Colorimetric and ratiometric fluorescent chemosensor based on diketopyrrolopyrrole for selective detection of thiols: an experimental and theoretical study

A colorimetric and ratiometric fluorescent thiol probe was devised with diketopyrrolopyrrole (DPP) fluorophore. The probe gives absorption and emission at 523 and 666 nm, respectively. In the presence of thiols, such as cysteine, the absorption and emission band shifted to 479 and 540 nm, respectively. Correspondingly, the color of the probe solution changed from purple to yellow, and the fluorescence changed from red to yellow. The emission intensity at 540 nm was enhanced by 140-fold. The Stokes shift of probe 1 (107 nm) is much larger than the unsubstituted DPP fluorophore (56 nm). Mass spectral analysis demonstrated that besides the expected Michael addition of thiols to the C═C bonds, the CN groups of the malonitrile moieties also react with thiols to form 4,5-dihydrothiazole structure. Probe 1 was used for fluorescence imaging of intracellular thiols. In the presence of thiols, both the green and red channel of the microscopy are active. With removal of the intracellular thiols, signal can only be detected through the red channel; thus, ratiometric bioimaging of intracellular thiols was achieved. The ratiometric response of probe 1 was rationalized by DFT calculations. Our complementary experimental and theoretical studies will be useful for design of ratiometric/colorimetric molecular probes.     

Surface plasmon spectroscopy of metal/dielectric structures

Surface electromagnetic waves (i.e. plasmons) were excited in metal—oxide—metal (MOM) multi-layer thin film structures by the tunnel current from an external dc source. Surface plasmons decayed to photons in the visible region with typically 10⁻¹⁰−10⁻¹²W cm⁻² light intensity.A very sensitive single channel optical spectrometer was constructed to study both spectral and angular distributions of light emitted from aluminum—oxide—noble-metal (Ag, Au, Cu) thin film diodes mounted into a cold-finger type liquid nitrogen optical cryostat. When MOM structures were prepared on substrates with regular surface modulation of 300–900 nm periods, spectral and angular measurements of the emitted light allowed one to construct the energy—wave-vector dispersion diagram of surface plasmons. This was of help in identifying the top meta/vacuum fast mode plasmons as the source of photon emission.     

ENCAPSULATED RADIOPHOSPHORESCENT STANDARDS FOR DAY-TO-DAY PHOTOMETER CALIBRATION

Solid, unquenched, radiophosphorescent standards for use in the day-to-day calibration of bottom viewing photometers (luminometers) were prepared by encapsulating commercially-available phosphor powders that are excited to phosphoresce by the beta- decay of 63Ni (t0.5 = 96 yr) or 14C (t0.5 = 5730 yr). The radionuclides are physically adsorbed on the phosphors by precipitation either as a "basic nickel carbonate" or as barium carbonate. The radioactive phosphors are then deposited by centrifugation as a thin layer at the bottom of the vials or tubes that are normally used in the photometer. The phosphor layer is infiltrated with a plastic resin and embedded. A light absorbing layer is subsequently cast over the phosphor layer to prevent stray light excitation of phosphorescence. The encapsulated photometer standards have remained mechanically and photometrically stable since their fabrication, which in some cases is 3 years ago. An equivalent level of visible luminescence emitted from the standards of up to 2.3 x 10(10) photons.s-1 was achieved by using an appropriate amount of radioactivity and the proper phosphor. The phosphor used in the standards could be chosen such that the radiophosphorescence emission spectrum corresponded approximately to the chemiluminescence or bioluminescence spectrum under investigation.     

Photoluminescence spectral reliance on aggregation order of 1,1-Bis(2'-thienyl)-2,3,4,5-tetraphenylsilole

