Erlotinib is an orally administered, highly effective, specific epidermal growth factor receptor tyrosine kinase inhibitor, used to treat non-small cell lung cancer and pancreatic cancer. The traditional synthetic met...Erlotinib is an orally administered, highly effective, specific epidermal growth factor receptor tyrosine kinase inhibitor, used to treat non-small cell lung cancer and pancreatic cancer. The traditional synthetic methods for Erlotinib exhibit long reaction time and safety concern. Herein, we describe a novel five-step route for the synthesis of Erlotinib in flow. These five steps comprise etherification, nitration, reduction,addition and cyclization reactions. All steps were optimized and converted to continuous flow process,which drastically reduces the reaction time and considerably improves the process safety as well as the total yield. Enabled by five continuous flow units, Erlotinib is efficiently afforded with an E-factor of 38,an overall yield of 83%, and a total residence time of 25.1 min. Majority steps in this process have been optimized for quantitative conversion, which offers the possibility of telescoping the entire process.展开更多
The aim of this study is to use a new configuration of porous media in a heat exchanger in continuous hydrothermal flow synthesis(CHFS)system to enhance the heat transfer and minimize the required length of the heat e...The aim of this study is to use a new configuration of porous media in a heat exchanger in continuous hydrothermal flow synthesis(CHFS)system to enhance the heat transfer and minimize the required length of the heat exchanger.For this purpose,numerous numerical simulations are performed to investigate performance of the system with porous media.First,the numerical simulation for the heat exchanger in CHFS system is validated by experimental data.Then,porous media is added to the system and six different thicknesses for the porous media are examined to obtain the optimum thickness,based on the minimum required length of the heat exchanger.Finally,by changing the flow rate and inlet temperature of the product as well as the cooling water flow rate,the minimum required length of the heat exchanger with porous media for various inlet conditions is assessed.The investigations indicate that using porous media with the proper thickness in the heat exchanger increases the cooling rate of the product by almost 40% and reduces the required length of the heat exchanger by approximately 35%.The results also illustrate that the most proper thickness of the porous media is approximately equal to 90% of the product tube's thickness.Results of this study lead to design a porous heat exchanger in CHFS system for various inlet conditions.展开更多
Size-controlled flow synthesis of nanoporous particles are of considerable interest for future industrial applications,however,is facing challenges due to lack of in-situ method for size-characterization in fluidic en...Size-controlled flow synthesis of nanoporous particles are of considerable interest for future industrial applications,however,is facing challenges due to lack of in-situ method for size-characterization in fluidic environment.We present that ultraviolet-visible(UV-vis)absorption spectroscopy can be integrated into a flow-synthesis system which was produced by femtosecond laser micro machining.The shift of the absorption peak position of the ex-situ and in-situ UV-vis spectra correlates to variation of size of porous metal-organic frameworks crystals.ZIF-67 crystals with a size in the range from 200 nm to1025 nm are fabricated with the assistance of tri-ethylamine under monitoring of in-situ UV-vis spectra.The ZIF-67 crystals are converted into nanoporous carbons particles with controlled sizes.These materials show size-dependent performance in Na-ion battery and size-independent performance in metal/H_(2)O seawater battery.展开更多
Cutting-edge research has primarily focused on flow synthesis of linear block copolymers,lacking the ability for manipulating chain architectures for more extensive applications.Herein,we develop a flow chemistry plat...Cutting-edge research has primarily focused on flow synthesis of linear block copolymers,lacking the ability for manipulating chain architectures for more extensive applications.Herein,we develop a flow chemistry platform for the continuous microflow synthesis of bottlebrush block copolymers(BBCPs)using a grafting-through method.This involves performing ring-opening metathesis polymerization(ROMP)of two different macromonomers within two microfluidic reactors connected in series.The microflow environment allows for complete monomer conversion within a few tens of seconds,benefiting from the superior mixing efficiency achieved in Z-shaped channels as indicated by both theoretical simulations and experimental results.Consequently,a library of well-defined BBCPs of up to 528 distinct samples can be produced within one day through automation of the continuous procedure,while keeping precise control on degree of polymerization(DP<4)and polydispersity indices(PDI<1.2).The synthetic method is generally applicable to different macromonomers with different compositions and contour lengths,yielding libraries of branched block copolymers with great diversity in physiochemical properties and chain architectures.This work presents a powerful platform for high-throughput production of branched copolymers,significantly lowering the costs of the materials for real applications.展开更多
