe(III) complexes are receiving ever-increasing attention as spin crossover (SCO) systems because they are usually air stable, as opposed to Fe(II) complexes, which are prone to oxidation. Here, we present the first systematic study exclusively devoted to assess the accuracy of several exchange-correlation functionals when it comes to predicting the energy gap between the high-spin (S = 5/2) and the low-spin (S = 1/2) states of Fe(III) complexes. Using a dataset of 24 different Fe(III) hexacoordinated complexes, it is demonstrated that the B3LYP* functional is an excellent choice not only for predicting spin-state energy gaps for Fe(III) complexes undergoing spin-transitions but also for discriminating Fe(III) complexes that are either low- or high-spin in the whole range of temperatures. Our benchmark study has led to the identification of a very versatile Fe(III) compound whose SCO properties can be engineered upon changing a single axial ligand. Overall, this work demonstrates that B3LYP* is a reliable functional for screening new spin-crossover systems with tailored properties.

Marketing activities nowadays play an important place in the enterprise management system. In conditions of high competition, companies must be able to promote their products and services so that the consumer remains satisfied. The purpose of this work is to determine and streamline the theoretical foundations of marketing product policy of the enterprise and create recommendations for its improvement. The article is devoted to the management of marketing activities at the enterprise with the help of the main tools of product policy. The study analyzes the necessary conditions and ways to improve goods and services in modern markets, provides recommendations for building effective strategies for marketing control of product policy, as well as highlights the main factors that may affect sales. On the example of the plant for the manufacture of household appliances "SATURN", located in the city of Cherkasy, it is determined what conditions are necessary for the normal functioning of the enterprise, and as a result for maximum profits. There are also examples of how marketing policy is applied in enterprises, what methods and strategies are used in Ukrainian enterprises in comparison with foreign ones. The main tasks for optimizing the work of the enterprise are determined and the influence of the enterprise 's goods on its work is analyzed, the risks of the marketing commodity policy are determined. The study also identified the implications of marketing control over marketing policy, namely strategies that help businesses grow. Since the optimal functioning of the enterprise depends on the development and implementation of an effective and productive marketing product strategy, the article identified the consequences of non-compliance with these strategies. It is also established what role the socio-economic situation in the country and the range and nomenclature play in the development of commodity policy. The following research methods were used in the course of work: method of comparison, analysis, synthesis, generalization, induction, deduction, explanation, as well as system and functional methods.

The mechanism of formic acid decomposition on the Pd(111) surface has been investigated by several theoretical methods in previous studies, including PBE and PW91. These results indicated that the mechanism is different from different methods, and even by using the same method (i.e., PBE), the mechanism is also different. In this study, we have revisited the formic acid decomposition on Pd(111) surface by using another density functional RPBE and by including van der Waals interaction which is neglected in the previous studies. Our results showed that the formic acid is decomposed via O–H bond cleavage to form bi-HCOO*, and the most favorable pathway is HCOOH* → bi-HCOO* + H* → CO2* + 2H*. The energy barrier is 0.55 eV at the rate-determining step. This conclusion is consistent with one of the PBE study. This demonstrated that computational methods have a great influence on the reaction mechanism, and care should be taken in selecting the appropriate computational methods.

Twelve common density functional methods and seven basis sets for geometry optimization were evaluated on the accuracy of1H/13C NMR chemical shift calculations for biaryls. For these functionals,1H shifts calculations for gas phase optimized geometries were significantly less accurate than those for in-solution optimized structures, while13C results were not strongly influenced by geometry optimization methods and solvent effects. B3LYP, B3PW91, mPW1PW91 andωB97XD were the best-performing functionals with lowest errors; among seven basis sets, DGDZVP2 and 6-31G(d,p) outperformed the others. The combination of these functionals and basis sets resulted in high accuracy with CMAEmin= 0.0327 ppm (0.76%) and 0.888 ppm (0.58%) for1H and13C, respectively. The selected functionals and basis set were validated when consistently producing optimized structures with high accuracy results for1H and13C chemical shift calculations of two other biaryls. This study highly recommends the IEFPCM/B3LYP, B3PW91, mPW1PW91 orωB97XD/DGDZVP2 or 6-31G(d,p) level of theory for the geometry optimization step, especially the solvent incorporation, which would lead to high accuracy1H/13C calculation. This work would assist in the fully structural assignments of biaryls and provide insights into in-solution biaryl conformations.

The animation community has spent significant effort trying to ease rigging procedures. This is necessitated because the increasing availability of 3D data makes manual rigging infeasible. However, object animations involve understanding elaborate geometry and dynamics, and such knowledge is hard to infuse even with modern data-driven techniques. Automatic rigging methods do not provide adequate control and cannot generalize in the presence of unseen artifacts. As an alternative, one can design a system for one shape and then transfer it to other objects. In previous work, this has been implemented by solving the dense point-to-point correspondence problem. Such an approach requires a significant amount of supervision, often placing hundreds of landmarks by hand. This paper proposes a functional approach for skeleton transfer that uses limited information and does not require a complete match between the geometries. To do so, we suggest a novel representation for the skeleton properties, namely the functional regressor, which is compact and invariant to different discretizations and poses. We consider our functional regressor a new operator to adopt in intrinsic geometry pipelines for encoding the pose information, paving the way for several new applications. We numerically stress our method on a large set of different shapes and object classes, providing qualitative and numerical evaluations of precision and computational efficiency. Finally, we show a preliminar transfer of the complete rigging scheme, introducing a promising direction for future explorations.