CN105527285A - Method for proving successful assembly of adamantane and beta-cyclodextrin - Google Patents

Method for proving successful assembly of adamantane and beta-cyclodextrin Download PDF

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Publication number
CN105527285A
CN105527285A CN201510967042.7A CN201510967042A CN105527285A CN 105527285 A CN105527285 A CN 105527285A CN 201510967042 A CN201510967042 A CN 201510967042A CN 105527285 A CN105527285 A CN 105527285A
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beta
diamantane
schardinger dextrin
cyclodextrin
acid
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CN105527285B (en
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雷忠利
舒士倡
杨红
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Shaanxi Normal University
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Shaanxi Normal University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/82—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a precipitate or turbidity

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plasma & Fusion (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
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  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The invention discloses a method for proving successful assembly of adamantane and beta-cyclodextrin. The method is used for proving whether adamantane and beta-cyclodextrin are successfully assembled after host molecules mercapto-beta-cyclodextrin and guest molecules pH-sensitive polymer modified adamantane are subjected to host-guest chemistry reaction; with utilization of interaction of gold and mercapto groups on the host molecules, gold is combined onto the host molecules; then through adjusting the pH value, a pH-sensitive polymer in the guest molecules is in a hydrophobic state; if adamantane and beta-cyclodextrin are successfully assembled, the guest molecules and the host molecules combined with gold are precipitated at the same time, that is to say, a purple floccule is generated and an upper layer is a colorless clarified solution; if adamantane and beta-cyclodextrin are not assembled, only the guest molecules are precipitated (a white floccule), and the host molecules combined with gold exist in an upper solution, that is to say, the upper layer is a purple clarified solution. The method has the advantages of no need for large-scale instrument detection, lower cost, and high accuracy of detection results.

