Future Challenges in Heterogeneous Catalysis: Understanding Catalysts under Dynamic Reaction Conditions

PubMed Central

Kalz, Kai F.; Kraehnert, Ralph; Dvoyashkin, Muslim; Dittmeyer, Roland; Gläser, Roger; Krewer, Ulrike; Reuter, Karsten

2016-01-01

Abstract In the future, (electro‐)chemical catalysts will have to be more tolerant towards a varying supply of energy and raw materials. This is mainly due to the fluctuating nature of renewable energies. For example, power‐to‐chemical processes require a shift from steady‐state operation towards operation under dynamic reaction conditions. This brings along a number of demands for the design of both catalysts and reactors, because it is well‐known that the structure of catalysts is very dynamic. However, in‐depth studies of catalysts and catalytic reactors under such transient conditions have only started recently. This requires studies and advances in the fields of 1) operando spectroscopy including time‐resolved methods, 2) theory with predictive quality, 3) kinetic modelling, 4) design of catalysts by appropriate preparation concepts, and 5) novel/modular reactor designs. An intensive exchange between these scientific disciplines will enable a substantial gain of fundamental knowledge which is urgently required. This concept article highlights recent developments, challenges, and future directions for understanding catalysts under dynamic reaction conditions. PMID:28239429

Three model space experiments on chemical reactions. [Gibbs adsorption, equilibrium shift and electrodeposition

NASA Technical Reports Server (NTRS)

Grodzka, P.; Facemire, B.

1977-01-01

Three investigations conducted aboard Skylab IV and Apollo-Soyuz involved phenomena that are of interest to the biochemistry community. The formaldehyde clock reaction and the equilibrium shift reaction experiments conducted aboard Apollo Soyuz demonstrate the effect of low-g foams or air/liquid dispersions on reaction rate and chemical equilibrium. The electrodeposition reaction experiment conducted aboard Skylab IV demonstrate the effect of a low-g environment on an electrochemical displacement reaction. The implications of the three space experiments for various applications are considered.

A regenerative process for carbon dioxide removal and hydrogen production in IGCC

NASA Astrophysics Data System (ADS)

Hassanzadeh Khayyat, Armin

Advanced power generation technologies, such as Integrated Gasification-Combined Cycles (IGCC) processes, are among the leading contenders for power generation conversion because of their significantly higher efficiencies and potential environmental advantages, compared to conventional coal combustion processes. Although the increased in efficiency in the IGCC processes will reduce the emissions of carbon dioxide per unit of power generated, further reduction in CO2 emissions is crucial due to enforcement of green house gases (GHG) regulations. In IGCC processes to avoid efficiency losses, it is desirable to remove CO2 in the temperature range of 300° to 500°C, which makes regenerable MgO-based sorbents ideal for such operations. In this temperature range, CO2 removal results in the shifting of the water-gas shift (WGS) reaction towards significant reduction in carbon monoxide (CO), and enhancement in hydrogen production. However, regenerable, reactive and attrition resistant sorbents are required for such application. In this work, a highly reactive and attrition resistant regenerable MgO-based sorbent is prepared through dolomite modification, which can simultaneously remove carbon dioxide and enhance hydrogen production in a single reactor. The results of the experimental tests conducted in High-Pressure Thermogravimetric Analyzer (HP-TGA) and high-pressure packed-bed units indicate that in the temperature range of 300° to 500°C at 20 atm more than 95 molar percent of CO2 can be removed from the simulated coal gas, and the hydrogen concentration can be increased to above 70 percent. However, a declining trend is observed in the capacity of the sorbent exposed to long-term durability analysis, which appears to level off after about 20 cycles. Based on the physical and chemical analysis of the sorbent, a two-zone expanding grain model was applied to obtain an excellent fit to the carbonation reaction rate data at various operating conditions. The modeling results indicate that more than 90 percent purification of hydrogen is achievable, either by increasing the activity of the sorbent towards water-gas shift reaction or by mixing the sorbent bed with a commercialized water-gas shift catalyst. The preliminary economical evaluation of the MgO-based process indicates that this process can be economically viable compared to the commercially available WGS/Selexol(TM) processes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yao, Siyu; Zhang, Xiao; Zhou, Wu

Here, the water-gas shift (WGS) reaction (where carbon monoxide plus water yields dihydrogen and carbon dioxide) is an essential process for hydrogen generation and carbon monoxide removal in various energy-related chemical operations. This equilibrium-limited reaction is favored at a low working temperature. Potential application in fuel cells also requires a WGS catalyst to be highly active, stable, and energy-efficient and to match the working temperature of on-site hydrogen generation and consumption units. We synthesized layered gold (Au) clusters on a molybdenum carbide (α-MoC) substrate to create an interfacial catalyst system for the ultralow-temperature WGS reaction. Water was activated over α-MoCatmore » 303 kelvin, whereas carbon monoxide adsorbed on adjacent Au sites was apt to react with surface hydroxyl groups formed from water splitting, leading to a high WGS activity at low temperatures.« less

Focused and shifting attention in children with heavy prenatal alcohol exposure.

PubMed

Mattson, Sarah N; Calarco, Katherine E; Lang, Aimée R

2006-05-01

Attention deficits are a hallmark of the teratogenic effects of alcohol. However, characterization of these deficits remains inconclusive. Children with heavy prenatal alcohol exposure and nonexposed controls were evaluated using a paradigm consisting of three conditions: visual focus, auditory focus, and auditory-visual shift of attention. For the focus conditions, participants responded manually to visual or auditory targets. For the shift condition, participants alternated responses between visual targets and auditory targets. For the visual focus condition, alcohol-exposed children had lower accuracy and slower reaction time for all intertarget intervals (ITIs), while on the auditory focus condition, alcohol-exposed children were less accurate but displayed slower reaction time only on the longest ITI. Finally, for the shift condition, the alcohol-exposed group was accurate but had slowed reaction times. These results indicate that children with heavy prenatal alcohol exposure have pervasive deficits in visual focused attention and deficits in maintaining auditory attention over time. However, no deficits were noted in the ability to disengage and reengage attention when required to shift attention between visual and auditory stimuli, although reaction times to shift were slower. Copyright (c) 2006 APA, all rights reserved.

Characterization of MoVTeNbO x catalysts during oxidation reactions using in situ/operando techniques: A review

DOE PAGES

Lwin, Soe; Diao, Weijian; Baroi, Chinmoy; ...

2017-04-08

The domestic fossil feedstock in recent years is shifting towards light hydrocarbons due to abundance of shale gas from hydraulic fracturing. This shift induces a need for greater flexibility in both new and existing processing plants to produce consumer products (polymers, paints, lubricants, etc.) from new feedstocks. The oxidative catalytic reactions operate at milder conditions than the processing of feedstocks through steam cracking. The conversion of light feedstocks (C3 and shorter hydrocarbons) to high value chemicals through highly selective catalysts in the presence of oxygen plays a crucial role in eliminating wastes, reducing greenhouse gas emissions and lowering market prices.more » Among all catalysts for light hydrocarbon processing through oxidation reactions, bulk mixed metal oxides such as MoVTe(Sb)NbO x catalysts are the most promising due to their performance under favorable reaction conditions (temperature, pressure, etc). Here, state-of-the-art in situ/operando techniques along with transient kinetics can revolutionize the development of catalysts by providing information about the nature of active sites, intermediates and kinetics under realistic industrial conditions. Only through detailed understanding of these catalyst behaviors can new synthesis methods be developed that will improve reactivity, selectivity and lifetimes of these catalysts. In this review, dynamic changes of this mixed oxide catalyst during the reaction (such as changes in surface composition, oxidation states, acidity, etc) are discussed mainly from knowledge and insights obtained from these in situ/operando approaches. The most common oxidation reactions driven by the MoVTeNbO x catalysts and studied under operando/in situ conditions to be discussed here are: (1) oxidative dehydrogenation of light alkanes (ethane and propane), (2) propane ammoxidation to acrylonitrile and (3) selective oxidation of propane to acrylic acid.« less

Characterization of MoVTeNbO x catalysts during oxidation reactions using in situ/operando techniques: A review

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lwin, Soe; Diao, Weijian; Baroi, Chinmoy

The domestic fossil feedstock in recent years is shifting towards light hydrocarbons due to abundance of shale gas from hydraulic fracturing. This shift induces a need for greater flexibility in both new and existing processing plants to produce consumer products (polymers, paints, lubricants, etc.) from new feedstocks. The oxidative catalytic reactions operate at milder conditions than the processing of feedstocks through steam cracking. The conversion of light feedstocks (C3 and shorter hydrocarbons) to high value chemicals through highly selective catalysts in the presence of oxygen plays a crucial role in eliminating wastes, reducing greenhouse gas emissions and lowering market prices.more » Among all catalysts for light hydrocarbon processing through oxidation reactions, bulk mixed metal oxides such as MoVTe(Sb)NbO x catalysts are the most promising due to their performance under favorable reaction conditions (temperature, pressure, etc). Here, state-of-the-art in situ/operando techniques along with transient kinetics can revolutionize the development of catalysts by providing information about the nature of active sites, intermediates and kinetics under realistic industrial conditions. Only through detailed understanding of these catalyst behaviors can new synthesis methods be developed that will improve reactivity, selectivity and lifetimes of these catalysts. In this review, dynamic changes of this mixed oxide catalyst during the reaction (such as changes in surface composition, oxidation states, acidity, etc) are discussed mainly from knowledge and insights obtained from these in situ/operando approaches. The most common oxidation reactions driven by the MoVTeNbO x catalysts and studied under operando/in situ conditions to be discussed here are: (1) oxidative dehydrogenation of light alkanes (ethane and propane), (2) propane ammoxidation to acrylonitrile and (3) selective oxidation of propane to acrylic acid.« less

Pre-Combustion Carbon Dioxide Capture by a New Dual Phase Ceramic-Carbonate Membrane Reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Jerry Y. S.

2015-01-31

This report documents synthesis, characterization and carbon dioxide permeation and separation properties of a new group of ceramic-carbonate dual-phase membranes and results of a laboratory study on their application for water gas shift reaction with carbon dioxide separation. A series of ceramic-carbonate dual phase membranes with various oxygen ionic or mixed ionic and electronic conducting metal oxide materials in disk, tube, symmetric, and asymmetric geometric configurations was developed. These membranes, with the thickness of 10 μm to 1.5 mm, show CO 2 permeance in the range of 0.5-5×10 -7 mol·m -2·s -1·Pa -1 in 500-900°C and measured CO 2/N 2more » selectivity of up to 3000. CO 2 permeation mechanism and factors that affect CO 2 permeation through the dual-phase membranes have been identified. A reliable CO 2 permeation model was developed. A robust method was established for the optimization of the microstructures of ceramic-carbonate membranes. The ceramic-carbonate membranes exhibit high stability for high temperature CO 2 separations and water gas shift reaction. Water gas shift reaction in the dual-phase membrane reactors was studied by both modeling and experiments. It is found that high temperature syngas water gas shift reaction in tubular ceramic-carbonate dual phase membrane reactor is feasible even without catalyst. The membrane reactor exhibits good CO 2 permeation flux, high thermal and chemical stability and high thermal shock resistance. Reaction and separation conditions in the membrane reactor to produce hydrogen of 93% purity and CO 2 stream of >95% purity, with 90% CO 2 capture have been identified. Integration of the ceramic-carbonate dual-phase membrane reactor with IGCC process for carbon dioxide capture was analyzed. A methodology was developed to identify optimum operation conditions for a membrane tube of given dimensions that would treat coal syngas with targeted performance. The calculation results show that the dual-phase membrane reactor could improve IGCC process efficiency but the cost of the membrane reactor with membranes having current CO 2 permeance is high. Further research should be directed towards improving the performance of the membranes and developing cost-effective, scalable methods for fabrication of dual-phase membranes and membrane reactors.« less

Effects of Fatigue on Driving Safety: A Comparison of Brake Reaction Times in Night Float and Postcall Physicians in Training.

PubMed

Talusan, Paul G; Long, Theodore; Halim, Andrea; Guliani, Laura; Carroll, Nicole; Reach, John

2014-12-01

Concerns about duty hour and resident safety have fostered discussion about postshift fatigue and driving impairment. We assessed how converting to a night float schedule for overnight coverage affected driving safety for trainees. Brake reaction times were measured for internal medicine and orthopaedic surgery resident volunteers after a traditional 28-hour call shift and after a night float shift. We conducted matched paired t tests of preshift and postshift reaction time means. Participants also completed the Epworth Sleepiness Scale pre- and postshift. From June to July 2013, we enrolled 58 interns and residents (28 orthopaedic surgery, 30 internal medicine). We included 24 (41%) trainees on night float rotations and 34 (59%) trainees on traditional 28-hour call shifts. For all residents on night float rotations, there was no significant difference pre- and postshift. An increase in reaction times was noted among trainees on 28-hour call rotations. This included no effect on reaction times for internal medicine trainees pre- and postshift, and an increase in reaction times for orthopaedic trainees. For both night float and traditional call groups, there were significant increases in the Epworth Sleepiness Scale. Trainees on traditional 28-hour call rotations had significantly worse postshift brake reaction times, whereas trainees on night float rotations had no difference. Orthopaedic trainees had significant differences in brake reaction times after a traditional call shift.

Understanding and controlling chromaticity shift in LED devices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Davis, Lynn; Mills, Karmann; Lamvik, Michael

Chromaticity shift in light-emitting diode (LED) devices arises from multiple mechanisms, and at least five different chromaticity shift modes (CSMs) have been identified to date. This paper focuses on the impacts of irreversible phosphor degradation as a cause of chromaticity shifts in LED devices. The nitride phosphors used to produce warm white LEDs are especially vulnerable to degradation due to thermal and chemical effects such as reactions with oxygen and water. As a result, LED devices utilizing these phosphors were found to undergo either a green shift or, less commonly, a red shift depending on the phosphor mix in themore » LED devices. These types of chromaticity shifts are classified as CSM-2 (green shift) and CSM-5 (red shift). This paper provides an overview of the kinetic processes responsible for green and red chromaticity shifts along with examples from accelerated stress testing of 6” downlights. Both CSMs appear to proceed through analogous mechanisms that are initiated at the surface of the phosphor. A green shift is produced by the surface oxidation of the nitride phosphor that changes the emission profile to lower wavelengths. As the surface oxidation reaction proceeds, reactant limitations slow the rate and bulk oxidation processes become more prevalent. We found that a red chromaticity shift arises from quenching of the green phosphor, also possibly due to surface reactions of oxygen, which shift the emission chromaticity in the red direction. In conclusion, we discuss the implications of these findings on projecting chromaticity.« less

Effect of working consecutive night shifts on sleep time, prior wakefulness, perceived levels of fatigue and performance on a psychometric test in emergency registrars.

PubMed

Haire, Julia Christine Lydia; Ferguson, Sally Anne; Tilleard, James D; Negus, Paul; Dorrian, Jillian; Thomas, Matthew Jw

2012-06-01

To evaluate the effect of working consecutive night shifts on sleep time, prior wakefulness, perceived levels of fatigue and psychomotor performance in a group of Australian emergency registrars. A prospective observational study with a repeated within-subjects component was conducted. Sleep time was determined using sleep diaries and activity monitors. Subjective fatigue levels and reciprocal reaction times were evaluated before and after day and night shifts. A total of 11 registrars participated in the study with 120 shifts analysed. Sleep time was found to be similar during consecutive night and day shifts. The mean number of hours spent awake before the end of a night shift was 14.33. Subjective fatigue scores were worst at the end of a night shift. There was no difference in reciprocal reaction time between the end of night shift and the start of day shift. Registrars sleep a similar amount of time surrounding night and day shifts. Despite reporting the highest levels of fatigue at the end of a night shift, there is no significant difference in reaction times at the end of night shift compared with the beginning of day shift. This correlates with the finding that at the end of night shift the registrars have been awake for less than 16 h, which is the point at which psychomotor performance is expected to decline. © 2012 The Authors. EMA © 2012 Australasian College for Emergency Medicine and Australasian Society for Emergency Medicine.

Fuel cell power supply with oxidant and fuel gas switching

DOEpatents

McElroy, James F.; Chludzinski, Paul J.; Dantowitz, Philip

1987-01-01

This invention relates to a fuel cell vehicular power plant. Fuel for the fuel stack is supplied by a hydrocarbon (methanol) catalytic cracking reactor and CO shift reactor. A water electrolysis subsystem is associated with the stack. During low power operation part of the fuel cell power is used to electrolyze water with hydrogen and oxygen electrolysis products being stored in pressure vessels. During peak power intervals, viz, during acceleration or start-up, pure oxygen and pure hydrogen from the pressure vessel are supplied as the reaction gases to the cathodes and anodes in place of air and methanol reformate. This allows the fuel cell stack to be sized for normal low power/air operation but with a peak power capacity several times greater than that for normal operation.

Fuel cell power supply with oxidant and fuel gas switching

DOEpatents

McElroy, J.F.; Chludzinski, P.J.; Dantowitz, P.

1987-04-14

This invention relates to a fuel cell vehicular power plant. Fuel for the fuel stack is supplied by a hydrocarbon (methanol) catalytic cracking reactor and CO shift reactor. A water electrolysis subsystem is associated with the stack. During low power operation part of the fuel cell power is used to electrolyze water with hydrogen and oxygen electrolysis products being stored in pressure vessels. During peak power intervals, viz, during acceleration or start-up, pure oxygen and pure hydrogen from the pressure vessel are supplied as the reaction gases to the cathodes and anodes in place of air and methanol reformate. This allows the fuel cell stack to be sized for normal low power/air operation but with a peak power capacity several times greater than that for normal operation. 2 figs.

Effects of Fatigue on Driving Safety: A Comparison of Brake Reaction Times in Night Float and Postcall Physicians in Training

PubMed Central

Talusan, Paul G.; Long, Theodore; Halim, Andrea; Guliani, Laura; Carroll, Nicole; Reach, John

2014-01-01

Background Concerns about duty hour and resident safety have fostered discussion about postshift fatigue and driving impairment. Objective We assessed how converting to a night float schedule for overnight coverage affected driving safety for trainees. Methods Brake reaction times were measured for internal medicine and orthopaedic surgery resident volunteers after a traditional 28-hour call shift and after a night float shift. We conducted matched paired t tests of preshift and postshift reaction time means. Participants also completed the Epworth Sleepiness Scale pre- and postshift. Results From June to July 2013, we enrolled 58 interns and residents (28 orthopaedic surgery, 30 internal medicine). We included 24 (41%) trainees on night float rotations and 34 (59%) trainees on traditional 28-hour call shifts. For all residents on night float rotations, there was no significant difference pre- and postshift. An increase in reaction times was noted among trainees on 28-hour call rotations. This included no effect on reaction times for internal medicine trainees pre- and postshift, and an increase in reaction times for orthopaedic trainees. For both night float and traditional call groups, there were significant increases in the Epworth Sleepiness Scale. Conclusions Trainees on traditional 28-hour call rotations had significantly worse postshift brake reaction times, whereas trainees on night float rotations had no difference. Orthopaedic trainees had significant differences in brake reaction times after a traditional call shift. PMID:26140113

Ceria-based model catalysts: fundamental studies on the importance of the metal–ceria interface in CO oxidation, the water–gas shift, CO 2 hydrogenation, and methane and alcohol reforming

DOE PAGES

Rodriguez, José A.; Grinter, David C.; Liu, Zongyuan; ...

2017-02-17

Model metal/ceria and ceria/metal catalysts have been shown to be excellent systems for studying fundamental phenomena linked to the operation of technical catalysts. In the last fifteen years, many combinations of well-defined systems involving different kinds of metals and ceria have been prepared and characterized using the modern techniques of surface science. So far most of the catalytic studies have been centered on a few reactions: CO oxidation, the hydrogenation of CO 2, and the production of hydrogen through the water–gas shift reaction and the reforming of methane or alcohols. By using model catalysts it is been possible to examinemore » in detail correlations between the structural, electronic and catalytic properties of ceria–metal interfaces. In situ techniques (X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, infrared spectroscopy, scanning tunneling microscopy) have been combined to study the morphological changes under reaction conditions and investigate the evolution of active phases involved in the cleavage of C–O, C–H and C–C bonds. Several studies with model ceria catalysts have shown the importance of strong metal–support interactions. Generally, a substantial body of knowledge has been acquired and concepts have been developed for a more rational approach to the design of novel technical catalysts containing ceria.« less

Studies of Hydrogen Production by the Water Gas Shift Reaction and Related Chemistry

DTIC Science & Technology

1983-04-15

STUDIES OF HYDROGEN PRODUCTION BY THE WATER GAS SHIFT REACTION AND RELATED CHEMISTRY Institution: The University of Rochester Department of Chemistry...been app-’.iv -7 for public release and sale; it di.,tribution is unlimited. Abstract Many systems have been investigated for the catalysis of the water ...temperatures (80 - 100’C). In addition aqueous acidic conditions for these systems have been pursued with particular interest in adopting water gas shift

Evaluation of the effects of one year's operation of the dynamic preferential runway system. [human reactions to overflight air traffic pattern

NASA Technical Reports Server (NTRS)

Borsky, P. N.

1974-01-01

The FAA introduced an experimental aircraft operations program at JFK Airport called the Dynamic Preferential Runway System (DPRS) in the summer of 1971. The program is designed to distribute air traffic as equally as possible over the surrounding communities, to limit periods of continuous overflight and to vary the same hours of overflight from day to day. After a full year's operation, an evaluation was made of the system's effectiveness. All of the operation's goals were moderately achieved with the greatest relief in reduced overflight afforded the most heavily impacted areas. Few residents, however, were aware of DPRS or felt that it had greatly reduced annoyance or represented a major effort by the aircraft authorities. Statistical analyses of reported annoyance obtained from two independent surveys in 1969 and 1972 reveal limited reductions in annoyance in 1972, with shifts from reported high annoyance to moderate annoyance.

Archimedes' principle for characterisation of recombinant whole cell biocatalysts.

PubMed

Schmitt, Steven; Walser, Marcel; Rehmann, Michael; Oesterle, Sabine; Panke, Sven; Held, Martin

2018-02-14

The ability of whole cells to catalyse multistep reactions, often yielding synthetically demanding compounds later used by industrial biotech or pharma, makes them an indispensable tool of synthetic chemistry. The complex reaction network employed by cellular catalysts and the still only moderate predictive power of modelling approaches leaves this tool challenging to engineer. Frequently, large libraries of semi-rationally generated variants are sampled in high-throughput mode in order to then identify improved catalysts. We present a method for space- and time-efficient processing of very large libraries (10 7 ) of recombinant cellular catalysts, in which the phenotypic characterisation and the isolation of positive variants for the entire library is done within one minute in a single, highly parallelized operation. Specifically, product formation in nanolitre-sized cultivation vessels is sensed and translated into the formation of catalase as a reporter protein. Exposure to hydrogen peroxide leads to oxygen gas formation and thus to a density shift of the cultivation vessel. Exploiting Archimedes' principle, this density shift and the resulting upward buoyancy force can be used for batch-wise library sampling. We demonstrate the potential of the method for both, screening and selection protocols, and envision a wide applicability of the system for biosensor-based assays.

Investigation of the characteristics of a compact steam reformer integrated with a water-gas shift reactor

NASA Astrophysics Data System (ADS)

Seo, Yong-Seog; Seo, Dong-Joo; Seo, Yu-Taek; Yoon, Wang-Lai

The objective of this study is to investigate numerically a compact steam methane reforming (SMR) system integrated with a water-gas shift (WGS) reactor. Separate numerical models are established for the combustion part, SMR and WGS reaction bed. The concentration of species at the exits of the SMR and WGS bed, and the temperatures in the WGS bed are in good agreement with the measured data. Heat transfer to the catalyst beds and the catalytic reactions in the SMR and WGS catalyst bed are investigated as a function of the operation parameters. The conversion of methane at the exit of the SMR catalyst bed is calculated to be 87%, and the carbon monoxide concentration at the outlet of the WGS bed is estimated to be 0.45%. The effects of the cooling heat flux at the outside wall of the system and steam-to-carbon (S/C) ratio are also examined. As the cooling heat flux increases, both the methane conversion and carbon monoxide content are reduced in the SMR bed, and the carbon monoxide conversion is improved in the WGS bed. Both methane conversion and carbon dioxide reduction increase with increasing steam-to-carbon ratio.

Reactor concepts for bioelectrochemical syntheses and energy conversion.

PubMed

Krieg, Thomas; Sydow, Anne; Schröder, Uwe; Schrader, Jens; Holtmann, Dirk

2014-12-01

In bioelectrochemical systems (BESs) at least one electrode reaction is catalyzed by microorganisms or isolated enzymes. One of the existing challenges for BESs is shifting the technology towards industrial use and engineering reactor systems at adequate scales. Due to the fact that most BESs are usually deployed in the production of large-volume but low-value products (e.g., energy, fuels, and bulk chemicals), investment and operating costs must be minimized. Recent advances in reactor concepts for different BESs, in particular biofuel cells and electrosynthesis, are summarized in this review including electrode development and first applications on a technical scale. A better understanding of the impact of reactor components on the performance of the reaction system is an important step towards commercialization of BESs. Copyright © 2014 Elsevier Ltd. All rights reserved.

Doped calcium manganites for advanced high-temperature thermochemical energy storage

DOE PAGES

Babiniec, Sean M.; Coker, Eric N.; Miller, James E.; ...

2015-12-16

Developing efficient thermal storage for concentrating solar power plants is essential to reducing the cost of generated electricity, extending or shifting the hours of operation, and facilitating renewable penetration into the grid. Perovskite materials of the CaB xMn 1-xO 3-δ family, where B = Al or Ti, promise improvements in cost and energy storage density over other perovskites currently under investigation. Thermogravimetric analysis of the thermal reduction and reoxidation of these materials was used to extract equilibrium thermodynamic parameters. Lastly, the results demonstrate that these novel thermochemical energy storage media display the highest reaction enthalpy capacity for perovskites reported tomore » date, with a reaction enthalpy of 390 kJ/kg, a 56% increase over previously reported compositions.« less

Operational Readiness Review Final Report for K Basin Fuel Transfer System

DOE Office of Scientific and Technical Information (OSTI.GOV)

DAVIES, T.H.

2002-10-01

An Operational Readiness Review (ORR) was conducted by the U.S. Department of Energy (DOE), Richland Operations Office (RL) to verify that an adequate state of readiness had been achieved for startup of the K Basin Fuel Transfer System (FTS). The DOE ORR was conducted during the period November 6-18, 2002. The DOE ORR team concluded that the K Basin Fuel Transfer System is ready to start operations, subject to completion and verification of identified pre-start findings. The ORR was conducted in accordance with the Spent Nuclear Fuel (SNF) K Basin Fuel Transfer System (FTS) Operational Readiness Review (ORR) Plan ofmore » Action and the Operational Readiness Review Implementation Plan for K Basin Fuel Transfer System. Review activities consisted of staff interviews, procedure and document reviews, and observations of normal facility operations, operational upset conditions, and an emergency drill. The DOE ORR Team also reviewed and assessed the adequacy of the contractor ORR3 and the RL line management review. The team concurred with the findings and observations identified in these two reports. The DOE ORR for the FTS evaluated the contractor under single-shift operations. Of concern to the ORR Team was that SNF Project management intended to change from a single-shift FTS operation to a two-shift operation shortly after the completion of the DOE ORR. The ORR team did not assess two-shift FTS operations and the ability of the contractor to conduct a smooth transition from shift to shift. However, the DOE ORR team did observe an operational upset drill that was conducted during day shift and carried over into swing shift; during this drill, swing shift was staffed with fewer personnel as would be expected for two-shift operations. The facility was able to adequately respond to the event with the reduced level of staff. The ORR Team was also able to observe a Shift Manager turnover meeting when one shift manager had to be relieved during the middle of the day. The ORR Team did not have the opportunity to observe a shift turnover from one crew to another. The ORR Team has evaluated the risk of not observing this activity and considers the risk to be minimal based on the fact that operating staff are very familiar with the FTS equipment and its procedures, and because existing Conduct of Operations processes and procedures are adequate and implemented. Because the ORR Team has not observed two-shift FTS operations, we recommend that additional RL oversight be provided at the start of two-shift FTS operations to evaluate the adequacy of crew turnovers.« less

Thermotolerance of apple tree leaves probed by chlorophyll a fluorescence and modulated 820 nm reflection during seasonal shift.

PubMed

Duan, Ying; Zhang, Mengxia; Gao, Jin; Li, Pengmin; Goltsev, Vasilij; Ma, Fengwang

2015-11-01

During the seasonal shift from June to August, air temperatures increase. To explore how apple trees improve their thermotolerance during this shift, we examined the photochemical reaction capacity of apple tree leaves by simultaneous measurement of prompt chlorophyll fluorescence, delayed chlorophyll fluorescence, and modulated 820 nm reflection at varying temperatures. It was found that the reaction centers and antennae of photosystem II (PSII) and photosystem I (PSI), the donor side of PSII, the electron transfer capacity from QA to QB, and the reoxidation capacity of plastoquinol were all sensitive to heat stress, particularly in June. As the season shifted, apple tree leaves improved in thermotolerance. Interestingly, the acclimation to seasonal shift enhanced the thermotolerance of PSII and PSI reaction centers more than that of their antennae, and the activity of PSII more than that of PSI. This may be a strategy for plant adaptation to changes in environmental temperatures. In addition, results from prompt and delayed fluorescence, as well as modulated 820 nm reflection corroborate each other. We suggest that the simultaneous measurement of the three independent signals may provide more information on thermal acclimation mechanisms of photochemical reactions in plant leaves. Copyright © 2015 Elsevier B.V. All rights reserved.

Investigation of the Reverse Water Gas Shift Reaction for Production of Oxygen From Mars Atmospheric Carbon Dioxide

NASA Technical Reports Server (NTRS)

Meyer, Tom; Zubrin, Robert

1997-01-01

The first phase of the research includes a comprehensive analytical study examining the potential applications for engineering subsystems and mission strategies made possible by such RWGS based subsystems, and will include an actual experimental demonstration and performance characterization of a full-scale brassboard RWGS working unit. By the time of this presentation the laboratory demonstration unit will not yet be operational but we will present the results of our analytical studies to date and plans for the ongoing work.

The effect of split sleep schedules (6h-on/6h-off) on neurobehavioural performance, sleep and sleepiness.

PubMed

Short, Michelle A; Centofanti, Stephanie; Hilditch, Cassie; Banks, Siobhan; Lushington, Kurt; Dorrian, Jillian

2016-05-01

Shorter, more frequent rosters, such as 6h-on/6h-off split shifts, may offer promise to sleep, subjective sleepiness and performance by limiting shift length and by offering opportunities for all workers to obtain some sleep across the biological night. However, there exists a paucity of studies that have examined these shifts using objective measures of sleep and performance. The present study examined neurobehavioural performance, sleepiness and sleep during 6h-on/6h-off split sleep schedules. Sixteen healthy adults (6 males, 26.13 y ± 4.46) participated in a 9-day laboratory study that included two baseline nights (BL, 10h time in bed (TIB), 2200 h-0800 h), 4 days on one of two types of 6h-on/6h-off split sleep schedules with 5h TIB during each 'off' period (6h early: TIB 0300 h-0800 h and 1500 h-20000 h, or 6-h late: TIB 0900 h-1400 h and 2100 h-0200 h), and two recovery nights (10h TIB per night, 2200 h-0800 h). Participants received 10h TIB per 24h in total across both shift schedules. A neurobehavioural test bout was completed every 2 h during wake, which included the Psychomotor Vigilance Task (PVT) and the Karolinska Sleepiness Scale (KSS). Linear mixed effects models were used to assess the effect of day (BL, shift days 1-4), schedule (6h early, 6h late) and trial (numbers 1-6) on PVT lapses (operationalised as the number of reaction times >500 ms), PVT total lapse time, PVT fastest 10% of reaction times and KSS. Analyses were also conducted examining the effect of day and schedule on sleep variables. Overall, PVT lapses and total lapse time did not differ significantly between baseline and shift days, however, peak response speeds were significantly slower on the first shift day when compared to baseline, but only for those in the 6h-late condition. Circadian variations were apparent in performance outcomes, with individuals in the 6h-late condition demonstrated significantly more and longer lapses and slower peak reaction times at the end of their night shift (0730 h) than at any other time during their shifts. In the 6h-early condition, only response speed significantly differed across trials, with slower response speeds occurring at trial 1 (0930 h) than in trials 3 (1330 h) or 4 (2130 h). While subjective sleepiness was higher on shift days than at baseline, sleepiness did not accumulate across days. Total sleep was reduced across split sleep schedules compared to baseline. Overall, these results show that while there was not a cumulative cost to performance across days of splitting sleep, participants obtained less sleep and reported lowered alertness on shift days. Tests near the circadian nadir showed higher sleepiness and increased performance deficits. While this schedule did not produce cumulative impairment, the performance deficits witnessed during the biological night are still of operational concern for industry and workers alike. Crown Copyright © 2015. Published by Elsevier Ltd. All rights reserved.

Reaction monitoring using hyperpolarized NMR with scaling of heteronuclear couplings by optimal tracking

NASA Astrophysics Data System (ADS)

Zhang, Guannan; Schilling, Franz; Glaser, Steffen J.; Hilty, Christian

2016-11-01

Off-resonance decoupling using the method of Scaling of Heteronuclear Couplings by Optimal Tracking (SHOT) enables determination of heteronuclear correlations of chemical shifts in single scan NMR spectra. Through modulation of J-coupling evolution by shaped radio frequency pulses, off resonance decoupling using SHOT pulses causes a user-defined dependence of the observed J-splitting, such as the splitting of 13C peaks, on the chemical shift offset of coupled nuclei, such as 1H. Because a decoupling experiment requires only a single scan, this method is suitable for characterizing on-going chemical reactions using hyperpolarization by dissolution dynamic nuclear polarization (D-DNP). We demonstrate the calculation of [13C, 1H] chemical shift correlations of the carbanionic active sites from hyperpolarized styrene polymerized using sodium naphthalene as an initiator. While off resonance decoupling by SHOT pulses does not enhance the resolution in the same way as a 2D NMR spectrum would, the ability to obtain the correlations in single scans makes this method ideal for determination of chemical shifts in on-going reactions on the second time scale. In addition, we present a novel SHOT pulse that allows to scale J-splittings 50% larger than the respective J-coupling constant. This feature can be used to enhance the resolution of the indirectly detected chemical shift and reduce peak overlap, as demonstrated in a model reaction between p-anisaldehyde and isobutylamine. For both pulses, the accuracy is evaluated under changing signal-to-noise ratios (SNR) of the peaks from reactants and reaction products, with an overall standard deviation of chemical shift differences compared to reference spectra of 0.02 ppm when measured on a 400 MHz NMR spectrometer. Notably, the appearance of decoupling side-bands, which scale with peak intensity, appears to be of secondary importance.

Catalytic Effect of Pd Clusters in the Poly( N-vinyl-2-pyrrolidone) Combustion

NASA Astrophysics Data System (ADS)

Schiavo, L.; De Nicola, S.; Carotenuto, G.

2018-01-01

Pd(0) is able to catalyze oxygen-involving reactions because of its capability to convert molecular oxygen to the very reactive atomic form. Consequently, the embedding of a little amount of Pd(0) clusters in polymeric phases can be technologically exploited to enhance the incineration kinetic of these polymers. The effect of nanostructuration on the Pd(0) catalytic activity in the polymer incineration reaction has been studied using poly( N-vinyl-2-pyrrolidone) ( \\overline{Mw} = 10,000 gmol-1) as polymeric model system. A change in the PVP incineration kinetic mechanism with significant increase in the reaction rate was experimentally found. The kinetic of the Pd(0)-catalyzed combustion has been studied by isothermal thermogravimetric analysis. After a short induction time, the combustion in presence of Pd(0) clusters shifted to a zero-order kinetic from a second-order kinetic control, which is operative in pure PVP combustion reaction. In addition, the activation energy resulted much lowered compared to the pure PVP incineration case (from 300 to 260 kJ/mol).

Water-gas shift reaction on alumina-supported Pt-CeO x catalysts prepared by supercritical fluid deposition

DOE PAGES

Deal, Jacob W.; Le, Phong; Corey, C. Blake; ...

2016-08-25

Alumina-supported platinum catalysts, both with and without ceria, were prepared by supercritical fluid deposition and evaluated for activity for water-gas shift reaction. The organometallic precursor, platinum(II) acetylacetonate, was deposited from solution in supercritical carbon dioxide. Analysis of the catalysts by high resolution scanning transmission electron microscopy indicated that platinum was present in the form of highly dispersed metal nanoparticles. Pretreatment of the alumina-supported ceria in hydrogen prior to the deposition of the platinum precursor resulted in more platinum nucleated on ceria than non-pretreated alumina-supported ceria but varied in both particle size and structure. The ceria-containing catalyst that was not pretreatedmore » exhibited a more uniform particle size, and the Pt particles were encapsulated in crystalline ceria. Reaction rate measurements showed that the catalyst was more active for water-gas shift, with reaction rates per mass of platinum that exceeded most literature values for water-gas shift reaction on Pt-CeO x catalysts. The high activity was attributed to the significant fraction of platinum/ceria interfacial contact. We found that these results show the promise of supercritical fluid deposition as a scalable means of synthesizing highly active supported metal catalysts that offer efficient utilization of precious metals.« less

Monitoring chemical reactions by low-field benchtop NMR at 45 MHz: pros and cons.

PubMed

Silva Elipe, Maria Victoria; Milburn, Robert R

2016-06-01

Monitoring chemical reactions is the key to controlling chemical processes where NMR can provide support. High-field NMR gives detailed structural information on chemical compounds and reactions; however, it is expensive and complex to operate. Conversely, low-field NMR instruments are simple and relatively inexpensive alternatives. While low-field NMR does not provide the detailed information as the high-field instruments as a result of their smaller chemical shift dispersion and the complex secondary coupling, it remains of practical value as a process analytical technology (PAT) tool and is complimentary to other established methods, such as ReactIR and Raman spectroscopy. We have tested a picoSpin-45 (currently under ThermoFisher Scientific) benchtop NMR instrument to monitor three types of reactions by 1D (1) H NMR: a Fischer esterification, a Suzuki cross-coupling, and the formation of an oxime. The Fischer esterification is a relatively simple reaction run at high concentration and served as proof of concept. The Suzuki coupling is an example of a more complex, commonly used reaction involving overlapping signals. Finally, the oxime formation involved a reaction in two phases that cannot be monitored by other PAT tools. Here, we discuss the pros and cons of monitoring these reactions at a low-field of 45 MHz by 1D (1) H NMR. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

Post-Plasma SiOx Coatings of Metal and Metal Oxide Nanoparticles for Enhanced Thermal Stability and Tunable Photoactivity Applications

PubMed Central

Post, Patrick; Jidenko, Nicolas; Weber, Alfred P.; Borra, Jean-Pascal

2016-01-01

The plasma-based aerosol process developed for the direct coating of particles in gases with silicon oxide in a continuous chemical vapor deposition (CVD) process is presented. It is shown that non-thermal plasma filaments induced in a dielectric barrier discharge (DBD) at atmospheric pressure trigger post-DBD gas phase reactions. DBD operating conditions are first scanned to produce ozone and dinitrogen pentoxide. In the selected conditions, these plasma species react with gaseous tetraethyl orthosilicate (TEOS) precursor downstream of the DBD. The gaseous intermediates then condense on the surface of nanoparticles and self-reactions lead to homogeneous solid SiOx coatings, with thickness from nanometer to micrometer. This confirms the interest of post-DBD injection of the organo-silicon precursor to achieve stable production of actives species with subsequent controlled thickness of SiOx coatings. SiOx coatings of spherical and agglomerated metal and metal oxide nanoparticles (Pt, CuO, TiO2) are achieved. In the selected DBD operating conditions, the thickness of homogeneous nanometer sized coatings of spherical nanoparticles depends on the reaction duration and on the precursor concentration. For agglomerates, operating conditions can be tuned to cover preferentially the interparticle contact zones between primary particles, shifting the sintering of platinum agglomerates to much higher temperatures than the usual sintering temperature. Potential applications for enhanced thermal stability and tunable photoactivity of coated agglomerates are presented. PMID:28335219

Reaction chemistry and collisional processes in multiple devices for resolving isobaric interferences in ICP-MS.

PubMed

Bandura, D R; Baranov, V I; Tanner, S D

2001-07-01

A low-level review of the fundamentals of ion-molecule interactions is presented. These interactions are used to predict the efficiencies of collisional fragmentation, energy damping and reaction for a variety of neutral gases as a function of pressure in a rf-driven collision/reaction cell. It is shown that the number of collisions increases dramatically when the ion energies are reduced to near-thermal (< 0.1 eV), because of the ion-induced dipole and ion-dipole interaction. These considerations suggest that chemical reaction can be orders of magnitude more efficient at improving the analyte signal/background ratio than can collisional fragmentation. Considerations that lead to an appropriate selection of type of gas, operating pressure, and ion energies for efficient operation of the cell for the alleviation of spectral interferences are discussed. High efficiency (large differences between reaction efficiencies of the analyte and interference ions, and concomitant suppression of secondary chemistry) might be required to optimize the chemical resolution (determination of an analyte in the presence of an isobaric interference) when using ion-molecule chemistry to suppress the interfering ion. In many instances atom transfer to the analyte, which shifts the analytical m/z by the mass of the atom transferred, provides high chemical resolution, even when the efficiency of reaction is relatively low. Examples are given of oxidation, hydroxylation, and chlorination of analyte ions (V+, Fe+, As+, Se+, Sr+, Y+, and Zr+) to improve the capability of determination of complex samples. Preliminary results are given showing O-atom abstraction by CO from CaO+ to enable the determination of Fe in high-Ca samples.

Can short-wavelength depleted bright light during single simulated night shifts prevent circadian phase shifts?

PubMed

Regente, J; de Zeeuw, J; Bes, F; Nowozin, C; Appelhoff, S; Wahnschaffe, A; Münch, M; Kunz, D

2017-05-01

In single night shifts, extending habitual wake episodes leads to sleep deprivation induced decrements of performance during the shift and re-adaptation effects the next day. We investigated whether short-wavelength depleted (=filtered) bright light (FBL) during a simulated night shift would counteract such effects. Twenty-four participants underwent a simulated night shift in dim light (DL) and in FBL. Reaction times, subjective sleepiness and salivary melatonin concentrations were assessed during both nights. Daytime sleep was recorded after both simulated night shifts. During FBL, we found no melatonin suppression compared to DL, but slightly faster reaction times in the second half of the night. Daytime sleep was not statistically different between both lighting conditions (n = 24) and there was no significant phase shift after FBL (n = 11). To conclude, our results showed positive effects from FBL during simulated single night shifts which need to be further tested with larger groups, in more applied studies and compared to standard lighting. Copyright © 2016 Elsevier Ltd. All rights reserved.

Syngas production by high temperature steam/CO2 coelectrolysis using solid oxide electrolysis cells.

PubMed

Chen, Xinbing; Guan, Chengzhi; Xiao, Guoping; Du, Xianlong; Wang, Jian-Qiang

2015-01-01

High temperature (HT) steam/CO2 coelectrolysis with solid oxide electrolysis cells (SOECs) using the electricity and heat generated from clean energies is an important alternative for syngas production without fossil fuel consumption and greenhouse gas emissions. Herein, reaction characteristics and the outlet syngas composition of HT steam/CO2 coelectrolysis under different operating conditions, including distinct inlet gas compositions and electrolysis current densities, are systematically studied at 800 °C using commercially available SOECs. The HT coelectrolysis process, which has comparable performance to HT steam electrolysis, is more active than the HT CO2 electrolysis process, indicating the important contribution of the reverse water-gas shift reaction in the formation of CO. The outlet syngas composition from HT steam/CO2 coelectrolysis is very sensitive to the operating conditions, indicating the feasibility of controlling the syngas composition by varying these conditions. Maximum steam and CO2 utilizations of 77% and 76% are achieved at 1.0 A cm(-2) with an inlet gas composition of 20% H2/40% steam/40% CO2.

Novel process and catalytic materials for converting CO2 and H2 containing mixtures to liquid fuels and chemicals.

PubMed

Meiri, Nora; Dinburg, Yakov; Amoyal, Meital; Koukouliev, Viatcheslav; Nehemya, Roxana Vidruk; Landau, Miron V; Herskowitz, Moti

2015-01-01

Carbon dioxide and water are renewable and the most abundant feedstocks for the production of chemicals and fungible fuels. However, the current technologies for production of hydrogen from water are not competitive. Therefore, reacting carbon dioxide with hydrogen is not economically viable in the near future. Other alternatives include natural gas, biogas or biomass for the production of carbon dioxide, hydrogen and carbon monoxide mixtures that react to yield chemicals and fungible fuels. The latter process requires a high performance catalyst that enhances the reverse water-gas-shift (RWGS) reaction and Fischer-Tropsch synthesis (FTS) to higher hydrocarbons combined with an optimal reactor system. Important aspects of a novel catalyst, based on a Fe spinel and three-reactor system developed for this purpose published in our recent paper and patent, were investigated in this study. Potassium was found to be a key promoter that improves the reaction rates of the RWGS and FTS and increases the selectivity of higher hydrocarbons while producing mostly olefins. It changed the texture of the catalyst, stabilized the Fe-Al-O spinel, thus preventing decomposition into Fe3O4 and Al2O3. Potassium also increased the content of Fe5C2 while shifting Fe in the oxide and carbide phases to a more reduced state. In addition, it increased the relative exposure of carbide iron on the catalysts surface, the CO2 adsorption and the adsorption strength. A detailed kinetic model of the RWGS, FTS and methanation reactions was developed for the Fe spinel catalyst based on extensive experimental data measured over a range of operating conditions. Significant oligomerization activity of the catalyst was found. Testing the pelletized catalyst with CO2, CO and H2 mixtures over a range of operating conditions demonstrated its high productivity to higher hydrocarbons. The composition of the liquid (C5+) was found to be a function of the potassium content and the composition of the feedstock.

First-principles study on C=C defects near SiC/SiO2 interface: Defect passivation by double-bond saturation

NASA Astrophysics Data System (ADS)

Tajima, Nobuo; Kaneko, Tomoaki; Yamasaki, Takahiro; Nara, Jun; Schimizu, Tatsuo; Kato, Koichi; Ohno, Takahisa

2018-04-01

Thermally produced SiC/SiO2 stacking in SiC MOSFETs creates defect-related interfacial states in and around the band gap of SiC. These interfacial states can cause serious reliability problems such as threshold voltage shift, as well as efficiency problems such as channel mobility degradation. Carbon species having C=C double bonds have been suggested as one of the origins of these interfacial states. We have theoretically shown that this type of defect produces interfacial states in and around the band gap of SiC, and that they can be removed by saturating the C=C double bond by reactions with H2 and F2. The single-bond products of these reactions are found to be stable at regular device operation temperatures.

Hydrolysis of Nerve Agents by Model Nucleophiles: A Computational Study

PubMed Central

Beck, Jeremy M.

2008-01-01

Density functional theory calculations were employed to study the reaction of five nerve agents with model nucleophiles, including EtX− and EtXH (X = O, S, Se) for serine, cysteine and selenocysteine, respectively. Calculations at the B3LYP/6-311++G(2d,p) level of theory predict an exothermic reaction between ethoxide and all of the nerve agents studied. As compared to EtO− as a nucleophile, these reactions become ~30 kcal/mol more endothermic for EtS−, and by ~40 kcal/mol for EtSe−. The equivalent reactions with the neutral nucleophiles (EtXH) were more endothermic. The effect of solvation on the reaction thermochemistry was determined using a polarizable continuum model simulating the dielectric constant of chloroform. While there was a large exothermic shift for reactions involving charged nucleophiles with solvation modeling, the corresponding shift was minimal for the reaction with neutral nucleophiles. PMID:18538754

Human reliability and plant operating efficiency: Are 12-hour work schedules cause for concern

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baker, T.L.

1992-01-01

Since the introduction of 12-h shifts to the US nuclear power industry only 8 yr ago, compressed workweek schedules have proliferated among operations departments at a phenomenal rate. Many plants that continue to use 8-h shifts during normal operations routinely change to scheduled 12-h shifts during refueling or maintenance outages. The most critical issue in the use of extended work shifts is whether alertness, physical stamina, or mental performance are compromised to the point of reducing safety or efficiency of nuclear power plant operation. Laboratory and field research sponsored by the National Institute of Occupational Safety and Health suggests thatmore » alertness, measured by self-ratings, and mental performance, measured by computer-based performance tests, are impaired on 12-h shifts compared with 8-h shifts. In contrast to these findings, plant operating efficiency and operator performance have been rated as improved in two field studies conducted in operating nuclear power plants (Fast Flux Test Facility, Washington and Ontario Hydro, Canada). A recent Electric Power Research Institute review of nuclear industry experience with 12-h shifts also suggests an overwhelmingly positive rating of 12-h schedules from both control room operators and management.« less

Molecular implementation of molecular shift register memories

NASA Technical Reports Server (NTRS)

Beratan, David N. (Inventor); Onuchic, Jose N. (Inventor)

1991-01-01

An electronic shift register memory (20) at the molecular level is described. The memory elements are based on a chain of electron transfer molecules (22) and the information is shifted by photoinduced (26) electron transfer reactions. Thus, multi-step sequences of charge transfer reactions are used to move charge with high efficiency down a molecular chain. The device integrates compositions of the invention onto a VLSI substrate (36), providing an example of a molecular electronic device which may be fabricated. Three energy level schemes, molecular implementation of these schemes, optical excitation strategies, charge amplification strategies, and error correction strategies are described.

Electronic shift register memory based on molecular electron-transfer reactions

NASA Technical Reports Server (NTRS)

Hopfield, J. J.; Onuchic, Jose Nelson; Beratan, David N.

1989-01-01

The design of a shift register memory at the molecular level is described in detail. The memory elements are based on a chain of electron-transfer molecules incorporated on a very large scale integrated (VLSI) substrate, and the information is shifted by photoinduced electron-transfer reactions. The design requirements for such a system are discussed, and several realistic strategies for synthesizing these systems are presented. The immediate advantage of such a hybrid molecular/VLSI device would arise from the possible information storage density. The prospect of considerable savings of energy per bit processed also exists. This molecular shift register memory element design solves the conceptual problems associated with integrating molecular size components with larger (micron) size features on a chip.

Reaction monitoring using hyperpolarized NMR with scaling of heteronuclear couplings by optimal tracking.

PubMed

Zhang, Guannan; Schilling, Franz; Glaser, Steffen J; Hilty, Christian

2016-11-01

Off-resonance decoupling using the method of Scaling of Heteronuclear Couplings by Optimal Tracking (SHOT) enables determination of heteronuclear correlations of chemical shifts in single scan NMR spectra. Through modulation of J-coupling evolution by shaped radio frequency pulses, off resonance decoupling using SHOT pulses causes a user-defined dependence of the observed J-splitting, such as the splitting of 13 C peaks, on the chemical shift offset of coupled nuclei, such as 1 H. Because a decoupling experiment requires only a single scan, this method is suitable for characterizing on-going chemical reactions using hyperpolarization by dissolution dynamic nuclear polarization (D-DNP). We demonstrate the calculation of [ 13 C, 1 H] chemical shift correlations of the carbanionic active sites from hyperpolarized styrene polymerized using sodium naphthalene as an initiator. While off resonance decoupling by SHOT pulses does not enhance the resolution in the same way as a 2D NMR spectrum would, the ability to obtain the correlations in single scans makes this method ideal for determination of chemical shifts in on-going reactions on the second time scale. In addition, we present a novel SHOT pulse that allows to scale J-splittings 50% larger than the respective J-coupling constant. This feature can be used to enhance the resolution of the indirectly detected chemical shift and reduce peak overlap, as demonstrated in a model reaction between p-anisaldehyde and isobutylamine. For both pulses, the accuracy is evaluated under changing signal-to-noise ratios (SNR) of the peaks from reactants and reaction products, with an overall standard deviation of chemical shift differences compared to reference spectra of 0.02ppm when measured on a 400MHz NMR spectrometer. Notably, the appearance of decoupling side-bands, which scale with peak intensity, appears to be of secondary importance. Copyright © 2016 Elsevier Inc. All rights reserved.

Design of a Molecular Memory Device: The Electron Transfer Shift Register Memory

NASA Technical Reports Server (NTRS)

Beratan, D.

1993-01-01

A molecular shift register memory at the molecular level is described. The memory elements consist of molecules can exit in either an oxidized or reduced state and the bits are shifted between the cells with photoinduced electron transfer reactions.

Integrated reformer and shift reactor

DOEpatents

Bentley, Jeffrey M.; Clawson, Lawrence G.; Mitchell, William L.; Dorson, Matthew H.

2006-06-27

A hydrocarbon fuel reformer for producing diatomic hydrogen gas is disclosed. The reformer includes a first reaction vessel, a shift reactor vessel annularly disposed about the first reaction vessel, including a first shift reactor zone, and a first helical tube disposed within the first shift reactor zone having an inlet end communicating with a water supply source. The water supply source is preferably adapted to supply liquid-phase water to the first helical tube at flow conditions sufficient to ensure discharge of liquid-phase and steam-phase water from an outlet end of the first helical tube. The reformer may further include a first catalyst bed disposed in the first shift reactor zone, having a low-temperature shift catalyst in contact with the first helical tube. The catalyst bed includes a plurality of coil sections disposed in coaxial relation to other coil sections and to the central longitudinal axis of the reformer, each coil section extending between the first and second ends, and each coil section being in direct fluid communication with at least one other coil section.

A New Kind of Shift Operators for Infinite Circular and Spherical Wells

DOE PAGES

Sun, Guo-Hua; Launey, K. D.; Dytrych, T.; ...

2014-01-01

A new kind of smore » hift operators for infinite circular and spherical wells is identified. These shift operators depend on all spatial variables of quantum systems and connect some eigenstates of confined systems of different radii R sharing energy levels with a common eigenvalue. In circular well, the momentum operators P ± = P x ± i P y play the role of shift operators. The P x and P y operators, the third projection of the orbital angular momentum operator L z , and the Hamiltonian H form a complete set of commuting operators with the SO(2) symmetry. In spherical well, the shift operators establish a novel relation between ψ l m ( r ) and ψ ( l ± 1 ) ( m ± 1 ) ( r ) .« less

Acoustic Sensing Based on Density Shift of Microspheres by Surface Binding of Gold Nanoparticles.

PubMed

Miyagawa, Akihisa; Inoue, Yoshinori; Harada, Makoto; Okada, Tetsuo

2017-01-01

Herein, we propose a concept for sensing based on density changes of microparticles (MPs) caused by a biochemical reaction. The MPs are levitated by a combined acoustic-gravitational force at a position determined by the density and compressibility. Importantly, the levitation is independent of the MPs sizes. When gold nanoparticles (AuNPs) are bound on the surface of polymer MPs through a reaction, the density of the MPs dramatically increases, and their levitation position in the acoustic-gravitational field is lowered. Because the shift of the levitation position is proportional to the number of AuNPs bound on one MP, we can determine the number of molecules involved in the reaction. The avidin-biotin reaction is used to demonstrate the effectiveness of this concept. The number of molecules involved in the reaction is very small because the reaction space is small for an MP; thus, the method has potential for highly sensitive detection.

Hydrologic influence on redox dynamics in estuarine environments

NASA Astrophysics Data System (ADS)

Michael, H. A.; Kim, K. H.; Guimond, J. A.; Heiss, J.; Ullman, W. J.; Seyfferth, A.

2017-12-01

Redox conditions in coastal aquifers control reactions that impact nutrient cycling, contaminant release, and carbon budgets, with implications for water resources and ecosystem health. Hydrologic changes can shift redox boundaries and inputs of reactants, especially in dynamic coastal systems subject to fluctuations on tidal, lunar, and longer timescales. We present two examples of redox shifts in estuarine systems in Delaware, USA: a beach aquifer and a saltmarsh. Beach aquifers are biogeochemical hot spots due to mixing between fresh groundwater and infiltrating seawater. At Cape Henlopen, DE, geochemical measurements identified reactions in the intertidal aquifer that include cycling of carbon, nitrogen, iron, and sulfur. Measurements and modeling illustrate that redox potential as well as the locations of redox reactions shift on tidal to seasonal timescales and in response to changing beach and aquifer properties, impacting overall rates of reactions such as denitrification that reduces N loads to coastal waters. In the St. Jones National Estuarine Research Reserve, tidal fluctuations in channels cause periodic groundwater-surface water exchange, water table movement, and intermittent flooding that varies spatially across the saltmarsh. These changes create shifts in redox potential that are greatest near channels and in the top 20 cm of sediments. The magnitude of redox change depends on hydrologic setting (near channels or in marsh interior), hydrologic conditions (tidal stage, seasonal shifts), as well as prevalence of macropores created by crab burrows that change seasonally with crab activity. These shifts correspond to changes in porewater chemistry that have implications for nutrient cycling and carbon export to the ocean. Understanding hydrologic influence on redox geochemistry is critical for predicting how these systems and their ecosystem services may change in the future in response to anthropogenic and climate change.

Variables affecting efficiency of molasses fermentation wastewater ozonation.

PubMed

Coca, M; Peña, M; González, G

2005-09-01

The main operating variables affecting ozonation efficiencies of wastewater from beet molasses alcoholic fermentation have been studied. Semibatch experiments have been performed in order to analyze the influence of pH, bicarbonate ion, temperature and stirring rate on color and organic matter removals. The efficiencies were similar regardless of the pH, which indicates that direct reactions of ozone with wastewater organics were predominant to radical reactions. Gel permeation chromatography confirmed the reduction in the concentration of organics absorbing light at 475 nm after ozonation. The elimination of bicarbonate ion, strong inhibitor of hydroxyl radical reactions, yielded an improvement in both color and COD reduction efficiencies. Acidification for removing bicarbonate ions produced a shift of colored compounds to smaller molecular weights. The highest efficiencies were achieved at 40 degrees C. Color and COD reductions at 40 degrees C were about 90% and 37%, respectively. In no case, the percentage of TOC removed was higher than 10-15%. Stirring rate had a slightly positive effect during the first stage of the ozonation showing that mass transfer played a role only during the initial reaction phase when direct attack of ozone molecules to aromatic/olefinic structures of colored substances was the predominant pathway.

In situ characterization of catalysts and membranes in a microchannel under high-temperature water gas shift reaction conditions

NASA Astrophysics Data System (ADS)

Cavusoglu, G.; Dallmann, F.; Lichtenberg, H.; Goldbach, A.; Dittmeyer, R.; Grunwaldt, J.-D.

2016-05-01

Microreactor technology with high heat transfer in combination with stable catalysts is a very attractive approach for reactions involving major heat effects such as methane steam reforming and to some extent, also the high temperature water gas shift (WGS) reaction. For this study Rh/ceria catalysts and an ultrathin hydrogen selective membrane were characterized in situ in a microreactor specially designed for x-ray absorption spectroscopic measurements under WGS conditions. The results of these experiments can serve as a basis for further development of the catalysts and membranes.

Stochastic surface walking reaction sampling for resolving heterogeneous catalytic reaction network: A revisit to the mechanism of water-gas shift reaction on Cu

NASA Astrophysics Data System (ADS)

Zhang, Xiao-Jie; Shang, Cheng; Liu, Zhi-Pan

2017-10-01

Heterogeneous catalytic reactions on surface and interfaces are renowned for ample intermediate adsorbates and complex reaction networks. The common practice to reveal the reaction mechanism is via theoretical computation, which locates all likely transition states based on the pre-guessed reaction mechanism. Here we develop a new theoretical method, namely, stochastic surface walking (SSW)-Cat method, to resolve the lowest energy reaction pathway of heterogeneous catalytic reactions, which combines our recently developed SSW global structure optimization and SSW reaction sampling. The SSW-Cat is automated and massively parallel, taking a rough reaction pattern as input to guide reaction search. We present the detailed algorithm, discuss the key features, and demonstrate the efficiency in a model catalytic reaction, water-gas shift reaction on Cu(111) (CO + H2O → CO2 + H2). The SSW-Cat simulation shows that water dissociation is the rate-determining step and formic acid (HCOOH) is the kinetically favorable product, instead of the observed final products, CO2 and H2. It implies that CO2 and H2 are secondary products from further decomposition of HCOOH at high temperatures. Being a general purpose tool for reaction prediction, the SSW-Cat may be utilized for rational catalyst design via large-scale computations.

Temperature-dependent responses of the photosynthetic and chlorophyll fluorescence attributes of apple (Malus domestica) leaves during a sustained high temperature event.

PubMed

Greer, Dennis H

2015-12-01

The objective of this study was to follow changes in the temperature-dependent responses of photosynthesis and photosystem II performance in leaves of field-grown trees of Malus domestica (Borkh.) cv. 'Red Gala' before and after exposure to a long-term heat event occurring late in the growing season. Light-saturated photosynthesis was optimal at 25 °C before the heat event. The high temperatures caused a reduction in rates at low temperatures (15-20 °C) but increased rates at high temperatures (30-40 °C) and a shift in optimum to 30 °C. Rates at all temperatures increased after the heat event and the optimum shifted to 33 °C, indicative of some acclimation to the high temperatures occurring. Photosystem II attributes were all highly temperature-dependent. The operating quantum efficiency of PSII during the heat event declined, but mostly at high temperatures, partly because of decreased photochemical quenching but also from increased non-photochemical quenching. However, a further reduction in PSII operating efficiency occurred after the heat event subsided. Non-photochemical quenching had subsided, whereas photochemical quenching had increased in the post-heat event period and consistent with a greater fraction of open PSII reaction centres. What remained uncertain was why these effects on PSII performance appeared to have no effect on the process of light-saturated photosynthesis. However, the results provide an enhanced understanding of the impacts of sustained high temperatures on the photosynthetic process and its underlying reactions, notably photochemistry. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

Using newly developed multiplex polymerase chain reaction and melting curve analysis for detection and discrimination of β-lactamases in Escherichia coli isolates from intensive care patients.

PubMed

Chromá, Magdaléna; Hricová, Kristýna; Kolář, Milan; Sauer, Pavel; Koukalová, Dagmar

2011-11-01

A total of 78 bacterial strains with known β-lactamases were used to optimize a rapid detection system consisting of multiplex polymerase chain reaction and melting curve analysis to amplify and identify blaTEM, blaSHV, and blaCTX-M genes in a single reaction. Additionally, to evaluate the applicability of this method, 32 clinical isolates of Escherichia coli displaying an extended-spectrum β-lactamase phenotype from patients hospitalized at intensive care units were tested. Results were analyzed by the Rotor-Gene operating software and Rotor-Gene ScreenClust HRM Software. The individual melting curves differed by a temperature shift or curve shape, according to the presence of β-lactamase genes. With the use of this method and direct sequencing, blaCTX-M-15-like was identified as the most prevalent β-lactamase gene. In conclusion, this novel detection system seems to be a suitable tool for rapid detection of present β-lactamase genes and their characterization. Copyright © 2011 Elsevier Inc. All rights reserved.

Hyperpolarizability and Operational Magic Wavelength in an Optical Lattice Clock

NASA Astrophysics Data System (ADS)

Brown, R. C.; Phillips, N. B.; Beloy, K.; McGrew, W. F.; Schioppo, M.; Fasano, R. J.; Milani, G.; Zhang, X.; Hinkley, N.; Leopardi, H.; Yoon, T. H.; Nicolodi, D.; Fortier, T. M.; Ludlow, A. D.

2017-12-01

Optical clocks benefit from tight atomic confinement enabling extended interrogation times as well as Doppler- and recoil-free operation. However, these benefits come at the cost of frequency shifts that, if not properly controlled, may degrade clock accuracy. Numerous theoretical studies have predicted optical lattice clock frequency shifts that scale nonlinearly with trap depth. To experimentally observe and constrain these shifts in an 171Yb optical lattice clock, we construct a lattice enhancement cavity that exaggerates the light shifts. We observe an atomic temperature that is proportional to the optical trap depth, fundamentally altering the scaling of trap-induced light shifts and simplifying their parametrization. We identify an "operational" magic wavelength where frequency shifts are insensitive to changes in trap depth. These measurements and scaling analysis constitute an essential systematic characterization for clock operation at the 10-18 level and beyond.

Atmospheric autoxidation is increasingly important in urban and suburban North America

NASA Astrophysics Data System (ADS)

Praske, Eric; Otkjær, Rasmus V.; Crounse, John D.; Caleb Hethcox, J.; Stoltz, Brian M.; Kjaergaard, Henrik G.; Wennberg, Paul O.

2018-01-01

Gas-phase autoxidation—regenerative peroxy radical formation following intramolecular hydrogen shifts—is known to be important in the combustion of organic materials. The relevance of this chemistry in the oxidation of organics in the atmosphere has received less attention due, in part, to the lack of kinetic data at relevant temperatures. Here, we combine computational and experimental approaches to investigate the rate of autoxidation for organic peroxy radicals (RO2) produced in the oxidation of a prototypical atmospheric pollutant, n-hexane. We find that the reaction rate depends critically on the molecular configuration of the RO2 radical undergoing hydrogen transfer (H-shift). RO2 H-shift rate coefficients via transition states involving six- and seven-membered rings (1,5 and 1,6 H-shifts, respectively) of α-OH hydrogens (HOC-H) formed in this system are of order 0.1 s‑1 at 296 K, while the 1,4 H-shift is calculated to be orders of magnitude slower. Consistent with H-shift reactions over a substantial energetic barrier, we find that the rate coefficients of these reactions increase rapidly with temperature and exhibit a large, primary, kinetic isotope effect. The observed H-shift rate coefficients are sufficiently fast that, as a result of ongoing NOx emission reductions, autoxidation is now competing with bimolecular chemistry even in the most polluted North American cities, particularly during summer afternoons when NO levels are low and temperatures are elevated.

7Li(d,p)8Li transfer reaction in the NCSM/RGM approach

NASA Astrophysics Data System (ADS)

Raimondi, F.; Hupin, G.; Navrátil, P.; Quaglioni, S.

2018-03-01

Recently, we applied an ab initio method, the no-core shell model combined with the resonating group method, to the transfer reactions with light p-shell nuclei as targets and deuteron as the projectile. In particular, we studied the elastic scattering of deuterium on 7Li and the 7Li(d,p)8Li transfer reaction starting from a realistic two-nucleon interaction. In this contribution, we review of our main results on the 7Li(d,p)8Li transfer reaction, and we extend the study of the relevant reaction channels, by showing the dominant resonant phase shifts of the scattering matrix. We assess also the impact of the polarization effects of the deuteron below the breakup on the positive-parity resonant states in the reaction. For this purpose, we perform an analysis of the convergence trend of the phase and eigenphase shifts, with respect to the number of deuteron pseudostates included in the model space.

[Perception of shift work, burnout and sleep disturbances: a study among call centre operators].

PubMed

Consiglio, Chiara; Tinelli, Erica

2016-01-20

Shift work is often considered to be a factor that can negatively affect health and sleep quality. However, it is usually considered as a structural factor of the job and not as a perception of a work demand. The study aimed at analyzing the relationship between perception of shift work, burnout and sleep disturbances in a potentially stressful context, namely the call centre setting. Call centre operators (N=510) completed a questionnaire encompassing the following scales: perceptions of shift work, monotony, time pressure, exhaustion, cynicism and sleep disturbances. We conducted two hierarchical regressions in order to analyze the contribution of the perception of shift work on burnout dimensions (exhaustion and cynicism), beyond the contribution of socio-demographical variables, and of two specific job stressors for call centre operators, namely monotony and time pressure. The mediating role of exhaustion and cynicism between the perception of shift work and sleep disturbances was also explored. The perception of shift work was associated with operators' burnout, beyond the effect of socio-demographic variables and other job stressors. In addition, the relationship between the perception of shift work and sleep disturbances was fully mediated by exhaustion and partially mediated by cynicism. Perceived shift work may represent a risk factor for the health of call centre operators that should be monitored and possibly managed through specific organizational interventions.

