Key Role of Equilibrium HONO Concentration over Soil in Quantifying Soil-Atmosphere HONO Fluxes.

Nitrous acid (HONO) is an important component of the global nitrogen cycle and can regulate the atmospheric oxidative capacity. Soil is an important source of HONO. [HONO]*, the equilibrium gas-phase concentration over the aqueous solution of nitrous acid in the soil, has been suggested as a key parameter for quantifying soil fluxes of HONO. However, [HONO]* has not yet been well-validated and quantified. Here, we present a method to retrieve [HONO]* by conducting controlled dynamic chamber experiments with soil samples applied with different HONO concentrations at the chamber inlet. We show a bi-directional soil-atmosphere exchange of HONO and confirm the existence of [HONO]* over soil: when [HONO]* is higher than the atmospheric HONO concentration, HONO will be released from soil; otherwise, HONO will be deposited. We demonstrate that [HONO]* is a soil characteristic, which is independent of HONO concentrations in the chamber but varies with different soil water contents. We illustrate the robustness of using [HONO]* for quantifying soil fluxes of HONO, whereas the laboratory-determined chamber HONO fluxes can largely deviate from those in the real world for the same soil sample. This work advances the understanding of the soil-atmosphere exchange of HONO and the evaluation of its impact on the atmospheric oxidizing capacity.

Reactive Nitrogen Hotspots Related to Microscale Heterogeneity in Biological Soil Crusts.

Biocrusts covering drylands account for major fractions of terrestrial biological nitrogen fixation and release large amounts of gaseous reactive nitrogen (Nr) as nitrous acid (HONO) and nitric oxide (NO). Recent investigations suggested that aerobic and anaerobic microbial nitrogen transformations occur simultaneously upon desiccation of biocrusts, but the spatio-temporal distribution of seemingly contradictory processes remained unclear. Here, we explore small-scale gradients in chemical concentrations related to structural characteristics and organism distribution. X-ray microtomography and fluorescence microscopy revealed mixed pore size structures, where photoautotrophs and cyanobacterial polysaccharides clustered irregularly in the uppermost millimeter. Microsensor measurements showed strong gradients of pH, oxygen, and nitrite, nitrate, and ammonium ion concentrations at micrometer scales in both vertical and lateral directions. Initial oxygen saturation was mostly low (∼30%) at full water holding capacity, suggesting widely anoxic conditions, and increased rapidly upon desiccation. Nitrite concentrations (∼6 to 800 µM) and pH values (∼6.5 to 9.5) were highest around 70% WHC. During further desiccation they decreased, while emissions of HONO and NO increased, reaching maximum values around 20% WHC. Our results illustrate simultaneous, spatially separated aerobic and anaerobic nitrogen transformations, which are critical for Nr emissions, but might be impacted by future global change and land management.

Synaptic Plasticity Depends on the Fine-Scale Input Pattern in Thin Dendrites of CA1 Pyramidal Neurons.

Coordinated long-term plasticity of nearby excitatory synaptic inputs has been proposed to shape experience-related neuronal information processing. To elucidate the induction rules leading to spatially structured forms of synaptic potentiation in dendrites, we explored plasticity of glutamate uncaging-evoked excitatory input patterns with various spatial distributions in perisomatic dendrites of CA1 pyramidal neurons in slices from adult male rats. We show that (1) the cooperativity rules governing the induction of synaptic LTP depend on dendritic location; (2) LTP of input patterns that are subthreshold or suprathreshold to evoke local dendritic spikes (d-spikes) requires different spatial organization; and (3) input patterns evoking d-spikes can strengthen nearby, nonsynchronous synapses by local heterosynaptic plasticity crosstalk mediated by NMDAR-dependent MEK/ERK signaling. These results suggest that multiple mechanisms can trigger spatially organized synaptic plasticity on various spatial and temporal scales, enriching the ability of neurons to use synaptic clustering for information processing.SIGNIFICANCE STATEMENT A fundamental question in neuroscience is how neuronal feature selectivity is established via the combination of dendritic processing of synaptic input patterns with long-term synaptic plasticity. As these processes have been mostly studied separately, the relationship between the rules of integration and rules of plasticity remained elusive. Here we explore how the fine-grained spatial pattern and the form of voltage integration determine plasticity of different excitatory synaptic input patterns in perisomatic dendrites of CA1 pyramidal cells. We demonstrate that the plasticity rules depend highly on three factors: (1) the location of the input within the dendritic branch (proximal vs distal), (2) the strength of the input pattern (subthreshold or suprathreshold for dendritic spikes), and (3) the stimulation of neighboring synapses.

