阅读说明：本技术 一种远红外线辅助多糖高效水解装置及方法 (Far infrared ray-assisted polysaccharide efficient hydrolysis device and method ) 是由 陈刚 梁培培 路滨宇 张鲁雁 于 2019-10-16 设计创作，主要内容包括：本发明属多糖结构分析技术领域,具体为一种远红外线辅助多糖高效水解装置及方法。本发明将远红外线发生器、回流冷凝管、水解容器和调压器组装成多糖水解装置,多糖溶于含挥发性酸的水溶液中后,于水解容器中进行远红外辅助水解,水解完毕抽去挥发性酸可用于后续单糖色谱分析。由于多糖和溶液分子强烈吸收远红外线,加速了多糖分子振动以及与酸性水溶液的作用,显著提高了多糖水解效率。本发明用远红外线辐射非接触加热技术代替传统多糖水解中使用的水浴,多糖水解时间从水浴加热水解的数小时大幅缩短到15分钟以内,而水解效果得到明显提高。远红外线辅助多糖高效水解方法具有设备简单、能耗低和操作简便的优点,在多糖结构分析技术中有良好的应用前景。(The invention belongs to the technical field of polysaccharide structure analysis, and particularly relates to a far infrared ray-assisted polysaccharide efficient hydrolysis device and a far infrared ray-assisted polysaccharide efficient hydrolysis method. The far infrared generator, reflux condenser tube, hydrolysis container and pressure regulator are assembled into polysaccharide hydrolyzing device, after polysaccharide is dissolved in water solution containing volatile acid, far infrared assisted hydrolysis is carried out in the hydrolysis container, after hydrolysis, volatile acid is extracted for subsequent monosaccharide chromatographic analysis. Because polysaccharide and solution molecules strongly absorb far infrared rays, the vibration of the polysaccharide molecules and the action of the polysaccharide molecules and an acidic aqueous solution are accelerated, and the hydrolysis efficiency of the polysaccharide is obviously improved. The invention uses far infrared radiation non-contact heating technology to replace the water bath used in the traditional polysaccharide hydrolysis, the polysaccharide hydrolysis time is greatly shortened to within 15 minutes from several hours of the water bath heating hydrolysis, and the hydrolysis effect is obviously improved. The far infrared ray-assisted polysaccharide efficient hydrolysis method has the advantages of simple equipment, low energy consumption and simple and convenient operation, and has good application prospect in the polysaccharide structure analysis technology.)

1. The utility model provides a high-efficient hydrolysis unit of polysaccharide is assisted to far infrared which characterized in that includes: a reflux condenser pipe, a hydrolysis container, a far infrared generator and a pressure regulator; the reflux condenser pipe and the hydrolysis container are respectively fixed on a vertical bracket through clamps, and the lower end of the reflux condenser pipe is connected with the upper opening of the hydrolysis container; the upper part of the reflux condenser pipe is provided with a water outlet, and the lower part of the reflux condenser pipe is provided with a water inlet for introducing cooling water; the hydrolysis container is used for containing an acidic aqueous solution of polysaccharide; the far infrared generator is placed on an iron support and positioned below the hydrolysis container and is used for carrying out far infrared radiation heating on the solution in the hydrolysis container; the lower end of the bracket is fixed on the iron support; the voltage regulator is connected with the far infrared generator and used for regulating the output power and the emitted infrared intensity of the far infrared generator of the voltage regulator and controlling the hydrolysis speed and degree of the polysaccharide by controlling the input voltage of the far infrared generator.

2. The far infrared ray-assisted polysaccharide high-efficiency hydrolysis device as claimed in claim 1, wherein the far infrared ray generator is a far infrared heating wire, a far infrared carbon fiber electric heating tube, an infrared lamp or a halogen infrared electric heating tube.

3. The far infrared ray-assisted polysaccharide high-efficiency hydrolysis device as claimed in claim 1, wherein the reflux condenser tube is a glass reflux condenser tube, a glass serpentine condenser tube, a glass straight condenser tube or a stainless steel condenser tube.

4. The far infrared ray-assisted polysaccharide high-efficiency hydrolysis device as claimed in claim 1, wherein the hydrolysis container is a round-bottom glass flask or a pear-shaped glass flask.

