Conformational and Solvent Effects on the Photoinduced Electron Transfer Dynamics of a Zinc Phthalocyanine-Benzoperylenetriimide Conjugate: A Nonadiabatic Dynamics Simulation.

Herein, we employed a combination of static electronic structure calculations and nonadiabatic dynamics simulations at linear-response time dependent density functional theory (LR-TDDFT) level with the optimally tuned range-separated hybrid (OT-RSH) functional to explore the ultrafast photoinduced dynamics of a zinc phthalocyanine-benzoperylenetriimide (ZnPc-BPTI) conjugate. Due to the flexibility of the linker, we identified two major conformations: the stacked conformation (ZnPc-BPTI-1) and the extended conformation (ZnPc-BPTI-2). Since the charge transfer states are much lower than the lowest local excitation in ZnPc-BPTI-1, which is contrary to ZnPc-BPTI-2, the ultrafast electron transfer (~3.6 ps) is only observed in the nonadiabatic simulations of ZnPc-BPTI-1 upon local excitation around the absorption maximum of ZnPc. However, when considering the solvent effects in benzonitrile: the lowest S1 states are both charge transfer states from ZnPc to BPTI for different conformers. Subsequent nonadiabatic dynamics simulations indicate that both conformers experience ultrafast electron transfer in benzonitrile with two time constants of 90 [100] fs and 1.40 [1.43] ps. Our present work not only agrees well with previous experimental study, but also points out the important role of conformational changes and solvent effects in regulating the photodynamics of organic donor-acceptor conjugates.

Two-dimensional silk.

Despite the promise of silk-based devices, the inherent disorder of native silk limits performance. Here, we report highly ordered two-dimensional silk fibroin (SF) films grown epitaxially on van der Waals (vdW) substrates. Using atomic force microscopy, nano-Fourier transform infrared spectroscopy, and molecular dynamics, we show that the films consist of lamellae of SF molecules that exhibit the same secondary structure as the nanocrystallites of native silk. Increasing the SF concentration results in multilayers that grow either by direct assembly of SF molecules into the lamellae or, at high concentrations, along a two-step pathway beginning with a disordered monolayer that then crystallizes. Scanning Kelvin probe measurements show that these films substantially alter the surface potential; thus, they provide a platform for silk-based electronics on vdW solids.

Photoinduced Nonadiabatic Dynamics of a Single-Walled Carbon Nanotube-Porphyrin Complex.

Single-walled carbon nanotubes (SWCNTs) have gained a lot of attention in the past few decades due to their promising optoelectronic properties. In addition, SWCNTs can form complexes that have good chemical stability and transport properties with other optical functional materials through noncovalent interactions. Elucidating the detailed mechanism of these complexes is of great significance for improving their optoelectronic properties. Nevertheless, simulating the photoinduced dynamics of these complexes accurately is rather challenging since they usually contain hundreds of atoms. To save computational efforts, most of the previous works have ignored the excitonic effects by employing nonadiabatic carrier (electron and hole) dynamics simulations. To properly consider the influence of excitonic effects on the photoinduced ultrafast processes of the SWCNT-tetraphenyl porphyrin (H2TPP) complex and to further improve the computational efficiency, we developed the nonadiabatic molecular dynamics (NAMD) method based on the extended tight binding-based simplified Tamm-Dancoff approximation (sTDA-xTB), which is applied to study the ultrafast photoinduced dynamics of the noncovalent SWCNT-porphyrin complex. In combination with statically electronic structure calculations, the present work successfully reveals the detailed microscopic mechanism of the ultrafast excitation energy transfer process of the complex. Upon local excitation on the H2TPP molecule, an ultrafast energy transfer process occurs from H2TPP (SWCNT-H2TPP*) to SWCNT (SWCNT*-H2TPP) within 10 fs. Then, two slower processes corresponding to the energy transfer from H2TPP to SWCNT and hole transfer from H2TPP to SWCNT take place in the 1 ps time scale. The sTDA-xTB-based electronic structure calculation and NAMD simulation results not only match the previous experimental observations from static and transient spectra but also provide more insights into the detailed information on the complex's photoinduced dynamics. Therefore, the sTDA-xTB-based NAMD method is a powerful theoretical tool for studying the ultrafast photoinduced dynamics in large extended systems with a large number of electronically excited states, which could be helpful for the subsequent design of SWCNT-based functional materials.

