CN114806579A - 一种近红外发光的磁性量子点及其制备方法与应用 - Google Patents
一种近红外发光的磁性量子点及其制备方法与应用 Download PDFInfo
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- CN114806579A CN114806579A CN202110109924.5A CN202110109924A CN114806579A CN 114806579 A CN114806579 A CN 114806579A CN 202110109924 A CN202110109924 A CN 202110109924A CN 114806579 A CN114806579 A CN 114806579A
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Abstract
本发明公开了一种兼具近红外发光和磁性的量子点(半导体纳米晶),其制备方法及应用。该量子点具有核壳型晶体结构,核为近红外发光的、不含重金属的半导体晶体材料,壳层为磁性的、不含重金属的宽带隙半导体晶体材料,条件温和,工艺简单,操作简便、成本低廉、方法灵活。纳米晶体尺寸为2‑15nm,近红外发射峰位在650‑1500nm范围可根据尺寸和组成任意调变,近红外发光效率最高达到80%。其中壳层晶格中磁性离子稳定标记,磁性离子含量可任意调变,具有高的纵向磁共振弛豫率和优异的磁共振造影性能,可构建近红外光学/磁共振成像多功能探针,用于近红外发光/磁共振多模态生物医学成像。
Description
技术领域
本发明所属技术领域为材料化学、纳米科学、光化学及生物医学,特别涉及一种近红外发光的磁性量子点(磁性半导体纳米晶)及其制备方法与应用。
背景技术
量子点(半导体纳米晶)作为一种新型的光吸收和发射材料,因其独特的电子和光学特性被广泛应用于光电及生物医学领域。此外,由于具有宽带激发窄带发射、发光颜色连续可调、高消光系数、高荧光效率、高发光稳定性以及大Stokes位移等优势,使其在高灵敏、高通量的体内外生物检测中应用前景广阔(Journal of the American ChemicalSociety,2011,133,1176;Chemical Reviews,2016,116,10731;ACS Nano,2014,8,3476)。此外,由于生物组织对近红外光(NIR~650-1700nm)的吸收和散射较低,近红外发光量子点可显著提高活体成像穿透深度和灵敏度,因而是一种很有前景的生物检测用荧光探针,例如活体肿瘤成像和光学手术导航等(Nature,2008,452,580;Journal of the AmericanChemical Society,2016,138,1893;Nature Biomedical Engineering,2017,1,0056)。然而,由于常见的近红外发光量子点多含有镉、铅、汞等重金属离子,如CdTe、CdHgTe、HgS、PbS等,其高毒性限制了其临床应用。因此,开发无毒、环境友好的量子点是至关重要的。
近年来,无重金属离子的I-III-VI或I-VI族等半导体纳米材料如CuInS2,AgInS2和CuInSe2量子点是一类生物安全性优异、低成本的半导体材料,结合其带隙不仅依赖于尺寸,更强烈依赖于阳离子比例的特点,有望获得尺寸相同、发光近红外可调的系列量子点,成为传统II-VI族量子点在体内荧光成像应用中很好的替代品。然而目前研究获得的上述量子点发光峰位普遍小于1000nm。此外,尽管近红外光学成像具有高的成像灵敏度,但是近红外光还面临组织穿透深度和成像分辨率均受限,并且无法提供空间解剖结构信息;而磁共振成像的优势就是组织穿透深度不受限,但其扫描时间较长。