CN107151329A - The fast synthesis method of cyclodextrin-metal-organic framework materials - Google Patents
The fast synthesis method of cyclodextrin-metal-organic framework materials Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
- A61K47/40—Cyclodextrins; Derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
Abstract
The invention provides the fast synthesis method of cyclodextrin-metal-organic framework materials.Specifically, the invention provides a kind of method of cyclodextrin-metal organic framework (CD-MOFs) material that cyclodextrin (CD) is based on using solvent heat volatilization/solvent heat/microwave/ultrasonic assistant method Fast back-projection algorithm, including step：Preparing metal salt and cyclodextrin aqueous solution, and a part of organic solvent of pre-add wherein；Volatilized/solvent heat/microwave/ultrasonic method by solvent heat so that reactant fast reaction；Take supernatant to add size conditioning agent after reaction certain time, obtain cyclodextrin-metal-organic framework materials.The inventive method is quick, simplicity, safety, yield are high, and raw materials used and solvent is cheap and easy to get, beneficial to industrialized production, gained CD-MOFs catalysis, adsorb, the field such as construct of pharmaceutical carrier and nano-device is with a wide range of applications.
Description
Technical field
The present invention relates to technical field of biological material, relate more specifically to a kind of utilize solvent heat volatilization/solvent heat/micro-
The method of cyclodextrin-metal-organic framework materials of the ripple/ultrasonic assistant method Fast back-projection algorithm based on cyclodextrin.
Background technology
Metal-organic framework materials (Metal-organic frameworks, MOFs) are by organic bridging ligand
Inorganic metal center is connected to the crystalline substance to form the network-like structure infinitely extended by way of coordinate bond
Body material.Due to the porosity and huge specific surface area of MOFs superelevation, and it is by inorganic and organic difference
Composition composition structure cause its various structures and can adjust, promote MOFs in many aspects as gas storage,
The fields such as catalysis, pharmaceutical carrier have potential application value.
Cyclodextrin is a series of cyclic oligosaccharides for acting on lower generation through glucosyltransferase by amylose
General name, usually contain 6~12 D- glucopyranose units.Wherein study more and with important
Practical significance be containing 6, the molecule of 7,8 glucose units, be referred to as α, β-and γ-ring paste
Essence.Cyclodextrin is the preferable host molecule similar to enzyme found so far, and itself just has catalator
Characteristic.Therefore, in the fields such as catalysis, separation, food and medicine, cyclodextrin is received greatly
Pay attention to and extensive use.
Due to solubility and inclusion ability of the cyclodextrin in water, change the physicochemical property of cyclodextrin turns into change
Learn one of free-revving engine of modification cyclodextrin.In pre-organized acceptor, the arrangement of-OCCO- chelating units, bag
Crown ether, cave ether are included, the metal ion for both contributing to its compound with first and second main group is combined.And cyclodextrin
Starch is extracted from, cyclodextrin presentation-OCCO- bidentate themes on its one-level, two grades of faces contribute to it
Combined with the metal ion of first and second main group.
Cyclodextrin-metal organic framework mainly uses cyclodextrin in aqueous can be with first and second main group gold
Category ion forms a kind of new crystal in the way of a kind of organic coordination, and this crystal has porous, surface area
Greatly, the features such as storing gas.This green, porous material can adsorb some structural unstable medicines,
Its huge cavity can play a protective role to medicine, and this make it that it is used for business development, especially
It is due to that cyclodextrin-metal organic framework is edible derivative, suitable for human consumption.
Using cyclodextrin as organic ligand, metal ion can form new, safety as inorganic metal center
Property higher, pharmaceutically useful cyclodextrin-metal organic framework, i.e. CD-MOFs.
It is that Angew.Chem.Int.Ed.2012,51,10566-10569, which is described CD-MOFs point,
One stage CD-MOF, second stage micron order CD-MOF, second stage nanoscale CD-MOF.First stage
CD-MOF refers to mix γ-CD with KOH, is evaporated by methanol steam, by certain time, directly separates out
The process of crystal, i.e. CD-MOF I；Second stage micron order CD-MOF refers to mix γ-CD with KOH, leads to
Methanol steam evaporation is crossed, when not producing also or only producing a small amount of first stage crystal, supernatant is taken out,
Surfactant cetyl trimethylammonium bromide (CTAB) is added, the process of crystal is then separated out again, i.e.,
CD-MOF II；Second stage nanoscale CD-MOF refers to mix γ-CD with KOH, is steamed by methanol steam
Hair, when not producing also or only producing a small amount of first stage crystal, supernatant is taken out, according to supernatant fluid
Product adds a large amount of methanol, adds CTAB, then separates out the process of nano-scale crystal, i.e. CD-MOF Nano.
Stoddart et al. (Angew.Chem.Int.Ed.2010,49,8630-8634) is first with γ
- CD and KOH be raw material, the method evaporated by normal temperature methanol steam, by 2-7 days, preparing particle diameter was
Hundreds of microns of CD-MOFs, yield is 66%.
Furukawa et al. (Angew.Chem.Int.Ed.2012,51,10566-10569) is with γ-CD
It is raw material with KOH, the method evaporated by normal temperature methanol steam, by 24h, prepares 40-500 μm
CD-MOFs, surfactant cetyl trimethylammonium bromide (CTAB) is added in 26-32h, further
Prepare 10 μm of second stage and nano level CD-MOFs.
US9085460B2 and US2012/0070904A1 are first molten by food-grade Potassium Benzoate and food-grade cyclodextrin
Solution in aqueous, is filtered by velveteen, then is slowly evaporated in the aqueous solution a couple of days by ethanol, is finally obtained
To complete edible product.
The octenyl amber that CN103549635A is obtained with octenyl succinic acid anhydride and resistant starch through esterification
Amber acid resistance starch ester is base material, and the γ-CD of metallo-organic framework are adsorbed in ocentyl succinic
The surface of resistant starch ester, constructs a kind of nutrition carrier with porous network structure, and this product advantage is
The functional mass such as nutrient can in solid form be embedded wherein, be prevented effectively from light irradiation, oxygen and soda acid
Deng destruction, and play certain slow release effect.But, the above method reaction time is long, last from days,
It is difficult to industrialized production.
Preparation Mx (L) y (OH) v (H2O) w is mentioned in CN201380030382.6, and (M is a kind of metal or a variety of gold
Category, L is the polycarboxylic acids of benzene salt connector) form MOFs method, mainly by L salt or its aqueous solution,
Mixed with the solution in metal salt/source, fully after dissolving, by gained mixed solution by rotary evaporator by water
Evaporate or be recovered by filtration, generated time only has -6 hours 30 minutes.
In summary, this area in the urgent need to exploitation is quick, easy cyclodextrin of the synthesis based on cyclodextrin-
The method of metal-organic framework materials.
The content of the invention
Solvent heat volatilization/solvent heat/microwave/ultrasonic assistant method is utilized it is an object of the invention to provide one kind
The method of cyclodextrin-metal-organic framework materials of the Fast back-projection algorithm based on cyclodextrin.
