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NASA NTRS2005

Polyimides by Photochemical Cyclopolymerization

The novel polyimides of this invention are derived from Diels-Alder cyclopolymerization of photochemically generated bisdienes with dienophiles, such as bismaleimides, trismaleimides and mixtures thereof with maleimide endcaps. Irradiation of one or more diketones produces two distinct hydroxy o-quinodimethane (photoenol) intermediates. These intermediates are trapped via Diels-Alder cycloaddition with appropriate dienophiles, e.g., bismaleimide and/or trismaleimides to give the corresponding polyimides in quantitative yields. When bismaleimides, trismaleimides or mixtures thereof with maleimide end-caps are used as the dienophile, the resulting polyimides have glass transition temperatures (Tg) as high as 300 C. Polyimide films can be prepared by ultraviolet irradiation of high solids content varnishes of the monomers in a small amount of solvent, e.g., cyclohexanone, dimethyl formamide, N-methylpyrollidone and the like. These novel polyimides are characterized as having high glass transition temperatures, good mechanical properties and improved processing in the manufacture of adhesives, electronic materials and films.

Meador, Michael A.↗

NASA NTRS2005

Polyimides by photochemical cyclopolymerization

The novel polyimides of this invention are derived from Diels-Alder cyclopolymerization of photochemically generated bisdienes with dienophiles, such as bismaleimides, trismaleimides and mixtures thereof with maleimide end-caps. Irradiation of one or more diketones produces two distinct hydroxy o-quinodimethane (photoenol) intermediates. These intermediates are trapped via Diels-Alder cycloaddition with appropriate dienophiles, e.g., bismaleimide and/or trismaleimides to give the corresponding polyimides in quantitative yields. When bismaleimides, trismaleimides or mixtures thereof with maleimide end-caps are used as the dienophile, the resulting polyimides have glass transition temperatures (Tg) as high as 300? C. Polyimide films can be prepared by ultraviolet irradiation of high solids content varnishes of the monomers in a small amount of solvent, e.g., cyclohexanone, dimethyl formamide, N-methylpyrollidone and the like. These novel polyimides are characterized as having high glass transition temperatures, good mechanical properties and improved processing in the manufacture of adhesives, electronic materials and films.

Meador, Michael A.↗

NASA NTRS2006

Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies Evaluation Number 15

This is the fifteenth in a series of evaluated sets of rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation. The data are used primarily to model stratospheric and upper tropospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. Copies of this evaluation are available in electronic form and may be printed from the following Internet URL: http://jpldataeval.jpl.nasa.gov/.

data evaluation↗

NASA NTRS2009

Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies Evaluation Number 16. Supplement to Evaluation 15: Update of Key Reactions

This is the supplement to the fifteenth in a series of evaluated sets of rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation. The data are used primarily to model stratospheric and upper tropospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. Copies of this evaluation are available in electronic form and may be printed from the following Internet URL: http://jpldataeval.jpl.nasa.gov/.

atmospheric modeling↗

NASA NTRS2004

Hairlike Percutaneous Photochemical Sensors

Instrumentation systems based on hairlike fiber-optic photochemical sensors have been proposed as minimally invasive means of detecting biochemicals associated with cancer and other diseases. The fiber-optic sensors could be mass-produced as inexpensive, disposable components. The sensory tip of a fiber-optic sensor would be injected through the patient's skin into subcutaneous tissue. A biosensing material on the sensory tip would bind or otherwise react with the biochemical(s) of interest [the analyte(s)] to produce a change in optical properties that would be measured by use of an external photonic analyzer. After use, a fiber-optic sensor could be simply removed by plucking it out with tweezers. A fiber-optic sensor according to the proposal would be of the approximate size and shape of a human hair, and its sensory tip would resemble a follicle. Once inserted into a patient's subcutaneous tissue, the sensor would even more closely resemble a hair growing from a follicle (see Figure 1). The biosensing material on the sensory tip could consist of a chemical and/or cells cultured and modified for the purpose. The biosensing material would be contained within a membrane that would cover the tip. If the membrane were not permeable by an analyte, then it would be necessary to create pores in the membrane that would be large enough to allow analyte molecules to diffuse to the biosensing material, but not so large as to allow cells (if present as part of the biosensing material) to diffuse out. The end of the fiber-optic sensor opposite the sensory tip would be inserted in a fiberoptic socket in the photonic analyzer.

