Role of benzophenone-3 additive in the effect of polyethylene microplastics on Daphnia magna population dynamics.

The adverse effects of microplastics (MPs) on Daphnia magna have been extensively studied; however, their population-level effects are relatively unknown. This study investigated the effect of polyethylene MP fragments (33.90 ± 17.44 µm) and benzophenone-3 (BP-3), which is a widely used plastic additive (2.91 ± 0.02% w/w), on D. magna population dynamics in a 34-day microcosm experiment. In the growth phase, neither MP nor MP/BP-3 fragments changed the population size of D. magna compared with the control. However, MP/BP-3 fragments significantly reduced (p < 0.05) the population biomass compared to that of the control, whereas MP fragments did not induce a significant reduction. The MP/BP-3 group had a significantly higher (p < 0.05) neonate proportion than that in the control and MP groups. MP/BP-3 fragments upregulated usp and downregulated ecrb, ftz-f1, and hr3, altering gene expression in the ecdysone signaling pathway linked to D. magna growth and development. These findings suggested that BP-3 in MP/BP-3 fragments may disrupt neonatal growth, thereby decreasing population biomass. In the decline phase, MP fragments significantly decreased (p < 0.05) the population size and biomass of D. magna compared with the control and MP/BP-3 fragments. This study highlights the importance of plastic additives in the population-level ecotoxicity of MPs.

Population Balance Equations for Reactive Separation in Polymer Upcycling.

Many polymer upcycling efforts aim to convert plastic waste into high-value liquid hydrocarbons. However, the subsequent cleavage of middle distillates to light gases can be problematic. The reactor often contains a vapor phase (light gases and middle distillates) and a liquid phase (molten polymers and waxes with a suspended or dissolved catalyst). Because the catalyst resides in the liquid phase, middle distillates that partition into the vapor phase are protected against further cleavage into light gases. In this paper, we consider a simple reactive separation strategy, in which a gas outflow removes the volatile products as they form. We combine vapor-liquid equilibrium models and population balance equations (PBEs) to describe polymer upcycling in a two-phase semibatch reactor. The results suggest that the temperature, headspace volume, and flow rate of the reactor can be used to tune selectivity toward the middle distillates, in addition to the molecular mechanism of catalysis. We anticipate that two-phase reactor models will be important in many polymer upcycling processes and that reactive separation strategies will provide ways to boost the yield of the desired products in these cases.

Ecotoxicity of polylactic acid microplastic fragments to Daphnia magna and the effect of ultraviolet weathering.

Biodegradable plastics (BPs) are widely used as alternatives to non-BPs due to their inherent ability to undergo facile degradation. However, the ecotoxicological impact of biodegradable microplastics (MPs) rarely remains scientific documented especially to aquatic ecosystem and organisms compared to conventional microplastics. Therefore, this study aimed to investigate the ecotoxicity of biodegradable polylactic acid (PLA) MPs to Daphnia magna with that of conventional polyethylene (PE) MPs with and without ultraviolet (UV) treatment (4 weeks). The acute toxicity (48 h) of PLA MPs was significantly higher than that of PE MPs, potentially attributable to their elevated bioconcentration resulting from their higher density. UV treatment notably reduced the particle size of PLA MPs and induced new hydrophilic functional groups containing oxygen. Thus, the acute lethal toxicity of PLA MPs exhibited noteworthy increase, compared to before UV treatment after UV treatment, which was greater than that of UV-PE MPs. In addition, UV-PLA MPs showed markedly elevated reactive oxygen species concentration in D. magna compared to positive control. However, there was no significant increase in the level of lipid peroxidation, possibly due to successful defense by antioxidant enzymes (superoxide dismutase and catalase). These findings highlight the ecotoxicological risks of biodegradable MPs to aquatic organisms, which require comprehensive long-term studies.

Mechanism of Enhanced Triplet-Triplet Upconversion in Organic Molecules.

We use time-dependent density functional theory (TDDFT) to investigate the mechanism of efficient triplet-triplet upconversion (TTU) in certain organic materials. In particular, we focus on materials where some singlets are generated in a two-step spin-nonconserving process (T1 + T1 → T2 → S1). For this mechanism to contribute significantly, the intersystem crossing (ISC) from the high-lying triplet to the singlet (T2 → S1) must outcompete the internal conversion (IC) to the low-lying triplet (T2 → T1). By considering multiple families of materials, we show that the T2 → S1 ISC can be enhanced in a number of ways: the substitution of electron-donating (ED) and electron-withdrawing (EW) groups at appropriate positions; the substitution of bulky groups that distort the molecular geometry; and the substitution of heavy atoms that enhance the spin-orbit coupling (SOC). In the first two cases, the enhancements are consistent with El-Sayed's rule in that rapid T2 → S1 ISC requires significant differences in the characters of the S1 and the T2 wavefunctions. Together, these effects enable a wide tunability of T2 → S1 ISC rates over at least 5 orders of magnitude. Meanwhile, the T2 → T1 IC is inhibited in these systems due to the large T2 - T1 energy gap >0.5 eV, which entails a high energy barrier to the T2 → T1 IC and the prediction of a slow rate regardless of the substituents or the presence of heavy atoms. In this way, tuning the T2 → S1 ISC appears to provide an effective strategy to achieve systematic improvement of TTU materials.