若能将量子点的近红外荧光成像和磁共振成像相结合,便可弥补近红外荧光成像的上述缺陷。目前磁性标记方式通常包括顺磁离子的络合物与量子点表面进行化学耦联(ACS Nano,2011,5,8193),以及将顺磁离子掺杂进入量子点晶格(J.Phys.Chem.Lett.,2011,2,2818)。前者在生理条件下顺磁离子易脱附导致两种信号基元发生分离,从而导致“假阳性”甚至“假阴性”的诊断结果;后者可直接将顺磁离子掺杂到量子点发光中心晶格中实现稳定掺杂,但掺杂引入的缺陷能级会大幅淬灭量子点荧光。因此,发展长波长近红外发光的、磁性离子稳定标记的量子点对于提高近红外成像的灵敏度和分辨率至关重要。
发明内容
本发明需要解决的技术问题是提供一种近红外发光波长可调、发光效率高、磁性标记的半导体纳米晶及其制备方法,以克服现有近红外发光半导体毒性大、发光波长短、发光效率低的缺陷。
本发明的目的之一是提供一种近红外发光波长可调且发光效率高、磁共振弛豫率高、尺寸小、单分散性好、生物安全性高的磁性量子点及其制备方法。
本发明所提供的磁性量子点为单分散性纳米颗粒,平均尺寸为2-15nm。
本发明所提供的磁性量子点发光波长在650-1500nm范围可任意调变,宽带激发,发射光谱半峰宽在30-250nm。
本发明的目的之二是提供一种原位包覆宽带隙半导体以提高近红外发光量子点发光效率的同时实现磁性稳定标记的方法,合成具有优异近红外发光性能和磁学性能的核壳结构量子点。
具体地,本发明采用磁性壳层包覆量子点核,
所述磁性壳层为宽带隙ZnxM1-xS、ZnxM1-xSe(0≤x<1)壳层,其中M为磁性离子,包含但不限于锰离子、铁离子、钴离子、镍离子、钆离子、镝离子等磁性离子;
所述核为包含但不限于I-III-VI,I-II-III-VI,I-VI,III-V族等半导体量子点,并包含它们的计量或非计量比的任意组成,以及包含但不限于它们任意的合金型、核壳型、异质型、掺杂型等形式的复合结构,具体可为Cu-In-S、Cu-In-Se、Cu-Al-S、Cu-Al-Se、Cu-In-Ga-S、Cu-In-Ga-Se、Cu-In-Zn-S、Cu-In-Zn-Se、Ag-In-S、Ag-In-Se、Ag2S、Ag2Se、InP等;
磁性壳层和近红外发光中心核的晶格错配率低(<30%),得到的核壳结构量子点单分散性好,没有ZnxM1-xS或ZnxM1-xSe(0≤x<1)单独成核,荧光发射峰位650-1500nm连续可调变;
改变壳层包覆温度(180~250℃)可调控壳层厚度和磁性离子含量,光谱半峰宽窄化明显,近红外发光核壳结构量子点的发光效率最高可以达到80%(绝对量子产率)。
本发明的目的之三是提供一种在近红外发光半导体量子点壳层晶格中进行原位磁性标记的方法,进而构建近红外发光波长连续可调、磁性离子含量可控的磁光量子点,赋予半导体量子点优异的近红外光学性质和磁学性质。
本发明所提供的磁性量子点壳层中磁性离子含量连续可调,具有优异的磁共振造影性能,并且磁性离子在壳层晶格中的稳定标记不显著影响量子点的光学性质。
技术方案
本发明提供的近红外发光波长可调变、发光效率高、磁性稳定标记的半导体纳米晶及其制备方法,通过下述方案实现:
液相化学法合成近红外发光、核壳结构磁性半导体纳米晶,其中,核为包含但不限于I-III-VI,I-II-III-VI,I-VI,III-V族等半导体量子点,并包含它们的计量或非计量比的任意组成,以及包含但不限于它们任意的合金型、核壳型、异质型、掺杂型等形式的复合结构,如Cu-In-S、Cu-In-Se、Cu-Al-S、Cu-Al-Se、Cu-In-Ga-S、Cu-In-Ga-Se、Cu-In-Zn-S、Cu-In-Zn-Se、Ag-In-S、Ag-In-Se、Ag2S、Ag2Se、InP等;壳为磁性壳层,为宽带隙ZnxM1-xS、ZnxM1-xSe(0≤x<1)壳层,其中M为磁性离子,包含但不限于锰离子、铁离子、钴离子、镍离子、钆离子、镝离子等磁性离子,作为钝化和磁性壳层。其制备方法,包括以下步骤:
