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At least 1,423 records · Page 79

Prenatal 2g Exposure Alters Placental Expression of Stress-Related Genes

Extra-terrestrial colonization is of growing interest to space agencies and private entities, emphasizing the importance of research on reproduction and development in the absence of Earth's 1G. Maternal stressors can modify offspring development, exerting significant lifespan and crossgenerational changes through prenatal programming. The space environment is stressful, therefore exposure to altered gravity during pregnancy may impact later life outcomes in offspring. In ground-based studies, we exposed pregnant rats to continuous +G (above Earth gravity), and observed overweight and elevated anxiety in adult male (but not female) offspring, common phenotypes associated with prenatal maternal stress. Here we hypothesize that exposure to increased gravity during pregnancy elicits changes in the expression of stress-related genes in placenta that may mediate emergence of later life outcomes. While the placenta transports maternal factors to the fetus and produces endogenous fetal hormones, stress-induced changes at the placental-uterine interface may also alter communication between mother and fetus, facilitating prenatal transmission of unfavorable later life outcomes and cross-generational epigenetic alterations. Maternal stress elevates maternal glucocorticoids however placental 11b-hydroxysteroid dehydrogenase type 2 (HSD11B2) buffers fetal exposure by converting cortisol/corticosterone into inactive metabolites. Maternal stress during pregnancy down-regulates this enzyme and can induce epigenetic changes in placental and fetal tissues accounting for heightened adult HPA reactivity. Past studies have shown a placenta-specific increase in DNA methyltransferase (DNMT3a) mRNA in stressed mothers, an effect with implications for genome-wide epigenetic changes that may account for diverse phenotypic outcomes following maternal stress. Here we exposed groups of pregnant rats to one of five gravity loads (1, 1.5, 1.75 and 2G) and analyzed placental samples during late gestation. We predicted a systematic dose-response relationship between gravity load and the expression of the HSD11B2 and DNMT3 genes, thereby linking maternal exposure to altered gravity during pregancy with maternal stress.

Kalotia, Simranjit K.↗

Biodiversity and Global Health: Intersection of Health, Security, and the Environment

One of the biggest consequences of large-scale environmental change is the loss of biodiversity. Recent studies predict a loss of 1 million species in the near future. Biodiversity loss and land use change through anthropogenic disturbance are known to affect disease exposure, disease severity, and disease impacts. It is becoming increasingly clear that biodiversity loss will lead to an increase in infectious diseases in certain regions. Changes in biodiversity may contain important signatures for prediction of infectious diseases and outbreaks. Here, we argue that areas of high or rapid biodiversity loss will be critical to monitor under the umbrella of global health security. Global Health Security consists of the actions and activities required to reduce the impact of public health events in populations living in different geographic regions and across international borders. Like infectious diseases, climate change and other causes of environmental changes do not respect international borders and are becoming more widespread in all parts of the world. Here, the relationships among biodiversity, climate and environmental changes, and pathogen prevalence are dynamic, context dependent, and complex. Accounting for this complexity requires the inclusion of the environment sector, presently missing, when evaluating the potential of global health security actions for mitigating disease risks.

59 BASIC BIOLOGICAL SCIENCES↗

Parametric Study of the Forward Attachment Geometry for the Space Launch System Next Generation Booster

Launch vehicle transonic buffet environments can generate large dynamic structural loads and vibratory responses. For the Space Launch System (SLS) vehicle, the highest transonic buffet environments have been observed in the multibody region between the core and solid rocket boosters, particularly downstream of the booster forward attachment. The buffet environment is particularly sensitive to the outer mold line (OML) of the forward attachment, and even relatively minor geometry changes can have large impacts on buffet and other aerodynamic environments. The SLS program is redesigning the booster for the Block 2 vehicle to support updated mission goals. This redesign necessitated changes in the forward attachment geometry, which raised concerns about the buffet and vibroacoustic environments. A preliminary study was conducted that developed multiple forward attachment geometries that satisfied the programmatic requirements, but the aerodynamic environment impacts were unclear. In March 2022, a wind-tunnel test was conducted at the NASA Ames 11- by 11-foot Transonic Wind Tunnel to study these environments generated from each of the configurations in order to select the most viable candidate. This paper will discuss this test campaign, the results from the parametric study, as well as general observations regarding OML features that impact the buffet environment. Buffet environments will be presented and compared for each configuration and comparisons presented where applicable.

buffet↗

Parametric Study of the Forward Attachment Geometry for the Space Launch System Next Generation Booster

