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Low-Temperature approach to highly emissive copper indium sulfide colloidal nanocrystals and their bioimaging applications

机译:低温法制备高发射率的铜铟硫胶体纳米晶体及其生物成像应用

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摘要

We report our newly developed low-temperature synthesis of colloidal photoluminescent (PL) CuInS2 nanocrystals (NCs) and their in vitro and in vivo imaging applications. With diphenylphosphine sulphide (SDPP) as a S precursor made from elemental S and diphenylphosphine, this is a noninjection based approach in 1-dodecanethiol (DDT) with excellent synthetic reproducibility and large-scale capability. For a typical synthesis with copper iodide (CuI) as a Cu source and indium acetate (In(OAc)3) as an In source, the growth temperature was as low as 160 C and the feed molar ratios were 1Cu-to-1In-to-4S. Amazingly, the resulting CuInS2 NCs in toluene exhibit quantum yield (QY) of \u223c23% with photoemission peaking at \u223c760 nm and full width at half maximum (FWHM) of \u223c140 nm. With a mean size of \u223c3.4 nm (measured from the vertices to the bases of the pyramids), they are pyramidal in shape with a crystal structure of tetragonal chalcopyrite. In situ 31P NMR (monitored from 30 C to 100 C) and in situ absorption at 80 C suggested that the Cu precursor should be less reactive toward SDPP than the In precursor. For our in vitro and in vivo imaging applications, CuInS 2/ZnS core-shell QDs were synthesized; afterwards, dihydrolipoic acid (DHLA) or 11-mercaptoundecanoic acid (MUA) were used for ligand exchange and then bio-conjugation was performed. Two single-domain antibodies (sdAbs) were used. One was 2A3 for in vitro imaging of BxPC3 pancreatic cancer cells. The other was EG2 for in vivo imaging of a Glioblastoma U87MG brain tumour model. The bioimaging data illustrate that the CuInS2 NCs from our SDPP-based low-temperature noninjection approach are good quality.
机译:我们报告了我们最新开发的胶体光致发光(PL)CuInS2纳米晶体(NCs)的低温合成及其体外和体内成像应用。硫化二苯膦硫化物(SDPP)作为由元素S和二苯膦制成的S前体,这是1-十二烷硫醇(DDT)中基于非注射的方法,具有出色的合成重现性和大规模生产能力。对于使用碘化铜(CuI)作为铜源和乙酸铟(In(OAc)3)作为In源的典型合成,生长温度低至160°C,进料摩尔比为1Cu与1In-至4S。令人惊讶的是,在甲苯中生成的CuInS2 NCs的量子产率(QY)为\ u223c23%,光发射峰位于\ u223c760 nm,并且半峰全宽(FWHM)为\ u223c140 nm。它们的平均大小为\ u223c3.4 nm(从顶点到金字塔底的尺寸),呈金字塔形,具有四方黄铜矿的晶体结构。原位31 P NMR(从30 C到100 C进行监测)和80 C的原位吸收表明,Cu前驱体对SDPP的反应性应低于In前驱体。对于我们的体外和体内成像应用,合成了CuInS 2 / ZnS核壳量子点;之后,使用二氢硫辛酸(DHLA)或11-巯基癸酸(MUA)进行配体交换,然后进行生物缀合。使用了两种单域抗体(sdAb)。一种是2A3,用于BxPC3胰腺癌细胞的体外成像。另一个是用于胶质母细胞瘤U87MG脑肿瘤模型体内成像的EG2。生物成像数据表明,基于我们基于SDPP的低温非注入方法的CuInS2 NC具有良好的质量。

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