Fluorescence characteristics and photostability of benzoxazole derived donor-acceptor dyes in constrained media

The spectroscopic properties and photoreactivity of 2-(4-dimethylaminostryl)benzoxazole and its butadienyl analogue (abbreviated as DMASBO and BODB, respectively) were investigated in thin films of PS, PMMA and PVA polymer matrices as well as immobilized on silica surface. The experimental results showed that the investigated benzoxazole derivatives are sensitive to the polarity of its microenvironment even in the glassy matrices and in the solid state. The micropolarity of PVA and silica surface is greater than that of PMMA and PS. The combined results of fluorescence quantum yield and photoisomerization indicated that the size of the free volume within the polymer matrix influence strongly the photochemical reactivity of the used dyes. In PVA, which offers the smaller free volume, the photoreaction is totally blocked while the fluorescence yield is extremely enhanced relative to those in solutions and other polymer matrices. This is associated with an emission of green laser from DMASBO-PVA doped film when pumped by nitrogen laser (337 nm). The results showed that the present dyes are excellent probes for non-fluorescent systems presenting constrained geometry. The spectra of amorphous solid thin films of both dyes were also measured and show large red shifts relative to those in solutions indicating symmetric aggregation of molecules in the solid crystals.     

Efficient NIR‐Light Emission from Solid‐State Complexes of Boron Difluoride with 2′‐Hydroxychalcone Derivatives

This article describes a series of nine complexes of boron difluoride with 2′‐hydroxychacone derivatives. These dyes were synthesized very simply and exhibited intense NIR emission in the solid state. Complexation with boron was shown to impart very strong donor–acceptor character into the excited state of these dyes, which further shifted their emission towards the NIR region (up to 855 nm for dye 5 b , which contained the strongly donating triphenylamine group). Strikingly, these optical features were obtained for crystalline solids, which are characterized by high molecular order and tight packing, two features that are conventionally believed to be detrimental to luminescence in organic crystals. Remarkably, the emission of light from the π‐stacked molecules did not occur at the expense of the emission quantum yield. Indeed, in the case of pyrene‐containing dye 4 , for example, a fluorescence quantum yield of about 15 % with a fluorescence emission maximum at 755 nm were obtained in the solid state. Moreover, dye 3 a and acetonaphthone‐based compounds 1 b , 2 b , and 3 b showed no evidence of degradation as solutions in CH₂Cl₂ that contained EtOH. In particular, solutions of brightly fluorescent compound 3 a (brightness: ε×Φ_f=45 000 M ^?1 cm^?1) could be stored for long periods without any detectable changes in its optical properties. All together, these new dyes possess a set of very interesting properties that make them promising solid‐state NIR fluorophores for applications in materials science.     

Solid‐state lasers based on inorganic–organic hybrid materials obtained by combined sol–gel polymer technology

Sol–gel glass matrices in which organic laser dyes are embedded can be used as the gain medium in solid‐state, continuously tunable lasers. Such lasers are very simple to construct, and potentially very compact and efficient. Unlike the commonly used liquid dye laser systems, solid‐state dye lasers can be made mechanically robust and portable. In this article, the development of sol–gel/dye lasers, including the sol–gel technology, dye properties, and laser operation, is reviewed. In addition, new solid‐state hosts (such as polyurethane/silica ORMOSILs), additional organic dyes (cyanines), and new studies on the stability of the dyes are presented. Copyright © 2004 John Wiley & Sons, Ltd.     

High-sensitivity, disposable lab-on-a-chip with thin-film organic electronics for fluorescence detection

We report a high-sensitivity, disposable lab-on-a-chip with a thin-film organic light-emitting diode (OLED) excitation source and an organic photodiode (OPD) detector for on-chip fluorescence analysis. A NPB/Alq3 thin-film green OLED with an active area of 0.1 cm(2) was used as the excitation source, while a CuPC/C(60) thin-film OPD with 0.6 cm(2) active area was used as a photodetector. A novel cost-effective, cross-polarization scheme was used to filter out excitation light from a fluorescent dye emission spectrum. The excitation light from the OLED was linearly polarized and used to illuminate a microfluidic device containing a 1 microL volume of dye dissolved in ethanol. The detector was shielded by a second polarizer, oriented orthogonally to the excitation light, thus reducing the photocurrent due to excitation light leakage on the detector by approximately 25 dB. The fluorescence emission light, which is randomly polarized, is only attenuated by approximately 3 dB. Fluorescence signals from Rhodamine 6G (peak emission wavelength of 570 nm) and fluorescein (peak emission wavelength of 494 nm) dyes were measured in a dilution series in the microfluidic device with emission signals detected by the OPD. A limit-of-detection of 100 nM was demonstrated for Rhodamine 6G, and 10 microM for fluorescein. This suggests that an integrated microfluidic device, with an organic photodiode and LED excitation source and integrated polarizers, can be fabricated to realize a compact and economical lab-on-a-chip for point-of-care fluorescence assays.     

