The investigation of the binding ability between sodium dodecyl sulfate and Cu (II) in urban stormwater runoff.

The simultaneous presence of heavy metals and surfactants in runoff induces complexation and ecological harm during migration. However, interactions between these pollutants are often overlooked in past studies. Thus, investigating heavy metal-surfactant complexes in runoff is imperative. In this work, Cu (II) and sodium dodecyl sulfate (SDS) were selected to investigate the interaction between heavy metals and surfactants due to the higher detected frequency in runoff. Through 1H NMR and FTIR observation of hydrogen atom nuclear displacement and functional group displacement of SDS, the change of SDS and Cu (II) complexation was obtained, and then the complexation form of Cu (II) and SDS was verified. The results showed that solution pH values and ionic strength had significant effects on the complexation of Cu (II). When the pH values increase from 3.0 to 6.0, the complexation efficiency of SDS with Cu (II) increased by 12.12% at low concentration of SDS, which may be attributed to the excessive protonation in the aqueous solution at acidic condition. The increase of ionic strength would inhibit the complexation reaction efficiency by 19.57% and finally reached the platform with concentration of NaNO3 was 0.10 mmol/L, which was mainly due to the competitive relationship between Na (I) and Cu (II). As a general filtering material in stormwater treatment measures, natural zeolite could affect the interaction between SDS and Cu (II) greatly. After the addition of SDS, the content of free Cu (II) in the zeolite-SDS-Cu (II) three-phase mixed system was significantly reduced, indicating that SDS had a positive effect on the removal of Cu (II) from runoff. This study is of great significance for investigating the migration and transformation mechanism of SDS and Cu (II) in the future and studying the control technology of storm runoff pollution.

Prospective association between perceived stress and anxiety among nursing college students: the moderating roles of career adaptability and professional commitment.

BACKGROUND: Anxiety may stay with nursing students throughout their internship and even persist afterwards. Although many studies have explored the effects of perceived stress on anxiety, the relationship between pre-internship perceived stress and post-internship anxiety levels has not been clarified. In addition, none had focused on the moderating roles of career adaptability and professional commitment between perceived stress and anxiety. This study aims to investigate the influence of pre-internship perceived stress on the post-internship anxiety level of nursing college students, and to analyze the moderating effects of career adaptability and professional commitment on their relationships. METHODS: A longitudinal study design was employed. Full-time nursing college students from a Chinese medical university were recruited by convenient sampling. All surveys were conducted via Wen Juan Xing ( www.wjx.cn ), a widely used web-based survey platform in China. Two waves of surveys were collected in the pre-internship and post-internship periods, with an interval of one year. Among 823 nursing students recruited, 692 students completed all two waves of the survey (response rate: 84.08%). Participants completed a series of questionnaires examining general demographic characteristics, perceived stress, anxiety, career adaptability, and professional commitment both before and after the internship. The bias-corrected bootstrap technique of the Hayes PROCESS macro (Model 2) was used to test the moderation effect. RESULTS: Pre-internship perceived stress was positively associated with post-internship anxiety (ß = 0.474, p < 0.001). Career adaptability would mitigate the effect of perceived stress on anxiety (ß = -0.009, p < 0.01, 95% CI = [-0.013, -0.004]), and this influence became stronger for nursing college students with higher levels of career adaptability. Instead, the professional commitment would enhance the effect of perceived stress on anxiety (ß = 0.004, p < 0.05, 95% CI = [0.001, 0.009]). CONCLUSIONS: Adequate career adaptability was key to alleviating anxiety among nursing interns. Nursing educators and clinical nursing managers should pay attention to cultivating the career adaptability of nursing college students in order to help them successfully achieve identity transformation and career development. Meanwhile, it is crucial to guide them to develop appropriate professional commitment.

Evaluating the effectiveness of a new student-centred laboratory training strategy in clinical biochemistry teaching.