1,1-Bis(2'-thienyl)-2,3,4,5-tetraphenylsilole (1) was prepared and characterized crystallographically. Silole 1 exhibited aggregation-induced emission (AIE) behavior like other 2,3,4,5-tetraphenylsiloles. Unexpectedly, aggregates formed in water/acetone (6:4 by volume) mixture emitted a blue light that peaked at 474 nm, while aggregates formed in the mixtures with higher water fractions emitted green light that peaked at 500 nm. Transmission electron microscopy demonstrated that the aggregates formed in the mixture with water fraction of 60% were single crystals, while aggregates that formed in the mixture with water fraction of 90% were irregular and poorly ordered particles. The unusual PL spectral reliance on aggregation order was further confirmed by PL emissions of macroscopic crystal powders and amorphous powders of the silole in the dry state. PL spectral blue shifting was observed upon aging of the poorly ordered aggregates formed in mixtures with water fractions of 70-90%, and they finally exhibited the same blue emission as the crystalline aggregates. The as-deposited thin solid film was amorphous and it could be transformed to a transparent crystalline film upon treatment in the vapor of an ethanol/water (1:1 by volume) mixture, along with PL spectral blue shifting due to changing of aggregation order. It was also found that the crystalline film showed a blue-shifted absorption spectrum relative to the amorphous film and the shift of the absorption edge of the spectra could match that of corresponding PL spectra. The FT-IR spectrum of crystal powders of 1 displayed more vibration modes compared with that of amorphous powders, suggesting the existence of different pi-overlaps or different molecular conformations. The crystals of 1-methyl-1,2,3,4,5-pentaphenylsilole and hexaphenylsilole also showed blue-shifted PL emissions of their amorphous solids, with a comparable PL spectral shift of 1. Developing of a silole solution on a TLC plate readily brought about an amorphous thin layer. Our results suggest that crystalline films of AIE-active siloles are potential emissive layers for efficient blue OLEDs with stable color and long lifetime.     

A Novel White Light Emitting Long-lasting Phosphor

A novel white light emitting long-lasting phosphor Cd1-xDyxSiO3 is reported in this letterThe Dy^3 doped CdSiO3 phosphor emits white light. The phosphorescence can be seen with the naked eye in the dark clearly even after the 254nm UV irradiation have been removed for about 30min. In the emission spectrum of 5% Dy^3 doped CdSiO3 phosphor, there are two emission peaks of Dy^3 , 580nm (^4F9/2→^6H13/2) and 486nm (^4F9/2→^6H15/2), as well as a broad band emission located at about 410nm. All the three emissions form a white light with CIE chromaticity coordinates x=0.3874, y=0.3760 and the color temperature is 4000 K under 254 nm excitation. It indicated that this phosphor is a promising new luminescent material for practice application.     

Enhanced self-host blue emission of CaSrSb2O7 materials via Bi3+ ion doping for high CRI WLEDs,security inks and flexible displays

Luminescent materials are indispensable in our daily lives and have already been widely applied in various fields. Herein, novel self-host blue-emitting CaSrSb₂O₇ and CaSrSb₂O₇:Bi³⁺ phosphors with orthorhombic space group Imma (74) were successfully prepared. The phase purity, elemental composition, morphology, luminescent behaviors, etc. were investigated in detail. To compare the luminescence properties of rare-earth-activated phosphors, the self-host blue-emitting CaSrSb₂O₇ phosphor with unique performance exhibited a good quantum yield (QY) of 39.81%, and its emission intensity and QY could also be improved by doping Bi³⁺ ions. The CaSrSb₂O₇:Bi³⁺ phosphor was located in the pure blue region with the Commission Internationale de I'Eclairage chromaticity coordinate of (0.151, 0.058) and good color purity of 89.35%. For identifying its potential applications, the packaged white light-emitting diode device emitted a high color rendering index value of 93.66 under a forward current of 300 mA, and it would be further applied in security inks and flexible displays owing to its strong emission by the naked eyes. These results suggest that novel self-host blue-emitting CaSrSb₂O₇:Bi³⁺ phosphors could be used in multifunctional applications.     

一种新型的红色荧光粉——Ca4GdO(BO3)3:Eu3+

采用高温固相法制备了一种新型的红色荧光粉——Ca₄GdO(BO₃)₃:Eu³⁺.研究了它在X射线、真空紫外和紫外激发下的发光性能,研究表明,样品无论是在X射线、真空紫外还是在紫外的激发条件下,样品都能发出很强的红光.它的主发射峰在610 nm,而且其它位置的发射峰都很弱;它很容易被254nm、172 nm和X射线所激发而发出很强的红光,因此是一种具有潜在应用价值的红色荧光粉.研究表明Gd³⁺离子与激活剂(Eu³⁺)存在着一种能量传递的过程,而这种能量的传递过程可能跟二次吸收有关.     

