Individual Nanoparticles Research Articles

Multicore@shell nanoparticle synthesis from a single multicomponent target by gas aggregation source

Synthesis of multifunctional nanomaterials is known as a critical challenge in advanced nanoscience. Multicore@shell nanostructures are generated here via a gas phase synthesis approach. To achieve this objective, we used a conventional DC magnetron sputtering in conjunction with a gas aggregation chamber. We employed a customized Au-Ti target to produce metal-metal oxide multicore@shell nanoparticles (NPs) with tunable properties. The deposited NPs were characterized with regard to their chemical composition, morphology, structural status, NP size distribution and optical properties. The obtained data clearly confirms that the crystalline Au cores are encapsulated in a TiOx matrix in each individual NP. Furthermore, the chemical composition and size distribution of the NPs can be affected by the operating pressure. Our approach provides a versatile route with many different possibilities to synthesize multicore@shell NPs from a variety of composite targets for well-desired applications including environmental, optical/plasmonic, and energy.

Surface Self-Diffusion Induced Sintering of Nanoparticles.

Despite the critical role of sintering phenomena in constraining the long-term durability of nanosized particles, a clear understanding of nanoparticle sintering has remained elusive due to the challenges in atomically tracking the neck initiation and discerning different mechanisms. Through the integration of in situ transmission electron microscopy and atomistic modeling, this study uncovers the atomic dynamics governing the neck initiation of Pt-Fe nanoparticles via a surface self-diffusion process, allowing for coalescence without significant particle movement. Real-time imaging reveals that thermally activated surface morphology changes in individual nanoparticles induce significant surface self-diffusion. The kinetic entrapment of self-diffusing atoms in the gaps between closely spaced nanoparticles leads to the nucleation and growth of atomic layers for neck formation. This surface self-diffusion-driven sintering process is activated at a relatively lower temperature compared to the classic Ostwald ripening and particle migration and coalescence processes. The fundamental insights have practical implications for manipulating the morphology, size distribution, and stability of nanostructures by leveraging surface self-diffusion processes.

Correlative Multi-Scale Characterization of Nanoparticles Using Transmission Electron Microscopy

Chemical and physical properties of nanoparticles (NPs) are strongly influenced not only by the crystal structure of the respective material, including crystal structure defects but also by the NP size and shape. Contemporary transmission electron microscopy (TEM) can describe all these NP characteristics, however typically with a different statistical relevance. While the size and shape of NPs are frequently determined on a large ensemble of NPs and thus with good statistics, the characteristics on the atomic scale are usually quantified for a small number of individual NPs and thus with low statistical relevance. In this contribution, we present a TEM-based characterization technique, which can determine relevant characteristics of NPs in a scale-bridging way—from the crystal structure and crystal structure defects up to the NP size and morphology—with sufficient statistical relevance. This technique is based on a correlative multi-scale TEM approach that combines information on atomic scale obtained from the high-resolution imaging with the results of the low-resolution imaging assisted by a semi-automatic segmentation routine. The capability of the technique is illustrated in several examples, including Au NPs with different shapes, Au nanorods with different facet configurations, and multi-core iron oxide nanoparticles with a hierarchical structure.

Disruption Dynamics and Charge Transfer of a Single Attoliter Emulsion Droplet Revealed by Combined Fast-Scan Sinusoidal Voltammetry and Short Time Fourier Transform Analysis.

Single-entity electrochemistry has gained significant attention for the analysis of individual cells, nanoparticles, and droplets, which is leveraged by robust electrochemical techniques such as chronoamperometry and cyclic voltammetry (CV) to extract information about single entities, including size, kinetics, mass transport, etc. For an in-depth understanding such as dynamic interaction between the electrode and a single entity, the unconventional fast electrochemical technique is essential for time-resolved analysis. This fast experimental technique is unfortunately hindered by a substantial nonfaradaic response. In this work, we introduce fast-scan sinusoidal voltammetry (FSSV) combined with a short-time Fourier transform (STFT) for analyzing single emulsion droplets. Utilizing ultramicroelectrode and fast potential sweeps up to apparent 200 V/s, we achieved high temporal resolution (8 ms per voltammogram) to capture the current signals during droplet collisions. STFT analysis reveals the amplitude and phase changes, allowing for the accurate detection of collision events even in the absence of redox species. By adopting an algorithm of drift-free baseline subtraction, a conventional CV shape was obtained in FSSV. The reacted charge from the single-entity voltammogram at every 8 ms was also plotted. This method effectively addresses limitations in traditional techniques, providing insights into emulsion dynamics such as droplet contact and droplet breakdown.