Self-consistent frequencies of the electron-photon system

NASA Astrophysics Data System (ADS)

Hawton, Margaret

1993-09-01

The Heisenberg equations describing the dynamics of coupled Fermion photon operators are solved self-consistently. Photon modes, for which ω~=kc, and particlelike Bohr modes with frequencies ωnI~=(En-EI)/ħ are both approximate solutions to the system of equations that results if the current density is the source in the operator Maxwell equations. Current fluctuations associated with the Bohr modes and required by a fluctuation-dissipation theorem are attributed to the point nature of the particle. The interaction energy is given by the Casimir-force-like expression ΔE=1/2ħtsum(ΔωnI+Δωkc) or by the expectation value of 1/2(qcphi-qp^.A^/mc+q2A2/mc2). It is verified that the equal-time momentum-density and vector-potential operators commute if the contributions of both the Bohr modes and vacuum fluctuations are included. Both electromagnetic and Bohr or radiation-reaction modes are found to contribute equally to spontaneous emission and to the Lamb shift.

Electrochemical formation of a Pt/Zn alloy and its use as a catalyst for oxygen reduction reaction in fuel cells.

PubMed

Sode, Aya; Li, Winton; Yang, Yanguo; Wong, Phillip C; Gyenge, Elod; Mitchell, Keith A R; Bizzotto, Dan

2006-05-04

The characterization of an electrochemically created Pt/Zn alloy by Auger electron spectroscopy is presented indicating the formation of the alloy, the oxidation of the alloy, and the room temperature diffusion of the Zn into the Pt regions. The Pt/Zn alloy is stable up to 1.2 V/RHE and can only be removed with the oxidation of the base Pt metal either electrochemically or in aqua regia. The Pt/Zn alloy was tested for its effectiveness toward oxygen reduction. Kinetics of the oxygen reduction reaction (ORR) were measured using a rotating disk electrode (RDE), and a 30 mV anodic shift in the potential of ORR was found when comparing the Pt/Zn alloy to Pt. The Tafel slope was slightly smaller than that measured for the pure Pt electrode. A simple procedure for electrochemically modifying a Pt-containing gas diffusion electrode (GDE) with Zn was developed. The Zn-treated GDE was pressed with an untreated GDE anode, and the created membrane electrode assembly was tested. Fuel cell testing under two operating conditions (similar anode and cathode inlet pressures, and a larger cathode inlet pressure) indicated that the 30 mV shift observed on the RDE was also evident in the fuel cell tests. The high stability of the Pt/Zn alloy in acidic environments has a potential benefit for fuel cell applications.

Biological monitoring of benzene exposure for process operators during ordinary activity in the upstream petroleum industry.

PubMed

Bråtveit, Magne; Kirkeleit, Jorunn; Hollund, Bjørg Eli; Moen, Bente E

2007-07-01

This study characterized the exposure of crude oil process operators to benzene and related aromatics during ordinary activity and investigated whether the operators take up benzene at this level of exposure. We performed the study on a fixed, integrated oil and gas production facility on Norway's continental shelf. The study population included 12 operators and 9 referents. We measured personal exposure to benzene, toluene, ethylbenzene and xylene during three consecutive 12-h work shifts using organic vapour passive dosimeter badges. We sampled blood and urine before departure to the production facility (pre-shift), immediately after the work shift on Day 13 of the work period (post-shift) and immediately before the following work shift (pre-next shift). We also measured the exposure to hydrocarbons during short-term tasks by active sampling using Tenax tubes. The arithmetic mean exposure over the 3 days was 0.042 ppm for benzene (range <0.001-0.69 ppm), 0.05 ppm for toluene, 0.02 ppm for ethylbenzene and 0.03 ppm for xylene. Full-shift personal exposure was significantly higher when the process operators performed flotation work during the shift versus other tasks. Work in the flotation area was associated with short-term (6-15 min) arithmetic mean exposure to benzene of 1.06 ppm (range 0.09-2.33 ppm). The concentrations of benzene in blood and urine did not differ between operators and referents at any time point. When we adjusted for current smoking in regression analysis, benzene exposure was significantly associated with the post-shift concentration of benzene in blood (P = 0.01) and urine (P = 0.03), respectively. Although these operators perform tasks with relatively high short-term exposure to benzene, the full-shift mean exposure is low during ordinary activity. Some evidence indicates benzene uptake within this range of exposure.

Hydromechanical transmission with hydrodynamic drive

DOEpatents

Orshansky, Jr., deceased, Elias; Weseloh, William E.

1979-01-01

This transmission has a first planetary gear assembly having first input means connected to an input shaft, first output means, and first reaction means, and a second planetary gear assembly having second input means connected to the first input means, second output means, and second reaction means connected directly to the first reaction means by a reaction shaft. First clutch means, when engaged, connect the first output means to an output shaft in a high driving range. A hydrodynamic drive is used; for example, a torque converter, which may or may not have a stationary case, has a pump connected to the second output means, a stator grounded by an overrunning clutch to the case, and a turbine connected to an output member, and may be used in a starting phase. Alternatively, a fluid coupling or other type of hydrodynamic drive may be used. Second clutch means, when engaged, for connecting the output member to the output shaft in a low driving range. A variable-displacement hydraulic unit is mechanically connected to the input shaft, and a fixed-displacement hydraulic unit is mechanically connected to the reaction shaft. The hydraulic units are hydraulically connected together so that when one operates as a pump the other acts as a motor, and vice versa. Both clutch means are connected to the output shaft through a forward-reverse shift arrangement. It is possible to lock out the torque converter after the starting phase is over.

Investigating daily fatigue scores during two-week offshore day shifts.

PubMed

Riethmeister, Vanessa; Bültmann, Ute; Gordijn, Marijke; Brouwer, Sandra; de Boer, Michiel

2018-09-01

This study examined daily scores of fatigue and circadian rhythm markers over two-week offshore day shift periods. A prospective cohort study among N = 60 offshore day-shift workers working two-week offshore shifts was conducted. Offshore day shifts lasted from 07:00 - 19:00 h. Fatigue was measured objectively with pre- and post-shift scores of the 3-minute psychomotor vigilance tasks (PVT-B) parameters (reaction times, number of lapses, errors and false starts) and subjectively with pre- and post-shift Karolinska Sleepiness Scale (KSS) ratings. Evening saliva samples were collected on offshore days 2,7 and 13 to measure circadian rhythm markers such as dim-light melatonin onset times and cortisol. Generalized and linear mixed model analyses were used to examine daily fatigue scores over time. Complete data from N = 42 offshore day shift workers was analyzed. Daily parameters of objective fatigue, PVT-B scores (reaction times, average number of lapses, errors and false starts), remained stable over the course of the two-week offshore day shifts. Daily subjective post-shift fatigue scores significantly increased over the course of the two-week offshore shifts. Each day offshore was associated with an increased post-shift subjective fatigue score of 0.06 points (95%CI: .03 - .09 p < .001). No significant statistical differences in subjective pre-shift fatigue scores were found. Neither a circadian rhythm phase shift of melatonin nor an effect on the pattern and levels of evening cortisol was found. Daily parameters of objective fatigue scores remained stable over the course of the two-week offshore day shifts. Daily subjective post-shift fatigue scores significantly increased over the course of the two-week offshore shifts. No significant changes in circadian rhythm markers were found. Increased post-shift fatigue scores, especially during the last days of an offshore shift, should be considered and managed in (offshore) fatigue risk management programs and fatigue risk prediction models. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effect of brain shift on the creation of functional atlases for deep brain stimulation surgery

PubMed Central

Pallavaram, Srivatsan; Remple, Michael S.; Neimat, Joseph S.; Kao, Chris; Konrad, Peter E.; D’Haese, Pierre-François

2011-01-01

Purpose In the recent past many groups have tried to build functional atlases of the deep brain using intra-operatively acquired information such as stimulation responses or micro-electrode recordings. An underlying assumption in building such atlases is that anatomical structures do not move between pre-operative imaging and intra-operative recording. In this study, we present evidences that this assumption is not valid. We quantify the effect of brain shift between pre-operative imaging and intra-operative recording on the creation of functional atlases using intra-operative somatotopy recordings and stimulation response data. Methods A total of 73 somatotopy points from 24 bilateral subthalamic nucleus (STN) implantations and 52 eye deviation stimulation response points from 17 bilateral STN implantations were used. These points were spatially normalized on a magnetic resonance imaging (MRI) atlas using a fully automatic non-rigid registration algorithm. Each implantation was categorized as having low, medium or large brain shift based on the amount of pneumocephalus visible on post-operative CT. The locations of somatotopy clusters and stimulation maps were analyzed for each category. Results The centroid of the large brain shift cluster of the somatotopy data (posterior, lateral, inferior: 3.06, 11.27, 5.36 mm) was found posterior, medial and inferior to that of the medium cluster (2.90, 13.57, 4.53 mm) which was posterior, medial and inferior to that of the low shift cluster (1.94, 13.92, 3.20 mm). The coordinates are referenced with respect to the mid-commissural point. Euclidean distances between the centroids were 1.68, 2.44 and 3.59 mm, respectively for low-medium, medium-large and low-large shift clusters. We found similar trends for the positions of the stimulation maps. The Euclidian distance between the highest probability locations on the low and medium-large shift maps was 4.06 mm. Conclusion The effect of brain shift in deep brain stimulation (DBS) surgery has been demonstrated using intra-operative somatotopy recordings as well as stimulation response data. The results not only indicate that considerable brain shift happens before micro-electrode recordings in DBS but also that brain shift affects the creation of accurate functional atlases. Therefore, care must be taken when building and using such atlases of intra-operative data and also when using intra-operative data to validate anatomical atlases. PMID:20033503

The Modality Shift Experiment in Adults and Children with High Functioning Autism

ERIC Educational Resources Information Center

Williams, Diane L.; Goldstein, Gerald; Minshew, Nancy J.

2013-01-01

This study used the modality shift experiment, a relatively simple reaction time measure to visual and auditory stimuli, to examine attentional shifting within and across modalities in 33 children and 42 adults with high-functioning autism as compared to matched numbers of age- and ability-matched typical controls. An exaggerated "modality shift…

Dynamical patterns and regime shifts in the nonlinear model of soil microorganisms growth

NASA Astrophysics Data System (ADS)

Zaitseva, Maria; Vladimirov, Artem; Winter, Anna-Marie; Vasilyeva, Nadezda

2017-04-01

Dynamical model of soil microorganisms growth and turnover is formulated as a system of nonlinear partial differential equations of reaction-diffusion type. We consider spatial distributions of concentrations of several substrates and microorganisms. Biochemical reactions are modelled by chemical kinetic equations. Transport is modelled by simple linear diffusion for all chemical substances, while for microorganisms we use different transport functions, e.g. some of them can actively move along gradient of substrate concentration, while others cannot move. We solve our model in two dimensions, starting from uniform state with small initial perturbations for various parameters and find parameter range, where small initial perturbations grow and evolve. We search for bifurcation points and critical regime shifts in our model and analyze time-space profile and phase portraits of these solutions approaching critical regime shifts in the system, exploring possibility to detect such shifts in advance. This work is supported by NordForsk, project #81513.

Synthesis of Polysubstituted Pyridines via a One-Pot Metal-Free Strategy.

PubMed

Wei, Hongbo; Li, Yun; Xiao, Ke; Cheng, Bin; Wang, Huifei; Hu, Lin; Zhai, Hongbin

2015-12-18

An efficient strategy for the one-pot synthesis of polysubstituted pyridines via a cascade reaction from aldehydes, phosphorus ylides, and propargyl azide is reported. The reaction sequence involves a Wittig reaction, a Staudinger reaction, an aza-Wittig reaction, a 6π-3-azatriene electrocyclization, and a 1,3-H shift. This protocol provides quick access to the polysubstituted pyridines from readily available substrates in good to excellent yields.

Measurement of key resonances for the 24Al(p ,γ )25Si reaction rate using in-beam γ -ray spectroscopy

NASA Astrophysics Data System (ADS)

Longfellow, B.; Gade, A.; Brown, B. A.; Richter, W. A.; Bazin, D.; Bender, P. C.; Bowry, M.; Elman, B.; Lunderberg, E.; Weisshaar, D.; Williams, S. J.

2018-05-01

Energy levels and branching ratios for the rp-process nucleus 25Si were determined from the reactions 9Be(26Si,25Si)X and 9Be(25Al,25Si)X using in-beam γ -ray spectroscopy with both high-efficiency and high-resolution detector arrays. Proton-unbound states at 3695(14) and 3802(11) keV were identified and assigned tentative spins and parities based on comparison to theory and the mirror nucleus. The 24Al(p ,γ )25Si reaction rate was calculated using the experimental states and states from charge-dependent USDA and USDB shell-model calculations with downward shifts of the 1 s1 /2 proton orbital to account for the observed Thomas-Ehrman shift, leading to a factor of 10-100 increase in rate for the temperature region of 0.22 GK as compared to a previous calculation. These shifts may be applicable to neighboring nuclei, impacting the proton capture rates in this region of the chart.

Core-level photoemission investigation of atomic-fluorine adsorption on GaAs(110)

NASA Astrophysics Data System (ADS)

McLean, A. B.; Terminello, L. J.; McFeely, F. R.

1989-12-01

The adsorption of atomic F on the cleaved GaAs(110) surface has been studied with use of high-resolution core-level photoelectron spectroscopy by exposing the GaAs(110) surfaces to XeF2, which adsorbs dissociatively, leaving atomic F behind. This surface reaction produces two chemically shifted components in the Ga 3d core-level emission which are attributed to an interfacial monofluoride and a stable trifluoride reaction product, respectively. The As 3d core level develops only one chemically shifted component and from its exposure-dependent behavior it is attributed to an interfacial monofluoride. Least-squares analysis of the core-level line shapes revealed that (i) the F bonds to both the anion and the cation , (ii) the GaF3 component (characteristic of strong interfacial reaction) and the surface core-level shifted component (characteristic of a well ordered, atomically clean surface) are present together over a relatively large range of XeF2 exposures, and (iii) it is the initial disruption of the GaAs(110) surface that is the rate-limiting step in this surface reaction. These results are compared with similar studies of Cl and O adsorption on GaAs(110).

Investigation into the effects of sulfur on syngas reforming inside a solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Li, Ting Shuai; Xu, Min; Gao, Chongxin; Wang, Baoqing; Liu, Xiyun; Li, Baihai; Wang, Wei Guo

2014-07-01

The electrochemical performance and long-term durability of a solid oxide fuel cell have been evaluated with a simulated coal syngas containing 2 ppm H2S as fuel. The resulting impedance spectra indicate that no observable power loss is caused by the addition of 2 ppm H2S, and the cell shows stability of nearly 500 h at 0.625 A cm-2. The composition of mixed gas is analyzed both at a current load of 0.625 A cm-2 and open circuit state. Hydrogen and carbon monoxide are directly consumed as fuels at the anode side, whereas methane stays unchanged during the operation. It seems the internal carbohydrate reforming and impurity poisoning interacts and weakens the poisoning effects. The oxidation of H2 and the water gas shift reaction take advantages over methane reforming at the cell operational conditions.

Direct Mapping of Band Positions in Doped and Undoped Hematite during Photoelectrochemical Water Splitting

DOE PAGES

Shavorskiy, Andrey; Ye, Xiaofei; Karslgolu, Osman; ...

2017-10-30

Photoelectrochemical water splitting is a promising pathway for the direct conversion of renewable solar energy to easy to store and use chemical energy. The performance of a photoelectrochemical device is determined in large part by the heterogeneous interface between the photoanode and the electrolyte, which we here characterize directly under operating conditions using interface-specific probes. Utilizing X-ray photoelectron spectroscopy as a noncontact probe of local electrical potentials, we demonstrate direct measurements of the band alignment at the semiconductor/electrolyte interface of an operating hematite/KOH photoelectrochemical cell as a function of solar illumination, applied potential, and doping. Here, we provide evidence formore » the absence of in-gap states in this system, which is contrary to previous measurements using indirect methods, and give a comprehensive description of shifts in the band positions and limiting processes during the photoelectrochemical reaction.« less

The Acclimation of Phaeodactylum tricornutum to Blue and Red Light Does Not Influence the Photosynthetic Light Reaction but Strongly Disturbs the Carbon Allocation Pattern

PubMed Central

Jungandreas, Anne; Schellenberger Costa, Benjamin; Jakob, Torsten; von Bergen, Martin; Baumann, Sven; Wilhelm, Christian

2014-01-01

Diatoms are major contributors to the aquatic primary productivity and show an efficient acclimation ability to changing light intensities. Here, we investigated the acclimation of Phaeodactylum tricornutum to different light quality with respect to growth rate, photosynthesis rate, macromolecular composition and the metabolic profile by shifting the light quality from red light (RL) to blue light (BL) and vice versa. Our results show that cultures pre-acclimated to BL and RL exhibited similar growth performance, photosynthesis rates and metabolite profiles. However, light shift experiments revealed rapid and severe changes in the metabolite profile within 15 min as the initial reaction of light acclimation. Thus, during the shift from RL to BL, increased concentrations of amino acids and TCA cycle intermediates were observed whereas during the BL to RL shift the levels of amino acids were decreased and intermediates of glycolysis accumulated. Accordingly, on the time scale of hours the RL to BL shift led to a redirection of carbon into the synthesis of proteins, whereas during the BL to RL shift an accumulation of carbohydrates occurred. Thus, a vast metabolic reorganization of the cells was observed as the initial reaction to changes in light quality. The results are discussed with respect to a putative direct regulation of cellular enzymes by light quality and by transcriptional regulation. Interestingly, the short-term changes in the metabolome were accompanied by changes in the degree of reduction of the plastoquinone pool. Surprisingly, the RL to BL shift led to a severe inhibition of growth within the first 48 h which was not observed during the BL to RL shift. Furthermore, during the phase of growth arrest the photosynthetic performance did not change. We propose arguments that the growth arrest could have been caused by the reorganization of intracellular carbon partitioning. PMID:25111046

Neural Dynamics of Object-Based Multifocal Visual Spatial Attention and Priming: Object Cueing, Useful-Field-of-View, and Crowding

ERIC Educational Resources Information Center

Foley, Nicholas C.; Grossberg, Stephen; Mingolla, Ennio

2012-01-01

How are spatial and object attention coordinated to achieve rapid object learning and recognition during eye movement search? How do prefrontal priming and parietal spatial mechanisms interact to determine the reaction time costs of intra-object attention shifts, inter-object attention shifts, and shifts between visible objects and covertly cued…

Best Practices in Shift Handover Communication: Mars Exploration Rover Surface Operations

NASA Astrophysics Data System (ADS)

Parke, Bonny; Mishkin, Andrew

2005-12-01

During its prime mission, Mars Exploration Rover (MER) had many shift handovers in its surface operations. Because of the increased rates of accidents and errors historically associated with shift handovers, MER Mission management paid close attention to shift handovers and, when possible, developed them in accordance with best handover practices.We review the most important of these best practices, and include a generic "Checklist for Effective Handovers" to aid in the development of handovers.We present charts that depict structured information transfer across shifts. These charts show personnel schedules, meetings attended, handovers, and hand-offs on both the MER and on the earlier Mars Pathfinder Mission (MPF). It is apparent from these charts that although the MER Mission had a much larger number of surface operations personnel than MPF (approximately 300 vs. 178), and had three shifts instead of two, that it used many of the successful MPF communication strategies. Charts such as these can be helpful to those designing complicated and unique mission surface operations.

Associations between heat exposure, vigilance, and balance performance in summer tree fruit harvesters.

PubMed

Spector, June T; Krenz, Jennifer; Calkins, Miriam; Ryan, Dawn; Carmona, Jose; Pan, Mengjie; Zemke, Anna; Sampson, Paul D

2018-02-01

We sought to evaluate potential mediators of the relationship between heat exposure and traumatic injuries in outdoor agricultural workers. Linear mixed models were used to estimate associations between maximum work-shift Wet Bulb Globe Temperature (WBGT max ) and post-shift vigilance (reaction time) and postural sway (total path length) in a cross-sectional sample of 46 Washington State tree fruit harvesters in August-September 2015. The mean (SD) WBGT max was 27.4 (3.2)°C in August and 21.2 (2.0)°C in September. The mean pre-work-shift participant urine specific gravity indicated minimal dehydration. Twenty-four percent of participants exhibited possible excessive sleepiness. There was no association between WBGT max and post-shift reaction time or total path length. Heat exposure was not associated with impaired vigilance or balance in this study, in which the overall mean (SD) WBGT max was 25.9 (4.2)°C. However, the study identified opportunities to ensure adequate pre-work-shift hydration and to optimize sleep and work-shift timing in order to reduce occupational injury and heat-related illness risk. Copyright © 2017 Elsevier Ltd. All rights reserved.

Is the Army Communicating Effectively in Today’s Information Environment

DTIC Science & Technology

2013-03-01

to undertake a rapid and fundamental shift in the education, training, and resourcing of its Public Affairs career field, personnel and operations to...rapid and fundamental shift in the education, training, and resourcing of its Public Affairs career field, personnel and operations to effectively...rapid and fundamental shift in the education, training, and resourcing of its Public Affairs career field, personnel and operations to effectively

[The vocal behavior of telemarketing operators before and after a working day].

PubMed

Amorim, Geová Oliveira de; Bommarito, Silvana; Kanashiro, Célia Akemi; Chiari, Brasilia Maria

2011-01-01

To evaluate the vocal behavior of receptive telemarketing operators in pre- and post-work shift moments, and to relate the results to the variable gender. Participants were 55 telemarketing operators (11 men and 44 women) working in a receptive mode in the city of Maceió (Alagoas, Brazil). A questionnaire was applied before the work shift to initially identify the vocal complaints. After that, vocal samples were recorded, comprising sustained emissions and connected speech produced 10 minutes before and 10 minutes after the workday to be later evaluated. Auditory-perceptual and acoustic analyses of voice were conducted. Vocal complaints and symptoms reported by the operators after the work shift were: dry throat (64%); neck and cervix pain (33%); hoarseness (31%); voice failure (26%); and vocal fatigue (22%).Telemarketing operators presented reduced maximum phonation time before and after the day of work (p=0.645). Data from the auditory-perceptual assessment of voice were similar in pre- and post-shift moments (p=0.645). No difference was found between moments also on acoustic analysis data (p=0.738). Telemarketing operators have high indexes of vocal symptoms after the work shift, and there are no differences between pre- and post-work shift in auditory-perceptual and acoustic assessments of voice.

A diesel fuel processor for fuel-cell-based auxiliary power unit applications

NASA Astrophysics Data System (ADS)

Samsun, Remzi Can; Krekel, Daniel; Pasel, Joachim; Prawitz, Matthias; Peters, Ralf; Stolten, Detlef

2017-07-01

Producing a hydrogen-rich gas from diesel fuel enables the efficient generation of electricity in a fuel-cell-based auxiliary power unit. In recent years, significant progress has been achieved in diesel reforming. One issue encountered is the stable operation of water-gas shift reactors with real reformates. A new fuel processor is developed using a commercial shift catalyst. The system is operated using optimized start-up and shut-down strategies. Experiments with diesel and kerosene fuels show slight performance drops in the shift reactor during continuous operation for 100 h. CO concentrations much lower than the target value are achieved during system operation in auxiliary power unit mode at partial loads of up to 60%. The regeneration leads to full recovery of the shift activity. Finally, a new operation strategy is developed whereby the gas hourly space velocity of the shift stages is re-designed. This strategy is validated using different diesel and kerosene fuels, showing a maximum CO concentration of 1.5% at the fuel processor outlet under extreme conditions, which can be tolerated by a high-temperature PEFC. The proposed operation strategy solves the issue of strong performance drop in the shift reactor and makes this technology available for reducing emissions in the transportation sector.

Systems analysis of electricity production from coal using fuel cells

NASA Technical Reports Server (NTRS)

Fleming, D. K.

1983-01-01

Gasifiers, heat transfer, gas stability, quench, water-gas shift reaction, reforming-methanation, other catalytic reactions, compressors and expanders, acid-gas removal, the fuel cell, and catalytic combustors are described. System pressure drops, efficiency of rotating power equipment, heat exchangers, chemical reactions, steam systems, and the fuel cell subsystems are discussed.

Synthesis and photophysical properties of a series of cyclopenta[b]naphthalene solvatochromic fluorophores.

PubMed

Benedetti, Erica; Kocsis, Laura S; Brummond, Kay M

2012-08-01

The synthesis and photophysical properties of a series of naphthalene-containing solvatochromic fluorophores are described within. These novel fluorophores are prepared using a microwave-assisted dehydrogenative Diels-Alder reaction of styrene, followed by a palladium-catalyzed cross coupling reaction to install an electron donating amine group. The new fluorophores are structurally related to Prodan. Photophysical properties of the new fluorophores were studied and intriguing solvatochromic behavior was observed. For most of these fluorophores, high quantum yields (60-99%) were observed in methylene chloride in addition to large Stokes shifts (95-226 nm) in this same solvent. As the solvent polarity increased, so did the observed Stokes shift with one derivative displaying a Stokes shift of ~300 nm in ethanol. All fluorophore emission maxima, and nearly all absorption maxima were significantly red-shifted when compared to Prodan. Shifting the absorption and emission maxima of a fluorophore into the visible region increases its utility in biological applications. Moreover, the cyclopentane portion of the fluorophore structure provides an attachment point for biomolecules that will minimize disruptions of the photophysical properties.

Production of alpha-hydroxy carboxylic acids and esters from higher sugars using tandem catalyst systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Orazov, Marat; Davis, Mark E.

The present disclosure is directed to methods and composition used in the preparation of alpha-hydroxy carboxylic acids and esters from higher sugars using a tandem catalyst system comprising retro-aldol catalysts and Lewis acid catalysts. In some embodiments, these alpha-hydroxy carboxylic acids may be prepared from pentoses and hexoses. The retro-aldol and Lewis catalysts may be characterized by their respective ability to catalyze a 1,2-carbon shift reaction and a 1,2-hydride shift reaction on an aldose or ketose substrate.

A novel series of 1, 4-Dihydropyridine (DHP) derivatives bearing thiazolidin-4-one: From synthesis to structure

NASA Astrophysics Data System (ADS)

Bade, Tahseen S.; Ebrahimi, Hossein Pasha; Alsalim, Tahseen A.; Titinchi, Salam J. J.; Abbo, Hanna S.; Bolandnazar, Zeinab; Ebrahimi, Amirpasha

2017-06-01

A novel series of 1, 4-Dihydropyridine (DHP) thiazolidin-4-one compounds derived from dihydropyridine hydrazones Schiff bases with thioglycolic acid were synthesized through an efficient Hantzsch reaction and experimentally characterized by spectral methods using IR, 1H NMR, 13C NMR, and mass spectroscopic methods. Herein, DHPs were synthesized by an improved Hantzsch procedure in the excellent yields by three different conditions including reflux condensation, fusion, and the microwave irradiation. An additional comparison of applied methodology routes was used to confirm the advantages including short reaction time, good yields, and operational simplicity. Furthermore, the structural and electronic properties of the studied molecules were theoretically investigated by performing density functional theory (DFT) to access reliable results to the experimental values. The molecular geometry, HOMO, and LUMO of the studied compounds were calculated. The theoretical 13C chemical shift results were also calculated using the gauge independent atomic orbital (GIAO) approach and their respective linear correlations were obtained.

Frequency stabilization in nonlinear MEMS and NEMS oscillators

DOEpatents

Lopez, Omar Daniel; Antonio, Dario

2014-09-16

An illustrative system includes an amplifier operably connected to a phase shifter. The amplifier is configured to amplify a voltage from an oscillator. The phase shifter is operably connected to a driving amplitude control, wherein the phase shifter is configured to phase shift the amplified voltage and is configured to set an amplitude of the phase shifted voltage. The oscillator is operably connected to the driving amplitude control. The phase shifted voltage drives the oscillator. The oscillator is at an internal resonance condition, based at least on the amplitude of the phase shifted voltage, that stabilizes frequency oscillations in the oscillator.

Multi-bit operations in vertical spintronic shift registers

NASA Astrophysics Data System (ADS)

Lavrijsen, Reinoud; Petit, Dorothée C. M. C.; Fernández-Pacheco, Amalio; Lee, JiHyun; Mansell, Mansell; Cowburn, Russell P.

2014-03-01

Spintronic devices have in general demonstrated the feasibility of non-volatile memory storage and simple Boolean logic operations. Modern microprocessors have one further frequently used digital operation: bit-wise operations on multiple bits simultaneously. Such operations are important for binary multiplication and division and in efficient microprocessor architectures such as reduced instruction set computing (RISC). In this paper we show a four-stage vertical serial shift register made from RKKY coupled ultrathin (0.9 nm) perpendicularly magnetised layers into which a 3-bit data word is injected. The entire four stage shift register occupies a total length (thickness) of only 16 nm. We show how under the action of an externally applied magnetic field bits can be shifted together as a word and then manipulated individually, including being brought together to perform logic operations. This is one of the highest level demonstrations of logic operation ever performed on data in the magnetic state and brings closer the possibility of ultrahigh density all-magnetic microprocessors.

Multi-bit operations in vertical spintronic shift registers.

PubMed

Lavrijsen, Reinoud; Petit, Dorothée C M C; Fernández-Pacheco, Amalio; Lee, Jihyun; Mansell, Mansell; Cowburn, Russell P

2014-03-14

Spintronic devices have in general demonstrated the feasibility of non-volatile memory storage and simple Boolean logic operations. Modern microprocessors have one further frequently used digital operation: bit-wise operations on multiple bits simultaneously. Such operations are important for binary multiplication and division and in efficient microprocessor architectures such as reduced instruction set computing (RISC). In this paper we show a four-stage vertical serial shift register made from RKKY coupled ultrathin (0.9 nm) perpendicularly magnetised layers into which a 3-bit data word is injected. The entire four stage shift register occupies a total length (thickness) of only 16 nm. We show how under the action of an externally applied magnetic field bits can be shifted together as a word and then manipulated individually, including being brought together to perform logic operations. This is one of the highest level demonstrations of logic operation ever performed on data in the magnetic state and brings closer the possibility of ultrahigh density all-magnetic microprocessors.

Differential Selectivity of the Escherichia coli Cell Membrane Shifts the Equilibrium for the Enzyme-Catalyzed Isomerization of Galactose to Tagatose▿

PubMed Central

Kim, Jin-Ha; Lim, Byung-Chul; Yeom, Soo-Jin; Kim, Yeong-Su; Kim, Hye-Jung; Lee, Jung-Kul; Lee, Sook-Hee; Kim, Seon-Won; Oh, Deok-Kun

2008-01-01

An Escherichia coli galactose kinase gene knockout (ΔgalK) strain, which contains the l-arabinose isomerase gene (araA) to isomerize d-galactose to d-tagatose, showed a high conversion yield of tagatose compared with the original galK strain because galactose was not metabolized by endogenous galactose kinase. In whole cells of the ΔgalK strain, the isomerase-catalyzed reaction exhibited an equilibrium shift toward tagatose, producing a tagatose fraction of 68% at 37°C, whereas the purified l-arabinose isomerase gave a tagatose equilibrium fraction of 36%. These equilibrium fractions are close to those predicted from the measured equilibrium constants of the isomerization reaction catalyzed in whole cells and by the purified enzyme. The equilibrium shift in these cells resulted from the higher uptake and lower release rates for galactose, which is a common sugar substrate, than for tagatose, which is a rare sugar product. A ΔmglB mutant had decreased uptake rates for galactose and tagatose, indicating that a methylgalactoside transport system, MglABC, is the primary contributing transporter for the sugars. In the present study, whole-cell conversion using differential selectivity of the cell membrane was proposed as a method for shifting the equilibrium in sugar isomerization reactions. PMID:18263746

Differential selectivity of the Escherichia coli cell membrane shifts the equilibrium for the enzyme-catalyzed isomerization of galactose to tagatose.

PubMed

Kim, Jin-Ha; Lim, Byung-Chul; Yeom, Soo-Jin; Kim, Yeong-Su; Kim, Hye-Jung; Lee, Jung-Kul; Lee, Sook-Hee; Kim, Seon-Won; Oh, Deok-Kun

2008-04-01

An Escherichia coli galactose kinase gene knockout (DeltagalK) strain, which contains the l-arabinose isomerase gene (araA) to isomerize d-galactose to d-tagatose, showed a high conversion yield of tagatose compared with the original galK strain because galactose was not metabolized by endogenous galactose kinase. In whole cells of the DeltagalK strain, the isomerase-catalyzed reaction exhibited an equilibrium shift toward tagatose, producing a tagatose fraction of 68% at 37 degrees C, whereas the purified l-arabinose isomerase gave a tagatose equilibrium fraction of 36%. These equilibrium fractions are close to those predicted from the measured equilibrium constants of the isomerization reaction catalyzed in whole cells and by the purified enzyme. The equilibrium shift in these cells resulted from the higher uptake and lower release rates for galactose, which is a common sugar substrate, than for tagatose, which is a rare sugar product. A DeltamglB mutant had decreased uptake rates for galactose and tagatose, indicating that a methylgalactoside transport system, MglABC, is the primary contributing transporter for the sugars. In the present study, whole-cell conversion using differential selectivity of the cell membrane was proposed as a method for shifting the equilibrium in sugar isomerization reactions.

Ab initio thermodynamic approach to identify mixed solid sorbents for CO 2 capture technology

DOE PAGES

Duan, Yuhua

2015-10-15

Because the current technologies for capturing CO 2 are still too energy intensive, new materials must be developed that can capture CO 2 reversibly with acceptable energy costs. At a given CO 2 pressure, the turnover temperature (T t) of the reaction of an individual solid that can capture CO 2 is fixed. Such T t may be outside the operating temperature range (ΔT o) for a practical capture technology. To adjust T t to fit the practical ΔT o, in this study, three scenarios of mixing schemes are explored by combining thermodynamic database mining with first principles density functionalmore » theory and phonon lattice dynamics calculations. Our calculated results demonstrate that by mixing different types of solids, it’s possible to shift T t to the range of practical operating temperature conditions. According to the requirements imposed by the pre- and post- combustion technologies and based on our calculated thermodynamic properties for the CO 2 capture reactions by the mixed solids of interest, we were able to identify the mixing ratios of two or more solids to form new sorbent materials for which lower capture energy costs are expected at the desired pressure and temperature conditions.« less

Shifting from Production to Service to Experience-Based Operations

NASA Astrophysics Data System (ADS)

Angelis, Jannis; de Lima, Edson Pinheiro

This chapter covers the shift in focus of value added business operations from ­production to services, and in turn, to experience-based operations where customer involvement itself becomes part of the offering. The shift has significant implications for how businesses are managed. The greater service focus affects the firm's unique value proposition, which necessitates considerations on strategy, supplier relations, post-sale offerings and so on. Meanwhile, the inclusion of customer ­experiences affect the way operations are designed and employed so that these are structurally systematically captured and capitalised.

Information storage at the molecular level - The design of a molecular shift register memory

NASA Technical Reports Server (NTRS)

Beratan, David N.; Onuchic, Jose Nelson; Hopfield, J. J.

1989-01-01

The control of electron transfer rates is discussed and a molecular shift register memory at the molecular level is described. The memory elements are made up of molecules which can exist in either an oxidized or reduced state and the bits can be shifted between the cells with photoinduced electron transfer reactions. The device integrates designed molecules onto a VLSI substrate. A control structure to modify the flow of information along a shift register is indicated schematically.

Collision energy dependence of the reactions of metastable neon with small molecules

NASA Astrophysics Data System (ADS)

Noroski, Joseph H.

The reaction dynamics of Ne* (2p53 s 3P2, 3 P0) + X → [NeX]+ + e- (X = H2, CO, N2, NO, O2, CO 2, and C2H2) were studied with supersonic beams at various collision energies (E) via electron spectroscopy. Increasing E decreases the interparticle distance at which ionization occurs, allowing for exploration of the reaction potential energy surfaces via the kinetic energy epsilon of the ejected electron. Data were fit to give vibrational populations and line shifts (Deltaepsilons ), the difference between the excitation energy of Ne* and the vibronic energy of the target molecules, where vibronic excitation is due to Ne*. The resulting populations were compared to calculated or experimental Franck-Condon factors (FCfs), and vibrational progressions were identified. Deviation from Franck-Condon (FC) behavior was observed in all cases except for C2H 2, and all spectra at all E showed a blue shift except CO2. With increasing E, Deltaepsilons for H2 +, CO+, and N2 + increased with increasing E, while Deltaepsilon s decreased for NO+ and C2H2 +. The CO2+ spectra revealed a nearly constant red shift for the lowest three E and a blue shift for the highest E. O2+ showed a very small blue shift, but the O2+ populations were not determined due to an underlying continuum. Penning, excitation transfer, and ion-pair mechanisms are the most widely accepted for the reactions of metastable atoms. The closed-shell structure of H2, CO, and N2 and the large, increasing Deltaepsilon s suggest that their Ne* reactions proceed via the Penning mechanism. The open-shell structure of NO and its decreasing Deltaepsilons indicates changing dynamics and possibly also competition between all three mechanisms for Ne* + NO. The very small Deltaepsilons for O 2+ implies the excitation transfer mechanism for Ne* + O2. Ne* reactions with CO2 and C2H 2 both exhibited constant Deltaepsilons values for more than one E. This suggests that an excitation transfer mechanism is at work in these systems, but changes in Deltaepsilons at other E indicate that competing mechanisms may also be relevant. Lastly, a retrospective on authoring a solutions manual for a freshman chemistry textbook is offered.

40 CFR 60.1185 - What types of operator certification must the chief facility operator and shift supervisor obtain...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 6 2011-07-01 2011-07-01 false What types of operator certification... Certification § 60.1185 What types of operator certification must the chief facility operator and shift... combustion unit initial startup. (2) December 6, 2001. (3) Six months after they transfer to the municipal...

40 CFR 60.1185 - What types of operator certification must the chief facility operator and shift supervisor obtain...

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 7 2014-07-01 2014-07-01 false What types of operator certification... Certification § 60.1185 What types of operator certification must the chief facility operator and shift... combustion unit initial startup. (2) December 6, 2001. (3) Six months after they transfer to the municipal...

40 CFR 60.1185 - What types of operator certification must the chief facility operator and shift supervisor obtain...

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 7 2012-07-01 2012-07-01 false What types of operator certification... Certification § 60.1185 What types of operator certification must the chief facility operator and shift... combustion unit initial startup. (2) December 6, 2001. (3) Six months after they transfer to the municipal...

40 CFR 60.1185 - What types of operator certification must the chief facility operator and shift supervisor obtain...

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 7 2013-07-01 2013-07-01 false What types of operator certification... Certification § 60.1185 What types of operator certification must the chief facility operator and shift... combustion unit initial startup. (2) December 6, 2001. (3) Six months after they transfer to the municipal...

Uncertainty Quantification Analysis of Both Experimental and CFD Simulation Data of a Bench-scale Fluidized Bed Gasifier

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shahnam, Mehrdad; Gel, Aytekin; Subramaniyan, Arun K.

Adequate assessment of the uncertainties in modeling and simulation is becoming an integral part of the simulation based engineering design. The goal of this study is to demonstrate the application of non-intrusive Bayesian uncertainty quantification (UQ) methodology in multiphase (gas-solid) flows with experimental and simulation data, as part of our research efforts to determine the most suited approach for UQ of a bench scale fluidized bed gasifier. UQ analysis was first performed on the available experimental data. Global sensitivity analysis performed as part of the UQ analysis shows that among the three operating factors, steam to oxygen ratio has themore » most influence on syngas composition in the bench-scale gasifier experiments. An analysis for forward propagation of uncertainties was performed and results show that an increase in steam to oxygen ratio leads to an increase in H2 mole fraction and a decrease in CO mole fraction. These findings are in agreement with the ANOVA analysis performed in the reference experimental study. Another contribution in addition to the UQ analysis is the optimization-based approach to guide to identify next best set of additional experimental samples, should the possibility arise for additional experiments. Hence, the surrogate models constructed as part of the UQ analysis is employed to improve the information gain and make incremental recommendation, should the possibility to add more experiments arise. In the second step, series of simulations were carried out with the open-source computational fluid dynamics software MFiX to reproduce the experimental conditions, where three operating factors, i.e., coal flow rate, coal particle diameter, and steam-to-oxygen ratio, were systematically varied to understand their effect on the syngas composition. Bayesian UQ analysis was performed on the numerical results. As part of Bayesian UQ analysis, a global sensitivity analysis was performed based on the simulation results, which shows that the predicted syngas composition is strongly affected not only by the steam-to-oxygen ratio (which was observed in experiments as well) but also by variation in the coal flow rate and particle diameter (which was not observed in experiments). The carbon monoxide mole fraction is underpredicted at lower steam-to-oxygen ratios and overpredicted at higher steam-to-oxygen ratios. The opposite trend is observed for the carbon dioxide mole fraction. These discrepancies are attributed to either excessive segregation of the phases that leads to the fuel-rich or -lean regions or alternatively the selection of reaction models, where different reaction models and kinetics can lead to different syngas compositions throughout the gasifier. To improve quality of numerical models used, the effect that uncertainties in reaction models for gasification, char oxidation, carbon monoxide oxidation, and water gas shift will have on the syngas composition at different grid resolution, along with bed temperature were investigated. The global sensitivity analysis showed that among various reaction models employed for water gas shift, gasification, char oxidation, the choice of reaction model for water gas shift has the greatest influence on syngas composition, with gasification reaction model being second. Syngas composition also shows a small sensitivity to temperature of the bed. The hydrodynamic behavior of the bed did not change beyond grid spacing of 18 times the particle diameter. However, the syngas concentration continued to be affected by the grid resolution as low as 9 times the particle diameter. This is due to a better resolution of the phasic interface between the gases and solid that leads to stronger heterogeneous reactions. This report is a compilation of three manuscripts published in peer-reviewed journals for the series of studies mentioned above.« less

The 1,5-H-shift in 1-butoxy: A case study in the rigorous implementation of transition state theory for a multirotamer system

NASA Astrophysics Data System (ADS)

Vereecken, Luc; Peeters, Jozef

2003-09-01

The rigorous implementation of transition state theory (TST) for a reaction system with multiple reactant rotamers and multiple transition state conformers is discussed by way of a statistical rate analysis of the 1,5-H-shift in 1-butoxy radicals, a prototype reaction for the important class of H-shift reactions in atmospheric chemistry. Several approaches for deriving a multirotamer TST expression are treated: oscillator versus (hindered) internal rotor models; distinguishable versus indistinguishable atoms; and direct count methods versus degeneracy factors calculated by (simplified) direct count methods or from symmetry numbers and number of enantiomers, where applicable. It is shown that the various treatments are fully consistent, even if the TST expressions themselves appear different. The 1-butoxy H-shift reaction is characterized quantum chemically using B3LYP-DFT; the performance of this level of theory is compared to other methods. Rigorous application of the multirotamer TST methodology in an harmonic oscillator approximation based on this data yields a rate coefficient of k(298 K,1 atm)=1.4×105 s-1, and an Arrhenius expression k(T,1 atm)=1.43×1011 exp(-8.17 kcal mol-1/RT) s-1, which both closely match the experimental recommendations in the literature. The T-dependence is substantially influenced by the multirotamer treatment, as well as by the tunneling and fall-off corrections. The present results are compared to those of simplified TST calculations based solely on the properties of the lowest energy 1-butoxy rotamer.

Bioaugmentation of anaerobic sludge digestion with iron-reducing bacteria: process and microbial responses to variations in hydraulic retention time.

PubMed

Baek, Gahyun; Kim, Jaai; Shin, Seung Gu; Lee, Changsoo

2016-01-01

Although anaerobic digestion (AD) is a widely used option to manage waste activated sludge (WAS), there are some drawbacks related to its slow reaction rate and low energy productivity. This study examined an anaerobic WAS digester, augmented with an iron-reducing microbial consortium, relative to changes in microbial community structure and process performance at decreasing hydraulic retention times (HRTs) of 20 to 10 days. The enhanced methanation performance (approximately 40 % increase in methane yield) by the bioaugmentation was sustained until the HRT was decreased to 12.5 days, under Fe(3+)-rich conditions (ferric oxyhydroxide, 20 mM Fe). Enhanced iron-reducing activity was evidenced by the increased Fe(2+) to total Fe ratio maintained above 50 % during the stable operational phases. A further decrease in HRT to 10 days resulted in a significant performance deterioration, along with a drop in the Fe(2+) to total Fe ratio to <35 %, after four turnovers of operation. Prevailing existence of putative iron-reducing bacteria (IRBs) was identified by denaturing gradient gel electrophoresis (DGGE), with Spirochaetaceae- and Thauera-related organisms being dominant members, and clear dominance shifts among them with respect to decrease in HRT were observed. Lowering HRT led to evident shifts in bacterial community structure likely associated with washout of IRBs, leading to decreases in iron respiration activity and AD performance at a lower HRT. The bacterial community structure shifted dynamically over phases, and the community transitions correlated well with the changes in process performance. Overall, the combined biostimulation and bioaugmentation investigated in this study proved effective for enhanced methane recovery from anaerobic WAS digestion, which suggests an interesting potential for high-rate AD.

Measurement of key resonances for the Al 24 ( p , γ ) Si 25 reaction rate using in-beam γ -ray spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Longfellow, B.; Gade, A.; Brown, B. A.

Energy levels and branching ratios for the rp-process nucleus 25Si were determined from the reactions 9Be ( 26Si, 25Si) X and 9Be ( 25Al, 25Si) X using in-beam γ-ray spectroscopy with both high-efficiency and high-resolution detector arrays. Proton-unbound states at 3695(14) and 3802(11) keV were identified and assigned tentative spins and parities based on comparison to theory and the mirror nucleus. The 24Al (p, γ) 25Si reaction rate was calculated using the experimental states and states from charge-dependent USDA and USDB shell-model calculations with downward shifts of the 1s 1/2 proton orbital to account for the observed Thomas-Ehrman shift, leadingmore » to a factor of 10–100 increase in rate for the temperature region of 0.22 GK as compared to a previous calculation. These shifts may be applicable to neighboring nuclei, impacting the proton capture rates in this region of the chart.« less

Measurement of key resonances for the Al 24 ( p , γ ) Si 25 reaction rate using in-beam γ -ray spectroscopy

DOE PAGES

Longfellow, B.; Gade, A.; Brown, B. A.; ...

2018-05-04

Energy levels and branching ratios for the rp-process nucleus 25Si were determined from the reactions 9Be ( 26Si, 25Si) X and 9Be ( 25Al, 25Si) X using in-beam γ-ray spectroscopy with both high-efficiency and high-resolution detector arrays. Proton-unbound states at 3695(14) and 3802(11) keV were identified and assigned tentative spins and parities based on comparison to theory and the mirror nucleus. The 24Al (p, γ) 25Si reaction rate was calculated using the experimental states and states from charge-dependent USDA and USDB shell-model calculations with downward shifts of the 1s 1/2 proton orbital to account for the observed Thomas-Ehrman shift, leadingmore » to a factor of 10–100 increase in rate for the temperature region of 0.22 GK as compared to a previous calculation. These shifts may be applicable to neighboring nuclei, impacting the proton capture rates in this region of the chart.« less

[Influence of work intensity on development of arterial hypertension in metal-mining workers].

PubMed

Ustinova, O Iu; Alekseev, V B; Rumiantseva, A N; Orehova, Ia V

2013-01-01

The article covers data on influence of working shifts duration and shift work intensity on cardiovascular system functioning in operators of mining excavators. Findings are that 8 hours shift with regular shift schedule (40 working hours per week) gives significant load on cardiovascular system of workers engaged into underground activities. 50% of mining excavator operators following this working schedule develop transitory arterial hypertension within 10 years. Longer work shift over 8 hours and more intensive shifting schedule over 40 hours per week causes stable arterial hypertension within 3 months in 60% of workers, in 10% of cases associated with lower functioning of sinus node.

Solvent-Induced Shift of Spectral Lines in Polar–Polarizable Solvents

DOE PAGES

Matyushov, Dmitry V.; Newton, Marshall D.

2017-03-09

Solvent-induced shift of optical transition lines is traditionally described by the Lippert- McRae equation given in terms of the Onsager theory for dipole solvation. It splits the overall shift into the equilibrium solvation by induced dipoles and the reaction field by the permanent dipoles in equilibrium with the chromophore in the ground state. Here we have reconsidered this classical problem from the perspective of microscopic solvation theories. A microscopic solvation functional is derived and continuum solvation is consistently introduced by taking the limit of zero wavevector in the reciprocal-space solvation susceptibility functions. We show that the phenomenological expression for themore » reaction field of permanent dipoles in the Lippert-McRae equation is not consistent with the microscopic theory. The main deficiency of the Lippert- McRae equation equation is the use of additivity of the response by permanent and induced dipoles of the liquid. An alternative closed-form equation for the spectral shift is derived. Its continuum limit allows a new, non-additive functionality for the solvent-induced shift in terms of the high-frequency and static dielectric constants. Finally, the main qualitative outcome of the theory is a significantly weaker dependence of the spectral shift on the polarizability of the solvent than predicted by the Lippert-McRae formula.« less

Solvent-Induced Shift of Spectral Lines in Polar-Polarizable Solvents.

PubMed

Matyushov, Dmitry V; Newton, Marshall D

2017-03-23

Solvent-induced shift of optical transition lines is traditionally described by the Lippert-McRae equation given in terms of the Onsager theory for dipole solvation. It splits the overall shift into the equilibrium solvation by induced dipoles and the reaction field by the permanent dipoles in equilibrium with the chromophore in the ground state. We have reconsidered this classical problem from the perspective of microscopic solvation theories. A microscopic solvation functional is derived, and continuum solvation is consistently introduced by taking the limit of zero wavevector in the reciprocal-space solvation susceptibility functions. We show that the phenomenological expression for the reaction field of permanent dipoles in the Lippert-McRae equation is not consistent with the microscopic theory. The main deficiency of the Lippert-McRae equation is the use of additivity of the response by permanent and induced dipoles of the liquid. An alternative closed-form equation for the spectral shift is derived. Its continuum limit allows a new, nonadditive functionality for the solvent-induced shift in terms of the high-frequency and static dielectric constants. The main qualitative outcome of the theory is a significantly weaker dependence of the spectral shift on the polarizability of the solvent than predicted by the Lippert-McRae formula.

Catalysts synthesized by selective deposition of Fe onto Pt for the water-gas shift reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aragao, Isaias Barbosa; Ro, Insoo; Liu, Yifei

FePt bimetallic catalysts with intimate contact between the two metals were synthesized by controlled surface reactions (CSR) of (cyclohexadiene)iron tricarbonyl with hydrogen-treated supported Pt nanoparticles. Adsorption of the iron precursor on a Pt/SiO2 catalyst was studied, showing that the Fe loading could be increased by performing multiple CSR cycles, and the efficiency of this process was linked to the renewal of adsorption sites by a reducing pretreatment. The catalytic activity of these bimetallic catalysts for the water gas shift reaction was improved due to promotion by iron, likely linked to H2O activation on FeOx species at or near the Ptmore » surface, mostly in the (II) oxidation state.« less

Catalysts synthesized by selective deposition of Fe onto Pt for the water-gas shift reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aragao, Isaias Barbosa; Ro, Insoo; Liu, Yifei

FePt bimetallic catalysts with intimate contact between the two metals were synthesized by controlled surface reactions (CSR) of (cyclohexadiene)iron tricarbonyl with hydrogen-treated supported Pt nanoparticles. Adsorption of the iron precursor on a Pt/SiO 2 catalyst was studied, showing that the Fe loading could be increased by performing multiple CSR cycles, and the efficiency of this process was linked to the renewal of adsorption sites by a reducing pretreatment. Here, the catalytic activity of these bimetallic catalysts for the water gas shift reaction was improved due to promotion by iron, likely linked to H 2O activation on FeO x species atmore » or near the Pt surface, mostly in the (II) oxidation state.« less

Atomically dispersed Au-(OH)x species bound on titania catalyze the low-temperature water-gas shift reaction.

PubMed

Yang, Ming; Allard, Lawrence F; Flytzani-Stephanopoulos, Maria

2013-03-13

We report a new method for stabilizing appreciable loadings (~1 wt %) of isolated gold atoms on titania and show that these catalyze the low-temperature water-gas shift reaction. The method combines a typical gold deposition/precipitation method with UV irradiation of the titania support suspended in ethanol. Dissociation of H2O on the thus-created Au-O-TiO(x) sites is facile. At higher gold loadings, nanoparticles are formed, but they were shown to add no further activity to the atomically bound gold on titania. Removal of this "excess" gold by sodium cyanide leaching leaves the activity intact and the atomically dispersed gold still bound on titania. The new materials may catalyze a number of other reactions that require oxidized active metal sites.

Catalysts synthesized by selective deposition of Fe onto Pt for the water-gas shift reaction

DOE PAGES

Aragao, Isaias Barbosa; Ro, Insoo; Liu, Yifei; ...

2017-10-04

FePt bimetallic catalysts with intimate contact between the two metals were synthesized by controlled surface reactions (CSR) of (cyclohexadiene)iron tricarbonyl with hydrogen-treated supported Pt nanoparticles. Adsorption of the iron precursor on a Pt/SiO 2 catalyst was studied, showing that the Fe loading could be increased by performing multiple CSR cycles, and the efficiency of this process was linked to the renewal of adsorption sites by a reducing pretreatment. Here, the catalytic activity of these bimetallic catalysts for the water gas shift reaction was improved due to promotion by iron, likely linked to H 2O activation on FeO x species atmore » or near the Pt surface, mostly in the (II) oxidation state.« less

Electrochemical models for the radical annihilation reactions in organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Armstrong, Neal R.; Anderson, Jeffrey D.; Lee, Paul A.; McDonald, Erin; Wightman, R. M.; Hall, Hank K.; Hopkins, Tracy; Padias, Anne; Thayumanavan, Sankaran; Barlow, Stephen; Marder, Seth R.

1998-12-01

Bilayer organic light emitting diodes (OLEDs), based upon vacuum deposited molecules, or single layer OLEDs, based upon spin-cast polymeric materials, doped with these same molecules, produce light from emissive states of the lumophores which are created through annihilation reactions of radical species, which can be modeled through solution electrochemistry. Difference seen in solution reduction and oxidation potentials of molecular components of OLEDs are a lower limit estimate to the differences in energy of these same radical species in the condensed phase environmental. The light emitted from an aluminum quinolate (Alq3)/triarylamine (TPD)-based OLED, or an Alq3/PVK single layers OLED, can be reproduce from solution cross reactions of Alq3/TPD+. The efficiency of this process increases as the oxidation potential of the TPD increases, due to added substituents. Radical cations and anions of solubilized version of quinacridone dopants (DIQA) which have been used to enhance efficiencies in these OLEDs, are shown to be electrochemically more stable than Alq3 and Alq3, and DIQA radical annihilation reactions produce the same emissive state as in the quinacridone-doped OLEDs. Electrochemical studies demonstrate the ways in which other dopants might enhance the efficiency and shift the color output of OLEDs, across the entire visible and near-IR spectrum. Chemical degradation pathways of these same molecular components, which they may undergo during OLED operation, are also revealed by these electrochemical studies.

Distributional analyses in the picture-word interference paradigm: Exploring the semantic interference and the distractor frequency effects.

PubMed

Scaltritti, Michele; Navarrete, Eduardo; Peressotti, Francesca

2015-01-01

The present study explores the distributional features of two important effects within the picture-word interference paradigm: the semantic interference and the distractor frequency effects. These two effects display different and specific distributional profiles. Semantic interference appears greatly reduced in faster response times, while it reaches its full magnitude only in slower responses. This can be interpreted as a sign of fluctuant attentional efficiency in resolving response conflict. In contrast, the distractor frequency effect is mediated mainly by a distributional shift, with low-frequency distractors uniformly shifting reaction time distribution towards a slower range of latencies. This finding fits with the idea that distractor frequency exerts its effect by modulating the point in time in which operations required to discard the distractor can start. Taken together, these results are congruent with current theoretical accounts of both the semantic interference and distractor frequency effects. Critically, distributional analyses highlight and further describe the different cognitive dynamics underlying these two effects, suggesting that this analytical tool is able to offer important insights about lexical access during speech production.

Probing the Intermediacy of Covalent RNA Enzyme Complexes in RNA Modification Enzymes

PubMed Central

Chervin, Stephanie M.; Kittendorf, Jeffrey D.; Garcia, George A.

2009-01-01

Within the large and diverse group of RNA-modifying enzymes, a number of enzymes seem to form stable covalent linkages to their respective RNA substrates. A complete understanding of the chemical and kinetic mechanisms of these enzymes, some of which have identified pathological roles, is lacking. As part of our ongoing work studying the posttranscriptional modification of tRNA with queuine, we wish to understand fully the chemical and kinetic mechanisms involved in this key transglycosylation reaction. In our previous investigations, we have used a gel mobility-shift assay to characterize an apparent covalent enzyme-RNA intermediate believed to be operative in the catalytic pathway. However, the simple observation of a covalent complex is not sufficient to prove intermediacy. To be a true intermediate, the complex must be both chemically and kinetically competent. As a case study for the proof of intermediacy, we report the use of this gel-shift assay under mildly denaturing conditions to probe the kinetic competency of the covalent association between RNA and the tRNA modifying enzyme tRNA-guanine transglycosylase (TGT). PMID:17673081

Moving attention - Evidence for time-invariant shifts of visual selective attention

NASA Technical Reports Server (NTRS)

Remington, R.; Pierce, L.

1984-01-01

Two experiments measured the time to shift spatial selective attention across the visual field to targets 2 or 10 deg from central fixation. A central arrow cued the most likely target location. The direction of attention was inferred from reaction times to expected, unexpected, and neutral locations. The development of a spatial attentional set with time was examined by presenting target probes at varying times after the cue. There were no effects of distance on the time course of the attentional set. Reaction times for far locations were slower than for near, but the effects of attention were evident by 150 msec in both cases. Spatial attention does not shift with a characteristic, fixed velocity. Rather, velocity is proportional to distance, resulting in a movement time that is invariant over the distances tested.

Matrix isolation infrared spectroscopic studies and density functional theory calculations of the MNN, (MN)2 (M = Y and La), and Y3NN molecules.

PubMed

Teng, Yun-Lei; Xu, Qiang

2008-04-24

The reactions of yttrium and lanthanum with dinitrogen were reinvestigated. Laser-ablated yttrium and lanthanum atoms were co-deposited at 4 K with dinitrogen in excess argon, and the low-temperature reactions of Y and La with N2 in solid argon were studied using infrared spectroscopy. The reaction products YNN, (YN)2, LaNN, and (LaN)2 were formed in the present experiments and characterized on the basis of 14N/15N isotopic shifts, mixed isotope splitting patterns, stepwise annealing, change of reagent concentration and laser energy, and comparison with theoretical predictions. Some assignments were made based on a previous report. Density functional theory calculations were performed on these systems to identify possible reaction products. The agreement between experimental and calculated vibrational frequencies, relative absorption intensities, and isotopic shifts of the MNN and (MN)2 (M = Y and La) molecules supports the identification of these molecules from the matrix infrared spectra. Plausible reaction mechanisms were proposed for the formation of these molecules along with tentative identification of the Y3NN molecule.

Adsorption Behavior, Thermodynamics, and Kinetics of the Methanol Decomposition Reaction on defective graphene-supported Pt13

NASA Astrophysics Data System (ADS)

Gasper, Raymond; Ramasubramaniam, Ashwin

Defective graphene has been shown experimentally to be an excellent support for transition-metal electrocatalysts in direct methanol fuel cells. Prior computational modeling has shown that the improved catalytic activity of graphene-supported metal clusters is in part due to increased resistance to catalyst sintering and CO poisoning, but the increased reaction rate for the methanol decomposition reaction (MDR) is not yet fully explained. Using DFT, we investigate the adsorption of MDR intermediates and reaction thermodynamics on defective graphene-supported Pt13 nanoclusters with realistic, low-symmetry morphologies. We find that the support-induced shifts in Pt13 electronic structure correlate well with a rigid shift in adsorption of MDR intermediates, and that adsorption energy scaling relationships perform well on the low-symmetry surface. We investigate the reaction kinetics and thermodynamics, including testing the effectiveness of scaling relationships for predicting reaction barriers on the nanoclusters. Using these fundamental data, we perform microkinetic modeling to quantify the effect of the support on the MDR, and to understand how the support influences surface coverages, CO poisoning, and the relationships between reaction pathways. Funded by U.S. Department of Energy under Award Number DE-SC0010610. Computational resources were provided by National Energy Research Scientific Computing Center.

Interplay between Surface Chemistry, Precursor Reactivity, and Temperature Determines Outcome of ZnS Shelling Reactions on CuInS2 Nanocrystals

PubMed Central

2018-01-01

ZnS shelling of I–III–VI2 nanocrystals (NCs) invariably leads to blue-shifts in both the absorption and photoluminescence spectra. These observations imply that the outcome of ZnS shelling reactions on I–III–VI2 colloidal NCs results from a complex interplay between several processes taking place in solution, at the surface of, and within the seed NC. However, a fundamental understanding of the factors determining the balance between these different processes is still lacking. In this work, we address this need by investigating the impact of precursor reactivity, reaction temperature, and surface chemistry (due to the washing procedure) on the outcome of ZnS shelling reactions on CuInS2 NCs using a seeded growth approach. We demonstrate that low reaction temperatures (150 °C) favor etching, cation exchange, and alloying regardless of the precursors used. Heteroepitaxial shell overgrowth becomes the dominant process only if reactive S- and Zn-precursors (S-ODE/OLAM and ZnI2) and high reaction temperatures (210 °C) are used, although a certain degree of heterointerfacial alloying still occurs. Remarkably, the presence of residual acetate at the surface of CIS seed NCs washed with ethanol is shown to facilitate heteroepitaxial shell overgrowth, yielding for the first time CIS/ZnS core/shell NCs displaying red-shifted absorption spectra, in agreement with the spectral shifts expected for a type-I band alignment. The insights provided by this work pave the way toward the design of improved synthesis strategies to CIS/ZnS core/shell and alloy NCs with tailored elemental distribution profiles, allowing precise tuning of the optoelectronic properties of the resulting materials. PMID:29657360

Design of a magnetic-tunnel-junction-oriented nonvolatile lookup table circuit with write-operation-minimized data shifting

NASA Astrophysics Data System (ADS)

Suzuki, Daisuke; Hanyu, Takahiro

2018-04-01

A magnetic-tunnel-junction (MTJ)-oriented nonvolatile lookup table (LUT) circuit, in which a low-power data-shift function is performed by minimizing the number of write operations in MTJ devices is proposed. The permutation of the configuration memory cell for read/write access is performed as opposed to conventional direct data shifting to minimize the number of write operations, which results in significant write energy savings in the data-shift function. Moreover, the hardware cost of the proposed LUT circuit is small since the selector is shared between read access and write access. In fact, the power consumption in the data-shift function and the transistor count are reduced by 82 and 52%, respectively, compared with those in a conventional static random-access memory-based implementation using a 90 nm CMOS technology.

Occupational Health Screenings of the Virtual Warrior: Distributed Common Ground System Intelligence Operators Compared with Non-Combatant Support Personnel

DTIC Science & Technology

2014-02-01

long hours , shift work , relational conflict...reasons for an increase in medication. Such sleep problems were often explained in textual responses to be the result of long work hours , shift work ...to be operational in nature [1]. Specifically, long hours , shift work , organizational and leadership challenges, nature of work , additional

Short-range correlations in carbon-12, oxygen-16, and neon-20: Intrinsic properties

NASA Technical Reports Server (NTRS)

Braley, R. C.; Ford, W. F.; Becker, R. L.; Patterson, M. R.

1972-01-01

The Brueckner-Hartree-Fock (BHF) method has been applied to nuclei whose intrinsic structure is nonspherical. Reaction matrix elements were calculated as functions of starting energy for the Hamada-Johnston interaction using the Pauli operator appropriate to O-16 and a shifted oscillator spectrum for virtual excited states. Binding energies, single particle energies, radii, and shape deformations of the intrinsic state, in ordinary as well as renormalized BHF, are discussed and compared with previous HF studies and with experiment when possible. Results are presented for C-12, 0-16 and Ne-20. It is found that the binding energies and radii are too small, but that separation energies are well reproduced when the renormalized theory is used.

[The social hygiene problems in the operator work of hydroelectric power station workers and the means for enhancing work capacity].

PubMed

Karakashian, A N; Lepeshkina, T R; Ratushnaia, A N; Glushchenko, S S; Zakharenko, M I; Lastovchenko, V B; Diordichuk, T I

1993-01-01

Weight, tension and harmfulness of professional activity, peculiarities of labour conditions and characteristics of work, shift dynamics of operative personnel's working capacity were studied in the course of 8-hour working day currently accepted at hydroelectric power stations (HEPS) and experimental 12-hour schedule. Working conditions classified as "admissible", positive dynamics of operators' state, their social and material contentment were a basis for 12-hour two-shift schedule to be recommended as more appropriate. At the same time, problem of optimal shift schedules for operative personnel of HEPS remains unsolved and needs to be further explored.

A combined field and laboratory design for assessing the impact of night shift work on police officer operational performance.

PubMed

Waggoner, Lauren B; Grant, Devon A; Van Dongen, Hans P A; Belenky, Gregory; Vila, Bryan

2012-11-01

This study assessed the utility of a combined field and laboratory research design for measuring the impact of consecutive night shift work on the sleepiness, vigilance, and driving performance of police patrol officers. For police patrol officers working their normal night shift duty cycles, simulated driving performance and psychomotor vigilance were measured in a laboratory on two separate occasions: in the morning after the last of five consecutive 10.7-h night shifts, and at the same time in the morning after three consecutive days off duty. Order of participation in conditions was randomized among subjects. Subjects experienced manipulation of sleep schedules due to working night shifts in a real operational environment, but performance testing was conducted under controlled laboratory conditions. N = 29 active-duty police patrol officers (27 male, 2 female; age 37.1 ± 6.3 years) working night shift schedules participated in this study. Simulated driving performance, psychomotor vigilance, and subjective sleepiness were significantly degraded following 5 consecutive night shifts as compared to 3 consecutive days off duty, indicating that active-duty police officers are susceptible to performance degradation as a consequence of working nights. This combined field and laboratory research design succeeded in bridging the gap between the realism of the operational environment and the control of laboratory performance testing, demonstrating that this is a useful approach for addressing the relationship between shift work induced fatigue and critical operational task performance.

