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At present, meteorites collected in Antarctica dominate the total number of the world's known meteorites. We focus here on the scientific advances in cosmochemistry and planetary science that have been enabled by access to, and investigations of, these Antarctic meteorites. A meteorite recovered during one of the earliest field seasons of systematic searches, Elephant Moraine (EET) A79001, was identified as having originated on Mars based on the composition of gases released from shock melt pockets in this rock. Subsequently, the first lunar meteorite, Allan Hills (ALH) 81005, was also recovered from the Antarctic. Since then, many more meteorites belonging to these two classes of planetary meteorites, as well as other previously rare or unknown classes of meteorites (particularly primitive chondrites and achondrites), have been recovered from Antarctica. Studies of these samples are providing unique insights into the origin and evolution of the Solar System and planetary bodies.
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Previous studies attributed the origin of metal veins penetrating graphite nodules in the Canyon Diablo IAB main group iron meteorite to condensation from vapor or melting of host metal. Abundances of 16 siderophile elements measured in kamacite within vein and host meteorite are most consistent with an origin by melting of the host metal followed by fractional crystallization of the liquid. The presence of the veins within graphite nodules may be explained by impact, as peak shock temperatures, and thus the most likely areas to undergo metal melting, are at metal-graphite interfaces. The origin of the veins is constrained by Re-Os chronometry to have occurred early (>4 Ga) in Solar System history.
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Laboratory studies of meteorites and robotic exploration of Mars reveal scant atmosphere, no evidence of plate tectonics, past evidence for abundant water, and a protracted igneous evolution. Despite indirect hints, direct evidence of a martian origin came with the discovery of trapped atmospheric gases in one meteorite. Since then, the study of martian meteorites and findings from missions have been linked. Although the meteorite source locations are unknown, impact ejection modeling and spectral mapping of Mars suggest derivation from small craters in terrains of Amazonian to Hesperian age. Whereas most martian meteorites are young (< 1.3 Ga), the spread of whole rock isotopic compositions results from crystallization of a magma ocean > 4.5 Ga and formation of enriched and depleted reservoirs. However, the history inferred from martian meteorites conflicts with results from recent Mars missions, calling into doubt whether the igneous histor y inferred from the meteorites is applicable to Mars as a whole. Allan Hills 84001 dates to 4.09 Ga and contains fluid-deposited carbonates. Accompanying debate about the mechanism and temperature of origin of the carbonates came several features suggestive of past microbial life in the carbonates. Although highly disputed, the suggestion spurred interest in habitable extreme environments on Earth and throughout the Solar System. A flotilla of subsequent spacecraft has redefined Mars from a volcanic planet to a hydrologically active planet that may have harbored life. Understanding the history and habitability of Mars depends on understanding the coupling of the atmosphere, surface, and subsurface. Sample return that brings back direct evidence from these diverse reservoirs is essential.
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Evolução Planetária , Meio Ambiente Extraterreno/química , Marte , Meteoroides , Voo Espacial/métodos , Voo Espacial/tendênciasRESUMO
A commonly encountered challenge with freeze-dried drug products is glass vial fogging. Fogging is characterized by a thin layer of product deposited upon the inner surface of the vial above the lyophilized cake. While considered to be a routine cosmetic defect in many instances, fogging around the shoulder and neck of the vial may potentially impact container closure integrity and reject rates during inspection. In this work, the influence of processing conditions i.e. vial pre-treatment, lyophilization cycle modifications and filling conditions on fogging was evaluated. A battery of analytical techniques was employed to investigate factors affecting glass vial fogging. A fogging score was used to quantify its severity in freeze-dried products. Additionally, a dye-based method was used to study solution upcreep (Marangoni flow) following product filling. Our lab-scale results indicate measurable improvement in fogging following the addition of an annealing step in the lyophilization cycle. Pre-freeze isothermal holding of the vials (at 5°C on the lyophilizer shelf) for an extended duration indicated a reduction in fogging whereas an increase in the freezing time exhibited no effect on fogging. Vial pre-treatment conditions were critical determinants of fogging for Type 1 vials whereas they had no impact on fogging in TopLyo® vials. The headspace relative humidity (RH) investigation also indicated sufficient increase in the water vapor pressure inside the vial to be conducive to the formulation of a hydration film - the precursor to Marangoni flow.