Waterborne Colloidal Polymer/Silica Hybrid Dispersions and Their Assembly into Mesoporous Poly(melamine-formaldehyde) Xerogels.

The acid-catalyzed polycondensation of oligo(melamine-formaldehyde) in aqueous phase and in the presence of silica nanoparticles leads to a stable dispersion of coexisting silica and polymer nanoparticles. The dispersion can be processed into mesoporous xerogels (SBET ≈ 200 m(2) g(-1)), whose porosity can be enhanced by etching of silica up to specific surface areas of >400 m(2) g(-1). The formation mechanism and the characteristics of the hybrid dispersion are crucial to the materials derived from it and analyzed in detail using a variety of experimental techniques (electron and force microscopy, light and X-ray scattering, ultracentrifugation, and spectroscopy). The transformation of the dispersion into xerogels by electrostatic destabilization is described. Furthermore, the obtained materials are characterized with regard to their porosity and morphology using microscopy and porosimetry. The impact of selected synthesis parameters on the obtained properties is discussed, and it was found (most interestingly) that stable porosity was only observed if silica nanoparticles were present within the dispersion.

Microwave-Assisted Synthesis of Defects Metal-Imidazolate-Amide-Imidate Frameworks and Improved CO2 Capture.

In this work, we report three isostructural 3D frameworks, named IFP-11 (R = Cl), IFP-12 (R = Br), and IFP-13 (R = Et) (IFP = Imidazolate Framework Potsdam) based on a cobalt(II) center and the chelating linker 2-substituted imidazolate-4-amide-5-imidate. These chelating ligands were generated in situ by partial hydrolysis of 2-substituted 4,5-dicyanoimidazoles under microwave (MW)-assisted conditions in DMF. Structure determination of these IFPs was investigated by IR spectroscopy and a combination of powder X-ray diffraction (PXRD) with structure modeling. The structural models were initially built up from the single-crystal X-ray structure determination of IFP-5 (a cobalt center and 2-methylimidazolate-4-amide-5-imidate linker based framework) and were optimized by using density functional theory calculations. Substitution on position 2 of the linker (R = Cl, Br, and Et) in the isostructural IFP-11, -12, and -13 allowed variation of the potential pore window in 1D hexagonal channels (3.8 to 1.7 Å). The potential of the materials to undergo specific interactions with CO2 was measured by the isosteric heat of adsorption. Further, we resynthesized zinc based IFPs, namely IFP-1 (R = Me), IFP-2 (R = Cl), IFP-3 (R = Br), and IFP-4 (R = Et), and cobalt based IFP-5 under MW-assisted conditions with higher yield. The transition from a nucleation phase to the pure crystalline material of IFP-1 in MW-assisted synthesis depends on reaction time. IFP-1, -3, and -5, which are synthesized by MW-assisted conditions, showed an enhancement of N2 and CO2, compared to the analogous conventional electrical (CE) heating method based materials due to crystal defects.

Detecting short-term change and variation in health-related quality of life: within- and between-person factor structure of the SF-36 health survey.