Performance on a strategy set shifting task during adolescence in a genetic model of attention deficit/hyperactivity disorder: Methylphenidate vs. atomoxetine treatments

PubMed Central

Harvey, Roxann C; Jordan, Chloe J; Tassin, David H; Moody, Kayla R; Dwoskin, Linda P; Kantak, Kathleen M

2013-01-01

Research examining medication effects on set shifting in teens with attention deficit/hyperactivity disorder (ADHD) is lacking. An animal model of ADHD may be useful for exploring this gap. The Spontaneously Hypertensive Rat (SHR) is a commonly used animal model of ADHD. SHR and two comparator strains, Wistar-Kyoto (WKY) and Wistar (WIS), were evaluated during adolescence in a strategy set shifting task under conditions of a 0-sec or 15-sec delay to reinforcer delivery. The task had three phases: initial discrimination, set shift and reversal learning. Under 0-sec delays, SHR performed as well as or better than WKY and WIS. Treatment with 0.3 mg/kg/day atomoxetine had little effect, other than to modestly increase trials to criterion during set shifting in all strains. Under 15-sec delays, SHR had longer lever press reaction times, longer latencies to criterion and more trial omissions than WKY during set shifting and reversal learning. These deficits were not reduced systematically by 1.5 mg/kg/day methylphenidate or 0.3 mg/kg/day atomoxetine. Regarding learning in SHR, methylphenidate improved initial discrimination, whereas atomoxetine improved set shifting but disrupted initial discrimination. During reversal learning, both drugs were ineffective in SHR, and atomoxetine made reaction time and trial omissions greater in WKY. Overall, WIS performance differed from SHR or WKY, depending on phase. Collectively, a genetic model of ADHD in adolescent rats revealed that neither methylphenidate nor atomoxetine mitigated all deficits in SHR during the set shifting task. Thus, methylphenidate or atomoxetine monotherapy may not mitigate all set shift task-related deficits in teens with ADHD. PMID:23376704

Solvent-dependent reactions for the synthesis of β-keto-benzo-δ-sultone scaffolds via DBU-catalyzed O-sulfonylation/intramolecular Baylis-Hillman/1,3-H shift or dehydration tandem sequences.

PubMed

Ghandi, Mehdi; Bozcheloei, Abolfazl Hasani; Nazari, Seyed Hadi; Sadeghzadeh, Masoud

2011-12-16

We have developed a solvent-dependent method for the synthesis of novel benzo-δ-sultone scaffolds. A variety of benzylbenzo[e][1,2]oxathiin-4(3H)-one-2,2-dioxides were obtained in high yields in DMF using a one-pot, DBU-catalyzed condensation of 2-hydroxybenzaldehydes with a number of (E)-2-phenylethenesulfonyl chlorides. On the other hand, the initially prepared 2-formylphenyl-(E)-2-phenylethenesulfonate derivatives underwent DBU-catalyzed reactions to a series of 3-[methoxy(phenyl)methyl]benzo[e][1,2]oxathiine-2,2-dioxides in moderate to good yields in MeOH. These reactions presumably proceed via DBU-catalyzed O-sulfonylation/intramolecular Baylis-Hillman/1,3-H shift or dehydration tandem sequences, respectively.

QEDMOD: Fortran program for calculating the model Lamb-shift operator

NASA Astrophysics Data System (ADS)

Shabaev, V. M.; Tupitsyn, I. I.; Yerokhin, V. A.

2018-02-01

We present Fortran package QEDMOD for computing the model QED operator hQED that can be used to account for the Lamb shift in accurate atomic-structure calculations. The package routines calculate the matrix elements of hQED with the user-specified one-electron wave functions. The operator can be used to calculate Lamb shift in many-electron atomic systems with a typical accuracy of few percent, either by evaluating the matrix element of hQED with the many-electron wave function, or by adding hQED to the Dirac-Coulomb-Breit Hamiltonian.

All-optical XNOR/NOT logic gates and LATCH based on a reflective vertical cavity semiconductor saturable absorber.

PubMed

Pradhan, Rajib

2014-06-10

This work proposes a scheme of all-optical XNOR/NOT logic gates based on a reflective vertical cavity semiconductor (quantum wells, QWs) saturable absorber (VCSSA). In a semiconductor Fabry-Perot cavity operated with a low-intensity resonance wavelength, both intensity-dependent saturating phase-shift and thermal phase-shift occur, which are considered in the proposed logic operations. The VCSSA-based logics are possible using the saturable behavior of reflectivity under the typical operating conditions. The low-intensity saturable reflectivity is reported for all-optical logic operations where all possible nonlinear phase-shifts are ignored. Here, saturable absorption (SA) and the nonlinear phase-shift-based all-optical XNOR/NOT gates and one-bit memory or LATCH are proposed under new operating conditions. All operations are demonstrated for a VCSSA based on InGaAs/InP QWs. These types of SA-based logic devices can be comfortably used for a signal bit rate of about 10 GHz corresponding to the carrier recovery time of the semiconductor material.

The Ammonia Synthesis Reaction: An Exception to the Le Chatelier Principle and Effects of Nonideality

ERIC Educational Resources Information Center

Uline, Mark J.; Corti, David S.

2006-01-01

Le Chatelier's principle states that the further addition of a particular component will cause the reaction to shift in the direction that reduces the total number of moles of the system. However, the addition of one reactant [N[subscript 2

Spectroturbidimitry as applied to biomedical and immunological investigations

NASA Astrophysics Data System (ADS)

Shchyogolev, Sergei Y.; Khlebtsov, Nikolai G.; Schwartsburd, Boris I.

1993-06-01

Methods of optical shifting spectroscopy and laser nephelometry may be used to register antigen-antibody reaction. Usage of laser nephelometry in serodiagnostics, characteristics of a specific step in humoral immune reaction in infections, postinfectious and postinoculation processes response and immunity tension in some infectious diseases were investigated.

Alertness, performance and off-duty sleep on 8-hour and 12-hour night shifts in a simulated continuous operations control room setting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baker, T.L.

A growing number of nuclear power plants in the United States have adopted routine 12-hr shift schedules. Because of the potential impact that extended work shifts could have on safe and efficient power plant operation, the U.S. Nuclear Regulatory Commission funded research on 8-hr and 12-hr shifts at the Human Alertness Research Center (HARC) in Boston, Massachusetts. This report describes the research undertaken: a study of simulated 8-hr and 12-hr work shifts that compares alertness, speed, and accuracy at responding to simulator alarms, and relative cognitive performance, self-rated mood and vigor, and sleep-wake patterns of 8-hr versus 12-hr shift workers.

Comparison of sugar molecule decomposition through glucose and fructose: a high-level quantum chemical study.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Assary, R. S.; Curtiss, L. A.; MSD)

Efficient chemical conversion of biomass is essential to produce sustainable energy and industrial chemicals. Industrial level conversion of glucose to useful chemicals, such as furfural, hydroxymethylfurfural, and levulinic acid, is a major step in the biomass conversion but is difficult because of the formation of undesired products and side reactions. To understand the molecular level reaction mechanisms involved in the decomposition of glucose and fructose, we have carried out high-level quantum chemical calculations [Gaussian-4 (G4) theory]. Selective 1,2-dehydration, keto-enol tautomerization, isomerization, retro-aldol condensation, and hydride shifts of glucose and fructose molecules were investigated. Detailed kinetic and thermodynamic analyses indicate that,more » for acyclic glucose and fructose molecules, the dehydration and isomerization require larger activation barriers compared to the retro-aldol reaction at 298 K in neutral medium. The retro-aldol reaction results in the formation of C2 and C4 species from glucose and C3 species from fructose. The formation of the most stable C3 species, dihydroxyacetone from fructose, is thermodynamically downhill. The 1,3-hydride shift leads to the cleavage of the C-C bond in the acyclic species; however, the enthalpy of activation is significantly higher (50-55 kcal/mol) than that of the retro-aldol reaction (38 kcal/mol) mainly because of the sterically hindered distorted four-membered transition state compared to the hexa-membered transition state in the retro-aldol reaction. Both tautomerization and dehydration are catalyzed by a water molecule in aqueous medium; however, water has little effect on the retro-aldol reaction. Isomerization of glucose to fructose and glyceraldehyde to dihydroxyacetone proceeds through hydride shifts that require an activation enthalpy of about 40 kcal/mol at 298 K in water medium. This investigation maps out accurate energetics of the decomposition of glucose and fructose molecules that is needed to help find more efficient catalysts for the conversion of hexose to useful chemicals.« less

Coupling DAEM and CFD for simulating biomass fast pyrolysis in fluidized beds

DOE PAGES

Xiong, Qingang; Zhang, Jingchao; Wiggins, Gavin; ...

2015-12-03

We report results from computational simulations of an experimental, lab-scale bubbling bed biomass pyrolysis reactor that include a distributed activation energy model (DAEM) for the kinetics. In this study, we utilized multiphase computational fluid dynamics (CFD) to account for the turbulent hydrodynamics, and this was combined with the DAEM kinetics in a multi-component, multi-step reaction network. Our results indicate that it is possible to numerically integrate the coupled CFD–DAEM system without significantly increasing computational overhead. It is also clear, however, that reactor operating conditions, reaction kinetics, and multiphase flow dynamics all have major impacts on the pyrolysis products exiting themore » reactor. We find that, with the same pre-exponential factors and mean activation energies, inclusion of distributed activation energies in the kinetics can shift the predicted average value of the exit vapor-phase tar flux and its statistical distribution, compared to single-valued activation-energy kinetics. Perhaps the most interesting observed trend is that increasing the diversity of the DAEM activation energies appears to increase the mean tar yield, all else being equal. As a result, these findings imply that accurate resolution of the reaction activation energy distributions will be important for optimizing biomass pyrolysis processes.« less

Effects of Napping During Shift Work on Sleepiness and Performance in Emergency Medical Services Personnel and Similar Shift Workers: A Systematic Review and Meta-Analysis.

PubMed

Martin-Gill, Christian; Barger, Laura K; Moore, Charity G; Higgins, J Stephen; Teasley, Ellen M; Weiss, Patricia M; Condle, Joseph P; Flickinger, Katharyn L; Coppler, Patrick J; Sequeira, Denisse J; Divecha, Ayushi A; Matthews, Margaret E; Lang, Eddy S; Patterson, P Daniel

2018-02-15

Scheduled napping during work shifts may be an effective way to mitigate fatigue-related risk. This study aimed to critically review and synthesize existing literature on the impact of scheduled naps on fatigue-related outcomes for EMS personnel and similar shift worker groups. A systematic literature review was performed of the impact of a scheduled nap during shift work on EMS personnel or similar shift workers. The primary (critical) outcome of interest was EMS personnel safety. Secondary (important) outcomes were patient safety; personnel performance; acute states of fatigue, alertness, and sleepiness; indicators of sleep duration and/or quality; employee retention/turnover; indicators of long-term health; and cost to the system. Meta-analyses were performed to evaluate the impact of napping on a measure of personnel performance (the psychomotor vigilance test [PVT]) and measures of acute fatigue. Of 4,660 unique records identified, 13 experimental studies were determined relevant and summarized. The effect of napping on reaction time measured at the end of shift was small and non-significant (SMD 0.12, 95% CI -0.13 to 0.36; p = 0.34). Napping during work did not change reaction time from the beginning to the end of the shift (SMD -0.01, 95% CI -25.0 to 0.24; p = 0.96). Naps had a moderate, significant effect on sleepiness measured at the end of shift (SMD 0.40, 95% CI 0.09 to 0.72; p = 0.01). The difference in sleepiness from the start to the end of shift was moderate and statistically significant (SMD 0.41, 95% CI 0.09 to 0.72; p = 0.01). Reviewed literature indicated that scheduled naps at work improved performance and decreased fatigue in shift workers. Further research is required to identify the optimal timing and duration of scheduled naps to maximize the beneficial outcomes.

Sources of Occupational Stress and Prevalence of Burnout and Clinical Distress Among U.S. Air Force Cyber Warfare Operators

DTIC Science & Technology

2013-01-01

distress within the cyber warfare community. This study involved cyber warfare operators including active duty (n = 376) and civilian contractor and...revealed that when compared to civilian cyber warfare operators, active duty cyber warfare operators are more likely to suffer from the facets of...8217 write-in responses revealed cyber warfare operators attributed shift work, shift changes, and hours worked as the primary sources of high occupational

Soviet Operational Art: Will There be a Significant Shift in the Focus of Soviet Operational Art

DTIC Science & Technology

1989-03-06

conduct of war. 4 The most important of the six main elements of military science is military art . Military art includes military strategy...AD-A215 778 SOVIET OPERATIONAL ART :, WILL THERE BE A SIGNIFICANT SHIFT IN THE FOCUS OF SOVIET OPERATIONAL ART ? Lwori I i %.Afl S FELECTE DEC 19 1989A...NO NO NO, ACCESSION NO 11 TITLE (Include Security Classification) 5,’ .... Soviet Operational Art : Wi

Carbon capture by sorption-enhanced water-gas shift reaction process using hydrotalcite-based material

DOE Office of Scientific and Technical Information (OSTI.GOV)

van Selow, E.R.; Cobden, P.D.; Verbraeken, P.A.

2009-05-15

A novel route for precombustion decarbonization is the sorption-enhanced water-gas shift (SEWGS) process. In this process carbon dioxide is removed from a synthesis gas at elevated temperature by adsorption. Simultaneously, carbon monoxide is converted to carbon dioxide by the water-gas shift reaction. The periodic adsorption and desorption of carbon dioxide is induced by a pressure swing cycle, and the cyclic capacity can be amplified by purging with steam. From previous studies is it known that for SEWGS applications, hydrotalcite-based materials are particularly attractive as sorbent, and commercial high-temperature shift catalysts can be used for the conversion of carbon monoxide. Tabletsmore » of a potassium promoted hydrotalcite-based material are characterized in both breakthrough and cyclic experiments in a 2 m tall fixed-bed reactor. When exposed to a mixture of carbon dioxide, steam, and nitrogen at 400{sup o}C, the material shows a breakthrough capacity of 1.4 mmol/g. In subsequent experiments the material was mixed with tablets of promoted iron-chromium shift catalyst and exposed to a mixture of carbon dioxide, carbon monoxide, steam, hydrogen, and nitrogen. It is demonstrated that carbon monoxide conversion can be enhanced to 100% in the presence of a carbon dioxide sorbent. At breakthrough, carbon monoxide and carbon dioxide simultaneously appear at the end of the bed. During more than 300 cycles of adsorption/reaction and desorption, the capture rate, and carbon monoxide conversion are confirmed to be stable. Two different cycle types are investigated: one cycle with a CO{sub 2} rinse step and one cycle with a steam rinse step. The performance of both SEWGS cycles are discussed.« less

Apparatus and method for simultaneous recovery of hydrogen from water and from hydrocarbons

DOEpatents

Willms, R. Scott; Birdsell, Stephen A.

2000-01-01

Apparatus and method for simultaneous recovery of hydrogen from water and from hydrocarbon feed material. The feed material is caused to flow over a heated catalyst which fosters the water-gas shift reaction (H.sub.2 O+COH.sub.2 +CO.sub.2) and the methane steam reforming reaction (CH.sub.4 +H.sub.2 O3 H.sub.2 +CO). Both of these reactions proceed only to partial completion. However, by use of a Pd/Ag membrane which is exclusively permeable to hydrogen isotopes in the vicinity of the above reactions and by maintaining a vacuum on the permeate side of the membrane, product hydrogen isotopes are removed and the reactions are caused to proceed further toward completion. A two-stage palladium membrane reactor was tested with a feed composition of 28% CQ.sub.4, 35% Q.sub.2 O (where Q=H, D, or T), and 31% Ar in 31 hours of continuous operation during which 4.5 g of tritium were processed. Decontamination factors were found to increase with decreasing inlet rate. The first stage was observed to have a decontamination factor of approximately 200, while the second stage had a decontamination factor of 2.9.times.10.sup.6. The overall decontamination factor was 5.8.times.10.sup.8. When a Pt/.alpha.-Al.sub.2 O.sub.3 catalyst is employed, decoking could be performed without catalyst degradation. However, by adjusting the carbon to oxygen ratio of the feed material with the addition of oxygen, coking could be altogether avoided.

40 CFR 60.1195 - What if all the certified operators must be temporarily offsite?

Code of Federal Regulations, 2010 CFR

2010-07-01

... corrective action summary to the Administrator every 4 weeks following the initial notification. If the... facility operator and certified shift supervisor are offsite for more than 12 hours, but for 2 weeks or... facility operator and certified shift supervisor are offsite for more than 2 weeks, and no other certified...

Carbocation Rearrangement in An Electrophilic Aromatic Substitution Discovery Laboratory

ERIC Educational Resources Information Center

Polito, Victoria; Hamann, Christian S.; Rhile, Ian J.

2010-01-01

In this discovery laboratory, students performed electrophilic aromatic substitution reactions between 1,4-dimethoxybenzene and either 2-methyl-2-butanol or 3-methyl-2-butanol with sulfuric acid as a catalyst. The carbocation from 3-methyl-2-butanol undergoes a hydride shift, and hence, both reactions afford…

Signal Amplification in Field Effect-Based Sandwich Enzyme-Linked Immunosensing by Tuned Buffer Concentration with Ionic Strength Adjuster.

PubMed

Kumar, Satyendra; Kumar, Narendra; Panda, Siddhartha

2016-04-01

Miniaturization of the sandwich enzyme-based immunosensor has several advantages but could result in lower signal strength due to lower enzyme loading. Hence, technologies for amplification of the signal are needed. Signal amplification in a field effect-based electrochemical immunosensor utilizing chip-based ELISA is presented in this work. First, the molarities of phosphate buffer saline (PBS) and concentrations of KCl as ionic strength adjuster were optimized to maximize the GOx glucose-based enzymatic reactions in a beaker for signal amplification measured by change in the voltage shift with an EIS device (using 20 μl of solution) and validated with a commercial pH meter (using 3 ml of solution). The PBS molarity of 100 μM with 25 mM KCl provided the maximum voltage shift. These optimized buffer conditions were further verified for GOx immobilized on silicon chips, and similar trends with decreased PBS molarity were obtained; however, the voltage shift values obtained on chip reaction were lower as compared to the reactions occurring in the beaker. The decreased voltage shift with immobilized enzyme on chip could be attributed to the increased Km (Michaelis-Menten constant) values in the immobilized GOx. Finally, a more than sixfold signal enhancement (from 8 to 47 mV) for the chip-based sandwich immunoassay was obtained by altering the PBS molarity from 10 to 100 μM with 25 mM KCl.

A molecular shift register based on electron transfer

NASA Technical Reports Server (NTRS)

Hopfield, J. J.; Onuchic, Josenelson; Beratan, David N.

1988-01-01

An electronic shift-register memory at the molecular level is described. The memory elements are based on a chain of electron-transfer molecules and the information is shifted by photoinduced electron-transfer reactions. This device integrates designed electronic molecules onto a very large scale integrated (silicon microelectronic) substrate, providing an example of a 'molecular electronic device' that could actually be made. The design requirements for such a device and possible synthetic strategies are discussed. Devices along these lines should have lower energy usage and enhanced storage density.

Operation, Modeling and Analysis of the Reverse Water Gas Shift Process

NASA Technical Reports Server (NTRS)

Whitlow, Jonathan E.

2001-01-01

The Reverse Water Gas Shift process is a candidate technology for water and oxygen production on Mars under the In-Situ Propellant Production project. This report focuses on the operation and analysis of the Reverse Water Gas Shift (RWGS) process, which has been constructed at Kennedy Space Center. A summary of results from the initial operation of the RWGS, process along with an analysis of these results is included in this report. In addition an evaluation of a material balance model developed from the work performed previously under the summer program is included along with recommendations for further experimental work.

Continuous wave operation of quantum cascade lasers with frequency-shifted feedback

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lyakh, A., E-mail: arkadiy.lyakh@ucf.edu; NanoScience Technology Center, University of Central Florida, 12424 Research Pkwy, Orlando, FL 32826; College of Optics and Photonics, University of Central Florida, 304 Scorpius St, Orlando, FL 32826

2016-01-15

Operation of continuous wave quantum cascade lasers with a frequency-shifted feedback provided by an acousto-optic modulator is reported. Measured linewidth of 1.7 cm{sup −1} for these devices, under CW operating conditions, was in a good agreement with predictions of a model based on frequency-shifted feedback seeded by spontaneous emission. Linewidth broadening was observed for short sweep times, consistent with sound wave grating period variation across the illuminated area on the acousto-optic modulator. Standoff detection capability of the AOM-based QCL setup was demonstrated for several solid materials.

pH-sensitive pHluorins as a molecular sensor for in situ monitoring of enzyme-catalyzed prodrug activation.

PubMed

Liu, Hui; Cao, Xiaodan; Wang, Ping; Ma, Xingyuan

2017-07-01

This work examines the feasibility of using a pH-sensitive fluorescent protein as a molecular reporter for enzyme-catalyzed prodrug activation reaction. Specifically, a ratiometric pHluorins was examined for detection of the activity of horseradish peroxidase (HRP) for the activation of indole-3-acetic acid. The pHluorins and HRP were conjugated chemically, forming a biocatalyst with a self-reporting function. Results showed that the characteristic fluorescence intensity ratio of the conjugate shifted from 1.47 to 1.40 corresponding to the progress of the prodrug activation reaction. The effectiveness of applying the conjugate for inhibition of the growth of Bcap-37 cells was also demonstrated simultaneously with reaction monitoring. The results reveal a very promising approach to realizing in situ monitoring of enzyme activities based on pH shifting for enzyme-based prodrug therapy applications. © 2016 International Union of Biochemistry and Molecular Biology, Inc.

The impact of a single 24 h working day on cognitive and psychomotor performance in staff anaesthesiologists.

PubMed

Karanovic, Nenad; Carev, Mladen; Kardum, Goran; Pecotic, Renata; Valic, Maja; Karanovic, Sandra; Ujevic, Ante; Dogas, Zoran

2009-10-01

The profession of anaesthesiologist is demanding and potentially hazardous. Extended work shifts combined with intensive work load may adversely affect physicians' performance. The aim of this study was to explore the impact of a single in-hospital 24 h shift on the cognitive and psychomotor performance of anaesthesiologists in a surgical emergency department. Following ethical and institutional approval, 11 staff anaesthesiologists [six men, five women, age 48 (35-50), years of experience 17 (7-20), median (range)] successfully completed the study protocol. Four computer-generated psychological tests (CRD, Complex Reactionmeter Drenovac, Croatia) consisting of light signal position discrimination (CRD 311), simple visual orientation (CRD 21), simple arithmetic operations (CRD 11), and complex psychomotor coordination (CRD 411) were used to measure objective parameters of cognitive and psychomotor performance at four time points (D1 = 8:00 a.m., D2 = 3:00 p.m., D3 = 11:00 p.m.; and D4 = 7:00-8:00 a.m. next day) during the 24 h working day. The control testing on an ordinary working day was performed at two time points (C1 = 8:00 a.m., C2 = 3:00 p.m.). Three parameters were recorded: total test solving time (TTST), total variability, and total number of errors for all four tests. TTST was significantly impaired during the 24 h shift in all tests, and TTST was prolonged in CRD 21 test at different time points from 1.6 +/- 1.4 to 5.5 +/- 1.6 s compared with the control (F = 6.39, P = 0.001). The reaction times were prolonged from 1.3 +/- 1.8 to 5.4 +/- 1.2 s (F = 3.49, P = 0.009) in CRD 311, from 3.8 +/- 9.0 to 34.3 +/- 5.8 s (F = 5.05, P = 0.002) in CRD 11 TTST, and from 0.8 +/- 3.0 to 16.3 +/- 8.6 s (F = 2.67, P = 0.034) in CRD 411. Total variability was significantly altered during the 24 h shift only in CRD 411 (F = 2.63, P = 0.036). There was no difference in the total number of errors between the 24 h shift and the ordinary working day. Anaesthesiologists' 24 h working day in the emergency department altered cognitive and psychomotor function in comparison with ordinary working days. Speed, reliability and mental endurance (measured by TTST) were significantly impaired in all four tests. Stability and reaction time (measured by total variability) were only slightly impaired. Paradoxically, attention and alertness (measured by total number of errors) were not adversely affected. In conclusion, anaesthesiologists' psychomotor performance was impaired during the single 24 h shift.

40 CFR 60.1185 - What types of operator certification must the chief facility operator and shift supervisor obtain...

Code of Federal Regulations, 2010 CFR

2010-07-01

.... (c) Each chief facility operator and shift supervisor must take one of three actions: (1) Obtain a... in your State. (2) Schedule a full certification exam with the American Society of Mechanical Engineers (QRO-1-1994) (incorporated by reference in § 60.17(h)(1)). (3) Schedule a full certification exam...

Bimolecular reactions of carbenes: Proton transfer mechanism

NASA Astrophysics Data System (ADS)

Abu-Saleh, Abd Al-Aziz A.; Almatarneh, Mansour H.; Poirier, Raymond A.

2018-04-01

Here we report the bimolecular reaction of trifluoromethylhydroxycarbene conformers and the water-mediated mechanism of the 1,2-proton shift for the unimolecular trans-conformer by using quantum chemical calculations. The CCSD(T)/cc-pVTZ//MP2/cc-pVDZ potential-energy profile of the bimolecular reaction of cis- and trans-trifluoromethylhydroxycarbene, shows the lowest gas-phase barrier height of 13 kJ mol-1 compared to the recently reported value of 128 kJ mol-1 for the unimolecular reaction. We expect bimolecular reactions of carbene's stereoisomers will open a valuable field for new and useful synthetic strategies.

Flight controller alertness and performance during MOD shiftwork operations

NASA Technical Reports Server (NTRS)

Kelly, Sean M.; Rosekind, Mark R.; Dinges, David F.; Miller, Donna L.; Gillen, Kelly A.; Gregory, Kevin B.; Aguilar, Ronald D.; Smith, Roy M.

1994-01-01

Decreased alertness and performance associated with fatigue, sleep loss, and circadian disruption are issues faced by a diverse range of shiftwork operations. During STS operations, MOD personnel provide 24 hr. coverage of critical tasks. A joint JSC and ARC project was undertaken to examine these issues in flight controllers during MOD shiftwork operations. An initial operational test of procedures and measures was conducted during STS-53 in Dec. 1992. The study measures included a background questionnaire, a subjective daily logbook completed on a 24 hr. basis (to report sleep patterns, work periods, etc.), and an 8 minute performance and mood test battery administered at the beginning, middle, and end of each shift period. Seventeen Flight controllers representing the 3 Orbit shifts participated. The initial results clearly support further data collection during other STS missions to document baseline levels of alertness and performance during MOD shiftwork operations. These issues are especially pertinent for the night shift operations and the acute phase advance required for the transition of day shift personnel into the night for shuttle launch. Implementation and evaluation of the countermeasure strategies to maximize alertness and performance is planned. As STS missions extend to further extended duration orbiters, timelines and planning for 24 circadian disruption will remain highly relevant in the MOD environment.

Catalytic conversion of nonfood woody biomass solids to organic liquids.

PubMed

Barta, Katalin; Ford, Peter C

2014-05-20

This Account outlines recent efforts in our laboratories addressing a fundamental challenge of sustainability chemistry, the effective utilization of biomass for production of chemicals and fuels. Efficient methods for converting renewable biomass solids to chemicals and liquid fuels would reduce society's dependence on nonrenewable petroleum resources while easing the atmospheric carbon dioxide burden. The major nonfood component of biomass is lignocellulose, a matrix of the biopolymers cellulose, hemicellulose, and lignin. New approaches are needed to effect facile conversion of lignocellulose solids to liquid fuels and to other chemical precursors without the formation of intractable side products and with sufficient specificity to give economically sustainable product streams. We have devised a novel catalytic system whereby the renewable feedstocks cellulose, organosolv lignin, and even lignocellulose composites such as sawdust are transformed into organic liquids. The reaction medium is supercritical methanol (sc-MeOH), while the catalyst is a copper-doped porous metal oxide (PMO) prepared from inexpensive, Earth-abundant starting materials. This transformation occurs in a single stage reactor operating at 300-320 °C and 160-220 bar. The reducing equivalents for these transformations are derived by the reforming of MeOH (to H2 and CO), which thereby serves as a "liquid syngas" in the present case. Water generated by deoxygenation processes is quickly removed by the water-gas shift reaction. The Cu-doped PMO serves multiple purposes, catalyzing substrate hydrogenolysis and hydrogenation as well as the methanol reforming and shift reactions. This one-pot "UCSB process" is quantitative, giving little or no biochar residual. Provided is an overview of these catalysis studies beginning with reactions of the model compound dihydrobenzofuran that help define the key processes occurring. The initial step is phenyl-ether bond hydrogenolysis, and this is followed by aromatic ring hydrogenation. The complete catalytic disassembly of the more complex organosolv lignin to monomeric units, largely propyl-cyclohexanol derivatives is then described. Operational indices based on (1)H NMR analysis are also presented that facilitate holistic evaluation of these product streams that within several hours consist largely of propyl-cyclohexanol derivatives. Lastly, we describe the application of this methodology with several types of wood (pine sawdust, etc.) and with cellulose fibers. The product distribution, albeit still complex, displays unprecedented selectivity toward the production of aliphatic alcohols and methylated derivatives thereof. These observations clearly indicate that the Cu-doped solid metal oxide catalyst combined with sc-MeOH is capable of breaking down the complex biomass derived substrates to markedly deoxygenated monomeric units with increased hydrogen content. Possible implementations of this promising system on a larger scale are discussed.

Anaesthesia-associated hypersensitivity reactions: seven years' data from a British bi-specialty clinic.

PubMed

Low, A E; McEwan, J C; Karanam, S; North, J; Kong, K-L

2016-01-01

Our bi-specialty clinic was established to systematically investigate patients with suspected peri-operative hypersensitivity reactions. Four hundred and ten patients were studied; 316 following an intra-operative reaction ('postoperative' group) and 94 with a previous history of reaction, referred before undergoing anaesthesia ('pre-operative' group). In the postoperative group, 173 (54.7%) were diagnosed with IgE-mediated reactions: 65 (37.6%) to neuromuscular blocking drugs; 54 (31.2%) antibiotics; 15 (8.7%) chlorhexidine and 12 (6.9%) patent blue dye. Reactions were severe in 114 patients (65.9%). All reactions to patent blue dye were severe. We identified IgE sensitisation in 22 (13.2%) cases with isolated mucocutaneous reactions. Only 173 (54.7%) patients had serum tryptase samples taken. Referrers' suspected causal agent was confirmed in only 37.2% of patients. Of 94 patients reviewed 'pre-operatively', 29 (30.8%) were diagnosed with IgE-mediated hypersensitivity reactions, reinforcing the importance of investigating this group of patients. Knowledge of the range of causative agents identified in our study should guide the investigation of suspected peri-operative hypersensitivity reactions. © 2015 The Association of Anaesthetists of Great Britain and Ireland.

[Industrial hygiene for subway train operators].

PubMed

Elizarov, B B; Sin'kov, A V

1995-01-01

Subway train drivers work in specific conditions of underground surroundings, face psychoemotional stress due to high intensity of signals analyzed in short time for the decision, prominent responsibility for passengers' lives. The work is also associated with significant levels of noise, minor artificial illumination, air pollution with dust and unfavorable microclimate. By the end of working shift the drivers demonstrate marked changes in blood pressure, prolonged oculomotor reactions, depressed visual function. Morbidity with transitory disablement is high among the drivers, presenting especially cardiovascular and gastrointestinal diseases. Unfavorable changes of ageing process are seen in the drivers over 35, in age group of 40-49 years (with length of service at least 20 years). The complex investigations helped to elaborate hygienic norms for new subway cars, to base rational schedule ot work and rest for the drivers.

Hard templating ultrathin polycrystalline hematite nanosheets: effect of nano-dimension on CO2 to CO conversion via the reverse water-gas shift reaction.

PubMed

Fishman, Zachary S; He, Yulian; Yang, Ke R; Lounsbury, Amanda W; Zhu, Junqing; Tran, Thanh Minh; Zimmerman, Julie B; Batista, Victor S; Pfefferle, Lisa D

2017-09-14

Understanding how nano-dimensionality impacts iron oxide based catalysis is central to a wide range of applications. Here, we focus on hematite nanosheets, nanowires and nanoparticles as applied to catalyze the reverse water gas shift (RWGS) probe reaction. We introduce a novel approach to synthesize ultrathin (4-7 nm) hematite nanosheets using copper oxide nanosheets as a hard template and propose a reaction mechanism based on density functional theory (DFT) calculations. Hematite nanowires and nanoparticles were also synthesized and characterized. H 2 temperature programmed reduction (H 2 -TPR) and RWGS reactions were performed to glean insights into the mechanism of CO 2 conversion to CO over the iron oxide nanomaterials and were compared to H 2 binding energy calculations based on density functional theory. While the nanosheets did exhibit high CO 2 conversion, 28% at 510 °C, we found that the iron oxide nanowires had the highest CO 2 conversion, reaching 50% at 750 °C under atmospheric pressure. No products besides CO and H 2 O were detected.

Can varying the number of teams in a shift schedule constitute a preventive strategy?

PubMed

Jeppesen, Hans Jeppe; Kleiven, Magnar; Bøggild, Henrik

2004-12-01

The study examines the implications for shiftworkers of applying different numbers of teams in the organization of shiftwork. The participating operators came from five different companies applying continuous shift rotation systems. The companies shared the same product organization and a common corporate culture belonging to the same multinational company. Each company had a shift system consisting of four, five or six teams, with the proportion of shifts outside day work decreasing as the number of teams increased. Questionnaire and documentary data were used as data sources. Operators in systems with additional teams had more daywork but also more irregular working hours due to both overtime and schedule changes. Operators using six teams used fewer social compensation strategies. Operators in four teams were most satisfied with their work hours. Satisfaction with the time available for various social activities outside work varied inconsistently between the groups. In rotating systems the application of more teams reduces the number of shifts outside day work. This apparent improvement for shiftworkers was counteracted by a concomitant irregularity produced by greater organizational requirements for flexibility. The balance of this interaction was found to have a critical impact on employees.

Experience gained from shifting a PK-19 boiler to operate with increased superheating and with a load higher than its rated value

NASA Astrophysics Data System (ADS)

Kholshchev, V. V.

2011-08-01

Failures of steam superheater tubes occurred after the boiler was shifted to operate with a steam temperature of 540°C. The operation of the steam superheater became more reliable after it had been subjected to retrofitting. The modernization scheme is described. An estimate is given to the temperature operating conditions of tubes taking into account the thermal-hydraulic nonuniformity of their heating.

Features of the reaction of heterocyclic analogs of chalcone with lanthanide shift reagents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Turov, A.V.; Khilya, V.P.

1994-10-01

The PMR spectra of heterocyclic analogs of 2-hydroxychalcone containing thiazole, benzofuran, triazole, imidazole, benzodioxane, or pyridine rings in the presence of lanthanide shift reagents are studied. It is found that the most effective reagent for modifying the spectra of these compounds is Yb(fod)3. The broadening of the spectra of 2-hydroxy chalcones in the presence of lanthanide shift reagents is explained by the dynamic effects of complex formation. An example is given of the determination of the conformation of molecules of 2-hydroxychalcone by the simultaneous use of lanthanide shift reagents and the homonuclear Overhauser effect. 9 refs., 1 fig., 1 tab.

Modeling and optimization of proton-conducting solid oxide electrolysis cell: Conversion of CO2 into value-added products

NASA Astrophysics Data System (ADS)

Namwong, Lawit; Authayanun, Suthida; Saebea, Dang; Patcharavorachot, Yaneeporn; Arpornwichanop, Amornchai

2016-11-01

Proton-conducting solid oxide electrolysis cells (SOEC-H+) are a promising technology that can utilize carbon dioxide to produce syngas. In this work, a detailed electrochemical model was developed to predict the behavior of SOEC-H+ and to prove the assumption that the syngas is produced through a reversible water gas-shift (RWGS) reaction. The simulation results obtained from the model, which took into account all of the cell voltage losses (i.e., ohmic, activation, and concentration losses), were validated using experimental data to evaluate the unknown parameters. The developed model was employed to examine the structural and operational parameters. It is found that the cathode-supported SOEC-H+ is the best configuration because it requires the lowest cell potential. SOEC-H+ operated favorably at high temperatures and low pressures. Furthermore, the simulation results revealed that the optimal S/C molar ratio for syngas production, which can be used for methanol synthesis, is approximately 3.9 (at a constant temperature and pressure). The SOEC-H+ was optimized using a response surface methodology, which was used to determine the optimal operating conditions to minimize the cell potential and maximize the carbon dioxide flow rate.

Use of Circadian Lighting System to improve night shift alertness and performance of NRC Headquarters Operations Officers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baker, T.L.; Morisseau, D.; Murphy, N.M.

1995-04-01

The Nuclear Regulatory Commission`s (NRC) Headquarters Operations Officers (HOOs) receive and respond to events reported in the nuclear industry on a 24-hour basis. The HOOs have reported reduced alertness on the night shift, leading to a potential deterioration in their on-shift cognitive performance during the early morning hours. For some HOOs, maladaptation to the night shift was also reported to be the principal cause of: (a) reduced alertness during the commute to and from work, (b) poor sleep quality, and (c) personal lifestyle problems. ShiftWork Systems, Inc. (SWS) designed and installed a Circadian Lighting System (CLS) at both the Bethesdamore » and Rockville HOO stations with the goal of facilitating the HOOs physiological adjustment to their night shift schedules. The data indicate the following findings: less subjective fatigue on night shifts; improved night shift alertness and mental performance; higher HOO confidence in their ability to assess event reports; longer, deeper and more restorative day sleep after night duty shifts; swifter adaptation to night work; and a safer commute, particularly for those with extensive drives.« less

Sleep duration and sleep-related problems in different occupations in the Hordaland Health Study.

PubMed

Ursin, Reidun; Baste, Valborg; Moen, Bente E

2009-05-01

The aim of this study was to examine the relationship between occupation and sleep duration, sleepiness, insufficient sleep, and insomnia in day and shift workers (including night work and watches). The study was population-based and cross-sectional, and relied on self-administered questionnaires. It was conducted as part of the 1997-1999 Hordaland Health Study in collaboration with the Norwegian National Health Screening Service. Aged 40-45 years, 7782 participants answered a sleep questionnaire, reporting their occupation and whether or not they were employed in shift work. Our study found differences in sleep duration during the working week between occupational groups; in both shift and day workers. Craft workers, plant operators, and drivers slept less than leaders, and non-personal and personal service workers. Within some occupations (leaders, personal service workers, and plant operators), shift workers slept less than day workers. The mean sleep duration of shift workers was 15 minutes shorter than that of day workers. Rise times, but not bedtimes, were earlier in craft-and construction workers, plant operators, and drivers than in leaders and non-personal and personal service workers, particularly day workers. When adjusted for shift work and working hours - compared to leaders - craft workers, plant operators, and drivers had an increased risk of daytime sleepiness (odds ratio 1.5, 1.8, and 1.8 respectively) and of falling asleep at work (odds ratio 1.6, 2.1 and 2.0 respectively). Shift workers had an increased risk of falling asleep at work and insomnia. Occupation has separate effects on sleep duration and sleep-related problems, independent of the effects of shift work.

View of Mission Control Center during the Apollo 13 emergency return

NASA Image and Video Library

1970-04-16

S70-35369 (16 April 1970) --- Discussion in the Mission Operations Control Room (MOCR) dealing with the Apollo 13 crewmen during their final day in space. From left to right are Glynn S. Lunney, Shift 4 flight director; Gerald D. Griffin, Shift 2 flight director; astronaut James A. McDivitt, manager, Apollo Spacecraft Program, MSC; Dr. Donald K. Slayton, director of Flight Crew Operations, MSC; and Dr. Willard R. Hawkins, M.D., Shift 1 flight surgeon.

Strong photoluminescence characteristics of sulforhodamine B attached on photonic crystal

NASA Astrophysics Data System (ADS)

Kim, Byoung-Ju; Kang, Kwang-Sun

2014-10-01

The optical properties of sulforhodamine B (SRH) impregnated in photonic crystal by two step synthetic processes including a urethane bond formation between a 3-isocyanatopropyl triethoxysilane (ICPTES, -N=C=O) and a SRH with elevated temperature in pyridine and hydrolysis-condensation reactions between synthesized ICPTES/SRH (ICPSRH) and tetraethoxyorthosilicate (TEOS) in NH4OH. The monodisperse silica spheres impregnated the ICPSRH (ICPSRHS) are fabricated. The reduction of the absorption peak at 2270 cm-1 representing asymmetric stretching vibration of -N=C=O indicates the progress of the reaction and new absorption peak at 1712 cm-1 characterizing -C=O stretching vibration indicates the formation of urethane bond. The UV-visible absorption spectra show the broadened spectral line width by intermolecular interaction. The photoluminescence (PL) peak of the SRH in methanol shows a hypsochromic shift with the increase the excitation wavelength. However, the PL peak for the ICPSRH exhibits a bathochromic shift as the excitation wavelength increases. The PL peak for the ICPSRH shows no hypsochromic or bathochromic shift. The PL peaks for SRH in methanol, ICPSRH and ICPSRHS are at 568, 598 and 572 nm, respectively. The main cause of the PL peak shift is due to the intermolecular interaction.

Exploring the activity of a novel Au/TiC(001) model catalyst towards CO and CO 2 hydrogenation

DOE PAGES

Asara, Gian Giacomo; Ricart, Josep M.; Rodriguez, Jose A.; ...

2015-02-02

Small metallic nanoparticles supported on transition metal carbides exhibit an unexpected high activity towards a series of chemical reactions. In particular, the Au/TiC system has proven to be an excellent catalyst for SO 2 decomposition, thiophene hydrodesulfurization, O 2 and H 2 dissociation and the water gas shift reaction. Recent studies have shown that Au/TiC is a very good catalyst for the reverse water–gas shift (CO 2 + H 2 → CO + H 2O) and CO 2 hydrogenation to methanol. The present work further expands the range of applicability of this novel type of systems by exploring the catalyticmore » activity of Au/TiC towards the hydrogenation of CO or CO 2 with periodic density functional theory (DFT) calculations on model systems. Hydrogen dissociates easily on Au/TiC but direct hydrogenation of CO to methanol is hindered by very high activation barriers implying that, on this model catalyst, methanol production from CO 2 involves the hydrogenation of a HOCO-like intermediate. Thus, when dealing with mixtures of syngas (CO/CO 2/H 2/H 2O), CO could be transformed into CO 2 through the water gas shift reaction with subsequent hydrogenation of CO 2 to methanol.« less

Process for operating equilibrium controlled reactions

DOEpatents

Nataraj, Shankar; Carvill, Brian Thomas; Hufton, Jeffrey Raymond; Mayorga, Steven Gerard; Gaffney, Thomas Richard; Brzozowski, Jeffrey Richard

2001-01-01

A cyclic process for operating an equilibrium controlled reaction in a plurality of reactors containing an admixture of an adsorbent and a reaction catalyst suitable for performing the desired reaction which is operated in a predetermined timed sequence wherein the heating and cooling requirements in a moving reaction mass transfer zone within each reactor are provided by indirect heat exchange with a fluid capable of phase change at temperatures maintained in each reactor during sorpreaction, depressurization, purging and pressurization steps during each process cycle.

In Situ UV-Visible Assessment of Iron-Based High-Temperature Water-Gas Shift Catalysts Promoted with Lanthana: An Extent of Reduction Study

DOE PAGES

Hallac, Basseem B.; Brown, Jared C.; Stavitski, Eli; ...

2018-02-04

Here, the extent of reduction of unsupported iron-based high-temperature water-gas shift catalysts with small (<5 wt %) lanthana contents was studied using UV-visible spectroscopy. Temperature- programmed reduction measurements showed that lanthana content higher than 0.5 wt % increased the extent of reduction to metallic Fe, while 0.5 wt % of lanthana facilitated the reduction to Fe 3O 4. In situ measurements on the iron oxide catalysts using mass and UV-visible spectroscopies permitted the quantification of the extent of reduction under temperature-programmed reduction and high-temperature water-gas shift conditions. The oxidation states were successfully calibrated against normalized absorbance spectra of visible lightmore » using the Kubelka-Munk theory. The normalized absorbance relative to the fully oxidized Fe 2O 3 increased as the extent of reduction increased. XANES suggested that the average bulk iron oxidation state during the water-gas shift reaction was Fe +2.57 for the catalyst with no lanthana and Fe +2.54 for the catalysts with 1 wt % lanthana. However, the UV-vis spectra suggest that the surface oxidation state of iron would be Fe +2.31 for the catalyst with 1 wt % lanthana if the oxidation state of iron in the catalyst with 0 wt % lanthana were Fe +2.57. The findings of this paper emphasize the importance of surface sensitive UV-visible spectroscopy for determining the extent of catalyst reduction during operation. Furthermore, the paper highlights the potential to use bench-scale UV-visible spectroscopy to study the surface chemistry of catalysts instead of less-available synchrotron X-ray radiation facilities.« less

In Situ UV-Visible Assessment of Iron-Based High-Temperature Water-Gas Shift Catalysts Promoted with Lanthana: An Extent of Reduction Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hallac, Basseem B.; Brown, Jared C.; Stavitski, Eli

Here, the extent of reduction of unsupported iron-based high-temperature water-gas shift catalysts with small (<5 wt %) lanthana contents was studied using UV-visible spectroscopy. Temperature- programmed reduction measurements showed that lanthana content higher than 0.5 wt % increased the extent of reduction to metallic Fe, while 0.5 wt % of lanthana facilitated the reduction to Fe 3O 4. In situ measurements on the iron oxide catalysts using mass and UV-visible spectroscopies permitted the quantification of the extent of reduction under temperature-programmed reduction and high-temperature water-gas shift conditions. The oxidation states were successfully calibrated against normalized absorbance spectra of visible lightmore » using the Kubelka-Munk theory. The normalized absorbance relative to the fully oxidized Fe 2O 3 increased as the extent of reduction increased. XANES suggested that the average bulk iron oxidation state during the water-gas shift reaction was Fe +2.57 for the catalyst with no lanthana and Fe +2.54 for the catalysts with 1 wt % lanthana. However, the UV-vis spectra suggest that the surface oxidation state of iron would be Fe +2.31 for the catalyst with 1 wt % lanthana if the oxidation state of iron in the catalyst with 0 wt % lanthana were Fe +2.57. The findings of this paper emphasize the importance of surface sensitive UV-visible spectroscopy for determining the extent of catalyst reduction during operation. Furthermore, the paper highlights the potential to use bench-scale UV-visible spectroscopy to study the surface chemistry of catalysts instead of less-available synchrotron X-ray radiation facilities.« less

Controlling reactivity of nanoporous catalyst materials by tuning reaction product-pore interior interactions: Statistical mechanical modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jing; Ackerman, David M.; Lin, Victor S.-Y.

2013-04-02

Statistical mechanical modeling is performed of a catalytic conversion reaction within a functionalized nanoporous material to assess the effect of varying the reaction product-pore interior interaction from attractive to repulsive. A strong enhancement in reactivity is observed not just due to the shift in reaction equilibrium towards completion but also due to enhanced transport within the pore resulting from reduced loading. The latter effect is strongest for highly restricted transport (single-file diffusion), and applies even for irreversible reactions. The analysis is performed utilizing a generalized hydrodynamic formulation of the reaction-diffusion equations which can reliably capture the complex interplay between reactionmore » and restricted transport.« less

Detection of Potential TNA and RNA Nucleoside Precursors in a Prebiotic Mixture by Pure Shift Diffusion-Ordered NMR Spectroscopy

PubMed Central

Islam, Saidul; Aguilar, Juan A; Powner, Matthew W; Nilsson, Mathias; Morris, Gareth A; Sutherland, John D

2013-01-01

In the context of prebiotic chemistry, one of the characteristics of mixed nitrogenous-oxygenous chemistry is its propensity to give rise to highly complex reaction mixtures. There is therefore an urgent need to develop improved spectroscopic techniques if onerous chromatographic separations are to be avoided. One potential avenue is the combination of pure shift methodology, in which NMR spectra are measured with greatly improved resolution by suppressing multiplet structure, with diffusion-ordered spectroscopy, in which NMR signals from different species are distinguished through their different rates of diffusion. Such a combination has the added advantage of working with intact mixtures, allowing analyses to be carried out without perturbing mixtures in which chemical entities are part of a network of reactions in equilibrium. As part of a systems chemistry approach towards investigating the self-assembly of potentially prebiotic small molecules, we have analysed the complex mixture arising from mixing glycolaldehyde and cyanamide, in a first application of pure shift DOSY NMR to the characterisation of a partially unknown reaction composition. The work presented illustrates the potential of pure shift DOSY to be applied to chemistries that give rise to mixtures of compounds in which the NMR signal resolution is poor. The direct formation of potential RNA and TNA nucleoside precursors, amongst other adducts, was observed. These preliminary observations may have implications for the potentially prebiotic assembly chemistry of pyrimidine threonucleotides, and therefore of TNA, by using recently reported chemistries that yield the activated pyridimidine ribonucleotides. PMID:23371787

Doping reaction of PH3 and B2H6 with Si(100)

NASA Astrophysics Data System (ADS)

Yu, Ming L.; Vitkavage, D. J.; Meyerson, B. S.

1986-06-01

The reaction of phosphine PH3 and diborane B2H6 on Si(100) surfaces was studied by surface analytical techniques in relation to the in situ doping process in the chemical vapor deposition of silicon. Phosphine chemisorbs readily either nondissociatively at room temperature or dissociatively with the formation of silicon-hydrogen bonds at higher temperatures. Hydrogen can be desorbed at temperatures above 400 °C to generate a phosphorus layer. Phosphorus is not effective in shifting the Fermi level until the coverage reaches 2×1014/cm2. A maximum shift of 0.45 eV toward the conduction band was observed. In contrast, diborane has a very small sticking coefficient and the way to deposit boron is to decompose diborane directly on the silicon surface at temperatures above 600 °C. Boron at coverages less than 2×1014/cm2 is very effective in shifting the Fermi level toward the valence band and a maximum change of 0.4 eV was observed.

Factors Influencing F/OSS Cloud Computing Software Product Success: A Quantitative Study

ERIC Educational Resources Information Center

Letort, D. Brian

2012-01-01

Cloud Computing introduces a new business operational model that allows an organization to shift information technology consumption from traditional capital expenditure to operational expenditure. This shift introduces challenges from both the adoption and creation vantage. This study evaluates factors that influence Free/Open Source Software…

Person-directed, non-pharmacological interventions for sleepiness at work and sleep disturbances caused by shift work.

PubMed

Slanger, Tracy E; Gross, J Valérie; Pinger, Andreas; Morfeld, Peter; Bellinger, Miriam; Duhme, Anna-Lena; Reichardt Ortega, Rosalinde Amancay; Costa, Giovanni; Driscoll, Tim R; Foster, Russell G; Fritschi, Lin; Sallinen, Mikael; Liira, Juha; Erren, Thomas C

2016-08-23

Shift work is often associated with sleepiness and sleep disorders. Person-directed, non-pharmacological interventions may positively influence the impact of shift work on sleep, thereby improving workers' well-being, safety, and health. To assess the effects of person-directed, non-pharmacological interventions for reducing sleepiness at work and improving the length and quality of sleep between shifts for shift workers. We searched CENTRAL, MEDLINE Ovid, Embase, Web of Knowledge, ProQuest, PsycINFO, OpenGrey, and OSH-UPDATE from inception to August 2015. We also screened reference lists and conference proceedings and searched the World Health Organization (WHO) Trial register. We contacted experts to obtain unpublished data. Randomised controlled trials (RCTs) (including cross-over designs) that investigated the effect of any person-directed, non-pharmacological intervention on sleepiness on-shift or sleep length and sleep quality off-shift in shift workers who also work nights. At least two authors screened titles and abstracts for relevant studies, extracted data, and assessed risk of bias. We contacted authors to obtain missing information. We conducted meta-analyses when pooling of studies was possible. We included 17 relevant trials (with 556 review-relevant participants) which we categorised into three types of interventions: (1) various exposures to bright light (n = 10); (2) various opportunities for napping (n = 4); and (3) other interventions, such as physical exercise or sleep education (n = 3). In most instances, the studies were too heterogeneous to pool. Most of the comparisons yielded low to very low quality evidence. Only one comparison provided moderate quality evidence. Overall, the included studies' results were inconclusive. We present the results regarding sleepiness below. Bright light Combining two comparable studies (with 184 participants altogether) that investigated the effect of bright light during the night on sleepiness during a shift, revealed a mean reduction 0.83 score points of sleepiness (measured via the Stanford Sleepiness Scale (SSS) (95% confidence interval (CI) -1.3 to -0.36, very low quality evidence). Another trial did not find a significant difference in overall sleepiness on another sleepiness scale (16 participants, low quality evidence).Bright light during the night plus sunglasses at dawn did not significantly influence sleepiness compared to normal light (1 study, 17 participants, assessment via reaction time, very low quality evidence).Bright light during the day shift did not significantly reduce sleepiness during the day compared to normal light (1 trial, 61 participants, subjective assessment, low quality evidence) or compared to normal light plus placebo capsule (1 trial, 12 participants, assessment via reaction time, very low quality evidence). Napping during the night shiftA meta-analysis on a single nap opportunity and the effect on the mean reaction time as a surrogate for sleepiness, resulted in a 11.87 ms reduction (95% CI 31.94 to -8.2, very low quality evidence). Two other studies also reported statistically non-significant decreases in reaction time (1 study seven participants; 1 study 49 participants, very low quality evidence).A two-nap opportunity resulted in a statistically non-significant increase of sleepiness (subjective assessment) in one study (mean difference (MD) 2.32, 95% CI -24.74 to 29.38, 1 study, 15 participants, low quality evidence). Other interventionsPhysical exercise and sleep education interventions showed promise, but sufficient data to draw conclusions are lacking. Given the methodological diversity of the included studies, in terms of interventions, settings, and assessment tools, their limited reporting and the very low to low quality of the evidence they present, it is not possible to determine whether shift workers' sleepiness can be reduced or if their sleep length or quality can be improved with these interventions.We need better and adequately powered RCTs of the effect of bright light, and naps, either on their own or together and other non-pharmacological interventions that also consider shift workers' chronobiology on the investigated sleep parameters.

High luminescent L-cysteine capped CdTe quantum dots prepared at different reaction times

NASA Astrophysics Data System (ADS)

Kiprotich, Sharon; Onani, Martin O.; Dejene, Francis B.

2018-04-01

This paper reports a facile synthesis route of high luminescent L-cysteine capped CdTe quantum dots (QDs). The effect of reaction time on the growth mechanism, optical and physical properties of the CdTe QDs was investigated in order to find the suitability of them towards optical and medical applications. The representative high-resolution transmission microscopy (HRTEM) analysis showed that the as-obtained CdTe QDs appeared as spherical particles with excellent monodispersity. The images exhibited clear lattice fringes which are indicative of good crystallinity. The X-ray diffraction (XRD) pattern displayed polycrystalline nature of the QDs which correspond well to zinc blende phase of bulk CdTe. The crystallite sizes calculated from the Scherrer equation were less than 10 nm for different reaction times which were in close agreement with the values estimated from HRTEM. An increase in reaction time improved crystallinity of the sample as explained by highest peak intensity of the XRD supported by the photoluminescence emission spectra which showed high intensity at a longer growth time. It was observed that for prolonged growth time the emission bands were red shifted from about 517-557 nm for 5-180 min of reaction time due to increase in particle sizes. Ultraviolet and visible analysis displayed well-resolved absorption bands which were red shifted upon an increase in reaction time. There was an inverse relation between the band gap and reaction time. Optical band gap decreases from 3.98 to 2.59 eV with the increase in reaction time from 15 to 180 min.

A Time-Dependent Quantum Dynamics Study of the H2 + CH3 yields H + CH4 Reaction

NASA Technical Reports Server (NTRS)

Wang, Dunyou; Kwak, Dochan (Technical Monitor)

2002-01-01

We present a time-dependent wave-packet propagation calculation for the H2 + CH3 yields H + CH4 reaction in six degrees of freedom and for zero total angular momentum. Initial state selected reaction probability for different initial rotational-vibrational states are presented in this study. The cumulative reaction probability (CRP) is obtained by summing over initial-state-selected reaction probability. The energy-shift approximation to account for the contribution of degrees of freedom missing in the 6D calculation is employed to obtain an approximate full-dimensional CRP. Thermal rate constant is compared with different experiment results.

Cationic Cyclizations and Rearrangements Promoted by a Heterogeneous Gold Catalyst

PubMed Central

2015-01-01

A heterogeneous gold catalyst with remarkable activity for promoting the electrophilic reactions of aryl vinyl ketones and aryl dienyl ketones is described. The catalyst is easy to prepare, is robust, and can be recycled. Low loadings are effective for different types of cationic reactions, including Nazarov cyclizations, lactonizations, and [1,2] shifts. PMID:24432741

Accurate evaluation of fast threshold voltage shift for SiC MOS devices under various gate bias stress conditions

NASA Astrophysics Data System (ADS)

Sometani, Mitsuru; Okamoto, Mitsuo; Hatakeyama, Tetsuo; Iwahashi, Yohei; Hayashi, Mariko; Okamoto, Dai; Yano, Hiroshi; Harada, Shinsuke; Yonezawa, Yoshiyuki; Okumura, Hajime

2018-04-01

We investigated methods of measuring the threshold voltage (V th) shift of 4H-silicon carbide (SiC) metal–oxide–semiconductor field-effect transistors (MOSFETs) under positive DC, negative DC, and AC gate bias stresses. A fast measurement method for V th shift under both positive and negative DC stresses revealed the existence of an extremely large V th shift in the short-stress-time region. We then examined the effect of fast V th shifts on drain current (I d) changes within a pulse under AC operation. The fast V th shifts were suppressed by nitridation. However, the I d change within one pulse occurred even in commercially available SiC MOSFETs. The correlation between I d changes within one pulse and V th shifts measured by a conventional method is weak. Thus, a fast and in situ measurement method is indispensable for the accurate evaluation of I d changes under AC operation.

Avoiding Focus Shifts in Surgical Telementoring Using an Augmented Reality Transparent Display.

PubMed

Andersen, Daniel; Popescu, Voicu; Cabrera, Maria Eugenia; Shanghavi, Aditya; Gomez, Gerardo; Marley, Sherri; Mullis, Brian; Wachs, Juan

2016-01-01

Conventional surgical telementoring systems require the trainee to shift focus away from the operating field to a nearby monitor to receive mentor guidance. This paper presents the next generation of telementoring systems. Our system, STAR (System for Telementoring with Augmented Reality) avoids focus shifts by placing mentor annotations directly into the trainee's field of view using augmented reality transparent display technology. This prototype was tested with pre-medical and medical students. Experiments were conducted where participants were asked to identify precise operating field locations communicated to them using either STAR or a conventional telementoring system. STAR was shown to improve accuracy and to reduce focus shifts. The initial STAR prototype only provides an approximate transparent display effect, without visual continuity between the display and the surrounding area. The current version of our transparent display provides visual continuity by showing the geometry and color of the operating field from the trainee's viewpoint.

30 CFR 62.174 - Follow-up corrective measures when a standard threshold shift is detected.

Code of Federal Regulations, 2012 CFR

2012-07-01

... threshold shift is detected. 62.174 Section 62.174 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION... measures when a standard threshold shift is detected. The mine operator must, within 30 calendar days of receiving evidence or confirmation of a standard threshold shift, unless a physician or audiologist...

Two-phase charge-coupled device

NASA Technical Reports Server (NTRS)

Kosonocky, W. F.; Carnes, J. E.

1973-01-01

A charge-transfer efficiency of 99.99% per stage was achieved in the fat-zero mode of operation of 64- and 128-stage two-phase charge-coupled shift registers at 1.0-MHz clock frequency. The experimental two-phase charge-coupled shift registers were constructed in the form of polysilicon gates overlapped by aluminum gates. The unidirectional signal flow was accomplished by using n-type substrates with 0.5 to 1.0 ohm-cm resistivity in conjunction with a channel oxide thickness of 1000 A for the polysilicon gates and 3000 A for the aluminum gates. The operation of the tested shift registers with fat zero is in good agreement with the free-charge transfer characteristics expected for the tested structures. The charge-transfer losses observed when operating the experimental shift registers without the fat zero are attributed to fast interface state trapping. The analytical part of the report contains a review backed up by an extensive appendix of the free-charge transfer characteristics of CCD's in terms of thermal diffusion, self-induced drift, and fringing field drift. Also, a model was developed for the charge-transfer losses resulting from charge trapping by fast interface states. The proposed model was verified by the operation of the experimental two-phase charge-coupled shift registers.

Plasmonic-Enhanced Catalysis

DTIC Science & Technology

2012-05-30

shifts that cannot be merely explained hydride formation. These unexpected LSPR shifts may be explained by Au/Pd interdiffusion or silicide formation...photocurrent on a chemically modified gold thin film of metal -semiconductor (TiO2) Schottky diodes. • Intrinsic correlation between the hot electron flow...reaction to study catalyst nanoparticles at the single particle level. As hydrogen gas dissociates and intercalates into Pd, Pd changes from a metal to

Domino reactions initiated by intramolecular hydride transfers from tri(di)arylmethane fragments to ketenimine and carbodiimide functions.

PubMed

Alajarin, Mateo; Bonillo, Baltasar; Ortin, Maria-Mar; Sanchez-Andrada, Pilar; Vidal, Angel; Orenes, Raul-Angel

2010-10-21

The ability of triarylmethane and diarylmethane fragments to behave as hydride donors participating in thermal [1,5]-H shift/6π-ERC tandem processes involving ketenimine and carbodiimide functions is disclosed. C-Alkyl-C-phenyl ketenimines N-substituted by a triarylmethane substructure convert into a variety of 3,3,4,4-tetrasubstituted-3,4-dihydroquinolines, as structurally related carbodiimides transform into 3,4,4-trisubstituted-3,4-dihydroquinazolines via transient ortho-azaxylylenes. The first step of these one-pot conversions, the [1,5]-H shift, is considered to be a hydride migration on the basis of the known hydricity of the tri(di)arylmethane fragment and the electrophilicity of the central heterocumulenic carbon atom, whereas the final electrocyclization involves the formation of a sterically congested C-C or C-N bond. In the cases of C,C-diphenyl substituted triarylmethane-ketenimines the usual 6π-ERC becomes prohibited by the presence of two phenyl rings at each end of the azatrienic system. This situation opens new reaction channels: (a) following the initial hydride shift, the tandem sequence continues with an alternative electrocyclization mode to give 9,10-dihydroacridines, (b) the full sequence is initiated by a rare 1,5 migration of an electron-rich aryl group, followed by a 6π-ERC which leads to 2-aryl-3,4-dihydroquinolines, or (c) a different [1,5]-H shift/6π-ERC sequence involving the initial migration of a hydrogen atom from a methyl group at the ortho position to the nitrogen atom of the ketenimine function. Diarylmethane-ketenimines bearing a methyl group at the benzylic carbon atom experience a tandem double [1,5]-H shift, the first one being the usual benzylic hydride transfer whereas the second one involves the methyl group at the initial benzylic carbon atom, the reaction products being 2-aminostyrenes. Diarylmethane-ketenimines lacking such a methyl group convert into 3,4-dihydroquinolines by the habitual tandem [1,5]-H shift/6π-ERC processes.

Fatigue in U.S. Astronauts Onboard the International Space Station: Environmental Factors, Operational Impacts, and Implementation of Countermeasures

NASA Technical Reports Server (NTRS)

Scheuring, R. A.; Moomaw, R. C.; Johnston, S. L.

2014-01-01

Since 2000, US astronauts have been supporting missions up to a six month duration on the International Space Station (ISS). Crewmembers have experienced fatigue for reasons similar to military deployments. Astronauts experience psychological stressors such as heavy workloads, extended duty periods, circadian misalignment, inadequate/ineffective sleep, and loss of the environmental cues of a gravity environment. Complicating the psychological stressors are environmental factors; distracting background noise, unexpected and variable mission schedules, unfavorable thermal control, elevated CO2 levels, and an unusual sleep environment with schedules that impinge on pre-sleep periods. Physiological contributors to poor sleep and fatigue include a cephalad fluid shift and back pain. Restful sleep is further challenged due to a lack of gravity-related proprioceptive cues and need for restraints. The term "space fog" has been used by astronauts to describe a phenomenon of forgetfulness, slowed reaction time and transient confusion while trying to complete tasks. There is a distinct temporal correlation with arrival on the Space Station and the onset of slowed cognitive skills and a spontaneous resolution that may take up to 6 weeks. The Genesis of this phenomenon may be chronic fatigue secondary to transitioning from a planar environment to a 360deg microgravity perspective. Recently, countermeasures to improve sleep duration and quality in astronauts on the ISS have been instituted with moderate degrees of success as measured by self-reaction time (psychomotor vigilance task testing), actigraphy, and subjective reports. Judicious use of stimulants and hypnotics, light therapy, controlled sleep periods and sleep shifting and reducing ambient CO2 levels are a few of the most promising countermeasures being used in space to improve sleep and reduce fatigue.

Imposed glutathione-mediated redox switch modulates the tobacco wound-induced protein kinase and salicylic acid-induced protein kinase activation state and impacts on defence against Pseudomonas syringae

PubMed Central

Matern, Sanja; Peskan-Berghoefer, Tatjana; Gromes, Roland; Kiesel, Rebecca Vazquez; Rausch, Thomas

2015-01-01

The role of the redox-active tripeptide glutathione in plant defence against pathogens has been studied extensively; however, the impact of changes in cellular glutathione redox potential on signalling processes during defence reactions has remained elusive. This study explored the impact of elevated glutathione content on the cytosolic redox potential and on early defence signalling at the level of mitogen-activated protein kinases (MAPKs), as well as on subsequent defence reactions, including changes in salicylic acid (SA) content, pathogenesis-related gene expression, callose depositions, and the hypersensitive response. Wild-type (WT) Nicotiana tabacum L. and transgenic high-glutathione lines (HGL) were transformed with the cytosol-targeted sensor GRX1-roGFP2 to monitor the cytosolic redox state. Surprisingly, HGLs displayed an oxidative shift in their cytosolic redox potential and an activation of the tobacco MAPKs wound-induced protein kinase (WIPK) and SA-induced protein kinase (SIPK). This activation occurred in the absence of any change in free SA content, but was accompanied by constitutively increased expression of several defence genes. Similarly, rapid activation of MAPKs could be induced in WT tobacco by exposure to either reduced or oxidized glutathione. When HGL plants were challenged with adapted or non-adapted Pseudomonas syringae pathovars, the cytosolic redox shift was further amplified and the defence response was markedly increased, showing a priming effect for SA and callose; however, the initial and transient hyperactivation of MAPK signalling was attenuated in HGLs. The results suggest that, in tobacco, MAPK and SA signalling may operate independently, both possibly being modulated by the glutathione redox potential. Possible mechanisms for redox-mediated MAPK activation are discussed. PMID:25628332

Analysis on logistic company action toward the access restriction policy on freight vehicle

NASA Astrophysics Data System (ADS)

Nur, Muhammad; Hadiwardoyo, Sigit P.; Nahry, Nahdalina

2017-06-01

The high volume of freight vehicles that enters, leaves or passes through the urban areas, especially Jakarta, has caused traffic congestion. Local authority plans to perform the access restriction on freight vehicles on the Jakarta Outer Ring Road (JORR) to reduce the congestion on that toll road. The study aims to analyze the alternative solutions of the logistics companies to overcome the impact of such policy. The data collection is done by interviewing 102 truck drivers and 7 staffs of logistic companies that use JORR. The results show that the most preferred action is shifting the operating time. Based on the open test, access restriction policy on JORR may cause a significant impact on the operational costs of delivery. Shifting the operational time will increase the operating cost by 1.71%, while turning the route will increase the operating costs by 4.35%. Moreover, changing the mode will reduce the operating expenses by 50%, and the combination action of shifting the route and the time will increase the operating costs by 5.39%.

