CN112675705A - Method for carrying out fractional purification on Maillard reaction intermediate - Google Patents
Method for carrying out fractional purification on Maillard reaction intermediate Download PDFInfo
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/18—Treatment of tobacco products or tobacco substitutes
- A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
- A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/58—Multistep processes
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Abstract
本发明提供一种对美拉德反应中间体进行分级纯化的方法，其特征在于，所述方法包括：利用膜分离工艺，从所述美拉德反应中间体中分离出具有特定分子量范围的美拉德反应中间体。进一步地，本发明还提供了由此得到的美拉德反应中间体及其用途。在膜分离后不同分子量的美拉德反应中间体中，内含成分不同，在受热裂解时的热裂解温度、裂解释放的致香成分都有各自的特征，可以一定程度实现裂解温度和裂解释放的致香成分的定向调控，从而控制美拉德反应中间体的香型和烟用效果。
The present invention provides a method for fractional purification of a Maillard reaction intermediate, characterized in that the method comprises: using a membrane separation process to separate the Maillard reaction intermediate from the Maillard reaction intermediate with a specific molecular weight range. Rad reaction intermediate. Further, the present invention also provides the thus obtained Maillard reaction intermediate and use thereof. In the Maillard reaction intermediates with different molecular weights after membrane separation, the internal components are different, the thermal cracking temperature during thermal cracking, and the aroma components released by cracking have their own characteristics, which can achieve the cracking temperature and cracking release to a certain extent. The directional regulation of the aroma components, thereby controlling the aroma and smoky effects of the Maillard reaction intermediates.
Description
Technical Field
The invention belongs to the field of cigarettes, and particularly relates to a method for carrying out fractional purification on a Maillard reaction intermediate, and also relates to the Maillard reaction intermediate obtained by the method and application of the Maillard reaction intermediate.
Background
The tobacco essence perfume has the functions of enriching the tobacco fragrance, improving the smoking quality, highlighting and forming the cigarette style in the cigarettes, and is one of the core technologies of the cigarettes. For traditional cigarettes, the most common is to apply the essence and the spice to cut tobacco or cigarette paper or a filter rod, and in the smoking process of a consumer, the flavor components enter the oral cavity of the consumer through volatilization, distillation, pyrolysis, cracking and the like, so that the smoking feeling is improved. The cigarette is heated, namely the cigarette is not combusted, tobacco substances are heated through an external heat source, and atomized media, flavor components and additional flavor in the tobacco substances generate smoke similar to the smoke of the traditional cigarette through heating, so that the consumers can obtain physiological satisfaction. The tobacco substances in the heated cigarette are only heated without burning, and the heating temperature (200-.
The Maillard reaction is an important means for preparing thermal reaction type spices, and the complete Maillard reaction end product has rich flavor, but the flavor is quick to volatilize and not durable, and is easy to lose in the processing and storage processes. Maillard reaction intermediates are intermediates of Maillard reactions, which are mixtures of sugars and amino acids that undergo non-enzymatic browning when heated. The mixture contains very complicated components, and according to different browning degrees, the mixture contains micromolecular alpha-diketone and ester, heterocyclic derivatives (mainly furan rings and pyran rings) with complicated structures and browning products with high molecular weight. Maillard reaction intermediates are precursors of important aroma components, which generally do not have an aroma themselves, but can be converted and cleaved under heat to a variety of end product components of Maillard reactions. The type of flavour released is related to the sugars and amino acids used. The Maillard reaction intermediates prepared from different types of sugar and amino acid have different flavors. The difference in flavor is also related to the degree of Maillard reaction progress. The longer the reaction time, the more thorough the Maillard reaction proceeds and the flavor profile varies.
The Maillard reaction intermediate is a substance with a complex structure, is a mixture of a plurality of Maillard reaction intermediate products, and can generate various reactions among the intermediates during thermal cracking, so that the final cracking product has complex components, and the odor released by heating is very complex, thus being a mixed odor type. This results in the use of maillard reaction intermediates that are not fine enough in odor control and in tobacco performance.