Maternal Effect of Polyethylene Microplastic Fragments Containing Benzophenone-3 in Different Ages and Broods of Daphnia Magna.

The maternal effect of microplastics (MPs) toxicity is likely influenced by age and brood of test species. This study investigated the maternal effect of polyethylene MP fragments (18.23 ± 8.02 µm) with benzophenone-3 (BP-3; 2.89 ± 0.20% w/w) on chronic toxicity to Daphnia magna over two generations. Neonate (< 24 h old) and adult (5 d old) daphnids in the F0 generation were exposed until 21 d old, then first and third brood neonates in the F1 generation were recovered in clean M4 medium for 21 d. Higher chronic toxicity and maternal effect of MP/BP-3 fragments were observed in the adult group compared with the neonate group, reducing growth and reproduction in both F0 and F1 generations. First brood neonates in the F1 generation showed a higher maternal effect of MP/BP-3 fragments than third brood ones, resulting in enhanced growth and reproduction relative to the control. This study provided insights into the ecological risk of MPs containing plastic additives in the natural environment.

Exchange controlled triplet fusion in metal-organic frameworks.

Triplet-fusion-based photon upconversion holds promise for a wide range of applications, from photovoltaics to bioimaging. The efficiency of triplet fusion, however, is fundamentally limited in conventional molecular and polymeric systems by its spin dependence. Here, we show that the inherent tailorability of metal-organic frameworks (MOFs), combined with their highly porous but ordered structure, minimizes intertriplet exchange coupling and engineers effective spin mixing between singlet and quintet triplet-triplet pair states. We demonstrate singlet-quintet coupling in a pyrene-based MOF, NU-1000. An anomalous magnetic field effect is observed from NU-1000 corresponding to an induced resonance between singlet and quintet states that yields an increased fusion rate at room temperature under a relatively low applied magnetic field of 0.14 T. Our results suggest that MOFs offer particular promise for engineering the spin dynamics of multiexcitonic processes and improving their upconversion performance.

Transgenerational effects of polyethylene microplastic fragments containing benzophenone-3 additive in Daphnia magna.

Maternal exposure to microplastics (MPs) plays an important role in the fitness of unexposed progeny. In this study, the transgenerational effects of polyethylene MP fragments (17.35 ± 5.50 µm) containing benzophenone-3 (BP-3; 2.85 ± 0.16% w/w) on chronic toxicity (21 d) in Daphnia magna were investigated across four generations. Only D. magna in the F0 generation was exposed to MP fragments, MP/BP-3 fragments, and BP-3 leachate to identify the transgenerational effect in the F3 generation. The mortality of D. magna induced by MP and MP/BP-3 fragments was recovered in the F3 generation, but somatic growth and reproduction significantly decreased compared to the control. Additionally, reproduction of D. magna exposed to BP-3 leachate significantly decreased in the F3 generation. These findings confirmed the transgenerational effects of MP fragment and BP-3 additive on D. magna. Particularly, the adverse effect on D. magna reproduction seemed to be cumulative across four generations for MP/BP-3 fragments, while it was an acclimation trend for BP-3 leachate. However, there was no significant difference in global DNA methylation in D. magna across four generations, thus requiring a gene-specific DNA methylation study to identify different epigenetic transgenerational inheritance.

Machine learning dynamic correlation in chemical kinetics.

Lattice models are a useful tool to simulate the kinetics of surface reactions. Since it is expensive to propagate the probabilities of the entire lattice configurations, it is practical to consider the occupation probabilities of a typical site or a cluster of sites instead. This amounts to a moment closure approximation of the chemical master equation. Unfortunately, simple closures, such as the mean-field and the pair approximation (PA), exhibit weaknesses in systems with significant long-range correlation. In this paper, we show that machine learning (ML) can be used to construct accurate moment closures in chemical kinetics using the lattice Lotka-Volterra model as a model system. We trained feedforward neural networks on kinetic Monte Carlo (KMC) results at select values of rate constants and initial conditions. Given the same level of input as PA, the ML moment closure (MLMC) gave accurate predictions of the instantaneous three-site occupation probabilities. Solving the kinetic equations in conjunction with MLMC gave drastic improvements in the simulated dynamics and descriptions of the dynamical regimes throughout the parameter space. In this way, MLMC is a promising tool to interpolate KMC simulations or construct pretrained closures that would enable researchers to extract useful insight at a fraction of the computational cost.

Maximizing TADF via Conformational Optimization.

We investigate a new strategy to enhance thermally activated delayed fluorescence (TADF) in organic light-emitting diodes (OLEDs). Given that the TADF rate of a molecule depends on its conformation, we hypothesize that there exists a conformation that maximizes the TADF rate. To test this idea, we use time-dependent density functional theory (TDDFT) to simulate the TADF rates of several TADF emitters while varying their geometries in a select subspace of internal coordinates. We find that geometric changes in this subspace can increase the TADF rate up to 3 orders of magnitude with respect to the minimum energy conformation, and the simulated TADF rate can even be brought into the submicrosecond time scales under the right conditions. Furthermore, the TADF rate enhancement can be maintained with a conformational energy that might be within the reach of modern synthetic chemistry. Analyzing the maximum TADF conformation, we extract a number of structural motifs that might provide a useful handle on the TADF rate of a donor-acceptor (DA) system. The incorporation of conformational engineering into the TADF technology could usher in a new paradigm of OLEDs.