Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “exclusive”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 541 records · Page 30
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Gas hydrate deposit formation in transient flowloop tests and mitigation with a surface treatment

Thermodynamic and thermal mitigation strategies are traditionally utilized to prevent gas hydrate formation but may be rendered ineffective for certain unplanned, extended shut-in scenarios. Unfortunately, the current knowledge regarding transient gas hydrate formation has been extremely limited to only a few studies and unable to address this complex issue adequately. This work, conducted in a lab-scale flowloop, aims to add to the understanding of this area by delving into the implications of transient conditions on gas hydrate formation mechanisms, while also exploring a possible mitigation strategy of a surface treatment. Specifically, the effects of phase separation on gas hydrate formation locations, transportability, and plugging are presented for an oil-dominated system. An omniphobic surface treatment is shown to affect initial gas hydrate deposition and its wall adherence strength, as well as the overall plugging outcome. Overall, this work combines observational information with process data measurements to provide a better understanding of phase separated gas hydrate systems and passive deposition mitigation strategies. This can further aid advanced gas hydrate modeling efforts, which currently do not adequately address transient flow effects on phase separation/dispersion. Here, it offers representative gas hydrate testing for coatings, which have exclusively been limited to non-flowing and/or bench-scale analysis, to give confidence in their potential application as advanced deposition prevention tools.

03 NATURAL GAS↗
DOE OSTI2020

Water and heat: New constraints on the evolution of the CV chondrite parent body

This paper focuses on the post-accretion history of CV3 chondrites, through a combination of petrographic and mineralogical characterization, magnetic measurements, spectral (Raman and Infrared) and thermo-gravimetric analysis of 31 meteorites (including 7 falls, 21 Antarctic and 3 non-Antarctic finds) spanning a wide metamorphic range. We classify the 21 Antarctic chondrites and the Bukhara fall into the CV Red , CV OxA , and CV OxB subgroups. We establish quantitative parameters relevant for this sub-classification. In comparison to CV Ox , CV Red chondrites are characterized by (i) a lower abundance of matrix, (ii) a higher abundance of metal, (iii) the presence of Ni-poor sulfides. In comparison to CV OxB , CV OxA are characterized by (i) similar matrix abundance, (ii) a higher abundance of metal, (iii) the presence of metal almost exclusively under the form of awaruite, (iv) lower Ni content of sulfides, (v) lower magnetic susceptibility and saturation remanence. In this work, both CV Ox (CV OxA and CV OxB ) and CV Red experienced aqueous alteration, and contain oxyhydroxides and phyllosilicates. We show that the abundance of these hydrated secondary minerals observed today in individual CV chondrites decreases with their peak metamorphic temperature. This is interpreted either as partial dehydration of these secondary minerals or limited hydration due to the rapid exhaustion of the water reservoir during parent body thermal metamorphism. Moreover, the lower abundance of oxyhydroxides (that have a lower thermal stability than phyllosilicates and may in large part postdate the peak of thermal metamorphism) in more metamorphosed CV chondrites is interpreted as lower availability of aqueous fluids during retrograde metamorphism in these meteorites. Lastly, we show that in comparison to CV OxB , CV OxA are systematically (i) more metamorphosed, (ii) less hydrated, (iii) depleted in ferromagnetic minerals, (iv) but enriched in metal in the form of secondary awaruite. CV OxA may be thermally metamorphosed CV OxB . CV Red are significantly different from CV Ox (matrix abundances, alteration products, opaque minerals), but span the same wide metamorphic range. This could be indicative of a laterally heterogeneous CV parent body, or suggest the existence of distinct parent bodies for CV Ox and CV Red chondrites.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Walking on the dark side: Anthropogenic factors limit suitable habitat for gray wolf ( Canis lupus ) in a large natural area covering Belarus and Ukraine

