CN105288723A - Method for treating titanium dioxide nano-tubes by using iridium coordination compound - Google Patents
Method for treating titanium dioxide nano-tubes by using iridium coordination compound Download PDFInfo
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Abstract
本发明公开了一种利用铱配合物处理二氧化钛纳米管的方法。该方法包括步骤如下：1)获取铱配合物；2)将铱配合物溶于水中；3)将二氧化钛纳米管浸泡于所述铱配合物溶液中，并通入氮气和微波处理；3)静置冷却至常温，加压到20-25Mpa，保持2-3分钟后降到常压，再离心30-60分钟；4)移去离心后的上清液，取下层溶液和固体置于100-120℃中，加压到20-25Mpa，保持2-3分钟，然后降到常压，干燥20-26个小时。本方法使得二氧化钛纳米管抗菌和抗癌能力强，而且能持久有效抑制有害细胞生长，尤其对于抗骨癌效果更为显著，能有效提高二氧化钛纳米管在医学上的利用效果。The invention discloses a method for treating titanium dioxide nanotubes with iridium complexes. The method comprises the following steps: 1) obtaining an iridium complex; 2) dissolving the iridium complex in water; 3) immersing titanium dioxide nanotubes in the iridium complex solution, passing nitrogen gas and microwave treatment; 3) statically Cool to normal temperature, pressurize to 20-25Mpa, keep for 2-3 minutes, drop to normal pressure, and then centrifuge for 30-60 minutes; At 120°C, pressurize to 20-25Mpa, keep for 2-3 minutes, then drop to normal pressure, and dry for 20-26 hours. The method enables the titanium dioxide nanotubes to have strong antibacterial and anticancer capabilities, and can effectively inhibit the growth of harmful cells for a long time, especially for bone cancer, and can effectively improve the utilization effect of the titanium dioxide nanotubes in medicine.
Description
Technical field
The present invention relates to the technical field that titania nanotube is antibacterial and anticancer, more particularly, is the method utilizing complex of iridium process titania nanotube.
Background technology
Along with social development, the use amount of medical material particularly graft increases, and its relevant bacteriological infection problem receives increasing concern.At present, more existing reports about raising material 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, complex of iridium, due to the physicochemical properties of its uniqueness, becomes a focus of research in recent years.But, the research that current utilization has the complex of iridium raising titania nanotube antibacterial effect of antibacterial effect is not reported, especially, this complex of iridium also has anticancer particularly anti-osteocarcinoma effect simultaneously, can give titania nanotube antibacterial and anticancer particularly anti-osteocarcinoma ability 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 utilizing complex of iridium process titania nanotube, this method makes titania nanotube antibacterial strong with anti-cancer ability, and can grow by effective anticancer lastingly, especially more remarkable for anti-osteocarcinoma effect, effectively can improve titania nanotube utilizing status medically.
In order to realize, according to these objects of the present invention and other advantages, providing a kind of method utilizing complex of iridium process titania nanotube, comprise the following steps:
1) 4-6g is dissolved in 10-15ml dehydrated alcohol to furyl benzaldehyde, and add 4-phenyl-3-thiosemicarbazide 1-2g, 65-75 DEG C of return stirring, reaction 5-6h obtains micro-purple solution, be spin-dried for 1-2ml, add 5-6ml ethanol and 5-6ml normal hexane, separate out white crystal for have formula (1) to furyl benzaldehyde contracting 4-phenyl-3-thiosemicarbazide;
2) take and iridium (III) dimer 31-40mg is closed to furyl benzaldehyde contracting 4-phenyl-3-thiosemicarbazide 23-30mg and dichloro (pentamethylcyclopentadiene base) add CH
2cl
26-8ml, stirring at normal temperature 6-7 hour, solution decompression is distilled to 1-3ml, leaves standstill and separate out red solid for having the complex of iridium of formula (2), namely a chlorine a pair furyl benzaldehyde contracting 4-phenyl-3-thiosemicarbazide First Five-Year Plan methyl cyclopentadienyl closes iridium (III);
3) by soluble in water for described complex of iridium, stir to obtain complex of iridium solution;
4) be soaked in by titania nanotube in described complex of iridium solution, and nitrogen be constantly filled with described complex of iridium solution bottom 5-10 minute, then microwave heating 20-30 second, the temperature of described microwave heating is 80-95 DEG C;
5) 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;
6) 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, described step 3) in the mass volume ratio of complex of iridium and water be 2-13g: 100ml.
Preferably, described step 4) in the caliber of titania nanotube be 20-50nm, pipe range is 150-500nm, and addition is 1-5 weight portion.
Preferably, described step 5) in centrifugal speed be 3500-4500rpm.
Preferably, described step 6) in remove supernatant amount be the 0.6-0.8 of total solution doubly.
