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At least 451 records · Page 25

Editorial: Cellular heterogeneity in plants

Multicellular eukaryotic organisms, such as plants, consist of various cell types. Despite possessing the same genetic information, each cell exhibits distinct utilization of this information, resulting in the development of unique molecular, physiological, and morphological properties as well as cellular heterogeneity within the organism. This cellular heterogeneity is needed to support plant development and adaptation to environmental changes. Identifying the mechanisms responsible for the differentiation of distinct cell types and precisely characterizing the molecular, biochemical, biophysical, and morphological characteristics of each cell type in various plant species remains a significant objective for plant scientists. Despite the biological importance of these cellular attributes, they have not been adequately described. In this Frontiers Research Topic, “Cellular Heterogeneity in Plants,” various scientific papers provide valuable new insights into the causes and consequences of cellular heterogeneity in plants.

59 BASIC BIOLOGICAL SCIENCES↗

Effect of Initiator Density, Catalyst Concentration, and Surface Curvature on the Uniformity of Polymers Grafted from Spherical Nanoparticles

Polymer-grafted nanoparticles (PGNPs) are versatile hybrid materials whose properties critically depend on brush dimensions, uniformity, and grafting density. Herein, we systematically investigated how initiator density, catalyst concentration, and nanoparticle curvature govern the growth of poly(methyl methacrylate) (PMMA) brushes grafted from spherical SiO 2 nanoparticles via surface-initiated activators regenerated by electron transfer atom transfer radical polymerization (SI-ARGET ATRP). By tuning the initiator density through a combination of “active” and “dummy” silane initiators anchored on the nanoparticles’ surface and controlling the catalyst concentration, we reveal that increased initiator crowding and smaller surface curvature amplify steric hindrance, leading to decreased initiation efficiency and broader molecular weight distributions. Correlation with the corresponding unattached chains by ARGET ATRP suggests the presence of permanently inaccessible (“buried”) initiation sites, which are a characteristic of surface-grafted systems. At sufficient Cu catalyst concentrations, uniform brush growth is attained across different initiator densities, whereas decreased catalyst concentrations accentuate nonconcurrent initiation and propagation. These findings provide mechanistic insights into the interplay of initiator density, catalyst concentration, and surface curvature, offering design principles for tailoring the PGNP architecture. These results can guide the structural engineering of densely grafted surfaces, including nanoparticles and flat substrates, for applications in nanocomposites, photonics, and functional coatings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lab Demonstration of the Hybrid Doppler Wind Lidar (HDWL) Transceiver

The recommended design approach for the 3D Tropospheric Winds mission is a hybrid Doppler lidar which combines the best elements of both a coherent aerosol Doppler lidar operating at 2 micron and a direct detection molecular Doppler lidar operating at 0.355 micron. In support of the mission, we built a novel, compact, light-weighted multi-field of view transceiver where multiple telescopes are used to cover the required four fields of view. A small mechanism sequentially selects both the "transmit" and "receive" fields of view. The four fields are combined to stimulate both the 0.355 micron receiver and the 2 micron receiver. This version is scaled (0.2 micron diameter aperture) from the space-based version but still demonstrates the feasibility of the hybrid approach. The primary mirrors were conventionally light-weighted and coated with dielectric, high reflectivity coatings with high laser damage thresholds at both 2 micron and 0.355 micron. The mechanical structure and mounts were fabricated from composites to achieve dimensional stability while significantly reducing the mass. In the laboratory, we demonstrated the system level functionality at 0.355 micron and at 2 micron raising the Technology Readiness Level (TRL) from 2 to 4.

