Platinum(Pt) based drugs, such as cisplatin, are widely used as anti-cancer agents, but their severe adverse reactions and resistance of cancer patients have limited their board clinical use. For the last few decades,...Platinum(Pt) based drugs, such as cisplatin, are widely used as anti-cancer agents, but their severe adverse reactions and resistance of cancer patients have limited their board clinical use. For the last few decades, Pt(Ⅱ) compounds, Pt(Ⅳ) prodrugs as well as smart drug delivery systems have been developed to overcome these problems. However, most conventional strategies rely on the similar anti-cancer mechanism with cisplatin and consequently only achieve limited success. Recently, Pt nanocrystals/nanoclusters(Pt NCs), with a brand new anti-cancer mechanism, have shown a promising potential in targeted cancer therapy, especially in Pt resistance circumvention. This review is helpful to understand the research strategies of Pt drugs, particularly, the recent developments and medical applications of Pt NCs.展开更多
A new series of mono-cyclometalated square planar platinum(Ⅱ) complexes have been synthesized and the single-crystal X-ray structures of complex 1 and 2 have been determined.The complexes have the general formula ppy...A new series of mono-cyclometalated square planar platinum(Ⅱ) complexes have been synthesized and the single-crystal X-ray structures of complex 1 and 2 have been determined.The complexes have the general formula ppyPt(O^O),where ppy is 2-phenylpyridyl,and O^O is β-diketonate ancillary ligands with the acyl substituent group in position 3 of(D)-(+)-camphor.Although,like the many Pt(Ⅱ) complexes with square-planar geometry,these complexes have plane stacking modes in crystal structure,the sterically bulky camphor-derived groups compel extensive slipping of the molecular stacking planes,resulting in the negligible overlapping of the aromatic ring fragments between molecules and the considerable Pt-Pt distance.The resolved spectra and a little shifted emission in solid state of complexes show that there is significant reduction of π-π interactions and Pt-Pt interactions,and suggest these complexes may be good candidates for doped phosphorescent organic light emitting diodes(PhOLEDs) and even for nondoped PhOLEDs.展开更多
DFT B3LYP/LANL2DZ method was employed to calculate electron properties and the second-order nonlinear optical(NLO) respond of platinum(Ⅱ) complexes which have been synthesized by Weinstein group.4,7-diphenyl-1,10-phe...DFT B3LYP/LANL2DZ method was employed to calculate electron properties and the second-order nonlinear optical(NLO) respond of platinum(Ⅱ) complexes which have been synthesized by Weinstein group.4,7-diphenyl-1,10-phenanthroline shows the ability to push electron in these complexes.Metal Pt plays a balancing charge role.Comparing complex 1b-6b with complex a,the βvec value of complex 1b-5b is larger than one of complex a,while the βvec value of complex 6b is smaller than one of com-plex a.In these seven complexes,the βvec values of complexes increase with decreasing of the energy difference between HOMO and LUMO.Moreover,the electron transfers from deeper layer occupied orbitals to empty orbitals have a distinct contribution to second-order NLO coefficient.展开更多
The interaction of tetracyline-Pt(Ⅱ)complex with DNA was studied.The studies on absorption spectrum and electrochemistry indicate that the interaction of tetracyline with DNA is not obvious.After tetracycline interac...The interaction of tetracyline-Pt(Ⅱ)complex with DNA was studied.The studies on absorption spectrum and electrochemistry indicate that the interaction of tetracyline with DNA is not obvious.After tetracycline interact with Pt(Ⅱ)to form complex,the complex can interact with calf thymus DNA by way of intercalation.And the formation of tetracyline-Pt(Ⅱ)complex could be affected by the pH value of the sulotion.展开更多
A mononuclear complex, cis-[meso-1, 3-bis(propylsulfinyl)propane]- dichloroplatinum(Ⅱ) (Pt(C9H20O2S2)Cl2) 1, has been prepared and structurally characterizated by single-crystal X-ray diffraction. The crystal belongs...A mononuclear complex, cis-[meso-1, 3-bis(propylsulfinyl)propane]- dichloroplatinum(Ⅱ) (Pt(C9H20O2S2)Cl2) 1, has been prepared and structurally characterizated by single-crystal X-ray diffraction. The crystal belongs to orthorhombic system, space group Pna21 with a = 22.800(3), b = 11.7662(13), c = 5.8115(6) ? V = 1559.0(3) ?, Mr = 490.36, Dc = 2.089 g/cm3, Z = 4, F(000) = 936, m (MoKa) = 9.596 mm-1 and l = 0.71073 ? The structure was refined to R = 0.0204 and wR = 0.0473 for 2703 reflections with I > 2(I). It is revealed that the central Pt(Ⅱ) ion in the title complex is bonded to two Cl atoms in a cis-configuration and two S atoms of the ligand to form the coordination geometry deviating slightly from the square planar.展开更多
