Suzuki coupling reaction is widely used in the construction of conjugated polymers; however, there is still no report describing the mechanism and coupling of 9,10-phenanthrenequinone(PQ) building blocks via Suzuki ...Suzuki coupling reaction is widely used in the construction of conjugated polymers; however, there is still no report describing the mechanism and coupling of 9,10-phenanthrenequinone(PQ) building blocks via Suzuki reaction because PQ is sensitive to bases and light. Herein is reported the efficient Suzuki coupling of PQ with 9,10-dialkylfluorene with Na2CO3 as basic species and high molecular weight PQ-Alt-Dialkyl-Fluorene conjugated copolymer obtained in an yield of 42%. Based on the characterization data and well-accepted literature, we proposed a step-by-step mechanistic explanation for the formation of the PQ containing alternating conjugated copolymer.展开更多
A functional amphiphile, N^6 -myristoyl-9-[ 8-( 1-trimethylamino) octyl ] adenine bromide (MTOAB), was used to form coliposomes of phosphatidyleholine(PC), PC/thymine, and PC/TOTB using sonication . The morpholo...A functional amphiphile, N^6 -myristoyl-9-[ 8-( 1-trimethylamino) octyl ] adenine bromide (MTOAB), was used to form coliposomes of phosphatidyleholine(PC), PC/thymine, and PC/TOTB using sonication . The morphologies of the coliposomes were characterized using TEM (transmission electron microscopy). The UV-Vis spectroscopic behavior of PC/MTOAB/thymine (molar ratio = 5: 1: 1 ) and PC/MTOAB/TOTB (molar ratio = 5: 1: 1 ) of coliposomal solutions showed that as a result of base pairing, absorption intensity showed a decrease at 263 nm with increase of time. The decrease of absorption intensity is ascribed to the hypochromic effect, which is because of the formation of hydrogen bonds between adenine and thymine in the coliposomes. The same effect was also observed for the mixture of aqueous PC/MTOAB liposomes and PC/TOTB liposomes after fusion, whereas the nocomplementary coliposomcs formed from PC/MTOAB and PC/TOTB did not show these spectroscopic changes. The molecular recognition through hydrogen interactions between adenine and thymine is very slow because of the possible occurrence of molecular lateral diffusion and exchange of amphiphile before recognition progresses in coliposomes. These results provide useful information for the design of supramolecular devices such as vesicles and liposomes,which can be used to mimic primitive recognition processes observed in biological systems.展开更多
The self-assembly behavior of the amphiphilic block copolymer poly( methyl methacrylate) -block-poly( lead dimethacrylate) (PMMA-b-PLDMA) with cross-linked hydrophilic block(PLDMA) in ethanol was investigated....The self-assembly behavior of the amphiphilic block copolymer poly( methyl methacrylate) -block-poly( lead dimethacrylate) (PMMA-b-PLDMA) with cross-linked hydrophilic block(PLDMA) in ethanol was investigated. The results show that the size and morphology of the resulting micelle or micellar aggregates are ascribed to the content of ethanol and the nature of the solvent mixture. PbS nanoparticles were formed in the micelle by in situ reaction with H2S gas. The morphology and size of the self-assembly objects were investigated using scanning electron microscopy (SEM) and transmission electron microscopy(TEM).展开更多
A soluble poly(meta-phenylene) derivative with rigid twisted biphenyl unit was synthesized by the Yamamoto coupling reaction. The polymer is soluble in common organic solvents, and the number-average molecular weigh...A soluble poly(meta-phenylene) derivative with rigid twisted biphenyl unit was synthesized by the Yamamoto coupling reaction. The polymer is soluble in common organic solvents, and the number-average molecular weight is about 6500. The UV-Vis and quantum chemical calculation indicate that the different conformation segments named "conformers" exist in the polymer backbones; it was also further confirmed by the single crystal X-ray diffraction study of the dimeric model compound. The π-π^* transition of biphenyl segments of twisted and planar conformations made the polymer exhibit a strong absorption around 256 nm and a weak absorption at about 300 nm. Furthermore, the polymer exhibits a strong UV photoluminescence at 372 nm when the excitation wavelengths are longer than 300 run. The ultraviolet-emitting electroluminescence(EL) device with the single layer structure shows EL λmax of the derivative at 370 nm.展开更多
基金the National Natural Science Foundation of China(Nos.20573040, 20474024, 20125421, 90101026 and 50303007)National Basic Research Program of China(Nos.2002CB6134003 and 2003CB314703) and PCSIRT
文摘Suzuki coupling reaction is widely used in the construction of conjugated polymers; however, there is still no report describing the mechanism and coupling of 9,10-phenanthrenequinone(PQ) building blocks via Suzuki reaction because PQ is sensitive to bases and light. Herein is reported the efficient Suzuki coupling of PQ with 9,10-dialkylfluorene with Na2CO3 as basic species and high molecular weight PQ-Alt-Dialkyl-Fluorene conjugated copolymer obtained in an yield of 42%. Based on the characterization data and well-accepted literature, we proposed a step-by-step mechanistic explanation for the formation of the PQ containing alternating conjugated copolymer.
