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At least 307 records · Page 17

Ultrasensitive microanalytical diagnostic methods for rickettsial pathogens

A strategic CRADA was established between Sandia National Laboratories (SNL) and the University of Texas Medical Branch (UTMB) at Galveston to address pressing needs for US protection against biological weapons of mass destruction (WMD) and emerging infectious diseases. The combination of unique expertise and facilities at UTMB and SNL enabled interdisciplinary research efforts in the development of rapid and accurate diagnostic methods for early detection of trace priority pathogen levels. Outstanding postdoctoral students were also trained at both institutions to help enable the next generation of scientists to tackle the challenging interdisciplinary problems in the area of biodefense and emerging infectious diseases. Novel approaches to diagnostics were developed and the both the speed of assays as well as the detection sensitivity were improved by over an order of magnitude compared to traditional methods. This is a significant step toward more timely and specific detection of dangerous infections. We developed in situ polymerized porous polymer monoliths that can be used as (1) size exclusion elements for capture and processing of rickettsial infected cells from a sample, (2) photopatternable framework for grafting high densities of functionalized antibodies/fluorescent particles using novel monolith chemistry. Grafting affinity reagents specific to rickettsial particles enables rapid, ultra-sensitive assays by overcoming transport limitations of traditional planar assay approaches. We have selectively trapped particles and bacteria at the cell trap and have also detected picomolar mouse IL-6 captured with only 20 minutes total incubation times using the densely patterned monolith framework. As predicted, the monolith exhibits >10x improvements in both capture speed and capture density compared to traditional planar approaches. The most significant advancements as part of this CRADA is the optimization of techniques allowing the detection of <10 rickettsial cells in a whole blood sample. This detection limit is over 2 orders of magnitude more sensitive that previously reported methods and overcomes a key hurdle in ability to sense dangerous infections before they are too late to treat and contain. We also showed that in the new format, cross-reactivity with interfering species is reduced thereby increasing the specificity of such tests. Promising options to treat whole blood and avoid clogging and non-specific fouling of sensors were also developed.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Superheater Corrosion Produced By Biomass Fuels

About 90% of the world's bioenergy is produced by burning renewable biomass fuels. Low-cost biomass fuels such as agricultural wastes typically contain more alkali metals and chlorine than conventional fuels. Although the efficiency of a boiler's steam cycle can be increased by raising its maximum steam temperature, alkali metals and chlorine released in biofuel boilers cause accelerated corrosion and fouling at high superheater steam temperatures. Most alloys that resist high temperature corrosion protect themselves with a surface layer of Cr{sub 2}O{sub 3}. However, this Cr{sub 2}O{sub 3} can be fluxed away by reactions that form alkali chromates or volatilized as chromic acid. This paper reviews recent research on superheater corrosion mechanisms and superheater alloy performance in biomass boilers firing black liquor, biomass fuels, blends of biomass with fossil fuels and municipal waste.

09 BIOMASS FUELS↗

Novel Materials for cell Studies and harvesting

Controlling cell growth on different surfaces is crucial for many applications. For instance after surgery, unspecific adhesion on exogenous materials can lead to fouling that may result in infections. On the other hand, fast attachment of tissue cells is pivotal for the healing process. Hence, specific regulation of cell adhesion to substrates is a significant task especially in the biomedical field. It has long been known that surface conditions like topology/roughness, wettability, charge, etc. are major factors in cell adhesion on various synthetic materials including Polytetrafluoroethylene, titanium or silicone. However, the literature is sparse on studies of cell growth on medical relevant substrates. We investigated the growth of different cells types on polyelectrolyte (PE) multilayers with and without lipid bilayers deposited and could observe confluence and multiplication of cells on both substrate types. Our neutron reflectometry studies of lipid bilayers deposited on polyelectrolyte multilayer demonstrates that the size of the water gap between the lipid bilayer and the PE covered substrate can be influenced by the environmental conditions, e.g. the pH of the surrounding medium. In principal, this 'floating' of a lipid bilayer can also be applied for growing monolayer of cells and detaching them by an environmental change. Such a fabrication would simplify cell growing and harvesting for various medical application, e.g. tissue engineering. Our approach for the fabrication of cellular monolayers that are easy to detach and transfer, creating free-floating sheets of cells also enables us to study those structures more conveniently and under in-situ conditions using neutron scattering.

