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1.
Kinetics of reduction of iron(IV) in ferrylmyoglobin by chlorogenate in neutral or moderately acidic aqueous solutions (0.16 M NaCl) to yield metmyoglobin was studied using stopped flow absorption spectroscopy. The reaction occurs by direct bimolecular electron transfer with (2.7 +/- 0.3) x 10(3) M(-)(1).s(-)(1) at 25.0 degrees C (DeltaH( )(#) = 59 +/- 6 kJ.mol(-)(1), DeltaS(#) = 15 +/- 22 J. mol(-)(1).K(-)(1)) for protonated ferrylmyoglobin (pK(a) = 4.95) and with 216 +/- 50 M(-)(1).s(-)(1) (DeltaH( )(#) = 73 +/- 8 kJ. mol(-)(1), DeltaS( )(#) = 41 +/- 30 J.mol(-)(1).K(-)(1)) for nonprotonated ferrylmyoglobin in parallel with reduction of a chlorogenate/ferrylmyoglobin complex by a second chlorogenate molecule with (8.6 +/- 1.1) x 10(2) M(-)(1).s(-)(1) (DeltaH( )(#) = 74 +/- 8 kJ.mol(-)(1), DeltaS( )(#) = 59 +/- 28 J.mol(-)(1).K(-)(1)) for protonated ferrylmyoglobin and with 61 +/- 9 M(-)(1).s(-)(1) (DeltaH( )(#) = 82 +/- 12 kJ.mol(-)(1), DeltaS( )(#) = 63 +/- 41 J. mol(-)(1).K(-)(1)) for nonprotonated ferrylmyoglobin. Previously published data on ascorbate reduction of ferrylmyoglobin are reevaluated according to a similar mechanism. For both protonated and nonprotonated ferrylmyoglobin the binding constant of chlorogenate is approximately 300 M(-)(1), and the modulation of ferrylmyoglobin as an oxidant by chlorogenate (or ascorbate) leads to a novel antioxidant interaction for reduction of ferrylmyoglobin by ascorbate in mixtures with chlorogenate.  相似文献   

2.
Malted cereals are rich sources of alpha-amylase, which catalyzes the random hydrolysis of internal alpha-(1-4)-glycosidic bonds of starch, leading to liquefaction. Amylases play a role in the predigestion of starch, leading to a reduction in the water absorption capacity of the cereal. Among the three cereal amylases (barley, ragi, and jowar), jowar amylase is found to be the most thermostable. The major amylase from malted jowar, a 47 kDa alpha-amylase, purified to homogeneity, is rich in beta structure ( approximately 60%) like other cereal amylases. T(m), the midpoint of thermal inactivation, is found to be 69.6 +/- 0.3 degrees C. Thermal inactivation is found to follow first-order kinetics at pH 4.8, the pH optimum of the enzyme. Activation energy, E(a), is found to be 45.3 +/- 0.2 kcal mol(-)(1). The activation enthalpy (DeltaH), entropy (DeltaS*), and free energy change (DeltaG) are calculated to be 44.6 +/- 0.2 kcal mol(-)(1), 57.1 +/- 0.3 cal mol(-)(1) K(-)(1), and 25.2 +/- 0.2 kcal mol(-)(1), respectively. The thermal stability of the enzyme in the presence of the commonly used food additives NaCl and sucrose has been studied. T(m) is found to decrease to 66.3 +/- 0.3, 58.1 +/- 0.2, and 48.1 +/- 0.5 degrees C, corresponding to the presence of 0.1, 0.5, and 1 M NaCl, respectively. Sucrose acts as a stabilizer; the T(m) value is found to be 77.3 +/- 0.3 degrees C compared to 69.6 +/- 0.3 degrees C in the control.  相似文献   

