CN103007302A - Gd2O3-TiO2 composite nanoparticle as well as preparation method and application thereof - Google Patents
Gd2O3-TiO2 composite nanoparticle as well as preparation method and application thereof Download PDFInfo
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- CN103007302A CN103007302A CN2012105397969A CN201210539796A CN103007302A CN 103007302 A CN103007302 A CN 103007302A CN 2012105397969 A CN2012105397969 A CN 2012105397969A CN 201210539796 A CN201210539796 A CN 201210539796A CN 103007302 A CN103007302 A CN 103007302A
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Abstract
The invention discloses a Gd2O3-TiO2 composite nanparticle as well as a preparation method and application thereof. Trivalent gadolinium salt is dissolved in polyhydric alcohol solution, alkaline polyhydric alcohol solution is added to have reaction, then tetravalent titanium salt solution is dropwise added to have reaction to obtain nanoparticle suspension or sol, and separation and free-drying are carried out to obtain the Gd2O3 and TiO2 composite nanoparticle. The Gd2O3-TiO2 composite nanparticle disclosed by the invention has a radiography function and also has a medical treatment function.
Description
Technical field
The present invention relates to nanoparticle, relate in particular to Gd
2O
3Composite Ti O
2Nanoparticle and its preparation method and application.
Background technology
Nuclear magnetic resonance (Magnetic resonance imaging, MRI) technology has now become a kind of important medical diagnosis means, can effectively detect tissue necrosis, ischemia and various malignant change such as tumor, and can carry out early diagnosis, also may monitor organ transplantation etc.Have highly sensitive, clear picture, inspection without advantages such as wounds.
Along with the extensive use of nuclear magnetic resonance in clinical, people express higher hope to MRI, especially improve it to the resolution of tissue, and some less focuses are found as early as possible.The MRI contrast agent can change the relaxation rate of water proton in the local organization, improves the image contrast of normal and disease sites, with the susceptiveness of MRI very important relation is arranged.
The material that can be used for the MRI contrast agent comprises the nano materials such as paramagnetic contrast medium and superparamagnetism contrast agent.Owing to have a plurality of azygous electronics, the electron spin magnetic moment is large, and relaxivity is high, and electric field is symmetrical, is easy to water coordination and water of coordination molecule and can reaches the advantages such as 7, and the paramagnetic rare-earth chemical compound is paid much attention to as magnetic resonance contrast agent, and is widely used in clinical.With compare gadolinium sesquioxide (Gd through the gadolinium co-ordination complex that is commonly used for the T1 contrast agent
2O
3) nanoparticle has that the sequestered gadolinium ion is few, the body inner penetration is forced down, magnetic susceptibility is high, be easy to finishing connects ligands specific, be conducive to strengthen relaxation ability and to advantages such as physical impairment are little, be expected to become the live body contrast agent of good biocompatibility.
In addition, independent Gd
2O
3Nanoparticle is got rid of rapidly behind The book of Changes renal metabolism because size is too little, and retention time is shorter in vivo, is unfavorable for the test in MRI.And, superparamagnetism Gd
2O
3Nanoparticle contrast agent generally only has the function of medical imaging diagnosis, the very difficult function that plays simultaneously treatment of being combined with biomolecule or drug molecule.
Therefore, still need to Gd in this area
2O
3Nanoparticle improves, and realizes medical science radiography and therapeutic treatment dual-use function, improves its application performance.
Summary of the invention
The object of the present invention is to provide a kind of novel Gd
2O
3-TiO
2Composite nanoparticle is realized medical science radiography and therapeutic treatment dual-use function.
A further object of the present invention is to provide the preparation method of this composite nanoparticle.
Another purpose of the present invention is to provide the application of this composite nanoparticle.
A first aspect of the present invention provides a kind of nanoparticle, and described nanoparticle comprises gadolinium sesquioxide and titanium dioxide.
In another preference, described nanoparticle is composited by titanium dioxide, gadolinium sesquioxide, and wherein said titanium dioxide wraps up described gadolinium sesquioxide.
In another preference, described titanium dioxide is single-phase anatase titania.
In another preference, in the gross weight of described nanoparticle, described nanoparticle comprises the 20wt%-80wt% titanium oxide, and surplus is gadolinium sesquioxide.
In another preference, the particle diameter of described nanoparticle is 25-200nm.
A second aspect of the present invention provides a kind of nanoparticle suspension or colloidal sol, comprises the described nanoparticle of first aspect and disperse medium, and described disperse medium is selected from: the mixed liquor of water and ethanol.
In another preference, the volume ratio of described water and ethanol is 1:0.2 ~ 6, preferably, is 1:4 ~ 4:1.
In another preference, contain surfactant in the described disperse medium, described surfactant is cetyl trimethyl ammonium bromide, ammonium lauryl sulfate, tween, citric acid or Polyethylene Glycol.
A third aspect of the present invention provides the preparation method of the described nanoparticle suspension of second aspect or colloidal sol, may further comprise the steps:
(i) trivalent gadolinium salt is dissolved in the polyhydric alcohol solutions, the polyhydric alcohol solutions that adds alkali reacts;
(ii) tetravalent salt of titanium solution is dropped in the reaction solution that step (i) makes, reaction obtains nanoparticle suspension claimed in claim 4 or colloidal sol, wherein,
Described trivalent gadolinium salt is selected from: Gadolinium trinitrate, Gadolinium trichloride, six water Gadolinium trinitrates, six water Gadolinium trichlorides or its combination;
Described alkali is selected from: sodium hydroxide, potassium hydroxide or its combination;
Described each polyhydric alcohol is independently selected from: diglycol or diethylene glycol or its combination;
Described tetravalent salt of titanium is selected from: butyl titanate or titanium tetrachloride or its combination;
Described tetravalent salt of titanium solution refers to the solution that tetravalent salt of titanium mixed liquor water-soluble and ethanol obtains.
