CN105457503A - Preparation and application of chlorogenic acid molecular imprinting chitosan membrane - Google Patents
Preparation and application of chlorogenic acid molecular imprinting chitosan membrane Download PDFInfo
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Abstract
The invention discloses a preparation method of a chlorogenic acid molecular imprinting chitosan membrane. The preparation method comprises the following steps: 1, dissolving chitosan and chlorogenic acid in an acetic acid solution with the volume fraction of 2%, fully stirring, filtering with a gauze filter, defoaming the filtrate, so as to obtain a casting membrane solution, wherein the mass ratio of chitosan to chlorogenic acid is 10:1; the volume dosage (calculated as the mass of chitosan) of the acetic acid solution is 40ml/g; 2, scraping the casting membrane solution and drying, so as to obtain a transparent membrane with the thickness of 60 micrometers; 3, placing the transparent membrane prepared in the step 2 in a sulfuric acid solution with the concentration of 0.5 mol/L for soaking for 24 h to carry out cross-linking reaction, eluting with an eluent, so as to obtain the chlorogenic acid molecular imprinting chitosan membrane. The chlorogenic acid molecular imprinting chitosan membrane provided by the invention can be used for adsorbing chlorogenic acid, the preparation method is simple and easy to operate, the mechanical strength is high, the prepared membrane is stable, acid-resistant and can be directly applied, and tedious preparation processes like crushing and grinding are not needed.
Description
Technical field
The invention belongs to sorbing material preparation technology field, relate to a kind of utilize molecular imprinting and phase conversion method to prepare chlorogenic acid molecular engram chitosan film method and performance study.
Background technology
The carboxylic phenolic acid that chlorogenic acid is made up of caffeic acid and chinic acid is a kind of plant polyphenol.Content in the plants such as the bark of eucommia, honeysuckle, coffee, chrysanthemum is very high; In addition, in the vegetable and fruit such as potato, carrot, spinach, apple also containing chlorogenic acid.Due to the principle active component that chlorogenic acid is in many Chinese medicinal materials and fruit and vegetable, so have multiple biologically active, as: cardiovascular protective effect, antioxidation, blood lipid-reducing blood sugar-decreasing effect etc.Traditional Chinese medicine active component complex structure, type are various, unstable and content is low, result in active ingredient of Chinese herbs separation and purification difficulty, pretend the chlorogenic acid also more difficult separation and purification into active ingredient of Chinese herbs.At present, the method of Isolation and purification chlorogenic acid has the water extracting alcohol precipitation method, the water extraction milk of lime precipitation method, alcohol extracting lead salt precipitation, supercritical ultrasonics technology, Thin-layer chromatography, enzyme process, supercritical methanol technology and macroreticular resin absorbing method etc., but these methods exist recovery rate low, selective not high, large to the destruction of chlorogenic acid, treating capacity is little, the process time is long, product purity is not high, safety and sanitation difference and high in cost of production shortcoming.
Due to advantages such as the precordainment of molecular imprinting in preparation, selectivitys in identifications, for the identification and analysis of the composition that content in natural products is low, drug effect is high and separation and purification provide method reference.Though the simple but subsequent treatment intricate operation of preparation method's polymerization process of conventional molecular imprinted polymer, time-consuming, product loss is serious, and shape of product is irregular, bad dispersibility.And have the molecular engram film of molecular imprinting and membrane separation technique dual characteristics concurrently because mill, so molecular engram hole retention rate is high without the need to pulverizing.
Shitosan is a kind of natural macromolecular material of function admirable, has good biocompatibility, biodegradable, the advantage such as nontoxic, inexpensive, owing to being rich in hydroxyl and amino in molecule, therefore can form hydrogen bond and ion pair effect with the hydroxyl in chlorogenic acid and carboxyl.But shitosan easily occurs swelling in aqueous, makes it apply and is subject to great restriction.Reacted by the amino in the functional group such as aldehyde radical, epoxy radicals and shitosan and hydroxyl, realize the crosslinked of shitosan, its swellability can be improved.At present conventional crosslinking agent has glutaraldehyde, epoxychloropropane, but due to their degree of cross linking high, cause crosslinked after film more crisp.