BACKGROUND: The error-proneness in the preanalytical and postanalytical stages is higher than that in the analytical stage of the total testing process. However, preanalytical and postanalytical quality management has not received enough attention in medical laboratory education and tests in clinical biochemistry courses. METHODS/APPROACH: Clinical biochemistry teaching program aim to improve students' awareness and ability of quality management according to international organization for standardization 15,189 requirements. We designed a student-centred laboratory training program, according to case-based learning that included 4 stages: "establish an overall testing process based on the patient's clinical indicator, clarify principles, improve operational skills, and review process and continuous improvement". The program was implemented in our college during the winter semesters of 2019 and 2020. A total of 185 undergraduate students majoring in medical laboratory science participated in the program as a test group, and the other 172 students were set up as the control group and adopted the conventional method. The participants were asked to finish an online survey to evaluate the class at the end. RESULTS/OUTCOMES: The test group had significantly better examination scores not only in experimental operational skills (89.27 ± 7.16 vs. 77.51 ± 4.72, p < 0.05 in 2019 grade, 90.31 ± 5.35 vs. 72.87 ± 8.41 in 2020 grade) but also in total examination (83.47 ± 6.16 vs. 68.90 ± 5.86 in 2019 grade, 82.42 ± 5.72 vs. 69.55 ± 7.54 in 2020 grade) than the control group. The results of the questionnaire survey revealed that the students in the test group better achieved classroom goals than those in the control group (all p < 0.05). CONCLUSIONS: The new student-centred laboratory training program based on case-based learning in clinical biochemistry is an effective and acceptable strategy compared with the conventional training program.

A Framework for Cybersecurity Requirements Management in the Automotive Domain.

The rapid development of intelligent connected vehicles has increased the attack surface of vehicles and made the complexity of vehicle systems unprecedented. Original equipment manufacturers (OEMs) need to accurately represent and identify threats and match corresponding security requirements. Meanwhile, the fast iteration cycle of modern vehicles requires development engineers to quickly obtain cybersecurity requirements for new features in their developed systems in order to develop system code that meets cybersecurity requirements. However, existing threat identification and cybersecurity requirement methods in the automotive domain cannot accurately describe and identify threats for a new feature while also quickly matching appropriate cybersecurity requirements. This article proposes a cybersecurity requirements management system (CRMS) framework to assist OEM security experts in conducting comprehensive automated threat analysis and risk assessment and to help development engineers identify security requirements prior to software development. The proposed CRMS framework enables development engineers to quickly model their systems using the UML-based (i.e., capable of describing systems using UML) Eclipse Modeling Framework and security experts to integrate their security experience into a threat library and security requirement library expressed in Alloy formal language. In order to ensure accurate matching between the two, a middleware communication framework called the component channel messaging and interface (CCMI) framework, specifically designed for the automotive domain, is proposed. The CCMI communication framework enables the fast model of development engineers to match with the formal model of security experts for threat and security requirement matching, achieving accurate and automated threat and risk identification and security requirement matching. To validate our work, we conducted experiments on the proposed framework and compared the results with the HEAVENS approach. The results showed that the proposed framework is superior in terms of threat detection rates and coverage rates of security requirements. Moreover, it also saves analysis time for large and complex systems, and the cost-saving effect becomes more pronounced with increasing system complexity.

Efficient Hot Electron Capture in CuPc/MoSe2 Heterostructure Assisted by Intersystem Crossing.

Efficient hot electron extraction is a promising approach to develop photovoltaic devices that exceed the Shockley-Queisser limit. However, experimental evidence of hot electron harvesting employing an organic-inorganic interface is still elusive. Here, we reveal the hot electron dynamics at a CuPc/MoSe2 interface using steady-state spectroscopy and transient absorption spectroscopy. A hot electron transfer efficiency of greater than 78% from MoSe2 to CuPc is observed, comparable to that achieved in quantum dot hybrid systems. The mechanism is proposed as follows: the photogenerated hot electrons in MoSe2 transfer to CuPc and form singlet charge transfer states, which subsequently transform into triplet charge transfer states assisted by the rapid intersystem crossing, inhibiting back-donation of electrons and facilitating exciton dissociation into CuPc polarons with a nanosecond lifetime. Our results demonstrate that the intersystem crossing of the hybrid electronic state at organic-inorganic interfaces may serve as a scheme to enable efficient hot electron extraction in photovoltaic devices.

