CN102283319B - Preparation method and application of chromium-carrying chitosan meat quality modifier - Google Patents

Preparation method and application of chromium-carrying chitosan meat quality modifier Download PDF

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Publication number
CN102283319B
CN102283319B CN2011101674309A CN201110167430A CN102283319B CN 102283319 B CN102283319 B CN 102283319B CN 2011101674309 A CN2011101674309 A CN 2011101674309A CN 201110167430 A CN201110167430 A CN 201110167430A CN 102283319 B CN102283319 B CN 102283319B
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shitosan
chromium
preparation
acid solution
emulsion
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CN102283319A (en
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王敏奇
叶珊珊
王超
杜勇杰
陶文静
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Zhejiang University ZJU
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Abstract

The invention discloses a preparation method and application of a chromium-carrying chitosan meat quality modifier. The preparation method comprises the following steps: 1) adding chitosan into an acid solution to obtain a chitosan acid solution; 2) adjusting the chitosan acid solution to enable the pH value to be 3-5, thus forming a micro-particle emulsion; 3) performing centrifugal separation on the micro-particle emulsion to obtain micro particles, adding the micro particles into a chromium salt solution, adjusting the pH value to 4.5-6.0, and reacting at room temperature for 5-10 hours to obtain an emulsion; 4) adjusting the pH value of the emulsion to 6.5-8.5, rinsing and filtering or centrifugally dehydrating; and 5) drying and crushing the solid product obtained in the step 4) to obtain the chromium-carrying chitosan meat quality modifier. The chromium-carrying chitosan meat quality modifier can be used as a feed additive for livestock and poultry or aquatic animals so as to effectively enhance the animal immunity and improve the lean meat percentage of the livestock and poultry.

