High freezing sensitivity of legumes relative to other herbaceous species in northern temperate plant communities.

BACKGROUND AND AIMS: Reduced snow cover and increased air temperature variability are predicted to expose overwintering herbaceous plants to more severe freezing in some northern temperate regions. Legumes are a key functional group that may exhibit lower freezing tolerance than other species these regions, but this trend only has been observed for non-native legumes. Our aim was to confirm if this trend is restricted to non-native legumes or whether native legumes in these regions also exhibit low freezing tolerance. METHODS: First, we transplanted legumes (five non-native species and four native species) into either an old field (non-native) or a prairie (native) and used snow removal to expose the plots to increased soil freezing. Second, we grew plants in mesocosms (old field) and pots (prairie species) and exposed them in controlled environment chambers to a range of freezing treatments (control, 0, -5 or -10 °C) in winter or spring. We assessed freezing responses by comparing differences in biomass, cover and nodulation between freezing (or snow removal) treatments and controls. KEY RESULTS: Among legume species, lower freezing tolerance was positively correlated with a lower proportion of nodulated plants and active nodules, and under controlled conditions, freezing-induced reductions in aboveground biomass were lower on average in native legumes than in non-native legumes. Nevertheless, both non-native and native legume (except Desmodium canadense) exhibited greater reductions in biomass in response to increased freezing than their non-leguminous neighbors, both in controlled environments and in the field. CONCLUSIONS: These results demonstrate that both native and non-native legumes exhibit low freezing tolerance relative to other herbaceous species in northern temperate plant communities. By reducing legume biomass and nodulation, increased soil freezing could reduce N inputs into these systems.

Short-versus long-term effects of nitrogen addition and warming on soil nitrogen mineralization and leaching in a grass-dominated old field.

Increased atmospheric nitrogen (N) deposition and climate warming are both anticipated to influence the N dynamics of northern temperate ecosystems substantially over the next century. In field experiments with N addition and warming treatments, cumulative treatment effects can be important for explaining variation in treatment effects on N dynamics over time; however, comparisons between data collected in the early vs. later years potentially can be confounded with interactions between treatment effects and inter-annual variation in environmental conditions or other factors. We compared the short-term versus long-term effects of N addition and warming on net N mineralization and N leaching in a grass-dominated old field using in situ soil cores. We added new N addition and warming plots (3 years old) to an existing field experiment (16 years old), which enabled comparison of the treatment effects at both time scales while controlling for potential inter-annual variation in other factors. For net N mineralization, there was a significant interaction between plot age and N addition over the growing season, and for extractable inorganic N there was a significant interaction between plot age and warming over winter. In both cases, the directions of the treatment effects differed among old and new plots. Moreover, the responses in the new plots differed from the responses observed previously when the 16-year-old plots had been new. These results demonstrate how inter-annual variation in responses, independent from cumulative treatment effects, can play an important role in interpreting long-term effects on soil N cycling in global change field experiments.

Consistent predictors of microbial community composition across spatial scales in grasslands reveal low context-dependency.

Environmental circumstances shaping soil microbial communities have been studied extensively. However, due to disparate study designs, it has been difficult to resolve whether a globally consistent set of predictors exists, or context-dependency prevails. Here, we used a network of 18 grassland sites (11 of those containing regional plant productivity gradients) to examine (i) if similar abiotic or biotic factors predict both large-scale (across sites) and regional-scale (within sites) patterns in bacterial and fungal community composition, and (ii) if microbial community composition differs consistently at two levels of regional plant productivity (low vs. high). Our results revealed that bacteria were associated with particular soil properties (such as base saturation) and both bacteria and fungi were associated with plant community composition across sites and within the majority of sites. Moreover, a discernible microbial community signal emerged, clearly distinguishing high and low-productivity soils across different grasslands independent of their location in the world. Hence, regional productivity differences may be typified by characteristic soil microbial communities across the grassland biome. These results could encourage future research aiming to predict the general effects of global changes on soil microbial community composition in grasslands and to discriminate fertile from infertile systems using generally applicable microbial indicators.

Dominance by non-native grasses suppresses long-term shifts in plant species composition and productivity in response to global change.