Launch vehicle transonic buffet environments can generate large dynamic structural loads and vibratory responses. For the Space Launch System (SLS) vehicle, the highest transonic buffet environments have been observed in the multibody region between the core and solid rocket boosters, particularly downstream of the booster forward attachment. The buffet environment is particularly sensitive to the outer mold line (OML) of the forward attachment, and even relatively minor geometry changes can have large impacts on buffet and other aerodynamic environments. The SLS program is redesigning the booster for the Block 2 vehicle to support updated mission goals. This redesign necessitated changes in the forward attachment geometry, which raised concerns about the buffet and vibroacoustic environments. A preliminary study was conducted that developed multiple forward attachment geometries that satisfied the programmatic requirements, but the aerodynamic environment impacts were unclear. In March 2022, a wind-tunnel test was conducted at the NASA Ames 11- by 11-foot Transonic Wind Tunnel to study these environments generated from each of the configurations in order to select the most viable candidate. This paper will discuss this test campaign, the results from the parametric study, as well as general observations regarding OML features that impact the buffet environment. Buffet environments will be presented and compared for each configuration and comparisons presented where applicable.

buffet↗

Microbial Response to Microgravity and Other Low Shear Environments

Microbial existence and survival requires the ability to sense and respond to environmental changes, including changes in physical forces. This is because microbes inhabit an amazingly diverse range of ecological niches and therefore must constantly adapt to a wide variety of changing environmental conditions, including alterations in temperature, pH, nutrient availability, oxygen levels, and osmotic pressure gradients. Microbes sense their environment through a variety of sensors and receptors which serve to integrate the different signals into the appropriate cellular response(s) that is optimal for survival. While numerous environmental stimuli have been examined for their effect on microorganisms, effects due to changes in mechanical and/or physical forces are also becoming increasingly apparent. Recently, several important studies have demonstrated a key role for microgravity and the low fluid shear dynamics associated with microgravity in the regulation of microbial gene expression, physiology and pathogenesis. The mechanosensory response of microorganisms to these environmental signals, which are relevant to those encountered during microbial life cycles on Earth, may provide insight into their adaptations to physiologically relevant conditions and may ultimately lead to eludicidation of the mechanisms important for mechanosensory transduction in living cells. This review summarizes the recent and potential future research trends aimed at understanding the effect of changes in mechanical forces that occur in microgravity and other low shear environments on different microbial parameters. The results of these studies provide an important step towards understanding how microbes integrate information from multiple mechanical stimuli to an appropriate physiological response.

Nickerson, C.↗

Context-Specific Adaptation of Gravity-Dependent Vestibular Reflex Responses

Stabilization of the eyes and head during body movements is important for maintaining balance and keeping the images of objects stationary on our retinas. Impairment of this ability can lead to disorientation and reduced performance in sensorimotor tasks such as piloting of spacecraft. In the absence of a normal earth gravity field, the dynamics of head stabilization, and the interpretation of vestibular signals that sense gravity and linear acceleration, are subject to change. Transitions between different gravitoinertial force environments - as during different phases of space flight - provide an extreme test of the adaptive mechanisms that maintain these reflexive abilities. It is vitally important to determine human adaptive capabilities in such a circumstance, so that we can know to what extent the sensorimotor skills acquired in one gravity environment will transfer to others. Our work lays the foundation for understanding these capabilities, and for determining how we can aid the processes of adaptation and readaptation. An integrated set of experiments addresses this issue. We use the general approach of adapting some type of reflexive eye movement (saccades, the angular vestibulo-ocular reflex (AVOR), the linear vestibulo-ocular reflex (LVOR)), or the vestibulo-collic reflex (VCR), to a particular change in gain or phase in one condition of gravitoiner-tial force, and adapting to a different gain or phase (or asking for no change) in a second gravitoinertial force condition, and then seeing if the gravitoinertial force itself - the context cue - can recall the previously learned adapted responses. The majority of the experiments in the laboratory use the direction of vertical gaze or the direction of gravity (head tilt) as the context cue. This allows us to study context-specificity in a ground-based setting. One set of experiments, to be performed in parabolic flight, specifically uses the magnitude of gravitoinertial force as a context cue. This is a much better analog of the situation encountered in space flight. Various experiments investigate the behavioral properties, neurophysiological basis, and anatomical substrate of context-specific learning mechanisms. We use otolith (gravity) signals as the contextual cue for switching between adapted states of the saccadic system, the angular and linear vestibulo-ocular reflexes, and the VCR. (By LVOR we mean the oculomotor response - horizontal, vertical, and torsional - to linear translation of the head and body.) We are studying the effect of context on adaptation of saccade gain, phase and gain of the AVOR and LVOR, on ocular counterrolling (OCR) in response to static head tilt, and on head/neck reflexes (VCR) in response to rotation in different orientations. Such research is particularly germane to potential problems of postural and oculomotor control upon exposure to different gravitational environments.