基金Supported by the National Natural Science Foundation of China(Nos. 50473005 and 20274015).
文摘A functional amphiphile, N^6 -myristoyl-9-[ 8-( 1-trimethylamino) octyl ] adenine bromide (MTOAB), was used to form coliposomes of phosphatidyleholine(PC), PC/thymine, and PC/TOTB using sonication . The morphologies of the coliposomes were characterized using TEM (transmission electron microscopy). The UV-Vis spectroscopic behavior of PC/MTOAB/thymine (molar ratio = 5: 1: 1 ) and PC/MTOAB/TOTB (molar ratio = 5: 1: 1 ) of coliposomal solutions showed that as a result of base pairing, absorption intensity showed a decrease at 263 nm with increase of time. The decrease of absorption intensity is ascribed to the hypochromic effect, which is because of the formation of hydrogen bonds between adenine and thymine in the coliposomes. The same effect was also observed for the mixture of aqueous PC/MTOAB liposomes and PC/TOTB liposomes after fusion, whereas the nocomplementary coliposomcs formed from PC/MTOAB and PC/TOTB did not show these spectroscopic changes. The molecular recognition through hydrogen interactions between adenine and thymine is very slow because of the possible occurrence of molecular lateral diffusion and exchange of amphiphile before recognition progresses in coliposomes. These results provide useful information for the design of supramolecular devices such as vesicles and liposomes,which can be used to mimic primitive recognition processes observed in biological systems.
基金Suppored by the National Natural Science Foundation of China ( Nos 20374024 and 20534040) and the Program forChangjiang Scholars and Innovative Research Team in Universities(No IRT0422)
文摘The self-assembly behavior of the amphiphilic block copolymer poly( methyl methacrylate) -block-poly( lead dimethacrylate) (PMMA-b-PLDMA) with cross-linked hydrophilic block(PLDMA) in ethanol was investigated. The results show that the size and morphology of the resulting micelle or micellar aggregates are ascribed to the content of ethanol and the nature of the solvent mixture. PbS nanoparticles were formed in the micelle by in situ reaction with H2S gas. The morphology and size of the self-assembly objects were investigated using scanning electron microscopy (SEM) and transmission electron microscopy(TEM).
基金Supported by the National Natural Science Foundation of China(Nos.20125421,90101026,50303007,20474024 and 50473001)Ministry of Science and Technology of China(No.2002CB6134003).
文摘A soluble poly(meta-phenylene) derivative with rigid twisted biphenyl unit was synthesized by the Yamamoto coupling reaction. The polymer is soluble in common organic solvents, and the number-average molecular weight is about 6500. The UV-Vis and quantum chemical calculation indicate that the different conformation segments named "conformers" exist in the polymer backbones; it was also further confirmed by the single crystal X-ray diffraction study of the dimeric model compound. The π-π^* transition of biphenyl segments of twisted and planar conformations made the polymer exhibit a strong absorption around 256 nm and a weak absorption at about 300 nm. Furthermore, the polymer exhibits a strong UV photoluminescence at 372 nm when the excitation wavelengths are longer than 300 run. The ultraviolet-emitting electroluminescence(EL) device with the single layer structure shows EL λmax of the derivative at 370 nm.