Comparative study of the cathodic cleavage of N-tosyl- and N-nosyl-protected amino acids

The electrochemical behaviour of alanine and phenylalanine protected by the toluenesulphonyl (tosyl) and nitrobenzesulphonyl (nosyl) groups was examined in dimethyl formamide. The N-tosyl-protected amino acids are reduced in one cathodic step (-2.4 V/SCE) leading to cleavage of the SN bond after a two-electron transfer process. The N-nosyl-protected amino acids are reduced in three cathodic steps. Cyclic voltammetry and controlled potential electrolysis of N-nosyl amino acids have been used to probe the mechanism of these reductions in an aprotic medium and lead to cleavage of the SN bond in good yields ( > 60%) at -1.10 V/SCE. The comparative study of these compounds is used to comment on the applicability of the electrochemical method of removing protecting groups from amino acids. © 1993.

Structural basis for the inhibition of a phospholipase A2-like toxin by caffeic and aristolochic acids

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Oxidation of Bovine Albumin by Hypochlorous and Hypobromous Acids: Structural and Functional Alterations

Aims: Hypochlorous (HOCl) and hypobromous (HOBr) acids are among the most powerful oxidants produced by the innate immune cells. Albumin is the predominant protein in most body fluids and is considered the most important antioxidant of blood plasma. Study Design: Oxidation of bovine albumin (BSA) and study of its structural and functional alterations. Place and Duration of Study: Faculty of Science and Faculty of Pharmaceutical Science, University of the State of Sao Paulo UNESP, between June and December 2012. Methodology: BSA was oxidized with excess of HOCl or HOBr and its structural and functional alterations were analyzed by spectroscopic techniques as UV-Vis absorption, intrinsic and synchronous fluorescence, fluorescence quenching, Rayleigh scattering and circular dichroism. Results: Both oxidants were able to deplete the intrinsic fluorescence of BSA, but HOBr was more effective than HOCl. The alterations in the synchronous fluorescence, UV-Vis absorption, and the appearance of a fluorescence band centered at 450 nm confirmed the difference between the oxidants. The oxidation did not induce aggregation of BSA as measured by Rayleigh scattering. The far-UV circular dichroism spectra showed a loss in the helical content and the near-UV-circular dichroism showed an alteration in the tertiary structure; HOBr was the more effective of the oxidants in this case. However, the oxidations did not induce significant alterations in the binding capacity of BSA, which was evaluated using hydrophobic (norfloxacin) and hydrophilic (ascorbic acid) drugs. Conclusion: These results suggest that, although highly susceptible to oxidation, the alterations did not inhibit BSA’s physiological function as a transport protein.

Oxidation of amino acids by chlorpromazine cation radical and co-catalysis by chlorpromazine

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The chemical oxygen demand / total volatile acids ratio as an anaerobic treatability indicator for landfill leachates

In some operational circumstances a fast evaluation of landfill leachate anaerobic treatability is necessary, and neither Biochemical Methane Potential nor BOD/COD ratio are fast enough. Looking for a fast indicator, this work evaluated the anaerobic treatability of landfill leachate from São Carlos-SP (Brazil) in a pilot scale Anaerobic Sequence Batch Biofilm Reactor (AnSBBR). The experiment was conducted at ambient temperature in the landfill area. After the acclimation, at a second stage of operation, the AnSBBR presented efficiency above 70%, in terms of COD removal, utilizing landfill leachate without water dilution, with an inlet COD of about 11,000 mg.L-1, a TVA/COD ratio of approximately 0.6 and reaction time equal to 7 days. To evaluate the landfill leachate biodegradability variation over time, temporal profiles of concentration were performed in the AnSBBR. The landfill leachate anaerobic biodegradability was verified to have a direct and strong relationship to the TVA/COD ratio. For a TVA/CODTotal ratio lower than 0.20, the biodegradability was considered low, for ratios between 0.20 and 0.40 it was considered medium, and above 0.40 it was considered high.

