CN104530255A - Method for preparing low-methoxy pectin by ultrasonic assisted acid process - Google Patents
Method for preparing low-methoxy pectin by ultrasonic assisted acid process Download PDFInfo
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- CN104530255A CN104530255A CN201410821611.2A CN201410821611A CN104530255A CN 104530255 A CN104530255 A CN 104530255A CN 201410821611 A CN201410821611 A CN 201410821611A CN 104530255 A CN104530255 A CN 104530255A
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- methoxy pectin
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Abstract
The invention discloses a method for preparing low-methoxy pectin by an ultrasonic assisted acid process, which comprises the following steps: 1) dissolving pectin in an acid solution to obtain a pectin solution; 2) carrying out ultrasonic degradation on the pectin solution obtained in the step 1), wherein the ultrasonic intensity is 19-760 W/cm<2>, and the ultrasonic degradation time is 30-150 minutes; 3) regulating the pH value of the substance obtained in the step 2) to 7, and sequentially carrying out ethanol solution precipitation and dialysis; and 4) freeze-drying the dialyzed solution to obtain the low-methoxy pectin. The method can implement energy-saving environment-friendly efficient preparation of the low-methoxy pectin.
Description
Technical field
The present invention relates to a kind of method that ultrasonic wave added acid system prepares low-methoxy pectin.
Background technology
Pectin is generally divided into high methoxyl pectin (high methoxy pectin, HMP) and the large class of low-methoxy pectin (low memoxylpectin, LMP) two.High methoxyl pectin generally refers to gamma value (Degree of Esterification or Degree ofmethoxylation, also known as DE value or DM value, be in pectin on each hundred galacturonic acid residues C6 position with esterification form exist per-cent) be greater than 50%, namely methoxy content higher than 7% pectin; Common low-methoxy pectin refers to that gamma value is less than 50%, between 25% ~ 50%, namely methoxy content lower than 7% pectin.LM-pectin, be not exclusively subject to the restriction of pH value and pol (altogether molten thing), it requires low to gelation condition.As long as have enough high volence metal ions as calcium ion combines with it can gel.Therefore, LM-pectin is meeting people to quite outstanding in low sugar, low in calories, low sugariness food requirement.In recent years, the quantity of diabetic subject is in rising trend, and fat-reducing becomes a kind of fashion, and its diet has just had special requirement.The various low sugar health care food that businessman develops for this feature, when selection glue, LM-pectin just shows its unrivaled advantage.
The method for making of LM-pectin mainly contains acidic ethanol method, alkalization method, amidation method, enzyme method, Physical etc.Acidic ethanol method is exactly the water soluble pectin of gained after pre-treatment, acidolysis is added acidic ethanol (keeping 6-10h at 30 DEG C, carrying out de-ester conversion, obtain LM-pectin.Acidic ethanol method reaction conditions is gentle, and the low shortcoming of pectin molecule chain degradation degree is that technique is more complicated, and de-ester conditional request is extremely strict.Alkalization method, Britain scientific research personnel uses alkali (generally using sodium carbonate) to do experiment recently, processes orange skin, bitter orange meat and mangrove bark respectively.Sample is scatter in 50 ml distilled waters, adds 0.5g Na
2cO
3, and under 25 DEG C of conditions, process 60 minutes, test-results represents: sample (no matter dried food and nuts or freezing goods) treated gained pectin is LM-pectin.Base catalysed de-esterification simple process, security is high and cost is lower, but β-elimination reaction can occur pectin molecule, and structure can depolymerization simultaneously, and pectin molecule amount is reduced.Amidated pectins is a kind of LM-pectin, and it uses ammonia treatment in the basic conditions, the product after making part methyl esters change primary alconol amine into.Its DE (Degree of methoxylation) usually in 20-45%, DA (Degree of amidation) value at 12-25%.Advantage is technique low power consuming and low stain, and product gamma value is low and gelation good; Shortcoming is that technique is extremely complicated, and product is soluble and may contain harmful side product.Enzyme process is prepared LM-pectin and is divided into endogenous enzyme effect to prepare LM-pectin, and additional enzyme prepares LM-pectin.It is exactly prepare the method for LM-pectin by adding endogenous enzyme activator activation Rohapect MPE PE that LM-pectin is prepared in endogenous enzyme effect.Additional enzyme is prepared low-ester pectin and from plant tissue or microorganism (mainly aspergillus niger) fermented liquid, is extracted PE exactly, recycles this Rohapect MPE production LM-pectin.Advantage is that molecular weight of product is higher, and reaction substrate has specificity; Shortcoming is that product gel-strength is low, and modification mode is confined to disconnect methyl esters key and glycosidic link.
