CN116217749A - Telechelic alginate-based amphiphilic particle emulsifier, stable Pickering emulsion and application thereof - Google Patents
Telechelic alginate-based amphiphilic particle emulsifier, stable Pickering emulsion and application thereof Download PDFInfo
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- sodium alginate
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
Abstract
The invention provides a sodium alginate-based telechelic molecule (ATMs), which is a 7-amino-4-methylcoumarin grafted sodium alginate derivative. The ATMs can form a large number of assemblies by self-assembly in aqueous solution, can effectively stabilize Pickering emulsion by adopting the ATMs as a stabilizer, can promote the adjustment of aggregate interaction in the solution, and can also serve as a physical cross-linking agent to enhance the droplet-droplet interaction when being adsorbed on the oil-water interface of the Pickering emulsion. In addition, ATMs dimerize under UV light (including photodimerization within aggregates and photodimerization between aggregates) and act as stabilizers to further enhance Pickering emulsion stability. The method provides a basis for researching the influence of the molecular structure on the stability of Pickering emulsion and deeply understanding the microstructure-property relationship of the amphiphilic macromolecular emulsifier.
Description
Technical Field
The invention relates to a telechelic alginate-based amphiphilic particle emulsifier, and stable Pickering emulsion and application thereof.
Background
A novel Pickering emulsion stabilized at the oil/water interface by polymeric "soft particles" has been developed with adjustable microstructure and viscoelasticity, providing an indispensable platform for meeting the specific needs of industrial and emerging applications. The utilization of amphiphilic self-assembled polymers such as micelles, vesicles, microgels and the like enables the polymer 'soft particle' emulsifier to have the advantages of both the polymer and the amphiphilic self-assembled body. The Pickering emulsion stabilized by the polymer 'soft particles' has obvious stability advantage compared with the traditional Pickering emulsion, and is very beneficial to the development of the emulsion field in terms of foundation and application. It is well known that the self-assembled microstructure of the oil-water interface, the viscoelasticity, the interfacial behavior and properties of particle-particle and droplet-droplet interactions are critical for exploring the stability mechanism of Pickering emulsions. Thus, pickering emulsions with tunable interfacial microstructure and viscoelasticity are worth further investigation.
At present, many studies have proposed the passage of temperature, pH, electricity, CO 2 /N 2 Or external stimuli such as magnetic fields, etc. to modulate the interfacial properties of the Pickering emulsion. The amphiphilic polymer adsorbed on the oil-water interface can act as a "soft" building block, and the interfacial properties of the Pickering emulsion can be tailored as desired, providing attractive properties for further applications. Light has been identified as a potential trigger for modulating the system viscoelasticity in a lossless manner, with high spatial-temporal resolution. Because coumarin can pass [ 2pi+2pi ] under ultraviolet irradiation]Cycloaddition produces photoinduced dimerization, forming covalent crosslinks. Therefore, coumarin has been widely used as a potential light response structure building unit for development of light response functional materials. In addition, coumarin has been reported to form a dynamic network in water as a telechelic molecule to enhance the rheological properties of solutions. However, the related research on interface information of photocrosslinked amphiphilic self-assembled polymer particles serving as Pickering emulsifiers is very little at present. Therefore, development of the amphiphilic self-assembled particles capable of regulating and controlling the oil-water interface property according to the requirement is of great significance for understanding the stability mechanism of the emulsion.
As the demand for green sustainable emulsifiers increases in the modern industry, there is a need to find available alternatives to chemical surfactants. Most polysaccharides and their derivatives are considered as sustainable emulsifiers. In recent years, sodium alginate has received increasing attention as a natural macromolecule that is non-toxic and biocompatible. The current research fully proves that the sodium alginate derivative obtained after the hydrophobic modification has excellent amphipathy. Since emulsion stability is highly dependent on the structure, composition, mechanical properties and evolution of the interfacial colloidal particle film. Thus, research into the properties of multiscale interfaces to gain insight into the microstructure-property relationships of amphiphilic macromolecular emulsifiers remains a challenge.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and aims to graft the Amphiphilic Telechelic Macromolecules (ATMs) based on sodium alginate of coumarin groups through Ugi condensation reaction. A unique network structure and covalently linked ATMs bridge are presented that describe interesting aggregation behavior at the oil-water interface. In addition, ATMs particles not only promote the regulation of aggregation interactions in solution, but also act as physical crosslinkers to enhance droplet-droplet interactions when adsorbed at the oil-water interface of Pickering emulsions.
