Towards Intelligently Designed Evolvable Processors.

Evolution-in-Materio is a computational paradigm in which an algorithm reconfigures a material's properties to achieve a specific computational function. This article addresses the question of how successful and well performing Evolution-in-Materio processors can be designed through the selection of nanomaterials and an evolutionary algorithm for a target application. A physical model of a nanomaterial network is developed which allows for both randomness, and the possibility of Ohmic and non-Ohmic conduction, that are characteristic of such materials. These differing networks are then exploited by differential evolution, which optimises several configuration parameters (e.g., configuration voltages, weights, etc.), to solve different classification problems. We show that ideal nanomaterial choice depends upon problem complexity, with more complex problems being favoured by complex voltage dependence of conductivity and vice versa. Furthermore, we highlight how intrinsic nanomaterial electrical properties can be exploited by differing configuration parameters, clarifying the role and limitations of these techniques. These findings provide guidance for the rational design of nanomaterials and algorithms for future Evolution-in-Materio processors.

Stronger together: understanding and protecting karst resources.

The United Nations Educational, Scientific, and Cultural Organization (UNESCO) has recognized more than 350 karst areas of global importance through various designations (Biosphere Reserve, World Heritage Sites, Ramsar Sites, and Global Geoparks) with at least one UNESCO protected area with karst in 86 countries (Gunn 2020). In August 2020, Western Kentucky University, the George Wright Society, and the UNESCO Mammoth Cave Biosphere Region hosted Conservation of Fragile Karst Resources: A Virtual Workshop on Sustainability and Community in support of UNESCO science programs. The purpose of this meeting was to enhance communication and the sharing of ideas and resources between major conservation and science programs that protect, study, or manage cave and karst resources, with particular interest to those of international significance. This special issue is published in celebration and support of the UIS International Year of Caves and Karst and as a call-to-action to better explore, understand, and protect the value of cave and karst areas to humanity in both our everyday lives as well as our natural and cultural heritage.

Monte carlo simulations of organic photovoltaics.

Monte Carlo simulations are a valuable tool to model the generation, separation, and collection of charges in organic photovoltaics where charges move by hopping in a complex nanostructure and Coulomb interactions between charge carriers are important. We review the Monte Carlo techniques that have been applied to this problem, and describe the results of simulations of the various recombination processes that limit device performance. We show how these processes are influenced by the local physical and energetic structure of the material, providing information that is useful for design of efficient photovoltaic systems.

Are hot charge transfer states the primary cause of efficient free-charge generation in polymer:fullerene organic photovoltaic devices? A kinetic Monte Carlo study.

Kinetic Monte Carlo simulations are used to examine the effect of high-energy, 'hot' delocalised charge transfer (HCT) states for donor:acceptor and mixed:aggregate blends, the latter relating to polymer:fullerene photovoltaic devices. Increased fullerene aggregation is shown to enhance charge generation and short-circuit device current - largely due to the increased production of HCT states at the aggregate interface. However, the instances where HCT states are predicted to give internal quantum efficiencies in the region of 50% do not correspond to HCT delocalisation or electron mobility measured in experiments. These data therefore suggest that HCT states are not the primary cause of high quantum efficiencies in some polymer:fullerene OPVs. Instead it is argued that HCT states are responsible for the fast charge generation seen in spectroscopy, but that regional variation in energy levels are the cause of long-term, efficient free-charge generation.

Nitrate fate and decadal shift impacted by land use change in a rural karst basin as revealed by dual nitrate isotopes.

Nitrate pollution in oxygenated karst aquifers is common due to nitrification and anthropogenic inputs. However, the shift of nitrogen sources influenced by enhanced rural tourism activities and land use changes are not well understood. In this study, hydrochemistry and dual nitrate isotopes of water samples from a rural karst basin in Chongqing, southwestern China were employed to investigate the nitrate fate and its decadal change during the periods from 2007-2008 and 2017-2019. The results showed that δ15N-NO3 and δ18O-NO3 values at the groundwater basin resurgence averaged 9 ± 3.4‰ and 2.5 ± 3.4‰, respectively, with a mean NO3- concentration of 19.7 ± 5.4 mg/L in 2017-2019, clearly exceeding natural background levels. The dual isotope results suggested that nitrification occurred at the sampled sites. From 2007-2008 to 2017-2019, the mean δ15N-NO3 values from the primary sink point and the resurgence of the underground river water samples increased from -0.2 ± 2.1 to 11.2 ± 4.8‰, 4.2 ± 0.9 to 9.0 ± 3.4‰, respectively. A Bayesian mixing model in R (MixSIAR) based on the isotopes revealed that soil organic nitrogen, and manure and sewage proportions for the groundwater increased by 34% and 23%, respectively, while chemical fertilizer and atmospheric precipitation proportions decreased by 32% and 25%, respectively. These decadal changes resulted from reforestation practices and enhanced rural tourism activities in the basin, which were evidenced by the change of land use patterns. The elevated nitrogen load from the rapid development of rural tourism is likely to increase this contamination in the near future if the infrastructure cannot meet the demands. The results from this study could contribute to minimizing environmental health risks in drinking water when rural tourism activities are increasing.

