Utilizing a pH‐Sensitive Dye in the Selective Fluorescent Recognition of Sulfate

A receptor containing amidopyrrole binding subunits and free amino groups, conjugated to a naphthalimide dye, has been designed and synthesized. The intrinsic selectivity of the binding motif for phosphate present in DMSO completely disappears in 10 % DMSO aqueous buffer at pH 3.6, at which the receptor is protonated. The electrostatic interactions between the receptor and an anion start to dominate, thus leading to selectivity for sulfate. The ability of the HSO₄^? anion to transfer the proton to the amino group during the recognition event suppresses the photoinduced electron transfer (PET) on the dye, resulting in a selective turn‐on fluorescent response. The choice of pH of the solution for sensing is dictated by the pK_a value of the dye.     

Reactions of excited states of phenoxazin-3-one dyes with amino acids

The interaction with amino acids of the excited states of the N-oxide resazurin and its deoxygenation product resorufin, has been studied in aqueous solution at pH 7.5. Steady-state and time-resolved studies show that the fluorescence is quenched by amino acids. Complexation of the dyes in the ground state with aromatic amino acids was also observed. The singlet quenching is attributed to electron transfer from the amino acids to the excited dye based on the dependence of the bimolecular rate constants with the ionization potential of quenchers. Flash photolysis experiments allowed determination of the quenching rate constants for the triplet deactivation of dyes by several amino acids, as well as the characterization of the transients formed in the process. These data show that the triplet is also deactivated by an electron transfer process. However, the deactivation of the N-oxide dye by tryptophan can be described by a hydrogen atom transfer. The protolytic dissociation constants of the dye radical ions are reported. The irradiation of rezasurin in the presence of amino acids leads to deoxygenation of the dye to give resorufin. This process involves the triplet excited state of resazurin and is efficient only in the presence of amino acids containing the -SH group.     

Spectral characteristics of the trypaflavine dye in a silica matrix

The mechanism of interaction of molecules of the dye trypaflavine with the surface and the bulk phase of silica gel has been investigated by electron spectroscopy. The character of the optical spectra of trypaflavine in a silica matrix is determined by the method of blending. Molecules of the dye are tied to the silicon dioxide substrate by an ionic bond; protonation of trypaflavine via the side amino groups and the acidic OH groups of the silica gel also takes place. In the simultaneous precipitation of the dye with polysilicic acid the encapsulated molecules possess an anomalously long afterglow, with extinguishment times ranging from tens of nanoseconds to seconds, which is not extinguished by oxygen. The mechanism of the retarded fluorescence of the adsorbed dye is discussed.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 6, pp. 748–753, November–December, 1985.     

Preparation and a time-resolved fluoroimmunoassay application of new europium fluorescent nanoparticles.

New silica-based europium fluorescent nanoparticles having surface amino groups were prepared by a covalent binding-copolymerization technique. In the nanoparticles, the fluorescent Eu3+ chelate molecules were covalently bound to silicon atoms to protect the nanoparticles from dye leaking in bio-applications. The amino groups on the surface of nanoparticles made the surface modification and bioconjugation of nanoparticles easier. The nanoparticles were characterized and developed as a new type of fluorescence probe for a highly sensitive time-resolved fluoroimmunoassay (TR-FIA) of human hepatitis B surface antigen (HBsAg).     

Functionalization of near-infrared cyanine dyes

An indolium heptamethine cyanine dye 11 containing an isothiocyanate function for selective coupling of the dye chromophore with a primary amino group of proteins has been synthesized. Functionalization of a benzothiazolium heptamethine cyanine 12 is discussed.     

Determination of direct orange 8 in effluent using a polypyrrole modified electrode

Electrochemical studies of direct orange 8 were carried out with a bare glassy carbon electrode (GCE) and a polypyrrole-coated GCE in aqueous acetonitrile medium using voltammetric techniques. One reversible couple around 0.3?V due to the redox reaction of the phenol group, one reduction peak around ?0.4?V due to reduction of the azo group and one oxidation peak around 1.0?V due to oxidation of the amino group were observed. Chronocoulometric studies revealed dye adsorption on the GCE. A square-wave stripping method was developed for the determination of the dye at pH 13.0, and a linear calibration equation obtained. The reproducibility in the measurement of peak currents was confirmed from the RSD value 2.8% at 0.001?mg?mL^?1 concentration. A comparison of the stripping voltammetric method with the UV-Vis spectrophotometric method was made. The determination limits are wider and the RSD value is lower in the stripping voltammetric method. The concentration of the dye present in dye effluent was determined using this method.     

