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Metal halide perovskites with excellent optical and electronic properties have become a trending material in the current research. However, their limited stability under ambient conditions degrades quality and threatens their potential commercialization as optoelectronic devices. Various approaches are adopted to improve the stability of perovskite nanocrystals (PeNC) while maintaining their advantageous optical properties, particularly strong luminescence. Among different possible improvement strategies, encapsulation of PeNCs within the amorphous glass matrices of inorganic oxides has drawn widespread attention because it ensures high resistance against chemical corrosion and high temperature, thus enhancing their chemical, thermal, and mechanical stability with improved light-emission characteristics. In this article, two types of materials, namely all-inorganic metal halide PeNCs and amorphous oxide glasses are briefly introduced, and then the methods are reviewed to fabricate and improve the quality of PeNC@glass composites. These methods are classified into three universal categories: compositional modification, structural modification, and dual encapsulation. In the final part of this review paper, examples of applications of PeNCs@glass composites in light-emitting devices and displays, data storage and anti-counterfeiting, lasing, photodetectors and X-ray detectors, photocatalysis, optical filters, solar concentrators, and batteries are provided.
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Reaching emissive nanomaterials at short wavelengths with a high quantum efficiency (QE) is an attractive task for researchers. This is more demanding in carbon dots (CDs) with diverse applications that usually emit photons at wavelengths around 450-620 nm. In this study, deep blue-emissive doped-CDs (d-CDs) with high photoluminescence (PL) QE up to 62% and excitation-independent properties were prepared via a short-time microwave irradiation method. The prepared CDs showed simultaneous amorphous and crystalline features, with average sizes of 4.75 nm and bright emission color located at 422 nm. It was found that the presence of sulfur-related dopant levels plays a key role in emission properties in such a way that the PL signal drops significantly in the absence of N-acetyl-l-cysteine (NAC) as a dopant source. On the other hand, the trisodium citrate dihydrate (TSC) was selected as a carbon source to form the main carbon skeleton without it no emission was recorded. Monoexponential-fitted recombination trend with an average lifetime of about 10 ns also confirmed excellent PL emission properties with uniform energy levels and minimized defect-contributing recombinations. The practical use of the as-prepared N, S-doped CDs was assessed in fingerprint detection indicating a bright and clear scheme for both core and termination regions of the fingerprint. Simplicity, cost-effectiveness, high-product yield, low toxicity, along with high/stable PL quantum efficiency in deep-blue wavelengths, and demonstrated ability for fingerprint purposes, support the prospective application of these dual doped-CDs for sensing and bioimaging applications.
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In this paper, an aqueous-based approach is introduced for facile, fast, and green synthesis of gradient-alloyed Fe-doped ZnSe(S)@ZnSe(S) core:shell quantum dots (QDs) with intense and stable emission. Co-utilization of co-nucleation and growth doping strategies, along with systematic optimization of emission intensity, provide a well-controllable/general method to achieve internally doped QDs (d-dots) with intense emission. Results indicate that the alloyed ZnSe(S)@ZnSe(S) core:shell QDs have a gradient structure that consists of a Se-rich core and a S-rich shell. This gradient structure cannot only passivate the core d-dots by means of the wider band gap S-rich shell, but also minimizes the lattice mismatch between alloyed core-shell structures. Using this novel strategy and utilizing the wider band gap S-rich shell can obviously increase the cyan emission intensity and also drastically improve the emission stability against chemical and optical corrosion. Furthermore, the cytotoxicity experiments indicate that the obtained d-dots are nontoxic nanomaterials, and thus they can be considered as a promising alternative to conventional Cd-based QDs for fluorescent probes in biological fields. Finally, it is demonstrated that the present low-toxicity and gradient-alloyed core:shell d-dots can be used as sensitive chemical detectors for Pb2+ ions with excellent selectivity, small detection limit, and rapid response time.