In another preference, the volume ratio of described water and ethanol is 1:0.2 ~ 6, preferably, is 1:4 ~ 4:1.
In another preference, described method also comprises the step that reaction solution that step (i) is obtained to make is dialysed; Perhaps
Also be included in the step of adding surfactant in nanoparticle suspension that step (ii) obtains or the colloidal sol, described surfactant is cetyl trimethyl ammonium bromide, ammonium lauryl sulfate, tween, citric acid or Polyethylene Glycol.
In another preference, described method also comprises:
The step that the nanoparticle suspension that step (ii) is obtained or colloidal sol carry out ripening; Or
Carry out the step of ripening add surfactant in nanoparticle suspension that step (ii) obtains or colloidal sol after, described surfactant is cetyl trimethyl ammonium bromide, ammonium lauryl sulfate, tween, citric acid or Polyethylene Glycol.
A fourth aspect of the present invention provides the preparation method of the described nanoparticle of first aspect, described method to comprise the described nanoparticle suspension of second aspect or colloidal sol are carried out centrifugal, and lyophilization is processed and obtained the described nanoparticle of first aspect.
In another preference, said method comprising the steps of:
(i) trivalent gadolinium salt is dissolved in the polyhydric alcohol solutions, the polyhydric alcohol solutions that adds alkali reacts;
(ii) tetravalent salt of titanium solution is dropped in the reaction solution that step (i) makes, reaction obtains nanoparticle suspension claimed in claim 4 or colloidal sol, wherein,
Described trivalent gadolinium salt is selected from: Gadolinium trinitrate, Gadolinium trichloride, six water Gadolinium trinitrates, six water Gadolinium trichlorides or its combination;
Described alkali is selected from: sodium hydroxide, potassium hydroxide or its combination;
Described each polyhydric alcohol is independently selected from: diglycol or diethylene glycol or its combination;
Described tetravalent salt of titanium is selected from: butyl titanate or titanium tetrachloride or its combination;
Described tetravalent salt of titanium solution refers to the solution that tetravalent salt of titanium mixed liquor water-soluble and ethanol obtains.
In another preference, the volume ratio of described water and ethanol is 1:0.2 ~ 6, preferably, is 1:4 ~ 4:1.
In another preference, described method also comprises the step that reaction solution that step (i) is obtained to make is dialysed; Perhaps
Also be included in the step of adding surfactant in nanoparticle suspension that step (ii) obtains or the colloidal sol, described surfactant is cetyl trimethyl ammonium bromide, ammonium lauryl sulfate, tween, citric acid or Polyethylene Glycol.
In another preference, described method also comprises:
The step that the nanoparticle suspension that step (ii) is obtained or colloidal sol carry out ripening; Or
Carry out the step of ripening add surfactant in nanoparticle suspension that step (ii) obtains or colloidal sol after, described surfactant is cetyl trimethyl ammonium bromide, ammonium lauryl sulfate, tween, citric acid or Polyethylene Glycol.
A fifth aspect of the present invention provides the purposes of the described nanoparticle of first aspect or the described nanoparticle suspension of second aspect or colloidal sol, for the preparation of:
(a) contrast agent; Or
(b) inorganic photosensitizer.
In another preference, the described nanoparticle of first aspect or the described nanoparticle suspension of second aspect or colloidal sol are for the preparation of inorganic photosensitizer.
Nanoparticle of the present invention is compared with the gadolinium complex contrast agent of medically clinical practice, and the radiography performance is significantly improved, and nanoparticle of the present invention also has the therapeutic treatment function.
In should be understood that within the scope of the present invention, above-mentioned each technical characterictic of the present invention and can making up mutually between specifically described each technical characterictic in below (eg embodiment), thus consist of new or preferred technical scheme.As space is limited, this tired stating no longer one by one.
Description of drawings
Fig. 1 is (a) XRD, (b) TEM of the prepared nanoparticle of embodiment 1 and (c) EDS figure.
Fig. 2 is (a) T1 signal and (b) the T2 signal results figure of the MRI test of the prepared nanoparticle of embodiment 1.
Fig. 3 is (a) TEM, (b) HRTEM, (c) EDS of the prepared nanoparticle of Comparative Examples 1 and (d) XRD figure.
Fig. 4 is the prepared Gd of Comparative Examples 1
2O
3(a) T1 signal of nanocrystalline MRI test and (b) T2 signal results figure.
The specific embodiment
The present inventor is through extensively and in depth research, and accident is developed a kind of novel gadolinium sesquioxide/titanium dioxide composite nanoparticle first, and this nanoparticle not only can be used as contrast agent, and can be used in therapeutic treatment.On this basis, finished the present invention.
Nanoparticle
Among the present invention, " Gd
2O
3-TiO
2Composite nanoparticle ", " Gd
2O
3/ TiO
2Composite nanoparticle ", " Gd
2O
3-TiO
2Nanoparticle ", " Gd
2O
3/ TiO
2Nanoparticle ", " Gd
2O
3-TiO
2Particle ", " Gd
2O
3/ TiO
2Particle ", " Gd
2O
3Composite Ti O
2Nanoparticle " all have identical implication, refer to comprise gadolinium sesquioxide (Gd
2O
3) and titanium dioxide (TiO
2) nanoparticle.
Nanoparticle of the present invention is by gadolinium sesquioxide (Gd
2O
3) and titanium dioxide (TiO
2) be composited, carry gadolinium sesquioxide by the titanium dioxide parcel.
Among the present invention, described titanium dioxide is single-phase anatase titania.
In the gross weight of described nanoparticle, described nanoparticle comprises the 20wt%-80wt% titanium oxide, and surplus is gadolinium sesquioxide.
The particle diameter of described nanoparticle is 25-200nm.
In a preference, the particle diameter of described nanoparticle is 25-100nm, preferably, is 30-160nm.
