Quantum information scrambling and chemical reactions.

The ultimate regularity of quantum mechanics creates a tension with the assumption of classical chaos used in many of our pictures of chemical reaction dynamics. Out-of-time-order correlators (OTOCs) provide a quantum analog to the Lyapunov exponents that characterize classical chaotic motion. Maldacena, Shenker, and Stanford have suggested a fundamental quantum bound for the rate of information scrambling, which resembles a limit suggested by Herzfeld for chemical reaction rates. Here, we use OTOCs to study model reactions based on a double-well reaction coordinate coupled to anharmonic oscillators or to a continuum oscillator bath. Upon cooling, as one enters the tunneling regime where the reaction rate does not strongly depend on temperature, the quantum Lyapunov exponent can approach the scrambling bound and the effective reaction rate obtained from a population correlation function can approach the Herzfeld limit on reaction rates: Tunneling increases scrambling by expanding the state space available to the system. The coupling of a dissipative continuum bath to the reaction coordinate reduces the scrambling rate obtained from the early-time OTOC, thus making the scrambling bound harder to reach, in the same way that friction is known to lower the temperature at which thermally activated barrier crossing goes over to the low-temperature activationless tunneling regime. Thus, chemical reactions entering the tunneling regime can be information scramblers as powerful as the black holes to which the quantum Lyapunov exponent bound has usually been applied.

Constraining Earth's nonlinear mantle viscosity using plate-boundary resolving global inversions.

Variable viscosity in Earth's mantle exerts a fundamental control on mantle convection and plate tectonics, yet rigorously constraining the underlying parameters has remained a challenge. Inverse methods have not been sufficiently robust to handle the severe viscosity gradients and nonlinearities (arising from dislocation creep and plastic failure) while simultaneously resolving the megathrust and bending slabs globally. Using global plate motions as constraints, we overcome these challenges by combining a scalable nonlinear Stokes solver that resolves the key tectonic features with an adjoint-based Bayesian approach. Assuming plate cooling, variations in the thickness of continental lithosphere, slabs, and broad scale lower mantle structure as well as a constant grain size through the bulk of the upper mantle, a good fit to global plate motions is found with a nonlinear upper mantle stress exponent of 2.43 [Formula: see text] 0.25 (mean [Formula: see text] SD). A relatively low yield stress of 151 [Formula: see text] 19 MPa is required for slabs to bend during subduction and transmit a slab pull that generates asymmetrical subduction. The recovered long-term strength of megathrusts (plate interfaces) varies between different subduction zones, with South America having a larger strength and Vanuatu and Central America having lower values with important implications for the stresses driving megathrust earthquakes.

Hotter is not (always) better: Embracing unimodal scaling of biological rates with temperature.

Rate-temperature scaling relationships have fascinated biologists for nearly two centuries and are increasingly important in our era of global climate change. These relationships are hypothesized to originate from the temperature-dependent kinetics of rate-limiting biochemical reactions of metabolism. Several prominent theories have formalized this hypothesis using the Arrhenius model, which characterizes a monotonic temperature dependence using an activation energy E. However, the ubiquitous unimodal nature of biological temperature responses presents important theoretical, methodological, and conceptual challenges that restrict the promise for insight, prediction, and progress. Here we review the development of key hypotheses and methods for the temperature-scaling of biological rates. Using simulations, we examine the constraints of monotonic models, illustrating their sensitivity to data nuances such as temperature range and noise, and their tendency to yield variable and underestimated E, with critical consequences for climate change predictions. We also evaluate the behaviour of two prominent unimodal models when applied to incomplete and noisy datasets. We conclude with recommendations for resolving these challenges in future research, and advocate for a shift to unimodal models that better characterize the full range of biological temperature responses.

Halide Ion Mixing across Colloidal 2D Ruddlesden-Popper Perovskites: Implication of Spacer Ligand on Mixing Kinetics.

