Facile Synthesis of Cadmium-Free Zn-In-S:Ag/ZnS Nanocrystals for Bio-Imaging.
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ABSTRACT:
SUBMITTER: Xuan TT
PROVIDER: S-EPMC4830992 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Cadmium-free I-III-VI nanocrystals (NCs) have recently attracted much research interests due to their excellent optical properties and low toxicity. In this work, with a simple heat-up synthetic system to prepare high quality Ag-In-S (AIS) NCs and their core/shell structures (AIS/ZnS NCs), we investigated the effect of different indium precursors (indium acetate and indium chloride) on NC optical properties. The measurements on photoluminescence spectra of AIS NCs show that the photoluminescence peak-wavelength of AIS NCs using indium acetate is in the range from 596 to 604 nm, and that of AIS NCs using indium chloride is from 641 to 660 nm. AIS and AIS/ZnS NCs using indium acetate present around 15% and 40% QYs, and both AIS and AIS/ZnS NCs using indium chloride present around 31% QYs. The photoluminescence decay study indicates that the lifetime parameters of AIS and AIS/ZnS using indium chloride are 2 ~ 4 times larger than those of AIS and AIS/ZnS NCs using indium acetate. Moreover, AIS NCs using indium chloride have a slower photobleaching dynamics than AIS NCs using indium acetate, and ZnS shell coating on both types of AIS NCs significantly enhances their photostability against UV exposure. We believe that the unique optical properties of AIS and AIS/ZnS NCs will open an avenue for these materials to be employed in broad electronic or biomedical applications.
| S-EPMC4730890 | biostudies-literature
Project description:This study advances the chemical research community toward the goal of replacing toxic cadmium-containing quantum dots (QDs) with environmentally benign InP QDs. The InP QD synthesis uniquely combines the previously reported use of InP magic-sized clusters (MSCs) as a single-source precursor for indium and phosphorus to form InP QDs, with zinc incorporation and subsequent ZnS shelling, to form InPZn/ZnS QDs with luminescence properties comparable to those of commonly used cadmium-containing luminescent QDs. The resulting InPZn/ZnS QDs have an emission quantum yield of about 50% across a broad range of emission peak wavelengths and emission peaks averaging 50 nm fwhm. The emission peak wavelength can be easily tuned by varying the Zn/In ratio in the reaction mixture. The strategy of using zinc stearate to tune the emission properties is advantageous as it does not lead to a loss of emission quantum yield or emission peak broadening. Although the initial optical properties of InP and InPZn/ZnS QDs are promising, thermal stability measurements of InPZn QDs show significant degradation in the absence of a shell compared to the CdSe QDs particularly at increased temperature in the presence of oxygen, which is indicative of thermal oxidation. There is no significant difference in the degradation rate of InP QDs made from molecular precursors and from MSCs. Additionally, the emission intensity and quantum yield of InPZn/ZnS QDs when purified and diluted in organic solvents under ambient conditions decrease significantly compared to those of CdSe/ZnS QDs. This indicates instability of the ZnS shell when prepared by common literature methods. This must be improved to realize high-quality, robust Cd-free QDs with the capability of replacing CdSe QDs in QD technologies.
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Project description:Here, we report efficient composition-tunable Cu-doped ZnInS/ZnS (core and core/shell) colloidal nanocrystals (CNCs) synthesized by using a colloidal non-injection method. The initial precursors for the synthesis were used in oleate form rather than in powder form, resulting in a nearly defect-free photoluminescence (PL) emission. The change in Zn/In ratio tunes the percentage incorporation of Cu in CNCs. These highly monodisperse Cu-doped ZnInS CNCs having variable Zn/In ratios possess peak emission wavelength tunable from 550 to 650 nm in the visible spectrum. The quantum yield (QY) of these synthesized Cd-free CNCs increases from 6.0 to 65.0% after coating with a ZnS shell. The CNCs possessing emission from a mixed contribution of deep trap and dopant states to only dominant dopant-related Stokes-shifted emission are realized by a careful control of stoichiometric ratio of different reactant precursors during synthesis. The origin of this shift in emission was understood by using steady state and time-resolved fluorescence (TRF) spectroscopy studies. As a proof-of-concept demonstration, these blue excitable Cu-doped ZnInS/ZnS CNCs have been integrated with commercial blue LEDs to generate white-light emission (WLE). The suitable combination of these highly efficient doped CNCs results led to a Commission Internationale de l'Enclairage (CIE) color coordinates of (0.33, 0.31) at a color coordinate temperature (CCT) of 3694 K, with a luminous efficacy of optical radiation (LER) of 170 lm/Wopt and a color rendering index (CRI) of 88.
