Proton exchange membrane with plasmon-active surface for enhancement of fuel cell effectivity.

The action of fuel cells with proton-exchanged membranes (PEMs) requires the implementation of the hydrogen oxidation reaction (HOR) and the oxygen reduction reaction (ORR) on the opposite sides of the PEMs. Recently, based on several models of electrochemical reactions a significant decrease in the thermodynamic activation barrier of both reactions under plasmon assistance was reported. In this work, we propose the design of a PEM fuel cell with a plasmon-active catalytic surface providing plasmonic triggering and enhancement of fuel cell efficiency. In particular, we deposited bimetallic (Au@Pt) nanostructures on the PEM surface and integrated them into the fuel cell design. Plasmon excitation occurs on the Au nanostructures under light illumination at the corresponding NIR wavelength, while the Pt shell is responsible for the introduction of catalytic sites. Light illumination results in a significant enhancement of the electric current produced by the fuel cell. In particular, the electric current increased several times. Control experiments indicated that the observed enhancement takes place only when the light wavelength is in compliance with the plasmon absorption band and the contribution from thermal effects is negligible. The present approach for the introduction of plasmon assistance into the design of advanced fuel cells makes them suitable for increasing the fuel cell efficiency under sunlight.

Plasmon-active optical fiber functionalized by metal organic framework for pesticide detection.

Functional plasmonic fiber for detection and on-line monitoring of organophosphorus pesticides in water or model soil samples is described. The appearance of the plasmon absorption band was realized through the deposition of a thin gold layer on the naked core of multimode optical fiber. The metalorganic frameworks (MOF-5) layer was deposited on the gold surface for the introduction of a high affinity towards the target pesticides. The MOF-5 layer affords the extraction of pesticides and their concentration primarily in the "plasmon evanescent wave" space, allowing the detection by the shift of plasmon absorption band. The growth of MOF-5 layer was confirmed using the Raman, XPS and XRD measurements. The entrapping of pesticides was checked using the Raman spectroscopy and ellipsometry, which also indicate the corresponding changes of MOF-5 refractive index. The series of further experiments demonstrate the applicability of proposed fiber sensor for detection of pesticides in soil without the false signals from surrounding media. The main advantages of proposed sensor can be attributed to simplicity, high sensitivity, low cost and the absence of organic solvents for the probe treatment.

Polypyrrole-coated cellulose nanofibers: influence of orientation, coverage and electrical stimulation on SH-SY5Y behavior.

In the field of tissue engineering, much research has been devoted to the surface topography of conductive materials. However, less work has been carried out on how the electrical stimulation of such materials influences nerve regeneration. Here, we investigated the effect of electrical stimulation on randomly- and uniaxially-aligned polypyrrole-coated cellulose acetate butyrate (PPy/CAB) nanofibers. First, SEM revealed that the conducting PPy coverage resulted in dramatic changes to the nanofiber morphology. In turn, these changes led to an increase in the sample wettability. Fourier transform spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of a PPy layer. Second, human neuroblastoma cells (SH-SY5Y) were seeded on the PPy/CAB nanofibers and stimulated by 100 mV mm-1 at 1 Hz pulses in vitro. We demonstrated that either with or without this electrical stimulation both nanofiber alignment and PPy coverage had a strong influence on cell morphology and attachment. Moreover, fluorescence microscopy revealed that the cells stimulated on PPy/CAB had longer neurite outgrowth. Collectively, our results shed light on the combined effect of scaffold morphology and external stimulation on neuronal cell behavior.

Porphyrin­silver nanoparticles hybrids: Synthesis, characterization and antibacterial activity.

The preparation of light-activated hybrid antibacterial agent combining the porphyrin molecules, bound to the silver nanoparticles (AgNPs) surface is reported. AgNPs were synthesized by N-methyl-2-pyrrolidone-initiated reduction without additional reducing agents. The chemical structure of protoporphyrin IX was modified with the aim to introduce thiol groups. The size distribution and shape features of AgNPs were checked using TEM and HRTEM microscopies. The introduction of thiol groups into the porphyrin was proved by IR spectroscopy. The AgNPs-porphyrin binding was performed in solution and confirmed by fluorescence quenching, Raman spectroscopy and energy-filtered transmission electron microscopy (EFTEM). The antibacterial tests were performed against S. epidermidis and E. coli upon to LED illumination and in the dark. The synergetic effect of AgNPs and porphyrin as well as light activation of the created antibacterial conjugates were observed.

Metal-organic framework (MOF-5) coated SERS active gold gratings: A platform for the selective detection of organic contaminants in soil.