Calcium dibutyryladenosine cyclophosphate is a widely used cardiovascular drug.The traditional batch synthesis process suffers from long reaction times,tedious operations,and unstable yields.Herein,a sequential contin...Calcium dibutyryladenosine cyclophosphate is a widely used cardiovascular drug.The traditional batch synthesis process suffers from long reaction times,tedious operations,and unstable yields.Herein,a sequential continuous flow synthesis combined with a multistage in-line purification process of calcium dibutyryladenosine cyclophosphate was developed.The acylation reaction was completed in a continuous coil reactor at 160℃in 20 min.And the high toxic solvent pyridine was replaced by acetonitrile.Furthermore,the multistage in-line purification process was integrated into the homemade 3D circular cyclone-type micromixer chip.Combining with the membrane phase separators,the residence time of the purification step was 30 s.The isolated yield of this sequential continuous process was 92%with 99%purity.展开更多
To enhance the reproducibility and scale up the synthesis of colloidal quantum dots(QDs),continuous flow synthesis is an appealing alternative to the widely used batch synthesis.Amongst other advantages,the strongly e...To enhance the reproducibility and scale up the synthesis of colloidal quantum dots(QDs),continuous flow synthesis is an appealing alternative to the widely used batch synthesis.Amongst other advantages,the strongly enhanced heat and mass transfer in small tubular reactors combined with controlled pressure can be cited.Nonetheless,the widespread use of this technique is hampered by special requirements such as the absence of solid or gaseous products and the room-temperature solubility of precursors.Therefore,the transfer of established reaction conditions from batch to flow is not straightforward and in most reported works the optical properties of the obtained QDs lag behind those prepared in batch reactions.This is also the case for PbS-based QDs,which are established near infrared(NIR)absorbers/emitters.Here we identified experimental conditions giving access to high-quality PbS core and PbS/CdS core/shell QDs obtained in an automated,easily scalable continuous flow synthesis.In particular,substituted thioureas have been selected as the sulfur source and ex-situ synthesized lead and cadmium oleate as the metal precursors,and appropriate solvent mixtures have been identified for each precursor.Highly luminescent PbS/CdS QDs emitting at the target wavelengths 940 and 1130 nm of special interest for NIR light-emitting diodes have been prepared,exhibiting a photoluminescence quantum yield up to 91%.展开更多
Triflumezopyrim(TFM)is a novel mesoionic pyrido[1,2-α]pyrimidinones insecticide,which acts on nicotinic acetylcholine receptors(n ACh Rs)and has no cross-resistance with other insecticides.Herein,we firstly developed...Triflumezopyrim(TFM)is a novel mesoionic pyrido[1,2-α]pyrimidinones insecticide,which acts on nicotinic acetylcholine receptors(n ACh Rs)and has no cross-resistance with other insecticides.Herein,we firstly developed a new continuous flow approach to synthesis 2-[3-(trifluoromethyl)phenyl]malonic acid,a key intermate of TFM,coupling with esterification,condensation,and hydrolysis.All three-step reactions were optimized and transformed into a continuous synthesis mode by three micro reaction units.Compared with the batch mode,the total reaction time and overall separation yield were improved from more than 12 h and 60%to 18 min and 73.38%,respectively.The solvent consumption and waste emission were significantly reduced,which also provides an eco-friendly and efficient potential tool for the development and production of mesoionic pyrido[1,2-α]pyrimidinones insecticide.展开更多
The first example of the microfluidic chips(MFCs) consisting of centimeter-level 3D channels with highdensity and large-volume fabricated by femtosecond laser micromachining were utilized to develop a time-saving, eco...The first example of the microfluidic chips(MFCs) consisting of centimeter-level 3D channels with highdensity and large-volume fabricated by femtosecond laser micromachining were utilized to develop a time-saving, economical and hazardless flow synthesis process, and its advantages have been proved by in situ formation of aryldiazonium salts and subsequent borylation with bis(pinacolato)diboron. There are several important advantages in our 3D MFC-based flow synthesis technology, including the following:(1) the reaction temperature was altered from ice bath to room temperature;(2) the residence time was reduced by 10 times;(3) the yield was greatly improved, that is, several arylboronates were successfully obtained with higher yield compared to traditional batch process. Therefore, it can be envisioned that a novel, simplified flow synthetic protocol will be developed toward green organic synthesis via MFCs.展开更多
