CN103805592A - Preparation method of biologic and natural nanoscale inorganic carrier material - Google Patents
Preparation method of biologic and natural nanoscale inorganic carrier material Download PDFInfo
- Publication number
- CN103805592A CN103805592A CN201310670571.1A CN201310670571A CN103805592A CN 103805592 A CN103805592 A CN 103805592A CN 201310670571 A CN201310670571 A CN 201310670571A CN 103805592 A CN103805592 A CN 103805592A
- Authority
- CN
- China
- Prior art keywords
- preparation
- technology
- carrier
- natural
- enzyme
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Abstract
The invention discloses a preparation method of a biologic and natural nanoscale inorganic carrier material. The preparation method comprises a supramolecular assembly chemical modification technology process on the basis of the micronization and vapor activation process. The preparation method is characterized in that a natural and environmentally-friendly substrate naming HP (Highporperty) material provided meets the ideal conditions of a carrier in the immobilization technology and also has the advantages that (1) an unique natural one-dimensional nanoparticle material and a nanoscale layered/ chained microstructure are provided; (2) thirteen of the fourteen trace life elements represented by iodine, selenium, zinc and iron are enriched; (3) three performances, namely, inertia, acid/alkali resistance and resistance to high temperature (1,300 DEG C), are realized. The preparation method has the advantages that the micronizing and purifying, acidic-thermal-mechanical chemical activating, supramolecular assembly chemical modifying and other technical processes are carried out by the hydrodynamic flexible depolymerizing, dispersing, separating and purifying technical process, and thus a high-purity and micro-nano biomolecule immobilization carrier (support) material can be prepared.
Description
Technical field
The present invention relates to the biomolecules such as a kind of enzyme, cell, ubcellular, microorganism and implement the preparation method of biological natural nano level inorganic carrier (upholder) material of immobilization technology and application.
Background technology
Bio-immobilized technology (immobilization of biological techology) is an emerging technology in modern biological project field, it is a kind of important means that the biology such as immobilized enzyme or immobilized cell obtains more extensively, more effectively uses, therefore, bio-immobilized technology is a core technology in modern biotechnology and industrialization link thereof.Wherein, along with the development of immobilization technology, immobilized biomolecule is more and more urgent to the demand of carrier, and the development of novel carriers is more and more important, and, research Showed Very Brisk.
Inorganic lamellar material, as the prop carrier of biomolecules, has the incomparable advantage of many other inorganic carriers, is the another new focus of recent Material Field to its research.Inorganic lamellar material has the special laminate structure of nano level, can there is corresponding variation along with embedding bulk of molecule in laminate structure constituting layer pitch space, it not only provides a prop carrier for biomolecules, and provides a nano level reaction compartment for biochemical reaction.This space; not only can effectively protect biomolecules; and; the spacious edge beam of stratified material; also can not stop up the signal transmission of biomolecules; show the moral character of excellent carrier, except high stability and catalytic activity enzyme immobilization as excellent carrier, also will there is potential using value in cell, ubcellular, microorganism and bio-sensing, biological label, medicament slow release field.
Life science and biotechnology and Nanometer scale science and technology also claim two large main flows of scientific technological advance in this century.The research of life science is the chief component of human activity process, and Nanometer scale science and technology is one of recent most active field, and the research in these two fields and the biological nano technology of applying combination, be noticeable focus naturally.Material and Materials science are guide and the bases of scientific and technological progress and industry development, can just become the focus in focus for the material that nanometer biotechnology provides support carrier.
The activity that enzyme, cell, ubcellular and microorganism exist and stability and catalytic performance are very responsive to environment, especially enzyme.The efficient single-minded catalytic performance of enzyme, causes people's extensive concern already.But enzyme is the application in biochemical reaction as catalyzer, also has certain limitation.Because enzyme is protein, its higher structure is very responsive to environment, various factors all likely makes enzyme loss of activity as physical factor (temperature, pressure, electromagnetic field), chemical factor (oxidation, reduction, organic solvent, heat, metal ion, pH) and biotic factor (enzyme liberating), even under optimum condition, enzyme also can inactivation, along with the prolongation in reaction times, speed of reaction declines, and reclaims difficulty after reaction.Therefore, to how keeping this efficient single-minded catalytic activity of enzyme, can overcome again the limitation of enzyme in application is the target that people dream of, and numerous scholars advance wave upon wave and made extensive work in this field, and final discovery comparatively effectively solution route is carry out enzyme fixing.
