Spectroscopic studies of a near-infrared absorbing pH sensitive aminodienone-carbocyanine dye system

Synthetic red and near-infrared absorbing dyes may be used as probe molecules in a large number of applications. Dyes exhibiting spectral changes with hydrogen ion concentration are useful as pH probes. Those dyes which have their absorption and fluorescence maxima in the long wavelength region of the visible spectral region are specially valuable because of decreased interference and semiconductor laser applications. In this paper we have evaluated an aminodienone dyes 1 which demostrates pH dependent absorption and fluorescence spectra as well as solvent polarity dependence. In organic solvents the long wavelength absorption band of the dye is in the reduced interference region. The absorption maximum is at 535 nm in neutral or alkaline solutions in methanol. The absorption spectra undergo a strong bathochromic shift in the presence of acids (lambda(max) = 709 nm) with a concomitant change in the fluorescence spectra. This pH sensitive dye was found to be specially especially useful for organic solvents. The analytical utility of this and similar near-infrared absorbing dyes is discussed.     

Evaluation of Near Infrared Dyes as Labels for Immunoassays Utilizing Laser Diode Detection: Development of Near Infrared Dye Immunoassay (NIRDIA)

Abstract

Many recent studies of near infrared (NIR) dyes have shown their usefulness as probes for many analytical applications. Since these dyes have absorption maxima between 600 and 1000 nm, a region of low interference by most bioorganic molecules, their use as a label for biomolecules is practical. We report here the first study to evaluate the use of near infrared dyes as a quantitative label for immunoassays. A near infrared dye was derivatized with an isothiocyanate functional group and conjugated to goat anti-human immunoglobulins (GAHG). After purification by G-25 size exclusion chromatography, the conjugate was used in an immunoassay to detect and quantitate human immunoglobulins (Ig), the antigen for GAHG. Polystyrene microtiter plate wells were coated with varying amounts of human Ig. The Ig-coated wells were then exposed to an excess of NIRD-GAHG, and were subsequently read and quantitated by laser diode spectroscopy. An identical immunoassay was performed which utilized an enzyme(peroxidase)-labeIed GAHG for comparison. From these studies, the effectiveness of the NIR dye-conjugate as an accurate and sensitive quantitative probe for immunoassays was evaluated.     

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.     

DYES AND DYE MIXTURES USEFUL FOR GENERATION OF UV IN A FLASHLAMP DRIVEN TUNABLE DYE LASER

Abstract— We have used a flashlamp driven tunable dye laser combined with angle tuned frequency doubling crystals for producing UV-B radiation for action spectra studies of various organisms. Optimum UV-B power generation is needed to provide biologically effective doses at wavelengths greater than 300 nm. Optimizing power will also serve to lengthen the lifetime of dyes and other laser components at shorter wavelengths where UV-B output is more than adequate. While much information is available on dyes and dye performance from manufacturers, little information is available on the use of dyes and dye mixtures for providing the continuous high power spectrum of wavelengths necessary for biological UV action spectroscopy. We have examined a number of dyes and dye mixtures for optimal laser performance at wavelengths from 260 to 330 nm. The dyes and dye mixtures discussed here provide adequate power output in the UV-B wavelength range and have allowed us to perform numerous UV-B action spectra studies using the tunable dye laser.     

Ultrafast Photoinduced Electron Transfer in Viologen‐Linked BODIPY Dyes

New boron‐dipyrromethene (BODIPY) dyes linked to viologen are prepared and their photophysical and electrochemical properties are investigated. Both synthesized molecules have similar electronic absorption spectra with the absorption maximum localized at 517 and 501 nm for dye 1 and dye 2 , respectively. They exhibit well‐defined redox behavior, highlighting the presence of BODIPY and viologen subunits, with little perturbation of the redox potential of both subunits with respect to the parent compounds. Both dyes are heavily quenched by photoinduced electron transfer from the BODIPY to the viologen subunit. The transient absorption technique demonstrates that dye 2 forms the viologen radical within a timeframe of 7.1 ps, and that the charge‐separated species has a lifetime of 59 ps. Sustained irradiation of dye 2 in the presence of a tertiary amine allows for the accumulation of BODIPY–methyl‐4,4′‐bipyridinium (BODIPY–MV⁺), as observed by its characteristic absorption at 396 and 603 nm. However, dye 2 does not generate catalytic amounts of hydrogen under standard conditions.     

