Solid-State NMR Characterization of Mefloquine Resinate Complexes Designed for Taste-Masking Pediatric Formulations.

Mefloquine (MQ) is an antimalarial medication prescribed to treat or malaria prevention.. When taken by children, vomiting usually occurs, and new doses of medication frequently need to be taken. So, developing pediatric medicines using taste-masked antimalarial drug complexes is mandatory for the success of mefloquine administration. The hypothesis that binding mefloquine to an ion-exchange resin (R) could circumvent the drug's bitter taste problem was proposed, and solid-state 13C cross-polarization magic angle spinning (CPMAS) NMR was able to follow MQ-R mixtures through chemical shift and relaxation measurements. The nature of MQ-R complex formation could then be determined. Impedimetric electronic tongue equipment also verified the resinate taste-masking efficiency in vitro. Variations in chemical shifts and structure dynamics measured by proton relaxation properties (e.g., T1ρH) were used as probes to follow the extension of mixing and specific interactions that would be present in MQ-R. A significant decrease in T1ρH values was observed for MQ carbons in MQ-R complexes, compared to the ones in MQ (from 100-200 ms in MQ to 20-50 ms in an MQ-R complex). The results evidenced that the cationic resin interacts strongly with mefloquine molecules in the formulation of a 1:1 ratio complex. Thus, 13C CPMAS NMR allowed the confirmation of the presence of a binding between mefloquine and polacrilin in the MQ-R formulation studied.

Structural and conformational changes on chitosan after green heterogeneous synthesis of phenyl derivatives.

Four aromatic acid compounds: benzoic acid (Bz), 4-hydroxyphenylpropionic acid (HPPA), gallic acid (GA) and 4-aminobenzoic acid (PABA) were covalently bonded to chitosan in order to improve water solubility at neutral pH. The synthesis was performed via a radical redox reaction in heterogeneous phase by employing ascorbic acid and hydrogen peroxide (AA/H2O2) as radical initiators in ethanol. The analysis of chemical structure and conformational changes on acetylated chitosan was also the focus of this research. Grafted samples exhibited as high as 0.46 M degree of substitution (MS) and excellent solubility in water at neutral pH. Results showed a correlation between the disruption of C3-C5 (O3…O5) hydrogen bonds with increasing solubility in grafted samples. Spectroscopic techniques such as FT-IR and 1H and 13C NMR showed modifications in both glucosamine and N-Acetyl-glucosamine units by ester and amide linkage at C2, C3 and C6 position, respectively. Finally, loss of crystalline structure of 2-helical conformation of chitosan after grafting was observed by XRD and correlated with 13C CP-MAS-NMR analyses.

Structural Studies of Mexican Husk Tomato (Physalis ixocarpa) Fruit Cutin.

Green tomato (Physalis ixocarpa) is a specie native to Mexico, and it is known as "tomatillo" or "husk tomato". The fruit contains vitamins, minerals, phenolic compounds, and steroidal lactones, presenting antimicrobial activity and antinarcotic effects. Therefore, it is not only used in traditional Mexican cuisine, but also in traditional medicine to relieve some discomforts such as fever, cough, and amygdalitis. However, it is a perishable fruit whose shelf life is very short. As a part of the peel, cuticle, and epicuticular waxes represent the most important part in plant protection, and the specific composition and structural characterization are significant to know how this protective biopolymer keeps quality characteristics in fresh fruits. P. ixocarpa cutin was obtained by enzymatic treatments (cellulase, hemicellulose, and pectinase) and different concentrations of TFA, and studied through Cross Polarization Magic Angle Spinning Nuclear Magnetic Resonance (CPMAS 13C NMR), Ultra-High Performance Liquid Chromatography coupled to Mass Spectrometry (UHPLC-MS), and was morphologically characterized by Confocal Laser Scanning Microscopy (CLSM) and Scanning Electron Microscopy (SEM). The main constituents identified under the basis of UHPLC-MS analysis were 9,10,18-trihydroxy-octadecanoic acid and 9,10-epoxy-18-hydroxy-octadecanoic acid with 44.7 and 37.5%, respectively. The C16 absence and low occurrence of phenolic compounds, besides the presence of glandular trichomes, which do not allow a continuous layer on the surface of the fruit, could be related to a lower shelf life compared with other common fruits such as tomato (Solanum lycopersicum).

Structural Studies of the Cutin from Two Apple Varieties: Golden Delicious and Red Delicious (Malus domestica).