In this work,a thin zirconium-based UiO-66 membrane was successfully prepared on an alumina hollow fiber tube by flow synthesis,and was used in an attempt to remove p-nitrophenol from water through a nanofiltration pr...In this work,a thin zirconium-based UiO-66 membrane was successfully prepared on an alumina hollow fiber tube by flow synthesis,and was used in an attempt to remove p-nitrophenol from water through a nanofiltration process.Two main factors,including flow rate and synthesis time,were investigated to optimize the conditions for membrane growth.Under optimal synthesis conditions,a thin UiO-66 membrane of approximately 2 um in thickness was fabricated at a flow rate of4 mL.h for 30 h.The p-nitrophenol rejection rate for the as-prepared UiO-66 membrane applied in the removal of p-nitrophenol from water was only 78.1%due to the existence of membrane defects caused by coordinative defects during membrane formation.Post-synthetic modification of the UiO-66 membrane was carried out using organic linkers with the same flow approach to further improve the nanofiltration performance.The result showed that the p-nitrophenol rejection for the post-modified membrane was greatly improved and reached over 95%.Moreover,the post-modified UiO-66 membrane exhibited remarkable long-term operational stability,which is vital for practical application.展开更多
3-Methylpyridine-N-oxide is an essential intermediate in the preparation of 2-chloro-5-methylpyridine,which can be used to synthesize nicotine insecticides such as imidacloprid and acetamiprid.The traditional method o...3-Methylpyridine-N-oxide is an essential intermediate in the preparation of 2-chloro-5-methylpyridine,which can be used to synthesize nicotine insecticides such as imidacloprid and acetamiprid.The traditional method of production of 3-methylpyridine-N-oxide is catalytic oxidation of 3-methylpyridine in semi-batch reactors.Due to strong exothermic reaction and explosive property of 3-methylpyridine,the reaction efficiency and safety is low using batch technology.Therefore,the development of a safer and efficient 3-methylpyridine-N-oxide production process is very necessary in industrial production.In this paper,microreaction systems were introduced into the preparation of 3-methylpyridine-N-oxide.The comparison of three different methods(traditional semibatch method,co-current microreaction method,and circular microreaction method)showed that the circular microreaction method was the most applicable,with relative higher product yield(~90%),less side reaction and better reaction control.展开更多
Recent developments in the utilization of microfluidic chips(MFCs) have shown their potential utility in multiphase organic synthesis by enabling efficient organic reactions in flow chemistry. However, MFCs technology...Recent developments in the utilization of microfluidic chips(MFCs) have shown their potential utility in multiphase organic synthesis by enabling efficient organic reactions in flow chemistry. However, MFCs technology has been wandering in the laboratory of small dose synthetic routes, which is limited to the level of "tiny" fluid flux. To address this issue, we herein report the first case of the chips with highthroughput 3D channels produced by femtosecond laser being used to create a time-saving, cost-effective and risk-free approach suitable for large-scale flow synthesis. Several multiphase reactions have been successfully prepared on demand in our designed flow synthesis system containing 3D MFCs: 1) benzyl alcohol was converted to benzaldehyde in 3 min with a yield of 97.50% by liquid-liquid two-phase transfer catalytic oxidation;2) organozinc reagents and α-cyano carbonyl carbon compounds were synthesized by solid-liquid two-phase metal insertion reaction in 7 min, and the yield was up to 100%;3) benzoic acid was synthesized by gas-liquid two-phase carboxylation reaction in 2.8 s with a yield of 96%. Significant gains in production rate result from the effective scaling of flow reactors from microliters per hour in MFCs to intermediate milliliters per minute without affecting mass transport performance. Meanwhile,our 3D MFCs show excellent mass and heat transfer efficiency in large-scale industrial units, breaking through the bottleneck in this field. As a result, it is possible to imagine the creation of a new, streamlined flow synthetic technique via MFCs for green multiphase organic synthesis.展开更多
