Fast phase-transferring was adopted in ethanol solution at the condition of n (oil-soluble tea pol-yphenol): N (As3﹢) = 2:1, 4:1, 6:1, pH = 4.0, temperature 40°C - 45°C, action period of 15 h to compo...Fast phase-transferring was adopted in ethanol solution at the condition of n (oil-soluble tea pol-yphenol): N (As3﹢) = 2:1, 4:1, 6:1, pH = 4.0, temperature 40°C - 45°C, action period of 15 h to compose the target, of which the productivity was 59%, UV was 267.50, 218.00, 220.50 nm, FTIR was 6291, 34158.6, 2850.2, 1708.2;1457.3;1370.4, 1224.2, 1144.0, 760.5 cm﹣1, fluorescence value λmax = 257, 591.1, 593.7, 590.3, 591.0, 591.5, XRD λ/nm is 3.6974, 4.186, 12.0762, 15.4747, 1H-NMRδ = 0.782, 1.193, 1.483 - 1.586, 1.959 - 2.184, 2.479, 3.116, 3.970 - 3.981, 5.231 - 5.753, 6.537 - 7.300. Finally it was ascertained through XRD as double-coordinated polycrystal compound.展开更多
The rapid identification of γ-emitting radionuclides with low activity levels in public areas is crucial for nuclear safety.However,classical methods rely on full-energy peaks in the integral spectrum,requiring suffi...The rapid identification of γ-emitting radionuclides with low activity levels in public areas is crucial for nuclear safety.However,classical methods rely on full-energy peaks in the integral spectrum,requiring sufficient count accumulation for evaluation,thereby limiting response time.The sequential Bayesian approach,which utilizes prior information and considers both photon energies and interarrival times,can significantly enhance the performance of radionuclides identification.This study proposes a theoretical optimization method for the traditional sequential Bayesian approach.Each photon is processed sequentially,and the corresponding posterior probability is updated in real time using a noninformative prior from the Bayesian theory.By comparing the posterior probabilities of the background and radionuclides based on the energy variance and time interval,the type of γ-rays can be identified(background characteristic γ-rays,Compton plateaus γ-rays,or radionuclide-specific characteristic γ-rays).By integrating the information from these multiple characteristic γ-rays,the presence and type of radionuclides were determined based on the final decision function and a set threshold.Based on theoretical research,verification experiments were conducted using a LaBr_(3)(Ce)detector in both low-and natural background radiation environments with typical radionuclides(^(137)Cs,^(60)Co,and ^(133)Ba).The results show that this approach can identify ^(137)Cs in 7.9 s and 8.5 s(source dose rate contribution:approximately 6.5×10^(−3)μGy/h),^(60)Co in 8.1 s and 9.8 s(approximately 4.8×10^(−2)μGy/h),and ^(133)Ba in 4.05 s and 5.99 s(approximately 3.4×10^(−2)μGy/h)under low and natural background radiation,respectively,with a miss rate below 0.01%.This demonstrates the effectiveness of the proposed approach for fast radionuclides identification,even at low activity levels and highlights its potential for enhancing public safety in diverse radiation environments.展开更多
To address the performance limitations of conventional LiPF6-carbonate electrolytes under extreme temperatures and high-rate charging,lithium difluoro(oxalato)borate(LiDFOB)is introduced into the LiPF6-carbonate elect...To address the performance limitations of conventional LiPF6-carbonate electrolytes under extreme temperatures and high-rate charging,lithium difluoro(oxalato)borate(LiDFOB)is introduced into the LiPF6-carbonate electrolyte to form a dual-salt system.The optimization mechanism enhancing the fast-charging capability of LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)(NCM523)cathode is systematically explored.Molecular dynamics simulations and electrochemical characterization demonstrate the reconstruction of Li+solvation structures,expanding the voltage window and reducting Li^(+)desolvation barriers.In addition,the incorporation of LiDFOB induces the generation of a LiF/Li_(x)BO_(y)F_(z)-enriched cathode-electrolyte interphase,which effectively suppresses the dissolution of transition metals.In situ impedance measurements reveal the accelerated interfacial charge transfer kinetics.As expected,the NCM523 cathode achieves an 82%state-of-charge(SOC)in 12 min at 5 C(25°C)with 87%capacity retention after 100 cycles,and exhibits a 65%higher discharge capacity at 1 C than the baseline at−20°C.The 1 Ah pouch cells based on LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)cathodes,graphite anodes,and 0.5 wt%LiDFOB-modified electrolyte demonstrate fast-charging capabilities:charging 97%of the pouch cell capacity within 30 min(2 C)and 80%within 15 min(4 C)at 25°C.This study offers a practical electrolyte design strategy that enhances the fast-charging performance of lithium-ion batteries(LIBs)over a wide temperature range(from−20 to 25°C).展开更多