Halide ion exchange seen in metal halide perovskites provide a substantial opportunity to control their halide composition and corresponding optoelectronic properties. Halide ion mixing across colloidal 3D perovskite nanocrystals have been extensively studied while the mixing within colloidal 2D counterparts remain underexplored. In this study, the halide ion exchange kinetics across colloidally stable 2D Ruddlesden-Popper layered bromide (Br) and iodide (I) perovskites using two different spacer ligands such as aromatic phenethylammonium (PEA) versus linear butyammonium (BA) is demonstrated. The halide exchange kinetic rate constant (k), as determined by tracking time-dependent absorbance changes, indicates that Br/I halide mixing in 2D PEA-based perovskites (2.7 × 10-3 min-1 ) occurs at an order of magnitude slower than in 2D BA-based perovskites (3.3 × 10-2 min-1 ). Concentration (≈1 mM to 100 mM) and temperature-dependent (50 to 80 °C) kinetic studies further allow for the determination of activation barrier for halide ion mixing across the 2D layered perovskites with 75.2 ± 4.4 kJ mol-1 (2D PEA) and 57.8 ± 7.8 kJ mol-1 (2D BA), respectively. The activation energy reveals that the type of spacer cations plays a crucial role in controlling the halide ion mobility and halide stability due mainly to the internal ligand chemical interaction within 2D structures.

Correlation between the activation energy of PLA respectively PLA/starch composites and mechanical properties with regard to differ accelerated aging conditions.

Within this research semi-crystalline polylactide and composites with 50 wt.% native potato starch were compounded and injection molded. The material was mechanically characterized by tensile, three-point bending, and Charpy impact tests. These tests were carried out in the freshly molded state and after 332 and 792 h of storage at accelerated temperature or humidity. The respective activation energy was calculated by applying the Flynn-Wall-Ozawa method. The focus of the study was to investigate the correlation between the activation energy and the related mechanical and thermal properties. The results showed that the addition of native potato starch as a filler prevents the decrease in activation energy over the course of the experiments. Thus, the PLA/starch composite is more resistant to the two aging conditions than the pure PLA. When considering the mechanical properties, the pure PLA showed a large deviation of results compared to the initial value in a range of +63.88% to -33.96% with regard to the respective aging conditions, whereas the PLA/starch composite properties nearly always remained at the initial values. Through the investigation of the mechanical and thermal properties, it was shown that the steady activation energies are consistent with the mechanical properties, as these have shown only a small deviation of the mechanical properties during the duration of experiments for the PLA/starch composite.

Flow Activation Energy of High-Concentration Monoclonal Antibody Solutions and Protein-Protein Interactions Influenced by NaCl and Sucrose.

The solution viscosity and protein-protein interactions (PPIs) as a function of temperature (4-40 °C) were measured at a series of protein concentrations for a monoclonal antibody (mAb) with different formulation conditions, which include NaCl and sucrose. The flow activation energy (Eη) was extracted from the temperature dependence of solution viscosity using the Arrhenius equation. PPIs were quantified via the protein diffusion interaction parameter (kD) measured by dynamic light scattering, together with the osmotic second virial coefficient and the structure factor obtained through small-angle X-ray scattering. Both viscosity and PPIs were found to vary with the formulation conditions. Adding NaCl introduces an attractive interaction but leads to a significant reduction in the viscosity. However, adding sucrose enhances an overall repulsive effect and leads to a slight decrease in viscosity. Thus, the averaged (attractive or repulsive) PPI information is not a good indicator of viscosity at high protein concentrations for the mAb studied here. Instead, a correlation based on the temperature dependence of viscosity (i.e., Eη) and the temperature sensitivity in PPIs was observed for this specific mAb. When kD is more sensitive to the temperature variation, it corresponds to a larger value of Eη and thus a higher viscosity in concentrated protein solutions. When kD is less sensitive to temperature change, it corresponds to a smaller value of Eη and thus a lower viscosity at high protein concentrations. Rather than the absolute value of PPIs at a given temperature, our results show that the temperature sensitivity of PPIs may be a more useful metric for predicting issues with high viscosity of concentrated solutions. In addition, we also demonstrate that caution is required in choosing a proper protein concentration range to extract kD. In some excipient conditions studied here, the appropriate protein concentration range needs to be less than 4 mg/mL, remarkably lower than the typical concentration range used in the literature.

Time and Temperature Dependence of Drug Crystallization─The Role of Molecular Mobility.