Climate warming and increased atmospheric nitrogen deposition are both predicted to alter the primary productivity of grass-dominated systems in the coming decades. In field experiments, while both factors can have substantial effects on productivity in the initial years, further changes can be delayed by lags in plant species composition responses. However, the effects of experiment age can be confounded by annual variability in environmental conditions, and a replicate experiment established at a later time is therefore needed to separate these effects. We added new warming and nitrogen plots to an ongoing (14 year-old) field experiment in a grass-dominated temperate old field to compare the short-term vs. long-term treatment effects on plant productivity and species composition, while controlling for interannual environmental variability. We predicted treatment effects on relative species abundances would be most pronounced in the old plots. Although treatment responses of productivity (specifically to N addition) were highest in the old plots in the first year, by the second year there were no interactions between treatment and plot age. Moreover, there were no plot age effects on plant species composition, which was associated with continued dominance of non-native grasses. Our results therefore suggest that despite initial increases in productivity in response to global change, dominance by non-native grasses can suppress the emergence of further long-term treatment effects on productivity by inhibiting the responses of other species.

Temperature and pH define the realised niche space of arbuscular mycorrhizal fungi.

The arbuscular mycorrhizal (AM) fungi are a globally distributed group of soil organisms that play critical roles in ecosystem function. However, the ecological niches of individual AM fungal taxa are poorly understood. We collected > 300 soil samples from natural ecosystems worldwide and modelled the realised niches of AM fungal virtual taxa (VT; approximately species-level phylogroups). We found that environmental and spatial variables jointly explained VT distribution worldwide, with temperature and pH being the most important abiotic drivers, and spatial effects generally occurring at local to regional scales. While dispersal limitation could explain some variation in VT distribution, VT relative abundance was almost exclusively driven by environmental variables. Several environmental and spatial effects on VT distribution and relative abundance were correlated with phylogeny, indicating that closely related VT exhibit similar niche optima and widths. Major clades within the Glomeraceae exhibited distinct niche optima, Acaulosporaceae generally had niche optima in low pH and low temperature conditions, and Gigasporaceae generally had niche optima in high precipitation conditions. Identification of the realised niche space occupied by individual and phylogenetic groups of soil microbial taxa provides a basis for building detailed hypotheses about how soil communities respond to gradients and manipulation in ecosystems worldwide.

The role of perennation traits in plant community soil frost stress responses.

BACKGROUND AND AIMS: Herbaceous plants can survive periods of prolonged freezing as below-ground structures or seed, which can be insulated from cold air by soil, litter or snow. Below-ground perennial structures vary in both form and their exposure to soil frost, and this structural variation thus may be important in determining the responses of plant communities to frost stress. METHODS: We conducted a suite of snow removal experiments in a northern temperate old field over 3 years to examine the relative freezing responses of different plant functional groups based on below-ground perennation traits. A litter removal treatment was added in the third year. Species-level percentage cover data were recorded in May, June and September then pooled by functional group. KEY RESULTS: Snow removal decreased total plant cover, and this response was particularly strong and consistent among years for tap-rooted and rhizomatous species. The snow removal responses of cover for plants with root buds and new recruits from seed varied from positive to negative among years. The cover of rootstock plants consistently increased in response to snow removal. Rhizomatous species were generally the most vulnerable to litter removal. CONCLUSIONS: This study is the first to explore the effects of variation in frost severity on the responses of different plant perennation trait functional groups. The responses of herbaceous species to frost may become increasingly important in northern temperate regions in the coming decades as a result of declining snow cover and increasing temperature variability. Our results reveal substantial variation in responses among perennation trait functional groups, which could drive changes in species abundance in response to variation in soil frost.

Interactions between soil heterogeneity and freezing: Implications for grassland plant diversity and relative species abundances.

Plant stress resulting from soil freezing is expected to increase in northern temperate regions over the next century due to reductions in snow cover caused by climate change. Within plant communities, soil spatial heterogeneity can potentially buffer the effects of plant freezing stress by increasing the availability of soil microsites that function as microrefugia. Moreover, increased species richness resulting from soil heterogeneity can increase the likelihood of stress-tolerant species being present in a community. We used a field experiment to examine interactions between soil heterogeneity and increased freezing intensity (achieved via snow removal) on plant abundance and diversity in a grassland. Patches of topsoil were mixed with either sand or woodchips to create heterogeneous and homogeneous treatments, and plant community responses to snow removal were assessed over three growing seasons. Soil heterogeneity interacted significantly with snow removal, but it either buffered or exacerbated the snow removal response depending on the specific substrate (sand vs. woodchips) and plant functional group. In turn, snow removal influenced plant responses to soil heterogeneity; for example, adventive forb cover responded to increased heterogeneity under ambient snow cover, but this effect diminished with snow removal. Our results reveal that soil heterogeneity can play an important role in determining plant responses to changes in soil freezing stress resulting from global climate change. While the deliberate creation of soil microsites in ecological restoration projects as a land management practice could increase the frequency of microrefugia that mitigate plant community responses to increased freezing stress, the design of these microsites must be optimized, given that soil heterogeneity also has the potential to exacerbate freezing stress responses.