The immobilization technology growing up the 1950's, makes immobilized enzyme compared with resolvase, has the following advantages:
(1) be easy to separate;
(2) improved the stability of enzyme;
(3) improved the efficiency of enzyme, reduced costs;
(4) production technique develops into serialization, automatization by original batch process.
The fixing means of enzyme is a lot, according to the chemical reaction type for combination, is broadly divided into three classes: non-covalent combined techniques, Chemical bond method and entrapping method.
Although immobilized enzyme has the incomparable advantage of a lot of resolvases, but enzyme immobilization has very high requirement to solid support material, as there being binding ability of good intensity, good thermostability, chemical stability, good antimicrobial and enzyme etc.Can the price of solid support material also directly affect immobilized enzyme and really be applied in actual production.
Owing to being difficult to find desirable solid support material, add enzyme and in immobilization process, inevitably lose part vigor, even when fixing means must not be at that time, can loss count absolutely greatly the reasons such as vigor, up to the present, also only have tens kinds of immobilized enzymes to be applied in production, therefore, develop easier, more applicable process for fixation and the solid support material of excellent performance, make more immobilized enzyme and cell obtain plant-scale application, remain the target that pursue in this field.
As far back as the sixties in 20th century, be easy to get based on layer silicate mineral raw material, cheap, as selected enzyme supporter stratiform material, and attract scholar's concern.Due to technical limitation at that time, educational circles has only utilized the adsorption of outside surface, does not make full use of stratified material internal surface area and interlayer provide protection, thereby, do not cause that scientific circles note widely and apply.Along with the rise of the later stage nano science eighties in last century, the raising of nano-intercalation technology, lift-off technology, stratified material causes the very big interest of people again as enzyme prop carrier, and sums up following advantage:
(1) can utilize stratified material more, but also the performances such as tool is optical, electrical, magnetic;
(2) interlamellar spacing of stratified material can be adjusted according to guest molecule size, to the not significantly disturbance of structure of fixing artifact molecule;
(3) stratified material, for fixing artifact molecule provides a protectiveness microenvironment, can effectively suppress biomolecules degraded.
So, utilize the biologic strut carrier of stratified material constructing function and matrix material to become a study hotspot in present material field.
HP material, except possessing the general advantage of above-mentioned stratified material, also has following 3 speciality:
1. natural 1-dimention nano particulate matter;
2. have a microtexture of layer, chain, fibrous crystals structure and nano grade pore, cave passage;
3. containing 13 kinds of 14 kinds of the essential nutritional trace elements of the organism take iodine, selenium, zinc, iron as representative.
These speciality, make stratified material in nanoscale, structure, structural strength, there is the raising of matter with aspects such as biological nutrition material are provided, it is not only increased dramatically at active biological enzyme high stability catalysis, and obtain important application, and be good biochemical reactor, the excellent material of biosensor at cell, semicell, microorganism field.
Summary of the invention
In order to address the above problem, the object of the invention is to the preparation method of the biological natural nano level inorganic carrier material that proposes the biomolecules enforcement immobilization technologies such as a kind of enzyme, cell, ubcellular, microorganism and application.
For achieving the above object, technical scheme that the present invention adopts is as follows:
The biomolecules such as enzyme, cell, ubcellular, microorganism are implemented a preparation method for the biological natural nano level inorganic carrier material of immobilization technology and application, it is characterized in that this preparation method has comprised the Supramolecular Assembling chemical modification technique technique on miniaturization, activating technology technique basis.
Further, the method comprises Supramolecular Assembling chemical modification technique technique.
Further, the method idiographic flow is: miniaturization, activation, modification technology technique.
