Probing the effects of cholesterol on pyrene-functionalized interfacial adlayers

We have synthesized a novel set of pyrene-functionalized, covalently bound surface adlayers with and without cholesterol derivatives coadded to the adlayer. We have deposited these adlayers on quartz, oxidized silicon wafers, and indium-doped tin oxide coated substrates. The addition of tethered cholesterol to the adlayer creates a hydrophobic, likely disordered, microenvironment in which the surface-bound pyrene resides. X-ray photoelectron spectroscopy measurements demonstrate the covalent attachment of both cholesterol and pyrene in our adlayers. The presence of the cholesterol moieties gives rise to a reduction in film thickness, as measured ellipsometrically, and contact angle data indicate significant surface heterogeneity. Steady-state fluorescence data show that the presence of cholesterol moieties reduces the extent of pyrene excimer formation and provides a less polar environment for the chromophore. Fluorescence lifetime measurements on surface-bound pyrene were biexponential, consistent with multiple local environments, regardless of whether tethered cholesterol was present or not. Cyclic voltammetry reveals competition between the pyrene and cholesterol moieties for binding to available surface sites on the epoxide-terminated surface-binding layer we use.     

Unique hydrophobic interactions of pyrene in aqueous solution as effected by polyelectrolytes and surfactants

Pyrene substituents covalently bounded to polyelectrolytes show not only excited-state interactions but also unique ground-state interactions in aqueous solution. The pyrene moieties in pyrenesubstituted ionic molecules also show these interactions when aqueous solutions of these molecules are treated with polyelectrolytes or surfactants well below their critical micelle concentrations. These hydrophobic interactions are revealed by changes in absorption, fluorescence, and excitation spectra. The well-resolved vibrational bands in the absorption and excitation spectra of pyrene become somewhat diffuse, whereas monomer fluorescence is reduced and replaced by excimer fluorescence. The rationale for these results is that the pyrene moieties in these ionic solutions seek out hydrophobic locations on the polyelectrolytes or surfactants, where pyrene aggregation is responsible for these interactions and the corresponding changes in spectra.     

An excimer-based, binuclear, on-off switchable calix[4]crown chemosensor

A new fluorescent chemosensor with two different types of cation binding sites on the lower rims of a 1,3-alternate calix[4]arene (1) is synthesized. Two pyrene moieties linked to a cation recognition unit composed of two amide groups form a strong excimer in solution. For 1, the excimer fluorescence is quenched by Pb2+, but revived by addition of K+ to the Pb2+ ligand complex. Thus, metal ion exchange produces an on-off switchable, fluorescent chemosensor. Computational results show that the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbitals (LUMO) of the two pyrene moieties interact under UV irradiation of 1 and its K+ complex, while such HOMO-LUMO interactions are absent in the Pb2+ complex.     

Electric field effects on absorption and fluorescence spectra of trimethylsilyl- and trimethylsilylethynyl-substituted compounds of pyrene in a PMMA film

External electric field effects on absorption and fluorescence spectra of 1,3,6,8-tetrakis(trimethylsilyl)pyrene and 1,3,6,8-tetrakis(trimethylsilylethynyl)pyrene (TMSPy and TMS(E)Py, respectively) have been examined in a poly(methyl methacrylate) (PMMA) film at various concentrations at various temperatures. TMS(E)Py preferentially forms an aggregate in a PMMA film, as the concentration increases, indicating that the acetylenic groups enhance the pi-pi interactions between pyrene molecules. The change in molecular polarizability following excitation has been determined both for the monomer and for the aggregate, based on the electroabsorption spectra. The change in molecular polarizability following emission has also been determined in both compounds, based on the electrofluorescence spectra. TMSPy exhibits two excimer fluorescence emissions at high concentrations which are ascribed to the partially overlapping excimer and the sandwich-type excimer, respectively, besides the monomer fluorescence emitted from the locally excited state. The sandwich-type excimer fluorescence as well as monomer fluorescence is quenched by an electric field, whereas the fluorescence of the partially overlapping excimer is enhanced by an electric field. Excimer fluorescence of TMS(E)Py, which arises from the sandwich-type excimer, is quenched by an electric field at any temperature. Only one species of the partially overlapping excimer is confirmed in TMSPy, while no partially overlapping excimer is confirmed in TMS(E)Py.     

