Tunable and Recyclable Polyesters from CO2 and Butadiene

Carbon dioxide is inexpensive and abundant, and its prevalence as waste makes it attractive as a sustainable chemical feedstock. Although there are examples of copolymerizations of CO2 with high-energy monomers, the direct copolymerization of CO2 with olefins has not been reported. Herein, an alternate route to tunable, recyclable polyesters derived from CO2 and butadiene via an intermediary lactone, 3-ethyl-6-vinyltetrahydro-2H-pyran-2-one, is described. Catalytic ring-opening polymerization of the lactone by 1,5,7-triazabicyclo[4.4.0]dec-5-ene yields polyesters with molar masses up to 13.6 kg/mol and pendent vinyl sidechains that can undergo post-polymerization functionalization. The polymer has a low ceiling temperature of 138 ºC, allowing for facile chemical recycling. These results mark the first example of a well-defined polyester derived solely from CO2 and olefins, expanding access to new feedstocks that were once considered unfeasible.

Predicting Seedling Emergence of Three Canarygrass (Phalaris) Species under Semi-Arid Conditions Using Parametric and Non-Parametric Models

The Phalaris genus includes annual weed species such as short-spiked canarygrass (Phalaris brachystachys Link.), little-seed canarygrass (Phalaris minor Retz.) and hood canarygrass (Phalaris paradoxa L.), which are especially problematic in Spain; as such, there is a need to develop models to predict the timing of their emergence. Field experiments were conducted at two different locations during two (2006/07 and 2007/08) and three (from 2005/06 to 2007/08) growing seasons. In both locations, 500 seeds of each Phalaris species were sown each growing season, simulating rain-fed cereal field conditions. In addition, the models were validated with three, four and eight independent experiments for P. brachystachys, P. minor and P. paradoxa, respectively. The emergence period of the three Phalaris species lasted between 31 and 48 days after sowing (DAS), showing two main flushes. The three cardinal points for parametric and non-parametric models were established to be between −1 °C and 1 °C for base temperature, between 9.8 °C and 11.8 °C for optimal temperature and between 21.2 °C and 23.4 °C for ceiling temperature; base water potential was estimated to be between −1 and −1.1 MPa. Both parametric and non-parametric models obtained similar results and were successfully validated in 12 out of 15 independent experiments.

Thermal requirements and germination niche breadth of Polygonum ferrugineum Wedd. from southeastern Brazil

Temperature may regulate seed dormancy and germination and determine the geographical distribution of species. The present study investigated the thermal limits for seed germination of Polygonum ferrugineum (Polygonaceae), an aquatic emergent herb distributed throughout tropical and subtropical America. Seed germination responses to light and temperature were evaluated both before (control) and after stratification at 10, 15 and 20°C for 7, 14 and 28 d. Germination of control seeds was ~50% at 10 and 15°C, and they did not germinate from 20 to 30°C. The best stratification treatment was 7 d at 10°C, where seed germination was >76% in the dark for all temperatures, except at 30°C, and < 60% in light conditions. A thermal time approach was applied to the seed germination results. Base temperature (Tb) was 6.3°C for non-dormant seeds and optimal temperature (To) was 20.6°C, ceiling temperature (Tc (<50)) was 32.8°C, and thermal time requirement for 50% germination was 44.4°Cd. We concluded that a fraction of P. ferrugineum seeds is dormant, has a narrow thermal niche to germinate (10 and 15°C) and that cold stratification (10°C) alleviated dormancy and amplified the thermal range permissive for germination of the species. Consequently, P. ferrugineum is expected to occur in colder environments, for example, at high altitudes. Higher temperatures decrease the probabilities of alleviate dormancy and the ability of their seeds to germinate.

Modeling emergence of sterile oat (Avena sterilis ssp. ludoviciana) under semiarid conditions

Winter wild oat [Avena sterilis ssp. ludoviciana (Durieu) Gillet & Magne; referred to as A. sterilis here] is one of the major weed species of the Avena genus, given its high competitive ability to infest cereal crops worldwide, with special concern in Spain. A nine-location field experiment was established across Spain where a total of 400 A. sterilis seeds per location were sowed in four replicates in autumn 2016 to monitor the emergence during two growing seasons in dryland conditions. The data were used to test the prediction ability of previously published thermal (TT) and hydrothermal time (HTT) models and to develop new models, if required. Overall, the average percentage of emergence was 30% during the first season and 21% during the second season. In both seasons, the main emergence flush occurred between November and February. According to the phenological stage, A. sterilis achieved the tillering earlier in southern sites, between November 25 and the end of December, compared with northern sites, where this stage was reached at the end of January. The newly developed model described the emergence with precision, using three cardinal temperatures to estimate the TT. The three cardinal points were established at −1.0, 5.8, and 18.0 C for base (Tb), optimum (To), and ceiling temperature (Tc), while the base water potential (Ψb) was established at −0.2 MPa for the HTT estimation. This study contributes to improving prediction of the emergence of A. sterilis and provides knowledge for decision support systems (DSS) for the control of this weed.