Synthesis of lupeol derivatives and their antileishmanial and antitrypanosomal activities

The natural product lupeol 1 was isolated from aerial parts of Vernonia scorpioides with satisfactory yield, which made it viable to be used as starting material in semisynthetic approach. Ten lupeol derivatives 2–11 were prepared by classical procedures. Including, five new esters derivatives 7–11, which were obtained by structural modifications in the isopropylidene fragment. All semisynthetic compounds and lupeol 1–11 were confirmed by ¹H NMR, ¹³C NMR and HRMS. Their antiprotozoal activity was evaluated in vitro against L. amazonensis and T. cruzi. Derivative 6 showed the best antitrypanosomal activity (IC₅₀ = 12.48 μg/mL) and the lowest cytotoxic derivative (CC₅₀ = 161.50 μg/mL). The mechanism of action of the most active derivatives (4, 6 and 11) is not dependent from the enzyme trypanothione reductase.     

Synthesis of new isoxazoles derivatives attached to sugar moieties

This work reports the synthesis of isoxazoles linked to sugar derivatives in different positions of furanosidic rings, by intramolecular oxidative cyclization of α,β‐unsaturated oximes with iodine, potassium iodide and sodium hydrogen carbonate. These oximes were obtained from aldehyde‐sugar derivatives.     

Metal speciation dynamics in colloidal ligand dispersions

In this work we propose a dynamic metal speciation theory for colloidal systems in which the complexing ligands are localized on the surface of the particles; i.e., there is spatial heterogeneity of binding sites within the sample volume. The differences between the complex formation and dissociation rate constants of complexes in colloidal dispersions and those in homogeneous solutions originate from the differences in kinetic and mass transport conditions. In colloidal systems, when the effective rate of dissociation of the surface complexes becomes fully diffusion controlled, its value is defined via the geometrical parameters of the particle. We assess the extent to which the conventional approach of assuming a homogeneously smeared-out ligand distribution overestimates the lability of surface complexes in colloidal ligand dispersions. The validity of the theory is illustrated by application to binding of lead and cadmium by carboxyl modified latex particles: our approach correctly predicts the formation/dissociation rate constants, which differ by several orders of magnitude from their homogeneous solution counterparts.     

Determination Of Formaldehyde And Acetaldehyde Associated To Atmospheric Aerosols By HPLC

Abstract

A rapid new analytical protocol was developed for the determination of formaldehyde and acetaldehyde associated to atmospheric particulate matter, at ng/m³ levels. The aerosols were collected on glass fiber filters (8″×10″) at face velocities ranging from 15 m/min to 23 m/min. Aliquots of 15.4 cm² were sonicated, for 20 min, with 5.0 mL of 0,01% 2,4-dinitrophenylhydrazine (DNPH), 1 % phosphoric acid. The liquid phase was then filtered and the separation and quantification of the corresponding 2,4-dinitrophenylhidrazone (DNPHo) derivatives carried out by reverse phase HPLC. Acetonitrile:water (57:43, v/v) as mobile phase at 1.0 mL/min and absorbance detection at 350 nm and 365 nm for, respectively, formaldehyde-DNPHo (0.04 AUFS) and acetaldehyde-DNPHo (0.01 AUFS) were used. The precision for four different aliquots, from a 8″×10″ glass fiber filter, were under 0.04% for formaldehyde and 14.16 % for acetaldehyde. In Salvador, Bahia, Brazil, formaldehyde and acetaldehyde were determined, respectively, in the range of 6.8 ng/m³ to 27.3 ng/m³ and 9.1 ng/m³ to 54.6 ng/m³.     

Mass‐Spectrometric Observation of Counter Anion Production in SU‐8 Exposed to UV Light and its Use for Dill C Parameter Determination

Photopolymerization is a phenomenon that is the basis of much of today's microfabrication technology and intense research is conducted to improve its control and the characteristics of end products for a variety of applications. The design of microscopic structures often relies on the accurate knowledge and modeling of photopolymer's behavior upon exposure, i.e. the Dill parameters, for each radiation species of interest and therefore the development of flexible characterization techniques is of great importance. SU‐8 is a popular compound that is representative of a whole class that relies on cationic polymerization, where an acid is obtained via photolysis of an onium salt during exposure. Here we report on the observation of SbF₆^? via laser desorption mass spectrometry on SU‐8 exposed to UV light at the wavelength of 365 nm and demonstrate that the yield of this counter‐anion as a function of exposure is consistent with the Dill C parameter value available in the literature. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 967–972     

Development and validation of a RP-HPLC method for Roflumilast and its degradation products

