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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.

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At least 181 records · Page 10

Rapid droplet introduction interface (RDII) for mass spectrometry

A system for the mass spectrometry analysis of an analyte includes a droplet ejection device, a spray head comprising a spray tip for ejecting the solvent as a spray, and a solvent delivery conduit for delivering solvent to the spray tip. The spray head includes a droplet inlet opening communicating with the surrounding atmosphere for receiving liquid droplets comprising the analyte. The droplet ejection device selectively ejects a liquid analyte droplet comprising the analyte through a surrounding atmosphere and the droplet inlet opening into a solvent flowing through the solvent delivery conduit. A method for the mass spectrometry analysis of an analyte is also disclosed.

Kertesz, Vilmos↗

Systems and methods lattice spray substrates for mass spectrometry

The present disclosure relates to a lattice substrate adapted for use in direct ionization mass spectrometry. The substrate may have a plurality of tessellated unit cells forming an integral structure. Each tessellated unit cell may have a dimension of no more than about 1.5 mm and may include a plurality of pores arranged in an ordered pattern. The substrate may further include a form factor suitable for use with a direct ionization mass spectrometry system.

Prieto Conaway, Maria C.↗

ISOCS-based Extended In Situ Gamma Spectrometry Services Tool SuperISOCS for Waste Measurements - 20275

Canberra's In Situ Object Counting System (ISOCS) is an established tool used for gamma spectrometry. It allows physical representation of complex geometries and mathematical calculation of the calibration function while avoiding the need for radioisotope standards. ISOCS provides a large range of templates to generate the geometry for most nuclear waste components in nuclear facilities. Nonetheless, there are some complex geometries where the accuracy attainable is limited by the conventional ISOCS templates. An ISOCS-based extended in-situ Gamma Spectrometry service tool has been developed, based on the so-called SuperISOCS (SISOCS) software. This tool was developed to generate the most complex geometries. The principle of geometry construction is based on the composition of 8 different primitive geometries. The primitive object is able to be cut and to change a part of an object. An object is able to overlap to another one to form a more complex object. These functions refine the modelled geometry compared to the real objects and decrease the measurement systematic error because they allow the mathematical model to represent the real-life geometry more faithfully through reducing the approximations and simplifications that need to be made The algorithm of SISOCS is the same as that of standard ISOCS. A set of calculations was done in comparison with MCNP efficiency calculation and SISOCS results. 80 different models were compared between SISOCS and MCNP, with added 30 cases compared between ISOCS and SISOCS. The average differences were less than 2%, for all energy's efficiency calculations. In this paper we illustrate the benefits that this new tool can provide, in terms of improved accuracy for complex realistic geometries, through simulation of some example scenarios. Furthermore, we demonstrate, through SISOCS modelling of the real object data test, the comparison between SISOCS to ISOCS calculations for the same geometry. This paper describes the added functions that are easily employed using SISOCS. Our results show the potential application and benefit of this technique for real waste assay projects and the way to integrate the tool into the waste assay systems. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Interlaboratory comparison of secondary ion mass spectrometry analysis results from the 7th international technical nuclear forensics working group collaborative material exercise

A review and interlaboratory comparison of secondary ion mass spectrometry (SIMS) data obtained by laboratories participating in the International Technical Nuclear Forensics Working Group (ITWG) 7th Collaborative Material Exercise (CMX-7) has been conducted. The analyzed materials were two uranium compounds in powder form and two pieces of uranium metal. The instruments used in this comparison were a small-geometry (SG) SIMS, CAMECA IMS 7f from the Research Centre Rez, and a large-geometry (LG) SIMS, CAMECA IMS 1280 from Los Alamos National Laboratory. Despite the differences in instruments and analytical procedures, e.g., sample preparation, SIMS setups, and data post-processing, there was good agreement for the 234 U/ 238 U, 235 U/ 238 U, and 236 U/ 238 U ratios in the analyzed materials. The main difference was in the precision, which was, as expected, higher for the LG-SIMS. In addition, a comparison between the laboratories was also made for the image processing algorithms applied to raw data acquired in automated particle measurement (APM) mode. In conclusion, the result of this comparison has led to identification of best practices for setting up parameters of the APM software.