Description

Carry the preparation method and its usage of chromium shitosan meat modifier
Technical field
The present invention relates to the preparation method and the purposes of a kind of year chromium shitosan meat modifier
Background technology
In recent years, " three height " crowd of hypertension, high fat of blood, high cholesterol increases gradually, and angiocardiopathy becomes the main killer who threatens human life's safety, and the consumer looks at the parent of low fat, high protein animal food and grows with each passing day.Around improve new technology that livestock body forms and additive exploitation from last century the nineties just become the focus that the livestock technology worker studies; A series of products such as growth hormone (GH), beta-stimulants have appearred in succession; These products really can obviously improve carcass quality, use inconvenient, many, the residual high drawbacks that are difficult to overcome of side effect but exist.Especially beta-stimulants, residual very big at pluck caused great harm to people healthy, and country's promulgation regulations are forbidded strictly to use.As develop and can significantly improve lean meat percentage, the safety-type feed addictive that improves meat is the difficult problem of the present producer, consumer and herding production management department common concern.
Trivalent chromium (Cr 3+) be growth of animal and the essential trace element of keeping glucose tolerance factor (GTF), enhance immune power and anti-stress ability are all played an important role.1993; Adding 200 μ g/kg chromium picolinates in the discovery diets such as Page can improve the fattening pig area of longissimus muscle, improve since the trunk composition; Domestic and international many scholar's research multi-form trivalent chromium pig growth performance, trunk are formed and the influence of meat; Mainly contain chromium chloride, yeast chromium, chromium picolinate, chromium propionate, chelating amino acids chromium etc., effect differs, and generally speaking is that the effect of Organic Chromium is superior to inorganic chromium; But, in actual production, use little because of DeGrain and less stable.
The shitosan chemical name is (1; 4)-2-acetamido-2-deoxidation-β-D-glucose; Be one type of enormous amount marine resources; For being that occurring in nature is only second to cellulosic second largest natural biological high polymer, owing to its excellent biological compatibility, degradability, nontoxic and unique physical and chemical properties and physiologically active receive extensive concern.Shitosan all has facilitation in various degree to animal body nospecific immunity and specific immunity, is a kind of good immunopotentiating agent.Shitosan has been applied to agricultural, industry and medicine and other fields as multiple functional materials such as feed addictive, heavy metal chelant, adsorbent and medicinal slow release agents.
Summary of the invention
The technical problem that the present invention will solve provides the preparation method and the purposes of a kind of year chromium shitosan meat modifier.
In order to solve the problems of the technologies described above, the present invention provides the preparation method of a kind of year chromium shitosan meat modifier, may further comprise the steps successively:
1), in 20~60 ℃, be that 0.1~5% acid solution adds shitosan in mass concentration, the shitosan acid solution; The mass concentration of shitosan in the shitosan acid solution is 0.1~5%;
2), to utilize mass concentration be that 0.1~5% acid solution is regulated the shitosan acid solution, making its pH value is 3~5; Thereby form the particulate emulsion;
3), centrifugation particulate emulsion, particulate;
(slowly) adds particulate in the chromium salt solution that chromium ion concentration is 100~500mg/L under stirring condition, mixed liquor, said chromic salts be in the step 1) shitosan weight 10~20%; Utilizing concentration then is that the pH value that the alkaline solution of 0.5~10mol/L is regulated mixed liquor is 4.5~6.0, room temperature reaction 5~10 hours, emulsion;
4), in the emulsion of step 3) gained, add concentration be the alkaline solution of 0.5~10mol/L to regulate pH value be 6.5~8.5, wash then 3~7 times, refilter or centrifugal dehydration; Collect solid product;
5), step 4) gained solid product oven dry back is pulverized, must carry chromium shitosan meat modifier.
Improvement as the preparation method of of the present invention year chromium shitosan meat modifier: the shitosan in the step 1) is that molecular weight is the shitosan of 2~80kDa.
Further improvement as the preparation method of of the present invention year chromium shitosan meat modifier: the chromic salts in the step 3) is chromium chloride, chromic nitrate, chromium sulfate, chromium chloride hydrate, chromic nitrate hydrate or chromium sulfate hydrate.
Further improvement as the preparation method of of the present invention year chromium shitosan meat modifier: step 1) and step 2) acid in is acetate or hydrochloric acid.
Further improvement as the preparation method of of the present invention year chromium shitosan meat modifier: alkali is NaOH, potassium hydroxide, sodium carbonate, potash, sodium acid carbonate or saleratus in step 3) and the step 4); More excellent alkaline solution concentration is 0.5~10mol/L.
Further improvement as the preparation method of of the present invention year chromium shitosan meat modifier: the bake out temperature of step 5) is 50~70 ℃, is crushed to and can crosses 300 purposes sieve at least.
