Luminescent Nanomaterials Research Articles

KHẢO SÁT TÍNH CHẤT CỦA VẬT LIỆU NANO PHÁT QUANG CHUYỂN ĐỔI NGƯỢC CHỨA Tm(III)/Yb(III) TRÊN NỀN NaYF4

This study aimed to investigate the properties of up-conversion luminescent nanomaterials containing Tm(III) and Yb(III) based on NaYF4 host. The materials were synthesized using the hydrothermal method. The morphology, structure and luminescent properties of the material were analyzed using field emission scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and photoluminescence spectroscopy. The results indicate that the synthesized nanomaterials were in the form of particles with a diameter ranging from 100-200 nm, had a hexagonal β-NaYF4 phase structure, and emitted blue light at a wavelength of 980 nm. These luminescent properties of the material indicate their potential application in biomedical fields.

Live synthesis of selective carbon dots as fluorescent probes for cobalt determination in water with an automatic microanalyzer

A new strategy integrating the straight synthesis of carbon dots (CDs) and their direct use for the determination of heavy metals by means of fluorescence quenching is presented. The proposal consists of a modular analyzer, which includes a low temperature co-fired ceramics (LTCC) microreactor for the synthesis of CDs and a cyclic olefin copolymer (COC) microfluidic platform, which automatically performs a reverse flow injection analysis (rFIA) protocol for the determination of heavy metal ions in water by CD fluorescence quenching. As a proof of concept, nitrogen-doped CDs were synthesized from acrylic acid and ethylenediamine (ED) with quantum yields (QYs) of up to 44%, which are selective to cobalt. With the described system, we synthesized homogeneous CDs without the need for further purification and with the minimum consumption of reagents, and optimized fluorescence measurements can be performed with freshly obtained luminescent nanomaterials that have not undergone decomposition processes. They have an average hydrodynamic diameter of 4.2 ± 0.9 nm and maximum excitation and emission wavelengths at 358 nm and 452 nm, respectively. The system allows the automatic dilution and buffering of the synthesized CDs and the sample prior to the determination of cobalt. The concentration of cobalt was determined with good sensitivity and a limit of detection of 7 μg·L−1 with a linear range of 0.02–1 mg·L−1 of Co2+. Spiked tap water and river water samples were analyzed, obtaining recovery from 98 to 104%. This demonstrates the potential of the equipment as an efficient on-site control system for heavy metal monitoring in water.Graphical abstract

Green, facial zinc doped hydrothermal synthesis of cinnamon derived fluorescent carbon dots (Zn-Cn-CDs) for highly selective and sensitive Cr6+ and Mn7+ metal ion sensing application

Carbon dots have demonstrated a great potential as luminescent nanoparticles in energy, drug delivery, sensors, and various biomedical applications as well as environmental pollutants and water analysis. Although, such nanoparticles appear to exhibit low toxicity compared to other semiconductor and metal based luminescent nanomaterials. Today, we know that toxicity of carbon dots (CDs) strongly depends on the protocol of fabrication. The various dopants or heteroatoms have been used to enhance the optical and physicochemical properties. In this work, zinc doped aqueous fluorescent Zn-Cn-CDs have been synthesized from cinnamon by hydrothermal synthesis method. The synthesized Zn-Cn-CDs were confirmed for their physicochemical properties by using various characterization techniques viz. UV–Vis. and spectrofluorometer for optical properties, Fourier transform infrared spectroscopy (FTIR) and XRD, as well as TEM and XPS, was done for morphological and chemical analysis. The successfully synthesized Zn-Cn-CDs showed outstanding optical performance for metal ion sensing applications. The developed heteroatom doped Zn-Cn-CDs as a fluorescent probe exhibited higher selectivity and sensitivity for Cr6+ and Mn7+ metal ions. The obtained results showed a better linear range with excellent limit of detection (LOD) 3.97 µg/mL and 2.05 µg/mL for Cr6+ and Mn7+ metal ions respectively. The low cost, simple and highly fluorescent probe can be effectively applicable for development of environmental pollutants sensing purposes.