Charge Transfer Properties of Heterostructures Formed by Bi2 O2 Se and Transition Metal Dichalcogenide Monolayers.

Atomically thin bismuth oxyselenide (Bi2 O2 Se) exhibits attractive properties for electronic and optoelectronic applications, such as high charge-carrier mobility and good air stability. Recently, the development of Bi2 O2 Se-based heterostructures have attracted enormous interests with promising prospects for diverse device applications. Although the electrical properties of Bi2 O2 Se-based heterostructures have been widely studied, the interlayer charge transfer in these heterostructures remains elusive, despite its importance in harnessing their emergent functionalities. Here, a comprehensive experimental investigation on the interlayer charge transfer properties of two heterostructures formed by Bi2 O2 Se and representative transition metal dichalcogenides (namely, WS2 /Bi2 O2 Se and MoS2 /Bi2 O2 Se) is reported. Kelvin probe force microscopy is used to measure the work functions of the samples, which are further employed to establish type-II band alignment of both heterostructures. Photoluminescence quenching is observed in each heterostructure, suggesting high charge transfer efficiency. Time-resolved and layer-selective pump-probe measurements further prove the ultrafast interlayer charge transfer processes and formation of long-lived interlayer excitons. These results establish the feasibility of integrating 2D Bi2 O2 Se with other 2D semiconductors to fabricate heterostructures with novel charge transfer properties and provide insight for understanding the performance of optoelectronic devices based on such 2D heterostructures.

Robust Interlayer Exciton in WS2/MoSe2 van der Waals Heterostructure under High Pressure.

The van der Waals (vdW) heterostructures have rich functions and intriguing physical properties, which has attracted wide attention. Effective control of excitons in vdW heterostructures is still urgent for fundamental research and realistic applications. Here, we successfully achieved quantitative tuning of the intralayer exciton of monolayers and observed the transition from intralayer excitons to interlayer excitons in WS2/MoSe2 heterostructures, via hydrostatic pressure. The energy of interlayer excitons is in a "locked" or "superstable" state, which is not sensitive to pressure. The first-principles calculation reveals the stronger interlayer interaction which leads to enhanced interlayer exciton behavior in WS2/MoSe2 heterostructures under external pressure and reveals the robust peak of interlayer excitons. This work provides an effective strategy to study the interlayer interaction in vdW heterostructures and reveals the enhanced interlayer excitons in WS2/MoSe2, which could be of great importance for the material and device design in various similar quantum systems.

Distinct Disease Severity Between Children and Older Adults With Coronavirus Disease 2019 (COVID-19): Impacts of ACE2 Expression, Distribution, and Lung Progenitor Cells.

BACKGROUND: Children and older adults with coronavirus disease 2019 (COVID-19) display a distinct spectrum of disease severity yet the risk factors aren't well understood. We sought to examine the expression pattern of angiotensin-converting enzyme 2 (ACE2), the cell-entry receptor for severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), and the role of lung progenitor cells in children and older patients. METHODS: We retrospectively analyzed clinical features in a cohort of 299 patients with COVID-19. The expression and distribution of ACE2 and lung progenitor cells were systematically examined using a combination of public single-cell RNA-seq data sets, lung biopsies, and ex vivo infection of lung tissues with SARS-CoV-2 pseudovirus in children and older adults. We also followed up patients who had recovered from COVID-19. RESULTS: Compared with children, older patients (>50 years.) were more likely to develop into serious pneumonia with reduced lymphocytes and aberrant inflammatory response (P = .001). The expression level of ACE2 and lung progenitor cell markers were generally decreased in older patients. Notably, ACE2 positive cells were mainly distributed in the alveolar region, including SFTPC positive cells, but rarely in airway regions in the older adults (P < .01). The follow-up of discharged patients revealed a prolonged recovery from pneumonia in the older (P < .025). CONCLUSIONS: Compared to children, ACE2 positive cells are generally decreased in older adults and mainly presented in the lower pulmonary tract. The lung progenitor cells are also decreased. These risk factors may impact disease severity and recovery from pneumonia caused by SARS-Cov-2 infection in older patients.