and nuclear chemistry↗

Impact of phenanthrene co-administration on the toxicokinetics of benzo[a]pyrene in humans. UPLC-accelerator mass spectrometry following oral microdosing

Current risk assessments for environmental carcinogens rely on animal studies utilizing doses orders of magnitude higher than actual human exposures. Epidemiological studies of people with high exposures (e.g., occupational) are of value, but rely on uncertain exposure data. In addition, exposures are typically not to a single chemical but to mixtures, such as polycyclic aromatic hydrocarbons (PAHs). The extremely high sensitivity of accelerator mass spectrometry (AMS) allows for dosing humans with known carcinogens with de minimus risk. In this study UPLC-AMS was used to assess the toxicokinetics of [ 14 C]-benzo[a]pyrene ([ 14 C]-BaP) when dosed alone or in a binary mixture with phenanthrene (Phe). Plasma was collected for 48 h following a dose of [ 14 C]-BaP (50 ng, 5.4 nCi) or the same dose of [ 14 C]-BaP plus Phe (1250 ng). Following the binary mixture, C max of [ 14 C]-BaP significantly decreased (4.4-fold) whereas the volume of distribution (V d ) increased (2-fold). Further, the toxicokinetics of twelve [ 14 C]-BaP metabolites provided evidence of little change in the metabolite profile of [ 14 C]-BaP and the pattern was overall reduction consistent with reduced absorption (decrease in C max ). Although Phe was shown to be a competitive inhibitor of the major hepatic cytochrome P-450 (CYP) responsible for metabolism of [ 14 C]-BaP, CYP1A2, the high inhibition constant (K i ) and lack of any increase in unmetabolized [ 14 C]-BaP in plasma makes this mechanism unlikely to be responsible. Rather, co-administration of Phe reduces the absorption of [ 14 C]-BaP through a mechanism yet to be determined. Furthermore, this is the first study to provide evidence that, at actual environmental levels of exposure, the toxicokinetics of [ 14 C]-BaP in humans is markedly altered by the presence of a second PAH, Phe, a common component of environmental PAH mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exploring new frontiers in type 1 diabetes through advanced mass-spectrometry-based molecular measurements

Type 1 diabetes (T1D) is a devastating autoimmune disease for which advanced mass spectrometry (MS) methods are increasingly used to identify new biomarkers and better understand underlying mechanisms. For example, integration of MS analysis and machine learning has identified multimolecular biomarker panels. In mechanistic studies, MS has contributed to the discovery of neoepitopes, and pathways involved in disease development and identifying therapeutic targets. However, challenges remain in understanding the role of tissue microenvironments, spatial heterogeneity, and environmental factors in disease pathogenesis. Recent advancements in MS, such as ultra-fast ion-mobility separations, and single-cell and spatial omics, can play a central role in addressing these challenges. Here, in this work, we review recent advancements in MS-based molecular measurements and their role in understanding T1D.

60 APPLIED LIFE SCIENCES↗

In-field alpha spectrometry system for uranium enrichment verification of uranium hexafluoride

A portable In-Field Alpha Spectrometry (IFAS) system was developed to support on-site uranium enrichment determination for samples taken at facilities working with gaseous UF 6 . It consists of a modified commercial alpha spectrometer, a vacuum pump, a laptop computer, and associated connectors and cables. The IFAS uses specially designed Single-Use Destructive Assay (SUDA) samplers to capture gaseous UF 6 and convert and store it as UO 2 F 2 in a thin-film zeolite. To examine the quantitative performance of the IFAS system a large number of replicate SUDA samples was acquired for natural uranium (NU, 0.72 wt%, 23 samples), low enriched uranium 1 (LEU1, 2.33 wt% 235 U, 10 samples), and low enriched uranium 2 (LEU2, 4.62 wt% 235 U, 10 samples). The standard deviation (SD) values for uranium enrichment determination with the IFAS for NU, LEU1, and LEU2, in 20-hour assays, were 0.037 wt% 235 U, 0.063 wt% 235 U, and 0.072 wt% 235 U, respectively. In addition, a separate analysis suggests that comparable SD values can be achieved in less time, approximately 8-10 hours. For context, these SD values are well below the International Atomic Energy Agency’s International Target Values for the determination of uranium enrichment in non-destructive assay measurements.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Cyanobacterial Phycobilisome Allostery as Revealed by Quantitative Mass Spectrometry

