Two-photon absorption of a supramolecular pseudoisocyanine J-aggregate assembly

Linear spectral properties, including excitation anisotropy, of pseudoisocyanine or 1,1′-diethyl-2,2′-cyanine iodide (PIC) J-aggregates in aqueous solutions with J-band position at 573 nm were investigated. Two-photon absorption of PIC J-aggregates and monomer molecules was studied using an open aperture Z-scan technique. A strong enhancement of the two-photon absorption cross-section of PIC in the supramolecular J-aggregate assembly was observed in aqueous solution. This enhancement is attributed to a strong coupling of the molecular transition dipoles. No two-photon absorption at the peak of the J-band was detected.     

Pseudoisocyanine J-aggregate to optical waveguiding crystallite transition: microscopic and microspectroscopic exploration

Using fluorescent microscopy and microspectroscopy, optical properties and morphology transformations in individual pseudoisocyanine (PIC) J-aggregates in aqueous electrolyte solutions have been explored. A stringlike structure of J-aggregates with a string diameter much less than 1 microm has been observed. Photodestruction of the strings under short-wavelength excitation has been revealed. Rodlike PIC crystallites, about 1 microm in diameter, have been observed with time. The fluorescence spectrum of rodlike crystallites has been found to differ from that of stringlike J-aggregate and from PIC crystal powder spectra. The crystallites are very stable, and their photodestruction has not been observed under any excitation conditions. It has been found that rodlike crystallites in contrast to stringlike J-aggregates possess optical waveguide properties. The luminescence of crystallites can be observed only at the excitation spot and at butt ends located up to hundreds of micrometers from the excitation spot.     

Exciton absorption spectra of optically excited linear molecular aggregates

Exciton absorption spectrum of optically excited linear molecular aggregate is theoretically investigated. The sum rules for the integral intensity of the absorption spectrum are derived. The dipole moments of the optical transitions from the one-exciton states to the two-exciton states are presented. The results obtained indicate an energy increase of the exciton transition after a single excitation of the aggregate. It accounts for the observed short-wavelength shift of the J-band of the pseudoisocyanine (PIC) J-aggregates after their optical excitation. The comparison of the experimental energy of the shift with its theoretical evaluation allows to estimate the number of monomers forming a typical PIC J-aggregate in the solutionN ?20–30.     

Studies on the interaction of achiral cationic pseudoisocyanine with chiral metal complexes

The effect of chiral metal complexes ([Co(en)(3)]I(3)·H(2)O, cis-[CoBr(NH(3))(en)(2)]Br(2), K[Co(edta)]·2H(2)O and [Ru(phen)(3)](PF(6))(2)) on the polymer-bound J-aggregates in aqueous mixtures of pesudoisocyanine (PIC) iodine and poly(acrylic acid, sodium)(PAAS) have been studied by UV-vis absorption, circular dichroism (CD) and fluorescence spectra. At low concentration, the PIC monomers could self-assemble to form supermolecules by binding to each of the COO(-) groups on the polymer chains through electrostatic interactions. After the addition of chiral metal complexes to the formed PIC-PAAS J-aggregates, we found that only the chiral multiple π-conjugated phenanthroline metal complexes could transfer their metal-centered chiral information to the formed J-aggregates. The chiral J-aggregates showed a characteristic induced circular dichroism (ICD) in the visible region of J-band chromophore, and the ICD signals depend on the absolute configuration, concentration of the chiral multiple π-conjugated metal complexes, as well as temperature. More interestingly, the supramolecular chirality of the polymer supported PIC J-aggregates could be memorized even after the addition of an excess opposite chiral complex enantiomers. This is in sharp contrast to the behavior in the high concentrated NaCl induced PIC-J aggregates, in which the optical rotation of a mixture of two enantiomers varies linearly with their ratio.     

