Exposure to poor indoor air conditions poses significant risks to human health, increasing morbidity and mortality rates. Soft measurement modeling is suitable for stable and accurate monitoring of air pollutants and ...Exposure to poor indoor air conditions poses significant risks to human health, increasing morbidity and mortality rates. Soft measurement modeling is suitable for stable and accurate monitoring of air pollutants and improving air quality. Based on partial least squares (PLS), we propose an indoor air quality prediction model that utilizes variational auto-encoder regression (VAER) algorithm. To reduce the negative effects of noise, latent variables in the original data are extracted by PLS in the first step. Then, the extracted variables are used as inputs to VAER, which improve the accuracy and robustness of the model. Through comparative analysis with traditional methods, we demonstrate the superior performance of our PLS-VAER model, which exhibits improved prediction performance and stability. The root mean square error (RMSE) of PLS-VAER is reduced by 14.71%, 26.47%, and 12.50% compared to single VAER, PLS-SVR, and PLS-ANN, respectively. Additionally, the coefficient of determination (R2) of PLS-VAER improves by 13.70%, 30.09%, and 11.25% compared to single VAER, PLS-SVR, and PLS-ANN, respectively. This research offers an innovative and environmentally-friendly approach to monitor and improve indoor air quality.展开更多
Photoredox catalysis can be induced to activate organic substrates or to modulate the oxidation state of transition-metal catalysts via unique singleelectron transfer processes,so as to achieve challenging C(sp^(3))-H...Photoredox catalysis can be induced to activate organic substrates or to modulate the oxidation state of transition-metal catalysts via unique singleelectron transfer processes,so as to achieve challenging C(sp^(3))-H functionalization under mild conditions.However,the specific reaction mechanism and relevant electron transfer process still need to be clarified.Here,a highly regioselective Ir^(Ⅲ)/Ni^(Ⅱ)-metallaphotoredox-catalyzed hydroalkylation of asymmetrical internal alkyne with an etherα-hetero C(sp^(3))-H bond has been investigated by density functional theory(DFT)calculations.A novel radical mechanism was predicted to merge oxidative quenching(Ir^(Ⅲ)-*Ir^(Ⅲ)-Ir^(Ⅳ)-Ir^(Ⅲ))and nickel catalytic cycles(NiⅡ-NiⅢ-NiI-NiⅢ-NiⅡ)for this C(sp^(3))-H functionalization to construct C(sp^(3))-C(sp^(2))bonds.It consists of seven major steps:the single-electron transfer involved in the photoredox cycle for generating active Ni(Ⅰ)-chloride complexes,proton-coupled electron transfer process to provide α-carbon-centered tetrahydrofuran(THF)radicals,radical capture by Ni(Ⅱ),reductive elimination to obtain 2-chlorotetrahydrofuran,alkyne oxidative hydrometallation,innersphere electron transfer,and σ-bond metathesis to yield the desired alkyne hydroalkylation product.Importantly,both the thermodynamic performance for redox potentials and the kinetic exploration for energy barriers and electron-transfer rates have also been evaluated for the corresponding electron transfer processes.In addition,the steric effects play a major role in determining the regioselectivity of alkyne oxidative hydrometallation.展开更多
基金supported by the Opening Project of Guangxi Key Laboratory of Clean Pulp&Papermaking and Pollution Control,China(No.2021KF11)the Shandong Provincial Natural Science Foundation,China(No.ZR2021MF135)+1 种基金the National Natural Science Foundation of China(No.52170001)the Natural Science Foundation of Jiangsu Provincial Universities,China(No.22KJA530003).
文摘Exposure to poor indoor air conditions poses significant risks to human health, increasing morbidity and mortality rates. Soft measurement modeling is suitable for stable and accurate monitoring of air pollutants and improving air quality. Based on partial least squares (PLS), we propose an indoor air quality prediction model that utilizes variational auto-encoder regression (VAER) algorithm. To reduce the negative effects of noise, latent variables in the original data are extracted by PLS in the first step. Then, the extracted variables are used as inputs to VAER, which improve the accuracy and robustness of the model. Through comparative analysis with traditional methods, we demonstrate the superior performance of our PLS-VAER model, which exhibits improved prediction performance and stability. The root mean square error (RMSE) of PLS-VAER is reduced by 14.71%, 26.47%, and 12.50% compared to single VAER, PLS-SVR, and PLS-ANN, respectively. Additionally, the coefficient of determination (R2) of PLS-VAER improves by 13.70%, 30.09%, and 11.25% compared to single VAER, PLS-SVR, and PLS-ANN, respectively. This research offers an innovative and environmentally-friendly approach to monitor and improve indoor air quality.
文摘Photoredox catalysis can be induced to activate organic substrates or to modulate the oxidation state of transition-metal catalysts via unique singleelectron transfer processes,so as to achieve challenging C(sp^(3))-H functionalization under mild conditions.However,the specific reaction mechanism and relevant electron transfer process still need to be clarified.Here,a highly regioselective Ir^(Ⅲ)/Ni^(Ⅱ)-metallaphotoredox-catalyzed hydroalkylation of asymmetrical internal alkyne with an etherα-hetero C(sp^(3))-H bond has been investigated by density functional theory(DFT)calculations.A novel radical mechanism was predicted to merge oxidative quenching(Ir^(Ⅲ)-*Ir^(Ⅲ)-Ir^(Ⅳ)-Ir^(Ⅲ))and nickel catalytic cycles(NiⅡ-NiⅢ-NiI-NiⅢ-NiⅡ)for this C(sp^(3))-H functionalization to construct C(sp^(3))-C(sp^(2))bonds.It consists of seven major steps:the single-electron transfer involved in the photoredox cycle for generating active Ni(Ⅰ)-chloride complexes,proton-coupled electron transfer process to provide α-carbon-centered tetrahydrofuran(THF)radicals,radical capture by Ni(Ⅱ),reductive elimination to obtain 2-chlorotetrahydrofuran,alkyne oxidative hydrometallation,innersphere electron transfer,and σ-bond metathesis to yield the desired alkyne hydroalkylation product.Importantly,both the thermodynamic performance for redox potentials and the kinetic exploration for energy barriers and electron-transfer rates have also been evaluated for the corresponding electron transfer processes.In addition,the steric effects play a major role in determining the regioselectivity of alkyne oxidative hydrometallation.
