CN106276818B - 双金属硫族三元半导体纳米颗粒及其制备方法 - Google Patents
双金属硫族三元半导体纳米颗粒及其制备方法 Download PDFInfo
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- CN106276818B CN106276818B CN201610575997.2A CN201610575997A CN106276818B CN 106276818 B CN106276818 B CN 106276818B CN 201610575997 A CN201610575997 A CN 201610575997A CN 106276818 B CN106276818 B CN 106276818B
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- water
- ternary semiconductor
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- OPMAIAZERBNUSE-UHFFFAOYSA-N copper selanylidenesilver Chemical compound [Cu].[Ag]=[Se] OPMAIAZERBNUSE-UHFFFAOYSA-N 0.000 description 2
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- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- IKHZKATVXPFKTI-UHFFFAOYSA-N tellanylideneiron Chemical compound [Fe].[Te] IKHZKATVXPFKTI-UHFFFAOYSA-N 0.000 description 2
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- FDKWRPBBCBCIGA-UWTATZPHSA-N D-Selenocysteine Natural products [Se]C[C@@H](N)C(O)=O FDKWRPBBCBCIGA-UWTATZPHSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
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- AUYYCJSJGJYCDS-LBPRGKRZSA-N Thyrolar Chemical class IC1=CC(C[C@H](N)C(O)=O)=CC(I)=C1OC1=CC=C(O)C(I)=C1 AUYYCJSJGJYCDS-LBPRGKRZSA-N 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
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- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- ZKZBPNGNEQAJSX-UHFFFAOYSA-N selenocysteine Natural products [SeH]CC(N)C(O)=O ZKZBPNGNEQAJSX-UHFFFAOYSA-N 0.000 description 1
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- 235000016491 selenocysteine Nutrition 0.000 description 1
- 125000001554 selenocysteine group Chemical group [H][Se]C([H])([H])C(N([H])[H])C(=O)O* 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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- 239000011781 sodium selenite Substances 0.000 description 1
