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Background: The incidence of tick-borne diseases is increasing across the USA, with cases concentrated in the northeastern and midwestern regions of the country. Ixodes scapularis is one of the most important tick-borne disease vectors and has spread throughout the northeastern USA over the past four decades, with established populations in all states of the region., Methods: To better understand the rapid expansion of I. scapularis and the pathogens they transmit, we aggregated and analyzed I. scapularis abundance and pathogen prevalence data from across the northeastern USA, including the states of Connecticut, Maine, New Hampshire, New York and Vermont, from 1989 to 2021. Maine was the only state to collect data during the entire time period, with the other states collecting data during a subset of this time period starting in 2008 or later. We harmonized I. scapularis abundance by county and tick season, where the nymph season is defined as May to September and the adult season is October to December, and calculated I. scapularis pathogen infection prevalence as the percentage of ticks that tested positive for Anaplasma phagocytophilum, Babesia microti, Borrelia burgdorferi, and Borrelia miyamotoi. We then explored temporal trends in I. scapularis abundance and pathogen prevalence data using linear models., Results: The resulting dataset is one of the most spatially and temporally comprehensive records of tick abundance and pathogen prevalence in the USA. Using linear models, we found small or insignificant changes in the abundance of nymphs and adults over time; however, A. phagocytophilum, B. microti and B. burgdorferi prevalence in both nymphs and adults has increased over time. For the period 2017-2021, the statewide average prevalence of B. burgdorferi ranged from 19% to 25% in I. scapularis nymphs and from to 49% to 54% in I. scapularis adults. The statewide average prevalence of all other pathogens in I. scapularis for 2017-2021, including A. phagocytophilum (4-6% for nymphs, 4-9% for adults), B. microti (4-8% for nymphs, 2-13% for adults) and B. miyamotoi (1-2% for nymphs, 1-2% for adults), was considerably less., Conclusions: Our efforts revealed the complications of creating a comprehensive dataset of tick abundance and pathogen prevalence across time and space due to variations in tick collection and pathogen testing methods. Although tick abundance has not changed along the more southern latitudes in our study over this time period, and only gradually changed in the more northern latitudes of our study, human risk for exposure to tick-borne pathogens has increased due to increased pathogen prevalence in I. scapularis. This dataset can be used in future studies of I. scapularis and pathogen prevalence across the northeastern USA and to evaluate models of I. scapularis ecology and population dynamics., Competing Interests: Declarations. Ethics approval and consent to participate: Not applicable. Consent for publication: Not applicable. Competing interests: The authors declare no competing interests., (© 2024. The Author(s).)

As the range of Ixodes scapularis Say expands, host abundance and land use can play important roles in regions where ticks and their associated pathogens are emerging. Small mammal hosts serve as reservoirs of tick-borne pathogens, with Peromyscus leucopus Rafinesque often considered a primary reservoir. A sympatric species Peromyscus maniculatus Wagner is also a competent reservoir and is notoriously difficult to differentiate from P. leucopus. Anthropogenic land use can alter host and habitat availability, potentially changing tick exposure risk. We tested the hypotheses that tick infestation and pathogen prevalence differ between the two Peromyscus spp. and that host-seeking I. scapularis density and pathogen prevalence differ across land use and ecotone gradients. We live trapped small mammals and collected ticks across 3 land-use classifications and ecotones in Maine, an emergent area for tick-borne disease. We tested each small mammal and tick sample for Borrelia burgdorferi, Anaplasma phagocytophilum, and Babesia microti. While both Peromyscus spp. serve as hosts for immature ticks, P. leucopus exhibited a higher tick infestation frequency and intensity. We did not detect any significant difference in pathogen infection prevalence between the two species. The density of I. scapularis nymphs and the density of infected nymphs did not differ significantly between land-use types, though did differ across ecotones. We also noted a significant north/south gradient, with higher tick densities and pathogen prevalence at the southern end of the study area. Our study highlights the potential variability in tick density and pathogen prevalence across fine spatial scales within an emerging region for tick-borne disease., (© The Author(s) 2024. Published by Oxford University Press on behalf of Entomological Society of America.)

The Zika virus epidemic of 2015-16, which caused over 1 million confirmed or suspected human cases in the Caribbean and Latin America, was driven by a combination of movement of infected humans and availability of suitable habitat for mosquito species that are key disease vectors. Both human mobility and mosquito vector abundances vary seasonally, and the goal of our research was to analyze the interacting effects of disease vector densities and human movement across metapopulations on disease transmission intensity and the probability of super-spreader events. Our research uses the novel approach of combining geographical modeling of mosquito presence with network modeling of human mobility to offer a comprehensive simulation environment for Zika virus epidemics that considers a substantial number of spatial and temporal factors compared to the literature. Specifically, we tested the hypotheses that 1) regions with the highest probability of mosquito presence will have more super-spreader events during dry months, when mosquitoes are predicted to be more abundant, 2) regions reliant on tourism industries will have more super-spreader events during wet months, when they are more likely to contribute to network-level pathogen spread due to increased travel. We used the case study of Colombia, a country with a population of about 50 million people, with an annual calendar that can be partitioned into overlapping cycles of wet and dry seasons and peak tourism and off tourism seasons that drive distinct cyclical patterns of mosquito abundance and human movement. Our results show that whether the first infected human was introduced to the network during the wet versus dry season and during the tourism versus off tourism season profoundly affects the severity and trajectory of the epidemic. For example, Zika virus was first detected in Colombia in October of 2015. Had it originated in January, a dry season month with high rates of tourism, it likely could have infected up to 60% more individuals and up to 40% more super-spreader events may have occurred. In addition, popular tourism destinations such as Barranquilla and Cartagena have the highest risk of super-spreader events during the winter, whereas densely populated areas such as Medellín and Bogotá are at higher risk of sustained transmission during dry months in the summer. Our research demonstrates that public health planning and response to vector-borne disease outbreaks requires a thorough understanding of how vector and host patterns vary due to seasonality in environmental conditions and human mobility dynamics. This research also has strong implications for tourism policy and the potential response strategies in case of an emergent epidemic., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2024 Lieberthal et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

The reaction center-light-harvesting complex 1 (RC-LH1) plays an essential role in the primary reactions of bacterial photosynthesis. Here, we present high-resolution structures of native monomeric and dimeric RC-LH1 supercomplexes from Rhodobacter ( Rba. ) blasticus using cryo-electron microscopy. The RC-LH1 monomer is composed of an RC encircled by an open LH1 ring comprising 15 αβ heterodimers and a PufX transmembrane polypeptide. In the RC-LH1 dimer, two crossing PufX polypeptides mediate dimerization. Unlike Rhodabacter sphaeroides counterpart, Rba. blasticus RC-LH1 dimer has a less bent conformation, lacks the PufY subunit near the LH1 opening, and includes two extra LH1 αβ subunits, forming a more enclosed S-shaped LH1 ring. Spectroscopic assays reveal that these unique structural features are accompanied by changes in the kinetics of quinone/quinol trafficking between RC-LH1 and cytochrome bc 1 . Our findings reveal the assembly principles and structural variability of photosynthetic RC-LH1 supercomplexes, highlighting diverse strategies used by phototrophic bacteria to optimize light-harvesting and electron transfer in competitive environments.

