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At least 415 records · Page 23

Tracking the first electron transfer step at the donor side of oxygen-evolving photosystem II by time-resolved infrared spectroscopy

In oxygen-evolving photosystem II (PSII), the multi-phasic electron transfer from a redox-active tyrosine residue (TyrZ) to a chlorophyll cation radical (P680 + ) precedes the water-oxidation chemistry of the S-state cycle of the Mn 4 Ca cluster. Here we investigate these early events, observable within about 10 ns to 10 ms after laser-flash excitation, by time-resolved single-frequency infrared (IR) spectroscopy in the spectral range of 1310–1890 cm -1 for oxygen-evolving PSII membrane particles from spinach. Comparing the IR difference spectra at 80 ns, 500 ns, and 10 µs allowed for the identification of quinone, P680 and TyrZ contributions. A broad electronic absorption band assignable P680 + was used to trace largely specifically the P680 + reduction kinetics. The experimental time resolution was taken into account in least-square fits of P680 + transients with a sum of four exponentials, revealing two nanosecond phases (30–46 ns and 690–1110 ns) and two microsecond phases (4.5–8.3 µs and 42 µs), which mostly exhibit a clear S-state dependence, in agreement with results obtained by other methods. Our investigation paves the road for further insight in the early events associated with TyrZ oxidation and their role in the preparing the PSII donor side for the subsequent water oxidation chemistry.

59 BASIC BIOLOGICAL SCIENCES↗

Ad Hoc File Systems for High-Performance Computing

Storage backends of parallel compute clusters are still based mostly on magnetic disks, while newer and faster storage technologies such as flash-based SSDs or non-volatile random access memory (NVRAM) are deployed within compute nodes. Including these new storage technologies into scientific workflows is unfortunately today a mostly manual task, and most scientists therefore do not take advantage of the faster storage media. One approach to systematically include nodelocal SSDs or NVRAMs into scientific workflows is to deploy ad hoc file systems over a set of compute nodes, which serve as temporary storage systems for single applications or longer-running campaigns. This paper presents results from the Dagstuhl Seminar 17202 “Challenges and Opportunities of User-Level File Systems for HPC” and discusses application scenarios as well as design strategies for ad hoc file systems using node-local storage media. The discussion includes open research questions, such as how to couple ad hoc file systems with the batch scheduling environment and how to schedule stage-in and stage-out processes of data between the storage backend and the ad hoc file systems. Also presented are strategies to build ad hoc file systems by using reusable components for networking and how to improve storage device compatibility. Various interfaces and semantics are presented, for example those used by the three ad hoc file systems BeeOND, GekkoFS, and BurstFS. Their presentation covers a range from file systems running in production to cutting-edge research focusing on reaching the performance limits of the underlying devices.

97 MATHEMATICS AND COMPUTING↗

Measurement of hybrid rocket solid fuel regression rate for a slab burner using deep learning

This study presents an imaging-based deep learning tool to measure the fuel regression rate in a 2D slab burner experiment for hybrid rocket fuels. The slab burner experiment is designed to verify mechanistic models of reacting boundary layer combustion in hybrid rockets by the measurement of fuel regression rates. A DSLR camera with a high intensity flash is used to capture images throughout the burn and the images are then used to find the fuel boundary to calculate the regression rate. A U-net convolutional neural network architecture is explored to segment the fuel from the experimental images. Here, a Monte-Carlo Dropout process is used to quantify the regression rate uncertainty produced from the network. The U-net computed regression rates are compared with values from other techniques from literature and show error less than 10%. An oxidizer flux dependency study is performed and shows the U-net predictions of regression rates are accurate and independent of the oxidizer flux, when the images in the training set are not over-saturated. Training with monochrome images is explored and is not successful at predicting the fuel regression rate from images with high noise. The network is superior at filtering out noise introduced by soot, pitting, and wax deposition on the chamber glass as well as the flame when compared to traditional image processing techniques, such as threshold binary conversion and spatial filtering. U-net consistently provides low error image segmentations to allow accurate computation of the regression rate of the fuel.

