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At least 1,513 records · Page 84

Perovskite Photocatalytic CO 2 Reduction or Photoredox Organic Transformation?

Abstract Metal‐halide perovskites have been explored as photocatalysts for CO 2 reduction. We report that perovskite photocatalytic CO 2 reduction in organic solvents is likely problematic. Instead, the detected products (i.e., CO) likely result from a photoredox organic transformation involving the solvent. Our observations have been validated using isotopic labeling experiments, band energy analysis, and new control experiments. We designed a typical perovskite photocatalytic setup in organic solvents that led to CO production of up to ≈1000 μmol g −1 h −1 . CO 2 reduction in organic solvents must be studied with extra care because photoredox organic transformations can produce orders of magnitude higher rate of CO or CH 4 than is typical for CO 2 reduction routes. Though CO 2 reduction is not likely to occur, in situ CO generation is extremely fast. Hence a suitable system can be established for challenging organic reactions that use CO as a feedstock but exploit the solvent as a CO surrogate.

14 SOLAR ENERGY↗

Methods for suspension culture, protoplast extraction, and transformation of high‐biomass yielding perennial grass Arundo donax

Abstract Arundo donax L. is a promising biofuel feedstock in the Mediterranean region. Despite considerable interest in its genetic improvement, Arundo tissue culture and transformation remains arduous. The authors developed methodologies for cell‐ and tissue culture and genetic engineering in Arundo . A media screen was conducted, and a suspension culture was established using callus induced from stem axillary bud explants. DBAP medium, containing 9 µM 2,4‐D and 4.4 µM BAP, was found to be the most effective medium among those tested for inducing cell suspension cultures, which resulted in a five‐fold increase in tissue mass over 14 days. In contrast, CIM medium containing 13 µM 2,4‐D, resulted in just a 1.4‐fold increase in mass over the same period. Optimized suspension cultures were superior to previously‐described solidified medium‐based callus culture methods for tissue mass increase. Suspension cultures proved to be very effective for subsequent protoplast isolation. Protoplast electroporation resulted in a 3.3 ± 1.5% transformation efficiency. A dual fluorescent reporter gene vector enabled the direct comparison of the CAMV 35S promoter with the switchgrass ubi2 promoter in single cells of Arundo . The switchgrass ubi2 promoter resulted in noticeably higher reporter gene expression compared with that conferred by the 35S promoter in Arundo .

Pigna, Gaia↗

Composition-Mediated Order-Disorder Transformation in FePt Nanoparticles

Thumbnail image of graphical abstract Heat-treated alloy FePt nanoparticles transform into L10 FePt and mixed L10/L12 FePt3 intermetallic phases. Enrichment in Pt in some nanoparticles, rather than intrinsic thermodynamic effects, drives phase segregation. FePt nanoparticles of uniform, equimolar composition are expected to transform into phase-pure, highly ordered L10 FePt nanoparticles.

Johnston-Peck, Aaron C.↗

Fast redox switches lead to rapid transformation of goethite in humid tropical soils: A Mössbauer spectroscopy study

Abstract Humid tropical forest soils experience frequent rainfall, which limits oxygen diffusion and creates redox heterogeneity in upland soils. In this study we gauged the effect of short‐term anoxic conditions on Fe mineralogy of relatively Fe‐ and C‐rich surface soils (C/Fe mole ratio ∼5) from a humid tropical forest in Puerto Rico. Soils subjected to 4‐d oxic/anoxic oscillation were characterized by selective chemical extractions, Mössbauer spectroscopy (MBS), and X‐ray diffraction. Chemical extraction data suggested that rapidly switching redox conditions had subtle effects on bulk Fe mineralogy. Mössbauer, on the other hand, indicated that (a) the soil Fe is a mixture of goethites of varying characteristics with minor contributions from ferrihydrite (<5%) and Fe(III)‐organic matter (OM) phases (∼10%), and (b) anoxic conditions rapidly transformed all forms of goethite to relatively stable Fe oxides. Such fast changes in goethite features could be due to rapid depletion and sorption of bio‐released structural Al or sorbed OM onto residual soil components. The rapid temporal changes in MBS parameters and corresponding pore water nominal oxidation state of C values suggest that Fe‐C transformations in these upland tropical soils are complex and intricately coupled. A comprehensive understanding of the fate of Fe, Al, and OM (Fe‐organic moieties) during redox switches and concurrent changes in pore water chemistry is critical for development of robust transport models in humid tropical soils, which are subject to episodic low‐redox events.