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Measurement of heat transfer coefficients (Kv) is an important part of freeze-dryers characterization and as well a necessary step for executing any modelling. In most cases only an average value of Kv is calculated, or an average value of center and edge vials is provided. Our aim is to go a step further and to describe the overall Kv distribution various vial/ freeze drier combinations, whatever the pressure. From an experimental point of view, in this article we propose three methods to calculate the Kv value for individual vials based on the ice sublimation gravimetric method. The first method we use is the most usual one, where the Kv value is calculated based on the mass of sublimated ice and the product temperature measured in selected vias. In the second method, the average product temperature is estimated for each vial, based on the mass difference before and after sublimation and the Kv value is calculated accordingly. In the third method, the Kv is estimated by comparison to sublimation results from a simulation. Results from methods 2 and 3 are very similar results and are slightly different from those of method 1. Method 1 was shown to exhibit a systematic bias due to the fact that it is based on the temperature of recording of selected vials only, which are not representative for all positions. Once the individual values of Kv have been calculated, it is possible to establish a distribution for each method. It was observed that an overlay of two normal distributions describing the center and the edge vials provides a good representation of the empirical distribution. Furthermore, we propose a holistic model aiming to calculate the Kv distribution for any specified pressure.
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Gelo , Tecnologia Farmacêutica , Tecnologia Farmacêutica/métodos , Temperatura , Temperatura Alta , Liofilização/métodosRESUMO
The succinic acid/succinate system has an excellent buffering capacity at acidic pH values (4.5-6.0), promising to be a buffer of choice for biologics having slightly acidic to basic isoelectric points (pI 6 - 9). However, its prevalence in drug products is limited due to the propensity (risk) of its components to crystallize during freezing and the consequent shift in the pH which might affect the product stability. Most of these previous assessments have been performed under operational conditions that do not simulate typical drug product processing conditions. In this work, we have characterized the physicochemical behavior of succinate formulations under representative pharmaceutical conditions. Our results indicate that the pH increases by â¼ 1.2 units in 25 mM and 250 mM succinate buffers at pharmaceutically relevant freezing conditions. X-ray diffractometry studies revealed selective crystallization of monosodium succinate, which is posed as the causative mechanism. This salt crystallization was not observed in the presence of 2% w/v sucrose, suggesting that this pH shift can be mitigated by including sucrose in the formulation. Additionally, three monoclonal antibodies (mAbs) that represent different IgG subtypes and span a range of pIs (5.9 - 8.8) were formulated with succinate and sucrose and subjected to freeze-thaw, frozen storage and lyophilization. No detrimental impact on quality attributes (QA) such as high molecular weight (HMW) species, turbidity, alteration in protein concentration and sub-visible particles, was observed of any of the mAbs tested. Lastly, drug formulations lyophilized in succinate buffer with sucrose demonstrated acceptable QA profiles upon accelerated kinetic storage stability, supporting the use of succinate buffers in mAb drug products.
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Produtos Biológicos , Ácido Succínico , Ácido Succínico/química , Soluções Tampão , Concentração de Íons de Hidrogênio , Liofilização/métodos , Succinatos , Sacarose/química , Estabilidade de MedicamentosRESUMO
The NASA Psyche mission's program to engage university undergraduates and the public in the mission is inspired by and built upon the extensive foundation of public engagement, educational outreach activities, and expertise of NASA and mission partner institutions. The program leverages the enthusiasm and contributions of undergraduates nationwide to the benefit of the mission, the students and their institutions and communities, and the broader public. Psyche Student Collaborations consists of four main programs, two (Psyche Capstone and Psyche Inspired) are available solely to undergraduates enrolled at universities or community colleges in the United States and its territories and two (Innovation Toolkit free online courses and Science Outreach Interns and Docents) invite broader participation by engaging the talents and creativity of undergraduate interns to help create content and events to reach the public and lifelong learners. Together, these offerings provide multiple entry points and a spectrum of intensity of experiences, numbers of participants, disciplinary diversity, and mode of delivery. Involving undergraduates in all phases of the program supports the development of the next generation of explorers, contributes to the nation's workforce preparation, and complements NASA's existing undergraduate offerings by providing long-term opportunities for students to participate with the mission through established postsecondary education structures like capstone courses.