Nuclear magnetic resonance(NMR)spectroscopy is a powerful tool for analyzing molecular structure and composition.However,traditional NMR experiments suffer from long acquisition times,especially in multidimensional NM...Nuclear magnetic resonance(NMR)spectroscopy is a powerful tool for analyzing molecular structure and composition.However,traditional NMR experiments suffer from long acquisition times,especially in multidimensional NMR spectroscopy.This problem,to some extent,limits broader applications of NMR techniques.Various methods have been proposed to accelerate sampling,including non-uniform sampling(NUS),multi-FID acquisition(MFA),Hadamard encoding,Fourier encoding,spatial encoding Ultrafast 2D NMR(UF2DNMR),and so on.The review focuses on rapid sampling methods developed in contemporary China,introducing their fundamental principles and applications while discussing their respective advantages and disadvantages.展开更多
Phenol is an important raw material.The pre-sent industrial method of a multistep and indirect syn-thesis of phenol from benzene has the disadvantages of a long synthetic route,large consumption of raw ma-terial and s...Phenol is an important raw material.The pre-sent industrial method of a multistep and indirect syn-thesis of phenol from benzene has the disadvantages of a long synthetic route,large consumption of raw ma-terial and serious environment pollution.The direct oxidization of benzene to phenol under mild conditions is being sought for researches[1~3].The reaction-con-trolled phase-transfer catalyst[4-6]developed recently is a kind of environmentally friendly catalyst.The re-action-controlled phase-transfer catalyst can be recov-ered,like a heterogeneous catalyst,but also acts as a homogeneous catalyst.The reaction-controlled phase-transfer catalyst possesses the above advantages and it is significant to design and synthesize such a catalyst,but there have been few reports concerning the prepa-ration of this kind of catalysts.展开更多
A series of heteropolytungstates has been synthesized and utilized as catalysts to catalyze oxidation of benzyl alcohol with aqueous hydrogen peroxide. The results indicated that three of these catalysts showed the pr...A series of heteropolytungstates has been synthesized and utilized as catalysts to catalyze oxidation of benzyl alcohol with aqueous hydrogen peroxide. The results indicated that three of these catalysts showed the properties of reaction-controlled phasetransfer catalysis, and they had excellent catalytic ability to the oxidation of benzyl alcohol. No other by-products were detected by gas chromatography. Once the hydrogen peroxide was consumed completely, the catalyst precipitated from solvent, and the results of the catalyst recycle showed that the catalyst had high stability.展开更多
A highly effective phase transfer of a quaternary ammonium gemini surfactant with ester groups（（diethylhexanedioate） diyl-a,v-bis（dimethyl dodecyl ammonium bromide） referred to as 12-10-12）was synthesized with h...A highly effective phase transfer of a quaternary ammonium gemini surfactant with ester groups（（diethylhexanedioate） diyl-a,v-bis（dimethyl dodecyl ammonium bromide） referred to as 12-10-12）was synthesized with high yield and characterized by infrared spectroscopy, elemental analysis and1 HNMR. Then, 12-10-12 was used as a phase transfer catalyst to study the catalytic effect on the reaction of anhydrous sodium acetate and 4-methylbenzyl chloride. The possible catalytic mechanism and the influence of surfactant concentration, temperature and type are also discussed. The experimental results showed that the catalysis efficiency was more active than the traditional, single-chained surfactant,tetrabutyl ammonium bromide. It also revealed that the reaction was first-order with respect to the concentration of 4-methylbenzyl chloride. The concentration of 4-methylbenzyl chloride grew linearly with the concentration of 12-10-12 and as the reaction temperature increased. The optimum reaction time was 7 h.展开更多
