CN100998872B - Polypeptide medicine intercalation hydrotalcite and its preparation method - Google Patents

Polypeptide medicine intercalation hydrotalcite and its preparation method Download PDF

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Publication number
CN100998872B
CN100998872B CN2007100627696A CN200710062769A CN100998872B CN 100998872 B CN100998872 B CN 100998872B CN 2007100627696 A CN2007100627696 A CN 2007100627696A CN 200710062769 A CN200710062769 A CN 200710062769A CN 100998872 B CN100998872 B CN 100998872B
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preparation
nitrate
anion
peptide
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CN100998872A (en
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卫敏
朱凤婕
段雪
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K38/00—Medicinal preparations containing peptides
    • A61K38/04—Peptides having up to 20 amino acids in a fully defined sequence; Derivatives thereof
    • A61K38/05—Dipeptides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P3/00—Drugs for disorders of the metabolism
    • A61P3/02—Nutrients, e.g. vitamins, minerals
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
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  • Bioinformatics & Cheminformatics (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Veterinary Medicine (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Inorganic Chemistry (AREA)
  • Obesity (AREA)
  • Hematology (AREA)
  • Diabetes (AREA)
  • Nutrition Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Gastroenterology & Hepatology (AREA)
  • Immunology (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Epidemiology (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
  • Peptides Or Proteins (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

A polypeptide medicine intercalated hydrotalcite with high thermal stability and a certain slow-release nature has a chemical formula: (M2+)1-x(M3+)x(OH)a(L-alanyl- L-glutamine)b.mH2O. Its preparing process including codeposition method and ion exchange method, which use microwave hydrothermal step for shorter reaction time, is disclosed.

