Resonance hyper-Raman scattering from conjugated organic donor-acceptor "push-pull" chromophores with large first hyperpolarizabilities

Resonance hyper-Raman spectra have been obtained using 1064 nm excitation for several electron donor-acceptor-substituted, pi-conjugated "push-pull" molecules that have large second harmonic hyperpolarizabilities. The hyper-Raman spectra are nearly identical to the resonance Raman spectra measured with 532 nm excitation. This indicates that both the second harmonic hyperpolarizability and the linear absorption are dominated by the same, single electronic transition that is both one- and two-photon allowed. Comparison of resonance Raman and resonance hyper-Raman spectra is proposed as an experimental test of the common two-electronic-state model for the first hyperpolarizability.     

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.     

用于细胞核成像的2,7-BHVC双光子荧光探针

分别合成了2,7-双(1-羟乙基-4-乙烯基吡啶) 咔唑碘盐(2,7-BHVC)与3,6-BHVC, 进行了荧光性能和细胞核成像测试, 结果表明, 2,7位的Ф×δ是3,6位的2.8~3.6倍, 染色实验也证实了2,7-BHVC有特定成像细胞核的能力.     

Novel Y-type two-photon active fluorophore: synthesis and application in fluorescent sensor for cysteine and homocysteine

A novel Y-shaped two-photon active material FD3 based on the imidazole core has been synthesized and exhibited intense two-photon excited fluorescence with two-photon absorption cross-section of more than 9000 GM. Importantly, FD3 could be used as a potential two-photon excited fluorescent sensor for cysteine and homocysteine.     

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 sensor for metal ions derived from azacrown ether

A two-photon sensor for the metal ions derived from azacrown ether as the receptor is reported. The sensor emits strong two-photon fluorescence when excited by 800 nm laser photons. Moreover, the binding constants measured by the one- and two-photon fluorescence are similar. This result may be useful for the design of efficient two-photon fluorescence probes for biological substrates.     

Two-photon excitation action cross-sections of the autofluorescent proteins

We report on the values of the two-photon excitation action cross-sections of commercially available enhanced cyan, green, yellow, and red fluorescent proteins. The two-photon absorption spectra are very similar in shape to those measured for one-photon absorption. However, they exhibit a significant blueshift, which is attributed to the participation of a vibrational mode in the two-photon absorption process. The two-photon spectra are compared to that of flavine mononucleotide, which constitutes the main source of autofluorescence in mammalian cells. The definition of a relative detection yield between the autofluorescent proteins and flavine allows us to quantify the applicability of autofluorescent proteins in two-photon single-molecule studies in living cells.     

Molecular two-photon sensor for metal ions derived from bis(2-pyridyl)amine

A molecular two-photon sensor for the metal ions derived from bis(2-pyridyl)amine as the receptor is reported. The sensor emits strong two-photon fluorescence when excited by 780 nm laser photons. Moreover, the binding constants measured by the one- and two-photon fluorescence are similar. This result may be useful for the design of efficient two-photon fluorescence probe for biological substrates.     

双光子光聚合与功能微纳结构制备

随着纳米光电子学及生物医学组织工程领域的发展,器件的小型化、结构多样化及高度集成化,给微纳结构与器件制造领域带来了新的挑战。本文围绕飞秒激光双光子聚合技术,简要综述了双光子光聚合基本原理与双光子引发剂分子的研究进展,并对飞秒激光双光子聚合技术在功能微纳结构与器件制备中的应用及发展前景进行了展望。     

Two-photon dispersion in conjugated polymers

The frequency dependence of the dispersive and absorptive parts of a strongly allowed two-photon transition is determined in a series of conjugated polymer solutions. The data analysis yields the energy and width of the two-photon transition, symmetry assignment for the two-photon transition (A_g → A_g), and oscillator strengths for both the one-photon and two-photon transitions.     

有机双光子吸收材料研究进展

有机双光子吸收材料是光电信息功能材料领域的研究热点之一.同无机双光子吸收材料相比,有机双光子吸收材料有更好的可设计性和可裁接性.从分子设计的角度介绍了国内外所取得的一些最新进展,并对有机双光子吸收材料的发展方向作了综述.     

Organically modified silica nanoparticles co-encapsulating photosensitizing drug and aggregation-enhanced two-photon absorbing fluorescent dye aggregates for two-photon photodynamic therapy

We report energy-transferring organically modified silica nanoparticles for two-photon photodynamic therapy. These nanoparticles co-encapsulate two-photon fluorescent dye nanoaggregates as an energy up-converting donor and a photosensitizing PDT drug as an acceptor. They combine two features: (i) aggregation-enhanced two-photon absorption and emission properties of a novel two-photon dye and (ii) nanoscopic fluorescence resonance energy transfer between this nanoaggregate and a photosensitizer, 2-devinyl-2-(1-hexyloxyethyl)pyropheophorbide. Stable aqueous dispersions of the co-encapsulating nanoparticles (diameter < or = 30 nm) have been prepared in the nonpolar interior of micelles by coprecipitating an organically modified silica sol with the photosensitizer and an excess amount of the two-photon dye which forms fluorescent aggregates by phase separation from the particle matrix. Using a multidisciplinary nanophotonic approach, we show: (i) indirect excitation of the photosensitizer through efficient two-photon excited intraparticle energy transfer from the dye aggregates in the intracellular environment of tumor cells and (ii) generation of singlet oxygen and in vitro cytotoxic effect in tumor cells by photosensitization under two-photon irradiation.     

