Responsive mechanism of 2-(2'-hydroxyphenyl)benzoxazole-based two-photon fluorescent probes for zinc and hydroxide ions

Response theory is used to investigate one- and two-photon absorption(TPA) as well as the emission properties of a series of potential zinc ion and pH sensitive materials containing 2-(2’-hydroxyphenyl)benzoxazole(HPBO) end groups.Special emphasis is placed on the evolution of their optical properties upon combining with zinc ions or deprotonation.Our calculated results indicate that upon combining with zinc ions or deprotonation,these HPBO derivatives show drastic changes in their one-photon absorption(OPA),emission,and TPA properties.Moreover,the mechanisms of the probes are analyzed and found to be an intramolecular charge transfer.These compounds are thus proved to be excellent candidates for two-photon fluorescent zinc and pH probes.     

Computational design of ratiometric two-photon fluorescent Zn2+ probes based on quinoline and di-2-picolylamine moieties

To improve two-photon absorption (TPA) response of a newly synthesized probe, a series of ratiometric two-photon fluorescent Zn²⁺ sensors based on quinoline and DPA moieties have been designed. The one-photon absorption, TPA, and emission properties of the experimental and designed probes before and after coordination with Zn²⁺ are investigated employing the density functional theory in combination with response functions. The design consists of two levels. In the first level of design, five probes are constructed through using several electron acceptors or donors to increase accepting or donating ability of the fluorophores. It shows that all the designed probes have stronger TPA intensities at longer wavelengths with respect to the experimental probe because of the increased intra-molecular charge transfer. Moreover, it is found that the probe 4 built by adding an acyl unit has the largest TPA cross section among the designed structures due to the form of longer conjugated length and more linear backbone. One dimethylamino terminal attached along the skeleton can improve TPA intensity more efficiently than two side amino groups. Therefore, in the second level of design, a new probe 7 is formed by both an acyl unit and a dimethylamino terminal. It exhibits that the TPA cross sections of probe 7 and its zinc complex increase dramatically. Furthermore, the fluorescence quantum yields of the designed probes 4 and 7 are calculated in a new way, which makes use of the relation between the computed difference of dipole moment and the measured fluorescence quantum yield. The result shows that our design also improves the fluorescence quantum yield considerably. All in all, the designed probes 4 and 7 not only possess enhanced TPA intensities but also have large differences of emission wavelength upon Zn²⁺ coordination and strong fluorescence intensity, which demonstrates that they are potential ratiometric two-photon fluorescent probes.     

Isomerism and coordination mode effects on two-photon absorption of tris(picolyl)amine-based fluorescent probes for zinc ions

One-photon absorption and two-photon absorption(TPA) properties of three tris(picolyl)amine-based zinc ion sensors are investigated by employing the density functional response theory in combination with the polarizable continuum model.The different isomer and coordination geometry of each probe are taken into account. Special emphasis is placed on the effects of isomerism and the coordination mode on the optical properties. The intra-molecular charge transfer(ICT)properties are specified by natural bond orbital charge analysis. It is shown that the isomerism has non-negligible effects on TPA properties of free ligands. It is found that both the TPA wavelength and the cross section are highly dependent on the coordination mode. When the zinc ion connects with the picolyl unit in the middle of a ligand, the zinc complex has a large TPA intensity in a long wavelength range due to the increased ICT mechanism.     

Theoretical studies on the one- and two-photon absorption properties of azulenylporphyrins and azulene-fused porphyrins

The electronic structures, one-photon absorption (OPA) and two-photon absorption (TPA) properties of the azulenylporphyrins and azulene-fused porphyrins have been comparatively studied by using DFT/B3LYP/6-31G(d) and the ZINDO/SDCI method. With the number of azulenyl groups increasing, the OPA wavelengths of all molecules are red-shifted in 400--600~nm and the two-photon absorption cross section is gradually enlarged. The azulene-fused structures facilitate an expanding conjugated area and increasing TPA cross section. The origin of TPA properties of studied compounds is studied with a two-level model. In summary, the azulene-fused porphyrins exhibit strong two-photon absorption.     