Due to successful conservation initiatives and legislations, the grey wolf (Canis lupus) is recolonising its historic range in Europe. However, wolves have never been extirpated across large areas in Eastern Europe but are often constrained to remote and inaccessible places due to centuries of persecution. This study aimed to identify the potentially suitable wolf habitats in Polesia, a massive cross-border lowland region extending over southern Belarus and northern Ukraine, which are often neglected in large carnivore studies at the continental scale. We hypothesized that anthropogenic rather than environmental factors govern wolf habitat suitability. We used a dataset of 4191 GPS locations obtained from radio-collared wolves (n = 26) and confirmed observations (n = 231) during 2014–2021 and applied maximum entropy method to estimate relative habitat suitability for wolves in Polesia. Artificial light at night (ALAN), proportion of cropland and tree cover were the most important factors affecting wolf habitat suitability. Road densities contributed poorly to predicting habitat suitability for wolves. Our models predicted a quarter of Polesia as suitable habitat and revealed priority areas connecting the important source populations in the Chornobyl Exclusion Zone in the east and the Bialowieza Forest in the west and thus essential for long-term wolf conservation. Our results provide the bases for effective, long-term wolf monitoring and management programs in both Belarus and Ukraine. However, national and transboundary wolf management in Polesia has been extremely challenging since 2022 due to the ongoing war and subsequent habitat degradation in this part of Europe.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Preclinical characterization of Pan-NKG2D ligand-binding NKG2D receptor decoys

NKG2D and its ligands are critical regulators of protective immune responses controlling infections and cancer, defining a crucial immune signaling axis. Current therapeutic efforts targeting this axis almost exclusively aim at enhancing NKG2D-mediated effector functions. However, this axis can drive disease processes when dysregulated, in particular, driving stem-like cancer cell reprogramming and tumorigenesis through receptor/ligand self-stimulation on tumor cells. Despite complexities with its structure and biology, we developed multiple novel engineered proteins that functionally serve as axis-blocking NKG2D “decoys” and report biochemical, structural, in vitro , and in vivo evaluation of their functionality.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Synergistic effect of microstructure and defects on the initiation of fatigue cracks in additively manufactured Inconel 718

Fatigue cracks in additively manufactured (AMed) Inconel 718 (IN-718) in machined surface condition often initiate from persistent slip bands (PSBs) unlike other popular AM alloys such as 17-4 PH stainless steel or Ti-6Al-4V, where fatigue crack initiation is exclusively from volumetric defects; therefore, a competition between PSB- vs. defect- mediated crack initiation clearly exists. To shed light on the factors governing the competition, this study investigates the characteristics of cyclic strain localization, PSB formation, and crack initiation via crystal plasticity (CP) modeling of cyclic loading on polycrystalline aggregates which are then validated by experiments. In this work, a physics-based, free slip distance (FSD) dependent slip strength evolution law is proposed, which is shown to enable the CP model to simulate the heterogeneous strain distribution in IN-718. Implementing a crack initiation criterion based on strain contrast, the locations and lives for crack initiation can also be calculated. It is shown that both FSD and resolve shear stress influence the strain localization and crack initiation behaviors. The distribution of a localization parameter calculated based on the multiplication of FSD and Schmid factor within a grain is found to correlate well with the locations of PSBs. The maximum values of the localization parameters within a microstructure are shown to correlate well with the experimentally obtained crack initiation lives. The presence of volumetric defects in IN-718 generally do not impact strain localization behavior unless their size is large compared to the grain size.