Dye-labeled silver nanoshell-bright particle

Silica beads with average diameters of 40-600 nm were prepared, and Ru(bpy)3(2+) complexes were incorporated into the beads. These beads were coated by silver layer by layer to generate porous but continuous metal nanoshells. The thicknesses of these metal shells were 5-50 nm. The emission band from the dyes in the silica cores was more narrow and the intensity was enhanced with growth of silver shell thickness due to coupling of the emission light from Ru(bpy)3(2+) in the cores with the metal plasmon from the silver shells. The enhancement of emission intensity was also dependent on the size of the silica core, showing that the enhancement efficiency decreased with an increase in the size of the silica beads. Lifetime measurements support the coupling mechanism between the dye and metal shell. This study can be used to develop novel dye-labeled metal particles with bright and narrow emission bands.     

Silica nanoparticles encapsulating near-infrared emissive cyanine dyes

We show that efficient near-infrared (NIR) cyanine fluorophores (1 and 2) can be encapsulated into silica nanoparticles providing a highly versatile and unique platform for in vivo diagnostics. Utilizing this platform, multiple fluorophores can be loaded within a single particle allowing the light absorption and emission properties of the nanoparticle to be controlled independent of particle size. Furthermore, such dyed nanoparticles may have extinction coefficients as high as about 100 x 10(6) Lmol(-1)cm(-1) in the NIR (on a per mole of particles basis), with quantum yields from about 8-10%. A simple synthetic method for varying particle size and dye-loading level is presented, and a modified Stober synthesis reduces deleterious exposure of the dye to the highly alkaline conditions used. The cyanine dyes are encapsulated in silica in a non-aggregated state and the fluorescence brightness is largely maintained to nominal dye concentrations approaching 50 muM. The ability to control light absorption and emission properties independent of particle size, and convenient access to particle sizes in the range of 20-100 nm (a size regime difficult to access with other nanoparticle approaches such as quantum dots), are important features for anatomical targeting in in vivo diagnostics and targeted therapeutic applications.     

Preparation and flow cytometry of uniform silica-fluorescent dye microspheres

Uniform fluorescent silica-dye microspheres have been prepared by coating preformed monodispersed silica particles with silica layers containing rhodamine 6G or acridine orange. The resulting dispersions exhibit intense fluorescent emission between 500 and 600 nm, over a broad excitation wavelength range of 460 to 550 nm, even with exceedingly small amounts of dyes incorporated into the silica particles (10-30 ppm, expressed as weight of dye relative to weight of dry particles). The fluorescent particles can be prepared in micrometer diameters suitable for analyses using flow cytometry with 488-nm laser excitation.     

Upconversion Luminescence of SrTiO3:Er3+ Ultrafine Powders Produced by 785 nm Laser

Er3+ doped SrTiO3 ultrafine powders were prepared by solid state reaction in a molten NaCl flux. The structural properties were characterized by X-ray diffraction, field emission scanning electron microscopy, and Fourier transform infrared spectroscopy. The Stokes emission spectra of Er3+ in SrTiO3:Er3+ ranging from green to near infrared region were investigated under 514.5 nm laser excitation. The green and redupconverted luminescence spectra of Er3+ were measured under excitation into the 4I9=2 level by 785 nm laser. The upconversion mechanisms were studied in detail through laser power dependence and Er3+ ion concentration dependence of upconverted emissions, and results show that excited state absorption and energy transfer process are the possible mechanisms for the upconversion. The upconversion properties indicate that SrTiO3:Er3+ may be used in upconversion phosphors.     