Marx, Catherine T.↗

Lab Demonstration of the Hybrid Doppler Wind Lidar (HDWL) Transceiver

The recommended design approach for the 3D Tropospheric Winds mission is a hybrid Doppler lidar which combines the best elements of both a coherent aerosol Doppler lidar operating at 2 microns and a direct detection molecular Doppler lidar operating at 0.355 microns. In support of the mission, we built a novel, compact, light-weighted multi-field of view transceiver where multiple telescopes are used to cover the required four fields of view. A small mechanism sequentially selects both the "transmit" and "receive" fields of view. The four fields are combined to stimulate both the 0.355 micron receiver and the 2 micron receiver. This version is scaled (0.2 m diameter aperture) from the space-based version but still demonstrates the feasibility of the hybrid approach. The primary mirrors were conventionally light-weighted and coated with dielectric, high reflectivity coatings with high laser damage thresholds at both 2 microns and 0.355 microns. The mechanical structure and mounts were fabricated from composites to achieve dimensional stability while significantly reducing the mass. In the laboratory, we demonstrated the system level functionality at 0.355 microns and at 2 microns, raising the Technology Readiness Level (TRL) from 2 to 4.

Marx, Catherine T.↗

Results from Optical Coatings Flown on MISSE-1 and MISSE-2 and other Flight Experiments

Selected optically transparent materials and coatings flown on a number of low Earth orbit (LEO) materials flight experiments will be reviewed and discussed. Effects of flight exposure for both magnesium fluoride and lithium fluoride specimens will be presented. Individual specimens of magnesium fluoride were flown on the EOIM I11 Space Shuttle experiment, the Long Duration Exposure Facility (LDEF), the Optical Properties Monitor and Passive Optical Sample Assembly experiments on Mir, and MISSE-1 and MISSE-2 International Space Station packages. Subsequent to the LDEF retrieval and EOIM I11 experiment in 1992, the question of atomic oxygen reaction with magnesium fluoride was raised. Atomic oxygen and solar exposures, molecular contamination levels, and varying exposure durations will each be considered in evaluating any observed changes in optical properties. A comparison of the thermodynamics of oxidation of magnesium fluoride and lithium fluoride will be summarized. Elemental composition as a function of depth, as determined using XPS, will be discussed for selected specimens, to gain insight into reactions that are thermodynamically allowed under the LEO conditions.

Finckenor, Miria↗

Solution-processable integrated CMOS circuits based on colloidal CuInSe2 quantum dots

Abstract The emerging technology of colloidal quantum dot electronics provides an opportunity for combining the advantages of well-understood inorganic semiconductors with the chemical processability of molecular systems. So far, most research on quantum dot electronic devices has focused on materials based on Pb- and Cd chalcogenides. In addition to environmental concerns associated with the presence of toxic metals, these quantum dots are not well suited for applications in CMOS circuits due to difficulties in integrating complementary n - and p -channel transistors in a common quantum dot active layer. Here, we demonstrate that by using heavy-metal-free CuInSe 2 quantum dots, we can address the problem of toxicity and simultaneously achieve straightforward integration of complimentary devices to prepare functional CMOS circuits. Specifically, utilizing the same spin-coated layer of CuInSe 2 quantum dots, we realize both p - and n -channel transistors and demonstrate well-behaved integrated logic circuits with low switching voltages compatible with standard CMOS electronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigating the impact of preparation routes on the properties of copper-decorated silicon particles as anode materials for lithium-ion batteries

In recent years, the calendar life of Si has been recognized as a significant issue that must be addressed prior to technology deployment: The carbon conductive additive is a potential source of parasitic side reactions. However, carbon remains essential due to the low electronic conductivity of Si. In this study, we investigate the use of Cu as a conductive additive and potential alternative to carbon. Some Cu-decorated silicon particles (Si Cu ) were prepared using physical vapor deposition (PVD) via sputtering and high-energy milling. Other Si Cu particles were prepared by using a solution method and examined briefly. The milling method caused Cu to appear as island-like features on the Si surface, whereas the PVD method initially produced similar island-like features that gradually developed into a continuous coating around the Si as sputtering time increased. Electrodes fabricated from Si Cu exhibited lower overall resistivity, demonstrating the beneficial effect of Cu in improving electronic percolation through the electrode. Electrochemical tests showed that the milled SiCu exhibited higher capacity retention, improved rate capability, and lower overpotential. Furthermore, Si Cu coupled with an NMC811 cathode exhibited lower leakage currents compared with the baseline silicon, indicating that incorporating Cu provided an additional advantage of minimizing parasitic currents in the cells.