The effectiveness of healthy meals at work on reaction time, mood and dietary intake: a randomised cross-over study in daytime and shift workers at an university hospital.

PubMed

Leedo, Eva; Beck, Anne Marie; Astrup, Arne; Lassen, Anne D

2017-07-01

Our dietary habits affect both cognitive performance and mood. The aim of the study was to examine the effect of increased availability of healthy meals and water at work on healthcare staff. The study used an 8-week randomised cross-over design. A total of sixty physicians, nurses and nursing assistants, including sixteen working on shifts, were recruited. The participants received a self-selected keyhole-labelled (Nordic nutrition label) lunch, snack and bottled water during each shift throughout the intervention period. Reaction time (Go/No-Go test), mood-related scores (POMS) and dietary intake were assessed at run-in, and at the end of the intervention and the control periods. The intake of fat (P=0·030) and PUFA (P=0·003) was lower, and the intake of carbohydrate (P=0·008), dietary fibre (P=0·031) and water (P<0·001) was greater in the intervention period than in the control period. The intervention had no effect on reaction time or any of the mood-related scores in the group as a whole. In shift-working participants, the intervention period resulted in a 31·1 % lower Fatigue-Inertia Score (P=0·003), a 15·3 % higher Vigour-Activity Score (P=0·041) and a 42·7 % lower Total Mood Disturbance Score (P=0·017), whereas the only dietary component that significantly improved was water intake (P=0·034), when compared with the control period. Providing healthy meals, snacks and water during working hours seems to be an effective way of improving employees' dietary intake. Moreover, increased intake of water may be associated with beneficial effects on fatigue, vigour and total mood in shift-working healthcare staff.

Hydrodesulphurization of Light Gas Oil using hydrogen from the Water Gas Shift Reaction

NASA Astrophysics Data System (ADS)

Alghamdi, Abdulaziz

2009-12-01

The production of clean fuel faces the challenges of high production cost and complying with stricter environmental regulations. In this research, the ability of using a novel technology of upgrading heavy oil to treat Light Gas Oil (LGO) will be investigated. The target of this project is to produce cleaner transportation fuel with much lower cost of production. Recently, a novel process for upgrading of heavy oil has been developed at University of Waterloo. It is combining the two essential processes in bitumen upgrading; emulsion breaking and hydroprocessing into one process. The water in the emulsion is used to generate in situ hydrogen from the Water Gas Shift Reaction (WGSR). This hydrogen can be used for the hydrogenation and hydrotreating reaction which includes sulfur removal instead of the expensive molecular hydrogen. This process can be carried out for the upgrading of the bitumen emulsion which would improve its quality. In this study, the hydrodesulphurization (HDS) of LGO was conducted using in situ hydrogen produced via the Water Gas Shift Reaction (WGSR). The main objective of this experimental study is to evaluate the possibility of producing clean LGO over dispersed molybdenum sulphide catalyst and to evaluate the effect of different promoters and syn-gas on the activity of the dispersed Mo catalyst. Experiments were carried out in a 300 ml Autoclave batch reactor under 600 psi (initially) at 391°C for 1 to 3 hours and different amounts of water. After the hydrotreating reaction, the gas samples were collected and the conversion of carbon monoxide to hydrogen via WGSR was determined using a refinery gas analyzer. The sulphur content in liquid sample was analyzed via X-Ray Fluorescence. Experimental results showed that using more water will enhance WGSR but at the same time inhibits the HDS reaction. It was also shown that the amount of sulfur removed depends on the reaction time. The plan is to investigate the effect of synthesis gas (syngas) molar ratio by varying CO to H2 ratio. It is also planned to use different catalysts promoters and compare them with the un-promoted Mo based catalysts to achieve the optimum reaction conditions for treating LGO. The results of this study showed that Ni and Co have a promoting effect over unpromoted Mo catalysts for both HDS and WGSR. Ni was found to be the best promoter for both reactions. Fe showed no significant effect for both WGSR and HDS. V and K have a good promoting effect in WGSR but they inhibited the HDS reaction. Potassium was found to be the strongest inhibitor for the HDS reaction since no sulfur was removed during the reaction. Keywords. LGO, HDS, in situ H2, WGSR, oil upgrading, syn-gas.

In Situ Solid-State Reactions Monitored by X-ray Absorption Spectroscopy: Temperature-Induced Proton Transfer Leads to Chemical Shifts.

PubMed

Stevens, Joanna S; Walczak, Monika; Jaye, Cherno; Fischer, Daniel A

2016-10-24

The dramatic colour and phase alteration with the solid-state, temperature-dependent reaction between squaric acid and 4,4'-bipyridine has been probed in situ with X-ray absorption spectroscopy. The electronic and chemical sensitivity to the local atomic environment through chemical shifts in the near-edge X-ray absorption fine structure (NEXAFS) revealed proton transfer from the acid to the bipyridine base through the change in nitrogen protonation state in the high-temperature form. Direct detection of proton transfer coupled with structural analysis elucidates the nature of the solid-state process, with intermolecular proton transfer occurring along an acid-base chain followed by a domino effect to the subsequent acid-base chains, leading to the rapid migration along the length of the crystal. NEXAFS thereby conveys the ability to monitor the nature of solid-state chemical reactions in situ, without the need for a priori information or long-range order. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pulse studies to decipher the role of surface morphology in CuO/CeO₂ nanocatalysts for the water gas shift reaction

DOE PAGES

Rodriguez, Jose A.; Zhao, Fuzhen; Liu, Zongyuan; ...

2015-01-23

The water-gas shift reaction (WGS, CO + H₂O → CO₂) was studied over CuO/CeO₂ catalysts with two different ceria particle morphohologies, in the form of nanospheres (ns) and nanocubes (nc). To understand the strong dependence of the WGS reaction activity on the ceria nanoshapes, pulses of CO (without and with water vapor) were employed during in situ X-ray diffraction (XRD) and X-ray absoprtion near edge structure (XANES) measurements done to characterize the catalysts. The results showed that CuO/CeO₂ (ns) exhibited a substantially better activity than CuO/CeO₂ (nc). The higher activity was associated with the unique properties of CuO/CeO₂ (ns), suchmore » as the easier reduction of highly dispersed CuO to metallic Cu, the stability of metallic Cu and a larger concentration Ce³⁺ in CeO₂ (ns).« less

Measuring subjective sleepiness at work in hospital nurses: validation of a modified delivery format of the Karolinska Sleepiness Scale.

PubMed

Geiger Brown, Jeanne; Wieroney, Margaret; Blair, Lori; Zhu, Shijun; Warren, Joan; Scharf, Steven M; Hinds, Pamela S

2014-12-01

Sleepiness during the work shift is common and can be hazardous to workers and, in the case of nurses, to patients under their care. Thus, measuring sleepiness in occupational studies is an important component of workplace health and safety. The Karolinska Sleepiness Scale (KSS) is usually used as a momentary assessment of a respondent's state of sleepiness; however, end-of-shift measurement is sometimes preferred based on the study setting. We assessed the predictive validity of the KSS as an end-of-shift recall measurement, asking for "average" sleepiness over the shift and "highest" level of sleepiness during the shift. Hospital registered nurses (N=40) working 12-h shifts completed an end-of-shift diary over 4 weeks that included the National Aeronautical and Space Administration Task Load Index (NASA-TLX) work intensity items and the KSS (498 shifts over 4 weeks). Vigilant attention was assessed by measuring reaction time, lapses, and anticipations using a 10-min performance vigilance task (PVT) at the end of the shift. The Horne-Ostberg Questionnaire, Epworth Sleepiness Scale, General Sleep Disturbance Scale, and Cleveland Sleep Habits Questionnaire were also collected at baseline to assess factors that could be associated with higher sleepiness. We hypothesized that higher KSS scores would correlate with vigilant attention parameters reflective of sleepiness (slower reaction times and more lapses and anticipations on a performance vigilance task) and also with those factors known to produce higher sleepiness. These factors included the following: (1) working night shifts, especially for those with "morningness" trait; (2) working sequential night shifts; (3) having low physical and mental work demands and low time pressure; (4) having concomitant organic sleep disorders; and (5) having greater "trait" sleepiness (Epworth Sleepiness Scale). Linear mixed models and generalized linear mixed models were used to test associations that could assess the predictive validity of this format of administering the KSS. Greater sleepiness, as measured by higher KSS scores, was found on shifts with nurses working night shift, the third sequential night compared to the first, those with sleep disorder symptoms (especially insomnia), and in nurses with trait sleepiness on the Epworth scale. Less sleepiness (lower KSS scores) was seen in shifts with a high level of time pressure and in nurses with a biologic predisposition to be more alert in the morning (morningness trait) who worked the day shift. We found partial support for using the Karolinska Sleepiness Scale in the recalled format based on our multiple tests of predictive validity.

Anaylyzing powers for the reaction π-p-->-->π0n at T-π=161 MeV

NASA Astrophysics Data System (ADS)

Görgen, J. J.; Comfort, J. R.; Averett, T.; Dekorse, J.; Franklin, B.; Ritchie, B. G.; Tinsley, J.; Kyle, G.; Berman, B.; Burleson, G.; Cranston, K.; Klein, A.; Faucett, J. A.; Jarmer, J. J.; Knudson, J. N.; Penttilä, S.; Tanaka, N.; Brinkmöller, B.; Dehnhard, D.; Yen, Y. F.; Høibrråten, S.; Breuer, H.; Flanders, B. S.; Khandaker, M. A.; Naples, D. L.; Zhang, D.; Barlett, M. L.; Hoffmann, G. W.; Purcell, M.

1990-10-01

Analyzing powers for the reaction π-p-->-->π0n were measured at an incident pion energy of T-π=161 MeV with a transversely polarized proton target over the angular range of about 20°-60°. The results are well described by calculations based on current sets of πN phase shifts.

Immune Reconstitution Reactions in Human Immunodeficiency Virus–Negative Patients

PubMed Central

Scharschmidt, Tiffany C.; Amerson, Erin H.; Rosenberg, Oren S.; Jacobs, Richard A.; McCalmont, Timothy H.; Shinkai, Kanade

2013-01-01

Background Immune reconstitution inflammatory syndrome (IRIS) is a phenomenon initially described in patients with human immunodeficiency virus. Upon initiation of combination antiretroviral therapy, recovery of cellular immunity triggers inflammation to a preexisting infection or antigen that causes paradoxical worsening of clinical disease. A similar phenomenon can occur in human immunodeficiency virus–negative patients, including pregnant women, neutropenic hosts, solidorgan or stem cell transplant recipients, and patients receiving tumor necrosis factor inhibitors. Observations We report a case of leprosy unmasking and downgrading reaction after stem cell transplantation that highlights some of the challenges inherent to the diagnosis of IRIS, especially in patients without human immunodeficiency virus infection, as well as review the spectrum of previously reported cases of IRIS reactions in this population. Conclusions The mechanism of immune reconstitution reactions is complex and variable, depending on the underlying antigen and the mechanism of immunosuppression or shift in immune status. Use of the term IRIS can aid our recognition of an important phenomenon that occurs in the setting of immunosuppression or shifts in immunity but should not deter us from thinking critically about the distinct processes that underlie this heterogeneous group of conditions. PMID:23324760

Effect of the Gouy phase on the coherent phase control of chemical reactions.

PubMed

Gordon, Robert J; Barge, Vishal J

2007-11-28

We show how the spatial phase of a focused laser beam may be used as a tool for controlling the branching ratio of a chemical reaction. Guoy discovered [Acad. Sci., Paris, C. R. 110, 1250 (1890)] that when an electromagnetic wave passes through a focus its phase increases by pi. In a coherent control scheme involving the absorption of n photons of frequency omega(m) and m photons of frequency omega(n), the overall phase shift produced by the Gouy phase is (n-m)pi. At any given point in space, this phase shift is identical for all reaction products. Nevertheless, if the yields for different reaction channels have different intensity dependencies, the Gouy phase produces a net phase lag between the products that varies with the axial coordinate of the laser focus. We obtain here analytical and numerical values of this phase as the laser focus is scanned across the diameter of the molecular beam, taking into account the Rayleigh range and astigmatism of the laser beam and saturation of the transition. We also show that the modulation depth of the interference pattern may be increased by optimizing the relative intensities of the two fields.

Flight controller alertness and performance during spaceflight shiftwork operations.

PubMed

Kelly, S M; Rosekind, M R; Dinges, D F; Miller, D L; Gillen, K A; Gregory, K B; Aguilar, R D; Smith, R M

1998-09-01

Decreased alertness and performance associated with fatigue, sleep loss, and circadian disruption are issues faced by a diverse range of shiftwork operations personnel. During Space Transportation System (STS) operations, Mission Operations Directorate (MOD) personnel provide 24-hr. coverage of critical tasks. A joint NASA Johnson Space Center and NASA Ames Research Center project was undertaken to examine these issues in flight controllers during MOD shiftwork operations. An initial operational test of procedures and measures was conducted during the STS-53 mission in December 1992. The study measures included a Background Questionnaire, a subjective daily logbook completed on a 24-hour basis (to report sleep patterns, work periods, etc.), and an 8 minute performance and mood test battery administered at the beginning, middle, and end of each shift period. Seventeen flight controllers representing the 3 Orbit shifts participated. The initial results clearly support the need for further data collection during other STS missions to document baseline levels of alertness and performance during MOD shiftwork operations. Countermeasure strategies specific to the MOD environment are being developed to minimize the adverse effects of fatigue, sleep loss, and circadian disruption engendered by shiftwork operations. These issues are especially pertinent for the night shift operations and the acute phase advance required for the transition of day shift personnel into the night for shuttle launch. Implementation and evaluation of the countermeasure strategies to maximize alertness and performance is planned. As STS missions extend to further EDO (extended duration orbiters), and timelines and planning for 24-hour Space Station operations continue, alertness and performance issues related to sleep and circadian disruption will remain highly relevant in the MOD environment.

Optimizing Fire Department Operations Through Work Schedule Analysis, Alternative Staffing, and Nonproductive Time Reduction

DTIC Science & Technology

2014-09-01

hour work shift. A longer shift offers more time off between shifts, which can improve the employee’s family life , and personal emotional stress . On...Enhancing Work / Life Balance ,” Conn.L.Rev. 42 (2010): 1081–1527. 19 Nicole Jansen et al., “Need for Recovery from Work : Evaluating Short-Term Effects...24-hour work shift. A longer shift offers more time off between shifts that can improve the employee’s family life and personal emotional stress

Reward Sensitivity and Waiting Impulsivity: Shift towards Reward Valuation away from Action Control

PubMed Central

Mechelmans, Daisy J; Strelchuk, Daniela; Doñamayor, Nuria; Banca, Paula; Robbins, Trevor W; Baek, Kwangyeol

2017-01-01

Abstract Background Impulsivity and reward expectancy are commonly interrelated. Waiting impulsivity, measured using the rodent 5-Choice Serial Reaction Time task, predicts compulsive cocaine seeking and sign (or cue) tracking. Here, we assess human waiting impulsivity using a novel translational task, the 4-Choice Serial Reaction Time task, and the relationship with reward cues. Methods Healthy volunteers (n=29) performed the monetary incentive delay task as a functional MRI study where subjects observe a cue predicting reward (cue) and wait to respond for high (£5), low (£1), or no reward. Waiting impulsivity was tested with the 4-Choice Serial Reaction Time task. Results For high reward prospects (£5, no reward), greater waiting impulsivity on the 4-CSRT correlated with greater medial orbitofrontal cortex and lower supplementary motor area activity to cues. In response to high reward cues, greater waiting impulsivity was associated with greater subthalamic nucleus connectivity with orbitofrontal cortex and greater subgenual cingulate connectivity with anterior insula, but decreased connectivity with regions implicated in action selection and preparation. Conclusion These findings highlight a shift towards regions implicated in reward valuation and a shift towards compulsivity away from higher level motor preparation and action selection and response. We highlight the role of reward sensitivity and impulsivity, mechanisms potentially linking human waiting impulsivity with incentive approach and compulsivity, theories highly relevant to disorders of addiction. PMID:29020291

Majority Group Members' Negative Reactions to Future Demographic Shifts Depend on the Perceived Legitimacy of Their Status: Findings from the United States and Portugal.

PubMed

Outten, H Robert; Lee, Timothy; Costa-Lopes, Rui; Schmitt, Michael T; Vala, Jorge

2018-01-01

Using concepts from social identity theory (Tajfel and Turner, 1979), we examined whether racial/ethnic majority group members' reactions to future demographic shifts is a function of the degree to which they perceive their ingroup's higher-status in society to be legitimate. In two studies, participants who varied in the degree to which they perceived their group's status to be legitimate were either exposed to real projections for 2060 (i.e., large decline in proportion of population that is the "majority" group), or fake projections for 2060-that resembled current figures (i.e., small decline). In Study 1, White Americans who perceived their status to be highly legitimate expressed greater intergroup threat, and negative feelings (anger and fear) toward minorities after exposure to projections with a large decline in the relative size of the White American population. In contrast, demographic shift condition had no effect on intergroup threat and negative feelings toward minorities among White Americans who perceived their status to be relatively illegitimate; negative feelings and threat remained low across both conditions. Similarly, in Study 2, ethnic Portuguese people in Portugal exposed to projections in which there was a large decline in the relative size of the ethnic Portuguese population experienced more intergroup threat and expressed a greater desire to engage in anti-immigration behaviors. The effect of demographic shift condition on intergroup threat and anti-immigration behaviors was stronger among ethnic Portuguese who perceived their status to be legitimate compared to ethnic Portuguese people who perceived their status to be relatively illegitimate. These results highlight that across different cultural contexts, majority group members' beliefs about the legitimacy of intergroup relations can affect their reactions to the prospect of increased diversity.

Hydricity-promoted [1,5]-H shifts in acetalic ketenimines and carbodiimides.

PubMed

Alajarín, Mateo; Bonillo, Baltasar; Ortín, María-Mar; Sánchez-Andrada, Pilar; Vidal, Angel

2006-11-23

2-monosubstituted 1,3-dioxolanes and dithiolanes act as hydride-releasing fragments, transferring intramolecularly their acetalic H atom to the central carbon of ketenimine functions. The presumed products of these migrations, o-quinomethanimines, undergo in situ 6pi-electrocyclization. A computational study supports this mechanism and the hydride-shift character of the first step. Carbodiimides were also suitable substrates, although less reactive. [reaction: see text].

Two-stage coal liquefaction without gas-phase hydrogen

DOEpatents

Stephens, H.P.

1986-06-05

A process is provided for the production of a hydrogen-donor solvent useful in the liquefaction of coal, wherein the water-gas shift reaction is used to produce hydrogen while simultaneously hydrogenating a donor solvent. A process for the liquefaction of coal using said solvent is also provided. The process enables avoiding the use of a separate water-gas shift reactor as well as high pressure equipment for liquefaction. 3 tabs.

A combined mechanistic and computational study of the gold(I)-catalyzed formation of substituted indenes.

PubMed

Nun, Pierrick; Gaillard, Sylvain; Poater, Albert; Cavallo, Luigi; Nolan, Steven P

2011-01-07

Substituted indenes can be prepared after a sequence [1,3] O-acyl shift-hydroarylation-[1,3] O-acyl shift. Each step is catalyzed by a cationic NHC-Gold(I) species generated in situ after reaction between [(IPr)AuOH] and HBF(4)·OEt(2). This interesting silver-free way is fully supported by a computational study justifying the formation of each intermediate.

The 1,2-hydrogen shift reaction for monohalogenophosphanes PH2X and HPX (X = F, Cl)

NASA Astrophysics Data System (ADS)

Viana, Rommel B.; Varela, Jaldyr J. G., Jr.; Tello, Ana C. M.; Savedra, Ranylson M. L.; da Silva, Albérico B. F.

2016-10-01

The aim of the present study was to perform a quantum chemical investigation in the 1,2-hydrogen shift reaction for the PH2X and HPX molecules (X = F,Cl). Several phosphorus-halogen-bearing molecules were studied, including PH2F, PH2Cl, HPF, HPCl, HPFH, HPClH, PFH and PClH. The energies of stationary and saddle points on the ground electronic potential energy surface were investigated with post-Hartree-Fock methods [CCSD(T), MP2, QCISD] and different DFT functionals. The PH2F 1,2-hydrogen shift energy barrier was 75 kcal mol-1 at the CCSD(T) level and only a small increase in this value was observed for the HPF isomerisation. In contrast, the HPCl 1,2-hydrogen shift barrier is higher than the PH2Cl one, which presented a barrier height of 69 kcal mol-1 among CCSD(T) and composite methods. The rate constants of these unimolecular rearrangements varied from 10-44 to 10-38 s-1, and these isomerisation channels exhibited large half-lives. In addition, the heat of formation of each monohalogenophosphane was also calculated. The Quantum Theory of Atoms in Molecules (QTAIM) and Natural Bond Orbital (NBO) analysis were also employed to characterise the differences between the phosphorous-halogen bonds.

Right hemispheric dominance in gaze-triggered reflexive shift of attention in humans.

PubMed

Okada, Takashi; Sato, Wataru; Toichi, Motomi

2006-11-01

Recent findings suggest a right hemispheric dominance in gaze-triggered shifts of attention. The aim of this study was to clarify the dominant hemisphere in the gaze processing that mediates attentional shift. A target localization task, with preceding non-predicative gaze cues presented to each visual field, was undertaken by 44 healthy subjects, measuring reaction time (RT). A face identification task was also given to determine hemispheric dominance in face processing for each subject. RT differences between valid and invalid cues were larger when presented in the left rather than the right visual field. This held true regardless of individual hemispheric dominance in face processing. Together, these results indicate right hemispheric dominance in gaze-triggered reflexive shifts of attention in normal healthy subjects.

Evolution of the composition, structure, and piezoelectric performance of (K1-xNax)NbO3 nanorod arrays with hydrothermal reaction time

NASA Astrophysics Data System (ADS)

Jin, Wenchao; Wang, Zhao; Li, Meng; He, Yahua; Hu, Xiaokang; Li, Luying; Gao, Yihua; Hu, Yongming; Gu, Haoshuang; Wang, Xiaolin

2018-04-01

Lead-free (K,Na)NbO3 (KNN) nanorod arrays were synthesized with the assistance of a Nb: SrTiO3 single-crystal substrate through the hydrothermal process. The evolutions of the morphology, composition, and structure of the as-synthesized KNN nanorods with the increase in reaction time were investigated. The results confirmed that the increase in reaction time up to 3 h led to the increase in the length and aspect ratio of the well-aligned KNN nanorods. All samples have K-rich orthorhombic crystal structures, while the diffraction peaks shifted towards a higher degree. The peak shifts should be attributed to the increase in the Na content in the KNN lattice, which could decrease the lattice parameters owing to the small ionic radius of Na+ than that of K+. Moreover, the increase in reaction time also resulted in the suppression of oxygen vacancies on the surface of the KNN nanorods. These evolutions of the composition and crystal structure, as well as the decrease in the defect content, lead to great enhancement of the nanorod's piezoelectric response, as their d33 value was increased from 19 to 64 pm/V. These results demonstrated the significant impact of reaction time on the hydrothermal growth of high-performance lead-free KNN one-dimensional nanomaterials.

Using Perovskite Nanoparticles as Halide Reservoirs in Catalysis and as Spectrochemical Probes of Ions in Solution

DOE PAGES

Doane, Tennyson L.; Ryan, Kayla L.; Pathade, Laxmikant; ...

2016-05-05

The ability of cesium lead halide (CsPbX 3; X = Cl –, Br –, I –) perovskite nanoparticles (P-NPs) to participate in halide exchange reactions, to catalyze Finkelstein organohalide substitution reactions, and to colorimetrically monitor chemical reactions and detect anions in real time is described. With the use of tetraoctylammonium halide salts as a starting point, halide exchange with the P-NPs was performed to calibrate reactivity, stability, and extent of ion exchange. Also, the exchange of CsPbI 3 with Cl – or Br – causes a significant blue-shift in absorption and photoluminescence, whereas reacting I – with CsPbBr 3 causesmore » a red-shift of similar magnitudes. With the high local halide concentrations and the facile nature of halide exchange in mind, we then explored the ability of P-NPs to catalyze organohalide exchange in Finkelstein like reactions. Results indicate that the P-NPs serve as excellent halide reservoirs for substitution of organohalides in nonpolar media, leading to not only different organohalide products, but also a complementary color change over the course of the reaction, which can be used to monitor kinetics in a precise manner. Finally, the merits of using P-NP as spectrochemical probes for real time assaying is then expanded to other anions which can react with, or result in unique, classes of perovskites.« less

Investigation of reactions in a fluidized bed reactor during chemical looping combustion of coal/steam with copper oxide-iron oxide-alumina oxygen carrier

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siriwardane, Ranjani; Benincosa, William; Riley, Jarrett

This paper presents data on conversion of two different coals with a chemical looping oxygen carrier, CuO-Fe 2O 3-alumina, and over a range of conditions including steam and various levels of reduction of the oxygen carrier. Reactions of coal/steam/CuO-Fe 2O 3-alumina oxygen carrier and coal/steam/partially reduced CuO-Fe 2O 3-alumina oxygen carrier were investigated with Wyodak coal and Illinois #6 coal in a fluidized bed reactor. Temperature programmed reaction studies indicated that the oxygen carrier enhanced the steam gasification/combustion rates of both coals. Rates of gasification/combustion were higher with Wyodak coal (sub bituminous) than that with Illinois #6 coal (bituminous). Inmore » addition to the increase in reaction rates, the total moles of carbon that were gasified and combusted from coal/steam increased in the presence of the oxygen carrier. The reduced oxygen carrier promoted the water-gas shift reaction when reacted with synthesis gas in the presence of steam, but the reverse water gas shift reaction was observed when steam was not present. The partially reduced oxygen carrier enhanced the production of H 2 from coal/steam, which was different from the observations with un-reduced oxygen carrier. Water splitting reaction to produce H 2 was also observed with the reduced oxygen carrier. CuO-Fe 2O 3-alumina reacted with coal during the temperature ramp to 850 °C even in the absence of steam due to the chemical-looping oxygen uncoupling (CLOU) reaction. Here, the fourier transform infra-red (FTIR) analysis indicated the presence of volatile aromatics during the temperature ramp and these may have also contributed to the reactions with the oxygen carrier in the absence of steam. Increasing steam concentration had a negative effect on the CLOU reaction.« less

Investigation of reactions in a fluidized bed reactor during chemical looping combustion of coal/steam with copper oxide-iron oxide-alumina oxygen carrier

DOE PAGES

Siriwardane, Ranjani; Benincosa, William; Riley, Jarrett; ...

2016-10-06

This paper presents data on conversion of two different coals with a chemical looping oxygen carrier, CuO-Fe 2O 3-alumina, and over a range of conditions including steam and various levels of reduction of the oxygen carrier. Reactions of coal/steam/CuO-Fe 2O 3-alumina oxygen carrier and coal/steam/partially reduced CuO-Fe 2O 3-alumina oxygen carrier were investigated with Wyodak coal and Illinois #6 coal in a fluidized bed reactor. Temperature programmed reaction studies indicated that the oxygen carrier enhanced the steam gasification/combustion rates of both coals. Rates of gasification/combustion were higher with Wyodak coal (sub bituminous) than that with Illinois #6 coal (bituminous). Inmore » addition to the increase in reaction rates, the total moles of carbon that were gasified and combusted from coal/steam increased in the presence of the oxygen carrier. The reduced oxygen carrier promoted the water-gas shift reaction when reacted with synthesis gas in the presence of steam, but the reverse water gas shift reaction was observed when steam was not present. The partially reduced oxygen carrier enhanced the production of H 2 from coal/steam, which was different from the observations with un-reduced oxygen carrier. Water splitting reaction to produce H 2 was also observed with the reduced oxygen carrier. CuO-Fe 2O 3-alumina reacted with coal during the temperature ramp to 850 °C even in the absence of steam due to the chemical-looping oxygen uncoupling (CLOU) reaction. Here, the fourier transform infra-red (FTIR) analysis indicated the presence of volatile aromatics during the temperature ramp and these may have also contributed to the reactions with the oxygen carrier in the absence of steam. Increasing steam concentration had a negative effect on the CLOU reaction.« less

Agile Science Operations: A New Approach for Primitive Exploration Bodies

NASA Technical Reports Server (NTRS)

Chien, Steve A.; Thompson, David R.; Castillo-Rogez, Julie C.; Doyle, Richard; Estlin, Tara; Mclaren, David

2012-01-01

Primitive body exploration missions such as potential Comet Surface Sample Return or Trojan Tour and Rendezvous would challenge traditional operations practices. Earth-based observations would provide only basic understanding before arrival and many science goals would be defined during the initial rendezvous. It could be necessary to revise trajectories and observation plans to quickly characterize the target for safe, effective observations. Detection of outgassing activity and monitoring of comet surface activity are even more time constrained, with events occurring faster than round-trip light time. "Agile science operations" address these challenges with contingency plans that recognize the intrinsic uncertainty in the operating environment and science objectives. Planning for multiple alternatives can significantly improve the time required to repair and validate spacecraft command sequences. When appropriate, time-critical decisions can be automated and shifted to the spacecraft for immediate access to instrument data. Mirrored planning systems on both sides of the light-time gap permit transfer of authority back and forth as needed. We survey relevant science objectives, identifying time bottlenecks and the techniques that could be used to speed missions' reaction to new science data. Finally, we discuss the results of a trade study simulating agile observations during flyby and comet rendezvous scenarios. These experiments quantify instrument coverage of key surface features as a function of planning turnaround time. Careful application of agile operations techniques can play a significant role in realizing the Decadal Survey plan for primitive body exploration

Aging and shiftwork: the effects of 20 years of rotating 12-hour shifts among petroleum refinery operators.

PubMed

Bourdouxhe, M A; Quéinnec, Y; Granger, D; Baril, R H; Guertin, S C; Massicotte, P R; Levy, M; Lemay, F L

1999-01-01

The survey was conducted in a Canadian refinery where operators have been working rotating 12-hour shifts for 20 years. A multidisciplinary approach was adopted, based on 12 sources of data. Descriptive statistics and chronoergonomic observations were used. The most marked consequences of the schedule were observed among former shiftworkers. Among current shift workers, sleep deficit, chronic fatigue, health problems, and disruption of social and family life were the most serious effects observed. Aging and under-staffing, however, interact with schedule by necessitating overtime and reducing the actual number of rest days, which in turn affects fatigue and reliability. In the near future, the low replacement rate of the workforce and the limitations on reassignment of aging workers to day shifts will probably prevent the selection process from playing its "protective" role. Besides, with the 5-year delay of the retirement age, the harmful effects in older operators active over the next 5-10 years may prove greater than those observed in this study.

One-pot synthesis of keto thioethers by palladium/gold-catalyzed click and pinacol reactions.

PubMed

Cadu, Alban; Watile, Rahul A; Biswas, Srijit; Orthaber, Andreas; Sjöberg, Per J R; Samec, Joseph S M

2014-11-07

An atom-efficient synthesis of keto thioethers was devised via tandem gold/palladium catalysis. The reaction proceeds through a regioselective thiol attack at the β-position of the alcohol, followed by an alkyl, aryl, or benzyl 1,2-shift. Both acyclic and cyclic systems were studied, in the latter case leading to the ring expansion of cyclic substrates.

SurfKin: an ab initio kinetic code for modeling surface reactions.

PubMed

Le, Thong Nguyen-Minh; Liu, Bin; Huynh, Lam K

2014-10-05

In this article, we describe a C/C++ program called SurfKin (Surface Kinetics) to construct microkinetic mechanisms for modeling gas-surface reactions. Thermodynamic properties of reaction species are estimated based on density functional theory calculations and statistical mechanics. Rate constants for elementary steps (including adsorption, desorption, and chemical reactions on surfaces) are calculated using the classical collision theory and transition state theory. Methane decomposition and water-gas shift reaction on Ni(111) surface were chosen as test cases to validate the code implementations. The good agreement with literature data suggests this is a powerful tool to facilitate the analysis of complex reactions on surfaces, and thus it helps to effectively construct detailed microkinetic mechanisms for such surface reactions. SurfKin also opens a possibility for designing nanoscale model catalysts. Copyright © 2014 Wiley Periodicals, Inc.

Pilot interaction with automated airborne decision making systems

NASA Technical Reports Server (NTRS)

Hammer, John M.

1990-01-01

Ways in which computers can aid the decision making of an human operator of an aerospace system are investigated. The approach taken is to aid rather than replace the human operator, because operational experience has shown that humans can enhance the effectiveness of systems. As systems become more automated, the role of the operator has shifted to that of a manager and problem solver. This shift has created the research area of how to aid the human in this role. Published research in four areas is described. A discussion is presented of the DC-8 flight simulator at Georgia Tech.

Cycom 977-2 Composite Material: Impact Test Results

NASA Technical Reports Server (NTRS)

Engel, Carl D.; Herald, Stephen; Watkins, Casey

2005-01-01

The reaction frequency data from 13A testing by MSFC and WSTF appear well behaved for the sample number used by each and exhibit the same type of energy level dependency. The reaction frequency shift in energy level is unexplained at this time. All the 13A data suggest that only a small amount of material is consumed when reactions take place. At ambient pressure, most of not all reactions are quenched as indicated by the small mass loss. As test pressure is increased in LOX using 13B results. Cycom does not support initiation of reactions or propagations of reactions in GOX at 100 psis based on tests at MSFC and WSTF at 72 ft-lb impact energy. No batch effect was identified in LOX or GOX.

Quantum displacement receiver for M-ary phase-shift-keyed coherent states

DOE Office of Scientific and Technical Information (OSTI.GOV)

Izumi, Shuro; Takeoka, Masahiro; Fujiwara, Mikio

2014-12-04

We propose quantum receivers for 3- and 4-ary phase-shift-keyed (PSK) coherent state signals to overcome the standard quantum limit (SQL). Our receiver, consisting of a displacement operation and on-off detectors with or without feedforward, provides an error probability performance beyond the SQL. We show feedforward operations can tolerate the requirement for the detector specifications.

Synthesis of cyclopentadiene-fused chromanones via one-pot multicomponent reactions.

PubMed

Ghandi, Mehdi; Ghomi, Ali-Tabatabaei; Kubicki, Maciej

2013-03-15

We have developed one-pot method for the synthesis of functionalized novel cyclopentadiene-fused chromanone scaffolds. A variety of 4-oxo-2,4-dihydrocyclopenta[c]chromene-1,2-dicarboxylates were obtained in moderate to good yields via condensation of 2-hydroxybenzaldehydes and ethyl acetoacetate with 1:1 acetylenecarboxylate-isocyanides in toluene. These reactions presumably proceed via reaction of the in situ generated 3-acetyl-2H-chromen-2-ones with acetylenecarboxylate-isocyanide zwitterionic intermediates through Michael addition/intramolecular cyclization and double [1,5] acyl shift rearrangement cascade.

[Analysis of relationship between shift-work and occupational stress among workers from different companies].

PubMed

Gu, Guizhen; Yu, Shanfa; Zhou, Wenhui; Wu, Hui

2016-01-01

To investigate the relationship between work in shifts and occupational stress. A total of 5338 employees from 13 companies were investigated by cluster sampling, and occupational stress measuring tools, job content questionnaire, and effort-reward imbalance questionnaire were used to investigate occupational stress factors, stress reaction, and the condition of work in shifts. The employees who worked in shifts accounted for 46.6%. The condition of work in shifts varied significantly across different companies, employees with different individual features (including sex, job title, degree of education, age, working years, smoking, and drinking), and employees with different weekly working times(P<0.01 or P<0.05); health status was associated with work in shifts(P<0.01); compared with the employees who did not work in shifts, those who worked in shifts had significantly lower scores of technology utilization, work control level, psychological need, reward, social support, and job satisfaction(P<0.01 or P<0.05), as well as significantly higher scores of physical demands, effort, depressive symptoms, and negative affectivity(P<0.01). Work in shifts can affect health status, and is associated with occupational stress.

Anticipating the reaction: public concern about sample return missions

NASA Technical Reports Server (NTRS)

Race, M. S.

1994-01-01

Shifts in public attitude that may affect extraterrestrial sample return include increased public participation in the legal and regulatory environment, institutionalized public vigilance, politicization of technological debates and shifts in the nature of public decision-making, and a risk-averse public accustomed to mass media coverage that focuses on hazards and disasters. The ice-minus recombinant DNA experiment is used as an example of the effects of public opinion on scientific experimentation.

The ALICE Glance Shift Accounting Management System (SAMS)

NASA Astrophysics Data System (ADS)

Martins Silva, H.; Abreu Da Silva, I.; Ronchetti, F.; Telesca, A.; Maidantchik, C.

2015-12-01

ALICE (A Large Ion Collider Experiment) is an experiment at the CERN LHC (Large Hadron Collider) studying the physics of strongly interacting matter and the quark-gluon plasma. The experiment operation requires a 24 hours a day and 7 days a week shift crew at the experimental site, composed by the ALICE collaboration members. Shift duties are calculated for each institute according to their correlated members. In order to ensure the full coverage of the experiment operation as well as its good quality, the ALICE Shift Accounting Management System (SAMS) is used to manage the shift bookings as well as the needed training. ALICE SAMS is the result of a joint effort between the Federal University of Rio de Janeiro (UFRJ) and the ALICE Collaboration. The Glance technology, developed by the UFRJ and the ATLAS experiment, sits at the basis of the system as an intermediate layer isolating the particularities of the databases. In this paper, we describe the ALICE SAMS development process and functionalities. The database has been modelled according to the collaboration needs and is fully integrated with the ALICE Collaboration repository to access members information and respectively roles and activities. Run, period and training coordinators can manage their subsystem operation and ensure an efficient personnel management. Members of the ALICE collaboration can book shifts and on-call according to pre-defined rights. ALICE SAMS features a user profile containing all the statistics and user contact information as well as the Institutes profile. Both the user and institute profiles are public (within the scope of the collaboration) and show the credit balance in real time. A shift calendar allows the Run Coordinator to plan data taking periods in terms of which subsystems shifts are enabled or disabled and on-call responsible people and slots. An overview display presents the shift crew present in the control room and allows the Run Coordination team to confirm the presence of both regular and trainees shift personnel, necessary for credit accounting.

Intermodal transport and distribution patterns in ports relationship to hinterland

NASA Astrophysics Data System (ADS)

Dinu, O.; Dragu, V.; Ruscă, F.; Ilie, A.; Oprea, C.

2017-08-01

It is of great importance to examine all interactions between ports, terminals, intermodal transport and logistic actors of distribution channels, as their optimization can lead to operational improvement. Proposed paper starts with a brief overview of different goods types and allocation of their logistic costs, with emphasis on storage component. Present trend is to optimize storage costs by means of port storage area buffer function, by making the best use of free storage time available, most of the ports offer. As a research methodology, starting point is to consider the cost structure of a generic intermodal transport (storage, handling and transport costs) and to link this to intermodal distribution patterns most frequently cast-off in port relationship to hinterland. The next step is to evaluate storage costs impact on distribution pattern selection. For a given value of port free storage time, a corresponding value of total storage time in the distribution channel can be identified, in order to substantiate a distribution pattern shift. Different scenarios for transport and handling costs variation, recorded when distribution pattern shift, are integrated in order to establish the reaction of the actors involved in port related logistic and intermodal transport costs evolution is analysed in order to optimize distribution pattern selection.

Doping Li and K into Na2ZrO3 Sorbent to Improve Its CO2 Capture Capability

NASA Astrophysics Data System (ADS)

Duan, Yuhua

Carbon dioxide is one of the major combustion products which once released into the air can contribute to global climate change. Solid sorbents have been reported in several previous studies to be promising candidates for CO2 sorbent applications due to their high CO2 absorption capacities at moderate working temperatures. However, at a given CO2 pressure, the turnover temperature (Tt) of an individual solid capture CO2 reaction is fixed and may be outside the operating temperature range (ΔTo) for a particularly capture technology. In order to shift such Tt for a solid into the range of ΔTo, its corresponding thermodynamic property must be changed by changing its structure by reacting (mixing) with other materials or doping with other elements. As an example, by combining thermodynamic database searching with ab initio thermodynamics calculations, in this work, we explored the Li- and K-doping effects on the Tt shifts of Na2ZrO3 at different doping levels. The obtained results showed that compared to pure Na2ZrO3, the Li- and K-doped mixtures Na2-αMαZrO3 (M =Li, K) have lower Tt and higher CO2 capture capacities.

Thermal analysis of cylindrical natural-gas steam reformer for 5 kW PEMFC

NASA Astrophysics Data System (ADS)

Jo, Taehyun; Han, Junhee; Koo, Bonchan; Lee, Dohyung

2016-11-01

The thermal characteristics of a natural-gas based cylindrical steam reformer coupled with a combustor are investigated for the use with a 5 kW polymer electrolyte membrane fuel cell. A reactor unit equipped with nickel-based catalysts was designed to activate the steam reforming reaction without the inclusion of high-temperature shift and low-temperature shift processes. Reactor temperature distribution and its overall thermal efficiency depend on various inlet conditions such as the equivalence ratio, the steam to carbon ratio (SCR), and the fuel distribution ratio (FDR) into the reactor and the combustor components. These experiments attempted to analyze the reformer's thermal and chemical properties through quantitative evaluation of product composition and heat exchange between the combustor and the reactor. FDR is critical factor in determining the overall performance as unbalanced fuel injection into the reactor and the combustor deteriorates overall thermal efficiency. Local temperature distribution also influences greatly on the fuel conversion rate and thermal efficiency. For the experiments, the operation conditions were set as SCR was in range of 2.5-4.0 and FDR was in 0.4-0.7 along with equivalence ratio of 0.9-1.1; optimum results were observed for FDR of 0.63 and SCR of 3.0 in the cylindrical steam reformer.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Xin-Ping, E-mail: xuxp@mail.ihep.ac.cn; Ide, Yusuke

In the literature, there are numerous studies of one-dimensional discrete-time quantum walks (DTQWs) using a moving shift operator. However, there is no exact solution for the limiting probability distributions of DTQWs on cycles using a general coin or swapping shift operator. In this paper, we derive exact solutions for the limiting probability distribution of quantum walks using a general coin and swapping shift operator on cycles for the first time. Based on the exact solutions, we show how to generate symmetric quantum walks and determine the condition under which a symmetric quantum walk appears. Our results suggest that choosing various coinmore » and initial state parameters can achieve a symmetric quantum walk. By defining a quantity to measure the variation of symmetry, deviation and mixing time of symmetric quantum walks are also investigated.« less

Concurrent error detecting codes for arithmetic processors

NASA Technical Reports Server (NTRS)

Lim, R. S.

1979-01-01

A method of concurrent error detection for arithmetic processors is described. Low-cost residue codes with check-length l and checkbase m = 2 to the l power - 1 are described for checking arithmetic operations of addition, subtraction, multiplication, division complement, shift, and rotate. Of the three number representations, the signed-magnitude representation is preferred for residue checking. Two methods of residue generation are described: the standard method of using modulo m adders and the method of using a self-testing residue tree. A simple single-bit parity-check code is described for checking the logical operations of XOR, OR, and AND, and also the arithmetic operations of complement, shift, and rotate. For checking complement, shift, and rotate, the single-bit parity-check code is simpler to implement than the residue codes.

Individual differences in choice (in)flexibility but not impulsivity in the common marmoset: an automated, operant-behavior choice task.

PubMed

Adriani, Walter; Romani, Chiara; Manciocco, Arianna; Vitale, Augusto; Laviola, Giovanni

2013-11-01

Individual differences in behavioural flexibility are a significant issue in human psychopathology as well as in its animal models. We aimed to investigate individual variations of operant-choice behaviour in the common marmoset (Callithrix jacchus), a small New World primate, using a new operant panel with two hand-poking holes. Experimental subjects (N=16) were presented with a choice between a Small & Soon (SS) vs a Large & Late (LL) food reward. After extensive training (31 daily sessions with no delay, during which a basal, large-reward preference developed), the delay before release of LL was progressively increased (from 0 to 60 s, during 16 daily sessions; indifferent point at delay=9 s). Subjects were classified as either "flexible" or "non-flexible", respectively, based on a decrease (or not) in the preference for LL with increasing delays. Each subject was also classified as "maximizer" (or "non-maximizer") based on capacity (or not) to maximize the food payoff as delay increased. Upon delays shorter than the indifferent point (<9s), none of the subjects showed a shift from LL to SS, denoting a lack of delay-induced, cognitive impulsivity. Individual differences only emerged upon delays longer than the indifferent point (>9 s), when a preference shift could be interpreted as economically-driven. In general, a profile of few unrewarded hand-pokes in reaction to initial delays (i.e., a low motor impulsivity) and of clear-cut basal LL preference seemed to predict elevated flexibility of choices and better food payoff, which was typical of subjects classified as both "flexible & maximizer". These results provide normative data on the marmosets, which can be used as a model for the investigation of 1) individual differences in behavioural flexibility, as well as 2) biological mechanisms rooted in our evolutionary history. Copyright © 2013 Elsevier B.V. All rights reserved.

Advanced investigation of two-phase charge-coupled devices

NASA Technical Reports Server (NTRS)

Kosonocky, W. F.; Carnes, J. E.

1973-01-01

The performance of experimental two phase, charge-coupled shift registers constructed using polysilicon gates overlapped by aluminum gates was studied. Shift registers with 64, 128, and 500 stages were built and operated. Devices were operated at the maximum clock frequency of 20 MHz. Loss per transfer of less than .0001 was demonstrated for fat zero operation. The effect upon transfer efficiency of various structural and materials parameters was investigated including substrate orientation, resistivity, and conductivity type; channel width and channel length; and method of channel confinement. Operation of the devices with and without fat zero was studied as well as operation in the complete charge transfer mode and the bias charge, or bucket brigade mode.

Ultrafast Electron Transfer Kinetics in the LM Dimer of Bacterial Photosynthetic Reaction Center from Rhodobacter sphaeroides.

PubMed

Sun, Chang; Carey, Anne-Marie; Gao, Bing-Rong; Wraight, Colin A; Woodbury, Neal W; Lin, Su

2016-06-23

It has become increasingly clear that dynamics plays a major role in the function of many protein systems. One system that has proven particularly facile for studying the effects of dynamics on protein-mediated chemistry is the bacterial photosynthetic reaction center from Rhodobacter sphaeroides. Previous experimental and computational analysis have suggested that the dynamics of the protein matrix surrounding the primary quinone acceptor, QA, may be particularly important in electron transfer involving this cofactor. One can substantially increase the flexibility of this region by removing one of the reaction center subunits, the H-subunit. Even with this large change in structure, photoinduced electron transfer to the quinone still takes place. To evaluate the effect of H-subunit removal on electron transfer to QA, we have compared the kinetics of electron transfer and associated spectral evolution for the LM dimer with that of the intact reaction center complex on picosecond to millisecond time scales. The transient absorption spectra associated with all measured electron transfer reactions are similar, with the exception of a broadening in the QX transition and a blue-shift in the QY transition bands of the special pair of bacteriochlorophylls (P) in the LM dimer. The kinetics of the electron transfer reactions not involving quinones are unaffected. There is, however, a 4-fold decrease in the electron transfer rate from the reduced bacteriopheophytin to QA in the LM dimer compared to the intact reaction center and a similar decrease in the recombination rate of the resulting charge-separated state (P(+)QA(-)). These results are consistent with the concept that the removal of the H-subunit results in increased flexibility in the region around the quinone and an associated shift in the reorganization energy associated with charge separation and recombination.

On NMR prediction of the effectiveness of p-phenylenediamine antioxidants

NASA Astrophysics Data System (ADS)

Puškárová, Ingrid; Šoral, Michal; Breza, Martin

2015-10-01

NMR shifts of N-phenyl-N‧-alkyl-p-phenylenediamines (PPD) in DMSO have been measured as well as evaluated by B3LYP calculations. According to Simon et al. Molar Antioxidant Effectiveness (AEM) of PPD antioxidants depends on the bond strength of hydrogens to amine nitrogens between aromatic rings (NA), to the side aliphatic chain nitrogens (NB) and to its neighboring tertiary carbon atoms (CT). AEM increases with NMR shifts of HA, HB, NA and probably also of CT atoms whereas NMR shifts of NB atoms exhibit a reverse trend. This is very surprising because similar reactions at A and B sites are supposed.

Performance Evaluation of Staged Bosch Process for CO2 Reduction to Produce Life Support Consumables

NASA Technical Reports Server (NTRS)

Vilekar, Saurabh A.; Hawley, Kyle; Junaedi, Christian; Walsh, Dennis; Roychoudhury, Subir; Abney. Morgan B.; Mansell, James M.

2012-01-01

Utilizing carbon dioxide to produce water and hence oxygen is critical for sustained manned missions in space, and to support both NASA's cabin Atmosphere Revitalization System (ARS) and In-Situ Resource Utilization (ISRU) concepts. For long term missions beyond low Earth orbit, where resupply is significantly more difficult and costly, open loop ARS, like Sabatier, consume inputs such as hydrogen. The Bosch process, on the other hand, has the potential to achieve complete loop closure and is hence a preferred choice. However, current single stage Bosch reactor designs suffer from a large recycle penalty due to slow reaction rates and the inherent limitation in approaching thermodynamic equilibrium. Developmental efforts are seeking to improve upon the efficiency (hence reducing the recycle penalty) of current single stage Bosch reactors which employ traditional steel wool catalysts. Precision Combustion, Inc. (PCI), with support from NASA, has investigated the potential for utilizing catalysts supported over short-contact time Microlith substrates for the Bosch reaction to achieve faster reaction rates, higher conversions, and a reduced recycle flows. Proof-of-concept testing was accomplished for a staged Bosch process by splitting the chemistry in two separate reactors, first being the reverse water-gas-shift (RWGS) and the second being the carbon formation reactor (CFR) via hydrogenation and/or Boudouard. This paper presents the results from this feasibility study at various operating conditions. Additionally, results from two 70 hour durability tests for the RWGS reactor are discussed.

Shaping-lathe headrig yields solid and molded-flake hardwood products.

Treesearch

P. Koch; R.A. Caughey

1978-01-01

A shaping-lathe headrig, operated one shift daily, can be used to manufacture hardwood cants to be resawed into pallet shook, one-piece and dowel-laminated crossties, posts and rail, and other solid wood products in lengths from 6 to 9 feet. Residual flakes machined by the headrig supply a three-shift operation in which molded pallets and 4- by 8-foot sheets of...

shaping-lathe headrig yields solid and molded-flake hardwood products

Treesearch

Peter Koch; R.A. Caughey

1978-01-01

A shaping-lathe headrig, operated one shift daily, can be used to manufacture hardwood cants to be resawed into pallet shook, one-piece and dowel-laminated crossties, posts and rails, and other solid wood products in lengths from 6 to 9 feet. Residual flakes machined by the headrig supply a three-shift operation in which molded pallets and 4- by 8-foot sheets of...

The Causes of Logging Truck Delays on Two West Virginia Logging Operations

Treesearch

John E. Baumgras

1978-01-01

Logging truck downtime increases timber harvesting costs. To determine the extent and causes of truck delays, four logging trucks on two separate operations were monitored for a 7-month period by recording speedometers and with tallies of delay causes. The results show the number of truck delays per shift, their duration, and the total delay time per shift for eight...

USAFRICOM Headquarters: The Complexity of Moving the Headquarters to the Continent of Africa and its Impact on the Army’s Organizational Design and Operational Approach

DTIC Science & Technology

2016-06-10

Accountability Office, GAO-13-646. 8 Ibid. 9 Ibid. 10 British Broadcast Corporation , “US Shifts on AFRICOM Base Plans,” BBC News, 18 February...integrate from afar with such intricate circumstances in our operating environments. 62 BIBLIOGRAPHY British Broadcast Corporation . “US Shifts On AFRICOM

Interpreting anomalies observed in oxide semiconductor TFTs under negative and positive bias stress

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin, Jong Woo; Nathan, Arokia, E-mail: an299@cam.ac.uk; Barquinha, Pedro

2016-08-15

Oxide semiconductor thin-film transistors can show anomalous behavior under bias stress. Two types of anomalies are discussed in this paper. The first is the shift in threshold voltage (V{sub TH}) in a direction opposite to the applied bias stress, and highly dependent on gate dielectric material. We attribute this to charge trapping/detrapping and charge migration within the gate dielectric. We emphasize the fundamental difference between trapping/detrapping events occurring at the semiconductor/dielectric interface and those occurring at gate/dielectric interface, and show that charge migration is essential to explain the first anomaly. We model charge migration in terms of the non-instantaneous polarizationmore » density. The second type of anomaly is negative V{sub TH} shift under high positive bias stress, with logarithmic evolution in time. This can be argued as electron-donating reactions involving H{sub 2}O molecules or derived species, with a reaction rate exponentially accelerated by positive gate bias and exponentially decreased by the number of reactions already occurred.« less

Highly active Pt/MoC and Pt/TiC catalysts for the low-temperature water-gas shift reaction: Effects of the carbide metal/carbon ratio on the catalyst performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rodriguez, José A.; Ramírez, Pedro J.; Gutierrez, Ramón A.

We present that Pt/MoC and Pt/TiC(001) are excellent catalysts for the low-temperature water-gas shift (WGS, CO + H 2O → H 2 + CO 2) reaction. They exhibit high-activity, stability and selectivity. The highest catalytic activities are seen for small coverages of Pt on the carbide substrates. Synergistic effects at the metal-carbide interface produce an enhancement in chemical activity with respect to pure Pt, MoC and TiC. A clear correlation is found between the ability of the Pt/MoC and Pt/TiC(001) surfaces to partially dissociate water and their catalytic activity for the WGS reaction. Finally, an overall comparison of the resultsmore » for Pt/MoC and Pt/Mo 2C(001) indicates that the metal/carbon ratio in the carbide support can have a strong influence in the stability and selectivity of WGS catalysts and is a parameter that must be taken into consideration when designing these systems.« less

Highly sensitive on-site detection of glucose in human urine with naked eye based on enzymatic-like reaction mediated etching of gold nanorods.

PubMed

Zhang, Zhiyang; Chen, Zhaopeng; Cheng, Fangbin; Zhang, Yaowen; Chen, Lingxin

2017-03-15

Based on enzymatic-like reaction mediated etching of gold nanorods (GNRs), an ultrasensitive visual method was developed for on-site detection of urine glucose. With the catalysis of MoO 4 2 - , GNRs were efficiently etched by H 2 O 2 which was generated by glucose-glucose oxidase enzymatic reaction. The etching of GNRs lead to a blue-shift of logitudinal localized surface plasmon resonance of GNRs, accompanied by an obvious color change from blue to red. The peak-shift and the color change can be used for detection of glucose by the spectrophotometer and the naked eyes. Under optimal condition, an excellent sensitivity toward glucose is obtained with a detection limit of 0.1μM and a visual detection limit of 3μM in buffer solution. Benefiting from the high sensitivity, the successful colorimetric detection of glucose in original urine samples was achieved, which indicates the practical applicability to the on-site determination of urine glucose. Copyright © 2016 Elsevier B.V. All rights reserved.

Solvent friction changes the folding pathway of the tryptophan zipper TZ2.

PubMed

Narayanan, Ranjani; Pelakh, Leslie; Hagen, Stephen J

2009-07-17

Because the rate of a diffusional process such as protein folding is controlled by friction encountered along the reaction pathway, the speed of folding is readily tunable through adjustment of solvent viscosity. The precise relationship between solvent viscosity and the rate of diffusion is complex and even conformation-dependent, however, because both solvent friction and protein internal friction contribute to the total reaction friction. The heterogeneity of the reaction friction along the folding pathway may have subtle consequences. For proteins that fold on a multidimensional free-energy surface, an increase in solvent friction may drive a qualitative change in folding trajectory. Our time-resolved experiments on the rapidly and heterogeneously folding beta-hairpin TZ2 show a shift in the folding pathway as viscosity increases, even though the energetics of folding is unaltered. We also observe a nonlinear or saturating behavior of the folding relaxation time with rising solvent viscosity, potentially an experimental signature of the shifting pathway for unfolding. Our results show that manipulations of solvent viscosity in folding experiments and simulations may have subtle and unexpected consequences on the folding dynamics being studied.

Highly active Pt/MoC and Pt/TiC catalysts for the low-temperature water-gas shift reaction: Effects of the carbide metal/carbon ratio on the catalyst performance

DOE PAGES

Rodriguez, José A.; Ramírez, Pedro J.; Gutierrez, Ramón A.

2016-09-20

We present that Pt/MoC and Pt/TiC(001) are excellent catalysts for the low-temperature water-gas shift (WGS, CO + H 2O → H 2 + CO 2) reaction. They exhibit high-activity, stability and selectivity. The highest catalytic activities are seen for small coverages of Pt on the carbide substrates. Synergistic effects at the metal-carbide interface produce an enhancement in chemical activity with respect to pure Pt, MoC and TiC. A clear correlation is found between the ability of the Pt/MoC and Pt/TiC(001) surfaces to partially dissociate water and their catalytic activity for the WGS reaction. Finally, an overall comparison of the resultsmore » for Pt/MoC and Pt/Mo 2C(001) indicates that the metal/carbon ratio in the carbide support can have a strong influence in the stability and selectivity of WGS catalysts and is a parameter that must be taken into consideration when designing these systems.« less

Interpreting lateral dynamic weight shifts using a simple inverted pendulum model.

PubMed

Kennedy, Michael W; Bretl, Timothy; Schmiedeler, James P

2014-01-01

Seventy-five young, healthy adults completed a lateral weight-shifting activity in which each shifted his/her center of pressure (CoP) to visually displayed target locations with the aid of visual CoP feedback. Each subject's CoP data were modeled using a single-link inverted pendulum system with a spring-damper at the joint. This extends the simple inverted pendulum model of static balance in the sagittal plane to lateral weight-shifting balance. The model controlled pendulum angle using PD control and a ramp setpoint trajectory, and weight-shifting was characterized by both shift speed and a non-minimum phase (NMP) behavior metric. This NMP behavior metric examines the force magnitude at shift initiation and provides weight-shifting balance performance information that parallels the examination of peak ground reaction forces in gait analysis. Control parameters were optimized on a subject-by-subject basis to match balance metrics for modeled results to metric values calculated from experimental data. Overall, the model matches experimental data well (average percent error of 0.35% for shifting speed and 0.05% for NMP behavior). These results suggest that the single-link inverted pendulum model can be used effectively to capture lateral weight-shifting balance, as it has been shown to model static balance. Copyright © 2014 Elsevier B.V. All rights reserved.

The development of the super-biodiesel production continuously from Sunan pecan oil through the process of reactive distillation

NASA Astrophysics Data System (ADS)

Yohana, Eflita; Yulianto, Moh. Endy; Ikhsan, Diyono; Nanta, Aditya Marga; Puspitasari, Ristiyanti

2016-06-01

In general, a vegetable oil-based biodiesel production commercially operates a batch process with high investments and operational costs. Thus, it is necessary to develop super-biodiesel production from sunan pecan oil continuously through the process of reactive distillation. There are four advantages of the reactive distillation process for the biodiesel production, as follows: (i) it incorporates the process of transesterification reaction, and product separation of residual reactants become one stage of the process, so it saves the investment and operation costs, (ii) it reduces the need for raw materials because the methanol needed corresponds to the stoichiometry, so it also reduces the operation costs, (iii) the holdup time in the column is relatively short (5±0,5 minutes) compared to the batch process (1-2 hours), so it will reduce the operational production costs, and (iv) it is able to shift the reaction equilibrium, because the products and reactants that do not react are instantly separated (based on Le Chatelier's principles) so the conversion will be increased. However, the very crucial problem is determining the design tools and process conditions in order to maximize the conversion of the transesterification reaction in both phases. Thus, the purpose of this research was to design a continuous reactive distillation process by using a recycled condensate to increase the productivity of the super-biodiesel from sunan pecan oil. The research was carried out in three stages including (i) designing and fabricating the reactive distillation equipment, (ii) testing the tool performance and the optimization of the biodiesel production, and (iii) biodiesel testing on the diesel engine. These three stages were needed in designing and scaling-up the process tools and the process operation commercially. The reactive distillation process tools were designed and manufactured with reference to the design system tower by Kitzer, et.al. (2008). The manufactured reactive distillation consisted of packing distillation columns equipped with a reboiler and condenser, with the prototype made of stainless steel material equipped with sigh glass. The filling column expands the contact of liquid-vapor phase so that the two reactants between methanol and oil would be converted into methyl ester and glycerol. The initial results of the study indicated that the relatively good condition is reached at the peak temperature and the base of the column of 62°C and 71°C with NaOH 2% of methanol weight as the catalyst at the feed ratio of methanol and the sunan pecan oil 4:1. The result of the performance test of the diesel engine indicated that the efficiency of the biodiesel fuel was achieved relatively good at 1.7% with 2500 rpm engine speed.

Highly active Au/δ-MoC and Au/β-Mo 2C catalysts for the low-temperature water gas shift reaction: effects of the carbide metal/carbon ratio on the catalyst performance

DOE PAGES

Posada-Pérez, Sergio; Gutiérrez, Ramón A.; Zuo, Zhijun; ...

2017-05-08

In this paper, the water gas shift (WGS) reaction catalyzed by orthorhombic β-Mo 2C and cubic δ-MoC surfaces with and without Au clusters supported thereon has been studied by means of a combination of sophisticated experiments and state-of-the-art computational modeling. Experiments evidence the importance of the metal/carbon ratio on the performance of these systems, where Au/δ-MoC is presented as a suitable catalyst for WGS at low temperatures owing to its high activity, selectivity (only CO 2 and H 2 are detected), and stability (oxycarbides are not observed). Periodic density functional theory-based calculations show that the supported Au clusters and themore » Au/δ-MoC interface do not take part directly in water dissociation but their presence is crucial to switch the reaction mechanism, drastically decreasing the effect of the reverse WGS reaction and favoring the WGS products desorption, thus leading to an increase in CO 2 and H 2 production. Finally, the present results clearly display the importance of the Mo/C ratio and the synergy with the admetal clusters in tuning the activity and selectivity of the carbide substrate.« less

Highly active Au/δ-MoC and Au/β-Mo 2C catalysts for the low-temperature water gas shift reaction: effects of the carbide metal/carbon ratio on the catalyst performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Posada-Pérez, Sergio; Gutiérrez, Ramón A.; Zuo, Zhijun

In this paper, the water gas shift (WGS) reaction catalyzed by orthorhombic β-Mo 2C and cubic δ-MoC surfaces with and without Au clusters supported thereon has been studied by means of a combination of sophisticated experiments and state-of-the-art computational modeling. Experiments evidence the importance of the metal/carbon ratio on the performance of these systems, where Au/δ-MoC is presented as a suitable catalyst for WGS at low temperatures owing to its high activity, selectivity (only CO 2 and H 2 are detected), and stability (oxycarbides are not observed). Periodic density functional theory-based calculations show that the supported Au clusters and themore » Au/δ-MoC interface do not take part directly in water dissociation but their presence is crucial to switch the reaction mechanism, drastically decreasing the effect of the reverse WGS reaction and favoring the WGS products desorption, thus leading to an increase in CO 2 and H 2 production. Finally, the present results clearly display the importance of the Mo/C ratio and the synergy with the admetal clusters in tuning the activity and selectivity of the carbide substrate.« less

Understanding the fate of the oxyallyl cation following Nazarov electrocyclization: sequential Wagner-Meerwein migrations and the synthesis of spirocyclic cyclopentenones

PubMed Central

Huang, Jie; Lebœuf, David; Frontier, Alison J.

2011-01-01

A general reaction sequence is described that involves Nazarov cyclization followed by two sequential Wagner Meerwein migrations, to afford spirocyclic compounds from divinyl ketones in the presence of one equivalent of copper(II) complexes. A detailed investigation of this sequence is described including a study of substrate scope and limitations. It was found that after 4π electrocyclization, two different pathways are available to the oxyallyl cation intermediate: elimination of a proton can give the usual Nazarov cycloadduct, or ring contraction can give an alternative tertiary carbocation. After ring contraction, either [1,2]-hydride or carbon migration can occur, depending upon the substitution pattern of the substrate, to furnish spirocyclic products. The rearrangement pathway is favored over the elimination pathway when catalyst loading was high and the copper(II) counterion is noncoordinating. Several ligands were found to be effective for the reaction. Thus, the reaction sequence can be controlled by judicious choice of reaction conditions to allow selective generation of richly functionalized spirocycles. The three steps of the sequence are stereospecific: electrocyclization followed by two [1,2]-suprafacial Wagner-Meerwein shifts: the ring contraction and then an hydride, alkenyl or aryl shift. The method allows stereospecific installation of adjacent stereocenters or adjacent quaternary centers arrayed around a cyclopentenone ring. PMID:21466152

Recovering a full dimensional quantum rate constant from a reduced dimensionality calculation: Application to the OH+CO{r_arrow}H+CO{sub 2} reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dzegilenko, F.N.; Bowman, J.M.

