CN105412982A - Method for improving antibacterial and anticancer effects of titanium dioxide nanotubes - Google Patents
Method for improving antibacterial and anticancer effects of titanium dioxide nanotubes Download PDFInfo
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
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- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
The invention discloses a method for improving antibacterial and anticancer effects of titanium dioxide nanotubes. The method comprises the steps of firstly, dissolving ruthenium complexes into water; secondly, submerging the titanium dioxide nanotubes in an aqueous solution, introducing nitrogen into the bottom layer of the aqueous solution continuously for 5-10 minutes and heating through microwave for 20-30 seconds at the temperature of 80-95 DEG C; thirdly, standing and cooling the mixture to the room temperature, performing pressurization to 20-25 Mpa to be kept for 2-3 minutes, reducing the pressure to the normal pressure, and then performing centrifugation for 30-60 minutes; fourthly, removing supernate after centrifugation, taking the solution on the lower layer and solids at the temperature of 100-120 DEG C, increasing the pressure to 20-25 Mpa, maintaining the pressure for 2-3 minutes, reducing the pressure to the normal pressure, and performing drying for 20-26 hours. By applying the method, the titanium dioxide nanotubes are high in antibacterial and anticancer capacity and inhibit growth of harmful cells effectively and permanently; the medical use effect of the titanium dioxide nanotubes can be effectively improved, and the titanium dioxide nanotubes are particularly remarkable in effect on bone cancer resistance.
Description
Technical field
The present invention relates to the technical field improving the antibacterial and antitumaous effect of titania nanotube, utilize ruthenium complex to improve the method for the antibacterial and antitumaous effect of titania nanotube more specifically.
Background technology
At present, titanium is widely used in orthopaedics clinically and dental implant thing, has played extremely important effect in shaping and beauty and surgical operation.But relevant bacteriological infection problem remains serious problems, result in the failure of a large amount of transplant operation, causes patient's surgery infectious-related complication, and bring the problem that healing time is elongated, expense increases considerably.At present, more existing reports about raising titanium antibacterial ability, as the antibacterial effect utilizing the antimicrobial molecules such as antibiotic to improve titanium.Titania nanotube, compared with titanium, has the effect that can promote that osteoblast generates, and is presenting huge potentiality and advantage as implant application aspect.Meanwhile, ruthenium complex is due to the physicochemical properties of its uniqueness, and the ferrum element character delivering hemoglobin in ruthenium and human body is close, receives increasing concern.But, the research that current utilization has the ruthenium complex raising titania nanotube antibacterial effect of antibacterial effect is not reported, especially, this ruthenium complex also has anticancer particularly anti-osteocarcinoma effect simultaneously, can give the antibacterial and anti-cancer ability that titania nanotube is stronger simultaneously.
Summary of the invention
An object of the present invention is to solve at least the problems referred to above and/or defect, and the advantage will illustrated at least is below provided.
A further object of the invention is just to provide a kind of method improving the antibacterial and antitumaous effect of titania nanotube, this method makes titania nanotube antibacterial strong with anti-cancer ability, and effectively suppress harmful cellular growths lastingly, effectively can improve titania nanotube utilizing status medically, especially more remarkable for anti-osteocarcinoma effect.
In order to realize according to these objects of the present invention and other advantages, provide a kind of method improving the antibacterial and antitumaous effect of titania nanotube, comprising the following steps:
1) ruthenium complex is soluble in water, stir to obtain aqueous solution;
2) be soaked in described aqueous solution by titania nanotube, and nitrogen be constantly filled with described aqueous solution bottom 5-10 minute, then microwave heating 20-30 second, the temperature of described microwave heating is 80-95 DEG C;
3) leave standstill and be cooled to room temperature, be pressurized to 20-25Mpa, keep dropping to normal pressure after 2-3 minute, more centrifugal 30-60 minute;
4) remove centrifugal after supernatant, take off layer solution and solid is placed in 100-120 DEG C, be pressurized to 20-25Mpa, keep 2-3 minute, then drop to normal pressure, dry 20-26 hour.