The present invention at least comprises following beneficial effect:
1. contain the aromatic rings such as the group such as furan, phenyl ring in complex of iridium of the present invention, provide to the transformation of the result of this compounds the site can reacted in a large number, especially imidazole group contains oxygen heteroatom, improves the multiformity of reaction.Be conducive to the combination of complex of iridium and titania nanotube, make the antibacterial anti-cancer ability of titania nanotube after processing strong, and persistent stablized, as application in bone collection, there is very large advantage.
2. complex of iridium of the present invention utilizes and has antibacterial effect and antitumous effect, can give titania nanotube antibacterial and anti-cancer ability simultaneously.Especially, complex of iridium of the present invention has excellent anti-osteocarcinoma ability.
3. be water with the solvent that complex of iridium process titania nanotube is used in invention, 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 utilizes the method for complex of iridium process titania nanotube, comprises the following steps:
1) 5g is dissolved in 12ml dehydrated alcohol to furyl benzaldehyde, and add 4-phenyl-3-thiosemicarbazide 1g, 70 DEG C of return stirrings, reaction 6h obtains micro-purple solution, be spin-dried for 2ml, add 5ml ethanol and 6ml normal hexane, separate out white crystal for have formula (1) to furyl benzaldehyde contracting 4-phenyl-3-thiosemicarbazide;
2) take and iridium (III) dimer 35mg is closed to furyl benzaldehyde contracting 4-phenyl-3-thiosemicarbazide 25mg and dichloro (pentamethylcyclopentadiene base) add CH
2cl
25ml, stirring at normal temperature 5 hours, solution decompression is distilled to 2ml, leaves standstill and separate out red solid for having the complex of iridium of formula (2), namely a chlorine a pair furyl benzaldehyde contracting 4-phenyl-3-thiosemicarbazide First Five-Year Plan methyl cyclopentadienyl closes iridium (III);
3) by soluble in water for described complex of iridium, stir to obtain complex of iridium solution;
4) be soaked in by titania nanotube in the solution of described complex of iridium, and nitrogen be constantly filled with described complex of iridium solution bottom 6 minutes, then microwave heating 25 seconds, the temperature of described microwave heating is 85 DEG C:
5) leave standstill and be cooled to room temperature, be pressurized to 22Mpa, keep dropping to normal pressure after 2 minutes, more centrifugal 40 minutes;
6) remove centrifugal after supernatant, take off layer solution and solid is placed in 110 DEG C, be pressurized to 22Mpa, keep 3 minutes, then drop to normal pressure, dry 24 hours.
Embodiment 2
This programme utilizes the method for complex of iridium process titania nanotube, comprises the following steps:
1) 4g is dissolved in 10ml dehydrated alcohol to furyl benzaldehyde, and add 4-phenyl-3-thiosemicarbazide 1g, 65 DEG C of return stirrings, reaction 5h obtains micro-purple solution, be spin-dried for 1ml, add 5ml ethanol and 5ml normal hexane, separate out white crystal for have formula (1) to furyl benzaldehyde contracting 4-phenyl-3-thiosemicarbazide;
2) take and iridium (III) dimer 31mg is closed to furyl benzaldehyde contracting 4-phenyl-3-thiosemicarbazide 23mg and dichloro (pentamethylcyclopentadiene base) add CH
2cl
26ml, stirring at normal temperature 6 hours, solution decompression is distilled to 1ml, leaves standstill and separate out red solid for having the complex of iridium of formula (2), namely a chlorine a pair furyl benzaldehyde contracting 4-phenyl-3-thiosemicarbazide First Five-Year Plan methyl cyclopentadienyl closes iridium (III);
3) be dissolved in 100ml water by 2g complex of iridium, stir to obtain complex of iridium solution;
4) be 20nm by caliber, pipe range is that the titania nanotube 1g of 300nm is soaked in the solution of described complex of iridium, and nitrogen being constantly filled with described complex of iridium solution bottom 5 minutes, then microwave heating 20 seconds, the temperature of described microwave heating is 80 DEG C;
5) leave standstill be cooled to room temperature, be pressurized to 20Mpa, keep dropping to normal pressure after 2 minutes, then be 3500rpm with centrifugal speed, centrifugal 30 minutes;
6) remove centrifugal after the amount of supernatant be 0.6 times of total solution, take 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.