Gradient distribution of cations in rhabdophane La0.27Y0.73PO4·nH2O nanoparticles

The structure of gradient rhabdophane nanoparticles of variable composition (La,Y)PO4·nH2O obtained by precipitation is considered. According to the data of HAADF TEM and EDX mapping using the Abel inversion procedure, it was shown that there is an inhomogeneous distribution of yttrium and lanthanum atoms in the particles from the central part to the periphery. At the same time, the nominal composition of both individual nanoparticles and the entire sample meets the value specified during synthesis within the error of the method – La0.27Y0.73PO4·nH2O. According to SAXS data, it was determined that in the particles of (La,Y)PO4·nH2O, there is a redistribution of scattering densities, which is caused by an increase in the fraction of YPO4 in the peripheral region of the particles. The observed effect of the distribution of cations over the particle made it possible to determine the size of the gradient layer, which reaches 50 % of the total particle size.

Exploiting the synergistic influence of AgNPs-TiO2NPs: enhancing phytostabilization of pb and mitigating its toxicity in Vigna unguiculata

In this study, a composite of silver and titanium dioxide nanoparticles (AgNPs-TiO2NPs) was examined for its synergistic effects on phytostabilization of lead (Pb) and mitigation of toxicity in cowpea (Vigna unguiculata (L) Walp). Seeds of V. unguiculata were wetted with water, 0.05 and 0.1 mgL−1 Pb and 25 mgmL−1 each of AgNPs, TiO2NPs, and AgNPs-TiO2NPs. Root lengths of V. unguiculata were reduced by 25% and 44% at 0.05 and 0.1 mgL−1 Pb, respectively, while shoot lengths were reduced by 2% and 7%. In V. unguiculata, AgNPs and TiO2NPs significantly improved physiological indicators and mitigated Pb effects, with TiO2NPs modulating physiological parameters more effectively than AgNPs. The composite (AgNPs-TiO2NPs) synergistically regulated V. unguiculata physiology better than individual nanoparticles. Compared to individual AgNPs and TiO2NPs, the composite (AgNPs-TiO2NPs) synergistically increased antioxidant activity by 12% and 9%, and carotenoid contents by 88%. Additionally, AgNPs-TiO2NPs effectively reduced malondialdehyde levels by 29%, thereby mitigating the effects of Pb on V. unguiculata better than individual nanoparticles. AgNPs-TiO2NPs enhanced Pb immobilization by 57%, reducing its translocation from soil to shoots compared to V. unguiculata wetted with water. The bioconcentration and translocation factors of Pb indicate that phytostabilization was most effective when the composite was used.

Uniform and delicate adjustment of plasmonic coupling upon evolved MoS2 crystalline shields on individual gold nanoparticles for photocatalytic water splitting

With the guided epitaxial growth of multiple MoS2 crystalline shields directly on individual gold nanoparticles and delicate control of shield thickness, the initiated self-assembly of hybrid nanoparticles in solutions results in various magnitudes of irradiation-stimulated plasmonic coupling. The theoretically derived medium ranges of separation distances for the optimization of plasmonic coupling has been experimentally verified and evaluated eventually, which is found critically subject to nanoparticles sizes and initiated tunneling currents. In addition to the enhancement of Raman scattering, the interfacial transition of hot electrons from Au cores to MoS2 shields has been clarified also to critically depend on the reached magnitudes of plasmonic coupling. Surprisingly, the activated plasmonic coupling is accompanied with the increase of work functions of hybrid nanoparticles, and capable to transfer Schottky contact to Ohmic contact with water molecules, revealed as a new mechanism to facilitate interfacial electronic transition. Furthermore, the plasmonic coupling is analyzed analogous to the result of mutual polarization between hybrid nanoparticles, which is also intensified with the created local electric fields and thus nanoparticle sizes. With activated plasmonic coupling subject to the thickness of MoS2 shields and nanoparticle sizes, the efficiency of hydrogen production upon photocatalytic water splitting by MoS2 shields is able to reach the record value of 35 mmol/g·hr, at least one-order-of-magnitude higher than other reported results. Accordingly, the adjustment of plasmonic coupling and thus nanoparticle polarization has been experimentally clarified as a promising strategy able to promote photocatalytic reactions in solutions.

