Direct Catalytic Conversion of Ethanol to C[subscript 5+] Ketones: Role of Pd-Zn Alloy on Catalytic Activity and Stability
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Sound crop and land management strategies can maintain land productivity and improve the environmental sustainability of agricultural crop and feedstock production. This study evaluates the improvement of water sustainability through an integrated landscaping management strategy, where landscaping design, land management operations, crop systems, and agricultural best management practices (BMPs) play equal roles. The strategy was applied to the watershed of the South Fork Iowa River in Iowa, with a focus on implementing riparian buffers and converting low productivity land to provide cellulosic biomass while benefiting soil and water quality. The Soil and Water Assessment Tool (SWAT) was employed to simulate the impact of integrated landscape design on nutrients, suspended sediments, and flow on the watershed and subbasin scales. First, the study evaluated the representation of buffer strip as a vegetative barrier and as a riparian buffer using trapping efficiency and area ratio methods in SWAT. For the riparian buffer, the area ratio method tends to be more conservative, especially in nitrate loadings, while the trapping efficiency method generates more optimistic results. The differences between the two methods increase with buffer width. The two methods may not be comparable for the field-scale vegetative barrier simulation because of limitations in model spatial resolution. Landscape scenarios were developed to quantify water quality under (1) current land use, (2) partial land conversion to switchgrass, and (3) riparian buffer implementation. Results show that when low productivity land (15.2% of total watershed land area) is converted to grow switchgrass, suspended sediment, total nitrogen, total phosphorus, and nitrate loadings are reduced by 69.3%, 55.5%, 46.1%, and 13.4%, respectively, in the watershed surface streams. The reduction was less extensive when riparian buffer strips (30 m or 50 m) were applied to the stream network at 1.4% of total land area in the watershed. At the subbasin level, the degree of nutrient and suspended sediment reduction varies extensively, ranging from a few percent up to 55%. Results indicate that effective landscape design on current agricultural land can potentially bring marked improvements in water quality and soil erosion control while producing food and fuel feedstock in the South Fork Iowa River watershed. The concept can be integrated with other watershed management programs to improve sustainability of land, water, and the ecosystem.
Abstract Many energy systems demand heat transfer at high temperatures to keep up with high demand for power, so high‐temperature material that can perform and last under these harsh conditions is needed for heat exchangers. The engineering requirements for these high‐temperature heat exchanger material call for high thermal conductivity, high resistance to fracture, high resistance to creep deformation, environmental stability in environments associated with the application, and high modulus of elasticity while maintaining low cost to make and maintain. Naturally, ceramics are a good solution for this endeavor. In the past, high‐temperature heat exchangers made from ceramics have been used. We provide examples of ceramics in relevant heat exchange applications and provide motivation where additive manufacturing (AM) can improve efficiency. AM for the relevant material is under development, and we provide insight on the AM of ceramic materials and examples of AM heat exchangers keeping cost in mind. The motivation of the review paper is to provide a framework for material and manufacturing selection for high‐temperature heat exchangers for AM to keep up with the demand for better efficiency, better material, better manufacturing, and cost moving forward with AM technology in high‐temperature ceramic heat exchangers.
Well-defined mixed-metal [CoMn 3 O 4 ] and [NiMn 3 O 4 ] cubane complexes were synthesized and used as precursors for heterogeneous oxygen evolution reaction (OER) electrocatalysts. The discrete clusters were dropcasted onto glassy carbon (GC) and indium tin oxide (ITO) electrodes, and the OER activities of the resulting films were evaluated. The catalytic surfaces were analyzed by various techniques to gain insight into the structure-function relationships of the electrocatalysts' heterometallic composition. Depending on preparation conditions, the Co-Mn oxide was found to change metal composition during catalysis, while the Ni-Mn oxides maintained the NiMn 3 ratio. XAS studies provided structural insights indicating that the electrocatalysts are different from the molecular precursors, but that the original NiMn 3 O 4 cubane-like geometry was maintained in the absence of thermal treatment ( 2-Ni ). In contrast, the thermally generated 3-Ni develops an oxide-like extended structure. Both 2-Ni and 3-Ni undergo structural changes upon electrolysis, but they do not convert into the same material. The observed structural motifs in these heterogeneous electrocatalysts are reminiscent of the biological oxygen-evolving complex in PhotosystemII, including the MMn 3 O 4 cubane moiety. The reported studies demonstrate the use of discrete heterometallic oxide clusters as precursors for heterogeneous water oxidation catalysts of novel composition and the distinct behavior of two sets of mixed metal oxides.
