CN112300404B - Preparation method of active supramolecular polymer based on layered double-hydroxide bionic confinement driving - Google Patents

Preparation method of active supramolecular polymer based on layered double-hydroxide bionic confinement driving Download PDF

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CN112300404B
CN112300404B CN202011206405.2A CN202011206405A CN112300404B CN 112300404 B CN112300404 B CN 112300404B CN 202011206405 A CN202011206405 A CN 202011206405A CN 112300404 B CN112300404 B CN 112300404B
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史文颖
宗映彤
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Beijing University of Chemical Technology
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Abstract

The invention discloses a preparation method of an active supramolecular polymer based on layered double hydroxide bionic limited domain driving. In the invention, the layered double hydroxide can be used as a nano material for providing a bionic confinement space, and various simple small molecular monomers are confined and assembled into orderly arranged supermonomers; after the lamina is removed, the supermolecule can temporarily maintain the shape and the property, and can be further assembled into the active supermolecule polymer with controllable length and narrow dispersity under proper conditions. Kinetic studies show that the layered double hydroxide overcomes the huge energy barrier and can inhibit the spontaneous nucleation of monomers and the depolymerization of metastable active supramolecular polymers. The polymerization degree of the active supermolecule polymer can reach 6000, which exceeds the polymerization degree of all the published active supermolecule polymers. This new living polymerization strategy will drive the exploration of other multifunctional molecules and promote the rapid development of functional living supramolecular polymers.

Description

Preparation method of active supramolecular polymer based on layered double-hydroxide bionic confinement driving
The technical field is as follows:
the invention belongs to the technical field of active supermolecule polymerization, and particularly relates to a preparation method of an active supermolecule polymer based on layered double hydroxide bionic confinement driving.
The background art comprises the following steps:
the development of supramolecular polymers provides a broad blueprint for new generation functional materials such as soft materials, drug delivery and catalysts, in particular the emergence of active supramolecular polymers (LSPs) with high efficiency controllability and uniform dispersibility, providing a novel preparation approach for the preparation of supramolecular polymers and their biological applications. In a strict sense, a supramolecular polymer can be defined as LSP only if it is demonstrated by cycling experiments that the living end of the polymer can be polymerized several times. In 2014, Sugiyasu and Takeuchi topic groups established the first seed-induced LSP and guided the implementation of later programmable LSPs by aggregates far from the path. However, LSP still needs to be controlled more precisely in terms of degree of polymerization, chain stereochemistry and lifetime. Thus, in 2015, the Aida and Miyajima groups first introduced a chain growth mechanism to achieve initiator-controlled LSPs, a unique LSP that provided inspiration for the development of future precision macromolecular engineering. However, LSPs are still in the break-away phase and the ultimate goal is to obtain a controlled, life-like active material. In 2018, the Balasubramanian and George topic group showed the first biomimetic LSP by consuming the chemical fuel ATP, making us closer to the realization of complex biological entities.
Even though the preparation of LSPs has made a great breakthrough, the monomer design still faces a serious challenge because the above work requires precise molecular design and complex functional group modification for a specific system, which inevitably increases the synthesis difficulty and material cost, greatly limiting their versatility and applicability. However, this strategy for making LSPs using commercially available monomers with simple structures is difficult to succeed from an energy principle, because the activation energy barrier of simple small molecules in the nucleation step is not high enough to control the kinetics of subsequent elongation compared to spontaneous nucleation. Therefore, it is necessary to find suitable protocols to rationally select the assembly route in order to achieve the preparation of active supramolecules.
Scientists have been motivated by biological systems to achieve time-controlled supramolecular polymers. In the case of self-assembly, the biologically restricted environment may promote the formation and stability of intermolecular interactions of the self-assembled system. For example, in a cellular confined environment, the rate of folding and self-assembly of polypeptide chains is dramatically increased. In a molecular chaperone constrained nanocage, abnormal folding and aggregation of protein can be inhibited, so that the folding rate of normal protein is improved. These biological confinement phenomena provide important inspiration for directing the ordered assembly of simple small molecules through biomimetic action.
