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At least 1,297 records · Page 72

Pectin methyltransferase QUASIMODO2 functions in the formation of seed coat mucilage in Arabidopsis

Pectin, cellulose, and hemicelluloses are major components of primary cell walls in plants. In addition to cell adhesion and expansion, pectin plays a central role in seed mucilage. Seed mucilage contains abundant pectic rhamnogalacturonan-I (RG-I) and lower amounts of homogalacturonan (HG), cellulose, and hemicelluloses. Previously, accumulated evidence has addressed the role of pectin RG-I in mucilage production and adherence. However, less is known about the function of pectin HG in seed coat mucilage formation. In this study, we analyzed a novel mutant, designated things fall apart2 (tfa2), which contains a mutation in HG methyltransferase QUASIMODO2 (QUA2). Etiolated tfa2 seedlings display short hypocotyls and adhesion defects similar to qua2 and tumorous shoot development2 (tsd2) alleles, and show seed mucilage defects. Here, the diminished uronic acid content and methylesterification degree of HG in mutant seed mucilage indicate the role of HG in the formation of seed mucilage. Cellulosic rays in mutant mucilage are collapsed. The epidermal cells of seed coat in tfa2 and tsd2 display deformed columellae and reduced radial wall thickness. Under polyethylene glycol treatment, seeds from these three mutant alleles exhibit reduced germination rates. Together, these data emphasize the requirement of pectic HG biosynthesis for the synthesis of seed mucilage, and the functions of different pectin domains together with cellulose in regulating its formation, expansion, and release.

59 BASIC BIOLOGICAL SCIENCES↗

Unpacking the drivers of diurnal dynamics of sun-induced chlorophyll fluorescence (SIF): Canopy structure, plant physiology, instrument configuration and retrieval methods

Sun-induced chlorophyll fluorescence (SIF) from spaceborne sensors is a promising tool for global carbon cycle monitoring, but its application is constrained by insufficient understanding of the drivers underlying diurnal SIF dynamics. SIF measurements from ground-based towers can reveal diurnal SIF dynamics across biomes and environmental conditions; however, meaningful interpretation of diurnal variations requires disentangling impacts from canopy structure, plant physiology, instrument configuration and retrieval methods, which often interact with and confound each other. This study aims to unpack these drivers using 1) concurrent ground and airborne canopy-scale and leaf-scale measurements at a corn field, 2) a mechanistic SIF model that explicitly considers the dynamics of photochemistry (via the fraction of open photosystem II reaction centers, qL) and photoprotection (via nonphotochemical quenching, NPQ) as well as their interactive dependence on the sub-canopy light environment, and 3) cross-comparison of SIF instrument configurations and retrieval methods. We found that crop row orientations and sun angles can introduce a distinctive midday dip in SIF in absence of stress, due to a midday drop of absorbed photosynthetically active radiation (APAR) when crop rows are north-south oriented. Canopy structure caused distinctive responses in both qL and NPQ at different positions within the vertical canopy that collectively influenced fluorescence quantum yield (Φ F ) at the leaf scale. Once integrated at the canopy scale, diurnal dynamics of both APAR and canopy escape probability (ε) are critical for accurately shaping diurnal SIF variations. While leaf-level qL and NPQ exhibited strong diurnal dynamics, their influence was attenuated at the canopy scale due to opposing effects on SIF at different canopy layers. Furthermore, different system configurations (i.e., bi-hemispherical vs. hemispherical-conical) and retrieval methods can bias the SIF magnitude and distort its diurnal shapes, therefore confounding the interpretation of inherent strength and dynamics of SIF emission. Our findings demonstrate the importance of crop row structures, interactive variations in canopy structure and plant physiology, instrument configuration, and retrieval method in shaping the measured dynamics of diurnal SIF. This study highlights the necessity to account for these factors to accurately interpret satellite SIF, and informs future synthesis work with different SIF instrumentation and retrieval methods across sites.

59 BASIC BIOLOGICAL SCIENCES↗

Synthesis of Tunable SnS-TaS 2 Nanoscale Superlattices

Nanoscale superlattices represent a compelling platform for designed materials as the specific identity and spatial arrangement of constituent layers can lead to tunable properties. A number of kinetically stabilized, nonepitaxial superlattices with almost limitless structural tunability have been reported in telluride and selenide chemistries but have not yet been extended to sulfides. Here, we present SnS-TaS 2 nanoscale superlattices with tunable layer architecture. Layered amorphous precursors are prepared as thin films programmed to mimic the targeted superlattice; subsequent low temperature annealing activates self-assembly into crystalline nanocomposites. We investigate structure and composition of superlattices comprised of monolayers of TaS 2 and 3–7 monolayers of SnS per repeating unit. Furthermore, a graded precursor preparation approach is introduced, allowing stabilization of superlattices with multiple stacking sequences in a single preparation. Controlled synthesis of the architecture of nanoscale superlattices is a critical path toward tuning their exotic properties and enabling integration with electronic, optical, or quantum devices.