(1)近红外发光中心量子点核的合成
将内核用阳离子前驱体混合于配体和溶剂中,反应混合物在真空下脱气,氮气保护,将内核用阴离子前驱体和内核用阳离子前驱体共同加入,或者后期注射,将所得反应混合物加热至180~300℃,惰性气体如氮气或氩气保护下反应,得到近红外发光中心量子点核;
(2)近红外发光的核壳结构磁性量子点的合成
在(1)合成反应后引入锌源、磁性前驱体作为壳层阳离子前驱体,加入壳层阴离子前驱体,在量子点核表面形成磁性宽带隙钝化壳层;
或,
(2’)在(1)合成反应后引入锌源作为壳层阳离子前驱体,加入壳层阴离子前驱体,反应,得到近红外发光核壳结构量子点;向反应后体系中加入磁性前驱体,加入壳层阴离子前驱体,进行磁性离子的掺杂,在量子点核表面形成磁性宽带隙钝化壳层;
(3)水溶性近红外发光磁性量子点的制备
采用水溶性分子对步骤(2)所得量子点进行配体置换,从而对量子点进行表面改性,所选水溶性分子包含但不限于水溶性小分子、聚乙二醇(PEG)及其衍生物、高分子聚合物、表面活性剂、多肽及蛋白。
上述方法步骤(1)中,所述内核用金属阳离子前驱体为金属硝酸盐、金属碘化盐、金属氯化盐、金属溴化盐、金属硫酸盐、金属亚硫酸盐、金属碳酸盐、金属硼酸盐、有机金属盐(如金属醋酸盐、金属甲酸盐、金属硬脂酸盐、金属油酸盐、金属柠檬酸盐、金属苯甲酸盐、金属醇盐)等中的至少一种,包含但不限于硝酸银、碘化亚铜、氯化亚铜、溴化亚铜、醋酸铟、硝酸铟、氯化铟、硫酸铟等;
内核用阴离子前驱体为硒单质及其化合物,硫单质及其化合物中的至少一种,包含但不限于硒粉、硫粉、硫化钠、硒代氨基酸、硫代氨基酸、硒代多肽、硫代多肽、硒代蛋白、硫代蛋白、硫脲、硒脲、硫醇、硒醇、硒吩、二甲基硒、噻唑、硫代乙酰胺、硫代丙酰胺、硫代乙酸、半胱氨酸、谷胱甘肽、硫化氢、亚硫酸及其盐、硫代硫酸钠、亚硒酸及其盐等;
所述配体为有机硫醇、有机醇、有机酸、有机胺、有机氧膦、有机磷、或有机烯烃中的至少一种,具体可为烷基硫醇、油酸、油胺、十六胺等;
其中,所述的烷基硫醇包含但不限于正十二硫醇、正庚硫醇、正辛硫醇或正癸硫醇等;
所述溶剂为有机硫醇、有机醇、有机酸、有机胺、有机氧膦、有机磷、或有机烯烃中的至少一种,包含但不限于烷基硫醇、油酸、油胺、十八烯等;
所述配体和溶剂比例根据阳离子化学性质调节;
反应温度和反应时间依据目标组成调节;
步骤(2)的操作为:将一定比例的锌前驱体、磁性前驱体,配体,以及溶剂混合,加热真空下脱气,得到壳层阳离子前驱体溶液;然后将壳层阳离子前驱体溶液和阴离子前驱体储备液加入步骤(1)中近红外发光中心量子点核的反应体系中,通过体系的高温引发壳层包覆;
通过改变前驱体加入速度、前驱体加入浓度、反应温度及反应时间等参数调节壳层厚度和发光效率;
所述锌前驱体为锌单质和锌盐等化合物中的至少一种,包含但不限于硬脂酸锌、醋酸锌、硝酸锌、硫酸锌、氯化锌、溴化锌、硼酸锌、碳酸锌、碘化锌、柠檬酸锌、乙酰丙酮锌、亚硫酸锌、油酸锌、磷酸锌、锌粉等;
所述磁性前驱体为含有磁性金属离子的金属硝酸盐、金属碘化盐、金属氯化盐、金属溴化盐、金属硫酸盐、金属亚硫酸盐、金属碳酸盐、金属硼酸盐、有机金属盐(如金属醋酸盐、金属甲酸盐、金属硬脂酸盐、金属油酸盐、金属柠檬酸盐、金属苯甲酸盐、金属醇盐、金属乙酰丙酮盐等)等中的至少一种,具体可为硬脂酸锰、醋酸锰、氯化锰、油酸锰、氯化铁、油酸铁、氯化钴、氯化镍、氯化钆等;
