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1.
SAGE Open Med ; 12: 20503121241257777, 2024.
Article in English | MEDLINE | ID: mdl-38895543

ABSTRACT

Objectives: ChatGPT is an advanced chatbot based on Large Language Model that has the ability to answer questions. Undoubtedly, ChatGPT is capable of transforming communication, education, and customer support; however, can it play the role of a doctor? In Poland, prior to obtaining a medical diploma, candidates must successfully pass the Medical Final Examination. Methods: The purpose of this research was to determine how well ChatGPT performed on the Polish Medical Final Examination, which passing is required to become a doctor in Poland (an exam is considered passed if at least 56% of the tasks are answered correctly). A total of 2138 categorized Medical Final Examination questions (from 11 examination sessions held between 2013-2015 and 2021-2023) were presented to ChatGPT-3.5 from 19 to 26 May 2023. For further analysis, the questions were divided into quintiles based on difficulty and duration, as well as question types (simple A-type or complex K-type). The answers provided by ChatGPT were compared to the official answer key, reviewed for any changes resulting from the advancement of medical knowledge. Results: ChatGPT correctly answered 53.4%-64.9% of questions. In 8 out of 11 exam sessions, ChatGPT achieved the scores required to successfully pass the examination (60%). The correlation between the efficacy of artificial intelligence and the level of complexity, difficulty, and length of a question was found to be negative. AI outperformed humans in one category: psychiatry (77.18% vs. 70.25%, p = 0.081). Conclusions: The performance of artificial intelligence is deemed satisfactory; however, it is observed to be markedly inferior to that of human graduates in the majority of instances. Despite its potential utility in many medical areas, ChatGPT is constrained by its inherent limitations that prevent it from entirely supplanting human expertise and knowledge.

2.
Spectrochim Acta A Mol Biomol Spectrosc ; 308: 123721, 2024 Mar 05.
Article in English | MEDLINE | ID: mdl-38086231

ABSTRACT

The spectroscopic properties of a series of para-hydroxyazobenzocrowns, including three novel compounds, were investigated using UV-Vis absorption and emission spectroscopy. This study presents, for the first time, determined quantum yield (QY) values for macrocycles of this category, ranging between 0.122 and 0.195. The highest values were obtained for crowns bearing two phenyl substituents in benzene rings. The impact of aromatic ring substituents and macroring size on the spectral characterization (1H NMR and FTIR) of p-hydroxyazobenzocrowns was examined in consideration of the azophenol â‡„ quinone-hydrazone tautomeric equilibrium. Dipole moments of p-hydroxyazobenzocrowns in the ground and excited states have been determined. The alignment between experimental findings and theoretical studies was established.

4.
Chempluschem ; 88(6): e202300175, 2023 Jun.
Article in English | MEDLINE | ID: mdl-37203359

ABSTRACT

New products of photo- and thermal rearrangements of 19-membered azoxybenzocrown with phenyl substituents in benzene rings in the para positions to oligooxyethylene fragments are characterized in this work. The yields of photochemical transformations depend on the solvent. Para-hydroxyazocrown is formed with yields over 50 % in propan-2-ol. Ortho-hydroxyazobenzocrown is obtained with yields up to 70 % in toluene/acetic acid mixture. Macrocyclic Ph-20-ester is obtained in yield 90 % under thermochemical rearrangement conditions. Structure of new hydroxyazobenzocrowns and also atypical product of rearrangements, 20-membered ester, was confirmed by X-ray diffraction analysis. Azophenol ← → ${ \mathbin{{\stackrel{\textstyle\rightarrow} { {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }$ quinone-hydrazone tautomeric equilibrium of new hydroxyazobenzocrowns and the influence of metal cations on tautomeric equilibrium was investigated using 1 H NMR and UV-Vis spectroscopy in acetonitrile. The highest value of stability constant (logK 7.25) was obtained for strontium complex of p-hydroxyazobenzocrown. For the first time p-hydroxyazobenzocrown was used as a chromoionophore in the receptor layer of an optical sensor. Comparative analysis with data obtained previously for series 19-membered analogs have shown the influence of the presence of substituents in benzene rings for the course and products distribution of photo and thermal rearrangement. The effect of substituents was also discussed against the tautomeric equilibrium and metal cation complexation properties.