Summary of the invention
The object of this invention is to provide a kind of chlorogenic acid molecular engram chitosan film and preparation method thereof and application, the present invention utilizes molecular imprinting, take chlorogenic acid as template molecule, shitosan is filmogen, sulfuric acid is crosslinking agent, chlorogenic acid molecular engram chitosan film has been prepared by phase inversion, chlorogenic acid molecular engram chitosan film prepared by the present invention can adsorb chlorogenic acid and separating chlorogenic acid and the caffeinic mixture of its analogue effectively, and its separating effect is better than corresponding blank film.
The technical solution used in the present invention is:
A preparation method for chlorogenic acid molecular engram chitosan film, described method comprises the steps:
(1) casting solution is prepared: shitosan and chlorogenic acid are dissolved in the acetum of volume fraction 2%, filtered through gauze after fully stirring, filtrate deaeration, obtained casting solution; The mass ratio of described shitosan and chlorogenic acid is 10:1, and the volumetric usage of described acetum counts 40mL/g with the quality of shitosan;
(2) be poured on the cleaned glass plate of horizontal positioned by casting solution obtained in step (1), use scraper knifing, after dry, obtained thickness is the hyaline membrane of 60 μm;
(3) hyaline membrane obtained in step (2) is placed in 0.5molL
-1sulfuric acid solution in soak 24h and carry out cross-linking reaction, by the film eluent after crosslinked, described eluant, eluent is the mixed solution of ethanol, acetic acid, water volume ratio 2:3:7, the acetic acid of film excess surface is washed away again with volume fraction 20% ethanolic solution, drying, namely obtains chlorogenic acid molecular engram chitosan film.
In described step (1), described stirring generally stirs 6h at 60 DEG C of lower magnetic forces.
Described deaeration generally uses vacuum defoamation.
In described step (2), baking temperature is generally 60 DEG C, and drying time is generally 12h.
In described step (3), by the film eluent after crosslinked, detect the chlorogenic acid composition in eluent, be eluted to till can't detect chlorogenic acid in eluent.
The present invention adopts sulfuric acid to be cross-linked, and its crosslinked equation is as follows:
Present invention also offers the application of above-mentioned chlorogenic acid molecular engram chitosan film in absorption chlorogenic acid.
Present invention also offers the application of above-mentioned chlorogenic acid molecular engram chitosan film in adsorbing separation chlorogenic acid and its analogue caffeic acid.
The present invention has following beneficial effect: chlorogenic acid molecular engram chitosan film provided by the invention has the dual characteristics of molecular imprinting and membrane separation technique concurrently:
(1) on chlorogenic acid molecular engram chitosan film, specific binding site and functional group can realize specific recognition to determinand;
(2) compare traditional molecularly imprinted polymer, molecular engram membrane preparation method of the present invention is simple, and easy to operate, mechanical strength is good, stable and acidproof, can directly apply, and does not need to pulverize the loaded down with trivial details preparation process such as to mill.
Accompanying drawing explanation
Fig. 1 is the reaction principle figure that the present invention prepares chlorogenic acid molecular engram chitosan film.
Fig. 2 is the electron scanning micrograph of shitosan blank film and chlorogenic acid molecular engram chitosan film, and the A figure on Fig. 2 left side is shitosan blank film, and the B figure on the right is chlorogenic acid molecular engram chitosan film.
Fig. 3 is the infrared spectrogram of shitosan blank film and chlorogenic acid molecular engram chitosan film, wherein the A figure of Fig. 3 is the infrared spectrogram of uncrosslinked shitosan blank film and uncrosslinked chlorogenic acid molecular engram chitosan film, and B figure is the infrared spectrogram before and after shitosan blank film is cross-linked; C figure is the infrared spectrogram that chlorogenic acid molecular engram chitosan film is cross-linked before and after rear eluted template molecule chlorogenic acid.
