Machine learning powered by principal component descriptors as the key for sorted structural fit of XANES.

Modern synchrotron radiation sources and free electron laser made X-ray absorption spectroscopy (XAS) an analytical tool for the structural analysis of materials under in situ or operando conditions. Fourier approach applied to the extended region of the XAS spectrum (EXAFS) allows the estimation of the number of structural and non-structural parameters which can be refined through a fitting procedure. The near edge region of the XAS spectrum (XANES) is also sensitive to the coordinates of all the atoms in the local cluster around the absorbing atom. However, in contrast to EXAFS, the existing approaches of quantitative analysis provide no estimation for the number of structural parameters that can be evaluated for a given XANES spectrum. This problem exists both for the classical gradient descent approaches and for modern machine learning methods based on neural networks. We developed a new approach for rational fit based on principal component descriptors of the spectrum. In this work the principal component analysis (PCA) is applied to a dataset of theoretical spectra calculated a priori on a grid of variable structural parameters of a molecule or cluster. Each principal component of the dataset is related then to a combined variation of several structural parameters, similar to the vibrational normal mode. Orthogonal principal components determine orthogonal deformations that can be extracted independently upon the analysis of the XANES spectrum. Applying statistical criteria, the PCA-based fit of the XANES determines the accessible structural information in the spectrum for a given system.

X-ray emission spectroscopy: highly sensitive techniques for time-resolved probing of cerium reactivity under catalytic conditions.

Oxygen storage materials such as ceria are used in many catalytic applications because they can reversibly bind and release oxygen. Tools are needed to observe and quantify this activity which involves a change in the cerium oxidation state and to understand the involvement of cerium in catalytic processes. To prove that cerium changes its oxidation state in the catalytic cycle the transient rates of Ce3+ formation and decay should be compared to the overall reaction rate. For such mechanistic studies the time resolution is essential as the quantification of the Ce3+ species should be faster than the reaction rate. However, it is challenging to follow the dynamic changes of the cerium oxidation state under reaction conditions, especially when the concentration of cerium atoms involved in the reaction cycle is low. In this paper, we evaluate the sensitivity of high-resolution X-ray emission-based methods for the in situ time-resolved quantification of small concentrations of Ce3+ in ceria-based materials. We demonstrate that resonant X-ray emission spectroscopy (RXES) at optimal excitation energy is more sensitive than high energy resolution off-resonant spectroscopy (HEROS) and non-resonant X-ray emission spectroscopy (non-resonant XES) and that it can track the reactivity of less than 0.3% of cerium atoms in a 1% Pt/CeO2 catalyst in a plug-flow reactor with sub-second time resolution. These results demonstrate that X-ray emission-based methods can be used as very sensitive tools and provide new insights into dynamic changes of the oxidation state in reducible oxides in a variety of applications.

Atomically dispersed rhodium on a support: the influence of a metal precursor and a support.

The influence of the support type and the metal precursor on the dispersion of rhodium after calcination and reduction was determined. The combination of electron microscopy and X-ray absorption analysis allowed the quantification of the amount of atomically dispersed rhodium in the samples. Higher amounts of atomically dispersed rhodium atoms are obtained when metal impregnation is performed with a rhodium acetate precursor in comparison to a rhodium chloride precursor over supports of the same composition. The stability of rhodium is improved with the addition of promoters; the co-presence of samaria and ceria in the support and metal impregnation with a rhodium acetate precursor leads to the highest amount of atomically dispersed rhodium remaining after reductive treatment at 773 K.

Assessing the environmental benefit of palladium-based single-atom heterogeneous catalysts for Sonogashira coupling.

The Pd-Cu catalysed Sonogashira coupling of terminal alkynes and aryl halides is a cornerstone synthetic strategy for C-C bond formation. Homogeneous organometallic systems conventionally applied are typically not reusable and require efficient downstream Pd removal steps for product purification, making it challenging to fully recover the precious metal. A holistic cradle-to-gate life cycle assessment (LCA) unveils that process footprint can be improved up to two orders of magnitude from repeated catalyst reuse. New classes of heterogeneous catalysts based on isolated metal atoms (single-atom catalysts, SACs) demonstrate promising potential to synergise the benefits of solid and molecular catalysts for efficient Pd utilisation. Here we show that using Pd atoms anchored on nitrogen-doped carbon permits full recovery of the metal and reuse of the catalyst over multiple cycles. A hybrid process using the Pd-SAC with a homogeneous CuI cocatalyst is more effective than a fully heterogeneous analogue based on a bimetallic Pd-Cu SAC, which deactivates severely due to copper leaching. In some scenarios, the LCA-based metrics demonstrate the footprint of the hybrid homogeneous-heterogeneous catalytic process is leaner than the purely homogeneous counterpart already upon single reuse. Combining LCA with experimental evaluation will be a useful guide to the implementation of solid, reusable catalysts for sustainable organic transformations.

