Feasible selective synthesis of 3-Acetylindoles and 3-Acetoacetylindoles from β-ethylthio-β-indoly α, β-unsaturated ketones

An efficient and selective synthesis of 3-acetyl free(N-H)/N-substituded indoles and 3-acetoacetyl free(N-H)/N-substituded indoles has been developed via the hydrolysis reaction of β-ethylthio-β-indoly α, β-unsaturated ketones in the presence of 3 equivalent of NaOH and 5?mol% of H₂SO₄, respectively. The procedure features easy operation, excellent yields, and high selectivity, compatibility and practicability.     

Photophysics and photocatalytic behavior of composite CdS-purine nanoparticles in the presence of certain indoles

The photophysics of purine-capped Q-CdS has been examined in the presence of certain indoles. The addition of indole does not modify electronic spectrum of purine-capped Q-CdS but it forms a fluorescing charge-transfer intermediate with illuminated CdS, which has an emissive peak at 495 nm. The intensity and the lifetime of this intermediate are enhanced initially with an increase in concentration of indole. In the presence of other indoles, the fluorescence is simply quenched in a dynamic process without forming any fluorescing intermediate. In contrast, emissive CT intermediate is not formed in the presence of indole or any of its derivatives with adenine-capped Q-CdS. In all the cases the quenching of fluorescence, monitored by steady state and time-resolved methods, follows the Stern-Volmer relationship and takes place with a bimolecular rate constant of approximately 10(10) dm(3)mol(-1)s(-1). Purine-capped Q-CdS sensitizes the reactions of the investigated indole(s)-O2 couple much more efficiently than adenine-capped Q-CdS. The differences in quenching of fluorescence and reactivity of holes between purine-capped Q-CdS and adenine-capped Q-CdS are explained by the difference in the binding of indole to the particle. In the case of purine-capped Q-CdS, specific channels for the binding of the solutes are created through the H-bond with the surface-capped purine.     

EXCITED STATES OF FLAVINES – V. THE QUENCHING OF FLAVINE LUMINESCENCE BY INDOLES

Abstract— The quenching of the fluorescence of flavines by indoles in aqueous solution has been studied as a function of concentration, viscosity and temperature. The quenching shows a negative temperature dependence, and is in part diffusion controlled. Static and dynamic processes both contribute to quenching.
In the presence of alcohol or denaturants static quenching is inhibited and dynamic quenching supervenes. The effect of indoles on the flavine fluorescence lifetimes and phosphorescence characteristics is consistent with the quenching mechanism proposed.     

Steady-state and time-resolved fluorescence studies on Trichosanthes cucumerina seed lectin

Steady-state and time-resolved fluorescence spectroscopic studies have been carried out on Trichosanthes cucumerina seed lectin (TCSL). The fluorescence emission maximum of TCSL in the native state as well as in the presence of 0.1 M lactose is centered around 331 nm, which shifts to 347 nm upon denaturation with 8 M urea, indicating that all the tryptophan residues of this protein in the native state are in a predominantly hydrophobic environment. The exposure and accessibility of the tryptophan residues of TCSL and the effect of ligand binding on them were probed by quenching studies employing two neutral quenchers (acrylamide and succinimide), an anionic quencher (I(-)) and a cationic quencher (Cs(+)). Quenching was highest with acrylamide and succinimide with the latter, which is bulkier, yielding slightly lower quenching values, whereas the extent of quenching obtained with the ionic quenchers, I(-) and Cs(+) was significantly lower. The presence of 0.1 M lactose led to a slight increase in the quenching with acrylamide and iodide, whereas quenching with succinimide and cesium ion was not significantly affected. When TCSL was denatured with 8 M urea, both acrylamide and succinimide yielded upward-curving Stern-Volmer plots, indicating that the quenching mechanism involves both dynamic and static components. Quenching data obtained with I(-) and Cs(+) on the urea-denatured protein suggest that charged residues could be present in close proximity to some of the Trp residues. The Stern-Volmer plots with Cs(+) yielded biphasic quenching profiles, indicating that the Trp residues in TCSL fall into at least two groups that differ considerably in their accessibility and/or environment. In time-resolved fluorescence experiments, the decay curves could be best fit to biexponential patterns, with lifetimes of 1.78 and 4.75 ns for the native protein and 2.15 and 5.14 ns in the presence of 0.1 M lactose.     