BACKGROUND: A major goal of much aging-related research and geriatric medicine is to identify early changes in health and functioning before serious limitations develop. To this end, regular collection of patient-reported outcome measure (PROMs) in a clinical setting may be useful to identify and monitor these changes. However, existing PROMs were not designed for repeated administration and are more commonly used as one-time screening tools; as such, their ability to detect variation and measurement properties when administered repeatedly remain unknown. In this study we evaluated the potential of the RAND SF-36 Health Survey as a repeated-use PROM by examining its measurement properties when modified for administration over multiple occasions. METHODS: To distinguish between-person (i.e., average) from within-person (i.e., occasion) levels, the SF-36 Health Survey was completed by a sample of older adults (N = 122, M age = 66.28 years) daily for seven consecutive days. Multilevel confirmatory factor analysis (CFA) was employed to investigate the factor structure at both levels for two- and eight-factor solutions. RESULTS: Multilevel CFA models revealed that the correlated eight-factor solution provided better model fit than the two-factor solution at both the between-person and within-person levels. Overall model fit for the SF-36 Health Survey administered daily was not substantially different from standard survey administration, though both were below optimal levels as reported in the literature. However, individual subscales did demonstrate good reliability. CONCLUSIONS: Many of the subscales of the modified SF-36 for repeated daily assessment were found to be sufficiently reliable for use in repeated measurement designs incorporating PROMs, though the overall scale may not be optimal. We encourage future work to investigate the utility of the subscales in specific contexts, as well as the measurement properties of other existing PROMs when administered in a repeated measures design. The development and integration of new measures for this purpose may ultimately be necessary.

Conditions potentially sensitive to a personal health record (PHR) intervention, a systematic review.

BACKGROUND: Personal Health Records (PHRs) are electronic health records controlled, shared or maintained by patients to support patient centered care. The potential for PHRs to transform health care is significant; however, PHRs do not always achieve their potential. One reason for this may be that not all health conditions are sensitive to the PHR as an intervention. The goal of this review was to discover which conditions were potentially sensitive to the PHR as an intervention, that is, what conditions have empirical evidence of benefit from PHR-enabled management. METHODS: A systematic review of Medline and CINAHL was completed to find articles assessing PHR use and benefit from 2008 to 2014 in specific health conditions. Two researchers independently screened and coded articles. Health conditions with evidence of benefit from PHR use were identified from the included studies. RESULTS: 23 papers were included. Seven papers were RCTs. Ten health conditions were identified, seven of which had documented benefit associated with PHR use: asthma, diabetes, fertility, glaucoma, HIV, hyperlipidemia, and hypertension. Reported benefits were seen in terms of care quality, access, and productivity, although many benefits were measured by self-report through quasi-experimental studies. No study examined morbidity/mortality. No study reported harm from the PHR. CONCLUSION: There is a small body of condition specific evidence that has been published. Conditions with evidence of benefit when using PHRs tended to be chronic conditions with a feedback loop between monitoring in the PHR and direct behaviours that could be self-managed. These findings can point to other potentially PHR sensitive health conditions and guide PHR designers, implementers, and researchers. More research is needed to link PHR design, features, adoption and health outcomes to better understand how and if PHRs are making a difference to health outcomes.

Opposing functions of two sub-domains of the SNARE-complex in neurotransmission.

The SNARE-complex consisting of synaptobrevin-2/VAMP-2, SNAP-25 and syntaxin-1 is essential for evoked neurotransmission and also involved in spontaneous release. Here, we used cultured autaptic hippocampal neurons from Snap-25 null mice rescued with mutants challenging the C-terminal, N-terminal and middle domains of the SNARE-bundle to dissect out the involvement of these domains in neurotransmission. We report that the stabilities of two different sub-domains of the SNARE-bundle have opposing functions in setting the probability for both spontaneous and evoked neurotransmission. Destabilizing the C-terminal end of the SNARE-bundle abolishes spontaneous neurotransmitter release and reduces evoked release probability, indicating that the C-terminal end promotes both modes of release. In contrast, destabilizing the middle or deleting the N-terminal end of the SNARE-bundle increases both spontaneous and evoked release probabilities. In both cases, spontaneous release was affected more than evoked neurotransmission. In addition, the N-terminal deletion delays vesicle priming after a high-frequency train. We propose that the stability of N-terminal two-thirds of the SNARE-bundle has a function for vesicle priming and limiting spontaneous release.

Polybenzoxazine: a powerful tool for removal of mercury salts from water.

