Colorectal cancer(CRC) is one of the most common malignancies with high prevalence and low 5-year survival.CRC is a heterogeneous disease with a complex,genetic and biochemical background.It is now generally accepted ...Colorectal cancer(CRC) is one of the most common malignancies with high prevalence and low 5-year survival.CRC is a heterogeneous disease with a complex,genetic and biochemical background.It is now generally accepted that a few important intracellular signaling pathways,including Wnt/β-catenin signaling,Ras signaling,and p53 signaling are frequently dysregulated in CRC.Patients with mutant p53 gene are often resistant to current therapies,conferring poor prognosis.Tumor suppressor p53 protein is a transcription factor inducing cell cycle arrest,senescence,and apoptosis under cellular stress.Emerging evidence from laboratories and clinical trials shows that some small molecule inhibitors exert anti-cancer effect via reactivation and restoration of p53 function.In this review,we summarize the p53 function and characterize its mutations in CRC.The involvement of p53 mutations in pathogenesis of CRC and their clinical impacts will be highlighted.Moreover,we also describe the current achievements of using p53 modulators to reactivate this pathway in CRC,which may have great potential as novel anti-cancer therapy.展开更多
The design of single-component broadband photoemitters with high stability is imperative for the development of next-generation WLEDs.In this work,1D cationic haloplumbate chains and rigid luminescent naphthalene dica...The design of single-component broadband photoemitters with high stability is imperative for the development of next-generation WLEDs.In this work,1D cationic haloplumbate chains and rigid luminescent naphthalene dicarboxylate(2,6-ndc)with a larger conjugated system were used to construct crystalline single-component broadband photoemitters.展开更多
The combination of D-π-A stilbazolium-type chromophores bearing ortho-N-alkyl substituents with iodocuprate resulted in three novel hybrids,these were,[(CMAMP)_(2)(CuI_(3))(acetone)_(0.5)]_(n)(1),[(HMAMP)(Cu_(3)I_(4)...The combination of D-π-A stilbazolium-type chromophores bearing ortho-N-alkyl substituents with iodocuprate resulted in three novel hybrids,these were,[(CMAMP)_(2)(CuI_(3))(acetone)_(0.5)]_(n)(1),[(HMAMP)(Cu_(3)I_(4))]n(2),and[(HMAHP)_(2)(Cu_(5)I_(7))]n(3),which present natural quantum-well architectures with void spaces of quasi-2-D organic layers occupied by iodocuprate anions via C-H⋯I hydrogen bonds.The D-π-A stilbazolium dyes exhibit head-to-tail arranged H-aggregations with face-to-faceπ⋯πstacking interactions.Theoretical calculations suggest that the charge densities on the benzenes can be strengthened from the electron-withdrawing group(-CN)to the electron-donating group(-OH),and the-C_(2)H_(5)OH substituents on the ortho-N of the pyridines not only help to open up the band gaps,but also provide a steric effect for better face-to-faceπ⋯πstacking interactions.Therefore,HMAHP^(+)in 3 possesses the strongest face-to-faceπ⋯πstacking interactions owing to the presence of a longer-C_(2)H_(5)OH group in the ortho-N position,and consequently,blue-shifted photoluminescence,a stronger photocurrent(0.28 mA),and a higher ON/OFF ratio(1.6×10^(4))can be observed in 3.In particular,electrical bistability performances can be observed in ITO/hybrids/poly(methyl methacrylate)(PMMA)/Ag devices,which are explained using Schottky emission,space-charge-limited current effect(SCLC)and Ohmic mechanisms.According to theoretical calculations,the band gap switching from the semi-conductor to the conductor(high resistance state(HRS)to low resistance state(LRS))after trapping electrons is exclusively dominated by theπbonding and anti-bonding orbitals of the stilbazolium dyes,which indicates a future direction for the design of stilbazolium-containingmemory devices.展开更多