Using the time-temperature-transformation diagrams, we demonstrated a correlation between molecular mobility and crystallization in amorphous solid dispersions of nifedipine (NIF) with each polyvinylpyrrolidone vinyl acetate (PVPVA64) and polyvinyl caprolactam polyvinyl acetate-polyethylene glycol graft copolymer (Soluplus). The behavior was compared with the NIF dispersions prepared with each polyvinylpyrrolidone (PVP) and hydroxypropyl methylcellulose acetate succinate (HPMCAS) [Lalge et al., Mol. Pharmaceutics 2023, 20(3), 1806-1817]. Each system was characterized by a unique temperature at which the crystallization onset time was the shortest. Below this temperature, a coupling was observed between the α-relaxation time determined by dielectric spectroscopy and crystallization onset time. Above this temperature, the activation barrier for crystallization had a more significant role than molecular mobility. In the solid state, PVP and PVPVA64 dispersion exhibited higher resistance to crystallization than HPMCAS and Soluplus. The role of polymers in inhibiting crystal growth in nucleated systems was discerned by monitoring crystallization following wetting of the amorphous dispersion with the dissolution medium. PVPVA64 and Soluplus dispersions exhibited higher resistance to crystal growth than PVP and HPMCAS.

Electrooxidation of chlorophene and dichlorophen by reactive electrochemical membrane: Key determining factors of removal efficiency.

This study systematically investigated the variable main electrooxidation mechanism of chlorophene (CP) and dichlorophen (DCP) with the change of reaction conditions at Ti4O7 anode operated in batch and reactive electrochemical membrane (REM) modes. Significant degradation of CP and DCP was observed, that is, CP exhibited greater removal efficiency in batch mode at 0.5-3.5 mA cm-2 and REM operation (0.5 mA cm-2) with a permeate flow rate of 0.85 cm min-1 under the same reaction conditions, while DCP exhibited a faster degradation rate with the increase of current density in REM operation. Density functional theory (DFT) simulation and electrochemical performance tests indicated that the electrooxidation efficiency of CP and DCP in batch mode was primarily affected by the mass transfer rates. And the removal efficiency when anodic potentials were less than 1.7 V vs SHE in REM operation was determined by the activation energy for direct electron transfer (DET) reaction, however, the adsorption function of CP and DCP on the Ti4O7 anode became a dominant factor in determining the degradation efficiency with the further increase of anodic potential due to the disappeared activation barrier. In addition, the degradation pathways of CP and DCP were proposed according to intermediate products identification and frontier electron densities (FEDs) calculation, the acute toxicity of CP and DCP were also effectively decreased during both batch and REM operations.

Mechanistic study of the differences in lactic acid bacteria resistance to freeze- or spray-drying and storage.

Lactobacillus delbrueckii subsp. bulgaricus and Lactiplantibacillus plantarum are two lactic acid bacteria (LAB) widely used in the food industry. The objective of this work was to assess the resistance of these bacteria to freeze- and spray-drying and study the mechanisms involved in their loss of activity. The culturability and acidifying activity were measured to determine the specific acidifying activity, while membrane integrity was studied by flow cytometry. The glass transitions temperature and the water activity of the dried bacterial suspensions were also determined. Fourier transform infrared (FTIR) micro-spectroscopy was used to study the biochemical composition of cells in an aqueous environment. All experiments were performed after freezing, drying and storage at 4, 23 and 37 °C. The results showed that Lb. bulgaricus CFL1 was sensitive to osmotic, mechanical, and thermal stresses, while Lpb. plantarum WCFS1 tolerated better the first two types of stress but was more sensitive to thermal stress. Moreover, FTIR results suggested that the sensitivity of Lb. bulgaricus CFL1 to freeze-drying could be attributed to membrane and cell wall degradation, whereas changes in nucleic acids and proteins would be responsible of heat inactivation of both strains associated with spray-drying. According to the activation energy values (47-85 kJ/mol), the functionality loss during storage is a chemically limited reaction. Still, the physical properties of the glassy matrix played a fundamental role in the rates of loss of activity and showed that a glass transition temperature 40 °C above the storage temperature is needed to reach good preservation during storage. KEY POINTS: • Specific FTIR bands are proposed as markers of osmotic, mechanic and thermal stress • Lb. bulgaricus CFL1 was sensitive to all three stresses, Lpb. plantarum WCFS1 to thermal stress only • Activation energy revealed chemically limited reactions ruled the activity loss in storage.

Theoretical and Experimental Study on Carbodiimide Formation.