The effects of long-term fertilizations on soil hydraulic properties vary with scales.

Soil structure is an indicator of soil quality and its alterations following cropping system conversion or fertilization change evolve slowly. How such alterations vary with scale remains elusive. We investigated this based on the Rothamsted long-term wheat experiment (since 1843) in the UK. Triplicate cores 7 cm high and 10 cm in diameter were taken from plots that have been under different fertilizations or returned to natural woodland for more than one century for imaging using X-ray computed tomography with the voxel size being 40 µm. We then broke each core and sampled three aggregates from it to scan with the voxel size being 1.5 µm. For each core and aggregate sample, we calculated its pore size distribution, permeability and tortuosity. The results showed that the fertilization change >170 years ago reshaped the soil structure differently between the core scale and the aggregate scale. Macro-porosity of the pores (>40 µm) in the cores unfertilized or fertilized with inorganic fertilizers was low and the pores were poorly connected in the top 10 cm of soil, compared to those given farmyard manure or in the woodland. In all treatments, the pores in the core images were hydraulically anisotropic with their permeability in the horizontal direction being higher than that in the vertical direction, whereas the aggregates were comparatively isotropic. The fertilization affected image porosity and permeability at core scale more significantly than at aggregate scale, and the aggregates fertilized with farmyard manure and in the woodland were more permeable than the aggregates in other treatments. It was also found that compared to no-fertilization or fertilization with complete fertilizers, fertilizing without phosphorus over the past 20 years increased the porosity and permeability of the aggregates but not of the cores. Fertilization with inorganic fertilizers increased the tortuosity of the macropores in the cores but not of the intra-aggregate pores, compared to no-fertilization. Porosity-permeability relationship for aggregates unfertilized or fertilized with inorganic fertilisers followed a power law with R 2 > 0.8. In contrast, the permeability of the aggregates in farmyard manure and in the woodland trended differently as their porosity increased. The results also revealed that the transport ability of the aggregates and cores responded differently to carbon in that with soil carbon increasing, the permeability of the aggregates increased asymptotically while the permeability of the cores, especially its horizontal component, increased exponentially.

Cough in hypereosinophilic syndrome: case report and literature review.

BACKGROUND: Cough and airway eosinophilic inflammation has not been highlighted in hypereosinophilic syndrome (HES). CASE PRESENTATION: We report 2 further cases and reviewed the clinical features and treatment of HES present with cough from the literature. Both cases were middle age male, presenting with chronic cough, airway eosinophilic inflammation and hyper eosinophilia who have been previous misdiagnosed as cough-variant asthma and failed anti-asthma treatment. PDGFRA fusion gene was confirmed in one case, but not in the other case. Both had evidence of myeloproliferative features. The tyrosine kinase inhibitor, imatinib, resulted in complete resolution of eosinophilia and cough. By searching PubMed, we found 8 HES cohorts of 411 cases between 1975 and 2013, where the incidence of cough was 23.11%. Sixteen case reports of HES presented with cough as predominant or sole symptom, with nine male patients with positive PDGFRA fusion gene, who responded well to imatinib. Six of seven patients, who tested negative for the PDGFRA, responded to systemic glucocorticoids. CONCLUSIONS: Cough and airway eosinophilic inflammation is common in some HES patients. PDGFRA+ HES patients present with chronic cough respond well to imatinib. Our case reports indicate that PDGFRA negative HES patients may respond to imatinib as well.

