Wide‐Range Tunable Fluorescence Lifetime and Ultrabright Luminescence of Eu‐Grafted Plasmonic Core–Shell Nanoparticles for Multiplexing

Wide‐range, well‐separated, and tunable lifetime nanocomposites with ultrabright fluorescence are highly desirable for applications in optical multiplexing such as multiplexed biological detection, data storage, and security printing. Here, a synthesis of tunable fluorescence lifetime nanocomposites is reported featuring europium chelate grafted onto the surface of plasmonic core–shell nanoparticles, and systematically investigated their optical performance. In a single red color emission channel, more than 12 distinct fluorescence lifetime populations with high fluorescence efficiency (up to 73%) are reported. The fluorescence lifetime of Eu‐grafted core–shell nanoparticles exhibits a wider tunable range, possesses larger lifetime interval and is more sensitive to separation distance than that of ordinary Eu‐doping core–shell type. These superior performances are attributed to the unique nanostructure of Eu‐grafed type. In addition, these as‐prepared nanocomposites are used for security printing to demonstrate optical multiplexing applications. The optical multiplexing experiments show an interesting pseudo‐information “a rabbit in a well” and conceal the real message “NKU.”     

Importance of nanoparticle size in colorimetric and SERS-based multimodal trace detection of Ni(II) ions with functional gold nanoparticles

Colorimetric detection of analytes using gold nanoparticles along with surface-enhanced Raman spectroscopy (SERS) are areas of intense research activity since they both offer sensing of very low concentrations of target species. Multimodal detection promotes the simultaneous detection of a sample by a combination of different techniques; consequently, surface chemistry design in the development of multimodal nanosensors is important for rapid and sensitive evaluation of the analytes by diverse analytical methods. Herein it is shown that nanoparticle size plays an important role in the design of functional nanoparticles for colorimetric and SERS-based sensing applications, allowing controlled nanoparticle assembly and tunable sensor response. The design and preparation of robust nanoparticle systems and their assembly is reported for trace detection of Ni(II) ions as a model system in an aqueous solution. The combination of covalently attached nitrilotriacetic acid moieties along with the L-carnosine dipeptide on the nanoparticle surface represents a highly sensitive platform for rapid and selective detection of Ni(II) ions. This systematic study demonstrates that significantly lower detection limits can be achieved by finely tuning the assembly of gold nanoparticles of different core sizes. The results clearly demonstrate the feasibility and usefulness of a multimodal approach.     

Encapsulation of Single Plasmonic Nanoparticles within ZIF‐8 and SERS Analysis of the MOF Flexibility

Hybrid nanostructures composed of metal nanoparticles and metal‐organic frameworks (MOFs) have recently received increasing attention toward various applications due to the combination of optical and catalytic properties of nanometals with the large internal surface area, tunable crystal porosity and unique chemical properties of MOFs. Encapsulation of metal nanoparticles of well‐defined shapes into porous MOFs in a core–shell type configuration can thus lead to enhanced stability and selectivity in applications such as sensing or catalysis. In this study, the encapsulation of single noble metal nanoparticles with arbitrary shapes within zeolitic imidazolate‐based metal organic frameworks (ZIF‐8) is demonstrated. The synthetic strategy is based on the enhanced interaction between ZIF‐8 nanocrystals and metal nanoparticle surfaces covered by quaternary ammonium surfactants. High resolution electron microscopy and tomography confirm a complete core–shell morphology. Such a well‐defined morphology allowed us to study the transport of guest molecules through the ZIF‐8 porous shell by means of surface‐enhanced Raman scattering by the metal cores. The results demonstrate that even molecules larger than the ZIF‐8 aperture and pore size may be able to diffuse through the framework and reach the metal core.     

