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At least 55 records · Page 3

Highly Ordered Eutectic Mesostructures via Template‐Directed Solidification within Thermally Engineered Templates

Template-directed self-assembly of solidifying eutectics results in emergence of unique microstructures due to diffusion constraints and thermal gradients imposed by the template. Here, the importance of selecting the template material based on its conductivity to control heat transfer between the template and the solidifying eutectic, and thus the thermal gradients near the solidification front, is demonstrated. Simulations elucidate the relationship between the thermal properties of the eutectic and template and the resultant microstructure. The overarching finding is that templates with low thermal conductivities are generally advantageous for forming highly organized microstructures. When electrochemically porosified silicon pillars (thermal conductivity < 0.3 Wm −1 K −1 ) are used as the template into which an AgCl-KCl eutectic is solidified, 99% of the unit cells in the solidified structure exhibit the same pattern. In contrast, when higher thermal conductivity crystalline silicon pillars (≈100 Wm −1 K −1 ) are utilized, the expected pattern is only present in 50% of the unit cells. The thermally engineered template results in mesostructures with tunable optical properties and reflectances nearly identical to the simulated reflectances of perfect structures, indicating highly ordered patterns are formed over large areas. This work highlights the importance of controlling heat flows in template-directed self-assembly of eutectics.

36 MATERIALS SCIENCE↗

STEM Analysis of Caenorhabditis elegans muscle thick filaments: evidence for microdifferentiated substructures

In the thick filaments of body muscle in Caenorhabditis elegans, myosin A and myosin B isoforms and a subpopulation of paramyosin, a homologue of myosin heavy chain rods, are organized about a tubular core. As determined by scanning transmission electron microscopy, the thick filaments show a continuous decrease in mass-per-length (MPL) from their central zones to their polar regions. This is consistent with previously reported morphological studies and suggests that both their content and structural organization are microdifferentiated as a function of position. The cores are composed of a second distinct subpopulation of paramyosin in association with the alpha, beta, and gamma-filagenins. MPL measurements suggest that cores are formed from seven subfilaments containing four strands of paramyosin molecules, rather than the two originally proposed. The periodic locations of the filagenins within different regions and the presence of a central zone where myosin A is located, implies that the cores are also microdifferentiated with respect to molecular content and structure. This differentiation may result from a novel "induced strain" assembly mechanism based upon the interaction of the filagenins, paramyosin and myosin A. The cores may then serve as "differentiated templates" for the assembly of myosin B and paramyosin in the tapering, microdifferentiated polar regions of the thick filaments.

NASA Discipline Musculoskeletal↗

Raspberry colloid-templated approach for the synthesis of palladium-based oxidation catalysts with enhanced hydrothermal stability and low-temperature activity

It is becoming increasingly urgent to develop and utilize novel, more efficient and stable materials for mobile and stationary emission control applications as the deleterious consequences of anthropogenic air pollution are becoming more evident and pressing. Tightening regulations, particularly related to automotive exhaust treatment, together with continued improvements in engine design, that result in lowering the engine operating temperatures and inadvertently lead to the release of an overwhelming proportion of pollutants during the cold start, present new challenges for materials design, specifically for oxidation catalysts. In particular, improvements in the low-temperature activity while maintaining catalyst stability at high temperatures are required from the next-generation catalyst. Typical catalysts for removal of pollutants from automotive exhaust streams incorporate platinum group metals (PGMs). They tend to be inefficient at low temperatures (below 250 °C), thus accounting for the cold start problem, yet sinter and lose their activity at high temperatures that are frequently encountered during catalyst operation. High PGM loadings are often employed to compensate for catalyst inefficiencies and fast degradation, ultimately resulting in high-cost catalytic converters. Here, we have developed a new approach for the design and formation of catalytic materials that allows for both significantly more efficient PGM incorporation and improved overall catalyst performance at reduced PGM loadings. The method provides control over the composition and geometry of the support through self-assembly of sacrificial composite template — “raspberry” polymeric colloids decorated with catalytic particles — accompanied by infiltration with metal-oxide precursor and subsequent removal of the colloids. This method simultaneously structures the porous network and organizes the catalytic particles within it. Uniquely, the resulting catalytic particles are partially embedded in the support matrix and partially exposed to the pore interior, producing catalytic sites that are both stable and accessible. Herein, the feasibility of this novel and versatile approach for automotive catalytic conversion is demonstrated: the studies include testing alumina-based raspberry-colloid-templated (RCT) catalysts containing Pd nanoparticles (RCT Pd/Al2O3) for oxidation of propane and carbon monoxide under simulated diesel exhaust conditions and hydrothermal aging at 800 °C for 50 h in the simulated stream. The RCT Pd/Al2O3 catalysts exhibit exceptional activity toward CO oxidation, reduced reaction onset temperature, and high stability to elevated temperatures (demonstrated through prolonged exposure to temperatures up to 950 °C) and reactive gas streams, without migration, sintering or loss of the precious metal NPs. Notably, the novel catalyst shows the same or slightly better performance than the commercial catalysts even when the PGM load is reduced by ~80 % compared to the commercial counterparts. These results provide confidence for the utilization of the RCT approach for the fabrication of robust nanostructured catalysts for next-generation, energy-efficient catalytic converters with improved performance at low and high temperatures and reduced costs. The RCT methodology is, in addition, highly generalizable, and can thus be applied for the design of a wide range of catalytic systems in the automotive sector and beyond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Differential assembly of alpha- and gamma-filagenins into thick filaments in Caenorhabditis elegans

