Extraction of nonstationarity information from correlation noise

A gas chromatograph is used as a model of a monitored process stream, and a method is developed to detect fixed-amplitude changes either in component concentration or system response to a perturbation. The multiple injection input and its advantages are based on the principles of correlation chromatography. The deconvolution of the aperiodic input pattern from the output results in a signal peak representing average system response and correlation “noise” which, when calibrated, gives the direction and magnitude of the change which has occurred. Because of the signal-averaging effect of the multiple inputs and deconvolution process, the effects of random fluctuations and noise are reduced.     

Impulse/response functions of individual components of flow-injection manifolds

The dispersion behaviour of the various individual parts making up a flow-injection manifold is often difficult to establish because it is virtually impossible to obtainthe required very small injection and detection volumes. It is shown that it is possible, under suitable experimental conditions, to find the impulse/response functionof each component by means of a deconvolution process of the response functions have been established, the response function of any arrangement can be predicted by convoluting the impulse/response functions of all the individuaol parts involved. Convolution and deconvolution were done in the Fourier domain, by using a fast FT algorithm.     

Electrochemical heat flow calorimeter

A device designed for research of heat phenomena occurring in chemical power sources (CPS) is described. The device includes two functional blocks: electrochemical and calorimetrical, operating under single control, which allows simultaneously performing electrochemical and calorimetric measurements. The calorimetric block is a heat flow calorimeter. The calorimetric chamber design provides the possibility of studying thermal processes in laboratory electrochemical cells and CPS of planar, disk, and prismatic design. The absolute measurement error of the heat flow is ±50 μW at the resolution of 1 μW. The operating temperature range of the calorimetric chamber is 0–90°C. The basis of the electrochemical block is a module of a four–range potentiostat–galvanostat. The maximum polarizing current of the potentiostat is ±200 mA at the maximum voltage on the auxiliary electrode of ±10 V. Multiuser remote access from the user computers over Ethernet to the device is provided for control and treatment of experimental data. Digital deconvolution filters allowing to compensate the response rate of the heat flow meter are used for processing primary data of calorimetric measurements.     

Synthesis of a positional scanning library of pentamers of N-alkylglycines assisted by microwave activation and validation via the identification of trypsin inhibitors

A positional scanning library of 625 N-alkylglycine pentamers has been synthesized on solid-phase, employing a set of 10 commercially available primary amines as a source of chemical diversity. The iterative synthetic steps were carried out in tea bags and accelerated by using microwave assisted organic synthesis (MAOS). The reactivity study of the primary amines used as diversity sources led to determine their relative reactivity values and equireactivity factors, which were applied to the library synthesis to ensure comparable concentrations of all final oligomers in the mixtures. This library was validated by the screening, deconvolution, and identification of trypsin inhibitors. These compounds are of potential interest for controlling the intracellular transport of TRPV1 channel.     

An absorbance-based micro-fluidic sensor for diffusion coefficient and molar mass determinations

The H-Sensor reported herein is a micro-fluidic device compatible with flow injection analysis (FIA) and high performance liquid chromatography (HPLC). The device detects analytes at two separate off-chip absorbance flow cells, providing two simultaneous absorbance measurements. The ratio of these two absorbance signals contains analyte diffusion coefficient information. A theoretical model for the sensing mechanism is presented. The model relates the signal Ratio to analyte diffusion coefficient. The model is qualitatively evaluated by comparing theoretical and experimental signal Ratio values. Experimental signal Ratios were collected via FIA for a variety of analytes, including sodium azide, benzoic acid, amino acids, peptides, and proteins. Measuring absorbance at multiple wavelengths provides higher order data allowing the analyte signals from mixtures to be deconvolved via classical least squares (CLS). As a result of the H-Sensor providing two simultaneous signals as a function of time for each sample injection, two simulated second-order HPLC chromatograms were generated using experimental H-Sensor data. The chemometric deconvolution method referred to as the generalized rank annihilation method (GRAM) was used to demonstrate chromatographic and spectroscopic deconvolution. GRAM also provides the signal Ratio value, therefore simultaneously obtaining the analyte diffusion coefficient information during deconvolution. The two chromatograms successfully serve as the standard and unknown for the GRAM deconvolution. GRAM was evaluated on chromatograms at various chromatographic resolutions. GRAM was found to function to a chromatographic resolution at and above 0.25 with a percent quantitative error of less then 10%.     

Chip-calorimeter for small samples

A method for measuring heat capacities of small samples using a chip-calorimeter and a heat pulse technique is described. The theoretical background to calculate the heat transport properties and the heat capacity of the sample from the pulse response function is given. Problems and potentials of the method are discussed. An example is given.     