A continuous synthesis method for the less than 10 nm core-shell upconversion nanoparticles was developed via coiled tube embedded flask reactors and a flow solvothermal co-participation reaction up to 300℃.Fast nucl...A continuous synthesis method for the less than 10 nm core-shell upconversion nanoparticles was developed via coiled tube embedded flask reactors and a flow solvothermal co-participation reaction up to 300℃.Fast nucleation of hexagonal nanocrystals in less than 9 min residence time was achieved owing to the excellent heating ability of the reactors,and a two-step reaction strategy was created for the synthesis of β-NaYF4:Gd,Yb,Er/Ho/Tm@NaYF_(4) particles without intermediate purification.展开更多
An efficient palladium-catalyzed electrooxidation C–H acylation reaction of N-nitrosoanilines with α-oxocarboxylic acids was developed. The anodic oxidation of the Pd(Ⅱ) intermediate was found to be the key to comp...An efficient palladium-catalyzed electrooxidation C–H acylation reaction of N-nitrosoanilines with α-oxocarboxylic acids was developed. The anodic oxidation of the Pd(Ⅱ) intermediate was found to be the key to complete the reaction. In this case, the N-nitroso group was observed to be an effective directing group for C–H activation reaction. Moreover, the synthetic transformation of derivatives of natural products(L-menthol, dehydroepiandrosterone, and pregnenolone) was successfully realized. Finally, flow electrochemical synthesis of some substrates was achieved.展开更多
A combinatorial library of twenty-three,phase pure,near-NMC111(LiNi_(0.33) Mn_(0.33)Co_(0,33)O_(2))composi-tions were synthesised and their electrochemical performance,was mapped(in lithium ion half-cells).Each of the...A combinatorial library of twenty-three,phase pure,near-NMC111(LiNi_(0.33) Mn_(0.33)Co_(0,33)O_(2))composi-tions were synthesised and their electrochemical performance,was mapped(in lithium ion half-cells).Each of the 23 compositions was made in series,using a two-step process of 1)a rapid initial contin-uous hydrothermal precipitation,followed by 2)solid state lithiation.The 23 lithiated NMC samples were then subjected to analytical methods including electron microscopy(selected samples),Powder X-ray Diffraction and electrochemical tests in half cell Li-ion configurations versus Li metal.A sample with a Ni:Mn:Co(NMC)ratio of 39:28:33,revealed a specific capacity of 150 mA h g^(-1) at a C/20 rate,which was 63 and 43% greater capacity than NMC111 and NMC433 samples produced in this work,respectively.The sample with NMC ratio 47:25:28,showed the best capacity retention characteristics,retaining 70%of its C/20 capacity at 1C,after 40 cycles.Further analysis of all the samples by cyclic voltammetry and elec-trochemical impedance spectroscopy,allowed compositional mapping of diffusion coefficients.Overall,the mapping data revealed a gradual change of properties across compositional space,which has vali-dated our combinatorial approach and allowed identification of the optimum performing near-NMC111 cathode materials.展开更多
This paper introduces the microarchitecture and physical implementation of the Godson-2E processor, which is a four-issue superscalar RISC processor that supports the 64-bit MIPS instruction set. The adoption of the a...This paper introduces the microarchitecture and physical implementation of the Godson-2E processor, which is a four-issue superscalar RISC processor that supports the 64-bit MIPS instruction set. The adoption of the aggressive out-of-order execution and memory hierarchy techniques help Godson-2E to achieve high performance. The Godson-2E processor has been physically designed in a 7-metal 90nm CMOS process using the cell-based methodology with some bitsliced manual placement and a number of crafted cells and macros. The processor can be run at 1GHz and achieves a SPEC CPU2000 rate higher than 500.展开更多
基金the National Natural Science Foundation of China(Nos.21878088, 21476077)Key Projects of Shanghai Science and Technology Commission (No.18DZ1112703) for financial support。
文摘Erlotinib is an orally administered, highly effective, specific epidermal growth factor receptor tyrosine kinase inhibitor, used to treat non-small cell lung cancer and pancreatic cancer. The traditional synthetic methods for Erlotinib exhibit long reaction time and safety concern. Herein, we describe a novel five-step route for the synthesis of Erlotinib in flow. These five steps comprise etherification, nitration, reduction,addition and cyclization reactions. All steps were optimized and converted to continuous flow process,which drastically reduces the reaction time and considerably improves the process safety as well as the total yield. Enabled by five continuous flow units, Erlotinib is efficiently afforded with an E-factor of 38,an overall yield of 83%, and a total residence time of 25.1 min. Majority steps in this process have been optimized for quantitative conversion, which offers the possibility of telescoping the entire process.
