CN106674258B - A kind of TMeQ [6] and D, l-methionine super molecular complex and preparation method and application - Google Patents
A kind of TMeQ [6] and D, l-methionine super molecular complex and preparation method and application Download PDFInfo
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- CN106674258B CN106674258B CN201610995974.7A CN201610995974A CN106674258B CN 106674258 B CN106674258 B CN 106674258B CN 201610995974 A CN201610995974 A CN 201610995974A CN 106674258 B CN106674258 B CN 106674258B
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- molecular complex
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- super molecular
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- FFEARJCKVFRZRR-UHFFFAOYSA-N methionine Chemical compound CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 title claims description 14
- 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 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 34
- FFEARJCKVFRZRR-SCSAIBSYSA-N D-methionine Chemical compound CSCC[C@@H](N)C(O)=O FFEARJCKVFRZRR-SCSAIBSYSA-N 0.000 claims description 32
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- AQGDXJQRVOCUQX-UHFFFAOYSA-N N.[S] Chemical compound N.[S] AQGDXJQRVOCUQX-UHFFFAOYSA-N 0.000 claims description 2
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 4
- 150000008546 L-methionines Chemical class 0.000 abstract 6
- 150000008565 D-methionines Chemical class 0.000 abstract 5
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 abstract 1
- 150000001413 amino acids Chemical class 0.000 description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 11
- 229940079593 drug Drugs 0.000 description 11
- 239000003814 drug Substances 0.000 description 11
- 229910002651 NO3 Inorganic materials 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 229960004452 methionine Drugs 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 229930182817 methionine Natural products 0.000 description 7
- 241000219112 Cucumis Species 0.000 description 6
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 6
- 230000003993 interaction Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229920001184 polypeptide Polymers 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 102000004196 processed proteins & peptides Human genes 0.000 description 5
- 108090000765 processed proteins & peptides Proteins 0.000 description 5
- -1 tetramethyl cucurbituril Chemical compound 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005564 crystal structure determination Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- QWWVBNODQCWBAZ-WHFBIAKZSA-N (2r)-2-amino-3-[(2r)-2-carboxy-2-(methylamino)ethyl]sulfanylpropanoic acid Chemical compound CN[C@H](C(O)=O)CSC[C@H](N)C(O)=O QWWVBNODQCWBAZ-WHFBIAKZSA-N 0.000 description 2
- 229930195722 L-methionine Natural products 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Chemical compound [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- MTCFGRXMJLQNBG-UWTATZPHSA-N D-Serine Chemical compound OC[C@@H](N)C(O)=O MTCFGRXMJLQNBG-UWTATZPHSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000019728 animal nutrition Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008827 biological function Effects 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010835 comparative analysis Methods 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
- 238000001514 detection method Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003446 ligand Substances 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
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000007479 molecular analysis Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 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
- 239000000758 substrate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/57—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
- C07C323/58—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fodder In General (AREA)
Abstract
The invention discloses a kind of TMeQ [6] and D, L glutamine super molecular complex and preparation method and application.TMeQ [6] the D methionines Cd synthesized with object D methionines including water-soluble melon ring TMeQ [6]2+Super molecular complex, TMeQ [6] L methionines Cd that water-soluble melon ring TMeQ [6] synthesizes with object L methionines2+Super molecular complex, TMeQ [6] D methionines Zn that water-soluble melon ring TMeQ [6] synthesizes with object D methionines2+Super molecular complex, and TMeQ [6] L methionines Zn that water solubility melon ring TMeQ [6] is synthesized with object L methionines2+Super molecular complex；Described TMeQ [6] the D methionines Cd2+Molecular formula be C45H55O14N25CdS；Described TMeQ [6] the L methionines Cd2+Molecular formula be C45H55O14N25CdS；Described TMeQ [6] the L methionines Cd2+Molecular formula be C45H55O14N25CdS；Described TMeQ [6] the D methionines Zn2+Molecular formula be C45H55O17N26ZnS；Described TMeQ [6] the L methionines Zn2+Molecular formula be C45H55O17N26ZnS.The present invention has and can identify D, the feature that L methionines and self-assembled structures are stablized.
