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Laser-driven hybridization of a collective surface plasmon mode of a monolayer of silver nanoparticles has been studied as a function of irradiation power density. Two collective surface plasmon modes were identified in the spectra, namely, T- and P-modes, associated with the induced particle dipoles parallel and perpendicular to the plane of the layer. The P-mode was in resonance with the laser irradiation wavelength (488 nm). The magnitude, spectral position, and bandwidth of the two modes depend significantly differently on the laser power density. The laser-driven changes of the T-mode were attributed to the thermal effects caused by laser heating of the sample. Meanwhile, the spectral behavior of the P-mode is governed by resonant excitation by an Ar laser.

We have fabricated gradient-grafted nanofoam films that are able to record the presence of volatile chemical compounds in an offline regime. In essence, the nanofoam film (100-300 nm thick) is anchored to a surface cross-linked polymer network in a metastable extended configuration that can relax back to a certain degree upon exposure to a chemical vapor. The level of the chain relaxation is associated with thermodynamic affinity between the polymer chains and the volatile compounds. In our design, the chemical composition of the nanofoam film is not uniform; therefore, the film possesses a gradually changing local affinity to a vapor along the surface. Upon vapor exposure, the nonuniform changes in local film morphology provide a permanent record or "fingerprint" for the chemical event of interest. This permanent modification in the film structure can be directly detected via changes not only in the film surface profile but also in the film optical characteristics. To this end, we demonstrated that sensing/recording nanofoam films can be prepared and interrogated on the surfaces of optical waveguides, microring optical resonators. It is important that the initial surface profile and structure of the nanofoam film are encrypted by the distinctive conditions that were used to fabricate the film and practically impossible to replicate without prior knowledge.

Three phosphonium polyelectrolytes have been prepared wherein the flexibility of the spacer between charge-bearing phosphonium units was varied from 1,2-ethyl to 1,4-phenyl to 1,1′-ferrocenyl. The influence of inter-phosphonium spacer flexibility on the ability of the polyelectrolyte to form ordered films via layer-by-layer supramolecular assembly with anionic polythiophene and anionic poly(p-phenylenevinylene) derivatives was also assessed through a combination of UV−visible spectroscopy and atomic force microscopy. The more flexible ionic polymers were found to be capable of forming thicker films and to maintain growth linearity up to at least 800 bilayers in some cases. © 2015 Society of Chemical Industry

Three ionic polymers featuring main chain tetraarylphosphonium units have been prepared by an underexplored polymerisation route that employs Ni-catalysed P–C bond formation. The three polymers include chromophores comprised of 2,5-dihexyloxy-p-phenylene, 9,9-dioctyl-2,7-fluorenylene, or 2,7-fluorenone segments between phosphonium sites so that the composite ionic polymers exhibit absorption and photoluminescence in the UV-visible region of the spectrum. The photophysical properties of the materials were evaluated to assess the applicability of the polymers for optoelectronic applications. The wettability and critical surface energies of dip-coated neat polymer films were also determined from contact angle measurements.

We established that metal–dielectric nanostructures (consisting of three stacked monolayers of silver nanoparticles incorporated into polymer cross-linked film) can demonstrate three different surface plasmon collective modes. The modes were detected when the extinction spectra of the nanostructures were studied as a function of the incident angle and polarization of the incident light. Two previously known surface plasmon collective modes, namely T and P, associated with particle dipoles parallel and perpendicular to plane of the layer were identified for the polymer films containing one, two, and three monolayers of the particles. The extinction bands of T and P modes exhibited different intensity and frequency dependences on the angle of incidence. More pronounced angular dependences for P mode band indicated the stronger coupling of dipoles for P mode than for T one. A new N mode was observed for the structures consisting of three nanoparticle layers. This mode originated from surface plasmon coupling between adjacent layers. The additional mode significantly increases amount of information that can be obtained from optical response of the nanostructures.

