BACKGROUND: Postoperative regional chemotherapy is one of the most effective methods to decrease the recurrent rate and improve the prognosis of primary hepatocarcinoma (PHC). This study was undertaken to assess the o...BACKGROUND: Postoperative regional chemotherapy is one of the most effective methods to decrease the recurrent rate and improve the prognosis of primary hepatocarcinoma (PHC). This study was undertaken to assess the optimal pathway to implant the drug delivery system (DDS) in the different ways of resecting PHC so as to offer a valuable reference to clinical implantation of the DDS. METHODS: One hundred and ninety cases were divided into two groups according to whether the tumors were resected completely (A) or not (B). Groups A and B were subdivided into three groups a, b and c according to the pathway selected for DDS implantation. The patients in subgroup a received DDS implantation through both the hepatic artery and portal vein (A+P-implanted group), the patients in subgroup b received DDS implantation through the portal vein (P-implanted group), and the patients in subgroup c received DDS implantation through the hepatic artery (A-implanted group). RESULTS: The 1- and 3-year recurrent rates of subgroup c in group A were higher than those of subgroup b, and there was no significant difference between subgroups a and b. Compared with subgroups a and c, the 1- and 3-year survival rates of subgroup b were similar to those of group a but higher than those of group c. The 1- and 3-year survival rates between subgroups a and b in group B were significantly different. The prognosis of subgroup c was lower than that of subgroup a and no significant difference was observed between subgroups b and c. CONCLUSIONS: The DDS should be implanted into the portal vein when PHC is resected completely. It may be better to implant it into both portal vein and hepatic artery if the tumor cannot be completely resected.展开更多
Pathway selection in a complex chemical reaction network(CRN)enables organisms to adapt,evolve,and even learn in response to changing environments.Inspired by this,herein we report an artificial system,where light sig...Pathway selection in a complex chemical reaction network(CRN)enables organisms to adapt,evolve,and even learn in response to changing environments.Inspired by this,herein we report an artificial system,where light signal was used to manipulate the reaction pathways in a disulfide-based nonequilibrium CRN.By changing the photon energy and irradiation window,the anion or new radical-mediated pathways were selectively triggered,resulting in a user-defined evolution pathway.Additional photodissipative cycles were achieved by UV(365 nm)irradiation,increasing the total number of reactions from 3 to 7.The emerging pathway selection of the CRN is accurately predictable and controllable even in complex organo-hydrogel materials.We demonstrate up to five-state autonomous sol-gel transitions and the formation of fuel-driven dissipative organo-hydrogel through both chemical and light input.This work represents a new approach to allowing CRNs to communicate with the environment that can be used in the development of materials with lifelike behaviors.展开更多
The formation of LiOH as the discharge product instead of Li_(2)O_(2)in Li-O_(2)batteries(LOBs)is highly desirable due to the associated drawbacks of Li_(2)O_(2)-based chemistry,which involves the generation of reacti...The formation of LiOH as the discharge product instead of Li_(2)O_(2)in Li-O_(2)batteries(LOBs)is highly desirable due to the associated drawbacks of Li_(2)O_(2)-based chemistry,which involves the generation of reactive oxygen intermediates responsible for substantial side reactions.However,the current challenge lies in the formation pathway of LiOH,which typically requires the chemical hydrolysis of the hazardous LiO_(2)or Li_(2)O_(2)intermediate,posing risks to the battery components.Herein,we report a direct 4e–electrochemical approach to LiOH enabled by a single atom catalyst(SAC)consisting of