The Role of Surface Complexes in Ketene Formation from Fatty Acids via Pyrolysis over Silica: from Platform Molecules to Waste Biomass.

Fatty acids (FA) are the main constituents of lipids and oil crop waste, considered to be a promising 2G biomass that can be converted into ketenes via catalytic pyrolysis. Ketenes are appraised as promising synthons for the pharmaceutical, polymer, and chemical industries. Progress in the thermal conversion of short- and long-chain fatty acids into ketenes requires a deep understanding of their interaction mechanisms with the nanoscale oxide catalysts. In this work, the interactions of fatty acids with silica are investigated using a wide range of experimental and computational techniques (TPD MS, DFT, FTIR, in situ IR, equilibrium adsorption, and thermogravimetry). The adsorption isotherms of linear and branched fatty acids C1-C6 on the silica surface from aqueous solution have been obtained. The relative quantities of different types of surface complexes, as well as kinetic parameters of their decomposition, were calculated. The formation of surface complexes with a coordination bond between the carbonyl oxygens and silicon atoms in the surface-active center, which becomes pentacoordinate, was confirmed by DFT calculations, in good agreement with the IR feature at ∼1680 cm 1. Interestingly, ketenes release relate to these complexes' decomposition as confirmed by the thermal evolution of the absorption band (1680 cm-1) synchronously with the TPD peak of the ketene molecular ion. The established regularities of the ketenezation are also observed for the silica-induced pyrolysis of glyceryl trimyristate and real waste, rapeseed meals.

Pros and cons of remote medical education in Ukraine in terms of COVID-19 pandemics.

Introduction: COVID-19 is an ongoing pandemic, which forced countries across the globe to adapt all daily activities to the new reality in order to stop the disease from spreading. The educational process was not an exception, it caused a sudden shift towards the exceptional introduction of online teaching and Kyiv Medical University was one of the first universities in Ukraine to assess the quality of education under the restrictive measures. Objectives: The aim was to analyze the advantages and disadvantages of online education during the COVID-19 pandemic in the learning of neurology at the Department of Neurology, Psychiatry and Physical Rehabilitation, Kyiv Medical University. Methods: 169 students were interviewed using an online questionnaire consisting of 18 items focused on different angles of educational process. Results: According to the obtained results, the biggest pros of online teaching included: flexibility of learning schedule, learning at your own pace; ability to develop deeper problem-solving and clinical thinking skills. Social distancing, family distractions, and internet connection issues negatively affected most students' feelings during online learning. One of the most prominent cons of online learning of neurology pointed out by the majority of medical students was a lack of practical component of training and contact with patients. Conclusions: Online teaching, along with a number of advantages, has significant disadvantages, especially in medical education in case of studying clinical disciplines.

Association of a polymorphism in exon 3 of the IGF1R gene with growth, body size, slaughter and meat quality traits in Colored Polish Merino sheep.

This study aimed to genotype the polymorphism (c.654G > A) in the exon 3 of the insulin-like growth factor 1 receptor gene (IGF1R) and to analyze its association with growth, body size, slaughter and meat quality traits in Colored Polish Merino sheep. In total, 67 traits were analyzed. The IGF1R polymorphism was genotyped using the polymerase chain reaction single-strand conformation polymorphism (PCR-SSCP) method. The MIXED procedure of the SAS software was used to assess the genotypic effects of the polymorphism (c.654G > A) on production traits of interest. The IGF1R c.654G > A genotypes were found to have a significant effect on the average daily gain between the 56th and 78th day of life, cold carcass, leg part, leg cut, fore shank, and kidney weights, as well as eye of loin depth, intramuscular fat content, and water-holding capacity of meat. The results suggest that the studied polymorphism may provide useful information for marker-assisted selection for increased meat performance in Colored Polish Merino sheep.

Age dependence of plasma endothelin levels in glaucoma patients.

The aim of the study was to investigate the endothelin-1 (ET-1) plasma level and its age dependence in patients with normal tension glaucoma (NTG), high tension glaucoma (HTG), and healthy controls. In blood samples from 35 NTG patients, 34 HTG patients, and 36 controls, ET-1 plasma levels were determined by enzyme-linked immunosorbent assay (ELISA). After adjustment for age and gender, the mean ET-1 levels were found to be similar in all three study groups. The age dependency however was highest in NTGs and significantly different from that of the controls. For the HTGs, this dependence was weaker and not significantly different from that of the controls. Our findings suggest that age had a significantly greater influence on ET plasma level in the NTG patients than in the HTG patients and controls. This supports previous reports indicating that ET plays a role in the pathogenesis of glaucoma, and in particular normal NTG.

Genotypic and allelic effects of the myostatin gene (MSTN) on carcass, meat quality, and biometric traits in Colored Polish Merino sheep.