Single-atom catalysts (SACs) with isolated metal centers are attracting great research interest because of their maximized metal utilization rates and unique structures. In the last decade, significant efforts have been made to design highly efficient and costeffective SACs with applications in automobile exhaust aftertreatment. SACs have not only demonstrated their high potential for improving the catalytic performance of current automobile exhaust catalysts but also provided an ideal platform for understanding the origins of catalyst reactivity. In this review, we summarize the general strategies for promoting the reactivity of metal SACs while maintaining their thermal stability during exhaust-abatement-related reactions. Highlights are provided on well-performed SACs for CO oxidation, unburnt hydrocarbon (HC) oxidation, and the selective catalytic reduction of NOx. The reaction mechanism and structure– performance relationship of SAC during these reactions are also discussed. Finally, perspectives are given on the trending research fields for designing more efficient single-atom automobile exhaust catalysts in the future.
Inducible T7 expression systems are capable of producing a wide range of proteins in E. coli . Improvements over common practice include: preventing unintended induction by establishing and maintaining expression strains in non-inducing growth media comprised entirely of purified components instead of complex growth media that may variably induce target proteins on approach to saturation; and expressing many target proteins in parallel by convenient and productive auto-induction in BL21(DE3) and other suitable hosts, instead of IPTG induction. From earliest days, basal expression prevented establishment of inducible strains for producing proteins that are stressful to the host. Newly developed pAL vectors now reduce basal expression to levels where coding sequences for even the most stressful proteins can be maintained and induced. In conclusion, asymmetric ligation allows simple and efficient cloning of individual coding sequences or simultaneous cloning of two or three coding sequences for co expression from a single pAL vector.
Abstract In fire‐prone regions, the occurrence of some faunal species is contingent on the presence of resources that arise through post‐fire plant succession. Through planned burning, managers can alter resource availability and aim to provide the conditions required to promote biodiversity. Understanding how species occurrence changes at different spatial and temporal scales after fire is essential to achieve this goal. However, many fire prescriptions are guided primarily by the responses of fire‐sensitive plants when setting tolerable fire intervals. This approach assumes that maintaining floristic diversity will satisfy the requirements of fauna. We surveyed bird species in two semi‐arid vegetation types across an environmental gradient in south‐eastern Australia. We conducted four surveys at each of 253 sites across a 75‐year chronosequence of time since fire and used generalized additive mixed models to examine changes in the occurrence of birds in response to time since fire. Model predictions were compared to plant‐derived fire prescriptions currently guiding fire management in the region. Time since fire was a significant predictor for 18 of 28 species modeled, in at least one vegetation type, over a gradient of 1.3° of latitude. We detected considerable variation in the responses of some species, both between vegetation types and geographically within a vegetation type. Our evaluation of plant‐derived fire prescriptions suggests that the intervals considered acceptable for maintaining floristic diversity may not be sustainable for populations of birds requiring longer unburnt vegetation, with 6 of the 12 species assessed attaining a mean occurrence probability of 20.3% by the minimum tolerable fire interval, and 57.3% by the maximum tolerable fire interval, in their respective vegetation types. Our findings highlight the potential vulnerability of fire‐responsive bird species if fire prescriptions are applied in a manner that fails to account for the slow development of habitat resources needed by some species, and the variation detected within the responses of species. This highlights the need for species‐specific data collected at an appropriate spatial scale to inform management plans.