The present invention also provides the purposes of carrying chromium shitosan meat modifier of utilizing above-mentioned any one method preparation and getting simultaneously, as the feed addictive of livestock and poultry or aquatic livestock.
In the present invention, molecular weight is that the corresponding deacetylation of shitosan of 2~80kDa is 80~95%.
Of the present invention year chromium shitosan meat modifier has low toxicity, characteristics efficient, safe in utilization, and effectively enhance immune power improves the lean meat percentage of livestock and poultry, reduces fat percentage, reduces the drip loss of meat, improves yellowish pink.
The specific embodiment
The preparation method of embodiment 1, a kind of year chromium shitosan meat modifier, carry out following steps successively:
1), in 25 ℃, in the acetic acid solution of mass concentration 0.5%, adding molecular weight is the shitosan of 8kDa, is mixed with the shitosan acid solution, the mass concentration of shitosan in the shitosan acid solution is 1%.
2), adopt the acetic acid solution of mass concentration 0.5% to regulate the shitosan acid solution, making its pH value is 3.5; Thereby form the particulate emulsion.
3), centrifugal (4000rpm/ minute rotating speed, the time is 15 minutes) separate fine particle emulsion, particulate;
Slowly particulate is added in the chromium chloride solution that chromium ion concentration is 200mg/L in stirring down, get mixed liquor; The pH value that uses concentration to regulate mixed liquor as the sodium hydroxide solution of 0.5mol/L then is 4.5, and room temperature reaction 5 hours gets emulsion; Said chromium chloride be in the step 1) shitosan weight 10%.
4), in the emulsion of step 3) gained, to add concentration be the sodium hydroxide solution of 0.5.mol/L, is 6.5 thereby regulate pH value, washes then 5 times (each water consumption equals the volume of step 3) gained emulsion), refilter; Get filter cake.
5), step 4) gained filter cake was dried 24 hours in 60 ℃; Be crushed to then and can cross 300 purposes sieve at least, must carry chromium shitosan meat modifier.
In this year chromium shitosan meat modifier, the mass concentration of chromium chloride and shitosan is respectively: contain chromium chloride and be about for 6% (chrome content is about 2%), shitosan content is about 94%.
Experiment 1, select that 180 body conditions are good, average weight is the DLY tri-crossbreeding of 65kg, be divided into 3 groups at random, every group of 3 repetitions, each repeats 20 pigs (public female half and half).
Experimental group: the feeding daily ration is: year chromium shitosan meat modifier (containing chromium concn is the 0.2mg/kg feed) that in every kg conventional feed, adds 10mg embodiment 1 gained;
Blank control group: the feeding daily ration is: conventional feed;
Contrast groups: the feeding daily ration is: in every kg conventional feed, add 0.6mg chromium chloride and 9.4mg shitosan (that is same experimental group of addition of assurance chromium chloride and shitosan.)
Above-mentioned experimental group, blank control group and contrast groups be free choice feeding and drinking-water under identical raising condition all, 5 days preliminary trial periods, is just trying 35 days phases.Duration of test writes down feed consumption every day.
After feeding experiment finishes, from experimental group, blank control group and contrast groups, respectively choose 12 of the approaching test pig of body weight (public female half and half), totally 36.Freely drink water, fasting 24 hours is weighed, and by conventional method butcher, the mensuration of sampling and physiological and biochemical index.Result of the test shows:
Experimental group is with respect to blank control group: lean meat percentage has improved 8.25% (P<0.05), and the fat percentage and the thickness of backfat reduce by 26.15% (P<0.05) and 10.60% (P<0.05) respectively; The longissimus dorsi muscle myoglobin content improves 7.94% (P<0.05); Subcutaneus adipose tissue fatty acid synthetase activity has reduced by 22.67% (P<0.05); Serum insulin and cortisol levels descended respectively 19.55% (P<0.05), 10.73% (P<0.05); Insulin like growth factor-1 (IGF-I) level has improved 25.35% (P<0.05), and lipase activity and free fatty acid content improve 27.87% (P<0.05), 169.23% (P<0.05) respectively.
Contrast groups is with respect to blank control group: lean meat percentage and fat percentage do not have significant difference, and the thickness of backfat has reduced by 7.25% (P<0.05), and subcutaneus adipose tissue fatty acid synthetase activity has reduced by 12.34% (P<0.05); Serum insulin level 10.25% (P<0.05) that descended, IGF and cortisol levels do not have significant difference, and lipase activity and free fatty acid content do not have significant change yet.
The preparation method of embodiment 2, a kind of year chromium shitosan meat modifier, carry out following steps successively:
1), in 40 ℃, in the acetic acid solution of mass concentration 1%, adding molecular weight is the shitosan of 10kDa, is mixed with the shitosan acid solution, the mass concentration of shitosan in the shitosan acid solution is 3%.
2), adopt the acetic acid solution of mass concentration 1% to regulate the shitosan acid solution, making its pH value is 4.0; Thereby form the particulate emulsion.
3), centrifugation particulate emulsion, particulate;