25 ENERGY STORAGE↗

Fluid models and simulations of biological cell phenomena

The dynamics of coated droplets are examined within the context of biofluids. Of specific interest is the manner in which the shape of a droplet, the motion within it as well as that of aggregates of droplets can be controlled by the modulation of surface properties and the extent to which such fluid phenomena are an intrinsic part of cellular processes. From the standpoint of biology, an objective is to elucidate some of the general dynamical features that affect the disposition of an entire cell, cell colonies and tissues. Conventionally averaged field variables of continuum mechanics are used to describe the overall global effects which result from the myriad of small scale molecular interactions. An attempt is made to establish cause and effect relationships from correct dynamical laws of motion rather than by what may have been unnecessary invocation of metabolic or life processes. Several topics are discussed where there are strong analogies droplets and cells including: encapsulated droplets/cell membranes; droplet shape/cell shape; adhesion and spread of a droplet/cell motility and adhesion; and oams and multiphase flows/cell aggregates and tissues. Evidence is presented to show that certain concepts of continuum theory such as suface tension, surface free energy, contact angle, bending moments, etc. are relevant and applicable to the study of cell biology.

Greenspan, H. P.↗

Optically transparent/colorless polyimides

Several series of linear aromatic polyimide films have been synthesized and characterized with the objective of obtaining maximum optical transparency. Two approaches have been used as part of this structure-property relationship study. The first approach is to vary the molecular structure so as to separate chromophoric centers and reduce electronic interactions between polymer chains to lower the intensity of color in the resulting polymer films. A second and concurrent approach is to perform polymerizations with highly purified monomers. Glass transition temperatures of thermally cured polyimide films are obtained by thermomechanical analysis and thermal decomposition temperatures are determined by thermogravimetric analysis. Transmittance UV-visible spectra of the polyimide films are compared to that of a commercial polyimide film. Fully imidized films are tested for solubility in common organic solvents. The more transparent films prepared in this study are evaluated for use on second-surface mirror thermal control coating systems. Lightly colored to colorless films are characterized by UV-visible spectroscopy before and after exposure to 300 equivalent solar hours UV irradiation and varying doses of 1 MeV electron irradiation. The effects of monomer purity, casting solvent and cure atmosphere on polyimide film transparency are also investigated.

Stclair, A. K.↗

320 x 256 Complementary Barrier Infrared Detector Focal Plane Array for Long-Wave Infrared Imaging

A 320 x 256 Complementary Barrier Infrared (CBIRD) focal plane array for long-wavelength infrared (LWIR) imaging is reported. The arrays were grown by molecular beam expitaxy (MBE) with a 300 period 1.9 um thick absorber. The mean dark current density of 2.2 x 10-4 A/cm2 was measured at an operating bias of 128 mV with a long wavelength cutoff of 8.8 ?m observed at 50% of the peak. The maximum quantum efficiency was 54% measured at 5.6 ?m. Operating at T = 80K, the array yielded an 81% fill factor with 97% operability. Good imagery with a mean noise equivalent different temperature (NE?T) of 18.6 mK and a mean detectivity of D* = 1.3 x 1011 cm-Hz1/2/W was achieved. The substrate was thinned using mechanical lapping and neither an AR coating nor a passivation layer was applied. This article provides the details of the fabrication process for achieving low-dark current LWIR CBIRD arrays. Discussion for an effective hard mask for excellent pattern transfer is given and appropriate mounting techniques for good thermal contact during the dry etching process is described. The challenges and differences between etching large 200 ?m test diodes and small 28 ?m FPA pixels are given.