Fig. 4 is the thermogravimetric analysis figure of shitosan blank film and chlorogenic acid molecular engram chitosan film.
Fig. 5 is the swelling curve figure of shitosan blank film and chlorogenic acid molecular engram chitosan film.
Fig. 6 is that shitosan blank film and chlorogenic acid molecular engram chitosan film are to the Dynamic Adsorption curve map of chlorogenic acid.
Fig. 7 is that shitosan blank film and chlorogenic acid molecular engram chitosan film are to the Static Adsorption curve map of chlorogenic acid and Scatchard curve map, wherein the little figure of Fig. 7 upper right be shitosan blank film and chlorogenic acid molecular engram chitosan film to the Static Adsorption curve map of chlorogenic acid, the large figure in Fig. 7 lower-left is Scatchard curve map.
Fig. 8 is that shitosan blank film and chlorogenic acid molecular engram chitosan film carry out one-component solution permeability test curve map.
Fig. 9 is the HPLC analysis chart that shitosan blank film and chlorogenic acid molecular engram chitosan film carry out mixed solution permeability test, and wherein (a) figure of Fig. 9 is the HPLC analysis chart of material liquid, (b) figure is that chlorogenic acid molecular engram chitosan film carries out the HPLC analysis chart of gained penetrating fluid in mixed solution permeability test, (c) figure is the HPLC analysis chart that shitosan blank film carries out gained penetrating fluid in mixed solution permeability test.
In Fig. 9: C represents chlorogenic acid; D represents caffeic acid.
Detailed description of the invention
With specific embodiment, technical scheme of the present invention is described further below, but protection scope of the present invention is not limited thereto.
The experimental technique used in following embodiment if no special instructions, is conventional method.
The material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
The preparation of embodiment 1, chlorogenic acid molecular engram chitosan film
(1) preparation of casting solution: by 1.25g shitosan and 0.125g chlorogenic acid, is dissolved in the aqueous acetic acid of 50mL volume fraction 2% simultaneously, and stir 6h in 60 DEG C of lower magnetic forces, filtered through gauze elimination insoluble matter, vacuum defoamation is spent the night, and obtains casting solution.
(2) preparation of film: casting solution obtained in above-mentioned (1) is poured on the cleaned glass plate of horizontal positioned, use scraper knifing, be placed in dry 12h at electric heating constant-temperature blowing drying box 60 DEG C again, namely obtain smooth and transparent film, thickness 60 μm.This film is uncrosslinked chlorogenic acid molecular engram chitosan film, is designated as uncrosslinked C-MIM
(3) film in above-mentioned (2) is placed in 0.5molL
-1sulfuric acid solution in soak 24h and carry out cross-linking reaction, by the film Ethanol-Acetic Acid-aqueous solution (volume ratio 2/3/7) after crosslinked repeatedly wash-out to remove chlorogenic acid, eluent high performance liquid chromatography detects, can't detect chlorogenic acid in eluent till, the acetic acid of film excess surface is washed away again with volume fraction 20% ethanolic solution, drying, namely obtains chlorogenic acid molecular engram chitosan film, is designated as C-MIM.
The preparation of comparative example 1 shitosan blank film
(1) preparation method of shitosan blank film is: be dissolved in by 1.25g shitosan in the acetum of 50mL volume fraction 2%, stirs 6h, filtered through gauze, filter vacuum deaeration in 60 DEG C of lower magnetic forces, obtained casting solution;
(2) casting solution is poured on the cleaned glass plate of horizontal positioned, uses scraper knifing, then be placed in dry 12h at electric heating constant-temperature blowing drying box 60 DEG C, namely obtain smooth and transparent film, thickness 60 μm.This is uncrosslinked shitosan blank film, is designated as uncrosslinked N-MIM
(3) film in above-mentioned (2) is placed in 0.5molL
-1sulfuric acid solution in soak 24h and carry out cross-linking reaction, film volume fraction 20% ethanolic solution after crosslinked is washed away the sulfuric acid on film surface, namely obtains shitosan blank film, be designated as N-MIM.