The interaction of 2-hydroquinone-5,10,15,20-tetra(p-hydroxyphenyl)porphyrin with surfactants: solubilization and J-aggregates

J-aggregates of 2-hydroquinone-5,10,15,20-tetra(p-hydroxyphenyl)porphyrin (HQTHPP) induced by N-lauroyl sarcosine (SKL) in aqueous neutral solutions have been studied by optical absorption, fluorescence, and resonance light-scattering spectroscopies. As SKL concentration increases, the spectra evolve to reveal the presence of four independent species with relative concentration. The most important species is J-aggregates. The J-aggregates have two strong exciton bands corresponding to the B-band and Q-bands of HQTHPP monomers, and are found to be stable when the surfactant concentration is below 8.0 mmol/L. But above 8.0 mmol/L, the J-aggregates dissolve gradually into another species: porphyrin monomers. The total fluorescence of HQTHPP is quenched due to the aggregate formation. A strong and sharply peaked resonance light-scattering signal (>1800 counts/s, centered at 490 nm) is observed just slightly to the red of the J-aggregate absorption maximum. In the case of cetyltrimethyl-ammonium bromide, increasing surfactant concentrations have only shown to favor solubilization of porphyrin monomers. Evidently, the nature of polar headgroups of surfactants influences the tendency of THPP to aggregate.     

Self-oriented pseudoisocyanine J-aggregates in solution

Highly oriented fiber-shaped J-aggregates of pseudoisocyanine (PIC) molecules were prepared by simply growing the aggregates in a narrow glass cell, which allows evaporation of the solution in one direction.     

Exciton energy transfer between optically forbidden states of molecular aggregates

3-ethyl-2-[3-(3-ethyl-2(3H)-benzoxazolylidene)-1-propenyl]benzoxazolium iodide (dye I) and pseudoisocyanine bromide are employed to form H aggregates as donors and J aggregates as acceptors. The energy of an H band of the H aggregates is higher than that of a J band of the J aggregates. It was confirmed that excitation of the H band does not emit fluorescence by comparison of excitation spectra of dye I H aggregates with that of dye I monomer. Absorption, fluorescence, and excitation spectra of spin-coated films of H aggregates mixed with various quantities of J aggregates have been observed. Excitation spectra probed at the J band are found to have a component of the H band. Fluorescence spectra originated from excitation of the H band are extracted and qualitatively analyzed. It is confirmed that excitation of the H band causes to emit fluorescence of a J band of the J aggregates. These phenomena show that exciton energy can transfer from the lowest energy in electronic states of the H aggregate, which state is optically forbidden, to electronic state of the J aggregate.     

Solvent-induced organization of squaraine dyes in solution capillary layers and adsorbed films

Unusual behavior of indolenine and hydroxyphenyl squaraines has been observed in solution capillary layers and adsorbed films. The confined solutions showed anomalous aggregation of squaraine molecules in contrast to their monomer behavior in the bulk solutions of the same concentration, along with formation of a macroscopic cell-like structure in the confined solution layer, with the diameter of cells being 3-5 microm. The aggregate structure, as observed through electronic absorption spectra, was strongly dependent on the chemical structure of squaraine used and solvent used, and it also was different from squaraine aggregates observed in aqueous solutions and films prepared by vacuum evaporation. It has been found that indolenine squaraine is capable of forming H-aggregates in confined dimethylformamide solutions and hydroxyphenyl squaraine is capable of forming J-aggregates in confined dimethylformamide solutions and adsorbed films. The results were compared with pseudoisocyanine, which forms J-aggregates in aqueous bulk solutions readily; however, no J-aggregates have been found in their capillary layers. The interplay of dye-dye, dye-surface, and dye-solvent interactions resulting in the above effects is discussed.     

Picosecond time-resolved kinetic studies on the formation of short-lived pseudoisocyanine iodide photoisomers in methanol and ethylene glycol

Upon exciting pseudoisocyanine iodide with 20 ps pulses at wavelengths between 490 and 530 nm within the absorption band, formation of a new transient absorption with a maximum at 545 nm was observed. It is attributed to an unstable photoisomer of pseudoisocyanine iodide. The quantum yield of the photoisomer is 31% in methanol and 6% in ethylene glycol     

