Gd_(3+) doped CuInS_2/ZnS nanocrystals with high quantum yield for bimodal fluorescence/magnetic resonance imaging
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摘要
Recently, CuInS_2/ZnS nanocrystals(CISZ NCs) have been widely used in many fields due to their excellent properties, such as tunable photoluminescence(PL) spectra, broad absorption, and non-toxicity. In order to expand the application of CISZ NCs, Gd~(3+) was introduced into the host serving as paramagnetic modules to achieve magnetic resonance imaging(MRI) enhancement. MRI probes could provide high-resolution anatomical information. The derived Gd-Cu-In-S/ZnS nanocrystals(GCISZNCs) exhibited the strong orange photoluminescence with a quantum yield of 57.6% and significantly high longitudinal relaxivity(r_1=20.4 mmol/s) in comparison with commercial Magnevist(Gd-DTPA, r_1=4.5 mmol/s). Effective enhancement of MRI and improved longitudinal relaxivity as well as lower cytotoxicity mode GCISZ NCs an ideal MRI probe, suggesting its potential and significance in practical biological and clinic applications in the future.
Recently, CuInS_2/ZnS nanocrystals(CISZ NCs) have been widely used in many fields due to their excellent properties, such as tunable photoluminescence(PL) spectra, broad absorption, and non-toxicity. In order to expand the application of CISZ NCs, Gd~(3+) was introduced into the host serving as paramagnetic modules to achieve magnetic resonance imaging(MRI) enhancement. MRI probes could provide high-resolution anatomical information. The derived Gd-Cu-In-S/ZnS nanocrystals(GCISZNCs) exhibited the strong orange photoluminescence with a quantum yield of 57.6% and significantly high longitudinal relaxivity(r_1=20.4 mmol/s) in comparison with commercial Magnevist(Gd-DTPA, r_1=4.5 mmol/s). Effective enhancement of MRI and improved longitudinal relaxivity as well as lower cytotoxicity mode GCISZ NCs an ideal MRI probe, suggesting its potential and significance in practical biological and clinic applications in the future.
Recently, CuInS_2/ZnS nanocrystals(CISZ NCs) have been widely used in many fields due to their excellent properties, such as tunable photoluminescence(PL) spectra, broad absorption, and non-toxicity. In order to expand the application of CISZ NCs, Gd~(3+) was introduced into the host serving as paramagnetic modules to achieve magnetic resonance imaging(MRI) enhancement. MRI probes could provide high-resolution anatomical information. The derived Gd-Cu-In-S/ZnS nanocrystals(GCISZNCs) exhibited the strong orange photoluminescence with a quantum yield of 57.6% and significantly high longitudinal relaxivity(r_1=20.4 mmol/s) in comparison with commercial Magnevist(Gd-DTPA, r_1=4.5 mmol/s). Effective enhancement of MRI and improved longitudinal relaxivity as well as lower cytotoxicity mode GCISZ NCs an ideal MRI probe, suggesting its potential and significance in practical biological and clinic applications in the future.
引文
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[23]Hu S J,Liu Y X,Wu X F,Tang Z J,Li Z M,Yan H Y,Chen Z H,Hu P,Yu Y.Remarkable red-shift of upconversion luminescence and anti-ferromagnetic coupling in Na Lu F4:Yb3+/Tm3+/Gd3+/Sm3+bifunctional microcrystals.J.Rare Earths,2016,34:166.
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[25]Danilo H J,Kevin G S,Prashant V K.Two distinct transitions in CuxIn S2 quantum dots.Band gap versus sub-band gap excitations in copper-deficient structures.J.Phys.Chem.Lett.,2016,7:1452.
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[27]Zheng J P,Liu Q L,Zhen M M,Jiang F,Shu C Y,Jin C,Yang Y J,Hisham A A,Wang C R.Multifunctional imaging probe based on gadofulleride nanoplatform.Nanoscale,2012,4:3669.
[28]Enzo T,Daniela D C,Alessandra V,Silvio A.Challenges for molecular magnetic resonance imaging.Chem.Rev.,2010,110:3019.