Bright and Stable Perovskite Nanocrystals Lighted Up Remotely by Means of Wireless Power Transfer

AbstractHalide perovskite nanocrystals (NCs) are an emerging family of low‐cost and high‐efficiency luminescent nanomaterials. They offer a broad gamut of emitted light colors owing to the broad bandgap tunability of the perovskite via anion variation. Previously, to lighten up perovskite NCs, they were placed between two electrodes to inject charge carriers or were integrated with commercial blue light‐emitting diodes powered by electric contacts. However, the opportunities for remote lighting of perovskite NCs have not been explored yet. In this work, the principles of wireless power transfer of electromagnetic energy are applied to light up perovskite NCs encapsulated into a polymer matrix. The photoluminescence and absorption spectra of the CsPbBr3 NCs in a polymer matrix on incident laser power density are experimentally studied. As a proof of concept, chess pieces are created consisting of the perovskite NCs and charge from a chessboard with an integrated metasurface‐based resonator that provides quasi‐homogeneous power distribution. The efficient lighting of the chess pieces with encapsulated NCs is demonstrated over the whole area of the chessboard at various heights up to ≈10 cm. The results of the study open the door for potential applications of perovskite NCs with remote lighting capability.

Homogeneous Dual Fluorescence Count of CD4 in Clinical HIV-Positive Samples via Parallel Catalytic Hairpin Assembly and Multiple Recognitions.

Regularly measuring the level of CD4+ cells is necessary for monitoring progression and predicting prognosis in patients suffering from an infection with the human immunodeficiency virus (HIV). However, the current flow cytometry standard detection method is expensive and complicated. A parallel catalytic hairpin assembly (CHA)-assisted fluorescent aptasensor is reported for homogeneous CD4 count by targeting the CD4 protein expressed on the membrane of CD4+ cells. Detection was achieved using CdTe quantum dots (QDs) and methylene blue (MB) as signal reporters. CdTe QDs distinguished CHA-assisted release of Ag+ and C-Ag+-C and MB that has differentiated cytosine (C)-rich single-stranded DNA (ssDNA) and C-Ag+-C, generating changes in fluorescence intensity. With the assistance of the CHA strategy and luminescent nanomaterials, this method reached limits of detection of 0.03 fg/mL for the CD4 protein and 0.3 cells/mL for CD4+ cells with linear ranges of 0.1 to 100 fg/mL and 1 to 1000 cells/mL, respectively. The method was validated in 50 clinical whole blood samples consisting of 30 HIV-positive patients, 10 healthy volunteers, and 10 patients with cancer or other chronic infections. The findings from this method were in good agreement with the data from clinical flow cytometry. Due to its sensitivity, affordability, and ease of operation, the current method has demonstrated great potential for routine CD4 counts for the management of HIV, especially in communities and remote areas.

Effect of the Elaboration Method on Structural and Optical Properties of Zn1.33Ga1.335Sn0.33O4:0.5%Cr3+ Persistent Luminescent Nanomaterials.

Near-infrared (NIR) persistent luminescence (PersL) materials have demonstrated promising developments for applications in many advanced fields due to their unique optical properties. Both high-temperature solid-state (SS) or hydrothermal (HT) methods can successfully be used to prepare PersL materials. In this work, Zn1.33Ga1.34Sn0.33O4:0.5%Cr3+ (ZGSO:0.5%Cr3+), a newly proposed nanomaterial for bioimaging, was prepared using SS and HT methods. The results show the crystal structure, morphology and optical properties of the samples that were prepared using both methods. Briefly, the crystallite size of the ZGSO:0.5%Cr3+ prepared using the SS method is ~3 µm, and as expected, is larger than materials prepared using the HT method. However, the growth process used in the hydrothermal environment promotes the formation of ZGSO:0.5%Cr3+ with more uniform shapes and smaller sizes (less than 500 nm). Different diameter ranges of nanoparticles were obtained using HT and ball milling (BM) methods (ranging from 25-50 nm) and by using SS and BM methods (25-200 nm) as well. In addition, the SS-prepared microstructure material has stronger PersL than HT-prepared particles before they go through ball milling to create nanomaterials. On the contrary, after BM treatment, ZGSO:0.5%Cr3+ HT and BM NPs present higher PersL and photoluminescence (PL) properties than ZGSO:0.5%Cr3+ SS and BM NPs, even though both kinds of NPs present worse PersL and PL compared to the original particles before BM. To summarize: preparation methods, whether by SS or HT, with additional grinding as a second step, can have a significant impact on the morphological and luminescent features of ZGSO:0.5%Cr3+ PersL materials.

