Tuning the spin-crossover properties of FeII4L6 cages via the interplay of coordination motif and linker modifications.

Despite the increasing number of spin-crossover FeII-based cages, the interplay between ligand modifications (e.g. coordination motif substituents and linker) is not well-understood in these multinuclear systems, limiting rational design. Here, we report a family of FeII4L6 spin-crossover cages based on 2,2'-pyridylbenzimidazoles where subtle ligand modifications lowered the spin crossover temperature in CD3CN by up to 186 K. Comparing pairs of cages, CH3 substituents on either the coordination motif or phenylene linker lowered the spin-crossover temperature by 48 K, 91 K or 186 K, attributed to electronic effects, steric effects and a combination of both, respectively. The understanding of the interplay between ligand modifications gained from this study could be harnessed on the path towards the improved rational design of spin-crossover cages.

Insight of CO2 and ethanol emission from maize silage: A case study with real-time identification of aerobic and anaerobic microbial respiration using a multi-sensor-fusion method.

Silage is produced worldwide for both livestock feeding and biogas production. Sustainable silage production requires characterization and mitigation of potential effects on environmental quality, particularly from greenhouse gas emissions during the production cycle. Ex-situ sampling has demonstrated that major emissions are carbon dioxide (CO2) and ethanol (EtOH). In-situ gas measurements from farm silo and bale silage are rare and may be important to improve our knowledge of the physical and biochemical causes, and constraints on these gas emissions. This study focused on tracking the kinetics of CO2 and EtOH emissions from bale maize silage, with real-time identification, quantification and separation of aerobic and anaerobic respiratory components in the period following opening of the silage. For this, an automatic multi-sensor gas-flux chamber (AMGC) was developed. Three bales (mean weight: 890 kg) of maize silage were tested (n = 3). Oxygen (O2) and temperature (Tsi) sensors were co-located at 10- and 20-cm behind the open face of the bales. Over the two weeks of the experiment we observed: (i) significant initial discharge of CO2 across the open face (1.68-2.55 mol m-2 h-1) and EtOH (0.027-0.034 mol m-2 h-1); (ii) peak CO2 emission occurred when O2 concentration (10 cm depth) was 3∼8% vol., while peak EtOH emission occurred below 2% vol. O2, (iii) dynamic conversion of O2 to CO2 from aerobic respiration; and (iv) the cumulative emission of EtOH during the anaerobic period was 4-6 times greater than that during aerobic plus semi-aerobic periods. These novel measurements provide mechanistic understanding, and may facilitate improved management of silage production to minimize environmental impact and aerobic loss of silage.

Long-Term Stable, High-Capacity Anode Material for Sodium-Ion Batteries: Taking a Closer Look at CrPS4 from an Electrochemical and Mechanistic Point of View.

Electrochemical performance of the layered compound CrPS4 for the usage as anode material in sodium-ion batteries (SIBs) was examined and exceptional reversible long-term capacity and capacity retention were found. After 300 cycles, an extraordinary reversible capacity of 687 mAh g-1 at a current rate of 1 A g-1 was achieved, while rate capability tests showed an excellent capacity retention of 100%. Detailed evaluation of the data evidence a change of the electrochemical reaction upon cycling leading to the striking long-term performance. Further investigations targeted the reaction mechanism of the first cycle by applying complementary techniques, i.e., powder X-ray diffraction (XRD), pair distribution function (PDF) analysis, X-ray absorption spectroscopy (XAS), and 23Na/31P magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The results indicated an unexpectedly complex reaction pathway including formation of several intercalation compounds, depending on the amount of Na inserted at the early discharge states and subsequent conversion to Na2S and strongly disordered metallic Cr at the completely discharged state. While XAS measurements suggest no further presence of intermediates after formation of Na intercalation compounds, several different phases are detected via MAS NMR upon continued discharging. Especially the data obtained from the MAS NMR investigations therefore point toward a very complex reaction pathway. Furthermore, solid electrolyte interphase (SEI) formation, resulting in the presence of NaF, was observed. After recharging the anode material, no structural long-range order occurred, but short-range order indeed resembled the local environment of the starting material, to a certain extent.