5.
J Ovarian Res ; 15(1): 87, 2022 Jul 26.
Article in English | MEDLINE | ID: mdl-35883110

ABSTRACT

BACKGROUND: Clinical outcomes of cancer cell senescence are still elusive. Here, we reveal and compare pro-cancerous activity of spontaneously and drug-inducible senescent ovarian cancer cells. Experiments were performed on tumors and tumor-derived primary epithelial ovarian cancer cells (pEOCs) that were obtained from chemotherapy-naïve patients and from patients who received carboplatin (CPT) and paclitaxel (PCT) before cytoreduction. RESULTS: The analysis of tumors showed that senescent cancer cells are present in patients from both groups, albeit most frequently and covering a greater area in tissues from chemotherapy-positive women. This in vivo senescence of pEOCs translated to an expression of senescence markers in early-passage cells in vitro. A conditioned medium from senescent pEOCs fueled the cancer progression, including adhesion of non-senescent pEOCs to normal peritoneal cells, and their increased proliferation, migration, invasion, and EMT. Senescent pEOCs' secretome promoted angiogenic activity of vascular endothelium, induced senescence of normal peritoneal cells, reprogrammed their secretome towards hypersecretion of cancer-promoting proteins, and stimulated motility of cancer cells subjected to a mesothelium- and fibroblast-derived medium. The most striking finding was, however, that spontaneously senescent pEOCs supported all the above pro-cancerous effects more efficiently than drug-inducible senescent cells, which was plausibly related to augmented release of several cancer spread mediators by these cells. The prevalence of spontaneously senescent pEOCs was most evident in experiments on mice when they were able, unlike the drug-inducible cells, to promote the development of drug-sensitive i.p. xenografts. CONCLUSIONS: Our study shows that spontaneous senescence of pEOCs should be treated as an independent pathogenetic factor of cancer progression.


Subject(s)
Ovarian Neoplasms , Animals , Carcinoma, Ovarian Epithelial/pathology , Cellular Senescence , Epithelium/metabolism , Female , Humans , Mice , Ovarian Neoplasms/pathology , Peritoneum/pathology
6.
Molecules ; 27(6)2022 Mar 11.
Article in English | MEDLINE | ID: mdl-35335196

ABSTRACT

The preparation and characterization of products of the photochemical and thermochemical rearrangements of 19-membered azoxybenzocrowns with two, bulky, tert-butyl substituents in benzene rings in the para positions to oligooxyethylene fragments (meta positions to azoxy group, i.e., t-Bu-19-Azo-O have been presented. In photochemical rearrangement, two colored typical products were expected, i.e., 19-membered o-hydroxy-m,m'-di-tert-butyl-azobenzocrown (t-Bu-19-o-OH) and 19-membered p-hydroxy-m,m'-di-tert-butyl-azobenzocrown (t-Bu-19-p-OH). In experiments, two colored atypical macrocyclic derivatives, one 6-membered and one 5-membered ring, bearing an aldehyde group (t-Bu-19-al) or intramolecular ester group (t-Bu-20-ester), were obtained. Photochemical rearrangement led to one more macrocyclic product being isolated and identified: a 17-membered colorless compound, without an azo moiety, t-Bu-17-p-OH. The yield of the individual compounds was significantly influenced by the reaction conditions. Thermochemical rearrangement led to t-Bu-20-ester as the main product. The structures of the four crystalline products of the rearrangement-t-Bu-19-o-OH, t-Bu-19-p-OH, t-Bu-20-ester and t-Bu-17-p-OH-were determined by the X-ray method. Structures in solution of atypical derivatives (t-Bu-19-al and t-Bu-20-ester) and t-Bu-19-p-OH were defined using NMR spectroscopy. For the newly obtained hydroxyazobenzocrowns, the azo-phenol⇄quinone-hydrazone tautomeric equilibrium was investigated using spectroscopic methods. Complexation studies of alkali and alkaline earth metal cations were studied using UV-Vis absorption spectroscopy. 1H NMR spectroscopy was additionally used to study the cation recognition of metal cations. Cation binding studies in acetonitrile have shown high selectivity towards calcium over magnesium for t-Bu-19-o-OH.