5. The device for hydrolyzing polysaccharide with far infrared ray assistance as claimed in claim 1, wherein the voltage regulator has an alternating current input voltage of 220V and an output voltage of 0-220V.

6. The method for efficiently hydrolyzing far infrared ray-assisted polysaccharide by using the apparatus for efficiently hydrolyzing far infrared ray-assisted polysaccharide according to any one of claims 1 to 5 comprises the following steps:

(1) dissolving a polysaccharide sample in an aqueous solution containing an acid catalyst, and placing the polysaccharide sample in a hydrolysis container of a far infrared auxiliary polysaccharide efficient hydrolysis device;

(2) introducing cooling water into the reflux condensing device, then turning on a power supply of a voltage regulator, setting the output voltage of the voltage regulator to be 20-220V, and applying the voltage regulator on a far infrared generator at the lower part of the hydrolysis container to carry out far infrared assisted hydrolysis;

the far infrared rays emitted by the far infrared ray generator are absorbed by the polysaccharide sample and the solution molecules, so that the vibration of the polysaccharide molecules and the action of the polysaccharide molecules and the acidic aqueous solution are accelerated, and the polysaccharide hydrolysis efficiency is obviously improved;

(3) the polysaccharide hydrolysis solution was collected and the volatile acids were removed under reduced pressure for subsequent chromatographic analysis of the monosaccharides.

7. The method for hydrolyzing polysaccharide with far infrared ray as assistant of claim 6, wherein the acid catalyst for hydrolyzing polysaccharide with far infrared ray as assistant is non-oxidizing volatile acid selected from trifluoroacetic acid, hydrochloric acid, formic acid, and trichloroacetic acid.

8. The method for hydrolyzing polysaccharide with high efficiency by far infrared ray as claimed in claim 6, wherein the concentration of the acid catalyst in step (1) is 1 to 6 mol/l, and the concentration of polysaccharide in the acidic aqueous solution is 0.1 to 10 mg/ml.

Technical Field

The invention belongs to the technical field of polysaccharide structure analysis, and particularly relates to a far infrared ray-assisted polysaccharide efficient hydrolysis device and method.

Background

Any sugar that can be hydrolyzed into multiple monosaccharide molecules or derivatives thereof is a polysaccharide. It is a macromolecular compound formed by condensing and dehydrating twenty to ten thousand monosaccharide molecules. Polysaccharides can be prepared by condensing a monosaccharide, such as starch, cellulose, etc., and are called homopolysaccharides; they may also be made up of different monosaccharides or their derivatives by condensation, for example, hemicellulose, which is called heteropolysaccharide. Polysaccharides are biopolymers with the most abundant content in nature, exist in almost all organisms, have various biological functions such as energy storage, structural support, defense function and antigen decisive function, and not only are important nutrients, but also some polysaccharides or derivatives thereof have various pharmacological activities such as anti-tumor, anti-virus, anti-aging, blood sugar reduction, blood fat reduction and the like, so that the polysaccharides have become a hot spot of natural medicine research in recent years.

The polysaccharide structure analysis technique requires knowledge of the monosaccharide composition of the polysaccharide and structural information such as the relative proportions of the monosaccharides. The traditional method is to mix the extracted polysaccharide with aqueous solutions of trifluoroacetic acid, hydrochloric acid, sulfuric acid, etc., and hydrolyze in a water bath at approximately 100 ℃ for more than 6 hours. The method has long hydrolysis time, high energy consumption and incomplete hydrolysis.

Infrared is an invisible electromagnetic wave having a wavelength of 0.76 to 1000 micrometers, and is widely present in sunlight. According to the difference of the wavelength, the infrared light can be divided into three wave bands of near infrared (0.76-1.40 micrometers), intermediate infrared (1.40-3.00 micrometers) and far infrared (3.00-1000 micrometers). The heat generating effect of far infrared radiation irradiating the object is greatly superior to that of near infrared radiation, because the wavelength of absorption spectrum of water and organic matter is mostly in the range of 3-100 micrometers, and is in the same range with the wavelength of far infrared ray, the absorption of far infrared ray is very strong, so that the far infrared radiation is very suitable for being used as a heating source. At present, far infrared radiation heating technology is widely used in the fields of household heaters, grain drying, paint drying, medical care and the like. However, the research on domestic and foreign documents and patents does not find the report of the far infrared ray assisted polysaccharide high-efficiency hydrolysis technology.