Description

A kind of proof diamantane and beta-schardinger dextrin-assemble successful method
Technical field
The present invention relates to one and prove that diamantane and beta-schardinger dextrin-assemble successful method.
Background technology
To be that a kind of space structure of molecule is all or part of wrap into another kind of molecule and form inclusion compound, the outer molecule with clathration is called host molecule, be called guest molecule by the small-molecule substance in the middle of inclusion to host molecule, therefore inclusion compound is also known as " molecular capsule ".In medicament slow release, inclusion compound, can as a kind of pharmaceutical carrier owing to having suitable particle diameter, excellent pharmaceutical carrier function.Because the pH value of cancer cell tissue is lower than the pH value of human normal tissue, Medicated Permeation rate variance, so when designing pharmaceutical carrier, being designed to pH sensitive property and having stronger perviousness, having more wide actual use value by pharmaceutical carrier.
Beta-schardinger dextrin-has the singularity of " outer hydrophilic, interior hydrophobic " and nontoxic premium properties due to its structure, can be used as host molecule and multiple guest inclusion, such as diamantane.But when preparing inclusion compound material, whether Subjective and Objective assembles is successfully a very crucial step, the technology such as current usual ultraviolet spectrum, mass spectrum, transmission electron microscope, laser particle analyzer characterize beta-schardinger dextrin-and inclusion compound thereof.But these are all that instrument goes to detect by experiment.Certainly, because a lot of laboratory limits due to condition, the material of working it out is not very pure, so method by experiment, is be difficult to characterize yet.
Summary of the invention
Technical matters to be solved by this invention be to provide a kind of simple to operate, do not need large-scale instrument detection and provable diamantane and beta-schardinger dextrin-to assemble successful method.
Solving the problems of the technologies described above adopted technical scheme is: after being reacted by host-guest chemistry by the diamantane of host molecule mercapto group-beta-cyclodextrin and the modification of guest molecule pH sensitive polymer, products therefrom adds the N of gold chloride, in N-DMF solution, react 12 ~ 24 hours at normal temperatures, centrifuging, gained solid is dissolved in deionized water completely, its pH value to pH sensitive polymer is regulated to be the pH value of hydrophobic state with acid or alkali, if have purple floccus generate and upper strata is colorless cleared solution, prove that diamantane and beta-schardinger dextrin-are assembled successfully, if adularescent floccus generates and upper strata is purple settled solution, illustrate diamantane and beta-schardinger dextrin-unassembled.
The concentration of the N of above-mentioned gold chloride, N-DMF solution is preferably 5 ~ 15g/L, and the mol ratio of gold chloride and mercapto group-beta-cyclodextrin is 1:1 ~ 1.5.
Above-mentioned pH sensitive polymer is have polymerization single polymerization monomer that is amino and carboxyl, concrete as polymethylacrylic acid (pH value of its hydrophobic state is less than 5.6), polyacrylic acid (pH value of its hydrophobic state is less than 5.4) polyacrylamide (pH value of its hydrophobic state is 10 ~ 13) etc.
Above-mentioned acid is boric acid, hydrochloric acid, nitric acid etc., and alkali is NaOH, potassium hydroxide etc.
The present invention utilizes the interaction on gold and host molecule mercapto group-beta-cyclodextrin between sulfydryl, gold is made to be attached on host molecule, then adjust ph is passed through, the pH sensitive polymer in guest molecule is made to be hydrophobic state, if diamantane and beta-schardinger dextrin-are assembled successfully, the host molecule of guest molecule and combination gold precipitates simultaneously, namely have purple floccus generate and upper strata is colorless cleared solution, if diamantane and beta-schardinger dextrin-unassembled, guest molecule is then only had to precipitate (White Flocculus), host molecule in conjunction with gold is present in upper solution, namely upper strata is purple settled solution.
The present invention is for after proving that the diamantane of host molecule mercapto group-beta-cyclodextrin and the modification of guest molecule pH sensitive polymer is reacted by host-guest chemistry, whether diamantane and beta-schardinger dextrin-are assembled successfully, method is simple to operate, large-scale instrument is not needed to detect, cost is lower, and testing result accuracy is high.
Accompanying drawing explanation
Fig. 1 is AD-PMAA (a), β-CD-(SH) 7(b), AD-PMAA and β-CD-(SH) 7physical mixed (c), β-CD-(SH) 7the X-ray diffractogram of/AD-PMAA (d).
Fig. 2 is AD-PMAA, β-CD-(SH) 7, β-CD-(SH) 7the Laser particle-size distribution figure of/AD-PMAA.
Fig. 3 is pH β-CD-(SH) when being 5.6 7the transmission electron microscope picture of/AD-PMAA.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in more detail, but protection scope of the present invention is not limited only to these embodiments.
The preparation method of the diamantane of the polymethylacrylic acid modification below in embodiment is: according to document (L.Yang, Y.GuoandZ.Lei, J.Mater.Chem.A, 2015, DOI:10.1039/C5TA03937A) diamantane (being denoted as AD-PTBMA) of polymethyl tert-butyl acrylate modification is synthesized, AD-PTBMA is dissolved in dry methylene chloride, in a nitrogen atmosphere, add the trifluoroacetic acid of AD-PTBMA molar weight 5 times, normal-temperature reaction is after 36 hours, steam with Rotary Evaporators and desolventize, loading molecular weight after surplus materials tetrahydrofuran dissolves is in the bag filter of 1000, a water is changed in gap for 3 hours, dialyse 3 days, finally by dislysate through freeze drying, the diamantane obtaining the modification of guest molecule polymethylacrylic acid (is denoted as AD-PMAA, its number-average molecular weight is 10000).
Embodiment 1
0.1g (0.1mmol) host molecule mercapto group-beta-cyclodextrin (is denoted as β-CD-(SH) 7) and 1g (0.1mmol) guest molecule AD-PMAA be dissolved in 50mL deionized water completely, stirring at normal temperature 24 hours, freeze drying, products therefrom is denoted as β-CD-(SH) 7/ AD-PMAA.
By products therefrom β-CD-(SH) 7/ AD-PMAA adds the N of 34mL10g/L gold chloride, in N-DMF solution, stirring at normal temperature 12 hours, centrifuging, is dissolved in gained solid in 25mL deionized water, completely below boric acid adjust ph to 5.6, if have purple floccus generate and upper strata is colorless cleared solution, prove that diamantane and beta-schardinger dextrin-assembles successfully, if adularescent floccus generation and upper strata is purple settled solution, illustrate diamantane and beta-schardinger dextrin-unassembled.Inventor is by boric acid adjust ph to 2.0, and experimental result shows, and has purple floccus to generate and upper strata is colorless cleared solution, proves that diamantane and beta-schardinger dextrin-are assembled successfully.
Said method also can be used for proving the diamantane self assembly success or not such as the diamantane of modification (such as polyacrylic acid, polyacrylic acid, the polyacrylamide) of mercapto group-beta-cyclodextrin and other pH sensitive polymer modifications, pH value when only pH value need to be adjusted to corresponding pH sensitive polymer be hydrophobic state, if have purple floccus generate and upper strata is colorless cleared solution, prove that diamantane and beta-schardinger dextrin-are assembled successfully, if adularescent floccus generate and upper strata is purple settled solution, illustrate diamantane and beta-schardinger dextrin-unassembled.
In order to prove the accuracy of the inventive method, inventor adopts X-ray diffractometer, laser particle analyzer, transmission electron microscope respectively to embodiment 1 products therefrom β-CD-(SH) 7/ AD-PMAA characterizes, and the results are shown in Figure 1 ~ 3.
In Fig. 1, clearly can judge it is AD-PMAA and β-CD-(SH) from curve c 7the simple superposition of spectrogram, and in curve d, AD-PMAA and β-CD-(SH) 7crystal characteristic peak disappear, there is new crystal diffraction characteristic peak, illustrated and define new solid-phase, be i.e. AD-PMAA and β-CD-(SH) 7interacted by weak chemical bond and form inclusion compound, β-CD-(SH) can be judged 7the host-guest inclusion complex of diamantane and beta-schardinger dextrin-is there is in/AD-PMAA.
As seen from Figure 2, β-CD-(SH) 7the particle diameter of/AD-PMAA is more bigger than the particle diameter of guest molecule AD-PMAA, illustrates that Subjective and Objective is successfully assembled.As seen from Figure 3, when pH is 5.6, β-CD-(SH) 7/ AD-PMAA defines globular micelle, because when 5.6 time, PMAA is hydrophobic, and β-CD-(SH) 7hydrophily, so only have them successfully to assemble can form micella.And as seen from Figure 3, the particle diameter of micella, between 100 ~ 200nm, is consistent with the testing result of laser particle analyzer, further illustrates AD-PMAA and β-CD-(SH) 7successfully assemble.
From above-mentioned experimental result, method of proof of the present invention and X-ray diffractometer, laser particle analyzer, transmission electron microscope testing result are all consistent, illustrate that the inventive method prepares reliably.

