CN105527285B - One kind proves that adamantane and beta cyclodextrin assemble successful method - Google Patents
One kind proves that adamantane and beta cyclodextrin assemble successful method Download PDFInfo
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- 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
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- 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
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Abstract
Prove that adamantane and beta cyclodextrin assemble successful method the invention discloses one kind,After this method is for proving that the adamantane of host molecule sulfydryl beta cyclodextrin and the modification of guest molecule pH sensitive polymers is reacted by host-guest chemistry,Whether adamantane and beta cyclodextrin assemble success,It utilizes the interaction between sulfydryl on gold and host molecule,Gold is set to be attached on host molecule,Then by adjusting pH value,It is in hydrophobic state to make the pH sensitive polymers in guest molecule,If adamantane and beta cyclodextrin assemble successfully,The host molecule of guest molecule and combination gold precipitates simultaneously,There is the generation of purple floccule and upper strata is colorless cleared solution,If adamantane and beta cyclodextrin are unassembled,Then only has guest molecule precipitation (White Flocculus),It is present in reference to the host molecule of gold in upper solution,I.e. upper strata is purple settled solution.The present invention does not need large-scale instrument detection, and cost is relatively low, and testing result accuracy is high.
Description
Technical field
The invention belongs to be tested or analysis of material technical field by means of determining the chemically or physically property of material, it is related to
One kind proves that adamantane and beta-schardinger dextrin assemble successful method.
Background technology
Inclusion compound is that a kind of space structure of molecule completely or partially wraps into another molecule and formed, and has clathration
Outer layer molecule is referred to as host molecule, is referred to as guest molecule by the small-molecule substance included among host molecule, therefore inclusion compound is again
Claim " molecular capsule ".In terms of medicament slow release, inclusion compound, can be with due to suitable particle diameter, excellent pharmaceutical carrier function
As a kind of pharmaceutical carrier.Because the pH value of cancer cell tissue is lower than the pH value of human normal tissue, Medicated Permeation rate is poor, institute
In design medicine carrier, pharmaceutical carrier is designed as into pH sensitive properties and there is stronger permeability, have broader
Actual use value.
Beta-schardinger dextrin, can conduct because its structure has the particularity of " outer hydrophilic, interior hydrophobic " and nontoxic premium properties
Host molecule and a variety of guest inclusions, such as adamantane.But when preparing inclusion compound material, whether Subjective and Objective, which assembles, is successfully
A very crucial step, at present generally with the technology such as ultraviolet spectra, mass spectrum, transmission electron microscope, laser particle analyzer to beta-schardinger dextrin and its
Inclusion compound is characterized.But these are all to go to detect by laboratory apparatus.Certainly, due to many laboratories because condition limits
System, the material worked it out is not very pure, so by experimental method, and be very difficult to characterize.
The content of the invention
The technical problems to be solved by the invention be to provide it is a kind of it is simple to operate, do not need large-scale instrument detection to demonstrate,prove
Bright adamantane and beta-schardinger dextrin assemble successful method.
Technical scheme is used by solving above-mentioned technical problem：By host molecule mercapto group-beta-cyclodextrin and guest molecule
After the adamantane that pH sensitive polymers are modified is reacted by host-guest chemistry, products therefrom adds the N of gold chloride, N- dimethyl
In amide solution, react 12~24 hours at normal temperatures, centrifuge, gained solid is dissolved completely in deionized water, use
Acid or alkali adjust its pH value to pH sensitive polymers and are the pH value of hydrophobic state, if having, purple floccule generates and upper strata is nothing
Color settled solution, it was demonstrated that adamantane and beta-schardinger dextrin assemble successfully, and White Flocculus generates and upper strata is that purple clarification is molten if having
Liquid, illustrate that adamantane and beta-schardinger dextrin are unassembled.
The concentration of the N of above-mentioned gold chloride, N- DMF solution is preferably 5~15g/L, gold chloride and sulfydryl-β-ring
The mol ratio of dextrin is 1:1~1.5.