54 ENVIRONMENTAL SCIENCES↗

Diffusional and Partitionless Ferrite‐to‐Austenite Phase Transformations during Intercritical Annealing of Medium‐Mn Steels

Experimental research on intercritical annealing of a cold‐rolled Fe–7Mn steel with ultralow carbon concentration is presented, providing insight into the efficacy of generating Mn‐enriched austenite during relatively short (≈1000 s) heat treatments compared with batch annealing, as well as the phase transformation mechanisms that can occur during intercritical annealing. It is shown through both bulk characterization and electron microscopy in conjunction with energy‐dispersive X‐ray spectroscopy that Mn partitioning to austenite occurs via diffusional, partitioning growth of austenite during these shorter treatments and that the intercritical temperature influences the level of Mn enrichment in austenite. Evidence of massive (partitionless) and diffusional (partitioning) transformations of ferrite to austenite occurring simultaneously in a single sample are also shown along with a thermodynamic rationale for this occurrence, which is suggested to be related to residual Mn‐banding that develops during solidification.

Mueller, Josh J.↗

Enhancing Mechanical Properties of Carbon–Silicon Steel through Two–Stage Quenching and Partitioning with Bainitic Transformation: Ultimate Tensile Strength of 1875 MPa and Total Elongation of 8.03%

To achieve the desired microstructural properties, the ongoing development and innovation in new structural steels require novel thermal processing. This study aims to improve the mechanical properties of a commercial spring carbon–silicon steel by tailoring its microstructure through a process involving quenching and partitioning (Q&P) followed by bainitic transformation. A two–stage Q&P process is proposed to generate a nanoscale dispersion of stable retained austenite and carbides within the tempered martensite and bainite microstructure. The resulting tensile properties demonstrate a yield strength of 1280 MPa, an ultimate tensile strength of 1875 MPa, and a total elongation of 8.03%. These values surpass those of conventional spring 9254 steel, highlighting the effectiveness of the thermal treatment design. Microstructure analysis reveals the presence of tempered martensite, bainite sheaves, nanoscale carbides, and aggregates of retained austenite. Moreover, the resulting body–centered cubic matrix exhibits minimal lattice tetragonality of ≈1.0051, coupled with stable retained austenite featuring a carbon concentration of ≈3.42 ± 0.5 wt%, resulting in outstanding strength–ductility properties. In conclusion, these findings indicate that the proposed two–stage Q&P process, followed by bainitic transformation, significantly enhances the mechanical properties of carbon–silicon steels, making it a promising candidate for high–performance spring applications.

36 MATERIALS SCIENCE↗

The Role of Fuels in Transforming Energy End-Use in Buildings and Industrial Processes

This book examines what role fuels have in the transformation of end-use in buildings and industrial processes. Energy efficient technologies are necessary to lower the carbon footprint for a transition towards clean energy in a sustainable manner. Efficient utilization of primary energy resources including renewables to support the current and future energy needs while targeting grid resiliency, energy and environmental security, at an affordable cost is of significant value. Analysis of configurations consisting of heat pumps, fuel driven thermal providers and power systems is presented. Sensitivity of electrical grid's carbon intensity towards carbon footprint in comparison with fuel driven technologies is necessary to recognize the true value proposition of currently available energy solutions for different end consumers. Similarly, the role of low carbon, zero carbon, and carbon negative fuels such as power to gas, power to liquid, hydrogen, biogas, etc. in conjunction with polygeneration technologies are discussed. Transformation of the primary energy resources from conventional fossil fuels to renewable fuels or electricity will have a significant impact on the overall carbon footprint of various end use sectors, including buildings. Hence, this book also examines two different scenarios focused on sensitivity of the pace of decarbonization of electrical grid and fuel supply on operational energy related carbon emissions.