In the first aspect of the present invention there is provided a kind of method for preparing cyclodextrin-metal-organic framework materials,
Including step：
(1) the first mixed solution is provided, first mixed solution is the solution containing metal ion and cyclodextrin；
(2) the first organic solvent is added into the first described mixed solution, the second mixed solution is obtained,
Wherein, the volume ratio of first organic solvent and first mixed solution is (0.01-5):1, preferably
For (0.1-2):1, it is most preferably (0.5-1):1；
(3) second mixed solution is pre-processed, pretreated first mixture is obtained, wherein described
Pretreatment be selected from the group：Solvent heat treatment, microwave treatment, ultrasonication or its combination,
(4) optionally, when in the first mixture containing the cyclodextrin-metal-organic framework materials separated out, from institute
State separation in the first mixture and obtain the cyclodextrin-metal-organic framework materials separated out；
(5) when isolating all or part of solution from first mixture, it is used as the 3rd mixed solution；And
The second organic solvent and/or size conditioning agent are added into the 3rd mixed solution, so as to separate out cyclodextrin-metal
Organic framework material；With
(6) optionally cyclodextrin-the metal-organic framework materials separated out in step (5) are separated and/or done
It is dry.
In another preference, described pretreatment is microwave treatment or ultrasonication；
In another preference, total time T of step (3) and step (5) is -12 hours 1 minute, is more preferably 1
- 3 hours minutes, are most preferably -1 hour 1 minute, or 1-30 minutes, or 5-30 minutes or 2-25 minutes.
Or, total time T of step (3) and step (5) is -12 hours 5 minutes, is more preferably -3 hours 5 minutes,
Most preferably it is -1 hour 10 minutes.
In another preference, described size conditioning agent is selected from the group：Polyethylene glycol, PVP, polysorbate,
(nonyl phenol polyethenoxy ether is condensed for sorbitan mono-laurate, Brij30, polyoxyethylene nonylphenol ether
Thing), breast lark A (polyoxyethylene aliphatic alcohol ether), pluronic (polyoxyethylene polypropylene glycol condensation product), dodecane
Base sodium sulphate, neopelex, dodecyl dimethyl benzyl ammonium bromide (benzalkonium bromide) or its combination.
In another preference, described size conditioning agent is polyethylene glycol.
In another preference, described polyethylene glycol include PEG200, PEG400, PEG600, PEG800,
PEG1000、PEG1500、PEG2000、PEG4000、PEG6000、PEG8000、PEG10000、PEG20000、
Or its combination.
In another preference, described PVP include PVP K12, PVP K15, PVP K17, PVP K25,
PVP K30, PVP K60, PVP K90, PVP K120 or its combination.
In another preference, described polysorbate includes polysorbas20, polysorbate40, polysorbate60, Tween 80, told
Temperature 85 or its combination.
In another preference, described sorbitan mono-laurate include span 20, span 40, sorbester p18,
Sorbester p17 or its combination.
In another preference, described size conditioning agent include PEG2000, PEG4000, PEG6000, PEG8000,
PEG10000, PEG20000 or its combination, preferably PEG 20000.
In another preference, the temperature of the pretreatment is 25-100 DEG C, preferably 30-80 DEG C, more preferably
For 40-60 DEG C.
In another preference, time of the pretreatment is 10min-24h, preferably 15min-1h, more preferably
Ground is 20-30min.
In another preference, described solvent heat treatment is to carry out heating water bath or oil bath heating to mixed solution.
In another preference, the power of the microwave treatment is 20-1000W, preferably 25-100W.
In another preference, the radiation frequency of the microwave treatment is 916-2450MHz, preferably 2450MHz.
In another preference, the power of the ultrasonication is 20-1000W, preferably 40W.
In another preference, the radiation frequency of the ultrasonication is 22-100KHz, preferably
30-50KHz。
In another preference, described the first organic solvent and the second organic solvent is each independently selected from the following group：
Methanol, ethanol, isopropanol, acetone, acetonitrile or its combination.
In another preference, described the first organic solvent and the second organic solvent is identical or different.
In another preference, the first described organic solvent and the second organic solvent are methanol.
In another preference, described step (4) can be carried out, also can be without.
In another preference, cyclodextrin-metal-organic framework materials of described preparation have one be selected from the group
Individual or multiple features：
(i) average grain diameter：50nm-50 microns, preferably 100-1000 nanometers (nanoscale) or 1-10 microns it is (micro-
Meter level)；
(ii) in the cyclodextrin-metal-organic framework materials, the mol ratio of CD and metal ion is 1~1.2：
6-10 (such as 1:6-10, or about 1:8)；
(iii) cyclodextrin-metal-organic framework materials described in are pharmaceutically acceptable carrier；
(iv) cyclodextrin-metal-organic framework materials described in can have preferably protection to make to thermally labile medicine
With.
In another preference, in step (5), the volume ratio of second organic solvent and the 3rd mixed liquor is
(0.01-5):1, preferably (0.5-2):1, it is more preferably 1:1.
In another preference, the 3rd described mixed solution is supernatant.
In another preference, in step (5), the amount of the size conditioning agent of addition is 1-20mg/mL, preferably
For 5-10mg/mL.
In another preference, in step (5), centrifugal treating is carried out to the first mixture, so that from described the
Part solution is isolated in one mixture.
In another preference, the rotating speed of the centrifugal treating is 1000-5000rpm, preferably
2000-3000rpm。
In another preference, the time of the centrifugal treating is 3-10min, preferably 5-8min.
In another preference, in step (6), including step：
(a) pretreated mixed solution is centrifuged, never obtains sediment；
(b) sediment is washed；With
(c) sediment after washing is dried in vacuo, so as to obtain cyclodextrin-metal organic framework material of crystallization
Material.
In another preference, in step (b), the sediment is washed with ethanol.
In another preference, in step (c), the vacuum drying temperature is 40-60 DEG C.
In another preference, in step (c), the vacuum drying time is 6-24h.
In another preference, in step (1), the aqueous solution of metallic compound and cyclodextrin aqueous solution are mixed,
So as to obtain the first described mixed solution.
In another preference, in step (1), by metallic compound and cyclodextrin in water, so as to obtain
Obtain the first described mixed solution.
In another preference, described metallic compound includes metal salt and metal base.
In another preference, described metallic compound is KOH.
In another preference, the concentration of metal ion is 0.05-0.4M in the first described mixed solution, preferably
Ground is 0.1-0.3M, is more preferably 0.2M.
In another preference, the concentration of the first described mixed solution cyclodextrin is 0.013-0.05M, preferably
Ground is 0.02-0.03M, is more preferably 0.025M.
In another preference, the first described mixed solution cyclodextrin and the mol ratio of metal ion are 1：
(6-10), preferably 1:8.
In another preference, described metal ion is selected from the group：Li+、K+、Rb+、Cs+、Na+、Mg2+、
Cd2+、Sn2+、Ag+、Yb+、Ba2+、Sr2+、Ca2+、Pb2+、La3+Or its combination.
In another preference, the metal ion is K+。
In another preference, described cyclodextrin is selected from the group：Alpha-cyclodextrin, beta-schardinger dextrin, γ-ring paste
Essence, hydroxypropyl-β-cyclodextrin, Sulfobutyl ether β _ cyclodextrin, methyl-B-cyclodextrin, carboxymethyl-beta-cyclodextrin,
Or its combination.
In another preference, described cyclodextrin is gamma-cyclodextrin.
In another preference, described cyclodextrin-metal-organic framework materials are used to prepare the production being selected from the group
Product：Catalyst, adsorbent and pharmaceutical carrier.