Claims (6)

1. one kind proves that diamantane and beta-schardinger dextrin-assemble successful method, it is characterized in that: after the diamantane of host molecule mercapto group-beta-cyclodextrin and the modification of guest molecule pH sensitive polymer is reacted by host-guest chemistry, products therefrom adds the N of gold chloride, in N-DMF solution, react 12 ~ 24 hours at normal temperatures, centrifuging, gained solid is dissolved in deionized water completely, its pH value to pH sensitive polymer is regulated to be the pH value of hydrophobic state with acid or alkali, if have purple floccus generate and upper strata is colorless cleared solution, prove that diamantane and beta-schardinger dextrin-are assembled successfully, if adularescent floccus generates and upper strata is purple settled solution, illustrate diamantane and beta-schardinger dextrin-unassembled.
2. proof diamantane according to claim 1 and beta-schardinger dextrin-assemble successful method, it is characterized in that: the concentration of the N of described gold chloride, N-DMF solution is 5 ~ 15g/L.
3. proof diamantane according to claim 1 and 2 and beta-schardinger dextrin-assemble successful method, it is characterized in that: the mol ratio of described gold chloride and mercapto group-beta-cyclodextrin is 1:1 ~ 1.5.
4. proof diamantane according to claim 1 and beta-schardinger dextrin-assemble successful method, it is characterized in that: described pH sensitive polymer is any one in polymethylacrylic acid, polyacrylic acid, polyacrylamide.
5. proof diamantane according to claim 1 and beta-schardinger dextrin-assemble successful method, it is characterized in that: described acid is any one in boric acid, hydrochloric acid, nitric acid.
6. proof diamantane according to claim 1 and beta-schardinger dextrin-assemble successful method, it is characterized in that: described alkali is NaOH or potassium hydroxide.
CN201510967042.7A 2015-12-21 2015-12-21 One kind proves that adamantane and beta cyclodextrin assemble successful method Expired - Fee Related CN105527285B (en)

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CN106634586A (en) * 2016-12-15 2017-05-10 东南大学 Preparation method for subject-object self-repairing transparent film
CN112111260A (en) * 2020-10-09 2020-12-22 西南石油大学 Displacement leading edge outburst locking agent system and preparation method thereof
CN114291909A (en) * 2021-12-21 2022-04-08 宁夏理工学院 Scale inhibition and dispersion agent

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106634586A (en) * 2016-12-15 2017-05-10 东南大学 Preparation method for subject-object self-repairing transparent film
CN112111260A (en) * 2020-10-09 2020-12-22 西南石油大学 Displacement leading edge outburst locking agent system and preparation method thereof
CN112111260B (en) * 2020-10-09 2022-06-24 西南石油大学 Displacement leading edge outburst locking agent system and preparation method thereof
CN114291909A (en) * 2021-12-21 2022-04-08 宁夏理工学院 Scale inhibition and dispersion agent
CN114291909B (en) * 2021-12-21 2023-09-08 宁夏理工学院 Scale inhibition dispersing agent

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