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Suppressing non-radiative energy loss (ΔE 3 ) mediated by the triplet charge transfer state is crucial for high-performance organic solar cells (OSCs). Here, we decode the energy inversion through multi-scale theoretical simulations, which inhibit the formation of non-emissive triplet (T 1 ) state. However, it is mystified by the system dependence. We first demonstrate a direct relationship of "the probability of Face-on orientation (P Face-on ) is proportional to the probability of energy inversion (P EI )", which is related to the function of terminal fluorination. Through Pearson's correlation coefficient and machine learning model, the useful stacking structural parameters were obtained to clarify the effect of π-bridge group on the function of terminal fluorination. Based on the molecular descriptors established, we explain that the fluorination effect is beneficial to Face-on orientation and thus energy inversion due to the enhanced intermolecular coupling. But the π-bridge inhibits this coupling with the interfacial stacking configuration appearing more "TT_IC". This work provides a directional standard for promoting energy inversion to reduce ΔE 3 for the high-performance OSCs., (© 2024 Wiley-VCH GmbH.)

Ternary solar cells have been rapidly developed in the realm of organic solar cells (OSCs). The incorporation of a third component into a cell results in a complicated active layer morphology, and the relation of this morphology to power conversion efficiency remains elusive. In this work, two ternary active layers, B1:Y7 (10 wt%):BO-4Cl and B1:Y7 (50 wt%):BO-4Cl are constructed, and the reasons for the differences in PCE caused by varying the Y7 content are investigated using theoretical calculations. Firstly, four groups of binary complexes (B1:BO-4Cl-10 wt%, B1:BO-4Cl-50 wt%, B1:Y7-10 wt%, B1:Y7-50 wt%) were examined using molecular dynamics simulation and the stacking patterns of the complexes could mainly be categorized into three groups (IC-T, IC-BDT, IC-RHD). The results showed that with an increase of the Y7 content, the proportion of IC-T stacking decreased while IC-BDT stacking increased. Moreover, the properties of each stacking pattern were calculated and IC-T stacking was found to have a greater charge separation coupling and rate, and a smaller interaction energy. With more IC-T stacking, the number of charge transfer (CT) states and CT mechanisms in B1:BO-4Cl-10 wt% and B1:Y7-10 wt% improves the PCE of B1:Y7 (10 wt%):BO-4Cl. For the trimers, a greater number of CT states and CT pathways can also facilitate efficient charge separation in B1:Y7 (10 wt%):BO-4Cl. Additionally, this work provides basic knowledge of the influence that the third component content on cell performance, providing theoretical instruction for experimental work based on Y-series non-fullerene acceptor materials.

The performance of organic solar cell (OSC) devices has been significantly enhanced by the dramatic evolution of A-D-A type non-fullerene acceptors (NFAs). Nevertheless, the structure-property-performance relationship of NFAs in the OSC device is unclear. Here, the intrinsic design factors of isomeric, fluorination and π-conjunction curtailing on the photophysical properties of benzodi (thienopyran) (BDTP) (named NBDTP-M, NBDTTP-M, NBDTP-F in , and NBDTP-F out )-based NFAs are discussed. The results show that fluorination on the terminal group of NBDTP-F out could effectively decrease the highest occupied orbital (HOMO) energy level and the lowest unoccupied orbital (LUMO) energy level. And the long π-conjugated donor unit for NBDTTP-M could increase the HOMO energy level and bring a small HOMO-LUMO energy bandgap. Meanwhile, the substitution of external oxygen atoms and the fluorine atoms in the terminal group could introduce positive changes to the electrostatic potential of the NBDTP-F out , favouring the charge separation at the donor/acceptor interface. Moreover, the structural design of external oxygen atom substitution, fluorination on the terminal group and curtailed π-conjugated donor unit could decrease the electron vibration-coupling of exciton diffusion, exciton dissociation and electronic transfer processes. The suppression of the exciton decay and charge recombination in those high-performance NFAs indicate that the investigated molecular designs could be effective for further improvement of OSCs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Proton exchange membrane fuel cells (PEMFCs) are developing into very meaningful clean energy to fundamentally address environmental pollution. Among which the most studied Nafion series membranes are limited under large-scale use, and some strong oxidizing groups such as hydrogen peroxide will attack the structure of Nafion, shortening the lifespan of PEMFCs. Therefore, it is crucial to develop a proton-conductive material with strong stability and broad application. In this study, a novel hourglass-type P 4 Mo 6 -based POMOFs denoted as (H 2 timb) 2 [Mn 3 (H 3 P 4 Mo 6 O 31 ) 2 ]·4H 2 O was synthesized using 1,3,5-tri(1 H -imidazole-1-yl)benzene (timb) as a ligand. It was found that CUST-577 exhibited an excellent proton conductivity of 8.9 × 10 -3 S cm -1 at 80 °C and 98% RH (relative humidity), proving that CUST-577 was conducted by protons. In addition, CUST-577 also had a greater H 2 O 2 decomposition ability, thereby improving the longevity of fuel cells. In a three-electrode system, CUST-577 displayed a specific capacitance (Cs) value of 308 F g -1 at a current density of 0.15 A g -1 , with a capacitance retention of 88.3% after 2000 cycles. Since the proton-conductive electrolyte can deliver protons for the redox reaction of various pseudocapacitor (PC) electrode materials, CUST-577 may be a promising polyacid-based proton conductor material and PC electrode material.

The power conversion efficiency (PCE) of organic solar cells (OSCs) devices has surpassed 19% owing to the blooming of fused-ring nonfullerene acceptors (NFAs), especially for acceptor-donor-acceptor (A-D-A) type NFAs. However, the structural effect of the angular/linear fusion mode and number of fused rings for A-D-A type NFAs on the photovoltaic performance in OSCs devices remains unclear. Herein, the A-D-A type NFAs ( F-0Cl , IDIC8-H , and ITIC ) have been selected to obtain the intrinsic role of structural design strategies including the angular/linear fusion mode and the number of fused rings. The results indicate that compared to the linear fusion mode in ITIC , the angular fusion mode in F-0Cl effectively diminishes electronic vibrational coupling within the low-frequency range, leading to lower charge reorganization during the exciton diffusion process. Meanwhile, it facilitates the generation of multiple charge transfer mechanisms at the donor/acceptor (D/A) interface and increases the rates of hole transfer. On the other hand, the decreased number of fused rings of NFAs could inhibit the exciton decay and charge recombination but increase the rates of exciton diffusion and exciton dissociation for individual NFAs and the rates of electron separation for D/A interface. This work provides theoretical insights into structural design strategies, such as linear/angular fusion, and the number of fused rings of NFA, which presents a promising outlook for further enhancing PCE of high-performance A-D-A type NFAs.

To select appropriate organic ligands is an effective strategy to enhance the proton conductivities of polyoxometalate-based metal-organic frameworks (POMOFs). Two new Dawson-type POMOFs, named CUST-961 and CUST-962, have been designed and synthesized via combining Htzbc selected by hard and soft acid and base theory and density functional theory calculation, transition metal ions, alkali metal ions (Na + and K + ), and Dawson-type polyoxometalates ([P 2 W 18 ] 6- ) under the hydrothermal method. Their stabilities under different temperatures and relative humidities (RHs) have been investigated through powder X-ray diffraction and thermogravimetric analysis. Both CUST-961 and CUST-962 exhibited excellent aqueous and thermal stabilities. The alternating current (AC) impedance spectrum tests revealed that the proton conductivity of CUST-961 could reach 1.4 × 10 -4 S cm -1 at 95 °C and 98% RH, which is about 3 times that of CUST-962. The different proton conductivities between the two compounds are due to the fact that CUST-961 possesses more uncoordinated carboxylic acid groups, as confirmed by attenuated total reflection infrared spectroscopy and 1 H solid-state nuclear magnetic resonance spectroscopy, which can not only act as the proton source but also establish a richer hydrogen bonding network to enhance proton conduction. This work provides a new strategy and insight for the design and preparation of polyoxometalate-based proton conductive materials.