In the second aspect of the present invention there is provided a kind of method for preparing cyclodextrin-metal-organic framework materials,
Including step：
(1) the first mixed solution is provided, first mixed solution is the solution containing metal ion and cyclodextrin；
(2) the first organic solvent is added into the first described mixed solution, the second mixed solution is obtained,
Wherein, the volume ratio of first organic solvent and first mixed solution is (0.01-0.5):1, preferably
Ground is (0.03-0.3):1, it is most preferably (0.05-0.2):1；
(3) second mixed solution is pre-processed, pretreated first mixture is obtained, wherein described
Pretreatment be selected from the group：
(a) solvent heat volatilization is handled；
(b) solvent heat volatilization processing and the combination of any processing mode selected from A groups, wherein A groups are included at solvent heat
Reason, microwave treatment, ultrasonication or its combination；
(4) when in the first mixture containing the cyclodextrin-metal-organic framework materials separated out, from the described first mixing
Separation obtains the cyclodextrin-metal-organic framework materials separated out in thing；
Or all or part of solution is isolated from first mixture, it is used as the 3rd mixed solution；And to
The second organic solvent and/or size conditioning agent are added in 3rd mixed solution, so that separating out cyclodextrin-metal has
Machine framework material；With
(5) optionally cyclodextrin-the metal-organic framework materials separated out in step (4) are separated and/or done
It is dry.
In another preference, in step (3), described solvent heat volatilization processing includes step：
(I) mixed solution is placed in an open containers I；
(II) an open containers II that organic solvent is housed is provided, the open containers I and open containers II is common
It is placed in a closed system；With
(III) organic solvent in the open containers II is carried out heating/isothermal holding so that the organic solvent
Evaporation and diffusion is into mixed solution.
In another preference, in step (III), overall heating is carried out to the closed system, so that
Heat the organic solvent in the open containers II
In another preference, in step (III), the heating includes heating water bath and oil bath heating.
In another preference, in step (III), the temperature of the heating is 25-100 DEG C, preferably
It it is more preferably 40-60 DEG C for 30-80 DEG C.
In another preference, in step (III), the time of the heating is 4-48h, preferably
6-24h。
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the invention and (such as implementation below
Example) in specifically describe each technical characteristic between can be combined with each other, so as to constitute new or preferred skill
Art scheme.As space is limited, no longer tire out one by one herein and state.
Brief description of the drawings
Fig. 1 is the CD-MOF I optical microscopy maps of solvent evaporation method preparation in embodiment 1.
The optical microscopy map that Fig. 2 is CD-MOF II obtained by solvent evaporation method in embodiment 2.
The scanning electron microscope (SEM) photograph that Fig. 3 is CD-MOF II obtained by solvent evaporation method in embodiment 2.
The scanning electron microscope (SEM) photograph that Fig. 4 is CD-MOF Nano obtained by solvent evaporation method in embodiment 3.
The X-ray powder diffraction figure that Fig. 5 is CD-MOF I obtained by solvent evaporation method in embodiment 1.
The X-ray powder diffraction figure that Fig. 6 is CD-MOF II obtained by solvent evaporation method in embodiment 2.
The X-ray powder diffraction figure that Fig. 7 is CD-MOF Nano obtained by solvent evaporation method in embodiment 3.
The grain size distribution that Fig. 8 is CD-MOF II obtained by solvent evaporation method in embodiment 2.
The optical microscopy map that Fig. 9 is CD-MOF II obtained by solvent-thermal method in embodiment 4.
The optical microscopy map that Figure 10 is CD-MOF II obtained by solvent-thermal method in embodiment 5.
The optical microscopy map that Figure 11 is CD-MOF II obtained by solvent-thermal method in embodiment 6.
The optical microscopy map that Figure 12 is CD-MOF II obtained by solvent-thermal method in embodiment 7.
The scanning electron microscope (SEM) photograph that Figure 13 is CD-MOF II obtained by solvent-thermal method in embodiment 4.
The scanning electron microscope (SEM) photograph that Figure 14 is CD-MOF Nano obtained by solvent-thermal method in embodiment 8.
The X-ray powder diffraction figure that Figure 15 is CD-MOF II obtained by solvent-thermal method in embodiment 4.
The X-ray powder diffraction figure that Figure 16 is CD-MOF Nano obtained by solvent-thermal method in embodiment 8.
The grain size distribution that Figure 17 is CD-MOF II obtained by solvent-thermal method in embodiment 4.
The grain size distribution that Figure 18 is CD-MOF II obtained by solvent-thermal method in embodiment 5.
The grain size distribution that Figure 19 is CD-MOF II obtained by solvent-thermal method in embodiment 6.
The grain size distribution that Figure 20 is CD-MOF II obtained by solvent-thermal method in embodiment 7.
The optical microscopy map that Figure 21 is CD-MOF II obtained by microwave method in embodiment 9.
The scanning electron microscope (SEM) photograph that Figure 22 is CD-MOF II obtained by microwave method in embodiment 9.
The scanning electron microscope (SEM) photograph that Figure 23 is CD-MOF Nano obtained by microwave method in embodiment 10.
The X-ray powder diffraction figure that Figure 24 is CD-MOF II obtained by microwave method in embodiment 9.
The X-ray powder diffraction figure that Figure 25 is CD-MOF Nano obtained by microwave method in embodiment 10.
The optical microscopy map that Figure 26 is CD-MOF II obtained by supercritical ultrasonics technology in embodiment 11.
The scanning electron microscope (SEM) photograph that Figure 27 is CD-MOF II obtained by supercritical ultrasonics technology in embodiment 11.
The scanning electron microscope (SEM) photograph that Figure 28 is CD-MOF Nano obtained by supercritical ultrasonics technology in embodiment 12.
The X-ray powder diffraction figure that Figure 29 is CD-MOF II obtained by supercritical ultrasonics technology in embodiment 11.
The X-ray powder diffraction figure that Figure 30 is CD-MOF Nano obtained by supercritical ultrasonics technology in embodiment 12.
Figure 31 carries IBU infrared spectrogram for CD-MOF II in CD-MOF II in embodiment 2 and embodiment 13.
Figure 32 carries IBU infrared spectrum for CD-MOF Nano in CD-MOF Nano in embodiment 3 and embodiment 14
Figure.
Figure 33 carries LPZ infrared spectrogram for CD-MOF II in CD-MOF II in embodiment 2 and embodiment 15.
Figure 34 carries LPZ infrared spectrum for CD-MOF Nano in CD-MOF Nano in embodiment 3 and embodiment 16
Figure.
Figure 35 is releasing curve diagram of the CD-MOF Nano load made microballoons of IBU in PBS7.4 in embodiment 14.
Figure 36 is releasing curve diagram of the CD-MOF Nano load made microballoons of LPZ in PBS7.4 in embodiment 16.
Embodiment
The present inventor have unexpectedly discovered that one kind using solvent heat volatilization first by extensively and in depth studying
The side of/solvent heat/microwave/metal-organic framework materials of the ultrasonic assistant method Fast back-projection algorithm based on cyclodextrin
Method.Specifically, it the described method comprises the following steps：Preparing metal salt and cyclodextrin aqueous solution, and wherein
A part of organic solvent of pre-add；Volatilized/solvent heat/microwave/ultrasonic method by solvent heat so that reaction
Thing fast reaction；Take supernatant to add size conditioning agent after reaction certain time, that is, obtain cyclodextrin-metal
Organic framework material.Conventional method needs time a couple of days to complete to react, and method employed in the present invention
Need several minutes to a few houres just can complete.The inventive method is quick, simplicity, safety, yield are high, raw materials used
It is cheap and easy to get with solvent, beneficial to industrialized production, gained CD-MOFs catalysis, absorption, pharmaceutical carrier and
The field such as construct of nano-device is with a wide range of applications.