42 ENGINEERING↗

Review of thermophysical property methods applied to fueled and un-fueled molten salts

Recent investigation into designs of molten salt reactors (MSR) requires accurate data of candidate salts. Review of the literature shows lacking thermophysical (TP) property data for coolants and fuel-bearing salts of Advanced High Temperature Reactors (AHTR). Measurement uncertainties of current data are even more deficient, and this affects ongoing research where MSR modeling and testing are being performed. Melting temperature, viscosity, density, specific heat capacity, and thermal and electrical conductivity measurements are often not arranged together or discussed in great detail, especially for fuel-bearing salts. Raw data from key findings spanning over 70 years for LiF, LiF-BeF 2 , LiF-NaF-KF, KCl-MgCl 2 , KF-ZrF 4 , and NaF-KF-MgF 2 have been organized and presented here. Brief description of methods used to obtain these results, in addition to the TP data of some of these salts as fuel carriers, has also been discussed. Thermal conductivity data are particularly weak due to older, high-error measurement techniques. More recent measurement systems to evaluate salt thermal conductivity show promise for obtaining consistent absolute values. This work concludes that measurement systems such as transient hot-wire method, forced Rayleigh scattering, and laser flash analysis provide the most promise to fill these data gaps and reduce current uncertainty in thermal conductivity measurements of both fueled and un-fueled molten salts.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Theoretical analysis of a refrigerant injection-enhanced air source heat pump with thermal energy storage for extended cold-climate and defrosting operations

This study investigates a conceptual refrigerant injection-enhanced air source heat pump with integrated thermal energy storage (ITES-ASHP) that combines two-phase flash tank injection with phase change material (PCM) thermal energy storage (TES) to extend cold-climate operation and maintain indoor heating during defrost. A steady-state, mode-based thermodynamic cycle model is developed to evaluate heating and defrosting modes with and without refrigerant injection and TES integration over an outdoor temperature range of 8 to −25 °C. The framework is applied to refrigerants R-290, R-454B, R-410 A, and R-32. A parametric study is conducted for an 18-kW system rated for an outdoor temperature of 8 °C, with the compressor frequency scheduled to 150 Hz. The optimal PCM phase-change temperature is identified as 20 °C for R-290, R-454B, and R-410 A, and 15 °C for R-32. At the design condition of −25 °C outdoor temperature, the proposed concept achieves a combined COP of 2.22 for R-290, corresponding to a 60% increase relative to the theoretical single-stage baseline for combined heating and defrosting operation. Safety screening based on compressor discharge temperature (≤ 120 °C) and injection quality (≥ 0.65), together with performance evaluation, indicates that R-290 is the most suitable candidate, followed by R-410 A and R-454B. Under the assumptions and constraints used here, R-32 is found to be less suitable due to excessive discharge temperatures and a higher risk of wet compression.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Conformational space exploration of cryo-EM structures by variability refinement

Cryo-EM observation of biological samples enables visualization of sample heterogeneity, in the form of discrete states that are separable, or continuous heterogeneity as a result of local protein motion before flash freezing. Variability analysis of this continuous heterogeneity describes the variance between a particle stack and a volume, and results in a map series describing the various steps undertaken by the sample in the particle stack. While this observation is absolutely stunning, it is very hard to pinpoint structural details to elements of the maps. Here, in order to bridge the gap between observation and explanation, we designed a tool that refines an ensemble of structures into all the maps from variability analysis. Using this bundle of structures, it is easy to spot variable parts of the structure, as well as the parts that are not moving. Comparison with molecular dynamics simulations highlights the fact that the movements follow the same directions, albeit with different amplitudes. Ligand can also be investigated using this method. Variability refinement is available in the Phenix software suite, accessible under the program name phenix.varref.