The far infrared ray has radiation energy spectrum distribution matched with the infrared absorption spectrum of the polysaccharide, the water and the acid catalyst, most of the radiation energy is absorbed by the hydrolysis system, the vibration of polysaccharide molecules and the action of the polysaccharide molecules and the acid aqueous solution are accelerated, and the polysaccharide hydrolysis efficiency can be greatly improved. Because of the strong penetrating power of far infrared rays, the heating of the acidic hydrolysis solution containing polysaccharide is different from the traditional surface heating, but the acidic hydrolysis solution containing polysaccharide is synchronously heated from inside to outside in a three-dimensional way, and the efficiency is higher. In addition, the far infrared heating has no thermal inertia, can start working in a short time, has high heating speed, can stop working in a short time, and is easy to control.

In view of the advantages of far infrared heating, the far infrared radiation source, the reflux condensing device, the hydrolysis container and the pressure regulator are assembled into the far infrared radiation-assisted polysaccharide hydrolysis system, intensive research is carried out, the far infrared-assisted polysaccharide efficient hydrolysis technology is successfully established, the polysaccharide hydrolysis time is greatly shortened to within 15 minutes from more than 6 hours of water bath heating hydrolysis, and the hydrolysis effect is obviously improved. The far infrared ray-assisted polysaccharide efficient hydrolysis method has the advantages of simple equipment, low energy consumption and simple and convenient operation, and has good application prospect in the polysaccharide structure analysis technology.

Disclosure of Invention

The invention aims to provide a far infrared ray-assisted polysaccharide hydrolysis device and a far infrared ray-assisted polysaccharide hydrolysis method, which can greatly improve the polysaccharide hydrolysis efficiency.

The structure of the far infrared ray-assisted polysaccharide high-efficiency hydrolysis device provided by the invention is shown in figure 1. It includes: a reflux condenser pipe, a hydrolysis container, a far infrared generator (also called as a far infrared radiation source) and a pressure regulator; the reflux condenser pipe and the hydrolysis container are respectively fixed on a vertical bracket through clamps, and the lower end of the reflux condenser pipe is connected with the upper opening of the hydrolysis container; the upper part of the reflux condenser pipe is provided with a water outlet, and the lower part of the reflux condenser pipe is provided with a water inlet for introducing cooling water; the hydrolysis container is used for containing an acidic aqueous solution of polysaccharide; the far infrared generator is placed on an iron support and positioned below the hydrolysis container and is used for carrying out far infrared radiation heating on the hydrolysis container; the lower end of the bracket is fixed on the iron support; the voltage regulator is connected with the far infrared generator and used for regulating the output power and the emitted infrared intensity of the far infrared generator of the voltage regulator, and the hydrolysis speed and degree of the polysaccharide can be controlled by controlling the input voltage of the far infrared generator.

In the invention, the far infrared generator can be a far infrared heating wire, a far infrared carbon fiber electric heating tube, an infrared lamp, a halogen infrared electric heating tube and the like.

In the invention, the reflux condenser pipe can be a glass reflux condenser pipe, a glass snake-shaped condenser pipe, a glass straight condenser pipe and a stainless steel condenser pipe column.

In the invention, the hydrolysis container can be a round-bottom glass flask and a pear-shaped glass flask.

In the invention, the alternating current input voltage of the voltage regulator is 220 volts, and the output voltage is 0-220 volts.

In the invention, the voltage regulator is actually an adjustable transformer, 220V alternating current is supplied to the inner coil, the outer coil and the inner coil have the same number of turns and are wound on the iron core formed by the same silicon steel sheet. One end of the external coil is a fixed output end, the outer side of the external coil is provided with a circle of exposed layers, a rotatable carbon brush connected with a wire is in contact with the exposed layers to form an adjustable output end capable of adjusting output voltage, and the output voltage can be set to be 0-220V through rotating the carbon brush.