1996-08-01

Two reduced dimensionality theories are used to calculate the thermal rate constant for the OH+CO{r_arrow}H+CO{sub 2} reaction. The standard theory employs energy-shift approximations to extract the full six degree-of-freedom quantum rate constant for this reaction from the previous two degree-of-freedom (2-DOF) quantum calculations of Hernandez and Clary [M.I. Hernandez and D.C. Clary, J. Chem. Phys. {bold 101}, 2779 (1994)]. Three extra bending modes and one extra {open_quote}{open_quote}spectator{close_quote}{close_quote} CO stretch mode are treated adiabatically in the harmonic fashion. The parameters of the exit channel transition state are used to evaluate the frequencies of those additional modes. A new reduced dimensionality theorymore » is also applied to this reaction. This theory explicitly addresses the finding from the 2-DOF calculations that the reaction proceeds mainly via complex formation. A J-shifting approximation has been used to take into account the initial states with non-zero values of total angular momentum in both reduced dimensionality theories. Cumulative reaction probabilities and thermal rate constants are calculated and compared with the previous quasiclassical and reduced dimensionality quantum calculations and with experiment. The rate constant from the new reduced dimensionality theory is between a factor of 5 and 100 times smaller than the statistical transition state theory result, and is in much better agreement with experiment. {copyright} {ital 1996 American Institute of Physics.}« less

A spectral mimetic least-squares method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bochev, Pavel; Gerritsma, Marc

We present a spectral mimetic least-squares method for a model diffusion–reaction problem, which preserves key conservation properties of the continuum problem. Casting the model problem into a first-order system for two scalar and two vector variables shifts material properties from the differential equations to a pair of constitutive relations. We also use this system to motivate a new least-squares functional involving all four fields and show that its minimizer satisfies the differential equations exactly. Discretization of the four-field least-squares functional by spectral spaces compatible with the differential operators leads to a least-squares method in which the differential equations are alsomore » satisfied exactly. Additionally, the latter are reduced to purely topological relationships for the degrees of freedom that can be satisfied without reference to basis functions. Furthermore, numerical experiments confirm the spectral accuracy of the method and its local conservation.« less

A spectral mimetic least-squares method

DOE PAGES

Bochev, Pavel; Gerritsma, Marc

2014-09-01

We present a spectral mimetic least-squares method for a model diffusion–reaction problem, which preserves key conservation properties of the continuum problem. Casting the model problem into a first-order system for two scalar and two vector variables shifts material properties from the differential equations to a pair of constitutive relations. We also use this system to motivate a new least-squares functional involving all four fields and show that its minimizer satisfies the differential equations exactly. Discretization of the four-field least-squares functional by spectral spaces compatible with the differential operators leads to a least-squares method in which the differential equations are alsomore » satisfied exactly. Additionally, the latter are reduced to purely topological relationships for the degrees of freedom that can be satisfied without reference to basis functions. Furthermore, numerical experiments confirm the spectral accuracy of the method and its local conservation.« less

Statistical Simulation of the Performance and Degradation of a PEMFC Membrane Electrode Assembly

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harvey, David; Bellemare-Davis, Alexander; Karan, Kunal

2012-07-01

A 1-D MEA Performance model was developed that considered transport of liquid water, agglomerate catalyst structure, and the statistical variation of the MEA characteristic parameters. The model was validated against a low surface area carbon supported catalyst across various platinum loadings and operational conditions. The statistical variation was found to play a significant role in creating noise in the validation data and that there was a coupling effect between movement in material properties with liquid water transport. Further, in studying the low platinum loaded catalyst layers it was found that liquid water played a significant role in the increasing themore » overall transport losses. The model was then further applied to study platinum dissolution via potential cycling accelerated stress tests, in which the platinum was found to dissolve nearest the membrane effectively resulting in reaction distribution shifts within the layer.« less

Microflow High-p,T Intensification of Vitamin D3 Synthesis Using an Ultraviolet Lamp

PubMed Central

2017-01-01

Herewith a new process concept for synthesis is presented which combines both UV-photoirradiation and high-p,T intensification (photo-high-p,T) in continuous flow. The application of this procedure to Vitamin D3 synthesis promotes thermal shifting of the equilibrium from the reaction intermediate to the product. This is enabled by microreactors which allow operation under harsh conditions such as the high temperature used here. This provides, to our best knowledge, a new kind of process combination (novel process window). As a result, in less than 1 min, 42% conversion of 7-dehydrocholesterol can be achieved giving a 17% yield and 40% selectivity of Vitamin D3. This approach enhances productivity by up to 2 orders of magnitude compared with the current capillary based vitamin D3 synthesis, because, under the microflow conditions, photochemistry can be performed at fairly high concentration and up to 20 times faster. PMID:29503521

Associations between number of consecutive night shifts and impairment of neurobehavioral performance during a subsequent simulated night shift.

PubMed

Magee, Michelle; Sletten, Tracey L; Ferguson, Sally A; Grunstein, Ronald R; Anderson, Clare; Kennaway, David J; Lockley, Steven W; Rajaratnam, Shantha Mw

2016-05-01

This study aimed to investigate sleep and circadian phase in the relationships between neurobehavioral performance and the number of consecutive shifts worked. Thirty-four shift workers [20 men, mean age 31.8 (SD 10.9) years] worked 2-7 consecutive night shifts immediately prior to a laboratory-based, simulated night shift. For 7 days prior, participants worked their usual shift sequence, and sleep was assessed with logs and actigraphy. Participants completed a 10-minute auditory psychomotor vigilance task (PVT) at the start (~21:00 hours) and end (~07:00 hours) of the simulated night shift. Mean reaction times (RT), number of lapses and RT distribution was compared between those who worked 2-3 consecutive night shifts versus those who worked 4-7 shifts. Following 4-7 shifts, night shift workers had significantly longer mean RT at the start and end of shift, compared to those who worked 2-3 shifts. The slowest and fastest 10% RT were significantly slower at the start, but not end, of shift among participants who worked 4-7 nights. Those working 4-7 nights also demonstrated a broader RT distribution at the start and end of shift and had significantly slower RT based on cumulative distribution analysis (5 (th), 25 (th), 50 (th), 75 (th)percentiles at the start of shift; 75th percentile at the end of shift). No group differences in sleep parameters were found for 7 days and 24 hours prior to the simulated night shift. A greater number of consecutive night shifts has a negative impact on neurobehavioral performance, likely due to cognitive slowing.

Operant licking for intragastric sugar infusions: differential reinforcing actions of glucose, sucrose and fructose in mice

PubMed Central

Sclafani, Anthony; Ackroff, Karen

2015-01-01

Intragastric (IG) flavor conditioning studies in rodents indicate that isocaloric sugar infusions differ in their reinforcing actions, with glucose and sucrose more potent than fructose. Here we determined if the sugars also differ in their ability to maintain operant self-administration by licking an empty spout for IG infusions. Food-restricted C57BL/6J mice were trained 1 h/day to lick a food-baited spout, which triggered IG infusions of 16% sucrose. In testing, the mice licked an empty spout, which triggered IG infusions of different sugars. Mice shifted from sucrose to 16% glucose increased dry licking, whereas mice shifted to 16% fructose rapidly reduced licking to low levels. Other mice shifted from sucrose to IG water reduced licking more slowly but reached the same low levels. Thus IG fructose, like water, is not reinforcing to hungry mice. The more rapid decline in licking induced by fructose may be due to the sugar's satiating effects. Further tests revealed that the Glucose mice increased their dry licking when shifted from 16% to 8% glucose, and reduced their dry licking when shifted to 32% glucose. This may reflect caloric regulation and/or differences in satiation. The Glucose mice did not maintain caloric intake when tested with different sugars. They self-infused less sugar when shifted from 16% glucose to 16% sucrose, and even more so when shifted to 16% fructose. Reduced sucrose self-administration may occur because the fructose component of the disaccharide reduces its reinforcing potency. FVB mice also reduced operant licking when tested with 16% fructose, yet learned to prefer a flavor paired with IG fructose. These data indicate that sugars differ substantially in their ability to support IG self-administration and flavor preference learning. The same post-oral reinforcement process appears to mediate operant licking and flavor learning, although flavor learning provides a more sensitive measure of sugar reinforcement. PMID:26485294

Theoretical study of water-gas shift reaction on the silver nanocluster

NASA Astrophysics Data System (ADS)

Arab, Ali; Sharafie, Darioush; Fazli, Mostafa

2017-10-01

The kinetics of water gas shift reaction (WGSR) on the silver nanocluster was investigated using density functional theory according to the carboxyl associative mechanism. The hybrid B3PW91 functional along with the 6-31+G* and LANL2DZ basis sets were used throughout the calculations. It was observed that CO and H2O molecules adsorb physically on the Ag5 cluster without energy barrier as the initial steps of WGSR. The next three steps including H2Oads dissociation, carboxyl (OCOHads) formation, and CO2(ads) formation were accompanied by activation barrier. Transition states, as well as energy profiles of these three steps, were determined and analyzed. Our results revealed that the carboxyl and CO2(ads) formation were fast steps whereas H2Oads dissociation was the slowest step of WGSR.

Influence of Shift Work on Manual Dexterity and Reaction Time in Tunisian Nurses.

PubMed

Merchaoui, Irtyah; Chaari, Neila; Bouhlel, Mohamed; Bouzgarrou, Lamia; Malchaire, Jacques; Akrout, Mohamed

2017-01-01

Major effects of shift schedule are related to sleep alertness and performance, but also to long term health outcomes. For nurses, these negative effects have consequences not only on the individual, but also on the workplace, as decreased alertness and reduced job performance could endanger human lives. The specific aim of our study is to assess the influence of shift schedule on nurses´ cognitive ability and rapidity of execution. Our survey is a cross sectional study which had been conducted for 15 months; it involved a sample of 293 participants representative of 1118 nurses working in two Tunisian university hospitals. It included an evaluation of the rapidity of execution performance through the manual dexterity test and the reaction time test. The study was completed by an assessment of the workability Index through a 7- item survey. No association was found between the groups of work schedules and the cognitive ability of execution speed. However, we found a significant decrease in cognitive performance in the nurses exceeding 10 years of job seniority for both schedules. We concluded to an impaired cognitive performance speed in the over 10-year seniority groups in both schedules. Recommendations should be focused on implementing periodic assessment of cognitive performance based on O'Connor finger dexterity test and time reaction test and on implementing effective preventive measures in hospitals after ten years of seniority at work. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Seasonal shifts in sex ratios are mediated by maternal effects and fluctuating incubation temperatures.

PubMed

Carter, Amanda W; Bowden, Rachel M; Paitz, Ryan T

2017-04-01

Sex-specific maternal effects can be adaptive sources of phenotypic plasticity. Reptiles with temperature-dependent sex determination (TSD) are a powerful system to investigate such maternal effects because offspring phenotype, including sex, can be sensitive to maternal influences such as oestrogens and incubation temperatures.In red-eared slider turtles ( Trachemys scripta ), concentrations of maternally derived oestrogens and incubation temperatures increase across the nesting season; we wanted to determine if sex ratios shift in a seasonally concordant manner, creating the potential for sex-specific maternal effects, and to define the sex ratio reaction norms under fluctuating temperatures across the nesting season.Eggs from early and late season clutches were incubated under a range of thermally fluctuating temperatures, maternally derived oestradiol concentrations were quantified via radioimmunoassay, and hatchling sex was identified. We found that late season eggs had higher maternal oestrogen concentrations and were more likely to produce female hatchlings. The sex ratio reaction norm curves systematically varied with season, such that with even a slight increase in temperature (0.5°C), late season eggs produced up to 49% more females than early season eggs.We found a seasonal shift in sex ratios which creates the potential for sex-specific phenotypic matches across the nesting season driven by maternal effects. We also describe, for the first time, systematic variation in the sex ratio reaction norm curve within a single population in a species with TSD.

Light as a chronobiologic countermeasure for long-duration space operations

NASA Technical Reports Server (NTRS)

Samel, Alexander (Editor); Gander, Philippa (Editor); Evans, Julie; Graeber, R. Curtis; Hackett, Elizabeth; Keil, Lanny; Maab, Hartmut; Raabe, Wolfgang; Rosekind, Mark; Rountree, Mike

1991-01-01

Long-duration space missions require adaptation to work-rest schedules which are substantially shifted with respect to earth. Astronauts are expected to work in two-shift operations and the environmental synchronizers (zeitgebers) in a spacecraft differ significantly from those on earth. A study on circadian rhythms, sleep, and performance was conducted by exposing four subjects to 6 deg head-down tilt bedrest (to simulate the effects of the weightless condition) and imposing a 12-h shift (6 h delay per day for two days). Bright light was tested in a cross-over design as a countermeasure for achieving faster resynchronization and regaining stable conditions for sleep and circadian rhythmicity. Data collection included objective sleep recording, temperature, heart rate, and excretion of hormones and electrolytes as well as performance and responses to questionnaires. Even without a shift in the sleep-wake cycle, the sleep quantity, circadian amplitudes and 24 h means decreased in many functions under bedrest conditions. During the shift days, sleepiness and fatigue increased, and alertness decreased. However, sleep quantity was regained, and resynchronization was completed within seven days after the shift for almost all functions, irrespective of whether light was administered during day-time or night-time hours. The time of day of light exposure surprisingly appeared not to have a discriminatory effect on the resynchronization speed under shift and bedrest conditions. The results indicate that simulated weightlessness alters circadian rhythms and sleep, and that schedule changes induce additional physiological disruption with decreased subjective alertness and increased fatigue. Because of their operational implications, these phenomena deserve additional investigation.

Lessons learned from the introduction of autonomous monitoring to the EUVE science operations center

NASA Technical Reports Server (NTRS)

Lewis, M.; Girouard, F.; Kronberg, F.; Ringrose, P.; Abedini, A.; Biroscak, D.; Morgan, T.; Malina, R. F.

1995-01-01

The University of California at Berkeley's (UCB) Center for Extreme Ultraviolet Astrophysics (CEA), in conjunction with NASA's Ames Research Center (ARC), has implemented an autonomous monitoring system in the Extreme Ultraviolet Explorer (EUVE) science operations center (ESOC). The implementation was driven by a need to reduce operations costs and has allowed the ESOC to move from continuous, three-shift, human-tended monitoring of the science payload to a one-shift operation in which the off shifts are monitored by an autonomous anomaly detection system. This system includes Eworks, an artificial intelligence (AI) payload telemetry monitoring package based on RTworks, and Epage, an automatic paging system to notify ESOC personnel of detected anomalies. In this age of shrinking NASA budgets, the lessons learned on the EUVE project are useful to other NASA missions looking for ways to reduce their operations budgets. The process of knowledge capture, from the payload controllers for implementation in an expert system, is directly applicable to any mission considering a transition to autonomous monitoring in their control center. The collaboration with ARC demonstrates how a project with limited programming resources can expand the breadth of its goals without incurring the high cost of hiring additional, dedicated programmers. This dispersal of expertise across NASA centers allows future missions to easily access experts for collaborative efforts of their own. Even the criterion used to choose an expert system has widespread impacts on the implementation, including the completion time and the final cost. In this paper we discuss, from inception to completion, the areas where our experiences in moving from three shifts to one shift may offer insights for other NASA missions.

Of duty hour violations and shift work: changing the educational paradigm.

PubMed

Kohlbrenner, Amanda; Dirks, Rachel; Davis, James; Wolfe, Mary; Maser, Christina

2016-06-01

Successful surgical education balances learning opportunities with Accreditation Council on Graduate Medical Education (ACGME) duty hour requirements. We instituted a night shift system and hypothesized that implementation would decrease duty hour violations while maintaining quality education. A system of alternating teams working 12-hour shifts was instituted and was assessed via an electronic survey distributed at 2, 6, and 12 months after implementation. Resident duty hour violations and resident case volume were evaluated for 1 year before and 2 years after implementation of the night shift system. Survey data revealed a decrease in the perception that residents had problems meeting duty hour restrictions from 44% to 14% at 12 months (P = .012). Total violations increased 26% in the 1st year, subsequently decreasing by 62%, with shift length violations decreasing by 90%. Resident availability for didactics was improved, and average operative cases per academic year increased by 65%. Night shift systems are feasible and help meet duty hour requirements. Our program decreased violations while increasing operative volume and didactic time. Copyright © 2015 Elsevier Inc. All rights reserved.

Anomalous diffusion with linear reaction dynamics: from continuous time random walks to fractional reaction-diffusion equations.

PubMed

Henry, B I; Langlands, T A M; Wearne, S L

2006-09-01

We have revisited the problem of anomalously diffusing species, modeled at the mesoscopic level using continuous time random walks, to include linear reaction dynamics. If a constant proportion of walkers are added or removed instantaneously at the start of each step then the long time asymptotic limit yields a fractional reaction-diffusion equation with a fractional order temporal derivative operating on both the standard diffusion term and a linear reaction kinetics term. If the walkers are added or removed at a constant per capita rate during the waiting time between steps then the long time asymptotic limit has a standard linear reaction kinetics term but a fractional order temporal derivative operating on a nonstandard diffusion term. Results from the above two models are compared with a phenomenological model with standard linear reaction kinetics and a fractional order temporal derivative operating on a standard diffusion term. We have also developed further extensions of the CTRW model to include more general reaction dynamics.

Using the principles of circadian physiology enhances shift schedule design

DOE Office of Scientific and Technical Information (OSTI.GOV)

Connolly, J.J.; Moore-Ede, M.C.

1987-01-01

Nuclear power plants must operate 24 h, 7 days a week. For the most part, shift schedules currently in use at nuclear power plants have been designed to meet operational needs without considering the biological clocks of the human operators. The development of schedules that also take circadian principles into account is a positive step that can be taken to improve plant safety by optimizing operator alertness. These schedules reduce the probability of human errors especially during backshifts. In addition, training programs that teach round-the-clock workers how to deal with the problems of shiftwork can help to optimize performance andmore » alertness. These programs teach shiftworkers the underlying causes of the sleep problems associated with shiftwork and also provide coping strategies for improving sleep and dealing with the transition between shifts. When these training programs are coupled with an improved schedule, the problems associated with working round-the-clock can be significantly reduced.« less

Clinical importance of voluntary and induced Bennett movement.

PubMed

Tupac, R G

1978-07-01

A total of 136 dentulous patients were divided into three groups for purposes of quantitative pantographic comparison of voluntary and induced Bennett movement. The effects of patient age and operator experience on recording the Bennett movement were also studied. The results indicates that for patients studied with Bennett movement iduced in the manner described: 1. Experienced operators can obtain more induced Bennett movement that inexperienced operators. 2. Inducing Bennett movement has a greater effect on the immediate side shift component than it has on the progressive side shift component. 3. For older individuals the amount and direction of induced immediate side shift is greater than for younger patients, statistically highly significant, and therefore clinically important. In conclusion, if the objective of a pantographic survey is to record the complete capacity of the joint to move, *lateral jaw movements must be induced.

Studies on the oxidation reaction of tyrosine (Tyr) with H2O2 catalyzed by horseradish peroxidase (HRP) in alcohol-water medium by spectrofluorimetry and differential spectrophotometry.

PubMed

Tang, Bo; Wang, Yan; Liang, Huiling; Chen, Zhenzhen; He, Xiwen; Shen, Hanxi

2006-03-01

An oxidation reaction of tyrosine (Tyr) with H(2)O(2) catalyzed by horseradish peroxidase (HRP) was studied by spectrofluorimetry and differential spectrophotometry in the alcohol(methanol, ethanol, 1-propanol and isopropanol)-water mutual solubility system. Compared with the enzymatic-catalyzed reaction in the water medium, the fluorescence intensities of the product weakened, even extinguished. Because the addition of alcohols made the conformation of HRP change, the catalytic reaction shifted to the side of polymerization and the polymer (A(n)H(2), n>or=3) exhibited no fluorescence. The four alcohols cannot deactivate HRP. Moreover isopropanol activated HRP remarkably.

Predicted Role of NAD Utilization in the Control of Circadian Rhythms during DNA Damage Response

PubMed Central

Luna, Augustin; McFadden, Geoffrey B.; Aladjem, Mirit I.; Kohn, Kurt W.

2015-01-01

The circadian clock is a set of regulatory steps that oscillate with a period of approximately 24 hours influencing many biological processes. These oscillations are robust to external stresses, and in the case of genotoxic stress (i.e. DNA damage), the circadian clock responds through phase shifting with primarily phase advancements. The effect of DNA damage on the circadian clock and the mechanism through which this effect operates remains to be thoroughly investigated. Here we build an in silico model to examine damage-induced circadian phase shifts by investigating a possible mechanism linking circadian rhythms to metabolism. The proposed model involves two DNA damage response proteins, SIRT1 and PARP1, that are each consumers of nicotinamide adenine dinucleotide (NAD), a metabolite involved in oxidation-reduction reactions and in ATP synthesis. This model builds on two key findings: 1) that SIRT1 (a protein deacetylase) is involved in both the positive (i.e. transcriptional activation) and negative (i.e. transcriptional repression) arms of the circadian regulation and 2) that PARP1 is a major consumer of NAD during the DNA damage response. In our simulations, we observe that increased PARP1 activity may be able to trigger SIRT1-induced circadian phase advancements by decreasing SIRT1 activity through competition for NAD supplies. We show how this competitive inhibition may operate through protein acetylation in conjunction with phosphorylation, consistent with reported observations. These findings suggest a possible mechanism through which multiple perturbations, each dominant during different points of the circadian cycle, may result in the phase advancement of the circadian clock seen during DNA damage. PMID:26020938

The effects of extended nap periods on cognitive, physiological and subjective responses under simulated night shift conditions.

PubMed

Davy, Jonathan; Göbel, Matthias

2018-02-01

Extended nap opportunities have been effective in maintaining alertness in the context of extended night shifts (+12 h). However, there is limited evidence of their efficacy during 8-h shifts. Thus, this study explored the effects of extended naps on cognitive, physiological and perceptual responses during four simulated, 8-h night shifts. In a laboratory setting, 32 participants were allocated to one of three conditions. All participants completed four consecutive, 8-h night shifts, with the arrangements differing by condition. The fixed night condition worked from 22h00 to 06h00, while the nap early group worked from 20h00 to 08h00 and napped between 00h00 and 03h20. The nap late group worked from 00h00 to 12h00 and napped between 04h00 and 07h20. Nap length was limited to 3 hours and 20 minutes. Participants performed a simple beading task during each shift, while also completing six to eight test batteries roughly every 2 h. During each shift, six test batteries were completed, in which the following measures were taken. Performance indicators included beading output, eye accommodation time, choice reaction time, visual vigilance, simple reaction time, processing speed and object recognition, working memory, motor response time and tracking performance. Physiological measures included heart rate and tympanic temperature, whereas subjective sleepiness and reported sleep length and quality while outside the laboratory constituted the self reported measures. Both naps reduced subjective sleepiness but did not alter the circadian and homeostatic-related changes in cognitive and physiological measures, relative to the fixed night condition. Additionally, there was evidence of sleep inertia following each nap, which resulted in transient reductions in certain perceptual cognitive performance measures. The present study suggested that there were some benefits associated with including an extended nap during 8-h night shifts. However, the effects of sleep inertia need to be effectively managed to ensure that post-nap alertness and performance is maintained.

Averaging of random walks and shift-invariant measures on a Hilbert space

NASA Astrophysics Data System (ADS)

Sakbaev, V. Zh.

2017-06-01

We study random walks in a Hilbert space H and representations using them of solutions of the Cauchy problem for differential equations whose initial conditions are numerical functions on H. We construct a finitely additive analogue of the Lebesgue measure: a nonnegative finitely additive measure λ that is defined on a minimal subset ring of an infinite-dimensional Hilbert space H containing all infinite-dimensional rectangles with absolutely converging products of the side lengths and is invariant under shifts and rotations in H. We define the Hilbert space H of equivalence classes of complex-valued functions on H that are square integrable with respect to a shift-invariant measure λ. Using averaging of the shift operator in H over random vectors in H with a distribution given by a one-parameter semigroup (with respect to convolution) of Gaussian measures on H, we define a one-parameter semigroup of contracting self-adjoint transformations on H, whose generator is called the diffusion operator. We obtain a representation of solutions of the Cauchy problem for the Schrödinger equation whose Hamiltonian is the diffusion operator.

Fatigue Management in Spaceflight Operations

NASA Technical Reports Server (NTRS)

Whitmire, Alexandra

2011-01-01

Sleep loss and fatigue remain an issue for crewmembers working on the International Space Station, and the ground crews who support them. Schedule shifts on the ISS are required for conducting mission operations. These shifts lead to tasks being performed during the biological night, and sleep scheduled during the biological day, for flight crews and the ground teams who support them. Other stressors have been recognized as hindering sleep in space; these include workload, thinking about upcoming tasks, environmental factors, and inadequate day/night cues. It is unknown if and how other factors such as microgravity, carbon dioxide levels, or increased radiation, may also play a part. Efforts are underway to standardize and provide care for crewmembers, ground controllers and other support personnel. Through collaborations between research and operations, evidenced-based clinical practice guidelines are being developed to equip flight surgeons with the tools and processes needed for treating circadian desynchrony (and subsequent sleep loss) caused by jet lag and shift work. The proper implementation of countermeasures such as schedules, lighting protocols, and cognitive behavioral education can hasten phase shifting, enhance sleep and optimize performance. This panel will focus on Fatigue Management in Spaceflight Operations. Speakers will present on research-based recommendations and technologies aimed at mitigating sleep loss, circadian desynchronization and fatigue on-orbit. Gaps in current mitigations and future recommendations will also be discussed.

A numerical scheme for singularly perturbed reaction-diffusion problems with a negative shift via numerov method

NASA Astrophysics Data System (ADS)

Dinesh Kumar, S.; Nageshwar Rao, R.; Pramod Chakravarthy, P.

2017-11-01

In this paper, we consider a boundary value problem for a singularly perturbed delay differential equation of reaction-diffusion type. We construct an exponentially fitted numerical method using Numerov finite difference scheme, which resolves not only the boundary layers but also the interior layers arising from the delay term. An extensive amount of computational work has been carried out to demonstrate the applicability of the proposed method.

Condensed tannins: The formation of a diarylpropanol-catechinic acid dimer from base-catalyzed reactions of (+)-catechin

Treesearch

Seiji Ohara; Richard W. Hemingway

1991-01-01

Reaction of (+ )-catechin at pH 12 and 40 DC results in the stereoselective (if not stereospecific) formation of an enolic form of 1-[6-(3',4'-dihydroxyphenyl)-7-hydroxybicyclo[3.3.1]nonane-2,4,9-trione-3-yl]-1-(3,4-dihyroxyphenyl)-3-(2,-4,6-trihydroxyphenyl)-propan-2-ol. The n.m.r. chemical shift assignments determined by a variety of two-dimensional...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lebarbier Dagel, Vanessa M.; Li, J.; Taylor, Charles E.

This collaborative joint research project is in the area of advanced gasification and conversion, within the Chinese Academy of Sciences (CAS)-National Energy Technology Laboratory (NETL)-Pacific Northwest National Laboratory (PNNL) Memorandum of Understanding. The goal for this subtask is the development of advanced syngas conversion technologies. Two areas of investigation were evaluated: Sorption-Enhanced Synthetic Natural Gas Production from Syngas The conversion of synthetic gas (syngas) to synthetic natural gas (SNG) is typically catalyzed by nickel catalysts performed at moderate temperatures (275 to 325°C). The reaction is highly exothermic and substantial heat is liberated, which can lead to process thermal imbalance andmore » destruction of the catalyst. As a result, conversion per pass is typically limited, and substantial syngas recycle is employed. Commercial methanation catalysts and processes have been developed by Haldor Topsoe, and in some reports, they have indicated that there is a need and opportunity for thermally more robust methanation catalysts to allow for higher per-pass conversion in methanation units. SNG process requires the syngas feed with a higher H2/CO ratio than typically produced from gasification processes. Therefore, the water-gas shift reaction (WGS) will be required to tailor the H2/CO ratio. Integration with CO2 separation could potentially eliminate the need for a separate WGS unit, thereby integrating WGS, methanation, and CO2 capture into one single unit operation and, consequently, leading to improved process efficiency. The SNG process also has the benefit of producing a product stream with high CO2 concentrations, which makes CO2 separation more readily achievable. The use of either adsorbents or membranes that selectively separate the CO2 from the H2 and CO would shift the methanation reaction (by driving WGS for hydrogen production) and greatly improve the overall efficiency and economics of the process. The scope of this activity was to develop methods and enabling materials for syngas conversion to SNG with readily CO2 separation. Suitable methanation catalyst and CO2 sorbent materials were developed. Successful proof-of-concept for the combined reaction-sorption process was demonstrated, which culminated in a research publication. With successful demonstration, a decision was made to switch focus to an area of fuels research of more interest to all three research institutions (CAS-NETL-PNNL). Syngas-to-Hydrocarbon Fuels through Higher Alcohol Intermediates There are two types of processes in syngas conversion to fuels that are attracting R&D interest: 1) syngas conversion to mixed alcohols; and 2) syngas conversion to gasoline via the methanol-to-gasoline process developed by Exxon-Mobil in the 1970s. The focus of this task was to develop a one-step conversion technology by effectively incorporating both processes, which is expected to reduce the capital and operational cost associated with the conversion of coal-derived syngas to liquid fuels. It should be noted that this work did not further study the classic Fischer-Tropsch reaction pathway. Rather, we focused on the studies for unique catalyst pathways that involve the direct liquid fuel synthesis enabled by oxygenated intermediates. Recent advances made in the area of higher alcohol synthesis including the novel catalytic composite materials recently developed by CAS using base metal catalysts were used.« less

Real life working shift assignment problem

NASA Astrophysics Data System (ADS)

Sze, San-Nah; Kwek, Yeek-Ling; Tiong, Wei-King; Chiew, Kang-Leng

2017-07-01

This study concerns about the working shift assignment in an outlet of Supermarket X in Eastern Mall, Kuching. The working shift assignment needs to be solved at least once in every month. Current approval process of working shifts is too troublesome and time-consuming. Furthermore, the management staff cannot have an overview of manpower and working shift schedule. Thus, the aim of this study is to develop working shift assignment simulation and propose a working shift assignment solution. The main objective for this study is to fulfill manpower demand at minimum operation cost. Besides, the day off and meal break policy should be fulfilled accordingly. Demand based heuristic is proposed to assign working shift and the quality of the solution is evaluated by using the real data.

[Working time and sleep in nursing staff employed in "3 x 8" and "2 x 12" fast rotating shift schedules].

PubMed

Castellini, G; Anelli, M M; Punzi, S; Boari, P; Camerino, D; Costa, G

2011-01-01

The study is aimed at assessing, in 200 nurses shift workers, the impact on sleep of two different working areas ("emergency" and "hospitalization") having the same "3 x 8" shift system, and of two different shift schedules at quick rotation ("2 x 12" and "3 x 8") in the same working area ("emergency"). Night and morning shifts prove to interfere to a greater extent with sleep in relation to both "2 x 12" and "3 x 8" shift systems as well as to the two operative areas. Hence the importance to consider in shift work planning, the direction of shift rotation and the length of the duty period according to the type of activity.

Molecular Electronic Shift Registers

NASA Technical Reports Server (NTRS)

Beratan, David N.; Onuchic, Jose N.

1990-01-01

Molecular-scale shift registers eventually constructed as parts of high-density integrated memory circuits. In principle, variety of organic molecules makes possible large number of different configurations and modes of operation for such shift-register devices. Several classes of devices and implementations in some specific types of molecules proposed. All based on transfer of electrons or holes along chains of repeating molecular units.

Shifting Paradigms in Music Education Research (1953-1978): A Theoretical and Quantitative Reassessment

ERIC Educational Resources Information Center

Jorgensen, Estelle R.; Ward-Steinman, Patrice Madura

2015-01-01

The purpose of this study was to examine evidence of a hypothesized shift in the operative research paradigms in music education during the first quarter century of the publication of the "Journal of Research in Music Education," during the period 1953 to 1978. This shift was from humanities-oriented historical and philosophical studies…

Simulation of Water Gas Shift Zeolite Membrane Reactor

NASA Astrophysics Data System (ADS)

Makertiharta, I. G. B. N.; Rizki, Z.; Zunita, Megawati; Dharmawijaya, P. T.

2017-07-01

The search of alternative energy sources keeps growing from time to time. Various alternatives have been introduced to reduce the use of fossil fuel, including hydrogen. Many pathways can be used to produce hydrogen. Among all of those, the Water Gas Shift (WGS) reaction is the most common pathway to produce high purity hydrogen. The WGS technique faces a downstream processing challenge due to the removal hydrogen from the product stream itself since it contains a mixture of hydrogen, carbon dioxide and also the excess reactants. An integrated process using zeolite membrane reactor has been introduced to improve the performance of the process by selectively separate the hydrogen whilst boosting the conversion. Furthermore, the zeolite membrane reactor can be further improved via optimizing the process condition. This paper discusses the simulation of Zeolite Membrane Water Gas Shift Reactor (ZMWGSR) with variation of process condition to achieve an optimum performance. The simulation can be simulated into two consecutive mechanisms, the reaction prior to the permeation of gases through the zeolite membrane. This paper is focused on the optimization of the process parameters (e.g. temperature, initial concentration) and also membrane properties (e.g. pore size) to achieve an optimum product specification (concentration, purity).

Free Surface Properties of III-V Compound Semiconductor Surfaces.

DTIC Science & Technology

1980-06-01

selvage. Most important is the fact that atomic displacements also occur up to two layers into the substrate in the IaSb (ll0) selvage, presumably because of...result is that the interaction is of a disordering nature. 1 2,1 3 We took LEED measurements for a very large range of exposure to molecular oxygen (103...which the Al replaces the Ga. Arguments in favor of this reaction are given by measured photoemission peak shifts: 1 8󈧗 the Ga 3-d core level shifts

Liquid chromatographic determination of water

DOEpatents

Fortier, N.E.; Fritz, J.S.

1990-11-13

A sensitive method for the determination of water in the presence of common interferences is presented. The detection system is based on the effect of water on the equilibrium which results from the reaction aryl aldehydes, such as cinnamaldehyde and methanol in the eluent to form cinnamaldehyde dimethylacetal, plus water. This equilibrium is shifted in a catalytic atmosphere of a hydrogen ion form past column reactor. The extent of the shift and the resulting change in absorbance are proportional to the amount of water present. 1 fig.

Liquid chromatographic determination of water

DOEpatents

Fortier, Nancy E.; Fritz, James S.

1990-11-13

A sensitive method for the determination of water in the presence of common interferences is presented. The detection system is based on the effect of water on the equilibrium which results from the reaction aryl aldehydes, such as cinnamaldehyde and methanol in the eluent to form cinnamaldehyde dimethylacetal, plus water. This equilibrium is shifted in a catalytic atmosphere of a hydrogen ion form past column reactor. The extent of the shift and the resulting change in absorbance are proportional to the amount of water present.

Ethanol internal steam reforming in intermediate temperature solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Diethelm, Stefan; Van herle, Jan

This study investigates the performance of a standard Ni-YSZ anode supported cell under ethanol steam reforming operating conditions. Therefore, the fuel cell was directly operated with a steam/ethanol mixture (3 to 1 molar). Other gas mixtures were also used for comparison to check the conversion of ethanol and of reformate gases (H 2, CO) in the fuel cell. The electrochemical properties of the fuel cell fed with four different fuel compositions were characterized between 710 and 860 °C by I- V and EIS measurements at OCV and under polarization. In order to elucidate the limiting processes, impedance spectra obtained with different gas compositions were compared using the derivative of the real part of the impedance with respect of the natural logarithm of the frequency. Results show that internal steam reforming of ethanol takes place significantly on Ni-YSZ anode only above 760 °C. Comparisons of results obtained with reformate gas showed that the electrochemical cell performance is dominated by the conversion of hydrogen. The conversion of CO also occurs either directly or indirectly through the water-gas shift reaction but has a significant impact on the electrochemical performance only above 760 °C.

Corrective Control to Handle Forecast Uncertainty: A Chance Constrained Optimal Power Flow

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roald, Line; Misra, Sidhant; Krause, Thilo

Higher shares of electricity generation from renewable energy sources and market liberalization is increasing uncertainty in power systems operation. At the same time, operation is becoming more flexible with improved control systems and new technology such as phase shifting transformers (PSTs) and high voltage direct current connections (HVDC). Previous studies have shown that the use of corrective control in response to outages contributes to a reduction in operating cost, while maintaining N-1 security. In this work, we propose a method to extend the use of corrective control of PSTs and HVDCs to react to uncertainty. We characterize the uncertainty asmore » continuous random variables, and define the corrective control actions through affine control policies. This allows us to efficiently model control reactions to a large number of uncertainty sources. The control policies are then included in a chance constrained optimal power flow formulation, which guarantees that the system constraints are enforced with a desired probability. Lastly, by applying an analytical reformulation of the chance constraints, we obtain a second-order cone problem for which we develop an efficient solution algorithm. In a case study for the IEEE 118 bus system, we show that corrective control for uncertainty leads to a decrease in operational cost, while maintaining system security. Further, we demonstrate the scalability of the method by solving the problem for the IEEE 300 bus and the Polish system test cases.« less

Corrective Control to Handle Forecast Uncertainty: A Chance Constrained Optimal Power Flow

DOE PAGES

Roald, Line; Misra, Sidhant; Krause, Thilo; ...

2016-08-25

Higher shares of electricity generation from renewable energy sources and market liberalization is increasing uncertainty in power systems operation. At the same time, operation is becoming more flexible with improved control systems and new technology such as phase shifting transformers (PSTs) and high voltage direct current connections (HVDC). Previous studies have shown that the use of corrective control in response to outages contributes to a reduction in operating cost, while maintaining N-1 security. In this work, we propose a method to extend the use of corrective control of PSTs and HVDCs to react to uncertainty. We characterize the uncertainty asmore » continuous random variables, and define the corrective control actions through affine control policies. This allows us to efficiently model control reactions to a large number of uncertainty sources. The control policies are then included in a chance constrained optimal power flow formulation, which guarantees that the system constraints are enforced with a desired probability. Lastly, by applying an analytical reformulation of the chance constraints, we obtain a second-order cone problem for which we develop an efficient solution algorithm. In a case study for the IEEE 118 bus system, we show that corrective control for uncertainty leads to a decrease in operational cost, while maintaining system security. Further, we demonstrate the scalability of the method by solving the problem for the IEEE 300 bus and the Polish system test cases.« less

Fatigue in airline pilots after an additional day's layover period.

PubMed

Powell, David M C; Spencer, Mick B; Petrie, Keith J

2010-11-01

We investigated the effect of an additional day's layover on reducing fatigue in two different duties: a two-pilot crew flying between Auckland and Brisbane, and a three-pilot crew flying between Auckland and Los Angeles. Pilots completed a reaction time task, the Samn-Perelli fatigue scale, and the Karolinska Sleepiness Scale on both outward and return flights. The flights were conducted with and without a 1-d layover (Brisbane) and with a 1- or 2-d layover (Los Angeles). On the Brisbane route, the addition of a layover resulted in a significant reduction of fatigue, sleepiness, and reaction time. At top of descent, Samn-Perelli fatigue was reduced from over 5.0 to under 4.5. In contrast, the addition of an extra day layover in Los Angeles had no significant effect on the same measures during the return flight; on both flights Samn-Perelli fatigue was over 5.0 at top of descent. The results suggest that the addition of an extra night's layover has different effects depending on the type of operation. Layover periods need to ensure adequate opportunity to recover from any sleep deficit arising from the outbound journey, but the benefit of increased layover time may be limited if time-zone shifts cause a mismatch between local time and the circadian rhythm of sleep.

The influence of nano-architectured CeOx supports in RhPd/CeO₂ for the catalytic ethanol steam reforming reaction

DOE PAGES

Divins, N. J.; Senanayake, S. D.; Casanovas, A.; ...

2015-01-19

The ethanol steam reforming (ESR) reaction has been tested over RhPd supported on polycrystalline ceria in comparison to structured supports composed of nanoshaped CeO₂ cubes and CeO₂ rods tailored towards the production of hydrogen. At 650-700 K the hydrogen yield follows the trend RhPd/CeO₂-cubes > RhPd/CeO₂ -rods > RhPd/CeO₂- polycrystalline, whereas at temperatures higher than 800 K the catalytic performance of all samples is similar and close to the thermodynamic equilibrium. The improved performance of RhPd/CeO₂-cubes and RhPd/CeO₂ -rods for ESR at low temperature is mainly ascribed to higher water-gas shift activity and a strong interaction between the bimetallic -more » oxide support interaction. STEM analysis shows the existence of RhPd alloyed nanoparticles in all samples, with no apparent relationship between ESR performance and RhPd particle size. X-ray diffraction under operating conditions shows metal reorganization on {100} and {110} ceria crystallographic planes during catalyst activation and ESR, but not on {111} ceria crystallographic planes. The RhPd reconstructing and tuned activation over ceria nanocubes and nanorods is considered the main reason for better catalytic activity with respect to conventional catalysts based on polycrystalline ceria« less

New developments of the in-source spectroscopy method at RILIS/ISOLDE

NASA Astrophysics Data System (ADS)

Marsh, B. A.; Andel, B.; Andreyev, A. N.; Antalic, S.; Atanasov, D.; Barzakh, A. E.; Bastin, B.; Borgmann, Ch.; Capponi, L.; Cocolios, T. E.; Day Goodacre, T.; Dehairs, M.; Derkx, X.; De Witte, H.; Fedorov, D. V.; Fedosseev, V. N.; Focker, G. J.; Fink, D. A.; Flanagan, K. T.; Franchoo, S.; Ghys, L.; Huyse, M.; Imai, N.; Kalaninova, Z.; Köster, U.; Kreim, S.; Kesteloot, N.; Kudryavtsev, Yu.; Lane, J.; Lecesne, N.; Liberati, V.; Lunney, D.; Lynch, K. M.; Manea, V.; Molkanov, P. L.; Nicol, T.; Pauwels, D.; Popescu, L.; Radulov, D.; Rapisarda, E.; Rosenbusch, M.; Rossel, R. E.; Rothe, S.; Schweikhard, L.; Seliverstov, M. D.; Sels, S.; Sjödin, A. M.; Truesdale, V.; Van Beveren, C.; Van Duppen, P.; Wendt, K.; Wienholtz, F.; Wolf, R. N.; Zemlyanoy, S. G.

2013-12-01

At the CERN ISOLDE facility, long isotope chains of many elements are produced by proton-induced reactions in target materials such as uranium carbide. The Resonance Ionization Laser Ion Source (RILIS) is an efficient and selective means of ionizing the reaction products to produce an ion beam of a chosen isotope. Coupling the RILIS with modern ion detection techniques enables highly sensitive studies of nuclear properties (spins, electromagnetic moments and charge radii) along an isotope chain, provided that the isotope shifts and hyperfine structure splitting of the atomic transitions can be resolved. At ISOLDE the campaign to measure the systematics of isotopes in the lead region (Pb, Bi, Tl and Po) has been extended to include the gold and astatine isotope chains. Several developments were specifically required for the feasibility of the most recent measurements: new ionization schemes (Po, At); a remote controlled narrow line-width mode of operation for the RILIS Ti:sapphire laser (At, Au, Po); isobar free ionization using the Laser Ion Source Trap, LIST (Po); isobar selective particle identification using the multi-reflection time-of-flight mass separator (MR-ToF MS) of ISOLTRAP (Au, At). These are summarized as part of an overview of the current status of the in-source resonance ionization spectroscopy setup at ISOLDE.

Neural network modelling of the influence of channelopathies on reflex visual attention.

PubMed

Gravier, Alexandre; Quek, Chai; Duch, Włodzisław; Wahab, Abdul; Gravier-Rymaszewska, Joanna

2016-02-01

This paper introduces a model of Emergent Visual Attention in presence of calcium channelopathy (EVAC). By modelling channelopathy, EVAC constitutes an effort towards identifying the possible causes of autism. The network structure embodies the dual pathways model of cortical processing of visual input, with reflex attention as an emergent property of neural interactions. EVAC extends existing work by introducing attention shift in a larger-scale network and applying a phenomenological model of channelopathy. In presence of a distractor, the channelopathic network's rate of failure to shift attention is lower than the control network's, but overall, the control network exhibits a lower classification error rate. The simulation results also show differences in task-relative reaction times between control and channelopathic networks. The attention shift timings inferred from the model are consistent with studies of attention shift in autistic children.

Comparing headphone and speaker effects on simulated driving.

PubMed

Nelson, T M; Nilsson, T H

1990-12-01

Twelve persons drove for three hours in an automobile simulator while listening to music at sound level 63dB over stereo headphones during one session and from a dashboard speaker during another session. They were required to steer a mountain highway, maintain a certain indicated speed, shift gears, and respond to occasional hazards. Steering and speed control were dependent on visual cues. The need to shift and the hazards were indicated by sound and vibration effects. With the headphones, the driver's average reaction time for the most complex task presented--shifting gears--was about one-third second longer than with the speaker. The use of headphones did not delay the development of subjective fatigue.

High pressure liquid gas pump

NASA Technical Reports Server (NTRS)

Acres, R. L.

1972-01-01

Design and development of two types of pumps for handling liquefied gases are discussed. One pump uses mechanical valve shift and other uses pneumatic valve shift. Illustrations of pumps are provided and detailed description of operation is included.

Neural dynamics of object-based multifocal visual spatial attention and priming: Object cueing, useful-field-of-view, and crowding

PubMed Central

Foley, Nicholas C.; Grossberg, Stephen; Mingolla, Ennio

2015-01-01

How are spatial and object attention coordinated to achieve rapid object learning and recognition during eye movement search? How do prefrontal priming and parietal spatial mechanisms interact to determine the reaction time costs of intra-object attention shifts, inter-object attention shifts, and shifts between visible objects and covertly cued locations? What factors underlie individual differences in the timing and frequency of such attentional shifts? How do transient and sustained spatial attentional mechanisms work and interact? How can volition, mediated via the basal ganglia, influence the span of spatial attention? A neural model is developed of how spatial attention in the where cortical stream coordinates view-invariant object category learning in the what cortical stream under free viewing conditions. The model simulates psychological data about the dynamics of covert attention priming and switching requiring multifocal attention without eye movements. The model predicts how “attentional shrouds” are formed when surface representations in cortical area V4 resonate with spatial attention in posterior parietal cortex (PPC) and prefrontal cortex (PFC), while shrouds compete among themselves for dominance. Winning shrouds support invariant object category learning, and active surface-shroud resonances support conscious surface perception and recognition. Attentive competition between multiple objects and cues simulates reaction-time data from the two-object cueing paradigm. The relative strength of sustained surface-driven and fast-transient motion-driven spatial attention controls individual differences in reaction time for invalid cues. Competition between surface-driven attentional shrouds controls individual differences in detection rate of peripheral targets in useful-field-of-view tasks. The model proposes how the strength of competition can be mediated, though learning or momentary changes in volition, by the basal ganglia. A new explanation of crowding shows how the cortical magnification factor, among other variables, can cause multiple object surfaces to share a single surface-shroud resonance, thereby preventing recognition of the individual objects. PMID:22425615

Neural dynamics of object-based multifocal visual spatial attention and priming: object cueing, useful-field-of-view, and crowding.

PubMed

Foley, Nicholas C; Grossberg, Stephen; Mingolla, Ennio

2012-08-01

How are spatial and object attention coordinated to achieve rapid object learning and recognition during eye movement search? How do prefrontal priming and parietal spatial mechanisms interact to determine the reaction time costs of intra-object attention shifts, inter-object attention shifts, and shifts between visible objects and covertly cued locations? What factors underlie individual differences in the timing and frequency of such attentional shifts? How do transient and sustained spatial attentional mechanisms work and interact? How can volition, mediated via the basal ganglia, influence the span of spatial attention? A neural model is developed of how spatial attention in the where cortical stream coordinates view-invariant object category learning in the what cortical stream under free viewing conditions. The model simulates psychological data about the dynamics of covert attention priming and switching requiring multifocal attention without eye movements. The model predicts how "attentional shrouds" are formed when surface representations in cortical area V4 resonate with spatial attention in posterior parietal cortex (PPC) and prefrontal cortex (PFC), while shrouds compete among themselves for dominance. Winning shrouds support invariant object category learning, and active surface-shroud resonances support conscious surface perception and recognition. Attentive competition between multiple objects and cues simulates reaction-time data from the two-object cueing paradigm. The relative strength of sustained surface-driven and fast-transient motion-driven spatial attention controls individual differences in reaction time for invalid cues. Competition between surface-driven attentional shrouds controls individual differences in detection rate of peripheral targets in useful-field-of-view tasks. The model proposes how the strength of competition can be mediated, though learning or momentary changes in volition, by the basal ganglia. A new explanation of crowding shows how the cortical magnification factor, among other variables, can cause multiple object surfaces to share a single surface-shroud resonance, thereby preventing recognition of the individual objects. Copyright © 2012 Elsevier Inc. All rights reserved.

Organometallic benzylidene anilines: donor-acceptor features in NCN-pincer Pt(ii) complexes with a 4-(E)-[(4-R-phenyl)imino]methyl substituent.

PubMed

Batema, Guido D; Lutz, Martin; Spek, Anthony L; van Walree, Cornelis A; van Klink, Gerard P M; van Koten, Gerard

2014-08-28

A series of organometallic 4,4'-substituted benzylidene aniline complexes 4-ClPt-3,5-(CH2NMe2)2C6H2CH[double bond, length as m-dash]NC6H4R'-4', abbreviated as PtCl[NCN(CH[double bond, length as m-dash]NC6H4R'-4')-4], with R' = NMe2, Me, H, Cl, CN (, respectively), was synthesized via a Schiff-base condensation reaction involving reaction of PtCl[NCN(CH[double bond, length as m-dash]O)-4] () with the appropriate 4-R'-substituted aniline derivative () in toluene. The resulting arylplatinum(ii) products were obtained in 75-88% yield. Notably, product was also obtained in 68% yield from a reaction in the solid state by grinding solid with aniline . The structures of , , and in the solid state (single crystal X-ray diffraction) showed a non-planar geometry, in particular for compound . The electronic interaction between the donor benzylidene fragment PtCl(NCN-CH) and the para-R' aniline substituent through the azomethine bridge was studied with NMR and UV/Vis spectroscopy. Linear correlations were found between the azomethine (1)H, the (195)Pt NMR and various (13)C NMR chemical shifts, and the substituent parameters σF and σR of R' at the aniline site. In common with organic benzylidene anilines, the azomethine (1)H NMR chemical shift showed anomalous substituent behavior. The (195)Pt NMR chemical shift of the platinum center can be used as a probe for the electronic properties of the delocalized π-system of the benzylidene aniline framework, to which it is connected. The dual substituent parameter treatment of the azomethine (13)C NMR shift gave important insight into the unique behaviour of the Pt-pincer group as a substituent. Inductively, it is a very strong electron-withdrawing group, whereas mesomerically it behaves like a very strong electron donating group.

In situ Mössbauer investigation of iron oxide catalyst in water gas shift reaction - Impact of oxyreduction potential and temperature

NASA Astrophysics Data System (ADS)

Cherkezova-Zheleva, Z.; Mitov, I.

2010-03-01

The aim of the study is to obtain the exact state of iron oxide catalyst active phase in reaction conditions, as well as the correlation between the active phase and catalytic properties of iron-containing catalysts. In situ Mössbauer spectroscopy is the major investigation technique. It is established that the change of reaction conditions (temperature and gas reaction mixture) lead to redistribution of the relative weight of spectra components and influence mainly tetrahedrally and octahedrally coordinated cations in Fe3O4 phase. It was concluded, that the active sites of the catalyst in studied reaction are probably pairs of Fe3++Fe2+-(Fe2.5+) ions, i.e. the mixed valance iron ions. The obtained catalytic activity can be explained with combination of the natural thermo-activated and catalytically induced electron exchange and better synchronizing of oxidation and reduction steps of the catalytic reaction.

Catalytic reactor

DOEpatents

Aaron, Timothy Mark [East Amherst, NY; Shah, Minish Mahendra [East Amherst, NY; Jibb, Richard John [Amherst, NY

2009-03-10

A catalytic reactor is provided with one or more reaction zones each formed of set(s) of reaction tubes containing a catalyst to promote chemical reaction within a feed stream. The reaction tubes are of helical configuration and are arranged in a substantially coaxial relationship to form a coil-like structure. Heat exchangers and steam generators can be formed by similar tube arrangements. In such manner, the reaction zone(s) and hence, the reactor is compact and the pressure drop through components is minimized. The resultant compact form has improved heat transfer characteristics and is far easier to thermally insulate than prior art compact reactor designs. Various chemical reactions are contemplated within such coil-like structures such that as steam methane reforming followed by water-gas shift. The coil-like structures can be housed within annular chambers of a cylindrical housing that also provide flow paths for various heat exchange fluids to heat and cool components.

Driver fatigue during extended rail operations.

PubMed

Jay, Sarah M; Dawson, Drew; Ferguson, Sally A; Lamond, Nicole

2008-09-01

Relay is an effective mode of freight transportation within Australia. Relay requires two crews to drive the train continuously from one specified destination to another and return with crews working in alternating shifts. The aim of the current investigation was to assess fatigue levels during extended relay operations. Nine drivers participated and data were collected from 16 four-day trips. Fatigue was assessed objectively and subjectively prior to and following each trip and before and after each 8h shift. Analyses revealed a trend for elevated fatigue at the end of each shift. Designated 8h rest periods appeared sufficient to reduce fatigue to levels recorded prior to departure and prevent accumulation of fatigue across the trip. Drivers seemed to cope well with the 8h rotating sleep/wake regime. While fatigue did not observably accumulate, it is possible that operational measures may better reflect fatigue experienced over the course of each trip.

Water-gas-shift over metal-free nanocrystalline ceria: An experimental and theoretical study

DOE PAGES

Guild, Curtis J.; Vovchok, Dimitriy; Kriz, David A.; ...

2017-01-23

A tandem experimental and theoretical investigation of a mesoporous ceria catalyst reveals the properties of the metal oxide are conducive for activity typically ascribed to metals, suggesting reduced Ce 3+ and oxygen vacancies are responsible for the inherent bi-functionality of CO oxidation and dissociation of water required for facilitating the production of H 2. The degree of reduction of the ceria, specifically the (1 0 0) face, is found to significantly influence the binding of reagents, suggesting reduced surfaces harbor the necessary reactive sites. The metal-free catalysis of the reaction is significant for catalyst design considerations, and the suite ofmore » in situ analyses provides a comprehensive study of the dynamic nature of the high surface area catalyst system. Finally, this study postulates feasible improvements in catalytic activity may redirect the purpose of the water-gas shift reaction from CO purification to primary hydrogen production.« less

Water-gas-shift over metal-free nanocrystalline ceria: An experimental and theoretical study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guild, Curtis J.; Vovchok, Dimitriy; Kriz, David A.

A tandem experimental and theoretical investigation of a mesoporous ceria catalyst reveals the properties of the metal oxide are conducive for activity typically ascribed to metals, suggesting reduced Ce 3+ and oxygen vacancies are responsible for the inherent bi-functionality of CO oxidation and dissociation of water required for facilitating the production of H 2. The degree of reduction of the ceria, specifically the (1 0 0) face, is found to significantly influence the binding of reagents, suggesting reduced surfaces harbor the necessary reactive sites. The metal-free catalysis of the reaction is significant for catalyst design considerations, and the suite ofmore » in situ analyses provides a comprehensive study of the dynamic nature of the high surface area catalyst system. Finally, this study postulates feasible improvements in catalytic activity may redirect the purpose of the water-gas shift reaction from CO purification to primary hydrogen production.« less

Unified connected theory of few-body reaction mechanisms in N-body scattering theory

NASA Technical Reports Server (NTRS)

Polyzou, W. N.; Redish, E. F.

1978-01-01

A unified treatment of different reaction mechanisms in nonrelativistic N-body scattering is presented. The theory is based on connected kernel integral equations that are expected to become compact for reasonable constraints on the potentials. The operators T/sub +-//sup ab/(A) are approximate transition operators that describe the scattering proceeding through an arbitrary reaction mechanism A. These operators are uniquely determined by a connected kernel equation and satisfy an optical theorem consistent with the choice of reaction mechanism. Connected kernel equations relating T/sub +-//sup ab/(A) to the full T/sub +-//sup ab/ allow correction of the approximate solutions for any ignored process to any order. This theory gives a unified treatment of all few-body reaction mechanisms with the same dynamic simplicity of a model calculation, but can include complicated reaction mechanisms involving overlapping configurations where it is difficult to formulate models.

Non-equilibrium reaction and relaxation dynamics in a strongly interacting explicit solvent: F + CD3CN treated with a parallel multi-state EVB model

NASA Astrophysics Data System (ADS)

Glowacki, David R.; Orr-Ewing, Andrew J.; Harvey, Jeremy N.

2015-07-01

We describe a parallelized linear-scaling computational framework developed to implement arbitrarily large multi-state empirical valence bond (MS-EVB) calculations within CHARMM and TINKER. Forces are obtained using the Hellmann-Feynman relationship, giving continuous gradients, and good energy conservation. Utilizing multi-dimensional Gaussian coupling elements fit to explicitly correlated coupled cluster theory, we built a 64-state MS-EVB model designed to study the F + CD3CN → DF + CD2CN reaction in CD3CN solvent (recently reported in Dunning et al. [Science 347(6221), 530 (2015)]). This approach allows us to build a reactive potential energy surface whose balanced accuracy and efficiency considerably surpass what we could achieve otherwise. We ran molecular dynamics simulations to examine a range of observables which follow in the wake of the reactive event: energy deposition in the nascent reaction products, vibrational relaxation rates of excited DF in CD3CN solvent, equilibrium power spectra of DF in CD3CN, and time dependent spectral shifts associated with relaxation of the nascent DF. Many of our results are in good agreement with time-resolved experimental observations, providing evidence for the accuracy of our MS-EVB framework in treating both the solute and solute/solvent interactions. The simulations provide additional insight into the dynamics at sub-picosecond time scales that are difficult to resolve experimentally. In particular, the simulations show that (immediately following deuterium abstraction) the nascent DF finds itself in a non-equilibrium regime in two different respects: (1) it is highly vibrationally excited, with ˜23 kcal mol-1 localized in the stretch and (2) its post-reaction solvation environment, in which it is not yet hydrogen-bonded to CD3CN solvent molecules, is intermediate between the non-interacting gas-phase limit and the solution-phase equilibrium limit. Vibrational relaxation of the nascent DF results in a spectral blue shift, while relaxation of the post-reaction solvation environment results in a red shift. These two competing effects mean that the post-reaction relaxation profile is distinct from what is observed when Franck-Condon vibrational excitation of DF occurs within a microsolvation environment initially at equilibrium. Our conclusions, along with the theoretical and parallel software framework presented in this paper, should be more broadly applicable to a range of complex reactive systems.

The effects of assisted cycling therapy (ACT) and voluntary cycling on reaction time and measures of executive function in adolescents with Down syndrome.

PubMed

Ringenbach, S D R; Holzapfel, S D; Mulvey, G M; Jimenez, A; Benson, A; Richter, M

2016-11-01

Reports of positive effects of aerobic exercise on cognitive function in persons with Down syndrome are extremely limited. However, a novel exercise intervention, termed assisted cycling therapy (ACT), has resulted in acutely improved cognitive planning ability and reaction times as well as improved cognitive planning after 8 weeks of ACT in adolescents and young adults with Down syndrome. Here, we report the effects of 8 weeks of ACT on reaction time, set-shifting, inhibition and language fluency in adolescents with Down syndrome. Adolescents with Down syndrome (age: ~18 years) were randomly assigned to 8 weeks of ACT (n = 17) or voluntary cycling (VC: n = 16), and a convenience sample (n = 11) was assigned to be an inactive comparison group (NC: n = 11). During ACT, the cycling cadence of the participants was augmented to an average cadence that was 80% faster than the voluntary cadence of the VC group. The increase in cadence was achieved with an electric motor in the stationary bicycle. Reaction time, set-shifting, inhibition and language fluency were assessed before and after 8 weeks of intervention. Power output and heart rates of the ACT and VC groups were almost identical, but the ACT cadence was significantly faster. The ACT group, but not the VC or NC groups, showed significantly improved reactions times (Hedges' g = -0.42) and inhibitory control (g = 0.18). Only the VC group showed improved set-shifting ability (g = 0.57). The ACT and VC groups displayed improved semantic language fluency (g = 0.25, g = 0.22, respectively). These and previous results support the hypothesis of increased neuroplasticity and prefrontal cortex function following ACT and, to a smaller extent, following VC. Both ACT and VC appear to be associated with cortical benefits, but based on current and previous results, ACT seems to maximize the benefits. © 2016 MENCAP and International Association of the Scientific Study of Intellectual and Developmental Disabilities and John Wiley & Sons Ltd.

In situ/operando studies for the production of hydrogen through the water-gas shift on metal oxide catalysts.

PubMed

Rodriguez, José A; Hanson, Jonathan C; Stacchiola, Dario; Senanayake, Sanjaya D

2013-08-07

In this perspective article, we show how a series of in situ techniques {X-ray diffraction (XRD), pair-distribution-function analysis (PDF), X-ray absorption fine structure (XAFS), environmental transmission electron microscopy (ETEM), infrared spectroscopy (IR), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS)} can be combined to perform detailed studies of the structural, electronic and chemical properties of metal oxide catalysts used for the production of hydrogen through the water-gas shift reaction (WGS, CO + H2O → H2 + CO2). Under reaction conditions most WGS catalysts undergo chemical transformations that drastically modify their composition with respect to that obtained during the synthesis process. Experiments of time-resolved in situ XRD, XAFS, and PDF indicate that the active phase of catalysts which combine Cu, Au or Pt with oxides such as ZnO, CeO2, TiO2, CeOx/TiO2 and Fe2O3 essentially involves nanoparticles of the reduced noble metals. The oxide support undergoes partial reduction and is not a simple spectator, facilitating the dissociation of water and in some cases modifying the chemical properties of the supported metal. Therefore, to optimize the performance of these catalysts one must take into consideration the properties of the metal and oxide phases. IR and AP-XPS have been used to study the reaction mechanism for the WGS on metal oxide catalysts. Data of IR spectroscopy indicate that formate species are not necessarily involved in the main reaction path for the water-gas shift on Cu-, Au- and Pt-based catalysts. Thus, a pure redox mechanism or associative mechanisms that involve either carbonate-like (CO3, HCO3) or carboxyl (HOCO) species should be considered. In the last two decades, there have been tremendous advances in our ability to study catalytic materials under reaction conditions and we are moving towards the major goal of fully understanding how the active sites for the production of hydrogen through the WGS actually work.

Rates for neutron-capture reactions on tungsten isotopes in iron meteorites. [Abstract only

NASA Technical Reports Server (NTRS)

Masarik, J.; Reedy, R. C.

1994-01-01

High-precision W isotopic analyses by Harper and Jacobsen indicate the W-182/W-183 ratio in the Toluca iron meteorite is shifted by -(3.0 +/- 0.9) x 10(exp -4) relative to a terrestrial standard. Possible causes of this shift are neutron-capture reactions on W during Toluca's approximately 600-Ma exposure to cosmic ray particles or radiogenic growth of W-182 from 9-Ma Hf-182 in the silicate portion of the Earth after removal of W to the Earth's core. Calculations for the rates of neutron-capture reactions on W isotopes were done to study the first possibility. The LAHET Code System (LCS) which consists of the Los Alamos High Energy Transport (LAHET) code and the Monte Carlo N-Particle(MCNP) transport code was used to numerically simulate the irradiation of the Toluca iron meteorite by galactic-cosmic-ray (GCR) particles and to calculate the rates of W(n, gamma) reactions. Toluca was modeled as a 3.9-m-radius sphere with the composition of a typical IA iron meteorite. The incident GCR protons and their interactions were modeled with LAHET, which also handled the interactions of neutrons with energies above 20 MeV. The rates for the capture of neutrons by W-182, W-183, and W-186 were calculated using the detailed library of (n, gamma) cross sections in MCNP. For this study of the possible effect of W(n, gamma) reactions on W isotope systematics, we consider the peak rates. The calculated maximum change in the normalized W-182/W-183 ratio due to neutron-capture reactions cannot account for more than 25% of the mass 182 deficit observed in Toluca W.

A comparison investigation of optical, structural and luminescence properties of CdOxTe1-x and CdTexSe1-x nanoparticles prepared by a simple one pot method

NASA Astrophysics Data System (ADS)

Kiprotich, Sharon; Onani, Martin O.; Dejene, Francis B.

2018-04-01

We present L-cysteine capped CdOXTe1-X and CdTeXSe1-X nanoparticles (NPs) prepared in one pot. The as-prepared CdOXTe1-X NPs were found to have a hexagonal crystal structure of CdTe with a cubic phase of CdO. There was, however, change in phase to cubic type when 2 mM of Se was introduced into the CdTe at 60 min of reaction time. The average crystallite sizes obtained from X-ray diffraction analysis for CdOXTe1-X and CdTeXSe1-X NPs were in the range of 10-36 nm. The diffraction peaks shifted to higher diffraction angle with longer growth time. Scanning electron microscope images display change in shape and size as reaction progress. Photoluminescence (PL) emission was observed to shift from 510-566 nm and 620-653 nm for CdOXTe1-X and CdTeXSe1-X NPs respectively followed by variation in the peak intensities. The emission spectra displayed a good symmetry and a narrow full width at half maximum ranging from 41 to 100 nm in both cases. The absorbance analysis of the as-prepared NPs displayed well-resolved absorption bands. The optical band gaps of the as-prepared NPs were found to decrease with increase in reaction time. Reaction parameters such as pH, reaction time, reaction temperature and the molar concentration could have major effects on the optical properties of the as-prepared nanoparticles hence their need to control them.

Tandem catalysis for the production of alkyl lactates from ketohexoses at moderate temperatures

DOE PAGES

Orazov, Marat; Davis, Mark E.

2015-09-08

Retro-aldol reactions have been implicated as the limiting steps in catalytic routes to convert biomass-derived hexoses and pentoses into valuable C2, C3, and C4 products such as glycolic acid, lactic acid, 2-hydroxy-3-butenoic acid, 2,4-dihydroxybutanoic acid, and alkyl esters thereof. Due to a lack of efficient retro-aldol catalysts, most previous investigations of catalytic pathways involving these reactions were conducted at high temperatures (≥160 °C). Here, we report moderate-temperature (around 100 °C) retro-aldol reactions of various hexoses in aqueous and alcoholic media with catalysts traditionally known for their capacity to catalyze 1,2-intramolecular carbon shift (1,2-CS) reactions of aldoses, i.e., various molybdenum oxidemore » and molybdate species, nickel(II) diamine complexes, alkali-exchanged stannosilicate molecular sieves, and amorphous TiO2–SiO2 coprecipitates. Solid Lewis acid cocatalysts that are known to catalyze 1,2-intramolecular hydride shift (1,2-HS) reactions that enable the formation of α-hydroxy carboxylic acids from tetroses, trioses, and glycolaldehyde, but cannot readily catalyze retro-aldol reactions of hexoses and pentoses at these moderate temperatures, are shown to be compatible with the aforementioned retro-aldol catalysts. The combination of a distinct retro-aldol catalyst with a 1,2-HS catalyst enables lactic acid and alkyl lactate formation from ketohexoses at moderate temperatures (around 100 °C), with yields comparable to best-reported chemocatalytic examples at high temperature conditions (≥160 °C). The use of moderate temperatures enables numerous desirable features such as lower pressure and significantly less catalyst deactivation.« less

Effects of hydrogen atom spin exchange collisions on atomic hydrogen maser oscillation frequency

NASA Technical Reports Server (NTRS)

Crampton, S. B.

1979-01-01

Frequency shifts due to collisions between hydrogen atoms in an atomic hydrogen maser frequency standard are studied. Investigations of frequency shifts proportional to the spin exchange frequency shift cross section and those proportional to the duration of exchange collisions are discussed. The feasibility of operating a hydrogen frequency standard at liquid helium temperatures is examined.

Cascaded c-cut Nd:YVO4 self-Raman laser operation with a single 259 cm-1 shift

NASA Astrophysics Data System (ADS)

Guo, Junhong; Zhu, Haiyong; Duan, Yanmin; Xu, Changwen; Ruan, Xiukai; Cui, Guihua; Yan, Lifen

2017-03-01

A cascaded c-cut Nd:YVO4 crystal self-Raman operation was demonstrated with a Raman shift of 259 cm-1. The Stokes oscillation with a primary Raman shift of 890 cm-1 was suppressed and a cascaded self-Raman with a single Raman shift of 259 cm-1 was realized based on suitable coating design. At an incident pump power of 13.3 W, the second Stokes at 1129 nm was obtained as the main output laser and the output power was about 0.81 W. As the incident pump power increased, dual Stokes at 1129 and 1163 nm were obtained. A maximum output power of up to 1.0 W with a conversion efficiency of 6.7% was achieved at an incident pump power of 14.9 W and a pulse repetition frequency of 15 kHz.

Response of Cryolite-Based Bath to a Shift in Heat Input/output Balance

NASA Astrophysics Data System (ADS)

Liu, Jingjing; Taylor, Mark; Dorreen, Mark

2017-04-01

A technology for low amperage potline operation is now recognized as a competitive advantage for the aluminum smelting industry in order to align smelter operations with the power and aluminum price markets. This study investigates the cryolite-based bath response to heat balance shifts when the heat extraction from the bath is adjusted to different levels in a laboratory analogue. In the analogue experiments, the heat balance shift is driven by a graphite `cold finger' heat exchanger, which can control the heat extraction from the analogue, and a corresponding change in heat input from the furnace which maintains the control temperature of the lab "cell." This paper reports the first experimental results from shifting the steady state of the lab cell heat balance, and investigates the effects on the frozen ledge and bath superheat. The lab cell energy balances are compared with energy balances in a published industrial cell model.

Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles

PubMed Central

Szymanski, Craig J.; Munusamy, Prabhakaran; Mihai, Cosmin; Xie, Yumei; Hu, Dehong; Gilles, Mary K.; Tyliszczak, Tolek; Thevuthasan, Suntharampillai; Baer, Donald R.; Orr, Galya

2015-01-01

Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce3+/Ce4+ ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantified the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce3+/Ce4+ ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of cells. PMID:26056725

Monotopic modifications derived from in vitro glycation of albumin with ribose.

PubMed

Pataridis, Statis; Stastná, Zdeňka; Sedláková, Pavla; Mikšík, Ivan

2013-06-01

Post-translational modifications are significant reactions that occur to proteins. One of these modifications is a non-enzymatic reaction between the oxo-group(s) of sugars and amino-group(s) of protein - glycation. This reaction plays an important role in the chronic complications of diabetes mellitus, or in the aging process of organisms, that is, it has an important role in the pathophysiology and "normal" physiology of animals. In the work presented here, we studied the glycation of albumins (HSA and BSA). Methodologically, we used nano-LC coupled to a QTOF mass spectrometer. In vitro-modified proteins were cleaved by trypsin and the arising peptides were separated on a C(18) nano column with a trap-column. Peptides and their modifications were analysed with a high-resolution QTOF mass spectrometer with a mass determination precision of better than 5 ppm. Non-enzymatic in vitro reaction products between albumin and ribose were identified. Besides well-known carboxymethyl lysine, new modifications were determined - creating mass shifts of 78 and 218. The origin of the first modification is discussed and its possible structure is presented. In addition, a mass shift of 132 belonging to a Schiff base was also identified. The location of all the modifications within the structure of the proteins was determined and their reactivity to various oxo-compounds was also examined. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Changes in H(+)-ATP Synthase Activity, Proton Electrochemical Gradient, and pH in Pea Chloroplast Can Be Connected with Variation Potential.

PubMed

Sukhov, Vladimir; Surova, Lyubov; Morozova, Ekaterina; Sherstneva, Oksana; Vodeneev, Vladimir

2016-01-01

Local stimulation induces generation and propagation of electrical signals, including the variation potential (VP) and action potential, in plants. Burning-induced VP changes the physiological state of plants; specifically, it inactivates photosynthesis. However, the mechanisms that decrease photosynthesis are poorly understood. We investigated these mechanisms by measuring VP-connected systemic changes in CO2 assimilation, parameters of light reactions of photosynthesis, electrochromic pigment absorbance shifts, and light scattering. We reveal that inactivation of photosynthesis in the pea, including inactivation of dark and light reactions, was connected with the VP. Inactivation of dark reactions decreased the rate constant of the fast relaxation of the electrochromic pigment absorbance shift, which reflected a decrease in the H(+)-ATP synthase activity. This decrease likely contributed to the acidification of the chloroplast lumen, which developed after VP induction. However, VP-connected decrease of the proton motive force across the thylakoid membrane, possibly, reflected a decreased pH in the stroma. This decrease may be another mechanism of chloroplast lumen acidification. Overall, stroma acidification can decrease electron flow through photosystem I, and lumen acidification induces growth of fluorescence non-photochemical quenching and decreases electron flow through photosystem II, i.e., pH decreases in the stroma and lumen, possibly, contribute to the VP-induced inactivation of light reactions of photosynthesis.

Attrition resistant catalysts for slurry-phase Fischer-Tropsch process

DOE Office of Scientific and Technical Information (OSTI.GOV)

K. Jothimurugesan

1999-11-01

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. Iron-based (Fe) catalysts are preferred catalysts for F-T because they are relatively inexpensive and possess reasonable activity for F-T synthesis (FTS). Their most advantages trait is their high water-gas shift (WGS) activity compared to their competitor, namely cobalt. This enables Fe F-T catalysts to process lowmore » H{sub 2}/CO ratio synthesis gas without an external shift reaction step. However, a serious problem with the use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, make the separation of catalyst from the oil/wax product very difficult if not impossible, an d result in a steady loss of catalyst from the reactor. The objectives of this research were to develop a better understanding of the parameters affecting attrition of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance.« less

Win-stay and win-shift lever-press strategies in an appetitively reinforced task for rats.

PubMed

Reed, Phil

2016-12-01

Two experiments examined acquisition of win-stay, win-shift, lose-stay, and lose-shift rules by which hungry rats could earn food reinforcement. In Experiment 1, two groups of rats were trained in a two-lever operant task that required them to follow either a win-stay/lose-shift or a win-shift/lose-stay contingency. The rates of acquisition of the individual rules within each contingency differed: lose-shift and lose-stay rules were acquired faster than win-stay and win-shift rules. Contrary to a number of previous reports, the win-shift rule was acquired less rapidly than any of the other rules. In Experiment 2, the four rules were taught separately, but subjects still acquired the win-shift rule more slowly than any of the other rules.

[BEHAVIORAL AND FUNCTIONAL VESTIBULAR DISTURBANCES AFTER SPACE FLIGHT. 2. FISHES, AMPHIBIANS AND BIRDS].

PubMed

Lychakov, D V

2016-01-01

The review contains data on functional shifts in fishes, amphibians and birds caused by changes in the otolith system operation after stay under weightlessness conditions. These data are of theoretical and practical significance and are important to resolve some fundamental problems of vestibulogy. The analysis of the results of space experiments has shown that weightlessness conditions do not exert a substantial impact on formation and functional state of the otolith system in embryonic fishes, amphibians and birds developed during space flight. Weightlessness conditions do pot inhibit embryonic development of lower vertebrates but even have rather beneficial effect on it. This is consistent with conclusions concerning development of mammalian fetuses. The experimental results show that weightlessness can cause similar functional and behavioral vestibular shifts both in lower vertebrates and in mammals. For example, immediately after an orbital flight the vestibuloocular reflex in fish larvae and tadpoles (without lordosis) was stronger than in control individuals. A similar shift of the otolith reflex was observed in the majority of cosmonauts after short-term orbital flights. Immediately after landing adult terrestrial vertebrates, as well as human beings, exhibit lower activity levels, worse equilibrium and coordination of movements. Another interesting finding observed after landing of the cosmic apparatus was an unusual looping character of tadpole swimming. It is supposed that the unusual motor activity of animals as well as appearance of illusions in cosmonauts and astronauts after switching from 1 to 0 g have the same nature and are related to the change in character of otolith organs stimulation. Considering this similarity of vestibular reactions, using animals seems rather perspective. Besides it allows applying in experiments various invasive techniques.

Comprehensive approach to image-guided surgery

NASA Astrophysics Data System (ADS)

Peters, Terence M.; Comeau, Roch M.; Kasrai, Reza; St. Jean, Philippe; Clonda, Diego; Sinasac, M.; Audette, Michel A.; Fenster, Aaron

1998-06-01

Image-guided surgery has evolved over the past 15 years from stereotactic planning, where the surgeon planned approaches to intracranial targets on the basis of 2D images presented on a simple workstation, to the use of sophisticated multi- modality 3D image integration in the operating room, with guidance being provided by mechanically, optically or electro-magnetically tracked probes or microscopes. In addition, sophisticated procedures such as thalamotomies and pallidotomies to relieve the symptoms of Parkinson's disease, are performed with the aid of volumetric atlases integrated with the 3D image data. Operations that are performed stereotactically, that is to say via a small burr- hole in the skull, are able to assume that the information contained in the pre-operative imaging study, accurately represents the brain morphology during the surgical procedure. On the other hand, preforming a procedure via an open craniotomy presents a problem. Not only does tissue shift when the operation begins, even the act of opening the skull can cause significant shift of the brain tissue due to the relief of intra-cranial pressure, or the effect of drugs. Means of tracking and correcting such shifts from an important part of the work in the field of image-guided surgery today. One approach has ben through the development of intra-operative MRI imaging systems. We describe an alternative approach which integrates intra-operative ultrasound with pre-operative MRI to track such changes in tissue morphology.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lei, Yu; Liu, Bin; Lu, Junling

The effect of residue chlorine on the synthesis of well-dispersed Pd nanoparticles on TiO2 supports using Pd atomic layer deposition (ALD) was investigated. The dispersion of Pd nanoparticles was compared over chlorine-containing and chlorine-free TiO2 supports prepared by selecting proper precursors. The detailed X-ray photoelectron spectroscopy and scanning transmission electron microscopy characterizations showed that higher dispersion of Pd nanoparticles was achieved on the chlorine-containing TiO2 surface than the chlorine-free TiO2. The preparation of TiO2 thin films and Pd nanoparticles was characterized by in situ FT-IR. The temperature required for complete deligation of palladium hexafluoroacetylacetonate decreased from 175 to 100 degreesmore » C with the presence of chlorine on the TiO2 surface. Density functional theory calculations confirm that Pdligand bond strength could be weakened as Pd binds to the Cl sites. The water-gas-shift reaction was chosen as the model reaction, and the catalytic performance of the ALD Pd catalysts was discussed. Compared to reported catalysts, the Pd nanocatalysts supported by TiO2/SiO2 mixed oxides showed promising performance in the low-temperature water-gas-shift reaction.« less

In Situ Characterization of Mesoporous Co/CeO 2 Catalysts for the High-Temperature Water-Gas Shift

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vovchok, Dimitriy; Guild, Curtis J.; Dissanayake, Shanka

Here, mesoporous Co/CeO 2 catalysts were found to exhibit significant activity for the high-temperature water-gas shift (WGS) reaction with cobalt loadings as low as 1 wt %. The catalysts feature a uniform dispersion of cobalt within the CeO 2 fluorite type lattice with no evidence of discrete cobalt phase segregation. In situ XANES and ambient pressure XPS experiments were used to elucidate the active state of the catalysts as partially reduced cerium oxide doped with oxidized cobalt atoms. In situ XRD and DRIFTS experiments suggest facile cerium reduction and oxygen vacancy formation, particularly with lower cobalt loadings. In situ DRIFTSmore » analysis also revealed the presence of surface carbonate and bidentate formate species under reaction conditions, which may be associated with additional mechanistic pathways for the WGS reaction. Deactivation behavior was observed with higher cobalt loadings. XANES data suggest the formation of small metallic cobalt clusters at temperatures above 400 °C may be responsible. Notably, this deactivation was not observed for the 1% cobalt loaded catalyst, which exhibited the highest activity per unit of cobalt.« less

In Situ Characterization of Mesoporous Co/CeO 2 Catalysts for the High-Temperature Water-Gas Shift

DOE PAGES

Vovchok, Dimitriy; Guild, Curtis J.; Dissanayake, Shanka; ...

2018-04-04

Here, mesoporous Co/CeO 2 catalysts were found to exhibit significant activity for the high-temperature water-gas shift (WGS) reaction with cobalt loadings as low as 1 wt %. The catalysts feature a uniform dispersion of cobalt within the CeO 2 fluorite type lattice with no evidence of discrete cobalt phase segregation. In situ XANES and ambient pressure XPS experiments were used to elucidate the active state of the catalysts as partially reduced cerium oxide doped with oxidized cobalt atoms. In situ XRD and DRIFTS experiments suggest facile cerium reduction and oxygen vacancy formation, particularly with lower cobalt loadings. In situ DRIFTSmore » analysis also revealed the presence of surface carbonate and bidentate formate species under reaction conditions, which may be associated with additional mechanistic pathways for the WGS reaction. Deactivation behavior was observed with higher cobalt loadings. XANES data suggest the formation of small metallic cobalt clusters at temperatures above 400 °C may be responsible. Notably, this deactivation was not observed for the 1% cobalt loaded catalyst, which exhibited the highest activity per unit of cobalt.« less

Quantum Dynamics Study of the Isotopic Effect on Capture Reactions: HD, D2 + CH3

NASA Technical Reports Server (NTRS)

Wang, Dunyou; Kwak, Dochan (Technical Monitor)

2002-01-01

Time-dependent wave-packet-propagation calculations are reported for the isotopic reactions, HD + CH3 and D2 + CH3, in six degrees of freedom and for zero total angular momentum. Initial state selected reaction probabilities for different initial rotational-vibrational states are presented in this study. This study shows that excitations of the HD(D2) enhances the reactivities; whereas the excitations of the CH3 umbrella mode have the opposite effects. This is consistent with the reaction of H2 + CH3. The comparison of these three isotopic reactions also shows the isotopic effects in the initial-state-selected reaction probabilities. The cumulative reaction probabilities (CRP) are obtained by summing over initial-state-selected reaction probabilities. The energy-shift approximation to account for the contribution of degrees of freedom missing in the six dimensionality calculation is employed to obtain approximate full-dimensional CRPs. The rate constant comparison shows H2 + CH3 reaction has the biggest reactivity, then HD + CH3, and D2 + CH3 has the smallest.

Internal reforming characteristics of cermet supported solid oxide fuel cell using yttria stabilized zirconia fed with partially reformed methane

NASA Astrophysics Data System (ADS)

Momma, Akihiko; Takano, Kiyonami; Tanaka, Yohei; Negishi, Akira; Kato, Ken; Nozaki, Ken; Kato, Tohru; Ichigi, Takenori; Matsuda, Kazuyuki; Ryu, Takashi

In order to investigate the internal reforming characteristics in a cermet supported solid oxide fuel cell (SOFC) using YSZ as the electrolyte, the concentration profiles of the gaseous species along the gas flow direction in the anode were measured. Partially reformed methane using a pre-reformer kept at a constant temperature is supplied to the center of the cell which is operated with a seal-less structure at the gas outlet. The anode gas is sucked in via silica capillaries to the initially evacuated gas tanks. The process is simultaneously carried out using five sampling ports. The sampled gas is analyzed by a gas chromatograph. Most of the measurements are made at the cell temperature (T cell) of 750 °C and at various temperatures of the pre-reformer (T ref) with various fuel utilizations (U f) of the cell. The composition of the fuel at the inlet of the anode was confirmed to be almost the same as that theoretically calculated assuming equilibrium at the temperature of the pre-reformer. The effect of internal reforming in the anode is clearly observed as a steady decrease in the methane concentration along the flow axis. The effect of the water-gas shift reaction is also observed as a decrease in the CO 2 concentration and an increase of CO concentration around the gas inlet region, as the water-gas shift reaction inversely proceeds when T cell is higher than T ref. The diffusion of nitrogen from the seal-less outermost edge is observed, and the diffusion is confirmed to be more significant as U f decreases. The observations are compared with the results obtained by the SOFC supported by lanthanum gallate electrolyte. With respect to the internal reforming performance, the cell investigated here is found to be more effective when compared to the previously reported electrolyte supported cell.

Imposed glutathione-mediated redox switch modulates the tobacco wound-induced protein kinase and salicylic acid-induced protein kinase activation state and impacts on defence against Pseudomonas syringae.

PubMed

Matern, Sanja; Peskan-Berghoefer, Tatjana; Gromes, Roland; Kiesel, Rebecca Vazquez; Rausch, Thomas

2015-04-01

The role of the redox-active tripeptide glutathione in plant defence against pathogens has been studied extensively; however, the impact of changes in cellular glutathione redox potential on signalling processes during defence reactions has remained elusive. This study explored the impact of elevated glutathione content on the cytosolic redox potential and on early defence signalling at the level of mitogen-activated protein kinases (MAPKs), as well as on subsequent defence reactions, including changes in salicylic acid (SA) content, pathogenesis-related gene expression, callose depositions, and the hypersensitive response. Wild-type (WT) Nicotiana tabacum L. and transgenic high-glutathione lines (HGL) were transformed with the cytosol-targeted sensor GRX1-roGFP2 to monitor the cytosolic redox state. Surprisingly, HGLs displayed an oxidative shift in their cytosolic redox potential and an activation of the tobacco MAPKs wound-induced protein kinase (WIPK) and SA-induced protein kinase (SIPK). This activation occurred in the absence of any change in free SA content, but was accompanied by constitutively increased expression of several defence genes. Similarly, rapid activation of MAPKs could be induced in WT tobacco by exposure to either reduced or oxidized glutathione. When HGL plants were challenged with adapted or non-adapted Pseudomonas syringae pathovars, the cytosolic redox shift was further amplified and the defence response was markedly increased, showing a priming effect for SA and callose; however, the initial and transient hyperactivation of MAPK signalling was attenuated in HGLs. The results suggest that, in tobacco, MAPK and SA signalling may operate independently, both possibly being modulated by the glutathione redox potential. Possible mechanisms for redox-mediated MAPK activation are discussed. © The Author 2015. Published by Oxford University Press on behalf of the Society for Experimental Biology.

Shift scheduling model considering workload and worker’s preference for security department

NASA Astrophysics Data System (ADS)

Herawati, A.; Yuniartha, D. R.; Purnama, I. L. I.; Dewi, LT

2018-04-01

Security department operates for 24 hours and applies shift scheduling to organize its workers as well as in hotel industry. This research has been conducted to develop shift scheduling model considering the workers physical workload using rating of perceived exertion (RPE) Borg’s Scale and workers’ preference to accommodate schedule flexibility. The mathematic model is developed in integer linear programming and results optimal solution for simple problem. Resulting shift schedule of the developed model has equally distribution shift allocation among workers to balance the physical workload and give flexibility for workers in working hours arrangement.

Selection in spatial working memory is independent of perceptual selective attention, but they interact in a shared spatial priority map.

PubMed

Hedge, Craig; Oberauer, Klaus; Leonards, Ute

2015-11-01

We examined the relationship between the attentional selection of perceptual information and of information in working memory (WM) through four experiments, using a spatial WM-updating task. Participants remembered the locations of two objects in a matrix and worked through a sequence of updating operations, each mentally shifting one dot to a new location according to an arrow cue. Repeatedly updating the same object in two successive steps is typically faster than switching to the other object; this object switch cost reflects the shifting of attention in WM. In Experiment 1, the arrows were presented in random peripheral locations, drawing perceptual attention away from the selected object in WM. This manipulation did not eliminate the object switch cost, indicating that the mechanisms of perceptual selection do not underlie selection in WM. Experiments 2a and 2b corroborated the independence of selection observed in Experiment 1, but showed a benefit to reaction times when the placement of the arrow cue was aligned with the locations of relevant objects in WM. Experiment 2c showed that the same benefit also occurs when participants are not able to mark an updating location through eye fixations. Together, these data can be accounted for by a framework in which perceptual selection and selection in WM are separate mechanisms that interact through a shared spatial priority map.

Variations of melatonin and stress hormones under extended shifts and radiofrequency electromagnetic radiation.

PubMed

Vangelova, Katia Koicheva; Israel, Mishel Salvador

2005-01-01

We studied the time-of-day variations in urinary levels of 6-sulphatoxy-melatonin and three stress hormones in operators working fast-rotating extended shifts under radiofrequency electromagnetic radiation (EMR). The excretion rate of the hormones was monitored by radioimmunoassay and spectrofluorimetry at 4-hour intervals in a group of 36 male operators comprising 12 broadcasting station operators, 12 TV station operators, and a control group of 12 satellite station operators. Measuring the time-weighted average (TWA) of EMR exposure revealed a high-level of exposure in broadcasting station operators (TWAmean= 3.10 microW/ cm2, TWAmax = 137.00 microW/cm2), a low-level in TV station operators (TWAmean = 1.89 microW/cm2, TWAmax = 5.24 microW/cm2), and a very low level in satellite station operators. The differences among the groups remained the same after confounding factors were taken into account. Radiofrequency EMR had no effect on the typical diurnal pattern of 6-sulphatoxymelatonin. High-level radiofrequency EMR exposure significantly increased the excretion rates of cortisol (p < 0.001), adrenaline (p = 0.028), and noradrenaline (p < 0.000), whereas changes under low-level exposure did not reach significance. The 24-hour excretion of cortisol and noradrenaline correlated with TWAmean and TWAmax. In conclusion, the excretion of 6-sulphatoxymelatonin retained a typical diurnal pattern under fast-rotating extended shifts and radiofrequency EMR, but showed an exposure-effect relation with stress hormones.

The relativistic theory of the chemical shift

NASA Astrophysics Data System (ADS)

Pyper, N. C.

1983-04-01

A relativistic theory of the NMR chemical shift for a closed-shell system is presented. The final expression for the shielding, derived by, applying two Gordon decompositions to the Dirac current operator, closely parallels the Ramsey non-relativistic result.

Use of wastewater treatment plant biogas for the operation of Solid Oxide Fuel Cells (SOFCs).

PubMed

Lackey, Jillian; Champagne, Pascale; Peppley, Brant

2017-12-01

Solid Oxide Fuel Cells (SOFCs) perform well on light hydrocarbon fuels, and the use of biogas derived from the anaerobic digestion (AD) of municipal wastewater sludges could provide an opportunity for the CH 4 produced to be used as a renewable fuel. Greenhouse gas (GHG), NO x , SO x , and hydrocarbon pollutant emissions would also be reduced. In this study, SOFCs were operated on AD derived biogas. Initially, different H 2 dilutions were tested (N 2 , Ar, CO 2 ) to examine the performance of tubular SOFCs. With inert gases as diluents, a decrease in cell performance was observed, however, the use of CO 2 led to a higher decrease in performance as it promoted the reverse water-gas shift (WGS) reaction, reducing the H 2 partial pressure in the gas mixture. A model was developed to predict system efficiency and GHG emissions. A higher electrical system efficiency was noted for a steam:carbon ratio of 2 compared to 1 due to the increased H 2 partial pressure in the reformate resulting from higher H 2 O concentration. Reductions in GHG emissions were estimated at 2400 tonnes CO 2 , 60 kg CH 4 and 18 kg N 2 O. SOFCs were also tested using a simulated biogas reformate mixture (66.7% H 2 , 16.1% CO, 16.5% CO 2 , 0.7% N 2 , humidified to 2.3 or 20 mol% H 2 O). Higher humidification yielded better performance as the WGS reaction produced more H 2 with additional H 2 O. It was concluded that AD-derived biogas, when cleaned to remove H 2 S, Si compounds, halides and other contaminants, could be reformed to provide a clean, renewable fuel for SOFCs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mechanistic Studies on the Galvanic Replacement Reaction between Multiply Twinned Particles of Ag and HAuCl4 in an Organic Medium

PubMed Central

Lu, Xianmao; Tuan, Hsing-Yu; Chen, Jingyi; Li, Zhi-Yuan; Korgel, Brian A; Xia, Younan

2008-01-01

This article presents a mechanistic study on the galvanic replacement reaction between 11- and 14-nm multiply twinned particles (MTPs) of Ag and HAuCl4 in chloroform. We monitored both morphological and spectral changes as the molar ratio of HAuCl4 to Ag was increased. The details of reaction were different from previous observations on single-crystal Ag nanocubes and cubooctahedrons. Because Au and Ag form alloys rapidly within small MTPs rich in vacancy and grain boundary defects, a complete Au shell did not form on the surface of each individual Ag template. Instead, the replacement reaction resulted in the formation of alloy nanorings and nanocages from Ag MTPs of decahedral or icosahedral shape. For the nanorings and nanocages derived from 11-nm Ag MTPs, the surface plasmon resonance (SPR) peak can be continuously shifted from 400 to 616 nm. When the size of Ag MTPs was increased to 14 nm, the SPR peak can be further shifted to 740 nm, a wavelength sought by biomedical applications. We have also investigated the effects of capping ligands and AgCl precipitate on the replacement reaction. While hollow structures were routinely generated from oleylamine-capped Ag MTPs, we obtained very few hollow structures by using a stronger capping ligand such as oleic acid or tri-n-octylphosphine oxide (TOPO). Addition of extra oleylamine was found to be critical to the formation of well-controlled, uniform hollow structures free of AgCl contamination thanks to the formation of a soluble complex between AgCl and oleylamine. PMID:17243691

Interfaces in heterogeneous catalytic reactions: Ambient pressure XPS as a tool to unravel surface chemistry

DOE PAGES

Palomino, Robert M.; Hamlyn, Rebecca; Liu, Zongyuan; ...

2017-04-27

In this paper we provide a summary of the recent development of ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and its application to catalytic surface chemistry. The methodology as well as significant advantages and challenges associated with this novel technique are described. Details about specific examples of using AP-XPS to probe surface chemistry under working reaction conditions for a number of reactions are explained: CO oxidation, water-gas shift (WGS), CO 2 hydrogenation, dry reforming of methane (DRM) and ethanol steam reforming (ESR). In conclusion, we discuss insights into the future development of the AP-XPS technique and its applications.

Interfaces in heterogeneous catalytic reactions: Ambient pressure XPS as a tool to unravel surface chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Palomino, Robert M.; Hamlyn, Rebecca; Liu, Zongyuan

In this paper we provide a summary of the recent development of ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and its application to catalytic surface chemistry. The methodology as well as significant advantages and challenges associated with this novel technique are described. Details about specific examples of using AP-XPS to probe surface chemistry under working reaction conditions for a number of reactions are explained: CO oxidation, water-gas shift (WGS), CO 2 hydrogenation, dry reforming of methane (DRM) and ethanol steam reforming (ESR). In conclusion, we discuss insights into the future development of the AP-XPS technique and its applications.

Biological detection and tagging using tailorable, reactive, highly fluorescent chemosensors.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shepodd, Timothy J.; Zifer, Thomas; McElhanon, James Ross

2006-11-01

This program was focused on the development of a fluorogenic chemosensor family that could tuned for reaction with electrophilic (e.g. chemical species, toxins) and nucleophilic (e.g. proteins and other biological molecules) species. Our chemosensor approach utilized the fluorescent properties of well-known berberine-type alkaloids. In situ chemosensor reaction with a target species transformed two out-of-plane, weakly conjugated, short-wavelength chromophores into one rigid, planar, conjugated, chromophore with strong long wavelength fluorescence (530-560 nm,) and large Stokes shift (100-180 nm). The chemosensor was activated with an isourea group which allowed for reaction with carboxylic acid moieties found in amino acids.

MRI of chemical reactions and processes.

PubMed

Britton, Melanie M

2017-08-01

As magnetic resonance imaging (MRI) can spatially resolve a wealth of molecular information available from nuclear magnetic resonance (NMR), it is able to non-invasively visualise the composition, properties and reactions of a broad range of spatially-heterogeneous molecular systems. Hence, MRI is increasingly finding applications in the study of chemical reactions and processes in a diverse range of environments and technologies. This article will explain the basic principles of MRI and how it can be used to visualise chemical composition and molecular properties, providing an overview of the variety of information available. Examples are drawn from the disciplines of chemistry, chemical engineering, environmental science, physics, electrochemistry and materials science. The review introduces a range of techniques used to produce image contrast, along with the chemical and molecular insight accessible through them. Methods for mapping the distribution of chemical species, using chemical shift imaging or spatially-resolved spectroscopy, are reviewed, as well as methods for visualising physical state, temperature, current density, flow velocities and molecular diffusion. Strategies for imaging materials with low signal intensity, such as those containing gases or low sensitivity nuclei, using compressed sensing, para-hydrogen or polarisation transfer, are discussed. Systems are presented which encapsulate the diversity of chemical and physical parameters observable by MRI, including one- and two-phase flow in porous media, chemical pattern formation, phase transformations and hydrodynamic (fingering) instabilities. Lastly, the emerging area of electrochemical MRI is discussed, with studies presented on the visualisation of electrochemical deposition and dissolution processes during corrosion and the operation of batteries, supercapacitors and fuel cells. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

Geobiochemistry: Placing Biochemistry in Its Geochemical Context

NASA Astrophysics Data System (ADS)

Shock, E.; Boyer, G. M.; Canovas, P. A., III; Prasad, A.; Dick, J. M.

2014-12-01

Goals of geobiochemistry include simultaneously evaluating the relative stabilities of microbial cells and minerals, and predicting how the composition of biomolecules can change in response to the progress of geochemical reactions. Recent developments in theoretical geochemistry make it possible to predict standard thermodynamic properties of proteins, nucleotides, lipids, and many metabolites including the constituents of the citric acid cycle, at all temperatures and pressures where life is known to occur, and beyond. Combining these predictions with constraints from geochemical data makes it possible to assess the relative stabilities of biomolecules. Resulting independent predictions of the environmental occurrence of homologous proteins and lipid side-chains can be compared with observations from metagenomic and metalipidomic data to quantify geochemical driving forces that shape the composition of biomolecules. In addition, the energetic costs of generating biomolecules from within a diverse range of habitable environments can be evaluated in terms of prevailing geochemical variables. Comparisons of geochemical bioenergetic calculations across habitats leads to the generalization that the availability of H2 determines the cost of autotrophic biosynthesis relative to the aquatic environment external to microbial cells, and that pH, temperature, pressure, and availability of C, N, P, and S are typically secondary. Increasingly reduced conditions, which are determined by reactions of water with mineral surfaces and mineral assemblages, allow many biosynthetic reactions to shift from costing energy to releasing energy. Protein and lipid synthesis, as well as the reverse citric acid cycle, become energy-releasing processes under these conditions. The resulting energy balances that determine habitability contrast dramatically with assumptions derived from oxic surface conditions, such as those where human biochemistry operates.

Interface formation during silica encapsulation of colloidal CdSe/CdS quantum dots observed by in situ Raman spectroscopy

NASA Astrophysics Data System (ADS)

Biermann, Amelie; Aubert, Tangi; Baumeister, Philipp; Drijvers, Emile; Hens, Zeger; Maultzsch, Janina

2017-04-01

We investigate the encapsulation of CdSe/CdS quantum dots (QDs) in a silica shell by in situ Raman spectroscopy and find a distinct shift of the CdS Raman signal during the first hours of the synthesis. This shift does not depend on the final silica shell thickness but on the properties of the initial core-shell QD. We find a correlation between the Raman shift rate and the speed of the silica formation and attribute this to the changing configuration of the outermost layers of the QD shell, where an interface to the newly formed silica is created. This dependence of Raman shift rate on the speed of silica formation process will give rise to many possible studies concerning the growth mechanism in the water-in-oil microemulsion, rendering in situ Raman a valuable instrument in monitoring this type of reaction.

Open quantum system approach to the modeling of spin recombination reactions.

PubMed

Tiersch, M; Steiner, U E; Popescu, S; Briegel, H J

2012-04-26

In theories of spin-dependent radical pair reactions, the time evolution of the radical pair, including the effect of the chemical kinetics, is described by a master equation in the Liouville formalism. For the description of the chemical kinetics, a number of possible reaction operators have been formulated in the literature. In this work, we present a framework that allows for a unified description of the various proposed mechanisms and the forms of reaction operators for the spin-selective recombination processes. On the basis of the concept that master equations can be derived from a microscopic description of the spin system interacting with external degrees of freedom, it is possible to gain insight into the underlying microscopic processes and develop a systematic approach toward determining the specific form of the reaction operator in concrete scenarios.

Potential predictors for the amount of intra-operative brain shift during deep brain stimulation surgery

NASA Astrophysics Data System (ADS)

Datteri, Ryan; Pallavaram, Srivatsan; Konrad, Peter E.; Neimat, Joseph S.; D'Haese, Pierre-François; Dawant, Benoit M.

2011-03-01

A number of groups have reported on the occurrence of intra-operative brain shift during deep brain stimulation (DBS) surgery. This has a number of implications for the procedure including an increased chance of intra-cranial bleeding and complications due to the need for more exploratory electrodes to account for the brain shift. It has been reported that the amount of pneumocephalus or air invasion into the cranial cavity due to the opening of the dura correlates with intraoperative brain shift. Therefore, pre-operatively predicting the amount of pneumocephalus expected during surgery is of interest toward accounting for brain shift. In this study, we used 64 DBS patients who received bilateral electrode implantations and had a post-operative CT scan acquired immediately after surgery (CT-PI). For each patient, the volumes of the pneumocephalus, left ventricle, right ventricle, third ventricle, white matter, grey matter, and cerebral spinal fluid were calculated. The pneumocephalus was calculated from the CT-PI utilizing a region growing technique that was initialized with an atlas-based image registration method. A multi-atlas-based image segmentation method was used to segment out the ventricles of each patient. The Statistical Parametric Mapping (SPM) software package was utilized to calculate the volumes of the cerebral spinal fluid (CSF), white matter and grey matter. The volume of individual structures had a moderate correlation with pneumocephalus. Utilizing a multi-linear regression between the volume of the pneumocephalus and the statistically relevant individual structures a Pearson's coefficient of r = 0.4123 (p = 0.0103) was found. This study shows preliminary results that could be used to develop a method to predict the amount of pneumocephalus ahead of the surgery.

Spin-Center Shift-Enabled Direct Enantioselective α-Benzylation of Aldehydes with Alcohols.

PubMed

Nacsa, Eric D; MacMillan, David W C

2018-03-07

Nature routinely engages alcohols as leaving groups, as DNA biosynthesis relies on the removal of water from ribonucleoside diphosphates by a radical-mediated "spin-center shift" (SCS) mechanism. Alcohols, however, remain underused as alkylating agents in synthetic chemistry due to their low reactivity in two-electron pathways. We report herein an enantioselective α-benzylation of aldehydes using alcohols as alkylating agents based on the mechanistic principle of spin-center shift. This strategy harnesses the dual activation modes of photoredox and organocatalysis, engaging the alcohol by SCS and capturing the resulting benzylic radical with a catalytically generated enamine. Mechanistic studies provide evidence for SCS as a key elementary step, identify the origins of competing reactions, and enable improvements in chemoselectivity by rational photocatalyst design.

Rapid pitch correction in choir singers.

PubMed

Grell, Anke; Sundberg, Johan; Ternström, Sten; Ptok, Martin; Altenmüller, Eckart

2009-07-01

Highly and moderately skilled choral singers listened to a perfect fifth reference, with the instruction to complement the fifth such that a major triad resulted. The fifth was suddenly and unexpectedly shifted in pitch, and the singers' task was to shift the fundamental frequency of the sung tone accordingly. The F0 curves during the transitions often showed two phases, an initial quick and large change followed by a slower and smaller change, apparently intended to fine-tune voice F0 to complement the fifth. Anesthetizing the vocal folds of moderately skilled singers tended to delay the reaction. The means of the response times varied in the range 197- 259 ms depending on direction and size of the pitch shifts, as well as on skill and anesthetization.

Lanthanide-cyclodextrin complexes as probes for elucidating optical purity by NMR spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wenzel, T.J.; Bogyo, M.S.; Lebeau, E.L.

1994-06-01

A multidentate ligand is bonded to cyclodextrins by the reaction of diethylenetriaminepentaacetic dianhydride with 6-mono- and 2-mono(ethylenediamine) derivatives of cyclodextrin. Adding Dy(III) to the cyclodextrin derivatives enhances the enantiomeric resolution in the [sup 1]H NMR spectra of carbionoxamine maleate, doxylamine succinate, pheniramine maleate, propranolol hydrochloride, and tryptophan. The enhancement is more pronounced with the secondary derivative. The Dy(III)-induced shifts can be used to elucidate the geometry of cyclodextrin-substrate inclusion complexes. Lanthanide-induced shifts are reported for complexes of aspartame, tryptophan, propranolol, and 1-anilino-8-naphthalenesulfonate with cyclodextrins, and the relative magnitudes of the shifts agree with previously reported structures of the complexes. 37more » refs., 9 figs., 5 tabs.« less

Theoretical lower bounds for parallel pipelined shift-and-add constant multiplications with n-input arithmetic operators

NASA Astrophysics Data System (ADS)

Cruz Jiménez, Miriam Guadalupe; Meyer Baese, Uwe; Jovanovic Dolecek, Gordana

2017-12-01

New theoretical lower bounds for the number of operators needed in fixed-point constant multiplication blocks are presented. The multipliers are constructed with the shift-and-add approach, where every arithmetic operation is pipelined, and with the generalization that n-input pipelined additions/subtractions are allowed, along with pure pipelining registers. These lower bounds, tighter than the state-of-the-art theoretical limits, are particularly useful in early design stages for a quick assessment in the hardware utilization of low-cost constant multiplication blocks implemented in the newest families of field programmable gate array (FPGA) integrated circuits.

Hydrogen enrichment of synthetic fuel

NASA Technical Reports Server (NTRS)

Jay, C. G.

1978-01-01

Synthetic gas may be produced at lower cost and higher efficiency by using outside source of hydrogen. Method is compatible with same temperatures and pressures as shift reaction. Process increases efficiency by using less coal and water to provide equal amount of synthetic gas.

FACILITATED CHEMICAL SYNTHESIS UNDER ALTERNATE REACTION CONDITIONS

EPA Science Inventory

The chemical research in the late 1990's witnessed a paradigm shift towards "environmentally-friendly chemistry" more popularly known as "green chemistry" due to the increasing environmental concerns and legislative requirements to curb the release of chemical waste into the atmo...

CHEMICAL SYNTHESIS USING 'GREENER' ALTERNATIVE REACTION CONDITIONS AND MEDIA

EPA Science Inventory

The chemical research during the last decade has witnessed a paradigm shift towards "environmentally-friendly chemistry" more popularly known as "green chemistry" due to the increasing environmental concerns and legislative requirements to curb the release of chemical waste into ...

Finite Element Analysis and Vibration Control of Lorry’s Shift Mechanism

NASA Astrophysics Data System (ADS)

Qiangwei, Li

2017-11-01

The transmission is one of the important parts of the automobile’s transmission system, Shift mechanism’s main function of transmission is to adjust the position of the shift fork, toggle the synchronizer’s tooth ring, so that the gears are separated and combined to achieve the shift. Therefore, in order to ensure the reliability and stability of the shift process, the vibration characteristics of the shift mechanism cannot be ignored. The static analysis of the shift fork is carried out, and the stress distribution of the shift fork is obtained according to the operating characteristics of the shift mechanism of the lorry transmission in this paper. The modal analysis of the shift mechanism shows the low-order vibration frequencies and the corresponding modal vibration shapes, and the vibration control analysis is carried out according to the simulation results. The simulation results provide the theoretical basis for the reasonable optimization design of the shift mechanism of the lorry transmission.

Synthesis of 2,3-Disubstituted Quinolines via Ketenimine or Carbodiimide Intermediates.

PubMed

Zhao, Hongyang; Xing, Yanpeng; Lu, Ping; Wang, Yanguang

2016-10-10

Cyclopenta[b]quinolines and cyclohexa[b]quinolines were prepared via the reactions of α-diazo ketones with N-(2-cyclopropylidenemethylphenyl)phosphanimines and N-(2-cyclobutylidenemethylphenyl) phosphanimine, respectively. The reaction proceeds in a cascade involving ketenimine formation, 6 π-electron ring closure, and 1,3-alkyl shift. A similar approach was developed for the synthesis of dihydropyrrolo-[2,3-b]quinolines from N-(2-cyclopropylidenemethylphenyl)phosphanimines and isocyanates. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impingement effect of service module reaction control system engine plumes. Results of service module reaction control system plume model force field application to an inflight Skylab mission proximity operation situation with the inflight Skylab response

NASA Technical Reports Server (NTRS)

Lobb, J. D., Jr.

1978-01-01

Plume impingement effects of the service module reaction control system thruster firings were studied to determine if previous flight experience would support the current plume impingement model for the orbiter reaction control system engines. The orbiter reaction control system is used for rotational and translational maneuvers such as those required during rendezvous, braking, docking, and station keeping. Therefore, an understanding of the characteristics and effects of the plume force fields generated by the reaction control system thruster firings were examined to develop the procedures for orbiter/payload proximity operations.

INFLIGHT - APOLLO X - MSC

NASA Image and Video Library

1969-05-19

S69-34038 (18 May 1969) --- View of activity at the flight director's console in the Mission Operations Control Room in the Mission Control Center, Building 30, on the first day of the Apollo 10 lunar orbit mission. Seated are Gerald D. Griffin (foreground) and Glynn S. Lunney, Shift 1 (Black Team) flight directors. Milton L. Windler, standing behind them, is the flight director of Shift 2 (Maroon Team). In the center background, standing, is Dr. Christopher C. Kraft Jr., MSC Director of Flight Operations.

A Framework for Synthesizing the United States Code in Support of Cyberspace Operations

DTIC Science & Technology

2016-03-01

inter- title operations, it is unclear whether this de facto shift in the application of U.S.C. statutes is necessary. The U.S.C. has a limited number of...de facto shift in the application of U.S.C. statutes is necessary. The U.S.C. has a limited number of exclusionary distinctions de jure, which is...NATION STATE Though statecraft has progressed through numerous iterations over the course of human history, in the current post -colonial era, the

Effects of operational conditions on sludge degradation and organic acids formation in low-critical wet air oxidation.

PubMed

Chung, Jinwook; Lee, Mikyung; Ahn, Jaehwan; Bae, Wookeun; Lee, Yong-Woo; Shim, Hojae

2009-02-15

Wet air oxidation processes are to treat highly concentrated organic compounds including refractory materials, sludge, and night soil, and usually operated at supercritical water conditions of high temperature and pressure. In this study, the effects of operational conditions including temperature, pressure, and oxidant dose on sludge degradation and conversion into subsequent intermediates such as organic acids were investigated at low critical wet oxidation conditions. The reaction time and temperature in the wet air oxidation process was shown an important factor affecting the liquefaction of volatile solids, with more significant effect on the thermal hydrolysis reaction rather than the oxidation reaction. The degradation efficiency of sludge and the formation of organic acids were improved with longer reaction time and higher reaction temperature. For the sludge reduction and the organic acids formation under the wet air oxidation, the optimal conditions for reaction temperature, time, pressure, and oxidant dose were shown approximately 240 degrees C, 30min, 60atm, and 2.0L/min, respectively.

Detection of endotoxin using a photonic crystal nanolaser

DOE Office of Scientific and Technical Information (OSTI.GOV)

Takahashi, Daichi; Hachuda, Shoji; Watanabe, Takumi

Fast and reliable detection of endotoxin (ET) in medical equipment and pharmaceutical products is an essential precursor to clinical treatment. In this study, we demonstrate the use of shifts in wavelength of photonic crystal nanolasers for sensing the Limulus amebocyte lysate reaction, which is a standard method for detecting ET. From working curves of wavelength shift vs ET concentration, whose correlation factors were as high as 98%, we detected a required concentration of 0.001 EU/ml within 33 min and detected a low concentration of 0.0001 EU/ml.

Detection of endotoxin using a photonic crystal nanolaser

NASA Astrophysics Data System (ADS)

Takahashi, Daichi; Hachuda, Shoji; Watanabe, Takumi; Nishijima, Yoshiaki; Baba, Toshihiko

2015-03-01

Fast and reliable detection of endotoxin (ET) in medical equipment and pharmaceutical products is an essential precursor to clinical treatment. In this study, we demonstrate the use of shifts in wavelength of photonic crystal nanolasers for sensing the Limulus amebocyte lysate reaction, which is a standard method for detecting ET. From working curves of wavelength shift vs ET concentration, whose correlation factors were as high as 98%, we detected a required concentration of 0.001 EU/ml within 33 min and detected a low concentration of 0.0001 EU/ml.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dagle, Robert A.; Lizarazo Adarme, Jair A.; Lebarbier, Vanessa MC

A composite Pd/ZnO/Al2O3-HZSM-5 (Si/Al=40) catalytic system was evaluated for the synthesis of gasoline-range hydrocarbons directly from synthesis gas. Bifunctional catalyst comprising PdZn metal and acid sites present the required catalytically active sites necessary for the methanol synthesis, methanol dehydration, and methanol-to-gasoline reactions. This system provides a unique catalytic pathway for the production of liquid hydrocarbons directly from syngas. However, selectivity control is difficult and poses many challenges. The composite catalytic system was evaluated under various process conditions. Investigated were the effects of temperature (310-375oC), pressure (300-1000 psig), time-on-stream (50 hrs), and gas-hour space velocity (740-2970 hr-1), using a H2/CO molarmore » syngas ratio of 2.0. By operating at the lower end of the temperature range investigated, liquid hydrocarbon formation was favored, as was decreased amounts of undesirable light hydrocarbons. However, lower operating temperatures also facilitated undesirable CO2 formation via the water-gas shift reaction. Higher operating pressures slightly favored liquid synthesis. Operating at relatively low pressures (e.g. 300 psig) was made possible, whereas for methanol synthesis alone higher pressure are usually required to achieve similar conversion levels (e.g. 1000 psig). Thermodynamic constraints on methanol synthesis are eased by pushing the equilibrium through hydrocarbon formation. Catalytic performance was also evaluated by altering Pd and Zn composition of the Pd/ZnO/Al2O3 catalyst. Of the catalysts and conditions tested, selectivity toward liquid hydrocarbon was highest when using a 5% Pd metal loading and Pd/Zn molar ratio of 0.25 and mixed with HZMS-5, operating at 310oC and 300 psig, CO conversion was 43 % and selectivity (carbon weight basis) to hydrocarbons was 49 wt. %. Of the hydrocarbon fraction, 44wt. % was in the C5-C12 liquid product range and consisted primarily of aromatic polymethylbenzenes. However, as syngas conversion increases with increasing temperature, selectivity to liquid product diminished. This is attributed, in large part, to increased saturation of the olefinic intermediates over PdZn metal sites. Under all the conditions and catalysts evaluated in this study, generating liquid product in high yield was challenging (<10 wt. % C5+ yield).« less

Speeding Up Sigmatropic Shifts-To Halve or to Hold.

PubMed

Tantillo, Dean J

2016-04-19

Catalysis is common. Rational catalyst design, however, is at the frontier of chemical science. Although the histories of physical organic and synthetic organic chemistry boast key chapters involving [3s,3s] sigmatropic shifts, catalysis of these reactions is much less common than catalysis of ostensibly more complex processes. The comparative dearth of catalysts for sigmatropic shifts is perhaps a result of the perception that transition state structures for these reactions, like their reactants, are nonpolar and therefore not amenable to selective stabilization and its associated barrier lowering. However, as demonstrated in this Account, transition state structures for [3s,3s] sigmatropic shifts can in fact have charge distributions that differ significantly from those of reactants, even for hydrocarbon substrates, allowing for barriers to be decreased and rates increased. In some cases, differences in charge distribution result from the inclusion of heteroatoms at specific positions in reactants, but in other cases differences are actually induced by catalysts. Perhaps surprisingly, strategies for complexation of transition state structures that remain nonpolar are also possible. In general, the strategies for catalysis employed can be characterized as involving either mechanistic intervention, where a catalyst induces a change from the concerted mechanism expected for a [3s,3s] sigmatropic shift to a multistep process (cutting the transformation into halves or smaller pieces) whose overall barrier is decreased relative to the concerted process, or transition state complexation, where a catalyst simply binds (holds) more tightly to the transition state structure for a [3s,3s] sigmatropic shift than to the reactant, leading to a lower barrier in the presence of the catalyst. Both of these strategies can be considered to be biomimetic in that enzymes frequently induce multistep processes and utilize selective transition state stabilization for the steps involved. In addition, transition state complexation was the principle around which catalytic antibodies were originally designed. The field of catalysis of sigmatropic shifts is now ready for rational design. The studies described here all provide evidence for the origins of rate acceleration, derived in large part from the results of quantum chemical calculations, that can now be applied to the design of new catalysts for [3s,3s] and other sigmatropic shifts.

Evaluation of the impact of shiftwork and chronotype on the workers of the imprint and cutting/welding sectors of a flexible packaging manufacturer.

PubMed

de M Guimarães, L B; Pessa, S L R; Biguelini, C

2012-01-01

This article presents a study on the impact of shiftwork and chronotype on the perception of the work conditions, workload and adjustment to shiftwork by the workers of two sectors of a flexible packaging manufacturer, which operates in three fixed shifts. The workers are allocated in one of the shifts (morning, evening and night shifts) without evaluation of their chronotype and/or social needs. The workers' evaluation of the shift system and their work show that they prefer a fixed shift and to work in a shift compatible with their chronotype. The workers with chonotype uncompatible with the shift time tend to be less satisfied with the work conditions and content and feel more discomfort/pain.

Characterization of poly(L-lactide/Propylene glycol) based polyurethane films using ATR-FTIR spectroscopy

NASA Astrophysics Data System (ADS)

Manap, Siti Munirah; Ahmad, Azizan; Anuar, Farah Hannan

2016-11-01

A polyurethane films consisting of PLLA, PPG and PLLA-PPG were prepared using solution casting method. Three types of polyurethane were prepared: PPLA:PMDI, PPG:PMDI and PLLA-PPG:PMDI in the presence of polymeric diphenylmethane diisocyanate (PMDI) as the coupling agent and catalyst, Sn(Oct)2. The aim of this research was to improve the physicals properties of PLLA and PPG homopolymers through copolymerization between the two polymers. The homopolymers and polyurethane films were characterized using ATR-FTIR spectroscopy. Chemical reaction between PLLA, PPG and PMDI before and after the reaction were confirmed by observing the shifting of wavenumber for the carbonyl and ether group. Other than that, the additional band for N-H after the reaction indicated that the reaction was successful.

Chemical Reaction Rate Coefficients from Ring Polymer Molecular Dynamics: Theory and Practical Applications

DOE PAGES

Suleimanov, Yury V.; Aoiz, F. Javier; Guo, Hua

2016-09-14

This Feature Article presents an overview of the current status of ring polymer molecular dynamics (RPMD) rate theory. We first analyze the RPMD approach and its connection to quantum transition-state theory. We then focus on its practical applications to prototypical chemical reactions in the gas phase, which demonstrate how accurate and reliable RPMD is for calculating thermal chemical reaction rate coefficients in multifarious cases. This review serves as an important checkpoint in RPMD rate theory development, which shows that RPMD is shifting from being just one of recent novel ideas to a well-established and validated alternative to conventional techniques formore » calculating thermal chemical rate coefficients. We also hope it will motivate further applications of RPMD to various chemical reactions.« less

Off-line real-time FTIR analysis of a process step in imipenem production

NASA Astrophysics Data System (ADS)

Boaz, Jhansi R.; Thomas, Scott M.; Meyerhoffer, Steven M.; Staskiewicz, Steven J.; Lynch, Joseph E.; Egan, Richard S.; Ellison, Dean K.

1992-08-01

We have developed an FT-IR method, using a Spectra-Tech Monit-IR 400 systems, to monitor off-line the completion of a reaction in real-time. The reaction is moisture-sensitive and analysis by more conventional methods (normal-phase HPLC) is difficult to reproduce. The FT-IR method is based on the shift of a diazo band when a conjugated beta-diketone is transformed into a silyl enol ether during the reaction. The reaction mixture is examined directly by IR and does not require sample workup. Data acquisition time is less than one minute. The method has been validated for specificity, precision and accuracy. The results obtained by the FT-IR method for known mixtures and in-process samples compare favorably with those from a normal-phase HPLC method.

Effects of night shift on the cognitive load of physicians and urinary steroid hormone profiles - a randomized crossover trial.

PubMed

Osterode, Wolf; Schranz, Sandra; Jordakieva, Galateja

2018-03-21

Mental and physical stress is common in physicians during night shifts. Neurocognitive effects of sleep deprivation as well as alterations in hormonal and metabolic parameters have previously been described. The aim of this crossover study was to evaluate the effects of night-shift work with partial sleep deprivation on steroid hormone excretion and possible associations with mood, sleep characteristics and cognitive functions in physicians. In total, 34 physicians (mean age 42 ± 8.5 years, 76.5% male) from different departments of the General Hospital of Vienna, Austria, were randomly assigned to two conditions: a regular day shift (8 h on duty, condition 1) and a continuous day-night shift (24 h on duty, condition 2). In both conditions, physicians collected a 24 h urine sample for steroid hormone concentration analysis and further completed psychological tests, including the sleep questionnaire (SF-A), the questionnaire for mental state (MDBF) and the computer-assisted visual memory test (FVW) before and at the end of their shifts, respectively. Although mean sleep deprivation during night shift was relatively small (~1.5 h) the impairment in participants' mental state was high in all three dimensions (mood, vigilance and agitation, p ≤ 0.001). Sleep quality (SQ), feeling of being recovered after sleep and mental balance decreased (p ≤ 0.001), whereas mental exhaustion increased (p < 0.05). Moreover, we could show a nearly linear relationship between most of these self-rating items. Testing visual memory participants made significantly more mistakes after night shift (p = 0.011), however, mostly in incorrectly identified items and not in correctly identified ones (FVW). SQ and false identified items were negatively correlated, whereas SQ and time of reaction were positively associated. It is assumed that after night shift, a tendency exists to make faster wrong decisions. SQ did not influence correctly identified items in FVW. In contrast to previous investigations, we found that only excretion rates for pregnanetriol and androsterone/etiocholanolone ratios (p < 0.05, respectively) were slightly reduced in 24-h urine samples after night shift. A considerable stimulation of the adrenocortical axis could not be affirmed. In general, dehydroepiandrosteron (DHEA) was negatively associated with the sense of recreation after sleep and with the time of reaction and positively correlated with correctly identified items in the FVW test. These results, on the one hand, are in line with previous findings indicating that stress and sleep deprivation suppress gonadal steroids, but, on the other hand, do not imply significant adrenocortical-axis stimulation (e.g. an increase of cortisol) during the day-night shift.

Exercise leads to faster postural reflexes, improved balance and mobility, and fewer falls in older persons with chronic stroke.

PubMed

Marigold, Daniel S; Eng, Janice J; Dawson, Andrew S; Inglis, J Timothy; Harris, Jocelyn E; Gylfadóttir, Sif

2005-03-01

To determine the effect of two different community-based group exercise programs on functional balance, mobility, postural reflexes, and falls in older adults with chronic stroke. A randomized, clinical trial. Community center. Sixty-one community-dwelling older adults with chronic stroke. Participants were randomly assigned to an agility (n=30) or stretching/weight-shifting (n=31) exercise group. Both groups exercised three times a week for 10 weeks. Participants were assessed before, immediately after, and 1 month after the intervention for Berg Balance, Timed Up and Go, step reaction time, Activities-specific Balance Confidence, and Nottingham Health Profile. Testing of standing postural reflexes and induced falls evoked by a translating platform was also performed. In addition, falls in the community were tracked for 1 year from the start of the interventions. Although exercise led to improvements in all clinical outcome measures for both groups, the agility group demonstrated greater improvement in step reaction time and paretic rectus femoris postural reflex onset latency than the stretching/weight-shifting group. In addition, the agility group experienced fewer induced falls on the platform. Group exercise programs that include agility or stretching/weight shifting exercises improve postural reflexes, functional balance, and mobility and may lead to a reduction of falls in older adults with stroke.

49 CFR 393.100 - Which types of commercial motor vehicles are subject to the cargo securement standards of this...

Code of Federal Regulations, 2011 CFR

2011-10-01

... AND ACCESSORIES NECESSARY FOR SAFE OPERATION Protection Against Shifting and Falling Cargo § 393.100..., spilling, blowing or falling from the motor vehicle. (c) Prevention against shifting of load. Cargo must be...

49 CFR 393.100 - Which types of commercial motor vehicles are subject to the cargo securement standards of this...

Code of Federal Regulations, 2012 CFR

2012-10-01

... AND ACCESSORIES NECESSARY FOR SAFE OPERATION Protection Against Shifting and Falling Cargo § 393.100..., spilling, blowing or falling from the motor vehicle. (c) Prevention against shifting of load. Cargo must be...

49 CFR 393.100 - Which types of commercial motor vehicles are subject to the cargo securement standards of this...

Code of Federal Regulations, 2014 CFR

2014-10-01

... AND ACCESSORIES NECESSARY FOR SAFE OPERATION Protection Against Shifting and Falling Cargo § 393.100..., spilling, blowing or falling from the motor vehicle. (c) Prevention against shifting of load. Cargo must be...

49 CFR 393.100 - Which types of commercial motor vehicles are subject to the cargo securement standards of this...

Code of Federal Regulations, 2010 CFR

2010-10-01

... AND ACCESSORIES NECESSARY FOR SAFE OPERATION Protection Against Shifting and Falling Cargo § 393.100..., spilling, blowing or falling from the motor vehicle. (c) Prevention against shifting of load. Cargo must be...

49 CFR 393.100 - Which types of commercial motor vehicles are subject to the cargo securement standards of this...

Code of Federal Regulations, 2013 CFR

2013-10-01

... AND ACCESSORIES NECESSARY FOR SAFE OPERATION Protection Against Shifting and Falling Cargo § 393.100..., spilling, blowing or falling from the motor vehicle. (c) Prevention against shifting of load. Cargo must be...

SITE: INNOVATION ON THE MOVE

EPA Science Inventory

A recent review of the SITE Program indicated that operational shifts are necessary to maintain the program's position as a progressive, "state-of-the-art" leader in the environmental field. The SITE Program will shift from a technology-driven focus to a more integrated approach ...

Split-personality transmission: shifts like an automatic, saves fuel like a manual

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scott, D.

1981-11-01

The design, operation and performance of a British-invented automatic transmission which claims to result in fuel economy valves equal to those attained with manual shifts are described. Developed for both 4-speed and 6-speed transmissions, this transmission uses standard parts made for existing manual transmissions, rearranges the gear pairings, and relies on a microcomputer to pick the optimal shift points according to load requirements. (LCL)

GPU-Accelerated Forward and Back-Projections with Spatially Varying Kernels for 3D DIRECT TOF PET Reconstruction.

PubMed

Ha, S; Matej, S; Ispiryan, M; Mueller, K

2013-02-01

We describe a GPU-accelerated framework that efficiently models spatially (shift) variant system response kernels and performs forward- and back-projection operations with these kernels for the DIRECT (Direct Image Reconstruction for TOF) iterative reconstruction approach. Inherent challenges arise from the poor memory cache performance at non-axis aligned TOF directions. Focusing on the GPU memory access patterns, we utilize different kinds of GPU memory according to these patterns in order to maximize the memory cache performance. We also exploit the GPU instruction-level parallelism to efficiently hide long latencies from the memory operations. Our experiments indicate that our GPU implementation of the projection operators has slightly faster or approximately comparable time performance than FFT-based approaches using state-of-the-art FFTW routines. However, most importantly, our GPU framework can also efficiently handle any generic system response kernels, such as spatially symmetric and shift-variant as well as spatially asymmetric and shift-variant, both of which an FFT-based approach cannot cope with.

GPU-Accelerated Forward and Back-Projections With Spatially Varying Kernels for 3D DIRECT TOF PET Reconstruction

NASA Astrophysics Data System (ADS)

Ha, S.; Matej, S.; Ispiryan, M.; Mueller, K.

2013-02-01

We describe a GPU-accelerated framework that efficiently models spatially (shift) variant system response kernels and performs forward- and back-projection operations with these kernels for the DIRECT (Direct Image Reconstruction for TOF) iterative reconstruction approach. Inherent challenges arise from the poor memory cache performance at non-axis aligned TOF directions. Focusing on the GPU memory access patterns, we utilize different kinds of GPU memory according to these patterns in order to maximize the memory cache performance. We also exploit the GPU instruction-level parallelism to efficiently hide long latencies from the memory operations. Our experiments indicate that our GPU implementation of the projection operators has slightly faster or approximately comparable time performance than FFT-based approaches using state-of-the-art FFTW routines. However, most importantly, our GPU framework can also efficiently handle any generic system response kernels, such as spatially symmetric and shift-variant as well as spatially asymmetric and shift-variant, both of which an FFT-based approach cannot cope with.

Evaluating the traditional day and night shift in an acute care surgery fellowship: Is the swing shift a better choice?

PubMed

Chestovich, Paul J; McNicoll, Christopher F; Ingalls, Nichole K; Kuhls, Deborah A; Fraser, Douglas R; Morrissey, Shawna L; Fildes, John J

2018-01-01

Fellowship trainees in acute care surgery require experience in the management of complex and operative trauma cases. Trauma center staffing usually follows standard 12-hour or 24-hour shifts, with resident and fellow trainees following a similar schedule. Although trauma admissions can be generally unpredictable, we analyzed temporal trends of trauma patient arrival times to determine the best time frame to maximize trainee experience during each day. We reviewed 10 years (2007-2016) of trauma registry data for blunt and penetrating trauma activations. Hourly volumetric trends were observed, and three specific events were chosen for detailed analysis: (1) trauma activation with Injury Severity Score (ISS) greater than 15, (2) laparotomy for trauma, and (3) thoracotomy for trauma. A retrospective shift log was created, which included day (7:00 AM to 7:00 PM), night (7:00 PM to 7:00 AM), and swing (noon to midnight) shifts. A swing shift was chosen because it captures the peak volume for all three events. Means and 95% confidence intervals were calculated, and comparisons were made between shifts using the Wilcoxon matched-pairs signed rank test with Bonferroni correction, and p less than 0.05 considered significant. During the 10-year study period, 28,287 patients were treated at our trauma center. This included the evaluation and management of 7,874 patients with ISS greater than 15, performance of 1,766 laparotomies, and 392 thoracotomies for trauma. Swing shift was superior to both day and night shifts for ISS greater than 15 (p < 0.001). Both swing and night shifts were superior to day shift for laparotomies (p < 0.001). Swing shift was superior to both day shift (p < 0.001) and night shift (p = 0.031). Shifts with the highest yield of ISS greater than 15, laparotomies, and thoracotomies include night and swing shifts on Fridays and Saturdays. Projected experience of acute care surgery fellows in managing complex trauma patients increases with the integration of swing shifts into the schedule. Daily trauma volume follows a temporal pattern which, when used correctly, can increase trainee exposure to complex and operative trauma cases. We encourage other centers to analyze their volume and adjust trainee schedules accordingly to maximize their educational experience. Therapeutic study, level IV.

Method and apparatus for executing an asynchronous clutch-to-clutch shift in a hybrid transmission

DOEpatents

Demirovic, Besim; Gupta, Pinaki; Kaminsky, Lawrence A.; Naqvi, Ali K.; Heap, Anthony H.; Sah, Jy-Jen F.

2014-08-12

A hybrid transmission includes first and second electric machines. A method for operating the hybrid transmission in response to a command to execute a shift from an initial continuously variable mode to a target continuously variable mode includes increasing torque of an oncoming clutch associated with operating in the target continuously variable mode and correspondingly decreasing a torque of an off-going clutch associated with operating in the initial continuously variable mode. Upon deactivation of the off-going clutch, torque outputs of the first and second electric machines and the torque of the oncoming clutch are controlled to synchronize the oncoming clutch. Upon synchronization of the oncoming clutch, the torque for the oncoming clutch is increased and the transmission is operated in the target continuously variable mode.

Glycerol etherification with TBA: high yield to poly-ethers using a membrane assisted batch reactor.

PubMed

Cannilla, Catia; Bonura, Giuseppe; Frusteri, Leone; Frusteri, Francesco

2014-05-20

In this work, a novel approach to obtain high yield to poly-tert-butylglycerolethers by glycerol etherification reaction with tert-butyl alcohol (TBA) is proposed. The limit of this reaction is the production of poly-ethers, which inhibits the formation of poly-ethers potentially usable in the blend with conventional diesel for transportation. The results herein reported demonstrate that the use of a water permselective membrane offers the possibility to shift the equilibrium toward the formation of poly-ethers since the water formed during reaction is continuously and selectively removed from the reaction medium by the recirculation of the gas phase. Using a proper catalyst and optimizing the reaction conditions, in a single experiment, a total glycerol conversion can be reached with a yield to poly-ethers close to 70%, which represents data never before reached using TBA as reactant. The approach here proposed could open up new opportunities for all catalytic reactions affected by water formation.

High Energy-Density and Reversibility of Iron Fluoride Cathode Enabled Via an Intercalation-Extrusion Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fan, Xiulin; Hu, Enyuan; Ji, Xiao

Iron fluoride, an intercalation-conversion cathode for lithium ion batteries, promises a high theoretical energy density of 1922 Wh Kg –1. However, poor electrochemical reversibility due to repeated breaking/reformation of metal-fluoride bonds poses a grand challenge for its practical application. Here we report that both a high reversibility over 1000 cycles and a high capacity of 420 mAh g –1 can be realized by concerted doping of cobalt and oxygen into iron fluoride. In the doped nanorods, an energy density of ~1000 Wh Kg –1 with a decay rate of 0.03% per cycle is achieved. The anion and cation’s co-substitutions thermodynamicallymore » reduce conversion-reaction potential and shift the reaction from less reversible intercalation-conversion reaction in iron fluoride to a highly reversible intercalation-extrusion reaction in doped material. Furthermore, the co-substitution strategy to tune the thermodynamic features of the reactions could be extended to other high energy conversion materials for improved performance.« less

High Energy-Density and Reversibility of Iron Fluoride Cathode Enabled Via an Intercalation-Extrusion Reaction

DOE PAGES

Fan, Xiulin; Hu, Enyuan; Ji, Xiao; ...

2018-05-30

Iron fluoride, an intercalation-conversion cathode for lithium ion batteries, promises a high theoretical energy density of 1922 Wh Kg –1. However, poor electrochemical reversibility due to repeated breaking/reformation of metal-fluoride bonds poses a grand challenge for its practical application. Here we report that both a high reversibility over 1000 cycles and a high capacity of 420 mAh g –1 can be realized by concerted doping of cobalt and oxygen into iron fluoride. In the doped nanorods, an energy density of ~1000 Wh Kg –1 with a decay rate of 0.03% per cycle is achieved. The anion and cation’s co-substitutions thermodynamicallymore » reduce conversion-reaction potential and shift the reaction from less reversible intercalation-conversion reaction in iron fluoride to a highly reversible intercalation-extrusion reaction in doped material. Furthermore, the co-substitution strategy to tune the thermodynamic features of the reactions could be extended to other high energy conversion materials for improved performance.« less

Carbon-Carbon Bond Formation and Hydrogen Production in the Ketonization of Aldehydes.

PubMed

Orozco, Lina M; Renz, Michael; Corma, Avelino

2016-09-08

Aldehydes possess relatively high chemical energy, which is the driving force for disproportionation reactions such as Cannizzaro and Tishchenko reactions. Generally, this energy is wasted if aldehydes are transformed into carboxylic acids with a sacrificial oxidant. Here, we describe a cascade reaction in which the surplus energy of the transformation is liberated as molecular hydrogen for the oxidation of heptanal to heptanoic acid by water, and the carboxylic acid is transformed into potentially industrially relevant symmetrical ketones by ketonic decarboxylation. The cascade reaction is catalyzed by monoclinic zirconium oxide (m-ZrO2 ). The reaction mechanism has been studied through cross-coupling experiments between different aldehydes and acids, and the final symmetrical ketones are formed by a reaction pathway that involves the previously formed carboxylic acids. Isotopic studies indicate that the carboxylic acid can be formed by a hydride shift from the adsorbed aldehyde on the metal oxide surface in the absence of noble metals. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mani, Tomoyasu; Grills, David C.

Delocalization of charges is one of the factors controlling charge transport in conjugated molecules. It is considered to play an important role in the performance of a wide range of molecular technologies, including organic solar cells and organic electronics. Dimerization reactions are well-suited as a model to investigate intermolecular spatial delocalization of charges. And while dimerization reactions of radical cations are well investigated, studies on radical anions are still scarce. Upon dimerization of radical anions with neutral counterparts, an electron is considered to delocalize over the two molecules. By using time-resolved infrared (TRIR) detection coupled with pulse radiolysis, we showmore » that radical anions of 4-n-hexyl-4'-cyanobiphenyl (6CB) undergo such dimerization reactions, with an electron equally delocalized over the two molecules. We have recently demonstrated that nitrile ν(C≡N) vibrations respond to the degree of electron localization of nitrile-substituted anions: we can quantify the changes in the electronic charges from the neutral to the anion states in the nitriles by monitoring the ν(C≡N) IR shifts. In the first part of this article, we show that the sensitivity of the ν(C≡N) IR shifts does not depend on solvent polarity. In the second part, we describe how probing the shifts of the nitrile IR vibrational band unambiguously confirms the formation of dimer radical anions, with K dim = 3 × 10 4 M –1. IR findings are corroborated by electronic absorption spectroscopy and electronic structure calculations. We find that the presence of a hexyl chain and the formation of π–π interactions are both crucial for dimerization of radical anions of 6CB with neutral 6CB. Our study provides clear evidence of spatial delocalization of electrons over two molecular fragments.« less

Effect of shoe inserts on kinematics, center of pressure, and leg joint moments during running.

