Mechanism of H2 histamine receptor dependent modulation of body temperature and neuronal activity in the medial preoptic nucleus

PubMed Central

Tabarean, Iustin V.; Sanchez-Alavez, Manuel; Sethi, Jasmine

2012-01-01

Histamine is involved in the central control of arousal, circadian rhythms and metabolism. The preoptic area, a region that contains thermoregulatory neurons is the main locus of histamine modulation of body temperature. Here we report that in mice histamine activates H2 subtype receptors in the medial preoptic nucleus (MPON) and induces hyperthermia. We also found that a population of glutamatergic MPON neurons express H2 receptors and are excited by histamine or H2 specific agonists. The agonists decreased the input resistance of the neuron and increased the depolarizing “sag” observed during hyperpolarizing current injections. Furthermore, at −60 mV holding potential activation of H2 receptors induced an inward current that was blocked by ZD7288, a specific blocker of the hyperpolarization activated cationic current (Ih). Indeed, activation of H2 receptors resulted in increased Ih amplitude in response to hyperpolarizing voltage steps and a depolarizing shift in its voltage-dependent activation. The neurons excited by H2 specific agonism expressed the HCN1 and HCN2 channel subunits. Our data indicate that at the level of the MPON histamine influences thermoregulation by increasing the firing rate of glutamatergic neurons that express H2 receptors. PMID:22366077

Use of and Reasons for Using Multiple Other Tobacco Products in Daily and Nondaily Smokers: Associations with Cigarette Consumption and Nicotine Dependence

PubMed Central

Dunbar, Michael S.; Shadel, William G.; Tucker, Joan S.; Edelen, Maria O.

2016-01-01

Background Use of other tobacco products (OTPs) among smokers is increasing. Little is known about types of OTP used and the reasons for use, and how OTP use and reasons for use correlate with smoking patterns and nicotine dependence in daily and nondaily smokers. This paper addresses these gaps in the literature. Methods 656 daily smokers and 203 nondaily smokers provided information on their use of different OTPs (hookah, e-cigarettes, chew/snuff, snus, cigars, dissolvables), and reasons for using OTPs (e.g., “to cut down on smoking”), as well as their cigarette consumption and nicotine dependence. Logistic regression models assessed the association of smoking status with OTP use (ever and current) and reasons for use. Within each smoking group, separate logistic regression models examined the associations of OTP use and reasons for use with cigarette consumption and nicotine dependence. Results Compared to daily smokers, nondaily smokers were more likely to use hookah and cigars, less likely to use dissolvables, and less likely to endorse using OTPs to reduce their smoking. Among non-daily smokers, nicotine dependence was associated with a higher likelihood of current OTP use (OR=1.04 [95% CI 1.01–1.07]; p < .05), whereas cigarette consumption was not. Conclusions Results suggest OTP use in nondaily smokers does not correlate with less frequent smoking, but may correlate with higher nicotine dependence. Use of combustible OTPs among nondaily smokers may offset any potential benefits achieved through less frequent cigarette consumption. Providers should explicitly address OTP use when discussing cigarette cessation and reduction. PMID:27664553

Use of and reasons for using multiple other tobacco products in daily and nondaily smokers: Associations with cigarette consumption and nicotine dependence.

PubMed

Dunbar, Michael S; Shadel, William G; Tucker, Joan S; Edelen, Maria O

2016-11-01

Use of other tobacco products (OTPs) among smokers is increasing. Little is known about types of OTP used and the reasons for use, and how OTP use and reasons for use correlate with smoking patterns and nicotine dependence in daily and nondaily smokers. This paper addresses these gaps in the literature. 656 daily smokers and 203 nondaily smokers provided information on their use of different OTPs (hookah, e-cigarettes, chew/snuff, snus, cigars, dissolvables), and reasons for using OTPs (e.g., "to cut down on smoking"), as well as their cigarette consumption and nicotine dependence. Logistic regression models assessed the association of smoking status with OTP use (ever and current) and reasons for use. Within each smoking group, separate logistic regression models examined the associations of OTP use and reasons for use with cigarette consumption and nicotine dependence. Compared to daily smokers, nondaily smokers were more likely to use hookah and cigars, less likely to use dissolvables, and less likely to endorse using OTPs to reduce their smoking. Among non-daily smokers, nicotine dependence was associated with a higher likelihood of current OTP use (OR=1.04 [95% CI 1.01-1.07]; p<0.05), whereas cigarette consumption was not. Results suggest OTP use in nondaily smokers does not correlate with less frequent smoking, but may correlate with higher nicotine dependence. Use of combustible OTPs among nondaily smokers may offset any potential benefits achieved through less frequent cigarette consumption. Providers should explicitly address OTP use when discussing cigarette cessation and reduction. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Homeodomain protein Otp affects developmental neuropeptide switching in oxytocin neurons associated with a long-term effect on social behavior

PubMed Central

Wircer, Einav; Blechman, Janna; Borodovsky, Nataliya; Tsoory, Michael; Nunes, Ana Rita; Oliveira, Rui F; Levkowitz, Gil

2017-01-01

Proper response to stress and social stimuli depends on orchestrated development of hypothalamic neuronal circuits. Here we address the effects of the developmental transcription factor orthopedia (Otp) on hypothalamic development and function. We show that developmental mutations in the zebrafish paralogous gene otpa but not otpb affect both stress response and social preference. These behavioral phenotypes were associated with developmental alterations in oxytocinergic (OXT) neurons. Thus, otpa and otpb differentially regulate neuropeptide switching in a newly identified subset of OXT neurons that co-express the corticotropin-releasing hormone (CRH). Single-cell analysis revealed that these neurons project mostly to the hindbrain and spinal cord. Ablation of this neuronal subset specifically reduced adult social preference without affecting stress behavior, thereby uncoupling the contribution of a specific OXT cluster to social behavior from the general otpa−/− deficits. Our findings reveal a new role for Otp in controlling developmental neuropeptide balance in a discrete OXT circuit whose disrupted development affects social behavior. DOI: http://dx.doi.org/10.7554/eLife.22170.001 PMID:28094761

Temperature-Dependent Rate Coefficients for the Reaction of CH2OO with Hydrogen Sulfide.

PubMed

Smith, Mica C; Chao, Wen; Kumar, Manoj; Francisco, Joseph S; Takahashi, Kaito; Lin, Jim Jr-Min

2017-02-09

The reaction of the simplest Criegee intermediate CH 2 OO with hydrogen sulfide was measured with transient UV absorption spectroscopy in a temperature-controlled flow reactor, and bimolecular rate coefficients were obtained from 278 to 318 K and from 100 to 500 Torr. The average rate coefficient at 298 K and 100 Torr was (1.7 ± 0.2) × 10 -13 cm 3 s -1 . The reaction was found to be independent of pressure and exhibited a weak negative temperature dependence. Ab initio quantum chemistry calculations of the temperature-dependent reaction rate coefficient at the QCISD(T)/CBS level are in reasonable agreement with the experiment. The reaction of CH 2 OO with H 2 S is 2-3 orders of magnitude faster than the reaction with H 2 O monomer. Though rates of CH 2 OO scavenging by water vapor under atmospheric conditions are primarily controlled by the reaction with water dimer, the H 2 S loss pathway will be dominated by the reaction with monomer. The agreement between experiment and theory for the CH 2 OO + H 2 S reaction lends credence to theoretical descriptions of other Criegee intermediate reactions that cannot easily be probed experimentally.

Accurate experimental determination of the isotope effects on the triple point temperature of water. I. Dependence on the 2H abundance

NASA Astrophysics Data System (ADS)

Faghihi, V.; Peruzzi, A.; Aerts-Bijma, A. T.; Jansen, H. G.; Spriensma, J. J.; van Geel, J.; Meijer, H. A. J.

2015-12-01

Variation in the isotopic composition of water is one of the major contributors to uncertainty in the realization of the triple point of water (TPW). Although the dependence of the TPW on the isotopic composition of the water has been known for years, there is still a lack of a detailed and accurate experimental determination of the values for the correction constants. This paper is the first of two articles (Part I and Part II) that address quantification of isotope abundance effects on the triple point temperature of water. In this paper, we describe our experimental assessment of the 2H isotope effect. We manufactured five triple point cells with prepared water mixtures with a range of 2H isotopic abundances encompassing widely the natural abundance range, while the 18O and 17O isotopic abundance were kept approximately constant and the 18O  -  17O ratio was close to the Meijer-Li relationship for natural waters. The selected range of 2H isotopic abundances led to cells that realised TPW temperatures between approximately  -140 μK to  +2500 μK with respect to the TPW temperature as realized by VSMOW (Vienna Standard Mean Ocean Water). Our experiment led to determination of the value for the δ2H correction parameter of A2H  =  673 μK / (‰ deviation of δ2H from VSMOW) with a combined uncertainty of 4 μK (k  =  1, or 1σ).

L to H mode transition: Parametric dependencies of the temperature threshold

DOE PAGES

Bourdelle, C.; Chone, L.; Fedorczak, N.; ...

2015-06-15

The L to H mode transition occurs at a critical power which depends on various parameters, such as the magnetic field, the density, etc. Experimental evidence on various tokamaks (JET, ASDEX-Upgrade, DIII-D, Alcator C-Mod) points towards the existence of a critical temperature characterizing the transition. This criterion for the L-H transition is local and is therefore easier to be compared to theoretical approaches. In order to shed light on the mechanisms of the transition, simple theoretical ideas are used to derive a temperature threshold (T th). They are based on the stabilization of the underlying turbulence by a mean radialmore » electric field shear. The nature of the turbulence varies as the collisionality decreases, from resistive ballooning modes to ion temperature gradient and trapped electron modes. The obtained parametric dependencies of the derived T th are tested versus magnetic field, density, effective charge. Furthermore, various robust experimental observations are reproduced, in particular T th increases with magnetic field B and increases with density below the density roll-over observed on the power threshold.« less

AOI [3] High-Temperature Nano-Derived Micro-H 2 and - H 2S Sensors

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

Sabolsky, Edward M.

2014-08-01

The emissions from coal-fired power plants remain a significant concern for air quality. This environmental challenge must be overcome by controlling the emission of sulfur dioxide (SO 2) and hydrogen sulfide (H 2S) throughout the entire coal combustion process. One of the processes which could specifically benefit from robust, low cost, and high temperature compatible gas sensors is the coal gasification process which converts coal and/or biomass into syngas. Hydrogen (H 2), carbon monoxide (CO) and sulfur compounds make up 33%, 43% and 2% of syngas, respectively. Therefore, development of a high temperature (>500°C) chemical sensor for in-situ monitoring ofmore » H 2, H 2S and SO2 2 levels during coal gasification is strongly desired. The selective detection of SO 2/H 2S in the presence of H 2, is a formidable task for a sensor designer. In order to ensure effective operation of these chemical sensors, the sensor system must inexpensively function within harsh temperature and chemical environment. Currently available sensing approaches, which are based on gas chromatography, electrochemistry, and IR-spectroscopy, do not satisfy the required cost and performance targets. This work focused on the development microsensors that can be applied to this application. In order to develop the high- temperature compatible microsensor, this work addressed various issues related to sensor stability, selectivity, and miniaturization. In the research project entitled “High-Temperature Nano-Derived Micro-H 2 and -H 2S Sensors”, the team worked to develop micro-scale, chemical sensors and sensor arrays composed of nano-derived, metal-oxide composite materials to detect gases like H 2, SO 2, and H 2S within high-temperature environments (>500°C). The research was completed in collaboration with NexTech Materials, Ltd. (Lewis Center, Ohio). NexTech assisted in the testing of the sensors in syngas with contaminate levels of H 2S. The idea of including nanomaterials as the

Temperature Dependence of Attenuation of Coplanar Waveguide on 4H High Resistivity SIC Through 540C

NASA Technical Reports Server (NTRS)

Ponchak, G. E.; Schwartz, Z.; Alterovitz, S. A.; Downey, A. N.; Freeman, J. C.

2003-01-01

For the first time, the temperature and frequency dependence of the attenuation of a Coplanar Waveguide (CPW) on 4H, High Resistivity Sic substrate is reported. The low frequency attenuation increases by 2 dB/cm at 500 C and the high frequency attenuation increases by 3.3 dB/cm at 500 C compared to room temperature.

Temperature dependence of tris(2,2'-bipyridine) ruthenium (II) device characteristics

NASA Astrophysics Data System (ADS)

Slinker, Jason D.; Malliaras, George G.; Flores-Torres, Samuel; Abruña, Héctor D.; Chunwachirasiri, Withoon; Winokur, Michael J.

2004-04-01

We have investigated the temperature dependence of the current, radiance, and efficiency from electroluminescent devices based on [Ru(bpy)3]2+(PF6-)2, where bpy is 2,2'-bipyridine. We find that the current increases monotonically with temperature from 200 to 380 K, while the radiance reaches a maximum near room temperature. For temperatures greater than room temperature, an irreversible, current-induced degradation occurs with thermal cycling that diminishes both the radiance and the photoluminescence (PL) quantum yield, but does not affect the current. The temperature dependence of the external quantum efficiency is fully accounted for by the dependence of the PL quantum yield as measured from the emissive area of the device. This implies that the contacts remain ohmic throughout the temperature range investigated. The quenching of the PL with temperature was attributed to thermal activation to a nonradiative d-d transition. The temperature dependence of the current shows a complex behavior in which transport appears to be thermally activated, with distinct low-temperature and high-temperature regimes.

Low-Temperature Rate Coefficients of C2H with CH4 and CD4 from 154 to 359 K

NASA Technical Reports Server (NTRS)

Opansky, Brian J.; Leone, Stephen R.

1996-01-01

Rate coefficients for the reaction C2H + CH4 yields C2H2 + CH3 and C2H + CD4 yields C2HD + CD3 are measured over the temperature range 154-359 K using transient infrared laser absorption spectroscopy. Ethynyl radicals are produced by pulsed laser photolysis of C2H2 in a variable temperature flow cell, and a tunable color center laser probes the transient removal of C2H (Chi(exp 2) Sigma(+) (0,0,0)) in absorption. The rate coefficients for the reactions of C2H with CH4 and CD4 both show a positive temperature dependence over the range 154-359 K, which can be expressed as k(sub CH4) = (1.2 +/- 0.1) x 10(exp -11) exp((-491 +/- 12)/T) and k(sub CD4) = (8.7 +/- 1.8) x 10(exp -12) exp((-650 +/- 61)/T) cm(exp 3) molecule(exp -1) s(exp -1), respectively. The reaction of C2H + CH4 exhibits a significant kinetic isotope effect at 300 K of k(sub CH4)/k(sub CD4) = 2.5 +/- 0.2. Temperature dependent rate constants for C2H + C2H2 were also remeasured over an increased temperature range from 143 to 359 K and found to show a slight negative temperature dependence, which can be expressed as k(sub C2H2) = 8.6 x 10(exp -16) T(exp 1.8) exp((474 +/- 90)/T) cm(exp 3) molecule(exp -1) s(exp -1).

H2/O2 three-body rates at high temperatures

NASA Technical Reports Server (NTRS)

Marinelli, William J.; Kessler, William J.; Carleton, Karen L.

1991-01-01

Hydrogen atoms are produced in the presence of excess O2, and the first-order decay are studied as a function of temperature and pressure in order to obtain the rate coefficient for the three-body reaction between H-atoms and O2. Attention is focused on the kinetic scheme employed as well as the reaction cell and photolysis and probe laser system. A two-photon laser-induced fluorescence technique is employed to detect H-atoms without optical-thickness or O2-absorption problems. Results confirm measurements reported previously for the H + O2 + N2 reaction at 300 K and extend these measurements to higher temperatures. Preliminary data indicate non-Arrehenius-type behavior of this reaction rate coefficient as a function of temperature. Measurements of the rate coefficient for H + O2 + Ar reaction at 300 K give a rate coefficient of 2.1 +/- 0.1 x 10 to the -32nd cm exp 6/molecule sec.

Photodissociation in the atmosphere of Mars - Impact of high resolution, temperature-dependent CO2 cross-section measurements

NASA Technical Reports Server (NTRS)

Anbar, A. D.; Allen, M.; Nair, H. A.

1993-01-01

We have investigated the impact of high resolution, temperature-dependent CO2 cross-section measurements, reported by Lewis and Carver (1983), on calculations of photodissociation rate coefficients in the Martian atmosphere. We find that the adoption of 50 A intervals for the purpose of computational efficiency results in errors in the calculated values for photodissociation of CO2, H2O, and O2 which are generally not above 10 percent, but as large as 20 percent in some instances. These are acceptably small errors, especially considering the uncertainties introduced by the large temperature dependence of the CO2 cross section. The inclusion of temperature-dependent CO2 cross sections is shown to lead to a decrease in the diurnally averaged rate of CO2 photodissociation as large as 33 percent at some altitudes, and increases of as much as 950 percent and 80 percent in the photodissociation rate coefficients of H2O and O2, respectively. The actual magnitude of the changes depends on the assumptions used to model the CO2 absorption spectrum at temperatures lower than the available measurements, and at wavelengths longward of 1970 A.

Temperature dependence of current-and capacitance-voltage characteristics of an Au/4H-SiC Schottky diode

NASA Astrophysics Data System (ADS)

Gülnahar, Murat

2014-12-01

In this study, the current-voltage (I-V) and capacitance-voltage (C-V) measurements of an Au/4H-SiC Schottky diode are characterized as a function of the temperature in 50-300 K temperature range. The experimental parameters such as ideality factor and apparent barrier height presents to be strongly temperature dependent, that is, the ideality factor increases and the apparent barrier height decreases with decreasing temperature, whereas the barrier height values increase with the temperature for C-V data. Likewise, the Richardson plot deviates at low temperatures. These anomaly behaviors observed for Au/4H-SiC are attributed to Schottky barrier inhomogeneities. The barrier anomaly which relates to interface of Au/4H-SiC is also confirmed by the C-V measurements versus the frequency measured in 300 K and it is interpreted by both Tung's lateral inhomogeneity model and multi-Gaussian distribution approach. The values of the weighting coefficients, standard deviations and mean barrier height are calculated for each distribution region of Au/4H-SiC using the multi-Gaussian distribution approach. In addition, the total effective area of the patches NAe is obtained at separate temperatures and as a result, it is expressed that the low barrier regions influence meaningfully to the current transport at the junction. The homogeneous barrier height value is calculated from the correlation between the ideality factor and barrier height and it is noted that the values of standard deviation from ideality factor versus q/3kT curve are in close agreement with the values obtained from the barrier height versus q/2kT variation. As a result, it can be concluded that the temperature dependent electrical characteristics of Au/4H-SiC can be successfully commented on the basis of the thermionic emission theory with both models.

CKA2 functions in H2O2-induced apoptosis and high-temperature stress tolerance by regulating NO accumulation in yeast.

PubMed

Liu, Wen-Cheng; Yuan, Hong-Mei; Li, Yun-Hui; Lu, Ying-Tang

2015-09-01

Nitric oxide (NO) plays key roles in yeast responses to various environmental factors, such as H2O2 and high temperature. However, the gene encoding NO synthase (NOS) in yeast has not yet been identified, and the mechanism underlying the regulation of NOS-like activity is poorly understood. Here, we report on the involvement of CKA2 in H2O2-induced yeast apoptosis and yeast high-temperature stress tolerance. Our results showed that although Δcka2 mutant had reduced NO accumulation with decreased apoptosis after H2O2 exposure, treatment with a NO donor, sodium nitroprusside, resulted in similar survival rate of Δcka2 mutant compared to that of wild-type yeast when subjected to H2O2 stress. This finding occurred because H2O2-enhanced NOS-like activity in wild-type yeast was significantly repressed in Δcka2. Our additional experiments indicated that both high-temperature-enhanced NO accumulation and NOS-like activity were also suppressed in Δcka2, leading to the hypersensitivity of the mutant to high temperature in terms of changes in survival rate. Thus, our results showed that CKA2 functioned in H2O2-induced apoptosis and high-temperature stress tolerance by regulating NOS-like-dependent NO accumulation in yeast. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Surgical stabilization of rib fractures using Inion OTPS wraps--techniques and quality of life follow-up.

PubMed

Campbell, Nicole; Conaglen, Paul; Martin, Katherine; Antippa, Phillip

2009-09-01

A variety of operative techniques have been described in the past for the surgical stabilization of fractured ribs. From February 2004 to November 2008, consecutive patients who underwent open reduction and internal fixation of traumatic fractured ribs during their index admission using the Inion orthopedic trauma plating system (OTPS) at a Level I trauma center were retrospectively analyzed. Demographics, Injury Severity Scores, number and site of rib fractures, operative details, and complications were recorded. All patients were followed-up with a questionnaire assessing chest symptoms, disability, and quality of life. Thirty-two patients underwent surgical stabilization with Inion OTPS. Road crashes were the commonest mechanism of injury (81%), followed by falls. Seventy-two percent of patients were male, with a median age at operation of 53 years (interquartile range [IQR], 40-64 years). Median number of ribs fixed was 3 (IQR, 2-4), while median number of fractures was 9 (IQR, 6-13). Median time to fixation was 5 days (IQR, 3-7 days), intensive care unit stay 3 days (IQR, 0.8-6.3 days), and total hospital stay 13.5 days (IQR, 8.8-22 days). Wound infection occurred in 19%, with nonunion of a fixed fracture in one patient. Sixty-three percent of patients completed the survey with a mean time between open reduction and internal fixation and questionnaire of 1,039 days (+/-480 days). Patients reported low levels of pain at rest and with coughing (median at rest 1.0/10 [IQR, 0-2.3/10]; with coughing 1.3/10 [IQR, 0-3.75/10]). Chest wall stiffness was experienced by 60% of patients, while dyspnoea at rest was reported by 20% of patients. Mean return to work (for 55%) was 3.9 months (+/-3.3 months). All patients were satisfied with the results of their operation. Patients demonstrated low levels of pain and satisfactory rehabilitation. The Inion OTPS system has several advantages including gradual transference of stress loads to bone, micromotion across the fracture

High temperature kinetic study of the reactions H + O2 = OH + O and O + H2 = OH + H in H2/O2 system by shock tube-laser absorption spectroscopy

NASA Technical Reports Server (NTRS)

Ryu, Si-Ok; Hwang, Soon Muk; Dewitt, Kenneth J.

1995-01-01

The reactions: (1) H + O2 = OH + O; and (2) O + H2 = OH + H are the most important elementary reactions in gas phase combustion. They are the main chain-branching reaction in the oxidation of H2 and hydrocarbon fuels. In this study, rate coefficients of the reactions and have been measured over a wide range of composition, pressure, density and temperature behind the reflected shock waves. The experiments were performed using the shock tube - laser absorption spectroscopic technique to monitor OH radicals formed in the shock-heated H2/O2/Ar mixtures. The OH radicals were detected using the P(1)(5) line of (0,0) band of the A(exp 2) Sigma(+) from X(exp 2) Pi transition of OH at 310.023 nm (air). The data were analyzed with the aid of computer modeling. In the experiments great care was exercised to obtain high time resolution, linearity and signal-to-noise. The results are well represented by the Arrhenius expressions. The rate coefficient expression for reaction (1) obtained in this study is k(1) = (7.13 +/- 0.31) x 10(exp 13) exp(-6957+/- 30 K/T) cu cm/mol/s (1050 K less than or equal to T less than or equal to 2500 K) and a consensus expression for k(1) from a critical review of the most recent evaluations of k(1) (including our own) is k(1) = 7.82 x 10(exp 13) exp(-7105 K/T) cu cm/mol/s (960 K less than or equal to T less than or equal to 5300 K). The rate coefficient expression of k(2) is given by k(2) = (1.88 +/- 0.07) x 10(exp 14) exp(-6897 +/- 53 K/T) cu cm/mol/s (1424 K less than or equal to T less than or equal to 2427 K). For k(1), the temperature dependent A-factor and the correlation between the values of k(1) and the inverse reactant densities were not found. In the temperature range of this study, non-Arrhenius expression of k(2) which shows the upward curvature was not supported.

The rate of the reaction between CN and C2H2 at interstellar temperatures.

PubMed

Woon, D E; Herbst, E

1997-03-01

The rate coefficient for the important interstellar reaction between CN and C2H2 has been calculated as a function of temperature between 10 and 300 K. The potential surface for this reaction has been determined through ab initio quantum chemical techniques; the potential exhibits no barrier in the entrance channel but does show a small exit channel barrier, which lies below the energy of reactants. Phase-space calculations for the reaction dynamics, which take the exit channel barrier into account, show the same unusual temperature dependence as determined by experiment, in which the rate coefficient at first increases as the temperature is reduced below room temperature and then starts to decrease as the temperature drops below 50-100 K. The agreement between theory and experiment provides strong confirmation that the reaction occurs appreciably at cool interstellar temperatures.

The Formation and Spatiotemporal Progress of the pH Wave Induced by the Temperature Gradient in the Thin-Layer H2O2-Na2S2O3-H2SO4-CuSO4 Dynamical System.

PubMed

Jędrusiak, Mikołaj; Orlik, Marek

2016-03-31

The H2O2-S2O3(2-)-H(+)-Cu(2+) dynamical system exhibits sustained oscillations under flow conditions but reveals only a single initial peak of the indicator electrode potential and pH variation under batch isothermal conditions. Thus, in the latter case, there is no possibility of the coupling of the oscillations and diffusion which could lead to formation of sustained spatiotemporal patterns in this process. However, in the inhomogeneous temperature field, due to dependence of the local reaction kinetics on temperature, spatial inhomogeneities of pH distribution can develop which, in the presence of an appropriate indicator, thymol blue, manifest themselves as the color front traveling along the quasi-one-dimensional reactor. In this work, we describe the experimental conditions under which the above-mentioned phenomena can be observed and present their numerical model based on thermokinetic coupling and spatial coordinate introduced to earlier isothermal homogeneous kinetic mechanism.

Infrared photodissociation spectroscopy of H(+)(H2O)6·M(m) (M = Ne, Ar, Kr, Xe, H2, N2, and CH4): messenger-dependent balance between H3O(+) and H5O2(+) core isomers.

PubMed

Mizuse, Kenta; Fujii, Asuka

2011-04-21

Although messenger mediated spectroscopy is a widely-used technique to study gas phase ionic species, effects of messengers themselves are not necessarily clear. In this study, we report infrared photodissociation spectroscopy of H(+)(H(2)O)(6)·M(m) (M = Ne, Ar, Kr, Xe, H(2), N(2), and CH(4)) in the OH stretch region to investigate messenger(M)-dependent cluster structures of the H(+)(H(2)O)(6) moiety. The H(+)(H(2)O)(6), the protonated water hexamer, is the smallest system in which both the H(3)O(+) (Eigen) and H(5)O(2)(+) (Zundel) hydrated proton motifs coexist. All the spectra show narrower band widths reflecting reduced internal energy (lower vibrational temperature) in comparison with bare H(+)(H(2)O)(6). The Xe-, CH(4)-, and N(2)-mediated spectra show additional band features due to the relatively strong perturbation of the messenger. The observed band patterns in the Ar-, Kr-, Xe-, N(2)-, and CH(4)-mediated spectra are attributed mainly to the "Zundel" type isomer, which is more stable. On the other hand, the Ne- and H(2)-mediated spectra are accounted for by a mixture of the "Eigen" and "Zundel" types, like that of bare H(+)(H(2)O)(6). These results suggest that a messenger sometimes imposes unexpected isomer-selectivity even though it has been thought to be inert. Plausible origins of the isomer-selectivity are also discussed.

Porous microspheres of MgO-patched TiO2 for CO2 photoreduction with H2O vapor: temperature-dependent activity and stability.

PubMed

Liu, Lianjun; Zhao, Cunyu; Zhao, Huilei; Pitts, Daniel; Li, Ying

2013-05-07

A novel MgO-patched TiO2 microsphere photocatalyst demonstrated 10 times higher activity toward CO production from CO2 photoreduction with H2O vapor, when the reaction temperature increased from 50 to 150 °C. The catalytic performance of hybrid MgO-TiO2 was much more stable than TiO2, particularly at a higher temperature, likely due to easier desorption of reaction intermediates and the enhanced CO2 adsorption by MgO.

Ternary recombination of H3+, H2D+, HD2+, and D3+ with electrons in He/Ar/H2/D2 gas mixtures

NASA Astrophysics Data System (ADS)

Kalosi, Abel; Dohnal, Petr; Plasil, Radek; Johnsen, Rainer; Glosik, Juraj

2016-09-01

The temperature dependence of the ternary recombination rate coefficients of H2D+ and HD2+ ions has been studied in the temperature range of 80-150 K at pressures from 500 to 1700 Pa in a stationary afterglow apparatus equipped with a cavity ring-down spectrometer. Neutral gas mixtures consisting of He/Ar/H2/D2 (with typical number densities 1017 /1014 /1014 /1014 cm-3) were employed to produce the desired ionic species and their fractional abundances were monitored as a function of helium pressure and the [D2]/[H2] ratio of the neutral gas. In addition, the translational and the rotational temperature and the ortho to para ratio were monitored for both H2D+ and HD2+ ions. A fairly strong pressure dependence of the effective recombination rate coefficient was observed for both ion species, leading to ternary recombination rate coefficients close to those previously found for (helium assisted) ternary recombination of H3+ and D3+. Work supported by: Czech Science Foundation projects GACR 14-14649P, GACR 15-15077S, GACR P209/12/0233, and by Charles University in Prague Project Nr. GAUK 692214.

Rate Coefficients of C2H with C2H4, C2H6, and H2 from 150 to 359 K

NASA Technical Reports Server (NTRS)

Opansky, Brian J.; Leone, Stephen R.

1996-01-01

Rate coefficients for the reactions C2H with C2H4, C2H6, and H2 are measured over the temperature range 150-359 K using transient infrared laser absorption spectroscopy. The ethynyl radical is formed by photolysis of C2H2 with a pulsed excimer laser at 193 nm, and its transient absorption is monitored with a color center laser on the Q(sub 11)(9) line of the A(sup 2) Pi-Chi(sup 2) Sigma transition at 3593.68 cm(exp -1). Over the experimental temperature range 150-359 K the rate constants of C2H with C2H4, C2H6, and H2 can be fitted to the Arrhenius expressions k(sub C2H4) = (7.8 +/- 0.6) x 10(exp -11) exp[(134 +/- 44)/T], k(sub C2H6) = (3.5 +/- 0.3) x 10(exp -11) exp[(2.9 +/- 16)/T], and k(sub H2) = (1.2 +/- 0.3) x 10(exp -11) exp[(-998 +/- 57)]/T cm(exp 3) molecule(exp -1) sec(exp -1). The data for C2H with C2H4 and C2H6 indicate a negligible activation energy to product formation shown by the mild negative temperature dependence of both reactions. When the H2 data are plotted together with the most recent high-temperature results from 295 to 854 K, a slight curvature is observed. The H2 data can be fit to the non-Arrhenius form k(sub H2) = 9.2 x 10(exp -18) T(sup 2.17 +/- 0.50) exp[(-478 +/- 165)/T] cm(exp 3) molecules(exp -1) sec(exp -1). The curvature in the Arrhenius plot is discussed in terms of both quantum mechanical tunneling of the H atom from H2 to the C2H radical and bending mode contributions to the partition function.

Room temperature CO and H2 sensing with carbon nanoparticles.

PubMed

Kim, Daegyu; Pikhitsa, Peter V; Yang, Hongjoo; Choi, Mansoo

2011-12-02

We report on a shell-shaped carbon nanoparticle (SCNP)-based gas sensor that reversibly detects reducing gas molecules such as CO and H(2) at room temperature both in air and inert atmosphere. Crystalline SCNPs were synthesized by laser-assisted reactions in pure acetylene gas flow, chemically treated to obtain well-dispersed SCNPs and then patterned on a substrate by the ion-induced focusing method. Our chemically functionalized SCNP-based gas sensor works for low concentrations of CO and H(2) at room temperature even without Pd or Pt catalysts commonly used for splitting H(2) molecules into reactive H atoms, while metal oxide gas sensors and bare carbon-nanotube-based gas sensors for sensing CO and H(2) molecules can operate only at elevated temperatures. A pristine SCNP-based gas sensor was also examined to prove the role of functional groups formed on the surface of functionalized SCNPs. A pristine SCNP gas sensor showed no response to reducing gases at room temperature but a significant response at elevated temperature, indicating a different sensing mechanism from a chemically functionalized SCNP sensor.

Temperature Dependences for the Reactions of Ar+, O2+, and C7H7+ with Toluene and Ethylbenzene

DTIC Science & Technology

2013-07-01

Miller, I. Dotan, M. Mendendez-Barreto, J. Seeley , J.S. Williamson, F. Dale, P.L. Mundis, R.A. Morris, J.F. Paulson, A.A. Viggiano, A flowing...9248. 32] J.V. Seeley , R.A. Morris, A.A. Viggiano, Gas phase reactions of hydrated halides with chlorine, Journal of Physical Chemistry 100 (1996) 15821...15826. 33] J.V. Seeley , R.A. Morris, A.A. Viggiano, H. Wang, W.L. Hase, Temperature dependencies of the rate constants and branching ratios for the

Temperature dependence of the Raman spectrum of UO2

NASA Astrophysics Data System (ADS)

Elorrieta, J. M.; Bonales, L. J.; Baonza, V. G.; Cobos, J.

2018-05-01

The position of the main spectral features (located at ∼445, ∼575, ∼625, ∼925 and ∼1145 cm-1) in the Raman spectrum of UO2 has been examined from room temperature up to 600 °C. The wavenumber shifts measured for the observed bands have allowed us to obtain the temperature dependence (dω/dT) of the different vibrational modes. Our measurements corroborate the assignment of the band observed at ∼1145 cm-1 to the 2LO overtone. In addition, the temperature dependence of the bandwidths of the T2g and 2LO modes has been analysed.

Corrosion of 310 stainless steel in H2-H2O-H2S gas mixtures: Studies at constant temperature and fixed oxygen potential

NASA Technical Reports Server (NTRS)

Rao, D. B.; Jacob, K. T.; Nelson, H. G.

1981-01-01

Corrosion of SAE 310 stainless steel in H2-H2O-H2S gas mixtures was studied at a constant temperature of 1150 K. Reactive gas mixtures were chosen to yield a constant oxygen potential of approximately 6 x 10 to the minus 13th power/cu Nm and sulfur potentials ranging from 0.19 x 10 to the minus 2nd power/cu Nm to 33 x 10 to the minus 2nd power/cu Nm. The kinetics of corrosion were determined using a thermobalance, and the scales were analyzed using metallography, scanning electron microscopy, and energy dispersive X-ray analysis. Two corrosion regimes, which were dependent on sulfur potential, were identified. At high sulfur potentials (p sub S sub 2 less than or equal to 2.7 x 10 to the minus 2nd power/cu Nm) the corrosion rates were high, the kinetics obeyed a linear rate equation, and the scales consisted mainly of sulfide phases similar to those observed from pure sulfication. At low sulfur potentials (P sub S sub 2 less than or equal to 0.19 x 10 to the minus 2nd power/cu Nm) the corrosion rates were low, the kinetics obeyed a parabolic rate equation, and scales consisted mainly of oxide phases.

Anisotropic H c 2 , thermodynamic and transport measurements, and pressure dependence of T c in K 2 Cr 3 As 3 single crystals

DOE PAGES

Kong, Tai; Bud'ko, Sergey L.; Canfield, Paul C.

2015-01-30

We present a detailed study of single crystalline K 2Cr 3As 3 and analyze its thermodynamic and transport properties, anisotropic H c2(T), and initial pressure dependence of T c. In zero field, the temperature-dependent resistivity is metallic. Deviation from a linear temperature dependence is evident below 100 K and a T 3 dependence is roughly followed from just above T c (~10K) to ~40K. Anisotropic H c2(T) data were measured up to 140 kOe with field applied along and perpendicular to the rodlike crystals. For the applied field perpendicular to the rod, H c2(T) is linear with a slope ~–70more » kOe/K. For field applied along the rod, the slope is about –120 kOe/K below 70 kOe. Above 70 kOe, the magnitude of the slope decreases to ~–70 kOe/K. The electronic specific heat coefficient γ, just above T c, is 73 mJ/mol K 2; the Debye temperature Θ D is 220 K. As a result, the specific heat jump at the superconducting transition ΔC~2.2γT c. Finally, for hydrostatic pressures up to ~7 kbar, T c decreases under pressure linearly at a rate of –0.034K/kbar.« less

Temperature-Dependent Evolution of the Oxidation States of Cobalt and Platinum in Co 1–xPt x Clusters under H 2 and CO + H 2 Atmospheres

DOE PAGES

Yang, Bing; Khadra, Ghassan; Tuaillon-Combes, Juliette; ...

2016-08-25

In this study, Co 1–xPt x clusters of 2.9-nm size with a range of atomically precise Pt/Co atomic ratios (x = 0, 0.25, 0.5, 0.75, 1) were synthesized using the mass-selected low-energy cluster beam deposition (LECBD) technique and soft-landed onto an amorphous alumina thin film prepared by atomic layer deposition (ALD). Utilizing ex situ X-ray photoemission spectroscopy (XPS), the oxidation state of the as-made clusters supported on Al 2O 3 was determined after both a 1-h-long exposure to air and aging for several weeks while exposed to air. Next, the aged cluster samples were characterized by grazing-incidence X-ray absorption spectroscopymore » (GIXAS) and then pretreated with diluted hydrogen and further exposed to the mixture of diluted CO and H 2 up to 225°C at atmospheric pressure, and the temperature-dependent evolutions of the particle size/shape and the oxidation states of the individual metal components within the clusters were monitored using in situ grazing-incidence small-angle X-ray scattering and X-ray absorption spectroscopy (GISAXS/GIXAS). The changes in the oxidation states of Co and Pt exhibited a nonlinear dependence on the Pt/Co atomic ratio of the clusters. For example, a low Pt/Co ratio (x ≤ 0.5) facilitates the formation of Co(OH) 2, whereas a high Pt/Co ratio (x = 0.75) stabilizes the Co 3O 4 composition instead through the formation of a Co–Pt core–shell structure where the platinum shell inhibits the reduction of cobalt in the core of the Co 1–xPt x alloy clusters. Finally, the obtained results indicate methods for optimizing the composition and structure of binary alloy clusters for catalysis.« less

Temperature-Dependent Evolution of the Oxidation States of Cobalt and Platinum in Co 1–x Pt x Clusters under H 2 and CO + H 2 Atmospheres

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

Yang, Bing; Khadra, Ghassan; Tuaillon-Combes, Juliette

2016-09-29

Co1-xPtx clusters of 2.9-nm size with a range of atomically precise Pt/Co atomic ratios (x = 0, 0.25, 0.5, 0.75, 1) were synthesized using the mass-selected low-energy cluster beam deposition (LECBD) technique and soft-landed onto an amorphous alumina thin film prepared by atomic layer deposition (ALD). Utilizing ex situ X-ray photoemission spectroscopy (XPS), the oxidation state of the as-made clusters supported on Al2O3 was determined after both a 1-h-long exposure to air and aging for several weeks while exposed to air. Next, the aged duster samples were characterized by grazing-incidence X-ray absorption spectroscopy (GIXAS) and then pretreated with diluted hydrogenmore » and further exposed to the mixture of diluted CO and H-2 up to 225 degrees C at atmospheric pressure, and the temperature-dependent evolutions of the particle size/shape and the oxidation states of the individual metal components within the dusters were monitored using in situ grazing-incidence small-angle X-ray scattering and X-ray absorption spectroscopy (GISAXS/GIXAS). The changes in the oxidation states of Co and Pt exhibited a nonlinear dependence on the Pt/Co atomic ratio of the dusters. For example, a low Pt/Co ratio (x <= 0.5) facilitates the formation of Co(OH)(2), whereas a high Pt/Co ratio (x = 0.75) stabilizes the Co3O4 composition instead through the formation of a Co-Pt core-shell structure where the platinum shell inhibits the reduction of cobalt in the core of the Co1-xPtx alloy dusters. The obtained results indicate methods for optimizing the composition and structure of binary alloy clusters for catalysis.« less

Origin of temperature dependent conduction of current from n-4H-SiC into silicon dioxide films at high electric fields

NASA Astrophysics Data System (ADS)

Xiang, An; Xu, Xingliang; Zhang, Lin; Li, Zhiqiang; Li, Juntao; Dai, Gang

2018-02-01

The conduction of current from n-4H-SiC into pyrogenic and dry oxidized films is studied. Anomalous current conduction was observed at a high electric field above 8 MV/cm for dry oxidized metal-oxide-semiconductor (MOS) capacitors, which cannot be interpreted in the framework of pure Fowler-Nordheim tunneling. The temperature-dependent current measurement and density of interface trap estimated from the hi-lo method for the SiO2/4H-SiC interface revealed that the combined current conduction of Fowler-Nordheim and Poole-Frenkel emission is responsible for the current conduction in both pyrogenic and dry oxidized MOS capacitors. Furthermore, the origin of temperature dependent current conduction is the Poole-Frenkel emission via the carbon pair defect trap level at 1.3 eV below the conduction band edge of SiO2. In addition, with the dry oxidized capacitors, the enhanced temperature dependent current above 8 MV/cm is attributed to the PF emission via a trap level at 1.47 eV below the conduction band edge of SiO2, which corresponds to another configuration of a carbon pair defect in SiO2 films.