The invention provides a far infrared ray-assisted polysaccharide efficient hydrolysis method, which uses the far infrared ray-assisted polysaccharide efficient hydrolysis device and comprises the following specific steps:

(1) dissolving a polysaccharide sample in an aqueous solution containing an acid catalyst, and placing the polysaccharide sample in a hydrolysis container of a far infrared auxiliary polysaccharide efficient hydrolysis device;

(2) introducing cooling water into the reflux condensing device, then turning on a power supply of a voltage regulator, setting the output voltage of the voltage regulator to be 20-220V, and applying the voltage regulator on a far infrared generator at the lower part of the hydrolysis container to carry out far infrared assisted hydrolysis;

the far infrared rays emitted by the far infrared ray generator are absorbed by the polysaccharide sample and the solution molecules, so that the vibration of the polysaccharide molecules and the action of the polysaccharide molecules and the acidic aqueous solution are accelerated, and the polysaccharide hydrolysis efficiency is obviously improved;

(3) collecting polysaccharide hydrolysis solution, removing volatile acid under reduced pressure, and performing chromatographic analysis on monosaccharide.

In the step (1) of the invention, the acid catalyst for far-infrared assisted hydrolysis of polysaccharide is non-oxidative volatile acid, such as trifluoroacetic acid, hydrochloric acid, formic acid, trichloroacetic acid and the like, and can be removed from polysaccharide hydrolysate by reduced pressure distillation, so that interference on subsequent chromatographic analysis is eliminated.

In step (2) of the present invention, the concentration of the acid catalyst is 1 to 6 mol/l, and the concentration of the polysaccharide in the acidic aqueous solution is 0.1 to 10 mg/ml.

The far infrared ray assisted polysaccharide efficient hydrolysis method provided by the invention is further detailed as follows:

(1) assembly of far infrared auxiliary polysaccharide efficient hydrolysis device

The far infrared generator 6 can be a far infrared heating wire, a far infrared carbon fiber electric heating tube, an infrared lamp, a halogen infrared electric heating tube and the like; the reflux condenser pipe 1 can be a glass reflux condenser pipe, a glass snake-shaped condenser pipe and a stainless steel condenser pipe column; the hydrolysis container 6 can be a round-bottom glass flask and a pear-shaped glass flask, when the polysaccharide hydrolysis solution is more, the round-bottom glass flask can be used, when the polysaccharide hydrolysis solution is less, the pear-shaped glass flask can be used, and the hydrolysis solution is concentrated at the conical part at the bottom of the pear-shaped glass flask, so that the hydrolysis solution is convenient to collect;

(2) selection of acid catalyst for far-infrared assisted hydrolysis of polysaccharide

The polysaccharide far infrared auxiliary hydrolysis uses an acidic catalyst for hydrolysis, and can be volatile acids without oxidability, such as trifluoroacetic acid, hydrochloric acid, formic acid, trichloroacetic acid and the like, wherein the hydrochloric acid and the formic acid are low in price, and the trichloroacetic acid and the trifluoroacetic acid are high in price; however, it is not possible to hydrolyze polysaccharides with an oxidizing acid such as nitric acid, and the concentration of the acid used is usually 1 to 6 mol/l because it oxidizes polysaccharides and monosaccharides produced by hydrolysis; non-volatile sulfuric acid can be used for polysaccharide hydrolysis, but barium carbonate needs to be added into hydrolysate and sulfate radicals need to be removed by filtration, so that the operation is complex and the use is not recommended;

(3) preparation of polysaccharides

The extracted polysaccharide sample can be directly dissolved in the water solution of the non-oxidizing volatile acid with a certain concentration for far infrared assisted hydrolysis, and the concentration of the polysaccharide in the acid water solution is usually 0.1-10 mg/ml; drying plant samples rich in polysaccharide such as Chinese medicinal materials in an oven at 40-70 deg.C for 1-5 hr, pulverizing, defatting with organic solvent such as n-hexane, extracting with water under heating, adding ethanol to the extractive solution to obtain crude polysaccharide, centrifuging, drying, removing protein with protease, and purifying with gel column to obtain refined polysaccharides with different molecular weights;

