Nm In Core Diameter Research Articles

Umbrella‐Shaped Amphiphiles: Internal Alkylation of an Aromatic Micelle and Its Impact on Cavity Features

AbstractTo develop new hybrid micelles with alkyl/polyaromatic core–shell structures, we synthesized umbrella‐shaped amphiphiles bearing a bent anthracene dimer with a linear alkyl chain (i.e., octyl and hexadecyl groups). The amphiphiles quantitatively assemble into spherical micelles (~2–3 nm in core diameter), possessing an alkylated cavity surrounded by a polyaromatic framework, in water. The alkylation significantly enhances the stability of the micellar structures against dilution (up to 9 μM) and heat (up to >120 °C). The highly condensed hexadecyl core of the hybrid micelle, as indicated by solvatochromic guest probes, displays increased uptake ability toward large alkylated metallodyes. Interestingly, efficient uptake of aromatic macrocycles (i.e., [n]cycloparaphenylenes) by the present micelle provides pseudorotaxane‐shaped host–guest composites with high emissivity (ΦF=up to 35 %). Internal multi‐alkylation of an aromatic micelle can thus successfully enhance its assembly stability/guest uptake functions.

Umbrella-Shaped Amphiphiles: Internal Alkylation of an Aromatic Micelle and Its Impact on Cavity Features.

To develop new hybrid micelles with alkyl/polyaromatic core-shell structures, we synthesized umbrella-shaped amphiphiles bearing a bent anthracene dimer with a linear alkyl chain (i.e., octyl and hexadecyl groups). The amphiphiles quantitatively assemble into spherical micelles (~2-3 nm in core diameter), possessing an alkylated cavity surrounded by a polyaromatic framework, in water. The alkylation significantly enhances the stability of the micellar structures against dilution (up to 9 μM) and heat (up to >120 °C). The highly condensed hexadecyl core of the hybrid micelle, as indicated by solvatochromic guest probes, displays increased uptake ability toward large alkylated metallodyes. Interestingly, efficient uptake of aromatic macrocycles (i.e., [n]cycloparaphenylenes) by the present micelle provides pseudorotaxane-shaped host-guest composites with high emissivity (ΦF=up to 35 %). Internal multi-alkylation of an aromatic micelle can thus successfully enhance its assembly stability/guest uptake functions.

Cholesterol Hinders the Passive Uptake of Amphiphilic Nanoparticles into Fluid Lipid Membranes.

Plasma membranes represent pharmacokinetic barriers for the passive transport of site-specific drugs within cells. When engineered nanoparticles (NPs) are considered as transmembrane drug carriers, the plasma membrane composition can affect passive NP internalization in many ways. Among these, cholesterol-regulated membrane fluidity is probably one of the most biologically relevant. Herein, we consider small (2–5 nm in core diameter) amphiphilic gold NPs capable of spontaneously and nondisruptively entering the lipid bilayer of plasma membranes. We study their incorporation into model 1,2-dioleoyl-sn-glycero-3-phosphocholine membranes with increasing cholesterol content. We combine dissipative quartz crystal microbalance experiments, atomic force microscopy, and molecular dynamics simulations to show that membrane cholesterol, at biologically relevant concentrations, hinders the molecular mechanism for passive NP penetration within fluid bilayers, resulting in a dramatic reduction in the amount of NP incorporated.

Toward Active-Site Tailoring in Heterogeneous Catalysis by Atomically Precise Metal Nanoclusters with Crystallographic Structures.

Heterogeneous catalysis involves solid-state catalysts, among which metal nanoparticles occupy an important position. Unfortunately, no two nanoparticles from conventional synthesis are the same at the atomic level, though such regular nanoparticles can be highly uniform at the nanometer level (e.g., size distribution ∼5%). In the long pursuit of well-defined nanocatalysts, a recent success is the synthesis of atomically precise metal nanoclusters protected by ligands in the size range from tens to hundreds of metal atoms (equivalently 1-3 nm in core diameter). More importantly, such nanoclusters have been crystallographically characterized, just like the protein structures in enzyme catalysis. Such atomically precise metal nanoclusters merge the features of well-defined homogeneous catalysts (e.g., ligand-protected metal centers) and enzymes (e.g., protein-encapsulated metal clusters of a few atoms bridged by ligands). The well-defined nanoclusters with their total structures available constitute a new class of model catalysts and hold great promise in fundamental catalysis research, including the atomically precise size dependent activity, control of catalytic selectivity by metal structure and surface ligands, structure-property relationships at the atomic-level, insights into molecular activation and catalytic mechanisms, and the identification of active sites on nanocatalysts. This Review summarizes the progress in the utilization of atomically precise metal nanoclusters for catalysis. These nanocluster-based model catalysts have enabled heterogeneous catalysis research at the single-atom and single-electron levels. Future efforts are expected to achieve more exciting progress in fundamental understanding of the catalytic mechanisms, the tailoring of active sites at the atomic level, and the design of new catalysts with high selectivity and activity under mild conditions.