Muscle thick filaments are highly organized supramolecular assemblies of myosin and associated proteins with lengths, diameters and flexural rigidities characteristic of their source. The cores of body wall muscle thick filaments of the nematode Caenorhabditis elegans are tubular structures of paramyosin sub-filaments coupled by filagenins and have been proposed to serve as templates for the assembly of native thick filaments. We have characterized alpha- and gamma-filagenins, two novel proteins of the cores with calculated molecular masses of 30,043 and 19,601 and isoelectric points of 10.52 and 11.49, respectively. Western blot and immunoelectron microscopy using affinity-purified antibodies confirmed that the two proteins are core components. Immunoelectron microscopy of the cores revealed that they assemble with different periodicities. Immunofluorescence microscopy showed that alpha-filagenin is localized in the medial regions of the A-bands of body wall muscle cells whereas gamma-filagenin is localized in the flanking regions, and that alpha-filagenin is expressed in 1.5-twofold embryos while gamma-filagenin becomes detectable only in late vermiform embryos. The expression of both proteins continues throughout later stages of development. C. elegans body wall muscle thick filaments of these developmental stages have distinct lengths. Our results suggest that the differential assembly of alpha- and gamma-filagenins into thick filaments of distinct lengths may be developmentally regulated.

NASA Discipline Musculoskeletal↗

Nonenzymatic, template-directed ligation of oligoribonucleotides is highly regioselective for the formation of 3'-5' phosphodiester bonds

We have found that nonenzymatic, template-directed ligation reactions of oligoribonucleotides display high selectivity for the formation of 3'-5' rather than 2'-5' phosphodiester bonds. Formation of the 3'-5'-linked product is favored regardless of the metal ion catalyst or the leaving group, and for several different ligation junction sequences. The degree of selectivity depends on the leaving group: the ratio of 3'-5'- to 2'-5'-linked products was 10-15:1 when the 5'-phosphate was activated as the imidazolide, and 60-80:1 when the 5'-phosphate was activated by the formation of a 5'-triphosphate. Comparison of oligonucleotide ligation reactions with previously characterized single nucleotide primer extension reactions suggests that the strong preference for 3'-5'-linkages in oligonucleotide ligation is primarily due to occurence of ligation within the context of an extended Watston-Crick duplex. The ability of RNA to correctly self-assemble by template-directed ligation is an intrinsic consequence of its chemical structure and need not be imposed by an external catalyst (i.e., an enzyme polymerase); RNA therefore provides a reasonable structural basis for a self-replicating system in a prebiological world.