A photo-controlled fluorescent switching based on carbon dots and photochromic diarylethene for bioimaging.

Carbon dots (CDs) as luminescent zero-dimensional carbon nanomaterials have good aqueous dissolution, photostability, high quantum yield, and tunability of emission color. It has great application potential in many fields, including bioimaging, labeling of biological species, drug delivery, and sensing in biomedical. However, controlling the fluorescence emission of carbon dots remains a formidable challenge. Herein, we designed and exploited a photo-controlled fluorescent switching based on photochromic diarylethene (DT) and CDs for bioimaging. It could be modulated reversibly between "ON" and "OFF" under UV/vis light exposure. The fluorescent modulation efficiency was as high as 95.3%. The fluorescent switching could be used to the bioimaging in HeLa cells with low cell toxicity. Therefore, this fluorescent switching could be a promising candidate in many potential application areas, especially in bioimaging.

Lemon-derived carbon dots as antioxidant and light emitter in fluorescent films applied to nanothermometry

The design of luminescent nanomaterials for the development of nanothermometers with high sensitivity and free of potentially toxic metals has developed in several fields, such as optoelectronics, sensors, and bioimaging. In addition, luminescent nanothermometers have advantages related to non-invasive measurement, with their wide detection range and high spatial resolution at the nano/microscale. Our study is the first, to our knowledge, to demonstrate a detailed study of a fluorescent film (Film-L) thermal sensor based on carbon dots derived from lemon bagasse extract (CD-L). The CD-L properties were explored as an antioxidant agent; their cytotoxicity was evaluated by using a human non-tumoral skin fibroblast (HFF-1) cell line from an MTT assay. The CD-L were characterized by HRTEM, DLS, FTIR, UV–VIS, and fluorescence spectroscopy. These confirmed their particle size distribution below 10 nm, graphitic structure in the core and surface organic groups, and strong blue emission. The CD-L showed cytocompatibility behavior and scavenging potential reactive species of biological importance: O2•− and HOCl, with IC50 of 276.8 ± 4.0 and 21.6 ± 0.7, respectively. The Film-L emission intensities (I425 nm) are temperature-dependent in the 298 to 333 K range. The Film-L luminescent thermometer shows a maximum relative thermal sensitivity of 2.69 % K−1 at 333 K.

Supramolecular self-assembly of carbon nanodots through edge functionalized interaction

Control of aggregation plays an important role in the photophysical behavior of luminescent nanomaterials. Herein, the concentration-dependent self-assembled hybrid of carbon nanodots (CDs) with the alteration spectral characters of H-/J-aggregation were observed. In detail, the CDs aging under different conditions presented obvious spectral variations ranging from visible to near-infrared regions, accompanied by the spontaneous evolution of nanoaggregates from CD nanoparticles. Theoretical calculations and experimental results confirmed the inhomogeneous surface functional groups could render CDs into nanoaggregates with the H- or J-aggregation through intraparticle or interparticle interaction, inducing the discrepant surface-confined charges in these intraparticle nanoaggregates and further contributing to their shift of absorption and emission bands. With the novel aggregation regulation, the CDs exhibited a tunable increase in their photothermal and photodynamic capability in comparison to their original counterparts. These findings shed a new light on the understanding of the photophysical behaviors for the self-assembled hybrid of CDs with the concept of supramolecular engineering.