The first aspect of the invention provides a sodium alginate-based telechelic molecule, which is a compound represented by structural formula (1):
in a second aspect of the invention there is provided a photodimerization reactant after UV irradiation of sodium alginate based telechelic molecules according to the first aspect of the invention.
The third aspect of the invention provides a preparation method of the sodium alginate-based telechelic molecule according to the first aspect of the invention, formaldehyde, 7-amino-4-methylcoumarin/DMSO solution and cyclohexyl isocyanide are added into sodium alginate solution with pH of 3.2-4, stirring reaction is completed at room temperature, and the sodium alginate-based telechelic molecule is obtained after purification.
In a fourth aspect, the invention provides an assembly formed by self-assembly of sodium alginate-based telechelic molecules according to the first aspect of the invention in aqueous solution.
In a fifth aspect of the present invention, a Pickering emulsion is provided, where the Pickering emulsion includes an oil-water phase, and the sodium alginate-based telechelic molecule according to the first aspect of the present invention is used as a stabilizer, or the sodium alginate-based telechelic molecule according to the first aspect of the present invention is photo-dimerized by UV irradiation, and then used as a stabilizer.
Wherein the volume ratio of the oil phase to the water phase of the emulsion is 1:0.1-10, preferably the volume fraction of the oil in the emulsion is not less than 0.5, more preferably not less than 0.7, more preferably not less than 0.8;
preferably, the concentration of sodium alginate based telechelic molecules in the aqueous phase is 0.05 to 0.5wt% in the absence of UV irradiation.
Preferably, the concentration of sodium alginate based telechelic molecules in the aqueous phase prior to irradiation is 0.05-0.5wt% in the presence of UV irradiation.
Wherein the oil phase comprises a water-insoluble or slightly water-soluble solvent, and the solvent is preferably any one or a mixture of at least two of silicone oil, fatty esters, aromatic hydrocarbons, alkanes and alcohols with a C chain length of 6-16, and petroleum hydrocarbons with a C chain length of 22-50, and more preferably any one or a mixture of at least two of fatty esters, alkanes or alcohols with a C chain length of 6-16.
The oil phase may be a common oil phase for preparing emulsion, and the present invention is not particularly limited herein, and may be reasonably selected by those skilled in the art according to the needs of practical application. Preferably, the oil phase may consist of only a solvent which is not or slightly soluble in water, preferably, the oil phase may contain other soluble substances selected from any one or a mixture of at least two of a fat-soluble drug, a fat-soluble label, a fat-soluble enzyme or a fat-soluble protein.
The aqueous phase may be a common aqueous phase for preparing an emulsion, and the present invention is not particularly limited herein, and may be appropriately selected by those skilled in the art according to the needs of practical applications. Preferably, the aqueous phase comprises any one or a mixture of at least two of water, phosphate buffer, acetate buffer, citrate buffer or Tris buffer.
Preferably, the aqueous phase further comprises other water-soluble substances, wherein the water-soluble substances are any one or a mixture of at least two of salts, antibodies, protein polypeptide drug enzymes, cytokines or saccharides. The salt substance is sodium chloride, sodium acetate, potassium chloride, calcium chloride, etc.
The sixth aspect of the invention provides a method for preparing the Pickering emulsion according to the fifth aspect of the invention, wherein the sodium alginate-based telechelic molecules according to the first aspect of the invention are dispersed in a water phase, added with an oil phase and emulsified, so as to obtain the sodium alginate-based telechelic emulsion; or dispersing the sodium alginate-based telechelic molecules in the first aspect of the invention in a water phase, performing UV irradiation to enable the sodium alginate-based telechelic molecules to photo-dimerize, adding an oil phase, and emulsifying to obtain the modified sodium alginate-based telechelic.
Wherein the UV irradiation is performed for at least 30min, preferably at least 1h, more preferably at least 2h, and still more preferably 2h to 5h.
