Controlling factors determining the selective HSCN addition to double bonds and their application to the synthesis of 7-isothiocyano-7,8-alpha-dihydro-bisabolene

The reactivity of terminal and trisubstituted double bonds of monoterpenes with HSCN has been examined by GC giving evidence that kinetics is responsible for the chemoselective addition to terminal double bonds in terpenes. The results show that the addition to the terminal double bond is about 17 times faster than for trisubstituted double bonds and that the presence of the first SCN group in the molecule prevents a second addition. The presence of a hydroxyl or methoxy group in the molecule, decreases the reaction kinetics. Based on these kinetic experiments a two steps synthesis of the natural product 7-isothiocyano-7,8-dihydro-alpha-bisabolene using bisabolol as starting material, was planned and successfully accomplished.A reatividade de duplas ligações terminal e trissubstituída de monoterpenos com HSCN foi examinada por CG evidenciando que fatores cinéticos são responsáveis pela adição quimiosseletiva em duplas ligações terminais em terpenos. O resultado mostra que a adição é cerca de 17 vezes mais rápida em duplas terminais do que em duplas trissubstituídas e que a presença do primeiro grupo SCN impede a entrada de um segundo grupo. A presença de um grupo hidroxila ou metoxila na molécula diminui sensivelmente a velocidade da reação. A partir do estudo acima foi possível elaborar e realizar a síntese do produto natural 7-isothiocyano-7,8-dihydro-alfa-bisabolene em duas etapas a partir do bisabolol.661666Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES

Rapid synthesis of MCM-41 and SBA-15 by microwave irradiation: promising adsorbents for CO2 adsorption

It is known that the world scenario is one of constant search for sustainable technologies that can reduce the emission of carbon dioxide (CO2) in the atmosphere. This is because CO2 is seen as the main responsible for the increase in the generation of greenhouse gases, which leads to global warming and climate change. The development of efficient adsorbents for CO2 capture is a current challenge. MCM-41 and SBA-15 were synthesized in a microwave reactor and used as adsorbents in this work. Microwave irradiation presents itself as an easy synthesis strategy with less preparation time and energy requirement. The silica synthesis period was extremely reduced (1 h) at a temperature of 60 and 80 °C in the microwave reactor, obtaining silica with good textural and chemical properties. The CO2 adsorption isotherms were performed at 0, 25, and 40 °C at 1 bar. The MCM-41 and SBA-15 present favorable results for CO2 capture processes, showing that pure silica synthesized by microwave already obtains promising results, reaching a maximum adsorption capacity of 2.16 mmol g−1 (1 bar—0 °C) and a good fit for the Langmuir, DsL and Toth models. Furthermore, to increase CO2 adsorption, the mesoporous silica was also modified via impregnation with branched polyethylene diamine (PEI) or tetraethylenepentamine (TEPA). It is worth mentioning that microwave irradiation reduced the synthesis steps and improved the properties and adsorption capacity of the silica. This work opens new opportunities in the efficient preparation of materials that require optimizing the adsorbent synthesis process.The authors thank you to Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq, National Council for Scientific and Technological Development, Brazil) and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (Higher Education Personnel Improvement Coordination, Brazil, CAPES—financing code 001) for financial support. This research was also funded by the Ministry of Science, Innovation and Universities (Spain), Grants Nos. RTI2018-099668-B-C22 and PID2021-126235OB-C32, and projects UMA18-FEDERJA-126 and P20_00375 of Junta de Andalucía and FEDER funds. // Funding for open access publishing: Universidad Málaga/CBUA

TOXICITY OF TAGETES MINUTA ESSENTIAL OIL IN SILVER CATFISH (RHAMDIA QUELEN)

Objective: Evaluation of Tagetes minuta L. essential oil (EOTM) toxicity in the silver catfish Rhamdia quelen.Methods: The EOTM extracted by hydrodistillation was identified qualitatively based on retention indices and the mass spectrum of its components by gas chromatography-mass spectrometry (GC-MS) and quantified by GC with flame ionization detector. Fish were exposed to 0, 50, 100, 200 mg l-1 EOTM and ethanol (1.5 ml) (n = 10 each concentration) and mortality observed after 24, 48 and 96 h (h).Results: The EOTM presented as the main constituents: di-hidrotagetone (7.66 %), Z-tagetone (29.50%) and E-tagetone (40.37%). Silver catfish mortality was 10% after 96 h at 50 mg l-1, 70 and 80% after 24 and 96 h, respectively, at 100 mg l-1 and 80, 90 and 100% after 24, 48 and 96 h, respectively, at 200 mg l-1.Conclusion: The use of EOTM is not recommended in fish farming at the concentrations measured in this study due to its toxic action.Keywords: Medicinal plants, Fish farming, Toxic effect, Cloves marigoldÂ

Impact of Resistance to Fluconazole on Virulence and Morphological Aspects of Cryptococcus neoformans and Cryptococcus gattii Isolates