Disclosure of Invention
The invention aims to solve the problem that the Maillard reaction intermediate is not fine enough in the aspect of flavor control during application, and provides a method for carrying out fractional purification on the Maillard reaction intermediate, namely a method for directionally obtaining the Maillard reaction intermediate with expected composition.
Accordingly, in one aspect, the present invention provides a process for the fractional purification of maillard reaction intermediates, said process comprising: and separating the Maillard reaction intermediate with a specific molecular weight range from the Maillard reaction intermediate by using a membrane separation process.
In one embodiment of the invention, the membrane separation process is selected from dialysis, reverse osmosis, ultrafiltration, microfiltration or nanofiltration based on membranes of different molecular weight cut-off.
In one embodiment of the invention, the membrane separation process comprises a plurality of membrane separation processes to separate a plurality of sets of maillard reaction intermediates having specific molecular weight ranges.
In one embodiment of the invention, the plurality of membrane separation processes have a high to low molecular weight cut-off in sequence.
In one embodiment of the invention, the plurality of membrane separation processes comprises membrane separation processes having molecular weight cut-offs of 500Da, 1000Da and 5000Da, respectively.
In one embodiment of the present invention, the Maillard reaction intermediate is obtained by Maillard reaction of amino acid and saccharide at 50-200 deg.C.
In one embodiment of the present invention, the amino acid is selected from at least one of glycine, alanine, arginine, glutamic acid, proline, leucine, and isoleucine.
In one embodiment of the present invention, the saccharide is selected from at least one of glucose, fructose, sucrose, lactose, mannose and galactose.
In another aspect, the present invention also provides a maillard reaction intermediate obtained by the method as described above.
In another aspect, the invention also provides the use of the Maillard reaction intermediate obtained as described above as a flavoring substance in cigarettes.
Compared with the prior art, the invention at least has the following beneficial technical effects:
(1) the Maillard reaction intermediates with different molecular weights obtained after membrane separation have different content components, the pyrolysis temperature and the aroma components released by pyrolysis have respective characteristics when heated and pyrolyzed, and the directional regulation and control of the pyrolysis temperature and the aroma components released by pyrolysis can be realized to a certain extent, so that the odor type and the cigarette effect of the Maillard reaction intermediates are controlled; (2) maillard reaction intermediates with different molecular weight ranges obtained after membrane separation can be selectively used according to different odor type requirements; (3) the membrane separation process is simple, the operation is simple and convenient, and the realization is easy; (4) when the Maillard reaction intermediates with different molecular weights obtained after membrane separation are applied to traditional cigarettes and heated cigarettes, the spice substances do not volatilize and lose at normal temperature, and even if the heated cigarettes are stored for a long time, the aroma is still lasting and stable during smoking; and (5) when the Maillard reaction intermediates with different molecular weights obtained after membrane separation are applied to traditional cigarettes and heated cigarettes, the aroma is rich and full during smoking, and the smoking quality and the consumption experience are improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIGS. 1a-1c show the results of DSC-DTG-TG test of Maillard reaction intermediates of example 1 (FIG. 1 a: 500-5000 Da; FIG. 1 b: 1000-5000 Da; and FIG. 1 c: >5000 Da); and is
FIGS. 2a-2c show the results of DSC-DTG-TG testing of the Maillard reaction intermediate of example 2 (FIG. 2 a: 500-5000 Da; FIG. 2 b: 1000-5000 Da; and FIG. 2 c: >5000 Da).
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Before describing the present invention in detail, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention which will be limited only by the appended claims. For a more complete understanding of the invention described herein, the following terms are used, and their definitions are set forth below. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In one aspect, the present invention provides a method for fractional purification of maillard reaction intermediates, comprising: and separating the Maillard reaction intermediate with a specific molecular weight range from the Maillard reaction intermediate by using a membrane separation process.
As the membrane separation process used in the present invention, a membrane separation process commonly used in the art may be used as long as it can separate a maillard reaction intermediate having a specific molecular weight range. For example, in a preferred embodiment, the membrane separation process may be selected from dialysis, reverse osmosis, ultrafiltration, microfiltration or nanofiltration based on membranes of different molecular weight cut-off.