Preferably, the chemical name of described ruthenium complex is: monochlor(in)ate one chlorine one O-methoxy benzene-2-contracting N4-phenyl thiosemicarbazide monomethyl cumene closes ruthenium (II), and its structural formula is:
Preferably, described ruthenium complex is obtained by following steps:
1) γ-terpinene of the hydrate ruthenium trichloride of 65-70 weight portion and 470-480 weight portion is dissolved in the dehydrated alcohol of 1450-1500 weight portion, reflux stirs 5-7 hour, standing precipitation obtains the compound with formula (1), and namely dichloride-two-cymol closes two rutheniums (II);
2) o-methoxybenzaldehyde of the N4-phenyl thiosemicarbazide and 25-28 weight portion that take 27-35 weight portion is dissolved in the dehydrated alcohol of 870-910 weight portion jointly, be placed in 60-80 DEG C and heat 3-5 hour, standing precipitation obtains the compound with formula (2), and namely o-methoxybenzaldehyde contracting benzene is for thiosemicarbazides;
3) the o-methoxybenzaldehyde contracting benzene of 4.5-5.5 weight portion is closed for dichloride-two-cymol of thiosemicarbazides and 4-6 weight portion the dichloromethane that two rutheniums (II) are dissolved in 1230-1250 weight portion, 2-4 hour is stirred at 22-25 DEG C, separate out dark red solid, be monochlor(in)ate one chlorine one O-methoxy benzene-2-contracting N4-phenyl thiosemicarbazide monomethyl cumene and close ruthenium (II).
Preferably, the ruthenium weight content of described hydrate ruthenium trichloride is 37%, and the purity of described γ-terpinene is 95%.
Preferably, described step 1) in the mass volume ratio of ruthenium complex and water be 1-10g: 100ml.
Preferably, described step 2) in the caliber of titania nanotube be 10-30nm, pipe range is 200-1000nm, and addition is 1-5 weight portion, and described centrifugal speed is 3500-4500rpm.
Preferably, described step 3) in remove supernatant amount be the 0.6-0.8 of total solution doubly.
The present invention at least comprises following beneficial effect:
1. the antibacterial effect that has by ruthenium complex of the present invention and antitumous effect, can give again the antibacterial and anti-cancer ability that titania nanotube is stronger.
2. the present invention obtains ruthenium complex method simply, and raw material is easy to get, and has the advantage that cost is low.
3. ruthenium complex of the present invention has excellent anti-osteocarcinoma ability, and the titania nanotube obtained with ruthenium complex process has very large advantage as application in bone collection.
4. improving titania nanotube solvent used with ruthenium complex process in the present invention is water, environmental protection.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, can implement according to this with reference to description word to make those skilled in the art.
Embodiment 1
This programme improves the method for the antibacterial and antitumaous effect of titania nanotube, comprises the following steps:
1) be dissolved in 100ml water by 1g ruthenium complex, stir to obtain aqueous solution;
2) be soaked in described aqueous solution by 1g titania nanotube, and nitrogen be constantly filled with described aqueous solution bottom 5 minutes, then microwave heating 20 seconds, the temperature of described microwave heating is 80 DEG C;
3) leave standstill and be cooled to room temperature, be pressurized to 20Mpa, keep dropping to normal pressure after 2 minutes, more centrifugal 30 minutes, centrifugal speed is 3500rpm, and the caliber of titania nanotube used is 10nm, and pipe range is 200nm;
4) remove centrifugal after supernatant, supernatant is 0.6 times of total solution on solution upper strata, takes off layer solution and solid is placed in 100 DEG C, be pressurized to 20Mpa, keep 2 minutes, then drop to normal pressure, dry 20 hours, antibiotic property and the very strong titania nanotube of cancer resistance can be obtained.