3.
The carotenoid composition of persimmon fruit purees of two cultivars, cvs. Rojo Brillante and Sharon, grown in Spain was determined by HPLC to assess the effects of high-pressure processing on some sensory (carotenoids), nutritional (provitamin A value), and health-related (radical-scavenging capacity) parameters. Total carotenoid content was higher in untreated Rojo Brillante puree (22. 11 microg g(-)(1)) than in untreated Sharon puree (15.22 microg g(-)(1)). Purees of both untreated cultivars showed similar carotenoid patterns after saponification with beta-cryptoxanthin, beta-carotene, and zeaxanthin as the main pigments. A high content of lycopene was quantified in Rojo Brillante (5.34 microg g(-)(1)), whereas only traces were detected in Sharon. The provitamin A value, reported as retinol equivalents (RE), was in untreated Rojo Brillante puree (77 RE/100 g) similar to that of Sharon (75 RE/100 g). Scavenging free radical capacity, measured as antiradical efficiency (AE), showed in untreated Rojo Brillante puree a value (12.14 x 10(-)(3)) 8.5 times higher than that in untreated Sharon (1. 42 x 10(-)(3)). Nonuniform behavior of high-pressure treatment was detected. Pressure treatments at 50 and 300 MPa/15 min/25 degrees C for Rojo Brillante and at 50 and 400 MPa/15 min/25 degrees C for Sharon increased the amount of extractable carotenoids (9-27%), which are related with the increase of vitamin A value (75-87 RE/100 g). No correlation with the increase of AE (from 1.42 x 10(-)(3) to 16.73 x 10(-)(3) and 19.58 x 10(-)(3)) after some pressure treatments (150 and 300 MPa/15 min/25 degrees C) was found.  相似文献   

4.
Hydrolysis of beta-lactoglobulin (in an equimolar mixture of the A and B variant) by trypsin in neutral aqueous solution [pH 7.7 at 25 degrees C, ionic strength 0.08 (NaCl)] was followed by capillary electrophoresis and thermodynamic parameters derived from a Michaelis-Menten analysis of rate data obtained at 10, 20, 30, and 40 degrees C for disappearance of beta-lactoglobulin. Enthalpy of substrate binding to the enzyme and the energy of activation for the catalytic process were found to have the values, DeltaH(bind) = -28 +/- 4 kJ mol(-)(1) and E(a) = 51 +/- 18 kJ mol(-)(1), respectively. Thus, beta-lactoglobulin shows an enthalpy of activation for free substrate reacting with free enzyme of about 21 kJ mol(-)(1), corresponding to a transition state stabilization of 60 kJ mol(-)(1) when compared to acid-catalyzed hydrolysis. The catalytic efficiency of trypsin in hydrolysis of beta-lactoglobulin is increased significantly by temperature; however, this effect is partly counteracted by a weaker substrate binding resulting in an increase by only 25%/10 degrees C in overall catalytic efficiency.  相似文献   

5.
The browning of glucose-fructose-glycine mixtures involves parallel glucose-glycine and fructose-glycine reactions, which share a common intermediate, the immediate precursor of melanoidins in the kinetic model. At pH 5.5, 55 degrees C glucose is converted into this intermediate in a two step process where k(1) = (7.8 +/- 1.1) x 10(-)(4) mol L(-)(1) h(-)(1) and k(2) = (1.84 +/- 0.31) x 10(-)(3) h(-)(1) according to established kinetics, whereas fructose is converted into this intermediate in a single step where k(4) = 5.32 x 10(-)(5)()()mol L(-)(1) h(-)(1). The intermediate is converted to melanoidins in a single rate limiting process where k(mix) = 0.0177 h(-)(1) and the molar extinction coefficient (based on the concentration of sugar converted) of the melanoidins so formed is 1073 +/- 4 mol(-)(1) L cm(-)(1). Whereas the value of k(mix) is the same when the individual sugars undergo browning, the value of the molar extinction coefficient is similar to that for melanoidins from the glucose-glycine reaction (955 +/- 45 mol(-)(1) L cm(-)(1)) but it is approximately double the value for melanoidins from the fructose-glycine reaction (478 +/- 18 mol(-)(1) L cm(-)(1)). This is the reason that the effects of glucose and fructose on the rate of browning are synergistic.  相似文献   

