Determination of methionine sulfoxide in biological materials using HPLC and its degradability in the rumen of cattle

doi:10.1016/0377-8401(94)90116-3

Animal Feed Science and Technology

Volume 48, Issues 1–2, July 1994, Pages 121-130

https://doi.org/10.1016/0377-8401(94)90116-3 Get rights and content

Abstract

A method was developed for estimating concentrations of methionine sulfoxide, methionine and other amino acids in feed protein using reverse phase high performance liquid chromatography. This incorporated pre-column o-phthaldialdehyde (OPA) derivatization and fluorometric detection. Samples were hydrolyzed prior to analysis using 4 M methanesulfonic acid containing 0.2% 3-(2-aminoethyl)indole (tryptamine) under vacuum at 120°C for 17 h. Hydrolyzates were diluted, adjusted to pH 7 and filtered.

A Beckman 507 autosampler with a precolumn derivatization cassette was used for the derivatization process. Fluorometric detection (excitation 338 nm and emission 425 nm) was used to measure OPA derivatives. Samples were prepared such that on column concentration was in the 10–200 pmole range. The mean recovery of the standard solution added to the feed samples was 96.8 ± 1.4% for seven tested feeds. Reproducibility of the method was evaluated by analyzing eight grass hay samples (0.39 ± 0.21 mg g⁻¹ DM) and eight alfalfa hay samples that had been incubated for 96 h in the rumen (0.14 ± 0.09 mg g⁻¹ DM). Relative standard deviations were 2.74% and 2.97%, respectively. The use of methanesulfonic acid as a hydrolyzing agent for feed protein, allowed for higher recovery of total methionine when compared with hydrochloric acid with or without sample oxidation (108.5%). The rumen degradability of protein from grass hay decreased as the amount of methionine sulphoxide increased.