36 MATERIALS SCIENCE↗

Seeing the Disturbed Forest for the Trees: Remote Sensing Is Underutilized to Quantify Critical Zone Response to Unprecedented Disturbance

Understanding the severity and extent of near surface critical zone (CZ) disturbances and their ecosystem response is a pressing concern in the face of increasing human and natural disturbances. Predicting disturbance severity and recovery in a changing climate requires comprehensive understanding of ecosystem feedbacks among vegetation and the surrounding environment, including climate, hydrology, geomorphology, and biogeochemistry. Field surveys and satellite remote sensing have limited ability to effectively capture the spatial and temporal variability of disturbance and CZ properties. Technological advances in remote sensing using new sensors and new platforms have improved observations of changes in vegetation canopy structure and productivity; however, integrating measures of forest disturbance from various sensing platforms is complex. By connecting the potential for remote sensing technologies to observe different CZ disturbance vectors, we show that lower severity disturbance and slower vegetation recovery are more difficult to quantify. Case studies in montane forests from the western United States highlight new opportunities, including evaluating post-disturbance forest recovery at multiple scales, shedding light on understory vegetation regrowth, detecting specific physiological responses, and refining ecohydrological modeling. Learning from regional CZ disturbance case studies, we propose future directions to synthesize fragmented findings with (a) new data analysis using new or existing sensors, (b) data fusion across multiple sensors and platforms, (c) increasing the value of ground-based observations, (d) disturbance modeling, and (e) synthesis to improve understanding of disturbance.

54 ENVIRONMENTAL SCIENCES↗

Observation of formation and local structures of metal-organic layers via complementary electron microscopy techniques

Abstract Metal-organic layers (MOLs) are highly attractive for application in catalysis, separation, sensing and biomedicine, owing to their tunable framework structure. However, it is challenging to obtain comprehensive information about the formation and local structures of MOLs using standard electron microscopy methods due to serious damage under electron beam irradiation. Here, we investigate the growth processes and local structures of MOLs utilizing a combination of liquid-phase transmission electron microscopy, cryogenic electron microscopy and electron ptychography. Our results show a multistep formation process, where precursor clusters first form in solution, then they are complexed with ligands to form non-crystalline solids, followed by the arrangement of the cluster-ligand complex into crystalline sheets, with additional possible growth by the addition of clusters to surface edges. Moreover, high-resolution imaging allows us to identify missing clusters, dislocations, loop and flat surface terminations and ligand connectors in the MOLs. Our observations provide insights into controllable MOL crystal morphology, defect engineering, and surface modification, thus assisting novel MOL design and synthesis.

36 MATERIALS SCIENCE↗

Metallic 2D Janus SNbSe layers driven by a structural phase change

Synthesis of 2D metallic Janus SNbSe and SeNbS in 1T phase from 1H-phase NbS 2 and NbSe 2 , respectively, is achieved through using a room temperature plasma-assisted technique that induces a structural phase transition.

Wu, Cheng-Lun [Materials Science and Engineering, ↗

Compact in situ probe for magnetotransport measurements of 2D materials under variable tensile strain

The recent development of freestanding oxide membranes has opened new opportunities for strain engineering of transition metal oxides beyond values accessible in bulk samples. While a number of studies have been performed with fixed strain, the ability to dynamically control the strain state during measurement would be greatly enabling. To this end, we present an in situ uniaxial strain probe optimized for transport measurements of tensile-strained 2D or quasi-2D materials down to 2 K. Utilizing a flexible polyimide substrate as the stress transfer medium, our platform simplifies the sample preparation process and allows precise alignment of strain fields relative to the crystalline axes. An in situ optical microscope monitors the macroscopic strain state operando and makes it possible to complete an entire magnetotransport study at cryogenic temperatures under continuous strain variations. We demonstrate the capabilities of the probe on a freestanding LaNiO 3 membrane, where we induce tensile strain up to 8% and observe a corresponding strong transport anisotropy. In view of the rapid developments in low-dimensional materials synthesis and the plethora of novel quantum phenomena they exhibit, this strain probe provides general instrumentation for examining and controlling these properties via strain.