Inverted Opal Fluorescent Film Chemosensor for the Detection of Explosive Nitroaromatic Vapors through Fluorescence Resonance Energy Transfer

This paper reports an inverted opal fluorescence chemosensor for the ultrasensitive detection of explosive nitroaromatic vapors through resonance‐energy‐transfer‐amplified fluorescence quenching. The inverted opal silica film with amino ligands was first fabricated by the acid–base interaction between 3‐aminopropyltriethoxysilane and surface sulfonic groups on polystyrene microsphere templates. The fluorescent dye was then chemically anchored onto the interconnected porous surface to form a hybrid monolayer of amino ligands and dye molecules. The amino ligands can efficiently capture vapor molecules of nitroaromatics such as 2,4,6‐trinitrotoluene (TNT) through the charge‐transfer complexing interaction between electron‐rich amino ligands and electron‐deficient aromatic rings. Meanwhile, the resultant TNT–amine complexes can strongly suppress the fluorescence emission of the chosen dye by the fluorescent resonance energy transfer (FRET) from the dye donor to the irradiative TNT–amino acceptor through intermolecular polar–polar resonance at spatial proximity. The quenching response of the highly ordered porous films with TNT is greatly amplified by at least 10‐fold that of the amorphous silica films, due to the interconnected porous structure and large surface‐to‐volume ratio. The inverted opal film with a stable fluorescence brightness and strong analyte affinity has lead to an ultrasensitive detection of several ppb of TNT vapor in air.     

Diffusion of monoanionic dyes in nylon

The diffusion of three monoanionic dyes [Orange II (C.I. Acid Red 7) and two chromium complex dyes] in nylon 6 is discussed on the basis of dye distribution obtained by the film-roll method. Variations of the diffusion coefficients with dye concentration depend characteristically on the dye species and in one case show a maximum near the dye concentration stoichiometric to the amino endgroup concentration in the nylon. These concentration dependences are interpreted on the assumption of two thermodynamically distinct dye populations in equilibrium.     

Local Extraction and Condensation under a Microscope Using the Optically Controlled Phase Separation of a Thermoresponsive Polymer

In‐situ extraction and condensation of various dyes were carried out in a phase‐separation region of a thermoresponsive polymer aqueous solution generated by near infrared (NIR) laser heating under a microscope. The NIR laser irradiation was directed at a chromium line deposited on a glass substrate, thereby causing local heating of the solution due to the photothermal effect. A phase‐separation region was formed by dehydration of the thermoresponsive polymer followed by ejection of water outside of the phase‐separation region. When various dyes were included in the solution, some dye molecules were extracted into the phase‐separation region, where they condensed. In the case of poly(N‐isopropylacrylamide) (PNIPAM, 10 wt % in an aqueous solution) as the thermoresponsive polymer and crystal violet (CV) as the dye (0.1 mM ), CV condensed by about 25 times. It was found that one of the necessary conditions for the extraction/condensation is the hydrophobicity of the dye molecule; however, the dominant cause for accumulating inside the PNIPAM chain is the molecular interaction between the amide group in the side chain of PNIPAM and the functional groups such as carbonyl or amino groups in the dye molecules.     

Switch‐On Fluorescence of a Perylene‐Dye‐Functionalized Metal–Organic Framework through Postsynthetic Modification

A perylene dye was introduced directly as a linker into a metal–organic framework (MOF) during synthesis. Depending on the dye concentration in the MOF synthesis mixture, different fluorescent materials were generated. The successful incorporation of the dye was proven by using ¹³C and ²⁷Al MAS NMR spectroscopy, by solution NMR spectroscopy after digestion of the MOF sample, and by synthesizing a reference dye without connecting groups, which could coordinate on the metal–oxo cluster inside the MOF. Fluorescence quenching effects of the MOF linker, 2‐aminoterephthalate, were observed and overcome by postsynthetic modification with acetic anhydride. We show here for the first time that amino groups, which can be used as anchoring points for covalent attachment of other molecules, are responsible for fluorescence quenching. Thus, a very promising strategy to implement switchable fluorescence into MOFs is shown here.     

Emission frequency modulation by electronic confinement effect: Congo Red incorporated within a dendritic structure

We have investigated the photophysical properties of an organic dye (Congo Red) incorporated within the internal cavities of a dendrimer (type polypropylenimine of fifth-generation modified with a dense shell of amino acids). In this paper we show that the luminescence properties of Congo Red encapsulated into the "dendritic box" can be modulated by the electronic confinement effect. The emission frequencies of this organic dye incorporated within the dendritic structure can be red shifted with respect to their emission in solution, and the magnitude of this shifting can be modulated under appropriate experimental conditions.     