Silyl-phenanthroline (NN'Si) ligand ancillary iridium-catalyzed C(sp 3 )-H borylation is investigated theoretically. Density functional theory calculations clearly disclose that the (NN'Si)Ir V (H)(Bpin) 3 (NN'Si = 6-[(di- tert -butylsilyl)methyl]-1,10-phenanthroline) complex is a resting state, and the (NN'Si)Ir III (Bpin) 2 complex serves as an active species in the catalytic cycle. The remarkably high activity of this type of a catalyst arises from the rapid reductive elimination of HBpin from (NN'Si)Ir V (H)(Bpin) 3 to generate the active species (NN'Si)Ir III (Bpin) 2 . The silyl group plays a crucial role in accelerating the crucial hydride-migration elementary step, which allows the isomerization of the (NN'Si)Ir V (R)(H)(Bpin) 2 intermediate to achieve the C(sp 3 )-B reductive elimination and afford the borylated product. Although C(sp 3 )-H borylation with HBpin is thermodynamically unfavorable, the Ir-dihydride intermediate (NN'Si)Ir V (H) 2 (Bpin) 2 generated after product formation is slightly more stable than resting-state (NN'Si)Ir V (H)(Bpin) 3 in this catalytic cycle, which is an important driving force for the HBpin reaction. Such success was not attained by many other traditional bidentate ligands. The unique regioselectivity of n -butyl ethyl ether and 2-methylheptane, induced by the NN'Si-pincer ligand, is well reproduced and the underlying reason for the selectivity is clearly elucidated.

Electrochemically upcycling polyvinyl chloride (PVC) into high-value small molecules represents a sustainable strategy for mitigating plastic pollution. Herein, a cost-effective self-supporting electrode with abundant vacancies, i.e., NiFe-layered double hydroxide nanoarrays in-situ grown on the surface of carbon paper (denoted as NiFe V -LDH/CP), is developed for the electro-Fenton degradation of PVC microplastics (MPs). The NiFe V -LDH catalyst shows a high selectivity of 76 % towards H 2 O 2 production via two-electron oxygen reduction reaction (2e - ORR). Density functional theory (DFT) calculations reveal that the energy barrier of rate-determining step (*H 2 O 2 desorption) decreases over the vacancy-enriched NiFe V -LDH related to the pristine NiFeZn-LDH. The influence of vacancy concentration, reaction temperature and initial concentration of PVC MPs were systematically investigated. Under optimized conditions, the NiFe V -LDH/CP electrode exhibits an outstanding degradation performance of PVC MPs via direct cathodic reduction and oxidation by hydroxyl radicals. This work demonstrates that the electro-Fenton technology using LDH-based self-supporting electrodes is a promising and environmentally-friendly approach for waste plastic treatment., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Neutral radicals have the potential to construct pure organic light-emitting diodes (OLEDs) with internal quantum efficiencies reaching 100%. However, neutral radical luminescent materials with emission wavelengths in the second near-infrared (NIR-II) window are rare. Herein, a serial of neutral donor-bridge-acceptor (D-π-A) type radical derivatives are investigated. The dominant elements influencing the luminescent properties of neutral radicals, such as chemical stability, excited state characteristics, radiative decay rate (k r ) and internal conversion rate (k IC ) constants are taken into consideration. Theoretical calculations reveal that introducing heteroatomic fused-rings into neutral radicals can modulate the chemical stability and result in a red shift of the emission wavelength spectrum. In the presence of charge transfer characteristics, by increasing the effective overlap between the hole and electron wavefunctions, the k r constants of the neutral D-π-A type radicals increase. In addition, avoiding the geometric relaxation between the lowest excited state (D 1 ) and the ground state (D 0 ), as well as reducing electron-vibration coupling and non-adiabatic coupling in the low-frequency region can effectively decrease the k IC constants. Our study proposes an innovative design approach aiming to develop stable and efficient NIR-II window neutral radical luminescent materials utilizing heteroatomic fused-rings as key elements., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A carbazolyl-based fluorescent metal-organic framework with deep-blue light emission and a high quantum yield (88%) has been screened out by changing the ratio of mixed ligands, named Cz-MOF-2, which was constructed by ZrO 4 (OH) 4 clusters, 3-(9-ethyl-9 H -carbazol-3-yl)-4-methylthieno[2,3- b ]thiophene-2,5-dicarboxylate (H 2 ECMTDC) and 3,4-dimethyl-dihydrothieno[2,3- b ]thiophene-2,5-dicarboxylate (H 2 DMTDC). Cz-MOF-2 has excellent sensitivity in fluorescent sensing of 2,6-dichloro-4-nitroaniline (DCN), nitrofurazone (NZF), and nitrofurantoin (NFT) with detection limits of 3.37 × 10 -7 , 1.64 × 10 -5 , and 1.76 × 10 -5 M, respectively. The quenching mechanisms involving electron transfer and competitive absorption were comprehensively elucidated through DFT calculations and UV absorption experiments. Cz-MOF-2 has been fabricated into a rapidly regenerated composite membrane with PVDF as a visualized fluorescent sensor for DCN. Furthermore, the carbazolyl groups covalently modified in the framework endowed Cz-MOF-2 with a suitable band gap (2.58 eV) for photocatalytic degradation of organic contaminants. It demonstrated superior photocatalytic efficiency compared to UiO-66 and NH 2 -UiO-66 in the degradation of tetracycline (TC), and the removal efficiency was up to 85% (20 mg of catalyst, 50 mL, 20 mg/L TC solution and 180 min) under simulated sunlight irradiation using a 300 W Xe lamp. Photoelectrochemical tests demonstrate that Cz-MOF-2 exhibits high photocurrent density and low charge transfer resistance, which provide evidence for the efficient charge separation capability. Radical trapping experiments and ESR detection have substantiated that · O 2 - and h + are the primary active species involved in this photocatalytic reaction. This work highlights the potential of MOFs in the targeted design and development of fluorescent sensors and photocatalysts for environmental detection and remediation.

The liquid-phase catalytic oxidation of p -cymene to 4-methylacetophenone is an industrially significant reaction. However, the targeted oxidation of a specific C-H bond of p -cymene is extremely difficult due to there being many branched chains in p -cymene. In here, we designed a simple method to synthesize mesoporous LaCoO 3 catalysts with rich oxygen vacancy (O ov ) sites. The as-prepared mesoporous LaCoO 3 after 550 °C calcination (mLaCoO 3 ) exhibits remarkable catalytic activity for solvent-free oxidation of the p -cymene reaction, with a selectivity of over 80.1% selectivity for 4-methylacetophenone and a conversion of 50.2% for p -cymene (120 °C, 3 MPa). Besides, recycling studies have demonstrated that the mLaCoO 3 catalysts can be reused ten times in the aerobic oxidation of the p -cymene reaction without significant catalytic activity reduce. The experimental and characterization results indicated that the mesoporous structure of the catalyst is conducive to the generation of surface O ov , which can properly facilitate ion spread during the catalytic process and afford enough O 2 for intermediate species, thus is beneficial for the generation of 4-methylacetophenone. This work demonstrates that the selectivity oxide p -cymene with an O 2 employing mLaCoO 3 catalyst is highly promising for chemical industrial applications.