Photophysics of aminobenzazole dyes in silica-based hybrid materials

In this work two aminobenzazole derivatives (5-AHBT and 5-AHBI) were dispersed in silica-based hybrid materials with different surface hydrophobicity, which were obtained by the sol?Cgel process using tetraethylorthosilicate as inorganic precursor and dimethyldimethoxysilane as organic precursor, with a molar percent of organic precursor changing from 0 to 50%. The photophysics of the obtained doped silica hybrid materials was investigated by means ultraviolet?Cvisible diffuse reflectance and steady-state fluorescence emission spectroscopy in the solid state. The materials present absorption maxima located around 353 and 318?nm when doped with 5-AHBT and 5-AHBI, respectively. The red shifted absorption maxima of the 5-AHBT can be explained by the better electron delocalization allowed by the sulfur atom in relation to the nitrogen. The fluorescence emission spectra are located in the blue-green regions and the high Stokes shift indicates that the ESIPT mechanism occurs in the excited state for both dyes. The photophysical behavior of 5-AHBT shows that this dye is more affected by the matrix polarity due to specific interactions that take place in the ground state.     

水滑石改性二氧化硅新材料去除养殖用水中的孔雀石绿及结晶紫

合成了水滑石改性的系列硅胶新材料HTS-n(s),该新材料同时包含有酸性位与碱性位,并通过碱腐蚀获得了3～4 nm的小孔和大的比表面积。该类材料可选择性吸附去除水产养殖用水中的工业染料类污染物孔雀石绿和结晶紫。吸附后水中剩余的染料浓度通过高效液相色谱-质谱/质谱联用仪进行检测,结果显示新材料的吸附性能超过常用的工业吸附剂NaY沸石和活性炭。     

Color Tuning of the Aggregation‐Induced Emission of Maleimide Dyes by Molecular Design and Morphology Control

Aggregation‐induced emission (AIE)‐active maleimide dyes, namely, 2‐p‐toluidino‐N‐p‐tolylmaleimide, 3‐phenyl‐2‐toluidino‐N‐p‐tolylmaleimide, 2‐p‐thiocresyl‐3‐p‐toluidino‐N‐p‐tolylmaleimide, and 2,3‐dithiocresyl‐N‐arylmaleimides, were synthesized by facile synthetic procedures. The dyes show intense emission in the solid state, and emission colors were controlled from green (λ_max=527 nm) to orange (λ_max=609 nm) by varying the substituents at the 2‐ and 3‐positions of the maleimide and the packing structures in the solid state. 2,3‐Disubstituted maleimide dyes effectively underwent redshifts of their emission wavelength. Furthermore, some of the dyes exhibited mechanochromism and polymorphism, and their emission properties were dramatically dependent on the morphology of the solid samples. The mechanisms of the emission behaviors were investigated by X‐ray diffraction. The substituent of the nitrogen atom of the maleimide ring affected the intermolecular interactions and short contacts, which were observed by single crystal X‐ray crystallography, to result in completely different emission properties.     

Bright white light through up-conversion of a single NIR source from sol-gel-derived thin film made with Ln3+-doped LaF3 nanoparticles

White light was generated from a single silica thin film made with Yb0.75La0.2Eu0.05F3, La0.45Yb0.5Er0.05F3, and La0.75Yb0.2Tm0.05F3 nanoparticles by exciting with a single source near-infrared light (980 nm CW diode laser). Eu3+ and Tm3+ ions are responsible for red and blue emission, respectively. Er3+ ion is responsible for green as well as red emission. The Commission Internationale de l'Eclairage (CIE) coordinates of the resulting light were easily adjusted by controlling the concentration of Ln3+ (Eu3+, Er3+, Tm3+) ions in the nanoparticles as well as the concentration of Ln3+-doped nanoparticles in the sol-gel thin layer.     

Negatively Charged Yellow‐Emitting 1‐Aminopyrene Dyes for Reductive Amination and Fluorescence Detection of Glycans

1‐Aminopyrenes with three ω‐hydroxylated N‐alkylsulfonamido or alkylsulfonyl residues in positions 3, 6, and 8 were prepared, O‐phosphorylated, and applied for reductive amination of oligosaccharides. The dyes (?≈20 000 m ^?1 cm^?1) with six negative charges (pH≥8) and low m/z ratios enable labeling and fluorescence detection of reducing sugars (glycans) related to the most structurally and functionally diverse class of natural products. Under excitation with a 488 nm laser, the new glycoconjugates emit yellow light of about 560 nm, outperforming (with respect to brightness and faster electrophoretic mobilities) the corresponding APTS derivatives (benchmark dye with green emission in conjugates).     

