1H chemical shift differences of prelog–djerassi lactone derivatives: DFT and NMR conformational studies

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)This work reports an experimental and theoretical study of the conformational preferences of several Prelog-Djerassi lactone derivatives, to elucidate the H-1 NMR chemical shift differences in the lactonic core that are associated with the relative stereochemistry of these derivatives. The boat-like conformation of 2 explains the anomalous H-1 chemical shift between H-5a and H-5b, in which the two methyl groups (C-8 and C-9) face H-5b, leading to its higher shielding effect.This work reports an experimental and theoretical study of the conformational preferences of several Prelog–Djerassi lactone derivatives, to elucidate the 1H NMR chemical shift differences in the lactonic core that are associated with the relative stereoc13721402145Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)FAPESP [13/02311-3]CNPq [477944/2013-2

A Soil Management Assessment Framework (SMAF) Evaluation of Brazilian Sugarcane Expansion on Soil Quality

The Soil Management Assessment Framework (SMAF) was developed to evaluate impacts of land use and management practices on soil quality (SQ), but its suitability for Brazilian tropical soils was unknown. We hypothesized that SMAF would be sensitive enough to detect SQ changes associated with sugarcane (Saccharum officinarum L.) expansion for ethanol production. Field studies were performed at three sites across the south-central region of Brazil, aiming to quantify the impacts of a land use change sequence (i.e., native vegetation–pasture–sugarcane) on SQ. Eight soil indicators were individually scored using SMAF curves developed primarily for North American soils and integrated into an overall Soil Quality Index (SQI) and its chemical, physical, and biological sectors. The SMAF scores were correlated with two other approaches used to assess SQ changes, soil organic C (SOC) stocks and Visual Evaluation of Soil Structure (VESS) scores. Our findings showed that the SMAF was an efficient tool for assessing land use change effects on the SQ of Brazilian tropical soils. The SMAF scoring curves developed using robust algorithms allowed proper assignment of scores for the soil chemical, physical, and biological indicators assessed. The SQI scores were significantly correlated with SOC stocks and VESS scores. Long-term transition from native vegetation to extensive pasture promoted significant decreases in soil chemical, physical, and biological indicators. Overall SQI suggested that soils under native vegetation were functioning at 87% of their potential capacity, while pasture soils were functioning at 70%. Conversions of pasture to sugarcane induced slight improvements in SQ, primarily because of improved soil fertility. Sugarcane soils are functioning at 74% of their potential capacity. Based on this study, management strategies were developed to improve SQ and the sustainability of sugarcane production in Brazil

1H NMR chemical profile and antioxidant activity of Eugenia punicifolia extracts over seasons: a metabolomic pilot study.

Eugenia punicifolia (Kunth) DC. is a medicinal plant used to treat diseases related to oxidative processes. In this work, H-1 nuclear magnetic resonance (NMR) spectroscopy and multivariate analysis have been employed to track the chemical changes and antioxidant activity of dimethyl sulfoxide (DMSO) extracts from E. punicifolia leaves over seasons. Principal component analysis (PCA) applied to H-1 NMR allowed discriminating DMSO extracts from leaves collected in the dry and rainy seasons and pointed out sucrose, catechin, and epicatechin as responsible for separating dry season samples and quercetin, acid gallic, glucose, and fatty acids contributed for rainy samples grouping. Notably, antioxidant assays revealed that dry season extracts exhibited a higher radical scavenging capacity. When those compounds were submitted to partial least squares-discriminant analysis (PLS-DA) only sucrose and fatty acids presented variable importance projection (VIP) score > 1, both metabolites are related somehow to the defense mechanisms of the plant. This pilot study may suggest new experimental approaches for more effectively monitoring the spectrum-effect relationship of E. punicifolia leaf extracts

Impact of amendments on the physical properties of soil under tropical long-term no till conditions

Tropical regions have been considered the world's primary agricultural frontier; however, some physico-chemical deficiencies, such as low soil organic matter content, poor soil structure, high erodibility, soil acidity, and aluminum toxicity, have affected their productive capacity. Lime and gypsum are commonly used to improve soil chemical fertility, but no information exists about the long-term effects of these products on the physical attributes and C protection mechanisms of highly weathered Oxisols. A field trial was conducted in a sandy clay loam (kaolinitic, thermic Typic Haplorthox) under a no-tillage system for 12 years. The trial consisted of four treatments: a control with no soil amendment application, the application of 2.1 Mg ha-1 phosphogypsum, the application of 2.0 Mg ha-1 lime, and the application of lime + phosphogypsum (2.0 + 2.1 Mg ha-1, respectively). Since the experiment was established in 2002, the rates have been applied three times (2002, 2004, and 2010). Surface liming effectively increased water-stable aggregates > 2.0 mm at a depth of up to 0.2 m; however, the association with phosphogypsum was considered a good strategy to improve the macroaggregate stability in subsoil layers (0.20 to 0.40 m). Consequently, both soil amendments applied together increased the mean weight diameter (MWD) and geometric mean diameter (GMD) in all soil layers, with increases of up to 118 and 89%, respectively, according to the soil layer. The formation and stabilization of larger aggregates contributed to a higher accumulation of total organic carbon (TOC) on these structures. In addition to TOC, the MWD and aggregate stability index were positively correlated with Ca2+ and Mg2+ levels and base saturation. Consequently, the increase observed in the aggregate size class resulted in a better organization of soil particles, increasing the macroporosity and reducing the soil bulk density and penetration resistance. Therefore, adequate soil chemical management plays a fundamental role in improving the soil's physical attributes in tropical areas under conservative management and highly affected by compaction caused by intensive farming