CN114773492B - Starch-based composite material, preparation method and application thereof, starch-based organic film, and preparation method and application thereof - Google Patents
Starch-based composite material, preparation method and application thereof, starch-based organic film, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of soil monitoring, and particularly relates to a starch-based composite material, a preparation method and application thereof, and a starch-based organic film, a preparation method and application thereof. The invention provides a starch-based composite material which has a structure shown in a formula 1 or a formula 2. The starch-based composite material provided by the invention grafts the organic group R with the structure shown in the formula 3 on a starch molecular chain through a boric acid ester bond, the starch-based composite material provided by the invention takes the R substituent with the structure shown in the formula 3 as a hydrogen sulfide photoresponse organic molecular probe, and the change of the fluorescence characteristic is realized due to the change of the R substituent structure to realize the response detection of hydrogen sulfide, so that the indirect detection of the concentration of vibrio desulfurizati in soil can be realized. The starch is used as a matrix, and the signal amplification function can be realized by utilizing the synergistic effect of a plurality of recognition sites, so that the response is quickly detected.
Description
Technical Field
The invention belongs to the technical field of soil monitoring, and particularly relates to a starch-based composite material, a preparation method and application thereof, and a starch-based organic film, a preparation method and application thereof.
Background
Inorganic sulfide is generated in the process of anaerobic decomposition of sulfur-containing organic matters in soil; under the condition of reducing state, the sulfate can also be acted by microorganism to generate sulfide. The sulfide generates hydrogen sulfide when meeting acid, the hydrogen sulfide is easy to escape into the air, odor is generated, and the toxicity is high. It can react with cytochrome, oxidase and disulfide bond in human body to affect cell oxidation process, and cause hypoxia of cell tissue, which endangers human life. Therefore, the sulfide/hydrogen sulfide is an important index for soil detection, and can be used as an indirect method for judging the concentration of the vibrio desulfurizating bacteria in the soil.
The detection method of desulfurization vibrio in soil includes mainly adopting soil substrate to make diethylaminoaniline colorimetric method and iodometry method to detect sulfide/hydrogen sulfide discharged from it, and the soil substrate can be sludge at bottom of river and its rotten animal and plant carcasses. However, the pretreatment operation of the sulfide/hydrogen sulfide analysis method in the substrate is very complicated, a set of complicated separation and fixing devices are required to be connected besides the high-purity nitrogen gas serving as the carrier gas, the occupied space is large, the method is inconvenient to apply, the air blowing time is about 60 minutes per sample generally, the efficiency is very low, and the method is not suitable for analyzing the soil on a large scale.
In the field of photochemical detection, researchers mainly focus on detection of various gas signal molecules in a biological system at present, and due to the particularity of the biological system, a traditional optical sensor for detecting sulfide/hydrogen sulfide is basically designed based on organic micromolecule functional materials, cannot be prepared into a solid detection device, and is limited in application range. Moreover, there is no optical sensor for detecting vibrio desulfovibrio in soil in the prior art.
Disclosure of Invention
In view of the above, the invention provides a starch-based composite material, a preparation method and an application thereof, and a starch-based organic film, a preparation method and an application thereof. The starch-based composite material provided by the invention can realize effective monitoring on hydrogen sulfide in soil quickly, efficiently, conveniently and visually.
In order to solve the technical problem, the invention provides a starch-based composite material, which has a structure shown in formula 1 or formula 2:
r in the formula 1 or the formula 2 is a structure shown in a formula 3:
preferably, the starch-based composite material has a structure represented by formula 1-1:
the invention provides a preparation method of a starch-based composite material, which comprises the following steps:
mixing starch, a photoresponse functional compound and an organic solvent to perform a grafting reaction to obtain a starch-based composite material with a structure shown in a formula 1; the photoresponse functional compound is 9- (4- ([ 2,2' -bithiophene ] -5-yl) -2- (2,4-dinitrophenoxy) styryl) -10- (3-boratabenzyl) acridine-10-salt, and the organic solvent is a good solvent of the photoresponse functional compound.
Preferably, the molar ratio of the photoresponsive functional compound to the starch is (0.033-10): 1.
The invention provides an application of the starch-based composite material in the technical scheme or the starch-based composite material prepared by the preparation method in the technical scheme in hydrogen sulfide detection.
The invention provides a starch-based organic film, which is prepared from the starch-based composite material or the starch-based composite material prepared by the preparation method in the technical scheme.
