CN110358107B - Method for regulating and controlling supermolecule polymerization - Google Patents
Method for regulating and controlling supermolecule polymerization Download PDFInfo
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Abstract
A method for regulating and controlling supermolecule polymerization relates to the field of response polymer materials. A class of methods is provided for orthogonal regulation of supramolecular polymerization processes driven by one non-covalent force and another non-covalent force. The specific operation method is to realize the process of metal coordination accurately and reversibly regulating quadruple hydrogen bond-driven supramolecular polymerization by introducing diethylene glycol groups into hydrogen bond polymerization monomers to be complexed with potassium ions. The invention has the beneficial effects that: the method is simple, convenient and quick, has low cost, does not influence the acting force of hydrogen bonds, and has strong anti-interference capability and specific response capability.
Description
Technical Field
The invention relates to the field of supramolecular chemistry, in particular to a method for accurately regulating and controlling supramolecular polymerization.
Background
Orthogonal self-assembly means that multiple non-covalent acting forces do not interfere with each other in the assembly process, so that the assembly is more accurate and efficient. In 2012, Li and Xiao et al reviewed advanced supramolecular polymers constructed by orthogonal self-assembly (chem.soc.rev.2012,41, 5950-. In 2015, Wei et al reviewed orthogonal self-assembly supramolecular polymers by metal coordination and host-guest interactions (chem. Soc. Rev.2015,44, 815. 832.). In 2019, Xiao et al further reviewed supramolecular polymers (chi. chem. lett.2020,31,1-9.) that self-assemble orthogonally by host-guest interactions and multiple hydrogen bonding interactions. Throughout the various studies, there is no case that the depolymerization and repolymerization of supramolecular polymers can be precisely and reversibly regulated through orthogonal response. Orthogonal response here means that the driving force for the formation of supramolecular polymers is not influenced by the modulation, which occurs mainly from another non-covalent force, orthogonal to the non-covalent force driving the polymerization of supramolecules. Specifically, hydrogen bond-driven supramolecular polymerization only responds to hydrogen bond competitive units, macrocyclic host-guest interaction-driven supramolecular polymerization only responds to host or guest competitive units, and metal coordination-driven supramolecular polymerization only responds to metal coordination competitive units. There is no case seen in which hydrogen bond-driven supramolecular polymerization responds to metal coordination competing units to enable reversible depolymerization/repolymerization.
The supramolecular polymer is known as a new-generation intelligent material due to reversibility, dynamic property and responsiveness, and is the leading edge of research in the field of polymer materials. Orthogonal self-assembly is the current leading edge of research on supramolecular polymers. Orthogonal regulation polymerization is the leading edge of the research field of orthogonal self-assembly supramolecular polymers, so a method is urgently needed to be invented at present, and the supramolecular polymerization process of a polymerization monomer can be accurately controlled through orthogonal regulation.
Disclosure of Invention
The invention aims to provide a method for orthogonally regulating and controlling supramolecular polymerization.
In order to achieve the above object, the present invention provides a catechol-bridged diureido pyrimidone compound, which has the following structure:
wherein the R group is methyl, ethyl, propyl, butyl, isoheptyl, undecyl and tridecyl.
The present invention mainly describes a novel method for the orthogonal controlled polymerization of the monomer, and as for the general method for monomer synthesis, refer to the patent with the application number of CN201811187277.4 of the present inventor.
The monomer has two remarkable characteristics, namely, two ends of a molecule are ureido pyrimidone units which can be dimerized through quadruple hydrogen bonds, and a connecting group between catechol and ureido pyrimidone is a diethylene glycol group. They impart two very important properties to the monomer.
The mode of autodimerization of ureidopyrimidinone units via quadruple hydrogen bonds is as follows:
wherein the R group is methyl, ethyl, propyl, butyl, isoheptyl, undecyl and tridecyl.
Wherein the dotted line in the above formula represents a hydrogen bond. The force of a single hydrogen bond is weak, but the force of four hydrogen bonds side by side like this is very strong (Science 1997,278, 1601-1604.).
It will therefore be appreciated that the monomers of the invention can form supramolecular polymers with multiple repeat units in high concentrations by means of a quadruple hydrogen bond pattern head-to-tail. That is, the driving force for the supramolecular polymer is the quadruple hydrogen bonding. The structure of the supramolecular polymer is as follows:
wherein the R group is methyl, ethyl, propyl, butyl, isoheptyl, undecyl and tridecyl. n is the degree of supramolecular polymerization, which is influenced by concentration and temperature.