Electrokinetic studies of cellulosic fibres

Results on surface conductivity of cotton fibres dyed with reactive dyes have been reported. In general the surface conductivity values were higher in alkaline pH, but lower in acidic pH as compared to the neutral pH. This observation has been attributed to the contribution of the functional groups present on the dye molecule reacted with the fibre. Results on the surface conductivity of fibres dyed with mono- and bifunctional reactive dyes suggest that dyes react with the hydroxyl groups of the fibre, and that the bifunctional dye molecule forms a crosslink between two cellulosic chains.     

Direct and sensitized photoprocesses of bis-benzimidazole dyes and the effects of surfactants and DNA

The photoprocesses of two bis-benzimidazole dyes, Hoechst 33258 (1) and an analog, where the phenolic group in p-position is replaced by an ethoxy group, Hoechst 33342 (2), were studied. For 1 and 2 in aqueous solution the quantum yield of fluorescence is strongly pH dependent; it decreases from a maximum value of phi f = 0.4 at pH 5 to phi f = 0.02 at pH 8. The effects of absorption and fluorescence, induced by sodium dodecyl sulfate surfactants below and above the critical micelle concentration and by double-stranded DNA, are interpreted by assuming that in bulk aqueous solution the dyes are essentially present as monomers. The strong enhancement of phi f, when the dye is bound to double-stranded DNA or solubilized in micelles, is suggested to be due to different environments at the benzimidazole rings. A quinoid intermediate with absorption maximum at 380 nm is formed for 1 at neutral pH using lambda exc = 248 or 308 nm. N-centered radicals of 1 or 2 in aqueous solution were observed by laser flash photolysis after electron ejection using wavelengths of 193 or 248 nm (mono and biphotonic, respectively). The precursor radical cation escaped observation but is transformed into the above radicals by deprotonation. Electron transfer from 1 in aqueous solution to triplet acetone takes place, and subsequent deprotonation is proposed to yield N-centered radicals. In addition, energy transfer from acetone to 1 is suggested, leading to T-T absorption with the maximum at 700 nm. The photoprocesses are discussed and the results compared with those known from pulse radiolysis.     

Exploration on Charge Transfer and Absorption Spectra of Spiro[fluorene-9,90-xanthene]-based Polyoxometalate Hybrids Toward High Performance Dye-sensitized Solar Cell

Based on spiro[fluorene-9,90-xanthene](SFX, dye 1), the Lindqvist-type polyoxometalate(POM) functionalized with SFX and its derivatives(dyes 2-4) used in dye-sensitized solar cells(DSSCs) were designed and investigated with the density functional theory(DFT) and time-dependent DFT(TD-DFT) calculations. The results indicate that Lindqvist-type POM is the main contribution to the lowest unoccupied molecular orbital(LUMO) and affects the LUMO energies of dyes 2-4. The maximum absorptions of the designed dyes containing POM(dyes 2-4) are red shifted comparing with that of dye 1. The introduction of electron-donating group onto SFX segment is helpful to red shift the absorption spectra. The major factors affecting the performance of DSSCs, including light harvesting and electron injection were evaluated. Considering the absorption spectra and photovoltaic parameters, dyes 3 and 4 are promising high performance dye sensitizers in n-type DSSCs.     

近红外激光防护染料

以激光防护和隐身材料为需求背景，概述了菁类染料(含多次甲基菁染料、方酸菁和克酮酸菁染料、薁染料)、酞菁类染料(含普通酞菁和萘酞菁)、金属络合物染料、醌型染料、偶氮染料、游离基型染料、芳甲烷型染料、苝类染料等近红外吸? 杖玖系难芯孔纯黾敖埂? $601$ADuetotherequirementofnear-infraredlaserprotectivedyesandlaserstealthmaterials,thisreviewfocusedontheresearchprogressofnear-infraredabsorbingdyes,andsomesuggestionswereputforwardonthefutureresearch.Someofthemostimportanttechnicalrequiremnetsforlaser-protectivedyeswithintheplasticareasfollows:sharpabsorptionbandsatspecificwavelengthscorrespondingtolaseremission,excellentlightfastness,robustthermalandchemicalstability,stabilitytoambientconditions,highopticaldensityandscotopicluminoustransmission,goodsolubilityinplasticandlowtoxicity.Thisreviewpaidattentiontothepropertiessuchasthemaximumabsorptionwavelengthandtheabsorptionintense,attentionhadbeendirectedtowardseighttypesnear-infrareddyes:cyaninedyeswhichincludedpolymethinedyesandsquaryliumorcroconiumdyes,phthalocyaninesandnaphthalocyanines,metalcomplexdyes,quinonedyes,azodyes,radicaldyes,multiphenylmethanedyesandperylenedyes.Otherkindsofnear-infrareddyeswerealsomentioned,suchasaromaticannulenes,planescontainignso-callednonbenzenoidaromaticrings,cycliccross-conjugatedhydrocarbonshavinginsertedp-quiniodring,fluorenyliumdyeswithinorganicanions,donor-acceptorcyclophanes,tetrapyrazinoporphyrazinesandpentaazadentateexpandedporphyrinsetal.Allofthedyesmentionedabovehadsomegoodpropertiesforuseasthenear-infraredlaserprotectivedyesandlaserstealthmaterials,buttherealsoexisteddefectsineverykindofdyes.     