The aim of this study was to identify polymorphisms in the first intron and c.*1232G>A position of the MSTN gene and analyze associations between the detected alleles/genotypes and carcass, meat quality, and biometric traits in Colored Polish Merino sheep. We analyzed 44 traits using the MIXED procedure of the SAS software. Five alleles (MSTN-A, MSTN-B, MSTN-C, MSTN-E and MSTN-E1) were detected. Significant genotypic effects were detected with regard to chest depth (live lamb) and fat depth over ribs, drip loss, subjective meat flavor and color, whereas significant allelic effects were found for chest depth (live lamb), pre-slaughter weight, hot carcass weight, cold carcass dressing out, leg depth (carcass), eye of loin width and area, intramuscular fat (IMF) content, water-holding capacity, and subjective meat tenderness, flavor and color. The results suggest MSTN gene polymorphisms may be considered a genetic marker of carcass quality, meat quality, and biometric traits in sheep.

Thermal transformation of bioactive caffeic acid on fumed silica seen by UV-Vis spectroscopy, thermogravimetric analysis, temperature programmed desorption mass spectrometry and quantum chemical methods.

Thermochemical studies of hydroxycinnamic acid derivatives and their surface complexes are important for the pharmaceutical industry, medicine and for the development of technologies of heterogeneous biomass pyrolysis. In this study, structural and thermal transformations of caffeic acid complexes on silica surfaces were studied by UV-Vis spectroscopy, thermogravimetric analysis, temperature programmed desorption mass spectrometry (TPD MS) and quantum chemical methods. Two types of caffeic acid surface complexes are found to form through phenolic or carboxyl groups. The kinetic parameters of the chemical reactions of caffeic acid on silica surface are calculated. The mechanisms of thermal transformations of the caffeic chemisorbed surface complexes are proposed. Thermal decomposition of caffeic acid complex chemisorbed through grafted ester group proceeds via three parallel reactions, producing ketene, vinyl and acetylene derivatives of 1,2-dihydroxybenzene. Immobilization of phenolic acids on the silica surface improves greatly their thermal stability.

Investigation of chemical transformations of thiophenylglycoside of muramyl dipeptide on the fumed silica surface using TPD-MS, FTIR spectroscopy and ES IT MS.

In this study, chemical transformations of benzyl ester of О-(phenyl-2-acetamido-2,3-dideoxy-1-thio-ß-d-glucopyranoside-3-yl)-d-lactoyl-l-alanyl-d-isoglutamine (SPhMDPOBn) on the fumed silica surface were examined, and the surface complex structure was characterized by temperature-programmed desorption mass spectrometry (TPD-MS), infrared spectroscopy (FTIR) and electrospray ion trap mass spectrometry (ES IT MS). Stages of pyrolysis of SPhMDPOBn in pristine state and on the silica surface have been determined. Probably, hydrogen-bonded complex forms between silanol surface groups and the C = O group of the acetamide moiety NH-(CH3)-C = O…H-O-Si≡. The thermal transformations of such hydrogen-bonded complex result in pyrolysis of SPhMDPOBn immobilized on the silica surface under TPD-MS conditions. The shifts ∆ν of amide I band (measured from 1,626 to 1,639 cm(-l) for SPhMDPOBn in pristine state) of 33 and 35 cm(-l) which occurred when SPhMDPOBn was immobilized on the silica surface may be caused by a weakening of the intramolecular hydrogen bonding of the SPhMDPOBn because the interaction with the silica surface as hydrogen bond with silanol groups is weaker than that in associates.

[The influence of 5-week relaxation therapy on arterial blood pressure in patients with borderline hypertension]. / Wplyw 5-tygodniowej terapii relaksacyjnej na wysokosc cisnienia tetniczego u chorych na nadcisnienie tetnicze graniczne.

The present study was performed to evaluate the influence of 5-week relaxation therapy on office and ambulatory blood pressure in young borderline hypertensives. Thirty patients were studied. The office blood pressure decreased significantly after 5 weeks of relaxation therapy (P < 0.001 for both systolic and diastolic blood pressure). Ambulatory monitoring revealed only a slight decrease of 24-hour blood pressure (P = 0.02). Our results indicate limited efficacy of relaxation therapy in treatment of borderline hypertensives.

[The influence of 5-week relaxation therapy on psychological state of patients with borderline hypertension]. / Ocena wplywu 5-tygodniowej terapii relaksacyjnej na stan psychiczny chorych na nadcisnienie tetnicze graniczne.

The aim of the present was to evaluate the influence of 5-week relaxation therapy on psychic state of patients with borderline hypertension. The study group consisted of 30 hypertensives. We observed significant changes in anxiety scale, defensiveness, self-confidence, intraception, nurturance, affiliation, heterosexuality, change and succorance scales. In conclusion, 5-week relaxation changes significantly psychological status of patients with borderline hypertension.