Phycobilisomes (PBSs) are the major photosynthetic light-harvesting complexes in cyanobacteria and red algae. PBS, a multisubunit protein complex, has two major interfaces that comprise intrinsically disordered regions (IDRs): rod–core and core-membrane. IDRs do not form regular, three-dimensional structures on their own. Their presence in the photosynthetic pigment–protein complexes portends their structural and functional importance. A recent model suggests that PB-loop, an IDR located on the PBS subunit ApcE and C-terminal extension (CTE) of the PBS subunit ApcG, forms a structural protrusion on the PBS core-membrane side, facing the thylakoid membrane. Here, the structural synergy between the rod–core region and the core-membrane region was investigated using quantitative mass spectrometry (MS). The AlphaFold-predicted CpcG-CTE structure was first modeled onto the PBS rod–core region, guided and justified by the isotopically encoded structural MS data. Quantitative cross-linking MS analysis revealed that the structural proximity of the PB-loop in ApcE and ApcG-CTE is significantly disturbed in the absence of six PBS rods, which are attached to PBS via CpcG-CTE, indicative of drastic conformational changes and decreased structural integrity. Furthermore, these results suggest that CpcG-rod attachment on the PBS rod–core side is essentially required for the PBS core-membrane structural assembly. The hypothesized long-range synergy between the rod–core interface (where the orange carotenoid protein also functions) and the terminal energy emitter of PBS must have important regulatory roles in PBS core assembly, light-harvesting, and excitation energy transmission. These data also lend strategies that genetic truncation of the light-harvesting antennas aimed for improved photosynthetic productivity must rely on an in-depth understanding of their global structural integrity.

59 BASIC BIOLOGICAL SCIENCES↗

Comparability of Liquid Chromatography Tandem Mass Spectrometry Analysis of Dissolved Organic Matter across Laboratories

Non-targeted liquid chromatography tandem highresolution mass spectrometry (LC−MS/MS) is increasingly applied for the structure-resolved chemical analysis of dissolved organic matter (DOM). With new developments in MS instrumentation and analysis software, the approach has gained substantial momentum over the past decade. However, achieving high-quality analytical data that is reproducible and comparable across laboratories can be a bottleneck in non-targeted metabolomics and organic matter chemical analysis, especially for data reuse in repository-scale analyses. Understanding the capabilities as well as challenges of comparing LC−MS/MS data from different laboratories is necessary for inferring global trends from public data sets. To illuminate instrumentation factors that drive differences and variability, we used a standardized data analysis pipeline, including classical (CMN) and featurebased molecular networking (FBMN), to analyze data from a ring trial by 24 laboratories on identical sample sets of algal and DOM extracts that were mixed in predefined concentrations and spiked with standards. Our results showed that data sets from similar mass spectrometer types with unified instrument parameters were qualitatively comparable, resolving the same general trends and shared mass spectral features. Interlaboratory comparability was best for high-intensity features, while low-intensity features showed greater detection variability. Our analysis also highlights challenges when comparing data from instruments with different acquisition rates or operating with less standardized methods. Lastly, we provide recommendations for data integration, public data sharing, standardization, and best practices for standardized LC−MS/MS data acquisition, which will be critical for long-term time series and intercomparability of DOM chemical analyses.

DOM↗

A Preprocessing Tool for Enhanced Ion Mobility–Mass Spectrometry-Based Omics Workflows