Heterogeneity in polymer solar cells: local morphology and performance in organic photovoltaics studied with scanning probe microscopy.

The use of organic photovoltaics (OPVs) could reduce production costs for solar cells because these materials are solution processable and can be manufactured by roll-to-roll printing. The nanoscale texture, or film morphology, of the donor/acceptor blends used in most OPVs is a critical variable that can dominate both the performance of new materials being optimized in the lab and efforts to move from laboratory-scale to factory-scale production. Although efficiencies of organic solar cells have improved significantly in recent years, progress in morphology optimization still occurs largely by trial and error, in part because much of our basic understanding of how nanoscale morphology affects the optoelectronic properties of these heterogeneous organic semiconductor films has to be inferred indirectly from macroscopic measurements. In this Account, we review the importance of nanoscale morphology in organic semiconductors and the use of electrical scanning probe microscopy techniques to directly probe the local optoelectronic properties of OPV devices. We have observed local heterogeneity of electronic properties and performance in a wide range of systems, including model polymer-fullerene blends such as poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM), newer polyfluorene copolymer-PCBM blends, and even all polymer donor-acceptor blends. The observed heterogeneity in local photocurrent poses important questions, chiefly what information is contained and what is lost when using average values obtained from conventional measurements on macroscopic devices and bulk samples? We show that in many cases OPVs are best thought of as a collection of nanoscopic photodiodes connected in parallel, each with their own morphological and therefore electronic and optical properties. This local heterogeneity forces us to carefully consider the adequacy of describing OPVs solely by "average" properties such as the bulk carrier mobility. Characterizing this local heterogeneity in the morphology of an OPV and the consequent variations in local performance is vital to understanding OPV operation.

Effect of charge trapping on geminate recombination and polymer solar cell performance.

In this letter, we examine the effect of charge trapping on geminate recombination and organic photovoltaic performance using a Monte Carlo model. We alter the degree of charge trapping by considering energetic disorder to be spatially uncorrelated or correlated. On correlating energetic disorder, and so reducing the degree of trapping, it is found that power conversion efficiency of blend and bilayer devices improves by factors of 3.1 and 2.6, respectively. These results are related to the experimental data and quantum chemical calculations for poly[9,9-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-1,4-phenylenediamine] (PFB)/poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT) as well as poly(3-hexylthiophene) (P3HT)/(6,6)-phenyl-C(61)-butyric acid methyl ester (PCBM) solar cell systems. The minimization of traps at the heterojunction between electron- and hole-accepting materials, perhaps by molecular design, appears to be a promising strategy to achieve large gains in PV performance. It is also shown that macroscopically measurable quantities such as mobility and energetic disorder are not necessarily good predictors of nanoscale geminate recombination process.

Electrical behaviour and evolutionary computation in thin films of bovine brain microtubules.

We report on the electrical behaviour of thin films of bovine brain microtubules (MTs). For samples in both their dried and hydrated states, the measured currents reveal a power law dependence on the applied DC voltage. We attribute this to the injection of space-charge from the metallic electrode(s). The MTs are thought to form a complex electrical network, which can be manipulated with an applied voltage. This feature has been exploited to undertake some experiments on the use of the MT mesh as a medium for computation. We show that it is possible to evolve MT films into binary classifiers following an evolution in materio approach. The accuracy of the system is, on average, similar to that of early carbon nanotube classifiers developed using the same methodology.

Simulation of loss mechanisms in organic solar cells: A description of the mesoscopic Monte Carlo technique and an evaluation of the first reaction method.

