Hyperspectral reflectance-based phenotyping for quantitative genetics in crops: Progress and challenges
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Soil carbon dioxide (CO 2 ) emissions from the field of corn (Zea mays L.) play an important role in global warming. This study investigated temporal variability of soil CO 2 fluxes (R s ) with soil temperature (T s ) and moisture (θ) and built DAYCENT models for predicting future impacts of climate changes on R s using the measured high-frequency data. R s trend was tested by Mann–Kendall and Sen Estimator. Predicted R s s under different climate scenarios were compared using Parallel-line Analysis. Herein, the findings indicated that daily R s exponentially increased with T s constrained by θ. During the θ of 27–31%, there was a strong exponential relationship between R s and T s , but the relationship was weaker for the θ of 38–41% and 22–26%. Soil environmental index (SEI, T s × θ) significantly impacted R s with linear regression R s 0.5 = 0.4599 + 0.002059 × SEI in 2008, 2009 and 2011. At the diurnal scale, there were different trends in R s s and relationships among R s and T s and θ in different years. Predicted yearly R s s, root R s s and corn yield in 2014–2049 increased with an increase in temperature scenarios, but the R s s significantly increased as temperature rose by 1°C or higher. Predicted yearly R s s, root R s s and yield reduced with precipitation scenario increase, and the root R s s and yield significantly diminished as precipitation increased by 15 and 30%. Predicted yearly R s from cornfields had a significantly increasing trend. Future research is needed to explore methods for mitigating cornfield R s and evaluating sensitivities of different cropland R s s to temperature changes.
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.
Human histidine triad nucleotide binding protein 1 (hHint1) is classified as an efficient nucleoside phosphoramidase and acyl-adenosine monophosphate hydrolase. Human Hint1 has been shown to be essential for the metabolic activation of nucleotide antiviral pronucleotides (i.e., proTides), such as the FDA approved hepatitis C drug, sofosbuvir. The active site of hHint1 comprises an ensemble of strictly conserved histidines, including nucleophilic His112. To structurally investigate the mechanism of hHint1 catalysis, herein we have designed and prepared nucleoside thiophosphoramidate substrates that are able to capture the transiently formed nucleotidylated-His112 intermediate (E*) using time-dependent crystallography. Utilizing a catalytically inactive hHint1 His112Asn enzyme variant and wild-type enzyme, the enzyme–substrate (ES 1 ) and product (EP 2 ) complexes were also cocrystallized, respectively, thus providing a structural map of the reaction trajectory. On the basis of these observations and the mechanistic necessity of proton transfers, proton inventory studies were carried out. Although we cannot completely exclude the possibility of more than one proton in flight, the results of these studies were consistent with the transfer of a single proton during the formation of the intermediate. Interestingly, structural analysis revealed that the critical proton transfers required for intermediate formation and hydrolysis may be mediated by a conserved active site water channel. Taken together, our results provide mechanistic insights underpinning histidine nucleophilic catalysis in general and hHint1 catalysis, in particular, thus aiding the design of future proTides and the elucidation of the natural function of the Hint family of enzymes.
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During routine operation, electrically percolating nanocomposites are subjected to high voltages, leading to spatially heterogeneous current distribution. The heterogeneity implies localized self-heating that may (self-consistently) reroute the percolation pathways and even irreversibly damage the material. In the absence of experiments that can spatially resolve the current distribution and a nonlinear percolation model suitable to interpret them, one relies on empirical rules and safety factors to engineer these materials. In this paper, we use ultrahigh resolution thermo-reflectance imaging, coupled with a new imaging processing technique, to map the spatial distribution ΔT(x, y; I) and histogram f(ΔT) of temperature rise due to self-heating in two types of 2D networks (percolating and copercolating). Remarkably, we find that the self-heating can be described by a simple two-parameter Weibull distribution, even under voltages high enough to reconfigure the percolation pathways. Given the generality of the phenomenological argument supporting the distribution, other percolating networks are likely to show similar stress distribution in response to sufficiently large stimuli. Furthermore, the spatial evolution of the self-heating of network was investigated by analyzing the spatial distribution and spatial correlation, respectively. An estimation of degree of hotspot clustering reveals a mechanism analogous to crystallization physics. Lastly, the results should encourage nonlinear generalization of percolation models necessary for predictive engineering of nanocomposite materials.