A STUDY OF THE METHYLENE BLUE-SENSITIZED OXIDATION OF AMINO ACIDS

Abstract— A study has been made of the effects of eight amino acids and a group of compounds related to tryptophan upon the photofading of methylene blue under anaerobic conditions and upon the excited species generated by flash photolysis of the dye. These effects are discussed in relation to the ease of sensitized photooxidation of the amino acids by methylene blue, in order to test the hydrogen-abstraction mechanism proposed for this reaction.
In general, amino acids susceptible to sensitized oxidation also act as reducing agents in the photoreduction of methylene blue, while the insensitive compounds do not reduce the light-excited dye molecule. Methionine, histidine and tyrosine are exceptions, but this is probably due to our choice of pH for the photofading experiments.
The flash-photolysis experiments give no clear-cut evidence for a reaction between amino acid and dye triplet excited state leading to an enhanced yield of the semi-reduced radical, thought to be an intermediate of the photofading reaction. The lifetime of the semi-oxidized radical is reduced by many of the amino acids, and this may be the reactive intermediate in their oxidation.     

功能化荧光素掺杂二氧化硅纳米粒子用于免疫层析试验

A simple but effective approach was developed to synthesize amino functionalized fluorescein isothiocyanate-doped silica nanoparticles based upon polycondensation of tetraethoxysilane. Organic dye molecule (fluorescein isothiocyanate) coupled with a silane coupling agent, 3-aminopropyltriethoxysilane, was incorporated into silica sphere through controlled hydrolysis and polymerization of tetraethoxysilane. The dye was connected with silica sphere through 3-aminopropyltriethoxysilane, which avoided the leakage of the dye. The cohydrolysis and polymerization of tetraethoxysilane and 3-aminopropyltriethoxysilane outside the surface of the silica sphere formed another thin silica shell with the functionalized amino groups on the surface. With amino groups on the surface, the nanoparticle surface was affluent in positive charges. The amino-functionalized nanoparticles were linked with mouse monoclonal antibody against hepatitis B virus surface antigen through electrostatic interaction to form fluorescence probes, which were tested by immunochromatographic assay using immunochromatography test strip. It was indicated that the fluorescence probe was suitable for immunoassay.     

Molecular orientation of rhodamine dyes on surfaces of layered silicates

Films of the layered silicates fluorohectorite (FH) and saponite (Sap) with various rhodamine dyes were prepared. The dyes with acidic as well as large hydrophobic groups in their molecule were not adsorbed on the surface of FH, which was interpreted in terms of high charge density on the surface of this silicate. All adsorbed dyes formed similar forms, such as isolated cations and H-type molecular aggregates, which were characterized by different spectral properties. Polarized ultraviolet-visible (UV-vis) spectroscopy was used for the characterization of the molecular orientation of dye chromophores on the silicate surface. The isolated dye cations and species, which absorbed light at the low energy part of the spectra, were only slightly tilted with respect to the plane of the silicate surface. The cations forming H-aggregates and absorbing light at low wavelengths were oriented in a nearly perpendicular fashion. The nearly perpendicular orientation was observed as a strong increase of dichroic ratio with film tilting. The orientation of the cations in H-aggregates depends partially on the structure of the dye molecule, namely, on the type of amino group (primary, secondary, or tertiary) in the dye molecule. The type of amino groups probably plays a role in the suitable orientation of dye cations for effective electrostatic interaction between the cations and the negatively charged siloxane surface. X-ray powder diffraction could not distinguish dye phases of dye monomers and molecular aggregates.     

Monitoring of amino functionalities on plasma-chemically modified polypropylene supports with a chromogenic and fluorogenic pyrylium reporter

A straightforward strategy toward the sensitive fluorometric detection of primary amino groups on plasma-chemically modified polypropylene supports is presented, exploiting the transformation of the sterically nonhindered pyrylium dye Py-1 into its pyridinium counterpart. The reaction-induced blue-shifted absorption and emission bands and an increased fluorescence quantum yield provide the basis for the spectroscopic distinction between covalently bound and free, that is, nonspecifically adsorbed label molecules. With this label, for the first time, plasma-chemically introduced amino functionalities could be monitored on the surface of a polymer film employing fluorescence spectroscopy and confocal laser scanning microscopy.     