Electronic communications between active sites on individual metallic nanoparticles in catalysis

Catalytic activity of metal particles is reported to originate from the appearance of nonmetallic states, but conductive metallic particles, as an electron reservoir, should render electron delivery between reactants more favorably so as to have higher activity. We present that metallic rhodium particle catalysts are highly active in the low-temperature oxidation of carbon monoxide, whereas nonmetallic rhodium clusters or monoatoms on alumina remain catalytically inert. Experimental and theoretical results evidence the presence of electronic communications in between vertex atom active sites of individual metallic particles in the reaction. The electronic communications dramatically lower apparent activation energies via coupling two electrochemical-like half-reactions occurring on different active sites, which enable the metallic particles to show turnover frequencies at least four orders of magnitude higher than the nonmetallic clusters or monoatoms. Similar results are found for other metallic particle catalysts, implying the importance of electronic communications between active sites in heterogeneous catalysis.

A Thin Polymer Layer Enables Peptide-Polycation Complexes with Ultrahigh Efficient Encapsulation.

A monolayer encapsulation is a new opportunity for engineering a system with high drug loading, but immobilizing polymer molecules on the surface of individual peptide nanoparticles is still an ongoing challenge. Herein, an individual peptide nanoparticle encapsulation strategy is proposed via surface adsorption, in which peptide molecules undergo granulation and subsequently aggregate with polymer molecules, forming a network via electrostatic interactions. Under the water phase, surplus polymer molecules dissolve, leading to a single nanoparticle encapsulation with a core-shell structure. As expected, the dense interfacial layer on the peptide nanoparticle surface achieves a superior loading degree of up to 95.4%. What's more, once the core-shell structure is established, the peptide mass fraction in individual encapsulation always exceeds 90% even under fierce external force. Following the individual nanoparticle encapsulation, the insulin-polycation complex (InsNp@PEI) reduces the inflammation from polymer and displays an effective glycemic control in type 1 diabetes. Overall, the newly developed single surface decoration encapsulates peptides with ultrahigh efficiency and opens up the possibility for further encapsulation.

Deterministic Assembly of Single-Emitter Plasmonic Antenna for Ultrahigh Photoluminescence Enhancement.

Single-emitter nanoantennas play a crucial role in the fabrication of nanosensors and integrated sources. Since the coupling of single emitter to nanoantennas is largely based on stochastic methods, low qualified rate still hinders a massive deployment. Here, we proposed a deterministic, optical-force-driven method to achieve gap-plasmonic photoluminescence enhancement. Two deterministic steps are carried out in sequence: a composite nanoemitter is first synthesized by linking quantum dots to a silica-rapped gold nanoparticle, followed by an optical delivery of the nanoparticle into a nanoaperture in a gold film. We reason that the nanoparticle-in-nanoaperture (NPiNA) structure efficiently couples out-of-plane excitation light into a gap-plasmon via a transverse electromagnetic mode (TEM)-like transmission mode. An in situ photoluminescence measurement demonstrates a 3× brightness as compared to the nanoparticle-on-mirror (NPoM). This approach paves the way toward deterministic positioning of individual nanoparticles for a wide range of applications on nanophotonics structures on-a-chip.

