Lijin Tian - Academia.edu (original) (raw)
Papers by Lijin Tian
Morphology impact on the upconverted luminescence of ZnO:Er3+ nanocrystals was studied with contr... more Morphology impact on the upconverted luminescence of ZnO:Er3+ nanocrystals was studied with controllable morphology of nanorod, prickly sphere-like, column-like, branch rod, prism-like, and grain-like, prepared via the cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal process. The upconversion emission of Er3+ with 980nm excitation demonstrated morphology sensitivity which was related with the local environments of Er3+ ions in ZnO and doping efficiency. Under ultraviolet
Silver nanoparticle aggregates have been shown to support very large enhancements of fluorescence... more Silver nanoparticle aggregates have been shown to support very large enhancements of fluorescence intensity from organic dye molecules coupled with an extreme reduction in observed fluorescence lifetimes. Here we show that for the same type of aggregates, similar enhancement factors (B75Â in intensity and B3400Â in lifetime compared to the native radiative lifetime) are observed for a ruthenium-based phosphorescent dye (when taking into account the effect of charge and the excitation/emission wavelengths). Additionally, the inherently long native phosphorescence lifetimes practically enable more detailed analyses of the distribution of lifetimes (compared with the case with fluorescence decays). It was thus possible to unambiguously observe the deviation from monoexponential decay which we attribute to emission from a distribution of fluorophores with different lifetimes, as we could expect from a random aggregation process. We believe that combining phosphorescent dyes with plasmonic structures, even down to the single dye level, will offer a convenient approach to better characterize plasmonic systems in detail. † Electronic supplementary information (ESI) available: Luminescence enhancement of the Ru-dye with time and lifetime of MB in Ag nanoparticle aggregates. See
Surface effects on nanoparticles have been explored by picosecond time-resolved spectroscopy usin... more Surface effects on nanoparticles have been explored by picosecond time-resolved spectroscopy using Ce3+ ions doped in yttrium aluminum garnet (YAG) nano-phosphors (NPS) as a probe. Non-exponential decays have been observed over the entire emission band that could be fitted well with four decay components varying from ∼150ps to ∼70ns. These components have been assigned to originate from sites different in
Morphology impact on the upconverted luminescence of ZnO:Er3+ nanocrystals was studied with contr... more Morphology impact on the upconverted luminescence of ZnO:Er3+ nanocrystals was studied with controllable morphology of nanorod, prickly sphere-like, column-like, branch rod, prism-like, and grain-like, prepared via the cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal process. The upconversion emission of Er3+ with 980nm excitation demonstrated morphology sensitivity which was related with the local environments of Er3+ ions in ZnO and doping efficiency. Under ultraviolet
Hierarchical cobalt assemblies such as spheres, flowers with dendritic petals, and flowers with s... more Hierarchical cobalt assemblies such as spheres, flowers with dendritic petals, and flowers with sharp petals are successfully synthesized via a facile liquid-phase reduction method by simply adjusting the reaction conditions. The morphology evolution process and transformation mechanism from spheres to dendrites and finally to flowers have been systematically investigated. It is determined that coercivity H c depends more on sample size than on shape anisotropy, while saturation magnetization M s is greatly affected by pinned surface magnetic moment. Even at a thinner thickness, as-synthesized cobalt samples exhibit stronger microwave absorbing ability compared with reported cobalt in the same frequency band. Especially, the cobalt flowers with dendritic petals exhibit the strongest absorption in middle frequency because incident wave and reflected wave are totally canceled at matching thickness. The architectural design of material morphologies is critical for improving properties toward future application.
