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At least 73 records · Page 4

LabVIEW-based control software for para-hydrogen induced polarization instrumentation

The elucidation of cell metabolic mechanisms is the modern underpinning of the diagnosis, treatment, and in some cases the prevention of disease. Para-Hydrogen induced polarization (PHIP) enhances magnetic resonance imaging (MRI) signals over 10 000 fold, allowing for the MRI of cell metabolic mechanisms. This signal enhancement is the result of hyperpolarizing endogenous substances used as contrast agents during imaging. PHIP instrumentation hyperpolarizes Carbon-13 ({sup 13}C) based substances using a process requiring control of a number of factors: chemical reaction timing, gas flow, monitoring of a static magnetic field (B{sub o}), radio frequency (RF) irradiation timing, reaction temperature, and gas pressures. Current PHIP instruments manually control the hyperpolarization process resulting in the lack of the precise control of factors listed above, resulting in non-reproducible results. We discuss the design and implementation of a LabVIEW based computer program that automatically and precisely controls the delivery and manipulation of gases and samples, monitoring gas pressures, environmental temperature, and RF sample irradiation. We show that the automated control over the hyperpolarization process results in the hyperpolarization of hydroxyethylpropionate. The implementation of this software provides the fast prototyping of PHIP instrumentation for the evaluation of a myriad of {sup 13}C based endogenous contrast agents used in molecular imaging.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Microwave-assisted synthesis of iron sulfide motifs for electrochemical applications

Abstract The syntheses of FeS 2 and Fe 3 S 4 nanomaterials were optimized using a novel facile, surfactant-free, and microwave-assisted, one-pot synthesis method, run under ambient and reasonably mild reaction conditions. Synthetic parameters, such as metal precursor salt identity, reaction time, reaction temperature, metal:sulfur molar ratios, and solvent combinations, were all systematically investigated and optimized. A series of FeS 2 (pyrite) samples was initially fabricated using thioacetamide (TAA) as the sulfur precursor to generate a distinctive, uniform octahedra-based morphology. Switching the sulfur precursor from TAA to L-cysteine resulted in a corresponding transformation in not only chemical composition from FeS 2 to an iron thiospinel structure, Fe 3 S 4 (otherwise known as greigite), but also an associated morphological evolution from octahedra to nanosheet aggregates. The study of these materials has enabled crucial insights into the formation mechanisms of these materials under a relatively non-conventional microwave-assisted setting. Furthermore, in separate experiments, multi-walled carbon nanotubes (MWNTs) and graphene were added in with underlying metal sulfide species to create conductive Fe–S/MWNT composites and Fe–S/graphene composites, respectively. The method of addition of either MWNTs or graphene was also explored, wherein an ‘ ex-situ ’ synthetic procedure was found to be the least disruptive means of attachment and immobilization onto iron sulfide co-reagents as a means of preserving the latter’s inherent composition and morphology. The redox acidity for the parent material and associated composites demonstrates the utility of our as-developed synthetic methods for creating motifs relevant for electrochemical applications, such as energy storage.

25 ENERGY STORAGE↗

Directional errors of movements and their correction in a discrete tracking task

Subjects can correct their own errors of movement more quickly than they can react to external stimuli by using three general categories of feedback: (1) knowledge of results, primarily visually mediated; (2) proprioceptive or kinaesthetic such as from muscle spindles and joint receptors, and (3) corollary discharge or efference copy within the central nervous system. The effects of these feedbacks on simple reaction time, choice reaction time, and error correction time were studied in four normal human subjects. The movement used was plantarflexion and dorsiflexion of the ankle joint. The feedback loops were modified, by changing the sign of the visual display to alter the subject's perception of results, and by applying vibration at 100 Hz simultaneously to both the agonist and antagonist muscles of the ankle joint. The central processing was interfered with when the subjects were given moderate doses of alcohol (blood alcohol concentration levels of up to 0.07%). Vibration and alcohol increase both the simple and choice reaction times but not the error correction time.

