9-戊基咔唑-3,6-双-(炔苯基-4-甲酸乙酯)的合成与双光子特性研究

采用钯催化的碳碳偶合反应合成了9-戊基咔唑-3,6-双-(炔苯基-4-甲酸乙酯)(I).进一步研究了化合物I在四氢呋喃和40%四氢呋喃水溶液中的光物理性质,结果显示,化合物I在40%四氢呋喃水溶液中的紫外吸收峰位置与其四氢呋喃溶液相比没有发生明显移动,它在40%四氢呋喃水溶液中的单光子荧光发射峰出现在453 nm,较其在四氢呋喃溶液的发射有42 nm红移,其荧光量子效率为0.44.用波长为660 nm飞秒激光激发时,化合物I在40%四氢呋喃水溶液中的双光子荧光发射最大峰红移至489 nm,其双光子吸收截面值为251GM,比其在四氢呋喃溶液中的截面(151 GM)增强了60%.     

Synthesis and Study of Two-photon Absorption Behavior of 3- (3-Arylacryloyl) -chromen-2-one Derivatives

The study on two-photon absorption materials has attracted a lot of attention in recent years, many good re search results have been obtained in the field of two-photon fluorescent microscopy and imaging. [ 1 ～ 4] It was found in our laboratory that some 3-(3-arylacryloyl)-chromen-2-one derivatives possess good two-photon absorption behav-ior, [5] therefore, a series of this family of compounds was synthesized.     

用于糖链抗原CA19-9实时动态活检的免疫双光子荧光标记试剂盒

采用双光子荧光标记探针LP制备了免疫双光子荧光抗体LP-Ab,以特异性识别肿瘤标志物CA19-9(Ag)形成抗原-抗体复合物(LP-Ab·Ag),基于双光子诱导荧光机制用近红外激光(740 nm)激发LP-Ab·Ag,利用LP-Ab·Ag的双光子荧光实现了CA19-9的高清晰度、高灵敏度及高分辨率的量化检测和实时动态成像,并制成用于糖链抗原CA19-9检测的简单便捷的双光子荧光标记试剂盒.     

Synthesis, and two photon absorption properties of 7,7'-(iminundecahydro-closo-dodecaborate)-9,9'-(dihexyl)-2,2'-bifluorene

Hybrid organic-inorganic bis-tetrabutylammonium-7,7'-(iminundecahydro-closo-dodecaborate)-9,9'-(dihexyl)-2,2'-bifluorene (5) was prepared, and the influence of the closo-dodecaborate cluster on the two-photon absorption properties of bi-fluorene derivatives was demonstrated.     

One-photon photophysics and two-photon absorption of 4-[9,9-di(2-ethylhexyl)-7-diphenylaminofluoren-2-yl]-2,2':6',2'-terpyridine and their platinum chloride complexes

The synthesis, one-photon photophysics and two-photon absorption (2PA) of three dipolar D-π-A 4-[9,9-di(2-ethylhexyl)-7-diphenylaminofluoren-2-yl]-2,2':6',2'-terpyridine and their platinum chloride complexes with different linkers between the donor and acceptor are reported. All ligands exhibit (1)π,π* transition in the UV and (1)π,π*/(1)ICT (intramolecular charge transfer) transition in the visible regions, while the complexes display a lower-energy (1)π,π*/(1)CT (charge transfer) transition in the visible region in addition to the high-energy (1)π,π* transitions. All ligands and the complexes are emissive at room temperature and 77 K, with the emitting excited state assigned as the mixed (1)π,π* and (1)CT states at RT. Transient absorption from the ligands and the complexes were observed. 2PA was investigated for all ligands and complexes. The two-photon absorption cross-sections (σ(2)) of the complexes (600-2000 GM) measured by Z-scan experiment are much larger than those of their corresponding ligands measured by the two-photon induced fluorescence method. The ligand and the complex with the ethynylene linker show much stronger 2PA than those with the vinylene linker.     