The SWR1 chromatin remodeling complex is recruited to +1 nucleosomes downstream of transcription start sites of eukaryotic promoters, where it exchanges histone H2A for the specialized variant H2A.Z. Here, we use cryoelectron microscopy (cryo-EM) to resolve the structural basis of the SWR1 interaction with free DNA, revealing a distinct open conformation of the Swr1 ATPase that enables sliding from accessible DNA to nucleosomes. A complete structural model of the SWR1-nucleosome complex illustrates critical roles for Swc2 and Swc3 subunits in oriented nucleosome engagement by SWR1. Moreover, an extended DNA-binding α helix within the Swc3 subunit enables sensing of nucleosome linker length and is essential for SWR1-promoter-specific recruitment and activity. The previously unresolved N-SWR1 subcomplex forms a flexible extended structure, enabling multivalent recognition of acetylated histone tails by reader domains to further direct SWR1 toward the +1 nucleosome. Altogether, our findings provide a generalizable mechanism for promoter-specific targeting of chromatin and transcription complexes., Competing Interests: Declaration of interests B.F.P. is an owner of and has a financial interest in Peconic, which uses the ChIP-exo technology (US Patent 20100323361A1) implemented in this study and could potentially benefit from the outcomes of this research., (Copyright © 2024 Elsevier Inc. All rights reserved.)

The controlled aggregation of organic chromophores into supramolecular structures offers a way to control and tune photocatalytic activity. However, the underlying mechanisms of charge transfer and accumulation are still unclear. Time-resolved vibrational spectroscopy is a powerful structural probe for studying photogenerated intermediates. Here, we employ time-resolved infrared (TRIR) spectroscopy to study CNP (2,6-bis(4-cyanophenyl)-4-(9-phenyl-9 H -carbazol-3-yl)pyridine-3,5-dicarbonitrile) and its supramolecular aggregates. We show that excitation of the charge transfer (CT) band of semi-crystalline nanofibers (CNP-f) gives rise to long-lived delocalised polarons, which form within the instrument response timescale. By contrast the CNP nanospheres (CNP-s) give rise to a shorter lived polaron that appears to have a greater degree of localization. CNP-f and CNP-s are known to show markedly different levels of photocatalytic activity for hydrogen and hydrogen peroxide formation which are rationalised owing to these differences in photodynamics immediately following photon absorption., Competing Interests: The authors declare no competing financial interests., (This journal is © The Royal Society of Chemistry.)

Biohybrid photocatalysts are composite materials that combine the efficient light-absorbing properties of synthetic materials with the highly evolved metabolic pathways and self-repair mechanisms of biological systems. Here, we show the potential of conjugated polymers as photosensitizers in biohybrid systems by combining a series of polymer nanoparticles with engineered Escherichia coli cells. Under simulated solar light irradiation, the biohybrid system consisting of fluorene/dibenzo [ b,d ]thiophene sulfone copolymer (LP41) and recombinant E. coli (i.e., a LP41/HydA BL21 biohybrid) shows a sacrificial hydrogen evolution rate of 3.442 mmol g -1 h -1 (normalized to polymer amount). It is over 30 times higher than the polymer photocatalyst alone (0.105 mmol g -1 h -1 ), while no detectable hydrogen was generated from the E. coli cells alone, demonstrating the strong synergy between the polymer nanoparticles and bacterial cells. The differences in the physical interactions between synthetic materials and microorganisms, as well as redox energy level alignment, elucidate the trends in photochemical activity. Our results suggest that organic semiconductors may offer advantages, such as solution processability, low toxicity, and more tunable surface interactions with the biological components over inorganic materials.

Forest management practices designed to meet varied landowner objectives affect wildlife habitat and may interrupt the life-cycle stages of disease vectors, including the black-legged tick, Ixodes scapularis Say (Acari: Ixodidae). Ixodes scapularis transmits multiple pathogens including Borrelia burgdorferi, the causative agent of Lyme disease, which is the most common tick-borne disease in the United States. There is evidence that a range of active forest management practices (e.g., invasive plant removal, prescribed burning) can alter tick densities and pathogen transmission. However, few studies have investigated relationships between forest stand structural variables commonly manipulated by timber harvesting and tick ecology. Foresters may harvest timber to create certain forest structural conditions like the mean number of trees, or basal area, per hectare. This study used a spatially replicated experiment in a blocked design to compare forest stands with a range of overstory structures and document variations in the midstory, understory, and forest floor, as well as microclimate conditions within tick off-host habitat. Greater numbers of trees or basal area per hectare correlated with greater canopy closure but less understory cover, stabilized microclimate temperature, higher microclimate humidity, and greater I. scapularis nymph densities. A random forest model identified understory forest structure as the strongest predictor of nymph densities. There was no relationship between the number of trees or basal area per hectare and daily deer (Odocoileus virginianus Zimmermann) activity or nymphal infection prevalence. These findings provide a deeper understanding of tick-habitat associations within a forest stand and have the potential to inform forest management decisions., (© The Author(s) 2024. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For commercial re-use, please contact reprints@oup.com for reprints and translation rights for reprints. All other permissions can be obtained through our RightsLink service via the Permissions link on the article page on our site—for further information please contact journals.permissions@oup.com.)

The activity of molecular electrocatalysts depends on the interplay of electrolyte composition near the electrode surface, the composition and morphology of the electrode surface, and the electric field at the electrode-electrolyte interface. This interplay is challenging to study and often overlooked when assessing molecular catalyst activity. Here, we use surface specific vibrational sum frequency generation (VSFG) spectroscopy to study the solvent and potential dependent activation of Mo(bpy)(CO) 4 , a CO 2 reduction catalyst, at a polycrystalline Au electrode. We find that the parent complex undergoes potential dependent reorientation at the electrode surface when a small amount of N -methyl-2-pyrrolidone (NMP) is present. This preactivates the complex, resulting in greater yields at less negative potentials, of the active electrocatalyst for CO 2 reduction.

Incidence of Lyme disease, a tick-borne illness prevalent in the US, is increasing in endemic regions and regions with no previous history of the disease, significantly impacting public health. We examined space-time patterns of Lyme disease incidence and the influence of ecological and social factors on spatial synchrony, i.e., correlated incidence fluctuations across US counties. Specifically, we addressed these questions: Does Lyme disease incidence exhibit spatial synchrony? If so, what geographic patterns does Lyme disease synchrony exhibit? Are geographic patterns of disease synchrony related to weather, land cover, access to health care, or tick-borne disease awareness? How do effects of these variables on Lyme disease synchrony differ geographically? We used network analysis and matrix regression to examine geographical patterns of Lyme disease synchrony and their potential mechanisms in 399 counties in the eastern and Midwestern US. We found two distinct regions of synchrony in Northeast and upper Midwest regions exhibiting opposing temporal fluctuations in incidence. Spatial patterns of Lyme disease synchrony were partly explained by land cover, weather, poverty, and awareness of tick-borne illness, with significant predictive variables changing regionally. However, the two regions may have become more synchronous over time, potentially leading to higher-amplitude nation-wide fluctuations in disease incidence., (© 2024. The Author(s).)