36 MATERIALS SCIENCE↗

Management of HL deposits for the D and D of UP1 reprocessing plant - retrieval and treatment scenarios - 15295

Built in 1958 on the Marcoule CEA site, the UP1 facility, was the 1. French industrial (500 t U / year) reprocessing plant based on the PUREX process. The plant, which has stopped operation in 1997, constitutes with its auxiliary workshop (vitrification workshop, glass canister storage), one of the largest and most challenging decommissioning project in France. In about 40 years of operation, various type of fuels elements such as metallic uranium, U-Al fuel rods, Phenix breeder elements or PWR fuel have been reprocessed, thereby requiring several plant and process adaptations. Resulting from these complex process chemistry and operation history, significant fouling of the chemical plant circuits and components has occurred. The fission product (FP) concentration process is particularly concerned. Preliminary investigation performed in 2010 in the evaporator's feeding tanks revealed the presence of significant amounts of sludge and dose rates as high as 250 Gy/h. Therefore a thorough investigation campaign, including visual inspection, volume quantification, deposits sampling, and radiological characterization of the components of this workshop has been initiated in 2013. Chemical analysis performed so far show that the solids are mainly composed of zirconium phosphates, 'MoZr' compounds and nitrate salt precipitates. But the presence of insoluble fines arising from the dissolution workshop and organic residues resulting from the TBP decomposition has also been evidenced in some of the tanks. The numerous constraints associated with the management of such highly active sludge, with Cs-137 specific activity ranging from 1 to 10 GBq/g, and a complex physico-chemical composition, lead CEA to investigate the implementation of an in situ conditioning treatment able to produce a waste package complying with existing evacuation routes and/or on-site storage facilities. The full paper presents an overview of the UP1 D and D project and then focuses on the possible dismantling scenarios for the FP concentration workshop, including the evaluation of different strategies for the highly active deposits management. The investigations and deposits characterization program will be developed so as the sampling methodologies that has been specifically tuned. In the light of the best actual knowledge of the deposits properties, the recovery and conditioning treatment scenarios will be exposed, considering, as a case study, the development of a specific vitrification tool to be implemented In Situ and specifically designed to match the requirements and constraints of the D and D project: adequately dimensioned, compact, flexible with respect to the feed composition, for a limited duration of use and designed to be dismantled. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Simultaneous “Clean-and-Repair” of Surfaces Using Smart Droplets

An autonomous self-healing system, inspired by transportation processes inherent to biology, is described for materials transportation and repair. The selected model system combines inorganic nanoparticles (NPs) on damaged substrates with functional emulsion droplets that pick up the particles from pristine portions of the substrate and deposit them into damaged regions. The droplets are stabilized by polymer surfactants containing phosphorylcholine groups, a polymer composition selected to impart surfactant properties for droplet stabilization as well as fouling resistance to prevent irreversible droplet adsorption on the substrates. Both the NP pickup (cleaning) and drop off (repair) steps are conducted in a system driven by an imposed flow and characterized by fluorescence microscopy. To evaluate and optimize the efficiency of this NP transportation process, the effect of both the chemical composition of the polymer surfactant and the NP surface chemistry is investigated in this work. Interfacial interactions proved enabling for these NP transportation processes, specifically those involving NP/droplet, NP/substrate, and droplet/substrate interactions. Ultimately, droplets capable of both picking up and dropping off NPs are realized by adjusting fluid/fluid and fluid/substrate interactions, with electrostatic interactions between NPs and droplets proving most effective.

