Importance of Spin Channels from Radical-Radical Reactions in Hydrogen-Oxygen Combustion Mechanisms at High Temperatures.

Radical-radical reactions can generate two channels with high and low spins. In this work, ten radical-radical reactions with different spin channels and four radical-molecule reactions in hydrogen-oxygen combustion were systematically investigated from a theoretical perspective. The potential energy surface (PES) of radical-radical reactions reveals that the high- and low-spin states of the reactant are energetically degenerate and the two channels are energetically feasible. The difference in rate constants between the high- and low-spin channels gradually decreases as the temperature increases. Then, the kinetic parameters of the 14 bimolecular reactions in the hydrogen-oxygen mechanism of the University of California, San Diego (UCSD), were replaced to simulate the ignition delay time and laminar flame speed. The simulation results agree well with the available experimental findings, indicating the necessity of considering both high- and low-spin channels for kinetic simulation.

High-Throughput Predictions of Accurate Enthalpies of Formation for Larger Molecules Utilizing the Bond Difference Correction Method.

The prediction of standard enthalpies of formation (EOFs) for larger molecules involves a trade-off between accuracy and cost, often resulting in non-negligible errors. The connectivity-based hierarchy (CBH) and simple bond additivity correction (BAC) are two promising means for evaluating EOFs, although they cannot achieve strict chemical accuracy. Calculated errors in the CBH are confirmed from accumulated systematic errors associated with bond differences in chemical environments. On the basis of a new set of bond descriptors, our developed bond difference correction (BDC) method effectively solves incremental errors with molecular size and inability applications for aromatic molecules. To balance the accuracy between non-aromatic and aromatic molecules, a more accurate BAC-based method with unpaired electrons and p hybrid orbitals (BAC-EP) is developed. With the incorporation of the two methods above, strict chemical accuracy by the largest deviation is achieved at low costs. These universal, ultrafast, and high-throughput methods greatly contribute to self-consistent thermodynamic parameters in combustion mechanisms.

Lyotropic Lamellar Nanostructures Enabled High-Voltage Windows, Efficient Charge Transport, and Thermally Safe Solid-State Electrolytes for Lithium-Ion Batteries.

Developing electrolytes combining solid-like instinct stability and liquid-like conducting performance will be satisfactory for efficient and durable Li-ion batteries. Herein lamellar lyotropic liquid crystals (LLCs) demonstrate high-voltage windows, efficient charge transport, and inherent thermal safety as solid-state electrolytes in lithium-ion batteries. Lamellar LLCs are simply prepared by nanosegregation of [C16 Mim][BF4 ] and LiBF4 /Propylene carbonate (PC) liquid solutions, which induce lamellar assembly of the liquids as dynamic conducting pathways. Broadened liquid conducting pathways will boost the conducting performance of the LLC electrolytes. The lyotropic lamellar nanostructures enable liquid-like ion conductivity of the LLC electrolytes at ambient temperatures, as well as provide solid-like stability for the electrolytes to resist high voltage and flammability overwhelming to LiBF4 /PC liquid electrolytes. Despite minor consumption of PC solvents (34.5 wt.%), the lamellar electrolytes show energy conversion efficiency comparable to the liquid electrolytes (PC wt. 92.8%) in Li/LiFePO4 batteries under ambient temperatures even at a 2 C current density, and exhibit attractively robust stability after 200th cyclic charge/discharge even under 60 °C. The work demonstrates LLC electrolytes have great potential to supersede traditional liquid electrolytes for efficient and durable Lithium-ion (Li-ion) batteries.

Spherical porous iron-nitrogen-carbon nanozymes derived from a tannin coordination framework for the preparation of L-DOPA by emulating tyrosine hydroxylase.