The incorporation of organic dyes into host matrices has attracted great interest for developing new functional materials.In this work,two Cd-based layered metal–organic complexes(Cd-LMOCs),i.e.[Cd_(3)(BTB)_(2)(DEF_(...The incorporation of organic dyes into host matrices has attracted great interest for developing new functional materials.In this work,two Cd-based layered metal–organic complexes(Cd-LMOCs),i.e.[Cd_(3)(BTB)_(2)(DEF_(4)]_(n),(1-DEF)and[Cd_(3)(BTB)_(2)(DMF)_(4)·2DMF]_(n),(2-DMF),were synthesized,and three different organic stilbazolium-type dyes were incorporated into the layered Cd-LMOCs:CMAS^(+),which contains an electron-withdrawing group(–CN)on the amine,and DAST^(+)and HMAS^(+),which contain electron-donating groups(–CH_(3),–OH)on their amines.Interestingly,solvent-dependent luminescence chromisms were observed;these only occurred in DMA solvent.The dye@Cd-MOC composites obtained from DMA solvent have been fully characterized by IR,UV-Vis,PXRD,SEM,TEM and TGA;they exhibit blue-shift photoemissions and enhanced quantum yields compared with the pristine Cd-LMOCs and dye samples.After loading with dyes,the photocurrents were diminished by 2 to 6 times.Based on a combination of experimental and theoretical simulations of the dye@Cd-LMOC systems,a two-step solvent-dependent chromism mechanism was proposed:solvent exchange reactions occur firstly,and the dyes then enter the Cd-LMOCs via direct or semi-coordinated bonds between the Cd centers and vip dyes.Specifically,(CMAS)I@1-DMA with direct Cd–N bonds exhibits the highest quantum yield,and a new electron transfer route from the metal centers of the host skeletons to the side groups of the vip dyes has been found.In all,the introduction of electron-withdrawing groups on dyes is beneficial for host–vip interactions.展开更多
By using squarates as coordination building units,six new complexes formulated as[Mg(C_(4)O_(4))(H_(2)O)_(2)]n(1),[Pr_(2)(C_(4)O_(4))_(2)(OA)(H_(2)O)_(4)]n(2),[Eu_(2)(C_(4)O_(4))3(H_(2)O)_(8)]n(3)[Cd_(2)(C_(4)O_(4))_(...By using squarates as coordination building units,six new complexes formulated as[Mg(C_(4)O_(4))(H_(2)O)_(2)]n(1),[Pr_(2)(C_(4)O_(4))_(2)(OA)(H_(2)O)_(4)]n(2),[Eu_(2)(C_(4)O_(4))3(H_(2)O)_(8)]n(3)[Cd_(2)(C_(4)O_(4))_(2)(bpdo)(H_(2)O)_(4)]n(4),[Cd(C_(4)HO_(4))_(2)(H_(2)O)_(4)]·(MV)_(2)·(C_(4)O_(4))_(2)(5),and[Cd(C_(4)HO_(4))_(2)(H_(2)O)_(4)]·(EV)·(C_(4)HO_(4))_(2)(6),where(C_(4)O_(4))_(2)-=squarate,OA=oxalic acid,MV=methyl viologen,EV=ethyl viologen,and bpdo=4,4’-dipyrdiyl-N,N’-dioxide,have been synthesized under hydro/solvothermal conditions.They present structural dimensions from 3-D networks(1,2),2-D layers(3,4)to 0-D clusters(5,6)based on the versatile bridged modes of squarates and the introduction of second ligands.In particular,5 and 6 are the first examples incorporating squarates(electronic-rich species)with viologens(electronic-poor species)in one lattice.Consequently,they exhibit not only photocurrent responses but also reversible thermochromism,which will be beneficial for the design of multi-functional materials.展开更多
Two new types of iodoargentate/iodobismuthate-based inorganic-organic hybrids were prepared and structurally characterized as{[Ln_(2)(dpdo)(DMF)_(14)](Ag_(12)I_(18))}_(n)(bpdo=4,4′-bipyridine N,N′-dioxide,Ln=La(1),N...Two new types of iodoargentate/iodobismuthate-based inorganic-organic hybrids were prepared and structurally characterized as{[Ln_(2)(dpdo)(DMF)_(14)](Ag_(12)I_(18))}_(n)(bpdo=4,4′-bipyridine N,N′-dioxide,Ln=La(1),Nd(2),Sm(3))and{[Ln(dpdo)(DMF)_(6)](Bi_(2)I_(9))_(2)}_(n)(Ln=La(4),Pr(5),Er(6)).These lanthanide-silver/bismuth heterometallic hybrids feature the novel templates of lanthanide-containing metalloviologen analogs,i.e.,[Ln_(2)(dpdo)(DMF)_(14)]^(6+)(dimers for 1-3)and[Ln(dpdo)(DMF)_(6)]_(n)^(3n-)(1-D chains for 4-6).The(Ag_(12)I_(18))_(n)^(6n-)chains in 1-3 are constructed from edge-sharing Ag_(6)I_(12)units,and(Bi_(2)I_(9))^(3-)clusters in 4-6 are defined by two face-sharing BiI_(6)otcahedra.The versatile weak interactions between metalloviologens and metal iodides stabilize the structures.Upon the introduction of metalloviologens,reversible thermochromism can be found in 1-6.Besides,electrodes with films of 1-6 exhibit effective and repeatable photocurrent responses.Finally,the possible thermochromism and photocurrent response mechanisms are also discussed.展开更多