分散染料染色法制备的彩色聚(苯乙烯-丙烯酸)纳米球

在低于聚合物纳米球玻璃化转变温度(110.69 ℃)的条件下,用两种分散染料对聚(苯乙烯-丙烯酸)[P(St-co-AA)]纳米球染色,研究了染色温度(75~95 ℃)和染料用量(1%~5%)对纳米球上染料吸附量的影响。 结果表明,染色温度越高,分散染料用量越大,所得到聚合物纳米球的颜色越深越鲜艳。 分子结构中氨基和羟基数量多的分散蓝2BLN在纳米球上的吸附量低于相同染料用量时分散红FB的吸附量。 经过染色后纳米球的表面变得很粗糙,粒径增加23 nm。 用彩色纳米球对经过阳离子化处理的棉织物进行染色,利用很少量的彩色纳米球,就可以使织物获得较深且鲜艳的颜色。     

Bifunctional Cage‐Type Cubic Mesoporous Silica SBA‐1 Nanoparticles for Selective Adsorption of Dyes

Bifunctional SBA‐1 mesoporous silica nanoparticles (MSNs) with carboxylic acid and amino groups (denoted as CNS‐10‐10) have been successfully synthesized, characterized, and employed as adsorbents for dye removal. Adsorbent CNS‐10‐10 shows high affinity towards cationic and anionic dyes in a wide pH range, and exhibits selective dye removal of a two‐dye mixture system of cationic methylene blue and anionic eosin Y. By changing the pH of the medium, the selectivity of the adsorption behavior can be easily modulated. For comparison purposes, the counterparts, that is, pure silica SBA‐1 MSNs (CS‐0) and those with either carboxylic acid or amino functional groups (denoted as CS‐10 and NS‐10, respectively) were also prepared to evaluate their dye‐adsorption behaviors. As revealed by the zeta‐potential measurements, the electrostatic interaction between the adsorbent surface and the dye molecule plays an important role in the adsorption mechanism. Adsorbent CNS‐10‐10 can be easily regenerated and reused, and maintains its adsorption efficiency up to 80 % after four cycles.     

Triarylborane Dyes as a Novel Non-Covalent and Non-Inhibitive Fluorimetric Markers for DPP III Enzyme

Novel dyes were prepared by simple “click CuAAC” attachment of a triarylborane–alkyne to the azide side chain of an amino acid yielding triarylborane dye 1 which was conjugated with pyrene (dye 2) forming a triarylborane–pyrene FRET pair. In contrast to previous cationic triarylboranes, the novel neutral dyes interact only with proteins, while their affinity to DNA/RNA is completely abolished. Both the reference triarylborane amino acid and triarylborane–pyrene conjugate bind to BSA and the hDPP III enzyme with high affinities, exhibiting a strong (up to 100-fold) fluorescence increase, whereby the triarylborane–pyrene conjugate additionally retained FRET upon binding to the protein. Furthermore, the triarylborane dyes, upon binding to the hDPP III enzyme, did not impair its enzymatic activity under a wide range of experimental conditions, thus being the first non-covalent fluorimetric markers for hDPP III, also applicable during enzymatic reactions with hDPP III substrates.     

The regulation of biothiol-responsive performance and bioimaging application of benzo[c][1,2,5]oxadiazole dyes

The different oxidation states of sulphur atom play a significant role on functional materials. In this work, a aryl-thioether and its sulphone substituted benzo[c][1,2,5]oxadiazole dyes were synthesized and utilized to determine thiol-containing amino acids. The result of selectivity experiments showed they detected the cysteine and homocysteine under physiological condition with negligible interference from other amino acids. In comparison to the thioether dye, the sulphone-based dye exhibited much faster response time for Cys and Hcy. However, the sulphone restricted its thiol-reactivity and bioimaging performance in living cells. By reducing the oxidation state of sulphur atom, we amazedly found that the sulfoxide-based dye still maintained high selectivity ultrafast response time for Cys/Hcy under physiological condition. It was worth mentioning that it also had high reactivity and good bioimaging performance that sulfone compounds did not have.     

The regulation of biothiol-responsive performance and bioimaging application of benzo[c][1,2,5]oxadiazole dyes

The different oxidation states of sulphur atom play a significant role on functional materials. In this work, a aryl-thioether and its sulphone substituted benzo[c][1,2,5]oxadiazole dyes were synthesized and utilized to determine thiol-containing amino acids. The result of selectivity experiments showed they detected the cysteine and homocysteine under physiological condition with negligible interference from other amino acids. In comparison to the thioether dye, the sulphone-based dye exhibited much faster response time for Cys and Hcy. However, the sulphone restricted its thiol-reactivity and bioimaging performance in living cells. By reducing the oxidation state of sulphur atom, we amazedly found that the sulfoxide-based dye still maintained high selectivity ultrafast response time for Cys/Hcy under physiological condition. It was worth mentioning that it also had high reactivity and good bioimaging performance that sulfone compounds did not have.