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 D, L-
Methionine super molecular complex and preparation method and application.
Background technology
Supramolecular chemistry (Supramolecular Chemistry) is that more than two molecules pass through a variety of weak interactions
(including hydrogen bond, coordinate bond, Van der Waals force, hydrophilic/hydrophobic effect etc.) is assembled into the chemistry of research object.Melon ring is supermolecular
Learn the symmetrical tubbiness macrocyclic host molecule of another novel high to grow up after relaying crown ether, cyclodextrin, calixarenes.Host and guest
The core research contents that body chemistry is learned as melon cyclisation, has received widespread attention.
Melon ring (Cucurbit [n] urils, Q [n]) one kind is linked up by n glycosides urea unit and 2n methylene bridge
Big ring cage compound.Since melon ring is only very slightly soluble in water (cucurbit(7)uril water solubility is a shade better), it is practically insoluble in organic solvent, is made
Its application is restricted.Therefore, being modified the synthesis of melon ring in recent years becomes an important topic of melon ring research.
Amino acid (amino acid) is divided into D types and L-type amino acid, is the basic composition of biological function macro-molecular protein
Unit constitutes the base substance of protein needed for Animal nutrition.Amino acid is very important organic molecule in organism,
Molecular structure (such as chiral and side-chain structure) is molecular information most basic in life.To knowing by the molecule of substrate of amino acid
Other Effect study contributes to the expression for understanding t-RNA identifications in more detail, shifting a certain specific amino acids for synthetic protein
Other different kinds of molecules recognition reaction mechanism in process and chemical field.
Molecular recognition is initially the Chemical Problem being used in molecular studies biosystem and proposes.Molecular recognition is logical
It crosses transformation and metathesis event generates catalytic action, be to understand that the object between different medium is transmitted in enzyme reaction, information in biosystem
The information source of kind energy transfer phenomenon is then the basic oversubscription for constituting separation, detection and quantitative determination in analytical chemistry field
The formation of sub- inclusion complex is then built upon on the basis of molecular recognition.
Invention content
The object of the present invention is to provide a kind of TMeQ [6] and D, l-methionine super molecular complex is of the present invention
TMeQ [6] and D, l-methionine super molecular complex have and can identify D, the spy that l-methionine and self-assembled structures are stablized
Point.
The invention is realized in this way：A kind of TMeQ [6] and D, l-methionine super molecular complex, including water-soluble melon
TMeQ [6]-D-Met-Cd that ring TMeQ [6] is synthesized with object D-Met2+Super molecular complex, water-soluble melon ring
TMeQ [6]-l-methionine-Cd that TMeQ [6] is synthesized with object l-methionine2+Super molecular complex, water-soluble melon ring
TMeQ [6]-D-Met-Zn that TMeQ [6] is synthesized with object D-Met2+Super molecular complex, and water-soluble melon ring
TMeQ [6]-l-methionine-Zn that TMeQ [6] is synthesized with object l-methionine2+Super molecular complex；The TMeQ
[6]-D-Met-Cd2+Molecular formula be C45H55O14N25CdS, structural formula are：
TMeQ [6]-l-methionine-Cd2+Molecular formula be C45H55O14N25CdS, structural formula are：
TMeQ [6]-D-Met-Zn2+Molecular formula be C45H55O17N26ZnS, structural formula are：
TMeQ [6]-l-methionine-Zn2+Molecular formula be C45H55O17N26ZnS, structural formula are：
TMeQ [6] above-mentioned and D, in l-methionine super molecular complex, the TMeQ [6] is super with D-Met
Molecular complex is prepared according to the following steps：
A. by TMeQ [6] and D-Met in molar ratio 0.8~1：6~12 mixing, obtain A product；
B. by Cd (NO3)2·4H2O or Zn (NO3)2·6H2O is by TMeQ [6] and Cd (NO3)2·4H2O or Zn (NO3)2·
6H2The molar ratio of O is 0.8~1：A product mixings are added in 4~6 amount, obtain B product；
C. B product are dissolved by heating at 50-60 DEG C, is stood later until crystallizing, which is TMeQ [6] and D-
The super molecular complex of methionine synthesis, i.e. TMeQ [6]-D-Met-Cd2+Or TMeQ [6]-D-Met-Zn2+
Super molecular complex.