A membrane biosensor based on colour differences encoded upconversion silica nanoparticles for multiplex nucleic acids detection

Upconversion luminescent nanomaterials provide a powerful tool for multiplex nucleic acids detection simultaneously. However, the conventional encoding methods based on emission spectrum or intensity have limitations due to spectral overlap and cross-relaxation quenching among various activators. Herein, we present a facile method for the preparation of high-capacity upconversion luminescent coding nanoparticles by multiple regulating the synthesis kinetics of lanthanide ions doped CaF2 nanocrystals in mesoporous silica nanotemplets (named C@S). The secondary growth of nanocrystals with different lanthanide ions inside mesopores has a similar performance to that of core/multi-shell-structured upconversion nanoparticles prepared through complicated processes. The textural properties and chemical conformations are maintained after repeated recombination, which is beneficial for reproducible multiplex bioassays. A membrane biosensor is constructed using various probe-modified C@S and a flexible graphene oxide-coated film to detect and identify multiple molecular species in one sample. The colour differences of encoded C@S derived from CIE-L*a*b* colour coordinate system are applied to quantify the divergence of upconversion luminescence for the first time, which allows the upconversion nanoparticles with similar spectra and luminescence colours to be used in the same multiplex detection platform and avoids subjective judgement. This work opens new opportunities for upconversion luminescent materials in the field of automatic high-throughput detection.

A brighter era for silver chalcogenide semiconductor nanocrystals

Silver chalcogenide semiconductor nanocrystals (Ag2E SNCs) have become a household name in the biomedical field, where they are used as contrast agents in bioimaging, photothermal therapy agents, and luminescent nanothermometers. The prominent position they have come to occupy in this field stems from a unique combination of features, above all near-infrared excitation and emission alongside low cytotoxicity. However, the first reports on Ag2E SNCs showed that a great limitation of these luminescent nanomaterials resided in their low photoluminescence quantum yield, which results in reduced brightness: a crippling feature in bioimaging and biosensing. In this article, we provide an overview of the strategies developed to overcome this hurdle. These strategies aim to remedy the presence of defects in the SNC core and/or surface, the presence of metallic silver, and off-stoichiometric composition. These features stem from the high mobility and redox potential of Ag+ ions, alongside the difficulty in controlling the nucleation and growth rate of Ag2E SNCs. The effectiveness of each approach is discussed. Lastly, a perspective on future research efforts to make Ag2E SNCs even brighter – and thus more effective in biomedical applications – is provided, with the hope of inspiring further investigation on these nanomaterials with a rich, complex set of physicochemical and spectroscopic properties.

Nonpolar Solvent Modulated Inkjet Printing of Nanoparticle Self-Assembly Morphologies.

Patterning of luminescent nanomaterials is critical in the fields of display and information encryption, and inkjet printing technology have shown remarkable significance with the advantage of fast, large-scalable and integrative. However, inkjet printing nanoparticle deposits with high-resolution and well controlled morphology from nonpolar solvent droplets is still challenging. Herein, a facile approach of nonpolar solvent modulated inkjet printing of nanoparticles self-assembly patterns driven by the shrinkage of the droplet and inner solutal convection is proposed. Through regulating the solvent composition and nanoparticle concentration, multicolor light-emissive upconversion nanoparticle self-assembly microarrays with tunable morphologies are achieved, showing the integration of designable microscale morphologies and photoluminescences for multimodal anti-counterfeit. Furthermore, inkjet printing of nanoparticles self-assembled continuous lines with adjustable morphologies by controlling the coalescence and drying of the ink droplets is achieved. The high resolution of inkjet printing microarrays and continuous lines' width < 5 and 10µm is realized, respectively. This nonpolar solvent-modulated inkjet printing of nanoparticle deposits approach facilitates the patterning and integration of different nanomaterials, and is expected to provide a versatile platform for fabricating advanced devicesapplied in photonics integration, micro-LED, and near-field display.

