Ferritin immunosensing on microfabricated electrodes based on the integration of immunoprecipitation and electrochemical signaling reactions.

A signal registration strategy from micropatterned immunosensors that converts antigen-antibody binding reactions into electrochemical signals was demonstrated. An array-type micropatterned gold electrode on a silicon wafer was fabricated, containing two electrode geometries of rectangular (100 microm x 500 microm) and circular (r. 50 microm) types, exhibiting electrochemical characteristics of bulk and micro-electrodes, respectively. Ferritin was employed as a model analyte for immunosensing because it has an advantageous molecular structure for functionalization to the sensing interface, and is regarded as a general marker protein for tumors and cancer recurrence. With the fabricated and ferritin-functionalized immunosensors, biospecific interactions were performed with antiferritin antiserum and secondary antibody samples, followed by electrochemical signaling via an immunoprecipitation reaction by the label enzyme. Under the optimized affinity-surface construction steps and reaction conditions, both types of microfabricated electrodes exhibited well-defined calibration results as a function of the protein concentration in antiserum samples. Furthermore, circular-type micropatterned immunoelectrodes exhibited voltammetric characteristics of microelectrodes, which is advantageous in terms of sensor operation under a fixed potential and low signal drift during the signaling reaction compared with the bulk-type electrodes. The results support that the employed signaling method with the proposed immunosensor configuration is fit for sensor miniaturization and integration to future biomicrosystems.     

Surface–plasmon-coupled photoluminescence from CdS nanoparticles with Au films

The enhancement of surface–plasmon-coupled photoluminescence from CdS nanoparticles was examined for various thicknesses of sputtered Au films. The improved luminescence with thickness control of Au correlated well with the increased density of surface–plasmon states, which was modified by the plasmon-dispersion relation at the planar Au/PMMA interface. By annealing the Au films to form a rough surface morphology, the emission in the CdS nanoparticles was further enhanced by the improved excitation and coupling of the surface–plasmon modes.     

Lorentz Invariant Decompositions of the State Vector Spaces and the Basis Problem

We consider a representation of the state reduction which depends neither on its reality nor on the details of when and how it emerges. Then by means of the representation we find necessary conditions, even if not the sufficient ones, for a decomposition of the state vector space to be a solution to the basis problem. The conditions are that the decomposition should be Lorentz invariant and orthogonal and that the associated projections should be continuous. They are shown to be able to determine a decomposition in each of a few examples considered if the other circumstances are taken into account together.     

Beam Recombination Characteristics in Array Laser Amplification Using Stimulated Brillouin Scattering Phase Conjugation

Beam recombination characteristics were numerically investigated in array laser amplification using stimulated Brillouin scattering phase conjugation. To clarify the effect of piston errors due to imperfect phase locking, spatial intensity profiles of the beam recombination output were calculated in both the near and the far field on the basis of Rayleigh-Sommerfeld diffraction theory. The analyses indicate that piston errors are seriously detrimental to the quality of a beam recombination output and should be eliminated by a proper phase locking. It is also found that the gap between the beam splitting-combining wedges has a negligible effect.Presented at 1996 International Workshop on Interferometry (IWI ‘96), August 27-29, Saitama, Japan.     

Pulse-amplitude equalization using a polarization-maintaining laser resonator

For the first time to our knowledge, pulse-amplitude equalization of rational-harmonically mode-locked fiber ring laser pulses has been experimentally demonstrated using a polarization-maintaining laser resonator without any additional device. The pulse-amplitude distribution of the laser pulses was controlled by the modulator driving power, and stable pulse-amplitude-equalized pulses with repetition rates of 20, 30, and 40 GHz have been obtained in the linear region of the modulator.     

Detection of Chemical Warfare Nerve Agents via a Beckmann Fragmentation of Aldoxime

Abstract

A new (E)-pyrene-1-carbaldehyde O-tert-butyldimethylsilyl oxime 3 was synthesized for the detection of chemical warfare nerve agents, O-isopropyl methylphosphonofluoridate (GB) and O-pinacolyl methylphosphonofluoridate (GD). ¹H NMR spectrum showed that the tert-butyldimethylsilyl (TBDMS) group was deprotected using TBAF and the oximate supernucleophile was made. Upon addition of chemical warfare agents (GB and GD) (50 mol%), the reaction was completely finished within 5 min and also the color change of reaction mixture was observed under a hand-held UV lamp with the naked eye.     

Progressive formation of fine and coarse ripples on SiC surface by repeated irradiation of femtosecond laser pulses

In this work, we report the progressive formation of first nanoparticles, next fine ripples, and eventually coarse ripples during the irradiation of single-crystal 6H-SiC surfaces with increasing number of femtosecond laser pulses (λ = 515 nm, τ = 250 fs, repetition rate = 100 kHz). At laser fluences greater than the single-pulse ablation threshold, nanoparticles were produced on the surface by the first few pulses over which fine ripple patterns overlapped at increased pulse numbers. As the pulse number was further increased over ten, the surface was gradually transformed into a coarse ripple–covered one. At laser fluence below the threshold, however, only fine ripples were formed nonuniformly.     