Carbodiimides are important crosslinkers in organic synthesis and are used in the isocyanate industry as modifier additives. Therefore, the understanding of their formation is of high importance. In this work, we present a theoretical B3LYP/6-31G(d) and SMD solvent model and experimental investigation of the formation of diphenylcarbodiimide (CDI) from phenyl isocyanate using a phosphorus-based catalyst (MPPO) in ortho-dichlorobenzene (ODCB) solvent. Kinetic experiments were based on the volumetric quantitation of CO2 evolved, at different temperatures between 40 and 80 °C. Based on DFT calculations, we managed to construct a more detailed reaction mechanism compared to previous studies which is supported by experimental results. DFT calculations revealed that the mechanism is composed of two main parts, and the rate determining step of the first part, controlling the CO2 formation, is the first transition state with a 52.9 kJ mol-1 enthalpy barrier. The experimental activation energy was obtained from the Arrhenius plot (ln k vs. 1/T) using the observed second-order kinetics, and the obtained 55.8 ± 2.1 kJ mol-1 was in excellent agreement with the computational one, validating the complete mechanism, giving a better understanding of carbodiimide production from isocyanates.

Temporal Evolution of Defects and Related Electric Properties in He-Irradiated YBa2Cu3O7-δ Thin Films.

Thin films of the superconductor YBa2Cu3O7-δ (YBCO) were modified by low-energy light-ion irradiation employing collimated or focused He+ beams, and the long-term stability of irradiation-induced defects was investigated. For films irradiated with collimated beams, the resistance was measured in situ during and after irradiation and analyzed using a phenomenological model. The formation and stability of irradiation-induced defects are highly influenced by temperature. Thermal annealing experiments conducted in an Ar atmosphere at various temperatures demonstrated a decrease in resistivity and allowed us to determine diffusion coefficients and the activation energy ΔE=(0.31±0.03) eV for diffusive oxygen rearrangement within the YBCO unit cell basal plane. Additionally, thin YBCO films, nanostructured by focused He+-beam irradiation into vortex pinning arrays, displayed significant commensurability effects in magnetic fields. Despite the strong modulation of defect densities in these pinning arrays, oxygen diffusion during room-temperature annealing over almost six years did not compromise the signatures of vortex matching, which remained precisely at their magnetic fields predicted by the pattern geometry. Moreover, the critical current increased substantially within the entire magnetic field range after long-term storage in dry air. These findings underscore the potential of ion irradiation in tailoring the superconducting properties of thin YBCO films.

Influence of ultrasound pretreatment on drying characteristics of cocoyam (Xanthosoma sagittifolium) slices during convective hot air drying.

BACKGROUND: Convective hot air drying of cocoyam is risk-free and inexpensive to a significant level. However, hot air drying causes negative changes to the color, texture, flavor and nutritional content of cocoyam as a result of the prolonged drying. Recently, the innovative technology of ultrasound pretreatment has been applied in food processing to reduce the processing time, conserve energy and preserve the quality of the food product. Thus, there is need to investigate the effect of ultrasound pretreatment with distilled water (UDW) and ultrasound with osmotic dehydration (UOD) for different ultrasonic times (10-30 min) on the drying kinetics of cocoyam slices during convective hot air drying. Ultrasound pretreatment was applied at a frequency of 20 kHz and an output power of 600 W for UDW and UOD. The ultrasound-pretreated samples were further dried in a convective hot-air drying oven at 70 °C. RESULTS: UDW and UOD samples, respectively, had a 25% and 46% reduction in drying time compared to untreated samples. The UOD samples had the lowest activation energy (10.697 × 10 3 kJ), as well as the highest moisture diffusivity (3.782 × 10-10 m2 s-1 ) and mass transfer coefficient (2.006 × 10-8 m s-1 ), among the untreated and UDW samples. Wang and Singh, Page and Peleg models were found to be the most fitted models with respect to the drying characteristics of cocoyam for untreated, UDW and UOD samples, respectively. CONCLUSION: Ultrasound pretreatment technology is a potential non-thermal process that can be incorporated as a pretreatment method in the convective drying of cocoyam to reduce processing time, conserve energy and enhance cocoyam product shelf life. © 2023 Society of Chemical Industry.