Embodiment 2
This programme improves the method for antibacterial property of titanium dioxide nanotube and cancer resistance: be dissolved in by 10g ruthenium complex in 100ml water, stirs 10min, obtains homogeneous solution; Be 30nm by 5g caliber, pipe range is that the titania nanotube of 1000nm is soaked in above-mentioned solution and by nitrogen and is constantly filled with described aqueous solution bottom 10 minutes, then microwave heating 30 seconds, and the temperature of described microwave heating is 95 DEG C; Leave standstill and be cooled to room temperature, be pressurized to 25Mpa, keep dropping to normal pressure after 2 minutes, then under being placed in 4000rpm centrifugal 60 minutes.Then remove supernatant 75ml, lower floor's solution and solid are taken out, is put in 120 DEG C, is pressurized to 20Mpa, keep 2 minutes, then drop to normal pressure, dry 24h, antibiotic property and the very strong titania nanotube of cancer resistance can be obtained.
Embodiment 3
This programme improves the method for the antibacterial and antitumaous effect of titania nanotube, comprises the following steps:
1) γ-terpinene of the hydrate ruthenium trichloride of 65 weight portions and 470 weight portions is dissolved in the dehydrated alcohol of 1450 weight portions, reflux stirs 5 hours, standing precipitation obtains the compound with formula (1), and namely dichloride-two-cymol closes two rutheniums (II);
2) N of 27 weight portions is taken
4the o-methoxybenzaldehyde of-phenyl thiosemicarbazide and 25 weight portions is dissolved in the dehydrated alcohol of 870 weight portions jointly, be placed in 60 DEG C of heating 3 hours, standing precipitation obtains the compound with formula (2), and namely o-methoxybenzaldehyde contracting benzene is for thiosemicarbazides;
3) the o-methoxybenzaldehyde contracting benzene of 4.5 weight portions is closed for dichloride-two-cymol of thiosemicarbazides and 4 weight portions the dichloromethane that two rutheniums (II) are dissolved in 1230 weight portions, stir 2 hours in 22 DEG C of temperature, separate out dark red solid, be monochlor(in)ate one chlorine one O-methoxy benzene-2-contracting N4-phenyl thiosemicarbazide monomethyl cumene and close ruthenium (II).
4) be dissolved in 100ml water by 10g ruthenium complex, stir to obtain aqueous solution;
5) be soaked in by 5g titania nanotube in described aqueous solution and by nitrogen and be constantly filled with described aqueous solution bottom 6 minutes, then microwave heating 25 seconds, the temperature of described microwave heating is 85 DEG C;
6) leave standstill and be cooled to room temperature, be pressurized to 25Mpa, keep dropping to normal pressure after 3 minutes, more centrifugal 30 minutes, centrifugal speed is 4000rpm, and the caliber of titania nanotube used is 30nm, and pipe range is 1000nm;
7) remove centrifugal after supernatant, supernatant is 0.6 times of total solution on solution upper strata, takes off layer solution and solid in 110 DEG C, be pressurized to 20Mpa, keep 2 minutes, then drop to normal pressure, dry 24 hours, antibiotic property and the very strong titania nanotube of cancer resistance can be obtained.
Wherein, the chemical name of ruthenium complex is: monochlor(in)ate one chlorine one O-methoxy benzene-2-contracting N4-phenyl thiosemicarbazide monomethyl cumene closes ruthenium (II), and its structural formula is:
The physicochemical property of this ruthenium complex is: kermesinus crystal, soluble in water and organic solvent, and its hydrogen nuclear magnetic resonance modal data is
1hNMR (CDCl
3solvent): δ: 8.866 (1H, s), 8.535-8.384 (2H, m), 7.517-7.432 (7H, m), 5.755 (1H, d, J=6.0Hz), 5.216 (1H, d, J=5.9Hz), 5.108 (1H, d, J=6.0Hz), 5.031 (1H, d, J=6.0Hz), (2.729-2.635 1H, m), 2.129 (3H, s), 1.216 (3H, d, J=6.9Hz), (1.158 3H, d, J=6.9Hz).