TMeQ [6] above-mentioned and D, in l-methionine super molecular complex, the TMeQ [6] is super with l-methionine
The preparation method of molecular complex and TMeQ [6] are identical as the preparation method of D-Met super molecular complex.
TMeQ [6] above-mentioned and D, the application of l-methionine super molecular complex are：The super molecular complex is for knowing
Other D-Met and l-methionine.
Advantageous effect：Compared with prior art, Symmetric tetramethyl cucurbituril of the invention and amino acid molecular supermolecule
The structural information of biomolecule effectively can be converted to physiochemical signal by self assembly, and Symmetric tetramethyl cucurbituril has
Hydrophobic cavity, being capable of inclusion amino acid formation Supramolecular self assembly body.This feature pair of melon ring and amino acid self-assembly
Advantage is provided in the molecular recognition of chiral amino acid.Moreover, because TMeQ [6] has smaller melon annular space chamber and amino
The small molecules such as acid have a variety of bonding patterns, can form 1:1 host-guest coordination compound；Add Metal Ions Cd2+、Zn2+Match
Position, can construct more novel supramolecular structure, can be preferably applied to organic-biological material or metal-organic framework material.
With the super molecular complex that TMeQ [6] is supermolecule main block, the amino of enantiomter each other can be selectively identified
Sour (D, l-methionine), the drug to make biologic material or the specific group of targets identification with specific selectivity carry
Body, in addition to this, the super molecular complex of melon ring and Amino acid synthesis can also be applied to the inclusion to drug, be specifically used for melon ring
With the inclusion of more skin class drugs, the principle of melon ring inclusion polypeptide drug molecule is with the principle of melon ring inclusion amino acid
, certain groups of melon annular space chamber inclusion polypeptide drug, on this basis, melon ring form supermolecule cooperation with polypeptide drug
Conveying of the melon ring to polypeptide drug molecule may be implemented in certain condition in object.
It is empty that the amino acid small molecule of the super molecular complex of the present invention can be located at Symmetric tetramethyl cucurbituril TMeQ [6]
Intracavitary or cavity port make melon ring be formed with amino acid small molecule and are coordinated, and can be carried by being coordinated the super molecular complex formed
The stability of high drug molecule, drug targeted release increase its water solubility, reduce toxicity.
Description of the drawings
Fig. 1 is TMeQ [6]-D-Met-Cd2+X-ray powder diffraction figure；
Fig. 2 is TMeQ [6]-l-methionine-Cd2+X-ray powder diffraction figure；
Fig. 3 is TMeQ [6]-D-Met-Zn2+The X-ray powder diffraction figure of super molecular complex crystal prototype；
Fig. 4 is TMeQ [6]-l-methionine-Zn2+The X-ray powder diffraction figure of super molecular complex crystal prototype；
Fig. 5 is TMeQ [6] and D-Met1H NMR figures；
Fig. 6 is TMeQ [6] and the MS of D-Met interaction schemes；
Fig. 7 is TMeQ [6]-D-Met-Cd2+Structural formula；
Fig. 8 is TMeQ [6]-l-methionine-Cd2+Structural formula；
Fig. 9 is TMeQ [6]-D-Met-Zn2+Structural formula；
Figure 10 is TMeQ [6]-l-methionine-Zn2+Structural formula.