A seventh aspect of the invention provides the use of a sodium alginate-based telechelic molecule according to the first aspect of the invention, or a product according to the second aspect of the invention, or an assembly according to the fourth aspect of the invention, or a Pickering emulsion according to the fifth aspect of the invention, for studying the relationship between molecular structure and stability of the Pickering emulsion
An eighth aspect of the invention provides the use of a sodium alginate-based telechelic molecule according to the first aspect of the invention, or a product according to the second aspect of the invention, or an assembly according to the fourth aspect of the invention, or a Pickering emulsion according to the fifth aspect of the invention, in the fields of biological medicine, cosmetics, food, petroleum and wastewater treatment.
The sodium alginate-based telechelic molecules (ATMs) can form a large number of assemblies by self-assembly in aqueous solution, and can effectively stabilize Pickering emulsion by adopting the sodium alginate-based telechelic molecules (ATMs) as a stabilizer, so that the ATMs not only can promote the adjustment of aggregation interaction in the solution, but also can serve as a physical cross-linking agent to enhance the interaction between liquid drops when being adsorbed on the oil-water interface of the Pickering emulsion. In addition, ATMs dimerize under UV light (including photodimerization within aggregates and photodimerization between aggregates) and act as stabilizers to further enhance Pickering emulsion stability. The microscopic structure-property relationship of the amphiphilic macromolecular emulsifier provides a basis for researching the relationship between the molecular structure and the stability of Pickering emulsion.
Drawings
FIG. 1 shows a synthetic procedure for amphiphilic telechelic molecules.
FIG. 2 (A) FTIR spectra of Alg and ATMs; (B) a plot of fluorescence intensity as a function of ATMs concentration.
FIG. 3 shows the morphology of ATMs micelles before (a) and after (b) irradiation.
FIG. 4 (a) UV-vis spectra of ATMs solutions, (b) schematic self-assembly of ATMs.
FIG. 5 shows the macroscopic stability of Pickering emulsions stabilized by ATMs at various oil fractions, wherein (a) the ATMs were solution-stabilized Pickering emulsions without illumination and (b) the ATMs were stabilized Pickering emulsions after UV illumination.
FIG. 6 is an optical picture of ATMs stabilized Pickering emulsions in the absence of light (a) and UV irradiation (c); laser confocal pictures of ATMs stabilized Pickering emulsion in absence of light (b) and UV irradiation (d).
FIG. 7 shows the difference phi between before (a, c) or after (b, d) irradiation of ultraviolet light o SEM image of the emulsion below.
Fig. 8 is the results of rheological tests of Pickering stabilized by ATMs micelles of different structures: (a) steady state shear rheology; (b) strain sweep; (c) frequency sweep test at 25℃with strain of 1%.
FIG. 9 is a schematic diagram showing interfacial adsorption of ATMs of different molecular structures at the oil-water interface. (a) The possible interface behavior of ATM before or after uv irradiation at the oil-water interface is depicted; (b) Δf and Δd curves of ATMs before or after adsorption and desorption; (c) ΔD- Δf plots of ATMs of different molecular structures; (d) Thickness h f The method comprises the steps of carrying out a first treatment on the surface of the (e) mass; (f) Shear viscosity eta r The method comprises the steps of carrying out a first treatment on the surface of the (g) Modulus of shear elasticity mu f The method comprises the steps of carrying out a first treatment on the surface of the The ATMs in the aqueous phase were all 0.1w%.
Detailed Description
The invention will be further described with reference to specific embodiments in order to provide a better understanding of the invention. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
1. Synthesis of sodium alginate-based telechelic molecule
Sodium alginate (Alg, G/M ratio of 1.74 as determined by round dichroism) and 7-amino-4-methylcoumarin were purchased from ala Ding Huaxue reagent limited (Shanghai, china). Both Azobisisobutyronitrile (AIBN) and cyclohexylisocyante were ordered from the carbofuran chemical company, inc. Styrene and formaldehyde were purchased from mikrin chemical company, inc. Solvent oil No.150 (S-150) was supplied by Jiangsu Huaren chemical Co., ltd. All reagents were used without further purification.