6.
Pectinmethylesterase of navel oranges shows two fractions greatly differing in thermostability. The most thermostable fraction accounts for approximately 10% of total activity. The thermal inactivation of this fraction follows first-order kinetics both in 5 mM, pH 3.5, citrate buffer and in orange juice at the same pH, showing a z value of 5.1 degrees C and an activation energy (E(a)) of 435 kJ mol(-)(1) K(-)(1). The heat resistance of the enzyme is approximately 25-fold higher in the juice than in citrate buffer. When ascorbic acid, sucrose, glucose, and fructose are added to the citrate buffer at the concentrations found in orange juice, the heat resistance of the enzyme increases 3-fold. The addition of pectin at 0.01% concentration multiplies it by a factor of 50. Manothermosonication (MTS), the simultaneous application of heat and ultrasound under moderate pressure (200 kPa), at 72 degrees C, increases the inactivation rate 25 times in buffer and >400 times in orange juice. MTS inactivation shows a higher z value (35.7 degrees C) and lower E(a) (56.9 kJ mol(-)(1) K(-)(1)) than simple heating.  相似文献   

7.
Pesticide sorption or binding to soil is traditionally characterized using batch slurry techniques. The objective of this study was to determine linuron sorption in field-moist or unsaturated soils. Experiments were performed using low-density (i.e., 0.25 g mL(-)(1)) supercritical carbon dioxide to remove linuron from the soil water phase, thus allowing calculation of sorption coefficients (K(d)) at low water contents. Both soil water content and temperature influenced sorption. K(d) values increased with increased water content, if less than saturated. K(d) values decreased with increased temperature. K(d) values for linuron sorption on silty clay and sandy loam soils at 12% water content and 40 degrees C were 3.9 and 7.0 mL g(-)(1), respectively. Isosteric heats of sorption (DeltaH(i)) were -41 and -35 kJ mol(-)(1) for the silty clay and sandy loam soils, respectively. The sorption coefficient obtained using the batch method was comparable (K(f) for sandy loam soil = 7. 9 microg(1)(-)(1/)(n)() mL(1/)(n)() g(-)(1)) to that obtained using the SFE technique. On the basis of these results, pesticide sorption as a function of water content must be known to more accurately predict pesticide transport through soils.  相似文献   

8.
Model systems were used to study the reaction kinetics of vanillin and pentalysine, lysine, glutathione, cysteine, aspartame, or phenylalanine (molar ratio 1:1) in phosphate buffer. The buffer pH was adjusted to the pK(a)(2) of the available alpha-amino group of each amino acid or peptide. Reductions of vanillin followed first-order kinetics at 55, 65, and 75 degrees C in the presence of each of the amino acids or peptides used. The reaction rates were accelerated as the temperature increased. The rate constants were highest for pentalysine followed by lysine, phenylalanine, glutathione/cysteine, and aspartame. The reduction of phenylalanine followed first-order kinetics, whereas the formation of its reaction product followed zero-order kinetics. The activation energy (E(a)) for the reaction ranged from 5.6 to 14.5 kcal/mol.  相似文献   

9.
A tungsten carbide coating on the integrated platform of a transversely heated graphite atomizer was used as a modifier for the direct determination of Se in soil extracts by graphite furnace atomic absorption spectrometry. Diethylenetriaminepentaacetic acid (0.0050 mol L(-1)) plus ammonium hydrogencarbonate (1.0 mol L(-1)) extracted predominantly available inorganic selenate from soil. The formation of a large amount of carbonaceous residue inside the atomizer was avoided with a first pyrolysis step at 600 degrees C assisted by air during 30 s. For 20 microL of soil extracts delivered to the atomizer and calibration by matrix matching, an analytical curve (10.0-100 microgram of L(-1)) with good linear correlation (r = 0.999) between integrated absorbance and analyte concentration was established. The characteristic mass was approximately 63 pg of Se, and the lifetime of the tube was approximately 750 firings. The limit of detection was 1.6 microgram L(-1), and the relative standard deviations (n = 12) were typically <4% for a soil extract containing 50 microgram of L(-1). The accuracy of the determination of Se was checked for soil samples by means of addition/recovery tests. Recovery data of Se added to four enriched soil samples varied from 80 to 90% and indicated an accurate method.  相似文献   