Roles of Nonadiabatic Processes, Reaction Mechanism, and Selectivity in Cu-Catalyzed [2 + 2] Photocycloaddition of Norbornene and Acetone to Oxetane.

Oxetane has been extensively studied for its applications in medicinal chemistry and as a reactive intermediate in synthesis. Experiments report a Cu-catalyzed [2 + 2] photocycloaddition of acetone and norbornene to oxetane, which is proposed to deviate from the conventional Paternò-Büchi reaction. However, its mechanism at the atomic level is not clear. In this study, we used a combination of multistate complete active space second-order perturbation theory (MS-CASPT2) and density functional theory to systematically investigate the reaction mechanism and elucidate the factors contributing to the diastereomeric selectivity. Initially, the formation of the TpCu(Norb) complex is achieved by strong interaction between tris(pyrazolyl)borate Cu(I) (TpCu) and norbornene in the ground state (S0). Upon photoexcitation, TpCu(Norb) eventually decays to the T1 state, in which TpCu(Norb) attacks acetone to initiate subsequent reactions and produces final endo- or exo-oxetane products. All these reactions initially involve the C-C bond formation in the T1 state thereto leading to a ring-opening intermediate. This intermediate then undergoes a nonradiative transition to the S0 state, producing a five-membered ring intermediate, from which the C-O bond is formed, leading to the experimentally dominant exo-product. In contrast, the endo-oxetane formation requires a rearrangement process after the C-C bond is formed because of the large steric effects. As a consequence, the different reaction pathways generating exo- and endo-products exhibit large differences in the free-energy barriers, which results in a diastereomeric selectivity observed experimentally. Additionally, the nonradiative transition is found to play an important role in facilitating these reaction steps. The present computational study provides valuable mechanistic insights into Cu-catalyzed photocycloaddition reactions.

"On-the-Fly" Nonadiabatic Dynamics Simulation on the Ultrafast Photoisomerization of a Molecular Photoswitch Iminothioindoxyl: An RMS-CASPT2 Investigation.

Iminothioindoxyl (ITI) is a new class of photoswitch that exhibits many excellent properties including well-separated absorption bands in the visible region for both conformers, ultrafast Z to E photoisomerization as well as the millisecond reisomerization at room temperature for the E isomer, and switchable ability in both solids and various solvents. However, the underlying ultrafast photoisomerization mechanism at the atomic level remains unclear. In this work, we have employed a combination of high-level RMS-CASPT2-based static electronic structure calculations and nonadiabatic dynamics simulations to investigate the ultrafast photoisomerization dynamics of ITI. Based on the minimum-energy structures, minimum-energy conical intersections, linear interpolation internal coordinate paths, and nonadiabatic dynamics simulations, the overall photoisomerization scenario of ITI upon excitation is established. Upon excitation around 416 nm, the molecule will be excited to the S2 state considering its close energy to the experimentally measured absorption maximum and larger oscillator strength, from which ultrafast decay of S2 to S1 state can take place efficiently with a time constant of 62 fs. However, the photoisomerization is not likely to complete in the S2 state since the dihedral associated with the Z to E isomerization changes little during the relaxation. Upon relaxing to the S1 state, the molecule will decay to the S0 state ultrafast with a time constant of 232 fs. In contrast, the decay of the S1 state is important for the isomerization considering that the dihedral related to the isomerization of the hopping structures is close to 90°. Therefore, the S1/S0 intersection region should be important for the isomerization of ITI. Arriving at the S0 state, the molecule can either go back to the original Z reactant or isomerize to the E products. At the end of the 500 fs simulation time, the E configuration accounts for nearly 37% of the final structures. Moreover, the photoisomerization mechanism is different from the isomerization mechanism in the ground state; i.e., instead of the inversion mechanism in the ground state, the photoisomerization prefers the rotation mechanism. Our results not only agree well with previous experimental studies but also provide some novel insights that could be helpful for future improvements in the performance of the ITI photoswitches.

Nuclear Quantum Effects on Nonadiabatic Dynamics of a Green Fluorescent Protein Chromophore Analogue: Ring-Polymer Surface-Hopping Simulation.