文摘The aim of this study is to use a new configuration of porous media in a heat exchanger in continuous hydrothermal flow synthesis(CHFS)system to enhance the heat transfer and minimize the required length of the heat exchanger.For this purpose,numerous numerical simulations are performed to investigate performance of the system with porous media.First,the numerical simulation for the heat exchanger in CHFS system is validated by experimental data.Then,porous media is added to the system and six different thicknesses for the porous media are examined to obtain the optimum thickness,based on the minimum required length of the heat exchanger.Finally,by changing the flow rate and inlet temperature of the product as well as the cooling water flow rate,the minimum required length of the heat exchanger with porous media for various inlet conditions is assessed.The investigations indicate that using porous media with the proper thickness in the heat exchanger increases the cooling rate of the product by almost 40% and reduces the required length of the heat exchanger by approximately 35%.The results also illustrate that the most proper thickness of the porous media is approximately equal to 90% of the product tube's thickness.Results of this study lead to design a porous heat exchanger in CHFS system for various inlet conditions.
基金supported by National Natural Science Foundation of China(Nos.11674340,21473059)Key Project of the Shanghai Science and Technology Committee(No.18DZ1112700)。
文摘Size-controlled flow synthesis of nanoporous particles are of considerable interest for future industrial applications,however,is facing challenges due to lack of in-situ method for size-characterization in fluidic environment.We present that ultraviolet-visible(UV-vis)absorption spectroscopy can be integrated into a flow-synthesis system which was produced by femtosecond laser micro machining.The shift of the absorption peak position of the ex-situ and in-situ UV-vis spectra correlates to variation of size of porous metal-organic frameworks crystals.ZIF-67 crystals with a size in the range from 200 nm to1025 nm are fabricated with the assistance of tri-ethylamine under monitoring of in-situ UV-vis spectra.The ZIF-67 crystals are converted into nanoporous carbons particles with controlled sizes.These materials show size-dependent performance in Na-ion battery and size-independent performance in metal/H_(2)O seawater battery.
基金financially supported by the National Natural Science Foundation of China(No.22071176)。
文摘Cutting-edge research has primarily focused on flow synthesis of linear block copolymers,lacking the ability for manipulating chain architectures for more extensive applications.Herein,we develop a flow chemistry platform for the continuous microflow synthesis of bottlebrush block copolymers(BBCPs)using a grafting-through method.This involves performing ring-opening metathesis polymerization(ROMP)of two different macromonomers within two microfluidic reactors connected in series.The microflow environment allows for complete monomer conversion within a few tens of seconds,benefiting from the superior mixing efficiency achieved in Z-shaped channels as indicated by both theoretical simulations and experimental results.Consequently,a library of well-defined BBCPs of up to 528 distinct samples can be produced within one day through automation of the continuous procedure,while keeping precise control on degree of polymerization(DP<4)and polydispersity indices(PDI<1.2).The synthetic method is generally applicable to different macromonomers with different compositions and contour lengths,yielding libraries of branched block copolymers with great diversity in physiochemical properties and chain architectures.This work presents a powerful platform for high-throughput production of branched copolymers,significantly lowering the costs of the materials for real applications.