Jaeger, R. J.↗

Sulfuric acid functional zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts for alkylation of phenol with tert-butyl alcohol

Several zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts (SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48) were prepared by the impregnation method and their physicochemical properties were characterized by means of XRD, FT-IR, TEM, NH{sub 3}-TPD and N{sub 2} physical adsorption. Also, the catalytic activities of these solid acid catalysts were evaluated by the alkylation of phenol with tert-butyl alcohol. The effect of weight hour space velocity (WHSV), reaction time and reaction temperature on catalytic properties was also studied. The results show that the SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48 still have good mesoporous structure and long range ordering. Compared with the Zr (or Al)–MCM-48 samples, SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48 solid acid catalysts have strong acidity and exhibit high activities in alkylation reaction of phenol with tert-butyl alcohol. The SO{sub 4}{sup 2−}/Zr-MCM-48-25 (molar ratio of Si/Zr=0.04) catalyst was found to be the most promising and gave the highest phenol conversion among all catalysts. A maximum phenol conversion of 91.6% with 4-tert-butyl phenol (4-TBP) selectivity of 81.8% was achieved when the molar ratio of tert-butyl alcohol:phenol is 2:1, reaction time is 2 h, the WHSV is 2 h{sup −1} and the reaction temperature is 140 °C. - Highlights: • Sulfuric acid functional mesoporous solid acid catalysts were prepared via impregnation method. • The alkylation of phenol with tert-butyl alcohol was carried out over these solid acid catalysts. • The catalytic activity of SO{sub 4}{sup 2−}/Zr-MCM-48-25 catalyst is much higher than that of the others. • A maximum phenol conversion of 91.6% was achieved under optimum reaction conditions for SO{sub 4}{sup 2−}/Zr-MCM-48-25.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fractional space–time nonlinear reaction–convection–diffusion

We comment the fractional space–time reaction–convection–diffusion defined by Grünwald–Letnikov, Riesz and Riesz–Feller fractional derivatives. We find the explicit travelling wave solution, using the similarity reduction. We plot its graphics to illustrate the anomalous behavior and investigate its properties associated with memory and distance effects.

97 MATHEMATICS AND COMPUTING↗

Employing ISRU Models to Improve Hardware Design

An analytical model for hydrogen reduction of regolith was used to investigate the effects of several key variables on the energy and mass performance of reactors for a lunar in-situ resource utilization oxygen production plant. Reactor geometry, reaction time, number of reactors, heat recuperation, heat loss, and operating pressure were all studied to guide hardware designers who are developing future prototype reactors. The effects of heat recuperation where the incoming regolith is pre-heated by the hot spent regolith before transfer was also investigated for the first time. In general, longer reaction times per batch provide a lower overall energy, but also result in larger and heavier reactors. Three reactors with long heat-up times results in similar energy requirements as a two-reactor system with all other parameters the same. Three reactors with heat recuperation results in energy reductions of 20 to 40 percent compared to a three-reactor system with no heat recuperation. Increasing operating pressure can provide similar energy reductions as heat recuperation for the same reaction times.

Linne, Diane L.↗

Fundamental study of furfuryl alcohol dehydration reaction over molybdenum oxide catalyst

Here, the conversion of furfuryl alcohol (FA) and selectivity towards dimers (C 9 -C 10 ) and trimers (C 14 -C 15 ) were investigated over molybdenum oxide (MoO 3 ) catalyst. It was observed that FA conversion increased as an increase of reaction time. However, longer reaction time tended to limit the selectivity to dimers and trimers. Characterization data obtained from XRD, Raman, and XPS showed that after the reaction the terminal Mo=O bond was elongated and the oxidation state was changed from Mo 6+ to Mo 5+ . This was likely caused by the delocalization of extra electron to the Mo center during the activation of FA on MoO 3 surface, instead of the formation of oxygen vacancy. After a proper regeneration process, the structure distortion caused by the elongation of Mo=O bond was fully restored, however, the oxidation state were only restored to Mo 5+ / 6+ . Finally, recyclability test using regenerated MoO 3 indicates Mo 5+ / 6+ can be as active as Mo 6+ .