Effect of leucinyl-phenylalanyl-valine on DMPC liposome membrane

Leucinyl-phenylalanyl-valine (LFV) is a hydrophobic tripeptide with a flat egg shaped structure with the long axis dimension of about 12 A. The effect of LFV on dimyristoylphosphatidylcholine (DMPC) liposome membrane has been studied by differential scanning calorimetry (DSC) and fluorescence spectroscopy. Calorimetric studies shows that incorporation of LFV completely abolishes the pretransition temperature with broadening of main transition temperature. Four conceptually different fluorescence probes, 1-naphthol (1-ROH) an excited state proton transfer probe, 8-anilino-1-naphthalenesulphonate (ANS) a solvent polarity probe, 1-6-diphenylhexatriene (DPH) an anisotropy probe and pyrene an excimer-forming probe have been used for fluorescence spectroscopic studies. For 1-ROH, ANS and DPH, a decreased partitioning with increasing mol.% of LFV was observed. Increasing LFV mol.% caused a decrease in the neutral form emission of 1-ROH, and a decrease in fluorescence intensity with red shift in ANS. The excimer formation ability of pyrene also decreased. The phase transition behavior of DMPC membrane in the presence of LFV was similar to the known effect of cholesterol on lipid bilayers. These results suggest that LFV cause an increased compactness of membrane.     

The use of doped crystals as a medium for the study of excited state bimolecular interactions

A molecular crystal is an attractive medium for the study of excited state intenmolecular interactions since the ground state positions of interacting molecules may be accurately determined. Besides excimer interactions in pure crystals it is possible to study (in doped crystals) exciplex interactions between host and guest molecules, and even excimer formation between two adjacent guest molecules. This approach has been utilized to observe excimer formation by several anthracene derivatives introduced as dopants in pyrene crystals. Photochemical reactions of some of these exciplexes and excimers are discussed. Excimer forming crystals are considered to be good candidates for excited state structure determination by means of pulsed x-ray diffraction.     

A fluoride-selective PCT chemosensor based on formation of a static pyrene excimer

[reaction: see text] Calixarene-based fluorescent chemosensor 1 with two fluorogenic pyrene units conjugated to amide groups as guest recognition sites is synthesized. Complexation of F(-) by 1 causes a red shift of its absorption band to 400 nm (Deltalambda = 54 nm) and a blue shift of the excimer emission to 470 nm (Deltalambda = 12 nm) together with enhanced fluorescence intensity. The blue-shifted excimer emission is attributed to a pyrene dimer formed in the ground state, a so-called static excimer.     

Existence of intramolecular triplet excimer of bis(9-fluorenyl)methane: phosphorescence and delayed fluorescence spectroscopic and ab initio studies

A concerted computational and experimental study has been undertaken to probe the conformational structure and excited-state dynamics of bis(9-fluorenyl)methane (BFM). We have observed that the relative intensity of the delayed excimer fluorescence of BFM is greatly enhanced in comparison with that of the normal fluorescence. This is presumably because the relative concentration of the triplet excimer is enhanced in comparison with the singlet excimer. B3LYP DFT/6-31G(d) calculations indicate that the sandwich conformer of BFM in the singlet ground state is unstable, whereas that in the triplet excited state has a bound state, being very slightly higher in internal and Gibbs free energies than that of the lowest state of the near-orthogonal conformer.     

Interactions of ionic surfactants with gelatin in fluid solutions and the gel state studied by fluorescence techniques,potentiometry, and measurements of viscosity and gel strength

The photobehavior of pyrene (fine structure of the monomeric fluorescence band; excited state lifetimes; excimer/monomeric fluorescence intensity ratios and excited state quenching rates by oxygen) in fluid solutions of gelatin and in the gel state, both in the absence and presence of ionic surfactants, has been examined. Surfactants considered were sodium dodecylsulfate and dodecyltrimethylammonium bromide. Potentiometric measurements performed by using surfactant selective electrodes allowed for the determination of the binding capacity of the surfactants onto gelatin in the gel state. When complemented with viscosity and gel strength measurements, the sesults obtained allow for a discussion of the effects of the surfactant-gelatin interactions on microscopic properties of the solutions or gels and their relation with macroscopic properties.     