In addition, the membrane separation process of the present invention may include a plurality of membrane separation processes, so that a plurality of groups of maillard reaction intermediates having a specific molecular weight range can be separated. The method with a plurality of membrane separation processes can enable the separated Maillard reaction intermediates to have more accurate or expected molecular weight ranges, and has positive effects on the situation that a plurality of groups of Maillard reaction intermediates with different specific molecular weight ranges are expected to be obtained simultaneously. It is also intended to underline that when the membrane separation process comprises a plurality of membrane separation processes, these membrane separation processes may be independently selected from dialysis, reverse osmosis, ultrafiltration, microfiltration or nanofiltration based on membranes of different molecular weight cut-off, independently of the other membrane separation processes.
According to the present invention, when the membrane separation process includes a plurality of membrane separation processes, the plurality of membrane separation processes may have high to low molecular weight cut-offs in order, so that maillard reaction intermediates having different molecular weight ranges may be obtained divided step by step. For example, in one preferred embodiment, the plurality of membrane separation processes comprises membrane separation processes having molecular weight cut-offs of 500Da, 1000Da, and 5000Da, respectively. In this case, the Maillard reaction intermediates can enter membrane separation processes with molecular weight cut-off of 5000Da, 1000Da and 500Da in sequence from high to low, so that Maillard reaction intermediates with molecular weight ranges of >5000Da, 1000-5000Da, 500-1000Da and <500Da can be obtained.
In the actual operation process, the intermediate solution of the Maillard reaction can pass through the membrane separation device in turn according to the molecular weight cut-off of the membrane component. And obtaining Maillard reaction intermediate solution with corresponding molecular weight from the trapped fluid obtained by each separation. The effluent liquid of each separation can be used for the stock solution of the next low molecular weight cut-off membrane component for separation. In addition, the Maillard reaction intermediate solution with different molecular weights can be concentrated until crystals appear, a small amount of deionized water is added for dissolution to form a solution, and the solution can also be freeze-dried to obtain a solid Maillard reaction intermediate.
According to the present invention, the term "maillard reaction", also known as non-enzymatic browning reaction, is a non-enzymatic browning reaction widely existing in the food industry, and is a reaction between a carbonyl compound (e.g. reducing saccharide) and an amino compound (e.g. amino acid and protein), which finally generates a brown or even black macromolecular substance melanoidin or melanoid through a complicated process, and is also known as carbonylamine reaction; the term "Maillard reaction intermediate" refers to an intermediate product during the Maillard reaction and can be obtained by carrying out an incomplete Maillard reaction from starting materials at a certain temperature.
Therefore, in a preferred embodiment of the present invention, the Maillard reaction intermediate can be obtained by carrying out Maillard reaction under 50-200 ℃ (e.g., 80 ℃, 100 ℃, 120 ℃, 150 ℃ or 180 ℃) from amino acids and saccharides (the molar ratio of the amino acids to the saccharides can be 1: 0.5-2, preferably 1: 1). Further, the maillard reaction can be carried out by a method well known to those skilled in the art, for example, by a basic method, i.e., catalyzing the above reaction with a basic catalyst, and adding an acidic reagent at the end of the reaction to adjust the pH to neutral; or may be carried out by an acidic method in which the above reaction is catalyzed with an acidic catalyst and an alkaline agent is added at the end of the reaction to adjust the pH to neutrality.
Still further, in a preferred embodiment of the present invention, the amino acid may be selected from at least one of glycine, alanine, arginine, glutamic acid, proline, leucine, and isoleucine; the saccharide may be selected from at least one of glucose, fructose, sucrose, lactose, mannose and galactose. Based on the above-described selection of specific amino acids and saccharide species, it is understood that the Maillard reaction intermediates of the present invention can be obtained by Maillard reaction from any combination of the above-described amino acids and saccharides.
In another aspect, the invention also provides maillard reaction intermediates, obtained by the process as described above. The Maillard reaction intermediate obtained in the way can have an expected molecular weight range according to actual needs, and can realize the directional regulation and control of the cracking temperature of the Maillard reaction intermediate and the aroma components released by cracking to a certain extent, thereby controlling the aroma type and the cigarette effect of the Maillard reaction intermediate.