Herein, we have used the "on-the-fly" ring-polymer surface-hopping simulation method with the centroid approximation (RPSH-CA), in combination with the multireference OM2/MRCI electronic structure calculations to study the photoinduced dynamics of a green fluorescent protein (GFP) chromophore analogue in the gas phase, i.e., o-HBI, at 50, 100, and 300 K with 1, 5, 10, and 15 beads (3600 1 ps trajectories). The electronic structure calculations identified five new minimum-energy conical intersection (MECI) structures, which, together with the previous one, play crucial roles in the excited-state decay dynamics of o-HBI. It is also found that the excited-state intramolecular proton transfer (ESIPT) occurs in an ultrafast manner and is completed within 20 fs in all the simulation conditions because there is no barrier associated with this ESIPT process in the S1 state. However, the other excited-state dynamical results are strongly related to the number of beads. At 50 and 100 K, the nuclear quantum effects (NQEs) are very important; therefore, the excited-state dynamical results change significantly with the bead number. For example, the S1 decay time deduced from time-dependent state populations becomes longer as the bead number increases. Nevertheless, an essentially convergent trend is observed when the bead number is close to 10. In contrast, at 300 K, the NQEs become weaker and the above dynamical results converge very quickly even with 1 bead. Most importantly, the NQEs seriously affect the excited-state decay mechanism of o-HBI. At 50 and 100 K, most trajectories decay to the S0 state via perpendicular keto MECIs, whereas, at 300 K, only twisted keto MECIs are responsible for the excited-state decay. The present work not only comprehensively explores the temperature-dependent photoinduced dynamics of o-HBI, but also demonstrates the importance and necessity of NQEs in nonadiabatic dynamics simulations, especially at relatively low temperatures.

Photoinduced Dynamics of a Single-Walled Carbon Nanotube with a sp3 Defect: The Importance of Excitonic Effects.

Herein, we employed linear-response time-dependent functional theory nonadiabatic dynamic simulations to explore the photoinduced exciton dynamics of a chiral single-walled carbon nanotube CNT(6,5) covalently doped with a 4-nitrobenzyl group (CNT65-NO2). The results indicate that the introduction of a sp3 defect leads to the splitting of the degenerate VBM/VBM-1 and CBM/CBM+1 states. Both the VBM upshift and the CBM downshift are responsible for the experimentally observed redshifted E11* trapping state. The simulations reveal that the photoinduced exciton relaxation dynamics completes within 500 fs, which is consistent with the experimental work. On the other hand, we also conducted the nonadiabatic carrier (electron and hole) dynamic simulations, which completely ignore the excitonic effects. The comparison demonstrates that excitonic effects are indispensable. Deep analyses show that such effects induce several dark states, which play an important role in regulating the photoinduced dynamics of CNT65-NO2. The present work demonstrates the importance of including excitonic effects in simulating photoinduced processes of carbon nanotubes. In addition, it not only rationalizes previous experiments but also provides valuable insights that will help in the future rational design of novel covalently doped carbon nanotubes with superior photoluminescent properties.

Flexible Meso Electronics and Photonics Based on Cocoon Silk and Applications.

Flexible electronics, applicable to enlarged health, AI big data medications, etc., have been one of the most important technologies of this century. Due to its particular mechanical properties, biocompatibility, and biodegradability, cocoon silk (or SF, silk fibroin) plays a key role in flexible electronics/photonics. The review begins with an examination of the hierarchical meso network structures of SF materials and introduces the concepts of meso reconstruction, meso doping, and meso hybridization based on the correlation between the structure and performance of silk materials. The SF meso functionalization was developed according to intermolecular nuclear templating. By implementation of the techniques of meso reconstruction and functionalization in the refolding of SF materials, extraordinary performance can be achieved. Relying on this strategy, particularly designed flexible electronic and photonic components can be developed. This review covers the latest ideas and technologies of meso flexible electronics and photonics based on SF materials/meso functionalization. As silk materials are biocompatible and human skin-friendly, SF meso flexible electronic/photonic components can be applied to wearable or implanted devices. These devices are applicable in human physiological signals and activities sensing/monitoring. In the case of human-machine interaction, the devices can be applicable in in-body information transmission, computation, and storage, with the potential for the combination of artificial intelligence and human intelligence.