Spectroscopic Characteristics of Hyperbranched Conjugated Polymers Studied by One- and Two-Photon Excitations

Spectroscopic properties of new hyperbranched conjugated polymers functionalized in periphery with N,N-dimethylaniline and tert-butyl-benzene as terminal groups are investigated by one- and two-photon excitations. The absorption, °uorescence excitation and emission spectra are examined in chloroform and N,N-dimethylformamide. The two-photon excitation measurements show that the new hyperbranched conjugated polymer possesses large two-photon excitation cross section which makes it a very attractive candidate for the potential application as nonlinear optical materials. As an example, the two-photon induced three-dimensional data storage is also demonstrated.     

Dipicolinate as acceptor in D-π-A chromophores: synthesis, characterization and fluorescence following single- and two-photon excitation

Three novel donor-π-acceptor type compounds with dipicolinate as acceptor have been synthesized. Their absorption, photoluminescence as well as their two-photon absorption properties have been investigated. Two of them show strong two-photon absorption and two-photon excited up-conversion fluorescence.     

Two-photon Lysotrackers for in vivo imaging

We report two-photon Lysotrackers (CLT-blue and CLT-yellow) that can be excited by 750-840 nm femtosecond laser pulses and emit at 470 and 550 nm, respectively. They can be easily loaded into cells and tissue slices for visualization of lysosomes in live cells and tissues for a long period of time through two-photon microscopy. When combined with appropriate two-photon probes for other biological targets, these novel probes would greatly facilitate the two-photon microscopy colocalization experiments.     

Two-photon induced blue fluorescent emission of heterocycle-based organic molecule

An organic molecule based on a heterocycle acceptor has been found to exhibit an intensive two-photon induced blue emission and a large two-photon absorption cross section, which implies that the molecule is a promising candidate for an application such as multi-channel two-photon microscopy.     

Fluorescence resonance energy transfer in a novel two-photon absorbing system

A novel fluorescence resonance energy transfer (FRET) system containing a two-photon absorbing dye and a nile red chromophore has been synthesized. Upon two-photon excitation by laser at 815 nm this molecule displays efficient energy transfer from the two-photon absorbing dye to the nile red moiety, with an 8-fold increase in emission compared to the model compound. Similarly, single-photon excitation of the two-photon absorbing moiety at 405 nm results in >99% energy-transfer efficiency, along with a 3.4-fold increase in nile red emission compared to direct excitation of the nile red chromophore at 540 nm. This system provides an effective way to use IR radiation to excite molecules that, by themselves, have little or no two-photon absorption.     

双光子技术在光生酸剂中的应用研究

自2000年以来,双光子技术开始应用于光生酸剂体系中,并取得了一定的研究进展。双光子技术在光生酸剂中的应用主要有两种情况:一是单分子体系,即光生酸剂分子本身具有较高的双光子吸收截面,可以在双光子激发下产生光酸;二是双分子体系,由具有较高吸收截面的敏化剂分子和光生酸剂分子组成,通过分子间电子转移的方式产生光酸。本文就这一类具有特殊光学性质的有机分子体系的构成及其应用进行了综述,介绍了不同类型的可以利用双光子技术的光生酸剂体系,总结了双光子技术在光生酸剂发展中面临的一些关键问题,展望了双光子技术在光生酸剂中的发展方向。     

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.     

On the Road Toward More Efficient Biocompatible Two-Photon Excitable Fluorophores

Red-to-NIR absorption and emission wavelengths are key requirements for intravital bioimaging. One of the way to reach such excitation wavelengths is to use two-photon excitation. Unfortunately, there is still a lack of two-photon excitable fluorophores that are both efficient and biocompatible. Thus, we design a series of biocompatible quadrupolar dyes in order to study their ability to be used for live-cell imaging, and in particular for two-photon microscopy. Hence, we report the synthesis of 5 probes based on different donor cores (phenoxazine, acridane, phenazasiline and phenothiazine) and the study of their linear and non-linear photophysical properties. TD-DFT calculations were performed and were able to highlight the structure-property relationship of this series. All these studies highlight the great potential of three of these biocompatible dyes for two-photon microscopy, as they both exhibit high two-photon cross-sections (up to 3650 GM) and emit orange to red light. This potential was confirmed through live-cell two-photon microscopy experiments, leading to images with very high brightness and contrast.