Above-mentioned often kind of preparation method has its relative merits, all cannot meet the requirement preparing low-methoxy pectin of energy-saving, environment-friendly and high-efficiency simultaneously.
Although there is the report of ultrasonic degradation pectin at present, to utilizing ultrasonic wave to prepare low-methoxy pectin, particularly controlled synthesis aspect has no report.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method that ultrasonic wave added acid system prepares low-methoxy pectin, and what adopt the method can realize energy-saving, environment-friendly and high-efficiency prepares low-methoxy pectin.
In order to solve the problems of the technologies described above, the invention provides a kind of method that ultrasonic wave added acid system prepares low-methoxy pectin, comprising the following steps:
1), by pectin be dissolved in acid solution, obtain pectin solution;
2), by step 1) the pectin solution ultrasonication of gained; Ultrasonic intensity is 19W/cm
2(amplitude 2%) ~ 760W/cm
2(amplitude 80%), the time of supersound process is 30 ~ 150min;
Remarks illustrate: better ultrasonic intensity is 95W/cm
2(amplitude 10%) ~ 475W/cm
2(amplitude 50%);
3), step 2) gains first regulate pH to 7, then carry out ethanolic soln precipitation, dialysis successively;
4), the freeze-drying of dialysis gained solution, obtain low-methoxy pectin (pectin after degraded).
The improvement of the method for low-methoxy pectin is prepared as ultrasonic wave added acid system of the present invention:
In order to accelerate step 1) in the dissolution rate of pectin, first by moistening for pectin ethanol, and then add acid solution and dissolve, obtain pectin solution.
Generally speaking, every 0.5g pectin ethanol of 2 ~ 4ml carries out moistening.
The further improvements in methods of low-methoxy pectin are prepared as ultrasonic wave added acid system of the present invention:
Described step 1) in, the HCl solution of acid solution to be volumetric molar concentration be 0.05 ~ 0.15mol/L (being such as 0.1mol/L); The HCl solution of every 0.2 ~ 0.8g (preferably 0.2 ~ 0.5g) pectin adapted 100mL.
Prepare the further improvements in methods of low-methoxy pectin as ultrasonic wave added acid system of the present invention: step 3) ethanolic soln in the mass concentration of ethanol be 20% ~ 80%.
The further improvements in methods of low-methoxy pectin are prepared: step 3 as ultrasonic wave added acid system of the present invention) in, utilize NaOH to carry out the adjustment (that is, being neutralized to pH=7) of pH.
The further improvements in methods of low-methoxy pectin are prepared: the esterification degree of the low-methoxy pectin of gained is 20% ~ 35% as ultrasonic wave added acid system of the present invention.
In step 2 of the present invention) in: ultrasonic frequency 20kHz, probe diameter 13mm, 1cm under probe insertion liquid level, liquid level keeps 3cm, and temperature is set to 25 DEG C, and the burst length is 2s, intermittent time 2s.
In step 3 of the present invention) in: generally speaking, the ethanolic soln of every 0.5g pectin (step 1) adapted 80 ~ 120ml precipitates, sedimentation time is 30 ~ 60min, and dialysis time is 40 ~ 50h, dialysis membrane used be only allow molecular weight be less than 10,000 molecule pass through.
In step 4 of the present invention) in: in-35 ~-45 DEG C of freeze-drying 30 ~ 40h.