Molecular dynamics simulation of pyrene solubilized in a sodium dodecyl sulfate micelle

In the present work, the structural and dynamical aspects of the solubilization process of pyrene within a sodium dodecyl sulfate micelle were studied using molecular dynamics simulations. Our results showed that free pyrene as the fluorescence probe can be spontaneously solubilized into the micelle and prefers to be located in the hydrophobic core region. As the local concentration of pyrene increased, two molecular probes could enter into the core hydrophobic region and the excited dimer of pyrene molecules was formed, showing a stacking mode of π-π conjugation. Since the π-π stacking interaction between the two pyrene molecules was very weak, formation of the excimer was a dynamic process with the two pyrene molecules alternately separating and associating with each other. In this case, the two pyrene molecules were found to be mainly distributed in the palisade layer of the micelle due to the balance between the weak π-π stacking interaction and the hydrophobic interaction of probe molecules with the surfactant tails.     

Intramolecular charge transfer in 1:1 Cu(II)/pyrenylcyclam dendrimer complexes

Two newly synthesized pyrenylcyclam dendrons (1 and 2) exhibit a new emission band centered at 450 nm when coordinated with copper triflate. Observed fluorescence shifts induced by coordinative metalation indicate an unusual intramolecular charge transfer from a pyrenyl excited state to the coordinated metal ion that competes with pyrene excimer formation. This interaction likely proceeds by photoexcitation of pi-complex of the appended arene, followed by intramolecular charge transfer within the dendritic 1:1 cyclam/metal complex, effecting reduction of the bound Cu(II) metal ion. The appended dendritic groups not only decrease the equilibrium binding constant with Cu(II) but also participate in a new excited-state pathway as an alternative to energy-dissipative excimer formation.     

Photoreactivity and emission properties of liquid-crystalline twin dimers containing cinnamic acid moieties at both ends of ethylene glycol spacers. II. Emission properties

Emission properties of liquid-crystalline twin dimers containing 4-methoxy-cinnamic acid moieties at both ends of various ethylene glycol derivatives (nEGMC), where n denotes the number of the ethylene glycol units in the spacers, have been explored by steady-state and time resolved fluorescence spectroscopy in relation to the morphology of the system. Characteristic emissions were observed in the twin dimers, particularly in 2EGMC and 5EGMC, which were ascribed to excimer emission, and the energy gap between the locally excited state (monomer emission) and the excimer state and could be correlated to the difference in the spatial orientation of the mesogenic 4-methoxycinnamate groups adopted in nEGMC in the ground state. The picosecond time resolved fluorescence spectroscopy revealed no observed rise in the excimer emission in any sample at any temperature, indicating that the excimer is most probably formed by direct excitation of the pair wise arrangement of the 4-methoxycinnamate moieties in the ground state; thus, the excimer formation behaviour reflects well the ground state morphology of the twin dimers.     

"标记"芘的激基缔合物荧光在水溶性高分子研究中的应用

首先介绍了芘的荧光发射光谱的特点及其激基缔合物荧光、然后给出了用芘标记高分子的各种方式和方法,讨论了水溶性高分子的”标记”芘形成激基缔合物的原理,评述了芘标记高分子箕缔合物荧光在水溶性分子疏水相互作用,静电相互作用、氢键、络合等研究中的应用,也介绍了芘标记激基缔的荧光在高分子凝胶体积相变、分子链运动等领域的研究进展。     

Fluorescent probe as reporter on the local structure and dynamics in hydrolysis-condensation process of organotrialkoxysilanes