Abstract The response of tropical forests to global warming is one of the largest uncertainties in predicting the future carbon balance of Earth. To determine the likely effects of elevated temperatures on tropical forest understory plants and soils, as well as other ecosystems, an infrared (IR) heater system was developed to provide in situ warming for the Tropical Responses to Altered Climate Experiment ( TRACE ) in the Luquillo Experimental Forest in Puerto Rico. Three replicate heated 4‐m‐diameter plots were warmed to maintain a 4°C increase in understory vegetation compared to three unheated control plots, as sensed by IR thermometers. The equipment was larger than any used previously and was subjected to challenges different from those of many temperate ecosystem warming systems, including frequent power surges and outages, high humidity, heavy rains, hurricanes, saturated clayey soils, and steep slopes. The system was able to maintain the target 4.0°C increase in hourly average vegetation temperatures to within ± 0.1°C. The vegetation was heterogeneous and on a 21° slope, which decreased uniformity of the warming treatment on the plots; yet, the green leaves were fairly uniformly warmed, and there was little difference among 0–10 cm depth soil temperatures at the plot centers, edges, and midway between. Soil temperatures at the 40–50 cm depth increased about 3°C compared to the controls after a month of warming. As expected, the soil in the heated plots dried faster than that of the control plots, but the average soil moisture remained adequate for the plants. The TRACE heating system produced an adequately uniform warming precisely controlled down to at least 50‐cm soil depth, thereby creating a treatment that allows for assessing mechanistic responses of tropical plants and soil to warming, with applicability to other ecosystems. No physical obstacles to scaling the approach to taller vegetation (i.e., trees) and larger plots were observed.
Abstract Hydrogenases are a diverse group of metalloenzymes which catalyze the reversible conversion between molecular hydrogen and protons at high rates. The catalytic activity of these enzymes does not require overpotential because their active site has been evolutionarily optimized to operate fast and efficiently. These enzymes have inspired the development of molecular catalysts, which have dramatically improved in efficiency in recent years, to the point that some synthetic catalysts even outperform hydrogenases under certain conditions. In this work, we use a reversible noble‐metal‐free homogeneous catalyst, the [Ni(P Cy 2 N Phe 2 ) 2 ] 2+ complex, and we covalently immobilize it on a functionalized highly oriented pyrolytic graphite “edge” (HOPG e ) electrode surface. This catalyst is not water soluble, but once it is surface‐confined on the electrode, it maintains its catalytic properties in aqueous solutions, showing reversibility for H 2 oxidation/reduction. Immobilization of the [Ni(P Cy 2 N Phe 2 ) 2 ] 2+ complex onto a multi‐walled carbon nanotubes coated electrode leads to even higher catalytic current densities and enhanced stability.
Abstract A new adaptive clipping‐and‐redistribution method is presented which provides bounds‐preservation for multidimensional interpolation in the context of high‐order finite‐volume discretizations with adaptive mesh refinement (AMR). The underlying finite‐volume method (FVM) for the computational fluid dynamics applications is fourth‐order accurate for smooth solutions and utilizes AMR for computational efficiency in solving multiscale problems involving turbulence and combustion. High‐order interpolation between different AMR levels is required. However, this operation often leads to numerical issues because combustion species must have physical bounds preserved. The present study overcomes two major challenges in the development of the high‐order interpolation method. First, the method needs to be bound‐preserving near extrema or discontinuities to prevent the emergence of unphysical oscillations while maintaining fourth‐order accuracy in smooth flows. Second, the method needs to satisfy the conservation requirement in multiple dimensions, particularly in the context of curvilinear coordinate transformations. Additionally, the method is designed to be localized and computationally inexpensive. The new interpolation scheme is demonstrated by solving reacting flows, which are extremely sensitive to unphysical overshoots in conserved quantities. The test problems are shock‐induced ‐ combustion and a ‐air flame in a practical bluff‐body combustor. Results show the method prevents new extrema near discontinuities while maintaining high‐order accuracy in smooth regions. In particular, the method is extremely beneficial for combustion with stiff chemistry. With the proposed new method, even if flame fronts cross AMR interfaces or new grids are created in the vicinity of the flame, solution stability is retained.
