CN106674234B - A kind of TMeQ [6] and amino acid super molecular complex and preparation method and application - Google Patents
A kind of TMeQ [6] and amino acid super molecular complex and preparation method and application Download PDFInfo
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- CN106674234B CN106674234B CN201610995968.1A CN201610995968A CN106674234B CN 106674234 B CN106674234 B CN 106674234B CN 201610995968 A CN201610995968 A CN 201610995968A CN 106674234 B CN106674234 B CN 106674234B
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- 150000001413 amino acids Chemical class 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000010668 complexation reaction Methods 0.000 title abstract description 4
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical group N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- KZSNJWFQEVHDMF-SCSAIBSYSA-N D-valine Chemical compound CC(C)[C@@H](N)C(O)=O KZSNJWFQEVHDMF-SCSAIBSYSA-N 0.000 claims description 19
- 239000013078 crystal Substances 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- WHUUTDBJXJRKMK-GSVOUGTGSA-N D-glutamic acid Chemical compound OC(=O)[C@H](N)CCC(O)=O WHUUTDBJXJRKMK-GSVOUGTGSA-N 0.000 abstract description 8
- ODHCTXKNWHHXJC-VKHMYHEASA-N 5-oxo-L-proline Chemical compound OC(=O)[C@@H]1CCC(=O)N1 ODHCTXKNWHHXJC-VKHMYHEASA-N 0.000 abstract description 7
- 235000001014 amino acid Nutrition 0.000 description 35
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 9
- 239000004474 valine Substances 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 6
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005564 crystal structure determination Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- 125000003625 D-valyl group Chemical group N[C@@H](C(=O)*)C(C)C 0.000 description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- MSBXTPRURXJCPF-DQWIULQBSA-N cucurbit[6]uril Chemical class N1([C@@H]2[C@@H]3N(C1=O)CN1[C@@H]4[C@@H]5N(C1=O)CN1[C@@H]6[C@@H]7N(C1=O)CN1[C@@H]8[C@@H]9N(C1=O)CN([C@H]1N(C%10=O)CN9C(=O)N8CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@@H]6[C@H]4N2C(=O)N6CN%10[C@H]1N3C5 MSBXTPRURXJCPF-DQWIULQBSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 235000013922 glutamic acid Nutrition 0.000 description 2
- 239000004220 glutamic acid Substances 0.000 description 2
- 229930182470 glycoside Natural products 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000002678 macrocyclic compounds Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- 108010001515 Galectin 4 Proteins 0.000 description 1
- 102100039556 Galectin-4 Human genes 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- ZDOBFUIMGBWEAB-XGFHMVPTSA-N cucurbit[7]uril Chemical compound N1([C@H]2[C@H]3N(C1=O)CN1[C@H]4[C@H]5N(C1=O)CN1[C@H]6[C@H]7N(C1=O)CN1[C@H]8[C@H]9N(C1=O)CN1[C@H]%10[C@H]%11N(C1=O)CN([C@@H]1N(C%12=O)CN%11C(=O)N%10CN9C(=O)N8CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@H]6[C@@H]4N2C(=O)N6CN%12[C@@H]1N3C5 ZDOBFUIMGBWEAB-XGFHMVPTSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000001046 glycoluril group Chemical class [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- -1 tetramethyl cucurbituril Chemical compound 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2201/00—Features of devices classified in G01N21/00
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- G01N2201/061—Sources
- G01N2201/06113—Coherent sources; lasers
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/05—Investigating materials by wave or particle radiation by diffraction, scatter or reflection
- G01N2223/056—Investigating materials by wave or particle radiation by diffraction, scatter or reflection diffraction
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/10—Different kinds of radiation or particles
- G01N2223/101—Different kinds of radiation or particles electromagnetic radiation
- G01N2223/1016—X-ray
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/60—Specific applications or type of materials
- G01N2223/604—Specific applications or type of materials monocrystal
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- General Health & Medical Sciences (AREA)
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- Pathology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
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Abstract
The invention discloses a kind of TMeQ [6] and amino acid super molecular complex and preparation method and application.It further include TMeQ [6]-Pidolidone super molecular complex that water-soluble melon ring TMeQ [6] synthesizes with object Pidolidone including TMeQ [6]-D-Glu super molecular complex that water-soluble melon ring TMeQ [6] synthesizes with object D-Glu；TMeQ [6]-D-Glu molecular formula is C45H55O17N25, structural formula are as follows:TMeQ [6]-Pidolidone molecular formula is C45H55O17N25, structural formula are as follows:The present invention has the characteristics that selectively identify amino acid and good water solubility.
