Gradient Polymer Nanofoams for Encrypted Recording of Chemical Events.

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.

Functional Reactive Polymer Electrospun Matrix.

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.

RNA Interference Using c-Myc-Conjugated Nanoparticles Suppresses Breast and Colorectal Cancer Models.

In this article, we report the development and preclinical validation of combinatorial therapy for treatment of cancers using RNA interference (RNAi). RNAi technology is an attractive approach to silence genes responsible for disease onset and progression. Currently, the critical challenge facing the clinical success of RNAi technology is in the difficulty of delivery of RNAi inducers, due to low transfection efficiency, difficulties of integration into host DNA and unstable expression. Using the macromolecule polyglycidal methacrylate (PGMA) as a platform to graft multiple polyethyleneimine (PEI) chains, we demonstrate effective delivery of small oligos (anti-miRs and mimics) and larger DNAs (encoding shRNAs) in a wide variety of cancer cell lines by successful silencing/activation of their respective target genes. Furthermore, the effectiveness of this therapy was validated for in vivo tumor suppression using two transgenic mouse models; first, tumor growth arrest and increased animal survival was seen in mice bearing Brca2/p53-mutant mammary tumors following daily intratumoral treatment with nanoparticles conjugated to c-Myc shRNA. Second, oral delivery of the conjugate to an Apc-deficient crypt progenitor colon cancer model increased animal survival and returned intestinal tissue to a non-wnt-deregulated state. This study demonstrates, through careful design of nonviral nanoparticles and appropriate selection of therapeutic gene targets, that RNAi technology can be made an affordable and amenable therapy for cancer.

Capillary force lithography: the versatility of this facile approach in developing nanoscale applications.

Since its inception as a simple, low cost alternative to more complicated lithographic techniques such as electron-beam and dip-pen lithography, capillary force lithography (CFL) has developed into a versatile tool to form sub-100 nm patterns. Utilizing the concept of a polymer melt, structures and devices generated by the technique have been used in applications varying from surfaces regulating cell growth to gas sensing. In this review, we discuss various CFL methodologies which have evolved, their application in both biological and non-biological research, and finally a brief outlook in areas of research where CFL is destined to make an enormous impact in the near future.

Temperature controlled shape change of grafted nanofoams.

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.

Mid-infrared materials and devices on a Si platform for optical sensing.

In this article, we review our recent work on mid-infrared (mid-IR) photonic materials and devices fabricated on silicon for on-chip sensing applications. Pedestal waveguides based on silicon are demonstrated as broadband mid-IR sensors. Our low-loss mid-IR directional couplers demonstrated in SiN x waveguides are useful in differential sensing applications. Photonic crystal cavities and microdisk resonators based on chalcogenide glasses for high sensitivity are also demonstrated as effective mid-IR sensors. Polymer-based functionalization layers, to enhance the sensitivity and selectivity of our sensor devices, are also presented. We discuss the design of mid-IR chalcogenide waveguides integrated with polycrystalline PbTe detectors on a monolithic silicon platform for optical sensing, wherein the use of a low-index spacer layer enables the evanescent coupling of mid-IR light from the waveguides to the detector. Finally, we show the successful fabrication processing of our first prototype mid-IR waveguide-integrated detectors.

Toward fabric-based flexible microfluidic devices: pointed surface modification for pH sensitive liquid transport.

Microfluidic fiber channels with switchable water transport are fabricated in flexible textile PET/PP materials using a preprogrammed yarn-based fabric and a yarn-selective surface modification method. The developed robust and scalable fabrication method is based on the selective functionalization of the PET yarns with an epoxide-containing polymer that is then followed by grafting patterns of different pH-sensitive polymers PAA [poly(acrylic acid) ] and P2VP [poly(2-vinyl pyridine)]. The selective functionalization of the fabric yields an array of amphiphilic channels that are constrained by hydrophobic PP boundaries. Aqueous solutions are transported in the amphiphilic channels by capillary forces where the direction of the liquid transport is defined by pH-response of the grafted polymers. The channels are fed with liquid through hydrophilic, pH insensitive PEG [polyethylene glycol] ports. The combination of the PAA and P2VP patterns in the amphiphilic channels is used to create pH-sensitive elements that redirect aqueous liquids toward PAA channels at pH > 4 and toward both PAA and P2VP channels at pH < 4. The system of pH-selective channels in the developed textile based microfluidic chip could find analytical applications and can be used for smart cloth.