The invention provides a preparation method of a starch-based organic film, which comprises the following steps:
mixing the starch-based composite material with water to obtain spinning mother liquor; the starch-based composite material is the starch-based composite material in the technical scheme or the starch-based composite material prepared by the preparation method in the technical scheme;
and performing electrostatic spinning on the spinning mother liquor on a substrate to obtain the starch-based organic film.
Preferably, the mass percentage of the spinning mother liquor is 0.1-30%.
Preferably, the parameters of the electrostatic spinning include: the substrate voltage is 5-30 kV, the distance between the substrate and the spinning mother liquor is 5-20 cm, and the spinning speed is 0.1-10 mL/h.
The invention provides an application of the starch-based organic film or the starch-based organic film prepared by the preparation method in the technical scheme in detection of soil hydrogen sulfide or soil vibrio desulfurizati.
The invention provides a starch-based composite material, which has a structure shown in formula 1 or formula 2:
r in the formula 1 or the formula 2 is a structure shown in a formula 3:
according to the starch-based composite material provided by the invention, an organic group R with a structure shown in a formula 3 is grafted on a starch molecular chain through a boric acid ester bond, an R substituent with the structure shown in the formula 3 contains a 2,4-dinitrophenyl ether and bithiophene quinoline salt conjugated structure, before the R substituent is not contacted with hydrogen sulfide, the 2,4-dinitrophenyl ether and bithiophene quinoline salt conjugated structure of the R substituent has a typical Intramolecular Charge Transfer (ICT) effect, and the luminous intensity of the composite material is extremely weak (almost no fluorescence) due to the existence of aromatic nitro; after the contact with hydrogen sulfide, 2,4-dinitrophenyl ether structure in R substituent group of the structure shown in formula 3 is easy to break bonds in the presence of hydrogen sulfide and remove from the R substituent group to obtain phenol, and the R substituent group in the starch-based composite material with the structure of 2,4-dinitrophenyl ether removed has fluorescence characteristics after losing a conjugated structure (a schematic diagram is shown in figure 1). Meanwhile, the starch is used as a matrix of the material, and the starch is used as a natural high molecular polymer substrate, so that an ideal signal amplification function can be realized by utilizing the synergistic effect of a plurality of recognition sites, and the rapid detection response can be realized, and the limitation that the traditional organic small molecular luminescent material cannot be prepared into a solid detection probe can be effectively overcome.
In addition, the starch-based composite material provided by the invention has an organic group with a photoresponse characteristic to hydrogen sulfide, so that the detection of hydrogen sulfide gas molecules in soil can be realized, and the detection of vibrio desulfurizati in soil can be further indirectly realized.
Meanwhile, when the starch-based composite material provided by the invention is used for detecting hydrogen sulfide in soil, the wavelength of a fluorescence emission peak value is close to 750nm, the self-luminous interference effect of partial components in the soil can be avoided, and the starch-based composite material has good chemical structure stability and is convenient to use in a complex soil microenvironment. The starch-based composite material provided by the invention is environment-friendly and degradable, and can not cause negative influence on soil.
The invention provides a preparation method of a starch-based composite material, which comprises the following steps: mixing starch, a photoresponse functional compound and an organic solvent to perform a grafting reaction to obtain a starch-based composite material with a structure shown in a formula 1; the photoresponse functional compound is 9- (4- ([ 2,2' -bithiophene ] -5-yl) -2- (2,4-dinitrophenoxy) styryl) -10- (3-borabenzyl) acridine-10-salt, and the organic solvent is a good solvent of the photoresponse functional compound. The preparation method provided by the invention has the advantages of simple and feasible preparation process, high yield, rich raw material sources and low cost, and is suitable for wide popularization and application.
The invention provides a starch-based organic film, which is prepared from the starch-based composite material or the starch-based composite material prepared by the preparation method in the technical scheme. The starch-based organic film provided by the invention can be used as a solid device to realize the detection of hydrogen sulfide, so that the visual detection of the vibrio desulfurating bacteria is indirectly realized, and the starch-based organic film is convenient to use and carry.
