CN110237254A - A kind of preparation method and applications of the food-borne anti-oxidation peptide optothermal material of multi-metal oxygen cluster- - Google Patents
A kind of preparation method and applications of the food-borne anti-oxidation peptide optothermal material of multi-metal oxygen cluster- Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of the food-borne anti-oxidation peptide optothermal material of multi-metal oxygen cluster-, comprising steps of soybean pentapeptide aqueous solution and multi-metal oxygen cluster aqueous solution are mixed, are placed in 5~10min of irradiation under ultraviolet light, obtain optothermal material；Wherein, the molar ratio of the soybean pentapeptide in the polypeptid solution and the polyoxy metal cluster in the polyoxy metal cluster aqueous solution is 3:1~1:1.Of the invention is easy to operate, prepared supramolecular materials structure is clear, of uniform size, physiological stability is high, cytotoxicity is low, with excellent photothermal conversion property and antibacterial activity, solve the problems, such as that technical generally existing multi-metal oxygen cluster optothermal material photo-thermal property is unstable at present, the material has excellent antibacterial activity simultaneously, can be to avoid the generation of inflammatory reaction during tumor thermal therapy.It has a good application prospect in terms of the exploitation of multi-metal oxygen cluster optothermal material and tumor thermal therapy.
Description
Technical field
The invention belongs to materials and biomedicine technical field, and in particular to a kind of based on multi-metal oxygen cluster and food-borne anti-
The preparation method of the photo-thermal transition material of oxidation activity peptide and its application in photo-thermal therapy and antibiosis.
Background technique
Cancer (malignant tumour) seriously endangers human health.Although up to the present there is great hair in terms for the treatment of of cancer
It is existing, but overall cancer related mortality rate still relatively stable (R.L.Siegel, K.D.Miller, A. Jemal, Cancer
statistics,2015.Ca A Cancer Journal for Clinicians 2015,65,5；D.L. Hoyert,75
years of mortality in the United States,2012,88,1).Currently, the treatment means of cancer are mainly wrapped
Include radiotherapy, chemotherapy, operation excision etc., however this treatment means still have significant limitation, such as side effect is big, damage
Human normal cell, drug resistance, advanced stage rate of transform height etc..In order to overcome this problem, people are dedicated to the cancer of Development of Novel
Disease treatment means, photo-thermal therapy have significant effect to the treatment of cancer as a kind of emerging technology.The original of photo-thermal therapy
Reason is that will there is the material of high photothermal conversion efficiency to be enriched near tumor tissues, and in external near-infrared laser (650nm-
Luminous energy is converted to thermal energy under 950nm) irradiating, to kill cancer cell (Z.Zhang, J.Wang, C.Chen, Adv.Mater.
2013,25,3869；L.Cheng,C.Wang,L.Feng,K.Yang,Z.Liu,Chem.Rev.2014,114, 10869；
D.Jaque,L.Martinez Maestro,B.del Rosal,P.Haro-Gonzalez,A.Benayas,J. L.Plaza,
E.Martin Rodriguez,J.Garcia Sole,Nanoscale 2014,6,9494；H.J.Kim,S. M.Lee,
K.H.Park,C.H.Mun,Y.B.Park,K.H.Yoo,Biomaterials 2015,61,95).Currently, photo-thermal therapy agent master
Will include noble metal nano particles (L.Kong, L.Yang, C.Q.Xin, S.J.Zhu, H.H.Zhang, M.Z.Zhang,
J.X.Yang,L.Li,H.P.Zhou,Y.P.Tian,Biosensors& Bioelectronics 2018,108,14；
Y.Wang,J.Xin,P.Peng,Y.Shi,D.Jian,J.Xu,J.Wu, B.Kirk,X.Wei,Journal of Materials
Chemistry B 2018,6, 10.1039.C1038TB00233A；S.Kang,W.Shin,K.Kang,M.H.Choi,
Y.J.Kim,Y.K. Kim,D.H.Min,H.Jang,Acs Applied Materials&Interfaces 2018,10,
13819), graphene (W.Gao, H.K.Lee, J.Hobley, T.Liu, I.Y.Phang, X.Y.Ling, Angewandte
Chemie 2015,127,4065), carbon nanotube (J.Song, F.Wang, X.Yang, B.Ning, M.G.Harp, S.H.
Culp,S.Hu,P.Huang,L.Nie,J.Chen,Journal of the American Chemical Society 2016,
138,7005), transient metal sulfide (MoS2、CuS…)(L.Kong,L.Xing,B.Zhou,L.Du, X.Shi,Acs
Appl Mater Interfaces 2017,9,15995-16005；X.Deng,K.Li,X.Cai,B. Liu,Y.Wei,
K.Deng, Z.Xie, Z.Wu, P.Ma, Z.Hou, Advanced Materials 2017,29), porphyrin liposome (S.Su,
Y.Ding, Y.Li, Y.Wu, G.Nie, Biomaterials 2016,80,169), near infrared absorption organic dyestuff (M.Lu,
N.Kang,C.Chen,L.Yang,Y.Li,M.Hong,X.Luo,L.Ren, X.Wang,Nanotechnology 2017,28,
445710) etc..But many optothermal materials include some uncertain problems, as photothermal conversion efficiency is not high, stability is poor,
Chemical structure and performance are indefinite, preparation is difficult, are not easy the problems such as storing, and during photo-thermal therapy, treatment temperature meeting
Reach 43 DEG C it is even higher, high temperature can cause the generation of tissue cell necrosis and proinflammatory reaction, be easy cause bacterium infection
(X.J.Zhu,W. Feng,J.Chang,Y.W.Tan,J.C.Li,M.Chen,Y.Sun,F.Y.Li,Nat.Commun.2015,
7, 10437；J.R.Melamed,R.S.Edelstein,E.S.Day,ACS Nano.2015,9,6).Therefore, develop a kind of new
The light thermal property of type is excellent and has the therapeutic agent of good anti-microbial property, is very valuable.
