CN101857638A - Method for preparing bovine hemoglobin/titanium-based titanium dioxide hybrid material - Google Patents
Method for preparing bovine hemoglobin/titanium-based titanium dioxide hybrid material Download PDFInfo
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- CN101857638A CN101857638A CN 201010181821 CN201010181821A CN101857638A CN 101857638 A CN101857638 A CN 101857638A CN 201010181821 CN201010181821 CN 201010181821 CN 201010181821 A CN201010181821 A CN 201010181821A CN 101857638 A CN101857638 A CN 101857638A
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Abstract
The invention relates to a method for preparing a bovine hemoglobin/titanium-based titanium dioxide hybrid material and belongs to the technical field of biological-inorganic hybridization. The method comprises the following steps of: preparing a titanium-based titanium dioxide nano array tubular film; and preparing a hemoglobin and titanium-based titanium dioxide nano array tube hybrid film. A highly ordered titanium dioxide nanotube array film is prepared by an anode oxidation method and the hemoglobin is fixed to the titanium-based titanium dioxide nanotube array film by using electrostatic self-assembly technology. The method has the advantages of simple operation and good enzyme activity keeping. The prepared hybrid film can be used in the fields of bio-sensing, biological electrochemical apparatuses and the like.
Description
Technical field
The invention belongs to the biological-inorganic hybrid technical field, particularly relate to a kind of method for preparing bovine hemoglobin and titanium-based titanium dioxide hybrid material, activity of proteins keeps good in this hybrid material, and is good to the catalytic oxidation activity of hydrogen peroxide.
Background technology
The biological-inorganic hybrid technology is as an emphasis that important branch is scientific research of supramolecular chemistry always, the constructing and functionalization people's research focus recently and in a very long time in the future especially of biological-inorganic hybrid material.Binding biomolecules has the characteristics of widespread use potentiality, realizes functionalization and the device of biomacromolecule by the biological-inorganic hybrid technology, thereby realizes biomolecules value in actual applications.Active biomolecule (as enzyme, amino acid, peptide) has broad application prospects in fields such as bio-sensing, catalysis, medicine, food-processings owing to its special physico-chemical property, but because temperature, the pH value narrow range of free molecule survival, easy sex change and inactivation, all stable inadequately to heat, strong acid, highly basic and organic solvent, cost an arm and a leg, hinder its research and application as a class important application material, the stability that therefore how to improve the enzyme molecule becomes the primary problem that solves of people.Inorganic materials is the object that material circle is pursued with excellent characteristic such as its good light, electricity, magnetic always, active biomolecule and inorganic materials assembling are obtained biological-inorganic hybrid material, for the activity of keeping biomacromolecule, the stability that improves biomacromolecule is heavy to closing.The peculiar property that the biological-inorganic nano hybrid material that assembling obtains based on active biomolecule and inorganic nano material has the two has simultaneously become the research focus in fields such as life science and Materials science.
Oxyphorase (hemoglobin, major function Hb) be in blood in conjunction with and transport oxygen.Produce a large amount of oxyphorases (each red corpuscle contains 300,000,000 Hb molecules approximately) at the red corpuscle ripening period, oxyphorase is dissolved in the red corpuscle colloidal sol with high density (be about quality 34%).Hb is about 96% oxygen saturation the arterial blood that arrives peripheral tissues from lung through heart.Hb only is 64% oxygen saturation in getting back to the venous blood of heart.Therefore every 100mL blood through organizing discharge 1/3 oxygen that Hb carries approximately or be equivalent to normal atmosphere and body temperature under 6.5mL oxygen.