Focal Plane Arrays (FPA)↗

Vacuum ultraviolet instrumentation for solar irradiance and thermospheric airglow

A NASA sounding rocket experiment was developed to study the solar extreme ultraviolet (EUV) spectral irradiance and its effect on the upper atmosphere. Both the solar flux and the terrestrial molecular nitrogen via the Lyman-Birge-Hopfield bands in the far ultraviolet (FUV) were measured remotely from a sounding rocket on October 27, 1992. The rocket experiment also includes EUV instruments from Boston University (Supriya Chakrabarti), but only the National Center for Atmospheric Research (NCAR)/University of Colorado (CU) four solar instruments and one airglow instrument are discussed here. The primary solar EUV instrument is a 1/4 meter Rowland circle EUV spectrograph which has flown on three rockets since 1988 measuring the solar spectral irradiance from 30 to 110 nm with 0.2 nm resolution. Another solar irradiance instrument is an array of six silicon XUV photodiodes, each having different metallic filters coated directly on the photodiodes. This photodiode system provides a spectral coverage from 0.1 to 80 nm with about 15 nm resolution. The other solar irradiance instrument is a silicon avalanche photodiode coupled with pulse height analyzer electronics. This avalanche photodiode package measures the XUV photon energy providing a solar spectrum from 50 to 12,400 eV (25 to 0.1 nm) with an energy resolution of about 50 eV. The fourth solar instrument is an XUV imager that images the sun at 17.5 nm with a spatial resolution of 20 arc-seconds. The airglow spectrograph measures the terrestrial FUV airglow emissions along the horizon from 125 to 160 nm with 0.2 nm spectral resolution. The photon-counting CODACON detectors are used for three of these instruments and consist of coded arrays of anodes behind microchannel plates. The one-dimensional and two-dimensional CODACON detectors were developed at CU by Dr. George Lawrence. The pre-flight and post-flight photometric calibrations were performed at our calibration laboratory and at the Synchrotron Ultraviolet Radiation Facility (SURF) at the National Institute of Standards and Technology (NIST) in Gaithersburg, Maryland.

Woods, Thomas N.↗

Interstellar Ice and Dust: The Feedstock of the Solar System

Studying the chemical and isotopic composition of interstellar ice and dust provides insight into the composition and chemical history of the solid bodies in the solar nebula and the nature of the material subsequently brought into the inner part of the solar system by comets and meteorites. It is now possible to probe the composition of these microscopic interstellar particles (some hundreds of light years away), thanks to substantial progress in two areas: astronomical spectroscopic techniques in the middle-infrared, the spectral region most diagnostic of composition; and laboratory simulations which realistically reproduce the critical conditions in various interstellar environments. High quality infrared spectra of many different astronomical sources, some associated with dark molecular clouds, and others in the diffuse interstellar medium (DISM) are now available. What comparisons of these spectra with laboratory spectra tell us about the complex organic components of these materials is the subject of this talk. Most interstellar material is concentrated in large molecular clouds where simple molecules are formed by gas phase and dust grain surface reactions. Gaseous species (except H2) striking the cold (10K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. One can compare spectra of the diffuse and dense interstellar medium with the spectra of analogs produced in the laboratory under conditions which mimic those in these different environments. In this way one can determine the composition and abundances of the major constituents present and place general constraints on the types and relative abundances of organics coating the grains. Ices in dense clouds contain H2O, CH3OH, CO, perhaps some NH3 and H2CO, as well as nitriles and ketones or esters. There is some evidence that the later, more complex species, are also present on the grains in the DISM. The evidence for these materials, in addition to carbon rich materials such as amorphous carbon, microdiamonds, and polycyclic aromatic hydrocarbons will be reviewed and the possible connection with meteoritic organics will be discussed.

Allamandola, L. J.↗

Astronomical Problems and Laboratory Solutions

Studying the chemical and isotopic composition of interstellar ice and dust provides insight into the composition and chemical history of the solid bodies in the solar nebula and the nature of the material subsequently brought into the inner part of the solar system by comets and meteorites. It is now possible to probe the composition of these microscopic interstellar particles (some hundreds of light years away), thanks to substantial progress in two areas: astronomical spectroscopic techniques in the middle-infrared, the spectral region most diagnostic of composition; and laboratory simulations which realistically reproduce the critical conditions in various interstellar environments. High quality infrared spectra of many different astronomical sources, some associated with dark molecular clouds, and others in the diffuse interstellar medium (DISM) are now available. What comparisons of these spectra with laboratory spectra tell us about the complex organic components of these materials is the subject of this talk. Most interstellar material is concentrated in large molecular clouds where simple molecules are formed by gas phase and dust grain surface reactions. Gaseous species (except H2) striking the cold (10K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. One can compare spectra of the diffuse and dense interstellar medium with the spectra of analogs produced in the laboratory under conditions which mimic those in these different environments. In this way one can determine the composition and abundances of the major constituents present and place general constraints on the types and relative abundances of organics coating the grains. Ices in dense clouds contain H2O, CH3OH, CO, perhaps some NH3 and H2CO, as well as nitriles and ketones or esters. there is some evidence that the later, more complex species, are also present on the grains in the DISM. The evidence for these materials, in addition to carbon rich materials such as amorphous carbon, microdiamonds, and polycyclic aromatic hydrocarbons will be reviewed and the possible connection with meteoritic organics will be discussed.