[Diagnostic criterion for anorexia nervosa].

Article presents a case of anorexia in 29 years old patient. Described the clinical symptoms of anorexia, the manifestations of the disease in patient; the premorbid characteristics of personality, the formation of which influences on relationships with parents.

[Treatment of tobacco dependence in patients with chronic diseases of digestive system].

The purpose of this study was to increase the effectiveness of tobacco control by improving the treatment of tobacco dependence. The article presents the data results of different methods of treatments of tobacco dependence among 135 patients with digestive diseases. As the most effective is a comprehensive approach combining psychotherapy and physiotherapy methods is designated. The possible reasons of due treatment effect absence are separately analysed: a sharp severity of tobacco withdrawal syndrome, inadequate primary motivation of smoking refusal, premorbid personality characteristics, a pathological variant of response to disease.

Dynamics and Site Isolation: Keys to High Propane Dehydrogenation Performance of Silica-Supported PtGa Nanoparticles.

Nonoxidative dehydrogenation of light alkanes has seen a renewed interest in recent years. While PtGa systems appear among the most efficient catalyst for this reaction and are now implemented in production plants, the origin of the high catalytic performance in terms of activity, selectivity, and stability in PtGa-based catalysts is largely unknown. Here we use molecular modeling at the DFT level on three different models: (i) periodic surfaces, (ii) clusters using static calculations, and (iii) realistic size silica-supported nanoparticles (1 nm) using molecular dynamics and metadynamics. The combination of the models with experimental data (XAS, TEM) allowed the refinement of the structure of silica-supported PtGa nanoparticles synthesized via surface organometallic chemistry and provided a structure-activity relationship at the molecular level. Using this approach, the key interaction between Pt and Ga was evidenced and analyzed: the presence of Ga increases (i) the interaction between the oxide surface and the nanoparticles, which reduces sintering, (ii) the Pt site isolation, and (iii) the mobility of surface atoms which promotes the high activity, selectivity, and stability of this catalyst. Considering the complete system for modeling that includes the silica support as well as the dynamics of the PtGa nanoparticle is essential to understand the catalytic performances.

[Smoking in elderly patients with chronic diseases of the digestive system].

The purpose of this study was to examine the features of smoking in elderly patients with chronic diseases of the digestive system. Results are based on an analysis of 762 questionnaires of patients were receiving hospital treatment in the Central Research Institute of Gastroenterology. The article presents data on the frequency and intensity of smoking in patients with digestive diseases in the age and gender. To increase the effectiveness of tobacco dependence treatment in elderly patients suggested treatment strategy targeting the early stages to reduce the daily dose of nicotine, rather than a one-time and full cessation of smoking tobacco.

[Complex treatment of tobacco dependence by means of psychotherapeutic correction in combination with mesodiencephalic modulation in patients with chronic diseases of digestive organs].

This paper deals with the problem of tobacco dependence and its medical treatment. Various methods available for this purpose are considered with special reference to their clinical efficiency. A scheme for combined treatment of the given pathology is proposed.

[Pharmacokinetics of the proton pump inhibitors and psychological status in patients as factors that influence the efficiency of treatment of GERD with pantoprazole].

Was made an investigation of the effectiveness of pantoprazole (sanpraz, "SanFarma", India) at gastroesophageal reflux disease (GERD). 53 patients with GERD, including 20--with reflux esophagitis, received a daily dose of pantoprazole 40 mg to 28 days. To the 7 day of treatment heartburn was broke in 63.3%, regurgitation--in 65% of patients initially experiencing these symptoms. The 14-th day of treatment heartburn was broke in 83.7%, regurgitation--in 90%. Endoscopic remission in 28-th day of treatment was obtained in 85% of patients with reflux esophagitis. Broking of symptoms was accompanied by significant improvement in well-being and quality of life of patients. Treatment of a standard dose of pantoprazole was ineffective in 16.3% of patients. The reasons for the conservation of heartburn in 4.1% of the cases was an individual characteristics of the pharmacokinetics drug, in 12.2%--non-reflux mechanisms of symptoms in the face of mental status.

[Restoration of the quality of life by eliminating and prevention of heartburn by alginate: results of multicenter study "VIA APIA"].

Was conducted a muIticenter study VIA APIA, in which the impact of gaviscon forte (suspension) on symptoms, general state and quality of life of 148 patients (male 53, female 95, age 42.9 +/- 15.6) with gastroesophageal reflux disease (GERD) were investigated. The patients had undergone clinical evaluation of dynamics of GERD symptoms (Likert scale), general state (Visual Analogue Scale, questionnaire SAN) and quality of life (SF-36). It was shown that 14-days treatment with gaviscon forte provided symptoms relief in 84.5% patients and conducted improvement of general state and quality of life. Gaviscon forte recommended as drug of choice in initial treatment for the first time visited patient with heartburn before endoscopy and for pathogenetic treatment of typical reflux syndrome.