Hb is that each polypeptide chain is called a subunit by two α chains and two tetramers that the β chain mutually combines and forms, and each subunit comprises a heme, so a Hb intramolecularly includes 4 protoheme prothetic groups altogether.These protoheme prothetic groups lay respectively in the hole, crack of each subunit of oxyphorase, constitute the structure of oxyphorase folder formula.4 subunits of Hb are arranged closely mutually, form the molecule of almost spherical, and the molecular weight of Hb is about 66000Da, and iso-electric point is 6.8, and molecular size is 5.0 * 5.5 * 6.5nm.The iron atom at protoheme porphyrin ring center has 6 coordinate bonds, the wherein N coordination on 4 keys and the porphyrin ring, form a plane, the iron atom of imidazoles nitrogen in the nearer histidine residues in protoheme plane and protoheme forms an axial coordination key in addition, so common heme iron atom can form 5 coordinate bonds, this moment, its axial diameter was bigger, can not all embed the porphyrin plane.When the 6th coordination of Hb heme iron atom with after oxygen combines, its reduced falls in the porphyrin ring plane.Promptly be accompanied by combining of Hb molecule and oxygen, corresponding variation has also taken place in the conformation of Hb.This " mutamerism " of Hb is the very efficient manner of regulating its functional activity, makes it carry out reversible oxygen with oxygen and combines.This phenomenon is similar to the combination between the enzyme-to-substrate, so oxyphorase is otherwise known as " fermentoid ".
Protoheme Fe in four peptide chains of oxyphorase
3+/ Fe
2+Average formula weight current potential about-70mV (vs.SCE), the current potential of independent α chain is than the high 40mV of current potential of β chain.The electron transfer rate constant of haemoglobin molecule is K
s=3 * 10
-3Mol
-1S
-1, when reacting with ferricyanate, the electron transfer rate constant K
s=7 * 10
4Mol
-1S
-1Oxidation is slow, so oxyphorase can be thought the molecule of " redox inertia ".
TiO
2Be a kind of multi-crystalline compounds, occurring in nature has rutile-type, Detitanium-ore-type, brookite type and TiO
2Four kinds of crystalline structures of-B.Detitanium-ore-type TiO wherein
2Because of its excellent biological compatibility, chemical stability is strong, and is cheap and easy to get and be widely used.Traditional TiO
2Powder body material has higher specific surface area, but can not operate continuously when using, and recycling causes use cost to increase.In addition, electrode materials also can't directly utilize powder to carry out performance test.Therefore, the immobilization of electrode materials and device just become the practical problems that presses for solution in its application.At present, with TiO
2The research of the immobilization that material is taken as the leading factor and device mainly is divided into two classes: a class is made up of unordered nanoparticle or is piled up the thin-film material that forms; The another kind of array mould material of being made up of the microtexture of high-sequential, main representative is exactly the TiO of high-sequential
2Nano-tube array.
Anonizing is to prepare porous titanium dioxide thin-film in fluorine-containing electrolyte solution, the high-sequential TiO of this method preparation
2Nano-tube array especially is suitable as electrode.This high-sequential nano tube structure helps the transmission of electronics along the vertical basad direction of nanotube, helps diffusion and electric charge the transmission on electrode of ion in solid-liquid interface, and reduces current loss.In addition, the semiconductor material of this nano tube structure has higher specific surface area of ratio nano thin-film material and more effective inner surface structure, and the reduction of geometry of not following or structurally ordered property, therefore at sun power sensitization battery, photocatalyst, there is important effect bio-pharmaceuticals and biosensor aspect.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of bovine hemoglobin/titanium-based titanium dioxide hybrid material, this method makes full use of titanium-based titanium dioxide nano-array pipe excellent biological compatibility and electroconductibility.
The bovine hemoglobin of the present invention preparation and titanium-based titanium dioxide hybrid material are that the red albumin of ox with cationization is by electrostatic attraction reactive force and the self-assembly of electronegative titanium-based titanium dioxide nano-array pipe, bovine hemoglobin secondary structure after the self-assembly does not change, and the microenvironment wetting ability of porphyrin ring strengthens simultaneously.
Described titanium-based titanium dioxide nano-array pipe can be sent out preparation by anodic oxidation, and protein is bovine hemoglobin.
