CN1810778A - Prepn of supermolecular structure nanometer reactor - Google Patents

Prepn of supermolecular structure nanometer reactor Download PDF

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Publication number
CN1810778A
CN1810778A CNA2006100113467A CN200610011346A CN1810778A CN 1810778 A CN1810778 A CN 1810778A CN A2006100113467 A CNA2006100113467 A CN A2006100113467A CN 200610011346 A CN200610011346 A CN 200610011346A CN 1810778 A CN1810778 A CN 1810778A
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preparation
hour
hydrotalcite
halfcystine
nitrate
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CN100383115C (en
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段雪
卫敏
史志宇
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Priority to PCT/CN2006/001105 priority patent/WO2007095786A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/16—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by oxidation of thiols, sulfides, hydropolysulfides, or polysulfides with formation of sulfo or halosulfonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K5/00—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof
    • C07K5/02—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing at least one abnormal peptide link
    • C07K5/0215—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing at least one abnormal peptide link containing natural amino acids, forming a peptide bond via their side chain functional group, e.g. epsilon-Lys, gamma-Glu

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Genetics & Genomics (AREA)
  • Biochemistry (AREA)
  • Biophysics (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Molecular Biology (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Peptides Or Proteins (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

The present invention provides preparation process of supermolecular structure nanometer reactor and belongs to the field of organic-inorganic composite material preparing and applying technology. Mercaptan compound is first inserted into hydrotalcite layers by means of co-precipitation or ion exchange process; and mercaptan compound is then oxidized with hydrotalcite as molecular reactor and through intercalating hydrotalcite with small amount of L-cysteine, adding CO2-eliminated deionized water, stirring under N2 protection for 1-3 hr for high dispersing, dropping small amount of oxidant to react for 0.5-1 hr, sucking filtering, washing, and vacuum drying at normal temperature for 24-48 hr to obtain oxidized product. The present invention is superior in that the laminated nanometer space of hydrotalcite is used as the reactor for oxidizing mercaptan compound so as to obtain single oxidized product.