Specific implementation mode
Embodiment 1.A kind of TMeQ [6] and D, l-methionine super molecular complex, including water-soluble melon ring TMeQ [6] with
TMeQ [6]-D-Met-Cd of object D-Met synthesis2+Super molecular complex further includes water-soluble melon ring TMeQ
[6] TMeQ [6]-l-methionine-Cd synthesized with object l-methionine2+Super molecular complex；Described TMeQ [the 6]-D-
Methionine-Cd2+Molecular formula be C45H55O14N25CdS, structural formula are：
TMeQ [6]-l-methionine-Cd2+Molecular formula be C45H55O14N25CdS, structural formula are：
The self assembly of D-Met and l-methionine and TMeQ [6] can be clearly told from above-mentioned structural formula
Structure.D-Met and l-methionine are with TMeQ [6] binding modes to interact when forming self-assembled structures：Object
There are hydrogen bonds and ion dipole to act between methionine and TMeQ [6], and the ratio between amount of forming material is 1：1 Subjective and Objective cooperation
Object.The chiral radicals of methionine molecules are located at outside TMeQ [6] port, and the hydrogen atom on alkyl and amino can be with TMeQ [6]
Carbonylic oxygen atom form hydrogen bond, remaining group enters in the cavity of melon ring to be coordinated therewith.Methionine and TMeQ [6] and metal
The ratio between amount of Cd ionic interaction forming materials is 1：1：1 host-guest coordination compound.
TMeQ [6] above-mentioned and D, l-methionine super molecular complex further include water-soluble melon ring TMeQ [6] and object
TMeQ [6]-D-Met-Zn of D-Met synthesis2+Super molecular complex, water-soluble melon ring TMeQ [6] and object L-
TMeQ [6]-l-methionine-Zn of methionine synthesis2+Super molecular complex；TMeQ [the 6]-D-Met-
Zn2+Molecular formula be C45H55O17N26ZnS, structural formula are：
TMeQ [6]-l-methionine-Zn2+Molecular formula be C45H55O17N26ZnS, structural formula are：
TMeQ [6]-D, l-methionine-Zn2+Its methionine of super molecular complex and TMeQ [6] and metal Zn ion phases
The ratio between amount of interaction forming material is 1：1：1 host-guest coordination compound.X-ray crystal structure analysis shows complex crystalline substance
There are one macrocyclic ligand TMeQ [6], a zinc ion, a l-methionine, a nitrate ion and five in body unit
The hydrone of coordination.
TMeQ [6]-Cd is investigated using powder diffraction methods2+- D, l-methionine crystal prototype and TMeQ [6]-Zn2+-
D, the X-ray diffractogram of l-methionine, and found with the comparative analysis of the X-ray diffraction spectrogram of known amorphous material：Sample
The X-ray diffractogram of product and the X-ray diffraction spectrogram of amorphous material diffraction maximum number, angle position, relative intensity order and
Diffraction maximum is all coincide substantially in shape, to confirm that the monocrystalline of gained is pure phase (shown in such as Fig. 1, Fig. 2, Fig. 3, Fig. 4).
The interaction of D-Ser and TMeQ [6] has been investigated using nuclear magnetic resonance technique, as shown in figure 5, TMeQ [6] with
The nuclear magnetic spectrogram of D-Met interaction, it can be seen that free object D-Met shares 4 groups of proton resonance peaks,
It coincides together since 2 groups of methene proton formant H2 and H3 chemical environments are substantially close.But be added main body TMeQ [6] with
Afterwards, the chemical shift for the methine resonance proton peak being connected with amino moves 0.08ppm to low field, shows it by melon ring end
The effect of deshielding of mouth carbonylic oxygen atom, and the chemical shift at remaining 3 groups of proton resonance peak is different degrees of to High-Field generation
Movement, the variation of specific chemical shift are respectively：δH2,0.24；δH3,0.71；δ H1,1.01, show object D-Met
This part be located at the inner cavity of melon ring TMeQ [6] and be shielded caused by effect, information above shows D-Met chirality base
Group's amino and carboxy moiety are located exactly on the outside of the port of TMeQ [6], and rest part is by the cavity institute inclusion of TMeQ [6].
Crystal structure through the invention can significantly identify that the chiral radicals of D-Met and l-methionine molecule are still exposed
Outside melon ring, achirality part enters inside melon annular space chamber so that complex is with chirality, so as to identify D- first
Methyllanthionine and l-methionine.