Method of the present invention has the following advantages:
1, ultrasonic wave added provided by the present invention prepares the acid solution selected by low-methoxy pectin is hydrochloric acid, after acid hydrolysis, removes hydrochloric acid by dialysis method, can avoid the reaction reagent introducing other after degrading, aftertreatment is simplified;
2, ultrasonic wave added provided by the present invention prepares low-methoxy pectin, solves pectic acid and prepares low-methoxy pectin and need high temperature to assist and the energy consumption issues caused, meet environmental requirement, for suitability for industrialized production provides new thinking.
In sum, the present invention's ultrasonic wave added prepares low-methoxy pectin, utilizes synergy between the two, solves the problem that acid system needs owing to adding strong acid to complete under high temperature is assisted, both complete the object that low-methoxyl prepares pectin, reach again the effect of energy-conserving and environment-protective.
Every test experience involved in the present invention is specific as follows:
The gamma value of former commodity pectin is quantitatively surveyed in experiment 1, volumetry:
Get 0.2g pectin, a small amount of ethanol wet, add 20ml distilled water 40 DEG C and stir 2h, add a phenolphthalein, 0.1mol/L NaOH is titrated to terminal and consumes NaOH volume V
1.Add 10mL NaOH stirring at room temperature 2h, then add 10mL HCl, consume NaOH volume V by 0.1mol/LNaOH titration end point
2.Calculation formula gamma value (%)=100 × V
2/ (V
1+ V
2).
Record the esterification degree DE%=78.1% of former commodity pectin.
The gamma value of pectin sample is quantitatively surveyed in experiment 2, fourier transform infrared spectroscopy:
Pectin is tested sample drying, under vacuum condition, grinds to form powdery.Get 4mg respectively, KBr grinds compressing tablet, adopts NicoletNexus FTIR in 4000 ~ 400cm
-1scope interscan.Scan 32 times, resolving power is 4cm
-1.The cardinal principle that fourier transform infrared spectroscopy measures gamma value is that the carboxyl of uronic acid in infrared spectrum is at 1613cm
-1there is absorption peak at place, and the carboxyl of esterification is at 1745cm
-1there is absorption peak at place, and absorption peak area is directly proportional to group numbers.Pectinesterase degree refers to carboxyl number/carboxylic group sum × 100% of esterification, therefore uses formula DE=A
1745(A
1613+ A
1745) (A
1613, A
1745represent 1613cm respectively
-1and 1745cm
-1the area of place's absorption peak).Arrive result as shown in the figure.
The gamma value of pectin sample is quantitatively surveyed in experiment 3, high performance liquid chromatography (HPLC):
A is measured under 530nm wavelength
530value draws the typical curve of galacturonic acid.Then the A of pectin sample is measured
530value and standard specimen compare the concentration obtaining galacturonic acid in sample, calculate the content of galacturonic acid according to concentration.Calculation formula: Gal A (%)=C
1/ C
2× 100, GalA (%) is galacturonic acid content, C
1for the galacturonic acid concentration checked in from typical curve, C
2for concentration of pectin.
Utilize high performance liquid chromatograph, with Virahol (IPA) for interior mark, be calculated as follows the response factor FR of methyl alcohol (MeOH), then calculate the esterification degree (DE) of pectin respectively.FR＝(M
MeOH or AcOH/M
IPA)(A
MeOH or AcOH/A
IPA)；DE＝FR(A
MeOH/A
IPA)(M
sample/A
IPA)(176×10
4/(GalA％×32)。When calculating FR: M
meOH or iPAbe respectively the quality of MeOH, IPA in mixed mark; A
meOH or iPAbe respectively the peak area of MeOH, IPA in mixed mark; When calculating DE: M
meOH or iPAbe respectively the quality of sample MeOH, IPA; A
meOH or iPAbe respectively the content of the peak area GalA%-galacturonic acid of MeOH, IPA in sample.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is the infared spectrum of ultrasonic degradation pectin.