CircRNA based multivalent neuraminidase vaccine induces broad protection against influenza viruses in mice

Developing broad-spectrum influenza vaccines is crucial for influenza control and potential pandemic preparedness. Here, we reported a novel vaccine design utilizing circular RNA (circRNA) as a delivery platform for multi-subtype neuraminidases (NA) (influenza A N1, N2, and influenza B Victoria lineage NA) immunogens. Individual NA circRNA lipid nanoparticles (LNP) elicited robust NA-specific antibody responses with neuraminidase inhibition activity (NAI), preventing the virus from egressing and infecting neighboring cells. Additionally, the administration of circRNA LNP induced cellular immunity in mice. To achieve a universal influenza vaccine, we combined all three subtypes of NA circRNA-LNPs to generate a trivalent circRNA vaccine. The trivalent vaccine elicited a balanced antibody response against all three NA subtypes and a Th1-biased immune response in mice. Moreover, it protected mice against the lethal challenge of matched and mismatched H1N1, H3N2, and influenza B viruses, encompassing circulating and ancestral influenza virus strains. This study highlights the potential of delivering multiple NA antigens through circRNA-LNPs as a promising strategy for effectively developing a universal influenza vaccine against diverse influenza viruses.

Magnetic heating of interacting nanoparticles under different driving field waveforms

This study explores the impact of different magnetic driving field waveforms on nanoparticle heating in magnetic hyperthermia. Our research, which shifts the usual focus from individual nanoparticle properties to interacting particle clusters, evidences that square waves induce more uniform and greater heating than sinusoidal waves. The sequential switching observed with sinusoidal waves, which additionally strongly depends on the alignment of the particle cluster with respect to the direction of the field, leads to less uniform heating within and among different clusters. In contrast, a square waveform leads to simultaneous particle switching, thereby homogenizing the heat and potentially mitigating hazardous hot spots. These findings reaffirm the potential advantages for magnetic hyperthermia treatments using non-harmonic field waveforms, offering more uniform heating and the possibility of reducing the applied field exposure.

Single and combined effects of titanium (TiO2) and zinc (ZnO) oxide nanoparticles in the rainbow trout gill cell line RTgill-W1.

Understanding the environmental impact of nanoparticle (NP) mixtures is essential to accurately assess the risk they represent for aquatic ecosystems. However, although the toxicity of individual NPs has been extensively studied, information regarding the toxicity of combined NPs is still comparatively rather scarce. Hence, this research aimed to investigate the individual and combined toxicity mechanisms of two widely consumed nanoparticles, zinc oxide (ZnO NPs) and titanium dioxide (TiO2 NPs), using an in vitro model, the RTgill-W1 rainbow trout gill epithelial cell line. Sublethal concentrations of ZnO NPs (0.1µgmL-1) and TiO2 (30µgmL-1) and a lethal concentration of ZnO NPs causing 10% mortality (EC10, 3µgmL-1) were selected based on cytotoxicity assays. Cells were then exposed to the NPs at the selected concentrations alone and to their combination. Cytotoxicity assays, oxidative stress markers, and targeted gene expression analyses were employed to assess the NP cellular toxicity mechanisms and their effects on the gill cells. The cytotoxicity of the mixture was identical to the one of ZnO NPs alone. Enzymatic and gene expression (nrf2, gpx, sod) analyses suggest that none of the tested conditions induced a strong redox imbalance. Metal detoxification mechanisms (mtb) and zinc transportation (znt1) were affected only in cells exposed to ZnO NPs, while tight junction proteins (zo1 and cldn1), and apoptosis protein p53 were overexpressed only in cells exposed to the mixture. Osmoregulation (Na + /K + ATPase gene expression) was not affected by the tested conditions. The overall results suggest that the toxic effects of ZnO and TiO2 NPs in the mixture were significantly enhanced and could result in the disruption of the gill epithelium integrity. This study provides new insights into the combined effects of commonly used nanoparticles, emphasizing the importance of further investigating how their toxicity may be influenced in mixtures.

Accessible Double Nanohole Raman Tweezer Analysis of Single Nanoparticles.

Raman spectroscopy allows for material characterization of nanoparticles; however, probing individual nanoparticles requires an efficient way of isolating and enhancing the signal. Past works have used optical trapping with nanoapertures in metal films to measure the Raman spectra of individual nanoparticles; however, those works required custom laser tweezer systems that provided a transmission signal to verify trapping events as well as costly top-down nanofabrication. Here, we trapped Titania nanoparticles in a commercial Raman system using double nanoholes (DNH) and measured their spectra while trapped. The microscope camera allowed for measuring the trapping event in reflection mode, and a simultaneous Raman spectrum was recorded to allow for material characterization. The Raman signal was comparable to a past work that used particles a million times larger in volume without utilizing double nanoholes, and all other features were similar. The DNHs were created with a colloidal lithography technique and identified in the microscope, as confirmed by electron microscopy registration. Therefore, this approach allows a simple way of characterizing the Raman signal of individual nanoparticles while in solution by using existing commercial Raman systems.

