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CN-121975148-A - Structured liquid drop and preparation method and application thereof

CN121975148ACN 121975148 ACN121975148 ACN 121975148ACN-121975148-A

Abstract

The invention discloses a structured liquid drop, a preparation method and application thereof, wherein the structured liquid drop comprises an interface film and a first solution, the first solution is arranged in a cavity surrounded by the interface film, the structured liquid drop is dispersed in a second solution, the second solution is not mutually dissolved with the first solution, and when the structured liquid drop is extruded by external force smaller than a threshold value, the structured liquid drop changes in shape. The invention takes the water-soluble star beta-cyclodextrin polymer with a definite structure as an assembly element, does not need to use any high molecular ligand, directly utilizes the interaction between the star beta-cyclodextrin polymer and the oil phase solvent to induce the star beta-cyclodextrin polymer interface assembly, constructs an assembly with excellent mechanical strength in situ at the water-oil interface, and realizes the preparation of the structured liquid drops by combining the external field effect.

Inventors

  • SHI SHAOWEI
  • LI PEIFAN
  • WANG MENG

Assignees

  • 北京化工大学

Dates

Publication Date
20260505
Application Date
20250822

Claims (10)

  1. 1. The structured liquid drop is characterized by comprising an interface film and a first solution, wherein the first solution is arranged in a cavity surrounded by the interface film, the structured liquid drop is dispersed in a second solution, the second solution is not mutually dissolved with the first solution, when the structured liquid drop is extruded by an external force smaller than a threshold value, the structured liquid drop changes in shape, the interface film comprises a star-beta cyclodextrin polymer, the star-beta cyclodextrin polymer comprises a central core molecule and n beta-cyclodextrin units, the beta-cyclodextrin units and the central molecule are connected through covalent bonds, and a star topology structure is formed, wherein n is more than or equal to 3.
  2. 2. The structured droplet of claim 1, wherein the structured droplet deformed by an external force reverts to a spherical structure within a temperature range of 45-90 ℃.
  3. 3. The structured droplet of claim 1, wherein the first solution has a functional component dispersed therein.
  4. 4. A structured liquid droplet according to claim 3, wherein the functional component is a magnetic nanoparticle.
  5. 5. A method of preparing structured droplets as claimed in claim 1, comprising the steps of: S1) fully dissolving star beta-cyclodextrin polymer in ultrapure water to obtain aqueous phase solution A; S2) selecting an oil phase solution B which is not compatible with the aqueous phase solution A; s3) dripping the aqueous phase solution A into the oil phase solution B or dripping the oil phase solution B into the aqueous phase solution A, assembling the star-beta cyclodextrin polymer on the surface of the liquid drop to form an interface film, and wrapping the liquid drop to form a structured liquid drop.
  6. 6. The method according to claim 5, wherein the concentration of the star beta-cyclodextrin polymer in the aqueous solution A is 0.1-100 mg/mL.
  7. 7. The method according to claim 5, wherein the oil phase solvent in the oil phase solution B is one or both of an aromatic hydrocarbon and a halogenated hydrocarbon having no halogen substituent.
  8. 8. The process according to claim 7, wherein the halogenated hydrocarbon is one or more of iodobenzene, bromobenzene, chlorobenzene, 2, 4-dichlorotoluene, 1, 2-dibromobenzene, 1, 2-dichlorobenzene, 1, 3-dibromobenzene, 1, 3-dichlorobenzene, (1-chloroethyl) benzene, 1-iodonaphthalene, 1-bromonaphthalene, 1-chloronaphthalene, iodocyclohexane, iodoethane, chloroiodomethane, 1, 2-dibromoethane, 1-bromobutane, carbon tetrachloride, chloroform and methylene chloride.
  9. 9. The method according to claim 7, wherein the aromatic hydrocarbon having no halogen substituent is one or more of benzene, toluene, o-xylene, p-xylene, cumene, 1,2, 3-trimethylbenzene, 1,2, 4-trimethylbenzene, 1, 3-diethylbenzene, 1-methylnaphthalene, 1-ethylnaphthalene, 1, 3-divinylbenzene, cyclohexylbenzene, phenylacetylene, ethylbenzene, propylbenzene, butylbenzene and pentylbenzene.
  10. 10. Use of structured droplets according to claim 1, characterized in that structured droplets are used for the production of plastic devices.