- 235000015921 sodium selenite Nutrition 0.000 description 1
- VOADVZVYWFSHSM-UHFFFAOYSA-L sodium tellurite Chemical compound [Na+].[Na+].[O-][Te]([O-])=O VOADVZVYWFSHSM-UHFFFAOYSA-L 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
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- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
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- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/06—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations
- A61K49/08—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by the carrier
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/22—Echographic preparations; Ultrasound imaging preparations ; Optoacoustic imaging preparations
- A61K49/222—Echographic preparations; Ultrasound imaging preparations ; Optoacoustic imaging preparations characterised by a special physical form, e.g. emulsions, liposomes
- A61K49/225—Microparticles, microcapsules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Public Health (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Engineering & Computer Science (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Radiology & Medical Imaging (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Acoustics & Sound (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
本发明提供一种双金属硫族三元半导体纳米颗粒和生物相容性的双金属硫族三元半导体纳米颗粒以及其制备方法,所述双金属硫族三元半导体的通式为AxByCZ,其中A是IB族金属元素,如Cu,Ag,0<x≤3;B是含有3d电子层的过渡金属元素、ⅢA‑ⅣA族金属元素和镧系元素中的一种,如Mn,Fe,Ni,Ga,In,Ag,Sn,Gd,0<y≤2;C是ⅥA族非金属元素,如S,Se,Te,1≤z≤2。制备方法操作简单,易于推广,产率高,该双金属硫族三元半导体纳米颗粒经过具有生物相容性的高分子材料修饰后可用于光声成像、核磁共振成像及光热治疗等生物医学方面。
Description
技术领域
本发明涉及生物医学领域,尤其涉及一种具有生物相容性的双金属硫族三元半导体纳米颗粒及其制备方法。
背景技术
金属硫族化合物是一类非常重要的半导体材料,尤其是双金属硫族三元半导体(Ax By CZ,其中A=Cu,Ag;B=Mn,Fe,Ni,Ga,In,Ag,Sn,Gd;C=S,Se,Te;0<x≤3,0<y≤2;1≤z≤2),纳米材料更是因其优异的光电性能、光热性能和热电性能而被应用于太阳能电池、气体传感器、光电探测器、声光器件和相变存储器等。最近,随着一些三元半导体纳米材料独特的物理和化学性质被发现,比如在近红外区的较高吸收系数和较高光热转换效率以及低毒性,使它们在光声成像、光热治疗等生物医学等领域具有广泛的应用前景。此外,它们中的有些元素还是生命必需的微量元素,对人体健康至关重要。如硒是硒代半胱氨酸和含硒酶如过氧化物酶的必需组分,参与人体中多个主要代谢途径,如甲状腺激素代谢、抗氧化防御系统和免疫功能,在抗癌、抗氧化等方面发挥重要作用。
光声成像是利用光热效应获得生物组织或材料的断层图像或三维立体图像的一种成像方法。光声成像造影剂是提高光声成像信号的对比增强剂,它通过改变局部组织的声学和光学特性,提高成像对比度和分辨率,从而显著增强光声成像的效果,是当前分子影像研究的热点之一。光声造影剂要求颗粒尺寸小、稳定性好、具有良好水溶性和优异的生物相容性。
核磁共振成像技术(MRI)是利用正常组织与病变组织中水质子的弛豫时间(或弛豫速率)不同来进行检测。为了增加病变组织与正常组织的对比度,通常需要使用造影增强剂。磁共振造影增强剂除了满足药物的基本要求,如生物相容性、水溶性和稳定性之外,还应具有高弛豫率、靶向性和适当的体内存留时间等特性。
光热治疗是采用近红外光照射病变部位,通过光热治疗剂将光转化为热,使照射部位温度升高杀死病变细胞,从而达到治疗目的。实验表明很多双金属硫族三元半导体纳米颗粒在近红外区具有较强的吸收和较高的光热转化效率,可以用于光声成像和光热治疗。然而,由于制备水溶性和生物相容性的双金属硫族三元半导体纳米颗粒较为困难,有关这一方面的报道较少。
双金属硫族三元半导体纳米材料的制备方法有以下几种:(1)固相反应法;(2)化学气相沉积法(CVD);(3)物理气相沉积法(PVD);(4)液相合成法。这些方法的制备过程较复杂、条件较为苛刻,所得产物的尺寸较大、水溶性和生物相容性较差,使得双金属硫族三元半导体纳米材料在生物医学方面的应用极少报道。因此,如何合成粒径均一而且具有水溶性和生物相容性的双金属硫族三元半导体纳米颗粒是其应用于生物医学的关键。
有鉴于上述的缺陷,本设计人,积极加以研究创新,以期创设一类双金属硫族三元半导体纳米颗粒及其制备方法,使其更具有产业上的利用价值。
发明内容
为解决上述技术问题,本发明的目的是提供一类双金属硫族三元半导体纳米颗粒及其制备方法,该制备方法操作简单,易于推广,产率高,该双金属硫族三元半导体纳米颗粒经过具有生物相容性的高分子材料修饰后可用于光声成像、核磁共振成像及光热治疗等生物医学方面。
本发明提出的一种双金属硫族三元半导体纳米颗粒,所述双金属硫族三元半导体的通式为Ax By CZ,其中A是IB族金属元素,如Cu,Ag,0<x≤3;B是含有3d电子层的过渡金属元素、ⅢA-ⅣA族金属元素或镧系元素,如Mn,Fe,Ni,Ga,In,Ag,Sn,Gd,0<y≤2;C是ⅥA族非金属元素,如S,Se,Te,1≤z≤2。
进一步的,所述双金属硫族三元半导体外包覆有生物相容性高分子材料,所述高分子材料为天然高分子材料或人工高分子材料,所述天然高分子材料为各种血清蛋白(如人血清蛋白、牛血清蛋白等)、葡聚糖及其衍生物、壳聚糖及其衍生物、果胶、羧甲基纤维素中的一种或多种;所述人工高分子材料为聚乙烯吡咯烷酮、聚乙烯亚胺、聚乙二醇、聚丙烯酸及其衍生物中的一种或多种,其中聚乙烯吡咯烷酮的分子量在8000-40000之间。
本发明提供的双金属硫族三元半导体纳米颗粒的制备方法,包括以下步骤:
(1)将C的单质和/或化合物溶解在水中,其中C的摩尔浓度为0.001-1mlo/L;搅拌速度为100-1500r/min,反应时间大约0.1-7h,其中C为ⅥA族非金属元素;
(2)向步骤(1)得到的溶液中加入水溶性的A的金属盐和水溶性的B的金属盐,其中A、B的总摩尔浓度为0.001-1mol/L,搅拌0.1-10h,得到含有双金属硫族三元半导体纳米颗粒;其中A为IB族金属元素,B为过渡金属元素、ⅢA-ⅣA族金属元素和镧系元素中的一种。
(3)将步骤(2)中的溶液通过离心得到沉淀物双金属硫族三元半导体纳米颗粒,离心速率为1000-20000r/min,用超纯水洗涤离心后的沉淀,并在20-80℃下真空干燥1-24h,得到所述双金属硫族三元半导体纳米颗粒。
进一步的,在步骤(2)中,还向溶液中加入生物相容性高分子材料,所述生物相容性高分子材料浓度为1-20g/L,搅拌速度为100-1500r/min,反应时间为0.1-10h;所述高分子材料为天然高分子材料或人工高分子材料,所述天然高分子材料为各种血清蛋白(如人血清蛋白、牛血清蛋白等)、葡聚糖及其衍生物、壳聚糖及其衍生物、果胶、羧甲基纤维素中的一种或多种;所述人工高分子材料为聚乙烯吡咯烷酮、聚乙烯亚胺、聚乙二醇、聚丙烯酸及其衍生物中的一种或多种,其中聚乙烯吡咯烷酮的分子量在8000-40000之间。
将步骤(2)的溶液中的沉淀通过离心去除,在离心速率为1000-20000r/min下离心5-30min;将离心后的上清液超滤浓缩后采用透析的方式去除游离的生物相容性高分子,透析袋截留分子质量为8000-100000,透析时间为1-120h;再次将透析后的上清液离心,去除可能存在的沉淀,得到含有生物相容性双金属硫族三元半导体纳米颗粒的溶液,在20-80℃下真空干燥1-24h,得到生物相容性的双金属硫族三元半导体纳米颗粒。
进一步的,在步骤(1)中,水溶性的C的化合物选自硫化钠或硫化铵、硫代硫酸钠、亚硒酸钠或亚碲酸钠。
进一步的,在步骤(1)中,非水溶性的C的化合物选自硒、碲、二氧化硒或二氧化碲。
更进一步的,在步骤(1)中,还向水中加入还原剂,所述还原剂为硼氢化钠和硼氢化钾中的一种或组合,所述C的化合物与还原剂的摩尔比为1:2-1:9。
进一步的,在步骤(2)中,水溶性金属盐为盐酸盐、硝酸盐、硫酸盐、醋酸盐、柠檬酸盐和草酸盐中的一种或几种。
进一步的,所述水为去离子水、纯水或超纯水。
进一步的,在步骤(1)中,水为除氧水,采用通入惰性气体并搅拌的方式除氧,如氮气或氩气,脱氧过程需0.5-2h。
为了改善双金属硫族三元半导体纳米材料的水溶性及生物相容性,我们采用生物相容性高分子进行修饰,生物相容性高分子包括天然高分子如各种血清蛋白、葡聚糖及其衍生物、壳聚糖及其衍生物、果胶、羧甲基纤维素等,以及人工合成的生物相容性高分子如聚乙二醇及其衍生物、聚乙烯吡咯烷酮、聚乙烯亚胺、聚丙烯酸、聚乙烯醇等。这些生物高分子材料具有良好的水溶性和优异的生物相容性,能溶于体内组织液中被组织迅速的排除于体外且不产生毒副作用,被广泛的应用于医药、食品、卫生、化工等领域。
借由上述方案,本发明至少具有以下优点:本发明提供的生物相容性双金属硫族三元半导体纳米颗粒是利用生物相容性高分子材料在其制备过程中对其进行原位修饰,使其具有良好的水分散性和生物相容性,本发明提供的制备方法操作简单,易于推广,产率高;所得的双金属硫族三元半导体纳米颗粒粒径均一、结晶度高和可控的物理化学性质(如光学性质和磁学性质),本发明提供的具有生物相容性的双金属硫族三元半导体纳米颗粒可用于光声成像、核磁共振成像和光热治疗等生物医学领域。
上述说明仅是本发明技术方案的概述,为了能够更清楚了解本发明的技术手段,并可依照说明书的内容予以实施,以下以本发明的较佳实施例并配合附图详细说明如后。
附图说明
图1为本发明实施例1中Cu2-xFexSe2(0<x<2)半导体纳米颗粒的X-射线衍射图;
图2为本发明实施例2中Cu2-xNixSe2(0<x<2)半导体纳米颗粒的X-射线衍射图;
图3为本发明实施例3中CuGaSe2半导体纳米颗粒的X-射线衍射图;
图4为本发明实施例3中CuGaSe2半导体纳米颗粒的X-射线光电子能谱图;
图5为本发明实施例4中Cu2-xMnxSe2(0<x<2)半导体纳米颗粒的X-射线衍射图;
图6为本发明实施例4中Cu2-xMnxSe2(0<x<2)半导体纳米颗粒的X-射线光电子能谱图;
图7为本发明实施例5中CuSnSe2半导体纳米颗粒的X-射线衍射图;
图8为本发明实施例5中CuSnSe2半导体纳米颗粒的X-射线光电子能谱图;
图9为本发明实施例6中Cu2-xGdxSe(0<x<2)半导体纳米颗粒的X-射线衍射图;
图10为本发明实施例6中Cu2-xGdxSe(0<x<2)半导体纳米颗粒的X-射线光电子能谱图;
图11为本发明实施例7中CuAgSe半导体纳米颗粒的X-射线衍射图;
图12为本发明实施例8中Cu3AgS2半导体纳米颗粒的X-射线衍射图;
图13为本发明实施例9中Cu1.01Fe1.23Te2半导体纳米颗粒的X-射线衍射图;
图14为本发明实施例10中所得包覆有聚乙烯吡咯烷酮的CuFeSe2纳米颗粒的的透射电镜图;
图15为本发明实施例10中所得包覆有聚乙烯吡咯烷酮的CuFeSe2纳米颗粒不同浓度的紫外吸收光谱图;
图16为本发明实施例10中所得不同浓度的包覆有聚乙烯吡咯烷酮的CuFeSe2纳米颗粒溶液的体外光声图像及其光声信号曲线图;
图17为本发明实施例10中所得不同浓度的包覆有聚乙烯吡咯烷酮的CuFeSe2纳米颗粒溶液的体外光热升温曲线图;
图18为本发明实施例10中所得包覆有聚乙烯吡咯烷酮的CuFeSe2纳米颗粒溶液(250μg/mL)的体外光热循环曲线图;
图19为本发明实施例11中所得包覆有PMAA-PTTM的CuFeSe2纳米颗粒的的透射电镜图;
图20为本发明实施例11中包覆有PMAA-PTTM的CuFeSe2纳米颗粒的X-射线光电子能谱图;
图21为本发明实施例11中不同浓度的包覆有PMAA-PTTM的CuFeSe2纳米颗粒溶液的体外核磁共振图像及其弛豫率曲线图。
具体实施方式
下面结合附图和实施例,对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明,但不用来限制本发明的范围。
实施例1
将100mL超纯水通氮气除氧后,称取硼氢化钠(2.27g,60mmol)加入该无氧水中溶解完全后,加入硒粉(1.57g,20mmol),硼氢化钠与硒单质的摩尔比为3:1,待硒粉反应完全后,将5mL溶有CuCl2·2H2O和FeSO4·7H2O(二者总摩尔量为20mmol,加入比例分别为nFe/n(Cu+Fe)=0.2(b)、0.4(c)、0.5(d)、0.6(e)、0.8(f)、单一CuCl2·2H2O、单一FeSO4·7H2O(g))的水溶液注射入硒前驱体中,溶液立即变为黑色,离心洗涤,真空干燥得黑色粉末,得到的铜铁硒半导体纳米颗粒的X-射线衍射(XRD)见图1。从图1中可以看出,所得的CuFeSe2(d)纳米颗粒的衍射峰与CuFeSe2-XRD的标准卡片相一致,且所得铜铁硒半导体纳米颗粒的衍射峰会随着铜和铁的加入比例的不同在CuFeSe2-XRD的标准卡片的左右偏移。
实施例2
将100mL超纯水通氮气除氧后,称取硼氢化钠(2.27g,60mmol)加入该无氧水中溶解完全后,加入硒单质(1.57g,20mmol),硼氢化钠与硒单质的摩尔比为3:1,待硒粉反应完全后,将5mL溶有CuCl2·2H2O(1.70mg,10mmol)和NiCl2·6H2O(2.38g,10mmol)的水溶液注射入硒前驱体溶液中,溶液立即变为黑色,离心洗涤,真空干燥得黑色粉末,得到的铜镍硒半导体纳米颗粒Cu2-xNixSe2(x=0-1)的X-射线衍射(XRD)见图2。从图2中可以看出所得的铜镍硒半导体纳米颗粒的衍射峰在Cu2-xSe和NiSe-XRD的标准卡片中间。
实施例3
将100mL超纯水通氮气除氧后,称取硼氢化钠(2.27g,60mmol)加入该无氧水中溶解完全后,加入硒单质1.57g(20mmol),硼氢化钠与硒单质的摩尔比为3:1,待硒粉反应完全后,将5mL溶有CuCl2·2H2O(1.70g,10mmol)和GaNO3·9H2O(1.18g,10mmol)的水溶液注射进入硒前驱体中,溶液立即变为深棕色,反应40min后离心洗涤,真空干燥得黑色粉末,得到的铜镓硒半导体纳米颗粒的X-射线衍射(XRD)见图3。从图中可以看出所得的铜镓硒半导体纳米颗粒的衍射峰与CuGaSe2-XRD的标准卡片一致。图4为所得的CuGaSe2半导体纳米颗粒的X-射线光电子能谱图,可以看出Cu、Ga、Se三种元素分别以+1、+3、-2的价态存在。
实施例4
将100mL超纯水通氮气除氧后,称取硼氢化钠(2.27g,60mmol)加入该无氧水中溶解完全后,加入硒单质(1.57g,20mmol),硼氢化钠与硒单质的摩尔比为3:1,待硒粉反应完全,将5mL溶有CuCl2·2H2O(1.70mg,10mmol)和MnCl2·4H2O(1.97g,10mmol)的水溶液注射入硒前驱体中,溶液立即变为黑色,离心洗涤,真空干燥得黑色粉末,得到的铜锰硒半导体纳米颗粒的X-射线衍射(XRD)见图5。XRD标准卡片库中并无相匹配的铜锰硒化合物的标准卡片,但我们发现所得的铜锰硒半导体纳米颗粒的衍射峰与CuFeSe2-XRD的标准卡片相一致。图6为所得的铜锰硒半导体纳米颗粒的X-射线光电子能谱图,可以看出Mn元素在该化合物中以+2的价态存在。
实施例5
将100mL超纯水通氮气除氧后,称取硼氢化钠(2.27g,60mmol)加入该无氧水中溶解完全后,加入硒单质(1.57g,20mmol),硼氢化钠与硒单质的摩尔比为3:1,待硒粉反应完全,将5mL溶有CuCl2·2H2O(1.70mg,10mmol)和SnCl2·2H2O(2.25g,10mmol)的水溶液注射入硒前驱体中,溶液立即变为黑色,离心洗涤,真空干燥得黑色粉末,得到的铜锡硒半导体纳米颗粒的X-射线衍射(XRD)见图7。从图中可以看出所得的铜锡硒半导体纳米颗粒的衍射峰与CuSnSe2-XRD的标准卡片相一致。图8为所得的CuSnSe2半导体的X-射线光电子能谱图,可以看出Sn元素在该化合物中以+4的价态存在。实施例6
将100mL超纯水通氮气除氧后,称取硼氢化钠(2.27g,60mmol)加入该无氧水中溶解完全后,加入硒单质(1.57g,20mmol),硼氢化钠与硒单质的摩尔比为3:1,待硒粉反应完全,将5mL溶有CuCl2·2H2O(1.70mg,10mmol)和GdCl2·6H2O(3.71g,10mmol)的水溶液注射入硒前驱体中,溶液立即变为深棕色,离心洗涤,真空干燥得黑色粉末,得到的铜钆硒半导体纳米颗粒的X-射线衍射(XRD)见图9。从图中可以看出所得的铜钆硒半导体纳米颗粒的衍射峰与Cu2Se-XRD的标准卡片相一致。图10为所得的Cu2-xGdxSe半导体的X-射线光电子能谱图,可以看出Gd元素在该化合物中以+3的价态存在。实施例7
将100mL超纯水通氮气除氧后,称取硼氢化钠(1.14g,30mmol)加入该无氧水中溶解完全后,加入硒单质(0.79g,10mmol),硼氢化钠与硒单质的摩尔比为3:1,待硒粉反应完全,将5mL溶有CuCl2·2H2O(1.70mg,10mmol)和AgNO3(1.70g,10mmol)的水溶液注射入硒前驱体中,溶液立即变为黑色,离心洗涤,真空干燥得深灰色粉末,得到的铜银硒半导体纳米颗粒的X-射线衍射(XRD)见图11。从图中可以看出所得的铜银硒半导体纳米颗粒含有两种不同晶型的CuAgSe。
实施例8
将50mL超纯水通氮气除氧后,称取Na2S·9H2O(120.09mg,0.5mmol)加入该无氧水中溶解完全后,将5mL溶有Cu(NO3)2·3H2O(120.8mg,0.5mmol)和AgNO3(84.94mg,0.5mmol),溶液立即变为棕黄色,离心洗涤,真空干燥得黑色粉末,得到的铜银硫半导体纳米颗粒的X-射线衍射(XRD)见图12。从图中可以看出所得的铜银硫半导体纳米颗粒的衍射峰与Cu3AgS2-XRD的标准卡片相一致。
实施例9
将100mL超纯水通氮气除氧后,称取硼氢化钠(2.27g,60mmol)加入该无氧水中溶解完全后,加入碲单质(1.57g,20mmol),硼氢化钠与碲单质的摩尔比为9:1,待碲粉反应完全5mL溶有CuCl2·2H2O(1.70mg,10mmol)和FeSO4·7H2O(2.7802g,10mmol)的水溶液注射入碲前驱体中,溶液立即变为黑色,离心洗涤,真空干燥得黑色粉末,得到的铜铁碲半导体纳米颗粒的X-射线衍射(XRD)见图13。从图中可以看出所得的铜铁碲半导体纳米颗粒的衍射峰与Cu1.01Fe1.23Te2-XRD的标准卡片相一致。
实施例10
将100mL超纯水通氮气除氧后,称取硼氢化钠(56.75mg,1.5mol)加入该无氧水中溶解完全后,加入硒单质(39.45mg,0.5mmol),硼氢化钠与硒单质的摩尔比为3:1,待硒粉完全反应后,将5mL溶有CuCl2·2H2O(42.62mg,0.25mmol)和FeSO4·7H2O(69.51mg,0.25mmol)及聚乙烯吡咯烷酮(1g,分子量为40000)的水溶液注射进入硒前驱体中,溶液立即变为黑色.将该溶液通过超滤(超滤管的截留分子质量为100kD)进行浓缩后透析(透析袋的截留分子质量为100000)72h除去游离的聚合物,即可得到具有生物相容性的CuFeSe2纳米颗粒。图14为所得采用聚乙烯吡咯烷酮包覆的CuFeSe2纳米颗粒的透射电镜照片。图15为所得的采用聚乙烯吡咯烷酮包覆的CuFeSe2纳米颗粒的不同浓度紫外吸收图。
将实施例10中所得CuFeSe2纳米颗粒稀释到不同浓度,采用多光谱光声断层扫描成像系统测试它们的光声信号,图16为不同浓度CuFeSe2纳米颗粒溶液的光声成像图以及它们对应的光声信号值,从图中可以看出,CuFeSe2纳米颗粒具有良好的光声成像效果,可以用作光声成像造影剂。包括以下步骤:
(1)各取一定量不同浓度具有生物相容性三元半导体纳米溶液进行体外光声成像实验,先进行多波长多位置扫描,扫描波长为680-980nm,选出最佳吸收波长,然后在此波长下进行扫描;
(2)取一定量三元半导体纳米溶液通过尾静脉注射打入带有肿瘤的老鼠体内,进行体内光声实验,在最佳吸收波长下对不同脏器进行扫描,扫描的脏器包括肿瘤、脑、心、肝、脾、肺、肾,观察不同时间下光声信号强度的变化,观察时间为0-72h。