Near-infrared tetra-substituted aluminum 2, 3-naphthalocyanine dyes for optical fiber applications

The synthesis and spectral characterization of several tetra-substituted aluminum 2, 3-naphthalocyanine dyes for the determination of metal ions is reported. The synthesis is done by means of a homogeneous phase reaction, replacing the previously used heterogeneous method. The new scheme allows for improved product yields, higher purity, better product reproducibility and can be monitored at different stages using UV-Vis-near-infrared spectroscopy. The incorporation of electron-donating or -withdrawing groups was found to influence the product yield and to cause a shift in the absorbance maximum. The typical shift in the excitation maximum (of up to 27 nm) enables the dye to match the output of semiconductor laser diodes. In addition the tetra-substituted groups were capable of undergoing an ion-exchange process with the metal ions which produced a change in the fluorescence signal of the dye. Similar results were achieved using an optical fiber metal probe. The detection of metal ions using the near-infrared dyes was accomplished via steady-state fluorescence using both a commerically available instrument and a fiber optic system and also via the fluorescence lifetime technique.     

Adsorption study of cationic dyes having a trimethylammonium anchor group on hectorite using electrooptic and spectroscopic methods

Clay minerals are natural or synthetic material of colloidal dimensions. Due to the sheetlike structure clay minerals offer a huge specific surface area and hence optimal properties for modification through adsorption. The current work studies the adsorption of five cationic dyes on the synthetic clay mineral hectorite. All dyes have a trimethylammonium anchoring group in common. The adsorbed dye molecules are characterized by means of pulsed electric linear dichroism and UV-VIS spectroscopy. With increasing dye loading a continuous shift in the absorption spectra is observed. But there is no occurrence of a new absorption band. Therefore we conclude that the dyes preferentially adsorb as amorphous aggregates on the clay surface. At low dye loadings the dye molecules lie flat on the clay mineral surface. Increasing dye concentration leads to a continuous increase in average tilt angle. However the orientation of the dye molecules is very sensitive to functional groups. The introduction of a nitro group to a particular dye increases significantly the tendency to lie flat on the surface whereas the introduction of a methoxy group at the same position has the opposite effect.     

Density functional theory as a guide for the design of pyran dyes for dye-sensitized solar cells

Abstract  

Using density functional theory and hybrids, we examined several derivatives of the dye 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran, with the objective of identifying modifications which would improve the properties of dyes for dye-sensitized solar cells. We calculated the electronic structure of numerous derivatives at the HOMO and LUMO energy levels, with the hypothesis that directing the flow of excited electrons to the point of the dye at which the molecule attaches to TiO₂ would increase the energy conversion efficiency of the cell. We also examined the UV–visible absorption spectra of the dyes, with the objective of capturing the maximum amount of solar light. By use of the derivatives we compared the use of two electron-donating groups instead of one, extension of the conjugated chain leading to the attachment point of the dye, use of oxygen versus sulfur or selenium in the dye, and the use of different electron-donating groups. We identified several promising donating groups and determined that the other modifications to the dye are likely to increase solar cell efficiency.     