Multi-metal oxygen cluster (POMs) is used as a kind of inorganic poly-metal deoxide nanocluster, by accurately controlling synthesis, opens up
Reveal physics abundant and chemical property (M.T.Pope, A.M ü ller, Angewandte Chemie International
Edition 2010,30,34；B.Li,W.Li,H.Li,L.Wu,Accounts of Chemical Research 2017,50,
1391), present huge application potential in field of biomedicine, be used as antibacterial and antiviral drugs (J.Li,
Z.Chen,M.Zhou,J.Jing,W.Li,Y.Wang,L.Wu,L.Wang,Y. Wang,M.Lee,Angewandte Chemie
2016,128,2638；J.Wang,Y.Liu,K.Xu,Y.Qi,J. Zhong,K.Zhang,J.Li,E.Wang,Z.Wu,Acs
Applied Materials&Interfaces 2014,6,9785), magnetic imaging contrast agent (S.Zhang, Y.Zheng,
S.Yin, J.Sun, B.Li, L.Wu, Chemistry-A European Journal 2017,23,2802) and protein suppression
Preparation (S.Y.Lee, A.Fiene, W.Li, T. Hanck, K.A.Brylev, V.E.Fedorov, J.Lecka, A.Haider,
H.J.Pietzsch, H. Zimmermann, Biochemical Pharmacology 2015,93,171) etc..More metals
Oxygen cluster reduction when due between valence electric charge transfer (IVCT) transition become heteropoly blue, effective photothermal conversion can be carried out, because
This in past 2 years, POMs start to be used as photo-thermal therapy agent (C.Zhang, W.Bu, D.Ni, C. Zuo, C.Cheng,
Q.Li,L.Zhang,Z.Wang,J.Shi,Journal of the American Chemical Society 2016,138,
8156；D.Ni,D.Jiang,H.F.Valdovinos,E.B.Ehlerding,B.Yu,T. E.Barnhart,P.Huang,
W.Cai,Nano Letters 2017,17,3282；S.Zhang,H.Chen,G. Zhang,X.Kong,S.Yin,B.Li,
L.Wu,Journal of Materials Chemistry B 2018,6, 241).As a kind of emerging optothermal material, greatly
Heteropoly blue state labile after most POMs reduction, exposure is oxidizable in air, greatly reduces the photothermal conversion of material
Efficiency, and individually POMs material is sensitive to acid, alkali and electrolyte, and poor biocompatibility, these factors seriously limit it
Development and application.Therefore, while how keeping material structure and light thermal property, inhibit the generation of oxidation process, improve physiology
Stability is POMs class photo-thermal therapy material key technical problem urgently to be resolved.
Food-borne anti-oxidation peptide is extracted from a variety of foods such as soybean, corn, peanut, milk, egg, fish and meat
Anti-oxidation peptide, molecular weight is small, it is easy absorb, be highly-safe, extra free radical can be removed, be a kind of natural
(X.J.Wang,X.Q.Zheng,N.K.Kopparapu,W.S.Cong,Y.P. Deng,X.J.Sun,X.L.Liu,Process
Biochemistry 2014,49,1562；R.Yang,X.Li,S. Lin,Z.Zhang,F.Chen,Food Chemistry
2017,219,311).Its antioxidation process can mainly be attributed to free radical quenching, be inhibited in food by delaying lipid oxidation
The formation of free radical is alternatively arranged as improving health in nutrient and healthcare products addition functional food, is widely used in food processing
With storage, medical manufacture and biomaterial processing etc. (E.G.Cjc, I.W.Hamley, Organic&Biomolecular
Chemistry 2017,15,5867)。
Summary of the invention
The purpose of the present invention is overcoming the prior art, it is excellent and with anti-microbial property to provide a kind of light thermal property
The preparation method of the novel food-borne anti-oxidation peptide optothermal material (rSP) of multi-metal oxygen cluster-, with food-borne anti-oxidation peptide and reduction
Multi-metal oxygen cluster Supramolecular Assembling, is expected to be prepared that a kind of photothermal conversion efficiency is high, photo and thermal stability is high, biocompatibility
It is good, and the photo-thermal with anti-microbial property treats material.
To achieve the above object, the present invention provides a kind of preparation of food-borne anti-oxidation peptide optothermal material of multi-metal oxygen cluster-
Method, comprising steps of
S1, it takes soybean pentapeptide soluble in water, is prepared into the polypeptid solution that five peptide concentration of soybean is 1~6mmol/L, it is described
The amino acid sequence of soybean pentapeptide is as shown in SEQ ID:1, molecular weight 590.68g/mol；
S2, take multi-metal oxygen cluster (POM) soluble in water, the multi-metal oxygen cluster aqueous solution that preparation concentration is 1~3mmol/L；
S3, multi-metal oxygen cluster aqueous solution described in polypeptid solution described in step S1 and step S2 is mixed, the polypeptide water
The molar ratio of soybean pentapeptide in solution and the polyoxy metal cluster in the polyoxy metal cluster aqueous solution is 3:1~1:1, is mixed,
Obtain assembly solution S P；
S4, assembly solution S P described in step S3 is placed under ultraviolet light and irradiates about 5~10min, multi-metal oxygen cluster-food source
Property anti-oxidation peptide optothermal material rSP；The food-borne anti-oxidation peptide optothermal material of multi-metal oxygen cluster-is navy blue.
Under preferred embodiment, soybean pentapeptide described in step S1 is synthesized using standard Fmoc solid phase synthetic strategy, with RP-C18 color
Spectrum column and ground substance assistant laser desorption/ionization time of flight mass spectrometry method are measured the purity of the soybean pentapeptide.
Under preferred embodiment, multi-metal oxygen cluster described in step S2 is H3PMo12O40。
Under preferred embodiment, the preparation method of the food-borne anti-oxidation peptide optothermal material of multi-metal oxygen cluster-, comprising steps of
S1, it takes 11.8mg soybean pentapeptide to be dissolved in 10mL water, stirs 10min, obtaining five peptide concentration of soybean is 2mmol/L
Polypeptid solution；The amino acid sequence of the soybean pentapeptide is as shown in SEQ ID:1；
S2,36.5mg multi-metal oxygen cluster H is weighed3PMo12O40It is dissolved in 10mL water, stirs 10min, obtaining concentration is 2mmol/L
Multi-metal oxygen cluster aqueous solution；
Under S3, room temperature, multi-metal oxygen cluster aqueous solution described in step S2 is added drop-wise to polypeptid solution described in step S1 dropwise
In, it stirs 3 hours, obtains the SP aqueous solution of total assembling；The room temperature is 24~26 DEG C；Soybean five in the polypeptid solution
The molar ratio of peptide and the polyoxy metal cluster in the polyoxy metal cluster aqueous solution is 1:1；
S4, SP aqueous solution described in step S3 is placed in ultraviolet lighting 10min, it is food-borne anti-oxidant obtains multi-metal oxygen cluster-
Peptide optothermal material rSP.