Solvatochromic Study of Highly Fluorescent Alkylated Isocyanonaphthalenes,Their π‐Stacking,Hydrogen‐Bonding Complexation,and Quenching with Pyridine

Mono‐ and dialkylated derivatives of 1‐amino‐5‐isocyanonaphthalene (ICAN) were studied as new members of a multifunctional, easy‐to‐prepare fluorophore family, which showed excellent solvatochromic properties. The monoallyl derivative and the starting ICAN exhibited strong fluorescence quenching in the presence of small amounts of pyridine. The formation of a hydrogen‐bonded ground‐state pyridine complex was detected; however, analysis of quantum chemical calculations suggested the presence of an additional π‐stacked pyridine complex. The Stern–Volmer plot of the quenching process exhibited a downward curvature and after reaching a minimum the fluorescence intensity increased back to a significant level at high pyridine concentrations. Significant fluorescence was observed even in pure pyridine. A new mechanism and a simple mathematical equation were derived to explain the downward curvature and the remaining fluorescence by the formation of a fluorescent π‐stacked complex.     

Photoinduced electron transfer across a molecular wall: coumarin dyes as donors and methyl viologen and TiO2 as acceptors

Coumarins C-153, C-480, and C-1 formed 1:2 (guest:host) complexes with a water-soluble cavitand having eight carboxylic acid groups (OA) in aqueous borate buffer solution. The complexes were photoexcited in the presence of electron acceptors (methyl viologen, MV(2+), or TiO(2)) to probe the possibility of electron transfer between a donor and an acceptor physically separated by a molecular wall. In solution at basic pH, the dication MV(2+) was associated to the exterior of the complex C-153@OA(2), as suggested by diffusion constants (~1.2 × 10(-6) cm(2)/s) determined by DOSY NMR. The fluorescence of C-153@OA(2) was quenched in the presence of increasing amounts of MV(2+) and Stern-Volmer plots of I(o)/I and τ(o)/τ vs [MV(2+)] indicated that the quenching was static. As per FT-IR-ATR spectra, the capsule C-153@OA(2) was bound to TiO(2) nanoparticle films. Selective excitation (λ(exc) = 420) of the above bound complex resulted in fluorescence quenching. When adsorbed on insulating ZrO(2) nanoparticle films, excitation of the complex resulted in a broad fluorescence spectrum centered at 500 nm and consistent with C-153 being within the lipophilic capsule interior. Consistent with the above results, colloidal TiO(2) quenched the emission while colloidal ZrO(2) did not.     

Detection of nitroaromatic explosives based on photoluminescent polymers containing metalloles

The synthesis, spectroscopic characterization, and fluorescence quenching efficiency of polymers and copolymers containing tetraphenylsilole or tetraphenylgermole with Si-Si, Ge-Ge, and Si-Ge backbones are reported. Poly(tetraphenyl)germole, 2, was synthesized from the reduction of dichloro(tetraphenyl)germole with 2 equivs of Li. Silole-germole alternating copolymer 3 was synthesized by coupling dilithium salts of tetraphenylsilole dianion with dichloro(tetraphenyl)germole. Other tetraphenylmetallole-silane copolymers, 4-12, were synthesized through the Wurtz-type coupling of the dilithium salts of the tetraphenylmetallole dianion and corresponding dichloro(dialkyl)silanes. The molecular weights (M(w)) of these metallole-silane copolymers are in the range of 4000 approximately 6000. Detection of nitroaromatic molecules, such as nitrobenzene (NB), 2,4-dinitrotoluene (DNT), 2,4,6-trinitrotoluene (TNT), and picric acid (PA), has been explored. A linear Stern-Volmer relationship was observed for the first three analytes, but not for picric acid. Fluorescence spectra of polymetalloles or metallole-silane copolymers obtained in either toluene solutions or thin polymer films displayed no shift in the maximum of the emission wavelength. This suggests that the polymetalloles or metallole-silanes exhibit neither pi-stacking of polymer chains nor excimer formation. Fluorescence lifetimes of polymetalloles and metallole-silanes were measured both in the presence and absence of TNT, and tau(o)/tau is invariant. This requires that photoluminescence quenching occurs by a static mechanism.     

Fluorometric determination of heparin based on self-quenching of fluorescein-labeled protamine

A new signaling technique for a fluorometric heparin assay has been developed using the self-quenching of fluoresceinisothiocyanate-labeled protamine (F-protamine). The binding between F-protamine and heparin led to a significant fluorescence quenching due to enhancing the proximity of the F-protamine molecules. The fluorescence of F-protamine (5.9 μg/mL) decreased to 13% in the presence of 2.0 μg/mL heparin. An advantage of this self-quenching system is that the detection can be carried out without using other indicators. With the present system, we could monitor the therapeutic level of heparin in bovine plasma, and the response was quick. These properties of the self-quenching system are suitable for practical use.     