A novel cationic Pt(Ⅱ)complex 2 with 2-(2,4-difluorophenyl)pyridine as the cyclometalating ligand and 1,10-phenanthroline as the auxiliary ligand has been synthesized and fully characterized.This complex exhibits muc...A novel cationic Pt(Ⅱ)complex 2 with 2-(2,4-difluorophenyl)pyridine as the cyclometalating ligand and 1,10-phenanthroline as the auxiliary ligand has been synthesized and fully characterized.This complex exhibits much higher aggregation-induced phosphorescent emission activity than that of a nonfluorinated complex 1 in CH_(3)CN/H_(2)O.The complex 2 demonstrates efficient detection on picric acid(PA)in CH_(3)CN/H_(2)O,providing a high quenching constant(K_(SV)=2.3×10^(4) L/mol)and a low limit of detection(LOD=0.26μmol/L).In addition,complex 2 shows high selectivity for detection of PA in real water samples.Density functional theory calculations and proton nuclear magnetic resonance spectra suggest that the detection mechanism is attributed to the photo-induced electron transfer.展开更多
D-A charge transfer, including through-bond charge transfer and through-space charge transfer between two different electron donors(D) and electron acceptors(A), is a fundamental and powerful tool to tune the optical ...D-A charge transfer, including through-bond charge transfer and through-space charge transfer between two different electron donors(D) and electron acceptors(A), is a fundamental and powerful tool to tune the optical properties of organic dyes. Herein,we demonstrate a unique strategy to tune phosphorescence and circularly polarized luminescence properties of axially chiral binuclear Pt(Ⅱ) complexes through long-range charge transfer, even though these molecules have two totally identical segments on either side of the chiral core. The presence of axial chirality would break not only the symmetry of molecular structure and π-conjugation system but also the symmetry of charge distribution for long-range charge transfer. These binaphthyl-based Pt(Ⅱ)complexes bearing coordinated atoms far away from chiral axis exhibit no Pt-Pt interactions but colorful concentrationdependent phosphorescence with quantum yield up to 86.4% and could be applied as emitters in highly efficient solutionprocessed organic light-emitting diodes to achieve luminance, luminance efficiency, power efficiency, external quantum efficiency, and asymmetry factor up to 8.94 × 10^(3)cd m^(-2), 41.9 cd A-1, 18.8 lm W^(-1), 12.6% and 2.98 × 10^(-3), respectively. Therefore,the present work affords a new and simple way to utilize the inherently asymmetric advantage of chirality for the design of D-Abased organic dyes.展开更多
基金supported by the National Key Research and Development Program of China(2016YFA0203600)the National Natural Science Foundation of China(51503180,5161101036)+1 种基金“Thousand Talents Program”for Distinguished Young Scholars(588020*G81501/048)Fundamental Research Funds for the Central Universities(520002*172210161)
文摘Platinum(Pt) based drugs, such as cisplatin, are widely used as anti-cancer agents, but their severe adverse reactions and resistance of cancer patients have limited their board clinical use. For the last few decades, Pt(Ⅱ) compounds, Pt(Ⅳ) prodrugs as well as smart drug delivery systems have been developed to overcome these problems. However, most conventional strategies rely on the similar anti-cancer mechanism with cisplatin and consequently only achieve limited success. Recently, Pt nanocrystals/nanoclusters(Pt NCs), with a brand new anti-cancer mechanism, have shown a promising potential in targeted cancer therapy, especially in Pt resistance circumvention. This review is helpful to understand the research strategies of Pt drugs, particularly, the recent developments and medical applications of Pt NCs.
基金support from the National Natural Science Foundation of China (Grant No. 20472060)the Basic Research Foundation of Sichuan Province,China (Grant No. 07JY029-015)
文摘A new series of mono-cyclometalated square planar platinum(Ⅱ) complexes have been synthesized and the single-crystal X-ray structures of complex 1 and 2 have been determined.The complexes have the general formula ppyPt(O^O),where ppy is 2-phenylpyridyl,and O^O is β-diketonate ancillary ligands with the acyl substituent group in position 3 of(D)-(+)-camphor.Although,like the many Pt(Ⅱ) complexes with square-planar geometry,these complexes have plane stacking modes in crystal structure,the sterically bulky camphor-derived groups compel extensive slipping of the molecular stacking planes,resulting in the negligible overlapping of the aromatic ring fragments between molecules and the considerable Pt-Pt distance.The resolved spectra and a little shifted emission in solid state of complexes show that there is significant reduction of π-π interactions and Pt-Pt interactions,and suggest these complexes may be good candidates for doped phosphorescent organic light emitting diodes(PhOLEDs) and even for nondoped PhOLEDs.