Red‐Emitting Rhodamines with Hydroxylated,Sulfonated, and Phosphorylated Dye Residues and Their Use in Fluorescence Nanoscopy

Fluorescent dyes emitting red light are frequently used in conventional and super‐resolution microscopy of biological samples, although the variety of the useful dyes is limited. We describe the synthesis of rhodamine‐based fluorescent dyes with absorption and emission maxima in the range of 621–637 and 644–660 nm, respectively and demonstrate their high performance in confocal and stimulated emission depletion (STED) microscopy. New dyes were prepared by means of reliable chemical transformations applied to a rhodamine scaffold with three variable positions. They feature polarity, water solubility, variable net charges, improved stabilities of N‐hydroxysuccinimidyl (NHS) esters, as well as large fluorescence quantum yields in dye solutions and antibody conjugates. The photophysical and imaging properties of dyes containing three different polar groups, namely primary phosphate, sulfonic acid (in two different positions), and hydroxyl were compared. A dye with two primary phosphate groups was explored as a valuable alternative to dyes with “classical” sulfonic acid groups. Due to the increased net charge of the phosphorylated dye (q=?4 at pH 8), it demonstrated a far better electrophoretic mobility compared with analogues with two sulfonic acid groups (q=?2). As an example, one fluorescent dye was designed to be especially convenient for practical use. It is characterized by sufficiently high chemical stability of the NHS ester, its simple isolation, handling, and solubility in aqueous buffers, as well as in organic solvents. All these features, accompanied by a zero net charge in conjugates, were accomplished by the introduction of hydrophilic groups of two types: two hydroxyl groups and one sulfonic acid residue.     

Organic Dyes in Laser Technology

Laser technology has been developed to a very high level since 1960. Significant advances have been made possible only by the use of organic dyes as optical shutters for the production of giant pulses. Ultrashort pulses in the picosecond range were first produced in 1966; their measurement was greatly facilitated by the use of organic dyes. Probably the most important recent advance in the laser field is the dye laser, which was first described in 1966, and in which the active medium is a solution of an organic dye.     

Controlling solubility and modulating peripheral function in dendrimer encapsulated dyes

The synthesis of large dendrons and dendrimers with site-isolated dyes at their core has been explored. The dyes selected for this work were coumarin 343 and pentathiophene, as energy transfer processes prevail when the two dyes are intimately mixed but each should behave independently of the other if site-isolation is achieved. Because the two dyes have very different functional characteristics, a protocol involving orthogonal protecting groups and allowing the use of a single family of electroactive dendrons for their encapsulation had to be developed. The synthetic protocol must balance the need to incorporate electroactive groups at the periphery of the dendrons with the requirement for high solubility and a size sufficient to fully encapsulate the central dye. Because of their poor solubility and tendency to crystallize, dendrons with uniform triarylamine substitution proved unsatisfactory leading to the development of new unsymmetrical dendrons with alternating branched alkyl groups and triarylamine moieties at their periphery. These dendrons, which show excellent solubility and no tendency to crystallize, were assembled into large dendrimers using a modular protocol with the light emitting dye at their core. It is expected that the large size of the dendritic shell will provide effective site-isolation for the encapsulated central dyes enabling them to exhibit their intrinsic emission properties with minimal energy transfer between neighboring core fluorophores when processed in bulk thin films.     

Human Serum Albumin Labelling with a New BODIPY Dye Having a Large Stokes Shift

BODIPY dyes are photostable neutral derivatives of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene. These are widely used as chemosensors, laser materials, and molecular probes. At the same time, BODIPY dyes have small or moderate Stokes shifts like most other fluorophores. Large Stokes shifts are preferred for fluorophores because of higher sensitivity of such probes and sensors. The new boron containing BODIPY dye was designed and synthesized. We succeeded to perform an annulation of pyrrole ring with coumarin heterocyclic system and achieved a remarkable difference in absorption and emission maximum of obtained fluorophore up to 100 nm. This BODIPY dye was equipped with linker arm and was functionalized with a maleimide residue specifically reactive towards thiol groups of proteins. BODIPY residue equipped with a suitable targeting protein core can be used as a suitable imaging probe and agent for Boron Neutron Capture Therapy (BNCT). As the most abundant protein with a variety of physiological functions, human serum albumin (HSA) has been used extensively for the delivery and improvement of therapeutic molecules. Thiolactone chemistry provides a powerful tool to prepare albumin-based multimodal constructions. The released sulfhydryl groups of the homocysteine functional handle in thiolactone modified HSA were labeled with BODIPY dye to prepare a labeled albumin-BODIPY dye conjugate confirmed by MALDI-TOF-MS, UV-vis, and fluorescent emission spectra. Cytotoxicity of the resulting conjugate was investigated. This study is the basis for a novel BODIPY dye-albumin theranostic for BNCT. The results provide further impetus to develop derivatives of HSA for delivery of boron to cancer cells.     