The preparation method of bovine hemoglobin/titanium-based titanium dioxide hybrid material of the present invention is as follows:
(1) preparation of titanium-based titanium dioxide nano-array pipe
The processing of a, substrate: with the small pieces that the titanium sheet is cut into, place Virahol, acetone and methyl alcohol ultrasonic cleaning successively, use the deionized water ultrasonic cleaning then, drying;
The preparation of b, electrolytic solution: the preparation of electrolytic solution: with NH
4F is dissolved in deionized water: the electrolytic solution that is configured to 0.09～0.12mol/L in the mixing solutions of ethylene glycol volume ratio=1: 49;
C, anodic oxidation legal system TiO
2Nano-tube array: the negative electrode and the anode that above-mentioned titanium sheet and platinized platinum electrode are connected to D.C. regulated power supply place above-mentioned electrolytic solution, apply 20～60 volts of electrolysis of volts DS 2～6 hours; After electrolysis is finished,, use N after the cleaning with the titanium sheet water ultrasonic cleaning after the electrolysis
2Dry up;
D, TiO
2The roasting of nano-tube array: sample after cleaning is put into muffle furnace, and beginning to heat up from room temperature adds thermal bake-out, is incubated 2～6 hours after being warming up to 450～600 ℃, cools to the furnace to obtain titanium-based titanium dioxide nano-array pipe sample after the room temperature and take out standby;
(2) preparation of bovine hemoglobin/titanium-based titanium dioxide hybrid material
The preparation of e, buffered soln: prepare the Sodium phosphate dibasic of 0.2mol/L and the sodium dihydrogen phosphate of 0.2mol/L respectively, in varing proportions the buffered soln of mixed preparing pH6～7;
The preparation of f, bovine hemoglobin solution: bovine hemoglobin is dissolved in the buffered soln of step e preparation, is mixed with the bovine hemoglobin solution of 0.5mg/ml;
G, at N
2Under the atmosphere, titanium-based titanium dioxide nano-array pipe sample is immersed in the bovine hemoglobin solution that step f prepared, adsorbed 8～24 hours, water is rinsed the not bovine hemoglobin of absorption of sample surfaces well N
2Dry up under the atmosphere, promptly obtain bovine hemoglobin/titanium-based titanium dioxide hybrid material.
Further, the preparation of described electrolytic solution: with NH
4It is the electrolytic solution that is mixed with 0.09～0.1mol/L in 1: 49 the mixing solutions that F is dissolved in deionized water and ethylene glycol volume ratio.
Further, described anodic oxidation legal system TiO
2Nano-tube array: the negative electrode and the anode that respectively titanium sheet and platinized platinum electrode are connected in D.C. regulated power supply apply volts DS 20V electrolysis 2 hours.
Further, described TiO
2The roasting of nano-array pipe: sample is put into muffle furnace, begin to add thermal bake-out with the temperature rise rate of 1 ℃/min from room temperature.
Bovine hemoglobin/the titanium-based titanium dioxide hybrid material of the present invention's preparation, can make the bovine hemoglobin molecular surface positively charged by regulation and control pH, and nano titania array tube-surface is electronegative, thereby makes bovine hemoglobin and titanium-based titanium dioxide nano-array pipe with static self-assembly mode film forming.This preparation method realizes the device of protein molecule, expands its range of application.
The advantage of present technique invention is that the preparation method is simple to operate, and is with low cost, only makes water as solvent in the preparation process, preparation method's environmental protection, and the hybrid material that makes is easy to device, and it is good that protein active keeps.
Description of drawings:
Fig. 1 is the attenuated total reflectance attenuated total refraction infrared spectra of bovine hemoglobin (a) and bovine hemoglobin/titanium-based titanium dioxide (b)
Fig. 2 is the cyclic voltammetry curve of titanium-based titanium dioxide (dotted line) and bovine hemoglobin/titanium-based titanium dioxide (solid line)
Embodiment
Embodiment 1
A, the titanium sheet of buying is cut into the rectangular-shaped pieces of 1.0 * 2.0cm, places Virahol, acetone and methyl alcohol ultrasonic cleaning 10 minutes successively.Used the deionized water ultrasonic cleaning then 10 minutes, N under the room temperature
2Dry up in the atmosphere;
B, get 0.045mol NH
4F is dissolved in the electrolytic solution that is configured to 0.09mol/L in the mixing solutions of 1mL deionized water and 49mL ethylene glycol;
C, anodic oxidation legal system TiO
2The nano-array pipe: respectively titanium sheet and platinized platinum electrode are connected in the anode and the negative electrode of D.C. regulated power supply, apply 40 volts of electrolysis of volts DS 6 hours, whole process keeps the temperature of the electrolytic solution that makes among the step b at 25 ℃.After electrolysis is finished, with sample with deionized water ultrasonic cleaning 30 seconds (divide and carry out for 3 times), sample after cleaning N
2Dry up.
