Broad band high resolution rotational spectroscopy for Laboratory Astrophysics.

We present a new experimental setup devoted to the study of gas phase molecules and processes using broad band high spectral resolution rotational spectroscopy. A reactor chamber has been equipped with radio receivers similar to those used by radio astronomers to search for molecular emission in space. The whole Q (31.5-50 GHz) and W bands (72-116.5 GHz) are available for rotational spectroscopy observations. The receivers are equipped with 16×2.5 GHz Fast Fourier Transform spectrometers with a spectral resolution of 38.14 kHz allowing the simultaneous observation of the complete Q band and one third of the W band. The whole W band can be observed in three settings in which the Q band is always observed. Species such as CH3CN, OCS, and SO2 are detected, together with many of their isotopologues and vibrationally excited states, in very short observing times. The system permits automatic overnight observations and integration times as long as 2.4×105 seconds have been reached. The chamber is equipped with a radiofrequency source to produce cold plasmas and with four ultraviolet lamps to study photochemical processes. Plasmas of CH4, N2, CH3CN, NH3, O2, and H2, among other species, have been generated and the molecular products easily identified by their rotational spectrum, and mass spectrometry and optical spectroscopy. Finally, the rotational spectrum of the lowest energy conformer of CH3CH2NHCHO (N-Ethylformamide), a molecule previously characterized in microwave rotational spectroscopy, has been measured up to 116.5 GHz allowing the accurate determination of its rotational and distortion constants and its search in space.

Precisely controlled fabrication, manipulation and in-situ analysis of Cu based nanoparticles.

The increasing demand for nanostructured materials is mainly motivated by their key role in a wide variety of technologically relevant fields such as biomedicine, green sustainable energy or catalysis. We have succeeded to scale-up a type of gas aggregation source, called a multiple ion cluster source, for the generation of complex, ultra-pure nanoparticles made of different materials. The high production rates achieved (tens of g/day) for this kind of gas aggregation sources, and the inherent ability to control the structure of the nanoparticles in a controlled environment, make this equipment appealing for industrial purposes, a highly coveted aspect since the introduction of this type of sources. Furthermore, our innovative UHV experimental station also includes in-flight manipulation and processing capabilities by annealing, acceleration, or interaction with background gases along with in-situ characterization of the clusters and nanoparticles fabricated. As an example to demonstrate some of the capabilities of this new equipment, herein we present the fabrication of copper nanoparticles and their processing, including the controlled oxidation (from Cu0 to CuO through Cu2O, and their mixtures) at different stages in the machine.

Using radio astronomical receivers for molecular spectroscopic characterization in astrochemical laboratory simulations: A proof of concept.

We present a proof of concept on the coupling of radio astronomical receivers and spectrometers with chemical reactors and the performances of the resulting setup for spectroscopy and chemical simulations in laboratory astrophysics. Several experiments including cold plasma generation and UV photochemistry were performed in a 40 cm long gas cell placed in the beam path of the Aries 40 m radio telescope receivers operating in the 41-49 GHz frequency range interfaced with fast Fourier transform spectrometers providing 2 GHz bandwidth and 38 kHz resolution. The impedance matching of the cell windows has been studied using different materials. The choice of the material and its thickness was critical to obtain a sensitivity identical to that of standard radio astronomical observations. Spectroscopic signals arising from very low partial pressures of CH3OH, CH3CH2OH, HCOOH, OCS, CS, SO2 (<10-3 mbar) were detected in a few seconds. Fast data acquisition was achieved allowing for kinetic measurements in fragmentation experiments using electron impact or UV irradiation. Time evolution of chemical reactions involving OCS, O2 and CS2 was also observed demonstrating that reactive species, such as CS, can be maintained with high abundance in the gas phase during these experiments.

Mimicking Martian dust: An in-vacuum dust deposition system for testing the ultraviolet sensors on the Curiosity rover.

We have designed and developed an in-vacuum dust deposition system specifically conceived to simulate and study the effect of accumulation of Martian dust on the electronic instruments of scientific planetary exploration missions. We have used this device to characterize the dust effect on the UV sensor of the Rover Environmental Monitoring Station in the Mars science Laboratory mission of NASA in similar conditions to those found on Mars surface. The UV sensor includes six photodiodes for measuring the radiation in all UV wavelengths (direct incidence and reflected); it is placed on the body of Curiosity rover and it is severely affected by the dust deposited on it. Our experimental setup can help to estimate the duration of reliable reading of this instrument during operation. We have used an analogous of the Martian dust in chemical composition (magnetic species), color, and density, which has been characterized by X-ray spectroscopy. To ensure a Brownian motion of the dust during its fall and a homogeneous coverage on the instrumentation, the operating conditions of the vacuum vessel, determined by partial pressures and temperature, have to be modified to account for the different gravities of Mars with respect to Earth. We propose that our designed device and operational protocol can be of interest to test optoelectronic instrumentation affected by the opacity of dust, as can be the degradation of UV photodiodes in planetary exploration.