所述壳层阴离子前驱体为硒单质及其化合物中的至少一种,具体可为硒粉、硫粉、硫化钠、硒代氨基酸、硫代氨基酸、硒代多肽、硫代多肽、硒代蛋白、硫代蛋白、硫脲、硒脲、硫醇、硒醇、硒吩、二甲基硒、噻唑、硫代乙酰胺、硫代丙酰胺、硫代乙酸、半胱氨酸、谷胱甘肽、硫化氢、亚硫酸及其盐、硫代硫酸钠、亚硒酸及其盐。
将锌源或磁性前驱体分别加入到含有烷基硫醇、十八烯等的有机溶剂中,分别制备锌和锰前驱体溶液,通过加入油酸或油胺等调节反应活性,然后加热真空下脱气;将此壳层阳离子前驱体溶液和壳层阴离子前驱体加入核的反应体系中,通过体系的高温引发反应,通过改变锌源、磁性离子源的投料比例及投料次序、投料速度、反应温度、反应时间等参数实现对壳层厚度及组成的调节,获得ZnxM1-xS或ZnxM1-xSe(0≤x<1)壳层,其中M为磁性离子,包含但不限于锰离子、铁离子、钴离子、镍离子、钆离子、镝离子等磁性离子;反应结束后将反应液冷却至室温;
上述水溶性核壳结构磁性半导体纳米晶或由上述方法制备得到的水溶性核壳结构磁性半导体纳米晶在制备体内外生物检测和疾病诊疗的产品中的应用也属于本发明的保护范围。
所述体内外生物检测和疾病治疗的产品包含但不限于用于疾病如肿瘤的靶向成像、单/多模态成像、手术导航、光动力治疗、化动力治疗、光声成像、光热治疗、免疫治疗、基因治疗、靶向治疗、复合治疗等产品,具体可为近红外发光/磁共振多模态成像探针。
近红外光学成像:利用近红外成像系统进行荷瘤小鼠的肿瘤成像。具体如下,小鼠麻醉后,注射水溶性的磁性量子点。采用可见光或近红外光激发,长波通滤光片收集荧光发射。成像时,将小鼠放置在恒温动物床上,采集不同时间点老鼠皮下肿瘤区域荧光成像。成像期间小鼠吸入混合异氟烷的氧气,处于麻醉状态。
磁共振(MR)成像:利用小动物核磁共振成像仪,对荷瘤小鼠进行T1和T2磁共振加权成像。具体如下:尾静脉注射水溶性的磁性量子点。成像时采集不同时间点小鼠肿瘤区域磁共振加权像。
本发明具有以下优点和有益效果:
1)本发明提供了一种兼具近红外发光和磁性的半导体量子点,其制备方法所涉及的前驱体、配体、溶剂等原料易得、条件温和、实验步骤简便、成本低廉。
2)本发明制备得到的兼具近红外发光和磁性的半导体量子点,其发光波长650-1500nm可根据尺寸和组成任意调变,近红外发光效率最高可达80%。
3)本发明制备得到的兼具近红外发光和磁性的半导体量子点,其磁离子在量子点的壳层晶格中稳定标记,其磁含量可连续可调,离子纵向摩尔弛豫率高,磁共振造影性能优异。
4)本发明制备得到的兼具近红外发光和磁性的半导体量子点,可构建近红外发光/磁共振双模态成像探针,用于体内外生物检测和成像。
附图说明
图1为本发明实施例1所得的CuInSe2量子点的透射电镜(TEM)照片。
图2为本发明实施例1所得的CuInSe2量子点光学性质表征,包括不同反应时间的近红外发射光谱(a)、发射峰位(b)、半峰宽(c)和发光强度(d)。
图3为本发明实施例6所得的AgInSe2@ZnS核壳结构量子点(反应温度200℃,反应时间3小时)的透射电镜(TEM)照片。
图4为本发明实施例7所得的CuInSe2@ZnS核壳结构量子点的透射电镜(TEM)照片。
图5为本发明实施例7所得的CuInSe2@ZnS核壳结构量子点光学性质表征,包括不同反应时间的发射光谱。
图6为本发明实施例7所得的CuInSe2@ZnS核壳结构量子点在不同壳层包覆温度下荧光发射峰位随包覆时间的变化(a)及不同包覆温度下荧光发射半峰宽随包覆时间的变化(b)。
图7为本发明实施例9所得的磁性离子掺杂CuInSe2@ZnS:Mn核壳结构量子点的透射电镜(TEM)照片。
图8为本发明实施例9所得的CuInSe2@ZnS:Mn核壳结构量子点光学性质表征,包括不同反应时间的发射光谱(a)、发射峰位(b上)半峰宽(b下)。