42 ENGINEERING↗
DOE OSTI2021

Bimodal particle distributions with increased thermal conductivity for solid particles as heat transfer media and storage materials

Solid particles are being considered in several high temperature thermal energy storage systems and as heat transfer media in a variety of advanced power generation systems, particularly in concentrated solar power plants. The downside of such an approach is the low overall heat transfer coefficients caused by the inherently low thermal conductivity values of the low-cost solid media when coupled to heat exchanger for the power cycle working fluid. Choosing the right particle size distribution, emittance, and material of the solid media can all make a substantial difference in packed bed thermal conductivity. Current research though exclusively focuses on continuous unimodal distributions of particles. Here, in this work, we propose the use of a binary particle system with a bimodal size distribution to significantly increase packed bed thermal conductivity by reducing packed bed porosity. This is the first study related to ceramic solid particle heat transfer that has considered the thermal conductivity of non-unimodal size distributions at room and elevated temperatures. The following study found that for the binary particle system using Carbo particles CP 16/30 – CP 70/140 where the large particle volume fraction was 50% there was an 17–47% increase in packed bed thermal conductivity when compared with a nearly unimodal particle size distribution of CP 16/30 between 50 and 300 °C. Two different porosity and effective thermal conductivity models were studied, with one providing better prediction of porosity but both effective thermal conductivity models providing less predictive capacity. Importantly this approach can have a substantial impact of thermal performance, with little to no impact on the particle cost.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Predicting critical heat flux using localized sensing at invisible vapor-liquid interfaces

Predicting critical heat flux (CHF) in two-phase electronics cooling systems remains a significant challenge due to the sudden onset of boiling crisis and the difficulty in directly visualizing vapor-liquid interfaces. Existing sensing methods rely on lagging temperature measurements, optically accessible systems, or spatially averaged signals that cannot pinpoint CHF initiation at localized high-heat-flux regions. Here, we report a planar capacitive sensing approach that enables real-time, localized detection of vapor-liquid interface dynamics for CHF prediction in boiling heat transfer. The capacitive sensor exploits the dielectric constant difference between liquid and vapor phases to capture bubble nucleation, growth, and departure dynamics with a temporal resolution down to 2 ms. The capacitive sensing reveals distinct signals across boiling regimes: from high-frequency fluctuations during strong nucleate boiling to low-frequency fluctuations with increased amplitudes when approaching CHF. The multi-sensor array experiments demonstrate real-time localized sensing, where each sensor responds exclusively to boiling in its immediate vicinity without crosstalk from neighboring regions. This non-intrusive sensing approach provides predictive rather than lagging sensing signals of CHF occurrence, offering predictive diagnosis of two-phase liquid cooling for the thermal management of high-power-density electronics.

CHF↗
DOE OSTI2025

A life cycle assessment of e-hydrogen production using proton-exchange membrane water electrolysis coupled with desalination in Saudi Arabia

Hydrogen, considered a crucial element in the transition towards a sustainable energy future, offers the potential to mitigate greenhouse gas (GHG) emissions and reduce reliance on fossil fuels. Here, this study explores the viability of hydrogen production using proton exchange membrane water electrolysis (PEMWE) as a key driver of decarbonization within the Vision 2030 framework in the Kingdom of Saudi Arabia. A first-of-a-kind life cycle assessment (LCA) of electrolytic hydrogen (e-hydrogen) production using PEMWE in the Kingdom is performed. As the hydrogen will be produced in a freshwater scarce region, the inclusion of water desalination processes adds an important dimension to the assessment, reflecting the local context and resource availability. Two main renewable energy scenarios are assessed: solar energy through photovoltaics (PV) and wind energy through onshore turbines. The global warming potential (GWP) results indicate a GHG emissions reduction of up to 95 % compared to the state-of-the-art steam methane reforming process if the electrolysis process is powered exclusively by renewable electricity. The scenarios powered by solar and wind energy result in 3.66 and 0.76 kg CO 2 eq/kg H 2 , respectively. The metal depletion is assessed to consider the requirement of rare materials, with a 7.19 × 10 −2 kg Cu eq/kg H 2 for the solar scenario and 2.82 × 10 −2 kg Cu eq/kg H 2 for the wind scenario. A contribution analysis reveals that the majority of emissions in both scenarios originate from the electricity used for electrolysis, with the electrolyser itself contributing minimally. The absolute impact of the water desalination process is the same in both scenarios; however, it appears more prominent in the wind-powered case due to the significantly lower overall emissions in that scenario. The findings underscore the importance of renewable energy integration and process optimization in minimizing environmental impacts and advancing the sustainability of e-hydrogen production.

