Responsive mechanism and molecular design of di-2-picolylamine-based two-photon fluorescent probes for zinc ions

The properties of one-photon absorption(OPA), emission and two-photon absorption(TPA) of a di-2-picolylaminebased zinc ion sensor are investigated by employing the density functional theory in combination with response functions.The responsive mechanism is explored. It is found that the calculated OPA and TPA properties are quite consistent with experimental data. Because the intra-molecular charge transfer(ICT) increases upon zinc ion binding, the TPA intensity is enhanced dramatically. According to the model sensor, we design a series of zinc ion probes which differ by conjugation center, acceptor and donor moieties. The properties of OPA, emission and TPA of the designed molecules are calculated at the same computational level. Our results demonstrate that the OPA and emission wavelengths of the designed probes have large red-shifts after zinc ions have been bound. Comparing with the model sensor, the TPA intensities of the designed probes are enhanced significantly and the absorption positions are red-shifted to longer wavelength range. Furthermore, the TPA intensity can be improved greatly upon zinc ion binding due to the increased ICT mechanism. These compounds are potential excellent candidates for two-photon fluorescent zinc ion probes.     

Influence of rotational isomerism on two-photon absorption properties of FTC chromophores

The influence of rotational isomerism on the two-photon absorption(TPA) of FTC chromophores has been investigated using the quadratic response theory with the B3LYP functional.Eight rotamers induced by three rotatable single bonds in the molecule are fully optimized,and it is found that their conformational energies are nearly degenerate.Our calculations demonstrate that rotational isomerism has an important effect on the TPA cross sections.For a certain rotamer,the maximum TPA cross section is enhanced significantly.In addition,in the longer wavelength region,the rotational isomerism could lead to a large shift of the TPA position.     

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.     

Two-photon absorption properties of D-A-D type chromophores containing tetraphenylethylene and triphenylamine moieties: a close look at the effects of the strength,position and number of donors

The two-photon absorption (TPA) properties of a series of D-A-D type chromophores containing tetraphenylethylene (TPE) and triphenylamine moieties have been investigated employing the density functional response theory in combination with the polarisable continuum model. Special emphases are placed on the effects of the strength, position and number of donors on TPA. Our calculations demonstrate that the TPA intensity enhances with the increase of the electron-donating ability of the substituents on the triphenylamine unit, which is consistent with experimental observations. It is shown that the position of donors has an important effect on TPA. The donor on the side position of TPE unit decreases the TPA cross section, thereby more donors could not necessarily produce stronger TPA. The cis-trans isomerism effect is also explored and it is found that all the cis structures have lower TPA intensities than those of corresponding trans forms. By considering a different number of donors on TPE and triphenylamine unit respectively, it is interesting to find that the structure with one terminal donor on TPE and two donors on triphenylamine unit has the largest TPA cross section. The few-state model and the natural bond orbital charge analysis are used to explore the reason behind it.     

有机染料HEASPS在不同波长时的激发态吸收和双光子吸收性质研究

提出了有机染料反式 4 [4′ (N 羟乙基 N 乙基胺基 )苯乙烯基 ] N 甲基吡啶对甲苯磺酸盐 (简称HEASPS)非线性吸收的三态模型。认为在较短波长 (<1 0 0 0nm)时 ,双光子吸收和激发态吸收同时存在。成功地解释了该染料双光子吸收峰相对线性吸收峰的两倍的明显蓝移 ,以及最高上转换效率波长相对最强吸收波长的明显红移。提出了一种新的计算方法 ,利用不同波长的非线性透过率和不同波长的上转换效率 ,求出了该染料的双光子吸收截面和激发态吸收系数。     

Quantum waves in zinc

The effect of quantization of charge carriers in a magnetic field on the wave properties of zinc is investigated theoretically. It is shown that the cyclotron absorption by holes in the microwave range acquires a clearly manifested quantum structure: the absorption as a function of the magnetic field has the form of a sequence of narrow quantum peaks separated by deep minima. The suppression of cyclotron absorption at the minima is so strong that the propagation of an electron doppleron—the mode characterized by strong damping under classical conditions and not observed in zinc—becomes possible.     