Synthesis and characterization of guest-host azo dyes with broad absorption bands

Three groups of dyes were synthesized and characterized in order to examine their solubility, absorption spectrum, and order parameter in liquid crystal hosts. Our synthesis method allowed the formation of the diazonium salts and the diazo coupling in ethyl acetate instead of an aqueous medium, permitting the formation of long and neutral azo dyes. In the liquid crystal BDH-E7, they showed order parameters in the range of 0.52 to 0.76. The two dyes with the longest molecular lengths were particularly interesting due to their very broad absorption spectra in the visible region. Each of these two compounds behave as single component black dye guest/host systems, which generally require a mixture of two or three dyes in the liquid crystal host. These dyes were also evaluated for use in polymer dispersed liquid crystal films.     

Difluoro-boron-triaza-anthracene: a laser dye in the blue region. Theoretical simulation of alternative difluoro-boron-diaza-aromatic systems

The synthesis, photophysical and laser properties of a difluoro-boron-triaza-anthracene (BTAA) compound are analyzed in the present paper. The molecular structure of this dye is an anthracene-like core with N atoms at 4a, 9 and 10a positions where two of them (4a and 10a) are linked through a BF(2)-bridge group. This structure is reminiscent of aza-BODIPY dye with an s-indacene core, BODIPY being one of the most commonly used laser dye family in the Vis region. The main absorption and emission bands of the new dye are localized in the blue part of the Vis region of the electromagnetic radiation, a spectral region practically unexploited by the BODIPY chromophore. Moreover, the new dye presents a higher laser efficiency and photostability than other commercial laser dyes operating in the same spectral region. In order to look for new molecular structures with potential laser emission covering the whole Vis spectral region, the spectroscopic properties of other different chromophoric systems based on BF(2)-linking aromatic groups are theoretically simulated by quantum mechanical calculations.     

Graphene Oxide Nanosheets at the Water–Organic Solvent Interface: Utilization in One‐Pot Adsorption and Reactive Extraction of Dye Molecules

Graphene oxide (GO) is amphiphilic in nature, due to its structure, which consists of hydrophilic oxygen‐containing functional groups and a hydrophobic basal plane of polyaromatic benzene rings. Due to this amphiphilicity, GO can create stable bubbles at water–organic solvent interfaces. In this study, the formation of bubbles at aqueous–organic interfaces in the presence of GO is investigated with different organic solvents. Bubble formation and transfer of GO from water to the organic phase is more prominent in aromatic solvents compared to aliphatic solvents, due to π–π interactions. Maximum transfer of GO from the aqueous to the organic phase is achieved at pH 2, and decreases with rising pH of the aqueous phase. Based on this property, and the ability of GO to adsorb cationic and anionic dye molecules, its application as a carrier for reactive extraction of cationic and anionic dye molecules is explored in toluene, kerosene, and carbon tetrachloride at pH 2 and 25 °C. The kinetics of the adsorption of the dyes onto GO nanosheets that takes place in the aqueous phase is also evaluated with different models, and a pseudo‐second‐order (linear) model is found to be the best fit. The adsorption isotherm data are also analyzed with different isotherm models. The electrostatic interaction and π–π interaction between the dye molecules and GO nanosheets leads to dye extraction of up to 98.2 % using this technique. The dye extraction is maximum in toluene and at low dye concentration.     

Carbazole- and Fluorene-Fused Aza-BODIPYs: NIR Fluorophores with High Brightness and Photostability

Three new aza-BODIPY dyes incorporating fused fluorene or carbazole moieties have been prepared. The dyes show significant enhancement of photophysical properties compared to the parent 1,3,5,7-tetraphenyl aza-BODIPY (TPAB): a bathochromic shift of the absorption maximum (up to 2700 cm⁻¹) and emission maximum (up to 2270 cm⁻¹); an almost threefold increase in molar absorption coefficients (to ca. 230 000 M⁻¹ cm⁻¹) and a significant increase in the fluorescence quantum yield to 49–66 %. Owing to the combination of these properties, the new aza-BODIPY dyes belong to the brightest NIR dyes reported. The dyes also show excellent photostability. Due to their outstanding properties, the new dyes represent a promising platform for further exploration in biomedical research. A pH indicator containing only one fused carbazole unit was also prepared and shows absorption and emission spectra that are bathochromically shifted by about 110 and 100 nm, respectively, compared to the indicator dye based on the TPAB chromophore.