Interactions of plant growth responses to spring freezing and summer drought: a multispecies comparison.

PREMISE OF THE STUDY: Freezing and drought both result in cellular dehydration, and similar physiological responses to these stressors may result in cross acclimation, whereby prior freezing exposure increases subsequent drought tolerance. We examined how spring freezing influences summer drought tolerance for a range of herbaceous old field species: 6 graminoids (Agrostis stolonifera, Arrhenatherum elatius, Bromus inermis, Festuca rubra, Lolium perenne, Poa compressa) and 2 forbs (Plantago lanceolata, Securigera varia), with the goal of examining the generality of cross acclimation responses. METHODS: We exposed the plants to -5°C in the spring and to a 3-week summer drought, and harvested the plants after a 3-week watering/recovery period. We also measured leaf soluble proteins and sugars to explore the potential mechanisms before and during drought stress. KEY RESULTS: For Agrostis stolonifera, Bromus inermis, Lolium perenne, Plantago lanceolata, and Poa compressa there was evidence of cross acclimation based on aboveground or belowground biomass, with a reduction in the severity of the drought effect for the plants previously exposed to freezing. Freezing and drought effects were additive for Arrhenatherum elatius, and for the remaining two species the test of the freezing-drought interaction was inconclusive, because significant drought and freezing effects did not co-occur. When present, freezing-drought interactions were not correlated with changes in leaf soluble protein or sugars. CONCLUSIONS: Our results reveal that the phenomenon of freezing-drought cross acclimation appears to be common in herbaceous species, and variation among species in cross acclimation indicates that multiple stresses could alter relative species abundances in plant communities.

Drought sensitivity of aboveground productivity in Leymus chinensis meadow steppe depends on drought timing.

There is limited understanding of the combined effects of discrete climate extremes and chronic environmental changes on ecosystem processes and functioning. We assessed the interactions of extreme drought timing (45 days, in spring or summer) and nitrogen (N) addition in a full factorial field experiment in a Leymus chinensis-dominated meadow steppe in northeast China. We evaluated the resistance and recovery of the grassland (calculated in terms of aboveground biomass) to these two drought events. The spring drought reduced aboveground biomass by 28% in the unfertilized plots and by 33% in the fertilized plots, and the effects persisted during the subsequent post-drought period within the same growing season; however, the summer drought had no significant influence on aboveground biomass. Although there were no significant interactive effects between drought timing and N addition, we observed a potential trend of N addition increasing the proportion of aboveground biomass suppressed by spring drought but not summer drought. Moreover, the drought resistance of the aboveground biomass was positively correlated with the response of the belowground biomass to drought. One year after the extreme drought events, the spring drought effects on aboveground and belowground biomass were negligible. Our results indicate that the drought sensitivity of productivity likely depends on the phenological and morphological traits of the single highly dominant species (Leymus chinensis) in this meadow steppe.

Plant responses to climatic extremes: within-species variation equals among-species variation.

Within-species and among-species differences in growth responses to a changing climate have been well documented, yet the relative magnitude of within-species vs. among-species variation has remained largely unexplored. This missing comparison impedes our ability to make general predictions of biodiversity change and to project future species distributions using models. We present a direct comparison of among- versus within-species variation in response to three of the main stresses anticipated with climate change: drought, warming, and frost. Two earlier experiments had experimentally induced (i) summer drought and (ii) spring frost for four common European grass species and their ecotypes from across Europe. To supplement existing data, a third experiment was carried out, to compare variation among species from different functional groups to within-species variation. Here, we simulated (iii) winter warming plus frost for four grasses, two nonleguminous, and two leguminous forbs, in addition to eleven European ecotypes of the widespread grass Arrhenatherum elatius. For each experiment, we measured: (i) C/N ratio and biomass, (ii) chlorophyll content and biomass, and (iii) plant greenness, root (15) N uptake, and live and dead tissue mass. Using coefficients of variation (CVs) for each experiment and response parameter, a total of 156 within- vs. among-species comparisons were conducted, comparing within-species variation in each of four species with among-species variation for each seed origin (five countries). Of the six significant differences, within-species CVs were higher than among-species CVs in four cases. Partitioning of variance within each treatment in two of the three experiments showed that within-species variability (ecotypes) could explain an additional 9% of response variation after accounting for the among-species variation. Our observation that within-species variation was generally as high as among-species variation emphasizes the importance of including both within- and among-species variability in ecological theory (e.g., the insurance hypothesis) and for practical applications (e.g., biodiversity conservation).

