Activity of a Recombinant Chitinase of the Atta sexdens Ant on Different Forms of Chitin and Its Fungicidal Effect against Lasiodiplodia theobromae.

This study evaluates the activity of a recombinant chitinase from the leaf-cutting ant Atta sexdens (AsChtII-C4B1) against colloidal and solid α- and ß-chitin substrates. 1H NMR analyses of the reaction media showed the formation of N-acetylglucosamine (GlcNAc) as the hydrolysis product. Viscometry analyses revealed a reduction in the viscosity of chitin solutions, indicating that the enzyme decreases their molecular masses. Both solid state 13C NMR and XRD analyses showed minor differences in chitin crystallinity pre- and post-reaction, indicative of partial hydrolysis under the studied conditions, resulting in the formation of GlcNAc and a reduction in molecular mass. However, the enzyme was unable to completely degrade the chitin samples, as they retained most of their solid-state structure. It was also observed that the enzyme acts progressively and with a greater activity on α-chitin than on ß-chitin. AsChtII-C4B1 significantly changed the hyphae of the phytopathogenic fungus Lasiodiplodia theobromae, hindering its growth in both solid and liquid media and reducing its dry biomass by approximately 61%. The results demonstrate that AsChtII-C4B1 could be applied as an agent for the bioproduction of chitin derivatives and as a potential antifungal agent.

Muscle growth affects the metabolome of the pectoralis major muscle in red-winged tinamou (Rhynchotus rufescens).

The aim of the present study was to identify and quantify the metabolites (metabolome analysis) of the pectoralis major muscle in male red-winged tinamou (Rhynchotus rufescens) selected for growth traits. A selection index was developed for females [body weight (BW), chest circumference (CC), and thigh circumference (TC)] and males [BW, CC, TC, semen volume, and sperm concentration] in order to divide the animals into 2 experimental groups: selection group with a higher index (TinamouS) and commercial group with a lower index (TinamouC). Twenty male offspring of the 2 groups (TinamouS, n = 10; TinamouC, n = 10) were confined for 350 d. The birds were slaughtered and pectoralis major muscle samples were collected, subjected to polar and apolar metabolites extractions and analyzed by proton nuclear magnetic resonance (1H NMR) spectroscopy. Analysis of the polar metabolomic profile identified 65 metabolites; 29 of them were differentially expressed between the experimental groups (P < 0.05). The TinamouS groups exhibited significantly higher concentrations (P < 0.05) of 25 metabolites, including anserine, aspartate, betaine, carnosine, creatine, glutamate, threonine, 3-methylhistidine, NAD+, pyruvate, and taurine. Significantly higher concentrations of cysteine, beta-alanine, lactose, and choline were observed in the TinamouC group (P < 0.05). The metabolites identified in the muscle provided information about the main metabolic pathways (higher impact value and P < 0.05), for example, phenylalanine, tyrosine and tryptophan biosynthesis; alanine, aspartate and glutamate metabolism; D-glutamine and D-glutamate metabolism; ß-alanine metabolism; glycine, serine and threonine metabolism; taurine and hypotaurine metabolism; histidine metabolism; phenylalanine metabolism. The NMR spectra of apolar fraction showed 8 classes of chemical compounds. The metabolome analysis shows that the selection index resulted in the upregulation of polyunsaturated fatty acids, unsaturated fatty acids, phosphocholines, phosphoethanolamines, triacylglycerols, and glycerophospholipids. The present study suggests that, despite few generations, the selection based on muscle growth traits promoted changes in metabolite concentrations in red-winged tinamou.

Ruminal and feces metabolites associated with feed efficiency, water intake and methane emission in Nelore bulls.