The cuticle, a protective cuticular barrier present in almost all primary aerial plant organs, has a composition that varies between plant species. As a part of the apple peel, cuticle and epicuticular waxes have an important role in the skin appearance and quality characteristic in fresh fruits destined for human consumption. The specific composition and structural characteristics of cutin from two apple varieties, "golden delicious" and "red delicious", were obtained by enzymatic protocols and studied by means of cross polarization magic angle spinning nuclear magnetic resonance (CP-MAS 13C NMR), attenuated total reflection infrared spectroscopy (ATR-FTIR), and mass spectrometry, and were morphologically characterized by specialized microscopy techniques (atomic force microscopy (AFM), confocal laser scanning microscopy (CLMS), and scanning electron microscopy (SEM)). According to CP-MAS 13C NMR and ATR-FTIR analysis, cutins from both varieties are mainly composed of aliphatics and a small difference is shown between them. This was corroborated from the hydrolyzed cutins analysis by mass spectrometry, where 9,10,18-trihydroxy-octadecanoic acid; 10,20-Dihydroxy-icosanoic acid; 10,16-dihydroxy hexadecenoic acid (10,16-DHPA); 9,10-epoxy-12-octadecenoic acid; and 9,10-epoxy-18-hydroxy-12-octadecenoic acid were the main monomers isolated. The low presence of polysaccharides and phenolics in the cutins obtained could be related to the low elastic behavior of this biocomposite and the presence of cracks in the apple cutin's surface. These cracks have an average depth of 1.57 µm ± 0.57 in the golden apple, and 1.77 µm ± 0.64 in those found in the red apple. The results obtained in this work may facilitate a better understanding that mechanical properties of the apple fruit skin are mainly related to the specific aliphatic composition of cutin and help to much better investigate the formation of microcracks, an important symptom of russet formation.

Cutin from Solanum Myriacanthum Dunal and Solanum Aculeatissimum Jacq. as a Potential Raw Material for Biopolymers.

Plant cuticles have attracted attention because they can be used to produce hydrophobic films as models for novel biopolymers. Usually, cuticles are obtained from agroresidual waste. To find new renewable natural sources to design green and commercially available bioplastics, fruits of S. aculeatissimum and S. myriacanthum were analyzed. These fruits are not used for human or animal consumption, mainly because the fruit is composed of seeds. Fruit peels were object of enzymatic and chemical methods to get thick cutins in good yields (approximately 77% from dry weight), and they were studied by solid-state resonance techniques (CPMAS 13C NMR), attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), atomic force microscopy (AFM) and direct injection electrospray ionization mass spectrometry (DIESI-MS) analytical methods. The main component of S. aculeatissimum cutin is 10,16-dihydroxypalmitic acid (10,16-DHPA, 69.84%), while S. myriacanthum cutin besides of 10,16-DHPA (44.02%); another two C18 monomers: 9,10,18-trihydroxy-octadecanoic acid (24.03%) and 18-hydroxy-9S,10R-epoxy-octadecanoic acid (9.36%) are present. The hydrolyzed cutins were used to produce films demonstrating that both cutins could be a potential raw material for different biopolymers.

Humic extracts from hydrochar and Amazonian Anthrosol: Molecular features and metal binding properties using EEM-PARAFAC and 2D FTIR correlation analyses.

Organic matter plays many roles in the soil ecosystem. One property of the substance concerns the metal complexation and interaction with organic contaminants. In this sense, the humic substances (HS), a heterogeneous mixture of compounds, naturally derived from degradation of biomass, have been widely studied in environmental sciences. Recent advances showed a new way to produce humic-like substances (HLS) through hydrothermal carbonization of biomass. Thus, this study aimed to evaluate the HLS of hydrochars, produced by using a mixture of sugarcane bagasse and vinasse with sulfuric acid added (1 and 4% v/v), and to assess their interactions with metal ions, (Fe(III), Al(III), Cu(II) and Co(II)) using EEM-PARAFAC and a two-dimensional FTIR correlation analysis. The results were compared to the humic substances extracted from the Amazonian Anthrosol, as a model of anthropogenic organic matter. NMR analysis showed that humic-like extracts from hydrochar are mainly hydrophobic, while the soil has a greater contribution of polar moieties. The HLS and HS showed similar complexation capacities for Fe(III), Al(III) and Cu(II) assays. For Co(II) HLS exhibited larger affinities than HS. Two-dimensional correlation analysis FTIR showed that chemical groups may undergo conformational alteration with metal additions to achieve more stable arrangements (higher stability constant). Therefore, these results contribute more knowledge about the mechanism of HS and metal ion interaction, as well as showing that HTC can be an interesting option for HLS production, to be used as humic based materials.

1H NMR spectra dataset and solid-state NMR data of cowpea (Vigna unguiculata).

In this article the NMR data from chemical shifts, coupling constants, and structures of all the characterized compounds were provided, beyond a complementary PCA evaluation for the corresponding manuscript (E.G. Alves Filho, L.M.A. Silva, E.M. Teofilo, F.H. Larsen, E.S. de Brito, 2017) [3]. In addition, a complementary assessment from solid-state NMR data was provided. For further chemometric analysis, numerical matrices from the raw 1H NMR data were made available in Microsoft Excel workbook format (.xls).