基金supported by the National Natural Science Foundation of China(No.22278087)。
文摘Calcium dibutyryladenosine cyclophosphate is a widely used cardiovascular drug.The traditional batch synthesis process suffers from long reaction times,tedious operations,and unstable yields.Herein,a sequential continuous flow synthesis combined with a multistage in-line purification process of calcium dibutyryladenosine cyclophosphate was developed.The acylation reaction was completed in a continuous coil reactor at 160℃in 20 min.And the high toxic solvent pyridine was replaced by acetonitrile.Furthermore,the multistage in-line purification process was integrated into the homemade 3D circular cyclone-type micromixer chip.Combining with the membrane phase separators,the residence time of the purification step was 30 s.The isolated yield of this sequential continuous process was 92%with 99%purity.
基金platforms of the Grenoble Instruct-ERIC center(ISBGUAR 3518 CNRSCEA-UGA-EMBL)within the Grenoble Partnership for Structural Biology(PSB)+1 种基金supported by FRISBI(ANR-10-INBS-0005-02)financed within the University Grenoble Alpes graduate school(Ecoles Universitaires de Recherche)CBH-EUR-GS(ANR-17-EURE-0003).
文摘To enhance the reproducibility and scale up the synthesis of colloidal quantum dots(QDs),continuous flow synthesis is an appealing alternative to the widely used batch synthesis.Amongst other advantages,the strongly enhanced heat and mass transfer in small tubular reactors combined with controlled pressure can be cited.Nonetheless,the widespread use of this technique is hampered by special requirements such as the absence of solid or gaseous products and the room-temperature solubility of precursors.Therefore,the transfer of established reaction conditions from batch to flow is not straightforward and in most reported works the optical properties of the obtained QDs lag behind those prepared in batch reactions.This is also the case for PbS-based QDs,which are established near infrared(NIR)absorbers/emitters.Here we identified experimental conditions giving access to high-quality PbS core and PbS/CdS core/shell QDs obtained in an automated,easily scalable continuous flow synthesis.In particular,substituted thioureas have been selected as the sulfur source and ex-situ synthesized lead and cadmium oleate as the metal precursors,and appropriate solvent mixtures have been identified for each precursor.Highly luminescent PbS/CdS QDs emitting at the target wavelengths 940 and 1130 nm of special interest for NIR light-emitting diodes have been prepared,exhibiting a photoluminescence quantum yield up to 91%.
基金the National Key Research and Development Program of China(Nos.2023YFD1700303,2022YFD17800)National Natural Science Foundation of China(Nos.21878088,21476077)for financial support。
文摘Triflumezopyrim(TFM)is a novel mesoionic pyrido[1,2-α]pyrimidinones insecticide,which acts on nicotinic acetylcholine receptors(n ACh Rs)and has no cross-resistance with other insecticides.Herein,we firstly developed a new continuous flow approach to synthesis 2-[3-(trifluoromethyl)phenyl]malonic acid,a key intermate of TFM,coupling with esterification,condensation,and hydrolysis.All three-step reactions were optimized and transformed into a continuous synthesis mode by three micro reaction units.Compared with the batch mode,the total reaction time and overall separation yield were improved from more than 12 h and 60%to 18 min and 73.38%,respectively.The solvent consumption and waste emission were significantly reduced,which also provides an eco-friendly and efficient potential tool for the development and production of mesoionic pyrido[1,2-α]pyrimidinones insecticide.
基金supported by the Shanghai Municipal Science and Technology Major Project (“Beyond Limits manufacture”)。
文摘The first example of the microfluidic chips(MFCs) consisting of centimeter-level 3D channels with highdensity and large-volume fabricated by femtosecond laser micromachining were utilized to develop a time-saving, economical and hazardless flow synthesis process, and its advantages have been proved by in situ formation of aryldiazonium salts and subsequent borylation with bis(pinacolato)diboron. There are several important advantages in our 3D MFC-based flow synthesis technology, including the following:(1) the reaction temperature was altered from ice bath to room temperature;(2) the residence time was reduced by 10 times;(3) the yield was greatly improved, that is, several arylboronates were successfully obtained with higher yield compared to traditional batch process. Therefore, it can be envisioned that a novel, simplified flow synthetic protocol will be developed toward green organic synthesis via MFCs.