08 HYDROGEN↗
DOE OSTI2021

Roles of retailers in the peer-to-peer electricity market: A single retailer perspective

Despite extensive research in the past five years and several successfully completed and on-going pilot projects, regulators are still reluctant to implement peer-to-peer trading at a large-scale in today’s electricity market. The reason could partly be attributed to the perceived disadvantage of current market participants like retailers due to their exclusion from market participation - a fundamental property of decentralized peer-to-peer trading. As a consequence, recently, there has been growing pressure from energy service providers in favor of retailers’ participation in peer-to-peer trading. However, the role of retailers in the peer-to peer market is yet to be established as no existing study has challenged this fundamental circumspection of decentralized trading. In this context, this perspective takes the first step to discuss the feasibility of retailers’ involvement in the peer-to-peer market. In doing so, we identify key characteristics of retail-based and peer-to-peer electricity markets and discuss our viewpoint on how to incorporate a single retailer in a peer-to-peer market without compromising the fundamental decision-making characteristics of both markets. Finally, we give an example of a hypothetical business model to demonstrate how a retailer can be a part of a peer-to-peer market with a promise of collective benefits for the participants.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2021

FtsZ-mediated fission of a cuboid bacterial symbiont

Less than a handful of cuboid and squared cells have been described in nature, which makes them a rarity. Here, we show how Candidatus Thiosymbion cuboideus, a cube-like gammaproteobacterium, reproduces on the surface of marine free-living nematodes. Immunostaining of symbiont cells with an anti-fimbriae antibody revealed that they are host-polarized, as these appendages exclusively localized at the host-proximal (animal-attached) pole. Moreover, by applying a fluorescently labeled metabolic probe to track new cell wall insertion in vivo, we observed that the host-attached pole started septation before the distal one. Similarly, Ca. T. cuboideus cells immunostained with an anti-FtsZ antibody revealed a proximal-to-distal localization pattern of this tubulin homolog. Although FtsZ has been shown to arrange into squares in synthetically remodeled cuboid cells, here we show that FtsZ may also mediate the division of naturally occurring ones. This implies that, even in natural settings, membrane roundness is not required for FtsZ function.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Biophysical analysis of the plant-specific GIPC sphingolipids reveals multiple modes of membrane regulation

The plant plasma membrane (PM) is an essential barrier between the cell and the external environment, controlling signal perception and transmission. It consists of an asymmetrical lipid bilayer made up of three different lipid classes: sphingolipids, sterols, and phospholipids. The glycosyl inositol phosphoryl ceramides (GIPCs), representing up to 40% of total sphingolipids, are assumed to be almost exclusively in the outer leaflet of the PM. However, their biological role and properties are poorly defined. In this study, we investigated the role of GIPCs in membrane organization. Because GIPCs are not commercially available, we developed a protocol to extract and isolate GIPC-enriched fractions from eudicots (cauliflower and tobacco) and monocots (leek and rice). Lipidomic analysis confirmed the presence of trihydroxylated long chain bases and 2-hydroxylated very long-chain fatty acids up to 26 carbon atoms. The glycan head groups of the GIPCs from monocots and dicots were analyzed by gas chromatograph-mass spectrometry, revealing different sugar moieties. Multiple biophysics tools, namely Langmuir monolayer, ζ-Potential, light scattering, neutron reflectivity, solid state 2H-NMR, and molecular modeling, were used to investigate the physical properties of the GIPCs, as well as their interaction with free and conjugated phytosterols. We showed that GIPCs increase the thickness and electronegativity of model membranes, interact differentially with the different phytosterols species, and regulate the gel-to-fluid phase transition during temperature variations. These results unveil the multiple roles played by GIPCs in the plant PM.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