Temperature dependence of the ClONO2 UV absorption spectrum

NASA Technical Reports Server (NTRS)

Burkholder, James B.; Talukdar, Ranajit K.; Ravishankara, A. R.

1994-01-01

The temperature dependence of the ClONO2 absorption spectrum has been measured between 220 and 298 K and between 195 and 430 nm using a diode array spectrometer. The absorption cross sections were determined using both: (1) absolute pressure measurements at 296 K and (2) measurements at various temperatures relative to 296 K using a dual absorption cell arrangement. The temperature dependence of the ClONO2 absorption spectrum shows very broad structure. The amplitude of the temperature dependence relative to that at 296 K is weak at short wavelengths, less than 2% at 215 nm and 220 K, but significant at the wavelengths important in the stratosphere, about 30% at 325 nm and 220 K. Our ClONO2 absorption cross section data are in good general agreement with the previous measurements of Molina and Molina (1979).

Stepwise formation of H3O(+)(H2O)n in an ion drift tube: Empirical effective temperature of association/dissociation reaction equilibrium in an electric field.

PubMed

Nakai, Yoichi; Hidaka, Hiroshi; Watanabe, Naoki; Kojima, Takao M

2016-06-14

We measured equilibrium constants for H3O(+)(H2O)n-1 + H2O↔H3O(+)(H2O)n (n = 4-9) reactions taking place in an ion drift tube with various applied electric fields at gas temperatures of 238-330 K. The zero-field reaction equilibrium constants were determined by extrapolation of those obtained at non-zero electric fields. From the zero-field reaction equilibrium constants, the standard enthalpy and entropy changes, ΔHn,n-1 (0) and ΔSn,n-1 (0), of stepwise association for n = 4-8 were derived and were in reasonable agreement with those measured in previous studies. We also examined the electric field dependence of the reaction equilibrium constants at non-zero electric fields for n = 4-8. An effective temperature for the reaction equilibrium constants at non-zero electric field was empirically obtained using a parameter describing the electric field dependence of the reaction equilibrium constants. Furthermore, the size dependence of the parameter was thought to reflect the evolution of the hydrogen-bond structure of H3O(+)(H2O)n with the cluster size. The reflection of structural information in the electric field dependence of the reaction equilibria is particularly noteworthy.

Temperature-dependent transitions between normal and inverse isotope effects pertaining to the interaction of H-H and C-H bonds with transition metal centers.

PubMed

Parkin, Gerard

2009-02-17

Deuterium kinetic isotope effects (KIEs) serve as versatile tools to infer details about reaction mechanisms and the nature of transition states, while equilibrium isotope effects (EIEs) associated with the site preferences of hydrogen and deuterium enable researchers to study aspects of molecular structure. Researchers typically interpret primary deuterium isotope effects based on two simple guidelines: (i) the KIE for an elementary reaction is normal (k(H)/k(D) > 1) and (ii) the EIE is dictated by deuterium preferring to be located in the site corresponding to the highest frequency oscillator. In this Account, we evaluate the applicability of these rules to the interactions of H-H and C-H bonds with a transition metal center. Significantly, experimental and computational studies question the predictability of primary EIEs in these systems based on the notion that deuterium prefers to occupy the highest frequency oscillator. In particular, the EIEs for (i) formation of sigma-complexes by coordination of H-H and C-H bonds and (ii) oxidative addition of dihydrogen exhibit unusual temperature dependencies, such that the same system may demonstrate both normal (i.e., K(H)/K(D) > 1) and inverse (i.e., K(H)/K(D) < 1) values. The transition between a normal and inverse EIE indicates that these systems do not demonstrate the typical monotonic variation predicted by the van't Hoff relationship. Instead, the calculated EIEs in these systems are 0 at 0 K, increase to a value greater than 1, and then decrease to unity at infinite temperature. This unusual behavior may be rationalized by considering the individual factors that contribute to the EIE. Specifically, the EIE may be expressed in the form EIE = SYM x MMI x EXC x ZPE (where SYM is the symmetry factor, MMI is the mass-moment of inertia term, EXC is the excitation term, and ZPE is the zero-point energy term), and the distinctive temperature profile results from the inverse ZPE (enthalpy) and normal [SYM x MMI x EXC

O2(b1Σg+) Quenching by O2, CO2, H2O, and N2 at Temperatures of 300-800 K.

PubMed

Zagidullin, M V; Khvatov, N A; Medvedkov, I A; Tolstov, G I; Mebel, A M; Heaven, M C; Azyazov, V N

2017-10-05

Rate constants for the removal of O 2 (b 1 Σ g + ) by collisions with O 2 , N 2 , CO 2 , and H 2 O have been determined over the temperature range from 297 to 800 K. O 2 (b 1 Σ g + ) was excited by pulses from a tunable dye laser, and the deactivation kinetics were followed by observing the temporal behavior of the b 1 Σ g + -X 3 Σ g - fluorescence. The removal rate constants for CO 2 , N 2 , and H 2 O were not strongly dependent on temperature and could be represented by the expressions k CO2 = (1.18 ± 0.05) × 10 -17 × T 1.5 × exp[Formula: see text], k N2 = (8 ± 0.3) × 10 -20 × T 1.5 × exp[Formula: see text], and k H2O = (1.27 ± 0.08) × 10 -16 × T 1.5 × exp[Formula: see text] cm 3 molecule -1 s -1 . Rate constants for O 2 (b 1 Σ g + ) removal by O 2 (X), being orders of magnitude lower, demonstrated a sharp increase with temperature, represented by the fitted expression k O2 = (7.4 ± 0.8) × 10 -17 × T 0.5 × exp[Formula: see text] cm 3 molecule -1 s -1 . All of the rate constants measured at room temperature were found to be in good agreement with previously reported values.

The viscosity and temperature dependence of 1H T1-NMRD of the Gd(H 2O) 83+ complex

NASA Astrophysics Data System (ADS)

Zhou, Xiangzhi; Westlund, Per-Olof

2005-11-01

Water proton T1-NMRD profiles of the Gd(H 2O) 83+ complex have been recorded at three temperatures and at four concentrations of glycerol. The analysis is performed using both the generalized Solomon-Bloembergen-Morgan (GSBM) theory [J. Magn. Reson. 167(2004), 147-160], and the stochastic Liouville approach (SLA). The GSBM approach uses a two processes dynamic model of the zero-field splitting (ZFS) correlation function whereas SLA uses a single process model. Both models reproduce the proton T1-NMRD profiles well. However, the model parameters extracted from the two analyses, yield different ESR X-band spectra which moreover do not reproduce the experimental ESR spectra. It is shown that the analyses of the proton T1-NMRD profiles recorded for a solution Gd(H 2O) 83+ ions are relatively insensitive to the slow modulation part of dynamic model of the ZFS interaction correlation function. The description of the electron spin system results in a very small static ZFS, while recent ESR lineshape analysis indicates that the contribution from the static ZFS is important. Analysis of proton T1-NMRD profiles of Gd(H 2O) 83+ complex do result in a description of the electron spin system but these microscopic parameters are uncertain unless they also are tested in a ESR-lineshape analysis.

Temperature Dependence of the Upper Critical Field in Disordered Hubbard Model with Attraction

NASA Astrophysics Data System (ADS)

Kuchinskii, E. Z.; Kuleeva, N. A.; Sadovskii, M. V.

2017-12-01

We study disorder effects upon the temperature behavior of the upper critical magnetic field in an attractive Hubbard model within the generalized DMFT+Σ approach. We consider the wide range of attraction potentials U—from the weak coupling limit, where superconductivity is described by BCS model, up to the strong coupling limit, where superconducting transition is related to Bose-Einstein condensation (BEC) of compact Cooper pairs, formed at temperatures significantly higher than superconducting transition temperature, as well as the wide range of disorder—from weak to strong, when the system is in the vicinity of Anderson transition. The growth of coupling strength leads to the rapid growth of H c2( T), especially at low temperatures. In BEC limit and in the region of BCS-BEC crossover H c2( T), dependence becomes practically linear. Disordering also leads to the general growth of H c2( T). In BCS limit of weak coupling increasing disorder lead both to the growth of the slope of the upper critical field in the vicinity of the transition point and to the increase of H c2( T) in the low temperature region. In the limit of strong disorder in the vicinity of the Anderson transition localization corrections lead to the additional growth of H c2( T) at low temperatures, so that the H c2( T) dependence becomes concave. In BCS-BEC crossover region and in BEC limit disorder only slightly influences the slope of the upper critical field close to T c . However, in the low temperature region H c2 ( T may significantly grow with disorder in the vicinity of the Anderson transition, where localization corrections notably increase H c2 ( T = 0) also making H c2( T) dependence concave.

Temperature and field dependent magnetization studies on nano-crystalline ZnFe2O4 thin films

NASA Astrophysics Data System (ADS)

Sahu, B. N.; Suresh, K. G.; Venkataramani, N.; Prasad, Shiva; Krishnan, R.

2018-05-01

Single phase nano-crystalline zinc ferrite (ZnFe2O4) thin films were deposited on fused quartz substrate using the pulsed laser deposition technique. The films were deposited at different substrate temperatures. The field dependence of magnetization at 10 K shows hysteresis loops for all the samples. Temperature dependence of the field cooled (FC) and zero field cooled (ZFC) magnetization indicated irreversible behavior between the FC and ZFC data, and the irreversibility depends on the measuring magnetic field. The thermo-magnetic irreversibility in the magnetization data is correlated with the magnitude of the applied field and the coercivity (HC) obtained from the M-H loops.

EPR investigation of local structure for [Mn(H 2O) 6] 2+ cluster in [M(H 2O) 6]XCl 6:Mn 2+ (M = Zn, Mg, Cd, Ca; X = Pt, Sn) systems at different temperatures

NASA Astrophysics Data System (ADS)

Tian, Wen-Yan; Kuang, Xiao-Yu; Li, Hui-Fang; Li, Yan-Fang; Ying-Li

2009-01-01

A theoretical method for studying the inter-relation between the local structure and EPR spectra is established by diagonalizing the complete energy matrices. For [M(H 2O) 6]XCl 6:Mn 2+ (M = Zn, Mg, Cd, Ca; X = Pt, Sn) systems, the calculated results demonstrate that the local structures around the octahedral Mn 2+ centers in the doped systems are very similar despite of the host crystals being different. Furthermore, it is shown that the EPR zero-field parameter D depends simultaneously on the local structure parameters R and θ while ( a - F) depends mainly on R, whether the doped systems are at liquid-nitrogen temperature or room temperature.

Milk pH as a function of CO2 concentration, temperature, and pressure in a heat exchanger.

PubMed

Ma, Y; Barbano, D M

2003-12-01

Raw skim milk, with or without added CO2, was heated, held, and cooled in a small pilot-scale tubular heat exchanger (372 ml/min). The experiment was replicated twice, and, for each replication, milk was first carbonated at 0 to 1 degree C to contain 0 (control), 600, 1200, 1800, and 2400 ppm added CO2 using a continuous carbonation unit. After storage at 0 to 1 degree C, portions of milk at each CO2 concentration were heated to 40, 56, 72, and 80 degrees C, held at the desired temperature for 30 s (except 80 degrees C, holding 20 s) and cooled to 0 to 1 degree C. At each temperature, five pressures were applied: 69, 138, 207, 276, and 345 kPa. Pressure was controlled with a needle valve at the heat exchanger exit. Both the pressure gauge and pH probe were inline at the end of the holding section. Milk pH during heating depended on CO2 concentration, temperature, and pressure. During heating of milk without added CO2, pH decreased linearly as a function of increasing temperature but was independent of pressure. In general, the pH of milk with added CO2 decreased with increasing CO2 concentration and pressure. For milk with added CO2, at a fixed CO2 concentration, the effect of pressure on pH decrease was greater at a higher temperature. At a fixed temperature, the effect of pressure on pH decrease was greater for milk with a higher CO2 concentration. Thermal death of bacteria during pasteurization of milk without added CO2 is probably due not only to temperature but also to the decrease in pH that occurs during the process. Increasing milk CO2 concentration and pressure decreases the milk pH even further during heating and may further enhance the microbial killing power of pasteurization.

Optimization of NO oxidation by H2O2 thermal decomposition at moderate temperatures.

PubMed

Zhao, Hai-Qian; Wang, Zhong-Hua; Gao, Xing-Cun; Liu, Cheng-Hao; Qi, Han-Bing

2018-01-01

H2O2 was adopted to oxidize NO in simulated flue gas at 100-500°C. The effects of the H2O2 evaporation conditions, gas temperature, initial NO concentration, H2O2 concentration, and H2O2:NO molar ratio on the oxidation efficiency of NO were investigated. The reason for the narrow NO oxidation temperature range near 500°C was determined. The NO oxidation products were analyzed. The removal of NOx using NaOH solution at a moderate oxidation ratio was studied. It was proven that rapid evaporation of the H2O2 solution was critical to increase the NO oxidation efficiency and broaden the oxidation temperature range. the NO oxidation efficiency was above 50% at 300-500°C by contacting the outlet of the syringe needle and the stainless-steel gas pipe together to spread H2O2 solution into a thin film on the surface of the stainless-steel gas pipe, which greatly accelerated the evaporation of H2O2. The NO oxidation efficiency and the NO oxidation rate increased with increasing initial NO concentration. This method was more effective for the oxidation of NO at high concentrations. H2O2 solution with a concentration higher than 15% was more efficient in oxidizing NO. High temperatures decreased the influence of the H2O2 concentration on the NO oxidation efficiency. The oxidation efficiency of NO increased with an increase in the H2O2:NO molar ratio, but the ratio of H2O2 to oxidized NO decreased. Over 80% of the NO oxidation product was NO2, which indicated that the oxidation ratio of NO did not need to be very high. An 86.7% NO removal efficiency was obtained at an oxidation ratio of only 53.8% when combined with alkali absorption.

Optimization of NO oxidation by H2O2 thermal decomposition at moderate temperatures

PubMed Central

Wang, Zhong-hua; Gao, Xing-cun; Liu, Cheng-hao; Qi, Han-bing

2018-01-01

H2O2 was adopted to oxidize NO in simulated flue gas at 100–500°C. The effects of the H2O2 evaporation conditions, gas temperature, initial NO concentration, H2O2 concentration, and H2O2:NO molar ratio on the oxidation efficiency of NO were investigated. The reason for the narrow NO oxidation temperature range near 500°C was determined. The NO oxidation products were analyzed. The removal of NOx using NaOH solution at a moderate oxidation ratio was studied. It was proven that rapid evaporation of the H2O2 solution was critical to increase the NO oxidation efficiency and broaden the oxidation temperature range. the NO oxidation efficiency was above 50% at 300–500°C by contacting the outlet of the syringe needle and the stainless-steel gas pipe together to spread H2O2 solution into a thin film on the surface of the stainless-steel gas pipe, which greatly accelerated the evaporation of H2O2. The NO oxidation efficiency and the NO oxidation rate increased with increasing initial NO concentration. This method was more effective for the oxidation of NO at high concentrations. H2O2 solution with a concentration higher than 15% was more efficient in oxidizing NO. High temperatures decreased the influence of the H2O2 concentration on the NO oxidation efficiency. The oxidation efficiency of NO increased with an increase in the H2O2:NO molar ratio, but the ratio of H2O2 to oxidized NO decreased. Over 80% of the NO oxidation product was NO2, which indicated that the oxidation ratio of NO did not need to be very high. An 86.7% NO removal efficiency was obtained at an oxidation ratio of only 53.8% when combined with alkali absorption. PMID:29668672

Temperature dependence of surface tension of molten iron under reducing gas atmosphere

NASA Astrophysics Data System (ADS)

Ozawa, S.; Takahashi, S.; Fukuyama, H.; Watanabe, M.

2011-12-01

Surface tension of molten iron was measured under Ar-He-5vol.%H2 gas by oscillating droplet method using electromagnetic levitation furnace in consideration of the temperature dependence of oxygen partial pressure, Po2, of the gas. For comparison, the measurement was carried under Ar-He atmosphere to fix the Po2 of the inlet gas at 10-2Pa. The surface tension was successfully measured over a wide temperature range of about 780K including undercooling condition. When Po2 is fixed at 10-2 Pa, the surface tension increased and then decreased with increasing temperature like a boomerang shape. When the measurement was carried out under the H2-containing gas atmosphere, the temperature dependence of the surface tension shows unique kink at around 1810K instead of liner relationship due to competition between the temperature dependence of the Po2 and that of the equilibrium constant of oxygen adsorption reaction. The relationship between the calculated lnKad with respect to inverse temperature using Szyszkowski model was different between the atmospheric gases.

Low LET radiolysis escape yields for reducing radicals and H2 in pressurized high temperature water

NASA Astrophysics Data System (ADS)

Sterniczuk, Marcin; Yakabuskie, Pamela A.; Wren, J. Clara; Jacob, Jasmine A.; Bartels, David M.

2016-04-01

Low Linear Energy Transfer (LET) radiolysis escape yields (G values) are reported for the sum (G(radH)+G(e-)aq) and for G(H2) in subcritical water up to 350 °C. The scavenger system 1-10 mM acetate/0.001 M hydroxide/0.00048 M N2O was used with simultaneous mass spectroscopic detection of H2 and N2 product. Temperature-dependent measurements were carried out with 2.5 MeV electrons from a van de Graaff accelerator, while room temperature calibration measurements were done with a 60Co gamma source. The concentrations and dose range were carefully chosen so that initial spur chemistry is not perturbed and the N2 product yield corresponds to those reducing radicals that escape recombination in pure water. In comparison with a recent review recommendation of Elliot and Bartels (AECL report 153-127160-450-001, 2009), the measured reducing radical yield is seven percent smaller at room temperature but in fairly good agreement above 150 °C. The H2 escape yield is in good agreement throughout the temperature range with several previous studies that used much larger radical scavenging rates. Previous analysis of earlier high temperature measurements of Gesc(radOH) is shown to be flawed, although the actual G values may be nearly correct. The methodology used in the present report greatly reduces the range of possible error and puts the high temperature escape yields for low-LET radiation on a much firmer quantitative foundation than was previously available.

Temperature dependence of lower critical field of YBCO superconductor

NASA Astrophysics Data System (ADS)

Rani, Poonam; Hafiz, A. K.; Awana, V. P. S.

2018-05-01

We report the detailed study of the temperature dependence of the lower critical field (Hc1) of the YBa2Cu3O7 superconductor by magnetization measurements. The curve shows the multiband gap behavior of the sample. It is found that the sample is not a single BCS type superconductor. Hc1 is measured as the point at which the curve deviates from a Meissner-like linear M(H) curve to a nonlinear path. The Hc1 for YBCO at different temperatures from 10K to 85K has been determined by magnetization measurements M(H) with applied field parallel to the c-axis. The sample phase purity has been confirmed by Rietveld fitted X-ray diffraction data. The amplitude (1-17Oe) dependent AC susceptibility confirms the granular nature of superconducting compound. Using Bean model we calculated the temperature dependency of inter-grain critical current density and Jc(0) is found as 699.14kAcm-2.

Solvent-Dependent Delamination, Restacking, and Ferroelectric Behavior in a New Charge-Separated Layered Compound: [NH4 ][Ag3 (C9 H5 NO4 S)2 (C13 H14 N2 )2 ]⋅8 H2 O.

PubMed

Sushrutha, Sringeri Ramesh; Mohana, Shivanna; Pal, Somnath; Natarajan, Srinivasan

2017-01-03

A new anionic coordination polymer, [NH 4 ][Ag 3 (C 9 H 5 NO 4 S) 2 (C 13 H 14 N 2 ) 2 ]⋅8 H 2 O, with a two-dimensional structure, has been synthesized by a reaction between silver nitrate, 8-hydroxyquinoline-5-sulfonic acid (HQS), and 4,4'-trimethylene dipyridine (TMDP). The compound stabilizes in a noncentrosymmetric space group, and the lattice water molecules and the charge-compensating [NH 4 ] + group occupy the inter-lamellar spaces. The lattice water molecules can be fully removed and reinserted, which is accompanied by a crystalline-amorphous-crystalline transformation. This transformation resembles the collapse/delamination and restacking of the layers. To the best of our knowledge, this is the first observation of delamination and restacking in an inorganic coordination polymer that contains silver. The presence of a natural dipole (the anionic framework and cationic ammonium ions) along with the noncentrosymmetric space group gives rise to the room-temperature ferroelectric behavior of the compound. The ferroelectric behavior is also water-dependent and exhibits a ferroelectric-paraelectric transformation. The temperature-dependent dielectric measurements indicate that the ferroelectric/ paraelectric transformation occurs at 320 K. This transformation has also been investigated by using in-situ IR spectroscopy and PXRD studies. The second-harmonic generation (SHG) study indicated values that are comparable to some of the known SHG solids, such as potassium dihydrogen phosphate (KDP) and urea. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Communication: H-atom reactivity as a function of temperature in solid parahydrogen: The H + N2O reaction

NASA Astrophysics Data System (ADS)

Mutunga, Fredrick M.; Follett, Shelby E.; Anderson, David T.

2013-10-01

We present low temperature kinetic measurements for the H + N2O association reaction in solid parahydrogen (pH2) at liquid helium temperatures (1-5 K). We synthesize 15N218O doped pH2 solids via rapid vapor deposition onto an optical substrate attached to the cold tip of a liquid helium bath cryostat. We then subject the solids to short duration 193 nm irradiations to generate H-atoms produced as byproducts of the in situ N2O photodissociation, and monitor the subsequent reaction kinetics using rapid scan FTIR. For reactions initiated in solid pH2 at 4.3 K we observe little to no reaction; however, if we then slowly reduce the temperature of the solid we observe an abrupt onset to the H + N2O → cis-HNNO reaction at temperatures below 2.4 K. This abrupt change in the reaction kinetics is fully reversible as the temperature of the solid pH2 is repeatedly cycled. We speculate that the observed non-Arrhenius behavior (negative activation energy) is related to the stability of the pre-reactive complex between the H-atom and 15N218O reagents.

Vacuum ultraviolet photolysis of hydrogenated amorphous carbons. III. Diffusion of photo-produced H2 as a function of temperature

NASA Astrophysics Data System (ADS)

Martín-Doménech, R.; Dartois, E.; Muñoz Caro, G. M.

2016-06-01

Context. Hydrogenated amorphous carbon (a-C:H) has been proposed as one of the carbonaceous solids detected in the interstellar medium. Energetic processing of the a-C:H particles leads to the dissociation of the C-H bonds and the formation of hydrogen molecules and small hydrocarbons. Photo-produced H2 molecules in the bulk of the dust particles can diffuse out to the gas phase and contribute to the total H2 abundance. Aims: We have simulated this process in the laboratory with plasma-produced a-C:H and a-C:D analogs under astrophysically relevant conditions to investigate the dependence of the diffusion as a function of temperature. Methods: Experimental simulations were performed in a high-vacuum chamber, with complementary experiments carried out in an ultra-high-vacuum chamber. Plasma-produced a-C:H and a-C:D analogs were UV-irradiated using a microwave-discharged hydrogen flow lamp. Molecules diffusing to the gas-phase were detected by a quadrupole mass spectrometer, providing a measurement of the outgoing H2 or D2 flux. By comparing the experimental measurements with the expected flux from a one-dimensional diffusion model, a diffusion coefficient D could be derived for experiments carried out at different temperatures. Results: Dependence on the diffusion coefficient D with the temperature followed an Arrhenius-type equation. The activation energy for the diffusion process was estimated (ED(H2) = 1660 ± 110 K, ED(D2) = 2090 ± 90 K), as well as the pre-exponential factor (D0(H2) = 0.0007 cm2 s-1, D0(D2) = 0.0045 cm2 s-1). Conclusions: The strong decrease of the diffusion coefficient at low dust particle temperatures exponentially increases the diffusion times in astrophysical environments. Therefore, transient dust heating by cosmic rays needs to be invoked for the release of the photo-produced H2 molecules in cold photon-dominated regions, where destruction of the aliphatic component in hydrogenated amorphous carbons most probably takes place.

Rate constant for the H˙ + H2O → ˙OH + H2 reaction at elevated temperatures measured by pulse radiolysis.

PubMed

Muroya, Y; Yamashita, S; Lertnaisat, P; Sanguanmith, S; Meesungnoen, J; Jay-Gerin, J-P; Katsumura, Y

2017-11-22

Maintaining the structural integrity of materials in nuclear power plants is an essential issue associated with safe operation. Hydrogen (H 2 ) addition or injection to coolants is a powerful technique that has been widely applied such that the reducing conditions in the coolant water avoid corrosion and stress corrosion cracking (SCC). Because the radiation-induced reaction of ˙OH + H 2 → H˙ + H 2 O plays a crucial role in these systems, the rate constant has been measured at operation temperatures of the reactors (285-300 °C) by pulse radiolysis, generating sufficient data for analysis. The reverse reaction H˙ + H 2 O → ˙OH + H 2 is negligibly slow at ambient temperature; however, it accelerates considerably quickly at elevated temperatures. Although the reverse reaction reduces the effectiveness of H 2 addition, reliable rate constants have not yet been measured. In this study, the rate constants have been determined in a temperature range of 250-350 °C by pulse radiolysis in an aqueous I - solution.

Concurrent separation of CO2 and H2O from air by a temperature-vacuum swing adsorption/desorption cycle.

PubMed

Wurzbacher, Jan Andre; Gebald, Christoph; Piatkowski, Nicolas; Steinfeld, Aldo

2012-08-21

A temperature-vacuum swing (TVS) cyclic process is applied to an amine-functionalized nanofibrilated cellulose sorbent to concurrently extract CO(2) and water vapor from ambient air. The promoting effect of the relative humidity on the CO(2) capture capacity and on the amount of coadsorbed water is quantified. The measured specific CO(2) capacities range from 0.32 to 0.65 mmol/g, and the corresponding specific H(2)O capacities range from 0.87 to 4.76 mmol/g for adsorption temperatures varying between 10 and 30 °C and relative humidities varying between 20 and 80%. Desorption of CO(2) is achieved at 95 °C and 50 mbar(abs) without dilution by a purge gas, yielding a purity exceeding 94.4%. Sorbent stability and a closed mass balance for both H(2)O and CO(2) are demonstrated for ten consecutive adsorption-desorption cycles. The specific energy requirements of the TVS process based on the measured H(2)O and CO(2) capacities are estimated to be 12.5 kJ/mol(CO2) of mechanical (pumping) work and between 493 and 640 kJ/mol(CO2) of heat at below 100 °C, depending on the air relative humidity. For a targeted CO(2) capacity of 2 mmol/g, the heat requirement would be reduced to between 272 and 530 kJ/mol(CO2), depending strongly on the amount of coadsorbed water.

The time dependent growth of H2O-H2SO4 aerosols by heteromolecular condensation

NASA Technical Reports Server (NTRS)

Hamill, P.

1975-01-01

A theory for the time-dependent growth of solution droplets by heteromolecular condensation is presented. The theory is applied to the growth of H2O-H2SO4 aerosols for relative humidities less than 100 per cent. Growth curves (droplet radius as a function of time) for different values of relative humidity are evaluated.

Temperature dependence of the ClONO{sub 2} UV absorption spectrum

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

Burkholder, J.B.; Talukdar, R.K.; Ravishankara, A.R.

1994-04-01

The temperature dependence of the ClONO{sub 2} absorption spectrum has been measured between 220 and 298 K and between 195 and 430 nm using a diode array spectrometer. The absorption cross sections were determined using both: (1) absolute pressure measurements at 296 K and (2) measurements at various temperatures relative to 296 K using a dual absorption cell arrangement. The temperature dependence of the ClONO{sub 2} absorption spectrum shows very broad structure. The amplitude of the temperature dependence relative to that at 296 K is weak at short wavelengths, < 2% at 215 nm and 220 K, but significant atmore » the wavelengths important in the stratosphere, {approximately} 30% at 325 nm and 220 K. The authors ClONO{sub 2} absorption cross section data are in good general agreement with the previous measurements of Molina and Molina.« less

Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature

NASA Astrophysics Data System (ADS)

Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

2016-01-01

Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C-O-H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred.

Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature

PubMed Central

Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

2016-01-01

Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C–O–H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred. PMID:26813580

Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature.

PubMed

Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

2016-01-27

Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C-O-H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred.

H2O2 Synthesis Induced by Irradiation of H2O with Energetic H(+) and Ar(+) Ions at Various Temperatures

NASA Technical Reports Server (NTRS)

Baragiola, R. A.; Loeffler, M. J.; Raut, U.; Vidal, R. A.; Carlson, R. W.

2004-01-01

The detection of H2O2 on Jupiter's icy satellite Europa by the Galileo NIMS instrument presented a strong evidence for the importance of radiation effects on icy surfaces. A few experiments have investigated whether solar flux of protons incident on Europa ice could cause a significant if any H2O2 production. These published results differ as to whether H2O2 can be formed by ions impacting water at temperatures near 80 K, which are appropriate to Europa. This discrepancy may be a result of the use of different incident ion energies, different vacuum conditions, or different ways of processing the data. The latter possibility comes about from the difficulty of identifying the 3.5 m peroxide OH band on the long wavelength wing of the much stronger water 3.1 m band. The problem is aggravated by using straight line baselines to represent the water OH band with a curvature, in the region of the peroxide band, that increases with temperature. To overcome this problem, we use polynomial baselines that provide good fits to the water band and its derivative.

In vitro selection of high temperature Zn(2+)-dependent DNAzymes.

PubMed

Nelson, Kevin E; Bruesehoff, Peter J; Lu, Yi

2005-08-01

In vitro selection of Zn(2+)-dependent RNA-cleaving DNAzymes with activity at 90 degrees C has yielded a diverse spool of selected sequences. The RNA cleavage efficiency was found in all cases to be specific for Zn(2+) over Pb(2+), Ca(2+), Cd(2+), Co(2+), Hg(2+), and Mg(2+). The Zn(2+)-dependent activity assay of the most active sequence showed that the DNAzyme possesses an apparent Zn(2+)-binding dissociation constant of 234 muM and that its activity increases with increasing temperatures from 50-90 degrees C. A fit of the Arrhenius plot data gave E(a) = 15.3 kcal mol(-1). Surprisingly, the selected Zn(2+)-dependent DNAzymes showed only a modest (approximately 3-fold) activity enhancement over the background rate of cleavage of random sequences containing a single embedded ribonucleotide within an otherwise DNA oligonucleotide. The result is attributable to the ability of DNA to sustain cleavage activity at high temperature with minimal secondary structure when Zn(2+) is present. Since this effect is highly specific for Zn(2+), this metal ion may play a special role in molecular evolution of nucleic acids at high temperature.

A novel technique for measurement of thermal rate constants and temperature dependences of dissociative recombination: CO{sub 2}{sup +}, CF{sub 3}{sup +}, N{sub 2}O{sup +}, C{sub 7}H{sub 8}{sup +}, C{sub 7}H{sub 7}{sup +}, C{sub 6}H{sub 6}{sup +}, C{sub 6}H{sub 5}{sup +}, C{sub 5}H{sub 6}{sup +}, C{sub 4}H{sub 4}{sup +}, and C{sub 3}H{sub 3}{sup +}

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

Fournier, Joseph A.; Shuman, Nicholas S.; Melko, Joshua J.

A novel technique using a flowing afterglow-Langmuir probe apparatus for measurement of temperature dependences of rate constants for dissociative recombination (DR) is presented. Low ({approx}10{sup 11} cm{sup -3}) concentrations of a neutral precursor are added to a noble gas/electron afterglow plasma thermalized at 300-500 K. Charge exchange yields one or many cation species, each of which may undergo DR. Relative ion concentrations are monitored at a fixed reaction time while the initial plasma density is varied between 10{sup 9} and 10{sup 10} cm{sup -3}. Modeling of the decrease in concentration of each cation relative to the non-recombining noble gas cationmore » yields the rate constant for DR. The technique is applied to several species (O{sub 2}{sup +}, CO{sub 2}{sup +}, CF{sub 3}{sup +}, N{sub 2}O{sup +}) with previously determined 300 K values, showing excellent agreement. The measurements of those species are extended to 500 K, with good agreement to literature values where they exist. Measurements are also made for a range of C{sub n}H{sub m}{sup +} (C{sub 7}H{sub 7}{sup +}, C{sub 7}H{sub 8}{sup +}, C{sub 5}H{sub 6}{sup +}, C{sub 4}H{sub 4}{sup +}, C{sub 6}H{sub 5}{sup +}, C{sub 3}H{sub 3}{sup +}, and C{sub 6}H{sub 6}{sup +}) derived from benzene and toluene neutral precursors. C{sub n}H{sub m}{sup +} DR rate constants vary from 8-12 Multiplication-Sign 10{sup -7} cm{sup 3} s{sup -1} at 300 K with temperature dependences of approximately T{sup -0.7}. Where prior measurements exist these results are in agreement, with the exception of C{sub 3}H{sub 3}{sup +} where the present results disagree with a previously reported flat temperature dependence.« less

Temperature dependence of partial conductivities of the BaZr0.7Ce0.2Y0.1O3-δ proton conductor

NASA Astrophysics Data System (ADS)

Heras-Juaristi, Gemma; Pérez-Coll, Domingo; Mather, Glenn C.

2017-10-01

Partial conductivities are presented for BaZr0.7Ce0.2Y0.1O3-δ, an important proton conductor for protonic-ceramic fuel cells and membrane reactors. Atmospheric dependencies of impedance performed in humidified and dry O2, air, N2 and H2(10%)/N2(90%) in the temperature range 300-900 °C, supported by the modified emf method, confirm significant electron-hole and protonic contributions to transport. For very reducing and wet atmospheres, the conductivity is predominantly ionic, with a higher participation of protons with decreasing temperature and increasing water-vapour partial pressure (pH2O). From moderately reducing conditions of wet N2 to wet O2, however, the conductivity is considerably influenced by electron holes as revealed by a significant dependence of total conductivity on oxygen partial pressure (pO2). With higher pH2O, proton transport increases, with a concomitant decrease of holes and oxygen vacancies. However, the effect of pH2O is also influenced by temperature, with a greater protonic contribution at both lower temperature and pO2. Values of proton transport number tH ≈ 0.63 and electronic transport number th ≈ 0.37 are obtained at 600 °C for pH2O = 0.022 atm and pO2 = 0.2 atm, whereas tH ≈ 0.95 and th ≈ 0.05 for pO2 = 10-5 atm. A hydration enthalpy of -109 kJ mol-1 is obtained in the range 600-900 °C.

Temperature sensitivity on growth and/or replication of H1N1, H1N2 and H3N2 influenza A viruses isolated from pigs and birds in mammalian cells.

PubMed

Massin, Pascale; Kuntz-Simon, Gaëlle; Barbezange, Cyril; Deblanc, Céline; Oger, Aurélie; Marquet-Blouin, Estelle; Bougeard, Stéphanie; van der Werf, Sylvie; Jestin, Véronique

2010-05-19

Influenza A viruses have been isolated from a wide range of animal species, aquatic birds being the reservoir for their genetic diversity. Avian influenza viruses can be transmitted to humans, directly or indirectly through an intermediate host like pig. This study aimed to define in vitro conditions that could prove useful to evaluate the potential of influenza viruses to adapt to a different host. Growth of H1N1, H1N2 and H3N2 influenza viruses belonging to different lineages isolated from birds or pigs prior to 2005 was tested on MDCK or NPTr cell lines in the presence or absence of exogenous trypsin. Virus multiplication was compared at 33, 37 and 40 degrees C, the infection site temperatures in human, swine and avian hosts, respectively. Temperature sensitivity of PB2-, NP- and M-RNA replication was also tested by quantitative real-time PCR. Multiplication of avian viruses was cold-sensitive, whatever cell type. By contrast, temperature sensitivity of swine viruses was found to depend on the virus and the host cell: for an H1N1 swine isolate from 1982, multiplication was cold-sensitive on NPTr cells and undetectable at 40 degrees C. From genetic analyses, it appears that temperature sensitivity could involve other residues than PB2 residue 627 and could affect other steps of the replication cycle than replication. Copyright 2009 Elsevier B.V. All rights reserved.

Temperature influences neuronal activity and CO2/pH sensitivity of locus coeruleus neurons in the bullfrog, Lithobates catesbeianus.

PubMed

Santin, Joseph M; Watters, Kayla C; Putnam, Robert W; Hartzler, Lynn K

2013-12-15

The locus coeruleus (LC) is a chemoreceptive brain stem region in anuran amphibians and contains neurons sensitive to physiological changes in CO2/pH. The ventilatory and central sensitivity to CO2/pH is proportional to the temperature in amphibians, i.e., sensitivity increases with increasing temperature. We hypothesized that LC neurons from bullfrogs, Lithobates catesbeianus, would increase CO2/pH sensitivity with increasing temperature and decrease CO2/pH sensitivity with decreasing temperature. Further, we hypothesized that cooling would decrease, while warming would increase, normocapnic firing rates of LC neurons. To test these hypotheses, we used whole cell patch-clamp electrophysiology to measure firing rate, membrane potential (V(m)), and input resistance (R(in)) in LC neurons in brain stem slices from adult bullfrogs over a physiological range of temperatures during normocapnia and hypercapnia. We found that cooling reduced chemosensitive responses of LC neurons as temperature decreased until elimination of CO2/pH sensitivity at 10°C. Chemosensitive responses increased at elevated temperatures. Surprisingly, chemosensitive LC neurons increased normocapnic firing rate and underwent membrane depolarization when cooled and decreased normocapnic firing rate and underwent membrane hyperpolarization when warmed. These responses to temperature were not observed in nonchemosensitive LC neurons or neurons in a brain stem slice 500 μm rostral to the LC. Our results indicate that modulation of cellular chemosensitivity within the LC during temperature changes may influence temperature-dependent respiratory drive during acid-base disturbances in amphibians. Additionally, cold-activated/warm-inhibited LC neurons introduce paradoxical temperature sensitivity in respiratory control neurons of amphibians.

Marburg Virus Glycoprotein GP2: pH-Dependent Stability of the Ectodomain α-Helical Bundle†

PubMed Central

Harrison, Joseph S.; Koellhoffer, Jayne F.; Chandran, Kartik; Lai, Jonathan R.

2012-01-01

Marburg virus (MARV) and Ebola virus (EBOV) constitute the family Filoviridae of enveloped viruses (filoviruses) that cause severe hemorrhagic fever. Infection by MARV is required for fusion between the host cell and viral membranes, a process that is mediated by the two subunits of the envelope glycoprotein GP1 (surface subunit) and GP2 (transmembrane subunit). Upon viral attachment and uptake, it is believed that the MARV viral fusion machinery is triggered by host factors and environmental conditions found in the endosome. Next, conformational rearrangements in the GP2 ectodomain result in the formation of a highly stable six-helix bundle; this refolding event provides the energetic driving force for membrane fusion. Both GP1 and GP2 from EBOV have been extensively studied, but there is little information available for the MARV glycoproteins. Here we have expressed two variants of the MARV GP2 ectodomain in Escherichia coli and analyzed their biophysical properties. Circular dichroism indicates that the MARV GP2 ectodomain adopts an α-helical conformation, and one variant sediments as a trimer by equilibrium analytical ultracentrifugation. Denaturation studies indicate the α-helical structure is highly stable at pH 5.3 (unfolding energy, ΔGunf H2O, of 33.4 ± 2.5 kcal/mol and melting temperature, Tm, of 75.3 ± 2.1 °C for one variant). Furthermore, we found the α-helical stability to be strongly dependent on pH with higher stability under lower pH conditions (Tm values ranging from ~92 °C at pH 4.0 to ~38 °C at pH 8.0). Mutational analysis suggests two glutamic acid residues (E579 and E580) are partially responsible for this pH-dependent behavior. Based on these results, we hypothesize that pH-dependent folding stability of the MARV GP2 ectodomain provides a mechanism to control conformational preferences such that the six-helix bundle ‘post-fusion’ state is preferred under conditions of appropriately matured endosomes. PMID:22369502

High temperature chemical kinetic study of the H2-CO-CO2-NO reaction system

NASA Technical Reports Server (NTRS)

Jachimowski, C. J.

1975-01-01

An experimental study of the kinetics of the H2-CO-CO2-NO reaction system was made behind incident shock waves at temperatures of 2460 and 2950 K. The overall rate of the reaction was measured by monitoring radiation from the CO + O yields CO2 + h upoilon reaction. Correlation of these data with a detailed reaction mechanism showed that the high-temperature rate of the reaction N + OH yields NO + H can be described by the low-temperature (320 K) rate coefficient. Catalytic dissociation of molecular hydrogen was an important reaction under the tests conditions.

Modeling the pH and temperature dependence of aqueousphase hydroxyl radical reaction rate constants of organic micropollutants using QSPR approach.