In this letter we evaluate the accuracy of the first reaction method (FRM) as commonly used to reduce the computational complexity of mesoscale Monte Carlo simulations of geminate recombination and the performance of organic photovoltaic devices. A wide range of carrier mobilities, degrees of energetic disorder, and applied electric field are considered. For the ranges of energetic disorder relevant for most polyfluorene, polythiophene, and alkoxy poly(phenylene vinylene) materials used in organic photovoltaics, the geminate separation efficiency predicted by the FRM agrees with the exact model to better than 2%. We additionally comment on the effects of equilibration on low-field geminate separation efficiency, and in doing so emphasize the importance of the energy at which geminate carriers are created upon their subsequent behavior.

Microbial atrazine breakdown in a karst groundwater system and its effect on ecosystem energetics.

In the absence of sunlight energy, microbial community survival in subterranean aquifers depends on integrated mechanisms of energy and nutrient scavenging. Because karst aquifers are particularly sensitive to agricultural land use impacts due to rapid and direct hydrologic connections for pollutants to enter the groundwater, we examined the fate of an exogenous pesticide (atrazine) into such an aquifer and its impact on microbial ecosystem function. Atrazine and its degradation product deethylatrazine (DEA) were detected in a fast-flowing karst aquifer underlying atrazine-impacted agricultural land. By establishing microbial cultures with sediments from a cave conduit within this aquifer, we observed two distinct pathways of microbial atrazine degradation: (i) in cave sediments previously affected by atrazine, apparent surface-derived catabolic genes allowed the microbial communities to rapidly degrade atrazine via hydroxyatrazine, to cyanuric acid, and (ii) in low-impact sediments not previously exposed to this pesticide, atrazine was also degraded by microbial activity at a much slower rate, with DEA as the primary degradation product. In sediments from both locations, atrazine affected nitrogen cycling by altering the abundance of nitrogen dissimulatory species able to use nitrogenous compounds for energy. The sum of these effects was that the presence of atrazine altered the natural microbial processes in these cave sediments, leading to an accumulation of nitrate. Such changes in microbial ecosystem dynamics can alter the ability of DEA to serve as a proxy for atrazine contamination and can negatively affect ecosystem health and water quality in karst aquifers.

Nitrate migration and transformations in groundwater quantified by dual nitrate isotopes and hydrochemistry in a karst World Heritage site.

Karst aquifers are extremely vulnerable to pollution, including from nitrate. This research advances a systematic evaluation of water quality dynamics and processes in a relatively pristine karst flow system impacted by seasonal tourism, in particular migration and transformation of nitrate. Water samples from the Shuifang Spring basin (Jinfoshan Karst World Heritage Site, Chongqing, China) were collected for analysis of ion concentrations and dual nitrate isotopes. The principal sampling sites included untreated tap water from the Jinfoshan Holiday Hotel (JHH), JHH septic system effluent, discharged effluent at Sinkhole #1, and groundwater at Shuifang Spring (SFS, the resurgence of the basin). Sampling from April 2017 through April 2018 showed that higher nitrate concentrations were observed at SFS during busy tourist seasons that occurred in the summer drought and winter dry seasons. Between the septic system and SFS, nitrate was diluted by rainwater and infiltration from the matrix regions of the karst aquifer in the wet season. The MixSIAR model quantitatively revealed that nitrate from manure and sewage (M&S), soil organic nitrogen (SON) and atmospheric precipitation (AP) contributed roughly 55%, 41% and 4% on average, respectively. The mixture of effluent and oxygen-rich tap water from the JHH underwent nitrification at the septic system and Sinkhole #1. After the nitrification and decomposition of organic matter with oxygen consumption in the effluent, denitrification was the dominant response to nitrate attenuation in the effluent of Sinkhole #1 during peak tourism periods. The septic effluent sinking into the aquifer deteriorated the groundwater quality, which was controlled by nitrification in the summer drought and winter dry seasons. In contrast, microorganisms in groundwater assimilated nitrate from effluent in the wet season. Because of the relatively pristine ambient background conditions and seasonal tourism, these results can inform interpretation of background and impacted nitrogen processes in a range of karst settings.

Nitrate sources and biogeochemical processes in karst underground rivers impacted by different anthropogenic input characteristics.