A reusable macroporous polybenzoxazine resin with high specific surface area was prepared as sorbent material for the removal of mercury salts. For this purpose, allyl-functionalized bis-benzoxazine was cured in dimethyl sulfoxide by thermally activated ring-opening polymerization at 180 °C for 3 d followed by a freeze-drying process. The porous structure of the resin was confirmed by SEM analysis and N2 adsorption/desorption studies at 77.3 K. Among various metal ions, namely, Pb(II), Fe(II), Mn(II), Cu(II), Zn(II), and Cd(II), the porous polybenzoxazine resin exhibited a specific sorption behaviour towards Hg(II). Mainly chemisorption and to some extent adsorption mechanisms were proposed for the observed high loading capacity of the resin. As evidenced by FTIR spectral analysis, the chemisorption is attributed to the coordination system formed between free OH and tertiary amino groups in the polybenzoxazine structure and Hg(II) ions. It was also demonstrated that the porous polybenzoxazine can be regenerated simply by treatment with acids. The resin was recycled for up to seven cycles without any significant loss of activity, as proved by sorption and desorption experiments.

Microbial composition of Saharan dust plumes deposited as red rain in Granada (Southern Spain).

During durst storms, also biological material is transported from arid areas such as the Sahara Desert. In the present work, rain samples containing significant amounts of mineral dust have been collected in Granada during different red rain episodes. Biological features (bacteria, biofilm, pollen grain and fungal spore) as well as size-particle distribution and mineralogical composition were studied by SEM. Nanobacteria were observed for the first time in red rain samples. A preliminary metabarcoding analysis was performed on three red rain samples. Here, Bacillota made up 18 % and Pseudomonadota 23 % of the whole prokaryotic community. The fungal community was characterized by a high abundance of Ascomycota and, dependent on the origin, the presence of Chytridiomycota. By means of 16S rRNA sequencing, 18 cultivable microorganisms were identified. In general, members of the phyla Pseudomonadota and Bacillota made up the majority of taxa. Some species, such as Peribacillus frigoritolerans and Bacillus halotolerans were isolated during three different red rain episodes. Generally, red rain carries a wide variety of microorganisms, being their ecosystem and health effects largely unknown.

Effective mercury sorption by thiol-laced metal-organic frameworks: in strong acid and the vapor phase.

Free-standing, accessible thiol (-SH) functions have been installed in robust, porous coordination networks to provide wide-ranging reactivities and properties in the solid state. The frameworks were assembled by reacting ZrCl4 or AlCl3 with 2,5-dimercapto-1,4-benzenedicarboxylic acid (H2DMBD), which features the hard carboxyl and soft thiol functions. The resultant Zr-DMBD and Al-DMBD frameworks exhibit the UiO-66 and CAU-1 topologies, respectively, with the carboxyl bonded to the hard Zr(IV) or Al(III) center and the thiol groups decorating the pores. The thiol-laced Zr-DMBD crystals lower the Hg(II) concentration in water below 0.01 ppm and effectively take up Hg from the vapor phase. The Zr-DMBD solid also features a nearly white photoluminescence that is distinctly quenched after Hg uptake. The carboxyl/thiol combination thus illustrates the wider applicability of the hard-and-soft strategy for functional frameworks.

Restricted access: on the nature of adsorption/desorption hysteresis in amorphous, microporous polymeric materials.

The phenomenon of low-pressure adsorption/desorption hysteresis, which is commonly observed in microporous polymers, is investigated by detailed gas adsorption studies. Diffusional limitations by pore blocking effects, which arise as a consequence of the micropore morphology and connectivity, are discussed as the origin of the hysteresis rather than swelling effects, which have been suggested previously. Micropores with narrow openings, which cannot be filled easily, are expected to be present next to open pores. Those pores are termed restricted-access pores and are only filled in the course of the adsorption process as a consequence of the increasing solvation pressure exhibited from already filled micropores. As a consequence of the results presented here, it is suggested to use the desorption branch in addition to the adsorption branch for the extraction of the porosity characteristics, such as specific surface area, pore volume, and pore size distribution. The magnitude of the low-pressure hysteresis might hence give an idea of the micropore connectivity, which is important information for potential applications.

A systems theory classification of EMR hazards: preliminary results.