Grafting 7-amino-4-methylcoumarin on a sodium alginate framework to prepare Amphiphilic Telechelic Molecules (ATMs), wherein the preparation process is as follows: a homogeneous solution of sodium alginate (2.5 wt%,80 mL) was adjusted to pH 3.6 by the addition of 0.5M hydrochloric acid. Subsequently, formaldehyde (1.8 mmol), a 7-amino-4-methylcoumarin/DMSO solution (1.3 mmol) and cyclohexyl isocyanide (1.8 mmol) were added sequentially to the solution, and the mixture was stirred at room temperature for 24h. The product was dialyzed against distilled water for 3 days and further lyophilized to give the desired ATMs product.
FTIR and for purified amphiphilic telechelic molecules ATMs 1 The H NMR spectrum was characterized in detail, demonstrating the successful synthesis of the amphiphilic polymer, as shown in fig. 2A. The result shows that hydrophobic groups (cyclohexyl and coumarin) are successfully grafted to the hydrophilic sodium alginate molecular skeleton, so that the amphiphilic functional group of the alginate is endowed.
1 H NMR(400MHz,D 2 O):δ＝3.5-5.5(br,m,H of Alg),6.38(s,1H,–ArH–),7.45(s,1H,–ArH–),7.89(s,1H,–ArH–),2.43(s,3H,–CH 3 –),1.37-1.90,1.12(m,–C 6 H 11 –).FTIR(KBr):υ＝2928.93cm -1 (C–H),2854.48cm -1 (–CH 2 ),1717.33cm -1 (C＝O),1615.17cm -1 (–COO–),1252.81cm -1 (C–O).
The amphiphilic telechelic molecules can self-assemble in aqueous solution to form an assembly. The prepared ATMs were prepared into ATMs solutions of different concentrations by adding distilled water, and the fluorescence intensity of the solutions was measured using a fluorescence spectrophotometer to determine the Critical Aggregation Concentration (CAC) of the ATMs. As the concentration of ATMs increases, the fluorescence intensity of the solution also increases. The inflection point demonstrated that ATMs formed a large number of assemblies in aqueous solution, and the CAC value of ATMs was measured to be about 0.233g/L (FIG. 2B).
2. Preparation of aqueous phases of different molecular structures
ATMs were dissolved in distilled water to obtain a 0.1% (w/w) solution. In addition, photo-dimerization of coumarin derivatives was achieved by irradiating the ATMs solution under an ultraviolet lamp (365 nm,10 w). The optical change in the appearance of the solution was measured by an ultraviolet-visible spectrophotometer.
The photo-crosslinking aggregation behavior of ATMs under UV irradiation is shown in FIGS. 3-4. The ATMs solution showed blue fluorescence under uv irradiation, while with the irradiation time the fluorescence intensity was significantly reduced and clustered together, the reaction could reach its photostable state, indicating that photodimerization of coumarin derivatives occurred in the molecules (fig. 3b, fig. 4 a). Driven by hydrophobic interactions, ATM self-assembles into aggregates prior to uv radiation, as shown in TEM images. The aggregates contracted after 120 minutes of uv irradiation, and larger aggregates were also observed. The photo-dimerization reaction between coumarin fragments occurs not only inside aggregates, but also between aggregates. The photodimerization within the aggregates makes the structure of the aggregates more dense, while the bulk is the photodimerization between the aggregates. The ATMs solution exhibits blue fluorescence under ultraviolet irradiation, and the fluorescence intensity is obviously reduced along with the extension of irradiation time, which indicates that the coumarin end group can generate photoinduced dimerization. Furthermore, the dimerization reached a light steady state within 300 minutes. The self-assembled behaviour of the amphiphilic telechelic molecule is schematically shown in figure 4 b.
3. Preparation of Pickering emulsion
ATMs solution (0.1 wt%, before and after uv irradiation) and oil phase (oil volume fraction phio= 0.5,0.67,0.7,0.8) were mixed at a speed of 10,000rpm for 3 minutes to prepare Pickering emulsion.