PubMed

Gupta, Shikha; Basant, Nikita

2017-11-01

Designing of advanced oxidation process (AOP) requires knowledge of the aqueous phase hydroxyl radical ( ● OH) reactions rate constants (k OH ), which are strictly dependent upon the pH and temperature of the medium. In this study, pH- and temperature-dependent quantitative structure-property relationship (QSPR) models based on the decision tree boost (DTB) approach were developed for the prediction of k OH of diverse organic contaminants following the OECD guidelines. Experimental datasets (n = 958) pertaining to the k OH values of aqueous phase reactions at different pH (n = 470; 1.4 × 10 6 to 3.8 × 10 10  M -1  s -1 ) and temperature (n = 171; 1.0 × 10 7 to 2.6 × 10 10  M -1  s -1 ) were considered and molecular descriptors of the compounds were derived. The Sanderson scale electronegativity, topological polar surface area, number of double bonds, and halogen atoms in the molecule, in addition to the pH and temperature, were found to be the relevant predictors. The models were validated and their external predictivity was evaluated in terms of most stringent criteria parameters derived on the test data. High values of the coefficient of determination (R 2 ) and small root mean squared error (RMSE) in respective training (> 0.972, ≤ 0.12) and test (≥ 0.936, ≤ 0.16) sets indicated high generalization and predictivity of the developed QSPR model. Other statistical parameters derived from the training and test data also supported the robustness of the models and their suitability for screening new chemicals within the defined chemical space. The developed QSPR models provide a valuable tool for predicting the ● OH reaction rate constants of emerging new water contaminants for their susceptibility to AOPs.

Hydrogen-atom tunneling through a very high barrier; spontaneous thiol → thione conversion in thiourea isolated in low-temperature Ar, Ne, H2 and D2 matrices.

PubMed

Rostkowska, Hanna; Lapinski, Leszek; Nowak, Maciej J

2018-05-23

Spontaneous thiol → thione hydrogen-atom transfer has been investigated for molecules of thiourea trapped in Ar, Ne, normal-H2 (n-H2) and normal-D2 (n-D2) low-temperature matrices. The most stable thione isomer was the only form of the compound present in the matrices after their deposition. According to MP2/6-311++G(2d,p) calculations, the thiol tautomer should be higher in energy by 62.5 kJ mol-1. This less stable thiol form of the compound was photochemically generated in a thione → thiol process, occurring upon UV irradiation of the matrix. Subsequently, a very slow spontaneous conversion of the thiol tautomer into the thione form was observed for the molecules isolated in Ar, Ne, n-H2 and n-D2 matrices kept at 3.5 K and in the dark. Since the thiol → thione transformation in thiourea is a process involving the dissociation of a chemical bond, the barrier for this hydrogen-atom transfer is very high (104-181 kJ mol-1). Crossing such a high potential-energy barrier at a temperature as low as 3.5 K, is possible only by hydrogen-atom tunneling. The experimentally measured time constants of this tunneling process: 52 h (Ar), 76 h (Ne), 94 h (n-H2) and 94 h (n-D2), do not differ much from one another. Hence, the dependence of the tunneling rate on the matrix environment is not drastic. The progress of the thiol → thione conversion was also monitored for Ar matrices at different temperature: 3.5 K, 9 K and 15 K. For this temperature range, the experiments revealed no detectable temperature dependence of the rate of the tunneling process.

Temperature-Dependent Friction and Wear Behavior of PTFE and MoS 2

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

Babuska, T. F.; Pitenis, A. A.; Jones, M. R.

2016-06-16

We present an investigation of the temperature-dependent friction behavior of PTFE, MoS 2, and PTFE-on- MoS 2. Friction behavior was measured while continuously varying contact temperature in the range -150 to 175°C while sliding in dry nitrogen, as well as for self-mated PTFE immersed in liquid nitrogen. These results contrast with previous reports of monotonic inverse temperature dependent friction behavior, as well as reported high-friction transitions and plateaus at temperatures below about -20°C that were not observed, providing new insights about the molecular mechanisms of macro-scale friction. The temperature-dependent friction behavior characteristic of self-mated PTFE was found also on themore » PTFE-on-MoS 2 sliding contact, suggesting that PTFE friction was defined by sub-surface deformation mechanisms and internal friction even when sliding against a lamellar lubricant with extremely low friction coefficient (μ ~ 0.02). The various relaxation temperatures of PTFE were found in the temperature-dependent friction behavior, showing excellent agreement with reported values acquired using torsional techniques measuring internal friction. Additionally, hysteresis in friction behavior suggests an increase in near-surface crystallinity at upon exceeding the high temperature relaxation, T α~ 116°C.« less

The solubility of gold in H 2 O-H 2 S vapour at elevated temperature and pressure

NASA Astrophysics Data System (ADS)

Zezin, Denis Yu.; Migdisov, Artashes A.; Williams-Jones, Anthony E.

2011-09-01

This experimental study sheds light on the complexation of gold in reduced sulphur-bearing vapour, specifically, in H 2O-H 2S gas mixtures. The solubility of gold was determined in experiments at temperatures of 300, 350 and 365 °C and reached 2.2, 6.6 and 6.3 μg/kg, respectively. The density of the vapour varied from 0.02 to 0.22 g/cm 3, the mole fraction of H 2S varied from 0.03 to 0.96, and the pressure in the cell reached 263 bar. Statistically significant correlations of the amount of gold dissolved in the fluid with the fugacity of H 2O and H 2S permit the experimental data to be fitted to a solvation/hydration model. According to this model, the solubility of gold in H 2O-H 2S gas mixtures is controlled by the formation of sulphide or bisulphide species solvated by H 2S or H 2O molecules. Formation of gold sulphide species is favoured statistically over gold bisulphide species and thus the gold is interpreted to dissolve according to reactions of the form: Au(s)+(n+1)HS(g)=AuS·(HS)n(g)+H(g) Au(s)+HS(g)+mHO(g)=AuS·(HO)m(g)+H(g) Equilibrium constants for Reaction (A1) and the corresponding solvation numbers ( K A1 and n) were evaluated from the study of Zezin et al. (2007). The equilibrium constants as well as the hydration numbers for Reaction (A2) ( K A2 and m) were adjusted simultaneously by a custom-designed optimization algorithm and were tested statistically. The resulting values of log K A2 and m are -15.3 and 2.3 at 300 and 350 °C and -15.1 and 2.2 at 365 °C, respectively. Using the calculated stoichiometry and stability of Reactions (A1) and (A2), it is now possible to quantitatively evaluate the contribution of reduced sulphur species to the transport of gold in aqueous vapour at temperatures up to 365 °C. This information will find application in modelling gold ore-forming processes in vapour-bearing magmatic hydrothermal systems, notably those of epithermal environments.

Quantitative Analysis of Temperature Dependence of Raman shift of monolayer WS2

NASA Astrophysics Data System (ADS)

Huang, Xiaoting; Gao, Yang; Yang, Tianqi; Ren, Wencai; Cheng, Hui-Ming; Lai, Tianshu

2016-08-01

We report the temperature-dependent evolution of Raman spectra of monolayer WS2 directly CVD-grown on a gold foil and then transferred onto quartz substrates over a wide temperature range from 84 to 543 K. The nonlinear temperature dependence of Raman shifts for both and A1g modes has been observed. The first-order temperature coefficients of Raman shifts are obtained to be -0.0093 (cm-1/K) and -0.0122 (cm-1/K) for and A1g peaks, respectively. A physical model, including thermal expansion and three- and four-phonon anharmonic effects, is used quantitatively to analyze the observed nonlinear temperature dependence. Thermal expansion coefficient (TEC) of monolayer WS2 is extracted from the experimental data for the first time. It is found that thermal expansion coefficient of out-plane mode is larger than one of in-plane mode, and TECs of and A1g modes are temperature-dependent weakly and strongly, respectively. It is also found that the nonlinear temperature dependence of Raman shift of mode mainly originates from the anharmonic effect of three-phonon process, whereas one of A1g mode is mainly contributed by thermal expansion effect in high temperature region, revealing that thermal expansion effect cannot be ignored.

H2O absorption spectroscopy for determination of temperature and H2O mole fraction in high-temperature particle synthesis systems.

PubMed

Torek, Paul V; Hall, David L; Miller, Tiffany A; Wooldridge, Margaret S

2002-04-20

Water absorption spectroscopy has been successfully demonstrated as a sensitive and accurate means for in situ determination of temperature and H2O mole fraction in silica (SiO2) particle-forming flames. Frequency modulation of near-infrared emission from a semiconductor diode laser was used to obtain multiple line-shape profiles of H2O rovibrational (v1 + v3) transitions in the 7170-7185-cm(-1) region. Temperature was determined by the relative peak height ratios, and XH2O was determined by use of the line-shape profiles. Measurements were made in the multiphase regions of silane/hydrogen/oxygen/ argon flames to verify the applicability of the diagnostic approach to combustion synthesis systems with high particle loadings. A range of equivalence ratios was studied (phi = 0.47 - 2.15). The results were compared with flames where no silane was present and with adiabatic equilibrium calculations. The spectroscopic results for temperature were in good agreement with thermocouple measurements, and the qualitative trends as a function of the equivalence ratio were in good agreement with the equilibrium predictions. The determinations for water mole fraction were in good agreement with theoretical predictions but were sensitive to the spectroscopic model parameters used to describe collisional broadening. Water absorption spectroscopy has substantial potential as a valuable and practical technology for both research and production combustion synthesis facilities.

Temperature- and Length-Dependent Energetics of Formation for Polyalanine Helices in Water: Assignment of wAla(n,T) and Temperature-Dependent CD Ellipticity Standards

PubMed Central

Job, Gabriel E.; Kennedy, Robert J.; Heitmann, Björn; Miller, Justin S.; Walker, Sharon M.; Kemp*, Daniel S.

2006-01-01

Length-dependent helical propensities wAla(n,T) at T = 10, 25, and 60 °C are assigned from t/c values and NMR 13C chemical shifts for series 1 peptides TrpLysmInp2tLeu–AlantLeuInp2LysmNH2, n = 15, 19, and 25, m = 5, in water. Van’t Hoff analysis of wAla(n,T) show that α-helix formation is primarily enthalpy-driven. For series 2 peptides Ac–Trp Lys5Inp2tLeu–βAspHel–Alan–beta–tLeuInp2Lys5NH2, n = 12 and 22, which contain exceptionally helical Alan cores, protection factor-derived fractional helicities FH are assigned in the range 10–30 °C in water and used to calibrate temperature-dependent CD ellipticities [θ]λ,H,n,T. These are applied to CD data for series 1 peptides, 12 ≤ n ≤ 45, to confirm the wAla(n,T) assignments at T = 25 and 60 °C. The [θ]λ,H,n,T are temperature dependent within the wavelength region, 222 ± 12 nm, and yield a temperature correction for calculation of FH from experimental values of [θ]222,n,T,Exp. PMID:16787087

Asparagine deamidation dependence on buffer type, pH, and temperature.

PubMed

Pace, Amanda L; Wong, Rita L; Zhang, Yonghua Taylor; Kao, Yung-Hsiang; Wang, Y John

2013-06-01

The deamidation of asparagine into aspartate and isoaspartate moieties is a major pathway for the chemical degradation of monoclonal antibodies (mAbs). It can affect the shelf life of a therapeutic antibody that is not formulated or stored appropriately. A new approach to detect deamidation using ion exchange chromatography was developed that separates papain-digested mAbs into Fc and Fab fragments. From this, deamidation rates of each fragment can be calculated. To generate kinetic parameters useful in setting shelf life, buffers prepared at room temperature and then placed at the appropriate stability temperatures. Solution pH was not adjusted to the same at different temperatures. Deamidation rate at 40°C was faster in acidic buffers than in basic buffers. However, this trend is reversed at 5°C, attributed to the change in hydroxide ion concentration influenced by buffer and temperature. The apparent activation energy was higher for rates generated in an acidic buffer than in a basic buffer. The rate-pH profile for mAb1 can be deconvoluted to Fc and Fab. The Fc deamidation showed a V-shaped profile: deamidation of PENNY peptide is responsible for the rate at high-pH, whereas deamidation of a new site, Asn323, may be responsible for the rate at low-pH. The profile for Fab is a straight line without curvature. Copyright © 2013 Wiley Periodicals, Inc.

Temperature dependence of luminescence behavior in Er3+-doped BaY2F8 single crystal

NASA Astrophysics Data System (ADS)

Wang, Shuai; Ruan, Yongfeng; Tsuboi, Taiju; Tong, Hongshuang; Wang, Youfa; Zhang, Shouchao

2013-12-01

BaY2F8 single crystals doped with Er3+ ions have been grown by the temperature gradient method. The absorption, excitation and emission spectra for Er3+-doped BaY2F8 crystals were measured at room temperature (297 K) and 12 K. The effect of temperature on the luminescence intensity and effective bandwidth was investigated in the range of 12-297 K. The temperature dependence of the fluorescence intensity ratio (FIR) for the 522 nm emission (2H11/2→4I15/2 transition) and the 552 nm emission (4S3/2→4I15/2 transition) was also studied in the range of 12-297 K. Based on the fitting FIR curve, the value of the constant term B (2.25) was obtained. The fitting FIR curve and FIR equation may have a potential application in the temperature measurement. In addition, the up-conversion spectrum at room temperature was recorded under excitation of 980 nm and the up-conversion mechanism was analyzed in detail.

Ab initio studies on Al(+)(H(2)O)(n), HAlOH(+)(H(2)O)(n-1), and the size-dependent H(2) elimination reaction.

PubMed

Siu, Chi-Kit; Liu, Zhi-Feng; Tse, John S

2002-09-11

We report computational studies on Al(+)(H(2)O)(n), and HAlOH(+)(H(2)O)(n-1), n = 6-14, by the density functional theory based ab initio molecular dynamics method, employing a planewave basis set with pseudopotentials, and also by conventional methods with Gaussian basis sets. The mechanism for the intracluster H(2) elimination reaction is explored. First, a new size-dependent insertion reaction for the transformation of Al(+)(H(2)O)(n), into HAlOH(+)(H(2)O)(n-1) is discovered for n > or = 8. This is because of the presence of a fairly stable six-water-ring structure in Al(+)(H(2)O)(n) with 12 members, including the Al(+). This structure promotes acidic dissociation and, for n > or = 8, leads to the insertion reaction. Gaussian based BPW91 and MP2 calculations with 6-31G* and 6-31G** basis sets confirmed the existence of such structures and located the transition structures for the insertion reaction. The calculated transition barrier is 10.0 kcal/mol for n = 9 and 7.1 kcal/mol for n = 8 at the MP2/6-31G** level, with zero-point energy corrections. Second, the experimentally observed size-dependent H(2) elimination reaction is related to the conformation of HAlOH(+)(H(2)O)(n-1), instead of Al(+)(H(2)O)(n). As n increases from 6 to 14, the structure of the HAlOH(+)(H(2)O)(n-1) cluster changes into a caged structure, with the Al-H bond buried inside, and protons produced in acidic dissociation could then travel through the H(2)O network to the vicinity of the Al-H bond and react with the hydride H to produce H(2). The structural transformation is completed at n = 13, coincident approximately with the onset of the H(2) elimination reaction. From constrained ab initio MD simulations, we estimated the free energy barrier for the H(2) elimination reaction to be 0.7 eV (16 kcal/mol) at n = 13, 1.5 eV (35 kcal/mol) at n = 12, and 4.5 eV (100 kcal/mol) at n = 8. The existence of transition structures for the H(2) elimination has also been verified by ab initio calculations

Air-Broadening of H2O as a Function of Temperature: 696 - 2163 cm(exp -1)

NASA Technical Reports Server (NTRS)

Toth, R. A.; Brown, L. R.; Smith, M. A. H.; Devi, V. Malathy; Benner, D. Chris; Dulick, M.

2006-01-01

The temperature dependence of air-broadened halfwidths are reported for some 500 transitions in the (000)-(000) and (010)-(000) bands of H2(16)O using gas sample temperatures ranging from 241 to 388 K. These observations were obtained from infrared laboratory spectra recorded at 0.006 to 0.011 cm(exp-1) resolution with the McMath-Pierce Fourier transform spectrometer located at Kitt Peak. The experimental values of the temperature dependence exponents, eta, were grouped into eight subsets and fitted to empirical functions in a semi-global procedure. Overall, the values of eta were found to decrease with increasing rotational quantum number J. The number of measurements (over 2200) and transitions (586) involved exceeds by a large margin that of any other comparable reported study.

Temperature dependence of piezoelectric properties for textured SBN ceramics.

PubMed

Kimura, Masahiko; Ogawa, Hirozumi; Kuroda, Daisuke; Sawada, Takuya; Higuchi, Yukio; Takagi, Hiroshi; Sakabe, Yukio

2007-12-01

Temperature dependences of piezoelectric properties were studied for h001i textured ceramics of bismuth layer-structured ferroelectrics, SrBi(2)Nb(2)O(9) (SBN). The textured ceramics with varied orientation degrees were fabricated by templated, grain-growth method, and the temperature dependences of resonance frequency were estimated. Excellent temperature stability of resonance frequency was obtained for the 76% textured ceramics. The resonance frequency of the 76% textured specimens varied almost linearly over a wide temperature range. Therefore, the variation was slight, even in a high temperature region above 150 degrees C. Temperature stability of a quartz crystal oscillator is generally higher than that of a ceramic resonator around room temperature. The variation of resonance frequency for the 76% textured SrBi(2)Nb(2)O(9) was larger than that of oscillation frequency for a typical quartz oscillator below 150 degrees C also in this study. However, the variation of the textured SrBi(2)Nb(2)O(9) was smaller than that of the quartz oscillator over a wide temperature range from -50 to 250 degrees C. Therefore, textured SrBi(2)Nb(2)O(9) ceramics is a major candidate material for the resonators used within a wide temperature range.

Temperature dependence of the dielectric response of anodized Al-Al2O3-metal capacitors

NASA Astrophysics Data System (ADS)

Hickmott, T. W.

2003-03-01

The temperature dependence of capacitance, CM, and conductance, GM, of Al-Al2O3-metal capacitors with Cu, Ag, and Au electrodes has been measured between 100 and 340 K at seven frequencies between 10 kHz and 1 MHz. Al2O3 films between 15 and 64 nm thick were formed by anodizing evaporated Al films in borate-glycol or borate-H2O electrolyte. The interface capacitance at the Al2O3-metal interface, CI, which is in series with the capacitance CD due to the Al2O3 dielectric, is determined from plots of 1/CM versus insulator thickness. CI is not fixed for a given metal-insulator interface but depends on the vacuum system used to deposit the metal electrode. CI is nearly temperature independent. When CI is taken into account the dielectric constant of Al2O3 determined from capacitance measurements is ˜8.3 at 295 K. The dielectric constant does not depend on anodizing electrolyte, insulator thickness, metal electrode, deposition conditions for the metal electrode or measurement frequency. By contrast, GM of Al-Al2O3-metal capacitors depends on both the deposition conditions of the metal and on the metal. For Al-Al2O3-Cu capacitors, GM is larger for capacitors with large values of 1/CI that result when Cu is evaporated in an oil-pumped vacuum system. For Al-Al2O3-Ag capacitors, GM does not depend on the Ag deposition conditions.

Photochemical Generation of H_{2}NCNX, H_{2}NNCX, H_{2}NC(NX) (x = O, s) in Low-Temperature Matrices

NASA Astrophysics Data System (ADS)

Voros, Tamas; Lajgut, Gyozo Gyorgy; Magyarfalvi, Gabor; Tarczay, Gyorgy

2017-06-01

The [NH_{2}, C, N, O] and the [NH_{2}, C, N, S] systems were investigated by quantum-chemical computations and matrix-isolation spectroscopic methods. The equilibrium structures of the isomers and their relative energies were determined by CCSD(T) method. This was followed by the computation of the harmonic and anharmonic vibrational wavenumbers, infrared intensities, relative Raman activities and UV excitation energies. These computed data were used to assist the identification of products obtained by UV laser photolysis of 3,4-diaminofurazan, 3,4-diaminothiadiazole and 1,2,4-thiadiazole-3,5-diamine in low-temperature Ar and Kr matrices. Experimentally, first the precursors were studied by matrix-isolation IR and UV spectroscopic methods. Based on these UV spectra, different wavelengths were selected for photolysis. The irradiations, carried out by a tunable UV laser-light source, resulted in the decomposition of the precursors, and in the appearance of new bands in the IR spectra. Some of these bands were assigned to cyanamide (H_{2}NCN) and its isomer, the carbodiimide molecule (HNCNH), generated from H_{2}NCN. By the analysis of the relative absorbance vs. photolysis time curves, the other bands were grouped to three different species both for the O- and the S-containing systems. In the case of the O-containing isomers, these bands were assigned to the H_{2}NNCO:H_{2}NCN, and H_{2}NCNO:H_{2}NCN complexes, and to the ring-structure H_{2}NC(NO) isomer. In a similar way, the complexes of H_{2}NNCS and H_{2}NCNS with the H_{2}NCN, and H_{2}NC(NS) were also identified. 1,2,4-thiadiazole-3,5-diamine was also investigated in similar way like the above mentioned precursors. The results of this study also support the identification of the new S-containing isomers. Except for H_{2}NNCO and H_{2}NCNS, these molecules were not identified previously. It is expected that at least some of these species, like the methyl isocyanate (CH_{3}CNO) isomer, are present and could be

Loss Process for the C2H5 Radical in the Atmospheres of Jupiter and Saturn: First Direct, Absolute Measurement of the Rate Constant for the Reaction H + C2H5 at Low Pressure and Temperature

NASA Astrophysics Data System (ADS)

Stief, L. J.; Pimentel, A. S.; Payne, W. A.; Nesbitt, F. L.; Cody, R. J.

2003-05-01

Photochemical models of the atmospheres of Jupiter and Saturn predict the reaction H + C2H5 to be the most important loss process for C2H5 in these atmospheres. In addition, the reaction channel H + C2H5 -> 2 CH3 is a significant source of the methyl radical. There are only two relatively modern studies of the H + C2H5 reaction, both of which depend on extensive modeling involving eight elementary reactions. The motivation for the present study is the lack of direct, absolute measurements of the rate constant for the H + C2H5 reaction at low pressures and temperatures appropriate for outer planet models. In the present experiments the reactants H and C2H5 are rapidly and simultaneously generated by reaction of F with appropriate mixtures of H2 and C2H6. Using the technique of discharge-flow with collision-free sampling to a mass spectrometer, we monitor the decay of C2H5 in excess H. In contrast to previous studies of this reaction, the primary H + C2H5 reaction is isolated and the radical decays only by reaction with H and by loss at the wall. Secondary reactions such as the self-reaction of C2H5 are negligible. At P = 1 Torr He we measure k (298K) = 1.13 x 10-10 cm3 molecule-1 s-1 and k (202K) = 1.18 x 10-10 cm3 molecule-1 s-1. Experiments at T = 155 K are in progress. The reaction is temperature independent as expected based on studies of other atom-radical reactions. Our result at T = 298 K lies between those of the two relatively modern but complex studies of this reaction. The present total rate constant data and planned product yield studies at low pressures and temperatures will then be available for use in future photochemical models of the atmospheres of the outer planets. The Planetary Atmospheres Program of NASA Headquarters is supporting this research.

Line intensities and temperature-dependent line broadening coefficients of Q-branch transitions in the v2 band of ammonia near 10.4 μm

NASA Astrophysics Data System (ADS)

Sur, Ritobrata; Spearrin, R. Mitchell; Peng, Wen Y.; Strand, Christopher L.; Jeffries, Jay B.; Enns, Gregory M.; Hanson, Ronald K.

2016-05-01

We report measured line intensities and temperature-dependent broadening coefficients of NH3 with Ar, N2, O2, CO2, H2O, and NH3 for nine sQ(J,K) transitions in the ν2 fundamental band in the frequency range 961.5-967.5 cm-1. This spectral region was chosen due to the strong NH3 absorption strength and lack of spectral interference from H2O and CO2 for laser-based sensing applications. Spectroscopic parameters were determined by multi-line fitting using Voigt lineshapes of absorption spectra measured with two quantum cascade lasers in thermodynamically-controlled optical cells. The temperature dependence of broadening was measured over a range of temperatures between 300 and 600 K. These measurements aid the development of mid-infrared NH3 sensors for a broad range of gas mixtures and at elevated temperatures.

Single diode laser sensor for wide-range H2O temperature measurements.

PubMed

Gharavi, Mohammadreza; Buckley, Steven G

2004-04-01

A single diode laser absorption sensor (near 1477 nm) useful for simultaneous temperature and H2O concentration measurements is developed. The diode laser tunes approximately 1.2 cm(-1) over three H2O absorption transitions in each measurement. The line strengths of the transitions are measured over a temperature range from 468 to 977 K, based on high-resolution absorption measurements in a heated static cell. The results indicate that the selected transitions are suitable for sensitive temperature measurements in atmospheric pressure combustion systems using absorption line ratios. Comparing the results with HITRAN 96 data, it appears that these transitions will be sensitive over a wide range of temperatures (450-2000 K), suggesting applicability for combustion measurements.

Oxygen Atom Exchange between H2O and Non-Heme Oxoiron(IV) Complexes: Ligand Dependence and Mechanism.

PubMed

Puri, Mayank; Company, Anna; Sabenya, Gerard; Costas, Miquel; Que, Lawrence

2016-06-20

Detailed studies of oxygen atom exchange (OAE) between H2(18)O and synthetic non-heme oxoiron(IV) complexes supported by tetradentate and pentadentate ligands provide evidence that they proceed by a common mechanism but within two different kinetic regimes, with OAE rates that span 2 orders of magnitude. The first kinetic regime involves initial reversible water association to the Fe(IV) complex, which is evidenced by OAE rates that are linearly dependent on [H2(18)O] and H2O/D2O KIEs of 1.6, while the second kinetic regime involves a subsequent rate determining proton-transfer step between the bound aqua and oxo ligands that is associated with saturation behavior with [H2(18)O] and much larger H2O/D2O KIEs of 5-6. [Fe(IV)(O)(TMC)(MeCN)](2+) (1) and [Fe(IV)(O)(MePy2TACN)](2+) (9) are examples of complexes that exhibit kinetic behavior in the first regime, while [Fe(IV)(O)(N4Py)](2+) (3), [Fe(IV)(O)(BnTPEN)](2+) (4), [Fe(IV)(O)(1Py-BnTPEN)](2+) (5), [Fe(IV)(O)(3Py-BnTPEN)](2+) (6), and [Fe(IV)(O)(Me2Py2TACN)](2+) (8) represent complexes that fall in the second kinetic regime. Interestingly, [Fe(IV)(O)(PyTACN)(MeCN)](2+) (7) exhibits a linear [H2(18)O] dependence below 0.6 M and saturation above 0.6 M. Analysis of the temperature dependence of the OAE rates shows that most of these complexes exhibit large and negative activation entropies, consistent with the proposed mechanism. One exception is complex 9, which has a near-zero activation entropy and is proposed to undergo ligand-arm dissociation during the RDS to accommodate H2(18)O binding. These results show that the observed OAE kinetic behavior is highly dependent on the nature of the supporting ligand and are of relevance to studies of non-heme oxoiron(IV) complexes in water or acetonitrile/water mixtures for applications in photocatalysis and water oxidation chemistry.

Rapid nondestructive spectrometric measurement of temperature-dependent gas-liquid solubility equilibria.

PubMed

Ma, Jian; Dasgupta, Purnendu K; Yang, Bingcheng

2011-02-01

Gas-liquid solubility equilibria (Henry's Law behavior) are of basic interest to many different areas. Temperature-dependent aqueous solubilities of various organic compounds are of fundamental importance in many branches of environmental science. In a number of situations, the gas/dissolved solute of interest has characteristic spectroscopic absorption that is distinct from that of the solvent. For such cases, we report facile nondestructive rapid measurement of the temperature-dependent Henry's law constant (K(H)) in a static sealed spectrometric cell. Combined with a special cell design, multiwavelength measurement permits a large range of K(H) to be spanned. It is possible to derive the K(H) values from the absorbance measured in the gas phase only, the liquid phase only (preferred), and both phases. Underlying principles are developed, and all three approaches are illustrated for a solute like acetone in water. A thermostatic spectrophotometer cell compartment, widely used and available, facilitates rapid temperature changes and allows rapid temperature-dependent equilibrium measurements. Applicability is shown for both acetone and methyl isobutyl ketone. Very little sample is required for the measurement; the K(H) for 4-hydroxynonenal, a marker for oxidative stress, is measured to be 56.9 ± 2.6 M/atm (n = 3) at 37.4 °C with 1 mg of the material available.

Surface Temperature Dependence of Hydrogen Ortho-Para Conversion on Amorphous Solid Water.

PubMed

Ueta, Hirokazu; Watanabe, Naoki; Hama, Tetsuya; Kouchi, Akira

2016-06-24

The surface temperature dependence of the ortho-to-para conversion of H_{2} on amorphous solid water is first reported. A combination of photostimulated desorption and resonance-enhanced multiphoton ionization techniques allowed us to sensitively probe the conversion on the surface of amorphous solid water at temperatures of 9.2-16 K. Within a narrow temperature window of 8 K, the conversion time steeply varied from ∼4.1×10^{3} to ∼6.4×10^{2}  s. The observed temperature dependence is discussed in the context of previously suggested models and the energy dissipation process. The two-phonon process most likely dominates the conversion rate at low temperatures.

Kinetics of the R + NO2 reactions (R = i-C3H7, n-C3H7, s-C4H9, and t-C4H9) in the temperature range 201-489 K.

PubMed

Rissanen, Matti P; Arppe, Suula L; Eskola, Arkke J; Tammi, Matti M; Timonen, Raimo S

2010-04-15

The bimolecular rate coefficients of four alkyl radical reactions with NO(2) have been measured in direct time-resolved experiments. Reactions were studied under pseudo-first-order conditions in a temperature-controlled tubular flow reactor coupled to a laser photolysis/photoionization mass spectrometer (LP-PIMS). The measured reaction rate coefficients are independent of helium bath gas pressure within the experimental ranges covered and exhibit negative temperature dependence. For i-C(3)H(7) + NO(2) and t-C(4)H(9) + NO(2) reactions, the dependence of ordinate (logarithm of reaction rate coefficients) on abscissa (1/T or log(T)) was nonlinear. The obtained results (in cm(3) s(-1)) can be expressed by the following equations: k(n-C(3)H(7) + NO(2)) = ((4.34 +/- 0.08) x 10(-11)) (T/300 K)(-0.14+/-0.08) (203-473 K, 1-7 Torr), k(i-C(3)H(7) + NO(2)) = ((3.66 +/- 2.54) x 10(-12)) exp(656 +/- 201 K/T)(T/300 K)(1.26+/-0.68) (220-489 K, 1-11 Torr), k(s-C(4)H(9) + NO(2)) = ((4.99 +/- 0.16) x 10(-11))(T/300 K)(-1.74+/-0.12) (241-485 K, 2 - 12 Torr) and k(t-C(4)H(9) + NO(2)) = ((8.64 +/- 4.61) x 10(-12)) exp(413 +/- 154 K/T)(T/300 K)(0.51+/-0.55) (201-480 K, 2-11 Torr), where the uncertainties shown refer only to the 1 standard deviations obtained from the fitting procedure. The estimated overall uncertainty in the determined bimolecular rate coefficients is about +/-20%.

Limits on a gravitational field dependence of the proton-electron mass ratio from H2 in white dwarf stars.

PubMed

Bagdonaite, J; Salumbides, E J; Preval, S P; Barstow, M A; Barrow, J D; Murphy, M T; Ubachs, W

2014-09-19

Spectra of molecular hydrogen (H2) are employed to search for a possible proton-to-electron mass ratio (μ) dependence on gravity. The Lyman transitions of H2, observed with the Hubble Space Telescope towards white dwarf stars that underwent a gravitational collapse, are compared to accurate laboratory spectra taking into account the high temperature conditions (T∼13 000  K) of their photospheres. We derive sensitivity coefficients Ki which define how the individual H2 transitions shift due to μ dependence. The spectrum of white dwarf star GD133 yields a Δμ/μ constraint of (-2.7±4.7stat±0.2syst)×10(-5) for a local environment of a gravitational potential ϕ∼10(4) ϕEarth, while that of G29-38 yields Δμ/μ=(-5.8±3.8stat±0.3syst)×10(-5) for a potential of 2×10(4) ϕEarth.

Dependences of contraction/expansion of stacking faults on temperature and current density in 4H-SiC p–i–n diodes

NASA Astrophysics Data System (ADS)

Okada, Aoi; Nishio, Johji; Iijima, Ryosuke; Ota, Chiharu; Goryu, Akihiro; Miyazato, Masaki; Ryo, Mina; Shinohe, Takashi; Miyajima, Masaaki; Kato, Tomohisa; Yonezawa, Yoshiyuki; Okumura, Hajime

2018-06-01

To investigate the mechanism of contraction/expansion behavior of Shockley stacking faults (SSFs) in 4H-SiC p–i–n diodes, the dependences of the SSF behavior on temperature and injection current density were investigated by electroluminescence image observation. We investigated the dependences of both triangle- and bar-shaped SSFs on the injection current density at four temperature levels. All SSFs in this study show similar temperature and injection current density dependences. We found that the expansion of SSFs at a high current density was converted to contraction at a certain value as the current decreased and that the value is temperature-dependent. It has been confirmed that SSF behavior, which was considered complex or peculiar, might be explained mainly by the energy change caused by SSFs.

Temperature Dependence of IP3-Mediated Local and Global Ca2+ Signals

PubMed Central

Dickinson, George D.; Parker, Ian

2013-01-01

We examined the effect of temperature (12–40°C) on local and global Ca2+ signals mediated by inositol trisphosphate receptor/channels (IP3R) in human neuroblastoma (SH-SY5Y) cells. The amplitudes and spatial spread of local signals arising from single IP3R (blips) and clusters of IP3R (puffs) showed little temperature dependence, whereas their kinetics (durations and latencies) were markedly accelerated by increasing temperature. In contrast, the amplitude of global Ca2+ waves increased appreciably at lower temperatures, probably as a result of the longer duration of IP3R channel opening. Several parameters, including puff and blip durations, puff latency and frequency, and frequency of repetitive Ca2+ waves, showed a biphasic temperature dependence on Arrhenius plots. In all cases the transition temperature occurred at ∼25°C, possibly reflecting a phase transition in the lipids of the endoplasmic reticulum membrane. Although the IP3-evoked Ca2+ signals were qualitatively similar at 25°C and 36°C, one should consider the temperature sensitivity of IP3-mediated signal amplitudes when extrapolating from room temperature to physiological temperature. Conversely, further cooling may be advantageous to improve the optical resolution of channel gating kinetics. PMID:23442860

Clofibric acid degradation in UV254/H2O2 process: effect of temperature.

PubMed

Li, Wenzhen; Lu, Shuguang; Qiu, Zhaofu; Lin, Kuangfei

2010-04-15

The degradation of clofibric acid (CA) in UV(254)/H(2)O(2) process under three temperature ranges, i.e. T1 (9.0-11.5 degrees C), T2 (19.0-21.0 degrees C) and T3 (29.0-30.0 degrees C) was investigated. The effects of solution constituents including NO(3)(-) and HCO(3)(-) anions, and humic acid (HA) on CA degradation were evaluated in Milli-Q waters. CA degradation behaviors were simulated with the pseudo-first-order kinetic model and the apparent rate constant (k(ap)) and half-life time (t(1/2)) were calculated. The results showed that higher temperature would favor CA degradation, and CA degradation was taken place mostly by indirect oxidation through the formation of OH radicals in UV(254)/H(2)O(2) process. In addition, the effects of both NO(3)(-) and HCO(3)(-) anions at two selected concentrations (1.0x10(-3) and 0.1 mol L(-1)) and HA (20 mg L(-1)) on CA degradation were investigated. The results showed that HA had negative effect on CA degradation, and this effect was much more apparent under low temperature condition. On the other hand, the inhibitive effect on CA degradation at both lower and higher concentrations of bicarbonate was observed, and this inhibitive effect was much more apparent at higher bicarbonate concentration and lower temperature condition. While, at higher nitrate concentration the inhibitive effect on CA degradation under three temperature ranges was observed, and with the temperature increase this negative effect was apparently weakened. However, at lower nitrate concentration a slightly positive effect on CA degradation was found under T2 and T3 conditions. Moreover, when using a real wastewater treatment plant (WWTP) effluent spiked with CA over 99% of CA removal could be achieved under 30 degrees C within only 15 min compared with 40 and 80 min under 20 and 10 degrees C respectively, suggesting a significant promotion in CA degradation under higher temperature condition. Therefore, it can be concluded that temperature plays an

Measuring temperature-dependent activation energy in thermally activated processes: a 2D Arrhenius plot method.

PubMed

Li, Jian V; Johnston, Steven W; Yan, Yanfa; Levi, Dean H

2010-03-01

Thermally activated processes are characterized by two key quantities, activation energy (E(a)) and pre-exponential factor (nu(0)), which may be temperature dependent. The accurate measurement of E(a), nu(0), and their temperature dependence is critical for understanding the thermal activation mechanisms of non-Arrhenius processes. However, the classic 1D Arrhenius plot-based methods cannot unambiguously measure E(a), nu(0), and their temperature dependence due to the mathematical impossibility of resolving two unknown 1D arrays from one 1D experimental data array. Here, we propose a 2D Arrhenius plot method to solve this fundamental problem. Our approach measures E(a) at any temperature from matching the first and second moments of the data calculated with respect to temperature and rate in the 2D temperature-rate plane, and therefore is able to unambiguously solve E(a), nu(0), and their temperature dependence. The case study of deep level emission in a Cu(In,Ga)Se(2) solar cell using the 2D Arrhenius plot method reveals clear temperature dependent behavior of E(a) and nu(0), which has not been observable by its 1D predecessors.

Temperature dependent behavior of localized and delocalized electrons in nitrogen-doped 6H SiC crystals as studied by electron spin resonance

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

Savchenko, D., E-mail: dariyasavchenko@gmail.com; National Technical University of Ukraine “Kyiv Polytechnic Institute”, Kyiv 03056; Kalabukhova, E.

2016-01-28

We have studied the temperature behavior of the electron spin resonance (ESR) spectra of nitrogen (N) donors in n-type 6H SiC crystals grown by Lely and sublimation sandwich methods (SSM) with donor concentration of 10{sup 17 }cm{sup −3} at T = 60–150 K. A broad signal in the ESR spectrum was observed at T ≥ 80 K with Lorentzian lineshape and g{sub ||} = 2.0043(3), g{sub ⊥} = 2.0030(3), which was previously assigned in the literature to the N donors in the 1s(E) excited state. Based on the analysis of the ESR lineshape, linewidth and g-tensor we attribute this signal to the conduction electrons (CE). The emergence of the CE ESRmore » signal at T > 80 K was explained by the ionization of electrons from the 1s(A{sub 1}) ground and 1s(E) excited states of N donors to the conduction band while the observed reduction of the hyperfine (hf) splitting for the N{sub k1,k2} donors with the temperature increase is attributed to the motional narrowing effect of the hf splitting. The temperature dependence of CE ESR linewidth is described by an exponential law (Orbach process) with the activation energy corresponding to the energy separation between 1s(A{sub 1}) and 1s(E) energy levels for N residing at quasi-cubic sites (N{sub k1,k2}). The theoretical analysis of the temperature dependence of microwave conductivity measured by the contact-free method shows that due to the different position of the Fermi level in two samples the ionization of free electrons occurs from the energy levels of N{sub k1,k2} donors in Lely grown samples and from the energy level of N{sub h} residing at hexagonal position in 6H SiC grown by SSM.« less

Diamagnetic Torque Signal and Temperature-Dependent Paramagnetism in Bi2Sr2CaCu2O8+δ

NASA Astrophysics Data System (ADS)

Tsuchiya, Satoshi; Mochiku, Takashi; Ooi, Shuichi; Hirata, Kazuto; Sugii, Kaori; Terashima, Taichi; Uji, Shinya

2017-11-01

Magnetic torque and resistance measurements for the superconducting cuprate Bi2Sr2CaCu2O8+δ with Tc = 87 K have been performed to determine the phase diagram in a parallel magnetic field fields up to 14 T. The anisotropy of the magnetization, derived from the torque, is found to decrease with decreasing temperature below 125 K, which can be ascribed to the temperature dependent paramagnetic spin susceptibility. The angular dependence of the torque clearly shows small diamagnetism due to fluctuating or inhomogeneous superconductivity at temperatures between Tc and ˜100 K. The results suggest that the pseudogap is not of superconducting origin.

Temperature dependence of the formation of sulfate aerosols in the stratosphere

NASA Technical Reports Server (NTRS)

Yue, G. K.; Deepak, A.

1982-01-01

Classical nucleation theory is used in calculations of the temperature dependence of the characteristics and nucleation rates of sulfate aerosols in the binary H2SO4-H2O vapor mixture, in order to assess the influence of temperature on the formation of sulfate aerosols in the stratosphere, and to explore the possibility of new particle formation through homogeneous nucleation processes at regions where temperature is as low as -75 C, rather than the often-assumed -50 or -55 C. Calculation results indicate that the number of particles formed at a lower temperature is larger by several orders of magnitude than at higher temperatures, when water and sulfuric acid vapor concentrations are kept constant, and that large quantities of ultrafine particles which cannot be detected by conventional methods may exist at low-temperature stratospheric regions.

Chip-to-chip SnO2 nanowire network sensors for room temperature H2 detection

NASA Astrophysics Data System (ADS)

Köck, A.; Brunet, E.; Mutinati, G. C.; Maier, T.; Steinhauer, S.

