CN109705368B - Supermolecule based on benzimidazole iodonium salt and preparation method thereof - Google Patents
Supermolecule based on benzimidazole iodonium salt and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a supermolecule organogel based on benzimidazole iodonium salts, which is characterized in that benzimidazole iodonium salts are used as an object, and are subjected to host-object inclusion reaction with macrocyclic host molecule cyclodextrin (alpha-CD) in pure water according to a molar ratio of 1: 1-1: 5 to obtain supermolecule host-object hydrogel SH-CD. The supermolecule hydrogel SH-CD has good aggregation-induced fluorescence emission performance, and when the excitation wavelength is 280nm, the supermolecule hydrogel SH-CD emits white fluorescence. In addition, the supermolecule host-guest hydrogel has good thermal stimulation, good chemical stimulation performance on organic dye molecules, namely methyl orange, and good application prospect in the aspect of fluorescent recognition of dye molecules.
Description
Technical Field
The invention relates to a supermolecule hydrogel, in particular to a supermolecule host-guest hydrogel based on benzimidazole iodonium salt and a preparation method thereof; the invention simultaneously researches the thermal stimulation and chemical stimulation response performance of the supermolecule hydrogel.
Background
In recent years, the supermolecule gel as an important intelligent soft material has unique superiority in constructing functional soft substances such as multiple stimulation responsiveness, photoelectric function, biocompatible material and the like. Have received favor from many supramolecular chemists. Especially for the gelation process of supramolecular hydrogels and their stimulus response properties. The supermolecular gel usually obtains a relatively uniform nano structure in the forming process and has structural diversity; on the other hand, most of the building units of the supramolecular gel are small molecules, and the supramolecular gel is also an important way for realizing the expression of the small molecules in a supramolecular level/nanometer level. They form supramolecular gels through non-covalent interactions, mainly including hydrogen bonding, hydrophobic interactions, pi-pi stacking, host-guest interactions, etc.
Cyclodextrins are cyclic oligosaccharides containing six, seven, or eight glucopyranose units, designated α -cyclodextrin (α -CD), β -cyclodextrin (β -CD), or γ -cyclodextrin (γ -CD), respectively. They have a truncated cone structure with a hydrophilic exterior and a hydrophobic interior, the unique structure of which enables them to encapsulate molecules of appropriate size by forming inclusion complexes, also known as host-guest interactions. Furthermore, the high density of hydroxyl groups allows for reaction with specific organic groups, which also makes it a versatile molecule for further modification. Thus, cyclodextrins have attracted considerable attention as specific macrocyclic host molecules in terms of host-guest assembly.
Imidazole is a five-membered aromatic heterocyclic compound containing two meta-position nitrogen atoms in a molecular structure, an unshared electron pair of the 1-position nitrogen atom in the imidazole ring participates in cyclic conjugation, and the electron density of the nitrogen atom is reduced, so that the hydrogen atom on the nitrogen atom is easy to leave in a hydrogen ion form. Has acidity and alkalinity, and can form salt with strong base. The method is favorable for the host-guest action of the supramolecular fluorescent soft material and cyclodextrin to prepare the supramolecular fluorescent soft material.
At present, various organogels, metal gels, etc. have been developed, but due to various advantages of pure aqueous phases, research for preparing aqueous supramolecular hydrogels and supramolecular hydrogels with their stimuli-responsive properties has become a hot topic. However, relatively few reports have been made on the preparation of pure aqueous supramolecular hydrogels by host-guest inclusion, especially supramolecular hydrogels with two-component small molecules interacting with large ring molecules.
Disclosure of Invention
The invention aims to provide a supermolecular hydrogel based on benzimidazole iodonium salt and a preparation method thereof.
Supermolecule hydrogel based on benzimidazole iodonium salt
The invention designs and synthesizes supermolecule hydrogel based on benzimidazole iodonium salt BS and macrocyclic host molecule cyclodextrin (alpha-CD), and in pure water, a guest molecule benzimidazole iodonium salt BS and cyclodextrin (alpha-CD) are self-assembled under the action of a host and a guest according to the molar ratio of 1: 1-1: 5 to obtain stable supermolecule host-guest hydrogel which is marked as SH-CD.