Roflumilast is a phosphodiesterase type 4 inhibitor that is administered orally as a long-term, in the clinical treatment of chronic obstructive pulmonary disease and asthma. Launched in 2010 for the European market, it currently does not have an official monograph. Here, a reproducible gradient RP-HPLC method was developed and validated for the separation and determination of Roflumilast in the presence of its six major degradation products. Separation was performed on a C₁₈ analytical column (250?×?4.6?mm, 5?µm) with a mobile phase-A of ACN and a phase-B of ammonium acetate buffer (5?mM, pH 4.2) containing triethylamine (0.5% v/v). The most effective RP-HPLC gradient program was determined to be 0/80, 35/10, 36/80, 40/80 (time in minutes/% mobile phase-B). The flow rate was 1.0?ml/min and the column temperature was 25°C. The success of separation of the degradation products with different chemical characteristics was obtained by extending the time of the gradient, changing the proportion of the mobile phases and increasing the velocity of the flow. Two detectors were evaluated for the identification of degradation products and Roflumilast: a diode-arrary detector and a charged aerosol detector. The inability of the charged aerosol detector to dectect one of the six degradation products indicated that the method developed with RP-HPLC and the diode-array detector was more suitable for Roflumilast analysis. The method was validated according to specificity, linearity, LOD, LOQ, accuracy, precision and robustness.     

Synthesis,Crystal Structures,and in Silico Toxicity Prediction of Thienopyridine Phosphoramidates

New thieno[2,3-b]pyridine phosphoramidates compounds were synthesized and characterized by infrared; ¹H, ¹³C, and ³¹P NMR spectroscopy; and high-resolution mass spectrometry. The products were obtained in good yields (64–82%) under mild conditions by nucleophilic aromatic substitution reaction of aminoalkylphosphoramidates over 4-chlorothieno[2,3-b]pyridine-5-carbonitrile. The crystal structures of two compounds were solved by x-ray diffraction and showed a network of intermolecular interactions involving phosphoramidate groups. Druglike properties and toxicity of the new compounds were studied with the help of the software Molinspiration, Osiris, and Toxtree, and were compared with the standard drugs amphotericin B, miltefosine, benznidazole, and nifurtimox.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

Chemical Composition of Volatile Compounds in Apis mellifera Propolis from the Northeast Region of Pará State,Brazil

Propolis is a balsamic product obtained from vegetable resins by exotic Africanized bees Apis mellifera L., transported and processed by them, originating from the activity that explores and maintains these individuals. Because of its vegetable and natural origins, propolis is a complex mixture of different compound classes; among them are the volatile compounds present in the aroma. In this sense, in the present study we evaluated the volatile fraction of propolis present in the aroma obtained by distillation and simultaneous extraction, and its chemical composition was determined using coupled gas chromatography, mass spectrometry, and flame ionization detection. The majority of compounds were sesquiterpene and hydrocarbons, comprising 8.2–22.19% α-copaene and 6.2–21.7% β-caryophyllene, with additional compounds identified in greater concentrations. Multivariate analysis showed that samples collected from one region may have different chemical compositions, which may be related to the location of the resin’s production. This may be related to other bee products.     

Morphologic changes in the urethral epithelium in an ethanol-drinking rat strain (UChA and UChB)

The extreme use of ethanol causes metabolic and pathologic changes in testes and urogenital system in different animal species. The enzyme alcohol dehydrogenase (ADH) catalyses the conversion of ethanol into carcinogenic metabolite acetaldehyde which is partly excreted into the urine. However, papers relating the chronic ethanol consumption to the urethral morphology are unknown. This work evaluates the toxic effect of the chronic ethanol ingestion on the urethral epithelium of UChA and UChB rats. Conventional techniques of histology, histochemistry, immunohistochemistry and ultrastructural analysis were used. The analysis showed the presence of lipid drops and intercellular spaces in the epithelial cells in the urethra of UChA and UChB rats compared to control rats. Urethral neuroendocrine cell were observed and characterized for presenting vesicles containing electron-dense granules associated with nervous fibers. We conclude that the chronic consumption of ethanol induces the presence lipid drops in the epithelial cells of the urethra of UChA and UChB rats. The NE cells of the urethra of UChA and UChB rats did not show alterations under chronic effect of the ethanol.     

Polymeric biocomposites of poly (butylene adipate-co-terephthalate) reinforced with natural Munguba fibers

In this work, polymeric biocomposites of poly (butylene adipate-co-terephthalate), PBAT, were reinforced with Munguba fibers (Pseudobombax munguba). This tree is found in great abundance in the marshy areas of the Amazon forest. The motivation for using this fiber in polymer composites comes from the fact that although research for this fiber has not been reported in the scientific literature, it is commonly used by the local population because its bark is strong and flexible. Most important is that the extraction of Munguba fibers does not damage the supplier tree because as it is extracted from the bark, its regeneration starts as it is removed. The fibers were chemically treated by mercerization/acetylation and evaluated by Fourier transform infrared spectroscopy, thermogravimetric analysis and tensile tests. The Munguba fiber presented mechanical properties similar to those of other natural fibers traditionally used in composites, and the chemical treatment provided improvements of its thermal stability and stiffness. The biocomposites showed a better elastic modulus in relation to the pure PBAT. The addition of fibers caused changes in the T _g, T _m and T _c of PBAT as observed by differential scanning calorimetry analysis. The Russel, Halpin-Tsai and Maxwell models were employed to provide the theoretical elastic modulus of the biocomposites.