Description

A kind of preparation of supermolecular structure nanometer reactor
Technical field
The invention belongs to organic inorganic composite materials preparation and applied technical field thereof, a kind of preparation of supermolecular structure nanometer reactor particularly is provided.Relate to a kind of intercalation configuration hydrotalcite composite material of preparation and adopt the interlevel oxidation method to study its reactor characteristic.
Background technology
The assembling that organism and vital process are the various biomolecules of product of evolving in 1 years by different levels by microcosmic to macroscopic view. spontaneously formed complexity but accurately assembly system realized each species specific biological function and other functions.The synthetic molecules that studies show that of modern supramolecule science can have this spontaneous assembly behavior equally.Adopt the bionical assembly behavior of process to prepare the supramolecule biomimetic material and the micro-system of structure and function bionics according to bionics principle, can simulate organism and realize multi-functional integrated and related preparation intelligent material or molecule machine: can bionical realization physiologically acceptable and biological function prepares bio-medical material and device provides unlimited innovative space and development space for the modern material the reach of science.Wherein, be expected making a breakthrough aspect analogue enztme and the molecular reactor by realizing molecule and supramolecular assembling and compound in nanometer and micro-meter scale.Natural enzyme is that the high specific of process nature long-term evolution acquisition and the biological microbody of high catalytic activity one of are.Because it and substrate specific molecule recognition reaction, the bionical microbody that becomes people's first-selection the earliest one of is.To the molecular recognition of enzyme and the manual simulation of catalysis, still be that enzymatic structure and function aspects are all being brought into play crucial effect in the organic evolution process of understanding enzyme own.
Sulphur has vital role in the life entity metabolism, and halfcystine (CySH), homocysteine (Hcy), gsh (GSH) are most important mercaptan in the life chemistry.These mercaptan contain the active thin base-SH with reductibility, easy oxidized deoxidation, and this specific structure makes it become main free-radical scavengers in the body.Many free radicals meeting damaging cells films that the body intracellular metabolic produces, the invasion and attack life macromolecule promotes body aging, and induced tumor or atherosclerotic generation.These mercaptan can be removed free radical as reductive agent important in the body, play strong provide protection.For example, in cell, generate small amount of H 2O 2The time, GSH is under the effect of Selenoperoxidase, H 2O 2Be reduced into H 2O, himself is oxidized to GSSG, and GSSG accepts H and is reduced into GSH by under the glutathione reductase katalysis that is present in liver and the red corpuscle, makes the cleaning reaction of interior free yl can continue to carry out.
Document J.Darkwa, C.Mundoma, R.H.Simoyi, J.Chem.Soc., Faraday Trans., 1998,94,1971 couples of L-halfcystines and BrO 3 -, Br 2And H 2O 2Oxidising process done comparatively detailed research, find the L-halfcystine under conditions in vitro with oxidant reaction, generate different oxidation productss with the difference of oxygenant add-on.
Summary of the invention:
The object of the present invention is to provide a kind of preparation of supermolecular structure nanometer reactor, solved the difficult problem of oxidation products single selective.
The present invention utilizes the intercalation of hydrotalcite with the thio-alcohol material, adopts coprecipitation method or ion exchange method to be inserted into hydrotalcite layers as L-halfcystine, gsh, and then adds oxygenant, utilizes hydrotalcite as molecular reactor mercaptan to be carried out oxidation; The step of oxidation is: at first get L-halfcystine intercalated houghite, add and take off CO 2Deionized water is at N 2Protection was stirred 1-3 hour down, made its high dispersing; Be 1: 2～3: 1 by oxygenant and L-halfcystine mol ratio then, dropping oxidizing agent, after question response 0.5-1 hour, filtering and washing under the normal temperature vacuum-drying 24-48 hour, obtains product after the oxidation.
Thio-alcohol material of the present invention is L-halfcystine or gsh, and described oxygenant is hydrogen peroxide and bromine water.Described thio-alcohol material is L-halfcystine or gsh, and described oxygenant is hydrogen peroxide and bromine water.
Concrete processing step is as follows:
Coprecipitation method:
A. prepare the mixing solutions of solubility divalence magnesium nitrate and solubility trivalent aluminum nitrate, wherein divalent-metal ion concentration is 0.8-1.6mol/L.
B. prepare the mixing solutions of interlayer object (L-halfcystine) 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 10-11,60 ℃-70 ℃ crystallization 12-48 hour, adopt except that CO 2Deionization hot water centrifuge washing to neutral, 70 ℃-100 ℃ dry 12-24 hour, obtain L-halfcystine intercalated houghite.
Ion exchange method:
A. prepare the mixing solutions of solubility divalence magnesium nitrate and solubility trivalent aluminum nitrate, wherein divalent-metal ion concentration is 0.8-1.6mol/L.
B. prepare the NaOH alkaline solution
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 lye 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 except that CO 2Deionization hot water centrifuge washing to neutral, obtain nitrate radical hydrotalcite precursor.
D. it is soluble in water to get gsh, adds undried nitrate radical hydrotalcite precursor, at 20 ℃ of ion-exchange 12-24 hours, adopts and removes CO 2Deionization hot water centrifuge washing to neutral, 70 ℃-100 ℃ dry 12-24 hour, obtain the intercalated houghite that the interlayer material is a gsh.
The oxidation of intercalated houghite:
A. get L-halfcystine intercalated houghite, add and take off CO 2Deionized water is at N 2Protection was stirred 1-3 hour down, made its high dispersing;
B. be 1: 2～3: 1 by oxygenant and L-halfcystine mol ratio, dropping oxidizing agent, after question response 0.5-1 hour, filtering and washing under the normal temperature vacuum-drying 24-48 hour, obtains product after the oxidation;
With product after the intercalated houghite that obtains and the oxidation carry out XRD, FT-IR, Raman, 13C NMR and elemental analysis show that object enters interlayer, form the hydrotalcite intercalation material that crystalline phase is single, structure is consistent.After various oxygenant oxidations, the interlayer object is success and oxygenant generation redox reaction in interlayer confinement space, obtains the intercalated houghite of oxidation products, has realized the function of hydrotalcite as nano-reactor.
The invention has the advantages that: the laminar nano space of adopting hydrotalcite can obtain single oxidation products as the reactor that mercaptan oxidation reacts, and has overcome to obtain multiple oxidation products, the shortcoming of reaction product poor selectivity in the common response device.
Embodiment
Embodiment 1
Steps A: with the solid Mg (NO of 20.48g (0.08mol) 3) 26H 2Solid Al (the NO of O and 15.00g (0.04mol) 3) 39H 2O is dissolved in 50mL and removes CO 2Deionized water in (solution 1); In addition 10.64g (0.08mol) L-halfcystine and 14.08g (0.352mol) NaOH are dissolved in 50mL except that CO 2Deionized water in (solution 2).
Step B: solution 2 is placed there-necked flask, at N 2Under the condition of gas shiled, Yi Bian vigorous stirring, Yi Bian solution 1 slowly is added dropwise to solution 2, dripped off in about 2 hours.
Step C: after being added dropwise to complete, its pH value is adjusted to 10, reflux 6 hours with the NaOH solution of 5mol/L.
Step D: with the freshly prepd CO that removes 2Deionization hot water centrifuge washing be about 7,70 ℃ of dryings 24 hours to pH, obtain magnalium type halfcystine intercalated houghite material.
By XRD spectra, FT-IR spectrogram, thermogravimetric spectrogram and ultimate analysis as can be known, the hydrotalcite layers negatively charged ion that obtains is a L-halfcystine acid group, is the hydrotalcite intercalation material that a kind of crystalline phase is single, structure is consistent.
Step e: get 1g L-halfcystine intercalated houghite, add in the there-necked flask, add 50ml and take off CO 2Deionized water, N 2Under the protection, violent stirring 3h makes its high dispersing.Slowly drip a little 1%H then 2O 2, behind the question response 1h, filtering and washing, vacuum-drying 48h under the normal temperature obtains product after the oxidation.
By XRD, FT-IR, Raman, 13C NMR and elemental analysis show that as can be known the oxidation products that obtains is the Gelucystine intercalated houghite, but its interlamellar spacing is less than the Gelucystine intercalated houghite that directly prepares with coprecipitation method.
Embodiment 2:
L-halfcystine intercalated houghite preparation method is with embodiment 1.
Get 1g L-halfcystine intercalated houghite, add in the there-necked flask, add 50ml and take off CO 2Deionized water, N 2Under the protection, violent stirring 3h makes its high dispersing.Slowly drip a little Br then 2([Br 2]/[CySH]=0.5), behind the question response 1h, filtering and washing, vacuum-drying 48h under the normal temperature obtains product after the oxidation.
By XRD, FT-IR, Raman, 13C NMR and elemental analysis demonstration are as can be known, and be different with open system, owing to be subjected to hydrotalcite layers confinement spatial to influence Br 2The diffusion difficulty that becomes comparatively.Br 2The oxidation products of oxidation hydrotalcite layers halfcystine does not change with the oxygenant consumption, and oxidation products is a cysteic acid.