Conventional LSP production schemes require high molecular fine-tuning and must be a dynamic driving system that temporarily maintains it in a metastable state. However, the activation barrier of aggregates of simple-structured monomers is not sufficient to control the subsequent growth kinetics, and therefore the preparation of LSPs of simple-structured monomers remains a considerable challenge.
The invention content is as follows:
the invention provides a preparation method of an active supramolecular polymer based on layered double hydroxide bionic confinement driving.
The preparation method comprises the following steps: simulating the biological confinement effect of endoplasmic reticulum by using the two-dimensional confinement space of the layered double hydroxide, and orderly arranging the organic micromolecules with negative charges between layers of the layered double hydroxide to form a molecular array by adopting an ion exchange method so as to inhibit spontaneous nucleation of the organic micromolecules; then adding acid to remove the layered double hydroxide, and maintaining the ordered arrangement of the interlaminar molecular arrays to form a super monomer; then mixing with organic small molecule solution, and the hypermonomer is driven by crystallization to elongate to form active supermolecular polymer.
The prepared active supermolecule polymer is mixed with the organic micromolecule solution for 1-5 times to obtain the active supermolecule polymer which continues to extend.
The selection of the organic small molecules has the following two conditions: 1) the molecule has a functional group capable of forming a hydrogen bond network; 2) the molecules have rigid planes, and can perform oriented long-range pi-pi stacking.
The organic micromolecules are one or more of 8-hydroxypyrene-1, 3, 6-trisulfonate (SG7), 3-aminobenzenesulfonic acid (3-ABSA), 2, 5-diaminobenzenesulfonic acid (2,5-DABSA) and Congo Red (CR).
The acid is trifluoroacetic acid.
The solvent of the organic micromolecule solution is a mixed solution of methanol and trifluoroacetic acid.
A preparation method of an active supermolecule co-assembly polymer based on layered double hydroxide bionic limited domain driving comprises the following steps: simulating the biological confinement effect of endoplasmic reticulum by using the two-dimensional confinement space of the layered double hydroxide, and orderly arranging the organic micromolecules with negative charges between layers of the layered double hydroxide to form a molecular array by adopting an ion exchange method so as to inhibit spontaneous nucleation of the organic micromolecules; then acid and arginine solution are added in sequence to obtain the active supermolecular co-assembly polymer.
The acid is trifluoroacetic acid.
The solvent of the arginine solution is a mixed solution of methanol and trifluoroacetic acid.
The arginine is L-arginine or D-arginine.
A method for chiral recognition of arginine comprises the following steps: simulating the biological confinement effect of endoplasmic reticulum by using the two-dimensional confinement space of the layered double hydroxide, and orderly arranging organic micromolecules with negative charges between layers of the layered double hydroxide to form a molecule array by adopting an ion exchange method; then sequentially adding acid and arginine solution, and performing visual chiral recognition by naked eyes by utilizing the time difference of respectively forming active supermolecule co-assembled polymers by L-arginine and D-arginine.
In the invention, layered double hydroxide (also called hydrotalcite, LDH) can be used as a nano material for providing a bionic restricted domain space, and various simple small molecule monomers can be restricted and assembled into orderly arranged super monomers. After the laminae are removed, the supermonomers can temporarily maintain their morphology and properties, and under appropriate conditions can be further assembled into LSPs with controllable length and narrow dispersibility. Kinetic studies show that LDH overcomes a huge energy barrier and can inhibit spontaneous nucleation of monomers and depolymerization of metastable LSPs. The degree of polymerisation of LSP could reach-6000, which is the minimum for LSP made from 3 μm LDH, but exceeds the degree of polymerisation of all published LSPs. This new active polymerization strategy will drive the exploration of other multifunctional molecules and promote the rapid development of functional LSPs.