As electronic devices are scaled down to submicron sizes, it has become critical to obtain uniform and robust insulating nanoscale polymer films. For that reason, we address the electrical properties of grafted polymer layers made of poly(glycidyl methacrylate), polyacrylic acid, poly(2-vinylpyridine), and polystyrene with thicknesses of 10-20 nm. It was found that layers insulating under normal ambient conditions can display a significant increase in conductivity as the environment changes. Namely, we demonstrated that the in-plane electrical conductivity of the polymer grafted layers can be changed by at least two orders of magnitude upon exposure to water or organic solvent vapors. Conductive properties of all polymer grafted films under study could also be significantly enhanced with an increase in temperature. The observed phenomenon makes possible the chemical design of polymer nanoscale layers with reduced or enhanced sensitivity to the anticipated change in environmental conditions. Finally, we demonstrated that the observed effects could be used in a micron-sized conductometric transducing scheme for the detection of volatile organic solvents.

Synthetic multifunctional electrospun composites are a new class of hybrid materials with many potential applications. However, the lack of an efficient, reactive large-area substrate has been one of the major limitations in the development of these materials as advanced functional platforms. Herein, we demonstrate the utility of electrospun poly(glycidyl methacrylate) films as a highly versatile platform for the development of functional nanostructured materials anchored to a surface. The utility of this platform as a reactive substrate is demonstrated by grafting poly(N-isopropylacrylamide) to incorporate stimuli–responsive properties. Additionally, we demonstrate that functional nanocomposites can be fabricated using this platform with properties for sensing, fluorescence imaging, and magneto-responsiveness.

The paradigm of using nanoparticle-based formulations for drug delivery relies on their enhanced passive accumulation in the tumor interstitium. Nanoparticles with active targeting capabilities attempt to further enhance specific delivery of drugs to the tumors via interaction with overexpressed cellular receptors. Consequently, it is widely accepted that drug delivery using actively targeted nanoparticles maximizes the therapeutic benefit and minimizes the off-target effects. However, the process of nanoparticle mediated active targeting initially relies on their passive accumulation in tumors. In this article, it is demonstrated that these two tumor-targeted drug delivery mechanisms are interrelated and dosage dependent. It is reported that at lower doses, actively targeted nanoparticles have distinctly higher efficacy in tumor inhibition than their passively targeted counterparts. However, the enhanced permeability and retention effect of the tumor tissue becomes the dominant factor influencing the efficacy of both passively and actively targeted nanoparticles when they are administered at higher doses. Importantly, it is demonstrated that dosage is a pivotal parameter that needs to be taken into account in the assessment of nanoparticle mediated targeted drug delivery.

We report the fabrication of flexible chains of ferromagnetic Ni nanoparticles that possess the ability to adapt other than the typically observed rigid (nearly) straight configurations in the absence of an external magnetic field. The dynamic mobility of the ferromagnetic chains originates from a layer of densely grafted polyethylene glycol macromolecules enveloping each nanoparticle in the chain. While ferromagnetic chains of unmodified Ni nanoparticles behave as stiff nickel nanorods, the chains made of the grafted nanoparticles demonstrate extreme flexibility. Upon changing the direction of the field, and inevitably going through a zero-field point, the shorter chains undergo chain–globule–chain transformation. The longer chains can bend to a high degree, attaining “snake-like” configurations.

We demonstrated that nanoscale-level actuation can be, in principle, achieved with grafted polymer nanofoams by forces associated with conformational changes of stretched macromolecular chains. The nanofoams are fabricated via a two-step procedure. First, the "grafting to" technique is used to obtain a 20-200 nm anchored and cross-linked poly(glycidyl methacrylate) film. Second, the film is swollen in solvent and freeze dried until the solvent is sublimated. The grafted nanofoam possesses the behavior of a shape-memory material, exhibiting gradual mechanical contraction at the nanometer scale as temperature is increased. Both the thickness and shape-recovery ratio of the nanofoam have a close to linear dependency on temperature. We also demonstrated that by modification of the poly(glycidyl methacrylate) nanofoam with grafting low molecular weight polymers, one can tune an absolute nanoscale mechanical response of the porous polymer film.