Cheekatamarla, Praveen↗

A note on large gauge transformations in double field theory

Here, we give a detailed proof of the conjecture by Hohm and Zwiebach in double field theory. Our result implies that their proposal for large gauge transformations in terms of the Jacobian matrix for coordinate transformations is, as required, equivalent to the standard exponential map associated with the generalized Lie derivative along a suitable parameter.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Identification and Characterization of Herbicide Penoxsulam Transformation Products in Aqueous Media by UPLC-QTOF-MS

Photodegradation is an important non-biodegradation process of pesticide degradation in aquatic environments. In this study, the effect of different forms of nitrogen on the photodegradation kinetics of penoxsulam was investigated. The photodegradation of penoxsulam was accelerated by NO{sup 3−} and NO{sup 2−} but was not affected by NH{sup 4+}. Ultra-high-performance liquid chromatography coupled with time-of-flight mass spectrometry was used to separate and identify the transformation products (TPs)converted by photodegradation of penoxsulam in an aqueous solution under UV–Vis (290–800 nm) irradiation. Seven major transformation products were identified based on mass spectral data. The structure was determined by elemental composition calculations, comparison of structural analogs, and existing literature. The main pathways of photodegradation were found to be sulfonamide bond cleavage, rearrangement, triazole ring cleavage, and hydroxylation. These findings are critical to elucidate the environmental fate of penoxsulam in aquatic ecosystems and provide a basis for further environmental risk assessment.

54 ENVIRONMENTAL SCIENCES↗

Rational development of transformation in Clostridium thermocellum ATCC 27405 via complete methylome analysis and evasion of native restriction–modification systems

A major barrier to both metabolic engineering and fundamental biological studies is the lack of genetic tools in most microorganisms. One example is Clostridium thermocellum ATCC 27405 T , where genetic tools are not available to help validate decades of hypotheses. A crucial barrier to DNA transformation is restriction–modification systems, which defend against foreign DNA methylated differently than the host. To determine the active restriction–modification systems in this strain, we performed complete methylome analysis via single-molecule, real-time sequencing to detect 6-methyladenine and 4-methylcytosine and the rarely used whole-genome bisulfite sequencing to detect 5-methylcytosine. Multiple active systems were identified, and corresponding DNA methyltransferases were expressed from the Escherichia coli chromosome to mimic the C. thermocellum methylome. Plasmid methylation was experimentally validated and successfully electroporated into C. thermocellum ATCC 27405. This combined method enabled genetic modification of the C. thermocellum -type strain and acts as a blueprint for transformation of other non-model microorganisms.

59 BASIC BIOLOGICAL SCIENCES↗

Riverine dissolved organic matter transformations increase with watershed area, water residence time, and Damköhler numbers in nested watersheds

Abstract Quantifying the relative influence of factors and processes controlling riverine ecosystem function is essential to predicting future conditions under global change. Dissolved organic matter (DOM) is a fundamental component of riverine ecosystems that fuels microbial food webs, influences nutrient and light availability, and represents a significant carbon flux globally. The heterogeneous nature of DOM molecular composition and its propensity for interaction (i.e., functional diversity) can characterize riverine ecosystem function across spatiotemporal scales. To investigate fundamental drivers of DOM diversity, we collected seasonal water samples from 42 nested locations within five watersheds spanning multiple watershed sizes (~ 5 to 30,000 km 2 ) across the United States. Patterns in DOM molecular richness, aromaticity, relative abundance of N-containing formulas, and putative biochemical transformations derived from high-resolution mass spectrometry were assessed across gradients of explanatory variables associated with watershed characteristics (e.g., watershed area, water residence time, land cover). We found that putative biochemical transformations were more strongly related to explanatory variables across watersheds than common bulk DOM parameters and that watershed area, surface water residence time and derived Damköhler numbers representing DOM reactivity timescales were strong predictors of DOM diversity. The data also indicate that catchment-specific land cover factors can significantly influence DOM diversity in diverging directions. Overall, the results highlight the importance of considering water residence time and land cover when interpreting longitudinal patterns in DOM chemistry and the continued challenge of identifying generalizable drivers that are transferable across watershed and regional scales for application in Earth system models. This work also introduces a Findable Accessible Interoperable Reusable (FAIR) dataset (> 300 samples) to the community for future syntheses.