Above-mentioned pH sensitive polymers are the polymerized monomer with amino and carboxyl, specific such as polymethylacrylic acid (its
The pH value of hydrophobic state is less than 5.6), (its is hydrophobic for polyacrylamide for polyacrylic acid (pH value of its hydrophobic state is less than 5.4)
The pH value of state is 10~13) etc..
Above-mentioned acid is boric acid, hydrochloric acid, nitric acid etc., and alkali is sodium hydroxide, potassium hydroxide etc..
The present invention makes gold be attached to main body using the interaction between sulfydryl on gold and host molecule mercapto group-beta-cyclodextrin
On molecule, then by adjusting pH value, it is in hydrophobic state to make the pH sensitive polymers in guest molecule, if adamantane and β-ring
Dextrin assembles successfully, and the host molecule of guest molecule and combination gold precipitates simultaneously, that is, has the generation of purple floccule and upper strata is nothing
Color settled solution, if adamantane and beta-schardinger dextrin are unassembled, only guest molecule precipitates (White Flocculus), with reference to the master of gold
Body molecule is present in upper solution, i.e., upper strata is purple settled solution.
The present invention is used for the Buddha's warrior attendant for proving that host molecule mercapto group-beta-cyclodextrin is modified with guest molecule pH sensitive polymers
After alkane is reacted by host-guest chemistry, whether adamantane and beta-schardinger dextrin assemble success, and method is simple to operate, it is not necessary to large-scale instrument
Device detects, and cost is relatively low, and testing result accuracy is high.
Brief description of the drawings
Fig. 1 is AD-PMAA (a), β-CD- (SH)7(b), AD-PMAA and β-CD- (SH)7Physical mixed (c), β-CD-
(SH)7/ AD-PMAA (d) X-ray diffractogram.
Fig. 2 is AD-PMAA, β-CD- (SH)7、β-CD-(SH)7/ AD-PMAA Laser particle-size distribution figure.
Fig. 3 is β-CD- (SH) when pH is 5.67/ AD-PMAA transmission electron microscope picture.
Embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
The preparation method for the adamantane that polymethylacrylic acid in example below is modified is：According to document (L.Yang,
Y.Guo and Z.Lei,J.Mater.Chem.A,2015,DOI:10.1039/C5TA03937A) synthesis polymethylacrylic acid uncle
The adamantane (being denoted as AD-PTBMA) that butyl ester is modified, AD-PTBMA is dissolved in dry dichloromethane, in a nitrogen atmosphere,
The trifluoroacetic acid of 5 times of AD-PTBMA moles is added, solvent, residue is evaporated off after 36 hours, with Rotary Evaporators in normal-temperature reaction
Matter is fitted into after being dissolved with tetrahydrofuran in the bag filter that molecular weight is 1000, and a water is changed in gap for 3 hours, dialyses 3 days, finally will
Dialyzate is freeze-dried, and the adamantane for obtaining the modification of guest molecule polymethylacrylic acid (is denoted as AD-PMAA, it counts equal molecule
Measure as 10000).
Embodiment 1
0.1g (0.1mmol) host molecule mercapto group-beta-cyclodextrin (is denoted as β-CD- (SH)7) and 1g (0.1mmol) object
Molecule AD-PMAA is dissolved completely in 50mL deionized waters, stirring at normal temperature 24 hours, and 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 34mL 10g/L gold chlorides, N- DMF solutions
In, stirring at normal temperature 12 hours, centrifuge, gained solid is dissolved completely in 25mL deionized waters, with boron acid for adjusting pH value
To less than 5.6, if having, purple floccule is generated and upper strata is colorless cleared solution, it was demonstrated that adamantane and beta-schardinger dextrin are assembled into
Work(, if having, White Flocculus generates and upper strata is purple settled solution, illustrates that adamantane and beta-schardinger dextrin are unassembled.Inventor uses
To 2.0, experimental result is shown boron acid for adjusting pH value, has the generation of purple floccule and upper strata is colorless cleared solution, it was demonstrated that Buddha's warrior attendant
Alkane and beta-schardinger dextrin assemble successfully.