Temperature-Responsive Ratiometric Au Nanoclusters (NCs) Fabricated through α-Cyclodextrin-Protected Au NCs and Au@GSH NCs

Low color rendering indices (CRIs), distorted chromaticity, and monotonous luminescence seriously hinder the application of luminescent nanomaterials. In this case, Au nanoclusters (Au NCs) are promising candidates for the fabrication of luminescent sensing systems attributed to their excellent luminescent properties and ultrafine size. Here, we synthesized Au@α-CD NCs with blue fluorescence emission adopting the host macrocyclic molecule (6-SH-α-CD) as the ligand and matched it elaborately with orange phosphorescence-emissive Au@GSH NCs to fabricate multicolor tunable ratiometric Au NC luminescent systems. Accordingly, a standard white-light emission was successfully achieved with Commission Internationale de L’Éclairage located at (0.33, 0.33) and a CRI as high as 93. In view of the difference in temperature sensitivity between the lowest excited states of the two Au NCs, the ratiometric blending Au NCs moved from the 3500 K warm light region to 14400 K cold light region when the temperature varied from 0 to 70 °C, which played a role in monitoring temperature changes with the naked eye.

Design, Synthesis, and Biomedical Application of Multifunctional Fluorescent Polymer Nanomaterials.

Luminescent polymer nanomaterials not only have the characteristics of various types of luminescent functional materials and a wide range of applications, but also have the characteristics of good biocompatibility and easy functionalization of polymer nanomaterials. They are widely used in biomedical fields such as bioimaging, biosensing, and drug delivery. Designing and constructing new controllable synthesis methods for multifunctional fluorescent polymer nanomaterials with good water solubility and excellent biocompatibility is of great significance. Exploring efficient functionalization methods for luminescent materials is still one of the core issues in the design and development of new fluorescent materials. With this in mind, this review first introduces the structures, properties, and synthetic methods regarding fluorescent polymeric nanomaterials. Then, the functionalization strategies of fluorescent polymer nanomaterials are summarized. In addition, the research progress of multifunctional fluorescent polymer nanomaterials for bioimaging is also discussed. Finally, the synthesis, development, and application fields of fluorescent polymeric nanomaterials, as well as the challenges and opportunities of structure-property correlations, are comprehensively summarized and the corresponding perspectives are well illustrated.

Synthesis of Nanocellulose‐Based Nitrogen‐Doped Carbon Quantum Dots with High Fluorescence Quantum Yields for Multifunctional Applications

AbstractCarbon quantum dots (CQDs) are one of the most promising luminescent nanomaterials for anti‐counterfeiting due to their excellent optical properties, low toxicity, and environmental friendliness. With the development of green chemistry, biomass carbon sources have attracted attention. Herein, nitrogen‐doped carbon quantum dots (N‐CQDs) are synthesized using waste corn bract nanocellulose as the carbon source and L‐histidine as the nitrogen source in a simple and quick one‐step microwave method. It is found that a raw material mass ratio of 1:4, a temperature of 100 °C, and a preparation time of 5 min are the optimum preparation conditions. The fluorescence quantum yield of N‐CQDs obtained under these conditions is 32.64%. Under the excitation of light at a wavelength of 365 nm, the emission peak of N‐CQDs is located at 430 nm and emits blue light. This study also provides a method to prepare fluorescent anti‐counterfeiting films with excellent performance and fluorescent detection probes solely from waste biomass corn bract leaves and L‐histidine.

Nanocomposites of Silicon Oxides and Carbon: Its Study as Luminescent Nanomaterials

In this work, hybrid structures formed by nanostructured layers, which contain materials, such as porous silicon (PSi), carbon nanotubes (CNTs), graphene oxide (GO), and silicon-rich oxide (SRO), were studied. The PSi layers were obtained by electrochemical etching over which CNTs and GO were deposited by spin coating. In addition, SRO layers, in which silicon nanocrystals are embedded, were obtained by hot filament chemical vapor deposition (HFCVD) technique. Photoluminescence (PL) spectra were obtained from the hybrid structures with which a comparative analysis was completed among different PL ones. The SRO layers were used to confine the CNTs and GO. The main purpose of making these hybrid structures is to modulate their PL response and obtain different emission energy regions in the PL response. It was found that the PL spectra of the CNTs/SRO and GO/SRO structures exhibit a shift towards high energies compared to those obtained from the PSi layers; likewise, the PSi/CNTs/SRO and PSi/GO/SRO structures show a similar behavior. To identify the different emission mechanisms originated by PSi, GO, CNTs, and SRO, the PL spectra were deconvolved. It was found that the Psi/CNTs/SRO and Psi/GO/SRO structures exhibit a PL shift in respect to the PSi layers, for this reason, the modulation of the PL emission of the structures makes these hybrid structures promising candidates to be applied in the field of photonic and electroluminescent devices.

