CN105288726B - Titanium metal material of ruthenium complex modification and its preparation method and application - Google Patents
Titanium metal material of ruthenium complex modification and its preparation method and application Download PDFInfo
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- CN105288726B CN105288726B CN201510793721.7A CN201510793721A CN105288726B CN 105288726 B CN105288726 B CN 105288726B CN 201510793721 A CN201510793721 A CN 201510793721A CN 105288726 B CN105288726 B CN 105288726B
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000010936 titanium Substances 0.000 title claims abstract description 67
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 67
- 239000012327 Ruthenium complex Substances 0.000 title claims abstract description 59
- 239000007769 metal material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000012986 modification Methods 0.000 title claims abstract description 7
- 230000004048 modification Effects 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 9
- 230000001093 anti-cancer Effects 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 6
- 239000005548 dental material Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- KKIGUVBJOHCXSP-UHFFFAOYSA-N 4-phenylthiosemicarbazide Chemical class NNC(=S)NC1=CC=CC=C1 KKIGUVBJOHCXSP-UHFFFAOYSA-N 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- PPWUDUBSVGQQAL-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)benzaldehyde Chemical compound O=CC1=CC=CC=C1C1=NC=CN1 PPWUDUBSVGQQAL-UHFFFAOYSA-N 0.000 claims description 19
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- YKFLAYDHMOASIY-UHFFFAOYSA-N γ-terpinene Chemical compound CC(C)C1=CCC(C)=CC1 YKFLAYDHMOASIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000012141 concentrate Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 208000002454 Nasopharyngeal Carcinoma Diseases 0.000 claims description 3
- 206010061306 Nasopharyngeal cancer Diseases 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 201000011216 nasopharynx carcinoma Diseases 0.000 claims description 3
- ODEKYHUPQWAKDE-UHFFFAOYSA-N CC1=C(C=CC=C1)C(C)C.C1(=CC=CC=C1)NC(NN)=S Chemical compound CC1=C(C=CC=C1)C(C)C.C1(=CC=CC=C1)NC(NN)=S ODEKYHUPQWAKDE-UHFFFAOYSA-N 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 7
- 125000005909 ethyl alcohol group Chemical group 0.000 description 6
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000000259 anti-tumor effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 210000002966 serum Anatomy 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000012565 NMR experiment Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012136 culture method Methods 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 239000004053 dental implant Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N ethylmethylbenzene Natural products CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003285 pharmacodynamic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 210000004881 tumor cell Anatomy 0.000 description 1
Abstract
The invention discloses a kind of titanium metal material, surface modification has ruthenium complex.Haemocyanin is introduced into surface of metal titanium first, then identify ruthenium complex and combines haemocyanin, obtains titanium metal material.Invention additionally discloses titanium metal materials to prepare antibacterial and the bone material of anticancer and the purposes of dental material.Its compatibility with organism is good, has antibacterial and anti-cancer ability, and preparation method is simple, raw material is easy to get, is good with reference to effect, the clinical meaning and social value having had.
Description
Technical field
The present invention relates to a kind of titanium metal materials.It is more particularly related to a kind of utilize ruthenium complex to serum
The recognition reaction of albumin and titanium metal material for modifying and its preparation method and application.
Background technology
Common material during titanium is performed the operation as a kind of Integrated implant, is clinically widely used.But one faced
Serious problems are relevant bacterium infection problems, result in the failure of a large amount of transfer operations.At present, have some about raising titanium
The report of metal antibacterial ability, such as the antibacterial effect using antibiotic antimicrobial molecule raising titanium.Recently, researcher
It is dedicated to improving the antibacterial ability and other abilities of titanium.How performance more excellent titanium metal material is obtained as one
It is a that there is very big science meaning and the research direction of application value.Ruthenium complex shows unique physicochemical properties, moreover,
Ruthenium is approached with delivering the ferro element property of hemoglobin in human body.If the ruthenium complex with special physiological performance can be used for
Titanium is modified, is expected to obtain the more excellent titanium metal material of performance.
Invention content
It is an object of the invention to solve at least the above, and provide the advantages of at least will be described later.
