Gemini cationic surfactant of 1, 3-bis (dodecyl dimethyl ammonium chloride) propane as a novel excellent inhibitor for the corrosion of cold rolled steel in HCl solution.

Gemini surfactants have become the research focus of novel excellent inhibitors because of their special structure (two amphiphilic moieties covalently connected at head group by a spacer) and excellent surface properties. It is proved by theoretical calculations that 1, 3-bis (dodecyl dimethyl ammonium chloride) propane (BDDACP) molecules can perform electron transfer with Fe (110). And it has a small fraction free volume, thus greatly reducing the diffusion and migration degree of corrosive particles. The potentiodynamic polarization curve showed that coefficients of cathodic and anodic reaction less than 1 and polarization resistance increased to 1602.9 Ω cm-2 after added BDDACP, confirming that BDDACP significantly inhibited the corrosion reaction by occupying the active site. The electrochemical impedance spectrum of imperfect semi-circle shows that the system resistance increases and double layer capacitance after added BDDACP. Weight loss tests also confirmed that BDDACP forms protective film by occupying the active sites on steel surface, and the maximum inhibition efficiency is 92 %. Comparison of the microscopic morphology showed that steel surface roughness was significantly reduced after added BDDACP. The results of time-of-flight secondary ion mass spectrometry show that steel surface contains some elements from BDDACP, which confirms the adsorption of BDDACP on steel surface.

N-doped Cu2O with the tunable Cu0 and Cu+ sites for selective CO2 electrochemical reduction to ethylene.

The electrochemical carbon dioxide reduction reaction (CO2RR) to high value-added fuels or chemicals driven by the renewable energy is promising to alleviate global warming. However, the selective CO2 reduction to C2 products remains challenge. Cu-based catalyst with the specific Cu0 and Cu+ sites is important to generate C2 products. This work used nitrogen (N) to tune amounts of Cu0 and Cu+ sites in Cu2O catalysts and improve C2-product conversion. The controllable Cu0/Cu+ ratio of Cu2O catalyst from 0.16 to 15.19 was achieved by adjusting the N doping amount using NH3/Ar plasma treatment. The major theme of this work was clarifying a volcano curve of the ethylene Faraday efficiency as a function of the Cu0/Cu+ ratio. The optimal Cu0/Cu+ ratio was determined as 0.43 for selective electroreduction CO2 to ethylene. X-ray spectroscopy and density functional theory (DFT) calculations were employed to elucidate that the strong interaction between N and Cu increased the binding energy of NCu bond and stabilize Cu+, resulting in a 92.3% reduction in the potential energy change for *CO-*CO dimerization. This study is inspiring in designing high performance electrocatalysts for CO2 conversion.

Rationally Designed Mo/Ru-Based Multi-Site Heterogeneous Electrocatalyst for Accelerated Alkaline Hydrogen Evolution Reaction.

The rational design of multi-site electrocatalysts with three different functions for facile H2O dissociation, H-H coupling, and rapid H2 release is desirable but difficult to achieve. This strategy can accelerate the sluggish kinetics of the hydrogen evolution reaction (HER) under alkaline conditions. To resolve this issue, a Mo/Ru-based catalyst with three different active sites (Ru/Mo2C/MoO2) is rationally designed and its performance in alkaline HER is evaluated. The experimental results and density functional theory calculations revealed that, at the heterogeneous Mo2C/MoO2 interface, the higher valence state of Mo (MoO2) and the lower valence state of Mo (Mo2C) exhibited strong OH- and H-binding energies, respectively, which accelerated H2O dissociation. Moreover, the interfacial Ru possessed an appropriate hydrogen binding energy for H-H coupling and subsequent H2 evolution. Thus, this catalyst significantly accelerated the Volmer step and the Tafel step and, consequently, HER kinetics. This catalyst also demonstrated low overpotentials of 19 and 160 mV at current densities of 10 and 1000 mA cm-2, respectively, in alkaline media and long-term stability superior to that of most state-of-the-art alkaline HER electrocatalysts. This work provides a rational design principle for advanced multi-site catalytic systems, which can realize multi-electron electrocatalytic reactions.

Highly Efficient Electrocatalytic Nitrate Reduction to Ammonia: Group VIII-Based Catalysts.