图9为本发明实施例9所得的CuInSe2@ZnS:Mn核壳结构量子点不同反应时间的绝对量子产率。
图10为本发明实施例7所得的CuInSe2@ZnS和实施例9所得的磁性离子掺杂CuInSe2@ZnS:Mn量子点的电子自旋共振谱图(77K下测试)。
图11为本发明实施例12所得的水溶性磁性离子掺杂CuInSe2@ZnS:Mn量子点纳米探针,接种皮下异质瘤的小鼠注射探针前后不同时间点的近红外II区活体成像图片。
图12为本发明实施例12所得的水溶性磁性离子掺杂CuInSe2@ZnS:Mn量子点纳米探针,接种皮下异质瘤和肺转移瘤的小鼠注射探针前后不同时间点的T1磁共振成像图片。
具体实施方式
下面通过具体实施例对本发明进行说明,但本发明并不局限于此。
下述实施例中所使用的实验方法如无特殊说明,均为常规方法;下述实施例中所用的试剂、生物材料等,如无特殊说明,均可从商业途径得到,如可从包含但不限于Sigma-Aldrich、TCI、Aladdin、伊诺凯、百灵威、Acros、国药试剂、阿法埃莎、默克、Abcam、Gibco、Thermo-Fisher、Fisher Scientific、ATCC、BPS Bioscience、Invitrogen、BD、Roche、Nanocs、BioLegend、eBioscience、Amgen、Gilead Sciences、Celgene、Ambion、Amresco、BioTek、Hyclone、Millipore、Promega、R&D system、Sartorius等购买。
在下面给出本发明的技术方案的具体示例,但本领域技术人员能够理解,以下具体表述仅是实施本发明的多种方案中的示例,它们不应被以任何方式理解为限制本发明的范围。
实施例1、
1.5mmol CuI和1.5mmol In(CH3COO)3混合于3mL十二硫醇和30mL十八烯中,真空下脱气20min,后在120℃下脱气40min。继而在氮气保护下加入Se源。将反应混合物加热在200℃并氮气保护下进行反应,具体可通过调节反应温度、反应时间和Cu:In比例实现对近红外发光峰位、发光半峰宽及发光强度的调变。反应结束后降温,纯化后分散在甲苯中。
图1为反应40分钟所得的计量比CuInSe2量子点的透射电镜(TEM)照片。
图2为所得的计量比CuInSe2量子点光学性质表征,说明通过调节反应时间可实现对近红外发光峰(a)、发射峰波长(b)、近红外发射半峰宽(c)和发光强度(d)的调控。
实施例2、
1.5mmol CuCl和1.5mmol In(CH3COO)3混合于3mL正癸硫醇和30mL十八烯中,真空下脱气20min,后在120℃下脱气40min。继而在氮气保护下加入Se源。将反应混合物加热在200℃并氮气保护下进行反应,具体可通过调节反应时间和Cu:In比例实现对Cu-In-Se的近红外发光峰位、发光半峰宽及发光强度的调变。反应结束后降温,纯化后分散在环己烷中。
实施例3、
1.5mmol AgNO3和1.5mmol In(CH3COO)3混合于3mL烷基硫醇和30mL十八烯中,真空下脱气20min,后在120℃下脱气40min。继而在氮气保护下加入Se源。将反应混合物加热在200℃并氮气保护下进行反应,具体可通过调节反应时间和Ag:In比例实现对Ag-In-Se量子点近红外发光峰位、发光半峰宽及发光强度的调变。反应结束后降温,纯化后分散在环己烷中。
实施例4、
0.9mmol CuI和0.75mmol In(CH3COO)3混合于1mL十二硫醇和15mL十八烯中,真空下脱气20min,后在120℃下脱气40min。继而在氮气保护下加入Se源。将反应混合物加热并氮气保护下进行反应,具体可通过调节反应温度、反应时间和Cu:In比例实现对Cu-In-Se近红外发光峰位、发光半峰宽及发光强度的调变。反应结束后降温,纯化后分散在环己烷中。