Shelhamer, Mark J.↗

Gravity and thermoregulation: metabolic changes and circadian rhythms

Gravity appears to alter thermoregulation through changes in both the regulated level of body temperature and the rhythmic organization of temperature regulation. Gravity has been hypothesized to have an associated metabolic cost. Increased resting energy expenditure and dietary intake have been observed in animals during centrifuge experiments at hypergravity. Thus far, only animals have shown a corresponding reduction in metabolism in microgravity. Altered heat loss has been proposed as a response to altered gravitational environments, but remains documented only as changes in skin temperature. Changes in circadian timing, including the body temperature rhythm, have been shown in both hypergravity and microgravity, and probably contribute to alterations in sleep and performance. Changes in body temperature regulation may result from circadian disturbance, from the direct or indirect actions of gravity on the regulated temperature, or from changes in thermoregulatory effectors (heat production and heat loss) due to altered gravitational load and convective changes. To date, however, we have little data on the underlying thermoregulatory changes in altered gravity, and thus the precise mechanisms by which gravity alters temperature regulation remain largely unknown.

Non-NASA Center↗

Toward an understanding of global change

In the international scientific community, the International Council of Scientific Unions has organized the International Geosphere Biosphere Program (IGBP) to address the problems of global change. The objective of the IGBP is to describe and understand the interactive physical, chemical, and biological processes that regulate the total earth system, the unique environment that it provides for life, the changes that are occurring in this system, and the manner in which they are influenced by human activities. The IGBP is currently in its preparatory phase, during which the program's goals and research components are slowly evolving and coming into focus. In this report, a limited number of high-priority research initiatives are recommended for early implementation as part of the U.S. contribution to the preparatory phase of the IGBP. The recommendations are based on the committee's analysis of the most critical gaps, not being addressed by existing programs, in the scientific knowledge needed to understand the changes that are occurring in the earth system on time scales of decades to centuries. These initiatives will build upon the capabilities of the U.S. program in global change.

Source record↗

Color Choice is Everything - Impacts Color makes to the Lighting Environment

When contracts are let out to design multiple systems in a vehicle, it is a challenge to maintain integration between system leads. Designers on niche systems, like lighting and control panel design, often get caught up in the challenge of designing the light source or visual interface and fail to include time in their schedule to work with system architects on how their lighting system will be integrated. Additionally, behavioral scientists, industrial designers, and materials engineers get caught up with the materials and look of the system, but often fail to consider how the selection of their materials could affect the certification or performance of electronic devices like lighting systems. Additionally, computer modeling of the system architecture often assumes a perfect environment without the clutter of actual human use (dirt, stowage, crowding). As a result, lighting systems, and backlit displays run the risk of being overdesigned or under designed. Engineers making the assumption that because they have no input or there is no requirement on work surface reflectance, make the assumption that they can t count on good material choices and thus may install more lighting than is necessary. While having more lights may seem better, for a vehicle that is trying to conserve power, more lights may not be a good option. On the other hand, designers who made the opposite assumption and designed a lighting system that only produced just enough light, often wind up with a system that did conserve power, but didn t produce enough light. These situations are exasperated when the system starts to be used and the models are not perfect anymore. The lack of coordination and iterative design not only can impact lighting levels within an environment, but also can affect color perception. This is because, if materials do not represent a gradation of white or black, the material unevenly absorbs and reflects light at different wavelengths of the visual spectrum. The lighting designer may have built a light that meets light spectra requirements, but the eventual light reaching the human user may not be the spectra of light architects intended, if materials near the light source change the spectrum just by how much color is absorbed or reflected. With the recent findings concerning Circadian rhythm, where the spectra of light is extremely important for addressing crew sleep and wake cycles, system architects should pay considerable attention on the impact material choices have in changing the light spectrum in an environment. This presentation will show examples of how material choices impact the resulting illuminance, color spectrum, and power usage of an illuminated space. Its goal is to encourage system designers and planners to use more care in development of requirements and the verification of systems intended for the human visual interface.