Accelerating Anhydrous Proton Transport in Covalent Organic Frameworks: Pore Chemistry and its Impacts.

Proton conduction is important in both fundamental research and technological development. Here we report designed synthesis of crystalline porous covalent organic frameworks as a new platform for high-rate anhydrous proton conduction. By developing nanochannels with different topologies as proton pathways and loading neat phosphoric acid to construct robust proton carrier networks in the pores, we found that pore topology is crucial for proton conduction. Its effect on increasing proton conductivity is in an exponential mode other than linear fashion, endowing the materials with exceptional proton conductivities exceeding 10-2 S cm-1 over a broad range of temperature and a low activation energy barrier down to 0.24 eV. Remarkably, the pore size controls conduction mechanism, where mesopores promote proton conduction via a fast-hopping mechanism, while micropores follow a sluggish vehicle process. Notably, decreasing phosphoric acid loading content drastically reduces proton conductivity and greatly increases activation energy barrier, emphasizing the pivotal role of well-developed proton carrier network in proton transport. These findings and insights unveil a new general and transformative guidance for designing porous framework materials and systems for high-rate ion conduction, energy storage, and energy conversion.

Partitioning the Apparent Temperature Sensitivity into Within- and Across-Taxa Responses: Revisiting the Difference between Autotrophic and Heterotrophic Protists.

AbstractConventional analyses suggest that the metabolism of heterotrophs is thermally more sensitive than that of autotrophs, implying that warming leads to pronounced trophodynamic imbalances. However, these analyses inappropriately combine within- and across-taxa trends. Our new analysis separates these, revealing that 92% of the difference in the apparent thermal sensitivity between autotrophic and heterotrophic protists does indeed arise from within-taxa responses. Fitness differences among taxa adapted to different temperature regimes only partially compensate for the positive biochemical relationship between temperature and growth rate within taxa, supporting the hotter-is-partially-better hypothesis. Our work highlights the importance of separating within- and across-taxa responses when comparing temperature sensitivities between groups, which is relevant to how trophic imbalances and carbon fluxes respond to warming.

An automated method for graph-based chemical space exploration and transition state finding.

Algorithms that automatically explore the chemical space have been limited to chemical systems with a low number of atoms due to expensive involved quantum calculations and the large amount of possible reaction pathways. The method described here presents a novel solution to the problem of chemical exploration by generating reaction networks with heuristics based on chemical theory. First, a second version of the reaction network is determined through molecular graph transformations acting upon functional groups of the reacting. Only transformations that break two chemical bonds and form two new ones are considered, leading to a significant performance enhancement compared to previously presented algorithm. Second, energy barriers for this reaction network are estimated through quantum chemical calculations by a growing string method, which can also identify non-octet species missed during the previous step and further define the reaction network. The proposed algorithm has been successfully applied to five different chemical reactions, in all cases identifying the most important reaction pathways.

Rapid evolution of unimodal but not of linear thermal performance curves in Daphnia magna.

Species may cope with warming through both rapid evolutionary and plastic responses. While thermal performance curves (TPCs), reflecting thermal plasticity, are considered powerful tools to understand the impact of warming on ectotherms, their rapid evolution has been rarely studied for multiple traits. We capitalized on a 2-year experimental evolution trial in outdoor mesocosms that were kept at ambient temperatures or heated 4°C above ambient, by testing in a follow-up common-garden experiment, for rapid evolution of the TPCs for multiple key traits of the water flea Daphnia magna. The heat-selected Daphnia showed evolutionary shifts of the unimodal TPCs for survival, fecundity at first clutch and intrinsic population growth rate toward higher optimum temperatures, and a less pronounced downward curvature indicating a better ability to keep fitness high across a range of high temperatures. We detected no evolution of the linear TPCs for somatic growth, mass and development rate, and for the traits related to energy gain (ingestion rate) and costs (metabolic rate). As a result, also the relative thermal slope of energy gain versus energy costs did not vary. These results suggest the overall (rather than per capita) top-down impact of D. magna may increase under rapid thermal evolution.

The Effect of Benzyl Alcohol on the Voltage-Current Characteristics of Tethered Lipid Bilayers.