D-Met, which has been investigated, using Matrix-Assisted Laser Desorption Ionization Time of Flight forms host and guest with TMeQ [6]
The case where body inclusion complexes.Fig. 6 illustrates the substance spectrogram that TMeQ [6] forms inclusion cooperation with D-Met, m/z
1002.62 be TMeQ [6]+D-Met (theoretical value 1002.14), and m/z 1091.98 is TMeQ [6]+K+(theoretical value is
1092.04), m/z 1075.51 is TMeQ [6]+Na+(theoretical value 1075.94), mass spectral results show TMeQ [6] and D- first
Methyllanthionine forms 1：1 host-guest inclusion complex.
TMeQ [6] above-mentioned is prepared according to the following steps with D-Met super molecular complex：
A. by TMeQ [6] and D-Met in molar ratio 0.8~1：6~12 mixing, obtain A product；
B. by Cd (NO3)2·4H2O or Zn (NO3)2·6H2O is by TMeQ [6] and Cd (NO3)2·4H2O or Zn (NO3)2·
6H2The molar ratio of O is 0.8~1：A product mixings are added in 4~6 amount, obtain B product；
C. B product are dissolved by heating at 50-60 DEG C, is stood later until crystallizing, which is TMeQ [6] and D-
The super molecular complex of methionine synthesis, i.e. TMeQ [6]-D-Met-Cd2+Or TMeQ [6]-D-Met-Zn2+
Super molecular complex.
The preparation method and TMeQ [6] and D-Met of TMeQ [6] above-mentioned and l-methionine super molecular complex
The preparation method of super molecular complex is identical.
TMeQ [6] above-mentioned and D, l-methionine super molecular complex amino acid for identification.
TMeQ [6] above-mentioned and D, l-methionine super molecular complex are additionally operable to the inclusion to drug, are specifically used for melon
The inclusion of ring and polypeptide drug.
Embodiment 2.A kind of TMeQ [6]-l-methionine-Cd2+The preparation method of super molecular complex, makes in the steps below
It is standby：
A. according to TMeQ [6]：L-methionine：Cd(NO3)2·4H2O molar ratios are (0.8~1:6~12:4~6) ratio
Example weighs TMeQ [6], l-methionine and Cd (NO respectively3)2·4H2O is spare；
B. TMeQ [6] is placed in beaker, takes l-methionine solid in the beaker for filling [6] TMeQ；It is added appropriate
Distilled water, heating 2min, which is dissolved by heating and shaken several minutes, at 55~65 DEG C is allowed to dissolving completely；
C. Cd (NO are finally added into system3)2·4H2O is sufficiently stirred, until without precipitating or have a small amount of precipitation in beaker,
It is cooled to room temperature and stands, have the clear crystal precipitation suitable for crystal structure determination after 6-7 days, yield is in 28-36%.
Embodiment 3.A kind of TMeQ [6]-l-methionine-Zn2+The preparation method of super molecular complex, makes in the steps below
It is standby：
A. according to TMeQ [6]：L-methionine：ZnNO3)2·6H2O molar ratios are (0.8~1:6~12:4~6) ratio
Example weighs TMeQ [6], l-methionine and ZnNO respectively3)2·6H2O is spare；
B. by TMeQ [6], Zn (NO3)2·6H2O is placed in beaker, and appropriate distilled water is added, and 2 are heated at 55~65 DEG C
~5min, which is dissolved by heating and shaken several minutes, is allowed to dissolving completely；
C. take solid L- first sulphur ammonia in the beaker for filling TMeQ [6] solution；2mL distilled water, fully shaking stirring is added；
D. two beaker solution are mixed, heats 2min at 55~65 DEG C again, until a small amount of heavy without precipitating or having in beaker
It forms sediment, is cooled to room temperature and stands, have the clear crystal precipitation suitable for crystal structure determination after 7-8 days, yield is in 35-45%.