L-3,4-Dihydroxyphenylalanine (L-DOPA) is widely used in Parkinson's disease treatment and is therefore in high demand. Development of an efficient method for the production of L-DOPA is urgently required. Nanozymes emulating tyrosine hydroxylase have attracted enormous attention for biomimetic synthesis of L-DOPA, but suffered from heterogeneity. Herein, a spherical porous iron-nitrogen-carbon nanozyme was developed for production of L-DOPA. Tannic acid chelated with ferrous ions to form a tannin-iron coordination framework as a carbon precursor. Iron and nitrogen co-doped carbon nanospheres were assembled via an evaporation-induced self-assembly process using urea as a nitrogen source, F127 as a soft template, and formaldehyde as a crosslinker. The nanozyme was obtained after carbonization and acid etching. The nanozyme possessed a dispersive iron atom anchored in the Fe-N coordination structure as an active site to mimic the active center of tyrosine hydroxylase. The material showed spherical morphology, uniform size, high specific surface area, a mesoporous structure and easy magnetic separation. The structural properties could promote the density and accessibility of active sites and facilitate mass transport and electron transfer. The nanozyme exhibited high activity to catalyze the hydroxylation of tyrosine to L-DOPA as tyrosine hydroxylase in the presence of ascorbic acid and hydrogen peroxide. The titer of DOPA reached 1.2 mM. The nanozyme showed good reusability and comparable enzyme kinetics to tyrosine hydroxylase with a Michaelis-Menten constant of 2.3 mM. The major active species was the hydroxyl radical. Biomimetic simulation of tyrosine hydroxylase using a nanozyme with a fine structure provided a new route for the efficient production of L-DOPA.

Mechanisms and energetics of benzophenone photosensitized thymine damage and repair from Paternò-Büchi cycloaddition.

Here, we report the detailed mechanisms of benzophenone (BZP) photosensitized thymine damage and repair by Paternò-Büchi (PB) cycloaddition. It was found that the head-to-head and head-to-tail PB cycloadditions lead to the formation of the C-O bonds in the 3(nπ*) state and the 3(ππ*) state, respectively. The conical intersection occurs before the head-to-tail C-O bonding. Then, the C-C bonds are formed via intersystem crossing (ISC). The C-O bonding is the rate-determining step of PB cycloaddition. For the cycloreversion reactions, the ring-opening processes completely occur in the singlet excited states of oxetanes. The head-to-head oxetane goes through a conical intersection before cycloreversion with a little energy barrier of 1.8 kcal mol-1. The head-to-tail oxetane splits without a barrier. Then, the ISC processes take place to restore thymine. Throughout the ring-closing and ring-opening processes, ISC plays an important role. These findings are in good agreement with the available experimental findings. We hope that this comprehensive work can provide a deeper understanding of photosensitive DNA damage and repair.

Controlling the repair mechanisms of oxetanes through functional group substitution.

Intersystem crossing (ISC) plays a key role in the photolysis processes of oxetanes formed by benzophenone (BP)-like and thymine structures. In this work, we systematically explored the photophysical processes of oxetanes and ring-splitting products and investigated the effect of substituents on the repair mechanisms of oxetanes. The regioselectivity of oxetanes (head-to-head, HH and head-to-tail, HT) and the electron-donating and electron-withdrawing substituents, including CH3, OCH3 and NO2, were considered. It was found that the substituents influence the ISC rates of these compounds more by changing their spin-orbit coupling (SOC) coefficients rather than energy gaps. The SOC coefficients of HH-oxetanes are more affected by these groups than HT-oxetanes and products, and they have greater ISC rates on the whole. Besides, the insertion of substituents can alter the radiative and nonradiative decay rates, thereby transforming the photoinduced cycloreversion mechanisms of oxetanes. The ring-splitting reactions of non-substituted oxetanes could occur via two pathways of singlet and triplet manifolds. Furthermore, oxetanes with NO2 at the X site have the largest ISC rates but hardly undergo repair processes, while the introduction of electron-donating substituents can effectively promote the repair of oxetanes. The singlet ring-splitting reactions of HH-oxetanes are more inclined to occur after introducing CH3 and OCH3 at two sites. However, HT-oxeatnes with CH3 are more likely to undergo triplet repair processes and OCH3-substituted structures tend to originate cycloreversion in the singlet manifolds. Moreover, the introduction of CH3 and OCH3 at the Y site rather than the X site can more significantly accelerate the repair processes of HH-oxetanes. Contrarily, HT-oxetanes with electron-donating groups at the X site exhibit faster repair rates than those at the Y site. We hope this work can provide valuable insights into BP-like drugs and photosensitive DNA repair.