As shown in fig. 5, ATMs before and after UV irradiation are capable of forming Pickering emulsions at different oil phase fractions, thus exhibiting good amphiphilicity. At the same polymer concentration, a higher oil volume fraction o results in a higher emulsified phase volume and lower flowability, resulting in an increase in stability. However, for low phio (0.5 and 0.67), there was no significant difference in the appearance of Pickering emulsions stabilized by ATMs. At phio=0.7, UV-free ATMs stabilized Pickering emulsions exhibited fluidity, indicating that photocrosslinked ATMs micelles could improve emulsifying properties. The Pickering emulsion at Φo=0.8 showed the highest stability. Thus, the Pickering emulsion system with phi o=0.8 was chosen as the subject in the following study.
4. Interfacial Properties of Pickering emulsions
To demonstrate that the interfacial activity of ATMs of different structures in the oil-water interface is not a special case, the interfacial properties of Pickering emulsions were studied on a microscopic scale.
For easy observation, rhodamine B (RhB) (concentration) is added into the oil phase<10 -6 mol/L), and then adding ATMs solution (0.1 wt% before and after ultraviolet irradiation) and oil phase (oil volume fraction phi o =0.8) was mixed at 10,000rpm for 3 minutes to prepare a Pickering emulsion, which was observed using a laser scanning confocal microscope (CLSM).
The microstructure of the ATMs at the oil/water interface is critical to the stability of the Pickering emulsion. The effect of interfacial activity of the different self-assembled structures of ATMs on emulsifying properties was confirmed by optical micrograph and CLSM images (fig. 5). By marking the polymer with RhB to make the soft particles visible, it can clearly be observed that adsorption and accumulation of ATM at the oil/water interface results in the formation of a dense interfacial film, which creates a dense barrier for the droplets, prevents coalescence and contributes to the stability of the Pickering emulsion (fig. 6a, c). The structure of ATM is an important parameter affecting the stability of the Pickering emulsion. When the oil volume fraction was kept at 0.8, the Pickering emulsion stabilized by photo-crosslinked ATMs showed smaller droplet size and thicker interfacial film than the emulsion prepared by ATMs without UV, as shown in FIG. 6 (b, d).
The structure of the amphiphilic substance plays a crucial role in influencing the interfacial behaviour and emulsifying properties. To further investigate the effect of photocrosslinking structures on micelle interface properties, oil-in-water (styrene) Pickering emulsions were prepared with styrene (containing initiator) instead of the oil phase. The surface morphology of the polystyrene microsphere is analyzed through SEM, so that the relationship between the structure and the emulsifying property of the polymer micelle is better understood. It can be seen that for different molecular structures, the ATMs Pickering emulsion without UV illumination had a small amount of self-assembled sphere aggregates present at the oil/water interface, as shown in FIG. 7 (a, c). In comparison, in fig. 7 (b, d), the UV-irradiated ATMs stabilized oil-water interface exhibited a rough surface and a denser interfacial particle film, indicating that photocrosslinked micelles could enhance interfacial adsorption, i.e., exhibited typical particle emulsifiers and enhanced particle aggregation due to the formation of stronger attractive interactions between adjacent particles. Furthermore, at different phi o And phi under the experimental conditions of (1) o Compared to =0.67, all samples were at Φ o The stable Pickering emulsions at =0.8 all exhibited greater interfacial coverage and smaller droplet size, indicating Φ o The increase in Pickering emulsion enhances the stability of the Pickering emulsion. These results are consistent with those observed in the macroscopic physical image of Pickering emulsion. Therefore, this also demonstrates that the interfacial assembly behavior of ATMs with different self-assembled structures in the oil-water interface is not a special case. It does support our initial hypothesis that cross-linked ATMs micelles enhance particle-particle interactions. The stability and droplet size of all Pickering emulsions depends on the structure of the soft particles.
5. Pickering emulsion viscoelasticity
The effect of photodimerization of coumarin groups on the viscoelasticity of Pickering emulsions was studied with the results of the above preliminary observations quantified on a microscopic scale by the rheological properties of Pickering emulsions.
Combining ATMs in solution(0.1 wt.% before and after UV irradiation) and an oil phase (oil volume fraction #) o =0.8) was mixed at 10,000rpm for 3 minutes to prepare a Pickering emulsion.