Impact of fluorine on the phase behavior of bis-p-tolyl propane in supercritical CO2, 1,1-difluoroethane,and 1,1,1,2-tetrafluoroethane

Fluorine substitution on a solute can have a significant effect on solute solubility in a given solvent and fluorine substitution on a solvent can also have a significant effect on solvent quality. The effect of fluorine is demonstrated with the phase behavior data for bis(p-tolyl)propane (BTP) compared to bis(p-tolyl)hexafluoropropane (BTHFP) in supercritical carbon dioxide, 1,1-difluoroethane (F152a), and 1,1,1,2-tetrafluoroethane (F134a). Semifluorinated BTHFP is more soluble than non-fluorinated BTP in all three solvents, especially CO₂. The CO₂–BTP system exhibits solid solubility behavior while the CO₂–BTHFP system exhibits liquid–liquid–vapor (LLV) behavior near the critical point of CO₂. Although the two dipolar hydrofluorocarbons (HFC) are better solvents than CO₂ for these two aromatic solid compounds, F152a is the superior HFC solvent, especially for BTP, because F152a has a smaller molar volume and a larger effective dipole moment than F134a. LLV behavior is also observed for the F134a–BTP system near the critical point of F134a although the F134a–BTHFP, F152a–BTP, and F152a–BTHFP systems all appear to exhibit type-I phase behavior and no liquid–liquid immiscibility near the respective critical points.     

New insight on the origin of the unusual acidity of Meldrum's acid from ab initio and combined QM/MM simulation study.

Ab initio molecular orbital and combined QM/MM Monte Carlo simulations have been carried out to investigate the origin of the unusually high acidity of Meldrum's acid. Traditionally, the high acidity of Meldrum's acid relative to that of methyl malonate has been attributed to an additive effect due to the presence of two E esters in the dilactone system. However, the present study reveals that there is significant nonadditive effect that also makes major contributions. This results from preferential stabilization of the enolate anion over that of Meldrum's acid due to anomeric stereoelectronic interactions. To investigate solvent effects on the acidity in aqueous solution, the relative acidities of Z and E conformers of methyl acetate have been determined in combined ab initio QM/MM simulations. There is significant solvent effect on the conformational equilibria for both the neutral ester and its enolate anion in water, leading to stabilization of the E stereoisomer. However, the computed solvent effect of 4.4 kcal/mol in favor of the E isomer of methyl acetate is largely offset by the favorable solvation of 3.4 kcal/mol for the E conformer of the enolate anion. This leads to an enhanced acidity of 3.4 kcal/mol for the (E)-methyl acetate in water over the Z conformer. In Meldrum's acid, it is the preferential stabilization of the enolate anion due to anomeric effects coupled with the intrinsically higher acidity of the E conformation of ester that is responsible for its high acidity.     

Chrysin Derivative CM1 and Exhibited Anti-Inflammatory Action by Upregulating Toll-Interacting Protein Expression in Lipopolysaccharide-Stimulated RAW264.7 Macrophage Cells

Although our previous study revealed that gamma-irradiated chrysin enhanced anti-inflammatory activity compared to intact chrysin, it remains unclear whether the chrysin derivative, CM1, produced by gamma irradiation, negatively regulates toll-like receptor (TLR) signaling. In this study, we investigated the molecular basis for the downregulation of TLR4 signal transduction by CM1 in macrophages. We initially determined the appropriate concentration of CM1 and found no cellular toxicity below 2 μg/mL. Upon stimulation with lipopolysaccharide (LPS), CM1 modulated LPS-stimulated inflammatory action by suppressing the release of proinflammatory mediators (cytokines TNF-α and IL-6) and nitric oxide (NO) and downregulated the mitogen-activated protein kinase (MAPK) and nuclear factor-κB (NF-κB) signaling pathways. Furthermore, CM1 markedly elevated the expression of the TLR negative regulator toll-interacting protein (Tollip) in dose- and time-dependent manners. LPS-induced expression of cell surface molecules (CD80, CD86, and MHC class I/II), proinflammatory cytokines (TNF-α and IL-6), COX-2, and iNOS-mediated NO were inhibited by CM1; these effects were prevented by the knockdown of Tollip expression. Additionally, CM1 did not affect the downregulation of LPS-induced expression of MAPKs and NF-κB signaling in Tollip-downregulated cells. These findings provide insight into effective therapeutic intervention of inflammatory disease by increasing the understanding of the negative regulation of TLR signaling induced by CM1.