Mechanisms and energetics for hydrogen abstraction of thymine photosensitized by benzophenone from theoretical principles.

The significant role of hydrogen abstraction in chemistry and biology has inspired many theoretical works to link its practical phenomena and mechanistic properties. Here, the photophysical processes and hydrogen abstraction mechanisms of benzophenone (BZP) photosensitized thymine damage were systematically investigated from theoretical principles. It was found that the BZP photosensitizer upon UV irradiation undergoes vertical excitation, internal conversion, vibrational relaxation and intersystem crossing into a triplet excited state. Then the triplet BZP damages thymine by a hydrogen abstraction process. However, the reverse reaction easily occurs due to the lower reaction energy, which causes a low yield of hydrogen abstraction products. We hope this comprehensive work can provide a deeper understanding of photosensitive DNA damage from hydrogen abstraction.

Biomimetic synthesis of L-DOPA inspired by tyrosine hydroxylase.

L-3,4-dihydroxyphenylalanine (L-DOPA) is in high demand as the cornerstone for treatment of Parkinson's disease. The current production of L-DOPA is associated with poor productivity and long production period. Biomimetic system inspired from tyrosine hydroxylase was developed to achieve the production of L-DOPA from tyrosine with high reactivity, efficiency, and specificity. The biomimetic system owned close resemblance of component and structure in comparison with tyrosine hydroxylase, consisting of tyrosine as substrate, a redox complex of Fe2+ and EDTA as the catalyst to simulate the active center of the natural tyrosine hydroxylase, hydrogen peroxide as the oxidant, and ascorbic acid as the reductant. HPLC, HPLC-MS/MS, 1H NMR, and specific rotation identified L-DOPA was generated. The system showed high catalytic activity and regioselectivity for hydroxylation of tyrosine as equal to tyrosine hydroxylase. FeIVO2+ was formed as the major active species, and NIH shift was observed. EDTA accelerated the reaction by reducing the redox potential of Fe3+/Fe2+ couple. Density functional theory calculation suggested formation of FeIVO2+ was more thermodynamically favorable. The biomimetic system shared analogous catalytic mechanism with TyrH. Process parameters was optimized for maximum production of L-DOPA, namely 6.4 mM tyrosine, 1.6 mM Fe2+, 1.92 mM EDTA, 150 mM H2O2, and 35 mM ascorbic acid in 0.2 M glycine-HCl buffer at pH 4.5 and 60 °C. The yield, titer, and productivity were obtained as 52.01%, 3.22 mM, and 48,210.68 mg L-1 h-1, respectively. The proposed method exhibited an amazing productivity, might provide a promising strategy to industrialize L-DOPA production.

Dynamics and mechanism of dimer dissociation of photoreceptor UVR8.

Photoreceptors are a class of light-sensing proteins with critical biological functions. UVR8 is the only identified UV photoreceptor in plants and its dimer dissociation upon UV sensing activates UV-protective processes. However, the dissociation mechanism is still poorly understood. Here, by integrating extensive mutations, ultrafast spectroscopy, and computational calculations, we find that the funneled excitation energy in the interfacial tryptophan (Trp) pyramid center drives a directional Trp-Trp charge separation in 80 ps and produces a critical transient Trp anion, enabling its ultrafast charge neutralization with a nearby positive arginine residue in 17 ps to destroy a key salt bridge. A domino effect is then triggered to unzip the strong interfacial interactions, which is facilitated through flooding the interface by channel and interfacial water molecules. These detailed dynamics reveal a unique molecular mechanism of UV-induced dimer monomerization.

