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At least 1,333 records · Page 74

Effect of Isomeric Structures of Branched Cyclic Hydrocarbons on Densities and Equation of State Predictions at Elevated Temperatures and Pressures

The cis and trans conformation of a branched cyclic hydrocarbon affects the packing and, hence, the density, exhibited by that compound. Reported here are density data for branched cyclohexane (C6) compounds including methylcyclohexane, ethylcyclohexane (ethylcC6), cis-1,2-dimethylcyclohexane (cis-1,2), cis-1,4-dimethylcyclohexane (cis-1,4), and trans-1,4-dimethylcyclohexane (trans-1,4) determined at temperatures up to 525 K and pressures up to 275 MPa. Of the four branched C6 isomers, cis-1,2 exhibits the largest densities and the smallest densities are exhibited by trans-1,4. The densities are modeled with the Peng–Robinson (PR) equation of state (EoS), the high-temperature, high-pressure, volume-translated (HTHP VT) PREoS, and the perturbed chain, statistical associating fluid theory (PC-SAFT) EoS. Model calculations highlight the capability of these equations to account for the different densities observed for the four isomers investigated in this study. The HTHP VT-PREoS provides modest improvements over the PREoS, but neither cubic EoS is capable of accounting for the effect of isomer structural differences on the observed densities. The PC-SAFT EoS, with pure component parameters from the literature or from a group contribution method, provides improved density predictions relative to those obtained with the PREoS or HTHP VT-PREoS. However, the PC-SAFT EoS, with either set of parameters, also cannot fully account for the effect of the C6 isomer structure on the resultant density.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sustained Nonphotochemical Quenching Shapes the Seasonal Pattern of Solar-Induced Fluorescence at a High-Elevation Evergreen Forest

Traditional methods of carbon monitoring in mountainous regions are challenged by complex terrain. Recently, solar-induced fluorescence (SIF) has been found to be an indicator of gross primary production (GPP), and the increased availability of remotely sensed SIF provides an opportunity to estimate GPP across the Western United States. Although the empirical linkage between SIF and GPP is strong, the current mechanistic understanding of this linkage is incomplete and depends upon changes in leaf biochemical processes in which absorbed sunlight leads to photochemistry, heat (via nonphotochemical quenching [NPQ]), fluorescence, or tissue damage. An improved mechanistic understanding is necessary to leverage SIF observations to improve representation of ecosystem processes within land surface models. Here we included an improved fluorescence model within the Community Land Model, Version 4.5 (CLM 4.5), to simulate seasonal changes in SIF at a subalpine forest in Colorado. We found that when the model accounted for sustained NPQ, this provided a larger seasonal change in fluorescence yield leading to simulated SIF that more closely resembled the observed seasonal pattern (Global Ozone Monitoring Experiment-2 [GOME-2] satellite platform and a tower-mounted spectrometer system). We found that an acclimation model based on mean air temperature was a useful predictor for sustained NPQ. Although light intensity was not an important factor for this analysis, it should be considered before applying the sustained NPQ and SIF to other cold climate evergreen biomes. More leaf-level fluorescence measurements are necessary to better understand the seasonal relationship between sustained and reversible components of NPQ and to what extent that influences SIF.

