Molecular Packing and Solid-State Photophysical Properties of 1,3,6,8-Tetraalkylpyrenes

The relationship between the photophysical properties and molecular orientation of 1,3,6,8-tetraalkylpyrenes in the solid state is described herein. The introduction of alkyl groups with different chain structures (in terms of length and branching) did not affect the photophysical properties in solution, but significantly shifted the emission wavelengths and fluorescence quantum yields in the solid state for some samples. Pyrenes bearing ethyl, isobutyl, or neopentyl groups at the 1-, 3-, 6-, and 8-positions showed similar emission profiles in both the solution and solid states. In contrast, pyrenes bearing other alkyl groups exhibited an excimer emission in the solid state, similar to that of the parent pyrene. On studying the photophysical properties in the solid state with respect to the obtained crystal structures, the observed solid-state photophysical properties were found to depend on the relative position of the pyrene chromophores. The solid-state photophysical properties can be controlled by the alkyl groups, which provide changing crystal packing. Among the pyrenes tested, 1,3,6,8-tetraethylpyrene showed the highest fluorescence quantum yield of 0.88 in the solid state.     

"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。     

Synthesis of polyfluorenes bearing lateral pyreneterminated alkyl chains for dispersion of single-walled carbon nanotubes

Two kinds of polyfluorenes bearing two lateral pyrene terminated alkyl chains and two alkyl chains per repeating unit were synthesized by Suzuki polycondensation and used to disperse single-walled carbon nanotubes(SWCNT) in organic solvents.Stable polymer-SWCNT complex can be formed via the multivalentπ-πstacking interaction of the lateral pyrene functional groups and the polyfluorene backbone with the outer surface of carbon nanotubes;meanwhile the lateral alkyl chains can impart good solubility to the complex.As expected,polyfluorenes bearing lateral pyrene functional groups and octyl chains exhibited much higher carbon nanotube solubility in common organic solvents than the corresponding polyfluorenes bearing only octyl chains.Photophysical studies indicated that the formation of polymer-SWCNT complex can effectively quench the fluorescence of polyfluorenes.     

Study of the diffusion of pyrene in silicone polymer coatings by steady state fluorescence technique: effects of pyrene concentration

The concentration dependence of the diffusion coefficient of pyrene in single component and two-component room temperature curing silicone polymer coatings is investigated by the steady state fluorescence technique by measuring the pyrene excimer fluorescence intensity. At pyrene concentrations lower than 10 mM, the intensity of excimer fluorescence is proportional to the concentration and at higher concentrations it deviates from this trend due to concentration quenching. Thermal aging studies show that this concentration quenching can be removed by thermal annealing and the excimer emission intensity approaches the value expected from the trend at lower concentrations. The diffusion coefficient of pyrene at low concentrations in silicone polymer coatings is obtained using the approximate solution of one-dimensional diffusion equation. A modified approach is employed to estimate the diffusion coefficient at higher pyrene concentrations. In this method, the excimer intensity and time scale are shifted, respectively to I_max the maximum value of excimer intensity attained during annealing and t_max, the time taken to reach this. The estimated diffusion coefficients at different pyrene concentrations show a negligible dependence on pyrene concentration in both types of polymers. These results are attributed to the high structural mobility of silicone polymer chains due to their molecular structure.     

本体与界面条件下MAPTMS水解-缩合过程中簇集行为比较研究

以甲基丙烯酰氧丙基三甲氧基硅烷(MAPTMS)为前驱体,利用荧光光谱、在线衰减全反射红外光谱(In-situ ATR-FT-IR),比较性地研究了在本体及气液界面条件下MAPTMS在酸性介质中的水解-缩合过程.借助于LB膜技术,测定了MAPTMS在气液界面水解-缩合反应过程中的π-A曲线.不论在本体相还是气液界面相,荧光探针芘均表现出明显的芘分子完全重叠及部分重叠的激基缔合物的荧光发射特征.结果表明:MAPTMS水解产物在水相中发生簇集,而且簇集体疏水端相互作用存在一定刚性.芘的荧光光谱随反应进行表现出显著变化,但本体相荧光光谱变化较气液界面相剧烈.ATR-FT-IR光谱在线检测表明:本体水解缩合产物具有较高的聚合度,而气液界面水解缩合产物聚合度较低.上述结果说明体系中存在簇集行为的显著变化,且在气液界面MAPTMS水解产物受限程度比本体相大.分子在气液界面上的聚集行为也由-πA曲线的结果得到进一步证实.文中依据MAPTMS水解产物具有类似表面活性剂的特性对上述实验结果给予了解释.     