The sign of the chlorogenic acid molecular engram chitosan film of embodiment 2, embodiment 1 preparation
(1) scanning electron microscope analysis
Characterized by the microstructure of SEM to shitosan blank film and chlorogenic acid molecular engram chitosan film, result is respectively as shown in Fig. 2 (left and right).
Can be learnt by Fig. 2, the surperficial smoother of the shitosan blank film of left side A figure and compact, have graininess projection a little; The chlorogenic acid molecular engram chitosan film surface ratio of the right B figure is more coarse and have loose sense, this is because define molecular engram structure on blotting membrane, this structure is conducive to contacting of substrate and binding site, thus improves the adsorbance of film.
Consider the design feature of blot conditions and known raw material, the composition principle of chlorogenic acid molecular engram chitosan film as shown in Figure 1, template molecule chlorogenic acid with hydroxyl and carboxyl is represented with the filmogen shitosan with amino and hydroxyl by ion pair effect and hydrogen bond action prepolymerization in Fig. 1, use Ethanol-Acetic Acid-aqueous solution (volume ratio 2/3/7) cyclic washing to form the molecular engram film with cavity structure to remove template molecule chlorogenic acid again, can be used for the absorption of chlorogenic acid and analogue thereof.
(2) infrared spectrum analysis
Carry out spectrum analysis with infrared spectrometer to shitosan blank film and chlorogenic acid molecular engram chitosan film, result is respectively as shown in A, B, C figure of Fig. 3.
The A figure of Fig. 3 is the infrared spectrum of uncrosslinked shitosan blank film and uncrosslinked chlorogenic acid molecular engram chitosan film.Shitosan blank film has typical chitosan structure, has obvious polysaccharide structures characteristic peak.Wherein, 1062cm
-1the absworption peak at place is C-O-C stretching vibration peak; 896cm
-1and 1151cm
-1place be the characteristic absorption peak of glycosidic bond in shitosan; 1323cm
-1what locate is C-O stretching vibration peak; 1407cm
-1that locate is CH
2deformation vibration absworption peak; 1548cm
-1what locate is N-H deformation vibration peak; 1632cm
-1for the remaining NH of shitosan
2cO absworption peak.Compared with shitosan blank film, chlorogenic acid molecular engram chitosan film is at 858cm
-1, 812cm
-1, 763cm
-1there is new peak in place, they are the out-of-plane bending vibration peaks of the C-H on the phenyl ring in chlorogenic acid, and visible chlorogenic acid and shitosan there occurs combination.In addition, the intensity of some absworption peaks there occurs change, such as, in chlorogenic acid molecular engram chitosan film 1629cm
-1place NH
2the stretching vibration absworption peak of the C=C double bond in CO absworption peak and chlorogenic acid strengthens to some extent, proves that microsphere chlorogenic acid has been combined with shitosan or-COOH on the chlorogenic acid and-NH on filmogen shitosan
2between define new NH
2cO.1263cm
-1for phenol-OH stretching vibration absworption peak, it significantly strengthens than shitosan blank film, proves that microsphere chlorogenic acid is combined with shitosan.
The B figure of Fig. 3 is the infrared spectrum before and after shitosan blank film is cross-linked, and both all have obvious chitosan structure.3350cm
-1the absworption peak at place is the N-H stretching vibration peak in primary amine, and after crosslinked, it disappears, and at 2080cm
-1there is NH in place
3 +new peak, be all shown to be sulfuric acid and chitosan crosslinked after define ammonium salt; In addition, after crosslinked, 1151cm
-1the peak of the glycosidic bond at place disappears, this is because glycosidic bond has been hydrolyzed in sulfuric acid.