A Multi-Sensor Mini-Bioreactor to Preselect Silage Inoculants by Tracking Metabolic Activity in situ During Fermentation.

The microbiome in silage may vary substantially from the onset to the completion of fermentation. Improved additives and inoculants are being developed to accelerate the ensiling process, to enhance fermentation quality, and to delay spoilage during feed-out. However, current methods for preselecting and characterizing these amendments are time-consuming and costly. Here, we have developed a multi-sensor mini-bioreactor (MSMB) to track microbial fermentation in situ and additionally presented a mathematical model for the optimal assessment among candidate inoculants based on the Bolza equation, a fundamental formula in optimal control theory. Three sensors [pH, CO2, and ethanol (EtOH)] provided data for assessment, with four additional sensors (O2, gas pressure, temperature, and atmospheric pressure) to monitor/control the fermentation environment. This advanced MSMB is demonstrated with an experimental method for evaluating three typical species of lactic acid bacteria (LAB), Lentilactobacillus buchneri (LB) alone, and LB mixed with Lactiplantibacillus plantarum (LBLP) or with Enterococcus faecium (LBEF), all cultured in De Man, Rogosa, and Sharpe (MRS) broth. The fermentation process was monitored in situ over 48 h with these candidate microbial strains using the MSMB. The experimental results combine acidification characteristics with production of CO2 and EtOH, optimal assessment of the microbes, analysis of the metabolic sensitivity to pH, and partitioning of the contribution of each species to fermentation. These new data demonstrate that the MSMB associated with the novel rapid data-processing method may expedite development of microbial amendments for silage additives.

Dual sensor measurement shows that temperature outperforms pH as an early sign of aerobic deterioration in maize silage.

High quality silage containing abundant lactic acid is a critical component of ruminant diets in many parts of the world. Silage deterioration, a result of aerobic metabolism (including utilization of lactic acid) during storage and feed-out, reduces the nutritional quality of the silage, and its acceptance by animals. In this study, we introduce a novel non-disruptive dual-sensor method that provides near real-time information on silage aerobic stability, and demonstrates for the first time that in situ silage temperature (Tsi) and pH are both associated with preservation of lactic acid. Aerobic deterioration was evaluated using two sources of maize silage, one treated with a biological additive, at incubation temperatures of 23 and 33 °C. Results showed a time delay between the rise of Tsi and that of pH following aerobic exposure at both incubation temperatures. A 11 to 25% loss of lactic acid occurred when Tsi reached 2 °C above ambient. In contrast, by the time the silage pH had exceeded its initial value by 0.5 units, over 60% of the lactic acid had been metabolized. Although pH is often used as a primary indicator of aerobic deterioration of maize silage, it is clear that Tsi was a more sensitive early indicator. However, the extent of the pH increase was an effective indicator of advanced spoilage and loss of lactic acid due to aerobic metabolism for maize silage.

Heterogeneity of Stomatal Pore Area Is Suppressed by Ambient Aerosol in the Homobaric Species, Vicia faba.

Stomatal pore area is heterogeneous across leaf surfaces. This has been considered as "patchy stomatal conductance," and may have substantial implications for photosynthetic efficiency. Aerosols have always been important elements of plant environments, but their effects on stomatal control of plant water relations, and stomatal heterogeneity specifically, have not been considered. Here we evaluate the spatial coordination of pore area in the glabrous and homobaric leaves of Vicia faba grown under two aerosol treatments and measured at four levels of VPD. We construct a large dataset (n > 88,000 discrete comparisons) of paired pore areas and distances between the pores. Plants were grown in ambient urban air and in filtered air (FA) to determine the effect of ambient aerosol on stomatal properties. Pore area exhibited spatial organization, as well as considerable variability among closely co-located pores. The difference between pore areas was positively correlated with the distance between the pores, in both aerosol treatments and at all VPDs. However, aerosol deposition reduced both the magnitude of variability between pores and the rate at which this variability increased with pore separation distance. These data support previous conclusions that deposition of hygroscopic aerosol may create a thin aqueous film across the leaf surface that connects neighboring stomata to each other and to the leaf interior. Aerosol impacts on stomatal heterogeneity and gas exchange are not adequately considered in current assessments of stomatal control.