As the core component of the all-metal micro resonant gyroscope, the structural parameters and form and position errors of the resonator significantly influence its vibration characteristics, and consequently, the accuracy of the gyroscope. By establishing the finite element model of an ideal hemispherical resonator and optimizing the meshing method, we refined the frequency difference to 0.1 Hz, enhancing the accuracy of the simulation model. Through finite element simulation, we examined the impact of various structural parameters and processing errors on the natural frequencies of each mode. We analyzed how form and position errors, including shell thickness error, central axis error, equatorial plane error, and edge rectangular tooth position error, affect the frequency splitting of the resonator. We provided optimization suggestions for the structural parameters, ensuring frequency splitting variations of less than 1 Hz. Theoretical modeling and simulation analysis indicated that the primary factors influencing the vibration modes and frequency splitting are the rectangular tooth structure and shell thickness. Following the optimized parameters, the frequency splitting of the All-Metal Micro Resonant Hemisphere was reduced by an order of magnitude to 14 Hz, demonstrating that these optimized conditions can significantly enhance the resonator's performance.

Metal-μhemispherical resonant gyros (M-μHRGs) are widely used in highly dynamic navigation systems in extreme environments due to their high accuracy and structural stability. However, the effect of temperature variations on the capacitance characteristics of M-μHRGs has not been fully investigated, which is crucial for optimizing the performance of the gyro. This study aims to systematically analyze the effect of temperature on the static and dynamic capacitances of M-μHRGs. In this study, an M-μHRG structure based on a 16-tooth metal oscillator is designed, and conducted simulation experiments using non-contact capacitance measurement method and COMSOL Multiphysics 6.2 finite element simulation software in the temperature range of 233.15 K to 343.15 K. The modeling analysis of the static capacitance takes into account the thermal expansion effect, and the results show that static capacitance remains stable across the measured temperature range, with minimal effect from temperature. The dynamic capacitance exhibits significant nonlinear variations under different temperature conditions, especially in the two end temperature intervals (below 273.15 K and above 313.15 K), where the capacitance values show local extremes and fluctuations. In order to capture this nonlinear behavior, the experimental data were smoothed and fitted using the LOESS method, revealing a complex trend of the capacitance variation with temperature. The results show that the M-μHRG has good capacitance stability in the mid-temperature range, but its dynamic performance is significantly affected at extreme temperatures. This study provides a theoretical reference for the optimal design of M-μHRGs in high- and low-temperature environments.

Oxygen evolution reaction is the essential anodic reaction for water splitting. Designing tunable electronic structures to overcome its slow kinetics is an effective strategy. Herein, the molecular ammonium iron sulfate dodecahydrate is employed as the precursor to synthesize the C, N, S triatomic co-doped Fe(Al)OOH on Ni foam (C,N,S-Fe(Al)OOH-NF) with asymmetric electronic structure. Both in situ oxygen vacancies and their special electronic configuration enable the electron transfer between the d-p orbitals and get the increase of OER activity. Density functional theory calculation further indicates the effect of electronic structure on catalytic activity and stability at the oxygen vacancies. In alkaline solution, the catalyst C,N,S-Fe(Al)OOH-NF shows good catalytic activity and stability for water splitting. For OER, the overpotential of 10 mA cm -2 is 264 mV, the tafel slope is 46.4 mV dec -1 , the HER overpotential of 10 mA cm -2 is 188 mV, the tafel slope is 59.3 mV dec -1 . The stability of the catalyst can maintain ≈100 h. This work has extraordinary implications for understanding the mechanistic relationship between electronic structure and catalytic activity for designing friendly metal (oxy)hydroxide catalysts., (© 2024 Wiley‐VCH GmbH.)

Iridium-catalyzed C-H borylation of aromatic and aliphatic hydrocarbons assisted by a directing group was theoretically investigated. Density functional theory (DFT) calculations revealed both Ir-catalyzed C(sp 2 )-H and C(sp 3 )-H borylations via an Ir III /Ir V catalytic cycle, where the tetra-coordinated (C, N)Ir III (Bpin) 2 complex with two vacant sites is an active species. Dramatically, the orientation of cyclometalation for C(sp 2 )-H bond activation assisted by a directing group is different from the C(sp 3 )-H one. The activation energy (Δ G °‡ = 28.5 kcal mol -1 ) of the C(sp 2 )-H bond via trans -chelation to form cyclometalation is lower than that (41.4 kcal mol -1 ) via cis -chelation. In contrast, the Δ G °‡ (26.6 kcal mol -1 ) of the C(sp 3 )-H bond via cis -chelation to form cyclometalation is lower than that (34.3 kcal mol -1 ) via trans -chelation. In addition, the rate-determining step of Ir-catalyzed C(sp 2 )-H borylation is oxidative addition of the C(sp 2 )-H bond, while that of C(sp 3 )-H analogues is hydride migration. Such differences arise from not only the differences in the steric hindrance of the C(sp 2 ) and secondary C(sp 3 ) atoms but also the differences in the trans effect and steric effect of the two vacant sites of active species. These findings were expected to facilitate further studies on the design and synthesis of innovative ligands for Ir-catalyzed C-H borylation.

The photophysical properties and luminescent mechanism of a series of tripod-type Cu(I) complexes in solution and solids were comprehensively investigated through theoretical simulations. From a microscopic perspective, the experimental phenomenon is explained: (1) The intrinsic reason for the quenching of complex 1 in solution was attributed to the significant nonradiative transition caused by structural deformation; (2) In the solid, the reduced Δ E ST for complex 2 effectively facilitate reverse intersystem crossing (RISC) and improves its luminescence efficiency; (3) The enhanced performance of complex 3 in solution is attributed to that its stronger steric hindrance is advantageous to decrease not only the Δ E ST but also the reorganization energy through intramolecular weak interactions. Based on complex 3 , the tert -butyl substituted isomeric complex 4 was designed. Complex 4 further amplifies the advantages of 3 to further promote the RISC to make full use of excitons. Meanwhile, it has an emission wavelength of 462.6 nm, which makes it an excellent candidate for high-efficiency deep-blue TADF materials. This study provides valuable information for obtaining efficient blue phosphorescence and TADF dual-channel luminescent materials.

The external electric field has emerged as a powerful tool for building molecular switches with excellent properties. In this work, we investigate the impact of an external electric field on the transition between lithium salt and electride-like molecule conformations in Li@corannulene. Remarkably, the distance between the Li atom and the corannulene bottom displays a sharp increase under the influence of an external electric field strength of F - z = 110 × 10 -4 a.u. As the external electric field strength increases, the Li atom brings about different directions of charge transfer (CT). The natural population analysis (NPA) charge and the molecular electrostatic potential (ESP) results show that the intermolecular CT occurs from the Li atom to the corannulene with the F - z ranging from 0 to 100 × 10 -4 a.u. Interestingly, when the external electric field reaches F - z = 110 × 10 -4 a.u., the CT is oriented from the corannulene to the Li atom. Moreover, electron localization function (ELF) basins are presented under an F - z of 110 × 10 -4 a.u., which indicates that Li@corannulene exhibits electride-like (e - ⋯[Li@corannulene] + ) molecules and lithiation salt (Li + [corannulene] - ) under an F - z of 0 to 100 × 10 -4 a.u. Significantly, the differences in charge transfer also contribute to a significant improvement in hyperpolarizabilities ( β tot ) during the conformation transition from lithiation salt (Li + [corannulene] - ) to electride-like (e - ⋯[Li@corannulene] + ) molecules. This study explores the potential of Li@corannulene as a promising second-order NLO material, and the external electric field provides an efficient strategy for designing and developing NLO switching devices.