Formation of iron plaque on roots of Iris pseudacorus and its consequence for cadmium immobilization is impacted by zinc concentration.

The impact of iron plaque (IP) on bioavailability of heavy metals to plants has been well documented, but the role of zinc (Zn) in modulating the associated processes remains elusive. We took Iris pseudacorus used in wetland for remediating Cd-contaminated water as an example and systematically studied the combined influence of Cd and Zn concentration on formation of IP and its consequence for immobilization and plant uptake of Cd. The experiment was conducted in hydroponic culture and in each treatment, we measured the physiological traits, activity of antioxidant enzymes (SOD, POD, CAT), mass of the IP, as well as the Cd content in both plant tissues and IP. The results showed that increasing Cd concentration resulted in a steady reduction in IP while the impact of zinc on IP was complicated and appeared to be coupled with Cd. When the Cd concentration was low (0.5 mg L-1 measured as CdCl2 2·5H2O) increasing Zn concentration reduced IP, while when the Cd concentration was increased to 5 mg L-1 increasing zinc concentration led to an increase in IP mass first followed by a decline after Zn concentration exceeded 100 mg L-1 (measured as ZnSO4·7H2O). The change in IP as affected by Zn had a strong consequence for immobilization and plant uptake of Cd. When Cd concentration was low, the IP was comparatively abundant and hence adsorbed most Cd. In contrast, when Cd concentration was high, the IP reduced and the amount of Cd taken up by plant roots and translocated to shoots and leaves increased. Both Cd immobilization and its plant uptake were modulated by Zn concentration. At low Cd concentration the combined Cd immobilized and taken up by plant peaked when the Zn concentration was 50 mg L-1, while at high Cd concentration the combined Cd reached maxima when theZn concentration was 100 mg L-1. The activity of the antioxidant enzymes changed significantly with Zn rather than with Cd. Regardless of Cd concentration, the activity of all three antioxidant enzymes increased first with zinc concentration before declining when the Zn concentration exceeded approximately 100 mg L-1 in all treatments, comparable with the change in immobilization and plant uptake of Cd as the Zn concentration increased. SEM analysis did prove the formation and variation of IP on the root surface of Iris pseudacorus in different treatments. We also found that the plant developed a survival strategy by scarifying its leaves with high Cd content. The results presented in this paper has wide implications as it revealed that care needs to be taken in applying Zn to enhance Cd immobilization and its plant uptake as exceeding the optimal application rate might reduce remediating efficiency rather than increase it.

Interfacial redox processes in memristive devices based on valence change and electrochemical metallization.

Memristive devices based on electrochemical processes are promising candidates for next-generation memory and neuromorphic applications. The redox processes happening at the interfaces are crucial steps for the ionization as well as generation of counter charges, and are thus indispensable for successful resistive switching, but their detailed mechanism has not been fully clarified. Here, we study the interfacial redox reactions in the forming process of memristive devices based on valence change and electrochemical metallization, using high-resolution electron microscopy and electrostatic force microscopy observations. We show direct evidence for the anodic oxidation of oxygen ions and cathodic reduction of moisture in HfO2- and Ta2O5-based valence change cells, which could take place in different horizontal locations. We further found that the anodic reactions always led to more pronounced structural damage to the electrode, indicating the possibility of additional cathodic reactions without producing gaseous products. When an active electrode is present, oxidation of metal atoms takes place at the anodic interface instead. Further investigations on electrochemical metallization cells have identified Cu ionization and moisture reduction as the anodic and cathodic reactions, respectively, and formation of Cu nuclei at the cathodic interface was directly observed. These findings with microscopic evidence could facilitate future development of memristive devices.

Uncontrolled asthma phenotypes defined from parameters using quantitative CT analysis.