某些金属酞菁配合物的单体电子吸收光谱和荧光光谱

研究了某些金属酞菁配合物在单体状态下的电子吸收光谱和荧光光谱,并探讨了溶剂、中心离子和取代基的影响效应。     

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.     

一种新型有机染料HEASPS在不同波长时的双光子吸收和频率上转换性质研究

报道了一种新型双光子吸收染料 ,即反式 - 4- [4′- (N-羟乙基 - N-乙基胺基 )苯乙烯基 ]- N-甲基吡啶对甲苯磺酸盐的非线性光学性质 ;测试了染料在 72 0～ 110 0 nm波段的非线性透过率曲线。结果发现 :双光子吸收最强波长相对线性吸收峰波长的两倍处有明显蓝移 ;计算出的相应波长的双光子吸收截面在 930 nm处染料有最大双光子吸收截面(2 .0 6× 10 - 4 7cm4·s/ photon) ;测量了染料在 90 0～ 110 0 nm波段的上转换效率 ,在 10 2 0 nm处有最高效率 (5 .1% ) ,最高激射效率的波长相对最强双光子吸收的波长有明显红移     

以二乙烯硫/砜基为中心的新型电荷转移分子双光子吸收特性

理论研究分子结构与双光子吸收性质之间的关系对于指导实验者设计与合成功能分子材料具有重要意义. 在杂化密度泛函水平上, 利用响应函数方法, 计算了一类以二乙烯硫/砜基为中心的新型电荷转移分子的双光子吸收截面, 并在相同计算水平上, 与联苯乙烯类强双光子吸收分子做了比较; 以新型电荷转移分子为基础, 利用异构效应, 设计出了可以增强双光子吸收强度的分子结构. 研究表明, 在可应用波长范围内, 该系列分子表现出较强的双光子吸收响应, 与相似共轭长度的强双光子吸收分子具有相同量级的双光子吸收截面; 二乙烯硫/砜基在分子中心作为吸电子基团可以形成有效的电荷转移分子; 改变咔唑基的连接方式可以有效提高双光子吸收截面. 该研究为实验合成新型双光子吸收分子材料提供了理论依据.     

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.     

Nonlinear optical characteristics and lasing ability of merocyanine dyes having different solvatochromic behaviour

Lasing characteristics and two-photon absorption (TPA) of merocyanine dyes with solvatochromism of different types are first investigated. Efficient lasing is excited in solutions pumped by radiation of the 2nd harmonic of a Nd-YAG laser (532 nm) with the lasing efficiency exceeding 40% and by XeCl laser radiation (308 nm) with the lasing efficiency up to 19%. The TPA cross-section at a wavelength of 1064 nm is determined. It is established that for merocyanines possessing the highest positive and negative values of solvatochromism, the TPA cross-section reaches maximum values of 115 and 125 GM, respectively. Influence of the special features of the electronic structure, spectral and luminescent properties, solvatochromic behavior, and nature of the medium on the lasing characteristics and nonlinear absorption of merocyanine dyes is investigated. Prospects for merocyanine application in modern optical technologies are demonstrated.     

吸收层特性和异质结界面电荷对12.5 μm长波HgCdTe光伏探测器响应率的影响研究

研究了12.5 μm长波HgCdTe探测器的吸收层厚度和异质结界面电荷对器件光响应率的影响.分析了吸收层厚度与吸收长度、扩散长度之间的联系,获得了设计最佳吸收层厚度的经验公式.研究结果显示入射光波长超过截止波长时,响应率随吸收层厚度增加单调增加,并逐渐饱和.响应率峰值对应的波长随吸收层厚度增加,有向长波偏移的趋势.最佳吸收层厚度值随少子寿命或入射光波长的增大而增大.同时,研究了衬底、钝化层与HgCdTe材料之间异质界面电荷对光响应率的影响,发现正的界面电荷在衬底异质结界面处形成诱导pn结,对响应率影响显著 关键词： 长波HgCdTe器件 光伏型红外探测器 光响应率 少子寿命     

Acyclic donor-acceptor-donor chromophores for large enhancement of two-photon absorption cross-section in the presence of Mg(II), Ca(II) or Zn(II) ions

Two new chromophores in the format, donor-acceptor-donor, have been synthesized in high yields from easily available starting materials. These compounds do not show any two-photon absorption (TPA) cross-section in the wavelength range, 780-900 nm when probed by the Z-scan technique with a femtosecond laser. However, in presence of Zn(II), Ca(II) or Mg(II) ion, each compound gives exceptionally large TPA cross-section in the same wavelength range.     