54 ENVIRONMENTAL SCIENCES↗

Subseasonal Variability of Elevated Dust Concentrations Over South Florida

Dust mass concentrations have been measured daily at Miami, Florida, in the summer months, and biweekly throughout the remaining months, since 1974. The 43-year record of dust mass concentrations indicate large daily, seasonal, and interannual variations, with most of the dust arriving within 5–8 episodes each summer. On average, dust arrives to Miami, Florida, 10 days after emission from North Africa, with measured concentrations depending on characteristics of the lower free-tropospheric winds due to the vast travel distance. Daily dust mass concentrations from July and August, the months that contribute the most to the annual mean, are used to characterize the synoptic conditions most favorable for dust transport. Two key regions are linked with the highest daily dust mass concentrations above Miami: (i) easterly winds, averaged over 850–500 mb, over the Tropical West Atlantic [15–25°N, 45–80°W], and (ii) southerly winds, similarly averaged, over the Florida Peninsula [20–30°N,75–80°W]. Winds within these two regions are enhanced when the North Atlantic subtropical high is displaced south and zonally elongated, relocating the western edge over Florida. A dust-transport-efficiency index, based on the maximum potential for dust to arrive above Miami with limited loss to deposition or mixing, identifies high-dust loading cases on the subseasonal scale. Monthly dust-transport-efficiency values agree well with the monthly dust trends over the 43-year time span. While seasonal dust loadings have been decreasing over Florida in the past decade, the transport efficiency has been increasing, possibly due to trends in the North Atlantic subtropical high.

54 ENVIRONMENTAL SCIENCES↗

Elevated Forest Canopy Loss After Wildfires in Moist and Cool Forests in the Pacific Northwest

Wildfire frequency, intensity, and rate of spread are increasing across the Western U.S, resulting in more severe ecosystem impacts. Significant tree mortality can occur years after fire events, but this has received little attention compared to the immediate tree loss during a fire. We overlapped forest cover loss data with burn severity maps in the U.S. Pacific Northwest and quantified the total and delayed forest canopy loss after fires. We found that wildfires resulted in total canopy loss fraction (CLF) of 84%, 53%, and 22% within 3 years in areas burned at high, moderate, and low severity, respectively. The delayed canopy loss accounted for approximately 1/3, 1/2, and 2/3 of the total canopy loss for high, moderate, and low severity burns. Delayed canopy loss was greater in moist and cool areas than in dry and warm areas, likely because tree species in wetter environments were less adapted to survive when fires did occur. Across all forests, delayed CLF doubled as temperature increased from the climatological mean to a hot anomaly and tripled as vapor pressure deficit increased from a wet anomaly to a dry anomaly. Fire impacts on forest ecosystems are likely to intensify under future climate scenarios as wildfires expand into areas that historically experienced infrequent fires. The impacts can also be exacerbated by more frequent compound extreme events, such as droughts, heatwaves, and fires. These findings highlight the urgent need for targeted forest management strategies, particularly in mesic forests, to mitigate future fire impacts.

54 ENVIRONMENTAL SCIENCES↗

A Greening Future Elevates Flash Drought Risk in Northern Mid‐to‐High Latitudes

Flash droughts have become a growing concern, as they can emerge rapidly and increase the risk of crop failure. Although past studies have investigated the meteorological drivers and future changes of flash drought, why flash drought is more frequent over humid and vegetated regions remains underexplored. This study delves further into the mechanism by which vegetation regulates flash drought and its future change using observations from multiple data sets and large ensemble simulations from three Earth system models. On an interannual timescale, both observations and simulations show robust increases in flash drought frequency and a higher flash-to-sub-seasonal drought ratio during spring or antecedent conditions with dense vegetation, supporting the important role of vegetation in flash drought occurrence, especially in the northern mid-to-high latitudes. In the latter regions, the large ensemble simulations show robust increases in flash drought (e.g., 67% and 46% increases in Eastern U.S. and North Asia in 2050–2100 relative to 1950–2000 under the high emission scenario), where the growing season is lengthening. Although greening might suggest reduced drought stress, it drives precipitation-soil moisture-evapotranspiration decoupling by increasing evapotranspiration partitioning to transpiration. As transpiration can access deep soil water through the plant root system, its increased portion can weaken the constraints of concurrent precipitation on evapotranspiration, thus accelerating soil moisture depletion under high evaporative demand, driving a slow-to-rapid drought transition. How vegetation regulates flash drought by regulating surface moisture budget is supported by observations and simulations. Although warming supports early planting, agriculture may increasingly be threatened by surging flash drought risk.