The objectives of this study were twofold: (1) to identify potential differences in the ruminal and fecal metabolite profiles of Nelore bulls under different nutritional interventions; and (2) to identify metabolites associated with cattle sustainability related-traits. We used different nutritional interventions in the feedlot: conventional (Conv; n = 26), and by-product (ByPr, n = 26). Thirty-eight ruminal fluid and 27 fecal metabolites were significantly different (P < 0.05) between the ByPr and Conv groups. Individual dry matter intake (DMI), residual feed intake (RFI), observed water intake (OWI), predicted water intake (WI), and residual water intake (RWI) phenotypes were lower (P < 0.05) in the Conv group, while the ByPr group exhibited lower methane emission (ME) (P < 0.05). Ruminal fluid dimethylamine was significantly associated (P < 0.05) with DMI, RFI, FE (feed efficiency), OWI and WI. Aspartate was associated (P < 0.05) with DMI, RFI, FE and WI. Fecal C22:1n9 was significantly associated with OWI and RWI (P < 0.05). Fatty acid C14:0 and hypoxanthine were significantly associated with DMI and RFI (P < 0.05). The results demonstrated that different nutritional interventions alter ruminal and fecal metabolites and provided new insights into the relationship of these metabolites with feed efficiency and water intake traits in Nelore bulls.

Quality Attributes and Metabolic Profiles of Uvaia (Eugenia pyriformis), a Native Brazilian Atlantic Forest Fruit.

The uvaia is a native Brazilian Atlantic Forest Myrtaceae fruit with a soft pulp, ranging from yellow to orange, with a sweet acidic flavor and sweet fruity aroma. Uvaias present consumption potential, but their physicochemical characteristics are still understudied. In this context, we describe herein the metabolites of uvaia that have been determined by nuclear magnetic resonance spectroscopy. We screened 41 accessions and selected 10 accessions based on their diversity of physicochemical attributes, i.e., their fresh mass, height, diameter, yield, seed mass, total soluble solids, and titratable acidity. Twenty-six metabolites were identified, including sugars, acids, and amino acids. The results of this study comprise the most complete report on sugars and acids in uvaias. The relevant metabolites in terms of abundance were the reducing sugars glucose and fructose, as well as malic and citric acids. Furthermore, this study represents the first description of the uvaia amino acid profile and an outline of its metabolic pathways. Uvaia quality attributes differ among accessions, demonstrating high variability, diversity, and several possibilities in different economic areas. Our findings may help in future breeding programs in the selection of plant material for industries such as food and pharmaceuticals.

NMR-Based Metabolomics Reveals Effects of Water Stress in the Primary and Specialized Metabolisms of Bauhinia ungulata L. (Fabaceae).

Bauhinia ungulata is a plant used in Brazilian traditional medicine for the treatment of diabetes. Phytochemical studies revealed flavonoids and the saccharide pinitol related to hypoglycemic activity of the Bauhinia species. To determine the effects of water deficit on ecophysiological parameter and metabolite fingerprints of B. ungulata, specimens were treated with the following water regimens under greenhouse conditions: daily watering (control), watering every 7 days (group 7D), and watering every 15 days (group 15D). Metabolite profiling of the plants subjected to water deficit was determined by LC-HRMS/MS. An NMR-based metabolomics approach applied to analyze the extracts revealed increased levels of known osmoprotective and bioactive compounds, such as D-pinitol, in the water deficit groups. Physiological parameters were determined by gas exchange in planta analysis. The results demonstrated a significant decrease in gas exchange under severe drought stress, while biomass production was not significantly different between the control and group 7D under moderate stress. Altogether, the results revealed that primary and specialized/secondary metabolism is affected by long periods of severe water scarcity downregulating the biosynthesis of bioactive metabolites such as pinitol, and the flavonoids quercetin and kaempferol. These results may be useful for guiding agricultural production and standardizing medicinal herb materials of this medicinal plant.

Dynamics of the role of LacMeta laccase in the complete degradation and detoxification of malachite green.