Jurisdictions in Canada, the US, the EU and Australia are struggling with regulation of ever evolving software in medicine. Recently this discussion has had a focus on electronic medical records (EMRs). There is a mountain of evidence that EMRs have actualized potential to lead to the injury of patients through the information they offer to facilitate care. We are undertaking a systematic review of relevant literature in the field to uncover some of the latent hazards. We hypothesize that this exploration, using a variation on Leveson's system theoretic accidents models and processes (STAMP) model as a classification tool, will provide two benefits. First, the model will be sufficient to capture the complexity of the domain and its hazards, thus providing a holistic perspective on the problem. Second, the classification process will provide insight as to what steps might be taken to mitigate the risk that medical errors associated with these software tools will arise in health care systems which employ them. In this continuation of our study we still have not been able to produce evidence which contradicts either hypothesis.

Société de Biomécanique Young Investigator Award 2019: Upper body behaviour of seated humans in vivo under controlled lateral accelerations.

BACKGROUND: A deep understanding of human reactions and stabilization strategies is required to predict their kinematics under external dynamic loadings, such as those that occur in vehicle passengers. Low-level frontal accelerations have been thoroughly investigated; however, the human response to different lateral accelerations is not well understood. The objective of this study is to gain insight regarding the responses of seated humans to lateral perturbations from volunteer experiments in different configurations. METHODS: Five volunteers anthropometrically comparable to the 50th-percentile American male, were seated on a sled and submitted to 21 lateral pulses. Seven configurations, each repeated three times, were investigated in this study: a relaxed muscular condition with four pulses, namely, sine and plateau pulses of 0.1 and 0.3 g in a straight spinal posture; a relaxed muscular condition with a plateau pulse of 0.3 g in a sagging spinal posture; and a braced condition with both plateau pulses in a straight spinal posture. Upper body segment kinematics were assessed using inertial measurement units. FINDINGS: The maximum lateral bending of the head was found to differ significantly among the four acceleration pulses (p < 0.001). Braced muscles significantly reduced lateral bending compared to relaxed muscles (p < 0.001). However, no significant difference was found in lateral bending between straight and sagging spinal postures (p = 0.23). INTERPRETATION: The study shows that not only pulse amplitude but also pulse shape influences human responses to low accelerations, while spinal posture does not influence lateral head bending. These data can be used to evaluate numerical active human body models.

Kinematic response of seated male volunteers in various reclined postures on a sled subjected to a braking pulse.

Vehicle occupants expect greater postural flexibility with the introduction of highly automated vehicles, such as reclined postures. Experiments have been conducted with post mortem human subjects to study the risk of injury under impact conditions in reclined postures. However, the influence of the pre-crash phase on the kinematics in reclined postures has not yet been thoroughly studied. The aim of the present study is to investigate human responses under low g braking conditions focusing on different backrest angles in a generic sled environment. Three 50th percentile male volunteers were recruited to participate in a sled experiment. Each of them was subjected to a total of fourteen trials under a braking pulse with a maximum acceleration of 0.7 g for 700 ms. Different sitting postures were investigated: from 23° to 45°, 60° and 75° backrest tilt with respect to the vertical axis. In addition, two different seat pan tilt angles were considered: a 16° tilt angle for 23°, 45° and 60° backrest inclination and a 36° tilt angle for 60° and 75° backrest inclination. Measurements of volunteer kinematics, muscle activation and interaction forces between the volunteers and the sled, among others, were acquired. Initial results show a significant reduction in maximum forward head displacement from the upright to the reclined postures (p < 0.02), with the exception of the 45° reclined posture. However, no significant difference in maximum head displacement was found between the different reclined postures (p > 0.1). Seat pan tilt angle did significantly influence forward head excursion when considering the same seatback inclination (p < 0.01). It is of great importance to investigate occupant kinematics during the pre-crash phase to understand its influence on the potential injuries that may occur with a reclined posture in the event of a collision.

An isoreticular family of microporous metal-organic frameworks based on zinc and 2-substituted imidazolate-4-amide-5-imidate: syntheses, structures and properties.