Zinc(II)- and copper(I)-mediated large two-photon absorption cross sections in a bis-cinnamaldiminato Schiff base

A Schiff base ligand has been synthesized by condensing 1,2-diaminobenzene with 4-(dimethylamino)cinnamaldehyde to give a donor-pi-acceptor-pi-donor system which does not show any two-photon absorption cross section but which does, upon complexation with Zn(II) or Cu(I), exhibit very high two-photon absorption cross sections.     

Single- and two-photon excited fluorescence in organic nonlinear optical single crystal 3-(1,1-dicyanoethenyl)-1-phenyl-4,5-dihydro-1H-pyrazole

Fluorescence of nonlinear optical organic single crystal of 3-(1,1-dicyanoethenyl)-1-phenyl-4,5-dihydro-1H-pyrazole (DCNP) excited by a nonabsorbed light pulses from Q-switched Nd:YAG laser λ = 1064 nm as well as absorbed λ = 532 nm light is reported. Two mechanisms of two-photon excited fluorescence are considered: (i) direct two-photon excited fluorescence and (ii) single-photon excitation due to reabsorption of light generated in process of second harmonic generation (SHG) by the crystal due to its nonlinear optical properties. Strong anisotropy of fluorescence that has been observed is linked with uniaxial molecular alignment. Fluorescence decay profile shows two- exponential decay with lifetimes of emitting species of 3.7 and 5.6 ns at 293 K. The excitation and fluorescence spectra of the DCNP single crystal have been measured at 294 K and in function of temperature down to 77.4 K. The strong bathochromic shift of fluorescence spectrum in crystal with respect to fluorescence of DCNP molecule in solution is observed and interpreted with possible formation of molecular aggregates.     

Large two-photon absorptivity of hemoglobin in the infrared range of 780-880 nm

Porphyrin molecules have a highly conjugated cyclic structure and are theorized to have unusually large two-photon absorptivities (sigmaTPA), i.e., sigmaTPA approximately 10(2) GM. The authors tested this claim. Ultrafast two-photon absorption (TPA) spectroscopy was performed on solutions of hemoglobin, which contains a naturally occurring metaloporphyrin. They used a pump-probe technique to directly detect the change in transmission induced by TPA over the wavelength range of lambda0=780-880 nm. As controls, they measured the TPA of the dyes rhodamine 6G and B; their measurements both verify and extend previously reported values. In new results, hemoglobin was found to have a peak two-photon absorptivity of sigmaTPA approximately 150 GM at lambda0=825 nm, near a resonance of the Soret band. This value supports theoretical expectations. They also found a significant difference in the TPA of carboxyhemoglobin versus oxyhemoglobin, e.g., sigmaTPA=61 GM versus sigmaTPA=18 GM, respectively, at lambda0=850 nm, which shows that the ligand affects the electronic states involved in TPA.     

Broadening and shift of theT1 6P 1/2-7P 1/2,3/2 two-photon lines perturbed by noble gases

Pressure broadening and shift coefficients of the T1 6P_1/2-7P_{1/2, 3/2} two-photon line, perturbed by noble gases, are measured by Doppler-free two-photon absorption. The experimental results are compared with theoretical values estimated with the Lindholm approximation using C₆ constants calculated as well from the Unsöld formula as from fits to pseudopotentials.     

N-甲基-2-{N-乙基-6-[2-(8-甲氧基喹啉基)乙烯基]咔唑基}富勒烯 吡咯烷的合成、电化学性质与双光子吸收特性

设计合成了N-甲基-2-{N-乙基-6-[2-(8-甲氧基喹啉基)乙烯基]咔唑基}富勒烯吡咯烷(6). 产物通过FT-IR, UV, 1H NMR, 13C NMR, MS等对其结构进行表征; 用循环伏安法测定了化合物6的电化学性质. 结果表明, 与参比化合物C60相比还原电位发生负移; 通过Z-扫描方法研究了化合物6的双光子吸收特性, 测得双光子吸收截面积可达62.58 GM. 运用Gaussian 03 量子化学程序包, 采用B3LYP密度泛函(DFT)的方法, 在3-21G(d)水平上对分子的几何构型进行了优化, 预测了化合物6的电化学性质, 与实验结果基本一致.     