The invention provides a preparation method of a starch-based organic film, which comprises the following steps: mixing the starch-based composite material with water to obtain spinning mother liquor; the starch-based composite material is the starch-based composite material prepared by the preparation method of the technical scheme or the starch-based composite material prepared by the preparation method of the technical scheme; and performing electrostatic spinning on the spinning mother liquor on a substrate to obtain the starch-based organic film. The starch-based organic film is prepared by electrostatic spinning, and compared with the traditional processing technology, the electrostatic spinning technology has the advantages of more convenient and efficient film forming process and better film forming effect; moreover, the starch-based organic film prepared by electrospinning has obvious porosity, and is beneficial to the diffusion of hydrogen sulfide gas molecules released by the vibrio desulfurization in the starch-based organic film, so that the detection effect can be obviously improved, and the determination on the concentration of the vibrio desulfurization is more accurate.
Drawings
FIG. 1 is a schematic diagram illustrating the principle of hydrogen sulfide detection of a starch-based composite material provided by the present invention;
FIG. 2 is an absorption spectrum before and after the response of the starch-based organic film prepared in test example 1 to hydrogen sulfide gas;
FIG. 3 is an emission spectrum before and after response of the starch-based organic film prepared in example 1 in test example 1 to hydrogen sulfide gas;
FIG. 4 is a graph showing the measurement of photostability of the starch-based organic film prepared in example 1 of test example 2;
FIG. 5 is a graph showing the change in intensity of fluorescence signals of the starch-based organic thin film prepared in application example 1 with respect to different doses of hydrogen sulfide impregnated in soil.
Detailed Description
The invention provides a starch-based composite material, which has a structure shown in a formula 1 or a formula 2:
r in the formula 1 or the formula 2 is a structure shown in a formula 3:
in the present invention, the starch-based composite material has a structure represented by formula 1-1:
the invention provides a preparation method of a starch-based composite material, which comprises the following steps:
mixing starch, a photoresponse functional compound and an organic solvent (hereinafter referred to as first mixing) to perform a grafting reaction to obtain a starch-based composite material with a structure shown in formula 1; the photoresponse functional compound is 9- (4- ([ 2,2' -bithiophene ] -5-yl) -2- (2,4-dinitrophenoxy) styryl) -10- (3-borabenzyl) acridine-10-salt, and the organic solvent is a good solvent of the photoresponse functional compound.
In the present invention, the starting materials are all commercially available products well known to those skilled in the art unless otherwise specified.
In the present invention, the starch preferably includes one or more of corn starch, mung bean starch, potato starch, wheat starch, sweet potato starch, lotus root starch, tapioca starch, potato starch, sweet potato starch, kudzu root starch, pea starch, water chestnut starch.
In the invention, the photoresponse functional compound is 9- (4- ([ 2,2' -bithiophene)]-5-yl) -2- (2,4-dinitrophenoxy) styryl) -10- (3-borabenzyl) acridine-10-salt, english name 9- (4- ([ 2,2' -bithiophene)]-5-yl) -2- (2,4-dinitrophenoxy) styryl) -10- (3-boronobenzyl) a cridin-10-ium, abbreviated as BPDBA and having a molecular formula of C 42 H 29 BN 3 O 7 S 2 + Molecular weight is 762.15.
In the present invention, the photoresponsive functional compound has a structure represented by formula 4:
in the present invention, the molar ratio of the photoresponsive functional compound to starch is preferably (0.033 to 10): 1, and more preferably (0.05 to 5): 1.
In a specific embodiment of the invention, the molar ratio of the photoresponsive functional compound to the starch is particularly preferably 0.033.
In the present invention, the organic solvent preferably includes a first organic solvent and a second organic solvent.
In the present invention, the first organic solvent is preferably the starch dispersion medium.
In the present invention, the second organic solvent is preferably a good solvent for the photoresponsive functional compound.
In the present invention, the first mixing preferably includes the steps of:
dispersing starch in a first organic solvent to obtain a starch dispersion liquid;
dissolving the photoresponse functional compound in a second organic solvent to obtain a photoresponse functional compound solution;
and dropwise adding the photoresponse functional compound solution into the starch dispersion liquid.
The invention disperses starch in a first organic solvent to obtain a starch dispersion.
In the present invention, the first organic solvent preferably includes one or more of methanol, ethyl acetate, ethanol, isopropanol, deionized water, tetrahydrofuran, N-dimethylformamide, and dioxane, and more preferably ethanol.
In the present invention, the dispersion is preferably carried out under mechanical stirring.
In the present invention, the molar concentration of the starch dispersion is preferably 1 to 10mol/L.