实施例5、
3.75mmol ZnSt2与1mL十二硫醇、30mL十八烯混合,将溶液加热并真空脱气,后通氮气。将得到的锌源储备液加入实施例1)计量比CuInSe2核的反应体系(不纯化)中,同时加入2mL十二硫醇。氮气保护下在200℃加热进行反应,具体可通过调节反应温度、反应时间实现对壳层厚度及近红外发光强度的调变。反应结束后将反应液冷却至室温,纯化后分散在甲苯里待用。
实施例6、
3.75mmol ZnSt2与1mL十二硫醇、30mL十八烯混合,将溶液加热并真空脱气,后通氮气。将得到的锌源储备液加入实施例3计量比AgInSe2核的反应体系(不纯化)中,同时加入2mL十二硫醇。氮气保护下在200℃加热进行反应,具体可通过调节反应温度、反应时间实现对壳层厚度及发光强度的调变。反应结束后将反应液冷却至室温,纯化后分散在甲苯里待用。
图3为所得的AgInSe2@ZnS核壳结构量子点(反应温度200℃,反应时间3小时)的透射电镜(TEM)照片。
实施例7、
7.5mmol ZnSt2与2mL十二烷基硫醇、40mL十八烯混合,将溶液加热并在真空脱气,后通氮气。将所得锌源储备液逐滴加入实施例1)计量比CuInSe2核的反应体系中,同时加入4mL十二硫醇。氮气保护下加热反应。反应结束后将反应液冷却至室温,纯化后分散在甲苯里待用。同时,调控ZnS额壳层的包覆温度180-250℃获得目标壳层厚度,按照上述步骤可制备ZnS壳层厚度可调变的CuInSe2@ZnS量子点。
图4为所得的CuInSe2@ZnS核壳结构量子点(反应温度215℃,反应时间3小时)的透射电镜(TEM)照片。
图5为所得的CuInSe2@ZnS核壳结构量子点光学性质表征,通过对反应时间的调节,可以实现对近红外发光强度的增强。
图6为所得的CuInSe2@ZnS核壳结构量子点,说明调节壳层反应温度可以有效调控近红外发射峰波长(a)和近红外发射半峰宽(b)。
实施例8、
7.5mmol Zn(CH3COO)2与2mL十二硫醇、15mL油胺、15mL十八烯混合,将溶液加热并在真空下脱气,后通氮气。使将锌源储备液加入到实施例1)CuInSe2核的反应体系中,同时加入4mL十二烷基硫醇。氮气保护下加热反应,具体可通过调节反应温度、反应时间实现对壳层厚度及近红外发光强度的调变。反应结束后将反应液冷却至室温,纯化后分散在甲苯里待用。
实施例9、
按照实施例7)合成核壳结构量子点的步骤,在215℃下反应3h后反应混合物不纯化,降温后加入含有0.75mmol MnSt2的十二烷基硫醇溶液,以启动Mn2+掺杂过程。间隔提取少量反应液来监控整个掺杂过程,具体通过掺杂反应温度和反应时间获得磁性离子含量可调变的磁性量子点。反应结束后将反应液冷却至室温,纯化后分散在甲苯里待用。
图7为磁性离子掺杂CuInSe2@ZnS:Mn核壳结构量子点的透射电镜(TEM)照片(掺杂反应温度180℃,掺杂反应时间2小时)
图8为所得的CuInSe2@ZnS:Mn核壳结构量子点光学性质表征,通过调节反应时间可对近红外发光峰(a)、近红外发射峰波长(b上)、发光半峰宽(b下)进行调控。
图9为所得的CuInSe2@ZnS:Mn核壳结构量子点不同反应时间的近红外发光绝对量子产率。
图10为实施例7所得的CuInSe2@ZnS和实施例9所得的磁性离子掺杂CuInSe2@ZnS:Mn量子点的电子自旋共振谱图(77K下测试)。
实施例10、
按照实施例8)合成核壳结构量子点的步骤,在210℃下反应3h后反应混合物不纯化,降温后加入含有0.75mmol Mn(CH3COO)2的十二硫醇溶液,以启动Mn2+掺杂过程,通过温度和反应时间获得磁性离子含量可调变的磁性量子点。反应结束后将反应液冷却至室温,纯化后分散在环己烷里待用。