Laccases highlight for xenobiotic bioremediation, as well as application in the fine chemical, textile, biofuel and food industries. In a previous work, we described the preliminary characterization of laccase LacMeta, a promising enzyme for the bioremediation of dyes, able to decolorization malachite green (MG), trypan blue, methylene blue. Here we demonstrate that LacMeta is indeed suitable for the complete degradation and detoxification of MG dye, not just for its discoloration, since some works show false positives due to the formation of colorless intermediates such as leucomalachite. The optimal pH and temperature parameters of LacMeta were 5.0 and 50 °C, respectively (MG as substrate). LacMeta was tolerant of up to 10 mmol L- 1 EDTA (82%) and up to 5% (V/V) acetone (91%) and methanol (71%), while SDS promoted severe inhibition. For ions, a high tolerance to cobalt, zinc, manganese, and calcium (10 mmol L- 1) was also observed (> 90%). Even under high-salinity conditions (1 mol L- 1 NaCl), the residual bleaching activity of the dye remained at 61%. Furthermore, the bleaching product of MG did not inhibit the germination of sorghum and tomato seeds and was inert to the vegetative structures of the germinated seedlings. Additionally, this treatment effectively reduced the cytotoxic effect of the dye on microorganisms (Escherichia coli and Azospirillum brasilense), which can be explained by H-NMR spectral analysis results since LacMeta completely degraded the peak signals corresponding to the aromatic rings in the dye, demonstrating extreme efficiency in the bioremediation of the xenobiotic at high concentrations (50 mg L- 1).

Magnetic Resonance and Vibrational Spectroscopy and Imaging in Food Analysis.

In the past two decades, there have been remarkable changes in the way we analyze the physical, chemical, and sensory properties of fresh and processed food products, with the progressive replacement of traditional wet analytical methods (destructive, laborious, time-consuming, and requiring the use of hazardous chemicals) with new, fast, non-destructive physical methods where the analysis is performed in a single step, after validation, and without the use of chemical reagents [...].

Effect of the application of vermicompost and millicompost humic acids about the soybean microbiome under water restriction conditions.

Humic substances (HSs) are constituent fractions of organic matter and are highly complex and biologically active. These substances include humic acids (HA), fulvic acids (FA), and humin. HS are known to stimulate the root system and plant growth and to mitigate stress damage, including hydric stress. Humic acids have already been reported to increase microbial growth, affecting their beneficial effect on plants. However, there is scarce information on whether HA from vermicompost and millicompost, along with Bradyrhizobium, improves the tolerance of soybean to water restriction. This study aimed to evaluate the responses of soybean plants to the application of vermicompost HA (HA-V) and millicompost (HA-M) along with Bradyrhizobium sp. under water restriction. The experiment was carried out in a greenhouse, and the treatments received Bradyrhizobium sp. inoculation with or without the application of HA from vermicompost and millicompost with or without water restriction. The results showed that HA provided greater soybean growth and nodulation than the control. The application of HA-M stimulated an increase in the richness of bacterial species in roots compared to the other treatments. After the application of water stress, the difference between the treatments disappeared. Microbial taxa were differentially abundant in plants, with the fungal fraction most affected by HA application in stressed roots. HA-V appears to be more prominent in inducing taxa under stress conditions. Although the results showed slight differences between HA from vermicompost and millicompost regarding plant growth, both humic acids promoted an increase in plant development compared to the control.

Head-to-Tail and Head-to-Head Molecular Chains of Poly(p-Anisidine): Combined Experimental and Theoretical Evaluation.

Poly(p-anisidine) (PPA) is a polyaniline derivative presenting a methoxy (-OCH3) group at the para position of the phenyl ring. Considering the important role of conjugated polymers in novel technological applications, a systematic, combined experimental and theoretical investigation was performed to obtain more insight into the crystallization process of PPA. Conventional oxidative polymerization of p-anisidine monomer was based on a central composite rotational design (CCRD). The effects of the concentration of the monomer, ammonium persulfate (APS), and HCl on the percentage of crystallinity were considered. Several experimental techniques such as X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), multifractal analysis, Nuclear Magnetic Resonance (13C NMR), Fourier-transform Infrared spectroscopy (FTIR), and complex impedance spectroscopy analysis, in addition to Density Functional Theory (DFT), were employed to perform a systematic investigation of PPA. The experimental treatments resulted in different crystal structures with a percentage of crystallinity ranging from (29.2 ± 0.6)% (PPA1HT) to (55.1 ± 0.2)% (PPA16HT-HH). A broad halo in the PPA16HT-HH pattern from 2θ = 10.0-30.0° suggested a reduced crystallinity. Needle and globular-particle morphologies were observed in both samples; the needle morphology might have been related to the crystalline contribution. A multifractal analysis showed that the PPA surface became more complex when the crystallinity was reduced. The proposed molecular structures of PPA were supported by the high-resolution 13C NMR results, allowing us to access the percentage of head-to-tail (HT) and head-to-head (HH) molecular structures. When comparing the calculated and experimental FTIR spectra, the most pronounced changes were observed in ν(C-H), ν(N-H), ν(C-O), and ν(C-N-C) due to the influence of counterions on the polymer backbone as well as the different mechanisms of polymerization. Finally, a significant difference in the electrical conductivity was observed in the range of 1.00 × 10-9 S.cm-1 and 3.90 × 10-14 S.cm-1, respectively, for PPA1HT and PPA16HT-HH.