Dual fluorescence sensor for trace oxygen and temperature with unmatched range and sensitivity

An optical dual sensor for oxygen and temperature is presented that is highly oxygen sensitive and covers a broad temperature range. Dual sensing is based on luminescence lifetime measurements. The novel sensor contains two luminescent compounds incorporated into polymer films. The temperature-sensitive dye (ruthenium tris-1,10-phenanthroline) has a highly temperature-dependent luminescence and is incorporated in poly(acrylonitrile) to avoid cross-sensitivity to oxygen. Fullerene C70 was used as the oxygen-sensitive probe owing to its strong thermally activated delayed fluorescence at elevated temperatures that is extremely oxygen sensitive. The cross-sensitivity of C70 to temperature is accounted for by means of the temperature sensor. C70 is incorporated into a highly oxygen-permeable polymer, either ethyl cellulose or organosilica. The two luminescent probes have different emission spectra and decay times, and their emissions can be discriminated using both parameters. Spatially resolved sensing is achieved by means of fluorescence lifetime imaging. The response times of the sensor to oxygen are short. The dual sensor exhibits a temperature operation range between at least 0 and 120 degrees C, and detection limits for oxygen in the ppbv range, operating for oxygen concentrations up to at least 50 ppmv. These ranges outperform all dual oxygen and temperature sensors reported so far. The dual sensor presented in this study is especially appropriate for measurements under extreme conditions such as high temperatures and ultralow oxygen levels. This dual sensor is a key step forward in a number of scientifically or commercially important applications including food packaging, for monitoring of hyperthermophilic microorganisms, in space technology, and safety and security applications in terms of detection of oxygen leaks.     

Precisely Size‐Tunable Monodisperse Hairy Plasmonic Nanoparticles via Amphiphilic Star‐Like Block Copolymers

In situ precision synthesis of monodisperse hairy plasmonic nanoparticles with tailored dimensions and compositions by capitalizing on amphiphilic star‐like diblock copolymers as nanoreactors are reported. Such hairy plasmonic nanoparticles comprise uniform noble metal nanoparticles intimately and perpetually capped by hydrophobic polymer chains (i.e., “hairs”) with even length. Interestingly, amphiphilic star‐like diblock copolymer nanoreactors retain the spherical shape under reaction conditions, and the diameter of the resulting plasmonic nanoparticles and the thickness of polymer chains situated on the surface of the nanoparticle can be readily and precisely tailored. These hairy nanoparticles can be regarded as hard/soft core/shell nanoparticles. Notably, the polymer “hairs” are directly and permanently tethered to the noble metal nanoparticle surface, thereby preventing the aggregation of nanoparticles and rendering their dissolution in nonpolar solvents and the homogeneous distribution in polymer matrices with long‐term stability. This amphiphilic star‐like block copolymer nanoreactor‐based strategy is viable and robust and conceptually enables the design and synthesis of a rich variety of hairy functional nanoparticles with new horizons for fundamental research on self‐assembly and technological applications in plasmonics, catalysis, energy conversion and storage, bioimaging, and biosensors.     

Surface-enhanced Raman scattering inside Au@Ag core/shell nanorods

The design and synthesis of plasmonic nanoparticles with Raman-active molecules embedded inside them are of significant interest for sensing and imaging applications.However,direct synthesis of such nanostructures with controllable shape,size,and plasmonic properties remains extremely challenging.Here we report on the preparation of uniform Au@Ag core/shell nanorods with controllable Ag shells of 1 to 25 nm in thickness.1,4-Aminothiophenol (4-ATP) molecules,used as the Raman reporters,were located between the Au core and the Ag shell.Successful embedding of reporter molecules inside the core/shell nanoparticles was confirmed by the absence of selective oxidation of the amino groups,as measured by Raman spectroscopy.The dependence of Raman intensity on the location of the reporter molecules in the inside and outside of the nanorods was studied.The molecules in the interior showed strong and uniform Raman intensity,at least an order of magnitude higher than that of the molecules on the nanoparticle surface.In contrast to the usual surface-functionalized Raman tags,aggregation and clustering of nanoparticles with embedded molecules decreased the surface-enhanced Raman scattering (SERS) signal.The findings from this study provide the basis for a novel detection technique of low analyte concentration utilizing the high SERS response of molecules inside the core/shell metal nanostructures.As an example,we show robust SERS detection of thiram fungicide as low as 10-9 M in solutions.     