Nanoparticle core size optimization for magnetic particle imaging

In magnetic particle imaging (MPI), the changing magnetization of magnetic nanoparticle (MNP) tracers subjected to an alternating magnetic field is detected. The physical properties of the MNP tracers have a direct effect on the quality of the resulting signal. In order to improve MPI image resolution and sensitivity, optimizing these properties, in particular the MNP core size, is essential. In this work, we investigate the existence of an optimal MNP core size for MPI using stochastic simulations of Langevin equations, supported by magnetic particle spectroscopy (MPS) measurements of highly monodisperse single-core nanoparticles with carefully tailored core sizes. We demonstrate that once the MNP core diameter exceeds around 28 nm (with the exact value depending on applied field properties and non-magnetic nanoparticle coating), relaxation effects will begin to dominate. Furthermore, as nanoparticle size is increased, interparticle interactions make it difficult to stabilize the particles in water and maintain their monodispersity. Taken together, we conclude that 28 nm in core diameter is an optimal size for single-core, monodisperse, magnetite particles used in MPI.

A Polyaromatic Gemini Amphiphile That Assembles into a Well-Defined Aromatic Micelle with Higher Stability and Host Functions.

A gemini-type amphiphilic molecule, constituted of two V-shaped polyaromatic amphiphiles linked by a linear acetylene spacer, was synthesized. The gemini amphiphile assembles into a well-defined aromatic micelle (ca. 2 nm in core diameter), providing higher stability in water even at low concentration (0.09 mm) and high temperature (>130 °C). Unlike common gemini amphiphiles with aliphatic chains, the present amphiphile and its micellar assembly emit green and orange fluorescence (ΦF =33 and 9 %), respectively. Despite strong and multiple π-stacks of the polyaromatic panels of the amphiphiles, the water-soluble gemini aromatic micelle incorporates medium-size to large hydrophobic compounds into the frameworks. Interestingly, the guest binding capability toward large planar molecules was enhanced by more than two times through the pre-encapsulation of spherical molecules in the cavity.

A Polyaromatic Gemini Amphiphile That Assembles into a Well‐Defined Aromatic Micelle with Higher Stability and Host Functions

AbstractA gemini‐type amphiphilic molecule, constituted of two V‐shaped polyaromatic amphiphiles linked by a linear acetylene spacer, was synthesized. The gemini amphiphile assembles into a well‐defined aromatic micelle (ca. 2 nm in core diameter), providing higher stability in water even at low concentration (0.09 mm) and high temperature (>130 °C). Unlike common gemini amphiphiles with aliphatic chains, the present amphiphile and its micellar assembly emit green and orange fluorescence (ΦF=33 and 9 %), respectively. Despite strong and multiple π‐stacks of the polyaromatic panels of the amphiphiles, the water‐soluble gemini aromatic micelle incorporates medium‐size to large hydrophobic compounds into the frameworks. Interestingly, the guest binding capability toward large planar molecules was enhanced by more than two times through the pre‐encapsulation of spherical molecules in the cavity.

Coulomb blockade and Coulomb staircase behavior observed at room temperature

A single-electron transistor (SET) consists of source, drain, Coulomb island, and gate to modulate the number of electrons and control the current. For practical applications, it is important to operate a SET at room temperature. One proposal towards the ability to operate at room temperature is to decrease Coulomb island size down to a few nanometres. We investigate a SET using Sn-porphyrin (Sn-por) protected gold nanoparticles (AuNPs) with 1.4 nm in core diameter as a Coulomb island. The fabrication method of nanogap electrodes uses the combination of a top-down technique by electron beam lithography (EBL) and a bottom-up process through electroless gold plating (ELGP) as our group have described before. The electrical measurement was conducted at room temperature (300 K). From current–voltage (Id–Vd) characteristics, we obtained clear Coulomb blockade phenomena together with a Coulomb staircase due to a Sn-por protected gold NP as a Coulomb island. Experimental results of Id–Vd characteristics agree with a theoretical curve based on using the orthodox model. Clear dId/dVd peaks are observed in the Coulomb staircase at 9 K which suggest the electron transports through excited energy levels of Au NPs. These results are a big step for obtaining SETs that can operate at room temperature.

