CN109705368A - A kind of supermolecule and preparation method thereof based on benzimidazole iodo salt - Google Patents
A kind of supermolecule and preparation method thereof based on benzimidazole iodo salt Download PDFInfo
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- CN109705368A CN109705368A CN201811579800.8A CN201811579800A CN109705368A CN 109705368 A CN109705368 A CN 109705368A CN 201811579800 A CN201811579800 A CN 201811579800A CN 109705368 A CN109705368 A CN 109705368A
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Abstract
The invention discloses a kind of supramolecular organogels based on benzimidazole iodo salt, it is that supermolecule Subjective and Objective hydrogel SH-CD is obtained by host-guest Inclusion property with the molar ratio of 1:1 ~ 1:5 with macrocyclic host molecule cyclodextrin (α-CD) in pure water using benzimidazole iodo salt as object.Supramolecular hydrogel SH-CD has good aggregation inducing fluorescent emission performance, and when excitation wavelength is 280nm, supramolecular hydrogel SH-CD issues white fluorescent.In addition, supermolecule Subjective and Objective hydrogel has good thermostimulation, and there is good chemical stimulation performance to organic dye molecule methyl orange, is had a good application prospect in terms of the fluorescence identifying of dye molecule.
Description
Technical field
The present invention relates to a kind of supramolecular hydrogel more particularly to a kind of supermolecule masters based on benzimidazole iodo salt
Object hydrogel and preparation method thereof；The present invention simultaneously to the thermostimulation of the supramolecular hydrogel and chemical stimulation response performance into
Row research.
Background technique
In recent years, supermolecular gel is as a kind of important intelligent soft material, in building multiple stimulation responsiveness, photoelectricity function
Unique superiority is shown in terms of the soft substance of the functions such as energy and biocompatible material.It has been subjected to many supermoleculars
The favor of scholar.Especially for the gelation process and its stimulus response performance of supramolecular hydrogel.Supermolecular gel is in shape
At being frequently resulted in the process than more uniform nanostructure, and there is structure diversity；And on the other hand, the structure of supermolecular gel
Building unit is largely small molecule, and supermolecular gel is also to realize that small molecule is important in oversubscription subhierarchy/nano-level expression
Approach.They mainly include that hydrogen bond, hydrophobic effect, pi-pi accumulation, Host-guest interaction etc. are formed by non-covalent interaction
Supermolecular gel.
Cyclodextrin be contain there are six, the cyclic oligosaccharide of seven or eight glucopyranose units is respectively designated as α-ring
Dextrin (α-CD), beta-cyclodextrin (β-CD) or gamma-cyclodextrin (γ-CD).They have the truncated cone of hydrophilic exterior and hydrophobic internal cavities
Structure, unique structure allow them to encapsulate the molecule with suitable size by forming inclusion complex, this is also referred to as
For host-guest interaction.In addition, highdensity hydroxyl allows to react with specific organic group, this also becomes use
In further modified general molecular.Therefore, cyclodextrin causes in terms of Subjective and Objective assembling as specific macrocyclic host molecule
Great concern.
Imidazoles is the five-membered heteroaromatic compounds of the meta position nitrogen-atoms containing there are two in molecular structure, the position the 1- nitrogen in imidazole ring
The unshared electron pair participation of atom is cyclic conjugated, and the electron density of nitrogen-atoms reduces, and keeps the hydrogen atom on this nitrogen-atoms easy
It is left away with hydrogen ion form.With acidity, it may have alkalinity, it can be with highly basic forming salt.This is conducive to it and is led with cyclodextrin
Object effect prepares supermolecule fluorescence soft material.
Currently, people have developed a variety of organogels, metal gel etc., but due to the various advantages of pure water phase,
Prepare the supramolecular hydrogel of aqueous supramolecular hydrogel and its stimulus response performance research have become one it is popular
Topic.However, it is opposite or fewer by the report that host-guest Inclusion property prepares the supramolecular hydrogel of pure water phase,
The especially supramolecular hydrogel of the small molecule of two-component and macrocycle molecule effect.
Summary of the invention
The object of the present invention is to provide a kind of supramolecular hydrogels and preparation method thereof based on benzimidazole iodo salt.
One, the supramolecular hydrogel based on benzimidazole iodo salt
Present invention design has synthesized the supermolecule based on benzimidazole iodo salt BS and macrocyclic host molecule cyclodextrin (α-CD)
Hydrogel, in pure water, guest molecule benzimidazole iodo salt BS is passed through with cyclodextrin (α-CD) with the molar ratio of 1:1 ~ 1:5
Host-guest interaction self assembly obtains stable supermolecule Subjective and Objective hydrogel, is labeled as SH-CD.
