Experimental manipulation of photoperiod influences migration timing in a wild, long-distance migratory songbird.

Previous laboratory studies have demonstrated the role of photoperiod in cueing the migration timing of small land birds; however, how migration timing of young birds in wild environments develops in relation to these cues have rarely been investigated. Such investigations can make important contributions to our developing understanding of the phenotypic plasticity of migration timing to new conditions with climate change, where changes in the timing of nesting may expose juvenile birds to different photoperiods. We investigated the impact of manipulating photoperiod during nestling development in a long-distance migratory songbird on the timing of post-breeding movements in the wild. Using programmable lighting installed in the nest-boxes of purple martins (Progne subis), we exposed developing nestlings, from hatch to fledge date, to an extended photoperiod that matched the day length of the summer solstice in Manitoba, Canada. We found that birds with a simulated, earlier photoperiod had a longer nesting period and later fledge and autumn departure dates than control group birds. This study demonstrates the phenotypic plasticity of first-year birds to the ontogenetic effect of their hatch date in the formation of the timing of their first post-breeding movements. Further, we discuss how these results have implications for the potential use of assisted evolution approaches to alter migration timing to match new conditions with climate change.

Weak effects of geolocators on small birds: A meta-analysis controlled for phylogeny and publication bias.

Currently, the deployment of tracking devices is one of the most frequently used approaches to study movement ecology of birds. Recent miniaturization of light-level geolocators enabled studying small bird species whose migratory patterns were widely unknown. However, geolocators may reduce vital rates in tagged birds and may bias obtained movement data. There is a need for a thorough assessment of the potential tag effects on small birds, as previous meta-analyses did not evaluate unpublished data and impact of multiple life-history traits, focused mainly on large species and the number of published studies tagging small birds has increased substantially. We quantitatively reviewed 549 records extracted from 74 published and 48 unpublished studies on over 7,800 tagged and 17,800 control individuals to examine the effects of geolocator tagging on small bird species (body mass <100 g). We calculated the effect of tagging on apparent survival, condition, phenology and breeding performance and identified the most important predictors of the magnitude of effect sizes. Even though the effects were not statistically significant in phylogenetically controlled models, we found a weak negative impact of geolocators on apparent survival. The negative effect on apparent survival was stronger with increasing relative load of the device and with geolocators attached using elastic harnesses. Moreover, tagging effects were stronger in smaller species. In conclusion, we found a weak effect on apparent survival of tagged birds and managed to pinpoint key aspects and drivers of tagging effects. We provide recommendations for establishing matched control group for proper effect size assessment in future studies and outline various aspects of tagging that need further investigation. Finally, our results encourage further use of geolocators on small bird species but the ethical aspects and scientific benefits should always be considered.

National contributions to global ecosystem values.

Current conservation templates prioritize biogeographic regions with high intensity ecosystem values, such as exceptional species richness or threat. Intensity-based targets are an important consideration in global efforts, but they do not capture all available opportunities to conserve ecosystem values, including those that accrue in low intensity over large areas. We assess six globally-significant ecosystem values-intact wilderness, freshwater availability, productive marine environments, breeding habitat for migratory wildlife, soil carbon storage, and latitudinal potential for range shift in the face of climate change-to highlight opportunities for high-impact broadly-distributed contributions to global conservation. Nations can serve as a cohesive block of policy that can profoundly influence conservation outcomes. Contributions to global ecosystem values that exceed what is predicted by a nation's area alone, can give rise to countries with the capacity to act as 'conservation superpowers', such as Canada and Russia. For these conservation superpowers, a relatively small number of national policies can have environmental repercussions for the rest of the world.

Ecological Causes and Consequences of Intratropical Migration in Temperate-Breeding Migratory Birds.