36 MATERIALS SCIENCE↗

Reducing ion diffusion at atmospheric pressure through intermingled positive and negative ions

Increasing ion molecule reaction times for ambient ionization techniques can increase sensitivity of detection. Longer reaction times result in an increase in analyte signal relative to the reactant ion signal, however with a subsequent decrease in the total ion intensity. This loss in the total number of ions reaching the detector limits the extent to which increased reaction time can improve detection in practical applications. In this study ion loss was measured using either electric fields or gas flow to control ion transit time. Ion transit times ranged from 40 ms to 8s, which resulted in ion densities ranging from 5 x 10 6 to 2 x 10 4 ions/cm 3 , respectively. These results provide insights into practical reaction time limitations or experimental boundaries when exploring sensitivity enhancements in ambient ionization. When exploring longer reaction times with an atmospheric flow tube coupled to a mass spectrometer (AFT-MS), an additional corona discharge ionization source of the same polarity was added in an attempt to increase total ion signal, but no improvement in signal was observed. This observation suggested that there was a maximum ion density being reached by the corona discharge that could not be increased by adding more of the same polarity ions. A hypothesis was that intermingling both polarities of ions would reduce ion loss and increase the measured ion signal. When two corona discharge sources—one each of positive and negative polarity—were used simultaneously in an AFT-MS, the total ion signal of either polarity measured by the MS was approximately double the current from a single corona discharge source. An increase in the negative ion signal was also observed when ~10 parts-per-trillion vapor levels of an explosive (RDX) were introduced. In this case both the nitrate reactant ions and the RDX signal more than doubled with the addition of a corona discharge source producing positive ions. When intermingling positive and negative ions, an increase in ion current was also observed when the AFT was coupled directly to a Faraday detector or to an ion mobility spectrometer. This was the first demonstration of interfacing the AFT to an IMS. The observations and developments from this work will help in creating more portable instruments with improved sensitivity for detection of chemicals.

47 OTHER INSTRUMENTATION↗

Catalytic Hydrotreatment of Humins to Bio‐Oil in Methanol over Supported Metal Catalysts

Abstract Valorization of humins, the polymeric byproducts formed during the acid‐catalyzed production of HMF (5‐hydroxymethylfurfural) or furfural, is necessary to improve process economics and make biorefineries viable. We report the one‐step catalytic hydrotreatment of humins in methanol to humin oil containing fully or partially deoxygenated compounds. First, we compare four commercial noble‐metal catalysts (Ru/C, Rh/C, Pt/C, and Pd/C). Aromatic hydrocarbons, phenols, and esters are the main products detected by GC. Rh/C achieves the best GC‐detectable oil yield and 75 % humins conversion in 3 h at 400 °C, 30 bar H 2 , and a catalyst‐to‐humins mass ratio of 1:10. High H 2 pressures and intermediate temperatures, reaction times, and catalyst loadings enhance GC‐detectable oil yields. In contrast, high temperatures and long reaction times enhance gasification. Aromatics and phenols are found at high temperatures and long reaction times, whereas esters are the major species at short reaction times and high catalyst loading. 13 C‐isotopic labeling studies confirm, for the first time, that methanol participates in the alkylation and esterification reactions to form aromatic, phenolic and ester products. The reactivity in isopropanol is also discussed.

Cheng, Ziwei↗

Modified inverse micelle synthesis for mesoporous alumina with a high D4 siloxane adsorption capacity

In this work, mesoporous aluminas (MAs) with uniform and monomodal pores were fabricated via a modified inverse micelle synthesis method, using a non-polar solvent (to minimize the effect of water content) and short reaction time (for a fast evaporation process). The effects of reaction times (4–8 h), surfactant chain lengths (non-ionic surfactants), and calcination temperatures and hold times (450–600 °C; 1–4 h) on the textural properties of MA were studied. Additionally, the targeted pore sizes of MA were obtained in the range of 3.1–5.4 nm by adjusting the surfactant and reaction time. The surface area and pore volume were controlled by the calcination temperature and hold time while maintaining the thermal stability of the materials. The tuned MA of the large mesopore volume achieved 168 mg/g octamethylcyclotetrasiloxane (D4 siloxane) adsorption capacity, a 32% improvement compared to commercially activated alumina. Finally, after three adsorption recycles, the synthesized MA still maintained approximate 85% of its original adsorption capacity, demonstrating a sustainable adsorption performance and high potential for related industrial applications.