The immune cell infiltration-associated molecular subtypes and gene signature predict prognosis for osteosarcoma patients.

Host immune dysregulation involves in the initiation and development of osteosarcoma (OS). However, the exact role of immune cells in OS remains unknown. We aimed to distinguish the molecular subtypes and establish a prognostic model in OS patients based on immunocyte infiltration. The gene expression profile and corresponding clinical feature of OS patients were obtained from TARGET and GSE21257 datasets. MCP-counter and univariate Cox regression analyses were applied to identify immune cell infiltration-related molecular subgroups. Functional enrichment analysis and immunocyte infiltration analysis were performed between two subgroups. Furthermore, Cox regression and LASSO analyses were performed to establish the prognostic model for the prediction of prognosis and metastasis in OS patients. The subgroup with low infiltration of monocytic lineage (ML) was related to bad prognosis in OS patients. 435 DEGs were screened between the two subgroups. Functional enrichment analysis revealed these DEGs were involved in immune- and inflammation-related pathways. Three important genes (including TERT, CCDC26, and IL2RA) were identified to establish the prognostic model. The risk model had good prognostic performance for the prediction of metastasis and overall survival in OS patients. A novel stratification system was established based on ML-related signature. The risk model could predict the metastasis and prognosis in OS patients. Our findings offered a novel sight for the prognosis and development of OS.

Theoretical insights into the photophysics of an unnatural base Z: A MS-CASPT2 investigation.

We have employed the highly accurate multistate complete active space second-order perturbation theory (MS-CASPT2) method to investigate the photoinduced excited state relaxation properties of one unnatural base, namely Z. Upon excitation to the S2 state of Z, the internal conversion to the S1 state would be dominant. From the S1 state, two intersystem crossing paths leading to the T2 and T1 states and one internal conversion path to the S0 state are possible. However, considering the large barrier to access the S1 /S0 conical intersection and the strong spin-orbit coupling between S1 and T2 states (>40 cm-1 ), the intersystem crossing to the triplet manifolds is predicted to be more preferred. Arriving at the T2 state, the internal conversion to the T1 state and the intersystem crossing back to the S1 state are both possible considering the S1 /T2 /T1 three-state intersection near the T2 minimum. Upon arrival at the T1 state, the deactivation to S0 can be efficient after overcoming a small barrier to access T1 /S0 crossing point, where the spin-orbit coupling (SOC) is as large as 39.7 cm-1 . Our present work not only provides in-depth insights into the photoinduced process of unnatural base Z, but can also help the future design of novel unnatural bases with better photostability.

Photocatalytic Reduction of CO2 to HCOOH and CO by a Phosphine-Bipyridine-Phosphine Ir(III) Catalyst: Photophysics, Nonadiabatic Effects, Mechanism, and Selectivity.

Photocatalytic CO2 reduction is one of the best solutions to solve the global energy crisis and to realize carbon neutralization. The tetradentate phosphine-bipyridine (bpy)-phosphine (PNNP)-type Ir(III) photocatalyst, Mes-IrPCY2, was reported with a high HCOOH selectivity but the photocatalytic mechanism remains elusive. Herein, we employ electronic structure methods in combination with radiative, nonradiative, and electron transfer rate calculations, to explore the entire photocatalytic cycle to either HCOOH or CO, based on which a new mechanistic scenario is proposed. The catalytic reduction reaction starts from the generation of the precursor metal-to-ligand charge transfer (3 MLCT) state. Subsequently, the divergence happens from the 3 MLCT state, the single electron transfer (SET) and deprotonation process lead to the formation of one-electron-reduced species and Ir(I) species, which initiate the reduction reaction to HCOOH and CO, respectively. Interestingly, the efficient occurrence of proton or electron transfer reduces barriers of critical steps. In addition, nonadiabatic transitions play a nonnegligible role in the cycle. We suggest a lower free-energy barrier in the reaction-limiting step and the very efficient SET in 3 MLCT are cooperatively responsible for a high HCOOH selectivity. The gained mechanistic insights could help chemists to understand, regulate, and design photocatalytic CO2 reduction reaction of similar function-integrated molecular photocatalyst.