2D materials↗

Bilin-dependent regulation of chlorophyll biosynthesis by GUN4

Significance Enzymes of the chlorophyll biosynthetic pathway, which bind protoporphyrin and Mg-porphyrins, are susceptible to damage by singlet oxygen production in the presence of light and oxygen. These studies show that heme-derived linear tetrapyrroles (bilins) both stimulate and protect the protoporphyrin-binding CHLH subunit of Mg chelatase, the first committed enzyme of the chlorophyll synthesis, from self-sensitized photodamage and turnover via formation of nonphotosensitizing GENOMES UNCOUPLED 4 (GUN4):bilin:porphyrin adducts, which deliver protoporphyrin to CHLH. GUN4:bilin adducts likely evolved to sustain chlorophyll biosynthesis in an oxic world, accounting for retention of bilin synthesis in nearly all oxygenic photosynthetic species on Earth.

photosynthesis↗

Pinoresinol rescues developmental phenotypes of Arabidopsis phenylpropanoid mutants overexpressing FERULATE 5-HYDROXYLASE

Most phenylpropanoid pathway flux is directed toward the production of monolignols, but this pathway also generates multiple bioactive metabolites. The monolignols coniferyl and sinapyl alcohol polymerize to form guaiacyl (G) and syringyl (S) units in lignin, components that are characteristic of plant secondary cell walls. Lignin negatively impacts the saccharification potential of lignocellulosic biomass. Although manipulation of its content and composition through genetic engineering has reduced biomass recalcitrance, in some cases, these genetic manipulations lead to impaired growth. Here, the reduced-growth phenotype is often attributed to poor water transport due to xylem collapse in low-lignin mutants, but alternative models suggest that it could be caused by the hyper- or hypoaccumulation of phenylpropanoid intermediates. In Arabidopsis thaliana, overexpression of FERULATE 5-HYDROXYLASE (F5H) shifts the normal G/S lignin ratio to nearly pure S lignin and does not result in substantial changes to plant growth. In contrast, when we overexpressed F5H in the low-lignin mutants cinnamyl dehydrogenase c and d (cadc cadd), cinnamoyl-CoA reductase 1, and reduced epidermal fluorescence 3, plant growth was severely compromised. In addition, cadc cadd plants overexpressing F5H exhibited defects in lateral root development. Exogenous coniferyl alcohol (CA) and its dimeric coupling product, pinoresinol, rescue these phenotypes. These data suggest that mutations in the phenylpropanoid pathway limit the biosynthesis of pinoresinol, and this effect is exacerbated by overexpression of F5H, which further draws down cellular pools of its precursor, CA. Overall, these genetic manipulations appear to restrict the synthesis of pinoresinol or a downstream metabolite that is necessary for plant growth.

59 BASIC BIOLOGICAL SCIENCES↗

Trivalent rare earth metal cofactors confer rapid NP-DNA polymerase activity

Here, a DNA polymerase with a single mutation and a divalent calcium cofactor catalyzes the synthesis of unnatural N3'→P5' phosphoramidate (NP) bonds to form NP-DNA. However, this template-directed phosphoryl transfer activity remains orders of magnitude slower than native phosphodiester synthesis. Here, we used time-resolved x-ray crystallography to show that NP-DNA synthesis proceeds with a single detectable calcium ion in the active site. Using insights from isotopic and elemental effects, we propose that one-metal-ion electrophilic substrate activation is inferior to the native two-metal-ion mechanism. We found that this deficiency in divalent activation could be ameliorated by trivalent rare earth and post–transition metal cations, substantially enhancing NP-DNA synthesis. Scandium(III), in particular, confers highly specific NP activity with kinetics enhanced by more than 100-fold over calcium(II), yielding NP-DNA strands up to 100 nucleotides in length.

59 BASIC BIOLOGICAL SCIENCES↗

Systems and methods for PTNI nanocages

A method for synthesis of PtNi nanocages by synthesizing Pt1Ni6 nanoparticles and acid leaching to form PtNi nanocages. The acid leaching removes nickel selectively from the core of the nanoparticle.

36 MATERIALS SCIENCE↗

Distinctive exchange bias and unusual memory effects in magnetically compensated Pr 0.75 Gd 0.25 ScGe

Tuning the chemistry of materials often leads to discoveries of interesting phenomena that expand basic science and support practical applications. Here we show how different spin–orbit coupling in light and heavy lanthanides can be exploited to create complex magnetic ground states and thereby unusual spontaneous exchange bias (SEB), conventional exchange bias (CEB), and magnetic memory effects in almost ideally magnetically compensated Pr 0.75 Gd 0.25 ScGe, which is a representative of the PrScGe–GdScGe solid solution. We report the synthesis and detailed characterization of Pr 0.75 Gd 0.25 ScGe by X-ray powder diffraction, scanning electron microscopy, and magnetization measurements in magnetic fields up to 140 kOe. Partial substitution of a light lanthanide, Pr, with a heavy lanthanide, Gd, results in a complex magnetic ground state, which includes large spontaneous and conventional exchange biases reaching magnitudes of ~1.7 kOe and ~3.5 kOe, respectively, at T = 2 K, as well as shape dependent magnetic compensation and bias phenomena occurring in small external fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Biology and the Exploration of Mars