Field-directed self-assembly with locking nanoparticles.

A reversible locking mechanism is established for the generation of anisotropic nanostructures by a magnetic field pulse in liquid matrices by balancing the thermal energy, short-range attractive and long-range repulsive forces, and dipole-dipole interactions using a specially tailored polymer shell of nanoparticles. The locking mechanism is used to precisely regulate the dimensions of self-assembled magnetic nanoparticle chains and to generate and disintegrate three-dimensional (3D) nanostructured materials in solvents and polymers.

In vivo imaging and biodistribution of multimodal polymeric nanoparticles delivered to the optic nerve.

The use of nanoparticles for targeted delivery of therapeutic agents to sites of injury or disease in the central nervous system (CNS) holds great promise. However, the biodistribution of nanoparticles following in vivo administration is often unknown, and concerns have been raised regarding potential toxicity. Using poly(glycidyl methacrylate) (PGMA) nanoparticles coated with polyethylenimine (PEI) and containing superparamagnetic iron oxide nanoparticles as a magnetic resonance imaging (MRI) contrast agent and rhodamine B as a fluorophore, whole animal MRI and fluorescence analyses are used to demonstrate that these nanoparticles (NP) remain close to the site of injection into a partial injury of the optic nerve, a CNS white matter tract. In addition, some of these NP enter axons and are transported to parent neuronal somata. NP also remain in the eye following intravitreal injection, a non-injury model. Considerable infiltration of activated microglia/macrophages occurs in both models. Using magnetic concentration and fluorescence visualization of tissue homogenates, no dissemination of the NP into peripheral tissues is observed. Histopathological analysis reveals no toxicity in organs other than at the injection sites. Multifunctional nanoparticles may be a useful mechanism to deliver therapeutic agents to the injury site and somata of injured CNS neurons and thus may be of therapeutic value following brain or spinal cord trauma.

Tuning fluorescent response of nanoscale film with polymer grafting.

An effective method for tuning fluorescent response of an ultrathin (5 nm) polymer film, which can be used for generation of sensing arrays, is reported. This method is distinctive in that the modification of the optical response is achieved with polymer grafting of a non-fluorescent polymer to a fluorescent film. Using this approach, a number of films demonstrating different fluorescent emission when exposed to solvent vapors were synthesized.

Regiospecific linear assembly of Pd nanocubes for hydrogen gas sensing.

Capillary force lithography was applied to generate large area polymer patterns. A "grafting to" approach was used on the patterns to induce linear assembly of Pd nanocubes through electrostatic interaction. Pd nanoarrays with high density were subjected to a hydrogen gas sensing test. We demonstrated a feasible method to build up a miniature hydrogen sensor using self-assembly with micrometre Pd nanoarrays.

Detecting trace amounts of water in hydrocarbon matrices with infrared fiberoptic evanescent field sensors.

Water is a common contaminant in a variety of industrial oils and petroleum products. Thus, the detection of water in these products is of substantial relevance. Hence, this study focuses on quantifying trace amounts of water in hydrocarbons using hexane as a model system for industrial oils and petroleum matrices via mid-infrared (MIR) evanescent field absorption spectroscopy. A silver halide fiberoptic waveguide was used to interrogate in situ water-in-hexane emulsions. Either unmodified fibers or waveguides surface-modified with polyacrylic acid layers were used. The limits of detection (LOD) and limits of quantification (LOQ) of water in hexane utilizing tin-crosslinked polyacrylic acid modified fibers were 76 and 170 ppm, respectively. Consequently, the IR absorption signature of water in hexane is detectable at concentrations as low as 10 ppm. The proposed fiberoptic sensing strategy requires a single measurement only, requires no sample preparation, and thus has potential for the direct in situ detection and monitoring of water in industrial oils and petroleum products.

In situ trace analysis of oil in water with mid-infrared fiberoptic chemical sensors.

The determination of trace amounts of oil in water facilitates the forensic analysis on the presence and origin of oil in the aqueous environment. To this end, the present study focuses on direct sensing schemes for quantifying trace amounts of oil in water using mid-infrared (MIR) evanescent field absorption spectroscopy via fiberoptic chemical sensors. MIR transparent silver halide fibers were utilized as optical transducer for interrogating oil-in-water emulsions via the evanescent field emanating from the waveguide surface, and penetrating the surrounding aqueous environment by a couple of micrometers. Unmodified fibers and fibers surface-modified with grafted epoxidized polybutadiene layers enabled the direct detection of crude oil in a deionized water matrix at the ppm level to ppb concentration level, respectively. Thus, direct chemical sensing of crude oil IR signatures without any sample preparation as low as 46 ppb was achieved with a response time of a few seconds.