新型多共轭链有机分子双光子吸收特性的理论研究

在密度泛函理论水平上,利用解析响应函数方法研究了以（4-{2-［4-（2-吡啶-4-乙烯基）-苯基］-乙烯基}-苯基）-胺为基本结构单元的单支、双支和三支共轭链有机分子的单光子和双光子吸收特性.计算结果表明,这三种有机分子都具有较大的线性和非线性吸收强度.在紫外-可见光区域,它们的单光子吸收谱都存在两个峰,这与实验结果符合较好.在近红外区域,多共轭链有机分子呈现出宽达300 nm的宽带双光子吸收,单支、双支和三支分子的最大双光子吸收截面比约为1.0∶2.3∶4.0,其中三支分子具有最大的双光子吸收截面101.73×10^-48 cm⁴·s.从理论上进一步证实,增加分子的共轭链可有效提高分子的双光子吸收特性.同时还给出了电荷转移态的电荷迁移过程. 关键词： 双光子吸收 响应函数方法 多共轭链有机分子     

Styryl Dyes as Two-Photon Excited Fluorescent Probes for DNA Detection and Two-Photon Laser Scanning Fluorescence Microscopy of Living Cells

Spectral-fluorescent properties of benzothiazole styryl monomer (Bos-3) and homodimer (DBos-21) dyes in presence of DNA were studied. The dyes enhance their fluorescence intensity in 2–3 orders of magnitude upon interaction with DNA. Studied styrylcyanines in DNA presence demonstrate rather high values of two-photon absorption (TPA) cross-section, which are comparable with the values of TPA cross section of the rhodamine dyes. An applicability of the styrylcyanines as probes for the fluorescence microscopy of living cells was studied. It was shown that both dyes are cell-permeable but homodimer dye DBos-21 produces noticeably brighter staining of HeLa cells comparing with monomer dye Bos-3. Molecules of DBos-21 initially bind to the nucleic acids- containing cell organelles (presumable mitochondria) and are able to penetrate into the cell nucleus. Thus, homodimer styryl DBos-21 dye is viewed as efficient stain for single-photon and two-photon excitation fluorescence imaging of living cells.     

Cooperative enhancement of TPA in cruciform double-chain DSB derivation: a femtosecond transient absorption spectra study

Femtosecond time-resolved transient absorption (TA) spectra study was adopted to study the mechanism of the cooperative enhancement of two-photon absorption (TPA) cross section from the linear structure 1,4-di(4′-N,N-diphenylaminostyryl)benzene (DPA-DSB) to its cruciform double-chain dimer DPA-TSB. The results suggested that a non-emissive intramolecular charge-transfer (ICT) state, ICT’, was present upon excitation in the dimer, which was absent in the monomer. The existence of this non-emissive state, indicating the enhancement of the intramolecular charge-transfer of the dimer, should be the reason for the cooperative enhancement of the TPA cross section of the dimer compared to the monomer.     

Efficient two-photon absorption of CdSe-CdS/ZnS core-multishell quantum dots under the excitation of near-infrared femtosecond pulsed laser

We report that two-photon absorption (TPA) properties of semiconductor CdSe-core CdS/ZnS-multishell quantum dots (QDs) in toluene under excitation of femtosecond laser at 800 nm. The results show efficient TPA process and large TPA cross section of three types of size QDs, which is 1900, 5710, and 16060 GM (1 GM = 10⁻⁵⁰ cm⁴ s photon⁻¹), respectively. TPA cross section dramatically increases with increased core size, showing a strong size-dependence effect. Furthermore, two-photon excitation (TPE) fluorescence intensity not only depends on TPA capacity, but also relies on improved quantum yield resulting from passivation of QD surface by different coated monolayers (MLs). These facts in combination with the narrow fluorescence bandwidth make these QDs as promising probes for multicolor two-photon microscopy.     

Zn2+ responsive two-photon fluorescent probes based on branch structure: a computational investigation

A series of zinc ion fluorescent probes on the basis of multi-branched ligands were investigated in theory. The three-branched ligand TPPA (N,N,N′,N′-tetraphenyl-p-phenylenediamine) has better three-dimensional spatial localisation, which can detect zinc at the parts per million level. The complex coordinated with Zn²⁺ can show a significant improvement in two-photon absorption (TPA) cross-section in the near-infrared (NIR) excitation region. The calculated results reveal that the stability and sensitivity of Zn²⁺ complexes will be enhanced by increasing the number of branches. The selectivity of double phenyl-p-phenylenediamine (DPPA) ligand to Zn²⁺ will be better compared to Cd²⁺. With regard to the studied ligands single phenyl-p-phenylenediamine (SPPA), two connected single phenyl-p-phenylenediamine (2CSPPA), DPPA and TPPA, λ^EM_max shows a red-shift and ?^EM gets stronger upon the addition of Zn²⁺. Most of the molecules exhibit TPA peaks in the NIR region. The theoretical investigations demonstrate that DPPA-Zn²⁺ shows good TPA activity at a telecommunication wavelength.     