Microglia are implicated as primarily detrimental in pain models; however, they exist across a continuum of states that contribute to homeostasis or pathology depending on timing and context. To clarify the specific contribution of microglia to pain progression, we take advantage of a temporally controlled transgenic approach to transiently deplete microglia. Unexpectedly, we observe complete resolution of pain coinciding with microglial repopulation rather than depletion. We find that repopulated mouse spinal cord microglia are morphologically distinct from control microglia and exhibit a unique transcriptome. Repopulated microglia from males and females express overlapping networks of genes related to phagocytosis and response to stress. We intersect the identified mouse genes with a single-nuclei microglial dataset from human spinal cord to identify human-relevant genes that may ultimately promote pain resolution after injury. This work presents a comprehensive approach to gene discovery in pain and provides datasets for the development of future microglial-targeted therapeutics., Competing Interests: Declaration of interests The authors declare that they have no competing interests., (Copyright © 2024 The Author(s). Published by Elsevier Inc. All rights reserved.)

The nature of the electrolyte cation is known to have a significant impact on electrochemical reduction of CO 2 at catalyst|electrolyte interfaces. An understanding of the underlying mechanism responsible for catalytic enhancement as the alkali metal cation group is descended is key to guide catalyst development. Here, we use in situ vibrational sum frequency generation (VSFG) spectroscopy to monitor changes in the binding modes of the CO intermediate at the electrochemical interface of a polycrystalline Cu electrode during CO 2 reduction as the electrolyte cation is varied. A CO bridge mode is observed only when using Cs + , a cation that is known to facilitate CO 2 reduction on Cu, supporting the proposed involvement of CO bridge sites in CO coupling mechanisms during CO 2 reduction. Ex situ measurements show that the cation dependent CO bridge modes correlate with morphological changes of the Cu surface., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Hard-bodied ticks have become a major concern in temperate regions because they transmit a variety of pathogens of medical significance. Ticks and pathogens interact with hosts in a complex social-ecological system (SES) that influences human exposure to tick-borne diseases (TBD). We argue that addressing the urgent public health threat posed by TBD requires an understanding of the integrated processes in the forest ecosystem that influence tick density and infection prevalence, transmission among ticks, animal hosts, and ultimately disease prevalence in humans. We argue that collaborative modeling of the human-tick SES is required to understand the system dynamics as well as move science toward policy action. Recent studies in human health have shown the importance of stakeholder participation in understanding the factors that contribute to human exposure to zoonotic diseases. We discuss how collaborative modeling can be applied to understand the impacts of forest management practices on ticks and TBD. We discuss the potential of collaborative modeling for encouraging participation of diverse stakeholders in discussing the implications of managing forest ticks in the absence of large-scale control policy., (© 2024. EcoHealth Alliance.)

Ticks are blood-feeding parasites with limited locomotion, known for transmitting multiple pathogens to vertebrates. England et al. suggest that ticks can be easily pulled, via electrostatic induction, toward charged hosts with fluffy coats that are prone to accumulate higher electrostatic potentials. Thus, static electricity may influence ticks' ecology and management., Competing Interests: Declaration of interests The authors declare no competing interests., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Elucidating the photosynthetic processes that occur within the reaction center-light-harvesting 1 (RC-LH1) supercomplexes from purple bacteria is crucial for uncovering the assembly and functional mechanisms of natural photosynthetic systems and underpinning the development of artificial photosynthesis. Here, we examined excitation energy transfer of various RC-LH1 supercomplexes of Rhodobacter sphaeroides using transient absorption spectroscopy, coupled with lifetime density analysis, and studied the roles of the integral transmembrane polypeptides, PufX and PufY, in energy transfer within the RC-LH1 core complex. Our results show that the absence of PufX increases both the LH1 → RC excitation energy transfer lifetime and distribution due to the role of PufX in defining the interaction and orientation of the RC within the LH1 ring. While the absence of PufY leads to the conformational shift of several LH1 subunits toward the RC, it does not result in a marked change in the excitation energy transfer lifetime.

Kinetic and structural investigations of the flavohemoglobin-type NO dioxygenase have suggested critical roles for transient Fe(III)O 2 complex formation and O 2 -forced movements affecting hydride transfer to the FAD cofactor and electron-transfer to the Fe(III)O 2 complex. Stark-effect theory together with structural models and dipole and internal electrostatic field determinations provided a semi-quantitative spectroscopic method for investigating the proposed Fe(III)O 2 complex and O 2 -forced movements. Deoxygenation of the enzyme causes Stark effects on the ferric heme Soret and charge-transfer bands revealing the Fe(III)O 2 complex. Deoxygenation also elicits Stark effects on the FAD that expose forces and motions that create a more restricted NADH access to FAD for hydride transfer and switch electron-transfer off. Glucose also forces the enzyme toward an off state. Amino acid substitutions at the B10, E7, E11, G8, D5, and F7 positions influence the Stark effects of O 2 on resting heme spin states and FAD consistent with the proposed roles of the side chains in the enzyme mechanism. Deoxygenation of ferric myoglobin and hemoglobin A also induces Stark effects on the hemes suggesting a common 'oxy-met' state. The ferric myoglobin and hemoglobin heme spectra are also glucose-responsive. A conserved glucose or glucose-6-phosphate binding site is found bridging the BC-corner and G-helix in flavohemoglobin and myoglobin suggesting novel allosteric effector roles for glucose or glucose-6-phosphate in the NO dioxygenase and O 2 storage functions. The results support the proposed roles of a ferric O 2 intermediate and protein motions in regulating electron-transfer during NO dioxygenase turnover., Competing Interests: Declaration of Competing Interest The authors declare that they have no conflict of interest with the contents of this article., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Tick-borne disease poses a growing public health burden in the United States and understanding the patterns of presence and density of infected vector ticks is key to developing and implementing effective public health management strategies. Citizen science has emerged as a highly effective means to generate data sets on the geographical distribution of tick species. But to date, nearly all citizen science studies of ticks are 'passive surveillance' programs in which researchers accept reports of ticks, together with either physical specimens or digital images, found opportunistically on people, pets, and livestock from community members for species identification and in some cases also tick-borne pathogen detection. These studies are limited because data are not collected systematically, making comparisons among locations and over time challenging, and introducing considerable reporting bias. In this study, we engaged citizen scientists in 'active surveillance' of host-seeking ticks, training volunteers to actively collect ticks on their woodland properties in an emergent region of tick-borne disease in the state of Maine, USA. We developed volunteer recruitment strategies, materials to train volunteers in data collection methods, field data collection protocols based on techniques used by professional scientists, and a variety of incentives to promote volunteer retention and satisfaction with their experiences, and we communicated research findings to participants. A total of 125 volunteers in 2020 and 181 volunteers in 2021 collected 7,246 ticks in southern and coastal Maine, including the American dog tick (Dermacentor variabilis, 4,023 specimens), the blacklegged tick (Ixodes scapularis, 3,092 specimens), and the rabbit tick (Haemaphysalis leporispalustris, 102 specimens). We demonstrated the feasibility of citizen scientists collecting ticks using active surveillance methods and found that volunteers were motivated to participate largely by their interest in the scientific problem and a desire to learn about ticks on their properties., Competing Interests: Declaration of Competing Interests The authors declare no competing interests., (Copyright © 2023 The Author(s). Published by Elsevier GmbH.. All rights reserved.)