Fig. 2 is the infared spectrum of ultrasonic wave added acid degradation pectin;
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail:
Embodiment 1, a kind of ultrasonic wave added acid system prepare the method for low-methoxy pectin, carry out following steps successively:
Get 0.5g pectin, moistening with a small amount of (2 ~ 3ml) ethanol, be dissolved in 100mL 0.1mol/L HCl, ultrasonic frequency 20kHz, probe diameter 13mm, 1cm under probe insertion liquid level, liquid level keeps 3cm, and temperature is set to 25 DEG C, burst length is 2s, intermittent time 2s, the treatment time 30min, 150min, ultrasonic intensity 285W/cm
2(amplitude 30%); Then NaOH is neutralized to pH 7.0, with 50% (quality %) alcohol settling 30min of 100ml, dialysis 48h, dialysis membrane used be only allow molecular weight be less than 10,000 molecule pass through, the solution of dialysing is obtained solid sample in-40 DEG C of freeze-drying 36h for subsequent use.
Experimentally described in 2, method detects: it is effective for qualitatively can obtaining this preparation method.Result as shown in Figure 2.
Experimentally 3 methods detect: when ultrasonic wave added acid system prepares low-methoxy pectin 30min, and methyl-esterification degree is DE
1(%)=39.9%; When ultrasonic wave added acid system prepares low-methoxy pectin 150min, methyl-esterification degree is DE
2(%)=29.28%.
Embodiment 2, by the ultrasonic intensity 285W/cm in embodiment 1
2(amplitude 30%) makes ultrasonic intensity 95W/cm respectively into
2(amplitude 10%), ultrasonic intensity 475W/cm
2(amplitude 50%), will make 90min in the treatment time; All the other are equal to embodiment 1.
The gamma value detected result of the pectin of final gained is as follows:
Experimentally described in 3, method detects: time ultrasonic intensity 95W/cm2 (amplitude 10%), ultrasonic wave added acid system prepare low-methoxy pectin 90min methyl-esterification degree be DE
3(%)=40.56%; Time ultrasonic intensity 475W/cm2 (amplitude 50%), ultrasonic wave added acid system prepare low-methoxy pectin 90min methyl-esterification degree be DE
4(%)=25.20%.
Comparative example 1, ultrasonic wave prepare low-methoxy pectin group
Get 0.5g pectin, (2 ~ 3ml) ethanol that takes a morsel is moistening, is dissolved in 100mL distilled water, ultrasonic frequency 20kHz, probe diameter 13mm, 1cm under probe insertion liquid level, liquid level keeps 3cm, and temperature is set to 25 DEG C, burst length is 2s, intermittent time 2s, treatment time 90min, ultrasonic intensity 95,475W/cm
2(amplitude 10%, 50%).50% (quality %) alcohol settling 30min of 100ml is added in above-mentioned ultrasonic gained solution, dialysis 48h, dialysis membrane used be only allow molecular weight be less than 10,000 molecule pass through, the solution of dialysing is obtained solid sample in-40 DEG C of freeze-drying 36h for subsequent use.
Experimentally 2 methods, it is effective for qualitatively can obtaining this preparation method.As shown in Figure 1.
Experimentally 3 methods record, ultrasonic intensity 95W/cm
2the methyl-esterification degree that (amplitude 10%) prepares low-methoxy pectin is: DE
5(%)=44.55%;
Experimentally 3 methods record, ultrasonic intensity 475W/cm
2the methyl-esterification degree that (amplitude 50%) prepares low-methoxy pectin is: DE
6(%)=32.56%.
Comparative example 2, acid system prepare low-methoxy pectin group (control temperature)
Get 0.5g pectin, moistening with a small amount of (2 ~ 3ml) ethanol, be dissolved in 100mL 0.1mol/L HCl, be placed in 70 DEG C and 90 DEG C of water-bath 3h respectively.Subsequent disposal is equal to embodiment 1.
Experimentally described in 3, method records: at 70 DEG C, acid system prepares the esterification degree DE of low-methoxy pectin
7(%)=38.74%; At 90 DEG C, acid system prepares the esterification degree of low-methoxy pectin is DE
8(%)=30.06%.