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Project description:A new indium precursor, namely, indium(II) chloride, was tested as a precursor in the synthesis of ternary Ag-In-S and quaternary Ag-In-Zn-S nanocrystals. This new precursor, being in fact a dimer of Cl2In-InCl2 chemical structure, is significantly more reactive than InCl3, typically used in the preparation of these types of nanocrystals. This was evidenced by carrying out comparative syntheses under the same reaction conditions using these two indium precursors in combination with the same silver (AgNO3) and zinc (zinc stearate) precursors. In particular, the use of indium(II) chloride in combination with low concentrations of the zinc precursor yielded spherical-shaped (D = 3.7-6.2 nm) Ag-In-Zn-S nanocrystals, whereas for higher concentrations of this precursor, rodlike nanoparticles (L = 9-10 nm) were obtained. In all cases, the resulting nanocrystals were enriched in indium (In/Ag = 1.5-10.3). Enhanced indium precursor conversion and formation of anisotropic, longitudinal nanoparticles were closely related to the presence of thiocarboxylic acid type of ligands in the reaction mixture. These ligands were generated in situ and subsequently bound to surfacial In(III) cations in the growing nanocrystals. The use of the new precursor of enhanced reactivity facilitated precise tuning of the photoluminescence color of the resulting nanocrystals in the spectral range from ca. 730 to 530 nm with photoluminescence quantum yield (PLQY) varying from 20 to 40%. The fabricated Ag-In-S and Ag-In-Zn-S nanocrystals exhibited the longest, reported to date, photoluminescence lifetimes of ∼9.4 and ∼1.4 μs, respectively. It was also demonstrated for the first time that ternary (Ag-In-S) and quaternary (Ag-In-Zn-S) nanocrystals could be applied as efficient photocatalysts, active under visible light (green) illumination, in the reaction of aldehydes reduction to alcohols.
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Project description:In this work, Mn doped AIZS/ZnS (Mn:AIZS/ZnS) nanocrystals (NCs) have been synthesized in an approach using heat-up and drop-wise addition of precursors. On the basis of the characterization of these doped NCs on their optical properties and materials, it is found that: (1) as more Mn atoms are doped into NCs, the doped NCs present photoluminescence (PL) red-shift and quantum yield quenching; (2) the doped NCs possess a short PL lifetime in tens of microseconds and a long PL lifetime in hundreds of microseconds, and the short lived PL is more dominant than the long lived one; and (3) the doped NCs present a reversible PL thermal quenching in a range from room temperature to 170°C. Possible PL mechanisms of these NCs were discussed by analyzing their time-resolved PL spectra and thermal stability.
| S-EPMC5724564 | biostudies-literature
Project description:Here we present a facile one-pot method to prepare high-quality CdTe nanocrystals in aqueous phase. In contrast to the use of oxygen-sensitive NaHTe or H(2)Te as Te source in the current synthetic methods, we employ more stable sodium tellurite as the Te source for preparing highly luminescent CdTe nanocrystals in aqueous solution. By selecting mercaptosuccinic acid (MSA) as capping agent and providing the borate-citrate acid buffering solution, CdTe nanocrystals with high quantum yield (QY >70% at pH range 5.0-8.0) can be conveniently prepared by this method. The influence of parameters such as the pH value of the precursor solution and the molar ratio of Cd(2+) to Na(2)TeO(3) on the QY of CdTe nanocrystals was systematically investigated in our experiments. Under optimal conditions, the QY of CdTe nanocrystals is even high up to 83%. The biological application of luminescent MSA-CdTe to HEK 293 cell imaging was also illustrated.