Responsive mechanism of three novel hypochlorous acid fluorescent probes and solvent effect on their sensing performance

Optical properties and responsive mechanisms of three newly synthesized fluorescent probes for hypochlorous acid(HOCl) are investigated by employing time-dependent density functional theory. The computational results show that the absorption and emission properties of these probes change obviously when they react with hypochlorous acid. It is found that the probe FHZ has the best performance according to the probing behavior. Moreover, the responsive mechanisms of the probes are studied by analyzing the distributions of molecular orbitals and charge transfer, which are shown as the photoninduced electron transfer(PET) for FHZ and the intramolecular charge transfer(ICT) for the other two probes. Specially,solvent effect on optical properties of the probe FHZ before and after reaction is studied within the polarizable continuum model(PCM). It is shown that performance of the probe depends crucially on the solvent polarity. Our computational results agree well with the experimental measurement, and provide information for design of efficient two-photon fluorescent probes.     

氧化石墨烯-卟啉复合材料光限幅性能的理论研究

利用时域有限差分法数值求解速率-场强方程,研究了一系列共价连接的氧化石墨烯-卟啉复合材料在纳秒时域内的光限幅性质和双光子吸收. 计算结果表明,氧化石墨烯-卟啉复合分子与单独的卟啉分子相比展现出增强的光限幅效应,并且有着更大的双光子吸收截面.与之前得到的含重金属的卟啉分子具有更强非线性光学性质的结论不同,不含金属元素的卟啉分子与氧化石墨烯结合后展现出了更强的非线性光学性质. 理论计算的结果与实验测量符合较好. 此外,着重研究了介质的厚度和脉冲宽度对分子双光子吸收截面的影响. 结果表明,随着介质厚度的增加或者脉宽的变宽分子的动态双光子吸收截面增大.     

双光子吸收材料二苯乙烯衍生物的合成及光谱性质

设计、合成并用红外光谱、1H NMR、元素分析表征了三种用于双光子吸收材料的二苯乙烯衍生物,4,4′-双(二苯氨基-反式-苯乙烯基)联苯(BPSBP),4,4′-双(二乙氨基-反式-苯乙烯基)联苯(BESBP)和4,4′-双(9-咔唑基-反式-苯乙烯基)联苯(BCSBP)。实验结果表明三者最强的单光子吸收出现在350～400 nm之间,且单光子吸收和荧光光谱中表现出明显的溶剂化显色效应,揭示了分子内对称电荷转移的本质,双光子荧光光谱则揭示了单光子和双光子吸收具有相同的发射机理。利用双光子上转换荧光法测试发现,三种双光子吸收材料在800 nm飞秒激光的激发下具有较大的吸收截面,分别为892,617和483 GM,这表明在双光子领域有潜在的应用价值。     

Photosensitization of Imidazole Derivative by ZnO Nanoparticle

A sensitive imidazole based fluorescent sensor like 4, 5-diphenyl-2(E)-styryl-1H-imidazole, for ZnO has been designed and synthesized via simple steps. The absorption, fluorescence, SEM, EDX and IR studies indicate that imidazole derivative is bound on the surface of ZnO semiconductor. Based on photo-induced electron transfer (PET) mechanism, fluorescent enhancement has been explained and apparent binding constant has been calculated. Ligand adsorption on ZnO nanoparticle lowers of the HOMO and LUMO energy levels of imidazole derivative and the chemical affinity between the nitrogen atom of the imidazole and zinc ion on the surface of the nano oxide may be a reason for strong adsorption of the ligand on nanoparticle. The electron injection from photo excited imidazole derivative to the ZnO conduction band (S(*)→S(+) + e (CB) (-) ) accounts for the enhanced fluorescence.     

强超短脉冲抽运下半导体光放大器中的非线性过程

建立了包含载流子浓度脉动(CDP)、自由载流子吸收(FCA)、受激辐射(SE)、双光子吸收(TPA)、光谱烧孔(SHB)和超快非线性折射(UNR)过程的半导体光放大器(SOA)理论模型,通过与已报道的实验结果的比较对模型进行了验证,实现了对已有 SOA模型的修正,并对UNR,FCA和TPA效应对强超短光脉冲传输特性的影响进行了分析.当脉宽为几个皮秒的强光脉冲注入工作于透明电流下的SOA时,其强度特性主要受FCA和TPA效应的影响.由于加入了FCA效应,使模型对200fs脉冲强度传输特性的仿真结果与实验结果 关键词： 非线性过程 强超短光脉冲 SOA理论模型 增益透明     

Optical Properties of a New Two-photon Absorption Dye DEASPI

The two-photon absorption (TPA), TPA-induced frequency up-conversion emission, and two-photon pumped (TPP) frequency up-conversion lasing properties of a new synthesized dye Trans-4-［p-(N,N-diethylamino)styryl］-N-methylpyridinium iodide (DEASPI) were experimentally studied. This new dye has a moderate TPA cross-section of σ2=6.9×10-48 cm4*s/photon at 1064 nm, but exhibits a high lasing efficiency. The overall superradiant lasing conversion efficiency is as high as 10.7% at the pump energy of 2.14 mJ.     