59 BASIC BIOLOGICAL SCIENCES↗

Nanoparticle-mediated antagonism of sustained endosomal signaling of the calcitonin receptor-like receptor provides enhanced and persistent relief of oral cancer pain

By improving the delivery and tumor retention of chemotherapeutics, nanomedicines hold potential for cancer treatment. The usefulness of nanoparticle (NP)-encapsulated analgesics for the cancer pain treatment is comparatively unexplored. We investigated whether NPs encapsulating olcegepant (OCP), an antagonist of the calcitonin receptor-like receptor (CLR) for the calcitonin gene-related peptide (CGRP), effectively relieved oral cancer pain in mice. Because persistent endosomal CLR signaling in Schwann cells mediates craniofacial pain, we reasoned that the predisposition of NPs to accumulate in endosomes could be leveraged to effectively relieve oral cancer pain. By expressing biosensors for activated CLR, Gα proteins and β-arrestins in HEK293T and Schwann cells, we found that CGRP activates CLR signaling first at the plasma membrane and then in early, late and recycling endosomes and the cis- and trans-Golgi apparatus. We synthesized biocompatible NPs encapsulating OCP and fluorophores by integrating hydrophobic ion pairing nanoformulation with Flash NanoPrecipitation. NPs slowly released OCP and accumulated in early endosomes, leading to sustained inhibition of endosomal CLR signaling in HEK293T and Schwann cells. Oral cancers were established in mice, which led to heightened pain-like responses. After intra-tumoral injection, NPs were retained in tumors for at least one week. OCP-loaded NPs almost completely reversed allodynia and hyperalgesia for a prolonged period, whereas unencapsulated OCP had small and transient effects. The NP accumulation in endosomal sites of pain signaling, the sustained release of antagonist, and the retention of NPs in tumors explain their beneficial actions. Thus, NP-encapsulation holds promise for the relief of painful cancers that are inadequately treated by opioids.

Calcitonin gene-related peptide↗

Early age hydration behavior of portland cement-based binders incorporating fly ash contaminated with flue gas desulfurization products

Fly ash co-mingled with flue gas desulfurization (FGD) products are currently discarded as off-specification materials based on their high SO3 content. However, previous studies have shown that performance of these fly ashes varies significantly based on FGD product type and as such they may be viable for use in low-CO2 concrete as supplementary cementitious materials (SCMs). In this study, fly ashes with three different types of FGD products including calcium sulfite hemihydrate, calcium sulfate (with some unreacted lime), and sodium sulfate (with some unreacted sodium carbonate) were evaluated. The early age hydration behavior in blended cementitious systems at 20% cement replacement level was studied using Vicat setting time tests, isothermal calorimetry, in-situ quantitative X-ray diffraction, and pore solution analysis. The cause of the setting time retardation and flash setting observed in fly ashes with calcium sulfite hemihydrate and sodium carbonate, respectively, were identified and suitable beneficiation options were suggested for the valorized use of these materials in low-CO 2 concrete.

36 MATERIALS SCIENCE↗

Fabrication, oxidation, and combustion of nanoscale magnesium diboride and tetraboride

The difficult ignition and low combustion efficiency of boron particles decrease the performance of boron-loaded, fuel-rich propellants for solid fuel ramjets and ducted rockets. One approach to solving this problem involves the use of magnesium diboride (MgB 2 ), which ignites easier than boron. Magnesium tetraboride (MgB 4 ) offers greater energy density owing to its higher boron content. However, the effect of B/Mg ratio on the ignition and combustion is unknown. Additionally, while nanoscale MgB₂ particles and quasi-2D structures are promising energetic additives, the oxidation and combustion properties of nanoscale MgB₄ have not been explored. To address these knowledge gaps, the present work included synthesis and high-energy ball milling of MgB 2 and MgB 4 powders, thermogravimetric analysis (TGA) of their oxidation, and combustion experiments with thin layers of the obtained powders. Comparison of two synthesis routes (a solid-state reaction in a tube furnace and combustion synthesis) has shown that the former is the superior method for producing magnesium borides. TGA has revealed that oxidation of both MgB 2 and MgB 4 results in a high conversion into the oxides (88–91 %), far exceeding the low conversion of boron (62.5 %). MgB 4 begins to oxidize rapidly at a much lower temperature (∼900 °C) than MgB 2 (∼1200 °C). The burning rates of milled MgB 2 and MgB 4 are about eight and five times, respectively, faster than that of submicron boron. Magnesium borides exhibit a stable, sustained boron flame, needed for high combustion efficiency, whereas physical Mg/B mixtures undergo Mg-driven "flash" combustion.