Clark, Toni A.↗

Acclimation of leaf respiration consistent with optimal photosynthetic capacity

Abstract Plant respiration is an important contributor to the proposed positive global carbon‐cycle feedback to climate change. However, as a major component, leaf mitochondrial (‘dark’) respiration ( R d ) differs among species adapted to contrasting environments and is known to acclimate to sustained changes in temperature. No accepted theory explains these phenomena or predicts its magnitude. Here we propose that the acclimation of R d follows an optimal behaviour related to the need to maintain long‐term average photosynthetic capacity ( V cmax ) so that available environmental resources can be most efficiently used for photosynthesis. To test this hypothesis, we extend photosynthetic co‐ordination theory to predict the acclimation of R d to growth temperature via a link to V cmax , and compare predictions to a global set of measurements from 112 sites spanning all terrestrial biomes. This extended co‐ordination theory predicts that field‐measured R d and V cmax accessed at growth temperature ( R d,tg and V cmax,tg ) should increase by 3.7% and 5.5% per degree increase in growth temperature. These acclimated responses to growth temperature are less steep than the corresponding instantaneous responses, which increase 8.1% and 9.9% per degree of measurement temperature for R d and V cmax respectively. Data‐fitted responses proof indistinguishable from the values predicted by our theory, and smaller than the instantaneous responses. Theory and data are also shown to agree that the basal rates of both R d and V cmax assessed at 25°C ( R d,25 and V cmax,25 ) decline by ~4.4% per degree increase in growth temperature. These results provide a parsimonious general theory for R d acclimation to temperature that is simpler—and potentially more reliable—than the plant functional type‐based leaf respiration schemes currently employed in most ecosystem and land‐surface models.

Wang, Han↗

Spacelab Life Sciences flight experiments: an integrated approach to the study of cardiovascular deconditioning and orthostatic hypotension

The microgravity environment of spaceflight produces rapid cardiovascular changes which are adaptive and appropriate in that setting, but are associated with significant deconditioning and orthostatic hypotension on return to Earth's gravity. The rapidity with which these space flight induced changes appear and disappear provides an ideal model for studying the underlying pathophysiological mechanisms of deconditioning and orthostatic hypotension, regardless of etiology. Since significant deconditioning is seen after flights of very short duration, muscle atrophy due to inactivity plays, at most, a small role. These changes in circulatory control associated with cephalad fluid shifts, rather than inactivity per se, are probably more important factors. In order to test this hypothesis in a systematic way, a multidisciplinary approach which defines and integrates inputs and responses from a wide variety of circulatory sub-systems is required. The cardiovascular experiments selected for Spacelab Life Sciences flights 1 and 2 provide such an approach. Both human and animal models will be utilized. Pre- and post-flight characterization of the payload crew includes determination of maximal exercise capacity (bicycle ergometry), orthostatic tolerance (lower body negative pressure), alpha and beta adrenergic sensitivity (isoproterenol and phenylephrine infusions), baroreflex sensitivity (ECG-gated, stepwise changes in carotid artery transmural pressure with a pneumatic neck collar), and responses to a 24 h period of 5 deg head-down tilt. Measurements of cardiac output (CO2 and C2H2 rebreathing), cardiac chamber dimensions (phased-array 2-dimensional echocardiography), direct central venous pressure, leg volume (Thornton sock), limb blood flow and venous compliance (occlusion plethysmography), blood and plasma volumes, renal plasma flow and glomerular filtration rates, and various hormonal levels including catecholamines and atrial natriuretic factor will also be obtained. The central venous catheter will be inserted immediately pre-launch and monitored with heart rate and blood pressure in-flight until cardiac output, respiratory gas exchange and quantitative 2D echocardiography measurements can be performed. In-flight hemodynamic measurements will be repeated at rest and during submaximal exercise daily and also during maximal exercise midway through the flight to document the timecourse and extent of cardiovascular changes in the payload crew. Parallel studies are planned for the animals. In addition to measurements of right atrial and aortic pressures and cardiac output, a dorsal micro-circulatory chamber will allow determinations of changes in capillary and venular architecture and function in six of the rats. The techniques and findings from many of the SLS-1 and 2 supporting studies have already yielded significant information about circulatory regulation in patients with both hypo- and hypertension. The flight experiments themselves will provide new data to test the validity of both animal and human models currently used for simulating the fluid shifts of a micro-gravity environment. The development of effective countermeasures, not only for short and long duration space travellers, but also for Earth-bound medical patients can then be physiologically based on experimental data rather than anecdote.

