Surface Of Metal Nanoparticles Research Articles

Microenvironment of MOF Channel Coordination with Pt NPs for Selective Hydrogenation of Unsaturated Aldehydes

Surface and interface states of noble metal nanoparticles (MNPs), closely related to the catalytic performance, have been of great concern to academics in the field of catalysis. The catalytic prop...

Photocatalytic properties of supramolecular nanoassociates based on gold and platinum nanoparticles, capped by amphiphilic calix[4]resorcinarenes, towards organic dyes

The synthesis of colloidal platinum nanoparticles (PtNPs) (dcore≈1-40 nm) in an aqueous solution was carried out using amido(dimethyl)amino- and carboxy- calix[4]resorcinarenes with alkyl substituents on the lower rim as stabilizer. The nanoparticles were characterized by spectrophotometry, IR, TEM, DLS, PXRD and SAXS. It was shown that PtNPs and gold nanoparticles (AuNPs) obtained, stabilized by calix[4]resorcinarenes, demonstrate the photocatalytic activity in the photodegradation of methyl orange and rhodamine B toxic dyes under visible light irradiation. The rate constants of catalytic reaction (K1, min−1) and activity of nanocatalysts (K2, min−1 mol−1) were calculated. It was found that size of metal core, structure of macrocycle stabilizing the surface of metal nanoparticles, its ability to form self-associates and bind dye molecules define the rate of dye photodegradation reaction. The study of the interaction of PtNPs and AuNPs capped with amidoamine macrocycles with organic photolinkers by spectrophotometry and fluorescence showed the binding of photolinkers by macrocycles, PtNPs and AuNPs. The photocatalytic activity of obtained cooperative nanoassociates was studied. The addition of photolinkers leads to both an increase and a decrease in the reaction rate, depending on the structure of linker and macrocycle. An increase in the reaction rate occurs due to the formation of photoactive supramolecular nanoassociates and the additional photosensitizing action of the photolinker on the surface of a metal nanoparticle. Such hybrid nanocatalysts based on metal nanoparticle and calixresorcinarenes have the potential to be used in the field of effective photodegradation of toxic water pollutants.

Correlative Study of Enhanced Excitonic Emission in ZnO Coated with Al Nanoparticles using Electron and Laser Excitation

Recently, metal nanoparticle surface coatings have been found to significantly enhance the ultra-violet luminescence intensity from ZnO, providing a viable means to mitigate optical losses and improve LED performance. Although there is general agreement that resonantly excited Localized Surface Plasmons (LSPs) in metal nanoparticles can directly couple to excitons in the semiconductor increasing their spontaneous emission rate, the exact mechanisms involved in this phenomenon are currently not fully understood. In this work, LSP-exciton coupling in bulk and nanostructured ZnO coated with a 2 nm Al nanoparticle layer is investigated using correlative photoluminescence and depth-resolved cathodoluminescence and time-resolved photoluminescence spectroscopy. Temperature-resolved cathodoluminescence and photoluminescence measurements from 10 K to 250 K show free exciton (FX) emission enhancement factors up to 12x at 80 K, and reveal that the FX couple more efficiently to the LSPs compared to the localized donor-bound excitons. A strong polarization dependence between the LSPs and FX is observed where FX transitions are more strongly enhanced when polarized in the same direction as the electric field of the incident excitation, which is different for laser and electron beam sources. This result indicates that selective enhancement of the excitonic emission peaks in the ZnO coated with Al nanoparticles can be achieved by choosing the appropriate ZnO substrate orientation.

Flickering nanometre-scale disorder in a crystal lattice tracked by plasmonic flare light emission

The dynamic restructuring of metal nanoparticle surfaces is known to greatly influence their catalytic, electronic transport, and chemical binding functionalities. Here we show for the first time that non-equilibrium atomic-scale lattice defects can be detected in nanoparticles by purely optical means. These fluctuating states determine interface electronic transport for molecular electronics but because such rearrangements are low energy, measuring their rapid dynamics on single nanostructures by X-rays, electron beams, or tunnelling microscopies, is invasive and damaging. We utilise nano-optics at the sub-5nm scale to reveal rapid (on the millisecond timescale) evolution of defect morphologies on facets of gold nanoparticles on a mirror. Besides dynamic structural information, this highlights fundamental questions about defining bulk plasma frequencies for metals probed at the nanoscale.