It is a still further object of the present invention to provide a kind of titanium metal materials, good with the compatibility of organism, have antibacterial
And anti-cancer ability, the clinical meaning having had and social value.
It is white to serum using ruthenium complex it is a still further object of the present invention to provide a kind of preparation method of titanium metal material
Ruthenium complex is introduced surface of metal titanium by the recognition reaction and combination of albumen, and preparation method is simple, raw material is easy to get, combines
Effect is good.
In order to realize these purposes and other advantages according to the present invention, a kind of titanium metal material, the titanium are provided
The surface modification for belonging to material has ruthenium complex.
Preferably, the titanium metal material, the structural formula of the ruthenium complex is formula (I)：
The chemical name of the ruthenium complex is：One chlorine of monochlor(in)ate, one imidazole radicals benzene -2- contractings N4Phenyl thiosemicarbazide one
Cymol closes ruthenium (II), and the molecular formula of the ruthenium complex is C27N5SH29RuCl2, opposite point of the ruthenium complex
Son amount is 627.597.
Preferably, the titanium metal material, the preparation method of the ruthenium complex include the following steps：
Step 1: hydrate ruthenium trichloride and γ-terpinene are dissolved in absolute ethyl alcohol, it is heated to reflux stirring 5~7 hours, it is quiet
Precipitation is put, dichloride-two-cymol is obtained and closes two rutheniums (II), structural formula is formula (III)：
Wherein, the hydrate ruthenium trichloride and γ-terpinene added in every milliliter of absolute ethyl alcohol is respectively 0.03~0.04 gram
With 0.2~0.4 milliliter；
Step 2: imidazolyl benzaldehyde is dissolved in absolute ethyl alcohol by between, 4- phenyl -3- thiosemicarbazides are added in, 60~70
It is reacted 4~6 hours at DEG C, obtains micro- purple solution, be spin-dried for concentrate, add in ethyl alcohol and n-hexane, white crystal is precipitated, obtains
To an imidazolyl benzaldehyde contracting 4- phenyl -3- thiosemicarbazides；
Wherein, imidazolyl benzaldehyde and 4- phenyl -3- thiosemicarbazides are respectively between being added in every milliliter of absolute ethyl alcohol
It 0.3~0.5 gram and 0.08~0.13 gram, is spin-dried for 1/12~1/8 milliliter of concentrate, the ethyl alcohol of every milliliter of concentrate addition and just
Hexane is 4~6 milliliters；
Step 3: by step 2 obtain between imidazolyl benzaldehyde contracting 4- phenyl -3- thiosemicarbazides and step 1 obtain
Dichloride-two-cymol close two rutheniums (II) and be dissolved in dichloromethane, stir 3 hours at 22~25 DEG C, precipitation
Dark red solid is to get the ruthenium complex that structural formula is formula (I)；
Wherein, imidazolyl benzaldehyde contracting 4- phenyl -3- thiosemicarbazides and dichloro between being added in every milliliter of dichloromethane
It is respectively 5~6 milligrams and 6~7 milligrams to change two chloro- two-cymols to close two rutheniums (II).
Preferably, the titanium metal material, in the step 1, the weight of ruthenium contains in the hydrate ruthenium trichloride
It is 37% to measure, and the purity of the γ-terpinene is 95%.
A kind of preparation method of titanium metal material, introduces surface of metal titanium by haemocyanin first, then matches the ruthenium
It closes object to identify and combine haemocyanin, obtains the titanium metal material.
Preferably, the preparation method of the titanium metal material, specifically includes following steps：
Step a, with the ruthenium complex solution that the ruthenium complex compound concentration is 0.4~0.6g/mL；
Step b, haemocyanin is added to the water, stirred evenly, be put into titanium, impregnated 20~40 minutes；
Step c, step b is taken out treated titanium, be put into the ruthenium complex solution that step a is obtained, impregnate 8~15
It is taken out after minute, 20~30 hours is dried at 100~120 DEG C to get titanium metal material.
Preferably, the preparation method of the titanium metal material, in the step b, the serum that is added in every milliliter of water
Albumen and titanium are respectively 0.05~0.15 gram and 0.1~0.3 gram.