Nano-TiO
2Be a kind of inorganic material of biocompatibility excellence, the application in the medical science optical dynamic therapy has obtained extensive concern.Utilize TiO
2Photocatalytic activity or with TiO
2Nanoparticle is combined with biomolecule or drug molecule and can be played therapeutical effect simultaneously.Nanoparticle of the present invention is by gadolinium sesquioxide (Gd
2O
3) and titanium dioxide (TiO
2) be composited, can improve Gd
2O
3The biocompatibility of nanoparticle, and Gd
2O
3Composite Ti O
2The Gd that the size of nanoparticle is more independent
2O
3Nanoparticle is large, causes gadolinium ion mobile restricted, and the speed of rotation slows down, more independent Gd
2O
3The nanoparticle relaxation ability is stronger.
Nanoparticle can exist with solid such as powder type, also can exist with suspension or colloidal form in disperse medium, have that particle size distribution is even, size is controlled, in the water favorable dispersibility do not reunite, the advantage such as good biocompatibility.
Described disperse medium is selected from: the mixed liquor of water or water and ethanol.The volume ratio of described water and ethanol is 1:0.2 ~ 6, preferably, is 1:4 ~ 4:1.
In preferred embodiment, can contain surfactant in the described disperse medium, described surfactant is cetyl trimethyl ammonium bromide, ammonium lauryl sulfate, tween, citric acid or Polyethylene Glycol.
Preparation method
The preparation method of nanoparticle suspension of the present invention or colloidal sol may further comprise the steps:
(i) trivalent gadolinium salt is dissolved in the polyhydric alcohol solutions, the polyhydric alcohol solutions that adds alkali reacts;
(ii) tetravalent salt of titanium solution is dropped in the reaction solution that step (i) makes, reaction obtains nanoparticle suspension claimed in claim 4 or colloidal sol, wherein,
Described trivalent gadolinium salt is selected from: Gadolinium trinitrate, Gadolinium trichloride, six water Gadolinium trinitrates, six water Gadolinium trichlorides or its combination;
Described alkali is selected from: sodium hydroxide, potassium hydroxide or its combination;
Described each polyhydric alcohol is independently selected from: diglycol or diethylene glycol or its combination;
Described tetravalent salt of titanium is selected from: butyl titanate or titanium tetrachloride or its combination;
Described tetravalent salt of titanium solution refers to that tetravalent salt of titanium is dissolved in the solution of the solvent acquisition that is selected from lower group: the mixed liquor of water and ethanol.The volume ratio of described water and ethanol is 1:0.2 ~ 6, preferably, is 1:4 ~ 4:1.
The molar concentration of the polyhydric alcohol solutions of described trivalent gadolinium salt is 0.05-1.5mol/L, and preferably, molar concentration is 0.1-0.5mol/L.
The molar concentration rate of the polyhydric alcohol solutions of described trivalent gadolinium salt and the polyhydric alcohol solutions of alkali is that 1:0.5 is to 1:2.
The mol ratio of described trivalent gadolinium salt and alkali is 1:1 to 1:4.
The concentration of described tetravalent salt of titanium solution is 0.1mol/L to 8mol/L, preferably, is 0.3mol/L to 5mol/L, more preferably, is 0.4mol/L to 3.5mol/L.
The mol ratio of described tetravalent salt of titanium and described trivalent gadolinium salt is that 1:1 is to 5:1.
Described step (i) is 100 ℃ to 200 ℃ reactions 0.5-6 hour, again in 140-250 ℃ of reaction 2-8 hour.Preferably, described step (i) is 120 ℃ to 160 ℃ reactions 40 minutes-2.5 hours, again in 160-220 ℃ of reaction 2.5-5.5 hour.
The reaction temperature of described step (ii) is 0-100 ℃, reacts 4-10 hour.
Described method also comprises the step that reaction solution that step (i) is obtained to make is dialysed; Perhaps also be included in the step of adding surfactant in nanoparticle suspension that step (ii) obtains or the colloidal sol, described surfactant is cetyl trimethyl ammonium bromide, ammonium lauryl sulfate, tween, citric acid or Polyethylene Glycol.
In another preference, the addition of described surfactant is 0.2mol/L to 2mol/L, and preferably, addition is 0.2mol/L to 1.5mol/L.
Described method also comprises: the step that the nanoparticle suspension that step (ii) is obtained or colloidal sol carry out ripening; Or carrying out the step of ripening after in nanoparticle suspension that step (ii) obtains or colloidal sol, adding surfactant, described surfactant is cetyl trimethyl ammonium bromide, ammonium lauryl sulfate, tween, citric acid or Polyethylene Glycol.
In another preference, the time of described ripening is 16-36 hour.
Nanoparticle suspension or colloidal sol are carried out centrifugal, lyophilization is processed and is obtained the nanoparticle pressed powder.
In a preferred implementation of the present invention, nanoparticle of the present invention can prepare by following steps:
1). take by weighing appropriate bases, it is dissolved in an amount of polyhydric alcohol solutions, obtaining concentration after magnetic agitation and the abundant dissolving is the A solution of 0.1mol/L to 1mol/L;
2). take by weighing an amount of trivalent gadolinium salt hydrate, it is dissolved in an amount of polyhydric alcohol solutions, obtaining concentration after magnetic agitation is fully dissolved is the B solution of 0.1mol/L to 1mol/L;
3). A solution is added in the B solution, stirred 1-3 hour at 120-160 ℃ of lower magnetic force, stirred 3-5 hour in 160-210 ℃ of lower magnetic force again, reactant liquor is dialysed: the molecular cut off 3500 of bag filter, changed water in 10-15 hour 1 time, dialyse 3-4 time, changed water 1 time, and dialysed 3-4 time in 20-30 hour;
4). be that the tetravalent salt of titanium solution of 0.1mol/L to 5mol/L dropwise adds above-mentioned dialysis solution with molar concentration, so that TiO
2Mass percent in composite nanoparticle is 20% to 80%(take the complex gross weight as benchmark) fully stir;
5). after reaction is finished, in product, add an amount of surfactant, continue to stir more than the 30min;
6). with prepared Gd
2O
3Composite Ti O
2Nanoparticle suspension or colloidal sol are packed in the reagent bottle, put into 4 ℃ refrigerator and treat the contrast agent as preparation MRI; Or with prepared Gd
2O
3Composite Ti O
2Nanoparticle suspension or colloidal sol product carry out centrifugal, and it is for subsequent use to obtain powdery product after lyophilization.