10.
Spin probes based on the 1,1,3,3-tetramethylisoindolin-2-yl structure have been used, in conjunction with electron spin resonance spectroscopy (ESR), to study the physical changes occurring in ice cream during freezing and melting. The ESR measurements allowed the rotational correlation times, tau(B), of the spin probes to be determined. Two probes were used together in a given sample of ice cream, namely, 1,1,3,3-tetramethylisoindolin-2-yl (TMIO), which samples the fat phase, and the sodium salt of 1,1,3,3-tetramethylisoindolin-2-yloxyl-5-sulfonate (NaTMIOS), which samples the aqueous phase. Data from the TMIO probe showed that when ice cream is cooled, the fat phase is a mixture of solid and liquid fat until a temperature of approximately -60 degrees C is reached. The water-soluble probe NaTMIOS showed that the aqueous phase changes completely from liquid to solid within 1 degrees C of -18 degrees C. On cooling further to -24.7 degrees C and then allowing it to warm to +25.0 degrees C, the rotational correlation times of the NaTMIOS were slow to recover to their previous values. For the lipid phase, tau(B)(298) was found to be 65.7 +/- 2.0 ps and the corresponding activation enthalpy, DeltaH, was 32.5 +/- 0.9 kJ mol(-)(1): These values are typical of those expected to be found in the type of fat used to make ice cream. The water phase gave corresponding values of 32.2 +/- 0.5 ps and 24.5 +/- 0.4 kJ mol(-)(1) values, which are those expected for a sucrose concentration of 24%.  相似文献   

11.
Soy isoflavones, present in many processed soy foods, are known for their phytoestrogenic and antioxidant activities. The aim of this work was to study the kinetics of genistein and daidzein degradation at elevated temperatures and to follow changes in their antioxidant activity. Daidzein and genistein in model solutions (pH 7 and 9) were thermally treated at 120 degrees C or incubated at 70, 80, and 90 degrees C. Isoflavone degradation was observed at all temperatures, with apparent first-order kinetics at 70-90 degrees C, and E(a) = 8.4 and 11.6 kcal/mol at pH 9, respectively. Microcalorimetric stability tests showed a similar pattern of degradation, however, with higher E(a) (genistein, 73.7 kcal/mol; daidzein, 34.1 kcal/mol) that may be attributed to the anaerobic conditions. The antioxidant activity of incubated isoflavone solutions, followed by the ABTS test, decreased rapidly at pH 9 for genistein, whereas only moderate reduction was observed for daidzein (pH 7 and 9) or genistein at pH 7. This may indicate different degradation mechanisms for genistein and daidzein.  相似文献   

12.
Hydrolyses of fenamiphos, fipronil, and trifluralin were studied in aqueous buffer solutions of pH 4.1, 7.1, and 9.1 at different temperatures, 5, 22 +/- 1, 32 +/- 1, and 50 +/- 1 degrees C. Fenamiphos, fipronil, and trifluralin were found to be more stable in acidic and neutral buffer solutions at temperatures of 5 and 22 +/- 1, and dissipation is rapid at 50 +/- 1 degrees C. In basic buffer and at higher temperature, degradation of fenamiphos was found to be very rapid when compared with fipronil and trifluralin. The rate constants calculated at 32 degrees C for fenamiphos were 2349.4 x 10(-)(8) (pH 4.1), 225.2 x 10(-)(8) (pH 7.1), and 30476.0 x 10(-)(8) (pH 9.1); for fipronil 1750.0 x 10(-)(8) (pH 4.1), 3103.0 x 10(-)(8) (pH 7.1), and 3883.0 x 10(-)(8) (pH 9.1); and for trifluralin 2331.0 x 10(-)(8) (pH 4.1), 2360.0 x 10(-)(8) (pH 7.1), and 3188.0 x 10(-)(8) (pH 9.1). On the basis of rate constant values, these pesticides appeared to be more susceptible to hydrolysis than synthetic organophosphorus compounds such as chlorpyriphos, diazinon, malathion, and ronnel. DT(50) values calculated at 32 degrees C were 228 (pH 4.1), 5310.24 (pH 7.1), and 37.68 (pH 9.1) h for fenamiphos; 608.6 (pH 4.1), 373.9 (pH 7.1), and 270.2 (pH 9.1) h for fipronil; and 502.1 (pH 4.1), 496.8 (pH 7.1), and 355.7 (pH 9.1) h for trifluralin.  相似文献   

