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Gas chromatography for in situ analysis of a cometary nucleus. II. Analysis of permanent gases and light hydrocarbons with a carbon molecular sieve porous layer open tubular column.

Considering the severe constraints of space instrumentation, a great improvement for the in situ gas chromatographic (GC) determination of permanent and noble gases in a cometary nucleus is the use of a new carbon molecular sieve porous layer open tubular (PLOT) column called Carbobond. No exhaustive data dealing with this column being available, studies were carried out to entirely characterize its analytical performances, especially when used under the operating conditions of the cometary sampling and composition (COSAC) experiment of the European Space Agency (ESA) Rosetta space mission to be launched in 2003 for a rendezvous with comet 46 P/Wirtanen in 2011. The high efficiency and speed of analysis of this column at both atmospheric and vacuum outlet column pressure is demonstrated, and the kinetic mass transfer contribution of this carbon molecular sieve adsorbent is calculated. Besides, differential adsorption enthalpies of several gases and light hydrocarbons were determined from the variation of retention volume with temperature. The data indicate close adsorption behaviors on the Carbobond porous layer adsorbent and on the carbon molecular sieve Carboxen support used to prepare the packed columns. Moreover, taking into account the in situ operating conditions of the experiment, a study of two columns with different porous layer thicknesses allowed one to optimize the separation of the target components and to select the column parameters compatible with the instrument constraints. Comparison with columns of similar selectivity shows that these capillary columns are the first ones able to perform the same work as the packed and micro-packed columns dedicated to the separation of this range of compounds in GC space exploration.

Adsorption↗

A bottom up approach towards the acquisition and expression of sequential representations applied to a behaving real-world device: Distributed Adaptive Control III.

Biological systems display a high degree of flexibility in problem solving. In this paper a model is presented, Distributed Adaptive Control III (DACIII), which is aimed at understanding these forms of behavior. DACIII is part of a larger modeling series directed at understanding how biological systems acquire, retain, and express knowledge of the world. This modeling series has its roots, on one hand, in the methodological consideration that brain and behavior need to be modeled from a multi-level perspective. On the other, the importance of the acquisition of representations of events in the world, as opposed to an a priori specification, is emphasized. DACIII is presented against the background of the paradigms of classical and operant conditioning. On the basis of an analysis of these experimental approaches towards the study of animal behavior a theoretical framework is defined aimed at identifying the minimal requirements of a control structure which could display these behaviors. The proposed model is evaluated in different configurations using both simulated and real robots. It is demonstrated that DACIII is able to fully bootstrap itself from a mode of control which solely relies on proximal sensors and predefined reflexes, to a level of control which is dominated by acquired representations of events transduced by distal sensors. This transition is reflected in the performance of the behaving device, from strongly variable trajectories to highly structured behavioral sequences. The results are compared with alternative models of classical and operant conditioning and models which attempt to capture the properties of its underlying neural substrate.

Journal Article↗

Comparison of the efficiency of large-scale ceramic and membrane aeration systems with the dynamic off-gas method.

The aeration systems of two full-scale activated sludge basins were compared over 2.5 years under the same operating conditions using dynamic off-gas testing. Only the material of the diffuser was different, membrane vs. ceramic tube diffusers. The experimental design took the complexity and dynamics of the system into consideration. The investigation has shown that, although the membrane diffusers have higher initial standard oxygen transfer efficiency (SOTE) and standard aeration efficiency (SAE), these decreased over time, while the SAE of the ceramic diffusers started lower, but increased slightly over the whole period. Measurement of air distribution in the basins along with dissolved oxygen concentration profiles have provided important information on improving process control and reducing energy costs. The results show that dynamic off-gas testing can effectively be used for monitoring the aeration system and to check design assumptions under operating conditions. The information can be used to improve the design of new aeration systems or in retro-fitting existing basins.

Ceramics↗

Selective spinal anesthesia for outpatient laparoscopy. I: characteristics of three hypobaric solutions.