D, TiO
2The roasting of nano-array pipe: the sample that makes among the step c is put into muffle furnace, begins to add thermal bake-out with the temperature rise rate of 1 ℃/min from room temperature, be warming up to 450 ℃ after insulation 6 hours, the roasting sample cool to the furnace take out after the room temperature standby
The preparation of e, buffered soln: prepare the Sodium phosphate dibasic of 0.2mol/L and the sodium dihydrogen phosphate of 0.2mol/L respectively,, be used to dissolve bovine hemoglobin with this buffered soln of preparing pH6.0
The preparation of f, bovine hemoglobin solution: take by weighing the 0.05g bovine hemoglobin and be dissolved in the 100ml phosphate buffer soln that e prepares;
G, at N
2In the atmosphere, titanium-based titanium dioxide nano-array pipe sample is immersed in the phosphate buffered saline(PBS) solution of bovine hemoglobin of f preparation, adsorb after 8 hours, rinse the bovine hemoglobin of not adsorbing of sample surfaces well N with pure water
2Dry up under the atmosphere, promptly obtain bovine hemoglobin/titanium-based titanium dioxide hybrid material.
Above-mentioned sample is carried out Infrared Characterization, as shown in Figure 1, compare with pure bovine hemoglobin, amino I district and peak, amino II district appear in bovine hemoglobin in bovine hemoglobin/titanium-based titanium dioxide hybrid material in the 1450-1700 wave-number range, illustrate that proteinic secondary structure does not change, the while electrochemical data, bovine hemoglobin has kept catalytic activity in accompanying drawing 2 explanation bovine hemoglobin/titanium-based titanium dioxide hybrid materials.The result of embodiment 2,3 is identical with embodiment 1.
Embodiment 2
The processing of a, substrate: the titanium sheet of buying is cut into the rectangular-shaped pieces of 1.0 * 2.0cm, places Virahol, acetone and methyl alcohol ultrasonic cleaning 10 minutes successively.Used the deionized water ultrasonic cleaning then 10 minutes, at N
2Dry up in the atmosphere;
The preparation of b, electrolytic solution: get 0.01mol NH
4F is dissolved in the mixing solutions of 2mL deionized water and 98mL ethylene glycol and is configured to electrolytic solution;
C, anodic oxidation legal system TiO
2The nano-array pipe: respectively titanium sheet and platinized platinum electrode are connected in the anode and the negative electrode of D.C. regulated power supply, apply 20 volts of electrolysis of volts DS 2 hours, whole process keeps the temperature of the electrolytic solution that makes among the step b at 25 ℃.After electrolysis was finished, with deionized water ultrasonic cleaning 30 seconds (divide and carry out for 3 times), sample after cleaning was at N with sample
2Dry up in the atmosphere;
D, TiO
2The roasting of nano-array pipe: the sample that makes among the step c is put into muffle furnace, begins to add thermal bake-out with the temperature rise rate of 1 ℃/min from room temperature, be warming up to 500 ℃ after insulation 2 hours, the roasting sample cool to the furnace take out after the room temperature standby;
The preparation of e, buffered soln: the Sodium phosphate dibasic of preparation 0.2mol/L and the sodium dihydrogen phosphate of 0.2mol/L with this buffered soln of preparing pH6.5, are used to dissolve bovine hemoglobin;
The preparation of f, bovine hemoglobin solution: take by weighing the 0.0125g bovine hemoglobin and be dissolved in the 25ml buffered soln that makes among the step e;
G, at N
2Under the atmosphere, titanium-based titanium dioxide nano-array pipe sample is immersed in the bovine hemoglobin solution that makes among the step f, adsorbs after 12 hours, rinse the not absorption bovine hemoglobin of sample surfaces well N with pure water
2Dry up in the atmosphere, promptly obtain bovine hemoglobin and titanium-based titanium dioxide hybrid material.