OBJECTIVE: Asthma is a heterogeneous disease with diverse clinical phenotypes that have been identified via cluster analyses. However, the classification of phenotypes based on quantitative CT (qCT) is poorly understood. The study was conducted to investigate CT determination of uncontrolled asthma phenotypes. METHODS: Sixty-five patients with uncontrolled asthma (37 with severe asthma, 28 with non-severe asthma) underwent detailed clinical, laboratory, and pulmonary function tests, as well as qCT analysis. Twenty-five healthy subjects were also included in this study and underwent clinical physical examinations, pulmonary function tests, and low-dose CT scans. RESULTS: The mean lumen area/body surface area ratio was smaller in patients with severe uncontrolled asthma compared with that in healthy subjects (9.84 mm2 [SD, 2.57 mm2], 11.96 mm2 [SD, 3.09 mm2]; p = 0.026). However, the percentage of mean wall area (WA) was greater (64.39% [SD, 2.55%], 62.09% [SD, 3.81%], p = 0.011). Air trapping (measured based on mean lung density and VI-856 [%] on expiratory scan) was greater in patients with severe uncontrolled asthma than in those with non-severe uncontrolled asthma and was higher in all patients with uncontrolled asthma than that in healthy subjects (all p < 0.001). Three CT-determined uncontrolled asthma phenotypes were identified. Cluster 1 had mild air trapping with or without proximal airway remodeling. Cluster 2 had moderate air trapping with or without proximal airway remodeling. Cluster 3 had severe air trapping with proximal airway remodeling. CONCLUSIONS: There was obvious air trapping and proximal airway remodeling in patients with severe uncontrolled asthma. The three CT-determined uncontrolled asthma phenotypes might reflect underlying mechanisms of disease in patient stratification and in the different stages of disease development. KEY POINTS: • Obvious air trapping and proximal airway remodeling were present in patients with severe uncontrolled asthma. • CT air trapping indices showed a good correlation with disease duration, total IgE, atopy, and OCS and ICS doses, and were even more strongly correlated with clinical lung function. • Three CT-determined uncontrolled asthma phenotypes were identified, which might reflect underlying mechanisms of disease in patient stratification and in the different stages of disease development.

Plant roots redesign the rhizosphere to alter the three-dimensional physical architecture and water dynamics.

The mechanisms controlling the genesis of rhizosheaths are not well understood, despite their importance in controlling the flux of nutrients and water from soil to root. Here, we examine the development of rhizosheaths from drought-tolerant and drought-sensitive chickpea varieties; focusing on the three-dimensional characterization of the pore volume (> 16 µm voxel spatial resolution) obtained from X-ray microtomography, along with the characterization of mucilage and root hairs, and water sorption. We observe that drought-tolerant plants generate a larger diameter root, and a greater and more porous mass of rhizosheath, which also has a significantly increased water sorptivity, as compared with bulk soil. Using lattice Boltzmann simulations of soil permeability, we find that the root activity of both cultivars creates an anisotropic structure in the rhizosphere, in that its ability to conduct water in the radial direction is significantly higher than in the axial direction, especially in the drought-tolerant cultivar. We suggest that significant differences in rhizosheath architectures are sourced not only by changes in structure of the volumes, but also from root mucilage, and further suggest that breeding for rhizosheath architectures and function may be a potential future avenue for better designing crops in a changing environment.

Nanopatterning on calixarene thin films via low-energy field-emission scanning probe lithography.

Field-emitted, low-energy electrons from the conducting tip of an atomic force microscope were adopted for nanolithography on calixarene ultrathin films coated on silicon wafers. A structural evolution from protrusion to depression down to a 30 nm spatial resolution was reproducibly obtained by tuning the sample voltage and exposure current in the lithography process. Close analyses of the profiles showed that the nanostructures formed by a single exposure with a high current are almost identical to those created by cumulative exposure with a lower current but an equal number of injected electrons. Surface potential imaging by Kelvin probe force microscopy found a negatively charged region surrounding the groove structures once the structures were formed. We conclude that the mechanism related to the formation of a temporary negative state and molecule decomposition, rather than thermal ablation, is responsible for the low-energy field-emission electron lithography on a calixarene molecular resist. We hope that our elucidation of the underlying mechanism is helpful for molecular resist design and further improving the reproducibility and throughput of nanolithography.