In the past research, the hydrogen bond supermolecule polymer also has dynamic property, and the supermolecule polymer can be degraded by adding a hydrogen bond competition monomer or a solvent. However, it is difficult to achieve reversible degradation and repolymerization of such supramolecular polymers without disrupting hydrogen bonds.
Through a large number of experimental researches, the inventor finds that the diethylene glycol group lays a foundation for the orthogonal regulation of the supramolecular polymer. Namely, the supramolecular polymerization driven by quadruple hydrogen bonds can be orthogonally regulated through the metal coordination of potassium ions.
The specific method comprises the following steps: potassium hexafluorophosphate, potassium ions and diethylene glycol groups are added into a supermolecular polymer solution formed by the monomers to perform metal coordination similar to crown ether, so that the conformation of the monomers is changed, a clamp-type structure is formed, and the clamp-type structure is selectively dimerized to form a stable cyclic dimer form, and the structure is as follows:
wherein the R group is methyl, ethyl, propyl, butyl, isoheptyl, undecyl and tridecyl.
Therefore, the supramolecular polymer is completely changed into a dimer form with small molecular weight under the induction of metal coordination of potassium ions, and the polymer is subjected to precise depolymerization. By adding benzo 18 crown 6, potassium ions are captured by benzo 18 crown 6 due to its stronger complexing force, and the monomer re-forms the supramolecular polymer. Thus, the orthogonal regulation process is reversible. Since the chemical environment of the H atoms in the cyclic dimer and the linear supramolecular polymer are different, the reversible process can be monitored by nmr hydrogen spectroscopy.
In summary, the present invention provides a strategy that utilizes orthogonal metal coordination to achieve precise control of hydrogen bond-driven supramolecular polymerization process, such that the topological structure of the assembly can be reversibly controlled between cyclic dimers and linear supramolecular polymers.
The invention has the following beneficial effects:
(1) it is proposed to use orthogonal non-covalent forces to modulate another non-covalent driven supramolecular polymerization;
(2) the metal coordination of potassium ions is utilized to change the conformation of the monomer, so that the reversible regulation and control of the assembly between the annular dimeric structure and the linear supramolecular polymer are realized;
(3) the method is simple, convenient and quick, has low cost, does not influence the hydrogen bond, has strong specific response capability, and has no effect on sodium ions and lithium ions in the same family with potassium ions;
(4) the method belongs to the field of leading-edge research of intelligent response materials, realizes curve overtaking, and realizes international leading in the field of supermolecule polymerization regulation.
Detailed Description
The invention is described in more detail below with reference to specific examples, without limiting the scope of the invention. Unless otherwise specified, the experimental methods adopted by the invention are all conventional methods, and the experimental devices, materials, reagents and the like used in the method can be purchased or synthesized from chemical companies.
Example 1
0.5 ml of deuterated chloroform and deuterated acetonitrile in a volume ratio of 1:1 are added into a nuclear magnetic tube, 48 mg of isoheptyl substituted monomer is added, and the mixture is dissolved by ultrasonic to prepare a 128mM solution. NMR hydrogen spectroscopy was performed, wherein characteristic peaks of ureidopyrimidinone NH, which represent polymer, were 13.07ppm, 11.86ppm and 10.17ppm, respectively. 1 equivalent of KPF was added6Then, the NMR spectrum was again measured, and the peaks of NH were shifted to high fields by shielding due to the formation of cyclic dimers in which the planes of ureido pyrimidone dimerization were parallel to each other, and were shifted to 13.05ppm, 11.72ppm and 9.74ppm, respectively.
Example 2
For adding KPF6The isoheptyl-substituted monomer and the independent monomer of (1) were separately subjected to viscosity testing. The independent monomer firstly keeps the increasing trend of the slope of 1 along with the increase of the concentration, and after the concentration is close to 10mM, the independent monomer begins to increase in the trend of the slope of 1.7, which indicates that the polymerization is generated; and adding KPF6The monomer (1) always maintained a rising trend with a slope of 1 with increasing concentration, indicating that it always maintained the small molecular weight dimer form.