Description of the drawings:
FIG. 1 is a schematic representation of the molecular formulae of SG7, BSA, 3-ABSA, 2,5-DABSA, CR, DHNS, L-arginine and D-arginine;
FIG. 2 shows the product (a) of BSA obtained according to the LSP preparation in example 1 and a control (b) of the same charge physically mixed without LDH confinement;
FIG. 3 is a 3-ABSA LSP (a) and its cycle1 product (b), cycle2 product (c) successfully prepared in example 1, and a control (d) of the same charge physically mixed without LDH domains;
FIG. 4 shows the product (a) of example 1, 2,5-DABSA obtained according to the LSP preparation and its cycle1 product (b), cycle2 product (c), and a control (d) of the same charge physically mixed without LDH limitation;
FIG. 5 shows the product (a) of example 1 obtained by SG7 according to the LSP preparation method and its cycle1 product (b), cycle2 product (c), as well as a control (d) of the same charge physically mixed without LDH confinement;
FIG. 6 is a comparison of the product (a) obtained by the LSP preparation of DHNS according to example 1 and of a control (b) of the same charge physically mixed without LDH confinement;
FIG. 7 shows the product (a) obtained by the LSP preparation of CR in example 1 and a control (b) of the same charge physically mixed without LDH confinement;
FIG. 8 is an SEM image of four sizes of LDH (a-d, 20nm, 50nm, 100nm and 3 μm in sequence) prepared in example 2 and their post-intercalation (e-h);
figure 9 is an XRD pattern of the four LDH precursors (a) prepared in example 2 and the corresponding intercalated SG7-LDH (b);
FIG. 10 shows the LSP prepared in example 2 after 1h of sonication20(a)，LSP50(b)，LSP100(c) And LSP3000(d) Static Light Scattering (SLS) map of (A), its corresponding SEM map (e-h), and LSP after 12h of standing20(i)，LSP50(j)，LSP100(k) And LSP3000(l) SEM picture of (1);
FIG. 11 shows LSP in example 220The resulting cycle 1 products (a), cycle 2 products (b), cycle 3 products (c), and the cycle 1 products SSP of the other three LSPs were prepared for seed50(d)，SSP100(e)，SSP3000(f) SEM picture of (1);
FIG. 12 is a graph showing fluorescence spectra of polymer-L and polymer-D, co-assembly products prepared in example 2 using LDH at 20nm, 50nm, 100nm and 3 μm as precursors.
The specific implementation mode is as follows:
for a better understanding of the invention, the contents of the invention are further illustrated below in combination with the small organic molecules SG7, BSA, 3-ABSA, 2,5-DABSA, CR and DHNS and the LDH precursors at 20nm, 50nm, 100nm and 3 μm, but the contents of the invention are not limited to the following examples.
Example 1:
step A: dropping NaOH solution (0.500mol/L) into solution containing 30.0mmol of MgCl2·6H2O and 10.0mmol AlCl 3·9H2O in saline solution (50.0mL), until pH ≈ 8.50, during which time the solutions used are all freshly prepared from distilled water deprived of carbon dioxide. The slurry was transferred to an autoclave and heated at 110 ℃ for 24 hours, washed 3 times with distilled water containing carbon dioxide, and dried in a vacuum oven at 70 ℃ for use, to give an LDH precursor of 50nm in size.
And B, step B: various small organic molecules are intercalated between the LDH layers using ion exchange. Stock solutions (pH. approximatively.8.00, 12.5mmol/L) of small organic molecules (SG7, BSA, 3-ABSA, 2,5-DABSA, CR and DHNS) were prepared first with distilled water of carbon dioxide, 50mL of the stock solutions were taken, 0.313g of LDH precursor powder was added thereto with stirring, the temperature was raised to 80 ℃ and the temperature was increased under N2Ion exchange is carried out for 24 hours in the atmosphere, and after washing is carried out for 3 times by using distilled water of carbon dioxide and absolute methanol, the obtained six kinds of intercalated hydrotalcite are respectively dispersed into the absolute methanol by 20g/L for standby.
And C: preparation of LSP by using six kinds of small molecules as monomers50. Taking 100 mu L of methanol dispersion (20g/L) of intercalated LDH, adding 300 mu L of TFA, and carrying out ultrasonic treatment for 1h to successfully obtain four metastable LSP50(consisting of SG7, 3-ABSA, 2,5-DABSA and CR, respectively).