Mimicking Mars: a vacuum simulation chamber for testing environmental instrumentation for Mars exploration.

We have built a Mars environmental simulation chamber, designed to test new electromechanical devices and instruments that could be used in space missions. We have developed this environmental system aiming at validating the meteorological station Rover Environment Monitoring Station of NASA's Mars Science Laboratory mission currently installed on Curiosity rover. The vacuum chamber has been built following a modular configuration and operates at pressures ranging from 1000 to 10(-6) mbars, and it is possible to control the gas composition (the atmosphere) within this pressure range. The device (or sample) under study can be irradiated by an ultraviolet source and its temperature can be controlled in the range from 108 to 423 K. As an important improvement with respect to other simulation chambers, the atmospheric gas into the experimental chamber is cooled at the walls by the use of liquid-nitrogen heat exchangers. This chamber incorporates a dust generation mechanism designed to study Martian-dust deposition while modifying the conditions of temperature, and UV irradiated.

Interplay between fast diffusion and molecular interaction in the formation of self-assembled nanostructures of S-cysteine on Au(111).

We have studied the first stages leading to the formation of self-assembled monolayers of S-cysteine molecules adsorbed on a Au(111) surface. Density functional theory (DFT) calculations for the adsorption of individual cysteine molecules on Au(111) at room temperature show low-energy barriers all over the 2D Au(111) unit cell. As a consequence, cysteine molecules diffuse freely on the Au(111) surface and they can be regarded as a 2D molecular gas. The balance between molecule-molecule and molecule-substrate interactions induces molecular condensation and evaporation from the morphological surface structures (steps, reconstruction edges, etc.) as revealed by scanning tunnelling microscopy (STM) images. These processes lead progressively to the formation of a number of stable arrangements, not previously reported, such as single-molecular rows, trimers, and 2D islands. The condensation of these structures is driven by the aggregation of new molecules, stabilized by the formation of electrostatic interactions between adjacent NH(3)(+) and COO(-) groups, together with adsorption at a slightly more favorable quasi-top site of the herringbone Au reconstruction.

Mechanical complications in chronic peritoneal dialysis.

BACKGROUND: A significant number of complications and catheter failures in CAPD are due to mechanical problems. METHODS: We reviewed 105 consecutive peritoneal dialysis catheters, generally implanted by blind insertion technique, in 80 patients over an 11-year period. 137 mechanical problems were collected and classified according to their etiologies into the following: those related to the insertion procedure (n = 21; 15.3%), those related to the presence of dialysate in peritoneum (n = 33; 24%), catheter-related malfunction (n = 28; 20.4%), secondaries to abdominal events (n = 3; 0.2%), catheter accidents (n = 37; 26.2%) and others (n = 15; 11%). RESULTS: Removal of the catheter was performed in 86 of 105 catheters: mechanical complications accounted for 19 of them (21.8%) and 9 patients were definitively transferred to hemodialysis due to this problem. The most frequent complications were catheter accidents, although only a few of them required catheter removal. CONCLUSION: The majority of the catheter removals were due to catheter displacement (31.5%), this problem being more frequent in straight than in Swan Neck catheters.

Lipid emulsions and reticuloendothelial system function in healthy and burned guinea pigs.

The effect of total parenteral nutrition (TPN) regimens containing various quantities of long-chain triglyceride (LCT) and medium-chain triglyceride (MCT) emulsions on bacterial clearance and organ sequestration was evaluated in healthy and burned guinea pigs. In healthy guinea pigs, increasing the LCT component of TPN to 75% or greater of the nonprotein calories resulted in hepatomegaly, splenomegaly, a significant reduction in the sequestration of intravenously administered Pseudomonas aeruginosa by the liver and spleen, and a markedly increased clearance of bacteria into the lung. In burned guinea pigs, replacement of LCT with MCT emulsions at 75% of the nonprotein caloric intake reduced the sequestration of bacteria in the lung and restored to normal hepatic and splenic uptake. These results suggest that LCT emulsions at 75% of nonprotein calories result in reticuloendothelial system overload and increased bacterial sequestration in the lungs in normal and burned animals. In contrast, administration of MCT emulsions to the burned animal is less likely to result in increased pulmonary sequestration and decreased hepatic or splenic reticuloendothelial system function.

Protein metabolism during total parenteral nutrition (TPN) in injured rats using medium-chain triglycerides.