Bio-immobilized technology (immobilized biotechnology) is the important new technology of modern bio-science field, it is by chemistry and the means of physics, free enzyme or cell, microorganism to be positioned in localized area, makes it keep active and also can recycle.The advantages such as fixed biologically technology tool biological density is high, be swift in response, biologically run off less, product is easily separated and reaction process is easy to control, be a kind of efficient low-consume, running management easily and there is the new technology of application future.
Bio-immobilized technology except carrier free is fixing, all the other no matter absorption method, covalent coupling method, crosslinking, entrapping method and system hold back, all have close association with carrier.Desirable fixation support should be: (1) is to enzyme, cell and microorganism nontoxicity; (2) good, the stable in properties of mass-transfer performance, be difficult for by biological decomposition; (3) intensity is high, the life-span is long; (4) cheap etc.
Natural substrates environmental friendliness HP provided by the present invention (High porperty) material, not only possess the desirable above-mentioned condition of immobilization technology carrier, also there is unique (1) natural 1-dimention nano particulate matter and nano-scale layers, chain microtexture; (2) be rich in 13 kinds in 14 kinds of life trace elements take iodine, selenium, zinc, iron as representative; (3) inertia, acid and alkali-resistance; Three performances of high temperature resistant (1300 ℃).Realize the technical matters such as fine and purifying, " acid-heat-mechanical force and chemical " activation, Supramolecular Assembling chemical modification through the flexible depolymerization dispersion of water power and purification technique technique, prepare high-purity, micro-nano biomolecule mobilization carrier (upholder) material.And can be used as the functional material of bio-reactor, biosensor.For the general character key-functional materials problem that solves biological industry development provides technical support, for development biological industry provides guide and basis.
Embodiment
Describe the present invention in detail below in conjunction with specific implementation method, be used for explaining the present invention in exemplary embodiment and description of the present invention, but not as a limitation of the invention.
embodiment 1:
1, the peeling off and recombinating of HP material
Between the microstructure layer of HP material, with weak electrostatic force or Van der Waals force combination, when in the time that interlayer is introduced molecule or ion, can cause that interfloor distance (interlamination region) increases; In the time increasing to a certain degree, layer by layer between reactive force weaken gradually to last disappearance, cause stratified material to exist in solution with chip slice status, this process becomes peeling off of stratified material.Then, by the electrostatic attraction of biomolecules and laminated structure unit, carry out interfacial assembly, reach and the restructuring of introducing biomolecules.The motivating force of peeling off rear restructuring is the electrostatic attraction of biomolecules and laminated structure unit, and its positive and negative charge of being with is to regulate and control by system pH, becomes the important factor that affects composite structure and performance.Peel off intercalation restructuring condition relatively gentle, and can obtain Stability Analysis of Structures and the product little to bio-molecular damage, thereby, enjoy the favor of bio industry.
HP material has certain swelling property, laminate electric density is low, interlaminar action power a little less than, in water medium, the swelling peeling of spontaneous appearance, shows high dispersive characteristic.Self-expanding based on HP material in water medium is peeled off character, and biomolecules and comparatively large vol polymer just can enter interlayer by carrying out ion-exchange in interlamination region.But the only spontaneous separability of HP material lacks artificial design and technology cutting, and concentration is low, the guest molecule limited amount that can assemble, thereby application is still restricted.
For above limitation, preparation embodiment to bio-carrier materials such as organized enzymes is following technical measures: reach the Optimal performances such as micro-nanoization, bigger serface, high reactivity center, high dispersive and abundant consistency, and become high-quality biomolecule carrier material.
(1) the flexible ultramicronising technical matters (comprise and adopt softening method) of pulverizing of the water medium of HP material.
By preparing ultra micro HP material support, adopt the flexible pulverizing of water medium, carry out working procedure parameter adjustment, reaching design granularity is the index of 800nm-1 μ m, make biomolecules not enter hole and passage, biomolecules is fixed on carrier surface, eliminate by hole at caused effect of intraparticle diffusion, because the adsorption surface area after ultramicronising is large, make biomolecules very easily be adsorbed in carrier surface, in obtaining the biomolecules such as high specific acitivity very and stable immobilized enzyme, solve the low problem of biomolecules concentration.