Description

A kind of polypeptide medicine intercalation hydrotalcite and preparation method thereof
Technical field
The invention belongs to the polypeptide drug technical field, power peptide intercalated houghite and preparation method thereof particularly is provided.Adopt the method for microwave hydrothermal in the preparation process, significantly shortened the crystallization time of coprecipitation and the response time of ion exchange.
Technical background
Peptide is one of important living matter basis, and its effect relates to each link of life process.Peptide affects many important physical biochemical functions in the organism, and in many cases, peptide is being brought into play irreplaceable effect.Known have 100 various active peptides to work in maincenter and peripheral nervous system, cardiovascular system, immune system and intestinal.Peptide also influences intercellular communication for information by the interaction with receptor, and participates in many biochemical processes, as metabolism, pain, regeneration and immunoreation etc.
Yet because chemistry and enzyme sensitivity, peptide is very limited as the application of medicine in clinical treatment.In recent years, the progress in preparation and movement system field has been facilitated several extremely successful polypeptide drugs.These improved main targets are not only the deficiency that overcomes oral artifact utilization rate, but also can avoid the relatively poor subcutaneous injection of patient's compliance.Reported several possible polypeptide route of administration, as oral, lung suction, mucosa or through approach such as subcutaneous administrations, these route of administration need usually specific transporter and (or) infiltration promotes and helps medicine to enter systemic circulation from point of release.
The bimetallic complex hydroxide is called brucite (Layered Double Hydroxides again, be abbreviated as LDHs) be a kind of novel multifunctional stratified material, its chemical stability is good, has strong heat resistanceheat resistant performance, and LDHs laminate species of metal ion and adjustable ratio become, and interlayer anion has interchangeability.Utilize this kind performance to form the supramolecular structure system with the polypeptide that has hydrophilic side group COO-by between the ion exchange interposed layer, this structural system can effectively improve the stability of polypeptide.Brucite with making it become the novel carriers that polypeptide drugs are stored and discharged, helps to develop the new effective route of administration of polypeptide drugs as the function of " molecule container " simultaneously.
The power peptide is by the little peptide of alanine and glutamic acid condensation, is used for the transfusion of parenteral nutrition, is to the replenishing of Freamine, and clinically is used for those patients that need replenish glutamine and comprises that those are in the patient of catabolism and hypermetabolism situation.But still have nothing to do both at home and abroad at present in hydrotalcite stratified material and bonded document of power peptide and patent report.
Summary of the invention
The object of the present invention is to provide a kind of polypeptide medicine intercalation hydrotalcite system and preparation method thereof.The present invention has not only improved the stability of power peptide, and brucite is applied to the storage and the release of polypeptide drugs as a kind of novel carriers, helps to develop the new effective route of administration of polypeptide drugs.
Polypeptide medicine intercalation hydrotalcite of the present invention keeps the Stability Analysis of Structures of polypeptide drugs by the space confinement effect of hydrotalcite layers in its storage process, play the effect of drug effect slow release by the host-guest interaction of brucite laminar composite, brucite also plays the effect of pharmaceutical carrier and control drug release simultaneously.
The formula of polypeptide medicine intercalation hydrotalcite of the present invention is: (M 2+) 1-x(M 3+) x(OH) a(L-alanyl-L-glutamine) bMH 2O.Wherein, M 2+, M 3+Be respectively the bivalence and the trivalent metal cation that are positioned on the main body laminate, the span of X is 0.17-0.34.
The present invention adopts coprecipitation or ion exchange to synthesize the anionic supermolecule stratified material that the polypeptide drugs anion accounts for hydrotalcite layers anion molal quantity sum 20%～80%.
The coprecipitation preparation process is as follows:
A. prepare the mixing salt solution of solubility bivalence magnesium nitrate and solubility trivalent aluminum nitrate, wherein bivalent metal ion concentration is 0.01-1.0M, preferred 0.8-1.6M; Magnesium, aluminum metal ion molar ratio range are 2-4, preferred 2-3;
B. prepare the mixed solution of interlayer object (L-alanyl-L-glutamine) and NaOH;
C. the nitrate mixed solution that steps A is prepared is at N 2Slowly be added drop-wise under the condition of protection in the mixed alkali liquor of step B preparation, stir, the NaOH that utilizes 1-5mol/L with the pH value range regulation of solution to 7-10,60 ℃-70 ℃ crystallization 12-24 hour, adopt and remove CO 2Deionization hot water centrifuge washing to neutral, 50-70 ℃ dry 12-24 hour, obtain power peptide intercalated houghite.
The ion exchange preparation process is as follows:
A. prepare the mixed solution of solubility bivalence magnesium nitrate and solubility trivalent aluminum nitrate, wherein bivalent metal ion concentration is 0.2-1.6M, preferred 0.8-1.6M; Magnesium, aluminum metal ion molar ratio range are 2-4, preferred 2-3;
B. prepare the NaOH aqueous slkali;
C. the nitrate mixed solution that steps A is prepared is at N 2Slowly be added drop-wise under the condition of protection in the alkali liquor of step B preparation, stir, the NaOH that utilizes 1-5mol/L with the pH value range regulation of solution to 8-10,60 ℃-100 ℃ crystallization 12-48 hour, adopt and remove CO 2Deionization hot water centrifuge washing to neutral, obtain nitrate anion brucite precursor;