We report on a new series of isoreticular frameworks based on zinc and 2-substituted imidazolate-4-amide-5-imidate (IFP-1-4, IFP = imidazolate framework Potsdam) that form one-dimensional, microporous hexagonal channels. Varying R in the 2-substitued linker (R = Me (IFP-1), Cl (IFP-2), Br (IFP-3), Et (IFP-4)) allowed the channel diameter (4.0-1.7 Å), the polarisability and functionality of the channel walls to be tuned. Frameworks IFP-2, IFP-3 and IFP-4 are isostructural to previously reported IFP-1. The structures of IFP-2 and IFP-3 were solved by X-ray crystallographic analyses. The structure of IFP-4 was determined by a combination of PXRD and structure modelling and was confirmed by IR spectroscopy and (1)H MAS and (13)C CP-MAS NMR spectroscopy. All IFPs showed high thermal stability (345-400 °C); IFP-1 and IFP-4 were stable in boiling water for 7 d. A detailed porosity analysis was performed on the basis of adsorption measurements by using various gases. The potential of the materials to undergo specific interactions with CO(2) was investigated by measuring the isosteric heats of adsorption. The capacity to adsorb CH(4) (at 298 K), CO(2) (at 298 K) and H(2) (at 77 K) at high pressure were also investigated. In situ IR spectroscopy showed that CO(2) is physisorbed on IFP-1-4 under dry conditions and that both CO(2) and H(2)O are physisorbed on IFP-1 under moist conditions.

Carbohydrate-derived hydrothermal carbons: a thorough characterization study.

Hydrothermal carbonization (HTC) is an aqueous-phase route to produce carbon materials using biomass or biomass-derived precursors. In this paper, a comprehensive physicochemical and textural characterization of HTC materials obtained using four different precursors, namely, xylose, glucose, sucrose, and starch, is presented. The development of porosity in the prepared HTC materials as a function of thermal treatment (under an inert atmosphere) was specifically monitored using N(2) and CO(2) sorption analysis. The events taking place during the thermal treatment process were studied by a combined thermogravimetric/infrared (TGA-IR) measurement. Interestingly, these inexpensive biomass-derived carbon materials show good selectivity for CO(2) adsorption over N(2) (CO(2)/N(2) selectivity of 20 at 273 K, 1 bar and 1:1 gas composition). Furthermore, the elemental composition, morphologies, degree of structural order, surface charge, and functional groups are also investigated.

Mesoporous polymer networks-ultraporous DVB resins by hard-templating of close-packed silica spheres.

The preparation of ultraporous polymer resins using a straightforward hard-templating synthesis is presented. Self-assembly of silica nanospheres into densely packed glasses allows an easy preparation of templates. Polydivinylbenzene resins with surface areas of up to 1000 m(2) g(-1) are synthesized as a model system and porosity analysis reveals bimodal porosity (spherical mesopores and micropores within the pore walls). The prepared systems can be further functionalized without loss of porosity as demonstrated by sulfonation. Because of their large pore sizes (13-28 nm), they are efficient adsorbents also for large molecules. Finally, the systems can also be used as model systems for the study of the pore drying and collapse process, which is of crucial importance for any application of mesoporous polymers.

Crosslinked poly(ionic liquid) nanoparticles: inner structure, size, and morphology.

In this contribution, we present the highly ordered inner structure of crosslinked poly(ionic liquid) nanoparticles. Cryogenic transmission electron microscopy revealed that they resembled centric multilamellar vesicles of different geometries, depending on the exact length of the quaternizing alkyl chains. The nanoparticle size was found to be sensitive to the polymerization conditions, such as the concentrations of monomers and crosslinking agents, the anion type and the externally added salt, but fairly inert to the polymerization temperature and the amount of initiator. The size expansion of the nanoparticles in different polymerization runs was found to be either isotropic or anisotropic via their linear attachment under certain polymerization conditions.

Intrinsically microporous polyesters from betulin - toward renewable materials for gas separation made from birch bark.

Betulin, an abundant triterpene, can be extracted from birch bark and can be used as a renewable monomer in the synthesis of microporous polyesters. Cross-linked networks and hyperbranched polymers are accessible by an A(2) + B(3) reaction, with betulin being the A(2) monomer and B(3) being a trifunctional acid chloride. Reaction of betulin with a diacid dichloride results in linear, soluble polyesters. The present communication proves that the polyreaction follows the classic schemes of polycondensation reactions. The resulting polymers are analyzed with regard to their micro-porosity by gas sorption, NMR spectroscopy, and X-ray scattering methods. The polymers feature intrinsic microporosity, having ultrasmall pores, which makes them candidates for gas separation membranes, e.g., for the separation of CO(2) from N(2) .