Description
Technical field
The present invention relates to a kind of super molecular complex and methods for making and using same more particularly to a kind of TMeQ [6] and amino
Sour super molecular complex and preparation method and application.
Background technique
Melon ring is the big ring caged chemical combination to be got up by glycosides urea unit by methylene-bridged as a kind of macrocyclic compound
Object, structure feature are the cavity with both ends open, and two-port size is identical, and port diameter is less than cavity diameter.Melon ring
Two-port is dispersed with carbonylic oxygen atom identical with its structural unit number respectively, cationic key binding site is formd, so energy
It interacts with hydrophilic substance, metal ion etc.；And its cavity be it is hydrophobic, not only can wrap knot organic molecule, also
It can be with inclusion inorganic molecules, inorganic anion.Compared with the macrocycle molecules such as crown ether, cyclodextrin, calixarenes, melon ring has stronger
Structural rigidity, it is not easy to change own form be suitble to guest molecule, so can be selective according to the size of own cavity
Accommodate size, the guest molecule that shape matches.
Due to common melon ring poorly water-soluble, in general, the water solubility of the common melon ring with the odd number degree of polymerization is preferably, such as room temperature
Under, the solubility of five yuan of melon rings (Q [5]) and cucurbit(7)uril (Q [7]) is the solubility phase of 20-30mM and beta-cyclodextrin (β-CD)
As (16mM)；And the water solubility of the common melon ring with the even number degree of polymerization is poor, and such as hexa-atomic melon ring (Q [6]), eight yuan of melon ring (Q
[8]) water solubility of Ji Shiyuan melon ring (Q [10]) is compared with (< 0.01mM), and common melon ring does not dissolve in organic solvent, is only capable of being dissolved in
The concentrated acids such as formic acid, acetic acid, hydrochloric acid.
Amino acid is very important small organic molecule in organism, its molecular structure (such as chiral and side-chain structure)
It is molecular information most basic in life.The total assembling of chiral amino acid molecule and functional organic molecule can be effectively by biology point
The structural information of son is converted to physiochemical signal.Facilitate in more detail to by the research of the Molecular Recognization of substrate of amino acid
Ground understands t-RNA identification, shifts a certain specific amino acids for other more in the expression process and chemical field of synthetic proteins matter
Kind Molecular Recognization mechanism.Amino acid refers to the carboxylic acid containing amino.The intracorporal various protein of biology are basic by 20 kinds
Amino acid profile.It is a-amino acid wherein (proline is a kind of alpha-imino acid) in addition to glycine.In addition to glycine,
The alpha -carbon atom of its gal4 amino acid is asymmetric carbon atom (each not phase of four substituent groups being bonded with alpha -carbon atom
Together), therefore amino acid can have stereoisomer, it can have different configurations (D- type and two kinds of configurations of type).
Summary of the invention
The object of the present invention is to provide a kind of TMeQ [6] and amino acid super molecular complex, TMeQ [6] of the present invention with
Amino acid super molecular complex has the characteristics that selectively identify amino acid and good water solubility.
The present invention is implemented as follows: a kind of TMeQ [6] and amino acid super molecular complex, including water-soluble melon ring TMeQ
[6] TMeQ [the 6]-D-Glu super molecular complex synthesized with object D-Glu further includes water-soluble melon ring TMeQ [6] with
TMeQ [6]-Pidolidone super molecular complex of object Pidolidone synthesis；TMeQ [6]-D-Glu molecular formula
For C45H55O17N25, structural formula are as follows:
TMeQ [6]-Pidolidone molecular formula is C45H55O17N25, structural formula are as follows:
TMeQ [6] above-mentioned and amino acid super molecular complex further include water-soluble melon ring TMeQ [6] and object D- figured silk fabrics ammonia
TMeQ [6]-D-Val super molecular complex of acid synthesis；TMeQ [6]-D-Val molecular formula is
C85H105O30N49Cd, structural formula are as follows:
The preparation method of TMeQ [6] and amino acid super molecular complex above-mentioned, the TMeQ [6]-D-Glu are super
Molecular complex is prepared according to the following steps:
A. TMeQ [6] is mixed with water, and heating dissolves TMeQ [6], obtains A product；
B. D- paddy ammonia is added into A product by the amount that the molar ratio of TMeQ [6] and D-Glu is 0.8~1.2:5.0~8.0
Acid obtains B product；
C. it is heated at 55~65 DEG C again, until be cooled to room temperature and stand without precipitating or having a small amount of precipitating in B product, 5~
There is clear crystal precipitation after 7 days, which is finished product；
The system of TMeQ [the 6]-Pidolidone super molecular complex and TMeQ [6]-D-Glu super molecular complex
Preparation Method is identical.