Non-NASA Center↗

High-strength, lightweight nano-architected silica

Continuous nanolattices are an emerging class of mechanical metamaterials that are highly attractive due to their superior strength-to-weight ratios, which originate from their spatial architectures and nanoscale-sized elements possessing near-theoretical strength. Rational design of frameworks remains challenging below 50 nm because of limited methods to arrange small elements into complex architectures. Here, we fabricate silica frameworks with ~4- to 20-nm-thick elements using self-assembly and silica templating of DNA origami nanolattices and perform in situ micro-compression testing to examine the mechanical properties. We observe strong effects of lattice dimensions on yield strength (σ $\mathcal{y}$ ) and failure mode. Silica nanolattices are found to exhibit yield strengths higher than those of any known engineering materials with similar mass density. The robust coordination of the nanothin and strong silica elements leads to the combination of lightweight and high-strength framework materials offering an effective strategy for the fabrication of nanoarchitected materials with superior mechanical properties.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Biomimetic mineralization of positively charged silica nanoparticles templated by thermoresponsive protein micelles: applications to electrostatic assembly of hierarchical and composite superstructures

High information content building blocks offer a path toward the construction of precision materials by supporting the organization and reconfiguration of organic and inorganic components through engineered functions. Here, we combine thermoresponsiveness with biomimetic mineralization by fusing the Car9 silica-binding dodecapeptide to the C-terminus of the (VPGVG) 54 elastin-like polypeptide (ELP). Using small angle X-ray scattering, we show that the short Car9 cationic block is sufficient to promote the conversion of disordered unimers into 30 nm micelles comprising about 150 proteins, 5 °C above the transition temperature of the ELP. While both species catalyze self-limiting silica precipitation, micelles template the mineralization of highly monodisperse (62 nm) nanoparticles, while unimers yield larger polydisperse species. Strikingly, and unlike traditional synthetic silica, these particles exhibit a positive surface charge, likely due to cationic Car9 sidechains projecting from their surface. Capitalizing on the high monodispersity and positive charge of the micelle-templated products, we use smaller silica and gold particles bearing a native negative charge to create a variety of superstructures via electrostatic co-assembly. Furthermore, this simple biomimetic route to positively charged silica eliminates the need for multiple precursors or surface modifications and enables the rapid creation of single-material and composite architectures in which components of different sizes or compositions are well dispersed and integrated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Virus‐Based Pyroelectricity

Abstract The first observation of heat‐induced electrical potential generation on a virus and its detection through pyroelectricity are presented. Specifically, the authors investigate the pyroelectric properties of the M13 phage, which possesses inherent dipole structures derived from the noncentrosymmetric arrangement of the major coat protein (pVIII) with an α‐helical conformation. Unidirectional polarization of the phage is achieved through genetic engineering of the tail protein (pIII) and template‐assisted self‐assembly techniques. By modifying the pVIII proteins with varying numbers of glutamate residues, the structure‐dependent tunable pyroelectric properties of the phage are explored. The most polarized phage exhibits a pyroelectric coefficient of 0.13 µC m −2 °C −1 . Computational modeling and circular dichroism (CD) spectroscopy analysis confirm that the unfolding of α‐helices within the pVIII proteins leads to changes in phage polarization upon heating. Moreover, the phage is genetically modified to enable its pyroelectric function in diverse chemical environments. This phage‐based approach not only provides valuable insights into bio‐pyroelectricity but also opens up new opportunities for the detection of various viral particles. Furthermore, it holds great potential for the development of novel biomaterials for future applications in biosensors and bioelectric materials.

Kim, Han↗

Tailoring Nanoporous Silica and Natural Straw Structural Insulation Composites

Nanoporous silica exhibits ultralow thermal conductivity as a result of its nanoscale pore size, high pore volume, and specific surface area. In this study, we report the self-assembled surfactant-templated synthesis of nanoporous silica, which is integrated with cellulose fibers derived from natural straw to manufacture high thermal insulation and mechanically robust nanocomposites. The nanocomposite shows a low thermal conductivity of 22.5 mW/(m·K), a compressive modulus of 0.93 MPa, and a hydrophobicity with a water contact angle of 125°. Moreover, we observed a marked reduction in water absorption capacity and a carbon footprint of 0.21 kg CO 2 equiv/kg. Here, this study provides a pathway toward the development of nanoporous structural insulation materials for energy-efficient building applications.