The present invention also provides the applications of the food-borne anti-oxidation peptide optothermal material of the multi-metal oxygen cluster-, with described mostly golden
Belong to oxygen cluster-food-borne anti-oxidation peptide optothermal material as active constituent, is used to prepare anticolibacillary drug；A kind of anti-large intestine
The food-borne anti-oxidation peptide optothermal material of multi-metal oxygen cluster-is added in pharmacy for the drug of bacillus；With the multi-metal oxygen cluster-food
Property anti-oxidation peptide photo-thermal therapy material in source is active constituent, is used to prepare the drug for photo-thermal therapy；A kind of photo-thermal therapy
The food-borne anti-oxidation peptide optothermal material of multi-metal oxygen cluster-is added in pharmacy for drug；The multi-metal oxygen cluster-is food-borne anti-
Oxidation peptide optothermal material is used to prepare optical-thermal conversion material；Multi-metal oxygen cluster-food is added in a kind of optical-thermal conversion material in the preparation
Source property anti-oxidation peptide optothermal material.
The beneficial effects of the present invention are:
(1) the food-borne anti-oxidation peptide optothermal material rSP of novel multi-metal oxygen cluster-prepared by the present invention has good physiology
Stability and biocompatibility；
(2) the food-borne anti-oxidation peptide optothermal material rSP light thermal property of novel multi-metal oxygen cluster-prepared by the present invention is good and pacifies
Quan Xinggao；
(3) the more traditional polyacid photo-thermal of the food-borne anti-oxidation peptide optothermal material rSP of novel multi-metal oxygen cluster-prepared by the present invention
It is more preferable to control agent photo and thermal stability；
(4) the food-borne anti-oxidation peptide optothermal material rSP of novel multi-metal oxygen cluster-prepared by the present invention has good antibacterial
Activity is expected to the inflammatory effector for avoiding photo-thermal therapy process high temperature from causing and occurs, and has wide application in photo-thermal therapy field
Prospect；
(5) the food-borne anti-oxidation peptide optothermal material rSP of novel multi-metal oxygen cluster-prepared by the present invention is polyoxometallic acid
Salt and polyoxometallic acid based material provide wide application prospect in the application of field of biomedicine.
Detailed description of the invention
Fig. 1 is the Mass Spectrometric Identification result of soybean pentapeptide described in 1 step S1 of the embodiment of the present invention.
Fig. 2 is obtained POM powder after the POM solution of 1 step S2 of embodiment of the present invention preparation is freeze-dried, 1 step of embodiment
RSP solution prepared by soybean pentapeptide powder made from after five peptide solution of soybean of rapid S1 preparation is freeze-dried and embodiment 1 is freeze-dried
The infrared spectrogram of rSP powder obtained afterwards.
Fig. 3 is the Zeta potential of the rSP of the preparation of the embodiment of the present invention 1 in aqueous solution.
Fig. 4 is the Zeta potential of the POM of the preparation of comparative example 2 of the present invention in aqueous solution.
Fig. 5 is the dynamic light scattering diagram of the 1mM rSP of the preparation of the embodiment of the present invention 1 in aqueous solution.
Fig. 6 is the high resolution transmission electron microscopy photo of the 1mM rSP of the preparation of the embodiment of the present invention 1 in aqueous solution.
Fig. 7 is prepared by the POM solution of the preparation of comparative example 2 of the present invention, the rPOM solution of the preparation of comparative example 3 and embodiment 1
Cytotoxicity test of the rSP solution to hepatocellular carcinoma H22.
Fig. 8 is prepared by the POM solution, the rPOM solution of the preparation of comparative example 3, embodiment 1 of the preparation of comparative example 2 of the present invention
The preparation of embodiment 1 after placing 24 hours in rPOM solution, air prepared by comparative example 3 for 24 hours is placed in rSP solution, air
RSP aqueous solution uv absorption spectra.
Fig. 9 is prepared by the POM solution, the rPOM solution of the preparation of comparative example 3, embodiment 1 of the preparation of comparative example 2 of the present invention
RSP solution, comparative example 3 prepare rPOM solution place in air 24 hours, embodiment 1 prepare rSP solution air in put
In 808nm, 1W/cm after setting 24 hours2Photo-thermal curve under laser irradiation.
Figure 10 is prepared by the POM solution, the rPOM solution of the preparation of comparative example 3, embodiment 1 of the preparation of comparative example 2 of the present invention
Places 24 hours in rPOM solution air prepared by rSP solution, comparative example 3, placement is 24 small in the rSP air for preparing of embodiment 1
When after aqueous solution in 808nm, 1W/cm2Thermal imaging picture under laser irradiation.
Figure 11 be the embodiment of the present invention 1 prepare rSP solution, place 24 hours rSP aqueous solutions to tumour cell in air
The cytotoxicity test figure of HepG2.
Figure 12 be comparative example 3 of the present invention prepare rPOM solution, to place 24 hours rPOM aqueous solutions in air thin to tumour
The cytotoxicity test figure of born of the same parents HepG2.
Figure 13 is rSP solution, the rPOM solution of the preparation of comparative example 3, the preparation of comparative example 1 prepared by the embodiment of the present invention 1
When polypeptid solution and control group are to Escherichia coli co-incubation the optical density of Escherichia coli with incubation time variation effect
Figure.
Figure 14 is antibacterial effect figure of the blank group to Escherichia coli.
Figure 15 is the antibacterial effect figure of rPOM solution on E. coli prepared by comparative example 3 of the present invention.
Figure 16 is antibacterial effect figure of the polypeptide solution to Escherichia coli of the preparation of comparative example 1 of the present invention.
Figure 17 is the antibacterial effect figure of rSP solution on E. coli prepared by the embodiment of the present invention 1.
Figure 18 is that the preparation process of the food-borne anti-oxidation peptide optothermal material rSP of novel multi-metal oxygen cluster-and photo-thermal therapy swell
Tumor and the application schematic diagram for inhibiting inflammation.