The preparation of supramolecular hydrogel SH-CD: individual guest molecule BS in pure water not at gel, and when main body is added
Stable supramolecular hydrogel SH-CD can be formed by Host-guest interaction after molecule alpha-CD.Wherein object benzimidazole iodo
Salt BS and the big ring gelator cyclodextrin α-CD of main body are added in pure water with the molar ratio of 1:1 ~ 1:5, and heating makes it completely
Dissolution；It then cools to room temperature, obtains stable supermolecule Subjective and Objective hydrogel SH-CD.
Guest molecule benzimidazole iodo salt is 0.08 ~ 0.20 mg/ml in the content of pure water with cyclodextrin α-CD.
Wherein, the structural formula of guest molecule benzimidazole iodo salt (BS) is as follows:
What wherein a ~ e was respectively represented is the different Hydrogen Protons of benzimidazole iodo salt compound BS.
The structural formula of host molecule cyclodextrin (α-CD) is as follows:
Wherein 1 ~ 6 respectively represent is different Hydrogen Protons on cyclodextrin α-CD.
The synthetic method of benzimidazole iodo salt (BS) is the 2- undecyl-using acetonitrile as solvent1-HBenzo miaow
Azoles -3- methyl acetate and iodomethane react 30 ~ 32 h with the molar ratio of 1:3 ~ 1:1.5 at 85 ~ 90 DEG C；It is cold after reaction
But it to room temperature, filters and removes solvent, product is recrystallized with acetone/water, and obtaining white solid product is benzimidazole iodo salt
(BS).
The hydrogen that Fig. 1 is benzimidazole iodo salt BS is composed.It can be obtained by hydrogen spectrum, the chemical displacement value of BS are as follows: δ 7.76-7.65
(multiplet, 4H), 5.49(singlet, 2H), 4.11(singlet, 3H), 3.81(singlet, 3H) and, 1.71-1.67 is (triple
Peak, J=12 Hz, 2H), 1.45-1.42(triplet, J=12 Hz, 2H), 1.21(singlet, 16H) and, 0.85-0.82(is triple
Peak, J=12 Hz, 3H).
Fig. 2 is BS(a), α-CD(b), BS/ α-CD(c) part nucleus magnetic hydrogen spectrum figure.It can be found that H in figure (c)a, Hb, Hc
(BS) proton peak is mobile to low field, shows that there are model ylid bloom action power in the system；Hydrogen Proton H3, H5 on α-CD is to height
Field is mobile, illustrates that the long alkyl of object BS and α-CD cavity are penetrated by host-guest interaction in the cavity of main body α-CD, is formed
Supramolecular hydrogel.
Fig. 3 is the two-dimentional nuclear magnetic spectrogram of SH-CD(BS with α-CD).Wherein A/B represents Hb(BS), H3, H5(α-CD) proton
There is correlation at peak, this long alkyl for further explaining BS penetrates into main body α-CD cavity.Its structural formula is as follows:
Fig. 4 is powder diffraction (XRD) spectrogram of supermolecule Subjective and Objective hydrogel SH-CD.As seen from Figure 4, in guest molecule
In BS: 2θ=6.30。AccordinglydIt is 14.01, less than the length of the C11 alkyl chain of two molecules [1], illustrate to deposit in BS molecule
Winding between long alkyl chain, while 2θ=23.31 and 24.42 is correspondingd=3.81,3.63, illustrate between benzimidazole
With the presence of pi-pi accumulation.After forming supermolecule Subjective and Objective hydrogel SH-CD, 2θValue anddValue is by original 6.30 and 14.01
Become 3.59 and 24.6, this explanation long alkyl chain in supermolecule Subjective and Objective hydrogel SH-CD has part to paste possibly into ring
The inner cavity of essence, so as to form supramolecular hydrogel.
Two, the fluorescence response performance of supramolecular hydrogel SH-CD
1, the thermal response fluorescence property of supramolecular hydrogel SH-CD
Fig. 5 is the fluorescence emission spectrum of supramolecular hydrogel SH-CD.As shown in Figure 5, supramolecular hydrogel SH-CD has good
Aggregation inducing fluorescent emission performance.With the transformation of sol-gel, it is existing that supramolecular hydrogel SH-CD shows apparent AIE
As.As shown in Figure 5, the mixed solution of BS and SH-CD is in hot water (T > Tgel) in have hypofluorescence.However, with the temperature of dampening
It is reduced to the T of SH-CDgelHereinafter, the fluorescent emission intensity at 468nm shows and increases continuously that this shows supramolecular hydrogel
The fluorescence of SH-CD is aggregation inducing transmitting (AIE), and along with strong white fluorescent (excitation wavelength 280nm).Meanwhile
The performance can make it be applied to the fluorescence identifying of dye molecule.