The C figure of Fig. 3 is the infrared spectrum before chlorogenic acid molecular engram chitosan film is cross-linked rear wash-out and after wash-out, with shitosan blank film, and 3350cm after crosslinked
-1and 1151cm
-1the peak at place disappears, simultaneously at 2080cm
-1there is new peak in place, this be all sulfuric acid and chitosan crosslinked after define the result of ammonium salt.In addition, after chlorogenic acid molecular engram chitosan film wash-out, 1263cm
-1place phenol-OH stretching vibration absworption peak significantly weakens, 858cm
-1, 812cm
-1, 763cm
-1place phenyl ring on C-H out-of-plane bending vibration peak disappear, these all declaratives chlorogenic acid be eluted.
(3) thermogravimetric analysis
Carry out spectrum analysis with microcomputer differential thermal analyzer to shitosan blank film and chlorogenic acid molecular engram chitosan film, result as shown in Figure 4.
Can learn from Fig. 4, between 30 ~ 200 DEG C, both have quality to volatilize, this is the loss of volatile component in film, mainly water, ethanol, acetic acid and unreacted sulfuric acid, and shitosan blank film is larger than chlorogenic acid molecular engram chitosan film weight loss.Between 200 ~ 250 DEG C, film quality volatilizees fast, and curve sharply declines, this mainly burned decomposition of filmogen shitosan.Between 250 ~ 800 DEG C, film quality slowly volatilizees, and almost reaches complete fired state, but differential thermal analysis curve difference obviously, may be that comparatively shitosan blank film is good because of chlorogenic acid molecular engram chitosan film structural order, therefore heat resistance is higher than blank film.In a word, chlorogenic acid molecular engram chitosan film and shitosan blank film weight-loss ratio are respectively 65.6% and 73.6%, better heat stability.
The research of embodiment 3, chlorogenic acid molecular engram chitosan film performance
(1) Study on Swelling Properties of chlorogenic acid molecular engram chitosan film
Shitosan blank film and chlorogenic acid molecular engram chitosan film to be placed at electric heating constant-temperature blowing drying box 60 DEG C drying about half an hour, taking-up is weighed.Be soaked in the ethanol water of different volumes mark under room temperature, no longer change to its quality, be placed in by film between two-layer absorbent filter and wipe film surface liquid away, weigh, the swellbility (DS) of film is calculated by following formula:
Wherein, m is dry film quality, m
1for the film quality after swelling.
The swelling curve drawn further by experimental data as shown in Figure 5.Experimental result shows, the swelling behavior of each film all changes with the change of volumes of aqueous ethanol mark.On the one hand, along with the increase of volumes of aqueous ethanol mark, the swelling ratio of chlorogenic acid molecular engram chitosan film and shitosan blank film all reduces, and swelling behavior makes moderate progress, and this is mainly because shitosan swellbility in water is comparatively large, and anti-ethanol ability is strong.On the other hand, compared with shitosan blank film, the swelling behavior of chlorogenic acid molecular engram chitosan film is more excellent, and this mainly because shitosan and chlorogenic acid combine because of hydrogen bond and ion pair effect in chlorogenic acid molecular engram chitosan film forming process, thus limits the swelling behavior of shitosan.
(2) the dynamic adsorption research of chlorogenic acid molecular engram chitosan film
Take the dry shitosan blank film of 9mg and each 11 parts of chlorogenic acid molecular engram chitosan film, be placed in 50mL conical flask respectively, each conical flask respectively labelled 1,4,8,12,20,30,40,50,60,75,90min, then add 40mL20mgL in each conical flask
-1chlorogenic acid 20% ethanolic solution, carry out constant temperature oscillation absorption at being placed in 30 DEG C, desk-top constant temperature oscillation case.Then, use liquid-transfering gun in the appointment moment to the solution sampling posted in the conical flask of this label, by ultraviolet-uisible spectrophotometer, 327nm place (UV-vis) measures absorbance, according to the further calculating concentration of calibration curve, then calculate the adsorption capacity in each moment according to following formula.Experimentally the Dynamic Adsorption curve of Plotting data as shown in Figure 6.