Polymer-filled nanoporous silica aerogels as hosts for highly stable solid-state dye lasers

New hybrid solid-state dye laser materials based on highly porous silica aerogels have been synthesized. The open porous network of the aerogel was saturated with laser dyes dissolved in appropriate organic monomers, and polymerization took place inside the silica structure. The resulting polymer-filled nanoporous aerogel (PFNPA) was cast in a cylindrical shape, forming monoliths that were used as gain media in solid-state dye lasers. When the PFNPA incorporated pyrromethene dyes, highly photostable laser emission with good lasing efficiency was obtained. Under the demanding conditions of tightly focused transversal pumping with 532 nm, 5 mJ pulses at 10 Hz repetition rate, the commercial dye Pyrromethene 567 exhibited laser action with only a 10% drop in the laser output after 10(6) pump pulses in the same position of the sample.     

Photostability of Silylated Coumarin Dyes in Polyceram Hosts

Numerous silylated coumarin dyes have been incorporated within silica : polydimethylsiloxane Polyceram hosts using the sol-gel process to form crack-free, polishable monoliths. The use of silylated laser dyes allows for covalently bonding the laser dyes to their hosts. Photostability of the samples was evaluated by measuring the decrease in the dye absorption in the Polyceram upon ultraviolet lamp exposure and by monitoring the fluorescence intensity as function of pump pulses from a N₂ laser at 337 nm. Both methods showed a significant improvement in photo- and thermal-stability of the silylated dye Polyceram compared to that of the unsilylated dye Polyceram at a dye : Si mole ratio of 10^-4 : 1. The improved stability is attributed to the immobilization and higher degree of caging of the silylated dye Polyceram with respect to the unsilylated dye Polyceram.     

Alkoxy-substituted difluoroboron benzoylmethanes for photonics applications: a photophysical and spectroscopic study

Two series of novel boron difluoride adducts (BDFs), namely [BF(2)(OO(R(n)))] (type I) and [BF(2)(OO(2R(n)))] (type II) (R = C(6)H(4)OC(n)H(2n+1); n = 10-18), containing β-diketonate ligands bearing 4-alkoxyphenyl substituents in position 1 or in positions 1,3 of the β-diketonate core, respectively, have been prepared. All of them display a strong interaction between the ligand and the BF(2) group, as deduced from the IR spectroscopic data, and strong blue-violet emission (λ(em)(max) from 400 to 440 nm), with fluorescence quantum yields from 0.69 to 0.84 (type I) and 0.48 to 0.66 (type II) and fluorescence lifetimes of 1.7 and 2.2 ns in diluted dichloromethane solution, respectively. The photophysical properties of I and II series of dyes are independent of the solvent polarity and the chain length of the alkoxyphenyl substituent(s). Moreover, they exhibit high photostability even under intense laser light. Contradicting previous interpretations, our detailed photophysical and spectroscopic study rules out excimer formation even in highly concentrated solution or in the solid state, demonstrating the resistance of these dyes to self-aggregation. All those features pave the way to the application of such fluorophores in OLEDs, solid dye lasers, chemical sensors and two-photon biological labels, to name a few.     

Dual‐fluorophore Raspberry‐like Nanohybrids for Ratiometric pH Sensing

We report on the development of raspberry‐like silica structures formed by the adsorption of 8‐hydroxypyrene‐1,3,6‐trisulfonate (HPTS)@silica nanoparticles (NPs) on rhodamine B isothiocyanate (RBTIC)@silica NPs for ratiometric fluorescence‐based pH sensing. To overcome the well‐known problem of dye leaching which occurs during encapsulation of anionic HPTS dye in silica NPs, we utilized a polyelectrolyte‐assisted incorporation of the anionic HPTS. The morphological and optical characterization of the as‐synthesized dye‐doped NPs and the resulting nanohybrids were carried out. The pH‐sensitive dye, HPTS, incorporated in the HPTS‐doped silica NPs provided a pH‐dependent fluorescence response while the RBITC‐doped silica provided the reference signal for ratiometric sensing. We evaluated the effectiveness of the nanohybrids for pH sensing; the ratio of the fluorescence emission intensity at 510 nm and 583 nm at excitation wavelengths of 454 nm and 555 nm, respectively. The results showed a dynamic response in the acidic pH range. With this approach, nanohybrids containing different dyes or receptors could be developed for multifunctioning and multiplexing applications.     

Absorption and fluorescence spectroscopy of rhodamine 6G in titanium dioxide nanocomposites

A comparison has been made between the spectroscopic properties of the laser dye rhodamine 6G (R6G) in mesostructured titanium dioxide (TiO(2)) and in ethanol. Steady-state excitation and emission techniques have been used to probe the dye-matrix interactions. We show that the TiO(2)-nanocomposite studied is a good host for R6G, as it allows high dye concentrations, while keeping dye molecules isolated, and preventing aggregation. Our findings have important implications in the context of solid state dye-lasers and microphotonic device applications.     