Wherein, described alkali, polyhydric alcohol, trivalent gadolinium salt, tetravalent salt of titanium, surfactant etc. is described as defined above.
By the prepared Gd of said method
2O
3Composite Ti O
2Nanoparticle can be dispersed in water or the aqueous solution, can long preservation in 4 ℃ environment, occur without deposited phenomenon, and prove Gd
2O
3Composite Ti O
2Nanoparticle has good dispersibility and stability.
Use
Nanoparticle of the present invention, good water solubility, good biocompatibility, nothing or low toxicity, magnetic susceptibility height.
Nanoparticle of the present invention has paramagnetism and photocatalytic activity double properties, on the one hand, and paramagnetism Gd
2O
3MRI radiography function with T1 weighting, imaging resolution is high, signal is abundant, can be used for preparing magnetic resonance imaging contrast, on the other hand, has the optical dynamic therapy effect, Gd
2O
3Component can make TiO
2The photohole of component Surface Creation separates with electronics, prolongs the binding time of hole and electronics, improves its photocatalytic activity, is conducive to improve TiO
2The treatment function of component.
Therefore, nanoparticle of the present invention or nanoparticle suspension or colloidal sol can be for the preparation of (a) contrast agent; Or (b) inorganic photosensitizer.
Described contrast agent is magnetic resonance imaging contrast.
Described photosensitizer is inorganic photosensitizer used in the optical dynamic therapy.
Based on Gd
2O
3Composite Ti O
2The novel MRI contrast agent of nanoparticle ensures that for improving the MRI detection sensitivity, reducing medical science test-and-treat cost people's life and health have great importance.
The above-mentioned feature that the present invention mentions, or the feature that embodiment mentions can combination in any.All features that this case description discloses can with any composition forms and usefulness, each feature that discloses in the description can be replaced by any alternative characteristics of identical, impartial or similar purpose that provides.Therefore except special instruction is arranged, the feature that discloses only is the general example of equalization or similar features.
Usefulness of the present invention is:
(1) the invention provides a kind of novel Gd
2O
3/ TiO
2Composite nanoparticle, particle size distribution is even, size is controlled, good biocompatibility.
(2) nanoparticle of the present invention not only has the radiography function, and has the therapeutic treatment function.
(3) nanoparticle preparation method of the present invention is simple, mild condition.
(4) nanoparticle radiography performance of the present invention is compared with the gadolinium complex contrast agent of medically clinical practice, and the radiography performance is significantly improved.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example is usually according to normal condition or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise percentage ratio and umber calculate by weight.
Unless otherwise defined, the same meaning that employed all specialties and scientific words and one skilled in the art are familiar with in the literary composition.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The usefulness that better implementation method described in the literary composition and material only present a demonstration.
Universal method
The TEM test
The JEOL-2100 transmission electron microscope, test condition: 200Kv, 101 μ A
The HRTEM test
The JEOL-2100 transmission electron microscope, test condition: 200Kv, 101 μ A
The EDS test
The JEOL-2100 transmission electron microscope, test condition: 200Kv, 101 μ A
Diameter characterization
Characterize particle size distribution (irregularly shaped just by the ultimate range measured value in the shape) according to ImageJ statistical result
The XRD test
Cu K α target (40kV, 40mA), 0.02 ° of step-length (2 θ), 3s/ step
The MRI test
Test condition is T1:TR=8000ms, TE=200ms, T2:TR=4000ms, TE=200ms
Embodiment 1
Take by weighing six water Gadolinium trinitrate (Gd (NO
3)
36H
2O) 6mmol is dissolved into it in 20mL diglycol, stirs at 140 ℃ of lower magnetic forces, to guarantee Gd (NO
3)
36H
2O fully dissolves, and obtains the A solution for later use.
Weighing sodium hydroxide (NaOH) 10mmol is dissolved into it in 40mL diglycol, and magnetic agitation is fully dissolved to guarantee NaOH, obtains the B solution for later use.
A solution is added in the B solution, 140 ℃ of lower magnetic forces stir 1 hour, 180 ℃ of lower magnetic forces stirred 4 hours.Reactant liquor is dialysed: the bag filter molecular cut off changed water in 3500,12 hours 1 time, dialysed 3 times, changed water 1 time, and dialysed 3 times in 24 hours.
Be that the butyl titanate solution 10mL of 1.8mol/L dropwise adds above-mentioned dialysis solution with molar concentration, continue to stir;
React after 8 hours, in product, add the CTAB15mL of 0.8mmol/L, and continue to stir 30min;
Product is carried out ripening at room temperature, and digestion time is 18 hours;
Product is carried out centrifugal, obtain pure Gd
2O
3Composite Ti O
2Nanoparticle, it is for subsequent use to obtain pressed powder through lyophilization; Or with Gd
2O
3Composite Ti O
2Nanoparticle suspension or colloidal sol are packed in the reagent bottle, and the refrigerator of putting into 4 ℃ is stand-by.
Adopt XRD, TEM and the Gd of EDS to making
2O
3Composite Ti O
2Nanoparticle is analyzed, the result as shown in Figure 1, the result shows the good dispersion of nanoparticle, particle diameter is even, according to ImageJ statistical result, particle size distribution is at 30-50nm, and patterned features is obvious, because TiO
2Patterned features clearly masks Gd
2O
3Patterned features, so the composite nanoparticle crystal formation shows as single-phase TiO
2Crystal formation: Anatase.