Effect of immobilization site on the orientation and activity of surface-tethered enzymes.

Tethering peptides and proteins to abiotic surfaces has the potential to create biomolecule-functionalized surfaces with useful properties. Commonly used methods of immobilization lack control over the orientation in which biological molecules are covalently or physically bound to the surface, leading to sub-optimal materials. Here we use an engineered beta-galactosidase that can be chemically immobilized on a surface with a well-defined orientation through unique surface-accessible cysteine residues. A combined study using sum frequency generation (SFG) vibrational spectroscopy and coarse grained molecular dynamics (MD) simulations was performed to determine the effects of enzyme immobilization site and abiotic surface chemistry on enzyme surface orientation, surface coverage, and catalytic activity. Two beta-galactosidase variants that were immobilized through cysteine introduced at positions 227 and 308 were studied. In both cases, when the abiotic surface was made more hydrophilic, the enzyme surface coverage decreased, but the activity increased. MD simulations indicated that this is due to the weakened interactions between the immobilized enzyme and the more hydrophilic surface. These studies provide improved understanding of how enzyme-surface interactions can be optimized to maximize the catalytic activity of surface tethered enzymes.

Water flow across the interface of contrasting materials: Pressure discontinuity and its implications.

Water flow along or across the interfaces of contrasting materials is ubiquitous in hydrology and how to solve them in macroscopic models derived from volumetric average of the pore-scale processes remains elusive. While the change in the average velocity and pressure at water-sediment interface has been well established for channel flow over porous beds, whether a volumetric average alerts the pressure continuity when water flows across the interface of two porous materials is poorly understood despite its imperative implications in hydrological modelling. The primary purpose of this paper is to provide evidences via pore-scale simulations that volumetrically averaging the pore-scale processes indeed yields a discontinuous pressure when water flows across a material interface. We simulated two columns numerically reconstructed by filling them with stratified media: One is an idealised two-layer system and the other one is a 3D column filled by fine glass beads over coarse glass beads with their pore geometry acquired using x-ray computed tomography. The pore-scale simulation is to mimic the column experiment by driving fluid to flow through the void space under an externally imposed pressure gradient. Once fluid flow reaches steady state, its velocity and pressure in all voxels are sampled and they are then spatially averaged over each section perpendicular to the average flow direction. The results show that the average pressure drops abruptly at the material interface no matter which direction the fluid flows. Compared with the effective permeability estimated from the homogenization methods well established in the literature, the emerged discontinuous pressure at the interface reduces the combined ability of the two strata to conduct water. It is also found that under certain circumstances fluid flow is direction-dependant, moving faster when flowing in the fine-coarse direction than in the coarse-to-fine direction under the same pressure gradient. Although significant efforts are needed to incorporate these findings into practical models, we do elicit the emergence of discontinuous pressure at material interface due to volumetric average as well as its consequent implications in modelling of flow in heterogeneous and stratified media.

Effects of cropping systems upon the three-dimensional architecture of soil systems are modulated by texture.

Soil delivers fundamental ecosystem functions via interactions between physical and biological processes mediated by soil structure. The structure of soil is also dynamic and modified by natural factors and management intervention. The aim of this study was to investigate the effects of different cropping systems on soil structure at contrasting spatial scales. Three systems were studied in replicated plot field experiments involving varying degrees of plant-derived inputs to the soil, viz. perennial (grassland), annual (arable), and no-plant control (bare fallow), associated with two contrasting soil textures (clayey and sandy). We hypothesized the presence of plants results in a greater range (diversity) of pore sizes and that perennial cropping systems invoke greater structural heterogeneity. Accordingly, the nature of the pore systems was visualised and quantified in 3D by X-ray Computed Tomography at the mm and µm scale. Plants did not affect the porosity of clay soil at the mm scale, but at the µm scale, annual and perennial plant cover resulted in significantly increased porosity, a wider range of pore sizes and greater connectivity compared to bare fallow soil. However, the opposite occurred in the sandy soil, where plants decreased the porosity and pore connectivity at the mm scale but had no significant structural effect at the µm scale. These data reveal profound effects of different agricultural management systems upon soil structural modification, which are strongly modulated by the extent of plant presence and also contingent on the inherent texture of the soil.