Embodiment 4.A kind of TMeQ [6]-D-Met-Cd2+The preparation method of super molecular complex, makes in the steps below
It is standby：
A. according to TMeQ [6]：D-Met：CdNO3)2·4H2O molar ratios are (0.8~1:6~12:4~6) ratio
Example weighs TMeQ [6], D-Met and CdNO respectively3)2·4H2O is spare；
B. D-Met is placed in beaker, then TMeQ [6] is added thereto；
C. 3mL Cd (NO are finally added into system3)2·4H2O solution, stirs evenly,
D. temperature control, which dissolves by heating at 50-60 DEG C and shakes several minutes, is allowed to dissolving completely, is cooled to room temperature and stands.
There is the clear crystal precipitation suitable for crystal structure determination after one week, yield is in 30-40%.
Embodiment 5.A kind of TMeQ [6]-D-Met-Zn2+The preparation method of super molecular complex, makes in the steps below
It is standby：
A. according to TMeQ [6]：D-Met：ZnNO3)2·6H2O molar ratios are (0.8~1:6~12:4~6) ratio
Example weighs TMeQ [6], D-Met and ZnNO respectively3)2·6H2O is spare；
B. TMeQ [6] is placed in beaker, takes Zn (NO3)2·6H2O solids are in the beaker for filling [6] TMeQ；
C. take D-Met solid in the beaker for filling [6] TMeQ；
D. 3-5mL distilled water is added, control temperature at 50-60 DEG C, dissolve by heating and shake several minutes in beaker without heavy
It forms sediment or has a small amount of precipitation, be cooled to room temperature and there is the clear crystal precipitation suitable for crystal structure determination, yield to exist after standing 3-5 days
35-45%.
Claims (3)
1. a kind of TMeQ [6] and D, l-methionine super molecular complex, it is characterised in that：It is water solubility melon ring TMeQ [6]
TMeQ [6]-D-Met-Cd synthesized with object D-Met2+Super molecular complex, water-soluble melon ring TMeQ [6] with
TMeQ [6]-l-methionine-Cd of object l-methionine synthesis2+Super molecular complex, water-soluble melon ring TMeQ [6] and visitor
TMeQ [6]-D-Met-Zn of body D-Met synthesis2+Super molecular complex, and water solubility melon ring TMeQ [6] and visitor
TMeQ [6]-l-methionine-Zn of body l-methionine synthesis2+Super molecular complex；TMeQ [6]-D- first sulphur ammonia
Acid-Cd2+The molecular formula of super molecular complex is C45H55O14N25CdS, structural formula are：
TMeQ [6]-l-methionine-Cd2+The molecular formula of super molecular complex is C45H55O14N25CdS, structural formula are：
TMeQ [6]-D-Met-Zn2+The molecular formula of super molecular complex is C45H55O17N26ZnS, structural formula are：
TMeQ [6]-l-methionine-Zn2+The molecular formula of super molecular complex is C45H55O17N26ZnS, structural formula are：
2. a kind of TMeQ as described in claim 1 [6] and D, the preparation method of l-methionine super molecular complex, feature
It is：The TMeQ [6] is prepared according to the following steps with D-Met super molecular complex：
A. by TMeQ [6] and D-Met in molar ratio 0.8~1：6~12 mixing, obtain A product；
B. by Cd (NO3)2·4H2O or Zn (NO3)2·6H2O is by TMeQ [6] and Cd (NO3)2·4H2O or Zn (NO3)2·6H2O's
Molar ratio is 0.8~1：A product mixings are added in 4~6 amount, obtain B product；
C. B product are dissolved by heating at 50-60 DEG C, is stood later until crystallizing, which is TMeQ [6] and D- first sulphur
The super molecular complex of propylhomoserin synthesis, i.e. TMeQ [6]-D-Met-Cd2+Or TMeQ [6]-D-Met-Zn2+Oversubscription
Sub- complex；
The preparation method and TMeQ [6] and D-Met oversubscription of the TMeQ [6] and l-methionine super molecular complex
The preparation method of sub- complex is identical.
3. a kind of TMeQ as described in claim 1 [6] and D, the application of l-methionine super molecular complex, feature exist
In：The super molecular complex D-Met and l-methionine for identification.
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