The accumulation of nitrates in the environment causes serious health and environmental problems. The electrochemical nitrate reduction reaction (e-NO3RR) has received attention for its ability to convert nitrate to value-added ammonia with renewable energy. The key to effective catalytic efficiency is the choice of materials. Group VIII-based catalysts demonstrate great potential for application in e-NO3RR because of their high activity, low cost, and good electron transfer capability. This review summarizes the Group VIII catalysts, including monatomic, bimetallic, oxides, phosphides, and other composites. On this basis, strategies to enhance the intrinsic activity of the catalysts through coordination environment modulation, synergistic effects, defect engineering and hybridization are discussed. Meanwhile, the ammonia recovery process is summarized. Finally, the current research status in this field is prospected and summarized. This review aims to realize the large-scale application of nitrate electrocatalytic reduction in industrial wastewater.

Modes of occurrence of beryllium in the Ge-rich coal deposit, Lincang, SW China: Theoretical insight into organic association and distribution.

The coal-hosted germanium (Ge) deposit in Lincang, China, contains an abnormally high concentration of beryllium (Be), which is of significant organic affinity. However, the specific species of Be at the atomic scale remain unclear. In this study, thirteen model compounds representing O/S/N-containing functional groups in coal were calculated to probe the local environment of Be. The results indicate that hydroxyl and carboxyl groups are the primary acceptors of Be. Various Be-O complexes with a saturated four coordination of Be can achieve best stabilization. In contrast, the heteroatoms S and N are less likely to act as the acceptors for Be. In addition, the calculation results provide theoretical insights into the vertical distribution of Be. Unlike the upper coal seam, a fraction of Be in the middle and lower seams occurs in a mineral phase, which can be attributed to the limited capacity of organic matter to bond with all available Be. Furthermore, competition from other organically-associated metals, such as Ge and W, for bonding sites affects the local distribution of Be. This study reveals the molecular mechanism for Be enrichment in the organic matter of the Lincang Ge deposit, and suggests potential strategies for the removal of organically bonded Be in coal through the destruction of O-bridged complexes.

Synthesis of Indolyl Isothiocyanate and Its Inhibitory Activity against Fungi.

Based on previous research, this study synthesized 24 compounds by splicing the substructures of the indolyl group and the isothiocyanate group. Alternaria alternata, Phytophthora capsici, Botrytis cinerea, and Valsa mali were used to test the activity of the target compounds. At 100 µg/mL, compounds 8, 13, 14, and 17 exhibited excellent inhibitory effects of more than 80% on P. capsici, B. cinerea, and V. mail. The EC50 values of compounds 13 and 14 were 0.64 and 2.08 µg/mL, respectively. Potted antifungal activity demonstrated that compounds 13 and 14 had a protective effect of around 80% against B. cinerea at 200 µg/mL. Further physiological and biochemical studies on B. cinerea revealed that compound 13 thickened cell walls and caused mitochondrial vacuolization. Moreover, theoretical calculations indicated that the charge distribution of indolyl isothiocyanate compounds played a crucial role in the observed fungicidal activity. In summary, this study provided fundamental reference data for the derivative synthesis of these indolyl isothiocyanate compounds.

Natural α-Methylene-γ-Butyrolactone Analogues: Synthesis and Evaluation of Isoaurone Derivatives as Antifungal Agents.

In order to develop novel, efficient and green fungicides, a series of novel isoaurone derivatives were designed and synthesized, which were characterized by 1H and 13C NMR, high-resolution mass spectra and melting points. The target compounds showed different inhibitory activities against seven plant pathogenic fungi. Compounds 1, 12, 17, 20, 22, 24 and intermediate A showed more than 90% inhibition rates against S. s at 50 mg/L. Interestingly, compound 22 and intermediate A showed the great inhibitory effect against S. s with EC50 values of 4.65 and 4.24 mg/L, which were better than the lead compound isoaurone (EC50 = 15.62 mg/L). The EC50 values of compounds 17 and 24 against B. c were 13.94 and 22.13 mg/L. Moreover, compound 19 displayed significant antifungal activity against G. g with the EC50 value of 11.88 mg/L. Theoretical calculations by DFT revealed that the α, ß-unsaturated carbonyl bond and the benzyl ring are very importantly linked to the strength of the fungicidal activity. Therefore, this study identified a valuable antifungal lead compound for further development of green fungicides.

Relatively reliable and rapid identification of colorant compounds in food matrices by HPLC-DAD-QTOF-MS combined with theoretical calculation.