Functionalization of Polypropylene by TiO2 Photocatalytic Nanoparticles: On the Importance of the Surface Oxygen Plasma Treatment.

A new two-step method for developing a nanocomposite of polypropylene (PP) decorated with photocatalytically active TiO2 nanoparticles (nTiO2) is proposed. This method involves the low-temperature plasma functionalization of polypropylene followed by the ultrasound-assisted anchoring of nTiO2. The nanoparticles, polymeric substrate, and resultant nanocomposite were thoroughly characterized using nanoparticle tracking analysis (NTA), microscopic observations (SEM, TEM, and EDX), spectroscopic investigations (XPS and FTIR), thermogravimetric analysis (TG/DTA), and water contact angle (WCA) measurements. The photocatalytic activity of the nanocomposites was evaluated through the degradation of methyl orange. The individual TiO2 nanoparticles ranged from 2 to 6 nm in size. The oxygen plasma treatment of PP generated surface functional groups (mainly -OH and -C=O), transforming the surface from hydrophobic to hydrophilic, which facilitated the efficient deposition of nTiO2. Optimized plasma treatment and sonochemical deposition parameters resulted in an active photocatalytic nTiO2/PP system, degrading 80% of the methyl orange under UVA irradiation in 200 min. The proposed approach is considered versatile for the functionalization of polymeric materials with photoactive nanoparticles and, in a broader perspective, can be utilized for the fabrication of self-cleaning surfaces.

Imaging Dissolution Dynamics of Individual NaCl Nanoparticles during Deliquescence with In Situ Transmission Electron Microscopy.

Water vapor condensation on hygroscopic aerosol particles plays an important role in cloud formation, climate change, secondary aerosol formation, and aerosol aging. Conventional understanding considers deliquescence of nanosized hygroscopic aerosol particles a nearly instantaneous solid to liquid phase transition. However, the nanoscale dynamics of water condensation and aerosol particle dissolution prior to and during deliquescence remain obscure due to a lack of high spatial and temporal resolution single particle measurements. Here we use real time in situ transmission electron microscopy (TEM) imaging of individual sodium chloride (NaCl) nanoparticles to demonstrate that water adsorption and aerosol particle dissolution prior to and during deliquescence is a multistep dynamic process. Water condensation and aerosol particle dissolution was investigated for lab generated NaCl aerosols and found to occur in three distinct stages as a function of increasing relative humidity (RH). First, a < 100 nm water layer adsorbed on the NaCl cubes and caused sharp corners to dissolve and truncate. The water layer grew to several hundred nanometers with increasing RH and was rapidly saturated with solute, as evidenced by halting of particle dissolution. Adjacent cube corners displayed second-scale curvature fluctuations with no net particle dissolution or water layer thickness change. We propose that droplet solute concentration fluctuations drove NaCl transport from regions of high local curvature to regions of low curvature. Finally, we observed coexistence of a liquid water droplet and aerosol particle immediately prior to deliquescence. Particles dissolved discretely along single crystallographic directions, separated by few second lag times with no dissolution. This work demonstrates that deliquescence of simple pure salt particles with sizes in the range of 100 nm to several microns is not an instantaneous phase transition and instead involves a range of complex dissolution and water condensation dynamics.

Plasmon-mediated photocatalytic conversion in Au or Ag nanorod aggregates by surface-enhanced Raman spectroscopy