D-，L-苯丙氨酸诱导非手性菁染料的手性组装

超分子手性与分子自组装是生命体中非常重要和有趣的现象．报道了D,L-苯丙氨酸等氨基酸在氯化钠溶液中通过非共价键相互作用诱导非手性菁染料（Pseudoisocyanine,PIC）J-聚集体超分子手性的形成．实验结果表明,诱导的手性菁染料PIC聚集体发色团在π-π^＊跃迁区域产生了特征的镜像圆二色性,其圆二色信号和强度强烈地依赖于氨基酸的绝对构型、浓度、侧链基团和溶液温度．原子力显微镜照片清楚地表明,^聚集体由相互交联的纳米纤维组成,诱导的圆二色性可能来源于纤维状聚集体的宏观螺旋排列．     

POLARIZED PHOTO ACOUSTIC SPECTRA OF PHYCOBILISOMES IN POLYVINYL ALCOHOL FILMS

Abstract— Phycobilisomes from Porphyridium cruentum , suspended in polyvinyl alcohol were found to be highly stable, and had normal absorption and fluorescence spectra. Intact phycobilisomes had a major emission peak at 680 nm, whereas upon partial dissociating the major emission was at 580 nm. Incorporation of phycobilisomes in thin polyvinyl alcohol films facilitated examination by photoacoustic spectroscopy. The photoacoustic spectra had a broad absorption maximum at 545–565 nm (phycoerythrin), which resolved as two peaks (545 and 563 nm) in absorption spectra. Stretching of films resulted in apparent chromophore reorientation in partially dissociated, but not in intact phycobilisomes. Only in dissociated phycobilisomes was observed a differential chromophore orientation at 685 nm by polarized fluorescence, which is attributed to a change in orientation of the terminal phycobilisome pigment relative to phycoerythrin.     

对叔丁基杯[8]芳烃/钼磷杂多酸纳米杂化LB膜的制备与表征

以含有共轭大π键的对叔丁基杯[8]芳烃(Cal8)和十八(烷)铵(ODA)与Keggin结构和Dawson结构钼磷杂多酸(HPA)做成膜材料, 用LB技术制备了2种新型无机-有机杂化LB膜. 用π-A曲线、UV-Vis吸收光谱、荧光光谱和原子力显微镜(AFM)对标题LB膜的成膜性质、结构及发光性质进行了表征. 结果表明在空气/水界面Cal8/ODA/HPA杂化可形成稳定的单层与多层膜. 标题杂化LB膜的崩溃压为39.0 mN/m, 其粒子具有纳米尺寸, 在激发波长为280 nm时, 可观察到322～387 nm处由Cal8分子π-π*跃迁引起的荧光发射峰及510 nm处 杂多阴离子的配体到金属的荷移跃迁(LMCT)三重发射谱带.     

Two-photon fluorescence spectroscopy of individually trapped pseudoisocyanine J-aggregates in aqueous solution

We have investigated a pseudoisocyanine dye aqueous solution including nanometer-sized J-aggregates by combining optical trapping and two-photon fluorescence spectroscopy. By focusing an intense near-infrared laser into an 8 x 10(-3) M solution, the intense fluorescence from J-aggregates for a few to tens of seconds is observed intermittently, indicating that individual J-aggregates are trapped in and diffuse out from a focal spot. The peak position and full width at half-maximum of the J-band are different from each other. By measuring 171 J-aggregates, it was found that J-aggregates can be classified largely into two groups. The existence of two kinds of groups of J-aggregates could be attributed to the difference in the nucleation process, which is affected by the substrate. J-aggregates possessing a J-band of a narrower bandwidth in a shorter wavelength region are trapped for a longer period of time, indicating that highly ordered J-aggregates are trapped for a longer period of time because of their high polarizability.     

Excitation and emission spectra of polyethylene terephthalate and polyethylene 2,6‐naphthalate films

With excitation by the light of the wavelengths longer than 320 nm, fluorescence spectra of polyethylene terephthalate (PET) films had somewhat different shapes from those excited below 300 nm through the intrinsic absorption of PET molecules. Also, in the measurements taken with a polarizer in front of the receiving monochoromator but none before the sample, the intensity ratio of parallel (to the draw axis of the film) and perpendicular components of the emission spectra was different if excited above 320 nm or below 300 nm. Discussion was made about the first step of pumping photon energy at the wavelengths above 320 nm. Fluorescence spectra of polyethylene 2,6‐naphthalate films showed a mirror image of their absorption spectra, consisting of one broad band having the same polarization as their absorption spectra. Their fluorescence occurred from the lowest excited level, conforming to the Kasha law. Copyright © 1999 John Wiley & Sons, Ltd.     