Step D: taking SG7 with larger size for easy observation as an example, SG7 is dissolved in CH 3A fresh stock solution (0.500g/L) in high concentration was prepared in a mixed solvent of OH/TFA (1:3 v/v). Taking fresh SG7 LSP as a seed, taking 100 mu L of SG7 LSP prepared in the step C, taking 100 mu L of SG7 stock solution, mixing the solution at a ratio of 1:1v/v, carrying out ultrasonic treatment for 1h to obtain a cycle 1 product of SG7 LSP, and repeating the step to obtain a cycle 2 product. This was also true for cycling experiments with 3-ABSA and 2, 5-DABSA.
The molecular formulas of six organic small molecules are shown in figure 1, and the molecular formulas are selected as candidate research objects of the method, and SEM pictures (figures 2-7) show that four molecules are suitable for the method: SG7, 3-ABSA, 2,5-DABSA and CR. These four molecules all undergo spontaneous nucleation without LDH domain-restricted driving, and cannot form LSPs in a rectangular parallelepiped shape with uniform size. The other two molecules, BSA only has one functional group capable of forming hydrogen bonds, and cannot form a hydrogen bond network; DHNS is difficult to form long-range effective pi-pi stacking due to the angle of intermolecular stacking. It is noted that although 2,5-DABSA has more hydrogen bonding functional groups than 3-ABSA, it also causes intermolecular hydrogen bonding, which affects the construction of hydrogen bonding network, and thus, the size of LSP constructed by 3-ABSA is larger.
Example 2:
step A: LDHs of various sizes were prepared (all solutions were prepared with distilled water with carbon dioxide and LDH products were washed with distilled water with carbon dioxide). LDH precursor at 20 nm: 50.0mL of a NaCl solution (1.00mol/L) was added to a 500mL four-necked flask, and 50.0mL of a solution containing 3.75mmol of MgCl2·6H2O and 1.25mmol AlCl3·9H2The salt solution of O is labeled solution A, 50.0mL NaOH solution (1.00mol/L) is labeled solution B, N2Dropwise adding the solution A, B into the flask under the atmosphere and stirring vigorously, maintaining the pH of the suspension at about 8.00 during the dropwise adding process, and after the dropwise adding is finished, adding the mixture into N2Aging at room temperature for 24 hr, washing with distilled water containing carbon dioxide for 3 times, and drying in vacuum drying oven at 70 deg.C; 50nm LDH precursor: the preparation method is shown in step A of example 1; 100nm LDH precursor: 50.0mL of NaCl solution (10.0mol/L) was added to a 500mL four-necked flask, and 50.0mL of NaCl solution containing 37.5mmol of MgCl was added2·6H2O and 12.5mmol AlCl3·9H2The salt solution of O is labeled solution A, 50.0mL NaOH solution (5.00mol/L) is labeled solution B, N2Dropwise adding the solution A, B into the flask under the atmosphere and stirring vigorously, maintaining the pH of the suspension at about 8.00 during the dropwise adding process, and after the dropwise adding is finished, adding the mixture into N 2Aging at room temperature for 24 hr, washing with distilled water containing carbon dioxide for 3 times, and drying in vacuum drying oven at 70 deg.C; 3 μm LDH precursor: will contain 4.00mmol MgCl2·6H2O，1.00mmol AlCl3·9H2Adding salt solution (70.0mL) of O and 20.0mmol of urea into a high-pressure reaction kettle, and heating for 24 hours at 100 ℃; mg obtained3Al-CO3LDHs (0.300g) was added to NaCl solution (1.00mol/L, 300mL, pH 6.50) under N at 100 deg.C2Ion exchange was carried out for 72h under an atmosphere, washed 3 times with distilled water deprived of carbon dioxide, and dried in a vacuum oven at 70 ℃.
And B, step B: SG7 was intercalated by ion exchange between LDH layers of sizes 20nm, 50nm, 100nm and 3 μm, respectively. A stock solution of SG7 (pH. apprxeq.8.00, 12.5mmol/L) was prepared first from distilled water with carbon dioxide removal, 50mL of SG7 stock solution were taken and added thereto with stirring0.313g of LDH precursor powder was added and the temperature was raised to 80 ℃ under N2Ion exchange is carried out for 24 hours under the atmosphere, and after washing for 3 times by using distilled water of carbon dioxide and absolute methanol, the obtained SG7-LDH with four sizes are respectively dispersed into the absolute methanol at the concentration of 20g/L for later use.