Nanoparticle Cookies Derived from Metal‐Organic Frameworks: Controlled Synthesis and Application in Anode Materials for Lithium‐Ion Batteries

The capacity of anode materials plays a critical role in the performance of lithium‐ion batteries. Using the nanocrystals of oxygen‐free metal‐organic framework ZIF‐67 as precursor, a one‐step calcination approach toward the controlled synthesis of CoO nanoparticle cookies with excellent anodic performances is developed in this work. The CoO nanoparticle cookies feature highly porous structure composed of small CoO nanoparticles (≈12 nm in diameter) and nitrogen‐rich graphitic carbon matrix (≈18 at% in nitrogen content). Benefiting from such unique structure, the CoO nanoparticle cookies are capable of delivering superior specific capacity and cycling stability (1383 mA h g^?1 after 200 runs at 100 mA g^?1) over those of CoO and graphite.     

Advances in the Application of Magnetic Nanoparticles for Sensing

Magnetic nanoparticles (MNPs) are of high significance in sensing as they provide viable solutions to the enduring challenges related to lower detection limits and nonspecific effects. The rapid expansion in the applications of MNPs creates a need to overview the current state of the field of MNPs for sensing applications. In this review, the trends and concepts in the literature are critically appraised in terms of the opportunities and limitations of MNPs used for the most advanced sensing applications. The latest progress in MNP sensor technologies is overviewed with a focus on MNP structures and properties, as well as the strategies of incorporating these MNPs into devices. By looking at recent synthetic advancements, and the key challenges that face nanoparticle‐based sensors, this review aims to outline how to design, synthesize, and use MNPs to make the most effective and sensitive sensors.     

Design of Multifunctional Fluorescent Hybrid Materials Based on SiO2 Materials and Core–Shell Fe3O4@SiO2 Nanoparticles for Metal Ion Sensing

Hybrid fluorescent materials constructed from organic chelating fluorescent probes and inorganic solid supports by covalent interactions are a special type of hybrid sensing platform that has gained much interest in the context of metal ion sensing applications owing to their excellent advantages, recyclability, and solubility/dispersibility in particular, as compared with single organic fluorescent molecules. In recent decades, SiO₂ materials and core–shell Fe₃O₄@SiO₂ nanoparticles have become important inorganic solid materials and have been used as inorganic solid supports to hybridize with organic fluorescent receptors, resulting in multifunctional fluorescent hybrid systems for potential applications in sensing and related research fields. Therefore, recent progress in various fluorescent‐group‐functionalized SiO₂ materials is reviewed, with a focus on mesoporous silica nanoparticles and core–shell Fe₃O₄@SiO₂ nanoparticles, as interesting fluorescent organic–inorganic hybrid materials for sensing applications toward essential and toxic metal ions. Selective examples of other types of silica/silicon materials, such as periodic mesoporous organosilicas, solid SiO₂ nanoparticles, fibrous silica spheres, silica nanowires, silica nanotubes, and silica hollow microspheres, are also mentioned. Finally, relevant perspectives of metal‐ion‐sensing‐oriented silica‐fluorescent probe hybrid materials are provided.     