Collectively induced exceptional points of quantum emitters coupled to nanoparticle surface plasmons

Exceptional points, resulting from non-Hermitian degeneracies, have the potential to enhance the capabilities of quantum sensing. Thus, finding exceptional points in different quantum systems is vital for developing such future sensing devices. Taking advantage of the enhanced light-matter interactions in a confined volume on a metal nanoparticle surface, here we theoretically demonstrate the existence of exceptional points in a system consisting of quantum emitters coupled to a metal nanoparticle of subwavelength scale. By using an analytical quantum electrodynamics approach, exceptional points are manifested as a result of a strong-coupling effect and observable in a drastic splitting of originally coalescent eigenenergies. Furthermore, we show that exceptional points can also occur when a number of quantum emitters are collectively coupled to the dipole mode of localized surface plasmons. Such a quantum collective effect not only relaxes the strong-coupling requirement for an individual emitter, but also results in a more stable generation of the exceptional points. Furthermore, we point out that the exceptional points can be explicitly revealed in the power spectra. A generalized signal-to-noise ratio, accounting for both the frequency splitting in the power spectrum and the system's dissipation, shows clearly that a collection of quantum emitters coupled to a nanoparticle provides a better performance of detecting exceptional points, compared to that of a single quantum emitter.

Hot-carrier dynamics in catalysis

Abstract

Pulsed plasma surface functionalized nanosilver for gene delivery.

Lack of suitable surface properties in biomaterials is an acute challenge for their utilization in nucleic acid delivery, since surface plays a vital role in cell adhesion/uptake and immunity. Low pressure cold plasma is a promising technology for functionalization and surface modification of materials, in an effective, environment friendly and economical way. In this investigation we have modified the surface of silver nanoparticles (AgNPs) with chitosan biopolymer, using plasma treatment, to extend their application scope in intracellular DNA delivery. The plasma functionalized; chitosan modified AgNPs (MetaloPolymeric Nanocarriers; MPNCs) possessed superior biocompatibility compared to unmodified AgNPs. Carboxylic groups were incorporated on the surface of nanosilver using 3600 rotating pulsed plasma reactor and acrylic acid vapors were used as precursor gas. Pulsed plasma polymerization process was optimized with respect to working pressure of the system, duty cycle for pulsing, time of treatment and flow rate. Biocompatibility of the plasma functionalized nanosilver was enhanced by coupling it with Chitosan Oligosaccharide (COS), using EDC (1-Ethyl-3-(3-dimethylaminopropyl) carbodiimide) to form amide linkages. The resulting MPNCs showed high cell viability and bio-stability, which was attributed to plasma processing of nanosilver and its association with COS. In vitro cellular studies illustrated significant uptake of nanoplexes. The study suggested the potential of plasma functionalization for manipulating surfaces of metallic nanoparticles to enhance their application in intracellular gene delivery.

Comment on "Thermal effects - an alternative mechanism for plasmon-assisted photocatalysis" by Y. Dubi, I. W. Un and Y. Sivan, Chem. Sci., 2020, 11, 5017.

A range of chemical reactions occurring on the surfaces of metal nanoparticles exhibit enhanced rates under plasmonic excitation. It is not straightforward to distinguish between photochemical and photothermal effect using Arrhenius fitting of the reaction rates alone.