CoN_(3)moieties embedded in graphene(CoN_(3)-G),while Li_(2)O_(2)is formed on the metal-free nitrogen-doped graphene(NG).The direct 4e–LiOH pathway significantly reduces the parasitic reactions,resulting in negligible damage to the electrolyte and cathode.This stands in strong contrast to the conventional 2e–Li_(2)O_(2)pathway mediated by NG and the indirect LiOH pathway by MnO_(2).Theoretical calculations further clarify that the presence of CoN_(3)sites enhances the adsorption of oxygen-containing intermediates like*OLiO and*Li_(2)O_(2),promoting the protonation of*Li_(2)O_(2)and the cleavage of the O–O bond to form LiOH.This work demonstrates a promising strategy to modulate the reaction pathways in LOBs and broadens the applications of SACs.展开更多
Developing efficient and robust electrocatalysts toward ethanol oxidation reaction(EOR)with high C1 pathway selectivity is critical for commercialization of direct ethanol fuel cells(DEFCs).Unfortunately,current most ...Developing efficient and robust electrocatalysts toward ethanol oxidation reaction(EOR)with high C1 pathway selectivity is critical for commercialization of direct ethanol fuel cells(DEFCs).Unfortunately,current most EOR electrocatalysts suffer from rapid activity degradation and poor C1 pathway selectivity for complete oxidation of ethanol.Herein,we report a novel electrocatalyst of five-fold twinned(FFT)Ir-alloyed Pt nanorods(NRs)toward EOR.Such FFT Pt-Ir NRs bounded by five(100)facets on the sides and ten(111)facets at two ends possess high percentage of(100)facets with tensile strain.Owing to the inherent characteristics of the FFT NR and Ir alloying,the as-prepared FFT Pt-Ir NRs display excellent alkaline EOR performance with a mass activity(MA)of 4.18 A·mgPt^(-1),a specific activity(SA)of 10.22 mA·cm^(-2),and a Faraday efficiency of 61.21%for the C1 pathway,which are 6.85,5.62,and 7.70 times higher than those of a commercial Pt black,respectively.Besides,our catalyst also exhibits robust durability.The large percentage of open tensile-strained(100)facets and Ir alloying significantly promote the cleavage of C-C bonds and facilitate oxidation of the poisonous intermediates,leading to the transformation of the dominant reaction pathway for EOR from C2 to C1 pathway,and effectively suppress the deactivation of the catalyst.展开更多
文摘BACKGROUND: Postoperative regional chemotherapy is one of the most effective methods to decrease the recurrent rate and improve the prognosis of primary hepatocarcinoma (PHC). This study was undertaken to assess the optimal pathway to implant the drug delivery system (DDS) in the different ways of resecting PHC so as to offer a valuable reference to clinical implantation of the DDS. METHODS: One hundred and ninety cases were divided into two groups according to whether the tumors were resected completely (A) or not (B). Groups A and B were subdivided into three groups a, b and c according to the pathway selected for DDS implantation. The patients in subgroup a received DDS implantation through both the hepatic artery and portal vein (A+P-implanted group), the patients in subgroup b received DDS implantation through the portal vein (P-implanted group), and the patients in subgroup c received DDS implantation through the hepatic artery (A-implanted group). RESULTS: The 1- and 3-year recurrent rates of subgroup c in group A were higher than those of subgroup b, and there was no significant difference between subgroups a and b. Compared with subgroups a and c, the 1- and 3-year survival rates of subgroup b were similar to those of group a but higher than those of group c. The 1- and 3-year survival rates between subgroups a and b in group B were significantly different. The prognosis of subgroup c was lower than that of subgroup a and no significant difference was observed between subgroups b and c. CONCLUSIONS: The DDS should be implanted into the portal vein when PHC is resected completely. It may be better to implant it into both portal vein and hepatic artery if the tumor cannot be completely resected.