In the preparation method of TMeQ [6] above-mentioned and amino acid super molecular complex, the TMeQ [6]-D-Val
Super molecular complex is prepared according to the following steps:
A. by TMeQ [6] and Cd (NO3)2·4H20.8~1.2:4.0~6.0 is mixed O in molar ratio, obtains A product；
B. D- figured silk fabrics ammonia is added into A product by the amount that the molar ratio of TMeQ [6] and D-Val is 0.8~1.2:5.0~8.0
Acid obtains B product；
C. it is dissolved in water into B product, and heats 2~5min at 55~65 DEG C, be cooled to room temperature and stand, 9~12 days
After have clear crystal precipitation, which is finished product.
TMeQ [6] above-mentioned and amino acid super molecular complex D for identification, Pidolidone.
TMeQ [6] above-mentioned and amino acid super molecular complex are also used to selectively identify D-Val.
The utility model has the advantages that compared with prior art, the present invention closes in such a way that glycoluril dimer replaces glycosides urea to combine with alkyl
At the method for part substituted cucurbituril, synthesized methyl substituted cucurbituril, it is water-soluble be improved significantly, wherein symmetrical tetramethyl six
First melon ring (TMeQ [6]) not only has good water solubility, but also TMeQ [6] has ellipsoidal structure, can be with a variety of organic points
Son and inorganic ions interaction.TMeQ [6] with this small molecule of amino acid when being coordinated to form super molecular complex, because of difference
Amino acid binding mode it is different, the property shown is just different, and effect is strong and weak different, so above-mentioned characteristic, this hair
Bright super molecular complex can selectively identify amino acid.With D, Pidolidone is object and TMeQ [6] interaction shape
When at self-assembled structures, the ratio between the amount for the substance that interacts is 1:1, and forms coordination polymer by hydrogen bond action.In body
In system, the chiral moiety of amino acid is exposed outside the port of melon ring, and rest part enters the cavity inside coordination of melon ring.Make in this way
The super molecular complex that must be formed also has chirality, and which provides a kind of identification D-Glu, the methods of Pidolidone.Simultaneously
For it is this kind of there is longer chain amino acid to interact as object and TMeQ [6] when, binding mode is amino acid
Chiral position is exposed outside port, and it is that the Subjective and Objective of 1:1 is matched that remaining position, which enters the ratio between amount of forming material in the cavity of melon ring,
Close object.
Symmetric tetramethyl cucurbituril (TMeQ [6]) of the invention and amino acid molecular Supramolecular self assembly can effectively by
The structural information of biomolecule is converted to physiochemical signal, and TMeQ [6] has hydrophobic cavity, being capable of inclusion amino acid shape
At Supramolecular self assembly body.Melon ring and this feature of amino acid self-assembly provide the molecular recognition of chiral amino acid
Advantage.Therefore, it is the super molecular complex of supermolecule main block with TMeQ [6], can be applied to selectively identify amino
Acid, to be made into the pharmaceutical carrier of biologic material or the specific group of targets identification with specific selectivity.
Have the characteristics that selectively identify amino acid further to verify the present invention, inventor has done following experiment:
Test the powder diagram of 1:TMeQ [6]-D-Val super molecular complex
Using powder diffraction methods investigate TMeQ [6]-D-Val X-ray diffraction (as shown in Figure 4), and with it is known
The comparative analysis of the X-ray diffraction spectrogram of amorphous material is found: the X-ray diffractogram of sample and the X-ray diffraction of amorphous material
Spectrogram all coincide substantially in shape diffraction maximum number, angle position, relative intensity order and diffraction maximum, to confirm institute
The monocrystalline obtained is pure phase.