Investigating Polymer Transformation during the Encapsulation of Metal Nanoparticles by Polystyrene-b-poly(acrylic acid) in Colloids

The colloidal self-assembly method holds great potential for large-scale synthesis at low expense of energy as compared to methods that assemble molecules by manipulating building blocks one after another. The development of the colloidal method, however, requires careful and intelligent design of the single building blocks as numerous degrees of freedom like isotropic nanoparticles (NPs) generally form highly repetitive, lattice-like structures or random aggregates upon self-assembly because of their identical surfaces throughout. Specifically, it is an interesting direction that if one can precisely control the localization of surface functionalities (i.e., ligands or polymer shells) on the NPs, a plethora of self-assembled structures (e.g., chains, sheets, rings, twisted, and even staircase structures) would be possible. Despite numerous simulations and modeling for this type of NPs, just a handful literature studies reported the controlling synthesis of metal-polymer patchy NPs through polymer shell shrinking/transformation in colloids. However, there are no detailed control experiments showing the mechanism of this polymer shell shrinking or transformation phenomenon. With the absence of a fundamental understanding of the driving forces and interactions between metal NP surface ligands and the hydrophobic polymer shell domain, simple and efficient design and synthesis of unique metal-polymer hybrid nanostructures are still obscure. Here, we report a detailed mechanistic study on the polymer shell transformation by using different types of surface ligands in encapsulation of metal NPs by polymer shells. The polymer shell transformation dynamic is studied after postheating treatment. The polymer shell transformation/shrinking on the metal NP surface depends on its surface ligand size being applied in the encapsulation step (polymer-ligand hydrophobic interaction effect). Longer-chain ligands provide stronger interactions between NPs and the hydrophobic domain of the polymer shell, which inhibits the polymer shell transformation. In contrast, short-chain ligands lead to weaker interactions, which assist in the polymer shell transformation. By understanding the underlying mechanisms, many new types of NPs, such as metal-polymer core-shell NPs, metal-polymer Janus NPs, silica-metal-polymer hybrid NPs, and silica-metal-polymer flower-like NPs have been synthesized for the first time. A new bottom-up platform for the synthesis of anisotropic NPs with the ability to control the patches in a precise manner has been created, which will benefit both nanotechnology (such as self-assembly in the nanoscale) and applications such as selective detection of the underlying ligands on the metal surface by using a surface-enhanced Raman spectrum study.

Physical principles of the formation of a nanoparticle electric double layer in metal hydrosols

The Brownian dynamics method is employed to study the formation of an electrical double layer (EDL) on the metal nanoparticle (NP) surface in hydrosols during adsorption of electrolyte ions from the interparticle medium. Also studied is the charge accumulation by NPs in the Stern layer. To simulate the process of the formation of EDL, we took into account the effect of image forces and specific adsorption, dissipative and random forces, and the degree of hydration of adsorbed ions on the EDL structure. The employed model makes it possible to determine the charge of NPs and the structure of EDL. For the first time, the charge of both the diffuse part of EDL and the dense Stern layer has been determined. A decrease in the electrolyte concentration (below c < 0.1 mol/l) has been found to result in dramatic changes in the formation of the Stern layer.

Protein-docking strategy boosting Raman detection sensitivity for aristolochic acid I

As one of the most potent carcinogens, aristolochic acid I (AAI) can be founded in many plants, which are widely used as raw materials in traditional Chinese medicine. Surface enhanced Raman scattering (SERS) method would be developed to detect the AAI in rapid way. However, hydrophobic AAI molecule with small scattering section hardly approaches onto the surface of metal nanoparticles, resulting in poor Raman detection sensitivity. In this work, bovine serum albumin (BSA) decorated silver nanoparticles (Ag NPs) with core-shell structure (Ag@BSA NPs) are successfully synthesized. The molecular docking induced strong interaction between BSA and AAI is validated by molecular simulation and Ag@BSA NPs could actively capture AAI and anchor the target molecule into the hot spots of Ag NPs, which greatly improves SERS response of AAI. The dynamic linear range for SERS detection of AAI is from 0.5 to 50 μM (R2 = 0.9910) and the lowest detectable concentration of 0.28 μM is reached, which meeting the strict limitation of national standard regulation for AAI in cosmetic products. In addition, the method is applied for AAI determination in skin care products and good results are achieved.