Effect of Graphene Nanoplatelets (GNPs) on Fatigue Properties of Asphalt Mastics.

To investigate the effect of graphene on the fatigue properties of base asphalt mastics, graphene nanoplatelets (GNPs)-modified asphalt mastics and base asphalt mastics were prepared. A dynamic shear rheometer (DSR) was used to conduct the tests in the stress-controlled mode of a time-sweep test. The results showed that GNPs can improve the fatigue life of asphalt mastic. Under a stress of 0.15 MPa, the average fatigue life growth rate (ω¯) was 17.7% at a filler-asphalt ratio of 0.8, 35.4% at 1.0, and 45.2% at 1.2; under a stress of 0.2 MPa, the average fatigue life growth rate (ω¯) was 17.9% at a filler-asphalt ratio of 0.8, 25.6% at 1.0, and 38.2% at 1.2. The growth value (ΔT) of fatigue life of GNPs-modified asphalt mastics increased correspondingly with the increase of filler-asphalt ratio, the correlation coefficient R2 was greater than 0.95, and the growth amount showed a good linear relationship with the filler-asphalt ratio. In the range of 0.8~1.2 filler-asphalt ratio, the increase of mineral powder can improve the fatigue life of asphalt mastics, and there is a good linear correlation between filler-asphalt ratio and fatigue life. The anti-fatigue mechanism of GNPs lies in the interaction between GNPs and asphalt, as well as its own lubricity and thermal conductivity.

Dynamical and allosteric regulation of photoprotection in light harvesting complex II.

Major light-harvesting complex of photosystem II (LHCII) plays a dual role in light-harvesting and excited energy dissipation to protect photodamage from excess energy. The regulatory switch is induced by increased acidity, temperature or both. However, the molecular origin of the protein dynamics at the atomic level is still unknown. We carried out temperature-jump time-resolved infrared spectroscopy and molecular dynamics simulations to determine the energy quenching dynamics and conformational changes of LHCII trimers. We found that the spontaneous formation of a pair of local α-helices from the 310-helix E/loop and the C-terminal coil of the neighboring monomer, in response to the increased environmental temperature and/or acidity, induces a scissoring motion of transmembrane helices A and B, shifting the conformational equilibrium to a more open state, with an increased angle between the associated carotenoids. The dynamical allosteric conformation change leads to close contacts between the first excited state of carotenoid lutein 1 and chlorophyll pigments, facilitating the fluorescence quenching. Based on these results, we suggest a unified mechanism by which the LHCII trimer controls the dissipation of excess excited energy in response to increased temperature and acidity, as an intrinsic result of intense sun light in plant photosynthesis.

A leap in quantum efficiency through light harvesting in photoreceptor UVR8.

Plants utilize a UV-B (280 to 315 nm) photoreceptor UVR8 (UV RESISTANCE LOCUS 8) to sense environmental UV levels and regulate gene expression to avoid harmful UV effects. Uniquely, UVR8 uses intrinsic tryptophan for UV-B perception with a homodimer structure containing 26 structural tryptophan residues. However, besides 8 tryptophans at the dimer interface to form two critical pyramid perception centers, the other 18 tryptophans' functional role is unknown. Here, using ultrafast fluorescence spectroscopy, computational methods and extensive mutations, we find that all 18 tryptophans form light-harvesting networks and funnel their excitation energy to the pyramid centers to enhance light-perception efficiency. We determine the timescales of all elementary tryptophan-to-tryptophan energy-transfer steps in picoseconds to nanoseconds, in excellent agreement with quantum computational calculations, and finally reveal a significant leap in light-perception quantum efficiency from 35% to 73%. This photoreceptor is the first system discovered so far, to be best of our knowledge, using natural amino-acid tryptophans to form networks for both light harvesting and light perception.

Spectrofluorometric method for the determination of ascorbic acid in pharmaceutical preparation using l-tyrosine as fluorescence probe.