Nitrate is one of the most common pollution sources in groundwater, particularly in highly vulnerable karst aquifers. The potential for nitrification and denitrification within karst aquifers varies in different settings depending on the extent of anthropogenic inputs, so that accurate identification of nitrate sources can be difficult. Geochemical data and dual nitrate isotopes were measured in this study, incorporating a Bayesian isotopic mixing model, and used to identify nitrate sources, nitrification and denitrification, and quantitatively determine nitrate sources under different extents of anthropogenic inputs in three karst catchments within Chongqing Municipality, SW China: Laolongdong (an urbanized area), Qingmuguan (a suburban village), and Shuifang Spring (a protected natural area). At the Laolongdong catchment, the groundwater was in a reducing condition and enriched in δ15NNO3 (averaging 18.9 ± 6.9‰) and δ18ONO3 (averaging 8.5 ± 4.6‰). Manure and sewage waste were the main contributing nitrate sources. A slope of 1.8: 1 of the dual isotopes suggested a denitrification process occurring in anaerobic conduit flow. Within the Qingmuguan catchment, groundwater had average δ15NNO3 and δ18ONO3 values of 9.7 ± 3.5‰, and 1.9 ± 3.4‰, respectively. The data showed evidence for nitrification, and the contribution of soil organic nitrogen was 52.1%, followed by a contribution of 44.8% from manure and wastewater. At the Shuifang Spring catchment, the mean δ15NNO3 and δ18ONO3 values in groundwater were 8.8 ± 2.9‰, 2.3 ± 4.6‰, respectively. Nitrification was the dominant process and most of the nitrate was derived from soil organic nitrogen. This study suggests that karst underground rivers overlain by urban land use undergo denitrification, while the suburban and relatively pristine karst aquifers are dominated by nitrification, allowing development of a conceptual model for nitrate sources and transformations in karst aquifers from the categories of land use (i.e., urban, suburban, and pristine areas). MAIN FINDING: Anthropogenic activities can change biogeochemical nitrogen dynamics of vulnerable karst aquifers, such that the groundwater overlain by an urban settlement has undergone denitrification, while suburban and pristine areas have been dominated by nitrification.

Coupled hydrogeochemical evaluation of a vulnerable karst aquifer impacted by septic effluent in a protected natural area.

Karst aquifers are highly vulnerable to pollution from human activities. Among sources of these contaminants, septic tank effluent can easily pollute karst aquifers, especially concentrated inputs such as those, for example, from tourist hotels. However, the impacts of septic effluent from relatively large, concentrated inputs on karst aquifers have seldom been assessed previously and therefore provide the focus of this study. Artificial tracer tests, geochemical analysis, and dual nitrate stable isotopes were employed to evaluate the impacts of a concentrated input of septic effluent from the Jinfoshan Holiday Hotel (JHH) on the vulnerable Shuifang Spring (SFS) karst aquifer in a remote mountainous area, the Jinfoshan Karst World Heritage Site within Chongqing Municipality of southwest China. The results of artificial tracer tests showed that the underground flow mainly occurred in a primary conduit with a pooled or bifurcated flow path that connects a sinkhole input to SFS. The high tracer recovery rates suggest that the karst aquifer was characterized by high intrinsic vulnerability to contamination. Chemographs at SFS responded rapidly to the episodic release of effluent from JHH. Decreased pH and dissolved oxygen and elevated turbidity, specific conductance and NH4+ concentrations of SFS resulted from the episodic release of septic tank effluent from the JHH during high-use periods. Although the nitrate concentrations were far below the guideline value of the Standard for Groundwater Quality of China, the isotopes of δ15NNO3 and δ18ONO3 suggest that nitrate flowing from SFS was primarily derived from manure and sewage, in addition to soil organic N. Thus, episodic release of septic effluent provides a challenge to the sustainability of karst groundwater management. The results of this study may be relevant to other remote and mountainous karst environments where tourism provide otherwise scarce economic resources and particularly to protected sites throughout the world.

Electron transport and recombination in dye-sensitized mesoporous TiO2 probed by photoinduced charge-conductivity modulation spectroscopy with Monte Carlo modeling.

We present a combined experimental and theoretical investigation into the charge transport and recombination in dye-sensitized mesoporous TiO2. We electronically probe the photoinduced change in conductivity through in-plane devices while simultaneously optically probing signatures of the charge species. Our quasi-continuous wave technique allows us to build data sets of electron mobility and recombination versus charge density over a wide temperature range. We observe that the charge density dependence of mobility in TiO2 is strong at high temperatures and gradually reduces with reducing temperature, to an extent where at temperatures below 260 K the mobility is almost independent of charge density. The mobility first increases and then decreases with reducing temperature at any given charge density. These observed trends are surprising and consistent with the multiple-trapping model for charge transport only if the trap density-of-states (DoS) is allowed to become less deep and narrower as the temperature reduces. Our recombination measurements and simulations over a broad range of charge density and temperature are also consistent with the above-mentioned varying DoS function when the recombination rate constant is allowed to increase with temperature, itself consistent with a thermally activated charge-transfer process. Further to using the Monte Carlo simulations to model the experimental data, we use the simulations to aid our understanding of the limiting factors to charge transport and recombination. According to our model, we find that the charge recombination is mainly governed by the recombination reaction rate constant and the charge density dependence is mainly a result of the bimolecular nature of the recombination process. The implication to future material design is that if the mobility can be enhanced without increasing the charge density in the film, for instance by reducing the average trap depth, then this will not be at the sacrifice of comparably enhanced recombination and it will greatly increase the charge carrier diffusion lengths in dye-sensitized or mesoscopic solar cells.