Chemically and thermally stable, emissive carbon dots as viable alternatives to semiconductor quantum dots for emissive nematic liquid crystal–nanoparticle mixtures with lower threshold voltage

ABSTRACTDispersions of chemically and thermally robust carbon dots (2.5 ± 0.5 nm in core diameter) were prepared and investigated by polarised optical microscopy, electro-optic measurements including dynamic tests and numerical simulations as well as fluorescence confocal microscopy. The carbon dots were prepared by a straightforward thermal decomposition method from citric acid and hexadecylamine, and they show typical excitation wavelength-dependent photoluminescence behaviour. All dispersions, ranging from 0.5 to 5.0 wt.%, showed lower values for isotropic–nematic phase transition temperature and broader isotropic–nematic biphasic temperature intervals with increasing carbon dot content in comparison to the neat material. Doping of the nematic host with the carbon dots resulted in lower values for the apparent threshold voltage and the elastic constants, but higher values for the rotational viscosity. At 2.5 wt.% and higher, carbon dots residing at the confining interfaces in planar cells induce an increasing initial pre-tilt of up to 8° at lower temperatures. Fluorescence confocal microscopy confirmed this, where the luminescence of the carbon dots permitted visualisation of the distribution of the carbon dots in the bulk with a noticeable, in some cases even pattern-like, segregation to the confining interfaces.

Towards integration of a liquid-filled fiber capillary for supercontinuum generation in the 1.2-2.4 μm range.

We demonstrate supercontinuum generation in unspliced as well as in integrated CS(2)-filled capillary fibers at different pump wavelengths of 1030 nm, 1510 nm, and 1685 nm. A novel method for splicing a liquid-filled capillary fiber to a standard single-mode optical fiber is presented. This method is based on mechanical splicing using a direct-laser written polymer ferrule using a femtosecond two-photon polymerization process. We maintain mostly single-mode operation despite the multi-mode capability of the liquid-filled capillaries. The generated supercontinua exhibit a spectral width of over 1200 nm and 1000 nm for core diameters of 5 μm and 10 μm, respectively. This is an increase of more than 50 percent compared to previously reported values in the literature due to improved dispersion properties of the capillaries.

Rapid detection of protein phosphatase activity using Zn(II)-coordinated gold nanosensors based on His-tagged phosphopeptides.

We report a rapid colorimetric assay to detect protein phosphatase (PP) activity based on the controlled assembly and disassembly of gold nanoparticles (AuNPs) via Zn(II)-specific coordination in the presence of His6-tagged phosphopeptides. Among divalent metal ions including Ni(II), Cu(II), Co(II), Mg(II), Mn(II), and Zn(II), only Zn(II) triggered a strong association between phosphopeptides with hexahistidine at a single end and nitrilotriacetic acid (NTA)-modified AuNPs (21.3 nm in core diameter), leading to the self-assembly of AuNPs and consequently changes in color of the AuNP solution. In contrast, unphosphorylated peptides and His6-deficient phosphopeptides did not change the color of the AuNP solution. As a result, protein phosphatase 1 (PP1) activity and its inhibition were easily quantified with high sensitivity by determining the extinction ratio (E520/E700) of colloidal AuNPs. Most importantly, this method was capable of detecting protein phosphatase 2A (PP2A) activity in immunoprecipitated plant extracts. Because PPs play pivotal roles in mediating diverse signal transduction pathways as primary effectors of protein dephosphorylation, we anticipate that our method will be applied as a rapid format method to analyze the activities of various PPs and their inhibition.