54 ENVIRONMENTAL SCIENCES↗

Hybrid Ultrasonic TOFD Imaging of Weld Flaws Using Wavelet Transforms and Image Registration

Ultrasonic time of flight diffraction (TOFD) is an effective weld crack inspection technique. Due to the intensity of diffraction wave is rather weak compared with the lateral wave and the bottom echo wave, thus the signal-to-ratio (SNR) of TOFD image is low. A new dichotomous method is comprised of two steps that contains wavelet shrinkage and image registration is proposed in this paper to reduce the noise and improve the resolution of TOFD images as well. In order to evaluate the reliability of our proposed method in this paper, we have established the experiment system, and sampled a number of TOFD data with random distribution of noise characteristics. We adopted one-dimension wavelet transform and two-dimension wavelet transform in the very beginning of the first step of the proposed algorithm respectively. The SNR of the result obtained in this step is improved significantly compared with the classic algorithms. Next, the image registration is applied. After the registered images have been added to form a new one, then it comes to the final result that shows not only the SNR but also the definition of the image is enhanced effectively.

42 ENGINEERING↗

Multi-segment Winding Application for Axial Short Circuit Force Reduction Under Tap Changer Operation in HTS Transformers

High-temperature superconducting (HTS) transformers have remarkable appealing advantages over conventional ones. But higher brittleness of HTS windings with respect to copper windings makes HTS transformers more vulnerable in short circuit and inrush current situations. During tap changer operation, appreciable asymmetry and non-uniform distribution of ampere-turn along the windings causes high axial component of short circuit forces and makes the situation more severe. In this paper, multi-segment winding method is employed for reduction of axial short circuit forces. An analytical method is presented for calculation of axial component of short circuit forces under tap changer operation. Analytical method shows that with utilizing HLHLHLH asymmetrical multi-segment windings, during tap changer operation, the axial component of short circuit forces reduces significantly. The results of the analytical method are compared with the results of finite element method (FEM) model simulations, and the consistency is demonstrated.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A{sub 1}-Regularity and Boundedness of Riesz Transforms in Banach Lattices of Measurable Functions

Let X be a Banach lattice of measurable functions on ℝ{sup n} × Ω having the Fatou property. We show that the boundedness of all Riesz transforms R{sub j} in X is equivalent to the boundedness of the Hardy–Littlewood maximal operator M in both X and X′, and thus to the boundedness of all Calderón–Zygmund operators in X. We also prove a result for the case of operators between lattices: If Y ⊃ X is a Banach lattice with the Fatou property such that the maximal operator is bounded in Y ′, then the boundedness of all Riesz transforms from X to Y is equivalent to the boundedness of the maximal operator from X to Y , and thus to the boundedness of all Calderón–Zygmund operators from X to Y .

