Effect of Redox Conditions on the Fission Products Release from Irradiated Oxide Fuel

An in-house designed system for inductive vaporization (InVap) enables the investigation of the fission product (FP) release from irradiated fuel at temperatures up to 2300°C and under different redox conditions. Via the direct connection of the InVap device to an inductively coupled plasma mass spectrometer (ICP-MS) the on-line monitoring of the FP release is possible. Theoretically modeled and data experimentally determined on thermal treatment of irradiated fuel and release of volatile FPs (Cs, I), semi-volatile FPs (Sr, Ba, Tc, Mo, Ru) and actinides (U, Pu or Am) are discussed regarding to the nuclear fuel reprocessing technology.     

On-line monitoring of traces of aromatic-, phenolic- and chlorinated components in flue gases of industrial scale incinerators and cigarette smoke by direct-inlet laser ionization-mass spectrometry (REMPI-TOFMS)

The combination of laser induced resonance-enhanced multiphoton ionization (REMPI) and time-of-flight mass spectrometry (TOFMS) represents a highly selective as well as sensitive analytical technique, well suited for species selective real-time, on-line monitoring of trace-gases. Results presented are obtained with a newly designed, mobile REMPI-TOFMS instrument, optimized for field applications. The mobile REMPI-TOFMS device either is equipped with a compact excimer laser (KrF, λ = 248 nm) or a small Nd:YAG laser (forth harmonic frequency, λ = 266 nm). A special effusive molecular beam inlet system was used, which allows direct inlet of flue gases from e.g. waste incinerators without memory effects for compounds of a molecular weight of up to 260–280 amu. Detection sensitivities in the sub-ppb region are achieved under field measurement conditions. Applications concerning on-line monitoring of combustion byproducts and fuel components are presented. This includes on-line analysis of polycyclic aromatic hydrocarbons (PAH) in the flue gas of a 0.5 MW waste incineration pilot plant, headspace analysis of wood gasification products and crude oil composition (fuel analysis) as well as highly time resolved (single puff resolution) on-line analysis of cigarette smoke. The application of the on-line REMPI-TOFMS monitor for continuous analysis of dioxin indicators in the flue gas of e.g. hazardous waste incinerators is discussed.     

On-line monitoring of traces of aromatic-, phenolic- and chlorinated components in flue gases of industrial scale incinerators and cigarette smoke by direct-inlet laser ionization-mass spectrometry (REMPI-TOFMS)

The combination of laser induced resonance-enhanced multiphoton ionization (REMPI) and time-of-flight mass spectrometry (TOFMS) represents a highly selective as well as sensitive analytical technique, well suited for species selective real-time, on-line monitoring of trace-gases. Results presented are obtained with a newly designed, mobile REMPI-TOFMS instrument, optimized for field applications. The mobile REMPI-TOFMS device either is equipped with a compact excimer laser (KrF, λ = 248 nm) or a small Nd:YAG laser (forth harmonic frequency, λ = 266 nm). A special effusive molecular beam inlet system was used, which allows direct inlet of flue gases from e.g. waste incinerators without memory effects for compounds of a molecular weight of up to 260–280 amu. Detection sensitivities in the sub-ppb region are achieved under field measurement conditions. Applications concerning on-line monitoring of combustion byproducts and fuel components are presented. This includes on-line analysis of polycyclic aromatic hydrocarbons (PAH) in the flue gas of a 0.5 MW waste incineration pilot plant, headspace analysis of wood gasification products and crude oil composition (fuel analysis) as well as highly time resolved (single puff resolution) on-line analysis of cigarette smoke. The application of the on-line REMPI-TOFMS monitor for continuous analysis of dioxin indicators in the flue gas of e.g. hazardous waste incinerators is discussed. Received: 25 September 1998 / Revised: 7 December 1998 / Accepted: 10 December 1998     

Possibilities and Limitations of Fast Temperature Programming as a Route towards Fast GC

One possible way to speed up a gas chromatographic analysis is the application of fast temperature programming by using resistive heating techniques. With this heating technique programming rates up to 20° per second can be reached. A relative standard deviation of retention times better than 0.2% is obtained. Using fast temperature programming the analysis-times of a mineral oil sample, an industrial oligomer sample, and toxic compounds in diesel fuel have been reduced 5 to 20 times, compared to a standard temperature programmed analysis. In most cases resistive heating cannot be applied to reduce the analysis time of a complex sample. The use of fast temperature programming is preferable to the use of short columns and columns operated at above-optimum carrier gas velocities.     