A new convenient method for identifying colorant compounds (CCs) in food matrices was developed using high-performance liquid chromatography with a diode array detector and quadrupole-time-of-flight mass spectrometer (HPLC-DAD-Q/TOF-MS) combined with theoretical calculations. A model sample containing three typical CCs was completely separated via HPLC-DAD. The obtained 3D ultraviolet-visible (UV-vis) spectra revealed the maximum absorption wavelengths (MAWs) of all CCs (yellow, 430 nm; red, 520 nm; blue, 620 nm) in the range of 400-800 nm, and their colors were determined based on their MAWs. Temporary structures of the CCs were obtained using Q/TOF-MS analysis. Theoretical calculations were then performed to obtain the theoretical MAWs and colors of the CCs according to their calculated UV-vis spectra based on temporary structures. The structures of the CCs were confirmed without the need for authoritative standards by comparing the consistency between their experimental and theoretical MAWs and colors. This method is particularly suitable for identifying CCs or compounds with UV-Vis absorption, including new compounds, compounds for which standards are difficult to obtain, and known compounds without reporting relevant molecular information.

Design, Synthesis, and Antifungal Evaluation of Novel Pyrazole-5-sulfonamide Derivatives for Plant Protection.

To develop further novel environmentally friendly antifungal agents with high efficacy, a series of pyrazole-5-sulfonamide derivatives were designed and synthesized by using the active molecules synthesized in previous works as lead compounds. Their antifungal activities were evaluated in vitro against ten highly destructive plant pathogenic fungi. The bioassay results indicated that more than half of the target compounds displayed potent antifungal activities (inhibition rate ≥85%) against Valsa mali and Sclerotinia sclerotiorum at 20 mg/L. Among them, compound C22 exhibited significant broad-spectrum antifungal activities against V. mali, S. sclerotiorum, Rhizoctonia solani, Botrytis cinerea, and Trichoderma viride, with EC50 values of 0.45, 0.49, 3.06, 0.57, and 1.43 mg/L, respectively. Moreover, compounds C21 and C22 exhibited remarkable protective effects on apple Valsa canker similar to tebuconazole (89.5%) at 50 mg/L. Preliminary antifungal mechanism investigations demonstrated that compound C22 may have inhibited V. mali mycelial growth by inducing oxidative damage to the mycelium and compromising the integrity of the cell membrane. Meanwhile, compounds C21 and C22 exhibited no obvious toxicity to worker bees (Apis mellifera ligustica). Taken together, these pyrazole-5-sulfonamide derivatives, particularly compound C22, possess huge potential to be developed as novel environmentally friendly fungicides with high efficacy.

Turning Waste into Treasure: Invasive Plant Ambrosia trifida L Leaves as a High-Efficiency Inhibitor for Steel in Simulated Pickling Solutions.

High toxicity is the main reason for the limited application of traditional corrosion inhibitors. Herein, it is critical to find a green, efficient, and long-term stable alternative substitute for the hazardous and conventional corrosion inhibitor. Ambrosia trifida L is widely distributed in fields and riverside wetlands as an invasive plant in China. According to the concept of turning waste into treasure, the extract of Ambrosia trifida L leaves (ATL) has the potential to address this issue due to its natural origin and abundant presence of heterocyclic organics. Therefore, ATL, as a green corrosion inhibitor, is prepared for the first time via a simple water-based extraction method. FT-IR (Fourier transform infrared spectroscopy) and UV-Vis (UV-visible) indicate that ATL extract contains abundant heterocyclic organics with conjugated structures, which exhibit the potential to become a high-efficiency inhibitor. Notably, the active sites of ATL molecules and their interaction with Q235 steel at the molecular/atomic level are revealed via theoretical calculations. The highest Ebinding value observed for the major components in the ATL extract is 259.66 kcal/mol, implying a significant adsorption capacity. The electrochemical results verify that microdose ATL extract can prominently inhibit steel corrosion, and the highest inhibition efficiency (η) is 97.5% (1000 mg/L). Following immersion for 24 h, the η value is enhanced to 99.0%, indicating a reliable and long-term ATL extract protection film is formed on the steel surface in harsh acidic solutions. The results of the weight loss, SEM (scanning electron microscope), and LSCM (laser scanning confocal microscopy) are consistent with the above conclusions. Finally, this study anticipates providing theoretical support for developing novel green plant extract inhibitors and aiding in their application in industrial pickling environments.

Interfacial interactions of nanoscale zero-valent iron particles with clay minerals in the aquatic environments: Experimental and theoretical calculation study.