A structural explanation for the mechanism and specificity of plant branching enzymes I and IIb

Branching enzymes (BEs) are essential in the biosynthesis of starch and glycogen and play critical roles in determining the fine structure of these polymers. The substrates of these BEs are long carbohydrate chains that interact with these enzymes via multiple binding sites on the enzyme’s surface. By controlling the branched-chain length distribution, BEs can mediate the physiological properties of starch and glycogen moieties; however, the mechanism and structural determinants of this specificity remain mysterious. In this study, we identify a large dodecaose binding surface on rice BE I (BEI) that reaches from the outside of the active site to the active site of the enzyme. Mutagenesis activity assays confirm the importance of this binding site in enzyme catalysis, from which we conclude that it is likely the acceptor chain binding site. Comparison of the structures of BE from Cyanothece and BE1 from rice allowed us to model the location of the donor-binding site. We also identified two loops that likely interact with the donor chain and whose sequences diverge between plant BE1, which tends to transfer longer chains, and BEIIb, which transfers exclusively much shorter chains. When the sequences of these loops were swapped with the BEIIb sequence, rice BE1 also became a short-chain transferring enzyme, demonstrating the key role these loops play in specificity. Taken together, these results provide a more complete picture of the structure, selectivity, and activity of BEs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Stabilization of glucose-6-phosphate dehydrogenase oligomers enhances catalytic activity and stability of clinical variants

Glucose-6-phosphate dehydrogenase (G6PD) deficiency is a genetic trait that can cause hemolytic anemia. To date, over 150 nonsynonymous mutations have been identified in G6PD, with pathogenic mutations clustering near the dimer and/or tetramer interface and the allosteric NADP + -binding site. Recently, our lab identified a small molecule that activates G6PD variants by stabilizing the allosteric NADP + and dimer complex, suggesting therapeutics that target these regions may improve structural defects. Here, we elucidated the connection between allosteric NADP + binding, oligomerization, and pathogenicity to determine whether oligomer stabilization can be used as a therapeutic strategy for G6PD deficiency (G6PD def ). We first solved the crystal structure for G6PD K403Q , a mutant that mimics the physiological acetylation of wild-type G6PD in erythrocytes and demonstrated that loss of allosteric NADP + binding induces conformational changes in the dimer. These structural changes prevent tetramerization, are unique to Class I variants (the most severe form of G6PD def ), and cause the deactivation and destabilization of G6PD. We also introduced nonnative cysteines at the oligomer interfaces and found that the tetramer complex is more catalytically active and stable than the dimer. Furthermore, stabilizing the dimer and tetramer improved protein stability in clinical variants, regardless of clinical classification, with tetramerization also improving the activity of G6PD K403Q and Class I variants. These findings were validated using enzyme activity and thermostability assays, analytical size-exclusion chromatography (SEC), and SEC coupled with small-angle X-ray scattering (SEC-SAXS). Taken together, our findings suggest a potential therapeutic strategy for G6PD def and provide a foundation for future drug discovery efforts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Expression, purification, and characterization of diacylated Lipo-YcjN from Escherichia coli

YcjN is a putative substrate binding protein expressed from a cluster of genes involved in carbohydrate import and metabolism in Escherichia coli. Here, we determine the crystal structure of YcjN to a resolution of 1.95 Å, revealing that its three-dimensional structure is similar to substrate binding proteins in subcluster D-I, which includes the well-characterized maltose binding protein. Furthermore, we found that recombinant overexpression of YcjN results in the formation of a lipidated form of YcjN that is posttranslationally diacylated at cysteine 21. Comparisons of size-exclusion chromatography profiles and dynamic light scattering measurements of lipidated and nonlipidated YcjN proteins suggest that lipidated YcjN aggregates in solution via its lipid moiety. Additionally, bioinformatic analysis indicates that YcjN-like proteins may exist in both Bacteria and Archaea, potentially in both lipidated and nonlipidated forms. Together, our results provide a better understanding of the aggregation properties of recombinantly expressed bacterial lipoproteins in solution and establish a foundation for future studies that aim to elucidate the role of these proteins in bacterial physiology.