Low-Voltage Solution-Processed Hybrid Light-Emitting Transistors.

We report the development of low operating voltages in inorganic-organic hybrid light-emitting transistors (HLETs) based on a solution-processed ZrO x gate dielectric and a hybrid multilayer channel consisting of the heterojunction In2O3/ZnO and the organic polymer "Super Yellow" acting as n- and p-channel/emissive layers, respectively. Resulting HLETs operate at the lowest voltages reported to-date (<10 V) and combine high electron mobility (22 cm2/(V s)) with appreciable current on/off ratios (≈103) and an external quantum efficiency of 2 × 10-2% at 700 cd/m2. The charge injection, transport, and recombination mechanisms within this HLET architecture are discussed, and prospects for further performance enhancement are considered.

The impact of outcome valence on the susceptibility to suggestion for post-event causal misinformation.

Recent research has demonstrated that people are especially susceptible to false memory development for suggested misinformation that fills a causal role (i.e., explains some known outcome) (Chrobak & Zaragoza, 2013). However, little is known about how factors associated with the witnessed outcome impact the likelihood of false memory development. In the present study, outcome valence (negative, positive, or neutral) was manipulated. Participants heard several short stories that contained an outcome (e.g., a counselor getting promoted) that lacked a causal explanation. Participants were subsequently exposed to suggested causal misinformation that explained that outcome (e.g., the counselor performed an impressive act the previous day) and then were tested on their memory for the original event. Results indicated that participants incorrectly reported the suggested causal information more when it explained either a positive or negative outcome as opposed to a neutral outcome. Theoretical and practical implications of these findings are discussed.

South China karst aquifer storm-scale hydrochemistry.

The peak cluster and peak forest karst regions of Southeast Asia form one of the earth's most extensive karst regions. Although there exists a rich, descriptive tradition of geomorphic work performed there, little quantitative study has been made of carbonate hydrochemistry and related aquifer/landscape behavior and evolution. In this paper, high-resolution measurements of ground water carbonate chemistry and flow were made and analyzed at two adjacent locations within the subtropical peak cluster karst of the Guilin Karst Experimental Site in Guangxi Province, China. While waters from a large, perennial spring represent the exit for the 2 km2 catchment's conduit flow, a nearby well (within 5 m) measures water in the conduit-adjacent, fractured media. Results indicate that within peak cluster karst aquifer flow systems, spatially heterogeneous flow conditions can exist with respect to timing, magnitude, and, in some cases, direction of responses, as different controls can operate in the different flow system components. Storm-scale chemical responses are controlled by dilution from rapid infiltration of rain water, CO2 gas sources and sinks, and water-carbonate rock interactions. At this particular location, there is also an influence from high pH recharge, apparently buffered by atmospheric limestone dust. An example of the varying controls on storm-scale responses within the flow system is that within the fractured medium, variations in the ground water calcite saturation index, a key parameter influencing rates of aquifer/landscape evolution, are small and controlled by CO2 gas, while in the conduit they are more significant and dominated instead by dilution with rain water.

'Stent in a stent'--an alternative technique for removing partially covered stents following sleeve gastrectomy complications.

Endoscopic stenting is a relatively new technique for the treatment of post sleeve gastrectomy complications. Partially covered stents are used in this method to minimise the risk of migration but they are associated with difficulties with removal. Patients requiring emergency stenting following sleeve gastrectomy underwent insertion of a partially covered metallic stent. One month later, if the stent was not easily removable, a fully covered overlapping stent was inserted and the patient was readmitted 2 weeks later for removal of both stents. Four patients required stenting following sleeve gastrectomy leaks, and one patient required stenting for a stricture. In these cases, a 'stent in a stent' technique was used for removal. This technique allows the safe removal of partially covered stents inserted following sleeve gastrectomy complications.