Synthesis and characterization of novel pyrene-dendronized porphyrins exhibiting efficient fluorescence resonance energy transfer: optical and photophysical properties

A novel series of pyrene dendronized porphyrins bearing two and four pyrenyl groups (Py(2)-TMEG1 and Py(4)-TMEG2) were successfully synthesized. First and second generation Fréchet type dendrons (Py(2)-G1OH and Py(4)-G2OH) were prepared from 1-pyrenylbutanol and 3,5-dihydroxybenzyl alcohol. These compounds were further linked to a trimesitylphenylporphyrin containing a butyric acid spacer via an esterification reaction to obtain the desired products. Dendrons and dendronized porphyrins were fully characterized by FTIR and (1)H NMR spectroscopy and their molecular weights were determined by matrix-assisted laser desorption ionization time of flight mass spectrometry. Their optical and photophysical properties were studied by absorption and fluorescence spectroscopies. The formation of dynamic excimers was detected in the pyrene-labeled dendrons, with more excimer being produced in the higher generation dendron. The fluorescence spectra of the pyrene dendronized porphyrins exhibited a significant decrease in the amount of pyrene monomer and excimer emission, jointly with the appearance of a new emission band at 661 nm characteristic of porphyrin emission, an indication that fluorescence resonance energy transfer (FRET) occurred from one of the excited pyrene species to the porphyrin. The FRET efficiency was found to be almost quantitative ranging between 97% and 99% depending on the construct. Model Free analysis of the fluorescence decays acquired with the pyrene monomer, excimer, and porphyrin core established that only residual pyrene excimer formation in the dendrons could occur before FRET from the excited pyrene monomer to the ground-state porphyrin core.     

Dinuclear Diphosphine Complexes of Gold(I) Alkynyls,the Effects of Alkynyl Substituents onto Photophysical Behavior

A series of dinuclear diphosphine complexes of gold(I) alkynyls containing bis(diphenylphosphanyl)ethane/propane and alkynyl ligands with aromatic substituents (biphenyl, pyrene, and azobenzene) was synthesized and characterized using X‐ray crystallography and NMR spectroscopy. Photophysical parameters of the compounds obtained strongly depend on the nature of aromatic substituents in the alkynyl ligands. Azobenzene containing derivatives are non‐luminescent, whereas biphenyl and pyrene containing complexes display moderate emission both in solution and in solid state. The complexes with biphenyl substituents display strong heavy atom effect and show typical phosphorescent emission. In contrast, the complexes containing pyrene chromophore are fluorescent that points to the absence of spin orbit coupling in these systems, which additionally display static excimer emission in solid phase due to ground state π‐stacking of the pyrene moieties.     

Study of properties on non-protected room temperature phosphorescence and delayed excimer fluorescence of pyrene solution

A strong and stable room temperature phosphorescence (RTP) and delayed excimer fluorescence signal located at 596 and 475 nm, respectively, can be induced for pyrene solution in the absence of any protective medium only use KI or TlNO3 as a heavy atom perturber (HAP) and Na2SO3 as a deoxygenator. Both lifetimes of RTP and the delayed fluorescence are in the order of X-ms and the intensities are changed with kind and amount of HAP, but the peak positions are same and there is a iso-luminescent point in the emission spectra corresponding to emission at 475 nm and at 596 nm. The optimum conditions and the effects of kind and amount of HAP and organic solvents on luminescence properties of pyrene solution were studies in detail, and the photophysical process in the presence of KI or TlNO3 for phosphorescence and delayed excimer fluorescence emission of pyrene solution was discussed.     

Ratiometry of monomer/excimer emissions of dipyrenyl calix[4]arene in aqueous media

Variations in the ratio of monomer/excimer emissions from pyrenyl groups bound to a calix[4]arene through facing carboxamidomethyl substituents have been investigated in H₂O/CH₃CN mixtures. Above a level of 50% H₂O, monomer emission declines and the excimer emission concomitantly increases. DFT calculations support the argument that disruption of intramolecular NHO bonds by water results in a geometry, which favors contact of the pyrene units and thus a strong excimer emission. Addition of Fe(III) to a H₂O/CH₃CN (4:1, v/v) solution of 1 at pH 6.1 quenches both monomer and excimer emissions through electron transfer (eT) from excited pyrene to the metal ion.     

Molecule-binding dependent assembly of split aptamer and γ-cyclodextrin: A sensitive excimer signaling approach for aptamer biosensors

A highly sensitive and selective fluorescence aptamer biosensors for the determination of adenosine triphosphate (ATP) was developed. Binding of a target with splitting aptamers labeled with pyrene molecules form stable pyrene dimer in the γ-cyclodextrin (γ-CD) cavity, yielding a strong excimer emission. We have found that inclusion of pyrene dimer in γ-cyclodextrin cavity not only exhibits additive increases in quantum yield and emission lifetime of the excimer, but also facilitates target-induced fusion of the splitting aptamers to form the aptamer/target complex. As proof-of-principle, the approach was applied to fluorescence detection of adenosine triphosphate. With an anti-ATP aptamer, the approach exhibits excimer fluorescence response toward ATP with a maximum signal-to-background ratio of 32.1 and remarkably low detection limit of 80 nM ATP in buffer solution. Moreover, due to the additive fluorescence lifetime of excimer induced by γ-cyclodextrin, time-resolved measurements could be conveniently used to detect as low as 0.5 μM ATP in blood serum quantitatively.     