To get some information on the aggregation behaviors of the products derived from different organotrialkoxysilanes, the hydrolysis-condensation processes of some organotrialkoxysilanes have been examined by means of pyrene as fluorescent probe. The organotrialkoxysilanes used in the research were n-octadecyltri-methoxysilane (ODTMS), n-octyltrimethoxysilane (OTMS), 3-glycidoxypropyltrimethoxysilane (GTMS), 3-methacryloxypropyltrimethoxysilane (MAPTMS), and propyltrimethoxy-silane (PTMS). The results show that pyrene as fluorescence probe can respond sensitively not only to the organization state of the hydrolysates but also to the change in the organization state during the condensation process. The organization states during the hydrolysis and condensation can be explained in terms of structures of the products. In the initial stage, the silanols with long organic chains are amphiphilic molecules, and such nature of the silanols can be compared to that of a surfactant. Therefore, the excimer emission of pyrene is extremely obvious because of such silanols being prone to form aggregates. In the case of silanols having short alkyl groups or epoxy groups, these silanols homogenously disperse in solution, which results in the appearance of an only monomer emission of pyrene. In the late stage, the fluorescence behavior of pyrene is also sensitive to structural evolution of the silicates. The fluorescence spectra of pyrene during the condensation of the silanols with short alkyl groups or epoxy groups are almost in silence, indicating that the condensation products, with a low condensation degree, homogeneously disperse in solution. For the silanols with long hydrophobic substituents in different lengths, the changes in fluorescence spectra of pyrene during the condensation are varied. Commonly, the excimer emission is noticeable, implying that the condensation products with high condensation degree inhomogenously disperse in solution. However, the relative excimer/monomer fluorescence intensity is alkyl chain-length dependent. The longer alkyl chains in the condensation products result in the appearance of the obvious excimer emission. These phenomena imply that the condensation degree of the products increases with the length of the alkyl chains. Additionally, the distorted spectrum of pyrene appears in the case of the organotrialkoxysilanes with side chain substituent, illustrating that the steric hindrance between the substituents can be monitored by fluorescence of pyrene. All these results are verified by the fluorescence-quenching measurements. The approach in the present study gives new insights into the local structure and dynamics in hydrolysis-condensation process of organotrialkoxysilanes and emphasizes the influence of the self-assembling behavior.     

A photophysical study of the interactions in poly(styrene-4-sulphonate)–n-butylvinylether block and random copolymers

Interactions between the moieties responsible for the conformations and hydrophobic microdomains in poly(styrene-4-sulphonate) (PSS) and its copolymers with n-butylvinylether (BVE) were studied by their emission spectra and the lifetimes of the phenyl groups and pyrene used as a photochemical probe. The emission spectra of PSS shows bands due to dimers and higher aggregates as well as the characteristic excimer band. At low concentrations, the random copolymers have spectra similar to that of the free monomer, whereas the block copolymers have spectra like that of PSS. At higher concentrations, the random copolymer also shows these excimer bands, due to interchain interactions. Results from the emission of pyrene prove that the behaviour of the copolymers with approximately 40% BVE seems to be relatively independent of having random or block configurations. Except at low concentrations (<0.05 g/dl), where the block copolymer already has a conformation with “stable” hydrophobic microdomains, both types of copolymers behave similarly. There is an initial aggregate equilibrium between individual chains and aggregates, associated with a relocation of the probes. At higher concentrations, both copolymers suffer a severe change in conformation, due to the formation of “stable” hydrophobic microdomains, resulting from interchain interactions. In both cases the lifetimes of pyrene are of the order of 240 ± 10 ns. Received: 27 August 1998 Accepted: 11 January 1999     

Indium(III)-induced fluorescent excimer formation and extinction in calix[4]arene-fluoroionophores

New fluorogenic or/and chromogenic calix[4]arenes 1-3 with two facing amide groups linked to fluorescent pyrene units are synthesized. Orientations of the pyrene units are remote from each other in 1 and face-to-face pi-stacked in 2, which produces different photophysical properties. In the excited state, the two pyrene units of 2 form a strong intramolecular excimer displaying an emission at 472 nm with a relatively weak monomer emission at 395 nm. In contrast, 1 exhibits only a monomer emission at 398 nm because intramolecular hydrogen bonding between the phenolic OH oxygens and the amide hydrogens prevents pi-stacking of the two pyrene groups. Fluorescence changes upon addition of various metal ions show that 1 has a remarkably high selectivity for In(3+) over the other metal ions tested. Compound 1 forms 2:1 (metal:ligand), as well as 1:1 complexes, with In(3+), with fluorescence varying uniquely with the complex stoichiometry. Compound 3, which possess two pyrene units and two chromogenic azo groups, shows almost the same binding behavior toward metal ions as does 1, together with additional bathochromic shifts of the absorption maximum. Compared with 1, compound 3 emits a considerably weaker fluorescence, which is attributed to electron transfer from the pyrene units to the nitro groups of the phenylazo moieties.     