PURPOSE: To determine the characteristics and recovery profiles of three hypobaric spinal anesthetic solutions. METHODS: Thirty outpatients undergoing outpatient laparoscopy were randomly assigned to receive spinal anesthesia with one of three small-dose solutions. Group I--20 mg lidocaine plus 25 microg fentanyl; Group II--20 mg lidocaine plus 10 microg sufentanil; Group III--10 mg lidocaine plus 10 microg sufentanil. Solutions were diluted to three ml with sterile water for injection. A 27-gauge Whitacre needle was inserted at L2-3 or L3-4 in the sitting position. Sensory and motor recovery were assessed with pinprick, proprioception, light touch and a modified Bromage scale. RESULTS: Operating conditions were good to excellent in all three groups. The incidence of shoulder tip discomfort, pruritus and nausea was not significantly different between groups. Light touch was present in all three groups and proprioception was present in most patients during and after surgery. Group III patients had a more rapid recovery of pinprick analgesia and Group II patients had the slowest recovery of pinprick analgesia. Motor block recovery was comparable in the three groups. Eighty percent of patients in Groups III and I were able to perform 'deep knee bends' and 'straight leg raises' at the end of surgery. CONCLUSION: For short duration laparoscopy, spinal 10 mg lidocaine with 1O microg sufentanil provided selective pin prick analgesia, with preserved touch, proprioception and limited motor block. Operating conditions were satisfactory and most patients were able to fulfill 'walk out' criteria at the end of surgery.

Adult↗

Development of advanced image analysis techniques for the in situ characterization of multiphase dispersions occurring in bioreactors.

Fermentation bioprocesses typically involve two liquid phases (i.e. water and organic compounds) and one gas phase (air), together with suspended solids (i.e. biomass), which are the components to be dispersed. Characterization of multiphase dispersions is required as it determines mass transfer efficiency and bioreactor homogeneity. It is also needed for the appropriate design of contacting equipment, helping in establishing optimum operational conditions. This work describes the development of image analysis based techniques with advantages (in terms of data acquisition and processing), for the characterization of oil drops and bubble diameters in complex simulated fermentation broths. The system consists of fully digital acquisition of in situ images obtained from the inside of a mixing tank using a CCD camera synchronized with a stroboscopic light source, which are processed with a versatile commercial software. To improve the automation of particle recognition and counting, the Hough transform (HT) was used, so bubbles and oil drops were automatically detected and the processing time was reduced by 55% without losing accuracy with respect to a fully manual analysis. The system has been used for the detailed characterization of a number of operational conditions, including oil content, biomass morphology, presence of surfactants (such as proteins) and viscosity of the aqueous phase.

Bacteria↗

Activity-dependent spinal cord plasticity in health and disease.

Activity-dependent plasticity occurs in the spinal cord throughout life. Driven by input from the periphery and the brain, this plasticity plays an important role in the acquisition and maintenance of motor skills and in the effects of spinal cord injury and other central nervous system disorders. The responses of the isolated spinal cord to sensory input display sensitization, long-term potentiation, and related phenomena that contribute to chronic pain syndromes; they can also be modified by both classical and operant conditioning protocols. In animals with transected spinal cords and in humans with spinal cord injuries, treadmill training gradually modifies the spinal cord so as to improve performance. These adaptations by the isolated spinal cord are specific to the training regimen and underlie new approaches to restoring function after spinal cord injury. Descending inputs from the brain that occur during normal development, as a result of supraspinal trauma, and during skill acquisition change the spinal cord. The early development of adult spinal cord reflex patterns is driven by descending activity; disorders that disrupt descending activity later in life gradually change spinal cord reflexes. Athletic training, such as that undertaken by ballet dancers, is associated with gradual alterations in spinal reflexes that appear to contribute to skill acquisition. Operant conditioning protocols in animals and humans can produce comparable reflex changes and are associated with functional and structural plasticity in the spinal cord, including changes in motoneuron firing threshold and axonal conduction velocity, and in synaptic terminals on motoneurons. The corticospinal tract has a key role in producing this plasticity. Behavioral changes produced by practice or injury reflect the combination of plasticity at multiple spinal cord and supraspinal sites. Plasticity at multiple sites is both necessary-to insure continued performance of previously acquired behaviors-and inevitable-due to the ubiquity of the capacity for activity-dependent plasticity in the central nervous system. Appropriate induction and guidance of activity-dependent plasticity in the spinal cord is an essential component of new therapeutic approaches aimed at maximizing function after spinal cord injury or restoring function to a newly regenerated spinal cord. Because plasticity in the spinal cord contributes to skill acquisition and because the spinal cord is relatively simple and accessible, this plasticity is a logical and practical starting point for studying the acquisition and maintenance of skilled behaviors.