The ability to improve the data quality of ion mobility–mass spectrometry (IM-MS) measurements is of great importance for enabling modular and efficient computational workflows and gaining better qualitative and quantitative insights from complex biological and environmental samples. We developed the PNNL PreProcessor, a standalone and user-friendly software housing various algorithmic implementations to generate new MS-files with enhanced signal quality and in the same instrument format. Different experimental approaches are supported for IM-MS based on Drift-Tube (DT) and Structures for Lossless Ion Manipulations (SLIM), including liquid chromatography (LC) and infusion analyses. The algorithms extend the dynamic range of the detection system, while reducing file sizes for faster and memory-efficient downstream processing. Specifically, multidimensional smoothing improves peak shapes of poorly defined low-abundance signals, and saturation repair reconstructs the intensity profile of high-abundance peaks from various analyte types. Further, other functionalities are data compression and interpolation, IM demultiplexing, noise filtering by low intensity threshold and spike removal, and exporting of acquisition metadata. Several advantages of the tool are illustrated, including an increase of 19.4% in lipid annotations and a two-times faster processing of LC-DT IM-MS data-independent acquisition spectra from a complex lipid extract of a standard human plasma sample. The software is freely available at https://omics.pnl.gov/software/pnnl-preprocessor.

59 BASIC BIOLOGICAL SCIENCES↗

mzPeak: Designing a Scalable, Interoperable, and Future-Ready Mass Spectrometry Data Format

Advances in mass spectrometry (MS) instrumentation, such as higher resolution, faster scan speeds, and improved sensitivity, have significantly increased the volume and complexity of data. The growing adoption of imaging and ion mobility further amplifies these challenges across MS-based omics fields, including proteomics, metabolomics, and lipidomics. While these technologies unlock new possibilities, they also present significant challenges in data management, storage, and accessibility. Existing open formats, such as the XML-based community standards mzML and imzML, struggle to meet the demands of modern MS workflows due to their large file sizes, slow data access, and limited metadata support. Vendor-specific formats, while optimized for proprietary instruments, lack interoperability, comprehensive metadata support and long-term archival reliability. This white paper lays the groundwork for mzPeak, a next-generation community data format designed to address these challenges and support high-throughput, multi-dimensional MS workflows. By adopting a hybrid model that combines efficient binary storage for numerical data and both human and machine-readable metadata storage, mzPeak will reduce file sizes, accelerate data access, and offer a scalable, adaptable solution for evolving MS technologies. For researchers, mzPeak will enable enhanced interoperability across platforms, seamless support for complex workflows including ion mobility and MS imaging, and faster data access compared to existing community formats such as mzML. Its design will ensure data is managed in compliance with regulatory standards, essential for applications such as precision medicine and chemical safety, where long-term data integrity and accessibility are critical. For vendors, mzPeak provides a streamlined, open alternative to proprietary formats, reducing the burden of regulatory compliance while aligning with the industry's push for transparency and standardization. By offering a high-performance, interoperable solution, mzPeak positions vendors to meet customer demands for sustainable data management tools which will be able to handle emerging and future data types and workflows. mzPeak aspires to become the cornerstone of MS data management, empowering researchers, vendors, and developers to innovate and collaborate more effectively.

data formats↗

Dynamic time-warping correction for shifts in ultrahigh resolving power ion mobility spectrometry and structures for lossless ion manipulations

Detection of arrival time shifts between ion mobility spectrometry (IMS) separations can limit achievable resolving power (Rp), particularly when multiple separations are summed or averaged, as commonly practiced. Such variations are more apparent in higher Rp measurements, and are particularly evident in long path length traveling wave structures for lossless ion manipulations (SLIM) IMS due to their typically much longer separation times. Here we explore the utility of a data processing approaches employing linear alignment (LA) and nonlinear dynamic time warping (DTW) of IMS separations to correct for variations between separations, such as due to pressure fluctuations. For multipass SLIM IMS separations, where narrow mobility range measurements have arrival times that can extend to several seconds, the LA approach effectively corrected for such variations, and significantly improvement Rp for summed separations. However, LA was much less effective for high Rp broad mobility range separations, such as obtained with multilevel SLIM IMS. Changes in IMS arrival times ions were observed to be correlated with small pressure changes, with approximately 0.6% relative arrival time shifts being common, sufficient to result in a loss of Rp for summed separations. Comparison of the approaches showed DTW alignment performed similarly to LA when used over a narrow mobility range, but was significantly better (providing narrower peaks and higher signal intensities) for wide mobility range data. We found the DTW approach increased Rp by as much as 115% for measurements in which 50 IMS separations over 2 seconds were summed, and leading to a large improvement in effective Rp. We conclude that DTW is superior to LA for ultrahigh resolution broad mobility range SLIM IMS separations, correcting for ion arrival time shifts regardless of the cause. Our tool is publicly available for use with universal ion mobility format (.UIMF) and text (.txt) files.