Cryptococcus spp. are responsible for around one million cases of meningitis every year. Fluconazole (FLU) is commonly used in the treatment of cryptococcosis, mainly in immunocompromised patients and the resistance is usually reported after long periods of treatment. In this study, the morphological characterization and virulence profile of FLU-susceptible and FLU-resistant clinical and environmental isolates of C. neoformans and C. gattii were performed both in vitro and in vivo using the Galleria mellonella model. FLU-susceptible isolates from C. neoformans were significantly more virulent than the FLU-resistant isolates. FLU-susceptible C. gattii isolates showed a different virulence profile from C. neoformans isolates where only the environmental isolate, CL, was more virulent compared with the resistant isolates. Cell morphology and capsule size were analyzed and the FLU-resistant isolates did not change significantly compared with the most sensitive isolates. Growth at 37°C was also evaluated and in both species, the resistant isolates showed a reduced growth at this temperature, indicating that FLU resistance can affect their growth. Based on the results obtained is possible suggest that FLU resistance can influence the morphology of the isolates and consequently changed the virulence profiles. The most evident results were observed for C. neoformans showing that the adaptation of isolates to antifungal selective pressure influenced the loss of virulence

High mobility group box 1 levels in large vessel vasculitis are not associated with disease activity but are influenced by age and statins

Introduction: Takayasu arteritis (TA) and giant cell arteritis (GCA) are large vessel vasculitides (LVV) that usually present as granulomatous inflammation in arterial walls. High mobility group box 1 (HMGB1) is a nuclear protein that acts as an alarmin when released by dying or activated cells. This study aims to evaluate whether serum HMGB1 can be used as a biomarker in LVV. Methods: Twenty-nine consecutive TA patients with 29 healthy controls (HC) were evaluated in a cross-sectional study. Eighteen consecutive GCA patients with 16 HC were evaluated at the onset of disease and some of them during follow-up. Serum HMGB1 levels were measured by enzyme-linked immunosorbent assay. Results: In GCA patients at disease onset mean serum HMGB1 levels did not differ from HC (5.74 +/- 4.19 ng/ml vs. 4.17 +/- 3.14 ng/ml; p = 0.230). No differences in HMGB1 levels were found between GCA patients with and without polymyalgia rheumatica (p = 0.167), ischemic manifestations (p = 0.873), systemic manifestations (p = 0.474) or relapsing disease (p = 0.608). During follow-up, no significant fluctuations on serum HMGB1 levels were observed from baseline to 3 months (n = 13) (p = 0.075), 12 months (n = 6) (p = 0.093) and at the first relapse (n = 4) (p = 0.202). Serum HMGB1 levels did not differ between TA patients and HC [1.19 (0.45-2.10) ng/ml vs. 1.46 (0.89-3.34) ng/ml; p = 0.181] and no difference was found between TA patients with active disease and in remission [1.31 (0.63-2.16) ng/ml vs. 0.75 (0.39-2.05) ng/ml; p = 0.281]. HMGB1 levels were significantly lower in 16 TA patients on statins compared with 13 patients without statins [0.59 (0.29-1.46) ng/ml vs. 1.93 (0.88-3.34) ng/ml; p = 0.019]. Age was independently associated with higher HMGB1 levels regardless of LVV or control status. Conclusions: Patients with TA and GCA present similar serum HMGB1 levels compared with HC. Serum HMGB1 is not useful to discriminate between active disease and remission. In TA, use of statins was associated with lower HMGB1 levels. HMGB1 is not a biomarker for LVV

Алгоритмическое и программное обеспечение выделения значимых предикторов из медицинской документации осмотра пациента

В рамках данной работы произведен отбор значимых текстовых признаков и построение модели машинного обучения для классификации фрагментов медицинской документации. Исследование проводилось на основе данных документов "Осмотр в стационаре при поступлении" из историй болезни пациентов, страдающих рожистыми воспалениями. Произведен выбор наилучшей модели классификатора, подбор оптимальных гиперпараметров, а также оценка качества классификации.In the present study selection of significant text features and the machine learning model for the classification of medical records were made. The study was conducted on the basis of "Inspection in the hospital at admission" documents from the records of patients suffering from erysipelas. The selection of the best classifier model, selection of optimal hyperparameters, as well as assessment of the quality of classification were made

Catalytic Thr or ser Residue Modulates Structural Switches in 2-Cys Peroxiredoxin by Distinct Mechanisms

Typical 2-Cys Peroxiredoxins (2-Cys Prxs) reduce hydroperoxides with extraordinary rates due to an active site composed of a catalytic triad, containing a peroxidatic cysteine (C P ), an Arg, and a Thr (or Ser). 2-Cys Prx are involved in processes such as cancer; neurodegeneration and host-pathogen interactions. During catalysis, 2-Cys Prxs switch between decamers and dimers. Analysis of 2-Cys Prx structures in the fully folded (but not locally unfolded) form revealed a highly conserved, non-conventional hydrogen bond (CH-π) between the catalytic triad Thr of a dimer with an aromatic residue of an adjacent dimer. In contrast, structures of 2-Cys Prxs with a Ser in place of the Thr do not display this CH-π bond. Chromatographic and structural data indicate that the Thr (but not Ser) destabilizes the decamer structure in the oxidized state probably through steric hindrance. As a general trend, mutations in a yeast 2-Cys Prx (Tsa1) favoring the dimeric state also displayed a decreased catalytic activity. Remarkably, yeast naturally contains Thr-Ser variants (Tsa1 and Tsa2, respectively) with distinct oligomeric stabilities in their disulfide states