Animals↗

Simultaneous determination of eight vitamin D2 isomers by high-speed liquid chromatography.

The simultaneous determination of vitamin D2 and its isomers by high-speed liquid chromatography (HSLC) is described. Preferred operating conditions for the resolution and quantitation of vitamin D2 5,6-trans-vitamin D2, ergosterol, lumisterol2, isovitamin D2, isotachysterol2, tachysterol2, and previtamin D2 are as follows: column, "Zorbax" SIL (25 cm x 2.1 mm i.d.); pressure, 100-120 kg/cm2; temperature, ambient; detector, UV 254 nm; mobile phase, 0.15% methanol + 2% ether in pentane (for the simultaneous determination), 10% ether in hexane (for quantitation of the practical sets of isomers), or 55% CHCl3 (distilled) in pentane (for separation of isovitamin D2 and 5,6-trans-vitamin D2); sample size, 1 mul (greater than 1-5 ng); internal standard, p-cresol or alpha-naphthol. High-speed, good resolution, precise and accurate trace analysis, greater analysis flexibility, no necessity for preparing derivatives, and gentle operating conditions are main potential advantages of our method which has proved to be very efficient and surpasses all analytical procedures hitherto proposed.

Chemical Phenomena↗

Generation of micro-particles of proteins for aerosol delivery using high pressure modified carbon dioxide.

PURPOSE: To investigate the feasibility of using the Aerosol Solvent Extraction System (ASES) to generate microparticles of proteins suitable for aerosol delivery from aqueous-based solutions. METHODS: The ASES technique using high-pressure carbon dioxide modified with ethanol was utilised for the generation of microparticles of proteins (lysozyme, albumin, insulin and recombinant human deoxyribonuclease (rhDNase)) from aqueous solutions. Particle size, morphology, size distributions and powder aerosol performance were examined. The biochemical integrity of the processed proteins was assessed by testing the level of molecular aggregation using size exclusion chromatography and by bioassay technique for lysozyme. RESULTS: Proteins were precipitated as spherical particles ranging in size from 100 to 500 nm. The primary nano-sized particles agglomerated to form micron-sized particles during the precipitation process. The median size of the particles was a function of the operating conditions. In-vitro aerosol performance tests showed that the percent fine particle mass (< 5 microm) was approximately 65%, 40% and 20% for lysozyme, albumin and insulin, respectively. Negligible loss in the monomer content or biological activity was observed for lysozyme. Insulin exhibited slight aggregation and 93% of the monomer was retained after processing. Albumin was affected by processing and only 50-75% of the monomer was retained compared with 86% in the original material. However, rhDNase was substantially denatured during processing as shown by the significantly reduced monomer content. CONCLUSIONS: Micron-sized particles of lysozyme, albumin and insulin with satisfactory inhalation performance were successfully generated from aqueous solutions using the modified ASES technique. The biochemical integrity of the processed proteins was a function of the operating conditions and the nature of the individual protein.

Administration, Inhalation↗

Vancomycin mass transfer characteristics of high-flux cellulosic dialysers.