The enhanced local fields around plasmonic structures can lead to enhancement of the excitation a... more The enhanced local fields around plasmonic structures can lead to enhancement of the excitation and modification of the emission quantum yield of fluorophores. So far, high enhancement of fluorescence intensity from dye molecules was demonstrated using bow-tie gap antenna made by e-beam lithography. However, the high manufacturing cost and the fact that currently there are no effective ways to place fluorophores only at the gap prevent the use of these structures for enhancing fluorescence-based biochemical assays. We report on the simultaneous modification of fluorescence intensity and lifetime of dye-labeled DNA in the presence of aggregated silver nanoparticles. The nanoparticle aggregates act as efficient plasmonic antennas, leading to more than 2 orders of magnitude enhancement of the average fluorescence. This is comparable to the best-reported fluorescence enhancement for a single molecule but here applies to the average signal detected from all fluorophores in the system. This highlights the remarkable efficiency of this system for surface-enhanced fluorescence. Moreover, we show that the fluorescence intensity enhancement varies with the plasmon resonance position and measure a significant reduction (300×) of the fluorescence lifetime. Both observations are shown to be in agreement with the electromagnetic model of surface-enhanced fluorescence.
Photosystems I (PSI) and II (PSII) are two major pigment-protein complexes of photosynthetic orga... more Photosystems I (PSI) and II (PSII) are two major pigment-protein complexes of photosynthetic organisms that function in series to convert sunlight energy into chemical energy. We have studied the picosecond fluorescence behaviour of the core of both photosystems in vivo by using two Synechocystis PCC 6803 mutants: BE cells contain PSI but are lacking both PSII and the light-harvesting complexes called phycobilisomes (PBs) whereas PAL cells contain both PSI and PSII but lack the PBs. Measurements were performed at room temperature and at 77 K. The fluorescence kinetics of PSI and PSII can nicely be separated, en passant providing the PSI/PSII ratio. At room temperature, the PSI kinetics are identical to those of isolated PSI whereas the PSII kinetics can equally well be described by the in vitro trap-limited model of Y. Miloslavina, M. Szczepaniak, M. G. Muller, J. Sander, M. Nowaczyk, M. Rogner and A. R. Holzwarth, Biophys J., 2009, 96(2), 621-631, and by the transfer-to-the-trap-limited model of C. D. van der Weij-de Wit, J. P. Dekker, R. van Grondelle and I. H. M. van Stokkum, J. Phys. Chem. A, 2011, 115(16), 3947-3956, albeit that the in vivo kinetics turn out to be somewhat slower. At 77 K several low-energy pigments are observed in both photosystems which complicate the overall dynamics but the PSII kinetics can still be described by both a trap-limited and a transfer-to-the-trap-limited model.
Strong red upconversion luminescence of rare-earth ions doped in nanocrystals is desirable for th... more Strong red upconversion luminescence of rare-earth ions doped in nanocrystals is desirable for the biological/biomedical applications. In this paper, we describe the great enhancement of red upconversion emission (4F9/2 --> I15/2 transition of Er3+ ion) in NaYF4:Yb3+, Er3+ nanocrystals at low doping level, which is ascribed to the effectiveness of the multiphonon relaxation process due to the existence of citrate as a chelator and cross relaxation between Er3+ ions. The dissolution-recrystallization transformation, governing both the intrinsic crystalline phase (cubic and/or hexagonal phase) and the growth regime (thermodynamic vs kinetic), is responsible for the phase control of the NaYF4 crystals. The possible formation mechanism of the NaYF4 crystals and the role of trisodium citrate which acts as a chelating agent and shape modifier are discussed in detail. It is also found that the alpha --> beta phase transition is favored by the high molar ratio of fluoride to lanthanide and high hydrothermal temperature as well as long hydrothermal time.
