Polyol-synthesized Zn0.9Mn0.1S nanoparticles as potential luminescent and magnetic bimodal imaging probes: synthesis, characterization, and toxicity study

Gaceur, Mériem; Giraud, Marion; Hémadi, Miryana; Nowak, Sophie; Menguy, Nicolas; Quisefit, J.P.; David, K. A. V.; Jahanbin, Tania; Benderbous, Soraya; Boissière, Michel; Ammar, Souad

doi:10.1007/s11051-012-0932-3

Cited by 36 publications

(26 citation statements)

References 62 publications

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“…At low Mn content, we observe a strong increase in relaxivity with increasing Mn content, from about 0.01 mM (Mn) À1 s À1 for QDs containing 1% Mn to 0.5 mM (Mn) À1 s À1 for QDs containing 20% Mn at 7 T. This increase suggests that several Mn participate cooperatively in the relaxation dynamics of water protons diffusing near the surface of the nanoparticle: when the Mn concentration is higher, each Mn participates more efficiently to the water relaxivity. 43)) and slightly lower than previously reported Mn-doped Si QDs, 44 Zn 0.9 Mn 0.1 S nanocrystals 45 and CdSe/Zn 0.94 Mn 0.06 S QDs. 40 It is unclear whether our continuous growth method actually leads to epitaxial growth of small MnS nanoclusters or if the Mn ions are dispersed homogeneously in the shell.…”

Section: Relaxivity Measurementscontrasting

confidence: 51%

Multimodal Mn-doped I–III–VI quantum dots for near infrared fluorescence and magnetic resonance imaging: from synthesis to in vivo application

et al. 2014

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The development of sensitive multimodal contrast agents is a key issue to provide better global, multi-scale images for diagnostic or therapeutic purposes. Here we present the synthesis of Zn-Cu-In-(S, Se)/Zn(1-x)Mn(x)S core-shell quantum dots (QDs) that can be used as markers for both near-infrared fluorescence imaging and magnetic resonance imaging (MRI). We first present the synthesis of Zn-Cu-In-(S, Se) cores coated with a thick ZnS shell doped with various proportions of Mn. Their emission wavelengths can be tuned over the NIR optical window suitable for deep tissue imaging. The incorporation of manganese ions (up to a few thousand ions per QD) confers them a paramagnetic character, as demonstrated by structural analysis and electron paramagnetic resonance spectroscopy. These QDs maintain their optical properties after transfer to water using ligand exchange. They exhibit T1-relaxivities up to 1400 mM(-1) [QD] s(-1) at 7 T and 300 K. We finally show that these QDs are suitable multimodal in vivo probes and demonstrate MRI and NIR fluorescence detection of regional lymph nodes in mice.

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Section: Relaxivity Measurementscontrasting

confidence: 51%

Multimodal Mn-doped I–III–VI quantum dots for near infrared fluorescence and magnetic resonance imaging: from synthesis to in vivo application

et al. 2014

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“…MnZnS nanoparticles were synthesized via polyol method using the protocol described elsewhere (Gaceur et al 2012) and adjusting the nominal zinc and manganese precursor concentrations to vary (0.1, 0.2 and 0.3). In brief, the certain amounts of zinc acetate, manganese acetate, thiourea and trioctylphosphine oxide were mixed in the 80 mL of diethylene glycol solution.…”

Section: Methodsmentioning

confidence: 99%

High potential of Mn-doped ZnS nanoparticles with different dopant concentrations as novel MRI contrast agents: synthesis and in vitro relaxivity studies

et al. 2015

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Over several decades, metal-doped quantum dots (QDs) with core-shell structure have been studied as dual probes: fluorescence and magnetic resonance imaging (MRI) probes (Dixit et al., Mater Lett 63(30):2669-2671). However, metal-doped nanoparticles, in which the majority of metal ions are close to the surface, can affect their efficacy as MRI contrast agents (CAs). In this context, herein the high potential of synthesized Mn-doped ZnS QDs via polyol method as imaging probe is demonstrated. The mean diameters of QDs were measured via transmission electron microscopy (TEM) and X-ray diffraction (XRD). Optical and magnetic properties of MnZnS nanoparticles were characterized using fluorescence spectroscopy and super quanducting interference devices magnetometer and electron paramagnetic resonance system, respectively. T1-and T2-weighted images of nanoparticles in aqueous solution were acquired from spin-echo sequences at 3 T. From TEM images and XRD spectra of the prepared nanoparticles, it is observed that the average diameter of particles does not significantly change with Mn dopant content (*1.6-1.9 nm). All three samples exhibit broad blue emission under UV light excitation. According to the MRI studies, MnZnS nanoparticles generate strong T1 contrast enhancement (bright T1-weighted images) at the low concentration (\0.1 mM). The MnZnS nanoparticles exhibit the high longitudinal (r 1 ) relaxivity that increases from 20.34 to 75.5 mM -1 s -1 with the Mn dopant contents varying between 10 and 30 %. Strong signal intensity on T1weighted images and high r 1 with r 2 r 1 % 1 can demonstrate the high potential of the synthesized Mn:ZnS nanoparticles, which can serve as an effective T1 CA.Scheme 1 Schematic of Mn:ZnS capped with mercaptoacetic acid and enlarge carboxylic acid interaction with water molecules J Nanopart Res (2015) 17:258

