Maskless Preparation of Spatially-Resolved Plasmonic Nanoparticles on Polydimethylsiloxane via In Situ Fluoride-Assisted Synthesis

Here, a fluoride-assisted route for the controlled in-situ synthesis of metal nanoparticles (NPs) (i.e., AgNPs, AuNPs) on polydimethylsiloxane (PDMS) is reported. The size and coverage of the NPs on the PDMS surface are modulated with time and over space during the synthetic process, leveraging the improved yield (10×) and faster kinetics (100×) of NP formation in the presence of F⁻ ions, compared to fluoride-free approaches. This enables the maskless preparation of both linear and step gradients and patterns of NPs in 1D and 2D on the PDMS surface. As an application in flexible plasmonics/photonics, continuous and step-wise spatial modulations of the plasmonic features of PDMS slabs with 1D and 2D AgNP gradients on the surface are demonstrated. An excellent spatially resolved tuning of key optical parameters, namely, optical density from zero to 5 and extinction ratio up to 100 dB, is achieved with AgNP gradients prepared in AgF solution for 12 minutes; the performance are comparable to those of commercial dielectric/interference filters. When used as a rejection filter in optical fluorescence microscopy, the AgNP-PDMS slabs are able to reject the excitation laser at 405 nm and retain the green fluorescence of microbeads (100 µm) used as test cases.     

Optical Characterization of High-Order 1-D Silicon Photonic Crystals

In this paper, we present numerical and experimental results on the spectral reflectivity of hybrid, high-order (up to 22nd) 1-D silicon photonic crystals (PCs) in the near-infrared region (wavelength range 1- 1.7 mum). Mechanically robust, vertical 1-D PCs with high aspect ratio and spatial period of 8 mum were fabricated by electrochemical micromachining of silicon, and tested in reflection with an improved optical setup, incorporating standard telecommunication single-mode optical fibers and a lensed fiber pigtail. A detailed theoretical, numerical analysis was performed to assess the effects of both non-idealities of the structures under test and constraints of the optical setup, on the spectral reflectivity. Experimental data were found in very good agreement with theoretical calculations, performed by using the characteristic matrix method, keeping into account an in-plane porosity variation for 1-D PCs, due to surface roughness of silicon walls, and the limited resolution bandwidth of the spectrum analyzer. Best optical performances, measured on the fabricated 1-D PC mirrors, consist of optical losses less than 0.8 dB in a bandgap around 1.5 mum and a -35 dB reflectivity minimum at a bandgap edge.     

Tyrosine quenching of tryptophan phosphorescence in glyceraldehyde-3-phosphate dehydrogenase from Bacillus stearothermophilus

Tyrosine is known to quench the phosphorescence of free tryptophan derivatives in solution, but the interaction between tryptophan residues in proteins and neighboring tyrosine side chains has not yet been demonstrated. This report examines the potential role of Y283 in quenching the phosphorescence emission of W310 of glyceraldehyde-3-phosphate dehydrogenase from Bacillus stearothermophilus by comparing the phosphorescence characteristics of the wild-type enzyme to that of appositely designed mutants in which either the second tryptophan residue, W84, is replaced with phenylalanine or Y283 is replaced by valine. Phosphorescence spectra and lifetimes in polyol/buffer low-temperature glasses demonstrate that W310, in both wild-type and W84F (Trp84-->Phe) mutant proteins, is already quenched in viscous low-temperature solutions, before the onset of major structural fluctuations in the macromolecule, an anomalous quenching that is abolished with the mutation Y283V (Tyr283-->Val). In buffer at ambient temperature, the effect of replacing Y283 with valine on the phosphorescence of W310 is to lengthen its lifetime from 50 micros to 2.5 ms, a 50-fold enhancement that again emphasizes how W310 emission is dominated by the local interaction with Y283. Tyr quenching of W310 exhibits a strong temperature dependence, with a rate constant kq = 0.1 s(-1) at 140 K and 2 x 10(4) s(-1) at 293 K. Comparison between thermal quenching profiles of the W84F mutant in solution and in the dry state, where protein flexibility is drastically reduced, shows that the activation energy of the quenching reaction is rather small, Ea < or = 0.17 kcal mol(-1), and that, on the contrary, structural fluctuations play an important role on the effectiveness of Tyr quenching. Various putative quenching mechanisms are examined, and the conclusion, based on the present results as well as on the phosphorescence characteristics of other protein systems, is that Tyr quenching occurs through the formation of an excited-state triplet exciplex.     

Bandgap Tuning of Silicon Micromachined 1-D Photonic Crystals by Thermal Oxidation

Fabrication and optical testing of high-aspect-ratio 1D photonic crystals, obtained by electrochemical micromachining of silicon, are discussed in this paper. The devices consist of high-aspect-ratio periodic (P=4 mum) arrays of 1.22-mum-thick silicon walls separated by 2.78-mum-wide air gaps, with 100 mum etching depth. They were designed as hybrid quarter-wavelength reflectors with photonic bandgaps in the near-IR region, one in particular centered at lambda=1.55 mum. The fabrication process was improved to increase structure uniformity and strength. Thermal oxidation of the silicon structures was exploited to tune the wavelength position and width of the bandgaps. Fabricated devices, also with different silicon dioxide thicknesses, were optically tested by measuring their spectral reflectivity in the wavelength range of 1.0-1.7 mum. Experimental results were found in good agreement with the calculated spectra.     