25 ENERGY STORAGE↗

A failure effects simulation of a low authority flight control augmentation system on a UH-1H helicopter

A two-pilot moving base simulator experiment was conducted to assess the effects of servo failures of a flight control system on the transient dynamics of a Bell UH-1H helicopter. The flight control hardware considered was part of the V/STOLAND system built with control authorities of from 20-40%. Servo hardover and oscillatory failures were simulated in each control axis. Measurements were made to determine the adequacy of the failure monitoring system time delay and the servo center and lock time constant, the pilot reaction times, and the altitude and attitude excursions of the helicopter at hover and 60 knots. Safe recoveries were made from all failures under VFR conditions. Pilot reaction times were from 0.5 to 0.75 sec. Reduction of monitor delay times below these values resulted in significantly reduced excursion envelopes. A subsequent flight test was conducted on a UH-1H helicopter with the V/STOLAND system installed. Series servo hardovers were introduced in hover and at 60 knots straight and level. Data from these tests are included for comparison.

Corliss, L. D.↗

Effect of Target Location on Dynamic Visual Acuity During Passive Horizontal Rotation

The vestibulo-ocular reflex (VOR) generates eye rotation to compensate for potential retinal slip in the specific plane of head movement. Dynamic visual acuity (DVA) has been utilized as a functional measure of the VOR. The purpose of this study was to examine changes in accuracy and reaction time when performing a DVA task with targets offset from the plane of rotation, e.g. offset vertically during horizontal rotation. Visual acuity was measured in 12 healthy subjects as they moved a hand-held joystick to indicate the orientation of a computer-generated Landolt C "as quickly and accurately as possible." Acuity thresholds were established with optotypes presented centrally on a wall-mounted LCD screen at 1.3 m distance, first without motion (static condition) and then while oscillating at 0.8 Hz (DVA, peak velocity 60 deg/s). The effect of target location was then measured during horizontal rotation with the optotypes randomly presented in one of nine different locations on the screen (offset up to 10 deg). The optotype size (logMar 0, 0.2 or 0.4, corresponding to Snellen range 20/20 to 20/50) and presentation duration (150, 300 and 450 ms) were counter-balanced across five trials, each utilizing horizontal rotation at 0.8 Hz. Dynamic acuity was reduced relative to static acuity in 7 of 12 subjects by one step size. During the random target trials, both accuracy and reaction time improved proportional to optotype size. Accuracy and reaction time also improved between 150 ms and 300 ms presentation durations. The main finding was that both accuracy and reaction time varied as a function of target location, with greater performance decrements when acquiring vertical targets. We conclude that dynamic visual acuity varies with target location, with acuity optimized for targets in the plane of motion. Both reaction time and accuracy are functionally relevant DVA parameters of VOR function.

Appelbaum, Meghan↗

Intercalation of Nanopolyaniline with Nanobentonite and Manganese Oxide Nanoparticles as a Novel Nanocomposite to Remediate Cobalt/Zinc and Their Radioactive Nuclides {sup 60}Co/{sup 65}Zn

A novel nanocomposite based on the combination of nanobentonite with nanopolyaniline and nanomanganese oxide (N-Bent–NPANI–NMn{sub 3}O{sub 4}) was synthesized and investigated to extract Co/Zn ions from water using batch technique and {sup 60}Co/{sup 65}Zn radionuclides from radioactive wastewater using column techniques. Characterization was established by High resolution-transmission electron microscopy (HR-TEM), Scanning electron microscope, X-ray diffraction (XRD), thermal gravimetric analysis (TGA) and Fourier transform infrared spectrophotometer. The image of HR-TEM indicated that the produced nanocomposite was ranged from 59.07 to 83.38 nm. Solution pH, time of reaction, amount of solid and metal concentration, all of these parameters were inspected and optimized as fundamental factors during the extraction process. The obtained results implied that the ideal conditions for extraction were pH 6 and 7, reaction time 10 and 20 min, for Co and Zn ions, respectively. The highest removal capacities were found 255.28 and 202.22 mg g{sup −1} for Co and Zn, respectively by using 5 mg nanocomposite. Excellent recoveries were obtained as 94.0–94.5% and 92.0–93.0% for removal of Co–{sup 60}Co and of Zn–{sup 65}Zn ions, respectively from the examined samples. Graphical Abstract: .