Until recent years the origin of life and its possible occurrence elsewhere in the universe have been matters for speculation only. The rapid growth of molecular biology since 1940 has, to be sure, made it possible to discuss life's origins in far more precise and explicit terms than was possible earlier; and the subject entered a new experimental phase in the 1950's with successful abiogenic synthesis of important biochemical substances in conditions simulating the presumptive environment of the primitive Earth. But the real transformation that the subject has undergone stems from the spectacular growth of space technology in the last decade. The possibility of life's origin and occurrence on planets other than ours is no longer limited to idle speculation: it has entered the realm of the testable, of science in the strict sense. Given the rockets now available, and especially those available by 1969, it has become fully realistic to consider plans for the biological exploration of Mars. The study that this report seeks to interpret was initiated in June, 1964, by the Space Science Board of the National Academy of Sciences to examine this possibility. The working group comprised 36 people representing a broad spectrum of scientific interests: evolutionary biology, genetics, microbiology, biochemistry and molecular biology, animal physiology, soil chemistry, organic chemistry, planetary astronomy, geochemistry, and theoretical physics. The participants included some with considerable prior involvement in problems of space exploration and others with none. Advice was also sought outside the group of immediate participants on the potentialities of selected analytical methods for the experimental study of extraterrestrial life and its environment. More than 30 individuals contributed in this fashion written assessments of techniques in which they were particularly well versed. Our task was to examine the scientific foundations and merits of the proposal to undertake a biological exploration of Mars. What are the potential scientific yields? How valuable, if attained, would they be? What, in fact, is the possibility of life occurring on Mars? And of our detecting it with available and foreseeable technology? What could be achieved by further astronomical work from Earth? by Martian fly-by missions? by Martian orbiters? and Martian Landers? What payloads would we recommend for planetary missions? What timing and over-all strategy would we recommend for Martian exploration were we to consider it worthwhile at all? In brief, the over-all purpose was to recommend to. the government, through the Academy's Space Science Board, whether or not a biological exploration of Mars should be included in the nation's space program over the next few decades; and, further, to outline what that program, if any, should be.

CONFERENCE↗

The Features of Self-Assembling Organic Bilayers Important to the Formation of Anisotropic Inorganic Materials in Microgravity Conditions

There is a growing need for inorganic anisotropic particles in a variety of materials science applications. Structural, optical, and electrical properties can be greatly augmented by the fabrication of composite materials with anisotropic microstructures or with anisotropic particles uniformly dispersed in an isotropic matrix. Examples include structural composites, magnetic and optical recording media, photographic film, certain metal and ceramic alloys, and display technologies including flat panel displays. While considerable progress has been made toward developing an understanding of the synthesis of powders composed of monodispersed, spherical particles, these efforts have not been transferred to the synthesis of anisotropic nanoparticles. The major objective of the program is to develop a fundamental understanding of the growth of anisotropic particles at organic templates, with emphasis on the chemical and structural aspects of layered organic assemblies that contribute to the formation of anisotropic inorganic particles.

Talham, Daniel R.↗

Non-Solvent Induced Phase Separation Enables Designer Redox Flow Battery Electrodes

Porous carbonaceous electrodes are performance-defining components in redox flow batteries (RFBs), where their properties impact the efficiency, cost, and durability of the system. The overarching challenge is to simultaneously fulfill multiple seemingly contradictory requirements—i.e., high surface area, low pressure drop, and facile mass transport—without sacrificing scalability or manufacturability. Here, non-solvent induced phase separation (NIPS) is proposed as a versatile method to synthesize tunable porous structures suitable for use as RFB electrodes. The variation of the relative concentration of scaffold-forming polyacrylonitrile to pore-forming poly(vinylpyrrolidone) is demonstrated to result in electrodes with distinct microstructure and porosity. Tomographic microscopy, porosimetry, and spectroscopy are used to characterize the 3D structure and surface chemistry. Flow cell studies with two common redox species (i.e., all-vanadium and Fe2+/3+) reveal that the novel electrodes can outperform traditional carbon fiber electrodes. It is posited that the bimodal porous structure, with interconnected large (>50 µm) macrovoids in the through-plane direction and smaller (<5 µm) pores throughout, provides a favorable balance between offsetting traits. Although nascent, the NIPS synthesis approach has the potential to serve as a technology platform for the development of porous electrodes specifically designed to enable electrochemical flow technologies.