Low-concentration NO/sub 2/ detection with an adsorption porous silicon FET

Adsorption porous silicon FET (APSFET) is a porous silicon (PS)-based device constituted of a FET structure with a porous adsorbing layer between drain and source. Adsorbed gas molecules in the porous layer induce an inverted channel in the crystalline silicon under the PS itself. The mobile charge per unit area in the channel depends on the molecular gas concentrations in the sensing layer so that adsorbed gas molecules play a role similar to the charge on the gate of a FET. In this work, NO/sub 2/ detection by using the APSFET is demonstrated for the first time. NO/sub 2/ concentration as low as 100 ppb was detected. Devices with both as-grown and oxidized PS layers were fabricated and compared in order to investigate the effect of a low-temperature thermal oxidation on the electrical performances of the sensor. Nonoxidized sensors show a high sensitivity only for fresh devices, which reduces with the aging of the sample. Oxidation of the PS layer improves the electrical performance of sensors, in terms of stability, recovery time, and interference with the relative humidity level, keeping the high sensitivity to nitrogen dioxide.     

Conformational changes in proteins induced by dynamic associations. A tryptophan phosphorescence study

Futility is a complex concept with several possible meanings. It has become an important concept in acute care as situations arise in which patients or their families request interventions that caregivers believe serve no purpose. Resolving these dilemmas requires an understanding of the concept of futility, knowledge of empirical data relevant to the particular situation, and unambiguous communication. The definitions, criteria, and application of the concept of futility are presented, followed by a discussion of the implications of decisions about futile care for nurses and others.     

Integrated optofluidic microsystem based on vertical high-order one-dimensional silicon photonic crystals

In this work, fabrication and testing of an optofluidic microsystem exploiting high aspect-ratio, vertical, silicon/air one-dimensional (1D) photonic crystals (PhC) are reported. The microsystem is composed of an electrochemically micromachined silicon substrate integrating a 1D PhC featuring high-order bandgaps in the near-infrared region, bonded to a glass cover provided with inlet/outlet holes for liquid injection/extraction in/out the PhC-itself. Wavelength shifts of the reflectivity spectrum of the photonic crystal, in the range 1.0–1.7?μm, induced by flow of different liquids through the PhC air gaps are successfully measured using an in-plane all-fibre setup, thanks to the PhC high aspect-ratio value. Experimental results well agree with theoretical predictions and highlight the good linearity and high sensitivity of such an optofluidic microsystem in measuring refractive index changes. The sensitivity value is estimated to be 1,049?nm/RIU around 1.55?μm, which is among the highest reported in the literature for integrated refractive index sensors, and explained in terms of enhanced interaction between light and liquid within the PhC.     

Tunable doping of a metal with molecular spins

The mutual interaction of localized magnetic moments and their interplay with itinerant conduction electrons in a solid are central to many phenomena in condensed-matter physics, including magnetic ordering and related many-body phenomena such as the Kondo effect, the Ruderman-Kittel-Kasuya-Yoshida interaction and carrier-induced ferromagnetism in diluted magnetic semiconductors. The strength and relative importance of these spin phenomena are determined by the magnitude and sign of the exchange interaction between the localized magnetic moments and also by the mean distance between them. Detailed studies of such systems require the ability to tune the mean distance between the localized magnetic moments, which is equivalent to being able to control the concentration of magnetic impurities in the host material. Here, we present a method for doping a gold film with localized magnetic moments that involves depositing a monolayer of a metal terpyridine complex onto the film. The metal ions in the complexes can be cobalt or zinc, and the concentration of magnetic impurities in the gold film can be controlled by varying the relative amounts of cobalt complexes (which carry a spin) and zinc complexes (which have zero spin). Kondo and weak localization measurements demonstrate that the magnetic impurity concentration can be systematically varied up to ～800?ppm without any sign of inter-impurity interaction. Moreover, we find no evidence for the unwanted clustering that is often produced when using alternative methods.     

Pressure-induced dissociation of yeast glyceraldehyde-3-phosphate dehydrogenase: heterogeneous kinetics and perturbations of subunit structure

In studies of pressure-induced subunit dissociation of oligomeric proteins, the thermodynamic dissociation constant and the dissociation volume change are derived by assuming that high pressure itself does not significantly perturb the structure of both oligomer and isolated subunit. In this report, the intrinsic phosphorescence emission of Trp reveals that high-pressure dissociation of tetrameric yeast glyceraldehyde-3-phosphate dehydrogenase results in a dramatic shortening of the phosphorescence lifetime, from 300 to less than 2 ms, that is consistent with a profound loosening of the polypeptide structure about the phosphorescence probe. On pressure release, subunit reassociation occurs readily whereas recovery of the native phosphorescence properties is a very slow, thermally activated, process which goes hand in hand with the recovery of the catalytic activity. Further, the comparison between the kinetic traces that describe the degree of dissociation and the change in phosphorescence lifetime, at various applied pressures, has established the following: (1) that high pressure plays a direct role on the structural rearrangement, the extent of which increases with pressure; (2) that the conformational change in the monomer is concomitant with, or follows closely after, the break up of the tetramer, in any case long before an apparent tetramer-monomer equilibrium is established; (3) that native tetramers are highly heterogeneous with regard to their rate of dissociation. The influence of temperature, of protein concentration, of binding of NAD+, and of the addition of 2 M urea on the dissociation/phosphorescence kinetic profiles was also examined. The complications arising from these conformational changes for the derivation of the dissociation free energy change as well as their relevance for understanding the lack of concentration dependence of the degree of dissociation are discussed.