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We report here on a one-pot, mild and low cost aqueous-based synthetic route for the preparation of colloidally stable and highly luminescent dual-doped Ag,Ni:ZnCdS/ZnS core/shell quantum dots (QDs). The pure dopant emission of the Ni-doped core/shell QDs was found to be highly affected by the presence of a second dopant ion (Ag+). Results showed that the PL emission intensity increases while its peak position experiences an obvious blue shift with an increase in the content of Ag+ ions. Regarding the optical observations, we provide a simple scheme for absorption-recombination processes of the carriers through impurity centers. To obtain optimum conditions with a better emission characteristic, we also study the effect of different reaction parameters, such as refluxing temperature, the pH of the core and shell solution, molar ratio of the dopant ions (Ni:(Zn+Cd) and Ag:(Zn+Cd)), and concentration of the core and shell precursors. Nonetheless, the most effective parameter is the presence of the ZnS shell in a suitable amount to eliminate surface trap states and enhance their emission intensity. It can also improve the bio-compatibility of the prepared QDs by restricting the Cd2+ toxic ions inside the core of the QDs. The present suggested route also revealed the remarkable optical and chemical stability of the colloidal QDs which establishes them as a decent kind of nano-scale structure for light emitting applications, especially in biological technologies. The suggested process also has the potential to be scaled-up while maintaining the emission characteristics and structural quality necessary for industrial applications in optoelectronic devices.
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In this paper, we describe a facile method for preparation of ZnSe quantum dots (QDs) using an inexpensive and biocompatible source of acetyl cysteine in aqueous media. The structural properties of the ZnSe QDs have been characterized using XRD, FT-IR, and TEM techniques. The optical properties of the as-prepared QDs were found to be size-dependent, due to the strong confinement regime at relatively low refluxing time. Effect of solution pH and refluxing temperature on absorption and emission characteristics of the ZnSe QDs was studied. The empirical effective mass approximation also reveals that, both solution pH and refluxing temperature parameters would effect on ZnSe QDs growth, and increase their size. However, the influence of the solution pH was found to be more prominent. Water-solubility, high emission intensity and sub-10 nm nanocrystals size are the most essential features that suggest our synthesized aqueous-based ZnSe QDs (with a very cost-effective and biocompatible capping agent) can be utilized for biological intentions.
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While Cd-based luminescent nanocrystals (NCs) are the most mature NCs for fabricating efficient red light-emitting diodes (LEDs), their toxicity related limitation is inevitable, making it necessary to find a promising alternative. From this point of view, multishell-coated, red-emissive InP-based NCs are excellent luminescent nanomaterials for use as an emissive layer in electroluminescent (EL) devices. However, due to the presence of oxidation states, they suffer from a wide emission spectrum, which limits their performance. This study uses tris(dimethylamino)phosphine (3DMA-P) as a low-cost aminophosphine precursor and a double HF treatment to suggest an upscaled, cost-effective, and one-pot hot-injection synthesis of purely red-emissive InP-based NCs. The InP core structures were coated with thick layers of ZnSe and ZnS shells to prevent charge delocalization and to create a narrow size distribution. The purified NCs showed an intense emission signal as narrow as 43 nm across the entire red wavelength range (626-670 nm) with an emission quantum efficiency of 74% at 632 nm. The purified samples also showed an emission quantum efficiency of 60% for far-red wavelengths of 670 nm with a narrow full width of 50 nm. The samples showed a relatively long average emission lifetime of 50-70 ns with a biexponential decay profile. To demonstrate the practical ability of the prepared NCs in optoelectronics, we fabricated a red-emissive InP-based LEDs. The best-performing device showed an external quantum efficiency (EQE) of 1.16%, a luminance of 1039 cd m-2, and a current efficiency of 0.88 cd A-1.
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Tremendous demands for simultaneous imaging of biological entities, along with the drawback of photobleaching in fluorescent dyes, have encouraged scientists to apply novel and non-toxic colloidal quantum dots (QDs) in biomedical researches. Herein, a novel aqueous-phase approach for the preparation of multicomponent In-based QDs is reported. Absorption and photoluminescence emission spectra of the as-prepared QDs were tuned by alteration of QDs' composition as Zn-Ag-In-S/ZnS, Ag-In-S/ZnS and Cu-Ag-In-S/ZnS core/shell QDs. In order to reach reproducibly intense and tunable light-emissive colloidal QDs with green, amber, and red color, various optimization steps were carefully performed. The structural characterizations such as EDX, ICP-AES, XRD, TEM and FT-IR measurements were also carried out to demonstrate the success of the present method to prepare extremely quantum-confined QDs capped with functional groups. Then, to ensure their promising biomedical applications, the generated intracellular reactive oxygen species (ROS) by QDs were quantitatively and qualitatively measured in dark conditions and under 405 nm laser irradiation. Our results verified an enhancement in the generation of reactive oxygen species (ROS) and cytotoxic effects in the presence of laser irradiation while their muted toxic effects in dark conditions confirmed biocompatible properties of un-excited In-based QDs. Moreover, bioimaging analysis revealed strong merits of the suggested synthetic route to achieve ideal fluorescent QDs as bright/multi-color optical nano-probes in imaging and transporting pumps in the cell membrane. This further emphasized the potential ability of the present AgInS-based/ZnS QDs in obtaining required results as theranostic agents for simultaneous treatment and imaging of cancer. The harmonized advantages in simplicity and effectiveness of synthesis procedure, excellent structural/optical properties enriched with confirmed biomedical merits in high contrast imaging and potential treatment highlight the present work.