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Corn stover fractions (leaves, cobs, and stalks) were studied for enzymatic digestibility after pretreatment with a white rot fungus, Ceriporiopsis subvermispora. Among the three fractions, leaves had the least recalcitrance to fungal pretreatment and the lignin degradation reached 45% after 30 days of pretreatment. The lignin degradation of stalks and cobs was similar but was significantly lower than that of leaves (p < 0.05). For all fractions, xylan and glucan degradation followed a pattern similar to lignin degradation, with leaves having a significantly higher percentage of degradation (p < 0.05). Hydrolytic enzyme activity also revealed that the fungus was more active in the degradation of carbohydrates in leaves. As a result of fungal pretreatment, the highest sugar yield, however, was obtained with corn cobs.
The average spatial dimensions between major biopolymers within the plant cell wall can be resolved using a solid-state NMR technique referred to as a {sup 13}C cross-polarization (CP) SELDOM (selectively by destruction of magnetization) with a mixing time delay for spin diffusion. Selective excitation of specific aromatic lignin carbons indicates that lignin is in close proximity to hemicellulose followed by amorphous and finally crystalline cellulose. {sup 13}C spin diffusion time constants (T{sub SD}) were extracted using a two-site spin diffusion theory developed for {sup 13}C nuclei under magic angle spinning (MAS) conditions. These time constants were then used to calculate an average lower-limit spin diffusion length between chemical groups within the plant cell wall. The results on untreated {sup 13}C enriched corn stover stem reveal that the lignin carbons are, on average, located at distances {approx}0.7-2.0 nm from the carbons in hemicellulose and cellulose, whereas the pretreated material had larger separations.
We investigated the effect of intermediate cylindrical confinement with locally repulsive walls on the segmental and entanglement dynamics of a polymer melt by quasielastic neutron scattering. As a reference, we measured the corresponding polymer melt under identical conditions. The locally repulsive confinement was realized by hydrophilic anodic alumina nanopores with a diameter of 20 nm. The end-to-end distance of the hydrophobic infiltrated polyethylene-alt-propylene was close to this diameter. In the case of hard wall repulsion with negligible local attraction, several simulations predicted an acceleration of segmental dynamics close to the wall. Other than in attractive or neutral systems, where the segmental dynamics is slowed down, we found that the segmental dynamics in the nanopores is identical to the local mobility in the bulk. Even under very careful scrutiny, we could not find any acceleration of the surface-near segmental motion. On the larger time scale, the neutron spin-echo experiment showed that the Rouse relaxation was not altered by confinement effects. Moreover, the entanglement dynamics was not affected. Thus at moderate confinement conditions, facilitated by locally repulsive walls, the dynamics remains as in the bulk melt, a result that is not so clear from simulations.
Electromigration (EM) is a phenomenon whereby the flow of current in metal wires moves the underlying atoms, potentially inducing electronic interconnect failures. The continued decrease in commercial lithographically defined feature sizes means that EM presents an increasing risk to the reliability of modern electronics. To mitigate these risks, it is important to look for novel mechanisms to extend lifetime without forfeiting miniaturization. Typically, only the overall increase in the interconnect resistance and failure voltage are characterized. However, if the current flows non-uniformly, spatially resolving the resulting hot spots during electromigration aging experiments may provide better insights into the fundamental mechanisms of this process. Here in this study, we focus on aluminum interconnects containing asymmetric reservoir and void pairs with contact pads on each end. Such reservoirs are potential candidates for self-healing. Thermoreflectance imaging was used to detect hot spots in electrical interconnects at risk of failure as the voltage was gradually increased. It reveals differential heating with increasing voltage for each polarity. We find that while current flow going from a constriction to a reservoir causes a break at the void, the identical structure with the opposite polarity can sustain higher current (J = 21 × 10 6 A/cm 2 ) and more localized joule heating and yet is more stable. Ultimately, a break takes place at the contact pad where the current flows from narrow interconnect to larger pads. In summary, thermoreflectance imaging with submicron spatial resolution provides valuable information about localized electromigration evolution and the potential role of reservoirs to create more robust interconnects.