Preparation of supramolecular hydrogel SH-CD: the single guest molecule BS does not form gel in pure water, and stable supermolecular hydrogel SH-CD can be formed through host-guest action after host molecule alpha-CD is added. The method comprises the following steps of adding a guest benzimidazole iodonium salt BS and a host macrocyclic gelator cyclodextrin alpha-CD into pure water according to a molar ratio of 1: 1-1: 5, and heating to completely dissolve the guest benzimidazole iodonium salt BS and the host macrocyclic gelator cyclodextrin alpha-CD; and then cooling to room temperature to obtain the stable supramolecular host-guest hydrogel SH-CD.
The content of the guest molecule benzimidazole iodonium salt and the cyclodextrin alpha-CD in pure water is 0.08-0.20 mg/ml.
Wherein the structural formula of the guest molecule benzimidazole iodonium salt (BS) is as follows:
wherein a to e represent different hydrogen protons of the benzimidazole iodonium salt compound BS.
The structural formula of the host molecule cyclodextrin (alpha-CD) is as follows:
wherein 1-6 represent different hydrogen protons on the cyclodextrin alpha-CD.
The synthesis method of benzimidazole iodonium salt (BS) uses acetonitrile as solvent and 2-undecyl-1-HReacting-benzimidazole-3-methyl acetate and methyl iodide at a molar ratio of 1: 3-1: 1.5 at 85-90 ℃ for 30-32 hours; and cooling to room temperature after the reaction is finished, performing suction filtration to remove the solvent, and recrystallizing the product with acetone/water to obtain a white solid product, namely the benzimidazole iodonium salt (BS).
FIG. 1 is a hydrogen spectrum of benzimidazolium iodonium salt BS. From the hydrogen spectra, the chemical shift values of BS are: δ 7.76-7.65 (multiplet, 4H), 5.49 (singlet, 2H), 4.11 (singlet, 3H), 3.81 (singlet, 3H), 1.71-1.67 (triplet, J =12 Hz, 2H), 1.45-1.42 (triplet, J =12 Hz, 2H), 1.21 (singlet, 16H), 0.85-0.82 (triplet, J =12 Hz, 3H).
FIG. 2 is a partial nuclear magnetic hydrogen spectrum of BS (a), alpha-CD (b), BS/alpha-CD (c). It can be found that H in the graph (c)a，Hb，Hc(BS) the proton peaks all move to low fields, indicating the presence of van der waals forces in the system; the hydrogen protons H3 and H5 on the alpha-CD move to a high field, which shows that the long alkyl group and the alpha-CD cavity of the guest BS penetrate into the alpha-CD cavity of the host through the actions of the host and the guest to form the supermolecule hydrogel.
FIG. 3 shows two-dimensional nuclear magnetic spectra of SH-CD (BS and alpha-CD). Wherein A/B represents HbThe (BS), H3, H5 (α -CD) proton peaks are correlated, which further illustrates the penetration of the long alkyl group of BS into the bulk α -CD cavity. The structural formula is as follows:
FIG. 4 is a powder diffraction (XRD) spectrum of the supramolecular host-guest hydrogel SH-CD. As can be seen from fig. 4, in the guest molecule BS: in 2θ=6.30。Corresponding todIs 14.01A, the length of the C11 alkyl chain being less than two molecules [1]Description of the presence in the BS moleculeEntanglement between long alkyl chains, 2θ=23.31 and 24.42 correspondingd3.81 a, 3.63 a, indicating that pi-pi stacking exists between benzimidazoles. After formation of the supramolecular guest-host hydrogel SH-CD, at 2θValue sumdThe values were changed from the original 6.30 and 14.01A to 3.59 and 24.6A, which indicates that a portion of the long alkyl chain may enter the internal cavity of cyclodextrin in the supramolecular host-guest hydrogel SH-CD, thereby forming a supramolecular hydrogel.
Fluorescent response performance of two-molecule and supermolecule hydrogel SH-CD
1. Thermal response fluorescence property of supermolecular hydrogel SH-CD
FIG. 5 shows fluorescence emission spectrum of supramolecular hydrogel SH-CD. As can be seen from FIG. 5, the supramolecular hydrogel SH-CD has good aggregation-induced fluorescence emission performance. With the transformation of sol-gel, the supermolecular hydrogel SH-CD presents obvious AIE phenomenon. As shown in FIG. 5, the mixed solution of BS and SH-CD was heated in hot water (T > T)gel) Has weak fluorescence. However, as the temperature of the water decreases to the T of the SH-CDgelBelow, the fluorescence emission intensity at 468nm shows a continuous increase, which indicates that the fluorescence of supramolecular hydrogel SH-CD is Aggregation Induced Emission (AIE) accompanied by intense white fluorescence (excitation wavelength 280 nm). Meanwhile, the performance can enable the fluorescent dye to be applied to fluorescent recognition of dye molecules.
