CN110003355A - A kind of glucan derivative and its preparation method and use with AIE feature - Google Patents

A kind of glucan derivative and its preparation method and use with AIE feature Download PDF

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Publication number
CN110003355A
CN110003355A CN201910291713.0A CN201910291713A CN110003355A CN 110003355 A CN110003355 A CN 110003355A CN 201910291713 A CN201910291713 A CN 201910291713A CN 110003355 A CN110003355 A CN 110003355A
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glucan
feature
glucan derivative
aie
preparation
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CN110003355B (en
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方敏
徐倩文
郭一帆
李村
朱维菊
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Anhui University
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Anhui University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/145—Heterocyclic containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom

Abstract

The invention discloses a kind of glucan derivative and its preparation method and use with AIE feature, wherein the structural formula of the glucan derivative with AIE feature is as follows:Wherein x=59.4, y=1.6.The present invention has the glucan derivative of AIE feature water-soluble, and has lower critical micelle concentration, which is 5 × 10‑3Mg/mL has good aggregation-induced emission feature at low concentrations, and the concentration range with aggregation-induced emission feature is 1 × 10‑3Mg/mL to 60 × 10‑3Mg/mL is worth in cell imaging and its Related Research Domain with important research.

Description

A kind of glucan derivative and its preparation method and use with AIE feature
Technical field
The present invention relates to a kind of glucan derivative and its preparation method and use with AIE feature, belongs to phosphor Expect technical field.
Background technique
In recent years, with the continuous development of bio-imaging technology, so that the nano-carrier with imaging function is studied The attention of person.However, (ACQ) effect, which is quenched, by aggregation in traditional fluorescence probe is influenced, its fluorescence efficiency at high concentrations It can significantly reduce, cause using fluorescence to be the detection and analysis means of output signal by serious restriction.And there is researcher to find one Kind new fluorescent molecule, it can issue strong fluorescence intensity in the collected state, and this new fluorescent molecule can be to avoid The fluorescent quenching phenomenon that traditional fluorescent molecule occurs under a high concentration condition, this phenomenon are referred to as aggregation-induced emission (AIE) effect.Researcher produces great interest to this fluorescent molecule, with going deep into for research, entire visible wavelength Range develops the system with aggregation-induced emission effect by researcher, these systems with AIE are widely used In cell imaging and its Related Research Domain.
However, the AIE system being reported at present, focuses primarily upon small molecule and organic polymer with pi-conjugated group. These contain the molecule of pi-conjugated group, and there is only poorly water-solubles for biologic applications, and have biggish cell toxicant Property, these disadvantages seriously limit them in the application of biomedicine field.On the other hand, amphiphilic that there is aggregation inducing hair The fluorescent molecule of light property is seldom reported that amphipathic molecule can be self-assembly of with hydrophobic core and hydrophilic shell structure by researcher Nano-micelle in aqueous solution, by with AIE feature small molecule fluorescent compound with have hydrophilic substance formed two The molecule of parent's property, in structure, this amphiphilic molecule had not only contained the hydrophobic fluorescent chemicals with AIE feature but also had contained There is hydrophilic structural unit.Dextran molecule can be compatible with biological tissue, and reason is on dextran molecule chain containing big The hydrophilic hydroxyl of amount, and can degrade under the action of enzyme, due to the hydrophily and biocompatibility of glucan, Allow glucan as a kind of carrier, is used widely in bio-imaging field.
Since cognition time of the researcher to aggregation-induced emission is not grown, up to the present, synthesis has aggregation inducing Luminous classes of compounds is extremely limited, and structure is relatively simple.
Summary of the invention
The present invention is intended to provide a kind of glucan derivative and its preparation method and use with AIE feature.The present invention By MOLECULE DESIGN, the novel compound with aggregation inducing feature is synthesized, by forming amphiphilicization with glucan Object is closed, can be used as cell imaging and its Related Research Domain.
The present invention has the glucan derivative of AIE feature, and structural formula is as follows:
Wherein x=59.4, y=1.6.
The present invention has the preparation method of the glucan derivative of AIE feature, is by glucan and with the change of AIE feature Closing object 1 --- N- ethoxy-4- (4- formylphenyl)-1,8- naphthalimide carries out esterification by carbonyl dimidazoles (CDI), Obtain target product.
The structural formula of the compound 1 is as follows:
The present invention has the preparation method of the glucan derivative of AIE feature, specifically comprises the following steps:
Step 1: reaction kit is sufficiently dry in 120 DEG C of baking oven, is put into drier and is cooled to room temperature.It is burnt in round bottom The anhydrous DMSO of 0.194g (1.2mmol) CDI and 3ml is added in bottle, is dispersed with stirring uniformly；Accurately weigh 0.345g (1mmol) Compound 1 is completely dissolved in the anhydrous DMSO of 8ml, is slowly added dropwise with constant pressure funnel into round-bottomed flask, is stirred under normal temperature condition Mix reaction 3h；
Step 2: weighing 0.31g glucan in the reactor being completely dried, appropriate anhydrous DMSO is added, in N2Under protection Heating stirring to glucan is completely dissolved, and then to the reaction solution that step 1 is slowly added dropwise in reactor, is stirred under the conditions of 70 DEG C Reaction is for 24 hours；Reaction solution is transferred in bag filter, dialyses in DMSO solution for 24 hours, then dialyses in deionized water first 72h, dialyzate 8h replacement are primary, product freeze-drying.
The synthetic route of target product of the present invention is as follows:
The present invention has the purposes of the glucan derivative of AIE feature, is during cell imaging as fluorescence probe Application.