Cyclodextrin-metal-organic framework materials
As used herein, term " metal-organic framework materials based on cyclodextrin ", " cyclodextrin-metal has
Machine framework material ", " cyclodextrin-metal organic framework compound " are used interchangeably, and are to utilize cyclodextrin
A kind of new crystalline substance can be formed in the way of a kind of organic coordination with first and second main group metal ion in aqueous
Body, the features such as this crystal has big porous, surface area, storage gas.This green, porous material energy
Some structural unstable medicines are enough adsorbed, its huge cavity can play a protective role to medicine, and this makes
It is used for business development and is possibly realized, it is edible derivative to be particularly due to cyclodextrin-metal organic framework
Thing, suitable for human consumption.Using cyclodextrin as organic ligand, metal ion, can as inorganic metal center
Form that new, security is higher, pharmaceutically useful cyclodextrin-metal organic framework, i.e. CD-MOFs.
As used herein, term " CD-MOF I " refer to first stage CD-MOF crystal, refer to by γ-CD with
KOH is mixed, and is evaporated by methanol steam, by certain time, the crystal obtained by directly separating out；This hair
The size of first stage CD-MOF crystal is about 40-500 μm made from bright method.
As used herein, " CD-MOF II " refer to second stage CD-MOF crystal to term, refer to γ-CD
Mix, evaporated by methanol steam with KOH, when not producing also or only producing a small amount of first stage crystal,
Supernatant is taken out, size conditioning agent is added, resulting crystal is then separated out again；The inventive method is made
The size of second stage CD-MOF crystal be about 1-10 μm.
As used herein, " CD-MOF Nano " refer to the CD-MOF crystal of nano-scale to term, refer to γ
- CD is mixed with KOH, is evaporated by methanol steam, when not producing also or only producing a small amount of first stage crystal,
Supernatant is taken out, a large amount of methanol is added according to supernatant volume, adds size conditioning agent, then analyse again
Go out resulting crystal；CD-MOF Nano size is about 200-500nm made from the inventive method.
Metal-organic framework materials
Metal-organic framework materials (Metal-organic frameworks, MOFs) are by organic bridging ligand
Inorganic metal center is connected to the crystalline substance to form the network-like structure infinitely extended by way of coordinate bond
Body material.Due to the porosity and huge specific surface area of MOFs superelevation, and it is by inorganic and organic difference
Composition composition structure cause its various structures and can adjust, promote MOFs in many aspects as gas storage,
The fields such as catalysis, pharmaceutical carrier have potential application value.
Cyclodextrin
Cyclodextrin is a series of cyclic oligosaccharides for acting on lower generation through glucosyltransferase by amylose
General name, usually contain 6~12 D- glucopyranose units.Wherein study more and with important
Practical significance be containing 6, the molecule of 7,8 glucose units, be referred to as α, β-and γ-ring paste
Essence.Cyclodextrin is the preferable host molecule similar to enzyme found so far, and itself just has catalator
Characteristic.
Pre-add organic solvent
In the method for the invention, before being reacted, pre-add is a certain amount of organic molten in reaction system
Agent, enables gained CD-MOFs crystal faster to separate out, while can not add excessive organic solvent again, otherwise
Easily the cyclodextrin dissolved is set directly to separate out, the CD-MOFs of final gained will adulterate some ring
Dextrin.
Pretreatment
In the method for the invention, in order to reach the purpose of fast reaction, to containing metal salt and cyclodextrin,
And the pre- mixed liquor added with organic solvent is pre-processed, the pretreatment includes solvent heat treatment, microwave
Processing, and/or ultrasonication.
Solvent-thermal method is the optimization of hydro-thermal method, and microwave treatment enables to material molecule to occur dither, no
Heat is only produced, temperature is quickly raised, while enhancing material transmission, reaction activity is reduced, promotees
Enter potassium hydroxide to react with gamma-cyclodextrin so that homogeneous heating, shorten the time of heat transfer, and
Be not in the drawbacks of conventional method heating is uneven.Ultrasonication mainly uses ultrasonic cavitation effect to make
There is a series of actions, produced chemical effect and the mechanical effects such as expansion, compression, collapse in reaction solution
Reaction condition can be improved, accelerate reaction speed.The generation and closing of microwave and ultrasonic wave energy be it is instantaneous,
There is no thermal inertia, it is safe and reliable, it is easy to Automated condtrol.
Particularly preferred preprocess method is microwave/ultrasonic method, and they effectively can be absorbed using substance to be processed
Microwave or ultrasonic wave produce molecular resonance and realize rapid and uniform heating, while ultrasonic cavitation, impact
Very big Accelerative mass transfer effect is acted on microjet, therefore even if can also cooperate with size conditioning agent at a lower temperature
Potassium hydroxide is promoted to be reacted with gamma-cyclodextrin.
Preparation method
Present invention also offers a kind of method for preparing the metal-organic framework materials based on cyclodextrin.
Typically, the inventive method comprises the steps：Metal salt solution is mixed in cyclodextrin aqueous solution
In one open containers, a part of organic solvent of pre-add in mixed solution, then open containers are placed in one be equipped with
In the closed system of organic solvent, under certain temperature, by the method for organic solvent evaporation, make steam-like
Organic solvent is diffused in open containers, after reaction certain time, and mixed solution system, which is absorbed, substantial amounts of to be had
Machine solvent, takes out supernatant, adds size conditioning agent, that is, obtains the metal based on cyclodextrin organic
Framework material；Or mix metal salt solution with cyclodextrin aqueous solution, a part of organic solvent of pre-add is put in
In one closed container, reaction medium is heated with solvent heat/microwave/ultrasonic wave so that reactant
Fast reaction, after reaction certain time, takes out supernatant, adds size conditioning agent, that is, obtain the base
In the metal-organic framework materials of cyclodextrin.
In another preference, the pre- solubilizer is added when being divided into incipient stage pre-add and size regulation.Open
In stage beginning pre- added-time, the organic solvent volume of pre-add is 0.001-5 times of metal salt and cyclodextrin mixed solution.
It is preferred that 0.6 times.Size is added when adjusting, and organic solvent volume is 0.001-5 times of gained supernatant volume.
It is preferred that 1 times.
A kind of method of the preferred preparation based on cyclodextrin-metal organic framework comprises the steps：By metal
After salting liquid is mixed with cyclodextrin aqueous solution, a part of organic solvent of pre-add, under certain temperature (be higher than room temperature),
By solvent vapo(u)r method of diffusion, certain time is reacted, size conditioning agent is added, so as to obtain the base
In the metal-organic framework materials of cyclodextrin；Or mix metal salt solution with cyclodextrin aqueous solution, pre-add one
Part organic solvent, with solvent heat/microwave/ultrasonic activation reaction medium so that reactant fast reaction,
React and size conditioning agent is added after certain time, so as to obtain the metal organic framework material based on cyclodextrin
Material.
Wherein, the cyclodextrin include alpha-cyclodextrin, beta-schardinger dextrin, gamma-cyclodextrin, hydroxy propyl-Beta-
Cyclodextrin, Sulfobutyl ether β _ cyclodextrin, methyl-B-cyclodextrin, carboxymethyl-beta-cyclodextrin, preferably γ-
Cyclodextrin.