Preliminary species diversity and community phylogenetics of wood-inhabiting basidiomycetous fungi in the Dabie Mountains, Central China reveal unexpected richness.

Wood-inhabiting fungi have important economic values as well as playing a major ecological role in forest ecosystem cycles. The Dabie Mountains, at the junction of Henan, Hubei, and Anhui Provinces, Central China, provide an ideal climate and favorable niches for the speciation and diversification of various forms of life including fungi. We studied the species diversity and community phylogenetics of wood-inhabiting basidiomycetous fungi that revealed 175 wood-inhabiting basidiomycetous species, of which 20 represented unidentified species, based on morphological and phylogenetic analyses of 575 specimens collected from ten sampling sites. These species belonged to two classes, 11 orders, 42 families, and 106 genera of Basidiomycota, and included 12 edible species, 28 medicinal species, four poisonous species, and seven forest pathogens. Four types of fungal distribution pattern at the genus level were recognized for 65 genera, while another 41 genera could not be placed in any known distribution pattern. The five sampling sites in the eastern part of the Dabie Mountains had significantly higher species diversity and phylogenetic diversity of wood-inhabiting basidiomycetous fungi than those in the western part, and thus deserve priority in terms of conservation. The community of wood-inhabiting basidiomycetous fungi in the Dabie Mountains is generally affected by a combination of habitat filtering and competitive exclusion. This study provides a basis on which to build actions for the comprehensive recognition, utilization, and conservation of wood-inhabiting basidiomycetous fungi in the region.

Nonadiabatic Dynamics Simulations for Photoinduced Processes in Molecules and Semiconductors: Methodologies and Applications.

Nonadiabatic dynamics (NAMD) simulations have become powerful tools for elucidating complicated photoinduced processes in various systems from molecules to semiconductor materials. In this review, we present an overview of our recent research on photophysics of molecular systems and periodic semiconductor materials with the aid of ab initio NAMD simulation methods implemented in the generalized trajectory surface-hopping (GTSH) package. Both theoretical backgrounds and applications of the developed NAMD methods are presented in detail. For molecular systems, the linear-response time-dependent density functional theory (LR-TDDFT) method is primarily used to model electronic structures in NAMD simulations owing to its balanced efficiency and accuracy. Moreover, the efficient algorithms for calculating nonadiabatic coupling terms (NACTs) and spin-orbit couplings (SOCs) have been coded into the package to increase the simulation efficiency. In combination with various analysis techniques, we can explore the mechanistic details of the photoinduced dynamics of a range of molecular systems, including charge separation and energy transfer processes in organic donor-acceptor structures, ultrafast intersystem crossing (ISC) processes in transition metal complexes (TMCs), and exciton dynamics in molecular aggregates. For semiconductor materials, we developed the NAMD methods for simulating the photoinduced carrier dynamics within the framework of the Kohn-Sham density functional theory (KS-DFT), in which SOC effects are explicitly accounted for using the two-component, noncollinear DFT method. Using this method, we have investigated the photoinduced carrier dynamics at the interface of a variety of van der Waals (vdW) heterojunctions, such as two-dimensional transition metal dichalcogenides (TMDs), carbon nanotubes (CNTs), and perovskites-related systems. Recently, we extended the LR-TDDFT-based NAMD method for semiconductor materials, allowing us to study the excitonic effects in the photoinduced energy transfer process. These results demonstrate that the NAMD simulations are powerful tools for exploring the photodynamics of molecular systems and semiconductor materials. In future studies, the NAMD simulation methods can be employed to elucidate experimental phenomena and reveal microscopic details as well as rationally design novel photofunctional materials with desired properties.

Solvent effects on the photoinduced charge separation dynamics of directly linked zinc phthalocyanine-perylenediimide dyads: a nonadiabatic dynamics simulation with an optimally tuned screened range-separated hybrid functional.