Specific embodiment
The present invention is achieved by the following technical solutions: synthesizing soybean five using standard Fmoc solid phase synthetic strategy first
Peptide.Its purity is measured with RP-C18 chromatographic column and ground substance assistant laser desorption/ionization time of flight mass spectrometry method.Pass through letter
It is single that soybean pentapeptide and multi-metal oxygen cluster aqueous solution is mixed, it is lyophilized, makes through freeze dryer after assembling it sufficiently altogether in the solution
It is standby to obtain multi-metal oxygen cluster-soybean pentapeptide hybrid material SP.By SP aqueous solution in ultraviolet light progress photo-reduction in 10 minutes,
In irradiation process, solution colour becomes navy blue from yellow, finally obtains reduction-state heteropoly blue material (rSP).Using infrared light
Spectrum (FT-IR), elemental analysis (EA), dynamic light scattering (DLS) and transmission electron microscope (TEM) are to rSP and single heteropoly blue material
RPOM is characterized, and evaluates rSP by MTT (3- (4,5- dimethylthiazole -2- acyl group) -2,5- diphenyltetrazolium bromide ammonium) method
Cytotoxicity of the material to human liver cancer cell HepG2, it was confirmed that rSP has very high biocompatibility on a cellular level, can
Do further biologic applications.By comparing rSP and single heteropoly blue material rPOM solution and in air after exposure for 24 hours
Temperature change of these solution under 808nm laser irradiation temperature change evaluation preparation material light thermal property and photo-thermal
Stability further studies its photo-thermal therapy effect to tumour cell, with MTT colorimetric method for determining cytotoxicity, result of study
Confirm that rSP can be used as a kind of efficient, stable tumor thermal therapy agent.Then we have rated rSP material to Escherichia coli
(E.coli) antibacterial activity, excellent antibacterial effect are expected to inhibit the bacterium infection of the high thermal process induction of photo-thermal therapy.It is logical
Cross simple Supramolecular Assembling, can be obtained light thermal property it is excellent and with anti-microbial property photo-thermal therapeutic agent, in photo-thermal
Treatment and antibiosis have potential application.
The present invention includes the following steps,
1) soybean pentapeptide is synthesized using standard Fmoc solid phase synthetic strategy, it is de- with RP-C18 chromatographic column and ground substance assistant laser
Attached/ionization time of flight mass spectrometry method is measured its purity.Take soybean pentapeptide soluble in water, being prepared into five peptide concentration of soybean is
The amino acid sequence of the polypeptid solution of 1~6mmol/L, the soybean pentapeptide is as shown in Figure 1；
2) multi-metal oxygen cluster aqueous solution multi-metal oxygen cluster (POM) is soluble in water, that preparation concentration is 1~3mmol/L；
3) the soybean pentapeptide aqueous solution and multi-metal oxygen cluster POM aqueous solution equimolar ratio obtained step 1) and step 2)
It is mixed for 3:1~1:1, concussion stirs to get assembly solution S P；
4) the SP solution that step 3) obtains is irradiated 5~10 minutes under ultraviolet light, until obtaining navy blue optothermal material
rSP。
During this, polyoxometallate used is H3PMo12O40, this anion cluster compound is very common, can be direct
It is used as raw material.
Main advantages of the present invention include the following aspects: (1) the photo-thermal material rSP prepared by has good
Physiological stability and biocompatibility；(2) the photo-thermal material rSP light thermal property prepared by is good and highly-safe；(3) made
It is more preferable that the standby more traditional polyacid photo-thermal of photo-thermal material rSP controls agent photo and thermal stability；(4) the photo-thermal material prepared by
RSP has good antibacterial activity, is expected to the inflammatory effector for avoiding photo-thermal therapy process high temperature from causing and occurs, and leads in photo-thermal therapy
Domain has broad application prospects；(5) the photo-thermal material rSP prepared by is polyoxometallate and polyoxometallate
Sill provides wide application prospect in the application of field of biomedicine.The photo-thermal therapy agent rSP of preparation of the invention is also
It can be used for: application of the photo-thermal therapeutic agent (rSP) in terms of optical-thermal conversion material；Photo-thermal therapeutic agent rSP is controlled in photo-thermal
Treat the application in terms of tumour；Application of the photo-thermal therapeutic agent rSP in terms of antibacterial anti-inflammatory.
Fig. 1 is the mass spectrogram of soybean pentapeptide.Small peptide is synthesized using the Fmoc solid phase synthesis process of standard.By using RP-
C18 column and substance assistant laser desorpted/ionization time of flight mass spectrometry method are determined its purity.
Fig. 2 is the infrared spectroscopy of POM, soybean pentapeptide and rSP.It can be seen that 3300,2933,2823,1630,1425,
1350、1325、1297cm-1Place belongs to methyl/methylene eigen vibration peak；In 1672cm-1Place belongs to the spy of amido
Levy peak；In 1203cm-1、1128cm-1Belong to the characteristic peak of imines and carbon-sulfur bond；In 1064cm-1(P-Od), 967cm-1(Mo=
Od), 867cm-1(Mo-Ob- Mo) and 791cm-1(Mo-Oc- Mo) at belong to the characteristic peaks of inorganic clusters, illustrate soybean pentapeptide and
POM frame structure keeps good in hybrid composite material.
Fig. 3 is the Zeta potential of rSP in aqueous solution, is the Zeta-potential value of rSP in aqueous solution, is+22.4 mV.
Fig. 4 is the Zeta potential of POM in aqueous solution, is the Zeta-potential value of POM in aqueous solution, is. -32.5mV.Figure
3,4 the result shows that, the polypeptide of positive charge covers multi-metal oxygen cluster surface, make the surface composite material rSP obtained in electropositive,
This supermolecule assembles enhance the stability of independent POM material altogether, and rSP is made to be suitable for vivo applications.
Fig. 5 is the dynamic light scattering diagram of 1mM rSP in aqueous solution.1mM rSP being averaged in aqueous solution as the result is shown
Hydrodynamic diameter is 60 ± 15.4nm (PDI=0.066).
Fig. 6 is the high resolution transmission electron microscopy photo of 1mM rSP in aqueous solution.Prove rSP size be about
60nm, transmission electron microscope picture are consistent with dynamic light scattering result, it was demonstrated that the assembly rSP of soybean pentapeptide and POM are 60 nanometers of left sides
Right spherical agglomerates.