The concentration of metal salt is 0.05-0.4M, preferably 0.2M in the metal salt solution.
The concentration of the cyclodextrin aqueous solution cyclodextrin is 0.013-0.05M, preferably 0.025M.
The metal salt includes Li+、K+、Rb+、Cs+、Na+、Mg2+、Cd2+、Sn2+、Ag+、Yb+、Ba2+、
Sr2+、Ca2+、Pb2+、La3+, preferably K+。
The pre- solubilizer is added when being divided into incipient stage pre-add and size regulation.The incipient stage pre- added-time, in advance
Plus organic solvent volume be 0.001-5 times of metal salt and cyclodextrin mixed solution.It is preferred that 0.6 times.Size
Added during regulation, organic solvent volume is 0.001-5 times of gained supernatant volume.It is preferred that 1 times.
Methods described includes the quick side for preparing first stage and second stage cyclodextrin-metal organic framework
Method.First stage is mainly the method volatilized by solvent heat, cyclodextrin metal organic framework is passed through organic
Solvent vapo(u)r evaporates, the process directly separated out from cyclodextrin-metal salt solution.Second stage solvent heat
Volatilization/solvent heat/four kinds of microwave/ultrasonic assistant method can be with, refers to reaction solution and reacts after a period of time,
Take its supernatant to add size conditioning agent, the process of cyclodextrin-metal organic framework is then separated out again.Wherein
Second stage can be subdivided into microscale/nanoscale cyclodextrin-metal organic framework, micron order cyclodextrin-gold again
It is first preparing metal salt and cyclodextrin aqueous solution to belong to organic backbone, and a part of organic solvent of pre-add passes through solvent
Hot volatilization/solvent heat/microwave/ultrasonic method, takes its supernatant to add size conditioning agent, then separates out again
The process of cyclodextrin-metal organic framework；Nanoscale cyclodextrin-metal organic framework be first preparing metal salt with
Cyclodextrin aqueous solution, a part of organic solvent of pre-add is volatilized/solvent heat/microwave/ultrasonic wave side with solvent heat
Method processing, takes its supernatant, then adds a part of organic solvent, then adds size conditioning agent, finally analyses
Go out the process of cyclodextrin-metal organic framework.In addition, methods described is additionally included in after reaction terminates to reaction
Liquid is centrifuged, collects the step of precipitating and wash and be dried in vacuo.
The size conditioning agent include polyethylene glycol (PEG 200,400,600,800,1000,1500,
2000th, 4000,6000,8000,10000,20000), PVP (PVP K12, K15, K17, K25,
K30, K60, K90, K120), polysorbate (polysorbas20,40,60,80,85), anhydrous sorbitol list
(nonyl phenol gathers for laurate (span 20,40,60,80), Brij30, polyoxyethylene nonylphenol ether
Oxygen vinethene condensation product), breast lark A (polyoxyethylene aliphatic alcohol ether), pluronic (polyoxyethylene poly- the third two
Alcohol condensation product), lauryl sodium sulfate, neopelex, cetyl trimethylammonium bromide
(CTAB), dodecyl dimethyl benzyl ammonium bromide (benzalkonium bromide) and one kind or several in their derivative
Kind, and several size conditioning agents combination.It is preferred that pharmaceutic adjuvant PEG 2000,4000,6000,8000,
10000,20000, concretely PEG 20000.
The organic solvent includes but is not limited to methanol, ethanol, acetone, isopropanol, acetonitrile, concretely
Methanol.
Second stage cyclodextrin-the metal organic framework, which is included in gained supernatant, is not added with organic solvent
PEG 20000, or addition 0.05-10ml organic solvents/5ml supernatants are directly added into, PEG is added afterwards
20000.The additions of PEG 20000 include 1-16mg PEG 20000/ml supernatants, preferably 8mg PEG
20000/ml supernatants.
The mol ratio of the cyclodextrin and aqueous metal salt is 0.06:0.5-0.25:2, preferably
0.125:1。
The solvent heat evaporation method, temperature include -100 DEG C of room temperature, reaction time 4-24h, preferably 50 DEG C,
6h。
The solvent thermal process, temperature include -100 DEG C of room temperature, reaction time 1min-24h, preferably 50 DEG C,
20min。
The microwave radiation frequencies use 916-2450MHz, and power is 20-1000W, temperature setting 25-100
DEG C, reaction time 1min-24h, preferably 2450MHz, 25W, 50 DEG C, 20min.
The Ultrasonic Radiation frequency uses 22-40KHz, and power is 100-1000W, temperature setting 25-100
DEG C, reaction time 1min-24h, preferably 30KHz, 300W, 50 DEG C, 20min.
Compared with existing method, main advantages of the present invention include：
1st, be swift in response simplicity, has saved the time, eliminates many red tapes, the reaction time is by 2-7
It is reduced to several minutes-a few houres.
2nd, method of the invention can avoid the waste of organic solvent.In particular by solvent heat/microwave/super
During sonic method, the waste of organic solvent in solvent volatilization process can be prevented effectively from.
3rd, CD-MOF prepared by solvent heat/microwave/supercritical ultrasonics technology can realize industrialized production completely, and general
Logical solvent evaporation method is difficult to carry out.
4th, gained CD-MOFs has first stage CD-MOF (CD-MOF I) and second stage CD-MOF, wherein the
Two-stage CD-MOF is divided into micron order, nanoscale, second stage micron order CD-MOF (CD-MOF I) size again
For 1-20 μm, second stage nanoscale CD-MOF (CD-MOF Nano) size is 100-1000nm, and text
The yield highest of middle first stage is offered less than 70%, the yield of second stage is lower.The method yield of the present invention
70-90% can be reached.
5th, the size rule of the metal-organic framework materials based on cyclodextrin made from method of the invention, yield
It is high.The size of crystal is adjusted with pharmaceutic adjuvant, it is safe, can be with medicinal, and if being not added with size tune
Save agent, be hardly obtained any crystal or only a small amount of crystal, and form and size very irregular are generally
Tens microns.
6. present method avoids solvent the letting out in volatilization process that conventional solvent evaporation method is caused
Leakage, it is more safe and reliable.
7. the present invention can effectively control CD-MOFs size.Size Control to CD-MOFs is conducive to metal to have
Application and some nano-devices of the machine framework compound in terms of catalysis, absorption, pharmaceutical carrier, such as gas
Sensor, membrane separation device, the preparation of capillary chromatographic column, dry powder suction etc..This method is for extension
In terms of the application of metal organic framework compound and the research of MOFs formation mechenisms, especially ground in pharmaceutical carrier etc.
Study carefully field to have great importance and wide application prospect.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate
The present invention rather than limitation the scope of the present invention.The experiment side of unreceipted actual conditions in the following example
Method, generally according to normal condition, or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise
Percentage and number are calculated by weight.