PubMed

Nigg, Benno M; Stergiou, Pro; Cole, Gerald; Stefanyshyn, Darren; Mündermann, Anne; Humble, Neil

2003-02-01

The purposes of this project were to assess the effect of four different shoe inserts on the path of the center of pressure (COP), to quantify the effect of these inserts on selected knee joint moments during running, and to assess the potential of COP data to predict the effects of inserts/orthotics on knee joint moments. Kinematics for the lower extremities, resultant ankle and knee joint moments, and the path of the COP were collected from the right foot of 15 male subjects while running heel-toe with five different shoe inserts (full or half with 4.5-mm postings). Individual movement changes with respect to the neutral insert condition were typically small and not systematic. Significant changes for the path of the COP were registered only for the full lateral insert condition with an average shift toward the lateral side. The mediolateral shift of the COP was not consistent for the full medial and the two half-shoe inserts. The subject-specific reactions to the inserts' intervention in the corresponding knee joint moments were typically not consistent. Compared with the neutral insert condition, subjects showed increases or decreases of the knee joint moments. The correlation between the individual COP shifts and the resultant knee joint moment was generally small. The results of this study showed that subject-specific reactions to the tested inserts were often not as expected. Additionally, reactions were not consistent between the subjects. This result suggests that the prescription of inserts and/or orthotics is a difficult task and that methods must be developed to test and assess these effects. Such methods, however, are not currently available.

Probing Intermolecular Electron Delocalization in Dimer Radical Anions by Vibrational Spectroscopy

DOE PAGES

Mani, Tomoyasu; Grills, David C.

2017-07-05

Delocalization of charges is one of the factors controlling charge transport in conjugated molecules. It is considered to play an important role in the performance of a wide range of molecular technologies, including organic solar cells and organic electronics. Dimerization reactions are well-suited as a model to investigate intermolecular spatial delocalization of charges. And while dimerization reactions of radical cations are well investigated, studies on radical anions are still scarce. Upon dimerization of radical anions with neutral counterparts, an electron is considered to delocalize over the two molecules. By using time-resolved infrared (TRIR) detection coupled with pulse radiolysis, we showmore » that radical anions of 4-n-hexyl-4'-cyanobiphenyl (6CB) undergo such dimerization reactions, with an electron equally delocalized over the two molecules. We have recently demonstrated that nitrile ν(C≡N) vibrations respond to the degree of electron localization of nitrile-substituted anions: we can quantify the changes in the electronic charges from the neutral to the anion states in the nitriles by monitoring the ν(C≡N) IR shifts. In the first part of this article, we show that the sensitivity of the ν(C≡N) IR shifts does not depend on solvent polarity. In the second part, we describe how probing the shifts of the nitrile IR vibrational band unambiguously confirms the formation of dimer radical anions, with K dim = 3 × 10 4 M –1. IR findings are corroborated by electronic absorption spectroscopy and electronic structure calculations. We find that the presence of a hexyl chain and the formation of π–π interactions are both crucial for dimerization of radical anions of 6CB with neutral 6CB. Our study provides clear evidence of spatial delocalization of electrons over two molecular fragments.« less

Effect of sulfur hexafluoride gas and post-annealing treatment for inductively coupled plasma etched barium titanate thin films

PubMed Central

2014-01-01

Aerosol deposition- (AD) derived barium titanate (BTO) micropatterns are etched via SF6/O2/Ar plasmas using inductively coupled plasma (ICP) etching technology. The reaction mechanisms of the sulfur hexafluoride on BTO thin films and the effects of annealing treatment are verified through X-ray photoelectron spectroscopy (XPS) analysis, which confirms the accumulation of reaction products on the etched surface due to the low volatility of the reaction products, such as Ba and Ti fluorides, and these residues could be completely removed by the post-annealing treatment. The exact peak positions and chemicals shifts of Ba 3d, Ti 2p, O 1 s, and F 1 s are deduced by fitting the XPS narrow-scan spectra on as-deposited, etched, and post-annealed BTO surfaces. Compared to the as-deposited BTOs, the etched Ba 3d 5/2 , Ba 3d 3/2 , Ti 2p 3/2 , Ti 2p 1/2 , and O 1 s peaks shift towards higher binding energy regions by amounts of 0.55, 0.45, 0.4, 0.35, and 0.85 eV, respectively. A comparison of the as-deposited film with the post-annealed film after etching revealed that there are no significant differences in the fitted XPS narrow-scan spectra except for the slight chemical shift in the O 1 s peak due to the oxygen vacancy compensation in O2-excessive atmosphere. It is inferred that the electrical properties of the etched BTO film can be restored by post-annealing treatment after the etching process. Moreover, the relative permittivity and loss tangent of the post-annealed BTO thin films are remarkably improved by 232% and 2,695%, respectively. PMID:25249824

Role of CO2 in the oxy-dehydrogenation of ethylbenzene to styrene on the CeO2(111) surface

NASA Astrophysics Data System (ADS)

Fan, Hong-Xia; Feng, Jie; Li, Wen-Ying; Li, Xiao-Hong; Wiltowski, Tomasz; Ge, Qing-Feng

2018-01-01

The role of CO2 in the ethylbenzene oxy-dehydrogenation to styrene on the CeO2(111) surface was thoroughly investigated by the density functional theory (DFT) calculations. Results show that the first Csbnd H bond of ethylbenzene is activated via the oxo-insertion with a barrier of 1.70 eV, resulting in a 2-phenylethyl species and an H atom adsorbed on two-adjacent-lattice oxygen. The H adatom forms a hydroxyl-like species (denoted as O*H). The subsequent dehydrogenation to styrene can be assisted by either the next lattice oxygen (pathway R1) or the O*H species (pathway R2). The two pathways have almost the same activation energy (0.84 eV for R1 and 0.85 eV for R2), forming a new O*H and desorbing a H2O molecule while leaving an oxygen vacancy on the surface, respectively. In the presence of CO2, it will react with O*H through the reverse water gas shift reaction with an activation barrier of 0.98 eV and reaction energy of 0.30 eV. The reverse water gas shift reaction helps to clear the H adatoms from the lattice oxygen, thereby competing with styrene formation via pathway R2. However, the activation energy following the reverse water gas shift mechanism is 0.13 eV higher than that of styrene formation via pathway R2. Therefore, the formation of oxygen vacancy cannot be inhibited, while CO2 can react with the surface oxygen vacancy to produce CO with a high activation energy of 2.10 eV.

Shift in Food Intake and Changes in Metabolic Regulation and Gene Expression during Simulated Night-Shift Work: A Rat Model.

PubMed

Marti, Andrea Rørvik; Meerlo, Peter; Grønli, Janne; van Hasselt, Sjoerd Johan; Mrdalj, Jelena; Pallesen, Ståle; Pedersen, Torhild Thue; Henriksen, Tone Elise Gjøtterud; Skrede, Silje

2016-11-08

Night-shift work is linked to a shift in food intake toward the normal sleeping period, and to metabolic disturbance. We applied a rat model of night-shift work to assess the immediate effects of such a shift in food intake on metabolism. Male Wistar rats were subjected to 8 h of forced activity during their rest (ZT2-10) or active (ZT14-22) phase. Food intake, body weight, and body temperature were monitored across four work days and eight recovery days. Food intake gradually shifted toward rest-work hours, stabilizing on work day three. A subgroup of animals was euthanized after the third work session for analysis of metabolic gene expression in the liver by real-time polymerase chain reaction (PCR). Results show that work in the rest phase shifted food intake to rest-work hours. Moreover, liver genes related to energy storage and insulin metabolism were upregulated, and genes related to energy breakdown were downregulated compared to non-working time-matched controls. Both working groups lost weight during the protocol and regained weight during recovery, but animals that worked in the rest phase did not fully recover, even after eight days of recovery. In conclusion, three to four days of work in the rest phase is sufficient to induce disruption of several metabolic parameters, which requires more than eight days for full recovery.

Citrus Juice: Green and Natural Catalyst for the Solvent-free Silica Supported Synthesis of β-Enaminones Using Grindstone Technique.

PubMed

Marvi, Omid; Fekri, Leila Zare

2018-01-01

Citrus Juice as an efficient, cost-effective and green catalyst employed for one-pot synthesis of various β-substituted enaminones through the reaction of β- dicarbonyl compounds with different primary amines in a solvent-free conditions on silica gel as solid surface using grindstone technique in high yields and short reaction times. The presented procedure is operationally simple, practical and green. The wide application of this procedure is demonstrated by the use of various substituted amines to react with β-dicarbonyl compounds. The method was successfully applied for primary amines (15 entries) and the related enaminones were well synthesized in good to excellent yields. Melting points were measured on an Electro thermal 9100 apparatus. 1HNMR and 13C NMR spectra were recorded on a FTNMR BRUKER DRX 500 Avence spectrometer. Chemical shifts were given in ppm from TMS as internal references and CDCl3 was used as the solvent as well. The IR spectra were recorded on a Perkin Elmer FT-IR GX instrument. The chemicals used in this work were purchased from Merck and Fluka chemical companies. Grinding synthesis of citrus juice catalyzed enamination of 1,3-dicarbonyls (acetylacetone, methyl and ethyl-3-oxobutanoate) with various primary amines (aromatic and aliphatic) under solvent-free silica supported conditions was examined and studied (15 entries) and the obtained enaminones were well synthesized in good to excellent yields. Furthermore, the effect of various catalysts on the yield and reaction time for grinding synthesis of 3-phenylamino- but- 2- enoic acid ethyl ester (1) by this method has evaluated as well. A novel, efficient and green protocol for the grinding synthesis of enaminones using citrus juice as natural catalyst has been presented. This methodology is user friendly, green and low cost procedure under mild reaction condition with faster reaction rates. The citrus juice is inexpensive and non-toxic which makes the process convenient, more economic and benign. Furthermore, applying grindstone technique in solvent-free conditions, use of silica gel as a solid and heterogeneous surface in reaction, high yields of products, cleaner reaction profiles, and availability of the reagents makes this method a better choice for synthetic chemists. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

In Vivo Healing after Capsular Plication in an Ovine Shoulder Model

PubMed Central

Kelly, BT; Turner, AS; Bansal, M; Terry, M; Wolf, BR; Warren, RF; Altchek, DW; Allen, AA

2005-01-01

Traditionally, arthroscopic management of shoulder instability has been reserved for patients with isolated Bankart lesions without any capsular laxity or injury. To date, there are no animal studies evaluating the healing potential of capsular plication and/or capsulo-labral repair. The purpose of this in vivo animal study was to determine if the histological capsular healing of an open capsular plication simulating an arthroscopic plication is equivalent to the more traditional open capsular shift involving cutting and advancing the capsule. Twenty-six skeletally mature sheep were randomized to either an open capsular plication simulating arthroscopic plication (n=13), or an open traditional capsular shift (n=13). A sham operation (n=4) was also performed involving exposure to visualize the capsule. Normal non-operated control shoulders were also analyzed. A pathologist blinded to the treatment evaluated both hematoxylin and eosin (H&E) sections and polarized light microscopy. Qualitative scoring evaluated fibrosis, mucinous degeneration, fat necrosis, granuloma formation, vascularity, inflammatory infiltrate and hemosiderin (0 to 3 points). Both the capsular plication and open shift groups demonstrated healing by fibrosis at the site of surgical manipulation. There were no statistical differences in the capsular healing responses between the two groups with regard to fibrosis, granuloma formation and vascularity. The open shift group demonstrated significantly more mucinous degeneration (p=0.038). Fat necrosis was present in 4/13 specimens in the open shift group and none in the capsular plication specimens. Both groups demonstrated disorganized collagen formation under polarized light microscopy. There were no differences between non-operated control specimens and sham surgery specimens. Our findings support the hypothesis that histologic capsular healing is equivalent between the plication group and the open shift group. In addition, the open shift group demonstrated significantly more changes indicative of tissue injury. This basic science model confirms capsular healing after simulated arthroscopic plication, providing support for arthroscopic capsular plication in practice. PMID:16089080

Optimal all-optical switching of a microcavity resonance in the telecom range using the electronic Kerr effect.

PubMed

Yüce, Emre; Ctistis, Georgios; Claudon, Julien; Gérard, Jean-Michel; Vos, Willem L

2016-01-11

We have switched GaAs/AlAs and AlGaAs/AlAs planar microcavities that operate in the "Original" (O) telecom band by exploiting the instantaneous electronic Kerr effect. We observe that the resonance frequency reversibly shifts within one picosecond when the nanostructure is pumped with low-energy photons. We investigate experimentally and theoretically the role of several parameters: the material backbone and its electronic bandgap, the quality factor, and the duration of the switch pulse. The magnitude of the frequency shift is reduced when the backbone of the central λ-layer has a greater electronic bandgap compared to the cavity resonance frequency and the frequency of the pump. This observation is caused by the fact that pumping with photon energies near the bandgap resonantly enhances the switched magnitude. We thus find that cavities operating in the telecom O-band are more amenable to ultrafast Kerr switching than those operating at lower frequencies, such as the C-band. Our results indicate that the large bandgap of AlGaAs/AlAs cavity allows to tune both the pump and the probe to the telecom range to perform Kerr switching without detrimental two-photon absorption. We observe that the magnitude of the resonance frequency shift decreases with increasing quality factor of the cavity. Our model shows that the magnitude of the resonance frequency shift depends on the pump pulse duration and is maximized when the duration matches the cavity storage time to within a factor two. In our experiments, we obtain a maximum shift of the cavity resonance relative to the cavity linewidth of 20%. We project that the shift of the cavity resonance can be increased twofold with a pump pulse duration that better matches the cavity storage time. We provide the essential parameter settings for different materials so that the frequency shift of the cavity resonance can be maximized using the electronic Kerr effect.

Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szymanski, Craig J.; Munusamy, Prabhakaran; Mihai, Cosmin

2015-09-01

Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce3+/Ce4+ ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantifiedmore » the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce3+/Ce4+ ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of cells.« less

Majors' Shift to Natural Gas, The

EIA Publications

2001-01-01

The Majors' Shift to Natural Gas investigates the factors that have guided the United States' major energy producers' growth in U.S. natural gas production relative to oil production. The analysis draws heavily on financial and operating data from the Energy Information Administration's Financial Reporting System (FRS)

Doppler-corrected differential detection system

NASA Technical Reports Server (NTRS)

Simon, Marvin K. (Inventor); Divsalar, Dariush (Inventor)

1991-01-01

Doppler in a communication system operating with a multiple differential phase-shift-keyed format (MDPSK) creates an adverse phase shift in an incoming signal. An open loop frequency estimation is derived from a Doppler-contaminated incoming signal. Based upon the recognition that, whereas the change in phase of the received signal over a full symbol contains both the differentially encoded data and the Doppler induced phase shift, the same change in phase over half a symbol (within a given symbol interval) contains only the Doppler induced phase shift, and the Doppler effect can be estimated and removed from the incoming signal. Doppler correction occurs prior to the receiver's final output of decoded data. A multiphase system can operate with two samplings per symbol interval at no penalty in signal-to-noise ratio provided that an ideal low pass pre-detection filter is employed, and two samples, at 1/4 and 3/4 of the symbol interval T sub s, are taken and summed together prior to incoming signal data detection.

ρ resonance from the I = 1 ππ potential in lattice QCD

NASA Astrophysics Data System (ADS)

Kawai, Daisuke

2018-03-01

We calculate the phase shift for the I = 1 ππ scattering in 2+1 flavor lattice QCD at mπ = 410 MeV, using all-to-all propagators with the LapH smearing. We first investigate the sink operator independence of the I = 2 ππ scattering phase shift to estimate the systematics in the LapH smearing scheme in the HAL QCD method at mπ = 870 MeV. The difference in the scattering phase shift in this channel between the conventional point sink scheme and the smeared sink scheme is reasonably small as long as the next-toleading analysis is employed in the smeared sink scheme with larger smearing levels. We then extract the I = 1 ππ potential with the smeared sink operator, whose scattering phase shift shows a resonant behavior (ρ resonance). We also examine the pole of the S-matrix corresponding to the ρ resonance in the complex energy plane.

Studies on hand-held visual communication device for the deaf and speech-impaired 2. Keyboard design.

PubMed

Thurlow, W R

1980-01-01

Experiments with keyboard arrangements of letters show that simple alphabetic letter-key sequences with 4 to 5 letters in a row lead to most rapid visual search performance. Such arrangements can be used on keyboards operated by the index finger of one hand. Arrangement of letters in words offers a promising alternative because these arrangements can be readily memorized and can result in small interletter distances on the keyboard for frequently occurring letter sequences. Experiments on operation of keyboards show that a space or shift key operated by the left hand (which also holds the communication device) results in faster keyboard operation than when space or shift keys on the front of the keyboard (operated by right hand) are used. Special problems of the deaf-blind are discussed. Keyboard arrangements are investigated, and matching tactual codes are suggested.

Sleep Quality and Vigilance Differ Among Inpatient Nurses Based on the Unit Setting and Shift Worked.

PubMed

Surani, Salim; Hesselbacher, Sean; Guntupalli, Bharat; Surani, Sara; Subramanian, Shyam

2015-12-01

Sleepiness in nurses has been shown to impact patient care and safety. The objectives of this study are to measure sleep quality, sleepiness, fatigue, and vigilance in inpatient nurses and to assess how setting (intensive care unit versus the general floor) and shift worked (day versus night) affect these measures. Nurses from both the ICU and floor were included in the study. Participants completed questionnaires assessing self-reported sleep quality (Pittsburgh Sleep Quality Index, PSQI), sleepiness (Stanford Sleepiness Scale and Epworth Sleepiness Scale, ESS), and fatigue (Fatigue Severity Scale, FSS). Vigilance was measured by means of the psychomotor vigilance test (PVT), before and after a 12-hour duty shift. The ESS was abnormal in 22% of all nurses, the FSS was abnormal in 33%, and the global PSQI was abnormal in 63%. More ICU nurses than floor nurses reported abnormal sleep quality (component 5) on the PSQI. Sleep medication use (PSQI component 6) was higher in night shift nurses. The FSS was greater in night shift nurses. On preshift PVT testing, day-shift nurses overall provided faster mean reaction time (RT) than night-shift nurses. ICU nurses working the day shift made more than twice as many total errors and false starts than day shift floor nurses. Floor nurses demonstrated a significant decrease from preshift to postshift in the mean of the fastest 10% RT. Our data indicate that a significant number of inpatient nurses have impaired sleep quality, excessive sleepiness, and abnormal fatigue, which may place them at a greater risk of making medical errors and harming patients; these problems are especially pronounced in night shift workers. PVT results were inconsistent, but floor and day shift nurses performed better on some tasks than ICU and night shift nurses.

Quasiclassical trajectory study of the Cl+CH4 reaction dynamics on a quadratic configuration interaction with single and double excitation interpolated potential energy surface.

PubMed

Castillo, J F; Aoiz, F J; Bañares, L

2006-09-28

An ab initio interpolated potential energy surface (PES) for the Cl+CH(4) reactive system has been constructed using the interpolation method of Collins and co-workers [J. Chem. Phys. 102, 5647 (1995); 108, 8302 (1998); 111, 816 (1999); Theor. Chem. Acc. 108, 313 (2002)]. The ab initio calculations have been performed using quadratic configuration interaction with single and double excitation theory to build the PES. A simple scaling all correlation technique has been used to obtain a PES which yields a barrier height and reaction energy in good agreement with high level ab initio calculations and experimental measurements. Using these interpolated PESs, a detailed quasiclassical trajectory study of integral and differential cross sections, product rovibrational populations, and internal energy distributions has been carried out for the Cl+CH(4) and Cl+CD(4) reactions, and the theoretical results have been compared with the available experimental data. It has been shown that the calculated total reaction cross sections versus collision energy for the Cl+CH(4) and Cl+CD(4) reactions is very sensitive to the barrier height. Besides, due to the zero-point energy (ZPE) leakage of the CH(4) molecule to the reaction coordinate in the quasiclassical trajectory (QCT) calculations, the reaction threshold falls below the barrier height of the PES. The ZPE leakage leads to CH(3) and HCl coproducts with internal energy below its corresponding ZPEs. We have shown that a Gaussian binning (GB) analysis of the trajectories yields excitation functions in somehow better agreement with the experimental determinations. The HCl(v'=0) and DCl(v'=0) rotational distributions are as well very sensitive to the ZPE problem. The GB correction narrows and shifts the rotational distributions to lower values of the rotational quantum numbers. However, the present QCT rotational distributions are still hotter than the experimental distributions. In both reactions the angular distributions shift from backward peaked to sideways peaked as collision energy increases, as seen in the experiments and other theoretical calculations.

Quasiclassical trajectory study of the Cl +CH4 reaction dynamics on a quadratic configuration interaction with single and double excitation interpolated potential energy surface

NASA Astrophysics Data System (ADS)

Castillo, J. F.; Aoiz, F. J.; Bañares, L.

2006-09-01

An ab initio interpolated potential energy surface (PES) for the Cl +CH4 reactive system has been constructed using the interpolation method of Collins and co-workers [J. Chem. Phys. 102, 5647 (1995); 108, 8302 (1998); 111, 816 (1999); Theor. Chem. Acc. 108, 313 (2002)]. The ab initio calculations have been performed using quadratic configuration interaction with single and double excitation theory to build the PES. A simple scaling all correlation technique has been used to obtain a PES which yields a barrier height and reaction energy in good agreement with high level ab initio calculations and experimental measurements. Using these interpolated PESs, a detailed quasiclassical trajectory study of integral and differential cross sections, product rovibrational populations, and internal energy distributions has been carried out for the Cl +CH4 and Cl +CD4 reactions, and the theoretical results have been compared with the available experimental data. It has been shown that the calculated total reaction cross sections versus collision energy for the Cl +CH4 and Cl +CD4 reactions is very sensitive to the barrier height. Besides, due to the zero-point energy (ZPE) leakage of the CH4 molecule to the reaction coordinate in the quasiclassical trajectory (QCT) calculations, the reaction threshold falls below the barrier height of the PES. The ZPE leakage leads to CH3 and HCl coproducts with internal energy below its corresponding ZPEs. We have shown that a Gaussian binning (GB) analysis of the trajectories yields excitation functions in somehow better agreement with the experimental determinations. The HCl(v'=0) and DCl(v'=0) rotational distributions are as well very sensitive to the ZPE problem. The GB correction narrows and shifts the rotational distributions to lower values of the rotational quantum numbers. However, the present QCT rotational distributions are still hotter than the experimental distributions. In both reactions the angular distributions shift from backward peaked to sideways peaked as collision energy increases, as seen in the experiments and other theoretical calculations.

XAFS Study on Chlorination of Y2O3 in LiCl-KCl-ZrCl4 Melt

NASA Astrophysics Data System (ADS)

Okamoto, Yoshihiro; Yaita, Tsuyoshi; Shiwaku, Hideaki; Suzuki, Shinichi

2008-11-01

The chlorination reaction of Y2O3 with ZrCl4 in LiCl-KCl eutectic melt was investigated by X-ray absorption fine structure (XAFS) technique. The chlorination reaction was observed between 773 K and 823 K as the 1st peak shift of the Fourier transform magnitude function |FT(k3χ(k))|. The peak corresponding to the nearest Y3+-Cl- correlation was observed in the XAFS analysis at 823 K as the result of the chlorination. It was confirmed that the mixture melts after the reaction is almost equivalent to a molten 5% YCl3-(LiCl-KCl eutectic) mixture.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suleimanov, Yury V.; Aoiz, F. Javier; Guo, Hua

This Feature Article presents an overview of the current status of ring polymer molecular dynamics (RPMD) rate theory. We first analyze the RPMD approach and its connection to quantum transition-state theory. We then focus on its practical applications to prototypical chemical reactions in the gas phase, which demonstrate how accurate and reliable RPMD is for calculating thermal chemical reaction rate coefficients in multifarious cases. This review serves as an important checkpoint in RPMD rate theory development, which shows that RPMD is shifting from being just one of recent novel ideas to a well-established and validated alternative to conventional techniques formore » calculating thermal chemical rate coefficients. We also hope it will motivate further applications of RPMD to various chemical reactions.« less

Cyclically optimized electrochemical processes

NASA Astrophysics Data System (ADS)

Ruedisueli, Robert Louis

It has been frequently observed in experiment and industry practice that electrochemical processes (deposition, dissolution, fuel cells) operated in an intermittent or cyclic (AC) mode show improvements in efficiency and/or quality and yield over their steady (DC) mode of operation. Whether rationally invoked by design or empirically tuned-in, the optimal operating frequency and duty cycle is dependent upon the dominant relaxation time constant for the process in question. The electrochemical relaxation time constant is a function of: double-layer and reaction intermediary pseudo-capacitances, ion (charge) transport via electrical migration (mobility), and diffusion across a concentration gradient to electrode surface reaction sites where charge transfer and species incorporation or elimination occurs. The rate determining step dominates the time constant for the reaction or process. Electrochemical impedance spectroscopy (EIS) and piezoelectric crystal electrode (PCE) response analysis have proven to be useful tools in the study and identification of reaction mechanisms. This work explains and demonstrates with the electro-deposition of copper the application of EIS and PCE measurement and analysis to the selection of an optimum cyclic operating schedule, an optimum driving frequency for efficient, sustained cyclic (pulsed) operation.

Prescribed Travel Schedules for Fatigue Management

NASA Technical Reports Server (NTRS)

Whitmire, Alexandra; Johnston, Smith; Lockley, Steven

2011-01-01

The NASA Fatigue Management Team is developing recommendations for managing fatigue during travel and for shift work operations, as Clinical Practice Guidelines for the Management of Circadian Desynchrony in ISS Operations. The Guidelines provide the International Space Station (ISS ) flight surgeons and other operational clinicians with evidence-based recommendations for mitigating fatigue and other factors related to sleep loss and circadian desynchronization. As much international travel is involved both before and after flight, the guidelines provide recommendations for: pre-flight training, in-flight operations, and post-flight rehabilitation. The objective of is to standardize the process by which care is provided to crewmembers, ground controllers, and other support personnel such as trainers, when overseas travel or schedule shifting is required. Proper scheduling of countermeasures - light, darkness, melatonin, diet, exercise, and medications - is the cornerstone for facilitating circadian adaptation, improving sleep, enhancing alertness, and optimizing performance. The Guidelines provide, among other things, prescribed travel schedules that outline the specific implementation of these mitigation strategies. Each travel schedule offers evidence based protocols for properly using the NASA identified countermeasures for fatigue. This presentation will describe the travel implementation schedules and how these can be used to alleviate the effects of jet lag and/or schedule shifts.

Thermodynamic analysis of Direct Urea Solid Oxide Fuel Cell in combined heat and power applications

NASA Astrophysics Data System (ADS)

Abraham, F.; Dincer, I.

2015-12-01

This paper presents a comprehensive steady state modelling and thermodynamic analysis of Direct Urea Solid Oxide Fuel Cell integrated with Gas Turbine power cycle (DU-SOFC/GT). The use of urea as direct fuel mitigates public health and safety risks associated with the use of hydrogen and ammonia. The integration scheme in this study covers both oxygen ion-conducting solid oxide fuel cells (SOFC-O) and hydrogen proton-conducting solid oxide fuel cells (SOFC-H). Parametric case studies are carried out to investigate the effects of design and operating parameters on the overall performance of the system. The results reveal that the fuel cell exhibited the highest level of exergy destruction among other system components. Furthermore, the SOFC-O based system offers better overall performance than that with the SOFC-H option mainly due to the detrimental reverse water-gas shift reaction at the SOFC anode as well as the unique configuration of the system.

Simultaneous formation of 3-deoxy-d-threo-hexo-2-ulose and 3-deoxy-d-erythro-hexo-2-ulose during the degradation of d-glucose derived Amadori rearrangement products: Mechanistic considerations.

PubMed

Kaufmann, Martin; Krüger, Sophie; Mügge, Clemens; Kroh, Lothar W

2018-03-22

Analyzing classical model reaction systems of Amadori rearrangement products (ARP) it became apparent that the formation of 3-deoxy-d-threo-hexo-2-ulose (3-deoxygalactosone, 3-DGal) during the degradation of ARPs is highly dependent on pH and the amino acid residue of the respective ARP. Based on a detailed analysis of the NMR chemical shifts of the sugar moieties of different ARPs, it could be derived that the formation of 3-DGal is sensitive to the stability of a co-operative hydrogen bond network which involves HO-C3, the deprotonated carboxyl functionality and the protonated amino nitrogen of the amino acid substituent. Participating in this bond network, HO-C3 is partially protonated which facilitates the elimination of water at C3. Based on that, a new mechanism of 3-deoxyglycosone formation is proposed. Copyright © 2018 Elsevier Ltd. All rights reserved.

Maximal regularity in lp spaces for discrete time fractional shifted equations

NASA Astrophysics Data System (ADS)

Lizama, Carlos; Murillo-Arcila, Marina

2017-09-01

In this paper, we are presenting a new method based on operator-valued Fourier multipliers to characterize the existence and uniqueness of ℓp-solutions for discrete time fractional models in the form where A is a closed linear operator defined on a Banach space X and Δα denotes the Grünwald-Letnikov fractional derivative of order α > 0. If X is a UMD space, we provide this characterization only in terms of the R-boundedness of the operator-valued symbol associated to the abstract model. To illustrate our results, we derive new qualitative properties of nonlinear difference equations with shiftings, including fractional versions of the logistic and Nagumo equations.

2J, 3J-HMBC: A New Long-Range Heteronuclear Shift Correlation Technique Capable of Differentiating 2JCH from 3JCH Correlations to Protonated Carbons

NASA Astrophysics Data System (ADS)

Krishnamurthy, V. V.; Russell, David J.; Hadden, Chad E.; Martin, Gary E.

2000-09-01

The development of a series of new, accordion-optimized long-range heteronuclear shift correlation techniques has been reported. A further derivative of the constant time variable delay introduced in the IMPEACH-MBC experiment, a STAR (Selectively Tailored Accordion F1 Refocusing) operator is described in the present report. Incorporation of the STAR operator with the capability of user-selected homonuclear modulation scaling as in the CIGAR-HMBC experiment, into a long-range heteronuclear shift correlation pulse sequence, 2J,3J-HMBC, affords for the first time in a proton-detected experiment the means of unequivocally differentiating two-bond (2JCH) from three-bond (3JCH) long-range correlations to protonated carbons.

Modeling and Recent Shift in the Composition of Atmospheric Reactive Nitrogen

EPA Science Inventory

Nitrogen is an essential building block of all proteins and thus an essential nutrient for all life. Reactive nitrogen, which is naturally produced via enzymatic reactions, forest fires and lightning, is continually recycled and cascades through air, water, and soil media. Human ...

The influence of reaction times on structural, optical and luminescence properties of cadmium telluride nanoparticles prepared by wet-chemical process

NASA Astrophysics Data System (ADS)

Kiprotich, Sharon; Dejene, Francis B.; Ungula, Jatani; Onani, Martin O.

2016-01-01

This paper explains one pot synthesis of type II water soluble L-cysteine capped cadmium telluride (CdTe) core shell quantum dots using cadmium acetate, potassium tellurite and L-cysteine as the starting materials. The reaction was carried out in a single three necked flask without nitrogen under reflux at 100 °C. Results from PL show a sharp absorption excitonic band edge of the CdTe core with respect to the core shell which loses its shoulder during the growth of the shell on the core. The PL spectra indicate a drastic shift in emission window of the core which is simultaneously accompanied by an increase in emission intensity. X-ray diffraction pattern confirms the formation of hexagonal phase for all samples. Some difference in absorption edges were observed due to varying synthesis time of CdTe NPs. The position of the absorption band is observed to shift towards the lower wavelength side for shorter durations of synthesis.

Direct detection and characterization of bioinorganic peroxo moieties in a vanadium complex by 17O solid-state NMR and density functional theory.

PubMed

Gupta, Rupal; Stringer, John; Struppe, Jochem; Rehder, Dieter; Polenova, Tatyana

2018-07-01

Electronic and structural properties of short-lived metal-peroxido complexes, which are key intermediates in many enzymatic reactions, are not fully understood. While detected in various enzymes, their catalytic properties remain elusive because of their transient nature, making them difficult to study spectroscopically. We integrated 17 O solid-state NMR and density functional theory (DFT) to directly detect and characterize the peroxido ligand in a bioinorganic V(V) complex mimicking intermediates non-heme vanadium haloperoxidases. 17 O chemical shift and quadrupolar tensors, measured by solid-state NMR spectroscopy, probe the electronic structure of the peroxido ligand and its interaction with the metal. DFT analysis reveals the unusually large chemical shift anisotropy arising from the metal orbitals contributing towards the magnetic shielding of the ligand. The results illustrate the power of an integrated approach for studies of oxygen centers in enzyme reaction intermediates. Copyright © 2018 Elsevier Inc. All rights reserved.

Scaling Relations for Adsorption Energies on Doped Molybdenum Phosphide Surfaces

DOE PAGES

Fields, Meredith; Tsai, Charlie; Chen, Leanne D.; ...

2017-03-10

Molybdenum phosphide (MoP), a well-documented catalyst for applications ranging from hydrotreating reactions to electrochemical hydrogen evolution, has yet to be mapped from a more fundamental perspective, particularly in the context of transition-metal scaling relations. In this work, we use periodic density functional theory to extend linear scaling arguments to doped MoP surfaces and understand the behavior of the phosphorus active site. The derived linear relationships for hydrogenated C, N, and O species on a variety of doped surfaces suggest that phosphorus experiences a shift in preferred bond order depending on the degree of hydrogen substitution on the adsorbate molecule. Thismore » shift in phosphorus hybridization, dependent on the bond order of the adsorbate to the surface, can result in selective bond weakening or strengthening of chemically similar species. As a result, we discuss how this behavior deviates from transition-metal, sulfide, carbide, and nitride scaling relations, and we discuss potential applications in the context of electrochemical reduction reactions.« less

Theoretical Study on Sers of Wagging Vibrations of Benzyl Radical Adsorbed on Silver Electrodes

NASA Astrophysics Data System (ADS)

Wu, De-Yin; Chen, Yan-Li; Tian, Zhong-Qun

2016-06-01

Electrochemical surface-enhanced Raman spectroscopy (EC-SERS) has been used to characterize adsorbed species widely but reaction intermediates rarely on electrodes. In previous studies, the observed SERS signals were proposed from surface benzyl species due to the electrochemical reduction of benzyl chloride on silver electrode surfaces. In this work, we reinvestigated the vibrational assignments of benzyl chloride and benzyl radical as the reaction intermediate. On the basis of density functional theoretical (DFT) calculations and normal mode analysis, our systematical results provide more reasonable new assignments for both surface species. Further, we investigated adsorption configurations, binding energies, and vibrational frequency shifts of benzyl radical interacting with silver. Our calculated results show that the wagging vibration displays significant vibrational frequency shift, strong coupling with some intramolecular modes in the phenyl ring, and significant changes in intensity of Raman signals. The study also provides absolute Raman intensity in benzyl halides and discuss the enhancement effect mainly due to the binding interaction with respect to free benzyl radical.

Chemoselective Alteration of Fluorophore Scaffolds as a Strategy for the Development of Ratiometric Chemodosimeters.

PubMed

Zhou, Xinqi; Lesiak, Lauren; Lai, Rui; Beck, Jon R; Zhao, Jia; Elowsky, Christian G; Li, Hui; Stains, Cliff I

2017-04-03

Ratiometric sensors generally couple binding events or chemical reactions at a distal site to changes in the fluorescence of a core fluorophore scaffold. However, such approaches are often hindered by spectral overlap of the product and reactant species. We provide a strategy to design ratiometric sensors that display dramatic spectral shifts by leveraging the chemoselective reactivity of novel functional groups inserted within fluorophore scaffolds. As a proof-of-principle, fluorophores containing a borinate (RF 620 ) or silanediol (SiOH2R) functionality at the bridging position of the xanthene ring system are developed as endogenous H 2 O 2 sensors. Both these fluorophores display far-red to near-infrared excitation and emission prior to reaction. Upon oxidation by H 2 O 2 both sensors are chemically converted to tetramethylrhodamine, producing significant (≥66 nm) blue-shifts in excitation and emission maxima. This work provides a new concept for the development of ratiometric probes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Advanced Air Traffic Management Research (Human Factors and Automation): NASA Research Initiatives in Human-Centered Automation Design in Airspace Management

NASA Technical Reports Server (NTRS)

Corker, Kevin M.; Condon, Gregory W. (Technical Monitor)

1996-01-01

NASA has initiated a significant thrust of research and development focused on providing the flight crew and air traffic managers automation aids to increase capacity in en route and terminal area operations through the use of flexible, more fuel-efficient routing, while improving the level of safety in commercial carrier operations. In that system development, definition of cognitive requirements for integrated multi-operator dynamic aiding systems is fundamental. The core processes of control and the distribution of decision making in that control are undergoing extensive analysis. From our perspective, the human operators and the procedures by which they interact are the fundamental determinants of the safe, efficient, and flexible operation of the system. In that perspective, we have begun to explore what our experience has taught will be the most challenging aspects of designing and integrating human-centered automation in the advanced system. We have performed a full mission simulation looking at the role shift to self-separation on board the aircraft with the rules of the air guiding behavior and the provision of a cockpit display of traffic information and an on-board traffic alert system that seamlessly integrates into the TCAS operations. We have performed and initial investigation of the operational impact of "Dynamic Density" metrics on controller relinquishing and reestablishing full separation authority. (We follow the assumption that responsibility at all times resides with the controller.) This presentation will describe those efforts as well as describe the process by which we will guide the development of error tolerant systems that are sensitive to shifts in operator work load levels and dynamic shifts in the operating point of air traffic management.

Nuclear field shift in natural environments

NASA Astrophysics Data System (ADS)

Moynier, Frédéric; Fujii, Toshiyuki; Brennecka, Gregory A.; Nielsen, Sune G.

2013-03-01

The nuclear field shift (NFS) is an isotope shift in atomic energy levels caused by a combination of differences in nuclear size and shape and electron densities at the nucleus. The effect of NFS in isotope fractionation was theoretically established by Bigeleisen in 1996 [Bigeleisen J. (1996) J. Am. Chem. Soc. 118:3676-3680] and has been analytically measured in laboratory chemical exchange reactions. More recently, some isotopic variations of heavy elements (Hg, Tl, U) measured in natural systems as well as isotopic anomalies measured for lower-mass elements in meteorites have been attributed to the NFS effect. These isotopic variations open up new and exciting fields of investigations in Earth sciences. In this paper, we review the different natural systems in which NFS has been proposed to be the origin of isotopic variations.

Pressurized diesel fuel processing using hydrogen peroxide for the fuel cell power unit in low-oxygen environments

NASA Astrophysics Data System (ADS)

Lee, Kwangho; Han, Gwangwoo; Cho, Sungbaek; Bae, Joongmyeon

2018-03-01

A novel concept for diesel fuel processing utilizing H2O2 is suggested to obtain the high-purity H2 required for air-independent propulsion using polymer electrolyte membrane fuel cells for use in submarines and unmanned underwater vehicles. The core components include 1) a diesel-H2O2 autothermal reforming (ATR) reactor to produce H2-rich gas, 2) a water-gas shift (WGS) reactor to convert CO to H2, and 3) a H2 separation membrane to separate only high-purity H2. Diesel and H2O2 can easily be pressurized as they are liquids. The application of the H2 separation membrane without a compressor in the middle of the process is thus advantageous. In this paper, the characteristics of pressurized ATR and WGS reactions are investigated according to the operating conditions. In both reactors, the methanation reaction is enhanced as the pressure increases. Then, permeation experiments with a H2 separation membrane are performed while varying the temperature, pressure difference, and inlet gas composition. In particular, approximately 90% of the H2 is recovered when the steam-separated rear gas of the WGS reactor is used in the H2 separation membrane. Finally, based on the experimental results, design points are suggested for maximizing the efficiency of the diesel-H2O2 fuel processor.

Methodology for Generating Conflict Scenarios by Time Shifting Recorded Traffic Data

NASA Technical Reports Server (NTRS)

Paglione, Mike; Oaks, Robert; Bilimoria, Karl D.

2003-01-01

A methodology is presented for generating conflict scenarios that can be used as test cases to estimate the operational performance of a conflict probe. Recorded air traffic data is time shifted to create traffic scenarios featuring conflicts with characteristic properties similar to those encountered in typical air traffic operations. First, a reference set of conflicts is obtained from trajectories that are computed using birth points and nominal flight plans extracted from recorded traffic data. Distributions are obtained for several primary properties (e.g., encounter angle) that are most likely to affect the performance of a conflict probe. A genetic algorithm is then utilized to determine the values of time shifts for the recorded track data so that the primary properties of conflicts generated by the time shifted data match those of the reference set. This methodology is successfully demonstrated using recorded traffic data for the Memphis Air Route Traffic Control Center; a key result is that the required time shifts are less than 5 min for 99% of the tracks. It is also observed that close matching of the primary properties used in this study additionally provides a good match for some other secondary properties.

Inflight Performance of Cassini Reaction Wheel Bearing Drag in 1997-2013

NASA Technical Reports Server (NTRS)

Lee, Allan Y.; Wang, Eric K.

2013-01-01

As the first spacecraft to achieve orbit at Saturn in 2004, Cassini has collected science data throughout its four-year prime mission (2004-08), and has since been approved for a first and second extended missions through September 2017. Cassini is a three-axis stabilized spacecraft. It uses reaction wheels to achieve high level of spacecraft pointing stability that is needed during imaging operations of several science instruments. The Cassini flight software makes in-flight estimates of reaction wheel bearing drag torque and made them available to the mission operations team. These telemetry data are being trended for the purpose of monitoring the long-term health of the reaction wheel bearings. Anomalous drag torque signatures observed over the past 15 years are described in this paper. One of these anomalous drag conditions is bearing cage instability that appeared (and disappeared) spontaneously and unpredictably. Cage instability is an uncontrolled vibratory motion of the bearing cage that can produce high-impact forces internal to the bearing that will cause intermittent and erratic torque transients. Characteristics of the observed cage instabilities and other drag torque "spikes" are described in this paper. In day-to-day operations, the reaction wheels' rates must be neither too high nor too low. To protect against operating the wheels in any undesirable conditions (such as prolonged low spin rate operations), a ground software tool named Reaction Wheel Bias Optimization Tool (RBOT) was developed for the management of the wheels. Disciplined and long-term use of this ground software has led to significant reduction in the daily consumption rate of the wheels' low spin rate dwell time. Flight experience on the use of this ground software tool as well as other lessons learned on the management of Cassini reaction wheels is given in this paper.

Confinement Effects on Carbon Dioxide Methanation: A Novel Mechanism for Abiotic Methane Formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Le, Thu; Striolo, Alberto; Turner, C. Heath

An important scientific debate focuses on the possibility of abiotic synthesis of hydrocarbons during oceanic crust-seawater interactions. While on-site measurements near hydrothermal vents support this possibility, laboratory studies have provided data that are in some cases contradictory. At conditions relevant for sub-surface environments it has been shown that classic thermodynamics favour the production of CO 2 from CH 4, while abiotic methane synthesis would require the opposite. However, confinement effects are known to alter reaction equilibria. This report shows that indeed thermodynamic equilibrium can be shifted towards methane production, suggesting that thermal hydrocarbon synthesis near hydrothermal vents and deeper inmore » the magma-hydrothermal system is possible. We report reactive ensemble Monte Carlo simulations for the CO 2 methanation reaction. We compare the predicted equilibrium composition in the bulk gaseous phase to that expected in the presence of confinement. In the bulk phase we obtain excellent agreement with classic thermodynamic expectations. When the reactants can exchange between bulk and a confined phase our results show strong dependency of the reaction equilibrium conversions, X CO2, on nanopore size, nanopore chemistry, and nanopore morphology. Some physical conditions that could shift significantly the equilibrium composition of the reactive system with respect to bulk observations are discussed.« less

Confinement Effects on Carbon Dioxide Methanation: A Novel Mechanism for Abiotic Methane Formation

DOE PAGES

Le, Thu; Striolo, Alberto; Turner, C. Heath; ...

2017-08-21

An important scientific debate focuses on the possibility of abiotic synthesis of hydrocarbons during oceanic crust-seawater interactions. While on-site measurements near hydrothermal vents support this possibility, laboratory studies have provided data that are in some cases contradictory. At conditions relevant for sub-surface environments it has been shown that classic thermodynamics favour the production of CO 2 from CH 4, while abiotic methane synthesis would require the opposite. However, confinement effects are known to alter reaction equilibria. This report shows that indeed thermodynamic equilibrium can be shifted towards methane production, suggesting that thermal hydrocarbon synthesis near hydrothermal vents and deeper inmore » the magma-hydrothermal system is possible. We report reactive ensemble Monte Carlo simulations for the CO 2 methanation reaction. We compare the predicted equilibrium composition in the bulk gaseous phase to that expected in the presence of confinement. In the bulk phase we obtain excellent agreement with classic thermodynamic expectations. When the reactants can exchange between bulk and a confined phase our results show strong dependency of the reaction equilibrium conversions, X CO2, on nanopore size, nanopore chemistry, and nanopore morphology. Some physical conditions that could shift significantly the equilibrium composition of the reactive system with respect to bulk observations are discussed.« less

Two-center three-electron bonding in ClNH 3 revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH 3 → ClNH 2 + H reaction

DOE PAGES

Moradi, Christopher P.; Xie, Changjian; Kaufmann, Matin; ...

2016-04-22

Pyrolytic dissociation of Cl 2 is employed to dope helium droplets with single Cl atoms. Sequential addition of NH 3 to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction Cl + NH 3 → ClNH 2 + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C 3v symmetric top. Frequency shifts from NH 3 and dipole moment measurements are consistent with a ClNH 3 complex containing a relatively strong two-center three-electron (2c–3e) bond. The nature of the 2c–3e bonding in ClNH 3more » is explored computationally and found to be consistent with the complexation-induced blue shifts observed experimentally. As a result, computations of interconversion pathways reveal nearly barrierless routes to the formation of this complex, consistent with the absence in experimental spectra of two other complexes, NH 3Cl and Cl–HNH 2, which are predicted in the entry valley to the hydrogen abstraction reaction Cl + NH 3 → HCl + NH 2.« less

Center of gravity estimation using a reaction board instrumented with fiber Bragg gratings

NASA Astrophysics Data System (ADS)

Oliveira, Rui; Roriz, Paulo; Marques, Manuel B.; Frazão, Orlando

2018-03-01

The purpose of the present work is to construct a reaction board based on fiber Bragg gratings (FBGs) that could be used for estimation of the 2D coordinates of the projection of center of gravity (CG) of an object. The apparatus is consisted of a rigid equilateral triangular board mounted on three supports at the vertices, two of which have cantilevers instrumented with FBGs. When an object of known weight is placed on the board, the bending strain of the cantilevers is measured by a proportional wavelength shift of the FBGs. Applying the equilibrium conditions of a rigid body and proper calibration procedures, the wavelength shift is used to estimate the vertical reaction forces and moments of force at the supports and the coordinates of the object's CG projection on the board. This method can be used on a regular basis to estimate the CG of the human body or objects with complex geometry and density distribution. An example is provided for the estimation of the CG projection coordinates of two orthopaedic femur bone models, one intact, and the other with a hip stem implant encased. The clinical implications of changing the normal CG location by means of a prosthesis have been discussed.

Cyanoketene and Iminopropadienones.

PubMed

Moloney, Daniel W. J.; Wong, Ming Wah; Flammang, Robert; Wentrup, Curt

1997-06-27

Cyanoketene (8) is generated in high yields on flash vacuum thermolysis (FVT) of suitably substituted Meldrum's acid derivatives (5-[(alkylamino)(methylthio or alkylamino)methylene]-2,2-dimethyl-1,3-dioxane-4,6-diones) (3e-j), and also on FVT of cyanoacetic acid derivatives 9e,f,g,j,k,m. The major reaction pathway from 3 proceeds via ketenimines 6 and (alkylimino)propadienones 7, the latter undergoing a retro-ene reaction to 8. A minor pathway is via imidoylketenes 4e,h and oxoketenimines 5e,h, which undergo retro-ene reactions to 9. All intermediates were characterized by Ar matrix FTIR and tandem mass spectrometry (collisional activation MS). Trapping of 4, 5, and 8 with nucleophiles is also reported. The preference of 1,3-X shifts over 1,5-H shifts in imidoylketenes 12 (X = SMe or NMe(2)) is corroborated by the calculated activation barriers. Neat cyanoketene is highly reactive, reacting at or below 80 K, and this is attributed to the availability of a low-lying ketene LUMO. The IR spectrum of cyanoketene (Ar, 14 K) is dominated by two absorptions at 2163 (s; C=C=O) and 2239 (w; CN) cm(-)(1) in excellent agreement with density functional (B3-LYP/6-31G) and ab initio (QCISD/6-31G) calculations.

Two-center three-electron bonding in ClNH{sub 3} revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH{sub 3} → ClNH{sub 2} + H reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moradi, Christopher P.; Douberly, Gary E., E-mail: douberly@uga.edu; Xie, Changjian

2016-04-28

Pyrolytic dissociation of Cl{sub 2} is employed to dope helium droplets with single Cl atoms. Sequential addition of NH{sub 3} to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction Cl + NH{sub 3} → ClNH{sub 2} + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C{sub 3v} symmetric top. Frequency shifts from NH{sub 3} and dipole moment measurements are consistent with a ClNH{sub 3} complex containing a relatively strong two-center three-electron (2c–3e) bond. The nature of the 2c–3e bonding in ClNH{sub 3}more » is explored computationally and found to be consistent with the complexation-induced blue shifts observed experimentally. Computations of interconversion pathways reveal nearly barrierless routes to the formation of this complex, consistent with the absence in experimental spectra of two other complexes, NH{sub 3}Cl and Cl–HNH{sub 2}, which are predicted in the entry valley to the hydrogen abstraction reaction Cl + NH{sub 3} → HCl + NH{sub 2}.« less

Zeolite Y encapsulated with Fe-TiO2 for ultrasound-assisted degradation of amaranth dye in water.

PubMed

Alwash, Atheel Hassan; Abdullah, Ahmad Zuhairi; Ismail, Norli

2012-09-30

A new heterogeneous catalyst for sonocatalytic degradation of amaranth dye in water was synthesized by introducing titania into the pores of zeolite (NaY) through ion exchange method while Fe (III) was immobilized on the encapsulated titanium via impregnation method. XRD results could not detect any peaks for titanium oxide or Fe(2)O(3) due to its low loading. The UV-vis analysis proved a blue shift toward shorter wavelength after the loading of Ti into NaY while a red shift was detected after the loading of Fe into the encapsulated titanium. Different reaction variables such as TiO(2) content, amount of Fe, pH values, amount of hydrogen peroxide, catalyst loading and the initial dye concentration were studied to estimate their effect on the decolorization efficiency of amaranth. The maximum decolorization efficiency achieved was 97.5% at a solution pH of 2.5, catalyst dosage of 2 g/L, 20 mmol/100 mL of H(2)O(2) and initial dye concentration of 10 mg/L. The new heterogeneous catalyst Fe/Ti-NaY was a promising catalyst for this reaction and showed minimum Fe leaching at the end of the reaction. Copyright © 2012 Elsevier B.V. All rights reserved.

Influence of chronobiology on the nanoparticle-mediated drug uptake into the brain.

PubMed

Kreuter, Jörg

2015-02-03

Little attention so-far has been paid to the influence of chronobiology on the processes of nanoparticle uptake and transport into the brain, even though this transport appears to be chronobiologically controlled to a significant degree. Nanoparticles with specific surface properties enable the transport across the blood-brain barrier of many drugs that normally cannot cross this barrier. A clear dependence of the central antinociceptive (analgesic) effects of a nanoparticle-bound model drug, i.e., the hexapeptide dalargin, on the time of day was observable after intravenous injection in mice. In addition to the strongly enhanced antinociceptive effect due to the binding to the nanoparticles, the minima and maxima of the pain reaction with the nanoparticle-bound drug were shifted by almost half a day compared to the normal circadian nociception: The maximum in the pain reaction after i.v. injection of the nanoparticle-bound dalargin occurred during the later rest phase of the animals whereas the normal pain reaction and that of a dalargin solution was highest during the active phase of the mice in the night. This important shift could be caused by an enhanced endo- and exocytotic particulates transport activity of the brain capillary endothelial cells or within the brain during the rest phase.

Experimental and Theoretical Studies on the Nazarov Cyclization/Wagner-Meerwein Rearrangement Sequence

PubMed Central

Lebœuf, David; Ciesielski, Jennifer

2012-01-01

Highly functionalized cyclopentenones can be generated stereospecifically by a chemoselective copper(II)-mediated Nazarov/Wagner-Meerwein rearrangement sequence of divinyl ketones. A detailed investigation of this sequence is described including a study of substrate scope and limitations. After the initial 4π electrocyclization, this reaction proceeds via two different sequential [1,2]-shifts, with selectivity that depends upon either migratory ability or the steric bulkiness of the substituents at C1 and C5. This methodology allows the creation of vicinal stereogenic centers, including adjacent quaternary centers. This sequence can also be achieved by using a catalytic amount of copper(II) in combination with NaBAr4f, a weak Lewis acid. During the study of the scope of the reaction, a partial or complete E / Z isomerization of the enone moiety was observed in some cases prior to the cyclization, which resulted in a mixture of diastereomeric products. Use of a Cu(II)-bisoxazoline complex prevented the isomerization, allowing high diastereoselectivity to be obtained in all substrate types. In addition, the reaction sequence was studied by DFT computations at the UB3LYP/6-31G(d,p) level, which are consistent with the proposed sequences observed, including E / Z isomerizations and chemoselective Wagner-Meerwein shifts. PMID:22471833

A combined experimental and computational study of water-gas shift reaction over rod-shaped Ce 0.75 M 0.25O 2 (M=Ti, Zr, and Mn) supported Cu catalysts

DOE PAGES

Ren, Zhibo; Peng, Fei; Chen, Biaohua; ...

2017-11-02

Water-gas shift (WGS) reaction over a series of ceria-based mixed oxides supported Cu catalysts was investigated using a combined experimental and theoretical method. The mixed rod-shaped Ce 0.75M 0.25O 2 (M = Ti 4+, Zr 4+, Mn 4+) solid solutions, which majorly expose the (110) and (100) facets, are synthesized by hydrothermal method and used to prepare supported Cu catalysts. We found that the Cu/Ce0.75Ti 0.25O 2 (Cu-CT) exhibits the highest CO conversion in the temperature range of 150-250 °C among all supported Cu catalysts. This is mainly attributed to (i) good dispersion of Cu; (ii) largest amount of moderatemore » copper oxide; and (iii) strongest Cu-support interaction of Cu-CT. And compared to other mixed metals, periodic density functional theory calculations performed, this work further suggest that the introduction of Ti into CeO 2 not only promotes oxygen vacancy formation and CO adsorption, but also facilitates the carboxyl (COOH) formation at the interface of the Cu cluster and the support, which leads to the enhanced catalytic activity of the Cu-CT toward WGS reaction.« less

Interactions between ingredients in IMX-101: Reactive Chemical Processes Control Insensitive Munitions Properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maharrey, Sean P.; Wiese-Smith, Deneille; Highley, Aaron M.

2014-03-01

Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry (STMBMS) measurements have been conducted on a new Insensitive Munitions (IM) formulation. IMX-101 is the first explosive to be fully IM qualified under new NATO STANAG guidelines for fielded munitions. The formulation uses dinitroanisole (DNAN) as a new melt cast material to replace TNT, and shows excellent IM performance when formulated with other energetic ingredients. The scope of this work is to explain this superior IM performance by investigating the reactive processes occurring in the material when subjected to a well-controlled thermal environment. The dominant reactive processes observed were a series of complex chemicalmore » interactions between the three main ingredients (DNAN, NQ, and NTO) that occurs well below the onset of the normal decomposition process of any of the individual ingredients. This process shifts the thermal response of the formulations to a much lower temperature, where the kinetically controlled reaction processes are much slower. This low temperature shift has the effect of allowing the reactions to consume the reactive solids (NQ, NTO) well before the reaction rates increase and reach thermal runaway, resulting in a relatively benign response to the external stimuli. The main findings on the interaction processes are presented.« less

49 CFR 383.111 - Required knowledge.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 49 Transportation 5 2013-10-01 2013-10-01 false Required knowledge. 383.111 Section 383.111... safe vehicle operations; (iii) The effects of fatigue, poor vision, hearing impairment, and general..., off tracking, right/left turns and right curves. (5) Shifting. The basic shifting rules and terms for...

49 CFR 383.111 - Required knowledge.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 49 Transportation 5 2012-10-01 2012-10-01 false Required knowledge. 383.111 Section 383.111... safe vehicle operations; (iii) The effects of fatigue, poor vision, hearing impairment, and general..., off tracking, right/left turns and right curves. (5) Shifting. The basic shifting rules and terms for...

49 CFR 383.111 - Required knowledge.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 49 Transportation 5 2014-10-01 2014-10-01 false Required knowledge. 383.111 Section 383.111... safe vehicle operations; (iii) The effects of fatigue, poor vision, hearing impairment, and general..., off tracking, right/left turns and right curves. (5) Shifting. The basic shifting rules and terms for...

Design of Iron(II) Phthalocyanine-Derived Oxygen Reduction Electrocatalysts for High-Power-Density Microbial Fuel Cells.

PubMed

Santoro, Carlo; Gokhale, Rohan; Mecheri, Barbara; D'Epifanio, Alessandra; Licoccia, Silvia; Serov, Alexey; Artyushkova, Kateryna; Atanassov, Plamen

2017-08-24

Iron(II) phthalocyanine (FePc) deposited onto two different carbonaceous supports was synthesized through an unconventional pyrolysis-free method. The obtained materials were studied in the oxygen reduction reaction (ORR) in neutral media through incorporation in an air-breathing cathode structure and tested in an operating microbial fuel cell (MFC) configuration. Rotating ring disk electrode (RRDE) analysis revealed high performances of the Fe-based catalysts compared with that of activated carbon (AC). The FePc supported on Black-Pearl carbon black [Fe-BP(N)] exhibits the highest performance in terms of its more positive onset potential, positive shift of the half-wave potential, and higher limiting current as well as the highest power density in the operating MFC of (243±7) μW cm -2 , which was 33 % higher than that of FePc supported on nitrogen-doped carbon nanotubes (Fe-CNT(N); 182±5 μW cm -2 ). The power density generated by Fe-BP(N) was 92 % higher than that of the MFC utilizing AC; therefore, the utilization of platinum group metal-free catalysts can boost the performances of MFCs significantly. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reduced order modeling of mechanical degradation induced performance decay in lithium-ion battery porous electrodes

DOE PAGES

Barai, Pallab; Smith, Kandler; Chen, Chien -Fan; ...

2015-06-17

In this paper, a one-dimensional computational framework is developed that can solve for the evolution of voltage and current in a lithium-ion battery electrode under different operating conditions. A reduced order model is specifically constructed to predict the growth of mechanical degradation within the active particles of the carbon anode as a function of particle size and C-rate. Using an effective diffusivity relation, the impact of microcracks on the diffusivity of the active particles has been captured. Reduction in capacity due to formation of microcracks within the negative electrode under different operating conditions (constant current discharge and constant current constantmore » voltage charge) has been investigated. At the beginning of constant current discharge, mechanical damage to electrode particles predominantly occurs near the separator. As the reaction front shifts, mechanical damage spreads across the thickness of the negative electrode and becomes relatively uniform under multiple discharge/charge cycles. Mechanical degradation under different drive cycle conditions has been explored. It is observed that electrodes with larger particle sizes are prone to capacity fade due to microcrack formation. Finally, under drive cycle conditions, small particles close to the separator and large particles close to the current collector can help in reducing the capacity fade due to mechanical degradation.« less

Analysis of operational comfort in manual tasks using human force manipulability measure.

PubMed

Tanaka, Yoshiyuki; Nishikawa, Kazuo; Yamada, Naoki; Tsuji, Toshio

2015-01-01

This paper proposes a scheme for human force manipulability (HFM) based on the use of isometric joint torque properties to simulate the spatial characteristics of human operation forces at an end-point of a limb with feasible magnitudes for a specified limb posture. This is also applied to the evaluation/prediction of operational comfort (OC) when manually operating a human-machine interface. The effectiveness of HFM is investigated through two experiments and computer simulations of humans generating forces by using their upper extremities. Operation force generation with maximum isometric effort can be roughly estimated with an HFM measure computed from information on the arm posture during a maintained posture. The layout of a human-machine interface is then discussed based on the results of operational experiments using an electric gear-shifting system originally developed for robotic devices. The results indicate a strong relationship between the spatial characteristics of the HFM and OC levels when shifting, and the OC is predicted by using a multiple regression model with HFM measures.

Short-term response of subadult white sturgeon to hopper dredge disposal operations

USGS Publications Warehouse

Parsley, Michael J.; Popoff, Nicholas D.; Romine, Jason G.

2011-01-01

The effect of dredged-material disposal operations on the behavior of seven white sturgeon Acipenser transmontanus (50–101 cm fork length) was examined by analysis of the movements and depth use of these fish before, during, and after a series of hopper dredge disposal operations in the lower Columbia River. Analyses of fish locations showed that 12 flow-lane disposal operations within a 24-h period had minimal effect on subadult white sturgeon behavior; six of the seven fish showed slight attraction to the disposal area during disposals, and one fish increased its distance from the disposal area. The core area for all fish combined shifted toward the disposal area during disposals. In the 24 h after completion of the disposal operations the fish core areas shifted back toward those areas occupied before the disposals. The rates of movement, depths used, and diel movement patterns of the white sturgeon showed little change over all periods, suggesting that natural behaviors were not altered during and immediately after hopper dredge disposal operations.

Automated High-Speed Video Detection of Small-Scale Explosives Testing

NASA Astrophysics Data System (ADS)

Ford, Robert; Guymon, Clint

2013-06-01

Small-scale explosives sensitivity test data is used to evaluate hazards of processing, handling, transportation, and storage of energetic materials. Accurate test data is critical to implementation of engineering and administrative controls for personnel safety and asset protection. Operator mischaracterization of reactions during testing contributes to either excessive or inadequate safety protocols. Use of equipment and associated algorithms to aid the operator in reaction determination can significantly reduce operator error. Safety Management Services, Inc. has developed an algorithm to evaluate high-speed video images of sparks from an ESD (Electrostatic Discharge) machine to automatically determine whether or not a reaction has taken place. The algorithm with the high-speed camera is termed GoDetect (patent pending). An operator assisted version for friction and impact testing has also been developed where software is used to quickly process and store video of sensitivity testing. We have used this method for sensitivity testing with multiple pieces of equipment. We present the fundamentals of GoDetect and compare it to other methods used for reaction detection.

Pauson-Khand reactions in a photochemical flow microreactor.

PubMed

Asano, Keisuke; Uesugi, Yuki; Yoshida, Jun-ichi

2013-05-17

Pauson-Khand reactions were achieved at ambient temperature without any additive using a photochemical flow microreactor. The efficiency of the reaction was better than that in a conventional batch reactor, and the reaction could be operated continuously for 1 h.

Method of forming and starting a sodium sulfur battery

DOEpatents

Paquette, David G.

1981-01-01

A method of forming a sodium sulfur battery and of starting the reactive capability of that battery when heated to a temperature suitable for battery operation is disclosed. An anodic reaction zone is constructed in a manner that sodium is hermetically sealed therein, part of the hermetic seal including fusible material which closes up openings through the container of the anodic reaction zone. The hermetically sealed anodic reaction zone is assembled under normal atmospheric conditions with a suitable cathodic reaction zone and a cation-permeable barrier. When the entire battery is heated to an operational temperature, the fusible material of the hermetically sealed anodic reaction zone is fused, thereby allowing molten sodium to flow from the anodic reaction zone into reactive engagement with the cation-permeable barrier.

Nonadiabatic conditional geometric phase shift with NMR.

PubMed

Xiang-Bin, W; Keiji, M

2001-08-27

A conditional geometric phase shift gate, which is fault tolerant to certain types of errors due to its geometric nature, was realized recently via nuclear magnetic resonance (NMR) under adiabatic conditions. However, in quantum computation, everything must be completed within the decoherence time. The adiabatic condition makes any fast conditional Berry phase (cyclic adiabatic geometric phase) shift gate impossible. Here we show that by using a newly designed sequence of simple operations with an additional vertical magnetic field, the conditional geometric phase shift gate can be run nonadiabatically. Therefore geometric quantum computation can be done at the same rate as usual quantum computation.

Computational Studies on the Pt(II)-Catalyzed Cycloisomerization of 1,6-dienes into Bicyclopropanes: A Mechanistic Quandary Evaluated by DFT

PubMed Central

Bell, Franziska; Holland, Jason; Green, Jennifer C.; Gagné, Michel R.

2009-01-01

The mechanism of the (bis(phosphanylethyl)phosphane)Pt2+ catalyzed cyclo-isomerization reaction of 7-methyl-octa-1,6-diene to form 1-isopropylbicyclo[3.1.0]hexane was studied using computational methods. The cyclopropanation step was found to be the turnover-limiting step. The overall reaction proceeds via both a 5-exo and a 6-endo route. W conformations were shown to facilitate cyclopropanation, but do not have any influence on the rate of the 1,2-hydride shifts. PMID:20161262

Community, Educational, and Social Impact Perspectives.

ERIC Educational Resources Information Center

Schoeny, Donna Hager, Ed.; Decker, Larry E., Ed.

This volume consists of edited versions of 17 papers and reaction papers that were commissioned to examine the community, educational, and social impact of community education. Various topics pertaining to the impact of community education are examined, including educational programs of students, school closings and shifting populations, the…

International Trends in Heritage and Environmental Interpretation: Future Directions for Australian Research and Practice.

ERIC Educational Resources Information Center

Ballantyne, Roy; Uzzell, David

1999-01-01

In the past decade, heritage and environmental interpretation shifted from technical emphasis to social perspective, reflected in five international trends: growing concern with theory, increasing ecotourism and consequent changes in environmental interpretation, reactions to globalization (homogeneity versus uniqueness), interpretation of…

30 CFR 77.1906 - Hoists; daily inspection.

Code of Federal Regulations, 2010 CFR

2010-07-01

... wheels, etc.), connections, links and chains, and other facilities. (b) Prior to each working shift, and... shall be run by the hoist operator through one complete cycle of operation before any person is...

The effect of the duration of jet aircraft flyover sounds on judged annoyance. [noise predictions and noise measurements of jet aircrafts and human reactions to the noise intensity

NASA Technical Reports Server (NTRS)

Shepherd, K. P.