13.
Production in a batch reactor with a solvent-free system of structured triacylglycerols containing short-chain fatty acids by Lipozyme RM IM-catalyzed acidolysis between rapeseed oil and caproic acid was optimized using response surface methodology (RSM). Reaction time (t(r)), substrate ratio (S(r)), enzyme load (E(l), based on substrate), water content (W(c), based on enzyme), and reaction temperature (T(e)), the five most important parameters for the reaction, were chosen for the optimization. The range of each parameter was selected as follows: t(r) = 5-17 h; E(l) = 6-14 wt %; T(e) = 45-65 degrees C; S(r) = 2-6 mol/mol; and W(c) = 2-12 wt %. The biocatalyst was Lipozyme RM IM, in which Rhizomucor miehei lipase is immobilized on a resin. The incorporation of caproic acid into rapeseed oil was the main monitoring response. In addition, the contents of mono-incorporated structured triacylglycerols and di-incorporated structured triacylglycerols were also evaluated. The optimal reaction conditions for the incorporation of caproic acid and the content of di-incorporated structured triacylglycerols were as follows: t(r) = 17 h; S(r) = 5; E(l) = 14 wt %; W(c) = 10 wt %; T(e) = 65 degrees C. At these conditions, products with 55 mol % incorporation of caproic acid and 55 mol % di-incorporated structured triacylglycerols were obtained.  相似文献   

14.
Pine kraft-anthraquinone (kraft-AQ) pulp was bleached in alkaline solution with hydrogen peroxide catalyzed by either [L(1)Mn(IV)(micro-O)(3)Mn(IV)L(1)](PF(6))(2)] (C1) or [LMn(IV)(2)(micro-O)(3)] (ClO(4))(2) (C2) at 60 and 80 degrees C for 120 min with a catalyst charge of 10 ppm on pulp. The resulting bleached pulp was hydrolyzed with cellulase to obtain insoluble and soluble residual lignins. The alkaline bleaching effluents were acidified to precipitate alkaline-soluble lignins. These lignin preparations were then characterized by 2D heteronuclear multiple-quantum coherence (HMQC) NMR spectroscopic techniques. The results showed that biphenyl (5-5) and stilbene structures of the residual lignin in the pulp are preferentially degraded in both the C1- and C2-catalyzed bleachings, whereas beta-O-4, beta-5, and beta-beta structures undergo degradation to a lesser extent. In both cases, the degradation of the residual lignin increased with the increase in reaction temperature from 60 to 80 degrees C. Thus, the result of C1-catalyzed delignification is not in agreement with the observed decrease in the disappearance rate for substrates in the C1-catalyzed oxidation of lignin model compounds with hydrogen peroxide when the reaction temperature is increased from 60 to 80 degrees C. In addition, the resulting residual lignins in the C2-catalyzed bleaching at 80 degrees C are less degraded than the corresponding lignins in the C1-catalyzed bleaching at both 60 and 80 degrees C. Thus, C1 is more effective than C2 as catalyst in the binucleus Mn(IV) complex-catalyzed bleaching of pine kraft-AQ pulp with hydrogen peroxide.  相似文献   