7-Deazapurine and 8-aza-7-deazapurine nucleoside and oligonucleotide pyrene "click" conjugates: synthesis, nucleobase controlled fluorescence quenching, and duplex stability

7-Deazapurine and 8-aza-7-deazapurine nucleosides related to dA and dG bearing 7-octadiynyl or 7-tripropargylamine side chains as well as corresponding oligonucleotides were synthesized. "Click" conjugation with 1-azidomethyl pyrene (10) resulted in fluorescent derivatives. Octadiynyl conjugates show only monomer fluorescence, while the proximal alignment of pyrene residues in the tripropargylamine derivatives causes excimer emission. 8-Aza-7-deazapurine pyrene "click" conjugates exhibit fluorescence emission much higher than that of 7-deazapurine derivatives. They are quenched by intramolecular charge transfer between the nucleobase and the dye. Oligonucleotide single strands decorated with two "double clicked" pyrenes show weak or no excimer fluorescence. However, when duplexes carry proximal pyrenes in complementary strands, strong excimer fluorescence is observed. A single replacement of a canonical nucleoside by a pyrene conjugate stabilizes the duplex substantially, most likely by stacking interactions: 6-12 °C for duplexes with a modified "adenine" base and 2-6 °C for a modified "guanine" base. The favorable photophysical properties of 8-aza-7-deazapurine pyrene conjugates improve the utility of pyrene fluorescence reporters in oligonucleotide sensing as these nucleoside conjugates are not affected by nucleobase induced quenching.     

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.     

A new pyrene-based fluorescent probe for the determination of critical micelle concentrations

A new pyrene-based fluorescent probe for the determination of critical micelle concentrations (CMC) is described. The title compound 1 is obtained in five steps, starting from pyrene. Fluorescence spectroscopic properties of 1 are studied in homogeneous organic solvents and aqueous micellar solutions. In a wide range of organic solvents, probe 1 exhibits a characteristic monomer emission of the pyrene fluorophore, with three distinct peak maxima at 382, 404, and 425 nm. The spectra change dramatically in aqueous solution, where no monomer emission of the pyrene fluorophore is detected. Instead, only strong excimer fluorescence with a broad, red-shifted emission band at lambda(max) = 465 nm is observed. In micellar aqueous solution, a superposition of the monomer and excimer emission is found. The appearance of the monomer emission in micellar solution can be explained on the basis of solubilization of 1 by the surfactant micelles. The ratio of the monomer to excimer fluorescence intensities of 1 is highly sensitive to changes in surfactant concentration. This renders 1 a versatile and sensitive probe molecule for studying the micellization of ionic and nonionic surfactants. For a representative selection of common surfactants, the critical micelle concentrations in aqueous solution are determined, showing excellent agreement with established literature data.     

Probes of the microenvironments of the cationic copolymers of styrene and vinylbenzenetrialkylammonium halides

The microenvironments of the cationic copolymers of styrene and vinylbenzenetrialkylammonium halides were explored by use of fluorescence spectroscopy. 5-Dimethylamino-1-naphthalenesulfonate (DANS) and 1-pyrenebutyrate (PB) were the fluorescent probes selected to bind to the polymers. The fluorescence energy of the former responds to the polarity or hydrophobicity of the microenvironment, whereas the absorption and fluorescence of the latter reveal the extent of ground-state and excited-state interactions. Polyelectrolyte coiling occurs in proportion to the fraction of binding sites occupied with charge-neutralizing, probe molecules. The bound DANS probe shows that coiling makes the binding-site environment more hydrophobic, and the bound PB probe shows that coiling facilitates excimer formation not only with nearest-neighbor pyrene moieties, but also with non-nearest neighbors. With methyl groups at the quaternary nitrogen binding sites, pyrene moiety interactions preceding excimer fluorescence occur in both ground and excited states. When the methyl groups are replaced with butyl or pentyl groups, pyrene excimers still form in the excited state, but the weak, hydrophobic interactions of the pyrene ground state decrease, because the longer alkyl groups serve as hosts for the hydrophobic pyrene moieties.     

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.     