The conversion of CO 2 into useful chemicals via photocatalysts is a promising strategy for resolving the environmental problems caused by the addition of CO 2 . Herein, a series of composite photocatalysts MOP@TpPa-CH 3 based on MOP-NH 2 and TpPa-CH 3 through covalent bridging have been prepared via a facile room-temperature evaporation method and employed for photocatalytic CO 2 reduction. The photocatalytic performances of MOP@TpPa-CH 3 are greater than those of TpPa-CH 3 and MOP-NH 2 , where the CO generation rate of MOP@TpPa-CH 3 under 10% CO 2 still reaches 119.25 μmol g -1 h -1 , which is 2.18 times higher than that under pure CO 2 (54.74 μmol g -1 h -1 ). To investigate the structural factors affecting the photocatalytic activity, MOP@TBPa-CH 3 without C═O groups is synthesized, and the photoreduction performance is also evaluated. The controlling experimental results demonstrate that the excellent photoreduction CO 2 performance of MOP@TpPa-CH 3 in a 10% CO 2 atmosphere is due to the presence of C═O groups in TpPa-CH 3 . This work offers a new design and construction strategy for novel MOP@COF composites.

Acetaldehyde (AA) and ethylene oxide (EO) are important fine chemicals, and are also substrates with wide applications for high-value chemical products. Direct electrocatalytic oxidation of ethylene to AA and EO can avoid the untoward effects from harmful byproducts and high energy emissions. The most central intermediate state is the co-adsorption and coupling of ethylene and active oxygen intermediates (*O) at the active site(s), which is restricted by two factors: the stability of the *O intermediate generated during the electrolysis of water on the active site at a certain applied potential and pH range; and the lower kinetic energy barriers of the oxidation process based on the thermo-migration barrier from the *O intermediate to produce AA/EO. The benefit of two adjacent active atoms is more promising, since diverse adsorption and flexible catalytic sites may be provided for elementary reaction steps. Motivated by this strategy, we explored the feasibility of various homonuclear TM 2 N 6 @graphenes with dual-atomic-site catalysts (DASCs) for ethylene electro-oxidation through first-principles calculations via thermodynamic evaluation, analysis of the surface Pourbaix diagram, and kinetic evaluation. Two reaction mechanisms through C-TM versus TM-TM synergism were determined. Between them, a TM-TM mechanism on 4 TM 2 N 6 @graphenes and a C-TM mechanism on 5 TM 2 N 6 @graphenes are built. All 5 TM 2 N 6 @graphenes through the C-TM mechanism exhibit lower kinetic energy barriers for AA and EO generation than the 4 TM 2 N 6 @graphenes through the TM-TM mechanism. In particular, Pd 2 N 6 @graphene exhibits the most excellent catalytic activity, with energy barriers for generating AA and EO of only 0.02 and 0.65 eV at an applied potential of 1.77 V vs. RHE for the generation of an active oxygen intermediate. Electronic structure analysis indicates that the intrinsic C-TM mechanism is more advantageous than the TM-TM mechanism for ethylene electro-oxidation, and this study also provides valuable clues for further experimental exploration., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Carbon dioxide (CO 2 ) coupled with epoxide to generate cyclic carbonate stands out in carbon neutrality due to its 100% atom utilization. In this work, the mechanism of CO 2 cycloaddition with propylene oxide (PO) cocatalyzed by windmill-shaped polyoxovanadate, [(C 2 N 2 H 8 ) 4 (CH 3 O) 4 V IV 4 V V 4 O 16 ]·4CH 3 OH (V 8 -1), and n -Bu 4 NX (X = Br, I) was thoroughly investigated using density functional theory (DFT) calculations. The ring-opening, CO 2 -insertion, and ring-closing steps of the process were extensively studied. Our work emphasizes the synergistic effect between V 8 -1 and n -Bu 4 NX (X = Br, I). Through the analysis of an independent gradient model based on Hirshfeld partition (IGMH), it was found that the attack of n -Bu 4 NX (X = Br, I) on C β of PO triggers a distinct attractive interaction between the active fragment and the surrounding framework, serving as the primary driving force for the ring opening of PO. Furthermore, the effect of different cocatalysts was explored, with n -Bu 4 NI being more favorable than n -Bu 4 NBr. Moreover, the role of V 8 -1 in the CO 2 cycloaddition reaction was clarified as not only acting as Lewis acid active sites but also serving as "electron sponges". This work is expected to advance the development of novel catalysts for organic carbonate formation.

Here, we explain why the Energy Gap Law and the energy inversion related to the charge-transfer state have opposite effects on the trend of nonradiative energy loss of organic solar cells. The root is the existing condition of energy inversion. There is indeed a certain probability of energy inversion, but it will eventually be implicit or explicit as determined by the hybridization, which depends on the electron-withdrawing unit of the donor, giving rise to different stacking sites. The triplet-state hybridization leads to an explicit characteristic, while singlet-state hybridization leads to an implicit characteristic.

Ex vivo tissue culture of the human corpus cavernosum (CC) can be used to explore the tissue structural changes and complex signaling networks. At present, artificial CC-like tissues based on acellular or three-dimensional (3D)-printed scaffolds are used to solve the scarcity of primary penis tissue samples. However, inconvenience and high costs limit the wide application of such methods. Here, we describe a simple, fast, and economical method of constructing artificial CC-like tissue. Human CC fibroblasts (FBs), endothelial cells (ECs), and smooth muscle cells (SMCs) were expanded in vitro and mixed with Matrigel in specific proportions. A large number of bubbles were formed in the mixture by vortexing combined with pipette blowing, creating a porous, spongy, and spatial structure. The CC FBs produced a variety of signaling factors, showed multidirectional differentiation potential, and grew in a 3D grid in Matrigel, which is necessary for CC-like tissue to maintain a porous structure as a cell scaffold. Within the CC-like tissue, ECs covered the surface of the lumen, and SMCs were located inside the trabeculae, similar to the structure of the primary CC. Various cell components remained stable for 3 days in vitro , but the EC content decreased on the 7 th day. Wingless/integrated (WNT) signaling activation led to lumen atrophy and increased tissue fibrosis in CC-like tissue, inducing the same changes in characteristics as in the primary CC. This study describes a preparation method for human artificial CC-like tissue that may provide an improved experimental platform for exploring the function and structure of the CC and conducting drug screening for erectile dysfunction therapy., (Copyright © 2024 Copyright: © The Author(s)(2024).)

The detection of ascorbic acid (AA), dopamine (DA), and uric acid (UA) is not only of great significance in the areas of biomedicine and neurochemistry but also helpful in disease diagnosis and pathology research. Due to their diverse structures, designability, and large specific surface areas, metal-organic frameworks (MOFs) have recently caught considerable attention in the electrochemical field. Herein, a family of heterometallic MOFs with amino modification, MIL-125(Ti-Al)- x NH 2 ( x = 0%, 25%, 50%, 75%, and 100%), were synthesized and employed as electrochemical sensors for the detection of AA, DA, and UA. Among them, MIL-125(Ti-Al)-75%NH 2 exhibited the most promising electrochemical behavior with 40% doping of carbon black in 0.1 M PBS (pH = 7.10), which displayed individual detection performance with wide linear detection ranges (1.0-6.5 mM for AA, 5-100 μM for DA and 5-120 μM for UA) and low limits of detection (0.215 mM for AA, 0.086 μM for DA, and 0.876 μM for UA, S/N = 3). Furthermore, the as-prepared MIL-125(Ti-Al)-75%NH 2 /GCE provided a promising platform for future application in real sample analysis, owing to its excellent anti-interference performance and good stability.