Ascorbic acid is a vital nutrient and antioxidant that is commonly used as an additive in commercial products. Quantitation of ascorbic acid is highly desired in the medical, food, and cosmetic industries. A spectrofluorometric assay for sensitive determination of ascorbic acid was developed using l-tyrosine as a fluorescent probe. The native fluorescence intensity of tyrosine was quenched using ascorbic acid. The linear range was 0.03-30.00 µM, and the limit of detection was 0.01 µM. The method exhibited excellent precision, accuracy, specificity, and robustness. Components of pharmaceutical preparations that are commonly found with ascorbic acid did not interfere with detection. The procedure was successfully employed for determination of ascorbic acid content in pharmaceutical tablets, injections, and nutrient supplements with satisfactory results. A Stern-Volmer plot and fluorescence lifetime revealed that quenching was attributed to the inner filter effect and static quenching. Isothermal titration calorimetry confirmed the formation of a complex between tyrosine and ascorbic acid, with a binding constant of 1.68 × 103 M-1 and reaction stoichiometry of 0.94. Thermodynamic parameters suggested spontaneous complexation via hydrophobic interactions as the dominant binding force. This method is promising for the simple and rapid determination of ascorbic in the pharmaceutical industry.

Dynamics and mechanism of light harvesting in UV photoreceptor UVR8.

Photosynthetic pigments form light-harvesting networks to enable nearly perfect quantum efficiency in photosynthesis via excitation energy transfer. However, similar light-harvesting mechanisms have not been reported in light sensing processes in other classes of photoreceptors during light-mediated signaling. Here, based on our earlier report, we mapped out a striking energy-transfer network composed of 26 structural tryptophan residues in the plant UV-B photoreceptor UVR8. The spectra of the tryptophan chromophores are tuned by the protein environments, funneling all excitation energy to a cluster of four tryptophan residues, a pyramid center, where the excitation-induced monomerization is initiated for cell signaling. With extensive site-directed mutagenesis, various time-resolved fluorescence techniques, and combined QM/MM simulations, we determined the energy-transfer rates for all donor-acceptor pairs, revealing the time scales from tens of picoseconds to nanoseconds. The overall light harvesting quantum efficiency by the pyramid center is significantly increased to 73%, compared to a direct excitation probability of 35%. UVR8 is the only photoreceptor discovered so far using a natural amino-acid tryptophan without utilizing extrinsic chromophores to form a network to carry out both light harvesting and light perception for biological functions.

First-principles study of the adsorption behaviors of Li atoms and LiF on the CF x (x = 1.0, 0.9, 0.8, 0.5, ∼0.0) surface.

Based on first principles calculation, the adsorption properties of Li atoms and LiF molecules on the fluorographene (CF x ) surface with different F/C ratios (x = 1.0, 0.9, 0.8, 0.5 and ∼0.0) have been studied in the present work. The calculated binding energy of Li and CF x is greater than 2.29 eV under different F/C ratios, indicating that the battery has the potential to maintain a high discharge platform during the whole discharge process. But the adsorption energies of LiF on a CF x layer for different F/C ratios are 0.12-1.04 eV, which means LiF is not easy to desorb from a CF x surface even at room temperature. It will stay on the surface for a long time and affect the subsequent discharge. Current calculations also show the structure of the CF x -skeleton will change greatly during the reaction, when there are many unsaturated carbon atoms on the CF x surface, such as at x = 0.8 and 0.5. Moreover, the discharge voltage is strongly dependent on the discharge site. After discharge, the CF x -skeleton may continue to relax and release a lot of heat energy.

ReacNetGenerator: an automatic reaction network generator for reactive molecular dynamics simulations.

Reactive molecular dynamics (MD) simulation makes it possible to study the reaction mechanism of complex reaction systems at the atomic level. However, the analysis of MD trajectories which contain thousands of species and reaction pathways has become a major obstacle to the application of reactive MD simulation in large-scale systems. Here, we report the development and application of the Reaction Network Generator (ReacNetGenerator) method. It can automatically extract the reaction network from the reaction trajectory without any predefined reaction coordinates and elementary reaction steps. Molecular species can be automatically identified from the cartesian coordinates of atoms and the hidden Markov model is used to filter the trajectory noises which makes the analysis process easier and more accurate. The ReacNetGenerator has been successfully used to analyze the reactive MD trajectories of the combustion of methane and 4-component surrogate fuel for rocket propellant 3 (RP-3), and it has great advantages in terms of efficiency and accuracy compared to traditional manual analysis.