Two-photon absorption properties of alkynyl-conjugated pyrene derivatives

A series of pyrene derivatives having 4-(N,N-dimethylamino)phenylethynyl groups as the substituent (1-5) have been synthesized and their two-photon absorption properties were investigated. Comparison of two-photon cross section (delta(max)) with related compounds reveals that pyrene is as efficient a pi-center as anthracene in two-photon materials. Moreover, the two-photon cross section (delta(max)) increased with the number of substituents reaching at the maximum value of 1150 GM for the tetra-substituted derivative (5). Furthermore, the two-photon action cross section (Phi delta(max)) of 5 is comparable to that the most efficient two-photon materials. This result provides a useful guideline to the design of efficient two-photon materials bearing pyrene as a pi-center.     

Two-photon excitation studies of hypocrellins for photodynamic therapy

The photophysical and photochemical properties of hypocrellins (HA and HB) are examined with two-photon excitations at 800 nm using femtosecond pulses from a Ti:sapphire laser. The two-photon excited fluorescence spectra of HA and HB are very similar to those obtained by one-photon excitation, which may indicate that the two-photon induced photodynamic processes of hypocrellins are similar to one-photon induced photodynamic processes. The two-photon excitation cross sections of HA and HB are measured at 800 nm as about 34.8 x 10(-50) cm(4) s/photon and 21.3 x 10(-50) cm(4) s/photon, respectively. The large two-photon cross sections of both HA and HB, suggest that the hypocrellins can be potential two-photon phototherapeutic agents. As an example for two-photon photodynamic therapy of hypocrellins, we also further examine the cell-damaging effects of HA upon two-photon illumination. Our preliminary results of cell viability test indicate hypocrellins can effectively damage the Hela cells under two-photon illumination.     

Charge-transfer Zn-porphyrin derivatives with very large two-photon absorption cross sections at 1.3-1.5 microm fundamental wavelengths

A series of charge-transfer Zn-porphyrin derivatives with large two-photon absorption cross sections at 1.3-1.5 microm fundamental wavelengths are designed using time-dependent hybrid density functional theory. The fluorescence of these chromospheres is expected to be in the region of 700-900 nm. These unique features make them suitable for a variety of biophotonic and telecommunication applications.     

Ab initio study of the one- and two-photon circular dichroism of R-(+)-3-methyl-cyclopentanone

One- and two-photon circular dichroism spectra of R-(+)-3-methyl-cyclopentanone, a system that has been the subject of recent experimental studies of (2+1) resonance-enhanced multiphoton ionization circular dichroism, have been calculated with an origin-invariant density functional theory approximation in the region of the lowest electronic excited states, both for the gas phase and for a selection of solvents. A polarizable continuum model is used in the calculations performed on the solvated system. Two low-lying conformers are analyzed, and a comparison of the intensities and characteristic features is made with the corresponding two-photon absorption for each species, also for the Boltzmann-averaged spectra. The effect of the choice of geometry, basis set, and exchange-correlation functional is carefully analyzed. It is found that a density functional theory approach using the Coulomb attenuating method variant of Becke's three-parameter exchange and the Lee-Yang-Parr correlation functionals with correlation-consistent basis sets of double-zeta quality can reproduce the experimental electronic circular dichroism spectra very well. The features appearing in experiment are characterized in terms of molecular excitations, and the differences in the response of each state in the one- and two-photon processes are highlighted.     