Subject(s)
Esters , Metals, Alkaline Earth , Crystallography, X-Ray , Magnetic Resonance Spectroscopy , Quinones
7.
Chempluschem ; 85(9): 2067-2083, 2020 09.
Article in English | MEDLINE | ID: mdl-32909681

ABSTRACT

The preparation and characterization of products of the chemical and photochemical rearrangements of a 19-membered o,o'-azoxybenzocrown are presented. In photochemical rearrangement, besides the expected product i. e. 19-membered o-hydroxy-o,o'-azobenzocrown (19-o-OH) obtained under defined conditions with 75 % yield, also other macrocyclic products were isolated and identified, namely: 19-membered p-hydroxy-o,o'-azobenzocrown (19-p-OH), 21-membered o'-hydroxy-o,p'-azobenzocrown (21-o'-OH) and 19-membered macrocycle containing a 5-membered ring bearing an aldehyde group (19-al). The structures of two atypical products of the photochemical rearrangement - 21-o'-OH and 19-al - were determined in the solid state by X-ray analysis and in solution using NMR spectroscopy. Tautomeric equilibrium of the formed hydroxyazobenzocrowns and its change depending on acidity/basicity of the environment and alkali and alkaline earth metal cations complexation were studied using UV-Vis spectrophotometry, spectrofluorimetry and 1 H NMR spectroscopy.

8.
PLoS One ; 15(4): e0231516, 2020.
Article in English | MEDLINE | ID: mdl-32298315

ABSTRACT

The aim of this study was to evaluate the effects of medicinal herbal mixtures rich in phenolic, flavonoid and alkaloid compounds on ruminal fermentation and microbial populations, and fatty acid (FA) concentrations and lipid oxidation in tissues of lambs infected with the gastrointestinal nematode (GIN) parasite (Haemonchus contortus). Parallel in vitro and in vivo studies were performed using two different herbal mixtures (Mix1 and Mix2). The in vitro study was conducted in a 2 (infection status; non-infected versus infected) × 3 (diets; control, Mix1 and Mix2) factorial design. In the in vivo study, 24 lambs were equally divided into four treatments: non-infected lambs fed a control diet, infected lambs fed the control diet, infected lambs fed a diet with Mix1 and infected lambs fed a diet with Mix2. Herbal mixtures (100 g dry matter (DM)/d) were added to the basal diets of meadow hay (ad libitum) and a commercial concentrate (500 g DM/d). The experimental period lasted for 70 days. Ruminal fermentation characteristics and methane production were not affected by infection in vivo or in vitro. Both herbal mixture supplementation increased total volatile fatty acid (VFA) concentrations (P < 0.01) and DM digestibility (P < 0.01) in vitro. Archaea population was slightly diminished by both herbal mixtures (P < 0.05), but they did not lower methane production in vitro or in vivo (P > 0.05). Infection of H. contortus or herbal mixtures modulated FA proportion mainly in the liver, especially the long chain FA proportion. Concentrations of thiobarbituric acid reactive substances (TBARS) in serum were significantly higher after 70 days post-infection in the infected lambs. Herbal Mix1 supplementation reduced TBARS concentrations in meat after seven days of storage. In conclusion, supplementing of herbal mixtures to the diets of GIN parasite infected lambs did not affect the basic ruminal fermentation parameters. Herbal mixtures may improve few FA proportions mainly in liver as well as decrease lipid oxidation in meat.


Subject(s)
Dietary Supplements , Fermentation/drug effects , Gastrointestinal Microbiome/drug effects , Haemonchiasis/veterinary , Haemonchus , Lipid Metabolism/drug effects , Plants, Medicinal/metabolism , Rumen/metabolism , Sheep Diseases/parasitology , Animals , Diet/veterinary , Fatty Acids/metabolism , Female , Haemonchiasis/metabolism , Rumen/microbiology , Rumen/parasitology , Sheep/metabolism , Sheep/microbiology , Sheep/parasitology , Sheep Diseases/metabolism
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