Limonene concentration in lemon (Citrus volkameriana) peel oil as a function of ripeness

The dependence of the limonene content of lemon (Citrus volkameriana) peel oil on the degree of ripeness of the fruit has been studied by using steam distillation and cold pressing to extract the oils from lemon fruit peel at different stages of maturation (green, greenish-yellow, and yellow-orange peel coloration). Samples of essential oils were analyzed by high resolution GC and GC-MS, using tetradecane as internal standard for quantitation. Forty components were detected; thirty eight were positively identified by comparison of their mass spectra (El, 70 eV) and Kováts retention indexes (determined using a non-logarithmic scale on capillary columns coated with both polar (DB-Wax) and non-polar (DB-1) stationary phases) with those of standards and with data reported in the literature. The limonene concentration reached a maximum level of 79.4% when the fruit was in the intermediate maturation stage characterized by greenish-yellow coloration.     

Spontaneous assembly of a hydrogen-bonded tetrahedron

Triphenylamine ortho-tricarboxylic acid (1) has been synthesized and the crystal structure reported. This molecule is shown to spontaneously self-assemble into a hydrogen-bonded tetrahedron. Furthermore, Electrospray Ionization Mass Spectroscopy shows evidence for the stability of such aggregates from an ethanol/water solution.     

Gas-phase ion-molecule reactions of transition metal complexes: the effect of different coordination spheres on complex reactivity

Using a modified quadrupole ion trap mass spectrometer, a series of metal complex ions have been reacted with acetonitrile in the gas phase. Careful control of the coordination number and the type of coordinating functionality in diethylenetriamine-substituted ligands enable the effects of the coordination sphere on metal complex reactivity to be examined. The association reaction kinetics of acetonitrile with these pentacoordinate complexes are followed in order to obtain information about the starting complexes and the reaction dynamics. The kinetics and thermodynamics of acetonitrile addition to the metal complex ions are strongly affected by the chemical environment around the metal center such that significant differences in reactivity are observed for Co(II) and Cu(II) complexes with various coordination spheres. When thiophene, furan, or benzene moieties are present in the coordination sphere of the complex, addition of two acetonitrile molecules is readily observed. In contrast, ligands with better sigma donors react mainly to add one acetonitrile molecule. Among the ligands with good sigma donors, a clear trend in reactivity is observed in which complexes with nitrogen-containing ligands are the least reactive, sulfur-containing complexes are more reactive, and oxygen-containing complexes are the most reactive. In general, equilibrium and reaction rate constants seem to be consistent with the hard and soft acid and base (HSAB) principle. Interestingly, the presence of certain groups (e.g., pyridine and imidazole) in the coordination sphere clearly can change the acid character of the metal as seen by their effect on the binding properties of other functional groups in the same ligand. Finally, we conclude that because complexes with different coordination spheres react to noticeably different extents, ion-molecule (I-M) reactions may be potentially useful for obtaining coordination structure information for transition metal complexes.     

Mass Balance and Compositional Analysis of Biomass Outputs from Cacao Fruits

The global chocolate value chain is based exclusively on cacao beans (CBs). With few exceptions, most CBs traded worldwide are produced under a linear economy model, where only 8 to 10% of the biomass ends up in chocolate-related products. This contribution reports the mass balance and composition dynamics of cacao fruit biomass outputs throughout one full year of the crop cycle. This information is relevant because future biorefinery developments and the efficient use of cacao fruits will depend on reliable, robust, and time-dependent compositional and mass balance data. Cacao husk (CH), beans (CBs), and placenta (CP) constitute, as dry weight, 8.92 ± 0.90 wt %, 8.87 ± 0.52 wt %, and 0.57 ± 0.05 wt % of the cacao fruit, respectively, while moisture makes up most of the biomass weight (71.6 ± 2.29 wt %). CH and CP are solid lignocellulosic outputs. Interestingly, the highest cellulose and lignin contents in CH coincide with cacao’s primary harvest season (October to January). CB contains carbohydrates, fats, protein, ash, and phenolic compounds. The total polyphenol content in CBs is time-dependent, reaching maxima values during the harvest seasons. In addition, the fruit contains 4.13 ± 0.80 wt % of CME, a sugar- and nutrient-rich liquid output, with an average of 20 wt % of simple sugars (glucose, fructose, and sucrose), in addition to minerals (mainly K and Ca) and proteins. The total carbohydrate content in CME changes dramatically throughout the year, with a minimum of 10 wt % from August to January and a maximum of 29 wt % in March.     

Models for capacitated lot-sizing problem with backlogging,setup carryover and crossover

Setup operations are significant in some production environments. It is mandatory that their production plans consider some features, as setup state conservation across periods through setup carryover and crossover. The modelling of setup crossover allows more flexible decisions and is essential for problems with long setup times. This paper proposes two models for the capacitated lot-sizing problem with backlogging and setup carryover and crossover. The first is in line with other models from the literature, whereas the second considers a disaggregated setup variable, which tracks the starting and completion times of the setup operation. This innovative approach permits a more compact formulation. Computational results show that the proposed models have outperformed other state-of-the-art formulation.     

Stability and convergence of the spectral Lagrange-Galerkin method for mixed periodic/non-periodic convection-dominated diffusion problems

We present a convergence analysis of the spectral Lagrange-Galerkinmethod for mixed periodic/non-periodic convection-diffusionproblems. The scheme is unconditionally stable, independentof the diffusion coefficient, even in the case when numericalquadrature is used. The theoretical predictions are illustratedby a series of numerical experiments. For the periodic case,our results present a significant improvement on those givenby Süli & Ware (1991) SIAM J. Numer.Anal.28, 423-445).     

HRGC/FID and HRGC/MSD Analysis of the Secondary Metabolites Obtained by Different Extraction Methods from Lepechinia schiedeana,and in Vitro Evaluation of Its Antioxidant Activity

Steam distillation (SD), simultaneous distillation-solvent extraction (SDE), microwave-assisted solvent extraction (MWE), and supercritical (CO₂) extraction (SFE) were used to isolate secondary metabolites from Lepechinia schiedeana. The various extracts were analyzed by capillary gas-chromatography, on poly (dimethylsiloxane) (DB-1) and poly(ethyleneglycol) (INNOWAX), 60 m columns, using FID or MSD (EI, 70 eV). Kováts indexes, mass spectra, or standard compounds were employed for compound identification. 43, 61, 67, and 79 compounds at concentrations above 0.01% were detected in the SD, SDE, MWE, and SFE extracts, respectively. Ledol, C₁₅H₂₆O, was the major constituent (20.04–36.87%) in all extracts. Oxygenated sesquiterpenes (24.36–43.14%), C₁₀H₁₆, monoterpenes (27.70–39.87%), and C₁₅H₂₄, sesquiterpenes (10.04–22.22%) were the main groups of compounds present in SD, SDE, MWE, and SFE extracts. Heavy hydrocarbons (C_n > 15), diterpenoids, and phytosterols were found only in MWE and SFE extracts. The antioxidant activity of Lepechinia schiedeana was measured by the HRGC quantification of the volatile carbonyl compounds, final products of lipoxidation, released in a model lipid system (sunflower oil) by the effect of the Fenton reagent. The concentration of volatile carbonyl compounds decreased by 65% when lipid oxidation was induced in the presence of macerated Lepechinia plant. The protection of polyunsaturated acids in sunflower oil was also studied by measuring their concentrations after heating of the oil (180°C, 2 h) with and without macerated Lepechinia plant.