Miniaturized Carbon Fiber Paper Electrodes for In Situ High Resolution NMR Analyses.

Combining spectroscopic techniques with electrochemistry is a promising strategy, as it allows the detailed investigation of the species that are consumed and produced by the reaction in real time. However, as with any in situ coupling technique, the junction between NMR and electrochemistry presents some challenges, notably the distortion of NMR signals due to the placement of electrodes close to or within the detection region. In this work, miniaturized electrodes made of carbon fiber paper were developed and later modified with platinum. Platinum decoration by cathodic deposition was chosen, as platinum is a prominent element in electrocatalysis, able to catalyze a large variety of reactions. To evaluate the efficiency of this electrochemical system, the oxidation of ascorbic acid was used as a model reaction. It was observed that the electrodes caused substantial signal distortion when placed within the detection region (full width at half-maximum equal to 1.46 Hz), whereas no distortion was observed when the electrodes were placed 1 mm above the detection region (full width at half-maximum equal to 0.95 Hz). With this system, it was also possible to monitor the magnetoelectrolysis effect, caused by the interaction of the magnetic field with the flowing ions, leading to a doubling of the ascorbic acid oxidation rate, compared to the reaction performed without a magnetic field. In addition to its low cost and simplicity in preparation, the developed electrode system allows the electrode surface to be easily modified with other suitable catalysts.

Impact of Cattle Feeding Strategy on the Beef Metabolome.

The present study explored changes in the meat metabolome of animals subjected to different finishing systems and growth rates. Thirty-six Angus × Nellore crossbred steers were used in a completely randomized design with four treatments: (1) feedlot system with high average daily gain (ADG; FH); (2) feedlot system with low ADG (FL); (3) pasture system with high ADG (PH); and (4) pasture system with low ADG (PL). After harvest and chilling, Longissimus thoracis (LT) muscle samples were taken for metabolite profile analysis using nuclear magnetic resonance. Spectrum was analyzed using chenomx software, and multi- and mega-variate data analyses were performed. The PLS-DA showed clear separation between FH and PL groups and overlap among treatments with different finishing systems but similar for matching ADG (FL and PH) treatments. Using a VIP cut-off of around 1.0, ATP and fumarate were shown to be greater in meat from PL cattle, while succinate, leucine, AMP, glutamate, carnosine, inosine, methionine, G1P, and choline were greater in meat from FH. Comparing FL and PH treatments, glutamine, carnosine, urea, NAD+, malonate, lactate, isoleucine, and alanine were greater in the meat of PH cattle, while G6P and betaine were elevated in that of FL cattle. Relevant pathways were also identified by differences in growth rate (FH versus PL) and finishing system were also noted. Growth rate caused a clear difference in meat metabolism that was highlighted by energy metabolism and associated pathways, while the feeding system tended to alter protein and lipid metabolism.

Non-Invasive Method to Predict the Composition of Requeijão Cremoso Directly in Commercial Packages Using Time Domain NMR Relaxometry and Chemometrics.