Embodiment 1
Solvent heat volatility process prepares first stage CD-MOF crystal
By 163.0mg γ-CD and 56.0mg KOH mixtures (γ-CD and KOH mol ratios are 0.125) dissolving
In 5mL water, ultrasound makes it fully dissolve in 10 minutes, 0.45 μm of membrane filtration.Then pre-add 0.5mL first
In alcohol to γ-CD and KOH mixed solutions, in closed container under the conditions of 50 DEG C heating methanol (closed container is whole
Body is heated), methanol steam is evaporated in γ-CD and KOH mixed systems.Begun with during reaction 6h a small amount of
Crystal is produced, after reaction 24h, obtains a large amount of colourless transparent crystals, abandoning supernatant, 3000rpm centrifugations 5
Min, is washed with ethanol (10mL × 3), and by 50 DEG C of vacuum drying 12h of gained crystal, produce to preserve for a long time
First stage CD-MOF crystal (CD-MOF I), size is 40-500 μm, such as Fig. 1 and Fig. 5, and yield is
76.3%.
Embodiment 2
Solvent heat volatility process prepares second stage micron order CD-MOF crystal
Weigh 163.0mg γ-CD and 56.0mg KOH mixtures (γ-CD and KOH mol ratios are 0.125) molten
Solution is in 5mL water, and ultrasound makes it fully dissolve in 10 minutes, 0.45 μm of membrane filtration.Then pre-add 0.5mL
In methanol to γ-CD and KOH mixed solutions, the heating methanol (closed container under the conditions of 50 DEG C in closed container
Overall heating), methanol steam is evaporated in γ-CD and KOH mixed systems.After reaction 6 hours, in taking-up
Clear liquid, adds PEG 20000 in the ratio of 8mg/mL supernatants, stands after half an hour, 3000rpm centrifugations
5min, is washed with ethanol (10mL × 2), dichloromethane (10mL × 2) respectively, and 50 DEG C of gained crystal is true
Sky dries 12h, produces second stage micron order CD-MOF crystal (CD-MOF II) with long preservation period, size
For 1-10 μm, such as Fig. 2, Fig. 3, Fig. 6 and Fig. 8, yield is 85.1%.
Embodiment 3
Solvent heat volatility process prepares second stage nanoscale CD-MOF crystal
163.0mg γ-CD and 56.0mg KOH mixtures (γ-CD and KOH mol ratios are 0.125) are dissolved in
In 5mL water, ultrasound makes it fully dissolve in 10 minutes, 0.45 μm of membrane filtration.Then pre-add 0.5mL methanol
To γ-CD and KOH mixed solutions, heating methanol (the closed container entirety under the conditions of 50 DEG C in closed container
Heating), methanol steam is evaporated in γ-CD and KOH mixed systems.After reaction 6 hours, supernatant is taken out,
Isometric methanol is added, then PEG 20000 is added in the ratio of 8mg/mL supernatants, is stood after half an hour,
3000rpm centrifuges 5min, is washed respectively with ethanol (10mL × 2), dichloromethane (10mL × 2), by gained
50 DEG C of vacuum drying 1h of crystal, produce second stage nanoscale CD-MOF crystal (CD-MOF Nano), size
For 200-500nm, such as Fig. 4 and Fig. 7, yield is 90.3%.
Embodiment 4
Solvent-thermal method prepares second stage micron order CD-MOF crystal
Using the mode of solvent heat, directly gamma-cyclodextrin is mixed with the KOH aqueous solution with a part of organic solvent
System is heated.Weigh 163.0mg γ-CD and 56.0mg KOH mixture (γ-CD and KOH mol ratios
0.125) to be dissolved in 5mL water, in pre-add 3mL methanol to mixed solution, after 50 DEG C of heating water bath 20min,
Solution is taken out, 64mg PEG 20000 are added, stood after half an hour, 3000rpm centrifugation 5min, respectively
Washed with ethanol (10mL × 2), dichloromethane (10mL × 2), by gained crystal, 50 DEG C are dried in vacuo 12h, i.e.,
Second stage micron order CD-MOF crystal (CD-MOF II) is obtained, size is 1-10 μm, such as Fig. 9, Figure 13, figure
15 and Figure 17, yield is 87.0%.
Embodiment 5
Solvent-thermal method prepares second stage micron order CD-MOF crystal
Using the mode of solvent heat, directly gamma-cyclodextrin is mixed with the KOH aqueous solution with a part of organic solvent
System is heated.Weigh 163.0mg γ-CD and 56.0mg KOH mixture (γ-CD and KOH mol ratios
0.125) to be dissolved in 5mL water, in pre-add 3mL methanol to mixed solution, after 50 DEG C of heating water bath 20min,
Solution is taken out, 16mg PEG 20000 are added, stood after half an hour, 3000rpm centrifugation 5min, respectively
Washed with ethanol (10mL × 2), dichloromethane (10mL × 2), by gained crystal, 50 DEG C are dried in vacuo 12h, i.e.,
Second stage micron order CD-MOF crystal (CD-MOF II) is obtained, size is 1-10 μm, such as Figure 10 and Figure 18,
Yield is 58.3%.
Embodiment 6
Solvent-thermal method prepares second stage micron order CD-MOF crystal
Using the mode of solvent heat, directly gamma-cyclodextrin is mixed with the KOH aqueous solution with a part of organic solvent
System is heated.Weigh 163.0mg γ-CD and 56.0mg KOH mixture (γ-CD and KOH mol ratios
0.125) to be dissolved in 5mL water, in pre-add 3mL methanol to mixed solution, after 50 DEG C of heating water bath 20min,
Solution is taken out, 64mg PEG 2000 are added, stood after half an hour, 3000rpm centrifugation 5min, respectively
Washed with ethanol (10mL × 2), dichloromethane (10mL × 2), by gained crystal, 50 DEG C are dried in vacuo 12h, i.e.,
Second stage micron order CD-MOF crystal (CD-MOF II) is obtained, size is 1-10 μm, such as Figure 11 and 19, production
Rate is 83.0%.
Embodiment 7
Solvent-thermal method prepares second stage micron order CD-MOF crystal
Using the mode of solvent heat, directly gamma-cyclodextrin is mixed with the KOH aqueous solution with a part of organic solvent
System is heated.Weigh 163.0mg γ-CD and 56.0mg KOH mixture (γ-CD and KOH mol ratios
0.125) to be dissolved in 5mL water, in pre-add 3mL methanol to mixed solution, after 50 DEG C of heating water bath 20min,
Solution is taken out, 64mg PEG 10000 are added, stood after half an hour, 3000rpm centrifugation 5min, respectively
Washed with ethanol (10mL × 2), dichloromethane (10mL × 2), by gained crystal, 50 DEG C are dried in vacuo 12h, i.e.,
Second stage micron order CD-MOF crystal (CD-MOF II) is obtained, size is 1-10 μm, such as Figure 12 and Figure 20,
Yield is 87.4%.
Embodiment 8
Solvent-thermal method prepares second stage nanoscale CD-MOF crystal
Using the mode of solvent heat, directly gamma-cyclodextrin is mixed with the KOH aqueous solution with a part of organic solvent
System is heated.Weigh 163.0mg γ-CD and 56.0mg KOH mixture (γ-CD and KOH mol ratios
0.125) to be dissolved in 5mL water, in pre-add 3mL methanol to mixed solution, after 50 DEG C of heating water bath 20min,
Solution is taken out, isometric methanol is added, 64mg PEG 20000 are added, stood after half an hour, 3000
Rpm centrifuges 5min, is washed respectively with ethanol (10mL × 2), dichloromethane (10mL × 2), by gained crystal 50
DEG C vacuum drying 12h, produce second stage nanoscale CD-MOF crystal (CD-MOF Nano), size is
200-500nm, such as Figure 14 and Figure 16, yield are 90.5%.