基金Supported by Program for Changjiang Scholars and Innovative Research Team in University, the Foundation of Jilin Provincial Excellent Youth (Grant No. 20050107)Youth Science Foundation of Northeast Normal University (Grant No. 111494117)
文摘DFT B3LYP/LANL2DZ method was employed to calculate electron properties and the second-order nonlinear optical(NLO) respond of platinum(Ⅱ) complexes which have been synthesized by Weinstein group.4,7-diphenyl-1,10-phenanthroline shows the ability to push electron in these complexes.Metal Pt plays a balancing charge role.Comparing complex 1b-6b with complex a,the βvec value of complex 1b-5b is larger than one of complex a,while the βvec value of complex 6b is smaller than one of com-plex a.In these seven complexes,the βvec values of complexes increase with decreasing of the energy difference between HOMO and LUMO.Moreover,the electron transfers from deeper layer occupied orbitals to empty orbitals have a distinct contribution to second-order NLO coefficient.
文摘The interaction of tetracyline-Pt(Ⅱ)complex with DNA was studied.The studies on absorption spectrum and electrochemistry indicate that the interaction of tetracyline with DNA is not obvious.After tetracycline interact with Pt(Ⅱ)to form complex,the complex can interact with calf thymus DNA by way of intercalation.And the formation of tetracyline-Pt(Ⅱ)complex could be affected by the pH value of the sulotion.
基金This work was financially supported by the NSFC (No. 29971019)
文摘A mononuclear complex, cis-[meso-1, 3-bis(propylsulfinyl)propane]- dichloroplatinum(Ⅱ) (Pt(C9H20O2S2)Cl2) 1, has been prepared and structurally characterizated by single-crystal X-ray diffraction. The crystal belongs to orthorhombic system, space group Pna21 with a = 22.800(3), b = 11.7662(13), c = 5.8115(6) ? V = 1559.0(3) ?, Mr = 490.36, Dc = 2.089 g/cm3, Z = 4, F(000) = 936, m (MoKa) = 9.596 mm-1 and l = 0.71073 ? The structure was refined to R = 0.0204 and wR = 0.0473 for 2703 reflections with I > 2(I). It is revealed that the central Pt(Ⅱ) ion in the title complex is bonded to two Cl atoms in a cis-configuration and two S atoms of the ligand to form the coordination geometry deviating slightly from the square planar.
基金financial support from the National Natural Science Foundation of China(No.21978042)the Fundamental Research Funds for the Central Universities(No.DUT22LAB610).
文摘A novel cationic Pt(Ⅱ)complex 2 with 2-(2,4-difluorophenyl)pyridine as the cyclometalating ligand and 1,10-phenanthroline as the auxiliary ligand has been synthesized and fully characterized.This complex exhibits much higher aggregation-induced phosphorescent emission activity than that of a nonfluorinated complex 1 in CH_(3)CN/H_(2)O.The complex 2 demonstrates efficient detection on picric acid(PA)in CH_(3)CN/H_(2)O,providing a high quenching constant(K_(SV)=2.3×10^(4) L/mol)and a low limit of detection(LOD=0.26μmol/L).In addition,complex 2 shows high selectivity for detection of PA in real water samples.Density functional theory calculations and proton nuclear magnetic resonance spectra suggest that the detection mechanism is attributed to the photo-induced electron transfer.
基金supported by the National Natural Science Foundation of China (21871192)the Major Program of Guangdong Basic and Applied Research (2019B030302009)。
文摘D-A charge transfer, including through-bond charge transfer and through-space charge transfer between two different electron donors(D) and electron acceptors(A), is a fundamental and powerful tool to tune the optical properties of organic dyes. Herein,we demonstrate a unique strategy to tune phosphorescence and circularly polarized luminescence properties of axially chiral binuclear Pt(Ⅱ) complexes through long-range charge transfer, even though these molecules have two totally identical segments on either side of the chiral core. The presence of axial chirality would break not only the symmetry of molecular structure and π-conjugation system but also the symmetry of charge distribution for long-range charge transfer. These binaphthyl-based Pt(Ⅱ)complexes bearing coordinated atoms far away from chiral axis exhibit no Pt-Pt interactions but colorful concentrationdependent phosphorescence with quantum yield up to 86.4% and could be applied as emitters in highly efficient solutionprocessed organic light-emitting diodes to achieve luminance, luminance efficiency, power efficiency, external quantum efficiency, and asymmetry factor up to 8.94 × 10^(3)cd m^(-2), 41.9 cd A-1, 18.8 lm W^(-1), 12.6% and 2.98 × 10^(-3), respectively. Therefore,the present work affords a new and simple way to utilize the inherently asymmetric advantage of chirality for the design of D-Abased organic dyes.