The rheological properties of the emulsions were determined with a DHR rotarheometer (TA, USA) equipped with a parallel plate clamp (diameter 60 mm) at 25 ℃. Stable shear flow test is carried out in a controlled rate mode, and the shear rate ranges from 0.01 to 1200s -1 . The linear viscoelastic region was determined by performing an oscillatory strain sweep experiment with an increase in the linear viscoelastic region of the emulsion at a frequency of 1Hz in the range of 0.01-1000%. The oscillation frequency sweep test was performed at a fixed strain amplitude of 1% in the linear range, the frequency sweep range was 0.01Hz to 100Hz, and the elastic modulus G' and the viscous modulus G "versus frequency curves were recorded.
Figure 8a shows that all emulsions exhibit typical shear thinning behavior. At a fixed shear rate, the viscosity of the crosslinked ATMs micelle stabilized Pickering emulsion was higher than the sample prior to light irradiation. Fig. 8b is a strain sweep test of a Pickering emulsion. The presence of the crossover point was observed under all pressure conditions. The test was performed under conditions where the Linear Viscoelastic Region (LVR) range was below 1%, ensuring data accuracy. Thus, as shown in fig. 8c, frequency sweep measurements were performed on Pickering emulsions prepared with ATMs before and after illumination at an amplitude of 1%. In all samples, G' was higher than G "over the entire frequency range, and thus, the Pickering emulsion exhibited a weak gel-like character from which it can be deduced that the elastic behavior of the oil-water interface film. In all cases, the G 'and G "of the corresponding samples after UV irradiation were increased, especially G', compared to the Pickering emulsion stabilized with non-irradiated ATMs, which means that the interfacial film formed at the oil-water interface of the ATMs after photo-dimerization was more elastic than that formed with non-irradiated ATMs. The results show that the photo-crosslinked ATMs enhance the strength of the three-dimensional network structure and the elasticity of the interfacial film formed by the oil-water interface, and the interaction between emulsion droplets stabilized by the photo-dimeric micelles can have a stronger barrier. This also does confirm our original hypothesis that the stronger interactions between adjacent viscous particles caused by photodimerization directly lead to higher emulsion viscosity and viscoelasticity (G' and G ").
Dissipative quartz crystal microbalances (QCM-D) are a powerful technique that can sensitively monitor the viscoelasticity of solid/liquid interfacial films. Adsorption behavior and interfacial properties of ATM on oil film surface were studied using QCM-D model of Q-Sense E4 system (Biolin Scientific AB, sweden) and gold sensor (QSX) to help understand the potential stability mechanism of Pickering emulsion on microscopic scale. The specific operation is as follows, 300mL oil/CHCl 3 The solution (0.5% w/v) was spin coated (30 s) onto a clean gold sheet surface at 3000 rpm. The gold flakes were then dried under vacuum at 40 ℃ for 12 hours. ATMs (before and after UV irradiation) were introduced into the test cell and QCM-D tested at a flow rate of 50mL/min (25 ℃). All gold pieces were washed with a washing solution (a 5:1:1 ratio mixture of Millipore water, 30% hydrogen peroxide and 25% ammonia) at 75 ℃ for 20 minutes, finally with water and dried with nitrogen.
Figure 9a depicts the possible interface behavior of an ATM before or after uv irradiation at the oil-water interface. Δf and Δd are the changes in frequency and dissipation, respectively. In fig. 9b, a decrease in Δf and an increase in Δd are observed during adsorption, which means that a large amount of ATMs is deposited on the sensor surface. With the addition of ATMs, the amphiphilic polysaccharide assemblies continue to interact with the oil layer. Adsorption equilibrium did not occur even at the end of the 22 hour adsorption period. ATM after UV irradiation (Δf-6 Hz, ΔD-7×10) -6 ) Shows the highest response in frequency and dissipation variation than before ultraviolet irradiation (Δf-4 Hz, Δd-5.5x10-6), probably due to the increase in the adsorption of the particulate emulsifier due to photodimerization.