Allamandola, L. J.↗

A methodology for selection of solid desiccants in energy recovery ventilators

Controlling indoor humidity levels is essential for maintaining acceptable indoor air quality in buildings. The use of energy recovery ventilators (ERVs) is an energy-efficient way to regulate indoor air humidity. Fixed-bed regenerators and rotary wheels are widely used ERVs because of their high sensible and latent effectiveness. These ERVs are made of desiccant-coated substrates, which enable them to transfer moisture between the supply and exhaust air streams. However, the moisture transfer ability of ERVs depends on the physiochemical and sorption properties of desiccants. Extensive, full-scale experiments are required to determine the best desiccant material for these systems. This paper presents a simplified method of selecting suitable desiccant materials for ERVs. The methodology involves important characterization methods, literature correlations for performance prediction, and cost-effective testing methods prior to full-scale testing, and full-scale test methods are discussed in detail. Furthermore, the performance of a few newly derived materials is evaluated and compared with that of conventional desiccants such as silica gel and molecular sieves. The highest latent effectiveness was obtained for composite of super absorbent polymer (SAP) with potassium formate (SAP-HCO2K-50 %), all-polymer porous solid desiccant (APPSD) and metal organic framework (MOF)–MIL–101 (Cr), followed by activated carbon fibre felt (ACFF) Silica sol-LiCl30, SAP, silica gel, MOF–303, and molecular sieve. Researchers and manufacturers would benefit from the proposed methodology and presented data in developing new desiccant materials for ERV applications.

Energy recovery↗

Spatio-Spectral Characterization of Multipolar Plasmonic Modes of Au Nanorods via Tip-Enhanced Raman Scattering

Tip-enhanced Raman (TER) spectral images of 4-thiobenzonitrile-coated Au nanorods map the spatial profiles and trace the resonances of dipolar and multipolar plasmonic modes that are characteristic of the imaged particles. For any particular rod, we observe sequential transitions between high-order modes at low frequency shifts and lower-order modes at higher frequencies. We also notice that higher-order modes (up to $m$ = 4) are generally observed for long rods as compared to their shorter analogues, where longitudinal dipolar resonances ($m$ = 1) are observable. In effect, this research adds a new dimension to local optical field mapping via TERS, which we have previously explored. Not only can the magnitudes, vector components, local/nonlocal characters of local optical fields be imaged through molecular TERS, but spatially varying local optical resonances are also direct observables.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Three-in-One Hybrid Strategy for High-Performance Semiconducting Polymers Processed from Anisole

The development of semiconducting polymers with good processability in green solvents and competitive electrical performance is essential for realizing sustainable large-scale manufacturing and commercialization of organic electronics. A major obstacle is the processability-performance dichotomy that is dictated by the lack of ideal building blocks with balanced polarity, solubility, electronic structures, and molecular conformation. Herein, through the integration of donor, quinoid and acceptor units, an unprecedented building block, namely TQBT, is introduced for constructing a serial of conjugated polymers. The TQBT, distinct in non-symmetric structure and high dipole moment, imparts enhanced solubility in anisole—a green solvent—to the polymer TQBT-T. Furthermore, PTQBT-T possess a highly rigid and planar backbone owing to the nearly coplanar geometry and quinoidal nature of TQBT, resulting in strong aggregation in solution and localized aggregates in film. Remarkably, PTQBT-T films spuncast from anisole exhibit a hole mobility of 2.30 cm 2 V -1 s -1 , which is record high for green solvent-processable semiconducting polymers via spin-coating, together with commendable operational and storage stability. The hybrid building block emerges as a pioneering electroactive unit, shedding light on future design strategies in high-performance semiconducting polymers compatible with green processing and marking a significant stride towards ecofriendly organic electronics.