Test the MS figure of 2:TMeQ [6]-D-Val super molecular complex
D-Val has been investigated using Matrix-Assisted Laser Desorption Ionization Time of Flight and TMeQ [6] form Subjective and Objective
The case where inclusion complexes.Fig. 5 illustrates TMeQ [6] and D-Val forms the mass spectrogram of inclusion complexes, m/z 1170.86
For TMeQ [6]+D-Val (theoretical value 1170.04), m/z 1091.11 is TMeQ [6]+K+(theoretical value 1092.04),
M/z 1075.59 is TMeQ [6]+Na+(theoretical value 1075.94), m/z 1053.09 are that (theoretical value is TMeQ [6]
1052.94), mass spectral results show that TMeQ [6] and D-Val form the host-guest inclusion complex of 1:1.
Experiment 3: press identical method, with Valine replace D-Val come synthetic compound, only Precipitation but
It is unable to get the clear crystal suitable for crystal structure determination, this phenomenon provides advantageous for the separation of D type and L-type valine
Condition.As shown in fig. 6, the A bottles of solution for being mixed with super molecular complex for TMeQ [6] and D-Val, B bottles are experimental result
TMeQ [6] and Valine are mixed with the solution of super molecular complex, are compared by two bottles, A bottles of clear solutions, and B bottles are muddy
Turbid can identify D-Val and Valine.
Experiment 4: replacing D-Val to carry out synthetic compound with (D, L)-valine (racemic modification, i.e., there is no chiralitys),
The clear crystal suitable for crystal structure determination is obtained, using crystal structure measured by Advances in crystal X-ray diffraction and TMeQ [6]-
D-Val complex is consistent.
Learn that TMeQ [6] and D-Val can form the super molecular complex of 1:1 by 1,2 experiment of experiment；Pass through reality
3,4 it is found that TMeQ [6] specific recognition D-Val is tested, cannot get TMeQ [6]-Valine complex.Prove TMeQ
[6] D-Val is selectively identified.
Detailed description of the invention
Fig. 1 is the structural formula of TMeQ [6]-D-Glu super molecular complex；
Fig. 2 is the structural formula of TMeQ [6]-Pidolidone super molecular complex；
Fig. 3 is the structural formula of TMeQ [6]-D-Val super molecular complex；
Fig. 4 is the X-ray powder diffraction pattern of TMeQ [6]-D-Val；
Fig. 5 is TMeQ [6] and the MS analysis chart of D-Val interaction；
Fig. 6 is TMeQ [6] and D, and Valine prepares the comparative experiments of super molecular complex.
Specific embodiment
Embodiment 1.A kind of TMeQ [6] and amino acid super molecular complex, including water-soluble melon ring TMeQ [6] and object D-
TMeQ [6]-D-Glu super molecular complex of glutamic acid synthesis, further includes water-soluble melon ring TMeQ [6] and object L- paddy ammonia
TMeQ [6]-Pidolidone super molecular complex of acid synthesis；TMeQ [6]-D-Glu molecular formula is
C45H55O17N25, structural formula are as follows:
TMeQ [6]-Pidolidone molecular formula is C45H55O17N25, structural formula are as follows:
TMeQ [6] above-mentioned and amino acid super molecular complex further include water-soluble melon ring TMeQ [6] and object D- figured silk fabrics ammonia
TMeQ [6]-D-Val super molecular complex of acid synthesis；TMeQ [6]-D-Val molecular formula is
C85H105O30N49Cd, structural formula are as follows:
TMeQ [6]-D-Glu super molecular complex above-mentioned is prepared according to the following steps:
A. TMeQ [6] is mixed with water, and heating dissolves TMeQ [6], obtains A product；
B. D- paddy ammonia is added into A product by the amount that the molar ratio of TMeQ [6] and D-Glu is 0.8~1.2:5.0~8.0
Acid obtains B product；
C. it is heated at 55~65 DEG C again, until be cooled to room temperature and stand without precipitating or having a small amount of precipitating in B product, 5~
There is clear crystal precipitation after 7 days, which is finished product.
The system of TMeQ [6]-Pidolidone super molecular complex and TMeQ [6]-D-Glu super molecular complex above-mentioned
Preparation Method is identical.