Herein, we have employed a combination of the optimally tuned screened range-separated hybrid (OT-SRSH) functional, the polarizable continuum model (PCM), and nonadiabatic dynamics (NAMD) simulations to investigate the photoinduced dynamics of directly linked donor-acceptor dyads formed using zinc phthalocyanine (ZnPc) and perylenediimide (PDI), in which ZnPc is the donor while PDI is the acceptor. Our simulations aim to analyze the behavior of these dyads upon local excitation of the ZnPc moiety in the gas phase and in benzonitrile. Our findings indicate that the presence of a solvent can significantly influence the excited state dynamics of ZnPc-PDI dyads. Specifically, the polar solvent benzonitrile effectively lowers the vertical excitation energies of the charge transfer (CT) state from ZnPc to PDI. As a result, the energetic order of the locally excited (LE) states of ZnPc and the CT states is reversed compared to the gas phase. Consequently, the photoinduced electron transfer (PET) dynamics from ZnPc to PDI, which is absent in the gas phase, takes place in benzonitrile with a time constant of 10.4 ps. Importantly, our present work not only qualitatively agrees with experimental results but also provides in-depth insights into the underlying mechanisms responsible for the photoinduced dynamics of ZnPc-PDI. Moreover, this study emphasizes the importance of appropriately considering solvent effects in NAMD simulation of organic donor-acceptor systems, taking into account the distinct excited state dynamics observed in the gas phase and benzonitrile. Furthermore, the combination of the OT-SRSH functional, the PCM solvent model, and nonadiabatic dynamics simulations shows promise as a strategy for investigating the complex excited state dynamics of organic donor-acceptor systems in solvents. These findings will be valuable for the future design of novel organic donor-acceptor structures with improved performance.

Anion-modulated CoP electrode as bifunctional electrocatalyst for anion-exchange membrane hydrazine-assisted water electrolyser.

The hydrazine oxidation reaction (HzOR) is considered as a promising alternative process of the oxygen evolution reaction (OER) to realize more energy-efficient hydrogen generation. However, the lack of highly active bifunctional catalysts poses a huge challenge to this strategy. In this work, we report a novel and universal electrodeposition strategy to rationally synthesize a self-supporting electrode. The utilization of ammonium fluoride helps to modulate not only the morphology of CoP, but also the synchronous formation of an anion-modified structure, leading to an excellent bifunctional performance. The optimal F-CoP/CF exhibits small potentials of -90 mV and 41 mV at 1 A cm-2, high stability and low Tafel slopes of 28 mV dec-1 and 3.26 mV dec-1 for the HER and HzOR, respectively. The highly efficient and stable bifunctional activity of F-CoP/CF can be further confirmed in an anion-exchange membrane hydrazine-assisted water electrolyzer (0.49 V at 1 A cm-2). Utilizing the density functional theory calculations, the optimized adsorption energy of water molecules and hydrogen intermediates of the HER as well as the rate-determining step of the HzOR are demonstrated for the F-CoP.

Cross-Scale Topography Achieved by MOPL with Positive Photoresist to Regulate the Cell Behavior.

Cross-scale micro-nano structures play an important role in semiconductors, MEMS, chemistry, and cell biology. Positive photoresist is widely used in lithography due to the advantages of high resolution and environmental friendliness. However, cross-scale micro-nano structures of positive photoresist are difficult to flexibly pattern, and the feature resolution is limited by the optical diffraction. Here, cross-scale patterned micro-nano structures are achieved using the positive photoresist based on the femtosecond laser maskless optical projection lithography (MOPL) technique. The dependence between exposure dose and groove width is comprehensively analyzed, and a feature size of 112 nm is obtained at 110 µW. Furthermore, large-area topography considering cell size is efficiently fabricated by the MOPL technique, which enables the regulation of cell behavior. The proposed protocol of achieving cross-scale structures with the exact size by MOPL of positive photoresist would provide new avenues for potential applications in nanoelectronics and tissue engineering.

Nonadiabatic Derivative Couplings Calculated Using Information of Potential Energy Surfaces without Wavefunctions: Ab Initio and Machine Learning Implementations.

In this work, we implemented an approximate algorithm for calculating nonadiabatic coupling matrix elements (NACMEs) of a polyatomic system with ab initio methods and machine learning (ML) models. Utilizing this algorithm, one can calculate NACMEs using only the information of potential energy surfaces (PESs), i.e., energies, and gradients as well as Hessian matrix elements. We used a realistic system, namely CH2NH, to compare NACMEs calculated by this approximate PES-based algorithm and the accurate wavefunction-based algorithm. Our results show that this approximate PES-based algorithm can give very accurate results comparable to the wavefunction-based algorithm except at energetically degenerate points, i.e., conical intersections. We also tested a machine learning (ML)-trained model with this approximate PES-based algorithm, which also supplied similarly accurate NACMEs but more efficiently. The advantage of this PES-based algorithm is its significant potential to combine with electronic structure methods that do not implement wavefunction-based algorithms, low-scaling energy-based fragment methods, etc., and in particular efficient ML models, to compute NACMEs. The present work could encourage further research on nonadiabatic processes of large systems simulated by ab initio nonadiabatic dynamics simulation methods in which NACMEs are always required.