基金supported by the National Natural Science Foundation of China(Grant Nos.21476039,21878032 and 21076030).
文摘In this work,a thin zirconium-based UiO-66 membrane was successfully prepared on an alumina hollow fiber tube by flow synthesis,and was used in an attempt to remove p-nitrophenol from water through a nanofiltration process.Two main factors,including flow rate and synthesis time,were investigated to optimize the conditions for membrane growth.Under optimal synthesis conditions,a thin UiO-66 membrane of approximately 2 um in thickness was fabricated at a flow rate of4 mL.h for 30 h.The p-nitrophenol rejection rate for the as-prepared UiO-66 membrane applied in the removal of p-nitrophenol from water was only 78.1%due to the existence of membrane defects caused by coordinative defects during membrane formation.Post-synthetic modification of the UiO-66 membrane was carried out using organic linkers with the same flow approach to further improve the nanofiltration performance.The result showed that the p-nitrophenol rejection for the post-modified membrane was greatly improved and reached over 95%.Moreover,the post-modified UiO-66 membrane exhibited remarkable long-term operational stability,which is vital for practical application.
基金the supports of the National Natural Science Foundation of China(21991101,2191100)the Key Project of Science&Technology Department of Sichuan Province(2017JZ0011)for this work。
文摘3-Methylpyridine-N-oxide is an essential intermediate in the preparation of 2-chloro-5-methylpyridine,which can be used to synthesize nicotine insecticides such as imidacloprid and acetamiprid.The traditional method of production of 3-methylpyridine-N-oxide is catalytic oxidation of 3-methylpyridine in semi-batch reactors.Due to strong exothermic reaction and explosive property of 3-methylpyridine,the reaction efficiency and safety is low using batch technology.Therefore,the development of a safer and efficient 3-methylpyridine-N-oxide production process is very necessary in industrial production.In this paper,microreaction systems were introduced into the preparation of 3-methylpyridine-N-oxide.The comparison of three different methods(traditional semibatch method,co-current microreaction method,and circular microreaction method)showed that the circular microreaction method was the most applicable,with relative higher product yield(~90%),less side reaction and better reaction control.
基金supported by the Shanghai Municipal Science and Technology Major Project (“Beyond Limits manufacture”)。
文摘Recent developments in the utilization of microfluidic chips(MFCs) have shown their potential utility in multiphase organic synthesis by enabling efficient organic reactions in flow chemistry. However, MFCs technology has been wandering in the laboratory of small dose synthetic routes, which is limited to the level of "tiny" fluid flux. To address this issue, we herein report the first case of the chips with highthroughput 3D channels produced by femtosecond laser being used to create a time-saving, cost-effective and risk-free approach suitable for large-scale flow synthesis. Several multiphase reactions have been successfully prepared on demand in our designed flow synthesis system containing 3D MFCs: 1) benzyl alcohol was converted to benzaldehyde in 3 min with a yield of 97.50% by liquid-liquid two-phase transfer catalytic oxidation;2) organozinc reagents and α-cyano carbonyl carbon compounds were synthesized by solid-liquid two-phase metal insertion reaction in 7 min, and the yield was up to 100%;3) benzoic acid was synthesized by gas-liquid two-phase carboxylation reaction in 2.8 s with a yield of 96%. Significant gains in production rate result from the effective scaling of flow reactors from microliters per hour in MFCs to intermediate milliliters per minute without affecting mass transport performance. Meanwhile,our 3D MFCs show excellent mass and heat transfer efficiency in large-scale industrial units, breaking through the bottleneck in this field. As a result, it is possible to imagine the creation of a new, streamlined flow synthetic technique via MFCs for green multiphase organic synthesis.
基金supports from the National Natural Science Foundation of China(Nos.21991104 and 92034303).