Fig. 7 is the cytotoxicity test of POM, rPOM and rSP to hepatocellular carcinoma H22.By MTT colorimetric method, have rated
The cytotoxicity of POM, rPOM and rSP to HepG2 cell under various concentration.The experimental results showed that even if when concentration increases to
104When nM, the survival rate of cell remains within 90% or so, this shows POM, rPOM and rSP of the present invention in cell
There is very high biocompatibility in level, and be likely to be suited for further biologic applications.
Fig. 8 is the aqueous solution after placing 24 hours in POM, rPOM, rSP, rPOM air, placing 24 hours in rSP air
Uv absorption spectra.It can be seen that rPOM, rSP have a strong absorption at 600-900nm absorption band, in rPOM air
Near infrared absorption disappears after placing 24 hours, still remains unchanged after placing 24 hours in rSP air.
Fig. 9 is the aqueous solution after placing 24 hours in POM, rPOM, rSP, rPOM air, placing 24 hours in rSP air
The photo-thermal curve under 808nm laser irradiation.
Figure 10 is after placing 24 hours in POM, rPOM, rSP, rPOM air, placing 24 hours in rSP air in 808nm
Thermal imaging picture under laser irradiation.It (is 1.0W/cm when 808nm in near-infrared laser irradiation2) under, rPOM and rSP solution
Temperature rises rapidly, and 57.1 DEG C are risen in 10 minutes, and temperature increases variation lower than 5 DEG C to pure POM under the same conditions, it was demonstrated that
Multi-metal oxygen cluster and rSP material photothermal conversion efficiency after reduction is high.Solution after being placed 24 hours in rPOM air,
Under identical laser irradiation condition, temperature change is unobvious, illustrates that rPOM photo and thermal stability is bad, and rSP exposes in air
Solution after 24 hours still has apparent temperature to increase under identical laser irradiation condition, it was confirmed that the peptide of invention with
The assembly rSP of POM has excellent photo and thermal stability.
Figure 11 is rSP, places 24 hours rSP aqueous solutions to the cytotoxicity test figure of tumour cell HepG2 in air.Benefit
24 hours rSP aqueous solutions are placed to the cell toxicant of HepG2 tumor cells of hepatocellular carcinoma in the rSP of the present invention of mtt assay test, air
Property experimental result.As a result the HepG2 tumor cells of hepatocellular carcinoma under the conditions of demonstrating rSP, placing 24 hours rSP in air obviously withers
It dies, the assembly rSP of the peptide and POM that illustrate invention has excellent tumour cell photo-thermal therapy effect.
Figure 12 is rPOM, places 24 hours rPOM aqueous solutions to the cytotoxicity test figure of tumour cell HepG2 in air.
24 hours rPOM aqueous solutions are placed to the thin of HepG2 tumor cells of hepatocellular carcinoma using the rPOM of the present invention of mtt assay test, in air
Cellular toxicity experimental result.As a result the obvious apoptosis of HepG2 tumor cells of hepatocellular carcinoma under the conditions of rPOM is demonstrated, and is put in rPOM air
This group does not have apparent cell death after setting 24 hours.
Figure 13 is rPOM, soybean pentapeptide, rSP are to the antibacterial activity test charts of Escherichia coli.
Figure 14 is antibacterial effect figure of the blank group to Escherichia coli.
Figure 15 is antibacterial effect figure of the rPOM to Escherichia coli of comparative example 3 of the present invention preparation.
Figure 16 is antibacterial effect figure of the soybean pentapeptide to Escherichia coli of comparative example 1 of the present invention preparation.
Figure 17 is antibacterial effect figure of the optothermal material rSP to Escherichia coli of preparation of the embodiment of the present invention.With control group phase
Than, soybean pentapeptide is used alone or rPOM does not have found apparent antibacterial effect, and the growth of rSP group Escherichia coli is obviously pressed down
System.Escherichia coli quantity figure in LB solid medium, it is consistent with antibacterial activity test result, illustrate the photo-thermal therapy agent of invention
RSP has excellent anti-microbial property.
Figure 18 describes the preparation process and preparation of the food-borne anti-oxidation peptide optothermal material rSP of novel multi-metal oxygen cluster-
Application of the material in photo-thermal therapy tumour and inhibition inflammation.
Below by specific implementation example, the present invention will be further described.
Embodiment 1
A kind of preparation method of the food-borne anti-oxidation peptide optothermal material rSP of multi-metal oxygen cluster-, comprising steps of
S1, soybean pentapeptide is synthesized using standard Fmoc solid phase synthetic strategy, with RP-C18 chromatographic column and ground substance assistant laser
Desorption/ionization time of flight mass spectrometry method is measured its purity, and mass spectral results are as shown in Figure 1；Weigh soybean described in 11.8mg
Pentapeptide is dissolved in 10mL water, stirs 10min, obtains the polypeptid solution that five peptide concentration of soybean is 2mmol/L；The soybean five
The amino acid sequence of peptide is as shown in SEQ ID:1；
S2,36.5mg multi-metal oxygen cluster H is weighed3PMo12O40It is dissolved in 10mL water, stirs 10min, obtaining concentration is 2mmol/L
Multi-metal oxygen cluster aqueous solution；
Multi-metal oxygen cluster aqueous solution described in step S2 is added drop-wise to polypeptid solution described in step S1 dropwise under S3, room temperature
In, soybean pentapeptide and H3PMo12Initial molar ratio be 1:1, stir 3 hours with this condition, the SP for obtaining total assembling is water-soluble
Liquid；The room temperature is 24~26 DEG C；
S4, SP aqueous solution described in step S3 is placed in ultraviolet lighting reduction 10min, it is food-borne anti-obtains multi-metal oxygen cluster-
Aoxidize peptide optothermal material rSP；The food-borne anti-oxidation peptide optothermal material rSP of multi-metal oxygen cluster-is dark blue solution.