Embodiment 4
This programme improves the method for the antibacterial and antitumaous effect of titania nanotube, comprises the following steps:
1) by containing ruthenium amount be 37% hydrate ruthenium trichloride 70 weight portion and purity be 95% γ-terpinene 480 weight portion be dissolved in the dehydrated alcohol of 1500 weight portions, reflux stirs 7 hours, standing precipitation obtains the compound with formula (1), and namely dichloride-two-cymol closes two rutheniums (II);
2) N of 35 weight portions is taken
4the o-methoxybenzaldehyde of-phenyl thiosemicarbazide and 28 weight portions is dissolved in the dehydrated alcohol of 910 weight portions jointly, be placed in 80 DEG C of heating 5 hours, standing precipitation obtains the compound with formula (2), and namely o-methoxybenzaldehyde contracting benzene is for thiosemicarbazides;
3) the o-methoxybenzaldehyde contracting benzene of 5.5 weight portions is closed for dichloride-two-cymol of thiosemicarbazides and 6 weight portions the dichloromethane that two rutheniums (II) are dissolved in 1250 weight portions, stir 4 hours in 25 DEG C of temperature, separate out dark red solid, be monochlor(in)ate one chlorine one O-methoxy benzene-2-contracting N4-phenyl thiosemicarbazide monomethyl cumene and close ruthenium (II).
4) be dissolved in 100ml water by 1g ruthenium complex, stir to obtain aqueous solution;
5) be soaked in described aqueous solution by 1g titania nanotube, and nitrogen be constantly filled with described aqueous solution bottom 10 minutes, then microwave heating 30 seconds, the temperature of described microwave heating is 90 DEG C;
6) leave standstill and be cooled to room temperature, be pressurized to 20Mpa, keep dropping to normal pressure after 2 minutes, more centrifugal 40 minutes, centrifugal speed is 3500rpm, and the caliber of titania nanotube used is 10nm, and pipe range is 200nm;
7) remove centrifugal after supernatant, supernatant is 0.7 times of total solution on solution upper strata, takes off layer solution and solid in 100 DEG C, be pressurized to 25Mpa, keep 3 minutes, then drop to normal pressure, dry 20 hours, antibiotic property and the very strong titania nanotube of cancer resistance can be obtained.
Wherein, the chemical name of ruthenium complex is: monochlor(in)ate one chlorine one O-methoxy benzene-2-contracting N4-phenyl thiosemicarbazide monomethyl cumene closes ruthenium (II), and its structural formula is:
The physicochemical property of this ruthenium complex is: kermesinus crystal, soluble in water and organic solvent, and its hydrogen nuclear magnetic resonance modal data is
1hNMR (CDCl
3solvent): δ: 8.866 (1H, s), 8.535-8.384 (2H, m), 7.517-7.432 (7H, m), 5.755 (1H, d, J=6.0Hz), 5.216 (1H, d, J=5.9Hz), 5.108 (1H, d, J=6.0Hz), 5.031 (1H, d, J=6.0Hz), (2.729-2.635 1H, m), 2.129 (3H, s), 1.216 (3H, d, J=6.9Hz), (1.158 3H, d, J=6.9Hz).
The titania nanotube pharmaceutically active after ruthenium complex process and application thereof is further illustrated below by pharmacodynamic experiment.
Experiment one: antibacterial ability is tested:
In 5 sterilizing test tubes, respectively add the bacterium liquid that 1mL concentration is 106cfu/ml, then add titania nanotube and conventional titania nanotube that 1mg embodiment 1-4 obtains respectively, cultivate 24h for 37 DEG C.Cultivate after time point, culture medium collects with doubling dilution, and extension rate is 10 times and spread plate method detection viable count.Result of the test shows: the product obtained by the present invention all has very strong bactericidal properties to staphylococcus aureus (ATCC6538), colon bacillus (ATCC25922), candida albicans (ATCC10231), Bacillus subtilis endophyticus (ATCC9372).Wherein, the sterilizing rate adding embodiment 1 reaches more than 99.99%, the sterilizing rate adding embodiment 2 reaches more than 99.998%, the sterilizing rate adding embodiment 3 reaches more than 99.999%, the sterilizing rate adding embodiment 4 reaches more than 99.999%, and the sterilizing rate adding conventional titania nanotube only has about 18%.