Adsorption capacity is calculated according to following formula
Wherein, Q
tfor adsorption capacity (μm olg of t
-1), C
0, C
tbe respectively the adsorption concentration (mmolL of initial time and t
-1), m is the quality of adsorbed film, and V is liquor capacity.
The Dynamic Adsorption curve drawn further by experimental data as shown in Figure 6.Experimental result shows, the diaphragm of 9mg is at 40mL20mgL
-1chlorogenic acid 20% ethanolic solution in when adsorbing, chlorogenic acid molecular engram chitosan film is faster than the initial rate of adsorption of shitosan blank film, this is mainly because there is specific adsorption site in chlorogenic acid molecular engram chitosan film, namely microsphere is by after wash-out, blotting membrane still remains the binding site that can mate completely with microsphere.Meanwhile, the time that chlorogenic acid molecular engram chitosan film reaches adsorption equilibrium is about 40min, longer than shitosan blank film time of equilibrium adsorption, and thus the adsorption capacity of chlorogenic acid molecular engram chitosan film is larger.
(3) the Static Adsorptive capacity research of chlorogenic acid molecular engram chitosan film
Take the dry blotting membrane of 9mg and each 10 parts of blank film, be placed in 50mL conical flask respectively, then add 40mL concentration and be respectively 0.1-5.0mmolL
-1chlorogenic acid 20% ethanol standard liquid, be placed in constant temperature oscillation 1h at 30 DEG C, desk-top constant temperature oscillation case, after leaving standstill, get chlorogenic acid measured by supernatant by UV-vis concentration in 327nm place, parallel determination three times, average, calculate chlorogenic acid concentration according to calibration curve, and then obtain adsorbance.
Wherein, V is the volume (mL) of solution, and m is the quality (mg) of blotting membrane, C
0, C
e(mmolL
-1) be respectively the concentration after the initial concentration of solution and adsorption equilibrium, Q
efor equilibrium adsorption capacities (μm olg
-1).
Shown in the Static Adsorption curve drawn further by experimental data figure as little in Fig. 7 upper right.Experimental result shows, along with the increase of chlorogenic acid concentration, shitosan blank film and the adsorption capacity of chlorogenic acid molecular engram chitosan film to chlorogenic acid all increase, but the rate of adsorption all reduces.In addition, under same concentrations, chlorogenic acid molecular engram chitosan film is always greater than the adsorption capacity of shitosan blank film significantly to the adsorption capacity of chlorogenic acid, this shows that chlorogenic acid molecular engram chitosan film is to the absorption of chlorogenic acid mainly specific adsorption, in other words, the avtive spot on microsphere " the trace hole " that stay in chlorogenic acid molecular engram chitosan film and hole determines chlorogenic acid molecular engram chitosan film to the affinity of chlorogenic acid and specific recognition.And for shitosan blank film, because it is not containing " trace hole ", can with substrate produce the functional group of combination although also have thereon, the arrangement of functional group is random, does not thus have molecular recognition performance to molecule.
Utilize Scatchard model by data analysis, evaluate the binding characteristic of chitosan film further.
Scatchard equation as shown in the formula:
Wherein, Q
e, Q
maxbe respectively the equilibrium adsorption capacities of adsorption site, maximum adsorption capacity (μm olg
-1); C
efor equilibrium adsorption concentration (mmolL
-1), K
dfor the equilibrium dissociation constant (mmolL of adsorption site
-1).