A kind of purposes of titanium metal material is used to prepare the bone material and dental material of antibacterial.
A kind of purposes of titanium metal material is used to prepare the bone material and dental material of anticancer.
Preferably, the purposes of the titanium metal material is used to prepare the bone material of anti-osteocarcinoma and anti-nasopharyngeal carcinoma.
The present invention includes at least following advantageous effect：
Firstth, the haemocyanin that uses of the present invention has good biocompatibility, obtained by can effectively improving product with
The compatibility of organism；
Secondth, using the metal of haemocyanin sulfydryl and titanium-sulfydryl bonding action, haemocyanin is introduced into titanium
Surface, binding force are very strong；
Third, ruthenium complex have seralbumin strong identification and combination, effect in this way to match ruthenium
It closes object and introduces surface of metal titanium；
4th, ruthenium complex utilize have antibacterial effect and antitumous effect, can assign simultaneously titanium metal material antibacterial and
Anti-cancer ability.
Part is illustrated to embody by further advantage, target and the feature of the present invention by following, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, to enable those skilled in the art with reference to specification
Word can be implemented according to this.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more
The presence or addition of a other element or combinations.
<Embodiment 1>
A kind of titanium metal material, preparation method include the following steps：
Step 1: prepare ruthenium complex：
S1：γ-pine that the hydrate ruthenium trichloride and 2 milliliters of purity that weight content by 0.305 gram of ruthenium is 37% are 95%
Oily alkene is dissolved in 10 milliliters of absolute ethyl alcohols, is heated to reflux stirring 5~7 hours, stands and is precipitated, it is different to obtain dichloride-two-methyl
Propylbenzene closes two rutheniums (II), and structural formula is formula (III)：
S2：Imidazolyl benzaldehyde between 3 grams is dissolved in 10 milliliters of absolute ethyl alcohols, adds in 0.8 gram of 4- phenyl -3- sulfo-amino
Urea reacts 4 hours at 60 DEG C, obtains micro- purple solution, is spin-dried for 0.85 milliliter of concentrate, adds in 3.4 milliliters of ethyl alcohol and 3.4
Milliliter n-hexane, is precipitated white crystal, obtains an imidazolyl benzaldehyde contracting 4- phenyl -3- thiosemicarbazides；
S3：Imidazolyl benzaldehyde contracting 4- phenyl -3- thiosemicarbazides and 30.3 milligrams of S1 between 25.2 milligrams of S2 are obtained
Obtained dichloride-two-cymol closes two rutheniums (II) and is dissolved in 5 milliliters of dichloromethane, and it is small that 3 are stirred at 22 DEG C
When, dark red solid is precipitated to get the ruthenium complex that structural formula is formula (I)：
The chemical name of the ruthenium complex is：One chlorine of monochlor(in)ate, one imidazole radicals benzene -2- contractings N4Phenyl thiosemicarbazide one
Cymol closes ruthenium (II), and the molecular formula of the ruthenium complex is C27N5SH29RuCl2, the ruthenium complex it is opposite
Molecular weight is 627.597；
Step 2: the ruthenium complex solution that the ruthenium complex compound concentration obtained with step 1 is 0.4g/mL, by 0.25 gram
Haemocyanin is added in 5 milliliters of water, is stirred evenly, and is put into 0.5 gram of titanium, is impregnated 20 minutes, the titanium that takes out that treated,
It is put into ruthenium complex solution, is taken out after impregnating 8 minutes, 20 hours are dried at 100 DEG C to get titanium metal material.