4‐Trifluoromethyl‐Substituted Coumarins with Large Stokes Shifts: Synthesis,Bioconjugates, and Their Use in Super‐Resolution Fluorescence Microscopy

Bright and photostable fluorescent dyes with large Stokes shifts are widely used as sensors, molecular probes, and light‐emitting markers in chemistry, life sciences, and optical microscopy. In this study, new 7‐dialkylamino‐4‐trifluoromethylcoumarins have been designed for use in bioconjugation reactions and optical microscopy. Their synthesis was based on the Stille reaction of 3‐chloro‐4‐trifluoromethylcoumarins and available (hetero)aryl‐ or (hetero)arylethenyltin derivatives. Alternatively, the acylation of 2‐trifluoroacetyl‐5‐dialkylaminophenols with available (hetero)aryl‐ or (hetero)arylethenylacetic acids followed by intramolecular condensation afforded coumarins with 3‐(hetero)aryl or 3‐[2‐(hetero)aryl]ethenyl groups. Hydrophilic properties were provided by the introduction of a sulfonic acid residue or by phosphorylation of a primary hydroxy group attached at C‐4 of the 2,2,4‐trimethyl‐1,2‐dihydroquinoline fragment fused to the coumarin fluorophore. For use in immunolabeling procedures, the dyes were decorated with an (activated) carboxy group. The positions of the absorption and emission maxima vary in the ranges 413–480 and 527–668 nm, respectively. The phosphorylated dye, 9 ,CH?CH‐2‐py,H, with the 1‐(3‐carboxypropyl)‐4‐hydroxymethyl‐2,2‐dimethyl‐1,2‐dihydroquinoline fragment fused to the coumarin fluorophore bearing the 3‐[2‐(2‐pyridyl)ethenyl] residue (absorption and emission maxima at 472 and 623 nm, respectively) was used in super‐resolution light microscopy with stimulated emission depletion and provided an optical resolution better than 70 nm with a low background signal. As a result of their large Stokes shifts, good fluorescence quantum yields, and adequate photostabilities, phosphorylated coumarins enable two‐color imaging (using several excitation sources and a single depletion laser) to be combined with subdiffractional optical resolution.     

Structurally integrated organic light emitting device-based sensors for gas phase and dissolved oxygen

A compact photoluminescence (PL)-based O2 sensor utilizing an organic light emitting device (OLED) as the light source is described. The sensor device is structurally integrated. That is, the sensing element and the light source, both typically thin films that are fabricated on separate glass substrates, are attached back-to-back. The sensing elements are based on the oxygen-sensitive dyes Pt- or Pd-octaethylporphyrin (PtOEP or PdOEP, respectively), which are embedded in a polystyrene (PS) matrix, or dissolved in solution. Their performance is compared to that of a sensing element based on tris(4,7-diphenyl-l,10-phenanthroline) Ru II (Ru(dpp)) embedded in a sol-gel film. A green OLED light source, based on tris(8-hydroxy quinoline Al (Alq3), was used to excite the porphyrin dyes; a blue OLED, based on 4,4'-bis(2,2'-diphenylviny1)-1,1'-biphenyl, was used to excite the Ru(dpp)-based sensing element. The O2 level was monitored in the gas phase and in water, ethanol, and toluene solutions by measuring changes in the PL lifetime tau of the O2-sensitive dyes. The sensor performance was evaluated in terms of the detection sensitivity, dynamic range, gas flow rate, and temperature effect, including the temperature dependence of tau in pure Ar and O2 atmospheres. The dependence of the sensitivity on the preparation procedure of the sensing film and on the PS and dye concentrations in the sensing element, whether a solid matrix or solution, were also evaluated. Typical values of the detection sensitivity in the gas phase, S(g) identical with tau(0% O2)/tau(100% O2), at 23 degrees C, were approximately 35 to approximately 50 for the [Alq3 OLED[/[PtOEP dye] pair; S(g) exceeded 200 for the Alq3/PdOEP sensor. For dissolved oxygen (DO) in water and ethanol, S(DO) (defined as the ratio of tau in de-oxygenated and oxygen-saturated solutions) was approximately 9.5 and approximately 11, respectively, using the PtOEP-based film sensor. The oxygen level in toluene was measured with PtOEP dissolved directly in the solution. That sensor exhibited a high sensitivity, but a limited dynamic range. Effects of aggregation of dye molecules, sensing film porosity, and the use of the OLED-based sensor arrays for O2 and multianalyte detection are also discussed.