A highly effective and mild protocol for ring opening of epoxides with NH4SCN in the presence of catalytic amount of a multi- site phase-transfer catalyst, α,α＇,α＂-N-hexakis（triethylammoniummethylene chloride）-...A highly effective and mild protocol for ring opening of epoxides with NH4SCN in the presence of catalytic amount of a multi- site phase-transfer catalyst, α,α＇,α＂-N-hexakis（triethylammoniummethylene chloride）-melamine, is developed. A variety of ^-hydroxy thiocyanates as important intermediates in agricultural and pharmaceutical chemistry were obtained in high yields with excellent regioselectivity and in short reaction times. 2009 Ali Reza Kiasat. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
A new reaction-controlled phase-transfer catalyst system was designed and synthesized. In this system, heteropolytungstate [C7H7N(CH3)3]9PW9O34 was used for catalytic epoxidation of cyclohexene with H2O2 as the oxida...A new reaction-controlled phase-transfer catalyst system was designed and synthesized. In this system, heteropolytungstate [C7H7N(CH3)3]9PW9O34 was used for catalytic epoxidation of cyclohexene with H2O2 as the oxidant. The conversion of H2O2 was 100% and the yield of cyclohexene oxide was 87.1% based on cyclohexene. Infrared spectra showed that both fresh catalyst and the recovered catalyst do have completely same absorption peak, indicating the structure of catalyst is very stability and can be recycled.展开更多
Ionic liquids （ILs） based on 1,3-dialkylimidazolium and tetraalkylammonium cations were employed as a series of efficient, environmentally benign phase-transfer catalysts （PTCs） for the base-promoted monoalkylatio...Ionic liquids （ILs） based on 1,3-dialkylimidazolium and tetraalkylammonium cations were employed as a series of efficient, environmentally benign phase-transfer catalysts （PTCs） for the base-promoted monoalkylation of diethyl malonate. The influence of various heterogeneous bases on yields was studied. Good yields and high selectivity were obtained. Solvent-free, mild reaction condition, short reaction time, and easy purification were the merits of this method. The catalytic system （IL-hase） could also be recycled after the extraction of products with ether.展开更多
Chiral phase-transfer catalysts, derived from cinchona alkaloids and Fréchet dendritic wedges up to generation two, have been synthesized. These chiral dendritic molecules have been used as PTCs in the epoxidatio...Chiral phase-transfer catalysts, derived from cinchona alkaloids and Fréchet dendritic wedges up to generation two, have been synthesized. These chiral dendritic molecules have been used as PTCs in the epoxidation of α, β-enones, showing a moderate level of asymmetric induction.展开更多
A new series of chiral phase-transfer catalysts 7a-7h were designed and synthesized from L-proline with moderate to good yields.＇The catalytic activity of 7a-Th for the asymmetric alkylation of glycine Schiff bases w...A new series of chiral phase-transfer catalysts 7a-7h were designed and synthesized from L-proline with moderate to good yields.＇The catalytic activity of 7a-Th for the asymmetric alkylation of glycine Schiff bases was evaluated, and some interesting relationships between structure and catalytic activity were revealed.展开更多
文摘Fast phase-transferring was adopted in ethanol solution at the condition of n (oil-soluble tea pol-yphenol): N (As3﹢) = 2:1, 4:1, 6:1, pH = 4.0, temperature 40°C - 45°C, action period of 15 h to compose the target, of which the productivity was 59%, UV was 267.50, 218.00, 220.50 nm, FTIR was 6291, 34158.6, 2850.2, 1708.2;1457.3;1370.4, 1224.2, 1144.0, 760.5 cm﹣1, fluorescence value λmax = 257, 591.1, 593.7, 590.3, 591.0, 591.5, XRD λ/nm is 3.6974, 4.186, 12.0762, 15.4747, 1H-NMRδ = 0.782, 1.193, 1.483 - 1.586, 1.959 - 2.184, 2.479, 3.116, 3.970 - 3.981, 5.231 - 5.753, 6.537 - 7.300. Finally it was ascertained through XRD as double-coordinated polycrystal compound.
基金supported by the Program for NIM-Basic Research Business Expenses Key Field Program,China(No.AKYCX2315).