Data alignment, dynamic time warping, ion mobility↗

Improving Signal to Noise Ratios in Ion Mobility Spectrometry and Structures for Lossless Ion Manipulations (SLIM) using a High Dynamic Range Analog-to-Digital Converter

Signal digitization is a commonly overlooked part of ion mobility-mass spectrometry (IMS-MS) workflows, yet it is a significant contributor for determining signal-to-noise ratios and MS resolution. Here we report on the integration of a 2 GS/s, 14-bit ADC with a structures for lossless ion manipulations (SLIM)-IMS-MS and compare the performance to a commonly used 8-bit ADC. The 14-bit ADC provided an effective reduction in digitized noise by factor of ~6, owing largely to the use of smaller bit sizes. The low baseline allowed the threshold voltage levels to be set very close to the MCP baseline voltage, allowing for as much signal to be acquired as possible without causing overloading or excessive digitization of MCP baseline noise. Analyses of Agilent tuning mixture ions and a complex mixture of heavy labeled phosphopeptides showed that the 14-bit ADC (compared to the 8-bit ADC) provided a modest signal-to-noise increase (~1.5 to 2-fold) for high intensity ions, such as the Agilent tuning mixture ions and the 2+ and 3+ charge states of many phosphopeptide constituents. However, signal enhancements were as much as 10-fold for low intensity ions, and the 14-bit ADC enabled discernable signal intensities otherwise lost using an 8-bit digitizer. Additionally, the 14-bit ADC required ~14-fold fewer mass spectra to be averaged to produce a mass spectrum with similar S/N as the 8-bit ADC under identical conditions, potentially providing an order of magnitude higher measurement throughput. The high resolution, low baseline, and fast speed of the new 14-bit ADC enables high performance digitization of MS, IMS-MS, and SLIM-IMS-MS spectra, and allows a much fuller picture of analyte profiles in complex mixtures to be acquired.

data acquisition, digitization, ion mobility spect↗

Accelerating strain phenotyping with desorption electrospray ionization-imaging mass spectrometry and untargeted analysis of intact microbial colonies

Significance Synthetic biology has entered an era in which reading and writing DNA sequences are no longer rate-limiting steps in microbial strain engineering. Indeed, analytical methods measuring the resulting metabolic outcomes of specific gene edits have lagged behind the ability to generate new recombinant strains. Herein, we report a mass spectrometry strategy to accelerate these analytical workflows by directly analyzing metabolites and molecules produced from engineered microorganisms in a multiplexed process. Using untargeted acquisitions and unsupervised analytics, we assess the molecular features that change across discrete strains including primary target species, secondary products, and species outside the engineered fatty acid biosynthesis pathway.

09 BIOMASS FUELS↗

Atomistic simulations for investigation of substrate effects on lipid in-source fragmentation in secondary ion mass spectrometry

In beam-based ionization methods, the substrate plays an important role on the desorption mechanism of molecules from surfaces. Both the specific orientation that a molecule adopts at a surface and the strength of the molecule-surface interaction can greatly influence desorption processes, which in turn will affect the ion yield and the degree of in-source fragmentation of a molecule. In the beam-based method of secondary ion mass spectrometry (SIMS), in-source fragmentation can be significant and molecule specific due to the hard ionization method of using a primary ion beam for molecule desorption. To investigate the role of the substrate on orientation and in-source fragmentation, we have used atomistic simulations—molecular dynamics in combination with density functional theory calculations—to explore the desorption of a sphingolipid (palmitoylsphingomyelin) from a model surface (gold). We then compare SIMS data from this model system to our modeling findings. Using this approach, we found that the combined adsorption and binding energy of certain bonds associated with the headgroup fragments (C3H8N+, C5H12N+, C5H14NO+, and C5H15PNO4+) was a good predictor for fragment intensities (as indicated by relative ion yields). This is the first example where atomistic simulations have been applied in beam-based ionization of lipids, and it presents a new approach to study biointerfacial lipid ordering effects on SIMS imaging.