Prior exposure to freezing stress enhances the survival and recovery of Poa pratensis exposed to severe drought.

PREMISE OF THE STUDY: Both freezing and drought cause cellular dehydration, and they elicit similar increases in protective compounds, which suggests that these stresses could potentially interact. We examined whether the physiological changes that occur in response to freezing in the fall and spring could affect subsequent survival and growth after summer drought. METHODS: We froze Poa pratensis tillers in the late fall, early spring, or late spring at 0, -5, or -10°C for 3 d and then subjected them to no drought (-0.025 MPa), moderate drought (-0.140 MPa), or severe drought (-0.250 MPa) for 3 wk in the summer. We quantified survival and total biomass after a 3-wk recovery period, and we determined leaf soluble sugar concentrations before and then 0, 30, and 55 d after freezing. KEY RESULTS: For survival and biomass, there were significant interactions between freezing and drought. Spring frozen tillers had the highest biomass and survival following severe drought, whereas fall freezing did not significantly increase the biomass of tillers following the severe drought. Increased drought tolerance after spring freezing did not appear to be associated with increased soluble sugar content, given that the freezing effects on leaf glucose, fructose, and sucrose content were absent 55 d post freezing. CONCLUSIONS: Our results demonstrate that multiple stresses that occur over different seasons can interact; this interaction is highly relevant to herbaceous species in northern temperate regions that are experiencing more intense and frequent stress as a result of changes in snow cover and extreme climatic events.

Soil freezing and N deposition: transient vs multi-year effects on plant productivity and relative species abundance.

Plant responses to increased atmospheric nitrogen (N) deposition must be considered in the context of a rapidly changing climate. Reductions in snow cover with climate warming can increase the exposure of herbaceous plants to freezing, but it is unclear how freezing damage may interact with increased N availability, and to what extent freezing effects may extend over multiple years. We explored potential interactions between freezing damage and N availability in the context of plant productivity and relative species abundance in a temperate old field using both snow removal and mesocosm experiments, and assessed the legacy effects of the freezing damage over 3 yr. As expected, N addition increased productivity and freezing damage decreased productivity, but these factors were nonadditive; N addition increased productivity disproportionately in the snow removal plots, whereas extreme freezing diminished N addition responses in the mesocosm experiment. Freezing altered relative species abundances, although only the most severe freezing treatments exhibited legacy effects on total productivity over multiple growing seasons. Our results emphasize that while both increased N deposition and freezing damage can have multi-year effects on herbaceous communities, the interactions between these global change factors are contingent on the intensities of the treatments.

Interactive responses of grass litter decomposition to warming, nitrogen addition and detritivore access in a temperate old field.

Plant litter decomposition has been studied extensively in the context of both climate warming and increased atmospheric N deposition. However, much of this research is based on microbial responses, despite the potential for detritivores to contribute substantially to litter breakdown. We measured litter mass-loss responses to the combined effects of warming, N addition and detritivore access in a grass-dominated old field. We concurrently assessed the roles of litter treatment origin vs. microenvironment (direct warming and N-addition effects) to elucidate the mechanisms through which these factors affect decomposition. After 6 weeks, mass loss increased in N-addition plots, and it increased with detritivore access in the absence of warming. After 1 year, warming, N addition, and detritivore access all increased litter mass loss, although the effects of N addition and warming were non-additive in the detritivore-access plots. For the litter-origin experiment, mass loss after 6 weeks increased in litter from N-addition plots and warmed plots, but unlike the overall decomposition response, the N-addition effect was enhanced by detritivore access. Conversely, for the microenvironment experiment, detritivore access only increased mass loss in unfertilized plots. After 1 year, detritivore access increased mass loss in the litter-origin and microenvironment experiments, but there were no warming or N-addition effects. Overall, our results provide support for a substantial role of detritivores in promoting litter mass loss in our system. Moreover, they reveal important interactions between litter origin, microclimate and detritivores in determining decomposition responses to global change.

Applied winter biology: threats, conservation and management of biological resources during winter in cold climate regions.