<Embodiment 2>
A kind of titanium metal material, preparation method include the following steps：
Step 1: prepare ruthenium complex：
S1：γ-pine that the hydrate ruthenium trichloride and 4 milliliters of purity that weight content by 0.400 gram of ruthenium is 37% are 95%
Oily alkene is dissolved in 10 milliliters of absolute ethyl alcohols, is heated to reflux stirring 7 hours, stands and is precipitated, obtains dichloride-two-methyl isopropyl
Base benzene closes two rutheniums (II), and structural formula is formula (III)：
S2：Imidazolyl benzaldehyde between 5 grams is dissolved in 10 milliliters of absolute ethyl alcohols, adds in 1.3 grams of 4- phenyl -3- sulfo-aminos
Urea reacts 6 hours at 70 DEG C, obtains micro- purple solution, is spin-dried for 1.25 milliliters of concentrates, adds in 7.5 milliliters of ethyl alcohol and 7.5
Milliliter n-hexane, is precipitated white crystal, obtains an imidazolyl benzaldehyde contracting 4- phenyl -3- thiosemicarbazides；
S3：Imidazolyl benzaldehyde contracting 4- phenyl -3- thiosemicarbazides and 35.5 milligrams of S1 between 30.3 milligrams of S2 are obtained
Obtained dichloride-two-cymol closes two rutheniums (II) and is dissolved in 5 milliliters of dichloromethane, and it is small that 3 are stirred at 25 DEG C
When, dark red solid is precipitated to get the ruthenium complex that structural formula is formula (I)：
The chemical name of the ruthenium complex is：One chlorine of monochlor(in)ate, one imidazole radicals benzene -2- contractings N4Phenyl thiosemicarbazide one
Cymol closes ruthenium (II), and the molecular formula of the ruthenium complex is C27N5SH29RuCl2, the ruthenium complex it is opposite
Molecular weight is 627.597；
Step 2: the ruthenium complex solution that the ruthenium complex compound concentration obtained with step 1 is 0.6g/mL, by 0.75 gram
Haemocyanin is added in 5 milliliters of water, is stirred evenly, and is put into 1.5 grams of titaniums, is impregnated 40 minutes, the titanium that takes out that treated,
It is put into ruthenium complex solution, is taken out after impregnating 15 minutes, 30 hours are dried at 120 DEG C to get titanium metal material.
<Embodiment 3>
A kind of titanium metal material, preparation method include the following steps：
Step 1: prepare ruthenium complex：
S1：γ-pine that the hydrate ruthenium trichloride and 3 milliliters of purity that weight content by 0.366 gram of ruthenium is 37% are 95%
Oily alkene is dissolved in 10 milliliters of absolute ethyl alcohols, is heated to reflux stirring 6 hours, stands and is precipitated, obtains dichloride-two-methyl isopropyl
Base benzene closes two rutheniums (II), and structural formula is formula (III)：
S2：Imidazolyl benzaldehyde between 4 grams is dissolved in 10 milliliters of absolute ethyl alcohols, adds in 1 gram of 4- phenyl -3- thiosemicarbazide,
Reacted 5 hours at 65 DEG C, obtain micro- purple solution, be spin-dried for 1 milliliter of concentrate, add in 5 milliliters of ethyl alcohol and 5 milliliters just oneself
Alkane is precipitated white crystal, obtains an imidazolyl benzaldehyde contracting 4- phenyl -3- thiosemicarbazides；
S3：31.5 milligrams of S1 of imidazolyl benzaldehyde contracting 4- phenyl -3- thiosemicarbazides are obtained between 27.3 milligrams of S2 are obtained
To dichloride-two-cymol close two rutheniums (II) and be dissolved in 5 milliliters of dichloromethane, stirred 3 hours at 23 DEG C,
Dark red solid is precipitated to get the ruthenium complex that structural formula is formula (I)：
The chemical name of the ruthenium complex is：One chlorine of monochlor(in)ate, one imidazole radicals benzene -2- contractings N4Phenyl thiosemicarbazide one
Cymol closes ruthenium (II), and the molecular formula of the ruthenium complex is C27N5SH29RuCl2, the ruthenium complex it is opposite
Molecular weight is 627.597；
Step 2: the ruthenium complex solution that the ruthenium complex compound concentration obtained with step 1 is 0.5g/mL, by 0.5 gram
Haemocyanin is added in 5 milliliters of water, is stirred evenly, and is put into 1 gram of titanium, is impregnated 30 minutes, the titanium that takes out that treated, is put
Enter in ruthenium complex solution, taken out after impregnating 12 minutes, 25 hours are dried at 150 DEG C to get titanium metal material.