(2) " heat-acid-mechanical force and chemical " of HP material activation promotes biomolecules bearing capacity
In order to improve assembling guest molecule quantity, HP material is adopted to the system technical matters of " acid activation-thermal activation-Mechanochemical Activation ", under 12% volume percent Hcl condition, soak and drench HP material, remove impurity and " H+ " displacement " Al+3 " " Mg+2 " etc., make the active raising of surface and negative electricity, thereby increase the carrying to guest molecule heavy dose; By the thermal treatment activation of 250 ℃ ± 10 ℃, HP material internal surface is held to broad variety water to be driven, vacate the inside and outside specific surface area occupying for water molecules, the inside and outside specific surface area of HP material is significantly increased, also further increased considerably thereby make to assemble biomolecules quantity; " Mechanochemical Activation " is that application ball mill device or electricity grind at normal temperatures, through the mechanical force and chemical reaction of 4h, in HP material material impacting process, material surface is because the destruction of balance lattice produces a large amount of lattice imperfections, these fault locations are active centre of charge unbalance, are the bases of improving specific activity and stability.
(3) modification of inorganic supermolecular intercalation Chemical assembly HP material
HP material, as high-performance biomaterial, forms matrix material with biopolymer, first will solve consistency and dispersion problem, otherwise cannot bring into play its corresponding function, and even its interpolation, intervention, compound, become introducing defect on the contrary.HP material is the polarity particulate matter of " hydrophilic ", compatible with biopolymer and dispersed, just must carry out modification, is exactly that to change " hydrophilic " be " hydrophobic " on conversational implication.
Apply inorganic supermolecular intercalation assembling chemical technology, adopt soft electrochemical conditions, utilize PH material layer, chain, mesoporous structure, application alkylammonium salt properties-correcting agent, complete the material modification to HP, realize the object of HP material as polymer composite, with biological substrate highly compatible, dispersed in biological substrate, reach effective catalysis high stable and biophysiological function.
Supramolecular chemistry is the chemistry that forms molecule aggregates based on intermolecular non-covalent interaction.Supramolecular chemistry is different from the traditional molecular chemistry that builds molecule based on atom, it is the chemistry of the above level of molecule, it is mainly studied two or more molecules and interacts by intermolecular non-covalent weak bond, as hydrogen bond, Van der Waals force, dipole-dipolar interaction, hydrophilic/hydrophobic interacts and acts synergistically and structure and the function of generation molecule aggregates between them, and unit molecule is expanded to molecular assembly.Open up the brand-new development space of creating novel substance and novel material and new function.
" molecular self-assembling " is two most important key elements with " molecular recognition and site identification ".Under " molecular self-assembling " refers to and do not instruct or handle by external force, the system constructing directly being undertaken by non-covalent interaction.Molecular recognition and site identification refer to take particular space environment as prerequisite, make several identical or different Intermolecular Forcess act synergistically on certain position, form the contact of catalysis." molecular recognition " can be defined as certain given acceptor to Substrate selective binding and produce the process of certain specific function, and molecular recognition is the basis of carrying out information processing in supramolecule level.The research of nano-supermolecule is a supramolecular field of completely newly, opening up.
Intercalation assembling chemical is to keep, under the prerequisite of stratiform main body framework, introducing functional object, forms and has Subjective and Objective feature intercalation configuration and supramolecular chemistry assembling.Intercalation assembling chemical be supramolecular chemistry building block principle instruct lower by intercalation assemble and molecule compound, the functional materials of optimizing with a kind of more convenient, economic means processability, wherein, comprise lamellar precursor, the identification of laminated body to interlayer object, the important content such as chemical reaction behavior and manipulation of confinement space in layer.
