Spectrophotometric determination of urea in sugar cane distilled spirits

Urea is an important precursor in the formation of ethyl carbamate, a known carcinogen in alcoholic beverages. Ethyl carbamate has recently been detected at high concentrations in sugar cane distilled spirits, but little is known about the concentration of urea in these beverages. The objectives of this study were to validate methodology for the determination of urea in sugar cane distilled spirits, to determine the levels in 68 samples from different regions within the state of Minas Gerais, Brazil, and to examine the relationship between the concentrations of urea and ethyl carbamate. The method, based on the reaction of urea with 1-phenyl-1,2-propanodione-2-oxime and spectrophotometric quantification at 540 nm, provided linear response from 0.5 to 15.0 mg/L. No purification of the sample was required. The limits of detection and quantification were 0.1 and 0.5 mg/L, respectively. Urea was detected in 69% of the samples at levels varying from 0.50 to 5.10 mg/L. There was no significant difference on the levels of urea in samples from different regions of the state. No significant correlation between the levels of urea and ethyl carbamate was observed for the samples analyzed.     

Furanoditerpene ester and thiocarbonyldioxy derivatives inhibit photosynthesis

6α,7β-Dihydroxyvouacapan-17β-oic acid (1) and methyl 6α,7β-dihydroxyvouacapan-17β-oate (8) were isolated from Pterodon polygalaeflorus Benth. 1 was modified to obtain 6α-hydroxyvouacapan-7-β,17β lactone (2). Then, 6-oxovouacapan-7β,17β lactone (3) was obtained from 2. The furanoditerpene ester derivatives: propyl 7β-hydroxy-6-oxovouacapan-17β-oate (4), butyl 7β-hydroxy-6-oxovouacapan-17β-oate (5), 2-methoxyethyl 7β-hydroxy-6-oxovouacapan-17β-oate (6) and 3-methylbut-2-enyl 7β-hydroxy-6-oxovouacapan-17β-oate (7) were synthesized from (3) and methyl 6α,7β-thiocarbonyldioxyvouacapan-17β-oate (9) was obtained from (8). In this work, the lactone ester derivatives 4-7 and 9 were tested on photosynthetic activities in an attempt to search for new compounds as potential herbicide agents that affect photosynthesis. All compounds inhibited ATP synthesis and electron flow from water to MV, therefore, they act as Hill reaction inhibitors, being 4- to 9-fold more potent than 2 and 3 as inhibitors of ATP synthesis. Their interaction site was located at PSII in a similar way to diuron. Furthermore, furanoditerpene esters 6 and 7 act as uncouplers, and were corroborated by enhancement of the light-activated Mg²⁺-ATPase, while 5 act as an energy transfer inhibitor. Finally 5-7 behave as herbicides, since they inhibit the biomass production of weeds assay.     

pH-Dependent Solution Structure and Activity of a Reduced Form of the Host-Defense Peptide Myticin C (Myt C) from the Mussel Mytilus galloprovincialis

Myticin C (Myt C) is a highly variable host-defense peptide (HDP) associated to the immune response in the mediterranean mussel (Mytilus galloprovincialis), which has shown to be active across species due to its strong antiviral activity against a fish rhabdovirus found in fish cells overexpressing this HDP. However, the potential antimicrobial properties of any synthetic analogue of Myt C has not yet been analysed. Thus, in this work we have synthesised the sequence of the mature peptide of Myt C variant c and analysed the structure activity relationships of its reduced (non-oxidized) form (red-MytCc). In contrast to results previously reported for oxidized isoforms of mussel myticins, red-MytCc was not active against bacteria at physiological pH and showed a moderate antiviral activity against the viral haemorrhagic septicaemia (VHS) rhabdovirus. However, its chemotactic properties remained active. Structure/function studies in neutral and acid environments by means of infrared spectroscopy indicated that the structure of red-MytCc is pH dependent, with acid media increasing its alpha-helical content. Furthermore, red-MytCc was able to efficiently aggregate artificial phospholipid membranes at low pH, as well as to inhibit the Escherichia coli growth, suggesting that this activity is attributable to its more structured form in an acidic environment. All together, these results highlight the dynamic and environmentally sensitive behavior of red-Myt C in solution, and provide important insights into Myt C structure/activity relationships and the requirements to exert its antimicrobial/immunomodulatory activities. On the other hand, the pH-dependent direct antimicrobial activity of Myt C suggests that this HDP may be a suitable template for the development of antimicrobial agents that would function selectively in specific pH environments, which are sorely needed in this “antibiotic-resistance era”.     

Purification of xylitol obtained by fermentation of corncob hydrolysates

Hydrolysates obtained by autohydrolysis-posthydrolysis of corncobs were detoxified with charcoal, concentrated, supplemented with nutrients, and fermented with Debaryomyces hansenii. After biomass removal, the fermented media contained 0.1137 kg of nonvolatile components (NVC)/kg of liquor, which corresponded mainly to xylitol (0.6249 kg/kg of NVC) but also to minor amounts of inorganic components (measured as ashes), proteins, nonfermented sugars (xylose and arabinose), uronic acids, arabitol, and other nonvolatile components (ONVC). The media were subjected to further processing (sequential stages of adsorption, concentration, ethanol precipitation, concentration, and crystallization) to obtain food-grade xylitol. Adsorption experiments were carried out at various solid-to-liquor ratios. Under selected conditions (1 kg of charcoal/15 kg of liquors), the xylitol content increased to 0.6873 kg/kg of NVC, and almost total decoloration was achieved. The resulting liquor was concentrated by evaporation to increase its NVC content to 0.4032 kg/kg of liquor (corresponding to a xylitol concentration of 0.280 kg/kg of liquor), and ethanol was added to precipitate a part of the NVC (mainly proteins, but also uronic acids, ashes, and other nonvolatile compounds). Refined liquors (containing 0.7303 kg of xylitol/kg of NVC) were concentrated again, and ethanol was added (to reach 40-60% volume of the stream) to allow crystallization at -10 or -5 degrees C. Under selected conditions, 43.7% of xylitol contained in the initial fermentation broth was recovered in well-formed, homogeneous crystals, in which xylitol accounted for 98.9% of the total oven-dry weight. Material balances are presented for the whole processing scheme considered in this work.