To the Gd that makes
2O
3Composite Ti O
2Nanoparticle carries out the test of T1 and the T2 relaxation rate of MRI.The MRI test condition is T1:TR=8000ms, TE=200ms, T2:TR=4000ms, TE=200ms.Prepared Gd as can be seen from Figure 2
2O
3Composite Ti O
2Nanoparticle r1=61.06mM
-1s
-1, r2=86.588mM
-1s
-1, r2/r1=1.418 near 1, proves that prepared nanoparticle can be used as good T1 contrast agent.
Take by weighing six water Gadolinium trinitrate (Gd (NO
3)
36H
2O) 6mmol is dissolved into it in 20mL diglycol, stirs at 140 ℃ of lower magnetic forces, to guarantee Gd (NO
3)
36H
2O fully dissolves, and obtains the A solution for later use.
Weighing sodium hydroxide (NaOH) 10mmol is dissolved into it in 40mL diglycol, and magnetic agitation is fully dissolved to guarantee NaOH, obtains the B solution for later use.
A solution is added in the B solution, stirred 1 hour at 140 ℃ of lower magnetic forces, 180 ℃ of lower magnetic forces stirred 4 hours.Reactant liquor is dialysed: the bag filter molecular cut off changed water in 3500,12 hours 1 time, dialysed 3 times, changed water 1 time, and dialysed 3 times in 24 hours.
Be that the butyl titanate solution 10mL of 0.6mol/L dropwise adds above-mentioned dialysis solution with molar concentration, continue to stir.
React after 5 hours, in product, add the cetyl trimethyl ammonium bromide CTAB15mL of 0.4mmol/L, and continue to stir 30min.
Product at room temperature placed carry out ripening, digestion time is 24 hours.
Product is carried out centrifugal, obtain pure Gd
2O
3/ TiO
2Composite nanoparticle, it is for subsequent use to obtain pressed powder through lyophilization; Or with Gd
2O
3/ TiO
2Composite nanoparticle suspension or colloidal sol are packed in the reagent bottle, and the refrigerator of putting into 4 ℃ is stand-by.
Be dispersed in the water obtaining nanoparticle after the lyophilization, place 4 ℃ of environment, observed afterwards all in 1 day, 3 days, 7 days, 30 days, 60 days, 90 days and to occur without deposited phenomenon, and do not reunite, show that nanoparticle has good dispersibility and water stability.
To the Gd that makes
2O
3Composite Ti O
2Nanoparticle carries out the test of T1 and the T2 relaxation rate of MRI, and r2/r1 proves that near 1 prepared nanoparticle can be used as good T1 contrast agent.
Take by weighing six water Gadolinium trinitrate (Gd (NO
3)
36H
2O) 6mmol is dissolved into it in 20mL diglycol, stirs at 140 ℃ of lower magnetic forces, to guarantee Gd (NO
3)
36H
2O fully dissolves, and obtains the A solution for later use.
Weighing sodium hydroxide (NaOH) 10mmol is dissolved into it in 40mL diglycol, and magnetic agitation is fully dissolved to guarantee NaOH, obtains the B solution for later use.
A solution is added in the B solution, stirred 1 hour at 160 ℃ of lower magnetic forces, 210 ℃ of lower magnetic forces stirred 4 hours.Reactant liquor is dialysed: the bag filter molecular cut off changed water in 3500,12 hours 1 time, dialysed 3 times, changed water 1 time, and dialysed 3 times in 24 hours.
Be that the butyl titanate solution 10mL of 1.2mol/L dropwise adds above-mentioned dialysis solution with molar concentration, continue to stir;
React after 5 hours, in product, add the CTAB15mL of 0.4mmol/L, and continue to stir 30min;
Product is carried out ripening at room temperature, and digestion time is 24 hours;
Product is carried out centrifugal, obtain pure Gd
2O
3Composite Ti O
2Nanoparticle, it is for subsequent use to obtain pressed powder through lyophilization; Or with Gd
2O
3Composite Ti O
2Nanoparticle suspension or colloidal sol are packed in the reagent bottle, and the refrigerator of putting into 4 ℃ is stand-by.
To the Gd that makes
2O
3Composite Ti O
2Nanoparticle carries out the test of T1 and the T2 relaxation rate of MRI.R1=18.31mM
-1s
-1, r2=59.22mM
-1s
-1, r2/r1=3.23 near 1, proves that prepared nanoparticle can be used as good T1 contrast agent.
Take by weighing six water Gadolinium trinitrate (Gd (NO
3)
36H
2O) 6mmol is dissolved into it in 20mL diglycol, stirs at 140 ℃ of lower magnetic forces, to guarantee Gd (NO
3)
36H
2O fully dissolves, and obtains the A solution for later use.
Weighing sodium hydroxide (NaOH) 8mmol is dissolved into it in 40mL diglycol, and magnetic agitation is fully dissolved to guarantee NaOH, obtains the B solution for later use.
A solution is added in the B solution, stirred 1 hour at 120 ℃ of lower magnetic forces, 200 ℃ of lower magnetic forces stirred 4 hours.Reactant liquor is dialysed: the bag filter molecular cut off changed water in 3500,12 hours 1 time, dialysed 3 times, changed water 1 time, and dialysed 3 times in 24 hours.
Be that the tetravalent salt of titanium solution 10mL of 0.6mol/L dropwise adds above-mentioned dialysis solution with molar concentration, continue to stir;
React after 5 hours, in product, add the tween Tween 15mL of 0.4mmol/L, and continue to stir 30min;
Product is carried out ripening at room temperature, and digestion time is 24 hours;
Product is carried out centrifugal, obtain pure Gd
2O
3Composite Ti O
2Nanoparticle, it is for subsequent use to obtain pressed powder through lyophilization; Or with Gd
2O
3Composite Ti O
2Nanoparticle suspension or colloidal sol are packed in the reagent bottle, and the refrigerator of putting into 4 ℃ is stand-by.