Carbon nanorings have attracted substantial interest from synthetic chemists due to their unique topological structures and distinct physical properties. An intriguing π-conjugated double-nanoring structure, denoted as [8]CPP-[10]cyclacene, was constructed via the integration of [8]cycloparaphenylene ([8]CPP) into [10]cyclacene. Using the external electric field stimuli-responsiveness of [8]CPP-[10]cyclacene, directional charge transfer can be induced, resulting in the emergence of intriguing properties. The effects of the external electric field in three specific directions were explored, vertically in the [8]CPP unit ( F y ), vertically in the [10]cyclacene unit ( F z ), and horizontally along the double nanorings diameter ( F x ). Interestingly, the external electric field vertically to the [10]cyclacene unit significantly enhanced the first hyperpolarizability ( β tot ) compared to that vertically to the [8]CPP unit. Notably, [8]CPP-[10]cyclacene under F x exhibited significantly larger the β tot values (1.48 × 10 5 a.u.) than those of vertical F y and F z . This work opens up a wide range of nonlinear optics, making it a compelling area to explore in the field of carbon nanomaterials.

Catalytic hydrogenation of nitrobenzene (Ph-NO 2 ) to aniline (Ph-NH 2 ) is a model reaction in the field of catalysis, in which the development of efficient catalysts remains a great challenge due to the lack of strategies to solve activity and selectivity problems. In this work, the mechanism of Ph-NO 2 hydrogenation over Pt 1 supported on phosphomolybdic acid (α-PMA) was proposed by density functional theory (DFT) calculations. The results show that the dissociation of the first and second N-O bonds is triggered by single H-induced and double H-induced mechanisms, respectively. The limiting potential of the reaction process is -0.19 V, which is the smallest potential in the field of Ph-NO 2 reduction reaction to date. In the whole reaction process, the catalytic active site is the Pt atom, and polyoxometalate plays the role of an electronic sponge in the reaction. Additionally, based on experimentally confirmed Pt 1 /Na 3 PMA, the reduction capacity of Pd 1 /Na 3 PMA toward Ph-NO 2 was predicted by DFT calculation. The distinctive adsorption patterns of Ph-NO 2 on Pt 1 /Na 3 PMA and Pd 1 /Na 3 PMA were elucidated using the DOS diagram and fragment molecular orbital analysis. We anticipate that our theoretical calculations can provide novel perspectives for experimental researchers.

Developing highly efficient, stable, and cost-effective two-dimensional (2D) conjugated polymers (CPs) for overall water splitting (OWS) is critical for producing clean and renewable hydrogen energy, yet it remains a great challenge. Here, we designed eight 2D CPs through the topological assembly of diacetylene and benzene-derived molecular linkers that can offer active sites for hydrogen and oxygen evolution reactions, and explored their structural, electronic, optical, and photocatalytic OWS properties by performing first-principles computations. It is shown that incorporating benzo-heterocyclic rings into CPs can significantly modulate the electronic structures of CPs and broaden the spectral absorption, suitable for visible-light-driven OWS. Remarkably, through a range of screening criteria, including stability, electronic band structures, band edge alignments, and photocatalytic activity, we found that CP-4 based on diacetylene and benzotrifuran can spontaneously trigger the OWS in a neutral environment under its own light-induced bias, eliminating the need for sacrificial agents or cocatalysts. Specifically, the HER active site is primarily located at diacetylene moieties, while the OER active site is mainly concentrated on the benzo-heterocyclic rings. Moreover, the ideal STH efficiency for OWS on CP-4 was estimated to be 13.87%, highlighting its potential as a prospective photocatalyst for large-scale industrial OWS. Our findings open a door to the rational design of novel polymer photocatalysts for OWS.

In this study, a new cobalt-based metal-organic framework ( JLNU-500 ), [Co 2 (OH)(PBA)(AIP)]·3DMA·0.75H 2 O (4-(pyridin-4-yl) benzoic acid (HPBA), 5-aminoisophthalic acid (H 2 AIP) and N , N -dimethylacetamide (DMA)), was fabricated using a solvothermal method. JLNU-500 has 3D network architecture with 1D nanopore channels. The prepared JLNU-500 can activate peroxymonosulfate (PMS) for Rhodamine B (RhB) dye decolorization. Interestingly, catalyst JLNU-500 exhibited high efficiency for PMS activation, and nearly 100% (above 99.8%) removal of RhB with a high concentration (50.0 mg L -1 , 100 mL) was achieved within 6 min. The reaction rate constant of the JLNU-500 /PMS system was 1.02 min -1 calculated based on the pseudo-first-order kinetics, which is higher than that of the other reported catalysts. Furthermore, the factors, which could influence PMS activation were also investigated, such as PMS dosage, catalyst dosage, pollutant RhB concentration, reaction temperature and solution pH. More importantly, the radical trapping experiments ferreted out that sulfate (SO 4 ˙ - ) and hydroxyl (˙OH) radicals were the dominating oxidants in the removal of RhB. Moreover, the possible degradation mechanism was elucidated. This study provides new prospects for fabricating new MOFs that can potentially be employed for high-efficiency catalytic oxidation as heterogeneous catalysts.

Recently, non-fullerene-based organic solar cells (OSCs) have made great breakthroughs, and small structural differences can have dramatic impacts on the power conversion efficiency (PCE). We take ITIC and its isomers as examples to study their effects on the performance of OSCs. ITIC and NFBDT only differed in the side chain position, and they were used as models with the same donor molecule, PBDB-T , to investigate the main reasons for the difference in their performance in terms of theoretical methods. In this work, a detailed comparative analysis of the electronic structure, absorption spectra, open circuit voltage and interfacial parameters of the ITIC and NFBDT systems was performed mainly by combining the density functional theory/time-dependent density functional theory and molecular dynamics simulations. The results showed that the lowest excited state of the ITIC molecule possessed a larger ∆ q and more hybrid FE/CT states, and PBDB-T/ITIC had more charge separation paths as well as a larger k CS and smaller k CR . The reason for the performance difference between PBDB-T/ITIC and PBDB-T/NFBDT was elucidated, suggesting that ITIC is a superior acceptor based on a slight modulation of the side chain and providing a guiding direction for the design of superior-performing small molecule acceptor materials.

Metal-organic frameworks constructed from Zr usually possess excellent chemical and physical stability. Therefore, they have become attractive platforms in various fields. In this work, two families of hybrid materials based on ZrSQU have been designed and synthesized, named Im@ZrSQU and Cu@ZrSQU, respectively. Im@ZrSQU was prepared through the impregnation method and employed for proton conduction. Im@ZrSQU exhibited terrific proton conduction performance in an anhydrous environment, with the highest proton conduction value of 3.6 × 10 -2 S cm -1 at 110 °C. In addition, Cu@ZrSQU was synthesized via the photoinduction method for the photoreduction of CO 2 , which successfully promoted the conversion of CO 2 into CO and achieved the CO generation rate of up to 12.4 μmol g -1 h -1 . The photocatalytic performance of Cu@ZrSQU is derived from the synergistic effect of Cu NPs and ZrSQU. Based on an in-depth study and discussion toward ZrSQU, we provide a versatile platform with applications in the field of proton conduction and photocatalysis, which will guide researchers in their further studies.

