3,4-Dihydroisoquinoline(DHIQ)is an important precursor used in the production of drugs for treating cancer,HIV,Alzheimer's disease,etc.Major studies on DHIQ synthesis show low catalytic selectivity due to the susc...3,4-Dihydroisoquinoline(DHIQ)is an important precursor used in the production of drugs for treating cancer,HIV,Alzheimer's disease,etc.Major studies on DHIQ synthesis show low catalytic selectivity due to the susceptible over-oxidation feedstock of1,2,3,4-tetrahydroisoquinoline(THIQ),which often requires alkali co-catalysts.Therefore,it is desirable yet challenging to explore a highly selective and efficient oxydehydrogenation capacity for DHIQ synthesis under eco-friendly reaction conditions.Herein,a novel framework 1 was synthesized,exhibiting 1D channels with the size of 4.6 A×9.6 A and high solvent/p H/thermal stability.A stable framework allows it to encapsulate Cu nanoparticles(NPs)to form Cu NPs@1-x(x=1,2,3,and 4)with varying loading amounts of Cu NPs at 2.0 wt%,3.0 wt%,4.0 wt%,and 6.0 wt%,respectively.Cu NPs@1-3 could selectively catalyze the reaction from THIQ to DHIQ with a high selectivity of 98%and a recorded turnover frequency(TOF)of 22.1 h-1under eco-friendly mild conditions.The corresponding catalytic activity can maintain at least five recyclings and can be further applied to gram-scale experiments.Additionally,the efficient preparation of DHIQ catalyzed by Cu NPs@1-3 could be realized even under air conditions.Importantly,the anticancer molecule precursor synthesis of 6,7-dimethoxy-3,4-dihydroisoquinoline was also selectively catalyzed by Cu NPs@1-3.Mechanism investigations revealed that high catalytic performance can be attributed to the stable framework and the synergistic catalytic effect of the loaded Cu NPs and Co metal centers.More importantly,this work represents the first example of MOF catalysts for selectively thermo-catalytic DHIQ synthesis and demonstrates a simple approach to obtain efficient catalysts for selective oxydehydrogenation in the production of unsaturated compounds.展开更多
In order to further optimize welding process of Nb-Ti-Mo microalloyed steel, welding thermal cycles on coarse-grained heat-affected zone (CGHAZ) of welded joints were simulated using Gleeble 1500. The microstructure...In order to further optimize welding process of Nb-Ti-Mo microalloyed steel, welding thermal cycles on coarse-grained heat-affected zone (CGHAZ) of welded joints were simulated using Gleeble 1500. The microstructure and low-temperature impact fracture were investigated using a scanning electron microscope and a pendulum impact machine, respectively. Moreover, the relationship between cooling time ts/5 and the microstructure of CGHAZ was discussed, and the effect of microstructure on impact toughness was also studied. As cooling time increased, martensite fraction decreased from 97.8% (3 s) to 3.0% (60 s). The fraction of martensite/austenite (M/A) constituent increased from 2.2% (3 s) to 39.0% (60 s), its shape changed from granular to strip, and the maximum length increased from 2.4 μm (3 s) to 7.0 μm (60 s). As cooling time increased, the prior austenite grain size increased from 34.0 μm (3 s) to 49.0 gm (60 s), the impact absorption energy reduced from 101.8 J (5 s) to 7.2 J (60 s), and the fracture mechanism changed from quasi-cleavage fracture to cleavage fracture. The decreased toughness of CGHAZ was due to the reduction of lath martensite-content, coarsening of original austenite grain, and increase and coarsening of M/A constituent. The heat input was controlled under 7 kJ cm-1 during actual welding for these steels.展开更多
In this paper, we investigate standing waves in discrete nonlinear Schr?dinger equations with nonperiodic bounded potentials. By using the critical point theory and the spectral theory of self-adjoint operators, we pr...In this paper, we investigate standing waves in discrete nonlinear Schr?dinger equations with nonperiodic bounded potentials. By using the critical point theory and the spectral theory of self-adjoint operators, we prove the existence and infinitely many sign-changing solutions of the equation. The results on the exponential decay of standing waves are also provided.展开更多