Bioinspired Conductive Enhanced Polyurethane Ionic Skin as Reliable Multifunctional Sensors.

Ionogels prepared from ionic liquid (IL) have the characteristics of nonevaporation and stable performance relative to traditional hydrogels. However, the conductivities of commonly used ionogels are at very low relative to traditional hydrogels because the large sizes of the cation and anion in an IL impedes ion migration in polymer networks. In this study, ultradurable ionogels with suitable mechanical properties and high conductivities are prepared by impregnating IL into a safe, environmentally friendly water-based polyurethane (WPU) network by mimicking the ion transport channels in the phospholipid bilayer of the cell membrane. The increase in electrical conductivity is attributed to the introduction of carboxylic acid in the hard segment of WPU; this phenomenon regularly arranges hard segment structural domains by hydrogen bonding, forming ionic conduction channels. The conductivities of their ionogels are >28-39 mS cm-1 . These ionogels have adjustable mechanical properties that make the Young's modulus value (0.1-0.6 MPa) similar to that of natural skin. The strain sensor has an ultrahigh sensitivity that ranges from 0.99 to 1.35, with a wide sensing range of 0.1%-200%. The findings are promising for various ionotronics requiring environmental stability and high conductivity characteristics.

Multiple Photoisomerization Pathways of the Green Fluorescent Protein Chromophore in a Reversibly Photoswitchable Fluorescent Protein: Insights from Quantum Mechanics/Molecular Mechanics Simulations.

Herein, we have employed a combined CASPT2//CASSCF approach within the quantum mechanics/molecular mechanics (QM/MM) framework to explore the early time photoisomerization of rsEGFP2 starting from its two OFF trans states, i.e., Trans1 and Trans2. The results show similar vertical excitation energies to the S1 state in their Franck-Condon regions. Considering the clockwise and counterclockwise rotations of the C11-C9 bond, four pairs of the S1 excited-state minima and low-lying S1/S0 conical intersections were optimized, based on which we determined four S1 photoisomerization paths that are essentially barrierless to the relevant S1/S0 conical intersections leading to efficient excited-state deactivation to the S0 state. Most importantly, our work first identified multiple photoisomerization and excited-state decay paths, which must be seriously considered in the future. This work not only sheds significant light on the primary trans-cis photoisomerization of rsEGFP2 but also aids in the understanding of the microscopic mechanism of GFP-like RSFPs and the design of novel GFP-like fluorescent proteins.

Silk fibroin based wearable electrochemical sensors with biomimetic enzyme-like activity constructed for durable and on-site health monitoring.

Flexible biomimetic sensors have encountered a bottleneck of sensitivity and durability, as the sensors must directly work within complex body fluid with ultra-trace biomarkers. In this work, a wearable electrochemical sensor on a modified silk fibroin substrate is developed using gold nanoparticles hosted into N-doped porous carbonizated silk fibroin (AuNPs@CSF) as active materials. Taking advantage of the inherent biocompatibility and flexibility of CSF, and the high stability and enzyme-like catalytic activity of AuNPs, AuNPs@CSF-based sensor exhibits durable stability and superior sensitivity to monitor H2O2 released from cancer cell (4T1) and glucose in sweat. The detection limits for H2O2 and glucose are low to be 1.88 µM and 23 µM respectively, and the sensor can be applied in succession within 30 days at room temperature. Further, physical cross-linking of polyurethane (PU) with SF well matches with the skin tissue mechanically and provides a flexible, robust and stable electrode-tissue interface. AuNPs@CSF is applied successfully for wearable electrochemical monitoring of glucose in human sweat.The present AuNPs@CSF will possess a potential application in clinical diagnosing of H2O2- or glucose-related diseases in future.