Non-NASA Center↗

LEGEND, a LEO-to-GEO Environment Debris Model

LEGEND (LEO-to-GEO Environment Debris model) is a three-dimensional orbital debris evolutionary model that is capable of simulating the historical and future debris populations in the near-Earth environment. The historical component in LEGEND adopts a deterministic approach to mimic the known historical populations. Launched rocket bodies, spacecraft, and mission-related debris (rings, bolts, etc.) are added to the simulated environment. Known historical breakup events are reproduced, and fragments down to 1 mm in size are created. The LEGEND future projection component adopts a Monte Carlo approach and uses an innovative pair-wise collision probability evaluation algorithm to simulate the future breakups and the growth of the debris populations. This algorithm is based on a new "random sampling in time" approach that preserves characteristics of the traditional approach and captures the rapidly changing nature of the orbital debris environment. LEGEND is a Fortran 90-based numerical simulation program. It operates in a UNIX/Linux environment.

Liou, Jer Chyi↗

Aluminum Metal–Organic Framework Triggers Carbon Dioxide Reduction Activity

Confinement of metal centers is a powerful tool to manipulate reactivity and tune selectivity in chemical transformations. While aluminum as a foil is inactive for carbon dioxide reduction and shows high selectivity for the hydrogen evolution reaction, here we show that aluminum confined in a metal-organic framework (MOF), MIL-53(Al), suppresses hydrogen evolution reaction activity and enhances carbon dioxide reduction. This aluminum MOF can produce up to 40% faradaic efficiency for carbon monoxide and formic acid. Here, this study demonstrates that the unique reaction environment created by the MOF enables changes in reaction selectivity and can impart atypical catalytic capabilities to metals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chromophore carbonyl twisting in fluorescent biosensors encodes direct readout of protein conformations with multicolor switching

Fluorescent labeling of proteins is a powerful tool for probing structure-function relationships with many biosensing applications. Structure-based rules for systematically designing fluorescent biosensors require understanding ligand-mediated fluorescent response mechanisms which can be challenging to establish. We installed thiol-reactive derivatives of the naphthalene-based fluorophore Prodan into bacterial periplasmic glucose-binding proteins. Glucose binding elicited paired color exchanges in the excited and ground states of these conjugates. X-ray structures and mutagenesis studies established that glucose-mediated color switching arises from steric interactions that couple protein conformational changes to twisting of the Prodan carbonyl relative to its naphthalene plane. Mutations of residues contacting the carbonyl can optimize color switching by altering fluorophore conformational equilibria in the apo and glucose-bound proteins. A commonly accepted view is that Prodan derivatives report on protein conformations via solvatochromic effects due to changes in the dielectric of their local environment. Here we show that instead Prodan carbonyl twisting controls color switching. These insights enable structure-based biosensor design by coupling ligand-mediated protein conformational changes to internal chromophore twists through specific steric interactions between fluorophore and protein.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning the Mechanical Properties of Crosslinked Copolymers via Sequence and Solvent‐Selective Swelling for Vat Photopolymerization

Block copolymers (BCPs) offer distinct advantages for vat photopolymerization by enabling mechanically programmable network structures through microphase-separated morphologies that can be kinetically trapped during curing, yielding properties unattainable in homogeneous resins. However, the respective roles of repeat-unit sequence and solvent environment, together with their interplay in directing network formation and mechanical performance, remain unclear. Here, we synthesize a series of CO 2 -based polycarbonate copolymers comprising a crosslinkable glassy poly(vinyl cyclohexene carbonate) (PVCHC, A block) and a non-crosslinkable soft poly(propylene carbonate) (PPC, B block). The polymer sequence is systematically varied (ABA, BAB, and statistical), and solvent choice controls block-selective swelling to jointly control gelation behavior, microphase morphology, and mechanical response through changes in the accessibility and local environment of photocrosslinkable vinyl groups during network formation, as revealed by photorheology and small angle x-ray scattering. By tuning polymer sequence and curing solvent, we transform nominally identical formulations from brittle to highly ductile materials, achieving a three-orders-of-magnitude range in toughness (0.003 to 9.1 MJ m −3 ). These results establish clear structure–processing–property relationships and identify polymer sequence and selective solvation as powerful strategies for programming both printability and performance of block copolymer resins for additive manufacturing.