The photoresponse functional compound is dissolved in a second organic solvent to obtain a photoresponse functional compound solution.
In the present invention, the second organic solvent preferably includes one or more of methanol, ethanol, tetrahydrofuran, N-dimethylformamide, and dimethylsulfoxide.
In the present invention, the dissolution is preferably performed under the condition of ultrasound.
In the present invention, the time for ultrasonic dissolution is preferably 0.1 to 1 hour.
In the present invention, the molar concentration of the photo-responsive functional compound solution is preferably 1 to 30mol/L.
After the photoresponse functional compound solution and the starch dispersion liquid are obtained, the photoresponse functional compound solution is dripped into the starch dispersion liquid.
In the present invention, the temperature at the time of the dropping is preferably performed under a room temperature condition.
In the present invention, the dropping rate is preferably 1 to 10 drops/s.
In the present invention, the volume of each drop of the photo-responsive functional compound solution at the time of the dropping is preferably 0.04 to 0.05mL.
In the present invention, the grafting reaction occurs after the photo-responsive functional compound solution at the time of the dropping and the starch dispersion are contacted.
In the present invention, the dropwise addition is preferably performed under stirring.
In the present invention, the stirring and dropping time is preferably 0.5 to 24 hours.
In the invention, a grafting reaction solution is obtained after the grafting reaction, and the grafting reaction solution is preferably subjected to post-treatment to obtain the starch-based composite material. In the present invention, the post-treatment preferably comprises: dialysis and drying were performed sequentially. In the present invention, the dialysis is preferably: transferring the grafting reaction liquid into the dialysis bag, and immersing the dialysis bag filled with the grafting reaction liquid into a dialysis medium for dialysis. In the present invention, the width of the flattened dialysis bag is preferably 18 to 44mm. In the present invention, the cut-off molecular weight of the dialysis bag is preferably 500 to 50000. In the present invention, the material of the dialysis bag is preferably Regenerated Cellulose (RC), cellulose Ester (CE), or polyvinylidene fluoride (PVDF). In the present invention, the dialysis medium preferably comprises one or more of Dimethylsulfoxide (DMSO), ethanol, tetrahydrofuran, N-dimethylformamide, acetonitrile, and water, preferably deionized water, and in the present invention, the dialysis time is preferably 1 to 120 hours.
In the present invention, the drying is preferably freeze-drying. In the present invention, the temperature of the freeze-drying is preferably-5 to-50 ℃, more preferably-10 to-40 ℃, and still more preferably-15 to-30 ℃. In the present invention, the freeze-drying time is preferably 1 to 120 hours, more preferably 10 to 100 hours, and still more preferably 20 to 80 hours.
The invention provides an application of the starch-based composite material in the technical scheme or the starch-based composite material prepared by the preparation method in the technical scheme in detection of hydrogen sulfide or soil vibrio desulfurization.
The starch-based composite material obtained by the invention is formed by combining an organic molecule (BPDBA) and a starch-based molecule, wherein the BPDBA is 9- (4- ([ 2,2' -bithiophene)]-5-yl) -2- (2,4-dinitrophenoxy) styryl) -10- (3-borabenzyl) acridin-10-salt, C 42 H 29 BN 3 O 7 S 2 + The molecular weight is 762.15, a 2,4-dinitrophenyl ether structure in the molecular structure of the high-molecular-weight thiodiphenyl ether has a good photoresponse characteristic to hydrogen sulfide, and the high-molecular-weight thiodiphenyl ether can be used as a solid molecular device to detect hydrogen sulfide gas in soil after being combined with a starch-based molecular chain, so that vibrio desulfurizati can be indirectly detected.
The starch-based composite material obtained by the invention has a typical 2,4-dinitrophenyl ether structure in the molecular structure, is easy to break in the presence of hydrogen sulfide to become phenol, has a typical Intramolecular Charge Transfer (ICT) effect, has extremely weak fluorescence signal (almost no fluorescence) due to the presence of aromatic nitro groups, releases fluorescence due to the removal of the aromatic nitro groups after the response of the hydrogen sulfide, and is shown in the schematic diagram in fig. 1 before and after the response.
The starch-based organic film is prepared from the starch-based composite material or the starch-based composite material prepared by the preparation method in the technical scheme.