<Experiment 1>
The ruthenium complex that the step of to embodiment 3 one obtains carries out physical property identification and nmr experiments, physics and chemistry
Property is：Kermesinus crystal, soluble easily in water and organic solvent；Its hydrogen nuclear magnetic resonance modal data is 1H NMR (CDCl3 solvents):
8.872 (1H, s), 8.368-8.395 (2H, m), 7.526-7.407 (3H, m), 5.746 (1H, d, J=5.8Hz), 5.221
(1H, d, J=5.7Hz), 5.115 (1H, d, J=5.8Hz), 5.035 (1H, d, J=6.0Hz), 2.719-2.633 (1H, m),
2.117 (3H, s), 1.253 (3H, d, J=6.9Hz), 1.110 (3H, d, J=6.9Hz).
<Experiment 2>
Ruthenium complex and seralbumin effect experiment are carried out to the titanium metal material that embodiment 3 obtains, passes through fluorescence light
It composes to detect the interaction between haemocyanin and the compound, excitation wavelength 295nm.We observe haemocyanin
Fluorescent quenching intensity becomes larger with the increase of cooperation object amount, shows to have between compound and haemocyanin very strong mutual
Effect.
Its pharmaceutical activity and its application are further illustrated below by pharmacodynamic experiment.
<Experiment 3>
Antibacterial ability is tested：
1mL a concentration of 10 is added in sterilizing test tubes6The bacterium solution of/ml adds in the titanium metal material that 1mg embodiments 3 obtain,
37 DEG C of cultures are for 24 hours.It cultivates to after time point, culture medium is collected with doubling dilution, and extension rate is for 10 times and coating culture
Method detects viable count.Result of the test shows：By the titanium metal material that embodiment 3 obtains to staphylococcus aureus (ATCC
6538), escherichia coli (ATCC 25922), candida albicans (ATCC 10231), Bacillus subtilis endophyticus
(ATCC 9372) all has very strong bactericidal properties, and sterilizing rate is up to more than 99.992%.
<Experiment 4>
Anti tumor activity in vitro is tested：
Using MTT methods, vitro cytotoxicity measure is carried out.The titanium metal material that embodiment 3 is obtained and osteocarcinoma U2-OS
Cell strain and nasopharyngeal carcinoma CNE-1 cell strains 72 hours action time of difference, the results are shown in Table 1.
1 product of table is to the medium effective concentration (IC of tumor cell line50)
| Cell strain | U2-OS | CNE-1 |
| IC50(umol/mL) | 11.3 | 28.9 |
As can be seen from Table 1, the titanium metal material of ruthenium complex of the invention modification shows this through anticancer experiment in vitro
Product has strong antitumor activity.The present invention orthopaedics and dental implant object material with excellent performance new for research and development
Provide new thinking.
Although the embodiments of the present invention have been disclosed as above, but its be not restricted in specification and embodiment it is listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, it is of the invention and unlimited
In specific details and embodiment shown and described herein.
Claims (7)
1. a kind of preparation method of titanium metal material, which is characterized in that the surface modification of the titanium metal material has ruthenium complex,
Specially：Haemocyanin is introduced into surface of metal titanium first, then identify the ruthenium complex and combines haemocyanin, is obtained
The titanium metal material；
The structural formula of the ruthenium complex is formula (I)：
The chemical name of the ruthenium complex is：One chlorine of monochlor(in)ate, one imidazole radicals benzene -2- contractings N4Phenyl thiosemicarbazide monomethyl
Cumene closes ruthenium (II), and the molecular formula of the ruthenium complex is C27N5SH29RuCl2, the relative molecular weight of the ruthenium complex
It is 627.597.
