Cacao (Theobromacacao L.) climate zones and its associated agrobiodiversity in Arauca, Colombia.

Background: Cacao (Theobromacacao L) is one of the most relevant crops in terms of economy and social rural development in Colombia. Cacao is also an important crop due to its potential to replace illicit crops and it is related to less deforestation and preserves the biodiversity. There are several cacao districts in Colombia, one of these being Arauca. The Department of Arauca is the second largest cocoa producing region in Colombia; however, it is heavily affected by armed conflict. To raise the knowledge and technology available in the region, integrating data on the occurrence of cacao farms with climatic variables becomes a powerful socioeconomic mapping tool for maintaining agrobiodiversity and food security in the region. Consequently, this type of agrodiversity data and agroclimatic approaches help to better manage agrobiodiversity, as in the cacao region of Arauca. These tools are even more relevant in biodiverse regions, such as flooded savannahs and tropical forest ecosystems, which are currently undergoing drastic changes due to agricultural expansion and climate change. One of the knowledge gaps in Colombia´s cacao regions is that there are currently no agroclimatic maps made with a social and scientific approach. This study aimed to provide a database of the spatial distribution of cacao farms in Arauca, as well as agroclimatic maps that identify and locate cacao climate regions in Arauca. We also present a presence-only matrix consisting of twenty-six tree species, or agrobiodiversity, distributed across the study region and specifically associated with the cacao forestry systems in Arauca. New information: We present the first database of both climate and agrobiodiversity data related to cacao farms in Arauca, developed with a research and socioeconomic vision that generated a novel approach for the agroclimatic zoning of cocoa in the Arauca Region and Colombia. Using 1,538 cacao farms at the regional scale, we identified two national and six regional-scale climate and soil regions. The selection at the local scale allowed us to classify 180 cacao farms comprising nine agroclimatic clusters in Arauca. We found twenty-six tree species distributed across the cacao climate zones. This dataset and its related maps also represent the agrobiodiversity of cultivated cacao locally. This is the most complete climate and agrobiodiversity dataset of cacao farms distribution in one of the top cocoa-producing regions in the country. These outputs are crucial because they constitute a baseline for developing research in the biodiversity of agroforestry systems, pests and diseases, pollutant presence, genetics, post-harvest processing and cocoa quality and safety.

Main urinary biomarkers of golden berries (Physalis peruviana) following acute and short-term nutritional intervention in healthy human volunteers.

The metabolites entering the bloodstream and being excreted in urine as a result of consuming golden berries are currently unidentified. However, these metabolites potentially underlie the health benefits observed in various in vitro, animal, and human models. A nutritional intervention with 18 healthy human volunteers was performed, and urine was collected at baseline and after acute and short-term fruit consumption for 19 days. After UPLC-ESI/QToF-MS analysis, untargeted metabolomics was performed on the urine samples, and from the 50 most discriminant ions (VIP > 2) generated by a validated PLS-DA model (CV-ANOVA = 3.7e-35; R^2Y = 0.86, Q^2Y = 0.62 and no overfitting), 22 compounds were identified with relatively high confidence. The most discriminant metabolites confirmed by DHS/GC-MS2 analysis of volatiles in urine were sesquiterpenes (C15H22): 3 stereoisomers, ß-vatirenene, ß-vetivenene, and ß-vetispirene, and 2 isomers, eremophila-1(10),8,11-triene and α-curcumene. Another major urinary biomarker was 4ß-hydroxywithanolide E and its phase II derivatives, which were observed in urine for all individual up to 24 h after the fruit was consumed; thus, the bioavailability of this biomarker in humans was demonstrated for the first time. Additionally, the excretion of certain acylcarnitines and hypoxanthine in urine increased after golden berry consumption, which may be associated with a detoxifying effect and may occur because fats were utilized rather than carbohydrates to meet the body's energy needs. The main biomarkers of golden berry consumption are specific to this fruit, confirming its potential for the functional food market.

Matrix effect on quantification of sugars and mannitol developed during the postharvest of cocoa: an alternative method for traceability of aroma precursors by liquid chromatography with an evaporative detector.