15.
The esterification reaction of geraniol with acetic acid catalyzed by Novozym was studied in supercritical ethane (sc-ethane) and in supercritical carbon dioxide (sc-CO(2)). Water activity (a(W)) had a very strong effect on enzyme activity, with reaction rates increasing up to a(W) = 0.25 and then decreasing for higher a(W). Salt hydrate pairs could not prevent changes in a(W) during the course of reaction but were able to control a(W) to some extent and had a beneficial effect on both initial rates of esterification and conversion in sc-ethane. The enzyme was more active in sc-ethane than in sc-CO(2), confirming the deleterious effect of the latter already observed with some enzymes. Temperatures between 40 and 60 degrees C did not have a strong effect on initial rates of esterification, although reaction progress declined considerably in that temperature range. For the mixture of 50 mM acetic acid plus 200 mM geraniol, 100% conversion was achieved at a reaction time of 10 h at 40 degrees C, 100 bar, an a(W) of incubation of 0.25, and a Novozym concentration of 0.55 mg cm(-)(3) in sc-ethane. Conversion was below 50% in sc-CO(2) at otherwise identical conditions. With an equimolar mixture of the two substrates (100 mM), 98% conversion was reached at 10 h of reaction in sc-ethane (73% conversion in sc-CO(2)).  相似文献   

16.
Characterization and esterification of hemicelluloses from rye straw   总被引：2，自引：0，他引：2  
Hemicelluloses were extracted with 10% KOH/0.5% Na(2)B(4)O(7). 10H(2)O from delignified rye straw. Esterification of the hemicelluloses with various acyl chlorides was performed in a homogeneous N,N-dimethylformamide and lithium chloride system using 4-(dimethylamino)pyridine catalyst and triethylamine as a neutralizer. The degree of substitution was controlled between 0.37 and 1.65. Under an optimum condition (sample 14, molar ratio 3:1), >90% of the free hydroxyl groups in native hemicelluloses were stearoylated at 75 degrees C for 40 min. Meanwhile, the products were characterized by FT-IR and GPC techniques as well as their solubilities. The molecular mass measurements (31400-123300 g mol(-)(1)) showed only a minimal degradation of the macromolecular hemicelluloses during rapid reactions at 48-75 degrees C for 20-40 min.  相似文献   

17.
A combined high-pressure carbon dioxide (HP-CO 2) and thermal degradation reaction of betanin and isobetanin in aqueous solution was investigated and can be described by a first-order decay. At 45 degrees C, the degradation rate constant ( k) for each pigment component significantly increased (the half-life ( t 1/2) decreased, p < 0.05) with elevated pressure. Furthermore, HP-CO 2 treatment led to lower k values (higher t 1/2 values) than thermal treatment. However, k and t 1/2 values approached those of thermal treatment when the pressure was >30 MPa combined with temperatures exceeding 55 degrees C. Moreover, betanin was more stable than isobetanin under HP-CO 2. E a values ranged from 94.01 kJ/mol for betanin and 97.16 kJ/mol for isobetanin at atmospheric pressure to 170.83 and 142.69 kJ/mol at 50 MPa, respectively. A higher pressure and temperature as well as longer exposure time resulted in higher values of L*, b*, C*, and h degrees . HP-CO 2 induced more degradation products from betanin and isobetanin than thermal treatment with an identical temperature and exposure time.  相似文献   