Embodiment 3
This programme utilizes the method for complex of iridium process titania nanotube, comprises the following steps:
1) 6g is dissolved in 15ml dehydrated alcohol to furyl benzaldehyde, and add 4-phenyl-3-thiosemicarbazide 2g, 65-75 DEG C of return stirring, reaction 6h obtains micro-purple solution, be spin-dried for 2ml, add 6ml ethanol and 6ml normal hexane, separate out white crystal for have formula (1) to furyl benzaldehyde contracting 4-phenyl-3-thiosemicarbazide;
2) take and iridium (III) dimer 40mg is closed to furyl benzaldehyde contracting 4-phenyl-3-thiosemicarbazide 30mg and dichloro (pentamethylcyclopentadiene base) add CH
2cl
28ml, stirring at normal temperature 7 hours, solution decompression is distilled to 3ml, leaves standstill and separate out red solid for having the complex of iridium of formula (2), namely a chlorine a pair furyl benzaldehyde contracting 4-phenyl-3-thiosemicarbazide First Five-Year Plan methyl cyclopentadienyl closes iridium (III);
3) be dissolved in 100ml water by 13g complex of iridium, stir to obtain complex of iridium solution;
4) be 50nm by caliber, pipe range is that the titania nanotube 5g of 500nm is soaked in the solution of described complex of iridium, and nitrogen being constantly filled with described complex of iridium solution bottom 10 minutes, then microwave heating 30 seconds, the temperature of described microwave heating is 95 DEG C;
5) leave standstill be cooled to room temperature, be pressurized to 25Mpa, keep dropping to normal pressure after 3 minutes, then be 4500rpm with centrifugal speed, centrifugal 60 minutes;
6) remove centrifugal after supernatant, the amount removed is 0.8 times of total solution, takes off layer solution and solid is placed in 120 DEG C, is pressurized to 25Mpa, keeps 3 minutes, then drop to normal pressure, dry 26 hours.
Embodiment 4
This programme utilizes the method for complex of iridium process titania nanotube, comprises the following steps:
1) 5g is dissolved in 10ml dehydrated alcohol to furyl benzaldehyde, and add 4-phenyl-3-thiosemicarbazide 2g, 65 DEG C of return stirrings, reaction 6h obtains micro-purple solution, be spin-dried for 1ml, add 6ml ethanol and 5ml normal hexane, separate out white crystal for have formula (1) to furyl benzaldehyde contracting 4-phenyl-3-thiosemicarbazide;
2) take and iridium (III) dimer 31mg is closed to furyl benzaldehyde contracting 4-phenyl-3-thiosemicarbazide 30mg and dichloro (pentamethylcyclopentadiene base) add CH
2cl
28ml, stirring at normal temperature 6 hours, solution decompression is distilled to 3ml, leaves standstill and separate out red solid for having the complex of iridium of formula (2), namely a chlorine a pair furyl benzaldehyde contracting 4-phenyl-3-thiosemicarbazide First Five-Year Plan methyl cyclopentadienyl closes iridium (III);
3) be dissolved in 100ml water by 9g complex of iridium, stir to obtain complex of iridium solution;
4) be 30nm by caliber, pipe range is that the titania nanotube 3g of 150nm is soaked in the solution of described complex of iridium, and nitrogen being constantly filled with described complex of iridium solution bottom 10 minutes, then microwave heating 20 seconds, the temperature of described microwave heating is 95 DEG C;
5) leave standstill be cooled to room temperature, be pressurized to 24Mpa, keep dropping to normal pressure after 3 minutes, then be 4000rpm with centrifugal speed, centrifugal 30 minutes;
6) remove centrifugal after the amount of supernatant be 0.7 times of total solution, take off layer solution and solid is placed in 115 DEG C, be pressurized to 21Mpa, keep 2 minutes, then drop to normal pressure, dry 25 hours.
Wherein, complex of iridium of the present invention is close iridium (III) to furyl benzaldehyde contracting 4-phenyl-3-thiosemicarbazide First Five-Year Plan methyl cyclopentadienyl between a chlorine one, its physicochemical property is: be red crystals, soluble in water and organic solvent, and its hydrogen nuclear magnetic resonance modal data is
1hNMR (CDCl
3solvent): δ=9.97 (br, 1H), 9.08 (br, 1H), 7.78 (s, 1H), 7.69 (s, 1H), 7.52 (m, 3H, J=7.6Hz), 7.46 (t, 1H, J=7.6Hz), 7.28 (t, 2H, J=7.7Hz), 7.13 (d, 1H, J=7.0Hz), 5.11 (d, 1H, J=6.0Hz), 4.76 (d, 1H, J=6.0Hz), 4.71 (d, 1H, J=5.2Hz), 4.65 (d, 1H, J=5.2Hz), 3.86 (s, 3H), 2.70 (m, 1H), 2.61 (m, 1H, J=6.9Hz), 2.53 (s, 3H), 1.58, 1.36 (2d, 6H, J=6.7Hz) ppm..
The titania nanotube pharmaceutically active after complex of iridium process and application thereof is further illustrated below by pharmacodynamic experiment.