The present invention has the glucan derivative of AIE feature water-soluble, and has lower critical micelle concentration, should Critical micelle concentration is 5 × 10-3Mg/mL has good aggregation-induced emission feature at low concentrations, has aggregation inducing hair The concentration range of light feature is 1 × 10-3Mg/mL to 60 × 10-3Mg/mL has weight in cell imaging and its Related Research Domain Want researching value.
Compared with prior art the beneficial effects of the present invention are embodied in:
The present invention selects the novel small molecule compound with aggregation-induced emission feature, it and glucan form amphiphilic Property glucan derivative, in aqueous solution have good solubility, and concentration in aqueous solution be higher than its critical glue Autofluorescence nano-micelle can be formed when beam concentration, it can be used as autofluorescence probe for being imaged into the cell.
Detailed description of the invention
Fig. 1 is the infrared spectrum for the glucan derivative that the present invention has AIE feature.
Fig. 2 is the nucleus magnetic hydrogen spectrum for the glucan derivative that the present invention has AIE feature.
Fig. 3 is the fluorescence spectrum (λ of the aqueous solution of the glucan derivative with AIE feature of various concentrationex= 360nm)。
Fig. 4 is fluorescence intensity and its concentration pair of the glucan derivative with AIE feature of various concentration at 460nm Number relational graph (λex=360nm).
Fig. 5 is the photobleaching figure for the glucan derivative that the present invention has AIE feature.
Fig. 6 is the Confocal Images of HeLa cell.Wherein, the fluorescent image (A) of HeLa cell, fluorescence and bright field image It is superimposed (B), bright field image (C).
Specific embodiment
The present invention can be further illustrated by the following examples, but be not limited solely to embodiment.
Embodiment 1: the preparation of the glucan derivative with AIE feature
1, reaction kit is sufficiently dry in 120 DEG C of baking oven, is put into drier and is cooled to room temperature.In round-bottomed flask The anhydrous DMSO of 0.194g (1.2mmol) CDI and 3ml is added, is dispersed with stirring uniformly；Accurately weigh 0.345g (1mmol) compound 1 It is completely dissolved in the anhydrous DMSO of 8ml, is slowly dropped in round-bottomed flask with constant pressure funnel, is stirred to react under normal temperature condition 3h。
2,0.31g glucan separately is accurately weighed in the three-neck flask being completely dried, appropriate anhydrous DMSO is added, in N2It protects It protects lower heating stirring to glucan to be completely dissolved, the reaction solution that step 1 is obtained is placed in constant pressure funnel, is slowly added drop-wise to circle In the flask of bottom, it is stirred to react for 24 hours under the conditions of 70 DEG C；Reaction solution is transferred in bag filter, is dialysed in DMSO solution first About for 24 hours, then dialyse 72h in deionized water, and dialyzate 8h replacement is primary, product freeze-drying.
Fig. 1 is that have the infrared spectrum of the glucan derivative of AIE feature (Dextran: glucan, Dex-CHO: Portugal is poly- Sugared fluorescent marker).FT-IR (KBr, cm-1): 3400 (O-H stretching vibration, 2929 (- CH2Stretching vibration), by with raw material phase Than the peak O-H of product is weaker than the peak O-H of raw material glucan, shows that the hydroxyl of raw material glucan is reacted.In 1747cm-1Place is The ester group peak newly formed, it was demonstrated that product successfully synthesizes.
Fig. 2 is the nucleus magnetic hydrogen spectrum figure with the glucan derivative of AIE feature.The solvent of selection is DMSO-d6,3.2- 4.9ppm belongs to the-CH of glucan2And the peak-OH, 7.8-8.5ppm belong to the hydrogen on the naphthalene nucleus and phenyl ring of compound 1, 10.1ppm belongs to the peak-CHO of compound 1, shows that product successfully synthesizes.
Embodiment 2: the aggregation-induced emission property of the glucan derivative with AIE feature
Target product 20mg is accurately weighed, is dissolved completely in DMSO solvent, it is molten to be configured to the deposit that concentration is 25mg/mL Stock solution is diluted to the solution to be measured that concentration is 1mg/mL with water, takes the pure water of 4mL in PE pipe by liquid, is managed in each PE In be separately added into 4 μ L, 8 μ L, 12 μ L, 20 μ L, 28 μ L, 36 μ L, 48 μ L, 72 μ L concentration be 1mg/mL solution to be measured, simultaneously respectively Take 3.84mL and 3.76mLH2O is separately added into 160 μ L, the solution to be measured that 240 μ L concentration are 1mg/mL, shakes in two PE pipes It is even, it is configured to the solution to be measured of various concentration, the fluorescence spectrum (as shown in Figure 3) of these solution to be measured is measured, as solution is dense The increase of degree, there is the fluorescence intensity of the glucan derivative of AIE feature to gradually increase for this, and excitation wavelength is in λex=360nm. Illustration is that concentration is 10 × 10-3Photo of the solution of mg/mL under the ultraviolet lamp of 365nm.
Fig. 4 is the fluorescence emission spectrum and log concentration relationship of the glucan derivative with AIE feature of various concentration Figure, CMC is 5 × 10-3Mg/mL shows that the product has lower critical micelle concentration.
Embodiment 3: the photobleaching experiment of the glucan derivative with AIE feature
The solution to be measured that concentration is 1mg/mL in 1.6mL embodiment 2 is taken, is added drop-wise in the water of 80mL, being configured to concentration is 20×10-3The solution of mg/mL is stirred continuously under 365 ultraviolet lamp, takes 3-4mL solution to measure according to certain time interval Fluorescence intensity (λem=360nm), its fluorescence intensity I (as shown in Figure 5), I in measurement 8h0It represents to be measured when light application time is 0 The fluorescence intensity of liquid finds that its fluorescence intensity is first declined slightly in 8h, is then tended towards stability, it is anti-light well to illustrate that it has It is Bleachability.
Embodiment 4: the cell imaging of the glucan derivative with AIE feature
Fig. 6 is the laser co-focusing that cell after HeLa cell 30min is handled with the glucan derivative with AIE feature Micro-image, A are fluorescence field picture, and B is the superposition of fluorescence and bright field image, and C is bright field image.As can be seen from Figure 6A, exist Under the laser excitation of 406nm, which launches apparent blue phosphor in HeLa into the cell.It can from Fig. 6 C Out, the cell co-cultured with the glucan derivative can keep its cellular morphology well, and it is good to show that the glucan has Biocompatibility.

