Characterization of Siloxane-poly(methyl methacrylate) Hybrid Films Obtained on a Tinplate Substrate Modified by the Addition of Organic and Inorganic Acids

Tinplate is used to food packaging and other types of packages. The corrosion resistance of the tinplate has been study due the necessity of an alternative to high environmental impact of chromatization process. Therefore protective coatings as hybrid films base elaborations with different acids are studied to improve the barrier effect against corrosion. The objective of this work is characterize hybrid films deposited on a tinplate from a sol made up of the alkoxide precursors 3-(trimethoxysilylpropyl) methacrylate (TMSM), tetraethoxysilane (TEOS) and poly(methyl methacrylate) (PMMA) together with one of three acids (acetic, hydrochloric or nitric acid) and to verify their action against the corrosion of the substrate. The films were obtained by a dip-coating process and cured for 3 hours at 160 °C. The film hydrophobicity was determined by contact angle measurements, and the morphology was evaluated by SEM. FTIR measurements were performed to characterize the chemical structures of the films. The electrochemical behavior of the coatings was evaluated by techniques open circuit potential monitoring (OCP), potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results demonstrate that the siloxane-PMMA films improve the protective properties of the tinplate, with the films obtained by acetic acid addition exhibiting the greatest improvement

Industrial scale isolation, structural and spectroscopic characterization of epiisopiloturine from Pilocarpus microphyllus stapf leaves: a promising alkaloid against schistosomiasis

This paper presents an industrial scale process for extraction, purification, and isolation of epiisopiloturine (EPI) (2(3H)- Furanone,dihydro-3-(hydroxyphenylmethyl)-4-[(1-methyl-1H-imidazol-4-yl)methyl]-, [3S-[3a(R*),4b]]), which is an alkaloid from jaborandi leaves (Pilocarpus microphyllus Stapf). Additionally for the first time a set of structural and spectroscopic techniques were used to characterize this alkaloid. EPI has shown schistomicidal activity against adults and young forms, as well as the reduction of the egg laying adult worms and low toxicity to mammalian cells (in vitro). At first, the extraction of EPI was done with toluene and methylene chloride to obtain a solution that was alkalinized with ammonium carbonate. The remaining solution was treated in sequence by acidification, filtration and alkalinization. These industrial procedures are necessary in order to remove impurities and subsequent application of the high performance liquid chromatography (HPLC). The HPLC was employed also to remove other alkaloids, to obtain EPI purity higher than 98%. The viability of the method was confirmed through HPLC and electrospray mass spectrometry, that yielded a pseudo molecular ion of m/z equal to 287.1 Da. EPI structure was characterized by single crystal X-ray diffraction (XRD), 1H and 13C nuclear magnetic resonance (NMR) in deuterated methanol/chloroform solution, vibrational spectroscopy and mass coupled thermal analyses. EPI molecule presents a parallel alignment of the benzene and the methyl imidazol ring separated by an interplanar spacing of 3.758 Å indicating a π-π bond interaction. The imidazole alkaloid melts at 225°C and decomposes above 230°C under air. EPI structure was used in theoretical Density Functional Theory calculations, considering the single crystal XRD data in order to simulate the NMR, infrared and Raman spectra of the molecule, and performs the signals attribution

Decline in subarachnoid haemorrhage volumes associated with the first wave of the COVID-19 pandemic

BACKGROUND: During the COVID-19 pandemic, decreased volumes of stroke admissions and mechanical thrombectomy were reported. The study\u27s objective was to examine whether subarachnoid haemorrhage (SAH) hospitalisations and ruptured aneurysm coiling interventions demonstrated similar declines. METHODS: We conducted a cross-sectional, retrospective, observational study across 6 continents, 37 countries and 140 comprehensive stroke centres. Patients with the diagnosis of SAH, aneurysmal SAH, ruptured aneurysm coiling interventions and COVID-19 were identified by prospective aneurysm databases or by International Classification of Diseases, 10th Revision, codes. The 3-month cumulative volume, monthly volumes for SAH hospitalisations and ruptured aneurysm coiling procedures were compared for the period before (1 year and immediately before) and during the pandemic, defined as 1 March-31 May 2020. The prior 1-year control period (1 March-31 May 2019) was obtained to account for seasonal variation. FINDINGS: There was a significant decline in SAH hospitalisations, with 2044 admissions in the 3 months immediately before and 1585 admissions during the pandemic, representing a relative decline of 22.5% (95% CI -24.3% to -20.7%, p\u3c0.0001). Embolisation of ruptured aneurysms declined with 1170-1035 procedures, respectively, representing an 11.5% (95%CI -13.5% to -9.8%, p=0.002) relative drop. Subgroup analysis was noted for aneurysmal SAH hospitalisation decline from 834 to 626 hospitalisations, a 24.9% relative decline (95% CI -28.0% to -22.1%, p\u3c0.0001). A relative increase in ruptured aneurysm coiling was noted in low coiling volume hospitals of 41.1% (95% CI 32.3% to 50.6%, p=0.008) despite a decrease in SAH admissions in this tertile. INTERPRETATION: There was a relative decrease in the volume of SAH hospitalisations, aneurysmal SAH hospitalisations and ruptured aneurysm embolisations during the COVID-19 pandemic. These findings in SAH are consistent with a decrease in other emergencies, such as stroke and myocardial infarction

Analytical HPLC used LiChrospher 60 RP column and eluted with potassium phosphate

<p>. (A) Standard EPI (20 µg/mL), (B) Standard pilocarpine (50 µg/mL), (C) “cultivated jaborandi leaves” solution, resulted from first extraction step, (D) “cultivated jaborandi acid” solution, obtained EPI under salt form, (E) Solution of “crude EPI” with some impurities as pilocarpine and other alkaloids, (F) last step of isolation showing EPI >98% purity.</p

Scheme of all necessary steps in obtaining Epiisopiloturine with >98% purity from Jaborandi leaves.

<p>Scheme of all necessary steps in obtaining Epiisopiloturine with >98% purity from Jaborandi leaves.</p

Mass spectrum obtained from ESI+/Ion Trap.

<p>(A) free EPI with a pseudo molecular ion m/z 287.1 Da [M+H]⁺, (B) MS² with characteristic fragment at m/z 269.1 Da [M – H₂O + H]⁺, (C) MS³ with fragments at m/z 251.0 Da [M – 2H₂O + H⁺] and 168.06 Da with proposed chemical structure.</p

Isolated Epiisopiloturine molecular structure.

<p>Isolated Epiisopiloturine molecular structure.</p

EPI bond angles obtained through x-ray diffraction (Experimental) and DFT results (Calculated).

<p>Atom labels accordingly to <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0066702#pone-0066702-g004" target="_blank">Figure 4</a>.</p

Infrared (IR) and Raman wavenumbers (cm⁻¹) of solid state EPI.

<p>Calculated vibrational wavenumbers (cm-1) for the isolated EPI molecule. A tentative assignment of the observed vibrational modes is also shown. See text for theoretical details. ν =  stretching, δ =  bending, β =  bending in plane, γ =  bending out of plane, r =  rocking, τ =  twist, sc =  scissoring, ω =  wagging, νs =  symmetric stretching, νa =  antisymmetric stretching, sh  =  shoulder.</p