Peripheral aryl-substituted pyrrole fluorophores for glassy blue-light-emitting diodes

In this work, a series of aryl-substituted pyrrole analogues were synthesized. These pyrrole analogues emit violet to blue light. Fluorescence and amorphous glassy properties of these pyrrole analogues were induced by manipulating the peripheral aryl groups. These crowded peripheral aryl groups would effectively prevent the fluorophores from aggregation, resulting in higher quantum efficiency and a stable emission spectrum in the solid state. One of the aryl-substituted pyrrole analogues, namely NPANPy can be used as hole-transporting material or hole-transporting/emitting material. The devices would emit blue light when the fluorophore NPANPy acts as the hole-transporting/emitting material. Their CIE coordinate is around (0.16, 0.14), whereas the maximum brightness can reach 4300-5000 cd m⁻². Apart from that, when the fluorophore was used only as the hole-transporting material, better device performances, especially in low current density, were found, as compared with the standard device.     

Mechano- and Photoresponsive Behavior of a Bis(cyanostyryl)benzene Fluorophore

The mechanoresponsive behavior and photochemical response of a new bis(cyanostyryl)benzene fluorophore (CSB-5) were investigated. Green fluorescence with λ_em,max of 507 nm was found for CSB-5 in chloroform solution, mirroring the behavior of a previously reported similar dye (CSB-6). Alternatively, crystalline samples of CSB-5 exhibited orange fluorescence with λ_em,max of 620 nm, attributable to excimer emission. Although the emission color change was not clearly noticeable by naked eye, CSB-5 exhibited mechanochromic luminescence, due to transformation into the amorphous state upon grinding the crystalline powder. Interestingly, rubbed films of CSB-5 prepared on glass substrates exhibited a pronounced emission color change from orange to green when exposed to UV light. This response is the result of a photochemical reaction that occurs in the amorphous state and which causes a decrease of the excimer emission sites so that the emission color changes from excimer to monomer. The crystalline material did not display such a photoinduced emission color change and the difference in photochemical reactivity between crystalline and amorphous states was exploited to pattern the emission color of rubbed films.     

Tb3+，Sm3+掺杂的YNbO4多色荧光材料的制备及发光性能

采用溶胶-凝胶法合成了YNbO4∶Tb^3+,Sm^3+系列荧光粉。光谱测试表明:体系中的NbO43-基团能够吸收紫外光并将能量传递给Tb^3+和Sm^3+,从而增强荧光粉的发光强度。在290 nm激发下,YNbO4∶Tb^3+,Sm^3+荧光粉的发射光谱中既出现了Tb^3+的绿光发射又出现了Sm^3+的橙光发射。通过改变Sm^3+的掺杂浓度,实现了荧光粉发射光的光色可调。     

Room‐Temperature Phosphorescence‐active Boronate Particles: Characterization and Ratiometric Afterglow‐sensing Behavior by Surface Grafting of Rhodamine B

We found that boronate particles ( BP ), as a self‐assembled system prepared by sequential dehydration of benzene‐1,4‐diboronic acid with pentaerythritol, showed greenish room‐temperature phosphorescence (RTP). This emission was observed in both solid and dispersion state in water. To understand the RTP properties, X‐ray crystallographic analysis, and density functional theory (DFT) and time‐dependent DFT at M06‐2X/6‐31G(d,p) level were performed using 3,9‐dibenzo‐2,4,8,10‐tetraoxa‐3,9‐diboraspiro[5.5]undecane ( 1 ) as a model compound. Our interest in functionalizing the RTP‐active particles led us to graft Rhodamine B onto their surface. The resulting system emitted a dual afterglow via a Förster‐type resonance energy transfer process from the BP in the excited triplet state to Rhodamine B acting as an acceptor fluorophore. This emission behavior was used for ratiometric afterglow sensing of water content in THF with a detection limit of 0.28 %, indicating that this study could pave the way for a new strategy for developing color‐variable afterglow chemosensors for various analytes.     

Doped Lead Halide White Phosphors for Very High Efficiency and Ultra‐High Color Rendering

Near‐UV‐pumped white‐light‐emitting diodes with ultra‐high color rendering and decreased blue‐light emission is highly desirable. However, discovering a single‐phase white light emitter with such characteristics remains challenging. Herein, we demonstrate that Mn doping as low as 0.027 % in the hybrid post‐perovskite type (TDMP)PbBr₄ (TDMP=trans‐2,5‐dimethylpiperaziniium) enables to achieve a bright pure white emission replicating the spectrum of the sun's rays. Thus, a white phosphor exhibiting an emission with CIE coordinates (0.330, 0.365), a high photoluminescence quantum yield of 60 % (new record for white light emission of hybrid lead halides), and an ultra‐high color rendering index (CRI=96, R9=91.8), corresponding to the record value for a single phase emitter was obtained. The investigation of the photoluminescence properties revealed how free excitons, self‐trapped excitons, and low amount of Mn dopants are coupled to give rise to such pure white emission.     