Differential responses of stomatal kinetics and steady-state conductance to abscisic acid in a fern: comparison with a gymnosperm and an angiosperm.

Origins of abscisic acid (ABA)-mediated metabolic control of stomatal conductance have been suggested to be recent, based on a gradualistic model of stomatal evolution. In ferns, steady-state stomatal conductance (gs ) was unresponsive to ABA in some studies, supporting this model. Stomatal kinetic responses to ABA have not been considered. We used dynamic gas exchange methods to characterise half times of stomatal opening and closing in response to step changes in light, across a range of ABA exposures in three diverse taxa. All taxa had asymmetric kinetics, with closure slower than opening in fern and cedar, but faster than opening in soybean. Closing was fastest in soybean but opening was slowest. Stomatal kinetics, particularly for closure, responded to ABA in all three taxa. Steady-state gs did not respond significantly to ABA in fern or cedar but responded strongly in soybean. Stomatal kinetics were responsive to ABA in fern. This finding supports a contrasting, single origin model, with ABA-mediated regulation of stomata arising early, in conjunction with stomata themselves. Stomatal kinetics are underutilised. Differential responses of opening and closing rates to environmental and hormonal stimuli may provide insights into phylogeny and stomatal regulatory strategies with potential application to selection for crop improvement.

Ambient aerosol increases minimum leaf conductance and alters the aperture-flux relationship as stomata respond to vapor pressure deficit (VPD).

Aerosols are important components of the global plant environment, with beneficial and deleterious impacts. The direct effects of aerosol deposition on plant-water relationships remain poorly characterized but potentially important. Vicia faba was grown in ambient urban air and in the same air with aerosol excluded, in a moderately polluted environment using two exposure protocols. Simultaneous measurement of gas exchange and stomatal pore aperture was combined with leaf dehydration kinetics and microscopic evaluation of leaf wetness formation and aerosol deposition patterns. The ambient aerosol was shown to be hygroscopic. Aerosol exposure increased minimum leaf conductance, shown by dehydration kinetics, and nocturnal water vapor flux, shown by dark-adapted gas exchange. Aerosol exposure decreased stomatal apertures at each level of vapor pressure deficit (VPD) and increased stomatal conductance at comparable levels of aperture. Overall, these effects were modest, and largest when stomata were wide open. The uncoupling of conductance (flux-based) from aperture (directly measured microscopically) implies that aerosol-induced water loss is not fully under stomatal control. This reduces drought tolerance and may provide a mechanism by which deposited aerosol plays a direct role in stomatal response to VPD.

CO2 production, dissolution and pressure dynamics during silage production: multi-sensor-based insight into parameter interactions.

Silage is a critical global feedstock, but is prone to aerobic deterioration. The dominant mechanism of O2 transport into silage remains unresolved. Here, multiple sensors tracked O2 and CO2, gas pressure (ΔP) between internal silage and ambient air, pH and silage temperature (Tsi) during the ensilage of maize and ryegrass. We report the first observation that CO2 produced from microbial respiration was partially dissolved in silage water, with evidence of negative or positive ΔP depending on the changing balance between CO2 production and dissolution. The ΔP < 0 reflected an apparent respiratory quotient (RQ) < 1. Net CO2 production was much greater in anaerobic fermentation stage than in initial aerobic phase or later aerobic feed-out phase. O2 transport into silage is intimately linked to the dynamics of net CO2, ΔP, microbial activity, pH and Tsi. These results suggested that both gas diffusion (based on Fick's law) and advective transfer (Darcy's law) play equally important roles in governing the complex temporal progression of inward and outward gas fluxes to and from the silage interior. Even though low pH suppressed microbial activity and supported aerobic stability, the negative ΔP increased the risk of O2 entry and aerobic deterioration during feed-out phase.

Xeromorphic traits help to maintain photosynthesis in the perhumid climate of a Taiwanese cloud forest.