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Project description:We have investigated the chemical state of In(Zn)P/ZnS core/shell nanocrystals (NCs) for color conversion applications using hard X-ray absorption spectroscopy (XAS) and photoluminescence excitation (PLE). Analyses of the edge energies as well as the X-ray absorption fine structure (XAFS) reveal that the Zn(2+) ions from ZnS remain in the shell while the S(2-) ions penetrate into the core at an early stage of the ZnS deposition. It is further demonstrated that for short growth times, the ZnS shell coverage on the core was incomplete, whereas the coverage improved gradually as the shell deposition time increased. Together with evidence from PLE spectra, where there is a strong indication of the presence of P vacancies, this suggests that the core-shell interface in the In(Zn)P/ZnS NCs are subject to substantial atomic exchanges and detailed models for the shell structure beyond simple layer coverage are needed. This substantial atomic exchange is very likely to be the reason for the improved photoluminescence behavior of the core-shell particles compare to In(Zn)P-only NCs as S can passivate the NCs surfaces.
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Project description:Construction of self-illuminating semiconducting nanocrystals, also called quantum dots (QDs), has attracted much attention recently due to their potential as highly sensitive optical probes for biological imaging applications. Here we prepared a self-illuminating QD system by doping positron-emitting radionuclide (64)Cu into CdSe/ZnS core/shell QDs via a cation-exchange reaction. The (64)Cu-doped CdSe/ZnS QDs exhibit efficient Cerenkov resonance energy transfer (CRET). The signal of (64)Cu can accurately reflect the biodistribution of the QDs during circulation with no dissociation of (64)Cu from the nanoparticles. We also explored this system for in vivo tumor imaging. This nanoprobe showed high tumor-targeting ability in a U87MG glioblastoma xenograft model (12.7% ID/g at 17 h time point) and feasibility for in vivo luminescence imaging of tumor in the absence of excitation light. The availability of these self-illuminating integrated QDs provides an accurate and convenient tool for in vivo tumor imaging and detection.
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Project description:Multi-drug resistant pathogens are a rising danger for the future of mankind. Iodine (I2) is a centuries-old microbicide, but leads to skin discoloration, irritation, and uncontrolled iodine release. Plants rich in phytochemicals have a long history in basic health care. Aloe Vera Barbadensis Miller (AV) and Salvia officinalis L. (Sage) are effectively utilized against different ailments. Previously, we investigated the antimicrobial activities of smart triiodides and iodinated AV hybrids. In this work, we combined iodine with Sage extracts and pure AV gel with polyvinylpyrrolidone (PVP) as an encapsulating and stabilizing agent. Fourier transform infrared spectroscopy (FT-IR), Ultraviolet-visible spectroscopy (UV-Vis), Surface-Enhanced Raman Spectroscopy (SERS), microstructural analysis by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-Ray-Diffraction (XRD) analysis verified the composition of AV-PVP-Sage-I2. Antimicrobial properties were investigated by disc diffusion method against 10 reference microbial strains in comparison to gentamicin and nystatin. We impregnated surgical sutures with our biohybrid and tested their inhibitory effects. AV-PVP-Sage-I2 showed excellent to intermediate antimicrobial activity in discs and sutures. The iodine within the polymeric biomaterial AV-PVP-Sage-I2 and the synergistic action of the two plant extracts enhanced the microbial inhibition. Our compound has potential for use as an antifungal agent, disinfectant and coating material on sutures to prevent surgical site infections.
| S-EPMC8230494 | biostudies-literature