The ΔD- Δf plot determines the conformational change and properties of the adsorption membrane. The change in ΔD/Δf slope represents a conformational change. After addition of amphiphilic polymer, the adsorption behavior represents "fast" kinetics, such as curves where scattering occurs and higher slopes. Subsequently, the curve follows a "slow" kinetics and exhibits a lower slope, indicating the possible presence of multi-layer adsorption. During slow adsorption, the ATMs slope after UV irradiation were higher than the ATMs before irradiation, indicating a soft interfacial film structure. Through thickness h f Mass, shear viscosity eta f And shear elastic modulus mu f The interfacial information of the ATM during adsorption and desorption of the interfacial film before and after photodimerization was further quantitatively evaluated as a function of time as shown in fig. 9 (d-g). ATMs after UV irradiation show the highest h during adsorption f Quality, eta f Sum mu f . Therefore, the dimerized ATMs have more adsorption on the oil-water interface, which is helpful for the increase of the thickness and the quality of the interfacial film. Adsorption of the dimerized ATMs at the oil-water interface shows a higher viscosity and elastic structure, which may be a key reason for the more stable emulsion.
The above description of the specific embodiments of the present invention has been given by way of example only, and the present invention is not limited to the above described specific embodiments. Any equivalent modifications and substitutions for this practical use will also occur to those skilled in the art, and are within the scope of the present invention. Accordingly, equivalent changes and modifications are intended to be included within the scope of the present invention without departing from the spirit and scope thereof.
Claims (10)
1. The sodium alginate-based telechelic molecule is characterized in that the molecule is a compound shown in a structural formula (1):
2. a photodimerization reactant after UV irradiation of the sodium alginate based telechelic molecule of claim 1.
3. The method for preparing the sodium alginate-based telechelic molecule according to claim 1, wherein formaldehyde, 7-amino-4-methylcoumarin/DMSO solution and cyclohexyl isocyanide are added into sodium alginate solution with pH of 3.2-4, stirred at room temperature for complete reaction, and purified to obtain the sodium alginate-based telechelic molecule.
4. The assembly of sodium alginate-based telechelic molecules of claim 1 self-assembled in aqueous solution.
5. The Pickering emulsion is characterized by comprising an oil-water phase and adopting the sodium alginate-based telechelic molecule as a stabilizer or adopting the sodium alginate-based telechelic molecule as a stabilizer after photo-dimerization by UV irradiation.
6. The seed Pickering emulsion according to claim 1, wherein the volume ratio of the oil phase to the water phase of the emulsion is 1:0.1-10, preferably the oil volume fraction in the emulsion is not less than 0.5, more preferably not less than 0.7, more preferably not less than 0.8;
the concentration of the sodium alginate-based telechelic molecules in the water phase is 0.05-0.5wt% when no UV radiation is generated; when UV irradiation is carried out, the concentration of sodium alginate-based telechelic molecules in the aqueous phase is 0.05-0.5wt% before irradiation.
7. A method for preparing Pickering emulsion according to claim 5 or 6, which is characterized in that sodium alginate-based telechelic molecules according to claim 1 are dispersed in a water phase, an oil phase is added, and emulsification is carried out, thus obtaining the Pickering emulsion; or alternatively
Dispersing the sodium alginate-based telechelic molecule of claim 1 in a water phase, adding an oil phase after photodimerization of the sodium alginate-based telechelic molecule by UV irradiation, and emulsifying to obtain the product.
8. The method according to claim 7, wherein the UV irradiation is performed for at least 30min, preferably at least 1h, more preferably for more than 2h, more preferably for 2h to 5h.
9. Use of a sodium alginate-based telechelic molecule of claim 1, or a product of claim 2, or an assembly of claim 4, or a Pickering emulsion of claim 5 or 6, for studying the relationship between the small molecule structure and the stability of the Pickering emulsion.
10. Use of the sodium alginate-based telechelic molecule of claim 1, or the product of claim 2, or the assembly of claim 4, or the Pickering emulsion of claim 5 or 6, in the fields of biomedical, cosmetic, food, petroleum and wastewater treatment.
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| CN109464395A (en) * | 2019-01-03 | 2019-03-15 | 中国科学院过程工程研究所 | A kind of oil-in-water packet gel emulsion and its preparation method and application |
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