Winter at high latitudes is characterized by low temperatures, dampened light levels and short photoperiods which shape ecological and evolutionary outcomes from cells to populations to ecosystems. Advances in our understanding of winter biological processes (spanning physiology, behaviour and ecology) highlight that biodiversity threats (e.g. climate change driven shifts in reproductive windows) may interact with winter conditions, leading to greater ecological impacts. As such, conservation and management strategies that consider winter processes and their consequences on biological mechanisms may lead to greater resilience of high altitude and latitude ecosystems. Here, we use well-established threat and action taxonomies produced by the International Union of Conservation of Nature-Conservation Measures Partnership (IUCN-CMP) to synthesize current threats to biota that emerge during, or as the result of, winter processes then discuss targeted management approaches for winter-based conservation. We demonstrate the importance of considering winter when identifying threats to biodiversity and deciding on appropriate management strategies across species and ecosystems. We confirm our expectation that threats are prevalent during the winter and are especially important considering the physiologically challenging conditions that winter presents. Moreover, our findings emphasize that climate change and winter-related constraints on organisms will intersect with other stressors to potentially magnify threats and further complicate management. Though conservation and management practices are less commonly considered during the winter season, we identified several potential or already realized applications relevant to winter that could be beneficial. Many of the examples are quite recent, suggesting a potential turning point for applied winter biology. This growing body of literature is promising but we submit that more research is needed to identify and address threats to wintering biota for targeted and proactive conservation. We suggest that management decisions consider the importance of winter and incorporate winter specific strategies for holistic and mechanistic conservation and resource management.

Interactions of herbivore exclusion with warming and N addition in a grass-dominated temperate old field.

Field experiments used to explore the effects of global change drivers, such as warming and nitrogen deposition on plant productivity and species composition, have typically focused on bottom-up processes. However, both direct and indirect responses of herbivores to the treatments could result in important interactions between top-down and bottom-up effects. These interactions may be complicated by the simultaneous effects of multiple herbivore taxa. We used rodent and mollusc exclosures in the plots of a warming and N addition field experiment to examine how herbivore removal would influence plant biomass responses to the treatments. The effect of rodent exclusion on grass biomass more than doubled in response to nitrogen addition, but did not respond to warming, whereas the effect of mollusc exclusion on grass biomass increased in response to warming, but not nitrogen. In contrast, the effect of rodent exclusion on total biomass (grasses and forbs combined) increased in response to both nitrogen and warming, while the effect of mollusc exclusion on total biomass was insensitive to nitrogen and warming. In no cases were there interactions between nitrogen and warming with respect to their influence on exclosure effects. Overall, our results demonstrated substantial and variable effects of multiple herbivore taxa on plant biomass responses to warming and N addition, despite the absence of conspicuous damage to the plant canopy. These results therefore highlight the potential importance of interactions between top-down and bottom-up factors in global change field experiments.

Net nitrogen mineralization and leaching in response to warming and nitrogen deposition in a temperate old field: the importance of winter temperature.

While climate warming can increase plant N availability over the growing season by increasing rates of N mineralization, increased N mineralization over winter at a time when plant roots are largely inactive, coupled with an increased frequency of soil freeze-thaw cycles, may increase soil N leaching losses. We examined changes in soil net N mineralization and N leaching in response to warming and N addition (6 g m(-2) year(-1)) in a factorial experiment conducted in a temperate old field. We used two warming treatments, year-round and winter-only warming, to isolate the effects of winter warming on soil N dynamics from the year-round warming effects. We estimated net N mineralization using in situ soil cores with resin bags placed at the bottom to catch throughput, and we measured N leaching using lysimeters located below the plant rooting zone at a depth of 50 cm. There were minor effects of warming on changes in soil extractable N and resin N in the soil cores over winter. Nevertheless, the overall effects of both warming and N addition on net N mineralization (the sum of changes in soil extractable N and resin N) were not significant over this period. Likewise, there were no significant treatment effects on the concentration of N in leachate collected below the plant rooting zone. However, in response to winter warming, net N mineralization over summer was approximately double that of both the ambient and year-round warming treatments. This result demonstrates a potentially large and unexpected effect of winter warming on soil N availability in this old field system.

Towards a mechanistic understanding of soil nitrogen availability responses to summer vs. winter drought in a semiarid grassland.