Embodiment 9
Microwave method prepares second stage micron order CD-MOF crystal
Using the mode of microwave, gamma-cyclodextrin is entered with the KOH aqueous solution with a part of organic solvent mixed system
Row microwave is heated.Weighing 163.0mg γ-CD and 56.0mg KOH mixtures, (γ-CD and KOH mol ratios are
0.125) it is dissolved in 5mL water, in pre-add 3mL methanol to mixed solution, 2450MHz microwave reactor,
After power setting 25W, 50 DEG C of temperature setting, reaction 20min, solution is taken out, 64mg PEG 20000 are added,
Stand half an hour after, 3000rpm centrifugation 5min, respectively with ethanol (10mL × 2), dichloromethane (10mL ×
2) wash, by 50 DEG C of vacuum drying 12h of gained crystal, produce second stage micron order CD-MOF crystal
(CD-MOF II), size is 1-10 μm, such as Figure 21, Figure 22 and Figure 24, and yield is 82.2%.
Embodiment 10
Microwave method prepares second stage nanoscale CD-MOF crystal
Using the mode of microwave, gamma-cyclodextrin is entered with the KOH aqueous solution with a part of organic solvent mixed system
Row microwave is heated.Weighing 163.0mg γ-CD and 56.0mg KOH mixtures, (γ-CD and KOH mol ratios are
0.125) it is dissolved in 5mL water, in pre-add 3mL methanol to mixed solution, 2450MHz microwave reactor,
After power setting 25W, 50 DEG C of temperature setting, reaction 20min, solution is taken out, isometric methanol is added,
64mg PEG 20000 are added, are stood after half an hour, 3000rpm centrifugation 5min, respectively with ethanol (10mL
× 2), dichloromethane (10mL × 2) washing, by 50 DEG C of gained crystal vacuum drying 12h, produce second stage
Nanoscale CD-MOF crystal (CD-MOF Nano), size is 200-500nm, such as Figure 10 and Figure 23, and yield is
90.1%.
Embodiment 11
Supercritical ultrasonics technology prepares second stage micron order CD-MOF crystal
Using the mode of ultrasonic wave, to gamma-cyclodextrin and the KOH aqueous solution and a part of organic solvent mixed system
Carry out Ultrasonic Heating.Weigh 163.0mg γ-CD and 56.0mg KOH mixture (γ-CD and KOH mol ratios
0.125) to be dissolved in 5mL water, in pre-add 3mL methanol to mixed solution, with 40KHz ultrasonic response
Supernatant is taken out after device, power setting 40W, temperature 50 C, reaction 20min, 64mg PEG 20000 are added,
Stand half an hour after, 3000rpm centrifugation 5min, respectively with ethanol (10mL × 2), dichloromethane (10mL ×
2) wash, by 50 DEG C of vacuum drying 12h of gained crystal, produce second stage micron order CD-MOF crystal
(CD-MOF II), size is 1-10 μm, such as Figure 26, and 27 and Figure 29, yield is 79.7%.
Embodiment 12
Supercritical ultrasonics technology quickly synthesizing nano level CD-MOF crystal
Using the mode of ultrasonic wave, to gamma-cyclodextrin and the KOH aqueous solution and a part of organic solvent mixed system
Carry out Ultrasonic Heating.Weigh 163.0mg γ-CD and 56.0mg KOH mixture (γ-CD and KOH mol ratios
0.125) to be dissolved in 5mL water, in pre-add 3mL methanol to mixed solution, with 40KHz ultrasonic response
Supernatant is taken out after device, power setting 40W, temperature 50 C, reaction 20min, 8mL methanol is added, then add
Enter 64mg PEG 20000, stand after half an hour, 3000rpm centrifugation 5min, respectively with ethanol (10mL ×
2), dichloromethane (10mL × 2) is washed, and by 50 DEG C of vacuum drying 12h of gained crystal, is produced second stage and is received
Meter level CD-MOF crystal (CD-MOF Nano), size is 200-500nm, such as Figure 28 and Figure 30, and yield is
85.2%.
Embodiment 13
Second stage micron order CD-MOF crystal carries the preparation of brufen (IBU)
The CD-MOF II dried powder 100.0mg prepared in embodiment 2 are weighed, 2.5mL IBU second is added to
Alcoholic solution (40mgmL-1) in, 37 DEG C, 150rpm shaking tables are interior to be incubated 4d, 3000rpm centrifugation 5min, uses
Ethanol (3mL × 3) is washed, and by 35 DEG C of vacuum drying 12h of gained crystal, carrying drug ratio can reach
12.0% (w/w), such as figure are the infrared spectrogram that CD-MOF II carry IBU.
Embodiment 14
Second stage nanoscale CD-MOF crystal carries the preparation of brufen (IBU) and its microballoon
The CD-MOF Nano dried powder 100.0mg prepared in embodiment 3 are weighed, 2.5mL IBU are added to
Ethanol solution (40mgmL-1) in, 37 DEG C, 150rpm shaking tables are interior to be incubated 4d, 3000rpm centrifugation 5min,
Washed with ethanol (3mL × 3), by 35 DEG C of vacuum drying 12h of gained crystal, carrying drug ratio can reach
13.0% (w/w).
Weigh 50mg and carry medicine CD-MOF Nano, be dispersed in 3mL acetone solns, add 450mg outstanding
Special strange RS100, ultrasonic 10min are allowed to dissolve, and add 120mg aluminum stearates, ultrasonic 5min is uniformly dispersed.
The dispersed phase containing aluminum stearate is added into atoleine (ice bath is to 10 DEG C), by above-mentioned suspension in
Under the conditions of 10 DEG C of ice-water baths, magnetic agitation 30s (500rpm), dispersion machine disperses (10000rpm, 5min),
Obtain S/O/O type emulsions.Above-mentioned emulsion is placed on magnetic stirring apparatus, under 500rpm stirring conditions, by 10 DEG C
35 DEG C are to slowly warm up to, stirring 3h (500rpm, 35 DEG C) is further continued for, most of acetone is removed.By above-mentioned liquid
Body is transferred in 50mL centrifuge tubes, is centrifuged (2000rpm, 5min), is discarded atoleine (upper strata)；Lower floor
Solid is washed 2 times with 30mL n-hexanes, 2000rpm, 5min centrifugations.After washing terminates, dried in fume hood
Overnight, such as the infrared spectrogram that Figure 32 is CD-MOF Nano loads IBU, Figure 35 shows to carry IBU microballoons in PBS7.4
In have obvious slow releasing function.
Embodiment 15
Second stage micron order CD-MOF crystal carries the preparation of Lansoprazole (LPZ)
The CD-MOF II dried powder 200.0mg prepared in embodiment 2 are weighed, 3.6mLLPZ second is added to
Alcoholic solution (14mgmL-1) in, 37 DEG C, 150rpm shaking tables are interior to be incubated 4d, 3000rpm centrifugation 5min, uses
Ethanol (3mL × 3) is washed, by 35 DEG C of vacuum drying 12h of gained crystal, and carrying drug ratio can reach 9.4% (w/w),
If Figure 33 is the infrared spectrogram that CD-MOF II carry LPZ.