Boron↗

Flow visualisation in real-size optical injectors of conventional, additised, and renewable gasoline blends

Research on renewable and alternative fuels is crucial for improving the energy and environmental efficiency of modern gasoline internal combustion engines. To highlight the influence of fuel rheological and thermodynamic properties on phase change and atomisation processes, three types of gasoline blends were tested. More specifically, the campaign comprised a reference gasoline, an ethanol/gasoline blend (10% v/v) representative of renewable fuels, and an additised gasoline sample treated with viscoelasticity-inducing agents. High-speed imaging of the transient two-phase flow field arising in the internal geometry and the near-nozzle spray region of gasoline injectors was performed employing Diffuse Backlight Illumination. The metallic body of a commercial injector was modified to fit transparent tips realising two nozzle layouts, namely a two-hole real size model resembling the Engine Combustion Network spray G injector and an enraged replica with an offset hole. Experiments were conducted at realistic operating conditions comprising an injection pressure of 100 bar and ambient pressures in the range of 0.1–6.0 bar to cover the entire range of chamber pressures prevailing in Gasoline Direct Injection engines. The action of viscoelastic additives was verified to have a suppressive effect on in-nozzle cavitation (6% reduction in cavitation extent) , while also enhancing spray atomisation at flash-boing conditions, in a manner resembling the more volatile gasoline/ethanol blends. Finally, persisting liquid ligaments were found to form after the end of injection for the additised sample, owing to the surfactant nature of the additives.

30 DIRECT ENERGY CONVERSION↗

Enhanced energy conversion efficiency promoted by cavitation in gasoline direct injection

High-pressure direct fuel injection plays the most crucial role in energy conversion and improving engine combustion efficiency and emission. The optimization of turbulent and multiphase fuel injection has focused on controlling hydrodynamic parameters such as injection pressure. While the thermodynamic influence is often considered in the flash boiling situation, we inquire into how gasoline-type fuel’s hydro- and thermodynamic properties impact the injection dynamics by fuel-temperature induced cavitation. The turbulent and cavitating flows emanating from the direct-injection nozzle is visualized by ultrafast x-ray imaging with an unprecedented spatiotemporal resolution. The ultrafast liquid-fuel dynamics are dominated by injection pressure as well as fuel temperature through cavitation, an important thermodynamic parameter but often difficult to control in engine combustion. With the most direct and quantitative measurement, we discovered that the near-nozzle fuel-jet dynamics can be perfectly scaled by a single dimensionless parameter, cavitation number, particularly sensitive to the fuel temperature, in a wide operation range. This universal scaling shows that cavitation can be harnessed to elevate the pneumatic-hydraulic to kinetic energy conversion efficiency, critical for promoting fuel atomization and engine combustion performance. This enhancement effect will have even more impact on engine combustion using alternative low-emission fuels with higher saturated vapor pressure.

30 DIRECT ENERGY CONVERSION↗

A model for droplet heating and evaporation of water-in-oil emulsified fuel

Water-in-oil (W/O) emulsified fuel is a promising alternative fuel by inducing flash boiling of water at high temperature that can improve the atomization of fuel spray. The heating and evaporation process of emulsified fuel droplet is affected by the diffusion and coalescence of small dispersed water droplets in oil during the heating. In this study, a model is developed for the droplet heating and evaporation of W/O emulsified fuel with these key physics considered. The diffusivity of dispersed water droplets in oil is calculated using the Stokes-Einstein equation. The deactivation temperature of surfactant is selected as a criterion for the water coalescence since the water coalescence is due to the deactivation of surfactant. The process of water coalescence is simplified that the dispersed water droplets coalesce into one single water sub-droplet at the center of the oil droplet instantly as the droplet temperature reaches the deactivation temperature of surfactant. The model is validated against experimental data of single droplet under different heating temperatures, surfactant concentrations, and sizes of dispersed water droplets. Based on the proposed model, the effects of fuel properties and heating conditions on the droplet heating and evaporation are analyzed.