TMeQ [6]-D-Val super molecular complex above-mentioned is prepared according to the following steps:
A. by TMeQ [6] and Cd (NO3)2·4H20.8~1.2:4.0~6.0 is mixed O in molar ratio, obtains A product；
B. D- figured silk fabrics ammonia is added into A product by the amount that the molar ratio of TMeQ [6] and D-Val is 0.8~1.2:5.0~8.0
Acid obtains B product；
C. it is dissolved in water into B product, and heats 2~5min at 55~65 DEG C, be cooled to room temperature and stand, 9~12 days
After have clear crystal precipitation, which is finished product.
TMeQ [6]-D above-mentioned, Pidolidone super molecular complex D for identification, Pidolidone.
TMeQ [6]-D-Val super molecular complex above-mentioned is for selectively identifying D-Val.
TMeQ [6] above-mentioned and amino acid super molecular complex are used for the inclusion to drug, are specifically used for melon ring and more skins
The inclusion of class drug.
Embodiment 2.A kind of TMeQ [6] and amino acid super molecular complex, including water-soluble melon ring TMeQ [6] and object D-
TMeQ [6]-D-Glu super molecular complex of glutamic acid synthesis, the TMeQ [6]-D-Glu molecular formula are
C45H55O17N25, structural formula are as follows:
TMeQ [6]-D-Glu super molecular complex above-mentioned is prepared according to the following steps:
A. by TMeQ [6] (0.09~0.15mol) in beaker, being dissolved by heating with 3mL distilled water and shaking several minutes makes
Dissolution it is complete；
B. take D-Glu (0.4~0.8mol) solid in the beaker for filling [6] TMeQ；
C. 2min is heated at 55~65 DEG C again, until being cooled to room temperature and quiet in beaker without precipitating or having a small amount of precipitating
It sets, about has the clear crystal precipitation suitable for crystal structure determination after a week, yield is 30% or so.
Embodiment 3.A kind of TMeQ [6] and amino acid super molecular complex, including water-soluble melon ring TMeQ [6] and object D-
TMeQ [6]-D-Val super molecular complex of valine synthesis；TMeQ [6]-D-Val molecular formula is
C85H105O30N49Cd, structural formula are as follows:
TMeQ [6]-D-Val super molecular complex above-mentioned is prepared according to the following steps:
A. TMeQ [6] (0.09~0.15mol), Cd (NO are weighed3)2·4H2O (0.36~0.60mol) is in beaker；
B. in the beaker for taking solid D-Val (0.40~0.80mol) Yu Shengyou TMeQ [6] solution；
C. 3mL distilled water is added to heat 2~5min at 55~65 DEG C and be allowed to dissolve for several minutes of concussion complete；It is cooled to
Room temperature is simultaneously stood, and has within 10 days or so the clear crystal precipitation suitable for crystal structure determination, yield is 35% or so.
Claims (3)
1. a kind of TMeQ [6] and amino acid super molecular complex, it is characterised in that: including water-soluble melon ring TMeQ [6] and object
TMeQ [6]-D-Val super molecular complex of D-Val synthesis；TMeQ [6]-D-Val molecular formula is
C85H105O30N49Cd, structural formula are as follows:
2. a kind of preparation method of TMeQ as described in claim 1 [6] and amino acid super molecular complex, it is characterised in that:
TMeQ [the 6]-D-Val super molecular complex is prepared according to the following steps:
A. by TMeQ [6] and Cd (NO3)2·4H20.8~1.2:4.0~6.0 is mixed O in molar ratio, obtains A product；
B. D-Val is added into A product by the amount that the molar ratio of TMeQ [6] and D-Val is 0.8~1.2:5.0~8.0,
Obtain B product；
C. it is dissolved in water into B product, and heats 2~5min at 55~65 DEG C, be cooled to room temperature and stand, have after 9~12 days
Clear crystal is precipitated, which is finished product.
3. a kind of application of TMeQ as described in claim 1 [6] and amino acid super molecular complex, it is characterised in that: this is super
Molecular complex is for selectively identifying D-Val.
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| WO2013091074A1 (en) * | 2011-12-21 | 2013-06-27 | Uvic Industry Partnerships Inc. | Method and array for identifying histone-code-related analytes |
| CN104447768A (en) * | 2013-09-23 | 2015-03-25 | 贵州大学 | Cucurbit [7] uril [3] rotaxane as well as preparation method and application thereof |
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