Electrocatalysis of Oxygen Reduction Reaction on Shape-Controlled Pt and Pd Nanoparticles-Importance of Surface Cleanliness and Reconstruction.

Shape-controlled precious metal nanoparticles have attracted significant research interest in the recent past due to their fundamental and scientific importance. Because of their crystallographic-orientation-dependent properties, these metal nanoparticles have tremendous implications in electrocatalysis. This review aims to discuss the strategies for synthesis of shape-controlled platinum (Pt) and palladium (Pd) nanoparticles and procedures for the surfactant removal, without compromising their surface structural integrity. In particular, the electrocatalysis of oxygen reduction reaction (ORR) on shape-controlled nanoparticles (Pt and Pd) is discussed and the results are analyzed in the context of that reported with single crystal electrodes. Accepted theories on the stability of precious metal nanoparticle surfaces under electrochemical conditions are revisited. Dissolution, reconstruction, and comprehensive views on the factors that contribute to the loss of electrochemically active surface area (ESA) of nanoparticles leading to an inevitable decrease in ORR activity are presented. The contribution of adsorbed electrolyte anions, in-situ generated adsorbates and contaminants toward the ESA reduction are also discussed. Methods for the revival of activity of surfaces contaminated with adsorbed impurities without perturbing the surface structure and its implications to electrocatalysis are reviewed.

A Tunable Nanoplatform of Nanogold Functionalised with Angiogenin Peptides for Anti-Angiogenic Therapy of Brain Tumours.

Angiogenin (ANG), an endogenous protein that plays a key role in cell growth and survival, has been scrutinised here as promising nanomedicine tool for the modulation of pro-/anti-angiogenic processes in brain cancer therapy. Specifically, peptide fragments from the putative cell membrane binding domain (residues 60–68) of the protein were used in this study to obtain peptide-functionalised spherical gold nanoparticles (AuNPs) of about 10 nm and 30 nm in optical and hydrodynamic size, respectively. Different hybrid biointerfaces were fabricated by peptide physical adsorption (Ang60–68) or chemisorption (the cysteine analogous Ang60–68Cys) at the metal nanoparticle surface, and cellular assays were performed in the comparison with ANG-functionalised AuNPs. Cellular treatments were performed both in basal and in copper-supplemented cell culture medium, to scrutinise the synergic effect of the metal, which is another known angiogenic factor. Two brain cell lines were investigated in parallel, namely tumour glioblastoma (A172) and neuron-like differentiated neuroblastoma (d-SH-SY5Y). Results on cell viability/proliferation, cytoskeleton actin, angiogenin translocation and vascular endothelial growth factor (VEGF) release pointed to the promising potentialities of the developed systems as anti-angiogenic tunable nanoplaftforms in cancer cells treatment.

Size and aspect ratio dependency of sensitivity of ellipsoidal metal nanoparticle based liquid sensor

Detection of bio chemical species in a liquid is very important for research and technical purposes. In the last decade, metallic nanoparticles have been shown to be potential for such measurement. Resonance wavelength (or frequency) of free electron oscillation on metallic nanoparticle surface is very sensitive to tiny changes of its surrounding environment. Change in surrounding medium shifts the resonance wavelength with a slope determined mainly by the size and geometry of nanoparticle. We numerically optimized size and aspect ratio of silver and gold nanoparticles to obtain the highest sensing sensitivity. Here, sensitivity is defined as the slope of resonance wavelength on refractive index of liquid. We found that size, aspect ratio, and material of metal affect sensing sensitivity of metal nanoparticle based sensor significantly.