To the Gd that makes
2O
3Composite Ti O
2Nanoparticle carries out the test of T1 and the T2 relaxation rate of MRI.R1=11.27mM
-1s
-1, r2=18.02mM
-1s
-1, r2/r1=1.60 near 1, proves that prepared nanoparticle can be used as good T1 contrast agent.
Embodiment 5
Take by weighing six water Gadolinium trinitrate (Gd (NO
3)
36H
2O) 6mmol is dissolved into it in 20mL diglycol, stirs at 140 ℃ of lower magnetic forces, to guarantee Gd (NO
3)
36H
2O fully dissolves, and obtains the A solution for later use.
Weighing sodium hydroxide (NaOH) 20mmol is dissolved into it in 40mL diglycol, and magnetic agitation is fully dissolved to guarantee NaOH, obtains the B solution for later use.
A solution is added in the B solution, stirred 1 hour at 160 ℃ of lower magnetic forces, 190 ℃ of lower magnetic forces stirred 4 hours.Reactant liquor is dialysed: the bag filter molecular cut off changed water in 3500,12 hours 1 time, dialysed 3 times, changed water 1 time, and dialysed 3 times in 24 hours.
Be that the tetraisopropyl titanate solution 10mL of 1.8mol/L dropwise adds above-mentioned dialysis solution with molar concentration, continue to stir;
React after 5 hours, in product, add the citric acid 15mL of 0.4mmol/L, and continue to stir 30min;
Product is carried out ripening at room temperature, and digestion time is 20 hours;
Product is carried out centrifugal, obtain pure Gd
2O
3Composite Ti O
2Nanoparticle, it is for subsequent use to obtain pressed powder through lyophilization; Or with Gd
2O
3Composite Ti O
2Nanoparticle suspension or colloidal sol are packed in the reagent bottle, and the refrigerator of putting into 4 ℃ is stand-by.
To the Gd that makes
2O
3Composite Ti O
2Nanoparticle carries out the test of T1 and the T2 relaxation rate of MRI, and r2/r1 near 1, proves that prepared nanoparticle can be used as good T1 contrast agent.
Take by weighing six water Gadolinium trinitrate (Gd (NO
3)
36H
2O) 6mmol is dissolved into it in 20mL diglycol, stirs at 140 ℃ of lower magnetic forces, to guarantee Gd (NO
3)
36H
2O fully dissolves, and obtains the A solution for later use.
Weighing sodium hydroxide (NaOH) 8.5mmol is dissolved into it in 40mL diglycol, and magnetic agitation is fully dissolved to guarantee NaOH, obtains the B solution for later use.
A solution is added in the B solution, stirred 1 hour at 160 ℃ of lower magnetic forces, 190 ℃ of lower magnetic forces stirred 4 hours.Reactant liquor is dialysed: the bag filter molecular cut off changed water in 3500,12 hours 1 time, dialysed 3 times, changed water 1 time, and dialysed 3 times in 24 hours.
Be that the titanium tetrachloride solution 10mL of 1.8mol/L dropwise adds above-mentioned dialysis solution with molar concentration, continue to stir;
React after 5 hours, in product, add the Polyethylene Glycol 15mL of 0.4mmol/L, and continue to stir 30min;
Product is carried out ripening at room temperature, and digestion time is 24 hours;
Product is carried out centrifugal, obtain pure Gd
2O
3Composite Ti O
2Nanoparticle, it is for subsequent use to obtain pressed powder through lyophilization; Or with Gd
2O
3Composite Ti O
2Nanoparticle suspension or colloidal sol are packed in the reagent bottle, and the refrigerator of putting into 4 ℃ is stand-by.
To the Gd that makes
2O
3Composite Ti O
2Nanoparticle carries out the test of T1 and the T2 relaxation rate of MRI.R1=12.23mM
-1s
-1, r2=17.77mM
-1s
-1, r2/r1=1.45 near 1, proves that prepared nanoparticle can be used as good T1 contrast agent.
Embodiment 7
Take by weighing six water Gadolinium trinitrate (Gd (NO
3)
36H
2O) 8mmol is dissolved into it in 20mL diglycol, stirs at 140 ℃ of lower magnetic forces, to guarantee Gd (NO
3)
36H
2O fully dissolves, and obtains the A solution for later use.
Weighing sodium hydroxide (NaOH) 12mmol is dissolved into it in 40mL diglycol, and magnetic agitation is fully dissolved to guarantee NaOH, obtains the B solution for later use.
A solution is added in the B solution, stirred 1 hour at 160 ℃ of lower magnetic forces, 190 ℃ of lower magnetic forces stirred 4 hours.Reactant liquor is dialysed: the bag filter molecular cut off changed water in 3500,12 hours 1 time, dialysed 3 times, changed water 1 time, and dialysed 3 times in 24 hours.
Be that the tetraisopropyl titanate solution 10mL of 1.8mol/L dropwise adds above-mentioned dialysis solution with molar concentration, continue to stir;
React after 5 hours, in product, add the ammonium lauryl sulfate 15mL of 0.4mmol/L, and continue to stir 30min;
Product is carried out ripening at room temperature, and digestion time is 20 hours;
Product is carried out centrifugal, obtain pure Gd
2O
3Composite Ti O
2Nanoparticle, it is for subsequent use to obtain pressed powder after lyophilization; Or with Gd
2O
3Composite Ti O
2Nanoparticle suspension or colloidal sol are packed in the reagent bottle, and the refrigerator of putting into 4 ℃ is stand-by.
To the Gd that makes
2O
3Composite Ti O
2Nanoparticle carries out the test of T1 and the T2 relaxation rate of MRI, and r2/r1 proves that near 1 prepared nanoparticle can be used as good T1 contrast agent.
Take by weighing six water Gadolinium trinitrate (Gd (NO
3)
36H
2O) 6mmol is dissolved into it in 20mL diglycol, stirs at 140 ℃ of lower magnetic forces, to guarantee Gd (NO
3)
36H
2O fully dissolves, and obtains the A solution for later use.