Two-photon absorption of high-power picosecond pulses in PbWO<Subscript>4</Subscript>, ZnWO<Subscript>4</Subscript>, PbMoO<Subscript>4</Subscript>, and CaMoO<Subscript>4</Subscript> crystals

The nonlinear process of two-photon interband absorption is studied in tungstate and molybdate oxide crystals excited by a sequence of high-power picosecond pulses with a wavelength of 523.5 nm. The transmission of the crystals is measured for the excitation pulse intensity up to 100 GW/cm². The pulse intensity in the crystals initially transparent at a wavelength of 523.5 nm is strongly limited due to two-photon absorption (TPA), and the reciprocal transmission in PbWO₄ and ZnWO₄ crystals reaches 50–60. In all crystals, TPA induces long-lived one-photon absorption, which affects the nonlinear process dynamics and leads to a hysteresis in the dependence of the transmission on the laser excitation intensity. Absorption dichroism manifests itself in a significant difference in the transmission intensities when the principal orthogonal optical axes of the crystals are excited. The TPA coefficients are determined during the excitation of two optical axes of the crystals. TPA coefficients β for the crystals vary over a wide range, namely, from β = 2.4 cm/GW for PbMoO₄ to β = 0.14 cm/GW for CaMoO₄, and the values of β can differ almost threefold when different optical axes of a crystal are excited. Good agreement is achieved between the measured intensities limited by TPA and the estimates calculated from the measured nonlinear coefficients. Stimulated Raman scattering (SRS) upon excitation at a wavelength of 523.5 nm is only detected in two of the four crystals under study. The experimental results make it possible to explain the suppression of SRS by its competition with TPA, and the measured nonlinear coefficients are used to estimate this suppression.     

The aggregation effects on the two-photon absorption properties of para-nitroaniline polymers by hydrogen-bond interactions

This paper has theoretically designed a series of aggregate polymers on the basis of several para-nitroaniline monomers by hydrogen-bond interactions. At the level of time-dependent hybrid density functional theory, it has optimized their geometrical structures and studied their two-photon absorption (TPA) properties by using analytical response theory. The calculated results exhibit that the aggregation effects not only bring out the considerable red shift of the excited energies but also greatly enhance the TPA intensities of the aggregate polymers in comparison with the para-nitroaniline monomer. The aggregate configurations also have an important influence on the TPA abilities of the polymers; the trimer has the largest TPA cross section. The electron transitions between the molecular orbits involving the strong TPA excitations of the trimer are depicted to illuminate the relationship between the intermolecular charge transfer and the TPA property.     

Optical Properties of a New Two-photon Absorption Dye DEASPI

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Role of doubled-frequency absorption in two-photon response of the Si MSM structure

The physical mechanism of two-photon response was studied in this paper by measuring characteristics of the two-photon response of the Si metal–semiconductor–metal (MSM) structure sample. The two-photon response includes two-photon absorption (TPA) and doubled-frequency absorption (DFA). An experiment was designed to measure the photocurrent dependence on incident light power, the dependence of the photoelectric signal on the applied voltage and the relationship between the photoelectric current and the light-spot position. The experimental fact that two-photon response of the silicon sample is relative to the applied electric field shows that DFA is the main physical mechanism of two-photon response and establishes the foundation for fabricating high-sensitivity two-photon response Si photodetector.     

9,10-Anthracene-centered oligo(p-phenyleneethynylene)s with end-capping didecylamines exhibiting enhanced two-photon fluorescence action cross-section

This study reports the synthesis and the two-photon absorption (TPA) properties of a series of 9,10-anthracene-centred oligo(p-phenyleneethynylene)s with end-capping didecylamine. The results show that both the maximal TPA cross-sections (δ_max) and the fluorescence quantum yields (Φ) of the oligomers increase with the extension of phenylethynyl bridges. Interestingly, the Φδ_max per repeating unit to is obviously enhanced by extending linearly conjugation size of the oligomers. Moreover, these oligomers all show the maximal two-photon absorption cross-sections at 800 nm and emit strong green to yellowish-green two-photon excited fluorescence. These materials may find applications in which two-photon excited fluorescence and photo-induced electron transfer are utilized.