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Convenient method of threonine, methionine and their related amino compounds by high-performance liquid chromatography and its application to rumen fluid
2000, Journal of Chromatography B: Biomedical Sciences and Applications
A high-performance liquid chromatographic procedure for the quantitative determination of cysteine (Cys), homocysteine (Hcys), methionine sulfoxide (MSO), methionine sulfone (MSO₂), homoserine (Hser), glycine (Gly), threonine (Thr), 2-aminobutyric acid (2AB), methionine (Met), cystathionine (Cysta) and its application to rumen fluid are described. The samples containing Thr, Met and other related amino compounds were derivatized with 9-fluorenylmethyl chloroformate. The separation of compounds was accomplished with a methanol gradient in 25 mM sodium citrate buffer (obtaining pH 6.40 and 3.80 by addition of 25 mM citric acid). All derivatized compounds were separated on a Mightysil RP-18 GP (150×4.6 mm I.D., 5 μm particle size) column. All analytes were detected at 265 nm with UV detection. The limits of detection (μM) (S/N ratio, 3:1) and quantification (μM) (S/N ratio, 10:1) of Cys, Hcys, MSO, MSO₂, Hser, Gly, Thr, 2AB, Met and Cysta were 0.50 and 1.68; 1.76 and 5.85; 0.85 and 2.88; 0.92 and 3.09; 1.04 and 3.52; 0.76 and 2.52; 0.65 and 2.18; 0.39 and 1.36; 0.31 and 1.03; 0.17 and 0.58, respectively. The recoveries of all compounds in rumen fluid were 97.93–102.3% in the within-day study and 94.52–98.69% on different day (6 days) studies. The average contents (μM) of Cys, Gly, Thr, 2AB, Met and Cysta were 1.72, 45.6, 20.0, 4.3, 2.11 and 3.42 before morning feeding. The concentration of Thr, 2AB and Cysta in rumen fluid tended to increase with time after feeding whereas Met showed the opposite tendency.
Use of the Cornell Net Carbohydrate and Protein System and Rumen-Protected Lysine and Methionine to Reduce Nitrogen Excretion from Lactating Dairy Cows
1998, Journal of Dairy Science
A study was carried out to determine whether the addition of rumen-protected Lys and Met to ration formulations allowed a reduction in dietary crude protein (CP) without jeopardizing total milk or milk protein yields. Eighteen multiparous Holstein cows were randomly assigned to treatment sequences in a replicated 3 × 3 Latin square design. Total mixed rations were balanced according to degradation and rates of passage of protein and carbohydrates using the Cornell Net Carbohydrate and Protein System. Rations differed in percentages of CP (18.3, 16.7, and 15.3% for rations 1, 2, and 3, respectively), but energy was held constant. Rations 2 and 3 were supplemented with rumen-protected Lys and Met. Milk, blood, and rumen fluid samples were taken during the 2nd and 3rd wk of each 28-d experimental period. Total collection of urine and feces occurred during the last 5 d of each experimental period. Cows fed ration 1 had a higher milk yield (34.2 vs. 32.8 kg/d) and DMI than did cows fed rations 2 or 3, but milk protein output was not different among groups. Nitrogen efficiency, milk N as a percentage of intake N, improved as percentages of CP in the rations were reduced. Blood urea N values were 15.9, 12.9, and 10.0 mg/dl for cows fed rations 1, 2, and 3, respectively. Apparent digestibilities of CP and urinary N excretion decreased as the percentages of CP in the rations decreased. Results indicated that it is possible to make more efficient use of CP by using rumen-protected amino acids. This procedure may result in less than maximum milk yield, but milk protein output can be maintained.
In Situ Disappearance of Amino Acids from Grass Silages in the Rumen and Intestine of Cattle
1998, Journal of Dairy Science
Nineteen grass silages were evaluated using the in situ rumen and mobile nylon bag techniques to determine the amino acid (AA) composition of rumen-undegradable protein and the possibility of predicting the concentrations of individual AA presented to the duodenum from the dietary AA profiles. All feeds and residues from the nylon bags were analyzed for diaminopimelic acid to correct for contamination by microbial proteins. All essential AA behaved similarly; the initial feed had the highest concentrations, and the material remaining in the mobile nylon bag had the lowest concentrations. The reduction in the concentration of methionine between the 12-h rumen residue and the residue in the mobile nylon bag was significant. With the exception of arginine (r² = 0.76) and serine (r² = 0.82), the relationship was poor between the concentrations of AA in the grass silage and those in the residue in the nylon bag following 12 h of rumen incubation. The lack of reliable relationships between concentrations of individual AA in the silages and concentrations of AA in the 12-h rumen residue indicated that degradability characteristics of AA in grass silage were not alike. This poor relationship was likely the reason that prediction equations could not be developed between the AA composition of the initial feed and the pattern of AA presented to the duodenum following 12 h of rumen incubation. The AA composition of the rumen-undegradable portion of grass silages differs from the AA composition of grass silages.
Influence of duodenal infusion of L-methionine and L-methionine-dl-sulfoxide on amino acid concentration and duodenal electrical activity in Friesian calves
1997, Animal Feed Science and Technology
Four, 28-day-old Friesian calves (50 ± 3 kg) fitted with duodenal, jugular catheters and duodenal electrodes were used to study absorption of duodenally infused L-methionine (Met) and L-methionine sulfoxide (MSO) and their effect on duodenal motor migrating complexes (MMC). Animals were fed milk replacer at 5% BW twice daily, but were starved overnight prior to experimental procedure. Animals received saline infusion for 2 h at 1 ml min⁻¹ prior to a 1-h infusion of 3.6 mmol of either Met or MSO. Infusion of saline was continued for another 2 h after cessation of amino acid infusion. Duodenal MMC were measured with the computer-based data acquisition system (MacLab, ADI, Australia). Initial plasma concentrations of Met were similar for both Met or MSO (19 μM) infusion. Plasma Met concentrations increased 20 min after initiating Met infusion. The highest plasma Met concentration (62 μM) occurred 15 min after Met infusion was ceased. Plasma MSO concentrations increased 40 min after the start of MSO infusion. The highest plasma MSO concentration occurred 45 min after cessation of MSO infusion (25 μM). No change in plasma Met concentration (P > 0.1) occurred with MSO infusion. Absorption of MSO was 52% that of Met. Met did not change the duration of MMC but reduced the number of spikes during the phase of irregular spiking activity (305.5 vs 660.3 spikes min⁻¹ MSO; P < 0.05). MSO prolonged the duration of irregular spiking activity (30.2 vs 22.3 min Met; P < 0.05). The velocity of migration of regular spiking activity increased as a result of Met infusion (39.3 vs 21.2 cm min⁻¹ MSO; P < 0.001).
Lack of change in Met concentration during MSO infusion indicates very little, if any, reduction of MSO in calves. Met at high concentrations may limit the absorption of nutrients through increased passage rate and decreased electrical activity during the absorption phase of MMC.
In vitro protein digestibility, amino acid profile and available iron of infant-weaning food prepared from maize flour and bovine blood
1997, Food Research International
In vitro multienzyme protein digestibility of an infant-weaning food produced from maize flour and bovine blood proteins was determined using the pH-stat and pH-drop procedures. A multienzyme digestion system consisting of trypsin, chymotrypsin and peptidase showed an improved protein digestibility when a blood protein concentrate was added to maize flour. The results obtained from the two methods for measuring protein digestibility were similar. Amino acid composition of infant-weaning food was satisfactory in meeting the requirement for essential amino acids of infants. After blending with the blood protein concentrate, the level of available iron was double that of maize flour alone.
Metabolic responses associated with confinement stress in tilapia: The role of cortisol
1997, Comparative Biochemistry and Physiology - C Pharmacology Toxicology and Endocrinology
We examined the effect of 2- or 24-hr confinement stress and cortisol treatment on plasma cortisol, glucose, lactate and free amino acids concentration and hepatic glycogen content and activities of certain enzymes involved in the intermediary metabolism in tilapia (Oreochromis mossambicus). Confinement of tilapia for 2 or 24 hr resulted in significantly higher plasma cortisol, glucose, lactate (2 hr), total and some of the free amino acids concentration (especially at 24 hr) and hepatic pyruvate kinase (PK), phosphoenolpyruvate carboxykinase (PEPCK; 24 hr) and lactate dehydrogenase activities (24 hr). Hepatic glycogen content was lower at 2 and 24 hr in the confined fish compared with the unstressed fish. Tilapia given cortisol implants (50 mg·kg⁻¹ body wt) had significantly higher plasma cortisol, glucose and some of the free amino acids concentration and hepatic PEPCK and aspartate aminotransferase activities, whereas PK activity ratio was significantly lower compared with the sham group. The results suggest that glucose production 2 hr after confinement may be due to glycogenolysis, whereas the maintenance of higher glucose at 24 hr after confinement is essentially due to gluconeogenesis. Furthermore, the changes in plasma metabolites and hepatic enzyme activities with cortisol implantation suggest that cortisol plays a role in the metabolic adjustment to 24-hr confinement stress in tilapia.