Weighing sodium hydroxide (NaOH) 10mmol is dissolved into it in 40mL diglycol, and magnetic agitation is fully dissolved to guarantee NaOH, obtains the B solution for later use.
A solution is added in the B solution, 140 ℃ of lower magnetic forces stir 1 hour, 180 ℃ of lower magnetic forces stirred 4 hours.Reactant liquor is dialysed: the bag filter molecular cut off changed water in 3500,12 hours 1 time, dialysed 3 times, changed water 1 time, and dialysed 3 times in 24 hours.
Be that the butyl titanate solution 10mL of 3mol/L dropwise adds above-mentioned dialysis solution with molar concentration, continue to stir;
React after 8 hours, in product, add the ammonium lauryl sulfate 15mL of 1.2mmol/L, and continue to stir 30min;
Product is carried out ripening at room temperature, and digestion time is 18 hours;
Product is carried out centrifugal, obtain pure Gd
2O
3Composite Ti O
2Nanoparticle, it is for subsequent use to obtain pressed powder after lyophilization; Or with Gd
2O
3Composite Ti O
2Nanoparticle suspension or colloidal sol are packed in the reagent bottle, and the refrigerator of putting into 4 ℃ is stand-by.
Adopt the Gd of TEM to making
2O
3Composite Ti O
2Nanoparticle is analyzed, and according to ImageJ statistical result, particle size distribution is at 80-160nm.
To the Gd that makes
2O
3Composite Ti O
2Nanoparticle carries out the test of T1 and the T2 relaxation rate of MRI.R1=9.23mM
-1s
-1, r2=16.45mM
-1s
-1, r2/r1=1.78 near 1, proves that prepared nanoparticle can be used as good T1 contrast agent.
Embodiment 9
Take by weighing six water Gadolinium trinitrate (Gd (NO
3)
36H
2O) 6mmol is dissolved into it in 20mL diglycol, stirs at 140 ℃ of lower magnetic forces, to guarantee Gd (NO
3)
36H
2O fully dissolves, and obtains the A solution for later use.
Weighing sodium hydroxide (NaOH) 10mmol is dissolved into it in 40mL diglycol, and magnetic agitation is fully dissolved to guarantee NaOH, obtains the B solution for later use.
A solution is added in the B solution, stirred 1 hour at 140 ℃ of lower magnetic forces, 180 ℃ of lower magnetic forces stirred 4 hours.
Reactant liquor is dialysed: the bag filter molecular cut off changed water in 3500,12 hours 1 time, dialysed 3 times, changed water 1 time, and dialysed 3 times in 24 hours.
Be that the butyl titanate solution 10mL of 0.6mol/L dropwise adds above-mentioned dialysis solution with molar concentration, continue to stir.
React after 5 hours, in product, add the cetyl trimethyl ammonium bromide CTAB15mL of 0.4mmol/L, and continue to stir 30min.
Product is carried out ripening at room temperature, and digestion time is 24 hours.
Product is carried out centrifugal, obtain pure Gd
2O
3/ TiO
2Composite nanoparticle, it is for subsequent use to obtain pressed powder through lyophilization; Or with Gd
2O
3/ TiO
2Composite nanoparticle suspension or colloidal sol are packed in the reagent bottle, and the refrigerator of putting into 4 ℃ is stand-by.
To the Gd that makes
2O
3Composite Ti O
2Nanoparticle carries out the test of T1 and the T2 relaxation rate of MRI, and r2/r1 near 1, proves that prepared nanoparticle can be used as good T1 contrast agent.
Gd to embodiment 1-9 preparation
2O
3/ TiO
2Composite nanoparticle carries out external illumination experiment, culture dish plantation MCF-7 tumor cell, density 1 * 10
5Individual/mL, a blank experimental group is set does not carry out ultra-vioket radiation; A blank experiment group is carried out ultra-vioket radiation; One adds 300 μ g/mL Gd
2O
3/ TiO
2Composite nanoparticle is at 37 ℃ of lower 5%CO
2Incubator in cultivated 30 minutes, it was carried out ultra-vioket radiation 30 minutes, irradiation power density is 100-250Mw/cm
2, energy density is 100-500J/cm
2, again at 37 ℃ of lower 5%CO
2Incubator in cultivated 24 hours, add 200 μ L 3-(4,5-dimethylthiazole-2)-2,5-diphenyl tetrazole bromine salt (MTT), continue to cultivate 4 hours, the sucking-off culture fluid, add 15 μ L dimethyl sulfoxide, survey cell survival rate: MTT with the MTT method and can act on respiratory chain in the living cells mitochondrion, tetrazole ring cracking under the effect of succinate dehydrogenase and cytochrome C, generate blue formazan(formazan) crystallization, the growing amount of crystallization only is directly proportional with the living cells number (in the dead cell succinate dehydrogenase disappear, MTT can not be reduced), the formazan(formazan that reduction generates) crystallization dissolves in dimethyl sulfoxide DMSO solution, utilize microplate reader to measure the optical density OD value at 550nm place, to reflect the living cells number.The result is as shown in table 1.
Table 1 survival rate relatively
End product shows that the survival rate of the tumor cell of the nanoparticle of adding embodiment 1-9 preparation is starkly lower than the survival rate (80%) of the tumor cell of independent ultra-vioket radiation, shows that nanoparticle of the present invention has good optical dynamic therapy effect.
Comparative Examples 1
Take by weighing six water Gadolinium trinitrate (Gd (NO
3)
36H
2O) 6mmol is dissolved into it in 20mL diglycol, stirs at 140 ℃ of lower magnetic forces, to guarantee Gd (NO
3)
36H
2O fully dissolves, and obtains the A solution for later use.
Weighing sodium hydroxide (NaOH) 10mmol is dissolved into it in 40mL diglycol, and magnetic agitation is fully dissolved to guarantee NaOH, obtains the B solution for later use.