Omega-3 fatty acids supplementation decreases metabolic syndrome prevalence after lifestyle modification program

The additional effect of omega-3 supplementation in association with lifestyle modification program (LSMP) in free living-adults was evaluated.We studied 39 adults (control group with LSMP (G1, n = 16) and LSMP plus supplementation of 3 g of fish oil per day (360 mg of docosahexaenoic acid and 540 mg of eicosapentaenoic acid) (G2, n = 23)) during 20 weeks. The fish oil group showed a significant decrease in waist circumference (1.3%) followed by metabolic syndrome reduction (29%) mainly due to normalization of blood pressure (33.3%) and triacylglycerol (27.3%). Omega-3 supplementation provided additional benefits to LSMP in the resolution of metabolic syndrome

Glyphosate effects on sugarcane metabolism and growth

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Probiotic caprine Coalho cheese naturally enriched in conjugated linoleic acid as a vehicle for Lactobacillus acidophilus and beneficial fatty acids

To obtain a probiotic caprine Coalho cheese naturally enriched in conjugated linoleic acid (CLA), goats' diet was supplemented with soybean oil to produce CLA-enhanced milk, and Lactobacillus acidophilus La5 was incorporated into cheeses. CLA concentration and probiotic viability were evaluated during 60 days. Four pilot-scale cheese-making trials were manufactured, in triplicates. Cheeses T1 and T2 were produced with control milk, and T3 and T4 with CLA-enhanced milk. L. acidophilus was added to cheeses T2 and T4 during processing. The CLA content (isomer C18:2 cis-9, trans-11) in T3 and T4 was 246% to 291% higher than in T1 and T2 (P < 0.01). Populations of L. acidophilus were around 7.5 log cfu g(-1) in T2 and T4 during the study, and the highest CLA content in T4 did not influence the probiotic viability (P > 0.01). The CLA-enriched probiotic caprine Coalho cheese obtained is proposed as a vehicle for beneficial microorganisms and fatty acids. (C) 2012 Elsevier Ltd. All rights reserved.

Growth, organic acids profile and sugar metabolism of Bifidobacterium lactis in co-culture with Streptococcus thermophilus: the inulin effect

The organic acids profile, sugar metabolism and biomass growth of Streptococcus thermophilus (St) and Bifidobacterium lactis (BI) have been studied in pure cultures or binary co-culture (St-BI) in skim milk either containing 40 mg/g of inulin or not. With inulin, the time required by St. BI and St-BI to complete fermentation (i.e., when the pH reached 4.5) was about 14, 8 and 49% shorter than without inulin, respectively. This prebiotic also enhanced the levels of lactic and acetic acids and volatile compounds, showing a positive synbiotic effect between pre- and probiotics. In particular, the St-BI co-culture showed final concentrations of both microorganisms about 15 and 38% higher than in their respective pure cultures, thus highlighting a clear synergistic effect between these microorganisms due to mutual interactions. In addition, the well-known bifidogenic effect of inulin was confirmed. (c) 2012 Elsevier Ltd. All rights reserved.

Amino acids in squamous cell carcinomas and adjacent normal tissues from patients with larynx and oral cavity lesions

Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP)

Metabolic and functional effects of beta-hydroxy-beta-methylbutyrate (HMB) supplementation in skeletal muscle

Beta-hydroxy-beta-methylbutyrate (HMB) is a metabolite derived from leucine. The anti-catabolic effect of HMB is well documented but its effect upon skeletal muscle strength and fatigue is still uncertain. In the present study, male Wistar rats were supplemented with HMB (320 mg/kg per day) for 4 weeks. Placebo group received saline solution only. Muscle strength (twitch and tetanic force) and resistance to acute muscle fatigue of the gastrocnemius muscle were evaluated by direct electrical stimulation of the sciatic nerve. The content of ATP and glycogen in red and white portions of gastrocnemius muscle were also evaluated. The effect of HMB on citrate synthase (CS) activity was also investigated. Muscle tetanic force was increased by HMB supplementation. No change was observed in time to peak of contraction and relaxation time. Resistance to acute muscle fatigue during intense contractile activity was also improved after HMB supplementation. Glycogen content was increased in both white (by fivefold) and red (by fourfold) portions of gastrocnemius muscle. HMB supplementation also increased the ATP content in red (by twofold) and white (1.2-fold) portions of gastrocnemius muscle. CS activity was increased by twofold in red portion of gastrocnemius muscle. These results support the proposition that HMB supplementation have marked change in oxidative metabolism improving muscle strength generation and performance during intense contractions.