Regioselective Mercury(I)/Palladium(II)-Catalyzed Single-Step Approach for the Synthesis of Imines and 2-Substituted Indoles

An efficient synthesis of ketimines was achieved through a regioselective Hg(I)-catalyzed hydroamination of terminal acetylenes in the presence of anilines. The Pd(II)-catalyzed cyclization of these imines into the 2-substituted indoles was satisfactorily carried out by a C-H activation. In a single-step approach, a variety of 2-substituted indoles were also generated via a Hg(I)/Pd(II)-catalyzed, one-pot, two-step process, starting from anilines and terminal acetylenes. The arylacetylenes proved to be more effective than the alkyl derivatives.     

Photophysical studies of anion-induced colorimetric response and amplified fluorescence quenching in dipyrrolylquinoxaline-containing conjugated polymers

The dipyrrolylquinoxaline (DPQ)-containing monomer and polymers were synthesized and employed as chromogenic and fluorescent chemosensors for inorganic anions. We have found that in the presence of fluoride or pyrophosphate, the receptors do not form hydrogen bonds between the pyrrole protons and anions. The colorimetric responses and fluorescence quenching in these chemosensors are indeed the result of deprotonation of the N-H proton. The anion selectivity is primarily determined by the relative basicity of anions. The sensitivity of DPQ-based chemosensor was found to display a 34-fold enhancement by incorporation into the conjugated polymer. The anion-induced deprotonation generates low-energy, non-fluorescent trapping sites and is responsible for the signal amplification where the quenching of the excited state occurs from the deprotonated DPQ site in the network by rapid exciton migration along the polymeric backbone.     

Photochemistry in solution-XX : Triplet reactivity of aliphatic aldehydes

The triplet self-quenching process of three aliphatic aldehydes has been investigated by inhibition with dienes (taking into account the singlet interaction with the dienes) and by laser flash photolysis. The results obtained for intersystem crossing, the setf-quenching process and product formation have been rationalized. The main reactivity observed for the three aldehydes is the self-quenching process which occurs from both the singlet and triplet state. The laser flash photolysis experiments carried out with butanal show two absorptions of a transient at 320 aod 355 nm; no evidence for two different species could be put forward. The similar decay of the two absorption maximas of the transient, as the concentration of aldehyde is increased, would be indicative of only one single absorbing species which could be either the triplet state of the aldehyde or a radical-pair formed by the self-quenching process or the 1,4-biradical resulting from γ-H abstraction. The fact that both the quenching experiments (by dienes or by 1-methylnaphthalene) and the laser flash measurements lead to about the same lifetime also indicates only one species.The products formed from the triplet setf-quenching process have also been obtained by a different method: excitation of benzophenone at 365 nm in the presence of butanal. The quantum yields for product formation is about the same as those obtained for the triplet by direct irradiation of butanal, except that of octane-4,5-dione which is increased if the photoreaction is carried out at 365 nm in the presence of beazophenone.     

OPTICAL EXCITATION OF THE EOSIN-HUMAN SERUM ALBUMIN COMPLEX*

Abstract The excitation of the eosin-human serum albumin complex has been investigated with spectral and photochemical techniques. Measurements of the changes in absorption and fluorescence spectra induced by complexing have shown that the first eosin molecule is held more strongly than the next few and that multiple binding leads to an enhanced fluorescence self-quenching. Flash photolytic measurements indicate that dye-dye quenching interactions enhance triplet eosin formation, and that oxygen quenching of the triplet is suppressed when the dye is singly bound. The quantum yield for aerobic photobleaching of the complex has been measured and is interpreted in terms of these findings.     

Cononsolvency-induced micellization kinetics of pyrene end-labeled diblock copolymer of N-isopropylacrylamide and oligo(ethylene glycol) methyl ether methacrylate studied by stopped-flow light-scattering and fluorescence