(4) polysaccharide far infrared auxiliary high-efficiency hydrolysis

Dissolving a polysaccharide sample in the aqueous solution of the volatile acid, placing the polysaccharide sample in a hydrolysis container 6 of a far infrared auxiliary polysaccharide efficient hydrolysis device, introducing cooling water into a reflux condensation pipe 1, and starting a far infrared generator 9 at the lower part of the hydrolysis container 6 to carry out far infrared auxiliary hydrolysis; after the emitted far infrared rays 8 are absorbed by the acidic solution 7 containing the polysaccharide sample, the vibration of polysaccharide molecules and the action of the polysaccharide molecules and the acidic aqueous solution are accelerated, and the polysaccharide hydrolysis efficiency is obviously improved; the distance between the bottom of the hydrolysis container 6 and the far infrared generator 9 is 5-50 mm, the output power and the emitted infrared intensity of the far infrared generator 9 are adjusted by a voltage regulator 11, the alternating current input voltage of the voltage regulator 11 is 220V, and the output voltage is 0-220V; the speed and degree of the polysaccharide far infrared auxiliary hydrolysis can be controlled by controlling the hydrolysis time and the input voltage of the far infrared radiation source 9;

(5) deacidification and drying of polysaccharide hydrolysates

The polysaccharide hydrolysate obtained by the far infrared assisted hydrolysis of the invention contains volatile acid and water, and can be removed by a reduced pressure distillation method so as to eliminate the interference on the chromatographic analysis of monosaccharide in the subsequent hydrolysate.

The invention uses far infrared radiation non-contact heating technology to replace the water bath used in the traditional polysaccharide hydrolysis, the polysaccharide hydrolysis time is greatly shortened to within 15 minutes from several hours of the water bath heating hydrolysis, and the hydrolysis effect is obviously improved. The far infrared ray-assisted polysaccharide efficient hydrolysis method has the advantages of simple equipment, low energy consumption and simple and convenient operation, and has good application prospect in the polysaccharide structure analysis technology.

Drawings

FIG. 1 is a schematic view of a device for hydrolyzing polysaccharide efficiently by far infrared ray in the present invention.

FIG. 2 is a capillary electrophoresis pattern of a mixed solution of galactose (a), glucose (b) and mannose (c) standards (1 mM). And (3) testing conditions are as follows: the separation voltage is + 9000V, the sample injection time is 6 seconds, the electrophoresis separation solution is 75 millimole/liter NaOH solution, the detection electrode is a copper disc electrode with the diameter of 300 micrometers, and the detection potential is + 0.65V (relative to a saturated calomel electrode).

FIG. 3 is a capillary electrophoresis chart of a hydrolysate obtained by far infrared ray-assisted hydrolysis of 3 mg of Cordyceps sinensis polysaccharide in 3 ml of 2 mol/L trifluoroacetic acid aqueous solution. Hydrolysis time: (A) 7.5 minutes; (B) for 15 minutes.

FIG. 4 is a capillary electrophoresis chart of a hydrolysate obtained by heating and hydrolyzing 3 mg of Cordyceps sinensis polysaccharide in 3 ml of 2 mol/L trifluoroacetic acid aqueous solution in a water bath at 100 ℃. Hydrolysis time: (A) 180 minutes; (B) for 360 minutes.

FIG. 5 shows the effect of far infrared ray assisted hydrolysis time of 3 mg Cordyceps sinensis polysaccharide in 3 ml of 2 mol/L trifluoroacetic acid aqueous solution on the peak height of galactose, glucose and mannose in the hydrolysate.

Reference numbers in the figures: 1 is the reflux condenser pipe, 2 is the reflux condenser pipe delivery port, and 3 are iron clamps, and 4 are the reflux condenser pipe water inlet, and 5 are iron clamps, and 6 are the glass flask, and 7 are for dissolving the trifluoroacetic acid aqueous solution that has the polysaccharide, and 8 are the far infrared, and 9 are far infrared generator, and 10 are the iron stand platform, and 11 are the voltage regulator.

Detailed Description

The invention is further described below by way of examples and figures: