CN110507829A - 铁钨复合氧化物纳米晶团簇的制备方法及其应用 - Google Patents

铁钨复合氧化物纳米晶团簇的制备方法及其应用 Download PDF

Info

Publication number
CN110507829A
CN110507829A CN201910702198.0A CN201910702198A CN110507829A CN 110507829 A CN110507829 A CN 110507829A CN 201910702198 A CN201910702198 A CN 201910702198A CN 110507829 A CN110507829 A CN 110507829A
Authority
CN
China
Prior art keywords
oxide nano
water
composite oxide
soluble
particle
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910702198.0A
Other languages
English (en)
Other versions
CN110507829B (zh
Inventor
徐祖顺
刘豪杰
喻春涵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hubei University
Original Assignee
Hubei University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hubei University filed Critical Hubei University
Priority to CN201910702198.0A priority Critical patent/CN110507829B/zh
Publication of CN110507829A publication Critical patent/CN110507829A/zh
Application granted granted Critical
Publication of CN110507829B publication Critical patent/CN110507829B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K49/00Preparations for testing in vivo
    • A61K49/0002General or multifunctional contrast agents, e.g. chelated agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K49/00Preparations for testing in vivo
    • A61K49/04X-ray contrast preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K49/00Preparations for testing in vivo
    • A61K49/06Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations
    • A61K49/08Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by the carrier
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K49/00Preparations for testing in vivo
    • A61K49/06Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations
    • A61K49/18Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by a special physical form, e.g. emulsions, microcapsules, liposomes
    • A61K49/1818Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by a special physical form, e.g. emulsions, microcapsules, liposomes particles, e.g. uncoated or non-functionalised microparticles or nanoparticles
    • A61K49/1887Agglomerates, clusters, i.e. more than one (super)(para)magnetic microparticle or nanoparticle are aggregated or entrapped in the same maxtrix
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00Compounds of tungsten
    • C01G41/02Oxides; Hydroxides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00Compounds of iron
    • C01G49/02Oxides; Hydroxides
    • C01G49/08Ferroso-ferric oxide [Fe3O4]
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/04Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Public Health (AREA)
  • Epidemiology (AREA)
  • Veterinary Medicine (AREA)
  • Organic Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Radiology & Medical Imaging (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
  • Compounds Of Iron (AREA)

Abstract

本发明提供了铁钨复合氧化物纳米晶团簇的制备方法及其应用,该方法包括:(1)以水溶性的三价铁盐和二价铁盐为原料,以水溶性阴离子有机物为表面活性剂,以去离子水为溶剂,加入碱源,采用化学共沉淀法制备水溶性的四氧化三铁纳米粒子;(2)以水溶性钨盐为原料,以水溶性聚合物为表面活性剂,以多元醇为溶剂,采用热分解法制备水溶性的氧化钨纳米粒子;(3)取四氧化三铁纳米粒子、氧化钨纳米粒子和聚乙烯亚胺在去离子水中进行自组装反应,得铁钨复合氧化物纳米晶团簇。本发明纳米晶团簇在水相中低温合成,方法简单,成本低廉,所合成纳米晶团簇具有较好的MR/CT成像增强效果。

Description

铁钨复合氧化物纳米晶团簇的制备方法及其应用
技术领域
本发明涉及材料科学与生物医药技术领域,具体为铁钨复合氧化物纳米晶团簇的制备方法及其应用。
背景技术
纳米复合材料,尤其是功能性纳米复合粒子近年来研究广泛。其中将具有磁性的无机材料(如Fe3O4,γ-Fe2O3,Ni,Co以及Mn的氧化物等)与其他各种具有功能性的纳米材料(如环境响应性,催化,生物成像,治疗等)相结合制备的复合纳米粒子,由于其多样的功能性,广泛应用于生物医药(如载药,蛋白质、基因、细胞分离,MRI、CT、光学造影成像)和工业应用(催化、污水处理等)等领域,均取得了很好的效果,因而其研究潜力巨大。
发明内容
本发明的目的是提供铁钨复合氧化物纳米晶团簇的制备方法及其应用。
本发明提供的铁钨复合氧化物纳米晶团簇的制备方法,包括:
(1)以水溶性的三价铁盐和二价铁盐为原料,以水溶性阴离子有机物为表面活性剂,以去离子水为溶剂,加入碱源,采用化学共沉淀法制备水溶性的四氧化三铁纳米粒子;
需要说明的是,此处指三价铁盐和二价铁盐均采用水溶性盐;
(2)以水溶性钨盐为原料,以水溶性聚合物为表面活性剂,以多元醇为溶剂,采用热分解法制备水溶性的氧化钨纳米粒子;
(3)取四氧化三铁纳米粒子、氧化钨纳米粒子和聚乙烯亚胺在去离子水中进行自组装反应,得铁钨复合氧化物纳米晶团簇。
步骤(1)获得的四氧化三铁纳米粒子为水溶性阴离子有机物修饰后的四氧化三铁纳米粒子,在水相中,该修饰后的纳米粒子表面呈现负电荷。步骤(2)获得的氧化钨纳米粒子为水溶性聚合物修饰后的氧化钨纳米粒子,在水相中,该修饰后的纳米粒子表面同样呈现负电荷。而聚乙烯亚胺在水相中呈现正电荷,通过静电作用和高分子链缠绕作用,则可使四氧化三铁纳米粒子和氧化钨纳米粒子形成纳米晶簇,从而成功合成稳定的铁钨复合氧化物纳米晶团簇。
进一步的,步骤(1)具体为:
溶剂中加入原料、表面活性剂和碱源,碱源用来控制反应溶液pH为11~12;在无氧条件下,在40~80℃温度下搅拌反应1~3h;经磁性分离、洗涤,将所得产物分散于去离子水中。
步骤(1)中,三价铁盐与二价铁盐中铁元素的摩尔比为1.06:1,水溶性阴离子有机物和铁离子的摩尔比为1:(3~10),铁离子包括二价铁离子和三价铁离子。
进一步的,二价铁盐优选为四水合氯化亚铁、七水合硫酸亚铁或柠檬酸亚铁。
进一步的,三价铁盐优选为六水合氯化铁、七水合硫酸铁或柠檬酸铁。
进一步的,水溶性阴离子有机物优选为柠檬酸钠、酒石酸钠、乙二胺四乙酸二钠、乙二胺四乙酸钠、柠檬酸、酒石酸或乙二胺四乙酸。
进一步的,碱源优选为氨水、氢氧化钠溶液、氢氧化钾溶液、碳酸钠溶液或碳酸钾溶液。本发明中碱源的作用是调节反应溶液的pH值,使得反应溶液pH值控制在11~12。
进一步的,步骤(2)具体为:
溶剂中加入钨盐和表面活性剂,在无氧条件下,在160~180℃温度下反应20~60min;冷却至室温后再经离心、洗涤,将所得产物分散于去离子水中。
进一步的,水溶性聚合物的用量为钨盐质量的1%~8%。
进一步的,钨盐优选为硒化钨、仲钨酸铵、钨酸钠、硫化钨或氯化钨。
进一步的,水溶性聚合物优选为聚乙二醇,聚乙烯醇、聚乙烯亚胺或聚丙烯酸。
进一步的,多元醇优选为苯甲醇、乙二醇或二乙二醇。
进一步的,步骤(3)具体为:
取四氧化三铁纳米粒子、氧化钨纳米粒子和聚乙烯亚胺溶于去离子水,在惰性环境中,在室温下反应3~5h,经离心得铁钨复合氧化物纳米晶团簇。
进一步的,所取四氧化三铁纳米粒子和氧化钨纳米粒子的摩尔比为(0.3~3):1,聚乙烯亚胺的用量为四氧化三铁纳米粒子和氧化钨纳米粒子质量和的3%~15%。
上述所制备的铁钨复合氧化物纳米晶团簇,四氧化三铁赋予了该纳米晶团簇加权磁共振成像功能,氧化钨纳米粒子赋予该纳米晶团簇CT成像增强效应,两种成像方式互补,使得该纳米晶团簇具有CT和MRI双重成像功能,可用作MRI/CT双模态成像造影剂。
本发明以纳米四氧化三铁和纳米氧化钨作为基本材料,采用静电自组装方法成功制备出粒径均一、且性能稳定的铁钨复合氧化物纳米晶团簇。因为纳米四氧化三铁具有较好的磁共振成像效果,纳米氧化钨具有较强的X射线吸收作用,可用作CT成像造影剂,两种成像方式进行互补,具有较好的MR/CT成像增强效果能够有效地提高成像诊断准确性。
相比于传统的高温溶剂热合成金属氧化物纳米材料,本发明在水相中低温合成,方法简单,成本低廉,故而本研究制备的铁钨复合氧化物纳米晶簇在医学成像应用领域具有潜在的应用价值。
该纳米晶团簇合成条件简单,生物相容性良好,两种成像方式进行互补,具有较好的MR/CT成像增强效果能够有效地提高成像诊断准确性,在医学成像方面具有潜在的应用价值。
概括来说,和现有技术相比,本发明具有如下优点和有益效果:
(1)制备条件简单,原料成本低,反应时间短,利于推广。
(2)作为一种新型的诊疗试剂,具有良好的T2、CT造影效果。
(3)制备的较小粒径纳米颗粒具有较高的血液半衰期,纳米粒子稳定,低的生物毒性,在临床诊断上具有较高的潜在应用价值。
附图说明
图1~2为实施例1所制备纳米晶团簇在不同放大倍数下的透射电镜图;
图3为实施例1所制备纳米晶团簇的体外T2MRI造影图;
图4为实施例1所制备纳米晶团簇的体外CT造影图。
具体实施方式
下面结合实施例对本发明做进一步的说明,以下所述,仅是对本发明的较佳实施例而已,并非对本发明做其他形式的限制,任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更为同等变化的等效实施例。凡是未脱离本发明方案内容,依据本发明的技术实质对以下实施例所做的简单修改或等同变化,均落在本发明的保护范围内。
下面的实施例是对本发明的进一步详细描述。
实施例1
本实施例具体步骤如下:
(1)将13.52g六水合氯化铁和2g柠檬酸钠溶于100ml去离子水中,超声溶解,加入到250ml四口烧瓶中。通氮气搅拌15min,然后加入6.76g四水合氯化亚铁,继续搅拌10min。加入50ml质量浓度为15%的氨水至反应溶液,并升温至80℃,反应1h。反应结束后,将反应溶液用磁铁分离,并多次去离子水洗涤,所得产物再次分散到去离子水中,得到水溶性四氧化三铁纳米粒子的溶液,所得溶液浓度为10mg/ml,将该溶液置于冰箱4℃保存备用。
(2)取0.8g氯化钨溶于50ml多元醇,置于100ml三口烧瓶中搅拌溶解。然后加入0.06g聚丙烯酸继续搅拌溶解,混合均匀后将上述反应溶液置于烧瓶中于180℃反应30min。反应结束后,将反应溶液冷却到室温,加入50ml去离子水,进行离心,并采用去离子水洗涤数次,所得产物再次分散到去离子水中,得到水溶性氧化钨纳米粒子的溶液,所得溶液浓度为5mg/ml,将该溶液置于冰箱4℃保存备用。
(3)取10ml四氧化三铁纳米粒子的溶液和10ml氧化钨纳米粒子的溶液,加入到20ml去离子水中,置于100ml的三口烧瓶。在氮气气氛中,进行机械搅拌30min,之后取20mg聚乙烯亚胺溶于10ml去离子水中得聚乙烯亚胺溶液,将聚乙烯亚胺溶液加入到纳米粒子混合溶液中,继续搅拌,室温反应3h。反应结束后,将反应溶液离心,并采用去离子水洗涤数次,得到铁钨复合氧化物纳米晶团簇,将铁钨复合氧化物纳米晶团簇分散到去离子水中,得铁钨复合氧化物纳米晶团簇分散液,将该分散液置于冰箱4℃保存备用。
图1和图2所示为本实施例所制备纳米晶团簇的透射电镜图,其中,图1和图2分别为不同放大倍数的透射电镜图,从图中可以看出,本实施例纳米晶团簇为尺寸统一的微球结构,粒径约80nm。图3所示为本实施例所制备纳米晶团簇的体外T2MRI造影图,从图中可以看出,随着Fe含量的升高,造影效果明显增强。图4所示为本实施例所制备纳米晶团簇的体外CT造影图,从图中可以看出,随着钨含量的升高,CT造影信号呈明显递增趋势。
实施例2
本实施例具体步骤如下:
(1)将13.52g六水合氯化铁和2g柠檬酸钠溶于100ml去离子水中,超声溶解,加入到250ml四口烧瓶中。通氮气搅拌15min,然后加入6.76g四水合氯化亚铁,继续搅拌10min。加入50ml质量浓度为15%的氨水至反应溶液,并升温至80℃,反应1h。反应结束后,将反应溶液用磁铁分离,并多次去离子水洗涤,所得产物再次分散到去离子水中,得到水溶性四氧化三铁纳米粒子的溶液,所得溶液浓度为10mg/ml,将该溶液置于冰箱4℃保存备用。
(2)取0.8g氯化钨溶于50ml多元醇,置于100ml三口烧瓶中搅拌溶解。然后加入0.06g聚丙烯酸继续搅拌溶解,混合均匀后将上述反应溶液置于烧瓶中于180℃反应30min。反应结束后,将反应溶液冷却到室温,加入50ml去离子水,进行离心,并采用去离子水洗涤数次,所得产物再次分散到去离子水中,得到水溶性氧化钨纳米粒子的溶液,所得溶液浓度为10mg/ml,将该溶液置于冰箱4℃保存备用。
(3)取10ml四氧化三铁纳米粒子的溶液和10ml氧化钨纳米粒子的溶液,加入到20ml去离子水中,置于100ml的三口烧瓶。在氮气气氛中,进行机械搅拌30min,之后取0.01g聚乙烯亚胺溶于10ml去离子水中得聚乙烯亚胺溶液,将聚乙烯亚胺溶液加入到纳米粒子混合溶液中,继续搅拌,反应3h。反应结束后,将反应溶液离心,并采用去离子水洗涤数次,得到铁钨复合氧化物纳米晶团簇,将铁钨复合氧化物纳米晶团簇分散到去离子水中,得铁钨复合氧化物纳米晶团簇分散液,将该分散液置于冰箱4℃保存备用。
实施例3
本实施例具体步骤如下:
(1)将13.52g六水合氯化铁和2g柠檬酸钠溶于100ml去离子水中,超声溶解,加入到250ml四口烧瓶中。通氮气搅拌15min,然后加入6.76g四水合氯化亚铁,继续搅拌10min。加入50ml质量浓度为15%的氨水至反应溶液,并升温至80℃,反应1h。反应结束后,将反应溶液用磁铁分离,并多次去离子水洗涤,所得产物再次分散到去离子水中,得到水溶性四氧化三铁纳米粒子的溶液,所得溶液浓度为10mg/ml,将该溶液置于冰箱4℃保存备用。
(2)取0.8g氯化钨溶于50ml多元醇,置于100ml三口烧瓶中搅拌溶解。然后加入0.06g聚丙烯酸继续搅拌溶解,混合均匀后将上述反应溶液置于烧瓶中于180℃反应30min。反应结束后,将反应溶液冷却到室温,加入50ml去离子水,进行离心,并采用去离子水洗涤数次,所得产物再次分散到去离子水中,得到水溶性氧化钨纳米粒子的溶液,所得溶液浓度为15mg/ml,将该溶液置于冰箱4℃保存备用。
(3)取10ml四氧化三铁纳米粒子的溶液和10ml氧化钨纳米粒子的溶液,加入到20ml去离子水中,置于100ml的三口烧瓶。在氮气气氛中,进行机械搅拌30min,之后取0.01g聚乙烯亚胺溶于10ml去离子水中得聚乙烯亚胺溶液,将聚乙烯亚胺溶液加入到纳米粒子混合溶液中,继续搅拌,反应3h。反应结束后,将反应溶液离心,并采用去离子水洗涤数次,得到铁钨复合氧化物纳米晶团簇,将铁钨复合氧化物纳米晶团簇分散到去离子水中,得铁钨复合氧化物纳米晶团簇分散液,将该分散液置于冰箱4℃保存备用。
实施例4
本实施例具体步骤如下:
(1)将13.52g六水合氯化铁和2g柠檬酸钠溶于100ml去离子水中,超声溶解,加入到250ml四口烧瓶中。通氮气搅拌15min,然后加入6.76g四水合氯化亚铁,继续搅拌10min。加入50ml质量浓度为15%的氨水至反应溶液,并升温至80℃,反应1h。反应结束后,将反应溶液用磁铁分离,并多次去离子水洗涤,所得产物再次分散到去离子水中,得到水溶性四氧化三铁纳米粒子的溶液,所得溶液浓度为10mg/ml,将该溶液置于冰箱4℃保存备用。
(2)取0.8g氯化钨溶于50ml多元醇,置于100ml三口烧瓶中搅拌溶解。然后加入0.06g聚丙烯酸继续搅拌溶解,混合均匀后将上述反应溶液置于烧瓶中于180℃反应30min。反应结束后,将反应溶液冷却到室温,加入50ml去离子水,进行离心,并采用去离子水洗涤数次,所得产物再次分散到去离子水中,得到水溶性氧化钨纳米粒子的溶液,所得溶液浓度为15mg/ml,将该溶液置于冰箱4℃保存备用。
(3)取15ml四氧化三铁纳米粒子的溶液和10ml氧化钨纳米粒子的溶液,加入到20ml去离子水中,置于100ml的三口烧瓶。在氮气气氛中,进行机械搅拌30min,之后取0.0225g聚乙烯亚胺溶于10ml去离子水中得聚乙烯亚胺溶液,将聚乙烯亚胺溶液加入到纳米粒子混合溶液中,继续搅拌,反应3h。反应结束后,将反应溶液离心,并采用去离子水洗涤数次,得到铁钨复合氧化物纳米晶团簇,将铁钨复合氧化物纳米晶团簇分散到去离子水中,得铁钨复合氧化物纳米晶团簇分散液,将该分散液置于冰箱4℃保存备用。
实施例5
本实施例具体步骤如下:
(1)将13.52g六水合氯化铁和2g柠檬酸钠溶于100ml去离子水中,超声溶解,加入到250ml四口烧瓶中。通氮气搅拌15min,然后加入6.76g四水合氯化亚铁,继续搅拌10min。加入50ml质量浓度为15%的氨水至反应溶液,并升温至80℃,反应1h。反应结束后,将反应溶液用磁铁分离,并多次去离子水洗涤,所得产物再次分散到去离子水中,得到水溶性四氧化三铁纳米粒子的溶液,所得溶液浓度为10mg/ml,将该溶液置于冰箱4℃保存备用。
(2)取0.8g氯化钨溶于50ml多元醇,置于100ml三口烧瓶中搅拌溶解。然后加入0.06g聚丙烯酸继续搅拌溶解,混合均匀后将上述反应溶液置于烧瓶中于180℃反应30min。反应结束后,将反应溶液冷却到室温,加入50ml去离子水,进行离心,并采用去离子水洗涤数次,所得产物再次分散到去离子水中,得到水溶性氧化钨纳米粒子的溶液,所得溶液浓度为15mg/ml,将该溶液置于冰箱4℃保存备用。
(3)取15ml四氧化三铁纳米粒子的溶液和10ml氧化钨纳米粒子的溶液,加入到20ml去离子水中,置于100ml的三口烧瓶。在氮气气氛中,进行机械搅拌30min,之后取0.045g聚乙烯亚胺溶于10ml去离子水中得聚乙烯亚胺溶液,将聚乙烯亚胺溶液加入到纳米粒子混合溶液中,继续搅拌,反应3h。反应结束后,将反应溶液离心,并采用去离子水洗涤数次,得到铁钨复合氧化物纳米晶团簇,将铁钨复合氧化物纳米晶团簇分散到去离子水中,得铁钨复合氧化物纳米晶团簇分散液,将该分散液置于冰箱4℃保存备用。
上述实施例仅为多种实施例中的一种,对于本领域内的技术人员,在上述说明基础上还可以做出其他不同形式的变化或变动,而这些属于本发明实质精神而衍生出的其他变化或变动仍属于本发明保护范围。

Claims (10)

1.铁钨复合氧化物纳米晶团簇的制备方法,其特征是,包括:
(1)以水溶性的三价铁盐和二价铁盐为原料,以水溶性阴离子有机物为表面活性剂,以去离子水为溶剂,加入碱源,采用化学共沉淀法制备水溶性的四氧化三铁纳米粒子;
(2)以水溶性钨盐为原料,以水溶性聚合物为表面活性剂,以多元醇为溶剂,采用热分解法制备水溶性的氧化钨纳米粒子;
(3)取四氧化三铁纳米粒子、氧化钨纳米粒子和聚乙烯亚胺在去离子水中进行自组装反应,得铁钨复合氧化物纳米晶团簇。
2.如权利要求1所述的铁钨复合氧化物纳米晶团簇的制备方法,其特征是:
步骤(1)具体为:
溶剂中加入原料、表面活性剂和碱源,碱源用来控制反应溶液pH为11~12;在无氧条件下,在40~80℃温度下搅拌反应1~3h;经磁性分离、洗涤,将所得产物分散于去离子水中。
3.如权利要求1所述的铁钨复合氧化物纳米晶团簇的制备方法,其特征是:
步骤(1)中,三价铁盐与二价铁盐中铁元素的摩尔比为1.06:1,水溶性阴离子有机物和铁离子的摩尔比为1:(3~10),铁离子包括二价铁离子和三价铁离子。
4.如权利要求1所述的铁钨复合氧化物纳米晶团簇的制备方法,其特征是:
所述水溶性阴离子有机物为柠檬酸钠、酒石酸钠、乙二胺四乙酸二钠、乙二胺四乙酸钠、柠檬酸、酒石酸或乙二胺四乙酸。
5.如权利要求1所述的铁钨复合氧化物纳米晶团簇的制备方法,其特征是:
步骤(2)具体为:
溶剂中加入钨盐和表面活性剂,在无氧条件下,在160~180℃温度下反应20~60min;冷却至室温后再经离心、洗涤,将所得产物分散于去离子水中。
6.如权利要求1所述的铁钨复合氧化物纳米晶团簇的制备方法,其特征是:
所述水溶性聚合物的用量为钨盐质量的1%~8%。
7.如权利要求1所述的铁钨复合氧化物纳米晶团簇的制备方法,其特征是:
所述水溶性聚合物为聚乙二醇,聚乙烯醇、聚乙烯亚胺或聚丙烯酸。
8.如权利要求1所述的铁钨复合氧化物纳米晶团簇的制备方法,其特征是:
步骤(3)具体为:
取四氧化三铁纳米粒子、氧化钨纳米粒子和聚乙烯亚胺溶于去离子水,在惰性环境中,在室温下反应3~5h,经离心得铁钨复合氧化物纳米晶团簇。
9.如权利要求1所述的铁钨复合氧化物纳米晶团簇的制备方法,其特征是:
步骤(3)中,所取四氧化三铁纳米粒子和氧化钨纳米粒子的摩尔比为(0.3~3):1,聚乙烯亚胺的用量为四氧化三铁纳米粒子和氧化钨纳米粒子质量和的3%~15%。
10.权利要求1~9任一项所制备的铁钨复合氧化物纳米晶团簇用来制作MRI/CT双模态成像造影剂的应用。
CN201910702198.0A 2019-07-31 2019-07-31 铁钨复合氧化物纳米晶团簇的制备方法及其应用 Active CN110507829B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910702198.0A CN110507829B (zh) 2019-07-31 2019-07-31 铁钨复合氧化物纳米晶团簇的制备方法及其应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910702198.0A CN110507829B (zh) 2019-07-31 2019-07-31 铁钨复合氧化物纳米晶团簇的制备方法及其应用