Panchromatic Fluorescence Emission from Thienosquaraines Dyes: White Light Electrofluorochromic Devices

Electrofluorochromic devices (EFCDs) that allow the modulation of the light emitted by electroactive fluorophores are very attractive in the research field of optoelectronics. Here, the electrofluorochromic behaviour of a series of squaraine dyes was studied for the first time. In solutions, all compounds are photoluminescent with maxima located in the range 665–690 nm, characterized by quantum yields ranging from 30% to 4.1%. Squaraines were incorporated in a polymer gel used as an active layer in all-in-one gel switchable EFCDs. An aggregation induced quenching occurs in the gel phase, causing a significant decrease in the emission quantum yield in the device. However, the squaraines containing the thieno groups (thienosquaraines, TSQs) show a panchromatic emission and their electrofluorochromism allows the tuning of the fluorescence intensity from 500 nm to the near infrared. Indeed, the application of a potential difference to the device induces a reversible quenching of their emission that is significantly higher and occurs at shorter switching times for TSQs-based devices compared to the reference squaraine dye (DIBSQ). Interestingly, the TSQs fluorescence spectral profile becomes more structured under voltage, and this could be explained by the shift of the aggregates/monomer equilibrium toward the monomeric species, due to electrochemical oxidation, which causes the disassembling of aggregates. This effect may be used to modulate the colour of the fluorescence light emitted by a device and paves the way for conceiving new electrofluorochromic materials based on this mechanism.     

A disposable microfluidic cassette for DNA amplification and detection

A pneumatically driven, disposable, microfluidic cassette comprised of a polymerase chain reaction (PCR) thermal cycler, an incubation chamber to label PCR amplicons with up-converting phosphor (UPT) reporter particles, conduits, temperature-activated, normally closed hydrogel valves, and a lateral flow strip, was constructed and tested. The hydrogel valves, which were opened and closed with the aid of electrically controlled thermoelectric units, provided a simple means to seal the PCR reactor and suppress bubble formation. The hydrogel-based flow control was electronically addressable, leakage-free, and biocompatible. To test the device, a solution laden with genomic DNA isolated from B. cereus was introduced into the microfluidic cassette and a specific 305 bp fragment was amplified. The PCR amplicons were labelled with the phosphor (UPT) reporter particles, applied to the lateral flow strip, bound to pre-immobilized ligands, and detected with an IR laser that scanned the lateral flow strip and excited the phosphor (UPT) particles that, in turn, emitted light in the visible spectrum. The UPT particles do not bleach, they provide a permanent record, and they readily facilitate the filtering of background noise. The cassette described herein will be used for rapid testing at the point of care.     

Doped Lead Halide White Phosphors for Very High Efficiency and Ultra-High Color Rendering

Near-UV-pumped white-light-emitting diodes with ultra-high color rendering and decreased blue-light emission is highly desirable. However, discovering a single-phase white light emitter with such characteristics remains challenging. Herein, we demonstrate that Mn doping as low as 0.027 % in the hybrid post-perovskite type (TDMP)PbBr₄ (TDMP=trans-2,5-dimethylpiperaziniium) enables to achieve a bright pure white emission replicating the spectrum of the sun's rays. Thus, a white phosphor exhibiting an emission with CIE coordinates (0.330, 0.365), a high photoluminescence quantum yield of 60 % (new record for white light emission of hybrid lead halides), and an ultra-high color rendering index (CRI=96, R9=91.8), corresponding to the record value for a single phase emitter was obtained. The investigation of the photoluminescence properties revealed how free excitons, self-trapped excitons, and low amount of Mn dopants are coupled to give rise to such pure white emission.     

Spectral imaging of single molecules by transmission grating-based epi-fluorescence microscopy

A spectral imaging method of single protein molecules labeled with a single fluorophore is presented. The method is based on a transmission grating and a routine fluorescence microscope. The bovine serum alubmin (BSA) and antiBSA molecules labeled with Alexa Fluor 488 and Alexa Fluor 594, respectively, are used as the model proteins. The fluorescence of single molecules is dispersed into zeroth-order spectrum and first-order spectrum by the transmission grating. Results show that the fluorescence emission spectrum of single molecule converted from the first-order spectral imaging is in good agreement with the bulk fluorescence spectrum. The spectral resolution of 2.4 nm/pixel is obtained, which is sufficient for identifying the molecular species in a multicomponent system.     