There are metabolic limitations to the infusion of large quantities of dextrose in critically ill patients receiving total parenteral nutrition. Of the alternative, nonprotein lipid sources, medium chain triglycerides (carbon chain length 8 and 10) are more rapidly oxidized and are deposited in the adipose tissue at rates much less than long chain triglycerides. In rats with burn injury receiving hypocaloric (dextrose and amino acids) parenteral feeding, we studied the changes in protein metabolism as a result of increasing the caloric intake by 33% by the addition of either dextrose, a soybean oil emulsion, a medium chain triglyceride emulsion, or a structured lipid emulsion of triglycerides synthesized from safflower oil (40%) and medium chain triglycerides (60%). Changes in body weight, blood glucose concentration, beta-hydroxybutyrate, lactate, amino acids, insulin, albumin, liver protein content, and nitrogen balance were measured during three days of feeding. Whole body leucine kinetics and muscle protein fractional synthetic rate were evaluated using a constant intravenous infusion of L-[1-14C]leucine. The addition of dextrose or soybean oil emulsion produced a significant increase in body weight and liver nitrogen but did not change albumin concentrations or leucine kinetics compared to those of the hypocaloric feeding group. Rats receiving medium chain triglycerides and structured lipid emulsions showed a reduction in branched chain amino acid concentrations and an improvement in serum albumin levels. However, the rats receiving the structured lipid emulsion also showed increased body weight, had a significant decrease in leucine oxidation, and showed a three day cumulative nitrogen balance significantly greater than zero.(ABSTRACT TRUNCATED AT 250 WORDS)

Structured medium-chain and long-chain triglyceride emulsions are superior to physical mixtures in sparing body protein in the burned rat.

The present study was undertaken to compare the effectiveness of a physical mixture of long-chain and medium-chain triglycerides with an emulsion consisting of chemically synthesized triglycerides composed of medium-chain and long-chain fatty acids in similar proportions. Sprague-Dawley rats received a 25% body surface area full-thickness scald burn on the dorsum. For the next three days, all rats received 300 kcal/kg/day as 160 kcal/kg/day glucose, 50 kcal/kg/day amino acid, and an additional 90 kcal/kg/day lipid emulsion as either long-chain triglyceride, medium-chain triglyceride, a 1:1 physical mix of medium-chain and long-chain triglycerides or a chemically structured triglyceride made up of 60% medium-chain fatty acid and a 40% safflower oil. Rats receiving the chemically structured lipid emulsion showed the greatest gain in body weight, the greatest positive nitrogen balance, and the highest serum albumin concentration, outstripping rats receiving the long-chain triglyceride, medium-chain triglyceride, and even the physical mixture long-chain and medium-chain triglycerides (P less than 0.01). A 30% increase in oxygen consumption and 35% increase in energy expenditure in rats given the medium-chain triglyceride emulsion alone (P less than 0.01) was observed. This study confirms that the metabolism of chemically structured triglycerides composed of medium-chain and long-chain fatty acids markedly differs from similar physical mixtures. For these reasons, the new structured lipid emulsions may prove advantageous in feeding the severely injured patient.

Hypocaloric lipid emulsions and amino acid metabolism in injured rats.

The present study was designed to determine the degree and mechanism by which administration of medium-chain triglyceride emulsions spare body protein after injury. Forty male rats underwent venous catheterization and received nonsterile bilateral femur fractures. All rats received 2.5 g/day amino acids and either no additional calories (group I) or 20 kcal/day of either glucose (group II), a long-chain triglyceride emulsion (group III), a medium-chain triglyceride emulsion (group IV), or a structured lipid emulsion composed of 40% sunflower oil and 60% medium-chain triglycerides (group V). The diets were administered for 3 days, and rates of plasma leucine flux, oxidation, and incorporation into protein as well as tissue protein synthetic rates in liver and muscle were measured using the constant infusion of L-[1-14C]leucine. Results demonstrated that the administration of glucose or various lipid emulsions improved cumulative nitrogen balance significantly when compared to a diet containing amino acids alone. In addition, the administration of glucose or lipid emulsions significantly stimulated protein synthesis in liver and muscle. Moreover, a structured lipid emulsion of medium- and long-chain fatty acids produced significant increases in liver protein synthesis greater than that observed with either glucose or long-chain triglyceride emulsions. We conclude that added energy as fat or glucose reduces net protein catabolism and improves tissue protein synthesis in these injures rats and that lipid emulsions are as effective as dextrose. A structured triglyceride emulsion synthesized from medium- and long-chain fatty acids appears to better support hepatic protein synthesis.

Protein dynamics during refeeding of protein-depleted rats: effects of increasing amino acid intake by TPN or enteral continuous feeding.