基金Supported by National Research Foundation Singapore and the Singapore Ministry of Education under its Research Centres of Excellence initiativeNMRC Clinician-Scientist IRG Grant CNIG11nov38(Zhou J)Chng WJ is also supported by NMRC Clinician Scientist Investigator award
文摘Colorectal cancer(CRC) is one of the most common malignancies with high prevalence and low 5-year survival.CRC is a heterogeneous disease with a complex,genetic and biochemical background.It is now generally accepted that a few important intracellular signaling pathways,including Wnt/β-catenin signaling,Ras signaling,and p53 signaling are frequently dysregulated in CRC.Patients with mutant p53 gene are often resistant to current therapies,conferring poor prognosis.Tumor suppressor p53 protein is a transcription factor inducing cell cycle arrest,senescence,and apoptosis under cellular stress.Emerging evidence from laboratories and clinical trials shows that some small molecule inhibitors exert anti-cancer effect via reactivation and restoration of p53 function.In this review,we summarize the p53 function and characterize its mutations in CRC.The involvement of p53 mutations in pathogenesis of CRC and their clinical impacts will be highlighted.Moreover,we also describe the current achievements of using p53 modulators to reactivate this pathway in CRC,which may have great potential as novel anti-cancer therapy.
基金supported by National Natural Science Foundation of China(No.21771038)National Natural Science Foundation of Fujian Province(2018J01684)the Open Project Program of the State Key Laboratory of Photocatalysis on Energy and Environment(Grant No.SKLPEE-202021,SKLPEE-202022),Fuzhou University.
文摘The design of single-component broadband photoemitters with high stability is imperative for the development of next-generation WLEDs.In this work,1D cationic haloplumbate chains and rigid luminescent naphthalene dicarboxylate(2,6-ndc)with a larger conjugated system were used to construct crystalline single-component broadband photoemitters.
基金supported by the National Natural Science Foundation of China(No.:21771038)the National Natural Science Foundation of Fujian Province(2018J01684).
文摘The combination of D-π-A stilbazolium-type chromophores bearing ortho-N-alkyl substituents with iodocuprate resulted in three novel hybrids,these were,[(CMAMP)_(2)(CuI_(3))(acetone)_(0.5)]_(n)(1),[(HMAMP)(Cu_(3)I_(4))]n(2),and[(HMAHP)_(2)(Cu_(5)I_(7))]n(3),which present natural quantum-well architectures with void spaces of quasi-2-D organic layers occupied by iodocuprate anions via C-H⋯I hydrogen bonds.The D-π-A stilbazolium dyes exhibit head-to-tail arranged H-aggregations with face-to-faceπ⋯πstacking interactions.Theoretical calculations suggest that the charge densities on the benzenes can be strengthened from the electron-withdrawing group(-CN)to the electron-donating group(-OH),and the-C_(2)H_(5)OH substituents on the ortho-N of the pyridines not only help to open up the band gaps,but also provide a steric effect for better face-to-faceπ⋯πstacking interactions.Therefore,HMAHP^(+)in 3 possesses the strongest face-to-faceπ⋯πstacking interactions owing to the presence of a longer-C_(2)H_(5)OH group in the ortho-N position,and consequently,blue-shifted photoluminescence,a stronger photocurrent(0.28 mA),and a higher ON/OFF ratio(1.6×10^(4))can be observed in 3.In particular,electrical bistability performances can be observed in ITO/hybrids/poly(methyl methacrylate)(PMMA)/Ag devices,which are explained using Schottky emission,space-charge-limited current effect(SCLC)and Ohmic mechanisms.According to theoretical calculations,the band gap switching from the semi-conductor to the conductor(high resistance state(HRS)to low resistance state(LRS))after trapping electrons is exclusively dominated by theπbonding and anti-bonding orbitals of the stilbazolium dyes,which indicates a future direction for the design of stilbazolium-containingmemory devices.
基金supported by the National Natural Science Foundation of China(no.:21771038)National Natural Science Foundation of Fujian Province(2018J01684,2016J01221).