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Materiais Biocompatíveis/química , Coloides/química , Luminescência , Nanopartículas/química , Imagem Óptica , Pontos Quânticos/química , Prata/química , Sulfetos/química , Compostos de Zinco/química , Animais , Morte Celular , Linhagem Celular Tumoral , Sobrevivência Celular , Humanos , Índio/química , Fenômenos Ópticos , Espécies Reativas de Oxigênio/metabolismo , Espectrometria por Raios X , Espectrofotometria Ultravioleta , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
Developing easy-to-use and miniaturized sensors for in-field monitoring of targets which is related to human health is necessary. Ractopamine (RAC) is a feed additive with serious side effects that is forbidden in many countries. This study reports the fabrication of an impedimetric aptasensor for ultrasensitive and selective detection of the RAC in human biological fluids. Accordingly, an efficient nanocomposites was synthesized by a beneficial combination of graphene quantum dots (GQDs), quantum dots (QDs) and silver nanoparticles (AgNPs) for modifying a glassy carbon electrode (GCE). This nanocomposite is promising to present a synergistic effect in the increase of the active surface area of the modified electrode to more load the biocapture of the target. Next, the RAC-binding aptamer (Apt) was attached to the AgNPs/QDs@GQDs/GCE surface and a sensitive layer for the RAC detection was embedded. A RAC-Apt complex was formed upon adding the RAC and the changes of the electrochemical behavior were studied by some electrochemical techniques such as electrochemical impedance spectroscopy (EIS). Under optimal conditions, the charge transfer resistance (Rct) value was increased linearly with increasing of the RAC concentrations in the range of 1 fM to 901.4 nM. Limit of detection (LOD) was calculated to be 330 aM which is superior by other reported electrochemical methods in the RAC sensing. The applicability of the aptasensor was tested in human urine and blood serum as the real samples and satisfactory results of specificity were achieved. It seems that the proposed strategy not only provides a new ultrasensitive strategy for RAC detection but also expands the application of the sensing interface to develop other aptasensors by changing the Apt sequence.
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Análise Química do Sangue/métodos , Impedância Elétrica , Nanopartículas Metálicas/química , Fenetilaminas/análise , Pontos Quânticos , Prata/química , Urinálise/métodos , Aptâmeros de Nucleotídeos/química , Técnicas Biossensoriais , Cobre/química , Espectroscopia Dielétrica , Técnicas Eletroquímicas , Eletrodos , Grafite/química , Humanos , Índio/química , Limite de Detecção , Microscopia Eletrônica de Varredura , Nanocompostos , Sulfetos/química , Enxofre/química , Compostos de Zinco/químicaRESUMO
This paper reports an aptamer-based green approach for the electrochemical evaluation of tyrosinamide (Tyr-NH2). In this regard, at the first step, an aqueous synthetic strategy for preparing N-acetyl-l-cysteine (NAC)-capped Ag-In-S (AIS) quantum dots (QDs) with bright yellow/orange emission was developed. The conjugation of AIS QDs to NAC-biomolecules provides opportunities for using them as luminescent contrast agents for living cell tracking and labeling or sensing studies. In the next step, the design stage of the aptasensor, the glassy carbon electrode (GCE) was modified with the AIS QDs and then the Tyr-NH2 special aptamer, which has an amine group at its end, interacts with silver and indium ions at the surface of the AIS QDs and through the formation of covalent bonding of AgN and InN, attaches to the GCE surface modified with the AIS QDs. In this approach, for the first time, NAC-capped AIS QDs have been used to modify the electrode surface in the aptamer-based electrochemical sensor. The response changes of the [Fe(CN)6]4-/3- as redox probe, during the modification of GCE surface, the fabrication and assessment of proposed aptasensing, using the cyclic voltammetry, differential pulse voltammetry and electrochemical impedance spectroscopy were recorded. The designed aptasensor for the Tyr-NH2 evaluation showed good linearity from 0.01 to 2.81â¯nM and 2.81-10.81â¯nM, and low detection limit of 3.34â¯pM. The obtained results of the stability, reproducibility and selectivity investigations implying that the reported aptasensor as the first aptamer-based electrochemical assay for Tyr-NH2, can be reliable for the determination of Tyr-NH2 in serum samples.