36 MATERIALS SCIENCE↗

Structural Changes during the Conversion Reaction of Tungsten Oxide Electrodes with Tailored, Mesoscale Porosity

In-plane tungsten oxide nanostructures, including hexagonally patterned cylinders and holes in a matrix, were fabricated via sequential infiltration synthesis (SIS) on self-assembled block copolymer templates. Using the tailored morphology and porosity of these model electrodes with in situ grazing incidence small angle X-ray scattering, the intrinsic structural change of nanoscale active materials during the conversion reaction of WO 3 + 6Li ↔ W + 3 Li 2 O was investigated at controlled electrochemical conditions. Reversible electrode volume expansion and contraction was observed during lithiation and delithiation cycles, respectively. The potential where electrode’s thickness expansion started was ~1.6 V, which is close to thermodynamically expected one for conversion reaction of WO 3 with lithium (1.65 V). The temporal evolution of the electrode volume at constant electrode potentials revealed high overpotential for bulk lithiation and slow conversion reaction kinetics, despite the tailored porosity of the SIS electrodes. Oxide cylinders showed smaller overall electrode thickness change, likely due to unconstrained lateral volume change, as compared to a matrix with holes. On the other hand, better connectivity and guided volume change of the latter electrode morphology provided improved cycling stability. Additionally, heterogeneity in an electrode, from internal pores and density gradients, was found to aggravate the fragmentation of the electrode during conversion reaction. Insights into oxide conversion reaction kinetics and the relationship between electrode mesostructure and cycling behavior obtained from this study can help guide the more rational design of conversion electrode for high performing batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystallization of binary nanocrystal superlattices and the relevance of short-range attraction

The synthesis of binary nanocrystal superlattices (BNSLs) enables the targeted integration of orthogonal physical properties, such as photoluminescence and magnetism, into a single superstructure, unlocking a vast design space for multifunctional materials. However, the formation mechanism of BNSLs remains poorly understood, restricting the prediction of the structure and properties of superlattices. Here we use a combination of in situ scattering and molecular simulation to elucidate the self-assembly of two common BNSLs (AlB 2 and NaZn 13 ) through emulsion templating. Our self-assembly experiments reveal that no intermediate structures precede the formation of the final binary phases, indicating that their formation proceeds through classical nucleation. Using simulations, we find that, despite the formation of AlB 2 and NaZn 13 typically being attributed to entropy, their self-assembly is most consistent with the nanocrystals possessing short-range interparticle attraction, which we find can accelerate nucleation kinetics in BNSLs. Here, we also find homogeneous, classical nucleation in simulations, corroborating our experiments. These results establish a robust correspondence between experiment and theory, paving the way towards prediction of BNSLs.

36 MATERIALS SCIENCE↗

How does your gyroid grow? A mesoatomic perspective on supramolecular, soft matter network crystals

We propose and describe a framework to understand the structure of supramolecular network crystals formed in soft matter in terms of mesoatomic building blocks, collective groupings of amphiphilic molecules that play a role analogous to atomic or molecular subunits of hard matter crystals. While the concept of mesoatoms is intuitive and widely invoked in crystalline arrangements of spherelike or cylinderlike (micellelike) domains, analogous notions of natural and physically meaningful building blocks of triply periodic network (TPN) crystals, like the double-gyroid or double-diamond structures are obscured by the complex, bicontinuous domain shapes and intercatenated topologies of the double networks. Focusing on the specific example of diblock copolymer melts, we propose generic rules for decomposing TPN crystals into a unique set of mesoatomic building blocks. Based on physically motivated principles, the combination of symmetries and topologies of these structures point to mesoatomic elements associated with the nodal connections, leading to mesoatomic volumes that are nonconvex and bound by smoothly curved faces, unlike the more familiar Voronoi polyhedral shapes associated with spherelike and cylinderlike mesoatoms. We analyze the shapes of these mesoatoms, their internal structure, and importantly, their local packing with neighbor mesoatomic units. Importantly, we hypothesize that mesoatoms are kinetically favored intermediate structures whose local shapes and packing template network crystal assembly on long time scales. We propose and study a minimal energetic model of mesoatom assembly for three different cubic double-network crystals, based on local shape packing, which predicts a detailed picture for kinetics of intercatenation and surface growth. Based on these analyses, we discuss several possible extensions and elaborations of the mesoatomic description of supramolecular soft matter network crystals, most notably the implications of mesoatomic malleability, a feature that distinguishes soft matter from hard matter crystals. We describe experimental observations of malleable mesoatomic units in the precursor sponge phase as well as in ordered cubic networks and suggest possibilities for observing mesoatoms in primordial, precrystalline states.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Mesoporous Thin Film Architectures: Addressing Material Demands through Molecular Self-Assembly