The environmental transport and fate of nanoscale zero-valent iron particles (nZVI) in soil and groundwater can be altered by their hetero-aggregation with clay mineral particles (CMP). This study examines the interactions between bare or carboxymethyl cellulose (CMC)-coated nZVI with typical CMP, specifically kaolinite and montmorillonite. Methods include co-settling experiments, aggregation kinetic studies, electron microscopy, Derjaguin-Landau-Verwey-Overbeek (DLVO) and extended DLVO (EDLVO) energy analysis, and density functional theory calculations, focusing on the pH dependency of these interactions. The EDLVO theory effectively described the interactions between nZVI and CMP in aquatic environments. Under acidic conditions (pH 3.5), the interfacial interaction between bare nZVI and kaolinite is regulated by van der Waals forces, while complexation, van der Waals forces, and electrostatic attraction govern the interaction of bare nZVI with montmorillonite, primarily depositing on the SiO face. In contrast, the positively charged AlO face and edge of CMP are the main deposition sites for CMC-coated nZVI through hydrogen bonding, van der Waals forces, and electrostatic attraction. At neutral (pH 6.5) and alkaline (pH 9.5) conditions, both bare and CMC-coated nZVI predominantly attach to the AlO face and edge, facilitated by complexation or hydrogen bonding, alongside van der Waals forces. The attachment of CMC-coated nZVI to CMP surfaces shows reversible aggregation or deposition due to the steric repulsion from the CMC coating. These findings hold significant implications for the environmental applications and risk of nZVI.

Hexagonal MoO3 Anode with Extremely High Capacity and Cyclability for Lithium-Ion Battery: A Combined Theoretical and Experimental Study.

It is essential and still remains a big challenge to obtain fast-charge anodes with large capacities and long lifespans for Li-ion batteries (LIBs). Among all of the alternative materials, molybdenum trioxide shows the advantages of large theoretical specific capacity, distinct tunnel framework, and low cost. However, there are also some key shortcomings, such as fast capacity decaying due to structural instability during Li insertion and poor rate performance due to low intrinsic electron conductivity and ion diffusion capability, dying to be overcome. A unique strategy is proposed to prepare Ti-h-MoO3-x@TiO2 nanosheets by a one-step hydrothermal approach with NiTi alloy as a control reagent. The density functional theory (DFT) calculations indicate that the doping of Ti element can make the hexagonal h-MoO3-x material show the best electronic structure and it is favor to be synthesized. Furthermore, the hexagonal Ti-h-MoO3-x material has better lithium storage capacity and lithium diffusion capacity than the orthogonal α-MoO3 material, and its theoretical capacity is more than 50% higher than that of the orthogonal α-MoO3 material. Additionally, it is found that Ti-h-MoO3-x@TiO2 as an anode displays extremely high reversible discharge/charge capacities of 1326.8/1321.3 mAh g-1 at 1 A g-1 for 800 cycles and 611.2/606.6 mAh g-1 at 5 A g-1 for 2000 cycles. Thus, Ti-h-MoO3-x@TiO2 can be considered a high-power-density and high-energy-density anode material with excellent stability for LIBs.

Theoretical insights into the linker effects on the turn-on fluorescence behaviors in pyridazinone-containing NO probes.

Fluorescent probes with preferred photophysical properties have attracted considerable attention for their advantages in real-time and accurate detection of signalling molecules in living organisms. Nitric oxide (NO) is a ubiquitous cellular messenger closely associated with many physiological and pathological processes. A NO fluorescent probe, PYSNO, based on the pyridazinone (PY) scaffold with o-phenylenediamine as the receptor and thiophene (S) as the linker has been synthesized. Inspired by the experimental guidance, three other dyes (PYSSNO, PYSONO and PYONO) were theoretically designed by replacing the S linker with thieno[3,2-b]thiophene (SS), thieno[3,2-b]thiophene 1,1-dioxide (SO) and thiophene 1,1-dioxide (O) groups. The photophysical properties were theoretically investigated in aqueous solution, by the combined time-dependent density functional theory, polarizable continuum model and thermal vibration correlation function approaches. Our results indicate that the emission wavelengths of all the designed dyes show red shifts due to either an increase in the conjugation length or electron-accepting ability of the linkers compared to PYSNO. The photoinduced electron transfer (PET) processes are all absent in these systems. PYSSNO and PYSONO are theoretically expected to be promising candidates for novel NO fluorescent probes, but the suitability of PYONO as a NO probe is compromised by the predicted non-luminescent emission before and after reaction with NO. Our study not only offers valuable insights into the detailed structure-property relationships, but also opens a new avenue for the rational design of efficient fluorescent sensors for NO detection.