1979-01-01

The effect of the duration of jet aircraft flyover sounds on humans and the annoyance factor are examined. A nine point numerical category scaling technique is utilized for the study. Changes in the spectral characteristics of aircraft sounds caused by atmospheric attenuation are discussed. The effect of Doppler shifts using aircraft noises with minimal pure tone content is reported. The spectral content of sounds independent of duration and Doppler shift are examined by analysis of variance.

Syntheses, structural characterization, and basic properties of unsymmetrically substituted biphenoquinones

NASA Astrophysics Data System (ADS)

Fujii, Ryotaro; Sugiura, Ken-ichi

2018-03-01

Unsymmetrically substituted biphenoquinones, 3,5-dimethyl-3‧,5‧-diphenylbiphenoquinone and 3,5-di-tert-butyl-3‧,5‧-diphenylbiphenoquinone, were prepared by a mixed oxidative coupling reaction of the corresponding phenols with potassium permanganate in CHCl3. The properties of the quinones such as reduction potential and visible light absorption were measured and positively shifted reduction potentials and bathochromic shifts as a result of light absorption were found to be characteristic of the π-expanded quinones. We also carried out single-crystal diffraction study and uncovered a unique packing motif attributable to their unsymmetrical structures.

Present and Future Supply of Registered Nurses.

ERIC Educational Resources Information Center

Altman, Stuart H.

During the 1960's, nursing education shifted dramatically away from hospital-operated diploma schools toward associate degree and baccalaureate programs. This report examines the nature of this shift in training and its anticipated impact on future supply. Other important factors affecting the future supply of nurses are analyzed, including the…

Single-step electron transfer on the nanometer scale: ultra-fast charge shift in strongly coupled zinc porphyrin-gold porphyrin dyads.

PubMed

Fortage, Jérôme; Boixel, Julien; Blart, Errol; Hammarström, Leif; Becker, Hans Christian; Odobel, Fabrice

2008-01-01

The synthesis, electrochemical properties, and photoinduced electron transfer processes of a series of three novel zinc(II)-gold(III) bisporphyrin dyads (ZnP--S--AuP(+)) are described. The systems studied consist of two trisaryl porphyrins connected directly in the meso position via an alkyne unit to tert-(phenylenethynylene) or penta(phenylenethynylene) spacers. In these dyads, the estimated center to center interporphyrin separation distance varies from 32 to 45 A. The absorption, emission, and electrochemical data indicate that there are strong electronic interactions between the linked elements, thanks to the direct attachment of the spacer on the porphyrin ring through the alkyne unit. At room temperature in toluene, light excitation of the zinc porphyrin results in almost quantitative formation of the charge shifted state (.+)ZnP--S--AuP(.), whose lifetime is in the order of hundreds of picoseconds. In this solvent, the charge-separated state decays to the ground state through the intermediate population of the zinc porphyrin triplet excited state. Excitation of the gold porphyrin leads instead to rapid energy transfer to the triplet ZnP. In dichloromethane the charge shift reactions are even faster, with time constants down to 2 ps, and may be induced also by excitation of the gold porphyrin. In this latter solvent, the longest charge-shifted lifetime (tau=2.3 ns) was obtained with the penta-(phenylenethynylene) spacer. The charge shift reactions are discussed in terms of bridge-mediated super-exchange mechanisms as electron or hole transfer. These new bis-porphyrin arrays, with strong electronic coupling, represent interesting molecular systems in which extremely fast and efficient long-range photoinduced charge shift occurs over a long distance. The rate constants are two to three orders of magnitude larger than for corresponding ZnP--AuP(+) dyads linked via meso-phenyl groups to oligo-phenyleneethynylene spacers. This study demonstrates the critical impact of the attachment position of the spacer on the porphyrin on the electron transfer rate, and this strategy can represent a useful approach to develop molecular photonic devices for long-range charge separations.

Molecular mechanisms in the pyrolysis of unsaturated chlorinated hydrocarbons: formation of benzene rings. 2. Experimental and kinetic modeling studies.

PubMed

McIntosh, Grant J; Russell, Douglas K

2013-05-23

The mechanism of formation of benzene rings during the pyrolysis of dichloro- and trichloroethylenes has been investigated by the method of laser powered homogeneous pyrolysis coupled with product analysis by gas chromatography. Additionally, selected (co)pyrolyses between the chlorinated ethylenes, CH2Cl2, C4Cl4, C4Cl6, and C2H2 have been performed to explicitly probe the roles of 2C3 and C4/C2 reaction pairs in aromatic growth. The presence of odd-carbon products in neat C4Cl6 pyrolyses indicates that 2C3 processes are operative in these systems; however, comparison with product yields from C2HCl3 suggests that C4/C2 processes dominate most other systems. This is further evidenced by an absence of C3 and other odd-carbon species in (co)pyrolyses with dichloromethane which should seed C3-based growth. The reactions of perchlorinated C4 species C4Cl5, C4Cl3, and C4Cl4 with C2Cl2 were subsequently explored through extensive kinetic simulations of the possible reaction pathways based on previous kinetic models and the exhaustive quantum chemical investigations of our preceding work. The experimental and theoretical results strongly suggest that, at moderate temperatures, aromatic ring formation from chlorinated ethylenes normally follows a Diels-Alder coupling of C4 and C2 molecular units followed by internal shifts; the one exception is the C4Cl4 + C2Cl2 system, where steric factors lead to the formation of nonaromatic products. There is little evidence for radical-based routes in these systems.

A Few Discrete Lattice Systems and Their Hamiltonian Structures, Conservation Laws

NASA Astrophysics Data System (ADS)

Guo, Xiu-Rong; Zhang, Yu-Feng; Zhang, Xiang-Zhi; Yue, Rong

2017-04-01

With the help of three shift operators and r-matrix theory, a few discrete lattice systems are obtained which can be reduced to the well-known Toda lattice equation with a constraint whose Hamiltonian structures are generated by Poisson tensors of some induced Lie-Poisson bracket. The recursion operators of these lattice systems are constructed starting from Lax representations. Finally, reducing the given shift operators to get a simpler one and its expanding shift operators, we produce a lattice system with three vector fields whose recursion operator is given. Furthermore, we reduce the lattice system with three vector fields to get a lattice system whose Lax pair and conservation laws are obtained, respectively. Supported by the National Natural Science Foundation of China under Grant No. 11371361, the Innovation Team of Jiangsu Province Hosted by China University of Mining and Technology (2014), the the Key Discipline Construction by China University of Mining and Technology under Grant No. XZD201602, the Shandong Provincial Natural Science Foundation, China under Grant Nos. ZR2016AM31, ZR2016AQ19, ZR2015EM042, the Development of Science and Technology Plan Projects of TaiAn City under Grant No. 2015NS1048, National Social Science Foundation of China under Grant No. 13BJY026, and A Project of Shandong Province Higher Educational Science and Technology Program under Grant No. J14LI58

Towards understanding the kinetic behaviour and limitations in photo-induced copper(i) catalyzed azide-alkyne cycloaddition (CuAAC) reactions.

PubMed

El-Zaatari, Bassil M; Shete, Abhishek U; Adzima, Brian J; Kloxin, Christopher J

2016-09-14

The kinetic behaviour of the photo-induced copper(i) catalyzed azide-alkyne cycloaddition (CuAAC) reaction was studied in detail using real-time Fourier transform infrared (FTIR) spectroscopy on both a solvent-based monofunctional and a neat polymer network forming system. The results in the solvent-based system showed near first-order kinetics on copper and photoinitiator concentrations up to a threshold value in which the kinetics switch to zeroth-order. This kinetic shift shows that the photo-CuAAC reaction is not susceptible from side reactions such as copper disproportionation, copper(i) reduction, and radical termination at the early stages of the reaction. The overall reaction rate and conversion is highly dependent on the initial concentrations of photoinitiator and copper(ii) as well as their relative ratios. The conversion was decreased when an excess of photoinitiator was utilized compared to its threshold value. Interestingly, the reaction showed an induction period at relatively low intensities. The induction period is decreased by increasing light intensity and photoinitiator concentration. The reaction trends and limitations were further observed in a solventless polymer network forming system, exhibiting a similar copper and photoinitiator threshold behaviour.

Towards understanding the kinetic behaviour and limitations in photo-induced copper(I) catalyzed azide-alkyne cycloaddition (CuAAC) reactions

PubMed Central

El-Zaatari, Bassil M.; Shete, Abhishek U.; Adzima, Brian J.; Kloxin, Christopher J.

2016-01-01

The kinetic behaviour of the photo-induced copper(I) catalyzed azide—alkyne cycloaddition (CuAAC) reaction was studied in detail using real-time Fourier Transform Infrared Spectroscopy (FTIR) on both a solvent-based monofunctional and a neat polymer network forming system. The results in the solvent-based system showed near first-order kinetics on copper and photoinitiator concentrations up to a threshold value in which the kinetics switch to zeroth-order. This kinetic shift shows that the photo-CuAAC reaction is not suseptible from side reactions such as copper disproportionation, copper(I) reduction, and radical termination at the early stages of the reaction. The overall reaction rate and conversion is highly dependent on the initial concentrations of photoinitiator and copper(II), as well as their relative ratios. The conversion was decreased when an excess of photoinitiator was utilized compared to its threshold value. Interestingly, the reaction showed an induction period at relatively low intensities. The induction period is decreased by increasing light intensity, and photoinitiator concentration. The reaction trends and limitations were further observed in a solventless polymer network forming system, exhibiting a similar copper and photoinitiator threshold behaviour. PMID:27711587

Testing of Two-Speed Transmission Configurations for Use in Rotorcraft

NASA Technical Reports Server (NTRS)

Lewicki, David G.; Stevens, Mark A.

2015-01-01

Large civil tiltrotors have been identified to replace regional airliners over medium ranges to alleviate next-generation air traffic. Variable rotor speed for these vehicles is required for efficient high-speed operation. Two-speed drive system research has been performed to support these advanced rotorcraft applications. Experimental tests were performed on two promising two-speed transmission configurations. The offset compound gear (OCG) transmission and the dual star/idler (DSI) planetary transmission were tested in the NASA Glenn Research Center variable-speed transmission test facility. Both configurations were inline devices with concentric input and output shafts and designed to provide 1:1 and 2:1 output speed reduction ratios. Both were designed for 200 hp and 15,000 rpm input speed and had a dry shift clutch configuration. Shift tests were performed on the transmissions at input speeds of 5,000, 8,000, 10,000, 12,500, and 15,000 rpm. Both the OCG and DSI configurations successfully perform speed shifts at full rated 15,000 rpm input speed. The transient shifting behavior of the OCG and DSI configurations were very similar. The shift clutch had more of an effect on shifting dynamics than the reduction gearing configuration itself since the same shift clutch was used in both configurations. For both OCG and DSI configurations, low-to-high speed shifts were limited in applied torque levels in order to prevent overloads on the transmission due to transient torque spikes. It is believed that the relative lack of appreciable slippage of the dry shifting clutch at operating conditions and pressure profiles tested was a major cause of the transient torque spikes. For the low-to-high speed shifts, the output speed ramp-up time slightly decreased and the peak out torque slightly increased as the clutch pressure ramp-down rate increased. This was caused by slightly less clutch slippage as the clutch pressure ramp-down rate increased.

Stress and salivary cortisol in emergency medical dispatchers: A randomized shifts control trial

PubMed Central

Bedini, Sarah; Braun, François; Weibel, Laurence; Aussedat, Michel; Pereira, Bruno; Dutheil, Frédéric

2017-01-01

Stress at work is a public health concern. Phone operators in emergency medical dispatch centers are particularly at risk. We aimed to demonstrate that the most stressful time for emergency medical dispatchers is the shift when they receive emergency incoming calls, with cortisol as a biomarker of stress. For each emergency medical dispatcher, we measured outcomes over a control day and during three types of shift: Incoming emergency call, Dispatch and Re-assessment. The pattern of shifts was randomized. Saliva was sampled every 15 minutes for 2 hours, i.e. 6 consecutive times, starting 15 minutes after the first life-and-death incoming emergency call between 2 and 5 pm during three types of shift. We measured saliva cortisol every 2 hours over a control day, from 7am to 9pm. Perceived stress was assessed by a visual analog scale. We recruited 22 phone operators aged 36.4+/-10.8 years old (14 women and 8 men). Cortisol values were higher during the Incoming emergency call shift than during the Dispatch (p = .04) and Re-assessment (p = .04) shifts. The increase in cortisol levels was greater in men than in women (p = .009). There were no differences between control values and those of the three shifts. The kinetics of cortisol increased with greater perceived stress overall (p < .001) and for each type of shift (Incoming emergency call, p = .02; Dispatch p = .03; Re-assessment: p < .001). The kinetics of cortisol in response to incoming emergency calls was greater when the call was an absolute emergency (p = .03), and also tended to further increase when a subsequent absolute incoming emergency call was received (p = 0.07). In conclusion, the incoming emergency call shift carries particular risk for dispatchers, who have greater perceived stress and a greater increase in cortisol levels. PMID:28505199

Stress and salivary cortisol in emergency medical dispatchers: A randomized shifts control trial.

PubMed

Bedini, Sarah; Braun, François; Weibel, Laurence; Aussedat, Michel; Pereira, Bruno; Dutheil, Frédéric

2017-01-01

Stress at work is a public health concern. Phone operators in emergency medical dispatch centers are particularly at risk. We aimed to demonstrate that the most stressful time for emergency medical dispatchers is the shift when they receive emergency incoming calls, with cortisol as a biomarker of stress. For each emergency medical dispatcher, we measured outcomes over a control day and during three types of shift: Incoming emergency call, Dispatch and Re-assessment. The pattern of shifts was randomized. Saliva was sampled every 15 minutes for 2 hours, i.e. 6 consecutive times, starting 15 minutes after the first life-and-death incoming emergency call between 2 and 5 pm during three types of shift. We measured saliva cortisol every 2 hours over a control day, from 7am to 9pm. Perceived stress was assessed by a visual analog scale. We recruited 22 phone operators aged 36.4+/-10.8 years old (14 women and 8 men). Cortisol values were higher during the Incoming emergency call shift than during the Dispatch (p = .04) and Re-assessment (p = .04) shifts. The increase in cortisol levels was greater in men than in women (p = .009). There were no differences between control values and those of the three shifts. The kinetics of cortisol increased with greater perceived stress overall (p < .001) and for each type of shift (Incoming emergency call, p = .02; Dispatch p = .03; Re-assessment: p < .001). The kinetics of cortisol in response to incoming emergency calls was greater when the call was an absolute emergency (p = .03), and also tended to further increase when a subsequent absolute incoming emergency call was received (p = 0.07). In conclusion, the incoming emergency call shift carries particular risk for dispatchers, who have greater perceived stress and a greater increase in cortisol levels.

Circadian and ultradian rhythms in the feeding behaviour and nutrient intakes of oil refinery operators with shift-work every 3--4 days.

PubMed

Reinberg, A; Migraine, C; Apfelbaum, M; Brigant, L; Ghata, J; Vieux, N; Laporte, A; Nicolai

1979-03-01

Seven healthy adult men, five shift-workers and two non-shift-workers (from 21 to 36 years; mean = 26.4) volunteered to record what and when they ate, both at work and at home, every day, during eight consecutive weeks (Oct. - Dec. 1974). 1) All the subjects maintained the timing of main-meal (lunch and supper) during all shifts. 2) The major intake of protein and lipid was concentrated on the two main meals during all shifts. 3) Only the pattern of carbohydrate intake was modified by the shift-work: e.g. night-shift is associated with nibbling behaviour. 4) However, shift-work and in particular the occurence of nibbling behaviour did not result in change either in the mean 24 h caloric intake, or in the percentage of protein calories. 5) The comparison between the constancy of the timing of major meals and the shift of the timing of circadian rhythm acrophases of the 5 shift-workers leads to conclude that meal timing had a poor synchronizing effect, if any.

Isotopic disproportionation during hydrogen isotopic analysis of nitrogen-bearing organic compounds

USGS Publications Warehouse

Nair, Sreejesh; Geilmann, Heike; Coplen, Tyler B.; Qi, Haiping; Gehre, Matthias; Schimmelmann, Arndt; Brand, Willi A.

2015-01-01

Rationale High-precision hydrogen isotope ratio analysis of nitrogen-bearing organic materials using high-temperature conversion (HTC) techniques has proven troublesome in the past. Formation of reaction products other than molecular hydrogen (H2) has been suspected as a possible cause of incomplete H2 yield and hydrogen isotopic fractionation. Methods The classical HTC reactor setup and a modified version including elemental chromium, both operated at temperatures in excess of 1400 °C, have been compared using a selection of nitrogen-bearing organic compounds, including caffeine. A focus of the experiments was to avoid or suppress hydrogen cyanide (HCN) formation and to reach quantitative H2 yields. The technique also was optimized to provide acceptable sample throughput. Results The classical HTC reaction of a number of selected compounds exhibited H2 yields from 60 to 90 %. Yields close to 100 % were measured for the experiments with the chromium-enhanced reactor. The δ2H values also were substantially different between the two types of experiments. For the majority of the compounds studied, a highly significant relationship was observed between the amount of missing H2and the number of nitrogen atoms in the molecules, suggesting the pyrolytic formation of HCN as a byproduct. A similar linear relationship was found between the amount of missing H2 and the observed hydrogen isotopic result, reflecting isotopic fractionation. Conclusions The classical HTC technique to produce H2 from organic materials using high temperatures in the presence of glassy carbon is not suitable for nitrogen-bearing compounds. Adding chromium to the reaction zone improves the yield to 100 % in most cases. The initial formation of HCN is accompanied by a strong hydrogen isotope effect, with the observed hydrogen isotope results on H2 being substantially shifted to more negative δ2H values. The reaction can be understood as an initial disproportionation leading to H2 and HCN with the HCN-hydrogen systematically enriched in 2H by more than 50 ‰. In the reaction of HCN with chromium, H2 and chromium-containing solid residues are formed quantitatively.

40 CFR 62.15130 - What types of operator certification must the chief facility operator and shift supervisor obtain...

Code of Federal Regulations, 2012 CFR

2012-07-01

... Requirements for Small Municipal Waste Combustion Units Constructed on or Before August 30, 1999 Good Combustion Practices: Operator Certification § 62.15130 What types of operator certification must the chief....W. Alexander Drive, Room C521C, RTP, NC 27709 or at the National Archives and Records Administration...

40 CFR 62.15130 - What types of operator certification must the chief facility operator and shift supervisor obtain...

Code of Federal Regulations, 2010 CFR

2010-07-01

... Requirements for Small Municipal Waste Combustion Units Constructed on or Before August 30, 1999 Good Combustion Practices: Operator Certification § 62.15130 What types of operator certification must the chief....W. Alexander Drive, Room C521C, RTP, NC 27709 or at the National Archives and Records Administration...

40 CFR 62.15130 - What types of operator certification must the chief facility operator and shift supervisor obtain...

Code of Federal Regulations, 2013 CFR

2013-07-01

... Requirements for Small Municipal Waste Combustion Units Constructed on or Before August 30, 1999 Good Combustion Practices: Operator Certification § 62.15130 What types of operator certification must the chief....W. Alexander Drive, Room C521C, RTP, NC 27709 or at the National Archives and Records Administration...

40 CFR 62.15130 - What types of operator certification must the chief facility operator and shift supervisor obtain...

Code of Federal Regulations, 2011 CFR

2011-07-01

... Requirements for Small Municipal Waste Combustion Units Constructed on or Before August 30, 1999 Good Combustion Practices: Operator Certification § 62.15130 What types of operator certification must the chief....W. Alexander Drive, Room C521C, RTP, NC 27709 or at the National Archives and Records Administration...

40 CFR 62.15130 - What types of operator certification must the chief facility operator and shift supervisor obtain...

Code of Federal Regulations, 2014 CFR

2014-07-01

... Requirements for Small Municipal Waste Combustion Units Constructed on or Before August 30, 1999 Good Combustion Practices: Operator Certification § 62.15130 What types of operator certification must the chief....W. Alexander Drive, Room C521C, RTP, NC 27709 or at the National Archives and Records Administration...

Light-meson masses in an unquenched quark model

NASA Astrophysics Data System (ADS)

Chen, Xiaoyun; Ping, Jialun; Roberts, Craig D.; Segovia, Jorge

2018-05-01

We perform a coupled-channels calculation of the masses of light mesons with the quantum numbers I JP =-, (I ,J )=0 , 1, by including q q ¯ and (q q ¯)2 components in a nonrelativistic chiral quark model. The coupling between two- and four-quark configurations is realized through a 3P0 quark-pair creation model. With the usual form of this operator, the mass shifts are large and negative, an outcome which raises serious issues of validity for the quenched quark model. Herein, therefore, we introduce some improvements of the 3P0 operator in order to reduce the size of the mass shifts. By introducing two simple factors, physically well motivated, the coupling between q q ¯ and (q q ¯)2 components is weakened, producing mass shifts that are around 10%-20% of hadron bare masses.

An Investigation of the Reverse Water Gas Shift Process and Operating Alternatives

NASA Technical Reports Server (NTRS)

Whitlow, Jonathan E.

2002-01-01

The Reverse Water Gas Shift (RWGS) process can produce water and ultimately oxygen through electrolysis. This technology is being investigated for possible use in the exploration of Mars as well as a potential process to aid in the regeneration of oxygen from carbon dioxide. The initial part of this report summarizes the results obtained from operation of the RWGS process at Kennedy Space Center during May and June of this year. It has been demonstrated that close to complete conversion can be achieved with the RWGS process under certain operating conditions. The report also presents results obtained through simulation for an alternative staged configuration for RWGS which eliminates the recycle compressor. This configuration looks promising and hence seems worthy of experimental investigation.

Shift in Food Intake and Changes in Metabolic Regulation and Gene Expression during Simulated Night-Shift Work: A Rat Model

PubMed Central

Marti, Andrea Rørvik; Meerlo, Peter; Grønli, Janne; van Hasselt, Sjoerd Johan; Mrdalj, Jelena; Pallesen, Ståle; Pedersen, Torhild Thue; Henriksen, Tone Elise Gjøtterud; Skrede, Silje

2016-01-01

Night-shift work is linked to a shift in food intake toward the normal sleeping period, and to metabolic disturbance. We applied a rat model of night-shift work to assess the immediate effects of such a shift in food intake on metabolism. Male Wistar rats were subjected to 8 h of forced activity during their rest (ZT2-10) or active (ZT14-22) phase. Food intake, body weight, and body temperature were monitored across four work days and eight recovery days. Food intake gradually shifted toward rest-work hours, stabilizing on work day three. A subgroup of animals was euthanized after the third work session for analysis of metabolic gene expression in the liver by real-time polymerase chain reaction (PCR). Results show that work in the rest phase shifted food intake to rest-work hours. Moreover, liver genes related to energy storage and insulin metabolism were upregulated, and genes related to energy breakdown were downregulated compared to non-working time-matched controls. Both working groups lost weight during the protocol and regained weight during recovery, but animals that worked in the rest phase did not fully recover, even after eight days of recovery. In conclusion, three to four days of work in the rest phase is sufficient to induce disruption of several metabolic parameters, which requires more than eight days for full recovery. PMID:27834804

103Rh NMR spectroscopy and its application to rhodium chemistry.

PubMed

Ernsting, Jan Meine; Gaemers, Sander; Elsevier, Cornelis J

2004-09-01

Rhodium is used for a number of large processes that rely on homogeneous rhodium-catalyzed reactions, for instance rhodium-catalyzed hydroformylation of alkenes, carbonylation of methanol to acetic acid and hydrodesulfurization of thiophene derivatives (in crude oil). Many laboratory applications in organometallic chemistry and catalysis involve organorhodium chemistry and a wealth of rhodium coordination compounds is known. For these and other areas, 103Rh NMR spectroscopy appears to be a very useful analytical tool. In this review, most of the literature concerning 103Rh NMR spectroscopy published from 1989 up to and including 2003 has been covered. After an introduction to several experimental methods for the detection of the insensitive 103Rh nucleus, a discussion of factors affecting the transition metal chemical shift is given. Computational aspects and calculations of chemical shifts are also briefly addressed. Next, the application of 103Rh NMR in coordination and organometallic chemistry is elaborated in more detail by highlighting recent developments in measurement and interpretation of 103Rh NMR data, in relation to rhodium-assisted reactions and homogeneous catalysis. The dependence of the 103Rh chemical shift on the ligands at rhodium in the first coordination sphere, on the complex geometry, oxidation state, temperature, solvent and concentration is treated. Several classes of compounds and special cases such as chiral rhodium compounds are reviewed. Finally, a section on scalar coupling to rhodium is provided. 2004 John Wiley & Sons, Ltd.

Analysis of the Electronic Structure of the Special Pair of a Bacterial Photosynthetic Reaction Center by 13 C Photochemically Induced Dynamic Nuclear Polarization Magic-Angle Spinning NMR Using a Double-Quantum Axis.

PubMed

Najdanova, Marija; Gräsing, Daniel; Alia, A; Matysik, Jörg

2018-01-01

The origin of the functional symmetry break in bacterial photosynthesis challenges since several decades. Although structurally very similar, the two branches of cofactors in the reaction center (RC) protein complex act very differently. Upon photochemical excitation, an electron is transported along one branch, while the other remains inactive. Photochemically induced dynamic nuclear polarization (photo-CIDNP) magic-angle spinning (MAS) 13 C NMR revealed that the two bacteriochlorophyll cofactors forming the "Special Pair" donor dimer are already well distinguished in the electronic ground state. These previous studies are relying solely on 13 C- 13 C correlation experiments as radio-frequency-driven recoupling (RFDR) and dipolar-assisted rotational resonance (DARR). Obviously, the chemical-shift assignment is difficult in a dimer of tetrapyrrole macrocycles, having eight pyrrole rings of similar chemical shifts. To overcome this problem, an INADEQUATE type of experiment using a POST C7 symmetry-based approach is applied to selectively isotope-labeled bacterial RC of Rhodobacter (R.) sphaeroides wild type (WT). We, therefore, were able to distinguish unresolved sites of the macromolecular dimer. The obtained chemical-shift pattern is in-line with a concentric assembly of negative charge within the common center of the Special Pair supermolecule in the electronic ground state. © 2017 The American Society of Photobiology.

Anomalous dielectric relaxation with linear reaction dynamics in space-dependent force fields.

PubMed

Hong, Tao; Tang, Zhengming; Zhu, Huacheng

2016-12-28

The anomalous dielectric relaxation of disordered reaction with linear reaction dynamics is studied via the continuous time random walk model in the presence of space-dependent electric field. Two kinds of modified reaction-subdiffusion equations are derived for different linear reaction processes by the master equation, including the instantaneous annihilation reaction and the noninstantaneous annihilation reaction. If a constant proportion of walkers is added or removed instantaneously at the end of each step, there will be a modified reaction-subdiffusion equation with a fractional order temporal derivative operating on both the standard diffusion term and a linear reaction kinetics term. If the walkers are added or removed at a constant per capita rate during the waiting time between steps, there will be a standard linear reaction kinetics term but a fractional order temporal derivative operating on an anomalous diffusion term. The dielectric polarization is analyzed based on the Legendre polynomials and the dielectric properties of both reactions can be expressed by the effective rotational diffusion function and component concentration function, which is similar to the standard reaction-diffusion process. The results show that the effective permittivity can be used to describe the dielectric properties in these reactions if the chemical reaction time is much longer than the relaxation time.

Class III / short line system inventory to determine 286,000 lb (129,844 kg) railcar operational status in Kansas : final report.

DOT National Transportation Integrated Search

2017-08-01

The rail industrys recent shift towards larger and heavier railcars has influenced Class III/short line railroad operation and track maintenance costs. Class III railroads earn less than $38.1 million in annual revenue and generally operate first ...

Operational Art of Maritime Straits

DTIC Science & Technology

2008-10-29

13  Operation CHEETAH ...Operational Art Paradigm Shift A strait is a narrow body of water navigationally constricted on two sides and usually connects two larger bodies of...level of risk. Space Space, in the terms of straits, encompasses more than just the body of water. Control of the approaches, shorelines and

Class III / short line system inventory to determine 286,000 lb (129,844 kg) railcar operational status in Kansas : technical summary.

DOT National Transportation Integrated Search

2017-08-01

The rail industrys recent shift towards larger and heavier railcars has influenced Class III/short line railroad operation and track maintenance costs. Class III railroads earn less than $38.1 million in annual revenue and generally operate first ...

Forest operations for ecosystem management

Treesearch

Robert B. Rummer; John Baumgras; Joe McNeel

1997-01-01

The evolution of modern forest resource management is focusing on ecologically sensitive forest operations. This shift in management strategies is producing a new set of functional requirements for forest operations. Systems to implement ecosystem management prescriptions may need to be economically viable over a wider range of piece sizes, for example. Increasing...

NEW TARGET AND CONTROL ASSAYS FOR QUANTITATIVE POLYMERASE CHAIN REACTION (QPCR) ANALYSIS OF ENTEROCOCCI IN WATER

EPA Science Inventory

Enterococci are frequently monitored in water samples as indicators of fecal pollution. Attention is now shifting from culture based methods for enumerating these organisms to more rapid molecular methods such as QPCR. Accurate quantitative analyses by this method requires highly...

Challenging Teacher Beliefs about Student Engagement in Mathematics

ERIC Educational Resources Information Center

Bobis, Janette; Way, Jennifer; Anderson, Judy; Martin, Andrew J.

2016-01-01

This study explored the beliefs about student engagement in mathematics of three Year 5 and 6 teachers, focusing on the shifts that occurred during a 10-week intervention. Data obtained from teacher surveys, interviews, video-recorded workshop observations and artefacts from teachers' classrooms reveal variations in their reactions to the…

Passing the Baton: An Experimental Study of Shift Handover

NASA Technical Reports Server (NTRS)

Parke, Bonny; Hobbs, Alan; Kanki, Barbara

2010-01-01

Shift handovers occur in many safety-critical environments, including aviation maintenance, medicine, air traffic control, and mission control for space shuttle and space station operations. Shift handovers are associated with increased risk of communication failures and human error. In dynamic industries, errors and accidents occur disproportionately after shift handover. Typical shift handovers involve transferring information from an outgoing shift to an incoming shift via written logs, or in some cases, face-to-face briefings. The current study explores the possibility of improving written communication with the support modalities of audio and video recordings, as well as face-to-face briefings. Fifty participants participated in an experimental task which mimicked some of the critical challenges involved in transferring information between shifts in industrial settings. All three support modalities, face-to-face, video, and audio recordings, reduced task errors significantly over written communication alone. The support modality most preferred by participants was face-to-face communication; the least preferred was written communication alone.

Sleep and cognitive function of crewmembers and mission controllers working 24-h shifts during a simulated 105-day spaceflight mission

NASA Astrophysics Data System (ADS)

Barger, Laura K.; Wright, Kenneth P.; Burke, Tina M.; Chinoy, Evan D.; Ronda, Joseph M.; Lockley, Steven W.; Czeisler, Charles A.

2014-01-01

The success of long-duration space missions depends on the ability of crewmembers and mission support specialists to be alert and maintain high levels of cognitive function while operating complex, technical equipment. We examined sleep, nocturnal melatonin levels and cognitive function of crewmembers and the sleep and cognitive function of mission controllers who participated in a high-fidelity 105-day simulated spaceflight mission at the Institute of Biomedical Problems (Moscow). Crewmembers were required to perform daily mission duties and work one 24-h extended duration work shift every sixth day. Mission controllers nominally worked 24-h extended duration shifts. Supplemental lighting was provided to crewmembers and mission controllers. Participants' sleep was estimated by wrist-actigraphy recordings. Overall, results show that crewmembers and mission controllers obtained inadequate sleep and exhibited impaired cognitive function, despite countermeasure use, while working extended duration shifts. Crewmembers averaged 7.04±0.92 h (mean±SD) and 6.94±1.08 h (mean±SD) in the two workdays prior to the extended duration shifts, 1.88±0.40 h (mean±SD) during the 24-h work shift, and then slept 10.18±0.96 h (mean±SD) the day after the night shift. Although supplemental light was provided, crewmembers' average nocturnal melatonin levels remained elevated during extended 24-h work shifts. Naps and caffeine use were reported by crewmembers during ˜86% and 45% of extended night work shifts, respectively. Even with reported use of wake-promoting countermeasures, significant impairments in cognitive function were observed. Mission controllers slept 5.63±0.95 h (mean±SD) the night prior to their extended duration work shift. On an average, 89% of night shifts included naps with mission controllers sleeping an average of 3.4±1.0 h (mean±SD) during the 24-h extended duration work shift. Mission controllers also showed impaired cognitive function during extended duration work shifts. These findings indicate that extended duration work shifts present a significant challenge to crewmembers and mission support specialists during long-duration space mission operations. Future research is needed to evaluate the efficacy of alternative work schedules and the development and implementation of more effective countermeasures will be required to maintain high levels of performance.

Randomized placebo-controlled field study of the effects of bright light and melatonin in adaptation to night work.

PubMed

Bjorvatn, Bjørn; Stangenes, Kristine; Oyane, Nicolas; Forberg, Knut; Lowden, Arne; Holsten, Fred; Akerstedt, Torbjørn

2007-06-01

This study evaluated the effects of bright light and melatonin on adaptation to night work on an oil rig in the North Sea. Seventeen persons working a schedule of 2 weeks on a 12-hour shift, with the first week on night shift and the second week on day shift (ie, the swing shift schedule) participated. In a randomized controlled crossover design, the shift workers received a placebo, melatonin (3 mg, 1 hour before bedtime), or bright light (30-minute exposure, individually scheduled) during the first 4 days on the night shift and during the first 4 days on the day shift. Subjective and objective measures of sleepiness (Karolinska Sleepiness Scale and a simple serial reaction-time test) and sleep (diary and actigraphy) were recorded. Subjective measures indicated that melatonin modestly reduced sleepiness at work during the day shift and increased sleep by 15-20 minutes per day. Bright light gave values in between those of melatonin and the placebo, but with few significant results. According to the objective measures, bright light improved sleep to a minor degree during the night shift. Hardly any side-effects were reported. Melatonin and bright light modestly improved sleep and sleepiness in this field study. In well-controlled simulated nightwork studies, both melatonin and bright light are more effective in alleviating sleepiness and sleep problems. The less effect in this field study may be due to competing or conflicting factors present in real life or to an inoptimal timing and duration of the treatments.

Raman spectra of adsorbed layers on space shuttle and AOTV thermal protection system surface

NASA Technical Reports Server (NTRS)

Willey, Ronald J.

1987-01-01

Surfaces of interest to space vehicle heat shield design were struck by a 2 W argon ion laser line while subjected to supersonic arc jet flow conditions. Emission spectra were taken at 90 deg to the angle of laser incidence on the test object. Results showed possible weak Raman shifts which could not be directly tied to any particular parameter such as surface temperature or gas composition. The investigation must be considered exploratory in terms of findings. Many undesirable effects were found and corrected as the project progressed. For instance, initial spectra settings led to ghosts which were eliminated by closing the intermediate of filter slit of the Spex from 8 to 3 mm. Further, under certain conditions, plasma lines from the laser were observed. Several materials were also investigated at room temperature for Raman shifts. Results showed Raman shifts for RCC and TEOS coated materials. The HRSI materials showed only weak Raman shifts, however, substantial efforts were made in studying these materials. Baseline materials showed the technique to be sound. The original goal was to find a Raman shift for the High-temperature Reusable Surface Insulation (HRSI) Reaction Cured borosilicate Glass (RCG) coated material and tie the amplitude of this peak to Arc jet conditions. Weak Raman shifts may be present, however, time limitations prevented confirmation.

Effects of reactant rotation on the dynamics of the OH + CH4 → H2O + CH3 reaction: a six-dimensional study.

PubMed

Song, Hongwei; Li, Jun; Jiang, Bin; Yang, Minghui; Lu, Yunpeng; Guo, Hua

2014-02-28

The dynamics of the hydrogen abstraction reaction between methane and hydroxyl radical is investigated using an initial state selected time-dependent wave packet method within a six-dimensional model. The ab initio calibrated global potential energy surface of Espinosa-García and Corchado was used. Integral cross sections from several low-lying rotational states of both reactants have been obtained using the centrifugal sudden and J-shifting approximations. On the empirical potential energy surface, the rotational excitation of methane has little effect on the reaction cross section, but excited rotational states of OH inhibit the reactivity slightly. These results are rationalized with the newly proposed sudden vector projection model.

On the dynamic nature of response criterion in recognition memory: effects of base rate, awareness, and feedback.

PubMed

Rhodes, Matthew G; Jacoby, Larry L

2007-03-01

The authors examined whether participants can shift their criterion for recognition decisions in response to the probability that an item was previously studied. Participants in 3 experiments were given recognition tests in which the probability that an item was studied was correlated with its location during the test. Results from all 3 experiments indicated that participants' response criteria were sensitive to the probability that an item was previously studied and that shifts in criterion were robust. In addition, awareness of the bases for criterion shifts and feedback on performance were key factors contributing to the observed shifts in decision criteria. These data suggest that decision processes can operate in a dynamic fashion, shifting from item to item.

Dynamics of CrO 3 –Fe 2 O 3 Catalysts during the High-Temperature Water-Gas Shift Reaction: Molecular Structures and Reactivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keturakis, Christopher J.; Zhu, Minghui; Gibson, Emma K.

2016-06-13

A series of supported CrO 3/Fe 2O 3 catalysts were investigated for the high-temperature water-gas shift (WGS) and reverse-WGS reactions and extensively characterized using in situ and operando IR, Raman, and XAS spectroscopy during the high-temperature WGS/RWGS reactions. The in situ spectroscopy examinations reveal that the initial oxidized catalysts contain surface dioxo (O=) 2Cr 6+O 2 species and a bulk Fe 2O 3 phase containing some Cr 3+ substituted into the iron oxide bulk lattice. Operando spectroscopy studies during the high-temperature WGS/RWGS reactions show that the catalyst transforms during the reaction. The crystalline Fe 2O 3 bulk phase becomes Femore » 3O 4 ,and surface dioxo (O=) 2Cr 6+O 2 species are reduced and mostly dissolve into the iron oxide bulk lattice. Consequently, the chromium–iron oxide catalyst surface is dominated by FeO x sites, but some minor reduced surface chromia sites are also retained. The Fe 3–-xCr xO 4 solid solution stabilizes the iron oxide phase from reducing to metallic Fe0 and imparts an enhanced surface area to the catalyst. Isotopic exchange studies with C 16O 2/H 2 → C 18O 2/H 2 isotopic switch directly show that the RWGS reaction proceeds via the redox mechanism and only O* sites from the surface region of the chromium–iron oxide catalysts are involved in the RWGS reaction. The number of redox O* sites was quantitatively determined with the isotope exchange measurements under appropriate WGS conditions and demonstrated that previous methods have undercounted the number of sites by nearly 1 order of magnitude. The TOF values suggest that only the redox O* sites affiliated with iron oxide are catalytic active sites for WGS/RWGS, though a carbonate oxygen exchange mechanism was demonstrated to exist, and that chromia is only a textural promoter that increases the number of catalytic active sites without any chemical promotion effect.« less

Construction of a ratiometric fluorescent probe with an extremely large emission shift for imaging hypochlorite in living cells

NASA Astrophysics Data System (ADS)

Song, Xuezhen; Dong, Baoli; Kong, Xiuqi; Wang, Chao; Zhang, Nan; Lin, Weiying

2018-01-01

Hypochlorite is one of the important reactive oxygen species (ROS) and plays critical roles in many biologically vital processes. Herein, we present a unique ratiometric fluorescent probe (CBP) with an extremely large emission shift for detecting hypochlorite in living cells. Utilizing positively charged α,β-unsaturated carbonyl group as the reaction site, the probe CBP itself exhibited near-infrared (NIR) fluorescence at 662 nm, and can display strong blue fluorescence at 456 nm when responded to hypochlorite. Notably, the extremely large emission shift of 206 nm could enable the precise measurement of the fluorescence peak intensities and ratios. CBP showed high sensitivity, excellent selectivity, desirable performance at physiological pH, and low cytotoxicity. The bioimaging experiments demonstrate the biological application of CBP for the ratiometric imaging of hypochlorite in living cells.

Cantilevered probe detector with piezoelectric element

DOEpatents

Adams, Jesse D; Sulchek, Todd A; Feigin, Stuart C

2014-04-29

A disclosed chemical detection system for detecting a target material, such as an explosive material, can include a cantilevered probe, a probe heater coupled to the cantilevered probe, and a piezoelectric element disposed on the cantilevered probe. The piezoelectric element can be configured as a detector and/or an actuator. Detection can include, for example, detecting a movement of the cantilevered probe or a property of the cantilevered probe. The movement or a change in the property of the cantilevered probe can occur, for example, by adsorption of the target material, desorption of the target material, reaction of the target material and/or phase change of the target material. Examples of detectable movements and properties include temperature shifts, impedance shifts, and resonant frequency shifts of the cantilevered probe. The overall chemical detection system can be incorporated, for example, into a handheld explosive material detection system.

Cantilevered probe detector with piezoelectric element

DOEpatents

Adams, Jesse D; Sulchek, Todd A; Feigin, Stuart C

2013-04-30

A disclosed chemical detection system for detecting a target material, such as an explosive material, can include a cantilevered probe, a probe heater coupled to the cantilevered probe, and a piezoelectric element disposed on the cantilevered probe. The piezoelectric element can be configured as a detector and/or an actuator. Detection can include, for example, detecting a movement of the cantilevered probe or a property of the cantilevered probe. The movement or a change in the property of the cantilevered probe can occur, for example, by adsorption of the target material, desorption of the target material, reaction of the target material and/or phase change of the target material. Examples of detectable movements and properties include temperature shifts, impedance shifts, and resonant frequency shifts of the cantilevered probe. The overall chemical detection system can be incorporated, for example, into a handheld explosive material detection system.

Cantilevered probe detector with piezoelectric element

DOEpatents

Adams, Jesse D [Reno, NV; Sulchek, Todd A [Oakland, CA; Feigin, Stuart C [Reno, NV

2012-07-10

A disclosed chemical detection system for detecting a target material, such as an explosive material, can include a cantilevered probe, a probe heater coupled to the cantilevered probe, and a piezoelectric element disposed on the cantilevered probe. The piezoelectric element can be configured as a detector and/or an actuator. Detection can include, for example, detecting a movement of the cantilevered probe or a property of the cantilevered probe. The movement or a change in the property of the cantilevered probe can occur, for example, by adsorption of the target material, desorption of the target material, reaction of the target material and/or phase change of the target material. Examples of detectable movements and properties include temperature shifts, impedance shifts, and resonant frequency shifts of the cantilevered probe. The overall chemical detection system can be incorporated, for example, into a handheld explosive material detection system.

Cantilevered probe detector with piezoelectric element

DOEpatents

Adams, Jesse D.; Sulchek, Todd A.; Feigin, Stuart C.

2010-04-06

A disclosed chemical detection system for detecting a target material, such as an explosive material, can include a cantilevered probe, a probe heater coupled to the cantilevered probe, and a piezoelectric element disposed on the cantilevered probe. The piezoelectric element can be configured as a detector and/or an actuator. Detection can include, for example, detecting a movement of the cantilevered probe or a property of the cantilevered probe. The movement or a change in the property of the cantilevered probe can occur, for example, by adsorption of the target material, desorption of the target material, reaction of the target material and/or phase change of the target material. Examples of detectable movements and properties include temperature shifts, impedance shifts, and resonant frequency shifts of the cantilevered probe. The overall chemical detection system can be incorporated, for example, into a handheld explosive material detection system.

Hemisynthesis and structural and chromatic characterization of delphinidin 3-O-glucoside-vescalagin hybrid pigments.

PubMed

García-Estévez, Ignacio; Jacquet, Rémi; Alcalde-Eon, Cristina; Rivas-Gonzalo, Julián C; Escribano-Bailón, M Teresa; Quideau, Stéphane

2013-11-27

During red wine maturation in the presence of oak wood, reactions involving anthocyanins and ellagitannins might affect wine organoleptic properties such as color and astringency. In this work, the condensation reaction between myrtillin (delphinidin 3-O-glucoside) and vescalagin has been performed to determine the behavior of this anthocyanin in this kind of reaction and to assess the possible impact of such a reaction in wine color modulation. Two different hybrid pigments have been hemisynthetized and characterized by HPLC-DAD-MS and NMR spectroscopy. These pigments have been identified as 1-deoxyvescalagin-(1β→8)-myrtillin (major) and 1-deoxyvescalagin-(1β→6)-myrtillin (minor). The minor pigment could be formed both by the condensation reaction and by a regioisomerization process from the major pigment. Moreover, the chromatic properties of these pigments have been studied and compared to those of myrtillin. The hybrid pigments showed an important bathochromic shift (ca. 20 nm) in the maximum absorbance wavelength and lower molar absorption coefficients.

Electron screening in nickel

NASA Astrophysics Data System (ADS)

Gajević, Jelena; Cvetinović, Aleksandra; Likar, Andrej; Lipoglavšek, Matej; Pelicon, Primož; Petrovič, Toni; Sánchez Ortiz, Alberto

2013-06-01

In order to investigate the interplay between nuclei and their surroundings, we studied proton-induced nuclear reactions over an energy range from 0.86 to 3.08MeV for different environments: Ni metal and NiO insulator. The measurements were based on the observation of the yields of 59, 61, 63, 64, 65Cu and 58, 60, 62Ni de-excitation γ-rays. Shifts in the resonance energy for the metallic target relative to the insulator one were not observed. Electron screening potential of Ue=31± 13 keV was deduced for 64Ni (p,nγ ) 64Cu reaction, while Ue=19± 4 keV was deduced for 58Ni(p,γ ) 59Cu and 60Ni(p,γ ) 61Cu reactions. The observed electron screening potentials for (p,n) and (p,γ) reactions are the same within error bars, but the comparison with previous measurements raises the question of the independence of the electron screening from the reaction exit channel.

Catalytic behavior of metal catalysts in high-temperature RWGS reaction: In-situ FT-IR experiments and first-principles calculations

PubMed Central

Choi, Sungjun; Sang, Byoung-In; Hong, Jongsup; Yoon, Kyung Joong; Son, Ji-Won; Lee, Jong-Ho; Kim, Byung-Kook; Kim, Hyoungchul

2017-01-01

High-temperature chemical reactions are ubiquitous in (electro) chemical applications designed to meet the growing demands of environmental and energy protection. However, the fundamental understanding and optimization of such reactions are great challenges because they are hampered by the spontaneous, dynamic, and high-temperature conditions. Here, we investigated the roles of metal catalysts (Pd, Ni, Cu, and Ag) in the high-temperature reverse water-gas shift (RWGS) reaction using in-situ surface analyses and density functional theory (DFT) calculations. Catalysts were prepared by the deposition-precipitation method with urea hydrolysis and freeze-drying. Most metals show a maximum catalytic activity during the RWGS reaction (reaching the thermodynamic conversion limit) with formate groups as an intermediate adsorbed species, while Ag metal has limited activity with the carbonate species on its surface. According to DFT calculations, such carbonate groups result from the suppressed dissociation and adsorption of hydrogen on the Ag surface, which is in good agreement with the experimental RWGS results. PMID:28120896

Nanosized CuO and ZnO Catalyst Supported on Honeycomb-Typed Monolith for Hydrogenation of Carbon Dioxide to Methyl Alcohol.

PubMed

Park, Chul-Min; Ahn, Won-Ju; Jo, Woong-Kyu; Song, Jin-Hun; Oh, Chang-Yeop; Jeong, Young-Shin; Chung, Min-Chul; Park, Kwon-Pil; Kim, Ki-Joong; Jeong, Woon-Jo; Sohn, Bo-Kyun; Jung, Sang-Chul; Lee, Do-Jin; Ahn, Byeong-Kwon; Ahn, Ho-Geun

2015-01-01

The greenhouse effect of carbon dioxide (CO2) has been recognized as one of the most serious problems in the world. Conversion of CO2 to methyl alcohol (CH3OH) was studied using catalytic chemical methods. Honeycomb-typed monolith used as catalyst support was 400 cell/inch2. Pretreatment of the monolith surface was carried out by thermal treatment and acid treatment. Monolith-supported nanosized CuO-ZnO catalysts were prepared by wash-coat method. The prepared catalysts were characterized by using SEM, TEM, and XRD. The catalytic activity for CO2 hydrogenation to CH3OH was investigated using a flow-type reactor with varying reaction temperature, reaction pressure and contact time. Conversion of CO2 was increased with increasing reaction temperature, but selectivity to CH3OH was decreased. Optimum reaction temperature was about 250 degrees C under 20 atm. Because of the reverse water gas shift reaction.

Catalytic behavior of metal catalysts in high-temperature RWGS reaction: In-situ FT-IR experiments and first-principles calculations.

PubMed

Choi, Sungjun; Sang, Byoung-In; Hong, Jongsup; Yoon, Kyung Joong; Son, Ji-Won; Lee, Jong-Ho; Kim, Byung-Kook; Kim, Hyoungchul

2017-01-25

High-temperature chemical reactions are ubiquitous in (electro) chemical applications designed to meet the growing demands of environmental and energy protection. However, the fundamental understanding and optimization of such reactions are great challenges because they are hampered by the spontaneous, dynamic, and high-temperature conditions. Here, we investigated the roles of metal catalysts (Pd, Ni, Cu, and Ag) in the high-temperature reverse water-gas shift (RWGS) reaction using in-situ surface analyses and density functional theory (DFT) calculations. Catalysts were prepared by the deposition-precipitation method with urea hydrolysis and freeze-drying. Most metals show a maximum catalytic activity during the RWGS reaction (reaching the thermodynamic conversion limit) with formate groups as an intermediate adsorbed species, while Ag metal has limited activity with the carbonate species on its surface. According to DFT calculations, such carbonate groups result from the suppressed dissociation and adsorption of hydrogen on the Ag surface, which is in good agreement with the experimental RWGS results.

Development of new UV-vis spectroscopic microwave-assisted method for determination of glucose in pharmaceutical samples

NASA Astrophysics Data System (ADS)

Mabood, Fazal; Hussain, Z.; Haq, H.; Arian, M. B.; Boqué, R.; Khan, K. M.; Hussain, K.; Jabeen, F.; Hussain, J.; Ahmed, M.; Alharasi, A.; Naureen, Z.; Hussain, H.; Khan, A.; Perveen, S.

2016-01-01

A new UV-Visible spectroscopic method assisted with microwave for the determination of glucose in pharmaceutical formulations was developed. In this study glucose solutions were oxidized by ammonium molybdate in the presence of microwave energy and reacted with aniline to produce a colored solution. Optimum conditions of the reaction including wavelength, temperature, and pH of the medium and relative concentration ratio of the reactants were investigated. It was found that the optimal wavelength for the reaction is 610 nm, the optimal reaction time is 80 s, the optimal reaction temperature is 160 °C, the optimal reaction pH is 4, and the optimal concentration ratio aniline/ammonium molybdate solution was found to be 1:1. The limits of detection and quantification of the method are 0.82 and 2.75 ppm for glucose solution, respectively. The use of microwaves improved the speed of the method while the use of aniline improved the sensitivity of the method by shifting the wavelength.

Adsorption and oxidation of formaldehyde on a polycrystalline Pt film electrode: An in situ IR spectroscopy search for adsorbed reaction intermediates

PubMed Central

Behm, R Jürgen

2014-01-01

Summary As part of a mechanistic study of the electrooxidation of C1 molecules we have systematically investigated the dissociative adsorption/oxidation of formaldehyde on a polycrystalline Pt film electrode under experimental conditions optimizing the chance for detecting weakly adsorbed reaction intermediates. Employing in situ IR spectroscopy in an attenuated total reflection configuration (ATR-FTIRS) with p-polarized IR radiation to further improve the signal-to-noise ratio, and using low reaction temperatures (3 °C) and deuterium substitution to slow down the reaction kinetics and to stabilize weakly adsorbed reaction intermediates, we could detect an IR absorption band at 1660 cm−1 characteristic for adsorbed formyl intermediates. This assignment is supported by an isotope shift in wave number. Effects of temperature, potential and deuterium substitution on the formation and disappearance of different adsorbed species (COad, adsorbed formate, adsorbed formyl), are monitored and quantified. Consequences on the mechanism for dissociative adsorption and oxidation of formaldehyde are discussed. PMID:24991512

Integrated Ceramic Membrane System for Hydrogen Production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schwartz, Joseph; Lim, Hankwon; Drnevich, Raymond

2010-08-05

Phase I was a technoeconomic feasibility study that defined the process scheme for the integrated ceramic membrane system for hydrogen production and determined the plan for Phase II. The hydrogen production system is comprised of an oxygen transport membrane (OTM) and a hydrogen transport membrane (HTM). Two process options were evaluated: 1) Integrated OTM-HTM reactor – in this configuration, the HTM was a ceramic proton conductor operating at temperatures up to 900°C, and 2) Sequential OTM and HTM reactors – in this configuration, the HTM was assumed to be a Pd alloy operating at less than 600°C. The analysis suggestedmore » that there are no technical issues related to either system that cannot be managed. The process with the sequential reactors was found to be more efficient, less expensive, and more likely to be commercialized in a shorter time than the single reactor. Therefore, Phase II focused on the sequential reactor system, specifically, the second stage, or the HTM portion. Work on the OTM portion was conducted in a separate program. Phase IIA began in February 2003. Candidate substrate materials and alloys were identified and porous ceramic tubes were produced and coated with Pd. Much effort was made to develop porous substrates with reasonable pore sizes suitable for Pd alloy coating. The second generation of tubes showed some improvement in pore size control, but this was not enough to get a viable membrane. Further improvements were made to the porous ceramic tube manufacturing process. When a support tube was successfully coated, the membrane was tested to determine the hydrogen flux. The results from all these tests were used to update the technoeconomic analysis from Phase I to confirm that the sequential membrane reactor system can potentially be a low-cost hydrogen supply option when using an existing membrane on a larger scale. Phase IIB began in October 2004 and focused on demonstrating an integrated HTM/water gas shift (WGS) reactor to increase CO conversion and produce more hydrogen than a standard water gas shift reactor would. Substantial improvements in substrate and membrane performance were achieved in another DOE project (DE-FC26-07NT43054). These improved membranes were used for testing in a water gas shift environment in this program. The amount of net H2 generated (defined as the difference of hydrogen produced and fed) was greater than would be produced at equilibrium using conventional water gas shift reactors up to 75 psig because of the shift in equilibrium caused by continuous hydrogen removal. However, methanation happened at higher pressures, 100 and 125 psig, and resulted in less net H2 generated than would be expected by equilibrium conversion alone. An effort to avoid methanation by testing in more oxidizing conditions (by increasing CO2/CO ratio in a feed gas) was successful and net H2 generated was higher (40-60%) than a conventional reactor at equilibrium at all pressures tested (up to 125 psig). A model was developed to predict reactor performance in both cases with and without methanation. The required membrane area depends on conditions, but the required membrane area is about 10 ft2 to produce about 2000 scfh of hydrogen. The maximum amount of hydrogen that can be produced in a membrane reactor decreased significantly due to methanation from about 2600 scfh to about 2400 scfh. Therefore, it is critical to eliminate methanation to fully benefit from the use of a membrane in the reaction. Other modeling work showed that operating a membrane reactor at higher temperature provides an opportunity to make the reactor smaller and potentially provides a significant capital cost savings compared to a shift reactor/PSA combination.« less

Adaptation rate of 6-sulfatoxymelatonin and cognitive performance in offshore fleet shift workers: a field study.

PubMed

Hansen, Jakob H; Geving, Ingunn H; Reinertsen, Randi E

2010-08-01

To determine the total phase delay and adaptation rate of 6-sulfatoxymelatonin (aMT6s) on subjective and objective sleep quality and cognitive performance after 7 days of working night shifts (1800-0600 hours). The subjects studied were offshore fleet workers (N = 7). Seven days of urine samples were collected to determine the total phase delay and adaptation rate of aMT6s. Subjective and objective sleep quality was registered with sleep diaries and actigraphy on a daily basis. Cognitive performance, as measured by vigilance and reaction time, was measured with the Vienna test system on days 1 and 7. Light exposure was measured in the vessel compartments daily. The rhythm of aMT6s shifted significantly from 4.78 +/- 0.94 h on day 1 to 8.84 +/- 1.76 h on day 7. Rate of adaptation was 0.84 h per day. Subjective sleep quality showed significant time effects on four variables, but objective sleep quality did not show any significant time effects. Vigilance and reaction time improved significantly from days 1 to 7. Light exposure intensities varied between 3 and 243 lux. This field study showed that offshore fleet workers are able to adapt to the imposed regimen of 12-h night shifts. The adaptation is slower compared to other branches of the offshore industry, which most likely is due to lower light exposure. Subjective sleep quality improved to some extent, but the results were not conclusive. No significant effects were observed in the objective measures. Cognitive performance improved significantly, which was likely to be caused by the extended working hours on day 1 and an entrainment of the suprachiasmatic nuclei (SCN).

Importance of Low Dimensional CeO x Nanostructures in Pt/CeO x –TiO 2 Catalysts for the Water–Gas Shift Reaction

DOE PAGES

Luo, Si; Barrio, Laura; Nguyen-Phan, Thuy-Duong; ...

2017-03-15

CO 2 and H 2 production from the water–gas shift (WGS) reaction was studied over Pt/CeO x–TiO 2 catalysts with incremental loadings of CeO x, which adopts variations in the local morphology. The lowest loading of CeO x (1 wt % to 0.5 at. %) that is configured in its smallest dimensions exhibited the best WGS activity over larger dimensional structures. We attribute this to several factors including the ultrafine dispersed one-dimensional nanocluster geometry, a large concentration of Ce 3+ and enhanced reducibility of the low loadings. We utilized several in situ experiments to monitor the active state of themore » catalyst during the WGS reaction. X-ray diffraction (XRD) results showed lattice expansion that indicated reduced ceria was prevalent during the WGS reaction. On the surface, Ce 3+ related hydroxyl groups were identified by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The enhanced reducibility of the catalyst with the introduction of ceria was further revealed by H 2-temperature programed reduction (H 2-TPR) and good thermal stability was confirmed by in situ environmental transmission electron microscopy (ETEM). Finally, we also investigated the formation of the low dimensional structures during catalyst preparation, through a two-stage crystal growth of ceria crystallite on TiO 2 nanoparticle: fine crystallites ~1D formed at ~250 °C, followed by crystal growth into 2D chain and 3D particle from 250–400 °C.« less

Circadian gene expression in peripheral blood leukocytes of rotating night shift nurses.

PubMed

Reszka, Edyta; Peplonska, Beata; Wieczorek, Edyta; Sobala, Wojciech; Bukowska, Agnieszka; Gromadzinska, Jolanta; Lie, Jenny-Anne; Kjuus, Helge; Wasowicz, Wojciech

2013-03-01

It has been hypothesized that the underlying mechanism of elevated breast cancer risk among long-term, night-working women involves circadian genes expression alteration caused by exposure to light at night and/or irregular work hours. The aim of the present study was to determine the effect of rotating night shift work on expression of selected core circadian genes. The cross-sectional study was conducted on 184 matched nurses and midwives, who currently work either day or rotating night shifts, to determine the effect of irregular work at night on circadian gene expression in peripheral blood leukocytes. Transcript levels of BMAL1, CLOCK, CRY1, CRY2, PER1, PER2, and PER3 were determined by means of quantitative real-time polymerase chain reaction (PCR). After adjusting for hour of blood collection, there were no statistically significant changes of investigated circadian genes among nurses and midwives currently working rotating night shifts compared to nurses working day shifts. The highest expression of PER1 messenger ribonucleic acid (mRNA) was observed for women currently working shifts who had worked >15 years in rotating night shift work. PER1 gene expression was associated with the lifetime duration of rotating night shift work among women currently working night shifts (P=0.04). PER1 and PER3 transcript levels in blood leukocytes were significantly down-regulated in the later versus early hours of the morning between 06.00-10.00 hours (β-coefficient -0.226, P=0.001 and β-coefficient -0.181, P<0.0001, respectively). These results suggest that current rotating night shift work does not affect circadian gene expression in human circulating leukocytes. In analysis of the peripheral clock in human studies, the hour of blood collection should be precisely specified.

System for computer controlled shifting of an automatic transmission

DOEpatents

Patil, Prabhakar B.

1989-01-01

In an automotive vehicle having an automatic transmission that driveably connects a power source to the driving wheels, a method to control the application of hydraulic pressure to a clutch, whose engagement produces an upshift and whose disengagement produces a downshift, the speed of the power source, and the output torque of the transmission. The transmission output shaft torque and the power source speed are the controlled variables. The commanded power source torque and commanded hydraulic pressure supplied to the clutch are the control variables. A mathematical model is formulated that describes the kinematics and dynamics of the powertrain before, during and after a gear shift. The model represents the operating characteristics of each component and the structural arrangement of the components within the transmission being controlled. Next, a close loop feedback control is developed to determine the proper control law or compensation strategy to achieve an acceptably smooth gear ratio change, one in which the output torque disturbance is kept to a minimum and the duration of the shift is minimized. Then a computer algorithm simulating the shift dynamics employing the mathematical model is used to study the effects of changes in the values of the parameters established from a closed loop control of the clutch hydraulic and the power source torque on the shift quality. This computer simulation is used also to establish possible shift control strategies. The shift strategies determine from the prior step are reduced to an algorithm executed by a computer to control the operation of the power source and the transmission.

RCS jet-flow field interaction effects on the aerodynamics of the space shuttle orbiter

NASA Technical Reports Server (NTRS)

Rausch, J. R.; Roberge, A. M.

1973-01-01

A study was conducted to determine the external effects caused by operation of the reaction control system during entry of the space shuttle orbiter. The effects of jet plume-external flow interactions were emphasized. Force data were obtained for the basic airframe characteristics plus induced effects when the reaction control system is operating. Resulting control amplification and/or coupling were derived and their effects on the aerodynamic stability and control of the orbiter and the reaction control system thrust were determined.

Investigation of the reactions of skin panels in relation to duration of acoustical loading

NASA Technical Reports Server (NTRS)

Kvitka, V. Y.; Kernes, G. I.

1973-01-01

Certain characteristics of the reactions of typical skin panels of a passenger aircraft to acoustical loading are being investigated, for development of an objective method of diagnostics for skin condition, under the operations and maintenance sections of civil aviation. There are a number of difficulties connected with the solution of this problem. The reactions of skin panels exposed to the noises of the exhaust jets are dependent on the aircraft operating conditions, the geometric parameters and limiting conditions of the panels.

Operation Valuation: Teaching Pricing Concepts in an Experiential Environment

ERIC Educational Resources Information Center

Mills, Adam J.; Treen, Emily

2016-01-01

Although marketing education has seen a dramatic shift toward hands-on, experiential learning in recent years, the teaching of pricing has fallen behind complementary elements of the marketing mix in pedagogical execution. Although the teaching of pricing has shifted focus from economic-based models to value-based pricing in theory, available…

World Bank Policy on Education: A Personal Account

ERIC Educational Resources Information Center

Psacharopoulos, George

2006-01-01

Based on the author's over two decades of association with the World Bank, this paper reviews the institution's policies and practice on education. It describes why education policy, as revealed by operations, shifted dramatically since the early Bank projects on education and identifies the reasons for such a shift. The paper argues that the…

Institutional Entrepreneurship in Higher Education. CELCEE Digest No. 98-5.

ERIC Educational Resources Information Center

Kozeracki, Carol

This digest reviews the literature examining ways in which the academic world is shifting toward more entrepreneurial approaches for running an institution and examines some programs that have been developed both at the community college and the senior college level. Reasons cited for the shift toward entrepreneurial ways of operating include cuts…

Initial Results of Illinois' Shifting Gears Pilot Demonstration Evaluation

ERIC Educational Resources Information Center

Bragg, Debra D.; Harmon, Timothy; Kirby, Catherine L.; Kim, Sujung

2009-01-01

This report provides initial results of Illinois' Shifting Gears Initiative that operated between July 1, 2007 and June 30, 2009. This mixed method (qualitative and quantitative) evaluation sought to accomplish three goals: (1) to assess program and student outcomes for two models (adult education and developmental education) for two target groups…

Novel windows for "solar commodities": a device for CO2 reduction using plasmonic catalyst activation.

PubMed

Navarrete, Alexander; Muñoz, Sergio; Sanz-Moral, Luis M; Brandner, Juergen J; Pfeifer, Peter; Martín, Ángel; Dittmeyer, Roland; Cocero, María J

2015-01-01

A novel plasmonic reactor concept is proposed and tested to work as a visible energy harvesting device while allowing reactions to transform CO2 to be carried out. Particularly the reverse water gas shift (RWGS) reaction has been tested as a means to introduce renewable energy into the economy. The development of the new reactor concept involved the synthesis of a new composite capable of plasmonic activation with light, the development of an impregnation method to create a single catalyst reactor entity, and finally the assembly of a reaction system to test the reaction. The composite developed was based on a Cu/ZnO catalyst dispersed into transparent aerogels. This allows efficient light transmission and a high surface area for the catalyst. An effective yet simple impregnation method was developed that allowed introduction of the composites into glass microchannels. The activation of the reaction was made using LEDs that covered all the sides of the reactor allowing a high power delivery. The results of the reaction show a stable process capable of low temperature transformations.

Advancing the Theory of Nuclear Reactions with Rare Isotopes. From the Laboratory to the Cosmos

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nunes, Filomena

2015-06-01

The mission of the Topical Collaboration on the Theory of Reactions for Unstable iSotopes (TORUS) was to develop new methods to advance nuclear reaction theory for unstable isotopes—particularly the (d,p) reaction in which a deuteron, composed of a proton and a neutron, transfers its neutron to an unstable nucleus. After benchmarking the state-of-the-art theories, the TORUS collaboration found that there were no exact methods to study (d,p) reactions involving heavy targets; the difficulty arising from the long-range nature of the well known, yet subtle, Coulomb force. To overcome this challenge, the TORUS collaboration developed a new theory where the complexitymore » of treating the long-range Coulomb interaction is shifted to the calculation of so-called form-factors. An efficient implementation for the computation of these form factors was a major achievement of the TORUS collaboration. All the new machinery developed are essential ingredients to analyse (d,p) reactions involving heavy nuclei relevant for astrophysics, energy production, and stockpile stewardship.« less

Fast reversible wavelet image compressor

NASA Astrophysics Data System (ADS)

Kim, HyungJun; Li, Ching-Chung

1996-10-01

We present a unified image compressor with spline biorthogonal wavelets and dyadic rational filter coefficients which gives high computational speed and excellent compression performance. Convolutions with these filters can be preformed by using only arithmetic shifting and addition operations. Wavelet coefficients can be encoded with an arithmetic coder which also uses arithmetic shifting and addition operations. Therefore, from the beginning to the end, the while encoding/decoding process can be done within a short period of time. The proposed method naturally extends form the lossless compression to the lossy but high compression range and can be easily adapted to the progressive reconstruction.

40 CFR 62.14100 - Scope and delegation of authority.

Code of Federal Regulations, 2011 CFR

2011-07-01

... section 111(d) and section 129 of the Clean Air Act and 40 CFR part 60, subparts B and Cb. This municipal... operators, shift supervisors, and control room operators who have obtained provisional certification on or...

40 CFR 62.14100 - Scope and delegation of authority.

Code of Federal Regulations, 2014 CFR

2014-07-01

... section 111(d) and section 129 of the Clean Air Act and 40 CFR part 60, subparts B and Cb. This municipal... operators, shift supervisors, and control room operators who have obtained provisional certification on or...