Embodiment 3
The processing of a, substrate: the titanium sheet of buying is cut into the rectangular-shaped pieces of 1.0 * 1.0cm, places Virahol, acetone and methyl alcohol ultrasonic cleaning 10 minutes successively.Used the deionized water ultrasonic cleaning then 10 minutes, at N
2Dry up in the atmosphere;
The preparation of b, electrolytic solution: get 0.012mol NH
4F is dissolved in the mixing solutions of 2mL deionized water and 98mL ethylene glycol and is configured to electrolytic solution;
C, anodic oxidation legal system TiO
2Nano-tube array: respectively titanium sheet and platinized platinum electrode are connected in the anode and the negative electrode of D.C. regulated power supply, apply 60 volts of electrolysis of volts DS 2 hours, whole process keeps the temperature of the electrolytic solution that makes among the step b at 25 ℃.After electrolysis was finished, with deionized water ultrasonic cleaning 30 seconds (divide and carry out for 3 times), sample after cleaning was at N with sample
2Dry up in the atmosphere;
D, TiO
2The roasting of nano-tube array: the sample that makes among the step c is put into muffle furnace, begins to add thermal bake-out with the temperature rise rate of 1 ℃/min from room temperature, be warming up to 600 ℃ after insulation 3 hours, the roasting sample cool to the furnace take out after the room temperature standby;
The preparation of e, buffered soln: the Sodium phosphate dibasic of preparation 0.2mol/L and the sodium dihydrogen phosphate of 0.2mol/L with this buffered soln of preparing pH7.0, are used to dissolve bovine hemoglobin;
The preparation of f, bovine hemoglobin solution: take by weighing the 0.0125g bovine hemoglobin and be dissolved in the 25ml buffered soln that makes among the step e;
G, at N
2Under the atmosphere, titanium-based titanium dioxide nano-array pipe sample is immersed in the bovine hemoglobin solution that makes among the step f, adsorbs after 24 hours, rinse the not absorption bovine hemoglobin of sample surfaces well N with pure water
2Dry up in the atmosphere, promptly obtain bovine hemoglobin and titanium-based titanium dioxide hybrid material.
Embodiment 1,2 and 3 gained bovine hemoglobin and titanium-based titanium dioxide hybrid material are carried out electrochemical property test to be obtained the bovine hemoglobin electrochemical activity and is respectively 15.3%, 16.9%, 14.7%.
Claims (4)
1. a method for preparing ox blood albumen/titanium-based titanium dioxide hybrid material is characterized in that, operation steps is:
(1) preparation of titanium-based titanium dioxide nano-array pipe
The processing of a, substrate: with the small pieces that the titanium sheet is cut into, place Virahol, acetone and methyl alcohol ultrasonic cleaning successively, use the deionized water ultrasonic cleaning then, drying;
The preparation of b, electrolytic solution: the preparation of electrolytic solution: with NH
4F is dissolved in deionized water: the electrolytic solution that is configured to 0.09～0.12mol/L in the mixing solutions of ethylene glycol volume ratio=1: 49;
C, anodic oxidation legal system TiO
2Nano-tube array: the negative electrode and the anode that above-mentioned titanium sheet and platinized platinum electrode are connected to D.C. regulated power supply place above-mentioned electrolytic solution, apply 20～60 volts of electrolysis of volts DS 2～6 hours; After electrolysis is finished,, use N after the cleaning with the titanium sheet water ultrasonic cleaning after the electrolysis
2Dry up;
D, TiO
2The roasting of nano-tube array: sample after cleaning is put into muffle furnace, and beginning to heat up from room temperature adds thermal bake-out, is incubated 2～6 hours after being warming up to 450～600 ℃, cools to the furnace to obtain titanium-based titanium dioxide nano-array pipe sample after the room temperature and take out standby;
(2) preparation of bovine hemoglobin/titanium-based titanium dioxide hybrid material
The preparation of e, buffered soln: prepare the Sodium phosphate dibasic of 0.2mol/L and the sodium dihydrogen phosphate of 0.2mol/L respectively, in varing proportions the buffered soln of mixed preparing pH6～7;
The preparation of f, bovine hemoglobin solution: bovine hemoglobin is dissolved in the buffered soln of step e preparation, is mixed with the bovine hemoglobin solution of 0.5mg/ml;
G, at N
2Under the atmosphere, titanium-based titanium dioxide nano-array pipe sample is immersed in the bovine hemoglobin solution that step f prepared, adsorbed 8～24 hours, water is rinsed the not bovine hemoglobin of absorption of sample surfaces well N
2Dry up under the atmosphere, promptly obtain bovine hemoglobin/titanium-based titanium dioxide hybrid material.