2012-06-01

The employment of nanowires is a very powerful strategy to improve gas sensor performance. We demonstrate a gas sensor device, which is based on silicon chip-to-chip synthesis of ultralong tin oxide (SnO2) nanowires. The sensor device employs an interconnected SnO2 nanowire network configuration, which exhibits a huge surface-to-volume ratio and provides full access of the target gas to the nanowires. The chip-to-chip SnO2 nanowire device is able to detect a H2 concentration of only 20 ppm in synthetic air with ~ 60% relative humidity at room temperature. At an operating temperature of 300°C a concentration of 50 ppm H2 results in a sensitivity of 5%. At this elevated temperature the sensor shows a linear response in a concentration range between 10 ppm and 100 ppm H2. The SnO2-nanowire fabrication procedure based on spray pyrolysis and subsequent annealing is performed at atmospheric pressure, requires no vacuum and allows upscale of the substrate to a wafer size. 3D-integration with CMOS chips is proposed as viable way for practical realization of smart nanowire based gas sensor devices for the consumer market.

Ionic strength dependence of the oxidation of SO2 by H2O2 in sodium chloride particles

NASA Astrophysics Data System (ADS)

Ali, H. M.; Iedema, M.; Yu, X.-Y.; Cowin, J. P.

2014-06-01

The reaction of sulfur dioxide and hydrogen peroxide in the presence of deliquesced (>75% RH) sodium chloride (brine) particles was studied by utilizing a cross flow mini-reactor. The reaction kinetics were followed by observing chloride depletion in particles by computer-controlled scanning electron microscope with energy dispersive X-ray analysis, namely CCSEM/EDX. The reactions take place in concentrated mixed salt brine aerosols, for which no complete kinetic equilibrium data previously existed. We measured the Henry's law solubility of H2O2 in brine solutions to close that gap. We also calculated the reaction rate as the particle transforms continuously from concentrated NaCl brine to, eventually, a mixed NaHSO4 plus H2SO4 brine solution. The reaction rate of the SO2 oxidation by H2O2 was found to be influenced by the change in ionic strength as the particle undergoes compositional transformation, following closely the dependence of the third order rate constant on ionic strength as predicted using established rate equations. This is the first study that has measured the ionic strength dependence of sulfate formation (in non-aqueous media) from oxidation of mixed salt brine aerosols in the presence of H2O2. It also gives the first report of the dependence of the Henry's law constant of H2O2 on ionic strength.

Ionic strength dependence of the oxidation of SO2 by H2O2 in sodium chloride particles

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

Ali, Hashim M.; Iedema, Martin J.; Yu, Xiao-Ying

The reaction of sulfur dioxide and hydrogen peroxide in the presence of deliquesced (>75% RH) sodium particles was studied by utilizing a crossflow-mini reactor. The reaction kinetics was followed by observing chloride depletion in particles by computer-controlled scanning electron microscope with energy dispersive X-ray analysis, namely SEM/EDX. The reactions take place in concentrated mixed salt brine aerosols, for which no complete kinetic equilibrium data previously existed. We measured the Henry’s law solubility of H2O2 to close that gap. We also calculated the reaction rate as the particle transforms continuously from concentrated NaCl brine to eventually a mixed NaHSO4 plus H2SO4more » brine solution. The reaction rate of the SO2 oxidation by H2O2 was found to be influenced by the change in ionic strength as the particle undergoes compositional transformation, following closely the dependence of the third order rate constant on ionic strength as predicted rates using previously established rate equations. This is the first study that has measured the ionic strength dependence of sulfate formation (in non-aqueous media) from oxidation of mixed salt brine aerosols in the presence of H2O2. It also gives the first report of the Henry’s law constant of H2O2 dependence on ionic strength.« less

The Orion Fingers: H2 Temperatures and Excitation in an Explosive Outflow

NASA Astrophysics Data System (ADS)

Youngblood, Allison; France, Kevin; Ginsburg, Adam; Hoadley, Keri; Bally, John

2018-04-01

We measure H2 temperatures and column densities across the Orion Becklin-Neugebauer/Kleinmann-Low (BN/KL) explosive outflow from a set of 13 near-infrared (IR) H2 rovibrational emission lines observed with the TripleSpec spectrograph on Apache Point Observatory’s 3.5 m telescope. We find that most of the region is well characterized by a single temperature (∼2000–2500 K), which may be influenced by the limited range of upper-energy levels (6000–20,000 K) probed by our data set. The H2 column density maps indicate that warm H2 comprises 10‑5–10‑3 of the total H2 column density near the center of the outflow. Combining column density measurements for co-spatial H2 and CO at T = 2500 K, we measure a CO/H2 fractional abundance of 2 × 10‑3 and discuss possible reasons why this value is in excess of the canonical 10‑4 value, including dust attenuation, incorrect assumptions on co-spatiality of the H2 and CO emission, and chemical processing in an extreme environment. We model the radiative transfer of H2 in this region with ultraviolet (UV) pumping models to look for signatures of H2 fluorescence from H I Lyα pumping. Dissociative (J-type) shocks and nebular emission from the foreground Orion H II region are considered as possible Lyα sources. From our radiative transfer models, we predict that signatures of Lyα pumping should be detectable in near-IR line ratios given a sufficiently strong source, but such a source is not present in the BN/KL outflow. The data are consistent with shocks as the H2 heating source.

Temperature dependence of the intensity of the vibration-rotational absorption band ν2 of H2O trapped in an argon matrix

NASA Astrophysics Data System (ADS)

Pitsevich, G.; Doroshenko, I.; Malevich, A..; Shalamberidze, E.; Sapeshko, V.; Pogorelov, V.; Pettersson, L. G. M.

2017-02-01

Using two sets of effective rotational constants for the ground (000) and the excited bending (010) vibrational states the calculation of frequencies and intensities of vibration-rotational transitions for J″ = 0 - 2; and J‧ = 0 - 3; was carried out in frame of the model of a rigid asymmetric top for temperatures from 0 to 40 K. The calculation of the intensities of vibration-rotational absorption bands of H2O in an Ar matrix was carried out both for thermodynamic equilibrium and for the case of non-equilibrium population of para- and ortho-states. For the analysis of possible interaction of vibration-rotational and translational motions of a water molecule in an Ar matrix by 3D Schrödinger equation solving using discrete variable representation (DVR) method, calculations of translational frequencies of H2O in a cage formed after one argon atom deleting were carried out. The results of theoretical calculations were compared to experimental data taken from literature.

The Temperature Dependence of the Partition of CH4 and C2H6 in Structure I Hydrates

NASA Astrophysics Data System (ADS)

Cheng, H.; Lu, W.

2017-12-01

At present, we mainly use hydrocarbon gas and carbon isotope composition to determine the gas source of natural gas hydrate. Judging the type of gas source plays a key role in the evaluation of hydrate reservoirs, but there is still controversy over this approach. Considering the crystal properties of hydrate, the process of aggregation and decomposition of natural gas hydrates may have an important effect on the gas composition. We used CH4 (C1), C2H6 (C2) and their mixture as gas sources to synthesize hydrates from aqueous solution in high-pressure capillary tubes. Gas concentration in hydrates grew at different temperatures was measured with quantitative Raman spectroscopy. The results show that concentrations of gas in pure methane and pure ethane hydrates increase with temperature. The results of the mixture are similar to pure gas below 288.15 K, the concentration of C1 in small cages (SC, 512) slowly increased, but the competitive relationship between methane and ethane in large cages (LC, 51262) become obvious after 288.15 K. From 278.15 K to 294.15 K, the value of C1/C2 decreased from 26.38 to 6.61, gradually closing to the original gas composition of 4. We find that gas hydrates are more likely to gather C1 when they accumulate. The lower the temperature is, the more obvious it will be, and the closer the value of C1/C2 is to the microbial gases.

Rate contants for CF{sub 3} + H{sub 2} {yields} CF{sub 3}H + H and CF{sub 3}H + H {yields} CF{sub 3} + H{sub 2} reactions in the temperature range 1100-1600 K.

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

Hranisavljevic, J.; Michael, V.; Chemistry

1998-09-24

The shock tube technique coupled with H-atom atomic resonance absorption spectrometry has been used to study the reactions (1) CF{sub 3} + H{sub 2} {yields} CF{sub 3}H + H and (2) CF{sub 3}H + H{yields} CF{sub 3} + H{sub 2} over the temperature ranges 1168-1673 K and 1111-1550 K, respectively. The results can be represented by the Arrhenius expressions k1 = 2.56 x 10{sup -11} exp(-8549K/T) and k2 = 6.13 x 10{sup -11} exp(-7364K/T), both in cm3 molecule-1 s-1. Equilibrium constants were calculated from the two Arrhenius expressions in the overlapping temperature range, and good agreement was obtained with themore » literature values. The rate constants for reaction 2 were converted into rate constants for reaction 1 using literature equilibrium constants. These data are indistinguishable from direct k1 measurements, and an Arrhenius fit for the joint set is k{sub 1} = 1.88 x 10{sup -11} exp(-8185K/T) cm3 molecule-1 s-1. The CF{sub 3} + H{sub 2} {yields} CF{sub 3}H + H reaction was further modeled using conventional transition-state theory, which included ab initio electronic structure determinations of reactants, transition state, and products.« less

Temperature Dependence of the Viscosity of Isotropic Liquids

NASA Astrophysics Data System (ADS)

Jadzyn, J.; Czechowski, G.; Lech, T.

1999-04-01

Temperature dependence of the shear viscosity measured for isotropic liquids belonging to the three homologous series: 4-(trans-4'-n-alkylcyclohexyl) isothiocyanatobenzenes (Cn H2n+1 CyHx Ph NCS; nCHBT, n=0-12), n-alkylcyanobiphenyls (CnH2n+1 Ph Ph CN; nCB, n=2-12) and 1,n-alkanediols (HO(CH2)nOH; 1,nAD, n=2-10) were analysed with the use of Arrhenius equation and its two modifications: Vogel--Fulcher and proposed in this paper. The extrapolation of the isothermal viscosity of 1,n-alkanediols (n=2-10) to n=1 leads to an interesting conclusion concerning the expected viscosity of methanediol, HOCH2OH, the compound strongly unstable in a pure state.

Novel HCN2 mutation contributes to febrile seizures by shifting the channel's kinetics in a temperature-dependent manner.

PubMed

Nakamura, Yuki; Shi, Xiuyu; Numata, Tomohiro; Mori, Yasuo; Inoue, Ryuji; Lossin, Christoph; Baram, Tallie Z; Hirose, Shinichi

2013-01-01

Hyperpolarization-activated cyclic nucleotide-gated (HCN) channel-mediated currents, known as I h, are involved in the control of rhythmic activity in neuronal circuits and in determining neuronal properties including the resting membrane potential. Recent studies have shown that HCN channels play a role in seizure susceptibility and in absence and limbic epilepsy including temporal lobe epilepsy following long febrile seizures (FS). This study focused on the potential contributions of abnormalities in the HCN2 isoform and their role in FS. A novel heterozygous missense mutation in HCN2 exon 1 leading to p.S126L was identified in two unrelated patients with FS. The mutation was inherited from the mother who had suffered from FS in a pedigree. To determine the effect of this substitution we conducted whole-cell patch clamp electrophysiology. We found that mutant channels had elevated sensitivity to temperature. More specifically, they displayed faster kinetics at higher temperature. Kinetic shift by change of temperature sensitivity rather than the shift of voltage dependence led to increased availability of I h in conditions promoting FS. Responses to cyclic AMP did not differ between wildtype and mutant channels. Thus, mutant HCN2 channels cause significant cAMP-independent enhanced availability of I h during high temperatures, which may contribute to hyperthermia-induced neuronal hyperexcitability in some individuals with FS.

Photolysis of H2O-H2O2 Mixtures: The Destruction of H2O2

NASA Technical Reports Server (NTRS)

Loeffler, M. J.; Fama, M.; Baragiola, R. A.; Carlson, R. W.

2013-01-01

We present laboratory results on the loss of H2O2 in solid H2O + H2O2 mixtures at temperatures between 21 and 145 K initiated by UV photolysis (193 nm). Using infrared spectroscopy and microbalance gravimetry, we measured the decrease of the 3.5 micrometer infrared absorption band during UV irradiation and obtained a photodestruction cross section that varies with temperature, being lowest at 70 K. We use our results, along with our previously measured H2O2 production rates via ionizing radiation and ion energy fluxes from the spacecraft to compare H2O2 creation and destruction at icy satellites by ions from their planetary magnetosphere and from solar UV photons. We conclude that, in many cases, H2O2 is not observed on icy satellite surfaces because the H2O2 photodestruction rate is much higher than the production rate via energetic particles, effectively keeping the H2O2 infrared signature at or below the noise level.

Temperature dependence of resonant secondary emission in NaNO 2: Spectral behavior

NASA Astrophysics Data System (ADS)

Kato, Riso; Kawaguchi, Yoshizo; Ashida, Masaaki

1990-05-01

Spectral behavior of resonant secondary emission in NaNO 2 has been investigated in the temperature range from 2 to 30 K under the excitation near the v00 line of the lowest singlet absorption. With increasing temperature, luminescence lines separated from multiple-order Raman lines become detectable even under the excitation with the off-resonance energy Δ c ≳ 13 cm -1. The intensity of the luminescence line IL( T) increases with temperature in proportion to the phonon number n( hvp, T) in the temperature range T ≲ Δ c/ k, while it increases more steeply in the range T ≳ Δ c/ k. The temperature dependence of IL( T) is ascribed to the increase in the luminescence from the v00 level after the one-phonon assisted transition to the level induced by the off-resonant incident light. The intensity of the Raman line IR( T) decreases gradually in 2-12 K range and shows rapid drop above 12 K. The temperature dependence of IR( T) is ascribed to the dephasing of the intermediate state due to the two-phonon interaction with the reservoir.

Frequency dependent polarisation switching in h-ErMnO3

NASA Astrophysics Data System (ADS)

Ruff, Alexander; Li, Ziyu; Loidl, Alois; Schaab, Jakob; Fiebig, Manfred; Cano, Andres; Yan, Zewu; Bourret, Edith; Glaum, Julia; Meier, Dennis; Krohns, Stephan

2018-04-01

We report an electric-field poling study of the geometrically-driven improper ferroelectric h-ErMnO3. From a detailed dielectric analysis, we deduce the temperature and the frequency dependent range for which single-crystalline h-ErMnO3 exhibits purely intrinsic dielectric behaviour, i.e., free from the extrinsic so-called Maxwell-Wagner polarisations that arise, for example, from surface barrier layers. In this regime, ferroelectric hysteresis loops as a function of frequency, temperature, and applied electric fields are measured, revealing the theoretically predicted saturation polarisation on the order of 5-6 μC/cm2. Special emphasis is put on frequency dependent polarisation switching, which is explained in terms of domain-wall movement similar to proper ferroelectrics. Controlling the domain walls via electric fields brings us an important step closer to their utilization in domain-wall-based electronics.

Resonances at very low temperature for the reaction D2 + H

NASA Astrophysics Data System (ADS)

Simbotin, I.; Côté, R.

2017-05-01

We present numerical results for rate coefficients of reaction and vibrational quenching in the collision of H with {{{D}}}2(v,j) at cold and ultracold temperatures. We explore both ortho-D{}2(j=0) and para-D{}2(j=1) for several initial vibrational states (v≤slant 5), and find resonant structures in the energy range 0.01-10 K, which are sensitive to the initial rovibrational state (v, j). We compare the reaction rates for D2 + H with our previously obtained results for the isotopologue reaction H2 + D, and discuss the implications of our detailed study of this benchmark system for ultracold chemistry.

Development of a TDLAS sensor for temperature and concentration of H2 O in high speed and high temperature flows

NASA Astrophysics Data System (ADS)

Sheehe, Suzanne; O'Byrne, Sean

2017-06-01

The development of a sensor for simultaneous temperature concentration of H2 O and temperature in high speed flows is presented. H2 O is a desirable target sensing species because it is a primary product in combustion systems; both temperature and concentration profiles can be used to assess both the extent of the combustion and the flow field characteristics. Accurate measurements are therefore highly desirable. The sensor uses a vertical-cavity surface emitting laser (VCSEL) scanned at 50 kHz from 7172 to 7186 cm-1. Temperatures and concentrations are extracted from the spectra by fitting theoretical spectra to the experimental data. The theoretical spectra are generated using GENSPECT in conjunction with line parameters from the HITRAN 2012 database. To validate the theoretical spectra, experimental spectra of H2 O were obtained at known temperatures (290-550 K) and pressures (30 torr) in a heated static gas cell. The results show that some theoretical lines deviate from the experimental lines. New line-strengths are calculated assuming that the line assignments and broadening parameters in HITRAN are correct. This data is essential for accurate H2 O concentration and temperature measurements at low pressure and high temperature conditions. US Air Force Asian Office of Aerospace Research and Development Grant FA2386-16-1-4092.

The primary solar-type atmosphere surrounding the accreting Earth: H2O-induced high surface temperature.

NASA Astrophysics Data System (ADS)

Sasaki, S.

In the solar nebula, a growing planet attracts ambient gas to form a solar-type atmosphere. The structure of this H2-He atmosphere is calculated assuming the Earth was formed in the nebula. The blanketing effect of the atmosphere renders the planetary surface molten when the planetary mass exceeds 0.2 ME (ME being the present Earth's mass). Reduction of the surface melt by atmospheric H2 should add a large amount of H2O to the atmosphere: under the quartz-iron-fayalite oxygen buffer, partial pressure ratio P(H2O)/P(H2) becomes higher than 0.1. Enhancing opacity and gas mean molecular weight, the excess H2O raises the temperature and renders the atmosphere in convective equilibrium, while the dissociation of H2 suppresses the adiabatic temperature gradient. The surface temperature of the proto-Earth can be as high as 4700K when its mass is 1 ME. Such a high temperature may accelerate the evaporation of surface materials. A deep totally-molten magma ocean should exist in the accretion Earth.

Pressure dependence of excited-state charge-carrier dynamics in organolead tribromide perovskites

NASA Astrophysics Data System (ADS)

Liu, X. C.; Han, J. H.; Zhao, H. F.; Yan, H. C.; Shi, Y.; Jin, M. X.; Liu, C. L.; Ding, D. J.

2018-05-01

Excited-state charge-carrier dynamics governs the performance of organometal trihalide perovskites (OTPs) and is strongly influenced by the crystal structure. Characterizing the excited-state charge-carrier dynamics in OTPs under high pressure is imperative for providing crucial insights into structure-property relations. Here, we conduct in situ high-pressure femtosecond transient absorption spectroscopy experiments to study the excited-state carrier dynamics of CH3NH3PbBr3 (MAPbBr3) under hydrostatic pressure. The results indicate that compression is an effective approach to modulate the carrier dynamics of MAPbBr3. Across each pressure-induced phase, carrier relaxation, phonon scattering, and Auger recombination present different pressure-dependent properties under compression. Responsiveness is attributed to the pressure-induced variation in the lattice structure, which also changes the electronic band structure. Specifically, simultaneous prolongation of carrier relaxation and Auger recombination is achieved in the ambient phase, which is very valuable for excess energy harvesting. Our discussion provides clues for optimizing the photovoltaic performance of OTPs.

Direct absorption spectroscopy sensor for temperature and H2O concentration of flat flame burner

NASA Astrophysics Data System (ADS)

Duan, Jin-hu; Jin, Xing; Wang, Guang-yu; Qu, Dong-sheng

2016-01-01

A tunable diode laser absorption sensor, based on direct absorption spectroscopy and time division multiplexing scheme, was developed to measure H2O concentration and temperature of flat flame burner. At the height of 15mm from the furnace surface, temperature and concentration were measured at different equivalence ratios. Then the distance between the laser and the furnace surface was changed while the equivalence ratio was fixed at 1 and experiments were performed to measure temperature and H2O concentration at every height. At last flame temperatures and H2O concentrations were obtained by simulation and computational analysis and these combustion parameters were compared with the reference. The results showed that the experimental results were in accordance with the reference values. Temperature errors were less than 4% and H2O component concentration errors were less than 5%and both of them reached their maximum when the equivalent ratio was set at 1. The temperature and H2O concentration increased with the height from furnace surface to laser when it varied from 3mm to 9mm and it decreased when it varied from 9mm to 30mm and they reached their maximum at the height of 9mm. Keywords: tunable diode laser, direct absorption spectroscopy

Mitigation of the hematopoietic and gastrointestinal acute radiation syndrome by octadecenyl thiophosphate, a small molecule mimic of lysophosphatidic acid.

PubMed

Deng, Wenlin; Kimura, Yasuhiro; Gududuru, Veeresh; Wu, Wenjie; Balogh, Andrea; Szabo, Erzsebet; Thompson, Karin Emmons; Yates, C Ryan; Balazs, Louisa; Johnson, Leonard R; Miller, Duane D; Strobos, Jur; McCool, W Shannon; Tigyi, Gabor J

2015-04-01

We have previously demonstrated that the small molecule octadecenyl thiophosphate (OTP), a synthetic mimic of the growth factor-like mediator lysophosphatidic acid (LPA), showed radioprotective activity in a mouse model of total-body irradiation (TBI) when given orally or intraperitoneally 30 min before exposure to 9 Gy γ radiation. In the current study, we evaluated the effects of OTP, delivered subcutaneously, for radioprotection or radiomitigation from -24 h before to up to +72 h postirradiation using a mouse TBI model with therapeutic doses at around 1 mg/kg. OTP was injected at 10 mg/kg without observable toxic side effects in mice, providing a comfortable safety margin. Treatment of C57BL/6 mice with a single dose of OTP over the time period from -12 h before to +26 h after a lethal dose of TBI reduced mortality by 50%. When administered at +48 h to +72 h postirradiation (LD50/30 to LD100/30), OTP reduced mortality by ≥34%. OTP administered at +24 h postirradiation significantly elevated peripheral white blood cell and platelet counts, increased crypt survival in the jejunum, enhanced intestinal glucose absorption and reduced endotoxin seepage into the blood. In the 6.4-8.6 Gy TBI range using LD50/10 as the end point, OTP yielded a dose modification factor of 1.2. The current data indicate that OTP is a potent radioprotector and radiomitigator ameliorating the mortality and tissue injury of acute hematopoietic as well as acute gastrointestinal radiation syndrome.

Effects of H{sub 2} and H preferential diffusion and unity Lewis number on superadiabatic flame temperatures in rich premixed methane flames

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

Liu, Fengshan; Guelder, OEmer L.

2005-11-01

The structures of freely propagating rich CH{sub 4}/air and CH{sub 4}/O{sub 2} flames were studied numerically using a relatively detailed reaction mechanism. Species diffusion was modeled using five different methods/assumptions to investigate the effects of species diffusion, in particular H{sub 2} and H, on superadiabatic flame temperature. With the preferential diffusion of H{sub 2} and H accounted for, significant amount of H{sub 2} and H produced in the flame front diffuse from the reaction zone to the preheat zone. The preferential diffusion of H{sub 2} from the reaction zone to the preheat zone has negligible effects on the phenomenon ofmore » superadiabatic flame temperature in both CH{sub 4}/air and CH{sub 4}/O{sub 2} flames. It is therefore demonstrated that the superadiabatic flame temperature phenomenon in rich hydrocarbon flames is not due to the preferential diffusion of H{sub 2} from the reaction zone to the preheat zone as recently suggested by Zamashchikov et al. [V.V. Zamashchikov, I.G. Namyatov, V.A. Bunev, V.S. Babkin, Combust. Explosion Shock Waves 40 (2004) 32]. The suppression of the preferential diffusion of H radicals from the reaction zone to the preheat zone drastically reduces the degree of superadiabaticity in rich CH{sub 4}/O{sub 2} flames. The preferential diffusion of H radicals plays an important role in the occurrence of superadiabatic flame temperature. The assumption of unity Lewis number for all species leads to the suppression of H radical diffusion from the reaction zone to the preheat zone and significant diffusion of CO{sub 2} from the postflame zone to the reaction zone. Consequently, the degree of superadiabaticity of flame temperature is also significantly reduced. Through reaction flux analyses and numerical experiments, the chemical nature of the superadiabatic flame temperature phenomenon in rich CH{sub 4}/air and CH{sub 4}/O{sub 2} flames was identified to be the relative scarcity of H radical, which leads to

Induction of a Torpor-Like State by 5’-AMP Does Not Depend on H2S Production

PubMed Central

Dugbartey, George J.; Bouma, Hjalmar R.; Strijkstra, Arjen M.; Boerema, Ate S.; Henning, Robert H.

2015-01-01

Background Therapeutic hypothermia is used to reduce ischemia/reperfusion injury (IRI) during organ transplantation and major surgery, but does not fully prevent organ injury. Interestingly, hibernating animals undergo repetitive periods of low body temperature called ‘torpor’ without signs of organ injury. Recently, we identified an essential role of hydrogen sulfide (H2S) in entrance into torpor and preservation of kidney integrity during hibernation. A torpor-like state can be induced pharmacologically by injecting 5’-Adenosine monophosphate (5’-AMP). The mechanism by which 5’-AMP leads to the induction of a torpor-like state, and the role of H2S herein, remains to be unraveled. Therefore, we investigated whether induction of a torpor-like state by 5-AMP depends on H2S production. Methods To study the role of H2S on the induction of torpor, amino-oxyacetic acid (AOAA), a non-specific inhibitor of H2S, was administered before injection with 5'-AMP to block endogenous H2S production in Syrian hamster. To assess the role of H2S on maintenance of torpor induced by 5’-AMP, additional animals were injected with AOAA during torpor. Key Results During the torpor-like state induced by 5’-AMP, the expression of H2S- synthesizing enzymes in the kidneys and plasma levels of H2S were increased. Blockade of these enzymes inhibited the rise in the plasma level of H2S, but neither precluded torpor nor induced arousal. Remarkably, blockade of endogenous H2S production was associated with increased renal injury. Conclusions Induction of a torpor-like state by 5’-AMP does not depend on H2S, although production of H2S seems to attenuate renal injury. Unraveling the mechanisms by which 5’-AMP reduces the metabolism without organ injury may allow optimization of current strategies to limit (hypothermic) IRI and improve outcome following organ transplantation, major cardiac and brain surgery. PMID:26295351

Sorption Properties of Iron-Magnesium and Nickel-Magnesium Mg2FeH6 and Mg2NiH4 Hydrides

NASA Astrophysics Data System (ADS)

Matysina, Z. A.; Zaginaichenko, S. Yu.; Shchur, D. V.; Gabdullin, M. T.

2016-06-01

Based on molecular-kinetic representations, theory of hydrogen absorption-desorption processes in binary Mg-Fe and Mg-Ni alloys is developed. Free energies of hydrides of these alloys are calculated. Equations of their thermodynamically equilibrium state determining the P-T-c diagrams are derived. A temperature dependence of the desorbed hydrogen concentration is established. A maximal desorption temperature is estimated. The state diagrams determining the concentration dependence of the maximal desorption temperature are constructed. Isopleths and isotherms of hydrogen solubility in the alloys are calculated. The possibility of manifestation of the hysteresis effect in hydrogen solubility isotherms is revealed and the decrease of the width and length of a hysteresis loop with increasing temperature is demonstrated together with the influence of the magnesium hydrate MgH2 in Mg2FeH6 samples and running of chemical reactions on the behavior of the isotherms and the occurrence of bends and jumps in them. All established functional dependences of the sorption properties of the examined alloys are compared with experimental data available from the literature.

Effect of mild-temperature H2O2 oxidation on solubilization and anaerobic digestion of waste activated sludge.

PubMed

Junga, Heejung; Kim, Jaai; Lee, Seungyong; Lee, Changsoo

2014-08-01

Efficient sludge management is among the most challenging issues in wastewater treatment today, and anaerobic digestion is regarded as a viable solution. Mild-temperature H202 oxidation was examined for enhanced solubilization and biogas production of waste activated sludge (WAS). The effects of pretreatment factors (i.e. temperature and H202 concentration) on the degree of WAS disintegration (DD) and biogas yield (BY) were assessed by response surface analysis within the design space of 60-90 degrees C and 0-200mM H202. Significant sludge disintegration (up to 23.0% DD) and visibly enhanced BY (up to 26.9%) were shown in the pretreatment trials. Two response surface models to describe how DD and BY respond to changes in the pretreatment conditions were successfully constructed (R2 > 0.95, p < 0.05). The models showed totally different response surface shapes, indicating the DD and BY were influenced by pretreatment conditions in very different ways. DD was dominantly affected by temperature and showed higher model responses at the high-temperature region, while the BY response peaked in the low-temperature and mid-level H2O2 region. This observation implies that the enhanced solubilization of WAS was not directly translated into an increase in biogas production. Our results showed that WAS can be efficiently disintegrated by H202 oxidation under mild-temperature conditions for enhanced anaerobic digestibility. Within the explored region of pretreatment conditions, the maximum BY was estimated to be 82.1 mL/gCODadded (32.8% greater than the untreated control) at (60.0 degrees C, 74.2 mM H2O2).

The Rate Constant for the Reaction H + C2H5 at T = 295 - 150K

NASA Technical Reports Server (NTRS)

Pimentel, Andre S.; Payne, Walter A.; Nesbitt, Fred L.; Cody, Regina J.; Stief, Louis J.

2004-01-01

The reaction between the hydrogen atom and the ethyl (C2H3) radical is predicted by photochemical modeling to be the most important loss process for C2H5 radicals in the atmospheres of Jupiter and Saturn. This reaction is also one of the major sources for the methyl radicals in these atmospheres. These two simplest hydrocarbon radicals are the initial species for the synthesis of larger hydrocarbons. Previous measurements of the rate constant for the H + C2H5 reaction varied by a factor of five at room temperature, and some studies showed a dependence upon temperature while others showed no such dependence. In addition, the previous studies were at higher temperatures and generally higher pressures than that needed for use in planetary atmospheric models. The rate constant for the reaction H + C2H5 has been measured directly at T = 150, 202 and 295 K and at P = 1.0 Torr He for all temperatures and additionally at P = 0.5 and 2.0 Torr He at T = 202 K. The measurements were performed in a discharge - fast flow system. The decay of the C2H5 radical in the presence of excess hydrogen was monitored by low-energy electron impact mass spectrometry under pseudo-first order conditions. H atoms and C2H5 radicals were generated rapidly and simultaneously by the reaction of fluorine atoms with H2 and C2H6, respectively. The total rate constant was found to be temperature and pressure independent. The measured total rate constant at each temperature are: k(sub 1)(295K) = (1.02+/-0.24)x10(exp -10), k(sub 1)(202K) = (1.02+/-0.22)x10(exp -10) and k(sub 1)(150K) = (0.93+/-0.21)x10(exp -10), all in units of cu cm/molecule/s. The total rate constant derived from all the combined measurements is k(sub 1) = (l.03+/-0.17)x10(exp -10) cu cm/molecule/s. At room temperature our results are about a factor of two higher than the recommended rate constant and a factor of three lower than the most recently published study.

Calculation of the rate constant for state-selected recombination of H+O2(v) as a function of temperature and pressure

NASA Astrophysics Data System (ADS)

Teitelbaum, Heshel; Caridade, Pedro J. S. B.; Varandas, António J. C.

2004-06-01

Classical trajectory calculations using the MERCURY/VENUS code have been carried out on the H+O2 reactive system using the DMBE-IV potential energy surface. The vibrational quantum number and the temperature were selected over the ranges v=0 to 15, and T=300 to 10 000 K, respectively. All other variables were averaged. Rate constants were determined for the energy transfer process, H+O2(v)-->H+O2(v''), for the bimolecular exchange process, H+O2(v)-->OH(v')+O, and for the dissociative process, H+O2(v)-->H+O+O. The dissociative process appears to be a mere extension of the process of transferring large amounts of energy. State-to-state rate constants are given for the exchange reaction, and they are in reasonable agreement with previous results, while the energy transfer and dissociative rate constants have never been reported previously. The lifetime distributions of the HO2 complex, calculated as a function of v and temperature, were used as a basis for determining the relative contributions of various vibrational states of O2 to the thermal rate coefficients for recombination at various pressures. This novel approach, based on the complex's ability to survive until it collides in a secondary process with an inert gas, is used here for the first time. Complete falloff curves for the recombination of H+O2 are also calculated over a wide range of temperatures and pressures. The combination of the two separate studies results in pressure- and temperature-dependent rate constants for H+O2(v)(+Ar)⇄HO2(+Ar). It is found that, unlike the exchange reaction, vibrational and rotational-translational energy are liabilities in promoting recombination.

Collisions of slow polyatomic ions with surfaces: dissociation and chemical reactions of C2H2+*, C2H3+, C2H4+*, C2H5+, and their deuterated variants C2D2+* and C2D4+* on room-temperature and heated carbon surfaces.

PubMed

Jasík, Juraj; Zabka, Jan; Feketeova, Linda; Ipolyi, Imre; Märk, Tilmann D; Herman, Zdenek

2005-11-17

Interaction of C2Hn+ (n = 2-5) hydrocarbon ions and some of their isotopic variants with room-temperature and heated (600 degrees C) highly oriented pyrolytic graphite (HOPG) surfaces was investigated over the range of incident energies 11-46 eV and an incident angle of 60 degrees with respect to the surface normal. The work is an extension of our earlier research on surface interactions of CHn+ (n = 3-5) ions. Mass spectra, translational energy distributions, and angular distributions of product ions were measured. Collisions with the HOPG surface heated to 600 degrees C showed only partial or substantial dissociation of the projectile ions; translational energy distributions of the product ions peaked at about 50% of the incident energy. Interactions with the HOPG surface at room temperature showed both surface-induced dissociation of the projectiles and, in the case of radical cation projectiles C2H2+* and C2H4+*, chemical reactions with the hydrocarbons on the surface. These reactions were (i) H-atom transfer to the projectile, formation of protonated projectiles, and their subsequent fragmentation and (ii) formation of a carbon chain build-up product in reactions of the projectile ion with a terminal CH3-group of the surface hydrocarbons and subsequent fragmentation of the product ion to C3H3+. The product ions were formed in inelastic collisions in which the translational energy of the surface-excited projectile peaked at about 32% of the incident energy. Angular distributions of reaction products showed peaking at subspecular angles close to 68 degrees (heated surfaces) and 72 degrees (room-temperature surfaces). The absolute survival probability at the incident angle of 60 degrees was about 0.1% for C2H2+*, close to 1% for C2H4+* and C2H5+, and about 3-6% for C2H3+.

The temperature-dependence of adenylate cyclase from baker's yeast.

PubMed Central

Londesborough, J; Varimo, K

1979-01-01

The Michaelis constant of membrane-bound adenylate cyclase increased from 1.1 to 1.8 mM between 7 and 38 degrees C (delta H = 13 kJ/mol). Over this temperature range, the maximum velocity increased 10-fold, and the Arrhenius plot was nearly linear, with an average delta H* of 51 kJ/mol. The temperature-dependence of the reaction rate at 2 mM-ATP was examined in more detail: for Lubrol-dispersed enzyme, Arrhenius plots were nearly linear with average delta H* values of 45 and 68 kJ/mol, respectively, for untreated and gel-filtered enzymes; for membrane-bound enzyme, delta H changed from 40 kJ/mol above about 21 degrees C to 62 kJ/mol below 21 degrees C, but this behaviour does not necessarily indicate an abrupt, lipid-induced, transition in the reaction mechanism. PMID:391221

Synthesis, crystal structure and high temperature phase transition in the new organic-inorganic hybrid [N(C4H9)4]3Zn2Cl7H2O crystals

NASA Astrophysics Data System (ADS)

Ben Gzaiel, Malika; Oueslati, Abderrazek; Lhoste, Jérôme; Gargouri, Mohamed; Bulou, Alain

2015-06-01

The present paper accounts for the synthesis, crystal structure, differential scanning calorimetry and vibrational spectroscopy of a new compound tri-tetrabutylammonium heptachloro-dizincate (I) grown at room temperature by slow evaporation of aqueous solution. From X-ray diffraction data collected at room temperature, it is concluded that it crystallizes in the monoclinic system (P21/n space group) containing ZnCl42- and ZnCl3H2O1- tetrahedra. The atomic arrangement can be described by an alternation of organic and organic-inorganic layers stacked along the c direction. Differential scanning calorimetry (DSC) in the range 250-450 K disclosed a reversible structural phase transition of order-disorder type at 358 K, prior to the melting at 395 K. The temperature dependence of the Raman spectra of [N(C4H9)4]3Zn2Cl7H2O single crystals was studied in the spectral range 100-3500 cm-1 and for temperatures between 300 and 386 K. The most important changes are observed for the line at 261 cm-1 issued from ν1(ZnCl4). The analysis of the wavenumber, intensity and the line width based on an order-disorder model allowed to obtain information relative to the activation energy and the correlation length. The decrease of the activation energy with increasing temperature has been interpreted in term of a change in the re-orientation motion of the anionic parts. The assumption of cluster fluctuations also allowed the critical exponents to be obtained for the transition δ = 0.011 and the correlation length ξ0 = 598 Å.

Temperature-Dependent Thermal Boundary Conductance of Monolayer MoS 2 by Raman Thermometry

DOE PAGES

Yalon, Eilam; Aslan, Ozgur Burak; Smithe, Kirby K. H.; ...

2017-10-20

The electrical and thermal behavior of nanoscale devices based on two-dimensional (2D) materials is often limited by their contacts and interfaces. Here we report the temperature-dependent thermal boundary conductance (TBC) of monolayer MoS 2 with AlN and SiO 2, using Raman thermometry with laser-induced heating. The temperature-dependent optical absorption of the 2D material is crucial in such experiments, which we characterize here for the first time above room temperature. We obtain TBC ~ 15 MW m –2 K –1 near room temperature, increasing as ~ T 0.65 in the range 300–600 K. The similar TBC of MoS 2 with themore » two substrates indicates that MoS 2 is the “softer” material with weaker phonon irradiance, and the relatively low TBC signifies that such interfaces present a key bottleneck in energy dissipation from 2D devices. As a result, our approach is needed to correctly perform Raman thermometry of 2D materials, and our findings are key for understanding energy coupling at the nanoscale.« less

Temperature-Dependent Thermal Boundary Conductance of Monolayer MoS 2 by Raman Thermometry

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

Yalon, Eilam; Aslan, Ozgur Burak; Smithe, Kirby K. H.

The electrical and thermal behavior of nanoscale devices based on two-dimensional (2D) materials is often limited by their contacts and interfaces. Here we report the temperature-dependent thermal boundary conductance (TBC) of monolayer MoS 2 with AlN and SiO 2, using Raman thermometry with laser-induced heating. The temperature-dependent optical absorption of the 2D material is crucial in such experiments, which we characterize here for the first time above room temperature. We obtain TBC ~ 15 MW m –2 K –1 near room temperature, increasing as ~ T 0.65 in the range 300–600 K. The similar TBC of MoS 2 with themore » two substrates indicates that MoS 2 is the “softer” material with weaker phonon irradiance, and the relatively low TBC signifies that such interfaces present a key bottleneck in energy dissipation from 2D devices. As a result, our approach is needed to correctly perform Raman thermometry of 2D materials, and our findings are key for understanding energy coupling at the nanoscale.« less

Quantum dynamics of the reaction H((2)S) + HeH(+)(X(1)Σ(+)) → H2(+)(X(2)Σg(+)) + He((1)S) from cold to hyperthermal energies: time-dependent wavepacket study and comparison with time-independent calculations.

PubMed

Gamallo, Pablo; Akpinar, Sinan; Defazio, Paolo; Petrongolo, Carlo

2014-08-21

We present the adiabatic quantum dynamics of the proton-transfer reaction H((2)S) + HeH(+)(X(1)Σ(+)) → H2(+)(X(2)Σg(+)) + He((1)S) on the HeH2(+) X̃(2)Σ(+) RMRCI6 (M = 6) PES of C. N. Ramachandran et al. ( Chem. Phys. Lett. 2009, 469, 26). We consider the HeH(+) molecule in the ground vibrational–rotational state and obtain initial-state-resolved reaction probabilities and the ground-state cross section σ0 and rate constant k0 by propagating time-dependent, coupled-channel, real wavepackets (RWPs) and performing a flux analysis. Three different wavepackets are propagated to describe the wide range of energies explored, from cold (0.0001 meV) to hyperthermal (1000 meV) collision energies, and in a temperature range from 0.01 to 2000 K. We compare our time-dependent results with the time-independent ones by D. De Fazio and S. Bovino et al., where De Fazio carried out benchmark coupled-channel calculations whereas Bovino et al. employed the negative imaginary potential and the centrifugal-sudden approximations. The RWP cross section is in good agreement with that by De Fazio, except at the lowest collision energies below ∼0.01 meV, where the former is larger than the latter. However, neither the RWP and De Fazio results possess the huge resonance in probability and cross section at 0.01 meV, found by Bovino et al., who also obtained a too low σ0 at high energies. Therefore, the RWP and De Fazio rate constants compare quite well, whereas that by Bovino et al. is in general lower.

Drying Temperature Dependence of Sol-gel Spin Coated Bilayer Composite ZnO/TiO2 Thin Films for Extended Gate Field Effect Transistor pH Sensor

NASA Astrophysics Data System (ADS)

Rahman, R. A.; Zulkefle, M. A.; Yusoff, K. A.; Abdullah, W. F. H.; Rusop, M.; Herman, S. H.