Claims (4)

1, a kind of preparation of supermolecular structure nanometer reactor, it is characterized in that: utilize the intercalation of hydrotalcite to adopt coprecipitation method or ion exchange method to be inserted into hydrotalcite layers the thio-alcohol material, and then the adding oxygenant, utilize hydrotalcite mercaptan to be carried out oxidation as molecular reactor; The step of oxidation is: at first get L-halfcystine intercalated houghite, add and take off CO 2Deionized water is at N 2Protection was stirred 1-3 hour down, made its high dispersing; Be 1: 2～3: 1 by oxygenant and L-halfcystine mol ratio then, dropping oxidizing agent, after question response 0.5-1 hour, filtering and washing under the normal temperature vacuum-drying 24-48 hour, obtains product after the oxidation; Described thio-alcohol material is L-halfcystine or gsh, and described oxygenant is hydrogen peroxide and bromine water.
2, in accordance with the method for claim 1, it is characterized in that: the processing step of described coprecipitation method is:
The mixing solutions of a, preparation solubility divalence magnesium nitrate and solubility trivalent aluminum nitrate, wherein divalent-metal ion concentration is 0.8-1.6mol/L;
The mixing solutions of b, preparation interlayer object L-halfcystine and NaOH;
C, with the nitrate mixed solution of step a preparation 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 10-11, at 60-70 ℃ of crystallization 12-48 hour, adopts the pH value range regulation of solution except that CO 2Deionization hot water centrifuge washing to neutral, 70 ℃-100 ℃ dry 12-24 hour, obtain L-halfcystine intercalated houghite.
3, in accordance with the method for claim 1, it is characterized in that: the processing step of described ion exchange method is:
The first step: the mixing solutions of preparation solubility divalence magnesium nitrate and solubility trivalent aluminum nitrate, wherein divalent-metal ion concentration is 0.8-1.6mol/L;
Second step: preparation NaOH alkaline solution;
The 3rd step: with the nitrate mixed solution of step the first step preparation at N 2Be added drop-wise under the condition of protection in the alkali lye of step the second step 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 except that CO 2Deionization hot water centrifuge washing to neutral, obtain nitrate radical hydrotalcite precursor.
4, in accordance with the method for claim 1, it is characterized in that: the processing step of described ion exchange method is: it is soluble in water to get gsh, adds undried nitrate radical hydrotalcite precursor, ion-exchange 12-24 hour, adopts and removes CO 2Deionization hot water centrifuge washing to neutral, 70 ℃-100 ℃ dry 12-24 hour, obtain the intercalated houghite that the interlayer material is a gsh.
CNB2006100113467A 2006-02-22 2006-02-22 Prepn of supermolecular structure nanometer reactor Expired - Fee Related CN100383115C (en)

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PCT/CN2006/001105 WO2007095786A1 (en) 2006-02-22 2006-05-26 A method for preparing a supermolecular-structure nano-reactor

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008086716A1 (en) * 2007-01-16 2008-07-24 Beijing University Of Chemical Technology Layered double hydroxide complex inserted by dipeptiven and the preparation method thereof
CN110898797A (en) * 2019-11-27 2020-03-24 清华大学深圳国际研究生院 Preparation method of layered double hydroxide, layered double hydroxide and application

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114956144A (en) * 2022-06-07 2022-08-30 秦迎 Hydrotalcite single-layer nano material and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1189427C (en) * 2002-06-24 2005-02-16 北京化工大学 Method for assembling anion type supramolecular intercalation structure material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008086716A1 (en) * 2007-01-16 2008-07-24 Beijing University Of Chemical Technology Layered double hydroxide complex inserted by dipeptiven and the preparation method thereof
CN110898797A (en) * 2019-11-27 2020-03-24 清华大学深圳国际研究生院 Preparation method of layered double hydroxide, layered double hydroxide and application

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