Slowly particulate is added in the chromium nitrate solution that chromium ion concentration is 400mg/L in stirring down, get mixed liquor; The pH value that uses concentration to regulate mixed liquor as the sodium hydroxide solution of 1mol/L then is 5.5, and room temperature reaction 8 hours gets emulsion; Said chromic nitrate be in the step 1) shitosan weight 20%.
4), in the emulsion of step 3) gained, to add concentration be the sodium hydroxide solution of 1mol/l, is 7.5 thereby regulate pH value, washes then 6 times, refilter; Get filter cake.
5), step 4) gained filter cake was dried 16 hours in 70 ℃; Be crushed to then and can cross 400 purposes sieve at least, must carry chromium shitosan meat modifier.
In this year chromium shitosan meat modifier, the mass concentration of chromic nitrate and shitosan is respectively: contain chromic nitrate and be about for 12% (chrome content is about 1.5%), shitosan content is about 88%.
Experiment 2,
Experimental group: the feeding daily ration is: year chromium shitosan meat modifier (containing chromium concn is the 0.2mg/kg feed) that in every kg conventional feed, adds 13mg embodiment 2 gained;
Blank control group: the feeding daily ration is: conventional feed;
Contrast groups: the feeding daily ration is: in the per kilogram conventional feed, add 1.6mg chromic nitrate and 11.4mg shitosan (that is same experimental group of addition of assurance chromic nitrate and shitosan.)
All the other are with experiment 1.
The result is:
Experimental group is with respect to blank control group: lean meat percentage has improved 5.38% (P<0.05), and the fat percentage and the thickness of backfat reduce by 18.25% (P<0.05) and 11.50% (P<0.05) respectively; Subcutaneus adipose tissue fatty acid synthetase activity has reduced by 25.88% (P<0.05); Serum insulin and cortisol levels descended respectively 23.46% (P<0.05), 15.23% (P<0.05); Insulin like growth factor-1 (IGF-I) level has improved 33.12% (P<0.05), and lipase activity and free fatty acid content improve 21.17% (P<0.05), 123.43% (P<0.05) respectively.
Contrast groups is with respect to blank control group: lean meat percentage and fat percentage do not have significant difference, and the thickness of backfat has reduced by 9.33% (P<0.05), and subcutaneus adipose tissue fatty acid synthetase activity has reduced by 10.42% (P<0.05); Serum insulin level 11.25% (P<0.05) that descended, IGF and cortisol levels do not have significant difference, and lipase activity and free fatty acid content do not have significant change yet.
The preparation method of embodiment 3, a kind of year chromium shitosan meat modifier, carry out following steps successively:
1), in 50 ℃, in the hydrochloric acid solution of mass concentration 2%, adding molecular weight is the shitosan of 80kDa, is mixed with the shitosan acid solution, the mass concentration of shitosan in the shitosan acid solution is 5%.
2), adopt the hydrochloric acid solution of mass concentration 2% to regulate the shitosan acid solution, making its pH value is 4.5; Thereby form the particulate emulsion.
3), centrifugation particulate emulsion, particulate;
Slowly particulate is added in the chromium sulfate solution that chromium ion concentration is 500mg/L in stirring down, get mixed liquor; The pH value that uses concentration to regulate mixed liquor as the sodium hydroxide solution of 2mol/L then is 6, and room temperature reaction 10 hours gets emulsion; Said chromium sulfate be in the step 1) shitosan weight 15%.
4), in the emulsion of step 3) gained, to add concentration be the sodium hydroxide solution of 2mol/L, is 8.5 thereby regulate pH value, washes then 6 times, refilter; Get filter cake.
5), step 4) gained filter cake was dried 26 hours in 50 ℃; Be crushed to then and can cross 500 purposes sieve at least, must carry chromium shitosan meat modifier.
The concentration of chromium sulfate and shitosan is respectively in this year chromium shitosan meat modifier: sulfur acid chromium was about for 11.5% (chrome content is about 3%), and shitosan content is about 88.5%
Experiment 3,
Experimental group: the feeding daily ration is: year chromium shitosan meat modifier (containing chromium concn is the 0.2mg/kg feed) that in every kg conventional feed, adds 6.7mg embodiment 3 gained;
Blank control group: the feeding daily ration is: conventional feed;
Contrast groups: the feeding daily ration is: in the per kilogram conventional feed, add 0.77mg chromium sulfate and 5.93mg shitosan (that is same experimental group of addition of assurance chromium sulfate and shitosan.)
All the other are with experiment 1.
The result is:
Experimental group is with respect to blank control group: lean meat percentage has improved 6.28% (P<0.05), and the fat percentage and the thickness of backfat reduce by 24.33% (P<0.05) and 9.59% (P<0.05) respectively; Subcutaneus adipose tissue fatty acid synthetase activity has reduced by 18.95% (P<0.05); Serum insulin and cortisol levels descended respectively 18.41% (P<0.05), 12.35% (P<0.05); Insulin like growth factor-1 (IGF-I) level has improved 27.52% (P<0.05), and lipase activity and free fatty acid content improve 34.12% (P<0.05), 149.25% (P<0.05) respectively.
And contrast groups is with respect to blank control group: lean meat percentage and fat percentage do not have significant difference, and the thickness of backfat has reduced by 8.33% (P<0.05), and subcutaneus adipose tissue fatty acid synthetase activity has reduced by 15.42% (P<0.05); Serum insulin, IGF and cortisol levels do not have significant difference, and lipase activity and free fatty acid content do not have significant change yet.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.