2. method according to claim 1 is characterized in that, the preparation of described electrolytic solution: with NH
4It is the electrolytic solution that is mixed with 0.09～0.1mol/L in 1: 49 the mixing solutions that F is dissolved in deionized water and ethylene glycol volume ratio.
3. according to the described method of claim 1, it is characterized in that described anodic oxidation legal system TiO
2Nano-tube array: the negative electrode and the anode that respectively titanium sheet and platinized platinum electrode are connected in D.C. regulated power supply apply 20 volts of electrolysis of volts DS 2 hours.
4. according to the described method of claim 1, it is characterized in that described TiO
2The roasting of nano-array pipe: sample is put into muffle furnace, begin to add thermal bake-out with the temperature rise rate of 1 ℃/min from room temperature.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109646675A (en) * | 2019-01-29 | 2019-04-19 | 郑州大学 | A kind of pharmaceutical composition of cellular membrane biomimetic titanium dioxide nano granule |
| CN110354304A (en) * | 2019-07-29 | 2019-10-22 | 湖州市中心医院 | Substrate and its preparation process for prosthese after artificial joint replacement |
| CN111000566A (en) * | 2019-12-13 | 2020-04-14 | 江南大学 | Wearable flexible sensor with photothermal effect and antibacterial function |
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|---|---|---|---|---|
| CN1884515A (en) * | 2006-07-07 | 2006-12-27 | 中国科学院上海硅酸盐研究所 | Method for reversiblely assembling enzyme using nano sheet-like TiO2 |
| CN101393160A (en) * | 2008-10-29 | 2009-03-25 | 北京化工大学 | Biological functional multilayer film modified electrode and method for making same |
| CN101393161A (en) * | 2008-10-29 | 2009-03-25 | 北京化工大学 | Bio-sensing multilayer film of titanium oxide contained nanometer sheet and method for making same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884515A (en) * | 2006-07-07 | 2006-12-27 | 中国科学院上海硅酸盐研究所 | Method for reversiblely assembling enzyme using nano sheet-like TiO2 |
| CN101393160A (en) * | 2008-10-29 | 2009-03-25 | 北京化工大学 | Biological functional multilayer film modified electrode and method for making same |
| CN101393161A (en) * | 2008-10-29 | 2009-03-25 | 北京化工大学 | Bio-sensing multilayer film of titanium oxide contained nanometer sheet and method for making same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109646675A (en) * | 2019-01-29 | 2019-04-19 | 郑州大学 | A kind of pharmaceutical composition of cellular membrane biomimetic titanium dioxide nano granule |
| CN110354304A (en) * | 2019-07-29 | 2019-10-22 | 湖州市中心医院 | Substrate and its preparation process for prosthese after artificial joint replacement |
| CN111000566A (en) * | 2019-12-13 | 2020-04-14 | 江南大学 | Wearable flexible sensor with photothermal effect and antibacterial function |
| CN111000566B (en) * | 2019-12-13 | 2021-05-11 | 江南大学 | Wearable flexible sensor with photothermal effect and antibacterial function |
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