77 NANOSCIENCE AND NANOTECHNOLOGY↗

An experimental, theoretical and kinetic modeling study of the N 2 O-H 2 system: Implications for N 2 O + H

The reaction of N 2 O with His the key step in consumption of nitrous oxide in thermal processes. The major product channel is N 2 + OH, while NH + NO constitute minor products. In addition, a pathway involving HNNO, initiated by N 2 O + H (+M)$\rightleftarrows$HNNO (+M) (R3, R4), has been inferred from experiment and theory by Burke and coworkers. At longer reaction times, the reaction may reach partial equilibration, and in addition to k 3 and k 4 the importance of this channel depends on the thermodynamic properties of HNNO and its consumption reactions, mainly HNNO + H. In the present work, we re-examined the thermochemistry of HNNO and calculated rate constants and branching fractions for the HNNO + H reaction. Experiments on the N 2 O-H 2 system were conducted in a high-pressure flow reactor at 100 atm as a function of temperature (600-925 K) and stoichiometry and explained in terms of an updated chemical kinetic model. The results support the importance of the HNNO pathway, which results in inhibition of N 2 O consumption and formation of NH 3 . In addition, selected literature results on the N 2 O-H 2 system are re-examined and the implications for the other product channels of N 2 O + H, in particular NH + NO, are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Formation of uranium disulfide from a uranium thioamidate single-source precursor

A single-source-precursor approach was developed to synthesize uranium-based materials outside of the typically-studied oxides. This approach allows for shorter reaction times, milder reaction conditions, and control over the chemicals present in synthesis. To this end, the first homoleptic uranium thioamidate complex was synthesized as a precursor for US 2 materials. Pyrolysis of the thioamidate results in decomposition via an alkene elimination pathway and formation of γ-US 2 , which has historically been hard to access without the need for a secondary sulfur source. Despite the oxophilicity of uranium, the method successfully forms US 2 without the inclusion of oxygen in the bulk final product. These findings are supported by simultaneous thermal analysis, elemental analysis, powder X-ray diffraction, and uranium L 3 -edge X-ray absorption fine-structure spectroscopy. This work represents the first example of a single-source precursor approach to target and synthesize actinide materials other than the oxides.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Synthesis and characterization of highly purified nanosilica from pyrophyllite ores

A simple method based on alkaline extraction followed by acid precipitation and acid dissolution has been developed to produce highly purified nanosilica from pyrophyllite materials. The reaction parameters such as molar ratio NaOH/SiO{sub 2}, reaction time and reaction temperature are varied for obtaining maximum nanosilica convertion. About 99,45% highly purified precipitated nanosilica measure with ICP, 259 m{sup 2}/gr measure with BET surface area, 97% whiteness and 3 ml/gr oil absorbtion from pyrophyllite materials has been achieved in closed system at 150°C within 180 min. The physicals and chemical properties (such as X-Ray Diffraction from PANalytical, X-Ray Fluorescence Minipal4 from PANanalytical, BET surface area, Forier Transform Infra Red Spectroscopy from Hitachi, and SEM-EDS Inspect-S50 from FEI Company) of the highly purity nanosilica were studied.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Passenger comfort response times as a function of aircraft motion

The relationship between a passenger's response time of changes in level of comfort experienced as a function of aircraft motion was examined. The aircraft used in this investigation was capable of providing a wide range of vertical and transverse accelerations by means of direct lift flap control surfaces and side force generator surfaces in addition to normal control surfaces. Response times to changes in comfort were recorded along with the passenger's rating of comfort on a five point scale. In addition, a number of aircraft motion variables including vertical and transverse accelerations were also recorded. Results indicate some relationship between human comfort response times to reaction time data.

Rinalducci, E. J.↗