Comparison of surface-enhanced resonance Raman scattering from unaggregated and aggregated nanoparticles

The effect of excitation frequency and state of aggregation on the sensitivity obtained in ultratrace analysis using colloidal suspensions of silver nanoparticles and surface-enhanced resonance Raman scattering (SERRS) detection is explored to define suitable conditions for quantitative analysis. Two structurally similar dyes, only one of which causes aggregation, were used as analytes without the use of external aggregating agents, thus simplifying the surface chemistry and removing a major source of error. Addition of the nonaggregating dye caused no change in particle charge or size and no time-dependent aggregation as measured by zeta potential and particle size analysis. The most intense single-particle scattering was obtained using excitation at the wavelength of the plasmon resonance. Molecular resonance added approximately 2 orders of magnitude in sensitivity. Addition of the aggregating dye caused a reduction in surface charge of the particles and initiated a time-dependent aggregation process. However, constant SERRS with time is obtained at some excitation wavelengths probably because a constant number of clusters active at these wavelengths is maintained in the dynamic aggregation process. The additional enhancement caused by aggregation and molecular resonance is spread over a range of excitation frequencies. However, electronic spectra suggested that plasmon resonance enhancement would be effective at the longest wavelength of excitation used (785 nm), but there was a significant drop in intensity this far away from the absorbance maximum of the dye (429 nm). Thus, sensitive analysis using suspensions of single nanoparticles is feasible provided the excitation frequency used is close to that of the plasmon resonance frequency. Aggregation adds only an enhancement of approximately 6 in the experiments performed since only some particles in aggregates will have an active plasmon at any one wavelength, but the range of excitation wavelengths at which good enhancement is obtained is wider giving more flexibility if more complexity.     

Metabolite-sensitive holographic biosensors

A new type of biosensor that combines the inexpensiveness and mass-produceability of reflection holograms with the selectivity and specificity of enzymes is described. pH-sensitive holographic sensors were fabricated from ionizable monomers incorporated into thin, polymeric, hydrogel films which were transformed into volume holograms using a diffusion method coupled with holographic recording, using a frequency-doubled Nd:YAG laser (532 nm). These holograms were used as transducer systems to monitor the pH changes associated with specific enzymatic reactions to construct prototype urea- and penicillin-sensitive biosensors. The diffraction wavelength (color) of the holographic biosensors was used to characterize their shrinkage and swelling behavior as a function of analyte concentration. The potential of these sensors for the measurement of the clinically and industrially important metabolites urea and penicillin G is demonstrated.     

Vicarious experience and partial reinforcement.

This study attempts to determine the conditions under which one can benefit from others' experience and to offer an explanation in terms of S-R theory using a mediational response mechanism. The apparatus was a modified slot machine which pays off on particular plays determined in advance by E. Ss were 200 university students divided into 5 pairs of groups, with one group in each pair having a 25% reward acquisition series and the other a 100% acquisition series. 5 different conditions of participation were used. The results showed that vicarious learning did take place as long as S actually participated in the winning during acquisition. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

A practical approach to fire hazard analysis for offshore structures

Offshore quantitative risk assessments (QRA) have historically been complex and costly. For large offshore design projects, the level of detail required for a QRA is often not available until well into the detailed design phase of the project. In these cases, the QRA may be unable to provide timely hazard understanding. As a result, the risk reduction measures identified often come too late to allow for cost effective changes to be implemented. This forces project management to make a number of difficult or costly decisions. This paper demonstrates how a scenario-based approached to fire risk assessment can be effectively applied early in a project's development. The scenario or design basis fire approach calculates the consequence of a select number of credible fire scenarios, determines the potential impact on the platform process equipment, structural members, egress routes, safety systems, and determines the effectiveness of potential options for mitigation. The early provision of hazard data allows the project team to select an optimum design that is safe and will meet corporate or regulatory risk criteria later in the project cycle. The focus of this paper is on the application of the scenario-based approach to gas jet fires. This paper draws on recent experience in the Gulf of Mexico (GOM) and other areas to outline an approach to fire hazard analysis and fire hazard management for deep-water structures. The methods presented will include discussions from the recent June 2002 International Workshop for Fire Loading and Response.     