Synthesis of triphenylamine-cored dendritic two-photon absorbing chromophores

[structure: see text]. A new series of dendritic two-photon absorbing chromophores containing triphenylamine moiety as a core or branching points have been synthesized through a convergent synthetic strategy. One-photon and two-photon optical properties of these molecules were characterized. In the nanosecond time domain, these molecules exhibited large two-photon absorption (TPA) cross sections up to 7.56-12.2 x 10(-44) s cm(4) at 800 nm, indicating that these molecular structures were viable candidates for various two-photon related applications.     

Spectroscopy of UO(2)Cl(4)(2)(-) in basic aluminum chloride-1-ethyl-3-methylimidazolium chloride

The optical absorption, emission, FT Raman, one-photon excitation, two-photon excitation, and luminescence lifetime measurements are reported for UO(2)Cl(4)(2)(-) in 40:60 AlCl(3)-EMIC (where EMIC identical with 1-ethyl-3-methylimidazolium chloride), a room-temperature ionic liquid. Comparison of the spectra with previous results from single crystals containing UO(2)Cl(4)(2)(-) allowed the characterization of four ground-state vibrational frequencies, two excited-state vibrational frequencies, and the location of eight electronic excited-state energy levels. The vibrational frequencies and electronic energy levels are found to be consistent with the UO(2)Cl(4)(2)(-) ion. Comparison of the one-photon and two-photon excitation spectra, and the relative intensities of the transitions in the emission spectrum indicate that the center of symmetry is perturbed by an interaction with the solvent.     

Two-photon fluorescent probes for long-term imaging of calcium waves in live tissue

2-Acetyl-6-(dimethylamino)naphthalene-derived two-photon fluorescent Ca2+ probes (ACa1-ACa3) are reported. They can be excited by a 780 nm laser beam, show 23-50-fold enhancement in one- and two-photon excited fluorescence in response to Ca2+, emit fourfold stronger two-photon excited fluorescence than Oregon Green 488 BAPTA-1 upon complexation with Ca2+, and can selectively detect intracellular free Ca2+ ions in live cells and living tissues with minimum interference from other metal ions and membrane-bound probes. Moreover, these probes are capable of monitoring calcium waves at a depth of 120-170 microm in live tissues for 1100-4000 s using two-photon microscopy with no artifacts of photobleaching.     

Two-photon fluorescent turn-on probe for lipid rafts in live cell and tissue

We report a new two-photon fluorescence turn-on probe 6-[(E)-3-oxo-1-dodecenyl]-2-[N-methyl-N-(carboxymethyl)amino]naphthalene (CL2) that is designed specifically for visualizing lipid rafts in living cells and tissues. This probe emits much brighter two-photon excited fluorescence in lipid rafts than in non-raft domains and allows direct visualization of the lipid rafts in the live cells and pyramidal neuron layer of the CA1 region at a depth of 100-250 mum in live tissues using two-photon microscopy.     

7-Dialkylamino-3-[1,5-diaryl(3-pyrazolinyl)]coumarins: two-photon absorption in solution and in polymer film

Cross section of the two-photon absorption in 7-dialkylamino-3-(3-pyrazolinyl)coumarins in acetone and polymethylmethacrylate films has been found to be dependent on the substrate and medium nature. 7-Dialkylamino-3-[1,5-diaryl(3-pyrazolinyl)]coumarins are shown to be effective in the photosensitive media with excitation at 1060 nm for optical recording of information.     

Synthesis, Characterization and Non-linear Optical Properties of a New Organic Dye： DEAHAS

Two-photon absorption (TPA) is a process in which two photons are simultaneously absorbed to an excited state via a virtual state. The synthesis of organic optical materials with large TPA cross section has become a subject of great interest in recent years due to various application such as three-dimensional fluorescence imaging1, optical data storage2,3 and lithographic microfabrication4-6. Recently we have synthesized a new organic dye DEAHAS that is a symmetrically substituted stilbe…