2. the preparation method of titanium metal material as described in claim 1, which is characterized in that the preparation method of the ruthenium complex
Include the following steps：
Step 1: hydrate ruthenium trichloride and γ-terpinene are dissolved in absolute ethyl alcohol, it is heated to reflux stirring 5~7 hours, stands analysis
Go out, obtain dichloride-two-cymol and close two rutheniums (II), structural formula is formula (III)：
Wherein, the hydrate ruthenium trichloride and γ-terpinene added in every milliliter of absolute ethyl alcohol is respectively 0.03~0.04 gram and 0.2
~0.4 milliliter；
Step 2: imidazolyl benzaldehyde is dissolved in absolute ethyl alcohol by between, 4- phenyl -3- thiosemicarbazides are added in, at 60~70 DEG C
Reaction 4~6 hours, obtains micro- purple solution, is spin-dried for concentrate, adds in ethyl alcohol and n-hexane, white crystal is precipitated, between obtaining
Imidazolyl benzaldehyde contracting 4- phenyl -3- thiosemicarbazides；
Wherein, between being added in every milliliter of absolute ethyl alcohol imidazolyl benzaldehyde and 4- phenyl -3- thiosemicarbazides be respectively 0.3~
It 0.5 gram and 0.08~0.13 gram, is spin-dried for 1/12~1/8 milliliter of concentrate, the ethyl alcohol and n-hexane of every milliliter of concentrate addition
It is 4~6 milliliters；
Step 3: by step 2 obtain between imidazolyl benzaldehyde contracting 4- phenyl -3- thiosemicarbazides and step 1 obtain two
Two chloro- two-cymol of chlorination closes two rutheniums (II) and is dissolved in dichloromethane, is stirred 3 hours at 22~25 DEG C, is precipitated dark red
Color solid is to get the ruthenium complex that structural formula is formula (I)；
Wherein, imidazolyl benzaldehyde contracting 4- phenyl -3- thiosemicarbazides and dichloride two between being added in every milliliter of dichloromethane
It is respectively 5~6 milligrams and 6~7 milligrams that chloro- two-cymol, which closes two rutheniums (II),.
3. the preparation method of titanium metal material as claimed in claim 2, which is characterized in that in the step 1, the water
The weight content for closing ruthenium in ruthenium trichloride is 37%, and the purity of the γ-terpinene is 95%.
4. the preparation method of titanium metal material as claimed in claim 3, which is characterized in that specifically include following steps：
Step a, with the ruthenium complex solution that the ruthenium complex compound concentration is 0.4~0.6g/mL；
Step b, haemocyanin is added to the water, stirred evenly, be put into titanium, impregnated 20~40 minutes；
Step c, step b is taken out treated titanium, be put into the ruthenium complex solution that step a is obtained, impregnate 8~15 minutes
After take out, at 100~120 DEG C dry 20~30 hours to get titanium metal material.
5. the preparation method of titanium metal material as claimed in claim 4, which is characterized in that in the step b, in every milliliter of water
The haemocyanin and titanium of addition are respectively 0.05~0.15 gram and 0.1~0.3 gram.
6. a kind of purposes of titanium metal material obtained such as Claims 1 to 5 any one of them preparation method, feature exist
In being used to prepare the bone material and dental material of anticancer.
7. purposes as claimed in claim 6, which is characterized in that be used to prepare the bone material of anti-osteocarcinoma and anti-nasopharyngeal carcinoma.
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| EP1604697A1 (en) * | 2004-06-09 | 2005-12-14 | J.A.C.C. GmbH | Implantable device |
| CN103463675A (en) * | 2013-08-23 | 2013-12-25 | 广州军区广州总医院 | Antibacterial and antitumor orthopaedic implantation material and preparation method thereof |
| CN104277076A (en) * | 2014-09-29 | 2015-01-14 | 广西中医药大学 | Compound for enhancing anti-infection capacity of plants, and preparation method and application thereof |
| CN104357814A (en) * | 2014-11-24 | 2015-02-18 | 重庆大学 | Titanium alloy containing antibacterial coating as well as preparation method and application thereof |
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|---|---|---|---|---|
| EP1604697A1 (en) * | 2004-06-09 | 2005-12-14 | J.A.C.C. GmbH | Implantable device |
| CN103463675A (en) * | 2013-08-23 | 2013-12-25 | 广州军区广州总医院 | Antibacterial and antitumor orthopaedic implantation material and preparation method thereof |
| CN104277076A (en) * | 2014-09-29 | 2015-01-14 | 广西中医药大学 | Compound for enhancing anti-infection capacity of plants, and preparation method and application thereof |
| CN104357814A (en) * | 2014-11-24 | 2015-02-18 | 重庆大学 | Titanium alloy containing antibacterial coating as well as preparation method and application thereof |
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