In this study a lipid bilayer membrane model was used in which the bilayer is tethered to a solid substrate with molecular tethers. Voltage-current (V-I) measurements of the tethered bilayer membranes (tBLM) and tBLM with benzyl alcohol (BZA) incorporated in their structures, were measured using triangular voltage ramps of 0-500 mV. The temperature dependence of the conductance deduced from the V-I measurements are described. An evaluation of the activation energies for electrical conductance showed that BZA decreased the activation/ Born energies for ionic conduction of tethered lipid membranes. It is concluded that BZA increased the average pore radius of the tBLM.

Coupling temperature-dependent spatial turnover of microbes and plants using the metabolic theory of ecology.

There is an urgent need to understand the coupled relationship between belowground microbes and aboveground plants in response to temperature under climate change. The metabolic theory of ecology (MTE) provides a way to predict the metabolic rate and species diversity, but the spatial scale dependence and connections between plants and microorganisms are still unclear. Here, we used two independent datasets to address this question. One is from comprehensive sampling of paddy fields targeting bacteria and microbial functional genes, and the other is a global metadata of spatial turnover for microorganisms (bacteria, fungi and archaea, n = 139) and plants (n = 206). Results showed that spatial turnover of bacterial communities and microbial functional genes increased with temperature and fitted MTE. Through meta-analysis, the temperature-dependent spatial scale pattern was further extended to the global scale, with the spatial turnover of microorganisms and plants being consistent with MTE. Belowground microorganisms and aboveground plants were closely linked with each other even when controlling for temperature, suggesting that factors other than shared relationships with temperature also contribute to their linkages. These results implied a broad application of MTE in biology and have important implications for predicting the ecological consequences of future climate warming.

Theoretical and Experimental Investigation of Autoxidation Propensity of Selected Drugs in Solution State.

The C-H bond dissociation energy (BDE) of drug molecules is often used to estimate their relative propensities to undergo autoxidation. BDE calculations based on electronic structures provide a convenient means to estimate the risk for a given compound to degrade via autoxidation. This study aimed to verify the utility of calculated C-H BDEs of a range of drug molecules in predicting their autoxidation propensities, in the solution state. For the autoxidation study, 2,2'-azobis (2-methylpropionitrile) was employed as the solution state stressor, and the experimental reaction rate constants were determined employing ultraperformance liquid chromatographic (UPLC) methods. Reaction rates in the solution state were compared to the calculated C-H BDE values of the respective compounds. The results indicated a poor correlation for compounds in the solution state, and their relative stabilities could not be explained with C-H BDE. On the other hand, a favorable relationship was observed between the relative extent of ionization and the autoxidation rates of the selected compounds. In the solution state, factors such as the type and extent of drug ionization, degree and type of solvation have been shown to contribute to differences in reactivity. By applying the computational method involving the effect of H-atom abstraction and potential ionization sites in the molecule, the calculated C-H BDE should relate better to the experimental autoxidation rates.

Temperature Sensitivity of Microbial Litter Decomposition in Freshwaters: Role of Leaf Litter Quality and Environmental Characteristics.

Ongoing global warming is expected to alter temperature-dependent processes. Nevertheless, how co-occurring local drivers will influence temperature sensitivity of plant litter decomposition in lotic ecosystems remains uncertain. Here, we examined the temperature sensitivity of microbial-mediated decomposition, microbial respiration, fungal biomass and leaf nutrients of two plant species varying in litter quality. We also assessed whether the type of microbial community and stream water characteristics influence such responses to temperature. We incubated alder (Alnus glutinosa) and eucalypt (Eucalyptus globulus) litter discs in three streams differing in autumn-winter water temperature (range 4.6-8.9 °C). Simultaneously, in laboratory microcosms, litter discs microbially conditioned in these streams were incubated at 5, 10 and 15 °C with water from the conditioning stream and with a water control from an additional stream. Both in the field and in the laboratory, higher temperatures enhanced litter decomposition rates, except for eucalypt in the field. Leaf quality modified the response of decomposition to temperature in the field, with eucalypt leaf litter showing a lower increase, whereas it did not in the laboratory. The origin of microbial community only affected the decomposition rates in the laboratory, but it did not modify the response to temperature. Water quality only defined the phosphorus content of the leaf litter or the fungal biomass, but it did not modify the response to temperature. Our results suggest that the acceleration in decomposition by global warming will be shaped by local factors, mainly by leaf litter quality, in headwater streams.