BACKGROUND: In comparison to conventional haemodialysis membranes, highly permeable membranes allow a broader spectrum of solute removal, including enhanced elimination of vancomycin (1448 Daltons). However, the mass transfer characteristics of vancomycin removal by highly permeable membranes have not been adequately assessed. An understanding of vancomycin's predominant dialytic mass transfer mechanism under a given set of operating conditions, including dialyser type and flow rates, may permit more accurate dosing of the drug. METHODS: We performed a mass transfer analysis of vancomycin removal by a high-flux dialyser, cellulose triacetate (CT). In a cross-over fashion with a 3-week washout between treatments, eight subjects received vancomycin 1000 mg (1) during the last hour of CT haemodialysis; or (2) after dialysis. Serial urea and vancomycin serum concentrations were used to assess dialytic removal. RESULTS: Dialysis removed 26.2% (mean; range 16-44%) of the administered vancomycin dose. While vancomycin removal and (Kt/V)urea were directly correlated (r = 0.88; P < 0.005), no correlation was observed between vancomycin removal and weight-normalized ultrafiltration rate. CONCLUSIONS: These findings suggest that for the CT dialyser and dialysis operating conditions employed in this study, vancomycin clearance was primarily mediated by diffusion. As such, these data challenge the general concept that convection is primarily responsible for the removal of solutes in the same molecular weight class as vancomycin during high-flux dialysis.

Adult↗

Decolorization and mineralization of a phthalocyanine dye C.I. Direct Blue 199 using UV/H2O2 process.

In this study, the successful decolorization and mineralization of phthalocyanine dye (C.I. Direct Blue 199, DB 199) by an advanced oxidation process (AOP), UV/H2O2, were observed while the experimental variables such as hydrogen peroxide dosage, UV dosage, initial dye concentration and pH were evaluated. The operating conditions for 90% decolorization of C.I. DB 199 and 74% removal of total organic carbon (TOC) were obtained for initial dye concentration of 20 mgl(-1), hydrogen peroxide dosage of 116.32 mM, UV dosage of 560 W and pH of 8.9 in 30 min. The pseudo-first order rate constant is a linear function of reverse of initial dye concentration. They linearly increased by incrementing UV dosage, yet were non-linear enhancement by increasing the hydrogen peroxide concentration. A higher pseudo-first order rate constant about 0.15 min(-1) was observed while hydrogen peroxide concentration within 5.82-116.32 mM. Moreover, the decolorization of C.I. DB 199 was observed to be more difficult than that of an azo dye, C.I. Acid Black 1, under the same operating conditions.

Azo Compounds↗

Evaluation of tocopherol recovery through simulation of molecular distillation process.

DISMOL simulator was used to determine the best possible operating conditions to guide, in future studies, experimental works. This simulator needs several physical-chemical properties and often it is very difficult to determine them because of the complexity of the involved components. Their determinations must be made through correlations and/or predictions, in order to characterize the system and calculate it. The first try is to have simulation results of a system that later can be validated with experimental data. To implement, in the simulator, the necessary parameters of complex systems is a difficult task. In this work, we aimed to determe these properties in order to evaluate the tocopherol (vitamin E) recovery using a DISMOL simulator. The raw material used was the crude deodorizer distillate of soya oil. With this procedure, it is possible to determine the best operating conditions for experimental works and to evaluate the process in the separation of new systems, analyzing the profiles obtained from these simulations for the falling film molecular distillator.

Antioxidants↗

Modeling, optimization and experimental assessment of continuous L-(-)-carnitine production by Escherichia coli cultures.

In a previous paper Cánovas et al. (Biotechnol Bioeng 2002;77:764-775) presented a model for L-(-)-carnitine production using Escherichia coli O44 K74, in a cell-recycle bioreactor for the biotransformation of crotonobetaine into L-carnitine. In this work we optimize this biotechnological setup and experimentally verify the predicted optimal parameter profiles. Provided with a reliable and robust S-system description of the cell-bioreactor combined system, we applied the Indirect Optimization Method described by Torres et al. (Biotechnol Bioeng 1997;55(5):758-772; Food Technol Biotechnol 1998;36(3):177-184). This optimization approach provides different parameter value profiles, all of which are compatible with the cell physiology and the bioreactor operating conditions, that yield increased rates of L-(-)-carnitine production. Three parameters were seen to be of critical importance for maximizing L-(-)-carnitine production: the dilution rate, the initial crotonobetaine concentration, and the carnitine dehydratase activity. When the first two were changed in the experimental setup, there was a 74% increase in the L-(-)-carnitine production rate, performance that was in close agreement with the predictions of the model. In accordance with the optimized solution, a further improvement (90% increase in the L-(-)-carnitine production rate) could be attained by over-expressing up to 5 times the carnitine dehydratase basal activity. Thus the optimization approach shown herein provides experimental evidence of a new strategy which demonstrates the possible variables that can be subjected to modifications compatible with the cell physiology and bioreactor operating conditions, and which are able to yield increased rates of L-(-)-carnitine production.