Plasmon-Driven Catalysis on Molecules and Nanomaterials

As a new class of photocatalysts, plasmonic noble metal nanoparticles with the unique ability to harvest solar energy across the entire visible spectrum and produce effective energy conversion have been explored as a promising pathway for the energy crisis. The resonant excitation of surface plasmon resonance allows the nanoparticles to collect the energy of photons to form a highly enhanced electromagnetic field, and the energy stored in the plasmonic field can induce hot carriers in the metal. The hot electron-hole pairs ultimately dissipate by coupling to phonon modes of the metal nanoparticles, resulting in a higher lattice temperature. The plasmonic electromagnetic field, hot electrons, and heat can catalyze chemical reactions of reactants near the surface of the plasmonic metal nanoparticles. This Account summarizes recent theoretical and experimental advances on the excitation mechanisms and energy transfer pathways in the plasmonic catalysis on molecules. Especially, current advances on plasmon-driven crystal growth and transformation of nanomaterials are introduced. The efficiency of the chemical reaction can be dramatically increased by the plasmonic electromagnetic field because of its higher density of photons. Similar to traditional photocatalysis, energy overlap between the plasmonic field and the HOMO-LUMO gap of the reactant is needed to realize resonant energy transfer. For hot-carrier-driven catalysis, hot electrons generated by plasmon decay can be transferred to the reactant through the indirect electron transfer or direct electron excitation process. For this mechanism, the energy of hot electrons needs to overlap with the unoccupied orbitals of the reactant, and the particular chemical channel can be selectively enhanced by controlling the energy distribution of hot electrons. In addition, the local thermal effect following plasmon decay offers an opportunity to facilitate chemical reactions at room temperature. Importantly, surface plasmons can not only catalyze chemical reactions of molecules but also induce crystal growth and transformation of nanomaterials. As a new development in plasmonic catalysis, plasmon-driven crystal transformation reveals a more powerful aspect of the catalysis effect, which opens the new field of plasmonic catalysis. We believe that this Account will promote clear understanding of plasmonic catalysis on both molecules and materials and contribute to the design of highly tunable catalytic systems to realize crystal transformations that are essential to achieve efficient solar-to-chemical energy conversion.

Direct observation of single plasmonic metal nanoparticle reaction in microcolumn with chromatic-aberration-free LASER light-sheet scattering imaging.

Direct observation and characterization of individual noble metal nanoparticles (MNPs) and their chemical reactions have attracted much attention owing to their unique physical and chemical properties and extensive applications. To achieve high-throughput information-rich evaluation of MNPs, it would be advantageous to combine highly efficient microcolumn separation technology with on-column high resolution plasmonic imaging technique. Here, with a chromatic aberration-suppressed supercontinuum laser light-sheet scattering imaging system and colorimetric detection, we monitored oxidation process of single gold nanorods inside a capillary under gravity driven flow, and observed heterogenous reaction intermediates and pathways for different MNP surface modifications. The results suggest that molecular interactions and bindings with MNPs have a significant impact on their reaction kinetics. This high-throughput on-line single particle detection technique could be potentially applied to chemical and biochemical reaction studies of other MNPs.

Ultrasound assisted-phytofabricated Fe3O4 NPs with antioxidant properties and antibacterial effects on growth, biofilm formation, and spreading ability of multidrug resistant bacteria

Complicated issue in infectious illnesses therapy is increasing of multidrug resistant (MDR) bacteria and biofilms in bacterial infections. In this way, emerging of nanotechnology as a new weapon specifically in the cases of metal nanoparticle (MNPs) synthesis and MNPs surface modification has obtained more attention. In this study, ultrasound-assisted green synthesis method was utilized for the preparation of Fe3O4 NPs with novel shape (dendrimer) through leaf aqueous extract of Artemisia haussknechtii Boiss. Ultraviolet–visible spectroscopy, energy dispersive X-ray spectroscopy (EDX), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), atomic force microscopic (AFM), X-ray diffraction (XRD) techniques were applied for MNPs physicochemical characterization. Also, disc diffusion assay, minimum inhibitory concentration (MIC), minimum bactericidal concentration (MBC), planktonic and biofilm morphology of three pathogenic bacteria involving Serratia marcescens ATCC 13880, Escherichia coli ATCC 25922, and methicillin-resistant Staphylococcus aureus (MRSA) were evaluated upon treatment of Fe3O4 NPs as antiplanktonic and antibiofilm analysis. Results showed efficient antiplanktonic and antibiofilm activities of biosynthesized Fe3O4 NPs with average diameter size of 83.4 nm. Reduction in biofilm formation of S. aureus ATCC under Fe3O4 NPs stress was significant (66%) in higher MNPs concentration (100 μg/mL). In addition, as first report, spreading ability of S. aureus as important factor in colony expansion on culture medium was reduced by increasing of Fe3O4 NPs. Present study demonstrates striking antiplanktonic, antibiofilm, antispreading mobility and antioxidant aspects of one-pot biosynthesized Fe3O4 NPs with novel shape.