Resolution of ultrafast pyrene excimer emission rise times in zeolites X and Y

Pyrene has been a favorite photophysical probe molecule for zeolite research because of its ability to exhibit both monomer and excimer emission upon excitation. This study combines the use of ultrafast time-resolved fluorescence spectroscopy with steady-state fluorescence spectroscopy to study the excimer emission of pyrene incorporated within zeolites LiY, NaY, KY and NaX. The effects of sealing technique and coincorporated solvents are also explored. Pyrene excimer emission is resolvable with the use of an ultrafast streak camera under all conditions examined in this study with a rise-time range of 6.8 to 16.0 picoseconds. For each zeolite sample the addition of cosolvents decreases the rise time, with a greater decrease for polar solvents than for a nonpolar solvent. The presence of a detectable rise time for excimer emission indicates that pyrene excimer formation is a dynamic process when pyrene is embedded within the cavities of zeolite host materials.     

Solvent-driven multiply configurable on/off fluorescent indicator of the pH window: a diethylenetriamine bearing two end pyrene fragments

Fluorescence behaviors of a simple-structured molecule (L), a diethylenetriamine bearing two end pyrene fragments, have been investigated in water. Effects of adding a less-polar organic solvent (acetonitrile: MeCN) on the emission behaviors have been studied by means of steady-state and time-resolved fluorescence measurements. L dissolved in water shows dual-mode fluorescence consisting of monomer and excimer emissions. The monomer emission shows an "on-off" intensity profile against the pH window (pH 2-12), whereas the excimer emission shows an "off-on" profile. Upon MeCN addition, the monomer emission maintains the "on-off" profile. In contrast, the "off-on" profile of the excimer emission is drastically changed: L shows two more types of profiles, "off-on-off-on" and "off-on-off", along with the MeCN concentration increase, thus behaving as a multiply configurable fluorescent indicator of the pH window. The MeCN-driven excimer emission switching of L is triggered by (i) the decrease in stability of the intramolecular ground-state dimer (GSD) formed between the end pyrene fragments, which suppresses the direct photoexcitation of GSD (suppression of the "static" excimer formation), leading to a decrease in the excimer emission intensity at basic pH; and (ii) the decrease in polarity of solution, which allows formation of a "dynamic" excimer via a monomer-to-excimer transition, resulting in an enhancement of the excimer emission intensity at acidic-neutral pH.     

MOLECULAR CONFORMATION OF IONIC SURFACTANTS IN AQUEOUS SOLUTION

The molecular conformation of ionic surfactant in aqueous solution is investigated withfluorescent probes which are intrinsic insurfactant molecules or externally introduced. Quench-lng or pyrene monomer fluorescence by alkyltriphenylphosphonium or N-alkylpyridiniumobeys Stern-Voimer equation, being diffusi6n-controlled dynamic quenching, but the behaviorof quenching with different lengths of alkyl chain is "abnormal", i.e. the longer the chain,the greater the quenching rate constant. The pyrene excimer fluorescence is observed in theaqueous solution of cetyltrimethylammonium bromide (CTMAB), and the inhibition (for cationicquenchers) and promotion (for anionic quenchers) effects of CTMAB on the quenching ofpyrene fluorescence are also observed. The self-coiling conformation of ionic surfactantmolecules in aqueous solution is proposed to be responsible for these observations and theconformation to be dynamic.     

Fusion-fission transport of probes and quenchers in microdomains of an amphiphilic ionene polyelectrolyte

In aqueous solution, amphiphilic ionenes such as the [3,22]-ionene spontaneously adopt globular conformations and form microdomains that are highly micelle-like, i.e. are capable of solubilizing organic molecules, binding and exchanging counterions and accelerating or inhibiting the rates of bimolecular reactions. Time-resolved fluorescence decay of pyrene and pyrene derivatives solubilized in these microdomains at concentrations where excimer formation occurs show that even water-insoluble probes can migrate between the hydrophobic microdomains formed in aqueous solution by a [3,22]-ionene chloride (with the N-terminal groups quaternized with benzyl chloride). Time-resolved studies of the quenching of pyrene fluorescence by alkylpyridine derivatives revealed similar behavior. The observed quenching behavior requires that the migration be between microdomains on the same ionene chain or same group of associated ionene chains and is consistent with migration dominated by fusion/fission transport of the probe and quencher.     

New cyclen-cored dendrimers functionalized with pyrene: Synthesis characterization,optical and photophysical properties

New cyclen (1,4,7,10-teraazacyclododecane) cored dendrimers up to the second generation, functionalized with 4, 8 and 16 pyrene units, respectively, were synthesized following a convergent procedure. All new compounds were characterized by NMR spectroscopies and ESI or MALDI TOF mass spectrometry. The optical and photophysical properties of the new dendrimers were studied in THF solution. Absorption spectra showed the typical absorption bands of pyrene moieties. In the fluorescence spectra, monomer as well as excimer emission were observed for all compounds. An increased proportion of excimer emission was observed in the dendrimer of the highest generation.