实施例11、
按照实施例8)合成核壳结构量子点的步骤,在210℃下反应5h后反应混合物不纯化,降温后加入0.75mmol Mn(CH3COO)2的正癸硫醇溶液,以启动Mn2+掺杂过程,通过温度和反应时间获得磁性离子含量可调变的磁性量子点。反应结束后将反应液冷却至室温,纯化后分散在正己烷里待用。
实施例12、
按照实施例9)合成的CuInSe2@ZnS:Mn,通过表面配体置换反应制备获得水溶性半导体纳米晶,并进行活体成像,表面配体置换方法具体为:选用一端为巯基、另一端为甲氧基的PEG分子(PEG分子量:2000),并同时选用一端为巯基、另一端为活性羧基官能团的PEG分子(PEG分子量:2000),以一定比例(10:1)共同做配体,将10mg CuInSe2@ZnS:Mn分散于5mL甲苯中,后将其加入到20mL含有200mg配体的甲苯溶液中,混合溶液加热到70℃通氮气搅拌反应3h,而后用水萃取,得到PEG修饰的水相量子点,透析或超滤纯化除去游离配体,最后分散在水溶液中,以备进行近红外和磁共振活体成像。
上述近红外和磁共振活体成像具体操作步骤如下:1)细胞培养:4T1细胞株由通派生物细胞库提供,在RPMI-1640培养基中加入10%胎牛血清和1%青霉素-链霉素溶液(100×),置于37℃,含5%CO2的细胞培养箱中进行培养,所述4T1细胞可换成其他各种肿瘤细胞;2)动物模型构建:在体重约为20g的Balb/c小鼠(购自北京大学医学院动物房),右后肢皮下注射100μL的1)细胞悬液,构建皮下肿瘤模型;3)近红外活体成像:荷瘤小鼠麻醉并脱毛后,经尾静脉注射纳米探针。将小鼠放置在恒温动物床上,光学成像采用808nm连续激光激发,采集不同时间点老鼠皮下肿瘤区域近红外发光成像。成像期间小鼠吸入混合2%异氟烷的氧气,处于麻醉状态,采集不同时间点的成像结果;4)磁共振活体成像:经尾静脉注射上述纳米探针,利用磁场强度为1.5T的小动物核磁共振成像仪,对小鼠肿瘤进行磁共振加权成像。成像期间小鼠吸入混合2%异氟烷的氧气,处于麻醉状态。
图11为实施例12所得的水溶性磁性离子掺杂CuInSe2@ZnS:Mn量子点纳米探针接种皮下异质瘤的小鼠注射探针前后不同时间点的近红外II区活体成像图片,证明所述磁性量子点可成功用于活体层面的近红外II区光学成像及肿瘤诊断应用。
图12为实施例12所得的水溶性磁性离子掺杂CuInSe2@ZnS:Mn量子点纳米探针接种皮下异质瘤和肺转移瘤的小鼠注射探针前后不同时间点的T1磁共振成像图片,证明所述磁性量子点可成功用于活体层面的磁共振成像及肿瘤诊断应用。
Claims (9)
1.一种兼具近红外发光性质和磁性性质的量子点,具有核壳型结构:其内核为近红外发光的半导体量子点,外壳为磁性宽带隙半导体材料。
2.根据权利要求1所述的磁性量子点,其特征在于:所述近红外发光的半导体量子点为I-III-VI,I-II-III-VI,III-V,I-VI族半导体量子点,并包含它们的计量或非计量比组成,以及它们任意的合金型、核壳型、异质型、掺杂型形式的复合结构;
所述磁性宽带隙半导体材料为宽带隙ZnxM1-xS、ZnxM1-xSe,0≤x<1,壳层,其中M为磁性离子,具体可为锰离子、铁离子、钴离子、镍离子、钆离子、镝离子中的至少一种。
3.制备权利要求1或2所述的量子点的方法,包括如下步骤:
(1)近红外发光中心量子点核的合成
将内核用阳离子前驱体混合于配体和溶剂中,反应混合物在真空下脱气,氮气保护,将内核用阴离子前驱体和内核用阳离子前驱体共同加入,或者后期注射,将所得反应混合物加热至180~300℃,惰性气体保护下反应,得到近红外发光中心量子点核;
(2)近红外发光的核壳结构磁性量子点的合成