On‐Chip Spiral Waveguides for Ultrasensitive and Rapid Detection of Nanoscale Objects

Ultrasensitive and rapid detection of nano‐objects is crucial in both fundamental studies and practical applications. Optical sensors using evanescent fields in microcavities, plasmonic resonators, and nanofibers allow label‐free detection down to single molecules, but practical applications are severely hindered by long response time and device reproducibility. Here, an on‐chip dense waveguide sensor to monitor single unlabeled nanoparticles in a strong optical evanescent field is demonstrated. The spiral nanowaveguide design enables two orders of magnitude enhancement in sensing area compared to a straight waveguide, significantly improving the particle capture ability and shortening the target analysis time. In addition, the measurement noise is suppressed to a level of 10^?4 in the transmitted power, pushing the detection limit of single particles down to the size of 100 nm. The waveguide sensor on the silicon‐on‐isolator platform can be fabricated reproducibly by the conventional semiconductor processing and compatible with surface functionalization chemistries and microfluidics, which could lead to widespread use for sensing in environmental monitoring and human health.     

In situ controllable synthesis of Ag@AgCl core–shell nanoparticles on graphene oxide sheets

Graphene oxide-supported uniform Ag@AgCl core–shell nanoparticle composites have been successfully prepared by a facile two-step synthetic process. First, graphene oxide sheets were used as carriers to anchor and disperse Ag nanoparticles on their surface. Then these fixed Ag nanoparticles on carbon sheets are utilized as precursors, around which AgCl nanocrystals form in situ using FeCl₃ as oxidant, forming graphene oxide-supported Ag@AgCl core–shell nanoparticle composites. The composition of these attached Ag@AgCl core–shell nanoparticles can be easily controlled by adjusting the usage of FeCl₃, resulting in the formation of controllable core–shell nanostructures. Furthermore, these as-prepared graphene oxide–Ag@AgCl nanoparticle composites display effective photodegradation of methylene orange dye under visible light irradiation, which indicates their potential applications in environmental areas.     

Versatile Yolk–Shell Encapsulation: Catalytic,Photothermal, and Sensing Demonstration

Here, a novel, versatile synthetic strategy to fabricate a yolk–shell structured material that can encapsulate virtually any functional noble metal or metal oxide nanocatalysts of any morphology in a free suspension fashion is reported. This strategy also enables encapsulation of more than one type of nanoparticle inside a single shell, including paramagnetic iron oxide used for magnetic separation. The mesoporous organosilica shell provides efficient mass transfer of small target molecules, while serving as a size exclusion barrier for larger interfering molecules. Major structural and functional advantages of this material design are demonstrated by performing three proof‐of‐concept applications. First, effective encapsulation of plasmonic gold nanospheres for localized photothermal heating and heat‐driven reaction inside the shell is shown. Second, hydrogenation catalysis is demonstrated under spatial confinement driven by palladium nanocubes. Finally, the surface‐enhanced Raman spectroscopic detection of model pollutant by gold nanorods is presented for highly sensitive environmental sensing with size exclusion.     

Influence of Temperature on the Colloidal Stability of Polymer‐Coated Gold Nanoparticles in Cell Culture Media

The temperature‐dependence of the hydrodynamic diameter and colloidal stability of gold‐polymer core‐shell particles with temperature‐sensitive (poly(N‐isopropylacrylamide)) and temperature‐insensitive shells (polyallylaminine hydrochloride/polystyrensulfonate, poly(isobutylene‐alt‐maleic anhydride)‐graft‐dodecyl) are investigated in various aqueous media. The data demonstrate that for all nanoparticle agglomeration, i.e., increase in effective nanoparticle size, the presence of salts or proteins in the dispersion media has to be taken into account. Poly(N‐isopropylacrylamide) coated nanoparticles show a reversible temperature‐dependent increase in size above the volume phase transition of the polymer shell when they are dispersed in phosphate buffered saline or in media containing protein. In contrast, the nanoparticles coated with temperature‐insensitive polymers show a time‐dependent increase in size in phosphate buffered saline or in medium containing protein. This is due to time‐dependent agglomeration, which is particularly strong in phosphate buffered saline, and induces a time‐dependent, irreversible increase in the hydrodynamic diameter of the nanoparticles. This demonstrates that one has to distinguish between temperature‐ and time‐induced agglomerations. Since the size of nanoparticles regulates their uptake by cells, temperature‐dependent uptake of thermosensitive and non‐thermosensitive nanoparticles by cells lines is compared. No temperature‐specific difference between both types of nanoparticles could be observed.     