Mesoporous thin films spark interest across a wide range of disciplines due to their tunable nanostructures, large internal surface areas, and strong compatibility with planar optical, electronic, and microfluidic devices. While attention in the porous materials community has shifted toward macroporous or disordered nanoporous systems, a resurgence in mesoporous thin film research is underway, driven by new molecular self-assembly methods, advanced materials chemistry, and improved characterization techniques. The integration of high-χN block copolymer design, kinetically persistent micelle templating, and postdeposition processing protocols now allows control over structural parameters such as pore size, wall thickness, porosity, and connectivity. These advances have overcome many of the thermodynamic and processing constraints that previously limited widespread adoption. Rather than serving only as high-surface-area supports, mesoporous thin films are engineered as active interfaces where responsive chemistries and nanoscale confinement act in tandem. Embedding switchable ligands, thermoresponsive polymers, redox mediators, or ion-selective groups directly within the pore walls enables real-time control over transport, optical, and electrochemical properties. These capabilities open up new directions in adaptive coatings, gated membranes, and fast-response biosensors. To further expand their functional scope, mesoporous films are integrated into hierarchical and multicomponent architectures. Techniques such as triblock terpolymer templating, crack-directed assembly, and nanoimprint lithography allow for control over spatial organization on the micron and submicron scale and pore system orientation. This enables programmable anisotropy, enhanced molecular diffusion, and wavelength-selective photonic behavior, essential for next-generation sensing, catalysis, and energy applications. Such structural and functional complexity requires equally sophisticated characterization. Multimodal and in situ techniques can track material dynamics under operational conditions. Recent progress includes extended-range ellipsometric porosimetry (EP) for hierarchical architectures, vacuum EP for interface energetics, time-resolved EP for diffusion kinetics, and correlative AFM-SAXS mapping. The introduction of advanced neutron-based spectroscopies, particularly quasielastic neutron scattering (QENS), promises to provide real-time access to ion transport dynamics and segmental motion under nanoscale confinement, offering a path toward deeper mechanistic understanding of structure-performance correlations in mesoporous systems. This Account reflects the technical advances made and the interdisciplinary collaborations that have shaped our collective vision. The particular dimensions of mesopores enable us to subtly tune interactions at the molecular, interfacial, and mesoscopic levels that permit us to harness nanoconfinement. What emerges is a versatile, modular platform capable of chemical gating, energy transduction, and sensing with a level of tunability unmatched by other porous materials. We highlight critical challenges including the need for more robust large-area processing, a deeper understanding of dynamic behavior under cycling, and better integration with device-level architectures. Our strategies support the transition of mesoporous thin films into active high-performance components in next-generation energy, environmental, and biomedical systems.

oxides↗

Engineered Silicon Carbide Three-Dimensional Frameworks through DNA-Prescribed Assembly

The ability to create nanoengineered silicon carbide (SiC) architectures is important for the diversity of optical, electronic, and mechanical applications. Here, we report a fabrication of periodic three-dimensional (3D) SiC nanoscale architectures using a self-assembled and designed 3D DNA-based framework. The assembly is followed by the templating into silica and subsequent conversion into SiC using a lower temperature pathway (<700 °C) via magnesium reduction. The formed SiC framework lattice has a unit size of about 50 nm and domains over 5 μm, and it preserves the integrity of the original 3D DNA lattice. The spectroscopic and electron microscopy characterizations reveal SiC crystalline morphology of 3D nanoarchitectured lattices, whereas electrical probing shows 2 orders of magnitude enhancements of electrical conductivity over the precursor silica framework. The reported approach offers a versatile methodology toward creating highly structured and spatially prescribed SiC nanoarchitectures through the DNA-programmable assembly and the combination of templating processes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Peptoid-based hierarchically-structured biomimetic nanomaterials: Synthesis, characterization and applications