New discoveries from direct tracking of temperate-breeding passerines show that intratropical migration (ITM) occurs in a growing number of species, which has important implications for understanding their evolution of migration, population dynamics, and conservation needs. Our large sample size ([Formula: see text]) for purple martins (Progne subis subis) tracked with geolocators to winter sites in Brazil, combined with geolocator deployments at breeding colonies across North America, allowed us to test hypotheses for ITM, something which has not yet been possible to do for other species. ITM in purple martins was not obligate; only 44% of individuals exhibited ITM, and movements were not coordinated in time or space. We found no evidence to support the resource hypothesis; rainfall and temperature experienced by individual birds during their last 2 weeks at their first roost site were similar to conditions at their second roost site after ITM. Birds generally migrated away from the heavily forested northwestern Amazon to less forested regions to the south and east. ITM in this aerial insectivore appears to support the competition-avoidance hypothesis and may be triggered by increasing local density in the core wintering region. Full life cycle models and migratory networks will need to incorporate ITM to properly address seasonal carryover effects and identify which wintering regions are most important for conservation.

Connectivity of wood thrush breeding, wintering, and migration sites based on range-wide tracking.

Many migratory animals are experiencing rapid population declines, but migration data with the geographic scope and resolution to quantify the complex network of movements between breeding and nonbreeding regions are often lacking. Determining the most frequently used migration routes and nonbreeding regions for a species is critical for understanding population dynamics and making effective conservation decisions. We tracked the migration of individual Wood Thrushes (Hylocichla mustelina) (n = 102) from across their range with light-level geolocators and, for the first time, quantified migration routes and wintering regions for distinct breeding populations. We identified regional and species-level migratory connectivity networks for this declining songbird by combining our tracking results with range-wide breeding abundance estimates and forest cover data. More than 50% of the species occupied the eastern wintering range (Honduras to Costa Rica), a region that includes only one-third of all wintering habitat and that is undergoing intensive deforestation. We estimated that half of all Wood Thrushes in North America migrate south through Florida in fall, whereas in spring approximately 73% funnel northward through a narrow span along the central U.S. Gulf Coast (88-93°W). Identifying migratory networks is a critical step for conservation of songbirds and we demonstrated with Wood Thrushes how it can highlight conservation hotspots for regional populations and species as a whole.

Ionic liquid modulation of swelling and LCST behavior of N-isopropylacrylamide polymer gels.

The physicochemical properties of free-standing cross-linked poly(N-isopropylacrylamide) (pNIPAAM) gels, generated in the presence of the Ionic liquids (ILs), 1-ethyl-3-methylimidazolium [C2mIm](+) salts of ethylsulfate [EtSO4](-), dicyanamide [DCA](-), bis(trifluoromethylsulfonyl)imide [NTf2](-), and trihexyltetradecylphosphonium dicyanamide ([P(6,6,6,14)][DCA]) are described. The Lower Critical Solution Temperature (LCST) of the resulting ionogel was found to vary between 24-31 °C. The behaviour of swelling is found to be as high as 31.55% (±0.47, n = 3) from the initial dehydrated state, while 28.04% (±0.42, n = 3) shrinking from the hydrated swollen state is observed. For ionogels based on the [DCA](-) anion an unexpected complete loss of the shrinking behaviour occurs, attributed to water interactions with the nitrile group of the [DCA](-) anion. Scanning Electron Microscopy also reveals distinct morphological changes, for example [C2mIm][EtSO4] displays a highly porous, nodule type morphology, efficiently pre-disposed for water uptake.

Swelling and shrinking properties of thermo-responsive polymeric ionic liquid hydrogels with embedded linear pNIPAAM.

In this study, varying concentrations of linear pNIPAAM have been incorporated for the first time into a thermo-responsive polymeric ionic liquid (PIL) hydrogel, namely tributyl-hexyl phosphonium 3-sulfopropylacrylate (P-SPA), to produce semi-interpenetrating polymer networks. The thermal properties of the resulting hydrogels have been investigated along with their thermo-induced shrinking and reswelling capabilities. The semi-interpenetrating networks (IPN) hydrogels were found to have improved shrinking and reswelling properties compared with their PIL counterpart. At elevated temperatures (50-80 °C), it was found that the semi-IPN with the highest concentration of hydrophobic pNIPAAM exhibited the highest shrinking percentage of ~40% compared to the conventional P-SPA, (27%). This trend was also found to occur for the reswelling measurements, with semi-IPN hydrogels producing the highest reswelling percentage of ~67%, with respect to its contracted state. This was attributed to an increase in water affinity due to the presence of hydrophilic pNIPAAM. Moreover, the presence of linear pNIPAAM in the polymer matrix leads to improved shrinking and reswelling response compared to the equivalent PIL.