And C: 100 μ L of methanol dispersion of SG7-LDH (20g/L) was added with 300 μ L of TFA, and subjected to sonication for 1h to obtain metastable LSP. The LSPs corresponding to LDH precursors at 20nm, 50nm, 100nm and 3 μm are designated as LSPs 20，LSP50，LSP100And LSP3000。
Step D: dissolving SG7 in CH3A fresh stock solution (0.500g/L) in high concentration was prepared in a mixed OH/TFA (1:3v/v) solvent. Taking fresh SG7 LSP as a seed, taking 100 mu L of SG7 LSP prepared in the step C, taking 100 mu L of SG7 stock solution, mixing the solution at a ratio of 1:1v/v, carrying out ultrasonic treatment for 1h to obtain a cycle 1 product of SG7 LSP, and repeating the step to obtain cycle 2 and cycle 3 products. LSP20，LSP50，LSP100And LSP3000The corresponding seed-induced supramolecular polymers are called SSP20，SSP50，SSP100And SSP3000。
Step E: new preparation of L-or D-arginine in CH3Stock solution (100mmol/L) in OH/TFA (1:3v/v) mixed solvent is prepared by taking 100 mu L of SG7-LDH (20.0g/L methanol stock solution), 60.0 mu L of TFA and 340 mu L of L-arginine (newly prepared stock solution of 100mmol/L), sequentially mixing, performing ultrasonic treatment for a certain time to generate polymer-L, and replacing the L-arginine in the step with D-arginine to obtain polymer-D. The process was similar for four sizes of SG7-LDH, except that the time to obtain the co-assembled polymer was different: performing ultrasonic treatment for 10min for 20nm LDH precursor; carrying out ultrasonic treatment for 15min on an LDH precursor with the particle size of 50 nm; carrying out ultrasonic treatment for 30min on an LDH precursor with the particle size of 100 nm; for 3 μm LDH precursor, sonication was carried out for 50 min.
The SEM of fig. 8 shows that LDHs of 20nm, 50nm, 100nm and 3 μm have all been successfully prepared and that there is little change in morphology before and after intercalation. The XRD pattern of FIG. 9 shows that all SG7-LDH of different sizes have been successfully intercalated, but the ratio of peak intensities of (003) to (006) has changed, indicating that different scales are used The size of LDH varied in the domain-limiting ability of SG7, and the resulting hypermonomers varied in activity and application. According to a-d in FIG. 10, LSP20，LSP50，LSP100And LSP3000In conjunction with the Rayleigh equation:
Figure BDA0002757222490000071
calculating the minimum size of LSP that can be freshly prepared20，LSP50，LSP100And LSP3000With corresponding SEM images in fig. 10e-h, the degrees of polymerization of (a) are 40, 400, 4000 and 6000, respectively. After 12h of standing, LSP20，LSP50，LSP100And LSP3000Corresponding SEM pictures are shown in FIGS. 10i-l, where LSPs50，LSP100And LSP3000Gradually increase in size, while the LSP20Then differently, its size is much larger than the LSP50This is probably due to the fact that 20nm LDH confers its supermonomer a minimal size, resulting in an increase in its active sites, and therefore the final size of LSP depends not only on the initial size but also on the activity conferred by the LDH. In FIG. 11 are LSPs20，LSP50，LSP100And LSP3000Performance in the cycling experiment, SEM pictures show that LSPs20The circulation effect of (3) is particularly outstanding, the LSP appearance is maintained, and the size of the LSP is increased. While the remaining LSPs, although maintaining the morphology of the LSPs, were reduced in size, indicating that disaggregation occurred while inducing ordered arrangement of SG7, thereby releasing more active sites to maintain activity. Cycling experiments demonstrated that LDH confers different activities on LSP.