Precise synthesis of polyoxometalates (POMs) is important for the fundamental understanding of the relationship between the structure and function of each building motif. However, it is a great challenge to realize the atomic-level tailoring of specific sites in POMs without altering the major framework. Herein, we report the case of Ce-mediated molecular tailoring on gigantic {Mo 132 }, which has a closed structural motif involving a never seen {Mo 110 } decamer. Such capped wheel {Mo 132 } undergoes a quasi-isomerism with known {Mo 132 } ball displaying different optical behaviors. Experiencing an 'Inner-On-Outer' binding process with the substituent of {Mo 2 } reactive sites in {Mo 132 }, the site-specific Ce ions drive the dissociation of {Mo 2 * } clipping sites and finally give rise to a predictable half-closed product {Ce 11 Mo 96 }. By virtue of the tailor-made open cavity, the {Ce 11 Mo 96 } achieves high proton conduction, nearly two orders of magnitude than that of {Mo 132 }. This work offers a significant step toward the controllable assembly of POM clusters through a Ce-mediated molecular tailoring process for desirable properties., (© 2023. Springer Nature Limited.)

In this work, we innovatively assembled two types of traditional photosensitizers, that is pyridine ruthenium/ferrum (Ru(bpy) 3 2+ /Fe(bpy) 3 2+ ) and porphyrin/metalloporphyrin complex (2HPor/ZnPor) by covalent linkage to get a series of dual photosensitizer-based three-dimensional metal-covalent organic frameworks (3D MCOFs), which behaved strong visible light-absorbing ability, efficient electron transfer and suitable band gap for highly efficient photocatalytic hydrogen (H 2 ) evolution. Rubpy-ZnPor COF achieved the highest H 2 yield (30 338 μmol g -1  h -1 ) with apparent quantum efficiency (AQE) of 9.68 %@420 nm, which showed one of the best performances among all reported COF based photocatalysts. Furthermore, the in situ produced H 2 was successfully tandem used in the alkyne hydrogenation with ≈99.9 % conversion efficiency. Theoretical calculations reveal that both the two photosensitizer units in MCOFs can be photoexcited and thus contribute optimal photocatalytic activity. This work develops a general strategy and shows the great potential of using multiple photosensitive materials in the field of photocatalysis., (© 2023 Wiley-VCH GmbH.)

Two-photon photodynamic therapy (TP-PDT), as a treatment technology with deep penetration and less damage, provides a broad prospect for cancer treatment. Nowadays, the development of TP-PDT suffers from the low two-photon absorption (TPA) intensity and short triplet state lifetime of photosensitizers (PSs) used in TP-PDT. Herein, we propose some novel modification strategies based on the thionated NpImidazole (the combination of naphthalimide and imidazole) derivatives to make efforts on those issues and obtain corresponding fluorescent probes for detecting ClO - and excellent PSs for TP-PDT. Density functional theory (DFT) and time-dependent DFT (TD-DFT) are used to help us characterize the photophysical properties and TP-PDT process of the newly designed compounds. Our results show that the introduction of different electron-donating groups at the position 4 of NpImidazole can effectively improve their TPA and emission properties. Specifically, 3s with a N , N -dimethylamino group has a large triplet state lifetime (τ = 699 μs) and TPA cross section value (δ TPA = 314 GM), which can effectively achieve TP-PDT; additionally, 4s (with electron-donating group 2-oxa-6-azaspiro[3.3]heptane in NpImidazole) effectively realizes the dual-function of a PS for TP-PDT (τ = 25,122 μs, δ TPA = 351 GM) and a fluorescent probe for detecting ClO - (Φ f = 29% of the product 4o ). Moreover, an important problem is clarified from a microscopic perspective, that is, why the transition property of 3s and 4s ( 1 π-π*) from S 1 to S 0 is different from that of 1s and 2s ( 1 n-π*). It is hoped that our work can provides valuable theoretical clues for the design and synthesis of heavy-atom-free NpImidazole-based PSs and fluorescent probes for the detection of hypochlorite.

Starting from the need for emergency rescue information transmission in tunnel engineering accidents, this article focuses on researching and solving the technical problems of information transmission between rescue personnel and trapped personnel after tunnel engineering collapse accidents, before and during the rescue process. The research objects are the information transmission channel and grounding electrode in the earth current field information transmission technology, and the electromagnetic characteristics of the earth medium and the electrical performance of the grounding electrode are studied and analyzed using the electromagnetic simulation software Maxwell based on finite element algorithm, establish a three-dimensional model based on the transmission of current field information of the ground electrode, analyze the effects of the electrode array, electrode depth, and radius on impedance. Research has shown that the impedance of the earth is related to the resistivity of the medium and is not a human-controllable factor. To reduce the contact impedance of an electric dipole antenna, one should start with the contact impedance of the earth electrode. The impedance of the transmitting end is an important factor affecting the efficiency of information transmission; parallel connection of multiple grounding electrodes, increasing the depth of grounding electrode penetration into the soil layer, and increasing the radius between grounding electrode pairs are all effective methods to reduce the contact impedance of electric dipole antennas, thereby improving information transmission capacity. To achieve wireless information transmission through the stratum, by appropriately selecting the operating frequency of electromagnetic waves, a certain distance of signal transmission can be achieved.

Photodynamic therapy (PDT) relying on photosensitizer-induced production of reactive oxygen species (ROS) for killing cancer cells has emerged as a non-invasive anti-cancer strategy. Compared with oxygen-dependent type-II photosensitizers (PSs) for PDT, the development of intrinsic oxygen-independent type-I ones is highly desired but remains a challenge. In this work, two netural Ir(III) complexes that can produce type-I reactive oxygen species, namely MPhBI-Ir-BIQ (Ir-1) and NPhBI-Ir-BIQ (Ir-2), were synthesized. Bright deep-red emitting nanoparticles with moderate particle size are beneficial for imaging-guided PDT. In in vitro experiments, importantly, the excellent biocompatibility, the targeting of lipid droplets (LDs), and the type-I ⋅OH and O 2 ⋅ - generation promoted effective photodynamic activity. This work will guide the building of type-I Ir(III) complexes PSs and can provide advantages for potential clinical applications under hypoxic conditions., (© 2023 Wiley-VCH GmbH.)

ITIC-series nonfullerene organic photovoltaics (NF OPVs) have realized the simultaneous increases of the short-circuit current density ( J SC ) and open-circuit voltage ( V OC ), called the positive correlation between J SC and V OC , which could improve the power conversion efficiency (PCE). However, it is complicated to predict the formation of positive correlation in devices through simple calculations of single molecules due to their dimensional differences. Here, a series of symmetrical NF acceptors blended with the PBDB-T donor were chosen to establish an association framework between the molecular modification strategy and positive correlation. It can be found that the positive correlation is modification site-dependent following the energy variation at the different levels. Furthermore, to illustrate a positive correlation, the energy gap differences (Δ E g ) and the energy level differences of the lowest unoccupied molecular orbitals (Δ E LUMO ) between the two changed acceptors were proposed as two molecular descriptors. Combined with the machine learning model, the accuracy of the proposed descriptor is more than 70% for predicting the correlation, which verifies the reliability of the prediction model. This work establishes the relative relationship between two molecular descriptors with different molecular modification sites and realizes the prediction of the trend of efficiency. Therefore, future research should focus on the simultaneous enhancement of photovoltaic parameters for high-performance NF OPVs.