George, Thomas↗

NASA NTRS2012

Will Organic Synthesis Within Icy Grains or on Dust Surfaces in the Primitive Solar Nebula Completely Erase the Effects of Photochemical Self Shielding?

There are at least 3 separate photochemical self-shielding models with different degrees of commonality. All of these models rely on the selective absorption of (12))C(16)O dissociative photons as the radiation source penetrates through the gas allowing the production of reactive O-17 and O-18 atoms within a specific volume. Each model also assumes that the undissociated C(16)O is stable and does not participate in the chemistry of nebular dust grains. In what follows we will argue that this last, very important assumption is simply not true despite the very high energy of the CO molecular bond.

Nuth, Joseph A., III↗

NASA NTRS2012

The Photochemical Reflectance Index from Directional Cornfield Reflectances: Observations and Simulations

The two-layer Markov chain Analytical Canopy Reflectance Model (ACRM) was linked with in situ hyperspectral leaf optical properties to simulate the Photochemical Reflectance Index (PRI) for a corn crop canopy at three different growth stages. This is an extended study after a successful demonstration of PRI simulations for a cornfield previously conducted at an early vegetative growth stage. Consistent with previous in situ studies, sunlit leaves exhibited lower PRI values than shaded leaves. Since sunlit (shaded) foliage dominates the canopy in the reflectance hotspot (coldspot), the canopy PRI derived from field hyperspectral observations displayed sensitivity to both view zenith angle and relative azimuth angle at all growth stages. Consequently, sunlit and shaded canopy sectors were most differentiated when viewed along the azimuth matching the solar principal plane. These directional PRI responses associated with sunlit/shaded foliage were successfully reproduced by the ACRM. As before, the simulated PRI values from the current study were closer to in situ values when both sunlit and shaded leaves were utilized as model input data in a two-layer mode, instead of a one-layer mode with sunlit leaves only. Model performance as judged by correlation between in situ and simulated values was strongest for the mature corn crop (r = 0.87, RMSE = 0.0048), followed by the early vegetative stage (r = 0.78; RMSE = 0.0051) and the early senescent stage (r = 0.65; RMSE = 0.0104). Since the benefit of including shaded leaves in the scheme varied across different growth stages, a further analysis was conducted to investigate how variable fractions of sunlit/shaded leaves affect the canopy PRI values expected for a cornfield, with implications for 20 remote sensing monitoring options. Simulations of the sunlit to shaded canopy ratio near 50/50 +/- 10 (e.g., 60/40) matching field observations at all growth stages were examined. Our results suggest in the importance of the sunlit/shaded fraction and canopy structure in understanding and interpreting PRI.

Cheng, Yen-Ben↗

NASA NTRS2013

Integrating Solar Induced Fluorescence and the Photochemical Reflectance Index for Estimating Gross Primary Production in a Cornfield

The utilization of remotely sensed observations for light use efficiency (LUE) and tower-based gross primary production (GPP) estimates was studied in a USDA cornfield. Nadir hyperspectral reflectance measurements were acquired at canopy level during a collaborative field campaign conducted in four growing seasons. The Photochemical Reflectance Index (PRI) and solar induced chlorophyll fluorescence (SIF), were derived. SIF retrievals were accomplished in the two telluric atmospheric oxygen absorption features centered at 688 nm (O2-B) and 760 nm (O2-A). The PRI and SIF were examined in conjunction with GPP and LUE determined by flux tower-based measurements. All of these fluxes, environmental variables, and the PRI and SIF exhibited diurnal as well as day-to-day dynamics across the four growing seasons. Consistent with previous studies, the PRI was shown to be related to LUE (r2 = 0.54 with a logarithm fit), but the relationship varied each year. By combining the PRI and SIF in a linear regression model, stronger performances for GPP estimation were obtained. The strongest relationship (r2 = 0.80, RMSE = 0.186 mg CO2/m2/s) was achieved when using the PRI and SIF retrievals at 688 nm. Cross-validation approaches were utilized to demonstrate the robustness and consistency of the performance. This study highlights a GPP retrieval method based entirely on hyperspectral remote sensing observations.

cornfield↗

NASA NTRS2012

Revisions to Photochemical Data for Use in Atmospheric Modeling

Solar and stellar flux incident on an atmosphere can cause molecules to dissociate into highly reactive species and allows for photochemical processes to play a fundamental role in atmospheric chemistry. While models have tried to simulate such processes, they are extremely sensitive to photoabsorption cross-sections and quantum yields: two parameters that are important in determining the photodissociation rate, and hence the lifetime, of atmospheric compounds. Obtaining high-resolution and current data for these parameters is therefore highly desirable. Due to this, database and literature searches for high-quality cross-sections and quantum yields were performed and compiled for KINETICS, a Caltech/JPL Chemical Transport Model that can be used in modeling planetary atmospheres. Furthermore, photodissociation rates determined by running a Titan 1-D model were used to verify the completeness of these latest revisions.