Predicting and preparing for the trajectory of disease epidemics relies on a knowledge of environmental and socioeconomic factors that affect transmission rates on local and global spatial scales. This article discusses the simulation of epidemic outbreaks on human metapopulation networks with community structure, such as cities within national boundaries, for which infection rates vary both within and between communities. We demonstrate mathematically, through next-generation matrices, that the structures of these communities, setting aside all other considerations such as disease virulence and human decision-making, have a profound effect on the reproduction rate of the disease throughout the network. In high modularity networks, with high levels of separation between neighboring communities, disease epidemics tend to spread rapidly in high-risk communities and very slowly in others, whereas in low modularity networks, the epidemic spreads throughout the entire network as a steady pace, with little regard for variations in infection rate. The correlation between network modularity and effective reproduction number is stronger in population with high rates of human movement. This implies that the community structure, human diffusion rate, and disease reproduction number are all intertwined, and the relationships between them can be affected by mitigation strategies such as restricting movement between and within high-risk communities. We then test through numerical simulation the effectiveness of movement restriction and vaccination strategies in reducing the peak prevalence and spread area of outbreaks. Our results show that the effectiveness of these strategies depends on the structure of the network and the properties of the disease. For example, vaccination strategies are most effective in networks with high rates of diffusion, whereas movement restriction strategies are most effective in networks with high modularity and high infection rates. Finally, we offer guidance to epidemic modelers as to the ideal spatial resolution to balance accuracy and data collection costs., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Molecular packing controls optoelectronic properties in organic molecular nanomaterials. Here we report a donor-acceptor organic molecule (2,6-bis(4-cyanophenyl)-4-(9-phenyl-9H-carbazol-3-yl)pyridine-3,5-dicarbonitrile) that exhibits two aggregate states in aqueous dispersions: amorphous nanospheres and ordered nanofibres with π-π molecular stacking. The nanofibres promote sacrificial photocatalytic H 2 production (31.85 mmol g -1  h -1 ) while the nanospheres produce hydrogen peroxide (H 2 O 2 ) (3.20 mmol g -1 h -1 in the presence of O 2 ). This is the first example of an organic photocatalyst that can be directed to produce these two different solar fuels simply by changing the molecular packing. These different packings affect energy band levels, the extent of excited state delocalization, the excited state dynamics, charge transfer to O 2 and the light absorption profile. We use a combination of structural and photophysical measurements to understand how this influences photocatalytic selectivity. This illustrates the potential to achieve multiple photocatalytic functionalities with a single organic molecule by engineering nanomorphology and solid-state packing., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

To understand the mechanisms of water oxidation on materials such as hematite it is important that accurate measurements and models of the interfacial fields at the semiconductor liquid junction are developed. Here we demonstrate how electric field induced second harmonic generation (EFISHG) spectroscopy can be used to monitor the electric field across the space-charge and Helmholtz layers in a hematite electrode during water oxidation. We are able to identify the occurrence of Fermi level pinning at specific applied potentials which lead to a change in the Helmholtz potential. Through combined electrochemical and optical measurements we correlate these to the presence of surface trap states and the accumulation of holes (h + ) during electrocatalysis. Despite the change in Helmholtz potential as h + accumulate we find that a population model can be used to fit the electrocatalytic water oxidation kinetics with a transition between a first and third order regime with respect to hole concentration. Within these two regimes there are no changes in the rate constants for water oxidation, indicating that the rate determining step under these conditions does not involve electron/ion transfer, in-line with it being O-O bond formation., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

Objective: To examine body shape perception in 218 adults without obesity or history of eating disorders during caloric restriction (CR)., Methods: Comprehensive Assessment of Long-term Effects of Reducing Intake of Energy (CALERIE) is a 2-year, randomized clinical trial using a 2:1 assignment (CR, 25% reduction in calories; Control, typical diet). For this secondary analysis, we examined perceived body shape using the Body Shape Questionnaire (BSQ). Analyses of BSQ scores are reported by group, over time, by sex, and by BMI. Data for body fat percentage, symptoms of depression, food cravings, maximal oxygen consumption, and stress were analyzed for their association with BSQ scores., Results: Compared to control, CR reduced BSQ scores. Women tended to have greater concern with body shape than men across all measurement times. There was no difference in change in BSQ scores at 12 or 24 months between those with a BMI < 25 kg/m 2 or ≥ 25 kg/m 2 . Change in body fat percentage was most correlated with change in BSQ score from 0 to 12 (r = 0.39) and 0-24 months (r = 0.38). For change in BSQ score, Akaike/ Bayesian information criterion (AIC/BIC) found that the model of best fit included the following three change predictors: change in body fat percentage, depression symptoms, and food cravings. For 0-12 months, AIC/BIC = 1482.0/1505.6 and for 0-24 months AIC/BIC = 1364.8/1386.5., Conclusions: CR is associated with reduced concern for body shape in men and women without obesity and with no history of eating disorders. Body shape perception among this sample was complex and influenced by multiple factors., Level of Evidence: Level I, randomized controlled trial., (© 2023. The Author(s).)

Experimental autoimmune encephalomyelitis (EAE), induced by the adoptive transfer of Th17 cells, typically presents with ascending paralysis and inflammatory demyelination of the spinal cord. Brain white matter is relatively spared. Here we show that treatment of Th17 transfer recipients with a highly selective inhibitor to the TAM family of tyrosine kinase receptors results in ataxia associated with a shift of the inflammatory infiltrate to the hindbrain parenchyma. During homeostasis and preclinical EAE, hindbrain microglia express high levels of the TAM receptor Mer. Our data suggest that constitutive TAM receptor signaling in hindbrain microglia confers region-specific protection against Th17 mediated EAE., Competing Interests: Declaration of Competing Interest The authors have no conflict of interest to report., (Copyright © 2023 The Author(s). Published by Elsevier B.V. All rights reserved.)