It is obtained after the food-borne anti-oxidation peptide optothermal material rSP solution of multi-metal oxygen cluster-made from the present embodiment is freeze-dried
The infrared spectroscopy structural characterization of rSP powder is as shown in Figure 2；It can be seen that 3300,2933,2823,1630,1425,1350,
1325、1297cm-1Place belongs to methyl/methylene eigen vibration peak；In 1672cm-1Place belongs to the characteristic peak of amido；
In 1203cm-1、1128cm-1Belong to the characteristic peak of imines and carbon-sulfur bond；In 1064cm-1(P-Od), 967cm-1(Mo=Od),
867cm-1(Mo-Ob- Mo) and 791cm-1(Mo-Oc- Mo) at belong to the characteristic peaks of inorganic clusters, illustrate soybean pentapeptide and POM
(i.e. H3PMo12) frame structure keeps good in hybrid composite material.Multi-metal oxygen cluster-the food source for taking 1mL embodiment 1 to prepare
Property anti-oxidation peptide optothermal material rSP solution, utilize Malvern dynamic light scattering test rSP partial size and Zeta in aqueous solution
Current potential.Test results are shown in figure 3 for Zeta potential；ζ-the potential value of SP in aqueous solution is+22.4mV.
The food-borne anti-oxidation peptide optothermal material rSP solution of multi-metal oxygen cluster-made from Example 1 is added dropwise in ultra-thin copper mesh
On, copper mesh is dried in air.Analysis is observed to the rSP done on the copper mesh after processing with high-resolution-ration transmission electric-lens.
Transmission electron microscope picture and dynamic light scattering test result are as shown in Figure 5,6；Fig. 5 dissipates for the dynamic optical of 1mM rSP in aqueous solution
Figure is penetrated, the average hydrodynamic diameter of 1mM rSP in aqueous solution is 60 ± 15.4nm (PDI=0.066) as the result is shown；Fig. 6 is
The high resolution transmission electron microscopy photo of 1mM rSP in aqueous solution, it was demonstrated that the size of rSP is about 60nm, transmission electron microscope picture
Piece is consistent with dynamic light scattering result, it was demonstrated that soybean pentapeptide and POM (i.e. H3PMo12O40) assembly rSP be 60 rans
Spherical agglomerates.
The food-borne anti-oxidation peptide optothermal material rSP aqueous solution of 1mL multi-metal oxygen cluster-manufactured in the present embodiment is taken, sample is placed on
Product pond (cross-sectional area 1cm2) in, it is 1W/cm with power2808nm laser illumination solution 10 minutes, with thermal imaging system every 1
The temperature of a minute solution of record.Temperature lowering curve of the recording solution under room temperature state after laser irradiation, similarly every 1 point
Clock record is primary.As shown in figure 9, being the photo-thermal heating curve of rSP aqueous solution, it is seen that rSP aqueous solution can under laser irradiation
It is rapidly heated, is expected to be used for photo-thermal therapy.
After taking optothermal material rSP aqueous solution prepared by 1mL the present embodiment to place 24 hours, it is placed on sample cell (cross section
Product 1cm2) in, it is 1W/cm with power2808nm laser illumination solution 10 minutes, with thermal imaging system every 1 minute record one
The temperature of secondary solution.Temperature lowering curve of the recording solution under room temperature state after laser irradiation similarly recorded one every 1 minute
It is secondary.It is illustrated in figure 9 the photo-thermal heating curve of the rSP aqueous solution after placing 24 hours, it is seen that the rSP after placing 24 hours is water-soluble
Liquid can still be rapidly heated under laser irradiation, keep good light thermal property.
Comparative example 1
It prepares soybean pentapeptide aqueous solution (SHCMN), comprising steps of
S1, it takes soybean pentapeptide soluble in water, is prepared into the polypeptid solution that five peptide concentration of soybean is 2mmol/L, it is described big
The amino acid sequence of beans pentapeptide is as shown in SEQ ID:1.
Comparative example 2
Multi-metal oxygen cluster (POM) aqueous solution is prepared, comprising steps of
S1,36.5mg multi-metal oxygen cluster H is taken3PMo12O40It is dissolved in 10mL water, stirs 10min, obtaining concentration is 2mmol/L's
Multi-metal oxygen cluster aqueous solution.
As shown in figure 4, in the polyoxy metal cluster aqueous solution of this comparative example preparation, POM (i.e. H3PMo12O40) in aqueous solution
Zeta-potential value, be -32.5mV；The Zeta-potential value of the rSP aqueous solution of 1 preparation is+22.4mV in conjunction with the embodiments；Positive surface charge
Polypeptide cover multi-metal oxygen cluster surface, make the surface composite material rSP obtained in electropositive, this supermolecule assembles altogether
Enhance independent POM (i.e. H3PMo12O40) material stability, so that rSP is suitable for vivo applications.
Comparative example 3
The multi-metal oxygen cluster aqueous solution of reduction is prepared, comprising steps of
S1, multi-metal oxygen cluster POM aqueous solution described in comparative example 2 is irradiated 5~10 minutes under ultraviolet light, is restored
Multi-metal oxygen cluster aqueous solution rPOM.
Comparative example 4
It prepares soybean pentapeptide-multi-metal oxygen cluster and assembles aqueous solution, comprising steps of
S1, by multi-metal oxygen cluster aqueous solution molar ratio 1 described in soybean pentapeptide aqueous solution described in comparative example 1 and comparative example 2:
1 mixing, mixes, obtains soybean pentapeptide-multi-metal oxygen cluster assembly solution S P.
Comparative example 1, comparative example 2, five peptide solution of soybean made from embodiment 1, POM solution, rSP solution is freeze-dried is made three
The infrared spectroscopy structural characterization of kind powder is as shown in Figure 2.It can be seen that 3300,2933,2823,1630,1425,1350,
1325、1297cm-1Place belongs to methyl/methylene eigen vibration peak；In 1672cm-1Place belongs to the characteristic peak of amido；?
1203cm-1、1128cm-1Belong to the characteristic peak of imines and carbon-sulfur bond；In 1064cm-1(P-Od), 967cm-1(Mo=Od),
867cm-1(Mo-Ob- Mo) and 791cm-1(Mo-Oc- Mo) at belong to the characteristic peaks of inorganic clusters, illustrate soybean pentapeptide and POM frame
Frame structure keeps good in hybrid composite material.
Fig. 8 is prepared by the POM solution, the rPOM solution of the preparation of comparative example 3, embodiment 1 of the preparation of comparative example 2 of the present invention
The preparation of embodiment 1 after placing 24 hours in rPOM solution, air prepared by comparative example 3 for 24 hours is placed in rSP solution, air
RSP aqueous solution uv absorption spectra, it can be seen that rPOM solution, rSP solution have by force at 600~900nm absorption band
Strong absorption, near infrared absorption disappears after rPOM solution is placed 24 hours in air, and rSP solution is placed 24 hours in air
It still remains unchanged afterwards.