The invention provides a preparation method of a starch-based organic film, which comprises the following steps:
mixing the starch-based composite material with water to obtain spinning mother liquor; the starch-based composite material is the starch-based composite material prepared by the preparation method of the technical scheme or the starch-based composite material prepared by the preparation method of the technical scheme;
and performing electrostatic spinning on the spinning mother liquor on a substrate to obtain the starch-based organic film.
The method comprises the steps of mixing a starch-based composite material with water (hereinafter referred to as second mixing) to obtain spinning mother liquor; the starch-based composite material is the starch-based composite material prepared by the preparation method of the technical scheme or the starch-based composite material prepared by the preparation method of the technical scheme.
In the present invention, the water is preferably deionized water.
In the present invention, the second mixing is preferably carried out under stirring, and the present invention has no particular requirement on the specific implementation process of the stirring.
In the present invention, the temperature of the second mixing is preferably 50 to 100 ℃, more preferably 55 to 90 ℃, and further preferably 60 to 80 ℃.
In the present invention, the holding time for the second mixing is preferably 1 to 6 hours, more preferably 2 to 5 hours.
In the present invention, the spinning mother liquor is preferably contained in an amount of 0.1 to 30% by mass (w/w).
After the spinning mother liquor is obtained, the invention carries out electrostatic spinning on the spinning mother liquor on a substrate to obtain the starch-based organic film.
The spinning mother liquor is preferably transferred into an injector for electrostatic spinning.
In the present invention, the parameters of the electrospinning preferably include: the substrate voltage is preferably 5 to 30kV, more preferably 10 to 25kV; the distance between the substrate and the spinning mother liquor is preferably 5-20 cm, and more preferably 10-15 cm; the spinning rate is preferably 0.1 to 10mL/h, more preferably 0.5 to 8mL/h, and still more preferably 1 to 5mL/h.
In the invention, a wet film is obtained after electrostatic spinning, and the wet film is preferably subjected to post-treatment to obtain the starch-based organic film. In the present invention, the post-treatment is preferably drying. In the present invention, the temperature for the drying is preferably 15 to 30 ℃, more preferably 20 to 25 ℃. In the present invention, the drying is preferably performed in a drying room. In the present invention, the drying is carried out with an air flow rate of preferably 0.1 to 0.6m/s, more preferably 0.2 to 0.5m/s.
The invention provides an application of the starch-based organic film or the starch-based organic film prepared by the preparation method in the technical scheme in detection of soil hydrogen sulfide or soil vibrio desulfurizati.
The invention preferably uses the starch-based organic film to indirectly measure the vibrio desulfurizate in the soil.
In the invention, the starch-based organic film in the technical scheme is adopted to determine hydrogen sulfide in the soil for qualitative detection, and the specific preference is as follows: and measuring the original fluorescence intensity signal of the starch-based organic film, inserting the starch-based organic film into soil, standing for 5-2 min, taking out the starch-based organic film, testing the fluorescence signal intensity of the starch-based organic film, and qualitatively detecting the hydrogen sulfide in the soil through the change of the fluorescence signal intensity.
In the invention, the specific preference of the starch-based organic film in the technical scheme for measuring the hydrogen sulfide in the soil for quantitative detection is as follows: measuring fluorescence signals of the starch-based organic film in contact with hydrogen sulfide with different concentrations to obtain a relation curve between the fluorescence intensity of the starch-based organic film and the concentration of the hydrogen sulfide; and then inserting the starch-based organic film in the technical scheme into soil, standing for 5-2 min, taking out the starch-based organic film, testing the fluorescence signal intensity of the starch-based organic film, and quantitatively detecting the hydrogen sulfide in the soil through the change of the fluorescence signal intensity and the relation curve of the fluorescence intensity of the starch-based organic film and the concentration of the hydrogen sulfide.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the organic micromolecule BPDBA is grafted on the molecular chain of the starch base, so that the organic micromolecule BPDBA has a photoresponse characteristic to hydrogen sulfide, the preparation process is simple and easy to implement, the auxiliary solvent used in the process is relatively environment-friendly, the yield is higher, the raw material source is rich, the cost is lower, and the organic micromolecule BPDBA is suitable for wide popularization and application.
The starch-based organic film prepared by the invention is ingenious in design, the concentration of hydrogen sulfide is judged by the strength of a fluorescent signal released by 2,4-dinitrophenyl ether, so that the relative concentration of the vibrio desulfurizating can be indirectly judged, and meanwhile, the starch is a natural polymer base material, so that various limitations of a traditional organic micromolecule luminescent material can be effectively overcome, and moreover, the polymer-based luminescent material can realize a relatively ideal signal amplification function and rapid detection response by utilizing the synergistic effect of a plurality of identification sites, and more importantly, the starch is an environment-friendly material, is environment-friendly and degradable, and cannot cause negative influence on soil.