National parks are unique and significant vector-borne pathogen transmission settings, engaging over 300 million people in outdoor recreation per year. In this study, we integrated vector surveys and ecological habitat feature data in spatial models to characterize tick-borne disease exposure risk in Acadia National Park (ANP), Maine. To determine the broad-scale patterns of blacklegged tick Ixodes scapularis Say (Acari: Ixodidae) densities in ANP, we conducted host-seeking tick collections at 114 sites across the park over two years. Using these tick survey data and geospatial landscape feature data (i.e., land cover, elevation, forest patch size, and aspect) we developed a random forest model of nymphal tick density. We found that host-seeking tick density varies significantly across the park and is particularly high in areas characterized by deciduous forest cover and relatively low elevation. To explore potential fine-scale ecological drivers of tick density spatial patterns, we quantified microclimate conditions, host activity, and vegetation characteristics at a subset of 19 sites. We identified significant differences in microclimate conditions but not host activity or vegetation metrics across broad-scale landscape feature classes. Mean temperature and mean humidity were correlated to nymphal densities and therefore may provide a mechanistic link between landscape features and blacklegged tick densities. Finally, we detected multiple tick-borne pathogens in both ticks and small mammals sampled in ANP, including Borrelia burgdorferi, Babesia microti, and Anaplasma phagocytophilum. Our findings demonstrate the value of using ecological metrics to estimate vector-borne disease exposure risk and provide insight into habitat characteristics that may drive tick-borne disease exposure risk., (© The Author(s) 2022. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

The incidence and geographic range of vector-borne diseases have been expanding in recent decades, attributed in part to global climate change. Blacklegged ticks (Ixodes scapularis), the primary vector for multiple tick-borne pathogens in North America, are spreading rapidly beyond their historic post-colonial range and are thought to be constrained mainly by winter temperature at northern latitudes. Our research explored whether winter climate currently limits the distribution of blacklegged ticks and the pathogens they transmit in Maine, U.S.A., by contributing to overwinter mortality of nymphs. We experimentally tested tick overwinter survival across large-scale temperature and snowfall gradients and assessed factors contributing to winter mortality in locations where blacklegged tick populations are currently established and locations where the blacklegged tick has not yet been detected. We also tested the hypothesis that insulation in the tick microhabitat (i.e., by leaf litter and snowpack) can facilitate winter survival of blacklegged tick nymphs despite inhospitable ambient conditions. Overwinter survival was not significantly different in coastal southern compared to coastal and inland northern Maine, most likely due to sufficient snowpack that protected against low ambient temperatures at high latitudes. Snow cover and leaf litter contributed significantly to overwinter survival at sites in both southern and northern Maine. To further assess whether the current distribution of blacklegged ticks in Maine aligns with patterns of overwinter survival, we systematically searched for and collected ticks at seven sites along latitudinal and coastal-inland climate gradients across the state. We found higher densities of blacklegged ticks in coastal southern Maine (90.2 ticks/1000 m 2 ) than inland central Maine (17.8 ticks/1000 m 2 ) and no blacklegged ticks in inland northern Maine. Our results suggest that overwinter survival is not the sole constraint on the blacklegged tick distribution even under extremely cold ambient conditions and additional mechanisms may limit the continued northward expansion of ticks., (Copyright © 2021. Published by Elsevier GmbH.)

Polymer photocatalysts are a synthetically diverse class of materials that can be used for the production of solar fuels such as H 2 , but the underlying mechanisms by which they operate are poorly understood. Time-resolved vibrational spectroscopy provides a powerful structure-specific probe of photogenerated species. Here we report the use of time-resolved resonance Raman (TR 3 ) spectroscopy to study the formation of polaron pairs and electron polarons in one of the most active linear polymer photocatalysts for H 2 production, poly(dibenzo[ b , d ]thiophene sulfone), P10. We identify that polaron-pair formation prior to thermalization of the initially generated excited states is an important pathway for the generation of long-lived photoelectrons.

In the northeastern USA, active forest management can include timber harvests designed to meet silvicultural objectives (i.e., harvesting trees that meet certain maturity, height, age, or quality criteria). Timber harvesting is an important tool in enhancing regeneration and maintaining forest health. It also has considerable potential to influence transmission dynamics of tick-borne pathogens, which are deeply embedded in the forest ecosystem. We conducted a 2-year study to test the hypotheses that recent timber harvesting impacts blacklegged tick density and infection prevalence in managed nonindustrial forests. We found that (1) recent harvesting reduces the presence of nymphal and density of adult blacklegged ticks, (2) recently harvested stands are characterized by understory microclimate conditions that may inhibit tick survival and host-seeking behavior, (3) capture rates of small mammal species frequently parasitized by immature ticks are lower in recently harvested stands compared to control stands with no recent harvest history. In addition, a 1-year pilot study suggests that harvesting does not affect nymphal infection prevalence. Collectively, our results demonstrate that forest structure and understory conditions may impact ticks and the pathogens they transmit via a range of mechanistic pathways, and moreover, active forest management may offer sustainable tools to inhibit entomological risk of exposure to tick-borne pathogens in the landscape., (© 2021. EcoHealth Alliance.)

The blacklegged tick (Ixodes scapularis) and the invasive European fire ant (Myrmica rubra) are both expanding throughout their sympatric range in coastal New England. Ixodes scapularis is the primary vector of the bacterium Borrelia burgdorferi, which is the causative agent of Lyme disease, and Mount Desert Island, Maine, home to Acadia National Park, currently is affected by a high Lyme disease burden. Ticks have many natural predators, including ants, although no previous studies have investigated interactions between these two species. To test the hypothesis that the presence of M. rubra alters I. scapularis abundance, we collected ticks by drag-sampling at eight ant-infested sites and eight uninfested control sites in Acadia National Park. We found that nymph density was significantly higher at ant-infested sites, while larval density was significantly higher at control sites. In addition, we conducted a laboratory bioassay to measure M. rubra aggression against I. scapularis larvae, nymphs, and adults and Dermacentor variabilis adults, and found that ant aggression was significantly higher against D. variabilis adults than I. scapularis adults. Our findings support the hypothesis that M. rubra has divergent effects across I. scapularis life stages, and we discuss possible ecological mechanisms, including optimal microclimate and predation, that could promote density of nymphs while inhibiting density of larvae., Competing Interests: The authors have declared that no competing interests exist.

The benefit of enhanced shear stress to the vascular endothelium has been well-documented in conduit arteries but is less understood in skin microcirculation. The aim of this study was to provide physiological evidence of the vascular changes in skin microcirculation induced by intermittent pneumatic compression (IPC) of 1 s cuff inflation (130 mmHg) every 20 s to the palm of the hand for 30 min. The oxygenation and hemodynamics of dorsal mid-phalangeal finger skin microcirculation were assessed by laser Doppler fluximetry and reflectance spectroscopy before, during, and after IPC in 15 young (18-39 years old) and 39 older (40-80 years old) controls and 32 older subjects with type 2 diabetes mellitus. Each individual cuff inflation induced: 1 ) brief surge in flux immediately after cuff deflation followed by 2 ) transitory reduction in blood oxygen for ∼4 s, and 3 ) a second increase in perfusion and oxygenation of the microcirculation peaking ∼11 s after cuff deflation in all subject groups. With no significant change in blood volume observed by reflectance spectroscopy, despite the increased shear stress at the observed site, this second peak in flux and blood oxygen suggests a delayed vasoactive response upstream inducing increased arterial influx in the microcirculation that was higher in older controls and subjects with diabetes compared to young controls ( P < 0.001, P < 0.001, respectively) and achieving maximum capillary recruitment in all subject groups. Transitory hypoxic stimuli with conducted vasodilation may be a mechanism through which IPC enhances capillary perfusion in skin microcirculation independent of age and type 2 diabetes mellitus. NEW & NOTEWORTHY This study demonstrates that hand intermittent pneumatic compression evokes transitory hypoxic stimuli in distal finger skin microcirculation inducing vasodilation of arterial inflow vessels, enhanced perfusion, and maximum capillary recruitment in young and older subjects and older subjects with type 2 diabetes mellitus. Enhanced shear stress in the microcirculation did not appear to induce local skin vasodilation.