It takes 1mL comparative example 2 to prepare multi-metal oxygen cluster (POM) aqueous solution, is placed on sample cell (cross-sectional area 1cm2) in, it uses
Power is 1W/cm2808nm laser illumination solution 10 minutes, with thermal imaging system every 1 minute record solution temperature
Degree.Temperature lowering curve of the recording solution under room temperature state after laser irradiation, it is similarly primary every 1 minute record.Such as Fig. 9 institute
It is shown as the photo-thermal heating curve of POM aqueous solution, it is seen that POM aqueous solution temperature change under laser irradiation is unobvious.
The rPOM aqueous solution for taking 1mL comparative example 3 to prepare, is placed on sample cell (cross-sectional area 1cm2) in, it is 1W/cm with power2
808nm laser illumination solution 10 minutes, with thermal imaging system every 1 minute record solution temperature.After laser irradiation
Temperature lowering curve of the recording solution under room temperature state, it is similarly primary every 1 minute record.It is illustrated in figure 9 rPOM aqueous solution
Photo-thermal heating curve, it is seen that rPOM aqueous solution is rapidly heated under laser irradiation.
After the rPOM aqueous solution for taking 1mL comparative example 3 to prepare is placed 24 hours, it is placed on sample cell (cross-sectional area 1cm2) in,
It is 1W/cm with power2808nm laser illumination solution 10 minutes, with thermal imaging system every solution of 1 minute record
Temperature.Temperature lowering curve of the recording solution under room temperature state after laser irradiation, it is similarly primary every 1 minute record.Such as Fig. 9 institute
It is shown as the photo-thermal heating curve of rPOM aqueous solution after placing 24 hours, it is seen that rPOM aqueous solution is in laser irradiation after placing 24 hours
Lower warming is unobvious.It can be seen that light thermal property is remarkably decreased after placing 24 hours.
Figure 10 is prepared by the POM solution, the rPOM solution of the preparation of comparative example 3, embodiment 1 of the preparation of comparative example 2 of the present invention
Places 24 hours in rPOM solution air prepared by rSP solution, comparative example 3, placement is 24 small in the rSP air for preparing of embodiment 1
When after aqueous solution in 808nm, 1W/cm2Thermal imaging picture under laser irradiation, near-infrared laser irradiation (be when 808nm
1.0W/cm2) under, the temperature of rPOM solution and rSP solution rises rapidly, rise to 57.1 DEG C in 10 minutes, and pure POM solution
Temperature increases variation and is lower than 5 DEG C under the same conditions, it was demonstrated that multi-metal oxygen cluster rPOM and rSP the material photothermal conversion after reduction
It is high-efficient.Solution after placing 24 hours in rPOM air, under identical laser irradiation condition, temperature change is unobvious, says
Bright rPOM photo and thermal stability is bad, and rSP in air expose 24 hours after solution, under identical laser irradiation condition,
Still apparent temperature increases, it was confirmed that the peptide of invention and the assembly rSP of POM have excellent photo and thermal stability.
Embodiment 2
The food-borne anti-oxidation peptide optothermal material rSP cytotoxicity test of multi-metal oxygen cluster-
It chooses HepG2 tumor cells of hepatocellular carcinoma and carries out cytotoxicity test.HepG2 tumour cell is seeded in the culture of 96 holes
Plate, every hole inoculation 104A cell, selection DMEM are culture medium, and every hole injects 100uLDMEM solution, is placed in 5%CO2, 37 DEG C
Cell incubator in cultivate 24 hours.Take various concentration POM solution, rPOM solution and rSP solution example (1250nM,
2500nM, 5000nM, 10000nM) 100uL is separately added into cell hole, with HepG2 cell incubation, it is cultivated for 24
Hour.20uL MTT solution is added, after culture solution in hole is sucked out after being further cultured for 4 hours under the same terms, to each Kong Zhongjia
Enter 150uL DMSO, the use of microplate reader measurement absorption peak is the absorption value at 570nm, according to each laboratory sample group OD value/control
Group OD value × 100%, calculates cell survival rate；Wherein, the rSP solution is the multi-metal oxygen of preparation of the embodiment of the present invention
The food-borne anti-oxidation peptide optothermal material rSP of cluster-；The POM solution is the metal oxygen cluster aqueous solution of comparative example 2 of the present invention preparation
POM；The rPOM solution is the multi-metal oxygen cluster aqueous solution rPOM of comparative example 3 of the present invention preparation.As a result as shown in fig. 7, control
Group is cell survival rate in blank assay, the results show that even if when concentration increases to 104When nM, the survival rate of cell is still tieed up
It holds 90% or so, this, which shows POM, rPOM and rSP of the present invention on a cellular level, has very high biocompatibility,
And it is likely to be suited for further biologic applications.
Embodiment 3
The food-borne anti-oxidation peptide optothermal material rSP of multi-metal oxygen cluster-takes the external treatment of HepG2 tumor cells of hepatocellular carcinoma
HepG2 tumor cells of hepatocellular carcinoma carries out photo-thermal therapy.HepG2 tumour cell is seeded in 96 well culture plates, every hole inoculation 104It is a thin
Born of the same parents, selection DMEM are culture medium, are placed in 5%CO2, cultivate 24 hours in 37 DEG C of cell incubator.Take rPOM solution, rSP
The rSP solution that rPOM solution for 24 hours is empty, places for 24 hours in air is placed in solution, air to be separately added into cell hole, with
HepG2 cell incubation.It by 808nm laser illumination 10 minutes after 1 hour, is cultivated for 24 hours, it is molten that MTT is added
DMSO is added after being further cultured for 4 hours under the same terms in liquid, the use of microplate reader measurement absorption peak is the absorption value at 570nm, root
According to OD value=lg (1/trans), cell survival rate is calculated.Wherein, the purpose placed 24 hours in air makes rSP and rPOM
It is fully oxidized.As a result as is illustrated by figs. 11 and 12；24 hours rSP solution processing groups are placed in Figure 11, in rSP solution, air
The obvious apoptosis of HepG2 tumor cells of hepatocellular carcinoma illustrates soybean pentapeptide and assembly multi-metal oxygen cluster-food-borne anti-oxidation peptide of POM
Optothermal material rSP has excellent tumour cell photo-thermal therapy effect；The HepG2 hepatic carcinoma of Figure 12, rPOM solution processing group
The obvious apoptosis of cell, and 24 hours post-processing HepG2 tumor cells of hepatocellular carcinoma are placed in rPOM solution air, without apparent cell
It is dead.