Cyanobacteria are oxygen-evolving photosynthetic organisms that harvest sunlight and convert exci... more Cyanobacteria are oxygen-evolving photosynthetic organisms that harvest sunlight and convert excitation energy into chemical energy. Most of the light is absorbed by large light harvesting complexes called phycobilisomes (PBs). In high-light conditions, cyanobacteria switch on a photoprotective mechanism called non-photochemical quenching (NPQ): During this process, absorption of blue-green light transforms the inactive orange form of the orange carotenoid protein OCP (OCP o ) into the red active form OCP r that subsequently binds to the PB, resulting in a substantial loss of excitation energy and corresponding decrease of the fluorescence. In wild-type cells, the quenching site is a bilin chomophore that fluoresces at 660 nm and which is called APC Q 660 . In the present work, we studied NPQ in two different types of mutant cells (CB and CK) that possess significantly truncated PBs, using spectrally resolved picosecond fluorescence spectroscopy. The results are in very good agreement with earlier in vitro experiments on quenched and unquenched PBs, although the fraction of quenched PBs is far lower in vivo. It is also lower than the fraction of PBs that is quenched in wild-type cells, but the site, rate, and location of quenching appear to be very similar.
In high light conditions, cyanobacteria dissipate excess absorbed energy as heat in the light-har... more In high light conditions, cyanobacteria dissipate excess absorbed energy as heat in the light-harvesting phycobilisomes (PBs) to protect the photosynthetic system against photodamage. This process requires the binding of the red active form of the Orange Carotenoid Protein (OCP r ), which can effectively quench the excited state of one of the allophycocyanin bilins. Recently, an in vitro reconstitution system was developed using isolated OCP and isolated PBs from Synechocystis PCC 6803. Here we have used spectrally resolved picosecond fluorescence to study wild-type and two mutated PBs. The results demonstrate that the quenching for all types of PBs takes place on an allophycocyanin bilin emitting at 660 nm (APC Q 660 ) with a molecular quenching rate that is faster than (1 ps) À1 . Moreover, it is concluded that both the mechanism and the site of quenching are the same in vitro and in vivo. Thus, utilization of the in vitro system should make it possible in the future to elucidate whether the quenching is caused by charge transfer between APC Q 660 and OCP or by excitation energy transfer from APC Q 660 to the S 1 state of the carotenoid-a distinction that is very hard, if not impossible, to make in vivo.
In cyanobacteria, activation of the Orange Carotenoid Protein (OCP) by intense blue-green light t... more In cyanobacteria, activation of the Orange Carotenoid Protein (OCP) by intense blue-green light triggers photoprotective thermal dissipation of excess absorbed energy leading to a decrease (quenching) of fluorescence of the light harvesting phycobilisomes and, concomitantly, of the energy arriving to the reaction centers. Using spectrally resolved picosecond fluorescence, we have studied cells of wild-type Synechocystis sp. PCC 6803 and of mutants without and with extra OCP (ΔOCP and OverOCP) both in the unquenched and quenched state. With the use of target analysis, we managed to spectrally resolve seven different pigment pools in the phycobilisomes and photosystems I and II, and to determine the rates of excitation energy transfer between them. In addition, the fraction of quenched phycobilisomes and the rates of charge separation and quenching were resolved. Under our illumination conditions, ∼72% of the phycobilisomes in OverOCP appeared to be substantially quenched. For wild-type cells, this number was only ∼29%. It is revealed that upon OCP activation, a bilin chromophore in the core of the phycobilisome, here called APC(Q)(660), with fluorescence maximum at 660 nm becomes an effective quencher that prevents more than 80% of the excitations in the phycobilisome to reach Photosystems I and II. The quenching rate of its excited state is extremely fast, that is, at least (∼240 ± 60 fs)(-1). It is concluded that the quenching is most likely caused by charge transfer between APC(Q)(660) and the OCP carotenoid hECN in its activated form.