2018-03-01

This study presents an investigation on zinc oxide (ZnO) and titanium dioxide (TiO2) bilayer film applied as the sensing membrane for extended-gate field effect transistor (EGFET) for pH sensing application. The influences of the drying temperatures on the pH sensing capability of ZnO/TiO2 were investigated. The sensing performance of the thin films were measured by connecting the thin film to a commercial MOSFET to form the extended gates. By varying the drying temperature, we found that the ZnO/TiO2 thin film dried at 150°C gave the highest sensitivity compared to other drying conditions, with the sensitivity value of 48.80 mV/pH.

Temperature dependent structural properties and bending rigidity of pristine and defective hexagonal boron nitride

NASA Astrophysics Data System (ADS)

Thomas, Siby; Ajith, K. M.; Chandra, Sharat; Valsakumar, M. C.

2015-08-01

Structural and thermodynamical properties of monolayer pristine and defective boron nitride sheets (h-BN) have been investigated in a wide temperature range by carrying out atomistic simulations using a tuned Tersoff-type inter-atomic empirical potential. The temperature dependence of lattice parameter, radial distribution function, specific heat at constant volume, linear thermal expansion coefficient and the height correlation function of the thermally excited ripples on pristine as well as defective h-BN sheet have been investigated. Specific heat shows considerable increase beyond the Dulong-Petit limit at high temperatures, which is interpreted as a signature of strong anharmonicity present in h-BN. Analysis of the height fluctuations, < {{h}2}> , shows that the bending rigidity and variance of height fluctuations are strongly temperature dependent and this is explained using the continuum theory of membranes. A detailed study of the height-height correlation function shows deviation from the prediction of harmonic theory of membranes as a consequence of the strong anharmonicity in h-BN. It is also seen that the variance of the height fluctuations increases with defect concentration.

Observations of CH4, C2H6, and C2H2 in the stratosphere of Jupiter

NASA Technical Reports Server (NTRS)

Sada, P. V.; Bjoraker, G. L.; Jennings, D. E.; McCabe, G. H.; Romani, P. N.

1998-01-01

We have performed high-resolution spectral observations at mid-infrared wavelengths of CH4 (8.14 micrometers), C2H6 (12.16 micrometers), and C2H2 (13.45 micrometers) on Jupiter. These emission features probe the stratosphere of the planet and provide information on the carbon-based photochemical processes taking place in that region of the atmosphere. The observations were performed using our cryogenic echelle spectrometer CELESTE, in conjunction with the McMath-Pierce 1.5-m solar telescope between November 1994 and February 1995. We used the methane observations to derive the temperature profile of the jovian atmosphere in the 1-10 mbar region of the stratosphere. This profile was then used in conjunction with height-dependent mixing ratios of each hydrocarbon to determine global abundances for ethane and acetylene. The resulting mixing ratios are 3.9(+1.9)(-1.3) x 10(-6) for C2H6 (5 mbar pressure level), and 2.3 +/- 0.5 x 10(-8) for C2H2 (8 mbar pressure level), where the quoted uncertainties are derived from model variations in the temperature profile which match the methane observation uncertainties. c1998 Academic Press.

Temperature-Dependent Fermentation of d-Sorbitol in Escherichia coli O157:H7

PubMed Central

Bouvet, O. M. M.; Pernoud, S.; Grimont, P. A. D.

1999-01-01

The influence of growth temperature on the ability to ferment d-sorbitol was investigated in Escherichia coli O157:H7. It was found that O157:H7 strains have a temperature-sensitive sorbitol phenotype. d-Sorbitol transport and sorbitol-6-phosphate dehydrogenase activities were expressed in sorbitol-fermenting cells grown at 30°C but only at a low level at 40°C. Sorbitol-positive variants able to transport d-sorbitol were easily selected at 30°C from culture of Sor− E. coli O157:H7 strains. PMID:10473445

Tunneling chemical reactions D +H2→DH+H and D +DH→D2+H in solid D2-H2 and HD -H2 mixtures: An electron-spin-resonance study

NASA Astrophysics Data System (ADS)

Kumada, Takayuki

2006-03-01

Tunneling chemical reactions D +H2→DH+H and D +DH→D2+H in solid HD -H2 and D2-H2 mixtures were studied in the temperature range between 4 and 8K. These reactions were initiated by UV photolysis of DI molecules doped in these solids for 30s and followed by measuring the time course of electron-spin-resonance (ESR) intensities of D and H atoms. ESR intensity of D atoms produced by the photolysis decreases but that of H atoms increases with time. Time course of the D and H intensities has the fast and slow processes. The fast process, which finishes within ˜300s after the photolysis, is assigned to the reaction of D atom with one of its nearest-neighboring H2 molecules, D(H2)n(HD)12-n→H(H2)n-1(HD)13-n or D(H2)n(D2)12-n→H(HD )(H2)n-1(D2)12-n for 12⩾n⩾1. Rate constant for the D +H2 reaction between neighboring D atom-H2 molecule pair is determined to be (7.5±0.7)×10-3s-1 in solid HD -H2 and (1.3±0.3)×10-2s-1 in D2-H2 at 4.1K, which is very close to that calculated based on the theory of chemical reaction in gas phase by Hancock et al. [J. Chem. Phys. 91, 3492 (1989)] and Takayanagi and Sato [J. Chem. Phys. 92, 2862 (1990)]. This rate constant was found to be independent of temperature up to 7K within experimental error of ±30%. The slow process is assigned to the reaction of D atom produced in a cage fully surrounded by HD or D2 molecules, D(HD)12 or D(D2)12. This D atom undergoes the D +DH reaction with one of its nearest-neighboring HD molecules in solid HD -H2 or diffuses to the neighbor of H2 molecules to allow the D +H2 reaction in solid HD -H2 and D2-H2. The former is the main channel in solid HD -H2 below 6K where D atoms diffuse very slowly, whereas the latter dominates over the former above 6K. Rate for the reactions in the slow process is independent of temperature below 6K but increases with the increase in temperature above 6K. We found that the increase is due to the increase in hopping rate of D atoms to the neighbor of H2 molecules. Rate

Temperature dependent relaxation of interface-states in graphene on SiO2

NASA Astrophysics Data System (ADS)

Singh, Anil Kumar; Gupta, Anjan Kumar

2018-04-01

We have studied the evolution of resistance relaxation with temperature in graphene field effect transistor on SiO2. At room temperature, piranha-cleaned-SiO2 devices show slow resistance relaxation while IPA-cleaned-SiO2 devices do not. With cooling the former devices show a decrease in magnitude and time constant of the slow relaxation and it becomes negligible at 250K. Relaxation study at elevated temperature of the IPA-cleaned devices show a gate voltage polarity dependent time constant with respect to the charge neutrality point but it remains almost independent of temperature. The magnitude of relaxation increases with temperature. Further, after annealing at elevated temperature, we found that the relaxation times become independent of gate voltage polarity and its magnitude becomes very small. These observations are discussed using increase in diffusion of interface-species with temperature.

Temperature Dependence of the Oxygen Reduction Mechanism in Nonaqueous Li–O 2 Batteries

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

Liu, Bin; Xu, Wu; Zheng, Jianming

The temperature dependence of the oxygen reduction mechanism in Li-O 2 batteries was investigated using carbon nanotube-based air electrodes and 1,2-dimethoxyethane-based electrolyte within a temperature range of 20C to 40C. It is found that the discharge capacity of the Li-O 2 batteries decreases from 7,492 mAh g -1 at 40C to 2,930 mAh g -1 at 0C. However, a sharp increase in capacity was found when the temperature was further decreased and a very high capacity of 17,716 mAh g -1 was observed at 20C at a current density of 0.1 mA cm-2. When the temperature increases from 20C tomore » 40C, the morphologies of the Li 2O 2 formed varied from ultra-small spherical particles to small flakes and then to large flake-stacked toroids. The lifetime of superoxide and the solution pathway play a dominate role on the battery capacity in the temperature range of -20C to 0C, but the electrochemical kinetics of oxygen reduction and the surface pathway dominate the discharge behavior in the temperature range of 0C to 40C. These findings provide fundamental understanding on the temperature dependence of oxygen reduction process in a Li-O 2 battery and will enable a more rational design of Li-O 2 batteries.« less

Amino acid modified Ni catalyst exhibits reversible H2 oxidation/production over a broad pH range at elevated temperatures

DOE PAGES

Dutta, Arnab; DuBois, Daniel L.; Roberts, John A.; ...

2014-11-18

Hydrogenases interconvert H2 and protons at high rates and with high energy efficiencies, providing inspiration for the development of molecular catalysts. Studies designed to determine how the protein scaffold can influence a catalytically active site has led to the synthesis of amino acid derivatives, [Ni(PCy2NAmino acid2)2]2+ (CyAA), of [Ni(PR2NR'2)2]2+ complexes. It is shown that these CyAA derivatives can catalyze fully reversible H2 production/oxidation, a feature reminiscent of enzymes. The reversibility is achieved in acidic aqueous solutions, 0.25% H2/Ar, and elevated temperatures (tested up to 348 K) for the glycine (CyGly), arginine (CyArg), and arginine methyl ester (CyArgOMe) derivatives. As expectedmore » for a reversible process, the activity is dependent upon H2 and proton concentration. CyArg is significantly faster in both directions than the other two derivatives (~300 s-1 H2 production and 20 s-1 H2 oxidation; pH=1, 348 K). The significantly slower rates for CyArgOMe (35 s-1 production and 7 s-1 oxidation) compared to CyArg suggests an important role for the COOH group during catalysis. That CyArg is faster than CyGly (3 s-1 production and 4 s-1 oxidation under the same conditions) suggests that the additional structural features imparted by the guanidinium groups facilitate fast and reversible H2 addition/release. These observations demonstrate that appended, outer coordination sphere amino acids work in synergy with the active site and can play an equally important role for synthetic molecular electrocatalysts as the protein scaffold does for redox active enzymes. This work was funded by the Office of Science Early Career Research Program through the US DOE, BES (AD, WJS), and the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US DOE, BES (DLD, JASR). PNNL is operated by Battelle for the US DOE.« less

An isopiestic study of aqueous NaBr and KBr at 50 °C: Chemical equilibrium model of solution behavior and solubility in the NaBr-H 2O, KBr-H 2O and Na-K-Br-H 2O systems to high concentration and temperature

NASA Astrophysics Data System (ADS)

Christov, Christomir

2007-07-01

The isopiestic method has been used to determine the osmotic coefficients of the binary solutions NaBr-H 2O (from 0.745 to 5.953 mol kg -1) and KBr-H 2O (from 0.741 to 5.683 mol kg -1) at the temperature t = 50 °C. Sodium chloride solutions have been used as isopiestic reference standards. The isopiestic results obtained have been combined with all other experimental thermodynamic quantities available in literature (osmotic coefficients, water activities, bromide mineral's solubilities) to construct a chemical model that calculates solute and solvent activities and solid-liquid equilibria in the NaBr-H 2O, KBr-H 2O and Na-K-Br-H 2O systems from dilute to high solution concentration within the 0-300 °C temperature range. The Harvie and Weare [Harvie C., and Weare J. (1980) The prediction of mineral solubilities in naturalwaters: the Na-K-Mg-Ca-Cl-SO 4-H 2O system from zero to high concentration at 25 °C. Geochim. Cosmochim. Acta44, 981-997] solubility modeling approach, incorporating their implementation of the concentration-dependent specific interaction equations of Pitzer [Pitzer K. (1973) Thermodynamics of electrolytes. I. Theoretical basis and general equations. J. Phys. Chem.77, 268-277] is employed. The model for binary systems is validated by comparing activity coefficient predictions with those given in literature, and not used in the parameterization process. Limitations of the mixed solutions model due to data insufficiencies are discussed. This model expands the variable temperature sodium-potassium model of Greenberg and Moller [Greenberg J., and Moller N. (1989) The prediction of mineral solubilities in natural waters: a chemical equilibrium model for the Na-K-Ca-Cl-SO 4-H 2O system to high concentration from 0 to 250 °C. Geochim. Cosmochim. Acta53, 2503-2518] by evaluating Br - pure electrolyte and mixing solution parameters and the chemical potentials of three bromide solid phases: NaBr-2H 2O (cr), NaBr (cr) and KBr (cr).

Gibbs free energy of reactions involving SiC, Si3N4, H2, and H2O as a function of temperature and pressure

NASA Technical Reports Server (NTRS)

Isham, M. A.

1992-01-01

Silicon carbide and silicon nitride are considered for application as structural materials and coating in advanced propulsion systems including nuclear thermal. Three-dimensional Gibbs free energy were constructed for reactions involving these materials in H2 and H2/H2O. Free energy plots are functions of temperature and pressure. Calculations used the definition of Gibbs free energy where the spontaneity of reactions is calculated as a function of temperature and pressure. Silicon carbide decomposes to Si and CH4 in pure H2 and forms a SiO2 scale in a wet atmosphere. Silicon nitride remains stable under all conditions. There was no apparent difference in reaction thermodynamics between ideal and Van der Waals treatment of gaseous species.

Material dependence of 2H(d,p)3H cross section at the very low energies

NASA Astrophysics Data System (ADS)

Kılıç, Ali İhsan; Czerski, Konrad; Kuştan-Kılıç, Fadime; Targosz-Sleczka, Natalia; Weissbach, Daniel; Huke, Armin; Ruprecht, Götz

2017-09-01

Calculations of the material dependence of 2H(d,p)3H cross section and neutron-to-proton branching ratio of d+d reactions have been performed including a concept of the 0+ threshold single particle resonance. The resonance has been assumed to explain the enhanced electron screening effect observed in the d+d reaction for different metallic targets. Here, we have included interference effects between the flat and resonance part of the cross section, which allowed us to enlighten observed suppression of the neutron channel in some metals such as Sr and Li. Since the position of the resonance depends on the screening energy that strongly depends on the local electron density. The resonance width, observed for the d+d reactions in the very hygroscopic metals (Sr and Li) and therefore probably contaminated by oxides, should be much larger than for other metals. Thus, the interference term of the cross section depending on the total resonance width provides the material dependences.

Rate constants for CF{sub 3} + H{sub 2} {r_arrow} CF{sub 3}H + H and CF{sub 3}H + H {r_arrow} CF{sub 3} + H{sub 2} reactions in the temperature range 1100--1600 K

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

Hranisavljevic, J.; Michael, J.V.

1998-09-24

The shock tube technique coupled with H-atom atomic resonance absorption spectrometry has been used to study the reactions (1) CF{sub 3} + H{sub 2} {r_arrow} CF{sub 3}H + H and (2) CF{sub 3}H + H {r_arrow} CF{sub 3} + H{sub 2} over the temperature ranges 1168--1673 K and 1111--1550 K, respectively. The results can be represented by the Arrhenius expressions k{sub 1} = 2.56 {times} 10{sup {minus}11} exp({minus}8549K/T) and k{sub 2} = 6.13 {times} 10{sup {minus}11} exp({minus}7364K/T), both in cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. Equilibrium constants were calculated from the two Arrhenius expressions in the overlapping temperature range, andmore » good agreement was obtained with the literature values. The rate constants for reaction 2 were converted into rate constants for reaction 1 using literature equilibrium constants. These data are indistinguishable from direct k{sub 1} measurements, and an Arrhenius fit for the joint set is k{sub 1} = 1.88 {times} 10{sup {minus}11} exp({minus}8185K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. The CF{sub 3} + H{sub 2} {r_arrow} CF{sub 3}H + H reaction was further modeled using conventional transition-state theory, which included ab initio electronic structure determinations of reactants, transition state, and products.« less

Electron-temperature dependence of dissociative recombination of electrons with N2/+/.N2 dimer ions

NASA Technical Reports Server (NTRS)

Whitaker, M.; Biondi, M. A.; Johnsen, R.

1981-01-01

The variation with electron temperature of the dissociative recombination of electrons with N2(+).N2 dimer ions is investigated in light of the importance of such ions in the lower ionosphere and in laser plasmas. Dissociative recombination coefficients were determined by means of a microwave afterglow mass spectrometer technique for electron temperatures from 300-5600 K and an ion and neutral temperature of 300 K. The recombination coefficient is found to be proportional to the -0.41 power of the electron temperature in this range, similar to that observed for the CO(+).CO dimer ion and consistent with the expected energy dependence for a fast dissociative process.

Broadening of spectral lines of CO2, N2O , H2CO, HCN, and H2S by pressure of gases dominant in planetary atmospheres (H2, He and CO2)

NASA Astrophysics Data System (ADS)

Samuels, Shanelle; Gordon, Iouli; Tan, Yan

2018-01-01

HITRAN1,2 is a compilation of spectroscopic parameters that a variety of computer codes use to predict and simulate the transmission and emission of light in planetary atmospheres. The goal of this project is to add to the potential of the HITRAN database towards the exploration of the planetary atmospheres by including parameters describing broadening of spectral lines by H2, CO2, and He. These spectroscopic data are very important for the study of the hydrogen and helium-rich atmospheres of gas giants as well as rocky planets with volcanic activities, including Venus and Mars, since their atmospheres are dominated by CO2. First step in this direction was accomplished by Wilzewski et al.3 where this was done for SO2, NH3, HF, HCl, OCS and C2H2. The molecules investigated in this work were CO2, N2O, H2CO, HCN and H2S. Line-broadening coefficients, line shifts and temperature-dependence exponents for transitions of these molecules perturbed by H2, CO2 and He have been assembled from available peer-reviewed experimental and theoretical sources. The data was evaluated and the database was populated with these data and their extrapolations/interpolations using semi-empirical models that were developed to this end.Acknowledgements: Financial support from NASA PDART grant NNX16AG51G and the Smithsonian Astrophysical Observatory Latino Initiative Program from the Latino Initiatives Pool, administered by the Smithsonian Latino Center is gratefully acknowledged.References: 1. HITRAN online http://hitran.org/2. Gordon, I.E., Rothman, L.S., Hill, C., Kochanov, R.V., Tan, Y., et al., 2017. The HITRAN2016 Molecular Spectroscopic Database. J. Quant. Spectrosc. Radiat. Transf. doi:10.1016/j.jqsrt.2017.06.0383. Wilzewski, J.S., Gordon, I.E., Kochanov, R. V., Hill, C., Rothman, L.S., 2016. H2, He, and CO2 line-broadening coefficients, pressure shifts and temperature-dependence exponents for the HITRAN database. Part 1: SO2, NH3, HF, HCl, OCS and C2H2. J. Quant. Spectrosc. Radiat

Surface electronic states of low-temperature H-plasma-exposed Ge(100)

NASA Astrophysics Data System (ADS)

Cho, Jaewon; Nemanich, R. J.

1992-11-01

The surface of low-temperature H-plasma-cleaned Ge(100) was studied by angle-resolved UV-photoemission spectroscopy and low-energy electron diffraction (LEED). The surface was prepared by an ex situ preclean followed by an in situ H-plasma exposure at a substrate temperature of 150-300 °C. Auger-electron spectroscopy indicated that the in situ H-plasma clean removed the surface contaminants (carbon and oxygen) from the Ge(100) surface. The LEED pattern varied from a 1×1 to a sharp 2×1, as the substrate temperature was increased. The H-induced surface state was identified at ~5.6 eV below EF, which was believed to be mainly due to the ordered or disordered monohydride phases. The annealing dependence of the spectra showed that the hydride started to dissociate at a temperature of 190 °C, and the dangling-bond surface state was identified. A spectral shift upon annealing indicated that the H-terminated surfaces were unpinned. After the H-plasma clean at 300 °C the dangling-bond surface state was also observed directly with no evidence of H-induced states.

Temperature dependence of the water vapor continuum absorption in the 3-5 μm spectral region

NASA Astrophysics Data System (ADS)

Klimeshina, T. E.; Rodimova, O. B.

2013-04-01

Asymptotic line wing theory allows one to construct the line shape describing the frequency and temperature dependence of the self-broadened H2O continuum in the 3-5 μm spectral region obtained experimentally by CAVIAR and NIST. The H2O transmission functions are adequately described as well, using this line shape up to temperatures of ˜675 K and pressures of ˜10 atm.

Ab initio molecular dynamics study of fluid H2O-CO2 mixture in broad pressure-temperature range

NASA Astrophysics Data System (ADS)

Fu, Jie; Zhao, Jijun; Plyasunov, Andrey V.; Belonoshko, Anatoly B.

2017-11-01

Properties of H2O and CO2 fluid and their mixtures under extreme pressures and temperatures are poorly known yet critically important in a number of applications. Several hundreds of first-principles molecular dynamics (FPMD) runs have been performed to obtain the pressure-volume-temperature (P-V-T) data on supercritical H2O, CO2, and H2O-CO2 mixtures. The pressure-temperature (P-T) range are from 0.5 GPa to 104 GPa (48.5 GPa for CO2) and from 600 K to 4000 K. Based on these data, we evaluate several existing equations of state (EOS) for the fluid H2O, CO2, and H2O-CO2 mixture. The results show that the EOS for H2O from Belonoshko et al. [Geochim. Cosmochim. Acta 55, 381-387; Geochim. Cosmochim. Acta 55, 3191-3208; Geochim. Cosmochim. Acta 56, 3611-3626; Comput. Geosci. 18, 1267-1269] not only can be used in the studied P-T range but also is accurate enough to be used for prediction of P-V-T data. In addition, IAPWS-95 EOS for H2O shows excellent extrapolation behavior beyond 1.0 GPa and 1273 K. However, for the case of CO2, none of the existing EOS produces data in agreement with the FPMD results. We created new EOS for CO2. The precision of the new EOS is tested by comparison to the calculated P-V-T data, fugacity coefficient of the CO2 fluid derived from high P-T experimental data as well as to the (very scarce) experimental volumetric data in the high P-T range. On the basis of our FPMD data we created a new EOS for H2O-CO2 mixture. The new EOS for the mixture is in reasonable agreement with experimental data.

Low-temperature methyl group dynamics of hexamethylbenzene in crystalline and glassy matrices as studied by 2H NMR

NASA Astrophysics Data System (ADS)

Börner, K.; Diezemann, G.; Rössler, E.; Vieth, H. M.

1991-07-01

2H NMR spectra of hexamethylbenzene (HMB) in protonated crystalline and amorphous matrices at low temperatures are presented. All spectra reveal lineshape changes which can be attributed to methyl group tunnelling. Compared to neat HMB, a drastic increase of the tunnelling frequency is found for all systems. This indicates that the hindering potential originates predominantly from intermolecular forces. We studied the temperature dependence of these spectra and the spin-lattice relaxation in order to exclude a distribution of motional correlation times describing a thermally activated process. In addition, we find a distortion of the methyl tetrahedron.

Leakage current conduction, hole injection, and time-dependent dielectric breakdown of n-4H-SiC MOS capacitors during positive bias temperature stress

NASA Astrophysics Data System (ADS)

Samanta, Piyas; Mandal, Krishna C.

2017-01-01

The conduction mechanism(s) of gate leakage current JG through thermally grown silicon dioxide (SiO2) films on the silicon (Si) face of n-type 4H-silicon carbide (4H-SiC) has been studied in detail under positive gate bias. It was observed that at an oxide field above 5 MV/cm, the leakage current measured up to 303 °C can be explained by Fowler-Nordheim (FN) tunneling of electrons from the accumulated n-4H-SiC and Poole-Frenkel (PF) emission of trapped electrons from the localized neutral traps located at ≈2.5 eV below the SiO2 conduction band. However, the PF emission current IPF dominates the FN electron tunneling current IFN at oxide electric fields Eox between 5 and 10 MV/cm and in the temperature ranging from 31 to 303 °C. In addition, we have presented a comprehensive analysis of injection of holes and their subsequent trapping into as-grown oxide traps eventually leading to time-dependent dielectric breakdown during electron injection under positive bias temperature stress (PBTS) in n-4H-SiC metal-oxide-silicon carbide structures. Holes were generated in the heavily doped n-type polycrystalline silicon (n+-polySi) gate (anode) as well as in the oxide bulk via band-to-band ionization by the hot-electrons depending on their energy and SiO2 film thickness at Eox between 6 and 10 MV/cm (prior to the intrinsic oxide breakdown field). Transport of hot electrons emitted via both FN and PF mechanisms was taken into account. On the premise of the hole-induced oxide breakdown model, the time- and charge-to-breakdown ( tBD and QBD ) of 8.5 to 47 nm-thick SiO2 films on n-4H-SiC were estimated at a wide range of temperatures. tBD follows the Arrhenius law with activation energies varying inversely with initial applied constant field Eox supporting the reciprocal field ( 1 /E ) model of breakdown irrespective of SiO2 film thicknesses. We obtained an excellent margin (6.66 to 6.33 MV/cm at 31 °C and 5.11 to 4.55 MV/cm at 303 °C) of normal operating field for a 10

Reversible clustering of pH- and temperature-responsive Janus magnetic nanoparticles.

PubMed

Isojima, Tatsushi; Lattuada, Marco; Vander Sande, John B; Hatton, T Alan

2008-09-23

Janus nanoparticles have been synthesized consisting of approximately 5 nm magnetite nanoparticles coated on one side with a pH-dependent and temperature-independent polymer (poly(acrylic acid), PAA), and functionalized on the other side by a second (tail) polymer that is either a pH-independent polymer (polystyrene sodium sulfonate, PSSNa) or a temperature-dependent polymer (poly(N-isopropyl acrylamide), PNIPAM). These Janus nanoparticles are dispersed stably as individual particles at high pH values and low temperatures, but can self-assemble at low pH values (PSSNa) or at high temperatures (>31 degrees C) (PNIPAM) to form stable dispersions of clusters of approximately 80-100 nm in hydrodynamic diameter. The Janus nanoparticle compositions were verified using FTIR and XPS, and their structures observed directly by TEM. Their clustering behavior is analyzed by dynamic light scattering and zeta potential measurements.

Temperature dependence of water-water and ion-water correlations in bulk water and electrolyte solutions probed by femtosecond elastic second harmonic scattering

NASA Astrophysics Data System (ADS)

Chen, Yixing; Dupertuis, Nathan; Okur, Halil I.; Roke, Sylvie

2018-06-01

The temperature dependence of the femtosecond elastic second harmonic scattering (fs-ESHS) response of bulk light and heavy water and their electrolyte solutions is presented. We observe clear temperature dependent changes in the hydrogen (H)-bond network of water that show a decrease in the orientational order of water with increasing temperature. Although D2O has a more structured H-bond network (giving rise to more fs-ESHS intensity), the relative temperature dependence is larger in H2O. The changes are interpreted in terms of the symmetry of H-bonds and are indicators of nuclear quantum effects. Increasing the temperature in electrolyte solutions decreases the influence of the total electrostatic field from ions on the water-water correlations, as expected from Debye-Hückel theory, since the Debye length becomes longer. The effects are, however, 1.9 times (6.3 times) larger than those predicted for H2O (D2O). Since fs-ESHS responses can be computed from known molecular coordinates, our observations provide a unique opportunity to refine quantum mechanical models of water.

Frequency and temperature dependent dielectric properties of TiO2-V2O5 nanocomposites

NASA Astrophysics Data System (ADS)

Ray, Apurba; Roy, Atanu; De, Sayan; Chatterjee, Souvik; Das, Sachindranath

2018-03-01

In this manuscript, we have reported the crystal structure, dielectric response, and transport phenomenon of TiO2-V2O5 nanocomposites. The nanocomposites were synthesized using a sol-gel technique having different molar ratios of Ti:V (10:10, 10:15, and 10:20). The phase composition and the morphology have been studied using X-ray diffraction and field emission scanning electron microscope, respectively. The impedance spectroscopy studies of the three samples over a wide range of temperature (50 K-300 K) have been extensively described using the internal barrier layer capacitor model. It is based on the contribution of domain and domain boundary, relaxations of the materials, which are the main crucial factors for the enhancement of the dielectric response. The frequency dependent ac conductivity of the ceramics strongly obeys the well-known Jonscher's power law, and it has been clearly explained using the theory of jump relaxation model. The temperature dependent bulk conductivity is fairly recognized to the variable-range hopping of localized polarons. The co-existence of mixed valence state of Ti ions (Ti3+ and Ti4+) in the sample significantly contributes to the change of dielectric property. The overall study of dielectric response explains that the dielectric constant and the dielectric loss are strongly dependent on temperature and frequency and decrease with an increase of frequency as well as temperature.

Unraveling the Transcriptional Basis of Temperature-Dependent Pinoxaden Resistance in Brachypodium hybridum

PubMed Central

Matzrafi, Maor; Shaar-Moshe, Lidor; Rubin, Baruch; Peleg, Zvi

2017-01-01

Climate change endangers food security and our ability to feed the ever-increasing human population. Weeds are the most important biotic stress, reducing crop-plant productivity worldwide. Chemical control, the main approach for weed management, can be strongly affected by temperature. Previously, we have shown that temperature-dependent non-target site (NTS) resistance of Brachypodium hybridum is due to enhanced detoxification of acetyl-CoA carboxylase inhibitors. Here, we explored the transcriptional basis of this phenomenon. Plants were characterized for the transcriptional response to herbicide application, high-temperature and their combination, in an attempt to uncover the genetic basis of temperature-dependent pinoxaden resistance. Even though most of the variance among treatments was due to pinoxaden application (61%), plants were able to survive pinoxaden application only when grown under high-temperatures. Biological pathways and expression patterns of members of specific gene families, previously shown to be involved in NTS metabolic resistance to different herbicides, were examined. Cytochrome P450, glucosyl transferase and glutathione-S-transferase genes were found to be up-regulated in response to pinoxaden application under both control and high-temperature conditions. However, biological pathways related to oxidation and glucose conjugation were found to be significantly enriched only under the combination of pinoxaden application and high-temperature. Analysis of reactive oxygen species (ROS) was conducted at several time points after treatment using a probe detecting H2O2/peroxides. Comparison of ROS accumulation among treatments revealed a significant reduction in ROS quantities 24 h after pinoxaden application only under high-temperature conditions. These results may indicate significant activity of enzymatic ROS scavengers that can be correlated with the activation of herbicide-resistance mechanisms. This study shows that up-regulation of genes

Measurement and modeling of temperature-dependent hydrogen embrittlement of chromium-molybdenum steel to enable fitness-for-service life prediction

NASA Astrophysics Data System (ADS)

Al-Rumaih, Abdullah M.

Thick-wall vessels in petrochemical applications, fabricated from 2.25Cr-1Mo steel, operate in pressurized H2 at elevated temperature for more than 20 years. There is a concern regarding the interactive effects of temper-embrittlement and hydrogen-embrittlement on fitness-for-service during startup/shutdown near ambient temperatures. The database of degraded material properties is inadequate to enable accurate assessment. Specifically, H loss from small fracture mechanics specimens was substantial during either long-term or elevated temperature experiments. In addition, the influence of temperature on H-embrittlement of Cr-Mo steel is not fundamentally understood. The objectives of this research are to (1) design a novel laboratory method to retain H in small fracture mechanics specimens, (2) characterize the temperature dependent internal hydrogen embrittlement (IHE) of Cr-Mo weld metal using the developed method, and (3) model H distribution near a stressed crack tip in a H-trap laden bainitic microstructure to fundamentally understand the temperature dependent IHE. The new slotted CT specimen approach, with 3.0 wppm total H produced on the slot surface from acidified thiosulfate charging, quantitatively characterized the temperature dependent threshold stress intensity (KIH and K TH) and kinetics (da/dtRISE and da/dtHOLD) of IHE in Cr-Mo weld metal during both rising and slowly falling K loading. IHE was produced successfully and damage was more severe during rising K loading due to the role of crack tip plasticity in H cracking of low to moderate strength steel. The critical temperature at which embrittlement ceased is in the range 45°C < Tc ≤ 60°C for the weld metal and H content studied. This method provides a useful new tool to generate fracture mechanics based fitness-for-service data. A three-dimensional finite element diffusion model, that accounts for the effect of crack tip plasticity and trapping on H transport, established K, dK/dt and temperature

Phonon-mediated nuclear spin relaxation in H2O

NASA Astrophysics Data System (ADS)

Yamakawa, Koichiro; Azami, Shinya; Arakawa, Ichiro

2017-03-01

A theoretical model of the phonon-mediated nuclear spin relaxation in H2O trapped by cryomatrices has been established for the first time. In order to test the validity of this model, we measured infrared spectra of H2O trapped in solid Ar, which showed absorption peaks due to rovibrational transitions of ortho- and para-H2O in the spectral region of the bending vibration. We monitored the time evolution of the spectra and analyzed the rotational relaxation associated with the nuclear spin flip to obtain the relaxation rates of H2O at temperatures of 5-15 K. Temperature dependence of the rate is discussed in terms of the devised model.

The TAED/H2O2/NaHCO3 system as an approach to low-temperature and near-neutral pH bleaching of cotton.

PubMed

Long, Xiaoxia; Xu, Changhai; Du, Jinmei; Fu, Shaohai

2013-06-05

A low-temperature and near-neutral pH bleaching system was conceived for cotton by incorporating TAED, H2O2 and NaHCO3. The TAED/H2O2/NaHCO3 system was investigated and optimized for bleaching of cotton using a central composite design (CCD) combined with response surface methodology (RSM). CCD experimental data were fitted to create a response surface quadratic model (RSQM) describing the degree of whiteness of bleached cotton fabric. Analysis of variance for the RSQM revealed that temperature was the most significant variable, followed by [TAED] and time, while [NaHCO3] was insignificant. An effective system was conducted by adding 5.75 g L(-1) TAED together with H2O2 and NaHCO3 at a molar ratio of 1:2.4:2.8 and applied to bleaching of cotton at 70 °C for 40 min. Compared to a commercial bleaching method, the TAED/H2O2/NaHCO3 system provided cotton with comparable degree of whiteness, slightly inferior water absorbency and acceptable dyeability, but had competitive advantage in protecting cotton from severe chemical damage in bleaching. Copyright © 2013 Elsevier Ltd. All rights reserved.

LOW-TEMPERATURE ION TRAP STUDIES OF N{sup +}({sup 3} P{sub ja} ) + H{sub 2}(j) {yields} NH{sup +} + H

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

Zymak, I.; Hejduk, M.; Mulin, D.

2013-05-01

Using a low-temperature 22-pole ion trap apparatus, detailed measurements for the title reaction have been performed between 10 K and 100 K in order to get some state specific information about this fundamental hydrogen abstraction process. The relative population of the two lowest H{sub 2} rotational states, j = 0 and 1, has been varied systematically. NH{sup +} formation is nearly thermo-neutral; however, to date, the energetics are not known with the accuracy required for low-temperature astrochemistry. Additional complications arise from the fact that, so far, there is no reliable theoretical or experimental information on how the reactivity of themore » N{sup +} ion depends on its fine-structure (FS) state {sup 3} P{sub ja} . Since in the present trapping experiment, thermalization of the initially hot FS population competes with hydrogen abstraction, the evaluation of the decay of N{sup +} ions over long storage times and at various He and H{sub 2} gas densities provides information on these processes. First assuming strict adiabatic behavior, a set of state specific rate coefficients is derived from the measured thermal rate coefficients. In addition, by recording the disappearance of the N{sup +} ions over several orders of magnitude, information on nonadiabatic transitions is extracted including FS-changing collisions.« less

Phase Equilibria and Transport Properties in the Systems AgNO3/RCN/H2O. R = CH3, C2H5, C3H7, C4H,, C6H5, and C6H5CH2

NASA Astrophysics Data System (ADS)

Das, Surjya P.; Wittekopf, Burghard; Weil, Konrad G.

1988-11-01

Silver nitrate can form homogeneous liquid phases with some organic nitriles and water, even when there is no miscibility between the pure liquid components. We determined the shapes of the single phase regions in the ternary phase diagram for the following systems: silver nitrate /RCN /H2O with R =CH3, C3H7, C6H5, and C6H5CH2 at room temperature and for R =C6H5 also at 60 °C and O °C. Furthermore we studied kinematic viscosities, electrical conductivities, and densities of mixtures containing silver nitrate, RCN, and water with the mole ratios X /4 /1 (0.2≦ X ≦S 3.4). In these cases also R = C2H5 and C4H9 were studied. The organic nitriles show different dependences of viscosity and conductivity on the silver nitrate content from the aliphatic ones.

Wavelength-modulation spectroscopy near 1.4 µm for measurements of H2O and temperature in high-pressure and -temperature gases

NASA Astrophysics Data System (ADS)

Goldenstein, C. S.; Spearrin, R. M.; Schultz, I. A.; Jeffries, J. B.; Hanson, R. K.

2014-05-01

The development, validation and demonstration of a two-color tunable diode laser (TDL) absorption sensor for measurements of temperature and H2O in high-pressure and high-temperature gases are presented. This sensor uses first-harmonic-normalized wavelength-modulation spectroscopy with second-harmonic detection (WMS-2f/1f) to account for non-absorbing transmission losses and emission encountered in harsh, high-pressure environments. Two telecommunications-grade TDLs were used to probe H2O absorption transitions near 1391.7 and 1469.3 nm. The lasers were frequency-multiplexed and modulated at 160 and 200 kHz to enable a measurement bandwidth up to 30 kHz along a single line-of-sight. In addition, accurate measurements are enabled at extreme conditions via an experimentally derived spectroscopic database. This sensor was validated under low-absorbance (<0.05) conditions in shock-heated H2O-N2 mixtures at temperatures and pressures from 700 to 2400 K and 2 to 25 atm. There, this sensor recovered the known temperature and H2O mole fraction with a nominal accuracy of 2.8% and 4.7% RMS, respectively. Lastly, this sensor resolved expected transients with high bandwidth and high precision in a reactive shock tube experiment and a pulse detonation combustor.

Distance-dependent radiation chemistry: Oxidation versus hydrogenation of CO in electron-irradiated H2O/CO/H2O ices

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

Petrik, Nikolay G.; Monckton, Rhiannon J.; Koehler, Sven

Electron-stimulated oxidation of CO in layered H2O/CO/H2O ices was investigated with infrared reflection-absorption spectroscopy (IRAS) as function of the distance of the CO layer from the water/vacuum interface. The results show that while both oxidation and reduction reactions occur within the irradiated water films, there are distinct regions where either oxidation or reduction reactions are dominant. At depths less than ~ 15 ML, CO oxidation dominates over the sequential hydrogenation of CO to methanol (CH3OH), and CO2 is the major product of CO oxidation, consistent with previous observations. At its highest yield, CO2 accounts for ~45% of all the reactedmore » CO. Another oxidation product is identified as the formate anion (HCO2-). In contrast, for CO buried more than ~ 35 ML below the water/vacuum interface, the CO-to-methanol conversion efficiency is close to 100%. Production of CO2 and formate are not observed for the more deeply buried CO layers, where hydrogenation dominates. Experiments with CO dosed on pre-irradiated ASW samples suggest that OH radicals are primarily responsible for the oxidation reactions. Possible mechanisms of CO oxidation, involving primary and secondary processes of water radiolysis at low temperature, are discussed. The observed distance-dependent radiation chemistry results from the higher mobility of hydrogen atoms that are created by the interaction of the 100 eV electrons with the water films. These hydrogen atoms, which are primarily created at or near the water/vacuum interface, can desorb from or diffuse into the water films, while the less-mobile OH radicals remain in the near-surface zone resulting in preferential oxidation reactions there. The diffusing hydrogen atoms are responsible for the hydrogenation reactions that are dominant for the more deeply buried CO layers.« less

First-principles binary diffusion coefficients for H, H 2 and four normal alkanes + N 2

DOE PAGES

Jasper, Ahren W.; Kamarchik, Eugene; Miller, James A.; ...

2014-09-30

Collision integrals related to binary (dilute gas) diffusion are calculated classically for six species colliding with N 2. The most detailed calculations make no assumptions regarding the complexity of the potential energy surface, and the resulting classical collision integrals are in excellent agreement with previous semiclassical results for H + N 2 and H 2 + N 2 and with recent experimental results for C n H 2n+2 + N 2, n = 2–4. The detailed classical results are used to test the accuracy of three simplifying assumptions typically made when calculating collision integrals: (1) approximating the intermolecular potential asmore » isotropic, (2) neglecting the internal structure of the colliders (i.e., neglecting inelasticity), and (3) employing unphysical R –12 repulsive interactions. The effect of anisotropy is found to be negligible for H + N 2 and H 2 + N 2 (in agreement with previous quantum mechanical and semiclassical results for systems involving atomic and diatomic species) but is more significant for larger species at low temperatures. For example, the neglect of anisotropy decreases the diffusion coefficient for butane + N 2 by 15% at 300 K. The neglect of inelasticity, in contrast, introduces only very small errors. Approximating the repulsive wall as an unphysical R –12 interaction is a significant source of error at all temperatures for the weakly interacting systems H + N 2 and H 2 + N 2, with errors as large as 40%. For the normal alkanes in N 2, which feature stronger interactions, the 12/6 Lennard–Jones approximation is found to be accurate, particularly at temperatures above –700 K where it predicts the full-dimensional result to within 5% (although with somewhat different temperature dependence). Overall, the typical practical approach of assuming isotropic 12/6 Lennard–Jones interactions is confirmed to be suitable for combustion applications except for weakly interacting systems, such as H + N 2. For these systems, anisotropy

Influence of H2O on Liquidus Temperatures of Primitive Basalts and Olivine-Liquid Thermometry.