Genomic architecture of migration timing in a long-distance migratory songbird.

The impact of climate change on spring phenology poses risks to migratory birds, as migration timing is controlled predominantly by endogenous mechanisms. Despite recent advances in our understanding of the underlying genetic basis of migration timing, the ways that migration timing phenotypes in wild individuals may map to specific genomic regions requires further investigation. We examined the genetic architecture of migration timing in a long-distance migratory songbird (purple martin, Progne subis subis) by integrating genomic data with an extensive dataset of direct migratory tracks. A moderate to large amount of variance in spring migration arrival timing was explained by genomics (proportion of phenotypic variation explained by genomics = 0.74; polygenic score R2 = 0.24). On chromosome 1, a region that was differentiated between migration timing phenotypes contained genes that could facilitate nocturnal flights and act as epigenetic modifiers. Overall, these results advance our understanding of the genomic underpinnings of migration timing.

Extensive regional variation in the phenology of insects and their response to temperature across North America.

Climate change models often assume similar responses to temperatures across the range of a species, but local adaptation or phenotypic plasticity can lead plants and animals to respond differently to temperature in different parts of their range. To date, there have been few tests of this assumption at the scale of continents, so it is unclear if this is a large-scale problem. Here, we examined the assumption that insect taxa show similar responses to temperature at 96 sites in grassy habitats across North America. We sampled insects with Malaise traps during 2019-2021 (N = 1041 samples) and examined the biomass of insects in relation to temperature and time of season. Our samples mostly contained Diptera (33%), Lepidoptera (19%), Hymenoptera (18%), and Coleoptera (10%). We found strong regional differences in the phenology of insects and their response to temperature, even within the same taxonomic group, habitat type, and time of season. For example, the biomass of nematoceran flies increased across the season in the central part of the continent, but it only showed a small increase in the Northeast and a seasonal decline in the Southeast and West. At a smaller scale, insect biomass at different traps operating on the same days was correlated up to ~75 km apart. Large-scale geographic and phenological variation in insect biomass and abundance has not been studied well, and it is a major source of controversy in previous analyses of insect declines that have aggregated studies from different locations and time periods. Our study illustrates that large-scale predictions about changes in insect populations, and their causes, will need to incorporate regional and taxonomic differences in the response to temperature.

Continent-wide tracking to determine migratory connectivity and tropical habitat associations of a declining aerial insectivore.

North American birds that feed on flying insects are experiencing steep population declines, particularly long-distance migratory populations in the northern breeding range. We determine, for the first time, the level of migratory connectivity across the range of a songbird using direct tracking of individuals, and test whether declining northern populations have higher exposure to agricultural landscapes at their non-breeding grounds in South America. We used light-level geolocators to track purple martins, Progne subis, originating from North American breeding populations, coast-to-coast (n = 95 individuals). We show that breeding populations of the eastern subspecies, P. s. subis, that are separated by ca. 2000 km, nevertheless have almost completely overlapping non-breeding ranges in Brazil. Most (76%) P. s. subis overwintered in northern Brazil near the Amazon River, not in the agricultural landscape of southern Brazil. Individual non-breeding sites had an average of 91 per cent forest and only 4 per cent agricultural ground cover within a 50 km radius, and birds originating from declining northern breeding populations were not more exposed to agricultural landscapes than stable southern breeding populations. Our results show that differences in wintering location and habitat do not explain recent trends in breeding population declines in this species, and instead northern populations may be constrained in their ability to respond to climate change.

Physicochemical study of spiropyran-terthiophene derivatives: photochemistry and thermodynamics.