On-site environmental analysis by membrane extraction with a sorbent interface combined with a portable gas chromatograph system

A novel device, membrane extraction with a sorbent interface (MESI) coupled with a portable gas chromatograph (GC) system, has been developed. The main components of this system include a membrane module, a microtrap, and a control unit for the heater and cooler. The membrane module, as an on-line sample-introduction device for this system, can be manipulated in different configurations, allowing for the selective permeation of analytes across the membrane into the carrier/stripping gas. The analytes are trapped and concentrated onto a microtrap, which serves as an injector for gas chromatography separation. A concentration pulse of the trapped analytes is generated through direct electrical heating of the microtrap. The characteristics of this system have been explored, and its applicability and effectiveness have been demonstrated in field monitoring applications including the analysis of toluene in wastewater, Volatile organic compounds (VOCs) in laboratory air, and chloroform in swimming-pool water. This system is very promising, as it is a simple, fast, and portable tool for on-site process environmental monitoring.     

Innovative Linker Strategies for Tumor-Targeted Drug Conjugates

The covalent conjugation of potent cytotoxic agents to either macromolecular carriers or small molecules represents a well-known approach to increase the therapeutic index of these drugs, thus improving treatment efficacy and minimizing side effects. In general, cytotoxic activity is displayed only upon cleavage of a specific chemical bond (linker) that connects the drug to the carrier. The perfect balance between the linker stability and its selective cleavage represents the key for success in these therapeutic approaches and the chemical toolbox to reach this goal is continuously expanding. In this Review article, we highlight recent advances on the different modalities to promote the selective release of cytotoxic agents, either by exploiting specific hallmarks of the tumor microenvironment (e.g. pH, enzyme expression) or by the application of external triggers (e.g. light and bioorthogonal reactions).     

Application of a device used for observation of controlled thermal processes in a furnace

This paper describes an appliance that allows to visually observe phenomena occurring in the studied materials during heating, from room temperature to 600 °C. The design criteria and device construction are described in details. The device allows for visual observation of physical phenomena of various material types, e.g., organic matter, polymers, and even observation of sintering mechanisms. Analysis of lubricant evaporation from powder metals (an aluminum alloy) in different atmospheres is shown. The featured device can also be used for interpretation of material defects. This is presented on the example of heating the aluminum alloy in an atmosphere containing oxygen (to simulate a furnace leakage). In addition, the influence of experimental atmosphere on melting and sintering processes is demonstrated. Another application of the presented device can be the visual observation of differences between combustion and pyrolysis processes. Our results show that the presented device is complementary with an advanced thermoanalysis apparatus which, in turn, does not allow visual observation of samples.     

SPR imaging biosensor for the 20S proteasome: sensor development and application to measurement of proteasomes in human blood plasma

The 20S proteasome is a multicatalytic enzyme complex responsible for intracellular protein degradation in mammalian cells. Its antigen level or enzymatic activity in blood plasma are potentially useful markers for various malignant and nonmalignant diseases. We have developed a method for highly selective determination of the 20S proteasome using a Surface Plasmon Resonance Imaging (SPRI) technique. It is based on the highly selective interaction between the proteasome’s catalytic β5 subunit and immobilized inhibitors (the synthetic peptide PSI and epoxomicin). Inhibitor concentration and pH were optimized. Analytical responses, linear ranges, accuracy, precision and interferences were investigated. Biosensors based on either PSI and epoxomicin were found to be suitable for quantitative determination of the proteasome, with a precision of ±10% for each, and recoveries of 102% and 113%, respectively, and with little interference by albumin, trypsin, chymotrypsin, cathepsin B and papain. The proteasome also was determined in plasma of healthy subjects and of patients suffering from acute leukemia. Both biosensors gave comparable results (2860 ng·mL-1 on average for control, and 42300 ng·mL-1 on average for leukemia patients).