NASA Astrophysics Data System (ADS)

Medard, E.; Grove, T. L.

2005-12-01

We have undertaken a systematic experimental study aimed at understanding the effect of water on olivine liquidus temperatures of primitive basalts. Experiments have been performed on a primitive tholeiitic basalt from Medicine Lake Volcano, California (sample 82-72f, Bartels et al. 1991). The dry liquidus has been characterized from 0.1 MPa to 1.2 GPa. The wet liquidus has been constrained to within 15 °C using water-saturated experiments performed in a MHC externally heated pressure vessel. Preliminary results show that the olivine-liquidus depression (i.e., the difference between dry and water-bearing liquidus) is essentially a linear function of the water content of the melt: ΔT = 560  X(HO0.5), where X(HO0.5) is the mole fraction of water, calculated on a single-cation oxide basis. For 82-72f, this roughly translates into a 30 °C / wt% H2O depression. Simple systems (e.g., diopside/H2O, albite/H2O) suggest that melt structure / composition may have an influence on H2O liquidus depression, and this potential influence is currently under investigation. Experimental phase equilibria and thermobarometry of primitive basalts provide the primary evidence for estimating melting conditions and thermal structures in the Earth's mantle. Assessing the influence of H2O is critical, because it is the dominant volatile component involved in igneous processes, and it has been shown to cause a significant reduction in liquidus temperatures. However, recent model parameterizations vary from very large effects at low H2O contents (about 75 °C at 1 wt% H2O, Falloon and Danyushevsky 2000) to linear effect of H2O vs liquidus temperature (about 25 °C at 1 wt% H2O, Sugawara 2000). Our experimental determination more closely approximates the latter model. A key consequence is that the presence of small amounts of water in MORB magmas (< 1wt%) will only have a very small effect (< 30 °C) on liquidus temperature determination for mid-ocean-ridges. For magmas that are more

Chitosan-phosphotungstic acid complex as membranes for low temperature H2-O2 fuel cell

NASA Astrophysics Data System (ADS)

Santamaria, M.; Pecoraro, C. M.; Di Quarto, F.; Bocchetta, P.

2015-02-01

Free-standing Chitosan/phosphotungstic acid polyelectrolyte membranes were prepared by an easy and fast in-situ ionotropic gelation process performed at room temperature. Scanning electron microscopy was employed to study their morphological features and their thickness as a function of the chitosan concentration. The membrane was tested as proton conductor in low temperature H2-O2 fuel cell allowing to get peak power densities up to 350 mW cm-2. Electrochemical impedance measurements allowed to estimate a polyelectrolyte conductivity of 18 mS cm-1.

Water Ice Radiolytic O2, H2, and H2O2 Yields for Any Projectile Species, Energy, or Temperature: A Model for Icy Astrophysical Bodies

NASA Astrophysics Data System (ADS)

Teolis, B. D.; Plainaki, C.; Cassidy, T. A.; Raut, U.

2017-10-01

O2, H2, and H2O2 radiolysis from water ice is pervasive on icy astrophysical bodies, but the lack of a self-consistent, quantitative model of the yields of these water products versus irradiation projectile species and energy has been an obstacle to estimating the radiolytic oxidant sources to the surfaces and exospheres of these objects. A major challenge is the wide variation of O2 radiolysis yields between laboratory experiments, ranging over 4 orders of magnitude from 5 × 10-7 to 5 × 10-3 molecules/eV for different particles and energies. We revisit decades of laboratory data to solve this long-standing puzzle, finding an inverse projectile range dependence in the O2 yields, due to preferential O2 formation from an 30 Å thick oxygenated surface layer. Highly penetrating projectile ions and electrons with ranges ≳30 Å are therefore less efficient at producing O2 than slow/heavy ions and low-energy electrons (≲ 400 eV) which deposit most energy near the surface. Unlike O2, the H2O2 yields from penetrating projectiles fall within a comparatively narrow range of (0.1-6) × 10-3 molecules/eV and do not depend on range, suggesting that H2O2 forms deep in the ice uniformly along the projectile track, e.g., by reactions of OH radicals. We develop an analytical model for O2, H2, and H2O2 yields from pure water ice for electrons and singly charged ions of any mass and energy and apply the model to estimate possible O2 source rates on several icy satellites. The yields are upper limits for icy bodies on which surface impurities may be present.

Oxidation of Microcystins by Permanganate: pH and Temperature-Dependent Kinetics, Effect of DOM Characteristics, and Oxidation Mechanism Revisited.

PubMed

Kim, Min Sik; Lee, Hye-Jin; Lee, Ki-Myeong; Seo, Jiwon; Lee, Changha

2018-05-23

Oxidative degradation of six representative microcystins (MCs) (MC-RR, -LR, -YR, -LF, -LW and -LA) by potassium permanganate (KMnO4; Mn(VII)) was investigated, focusing on the temperature- and pH-dependent reaction kinetics, the effect of dissolved organic matter (DOM), and the oxidation mechanisms. Second-order rate constants for the reactions of the six MCs with Mn(VII) (kMn(VII),MC) were determined to be 160.4-520.1 M-1 s-1 (MC-RR > -LR  -YR > -LF  -LW > -LA) at pH 7.2 and 21°C. The kMn(VII),MC values exhibited activation energies ranging from 15.1 to 22.4 kJ mol-1. With increasing pH from 2 to 11, the kMn(VII),MC values decreased until pH 5, and plateaued over the pH range of 5-11, except for that of MC-YR (which increased at pH > 8). Species-specific second-order rate constants were calculated using predicted pKa values of MCs. The oxidation of MCs in natural waters was accurately predicted by the kinetic model using kMn(VII),MC and Mn(VII) exposure ([Mn(VII)]dt) values. Among different characteristics of DOM in natural waters, UV254, SUVA254, and the abundance of humic-like substances characterized by fluorescence spectroscopy exhibited good correlation with [Mn(VII)]dt. A thorough product study of MC-LR oxidation by Mn(VII) was performed using liquid chromatography-mass spectrometry.

Temperature dependence of the hydrogen-broadening coefficient for the nu 9 fundamental of ethane

NASA Technical Reports Server (NTRS)

Halsey, G. W.; Hillman, J. J.; Nadler, Shacher; Jennings, D. E.

1988-01-01

Experimental results for the temperature dependence of the H2-broadening coefficient for the nu 9 fundamental of ethane are reported. Measurements were made over the temperature range 95-300 K using a novel low-temperature absorption cell. These spectra were recorded with the Doppler-limited diode laser spectrometer at NASA Goddard. The results are compared with recent measurements and model predictions.

Exploring external time-dependent sources of H2O into Titan's atmosphere

NASA Astrophysics Data System (ADS)

Lara, Luisa-Maria; Lellouch, Emmanuel; González, Marta; Moreno, Raphael; Rengel, Miriam

2014-05-01

Recent observations (Cottini et al., 2012, and Moreno et al., 2012) and steady-state photochemical modelling (Moreno et al., 2012; Dobrijevic et al., 2014) indicate that the amounts of CO2 and H2O in Titan's stratosphere imply relatively inconsistent values of the OH/H2O input flux. Moreno et al. (2012) proposed that the oxygen source is time-variable, whereas Dobrijevic et al. (2014) arrived to the same conclusion of Moreno et al. (2012) that the HSO (Herschel Space Observatory) measured H2O profile is'inconsistent" with the CO2 abundance. Furthermore, Dobrijevic et al. (2014) also found that reconciliation was possible if abundances reported by Cottini et al. (2012) are correct instead, though in this situation and for an Enceladus source, their model tended to overpredict the thermospheric abundance of H2O , compared to the upper limit by Cui et al. (2009). We attempt to reconcile the H2O and CO2 observed profiles in Titan's atmosphere by considering several time-dependent scenarios for the infux/evolution of oxygen species. To explore this, we use a time-dependent photochemical model of Titan's atmosphere to calculate effective lifetimes and the response of Titan's oxygen compounds to changes in the oxygen input flux. We consider a time-variable Enceladus source, as well as the evolution of material delivered by a cometary impact. We will show results on effective H2O and CO2 effective lifetimes, on the feasibility of time-variable Enceladus source, and on an additional H2O loss-to-the-haze. Regarding CO2, we will analyse its production following a cometary impact. A summary on viable scenarios to explain the H2O / CO2 puzzle will be given. References Moreno, R., Lellouch, E., Lara, L. M., et al. 2012, Icarus, 221, 753. Cottini, V., Nixon, C. A., Jennings, D. E., et al. 2012, Icarus, 220, 855. Cui, J., Yelle, R. V., Vuitton, V., et al. 2009, Icarus, 200, 581. Dobrijevic, M., Hébrard, E., Loison, J., and Hickson, K. 2014, Icarus, 228, 324.

Temperature- and pH-dependent aqueous-phase kinetics of the reactions of glyoxal and methylglyoxal with atmospheric amines and ammonium sulfate

NASA Astrophysics Data System (ADS)

Sedehi, Nahzaneen; Takano, Hiromi; Blasic, Vanessa A.; Sullivan, Kristin A.; De Haan, David O.

2013-10-01

Reactions of glyoxal (Glx) and methylglyoxal (MG) with primary amines and ammonium salts may produce brown carbon and N-containing oligomers in aqueous aerosol. 1H NMR monitoring of reactant losses and product appearance in bulk aqueous reactions were used to derive rate constants and quantify competing reaction pathways as a function of pH and temperature. Glx + ammonium sulfate (AS) and amine reactions generate products containing C-N bonds, with rates depending directly on pH: rate = (70 ± 60) M-1 s-1fAld [Glx]totfAm [Am]tot, where fAld is the fraction of aldehyde with a dehydrated aldehyde functional group, and fAm is the fraction of amine or ammonia that is deprotonated at a given pH. MG + amine reactions generate mostly aldol condensation products and exhibit less pH dependence: rate = 10[(0.36 ± 0.06) × pH - (3.6 ± 0.3)] M-1 s-1fAld [MG]tot [Am]tot. Aldehyde + AS reactions are less temperature-dependent (Ea = 18 ± 8 kJ mol-1) than corresponding amine reactions (Ea = 50 ± 11 kJ mol-1). Using aerosol concentrations of [OH] = 10-12 M, [amine]tot = [AS] = 0.1 M, fGlx = 0.046 and fMG = 0.09, we estimate that OH radical reactions are normally the major aerosol-phase sink for both dicarbonyl compounds. However, reactions with AS and amines together can account for up to 12 and 45% of daytime aerosol-phase glyoxal and methylglyoxal reactivity, respectively, in marine aerosol at pH 5.5. Reactions with AS and amines become less important in acidic or non-marine aerosol, but may still be significant atmospheric sources of brown carbon, imidazoles, and nitrogen-containing oligomers.

A set of new transition metal-based coordination complexes dependent upon Hpztza ligand (Hpztza=2-(5-(pyrazin-2-yl)-2H-tetrazol-2-yl) acetic acid)

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

Yang Jie; Shen Lei; Yang Gaowen, E-mail: ygwsx@126.com

2012-02-15

Reaction of MCl{sub 2}{center_dot}4H{sub 2}O (M=Zn, Cd, Mn, Co, Ni) with 2-(5-(pyrazin-2-yl)-2H-tetrazol-2-yl) acetic acid (Hpztza) yielded a set of new M(II)/pztza complexes, [Cd(pztza){sub 2}(H{sub 2}O){sub 6}]{center_dot}3H{sub 2}O{center_dot}(Hpztza) (1), [M(pztza){sub 2}(H{sub 2}O){sub 2}; M=Cd(2), Zn(7), Mn(9)], [Cd(pztza){sub 2}]{center_dot}2(CH{sub 3}OH) (3), [Co(pztza){sub 2}(H{sub 2}O){sub 2}]{center_dot}6H{sub 2}O (4), [Co(pztza)(H{sub 2}O)Cl] (6) and [M(pztza){sub 2}(H{sub 2}O){sub 2}]{center_dot}2H{sub 2}O [M=Co(5), Zn(8), Ni(10)]. These compounds were structurally characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Complex 1 featured a mononuclear structure, complexes 4, 5, 7, 8, 10 showed 1D chains and complexes 2, 3, 6, 9 displayed 2D layer structures. Furthermore, the luminescence propertiesmore » of 1-10 were investigated at room temperature in the solid state. - Graphical abstract: Ten new coordination polymers with 2-(5-(pyrazin-2-yl)-2H-tetrazol-2-yl) acetic acid (Hpztza) ligand have been synthesized and their structures have been characterized. All of the complexes show photoluminescence at room temperature. Highlights: Black-Right-Pointing-Pointer Ten novel transition metal-based coordination complexes with 2-(5-(pyrazin-2-yl)-2H-tetrazol-2-yl) acetic acid (Hpztza) are reported. Black-Right-Pointing-Pointer Complexes 1-10 are described as mononuclear structure, 1D and 2D frameworks with diverse architecture. Black-Right-Pointing-Pointer Six coordination complexes show emission at room temperature in the solid state.« less

Carbonate mineral solubility at low temperatures in the Na-K-Mg-Ca-H-Cl-SO 4-OH-HCO 3-CO 3-CO 2-H 2O system

NASA Astrophysics Data System (ADS)

Marion, Giles M.

2001-06-01

Carbonate minerals have played an important role in the geochemical evolution of Earth, and may have also played an important role in the geochemical evolution of Mars and Europa. Several models have been published in recent years that describe chloride and sulfate mineral solubilities in concentrated brines using the Pitzer equations. Few of these models are parameterized for subzero temperatures, and those that are do not include carbonate chemistry. The objectives of this work are to estimate Pitzer-equation bicarbonate-carbonate parameters and carbonate mineral solubility products and to incorporate them into the FREZCHEM model to predict carbonate mineral solubilities in the Na-K-Mg-Ca-H-Cl-SO 4-OH-HCO 3-CO 3-CO 2-H 2O system at low temperatures (≤25°C) with a special focus on subzero temperatures. Most of the Pitzer-equation parameters and equilibrium constants are taken from the literature and extrapolated into the subzero temperature range. Solubility products for 14 sodium, potassium, magnesium, and calcium bicarbonate and carbonate minerals are included in the model. Most of the experimental data are at temperatures ≥ -8°C; only for the NaHCO 3-NaCl-H 2O and Na 2CO 3-NaCl-H 2O systems are there bicarbonate and carbonate data to temperatures as low as -21.6°C. In general, the fit of the model to the experimental data is good. For example, calculated eutectic temperatures and compositions for NaHCO 3, Na 2CO 3, and their mixtures with NaCl and Na 2SO 4 salts are in good agreement with experimental data to temperatures as low as -21.6°C. Application of the model to eight saline, alkaline carbonate waters give predicted pHs ranging from 9.2 to 10.2, in comparison with measured pHs that range from 8.7 to 10.2. The model suggests that the CaCO 3 mineral that precipitates during seawater freezing is probably calcite and not ikaite. The model demonstrates that a proposed salt assemblage for the icy surface of Europa consisting of highly hydrated MgSO 4

pH dependent green synthesis of gold nanoparticles by completely C6-carboxylated curdlan under high temperature and various pH conditions.

PubMed

Qiu, Wen-Yi; Wang, Kai; Wang, Yao-Yao; Ding, Zhi-Chao; Wu, Li-Xia; Cai, Wu-Dan; Yan, Jing-Kun

2018-01-01

A C6-carboxylated curdlan (C6-Cc) obtained from 4-acetamido-TEMPO-mediated oxidation of curdlan was used both as a reducing and stabilizing agent for green synthesis of pH-responsive AuNPs, which was carried out by controlling the pH of the C6-Cc solution at a high temperature (100°C). C6-Cc presented a semi-flexible random coil chain in the aqueous medium at pH 5.5 and became more expanded and rigid in alkaline conditions (pH 7.1-12.0), though the primary chemical structure of C6-Cc was virtually unchanged with the pH variation. The AuNPs prepared with C6-Cc at various pHs were characterized by various instrumental measurements. The shapes and sizes of AuNPs were found to be strongly dependent on the pH of the C6-Cc solution. The C6-Cc-decorated AuNPs exhibited a more well-dispersed spherical morphology with smaller particle sizes under alkaline conditions (pH 7.1-12.0). Through this study, a facile, simple, and green method has been demonstrated for preparation of stimuli-sensitive AuNPs using biocompatible polyanionic polysaccharides. Copyright © 2017 Elsevier B.V. All rights reserved.

Room-temperature H2S Gas Sensor Based on Au-doped ZnFe2O4 Yolk-shell Microspheres.

PubMed

Yan, Yin; Nizamidin, Patima; Turdi, Gulmira; Kari, Nuerguli; Yimit, Abliz

2017-01-01

Room-temperature type H 2 S sensing devices that use Au-doped ZnFe 2 O 4 yolk-shell microspheres as the active material have been fabricated using a solvothermal method as well as subsequent annealing and a chemical etching process. The samples are characterized using X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), field-emission scanning electron microscopy (FESEM), and X-ray photoelectron spectroscopy (XPS). The results demonstrate that the doping of Au does not change the spinel structure of the products, which were yolk-shell microspheres, while the particle size varied with the Au doping concentration. Also, the as-fabricated sensor device exhibited excellent selectivity toward H 2 S gas at the room temperature; the gas-sensing property of 2 wt% Au-doped ZnFe 2 O 4 microspheres was the best. The Au-doped ZnFe 2 O 4 yolk-shell microspheres can be promising as a sensing material for H 2 S gas detecting at room temperature.

Temperature Dependence of Irradiation Damage to Polythene

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

TODD, G.; WILD, G. A.

1963-07-13

Comparison of measurements of radiation damage to polythene exposed to a 4.3-Mev linear accelerator and in a reactor led to the conclusion that radiation damage of polythene is temperature dependent. Applications of radiation in raising or lowering the elastic modulus of polythene are suggested. (C.H.)

Thermoelectric properties of the 3C, 2H, 4H, and 6H polytypes of the wide-band-gap semiconductors SiC, GaN, and ZnO

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

Huang, Zheng; Lü, Tie-Yu; Wang, Hui-Qiong

We have investigated the thermoelectric properties of the 3C, 2H, 4H, and 6H polytypes of the wide-band-gap(n-type) semiconductors SiC, GaN, and ZnO based on first-principles calculations and Boltzmann transport theory. Our results show that the thermoelectric performance increases from 3C to 6H, 4H, and 2H structures with an increase of hexagonality for SiC. However, for GaN and ZnO, their power factors show a very weak dependence on the polytype. Detailed analysis of the thermoelectric properties with respect to temperature and carrier concentration of 4H-SiC, 2H-GaN, and 2H-ZnO shows that the figure of merit of these three compounds increases with temperature,more » indicating the promising potential applications of these thermoelectric materials at high temperature. The significant difference of the polytype-dependent thermoelectric properties among SiC, GaN, and ZnO might be related to the competition between covalency and ionicity in these semiconductors. Our calculations may provide a new way to enhance the thermoelectric properties of wide-band-gap semiconductors through atomic structure design, especially hexagonality design for SiC.« less

In situ combustion measurements of H2O and temperature near 2.5 µm using tunable diode laser absorption

NASA Astrophysics Data System (ADS)

Farooq, Aamir; Jeffries, Jay B.; Hanson, Ronald K.

2008-07-01

In situ combustion measurements of water vapor concentration and gas temperature were carried out with a new tunable diode laser sensor near 2.5 µm. Recent availability of room-temperature semiconductor diode lasers operating at longer wavelengths provides access to fundamental vibrational bands (ν1 and ν3) of H2O. These bands have stronger absorption line strength compared to the overtone (2ν1, 2ν3) and combination (ν1 + ν3) vibrational bands in the near-infrared region probed previously with telecommunication diode lasers. The absorption transitions of H2O vapor in the 2.5-3.0 µm region are systematically analyzed via spectral simulation, and optimal spectral line pairs are selected for combustion measurements in the temperature range of 1000-2500 K. Fundamental spectroscopic parameters (line strength, line position and line-broadening coefficients) of the selected transitions are determined via laboratory measurements in a heated cell. Absorption measurements of H2O concentration and temperature are then made in a laboratory flat-flame burner to illustrate the potential of this sensor for sensitive and accurate measurements in combustion gases with short optical path lengths.

Pressure dependence of the absolute rate constant for the reaction OH + C2H2 from 228 to 413K

NASA Technical Reports Server (NTRS)

Michael, J. V.; Nava, D. F.; Borokowski, R. P.; Payne, W. A.; Stief, L. J.

1980-01-01

The pressure dependence of absolute rate constants for the reaction of OH + C2H2 yields products has been examined at five temperatures ranging from 228 to 413 K. The experimental techniques which was used is flash photolysis-resonance fluoresence. OH was produced by water photolysis and hydroxyl resonance fluorescent photons were measured by multiscaling techniques. The results indicate that the low pressure bimolecular rate constant is 4 x 10 the the minus 13th power cu cm molecule (-1) s(-1) over the temperature range studied. A substantial increase in the bimolecular rate constant with an increase in pressure was observed at all temperatures except 228 K. This indicates the importance of initial adduct formation and subsequent stablization. The high pressure results are well represented by the Arrhenius expression (k sub bi) sub infinity = (6.83 + or - 1.19) x 10 to the minus 12th power exp(-646 + or - 47/T)cu cm molecule (-1) s(-1). The results are compared to previous investigated and are theoretically discussed. The implications of these results on modeling of terrestrial and planetary atmospheres and also in combustion chemistry are discussed.

FRET ratiometric probes reveal the chiral-sensitive cysteine-dependent H2S production and regulation in living cells

NASA Astrophysics Data System (ADS)

Wei, Lv; Yi, Long; Song, Fanbo; Wei, Chao; Wang, Bai-Fan; Xi, Zhen

2014-04-01

Hydrogen sulfide (H2S) is an endogenously produced gaseous signalling molecule with multiple biological functions. In order to visualize and quantify the endogenous in situ production of H2S in living cells, here we developed two new sulphide ratiometric probes (SR400 and SR550) based on fluorescence resonance energy transfer (FRET) strategy for live capture of H2S. The FRET-based probes show excellent selectivity toward H2S in a high thiol background under physiological buffer. The probe can be used to in situ visualize cysteine-dependent H2S production in a chiral-sensitive manner in living cells. The ratiometric imaging studies indicated that D-Cys induces more H2S production than that of L-Cys in mitochondria of human embryonic kidney 293 cells (HEK293). The cysteine mimics propargylglycine (PPG) has also been found to inhibit the cysteine-dependent endogenous H2S production in a chiral-sensitive manner in living cells. D-PPG inhibited D-Cys-dependent H2S production more efficiently than L-PPG, while, L-PPG inhibited L-Cys-dependent H2S production more efficiently than D-PPG. Our bioimaging studies support Kimura's discovery of H2S production from D-cysteine in mammalian cells and further highlight the potential of D-cysteine and its derivatives as an alternative strategy for classical H2S-releasing drugs.

First Time-dependent Study of H2 and H_3^+ Ortho-Para Chemistry in the Diffuse Interstellar Medium: Observations Meet Theoretical Predictions

NASA Astrophysics Data System (ADS)

Albertsson, T.; Indriolo, N.; Kreckel, H.; Semenov, D.; Crabtree, K. N.; Henning, Th.

2014-05-01

The chemistry in the diffuse interstellar medium (ISM) initiates the gradual increase of molecular complexity during the life cycle of matter. A key molecule that enables build-up of new molecular bonds and new molecules via proton donation is H_3^+. Its evolution is tightly related to molecular hydrogen and thought to be well understood. However, recent observations of ortho and para lines of H2 and H_3^+ in the diffuse ISM showed a puzzling discrepancy in nuclear spin excitation temperatures and populations between these two key species. H_3^+, unlike H2, seems to be out of thermal equilibrium, contrary to the predictions of modern astrochemical models. We conduct the first time-dependent modeling of the para-fractions of H2 and H_3^+ in the diffuse ISM and compare our results to a set of line-of-sight observations, including new measurements presented in this study. We isolate a set of key reactions for H_3^+ and find that the destruction of the lowest rotational states of H_3^+ by dissociative recombination largely controls its ortho/para ratio. A plausible agreement with observations cannot be achieved unless a ratio larger than 1:5 for the destruction of (1, 1)- and (1, 0)-states of H_3^+ is assumed. Additionally, an increased cosmic-ray ionization rate to 10-15 s-1 further improves the fit whereas variations of other individual physical parameters, such as density and chemical age, have only a minor effect on the predicted ortho/para ratios. Thus, our study calls for new laboratory measurements of the dissociative recombination rate and branching ratio of the key ion H_{3}^{+} under interstellar conditions. Partly based on observations collected at the European Organization for Astronomical Research in the Southern Hemisphere, Chile, as part of program 088.C-0351.

Sperm motility in fishes. I. Effects of temperature and pH: a review.

PubMed

Alavi, Sayyed Mohammad Hadi; Cosson, Jacky

2005-02-01

Sperm motility is a key factor in allowing us to determine semen quality and fertilizing capacity. Motility in semen is mainly controlled by K+ in salmonids, and probably also in sturgeons, and by osmotic pressure in other freshwater and seawater fish species, but other factors, such as concentration of surrounding metabolites and ions (Ca2+, Mg2+, etc.), pH and temperature also influence motility characteristics. In the present study, we have mainly reviewed and summarized the effects of temperature and pH on the motility of spermatozoa in three fish species: salmonids, cyprinids and sturgeons. Data in the literature show that motility, fertilizing ability and velocity of spermatozoa, as well as the duration of the motility period, depend on the temperature of the assay medium and also of that of the brood fish holding tank. In contrast, the pH of the swimming medium, and thus the intracellular pH of spermatozoa, has less influence on sperm motility parameters in cyprinids, salmonids and sturgeons.

Vibrations and reorientations of H2O molecules in [Sr(H2O)6]Cl2 studied by Raman light scattering, incoherent inelastic neutron scattering and proton magnetic resonance.

PubMed

Hetmańczyk, Joanna; Hetmańczyk, Lukasz; Migdał-Mikuli, Anna; Mikuli, Edward; Florek-Wojciechowska, Małgorzata; Harańczyk, Hubert

2014-04-24

Vibrational-reorientational dynamics of H2O ligands in the high- and low-temperature phases of [Sr(H2O)6]Cl2 was investigated by Raman Spectroscopy (RS), proton magnetic resonance ((1)H NMR), quasielastic and inelastic incoherent Neutron Scattering (QENS and IINS) methods. Neutron powder diffraction (NPD) measurements, performed simultaneously with QENS, did not indicated a change of the crystal structure at the phase transition (detected earlier by differential scanning calorimetry (DSC) at TC(h)=252.9 K (on heating) and at TC(c)=226.5K (on cooling)). Temperature dependence of the full-width at half-maximum (FWHM) of νs(OH) band at ca. 3248 cm(-1) in the RS spectra indicated small discontinuity in the vicinity of phase transition temperature, what suggests that the observed phase transition may be associated with a change of the H2O reorientational dynamics. However, an activation energy value (Ea) for the reorientational motions of H2O ligands in both phases is nearly the same and equals to ca. 8 kJ mol(-1). The QENS peaks, registered for low temperature phase do not show any broadening. However, in the high temperature phase a small QENS broadening is clearly visible, what implies that the reorientational dynamics of H2O ligands undergoes a change at the phase transition. (1)H NMR line is a superposition of two powder Pake doublets, differentiated by a dipolar broadening, suggesting that there are two types of the water molecules in the crystal lattice of [Sr(H2O)6]Cl2 which are structurally not equivalent average distances between the interacting protons are: 1.39 and 1.18 Å. However, their reorientational dynamics is very similar (τc=3.3⋅10(-10) s). Activation energies for the reorientational motion of these both kinds of H2O ligands have nearly the same values in an experimental error limit: and equal to ca. 40 kJ mole(-1). The phase transition is not seen in the (1)H NMR spectra temperature dependencies. Infrared (IR), Raman (RS) and inelastic

Quasipermanent magnets of high temperature superconductor - Temperature dependence

NASA Technical Reports Server (NTRS)

Chen, In-Gann; Liu, Jianxiong; Ren, Yanru; Weinstein, Roy; Kozlowski, Gregory; Oberly, Charles E.

1993-01-01

We report on persistent field in quasi-permanent magnets of high temperature superconductors. Magnets composed of irradiated Y(1+)Ba2Cu3O7 trapped field Bt = 1.52 T at 77 K and 1.9 T at lower temperature. However, the activation magnet limited Bt at lower temperature. We present data on Jc(H,T) for unirradiated materials, and calculate Bt at various T. Based upon data at 65 K, we calculate Bt in unirradiated single grains at 20 K and find that 5.2 T will be trapped for grain diameter d about 1.2 cm, and 7.9 T for d = 2.3 cm. Irradiated grains will trap four times these values.

Electrical transport properties of thermally evaporated phthalocyanine (H 2Pc) thin films

NASA Astrophysics Data System (ADS)

El-Nahass, M. M.; Farid, A. M.; Attia, A. A.; Ali, H. A. M.

2006-08-01

Thin films of H 2Pc of various thicknesses have been deposited onto glass substrates using thermal evaporation technique at room temperature. The dark electrical resistivity measurements were carried out at different temperatures in the range 298-473 K. An estimation of mean free path ( lo) of charge carriers in H 2Pc thin films was attempted. Measurements of thermoelectric power confirm that H 2Pc thin films behave as a p-type semiconductor. The current density-voltage characteristics of Au/H 2Pc/Au at room temperature showed ohmic conduction mechanism at low voltages. At higher voltages the space-charge-limited conduction (SCLC) accompanied by an exponential trap distribution was dominant. The temperature dependence of current density allows the determination of some essential parameters such as the hole mobility ( μh), the total trap concentration ( Nt), the characteristic temperature ( Tt) and the trap density P( E).

Equations for O2 and CO2 solubilities in saline and plasma: combining temperature and density dependences.

PubMed

Christmas, Kevin M; Bassingthwaighte, James B

2017-05-01

Solubilities of respiratory gasses in water, saline, and plasma decrease with rising temperatures and solute concentrations. Henry's Law, C = α·P, states that the equilibrium concentration of a dissolved gas is solubility times partial pressure. Solubilities in the water of a solution depend on temperature and the content of other solutes. Blood temperatures may differ more than 20°C between skin and heart, and an erythrocyte will undergo that range as blood circulates. The concentrations of O 2 and CO 2 are the driving forces for diffusion, exchanges, and for reactions. We provide an equation for O 2 and CO 2 solubilities, α, that allows for continuous changes in temperature, T, and solution density, ρ, in dynamically changing states:[Formula: see text]This two-exponential expression with a density scalar γ, and a density exponent β, accounts for solubility changes due to density changes of an aqueous solution. It fits experimental data on solubilities in water, saline, and plasma over temperatures from 20 to 40°C, and for plasma densities, ρ sol up to 1.020 g/ml with ~0.3% error. The amounts of additional bound O 2 (to Hb) and CO 2 (bicarbonate and carbamino) depend on the concentrations in the local water space and the reaction parameters. During exercise, solubility changes are large; both ρ sol and T change rapidly with spatial position and with time. In exercise hemoconcentration plasma, ρ sol exceeds 1.02, whereas T may range over 20°C. The six parameters for O 2 and the six for CO 2 are constants, so solubilities are calculable continuously as T and ρ sol change. NEW & NOTEWORTHY Solubilities for oxygen and carbon dioxide are dependent on the density of the solution, on temperature, and on the partial pressure. We provide a brief equation suitable for hand calculators or mathematical modeling, accounting for these factors over a wide range of temperatures and solution densities for use in rapidly changing conditions, such as extreme exercise or

High temperature regenerative H.sub.2 S sorbents

NASA Technical Reports Server (NTRS)

Flytani-Stephanopoulos, Maria (Inventor); Gavalas, George R. (Inventor); Tamhankar, Satish S. (Inventor)

1988-01-01

Efficient, regenerable sorbents for removal of H.sub.2 S from high temperature gas streams comprise porous, high surface area particles. A first class of sorbents comprise a thin film of binary oxides that form a eutectic at the temperature of the gas stream coated onto a porous, high surface area refractory support. The binary oxides are a mixture of a Group VB or VIB metal oxide with a Group IB, IIB or VIII metal oxide such as a film of V-Zn-O, V-Cu-O, Cu-Mo-O, Zn-Mo-O or Fe-Mo-O coated on an alumina support. A second class of sorbents consist of particles of unsupported mixed oxides in the form of highly dispersed solid solutions of solid compounds characterized by small crystallite size, high porosity and relatively high surface area. The mixed oxide sorbents contain one Group IB, IIB or VIIB metal oxide such as copper, zinc or manganese and one or more oxides of Groups IIIA, VIB or VII such as aluminum, iron or molybdenum. The presence of iron or aluminum maintains the Group IB, IIB or VIIB metal in its oxidized state. Presence of molybdenum results in eutectic formation at sulfidation temperature and improves the efficiency of the sorbent.

In situ H2O and temperature detection close to burning biomass pellets using calibration-free wavelength modulation spectroscopy

NASA Astrophysics Data System (ADS)

Qu, Zhechao; Schmidt, Florian M.

2015-04-01

The design and application of an H2O/temperature sensor based on scanned calibration-free wavelength modulation spectroscopy (CF-WMS) and a single tunable diode laser at 1.4 µm is presented. The sensor probes two H2O absorption peaks in a single scan and simultaneously retrieves H2O concentration and temperature by least-squares fitting simulated 1f-normalized 2f-WMS spectra to measured 2f/ 1f-WMS signals, with temperature, concentration and nonlinear modulation amplitude as fitting parameters. Given a minimum detectable absorbance of 1.7 × 10-5 cm-1 Hz-1/2, the system is applicable down to an H2O concentration of 0.1 % at 1,000 K and 20 cm path length (200 ppm·m). The temperature in a water-seeded laboratory-scale reactor (670-1220 K at 4 % H2O) was determined within an accuracy of 1 % by comparison with the reactor thermocouple. The CF-WMS sensor was applied to real time in situ measurements of H2O concentration and temperature time histories (0.25-s time resolution) in the hot gases 2-11 mm above biomass pellets during atmospheric combustion in the reactor. Temperatures between 1,200 and 1,600 K and H2O concentrations up to 40 % were detected above the biofuels.

Dependence of electrical and optical properties of amorphous SiC:H thin films grown by rf plasma enhanced chemical vapor deposition on annealing temperature

NASA Astrophysics Data System (ADS)

Park, M. G.; Choi, W. S.; Hong, B.; Kim, Y. T.; Yoon, D. H.

2002-05-01

In this article, we investigated the dependence of optical and electrical properties of hydrogenated amorphous silicon carbide (a-SiC:H) films on annealing temperature (Ta) and radio frequency (rf) power. The substrate temperature (Ts) was 250 °C, the rf power was varied from 30 to 400 W, and the range of Ta was from 400 to 600 °C. The a-SiC:H films were deposited by using the plasma enhanced chemical vapor deposition system on Corning 7059 glasses and p-type Si (100) wafers with a SiH4+CH4 gas mixture. The experimental results have shown that the optical bandgap energy (Eg) of the a-SiC:H thin films changed little on the annealing temperature while Eg increased with the rf power. The Raman spectrum of the thin films annealed at high temperatures showed that graphitization of carbon clusters and microcrystalline silicon occurs. The current-voltage characteristics have shown good electrical properties in relation to the annealed films.

Temperature dependence of corrosion of ferritic stainless steel in dual atmosphere at 600-800 °C

NASA Astrophysics Data System (ADS)

Alnegren, Patrik; Sattari, Mohammad; Svensson, Jan-Erik; Froitzheim, Jan

2018-07-01

The ferritic stainless steel AISI 441 (EN 1.4509) is exposed for 1000 h to air - 3% H2O on one side and to Ar - 5% H2 - 3% H2O on the other at temperatures 600, 700, and 800 °C. Conditions are chosen to mimic the environment of metallic interconnects in an operating solid oxide fuel cell (SOFC). At 600 °C, ∼25 μm thick Fe2O3/(Fe,Cr)3O4 forms on large parts of the air side of the samples. Reference samples exposed to air - 3% H2O on both sides form thin protective layers of (Cr,Mn)3O4/Cr2O3 at the same temperature. At higher temperatures, 700 and 800 °C, all samples form protective layers of (Cr,Mn)3O4/Cr2O3 regardless of exposure to single or dual atmosphere. It is concluded that corrosion resistance in a dual atmosphere has an inverse dependence on temperature. Different hypotheses for the underlying cause for the dual atmosphere effect are discussed and compared to the experimental data.

Reflected shock tube studies of high-temperature rate constants for OH + CH4 --> CH3 + H2O and CH3 + NO2 --> CH3O + NO.

PubMed

Srinivasan, N K; Su, M-C; Sutherland, J W; Michael, J V

2005-03-10

The reflected shock tube technique with multipass absorption spectrometric detection of OH radicals at 308 nm has been used to study the reactions OH + CH(4) --> CH(3) + H(2)O and CH(3) + NO(2) --> CH(3)O + NO. Over the temperature range 840-2025 K, the rate constants for the first reaction can be represented by the Arrhenius expression k = (9.52 +/- 1.62) x 10(-11) exp[(-4134 +/- 222 K)/T] cm(3) molecule(-1) s(-1). Since this reaction is important in both combustion and atmospheric chemistry, there have been many prior investigations with a variety of techniques. The present results extend the temperature range by 500 K and have been combined with the most accurate earlier studies to derive an evaluation over the extended temperature range 195-2025 K. A three-parameter expression describes the rate behavior over this temperature range, k = (1.66 x 10(-18))T(2.182) exp[(-1231 K)/T] cm(3) molecule(-1) s(-1). Previous theoretical studies are discussed, and the present evaluation is compared to earlier theoretical estimates. Since CH(3) radicals are a product of the reaction and could cause secondary perturbations in rate constant determinations, the second reaction was studied by OH radical production from the fast reactions CH(3)O --> CH(2)O + H and H + NO(2) --> OH + NO. The measured rate constant is 2.26 x 10(-11) cm(3) molecule(-1) s(-1) and is not dependent on temperature from 233 to 1700 K within experimental error.

Temperature-dependent elastic stiffness constants of α- and θ-Al2O3 from first-principles calculations

NASA Astrophysics Data System (ADS)

Shang, Shun-Li; Zhang, Hui; Wang, Yi; Liu, Zi-Kui

2010-09-01

Temperature-dependent elastic stiffness constants (cijs), including both the isothermal and isoentropic ones, have been predicted for rhombohedral α-Al2O3 and monoclinic θ-Al2O3 in terms of a quasistatic approach, i.e., a combination of volume-dependent cijs determined by a first-principles strain versus stress method and direction-dependent thermal expansions obtained by first-principles phonon calculations. A good agreement is observed between the predictions and the available experiments for α-Al2O3, especially for the off-diagonal elastic constants. In addition, the temperature-dependent cijs predicted herein, in particular the ones for metastable θ-Al2O3, enable the stress analysis at elevated temperatures in thermally grown oxides containing α- and θ-Al2O3, which are crucial to understand the failure of thermal barrier coatings in gas-turbine engines.

Time-dependent quantum wave packet calculation for nonadiabatic F(2P3/2,2P1/2)+H2 reaction

NASA Astrophysics Data System (ADS)

Zhang, Yan; Xie, Ting-Xian; Han, Ke-Li; Zhang, John Z. H.

2003-12-01

In this paper we present a time-dependent quantum wave packet calculation for the reaction of F(2P3/2,2P1/2)+H2 on the Alexander-Stark-Werner potential energy surface. The reaction probabilities and the integral cross sections for the reaction of F(2P3/2,2P1/2)+H2 (v=j=0) are computed using time-dependent quantum methods with the centrifugal sudden approximate. The results are compared with recent time-independent quantum calculations. The two-surface reaction probability for the initial ground spin-orbit state of J=0.5 is similar to the time-independent result obtained by Alexander et al. [J. Chem. Phys. 113, 11084 (2000)]. Our calculation also shows that electronic coupling has a relatively minor effect on the reactivity from the 2P3/2 state but a non-negligible one from the 2P1/2 state. By comparison with exact time-independent calculations, it is found that the Coriolis coupling plays a relatively minor role. In addition, most of the reactivity of the excited state of fluorine atom results from the spin-orbit coupling.

Temperature dependence of the Raman spectrum of 1-(4-chlorophenyl)-3-(2-thienyl)prop-2-en-1-one

NASA Astrophysics Data System (ADS)

de Toledo, T. A.; da Costa, R. C.; Al-Maqtari, H. M.; Jamalis, J.; Pizani, P. S.