Disease epidemic outbreaks on human metapopulation networks are often driven by a small number of superspreader nodes, which are primarily responsible for spreading the disease throughout the network. Superspreader nodes typically are characterized either by their locations within the network, by their degree of connectivity and centrality, or by their habitat suitability for the disease, described by their reproduction number (R). Here we introduce a model that considers simultaneously the effects of network properties and R on superspreaders, as opposed to previous research which considered each factor separately. This type of model is applicable to diseases for which habitat suitability varies by climate or land cover, and for direct transmitted diseases for which population density and mitigation practices influences R. We present analytical models that quantify the superspreader capacity of a population node by two measures: probability-dependent superspreader capacity, the expected number of neighboring nodes to which the node in consideration will randomly spread the disease per epidemic generation, and time-dependent superspreader capacity, the rate at which the node spreads the disease to each of its neighbors. We validate our analytical models with a Monte Carlo analysis of repeated stochastic Susceptible-Infected-Recovered (SIR) simulations on randomly generated human population networks, and we use a random forest statistical model to relate superspreader risk to connectivity, R, centrality, clustering, and diffusion. We demonstrate that either degree of connectivity or R above a certain threshold are sufficient conditions for a node to have a moderate superspreader risk factor, but both are necessary for a node to have a high-risk factor. The statistical model presented in this article can be used to predict the location of superspreader events in future epidemics, and to predict the effectiveness of mitigation strategies that seek to reduce the value of R, alter host movements, or both., Competing Interests: The authors have declared that no competing interests exist.

Orthopedic injury can occur from a variety of causes including motor vehicle collision, battlefield injuries or even falls from standing. Persistent limb pain is common after orthopedic injury or surgery and presents a unique challenge, as the initiating event may result in polytrauma to bone, muscle, and peripheral nerves. It is imperative that we understand the tissue-specific and multicellular response to this unique type of injury in order to best develop targeted treatments that improve healing and regeneration. In this Mini Review we will first discuss current rodent models of orthopedic trauma/complex orthotrauma. In the second section, we will focus on bone-specific outcomes including imaging modalities, biomechanical testing and immunostaining for markers of bone healing/turnover. In the third section, we will discuss muscle-related pathology including outcome measures of fibrosis, muscle regeneration and tensile strength measurements. In the fourth section, we will discuss nervous system-related pathology including outcome measures of pain-like responses, both reflexive and non-reflexive. In all sections we will consider parallels between preclinical outcome measures and the functional and mechanistic findings of the human condition., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Shen, Gardner, Vyas, Ishida and Tawfik.)

Geographical range expansions of blacklegged tick [Ixodes scapularis Say (Acari: Ixodidae)] populations over time in the United States have been attributed to a mosaic of factors including 20th century reforestation followed by suburbanization, burgeoning populations of the white-tailed deer [Odocoileus virginianus Zimmerman (Artiodactyla: Cervidae)], and, at the northern edge of I. scapularis' range, climate change. Maine, a high Lyme disease incidence state, has been experiencing warmer and shorter winter seasons, and relatively more so in its northern tier. Maine served as a case study to investigate the interacting impacts of deer and seasonal climatology on the spatial and temporal distribution of I. scapularis. A passive tick surveillance dataset indexed abundance of I. scapularis nymphs for the state, 1990-2013. With Maine's wildlife management districts as the spatial unit, we used a generalized additive model to assess linear and nonlinear relationships between I. scapularis nymph abundance and predictors. Nymph submission rate increased with increasing deer densities up to ~5 deer/km2 (13 deer/mi2), but beyond this threshold did not vary with deer density. This corroborated the idea of a saturating relationship between I. scapularis and deer density. Nymphs also were associated with warmer minimum winter temperatures, earlier degree-day accumulation, and higher relative humidity. However, nymph abundance only increased with warmer winters and degree-day accumulation where deer density exceeded ~2 deer/km2 (~6/mi2). Anticipated increases in I. scapularis in the northern tier could be partially mitigated through deer herd management., (© The Author(s) 2020. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

The substrates O 2 and NO cooperatively activate the NO dioxygenase function of Escherichia coli flavohemoglobin. Steady-state and transient kinetic measurements support a structure-based mechanistic model in which O 2 and NO movements and conserved amino acids at the E11, G8, E2, E7, B10, and F7 positions within the globin domain control activation. In the cooperative and allosteric mechanism, O 2 migrates to the catalytic heme site via a long hydrophobic tunnel and displaces LeuE11 away from the ferric iron, which forces open a short tunnel to the catalytic site gated by the ValG8/IleE15 pair and LeuE11. NO permeates this tunnel and leverages upon the gating side chains triggering the CD loop to furl, which moves the E and F-helices and switches an electron transfer gate formed by LysF7, GlnE7, and water. This allows FADH 2 to reduce the ferric iron, which forms the stable ferric-superoxide-TyrB10/GlnE7 complex. This complex reacts with internalized NO with a bimolecular rate constant of 10 10  M -1  s -1 forming nitrate, which migrates to the CD loop and unfurls the spring-like structure. To restart the cycle, LeuE11 toggles back to the ferric iron. Actuating electron transfer with O 2 and NO movements averts irreversible NO poisoning and reductive inactivation of the enzyme. Together, structure snapshots and kinetic constants provide glimpses of intermediate conformational states, time scales for motion, and associated energies., Competing Interests: Conflict of interest The authors declare that they have no conflicts of interest with the contents of this article., (Copyright © 2020 The Authors. Published by Elsevier Inc. All rights reserved.)

Retroviral integrases must navigate host DNA packaged as chromatin during integration of the viral genome. Prototype foamy virus (PFV) integrase (IN) forms a tetramer bound to two viral DNA (vDNA) ends in a complex termed an intasome. PFV IN consists of four domains: the amino terminal extension domain (NED), amino terminal domain (NTD), catalytic core domain (CCD), and carboxyl terminal domain (CTD). The domains of the two inner IN protomers have been visualized, as well as the CCDs of the two outer IN protomers. However, the roles of the amino and carboxyl terminal domains of the PFV intasome outer subunits during integration to a nucleosome target substrate are not clear. We used the well-characterized 601 nucleosome to assay integration activity as well as intasome binding. PFV intasome integration to 601 nucleosomes occurs in clusters at four independent sites. We find that the outer protomer NED and NTD domains have no significant effects on integration efficiency, site selection, or binding. The CTDs of the outer PFV intasome subunits dramatically affect nucleosome binding but have little effect on total integration efficiency. The outer PFV IN CTDs did significantly alter the integration efficiency at one site. Histone tails also significantly affect intasome binding, but have little impact on PFV integration efficiency or site selection. These results indicate that binding to nucleosomes does not correlate with integration efficiency and suggests most intasome-binding events are unproductive., Competing Interests: Conflict of interest The authors declare that they have no conflicts of interest with the contents of this article., (Copyright © 2021 The Authors. Published by Elsevier Inc. All rights reserved.)