The profile of reducing sugars developed during each stage of the postharvest of cocoa beans is an important quality index; these sugars are found to be one of the main precursors of flavor and neoformed compounds. However, its quantification after extraction from different parts of the bean is a challenge due to the complexity of the matrix. The primary aim of this study was to track the formation of reducing sugars and mannitol in samples obtained from various steps of the fermentation and drying processes of cocoa beans by validating a rapid matrix-corrected chromatographic method utilizing a corona-charged aerosol detector for improved sensitivity. The analytes were extracted from ground cocoa beans by solid phase extraction without a defatting step (20 mg raw fermented and 10 mg dried). The experimental variables influencing the effective detection were evaluated at different temperatures and signal filtering levels. Method validation studies showed an average recovery between 77.8 and 120% for fermented cocoa and between 79.6 and 117.7% for dried cocoa. A linear response was achieved for fructose, glucose, sucrose, and mannitol for a concentration range of 0.1-40 mg/L, and maltose showed linearity in the range of 0.1-70 mg/L. Regression coefficients (R) were 0.9991, 0.9993, 0.9992, 0.9995 and 0.9994, respectively. This method was successfully applied to a clone mix of cocoa from Antioquia, Colombia, to confirm the hydrolysis reaction of sucrose into glucose and fructose during fermentation and drying. A quality indicator of an efficient postharvest process in this study was determined to be a glucose percentage of 0.66% w/w and a fructose percentage of 1.46% w/w, which were higher than the values reported by other studies.

Chemometric approaches for postharvest quality tracing of cocoa: An efficient method to distinguish plant material origin.

The aim of this study was to compare the quality of a mixture of cocoa harvested and fermented in three subregions of Antioquia (Colombia), from the chemometric profile based on multivariate statistical analysis. A mixture of clones CCN-52, ICS-1, FLE-2, and FEC-2 harvested in Bajo Cauca, Uraba and Magdalena Medio were subjected to a spontaneous fermentation. The characterization of raw and well-fermented cocoa was performed through 38 parameters, and results were compared by a Principal Component Analysis (PCA) and a Cluster Analysis (CA), followed by a Principal Factors Analysis (PFA- CA). The CA showed that there are differences among subregions only in raw cocoa from Bajo Cauca. PCA allowed identifying the variability between raw and fermented cocoa in a representative way and these results were consistent with the chemical profile. Besides, the number of parameters to differentiate raw cocoa from different subregions was reduced (11-13 parameters) and it was possible to characterize well fermented cocoa with only 10 parameters of 38. PFA-CA consolidated in three factors a grouping to identify the cocoa quality according to the process or interest of the sensory or functional properties. Factor 1 (cocoa quality indicators with functional properties), Factor 2 (indicators of quality of the beginning of fermentation) and Factor 3 (indicators of quality of well-fermented cocoa) each one with a weight of 39, 35 and 26 respectively.

Antioxidant activity of curcuminoids.

An exploration of the antioxidant power of curcumin, demethoxycurcumin, and bisdemethoxycurcumin, three natural antioxidants found in Curcuma longa, is reported in this work. We exhaust all structural possibilities leading to intramolecular hydrogen bonding and evaluate 15 isomers in total. Calculations were carried out in the gas phase and in the presence of solvents (water, to mimic biological media, and ethanol, to reproduce experimental assays) following the hydrogen atom transfer (HAT) and single electron transfer (SET) mechanisms. CH3OH-O hydrogen bonds are directly related to the antioxidant power via both mechanisms. We provide evidence to explain the experimental observations and to understand the fundamental factors driving antioxidant activity from a molecular perspective. Noticeably, the solvent enhances the antioxidant power in every case. All structures considered here are predicted to have better antioxidant abilities than phenol, and come very close to or surpass vitamin E.

Untargeted metabolomics reveals specific withanolides and fatty acyl glycoside as tentative metabolites to differentiate organic and conventional Physalis peruviana fruits.

The agronomic production systems may affect the levels of food metabolites. Metabolomics approaches have been applied as useful tool for the characterization of fruit metabolome. In this study, metabolomics techniques were used to assess the differences in phytochemical composition between goldenberry samples produced by organic and conventional systems. To verify that the organic samples were free of pesticides, individual pesticides were analyzed. Principal component analysis showed a clear separation of goldenberry samples from two different farming systems. Via targeted metabolomics assays, whereby carotenoids and ascorbic acid were analyzed, not statistical differences between both crops were found. Conversely, untargeted metabolomics allowed us to identify two withanolides and one fatty acyl glycoside as tentative metabolites to differentiate goldenberry fruits, recording organic fruits higher amounts of these compounds than conventional samples. Hence, untargeted metabolomics technology could be suitable to research differences on phytochemicals under different agricultural management practices and to authenticate organic products.