Experiment one: antibacterial ability is tested:
In 5 sterilizing test tubes, respectively add 1mL concentration is 10
6the bacterium liquid of cfu/ml, then adds titania nanotube and conventional titania nanotube that 1mg embodiment 1-4 obtains respectively, cultivates 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 99.992%, the sterilizing rate adding embodiment 2 reaches more than 99.996%, the sterilizing rate adding embodiment 3 reaches more than 99.995%, the sterilizing rate adding embodiment 4 reaches more than 99.997%, 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 complex of iridium 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 | 9.1 | 19.6 |
| Embodiment 2 | 9.2 | 19.5 |
| Embodiment 3 | 9.0 | 19.4 |
| Embodiment 4 | 9.0 | 19.2 |
| 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 | 0.52 | 1.55 |
| Embodiment 2 | 0.19 | 0.52 | 1.53 |
| Embodiment 3 | 0.19 | 0.56 | 1.58 |
| Embodiment 4 | 0.18 | 0.51 | 1.53 |
| Conventional | 1.21 | 3.12 | 8.10 |
Table 3:
| 4 days | 7 days | 10 days |
| Embodiment 1 | 0.13 | 0.35 | 1.29 |
| Embodiment 2 | 0.14 | 0.38 | 1.29 |
| Embodiment 3 | 0.13 | 0.36 | 1.30 |
| Embodiment 4 | 0.15 | 0.38 | 1.40 |
| 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 complex of iridium and titania nanotube, the speed that complex of iridium 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 (5)
1. utilize a method for complex of iridium process titania nanotube, it is characterized in that, comprise step as follows:
1) 4-6g is dissolved in 10-15ml dehydrated alcohol to furyl benzaldehyde, and add 4-phenyl-3-thiosemicarbazide 1-2g, 65-75 DEG C of return stirring, reaction 5-6h obtains micro-purple solution, be spin-dried for 1-2ml, add 5-6ml ethanol and 5-6ml normal hexane, separate out white crystal for have formula (1) to furyl benzaldehyde contracting 4-phenyl-3-thiosemicarbazide;
2) take and iridium (III) dimer 31-40mg is closed to furyl benzaldehyde contracting 4-phenyl-3-thiosemicarbazide 23-30mg and dichloro (pentamethylcyclopentadiene base) add CH
2cl
26-8ml, stirring at normal temperature 6-7 hour, solution decompression is distilled to 1-3ml, leaves standstill and separate out red solid for having the complex of iridium of formula (2), namely a chlorine a pair furyl benzaldehyde contracting 4-phenyl-3-thiosemicarbazide First Five-Year Plan methyl cyclopentadienyl closes iridium (III);
3) by soluble in water for described complex of iridium, stir to obtain complex of iridium solution;
4) be soaked in by titania nanotube in described complex of iridium solution, and nitrogen be constantly filled with described complex of iridium solution bottom 5-10 minute, then microwave heating 20-30 second, the temperature of described microwave heating is 80-95 DEG C;
5) 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;
6) 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. utilize the method for complex of iridium process titania nanotube according to claim 1, it is characterized in that, described step 3) in the mass volume ratio of complex of iridium and water be 2-13g: 100ml.
3. utilize the method for complex of iridium process titania nanotube according to claim 1, it is characterized in that, described step 4) in the caliber of titania nanotube be 20-50nm, pipe range is 150-500nm, and addition is 1-5 weight portion.
4. utilize the method for complex of iridium process titania nanotube according to claim 3, it is characterized in that, described step 5) in centrifugal speed be 3500-4500rpm.
5. utilize the method for complex of iridium process titania nanotube according to claim 4, it is characterized in that, described step 6) in remove supernatant amount be the 0.6-0.8 of total solution doubly.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1604697A1 (en) * | 2004-06-09 | 2005-12-14 | J.A.C.C. GmbH | Implantable device |
| CN102583530A (en) * | 2012-04-07 | 2012-07-18 | 河南工业大学 | Preparation method of nanometer titanium dioxide with ultralarge specific surface area |
| CN104402939A (en) * | 2014-11-18 | 2015-03-11 | 广西中医药大学 | Iridium complex as well as preparation method and application thereof |
| CN104826159A (en) * | 2015-04-24 | 2015-08-12 | 湖北大学 | Medical titanium metal implant material and preparation method thereof |
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2015
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1604697A1 (en) * | 2004-06-09 | 2005-12-14 | J.A.C.C. GmbH | Implantable device |
| CN102583530A (en) * | 2012-04-07 | 2012-07-18 | 河南工业大学 | Preparation method of nanometer titanium dioxide with ultralarge specific surface area |
| CN104402939A (en) * | 2014-11-18 | 2015-03-11 | 广西中医药大学 | Iridium complex as well as preparation method and application thereof |
| CN104826159A (en) * | 2015-04-24 | 2015-08-12 | 湖北大学 | Medical titanium metal implant material and preparation method thereof |
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