Alcohol Oxidoreductases↗

Simulation and optimization of a supercritical extraction process for recovering provitamin A.

In this work, a simulation procedure of a supercritical extraction process was developed through the use of the commercial simulator HYSYS (Hyprotech Ltd.), adapting the existing units to the operating conditions typical of the supercritical extraction process. The objective is to recover provitamin A (beta-carotene) from palm oil (esterified) using carbon dioxide/ethanol as the supercritical mixed solvent. This example characterizes the problem for recovering high added value product from natural sources, as the palm oil, which is desired by the market. Owing to the fact that esterified palm oil is a complex mixture, made by several components, in order to characterize this system in the simulator, it was necessary to create hypothetical components using the UNIFAC (universal function-group activity coefficients model) group contribution, because they are not present in a conventional database and, then, their physical properties must be estimated and/or predicted before the simulation. The optimization was carried out in each simulation for each equipment, in terms of operating conditions (temperature and pressure), in order to obtain the maximum recovery of carotenes. According to the results, it was possible to concentrate carotenes through two cycles of supercritical extraction with high yield. Furthermore, ethyl esters (biodiesel) were also obtained, as a byproduct of the proposed process, which can also be used as an alternative fuel, with the important characteristic that it is renewable.

Carbon Dioxide↗

Influence of formulation and process parameters on pellet production by powder layering technique.

The goal of the present study was to evaluate the influence of the formulation and operating conditions on pellet preparation by pan technique. To this end, a new pelletization process, typified by the application of powdered drug on sugar-based cores using the GS coating system was studied. Inert cores were intermittently treated with micronized drug powder and adhesive solution. This treatment led to the formation of multiple layers of drug particles around an inert core resulting in the production of pellets that can further be coated by different polymers to obtain modified release formulations. Different procedures have been used to evaluate a series of important parameters such as initial core weight; speed of powder application; speed, type, and position of the atomizers; atomization degree; temperature; and air cap. Good yield of drug layering was obtained by adjusting the quantity of both the drug powder to apply and the binder solution. Pellets obtained following the optimal operating conditions (defined in a pre-formulation study) were film coated with the acrylic polymer Eudragit L30D in order to produce a model formulation consisting of enteric polymer-coated pellets containing ibuprofen. During its preparation, the formulation showed no degradation of the drug; moreover, a low percentage of residual humidity was obtained, indicating that this system is very efficient for the production of highly stable formulations. This study showed the good performance of the GS automated pan-coating system in obtaining enteric coated pellets prepared by powder layering technique using aqueous solutions.

Chemistry, Pharmaceutical↗

Development of a balloon volume sensor for pulsating balloon catheters.

Helium pulsed balloons are integral components of several cardiovascular devices, including intraaortic balloon pumps (IABP) and a novel intravenous respiratory support catheter. Effective use of these devices clinically requires full inflation and deflation of the balloon, and improper operating conditions that lead to balloon under-inflation can potentially reduce respiratory or cardiac support provided to the patient. The goal of the present study was to extend basic spirographic techniques to develop a system to dynamically measure balloon volumes suitable for use in rapidly pulsating balloon catheters. The dynamic balloon volume sensor system (DBVSS) developed here used hot wire anemometry to measure helium flow in the drive line from console to catheter and integrated the flow to determine the volume delivered in each balloon pulsation. An important component of the DBVSS was an algorithm to automatically detect and adjust flow signals and measured balloon volumes in the presence of gas composition changes that arise from helium leaks occurring in these systems. The DBVSS was capable of measuring balloon volumes within 5-10% of actual balloon volumes over a broad range of operating conditions relevant to IABP and the respiratory support catheter. This includes variations in helium concentration from 70-100%, pulsation frequencies from 120-480 beats per minute, and simulated clinical conditions of reduced balloon filling caused by constricted vessels, increased driveline, or catheter resistance.