[Choroidal osteoma]. / Kostniak blony naczyniowej.

Choroidal osteoma is a benign, ossifying tumor, first described by Gass and Williams in 1978, typically found in healthy young females. Usually it is localized in the posterior pole of the eye, near the optic disc and the macula. Its aetiology is unknown: it may be caused by osseous metaplasia of the retinal pigment epithelium, or it may represent a kind of choristoma. The diagnosis of the choroidal osteoma is based mainly on its very characteristic clinical picture, ultrasonography and computed tomography--both demonstrating calcific plaque corresponding to the lesion. The most important complications of the tumor are: subretinal neovascularisation, subretinal and intraretinal haemorrhages, serous and haemorrhagic retinal detachments. Neovascularisation can be successfully treated by laser photocoagulation, which can even lead to decalcification and involution of the tumor. Choroidal osteoma must be differentiated mainly from amelanotic choroidal melanoma, choroidal nevus, choroidal haemangioma, choroidal metastasis, granuloma, organized subretinal haemorrhage, sclerochoroidal calcification and age-related macular degeneration. In this paper we present a case of a choroidal osteoma recognized in an 11-year-old girl. There have been no signs of tumor's growth or signs of subretinal neovascularisation for three years of follow-up. As far as we know, it is the first case of this disease described in Polish literature.

[The influence of RS-Timolol in comparison with R-Timolol and S-Timolol on the intraocular pressure in water-loaded rabbits]. / Wplyw racematu RS-timololu w porównaniu z enancjomerami S-timololu i R-timololu na cisnienie sródgalkowe królików w modelu obciazenia wodnego.

PURPOSE: It is assumed that S-timolol can produce more severe systemic adverse reactions than R-timolol. The aim of this study was to estimate the intraocular pressure-lowering effect of RS-timolol in comparison to R-timolol and S-timolol in water-loaded rabbits. MATERIAL AND METHODS: Ocular hypertension was provoked in rabbits by orogastric water loading. Topical administration of one of three timolol solutions: 0.85%, RS-timolol, or 3% R-timolol, or 0.5% S-timolol was performed to the right eyes 40 min before starting the water loading procedure. Left eyes served as a control group. Intraocular pressure was measured before and 30, 60, 90, 120 min after the water loading. RESULTS: Intraocular pressure-lowering effect of all three timolol solutions was comparable. CONCLUSION: RS-timolol can be effective for lowering intraocular pressure in rabbits.

[Psychiatric and psychological aspects of anorexia nervosa]. / Anorexia nervosa w aspekcie psychiatrycznym i psychologicznym.

A group of 38 patients treated in the Department of Psychiatry, Medical Academy of Gdansk, from 1972 to 1988, because of anorexia nervosa (0.33% patients treated in the Department) was studied. There was 36 women and 2 men aged 14 to 39 years (average 21 years). Half of the patients finished only secondary school, the others started university education--most of them were still students. Except one, they presented good intellectual abilities; 6 women were married. In 42% cases a conflict situation at school or family was found (adaptational problems, competition at home); in 18% cases problems with acceptance of the role of woman. In 25% cases minimal brain damage symptoms were found in the EEG and psychologic tests. In the rest of the cases neurotic traits were present--the schizophrenic process was not found at all. Frequently the patients did show fearful attitude, difficulties with emotional relation towards other persons, egocentrism; a tendency to use regression, resignation, repression, over intellectualism and conversion as defence mechanisms. The pharmacological and psychotherapeutic treatment did results in clinical improvement (weight gain, mood and sleep normalization, reduced anxiety) in all cases studied.

[Intro- and extraversion in patients with neuroses as factors differentiating the effect of diazepam on psychomotor function]. / Intro-ekstrawersja u pacjentów chorych na nerwice jako czynnik róznicujacy wplyw diazepamu na funkcje psychomotoryczne.

The influence of various diazepam doses on selected psychomotor functions in neurotic patients was studied with regard to introversion and extraversion. The group consisted of 110 patients randomly selected into diazepam group (60 cases) and placebo group (50 subjects). In each group introvertics (24 treated with diazepam and 13 with placebo) as well as extravertics (15 subjects receiving diazepam and 12 placebo) were selected. Further analysis excluded 36 ambivertics. Results did not suggest substantial dependence between introversion and extraversion, and effect of diazepam on psychomotor functions. Only the negative effect of certain diazepam doses on visualmotor coordination in introvertic patients, as well as such influence on time of reaction with choice was found. It regards to diazepam doses of 10 mg t.i.d. after 7-10 days of treatment, and also the influence of single dose of 10 mg diazepam after 3-4 hours on visual-motor coordination as well.