文摘The rapid identification of γ-emitting radionuclides with low activity levels in public areas is crucial for nuclear safety.However,classical methods rely on full-energy peaks in the integral spectrum,requiring sufficient count accumulation for evaluation,thereby limiting response time.The sequential Bayesian approach,which utilizes prior information and considers both photon energies and interarrival times,can significantly enhance the performance of radionuclides identification.This study proposes a theoretical optimization method for the traditional sequential Bayesian approach.Each photon is processed sequentially,and the corresponding posterior probability is updated in real time using a noninformative prior from the Bayesian theory.By comparing the posterior probabilities of the background and radionuclides based on the energy variance and time interval,the type of γ-rays can be identified(background characteristic γ-rays,Compton plateaus γ-rays,or radionuclide-specific characteristic γ-rays).By integrating the information from these multiple characteristic γ-rays,the presence and type of radionuclides were determined based on the final decision function and a set threshold.Based on theoretical research,verification experiments were conducted using a LaBr_(3)(Ce)detector in both low-and natural background radiation environments with typical radionuclides(^(137)Cs,^(60)Co,and ^(133)Ba).The results show that this approach can identify ^(137)Cs in 7.9 s and 8.5 s(source dose rate contribution:approximately 6.5×10^(−3)μGy/h),^(60)Co in 8.1 s and 9.8 s(approximately 4.8×10^(−2)μGy/h),and ^(133)Ba in 4.05 s and 5.99 s(approximately 3.4×10^(−2)μGy/h)under low and natural background radiation,respectively,with a miss rate below 0.01%.This demonstrates the effectiveness of the proposed approach for fast radionuclides identification,even at low activity levels and highlights its potential for enhancing public safety in diverse radiation environments.
基金financially supported by the National Natural Science Foundation of China (Grant No. 52372191)the National Natural Science Foundation of China (Grant No. 22271106)+2 种基金the National Science Foundation of China (Grant Nos. 52073286 (C.-Z.L.), 22275185 (C.-Z.L.))the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZZ115 (C.-Z.L.)the XMIREM Autonomously Deployment Project (2023GG01 (C.-Z.L.))
文摘To address the performance limitations of conventional LiPF6-carbonate electrolytes under extreme temperatures and high-rate charging,lithium difluoro(oxalato)borate(LiDFOB)is introduced into the LiPF6-carbonate electrolyte to form a dual-salt system.The optimization mechanism enhancing the fast-charging capability of LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)(NCM523)cathode is systematically explored.Molecular dynamics simulations and electrochemical characterization demonstrate the reconstruction of Li+solvation structures,expanding the voltage window and reducting Li^(+)desolvation barriers.In addition,the incorporation of LiDFOB induces the generation of a LiF/Li_(x)BO_(y)F_(z)-enriched cathode-electrolyte interphase,which effectively suppresses the dissolution of transition metals.In situ impedance measurements reveal the accelerated interfacial charge transfer kinetics.As expected,the NCM523 cathode achieves an 82%state-of-charge(SOC)in 12 min at 5 C(25°C)with 87%capacity retention after 100 cycles,and exhibits a 65%higher discharge capacity at 1 C than the baseline at−20°C.The 1 Ah pouch cells based on LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)cathodes,graphite anodes,and 0.5 wt%LiDFOB-modified electrolyte demonstrate fast-charging capabilities:charging 97%of the pouch cell capacity within 30 min(2 C)and 80%within 15 min(4 C)at 25°C.This study offers a practical electrolyte design strategy that enhances the fast-charging performance of lithium-ion batteries(LIBs)over a wide temperature range(from−20 to 25°C).
基金financially supported by the National Natural Science Foundation of China(grant numbers 22174118,12411530077,and 22374124).
文摘Nuclear magnetic resonance(NMR)spectroscopy is a powerful tool for analyzing molecular structure and composition.However,traditional NMR experiments suffer from long acquisition times,especially in multidimensional NMR spectroscopy.This problem,to some extent,limits broader applications of NMR techniques.Various methods have been proposed to accelerate sampling,including non-uniform sampling(NUS),multi-FID acquisition(MFA),Hadamard encoding,Fourier encoding,spatial encoding Ultrafast 2D NMR(UF2DNMR),and so on.The review focuses on rapid sampling methods developed in contemporary China,introducing their fundamental principles and applications while discussing their respective advantages and disadvantages.