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Animal Feed Science and Technology

Abstract

References (20)

Effect of hydrogen peroxide treatment on the nutritional quality of rapeseed flour fed to weaning rats

J. Nutr.

Simplified protein hydrolysis with methanesulphonic acid at elevated temperature for the complete amino acid analysis of proteins

J. Chrom.

Mobile nylon for estimating intestinal availability of rumen undegradable protein

J. Dairy Sci.

The purification of methionine sulfoxide reductase from Escherichia coli

Anal. Biochem.

Transport and utilization of methionine sulfoxide in the rabbit

Biochim. Biophys. Acta.

Complete amino acid analysis of proteins from single hydrolysate

J. Biol. Chem.

Effects of equimolar doses of l-methionine, d-methionine, l-methionine-dl-sulfoxide on plasma and urinary amino acids levels in normal adult humans

J. Nutr.

Methionine oxidation in human growth hormone and human chorionic somatotropin

J. Biol. Chem.

Periodate oxidation of methionine in protein

Anal. Biochem.

A chemical approach to the nutritional availability of methionine in food proteins

Ann. Nutr. Alim.

Cited by (21)

Convenient method of threonine, methionine and their related amino compounds by high-performance liquid chromatography and its application to rumen fluid

Use of the Cornell Net Carbohydrate and Protein System and Rumen-Protected Lysine and Methionine to Reduce Nitrogen Excretion from Lactating Dairy Cows

In Situ Disappearance of Amino Acids from Grass Silages in the Rumen and Intestine of Cattle

Influence of duodenal infusion of L-methionine and L-methionine-dl-sulfoxide on amino acid concentration and duodenal electrical activity in Friesian calves

In vitro protein digestibility, amino acid profile and available iron of infant-weaning food prepared from maize flour and bovine blood

Metabolic responses associated with confinement stress in tilapia: The role of cortisol