Computerized separation of chromatographically unresolved peaks

A computerized peak deconvolution software and mass spectra were successfully applied for the deconvolution of overlapped peak cluster in the chromatogram obtained separating the complex mixture of pesticides by retention time locking gas chromatography-mass spectroscopy. The method based on the unique fragment ions in the spectra can be used for deconvolution of peak clusters if mass spectra of overlapped peaks differ. This method allows determining actual retention times of overlapped peaks. Peak areas found by this method however, cannot be used naturally for the quantitative purposes as the abundance of fragment ions used for this deconvolution procedure can dramatically differ. Computer assisted deconvolution of peaks in the peak clusters gives more realistic peak area ratios as at this method it is supposed equal response for all peaks overlapped in a cluster.     

A simple model for calorimeters with temperature programming

We present a theoretical study of an RC-model constituted only by one heat capacity and one coupling with the thermostat. It is assumed that the thermostat temperature varies as a function of time, and the heat capacity variation is due to its dependence either on temperature or on the mass exchange with the exterior.The results are parallel to the corresponding RC-models where the thermostat temperature is constant. The variations of sensibility are shown, as well as a criterion for the applicability of inverse filtering as a deconvolution technique in calorimeters with temperature programming.     

Energy transport in peptide helices: a comparison between high- and low-energy excitations

Energy transport in a short helical peptide in chloroform solution is studied by time-resolved femtosecond spectroscopy and accompanying nonequilibrium molecular dynamics (MD) simulations. In particular, the heat transport after excitation of an azobenzene chromophore attached to one terminus of the helix with 3 eV (UV) photons is compared to the excitation of a peptide C=O oscillator with 0.2 eV (IR) photons. The heat in the helix is detected at various distances from the heat source as a function of time by employing vibrational pump-probe spectroscopy. As a result, the carbonyl oscillators at different positions along the helix act as local thermometers. The experiments show that heat transport through the peptide after excitation with low-energy photons is at least 4 times faster than after UV excitation. On the other hand, the heat transport obtained by nonequilibrium MD simulations is largely insensitive to the kind of excitation. The calculations agree well with the experimental results for the low-frequency case; however, they give a factor of 5 too fast energy transport for the high-energy case. Employing instantaneous normal mode calculations of the MD trajectories, a simple harmonic model of heat transport is adopted, which shows that the heat diffusivity decreases significantly at temperatures initially reached by high-energy excitation. This finding suggests that the photoinduced energy gets trapped, if it is deposited in high amounts. The various competing mechanisms, such as vibrational T(1) relaxation, resonant transfer between excitonic states, cascading down relaxation, and low-frequency mode transfer, are discussed in detail.     

Dynamic mechanical and dielectric relaxations in poly(monoethylphenyl itaconate)

Dynamic mechanical and dielectric relaxational behavior of poly(monoethylphenyl itaconate) at different frequencies and temperatures was studied. Three relaxation zones are found. The dynamic mechanical response is dominated by a relaxation peak at room temperature, labeled β relaxation. Two prominent shoulders labelled as γ and α relaxations are observed. Because of the overlapping of the α and γ with the β relaxation, a deconvolution method to improve the understanding of these phenomena is proposed. In spite of the complexity of the experimental spectra, the proposed deconvolution method seems to be a convenient approach to interpret the relaxational behavior of this polymer. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2749–2756, 1997     

Melting of polymers by non-isothermal, temperature-modulated calorimetry: analysis of various irreversible latent heat contributions to the reversing heat capacity

This paper provides an analysis of contributions to the apparent, reversing heat capacity when measured by temperature-modulated differential scanning analysis (TMDSC) with an underlying heating rate in the temperature range where irreversible transitions with latent heats occur. To deconvolute the data of a TMDSC scan into a total and reversing part, it is common practice to use the sliding averages and the first harmonics of the Fourier series of temperature and heat-flow rate. Under certain conditions, this procedure produces erroneous reversing contributions which are detailed by experiment and simulation. Unless the response to the temperature modulation is linear, the total heat-flow rate is stationary, and the transition is truly reversible and occurs only once during the temperature scan, one cannot expect a true deconvolution of total and reversible effects. In the presence of multiple, irreversible transitions within a modulation period, however, each process involving latent heat can increase the modulation amplitude, as demonstrated by computer-simulation of polymer melting. As a result, the multiple transitions may give erroneously high latent heats when integrating the apparent reversing heat capacity with respect to temperature.     

Stable-isotope ratio analysis based on atomic hyperfine structure and optogalvanic spectroscopy

Atomic hyperfine structures were measured for the Cu I transition at 5782 A by optogalvanic spectroscopy at high resolution, with a cw dye laser. Samples were electro-deposited on the demountable cathode of a home-made hollow-cathode lamp. By spectral deconvolution, the relative isotopic abundances of (63)Cu and (65)Cu could be determined with good accuracy and precision. The technique is applicable to copper concentrations as low as 1.6 ppm.     