Environmentally friendly fuel briquettes and pellets based on renewable lignocellulosic raw material and recycling thereof

This paper presents data regarding developments in the field of renewable energy sources based on lignocellulosic raw material, which can continuously provide a wide range of energy services. Data regarding reserves of nonhydrocarbon raw materials are presented: Russian forests represent 25% of the world timber reserves (perennial lignocellulosic materials), while fields and croplands represent 9% of the annual plants growing in the world. Processing of renewable lignocellulosic raw materials and biomass into fuel pellets and briquettes is capable of providing reliable supply of heating, electricity, and transport energy without green-house gas emissions and affecting the climate (in compliance with the Kyoto Protocol). The features of catalytic biomass gasification, which can be used to design the combined processes of biomass processing with simultaneous obtaining of fuel gas or synthesis gas, as well as nanoporous carbon materials, are discussed.     

Microfabricated chemical preconcentrators for gas-phase microanalytical detection systems

The gas or vapor preconcentrator is an analytical device that significantly improves the detection limit of a microanalytical system by preconcentrating the analyte. The preconcentrator performs front-end sampling and preconcentration of analyte by collecting and concentrating analyte over a period of time. After the analyte-collection phase is complete, a heat pulse releases the analyte as a concentrated wave into the detector. Desirable features of the preconcentrator device include the capability of operating at high flow rates, thermal heating with short-time constants, and selective collection of the analyte(s) of interest. The preconcentrators presented in this review are used as a generic front-end modification to gas-phase microanalytical detection systems, such as gas chromatographs, mass spectrometers, ion-mobility spectrometers, and microelectromechanical system (MEMS)-based chemical sensors. The advantages of the detector in incorporating a preconcentrator device are enhanced sensitivity and improved selectivity. Target analytes concentrated by the preconcentrators described in this review include various organic compounds in gas or vapor phase, such as explosives 2,4,6-trinitrotouluene (TNT) and 1,3,5 trinitro-1,3,5-triazine (RDX), chemical agent dimethyl methylphosphonate (DMMP), a broad range of organic vapors, such as toluene, benzene, ethylene and acetone, and mixtures of these gas-phase organic compounds. We discuss examples of the current trends in microfabricated preconcentrator technology as well as several applications of microfabricated preconcentrators.     

Modelling of the Plasma–Sheath Boundary Region in Wall-Stabilized Arc Plasmas: Unipolar Discharge Properties

A two-dimensional model of the non-equilibrium unipolar discharge occurring in the plasma–sheath boundary region of a transferred-arc was developed. This model was used to study the current transfer to the nozzle (1 mm diameter) of a 30 A arc cutting torch operated with oxygen. The energy balance and chemistry processes in the discharge were described by using a kinetic block of 45 elementary reactions and processes with the participation of 13 species including electronically excited particles. The nonlocal transport of electrons was accounted for into the fluid model. The dependence of the ion mobility with the electric field was also considered. Basic discharge properties were described. It has been found that a large part (~ 80%) of the total electric power (1700 mW) delivered in the bulk of the sheath region is spent in heating the positive ions and further dissipated through collisions with the neutral particles. The results also showed that the electron energy loss in inelastic collisions represents only ~ 25% of the electron power and that about 63% of the power spent on gas heating is produced by the ion–molecule reaction, the electron–ion and ion–ion recombination reactions, and by the electron attachment. The rest of the power converted into heat is contributed by dissociation by electron-impact, dissociative ionization and quenching of O(¹D). Some fast gas heating channels which are expected to play a key role in the double-arcing phenomena in oxygen gas were also identified.     