Chemical Transport Model (CTM)↗

NASA NTRS2011

Condensed-Phase Photochemical Processes in Titan's Aerosols and Surface: The Role of Longer Wavelength Photochemistry

We will discuss photochemical properties of Titan's organic molecules in the condensed phase as solid aerosols or surface material, from small linear polyyenes (polyacetylenes and polycyanoacetylenes) such as C2H2, C4N2, HC5N, etc. In particular we will focus on photochemistry caused by longer wavelength UV-VIS photons (greater than 250 nm) photons that make it through Titan's atmosphere to the haze region (approximately 100 km) and on to the surface of Titan.

Surface area↗

NASA NTRS2015

Remotely Sensing the Photochemical Reflectance Index (PRI)

In remote sensing, the Photochemical Reflectance Index (PRI) provides insight into physiological processes occurring inside the leaves in a stand of plants. Developed by Gamon et al., (1990 and 1992), PRI evolved from laboratory measurements of the reflectance of individual leaves (Bilger et al.,1989). Yet in a remotely sensed image, a pixel measurement may include light from both reflecting and transmitting leaves. We conducted laboratory experiments comparing values of PRI based upon polarized reflectance and transmittance measurements of water and nutrient stressed leaves. We illuminated single detached leaves using a current controlled light source (Oriel model 66881) and measured the leaf weight using an analytical balance (Mettler model AE 260) and the light reflected and transmitted by the leaf during dry down using two Analytical Spectral Devices spectroradiometers. Polarizers on the incident and reflected light beams allowed us to divide the leaf reflectance into two parts: a polarized surface reflectance and a non-polarized 'leaf interior' reflectance. Our results underscore the importance when calculating PRI of removing the leaf surface reflection, which contains no information about physiological processes ongoing in the leaf interior. The results show that the leaf physiology information is in the leaf interior reflectance, not the leaf transmittance. Applied to a plant stand, these results suggest use of polarization measurements in sun-view directions that minimize the number of sunlit transmitting leaves in the sensor field of view.

Leaves↗

NASA NTRS2015

Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies: Evaluation Number 18

This is the eighteenth in a series of evaluated sets of rate constants, photochemical cross sections, heterogeneous parameters, and thermochemical parameters compiled by the NASA Panel for Data Evaluation. The data are used primarily to model stratospheric and upper tropospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. The evaluation is available in electronic form from the following Internet URL: http://jpldataeval.jpl.nasa.gov/

Atmospheric Chemistry↗

NASA NTRS2016

Integrating Chlorophyll fapar and Nadir Photochemical Reflectance Index from EO-1/Hyperion to Predict Cornfield Daily Gross Primary Production

The concept of light use efficiency (Epsilon) and the concept of fraction of photosynthetically active ration (PAR) absorbed for vegetation photosynthesis (PSN), i.e., fAPAR (sub PSN), have been widely utilized to estimate vegetation gross primary productivity (GPP). It has been demonstrated that the photochemical reflectance index (PRI) is empirically related to ε. An experimental US Department of Agriculture (USDA) cornfield in Maryland was selected as our study field. We explored the potential of integrating fAPAR(sub chl) (defined as the fraction of PAR absorbed by chlorophyll) and nadir PRI (PRI(sub nadir)) to predict cornfield daily GPP. We acquired nadir or near-nadir EO-1/Hyperion satellite images that covered the cornfield and took nadir in-situ field spectral measurements. Those data were used to derive the PRI(sub nadir) and fAPAR (sub chl). The fAPAR (sub chl) is retrieved with the advanced radiative transfer model PROSAIL2 and the Metropolis approach, a type of Markov Chain Monte Carlo (MCMC) estimation procedure. We define chlorophyll light use efficiency Epsilon (sub chl) as the ratio of vegetation GPP as measured by eddy covariance techniques to PAR absorbed by chlorophyll (Epsilon(sub chl) = GPP/APAR (sub chl). Daily Epsilon (sub chl) retrieved with the EO-1 Hyperion images was regressed with a linear equation of PRI (sub nadir) Epsilon (sub chl) = Alpha × PRI (sub nadir) + Beta). The satellite Epsilon(sub chl- PRI (sub nadir) linear relationship for the cornfield was implemented to develop an integrated daily GPP model [GPP = (Alpha × PRI(sub nadir) + Beta) × fAPAR (sub chl) × PAR], which was evaluated with fAPAR (sub chl) and PRI (sub nadir) retrieved from field measurements. Daily GPP estimated with this fAPAR (sub chl-) PRI (nadir) integration model was strongly correlated with the observed tower in-situ daily GPP (R(sup 2) = 0.93); with a root mean square error (RMSE) of 1.71 g C mol−(sup -1) PPFD and coefficient of variation (CV) of 16.57%. Both seasonal Epsilon (sub chl) and PRI (sub nadir) were strongly correlated with fAPAR (sub chl ) retrieved from field measurements, which indicates that chlorophyll content strongly affects seasonal epsilon (sub chl) and PRI (sub nadir). We demonstrate the potential capacity to monitor GPP with space-based visible through shortwave infrared (VSWIR) imaging spectrometers such as NASA's soon to be decommissioned EO- 1/Hyperion and the future Hyperspectral Infrared Imager (HyspIRI).