Drought↗

Alkali cation stabilization of defects in 2D MXenes at ambient and elevated temperatures

Transition metal carbides have been adopted in energy storage, conversion, and extreme environment applications. Advancements in their 2D counterparts, known as MXenes, enable the design of unique structures at the ~1 nm thickness scale. Alkali cations have been essential in MXenes manufacturing processing, storage, and applications, however, exact interactions of these cations with MXenes are not fully understood. In this study, using Ti 3 C 2 T x , Mo 2 TiC 2 T x , and Mo 2 Ti 2 C 3 T x MXenes, we present how transition metal vacancy sites are occupied by alkali cations, and their effect on MXene structure stabilization to control MXene’s phase transition. We examine this behavior using in situ high-temperature x-ray diffraction and scanning transmission electron microscopy, ex situ techniques such as atomic-layer resolution secondary ion mass spectrometry, and density functional theory simulations. In MXenes, this represents an advance in fundamentals of cation interactions on their 2D basal planes for MXenes stabilization and applications. Broadly, this study demonstrates a potential new tool for ideal phase-property relationships of ceramics at the atomic scale.

42 ENGINEERING↗

Anti-Ebola virus mAb 3A6 protects highly viremic animals from fatal outcome via binding GP(1,2) in a position elevated from the virion membrane

Abstract Monoclonal antibodies (mAbs) against Ebola virus (EBOV) glycoprotein (GP 1,2 ) are the standard of care for Ebola virus disease (EVD). Anti-GP 1,2 mAbs targeting the stalk and membrane proximal external region (MPER) potently neutralize EBOV in vitro and are protective in a mouse model of EVD. However, their neutralization mechanism is poorly understood because they target a GP 1,2 epitope that has evaded structural characterization. Using X-ray crystallography and cryo-electron tomography of mAb 3A6 complexed with its stalk–MPER epitope, we reveal a previously undescribed mechanism in which 3A6 binds to a conformation of GP 1,2 that is lifted from the virion membrane. We further show that in both domestic guinea pig and rhesus monkey EVD models, 3A6 provides therapeutic benefit at high-viremia advanced disease stages and at the lowest dose yet demonstrated for any anti-EBOV mAb-based monotherapy. The findings reported here can guide design of next-generation highly potent anti-EBOV therapeutics and vaccines.

Science & Technology - Other Topics↗

On the Elevated Temperature Thermal Stability of Nanoscale Mn-Ni-Si Precipitates Formed at Lower Temperature in Highly Irradiated Reactor Pressure Vessel Steels

Atom probe tomography (APT) and scanning transmission electron microscopy (STEM) techniques were used to probe the long-time thermal stability of nm-scale Mn-Ni-Si precipitates (MNSPs) formed in intermediate and high Ni reactor pressure vessel steels under high fluence neutron irradiation at ≈320 °C. Post irradiation annealing (PIA) at 425 °C for up to 57 weeks was used to determine if the MNSPs are: (a) non-equilibrium solute clusters formed and sustained by radiation induced segregation (RIS); or, (b) equilibrium G or Γ 2 phases, that precipitate at accelerated rates due to radiation enhanced diffusion (RED). Note the latter is consistent with both thermodynamic models and x-ray diffraction (XRD) measurements. Both the experimental and an independently calibrated cluster dynamics (CD) model results show that the stability of the MNSPs is very sensitive to the alloy Ni and, to a lesser extent, Mn content. Thus, a small fraction of the largest MNSPs in the high Ni steel persist, and begin to coarsen at long times. These results suggest that the MNSPs remain a stable phase, even at 105 °C higher than they formed at, thus are most certainly equilibrium phases at much lower service relevant temperatures of ≈290 °C.