2. Thermal stimulation response performance of supermolecular hydrogel SH-CD
FIG. 6 shows the thermal response cycle experiment (excitation wavelength is 280 nm) of the supramolecular hydrogel SH-CD. As shown in fig. 6, the supramolecular hydrogel SH-CD can realize multiple sol-gel cycles under heating and cooling conditions, and the melting temperature thereof is 43 ℃; meanwhile, the closing-opening of fluorescence is accompanied, so that the supermolecular hydrogel SH-CD has good thermal stimulation response performance. The performance can be applied to the aspect of temperature sensitive soft materials.
3. Chemical stimulation response performance of supermolecular hydrogel SH-CD
0.2ml (1.6X 10) of the hot SH-CD hydrosol prepared is removed-5M) in a small gel bottle, after it has cooled to gel, in a small gelThe organic dye molecule Methyl Orange (MO) was added to the bottle in an equimolar amount to BS, and then the fluorescence color and the change in gel state of the gel were observed under a fluorescent lamp and an ultraviolet lamp. Chemical stimulus response experiments of supramolecular hydrogel SH-CD as shown in figure 7. The result shows that the white fluorescence of the supramolecular hydrogel SH-CD can be quenched after Methyl Orange (MO) is added, and the gel state of the hydrogel is destroyed, which indicates that the supramolecular hydrogel SH-CD has a certain chemical stimulus response performance for the Methyl Orange (MO). And the performance can make the fluorescent dye be applied to the field of fluorescent recognition of dye molecules.
FIG. 8 shows SEM pictures of BS (a), SH-CD (b), SH-CD-MO (c) xerogel. It can be seen that the microscopic morphology of the gelator BS appears as amorphous state (a); after cyclodextrin (alpha-CD) is added to carry out host-guest assembly to form the supermolecular hydrogel SH-CD, the appearance of the supermolecular hydrogel is changed into a lamellar structure (b), and after competitive dye molecule Methyl Orange (MO) is continuously added, the appearance of the supermolecular hydrogel is changed into an amorphous small blocky structure (c).
In conclusion, the stable supermolecule host-guest hydrogel SH-CD is obtained by taking benzimidazole iodonium salt as a guest molecule and taking macrocyclic cyclodextrin alpha-CD as a host molecule through host-guest inclusion in pure water; the supermolecule hydrogel SH-CD has good aggregation-induced fluorescence emission performance, and when the excitation wavelength is 280nm, the supermolecule hydrogel SH-CD emits white fluorescence. In addition, the supermolecule host-guest hydrogel has good thermal stimulation performance, has good chemical stimulation performance on organic dye molecules, namely Methyl Orange (MO), and has good application prospect in the stimulation responsiveness of temperature-sensitive materials and azo dye molecules.
Drawings
FIG. 1 is a hydrogen spectrum of benzimidazolium iodonium salt BS.
FIG. 2 is a partial nuclear magnetic hydrogen spectrum of BS, α -CD, BS/α -CD.
FIG. 3 is a two-dimensional nuclear magnetic spectrum of BS/α -CD.
FIG. 4 is an XRD pattern of BS and SH-CD.
FIG. 5 shows the fluorescence spectrum of SH-CD (excitation wavelength of 280 nm).
FIG. 6 shows the thermal response cycle experiment (excitation wavelength is 280 nm) of the supramolecular hydrogel SH-CD.
FIG. 7 is a photograph showing the chemical stimulus responsiveness of the supramolecular hydrogel SH-CD to Methyl Orange (MO).
FIG. 8 is a scanning electron micrograph of BS, SH-CD, SH-CD-MO.
Detailed Description
The preparation and use of the supramolecular hydrogels of the present invention are further illustrated by the specific examples below.