The effect of increasing nitrogen intake with constant calorie supply was studied in protein-depleted rats. Animals were randomized into three paired groups to receive either total parenteral nutrition (TPN) or enteral (EF) isocaloric feedings (240 kcal X kg-1 X day-1) differing only in their amount of amino acids. The diets, composed of dextrose, a safflower oil emulsion and crystalline amino acids, were infused continuously for 5 days. Daily nitrogen intakes were for controls (EF, n = 7; TPN, n = 6) 0.25 g/kg; for groups 1 (EF, n = 7; TPN, n = 8) 1.4 g/kg and for groups 2 (EF, n = 7; TPN, n = 7) 2.5 g/kg. The rats in groups 1 and 2 obtained significant protein repletion in terms of body weight, nitrogen retention, liver protein and serum albumin regardless of the route of nutrient delivery. However, rats in groups 2 (higher nitrogen intake) presented a more rapid and greater recovery despite a reduction in nitrogen utilization. Whole-body leucine kinetics studied at the end of controlled feeding periods were similar for EF and TPN rats. However, increasing nitrogen intake (1 and 2) increased whole-body leucine flux and incorporation into protein resulting in a better balance, since leucine release from protein breakdown was comparable to controls. Liver protein fractional synthetic rates were reduced in EF while remaining at a high rate in TPN group 2 and still more elevated in TPN group 1, suggesting a preferential support of liver protein by enteral feeding or the effect of TPN as a non-physiologic route.

A rationale for administering leukocyte endogenous mediator to protein malnourished, hospitalized patients.

Leukocyte endogenous mediator is a low molecular-weight protein synthesized by circulating monocytes and fixed macrophages of the reticuloendothelial system. Exogenous administration of leukocyte endogenous mediator to a well-nourished animal stimulates both specific and nonspecific immune function and replicates the protein metabolic response to infection, characterized by fever and increased amino acid oxidation, skeletal protein degradation and synthesis of "acute-phase" proteins. Leukocyte endogenous mediator administration also affords protection against semi-lethal doses of bacteremia in the well-nourished animal. In the protein-depleted host, synthesis or release of leukocyte endogenous mediator in response to infection appears to be reduced and the attenuated metabolic response may be attributed, in part, to a deficit in its production. However, nutritional repletion of the malnourished patient results in restoration of the capacity to produce leukocyte endogenous mediator usually within three to seven days, if adequate dietary protein is provided. Since protein malnutrition is associated with increased incidence and severity of bacterial infections, we postulate that the reduced synthesis and/or release of leukocyte endogenous mediator in protein malnutrition is detrimental. In those critically-ill, malnourished patients who cannot endogenously synthesize leukocyte endogenous mediator, and for clinical reasons cannot be repleted rapidly or are already infected and/or undergoing operative stress, exogenous administration of leukocyte endogenous mediator should be considered along with nutritional support. Administration of this protein to a seriously-ill malnourished individual should produce a metabolic profile of fever, increased urinary nitrogen excretion and falls in serum albumin concentrations that are generally considered pathologic. However, administration of leukocyte endogenous mediator over short periods of time should also provide the anabolic impetus for the augmented synthesis of proteins beneficial to recovery.(ABSTRACT TRUNCATED AT 400 WORDS)

Effect of ibuprofen on fever and metabolic changes induced by continuous infusion of leukocytic pyrogen (interleukin 1) or endotoxin.

Many of the metabolic sequelae to infection and inflammation, such as fever, trace mineral redistribution, skeletal muscle catabolism, and the acute-phase protein response, are mediated by leukocytic pyrogen (interleukin 1). In the anterior hypothalamus and in skeletal muscles leukocytic pyrogen appears to induce the synthesis of prostaglandin E2 which mediates fever and skeletal protein catabolism. It is unclear whether any additional metabolic responses to leukocytic pyrogen result from prostaglandin production. This study was undertaken to investigate the ability of ibuprofen, a specific cyclooxygenase inhibitor, to alter protein and trace metal responses to leukocytic pyrogen or endotoxin when given in quantities sufficient to block the febrile response. In guinea pigs given continuous infusions of leukocytic pyrogen or endotoxin, a 0.6 to 0.8 degrees C fever was observed within 4 h, and zinc and iron concentrations in serum fell by 63 to 78% (P less than 0.01). Rates of whole body amino acid appearance, oxidation, and incorporation into protein were all significantly increased by leukocytic pyrogen and endotoxin treatment, (P less than 0.05) as were the fractional hepatic and seromucoid protein synthesis rates in leukocytic pyrogen-treated animals (P less than 0.01). Muscle protein synthesis was unchanged. Although pretreatment with infusions of ibuprofen completely ablated the febrile response to leukocytic pyrogen and endotoxin, decreases in zinc and iron concentrations in serum and leukocytosis were unaffected. Overall increases in whole body amino acid kinetics induced by leukocytic pyrogen or endotoxin were only minimally affected by ibuprofen. We concluded that treatment with prostaglandin synthesis inhibitor ibuprofen did not affect whole body trace metal, hematological, or hepatic acute-phase-induced responses to leukocytic pyrogen or endotoxin, either because these responses are prostanoid independent or because they are only partially mediated by eicosanoid products.