具有电子推拉结构的多支化分子的光物理特性的研究

利用稳态光谱和飞秒时间分辨荧光亏蚀的技术,研究了不同溶剂中一系列有分子内电荷转移特性的分子的结构与光物理性质的关系,研究体系为三苯胺作为电子给体,2,1,3-苯并噻二唑作为受体的单支分子及其对应的两支和三支分子. 并结合TD-DFT计算进一步解释了实验中所观察到的现象. 三个分子相似的吸收和荧光光谱以及强的溶剂依赖光谱特性表明两支与三支分子激发态与单支分子相似,表明激发态都定域在其中一支上. 激发时多支分子内发生多维电荷转移,然后快速地定域到某一支上发射. 另一方面多支分子相对于单支分子吸收和发射光谱的红     

双光子吸收光谱

本文报道以皮秒脉冲激光抽运的光参量放大器为宽带可调谐激发光源，直接测量非线性光学材料的双光子吸收谱的方法。光参量放大器不但可调谐谱带很宽，而且可用一对尼科尔棱镜很容易地实现全波段功率足够强和相等，使此方法的测量结果准确可靠。用此方法研究了一个新有机化合物的双光子吸收谱。实验结果表明所测的新有机化合物在很宽的波长范围内呈现出很大的双光子吸收截面。     

溶胶CdS毫微晶的双光子吸收及其量子尺寸效应

本文利用单光束透过率法研究了溶胶CdS毫微晶的双光子吸收。对于毫微晶尺寸为5.5～11.0nm的样品,测得其在波长510.6nm时的双光子吸收系数为1.31～5.24/GW,并由此得到相应的x~(3)为2.8×10~(-12)～1.1×10~(-11)esu。文中还从理论上分析了CdS溶胶的双光子吸收与毫微晶尺寸的关系,理论计算与实验结果基本符合。     

吸收对垂直腔面发射激光器光学特性的影响

采用光学传输矩阵方法，详细分析了反射镜以及键合界面的吸收对垂直腔面发射激光器光学特性的影响. 结果表明，反射镜以及键合界面的吸收对反射镜和垂直腔面发射激光器的反射率和势透射率有较大影响，而对反射镜中心波长处的反射相移以及垂直腔面发射激光器模式的反射相移和模式位置影响很小. 随着反射镜以及键合界面的吸收增大，反射镜中心波长处的反射率逐渐减小，垂直腔面发射激光器的模式反射率变化则是先急剧减小，达到一个极小值，然后再逐渐增大，而反射镜中心波长处以及垂直腔面发射激光器模式处的势透射率则都是迅速降低的. 此外，将有吸收的键合界面离有源区的距离远一些，有利于提高垂直腔面发射激光器模式处的光输出效率.     

用一维光子带隙结构增强硫化镉双光子吸收研究

用真空镀膜方法制备了含有单个CdS缺陷层的具有不同周期和结构参量的TiO2／SiO2一维光子晶体。用抽运一探测技术研究了CdS缺陷层的双光子吸收（TPA）现象。实验结果表明：一维光子晶体中CdS缺陷层的双光子吸收显著增强。不同周期和结构参量的一维光子晶体中CdS缺陷层的双光子吸收系数不同。双光子吸收的增强来源于由光局域化导致的缺陷层的电场强度的增加。缺陷层电场强度与一维光子晶体的结构有关,如周期,光子带隙的位置与宽度及缺陷模式等因素都会影响缺陷层电场强度。采用四分之一波长的高低折射率介质层和与入射波长匹配的缺陷模可以得到最大的缺陷层电场强度。