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“…Luminescent, paramagnetic colloidal quantum dots, QDs (e.g., Mn-doped Si, ZnS, CdS/ZnS QDs) have also been previously studied. [7][8][9] However, these nanostructures require phase transfer to address water solubility and/or the visible photoluminescence (PL) emission limits their application in in vivo imaging due to strong photon absorption by biological tissues. Thus despite extensive research in this fi eld, paramagnetic nanoparticles with fl uorescence in the near-infrared (NIR) spectral region of the biological optical window are still not available.…”

Section: Doi: 101002/ppsc201300184mentioning

confidence: 99%

Paramagnetic, Near‐Infrared Fluorescent Mn‐Doped PbS Colloidal Nanocrystals

Turyanska

Moro

Knott

et al. 2013

Part & Part Syst Charact

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The nanoscale design of nanocrystals by the controlled incorporation of dopant impurities is a research fi eld of fundamental interest with great potential for numerous disruptive technologies. [1][2][3] In particular, 3 d transition metal ions (Mn, Co, etc.) with their d -shell electronic confi gurations can imprint a nanocrystal with magnetic properties of relevance for innovative applications ranging from bio-imaging [ 4,5 ] to spintronics. [ 1,5 ] For example, colloidal nanocrystals doped with transition metals could provide versatile contrast agents for multimodal medical imaging, i.e., for contrast-enhanced magnetic resonance imaging (MRI) and confocal microscopy. [ 4 ] To date, a variety of nanoparticles (e.g., Fe 3 O 4 , FePt, MnFe 2 O 4 , and MnO) have been used for enhancedcontrast MRI, [ 5,6 ] but these require functionalization with fl uorescent organic dyes for optical imaging and their solubility in physiological solvents demands modifi cation of the nanocrystal surface. Luminescent, paramagnetic colloidal quantum dots, QDs (e.g., Mn-doped Si, ZnS, CdS/ZnS QDs) have also been previously studied. [7][8][9] However, these nanostructures require phase transfer to address water solubility and/or the visible photoluminescence (PL) emission limits their application in in vivo imaging due to strong photon absorption by biological tissues. Thus despite extensive research in this fi eld, paramagnetic nanoparticles with fl uorescence in the near-infrared (NIR) spectral region of the biological optical window are still not available.In this work, we report paramagnetic, NIR fl uorescent Mndoped PbS colloidal nanocrystals in an aqueous solution. We demonstrate the successful incorporation of Mn atoms in the nanocrystals, which contain up to 8% Mn. The nanocrystals are optically active at room temperature in the technologically important biological window between 1.2 μ m and 0.8 μ m; also, the Mn atoms imprint the nanoparticles with paramagnetic properties. Preliminary cytoxicity studies show that the exposure of human cell lines to the nanoparticles at concentrations up to 0.2 mg mL −1 does not induce any adverse effect, thus providing guidelines on safe doses for further toxicology studies and future applications in medical imaging.Our Mn-doped PbS nanocrystals in an aqueous solution differ from previously reported nanostructures based on PbS nanowires [ 10,11 ] and PbS nanocrystals in glass matrices [ 12,13 ] or in organic solvents. [ 14 ] To synthesize the Mn-doped PbS nanoparticles, we prepared a Pb 2+ precursor solution containing 2.5 × 10 −4 mol of lead acetate Pb(CH 3 COO) 2 , 1.5 × 10 −3 mol of thioglycerol (TGL) and 5 × 10 −4 mol of dithioglycerol (DTG) in 15 mL of deionized water, where the thiols act as capping agents. [ 15,16 ] The pH of the solution was adjusted to a value of 11.0 by addition of triethylamine. While maintaining the pH of the solution, manganese acetate Mn(CH 3 COO) 2 salt was added with Mn concentration, x , up to 18%. To facilitate the incorporation of the Mn atoms during the nu...

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Polyol-synthesized Zn0.9Mn0.1S nanoparticles as potential luminescent and magnetic bimodal imaging probes: synthesis, characterization, and toxicity study

Cited by 36 publications

References 62 publications

Multimodal Mn-doped I–III–VI quantum dots for near infrared fluorescence and magnetic resonance imaging: from synthesis to in vivo application

Multimodal Mn-doped I–III–VI quantum dots for near infrared fluorescence and magnetic resonance imaging: from synthesis to in vivo application

High potential of Mn-doped ZnS nanoparticles with different dopant concentrations as novel MRI contrast agents: synthesis and in vitro relaxivity studies

Paramagnetic, Near‐Infrared Fluorescent Mn‐Doped PbS Colloidal Nanocrystals

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