Eddy Current Sensor Array for Electromagnetic Sensing and Crack Reconstruction with High Lift-Off in Railway Tracks.

A reliable and efficient rail track defect detection system is essential for maintaining rail track integrity and avoiding safety hazards and financial losses. Eddy current (EC) testing is a non-destructive technique that can be employed for this purpose. The trade-off between spatial resolution and lift-off should be carefully considered in practical applications to distinguish closely spaced cracks such as those caused by rolling contact fatigue (RCF). A multi-channel eddy current sensor array has been developed to detect defects on rails. Based on the sensor scanning data, defect reconstruction along the rails is achieved using an inverse algorithm that includes both direct and iterative approaches. In experimental evaluations, the EC system with the developed sensor is used to measure defects on a standard test piece of rail with a probe lift-off of 4-6 mm. The reconstruction results clearly reveal cracks at various depths and spacings on the test piece.

Recent Advances in Revealing the Electrocatalytic Mechanism for Hydrogen Energy Conversion System.

In light of the intensifying global energy crisis and the mounting demand for environmental protection, it is of vital importance to develop advanced hydrogen energy conversion systems. Electrolysis cells for hydrogen production and fuel cell devices for hydrogen utilization are indispensable in hydrogen energy conversion. As one of the electrolysis cells, water splitting involves two electrochemical reactions, hydrogen evolution reaction and oxygen evolution reaction. And oxygen reduction reaction coupled with hydrogen oxidation reaction, represent the core electrocatalytic reactions in fuel cell devices. However, the inherent complexity and the lack of a clear understanding of the structure-performance relationship of these electrocatalytic reactions, have posed significant challenges to the advancement of research in this field. In this work, the recent development in revealing the mechanism of electrocatalytic reactions in hydrogen energy conversion systems is reviewed, including in situ characterization and theoretical calculation. First, the working principles and applications of operando measurements in unveiling the reaction mechanism are systematically introduced. Then the application of theoretical calculations in the design of catalysts and the investigation of the reaction mechanism are discussed. Furthermore, the challenges and opportunities are also summarized and discussed for paving the development of hydrogen energy conversion systems.

Differentiation of Cis/trans-geometrical isomers in long-chain unsaturated fatty acids based on ion mobility and theoretical calculations.

In recent years, fatty acids containing conjugated CCs have attracted extensive research attention due to their biological activities against human diseases. However, their differentiation is challenging. This study developed a comprehensive analytical solution to accurately differentiate cis/trans-fatty acid isomers using ion mobility mass spectrometry (IM-MS) and theoretical calculations. Cis/trans-fatty acids were mobility-differentiated via simple complexation with 1,5,9-triazacyclododecane (9C3N) or 1,4,8,11-tetraazacyclotetradecane (10C4N) and metal ions, obtaining baseline separation with a peak-to-peak resolution of 0.35-0.92. Moreover, the conformation of the complexes was optimized theoretically, revealing different binding modes between the cis/trans-fatty acid-9C3N/10C4N-metal ion systems, yielding in-depth structural data on the complexes and elucidating the principles of mobility separation. Furthermore, the proposed method was assessed in terms of quantification, accuracy, and precision repeatability. Finally, the method was applied to analyze oil samples. Given its simplicity, speed, and lack of chemical derivatization or chromatographic separation, this technique has potential applications in food analysis.

Theoretical studies on the aqueous phase and graphene heterogeneous degradation of acrylamide and acrylonitrile by HO, ClO, and BrO radicals.

The newly discovered ClO• and BrO• contribute to pollutant degradation in advanced oxidation processes, while acrylamide (AM) and acrylonitrile (ACN) are always the focus of scientists concerned due to their continuous production and highly toxic effects. Moreover, various particles with a graphene-like structure are the companions of AM/ACN in dry/wet sedimentation or aqueous phase existence, which play an important role in heterogeneous oxidation. Thus, this work focuses on the reaction mechanism and environmental effect of AM/ACN with ClO•/BrO•/HO• in the water environment under the influence of graphene (GP). The results show that although the reactivity sequence of AM and ACN takes the order of with HO• > with BrO• > with ClO•, the easiest channel always occurs at the same C-position of the two reactants. The reaction rate constants (k) of AM with three radicals are 2 times larger than that with ACN, and amide groups have a better ability to activate CC bonds than cyanide groups. The existence of GP can accelerate the target reaction, and the k increased by 9-13 orders of magnitude. The toxicity assessment results show that the toxic effect of most products is lower than that of parent compounds, but the environmental risk of products from ClO•/BrO•-adducts is higher than those from HO•-adducts. The oxidative degradation process based on ClO• and BrO• deserves special attention, and the catalytic effect of GP and its derivatives on the oxidation process is non-negligible.