Previous flux measurements in the perhumid cloud forest of northeastern Taiwan have shown efficient photosynthesis of the endemic tree species Chamaecyparis obtusa var. formosana even under foggy conditions in which leaf surface moisture would be expected. We hypothesized this to be the result of 'xeromorphic' traits of the Chamaecyparis leaves (hydrophobicity, stomatal crypts, stomatal clustering), which could prevent coverage of stomata by precipitation, fog, and condensation, thereby maintaining CO2 uptake. Here we studied the amount, distribution, and composition of moisture accumulated on Chamaecyparis leaf surfaces in situ in the cloud forest. We studied the effect of surface tension on gas penetration to stomata using optical O2 microelectrodes in the laboratory. We captured the dynamics of condensation to the leaf surfaces with an environmental scanning electron microscope (ESEM). In spite of substantial surface hydrophobicity, the mean water film thickness on branchlets under foggy conditions was 80 µm (upper surface) and 40 µm (lower surface). This amount of water could cover stomata and prevent CO2 uptake. This is avoided by the clustered arrangement of stomata within narrow clefts and the presence of Florin rings. These features keep stomatal pores free from water due to surface tension and provide efficient separation of plant and atmosphere in this perhumid environment. Air pollutants, particularly hygroscopic aerosol, may disturb this functionality by enhancing condensation and reducing the surface tension of leaf surface water.

Stable isotopic composition of perchlorate and nitrate accumulated in plants: Hydroponic experiments and field data.

Natural perchlorate (ClO4-) in soil and groundwater exhibits a wide range in stable isotopic compositions (δ37Cl, δ18O, and Δ17O), indicating that ClO4- may be formed through more than one pathway and/or undergoes post-depositional isotopic alteration. Plants are known to accumulate ClO4-, but little is known about their ability to alter its isotopic composition. We examined the potential for plants to alter the isotopic composition of ClO4- in hydroponic and field experiments conducted with snap beans (Phaseolus vulgaris L.). In hydroponic studies, anion ratios indicated that ClO4- was transported from solutions into plants similarly to NO3- but preferentially to Cl- (4-fold). The ClO4- isotopic compositions of initial ClO4- reagents, final growth solutions, and aqueous extracts from plant tissues were essentially indistinguishable, indicating no significant isotope effects during ClO4- uptake or accumulation. The ClO4- isotopic composition of field-grown snap beans was also consistent with that of ClO4- in varying proportions from irrigation water and precipitation. NO3- uptake had little or no effect on NO3- isotopic compositions in hydroponic solutions. However, a large fractionation effect with an apparent ε (15N/18O) ratio of 1.05 was observed between NO3- in hydroponic solutions and leaf extracts, consistent with partial NO3- reduction during assimilation within plant tissue. We also explored the feasibility of evaluating sources of ClO4- in commercial produce, as illustrated by spinach, for which the ClO4- isotopic composition was similar to that of indigenous natural ClO4-. Our results indicate that some types of plants can accumulate and (presumably) release ClO4- to soil and groundwater without altering its isotopic characteristics. Concentrations and isotopic compositions of ClO4- and NO3- in plants may be useful for determining sources of fertilizers and sources of ClO4- in their growth environments and consequently in food supplies.

Plant hydraulic responses to long-term dry season nitrogen deposition alter drought tolerance in a Mediterranean-type ecosystem.

Anthropogenic nitrogen (N) deposition represents a significant N input for many terrestrial ecosystems. N deposition can affect plants on scales ranging from photosynthesis to community composition, yet few studies have investigated how changes in N availability affect plant water relations. We tested the effects of N addition on plant water relations, hydraulic traits, functional traits, gas exchange, and leaf chemistry in a semi-arid ecosystem in Southern California using long-term experimental plots fertilized with N for over a decade. The dominant species were Artemisia california and Salvia mellifera at Santa Margarita Ecological Reserve and Adenostoma fasciculatum and Ceanothus greggii at Sky Oaks Field Station. All species, except Ceanothus, showed increased leaf N concentration, decreased foliar carbon to N ratio, and increased foliar N isotopic composition with fertilization, indicating that added N was taken up by study species, yet each species had a differing physiological response to long-term N addition. Dry season predawn water potentials were less negative with N addition for all species except Adenostoma, but there were no differences in midday water potentials, or wet season water potentials. Artemisia was particularly responsive, as N addition increased stem hydraulic conductivity, stomatal conductance, and leaf carbon isotopic composition, and decreased wood density. The alteration of water relations and drought resistance parameters with N addition in Artemisia, as well as Adenostoma, Ceanothus, and Salvia, indicate that N deposition can affect the ability of native Southern California shrubs to respond to drought.