Low Field Time-Domain Nuclear Magnetic Resonance (TD-NMR) relaxometry was used to determine moisture, fat, and defatted dry matter contents in "requeijão cremoso" (RC) processed cheese directly in commercial packaged (plastic cups or tubes with approximately 200 g). Forty-five samples of commercial RC types (traditional, light, lactose-free, vegan, and fiber) were analyzed using longitudinal (T1) and transverse (T2) relaxation measurements in a wide bore Halbach magnet (0.23 T) with a 100 mm probe. The T1 and T2 analyses were performed using CWFP-T1 (Continuous Wave Free Precession) and CPMG (Carr-Purcell-Meiboom-Gill) single shot pulses. The scores of the principal component analysis (PCA) of CWFP-T1 and CPMG signals did not show clustering related to the RC types. Optimization by variable selection was carried out with ordered predictors selection (OPS), providing simpler and predictive partial least squares (PLS) calibration models. The best results were obtained with CWFP-T1 data, with root-mean-square errors of prediction (RMSEP) of 1.38, 4.71, 3.28, and 3.00% for defatted dry mass, fat in the dry and wet matter, and moisture, respectively. Therefore, CWFP-T1 data modeled with chemometrics can be a fast method to monitor the quality of RC directly in commercial packages.

Monitoring Stimulated Darkening from UV-C Light on Different Bean Genotypes by NMR Spectroscopy.

The use of UV-C cool white light on bean (Phaseolus vulgaris L.) seeds significantly increases the biochemical seed coat post-harvest darkening process, whilst preserving seed germination. The aim of this work consists in monitoring the effect caused by the incidence of UV-C light on different bean genotypes using NMR spectroscopy. The genotype samples named IAC Alvorada; TAA Dama; BRS Estilo and BRS Pérola from the Agronomic Institute (IAC; Campinas; SP; Brazil) were evaluated. The following two methodologies were used: a prolonged darkening, in which the grain is placed in a room at a controlled temperature (298 K) and humidity for 90 days, simulating the supermarket shelf; an accelerated darkening, where the grains are exposed to UV-C light (254 nm) for 96 h. The experiments were performed using the following innovative time-domain (TD) NMR approaches: the RK-ROSE pulse sequence; one- and two-dimensional high resolution (HR) NMR experiments (1H; 1H-1H COSY and 1H-13C HSQC); chemometrics tools, such as PLS-DA and heat plots. The results suggest that the observed darkening occurs on the tegument after prolonged (90 days) and accelerated (96 h) conditions. In addition, the results indicate that phenylalanine is the relevant metabolite within this context, being able to participate in the chemical reactions accounted for by the darkening processes. Additionally, it is possible to confirm that a UV-C lamp accelerates oxidative enzymatic reactions and that the NMR methods used were a trustworthy approach to monitor and understand the darkening in bean seeds at metabolite level.

Composite Graphite-Epoxy Electrodes for In Situ Electrochemistry Coupling with High Resolution NMR.

The in situ coupling between electrochemistry and spectrometric techniques can help in the identification and quantification of the compounds produced and consumed during electrochemical reactions. The combination of electrochemistry with nuclear magnetic resonance is quite attractive in this respect, but it has some challenges to be addressed, namely, the reduction in the quality of the NMR signal when the metallic electrodes are placed close to or in the detection region. Since NMR is not a passive technique, the convective effect of the magnetic force (magnetoelectrolysis), which acts by mixing the solution and increasing the mass transport, has to be considered. In seeking to solve the aforementioned problems, we developed a system of miniaturized electrodes inside a 5 mm NMR tube (outer diameter); the working and counter electrodes were prepared with a mixture of graphite powder and epoxy resin. To investigate the performance of the electrodes, the benzoquinone reduction to hydroquinone and the isopropanol oxidation to acetone were monitored. To monitor the alcohol oxidation reaction, the composite graphite-epoxy electrode (CGEE) surface was modified through platinization. The electrode was efficient for in situ monitoring of the aforementioned reactions, when positioned 1 mm above the detection region of the NMR spectrometer. The magnetoelectrolysis effect acts by stirring the solution and increases the reaction rate of the reduction of benzoquinone, because this reaction is limited by mass transport, while no effect on the reaction rate is observed for the isopropanol oxidation reaction.