Synthesis of biscarbazole derivative, detection of the "on-off" sensor property of Cu2+ by fluorimetry, and anti-cancer evaluation.

Biscarbazole derivative probe (6) (Z)-2-(3-(((9-heptyl-9H-carbazol-3-yl)methylene)amino)-9H-carbazol-9-yl)ethan-1-ol containing an imine group, which is a sensitive and selective fluorescence chemosensor, was designed and synthesized for the effective evaluation of Cu2+ metal ion levels. The synthesized compounds were characterized using 1H NMR, 13C NMR, FT-IR, and MALDI-TOF MS (for compound 6) spectroscopic data. The interaction model between probe 6 and Cu2+ was determined by combining fluorescence methods, 1H NMR titration, Job's plot, and theoretical calculations. For probe 6, the fluorogenic recognition of Cu2+ was investigated by fluorescence spectroscopy, and the optical changes caused by Cu2+ ions were carried out in ACN/H2O (50:50) solution at pH 7.0. Fluorescence probe 6 was found to "turn-off" its fluorescence in the presence of paramagnetic Cu2+ ions. Probe 6 was determined to have a rapid response within 40s and showed a fluorescence response to Cu2+ with a low detection limit of 0.16 µM. Additionally, in vitro anticancer activity and cell imaging studies of probe 6 against the prostate cell line (PC-3) were performed.

NbC Nanoparticles Decorated Carbon Nanofibers as Highly Active and Robust Heterostructural Electrocatalysts for Ammonia Synthesis.

Transition-metal carbides with metallic properties have been extensively used as electrocatalysts due to their excellent conductivity and unique electronic structures. Herein, NbC nanoparticles decorated carbon nanofibers (NbC@CNFs) are proposed as an efficient and robust catalyst for electrochemical synthesis of ammonia from nitrate/nitrite reduction, which achieves a high Faradaic efficiency (FE) of 94.4 % and a large ammonia yield of 30.9 mg h-1 mg-1 cat.. In situ electrochemical tests reveal the nitrite reduction at the catalyst surface follows the *NO pathway and theoretical calculations reveal the formation of NbC@CNFs heterostructure significantly broadens density of states nearby the Fermi energy. Finite element simulations unveil that the current and electric field converge on the NbC nanoparticles along the fiber, suggesting the dispersed carbides are highly active for nitrite reduction.

Theoretical simulation of TADF character of 3,9'-bicarbazole-modified 2,4,6-triphenyl-1,3,5-triazine.

CONTEXT: Three donor (D)-acceptor (A)-type temperature-activated delayed fluorescent (TADF) molecules of 9-(2-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9H-3,9'-bicarbazole (o-TrzDCz), 9-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9H-3,9'-bicarbazole (m-TrzDCz), and 9-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9H-3,9'-bicarbazole (p-TrzDCz) were designed in this paper, and the photophysical properties, including the intersystem crossing rate, the reorganization energies (λ), and the intersystem crossing/reverse intersystem crossing (ISC/RISC) rate, were simulated to explore the effect of substitution sites on their TADF character. The values of the twist angle between the D and A moieties in ground state and the molecular root-mean-square deviation (RMSD) of the S1 and T1 states referenced to the S0 state indicate that o-TrzDCz possess bigger steric hindrance and stabler molecular configuration. The λ values of the ISC/RISC process should be 0.06/0.04 eV for o-TrzDCz, which are much smaller than those of m-TrzDCz (0.51/0.41 eV) and p-TrzDCz (1.93/1.06 eV). At the same time, o-TrzDCz possess the biggest kRISC (7.28 × 106 s-1) and kr (3.12 × 106 s-1) values and the smallest kp (0.10 s-1) value among the three titled molecules. These data indicate that o-TrzDCz should have more excellent TADF character than m-TrzDCz and p-TrzDCz. In a word, this research presents that adjusting the molecular linking manner should be a charming way to explore novel high-efficient TADF molecules. METHODS: Quantum chemical calculations were performed at PBE0/6-31G* level by Gaussian 09 and ORCA 4.1.0 software packages, and reorganization energies and Huang-Rhys were performed by the DUSHIN program and MOMAP 2019B software package based on the Gaussian 09 output files, while the phosphorescence rates were performed at B3LYP/6-31G* level by Dalton 2021.