The photochemistry and thermodynamics of two terthiophene (TTh) derivatives bearing benzospiropyran (BSP) moieties, 1-(3,3″-dimethylindoline-6'-nitrobenzospiropyranyl)-2-ethyl 4,4″-didecyloxy-2,2':5',2″-terthiophene-3'-acetate (BSP-2) and 1-(3,3″-dimethylindoline-6'-nitrobenzospiropyranyl)-2-ethyl 4,4″-didecyloxy-2,2':5',2″-terthiophene-3'-carboxylate (BSP-3), differing only by a single methylene spacer unit, have been studied. The kinetics of photogeneration of the equivalent merocyanine (MC) isomers (MC-2 and MC-3, respectively), the isomerisation properties of MC-2 and MC-3, and the thermodynamic parameters have been studied in acetonitrile, and compared to the parent, non-TTh-functionalised, benzospiropyran derivative, BSP-1. Despite the close structural similarity of BSP-2 and BSP-3, their physicochemical properties were found to differ significantly; examples include activation energies (E(a(MC-2)) = 75.05 kJ mol(-1), E(a(MC-3)) = 100.39 kJ mol(-1)) and entropies of activation (ΔS = 43.38 J K(-1) mol(-1), ΔS = 37.78 J K(-1) mol(-1)) for the thermal relaxation from MC to BSP, with the MC-3 value much closer to the unmodified MC-1 value (46.48 J K(-1) mol(-1)) for this latter quantity. The thermal relaxation kinetics and solvatochromic behaviour of the derivatives in a range of solvents of differing polarity (ethanol, dichloromethane, acetone, toluene and diethyl ether) are also presented. Differences in the estimated values of these thermodynamic and kinetic parameters are discussed with reference to the molecular structure of the derivatives.

Central-place foraging poses variable constraints year-round in a neotropical migrant.

BACKGROUND: "Central-place foragers" are constrained in their habitat selection and foraging range by the frequency with which they need to return to a central place. For example, chick-rearing songbirds that must feed their offspring hourly might be expected to have smaller foraging ranges compared to non-breeding songbirds that return nightly to a roost. METHODS: We used GPS units to compare the foraging behaviour of an aerial insectivorous bird, the purple martin (Progne subis), during the breeding season in three regions across North America, as well as the non-breeding season in South America. Specifically, we tested foraging range size and habitat selection. RESULTS: Foraging range did not vary among regions during breeding (14.0 ± 39.2 km2) and was larger during the nonbreeding period (8840 ± 8150 km2). Purple martins strongly preferred aquatic habitats to other available habitats year-round and in the Amazon commuted from night roosts in low productivity sediment-poor water, where risk of predation was probably low, to daytime foraging sites in productive sediment-rich water sites. CONCLUSIONS: We provide the first estimates for foraging range size in purple martins and demonstrate foraging preference for aquatic habitats throughout two stages of the annual cycle. Understanding foraging constraints and habitat of aerial insectivores may help plan conservation actions throughout their annual cycle. Future research should quantify foraging behaviour during the post-breeding period and during migration.

Pre-migration artificial light at night advances the spring migration timing of a trans-hemispheric migratory songbird.

Artificial light at night (ALAN) is increasing at a high rate across the globe and can cause shifts in animal phenology due to the alteration of perceived photoperiod. Birds in particular may be highly impacted due to their use of extra-retinal photoreceptors, as well as the use of photoperiodic cues to time life events such as reproduction, moult, and migration. For the first time, we used light-logging geolocators to determine the amount of ALAN experienced by long-distance migratory songbirds (purple martin; Progne subis) while at their overwintering sites in South America to measure its potential relationship with spring migration timing. Almost a third of birds (48/155; 31%) were subjected to at least one night with ALAN over 30 days prior to spring migration. Birds that experienced the highest number of nights (10+) with artificial light departed for spring migration on average 8 days earlier and arrived 8 days earlier at their breeding sites compared to those that experienced no artificial light. Early spring migration timing due to pre-migration ALAN experienced at overwintering sites could lead to mistiming with environmental conditions and insect abundance on the migratory route and at breeding sites, potentially impacting survival and/or reproductive success. Such effects would be particularly detrimental to species already exhibiting steep population declines such as purple martins and other migratory aerial insectivores.