Facts have proved, softening method is prepared composite function nano material, compared with conventional high-temperature solid state reaction preparation method, is comparatively desirable method.Softening method is to carry out in lower temperature environments, can make and multiplely have the matrix material of " being situated between steady " state and tool potentiality.Because soft chemistry technique is the chemical reaction process that a class realizes under mild conditions, be easy to realize the control to its chemical reaction process, path and mechanism, thereby can control as required the condition of reaction process, component and structure to product design, and then reach the object of " cutting out " its physical properties.Its advantage is the cutting edge technology of fabrication of new materials to free from the physical method of high temperature, high pressure, high vacuum, high energy and costliness.The key of softening method is molecular designing and the technology of preparing of presoma.
The microtexture of HP material, except layer, chain, fibrous crystalline structure, remains at many nano levels hole and passage, and is " mesoporous solid ".Although it is unordered mesoporous solid, compared with body phase material, surface-area increases and increases with active part is significant advantage, still has available part, and still has secondary space between particulate.At present, educational circles is thought, can not characterize with average pore size merely, and porosity is also to evaluate the important parameter of mesoporous solid, and the pore size distribution that also has mesoporous solid is also a parameter evaluating mesoporous solid.Also think: aperture is greater than 2nm, and the porosu solid with remarkable surface effects may be defined as mesoporous solid.
The HP material properties-correcting agent that " organises " has been selected alkylammonium salt (alkylammonium) tensio-active agent with Cationic functional groups, alkylammonium salt effectively by hydrated inorganic cationic exchange in HP material out, enter the sheet sheaf space (interlamination region) of HP material, when enlargement layer spacing, reduce the surface energy of electricity layer.In addition, alkylammonium salt can have stronger physics or chemical action with biomolecules chain, improve the avidity between HP sheet of material and biological substrate, thereby realize designing material and significant biological physiology comprehensive function on molecular level, and compatible and dispersed in biological substrate.
Thereby, the modification technology of the inorganic supermolecular intercalation assembling chemical of this project, the low temperature softening method of the inorganic supermolecular intercalation assembling chemical technology that has been coupled and 60 ℃ of-80 ℃ of temperature, utilize the interfacial effect of HP material layer, chain and mesoporous structure, and select multinomial cutting edge technology and the material functions such as the alkylammonium salt properties-correcting agent of high maturity, for realizing abundant compatible in biological substrate of HP material and dispersedly providing technical support.
2, application example
HP material is being applied aspect the initiative of following biologics for animals as the carrier of biologically active drug compound formulation:
1) in pleuromutilin fermentation, purifying and crystallization processes technical process, apply.The initiative of pleuromutilin adopts the mutafacient system of nuclear physics first, has screened good quality and high output bacterial strain optimization for fermentation technology, stable goes down to posterity, obtains first at home 20000U/ml high-yield strains.
2) extraction of Herba Sophorae alopecuroidis alkali effective monomer.
3) preparation of Spina Date Seed structure of modification product.
The initiative of above-mentioned bio-pharmaceutical has all been applied through ultramicronising, has been combined the HP material of activation and modification, all utilized that its natural ecological matrix, specific surface area are large, nanoparticle material and structure and be rich in the features such as multiple life nutritional trace element, by methods such as absorption, non-covalent combination, chemical structure, embeddings, keep stability and the activity of bio-pharmaceutical, and promoted antiviral, the anti-microbial property of composite biological agent.
3, the structural characterization of biomolecules intercalated compound
Biomolecules intercalation enters before and after laminate structure HP material interlamination region, and the structure situation that changes, generally use spectrum means, and the composite structure forming after intercalation is generally tested by X diffractive approach; The variation of pattern after intercalation, observes by Electronic Speculum means.
1) spectrographic technique
The means of report detection of biological enzyme or protein molecular structure mainly at present: UV spectrum (Uv-Vis), infrared transmission absorption spectrum (FT-IR), fluorescence spectrum (RF) etc.
2) X-ray diffraction
Whether biomolecules has been incorporated between stratiform HP material layer, X-ray diffraction provides the most directly and proved, works as well-crystallized, often there will be a series of diffraction peak.The ownership of these diffraction peaks is calculated according to bragg's formula.