Escherichia coli↗
DOE OSTI2025

Regulatory helix plays a key role in genetic ON-OFF switching for the 2’-deoxyguanosine sensing mRNA element

Transcriptional riboswitches, noncoding mRNA elements that operate in cis to regulate gene expression, have a promising potential in medicine, synthetic biology and directed evolution. They bind to cellular metabolites or metal ions with high specificity, leading to conformational rearrangements that facilitate the activation or premature termination of transcription for downstream genes. This elegant mechanism for feedback regulation of metabolic pathways has been identified in prokaryotes and a few in eukaryotes. Our chemical probing of the 2’-deoxyguanosine (2’-dG)-sensing riboswitch demonstrates that the overall conformational state of the full-length riboswitch (dGsw-fl) is unresponsive to the 2’-dG. Although binding proceeds as expected, dGsw-fl exclusively populates an OFF state of transcriptional inhibition. We chemically probed the structure of a known dGsw transcriptional intermediate (dGsw-int) to evaluate the possibility of a cotranscriptional regulatory role. Interestingly, apo dGsw-int adopts an alternative conformation in which a stable anti-terminator helix is formed, leading to an ON state where transcription can proceed. In the presence of 2’-dG, this anti-terminator helix is destabilized to produce a conformation reminiscent of the full-length, OFF-state dGsw. Using a fluorescence quenching assay, we demonstrate that binding 2’-dG to early transcriptional intermediates can inhibit the formation of the anti-terminator helix, locking dGsw in an OFF state. These data suggest that metabolite sensing occurs during a brief window of time between the synthesis of two transcriptional intermediates. Our studies indicate that dGsw does not function as a binary ON−OFF switch, but instead fine-tunes the transcription of downstream genes during RNA synthesis using key intermediates.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

The HypA and HypB metallochaperones from Methanococcus maripaludis have unique metal-binding properties and a distinct nickel transfer mechanism

[NiFe] hydrogenases are widespread microbial metalloenzymes that catalyze the reversible conversion of hydrogen (H2) to protons and electrons, playing key roles in energy metabolism. The biosynthesis of the NiFe(CN) 2 CO cofactor involves a suite of maturation proteins, including the HypA and HypB nickel metallochaperones. Here, we define the metal-binding properties, nucleotide-dependent behavior, and functional interplay of HypA and HypB from the hydrogenotrophic methanogenic archaeon, Methanococcus maripaludis . Methanogens have multiple essential nickel-dependent enzymes, so they require efficient systems for nickel delivery that remain largely unexplored. Purified M. maripaludis HypA binds zinc or mononuclear iron at the C-terminal metal binding site, the latter of which has not been reported in other HypA proteins and may serve a unique regulatory role in methanogens. The G-protein metallochaperone HypB binds nickel at the G-domain, which stimulates GTPase activity. Size exclusion chromatography experiments reveal that HypA and HypB form complexes in the presence of nickel, and zinc-bound HypA is optimized for nickel transfer from HypB. The identity of the nucleotide bound to HypB (GDP or GTP) alters the oligomeric state of HypA-HypB complexes, supporting a GTPase-mediated nickel delivery pathway. The HypA-HypB 2 complex configuration is enriched and stable in the presence of GDP and nickel, indicating that this complex delivers nickel to the hydrogenase as opposed to HypA alone. Interestingly, affinity purification-mass spectrometry revealed that HypB interacts with several nickel-dependent proteins, suggesting that HypB may play a broader role in nickel homeostasis in M. maripaludis . Together, this work establishes a biochemical framework for HypAB-mediated nickel trafficking in methanogens.