The invention adopts the electrospinning during the preparation of the starch-based organic film, the electrospinning has a more convenient and efficient film forming process and a better film forming effect compared with the traditional processing technology, and more importantly, the introduction of the electrospinning can ensure that the starch-based film has obvious porosity, which is beneficial to the diffusion of hydrogen sulfide gas molecules in the starch-based film, so that the detection effect can be obviously improved, and the detection of the vibrio devulcani is more accurate.
The starch-based organic film provided by the invention has the emission wavelength close to 750nm, can avoid the self-luminous interference effect of partial components in soil, has good chemical structure stability and is convenient to use in a complex soil microenvironment.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Dispersing corn starch in ethanol, and mechanically stirring uniformly to obtain a starch dispersion liquid with the molar concentration of 2 mol/L; dissolving 20mol of BPDBA in dimethyl sulfoxide, and carrying out ultrasonic treatment for 0.5h to obtain a BPDBA solution with the molar concentration of 10 mol/L; dropwise adding a BPDBA solution into a starch dispersion liquid at the speed of 2 drops/s, mixing and stirring for 3 hours, controlling the molar ratio of the BPDBA to the starch to be 0.1, carrying out grafting reaction in the stirring process to obtain a grafting reaction liquid, then transferring the grafting reaction liquid into a Regenerated Cellulose (RC) dialysis bag with the flattening width of 40mm and the molecular weight cutoff of 500-50000, dialyzing for 72 hours in a deionized water system, and finally carrying out freeze drying at-40 ℃ for 36 hours to obtain dark red powder, namely the DBBPA-grafted starch-based composite material powder;
adding the obtained starch-based composite material powder into deionized water to prepare a spinning mother solution, wherein the mass percentage content of the starch-based composite material powder is 20% (w/w), stirring for 2h at 80 ℃, transferring the uniform starch-based composite material powder into an injector, controlling the substrate voltage to be 15kV, controlling the distance between a substrate and the injector to be 10cm, spinning at the speed of 1mL/h, drying the obtained film in a drying room, controlling the drying temperature to be 25 ℃ and the airflow rate to be 0.3m/s, and finally obtaining the starch-based organic film with the photoresponse characteristic to hydrogen sulfide.
Example 2
Dispersing wheat starch in ethanol, and mechanically stirring uniformly to obtain a starch dispersion liquid with the molar concentration of 10 mol/L; dissolving 25mol of BPDBA in dimethyl sulfoxide, and carrying out ultrasonic treatment for 1h to obtain a BPDBA solution with the molar concentration of 1 mol/L; dropwise adding a BPDBA solution into a starch dispersion liquid at the speed of 1 drop/s, mixing and stirring for 0.5h, controlling the molar ratio of the BPDBA to the starch to be 10, carrying out grafting reaction in the stirring process to obtain a grafting reaction liquid, then transferring the grafting reaction liquid into a Cellulose Ester (CE) dialysis bag with the flattening width of 18mm and the molecular weight cutoff of 500-50000, dialyzing for 1h in a deionized water system, and finally carrying out freeze drying at the temperature of-5 ℃ for 1h to obtain dark red powder, namely the starch-based composite material powder grafted by the BPDBA;
adding the obtained starch-based composite material powder into deionized water to prepare spinning mother liquor, wherein the mass percentage of the starch-based composite material powder is 30% (w/w), stirring for 1h at 100 ℃, transferring the uniform starch-based composite material powder into an injector, controlling the substrate voltage to be 5kV, controlling the distance between a substrate and the injector to be 5cm, spinning at the speed of 0.1mL/h, drying the obtained film in a drying room, controlling the drying temperature to be 15 ℃, and controlling the air flow rate to be 0.1m/s, and finally obtaining the starch-based organic film with the photoresponse characteristic to hydrogen sulfide.