On the other hand, the Maillard reaction intermediate obtained by the separation is used as a spice substance in cigarettes. The Maillard reaction intermediate of the invention can be used for preparing cigarettes in different ways according to different types of cigarettes.
For example, when the cigarette is a heated cigarette, the maillard reaction intermediate solids with different molecular weights after membrane separation can be uniformly mixed with tobacco powder to prepare a tobacco sheet thread, the tobacco thread is wrapped by cigarette paper to form a tobacco section, and the tobacco section is connected with a cooling filter rod through tipping paper to form a heated cigarette; the Maillard reaction intermediates with different molecular weights after membrane separation can be prepared into water, ethanol, propylene glycol, glycerol solution or a combination thereof, and then are uniformly mixed with tobacco powder to prepare tobacco sheet threads, the tobacco threads are wrapped by cigarette paper to form a tobacco section, and the tobacco section is connected with a cooling filter rod through tipping paper to form a heating cigarette; preparing Maillard reaction intermediates with different molecular weights after membrane separation into water, ethanol, propylene glycol, glycerol solution or a combination thereof, uniformly applying the water, ethanol, propylene glycol and glycerol solution on the surface of the tobacco sheet threads, wrapping the tobacco threads with cigarette paper to form a tobacco section, and connecting the tobacco section with a cooling filter rod through tipping paper to form a heated cigarette; preparing Maillard reaction intermediates with different molecular weights after membrane separation into a solution of water or ethanol or propylene glycol or glycerol, uniformly applying the solution on the surface of a tow to prepare a cooling filter rod, wrapping tobacco filaments with cigarette paper to form a tobacco section, and connecting the tobacco section with the cooling filter rod through tipping paper to form a heated cigarette; uniformly applying Maillard reaction intermediate solids with different molecular weights after membrane separation to the silk bundles to prepare a cooling filter rod, wrapping tobacco filaments by cigarette paper to form a tobacco section, and connecting the tobacco section and the cooling filter rod through tipping paper to form a heated cigarette; and filling Maillard reaction intermediate solids with different molecular weights after membrane separation into a cavity of the hollow section of the filter rod to prepare a cooling filter rod, wrapping tobacco threads with cigarette paper to form a tobacco section, and connecting the tobacco section and the cooling filter rod through tipping paper to form the heated cigarette.
For another example, when the cigarette is a traditional cigarette, the maillard reaction intermediates with different molecular weights after membrane separation can be prepared into a solution of water, ethanol, propylene glycol or glycerol, the solution is uniformly applied to the surface of tobacco shreds, the tobacco shreds are wrapped by cigarette paper to form a tobacco section, and the tobacco section is connected with a filter rod through tipping paper to form a cigarette; preparing Maillard reaction intermediates with different molecular weights after membrane separation into a solution of water or ethanol or propylene glycol or glycerol, uniformly applying the solution on the surface of cigarette paper, wrapping tobacco shreds with the cigarette paper to form a tobacco section, and connecting the tobacco section and a filter rod through tipping paper to form cigarette cigarettes; preparing Maillard reaction intermediates with different molecular weights after membrane separation into a solution of water or ethanol or propylene glycol or glycerol, uniformly applying the solution on the surface of a tow to prepare a filter rod, wrapping tobacco shreds with cigarette paper to form a tobacco section, and connecting the tobacco section and the filter rod through tipping paper to form a cigarette; uniformly applying Maillard reaction intermediate solids with different molecular weights after membrane separation to the silk bundles to prepare the filter tip, wrapping the tobacco shreds with cigarette paper to form a tobacco section, and connecting the tobacco section and the filter tip through tipping paper to form the cigarette.
The inventor finds that the Maillard reaction intermediates with different molecular weights after membrane separation have different content components, the pyrolysis temperature during pyrolysis by heating and the aroma components released by pyrolysis have respective characteristics, and the directional regulation and control of the pyrolysis temperature and the aroma components released by pyrolysis can be realized to a certain degree, so that the aroma type and the cigarette effect of the Maillard reaction intermediates are controlled.
Hereinafter, the effect of the fractional purification method of the present invention will be described in detail by examples.