文摘The incorporation of organic dyes into host matrices has attracted great interest for developing new functional materials.In this work,two Cd-based layered metal–organic complexes(Cd-LMOCs),i.e.[Cd_(3)(BTB)_(2)(DEF_(4)]_(n),(1-DEF)and[Cd_(3)(BTB)_(2)(DMF)_(4)·2DMF]_(n),(2-DMF),were synthesized,and three different organic stilbazolium-type dyes were incorporated into the layered Cd-LMOCs:CMAS^(+),which contains an electron-withdrawing group(–CN)on the amine,and DAST^(+)and HMAS^(+),which contain electron-donating groups(–CH_(3),–OH)on their amines.Interestingly,solvent-dependent luminescence chromisms were observed;these only occurred in DMA solvent.The dye@Cd-MOC composites obtained from DMA solvent have been fully characterized by IR,UV-Vis,PXRD,SEM,TEM and TGA;they exhibit blue-shift photoemissions and enhanced quantum yields compared with the pristine Cd-LMOCs and dye samples.After loading with dyes,the photocurrents were diminished by 2 to 6 times.Based on a combination of experimental and theoretical simulations of the dye@Cd-LMOC systems,a two-step solvent-dependent chromism mechanism was proposed:solvent exchange reactions occur firstly,and the dyes then enter the Cd-LMOCs via direct or semi-coordinated bonds between the Cd centers and vip dyes.Specifically,(CMAS)I@1-DMA with direct Cd–N bonds exhibits the highest quantum yield,and a new electron transfer route from the metal centers of the host skeletons to the side groups of the vip dyes has been found.In all,the introduction of electron-withdrawing groups on dyes is beneficial for host–vip interactions.
基金support for this research by the National Natural Science Foundation of China(No.:21271043,21771038)the Qishan Scholars Program of Fuzhou University(No.:XQS-1403).
文摘By using squarates as coordination building units,six new complexes formulated as[Mg(C_(4)O_(4))(H_(2)O)_(2)]n(1),[Pr_(2)(C_(4)O_(4))_(2)(OA)(H_(2)O)_(4)]n(2),[Eu_(2)(C_(4)O_(4))3(H_(2)O)_(8)]n(3)[Cd_(2)(C_(4)O_(4))_(2)(bpdo)(H_(2)O)_(4)]n(4),[Cd(C_(4)HO_(4))_(2)(H_(2)O)_(4)]·(MV)_(2)·(C_(4)O_(4))_(2)(5),and[Cd(C_(4)HO_(4))_(2)(H_(2)O)_(4)]·(EV)·(C_(4)HO_(4))_(2)(6),where(C_(4)O_(4))_(2)-=squarate,OA=oxalic acid,MV=methyl viologen,EV=ethyl viologen,and bpdo=4,4’-dipyrdiyl-N,N’-dioxide,have been synthesized under hydro/solvothermal conditions.They present structural dimensions from 3-D networks(1,2),2-D layers(3,4)to 0-D clusters(5,6)based on the versatile bridged modes of squarates and the introduction of second ligands.In particular,5 and 6 are the first examples incorporating squarates(electronic-rich species)with viologens(electronic-poor species)in one lattice.Consequently,they exhibit not only photocurrent responses but also reversible thermochromism,which will be beneficial for the design of multi-functional materials.
基金support of this research by the National Natural Science Foundation of China(No.21771038 and 21271043).
文摘Two new types of iodoargentate/iodobismuthate-based inorganic-organic hybrids were prepared and structurally characterized as{[Ln_(2)(dpdo)(DMF)_(14)](Ag_(12)I_(18))}_(n)(bpdo=4,4′-bipyridine N,N′-dioxide,Ln=La(1),Nd(2),Sm(3))and{[Ln(dpdo)(DMF)_(6)](Bi_(2)I_(9))_(2)}_(n)(Ln=La(4),Pr(5),Er(6)).These lanthanide-silver/bismuth heterometallic hybrids feature the novel templates of lanthanide-containing metalloviologen analogs,i.e.,[Ln_(2)(dpdo)(DMF)_(14)]^(6+)(dimers for 1-3)and[Ln(dpdo)(DMF)_(6)]_(n)^(3n-)(1-D chains for 4-6).The(Ag_(12)I_(18))_(n)^(6n-)chains in 1-3 are constructed from edge-sharing Ag_(6)I_(12)units,and(Bi_(2)I_(9))^(3-)clusters in 4-6 are defined by two face-sharing BiI_(6)otcahedra.The versatile weak interactions between metalloviologens and metal iodides stabilize the structures.Upon the introduction of metalloviologens,reversible thermochromism can be found in 1-6.Besides,electrodes with films of 1-6 exhibit effective and repeatable photocurrent responses.Finally,the possible thermochromism and photocurrent response mechanisms are also discussed.