Embodiment 16
Second stage nanoscale CD-MOF crystal carries the preparation of Lansoprazole (LPZ) and its microballoon
The CD-MOF Nano dried powder 200.0mg prepared in embodiment 3 are weighed, 3.6mL LPZ are added to
Ethanol solution (14mgmL-1) in, 37 DEG C, 150rpm shaking tables are interior to be incubated 4d, 3000rpm centrifugation 5min,
Washed with ethanol (3mL × 3), by 35 DEG C of vacuum drying 12h of gained crystal, carrying drug ratio can reach
1.6% (w/w).
Weigh 50mg and carry medicine CD-MOF Nano, be dispersed in 3mL acetone solns, add 450mg outstanding
Special strange RS100, ultrasonic 10min are allowed to dissolve, and add 120mg aluminum stearates, ultrasonic 5min is uniformly dispersed.
The dispersed phase containing aluminum stearate is added into atoleine (ice bath is to 10 DEG C), by above-mentioned suspension in
Under the conditions of 10 DEG C of ice-water baths, magnetic agitation 30s (500rpm), dispersion machine disperses (10000rpm, 5min),
Obtain S/O/O type emulsions.Above-mentioned emulsion is placed on magnetic stirring apparatus, under 500rpm stirring conditions, by 10 DEG C
35 DEG C are to slowly warm up to, stirring 3h (500rpm, 35 DEG C) is further continued for, most of acetone is removed.By above-mentioned liquid
Body is transferred in 50mL centrifuge tubes, is centrifuged (2000rpm, 5min), is discarded atoleine (upper strata)；Lower floor
Solid is washed 2 times with 30mL n-hexanes, 2000rpm, 5min centrifugations.After washing terminates, dried in fume hood
Overnight.Such as Figure 34 is the infrared spectrogram that CD-MOF Nano carry LPZ, and Figure 36 shows that carrying LPZ microballoons exists
There is showing sustained release effect in PBS7.4.
Embodiment 17
Embodiment 4,9,11 is repeated, the CD-MOFs crystal of size needed for obtaining is remained to, difference is to change
Become the heat time, the specific time is as follows：
As described in above-mentioned embodiment, the inventive method only need several minutes to a few houres just can complete, with quickly,
The advantages of simplicity, safety, high yield.
The size and yield data of obtained portioned product are summarized in following table in above-described embodiment.
* size conditioning agent is added by 8mg/mL supernatants liquid proportional
All documents referred in the present invention are all incorporated as reference in this application, just as each document
It is individually recited as with reference to such.In addition, it is to be understood that after the above-mentioned instruction content of the present invention has been read,
Those skilled in the art can make various changes or modifications to the present invention, and these equivalent form of values equally fall within this Shen
Please appended claims limited range.
Claims (10)
1. a kind of method for preparing cyclodextrin-metal-organic framework materials, it is characterised in that including step：
(1) the first mixed solution is provided, first mixed solution is the solution containing metal ion and cyclodextrin；
(2) the first organic solvent is added into the first described mixed solution, the second mixed solution is obtained,
Wherein, the volume ratio of first organic solvent and first mixed solution is (0.01-5):1, preferably
For (0.1-2):1, it is most preferably (0.5-1):1；
(3) second mixed solution is pre-processed, pretreated first mixture is obtained, wherein described
Pretreatment be selected from the group：Solvent heat treatment, microwave treatment, ultrasonication or its combination,
(4) optionally, when in the first mixture containing the cyclodextrin-metal-organic framework materials separated out, from institute
State separation in the first mixture and obtain the cyclodextrin-metal-organic framework materials separated out；
(5) when isolating all or part of solution from first mixture, it is used as the 3rd mixed solution；And
The second organic solvent and/or size conditioning agent are added into the 3rd mixed solution, so as to separate out cyclodextrin-metal
Organic framework material；With
(6) optionally cyclodextrin-the metal-organic framework materials separated out in step (5) are separated and/or done
It is dry.
2. the method as described in claim 1, it is characterised in that total time T of step (3) and step (5) is 1
- 12 hours minutes, it is more preferably -3 hours 1 minute, is most preferably -1 hour 1 minute.
3. the method as described in claim 1, it is characterised in that described size conditioning agent is selected from the group：Poly- second
Glycol, PVP, polysorbate, sorbitan mono-laurate, Brij30, polyoxyethylene nonylphenol ether,
Newborn lark A, pluronic, lauryl sodium sulfate, neopelex, dodecyl dimethyl benzyl
Ammonium bromide or its combination.
4. the method as described in claim 1, it is characterised in that the temperature of the pretreatment is 25-100 DEG C, compared with
It is goodly 30-80 DEG C, is more preferably 40-60 DEG C.
5. the method as described in claim 1, it is characterised in that the first described organic solvent and second organic molten
Agent is each independently selected from the following group：Methanol, ethanol, isopropanol, acetone, acetonitrile or its combination.
6. the method as described in claim 1, it is characterised in that the organic bone of cyclodextrin-metal of described preparation
Frame material has the one or more features being selected from the group：
(i) average grain diameter：50 nanometers -50 microns, preferably 100-1000 nanometers (nanoscale) or 1-10 microns it is (micro-
Meter level)；
(ii) in the cyclodextrin-metal-organic framework materials, the mol ratio of CD and metal ion for 1~
1.2:6-10；
(iii) cyclodextrin-metal-organic framework materials described in are pharmaceutically acceptable carrier；
(iv) cyclodextrin-metal-organic framework materials described in have protective effect to thermally labile medicine.
7. the method as described in claim 1, it is characterised in that metal ion in the first described mixed solution
Concentration is 0.05-0.4M, preferably 0.1-0.3M, is more preferably 0.2M；And
The first described mixed solution cyclodextrin and the mol ratio of metal ion are 1：(6-10), preferably 1:8.
8. the method as described in claim 1, it is characterised in that described metal ion is selected from the group：Li+、
K+、Rb+、Cs+、Na+、Mg2+、Cd2+、Sn2+、Ag+、Yb+、Ba2+、Sr2+、Ca2+、Pb2+、La3+Or its group
Close.
9. the method as described in claim 1, it is characterised in that described cyclodextrin-metal-organic framework materials
For preparing the product being selected from the group：Catalyst, adsorbent and pharmaceutical carrier.
10. a kind of method for preparing cyclodextrin-metal-organic framework materials, it is characterised in that including step：
(1) the first mixed solution is provided, first mixed solution is the solution containing metal ion and cyclodextrin；
(2) the first organic solvent is added into the first described mixed solution, the second mixed solution is obtained,
Wherein, the volume ratio of first organic solvent and first mixed solution is (0.01-0.5):1, preferably
Ground is (0.03-0.3):1, it is most preferably (0.05-0.2):1；
(3) second mixed solution is pre-processed, pretreated first mixture is obtained, wherein described
Pretreatment be selected from the group：
(a) solvent heat volatilization is handled；
(b) solvent heat volatilization processing and the combination of any processing mode selected from A groups, wherein A groups include solvent
Heat treatment, microwave treatment, ultrasonication or its combination；
(4) it is mixed from described first when in the first mixture containing the cyclodextrin-metal-organic framework materials separated out
Separation obtains the cyclodextrin-metal-organic framework materials separated out in compound；
Or all or part of solution is isolated from first mixture, it is used as the 3rd mixed solution；And to
The second organic solvent and/or size conditioning agent are added in 3rd mixed solution, so that separating out cyclodextrin-metal has
Machine framework material；With
(5) optionally cyclodextrin-the metal-organic framework materials separated out in step (4) are separated and/or done
It is dry.
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