Chemical-looping gasification of biomass in a 10 kW_(th) interconnected fluidized bed reactor using Fe_2O_3/Al_2O_3 oxygen carrier

Abstract:The aim of this research is to design and operate a 10 kW hot chemical-looping gasification(CLG)unit using Fe2O3/Al2O3as an oxygen carrier and saw dust as a fuel.The effect of the operation temperature on gas composition in the air reactor and the fuel reactor,and the carbon conversion of biomass to CO2and CO in the fuel reactor have been experimentally studied.A total60 h run has been obtained with the same batch of oxygen carrier of iron oxide supported with alumina.The results show that CO and H2concentrations are increased with increasing temperature in the fuel reactor.It is also found that with increasing fuel reactor temperature,both the amount of residual char in the fuel reactor and CO2concentration of the exit gas from the air reactor are degreased.Carbon conversion rate and gasification efficiency are increased by increasing temperature and H2production at 870℃reaches the highest rate.Scanning electron microscopy(SEM),X-ray diffraction(XRD)and BET-surface area tests have been used to characterize fresh and reacted oxygen carrier particles.The results display that the oxygen carrier activity is not declined and the specific surface area of the oxygen carrier particles is not decreased significantly.     

Control of block copolymer morphology: An example of selective morphology induced by self‐assembly formation condition

An example case of selective morphology by simply varying pH and heating profile based on a diblock copolymer, i.e., poly(N‐isopropylacrylamide) (PNIPAAM) and poly[2‐(dimethylamino)ethyl acrylate] (PDMAEA) is reported. A variation of pH induces an aggregation of the block copolymers in either micelles or vesicles. In a subsequent step, temperature variation triggers the formation of vesicular structures. This demonstrates not only the temperature but also the heating rate that tunes the nanostructures from micelles to vesicles. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009     

Studies of pyrolysis and air heating of rayon by inverse gas chromatography

Inverse gas chromatography using water probing at 110°C was carried out to characterize rayon yarns after prior heating at 200 and 250°C in both inert (nitrogen) and oxidative (dry air) atmospheres for successively longer time intervals. During the early stages of heating in either atmosphere, the affinity of the rayon for water drops rapidly. However, whereas continued heating in N₂ results in a further loss of activity, data have been obtained showing that after an initial period yarns heated in air at 250°C exhibit an increasing attraction for water even while losing more weight.     

Stability of the FID sensitivity during an analysis in capillary GC

The sensitivity of an FID may change when the carrier gas flow rate changes during a chromatographic run. Sample parts which are eluted at reduced FID sensitivity produce a reduced peak area, hence are discriminated as compared to other components. Sensitivity changes were studied for hydrogen as carrier gas. For the detector tested, differences in the carrier gas flow rates of 1 ml/min shifted the FID sensitivity by 1 to 5% (depending on the fuel gas supply). Thus the stability of the sensitivity is no longer ensured as soon as the carrier gas flow rate is changed manually or by an automatic programmer during an analysis. Sensitivity drifts may also occur during temperature programmed runs with a pressure regulated carrier gas supply since the gas flow through the capillary drops with increasing temperature. Such shifts in the response became noticeable as soon as relatively high carrier gas flow rates combined with long range temperature programmes were used. The typical patterns of such discriminations are shown, closing with a discussion on the possibilities for minimizing such undesired effects.     

Micropumping of liquid by directional growth and selective venting of gas bubbles