Example 3
0.5 ml of deuterated chloroform and deuterated acetonitrile in a volume ratio of 1:1 are added into a nuclear magnetic tube, 48 mg of isoheptyl substituted monomer is added, and the mixture is dissolved by ultrasonic to prepare a 128mM solution. NMR hydrogen spectroscopy was performed, wherein characteristic peaks of ureidopyrimidinone NH, which represent polymer, were 13.07ppm, 11.86ppm and 10.17ppm, respectively. 1 equivalent of KPF was added6Then, the NMR spectrum was again measured, and the peaks of NH were shifted to high fields by shielding due to the formation of cyclic dimers in which the planes of ureido pyrimidone dimerization were parallel to each other, and were shifted to 13.05ppm, 11.72ppm and 9.74ppm, respectively. After further addition of 1 equivalent of benzo 18 crown 6 to the above solution, the NH peak again shifted low to 13.07ppm, 11.86ppm and 10.17ppm, indicating that the dimer re-polymerized supramolecular as a result of the release of potassium ions after the potassium ions were captured by benzo 18 crown 6.
Example 4
0.5 ml of deuterated chloroform and deuterated acetonitrile in a volume ratio of 1:1 are added into a nuclear magnetic tube, 48 mg of isoheptyl substituted monomer is added, and the mixture is dissolved by ultrasonic to prepare a 128mM solution. NMR hydrogen spectroscopy was performed, wherein characteristic peaks of ureidopyrimidinone NH, which represent polymer, were 13.07ppm, 11.86ppm and 10.17ppm, respectively. 1 equivalent of KPF was added6Then, the NMR spectrum was again measured, and the peaks of NH were shifted to high fields by shielding due to the formation of cyclic dimers in which the planes of ureido pyrimidone dimerization were parallel to each other, and were shifted to 13.05ppm, 11.72ppm and 9.74ppm, respectively. After 1 equivalent of benzo 18 crown 6 was added to the solution, the NH peak again shifted to 13.07ppm, 11.86ppm and 10.17ppm, indicating that the dimer was released due to the capture of potassium ions by benzo 18 crown 6Potassium ion to re-polymerize supramolecular. After 1 equivalent potassium ion is added into the solution, the supermolecular polymer is depolymerized again, and the NH peak moves to high field and respectively moves to 13.05ppm, 11.72ppm and 9.74 ppm.
Comparative example 1
0.5 ml of deuterated chloroform and deuterated acetonitrile in a volume ratio of 1:1 are added into a nuclear magnetic tube, 48 mg of isoheptyl substituted monomer is added, and the mixture is dissolved by ultrasonic to prepare a 128mM solution. NMR hydrogen spectroscopy was performed, wherein characteristic peaks of ureidopyrimidinone NH, which represent polymer, were 13.07ppm, 11.86ppm and 10.17ppm, respectively. 1 equivalent of NaPF is added6After that, the nuclear magnetic resonance hydrogen spectrum test is carried out, and the NH peak has no change.
Comparative example 2
0.5 ml of deuterated chloroform and deuterated acetonitrile in a volume ratio of 1:1 are added into a nuclear magnetic tube, 48 mg of isoheptyl substituted monomer is added, and the mixture is dissolved by ultrasonic to prepare a 128mM solution. NMR hydrogen spectroscopy was performed, wherein characteristic peaks of ureidopyrimidinone NH, which represent polymer, were 13.07ppm, 11.86ppm and 10.17ppm, respectively. 1 equivalent of LiPF is added6After that, the nuclear magnetic resonance hydrogen spectrum test is carried out, and the NH peak has no change.
Claims (4)
1. A method for regulating and controlling supermolecule polymerization relates to a method for orthogonally regulating and controlling a supermolecule polymerization process driven by a non-covalent acting force by another non-covalent acting force, which is realized in the following supermolecule polymerization monomers:
wherein the R group is methyl, ethyl, propyl, butyl, isoheptyl, undecyl, tridecyl;
the supramolecular polymer monomer can generate supramolecular polymerization through quadruple hydrogen bonds to generate a polymer structure as follows:
potassium hexafluorophosphate, potassium ions and diethylene glycol groups are added into a supermolecular polymer solution formed by the monomers to perform metal coordination similar to crown ether, so that the conformation of the monomers is changed, a clamp-type structure is formed, and the clamp-type structure is selectively dimerized to form a stable cyclic dimer form, and the structure is as follows:
2. method for modulating supramolecular polymerization according to claim 1, characterized in that the equivalent weight of added potassium ion is 1-2.
3. Method for modulating supramolecular polymerization according to claim 1, characterized in that the process is reversible, by adding benzo 18 crown 6, potassium ions are captured by benzo 18 crown 6 due to its stronger complexing power, the monomer in turn re-generates supramolecular polymer, which process can be modulated back and forth by alternating potassium ions and benzo 18 crown 6.
4. Method for modulating the polymerization of supramolecules as claimed in claim 1, characterized by the specificity of the response of the process, which is not the case for sodium and lithium ions of the same family as potassium ions.
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