The use of nocturnal flights for barrier crossing in a diurnally migrating songbird.

BACKGROUND: The migration patterns of land birds can generally be divided into those species that migrate principally during the day and those that migrate during the night. Some species may show individual plasticity in the use of day or night flight, particularly when crossing large, open-water or desert barriers. However, individual plasticity in circadian patterns of migratory flights in diurnally migrating songbirds has never been investigated. METHODS: We used high precision GPS tracking of a diurnal, migratory swallow, the purple martin (Progne subis), to determine whether individuals were flexible in their spring migration strategies to include some night flight, particularly at barrier crossing. RESULTS: Most (91%) of individuals made large (sometimes > 1000 km), open-water crossings of the Caribbean Sea and the Gulf of Mexico that included the use of night flight. 32% of all water crossings were initiated at night, demonstrating that night flight is not only used to complete large crossings but may confer other advantages for diurnal birds. Birds were not more likely to initiate crossings with supportive winds, however crossings were more likely when they reduced travel distances. Our results are consistent with diurnal birds using night flight to help achieve time- and energy-savings through 'short cuts' at barrier crossings, at times and locations when foraging opportunities are not available. CONCLUSIONS: Overall, our results demonstrate the use of nocturnal flight and a high degree of individual plasticity in migration strategies on a circadian scale in a species generally considered to be a diurnal migrant. Nocturnal flights at barrier crossing may provide time and energy savings where foraging opportunities are low in an otherwise diurnal strategy. Future research should target how diel foraging and refueling strategies support nocturnal flights and barrier crossing in this and other diurnal species.

Photochromic imidazolium based ionic liquids based on spiropyran.

We investigate the physicochemical properties of a novel imidazolium benzospiropyran derivative, SP(Im), in imidazolium based ionic liquids (ILs). SP(Im) was prepared through alkylation of an imidazole to the photoswitchable compound and this derivative was characterised in imidazolium based ILs with increasing chain length to examine the stability of its merocyanine (MC) and spiropyran (SP) forms and compared to standard spiropyran, BSP. The rate of thermal relaxation of the new derivative is found to be about ten times faster than that of BSP as reflected in rates of 13.9 x 10(-3) s(-1) and 1.0 x 10(-3) s(-1) for SP(Im) and BSP, respectively, in [C(6)mIm][NTf(2)]. Since ILs are believed to form nano-structured domains it is proposed that the covalent attachment of the imidazolium side group of SP(Im) fully integrates the photoswitchable moiety into the non-polar region through side-chain association. In contrast, unbound BSP is relatively free to migrate between both polar and non-polar regions and the MC form is more readily stabilised by the IL charge via through space interactions and spontaneous movement to charged nano-domains leading to enhancement of the MC lifetime. At higher concentrations, rheological and transport properties were investigated to determine the impact of covalent attachment of the BSP fragment to an imidazolium cation on the ionic liquid structure. Ionic conductivity was found to decrease by up to 23% for SP(Im) with effects increasing with cation side-chain length. Unlike BSP, the photoswitching of the SP(Im) did not affect conductivity or viscosity values. This may indicate that the mobility of the photoswitchable compound and the resulting disruption of such movement may be critical to the control of this physical property.

Liquids intermediate between "molecular" and "ionic" liquids: liquid ion pairs?

Ionic liquids comprised of tetradecyltrihexyl- and tetrabutyl-phosphonium cations paired with chloride or sulfonyl amide anions exhibit properties that reflect strong ion association, including comparatively low viscosity as well as a degree of volatility, and hence exemplify an interesting intermediate state between true ionic and true molecular liquids.

Tracking from the tropics reveals behaviour of juvenile songbirds on their first spring migration.