ABSTRACT Paget's disease of bone (PDB) is the second most common bone disease mostly developing after 50 years of age at one or more localized skeletal sites; it is associated with severely high bone turnover, bone enlargement, bowing/deformity, cracking, and pain. Here, to specifically address the origins of the deteriorated mechanical integrity, we use a cohort of control and PDB human biopsies to investigate multiscale architectural and compositional modifications to the bone structure (ie, bone quality) and relate these changes to mechanical property measurements to provide further insight into the clinical manifestations (ie, deformities and bowing) and fracture risk caused by PDB. Here, at the level of the collagen and mineral (ie, nanometer-length scale), we find a 19% lower mineral content and lower carbonate-to-phosphate ratio in PDB, which accounts for the 14% lower stiffness and 19% lower hardness promoting plastic deformation in pathological bone. At the microstructural scale, trabecular regions are known to become densified, whereas cortical bone loses its characteristic parallel-aligned osteonal pattern, which is replaced with a mosaic of lamellar and woven bone. Although we find this loss of anisotropic alignment produces a straighter crack path in mechanically-loaded PDB cases, cortical fracture toughness appears to be maintained due to increased plastic deformation. Clearly, the altered quality of the bone structure in PDB affects the mechanical integrity leading to complications such as bowing, deformities, and stable cracks called fissure fractures associated with this disease. Although the lower mineralization and loss of aligned Haversian structures do produce a lower modulus tissue, which is susceptible to deformities, our results indicate that the higher levels of plasticity may compensate for the lost microstructural features and maintain the resistance to crack growth. © 2014 American Society for Bone and Mineral Research
Accelerated bone loss significantly increases the risk of osteoporosis and fracture. The mechanisms underlying bone loss remain incompletely understood, and there are few available biomarkers. We utilized a novel proteomics approach to identify serum peptides and proteins associated with bone loss in 1967 older men who were randomly chosen from the Osteoporotic Fracture in Men Study (MrOS study) (age ≥ 65 yrs). Men had 2-3 measures of femoral neck BMD over an average follow-up of 4.6 years. Change in BMD was estimated and then categorized into three groups: maintained BMD (n=453), expected loss (n=1185) and accelerated loss (n=237). A liquid chromatography–ion mobility separation-mass spectrometry (LC-IMS-MS) proteomics platform was used to identify and quantify peptides from serum proteins. The whole cohort was randomly divided into discovery (N= 960) and validation (N= 915) sub-cohorts. Linear regression models and a random forest approach were used to discover differentially abundant individual peptides and a proteomic signature that distinguished individuals with accelerated bone loss from those who maintained BMD. Network analyses were performed using the MetaCore knowledgebase. We identified 12 peptides that were associated with BMD loss in both discovery (P< 0.1 FDR) and replication sub-cohorts (P<0.05). Those 12 peptides mapped to the following proteins: ALS, LYVE1, RNAS1, C2, ICOSL, C163A, C7, HEMO, CD14, CERU, CRAC1 and CD59. Meta-analysis of peptidesassociated with bone loss identified 6 additional proteins including GRP78, IGF-2, SHBG, ENPP2, IBP2 and IBP6. We also identified a proteomic signature that was predictive of BMD loss with a discriminative value similar to serum bone marker carboxy-terminal collagen crosslink peptide (CTX). Interestingly, combining the proteomic signature with CTX significantly improved the ability to discriminate men with accelerated loss. In summary, we have identified potential new biomarkers for bone loss that provide a more in depth understanding of its pathophysiology.