In Vivo Safety Evaluation of Polyarginine Coated Magnetic Nanovectors

Safety and efficacy are of critical importance to any nanomaterial-based diagnostic and therapy. The innocuity and functionality of a nanomaterial in vivo is largely dependent on the physicochemical properties of the material, particularly its surface coating. Here, we evaluated the influence of polycationic coating on the efficacy, clearance organ uptake, and safety of magnetic nanovectors designed for siRNA delivery. Polyethylene glycol (PEG) coated superparamagnetic iron oxide nanoparticles (NPs) of 12 nm in core diameter were modified with a polycationic coating of either poly-l-arginine (pArg) or polyethylenimine (PEI) and further covalently functionalized with siRNA oligonucleotides. The produced NP-pArg-siRNA and NP-PEI-siRNA nanovectors were similar in hydrodynamic size (21 and 22 nm, respectively) but significantly differed in zeta potentials (+2.1 mV and +29.8 mV, respectively). Fluorescence quantification assays revealed that the NP-pArg-siRNA nanovector was 3-fold more potent than NP-PEI-siRNA in delivering siRNA and 1.8-fold more effective in gene silencing when tested in rat C6 glioblastoma cells. In vivo, both nanovector formulations were similarly taken up by the spleen and liver as determined by histopathological and hemopathological assays. However, PEI coated nanovectors elicited severe hemoincompatibility and damage to the liver and spleen, while pArg coated nanovectors were found to be safe and tolerable. Combined, our findings suggest that polycationic coatings of pArg were more effective and safer than commonly used PEI coatings for preparation of nanovectors. The NP-pArg-siRNA nanovector formulation developed here shows great potential for in vivo based biomedical applications.

Gold nanoparticle-based fluorescence quenching via metal coordination for assaying protease activity

We report a gold nanoparticle (AuNP)-based fluorescence quenching system via metal coordination for the simple assay of protease activity. Carboxy AuNPs (5 nm in core diameter) functioned as both quenchers and metal chelators without requiring further modification with multidentate ligands; therefore, they were strongly associated with the hexahistidine regions of dye-tethered peptides in the presence of Ni(II) ions, leading to notable fluorescence quenching over the varying molar ratios of dye to AuNP. Upon the addition of matrix metalloproteinase-7 (MMP-7), the fluorescent intensity was efficiently recovered in one-pot mixture especially at 10:1–100:1 molar ratios of dye to AuNP. Consequently, the dequenching degree was dependent on the MMP-7 concentration in a hyperbolic manner, ranging from as low as 10 to 1,000 ng mL−1. In this regard, we anticipate that the developed system will give us a general way to construct nanoparticle–dye conjugates and will find applications in the analyses of many other proteases mediating significant biological processes with low background and high sensitivity.

Photoelectrochemical analysis of size-dependent electronic structures of gold clusters supported on TiO2

Size-dependent electronic structures around the Fermi level of glutathione-protected gold clusters (0.9-1.4 nm in core diameter) were analyzed on the basis of photoinduced charge separation at the interface between the gold cluster and TiO(2). Electron levels such as HOMO and LUMO were estimated from the dependencies of the photocurrents on the irradiation wavelength and the standard electrode potentials of electron donors employed. The potential of the occupied levels involved in the charge separation under visible or near infrared light shifts negatively as the cluster size increases.

Nanoparticle-Promoted Thermal Stabilization of Room Temperature Cholesteric Blue Phase Mixtures

A blue phase (BP*) liquid crystal mixture was stabilised via doping with three different types of colloidal particles, smaller hexane thiolate-capped gold nanoparticles (NP1) with a size around 2.2 nm, larger oleylamine capped gold nanoparticles (NP2) with an average size of 13.2 nm, and manganese oxide nanoparticles (NP3) capped with oleic acid (10 nm in core diameter). We have experimentally studied the thermal stability of the blue phases by varying the core material of the nanoparticle additives (metal vs. metal oxide), the nature of the capping agents, and the core size. We have used polarized optical microscopy (POM) and the selective reflection of blue phases to identify the type of blue phase as well as the mesomorphic range. For the doped colloidal mixtures, POM and UV-vis spectrophotometry results confirmed the thermal stabilisation of the used BP* mixtures.

Photoinduced processes in chromophore–gold nanoparticle assemblies

Development of nanotechnology requires that the interaction between components of nanoscale devices can be studied and understood better. Photoinduced processes between small (2–5 nm in core diameter) gold nanoparticles (GNPs) and chromophores, including porphyrin, fullerene, and phthalocyanine, were studied. Two methods were selected for controlled assembly of chromophores and gold particles at close distances: thin films and covalent attachment, which yields chromophore-functionalized particles. Time-resolved spectroscopic and photoelectrical measurements carried out further confirmed the known strong effect of GNPs on photoexcited chromophores that leads to fast photoinduced processes. When GNPs are combined with suitable chromophores, the particles can act as electron donors or acceptors. GNPs are efficient energy acceptors, and some indications of their ability to act as energy donors were obtained. The participation of the GNPs in photoinduced charge transfer in addition to energy-transfer processes makes them attractive components for photoactive devices.