Circularly polarized emission from a narrow bandwidth dye doped into a chiral nematic liquid crystal

We report on circularly polarized light emitted from a chiral nematic liquid crystal doped with a luminescent organolanthanide dye. The organolanthanide emission displays an extremely narrow spectral bandwidth of ΔλE =8 nm. This is considerably narrower than the CNLC selective reflection bandwidth ΔλR =60 nm. When conventional dyes with broader emission bandwidths are dissolved into CNLCs, the average degree of circular polarization g of emitted light is reduced from the maximum degree g MAX ; this is due to the overlap of the emission band with the reflection band edges, and spectral regions outside the reflection band. Here, however, we can place the entire emission band inside the reflection band and achieve g ≈g MAX =1.27. Furthermore, a high degree of circular polarization is maintained under off-axis viewing up to a viewing angle of ≈30° to the normal.     

Bioluminescence resonance energy transfer from aequorin to a fluorophore: an artificial jellyfish for applications in multianalyte detection

In nature, the green light emission observed in the jellyfish Aequorea victoria is a result of a non-radiative energy transfer from the excited-state aequorin to the green fluorescent protein. In this work, we have modified the photoprotein aequorin by attaching selected fluorophores at a unique site on the protein. This will allow for in vitro transfer of bioluminescent energy from aequorin to the fluorophore thus creating an artificial jellyfish. The fluorophores are selected such that the excitation spectrum of the fluorophore overlaps with the emission spectrum of aequorin. By modifying aequorin with different fluorophores, bioluminescent labels with different emission maxima are produced, which will allow for the simultaneous detection of multiple analytes. By examining the X-ray crystal structure of the protein, four different sites for introduction of the unique cysteine residue were evaluated. Two fluorophores with differing emission maxima were attached individually to the mutants through the sulfhydryl group of the cysteine molecule. Two of the fluorophore-labeled mutants showed a peak corresponding to fluorophore emission thus indicating resonance energy transfer from aequorin to the fluorophore.     

TiO2对ZnO/ZnS:Eu3+荧光粉发光性能的影响

采用溶胶-凝胶-沉淀法制备ZnO/ZnS/2TiO2:Eu3+荧光粉,并采用X射线衍射(XRD)、红外光谱(IR)、透射电镜(TEM)以及荧光光谱技术对其结构、组成、形貌和发光性能进行表征,探讨其发光机理。结果显示,ZnO/ZnS/2TiO2:Eu3+荧光粉的结构在温度高于600℃时趋于稳定状态,呈不规则结构,由ZnO、TiO2和ZnS构成。IR谱图表明,Ti-O-Ti桥氧键网络结构有利于Eu3+之间的能量传递。荧光光谱分析表明,引入TiO2使Eu3+光谱选律禁阻解除,提高了ZnO/ZnS/2TiO2:Eu3+荧光粉的发光性能,且当nZn(NO3)2:nTiO2=1:2时荧光粉的发光性能最好,612 nm处的5D0→7F2电偶极跃迁为最强发射峰,最佳退火温度为600℃。     

Single fiber absorption measurements for remote detection of 2,4,6-trinitrotoluene

Single fiber optical measurements have been used to follow changes in the color of an initially clear poly(vinyl chloride) membrane as it reacts with aqueous 2,4,6-trinitrotoluene (TNT) to form a colored product that absorbs strongly at 500 nm. Attempts to make this measurement via the effect of the colored product on the emission spectrum of a fluorophore incorporated into the PVC membrane were unsuccessful. However, single fiber absorption measurements were successful. Refractive index matching to reduce stray light and a reflector behind the membrane to increase the reflected intensity were essential to keep the stray light levels small relative to the signal of interest. To compensate for drift, the reflected intensity at 500 nm is measured relative to the reflected intensity at 824 nm, a wavelength at which intensity is not affected by color formation in the membrane. The rate at which the ratio of reflected intensity at 824 nm to that at 500 nm increases is a function of TNT concentration. It is estimated that TNT levels as low as 0.10 mg 1^?1 can be determined by this technique.