36 MATERIALS SCIENCE↗

Evaluation of Iron‐Phosphate Glass–Ceramic Waste Form for Electrorefiner Salt Waste Simulant Dechlorinated With Phosphoric Acid

The importance of glass and glass–ceramic nuclear waste forms has been reaffirmed in recent years by the growing interest in nuclear power as a reliable energy source. Determination of processing methods for the disposal of halide-containing wastes will be essential for the advancement of nuclear technologies such as non-aqueous fuel reprocessing. Phosphate-based dechlorination and subsequent vitrification of radioactive salt waste into an iron-phosphate waste form have been identified as a potential processing scheme for electrochemical processing waste. The impact of H 3 PO 4 -based dechlorination of complex salt mixtures on the vitrification process and structure of the final iron-phosphate waste form has not yet been investigated. In this work, iron-phosphate glass–ceramics were made from simulant salt waste (48LiCl–33KCl–19NaCl mol%) dechlorinated with the H3PO4-based method. The glass-forming region was compared to that of traditionally prepared Na 2 O–Fe 2 O 3 –P 2 O 5 systems. For a candidate glass-forming composition, the processing scheme presented here was determined to favor Fe 3+ species. The O/P molar ratio was consistent for the candidate composition when dechlorinated at 400°C and 600°C in air and argon environments, indicating glass network connectivity was maintained despite variations in processing parameters. The results presented here validate processing schemes requiring iron-phosphate waste form synthesis following H 3 PO 4 -based dechlorination.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Breakthrough innovations in carbon dioxide mineralization for a sustainable future

Greenhouse gas emissions and climate change concerns have prompted worldwide initiatives to lower carbon dioxide (CO 2 ) levels and prevent them from rising in the atmosphere, thereby controlling global warming. Effective CO 2 management through carbon capture and storage is essential for safe and permanent storage, as well as synchronically meeting carbon reduction targets. Lowering CO 2 emissions through carbon utilization can develop a wide range of new businesses for energy security, material production, and sustainability. CO 2 mineralization is one of the most promising strategies for producing thermodynamically stable solid calcium or magnesium carbonates for long-term sequestration using simple chemical reactions. Current advancements in CO 2 mineralization technologies, focusing on pathways and mechanisms using different industrial solid wastes, including natural minerals as feedstocks, are briefly discussed. However, the operating costs, energy consumption, reaction rates, and material management are major barriers to the application of these technologies in CO 2 mineralization. Further, the optimization of operating parameters, tailor-made equipment, and smooth supply of waste feedstocks require more attention to make the carbon mineralization process economically and commercially viable. Here, carbonation mechanisms, technological options to expedite mineral carbonation, environmental impacts, and prospects of CO 2 mineralization technologies are critically evaluated to suggest a pathway for mitigating climate change in the future. The integration of industrial wastes and brine with the CO 2 mineralization process can unlock its potential for the development of novel chemical pathways for the synthesis of calcium or magnesium carbonates, valuable metal recovery, and contribution to sustainability goals while reducing the impact of global warming.

54 ENVIRONMENTAL SCIENCES↗

Mechanistic insights into the colloidal assembly of mesoporous silica using in-operando cross-scale X-ray scattering and spectroscopic measurements

Advancing a mechanistic understanding of the colloidal to solid-phase transformations of silica allows us to tune these meso-scale structures. In this study, we probe the structural transformations associated with the formation of mesoporous silica particles, SBA-15 using in-operando Small Angle X-ray Scattering (SAXS) and Grazing Incidence-Small Angle X-ray Scattering (GI-SAXS). The chemical transformations associated with the hydrolysis and condensation of silica particles is investigated using Attenuated Total Reflection – Fourier Transform Infrared Spectroscopy (ATR-FTIR) measurements. Fast polymerization of Si-O-Si species to form mesoporous silica is noted when SBA-15 is synthesized in the presence of nitrate salts, due to the “salting-in” effect or enhanced solubility of polymers. However, aging the silica particles resulted in plate-like morphologies in the absence of the nitrate salt and spherical morphologies in the presence of nitrate salt. Early onset of nucleation of silica particles in the presence of nitrate salts was captured using GI-SAXS measurements. These studies show that the rational basis for developing new synthesis routes for accelerated kinetics or specific meso-scale structures can be informed by detailed characterization of the evolution in chemistry and meso-scale structure of these materials.

36 MATERIALS SCIENCE↗