New Insight on Hydrogen Evolution Reaction Activity of MoP2 from Theoretical Perspective.

We systematically investigated the hydrogen evolution reaction (HER) of six facets of MoP2 based on the periodic density functional theory (DFT). The calculated values of Gibbs free energy of hydrogen adsorption (ΔGH) indicated that the (111) facet has a good HER activity for a large range of hydrogen coverages. The zigzagged patterns before 75% hydrogen coverage suggest a facilitation among Mo1, P1 and Mo2 sites, which are attributed to repeat occupancy sites of H atoms. From ab initial atomistic thermodynamics analysis of hydrogen coverage, we gained that the most stable coverage of hydrogen is 18.75% at 1 atm H2 and 298 K. Finally, the doping effects on HER activity were investigated and found that catalytic performance can be improved by substituting P with an S or N atom, as well as substituting the Mo atom with an Fe atom, respectively. We hope this work can provide new insights on further understanding of HER for MoP2 and give instructions for the experimental design and synthesis of transition metal phosphides (TMPs)-based high-performance catalysts.

A Pore-Forming Tripeptide as an Extraordinarily Active Anion Channel.

Compared to the most active anion-transporting channel that requires a channel:lipid molar ratio of 1:330 (0.3 mol % relative to lipid) to achieve 50% activity, a structurally simple pore-forming tripeptide 6L310 was found to exhibit an extraordinarily strong ability to self-assemble into stable possibly barrel-shaped exceptionally active channels, with record-low EC50 values of 4.0, 3.0, 1.6, 2.6, and 2.6 nM (e.g., 0.005-0.013 mol % relative to lipid) for Cl-, Br-, I-, NO3-, and ClO4-, respectively.

Absorption Spectra of Acetylene, Vinylidene, and Their Deuterated Isotopologues on Ab Initio Potential Energy and Dipole Moment Surfaces.

The absorption spectra of acetylene (HCCH) and vinylidene (H2CC) as well as their deuterated isotopologues are investigated theoretically on a near spectroscopically accurate full-dimensional potential energy surface reported in an earlier publication, using dipole moment surfaces reported in this work, which are constructed with a neural network method from a large number of ab initio data points. These global surfaces cover not only the deep acetylene well but also the vinylidene well, as well as the transition region between the two isomers. The agreement with available experimental data for acetylene is excellent, validating both the potential energy surface and the dipole moment surfaces. The infrared spectra of vinylidene and its deuterated isotopologues are predicted. The potential and dipole moment surfaces lay the foundation for future spectroscopic studies of the acetylene-vinylidene isomerization involving large-amplitude motions.

Relationship between Energetic Performance and Clustering Effects on Incremental Nitramine Groups: A Theoretical Perspective.

Nitramine compounds are typical high-energy-density materials (HEDMs) and are widely used as explosives because of their superior explosive performance over conventional energetic materials. In this work, the thermal properties of 1-nitropiperidine (NPIP), 1,4-dinitropiperazine (DNP), and 1,3,5-trinitro-1,3,5-triazinane (RDX) were investigated from quantum mechanics (QM) and reactive force field (ReaxFF) molecular dynamics simulations. We found that the bond dissociation energy of the N-NO2 bond, heat of formation, released energy, produced fragments, and oxygen balance are closely related to the incremental nitramine group. The nitramine group has a significant effect on the energetic performance of these nitramine compounds. In addition, the increase of the nitramine group will improve thermal decomposition activity, promote the generation of small molecules, and restrain the formation of carbon clusters. We hope that this work can shed new light on the design of energetic materials.