97 MATHEMATICS AND COMPUTING↗

Transformation of amplification and attenuation through PT-symmetry structure under modulation of resonators

In order to achieve the transformation of amplification and attenuation with one device, we design a parity-time—symmetry structure through resonator modulation. We use the transfer matrix method to study the optical properties of the designed structure. The structure performs amplification along one incidence direction, and attenuation by absorption along the other incidence direction. The contrast of amplification and attenuation, and the corresponding bandwidth can be modulated through the structure parameters. An optimized structure is obtained with the transformation of large amplification and perfect absorption.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Phase transformations in Cd–Ni nanostructured system at elevated temperatures

Using X-ray diffraction (both in vacuum and in air), derivatomass-spectrometry and thermo-programmed oxidation, phase transformations in nanostructured Cd–Ni system occurring while heating up 720 °C were described. These metal powders were obtained by joint reduction from aqueous solutions of salts with hydrazine. When study their composition, earlier unknown phases were detected (intermetallide CdNi{sub 3} and solid solution Cd{sub x}Ni{sub 1–x} with face centered cubic structure) and among the known intermetallides (Cd{sub 5}Ni and CdNi), only Cd{sub 5}Ni was found. As a consequence, phase transformations in the obtained nanostructured powders were remarkably different from those present on the Cd–Ni phase diagram. The intermediates and FCC phase decompose independently with formation of individual initial components (Cd and Ni) without intermediate product. At relatively high Cd concentration in the system, intermediate CdNi{sub 3} phase formation from Cd{sub 5}Ni and Cd{sub x}Ni{sub 1–x} phases, which are polar opposites in composition, is possible. The decomposition temperatures of Cd{sub 5}Ni and melting point of Cd in the nanostructured state were lower than those specified by the phase diagram by 170 and 70 °C, respectively, which well corresponded to the concept of effective (high) temperatures attributed to the nanostructured systems due to the energy saturation of the con stituent nanocrystallites.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

On the Structural Transformation of Ni/BaH 2 During a N 2 -H 2 Chemical Looping Process for Ammonia Synthesis: A Joint In Situ Inelastic Neutron Scattering and First-Principles Simulation Study

The demand for decarbonizing the ammonia industry by using renewable energy has invoked increasing research interests into catalyst development for effective N 2 reduction under mild conditions. Hydride-based materials are among some of the emerging catalysts for ammonia synthesis at ambient pressure and low temperatures (< 673 K). A recent chemical looping process based on Ni/BaH 2 showed the most promise as it can realize ammonia production at a temperature as low as 373 K and under ambient pressure. However, the chemical transformation of the hydride catalyst at the molecular level remains unclear in this process. Here, we report detailed in situ neutron spectroscopy and diffraction investigations along with first-principles simulations on the structural transformation of Ni/BaH 2 during the nitridation and hydrogenation steps in the chemical looping process for ammonia synthesis. It was shown that a ball-milling process of the starting Ni/BaH 2 could significantly decrease the size of BaH 2 and increase the density of defects, thus potentially enhancing the reactivity of the hydride. The evolution from BaH 2 to barium imide (BaNH) was evidenced in the inelastic neutron scattering (INS) and neutron diffraction results during the N 2 reaction step. During the hydrogenation study, in addition to the recovery of BaH 2 , a possible intermediate species, N-deficient barium imide, was also detected. In comparing the N 2 and H 2 reaction steps, the neutron results indicate that the hydrogenation step appears more difficult than the nitridation step, confirming the facile N 2 fixation property of Ni/BaH 2 catalyst in ammonia synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization of the Martensitic Transformation in NiPtAl Alloy Using Digital Holographic Imaging

Surface reliefs due to phase transformations in a 56.8Ni-5.6Pt-37.6Al at. pct alloy were characterized in situ using digital holographic imaging during thermal cycling from room temperature up to 405 K (132 °C). The 3D images of the surface revealed that the austenite plates formed during heating are exactly the same for each cycle, which is not the case for the martensite plates formed during cooling. The martensite start temperature was found to vary by up to ~ 20 K from one grain to another within the same specimen. The absence of Ni 3 Al γ' precipitates, due to the relatively high Al content, results in the propagation of the martensitic transformation over grains up to a millimeter in size. Bright-field optical imaging showed the formation of large martensite plates in some grains, with cracks perpendicular to these plates, upon cycling. Cracks were also observed at grain boundaries and could be related to the height variations across the grain boundaries.

36 MATERIALS SCIENCE↗