Amphiphilic copolymers with increased affinity for substrates

The copolymers of methyl quaternized 2-dimethylaminoethyl acrylate and styrene, 2-vinyl naphthalene, acrylic acid iso-octyl ester, or acrylic acid n-butyl ester have been prepared. Studies were made of the binding of a “binding probe,” methyl orange, by the copolymers in aqueous solution. The first binding constants and the thermodynamic parameters in the course of the binding were evaluated. Furthermore, the intensity of fluorescence of a hydrophobic fluorescent probe, 2-p-toluidinylnaphthalene-6-sulfonate, in the presence of these polymers was investigated. In addition, the fluorescence spectra of monomer and excimer emissions of the polymers with aromatic residues were measured. The excimer/monomer fluorescence intensity ratio was studied in the presence of various additives such as methyl orange, urea, methanol, and NaCl to gain an insight into the nature of microdomains in the polymer. The nature and phenomena of dye binding and hydrophobic fluorescent probe binding with the polymers are discussed. © 1993 John Wiley & Sons, Inc.     

分子动力学模拟研究荧光分子芘在磺基甜菜碱胶束中的增溶

采用分子动力学模拟研究了荧光分子芘在磺基甜菜碱两性表面活性剂聚集体中的增溶现象．结果表明,芘分子自发地自溶液中增溶进入胶束疏水内核的栅栏层区域．当胶束溶液中芘分子的局部浓度增大时,两个芘分子可以同时增溶进胶束的栅栏层区域,此时两个芘分子形成π-π共轭堆积的激发态络合物．但是由于荧光分子之间的弱兀．兀相互作用,激发态络合物在胶束中是不稳定的,表现为两个芘分子的多次结合和分离．模拟表明,分子动力学方法可以在分子水平上研究荧光探针分子在表面活性剂胶束中的增溶位点,解释荧光分子在胶束中的动力学现象．     

离子型芘衍生物同聚电解质键合平衡的模拟

利用平衡键合模型模拟了聚电解质同荧光探针离子键合过程的计量关系 ,以及添加盐竞争键合时的计量关系 .计算的结果能够描述荧光实验结果 .芘离子探针PyMeA·HCl的IE IM 随着探针浓度的增加 ,会出现一个极大值 ,此极大值能够定量地给出饱和键合计量关系 .当盐浓度和聚电解质荷电单元浓度相当时 ,盐离子和芘离子探针发生明显的竞争键合 ,部分离子探针被排挤入水相 ,实验的IE IM 随盐浓度增大急剧减小     

Fluorescence studies on phenylene moieties embedded in a framework of periodic mesoporous organosilica

The excited state characteristics of phenylene (Ph)-bridged periodic mesoporous organosilica (PMO) powders with crystal-like and amorphous wall structures are investigated. Crystal-like Ph-PMO has a molecular ordering of the bridging organic moieties with intervals of 0.76 and 0.44 nm parallel and perpendicular to the mesochannel direction, respectively, whereas amorphous Ph-PMO has no molecular-level periodicity in the wall. Fluorescence from the exciton and excimer of the Ph moieties and the defect center in the silicate network were detected at room temperature, but fluorescence from the excimer and the defect center were not detected at 77 K for crystal-like Ph-PMO dispersed in a methanol/ethanol mixed solvent. The decay curve of the exciton fluorescence of crystal-like Ph-PMO at room temperature was analyzed successfully using a one-dimensional diffusion model quenched by the defect center and the excimer site. The results were discussed in comparison with those for the crystal-like biphenylene-bridged PMO reported in the preceding paper (Yamanaka et al., Phys. Chem. Chem. Phys., 2010, 12, 11688-11696). The existence of excited states with various conformations including ground state dimers or aggregates of the Ph moieties was suggested for amorphous Ph-PMO. It was clearly apparent that the differences in the excited state dynamics reflected the differences in the molecular-level structure in the wall.