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The Psyche mission's Oxidation-Reduction Working Group is focused on understanding, determining, and applying the redox state of (16) Psyche to understand the origin of a metal-rich world. The oxidation-reduction state of an asteroid, along with its temperature, parent body size, and composition, is a key parameter in determining the history of an asteroid. Determining the redox state from spacecraft data is most easily done by examining potential metal-oxide buffer pairs. The occurrence of Ni, Fe, C, Cr, P and Si, in that order, in the metal or sulfide phase of an asteroidal body indicates increasingly reduced conditions. Key observations by the Imager and Gamma-Ray and Neutron Spectrometer (GRNS) of Psyche can bracket the redox state using metal-oxide buffers. The presence of Fe,Ni metal can be confirmed by the ratios of Fe/O or Fe/Si and the concentration of Ni variability in metal across the asteroid can be determined by GRNS. The FeO concentration of silicates is complementary to the Ni concentration of metal and can be constrained using filters on the Imager. The presence of FeO in silicates from ground-based observations is one of the few measurements we already have of redox state, although available data permit a wide range of silicate compositions and mineralogies. The presence of C, P or Si concentrated in the metallic, Fe-rich portion of the asteroid, as measured by GRNS, or Ca-sulfide, determined by imaging, would indicate increasingly reducing conditions. Linkage to known types of meteorites, whether metal-rich chondrites, stony-irons or irons, expands the mineralogical, chemical and isotopic data not available from remote observations alone. Redox also controls both silicate and metal mineralogy, influencing differentiation, solidification, and subsolidus cooling, including the relative abundance of sulfur in the core and possible magnetic signatures. The redox state of Psyche, if a fully-differentiated metallic core, might constrain the location and timing of both the formation of Psyche and any oxidation it might have experienced.
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The asteroid (16) Psyche may be the metal-rich remnant of a differentiated planetesimal, or it may be a highly reduced, metal-rich asteroidal material that never differentiated. The NASA Psyche mission aims to determine Psyche's provenance. Here we describe the possible solar system regions of origin for Psyche, prior to its likely implantation into the asteroid belt, the physical and chemical processes that can enrich metal in an asteroid, and possible meteoritic analogs. The spacecraft payload is designed to be able to discriminate among possible formation theories. The project will determine Psyche's origin and formation by measuring any strong remanent magnetic fields, which would imply it was the core of a differentiated body; the scale of metal to silicate mixing will be determined by both the neutron spectrometers and the filtered images; the degree of disruption between metal and rock may be determined by the correlation of gravity with composition; some mineralogy (e.g., modeled silicate/metal ratio, and inferred existence of low-calcium pyroxene or olivine, for example) will be detected using filtered images; and the nickel content of Psyche's metal phase will be measured using the GRNS.
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NASA's first asteroid sample return mission, OSIRIS-REx, collected a sample from the surface of near-Earth asteroid Bennu in October 2020 and will deliver it to Earth in September 2023. Selecting a sample collection site on Bennu's surface was challenging due to the surprising lack of large ponded deposits of regolith particles exclusively fine enough ( ≤ 2 cm diameter) to be ingested by the spacecraft's Touch-and-Go Sample Acquisition Mechanism (TAGSAM). Here we describe the Sampleability Map of Bennu, which was constructed to aid in the selection of candidate sampling sites and to estimate the probability of collecting sufficient sample. "Sampleability" is a numeric score that expresses the compatibility of a given area's surface properties with the sampling mechanism. The algorithm that determines sampleability is a best fit functional form to an extensive suite of laboratory testing outcomes tracking the TAGSAM performance as a function of four observable properties of the target asteroid. The algorithm and testing were designed to measure and subsequently predict TAGSAM collection amounts as a function of the minimum particle size, maximum particle size, particle size frequency distribution, and the tilt of the TAGSAM head off the surface. The sampleability algorithm operated at two general scales, consistent with the resolution and coverage of data collected during the mission. The first scale was global and evaluated nearly the full surface. Due to Bennu's unexpected boulder coverage and lack of ponded regolith deposits, the global sampleability efforts relied heavily on additional strategies to find and characterize regions of interest based on quantifying and avoiding areas heavily covered by material too large to be collected. The second scale was site-specific and used higher-resolution data to predict collected mass at a given contact location. The rigorous sampleability assessments gave the mission confidence to select the best possible sample collection site and directly enabled successful collection of hundreds of grams of material.