基金supported by the National Natural Science Foundation of China(grant no.52073175)National Natural Science Foundation of Shanghai(grant no.23ZR1442700)。
文摘Pathway selection in a complex chemical reaction network(CRN)enables organisms to adapt,evolve,and even learn in response to changing environments.Inspired by this,herein we report an artificial system,where light signal was used to manipulate the reaction pathways in a disulfide-based nonequilibrium CRN.By changing the photon energy and irradiation window,the anion or new radical-mediated pathways were selectively triggered,resulting in a user-defined evolution pathway.Additional photodissipative cycles were achieved by UV(365 nm)irradiation,increasing the total number of reactions from 3 to 7.The emerging pathway selection of the CRN is accurately predictable and controllable even in complex organo-hydrogel materials.We demonstrate up to five-state autonomous sol-gel transitions and the formation of fuel-driven dissipative organo-hydrogel through both chemical and light input.This work represents a new approach to allowing CRNs to communicate with the environment that can be used in the development of materials with lifelike behaviors.
基金the National Natural Science Foundation of China(grant no.92163116)Major Program of the Natural Science Foundation of Hunan Province(grant no.2021JC0006)the National Natural Science Foundation of China(grant no.22209043).
文摘The formation of LiOH as the discharge product instead of Li_(2)O_(2)in Li-O_(2)batteries(LOBs)is highly desirable due to the associated drawbacks of Li_(2)O_(2)-based chemistry,which involves the generation of reactive oxygen intermediates responsible for substantial side reactions.However,the current challenge lies in the formation pathway of LiOH,which typically requires the chemical hydrolysis of the hazardous LiO_(2)or Li_(2)O_(2)intermediate,posing risks to the battery components.Herein,we report a direct 4e–electrochemical approach to LiOH enabled by a single atom catalyst(SAC)consisting of CoN_(3)moieties embedded in graphene(CoN_(3)-G),while Li_(2)O_(2)is formed on the metal-free nitrogen-doped graphene(NG).The direct 4e–LiOH pathway significantly reduces the parasitic reactions,resulting in negligible damage to the electrolyte and cathode.This stands in strong contrast to the conventional 2e–Li_(2)O_(2)pathway mediated by NG and the indirect LiOH pathway by MnO_(2).Theoretical calculations further clarify that the presence of CoN_(3)sites enhances the adsorption of oxygen-containing intermediates like*OLiO and*Li_(2)O_(2),promoting the protonation of*Li_(2)O_(2)and the cleavage of the O–O bond to form LiOH.This work demonstrates a promising strategy to modulate the reaction pathways in LOBs and broadens the applications of SACs.
基金This work was supported by the National Natural Science Foundation of China(No.21908036)the China Postdoctoral Science Foundation(No.2019M662143)+1 种基金the Natural Science Foundation of Anhui Province(No.2008085QB74)the Fundamental Research Funds for the Central Universities(No.JZ2021HGTB0116).
文摘Developing efficient and robust electrocatalysts toward ethanol oxidation reaction(EOR)with high C1 pathway selectivity is critical for commercialization of direct ethanol fuel cells(DEFCs).Unfortunately,current most EOR electrocatalysts suffer from rapid activity degradation and poor C1 pathway selectivity for complete oxidation of ethanol.Herein,we report a novel electrocatalyst of five-fold twinned(FFT)Ir-alloyed Pt nanorods(NRs)toward EOR.Such FFT Pt-Ir NRs bounded by five(100)facets on the sides and ten(111)facets at two ends possess high percentage of(100)facets with tensile strain.Owing to the inherent characteristics of the FFT NR and Ir alloying,the as-prepared FFT Pt-Ir NRs display excellent alkaline EOR performance with a mass activity(MA)of 4.18 A·mgPt^(-1),a specific activity(SA)of 10.22 mA·cm^(-2),and a Faraday efficiency of 61.21%for the C1 pathway,which are 6.85,5.62,and 7.70 times higher than those of a commercial Pt black,respectively.Besides,our catalyst also exhibits robust durability.The large percentage of open tensile-strained(100)facets and Ir alloying significantly promote the cleavage of C-C bonds and facilitate oxidation of the poisonous intermediates,leading to the transformation of the dominant reaction pathway for EOR from C2 to C1 pathway,and effectively suppress the deactivation of the catalyst.