Droplet coalescence↗

A systematic method for selecting molecular descriptors as features when training models for predicting physiochemical properties

Machine learning has proven to be a powerful tool for accelerating biofuel development. Although numerous models are available to predict a range of properties using chemical descriptors, there is a trade-off between interpretability and performance. Neural networks provide predictive models with high accuracy at the expense of some interpretability, while simpler models such as linear regression often lack in accuracy. In addition to model architecture, feature selection is also critical for developing interpretable and accurate predictive models. We present a method for systematically selecting molecular descriptor features and developing interpretable machine learning models without sacrificing accuracy. Our method simplifies the process of selecting features by reducing feature multicollinearity and enables discoveries of new relationships between global properties and molecular descriptors. To demonstrate our approach, we developed models for predicting melting point, boiling point, flash point, yield sooting index, and net heat of combustion with the help of the Tree-based Pipeline Optimization Tool (TPOT). For training, we used publicly available experimental data for up to 8351 molecules. Our models accurately predict various molecular properties for organic molecules (mean absolute percent error (MAPE) ranges from 3.3% to 10.5%) and provide a set of features that are well-correlated to the property. This method enables researchers to explore sets of features that significantly contribute to the prediction of the property, offering new scientific insights. To help accelerate early stage biofuel research and development, we also integrated the data and models into a open-source, interactive web tool.

09 BIOMASS FUELS↗

Blended fuel property analysis of butyl-exchanged polyoxymethylene ethers as renewable diesel blendstocks

Methyl-terminated polyoxymethylene ethers (MM-POMEs), having the formula CH 3 O-(CH 2 O)n-CH 3 (n = 3-6), are a class of oxygenates with desirable diesel-like fuel properties including high cetane number and low soot formation. However, their low energy density and high water-solubility present barriers to their adoption. Both concerns were recently addressed by our research group by synthesizing a mixture of POME structures having butyl end-groups and n = 1-6, termed B*POME1-6. B*POME1-6 maintained the advantageous properties of the parent MM-POMEs, and exhibited improved energy density and most notably, dramatically decreased water solubility. For evaluation against a set of criteria for a blended diesel blendstock, a 20 vol% blend of B*POME1-6 with a base diesel fuel was investigated here. Oxidation stability, cetane number, sooting tendency, lubricity and conductivity were improved in the B*POME1-6 blend compared with the base diesel, while also maintaining the flash point, cloud point, energy density, viscosity, and boiling point requirements. The B*POME1-6 product demonstrated a synergistic blending behavior at 10 vol% and a linear blending behavior at 20-30 vol% blends, in agreement with similar POME blends at comparable blend levels. Finally, common environmental and toxicity models performed on B*POME1-6 component molecules suggested they have a greater propensity to partition into the water compartment compared to a common diesel surrogate, but with a lower tendency to bioaccumulate.

33 ADVANCED PROPULSION SYSTEMS↗

A structured framework for predicting sustainable aviation fuel properties using liquid-phase FTIR and machine learning

Sustainable aviation fuels have the potential to improve efficiency, reduce emissions, and enhance energy security. To help identify viable sustainable aviation fuels and accelerate research, machine learning models have been developed to predict relevant physicochemical properties. However, many models have limited applicability, leverage data from complex analytical techniques with confined spectral ranges, or use feature decomposition methods that offer limited interpretability. Using liquid-phase Fourier Transform Infrared (FTIR) spectra, this study presents a structured method for creating accurate and interpretable property prediction models for neat molecules, aviation fuels, and blends. Liquid FTIR spectra can be collected quickly and consistently, offering high reliability, sensitivity, and component specificity using less than 2 ml of sample. The method first decomposes FTIR spectra into fundamental building blocks using non-negative matrix factorization (NMF) to enable scientific analysis of FTIR spectra attributes and fuel properties. The NMF features are then used to create five ensemble models for predicting final boiling point, flash point, freezing point, density at 15°C, and kinematic viscosity at -20°C. All models were trained using experimental property data from neat molecules, aviation fuels, and blends. The models accurately predict key properties across a broad range of neat molecules and representative fuels and blends, while enabling interpretation of relationships between compositional elements, such as functional groups or chemical classes, and their resulting properties. This demonstrates strong potential to support sustainable aviation fuel research and development. The models and data are available on an interactive web tool.