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Determining compositional trends among individual minerals is key to understanding the thermodynamic conditions under which they formed and altered, and is also essential to maximizing the scientific value of small extraterrestrial samples, including returned samples and meteorites. Here we report the chemical compositions of Fe-sulfides, focusing on the pyrrhotite-group sulfides, which are ubiquitous in chondrites and are sensitive indicators of formation and alteration conditions in the protoplanetary disk and in small Solar System bodies. Our data show that while there are trends with the at.% Fe/S ratio of pyrrhotite with thermal and aqueous alteration in some meteorite groups, there is a universal trend between the Fe/S ratio and degree of oxidation. Relatively reducing conditions led to the formation of troilite during: (1) chondrule formation in the protoplanetary disk (i.e., pristine chondrites) and (2) parent body thermal alteration (i.e., LL4 to LL6, CR1, CM, and CY chondrites). Oxidizing and sulfidizing conditions led to the formation of Fe-depleted pyrrhotite with low Fe/S ratios during: (1) aqueous alteration (i.e., CM and CI chondrites), and (2) thermal alteration (i.e., CK and R chondrites). The presence of troilite in highly aqueously altered carbonaceous chondrites (e.g., CY, CR1, and some CM chondrites) indicates they were heated after aqueous alteration. The presence of troilite, Fe-depleted pyrrhotite, or pyrite in a chondrite can provide an estimate of the oxygen and sulfur fugacities at which it was formed or altered. The data reported here can be used to estimate the oxygen fugacity of formation and potentially the aqueous and/or thermal histories of sulfides in extraterrestrial samples, including those returned by the Hayabusa2 mission and due to be returned by the OSIRIS-REx mission in the near future.
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BACKGROUND: Large healthcare systems provide an opportunity to disseminate evidence-based interventions to primary care. We evaluated the impact of a train-the-trainer model in two large systems to disseminate the Announcement Approach Training, which teaches providers to communicate about HPV vaccination more effectively. METHODS: In collaboration with the American Cancer Society, we partnered with two midwestern healthcare systems that served over 77,000 patients ages 11 through 17. Both systems hosted a 2-hour train-the-trainer workshop. Providers from one system then conducted in-person 1-hour CME-eligible trainings, using our standard slide set and script (available at hpvIQ.org). The other system did not implement trainings, providing a natural experiment. RESULTS: The train-the-trainer workshop included physicians, nurses and other clinical staff (n = 11/13 for intervention/comparison systems). The intervention system delivered 18 trainings to 234 physicians, nurses, and other clinic staff. From baseline to 6-month follow-up, the intervention system had an increase in HPV vaccine uptake that was larger than that of the comparison system for adolescents ages 11 through 12 (1.9%, p = .002) and ages 13 through 17 (1.5%, p = .015). Attending the training was associated with increased intentions to routinely recommend HPV vaccine when patients turn 11 or 12 (mean 4.19 (SD = 0.95) vs. 4.43 (SD = 0.83) as well as increased positive vaccine attitudes, self-efficacy, and norms (all p < .001). Participant satisfaction with the trainings was high (90%-94%). CONCLUSION: The train-the-trainer model was effective in increasing provider motivation to recommend HPV vaccination and led to a small increase in vaccine uptake. Dissemination through large healthcare systems is promising but faces some challenges.