Between HP material layer, introduce after cetyltrimethyl ammonium (HPTMA+) ion, HP material water-wetted surface becomes hydrophobic surface, make it fix Herba Sophorae alopecuroidis alkali by hydrophobic interaction, according to the variation of interlamellar spacing, can prove that Herba Sophorae alopecuroidis alkali is absorbed and fixed in surface or internal structure.According to X-ray diffraction result, not only can prove that whether intercalation is successful, but also can simulate the structure of intercalated compound.
If adopt the X-ray diffraction result of the glucose oxidase molecule of the fixing different amounts of stratified material of same structure.Method for making sample is: immobilization sample dispersion is in the acetic acid buffer solution of Ph=4, then auxiliary on sheet glass, after dry air, test.From diffractogram, can find out, in the time that charge capacity is 97%, the interlamellar spacing of mixture is 44A °, deduction falls the thickness 9.6A ° of this material laminate own, the interlamellar spacing increasing is 44A °, and the size that this interlamellar spacing is less than biomolecules 70 A itself °, proves that biomolecules is adsorbed on the surface of carrier.
3) Electronic Speculum method
Biomolecules intercalation enters after stratiform HP material, and structure changes, and can directly observe by Electronic Speculum (TEM, STM); And, by Electronic Speculum method, also can observe directly after biomolecules intercalation the variation of interlamellar spacing.Electronic Speculum method is characterising biological molecule intercalation the most a kind of method.
4) ultimate analysis
Ultimate analysis is by characterizing the elementary composition of intercalated compound, further determining the successful a kind of householder method of intercalation, and can determine quantitatively the amount of intercalation thing.
The technical scheme above embodiment of the present invention being provided is described in detail, applied principle and the embodiment of specific case to the embodiment of the present invention herein and set forth, the explanation of above embodiment is only applicable to help to understand the principle of the embodiment of the present invention; , for one of ordinary skill in the art, according to the embodiment of the present invention, in embodiment and range of application, all will change, in sum, this description should not be construed as limitation of the present invention meanwhile.
Claims (3)
1. the biomolecules such as enzyme, cell, ubcellular, microorganism is implemented a preparation method for the biological natural nano level inorganic carrier material of immobilization technology and application, it is characterized in that this preparation method has comprised the Supramolecular Assembling chemical modification technique technique on miniaturization, activating technology technique basis.
2. preparation method according to claim 1, is characterized in that: the method comprises Supramolecular Assembling chemical modification technique technique.
3. preparation method according to claim 1, is characterized in that: the method idiographic flow is: miniaturization, activation, modification technology technique.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310670571.1A CN103805592A (en) | 2013-12-11 | 2013-12-11 | Preparation method of biologic and natural nanoscale inorganic carrier material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310670571.1A CN103805592A (en) | 2013-12-11 | 2013-12-11 | Preparation method of biologic and natural nanoscale inorganic carrier material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103805592A true CN103805592A (en) | 2014-05-21 |
Family
ID=50702979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310670571.1A Pending CN103805592A (en) | 2013-12-11 | 2013-12-11 | Preparation method of biologic and natural nanoscale inorganic carrier material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103805592A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321397A (en) * | 2011-06-02 | 2012-01-18 | 杭州正博新型建筑材料有限公司 | Preparation process for high-performance environmentally-friendly PAL (Phenylalanine Ammonia-Lyase) flame-retardant material |
| CN102649954A (en) * | 2012-05-17 | 2012-08-29 | 兰州大学 | Immobilized enzyme for magnetic nanometer clay carrier and regenerating method thereof |
-
2013
- 2013-12-11 CN CN201310670571.1A patent/CN103805592A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321397A (en) * | 2011-06-02 | 2012-01-18 | 杭州正博新型建筑材料有限公司 | Preparation process for high-performance environmentally-friendly PAL (Phenylalanine Ammonia-Lyase) flame-retardant material |