基金supported by the National Natural Science Foundation of China(92161202,22271159,22121005,21971125)。
文摘3,4-Dihydroisoquinoline(DHIQ)is an important precursor used in the production of drugs for treating cancer,HIV,Alzheimer's disease,etc.Major studies on DHIQ synthesis show low catalytic selectivity due to the susceptible over-oxidation feedstock of1,2,3,4-tetrahydroisoquinoline(THIQ),which often requires alkali co-catalysts.Therefore,it is desirable yet challenging to explore a highly selective and efficient oxydehydrogenation capacity for DHIQ synthesis under eco-friendly reaction conditions.Herein,a novel framework 1 was synthesized,exhibiting 1D channels with the size of 4.6 A×9.6 A and high solvent/p H/thermal stability.A stable framework allows it to encapsulate Cu nanoparticles(NPs)to form Cu NPs@1-x(x=1,2,3,and 4)with varying loading amounts of Cu NPs at 2.0 wt%,3.0 wt%,4.0 wt%,and 6.0 wt%,respectively.Cu NPs@1-3 could selectively catalyze the reaction from THIQ to DHIQ with a high selectivity of 98%and a recorded turnover frequency(TOF)of 22.1 h-1under eco-friendly mild conditions.The corresponding catalytic activity can maintain at least five recyclings and can be further applied to gram-scale experiments.Additionally,the efficient preparation of DHIQ catalyzed by Cu NPs@1-3 could be realized even under air conditions.Importantly,the anticancer molecule precursor synthesis of 6,7-dimethoxy-3,4-dihydroisoquinoline was also selectively catalyzed by Cu NPs@1-3.Mechanism investigations revealed that high catalytic performance can be attributed to the stable framework and the synergistic catalytic effect of the loaded Cu NPs and Co metal centers.More importantly,this work represents the first example of MOF catalysts for selectively thermo-catalytic DHIQ synthesis and demonstrates a simple approach to obtain efficient catalysts for selective oxydehydrogenation in the production of unsaturated compounds.
基金This work was financially supported by the National Natural Science Foundation of China (No. 51775102), Open Research Fund from the State Key Laboratory of Roiling and Automation, Northeastern University (No. 2016005) and Project Funded by China Postdoctoral Science Foundation (No. 2016M601877).
文摘In order to further optimize welding process of Nb-Ti-Mo microalloyed steel, welding thermal cycles on coarse-grained heat-affected zone (CGHAZ) of welded joints were simulated using Gleeble 1500. The microstructure and low-temperature impact fracture were investigated using a scanning electron microscope and a pendulum impact machine, respectively. Moreover, the relationship between cooling time ts/5 and the microstructure of CGHAZ was discussed, and the effect of microstructure on impact toughness was also studied. As cooling time increased, martensite fraction decreased from 97.8% (3 s) to 3.0% (60 s). The fraction of martensite/austenite (M/A) constituent increased from 2.2% (3 s) to 39.0% (60 s), its shape changed from granular to strip, and the maximum length increased from 2.4 μm (3 s) to 7.0 μm (60 s). As cooling time increased, the prior austenite grain size increased from 34.0 μm (3 s) to 49.0 gm (60 s), the impact absorption energy reduced from 101.8 J (5 s) to 7.2 J (60 s), and the fracture mechanism changed from quasi-cleavage fracture to cleavage fracture. The decreased toughness of CGHAZ was due to the reduction of lath martensite-content, coarsening of original austenite grain, and increase and coarsening of M/A constituent. The heat input was controlled under 7 kJ cm-1 during actual welding for these steels.
基金Supported by Science and technology plan foundation of Guangzhou(No.201607010218)by Public Research&Capacity-Building Project of Guangdong(No.2015A070704059).
文摘In this paper, we investigate standing waves in discrete nonlinear Schr?dinger equations with nonperiodic bounded potentials. By using the critical point theory and the spectral theory of self-adjoint operators, we prove the existence and infinitely many sign-changing solutions of the equation. The results on the exponential decay of standing waves are also provided.