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Infecções por Papillomavirus , Vacinas contra Papillomavirus , Médicos , Adolescente , Criança , Comunicação , Atenção à Saúde , Conhecimentos, Atitudes e Prática em Saúde , Humanos , Motivação , Infecções por Papillomavirus/prevenção & controle , VacinaçãoRESUMO
Near-infrared (NIR) and frequency modulated spectroscopy (FMS) were employed, for non-invasive moisture determination of a lyophilized biologic drug product (DP). Development of NIR and FMS provides a rapid non-invasive means of residual moisture measurement, and would be beneficial compared with traditional time consuming, product destructive methods such as Karl Fischer (KF). A model therapeutic enzyme in a sucrose-based formulation was employed for proof of concept studies, and NIR and FMS methods were compared side by side for residual moisture analysis. Moisture models were created using lyophilized vials and comparisons were made between the methods using different moisture preparation approaches:1) direct water droplet addition to the vial headspace, 2) use of elevated temperature (80°C), and 3) using various levels of moisture in stoppers generated during the washing and drying procedures, then lyophilizing using the stoppers and placing the sealed vials on stability. The results for direct water addition gave an average percent error for residual moisture of 5.7% for NIR and 9.4% for FMS when compared to KF. The elevated temperature method resulted in an average percent error for residual moisture of 54% for NIR and 43% for FMS compared to KF. The stopper moisture stability study, for FMS, provided an average percent error for residual moisture of 31% compared to KF. The error was greater for the elevated temperature and stopper methods, due to the low moisture values, which resulted in greater error. At this lower range of moisture (<1%) both NIR and FMS were less accurate, but from 1 to 5% their accuracy increased, based on the models used in this study. NIR and FMS methods can be used to complement KF at these lower moisture levels and models could be further improved with additional data points. NIR and FMS methods have advantages and disadvantages for residual moisture analysis when compared to each other, but both provided an accurate measurement of drug product moisture (depending on the method used for moisture increase), they can be used as process analytical technology (PAT), and both can be used for fast non-invasive moisture determination.
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Produtos Biológicos , Espectroscopia de Luz Próxima ao Infravermelho , Liofilização , Sacarose , ÁguaRESUMO
Although many biotech products are successfully stored in the frozen state, there are cases of degradation of biologicals during freeze storage. These examples are discussed in the Perspective to emphasize the fact that stability of frozen biologicals should not be taken for granted. Frozen-state degradation (predominantly, aggregation) has been linked to crystallization of a cryoprotector in many cases. Other factors, for example, protein unfolding (either due to cold denaturation or interaction of protein molecules with ice crystals), could also contribute to the instability. As a hypothesis, additional freezing-related destabilization pathways are introduced in the paper, that is, air bubbles formed on the ice crystallization front, and local pressure and mechanical stresses due to volume expansion during water-to-ice transformation. Furthermore, stability of frozen biologicals can depend on the sample size, via its impact on the freezing kinetics (i.e., cooling rates and freezing time) and cryoconcentration effects, as well as on the mechanical stresses associated with freezing. We conclude that, although fundamentals of freezing processes are fairly well described in the current literature, there are important gaps to be addressed in both scientific foundations of the freezing-related manufacturing processes and implementation of the available knowledge in practice.
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Produtos Biológicos/química , Excipientes/química , Congelamento/efeitos adversos , Proteólise , Produtos Biológicos/metabolismo , Cristalização/métodos , Estabilidade de Medicamentos , Excipientes/metabolismo , HumanosRESUMO
The nucleosynthetic Mo, Ru, and W isotopic compositions of the South Byron Trio iron meteorite grouplet (SBT) are consistent with all three meteorites originating on a single parent body that formed in the carbonaceous chondrite (CC) isotopic domain within the Solar nebula. Consistent with a common origin, the highly siderophile element (HSE) concentrations of the SBT can be related to one another by moderate degrees of fractional crystallization of a parental melt with initially chondritic relative abundances of HSE, and with initial S and P contents of ~7 and ~1 wt. %, respectively. Tungsten-182 isotopic data for the SBT indicate the parent body underwent metal-silicate differentiation 2.1 ± 0.8 Myr after calcium aluminum rich inclusion formation, and thermal modeling suggests the parent body formed 1.1 ± 0.5 Myr after CAI formation. This accretion age is not resolved from the accretion ages of other CC and most noncarbonaceous (NC) type iron meteorite parent bodies. Comparison of the projected parental melt composition of the SBT to those projected for the IVA and IVB iron meteorite groups suggests that at least some portions of the CC nebular domain were more oxidized compared to the NC domain. In addition, comparison of the SBT parental melt S content to estimates for parent bodies of the IIAB, IIIAB, IVA, IID, and IVB "magmatic" iron meteorite groups suggests that CC type iron meteorite parental melts were characterized by a general depletion in S, in addition to depletions in some other moderately volatile elements. Based on chemical and O isotope similarities, prior studies have suggested the possibility of a common parent body for the SBT and the Milton pallasite. Molybdenum and Ru isotopic compositions of Milton also provide permissive evidence for this. The HSE concentrations in the Milton metal, however, cannot be related to the SBT by any known crystal-liquid fractionation or mixing path. Thus, Milton more likely formed on a different, chemically distinct, but genetically identical parent body present in the CC nebular domain.