36 MATERIALS SCIENCE↗

Elemental Zn and its Binding Protein Zinc-α2-Glycoprotein are Elevated in HPV-Positive Oropharyngeal Squamous Cell Carcinoma

Human papillomavirus (HPV)-positive head and neck squamous cell carcinoma (HNSCC) is biologically distinct from HPV-negative HNSCC. Outside of HPV-status, few tumor-intrinsic variables have been identified that correlate to improved survival. As part of exploratory analysis into the trace elemental composition of oropharyngeal squamous cell carcinoma (OPSCC), we performed elemental quanitification by X-ray fluorescence microscopy (XFM) on a small cohort (n = 32) of patients with HPV-positive and -negative OPSCC and identified in HPV-positive cases increased zinc (Zn) concentrations in tumor tissue relative to normal tissue. Subsequent immunohistochemistry of six Zn-binding proteins-zinc-alpha 2-glycoprotein (AZGP1), Lipocalin-1, Albumin, S100A7, S100A8 and S100A9-revealed that only AZGP1 expression significantly correlated to HPV-status (p < 0.001) and was also increased in tumor relative to normal tissue from HPV-positive OPSCC tumor samples. AZGP1 protein expression in our cohort significantly correlated to a prolonged recurrence-free survival (p = 0.029), similar to HNSCC cases from the TCGA (n = 499), where highest AZGP1 mRNA levels correlated to improved overall survival (p = 0.023). By showing for the first time that HPV-positive OPSCC patients have increased intratumoral Zn levels and AZGP1 expression, we identify possible positive prognostic biomarkers in HNSCC as well as possible mechanisms of increased sensitivity to chemoradiation in HPV-positive OPSCC.

60 APPLIED LIFE SCIENCES↗

Orthologs of human circulating miRNAs associated with hepatocellular carcinoma are elevated in mouse plasma months before tumour detection

Research examining the potential for circulating miRNA to serve as markers for preneoplastic lesions or early-stage hepatocellular carcinoma (HCC) is hindered by the difficulties of obtaining samples from asymptomatic individuals. As a surrogate for human samples, we identified hub miRNAs in gene co-expression networks using HCC-bearing C3H mice. We confirmed 38 hub miRNAs as associated with HCC in F2 hybrid mice derived from radiogenic HCC susceptible and resistant founders. When compared to a panel of 12 circulating miRNAs associated with human HCC, two had no mouse ortholog and 7 of the remaining 10 miRNAs overlapped with the 38 mouse HCC hub miRNAs. Using small RNA sequencing data generated from serially collected plasma samples in F2 mice, we examined the temporal levels of these 7 circulating miRNAs and found that the levels of 4 human circulating markers, miR-122-5p, miR-100-5p, miR-34a-5p and miR-365-3p increased linearly as the time approaching HCC detection neared, suggesting a correlation of miRNA levels with oncogenic progression. Estimation of change points in the kinetics of the 4 circulating miRNAs suggested the changes started 17.5 to 6.8 months prior to HCC detection. These data establish these 4 circulating miRNAs as potential sentinels for preneoplastic lesions or early-stage HCC.

60 APPLIED LIFE SCIENCES↗

Corn grown on dredged sediments alters rat behavior in the elevated plus maze via the gut mycobiome

The use of marginal lands for growing food has increased worldwide. Many of these lands are supplemented with soil amendments to enhance their productivity, but they may also introduce contaminants depending on their origin. The use of sediments dredged from commercial waterways as a soil amendment has increased in recent years. However, there is significant concern regarding their potential to negatively affect public health by transferring contaminants, like metals, to the food supply. This study examined the behavior, microbiome and physiology of rats fed corn grown on dredged sediments with rats fed commercial feed corn and related those metrics to kernel metal content. Metal content did not differ between kernels grown on dredged sediments and feed corn for most metals except iron which was greater in commercial feed corn. Although there is some variability by animal response, animals fed corn grown on dredged sediments had a gut microbial community that generally promoted anxiety-like behavior while animals fed feed corn had a gut microbial community that promoted a more typical response. These findings suggest the effect of corn grown on dredged sediments on public health is complex and highlights the need for further investigation.

Rua, Megan [Wright State University, Dayton, OH]↗