[Evaluation of action, efficacy, and onset dynamics of a single dose of alginates in patients with heartburn and GERD].

We conducted a crossover study, in which the efficacy and the onset of action of a single dose of Gaviscon (suspension) and Gaviscon forte (suspension) in 52 patients with heartburn of moderate intensity and gastroesophageal reflux disease (GERD) have been investigated. The average age of the patients was 44.0 +/- 17.3-years-old. The patients have undergone clinical evaluation of intensity of GERD symptoms and psychological assessment (questionnaires SF-36, SMOL, LOBI). Alginates' effects and qualities were evaluated using stopwatch technique, clinical examination, and organoleptic assessment. Primary sensation of a cooling (soothing) effect after use of a single dose of Gaviscon has been reported in 65.7 seconds (on average), and Gaviscon forte--in 66.1 seconds. Fourty three (82.7%) patients with heartburn have described the effects of both medications as "instant" cooling effects. Heartburn was relieved in 3.3 minutes in all patients after a single dose of Gaviscon, and in 3.6 minutes in 51 (98.1%) patients who have received a single dose of Gaviscon forte. Organoleptic qualities averaged at 3.6 points (on a scale of 1-5) for Gaviscon, and at 3.5 points for Gaviscon forte. Assessment of mental status of the patients suggested that a "delayed" effect of the medications in relieving heartburn in some patients may have occurred due to possible physical disadaptation.

Assessment of the patient's quality of life in the long-term postoperative period after reconstructions on lower extremity arteries.

The study accrued 28 male patients provided reconstruction for atherosclerotic lesion of lower extremity arteries. Their ages ranged from 36 to 69 years, with a mean of 57.73+/-8.75 years. Degree IIB ischemia according to the R. Fontaine classification modified by A. V. Pokrovsky was present in 10, degree III in 17 patients, and degree IV in one patient. The level end degree of lesion were assessed using contrast angiography and Doppler ultrasound. Before and after operation all the patients underwent measurements of the painless walking distance and regional systolic pressure on the shoulder and ankle as well as of the ankle/brachial pressure index. The quality of life was evaluated in all the patients with the aid of a MOS SF36 questionnaire before and 3 months after operation. The individual and typological personality properties were defined by the psychodiagnostic test (PDT). Operation was followed by a significant rise of the pressure index, painless walking index, and an improvement of the patient's quality of life according to the scales "physical function" and "physical pain". The correlation was established between the painless walking distance and indicators of the "physical function" scale (r=0.48, p<0.05) and "physical pain " (r=0.44, p>0.05) as well as between the ankle/brachial pressure index and general health status (r=0.58, p<0.02). The relationship was revealed between the change in the patient's quality of life after operation and individual-typological personality properties. The correlation coefficient between the scales of "neurotism" according to the PDT: and "physical function", "physical role" and "emotional role" according to the SF36 constituted -0.47, -0.54 and - -0.49 respectively (p<0.05) that between psychotism and the general health status was -0.49 (p<0.05), and that between mental instability and physical and emotional role -0.66 and -0,61 respectively (p<0.01).

[Quality of life of patients with atherosclerotic lesion of lower extremity arteries as dependent on individual and typological properties of the patient personality]. / Kachestvo zhizni bol'nykh s ateroskleroticheskim porazheniem arterii nizhnikh konechnostei v zavisimosti ot individual'no-tipologicheskikh svoistv lichnosti patsienta.

Twenty men with atherosclerotic lesion of lower extremity arteries verified by contrast angiography and ultrasound Doppler were examined. The patients' age varied from 36 to 69 years (mean 57 years). Six patients had IIB ischemia, 13 presented with degree III and one patient had degree IV ischemia according to the R. Fontaine classification modified by A. V. Pokrovsky. The MOS SF = 36 questionnaire was used to estimate the quality of life of all the patients. The individual typological properties of the personality were defined using the psychodiagnostic test (PDT). A significant decrease of the patients' quality of life was revealed according to the scales: physical function, physical role, physical pain, general health condition. A correlation was recorded between the patient's age and the parameters of the "physical function scale" (r=-0.63; p<0.005). The individual typological properties of the personality exert an effect on five of the eight SF = 36 scales. A feedback was discovered between neurotism and mental health (r=-0.455; P<0.05), conscientiousness and the physical role (r=-0,487; p<0.05); a direct relationship was found between disinhibition and physical pain (r=0.451; p<0.05), general activity and physical pain (r=0.535; p<0.05). An indistinctly pronounced feed back manifested itself between the "neurotism" and "physical pain" scales (r=-0.409), "psychotism" end the "physical role", (r=-0.437), "introversion" and "vitality" (r=-0.408), "femininity" and the "emotional role" (r=-0.404), and a direct relationship was established between the scales "esthetic impressionability" and "vitality" (r=0.406).