Noise Immunity of High-Precision Low-Temperature Experiments

In the high-precision low-temperature experiments, noise immunity has long been an important issue. We consider the problem of measuring the slowly changing data in the presence of both white noise and sudden, short noise spikes. The Kalman filter is applied to attenuate the white noise and a spike detecting algorithm is applied to remove spikes resulting from the charged particles. Experimental data show that, with the Kalman filter, the RMS of the measurement noise in a 0.5 Hz bandwidth can be attenuated from 4 nK to 0.2 nK in the best case. A simple spike detecting algorithm worked effectively to remove spikes without increasing the random noise level.     

Robust maximum principle for multi-model LQ-problem

This paper presents the version of the robust maximum principle in the context of multi-model control formulated as the minimax Bolza problem. The cost function contains a terminal term as well as an integral one. A fixed horizon and terminal set are considered. The necessary conditions of the optimality are derived for the class of uncertain systems given by an ordinary differential equation with parameters from a given finite set. This problem consists in the control design providing a good behaviour for a given class of multi-model system. It is shown that the design of the minimax optimal controller is reduced to a finite-dimensional optimization problem given at the corresponding simplex set containing the weight parameters to be found. The robust optimal control may be interpreted as a mixture (with the optimal weights) of the controls which are optimal for each fixed parameter value. The proof is based on the recent results obtained for minimax Mayer problem (Boltyanski and Poznyak 1999a). The minimax linear quadratic control problem is considered in detail and the illustrative examples dealing with finite as well as infinite horizons conclude this paper.     

Interphase Formation and the Characterisation of Polymer/Ceramic Adhesion

The adhesion of photocured resins to ceramic substrates has been investigated using a variety of surface analytical techniques. Work has been aimed at establishing the physical and chemical interactions between resin and substrate in the interphase region and the effect of environmental exposure on these Analysis was aided by use of specially-designed, in-situ fracture facilities attached by an X-ray photoelectron spectrometer. Specific attention was focused on identification of localised regions of varying chemical composition in adhesive and adherend by imaging spectroscopies (imaging XPS and ToF SIMS imaging) and the study of the significance of such heterogeneities on adhesion and subsequent failure mechanisms.     

Awareness of coeliac disease and the gluten status of ‘gluten‐free’ food obtained on request in catering outlets in Ireland

The only current effective treatment for coeliac disease (CD) is a lifelong diet that is as free from gluten as possible. This study provides baseline evidence to inform future interventions of benefit to CD sufferers by examining awareness of CD issues by food servers and preparation staff, assessing their claims to provide gluten‐free foods by analysis of a meal concurrently sampled. While the majority of attempts to purchase a ‘gluten‐free’ meal on request in restaurants were successful, some 10% of all samples contained gluten, 2.7% between 21 and 100 mg kg^?1, and 7.7% >100 mg kg^?1 and two unsatisfactory samples were purchased from so‐called coeliac‐friendly restaurants. These findings were consistent with those obtained previously by Collin et al. [Alimentary Pharmacology & Therapeutics 19 (2004) 1277], Størsrud et al. [European Food Research & Technology 217 (2003) 481], Gélinas et al. [International Journal of Food Science & Technology 43 (2008) 1245] for cross contamination with gluten. Staff confidence, ‘gluten‐free’ notices, signs and menu choices were no guarantee of risk‐free dining for CD sufferers. Based on our findings we suggest the need for further training, specifically for chefs and managers.     

Extended Thermodynamics Derivation of Energy Dissipation in Unsteady Pipe Flow

Extended irreversible thermodynamics (EIT) provides a framework for deriving extensions to phenomenological equations (e.g., Newton's law of viscosity, Fick's law of mass transport, and Darcy's law for porous media flow) for problems involving high frequencies (i.e., rapid transients). In this paper, a phenomenological equation is derived for energy loss in 1D unsteady pipe flow using an EIT formalism. The resulting wall shear stress is equal to the sum of (1) the steady-state shear stress; (2) a term that is proportional to the local (i.e., temporal) acceleration; and (3) a term that is proportional to the product of the velocity and the convective (i.e., spatial) acceleration. The form of this EIT-based wall shear stress formula shows that EIT provides a physical basis for instantaneous acceleration based unsteady friction formulas. It also illustrates the limitations and underlying assumptions of these models. For example, instantaneous acceleration based unsteady friction formulas are limited to fast transients (i.e., transients in which the water hammer timescale is significantly smaller than the diffusion timescale). A characteristics solution for unsteady pipe flow is proposed in which the phenomenological equation is used to model energy dissipation. Comparison of numerical test results with measured data from upstream and downstream valve closure laboratory experiments shows excellent agreement.