Luminescence properties of the mixed J-aggregate of oxacyanine dye and thiacyanine dye. Formation of a persistence-type aggregate

The monolayer assemblies incorporating the J-aggregates of oxacyanine dye, N,N'-dioctadecyloxacyanine perchlorate (S9), and thiacyanine dye, N,N'-dioctadecylthiacyanine perchlorate (S11), S9(J) + S11(J), have been fabricated by the Langmuir-Blodgett (LB) technique. The mole fraction X of S11, X = [S11]/([S9] + [S11]), was varied from 0 to 1. Steady-state absorption spectra, fluorescence spectra, and picosecond fluorescence decay curves of the monolayer assemblies have been measured. Spectroscopic properties of the monolayer assemblies incorporating the individual dye aggregates, S9 J-aggregate (S9(J), X = 0) or S11 J-aggregate (S11(J), X = 1), are characterized by a distinct J-band and resonance fluorescence at lambda(ab) = 403 nm and lambda(em) = 403 nm for S9(J) and lambda(ab) = 456 nm and lambda(em) = 463 nm for S11(J). On the other hand, absorption spectra of the S9(J) + S11(J) assemblies for X = 0.1-0.9 display two absorption bands, a shorter wavelength one and a longer wavelength one, whose peak positions are blue-shifted from those of the corresponding J-bands of the S9 J-aggregate and the S11 J-aggregate, respectively. Furthermore, fluorescence spectra are characterized by a single band (longer wavelength fluorescence) which is somewhat blue-shifted from the resonance fluorescence of the S11 J-aggregate. The fluorescence lifetimes of the S11 J-aggregate and isolated S11 molecules in LB films appear to be tau = 110 and 1900 ps, respectively, while the fluorescence lifetime of the longer wavelength fluorescence of the S9(J) + S11(J) assemblies takes practically a constant value of tau = 170-180 ps for X = 0.2-0.8. These observations would indicate that S9 and S11 molecules in the S9(J) + S11(J) assembly can form a specific mixed aggregate distinct from the individual S9 and S11 J-aggregates. From detailed considerations of the former works on luminescence properties of the S9 J-aggregate doped with isolated S11 molecules, as well as the mosaic-type mixed J-aggregate (M-aggregate) composed of a certain thiacyanine dye, 3,3'-disulfopropyl- 5,5'-dichlorothiacyanine sodium salt, and thiacarbocyanine dye, meso-substituted 3,3'-disulfopropyl-5,5'-dichlorothiacarbocyanine potassium salt, it is suggested that S9 and S11 can form a homogeneous aggregate of the persistence type (HP-aggregate). The HP-aggregate is distinguished from the M-aggregate because it is characterized by homogeneous mixing of two component dyes and persistence of two absorption bands.     

J-aggregation of anionic ethyl meso-thiacarbocyanine dyes induced by binding to proteins

The effects of ribonuclease A (RNase), lysozyme, trypsin, and bovine serum albumin (BSA) on the J-aggregation behavior of 3,3'-bis[sulfopropyl]-5-methoxy-4',5'-benzo-9-ethylthiacarbocyanine (1), 3,3'-bis[sulfopropyl]-4,5,4',5'-dibenzo-9-ethylthiacarbocyanine (2), and 3,3'-bis[sulfopropyl]-5,5'-dimethoxy-9-ethylthiacarbocyanine (3) were studied in aqueous solution. The formation of J-aggregates at pH 6 is induced by RNase for 1-3, by lysozyme for 1 and 2, and by trypsin for 2. The formation of J-aggregates correlates with decay of the dimers and is supported by induced circular dichroism spectra. The concentration of J-aggregates for lysozyme/1 increases with an increase in the protein/dye concentration ratio, reaches a plateau, and then gradually decreases. J-aggregates are characterized by relatively weak fluorescence; e.g., Phi(f) = 0.01 for lysozyme/1, and by a small Stokes shift of 6-8 nm, indicating almost resonance fluorescence. J-aggregation proceeds in the range of seconds to minutes with sigmoidal type kinetic curves for trypsin/2 and nonsigmoidal kinetics in the other cases. The presence of BSA, in contrast to RNase, lysozyme, and trypsin, results in deaggregation of dimers of 1-3 and formation of bound monomers and exhibits intense fluorescence from the trans-monomer; e.g., Phi(f) = 0.22 for BSA/1. Generally, the binding of 1-3 to the proteins is a cooperative process, where the number of binding sites changes from n = 15 for lysozyme/1 to n = 6 for trypsin/2 and n = 0.3 and 1 for BSA/3.     