With new data from the Galactic O-Star Spectroscopic Survey, we confirm and expand the ONn category of late-O, nitrogen-enriched (N), rapidly rotating (n) giants. In particular, we have discovered two 'clones' (HD 102415 and HD 117490) of one of the most rapidly rotating O stars previously known (HD 191423, 'Howarth's Star'). We compare the locations of these objects in the theoretical H-R diagram to those of slowly rotating ON dwarfs and supergiants. All ON giants known to date are rapid rotators, whereas no ON dwarf or supergiant is, but all ON stars are small fractions of their respective spectral-type/luminosity-class/rotational subcategories. The ONn giants, displaying both substantial processed material and high rotation at an intermediate evolutionary stage, may provide significant information about the development of these properties. They may have preserved high initial rotational velocities or may have been spun up by terminal-age main-sequence core contraction; alternatively, and perhaps more likely, they may be products of binary mass transfer. At least some of them are also runaway stars.
Abstract Climate benefit assessments of bioenergy crops often focus on biogeochemical impacts, paying little if any attention to biogeophysical impacts. However, land conversions required for large-scale bioenergy crop production are substantial and may directly affect the climate by altering surface energy balance. In the US, such land conversions are likely to be met in part by converting Conservation Reserve Program (CRP) grassland to bioenergy crops. Here, we converted three 22 year old CRP smooth brome grass fields into no-till corn, switchgrass, or restored prairie bioenergy crops. We assessed the biogeophysical climate impact of the conversions using albedo changes relative to unconverted reference CRP grassland. The corn and perennial fields had higher annual albedo than the grassland they replaced—causing cooling of the local climate. The cooling of the corn field occurred solely during the non-growing season—especially when surfaces were snow-covered, whereas the cooling of the perennial fields was more prominent during the growing season. Compared to biogeochemical impacts with fossil fuel offsets for the same land conversions over eight years, the annual albedo-induced climate benefits add ∼35% and ∼78% to the annual biogeochemical benefits provided from the switchgrass and restored prairie fields, respectively, and offset ∼3.3% of the annual greenhouse gas (GHG) emissions from the corn field. We conclude that albedo-induced climate mitigation from conversion of CRP lands to perennial but not annual bioenergy crops can be substantial, and future climate impact assessments of bioenergy crops should include albedo changes in addition to GHG balances in order to better inform climate policies.
Understanding agroecosystem carbon (C) cycle response to climate change and management is vital for maintaining their long-term C storage. We demonstrate this importance through an in-depth examination of a ten-year eddy covariance dataset from a corn–corn–soybean crop rotation grown in the Midwest United States. Ten-year average annual net ecosystem exchange (NEE) showed a net C sink of –0.39 Mg C ha –1 yr –1 . However, NEE in 2014 and 2015 from the corn ecosystem was 3.58 and 2.56 Mg C ha –1 yr –1 , respectively. Most C loss occurred during the growing season, when photosynthesis should dominate and C fluxes should reflect a net ecosystem gain. Partitioning NEE into gross primary productivity (GPP) and ecosystem respiration (ER) showed this C 'burp' was driven by higher ER, with a 51% (2014) and 57% (2015) increase from the ten-year average (15.84 Mg C ha –1 yr –1 ). GPP was also higher than average (16.24 Mg C ha –1 yr –1 ) by 25% (2014) and 37% (2015), but this was not enough to offset the C emitted from ER. This increased ER was likely driven by enhanced soil microbial respiration associated with ideal growing season climate, substrate availability, nutrient additions, and a potential legacy effect from drought.
Here, we present an estimate of the characteristic wavelengths of the evanescent modes, which define the main contribution to the thermal part of the Casimir force. This estimate is more precise than the one in the preceding Comment by Bimonte et al.[Phys. Rev. A 84, 036501 (2011)]. The wavelengths we derive are indeed smaller than the sizes of the interacting bodies. We also discuss the results of several experiments on the thermal effects in the Casimir force.
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