Laccase induction by synthetic dyes in Pycnoporus sanguineus and their possible use for sugar cane bagasse delignification.

The use of synthetic dyes for laccase induction in vivo has been scarcely explored. We characterized the effect of adding different synthetic dyes to liquid cultures of Pycnoporus sanguineus on laccase production. We found that carminic acid (CA) can induce 722 % and alizarin yellow 317 % more laccase than control does, and they promoted better fungal biomass development in liquid cultures. Aniline blue and crystal violet did not show such positive effect. CA and alizarin yellow were degraded up to 95 % during P. sanguineus culturing (12 days). With this basis, CA was selected as the best inducer and used to evaluate the induction of laccase on solid-state fermentation (SSF), using sugarcane bagasse (SCB) as substrate, in an attempt to reach selective delignification. We found that laccase induction occurred in SSF, and a slight inhibition of cellulase production was observed when CA was added to the substrate; also, a transformation of SCB under SSF was followed by the 13C cross polarization magic angle spinning (CPMAS) solid-state nuclear magnetic resonance (NMR). Results showed that P. sanguineus can selectively delignify SCB, decreasing aromatic C compounds by 32.67 % in 16 days; O-alkyl C region (polysaccharides) was degraded less than 2 %; delignification values were not correlated with laccase activities. Cellulose-crystallinity index was increased by 27.24 % in absence of CA and 15.94 % when 0.01 mM of CA was added to SCB; this dye also inhibits the production of fungal biomass in SSF (measured as alkyl C gain). We conclude that CA is a good inducer of laccase in liquid media, and that P. sanguineus is a fungus with high potential for biomass delignification.

Solution and Solid State Nuclear Magnetic Resonance Spectroscopic Characterization of Efavirenz.

Samples of efavirenz (EFZ) were evaluated to investigate the influence of the micronization process on EFZ stability. A combination of X-ray diffraction, thermal analysis, FTIR, observations of isotropic chemical shifts of (1)H in distinct solvents, their temperature dependence and spin-lattice relaxation time constants (T1), solution (1D and 2D) (13)C nuclear magnetic resonance (NMR), and solid-state (13)C NMR (CPMAS NMR) provides valuable structural information and structural elucidation of micronized EFZ and heptane-recrystallized polymorphs (EFZ/HEPT). This study revealed that the micronization process did not affect the EFZ crystalline structure. It was observed that the structure of EFZ/HEPT is in the same form as that obtained from ethyl acetate/hexane, as shown in the literature. A comparison of the solid-state NMR spectra revealed discrepancies regarding the assignments of some carbons published in the literature that have been resolved.

Phosphatase activity and its relationship with physical and chemical parameters during vermicomposting of filter cake and cattle manure.

BACKGROUND: Recycling of phosphorus (P) from organic residues (ORs) is important to develop environmentally friendly agriculture. The use of this P source depends on phosphatase enzymes, which can be affected by a chain of parameters during maturation of ORs. In this study the phosphatase activity levels throughout vermicomposting of filter cake (FC) and cattle manure (CM) were correlated with different physical and chemical parameters in an effort to increase the knowledge about recycling of P from ORs. RESULTS: FC presented higher total nitrogen content (TNC), total organic carbon (TOC), humic acid (HA) content, water-soluble P (WSP), phosphatase activities and nanopore volume than CM during vermicomposting. Decreases in TOC of CM resulted from carbohydrate mineralization, which was not observed for FC. CM showed increased hydrophobic index during vermicomposting while FC showed a slight decrease. CONCLUSION: Phosphatase activities correlated positively with TOC, pH and WSP and negatively with HA content for both vermicomposts. Nanopore volume was negatively correlated with phosphatase activities for FC but not for CM. No correlations between hydrophobicity and phosphatase activities were found for FC. Increased hydrophobicity throughout vermicomposting of CM could be partially associated with decreases in phosphatase levels.

Organomineral Interactions and Herbicide Sorption in Brazilian Tropical and Subtropical Oxisols under No-Tillage.

We evaluated the effects of the soil organic matter (SOM) composition, distribution between soil aggregates size, and their interactions with the mineral phase on herbicide sorption (alachlor, bentazon, and imazethapyr) in tropical and subtropical Oxisols under no-till systems (NT). Using soil physical fractionation approach, sorption experiments were performed on whole soils and their aggregates. SOM chemistry was assessed by CP/MAS (13)C NMR. The lower sorption observed in tropical soils was attributed to the greater blockage of SOM sorption sites than in subtropical soils. When these sites were exposed upon physical fractionation, sorption of the three herbicides in tropical soils increased, especially for imazethapyr. High amounts of poorly crystallized sesquioxides in these soils may have contributed to masking of sorption sites, indicating that organomineral interactions may lead to blockage of sorption sites on SOM in tropical soils.