Claims (6)

1. carry the preparation method of chromium shitosan meat modifier, it is characterized in that may further comprise the steps successively:
1), in 20 ~ 60 ℃, be that 0.1 ~ 5% acid solution adds shitosan in mass concentration, the shitosan acid solution; The mass concentration of said shitosan in the shitosan acid solution is 0.1 ~ 5%;
Said shitosan be deacetylation be 80 ~ 95% and molecular weight be the shitosan of 2 ~ 80kDa;
2), to utilize mass concentration be that 0.1 ~ 5% acid solution is regulated the shitosan acid solution, making its pH value is 3 ~ 5; Thereby form the particulate emulsion;
3), centrifugation particulate emulsion, particulate;
Under stirring condition, particulate is added in the chromium salt solution that chromium ion concentration is 100 ~ 500mg/L, mixed liquor, said chromic salts be in the step 1) shitosan weight 10 ~ 20%; Utilizing concentration then is that the pH value that the alkaline solution of 0.5 ~ 10mol/L is regulated mixed liquor is 4.5 ~ 6.0, room temperature reaction 5 ~ 10 hours, emulsion;
4), in the emulsion of step 3) gained, add concentration be the alkaline solution of 0.5 ~ 10mol/L to regulate pH value be 6.5 ~ 8.5, wash then 3 ~ 7 times, refilter or centrifugal dehydration; Collect solid product;
5), step 4) gained solid product oven dry back is pulverized, must carry chromium shitosan meat modifier.
2. the preparation method of according to claim 1 year chromium shitosan meat modifier is characterized in that: the chromic salts in the said step 3) is chromium chloride, chromic nitrate, chromium sulfate, chromium chloride hydrate, chromic nitrate hydrate or chromium sulfate hydrate.
3. the preparation method of according to claim 2 year chromium shitosan meat modifier is characterized in that: said step 1) and step 2) in acid be acetate or hydrochloric acid.
4. the preparation method of according to claim 3 year chromium shitosan meat modifier is characterized in that: alkali is NaOH, potassium hydroxide, sodium carbonate, potash, sodium acid carbonate or saleratus in said step 3) and the step 4).
5. the preparation method of according to claim 4 year chromium shitosan meat modifier is characterized in that: the bake out temperature of said step 5) is 50 ~ 70 ℃, is crushed to and can crosses 300 purposes sieve at least.
6. the purposes of carrying chromium shitosan meat modifier of utilizing any one method preparation in the claim 1 ~ 5 and getting is characterized in that: as the feed addictive of livestock and poultry or aquatic livestock.
CN2011101674309A 2011-06-20 2011-06-20 Preparation method and application of chromium-carrying chitosan meat quality modifier Expired - Fee Related CN102283319B (en)

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Families Citing this family (3)

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Publication number Priority date Publication date Assignee Title
CN103931900A (en) * 2014-04-22 2014-07-23 无锡正大畜禽有限公司 Functional flavoring agent for feed and preparation method of functional flavoring agent
CN105285441A (en) * 2015-10-26 2016-02-03 张静 High-efficiency meat duck feed based on organic chromium loaded by modified chitosan anions, and with high lean meat percentage, and preparation method of high-efficiency meat duck feed
WO2019051754A1 (en) * 2017-09-14 2019-03-21 南通优元美术图案设计有限公司 Preparation method for new energy material of chitosan chromate

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