[29]Xuan T T,Wang S,Wang X J,Liu J Q,Chen J Y,Li H L,Pan L K,Sun Z.Single-step non-injection synthesis of highly luminescent water soluble Cu+doped Cd S quantum dots:application as bio-imaging agents.Chem.Commun.,2013,49:9045.
[30]Abdullah M M,Rahman M M,Bouzid H,Faisal M,Khan S B,Al-Sayari S A,Ismail A A.Sensitive and fast response ethanol chemical sensor based on as-grown Gd2O3nanostructures.J.Rare Earths,2015,33:214.
[2]Xuan T T,Liu J Q,Yu C Y,Xie R J,Li H L.Facile synthesis of cadmium-free Zn-In-S:Ag/Zn S nanocrystals for bio-imaging.Sci.Rep.,2016,6:24459.
[3]Xuan T T,Liu J Q,Li H L,Sun H C,Pan L K,Chen X H,Sun Z.Microwave synthesis of high luminescent aqueous Cd Se/Cd S/Zn S quantum dots for crystalline silicon solar cells with enhanced photovoltaic performance.RSC Adv.,2015,5:7673.
[4]Hong M,Xuan T T,Liu J Q,Jiang Z Y,Chen Y W,Chen X H,Li H L.Air-exposing microwave-assisted synthesis of Cu In S2/Zn S quantum dots for silicon solar cells with enhanced photovoltaic performance.RSC Adv.,2015,5:102682.
[5]Pan D C,Weng D,Wang X L,Xiao X F,Chen W,Xu C L,Yang Z Z,Lu Y F.Alloyed semiconductor nanocrystals with broad tunable band gaps.Chem.Commun.,2009,(28):4221.
[6]Jiang T T,Song J L Q,Wang H J,Ye X C,Wang H,Zhang W T,Yang M Y,Xia R X,Zhu L X,Xu X L.Aqueous synthesis of color tunable Cu doped Zn-In-S/Zn Snanoparticles in the whole visible region for cellular imaging.J.Mater.Chem.B,2015,3:2402.
[7]Park J,Kim S W.Cu In S2/Zn S core/shell quantum dots by cation exchange and their blue-shifted photoluminescence.J.Mater.Chem.,2011,21:3745.
[8]Leng Z H,Huang L,Shao F,Lv Z C,Li T T,Gu X X,Han H Y.Facile synthesis of Cu-In-Zn-S alloyed nanocrystals with temperature-dependent photoluminescence spectra.Mater.Lett.,2014,119:100.
[9]Chen W,Wu D Y,Chan Y C,Lin C C,Chung P H,Michael H,Liu R S.Evaluations of the chemical stability and cytotoxicity of Cu In S2 and Cu In S2/Zn S core/shell quantum dots.J.Phys.Chem.C,2015,119:2852.
[10]Li L,Daou T J,Texier I,Chi T H K,Liem N Q,Reiss P.Highly luminescent Cu In S2/Zn S core/shell nanocrystals:cadmium-free quantum dots for in vivo imaging.Chem.Mater.,2009,21:2422.
[11]Yang W T,Guo W S,Gong X Q,Zhang B B,Wang S,Chen N,Yang W T,Tu Y,Fang X M,Chang J.Facile synthesis of Gd-Cu-In-S/Zn S bimodal quantum dots with optimized properties for tumor targeted fluorescence/MRin vivo imaging.ACS Appl.Mater.Interfaces,2015,7:18759.
[12]Wu Y L,Xu X Z,Li Q L,Yang R C,Ding H X,Xiao Q.Synthesis of bi-functional Gd2O3:Eu3+nanocrystals and their applications in biomedical imaging.J.Rare Earths,2015,33(5):529.
[13]Guillet N R,Bridot J L,Seo Y,Fortin M A,Kleitz F.Enhanced relaxometric properties of MRI“positive”contrast agents confined in three-dimensional cubic mesoporous silica nanoparticles.Adv.Funct.Mater.,2011,21:4653.
[14]Yeh C S,Su C H,Ho W H,Huang C C,Chang J C,Chien Y H,Hung S T,Liau M C,Ho H Y.Tumor targeting and MR imaging with lipophilic cyanine-mediated near-infrared responsive porous Gd silicate nanoparticles.Biomaterials,2013,34:5677.