Example 3
Dispersing potato starch in ethanol, and mechanically stirring uniformly to obtain a starch dispersion liquid with a molar concentration of 1 mol/L; dissolving 1mol of BPDBA in dimethyl sulfoxide, and carrying out ultrasonic treatment for 0.1h to obtain a BPDBA solution with the molar concentration of 30 mol/L; dripping a BPDBA solution into a starch dispersion liquid at the speed of 10 drops/s, mixing and stirring for 24 hours, controlling the mole ratio of BPDBA to starch to be 0.033, carrying out grafting reaction in the stirring process to obtain a grafting reaction liquid, transferring the grafting reaction liquid into a polyvinylidene fluoride (PVDF) dialysis bag with the flattening width of 44mm and the molecular weight cutoff of 500-50000, dialyzing for 120 hours in a deionized water system, and finally carrying out freeze drying at-50 ℃ for 120 hours to obtain dark red powder, namely the DBBPA grafted starch-based composite powder;
adding the obtained starch-based composite material powder into deionized water to prepare a spinning mother solution, wherein the mass percentage content of the starch-based composite material powder is 0.1% (w/w), stirring for 6h at 50 ℃, transferring the uniform starch-based composite material powder into an injector, controlling the substrate voltage to be 30kV, controlling the distance between the substrate and the injector to be 20cm, spinning at the speed of 10mL/h, drying the obtained film in a drying room, controlling the drying temperature to be 30 ℃, and controlling the air flow rate to be 0.6m/s, and finally obtaining the starch-based organic film with the photoresponse characteristic to hydrogen sulfide.
Test example 1
Spectroscopic response test on the starch-based organic film prepared in example 1;
100 mu mol/L of hydrogen sulfide test solution is prepared, and the starch-based organic film obtained in example 1 is dried before testing. In specific testing, the hydrogen sulfide to be tested is directly sprayed on the starch-based organic film prepared in example 1, and the response effect of the starch-based organic film to the hydrogen sulfide is tested under the excitation wavelength of 510nm, wherein the response effect comprises the change of the absorption wavelength before and after response and the release effect of a fluorescence signal. The test results are shown in fig. 2 and 3. As can be seen from FIG. 2, the maximum absorption peak of the spectrum is red-shifted from 507.3nm to around 532.2nm before and after the starch-based film responds, which may be due to the change of electron push-pull effect in BPDBA molecules caused by the removal of 2,4-dinitroanisole during the response process, and the exposure of phenolic hydroxyl groups after the response causes the increase of electron donating ability, thereby causing the red shift of the spectrum. As can be seen from FIG. 3, the fluorescence intensity of the test solution is very weak (almost no signal) before the test solution is not contacted with hydrogen sulfide, and after the hydrogen sulfide is added, the test solution releases a strong optical signal around 748.8nm, which indicates that the signal release of BPDBA can be significantly changed by the presence of the hydrogen sulfide, i.e. the BPDBA has a good response effect on the hydrogen sulfide.
Test example 2
Photostability test of the starch-based organic film prepared in example 1:
preparing hydrogen sulfide test solution with the test concentration of 100 mu mol/L, and storing at low temperature before the experiment. In a specific experiment, a hydrogen sulfide test solution with a concentration of 100 mu mol/L is sprayed on the starch-based organic film, the starch-based organic film is placed under a 365nm ultraviolet lamp and is respectively irradiated for different time lengths, the irradiation time range is 0-120min, the starch-based organic film irradiated for different time lengths is respectively subjected to spectroscopy test in 10min, 30min, 60min and 120min, and a specific test result is shown in fig. 4. As can be seen from the attached figure 4, the starch-based organic film has a relatively stable fluorescence intensity signal for the release of hydrogen sulfide within the range of the tested time length, which indicates that the organic film has relatively good light stability and a relatively wide application range.