Detecting the micellization of anionic surfactants by a colorimetric and fluorescent probe based on electrostatic attraction

A novel fluorescent probe labeled with cation, N-n-alkyl-4-(1-methylpiperazine)-1,8-naphthalimide iodide ([C₈ndi]I), has been applied as a colorimetric and fluorometric probe for detecting the micellization of anionic surfactants. The critical micellization concentration (cmc) of anionic surfactants can be conveniently determined by the change on absorption and fluorescence spectra of [C₈ndi]I. The probe displays highly sensitive and selective spectroscopic responses accompanied with distinctive color change (from colorless to light green). These methods are proved to be reliable as the results are in accordance with those of the standard methods. Besides the advantage of visual detection, the multiple spectroscopic methods (absorption and fluorescence) by using [C₈ndi]I as probe are also simple and convenient. One can choose any spectroscopic parameter, such as position or intensity of the absorption and emission peaks, to monitor the micelle formation process of anionic surfactants.     

Nanostructured oligo(p-phenylene vinylene)/silicate hybrid films: one-step fabrication and energy transfer studies

Novel hybrid materials containing silicate and charged oligo(p-phenylene vinylene) (OPV) amphiphiles were fabricated in one step by spin casting using evaporation-induced self assembly. The conjugated segments were substituted with trimethylammonium bromide groups at both termini, and tetraethyl orthosilicate served as the silicate precursor. X-ray diffraction scans of the hybrid films revealed Bragg diffraction peaks with d-spacings of 2.76 and 1.37 nm, indicating the presence of order in the hybrid structure. Optical properties of the hybrid films were characterized by UV-vis absorption and fluorescence spectra, and molecular orientation was characterized by IR spectroscopy. A rhodamine B derivative containing a triethoxysilane group was covalently incorporated into the silicate network of the films during the sol-gel reaction. Relative to disordered polymer films with identical organic composition, the ordered hybrid films revealed significantly enhanced emission from rhodamine B and also fluorescence quenching from OPV segments. These results indicate that the ordered and nanostructured environment leads to highly efficient energy transfer among organic components in these hybrid films.     

三氟化硼乙醚溶液中卤代芴的电化学聚合

在三氟化硼乙醚(BFEE)溶液中9-溴芴和9,9-二氯芴可以直接阳极氧化制备聚(9-溴芴)和聚(9,9-二氯芴).单体在BFEE中的起始氧化电位远低于在乙腈体系中的起始氧化电位.聚(9-溴芴)和聚(9,9-二氯芴)均可溶于强极性有机溶剂,如二甲基亚砜、四氢呋喃等,并分别表现出良好的蓝色和黄绿色发光性能,其电导率测定为10-1S/cm.红外光谱和核磁共振波谱表明聚合反应主要发生在2,7位.     

Mega three-photon absorption cross-section enhancement in pseudoisocyanine J-aggregates

Herein we report an extraordinary three-photon absorption cross-section (sigma'3) enhancement in J-aggregates supramolecular systems. The much higher value of sigma'3 in PIC J-aggregate (2.5 x 10(-71) cm6 s2 ph(-2)) compared to typical values obtained in organic molecules (10(-80) cm6 s2 ph(-2)) is attributed to the strong molecular transition dipole moment coupling in the supramolecular assembly. Three-photon absorption of PIC J-aggregates and monomer aqueous solutions were measured using the well known open aperture Z-scan technique pumping with a 25 ps pulse laser-OPG system at 1720 nm. This novel result opens new expectations for applications of supramolecular systems in bioimaging and medicine.