36 MATERIALS SCIENCE↗

Direct Chemical Vapor Deposition Synthesis of Porous Single-Layer Graphene Membranes with High Gas Permeances and Selectivities

Single-layer graphene containing molecular-sized in-plane pores is regarded as a promising membrane material for high-performance gas separations due to its atomic thickness and low gas transport resistance. However, typical etching-based pore generation methods cannot decouple pore nucleation and pore growth, resulting in a trade-off between high areal pore density and high selectivity. In contrast, intrinsic pores in graphene formed during chemical vapor deposition are not created by etching. Therefore, intrinsically porous graphene can exhibit high pore density while maintaining its gas selectivity. Here in this work, the density of intrinsic graphene pores is systematically controlled for the first time, while appropriate pore sizes for gas sieving are precisely maintained. As a result, single-layer graphene membranes with the highest H 2 /CH 4 separation performances recorded to date (H 2 permeance > 4000 GPU and H 2 /CH 4 selectivity > 2000) are fabricated by manipulating growth temperature, precursor concentration, and non-covalent decoration of the graphene surface. Moreover, it is identified that nanoscale molecular fouling of the graphene surface during gas separation where graphene pores are partially blocked by hydrocarbon contaminants under experimental conditions, controls both selectivity and temperature dependent permeance. Overall, the direct synthesis of porous single-layer graphene exploits its tremendous potential as high-performance gas-sieving membranes.

chemical vapor deposition↗

Engineering In Situ Catalytic Cleaning Membrane Via Prebiotic-Chemistry-Inspired Mineralization

Pressure-driven membrane separation promises a sustainable energy-water nexus but is hindered by ubiquitous fouling. Natural systems evolved from prebiotic chemistry offer a glimpse of creative solutions. Herein, a prebiotic-chemistry-inspired aminomalononitrile (AMN)/Mn 2+ -mediated mineralization method is reported for universally engineering a superhydrophilic hierarchical MnO 2 nanocoating to endow hydrophobic polymeric membranes with exceptional catalytic cleaning ability. Green hydrogen peroxide catalytically triggered in-situ cleaning of the mineralized membrane and enabled operando flux recovery to reach 99.8%. The mineralized membrane exhibited a 9-fold higher recovery compared to the unmineralized membrane, which is attributed to active catalytic antifouling coupled with passive hydration antifouling. Electron density differences derived from the precursor interaction during mediated mineralization unveiled an electron-rich bell-like structure with an inner electron-deficient Mn core. This work paves the way to construct multifunctional engineered materials for energy-efficient water treatment as well as for diverse promising applications in catalysis, solar steam generation, biomedicine, and beyond.

36 MATERIALS SCIENCE↗

Molecular and Topographical Organization: Influence on Cicada Wing Wettability and Bactericidal Properties

Numerous natural surfaces have micro/nanostructures that result in extraordinary functionality, such as superhydrophobicity, self-cleaning, antifogging, and antimicrobial properties. One such example is the cicada wing, where differences in nanopillar geometry and composition among species can impact and influence the degree of exhibited properties. To understand the relationships between surface topography and chemical composition with multifunctionality, the wing properties of Neotibicen pruinosus (superhydrophobic) and Magicicada cassinii (hydrophobic) cicadas are investigated at time points after microwave-assisted extraction of surface molecules to characterize the chemical contribution to nanopillar functionality. Electron microscopy of the wings throughout the extraction process illustrates nanoscale topographical changes, while concomitant changes in hydrophobicity, bacterial fouling, and bactericidal properties are also measured. Extract analysis reveals the major components of the nanostructures to be fatty acids and saturated hydrocarbons ranging from C17 to C44. Effects on the antimicrobial character of a wing surface with respect to the extracted chemicals suggest that the molecular composition of the nanopillars plays both a direct and an indirect role in concert with nanopillar geometry. The data presented not only correlates the nanopillar molecular organization to macroscale functional properties, but it also presents design guidelines to consider during the replication of natural nanostructures onto engineered substrates to induce desired properties.