Examples
Example 1
Synthesis of acid method maillard reaction intermediate: glucose and alanine in a certain amount (1: 1 molar ratio) were reacted in 5% (ratio to the total weight of L-alanine and glucose) of malonic acid as a catalyst at 65 ℃ for 8h in four times (ratio to the total weight of L-alanine and glucose) of methanol. After the reaction is completed, adding sodium hydroxide to neutralize the reaction product to be neutral, obtaining Maillard reaction intermediates with different molecular weight ranges (respectively 500-1000Da, 1000-5000Da and >5000Da) from the obtained Maillard crude product by a dialysis method of a membrane separator, and then freeze-drying the Maillard reaction intermediates to remove the solvent or moisture in the Maillard reaction intermediates, thereby obtaining the solid Maillard intermediates.
The cells were lysed and analyzed in a CDS 5250T pyrolyzer. The sample cells used in the cracking test are all stainless steel high-pressure crucibles with gold-plated gaskets, the capacity is 30 mu L, the highest pressure resistance is 15MPa, and the reference crucibles are all high-pressure stainless steel crucibles made of the same material. The temperature rise rate beta of the dynamic DSC test is 10 ℃/min respectively, the test temperature range is 30-800 ℃, and the sample mass m is 3.5 +/-0.05 mg.
The glucose-alanine Maillard reaction intermediate prepared by the acidic method is subjected to membrane treatment and classification to obtain three samples with different molecular weights, wherein the molecular weights are respectively 500-1000Da, 1000-5000Da and more than 5000 Da. FIGS. 1a-c are thermal analysis curves of the three samples in sequence, including a differential thermal analysis curve DSC, a differential thermogravimetric analysis curve DTG and a thermogravimetric analysis curve TG. DTG and TG showed that the three samples all showed thermal weight loss peaks in the range of 140-150 ℃ and weight loss of about 40%. However, DSC differential thermal analysis shows that the endothermic peaks of the three are obviously different. The endothermic peak of the low molecular weight intermediate is about 125 ℃, the endothermic peak of the high molecular weight intermediate is 142-145 ℃, and the intermediate molecular weight intermediate has more obvious endothermic peaks at both temperatures. This indicates that the molecular weight of the intermediate of Maillard reaction is different, the structure of the inclusion is different, and the thermal cracking behavior is also different.
The lysis and analysis was carried out at 200 deg.C, 300 deg.C and 400 deg.C using a CDS 5250T pyrolyser and an Agilent 7890A-5975C GC gas chromatograph-Mass spectrometer. About 1mg of the sample was weighed and placed on quartz wool in a cracker tube, which was then placed on a cracker to be cracked. Cracking temperature rise procedure: the initial temperature was 50 ℃ and ramped up to the set pyrolysis temperature at 30 ℃/s for 5 s. The cracking atmosphere is helium, and the gas flow is as follows: 70mL/min, temperature of the cracker valve box: 280 ℃, transmission line temperature of the cracker: 280 ℃. GC-MS method: an elastic quartz capillary column; the stationary phase is 5% of phenyl-95% of methyl polysiloxane; the specification is [30m (length) × 0.25mm (inner diameter) × 0.25 μm (film thickness) ]; carrier gas flow, 1.0 mL/min; the split ratio is 100: 1; heating, wherein the initial temperature is 40 ℃, keeping for 3min, increasing to 240 ℃ at the speed of 10 ℃/min, increasing to 280 ℃ at the speed of 20 ℃/min, and keeping for 15 min; the mass spectrum transmission line temperature is 280 ℃; the ion source temperature is 230 ℃; the temperature of the quadrupole rods is 150 ℃; the mass scan range is 29-450 amu. The cleavage product results are shown in tables 1-3 below:
TABLE 1 glucose-alanine Maillard reaction intermediates of different molecular weights (acid method) Py-GC/MS results under nitrogen atmosphere (200 ℃ C.)
TABLE 2 glucose-alanine Maillard reaction intermediates of different molecular weights (acid method) Py-GC/MS results under nitrogen atmosphere (300 ℃ C.)