More frequent and intense drought events resulting from climate change are anticipated to become important drivers of change for terrestrial ecosystem function by affecting water and nutrient cycles. In semiarid grasslands, the responses of soil nitrogen availability to severe drought and the underlying mechanisms are largely unknown. Moreover, the responses and mechanisms may vary between summer and winter drought. We examined soil nitrogen availability responses to extreme reductions in precipitation over summer and winter using a field experiment in a semiarid grassland located in northeast China, and we explored the mechanisms by examining associated changes in abiotic factors (soil property responses) and biotic factors (plant and soil microbial responses). The results demonstrated that both the summer and winter severe drought treatments significantly reduced plant and microbial biomass, whereas summer drought also changed soil microbial community structure. Summer drought, winter drought and combined summer and winter drought decreased the resistance of soil nitrogen availability by 38.7 ± 11.1%, 43.3 ± 11.4% and 43.8 ± 6.0%, respectively. While both changes in abiotic factors (reduced soil water content and total nitrogen content) and biotic factors (reduced plant and microbial biomass) explained the resistance of soil nitrogen availability to drought over summer, only changes in biotic factors (reduced plant and microbial biomass) explained the legacy effect of winter drought. Our results highlight that severe drought can have important consequences for nitrogen cycling in semiarid grasslands, and that both the effects of summer and winter drought must be accounted for in predicting these responses.

Brachypodium histone deacetylase BdHD1 positively regulates ABA and drought stress responses.

Despite recent evidence that HDACs are involved in the environmental stress responses of plants, their roles in the abiotic stress responses of monocot plants remain largely unexplored. We investigated a HDAC gene, Bradi3g08060 (BdHD1), in Brachypodium distachyon. The Brachypodium BdHD1-overexpression plants displayed a hypersensitive phenotype to ABA and exhibited better survival under drought conditions. On the other hand, the RNA-interference plants were insensitive to ABA and showed low survival under drought stress. At the genome-wide level, overexpression of BdHD1 led to lower H3K9 acetylation at the transcriptional start sites of 230 genes than in the wild type plants under the drought treatment. We validated our ChIP-Seq data on 10 selected transcription factor genes from the 230 drought-specific genes. These genes exhibited much lower expression in the BdHD1-overexpression plants compared to the wild type plants under drought stress. We further identified an ABA-inducible transcription factor gene BdWRKY24 that was repressed in BdHD1-OE plants, but highly expressed in RNA-interference plants under drought stress. These results indicate that BdHD1 plays a positive role in ABA sensitivity and drought stress tolerance and they provide a link between the role of BdHD1 and the drought stress response at a genome-wide level in Brachypodium.

Development of Fertilizer Coatings from Polyglyoxylate-Polyester Blends Responsive to Root-Driven pH Change.

Many current controlled-release fertilizers (CRFs) are coated with nonbiodegradable polymers that can contribute to microplastic pollution. Here, coatings of self-immolative poly(ethyl glyoxylate) (PEtG) capped with a carbamate and blended with polycaprolactone (PCL) or poly(l-lactic acid) (PLA) were evaluated. They were designed to depolymerize and release fertilizers in the vicinity of plant roots, where the pH is lower than that in the surrounding environment. PEtG/PCL coatings exhibited significant temperature and pH effects, requiring 18 days at pH 5 and 30 °C, compared to 77 days at pH 7 and 22 °C, to reach 15% mass loss. Plant roots were also effective in triggering coating degradation. Spray-coating and melt-coating were explored, with the latter being more effective in providing pellets that retained urea prior to polymer degradation. Finally, PEtG/PCL-coated pellets promoted plant growth to a similar degree or better than currently available CRFs.

Photoinduced Degradation of Polymer Films Using Polyglyoxylate-Polyester Blends and Copolymers.

Polymeric coatings are commonly employed to alter surface properties. While some coatings are designed to remain stable over a prolonged period, in applications such as pharmaceuticals or fertilizers, the coating is designed to erode and reveal or release the underlying material. Self-immolative polymers (SIPs) undergo depolymerization following the cleavage of stimuli-responsive end-caps from their termini, enabling controlled depolymerization in the solid state and in solution. Poly(ethyl glyoxylate) (PEtG) is a promising SIP because of its depolymerization to benign products, but its amorphous structure and low glass-transition temperature make it unsuitable alone for coating applications. This study explored the blending of PEtG with polyesters including polycaprolactone (PCL), poly(l-lactic acid), and poly(R-3-hydroxybutyrate). Block copolymers of PEtG with PCL were also synthesized and studied. It was found that the phase separation behavior and consequently the thermal and mechanical properties of the materials could be tuned according to the composition of the blend, while the stimuli-responsive degradation of PEtG was retained in the blends. This work therefore provides a framework for the application of PEtG-based coatings in applications ranging from pharmaceuticals to agricultural products.