Objective: Fondaparinux is a synthetic anticoagulant for the prevention of venous thromboembolism (VTE), and its administration in Chinese cancer patients is rarely reported. This study aimed to assess the efficacy and safety of fondaparinux in preventing VTE in Chinese cancer patients., Methods: A total of 224 cancer patients who received fondaparinux treatment were reviewed in this single-arm, multicenter, retrospective study. Meanwhile, VTE, bleeding, death, and adverse events of those patients in the hospital and at 1 month after treatment (M1) were retrieved, respectively., Results: The in-hospital VTE rate was 0.45% and there was no (0.00%) VTE occurrence at M1. The in-hospital bleeding rate was 2.68%, among which the major bleeding rate was 2.23% and the minor bleeding rate was 0.45%. Moreover, the bleeding rate at M1 was 0.90%, among which both the major and minor bleeding rates were 0.45%. The in-hospital death rate was 0.45% and the death rate at M1 was 0.90%. Furthermore, the total rate of adverse events was 14.73%, including nausea and vomiting (3.13%), gastrointestinal reactions (2.23%), and reduced white blood cells (1.34%)., Conclusion: Fondaparinux could effectively prevent VTE with low bleeding risk and acceptable tolerance in cancer patients., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Wang, Su, Xie, Li, Pan, Xu, Chen and Cheng.)

To elucidate the luminescence mechanism of highly efficient blue Cu(N^N)(POP) + -type thermally activated delayed fluorescence (TADF) materials, we have selected Cu(pytfmpz)(POP) + ( 1 ) and Cu(pympz)(POP) + ( 2 ) as targets to investigate the photophysical properties in both solution and solid phases. The self-consistent electrostatic potential (ESP) embedded charge within the quantum mechanics/molecular mechanics (QM/MM) method demonstrates a greater advantage over the charge equilibrium (QEQ) in accurately calculating atomic charges and reasonably describing the polarization effect, ultimately resulting in a favorable consistency between simulation and experimental measurements. After systematic and quantitative simulation, it has been found that complex 2 , with an electron-donating group of -CH 3 , exhibits a much more blue-shifted spectrum and a significantly enhanced efficiency in comparison to complex 1 with -CF 3 . This is due to the widened HOMO-LUMO gap as well as the narrowed energy gap between the lowest singlet and triplet excited states (Δ E ST ), respectively. Then, the designed complex 3 is introduced with a stronger electron donor and larger tert -butyl group, which plays a key role in simultaneously suppressing the structural distortion and reducing the Δ E ST . This leads to a faster reverse intersystem crossing process than that of the two experimental complexes in solution, turning out to be a new deep-blue-emitting material with excellent TADF performance.

Metal-organic frameworks (MOFs) as types of proton conductive materials have attracted much attention. Here, an acylamide-functionalized 3D MOF, [Ni 3 (TPBTC) 2 (stp) 2 (H 2 O) 4 ]·2DMA·32H 2 O, has been successfully constructed via combining Ni(NO 3 ) 2 , TPBTC (TPBTC = benzene-1,3,5-tricarboxylic acid tris-pyridin-4-ylamide) and 2-H 2 stp (2-H 2 stp = 2-sulfoterephthalic acid monosodium salt) under solvothermal conditions. Single-crystal X-ray diffraction revealed that there are uncoordinated guest DMA molecules in the pores of the compound. On removal of guest DMA molecules, the proton conductivity of the compound increased to 2.25 × 10 -3 S cm -1 at 80 °C and 98% RH which is about 110 times that of the original material. It is hoped that this work can provide essential insight for designing and obtaining improved crystalline-state proton conducting materials by considering the influences of guest molecules on proton conduction properties of porous materials.

Purpose. This dosimetric study is intended to lower the modulation factor in lung SBRT plans generated in the Eclipse TPS that could replace highly modulated plans that are prone to the interplay effect. Materials and methods. Twenty clinical lung SBRT plans with high modulation factors (≥4) were replanned in Varian Eclipse TPS version 15.5 utilizing 2 mm craniocaudal and 1 mm axial block margins followed by light optimization in order to reduce modulation. A unique plan optimization methodology, which utilizes a novel shell structure (OptiForR 50 ) for R 50% optimization in addition to five consecutive concentric 5 mm shells, was utilized to control dose falloff according to RTOG 0813 and 0915 recommendations. The prescription varied from 34-54 Gy in 1-4 fractions, and the dose objectives were PTV D 95% = Rx, PTV D max < 140% of Rx, and minimizing the modulation factor. Plan evaluation metrics included modulation factor, CI RTOG , homogeneity index (HI), R 50% , D 2cm , V 105% , and lung V 8-12.8Gy (Timmerman Constraint). A random-intercept linear mixed effects model was used with a p ≤ 0.05 threshold to test for statistical significance. Results. The retrospectively generated plans had significantly lower modulation factors (3.65 ± 0.35 versus 4.59 ± 0.54; p < 0.001), lower CI RTOG (0.97 ± 0.02 versus 1.02 ± 0.06; p = 0.001), higher HI (1.35 ± 0.06 versus 1.14 ± 0.04; p < 0.001), lower R 50% (4.09 ± 0.45 versus 4.56 ± 0.56; p < 0.001), and lower lungs V 8-12.8Gy (Timmerman) (4.61% ± 3.18% versus 4.92% ± 3.37%; p < 0.001). The high dose spillage V 105% was borderline significantly lower (0.44% ± 0.49% versus 1.10% ± 1.64%; p = 0.051). The D 2cm was not statistically different (46.06% ± 4.01% versus 46.19% ± 2.80%; p = 0.835). Conclusion. Lung SBRT plans with significantly lower modulation factors can be generated that meet the RTOG constraints, using our planning strategy., (© 2023 IOP Publishing Ltd.)

Purpose: Child head injury under impact scenarios (e.g. falls, vehicle crashes, etc.) is an important topic in the field of injury biomechanics. The head of piglet was commonly used as the surrogate to investigate the biomechanical response and mechanisms of pediatric head injuries because of the similar cellular structures and material properties. However, up to date, piglet head models with accurate geometry and material properties, which have been validated by impact experiments, are seldom. We aim to develop such a model for future research., Methods: In this study, first, the detailed anatomical structures of the piglet head, including the skull, suture, brain, pia mater, dura mater, cerebrospinal fluid, scalp and soft tissue, were constructed based on CT scans. Then, a structured butterfly method was adopted to mesh the complex geometries of the piglet head to generate high-quality elements and each component was assigned corresponding constitutive material models. Finally, the guided drop tower tests were conducted and the force-time histories were ectracted to validate the piglet head finite element model., Results: Simulations were conducted on the developed finite element model under impact conditions and the simulation results were compared with the experimental data from the guided drop tower tests and the published literature. The average peak force and duration of the guide drop tower test were similar to that of the simulation, with an error below 10%. The inaccuracy was below 20%. The average peak force and duration reported in the literature were comparable to those of the simulation, with the exception of the duration for an impact energy of 11 J. The results showed that the model was capable to capture the response of the pig head., Conclusion: This study can provide an effective tool for investigating child head injury mechanisms and protection strategies under impact loading conditions., (Copyright © 2022 Chinese Medical Association. Production and hosting by Elsevier B.V. All rights reserved.)

In order to resolve the problem that the sample of image for internal detection of DN100 buried gas pipeline microleakage is single and difficult to identify, a recognition method of microleakage image of the pipeline internal detection robot is proposed. First, nongenerative data augmentation is used to expand the microleakage images of gas pipelines. Secondly, a generative data augmentation network, Deep Convolutional Wasserstein Generative Adversarial Networks (DCWGANs), is designed to generate microleakage images with different features for detection in the pipeline of gas pipelines to achieve sample diversity of microleakage images of gas pipelines. Then, a bi-directional feature pyramid network (BiFPN) is introduced into You Only Look Once (YOLOv5) to retain more deep feature information by adding cross-scale connecting lines in the feature fusion structure; finally, a small target detection layer is constructed in YOLOv5 so that more shallow feature information can be retained to achieve small-scale leak point recognition. The experimental results show that the precision of this method for microleak identification is 95.04%, the recall rate is 94.86%, the mAP value is 96.31%, and the minimum size of identifiable leaks is 1 mm.