7 article info 8 I (PSI) is an essential component of photosynthetic membranes. Despite the high ... more 7 article info 8 I (PSI) is an essential component of photosynthetic membranes. Despite the high sequence and 23 structural homology, its absorption properties differ substantially in algae, plants and cyanobacteria. In particular 24 it is characterized by the presence of low-energy chlorophylls (red forms), the number and the energy of which 25 vary in different organisms. The PSI-LHCI (PSI-light harvesting complex I) complex of the green alga 26
Morphology impact on the upconverted luminescence of ZnO:Er3+ nanocrystals was studied with contr... more Morphology impact on the upconverted luminescence of ZnO:Er3+ nanocrystals was studied with controllable morphology of nanorod, prickly sphere-like, column-like, branch rod, prism-like, and grain-like, prepared via the cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal process. The upconversion emission of Er3+ with 980nm excitation demonstrated morphology sensitivity which was related with the local environments of Er3+ ions in ZnO and doping efficiency. Under ultraviolet
Silver nanoparticle aggregates have been shown to support very large enhancements of fluorescence... more Silver nanoparticle aggregates have been shown to support very large enhancements of fluorescence intensity from organic dye molecules coupled with an extreme reduction in observed fluorescence lifetimes. Here we show that for the same type of aggregates, similar enhancement factors (B75Â in intensity and B3400Â in lifetime compared to the native radiative lifetime) are observed for a ruthenium-based phosphorescent dye (when taking into account the effect of charge and the excitation/emission wavelengths). Additionally, the inherently long native phosphorescence lifetimes practically enable more detailed analyses of the distribution of lifetimes (compared with the case with fluorescence decays). It was thus possible to unambiguously observe the deviation from monoexponential decay which we attribute to emission from a distribution of fluorophores with different lifetimes, as we could expect from a random aggregation process. We believe that combining phosphorescent dyes with plasmonic structures, even down to the single dye level, will offer a convenient approach to better characterize plasmonic systems in detail. † Electronic supplementary information (ESI) available: Luminescence enhancement of the Ru-dye with time and lifetime of MB in Ag nanoparticle aggregates. See
Surface effects on nanoparticles have been explored by picosecond time-resolved spectroscopy usin... more Surface effects on nanoparticles have been explored by picosecond time-resolved spectroscopy using Ce3+ ions doped in yttrium aluminum garnet (YAG) nano-phosphors (NPS) as a probe. Non-exponential decays have been observed over the entire emission band that could be fitted well with four decay components varying from ∼150ps to ∼70ns. These components have been assigned to originate from sites different in
Morphology impact on the upconverted luminescence of ZnO:Er3+ nanocrystals was studied with contr... more Morphology impact on the upconverted luminescence of ZnO:Er3+ nanocrystals was studied with controllable morphology of nanorod, prickly sphere-like, column-like, branch rod, prism-like, and grain-like, prepared via the cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal process. The upconversion emission of Er3+ with 980nm excitation demonstrated morphology sensitivity which was related with the local environments of Er3+ ions in ZnO and doping efficiency. Under ultraviolet
Hierarchical cobalt assemblies such as spheres, flowers with dendritic petals, and flowers with s... more Hierarchical cobalt assemblies such as spheres, flowers with dendritic petals, and flowers with sharp petals are successfully synthesized via a facile liquid-phase reduction method by simply adjusting the reaction conditions. The morphology evolution process and transformation mechanism from spheres to dendrites and finally to flowers have been systematically investigated. It is determined that coercivity H c depends more on sample size than on shape anisotropy, while saturation magnetization M s is greatly affected by pinned surface magnetic moment. Even at a thinner thickness, as-synthesized cobalt samples exhibit stronger microwave absorbing ability compared with reported cobalt in the same frequency band. Especially, the cobalt flowers with dendritic petals exhibit the strongest absorption in middle frequency because incident wave and reflected wave are totally canceled at matching thickness. The architectural design of material morphologies is critical for improving properties toward future application.