The above method can also be used for proving the adamantane (example that mercapto group-beta-cyclodextrin is modified with other pH sensitive polymers
Such as modified adamantane of polyacrylic acid, polyacrylic acid, polyacrylamide) self assembly success or not, pH value need to only be adjusted to
PH value when corresponding pH sensitive polymers are hydrophobic state, if having, purple floccule generates and upper strata is colorless cleared solution,
Prove that adamantane and beta-schardinger dextrin assemble successfully, White Flocculus generates and upper strata is purple settled solution if having, and illustrates Buddha's warrior attendant
Alkane and beta-schardinger dextrin are unassembled.
In order to prove the accuracy of the inventive method, inventor is using X-ray diffractometer, laser particle analyzer, transmitted electron
Microscope is respectively to the products therefrom β-CD- (SH) of embodiment 17/ AD-PMAA is characterized, and as a result sees Fig. 1~3.
In Fig. 1, can clearly judge it is AD-PMAA and β-CD- (SH) from curve c7The 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, illustrate formation
New solid phase, i.e. AD-PMAA and β-CD- (SH)7Interact to form inclusion compound by weak chemical bond, it is possible to determine that β-
CD-(SH)7There is adamantane and the host -guest inclusion complex of beta-schardinger dextrin in/AD-PMAA.
From Figure 2 it can be seen that β-CD- (SH)7/ AD-PMAA particle diameter is more bigger than guest molecule AD-PMAA particle diameter, explanation
Subjective and Objective successfully assembles.As seen from Figure 3, when pH is 5.6, β-CD- (SH)7/ AD-PMAA forms globular micelle, because
For when 5.6, PMAA is hydrophobic, and β-CD- (SH)7It is hydrophily, can shape so only having them successfully to assemble
Into micella.And as seen from Figure 3, between 100~200nm, the testing result with laser particle analyzer is the particle diameter of micella
Consistent, further illustrate AD-PMAA and β-CD- (SH)7Successfully assemble.
From the above experiments, it was found that present invention demonstrates that method shows with X-ray diffractometer, laser particle analyzer, transmitted electron
Micro mirror testing result is consistent, and it is to prepare reliably to illustrate the inventive method.
Claims (6)
1. one kind proves that adamantane and beta-schardinger dextrin assemble successful method, it is characterised in that：By host molecule sulfydryl-β-ring paste
After the adamantane that essence is modified with guest molecule pH sensitive polymers is reacted by host-guest chemistry, products therefrom adds gold chloride
N, in N- DMF solutions, react 12~24 hours at normal temperatures, centrifuge, gained solid is dissolved completely in
In ionized water, adjusted its pH value to pH sensitive polymers with acid or alkali and be the pH value of hydrophobic state, if there is the life of purple floccule
Into and upper strata be colorless cleared solution, it was demonstrated that adamantane and beta-schardinger dextrin assemble successfully, if having White Flocculus generate and upper strata
For purple settled solution, illustrate that adamantane and beta-schardinger dextrin are unassembled.
2. proof adamantane according to claim 1 and beta-schardinger dextrin assemble successful method, it is characterised in that：The chlorine
The concentration of the N of auric acid, N- DMF solution is 5~15g/L.
3. proof adamantane according to claim 1 or 2 and beta-schardinger dextrin assemble successful method, it is characterised in that：Institute
The mol ratio for stating gold chloride and mercapto group-beta-cyclodextrin is 1:1~1.5.
4. proof adamantane according to claim 1 and beta-schardinger dextrin assemble successful method, it is characterised in that：Described
PH sensitive polymers are any one in polymethylacrylic acid, polyacrylic acid, polyacrylamide.
5. proof adamantane according to claim 1 and beta-schardinger dextrin assemble successful method, it is characterised in that：Described
Acid is any one in boric acid, hydrochloric acid, nitric acid.
6. proof adamantane according to claim 1 and beta-schardinger dextrin assemble successful method, it is characterised in that：Described
Alkali is sodium hydroxide or potassium hydroxide.
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| CN106634586B (en) * | 2016-12-15 | 2020-02-18 | 东南大学 | Preparation method of self-repairing transparent film of host and guest |
| 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 |
| CN114291909B (en) * | 2021-12-21 | 2023-09-08 | 宁夏理工学院 | Scale inhibition dispersing agent |
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