Fatty acid composition of the longissimus dorsi muscle in crossbred steers fed different sources of fatty acids

The objective of this study was to evaluate the fatty acid composition of the longissimus dorsi muscle in carcasses of 3/4 Bos taurus taurus 1/4 Bos taurus indicus steers fed different sources of fatty acids. Thirty-six steers aged 14 months, with a mean live weight of 320 kg, were fed the following diets for 96 days:1) control diet, containing no supplemental fat source; 2) CaSFA, diet containing 50 g calcium salts of fatty acids per kg total dry matter; 3) CS diet, containing 210 g cottonseed per kg total dry matter. The fatty acid composition of the longissimus dorsi muscle was determined by gas chromatography. No difference in slaughter weight, carcass weight, backfat thickness, or longissimus dorsi muscle area was observed between animals receiving the diets CaSFA and CS. Animals consuming the two fat-supplemented diets presented higher concentrations of oleic (C18:1), palmitic (C16:0) and stearic (C18:0) acids, corresponding to an average 80.76% of total fatty acids, and higher concentrations of vaccenic acid (C18:1 t11) in the muscle when compared with the control group. Supplementation of the diet of feedlot crossbred steers with CaSFA or cottonseed did not promote significant alterations in the lipid composition of the longissimus dorsi muscle.

ABSORPTION AND METABOLISM OF VOLATILE FATTY ACIDS BY RUMEN AND OMASUM

Volatile fatty acids (VFA) absorption and metabolic capacity of rumen and omasum were compared, in vitro. Fragments of rumen wall and omasum laminae were taken from eight adult crossbred bovines. An isolated fragment of the mucosa was fitted in a tissue diffusion chamber. Valeric acid and CrEDTA were added to ruminal fluid and placed on the mucosal side and buffer solution was placed on the serosal side. Fractional absorption rates were measured by exponential VFA:Cr ratio decay over time. Metabolism rate was determined as the difference between VFA absorbed and VFA which appeared on the serosal side over time. Mitotic index was higher in omasum (0.52%) than in rumen epithelium (0.28%). VFA fractional absorption rate was higher in omasum (4.6%/h.cm(2)) than in rumen (0.4%/h.cm(2)). Acetate, propionate, butyrate, and valerate showed similar fractional absorption rates in both fragments. Percentage of metabolized acetate and propionate was lower than butyrate and valerate in both stomach compartments. In the rumen, individual VFA metabolism rates were similar (mean of 7.7 mu mol/h.cm(2)), but in the omasum, valerate (90.0 mu mol/h.cm(2)) was more metabolized than butyrate (59.6 mu mol/h.cm(2)), propionate (69.8 mu mol/h.cm(2)) and acetate (51.7 mu mol/h.cm(2)). Correlation between VFA metabolism and mitotic index was positive in the rumen and in the omasum. In conclusion, VFA metabolism and absorption potential per surface of the omasum is higher than that of the rumen. Variations on rumen and omasum absorption capacities occur in the same way, and there are indications that factors capable of stimulating rumen wall proliferation are similarly capable of stimulating omasum walls.

Immbolization of uricase enzyme in Langmuir and Langmuir-Blodgett films of fatty acids: Possible use as a uric acid sensor

Preserving the enzyme structure in solid films is key for producing various bioelectronic devices, including biosensors, which has normally been performed with nanostructured films that allow for control of molecular architectures. In this paper, we investigate the adsorption of uricase onto Langmuir monolayers of stearic acid (SA), and their transfer to solid supports as Langmuir Blodgett (LB) films. Structuring of the enzyme in beta-sheets was preserved in the form of 1-layer LB film, which was corroborated with a higher catalytic activity than for other uricase-containing LB film architectures where the beta-sheets structuring was not preserved. The optimized architecture was also used to detect uric acid within a range covering typical concentrations in the human blood. The approach presented here not only allows for an optimized catalytic activity toward uric acid but also permits one to explain why some film architectures exhibit a superior performance. (C) 2011 Elsevier Inc. All rights reserved.

Oral Administration of Oleic or Linoleic Acids Modulates the Production of Inflammatory Mediators by Rat Macrophages

Oleic (OLA) and linoleic (LNA) acids are commonly consumed fatty acids and they can modulate the inflammatory response, in which macrophages play an important role. The aim of this study was to investigate the effects of these two fatty acids on the production of inflammatory mediators by macrophages. Rats received oral administration of water (control), OLA or LNA (0.22 g/kg body weight) daily for 10 days and peritoneal resident macrophages were then isolated. Subsequently, they were seeded in culture plates and the production of various inflammatory mediators was assessed. Oral administration with OLA decreased the production of IL-1 beta, IL-6 and CINC-2 alpha beta by resident macrophages and LNA decreased the production of IL-1 beta, IL-6 and VEGF in the absence of lipopolysaccharide (LPS), although it accelerated IL-1 beta release and decreased IL-10 synthesis when cells were stimulated with LPS. Neither fatty acid affected the production of superoxide anion, hydrogen peroxide, nitrite, TNF-alpha, PGE(2), LTB4 or 15(S)-HETE. Thus, OLA and LNA influence the production of several inflammatory mediators by macrophages.