Air Pressure↗

Model-based optimization of a preparative ion-exchange step for antibody purification.

A method using a model-based approach to design and optimize an ion-exchange step in a protein purification process is proposed for the separation of IgG from a mixture containing IgG, BSA and myoglobin. The method consists of three steps. In the first step, the model is calibrated against carefully designed experiments. The chromatographic model describes the convective and dispersive flow in the column, the diffusion in the adsorbent particles, and the protein adsorption using Langmuir kinetics with mobile phase modulators (MPM). In the second step, the model is validated against a validation experiment and analyzed. In the third and final step, the operating conditions are optimized. In the optimization step, the loading volume and the elution gradient are optimized with regard to the most important costs: the fixed costs and the feed cost. The optimization is achieved by maximizing the objective functions productivity (i.e. the production rate for a given amount of stationary phase) and product yield (i.e. the fraction of IgG recovered in the product stream). All optimization is conducted under the constraint of 99% purity of the IgG. The model calibration and the analysis show that this purification step is determined mainly by the kinetics, although as large a protein as IgG is used in the study. The two different optima resulting from this study are a productivity of 2.7 g IgG/(s m3) stationary phase and a yield of 90%. This model-based approach also gives information of the robustness of the chosen operating conditions. It is shown that the bead diameter could only be increased from 15 microm to 35 microm with maximum productivity and a 99% purity constraint due to increased diffusion hindrance in larger beads.

Antibodies↗

Degradation of trace contaminants using coupled sonochemistry and Fenton's reagent.

The degradations of phenol in air-equilibrated aqueous media were investigated using coupled sonochemistry and Fenton's reagent for a variety of operating conditions. The decomposition yields of phenol (100-500 microM) were substantially enhanced due to the addition of Fenton's reagent (FeSO4 into the solutions irradiated at 608 kHz with 30 W and with reaction temperature 25 +/- 1 degree C. The decomposition process follows a pseudo-first-order reaction kinetics with respect to phenol concentration, and the rate constant of phenol disappearance observed increases by approximately 2-3 fold when FeSO4 was between 400 and 1000 M at pH = 3.5 +/- 0.2 (controlled by phosphate buffer) as a result of Fe(II) reaction with H2O2 enabling further production of additional OH* radicals. The results obtained here also indicate that the decomposition rate of aqueous phenol using coupled ultrasound and Fenton's reagent was strongly dependant on the initial concentration of reactant, the amount of Fe(II) added as well as the pH of solution. The optimal operating conditions for 100-500 microM phenol decomposition in the air-equilibrated aqueous media were obtained when FeSO4 concentration was between 400 and 1,000 microM with pH in the range 3.5-4.2 under ultrasonic irradiation at 608 kHz, 30 W and reaction temperature 25 +/- 1 degree C.

Disinfectants↗

Cognitive dimensions of chronic pain.

Behavioral interventions have now found widespread acceptance in the treatment of chronic benign pain. Among those with demonstrated therapeutic efficacy are operant conditioning, biofeedback and cognitive-behavior therapy. Since these interventions are based on different assumptions about the etiology of chronic pain, behavioral clinicians are often in the position of using different causal models to justify the use of different treatment procedures. In an effort to address this problem, the present paper proposes an explanatory framework based on the principles of cognitive psychology. Such a framework is parsimonious, empirically-based and offers an internally-consistent approach to understanding the development and maintenance of chronic pain symptoms. An important implication of this approach is that all behavioral interventions may exert an influence on chronic pain through a common mechanism, namely by changing the way clients think about their pain. Specific patterns of dysfunctional thinking are proposed to account for each of the major symptoms of chronic pain. These cognitive patterns include: awfulizing; low frustration tolerance; self-downing; and overgeneralizing. A conceptual analysis of biofeedback and operant conditioning found no evidence to suggest that either modality can effect changes in clients through noncognitive means. It was concluded that behavioral interventions are effective because they facilitate the development of new thinking skills that explicitly challenge the cognitive causes of chronic pain.

Behavior Therapy↗