Constantly evolving technology and techniques within radiation therapy require practitioners to maintain a continuous approach to professional development and training. Systems of performance appraisal and adoption of regular feedback mechanisms are vital to support this development yet frequently lack structure and rely on informal peer support. A Radiation Therapy Performance Appraisal Framework (RT-PAF) for radiation therapists in planning and simulation was developed to define expectations of practice and promote a supportive and objective culture of performance and skills appraisal. Evaluation of the framework was conducted via an anonymous online survey tool. Nine peer reviewers and fourteen recipients provided feedback on its effectiveness and the challenges and limitations of the approach. Findings from the evaluation were positive and suggested that both groups gained benefit from and expressed a strong interest in embedding the approach more routinely. Respondents identified common challenges related to the limited ability to implement suggested development strategies; this was strongly associated with time and rostering issues. This framework successfully defined expectations for practice and provided a fair and objective feedback process that focussed on skills development. It empowered staff to maintain their skills and reach their professional potential. Management support, particularly in regard to provision of protected time was highlighted as critical to the framework's ongoing success. The demonstrated benefits arising in terms of staff satisfaction and development highlight the importance of this commitment to the modern radiation therapy workforce.
Fleshy fruit is a key food resource for many vertebrates and may be particularly important energy source to birds during fall migration and winter. Hence, land managers should know how fruit availability varies among forest types, seasons, and years. We quantified fleshy fruit abundance monthly for 9 years (1995–2003) in 56 0.1-ha plots in 5 forest types of South Carolina's upper Coastal Plain, USA. Forest types were mature upland hardwood and bottomland hardwood forest, mature closed-canopy loblolly ( Pinus taeda ) and longleaf pine ( P. palustris ) plantation, and recent clearcut regeneration harvests planted with longleaf pine seedlings. Mean annual number of fruits and dry fruit pulp mass were highest in regeneration harvests (264,592 ± 37,444 fruits; 12,009 ± 2,392 g/ha), upland hardwoods (60,769 ± 7,667 fruits; 5,079 ± 529 g/ha), and bottomland hardwoods (65,614 ± 8,351 fruits; 4,621 ± 677 g/ha), and lowest in longleaf pine (44,104 ± 8,301 fruits; 4,102 ± 877 g/ha) and loblolly (39,532 ± 5,034 fruits; 3,261 ± 492 g/ha) plantations. Fruit production was initially high in regeneration harvests and declined with stand development and canopy closure (1995–2003). Fruit availability was highest June–September and lowest in April. More species of fruit-producing plants occurred in upland hardwoods, bottomland hardwoods, and regeneration harvests than in loblolly and longleaf pine plantations. Several species produced fruit only in 1 or 2 forest types. In sum, fruit availability varied temporally and spatially because of differences in species composition among forest types and age classes, patchy distributions of fruiting plants both within and among forest types, fruiting phenology, high inter-annual variation in fruit crop size by some dominant fruit-producing species, and the dynamic process of disturbance-adapted species colonization and decline, or recovery in recently harvested stands. As a result, land managers could enhance fruit availability for wildlife by creating and maintaining diverse forest types and age classes.
Abstract Objective Northern Pike Esox lucius recently invaded Box Canyon Reservoir, Washington, expanding to over 10,000 individuals by 2011. To limit further impacts, a significant reduction in population abundance was required. Project objectives were to reduce relative abundance (catch per unit effort [CPUE]) to less than 1.7 Northern Pike/net (87% reduction) in the core area and to less than 0.5 Northern Pike/net in the northern reservoir section within 3 years and then maintain those abundance targets thereafter. Methods Using gill nets, we conducted intensive annual (2012–2018) suppression each spring, focusing on spawning aggregations in shallow (<2-m), flooded habitats. To evaluate CPUE, a standardized spring pike index netting (SPIN) survey was conducted annually in May and compared to suppression netting CPUE. Result In total, 17,464 Northern Pike were removed in 4868 net sets, with 92.9% captured in the first 3 years, limiting future recruitment. Mean SPIN CPUE in the core area declined from a presuppression (2011) high of 13.2 Northern Pike/net to less than 1.0 Northern Pike/net by 2014. Effort was reduced by up to 80% as the project transitioned from the initial suppression phase (2012–2014) to a control phase (2015–2018), which explored the minimum effort required to maintain abundance targets. A significant rebound in CPUE occurred from 2017 to 2018, indicating that over 267 net sets annually may be required for long-term control. Although the mean CPUE (±95% confidence interval) increased slightly in 2018 (0.6 ± 0.5 Northern Pike/net), the target abundance in the core area was achieved annually from 2013 to 2018. Changes in suppression CPUE reflected those observed in SPIN surveys, further validating the survey and corroborating abundance trends. Conclusion Results demonstrate that the suppression of Northern Pike in large, complex waters is feasible but requires a substantial long-term commitment. We expect the suppression of this invasive species to become standard practice outside of its native range. The methodology and equipment described here could be applied directly or modified by others to suppress Northern Pike.