Ultrasensitive detection of the reduced form of nicotinamide adenine dinucleotide based on carbon nanotube field effect transistor

We developed a simple, ultrasensitive, and quantitative detection method for the reduced form of nicotinamide adenine dinucleotide (NADH), based on carbon nanotube field effect transistors (CNTFETs). Following the injection of NADH at different concentrations, we obtained different electrical signals from a semiconductor characterization system mimicking biological catalysis of NADH dehydrogenase (CoI). Here, FET was fabricated via photolithography, attaching silicon wells, as the detection chamber, on the channel area of the single wall carbon nanotube (SWCNT). SWCNTs were functionalized with phenazine derivant, a counterpart of the key functional prosthetic group of CoI enzyme. In the presence of NADH, electrons transferred to phenazine derivant through SWCNT, by analogous means of the electron transport chain formed by a series of iron-sulfur (FeS) clusters in CoI. Using this method, the limit of detection was as low as 1 pM, and the range of linear response was 10 pM to 500 nM. Significantly, this approach possesses great potential for applications in real-time detection of NADH at extremely low concentrations, and rigorous analysis for NADH in electrochemical fields.     

Thermophysical Properties of High-Temperature Reacting Mixtures of Carbon and Water in the Range 400–30,000 K and 0.1–10 atm. Part 1: Equilibrium Composition and Thermodynamic Properties

This paper is devoted to the calculation of the chemical equilibrium composition and thermodynamic properties of reacting mixtures of carbon and water at high temperature. Equilibrium particle concentrations and thermodynamic properties including mass density, molar weight, entropy, enthalpy and specific heat at constant pressure, sonic velocity, and heat capacity ratio are determined by the method of Gibbs free energy minimization, using species data from standard thermodynamic tables. The calculations, which assume local thermodynamic equilibrium, are performed in the temperature range from 400 to 30,000 K for pressures of 0.10, 1.0, 3.0, 5.0 and 10.0 atm. The properties of the reacting mixture are affected by the possible occurrence of solid carbon formation at low temperature, and therefore attention is paid to the influence of the carbon phase transition by comparing the results obtained with and without considering solid carbon formation. The results presented here clarify some basic chemical process and are reliable reference data for use in the simulation of plasmas in reacting carbon and water mixtures together with the need of transport coefficients computation.     

Determination of heat-exposure effects on the concentration of catecholamines in bovine plasma and milk

A reversed-phase high-performance liquid chromatographic method with electrochemical detection has been adapted for the determination of picogram concentrations of norepinephrine and epinephrine in bovine plasma and milk. This method has been used to monitor the levels of these catecholamines when lactating cows are exposed to heat stress under controlled conditions. In response to heat stress, epinephrine concentrations in milk and plasma were similar. However, norepinephrine concentrations in milk were one tenth of that in plasma.     

A study of the transport of ions against their concentration gradient across ion-exchange membranes using the network method

The network method has been used to analyze the conditions that favour the uphill transport across ion-exchange membranes. A model for the Nernst-Planck-Poisson equations describing the ionic transport in such system is proposed, including the Donnan equilibrium relations at the membrane/solution interfaces. With this model and the electric circuit simulation program PSPICE, the transient response of the system under open circuit conditions (I=0) and the response of the system subject to an applied potential difference are simulated. The ionic concentrations and electric potential profiles, as well as the electric current density, the ionic fluxes and the charge density, have been obtained as a function of time.     

Charge injection across self-assembly monolayers in organic field-effect transistors: odd-even effects

We investigate the role of self-assembly monolayers in modulating the response of organic field-effect transistors. Alkanethiol monolayers of chain length n are self-assembled on the source and drain electrodes of pentacene field-effect transistors. The charge carrier mobility mu exhibits large fluctuations correlated with odd-even n. For n < 8, mu increases by 1 order of magnitude owing to the decrease of the hole injection barrier and the improved molecular order at the organic-metallic interface. For n > or = 8, mu decays exponentially with an inverse decay length beta = 0.6 A(-1). Our results show that (i) charge injection across the interface occurs by through-bond tunneling of holes mediated by the alkanethiol layer; (ii) in the long-chain regime, the charge injection across the alkanethiol monolayer completely governs the transistor response; (iii) the transistor is a sensitive gauge for probing charge transport across single monolayers. The odd-even effect is ascribed to the anisotropic coupling between the alkanethiol terminal sigma bond and the HOMO level of ordered pentacene molecules.     

Thermoelectric transport properties in atomic scale conductors

The thermoelectric transport properties in atomic scale conductors consisting of a Si atom connected by two electrodes are investigated. It is found that both the electrical current and the heat current have two contributions, one from the voltage and the other from the temperature gradient. The quantities such as the Seebeck thermopower and the thermal conductance that characterize the thermoelectric transport properties of the tunnel atomic junction are studied quantitatively with a first-principles technique within the framework of Landauer-Buttiker formalism in the linear response regime. A finite thermopower only exists in a very narrow range where the energy derivative of the transmission function is nonzero. The thermopower anomaly is observed in the tunneling regime in this device but this does not violate the thermodynamic law with respect to the heat current.