Micelle nanoparticles for FRET-based ratiometric sensing of mercury ions in water, biological fluids and living cells

A fluorescence resonance energy transfer (FRET) based ratiometric sensing system for mercury ions is built in nano-sized core/corona micelles formed by a poly(ethylene oxide)-b-polystyrene diblock copolymer. For this system, a hydrophobic fluorescein derivative (FLS-C12), which serves as the energy transfer donor, is incorporated into the micelle core during the micelle formation; and a spirolactam-rhodamine derivative (RhB-CS) as a probe for mercury ions is located at the micelle core/corona interface. An efficient ring-opening reaction of RhB-CS induced by mercury ions generates the long-wavelength rhodamine B fluorophore which can act as the energy acceptor, affording the micelle nanoparticles the water-dispersible FRET-based ratiometric detection system for mercury ions, with a detection limit of 0.1 μM in water. The donor and the probe fluorophores, with their structure being appropriately modified, can strongly bind (non-covalently) to the specific sites of the micelles and form a stable ratiometric sensor in water and in some biological fluids. In addition, with the water-soluble and biocompatible poly(ethylene oxide) (PEO) as the corona of the micelles, the nano-sized sensing system can readily permeate through cell membrane and detect intracellular Hg(2+) level changes.     

Synthesis of dendrimer-stabilized gold-polypyrrole core-shell nanoparticles

Core-shell composite nanoparticles consisting of a gold core and polypyrrole shell were prepared and stabilized with the poly(amidoamine) dendrimer. An in situ redox polymerization technique was used in which pyrrole reduced Au3+ to Au and then oxidized to polypyrrole. The presence of gold nanoparticles as a core was characterized by its surface plasmon absorption peak at 534 nm. Fourier transform infrared spectroscopy confirmed the presence of polypyrrole on the nanoparticle surfaces. The average diameter of the core-shell nanoparticle is 8.7 +/- 1.8 nm with a shell thickness of approximately 1.5-2.0 nm as estimated from the transmission electron microscopy image. Dissolution of the Au core using KCN enabled the formation of hollow polymer nanospheres.     

Magnetic and fluorescent core-shell nanoparticles for ratiometric pH sensing

This paper describes the preparation of nanoparticles composed of a magnetic core surrounded by two successive silica shells embedding two fluorophores, showing uniform nanoparticle size (50-60 nm in diameter) and shape, which allow ratiometric pH measurements in the pH range 5-8. Uncoated iron oxide magnetic nanoparticles (～10 nm in diameter) were formed by the coprecipitation reaction of ferrous and ferric salts. Then, they were added to a water-in-oil microemulsion where the hydrophilic silica shells were obtained through hydrolysis and condensation of tetraethoxyorthosilicate together with the corresponding silylated dye derivatives-a sulforhodamine was embedded in the inner silica shell and used as the reference dye while a pH-sensitive fluorescein was incorporated in the outer shell as the pH indicator. The magnetic nanoparticles were characterized using vibrating sample magnetometry, dynamic light scattering, transmission electron microscopy, x-ray diffraction and Fourier transform infrared spectroscopy. The relationship between the analytical parameter, that is, the ratio of fluorescence between the sensing and reference dyes versus the pH was adjusted to a sigmoidal fit using a Boltzmann type equation giving an apparent pK(a) value of 6.8. The fluorescence intensity of the reference dye did not change significantly (～3.0%) on modifying the pH of the nanoparticle dispersion. Finally, the proposed method was statistically validated against a reference procedure using samples of water and physiological buffer with 2% of horse serum, indicating that there are no significant statistical differences at a 95% confidence level.     