Gliomas account for about 80% of malignant brain tumors. The incidence of a new brain tumor is 6.4 per 100,000 persons per year with an overall 5-year survival rate of 33.4%. Regardless of the great advances that have been made in recent years, the causes and pathogenesis of glioma remain unclear. Here we study how phosphoglycerate mutase 4 (PGAM4) contributes to glioma. Using a variety of methods to examine glioma cell viability, proliferation, apoptosis, glycolysis, as well as ChIP coanalysis with modified histone H3, we showed that PGAM4 was significantly upregulated in patients with glioma and associated with poor survival. Silencing PGAM4 attenuated cell viability, proliferation, and glycolysis in T98G cells and suppressed tumor growth in vivo, while overexpressing PGAM4 promoted cell viability, proliferation, and glycolysis in U251 cells via regulating glycolysis pathway. Study also revealed that PGAM4 was regulated by EP300-mediated modifications of H3K27ac. PGAM4 silencing inhibited cell viability and proliferation, suppressed tumor growth, and decreased chemoresistance to temozolomide in glioma cells through suppressing glycolysis., (© 2022 International Federation for Cell Biology.)

Host-guest doping systems with phthalimides ( BI ) and N -methylphthalimide ( NMeBI ) as the host and 1,8-naphthalimide ( NI ) and 4-bromo-1,8-naphthalimide ( 4BrNI ) as the guest have been developed. The 0.2% NI/BI (molar ratio) with a strong C=O···H-N hydrogen bond exhibited a phosphorescence quantum efficiency (29.2%) higher than that of NI/NMeBI with a weak C=O···H-C hydrogen bond (10.1%). A similar trend was observed in the 4BrNI guest system. A remarkable phosphorescent efficiency of 42.1% was achieved in a 0.5% 4BrNI/BI composite, which represents the highest value in NI -based phosphors. This research indicates stronger hydrogen bonding may have a greater contribution in boosting the phosphorescence efficiency.

The exciplex-thermally activated delayed fluorescence (exciplex-TADF) system is an excellent candidate for the fabrication of high-efficiency organic light-emitting diodes (OLEDs) because of its more easily achieved small singlet-triplet energy splitting (Δ E ST ) and doping control. However, exciplex-TADF is still faced with the problems of low external quantum efficiency (η ext ) and unclear effect of structure modification in electron acceptors. Herein, we provide a steric hindrance increase strategy to obtain high-efficiency exciplex emissions. Through introducing a 9-phenylfluorene group into N -ethylcarbazole of the dicyano-substituted 9-phenylfluorene, an electron acceptor material with increased steric hindrance is obtained, which helps the exciplex harvest a larger driving force and higher emission efficiencies. Encouragingly, the obtained OLED displays a maximum η ext of 25.8%, which is one of the best efficiency values among reported exciplex-OLEDs, simultaneously possessing excellent current efficiency of 83.6 cd A -1 and power efficiency of 93.7 lm W -1 . It is expected that this work will offer a new avenue for designing electron acceptors for highly efficient exciplex emissions.

Interest in defect engineering for lithium-ion battery (LIB) materials is sparked by its ability to tailor electrical conductivity and introduce extra active sites for electrochemical reactions. However, harvesting excessive intrinsic defects in the bulk of the electrodes rather than near their surface remains a long-standing challenge. Here, a versatile strategy of quenching is demonstrated, which is exercised in lithium titanate (Li 4 Ti 5 O 12 , LTO), a renowned anode for LIBs, to achieve off-stoichiometry in the interior region. In situ synchrotron analysis and atomic-resolution microscopy reveal the enriched oxygen vacancies and cation redistribution after ice-water quenching, which can facilitate the native unextractable Li ions to participate in reversible cycling. The fabricated LTO anode delivers a sustained capacity of 202 mAh g -1 in the 1.0-2.5 V range with excellent rate capability and overcomes the poor cycling stability seen in conventional defective electrodes. The feasibility of tuning the degree of structural defectiveness via quenching agents is also proven, which can open up an intriguing avenue of research to harness the intrinsic defects for improving the energy density of rechargeable batteries., (© 2022 Wiley-VCH GmbH.)

The anhydrous proton conductivity of Im@IEF-11 resulting from the integration of imidazole and porous IEF-11 has been investigated, and the highest proton conductive value can reach up to 7.64 × 10 -2 S cm -1 . Furthermore, IEF-11 is also developed to reduce CO 2 due to its reasonable structure and suitable energy band, and its CO formation rate is 31.86 μmol g -1 h -1 .

Iridium/nickel (Ir/Ni) metallaphotoredox dual catalysis overcomes the challenging reductive elimination (RE) of Ni(II) species and has made a breakthrough progress to construct a wide range of C-X (X = C, N, S, and P) bonds. However, the corresponding reaction mechanisms are still ambiguous and controversial because the systematic research on the nature of this synergistic catalysis is not sufficient. Herein, Ir III /Ni II and Ir III /Ni 0 metallaphotoredox catalysis have been theoretically explored taking the aryl esterification reaction of benzoic acid and aryl bromide as an example by a combination of density functional theory (DFT), molecular dynamics, and time-dependent DFT computations. It is found that an electron-transfer mechanism is applicable to Ir III /Ni II metallaphotoredox catalysis, but an energy-transfer mechanism is applicable to Ir III /Ni 0 combination. The Ir III /Ni II metallaphotoredox catalysis succeeds to construct a Ni I -Ni III catalytic cycle to avoid the challenging RE of Ni(II) species, while the RE occurs from triplet excited-state Ni(II) species in the Ir III /Ni 0 metallaphotoredox catalysis. In addition, the lower lowest unoccupied molecular orbital energy level of Ni(III) species than that of Ni(II) species accelerates RE from Ni(III) one. The triplet excited-state Ni(II) species can resemble a Ni(III) center, considering the metal-to-ligand charge transfer character to promote the RE.

Building metal-organic frameworks (MOFs) covalently modified by onium halides is a promising approach to develop efficient MOF-based heterogeneous catalysts for the cycloaddition of CO 2 to epoxides (CCE) into cyclic carbonates. Herein, we report a novel zirconium-based MOF covalently modified by methyl pyridinium bromide, Zr 6 O 4 (OH) 4 (MPTDC) 2.2 (N-CH 3 -MPTDC) 3.8 Br 3.8 ((Br-)CH3-Pyridinium-MOF-1), where MPTDC denotes 3-methyl-4-pyridin-4-yl-thieno[2,3- b ] thiophene-2,5-dicarboxylate. The structure and composition of this complex were fully characterized with PXRD, NMR, XPS, TEM and so on. CO 2 adsorption experiments show that (Br-)CH3-Pyridinium-MOF-1 has a higher affinity for CO 2 than its electrically neutral precursor, which should be attributed to the fact that charging frameworks containing pyridinium salt have stronger polarization to CO 2 . (Br-)CH3-Pyridinium-MOF-1 integrated reactive Lewis acid sites and Br - nucleophilic anions and exhibited efficient catalytic activity for CCE under ambient pressure in the absence of co-catalysts and solvents. Furthermore, (Br-)CH3-Pyridinium-MOF-1 was recycled after five successive cycles without substantial loss in catalytic activity. The corresponding reaction mechanism also was speculated.