Abstract Cell walls surround all plant cells, and their composition and structure are tightly regulated to maintain cellular and organismal homeostasis. In response to wall damage, the cell wall integrity (CWI) system is engaged to ameliorate effects on plant growth. Despite the central role CWI plays in plant development, our current understanding of how this system functions at the molecular level is limited. Here, we investigated the transcriptomes of etiolated seedlings of mutants of Arabidopsis thaliana with defects in three major wall polysaccharides, pectin ( quasimodo2 ), cellulose ( cellulose synthase3 je5 ), and xyloglucan ( xyloglucan xylosyltransferase1 and 2 ), to probe whether changes in the expression of cell wall‐related genes occur and are similar or different when specific wall components are reduced or missing. Many changes occurred in the transcriptomes of pectin‐ and cellulose‐deficient plants, but fewer changes occurred in the transcriptomes of xyloglucan‐deficient plants. We hypothesize that this might be because pectins interact with other wall components and/or integrity sensors, whereas cellulose forms a major load‐bearing component of the wall; defects in either appear to trigger the expression of structural proteins to maintain wall cohesion in the absence of a major polysaccharide. This core set of genes functioning in CWI in plants represents an attractive target for future genetic engineering of robust and resilient cell walls.
C 3 photosynthesis can be complemented with a C 4 carbon concentrating mechanism (CCM) to minimize photorespiratory losses. C 4 photosynthesis is often more efficient than C 3 under steady-state conditions. However, the C 4 CCM depends on inter-cellular metabolite concentration gradients, which must increase following increases in light intensity and could decrease rates of C 4 photosynthesis under fluctuating light. Additionally, incomplete flux through photorespiration could prove beneficial to C 4 assimilation during light induction of the CCM. Here, we compare metabolic profiles in the closely related C 3 Flaveria robusta and C 4 Flaveria bidentis during a light transient from low to high light to determine if these non-steady state accumulation patterns provide insight to the induction of the metabolite gradients needed to drive C 4 intermediate transport and if there is incomplete cycling of photorespiratory intermediates. In these C 3 and C 4 species, metabolite steady-state pool sizes suggest that C 4 transport acids maintain concentration gradients across the bundle sheath and mesophyll cell types under these light fluctuations. However, there was incomplete flux through photorespiration in the C 4 F. bidentis, which could reduce photorespiratory CO 2 loss via glycine decarboxylation and help maintain higher rates of assimilation during following induction periods.
Anion exchange membranes (AEMs) are a promising class of materials for applications that require selective ion transport, such as fuel cells, water purification, and electrolysis devices. Studies of structure–morphology–property relationships of ion-exchange membranes revealed that block copolymers exhibit improved ion conductivity and mechanical properties due to their microphase-separated morphologies with well-defined ionic domains. While most studies focused on symmetric diblock or triblock copolymers, here, the first example of a midblock quaternized pentablock AEM is presented. A symmetric ABCBA pentablock copolymer was functionalized to obtain a midblock brominated polymer. Solution cast films were then quaternized to obtain AEMs with resulting ion exchange capacities (IEC) ranging from 0.4 to 0.9 mmol/g. Despite the relatively low IEC, the polymers were highly conductive (up to 60 mS/cm Br- at 90 °C and 95%RH) with low water absorption (<25 wt %) and maintained adequate mechanical properties in both dry and hydrated conditions. X-ray scattering and transmission electron microscopy (TEM) revealed formation of cylindrical non-ionic domains in a connected ionic phase.