The large figure of Fig. 7 is Scatchard curve map.For chlorogenic acid molecular engram chitosan film, Q can be found
e/ C
eto Q
ein non-linear relation, but there are two parts can present good linear relationship, show the adsorption site that there are two class different performances in chlorogenic acid molecular engram chitosan film, linear fit is carried out respectively to them and obtains two straight lines, obtained the dissociation constant in two class compatibility sites and maximum apparent adsorption quantity from the intercept of straight line and slope.To high-affinity site: K
d1=0.17mmolL
-1, Q
max=139.57 μm of olg
-1; To low compatibility site: K
d2=1.27mmolL
-1, Q
max=287.86 μm of olg
-1.For shitosan blank film, Q can be found
e/ C
eto Q
elinear, show only there is non-specific adsorption sites in shitosan blank film.Wherein, K
d=0.76mmolL
-1, Q
max=83.84 μm of olg
-1.
(4) selective through performance research
Film is fixed between two osmotic cells, in feed reservoir, adds 150mL650mgL
-1chlorogenic acid 20% ethanolic solution, 150mL20% ethanolic solution is added in through pond, electric stirring is all carried out in two ponds, liquid is got at set intervals from through pond sample tap, absorbance is measured by UV-vis, and then draw penetrating fluid and remaining liquid concentration, determine the permeability in one-component solution permeability test.
Permeability test and the above-mentioned experiment of mixed solution are similar, and that just feed reservoir side adds is 150mL650mgL
-1chlorogenic acid and 650mgL
-1caffeic acid 20% alcohol mixed solution, add 150mL20% ethanolic solution through side, pond, Liang Chijun carries out electric stirring, after infiltration 24h, get liquid from through pond sample tap, measure peak area by high performance liquid chromatography (HPLC), and then draw penetrating fluid concentration, determine permeability.
Computing permeability is as follows: first before being HPLC is abscissa with standard solution concentration, peak area is ordinate drawing standard curve, obtain curvilinear equation, then obtain the concentration of penetrating fluid according to the peak area of penetrating fluid detection HPLC, with the concentration of penetrating fluid divided by concentration of raw material 650mgL
-1obtain permeability.
The one-component solution penetration curve of being drawn by experimental data as shown in Figure 8.Experimental result shows, along with the prolongation of time of penetration, penetrating fluid concentration is higher, and the molecule through film is more.Shitosan blank film, owing to only there is the hole of non-specific adsorption, thus can only be adsorbed onto the surface of feed reservoir one side form the chlorogenic acid of only a few and be difficult to transfer to through side, pond, so permeability is extremely low.And also there is the hole of specific adsorption due to chlorogenic acid molecular engram chitosan film, it is documented, this hole can form passage in film inside, so chlorogenic acid can be transferred to the opposite side of film through passage by the side of blotting membrane, so to increase along with the prolongation of time through the chlorogenic acid content of blotting membrane and chlorogenic acid content in remaining liquid reduces along with the prolongation of time, but infiltration rate reduces along with the prolongation of time, this is because initial period, chlorogenic acid mainly permeates by concentration gradient power, and absorption is very fast; Along with the carrying out of adsorption process, the concentration of solution Content of Chlorogenic Acid reduces gradually, and adsorbate internally spreads along micropore simultaneously, and diffusional resistance is cumulative, causes the rate of adsorption slack-off.Make a general survey of full figure, the concentration of the penetrating fluid Content of Chlorogenic Acid of chlorogenic acid molecular engram chitosan film is all the time higher than the concentration of shitosan blank film penetrating fluid Content of Chlorogenic Acid, and the concentration of the remaining liquid Content of Chlorogenic Acid of chlorogenic acid molecular engram chitosan film is all the time lower than the concentration of liquid Content of Chlorogenic Acid more than shitosan blank film; After infiltration 24h, as calculated, the permeability of chlorogenic acid molecular engram chitosan film Content of Chlorogenic Acid is 22.43%, and the permeability of shitosan blank film Content of Chlorogenic Acid is 20.26%, thus chlorogenic acid molecular engram shitosan permeability of the membrane comparatively shitosan blank film is slightly well.