Two-Dimensional Infrared Spectroscopy Reveals Molecular Self-Assembly on the Surface of Silver Nanoparticles

The conformation of molecules, peptides, and proteins, self-assembled into structured monolayers on the surface of metal nanoparticles (NPs), can strongly affect their properties and use in chemical or nanobiomedical applications. Elucidating molecular conformations on the NP surface is highly challenging, and the microscopic details mostly remain elusive. Using polarization-selective third-order two-dimensional ultrafast infrared spectroscopy, we revealed the highly ordered intermolecular structure of γ-tripeptide glutathione on the surface of silver NPs in aqueous solution. Glutathione is an antioxidant thiol abundant in living cells; it is extensively used in NP chemistry and related research. We identified conditions where the interaction of glutathione with the NP surface facilitates formation of a β-sheet-like structure enclosing the NPs. A spectroscopic signature associated with the assembly of β-sheets into an amyloid fibril-like structure was also observed. Remarkably, the interaction with the metal surface promotes formation of a fibril-like structure by a small peptide involving only two amino acids.

Intermolecular energy flows between surface molecules on metal nanoparticles.

Three model systems are designed to investigate energy transport between molecules on metal nanoparticle surfaces. Energy is rapidly transferred from one carbon monoxide (CO) molecule to another CO molecule or an organic molecule on adjacent surface sites of 2 nm Pt particles within a few picoseconds. On the contrary, energy flow from a surface organic molecule to an adjacent CO molecule is significantly slower and, in fact, within experimental sensitivity and uncertainty the transfer is not observed. The energy transport on particle surfaces (about 2 km s-1) is almost ten times faster than inside a molecule (200 m s-1). The seemingly perplexing observations can be well explained by the combination of electron/vibration and vibration/vibration coupling mechanisms, which mediate molecular energy dynamics on metal nanoparticle surfaces: the strong electron/vibration coupling rapidly converts CO vibrational energy into heat that can be immediately sensed by nearby molecules; but the vibration/vibration coupling dissipates the vibrational excitation in the organic molecule as low-frequency intramolecular vibrations that may or may not couple to surface electronic motions.

Plasmonic Effects in Noble Metal-liquid Metal Based Nanoparticles

In the era of flexible and foldable devices, liquid metals emerge as a champion because they are being liquid at or near room temperature in addition to having high electrical and thermal conductivities. Plasmonic resonance occurs when conduction band electrons on metal nanoparticle surface collectively oscillates with same frequency as that irradiated light. This plasmonic resonance has attracted great attention because of large electromagnetic field enhancements near metal nanoparticle and the regulating resonance wavelength with change in material, size, shape and surrounding medium of metallic nanoparticle. Incorporation of liquid metal nanoparticles in plasmonics provides unique properties towards sensing (heart rate monitors etc.) which can become wearable. So, developing liquid metal based low-cost and large-scale plasmonic nanostructures may provide more optical efficiencies, fast kinetics, low temperature processing, versatility, easy embedding in structures and stretchy devices. Present work focuses on literature review highlighting the study of optical properties (absorption and scattering efficiencies, LSPR tunability, Figure of Merit (FOM) and Refractive Index Sensitivity (RIS)) of noble metal-liquid metal nanostructures and future scope of the field. Simulations can be performed on the basis of Mie Theory for spherical nanoparticles and by DDA/FDTD method for non-spherical particles or arrays. The results can help to optimize the plasmonic nanostructures of suitable material, size and shape according to the need of application in particular region of EM spectrum.