additive manufacturing↗

Realizing the Materials-Designed-To-Environments Promise of Additive Manufacturing Through a Fundamentally Different Approach to Optimization of Nonlinear Solid Mechanics Structures

Additive Manufacturing (AM) is expected to play a large role in the labs-wide goals of accelerating innovation and leading in modern engineering. More specifically, AM is seen as a key enabling technology for increasing the agility of nuclear deterrence and other national security applications involving complex coupled environments. However, the impact of AM on these initiatives has not been as wide-ranging as hoped because – despite its unique qualities – the focus has mostly been on detailed qualification to force AM components into pre-existing performance envelopes. This paradigm fundamentally precludes the novel possibilities afforded by the geometric and material flexibility of AM. In particular, the engineering of small-scale features to undergo buckling and contact can cause large geometric and symmetry changes which provide responsiveness to different environments. Despite almost a decade of observing such behavior, there exists no way to systematically design for AM to exploit it. Our goal for this project was to connect material design to multi-environment component performance by reconceptualizing how to design for AM to exploit the buckling and contact of small-scale features.

36 MATERIALS SCIENCE↗

Aldol Condensation and Esterification over Ti-Substituted *BEA Zeolite: Mechanisms and Effects of Pore Hydrophobicity

Aldol condensation and esterification reactions provide paths to upgrade ethanol and acetaldehyde to higher- value molecules useful as fuels or intermediates for the synthesis of polymers. Transition-metal-substituted BEA zeolites (M-BEA) catalyze these reactions; however, the mechanisms for these processes in M-BEA and the effects of incidental or purposefully included silanol groups are not reported. Here, we combine kinetic and spectroscopic measurements obtained during catalytic reactions of acetaldehyde (CH 3 CHO), ethanol (C 2 H 5 OH), and hydrogen (H 2 ) mixtures over a series of Ti-BEA catalysts that possess a known range of silanol group densities to examine the kinetic relevance of intervening steps and the impact of silanol groups on catalytic rates. Across all Ti-BEA, rates for aldol condensation and esterification increase with the pressure of CH 3 CHO; however, C 2 H 5 OH and H 2 O weakly inhibit the rates of these reactions. The substitution of CD 3 CDO for CH 3 CHO decreases aldol condensation rates slightly (~10%) but leads to greater esterification rates (2- to 5-fold). The kinetic isotope effects together with the measured dependence of rates on reactant pressures suggest that aldol condensation and esterification occur on unoccupied Ti sites and involve multiple kinetically relevant steps. CH 3 CHO deprotonates irreversibly, and the kinetically relevant nucleophilic attack of the enolate to CH 3 CHO* (i.e., adsorbed CH 3 CHO on Ti sites) leads to aldol products, while the nucleophilic attack of the enolate to C 2 H 5 OH* gives esters. Selectivities toward aldol condensation increase with the ratio of CH 3 CHO to C 2 H 5 OH pressure and with increases in the silanol density of the as-synthesized Ti-BEA. During catalysis, in situ infrared spectroscopy demonstrates that these silanol groups react with C 2 H 5 OH to form ethoxysilane groups (i.e., SiOC 2 H 5 ) that modify the polarity of the environment near Ti active sites. As initial silanol densities increase, steady-state turnover rates for aldol condensation and esterification increase by factors of 5 and 2, respectively. The changes in rates and selectivities among Ti-BEA catalysts likely reflect changes in excess free energies of transition states for enolization and nucleophilic attack of the enolate to adsorbed coreactants. The differences in excess stability report on the interactions among reactive intermediates at framework Ti atoms and the ethoxysilane and remaining silanol groups present. Furthermore, the in situ modification of these pore environments confers changes in the stability of reactive species in a manner that contradicts intuition when considering the initial state of the catalyst but can be reconciled after accounting for the formation of persistent alkoxy surface moieties in the pores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of secondary yield parameter variation on predicted equilibrium potential of an object in a charging environment

The sensitivity of predicted equilibrium potential to changes in secondary electron yield parameters was investigated using MATCHG, a simple charging code which incorporates the NASCAP material property formulations. The equilibrium potential was found to be a sensitive function of one of the two parameters specifying secondary electron yield due to proton impact and of essentially all the parameters specifying yield due to electron impact. The information on the electron generated secondary yield parameters was discovered to be obtainable from monoenergetic beam charging data if charging rates as well as equilibrium potentials are accurately recorded.

Purvis, C. K.↗