A solution is added in the B solution, stirred 1 hour at 140 ℃ of lower magnetic forces, 180 ℃ of lower magnetic forces stirred 4 hours.Reactant liquor is dialysed: the bag filter molecular cut off changed water in 3500,12 hours 1 time, dialysed 3 times, changed water 1 time in 24 hours, dialysed 3 times, obtained pure monomer Gd
2O
3, the refrigerator of putting into 4 ℃ is stand-by.
Adopt TEM, HRTEM, EDS, XRD that the nanoparticle that makes is analyzed, the result as shown in Figure 3, the result shows the good dispersion of nanoparticle, particle diameter is even, according to ImageJ statistical result, particle size distribution is at 3-5nm, and patterned features is obvious: be cubic.
The monomer Gd of preparation
2O
3With the Gd among the embodiment 3
2O
3/ TiO
2Composite nanoparticle carries out the MRI test comparison, the result as shown in Figure 4, r1=42.59mM
-1s
-1, r2=73.68mM
-1s
-1, r2/r1=1.73.Show: the Gd among the embodiment 3
2O
3/ TiO
2Composite nanoparticle is than the monomer Gd in the Comparative Examples 1
2O
3Relaxation rate be significantly increased TiO
2Improved Gd
2O
3Water solublity, and water proton is near nanoparticle the time, the rotational time in sample prolongs, and causes the T1 relaxation signals to strengthen.
All quote in this application as a reference at all documents that the present invention mentions, just as each piece document is quoted separately as a reference.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. a nanoparticle is characterized in that, described nanoparticle comprises gadolinium sesquioxide and titanium dioxide.
2. nanoparticle as claimed in claim 1 is characterized in that, in the gross weight of described nanoparticle, described nanoparticle comprises 20wt%-80wt% titanium dioxide, and surplus is gadolinium sesquioxide.
3. such as right 1 described nanoparticle, it is characterized in that the particle diameter of described nanoparticle is 25-200nm.
4. a nanoparticle suspension or colloidal sol is characterized in that comprise nanoparticle claimed in claim 1 and disperse medium, described disperse medium is selected from: the mixed liquor of water and ethanol.
5. nanoparticle suspension as claimed in claim 1 or colloidal sol, it is characterized in that, contain surfactant in the described disperse medium, described surfactant is cetyl trimethyl ammonium bromide, ammonium lauryl sulfate, tween, citric acid or Polyethylene Glycol.
6. the preparation method of a nanoparticle suspension claimed in claim 4 or colloidal sol is characterized in that, may further comprise the steps:
(i) trivalent gadolinium salt is dissolved in the polyhydric alcohol solutions, the polyhydric alcohol solutions that adds alkali reacts;
(ii) tetravalent salt of titanium solution is dropped in the reaction solution that step (i) makes, reaction obtains nanoparticle suspension claimed in claim 4 or colloidal sol, wherein,
Described trivalent gadolinium salt is selected from: Gadolinium trinitrate, Gadolinium trichloride, six water Gadolinium trinitrates, six water Gadolinium trichlorides or its combination;
Described alkali is selected from: sodium hydroxide, potassium hydroxide or its combination;
Described each polyhydric alcohol is independently selected from: diglycol or diethylene glycol or its combination;
Described tetravalent salt of titanium is selected from: butyl titanate or titanium tetrachloride or its combination;
Described tetravalent salt of titanium solution refers to the solution that tetravalent salt of titanium mixed liquor water-soluble and ethanol obtains.
7. preparation method as claimed in claim 6 is characterized in that, described method also comprises the step that reaction solution that step (i) is obtained to make is dialysed; Perhaps
Also be included in the step of adding surfactant in nanoparticle suspension that step (ii) obtains or the colloidal sol, described surfactant is cetyl trimethyl ammonium bromide, ammonium lauryl sulfate, tween, citric acid or Polyethylene Glycol.
8. preparation method as claimed in claim 6 is characterized in that, described method also comprises:
The step that the nanoparticle suspension that step (ii) is obtained or colloidal sol carry out ripening; Or
Carry out the step of ripening add surfactant in nanoparticle suspension that step (ii) obtains or colloidal sol after, described surfactant is cetyl trimethyl ammonium bromide, ammonium lauryl sulfate, tween, citric acid or Polyethylene Glycol.
9. the preparation method of nanoparticle as claimed in claim 1 is characterized in that, described method comprises carries out nanoparticle suspension claimed in claim 4 or colloidal sol centrifugal, and lyophilization is processed and obtained nanoparticle claimed in claim 1.
10. the purposes of nanoparticle as claimed in claim 1 or nanoparticle suspension claimed in claim 4 or colloidal sol is characterized in that, for the preparation of:
(a) contrast agent; Or
(b) inorganic photosensitizer.
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| CN110606742A (en) * | 2019-10-24 | 2019-12-24 | 中国核动力研究设计院 | TiO for nuclear power2-Gd2O3Burnable poison ceramic material and preparation method thereof |
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| CN112089837A (en) * | 2020-09-17 | 2020-12-18 | 西南交通大学 | Multi-modal imaging/photothermal therapy compound agent and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106421822A (en) * | 2015-08-17 | 2017-02-22 | 中国科学院宁波材料技术与工程研究所 | Composite nanoparticle with Janus structure and preparation method and application thereof |
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| CN111629755A (en) * | 2017-11-17 | 2020-09-04 | 施里昂医疗有限公司 | Particles for combined radiation therapy treatment of cancer |
| CN110606742A (en) * | 2019-10-24 | 2019-12-24 | 中国核动力研究设计院 | TiO for nuclear power2-Gd2O3Burnable poison ceramic material and preparation method thereof |
| CN110606742B (en) * | 2019-10-24 | 2022-02-22 | 中国核动力研究设计院 | TiO for nuclear power2-Gd2O3Burnable poison ceramic material and preparation method thereof |
| CN112089837A (en) * | 2020-09-17 | 2020-12-18 | 西南交通大学 | Multi-modal imaging/photothermal therapy compound agent and preparation method and application thereof |
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