采用实施例10中所得CuFeSe2纳米颗粒溶液进行体外光热实验。取出1mL不同浓度的聚乙烯吡咯烷酮修饰的具有生物相容性的CuFeSe2纳米颗粒放入4mL石英比色皿中,用808nm,0.75W/cm2的激光照射CuFeSe2纳米溶液5分钟。图17为不同浓度的CuFeSe2纳米颗粒的体外光热曲线,图18为将250μg/mL的CuFeSe2纳米溶液的光热循环曲线,可以看出CuFeSe2纳米颗粒具有良好的光热效果和优异的光热稳定性,可以用作光热治疗剂。包括以下步骤:
(1)各取一定量不同浓度的具有生物相容性的双金属硫族三元半导体纳米溶液放入离心管或玻璃管中进行体外光热实验;
(2)体内光热治疗是将双金属硫族三元半导体纳米溶液通过老鼠尾静脉注射或者瘤内注射,采用激光照射一定时间后,观察老鼠肿瘤的体积随时间变化,并通过病理分析判断治疗效果,所述激光照射的波长为808nm、980nm或1064nm,光照强度为0-2W/cm2,照射时间为0-30min,观察治疗时间0-12month。
实施例11
将100mL超纯水通氮气除氧后,称取硼氢化钠(56.75mg,1.5mol)加入该无氧水中溶解完全后,加入硒单质(39.45mg,0.5mmol),硼氢化钠与硒单质的摩尔比为3:1,待硒粉完全反应后,即溶液变为无色,将5mL溶有CuCl2·2H2O(42.62mg,0.25mmol)和FeSO4·7H2O(69.51mg,0.25mmol)及PMAA-PTTM(400mg,0.0625mmol)的水溶液注射入硒前驱体中,溶液立即变为黑色。将该溶液通过超滤(超滤管的截留分子质量为30kD)进行浓缩,然后透析(透析袋的截留分子质量为8000-14000)72h除去游离的聚合物,即可得到具有生物相容性的CuFeSe2纳米颗粒。图19为所得的CuFeSe2纳米颗粒的透射电镜照片。将所得的CuFeSe2纳米颗粒溶液进行真空冷冻干燥,得CuFeSe2纳米颗粒的X-射线光电子能谱图,见图20,可以看出Cu、Fe、Se三种元素分别以+1、+3、-2的价态存在。
采用实施例11中所得CuFeSe2纳米颗粒溶液进行体外核磁共振成像实验。取出2mL不同浓度的PMAA-PTTM修饰的具有生物相容性的CuFeSe2纳米颗粒放入2mL石英比色皿中,在1.5T的磁场下观察其造影效果。图21为不同浓度CuFeSe2纳米颗粒溶液的T1加权成像图以及对应的T1弛豫率拟合图,从图中可以看出,CuFeSe2纳米颗粒具有良好的核磁共振增强效果,可以用作核磁共振增强造影剂。包括以下步骤:
(1)各取一定量不同浓度具有生物相容性的双金属硫族三元半导体纳米溶液放入离心管或玻璃管中进行体外核磁共振成像;
(2)将双金属硫族三元半导体纳米溶液通过老鼠尾静脉注射或者瘤内注射,在磁场下老鼠肿瘤中评价其在体内造影能力,观察老鼠肿瘤的T1、T2信号强度随时间的变化,所述磁场强度为1.5T、3.0T或4.7T,观察时间为0-72h。
以上所述仅是本发明的优选实施方式,并不用于限制本发明,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和变型,这些改进和变型也应视为本发明的保护范围。
Claims (5)
1.一种双金属硫族三元半导体纳米颗粒,其特征在于:所述双金属硫族三元半导体为CuFeSe2;所述双金属硫族三元半导体外包覆有聚乙烯吡咯烷酮。
2.一种如权利要求1所述的双金属硫族三元半导体纳米颗粒的制备方法,其特征在于,包括以下步骤:
(1)将硒的单质和/或水溶性的化合物溶解在加入硼氢化钠的除氧水中,其中硒的摩尔浓度为0.001-1mol/L,硼氢化钠与硒的摩尔比为3:1;
(2)向步骤(1)得到的溶液中加入水溶性的铜的金属盐和水溶性的铁的金属盐,其中铜、铁的总摩尔浓度为0.001-1mol/L,搅拌0.1-1h,得到含有双金属硫族三元半导体纳米颗粒;
在步骤(2)中,还向溶液中加入聚乙烯吡咯烷酮。
3.根据权利要求2所述的制备方法,其特征在于:在步骤(1)中,硒的水溶性的化合物为二氧化硒。
4.根据权利要求2所述的制备方法,其特征在于:在步骤(2)中,水溶性金属盐为盐酸盐、硝酸盐、硫酸盐、醋酸盐、柠檬酸盐和草酸盐中的一种或几种。
5.根据权利要求2所述的制备方法,其特征在于:所述水为去离子水。
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