Plasmonic nanoparticles (NPs) hold considerable potential as photocatalysts owing to their robust light–matter interactions across diverse electromagnetic wavelengths, which significantly influence the photophysical characteristics of the adjacent molecular entities. Despite the widespread use of noble-metal NPs in surface-enhanced Raman scattering (SERS) applications, little is known about the kinetics of nanoparticle aggregation and how it affects their configurations. This study investigates the plasmon-driven photochemical conversion of 4-nitrobenzenethiol (NBT) to 4,4′-dimercaptoazobenzene (DMAB) on Au and Ag nanorods (NRs) through SERS. Significantly, photoconversion phenomena were observed on Ag NRs but not on Au NRs upon laser excitation at 633 nm. Finite-difference time-domain simulations revealed the presence of stronger electromagnetic fields on Ag NRs than on Au NRs. The aspect ratios and gaps between individual NPs in dimer configurations were determined to elucidate their effects on electromagnetic fields. The Ag NR dimer with an end-to-end configuration, an aspect ratio of 3.3, and a 1-nm gap exhibited the highest enhancement factor of 1.05 × 1012. Our results demonstrate that the primary contribution from diverse configurations in NR aggregates is the end-to-end configuration. The proposed NP design with adjustable parameters is expected to advance research in plasmonics, sensing, and wireless communications. These findings also contribute to the understanding of plasmon-driven photochemical processes in metallic nanostructures.

Tracking surface charge dynamics on single nanoparticles.

Surface charges play a fundamental role in physics and chemistry, in particular in shaping the catalytic properties of nanomaterials. However, tracking nanoscale surface charge dynamics remains challenging due to the involved length and time scales. Here, we demonstrate time-resolved access to the nanoscale charge dynamics on dielectric nanoparticles using reaction nanoscopy. We present a four-dimensional visualization of the spatiotemporal evolution of the charge density on individual SiO2 nanoparticles under strong-field irradiation with femtosecond-nanometer resolution. The initially localized surface charges exhibit a biexponential redistribution over time. Our findings reveal the influence of surface charges on surface molecular bonding through quantum dynamical simulations. We performed semi-classical simulations to uncover the roles of diffusion and charge loss in the surface charge redistribution process. Understanding nanoscale surface charge dynamics and its influence on chemical bonding on a single-nanoparticle level unlocks an increased ability to address global needs in renewable energy and advanced health care.

Atomic Layer Deposition of Noble Metal Nanoparticles for Electrocatalytic Applications

Noble metals such as Pt, Ru, Pd, Ir, etc., have superior performance for various catalytic applications [1]. Due to their scarcity, efforts were being made to reduce the mass/loading or replace these noble metals. Atomic Layer Deposition (ALD) is one among the best technique to facilitate lowering of loading mass on a support of interest [2,3]. Due to the governing surface energy variations between noble metals and support surfaces, the growth initiates as nanoparticles (NP) and with a further increase in ALD cycles the agglomeration among NP’s dominates over the individual NP size increase, thus developing thin films of relatively higher thickness.For electrocatalytic applications, it is important to choose the right substrates. Among available substrates, carbon papers and titania nanotube layers are best choices considering their physio-chemical properties, availability and low costs incurred.The uniform decoration of these substrates by NPs of catalysts proved to be highly efficient in electrocatalysis, as shown in our recent papers [3-5].The presentation will introduce and describe the synthesis of different noble metal NPs by ALD on important substrates. It will also include the corresponding physical and electrochemical characterization and encouraging results obtained in electrocatalysis.

Disorder and demixing in bidisperse particle systems assembling bcc crystals.

Colloidal and nanoparticle self-assembly enables the creation of ordered structures with a variety of electronic and photonic functionalities. The outcomes of the self-assembly processes used to synthesize such structures, however, strongly depend on the uniformity of the individual nanoparticles. Here, we explore the simplest form of particle size dispersity-bidispersity-and its impact on the self-assembly process. We investigate the robustness of self-assembling bcc-type crystals via isotropic interaction potentials in binary systems with increasingly disparate particle sizes by determining their terminal size ratio-the most extreme size ratio at which a mixed binary bcc crystal forms. Our findings show that two-well pair potentials produce bcc crystals that are more robust with respect to particle size ratio than one-well pair potentials. This suggests that an improved self-assembly process is accomplished with a second attractive length scale encoded in the particle-particle interaction, which stabilizes the second-nearest neighbor shell. In addition, we document qualitative differences in the process of ordering and disordering: in bidisperse systems of particles interacting via one-well potentials, we observe a breakdown of order prior to demixing, while in systems interacting via two-well potentials, demixing occurs first and bcc continues to form in parts of the droplet down to low size ratios.