Juvenile songbirds on spring migration travel from tropical wintering sites to temperate breeding destinations thousands of kilometres away with no prior experience to guide them. We provide a first glimpse at the migration timing, routes, and stopover behaviour of juvenile wood thrushes (Hylocichla mustelina) on their inaugural spring migration by using miniaturized archival geolocators to track them from Central America to the U.S. and Canada. We found significant differences between the timing of juvenile migration and that of more experienced adults: juveniles not only departed later from tropical wintering sites relative to adults, they also became progressively later as they moved northward. The increasing delay was driven by more frequent short stops by juveniles along their migration route, particularly in the U.S. as they got closer to breeding sites. Surprisingly, juveniles were just as likely as adults to cross the Gulf of Mexico, an open-water crossing of 800-1000 km, and migration route at the Gulf was not significantly different for juveniles relative to adults. To determine if the later departure of juveniles was related to poor body condition in winter relative to adults, we examined percent lean body mass, fat scores, and pectoral muscle scores of juvenile versus adult birds at a wintering site in Belize. We found no age-related differences in body condition. Later migration timing of juveniles relative to adults could be an adaptive strategy (as opposed to condition-dependent) to avoid the high costs of fast migration and competition for breeding territories with experienced and larger adults. We did find significant differences in wing size between adults and juveniles, which could contribute to lower flight efficiency of juveniles and thus slower overall migration speed. We provide the first step toward understanding the "black box" of juvenile songbird migration by documenting their migration timing and en route performance.

A portable centrifugal analyser for liver function screening.

Mortality rates of up to 50% have been reported after liver failure due to drug-induced hepatotoxicity and certain viral infections (Gao et al., 2008). These adverse conditions frequently affect HIV and tuberculosis patients on regular medication in resource-poor settings. Here, we report full integration of sample preparation with the read-out of a 5-parameter liver assay panel (LAP) on a portable, easy-to-use, fast and cost-efficient centrifugal microfluidic analysis system (CMAS). Our unique, dissolvable-film based centrifugo-pneumatic valving was employed to provide sample-to-answer fashion automation for plasma extraction (from finger-prick of blood), metering and aliquoting into separate reaction chambers for parallelized colorimetric quantification during rotation. The entire LAP completes in less than 20 min while using only a tenth the reagent volumes when compared with standard hospital laboratory tests. Accuracy of in-situ liver function screening was validated by 96 separate tests with an average coefficient of variance (CV) of 7.9% compared to benchtop and hospital lab tests. Unpaired two sample statistical t-tests were used to compare the means of CMAS and benchtop reader, on one hand; and CMAS and hospital tests on the other. The results demonstrate no statistical difference between the respective means with 94% and 92% certainty of equivalence, respectively. The portable platform thus saves significant time, labour and costs compared to established technologies, and therefore complies with typical restrictions on lab infrastructure, maintenance, operator skill and costs prevalent in many field clinics of the developing world. It has been successfully deployed to a centralised lab in Nigeria.

An electrochromic ionic liquid: design, characterization, and performance in a solid-state platform.

This work describes the synthesis and characteristics of a novel electrochromic ionic liquid (IL) based on a phosphonium core tethered to a viologen moiety. When integrated into a solid-state electrochromic platform, the viologen modified IL behaved as both the electrolyte and the electrochromic material. Platform fabrication was achieved through in situ photo-polymerization and encapsulation of this novel IL within a hybrid sol-gel. Important parameters of the platform performance, including its coloration efficiency, switching kinetics, and optical properties were characterised using UV-vis spectroscopy and cyclic voltammetry in tandem. The electrochromic platform exhibits a coloration efficiency of 10.72 cm(2) C(-1) and a varied optical output as a function of the incident current. Despite the rather viscous nature of the material, the platform exhibited approximately 2 orders of magnitude faster switching kinetics (221 s to reach 95 % absorbance) when compared to previously reported electrochromic ILs (18,000 s).

Temperature and pH triggered release characteristics of water/fluorescein from 1-ethyl-3-methylimidazolium ethylsulfate based ionogels.

A crosslinked poly(N-isopropylacrylamide) ionogel encapsulating an ionic liquid exhibits improved transmittance properties, enhanced water uptake/release, greater thermal actuation behaviour and distinct solvatomorphology over its hydrogel equivalent. It was also found that the rate of release of fluorescein pre-loaded into membranes was considerably enhanced for ionogels compared to equivalent hydrogels, and could be triggered through changes in pH and temperature.