Publications (2)

Publication Number Publication Date
CN110507829A true CN110507829A (zh) 2019-11-29
CN110507829B CN110507829B (zh) 2021-08-31

Family

ID=68623811

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910702198.0A Active CN110507829B (zh) 2019-07-31 2019-07-31 铁钨复合氧化物纳米晶团簇的制备方法及其应用

Country Status (1)

Country Link
CN (1) CN110507829B (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114053966A (zh) * 2021-03-04 2022-02-18 中国科学院宁波材料技术与工程研究所 一种亲水性磁性纳米材料及其制备方法与应用
CN114229898A (zh) * 2021-12-09 2022-03-25 沈阳化工大学 一种用模板制备多面体三氧化钨方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103341183A (zh) * 2013-06-13 2013-10-09 上海师范大学 纳米氧化钨wo2.9在ct造影剂材料中的应用
CN107899023A (zh) * 2017-12-28 2018-04-13 山西省肿瘤医院 一种纳米造影剂及其制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103341183A (zh) * 2013-06-13 2013-10-09 上海师范大学 纳米氧化钨wo2.9在ct造影剂材料中的应用
CN107899023A (zh) * 2017-12-28 2018-04-13 山西省肿瘤医院 一种纳米造影剂及其制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ZHIYIN XIAO等: "Polypyrrole-encapsulated Iron Tungstate Nanocomposites: A Versatile Platform for Multimodal Tumor Imaging and Photothermal Therapy", 《NANOSCALE》 *
吴可嘉: "Fe3O4-WOx-CQD多功能体系的构筑、表征及性能研究", 《万方数据平台》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114053966A (zh) * 2021-03-04 2022-02-18 中国科学院宁波材料技术与工程研究所 一种亲水性磁性纳米材料及其制备方法与应用
CN114229898A (zh) * 2021-12-09 2022-03-25 沈阳化工大学 一种用模板制备多面体三氧化钨方法

Also Published As

Publication number Publication date
CN110507829B (zh) 2021-08-31

Similar Documents

Publication Publication Date Title
Olsson et al. Controlled synthesis of near-stoichiometric cobalt ferrite nanoparticles
Cai et al. Large-scale, facile transfer of oleic acid-stabilized iron oxide nanoparticles to the aqueous phase for biological applications
CN105288666B (zh) 一种水溶性蛋白包覆的磁性纳米颗粒及其制备方法
CN102125699B (zh) Fe3O4复合TiO2纳米粒子及其制备方法以及在磁共振成像造影剂中的应用
JP5765520B2 (ja) 磁性粒子含有水分散体の製造方法
CN101417822B (zh) 超顺磁介孔四氧化三铁纳米粒子的制备方法
CN100446134C (zh) 氧化铁粒子悬浮液的制备方法
Puvvada et al. Shape dependent peroxidase mimetic activity towards oxidation of pyrogallol by H 2 O 2
CN106913885B (zh) 一种磁性纳米粒子及其制备方法和应用
CN105271433B (zh) 一种锌掺杂的超顺磁四氧化三铁纳米颗粒的水热合成制备方法
CN110507829A (zh) 铁钨复合氧化物纳米晶团簇的制备方法及其应用
CN101935070A (zh) 丙烯酸类聚合物纳米水凝胶诱导原位合成超顺磁性四氧化三铁纳米粒子的方法
CN101279769B (zh) 强磁性四氧化三铁纳米材料的制备方法
CN110665465A (zh) 用于糖肽富集的磁性共价有机框架材料及其制备方法与应用
CN114042168B (zh) 一种双金属硫化物纳米探针的制备及应用
CN106010500A (zh) 一种具有核壳结构的磁性纳米发光材料及其制备方法
CN111228487B (zh) 含石墨化荧光碳点且具有yolk-shell结构的磁性粒子及其制备方法和应用
CN110550666B (zh) 一种单分散、超顺磁性四氧化三铁纳米花及其制备方法
CN108455682A (zh) 一种水性Fe3O4纳米粉体的制备方法
CN107213474A (zh) 一种铁基磁性纳米晶磁共振t1造影剂的制备方法及其应用
CN102430130B (zh) 一种医药用改性葡聚糖包覆磁性纳米颗粒复合材料及其制备方法
CN103007302A (zh) Gd2O3-TiO2复合纳米粒子及其制备方法和应用
Zheng et al. Breast cancer diagnosed by MRI using mesoporous TiO2-coated (Fe3O4) nanoparticles
CN115180654A (zh) 高纯度硫化铁纳米酶的制备方法和应用
CN102910684A (zh) 单分散四氧化三铁纳米颗粒的克规模合成方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
EE01 Entry into force of recordation of patent licensing contract
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20191129