文摘Phenol is an important raw material.The pre-sent industrial method of a multistep and indirect syn-thesis of phenol from benzene has the disadvantages of a long synthetic route,large consumption of raw ma-terial and serious environment pollution.The direct oxidization of benzene to phenol under mild conditions is being sought for researches[1~3].The reaction-con-trolled phase-transfer catalyst[4-6]developed recently is a kind of environmentally friendly catalyst.The re-action-controlled phase-transfer catalyst can be recov-ered,like a heterogeneous catalyst,but also acts as a homogeneous catalyst.The reaction-controlled phase-transfer catalyst possesses the above advantages and it is significant to design and synthesize such a catalyst,but there have been few reports concerning the prepa-ration of this kind of catalysts.
文摘A series of heteropolytungstates has been synthesized and utilized as catalysts to catalyze oxidation of benzyl alcohol with aqueous hydrogen peroxide. The results indicated that three of these catalysts showed the properties of reaction-controlled phasetransfer catalysis, and they had excellent catalytic ability to the oxidation of benzyl alcohol. No other by-products were detected by gas chromatography. Once the hydrogen peroxide was consumed completely, the catalyst precipitated from solvent, and the results of the catalyst recycle showed that the catalyst had high stability.
基金supported by the Talent Foundation of Anhui Science and Technology University (No. ZRC2014401)
文摘A highly effective phase transfer of a quaternary ammonium gemini surfactant with ester groups（（diethylhexanedioate） diyl-a,v-bis（dimethyl dodecyl ammonium bromide） referred to as 12-10-12）was synthesized with high yield and characterized by infrared spectroscopy, elemental analysis and1 HNMR. Then, 12-10-12 was used as a phase transfer catalyst to study the catalytic effect on the reaction of anhydrous sodium acetate and 4-methylbenzyl chloride. The possible catalytic mechanism and the influence of surfactant concentration, temperature and type are also discussed. The experimental results showed that the catalysis efficiency was more active than the traditional, single-chained surfactant,tetrabutyl ammonium bromide. It also revealed that the reaction was first-order with respect to the concentration of 4-methylbenzyl chloride. The concentration of 4-methylbenzyl chloride grew linearly with the concentration of 12-10-12 and as the reaction temperature increased. The optimum reaction time was 7 h.
基金the partial support of this work by Shahid Chamran Research Council
文摘A highly effective and mild protocol for ring opening of epoxides with NH4SCN in the presence of catalytic amount of a multi- site phase-transfer catalyst, α,α＇,α＂-N-hexakis（triethylammoniummethylene chloride）-melamine, is developed. A variety of ^-hydroxy thiocyanates as important intermediates in agricultural and pharmaceutical chemistry were obtained in high yields with excellent regioselectivity and in short reaction times. 2009 Ali Reza Kiasat. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
文摘A new reaction-controlled phase-transfer catalyst system was designed and synthesized. In this system, heteropolytungstate [C7H7N(CH3)3]9PW9O34 was used for catalytic epoxidation of cyclohexene with H2O2 as the oxidant. The conversion of H2O2 was 100% and the yield of cyclohexene oxide was 87.1% based on cyclohexene. Infrared spectra showed that both fresh catalyst and the recovered catalyst do have completely same absorption peak, indicating the structure of catalyst is very stability and can be recycled.
文摘Ionic liquids （ILs） based on 1,3-dialkylimidazolium and tetraalkylammonium cations were employed as a series of efficient, environmentally benign phase-transfer catalysts （PTCs） for the base-promoted monoalkylation of diethyl malonate. The influence of various heterogeneous bases on yields was studied. Good yields and high selectivity were obtained. Solvent-free, mild reaction condition, short reaction time, and easy purification were the merits of this method. The catalytic system （IL-hase） could also be recycled after the extraction of products with ether.
文摘Chiral phase-transfer catalysts, derived from cinchona alkaloids and Fréchet dendritic wedges up to generation two, have been synthesized. These chiral dendritic molecules have been used as PTCs in the epoxidation of α, β-enones, showing a moderate level of asymmetric induction.
基金National Natural Science Foundation of China (Grant No. 20802004)
文摘A new series of chiral phase-transfer catalysts 7a-7h were designed and synthesized from L-proline with moderate to good yields.＇The catalytic activity of 7a-Th for the asymmetric alkylation of glycine Schiff bases was evaluated, and some interesting relationships between structure and catalytic activity were revealed.