Real-Time Monitoring Polymerization Reactions Using Dipolar Echoes in 1H Time Domain NMR at a Low Magnetic Field.

1H time domain nuclear magnetic resonance (1H TD-NMR) at a low magnetic field becomes a powerful technique for the structure and dynamics characterization of soft organic materials. This relies mostly on the method sensitivity to the 1H-1H magnetic dipolar couplings, which depend on the molecular orientation with respect to the applied magnetic field. On the other hand, the good sensitivity of the 1H detection makes it possible to monitor real time processes that modify the dipolar coupling as a result of changes in the molecular mobility. In this regard, the so-called dipolar echoes technique can increase the sensitivity and accuracy of the real-time monitoring. In this article we evaluate the performance of commonly used 1H TD-NMR dipolar echo methods for probing polymerization reactions. As a proof of principle, we monitor the cure of a commercial epoxy resin, using techniques such as mixed-Magic Sandwich Echo (MSE), Rhim Kessemeier-Radiofrequency Optimized Solid Echo (RK-ROSE) and Dipolar Filtered Magic Sandwich Echo (DF-MSE). Applying a reaction kinetic model that supposes simultaneous autocatalytic and noncatalytic reaction pathways, we show the analysis to obtain the rate and activation energy for the epoxy curing reaction using the NMR data. The results obtained using the different NMR methods are in good agreement among them and also results reported in the literature for similar samples. This demonstrates that any of these dipolar echo pulse sequences can be efficiently used for monitoring and characterizing this type of reaction. Nonetheless, the DF-MSE method showed intrinsic advantages, such as easier data handling and processing, and seems to be the method of choice for monitoring this type of reaction. In general, the procedure is suitable for characterizing reactions involving the formation of solid products from liquid reagents, with some adaptations concerning the reaction model.

Data fusion of middle-resolution NMR spectroscopy and low-field relaxometry using the Common Dimensions Analysis (ComDim) to monitor diesel fuel adulteration.

Medium-resolution (MR-NMR) and time-domain NMR relaxometry (TD-NMR) using benchtop and low-field NMR instruments are powerful tools to tackle fuel adulteration issues. In this work, for the first time, we investigate the possibility of enhancing the low-field NMR capability on fuel analysis using data fusion of MR and TD-NMR. We used the ComDim (Common Dimensions Analysis) multi-block analysis to join the data, which allowed exploration, classification, and quantification of common adulterations of diesel fuel by vegetable oils, biodiesel, and diesel of different sources as well as the sulfur content. After data exploration using ComDim, classification (applying linear discriminant analysis, LDA), and regression (applying multiple linear regression, MLR), models were built using ComDim scores as input variables on the LDA and MLR analyses. This approach enabled 100% of accuracy in classifying diesel fuel source (refinery), sulfur content (S10 or S500), vegetable oil, and biodiesel source. Moreover, in the quantification step, all MLR models showed a root mean square error of prediction (RMSEP) and the residual prediction deviation (RPD) values comparable to the literature for determining diesel, vegetable oil, and biodiesel contents.

Insight into morphological, physicochemical and spectroscopic properties of ß-chitin nanocrystalline structures.

We systematically investigated the effect of ß-chitin (BCH) particle size on the preparation of nanocrystals/nanowhiskers (CWH) by acid hydrolysis. Regardless this variable, CWH aqueous suspension exhibited outstanding stability and the average degree of acetylation remained nearly constant after the acid treatment. In contrast, the morphology, dimensions, crystallinity, and molecular weight of CHW were significantly affect by the particle size. Although needle-like crystals have predominated, BCH particles sizes significantly affected the dimensions and asymmetry of CWH, as confirmed by the rheological and NMR relaxation (T2) behaviors. According to different SSNMR approaches, the acid hydrolysis meaningless affected the local chain conformation, while the spatial freedom of BCH intersheets, rated upon the mobility of methyl segments, was taken as evidence of higher permeability of acid into small particle sizes. Thus, this study demonstrated the importance of standardizing the surface/bulk proportions of ß-chitin aiming to predict and control the CWH morphology and related properties.