Experiment two: anti tumor activity in vitro is tested
Adopt MTT method, carry out vitro cytotoxicity mensuration.Titania nanotube after the ruthenium complex process obtained by embodiment 1-4 and ordinary titanium dioxide nanotube and osteocarcinoma U2-OS cell strain and nasopharyngeal carcinoma CNE-1 cell strain 72 hours action time respectively, measure IC
50(umol/mL) result is as shown in table 1.IC
50refer to the medium effective concentration to tumor cell line.
Table 1:
| Cell strain | U2-OS | CNE-1 |
| Embodiment 1 | 9.2 | 22.8 |
| Embodiment 2 | 9.1 | 22.5 |
| Embodiment 3 | 8.2 | 21.8 |
| Embodiment 4 | 9.0 | 22.1 |
| Conventional | ＞100 | ＞100 |
Experiment three: inoculation experiments
Human osteosarcoma cell 143B and neonate rat Calvarial osteoblast is inoculated respectively respectively at the titania nanotube of embodiment 1-4 and the surface of conventional titania nanotube, inoculum density is 40000/cm2,4 days, 7 days and 10 days are cultivated respectively by the DMEM culture medium of the new-born calf serum containing volume fraction being 10%, within every 2 days, change liquid, then every hole adds MTT100 μ L, cultivate 4 hours for 37 DEG C, supernatant is abandoned in suction, every hole adds DMSO0.5mL again, measures absorbance by microplate reader in wavelength 490nm place.They respectively to the situation of cells of tumorous bone activity (ABS490 nanometer) as table 2, they are as shown in table 3 to the situation of normal osteoblast activity (ABS490 nanometer) respectively.
Table 2:
| 4 days | 7 days | 10 days | |
| Embodiment 1 | 0.20 | 0.51 | 1.53 |
| Embodiment 2 | 0.21 | 0.53 | 1.56 |
| Embodiment 3 | 0.19 | 0.50 | 1.51 |
| Embodiment 4 | 0.20 | 0.50 | 1.52 |
| Conventional | 1.21 | 3.12 | 8.10 |
Table 3:
| 4 days | 7 days | 10 days | |
| Embodiment 1 | 0.11 | 0.36 | 1.25 |
| Embodiment 2 | 0.11 | 0.35 | 1.25 |
| Embodiment 3 | 0.12 | 0.39 | 1.30 |
| Embodiment 4 | 0.12 | 0.37 | 1.28 |
| Conventional | 0.06 | 0.18 | 0.54 |
From experiment one, the result of experiment two and experiment three can be found out, the titania nanotube obtained according to method of the present invention not only antibiotic property is strong, and has very strong anti-tumor activity, especially osteocarcinoma to prevent and treat aspect more remarkable; And the titania nanotube IC50 value > 100 of routine, show that it does not have active anticancer; Although there is pertinent literature to report, nano titanium oxide can produce Oxidation and kill and wound cancerous cell under the condition of ultraviolet radiation, but enter after in body as graft materials, this active oxygen is easy to a large amount of antioxidant existed in body and removes, can not be played it and kill and wound cancerous cell effect, and can be injured further other healthy cells, so not only effect is bad by the irradiation of ultraviolet light, and side effect is large, is unfavorable for extensive safe handling; And the present invention is in conjunction with the combined effect of ruthenium complex and titania nanotube, the speed that ruthenium complex effective ingredient is discharged in body is slowly stablized, the active function time is long, the growth of cells of tumorous bone can be suppressed for a long time, and do not hinder Normocellular growth, can facilitation be played on the contrary.Therefore, the present invention is that the new orthopaedics with premium properties of research and development and dental implant thing material provide new thinking.