Multivariate regulation of soil CO2 and N2 O pulse emissions from agricultural soils.

Climate and land-use models project increasing occurrence of high temperature and water deficit in both agricultural production systems and terrestrial ecosystems. Episodic soil wetting and subsequent drying may increase the occurrence and magnitude of pulsed biogeochemical activity, affecting carbon (C) and nitrogen (N) cycles and influencing greenhouse gas (GHG) emissions. In this study, we provide the first data to explore the responses of carbon dioxide (CO2 ) and nitrous oxide (N2 O) fluxes to (i) temperature, (ii) soil water content as percent water holding capacity (%WHC), (iii) substrate availability throughout, and (iv) multiple soil drying and rewetting (DW) events. Each of these factors and their interactions exerted effects on GHG emissions over a range of four (CO2 ) and six (N2 O) orders of magnitude. Maximal CO2 and N2 O fluxes were observed in environments combining intermediate %WHC, elevated temperature, and sufficient substrate availability. Amendments of C and N and their interactions significantly affected CO2 and N2 O fluxes and altered their temperature sensitivities (Q10 ) over successive DW cycles. C amendments significantly enhanced CO2 flux, reduced N2 O flux, and decreased the Q10 of both. N amendments had no effect on CO2 flux and increased N2 O flux, while significantly depressing the Q10 for CO2 , and having no effect on the Q10 for N2 O. The dynamics across DW cycles could be attributed to changes in soil microbial communities as the different responses to wetting events in specific group of microorganisms, to the altered substrate availabilities, or to both. The complex interactions among parameters influencing trace gas fluxes should be incorporated into next generation earth system models to improve estimation of GHG emissions.

The ozone component of global change: potential effects on agricultural and horticultural plant yield, product quality and interactions with invasive species.

The productivity, product quality and competitive ability of important agricultural and horticultural plants in many regions of the world may be adversely affected by current and anticipated concentrations of ground-level ozone (O3). Exposure to elevated O3 typically results in suppressed photosynthesis, accelerated senescence, decreased growth and lower yields. Various approaches used to evaluate O3 effects generally concur that current yield losses range from 5% to 15% among sensitive plants. There is, however, considerable genetic variability in plant responses to O3. To illustrate this, we show that ambient O3 concentrations in the eastern United States cause substantially different levels of damage to otherwise similar snap bean cultivars. Largely undesirable effects of O3 can also occur in seed and fruit chemistry as well as in forage nutritive value, with consequences for animal production. Ozone may alter herbicide efficacy and foster establishment of some invasive species. We conclude that current and projected levels of O3 in many regions worldwide are toxic to sensitive plants of agricultural and horticultural significance. Plant breeding that incorporates O3 sensitivity into selection strategies will be increasingly necessary to achieve sustainable production with changing atmospheric composition, while reductions in O3 precursor emissions will likely benefit world food production and reduce atmospheric concentrations of an important greenhouse gas.

Uncertainties in the current knowledge of some atmospheric trace gases associated with U.S. agriculture: a review.

Approximately 80 different crop species are grown in the United States in widely differing geographic areas, climatic and edaphic conditions, and management practices. Although the majority of cultivated acreage in the United States is planted with only about 10 primary crops, uncertainties associated with trace gas emissions arise from: (1) limited data availability, (2) inaccurate estimates because of large temporal and spatial variability in trace gas composition and magnitude of trace gas emissions from agricultural activities, (3) differing characteristics of pollutant emissions from highly dispersed animal feed-lots, and (4) limited understanding of the emissions of semi-volatile organic compounds (SVOCs) associated with agriculture. Although emission issues are of concern, so also is atmospheric deposition to cropping systems, including wet and dry nitrogen, minerals, and organic compounds. These can have feedback effects on trace gas emissions. Overall, the many gaps in our understanding of these aspects of agricultural systems deserve serious attention.