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Acetilcisteína/química , Aptâmeros de Nucleotídeos/química , Técnicas Biossensoriais/métodos , Carbono/química , Técnicas Eletroquímicas/métodos , Vidro/química , Pontos Quânticos/química , Tirosina/análogos & derivados , Espectroscopia Dielétrica , Eletrodos , Humanos , Índio/química , Pontos Quânticos/ultraestrutura , Reprodutibilidade dos Testes , Prata/química , Enxofre/química , Fatores de Tempo , Tirosina/sangueRESUMO
Developing novel aqueous-soluble quantum dots (QDs) can create new opportunities for better biological utilization. In the present work, novel, high emissive and biocompatible N-acetyl-L-cysteine-capped Ag-In-S QDs (as an I-III-VI structure) were prepared in a facile and straightforward way. The dominance of the strong confinement regime was observed due to the very small size of nanoparticles, which was smaller than their excitonic Bohr radius. To prepare reproducible Ag-In-S QDs, their emission characteristics were improved by optimizing the experimental variables which resulted in the enhancement of their emission quantum yield to near 32% at 615 nm. The absorption and emission results support the contribution of band edge-independent radiative recombination pathways for charge carriers in the prepared Ag-In-S QDs. The possible mechanisms for such donor-acceptor recombination were also discussed. To explore the antibacterial ability of the Ag-In-S QDs, their bactericidal activity was evaluated against different types of Gram-positive (Staphylococcus aureus and Bacillus subtilis) and Gram-negative (Escherichia coli and Salmonella enterica) bacteria. Precise measurements confirmed a remarkable bactericidal activity of Ag-In-S QDs against the different pathogenic bacteria even at low concentration of QDs (15 µg/mL). It was found that the QDs are more effective on Gram-negative bacteria. While the preparation method was simple and cost-effective, the as-synthesized QDs were highly emissive and stable with significant antibacterial activity. This demonstrates the great potential of present Ag-In-S QDs for future hygienic and medical purposes.
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Antibacterianos/administração & dosagem , Bactérias/efeitos dos fármacos , Pontos Quânticos/administração & dosagem , Prata/química , Água/química , Acetilcisteína/química , Antibacterianos/síntese química , Antibacterianos/química , Bacillus subtilis/efeitos dos fármacos , Bactérias/classificação , Escherichia coli/efeitos dos fármacos , Testes de Sensibilidade Microbiana/métodos , Microscopia Eletrônica de Transmissão , Pontos Quânticos/química , Pontos Quânticos/ultraestrutura , Salmonella enterica/efeitos dos fármacos , Solubilidade , Especificidade da Espécie , Análise Espectral , Staphylococcus aureus/efeitos dos fármacos , Difração de Raios XRESUMO
The effective insertion of intentional impurities in direct aqueous preparation of doped QDs still needs a chemical route with well-designed strategy. The present work reports a facile, one-pot, and aqueous-based method for green synthesis of Fe-doped ZnSe(S)/ZnSe(S) core/shell QDs with improved emission intensity. In the proposed strategy, by using a sulfur rich ZnSe(S) shell, we can provide a wider band gap shell with low structural defects in the interface between core and shell. Utilization of combined co-nucleation and growth doping strategies along with increasing the shell refluxing time all are the chemo-physical tactics which led to high intensity dopant-related emission. The antibacterial activity of the as-prepared doped core/shell QDs was investigated using agar disk diffusion method. The results show, these QDs have a significant antibacterial activity against different pathogenic bacteria comparing with the conventional antibiotics. The facility of suggested aqueous route for reaching a dopant emission, the bio-compatibility and considerable antibacterial characteristics of present QDs, nominate them as good candidates in further biological applications.