The enhanced local fields around plasmonic structures can lead to enhancement of the excitation a... more The enhanced local fields around plasmonic structures can lead to enhancement of the excitation and modification of the emission quantum yield of fluorophores. So far, high enhancement of fluorescence intensity from dye molecules was demonstrated using bow-tie gap antenna made by e-beam lithography. However, the high manufacturing cost and the fact that currently there are no effective ways to place fluorophores only at the gap prevent the use of these structures for enhancing fluorescence-based biochemical assays. We report on the simultaneous modification of fluorescence intensity and lifetime of dye-labeled DNA in the presence of aggregated silver nanoparticles. The nanoparticle aggregates act as efficient plasmonic antennas, leading to more than 2 orders of magnitude enhancement of the average fluorescence. This is comparable to the best-reported fluorescence enhancement for a single molecule but here applies to the average signal detected from all fluorophores in the system. This highlights the remarkable efficiency of this system for surface-enhanced fluorescence. Moreover, we show that the fluorescence intensity enhancement varies with the plasmon resonance position and measure a significant reduction (300×) of the fluorescence lifetime. Both observations are shown to be in agreement with the electromagnetic model of surface-enhanced fluorescence.
Photosystems I (PSI) and II (PSII) are two major pigment-protein complexes of photosynthetic orga... more Photosystems I (PSI) and II (PSII) are two major pigment-protein complexes of photosynthetic organisms that function in series to convert sunlight energy into chemical energy. We have studied the picosecond fluorescence behaviour of the core of both photosystems in vivo by using two Synechocystis PCC 6803 mutants: BE cells contain PSI but are lacking both PSII and the light-harvesting complexes called phycobilisomes (PBs) whereas PAL cells contain both PSI and PSII but lack the PBs. Measurements were performed at room temperature and at 77 K. The fluorescence kinetics of PSI and PSII can nicely be separated, en passant providing the PSI/PSII ratio. At room temperature, the PSI kinetics are identical to those of isolated PSI whereas the PSII kinetics can equally well be described by the in vitro trap-limited model of Y. Miloslavina, M. Szczepaniak, M. G. Muller, J. Sander, M. Nowaczyk, M. Rogner and A. R. Holzwarth, Biophys J., 2009, 96(2), 621-631, and by the transfer-to-the-trap-limited model of C. D. van der Weij-de Wit, J. P. Dekker, R. van Grondelle and I. H. M. van Stokkum, J. Phys. Chem. A, 2011, 115(16), 3947-3956, albeit that the in vivo kinetics turn out to be somewhat slower. At 77 K several low-energy pigments are observed in both photosystems which complicate the overall dynamics but the PSII kinetics can still be described by both a trap-limited and a transfer-to-the-trap-limited model.
Strong red upconversion luminescence of rare-earth ions doped in nanocrystals is desirable for th... more Strong red upconversion luminescence of rare-earth ions doped in nanocrystals is desirable for the biological/biomedical applications. In this paper, we describe the great enhancement of red upconversion emission (4F9/2 --> I15/2 transition of Er3+ ion) in NaYF4:Yb3+, Er3+ nanocrystals at low doping level, which is ascribed to the effectiveness of the multiphonon relaxation process due to the existence of citrate as a chelator and cross relaxation between Er3+ ions. The dissolution-recrystallization transformation, governing both the intrinsic crystalline phase (cubic and/or hexagonal phase) and the growth regime (thermodynamic vs kinetic), is responsible for the phase control of the NaYF4 crystals. The possible formation mechanism of the NaYF4 crystals and the role of trisodium citrate which acts as a chelating agent and shape modifier are discussed in detail. It is also found that the alpha --> beta phase transition is favored by the high molar ratio of fluoride to lanthanide and high hydrothermal temperature as well as long hydrothermal time.