59 BASIC BIOLOGICAL SCIENCES↗

Understanding Biomass and Polymer Feedstock Variability Through Analytical Pyrolysis and Two Dimensional Gas Chromatography and Mass Spectrometry

Moving toward a circular carbon economy requires enabling reuse of carbon-based macromolecules like those in biomass and polymers. Meeting this goal requires increased upcycling of waste products into higher value products. For biomass waste such as corn stover, pine needles, or bark, one approach is using pyrolysis to convert these feedstocks into bio-oil that can be used for liquid fuel or transformed into other hydrocarbon based products, like bio-polymers. Waste plastics can be upcycled or recycled into new products, or alternatively converted into bio-oil by pyrolysis. Macromolecules from biomass and polymers are challenging to convert into liquid fuel or chemical feedstocks, due to large and sometimes heterogeneous networks of polymeric bonds. We work with the Idaho National Laboratory’s Biomass Feedstock National User Facility and Department of Energy’s Feedstock Conversion Interface Consortium to develop a molecular understanding of biomass variability that occurs naturally and as a result of storage or preprocessing techniques applied to feedstocks, to understand chemical reactions occurring during pyrolysis and other biomass or polymer conversion techniques. Using two dimensional gas chromatography mass spectrometry coupled to analytical pyrolysis provides insight into the molecular changes that occur during the pyrolysis event, and these insights can extend to bench or pilot scale pyrolysis conversions. Understanding pyrolysis of biomass and polymers at a molecular level contributes to development of new tools to predict and manipulate the optimum conditions and identify the best storage, preprocessing, and conversion techniques to maximize output of specific high-value chemical species in the conversion to fuels, or to characterize feedstocks for blending before pyrolysis. Identification and understanding of the molecular level changes resulting from novel preprocessing techniques that can be used to control and manipulate the chemical output of bench or pilot scale pyrolysis is another focus of investigation, including the use of gamma irradiation, acid, or enzyme pre-treatments. We also focus on the impacts of storage conditions and techniques, which can affect moisture levels, degradation, and impacts from naturally occurring microbes in the environment.

09 BIOMASS FUELS↗

From cytoplasm to lumen—mapping the free pools of protein subunits of three photosynthetic complexes using quantitative mass spectrometry

The phycobilisome (PBS) captures light energy and transfers it to photosystem I (PSI) and photosystem II (PSII). Which and how many copies of protein subunits in PBSs, PSI, and PSII remain unbound in thylakoids are unknown. Here, quantitative mass spectrometry (QMS) was used to quantify substantial pools of free extrinsic subunits of PSII and PSI. Interestingly, the membrane intrinsic PsaL is 3-fold higher than PsaA/B. This scenario complements the static structures of these complexes as revealed by X-ray crystallography and cryo-EM. Furthermore, the ratios of ApcG and photoprotective OCP over PBS indicate a pool of extra ApcG. The 2.5 ratio of CpcG-PBS over CpcL-PBS improves our understanding of these light-harvesting complexes involved in energy capture and photoprotection in cyanobacteria.

cyanobacteria↗

Secondary Ion Mass Spectrometry (SIMS) for Chemical Characterization of Metal Halide Perovskites

Metal halide perovskite (MHP) solar cells have attracted much attention due to the rapidly growing power conversion efficiency that has reached 25.2% in a decade, comparable to established commercial photovoltaic modules. Compositional engineering is one of the most effective methods to boost the performance of MHP solar cells. Further improving the efficiency and the stability of MHP solar cells necessitates good understanding of the chemical–efficiency correlation and the chemical evolution during the degradation of MHP solar cells. In this regard, time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a powerful tool to investigate the chemical aspect of MHPs and has played an important role in advancing the development of MHP optoelectronics. However, up to date, a review that can guide future utilization of ToF-SIMS in the MHP development is missing. In this paper, the capabilities of ToF-SIMS in MHP investigations are summarized and analyzed from simple material synthesis and chemical distribution to more complicated device operation mechanism and stability. The strength of ToF-SIMS in resolving important issues in this field, such as interface composition, ion migration, and degradation in MHP is highlighted. Finally, an outlook with an emphasis on making the utmost of ToF-SIMS in developing MHP devices is provided.

36 MATERIALS SCIENCE↗