文摘A continuous synthesis method for the less than 10 nm core-shell upconversion nanoparticles was developed via coiled tube embedded flask reactors and a flow solvothermal co-participation reaction up to 300℃.Fast nucleation of hexagonal nanocrystals in less than 9 min residence time was achieved owing to the excellent heating ability of the reactors,and a two-step reaction strategy was created for the synthesis of β-NaYF4:Gd,Yb,Er/Ho/Tm@NaYF_(4) particles without intermediate purification.
基金the Guangxi Natural Science Foundation of China (No. 2021GXNSFFA220005)the Central Government Guides Local Science and Technology Development Fund Projects (No. guike ZY21195014)+2 种基金National Natural Science Foundation of China (Nos. 22061003, 22161008, 22161007)middle-aged and young teachers’ basic scientific research ability improvement project of Guangxi (No. RZ1900005748)the Opening Project of Hunan Engineering Laboratory for analyse and Drugs Development of Ethnomedicine in Wuling Mountain (No. hgxy2101) for financial support。
文摘An efficient palladium-catalyzed electrooxidation C–H acylation reaction of N-nitrosoanilines with α-oxocarboxylic acids was developed. The anodic oxidation of the Pd(Ⅱ) intermediate was found to be the key to complete the reaction. In this case, the N-nitroso group was observed to be an effective directing group for C–H activation reaction. Moreover, the synthetic transformation of derivatives of natural products(L-menthol, dehydroepiandrosterone, and pregnenolone) was successfully realized. Finally, flow electrochemical synthesis of some substrates was achieved.
基金Jawwad A.Darr and Daniel Commandeur would like to thank Innovate UK for funding the research under the Faraday Battery Challenge:innovation R&D,round 3 Project title:Scalable Ultra-Power Electric-vehicle Batteries(SUPErB)[project reference 105300]Thomas Ashton and Jawwad A.Darr would like to thank the EPSRC for funding the JUICED Energy Hub(EP/R023662/1)。
文摘A combinatorial library of twenty-three,phase pure,near-NMC111(LiNi_(0.33) Mn_(0.33)Co_(0,33)O_(2))composi-tions were synthesised and their electrochemical performance,was mapped(in lithium ion half-cells).Each of the 23 compositions was made in series,using a two-step process of 1)a rapid initial contin-uous hydrothermal precipitation,followed by 2)solid state lithiation.The 23 lithiated NMC samples were then subjected to analytical methods including electron microscopy(selected samples),Powder X-ray Diffraction and electrochemical tests in half cell Li-ion configurations versus Li metal.A sample with a Ni:Mn:Co(NMC)ratio of 39:28:33,revealed a specific capacity of 150 mA h g^(-1) at a C/20 rate,which was 63 and 43% greater capacity than NMC111 and NMC433 samples produced in this work,respectively.The sample with NMC ratio 47:25:28,showed the best capacity retention characteristics,retaining 70%of its C/20 capacity at 1C,after 40 cycles.Further analysis of all the samples by cyclic voltammetry and elec-trochemical impedance spectroscopy,allowed compositional mapping of diffusion coefficients.Overall,the mapping data revealed a gradual change of properties across compositional space,which has vali-dated our combinatorial approach and allowed identification of the optimum performing near-NMC111 cathode materials.
基金Supported by the National Natural Science Foundation of China for Distinguished Young Scholars under Grant No. 60325205, the National Natural Science Foundation of China under Grant No. 60673146, the National High Technology Development 863 Program of China under Grants No. 2002AAl10010, No. 2005AAl10010, No. 2005AAl19020, and the National Grand Fundamental Research 973 Program of China under Grant No. 2005CB321600.
文摘This paper introduces the microarchitecture and physical implementation of the Godson-2E processor, which is a four-issue superscalar RISC processor that supports the 64-bit MIPS instruction set. The adoption of the aggressive out-of-order execution and memory hierarchy techniques help Godson-2E to achieve high performance. The Godson-2E processor has been physically designed in a 7-metal 90nm CMOS process using the cell-based methodology with some bitsliced manual placement and a number of crafted cells and macros. The processor can be run at 1GHz and achieves a SPEC CPU2000 rate higher than 500.