FIG. 12 shows sonication for 10min, polymer-L20With polymer-D20Simultaneously forming; sonication for 15min, polymer-L50With polymer-D50Formed at the same time, but the light-emitting spectra are slightly different; sonicate for 30min, polymer-L100Formation of, but Polymer-D20Formed 20min after stopping ultrasound; sonication for 50min, polymer-L3000Formation of polymer-D1000Formed several days or even one week after cessation of sonication. Indicating that 20nm LDH confers extremely high activity on the macromer and forms rapidlyAnd (4) assembling the components. Therefore, the LDH with the larger size of 100nm and the LDH with the size of 3 μm have lower activity due to the larger size, can slowly present the formation of the co-assembly product, and can effectively recognize that different competitive units generate strong and different blocking effects in the assembly kinetics process, namely amplifying the different blocking effects of the functional group of the chiral arginine in the assembly kinetics, so as to realize chiral effective recognition, as shown in fig. 12 c-d. The experiment shows that the size of LDH can be adjusted according to the experiment requirement, so that LSP with different activities can be obtained.

Claims (9)

1. A preparation method of an active supramolecular polymer based on layered double hydroxide bionic confinement driving is characterized by comprising the following specific steps: simulating the biological confinement effect of endoplasmic reticulum by using the two-dimensional confinement space of the layered double hydroxide, and orderly arranging the organic micromolecules with negative charges between layers of the layered double hydroxide to form a molecular array by adopting an ion exchange method so as to inhibit spontaneous nucleation of the organic micromolecules; then adding acid to remove the layered double hydroxide, and maintaining the ordered arrangement of the interlaminar molecular arrays to form a super monomer; then mixing with organic small molecule solution, and the hypermonomer is driven by crystallization to extend to form active supermolecule polymer; the organic small molecule is selected according to the following two conditions: 1) the molecule has a functional group capable of forming a hydrogen bond network; 2) the molecules have rigid planes, and can perform oriented long-range pi-pi stacking.
2. The method of claim 1, wherein the living supramolecular polymer obtained by the method is mixed with the solution of small organic molecules 1-5 times to obtain a living supramolecular polymer that continues to elongate.
3. The preparation method according to claim 1 or 2, characterized in that the organic small molecule is one or more of 8-hydroxypyrene-1, 3, 6-trisulfonate, 3-aminobenzenesulfonic acid, 2, 5-diaminobenzenesulfonic acid and congo red.
4. The process according to claim 1 or 2, wherein the acid is trifluoroacetic acid.
5. The method according to claim 1 or 2, wherein the solvent of the organic small molecule solution is a mixture of methanol and trifluoroacetic acid.
6. A preparation method of an active supramolecular co-assembly polymer based on layered double hydroxide bionic confinement driving is characterized by comprising the following specific steps: simulating the biological confinement effect of endoplasmic reticulum by using the two-dimensional confinement space of the layered double hydroxide, and orderly arranging the organic micromolecules with negative charges between the layers of the layered double hydroxide to form a molecule array by adopting an ion exchange method so as to inhibit spontaneous nucleation of the organic micromolecules; then sequentially adding acid and arginine solution to obtain an active supermolecule co-assembled polymer; the organic small molecule is selected according to the following two conditions: 1) the molecule has a functional group capable of forming a hydrogen bond network; 2) the molecules have rigid planes, and can perform oriented long-range pi-pi stacking.
7. The process of claim 6, wherein the acid is trifluoroacetic acid; the solvent of the arginine solution is a mixed solution of methanol and trifluoroacetic acid; the arginine is L-arginine or D-arginine.
8. The method for chiral recognition of arginine is characterized by comprising the following specific steps: simulating the biological confinement effect of endoplasmic reticulum by using the two-dimensional confinement space of the layered double hydroxide, and orderly arranging the organic micromolecules with negative charges between layers of the layered double hydroxide to form a molecular array by adopting an ion exchange method; then sequentially adding acid and arginine solution, and performing visual chiral recognition by naked eyes by utilizing the time difference of respectively forming active supermolecule co-assembled polymers by using L-arginine and D-arginine; the organic small molecule is selected according to the following two conditions: 1) the molecule has a functional group capable of forming a hydrogen bond network; 2) the molecules have rigid planes, and can perform oriented long-range pi-pi stacking.
9. The method of claim 8, wherein the acid is trifluoroacetic acid; the solvent of the arginine solution is a mixed solution of methanol and trifluoroacetic acid; the arginine is L-arginine or D-arginine.
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