Personalized AAC intervention refers to an approach in which intervention is tailored to the individual's needs and skills, the needs and priorities of the individual's family and other social environments, the evidence base, and the individual's response to intervention. This approach is especially relevant to AAC intervention for young children with complex communication needs given their unique constellations of strengths and challenges, and the qualitative and quantitative changes that they experience over time as they develop, as well as the diversity of their families, schools, and communities. This paper provides detailed documentation of personalized AAC intervention over a six-month period for a 3-year-old girl with developmental delay and complex communication needs. The paper describes (1) personalization of multimodal AAC supports to provide this child with the tools to communicate; (2) personalized intervention to build semantic and morphosyntactic skills; and, (3) personalized instruction in literacy skills (i.e., letter-sound correspondences, sound blending, decoding, sight word recognition, reading simple stories, reading comprehension, and encoding skills). Specific goals, instructional materials, and procedures are described; data on speech, language, and literacy outcomes are presented.

Lyme disease, the most prevalent vector-borne disease in North America, is increasing in incidence and geographic distribution as the tick vector, Ixodes scapularis , spreads to new regions. We re-construct the spatial-temporal invasion of the tick and human disease in the Midwestern US, a major focus of Lyme disease transmission, from 1967 to 2018, to analyse the influence of spatial factors on the geographic spread. A regression model indicates that three spatial factors-proximity to a previously invaded county, forest cover and adjacency to a river-collectively predict tick occurrence. Validation of the predictive capability of this model correctly predicts counties invaded or uninvaded with 90.6% and 98.5% accuracy, respectively. Reported incidence increases in counties after the first report of the tick; based on this modelled relationship, we identify 31 counties where we suspect I. scapularis already occurs yet remains undetected. Finally, we apply the model to forecast tick establishment by 2021 and predict 42 additional counties where I. scapularis will probably be detected based upon historical drivers of geographic spread. Our findings leverage resources dedicated to tick and human disease reporting and provide the opportunity to take proactive steps (e.g. educational efforts) to prevent and limit transmission in areas of future geographic spread.

Man-made stormwater and sewage infrastructure, particularly roadside catch basins, provides widespread habitats for immature mosquitoes in urban and suburban environments. Historically, throughout much of the USA, stormwater, sewage, and industrial wastewater were conducted together through "combined" sewer systems, discharging a combination of stormwater and wastewater into streams. Within recent decades, many cities have replaced these combined sewers with "stormwater only" systems that separate stormwater from wastewater. The objective of this research was to evaluate the implications of this infrastructure conversion for production of Culex pipiens, a primary vector for West Nile virus. On a weekly basis over 14 wk, 20 catch basins (10 combined sewer and 10 stormwater only) were sampled for mosquito larvae and emerging adults using the dipping collection method and floating emergence traps. Abundance of larval Cx. pipiens was higher in combined sewer compared with stormwater-only catch basins, while to the contrary, abundance of adult Cx. pipiens was lower in combined sewer compared with stormwater-only catch basins. This study is the first to reveal that habitat attractiveness and quality for Cx. pipiens may vary between combined sewer and stormwater-only catch basins, and our results contribute to a growing body of research to inform vector management and urban planning efforts as municipalities consider the environmental and public health implications of conversion from combined sewage management to separation of stormwater and wastewater., (Copyright © 2020 by The American Mosquito Control Association, Inc.)

Here, we discuss the application, advantages, and potential pitfalls of using transient UV/Vis (ultraviolet-visible) absorption spectroscopy to study photoelectrodes for water splitting. We revisit one of the most commonly studied water oxidation photoanodes (α-Fe 2 O 3-x ) to provide commentary and guidelines on experiment design and data analysis for transient absorption (TA) studies of photoelectrodes within a photoelectrochemical cell. We also assess the applicability of such in situ TA studies to understand photoelectrodes under operating conditions. A major limitation is that most, if not all, past in situ TA studies have been carried out using only pulsed light sources to generate carriers, with the electrode held in the dark at other times, which is shown to be a poor model for operating conditions. However, with a simple modification of existing TA experiments, a simple operando TA measurement is reported.

Photocatalytic conversion of CO 2 into fuels is an important challenge for clean energy research and has attracted considerable interest. Here we show that tethering molecular catalysts-a rhenium complex, [Re(bpy)(CO) 3 Cl]-together in the form of a crystalline covalent organic framework (COF) affords a heterogeneous photocatalyst with a strong visible light absorption, a high CO 2 binding affinity, and ultimately an improved catalytic performance over its homogeneous Re counterpart. The COF incorporates bipyridine sites, allowing for ligation of the Re complex, into a fully π-conjugated backbone that is chemically robust and promotes light-harvesting. A maximum rate of 1040 μmol g -1 h -1 for CO production with 81% selectivity was measured. CO production rates were further increased up to 1400 μmol g -1 h -1 , with an improved selectivity of 86%, when a photosensitizer was added. Addition of platinum resulted in production of syngas, hence, the co-formation of H 2 and CO, the chemical composition of which could be adjusted by varying the ratio of COF to platinum. An amorphous analog of the COF showed significantly lower CO production rates, suggesting that crystallinity of the COF is beneficial to its photocatalytic performance in CO 2 reduction., (This journal is © The Royal Society of Chemistry 2020.)

A deceptively simple feature in the S 1 ← S 0 spectrum of p-fluorotoluene (pFT), 1013 cm -1 above the origin, is studied using both zero-electron-kinetic-energy (ZEKE) and two-dimensional laser-induced fluorescence (2D-LIF) spectroscopy. It is found to consist of a cornucopia of overlapped transitions to eigenstates that arise from numerous interacting levels. A significant variation in the activity is seen employing both the ZEKE and 2D-LIF techniques. Detailed insight into the complicated spectra can be achieved, owing to the large number of vibrational wavenumbers that have been previously determined for the S 0 , S 1 , and D 0 + states, summarized herein. It is found that the activity is dominated by two overtones, which are individually interacting with other levels, so providing largely independent routes for vibrational energy flow at the same internal energy. Additionally, other weak features located 900-1050 cm -1 above the origin are examined.