59 BASIC BIOLOGICAL SCIENCES↗

CO2 Hydrogenation to Hydrocarbons over Fe/BZY Catalysts

This manuscript reports a CO2 hydrogenation process in a catalytic laboratory-scale packed-bed reactor using an Fe/BZY15 (BaZr0.8Y0.15O3-d) catalyst to form hydrocarbons (e.g., CH4, C2+) at elevated pressure of 30 bar and temperatures in the range 270 = T = 375 degrees C. The effects of temperature, feed composition (i.e., CO2/H2 ratio, and residence time (i.e., Weight Hourly Space Velocity (WHSV) are studied to understand the relationship between CO2 conversion and carbon selectivity. Catalyst characterization elucidates the relationships between the catalyst structure, surface adsorbates, and reaction pathways. Thermodynamic analyses guide the experimental conditions and assist interpreting results. While the feed composition and temperature influence the product distribution, the results suggest that the higher-carbon (C2+) selectivity and yield depend strongly on residence time. The results suggest that the CO2 hydrogenation reaction pathway is similar to Fischer-Tropsch (FT) synthesis. The reaction begins with CO2 activation to form CO, followed by chain-growth reactions similar to the FT process. The CO2 activation depends on the redox activity of the catalyst. However, the carbon chain growth depends primarily on the residence time. as is the case for the FT synthesis, high residence time (on the orders of hours) is required to achieve high C2+ yield. For such high residence times, catalyst-fouling carbon deposition can be problematic. The coke-resistant BZY15 catalyst support contributes to the catalytic activity and enables a coke-free operation for more than 100 h time-on-stream.

bi-functional catalyst↗

Influence of Linker Group on Bipolar Redox-Active Molecule Performance in Non-Aqueous Redox Flow Batteries

Redox flow batteries (RFBs) are an attractive choice for stationary energy storage of renewables such as solar and wind. Non-aqueous redox flow batteries (NARFBs) have garnered broad interest due to their high voltage operation compared to their aqueous counterparts. Further, the utilization of bipolar redox-active molecules (BRMs) is a practical way to alleviate crossover faced by asymmetric RFBs. In this work, ferrocene (Fc) and phthalimide (PI) are covalently linked with various tethering groups which vary in structure and length. The compiled results suggest that the length and steric shielding ability of the linker group can greatly influence the stability and overall performance of Fc-n-PI BRM-based NARFBs. Primary sources of capacity loss are found to be BRM degradation for straight chain spacers <6 carbons and membrane (Nafion) fouling. Fc-hexyl-PI provided the most stable battery cycling and coulombic efficiencies of >98 % over 100 cycles (~13 days). NARFB using Fc-hexyl-PI as an active material exhibited high working voltage (1.93 V) and maximum capacity (1.28 Ah L -1 ). Additionally, this work highlights rational strategies to improve cycling stability and optimize NARFB performance.

25 ENERGY STORAGE↗

Adaptable SEC‐SAXS data collection for higher quality structure analysis in solution

Abstract The two major challenges in synchrotron size‐exclusion chromatography coupled in‐line with small‐angle x‐ray scattering (SEC‐SAXS) experiments are the overlapping peaks in the elution profile and the fouling of radiation‐damaged materials on the walls of the sample cell. In recent years, many post‐experimental analyses techniques have been developed and applied to extract scattering profiles from these problematic SEC‐SAXS data. Here, we present three modes of data collection at the BioSAXS Beamline 4–2 of the Stanford Synchrotron Radiation Lightsource (SSRL BL4‐2). The first mode, the High‐Resolution mode, enables SEC‐SAXS data collection with excellent sample separation and virtually no additional peak broadening from the UHPLC UV detector to the x‐ray position by taking advantage of the low system dispersion of the UHPLC. The small bed volume of the analytical SEC column minimizes sample dilution in the column and facilitates data collection at higher sample concentrations with excellent sample economy equal to or even less than that of the conventional equilibrium SAXS method. Radiation damage problems during SEC‐SAXS data collection are evaded by additional cleaning of the sample cell after buffer data collection and avoidance of unnecessary exposures through the use of the x‐ray shutter control options, allowing sample data collection with a clean sample cell. Therefore, accurate background subtraction can be performed at a level equivalent to the conventional equilibrium SAXS method without requiring baseline correction, thereby leading to more reliable downstream structural analysis and quicker access to new science. The two other data collection modes, the High‐Throughput mode and the Co‐Flow mode, add agility to the planning and execution of experiments to efficiently achieve the user's scientific objectives at the SSRL BL4‐2.