[15]Zhang F,Sun T T,Zhang Y,Li Q,Chai C,Lu L,Shen W,Yang J,He X W,Zhang Y K,Li W Y.Facile synthesis of functional gadolinium-doped Cd Te quantum dots for tumor-targeted fluorescence and magnetic resonance dualmodality imaging.J.Mater.Chem.B,2014,2:7201.
[16]Gong N Q,Wang H,Li S,Deng Y L,Chen X A,Ye L,Gu W.Microwave-assisted polyol synthesis of gadolinium-doped green luminescent carbon dots as a bimodal nanoprobe.Langmuir,2014,30:10933.
[17]Jiang C L,Shen Z T,Luo C H,Lin H C,Huang R,Wang Y T,Peng H.One-pot aqueous synthesis of gadolinium doped Cd Te quantum dots with dual imaging modalities.Talanta,2016,155:14.
[18]Cheng C Y,Ou K L,Huang W T,Chen J K,Chang J Y,Yang C H.Gadolinium-based Cu In S2/Zn S nanoprobe for dual-modality magnetic resonance/optical imaging.ACSAppl.Mater.Interfaces,2013,5:4389.
[19]Guo W S,Yang W T,Wang Y,Sun X L,Liu Z Y,Zhang B B,Chang J,Chen X Y.Color tunable Gd-Zn-Cu-In-S/Zn S quantum dots for dual modality magnetic resonance and fluorescence imaging.Nano Res.,2014,7:1581.
[20]Tang X S,Cheng W L,Eugene S G C,Xue J M.Synthesis of Cu In S2-Zn S alloyed nanocubes with high luminescence.Chem.Commun.,2010,47:5217.
[21]Chang J Y,Chang S C,Tzing S H,Li C H.Development of nonstoichiometric Cu In S2 as a light-harvesting photoanode and catalytic photocathode in a sensitized solar cell.ACS Appl.Mater.Interfaces,2014,6:22272.
[22]Samiran H,Dambarudhar M.Oriented attachment(OA)mediated characteristic growth of Gd2O3 nanorods from nanoparticle seeds.J.Rare Earths,2016,34:158.
[23]Hu S J,Liu Y X,Wu X F,Tang Z J,Li Z M,Yan H Y,Chen Z H,Hu P,Yu Y.Remarkable red-shift of upconversion luminescence and anti-ferromagnetic coupling in Na Lu F4:Yb3+/Tm3+/Gd3+/Sm3+bifunctional microcrystals.J.Rare Earths,2016,34:166.
[24]Han W,Yi L X,Zhao N,Tang A W,Gao M Y,Tang Z Y.Synthesis and shape-tailoring of copper sulfide/indium sulfide-based nanocrystals.J.Am.Chem.Soc.,2008,130:13152.
[25]Danilo H J,Kevin G S,Prashant V K.Two distinct transitions in CuxIn S2 quantum dots.Band gap versus sub-band gap excitations in copper-deficient structures.J.Phys.Chem.Lett.,2016,7:1452.
[26]Chen Y,Li S,Huang L,Pan D.Green and facile synthesis of water-soluble Cu-In-S/Zn S core/shell quantum dots.Inorg.Chem.,2013,52:7819.
[27]Zheng J P,Liu Q L,Zhen M M,Jiang F,Shu C Y,Jin C,Yang Y J,Hisham A A,Wang C R.Multifunctional imaging probe based on gadofulleride nanoplatform.Nanoscale,2012,4:3669.
[28]Enzo T,Daniela D C,Alessandra V,Silvio A.Challenges for molecular magnetic resonance imaging.Chem.Rev.,2010,110:3019.
[29]Xuan T T,Wang S,Wang X J,Liu J Q,Chen J Y,Li H L,Pan L K,Sun Z.Single-step non-injection synthesis of highly luminescent water soluble Cu+doped Cd S quantum dots:application as bio-imaging agents.Chem.Commun.,2013,49:9045.
[30]Abdullah M M,Rahman M M,Bouzid H,Faisal M,Khan S B,Al-Sayari S A,Ismail A A.Sensitive and fast response ethanol chemical sensor based on as-grown Gd2O3nanostructures.J.Rare Earths,2015,33:214.