Embodiment 4
The rPOM solution of polypeptid solution, the preparation of comparative example 3 prepared by the rSP solution of the preparation of Example 1, comparative example 1
With blank group pure water solution and Escherichia coli (Escherichia coli) co-incubation, wherein being trained altogether on each plating medium
Support 108CFU Escherichia coli, sample used sample concentration are 100uM, and wherein culture medium is beef-protein medium, in
The change curve for testing the optical density of Escherichia coli for 24 hours with incubation time is cultivated in 37 DEG C of incubators, by three kinds of solution in solid
It is cultivated on LB culture medium, 37 DEG C after incubator constant temperature incubation 48 hours, are observed its bacterium colony phenomenon, photographed to record.As a result such as Figure 13
Shown in~Figure 17；The rPOM solution and blank group pure water solution of polypeptid solution, the preparation of comparative example 3 prepared by comparative example 1 are seen
It is grown to apparent E. coli clones, and rSP solution experiments group E. coli clones quantity prepared by embodiment 1 is few, this
One phenomenon illustrates that the growth of rSP solution on E. coli prepared by embodiment 1 has good inhibitory effect.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art within the technical scope of the present disclosure, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Sequence table
<110>Dalian Polytechnic University
<120>preparation method and applications of the food-borne anti-oxidation peptide optothermal material of a kind of multi-metal oxygen cluster-
<130> ZR191169LQ
<160> 1
<170> SIPOSequenceListing 1.0
<210> 1
<211> 5
<212> PRT
<213>artificial sequence (Artificial Sequence)
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Ser His Cys Met Asn
1 5
Claims (10)
1. a kind of preparation method of the food-borne anti-oxidation peptide optothermal material of multi-metal oxygen cluster-, which is characterized in that comprising steps of
S1, it takes soybean pentapeptide soluble in water, is prepared into the polypeptid solution that five peptide concentration of soybean is 1~6mmol/L, the soybean
The amino acid sequence of pentapeptide is as shown in SEQ ID:1；
S2, take multi-metal oxygen cluster soluble in water, the multi-metal oxygen cluster aqueous solution that preparation concentration is 1~3mmol/L；
S3, multi-metal oxygen cluster aqueous solution described in polypeptid solution described in step S1 and step S2 is mixed, obtains assembly solution S P；
Wherein, the molar ratio of the soybean pentapeptide in the polypeptid solution and the polyoxy metal cluster in the polyoxy metal cluster aqueous solution is
3:1~1:1；
S4, assembly solution S P described in step S3 is placed in 5~10min of ultraviolet lower irradiation, obtains the food-borne antioxygen of multi-metal oxygen cluster-
Change peptide optothermal material rSP.
2. the preparation method of the food-borne anti-oxidation peptide optothermal material of multi-metal oxygen cluster-, feature exist according to claim 1
In soybean pentapeptide described in step S1 is synthesized using standard Fmoc solid phase synthetic strategy, is swashed with RP-C18 chromatographic column and Matrix-assisted
Light desorption/ionization time of flight mass spectrometry method is measured the purity of the soybean pentapeptide.
3. the preparation method of the food-borne anti-oxidation peptide optothermal material of multi-metal oxygen cluster-, feature exist according to claim 1
In multi-metal oxygen cluster described in step S2 is H3PMo12O40。
4. the preparation method of the food-borne anti-oxidation peptide optothermal material of multi-metal oxygen cluster-, feature exist according to claim 1
In, comprising steps of
S1, it takes 11.8mg soybean pentapeptide to be dissolved in 10mL water, stirs 10min, obtain the polypeptide that five peptide concentration of soybean is 2mmol/L
Aqueous solution；The amino acid sequence of the soybean pentapeptide is as shown in SEQ ID:1；
S2,36.5mg multi-metal oxygen cluster H is weighed3PMo12O40It is dissolved in 10mL water, stirs 10min, obtaining concentration is the more of 2mmol/L
Metal oxygen cluster aqueous solution；
Under S3, room temperature, multi-metal oxygen cluster aqueous solution described in step S2 is added drop-wise to dropwise in polypeptid solution described in step S1, is stirred
It mixes 3 hours, obtains the SP aqueous solution of total assembling；The room temperature is 24~26 DEG C；Soybean pentapeptide in the polypeptid solution and
The molar ratio of polyoxy metal cluster in the polyoxy metal cluster aqueous solution is 1:1；
S4, SP aqueous solution described in step S3 is placed in ultraviolet lighting 10min, obtains the food-borne anti-oxidation peptide light of multi-metal oxygen cluster-
Hot material rSP.
5. a kind of application of the food-borne anti-oxidation peptide optothermal material of multi-metal oxygen cluster-of method preparation as described in claim 1,
It is characterized in that, using the food-borne anti-oxidation peptide optothermal material of the multi-metal oxygen cluster-as active constituent, is used to prepare anti-large intestine bar
The drug of bacterium.
6. a kind of application of the food-borne anti-oxidation peptide optothermal material of multi-metal oxygen cluster-of method preparation as described in claim 1,
It is characterized in that, using the food-borne anti-oxidation peptide photo-thermal therapy material of the multi-metal oxygen cluster-as active constituent, is used to prepare for light
The drug of heat cure.
7. a kind of application of the food-borne anti-oxidation peptide optothermal material of multi-metal oxygen cluster-of method preparation as described in claim 1,
It is characterized in that, the food-borne anti-oxidation peptide optothermal material of the multi-metal oxygen cluster-is used to prepare optical-thermal conversion material.
8. a kind of anticolibacillary drug, which is characterized in that the food-borne anti-oxidation peptide light of multi-metal oxygen cluster-is added in pharmacy
Hot material.
9. a kind of drug of photo-thermal therapy, which is characterized in that the food-borne anti-oxidation peptide photo-thermal of multi-metal oxygen cluster-is added in pharmacy
Material.
10. a kind of optical-thermal conversion material, which is characterized in that the food-borne anti-oxidation peptide photo-thermal of multi-metal oxygen cluster-is added in the preparation
Material.
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