Matsui, Tsutomu↗

Electrochemical Reduction Selectivity of Crotonaldehyde on Copper

Lignocellulosic waste is a potential feedstock for the generation of fuels and commodity chemicals, but existing conversion methods are too cost-intensive to be viable long-term solutions. Electrochemical reductions are promising for decentralized biomass valorization due to their modular scaling and capacity to run intermittently and without high temperatures or pressures. Using crotonaldehyde as a multi-functional model compound for the many partially unsaturated oxygenates found in processed biomass, we here demonstrate the production of butanal, butanol, butene, and butane (variously useful as commodity chemicals and major components of liquified petroleum gas) under ambient conditions by reductive bulk electrolysis with a copper mesh working electrode. We identify an optimum potential for reduced organic production under the reaction conditions and compare product distributions from reductions of intermediate species to further propose branching reaction pathways. Though butanal is typically the most abundant product from crotonaldehyde reduction, most of the butene and butane appear to result from a pathway involving initial reduction of the aldehyde group. We discuss evidence that selectivity is driven by interplay between crotonaldehyde reduction, local pH shifts due to the hydrogen evolution reaction, and changes in site reactivity and availability due to electrode fouling. This demonstration of model electrochemical biomass valorization also serves to inform further exploration into reduction of multi-functional molecules and electrochemical biomass processing in general.

biomass↗

Additively manufactured polymer composites for heat exchanger applications: evaluation of critical thermophysical properties

Polymeric heat exchangers (PHXs) have been used in applications involving weight restrictions, chemical compatibility, and fouling issues. Additive manufacturing (AM) or 3D printing provide new solutions to previously inaccessible combinations of properties and geometries. There are some advancements in the PHXs by AM; however, the process and the properties of materials still need further investigation to improve the overall performance. In this study, additively manufactured polyethylene terephthalate glycol (PETG) composites reinforced with graphite and pitch-based carbon fibers were evaluated for their potential application as PHXs. The thermal conductivity, volumetric heat capacity, coefficient of thermal expansion, creep behavior, and long-term performance were studied in detail. Our results reveal that the composites have an anisotropic thermal conductivity. The thermal conductivity along the printing direction is higher than the layer building direction due to the shear-induced alignment of the fillers. The printed composites achieve good thermal stability with 80% lower CTE at room temperature than neat PETG. Creep tests suggest the creep and creep recovery were highly temperature-dependent, and the deformation can be recovered when the temperature is below glass transition. These results suggest additive manufactured composites be potentially used for heat exchanger applications at low temperatures.

36 MATERIALS SCIENCE↗

Characterization of Deactivated Bio-oil Hydrotreating Catalysts

Deactivation of bio-oil hydrotreating catalysts remains a significant challenge because of the poor quality of pyrolysis bio-oil input for hydrotreating and understanding their deactivation mode is critical to developing improved catalysts and processes. In this research, we developed an understanding of the deactivation of two-step bio-oil hydrotreating catalysts (sulfided Ru/C and sulfided CoMo/C) through detailed characterization of the catalysts using various complimentary analytical techniques. Severe fouling of both catalysts by carbonaceous species was the major form of deactivation, which is consistent with the significant loss of surface area and pore volume of both deactivated catalysts and the significant increase of the bulk density. Further analysis of the carbonaceous species by thermogravimetric analysis and x-ray photoelectron spectroscopy indicated that the carbonaceous species was formed by condensation reaction of active species such as sugars and sugar derivatives (aldehydes and ketones) in bio-oil feedstock during bio-oil hydrotreating under the conditions and catalysts used. Microscopy results did not show metal sintering of the Ru/C catalyst. However, X-ray diffraction indicated a probable transformation of the highly-active CoMoS phase in the sulfided CoMo/C catalyst to Co8S9 and MoS2 phase with low activity. Loss of the active site by transport of inorganic elements from the bio-oil and the reactor construction material onto the catalyst surface also might be a cause of deactivation as indicated by elemental analysis of spent catalysts.

bio-oil hydrotreating↗

Non-contact electrochemical evaluation of biofilms

Abstract Here, we demonstrate a non-contact technique for electrochemical evaluation of biofilms on surfaces in relation to corrosion. Electrochemical impedance spectrometry was employed, incorporating flat patterned electrodes positioned over the surfaces of aluminum and glass with and without biofilms. Signal communication from the working electrode to the counter electrode followed electric field lines passing tangentially through the biofilms. Electrochemical impedance parameters that were evaluated included complex impedance, phase angle, imaginary (out of phase) conductivity and Cole–Cole plots with a corresponding equivalent circuit. Changes in the impedance properties due to the presence of biofilms were monitored and correlated through microbiological, chemical and electrochemical assays. Impedance parameters associated with microbial activity correlated with biofilms on aluminum and glass surfaces. This technical approach provides impedance information about the biofilm without the signal traveling through the underlying conductive media or disrupting the biofilm. In this way, biological contributions to surface fouling can be evaluated with minimal contribution from the inorganic surface under the biofilm. In addition, this technique can be used to monitor biofilms on electrochemically inert surfaces as well as electrically conductive surfaces. Graphic abstract