在(1)合成反应后引入锌源、磁性前驱体作为壳层阳离子前驱体,加入壳层阴离子前驱体,在量子点核表面形成磁性宽带隙钝化壳层;
或,
(2’)在(1)合成反应后引入锌源作为壳层阳离子前驱体,加入壳层阴离子前驱体,反应,得到近红外发光核壳结构量子点;向反应后体系中加入磁性前驱体,加入壳层阴离子前驱体,进行磁性离子的掺杂,在量子点核表面形成磁性宽带隙钝化壳层;
(3)水溶性近红外发光磁性量子点的制备
采用水溶性分子对步骤(2)所得量子点进行配体置换,从而对量子点进行表面改性,
所选水溶性分子选自:水溶性小分子、聚乙二醇及其衍生物、高分子聚合物、表面活性剂、多肽及蛋白。
4.根据权利要求3所述的方法,其特征在于:步骤(1)中,所述内核用阳离子前驱体为金属硝酸盐、金属碘化盐、金属氯化盐、金属溴化盐、金属硫酸盐、金属亚硫酸盐、金属碳酸盐、金属硼酸盐、有机金属盐中的至少一种,
具体可为硝酸银、碘化亚铜、氯化亚铜、溴化亚铜、醋酸铟、硝酸铟、氯化铟、硫酸铟、异丙醇铟;
内核用阴离子前驱体为硒单质及其化合物,硫单质及其化合物中的至少一种,具体可为硒粉、硫粉、硫化钠、硒代氨基酸、硫代氨基酸、硒代多肽、硫代多肽、硒代蛋白、硫代蛋白、硫脲、硒脲、硫醇、硒醇、硒吩、二甲基硒、噻唑、硫代乙酰胺、硫代丙酰胺、硫代乙酸、半胱氨酸、谷胱甘肽、硫化氢、亚硫酸及其盐、硫代硫酸钠、亚硒酸及其盐。
5.根据权利要求3或4所述的方法,其特征在于:步骤(2)的操作为:将锌前驱体、磁性前驱体,配体,以及溶剂混合,加热真空下脱气,得到壳层阳离子前驱体溶液;然后将壳层阳离子前驱体溶液和阴离子前驱体储备液加入步骤(1)中近红外发光中心量子点核的反应体系中,通过体系的高温引发壳层包覆,在量子点核表面形成磁性宽带隙钝化壳层。
所述配体为有机硫醇、有机醇、有机酸、有机胺、有机氧膦、有机磷、和有机烯烃中的至少一种,具体可为烷基硫醇、油酸、油胺、十六胺;
其中,所述的烷基硫醇具体可为正十二硫醇、正庚硫醇、正辛硫醇或正癸硫醇;
所述溶剂为有机硫醇、有机醇、有机酸、有机胺、有机氧膦、有机磷、和有机烯烃中的至少一种,具体可为烷基硫醇、油酸、油胺和十八烯。
6.根据权利要求3-5中任一项所述的方法,其特征在于:所述锌前驱体为锌单质和锌盐化合物中的至少一种,具体可为硬脂酸锌、醋酸锌、硝酸锌、硫酸锌、氯化锌、溴化锌、硼酸锌、碳酸锌、碘化锌、柠檬酸锌、乙酰丙酮锌、亚硫酸锌、油酸锌、磷酸锌、锌粉;
所述磁性前驱体为含有磁性金属离子的金属硝酸盐、金属碘化盐、金属氯化盐、金属溴化盐、金属硫酸盐、金属亚硫酸盐、金属碳酸盐、金属硼酸盐、有机金属盐中的至少一种,具体可为硬脂酸锰、醋酸锰、氯化锰、油酸锰、氯化铁、油酸铁、氯化钴、氯化钆;
所述壳层阴离子前驱体为硒单质及其化合物,硫单质及其化合物中的至少一种,具体可为硒粉、硫粉、硫化钠、硒代氨基酸、硫代氨基酸、硒代多肽、硫代多肽、硒代蛋白、硫代蛋白、硫脲、硒脲、硫醇、硒醇、硒吩、二甲基硒、噻唑、硫代乙酰胺、硫代丙酰胺、硫代乙酸、半胱氨酸、谷胱甘肽、硫化氢、亚硫酸及其盐、硫代硫酸钠、亚硒酸及其盐。
7.权利要求1或2所述的量子点或由权利要求3-6中任一项所述方法制备得到的水溶性核壳结构磁性半导体纳米晶在制备体内外生物检测和疾病诊疗的产品中的应用。
8.根据权利要求7所述的应用,其特征在于:所述体内外生物检测和疾病诊疗的产品,具体可为:用于多肽、核酸及蛋白等生物分子的检测,细胞/组织的检测,疾病如肿瘤的靶向成像、单/多模态成像、手术导航、光动力治疗、化动力治疗、光声成像、光热治疗、免疫治疗、基因治疗、靶向治疗、复合治疗的产品。
9.根据权利要求8所述的应用,其特征在于:所述体内外生物检测和疾病诊疗的产品为红外发光/磁共振双模态成像探针。
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