| CN102649954A (en) * | 2012-05-17 | 2012-08-29 | 兰州大学 | Immobilized enzyme for magnetic nanometer clay carrier and regenerating method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张宏: "无机纳米粒子/聚合物复合材料的制备与性能研究", 《中国博士学位论文全文数据库》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tiwari et al. | Methods for the conversion of biomass waste into value-added carbon nanomaterials: Recent progress and applications | |
| Liu et al. | Characterization of immobilization of an enzyme in a modified Y zeolite matrix and its application to an amperometric glucose biosensor | |
| Kaur et al. | Characterization of magnetic nanoparticle–immobilized cellulases for enzymatic saccharification of rice straw | |
| CN108455597A (en) | A kind of method and application preparing N doping porous carbon using cotton seed hulls as raw material | |
| CN102716723B (en) | Method for preparing environment-friendly starch/bentonite composite material | |
| CN102924755B (en) | Preparation method of graphene/bacterial cellulose composite material | |
| Li et al. | Preparation and characterization of Saccharomyces cerevisiae alcohol dehydrogenase immobilized on magnetic nanoparticles | |
| CN101811689A (en) | Three-dimensional network carbon nanofiber and preparation method and application thereof | |
| CN102509781A (en) | Silicon-carbon composite anode material and preparing method thereof | |
| CN103804719A (en) | Graphene oxide-bacterial cellulose composite material and preparation method thereof | |
| Cui et al. | Two-dimensional porous SiO2 nanostructures derived from renewable petal cells with enhanced adsorption efficiency for removal of hazardous dye | |
| CN107099287B (en) | Hydrothermal preparation method of carbon quantum dots serving as visible light catalytic photosensitizer | |
| CN104944405A (en) | Preparation method of carbon spheres | |
| Wei et al. | High yield controlled synthesis of nano-graphene oxide by water electrolytic oxidation of glassy carbon for metal-free catalysis | |
| CN106025303A (en) | Composite nano material as well as preparation method and application thereof | |
| CN109850863A (en) | A kind of mesoporous carbon nanospheres material of type gear shape, preparation method and application | |
| CN104275196A (en) | Ferroferric oxide/carbon/cadmium sulfide composite nano material and preparation method thereof | |
| CN112675805A (en) | Preparation method of hydroxyapatite nanowire composite molybdenum disulfide adsorbent | |
| WO2016140369A1 (en) | Cellulose three-dimensional structure and production method therefor | |
| CN108409984A (en) | A kind of method that Fast synchronization prepares lignin nanoparticle and carbon quantum dot | |
| Zhang et al. | Visible light assisted enzyme-photocatalytic cascade degradation of organophosphorus pesticides | |
| Yujian et al. | High-rate ferrous iron oxidation by immobilized Acidithiobacillus ferrooxidans with complex of PVA and sodium alginate | |
| Malpani et al. | Synthesis, analysis, and multi-faceted applications of solid wastes-derived silica nanoparticles: A comprehensive review (2010–2022) | |
| Jin et al. | Innovative and economically beneficial use of corn and corn products in electrochemical energy storage applications | |
| Chakroborty et al. | Sustainable synthesis of multifunctional nanomaterials from rice wastes: a comprehensive review |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: LANZHOU WOODY RESEARCH INSTITUTE OF DAMAGED LAND R Free format text: FORMER OWNER: GANSU JINYU ECOLOGICAL ENVIRONMENT ENGINEERING CO., LTD. Effective date: 20150504 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Cao Fakui Inventor after: Shi Zhenye Inventor after: Yue Dachang Inventor before: Cao Fakui Inventor before: Shi Zhenye Inventor before: Sun Kuangsheng |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: CAO FAKUI SHI ZHENYE SUN KUANGSHENG TO: CAO FAKUI SHI ZHENYE YUE DACHANG |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20150504 Address after: Chengguan District of Gansu city of Lanzhou province Donggang West Road 730000 No. 382 (Chinese Academy of Sciences, Lanzhou Institute of Geology) 7 floor, room 713) Applicant after: LANZHOU WODEI DAMAGED LAND RESTORATION AND ENVIRONMENT ENGINEERING RESEARCH INSTITUTE Address before: 730000 weft three, Lanzhou New District, Gansu, Lanzhou Applicant before: GANSU JINYU ECOLOGICAL ENVIRONMENT ENGINEERING CO., LTD. |
|
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140521 |
|
| RJ01 | Rejection of invention patent application after publication |