Fourier transform infrared spectroscopy↗

Levelized Cost of CO 2 Captured Using Five Physical Solvents in Pre-combustion Applications

Aspen Plus v8.8 was used to perform techno-economic analysis (TEA) of a CO 2 capture process from a typical fuel gas stream in a 543-MW pre-combustion power plant using five different physical solvents (Selexol, PEGPDMS-1, NMP, [aPy][Tf 2 N] and [hmim][Tf 2 N]). The process included a countercurrent packed-bed absorber operating under high-pressure over a wide range of temperatures and three pressure-swing flash drums for solvent regeneration. Furthermore, two packings, Mellapak 250Y and IMTP50, were used and the Levelized costs of CO 2 captured (LCOC) were calculated. The simulation results indicated that using Mellapak 250Y exhibited lower LCOC values than those when using IMTP50 for the five solvents under all conditions used as it offered better mass transfer. The CO 2 capture process carried out at low temperatures showed lower LCOC values than those at higher temperatures due to the increased CO 2 solubility in the solvents at lower temperatures, requiring smaller absorber diameter and lower solvent circulation rates, which offset the cooling requirements. Comparing the lowest LCOC values for the five solvents, the hydrophobic PEGPDMS-1 solvent was the most promising one compared to the other four solvents, due to its lowest capital and operating costs and noncorrosive, which enabled using less expensive materials for the process equipment.

42 ENGINEERING↗

A unified non-equilibrium phase change model for injection flow modeling

The homogenous relaxation model (HRM) is one of the most widely used models to describe the liquid- gas phase transition. However, in its original formulation, it is unable to handle multispecies vapor-liquid equilibrium (VLE), which limits its applicability to single-component fluids. In this work, a unified non-equilibrium phase change model that considers the VLE of multicomponent mixtures is proposed building upon the HRM's structure. A time factor is introduced to mimic the effect of different phase change timescales due to different mechanisms, e.g., cavitation, flash-boiling, and evaporation. Here to assess the model's performance, computational fluid dynamics simulations of the internal and near-nozzle injection flow of the Engine Combustion Network's Spray G injector were performed using the nine-component PACE-20 fuel with both the unified model and the original HRM. The predicted fuel density in the near-nozzle region matched well with X-ray tomography measurements. The simulation results indicated that, whereas the HRM failed to capture the vaporization due to convective mixing between the fuel and ambient gas, the unified model performed well in predicting the mixing-driven vaporization and the corresponding evaporative cooling. Further comparisons using the nine-component fuel formula and a single-component fuel surrogate demonstrated the unified model's ability to predict preferential vaporization, which affects the predictions of local mixture composition and rate of vaporization. Finally, it is shown that the unified model is capable of representing multiple phase change mechanisms, and the relaxation time factor plays an important role in determining the degree of phase change due to the different mechanisms.

33 ADVANCED PROPULSION SYSTEMS↗

Thermal conductivity measurement using modulated photothermal radiometry for nitrate and chloride molten salts

Molten salts are being used or explored for thermal energy storage and conversion systems in concentrating solar power and nuclear power plants. Thermal conductivity of molten salts is an important thermophysical property dictating the performance and cost of these systems, but its accurate measurement has been challenging, as evidenced by wide scattering of existing data in literature. The corrosive and conducting nature of these fluids also leads to time consuming sample preparation processes of many contact-based measurements. Here, in this work, we report the measurement of thermal conductivity of molten salts using a modulated photothermal radiometry (MPR) technique, which is a laser-based, non-contact, frequency-domain method adopted for molten salts for the first time. By unitizing the advantages of front side sensing of frequency-domain measurements and the vertical holder orientation, the technique can minimize the natural convection and salt creeping effects, thus yielding accurate molten salt thermal conductivity . The MPR technique is first calibrated using standard molten materials including paraffin wax and sulfur. It is then applied on measuring pure nitrate salts (NaNO 3 and KNO 3 ), solar salt (NaNO 3 –KNO 3 mixture), and chloride salt (NaCl–KCl–MgCl 2 ). The measurement results are compared with data from literature, especially those obtained from laser flash analysis (LFA). Our results demonstrate that the MPR is a convenient and reliable technique of measuring thermal conductivity of molten salts. Accurate thermal conductivity data of molten salts will be valuable in developing the next-generation high-temperature thermal energy storage and conversion systems.

14 SOLAR ENERGY↗