The HPLC of mixed solution permeability test analyzes as shown in Figure 9.Due to caffeic acid and chlorogenic acid similar, therefore select caffeic acid as homologue, determine the transmitance through chlorogenic acid molecular engram chitosan film and shitosan blank film when both coexist.As calculated, in chlorogenic acid molecular engram chitosan film, chlorogenic acid and caffeinic permeability are respectively 33.54% and 31.99%; In shitosan blank film, chlorogenic acid and caffeinic infiltration are respectively 22.12%, 23.15%.Visible, comparatively shitosan blank film is slightly well for chlorogenic acid molecular engram shitosan permeability of the membrane, selective also than slightly well, a part for selective significant not reason may to be caffeinic chemical constitution be chlorogenic acid chemical constitution, also containing-COOH and-OH on caffeic acid, therefore also can be combined with imprinted sites.Relatively the permeability test of one-component solution and the permeability test of mixed solution known, when chlorogenic acid and caffeic acid coexist, chlorogenic acid transmitance in chlorogenic acid molecular engram chitosan film and shitosan blank film increases all to some extent, and chlorogenic acid molecular engram chitosan film is more remarkable, this may be owing to containing chlorogenic acid and caffeic acid in mixed solution, therefore solution concentration comparatively one-component solution is higher, concentration gradient power is larger.
Claims (7)
1. a preparation method for chlorogenic acid molecular engram chitosan film, is characterized in that described method comprises the steps:
(1) casting solution is prepared: shitosan and chlorogenic acid are dissolved in the acetum of volume fraction 2%, filtered through gauze after fully stirring, filtrate deaeration, obtained casting solution; The mass ratio of described shitosan and chlorogenic acid is 10:1, and the volumetric usage of described acetum counts 40mL/g with the quality of shitosan;
(2) be poured on the cleaned glass plate of horizontal positioned by casting solution obtained in step (1), use scraper knifing, after dry, obtained thickness is the hyaline membrane of 60 μm;
(3) hyaline membrane obtained in step (2) is placed in 0.5molL
-1sulfuric acid solution in soak 24h and carry out cross-linking reaction, by the film eluent after crosslinked, described eluant, eluent is the mixed solution of ethanol, acetic acid, water volume ratio 2:3:7, the acetic acid of film excess surface is washed away again with volume fraction 20% ethanolic solution, drying, namely obtains chlorogenic acid molecular engram chitosan film.
2. the method for claim 1, is characterized in that in described step (1), described in be stirred in 60 DEG C of lower magnetic forces and stir 6h.
3. the method for claim 1, is characterized in that in described step (1), and described filtrate deaeration adopts vacuum defoamation.
4. the method for claim 1, it is characterized in that, in described step (2), baking temperature is 60 DEG C, drying time is 12h.
5. the chlorogenic acid molecular engram chitosan film that the method as described in one of Claims 1 to 4 prepares.
6. the application of chlorogenic acid molecular engram chitosan film as claimed in claim 5 in absorption chlorogenic acid.
7. the application of chlorogenic acid molecular engram chitosan film in adsorbing separation chlorogenic acid and caffeic acid as claimed in claim 5.
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| CN108239286A (en) * | 2018-01-25 | 2018-07-03 | 南京医科大学 | Silanization carbon quantum dot surface caffeic acid molecularly imprinted polymer, preparation method and its application |
| CN108727516A (en) * | 2018-09-19 | 2018-11-02 | 中国科学院烟台海岸带研究所 | A kind of chitosan chlorogenic acid salt and its preparation method and application |
| CN111592670A (en) * | 2020-06-24 | 2020-08-28 | 上海应用技术大学 | Preparation method of gamma-polyglutamic acid molecularly imprinted polymer membrane |
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| CN111592670A (en) * | 2020-06-24 | 2020-08-28 | 上海应用技术大学 | Preparation method of gamma-polyglutamic acid molecularly imprinted polymer membrane |
| CN114062455A (en) * | 2021-11-11 | 2022-02-18 | 福州大学 | Molecular imprinting photoelectric chemical sensor based on MXene/bismuth sulfide composite material and preparation method and application thereof |
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