SYNTHESIS AND CHARACTERIZATION OF CoFe2O4/Ni0.5Zn0.5Fe2O4 CORE/SHELL MAGNETIC NANOCOMPOSITE BY THE WET CHEMICAL ROUTE

A cobalt ferrite/nickel-zinc ferrite core/shell nanocomposite was synthesized by a polymerized complex method using iron citrate, cobalt nitrate, nickel nitrate, zinc nitrate, citric acid, ethylene glycol, benzoic acid and sodium citrate as starting materials. The XRD, TEM and VSM techniques were employed to evaluate the phase composition, morphology and magnetic properties of the samples. The XRD results indicated the coexistence of characteristic reflections of CoFe 2 O 4 and Ni 0.5 Zn 0.5 Fe 2 O 4 spinel ferrites in the composite sample. The core/shell structure of the composite sample has been confirmed by TEM images. The size of obtained spherical core/shell nanoparticles was 20–40 nm in core diameter and about 10 nm in shell thickness. The VSM results showed that both the coercivity and the saturation magnetization of the resulting core/shell nanocomposite were decreased compared to those of the CoFe 2 O 4 core, due to the interaction at the interface of CoFe 2 O 4 and Ni 0.5 Zn 0.5 Fe 2 O 4.

Fracture in electrophoretically deposited CdSe nanocrystal films

We have studied the fracture, strain, and stress of electrophoretically deposited (EPD) films of CdSe nanocrystals as a function of the film thickness, nanocrystal size, and drying method. Fracture results from the film stress that develops with the loss of residual solvent after EPD when the film exceeds a threshold thickness that increases with nanocrystal core diameter from ∼300 to 1200 nm for core diameters from 2.3 to 5.0 nm, respectively. A hierarchical pattern of wider first generation and then narrower higher-generation cracks is observed after drying and this generational crack formation and a preferred direction for film drying are observed in real time. Delamination is seen to initiate from wider cracks, mostly between the bulk of the film and a very thin layer of nanocrystals strongly bound to the Au-coated silicon substrate. Estimates of the film toughness are made for channel cracking and delamination.

Chiral Functionalization of Optically Inactive Monolayer-Protected Silver Nanoclusters by Chiral Ligand-Exchange Reactions

We report the ligand-exchange reaction between the optically inactive racemic penicillamine monolayer on a silver nanocluster surface and enantiopure D- or L-penicillamine dissolved in solution. Emergence of the identical band positions in the gel electrophoresis separation assures the presence of size-invariant silver nanoclusters (1.05 and 1.30 nm in core diameter) during the ligand-exchange reaction and allows us to further examine the optical/chiroptical properties of these nanoclusters. Consequently, chiral functionalization of the achiral silver nanoclusters has been demonstrated, yielding large Cotton effects in metal-based electronic transitions with an almost mirror-image relationship between the enantiomeric compounds. The ligand-exchange experiments as well as the normal syntheses of the silver nanoclusters revealed that their absorption profiles and anisotropy factors were strongly dependent on the enantiomeric purity (or enantiomeric excess) of surface chiral penicillamine, so that (several-fold) larger chiroptical responses of the silver nanoclusters as compared to those of the analogous gold clusters with a comparable size could be induced by the metal core deformation or rearrangement along with a universally influential vicinal contribution from the chiral ligand field.

Tunable Plasmonic Response from Alkanethiolate-Stabilized Gold Nanoparticle Superlattices: Evidence of Near-Field Coupling

We report on the self-assembly of large-area, highly ordered 2D superlattices of alkanethiolate-stabilized gold nanoparticles ( approximately 10.5 nm in core diameter) onto quartz substrates with varying lattice constants, which can be controlled by the alkyl chain lengths, ranging from C12 (1-dodecanethiolate), C14 (1-tetradecanethiolate), C16 (1-hexadecanethiolate), to C18 (1-octadecanethiolate). These 2D nanoparticle superlattices exhibit strong collective surface plasmon resonance that is tunable via the near-field coupling of adjacent nanoparticles. The approach presented here provides a unique and viable means of building artificial "plasmonic crystals" with precisely designed optical properties, which can be useful for the emerging fields of plasmonics, such as subwavelength integrated optics.