2017-06-01

The heterocyclic chalcone containing thiophene ring 1-(4-chlorophenyl)-3-(2-thienyl)prop-2-en-1-one, C13H9ClOS was synthesized and investigated using experimental techniques such as nuclear magnetic resonance (1H and 13C NMR), Fourier transform infrared spectroscopy (FTIR) at room temperature, differential scanning calorimeter (DSC) from room temperature to 500 K and Raman scattering at the temperature range 10-413 K in order to study its structure and vibrational properties as well as stability and possible phase transition. Density functional theory (DFT) calculations were performed to determine the vibrational spectrum viewing to improve the knowledge of the material properties. A reasonable agreement was observed between theoretical and experimental Raman spectrum taken at 10 K since anharmonic effects of the molecular motion is reduced at low temperatures, leading to a more comprehensive assignment of the vibrational modes. Increasing the temperature up to 393 K, was observed the typical phonon anharmonicity behavior associated to changes in the Raman line intensities, line-widths and red-shift, in special in the external mode region, whereas the internal modes region remains almost unchanged due its strong chemical bonds. Furthermore, C13H9ClOS goes to melting phase transition in the temperature range 393-403 K and then sublimates in the temperature range 403-413 K. This is denounced by the disappearance of the external modes and the absence of internal modes in the Raman spectra, in accordance with DSC curve. The enthalpy (ΔH) obtained from the integration of the endothermic peak in DSC curve centered at 397 K is founded to be 121.5 J/g.

Temperature- and pH-dependent effect of lactate on in vitro redox stability of red meat myoglobins.

PubMed

Nair, M N; Suman, S P; Li, S; Ramanathan, R; Mancini, R A

2014-01-01

Our objective was to evaluate the influence of lactate on in vitro redox stability and thermostability of beef, horse, pork, and sheep myoglobins. Lactate (200 mM) had no effect (P>0.05) on redox stability at physiological (pH7.4, 37°C) and meat (pH 5.6, 4°C) conditions. However, lactate increased (P<0.05) metmyoglobin formation at a condition simulating stressed live skeletal muscle (pH 6.5, 37°C). The redox stability of myoglobins at stressed live skeletal muscle and meat conditions was species-specific (P<0.05). Myoglobin thermostability at 71°C was lower (P<0.05) in the presence of lactate compared with controls and was influenced (P<0.05) by species. The results of the present study indicate that the effects of lactate on myoglobin are temperature and pH dependent. The observed lack of influence of lactate on myoglobin redox stability at meat condition suggests that the color stability of lactate-enhanced fresh meat is not due to direct interactions between the ingredient and the heme protein. © 2013.

H2-broadening, shifting and mixing coefficients of the doublets in the ν2 and ν4 bands of PH3 at room temperature

NASA Astrophysics Data System (ADS)

Salem, Jamel; Blanquet, Ghislain; Lepère, Muriel; Younes, Rached ben

2018-05-01

The broadening, shifting and mixing coefficients of the doublet spectral lines in the ν2 and ν4 bands of PH3 perturbed by H2 have been determined at room temperature. Indeed, the collisional spectroscopic parameters: intensities, line widths, line shifts and line mixing parameters, are all grouped together in the collisional relaxation matrix. To analyse the collisional process and physical effects on spectra of phosphine (PH3), we have used the measurements carried out using a tunable diode-laser spectrometer in the ν2 and ν4 bands of PH3 perturbed by hydrogen (H2) at room temperature. The recorded spectra are fitted by the Voigt profile and the speed-dependent uncorrelated hard collision model of Rautian and Sobelman. These profiles are developed in the studies of isolated lines and are modified to account for the line mixing effects in the overlapping lines. The line widths, line shifts and line mixing parameters are given for six A1 and A2 doublet lines with quantum numbers K = 3n, (n = 1, 2, …) and overlapped by collisional broadening at pressures of less than 50 mbar.

Quantum and quasiclassical dynamics of the multi-channel H + H2S reaction.

PubMed

Qi, Ji; Lu, Dandan; Song, Hongwei; Li, Jun; Yang, Minghui

2017-03-28

The prototypical multi-channel reaction H + H 2 S → H 2 + SH/H + H 2 S has been investigated using the full-dimensional quantum scattering and quasi-classical trajectory methods to unveil the underlying competition mechanism between different product channels and the mode specificity. This reaction favors the abstraction channel over the exchange channel. For both channels, excitations in the two stretching modes promote the reaction with nearly equal efficiency and are more efficient than the bending mode excitation. However, they are all less efficient than the translational energy. In addition, the experimentally observed non-Arrhenius temperature dependence of the thermal rate constants is reasonably reproduced by the quantum dynamics calculations, confirming that the non-Arrhenius behavior is caused by the pronounced quantum tunneling.

Studies on two-gap superconductivity in 2H-NbS2

NASA Astrophysics Data System (ADS)

Kačmarčík, J.; Pribulová, Z.; Marcenat, C.; Klein, T.; Rodière, P.; Cario, L.; Samuely, P.

2010-12-01

We present the ac-calorimetry measurements of superconducting 2H-NbS2 in the temperature range down to 0.6 K and magnetic fields up to 8 T. The temperature and magnetic field dependence of the electronic specific heat consistently indicate existence of two superconducting energy gaps in the system - one of them with the coupling ratio below the BCS weak-coupling limit and the other above that value. These results support previous findings by scanning tunneling microscopy and spectroscopy measurements [I. Guillamón, H. Suderow, S. Vieira, L. Cario, et al., Phys. Rev. Lett. 101 (2008) 166407] of two pronounced features in density of states related to a two-gap superconductivity in this system.

Temperature-dependence laws of absorption line shape parameters of the CO2 ν3 band

NASA Astrophysics Data System (ADS)

Wilzewski, J. S.; Birk, M.; Loos, J.; Wagner, G.

2018-02-01

To improve the understanding of temperature-dependence laws of spectral line shape parameters, spectra of the ν3 rovibrational band of CO2 perturbed by 10, 30, 100, 300 and 1000 mbar of N2 were recorded at nine temperatures between 190 K and 330 K using a 22 cm long single-pass absorption cell in a Bruker IFS125 HR Fourier Transform spectrometer. The spectra were fitted employing a quadratic speed-dependent hard collision model in the Hartmann-Tran implementation extended to account for line mixing in the Rosenkranz approximation by means of a multispectrum fitting approach developed at DLR. This enables high accuracy parameter retrievals to reproduce the spectra down to noise level and we present the behavior of line widths, shifts, speed-dependence-, collisional narrowing- and line mixing-parameters over this 140 K temperature range.

CO Diffusion into Amorphous H2O Ices

NASA Astrophysics Data System (ADS)

Lauck, Trish; Karssemeijer, Leendertjan; Shulenberger, Katherine; Rajappan, Mahesh; Öberg, Karin I.; Cuppen, Herma M.

2015-03-01

The mobility of atoms, molecules, and radicals in icy grain mantles regulates ice restructuring, desorption, and chemistry in astrophysical environments. Interstellar ices are dominated by H2O, and diffusion on external and internal (pore) surfaces of H2O-rich ices is therefore a key process to constrain. This study aims to quantify the diffusion kinetics and barrier of the abundant ice constituent CO into H2O-dominated ices at low temperatures (15-23 K), by measuring the mixing rate of initially layered H2O(:CO2)/CO ices. The mixed fraction of CO as a function of time is determined by monitoring the shape of the infrared CO stretching band. Mixing is observed at all investigated temperatures on minute timescales and can be ascribed to CO diffusion in H2O ice pores. The diffusion coefficient and final mixed fraction depend on ice temperature, porosity, thickness, and composition. The experiments are analyzed by applying Fick’s diffusion equation under the assumption that mixing is due to CO diffusion into an immobile H2O ice. The extracted energy barrier for CO diffusion into amorphous H2O ice is ˜160 K. This is effectively a surface diffusion barrier. The derived barrier is low compared to current surface diffusion barriers in use in astrochemical models. Its adoption may significantly change the expected timescales for different ice processes in interstellar environments.

Temperature- and Phase-Dependent Phonon Renormalization in 1T'-MoS2.

PubMed

Tan, Sherman Jun Rong; Sarkar, Soumya; Zhao, Xiaoxu; Luo, Xin; Luo, Yong Zheng; Poh, Sock Mui; Abdelwahab, Ibrahim; Zhou, Wu; Venkatesan, Thirumalai; Chen, Wei; Quek, Su Ying; Loh, Kian Ping

2018-05-22

Polymorph engineering of 2H-MoS 2 , which can be achieved by alkali metal intercalation to obtain either the mixed 2H/1T' phases or a homogeneous 1T' phase, has received wide interest recently, since this serves as an effective route to tune the electrical and catalytic properties of MoS 2 . As opposed to an idealized single crystal-to-single crystal phase conversion, the 2H to 1T' phase conversion results in crystal domain size reduction as well as strained lattices, although how these develop with composition is not well understood. Herein, the evolution of the phonon modes in Li-intercalated 1T'-MoS 2 (Li x MoS 2 ) are investigated as a function of different 1T'-2H compositions. We observed that the strain evolution in the mixed phases is revealed by the softening of four Raman modes, B g ( J 1 ), A g ( J 3 ), E 1 2g , and A 1g , with increasing 1T' phase composition. Additionally, the first-order temperature coefficients of the 1T' phonon mode vary linearly with increasing 1T' composition, which is explained by increased electron-phonon and strain-phonon coupling.

Diurnal variation of intraoral pH and temperature.

PubMed

Choi, Jung Eun; Lyons, Karl M; Kieser, Jules A; Waddell, Neil J

2017-01-01

The aim of this study was to measure continuously the intraoral pH and temperature of healthy individuals to investigate their diurnal variations. Seventeen participants (mean age, 31±9 years) wore a custom-made intraoral appliance fitted with a pH probe and thermocouple for two sets of 24 h, while carrying out normal daily activities including sleep. The continuous changes in intraoral pH and temperature were captured using a sensor placed on the palatal aspect of the upper central incisors. The collected data were categorised into different status (awake and sleep) and periods (morning, afternoon, evening and night). Both quantitative and qualitative analyses were conducted. The intraoral pH change was found to show a distinctive daily rhythm, showing a 12-h interval between maximum (7.73) and minimum (6.6) pH values. The maximum and minimum values were found to repeat after 24 h. The mean pH over 48 h (two sets of 24 h) was found to be 7.27 (±0.74). There was significant difference found in pH when subjects were awake and asleep and different periods during the day ( P <0.001). The mean intraoral temperature was 33.99 °C (±4.9), with less distinctive daily rhythm compared with pH. There was a significant difference found in temperature depending on the time of the day, except between morning and afternoon ( P =0.78). Our results showed that there is a distinctive daily, circadian-like pattern in intraoral pH variation over a 24-h period, which has been considered as one of the risk factors in sleep-related dental diseases.

Low-temperature electronic transport in single K(0.27)MnO(2)·0.5H(2)O nanowires: enhanced electron-electron interaction.

PubMed

Long, Y Z; Yin, Z H; Chen, Z J; Jin, A Z; Gu, C Z; Zhang, H T; Chen, X H

2008-05-28

The current-voltage (I-V) characteristics and electrical resistivity of isolated potassium manganese oxide (K(0.27)MnO(2)·0.5H(2)O) nanowires prepared by a simple hydrothermal method were investigated over a wide temperature range from 300 to 4 K. With lowering temperature, a transition from linear to nonlinear I-V curves was observed around 50 K, and a clear zero bias anomaly (i.e., Coulomb gap-like structure) appeared on the differential conductance (dI/dV) curves, possibly due to enhanced electron-electron interaction at low temperatures. The temperature dependence of resistivity, [Formula: see text], follows the Efros-Shklovskii (ES) law, as expected in the presence of a Coulomb gap. Here we note that both the ES law and Coulomb blockade can in principle lead to a reduced zero bias conductance at low temperatures; in this study we cannot exclude the possibility of Coulomb-blockade transport in the measured nanowires, especially in the low-temperature range. It is still an open question how to pin down the origin of the observed reduction to a Coulomb gap (ES law) or Coulomb blockade.

Diagnostic system for measuring temperature, pressure, CO2 concentration and H2O concentration in a fluid stream

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

Partridge, Jr., William P.; Jatana, Gurneesh Singh; Yoo, Ji-Hyung

A diagnostic system for measuring temperature, pressure, CO.sub.2 concentration and H.sub.2O concentration in a fluid stream is described. The system may include one or more probes that sample the fluid stream spatially, temporally and over ranges of pressure and temperature. Laser light sources are directed down pitch optical cables, through a lens and to a mirror, where the light sources are reflected back, through the lens to catch optical cables. The light travels through the catch optical cables to detectors, which provide electrical signals to a processer. The processer utilizes the signals to calculate CO.sub.2 concentration based on the temperaturesmore » derived from H.sub.2O vapor concentration. A probe for sampling CO.sub.2 and H.sub.2O vapor concentrations is also disclosed. Various mechanical features interact together to ensure the pitch and catch optical cables are properly aligned with the lens during assembly and use.« less

A new metal-organic framework for separation of C2H2/CH4 and CO2/CH4 at room temperature

NASA Astrophysics Data System (ADS)

Duan, Xing; Zhou, You; Lv, Ran; Yu, Ben; Chen, Haodong; Ji, Zhenguo; Cui, Yuanjing; Yang, Yu; Qian, Guodong

2018-04-01

A 3D microporous metal-organic framework with open Cu2+ sites and suitable pore space, [Cu2(L)(H2O)2]·(H2O)4(DMF)8 (ZJU-15, H4L = 5,5‧-(9H-carbazole-2,7-diyl)diisophthalic acid; DMF = N,N-dimethylformamide; ZJU = Zhejiang University), has been constructed and characterized. The activated ZJU-15a has three different types of cages and exhibits BET surface area of 1660 m2 g-1, and can separate gas mixture of C2H2/CH4 and CO2/CH4 at room temperature.

Thermodynamics of Silicon-Hydroxide Formation in H2O Containing Atmospheres

NASA Technical Reports Server (NTRS)

Copland, Evan; Myers, Dwight; Opila, Elizabeth J.; Jacobson, Nathan S.

2001-01-01

The formation of volatile silicon-hydroxide species from SiO2 in water containing atmospheres has been identified as a potentially important mode of degradation of Si-based ceramics. Availability of thermodynamic data for these species is a major problem. This study is part of an ongoing effort to obtain reliable, experimentally determined thermodynamic data for these species. The transpiration method was used to measure the pressure of Si-containing vapor in equilibrium with SiO2 (cristobalite) and Ar + H2O(g) with various mole fractions of water vapor, X(sub H2O), at temperatures ranging from 1000 to 1780 K. Enthalpies and entropies for the reaction, SiO2(s) + 2H2O(g) = Si(OH)4(g), were obtained, at X(sub H2O) = 0.15 and 0.37, from the variation of lnK with 1/T according to the 'second law method'. The following data were obtained: delta(H)deg = 52.9 +/- 3.7 kJ/mole and delta(S)deg = -68.6 +/- 2.5 J/mole K at an average temperature of 1550 K, and delta(H)deg = 52.5+/-2.0 kJ/mole and delta(S)deg= -69.7 +/- 1.5 J/moleK at an average temperature of 1384 K, for X(sub H2O)= 0.15 and 0.37, respectively. These data agree with results from the literature obtained at an average temperature of 1600 K, and strongly suggest Si(OH)4(g) is the dominant vapor species. Contradictory results were obtained with the determination of the dependence of Si-containing vapor pressure on the partial pressure of water vapor at 1187 and 1722 K. These results suggested the Si-containing vapor could be a mixture of Si(OH)4 + SiO(OH)2. Further pressure dependent studies are in progress to resolve these issues.

The roles of two O-donor ligands in the Fe2+-binding and H2O2-sensing by the Fe2+-dependent H2O2 sensor PerR.

PubMed

Ji, Chang-Jun; Yang, Yoon-Mo; Kim, Jung-Hoon; Ryu, Su-Hyun; Youn, Hwan; Lee, Jin-Won

2018-05-10

PerR is a metal-dependent peroxide sensing transcription factor which controls the expression of genes involved in peroxide resistance. The function of Bacillus subtilis PerR is mainly dictated by the regulatory metal ion (Fe 2+ or Mn 2+ ) coordinated by three N-donor ligands (His37, His91, and His93) and two O-donor ligands (Asp85 and Asp104). While H 2 O 2 sensing by PerR is mediated by Fe 2+ -dependent oxidation of N-donor ligand (either His37 or His91), one of the O-donor ligands (Asp104), but not Asp85, has been proposed as the key residue that regulates the sensitivity of PerR to H 2 O 2 . Here we systematically investigated the relative roles of two O-donor ligands of PerR in metal-binding affinity and H 2 O 2 sensitivity in vivo and in vitro. Consistent with the previous report, in vitro the D104E-PerR could not sense low levels of H 2 O 2 in the presence of excess Fe 2+ sufficient for the formation of the Fe 2+ -bound D104E-PerR. However, the expression of PerR-regulated reporter fusion was not repressed by D104E-PerR in the presence of Fe 2+ , suggesting that Fe 2+ is not an effective corepressor for this mutant protein in vivo. Furthermore, in vitro metal titration assays indicate that D104E-PerR has a significantly reduced affinity for Fe 2+ , but not for Mn 2+ , when compared to wild type PerR. These data indicate that the type of O-donor ligand (Asp vs. Glu) at position 104 is an important determinant in providing high Fe 2+ -binding affinity required for the sensing of the physiologically relevant Fe 2+ -levels, in addition to its role in rendering PerR highly sensitive to physiological levels of H 2 O 2 . In comparison, the D85E-PerR did not show a perturbed change in Fe 2+ -binding affinity, however, it displayed a slightly decreased sensitivity to H 2 O 2 both in vivo and in vitro, suggesting that the type of O-donor ligand (Asp vs. Glu) at position 85 may be important for the fine-tuning of H 2 O 2 sensitivity. Copyright © 2018 Elsevier

Low Temperature Ohmic Contact Formation of Ni2Si on N-type 4H-SiC and 6H-SiC

NASA Technical Reports Server (NTRS)

Elsamadicy, A. M.; Ila, D.; Zimmerman, R.; Muntele, C.; Evelyn, L.; Muntele, I.; Poker, D. B.; Hensley, D.; Hirvonen, J. K.; Demaree, J. D.;

Removal of H{sub 2}S using molten carbonate at high temperature

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

Kawase, Makoto, E-mail: kawase@criepi.denken.or.jp; Otaka, Maromu

2013-12-15

Highlights: • The performance of molten carbonate for the removal of H{sub 2}S improves at higher temperatures. • The degree of H{sub 2}S removal is significantly affected by the CO{sub 2} concentration in syngas. • Addition of carbon elements, such as char and tar, decrease the negative effects of CO{sub 2}. • Continuous addition of carbon elements into molten carbonate enables continuous desulfurization. • Desulfurization using molten carbonate is suitable for gasification gas. - Abstract: Gasification is considered to be an effective process for energy conversion from various sources such as coal, biomass, and waste. Cleanup of the hot syngasmore » produced by such a process may improve the thermal efficiency of the overall gasification system. Therefore, the cleanup of hot syngas from biomass gasification using molten carbonate is investigated in bench-scale tests. Molten carbonate acts as an absorbent during desulfurization and dechlorination and as a thermal catalyst for tar cracking. In this study, the performance of molten carbonate for removing H{sub 2}S was evaluated. The temperature of the molten carbonate was set within the range from 800 to 1000 °C. It is found that the removal of H{sub 2}S is significantly affected by the concentration of CO{sub 2} in the syngas. When only a small percentage of CO{sub 2} is present, desulfurization using molten carbonate is inadequate. However, when carbon elements, such as char and tar, are continuously supplied, H{sub 2}S removal can be maintained at a high level. To confirm the performance of the molten carbonate gas-cleaning system, purified biogas was used as a fuel in power generation tests with a molten carbonate fuel cell (MCFC). The fuel cell is a high-performance sensor for detecting gaseous impurities. When purified gas from a gas-cleaning reactor was continuously supplied to the fuel cell, the cell voltage remained stable. Thus, the molten carbonate gas-cleaning reactor was found to afford

Correlation between Temperature-dependent Fatigue Resistance and Differential Scanning Calorimetry Analysis for 2 Contemporary Rotary Instruments.

PubMed

Arias, Ana; Macorra, José C; Govindjee, Sanjay; Peters, Ove A

2018-04-01

The aim of this study was to assess differences in cyclic fatigue (CF) life of contemporary heat-treated nickel-titanium rotary instruments at room and body temperatures and to document corresponding phase transformations. Forty Hyflex EDM (H-EDM) files (Coltene, Cuyahoga Falls, OH [#25/.08, manufactured by electrical discharge machining]) and 40 TRUShape (TS) files (Dentsply Tulsa Dental Specialties, Tulsa, OK [#25/.06v, manufactured by grinding and shape setting]) were divided into 2 groups (n = 20) for CF resistance tests in a water bath either at room (22°C ± 0.5°C) or body temperature (37°C ± 0.5°C). Instruments were rotated in a simulated canal (angle = 60°, radius = 3 mm, and center of the curvature 5 mm from the tip) until fracture occurred. The motor was controlled by an electric circuit that was interrupted after instrument fracture. The mean half-life and beta and eta Weibull parameters were determined and compared. Two instruments of each brand were subjected to differential scanning calorimetry (DSC). While TS instruments lasted significantly longer at room temperature (mean life = 234.7 seconds; 95% confidence interval [CI], 209-263.6) than at body temperature (mean life = 83.2 seconds; 95% CI, 76-91.1), temperature did not affect H-EDM behavior (room temperature mean life = 725.4 seconds; 95% CI, 658.8-798.8 and body temperature mean life = 717.9 seconds; 95% CI, 636.8-809.3). H-EDM instruments significantly outlasted TS instruments at both temperatures. At body temperature, TS was predominantly austenitic, whereas H-EDM was martensitic or in R-phase. TS was in a mixed austenitic/martensitic phase at 22°C, whereas H-EDM was in the same state as at 37°C. H-EDM had a longer fatigue life than TS, which showed a marked decrease in fatigue life at body temperature; neither the life span nor the state of the microstructure in the DSC differed for H-EDM between room or body temperature. Copyright © 2017 American Association of

Tunneling chemical reactions D+H{sub 2}{yields}DH+H and D+DH{yields}D{sub 2}+H in solid D{sub 2}-H{sub 2} and HD-H{sub 2} mixtures: An electron-spin-resonance study

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

Kumada, Takayuki

2006-03-07

Tunneling chemical reactions D+H{sub 2}{yields}DH+H and D+DH{yields}D{sub 2}+H in solid HD-H{sub 2} and D{sub 2}-H{sub 2} mixtures were studied in the temperature range between 4 and 8 K. These reactions were initiated by UV photolysis of DI molecules doped in these solids for 30 s and followed by measuring the time course of electron-spin-resonance (ESR) intensities of D and H atoms. ESR intensity of D atoms produced by the photolysis decreases but that of H atoms increases with time. Time course of the D and H intensities has the fast and slow processes. The fast process, which finishes within {approx}300more » s after the photolysis, is assigned to the reaction of D atom with one of its nearest-neighboring H{sub 2} molecules, D(H{sub 2}){sub n}(HD){sub 12-n}{yields}H(H{sub 2}){sub n-1}(HD){sub 13-n} or D(H{sub 2}){sub n}(D{sub 2}){sub 12-n}{yields}H(HD)(H{sub 2}){sub n-1}(D{sub 2}){sub 12-n} for 12{>=}n{>=}1. Rate constant for the D+H{sub 2} reaction between neighboring D atom-H{sub 2} molecule pair is determined to be (7.5{+-}0.7)x10{sup -3} s{sup -1} in solid HD-H{sub 2} and (1.3{+-}0.3)x10{sup -2} s{sup -1} in D{sub 2}-H{sub 2} at 4.1 K, which is very close to that calculated based on the theory of chemical reaction in gas phase by Hancock et al. [J. Chem. Phys. 91, 3492 (1989)] and Takayanagi and Sato [J. Chem. Phys. 92, 2862 (1990)]. This rate constant was found to be independent of temperature up to 7 K within experimental error of {+-}30%. The slow process is assigned to the reaction of D atom produced in a cage fully surrounded by HD or D{sub 2} molecules, D(HD){sub 12} or D(D{sub 2}){sub 12}. This D atom undergoes the D+DH reaction with one of its nearest-neighboring HD molecules in solid HD-H{sub 2} or diffuses to the neighbor of H{sub 2} molecules to allow the D+H{sub 2} reaction in solid HD-H{sub 2} and D{sub 2}-H{sub 2}. The former is the main channel in solid HD-H{sub 2} below 6 K where D atoms diffuse very slowly, whereas the latter dominates

Simulation of temperature dependent dielectric breakdown in n{sup +}-polySi/SiO{sub 2}/n-6H-SiC structures during Poole-Frenkel stress at positive gate bias

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

Samanta, Piyas, E-mail: piyas@vcfw.org; Mandal, Krishna C., E-mail: mandalk@cec.sc.edu

2016-08-14

We present for the first time a thorough investigation of trapped-hole induced gate oxide deterioration and simulation results of time-dependent dielectric breakdown (TDDB) of thin (7–25 nm) silicon dioxide (SiO{sub 2}) films thermally grown on (0 0 0 1) silicon (Si) face of n-type 6H-silicon carbide (n-6H-SiC). Gate oxide reliability was studied during both constant voltage and current stress with positive bias on the degenerately doped n-type poly-crystalline silicon (n{sup +}-polySi) gate at a wide range of temperatures between 27 and 225 °C. The gate leakage current was identified as the Poole-Frenkel (PF) emission of electrons trapped at an energy 0.92 eV belowmore » the SiO{sub 2} conduction band. Holes were generated in the n{sup +}-polySi anode material as well as in the oxide bulk via band-to-band ionization depending on the film thickness t{sub ox} and the energy of the hot-electrons (emitted via PF mechanism) during their transport through oxide films at oxide electric fields E{sub ox} ranging from 5 to 10 MV/cm. Our simulated time-to-breakdown (t{sub BD}) results are in excellent agreement with those obtained from time consuming TDDB measurements. It is observed that irrespective of stress temperatures, the t{sub BD} values estimated in the field range between 5 and 9 MV/cm better fit to reciprocal field (1/E) model for the thickness range studied here. Furthermore, for a 10 year projected device lifetime, a good reliability margin of safe operating field from 8.5 to 7.5 MV/cm for 7 nm and 8.1 to 6.9 MV/cm for 25 nm thick SiO{sub 2} was observed between 27 and 225 °C.« less

Resonances in the reaction ortho- and para- D2 + H at temperatures below 10 K

NASA Astrophysics Data System (ADS)

Simbotin, I.; Côté, R.

2016-05-01

In a previous study we reported cross sections for the reaction H2 + D in the temperature regime 10-6 < T < 10 K, and found pronounced shape resonances, especially in the p and d partial waves. We found that the resonant structures were sensitive to the initial rovibrational state of H2; in particular, we showed that the effect of the nuclear-spin symmetry was very important, since ortho- and para- H2 gave significantly different results. We now investigate the reaction D2 + H for vibrationally excited ortho- and para- D2, and compare and contrast these results with those for H2 + D. We remark that this benchmark system is a prototypical example of reactions with a strong barrier, which have very small cross sections in the cold and ultracold regimes. However, shape resonances can enhance the reaction cross sections by orders of magnitude for temperatures around and below T = 1 K. Moreover, resonant features would provide stringent tests for quantum chemistry calculations of potential energy surfaces. Partial support from the US Army Research Office (Grant No. W911NF-13-1-0213).

A study on the temperature dependence of the threshold switching characteristics of Ge2Sb2Te5

NASA Astrophysics Data System (ADS)

Lee, Suyoun; Jeong, Doo Seok; Jeong, Jeung-hyun; Zhe, Wu; Park, Young-Wook; Ahn, Hyung-Woo; Cheong, Byung-ki

2010-01-01

We investigated the temperature dependence of the threshold switching characteristics of a memory-type chalcogenide material, Ge2Sb2Te5. We found that the threshold voltage (Vth) decreased linearly with temperature, implying the existence of a critical conductivity of Ge2Sb2Te5 for its threshold switching. In addition, we investigated the effect of bias voltage and temperature on the delay time (tdel) of the threshold switching of Ge2Sb2Te5 and described the measured relationship by an analytic expression which we derived based on a physical model where thermally activated hopping is a dominant transport mechanism in the material.

Formation of H{sub 2} from internally heated polycyclic aromatic hydrocarbons: Excitation energy dependence

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

Chen, T., E-mail: tao.chen@fysik.su.se, E-mail: henning@fysik.su.se; Gatchell, M.; Stockett, M. H.

2015-04-14

We have investigated the effectiveness of molecular hydrogen (H{sub 2}) formation from Polycyclic Aromatic Hydrocarbons (PAHs) which are internally heated by collisions with keV ions. The present and earlier experimental results are analyzed in view of molecular structure calculations and a simple collision model. We estimate that H{sub 2} formation becomes important for internal PAH temperatures exceeding about 2200 K, regardless of the PAH size and the excitation agent. This suggests that keV ions may effectively induce such reactions, while they are unlikely due to, e.g., absorption of single photons with energies below the Lyman limit. The present analysis alsomore » suggests that H{sub 2} emission is correlated with multi-fragmentation processes, which means that the [PAH-2H]{sup +} peak intensities in the mass spectra may not be used for estimating H{sub 2}-formation rates.« less

Line shape parameters for the H2O-H2 collision system for application to exoplanet and planetary atmospheres

NASA Astrophysics Data System (ADS)

Renaud, Candice L.; Cleghorn, Kara; Hartmann, Léna; Vispoel, Bastien; Gamache, Robert R.

2018-05-01

Water can be detected throughout the universe: in comets, asteroids, dwarf planets, the inner and outer planets in our solar system, cool stars, brown dwarfs, and on many exoplanets. Here the focus is on locations rich in hydrogen gas. To properly study these environments, there is a need for the line shape parameters for H2O transitions in collision with hydrogen. This work presents calculations of the half-width and line shift, made using the Modified Complex Robert-Bonamy (MCRB) formalism, at a number of temperatures. It is shown that this collision system is strongly off-resonance. For such conditions, the atom-atom part of the intermolecular potential dominates the interaction of the radiating and perturbing molecules. The atom-atom parameters were adjusted by fitting the H2O-H2 measurements of Brown and Plymate (1996). Several techniques were used to extract lines for which there is more confidence in the quality of the data. The final potential yields results that agree with the measurements with ∼0.3% difference and a 5.9% standard deviation. Using this potential, MCRB calculations were made for all transitions in the pure rotation, ν2, ν1, and ν3 bands. The structure of the line shape parameters and the temperature dependence of the half-width, as a function of the rotational and vibrational quantum numbers, are discussed. It is shown that the power law model of the T-dependence of the half-width is inadequate over large temperature ranges.

Temperature and field dependence of critical currents in V/sub 3/Ga wire produced by the MJR technique

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

Francavilla, T.L.; Gubser, D.U.; Pande, C.S.

1985-03-01

The temperature dependence of V/sub 3/Ga multifilamentary wire produced by the modified jelly roll technique is reported as a function of applied magnetic field in the range 10K - 14K and 0-13T. Parameters which relate J /SUB c/ to H at 4.2K were found to apply at these temperatures and fields. The form of the temperature dependence of the critical current density is compared with theory.

Evaluation of lophine derivatives as L-012 (luminol analog)-dependent chemiluminescence enhancers for measuring horseradish peroxidase and H2O2.

PubMed

Ichibangase, T; Ohba, Y; Kishikawa, N; Nakashima, K; Kuroda, N

2014-03-01

8-Amino-5-chloro-7-phenylpyrido[3,4-d]pyridazine-1,4(2H,3H)dione (L-012) was recently synthesized as a new chemiluminescence (CL) probe; the light intensity and the sensitivity of L-012 are higher than those of other CL probes such as luminol. Previously, our group developed four lophine-based CL enhancers of the horseradish peroxidase (HRP)-catalyzed CL oxidation of luminol, namely 2-(4-hydroxyphenyl)-4,5-diphenylimidazole (HDI), 2-(4-hydroxyphenyl)-4,5-di(2-pyridyl)imidazole (HPI), 4-(4,5-diphenyl-1H-imidazol-2-yl)phenylboronic acid (DPA), and 4-[4,5-di(2-pyridyl)-1H-imidazol-2-yl]phenylboronic acid (DPPA), and showed that DPPA was suitable for the photographic detection of HRP. In this study, we replaced luminol with L-012 and evaluated these as L-012-dependent CL enhancers. In addition, to detect HRP and/or H2O2 with higher sensitivity, each detection condition for the L-012-HRP-H2O2 enhanced CL was optimized. All the derivatives enhanced the L-012-dependent CL as well as luminol CL; HPI generated the highest enhanced luminescence. Under optimized conditions for HRP detection, the detection limit of HRP was 0.08 fmol. By contrast, the detection limit of HRP with the enhanced L-012-dependent CL using 4-iodophenol, which is a common enhancer of luminol CL, was 1.1 fmol. With regard to H2O2 detection, the detection limits for enhanced CL with HPI and 4-iodophenol were 0.29 and 1.5 pmol, respectively. Therefore, it is demonstrated that HPI is the most superior L-012-dependent CL enhancer. Copyright © 2013 John Wiley & Sons, Ltd.

Cryogenic Temperature-Dependent Refractive Index Measurements of CaF2 and Infrasil 301

NASA Technical Reports Server (NTRS)

Frey, Bradley J.; Leviton, Douglas B.; Madison, TImothy J.

2007-01-01

In order to enable high quality lens design using calcium fluoride (CaF2) and Heraeus Infrasil 30 (Infrasil) at cryogenic temperatures, we have measured the absolute refractive index of prisms of these two materials using the Cryogenic, High-Accuracy Refraction Measuring System (CHARMS) at NASA's Goddard Space Flight Center, as a function of both wavelength and temperature. For CaF2, we report absolute refractive index and thermo-optic coefficient (dn/dT) at temperatures ranging from 25 to 300 K at wavelengths from 0.4 to 5.6 micrometers; for Infrasil we cover temperatures ranging from 35 to 300K and wavelengths from 0.4 to 3.6 micrometers. We investigate the interspecimen variability between measurements of two unrelated samples of CaF2, and we also compare our results for Infrasil to previous measurements fo Corning 7980 fused silica. Finally, we provide temperature-dependent Sellmeier coefficients based on our data to allow accurate interpolation of index to other wavelengths and temperatures and compare those results to other data found in the literature.

Muscovite dissolution kinetics as a function of pH at elevated temperature

DOE PAGES

Lammers, Kristin; Smith, Megan M.; Carroll, Susan A.

2017-06-07

We report that mineral reactivity can play an important role in fracture-controlled fluid networks where maintaining or increasing permeability is a goal, such as enhanced geothermal systems. In these systems, dissolution generates new void space, removes cement and physically transports less reactive mineral grains, while secondary precipitation acts to narrow or seal off fluid pathways. Sheet silicate mineral reactivity is likely to affect permeability evolution at the elevated temperatures of geothermal reservoirs because of the high reactive surface area and prevalence of these minerals in hydrothermal zones. To better describe the reactivity of one common sheet silicate, muscovite, we conducted kinetic dissolution experiments using flow-through reactors at temperatures of 100–280 °C and a pH range of 2–9. Surface area-normalized muscovite dissolution rates ranged from 0.17–155 · 10 - 11 mol m - 2 s - 1 over this temperature range, but showed little variation with pH above 150 °C. Aluminum was released to solution nonstoichiometrically with respect to dissolved silica, most likely resulting from secondary precipitation of an aluminum oxy-hydroxide identified as boehmite (γ-AlO(OH)( s)) by X-ray diffraction in reaction products from experiments conducted at pH ≤ 6. Surface area-normalized muscovite dissolution rates, Rate mus (mol m - 2 s - 1), can be described from 25 to 280 °C with the following kinetic rate equation: Rate mus = ([3∙10 -3∙e -44 /R∙T∙amore » $$0.8\\atop{H+}$$] + [9∙10 -6∙e- 45/R∙T] + [5∙10 -1∙ e-61/R∙T ∙a$$0.6\\atop{OH-}$$] ∙ (1-e -ΔGr/RT) where the rate and pre-exponential factors are in mol m - 2 s - 1; the activation energies, E, are in kJ mol - 1; a H+ and a OH- represent the activities of H + and OH -, respectively; R (kJ mol - 1 K - 1) is the gas constant; T is the temperature in Kelvins; and ΔG r (kJ mol - 1) is a measure of how close the aqueous solution is to muscovite equilibrium. The rate

Muscovite dissolution kinetics as a function of pH at elevated temperature

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

Lammers, Kristin; Smith, Megan M.; Carroll, Susan A.

We report that mineral reactivity can play an important role in fracture-controlled fluid networks where maintaining or increasing permeability is a goal, such as enhanced geothermal systems. In these systems, dissolution generates new void space, removes cement and physically transports less reactive mineral grains, while secondary precipitation acts to narrow or seal off fluid pathways. Sheet silicate mineral reactivity is likely to affect permeability evolution at the elevated temperatures of geothermal reservoirs because of the high reactive surface area and prevalence of these minerals in hydrothermal zones. To better describe the reactivity of one common sheet silicate, muscovite, we conducted kinetic dissolution experiments using flow-through reactors at temperatures of 100–280 °C and a pH range of 2–9. Surface area-normalized muscovite dissolution rates ranged from 0.17–155 · 10 - 11 mol m - 2 s - 1 over this temperature range, but showed little variation with pH above 150 °C. Aluminum was released to solution nonstoichiometrically with respect to dissolved silica, most likely resulting from secondary precipitation of an aluminum oxy-hydroxide identified as boehmite (γ-AlO(OH)( s)) by X-ray diffraction in reaction products from experiments conducted at pH ≤ 6. Surface area-normalized muscovite dissolution rates, Rate mus (mol m - 2 s - 1), can be described from 25 to 280 °C with the following kinetic rate equation: Rate mus = ([3∙10 -3∙e -44 /R∙T∙amore » $$0.8\\atop{H+}$$] + [9∙10 -6∙e- 45/R∙T] + [5∙10 -1∙ e-61/R∙T ∙a$$0.6\\atop{OH-}$$] ∙ (1-e -ΔGr/RT) where the rate and pre-exponential factors are in mol m - 2 s - 1; the activation energies, E, are in kJ mol - 1; a H+ and a OH- represent the activities of H + and OH -, respectively; R (kJ mol - 1 K - 1) is the gas constant; T is the temperature in Kelvins; and ΔG r (kJ mol - 1) is a measure of how close the aqueous solution is to muscovite equilibrium. The rate

Zr/ZrO2 sensors for in situ measurement of pH in high-temperature and -pressure aqueous solutions.

PubMed

Zhang, R H; Zhang, X T; Hu, S M

2008-04-15

The aim of this study is to develop new pH sensors that can be used to test and monitor hydrogen ion activity in hydrothermal conditions. A Zr/ZrO2 oxidation electrode is fabricated for in situ pH measurement of high-temperature aqueous solutions. This sensor responds rapidly and precisely to pH over a wide range of temperature and pressure. The Zr/ZrO2 electrode was made by oxidizing zirconium metal wire with Na2CO3 melt, which produced a thin film of ZrO2 on its surface. Thus, an oxidation-reduction electrode was produced. The Zr/ZrO2 electrode has a good electrochemical stability over a wide range of pH in high-temperature aqueous solutions when used with a Ag/AgCl reference electrode. Measurements of the Zr/ZrO2 sensor potential against a Ag/AgCl reference electrode is shown to vary linearly with pH between temperatures 20 and 200 degrees C. The slope of the potential versus pH at high temperature is slightly below the theoretical value indicated by the Nernst equation; such deviation is attributed to the fact that the sensor is not strictly at equilibrium with the solution to be tested in a short period of time. The Zr/ZrO2 sensor can be calibrated over the conditions that exist in the natural deep-seawater. Our studies showed that the Zr/ZrO2 electrode is a suitable pH sensor for the hydrothermal systems at midocean ridge or other geothermal systems with the high-temperature environment. Yttria-stabilized zirconia sensors have also been used to investigate the pH of hydrothermal fluids in hot springs vents at midocean ridge. These sensors, however, are not sensitive below 200 degrees C. Zr/ZrO2 sensors have wider temperature range and can be severed as good alternative sensors for measuring the pH of hydrothermal fluids.

Application of TAED/H2O2 system for low temperature bleaching of crude cellulose extracted from jute fiber

NASA Astrophysics Data System (ADS)

Wen, Zuoqiang; Zou, Linbo; Wang, Weiming

2018-03-01

Tetraacetylethylenediamine (TAED) activated hydrogen peroxide system had been applied for bleaching of crude cellulose extracted from jute fiber. Comparing with conventional hydrogen peroxide bleaching system, those results showed that bleaching temperature and time could be effectively reduced, and a preferable whiteness could be produced under faint alkaline condition. And the optimum conditions for activated bleaching system could be summarized as molar ratio of H2O2/TAED 1:0.7, pH 8, pure hydrogen peroxide 0.09 mol/L, temperature 70 °C and time 60min.

Molecular Gibbs Surface Excess and CO2-Hydrate Density Determine the Strong Temperature- and Pressure-Dependent Supercritical CO2-Brine Interfacial Tension.