Although embodiment of the present invention are open as above, but it is not restricted to listed in description and embodiment utilization, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the general concept that claim and equivalency range limit, the present invention is not limited to specific details and illustrates here and the embodiment described.
Claims (7)
1. improve a method for the antibacterial and antitumaous effect of titania nanotube, it is characterized in that, comprise step as follows:
1) ruthenium complex is soluble in water, stir to obtain aqueous solution;
2) be soaked in described aqueous solution by titania nanotube, and nitrogen be constantly filled with described aqueous solution bottom 5-10 minute, then microwave heating 20-30 second, the temperature of described microwave heating is 80-95 DEG C;
3) leave standstill and be cooled to room temperature, be pressurized to 20-25Mpa, keep dropping to normal pressure after 2-3 minute, more centrifugal 30-60 minute;
4) remove centrifugal after supernatant, take off layer solution and solid is placed in 100-120 DEG C, be pressurized to 20-25Mpa, keep 2-3 minute, then drop to normal pressure, dry 20-26 hour.
2. improve the method for the antibacterial and antitumaous effect of titania nanotube according to claim 1, it is characterized in that, the chemical name of described ruthenium complex is: monochlor(in)ate one chlorine one O-methoxy benzene-2-contracting N
4-phenyl thiosemicarbazide monomethyl cumene closes ruthenium (II), and its structural formula is:
。
3. improve the method for the antibacterial and antitumaous effect of titania nanotube according to claim 2, it is characterized in that, described ruthenium complex is obtained by following steps:
1) γ-terpinene of the hydrate ruthenium trichloride of 65-70 weight portion and 470-480 weight portion is dissolved in the dehydrated alcohol of 1450-1500 weight portion, reflux stirs 5-7 hour, standing precipitation obtains the compound with formula (1), and namely dichloride-two-cymol closes two rutheniums (II);
2) N of 27-35 weight portion is taken
4the o-methoxybenzaldehyde of-phenyl thiosemicarbazide and 25-28 weight portion is dissolved in the dehydrated alcohol of 870-910 weight portion jointly, be placed in 60-80 DEG C and heat 3-5 hour, standing precipitation obtains the compound with formula (2), and namely o-methoxybenzaldehyde contracting benzene is for thiosemicarbazides;
3) the o-methoxybenzaldehyde contracting benzene of 4.5-5.5 weight portion is closed for dichloride-two-cymol of thiosemicarbazides and 4-6 weight portion the dichloromethane that two rutheniums (II) are dissolved in 1230-1250 weight portion, 2-4 hour is stirred at 22-25 DEG C, separate out dark red solid, be monochlor(in)ate one chlorine one O-methoxy benzene-2-contracting N
4-phenyl thiosemicarbazide monomethyl cumene closes ruthenium (II).
4. improve the method for the antibacterial and antitumaous effect of titania nanotube according to claim 3, it is characterized in that, the ruthenium weight content of described hydrate ruthenium trichloride is 37%, and the purity of described γ-terpinene is 95%.
5. improve the method for the antibacterial and antitumaous effect of titania nanotube according to claim 1, it is characterized in that, described step 1) in the mass volume ratio of ruthenium complex and water be 1-10g: 100ml.
6. improve the method for the antibacterial and antitumaous effect of titania nanotube according to claim 5, it is characterized in that, described step 2) in the caliber of titania nanotube be 10-30nm, pipe range is 200-1000nm, addition is 1-5 weight portion, and described centrifugal speed is 3500-4500rpm.
7. improve the method for the antibacterial and antitumaous effect of titania nanotube according to claim 6, it is characterized in that, described step 3) in remove supernatant amount be the 0.6-0.8 of total solution doubly.
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