Assignee: Yunnan Benyi Biotechnology Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023530000011

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230403

Application publication date: 20191129

Assignee: Kunming Junxiang Pharmaceutical Technology Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023530000013

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230403

Application publication date: 20191129

Assignee: Kunming Daren Medical Equipment Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023530000012

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230403

EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20191129

Assignee: Hubei yapunodi Technology Development Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000144

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230606

Application publication date: 20191129

Assignee: Hubei Yunyihui Medical Technology Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000143

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230606

EE01 Entry into force of recordation of patent licensing contract
EE01 Entry into force of recordation of patent licensing contract
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20191129

Assignee: Hubei Yueming Technology Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000151

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230608

Application publication date: 20191129

Assignee: BORUNCHENG (WUHAN) PHARMACEUTICAL CO.,LTD.

Assignor: Hubei University

Contract record no.: X2023420000155

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230608

Application publication date: 20191129

Assignee: Wuhan Dorman Health Technology Partnership (L.P.)

Assignor: Hubei University

Contract record no.: X2023420000149

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230607

Application publication date: 20191129

Assignee: Wuhan Zhencai Intelligent Manufacturing Technology Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000150

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230608

Application publication date: 20191129

Assignee: Wuhan Hengtai Bainian Trading Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000157

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230609

Application publication date: 20191129

Assignee: Wuhan Yihui Medical Technology Service Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000158

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230609

Application publication date: 20191129

Assignee: Hubei Wanhai Saikang Life Science Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000154

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230608

Application publication date: 20191129

Assignee: Wuhan golden Jirui Medical Technology Development Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000152

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230608

Application publication date: 20191129

Assignee: Wuhan Zero Action Medical Technology Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000148

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230607

Application publication date: 20191129

Assignee: Wuhan Weier Laibo Technology Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000153

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230608

Application publication date: 20191129

Assignee: Wuhan Ruixin Zetai Technology Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000156

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230608

EE01 Entry into force of recordation of patent licensing contract
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20191129

Assignee: Wuhan Kaikang Technology Development Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000164

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230612

Application publication date: 20191129

Assignee: Wuhan Lingyi Medical Technology Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000160

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230612

Application publication date: 20191129

Assignee: Hubei Zeshunzhi Science and Trade Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000174

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230614

Application publication date: 20191129

Assignee: Wuhan Jingdong Medical Technology Partnership (L.P.)

Assignor: Hubei University

Contract record no.: X2023420000159

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230612

Application publication date: 20191129

Assignee: Wuhan Warmth Medical Services Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000178

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230615

Application publication date: 20191129

Assignee: Wuhan Zhencai Zhizao Medical Technology Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000162

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230612

Application publication date: 20191129

Assignee: Hubei Zheshunkai Technology Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000177

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230615

Application publication date: 20191129

Assignee: Hubei Shengrui Medical Equipment Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000163

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230612

Application publication date: 20191129

Assignee: Wuhan Dorman Health Technology Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000161

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230612

Application publication date: 20191129

Assignee: WUHAN JUNAN YOULIAN MEDICAL TECHNOLOGY Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000165

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230612

EE01 Entry into force of recordation of patent licensing contract
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20191129

Assignee: Wuhan Shuidi 1872 Medical Technology Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000180

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230616

Application publication date: 20191129

Assignee: Wuhan Youyimo Medical Technology Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000179

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230616

Application publication date: 20191129

Assignee: Hanli Kechuang (Wuhan) Medical Service Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000182

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230616

Application publication date: 20191129

Assignee: Wuhan Yiran Biotechnology Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000181

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230616

Application publication date: 20191129

Assignee: Wuhan Youyimo Hankou Medical Management Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023420000184

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230616

EE01 Entry into force of recordation of patent licensing contract
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20191129

Assignee: Weimi Medical (Yunnan) Co.,Ltd.

Assignor: Hubei University

Contract record no.: X2023980040027

Denomination of invention: Preparation Method and Application of Iron Tungsten Composite Oxide Nanocrystalline Clusters

Granted publication date: 20210831

License type: Common License

Record date: 20230822