Description

Structured liquid drop and preparation method and application thereof Technical Field The invention belongs to the field of preparation of soft material, and relates to a structured liquid drop constructed by utilizing star beta-cyclodextrin polymer water/oil interface self-assembly, and a preparation method and application thereof. Background Structured liquid drops are novel soft condensed state substances with liquid fluidity and solid structure stability, and have unique advantages in the fields of drug delivery, microreactors, flexible electronic devices and the like. Such non-equilibrium liquids can be built by self-assembly and plug-transition of colloidal particles at immiscible two-phase interfaces (e.g., water-oil interfaces), but generally require a strict neutral wetting of the particles at the interface, maximizing the interfacial binding energy of the particles, which places very stringent demands on particle preparation and surface modification (Science 2005,309,2198-2201; nat. Mater.2007,6, 966-971). The current approach of great interest is to construct Janus-type nanoparticle surfactants (Science 2013,342,460-463) using in situ co-assembly of water-dispersible nanoparticles and oil-soluble polymeric ligands at the water-oil interface. The nanoparticle surfactant constructed based on weak interaction has a self-regulating mechanism, and can reduce interface energy to the greatest extent by regulating the quantity of polymer ligands grafted on the surface of the nanoparticle. The method reduces the requirement on the wettability of the particle surface, but the method needs to specially design the nano particles and the macromolecular ligands with complementary functional groups (such as positive-negative ions, host-object, electron donor-acceptor and the like), increases the complexity (Adv.Mater.2018,30,1705800;J.Am.Chem.Soc.2020,142,8591-8595.;ACS Appl.Mater.Interfaces 2024,16,47,65592-65599); of the system, combines the interfacial activity and the oil solubility of the macromolecular ligands and limits the selection range of the ligands. Therefore, it is important to develop a simple and universal, low cost method of structured droplet preparation. Disclosure of Invention Therefore, the invention aims to provide a structured liquid drop, a preparation method and application thereof, wherein a water-soluble star beta-cyclodextrin polymer with a definite structure is used as an assembly element, any macromolecular ligand is not needed, interaction between the star beta-cyclodextrin polymer and an oil phase solvent is directly utilized to induce the assembly of the star beta-cyclodextrin polymer interface, an assembly body with excellent mechanical strength is constructed in situ at a water-oil interface, and the preparation of the structured liquid drop is realized by combining an external field effect. In order to solve the technical problems, the invention provides the following technical scheme: The structured liquid drop comprises an interface film and a first solution, wherein the first solution is arranged in a cavity surrounded by the interface film, the structured liquid drop is dispersed in a second solution, the second solution is not mutually dissolved with the first solution, when the structured liquid drop is extruded by an external force smaller than a threshold value, the structured liquid drop changes in shape, the interface film comprises a star-shaped beta cyclodextrin polymer, the star-shaped beta cyclodextrin polymer comprises a central core molecule and n beta-cyclodextrin units, the beta-cyclodextrin units are connected with the central molecule through covalent bonds, and a star topology structure is formed, wherein n is more than or equal to 3. Wherein, the star beta-cyclodextrin polymer is one or more of trimer (shown as a in figure 1), tetramer (shown as b in figure 1), hexamer (shown as c in figure 1) and polymer with hyperbranched structure (shown as d in figure 1), and the specific structure is shown in figure 1. And the structured liquid drops deform under the action of external force, and recover to a spherical structure within the temperature range of 45-90 ℃. The structured drop described above, the first solution having the functional component dispersed therein. The functional component of the structured liquid drop is magnetic nanoparticles, wherein the magnetic nanoparticles are one or more of oleic acid modified ferroferric oxide nanoparticles, stearic acid modified ferroferric oxide nanoparticles, myristic acid modified ferroferric oxide nanoparticles, dodecanoic acid modified ferroferric oxide nanoparticles, octadecanoic acid modified ferroferric oxide nanoparticles, oleylamine modified ferroferric oxide nanoparticles, dodecylamine modified ferroferric oxide nanoparticles, hexadecylamine modified ferroferric oxide nanoparticles, dioctylphosphoric acid modified ferroferric oxide nanoparticles, polystyrene coated ferroferric oxide nanoparticles and po