Classical Food Quality Attributes and the Metabolic Profile of Cambuci, a Native Brazilian Atlantic Rainforest Fruit.

The cambuci is a native Brazilian fruit from the Atlantic Forest biome. A soft and astringent pulp, a green color, and a sweet aroma are its main characteristics. Classical food quality attributes (fresh fruit mass, fruit height, diameters, total soluble solid, titratable acidity, and ratio) and the metabolic profile from ten accessions from three different locations were analyzed herein by analytical methods (refractometry and neutralization titration) and nuclear magnetic resonance spectroscopy. Concerning sugar content, sucrose was the predominant compound, with glucose and fructose alternating in second, depending on the accession. Citric acid was the most relevant acid, followed by shikimic and quinic acids in quite variable amounts. These three main acids vary in amounts for each accession. Ascorbic acid content emerges as an important quality attribute and makes this fruit nutritionally attractive, due to values comparable to those contained in citric fruits. The main amino acids identified in cambuci were glutamic acid individually or in comprising the tripeptide glutathione (glutamic acid, cysteine, glycine). The quality diversity of the evaluated accessions suggests the potentiality of cambuci use in future breeding programs.

Phytotoxicity of Schiekia timida Seed Extracts, a Mixture of Phenylphenalenones.

Phenylphenalenones, metabolites found in Schiekia timida (Haemodoraceae), are a class of specialized metabolites with many biological activities, being phytoalexins in banana plants. In the constant search to solve the problem of glyphosate and to avoid resistance to commercial herbicides, this work aimed to investigate the phytotoxic effect of the methanolic extract of S. timida seeds. The chemical composition of the seed extract was directly investigated by NMR and UPLC-QToF MS and the pre- and post-emergence phytotoxic effect on a eudicotyledonous model (Lactuca sativa) and a monocotyledonous model (Allium cepa) was evaluated through germination and seedling growth tests. Three concentrations of the extract (0.25, 0.50, and 1.00 mg/mL) were prepared, and four replicates for each of them were analyzed. Three major phenylphenalenones were identified by NMR spectroscopy: 4-hydroxy-anigorufone, methoxyanigorufone, and anigorufone, two of those reported for the first time in S. timida. The presence of seven other phenylphenalenones was suggested by the LC-MS analyses. The phenylphenalenone mixture did not affect the germination rate, but impaired radicle and hypocotyl growth on both models. The effect in the monocotyledonous model was statistically similar to glyphosate in the lowest concentration (0.25 mg/mL). Therefore, although more research on this topic is required to probe this first report, this investigation suggests for the first time that phenylphenalenone compounds may be post-emergence herbicides.

Comparative untargeted metabolome analysis of ruminal fluid and feces of Nelore steers (Bos indicus).

We conducted a study to identify the fecal metabolite profile and its proximity to the ruminal metabolism of Nelore steers based on an untargeted metabolomic approach. Twenty-six Nelore were feedlot with same diet during 105 d. Feces and rumen fluid were collected before and at slaughter, respectively. The metabolomics analysis indicated 49 common polar metabolites in the rumen and feces. Acetate, propionate, and butyrate were the most abundant polar metabolites in both bio-samples. The rumen presented significantly higher concentrations of the polar compounds when compared to feces (P < 0.05); even though, fecal metabolites presented an accentuated representability of the ruminal fluid metabolites. All fatty acids present in the ruminal fluid were also observed in the feces, except for C20:2n6 and C20:4n6. The identified metabolites offer information on the main metabolic pathways (higher impact factor and P < 0.05), as synthesis and degradation of ketone bodies; the alanine, aspartate and glutamate metabolisms, the glycine, serine; and threonine metabolism and the pyruvate metabolism. The findings reported herein on the close relationship between the ruminal fluid and feces metabolic profiles may offer new metabolic information, in addition to facilitating the sampling for metabolism investigation in animal production and health routines.