EXAMPLE one preparation of supramolecular hydrogel SH-CD
1. Synthesis of benzimidazole iodonium salt BS: 1.03 g (3.0 mmol) of 2-undecyl-1-H-benzimidazole-3-acetic acid methyl ester, 1.27 g (9.0 mmol) iodomethane, dissolved in 50ml acetonitrile, reacted at 85-90 ℃ for 30 h; after the reaction, the reaction mixture was cooled to room temperature, the solvent was removed by suction filtration, and the mixture was recrystallized from acetone/water to precipitate 1.3747g of a white crystalline solid, the yield was 95%, and the melting point: 108-110 ℃.
2. Preparation of supramolecular hydrogel (SH-CD): taking BS: 0.0040g (8.2X 10)-6mol），α-CD：0.0076g（8.2×10-6mol) is added into 0.2ml of pure water and heated to be completely dissolved; and then cooling to room temperature to obtain the stable supramolecular host-guest hydrogel SH-CD. When the excitation wavelength is 280nm, the supermolecular hydrogel SH-CD emits white fluorescence.
Example 2 SH-CD stimulus response Properties of supramolecular host-guest hydrogels
1. Thermal stimulus responsiveness of supramolecular hydrogel SH-CD: weighing a certain amount of gelator BS and cyclodextrin alpha-CD in a small gel bottle, heating to 70 deg.C to completely become hot hydrosol (0.2 ml, 1.6X 10)-5M), it is slowly cooled to room temperature (25 ℃), supramolecular hydrogel formation. Meanwhile, the sol-gel circulation can be realized for many times under the condition of continuous heating and cooling; meanwhile, the closing-opening of fluorescence is accompanied, so that the supermolecular hydrogel SH-CD has good thermal stimulation response performance.
2. Chemical stimulus responsiveness of supramolecular hydrogel SH-CD: in that0.2ml (1.6X 10) was pipetted into a small gel bottle- 5M) is cooled to gel, then the organic dye molecule Methyl Orange (MO) is added into the small gel bottles in the same molar quantity as BS, and then the fluorescence color change of the gel is observed under a fluorescent lamp and an ultraviolet lamp. The addition of methyl orange is found to quench the white fluorescence of the supramolecular hydrogel SH-CD, and the gel state of the hydrogel is destroyed, which indicates that the supramolecular hydrogel SH-CD has a certain chemical stimulus response performance to the methyl orange.
Claims (5)
1. A supramolecular hydrogel based on benzimidazole iodonium salt is characterized in that: the supermolecule hydrogel is prepared by performing inclusion reaction on a guest molecule, namely benzimidazole iodonium salt and macrocyclic host molecule cyclodextrin alpha-CD (alpha-CD) in a molar ratio of 1: 1-1: 5 in pure water to obtain stable supermolecule guest-host hydrogel SH-CD; the structural formula of the guest molecule benzimidazole iodonium salt BS is as follows:
wherein a-e respectively represent different hydrogen protons on the benzimidazole iodonium salt compound BS;
the structural formula of the cyclodextrin alpha-CD of the host molecule is as follows:
wherein 1-6 represent different hydrogen protons on the cyclodextrin alpha-CD.
2. Supramolecular hydrogel based on iodonium benzimidazoles according to claim 1, characterized in that: the supermolecule hydrogel SH-CD has good aggregation-induced fluorescence emission performance, and when the excitation wavelength is 280nm, the supermolecule hydrogel SH-CD emits white fluorescence.
3. Supramolecular hydrogel based on iodonium benzimidazoles according to claim 1, characterized in that: the supermolecule hydrogel SH-CD has thermal stimulation responsiveness, can realize the phase state transformation of sol-gel under the conditions of heating and cooling, and has the transfusive temperature of 43 ℃.
4. Supramolecular hydrogel based on iodonium benzimidazoles according to claim 1, characterized in that: the supermolecule hydrogel SH-CD has good chemical stimulation performance on organic dye molecule methyl orange, and the addition of methyl orange into the supermolecule hydrogel based on benzimidazole iodonium salt can destroy the gel state of the supermolecule hydrogel SH-CD and quench white fluorescence.
5. The method for the synthesis of supramolecular hydrogels based on iodonium benzimidazoles according to claim 1, wherein: adding a guest benzimidazole iodonium salt BS and a host macrocyclic gelator cyclodextrin alpha-CD into pure water according to a molar ratio of 1: 1-1: 5, and heating to completely dissolve the guest benzimidazole iodonium salt BS and the host macrocyclic gelator cyclodextrin alpha-CD; and then cooling to room temperature to obtain the stable supramolecular host-guest hydrogel SH-CD.
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