TABLE 3 glucose-alanine Maillard reaction intermediates of different molecular weights (acid method) Py-GC/MS results under nitrogen atmosphere (400 ℃ C.)
Tables 1-3 show the results of thermal cracking-gas chromatography/mass spectrometry (Py-GC/MS) of glucose-alanine Maillard reaction intermediates of different molecular weights (acid method, molecular weight 500-. As can be seen from Table 1, the low molecular weight intermediates release more material at low temperatures (200 ℃) than do the high molecular weight intermediates, which may be related to the cleavage process as indicated by the endothermic peak at low temperatures. As the cracking temperature increases, the cracking substances of the high molecular weight intermediate are increased in types, similar to the low molecular weight intermediate in types, and have obvious trends at 300 ℃ and 400 ℃, but the obtained cracking substances are different at different temperatures. This indicates that the different molecular weight intermediates have different contents and that the cleavage products obtained are also not uniform.
The application in heating cigarettes comprises the following steps: uniformly applying Maillard reaction intermediates with molecular weight of 500-1000Da after membrane separation to the tows (the weight ratio of the Maillard reaction intermediates to the tows is 1:400), preparing a cooling filter rod, wrapping tobacco shreds with cigarette paper to form a tobacco section, connecting the tobacco section and the cooling filter rod through tipping paper to form a heated cigarette, and evaluating the smoking result shows that the baked aroma is obvious; in addition, after membrane separation, the Maillard reaction intermediate with the molecular weight of 1000-5000Da and the tobacco powder are mixed according to the weight ratio of 1: 500, preparing tobacco thin slices, wrapping the tobacco thin slices with cigarette paper to form a tobacco section, connecting the tobacco section and a cooling filter tip through tipping paper to form a heated cigarette, and evaluating smoking results show that the roasted sweet and fragrant aroma is obvious and full.
The application in the traditional cigarette is as follows: preparing an ethanol solution from a Maillard reaction intermediate with the molecular weight of 500-1000Da after membrane separation, uniformly applying the ethanol solution on the surface of a tow (the weight ratio of the ethanol solution to the tow is 1:400), preparing a filter rod, wrapping tobacco shreds with cigarette paper to form a tobacco section, connecting the tobacco section and the filter rod through tipping paper to form a cigarette, and evaluating the smoking result to show that the baked aroma is obvious; in addition, the Maillard reaction intermediate with the molecular weight of 1000-5000Da after membrane separation is prepared into ethanol solution and is uniformly applied to the surface of the tobacco shred (the weight ratio of the ethanol solution to the tobacco shred is 1: 1000), the tobacco shred is wrapped by the cigarette paper to form a tobacco section, the tobacco section is connected with the filter rod through tipping paper to form the cigarette, and the evaluation result shows that the cigarette has obvious scorched sweet aroma and harmonious aroma.
Example 2
Synthesis of alkaline maillard intermediates: mixing L-glycine and glucose according to the proportion of 1: mixing according to a molar ratio of 1, adding 4 times (the ratio of the total weight of the L-glycine and the glucose) of ethylene glycol solvent, adding 10% (the ratio of the total weight of the L-glycine and the glucose) of NaOH catalyst, reacting at 130 ℃ for 6 hours, adjusting the pH value to be neutral by using 1.0mol/L HCl solution, obtaining Maillard reaction intermediates with different molecular weight ranges (respectively 500 plus materials 1000Da, 1000 plus materials 5000Da and >5000Da) by using a membrane separator dialysis method for the obtained Maillard crude product, and then freezing and drying to remove the solvent or moisture in the Maillard reaction intermediates, thereby obtaining the solid Maillard intermediate.
Pyrolysis was carried out under the same conditions as in example 1: the glucose-alanine Maillard reaction intermediate prepared by the alkaline method is subjected to membrane treatment and classification to obtain three samples with different molecular weights (the molecular weights are respectively 500-1000Da, 1000-5000Da and >5000 Da). FIGS. 2a-c are thermal analysis curves of the three samples in sequence, including differential thermal analysis curve DSC, differential thermogravimetric analysis curve DTG and thermogravimetric analysis curve TG. Different from the acid catalytic intermediate, DTG and TG show that the three samples have a thermal weight loss peak at about 150-160 ℃ and a weight loss of about 15 percent, but the high molecular weight intermediate also has a thermal weight loss peak at 390 ℃. DSC differential thermal analysis shows that only the low molecular weight intermediate has an obvious endothermic peak accompanied with the thermal weight loss peak at about 150-160 ℃. This indicates that the differences in molecular weight of the maillard reaction intermediates lead to inconsistent thermal cracking behavior.