Although acid system prepares low-methoxy pectin group also certain effect, power consumption very large (needing the long-time water-bath of high temperature).
Comparative example 3, acid system prepare low-methoxy pectin group (control acid concentration)
Get 0.5g pectin, moistening with a small amount of (2 ~ 3ml) ethanol, be dissolved in 100mL 0.1mol/L HCl or 0.001mol/L HCl, be placed in 80 DEG C of water-bath 3h.Subsequent disposal is equal to embodiment 1.
Experimentally described in 3, method records: 0.1mol/L HCl prepares the esterification degree DE of pectin
9(%)=36.52%; The esterification degree that 0.001mol/L HCl prepares pectin is DE
10(%)=43.23%.
Although acid system prepares low-methoxy pectin group also certain effect, power consumption very large (needing the long-time water-bath of high temperature).
Finally, it is also to be noted that what enumerate above is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (6)
1. ultrasonic wave added acid system prepares the method for low-methoxy pectin, it is characterized in that comprising the following steps:
1), by pectin be dissolved in acid solution, obtain pectin solution;
2), by step 1) the pectin solution ultrasonic degradation of gained; Ultrasonic intensity is 19W/cm
2~ 760W/cm
2, the time of ultrasonic degradation is 30 ~ 150min;
3), step 2) gains first regulate pH to 7, then carry out ethanolic soln precipitation, dialysis successively;
4), the freeze-drying of dialysis gained solution, obtain low-methoxy pectin.
2. ultrasonic wave added acid system according to claim 1 prepares the method for low-methoxy pectin, it is characterized in that:
In order to accelerate step 1) in the dissolution rate of pectin, first by moistening for pectin ethanol, and then add acid solution and dissolve, obtain pectin solution.
3. ultrasonic wave added acid system according to claim 1 and 2 prepares the method for low-methoxy pectin, it is characterized in that:
Described step 1) in, the HCl solution of acid solution to be volumetric molar concentration be 0.05 ~ 0.15mol/L; The HCl solution of every 0.2 ~ 0.8g pectin adapted 100mL.
4. ultrasonic wave added acid system according to claim 3 prepares the method for low-methoxy pectin, it is characterized in that: described step 3) ethanolic soln in the mass concentration of ethanol be 20% ~ 80%.
5. ultrasonic wave added acid system according to claim 4 prepares the method for low-methoxy pectin, it is characterized in that: described step 3) in, utilize NaOH to carry out the adjustment of pH.
6. prepare the method for low-methoxy pectin according to the arbitrary described ultrasonic wave added acid system of Claims 1 to 5, it is characterized in that: the esterification degree of the low-methoxy pectin of gained is 20% ~ 35%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104877861A (en) * | 2015-05-29 | 2015-09-02 | 河北农业大学 | Red date brandy extracting and preparing method |
| CN106866839A (en) * | 2017-03-13 | 2017-06-20 | 浙江大学 | The method that ultrasonic hot acid method extracts LM in Hu shaddock ped |
| CN106893001A (en) * | 2017-02-22 | 2017-06-27 | 浙江大学 | A kind of preparation method of the Ultra-low molecular weight pectin rich in RG I |
-
2014
- 2014-12-25 CN CN201410821611.2A patent/CN104530255A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104877861A (en) * | 2015-05-29 | 2015-09-02 | 河北农业大学 | Red date brandy extracting and preparing method |
| CN106893001A (en) * | 2017-02-22 | 2017-06-27 | 浙江大学 | A kind of preparation method of the Ultra-low molecular weight pectin rich in RG I |
| CN106893001B (en) * | 2017-02-22 | 2019-08-09 | 浙江大学 | A kind of preparation method of the Ultra-low molecular weight pectin rich in RG-I |
| CN106866839A (en) * | 2017-03-13 | 2017-06-20 | 浙江大学 | The method that ultrasonic hot acid method extracts LM in Hu shaddock ped |
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Application publication date: 20150422 |