Peptoids (or poly-N-substituted glycines) is a promising class of bioinspired sequence-defined polymers due to their highly efficient synthesis, high chemical stability, enzyme hydrolysis resistance, and biocompatibility. By tuning the side chain chemistry of peptoids, it allows for a precise control over sequences and achieving a large side-chain diversity. Due to these unique features, in the last several years, many amphiphilic peptoids were designed as highly tunable building blocks for the preparation of biomimetic nanomaterials with well-defined hierarchical structures and desired functionalities. In this paper, we provide an overview of the recent achievements in this area by dividing them into the following three aspects. First, mica- and silica-templated peptoid self-assembly was summarized. Here, the presence of inorganic substrates provides the guarantee of investigating their self-assembly mechanisms and interactions between peptoids and substrates using nanoscale characterization techniques, particularly in situ atomic force spectroscopy (AFM) and AFM-based dynamic force spectroscopy (AFM-DFS). Second, solution-phase self-assembly of peptoids into nanotubes and nanosheets was presented, as well as their self-repair properties. Third, the applications of peptoid based nanomaterials were outlined, including the construction of catalytic nanomaterials as a template and cytosolic delivery as cargoes.

36 MATERIALS SCIENCE↗

Standalone Block Copolymer Nanoballoons: Decoupling Self-Assembly from Implementation in Nanomanufacturing

Here we report a facile method to produce isolatable hollow-core elastomeric vesicles, “nanoballoons”, prepared via block copolymer self-assembly in a polymer blend. Poly(isoprene-block-dimethylsiloxane) (PI-PDMS) diblock copolymers are blended with PDMS homopolymers (h-PDMS) as a “solvent” phase to template the self-assembly of PDMS-tethered vesicles with PI walls. The walls are subsequently crosslinked to yield mechanically stabilized elastomeric vesicles. The h-PDMS inner-core and matrix are separated from the vesicles by dialysis to yield the matrix-free nanoballoons. These objects, 0.3 – 1 μm in diameter, can be further reincorporated into a crosslinkable PDMS. Throughout the self-assembly, recovery, and reincorporation processes we apply several techniques including solvent dispersion/dynamic light scattering (DLS) measurements, transmission electron microscopy (TEM)/energy-dispersive X-ray spectroscopy (EDS), and small-angle X-ray scattering (SAXS) to provide a consilient body of evidence that the nanoballoon morphology is retained. Furthermore, this work presents advanced nanomanufacturing schema that illustrate the decoupling of the thermodynamic and dynamic factors that govern macromolecular self-assembly from the environment in which the self-assembled objects are deployed.

36 MATERIALS SCIENCE↗

Kinetic preference for the 3'-5'-linked dimer in the reaction of guanosine 5'-phosphorylmorpholinamide with deoxyguanosine 5'-phosphoryl-2-methylimidazolide as a function of poly(C) concentration

The formation of the internucleotide bond in diguanylate synthesis was studied in aqueous solution at pH 8 and 0.2 M Mg2+ in the presence and absence of polycytidylate, poly(C). The investigation was simplified by using guanosine 5'-phosphorylmorpholinamide, mor-pG, which can act only as a nucleophile, and deoxyguanosine 5'-phosphoryl-2-methylimidazolide, 2-MeImpdG, which can act only as an electrophile. The time-dependent product distribution was monitored by high-performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC/MS). In the absence of poly(C) the reaction between mor-pG and 2-MeImpdG yielded small amounts of the dimer mor-pGpdG with a regioselectivity of 2'-5':3'-5' = 3.5. In the presence of poly(C) dimer yields increased and a reversal in regioselectivity occurred; both effects were in proportion to the concentration of the polymer. The results can be quantitatively explained with the proposition that poly(C), acting as the template, catalyzes the reaction between template-bound monomers by about a factor of 4-5 over the reaction in solution and yields dimers with a regioselectivity of 2'-5':3'-5' approximately 0.33. These findings illustrate the intrinsic preference of guanosine monomers to correctly self-assemble on the appropriate template.

NASA Discipline Exobiology↗