PubMed

Ji, Jiayuan; Zhao, Lingling; Tao, Lu; Lin, Shangchao

2017-06-29

In CO 2 geological storage, the interfacial tension (IFT) between supercritical CO 2 and brine is critical for the storage capacitance design to prevent CO 2 leakage. IFT relies not only on the interfacial molecule properties but also on the environmental conditions at different storage sites. In this paper, supercritical CO 2 -NaCl solution systems are modeled at 343-373 K and 6-35 MPa under the salinity of 1.89 mol/L using molecular dynamics simulations. After computing and comparing the molecular density profile across the interface, the atomic radial distribution function, the molecular orientation distribution, the molecular Gibbs surface excess (derived from the molecular density profile), and the CO 2 -hydrate number density under the above environmental conditions, we confirm that only the molecular Gibbs surface excess of CO 2 molecules and the CO 2 -hydrate number density correlate strongly with the temperature- and pressure-dependent IFTs. We also compute the populations of two distinct CO 2 -hydrate structures (T-type and H-type) and attribute the observed dependence of IFTs to the dominance of the more stable, surfactant-like T-type CO 2 -hydrates at the interface. On the basis of these new molecular mechanisms behind IFT variations, this study could guide the rational design of suitable injecting environmental pressure and temperature conditions. We believe that the above two molecular-level metrics (Gibbs surface excess and hydrate number density) are of great fundamental importance for understanding the supercritical CO 2 -water interface and engineering applications in geological CO 2 storage.

H2O2 mediates ALA-induced glutathione and ascorbate accumulation in the perception and resistance to oxidative stress in Solanum lycopersicum at low temperatures.

PubMed

Liu, Tao; Hu, Xiaohui; Zhang, Jiao; Zhang, Junheng; Du, Qingjie; Li, Jianming

2018-02-15

Low temperature is a crucial factor influencing plant growth and development. The chlorophyll precursor, 5-aminolevulinic acid (ALA) is widely used to improve plant cold tolerance. However, the interaction between H 2 O 2 and cellular redox signaling involved in ALA-induced resistance to low temperature stress in plants remains largely unknown. Here, the roles of ALA in perceiving and regulating low temperature-induced oxidative stress in tomato plants, together with the roles of H 2 O 2 and cellular redox states, were characterized. Low concentrations (10-25 mg·L - 1 ) of ALA enhanced low temperature-induced oxidative stress tolerance of tomato seedlings. The most effective concentration was 25 mg·L - 1 , which markedly increased the ratio of reduced glutathione and ascorbate (GSH and AsA), and enhanced the activities of superoxide dismutase, catalase, ascorbate peroxidase, dehydroascorbate reductase, and glutathione reductase. Furthermore, gene expression of respiratory burst oxidase homolog1 and H 2 O 2 content were upregulated with ALA treatment under normal conditions. Treatment with exogenous H 2 O 2 , GSH, and AsA also induced plant tolerance to oxidative stress at low temperatures, while inhibition of GSH and AsA syntheses significantly decreased H 2 O 2 -induced oxidative stress tolerance. Meanwhile, scavenging or inhibition of H 2 O 2 production weakened, but did not eliminate, GSH- or AsA- induced tomato plant tolerance to oxidative stress at low temperatures. Appropriate concentrations of ALA alleviated the low temperature-induced oxidative stress in tomato plants via an antioxidant system. The most effective concentration was 25 mg·L - 1 . The results showed that H 2 O 2 induced by exogenous ALA under normal conditions is crucial and may be the initial step for perception and signaling transmission, which then improves the ratio of GSH and AsA. GSH and AsA may then interact with H 2 O 2 signaling, resulting in enhanced antioxidant capacity

Scaling of the Stress and Temperature Dependence of the Optical Anisotropy in Ba(Fe 1-x Co x ) 2As 2

DOE PAGES

Mirri, C.; Dusza, A.; Bastelberger, S.; ...

2016-09-15

We revisit our recent investigations of the optical properties in the underdoped regime of the title compounds with respect to their anisotropic behavior as a function of both temperature and uniaxial stress across the ferro-elastic tetragonal-to-orthorhombic transition. By exploiting a dedicated pressure device, we can tune and control uniaxial stress in situ thus changing the degree of detwinning of the samples in the orthorhombic SDW state as well as pressure-inducing an orthorhombicity in the paramagnetic tetragonal phase. Here we discover a hysteretic behavior of the optical anisotropy; its stress versus temperature dependence across the structural transition bears testimony to themore » analogy with the magnetic-field versus temperature dependence of the magnetization in a ferromagnet when crossing the Curie temperature. In this context, we find furthermore an intriguing scaling of the stress and temperature dependence of the optical anisotropy in Ba(Fe 1-xCo x) 2As 2.« less

Catalase-dependent H2O2 consumption by cardiac mitochondria and redox-mediated loss in insulin signaling.

PubMed

Rindler, Paul M; Cacciola, Angela; Kinter, Michael; Szweda, Luke I

2016-11-01

We have recently demonstrated that catalase content in mouse cardiac mitochondria is selectively elevated in response to high dietary fat, a nutritional state associated with oxidative stress and loss in insulin signaling. Catalase and various isoforms of glutathione peroxidase and peroxiredoxin each catalyze the consumption of H 2 O 2 Catalase, located primarily within peroxisomes and to a lesser extent mitochondria, has a low binding affinity for H 2 O 2 relative to glutathione peroxidase and peroxiredoxin. As such, the contribution of catalase to mitochondrial H 2 O 2 consumption is not well understood. In the current study, using highly purified cardiac mitochondria challenged with micromolar concentrations of H 2 O 2 , we found that catalase contributes significantly to mitochondrial H 2 O 2 consumption. In addition, catalase is solely responsible for removal of H 2 O 2 in nonrespiring or structurally disrupted mitochondria. Finally, in mice fed a high-fat diet, mitochondrial-derived H 2 O 2 is responsible for diminished insulin signaling in the heart as evidenced by reduced insulin-stimulated Akt phosphorylation. While elevated mitochondrial catalase content (∼50%) enhanced the capacity of mitochondria to consume H 2 O 2 in response to high dietary fat, the selective increase in catalase did not prevent H 2 O 2 -induced loss in cardiac insulin signaling. Taken together, our results indicate that mitochondrial catalase likely functions to preclude the formation of high levels of H 2 O 2 without perturbing redox-dependent signaling. Copyright © 2016 the American Physiological Society.

Evaluation of molecular volume change of block copolymer depending on temperature: A SANS study

DOE PAGES

Kim, Tae-Hwan; Do, Changwoo; Han, Young-Soo

2017-12-24

Amphiphilic Pluronic triblock copolymers form various self-assembled structures such as sphere, cylinder, lamellae and so on, depending on temperature, leading to the increase of hydrophobicity of block copolymers. However, the effective molecular volume change of the block copolymer has not been fully exploited yet, when temperature increases. Here in this paper, we have investigated the effective molecular volume change of the block copolymer upon heating by using the contrast variation small angle neutron scattering. The scattering length densities (SLDs) of the block copolymer were experimentally obtained from the neutron scattering contrast variation method between the solvent and the block copolymermore » at varying temperature. Even though the SLD, which is the intrinsic property of the material, should not be changed by temperature elevation, it was dependent on temperature, indicating that the molecular volume is changed. Therefore, we obtained the increase rate of the molecular volume change of the block copolymer (the effective molecular volume change) from the comparison of the calculated SLD and the standard SLD, which is evaluated by plotting the SANS intensity at the first order Bragg peak as the function of temperature at each volume fraction of D 2O and H 2O that is about 25.5%–51.3% depending on temperature.« less

Evaluation of molecular volume change of block copolymer depending on temperature: A SANS study

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

Kim, Tae-Hwan; Do, Changwoo; Han, Young-Soo

Amphiphilic Pluronic triblock copolymers form various self-assembled structures such as sphere, cylinder, lamellae and so on, depending on temperature, leading to the increase of hydrophobicity of block copolymers. However, the effective molecular volume change of the block copolymer has not been fully exploited yet, when temperature increases. Here in this paper, we have investigated the effective molecular volume change of the block copolymer upon heating by using the contrast variation small angle neutron scattering. The scattering length densities (SLDs) of the block copolymer were experimentally obtained from the neutron scattering contrast variation method between the solvent and the block copolymermore » at varying temperature. Even though the SLD, which is the intrinsic property of the material, should not be changed by temperature elevation, it was dependent on temperature, indicating that the molecular volume is changed. Therefore, we obtained the increase rate of the molecular volume change of the block copolymer (the effective molecular volume change) from the comparison of the calculated SLD and the standard SLD, which is evaluated by plotting the SANS intensity at the first order Bragg peak as the function of temperature at each volume fraction of D 2O and H 2O that is about 25.5%–51.3% depending on temperature.« less

O(2)-dependent K(+) fluxes in trout red blood cells: the nature of O(2) sensing revealed by the O(2) affinity, cooperativity and pH dependence of transport.

PubMed

Berenbrink, M; Völkel, S; Heisler, N; Nikinmaa, M

2000-07-01

The effects of pH and O(2) tension on the isotonic ouabain-resistant K(+) (Rb+) flux pathway and on haemoglobin O2 binding were studied in trout red blood cells (RBCs) in order to test for a direct effect of haemoglobin O(2) saturation on K(+) transport across the RBC membrane. At pH values corresponding to in vivo control arterial plasma pH and higher, elevation of the O(2) partial pressure (PO(2)) from 7.8 to 157 mmHg increased unidirectional K(+) influx across the RBC membrane several-fold. At lower extracellular pH values, stimulation of K(+) influx by O(2) was depressed, exhibiting an apparent pK(a) (pK'(a)) for the process of 8.0. Under similar conditions the pK'(a) for acid-induced deoxygenation of haemoglobin (Hb) was 7.3. When trout RBCs were exposed to PO(2) values between 0 and 747 mmHg, O(2) equilibrium curves typical of Hb O(2) saturation were also obtained for K(+) influx and efflux. However, at pH 7.9, the PO(2) for half-maximal K(+) efflux and K(+) influx (P50) was about 8- to 12-fold higher than the P(50) for Hb-O(2) binding. While K(+) influx and efflux stimulation by O(2) was essentially non-cooperative, Hb-O(2) equilibrium curves were distinctly sigmoidal (Hill parameters close to 1 and 3, respectively). O(2)-stimulated K(+) influx and efflux were strongly pH dependent. When the definition of the Bohr factor for respiratory pigments (Phi = delta logP50 x delta pH(-1)) was extended to the effect of pH on O(2)-dependent K(+) influx and efflux, extracellular Bohr factors (Phi(o) of -2.00 and -2.06 were obtained, values much higher than that for Hb (Phi(o) = -0.49). The results of this study are consistent with an O(2) sensing mechanism differing markedly in affinity and cooperativity of O(2) binding, as well as in pH sensitivity, from bulk Hb.

Reactions of Fe+ and FeO+ with C2H2, C2H4, and C2H6: Temperature-Dependent Kinetics

DTIC Science & Technology

2013-09-12

studies to lead to the development of efficient quantum chemical calculation methods by offering benchmarks for testing and refinement. Due to the...EXPERIMENTAL METHODS All measurements were performed on the Air Force Research Laboratory’s variable temperature selected ion flow tube (VT- SIFT) instrument...correct within error, indicating that they are in the low-pressure limit,52,53 and the termolecular rate constant is obtained from the slope. In contrast

Temperature Dependence of the Collisional Removal of O2(A(sup 3)Sigma(sup +)(sub u), upsilon=9 ) with O2 and N2

NASA Technical Reports Server (NTRS)

Hwang, Eunsook S.; Copeland, Richard A.

1997-01-01

The temperature dependence of the collisional removal of O2 molecules in the upsilon = 9 level of the A(sup 3)Sigma(sup +)(sub u) electronic state has been studied for the colliders O2 and N2, over the temperature range 150 to 300 K. In a cooled flow cell, the output of a pulsed dye laser excites the O2 to the upsilon = 9 level of the A(sup 3)Sigma(sup +)(sub u) state, and the output of a time-delayed second laser monitors the temporal evolution of this level via a resonance-enhanced ionization. We find the u thermally averaged removal cross section for O2 collisions is constant (approx. 10 A(sup 2)) between room temperature and 200 K, then increases rapidly with decreasing temperature, doubling by 150 K. In contrast, the N2 cross section at 225 K is approx. 8% smaller and gradually increases to a value at 150 K that is approx. 60% larger than the room temperature value. The difference between the temperature dependence of the O2 and N2 collision cross section implies that the removal by oxygen becomes more important at the lower temperatures found in the mesosphere, but removal by N2 still dominates.

Orientation and temperature dependent adsorption of H 2S on GaAs: Valence band photoemission

NASA Astrophysics Data System (ADS)

Ranke, W.; Kuhr, H. J.; Finster, J.

A cylindrically shaped GaAs single crystal was used to study the adsorption of H 2S on the six inequivalent orientations (001), (113), (111), (110), (111) and (113) by angle resolved valence band photoelectron spectroscopy and surface dipole measurements. Adsorption at 150 K on the surface prepared by molecular beam epitaxy (MBE) yields similar adsorbate induced emission on all orientations which were ascribed to SH radicals. On (110), where preferential adsorption occurs additional features from molecular H 2S are observed. The adsorbate spectra at 720 K are ascribed to atomic sulphur. On the surface prepared by ion bombardment and annealing, defect enhanced adsorption occurs in the range (111)-(113). The adsorbate spectra are very similar to those on the MBE surface at 720 K. Thus, no new species are adsorbed on defects but only sticking probability and penetration capability are increased.

Species-to-species rate coefficients for the H3+ + H2 reacting system

NASA Astrophysics Data System (ADS)

Sipilä, O.; Harju, J.; Caselli, P.

2017-10-01

Aims: We study whether or not rotational excitation can make a large difference to chemical models of the abundances of the H3+ isotopologs, including spin states, in physical conditions corresponding to starless cores and protostellar envelopes. Methods: We developed a new rate coefficient set for the chemistry of the H3+ isotopologs, allowing for rotational excitation, using previously published state-to-state rate coefficients. These new so-called species-to-species rate coefficients are compared with previously-used ground-state-to-species rate coefficients by calculating chemical evolution in variable physical conditions using a pseudo-time-dependent chemical code. Results: We find that the new species-to-species model produces different results to the ground state-to-species model at high density and toward increasing temperatures (T> 10 K). The most prominent difference is that the species-to-species model predicts a lower H3+ deuteration degree at high density owing to an increase of the rate coefficients of endothermic reactions that tend to decrease deuteration. For example at 20 K, the ground-state-to-species model overestimates the abundance of H2D+ by a factor of about two, while the abundance of D3+ can differ by up to an order of magnitude between the models. The spin-state abundance ratios of the various H3+ isotopologs are also affected, and the new model better reproduces recent observations of the abundances of ortho and para H2D+ and D2H+. The main caveat is that the applicability regime of the new rate coefficients depends on the critical densities of the various rotational transitions which vary with the abundances of the species and the temperature in dense clouds. Conclusions: The difference in the abundances of the H3+ isotopologs predicted by the species-to-species and ground state-to-species models is negligible at 10 K corresponding to physical conditions in starless cores, but inclusion of the excited states is very important in studies

Spectro-imaging observations of Jupiter's 2-μm auroral emission. I. H 3+ distribution and temperature

NASA Astrophysics Data System (ADS)

Raynaud, E.; Lellouch, E.; Maillard, J.-P.; Gladstone, G. R.; Waite, J. H.; Bézard, B.; Drossart, P.; Fouchet, T.

2004-09-01

We report on spectro-imaging infrared observations of Jupiter's auroral zones, acquired in October 1999 and October 2000 with the FTS/BEAR instrument at the Canada-France-Hawaii Telescope. The use of narrow-band filters at 2.09 and 2.12 μm, combined with high spectral resolution (0.2 cm -1), allowed us to map emission from the H 2S1(1) quadrupole line and from several H 3+ lines. The H 2 and H 3+ emission appears to be morphologically different, especially in the north, where the latter notably exhibits a "hot spot" near 150°-170° System III longitude. This hot spot coincides in position with the region of increased and variable hydrocarbon, FUV and X-ray emission, but is not seen in the more uniform H 2S1(1) emission. We also present the first images of the H 2 emission in the southern polar region. The spectra include a total of 14 H 3+ lines, including two hot lines from the 3 ν2- ν2 band, detected on Jupiter for the first time. They can be used to determine H 3+ column densities, rotational ( Trot) and vibrational ( Tvib) temperatures. We find the mean Tvib of the v2=3 state to be lower (960±50 K) than the mean Trot in v2=2 (1170±75 K), indicating an underpopulation of the v2=3 level with respect to local thermodynamical equilibrium. Rotational temperatures and associated column densities are generally higher and lower, respectively, than inferred previously from ν2 observations. This is a likely consequence of a large positive temperature gradient in the sub-microbar auroral atmosphere. While the signal-to-noise is not sufficient to take full advantage of the 2-D capabilities of the observations, the search for correlations between line intensities, Tvib and column densities, indicates that variations in line intensities are mostly due to correlated variations in the H 3+ column densities. The thermostatic role played by H 3+ at ionospheric levels may provide an explanation. The exception is the northern "hot spot," which exhibits a Tvib about 250 K

Room-Temperature Wet Chemical Synthesis of Au NPs/TiH2/Nanocarved Ti Self-Supported Electrocatalysts for Highly Efficient H2 Generation.

PubMed

Amin, Mohammed A; Fadlallah, Sahar A; Alosaimi, Ghaida S; Ahmed, Emad M; Mostafa, Nasser Y; Roussel, Pascal; Szunerits, Sabine; Boukherroub, Rabah

2017-09-06

Self-supported electrocatalysts are a new class of materials exhibiting high catalytic performance for various electrochemical processes and can be directly equipped in energy conversion devices. We present here, for the first time, sparse Au NPs self-supported on etched Ti (nanocarved Ti substrate self-supported with TiH 2 ) as promising catalysts for the electrochemical generation of hydrogen (H 2 ) in KOH solutions. Cleaned, as-polished Ti substrates were etched in highly concentrated sulfuric acid solutions without and with 0.1 M NH 4 F at room temperature for 15 min. These two etching processes yielded a thin layer of TiH 2 (the corrosion product of the etching process) self-supported on nanocarved Ti substrates with different morphologies. While F - -free etching process led to formation of parallel channels (average width: 200 nm), where each channel consists of an array of rounded cavities (average width: 150 nm), etching in the presence of F - yielded Ti surface carved with nanogrooves (average width: 100 nm) in parallel orientation. Au NPs were then grown in situ (self-supported) on such etched surfaces via immersion in a standard gold solution at room temperature without using stabilizers or reducing agents, producing Au NPs/TiH 2 /nanostructured Ti catalysts. These materials were characterized by scanning electron microscopy/energy-dispersive spectroscopy (SEM/EDS), grazing incidence X-ray diffraction (GIXRD), and X-ray photoelectron spectroscopy (XPS). GIXRD confirmed the formation of Au 2 Ti phase, thus referring to strong chemical interaction between the supported Au NPs and the substrate surface (also evidenced from XPS) as well as a titanium hydride phase of chemical composition TiH 2 . Electrochemical measurements in 0.1 M KOH solution revealed outstanding hydrogen evolution reaction (HER) electrocatalytic activity for our synthesized catalysts, with Au NPs/TiH 2 /nanogrooved Ti catalyst being the best one among them. It exhibited fast kinetics

Temperature and pressure dependence of the absolute rate constant for the reactions of NH2 radicals with acetylene and ethylene

NASA Technical Reports Server (NTRS)

Bosco, S. R.; Nava, D. F.; Brobst, W. D.; Stief, L. J.

1984-01-01

The absolute rate constants for the reaction between the NH2 free radical and acetylene and ethylene is measured experimentally using a flash photolysis technique. The constant is considered to be a function of temperature and pressure. At each temperature level of the experiment, the observed pseudo-first-order rate constants were assumed to be independent of flash intensity. The results of the experiment indicate that the bimolecular rate constant for the NH2 + C2H2 reaction increases with pressure at 373 K and 459 K but not at lower temperatures. Results near the pressure limit conform to an Arrhenius expression of 1.11 (+ or -) 0.36 x 10 to the -13th over the temperature range from 241 to 459 K. For the reaction NH2 + C2H4, a smaller rate of increase in the bimolecular rate constant was observed over the temperature range 250-465 K. The implications of these results for current theoretical models of NH2 + C2H2 (or H4) reactions in the atmospheres of Jupiter and Saturn are discussed.

Low Temperature Flux Growth of 2H-SiC and Beta-Gallium Oxide

NASA Technical Reports Server (NTRS)

Singh, N. B.; Choa, Fow-Sen; Su, Ching-Hua; Arnold, Bradley; Kelly, Lisa

2016-01-01

We present brief overview of our study on the low temperature flux growth of two very important novel wide bandgap materials 2H-SiC and Beta-gallium oxide (Beta-Ga2O3). We have synthesized and grown 5 millimeter to 1 centimeter size single crystals of Beta-gallium oxide (Beta-Ga2O3). We used a flux and semi wet method to grow transparent good quality crystals. In the semi-wet method Ga2O3 was synthesized with starting gallium nitrate solution and urea as a nucleation agent. In the flux method we used tin and other metallic flux. This crystal was placed in an alumina crucible and temperature was raised above 1050 degrees Centigrade. After a time period of thirty hours, we observed prismatic and needle shaped crystals of gallium oxide. Scanning electron microscopic studies showed step growth morphology. Crystal was polished to measure the properties. Bandgap was measured 4.7electronvolts using the optical absorption curve. Another wide bandgap hexagonal 2H-SiC was grown by using Si-Al eutectic flux in the graphite crucible. We used slight AlN also as the impurity in the flux. The temperature was raised up to 1050 degrees Centigrade and slowly cooled to 850 degrees Centigrade. Preliminary characterization results of this material are also reported.

High-bandwidth scanned-wavelength-modulation spectroscopy sensors for temperature and H2O in a rotating detonation engine

NASA Astrophysics Data System (ADS)

Goldenstein, Christopher S.; Almodóvar, Christopher A.; Jeffries, Jay B.; Hanson, Ronald K.; Brophy, Christopher M.

2014-10-01

The design and use of two-color tunable diode laser (TDL) absorption sensors for measurements of temperature and H2O in a rotating detonation engine (RDE) are presented. Both sensors used first-harmonic-normalized scanned-wavelength-modulation spectroscopy with second-harmonic detection (scanned-WMS-2f/1f) to account for non-absorbing transmission losses and emission encountered in the harsh combustion environment. One sensor used two near-infrared (NIR) TDLs near 1391.7 nm and 1469.3 nm that were modulated at 225 kHz and 285 kHz, respectively, and sinusoidally scanned across the peak of their respective H2O absorption transitions to provide a measurement rate of 50 kHz and a detection limit in the RDE of 0.2% H2O by mole. The other sensor used two mid-infrared (MIR) TDLs near 2551 nm and 2482 nm that were modulated at 90 kHz and 112 kHz, respectively, and sinusoidally scanned across the peak of their respective H2O transitions to provide a measurement rate of 10 kHz and a detection limit in the RDE of 0.02% H2O by mole. Four H2O absorption transitions with different lower-state energies were used to assess the homogeneity of temperature in the measurement plane. Experimentally derived spectroscopic parameters that enable temperature and H2O sensing to within 1.5-3.5% of known values are reported. The sensor design enabling the high-bandwidth scanned-WMS-2f/1f measurements is presented. The two sensors were deployed across two orthogonal and coplanar lines-of-sight (LOS) located in the throat of a converging-diverging nozzle at the RDE combustor exit. Measurements in the non-premixed H2-fueled RDE indicate that the temperature and H2O oscillate at the detonation frequency (≈3.25 kHz) and that production of H2O is a weak function of global equivalence ratio.

Simultaneous measurement of 2-dimensional H2O concentration and temperature distribution in premixed methane/air flame using TDLAS-based tomography technology

NASA Astrophysics Data System (ADS)

Wang, Fei; Wu, Qi; Huang, Qunxing; Zhang, Haidan; Yan, Jianhua; Cen, Kefa

2015-07-01

An innovative tomographic method using tunable diode laser absorption spectroscopy (TDLAS) and algebraic reconstruction technique (ART) is presented in this paper for detecting two-dimensional distribution of H2O concentration and temperature in a premixed flame. The collimated laser beam emitted from a low cost diode laser module was delicately split into 24 sub-beams passing through the flame from different angles and the acquired laser absorption signals were used to retrieve flame temperature and H2O concentration simultaneously. The efficiency of the proposed reconstruction system and the effect of measurement noise were numerically evaluated. The temperature and H2O concentration in flat methane/air premixed flames under three different equivalence ratios were experimentally measured and reconstruction results were compared with model calculations. Numerical assessments indicate that the TDLAS tomographic system is capable for temperature and H2O concentration profiles detecting even the noise strength reaches 3% of absorption signal. Experimental results under different combustion conditions are well demonstrated along the vertical direction and the distribution profiles are in good agreement with model calculation. The proposed method exhibits great potential for 2-D or 3-D combustion diagnostics including non-uniform flames.

Thermodynamic and transport properties of frozen and reacting pH2-oH2 mixtures

NASA Technical Reports Server (NTRS)

Carter, H. G.; Bullock, R. E.

1972-01-01

Application of experimental state data and spectroscopic term values shows that the thermodynamic and transport properties of reacting pH2-oH2 mixtures are considerably different than those of chemically frozen pH2 at temperatures below 300 R. Calculated H-S data also show that radiation-induced pH2-oH2 equilibration at constant enthalpy produces a temperature drop of at least 28 R, corresponding to an ideal shaft work loss of 15% or more for a turbine operating downstream from the point of conversion. Aside from differences in thermodynamic and transport properties, frozen pH2-oH2 mixtures may differ from pure pH2 on a purely hydrodynamical basis.

Calculation of composition distribution of ultrafine ion-H2O-H2SO4 clusters using a modified binary ion nucleation theory

NASA Technical Reports Server (NTRS)

Singh, J. J.; Smith, A. S.; Chan, L. Y.; Yue, G. K.

1982-01-01

Thomson's ion nucleation theory was modified to include the effects of curvature dependence of the microscopic surface tension of field dependent, nonlinear, dielectric properties of the liquid; and of sulfuric acid hydrate formation in binary mixtures of water and sulfuric acid vapors. The modified theory leads to a broadening of the ion cluster spectrum, and shifts it towards larger numbers of H2O and H2SO4 molecules. Whether there is more shifting towards larger numbers of H2O or H2SO4 molecules depends on the relative humidity and relative acidity of the mixture. Usually, a broadening of the spectrum is accompanied by a lowering of the mean cluster intensity. For fixed values of relative humidity and relative acidity, a similar broadening pattern is observed when the temperature is lowered. These features of the modified theory illustrate that a trace of sulfuric acid can facilitate the formation of ultrafine, stable, prenucleation ion clusters as well as the growth of the prenucleation ion clusters towards the critical saddle point conditions, even with low values of relative humidity and relative acidity.

Temperature-Dependent Electrical Characteristics of Au/Si3N4/4H n-SiC MIS Diode

NASA Astrophysics Data System (ADS)

Yigiterol, F.; Güllü, H. H.; Bayraklı, Ö.; Yıldız, D. E.

2018-03-01

Electrical characteristics of the Au/Si3N4/4H n-SiC metal-insulator-semiconductor (MIS) diode were investigated under the temperature, T , interval of 160-400 K using current-voltage (I-V), capacitance-voltage ( C {-} V ) and conductance-voltage ( G/ω {-} V ) measurements. Firstly, the Schottky diode parameters as zero-bias barrier height ( Φ_{B0} ) and ideality factor ( n ) were calculated according to the thermionic emission (TE) from forward bias I-V analysis in the whole working T . Experimental results showed that the values of Φ_{B0} were in increasing behavior with increasing T while n values decreased with inverse proportionality in n versus Φ_{{{{B}}0}} plot. Therefore, the non-ideal I-V behavior with inhomogeneous barrier height (BH) formation has been discussed under the assumption of Gaussian distribution (GD). From the GD of BHs, the mean BH was found to be about 1.40 eV with 0.1697 standard deviation and the modified Richardson constant A^{*} of this diode was obtained as 141.65 A/cm2 K2 in good agreement with the literature (the theoretical value of A^{*} is 137.21 A/cm2 K2). The relationship between Φ_{B0} and n showed an abnormal I-V behavior depending on T , and it was modeled by TE theory with GD of BH due to the effect in inhomogeneous BH at the interface. Secondly, according to Cheung's model, series resistance, R_{{S}} values were calculated in the T range of 160-400 K and these values were found to decrease with increasing T . Finally, the density of interface states, D_{{it}} was calculated and the T dependence of energy distribution of D_{{it}} profiles determined the forward I {-} V measurements by taking into account the bias dependence of the effective BH, Φ_{{e}} and n . D_{{it}} were also calculated according to the Hill-Coleman method from C {-} V and G/ω {-} V analysis. Furthermore, the variation of D_{{it}} as a function of frequency, f and T were determined.

Temperature dependencies of Henry's law constants and octanol/water partition coefficients for key plant volatile monoterpenoids.

PubMed

Copolovici, Lucian O; Niinemets, Ulo

2005-12-01

To model the emission dynamics and changes in fractional composition of monoterpenoids from plant leaves, temperature dependencies of equilibrium coefficients must be known. Henry's law constants (H(pc), Pa m3 mol(-1) and octanol/water partition coefficients (K(OW), mol mol(-1)) were determined for 10 important plant monoterpenes at physiological temperature ranges (25-50 degrees C for H(pc) and 20-50 degrees C for K(OW)). A standard EPICS procedure was established to determine H(pc) and a shake flask method was used for the measurements of K(OW). The enthalpy of volatilization (deltaH(vol)) varied from 18.0 to 44.3 kJ mol(-1) among the monoterpenes, corresponding to a range of temperature-dependent increase in H(pc) between 1.3- and 1.8-fold per 10 degrees C rise in temperature. The enthalpy of water-octanol phase change varied from -11.0 to -23.8 kJ mol(-1), corresponding to a decrease of K(OW) between 1.15- and 1.32-fold per 10 degrees C increase in temperature. Correlations among physico-chemical characteristics of a wide range of monoterpenes were analyzed to seek the ways of derivation of H(pc) and K(OW) values from other monoterpene physico-chemical characteristics. H(pc) was strongly correlated with monoterpene saturated vapor pressure (P(v)), and for lipophilic monoterpenes, deltaH(vol) scaled positively with the enthalpy of vaporization that characterizes the temperature dependence of P(v) Thus, P(v) versus temperature relations may be employed to derive the temperature relations of H(pc) for these monoterpenes. These data collectively indicate that monoterpene differences in H(pc) and K(OW) temperature relations can importantly modify monoterpene emissions from and deposition on plant leaves.

Temperature and H2O sensing in laminar premixed flames using mid-infrared heterodyne phase-sensitive dispersion spectroscopy

NASA Astrophysics Data System (ADS)

Ma, Liuhao; Wang, Zhen; Cheong, Kin-Pang; Ning, Hongbo; Ren, Wei

2018-06-01

We report the first demonstration of heterodyne phase-sensitive dispersion spectroscopy (HPSDS) for the simultaneous temperature and H2O concentration measurements in combustion environments. Two continuous-wave distributed-feedback quantum cascade lasers (DFB-QCLs) at 5.27 and 10.53 µm were used to exploit the strong H2O transitions (1897.52 and 949.53 cm-1) at high temperatures. The injection current of each QCL was modulated at sub-GHz or GHz to generate the three-tone radiation and the dispersion signal was detected by the radio-frequency down-conversion heterodyning. The peak-to-peak ratio of the two H2O dispersion spectra exhibits a monotonic relationship with temperature over the temperature range of 1000-3000 K, indicating the capability of performing two-line thermometry using laser dispersion spectroscopy. We measured the temperatures of CH4/air flames at different equivalence ratios ( Φ = 0.8-1.2), yielding a good agreement with the corresponding thermocouple measurements. In addition, one-dimensional kinetic modeling coupled with a detailed chemical kinetic mechanism (GRI 3.0) was conducted to compare with the measured H2O concentrations using HPSDS. Finally, we demonstrated HPSDS is immune to optical power fluctuations by measuring the dispersion spectra at varied incident laser powers.

Zero-point corrections and temperature dependence of HD spin-spin coupling constants of heavy metal hydride and dihydrogen complexes calculated by vibrational averaging.

PubMed

Mort, Brendan C; Autschbach, Jochen

2006-08-09

Vibrational corrections (zero-point and temperature dependent) of the H-D spin-spin coupling constant J(HD) for six transition metal hydride and dihydrogen complexes have been computed from a vibrational average of J(HD) as a function of temperature. Effective (vibrationally averaged) H-D distances have also been determined. The very strong temperature dependence of J(HD) for one of the complexes, [Ir(dmpm)Cp*H2]2 + (dmpm = bis(dimethylphosphino)methane) can be modeled simply by the Boltzmann average of the zero-point vibrationally averaged JHD of two isomers. For this complex and four others, the vibrational corrections to JHD are shown to be highly significant and lead to improved agreement between theory and experiment in most cases. The zero-point vibrational correction is important for all complexes. Depending on the shape of the potential energy and J-coupling surfaces, for some of the complexes higher vibrationally excited states can also contribute to the vibrational corrections at temperatures above 0 K and lead to a temperature dependence. We identify different classes of complexes where a significant temperature dependence of J(HD) may or may not occur for different reasons. A method is outlined by which the temperature dependence of the HD spin-spin coupling constant can be determined with standard quantum chemistry software. Comparisons are made with experimental data and previously calculated values where applicable. We also discuss an example where a low-order expansion around the minimum of a complicated potential energy surface appears not to be sufficient for reproducing the experimentally observed temperature dependence.

Temperature Effects on Stainless Steel 316L Corrosion in the Environment of Sulphuric Acid (H2SO4)

NASA Astrophysics Data System (ADS)

Ayu Arwati, I. G.; Herianto Majlan, Edy; Daud, Wan Ramli Wan; Shyuan, Loh Kee; Arifin, Khuzaimah Binti; Husaini, Teuku; Alfa, Sagir; Ashidiq, Fakhruddien

2018-03-01

In its application, metal is always in contact with its environment whether air, vapor, water, and other chemicals. During contact, chemical interactions emerge between metals and their respective environments such that the metal surface corrodes. This study aims to determine the corrosion rate of 316L stainless steel sulphuric acid environment (H2SO4) with weight loss and electrochemical methods. The corrosion rate (CR) is value of 316L stainless steel by weight loss method with sulfuric acid (H2SO4) with concentration of 0.5 M. The result obtained in conjunction with the increase of temperature the rate of erosion obtained appears to be larger, with a consecutive 3 hour the temperature of 50°C is 0.27 mg/cm2h, temperature 70°C 0.38 mg/cm2h, and temperature 90 °C 0.52 mg/cm2h. With the electrochemical method, the current value increases by using a C350 potentiostal tool. The higher the current, the longer the time the corrosion rate increases, where the current is at 90 °C with a 10-minute treatment time of 0.0014736 A. The 316L stainless steel in surface metal morphology is shown by using a Scanning Electron Microscope (SEM).

Temperature-dependent sex-reversal by a transformer-2 gene-edited mutation in the spotted wing drosophila, Drosophila suzukii.

PubMed

Li, Jianwei; Handler, Alfred M

2017-09-28

Female to male sex reversal was achieved in an emerging agricultural insect pest, Drosophila suzukii, by creating a temperature-sensitive point mutation in the sex-determination gene, transformer-2 (tra-2), using CRISPR/Cas9 (clustered regularly interspaced palindromic repeats/CRISPR-associated) homology-directed repair gene-editing. Ds-tra-2 ts2 mutants developed as normal fertile XX and XY adults at permissive temperatures below 20 °C, but at higher restrictive temperatures (26 to 29 °C) chromosomal XX females developed as sterile intersexuals with a predominant male phenotype, while XY males developed with normal morphology, but were sterile. The temperature-dependent function of the Ds-TRA-2 ts2 protein was also evident by the up- and down-regulation of female-specific Ds-Yolk protein 1 (Ds-Yp1) gene expression by temperature shifts during adulthood. This study confirmed the temperature-dependent function of a gene-edited mutation and provides a new method for the more general creation of conditional mutations for functional genomic analysis in insects, and other organisms. Furthermore, it provides a temperature-dependent system for creating sterile male populations useful for enhancing the efficacy of biologically-based programs, such as the sterile insect technique (SIT), to control D. suzukii and other insect pest species of agricultural and medical importance.

Room temperature stable COx-free H2 production from methanol with magnesium oxide nanophotocatalysts

PubMed Central

Liu, Zhengqing; Yin, Zongyou; Cox, Casandra; Bosman, Michel; Qian, Xiaofeng; Li, Na; Zhao, Hongyang; Du, Yaping; Li, Ju; Nocera, Daniel G.

2016-01-01

Methanol, which contains 12.6 weight percent hydrogen, is a good hydrogen storage medium because it is a liquid at room temperature. However, by releasing the hydrogen, undesirable CO and/or CO2 byproducts are formed during catalytic fuel reforming. We show that alkaline earth metal oxides, in our case MgO nanocrystals, exhibit stable photocatalytic activity for CO/CO2-free H2 production from liquid methanol at room temperature. The performance of MgO nanocrystals toward methanol dehydrogenation increases with time and approaches ~320 μmol g−1 hour−1 after a 2-day photocatalytic reaction. The COx-free H2 production is attributed to methanol photodecomposition to formaldehyde, photocatalyzed by surface electronic states of unique monodispersed, porous MgO nanocrystals, which were synthesized with a novel facile colloidal chemical strategy. An oxygen plasma treatment allows for the removal of organic surfactants, producing MgO nanocrystals that are well dispersible in methanol. PMID:28508036

Spectroscopic study of low pressure, low temperature H2-CH4-CO2 microwave plasmas used for large area deposition of nanocrystalline diamond films. Part II: on plasma chemical processes

NASA Astrophysics Data System (ADS)

Nave, A. S. C.; Baudrillart, B.; Hamann, S.; Bénédic, F.; Lombardi, G.; Gicquel, A.; van Helden, J. H.; Röpcke, J.

2016-12-01

In a distributed antenna array (DAA) reactor, microwave H2 plasmas with admixtures of 2.5% CH4 and 1% CO2 used for the deposition of nanocrystalline diamond films have been studied by infrared laser absorption and optical emission spectroscopy (OES) techniques. The experiments were carried out in order to analyze the dependence of plasma chemical phenomena on power and pressure at relatively low pressures, up to 0.55 mbar, and power values, up to 3 kW. The evolution of the concentration of the methyl radical, CH3, of five stable molecules, CH4, CO2, CO, C2H2 and C2H6, and of vibrationally excited CO in the first and second hot band was monitored in the plasma processes by in situ infrared laser absorption spectroscopy using tunable lead salt diode lasers (TDL) and an external-cavity quantum cascade laser (EC-QCL) as radiation sources. OES was applied simultaneously to obtain complementary information about the degree of dissociation of the H2 precursor and of its gas temperature. The experimental results are presented in two separate parts. In Part I, the first paper in a two-part series, the measurement of the gas (T gas), rotational (T rot) and vibrational (T vib) temperatures of the various species in the complex plasma was the main focus of interest. Depending on the different plasma zones the gas temperature was found to range between about 360 and 1000 K inside the DAA reactor (Nave et al 2016 Plasma Sources Sci. Technol. 25 065002). In Part II, the present paper, taking into account the temperatures determined in the first paper, the concentrations of the various species, which were found to be in a range between 1011 and 1015 cm-3, are the focus of interest. The influence of the discharge parameters power and pressure on the molecular concentrations has been studied. To achieve further insight into general plasma chemical aspects the dissociation of the carbon precursor gases including their fragmentation and conversion to the reaction products has been

First time-dependent study of H{sub 2} and H{sub 3}{sup +} ortho-para chemistry in the diffuse interstellar medium: Observations meet theoretical predictions

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

Albertsson, T.; Semenov, D.; Henning, Th.

The chemistry in the diffuse interstellar medium (ISM) initiates the gradual increase of molecular complexity during the life cycle of matter. A key molecule that enables build-up of new molecular bonds and new molecules via proton donation is H{sub 3}{sup +}. Its evolution is tightly related to molecular hydrogen and thought to be well understood. However, recent observations of ortho and para lines of H{sub 2} and H{sub 3}{sup +} in the diffuse ISM showed a puzzling discrepancy in nuclear spin excitation temperatures and populations between these two key species. H{sub 3}{sup +}, unlike H{sub 2}, seems to be outmore » of thermal equilibrium, contrary to the predictions of modern astrochemical models. We conduct the first time-dependent modeling of the para-fractions of H{sub 2} and H{sub 3}{sup +} in the diffuse ISM and compare our results to a set of line-of-sight observations, including new measurements presented in this study. We isolate a set of key reactions for H{sub 3}{sup +} and find that the destruction of the lowest rotational states of H{sub 3}{sup +} by dissociative recombination largely controls its ortho/para ratio. A plausible agreement with observations cannot be achieved unless a ratio larger than 1:5 for the destruction of (1, 1)- and (1, 0)-states of H{sub 3}{sup +} is assumed. Additionally, an increased cosmic-ray ionization rate to 10{sup –15} s{sup –1} further improves the fit whereas variations of other individual physical parameters, such as density and chemical age, have only a minor effect on the predicted ortho/para ratios. Thus, our study calls for new laboratory measurements of the dissociative recombination rate and branching ratio of the key ion H{sub 3}{sup +} under interstellar conditions.« less