[NiFe] hydrogenase↗
DOE OSTI2026

Excipient screening by lyophilization provides insights into spray drying formulations for nanoparticle vaccines

Nanoparticles have shown great promise as delivery platforms in the development of tunable and safe vaccines. Nanolipoprotein particles (NLPs), also known as nanodiscs, are discoidal nanoparticles composed of a lipid bilayer stabilized at their periphery by apolipoproteins. Under the right conditions, the NLP self-assembly process is highly customizable in terms of lipids and apolipoprotein constituents, allowing for tunable physical and chemical characteristics. This flexibility allows a wide range of vaccine antigens and adjuvants to be incorporated onto the NLP platform for tailored vaccine design. The stability of NLPs during long term storage is a very important factor in developing a vaccine delivery platform suitable for widespread global use. When stored in a solution for extended periods of time, NLPs dissociate into their corresponding lipids and protein constituents, leading to particle degradation. Proper stabilization of NLPs can often be achieved by lyophilization (i.e. freeze-drying), a method widely used for various applications including pharmaceuticals. This process, however, can be damaging to particles without the presence of lyoprotectants or excipients that help maintain particle stability during lyophilization. Another method used to stabilize vaccines and pharmaceuticals is spray drying, a process that converts liquid formulations into dry powders through controlled heating and airflow. While spray drying is rapid, scalable, and cost-effective, lyophilization is typically a gentler process that better retains biomolecule structure and function. Both processes use excipients for particle stabilization, so lyophilization can be used as a surrogate to test stability of NLPs, to down-select formulations that may withstand the harsher conditions of spray drying. To screen different formulations, NLPs were synthesized and purified to homogeneity by size exclusion chromatography (SEC) and samples were prepared with a wide range of lyoprotectants and/or excipients. To assess the protective effects of excipients on NLPs upon spray drying, both pre- and post-lyophilized samples were analyzed by SEC. To assess the protective effects upon heating (encountered during the spray drying process), NLP samples were incubated at elevated temperatures prior to SEC analysis. The lyoprotectants and excipients evaluated in this study had different efficiencies in protecting NLPs during lyophilization and heating tests. Trehalose, for example, exhibits stabilization on NLPs both upon lyophilization and heating whereas leucine accelerated NLP dissociation. Although some lyoprotectants are effective by themselves, different combinations can decrease the stabilization of NLPs. Shelf-stable vaccines that do not require cold-chain storage are essential for global accessibility and our findings provide fundamental insight into how to advance NLP-based vaccines for these applications.

Serrano, Litzay J [Lawrence Livermore National Lab↗
DOE OSTI2022

Selective dehydra-decyclization of cyclic ethers to conjugated dienes over zirconia

ZrO 2 provides high selectivity (>90%) to conjugated pentadienes through the dehydra-decyclization of C-5 cyclic ethers, even at high conversions. 1,3-Pentadiene was the major product in both reaction of 2-methyltetrahydrofuran and tetrahydropyran over ZrO 2 . The reaction of 3-methyltetrahydrofuran produced nearly stoichiometric amounts of isoprene. Other catalysts, including TiO 2 , γ-Al 2 O 3 , and H-ZSM-5, were generally much less selective and produced a mixture of diene isomers. A combination of TPD and steady-state measurements revealed that both piperylenes are exclusively produced through primary catalytic pathways from 2-methyltetrahydrofuran, avoiding any isomerization once formed. First-principle calculations on ZrO 2 imply the presence of an energetically favored, surface isomerization of ring-opened intermediates to conjugated alkenolates that selectively dehydrate to conjugated dienes, providing high selectivity to the desired products. Finally, the stabilization of the conjugated alkenolate is key for understanding the ability of ZrO 2 to selectively produce conjugated dienes from cyclic ethers, without the need for the thermo-limited diene isomerization.

1,3 -pentadiene↗