Ni@Ru and NiCo@Ru Core–Shell Hexagonal Nanosandwiches with a Compositionally Tunable Core and a Regioselectively Grown Shell

The development of highly active electrocatalysts is crucial for the advancement of renewable energy conversion devices. The design of core–shell nanoparticle catalysts represents a promising approach to boost catalytic activity as well as save the use of expensive precious metals. Here, a simple, one‐step synthetic route is reported to prepare hexagonal nanosandwich‐shaped Ni@Ru core–shell nanoparticles (Ni@Ru HNS), in which Ru shell layers are overgrown in a regioselective manner on the top and bottom, and around the center section of a hexagonal Ni nanoplate core. Notably, the synthesis can be extended to NiCo@Ru core–shell nanoparticles with tunable core compositions (Ni₃Co_x@Ru HNS). Core–shell HNS structures show superior electrocatalytic activity for the oxygen evolution reaction (OER) to a commercial RuO₂ black catalyst, with their OER activity being dependent on their core compositions. The observed trend in OER activity is correlated to the population of Ru oxide (Ru⁴⁺) species, which can be modulated by the core compositions.     

Preparation and characterization of ultra-stable biocompatible magnetic fluids using citrate-coated cobalt ferrite nanoparticles

Preparation and characterization of ultra-stable biocompatible cobalt ferrite-based magnetic fluids has been reported. Synthesized samples have core particle diameter in the range of 4.7 to 14.8 nm, as indicated by TEM. Chemical and crystalline data show that the prepared nanoparticles are cobalt ferrite with a slight deviation from the Fe : Co :: 2 : 1 stoichiometry. ATR-FTIR spectroscopy was used to investigate the citrate adsorption onto the nanoparticle surface. The fitted adsorption time-constants were 0.006 and 0.033 min^− 1 for nanoparticle diameter of 4.7 and 14.8 nm, respectively.     

Packaging of gold particles in viral capsids

In-vitro self-assembly conditions known to result in generating infectious virions have been used in vitro to reassemble bromovirus capsid proteins around negatively charged gold nanoparticles cores. We discuss here the optical properties (elastic light scattering) and the influence of the core size and of the functional moiety on the resulting virus-like particles. Our results indicate that the formation of a closed shell, as opposed to an amorphous protein coat, does occur and that the shell/core interactions can be tuned using different coatings on the nanoparticle core. Such studies may lead to real-time monitoring of viral traffic on the scale of a single virus, as well as to the possibility of chemical sensing along the intracellular and intercellular viral pathways and contribute to a better understanding of the virus transport and cellular compartmentalization.     

Visualizing Oxidative Cellular Stress Induced by Nanoparticles in the Subcytotoxic Range Using Fluorescence Lifetime Imaging

Nanoparticles hold a great promise in biomedical science. However, due to their unique physical and chemical properties they can lead to overproduction of intracellular reactive oxygen species (ROS). As an important mechanism of nanotoxicity, there is a great need for sensitive and high‐throughput adaptable single‐cell ROS detection methods. Here, fluorescence lifetime imaging microscopy (FLIM) is employed for single‐cell ROS detection (FLIM‐ROX) providing increased sensitivity and enabling high‐throughput analysis in fixed and live cells. FLIM‐ROX owes its sensitivity to the discrimination of autofluorescence from the unique fluorescence lifetime of the ROS reporter dye. The effect of subcytotoxic amounts of cationic gold nanoparticles in J774A.1 cells and primary human macrophages on ROS generation is investigated. FLIM‐ROX measures very low ROS levels upon gold nanoparticle exposure, which is undetectable by the conventional method. It is demonstrated that cellular morphology changes, elevated senescence, and DNA damage link the resulting low‐level oxidative stress to cellular adverse effects and thus nanotoxicity. Multiphoton FLIM‐ROX enables the quantification of spatial ROS distribution in vivo, which is shown for skin tissue as a target for nanoparticle exposure. Thus, this innovative method allows identifying of low‐level ROS in vitro and in vivo and, subsequently, promotes understanding of ROS‐associated nanotoxicity.