We introduce a new mechanism to pump liquid in microchannels based on the directional growth and displacement of gas bubbles in conjunction with the non-directional and selective removal of the bubbles. A majority of the existing bubble-driven micropumps employs boiling despite the unfavorable scaling of energy consumption for miniaturization because the vapor bubbles can be easily removed by condensation. Other gas generation methods are rarely suitable for micropumping applications because it is difficult to remove the gas bubbles promptly from a pump loop. In order to eradicate this limitation, the rapid removal of insoluble gas bubbles without liquid leakage is achieved with hydrophobic nanopores, allowing the use of virtually any kind of bubbles. In this paper, electrolysis and gas injection are demonstrated as two distinctively different gas sources. The proposed mechanism is first proved by circulating water in a looped microchannel. Using H(2) and O(2) gas bubbles continuously generated by electrolysis, a prototype device with a looped channel shows a volumetric flow rate of 4.5-13.5 nL s(-1) with a direct current (DC) power input of 2-85 mW. A similar device with an open-ended microchannel gives a maximum flow rate of approximately 65 nL s(-1) and a maximum pressure head of approximately 195 Pa with 14 mW input. The electrolytic-bubble-driven micropump operates with a 10-100 times higher power efficiency than its thermal-bubble-driven counterparts and exhibits better controllability. The pumping mechanism is then implemented by injecting nitrogen gas bubbles to demonstrate the flexibility of bubble sources, which would allow one to choose them for specific needs (e.g., energy efficiency, thermal sensitivity, biocompatibility, and adjustable flow rate), making the proposed mechanism attractive for many applications including micro total analysis systems (microTAS) and micro fuel cells.     

Use of a recently developed thermal modulator within the context of comprehensive two‐dimensional gas chromatography combined with time‐of‐flight mass spectrometry: Gas flow optimization aspects

The present research is based on the use of a recently developed comprehensive two‐dimensional gas chromatography thermal modulator, which is defined as solid‐state modulator. The transfer device was installed on top of a single gas chromatography oven, while benchtop low‐resolution time‐of‐flight mass spectrometry was used to monitor the compounds exiting the second analytical column. The solid‐state modulator was first described by Luong et al. in 2016, and it is a moving modulator that does not require heating and cooling gases to generate comprehensive two‐dimensional gas chromatography data. The accumulation and remobilization steps occur on a trapping capillary, this being subjected to thermoelectric cooling and micathermic heating. In this study, the effects of the gas linear velocity on the modulation performance were evaluated by using two different uncoated trapping capillaries, viz., 0.8 m × 0.25 mm id and 0.8 m × 0.20 mm id. Solid‐state modulator applications were carried out on a standard solution containing n‐alkanes (C_9, C_10, C₁₂), and on a sample of diesel fuel. The results indicated that the type of trapping capillary and gas velocity have a profound effect on modulation efficiency.     

Fuel cell with polymer electrolyte: calculation of overall characteristics of oxygen cathode with account for processes of gas,vapor, and heat exchange

Computer simulation was performed for the processes occurring in the basic elements of the cathode (active layer, gas-diffusion layer) and bipolar plate of a fuel cell with Nafion as electrolyte and a platinum catalyst. Current generation in the active layer was considered together with the heat exchange processes (release of the heat formed in the active layer through the gas-diffusion layer into the bipolar plate), gas and vapor exchange in the gas-diffusion layer and process of the gas reagent (oxygen) saturation by water vapor in the bipolar plate channels. Voltammetric curves and dependences on the cathode potential of the power density, vapor flow dissipated from the active layer to the bipolar plate, actual active layer temperature and reduced partial pressures of oxygen and water vapors near the interface between the active and gas-diffusion layers were calculated. Analysis is performed of the way the heating of the cathode active layer intensifies the process of current generation in it, significantly increasing the value of overall characteristics of the cathode (current and power density).     

Supercritical fluid extraction coupled with chromatography-mass spectrometry: Hair analysis. Chromatography-mass spectrometry data processing using the CODA mathematical algorithm

The composition of medium-volatility organic compounds extracted from human hair using supercritical fluid extraction (SFE) was determined. The entire extract was trapped from a gas flow in a sorption device at the extractor outlet and thermally desorbed into a gas chromatography-mass spectrometry (GC-MS) instrument. The extracted compounds were identified either by the direct processing of GC-MS data or using the CODA mathematical algorithm. The combination of solventless SFE with the transfer of the entire extract into a GC-MS instrument with the direct analysis of GC-MS data allowed us to determine organic compounds at a level of 3.9 pg/mg hair. The CODA mathematical algorithm for the processing of GC-MS data allowed us to determine compounds at a level of 1.7 pg/mg hair; in the majority of publications, this determination limit was achieved either by selective ion detection or using a GC-MS-MS technique.