D. the power taking peptide is soluble in water, adds undried nitrate anion brucite precursor, at 60-70 ℃ of water-bath and N 2Under the condition of protection ion exchange 12-24 hour, adopt to remove CO 2Deionization hot water centrifuge washing to neutral, 50-70 ℃ dry 12-24 hour, obtain the intercalated houghite that the interlayer material is the power peptide.
With above-mentioned prepared material carry out XRD, IR, NMR, elemental analysis shows that the power peptide successfully inserts hydrotalcite layers; Carrying out In-situ XRD, In-situ IR, TG-DTA, TG-MAS characterizes the heat stability that shows this composite and has had and significantly improve; Carry out in-vitro simulated release experiment and show that this composite system can reach certain sustained release performance.
The crystallization process of preferred version coprecipitation or the course of reaction of ion exchange are used the method for microwave hydrothermal.
The invention has the advantages that: adopted the method for microwave hydrothermal in the process of preparation power peptide intercalated houghite, significantly shortened the crystallization time of coprecipitation and the response time of ion exchange; Prepared polypeptide drugs---power peptide intercalated hydrotalcite composite material is owing to utilized the space confinement effect of brucite and the interaction between the Subjective and Objective, thereby have heat stability and certain sustained release performance preferably under normal conditions, help its storage and open up new route of administration.
The specific embodiment
[embodiment 1]
Steps A: with the solid Mg (NO of 3.846g (0.015mol) 3) 26H 2Solid Al (the NO of O and 2.8135g (0.0075mol) 3) 39H 2O is dissolved in 50mL and removes CO 2Deionized water in (solution I); In addition 4g (0.018mol) power peptide and 2.5g (0.0625mol) NaOH are dissolved in 50mL except that CO 2Deionized water in (solution II);
Step B: solution II is placed four-hole bottle, at N 2Under the condition of gas shiled, Yi Bian vigorous stirring, Yi Bian solution I slowly is added dropwise to solution II, about 0.5h drips off.After being added dropwise to complete, its pH value is adjusted to 8 with the NaOH solution of 5mol/L;
Step C:60 ℃ of water-bath 24h;
Step D: with removing CO 2Deionization hot water centrifuge washing to pH be 7,70 ℃ of dry 12h, obtain magnalium type power peptide intercalated hydrotalcite composite material.
By XRD spectra, FT-IR spectrogram, NMR and elementary analysis as can be known, the hydrotalcite layers anion that obtains is a power peptide anion.
[embodiment 2]
The serosity that step B among the embodiment 1 obtains is transferred in the quick counteracting tank of microwave, and at 90 ℃ of microwave heating temperature control 0.5h, the product that obtains is with removing CO 2Deionization hot water centrifuge washing be about 7,70 ℃ of dry 12h to pH.
By XRD spectra, FT-IR spectrogram, NMR and elementary analysis as can be known, the hydrotalcite layers anion that obtains is a power peptide anion.
[embodiment 3]
Steps A: take by weighing 15.384g Mg (NO 3) 26H 2O and 11.2539g Al (NO 3) 39H 2O is dissolved in 100ml and removes CO 2, deionized water preparation mixing salt solution i, other gets 7.2g NaOH and is dissolved in 100ml and removes CO 2, (aqueous slkali ii) and be positioned in the 500mL four-hole boiling flask for deionized water;
Step B: at 70 ℃ of water-baths, N 2Under protection, the strong agitation condition saline solution i slowly is added drop-wise among the aqueous slkali ii, regulates about pH value to 10.0, reaction 40h;
Step C: the product washing and filtering to pH be 7; Keep a large amount of fresh filter cakes in order to ion exchange usefulness, only take out small amount of sample and characterize behind the dry 18h down, obtain NO at 70 ℃ 3-Mg 2Al-LDHs, its Mg 2+/ Al 3+=2;
Step D: get an amount of power peptide and be dissolved in 200mL and remove CO 2, deionized water and place the 500mL four-hole boiling flask, get the filter cake that an amount of step C obtains again and add wherein, regulating pH is 9;
Step e: at N 2Protection, strong agitation, ion exchange 24h under 60 ℃ of conditions of temperature control, the product that obtains spends CO 2, deionized water wash centrifugalize 4 times, will be deposited in the vacuum drying oven dryly, can obtain interlayer and contain the anionic laminar composite of power peptide.
By XRD spectra, FT-IR spectrogram, NMR and elementary analysis as can be known, the hydrotalcite layers anion that obtains is a power peptide anion.
[embodiment 4]
The mixed solution that step D among the embodiment 3 obtains is transferred in the quick counteracting tank of microwave, and at 90 ℃ of microwave heating temperature control 0.5h, the product that obtains is with removing CO 2Deionization hot water centrifuge washing be about 7,70 ℃ of dry 12-24h to pH.
By XRD spectra, FT-IR spectrogram, NMR and elementary analysis as can be known, the hydrotalcite layers anion that obtains is a power peptide anion.
[embodiment 5]
Steps A: the mixing salt solution i in embodiment 3 steps A is added among the aqueous slkali ii under the condition of high-speed stirred fast, stir after 20 minutes, the product that obtains spends CO 2, deionized water wash centrifugalize 4 times;
Step B: get precipitation that an amount of steps A obtains and an amount of power peptide and be dissolved in CO 2, in the deionized water, transferring pH is 8;
Step C: the solution that step B obtains is transferred in the autoclave 90 ℃ of reactions of constant temperature 16h;
Step D: product spends CO 2, deionized water wash centrifugalize 4 times, will precipitate drying at room temperature in a vacuum, can obtain interlayer and contain the anionic laminar composite of power peptide.
By XRD spectra, FT-IR spectrogram, NMR and elementary analysis as can be known, the hydrotalcite layers anion that obtains is a power peptide anion.