In this work, we proposed the functionalization of a surface plasmon-polariton (SPP)-supported gold grating surface with the metal-organic framework (MOF-5) for sensitive, selective and reproducible surface-enhanced Raman scattering (SERS) detection of organophosphorus pesticides. Homogeneous distribution of plasmon intensity along the Au grating surface ensures the high reproducibility of SERS results (deviation of Raman peak intensity does not exceed the 4% along the sample). The surface-assisted growth of thin MOF-5 film was accomplished in two steps procedure: (i) covalent grafting by 4-carboxyphenyl groups and (ii) the immersion of samples in the mother liquid of MOF-5. Proposed SERS chip proved itself to be a perfect analytical probe for the detection of organophosphorus pesticides with high reliability and low detection limit up to 10-12 M. Moreover, selective detection and recognition of several relevant organic contaminants (azo-dye, mycotoxin, and pesticide) from the simulated soil was successfully demonstrated. All SERS measurements were performed using portable Raman spectrometer and can easily be expanded to environmental conditions. Our work combines the high affinity of organic contaminants to the MOF-5 with excellent plasmonic excitation on the surface plasmon-polariton supported structure and shows the way to the realization of closed-to-ideal analytical SERS chip.

Vapor Annealing and Colloid Lithography: An Effective Tool To Control Spatial Resolution of Surface Modification.

Colloid lithography represents a simple and efficient method for creation of a large-scale template for subsequent surface patterning, deposition of regular metal nanostructures, or periodical surface structures. However, this method is significantly restricted by its ability to create only a limited number of structures with confined geometry and symmetry features. To overcome this limitation, different techniques, such as plasma treatment or tilting angle metal deposition, have been proposed. In this paper, an alternative method based on the vapor annealing of ordered single polystyrene (PS) microspheres layer, followed by the surface grafting with arenediazonium tosylates is proposed. Application of vapor treatment before surface grafting allows effective control of the area screened by PS microspheres. Pristine and vapor-annealed microsphere arrays on the gold substrate were electrochemically modified using ADTs. Subsequent removal of the PS microsphere mask enabled to prepare well-defined nanostructures with controllable surface features. In particular, prepared periodic arrangements were achieved by the grafting of OFGs to the empty interspaces between nanopore arrays. The process of sample preparation was controlled, and the properties of prepared structures were characterized by various techniques, including atomic force microscopy (AFM), conductive AFM, scanning electron microscopy energy-dispersive X-ray spectrometry, Raman spectroscopy, and voltammetry.

Laser patterning of transparent polymers assisted by plasmon excitation.

Plasmon-assisted lithography of thin transparent polymer films, based on polymer mass-redistribution under plasmon excitation, is presented. The plasmon-supported structures were prepared by thermal annealing of thin Ag films sputtered on glass or glass/graphene substrates. Thin films of polymethylmethacrylate, polystyrene and polylactic acid were then spin-coated on the created plasmon-supported structures. Subsequent laser beam writing, at the wavelength corresponding to the position of plasmon absorption, leads to mass redistribution and patterning of the thin polymer films. The prepared structures were characterized using UV-Vis spectroscopy and confocal and AFM microscopy. The shape of the prepared structures was found to be strongly dependent on the substrate type. The mechanism leading to polymer patterning was examined and attributed to the plasmon-heating. The proposed method makes it possible to create different patterns in polymer films without the need for wet technological stages, powerful light sources or a change in the polymer optical properties.

Sandwiched gold/PNIPAm/gold microstructures for smart plasmonics application: towards the high detection limit and Raman quantitative measurements.

A smart plasmonic sensor, comprising a layer of a stimuli-responsive polymer sandwiched between two gold layers, is reported. As a stimuli-responsive material, a monolayer of poly(N-isopropylacrylamide) (PNIPAm) crosslinked globules is used. A quasi-periodic structure of the top gold layer facilitates efficient excitation and serves as a support for plasmon excitation and propagation. The intermediate layer of PNIPAm efficiently entraps targeted molecules from solutions. The sensor structure was optimized for efficient light focusing in the "active" PNIPAm layer. The optimization was based on the time-resolved finite-element simulations, which take into account the thickness of gold layers, size of PNIPAm globules and Raman excitation wavelength (780 nm). The prepared structures were characterized using SEM, AFM, UV-Vis refractometry and goniometry. Additional AFM scans were performed in water at two temperatures corresponding to the collapsed and swollen PNIPAm states. The Raman measurements demonstrate a high detection limit and perfect reproducibility of the Raman scattering signal for the prepared sensor. In addition, the use of created SERS structures for the detection of relevant molecules in the medical, biological and safety fields was demonstrated.