Multimodal analysis of PEI-mediated endocytosis of nanoparticles in neural cells.

Polymer nanoparticles are widely used as a highly generalizable tool to entrap a range of different drugs for controlled or site-specific release. However, despite numerous studies examining the kinetics of controlled release, the biological behavior of such nanoparticles remains poorly understood, particularly with respect to endocytosis and intracellular trafficking. We synthesized polyethylenimine-decorated polymer nanospheres (ca. 100-250 nm) of the type commonly used for drug release and used correlated electron microscopy, fluorescence spectroscopy and microscopy, and relaxometry to track endocytosis in neural cells. These capabilities provide insight into how polyethylenimine mediates the entry of nanoparticles into neural cells and show that polymer nanosphere uptake involves three distinct steps, namely, plasma membrane attachment, fluid-phase as well as clathrin- and caveolin-independent endocytosis, and progressive accumulation in membrane-bound intracellular vesicles. These findings provide detailed insight into how the intracellular delivery of nanoparticles is mediated by polyethylenimine, which is presently the most commonly used nonviral gene transfer agent. This fundamental knowledge may also assist in the preparation of next-generation nonviral vectors.

A major constituent of brown algae for use in high-capacity Li-ion batteries.

The identification of similarities in the material requirements for applications of interest and those of living organisms provides opportunities to use renewable natural resources to develop better materials and design better devices. In our work, we harness this strategy to build high-capacity silicon (Si) nanopowder-based lithium (Li)-ion batteries with improved performance characteristics. Si offers more than one order of magnitude higher capacity than graphite, but it exhibits dramatic volume changes during electrochemical alloying and de-alloying with Li, which typically leads to rapid anode degradation. We show that mixing Si nanopowder with alginate, a natural polysaccharide extracted from brown algae, yields a stable battery anode possessing reversible capacity eight times higher than that of the state-of-the-art graphitic anodes.

Multifunctional nanoadditives for the thermodynamic and kinetic stabilization of enzymes.

Stabilization of enzymes has become a major focus in the quest to improve the activity, sustainability and recyclability of enzymes for their successful integration into both industry and medicine. Here, we describe the kinetic and thermodynamic stabilization of a variety of enzymes in the presence of cationic multifunctional polymeric nanoparticles.

Towards universal enrichment nanocoating for IR-ATR waveguides.

Polymer multilayered nanocoating capable of concentrating various chemical substances at IR-ATR waveguide surfaces is described. The coating affinity to an analyte played a pivotal role in sensitivity enhancement of the IR-ATR measurements, since the unmodified waveguide did not show any analyte detection.

Pd-induced ordering of 2D Pt nanoarrays on phosphonated calix[4]arenes stabilised graphenes.

p-Phosphonic acid calix[4]arenes render high stability to exfoliated graphenes in water. These calix[4]arenes modified graphenes can be used as highly effective substrates to nucleate ultra-small Pd nanoparticles, which in turn serve as galvanic reaction templates for the generation of high density 2D arrays of Pt nanoparticles.

Polymer brushes by the "grafting to" method.

This paper focuses on the attachment of densely grafted polymer layers (polymer brushes) to various inorganic and polymeric substrates by the "grafting to" method. A brief overview of synthesis of polymer brushes by the method is first provided, with emphasis on chemical approaches to polymer attachment. The second part of the paper covers the synthesis of polymer layers via a recently developed macromolecular anchoring layer approach. Several examples of application of the grafting technique are presented for generation of hydrophobic, hydrophilic, gradient, and switchable surfaces.

The effects of concentration-dependent morphology of self-assembling RADA16 nanoscaffolds on mixed retinal cultures.

RADA16 self-assembling peptide nanofiber scaffolds (SAPNSs) have been shown to have positive effects on neural regeneration following injury to the central nervous system in vivo, but mechanisms are unclear. Here we show that RADA16 SAPNSs form scaffolds of increasing fiber density with increasing peptide concentration which in turn has a concentration-dependent effect on neurons and astrocytes in mixed retinal cultures. Importantly, we report that the final nanoscale fiber architecture is an important factor to consider in designing scaffolds to promote regeneration in the central nervous system.