2, the thermostimulation response performance of supramolecular hydrogel SH-CD
Fig. 6 is the thermal response circulation experiment (excitation wavelength 280nm) of supramolecular hydrogel SH-CD.As shown in fig. 6, supermolecule
The circulation of multiple molten sol-gel may be implemented under conditions of heating and cooling in hydrogel SH-CD, and its peritectic temperature is
43℃；It is accompanied by closing-opening of fluorescence simultaneously, illustrates that supramolecular hydrogel SH-CD has good thermostimulation response performance.
Illustrate that the performance can be such that it applies in terms of Thermo-sensitive soft material.
3, the chemical stimulation response performance of supramolecular hydrogel SH-CD
By the SH-CD hydrosol of the heat prepared, 0.2ml(1.6 × 10 are pipetted-5M it) in small gel bottle, is cooled to it
After gel, be added in small gel bottle with the organic dye molecule methyl orange (MO) of BS equimolar amounts, then in fluorescent lamp and
Fluorescence color and the gel state variation of gel are observed under ultraviolet lamp.As the chemical stimulation of the supramolecular hydrogel SH-CD of Fig. 7 is rung
It should test.The results show that the white fluorescent of supramolecular hydrogel SH-CD can be made to quench after methyl orange (MO) is added, and the water
The gel state of gel is destroyed, and illustrates that supramolecular hydrogel SH-CD has certain chemical stimulation for methyl orange (MO)
Response performance.And the performance can be such that it applies in the fluorescence identifying field of dye molecule.
Fig. 8 is BS(a), SH-CD(b), SH-CD-MO(c) xerogel scanning electron microscope (SEM) photograph.It can be seen that gelator BS
Microscopic appearance be rendered as amorphous state (a)；Supramolecular hydrogel is assembled into cyclodextrin (α-CD) progress Subjective and Objective is added
After SH-CD, pattern becomes laminar structured (b), and continuously adds competitive dyes molecule methyl orange (MO) pattern turn afterwards
Become unformed small block structure (c).
In conclusion the present invention is using benzimidazole iodo salt as guest molecule, based on macrocycle molecule cyclodextrin α-CD
Molecule obtains stable supermolecule Subjective and Objective hydrogel SH-CD by the Inclusion property of host-guest in pure water；Supermolecule water
Gel SH-CD has good aggregation inducing fluorescent emission performance, when excitation wavelength is 280nm, supramolecular hydrogel SH-CD
Issue white fluorescent.In addition, supermolecule Subjective and Objective hydrogel has good thermostimulation performance, and to organic dye molecule methyl
Orange (MO) has good chemical stimulation performance, has in terms of the stimulating responsive of Thermo-sensitive material and azo dyes molecule
Good application prospect.
Detailed description of the invention
Fig. 1 is the hydrogen spectrogram of benzimidazole iodo salt BS.
Fig. 2 is BS, the part nucleus magnetic hydrogen spectrum figure of α-CD, BS/ α-CD.
Fig. 3 is the two-dimentional nuclear magnetic spectrogram of BS/ α-CD.
Fig. 4 is the XRD diagram of BS and SH-CD.
Fig. 5 is the fluorescence spectra (excitation wavelength 280nm) of SH-CD.
Fig. 6 is the thermal response circulation experiment (excitation wavelength 280nm) of supramolecular hydrogel SH-CD.
Fig. 7 is chemical stimulation responsiveness photo of the supramolecular hydrogel SH-CD to methyl orange (MO).
Fig. 8 is BS, the scanning electron microscope (SEM) photograph of SH-CD, SH-CD-MO.
Specific embodiment
The preparation of supramolecular hydrogel of the present invention and application are described further below by specific embodiment.
The preparation of embodiment one, supramolecular hydrogel SH-CD
1,1.03 g(3.0 mmol the synthesis of benzimidazole iodo salt BS: are weighed) 2- undecyl-1-HBenzimidazole -3-
Methyl acetate, 1.27 g(9.0 mmol) iodomethane, it is dissolved in 50ml acetonitrile, reacts 30h at 85 ~ 90 DEG C；After reaction
It is cooled to room temperature, filters and remove solvent, recrystallized with acetone/water, white crystalline solid 1.3747g is precipitated, yield 95% melts
Point: 108 ~ 110 DEG C.