Claims (6)

1. a kind of glucan derivative with AIE feature, it is characterised in that its structural formula is as follows:
Wherein x=59.4, y=1.6.
2. a kind of preparation method of the glucan derivative described in claim 1 with AIE feature, it is characterised in that:
It is by glucan and with compound 1 --- N- ethoxy-4- (4- formylphenyl)-1,8- naphthalimide of AIE feature Esterification is carried out by carbonyl dimidazoles, obtains target product；
The structural formula of the compound 1 is as follows:
3. preparation method according to claim 2, it is characterised in that include the following steps:
Step 1: 1.2mmol CDI and anhydrous DMSO being added in the round-bottomed flask being completely dried, is dispersed with stirring uniformly；It weighs 1mmol compound 1 is completely dissolved in anhydrous DMSO, is slowly added dropwise with constant pressure funnel into round-bottomed flask, under normal temperature condition It is stirred to react 3h；
Step 2: weighing 0.31g glucan in the reactor being completely dried, anhydrous DMSO is added, in N2Protect lower heating stirring It is completely dissolved to glucan, then to the reaction solution that step 1 is slowly added dropwise in reactor, is stirred to react for 24 hours under the conditions of 70 DEG C； Reaction solution is transferred in bag filter, is dialysed in DMSO solution first for 24 hours, then dialyse 72h in deionized water, dialyzate 8h replacement is primary, product freeze-drying.
4. a kind of purposes of the glucan derivative described in claim 1 with AIE feature, it is characterised in that: the Portugal is poly- Sugar derivatives is during cell imaging as the application of fluorescence probe.
5. purposes according to claim 4, it is characterised in that:
The glucan derivative is water-soluble, 1 × 10-3Mg/mL to 60 × 10-3Have in mg/mL concentration range apparent Aggregation-induced emission feature.
6. purposes according to claim 4, it is characterised in that:
The critical micelle concentration of the glucan derivative is 5 × 10-3mg/mL。
CN201910291713.0A 2019-04-12 2019-04-12 Glucan derivative with AIE characteristic and synthesis method and application thereof Active CN110003355B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050214807A1 (en) * 2003-11-19 2005-09-29 Iain Johnson Environmental sensitive fluorogenic compounds and their application for singlet oxygen and protein detection
CN108774301A (en) * 2018-07-11 2018-11-09 西南大学 The preparation method and applications of sour responsive polymer drug of the one kind based on glucan

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050214807A1 (en) * 2003-11-19 2005-09-29 Iain Johnson Environmental sensitive fluorogenic compounds and their application for singlet oxygen and protein detection
CN108774301A (en) * 2018-07-11 2018-11-09 西南大学 The preparation method and applications of sour responsive polymer drug of the one kind based on glucan

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HONGYE HUANGA等: "One-step preparation of AIE-active dextran via formation of phenyl borate and their bioimaging application", 《CHEMICAL ENGINEERING JOURNAL》 *
WANFU XU等: "A far-red-emissive AIE active fluorescent probe with large stokes shift for detection of inflammatory bowel disease in vivo", 《JOURNAL OF MATERIALS CHEMISTRY B》 *

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