Application example 1
Detection of hydrogen sulfide impregnation in soil: selecting common soil (such as clay), adding hydrogen sulfide solutions with different concentrations (0 mu M, 5 mu M, 10 mu M and 20 mu M) (simulating the process of reducing sulfate into hydrogen sulfide by vibrio desulfurizate under anaerobic conditions), soaking at room temperature for a period of time, inserting the starch-based organic film prepared in example 1 into the soil, standing for 0.5-2 min, taking out the starch-based organic film, and testing the signal intensity of the starch-based organic film, wherein the specific result is shown in fig. 5. As can be seen from FIG. 5, the fluorescence signal intensity of the soil is gradually increased with the increase of the concentration of hydrogen sulfide in the soil, which indicates that the concentration of hydrogen sulfide in the soil can be measured through the change of the fluorescence signal intensity, and based on the result, the relative concentration of the vibrio desulfovibrio in the soil can be indirectly judged, namely the prepared starch-based organic film can realize visual detection of the vibrio desulfovibrio in the soil, which is of great significance for studying colony ecology in the soil microenvironment.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. A starch-based composite material having a structure represented by formula 1 or formula 2:
r in the formula 1 or the formula 2 is a structure shown in a formula 3:
2. the starch-based composite material according to claim 1, wherein the starch-based composite material has a structure represented by formula 1-1:
3. a method for preparing a starch-based composite material according to claim 1 or 2, comprising the steps of:
mixing starch, a photoresponse functional compound and an organic solvent to perform a grafting reaction to obtain a starch-based composite material with a structure shown in a formula 1; the photoresponse functional compound is 9- (4- ([ 2,2' -bithiophene ] -5-yl) -2- (2,4-dinitrophenoxy) styryl) -10- (3-borabenzyl) acridine-10-salt, and the organic solvent is a good solvent of the photoresponse functional compound.
4. The method according to claim 3, wherein the molar ratio of the photoresponsive functional compound to the starch is (0.033 to 10): 1.
5. Use of the starch-based composite material according to claim 1 or 2 or the starch-based composite material obtained by the preparation method according to claim 3 or 4 for detecting hydrogen sulfide.
6. A starch-based organic film produced from the starch-based composite material according to claim 1 or 2 or the starch-based composite material produced by the production method according to claim 3 or 4.
7. The method of preparing a starch-based organic film according to claim 6, comprising the steps of:
mixing the starch-based composite material with water to obtain spinning mother liquor; the starch-based composite material is the starch-based composite material of claim 1 or 2 or the starch-based composite material prepared by the preparation method of claim 3 or 4;
and performing electrostatic spinning on the spinning mother liquor on a substrate to obtain the starch-based organic film.
8. The preparation method of claim 7, wherein the mass percentage of the spinning mother liquor is 0.1-30%.
9. The method for preparing according to claim 7 or 8, wherein the parameters of the electrospinning comprise: the substrate voltage is 5-30 kV, the distance between the substrate and the spinning mother liquor is 5-20 cm, and the spinning speed is 0.1-10 mL/h.
10. Use of the starch-based organic film according to claim 6 or the starch-based organic film prepared by the preparation method according to any one of claims 7 to 9 in soil hydrogen sulfide detection.
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| US6063914A (en) * | 1997-01-25 | 2000-05-16 | Stockhausen Gmbh & Co. Kg | Method of producing swellable, non-aging starch maleates, biologically degradable starch maleates as well as use |
| EP1473308A1 (en) * | 2003-04-28 | 2004-11-03 | B. Braun Melsungen Ag | Derivatives of starch for clinic use, especially parenteral |
| EP2899213A1 (en) * | 2014-01-27 | 2015-07-29 | Basf Se | Modified polysaccharides, method for their production and their use |
| CN104877667A (en) * | 2015-04-01 | 2015-09-02 | 北京师范大学 | Fluorescent response thin-film material having humidity sensitive characteristics and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7674354B2 (en) * | 2004-07-01 | 2010-03-09 | Cargill, Incorporated | Starch derivatives for use in paper sizing and/or coating compositions |
| RU2017135502A (en) * | 2015-03-12 | 2019-04-12 | Геркулес Ллк | COMPOSITION FOR OIL AND GAS WELL HANDLING, INCLUDING HYDROXYETHYL CELLULOSE AND STAINED POLYVINYLPIRROLIDONE |
| WO2016160737A1 (en) * | 2015-04-03 | 2016-10-06 | E I Du Pont De Nemours And Company | Oxidized dextran |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6063914A (en) * | 1997-01-25 | 2000-05-16 | Stockhausen Gmbh & Co. Kg | Method of producing swellable, non-aging starch maleates, biologically degradable starch maleates as well as use |
| EP1473308A1 (en) * | 2003-04-28 | 2004-11-03 | B. Braun Melsungen Ag | Derivatives of starch for clinic use, especially parenteral |
| EP2899213A1 (en) * | 2014-01-27 | 2015-07-29 | Basf Se | Modified polysaccharides, method for their production and their use |
| CN104877667A (en) * | 2015-04-01 | 2015-09-02 | 北京师范大学 | Fluorescent response thin-film material having humidity sensitive characteristics and preparation method thereof |
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