The cleavage experiments at 200 deg.C, 300 deg.C and 400 deg.C were carried out under the same conditions as in example 1. The cleavage product results are shown in tables 4-6 below:
TABLE 4 glucose-alanine Maillard reaction intermediates of different molecular weights (basic method) Py-GC/MS results under nitrogen atmosphere (200 ℃ C.)
TABLE 5 glucose-alanine Maillard reaction intermediates of different molecular weights (basic method) Py-GC/MS results under nitrogen atmosphere (300 ℃ C.)
TABLE 6 glucose-alanine Maillard reaction intermediates of different molecular weights (basic method) Py-GC/MS results under nitrogen atmosphere (400 ℃ C.)
Tables 4-6 show the results of thermal cracking-gas chromatography/mass spectrometry (Py-GC/MS) under nitrogen atmosphere for glucose-alanine Maillard reaction intermediates of different molecular weights (basic method, molecular weight 500-5000 kDa). As can be seen from Table 4, all intermediates at low temperature (200 deg.C, 300 deg.C) have no significant component release of cracked gas, and it is possible that the molecular weight of the basic process intermediate itself is high, and cracking at low temperature does not result in the release of low molecular cracked gas. At the high temperature of 400 ℃, although no obvious thermal weight loss peak appears, substances released by the low molecular weight intermediate are still more than those released by the high molecular weight intermediate, and may be related to a cracking process shown by an endothermic peak at about 150-.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A method for the fractional purification of maillard reaction intermediates, comprising: and separating the Maillard reaction intermediate with a specific molecular weight range from the Maillard reaction intermediate by using a membrane separation process.
2. The method of claim 1, wherein the membrane separation process is selected from dialysis, reverse osmosis, ultrafiltration, microfiltration or nanofiltration based on membranes of different molecular weight cut-off.
3. The method of claim 1 or 2, wherein the membrane separation process comprises a plurality of membrane separation processes to separate out a plurality of sets of maillard reaction intermediates having a specific molecular weight range.
4. The method of claim 3, wherein the plurality of membrane separation processes have a high to low molecular weight cut-off in sequence.
5. The method of claim 4, wherein the plurality of membrane separation processes comprise membrane separation processes having molecular weight cut-offs of 500Da, 1000Da, and 5000Da, respectively.
6. The method according to claim 1, wherein the Maillard reaction intermediate is obtained by Maillard reaction of amino acid and saccharide at 50-200 deg.C.
7. The method of claim 5, wherein the amino acid is selected from at least one of glycine, alanine, arginine, glutamic acid, proline, leucine, and isoleucine.
8. The method of claim 5, wherein the saccharide is selected from at least one of glucose, fructose, sucrose, lactose, mannose, and galactose.
9. A maillard reaction intermediate obtained by the process of any one of claims 1-8.
10. Use of the maillard reaction intermediate according to claim 9 as a flavoring substance in cigarettes.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113373730A (en) * | 2021-07-12 | 2021-09-10 | 云南中烟工业有限责任公司 | Amino acid polymer Maillard reaction product double-side coated black cigarette paper and preparation method thereof |
| CN113445367A (en) * | 2021-07-12 | 2021-09-28 | 云南中烟工业有限责任公司 | Colored cigarette paper containing Maillard reaction intermediate and preparation method thereof |
| CN113445366A (en) * | 2021-07-12 | 2021-09-28 | 云南中烟工业有限责任公司 | Black cigarette paper and preparation method thereof |
| WO2022126989A1 (en) * | 2020-12-14 | 2022-06-23 | 湖北中烟工业有限责任公司 | Method for fractional purification of maillard reaction intermediates |
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| WO2022126989A1 (en) | 2022-06-23 |
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