Turick, Charles E. (ORCID:0000000307815846)↗

Catalytic Conversion of Model Compounds of Plastic Pyrolysis Oil over ZSM-5

Mechanistic investigation of the catalytic conversion of model compounds for plastic pyrolysis oil (1-octene, octadiene, octane, and toluene) over ZSM-5 in a fixed-bed reactor was studied. 1-Octene breaks down into smaller olefins, which undergo further cracking, oligomerization, cyclization, and hydrogen transfer to eventually produce benzene, toluene, xylene (BTX), coke, and hydrogen. The effect of contact time on 1-octene conversion was further investigated and compared with thermodynamics analyses to elucidate the reaction network. Under the reaction conditions (500 oC, 1 atm), octadiene undergoes thermal coking, significantly contributing to reactor fouling. The products from octane cracking are similar to the products from 1-octene conversion whereas toluene undergoes disproportionation, dealkylation and coking. The analysis of spent catalyst showed long-chain hydrocarbons created by oligomerization reactions filled the pores and covered the surface of the catalyst. As a result, when mesoporous ZSM-5 is used instead of conventional, product selectivity is maintained for 70 hours in time-on-stream experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A critical review of electrochemical heat pump technologies: Status, challenges, and perspectives

The development of advanced heat pump technologies is critical for reducing global energy consumption in the building sector, where space heating and cooling account for nearly 50% of energy use. Electrochemical heat pumps (EHPs) offer a promising alternative to vapor compression systems by enabling direct electrochemical-to-thermal energy conversion, often with environmentally benign working fluids that exhibit low or zero global warming potential (GWP). Prior literature has predominantly focused on chemically reactive heat pumps, while comprehensive assessments of electrochemical mechanisms remain limited. Here, this review addresses this gap by systematically evaluating the underlying principles, architectures, and performance metrics of EHP systems. Compared to conventional vapor compression systems, EHPs can achieve 10%-30% higher energy efficiency, with reported cooling coefficients of performance (COP c ) ranging from 3.5 to 14.3 under standard operating conditions. Despite these advantages, widespread adoption is hindered by challenges including membrane degradation, electrode fouling, sluggish redox kinetics, and elevated system-level capital costs. To address these limitations, the review outlines three research priorities: (i) the development of advanced membranes, catalysts, and electrode materials with enhanced chemical and mechanical stability; (ii) the application of molecular-level simulations for the rational design of high-performance redox-active working fluids; and (iii) the integration of advanced diagnostic techniques for real-time monitoring and sustained operation of EHPs. By consolidating recent advances and explicitly identifying technological and scientific gaps, this work uniquely contributes a comprehensive framework for guiding future electrochemical heat pump research and facilitating the transition to sustainable thermal management technologies.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Toward understanding barnacle cementing by characterization of one cement protein-100kDa in Amphibalanus amphitrite

Barnacles, as major fouling organisms, have attracted more attentions. It is no doubt that the study on cement proteins is required to illustrate the mechanism of barnacle cementing. A cement protein defined as Aa-cp100k was characterized from Amphibalanus amphitrite in this study. The amino acid sequence of Aa-cp100k was shown a high similarity to other three barnacles including Megabalanus rosa (Mr-cp100k), Tetraclita japonica formosana (Tj-cp100k) and Pollicipes pollicipes (Pp-cp100k). Moreover, the localization of Aa-cp100k in the vacuoles of cyprid β secretory cells and the adult cement gland cells by immunofluorescence microscopy, indicating that Aa-cp100k existed in both cyprid and adult barnacle. Aa-cp100k from basal plate could be dissolved in urea buffer without high concentration of dithiothreitol (DTT), different from that in Megabalanus rosa, implying diverse possible roles of cp100k in cementing.

60 APPLIED LIFE SCIENCES↗