CsPbBr3 nanocrystals as luminescent probe for in situ detection of chloride and iodide ions in water

All-inorganic cesium lead halide (CsPbX3, X = Cl, Br, I) Perovskite nanocrystals (PNCs) are promising new luminescent nanomaterials. However, PNCs are less stable in ambient environments. The fully encapsulated protective layer greatly improves the stability but limits direct contact with substances in the environment, leading to great challenges for luminescent probe applications. We developed a simple approach that hydrogen-bond cross-linking reinforcement to deal with the challenge. Target ACD-PNCs, which use β-CD (β- cyclodextrin) as the ligand with addition of Arginine, were prepared by adding arginine to an ethanol solution of CsPbBr3 stabilized by β-CD. The ACD-PNCs have a luminescence efficiency of 82% and show good stability in external environments including high temperature, humidity, and ethanol–water mixed solvents. It is worth noting that neither arginine nor cyclodextrin alone could have allowed PNCs to perform so well. More interestingly, the hydrogen-bond network permits the passage of chloride and iodide ions. Through the response of luminescence color upon ion exchange, the ACD-PNCs can detect aqueous Cl− and I− with good selectivity and sensitivity. Under optimum conditions, the LOD and % RSD were determined as 3.2*10−6 M and 5.7% for Cl−, 9.0*10−6 M and 6.7% for I−, respectively. To identify halide ions in samples like sweat, saliva, and kelp, conveniently prepared ACD-PNCs test strips were employed. This work provides insights into the design and development of perovskite probes capable of detection in aqueous solution, and also demonstrates the importance of rapidly forming hydrogen-bonding networks when studying such sensing systems.

Triple-Mode upconversion emission for dynamic multicolor luminescent anti-Counterfeiting

Lanthanide (Ln3+) luminescent materials play a crucial role in information security and data storage owing to their excellent and unique optical properties. The advances in dynamic colorful luminescent anti-counterfeiting nanomaterials enable the generation of a high-level information encryption. In this work, a superior thermal, optical wavelength and excitation power triple-mode stimuli-responsive emission color modulation is demonstrated in a lanthanide-doped nanostructured luminescent material. The plentiful emission colors are manipulated by modulating the composition of a fluoride core–shell nanostructure with different Ln3+ at different doping concentrations. The nanomaterials display remarkable excitation wavelength/power-dependent color change, along with temperature-dependent color variation in the range from 298 K to 437 K, with a good relative sensitivity Sr of 1.1387% K−1 at 398 K. The universal optical modulation, combined with the excellent optical and structural stability of the luminescent nanoparticles, renders many advantages for the anti-counterfeiting application. This work explores a universal strategy for the manipulation of triple-mode stimuli-responsive dynamic luminescence and demonstrates its good potential for anti-counterfeiting application.

Luminescence Nanomaterials and Applications

We are pleased to introduce to you this Special Issue of Nanomaterials on 'Luminescence Nanomaterials and Applications' [...].

Controlling persistent luminescence in nanocrystalline phosphors.

Persistent luminescent phosphors can store light energy in advance and release it with a long-lasting afterglow emission. With their ability to eliminate in situ excitation and store energy for long periods of time, they are promising for broad applications, including background-free bioimaging, high-resolution radiography, conformal electronics imaging and multilevel encryption. This Review provides an overview of various strategies for trap manipulation in persistent luminescent nanomaterials. We highlight key examples in the design and preparation of nanomaterials with tunable persistent luminescence, particularly in the near-infrared range. In subsequent sections, we cover the most current developments and trends concerning the use of these nanomaterials in biological applications. Moreover, we assess their advantages and disadvantages compared with conventional luminescent materials for biological applications. We also discuss future research directions and challenges, such as insufficient brightness at the single-particle level, and possible solutions to these challenges.