36 MATERIALS SCIENCE↗

Catalytic Chemical Recycling of Post-Consumer Polyethylene

Among commercial plastics, polyolefins are the most widely produced worldwide but have limited recyclability. Here, we report a chemical recycling route for the conversion of post-consumer high-density polyethylene (HDPE) into telechelic macromonomers suitable for circular reprocessing. Unsaturation was introduced into HDPE by catalytic dehydrogenation using an Ir-POCOP catalyst without an alkene acceptor. Cross-metathesis with 2-hydroxyethyl acrylate followed by hydrogenation transformed the partially unsaturated HDPE into telechelic macromonomers. The direct repolymerization of the macromonomers gave a brittle material due to the low overall weight-average molecular weight. Aminolysis of telechelic macromonomers with a small amount of diethanolamine increased the overall functionality. The resulting macromonomers were repolymerized through transesterification to generate a polymer with comparable mechanical properties to the starting post-consumer HDPE waste. Finally, depolymerization of the repolymerized material catalyzed by an organic base regenerated the telechelic macromonomers, thereby allowing waste polyethylene materials to enter a chemical recycling pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

LDEF materials: An overview of the interim findings

The flight and retrieval of the National Aeronautics and Space Administration's Long Duration Exposure Facility (LDEF) provided an opportunity for the study of the low-Earth orbit (LEO) environment and long-duration space environmental effect (SEE) on materials that are unparalleled in the history of the U.S. space program. The 5.8-year flight of LDEF greatly enhanced the potential value of materials data from LDEF to the international SEE community, compared to that of the original 1-year flight plan. The remarkable flight attitude stability of LDEF enables specific analyses of various individual and combined effects of LEO environmental parameters on identical materials of the same space vehicle. NASA recognized the potential by forming the LDEF Space Environmental Effects on Materials Special Investigation Group (MSIG) to address the greatly expanded materials and LEO space environment parameter analysis opportunities available in the LDEF structure, experiment trays, and corollary measurements, so that the combined value of all LDEF materials data to current and future space missions will be assessed and documented. This paper provides an overview of the interim LDEF materials findings of the Principal Investigators and the Materials Special Investigation Group. These revelations are based on observations of LEO environmental effects on materials made in-space during LDEF retrieval and during LDEF tray deintegration at the Kennedy Space Center, and on findings of approximately 1.5 years of laboratory analyses of LDEF materials by the LDEF materials scientists. These findings were extensively reviewed and discussed at the MSIG-sponsored LDEF Materials Workshop '91. The results are presented in a format which categorizes the revelations as 'clear findings' or 'confusing/unexplained findings' and resultant needs for new space materials developments and ground simulation testing/analytical modeling in seven categories: environmental parameters and data bases; LDEF contamination; thermal control coatings and protective treatments; polymers and films; polymer-matrix composites; metals, ceramics, and optical materials; and systems-related materials. General outlines of findings of the other LDEF Special Investigation Groups (Ionizing Radiation, Meteoroid and Debris, and Systems) are also included. The utilization of LDEF materials data for future low-earth orbit missions is also discussed, concentrating on Space Station Freedom. Some directions for continuing studies of LDEF materials are outlined. In general, the LDEF data is remarkable consistent; LDEF will provide a 'benchmark' for materials design data bases for satellites in low-Earth orbit. Some materials were identified to be encouragingly resistant to LEO SEE for 5.8-years; other 'space qualified' materials displayed significant environmental degradation. Molecular contamination was widespread; LDEF offers an unprecedented opportunity to provide a unified perspective of unmanned LEO spacecraft contamination mechanisms. New material development requirements for long-term LEO missions have been identified and current ground simulation testing methods/data for new, durable materials concepts can be validated with LDEF results. LDEF findings are already being integrated into the design of Space Station Freedom.

Stein, Bland A.↗