Claims (2)

1. the preparation method of a polypeptide medicine intercalation hydrotalcite is characterized in that, adopts coprecipitation synthetic polypeptide medicaments power peptide anion to account for the anionic supermolecule stratified material of interlayer anion molal quantity sum 20～80%; Its concrete steps are:
A. prepare the mixing salt solution of solubility bivalence magnesium nitrate and solubility trivalent aluminum nitrate, wherein bivalent metal ion concentration is 0.8-1.6M, and magnesium, aluminum metal ion molar ratio range are 2-3;
B. prepare the mixed solution of interlayer object L-alanyl-L-glutamine and NaOH;
C. the nitrate mixed solution that step a is prepared is at N 2Slowly be added drop-wise under the condition of protection in the mixed alkali liquor of step b preparation, stir, the NaOH that utilizes 1-5mol/L to 7-10, transfers to the pH value range regulation of solution in the quick counteracting tank of microwave then, 90 ℃ of microwave heating temperature controls 0.5 hour, adopts and removes CO 2Deionization hot water centrifuge washing to neutral, 50-70 ℃ dry 12-24 hour, obtain power peptide intercalated houghite.
2. the preparation method of a polypeptide medicine intercalation hydrotalcite is characterized in that, adopts ion exchange synthetic polypeptide medicaments power peptide anion to account for the anionic supermolecule stratified material of interlayer anion molal quantity sum 20～80%, and its concrete steps are:
(1) mixed solution of preparation solubility bivalence magnesium nitrate and solubility trivalent aluminum nitrate, wherein bivalent metal ion concentration is 0.8-1.6M, magnesium, aluminum metal ion molar ratio range are 2-3;
(2) preparation NaOH aqueous slkali;
(3) nitrate mixed solution that step (1) is prepared is at N 2Slowly be added drop-wise under the condition of protection in the alkali liquor of step (2) preparation, stir, the NaOH that utilizes 1-5mol/L to 8-10, at 60-100 ℃ of crystallization 12-48 hour, adopts the pH value range regulation of solution to remove CO 2Deionization hot water centrifuge washing to neutral, obtain nitrate anion brucite precursor;
(4) the power taking peptide is soluble in water, adds undried nitrate anion brucite precursor, transfers to then in the quick counteracting tank of microwave, 90 ℃ of microwave heating temperature controls 0.5 hour, adopts and removes CO 2Deionization hot water centrifuge washing to neutral, 50-70 ℃ dry 12-24 hour, obtain the intercalated houghite that the interlayer material is the power peptide.
CN2007100627696A 2007-01-16 2007-01-16 Polypeptide medicine intercalation hydrotalcite and its preparation method Expired - Fee Related CN100998872B (en)

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CN101530621A (en) * 2009-03-18 2009-09-16 北京化工大学 Oxidation resisting dipeptide medicament intercalated houghite and preparation method thereof
CN105214102B (en) * 2015-10-22 2018-10-23 北京化工大学 A kind of supermolecule composite optothermal reagent and its application in terms of photo-thermal therapy and near infrared imaging
CN107774283B (en) * 2017-10-24 2020-02-14 中南大学 Molybdenum disulfide intercalated hydrotalcite composite material and preparation method and application thereof
CN112587669B (en) * 2020-04-23 2023-01-13 复旦大学附属中山医院青浦分院 Ac-SDKP-LDH nano preparation and preparation method and application thereof
CN112806357B (en) * 2021-01-15 2022-12-20 中国农业大学 Mepighiaum controlled-release agent and application thereof in chemical regulation of crops

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