We consider two key parameters that have been proposed to be important for vibrational energy delocalization, closely related to intramolecular vibrational redistribution (IVR), in molecules. These parameters are the symmetry of the molecule, and the presence of torsional (internal rotor) modes of a methyl group. We consider four para-disubstituted benzene molecules and examine their vibrational character. The molecules selected are para-difluorobenzene, para-chlorofluorobenzene, para-fluorotoluene, and para-xylene. This set of molecules allows the above parameters to be assessed in a systematic way. The probe we use is zero-electron-kinetic-energy (ZEKE) spectroscopy, which is employed in a resonant scheme, where the intermediate levels are selected vibrational levels of the S1 excited electronic state, with wavenumbers up to 1300 cm-1. We conclude that symmetry, and the presence of a methyl groups, do indeed have a profound effect on "restricted" IVR at low energies. This is underpinned by serendipitous coincidences in the energies of the levels, owing to small shifts in vibrational wavenumbers between molecules, so bringing levels into resonance. Additionally, methyl groups play an important role in opening up new routes for coupling between vibrations of different symmetry, and this is critical in the transition to "statistical" IVR at lower energies for molecules that contain them. Further, the presence of two methyl groups in the symmetrically-substituted p-xylene causes more widespread IVR than does the single methyl group in the asymmetrically-substituted p-fluorotoluene.

The electrocatalytic oxidation of water coupled to the reduction of carbon dioxide, to make carbon based products, or the reduction of protons to provide hydrogen, offers a sustainable route to generating useful fuels. However new improved electrocatalysts and electrode materials are needed for these reactions. Similarly fuel cells for fuel utilisation rely on precious metal electrodes and new lower-cost materials are needed. Developing efficient catalysts for sustainable fuel generation can be accelerated with an improved understanding of the underlying mechanisms. Herein, we present a perspective on the use of vibrational sum-frequency generation (VSFG) spectroscopy to study such electrocatalytic mechanisms. We briefly outline the basic principles of VSFG spectroscopy pertinent to the study of electrochemical interfaces. We then review the use of VSFG to study water at charged and electrode interfaces, relevant to the mechanisms of water oxidation, the mechanisms of alcohol oxidation and also molecular electrocatalysts for carbon dioxide reduction.

Aedes aegypti L. and Aedes albopictus Skuse co-occur in a variety of water-filled containers where they compete for resources. Larvae of Ae. albopictus Skuse often outcompete those of Ae. aegypti L., but variation in biotic and abiotic parameters can modify the outcome of this interspecific competition. We tested whether container size can alter the magnitude and direction of intra- and interspecific competition by rearing three Ae. aegypti and Ae. albopictus larval combinations (100:0, 50:50 and 0:100) in three container sizes (small, medium, and large). For both mosquito species, individuals raised in small- and medium-sized containers had shorter development time to adulthood, higher survival to adulthood, and larger adult body size compared to individuals from large containers. For Ae. aegypti but not Ae. albopictus, survival to adulthood was significantly influenced by a two-way interaction between container size and larval competition. The negative effect of interspecific competition was stronger in the small and medium containers and the negative effect of intraspecific competition was stronger in large containers. Our results show that container size can affect the outcome of intra- and interspecific competition between Ae. aegypti and Ae. albopictus and may help account for the observed patterns of both competitive exclusion and coexistence documented in the field for these two medically important mosquito species., (© The Author(s) 2018. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

Eukaryotic DNA binding proteins must access genomic DNA that is packaged into chromatin in vivo. During a productive infection, retroviral integrases (IN) must similarly interact with chromatin to integrate the viral cDNA genome. Here we examine the role of nucleosome DNA unwrapping in the retroviral integrase search for a target site. These studies utilized PFV intasomes that are comprised of a tetramer of PFV IN with two oligomers mimicking the viral cDNA ends. Modified recombinant human histones were used to generate nucleosomes with increased unwrapping rates at different DNA regions. These modifications included the acetylmimetic H3(K56Q) and the chemically engineered H4(K77ac, K79ac). While transcription factors and DNA damage sensors may search nucleosome bound DNA during transient unwrapping, PFV intasome mediated integration appears to be unaffected by increased nucleosome unwrapping. These studies suggest PFV intasomes do not utilize nucleosome unwrapping to search nucleosome targets., Competing Interests: The authors have declared that no competing interests exist.

Two-dimensional laser-induced fluorescence (2D-LIF) spectroscopy is a powerful tool allowing overlapped features in an electronic spectrum to be separated, and interactions between vibrations and torsions to be identified. Here the technique is employed to assign the 790-825 cm -1 region above the origin of the S 1 ← S 0 transition in para-fluorotoluene, which provides insight into the unusual time-resolved results of Davies and Reid [Phys. Rev. Lett. 109, 193004 (2012)]. The region is dominated by a pair of bands that arise from a Fermi resonance; however, the assignment is complicated by contributions from a number of overtones and combinations, including vibration-torsion ("vibtor") levels. The activity in the 2D-LIF spectra is compared to the recently reported zero-electron-kinetic-energy spectra [Tuttle et al., J. Chem. Phys. 146, 244310 (2017)] to arrive at a consistent picture of the energy levels in this region of the spectrum.

Ticks use a variety of chemical cues to locate hosts, the main cue being carbon dioxide, which is exhaled by hosts. This study sought to experimentally determine whether ticks exhibit preference among human hosts based on host sex, as the chemical components of human male and female breath have been shown to differ. We focused on the lone star tick, Amblyomma americanum, due to its importance as a disease vector in the United States and its active host-seeking behavior. To test the hypothesis that ticks exhibit preference based upon host sex, we conducted a binary choice behavioral bioassay. Male and female human volunteers (n = 20 pairs) breathed into opposite sides of a secured polycarbonate tube containing 10 adult A. americanum and the proportion of ticks that exhibited a host preference was recorded. We found that under controlled conditions, human females attract a significantly larger proportion of ticks than males. Possible mechanisms to explain these results include that (1) female breath contains components that ticks find attractive, and/or (2) male breath contains a repellent chemical component.

Ecological traps occur due to a mismatch between a habitat's attractiveness and quality, wherein organisms show preference for low-quality habitats over other available high-quality habitats. Our previous research identified leaf litter from common blackberry ( Rubus allegheniensis ) as a natural ecological trap for an important vector for West Nile virus ( Culex pipiens ), attracting mosquitoes to oviposit in habitats deleterious to the survival of their larvae. Here we demonstrate that manipulation of leaf litter in stormwater catch basins, an important source of disease vector mosquitoes in urban environments, can increase Cx. pipiens oviposition but reduce survival. In a series of experiments designed to elucidate the mechanisms that explain the attractive and lethal properties of this native plant, behavioural bioassays suggest that oviposition site selection by Cx. pipiens is mediated primarily by chemical cues as leaves decompose. However, we also show that juvenile mosquito survival is mainly related to the suitability of the bacterial community in the aquatic habitat for mosquito nutritional needs, which does not appear to create a cue that influences oviposition choice. This mismatch between oviposition cues and drivers of larval habitat quality may account for the ecological trap phenomenon detected in this study. Our findings provide new insights into potential mechanistic pathways by which ecological traps may occur in nature and proof-of-concept for a new 'attract-and-kill' tool for mosquito control., (© 2018 The Author(s).)