HyspIRI↗

NASA NTRS2016

Photosynthetic Efficiency of Northern Forest Ecosystems Using a MODIS-Derived Photochemical Reflectance Index (PRI)

This study evaluates a direct remote sensing approach from space for the determination of ecosystem photosynthetic light use efficiency (LUE), through measurement of vegetation reflectance changes expressed with the Photochemical Reflectance Index (PRI). The PRI is a normalized difference index based on spectral changes at a physiologically active wavelength (approximately 531 nanometers) as compared to a reference waveband, and is only available from a very few satellites. These include the two Moderate-Resolution Imaging Spectroradiometers (MODIS) on the Aqua and Terra satellites each of which have a narrow (10-nanometer) ocean band centered at 531 nanometers. We examined several PRI variations computed with candidate reference bands, since MODIS lacks the traditional 570-nanometer reference band. The PRI computed using MODIS land band 1 (620-670 nanometers) gave the best performance for daily LUE estimation. Through rigorous statistical analyses over a large image collection (n equals 420), the success of relating in situ daily tower-derived LUE to MODIS observations for northern forests was strongly influenced by satellite viewing geometry. LUE was calculated from CO2 fluxes (moles per moles of carbon absorbed quanta) measured at instrumented Canadian Carbon Program flux towers in four Canadian forests: a mature fir site in British Columbia, mature aspen and black spruce sites in Saskatchewan, and a mixed deciduous/coniferous forest site in Ontario. All aspects of the viewing geometry had significant effects on the MODIS-PRI, including the view zenith angle (VZA), the view azimuth angle, and the displacement of the view azimuth relative to the solar principal plane, in addition to illumination related variables.Nevertheless, we show that forward scatter sector views (VZA, 16 degrees-45 degrees) provided the strongest relationships to daily LUE, especially those collected in the early afternoon by Aqua (r squared = 0.83, RMSE (root mean square error) equals 0.003 moles per moles of carbon absorbed quanta). Nadir (VZA, 0 degrees plus or minus 15 degrees) and backscatter views (VZA, −16 degrees to −45 degrees) had lower performance in estimating LUE (nadir: r squared approximately equal to 0.62-0.67; backscatter: r squared approximately equal to 0.54-0.59) and similar estimation error (RMSE equals 0.004-0.005).When directional effects were not considered, only a moderately successful MODIS-PRI vs. LUE relationship (r squared equals 0.34, RMSE equals 0.007) was obtained in the full dataset (all views & sites, both satellites), but site-specific relationships were able to discriminate between coniferous and deciduous forests. Overall, MODIS-PRI values from Terra (late morning) were higher than those from Aqua (early afternoon), before/after the onset of diurnal stress responses expressed spectrally. Therefore, we identified ninety-two Terra-Aqua "same day" pairs, for which the sum of Terra morning and Aqua afternoon MODIS-PRI values (PRI (sub sum) using all available directional observations was linearly correlated with daily tower LUE (r squared equals 0.622, RMSE equals 0.013) and independent of site differences or meteorological information. Our study highlights the value of off-nadir directional reflectance observations, and the value of pairing morning and afternoon satellite observations to monitor stress responses that inhibit carbon uptake in Canadian forest ecosystems. In addition, we show that MODIS-PRI values, when derived from either: (i) forward views only, or (ii) Terra/Aqua same day (any view) combined observations, provided more accurate estimates of tower-measured daily LUE than those derived from either nadir or backscatter views or those calculated by the widely used semi-operational MODIS GPP model (MOD17) which is based on a theoretical maximum LUE and environmental data. Consequently, we demonstrate the importance of diurnal as well as off-nadir satellite observations for detecting vegetation physiological processes.