Effect of Interfacial Molecular Orientation on Power Conversion Efficiency of Perovskite Solar Cells.

A wide variety of charge carrier dynamics, such as transport, separation, and extraction, occur at the interfaces of planar heterojunction solar cells. Such factors can affect the overall device performance. Therefore, understanding the buried interfacial molecular structure in various devices and the correlation between interfacial structure and function has become increasingly important. Current characterization techniques for thin films such as X-ray diffraction, cross section scanning electronmicroscopy, and UV-visible absorption spectroscopy are unable to provide the needed molecular structural information at buried interfaces. In this study, by controlling the structure of the hole transport layer (HTL) in a perovskite solar cell and applying a surface/interface-sensitive nonlinear vibrational spectroscopic technique (sum frequency generation vibrational spectroscopy (SFG)), we successfully probed the molecular structure at the buried interface and correlated its structural characteristics to solar cell performance. Here, an edge-on (normal to the interface) polythiophene (PT) interfacial molecular orientation at the buried perovskite (photoactive layer)/PT (HTL) interface showed more than two times the power conversion efficiency (PCE) of a lying down (tangential) PT interfacial orientation. The difference in interfacial molecular structure was achieved by altering the alkyl side chain length of the PT derivatives, where PT with a shorter alkyl side chain showed an edge-on interfacial orientation with a higher PCE than that of PT with a longer alkyl side chain. With similar band gap alignment and bulk structure within the PT layer, it is believed that the interfacial molecular structural variation (i.e., the orientation difference) of the various PT derivatives is the underlying cause of the difference in perovskite solar cell PCE.

Influence of the side chain and substrate on polythiophene thin film surface, bulk, and buried interfacial structures.

The molecular structures of organic semiconducting thin films mediate the performance of various devices composed of such materials. To fully understand how the structures of organic semiconductors alter on substrates due to different polymer side chains and different interfacial interactions, thin films of two kinds of polythiophene derivatives with different side-chains, poly(3-hexylthiophene) (P3HT) and poly(3-potassium-6-hexanoate thiophene) (P3KHT), were deposited and compared on various surfaces. A combination of analytical tools was applied in this research: contact angle goniometry and X-ray photoelectron spectroscopy (XPS) were used to characterize substrate dielectric surfaces with varied hydrophobicity for polymer film deposition; X-ray diffraction and UV-vis spectroscopy were used to examine the polythiophene film bulk structure; sum frequency generation (SFG) vibrational spectroscopy was utilized to probe the molecular structures of polymer film surfaces in air and buried solid/solid interfaces. Both side-chain hydrophobicity and substrate hydrophobicity were found to mediate the crystallinity of the polythiophene film, as well as the orientation of the thiophene ring within the polymer backbone at the buried polymer/substrate interface and the polymer thin film surface in air. For the same type of polythiophene film deposited on different substrates, a more hydrophobic substrate surface induced thiophene ring alignment with the surface normal at both the buried interface and on the surface in air. For different films (P3HT vs. P3KHT) deposited on the same dielectric substrate, a more hydrophobic polythiophene side chain caused the thiophene ring to align more towards the surface at the buried polymer/substrate interface and on the surface in air. We believe that the polythiophene surface, bulk, and buried interfacial molecular structures all influence the hole mobility within the polythiophene film. Successful characterization of an organic conducting thin film surface, buried interfacial, and bulk structures is a first crucial step in understanding the structure-function relationship of such films in order to optimize device performance. An in-depth understanding on how the side-chain influences the interfacial and surface polymer orientation will guide the future molecular structure design of organic semiconductors.