2, BS:0.0040g(8.2 × 10 preparation of supramolecular hydrogel (SH-CD): are taken-6Mol), α-CD:0.0076g
(8.2 × 10-6Mol), it is added in 0.2ml pure water, heating makes it completely dissolved；Then it is cooled to room temperature, is obtained stable
Supermolecule Subjective and Objective hydrogel SH-CD.When excitation wavelength is 280nm, supramolecular hydrogel SH-CD issues white fluorescent.
Embodiment 2, supermolecule Subjective and Objective hydrogel SH-CD stimulus response performance
1, a certain amount of gelator BS and cyclodextrin α-CD the thermostimulation responsiveness of supramolecular hydrogel SH-CD: are weighed in small
In gel bottle, be heated to 70 DEG C become completely heat the hydrosols (0.2ml, 1.6 × 10-5M), it is slowly cooled to room temperature
(25 DEG C), supramolecular hydrogel is formed.Meanwhile it is solidifying that multiple colloidal sol-may be implemented under conditions of continuous heating and cooling in discovery
The circulation of glue；It is accompanied by closing-opening of fluorescence simultaneously, illustrates that supramolecular hydrogel SH-CD has good thermostimulation to respond
Performance.
2,0.2ml(1.6 × 10 the chemical stimulation responsiveness of supramolecular hydrogel SH-CD: are pipetted in small gel bottle- 5M) prepared and heat the hydrosol, after it is cooled to gel, in these small gel bottles be added with BS equimolar amounts
Organic dye molecule methyl orange (MO), then under fluorescent lamp and ultraviolet lamp observe gel fluorescence color variation.It was found that adding
Entering methyl orange can be such that the white fluorescent of supramolecular hydrogel SH-CD quenches, and the gel state of the hydrogel is destroyed, and illustrates this
Supramolecular hydrogel SH-CD has certain chemical stimulation response performance for methyl orange.
Claims (7)
1. a kind of supramolecular hydrogel based on benzimidazole iodo salt is the guest molecule benzimidazole iodo in pure water
Salt and macrocyclic host molecule cyclodextrin α-CD, by the Inclusion property of host-guest, are obtained stable with the molar ratio of 1:1 ~ 1:5
Supermolecule Subjective and Objective hydrogel SH-CD；The structural formula of the guest molecule benzimidazole iodo salt BS is as follows:
What wherein a ~ e was respectively represented is the different Hydrogen Protons on benzimidazole iodo salt compound BN；
The structural formula of host molecule cyclodextrin α-CD is as follows:
Wherein 1 ~ 6 respectively represent is different Hydrogen Protons on cyclodextrin α-CD.
2. the supramolecular hydrogel as described in claim 1 based on benzimidazole iodo salt, it is characterised in that: the guest molecule
The long alkyl chain of sub- benzimidazole iodo salt has part to penetrate into the cavity of host cyclodextrin α-CD.
3. the supramolecular hydrogel as described in claim 1 based on benzimidazole iodo salt, it is characterised in that: supramolecular hydrogel
Glue SH-CD has good aggregation inducing fluorescent emission performance, when excitation wavelength is 280nm, supramolecular hydrogel SH-CD hair
White fluorescent out.
4. the supramolecular hydrogel as described in claim 1 based on benzimidazole iodo salt, it is characterised in that: supramolecular hydrogel
Glue SH-CD has thermostimulation responsiveness, and under conditions of heating and cooling, supramolecular hydrogel is able to achieve the phase of sol-gel
State transformation, and its peritectic temperature is 43 DEG C.
5. the supramolecular hydrogel as described in claim 1 based on benzimidazole iodo salt, it is characterised in that: supramolecular hydrogel
Glue SH-CD has good chemical stimulation performance to organic dye molecule methyl orange (MO), is being based on benzimidazole iodo salt
Supramolecular hydrogel in, be added methyl orange (MO) gel state of supramolecular hydrogel SH-CD can be made to be destroyed, white fluorescent
Quenching.
6. the synthetic method of the supramolecular hydrogel as described in claim 1 based on benzimidazole iodo salt, it is characterised in that:
The object benzimidazole iodo salt BS and big ring gelator cyclodextrin α-CD of main body is added to the molar ratio of 1:1 ~ 1:5 pure
In water, heating is made it completely dissolved；It then cools to room temperature, obtains stable supermolecule Subjective and Objective hydrogel SH-CD.
7. the synthetic method of the supramolecular hydrogel as claimed in claim 4 based on benzimidazole iodo salt, it is characterised in that:
Guest molecule benzimidazole iodo salt is 0.08 ~ 0.20 mg/ml in the content of pure water with cyclodextrin α-CD.
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| CN114671853A (en) * | 2022-03-30 | 2022-06-28 | 常州大学 | Green fluorescent molecule, preparation method and fluorescent color regulation method |
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