18.
Aqueous crude extracts of a series of plant wastes (agricultural, wild plants, residues from sports activities (grass), ornamental residues (gardens)) from 17 different plant species representative of the typical biodiversity of the Iberian peninsula were investigated as new sources of peroxidases (EC 1.11.1.7). Of these, lentil (Lens culinaris L.) stubble crude extract was seen to provide one of the highest specific peroxidase activities, catalyzing the oxidation of guaiacol in the presence of hydrogen peroxide to tetraguaiacol, and was used for further studies. For the optimum extraction conditions found, the peroxidase activity in this crude extract (110 U mL(-1)) did not vary for at least 15 months when stored at 4 °C (k(inact) = 0.146 year(-1), t(1/2 inact) = 4.75 year), whereas, for comparative purposes, the peroxidase activity (60 U mL(-1)) of horseradish (Armoracia rusticana L.) root crude extract, obtained and stored under the same conditions, showed much faster inactivation kinetics (k(inact) = 2.2 × 10(-3) day(-1), t(1/2 inact) = 315 days). Using guaiacol as an H donor and a universal buffer (see above), all crude extract samples exhibited the highest peroxidase activity in the pH range between 4 and 7. Once semipurified by passing the crude extract through hydrophobic chromatography on phenyl-Sepharose CL-4B, the novel peroxidase (LSP) was characterized as having a purity number (RZ) of 2.5 and three SDS-PAGE electrophoretic bands corresponding to molecular masses of 52, 35, and 18 kDa. The steady-state kinetic study carried out on the H(2)O(2)-mediated oxidation of guaiacol by the catalytic action of this partially purified peroxidase pointed to apparent Michaelian kinetic behavior (K(m)(appH(2)O(2)) = 1.87 mM; V(max)(appH(2)O(2)) = 6.4 mM min(-1); K(m)(app guaicol) = 32 mM; V(max)(app guaicol) = 9.1 mM min(-1)), compatible with the two-substrate ping-pong mechanism generally accepted for peroxidases. Finally, after the effectiveness of the crude extracts of LSP in oxidizing and removing from solution a series of last-generation dyes present in effluents from textile industries (1) had been checked, a steady-state kinetic study of the H(2)O(2)-mediated oxidation and decolorization of Green Domalan BL by the catalytic action of the lentil stubble extract was carried out, with the observation of the same apparent Michaelian kinetic behavior (K(m)(appGD) = 471 μM; V(max)(appGD)= 23 μM min(-1)). Further studies are currently under way to address the application of this LSP crude extract for the clinical and biochemical analysis of biomarkers.  相似文献   

19.
A residue depletion study of amoxicillin (AMO) and its major metabolites, amoxicilloic acid (AMA) and amoxicillin diketopiperazine-2',5'-dione, was performed after a single oral (p.o.) and intravenous (i.v.) administration of amoxicillin (20 mg kg (-1)) and amoxicillin/clavulanic acid (20 and 5 mg kg (-1)) to pigs. Animals were slaughtered 12, 36, 48, 60, 72, and 84 h after dosing. Tissue samples were analyzed using liquid chromatography-tandem mass spectrometry. Kidney samples contained high concentrations of amoxicilloic acid metabolite, which depleted much slower from tissues than amoxicillin, both after p.o. (t1/2AMO = 4.5 h vs t1/2AMA = 8 h) and i.v. (t1/2AMO = 4 h vs t1/2AMA = 8 h) administration. Moreover, after oral administration, significantly higher amoxicilloic acid concentrations were measured in liver and kidney than after i.v. administration. The coadministration of amoxicillin with clavulanic acid provoked no significant differences in amoxicilloic acid tissue concentrations as compared to an amoxicillin dosing. The prolonged presence of residues of amoxicilloic acid in edible tissues can play an important role in food safety, because the compound could give rise to a possible health risk, although it is not included in the maximum residue limit legislation.  相似文献   

20.
The kinetics of the thermal degradation of the natural cis carotenoid bixin in a water/ethanol (8:2) solution was studied as a function of temperature (70-125 degrees C), using high-performance liquid chromatography. The curves for the decay of bixin and formation of products (e.g., di-cis and all-trans isomers and a C17 degradation compound) did not adjust well to a first-order rate law, but very good fits were obtained using a biexponential model. This mathematical modeling gave the rate constant values for the formation of the primary products from bixin, and the energy barrier for each step was obtained. The di-cis isomers were formed immediately (15 kcal/mol) together with the decay of bixin, followed by a slow consumption, indicating their role as reaction intermediates. In fact, the di-cis isomers could easily revert to bixin (Ea approximately 3 kcal/mol) or yield the primary C17 degradation product, with an energy barrier of 6.5 kcal/mol. In turn, 24 kcal/mol was necessary for the Bix --> all-trans step, explaining its slower formation.  相似文献   

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