Cyanobacteria are oxygen-evolving photosynthetic organisms that harvest sunlight and convert exci... more Cyanobacteria are oxygen-evolving photosynthetic organisms that harvest sunlight and convert excitation energy into chemical energy. Most of the light is absorbed by large light harvesting complexes called phycobilisomes (PBs). In high-light conditions, cyanobacteria switch on a photoprotective mechanism called non-photochemical quenching (NPQ): During this process, absorption of blue-green light transforms the inactive orange form of the orange carotenoid protein OCP (OCP o ) into the red active form OCP r that subsequently binds to the PB, resulting in a substantial loss of excitation energy and corresponding decrease of the fluorescence. In wild-type cells, the quenching site is a bilin chomophore that fluoresces at 660 nm and which is called APC Q 660 . In the present work, we studied NPQ in two different types of mutant cells (CB and CK) that possess significantly truncated PBs, using spectrally resolved picosecond fluorescence spectroscopy. The results are in very good agreement with earlier in vitro experiments on quenched and unquenched PBs, although the fraction of quenched PBs is far lower in vivo. It is also lower than the fraction of PBs that is quenched in wild-type cells, but the site, rate, and location of quenching appear to be very similar.
In high light conditions, cyanobacteria dissipate excess absorbed energy as heat in the light-har... more In high light conditions, cyanobacteria dissipate excess absorbed energy as heat in the light-harvesting phycobilisomes (PBs) to protect the photosynthetic system against photodamage. This process requires the binding of the red active form of the Orange Carotenoid Protein (OCP r ), which can effectively quench the excited state of one of the allophycocyanin bilins. Recently, an in vitro reconstitution system was developed using isolated OCP and isolated PBs from Synechocystis PCC 6803. Here we have used spectrally resolved picosecond fluorescence to study wild-type and two mutated PBs. The results demonstrate that the quenching for all types of PBs takes place on an allophycocyanin bilin emitting at 660 nm (APC Q 660 ) with a molecular quenching rate that is faster than (1 ps) À1 . Moreover, it is concluded that both the mechanism and the site of quenching are the same in vitro and in vivo. Thus, utilization of the in vitro system should make it possible in the future to elucidate whether the quenching is caused by charge transfer between APC Q 660 and OCP or by excitation energy transfer from APC Q 660 to the S 1 state of the carotenoid-a distinction that is very hard, if not impossible, to make in vivo.
In cyanobacteria, activation of the Orange Carotenoid Protein (OCP) by intense blue-green light t... more In cyanobacteria, activation of the Orange Carotenoid Protein (OCP) by intense blue-green light triggers photoprotective thermal dissipation of excess absorbed energy leading to a decrease (quenching) of fluorescence of the light harvesting phycobilisomes and, concomitantly, of the energy arriving to the reaction centers. Using spectrally resolved picosecond fluorescence, we have studied cells of wild-type Synechocystis sp. PCC 6803 and of mutants without and with extra OCP (ΔOCP and OverOCP) both in the unquenched and quenched state. With the use of target analysis, we managed to spectrally resolve seven different pigment pools in the phycobilisomes and photosystems I and II, and to determine the rates of excitation energy transfer between them. In addition, the fraction of quenched phycobilisomes and the rates of charge separation and quenching were resolved. Under our illumination conditions, ∼72% of the phycobilisomes in OverOCP appeared to be substantially quenched. For wild-type cells, this number was only ∼29%. It is revealed that upon OCP activation, a bilin chromophore in the core of the phycobilisome, here called APC(Q)(660), with fluorescence maximum at 660 nm becomes an effective quencher that prevents more than 80% of the excitations in the phycobilisome to reach Photosystems I and II. The quenching rate of its excited state is extremely fast, that is, at least (∼240 ± 60 fs)(-1). It is concluded that the quenching is most likely caused by charge transfer between APC(Q)(660) and the OCP carotenoid hECN in its activated form.
7 article info 8 I (PSI) is an essential component of photosynthetic membranes. Despite the high ... more 7 article info 8 I (PSI) is an essential component of photosynthetic membranes. Despite the high sequence and 23 structural homology, its absorption properties differ substantially in algae, plants and cyanobacteria. In particular 24 it is characterized by the presence of low-energy chlorophylls (red forms), the number and the energy of which 25 vary in different organisms. The PSI-LHCI (PSI-light harvesting complex I) complex of the green alga 26