Middleton, E. M.↗

NASA NTRS2017

Observations of VOC Emissions and Photochemical Products over US Oil- and Gas-Producing Regions Using High-Resolution H3O+ CIMS (PTR-ToF-MS)

VOCs (Volatile Organic Compounds) related to oil and gas extraction operations in the United States were measured by H3O (sup plus) chemical ionization time-of-flight mass spectrometry (H3O (sup plus) ToFCIMS/PTR-ToF-MS (Time of Flight Chemical Ionization Mass Spectrometry/Proton Transfer Reaction-Time of Flight-Mass Spectroscopy) from aircraft during the Shale Oil and Natural Gas Nexus (SONGNEX) campaign in March-April 2015. This work presents an overview of major VOC species measured in nine oil- and gas-producing regions, and a more detailed analysis of H3O (sup plus) ToF-CIMS measurements in the Permian Basin within Texas and New Mexico. Mass spectra are dominated by small photochemically produced oxygenates and compounds typically found in crude oil: aromatics, cyclic alkanes, and alkanes. Mixing ratios of aromatics were frequently as high as those measured downwind of large urban areas. In the Permian, the H3O (sup plus) ToF-CIMS measured a number of underexplored or previously unreported species, including aromatic and cycloalkane oxidation products, nitrogen heterocycles including pyrrole (C4H5N) and pyrroline (C4H7N), H2S, and a diamondoid (adamantane) or unusual monoterpene. We additionally assess the specificity of a number of ion masses resulting from H3O (sup plus) ion chemistry previously reported in the literature, including several new or alternate interpretations.

mass spectrometr↗

NASA NTRS2021

Accounting for the photochemical variation in stratospheric NO2 in the SAGE III/ISS solar occultation retrieval

The Stratospheric Aerosol and Gas Experiment (SAGE) III has been operating on the International Space Station (ISS) since mid-2017. Nitrogen dioxide (NO2) number density profiles are routinely retrieved from SAGE III/ISS solar occultation measurements in the middle atmosphere. Although NO2 density varies throughout the day due to photochemistry, the standard SAGE NO2 retrieval algorithm neglects these variations along the instrument’s line of sight by assuming that the number density has a constant gradient within a given vertical layer of the atmosphere. This assumption will result in a retrieval bias for a species like NO2 that changes rapidly across the terminator. In this work we account for diurnal variations in retrievals of NO2 from the SAGE III/ISS measurements, and we determine the impact of this algorithm improvement on the resulting NO2 number densities. The first step in applying the diurnal correction is to use publicly available SAGE III/ISS products to convert the retrieved number density profiles to optical depth profiles. The retrieval is then re-performed with a new matrix that applies photochemical scale factors for each point along the line of sight according to the changing solar zenith angle. In general NO2 that is retrieved by accounting for these diurnal variations is more than 10% lower than the standard algorithm below 30 km. This effect is greatest in winter at high latitudes and generally greater for sunrise occultations than sunset. Comparisons with coincident profiles from the Optical Spectrograph and InfraRed Imager System (OSIRIS) show that NO2 from SAGE III/ISS is generally biased high; however the agreement improves by up to 20% in the mid-stratosphere when diurnal variations are accounted for in the retrieval. We conclude that diurnal variations along the SAGE III/ISS line of sight are an important term to consider for NO2 analyses at altitudes below 30 km.

Stratospheric NO2↗

NASA NTRS2006

Chemical kinetics and photochemical data for use in Atmospheric Studies Evaluation Number 15

Orkin, V. L.↗

NASA NTRS2020

Chemical kinetics and photochemical data for use in atmospheric studies; evaluation number 19

This is the nineteenth in a series of evaluated sets of rate constants, photochemical cross sections,heterogeneous parameters, and thermochemical parameters compiled by the NASA Panel for Data Evaluation.The data are used primarily to model stratospheric and upper tropospheric processes, with particularemphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena.The evaluation is available in electronic form from the following Internet URL: http://jpldataeval.jpl.nasa.gov

Wine, P.H.↗