Cononsolvency-induced micellization kinetics of a pyrene end-labeled diblock copolymer of N-isopropylacrylamide and oligo(ethylene glycol) methyl ether methacrylate, Py-PNIPAM-b-POEGMA, was investigated in detail via a combination of stopped-flow light-scattering and fluorescence techniques. Upon a stopped-flow jump from pure methanol to proper methanol/water mixtures, scattered light intensity exhibited an initial increase and then stabilized out; whereas the time-dependence of monomer to excimer fluorescence intensity ratios (I E/I M) revealed an abrupt increase followed by a gradual decrease to plateau values. The dynamic traces of scattered intensity can be well fitted by double exponential functions, the obtained tau 1, scat and tau 2, scat can be ascribed to processes of forming quasi-equilibrium micelles and their relaxation into final equilibrium states, respectively. On the other hand, a triple exponential function was needed to fit the dynamic traces of I E/I M, leading to three characteristic relaxation times (tau 1, fluo, tau 2, fluo, and tau 3, fluo). It was found that the time scales of tau 1, scat and tau 2, scat obtained from stopped-flow light scattering were in general agreement with tau 2, fluo and tau 3, fluo obtained from stopped-flow fluorescence. Considering that excimer fluorescence is extremely sensitive to small aggregates, the newly detected fast process (tau 1, fluo) approximately 10 ms) by stopped-flow fluorescence should be ascribed to the early stage of micellization, i.e., the burst formation of small transient micelles, in which light scattering detection was still not sensitive enough. These small transient micelles fused and grew into quasi-equilibrium micelles, which then slowly relaxed into the final equilibrium state.     

A novel 2,6-dicarbonylpyridine-based fluorescent chemosensor for Co2+ with high selectivity and sensitivity

A novel fluorescence chemosensor based on 2,6-dicarbonylpyridine was designed and synthesized and its photophysical properties were characterized. Upon coordination of Co(2+) by the central 2,6-dicarbonylpyridinyl functional group, the chemosensor 2,6-bis(4-diphenylamino-styrylcarbonyl)pyridine (PhPy) showed nearly complete fluorescence quenching, while no fluorescence response was seen towards other competing cations. The experimental results show the chemosensor is highly selective and sensitive towards Co(2+) in the presence of competing ions, even in the ppb range. Job plot analysis was carried out and the results suggested that the binding of PhPy and Co(2+) was probably a 2?:?1 stoichiometry.     

THE INTERACTION OF MELANIN WITH 8-METHOXYPSORALEN: EFFECT ON RADIATIVE AND NONRADIATTVE TRANSITIONS. A FLUORESCENCE AND PULSED PHOTOACOUSTIC STUDY

Abstract: The interaction of 8-methoxypsoralen (8-MOP) with synthetic eumelanin was investigated using static and time-resolved fluorescence and pulsed photoacoustic calorimetry. Due to the strong overlap of the absorption bands of melanin and 8-MOP, a method is presented to account for the systematic errors introduced by the optical filter effect exerted by each absorbing species in the fluorescence and the photoacoustic measurements. As a preliminary step to the understanding of the nonradiative behavior of the psoralen-melanin complexes, the photoacoustic parameters of 8-MOP in various solvents were determined. Spectroscopic data indicate the absence of interaction at the ground-state level, whereas the singlet excited state of 8-MOP is quenched by the pigment; the average fluorescence lifetimes are independent of the melanin concentration, thus indicating a static quenching mechanism. The photoacoustic data show that the quenching process involves an increased intersystem crossing probability, which is almost unaffected by the presence of oxygen, as expected for a molecule essentially acting as a type I photosensitizing agent.     

THE INTERACTION OF MELANIN WITH 8-METHOXYPSORALEN: EFFECT ON RADIATIVE and NONRADIATIVE TRANSITIONS. A FLUORESCENCE and PULSED PHOTOACOUSTIC STUDY

Abstract –The interaction of 8-methoxypsoralen (8-MOP) with synthetic eumelanin was investigated using static and time-resolved fluorescence and pulsed photoacoustic calorimetry. Due to the strong overlap of the absorption bands of melanin and 8-MOP, a method is presented to account for the systematic errors introduced by the optical filter effect exerted by each absorbing species in the fluorescence and the photoacoustic measurements. As a preliminary step to the understanding of the nonradiative behavior of the psoralen-melanin complexes, the photoacoustic parameters of 8-MOP in various solvents were determined. Spectroscopic data indicate the absence of interaction at the ground-state level, whereas the singlet excited state of 8-MOP is quenched by the pigment; the average fluorescence lifetimes are independent of the melanin concentration, thus indicating a static quenching mechanism. The photoacoustic data show that the quenching process involves an increased intersystem crossing probability, which is almost unaffected by the presence of oxygen, as expected for a molecule essentially acting as a type I photosensitizing agent.     

Catalysis of ionic reactions by polyelectrolytes. IV. Quenching of the quinine cation fluorescence by Fe++, Ag+, and Br− in solutions of poly(vinylsulfonic acid)

The fluorescence quenching of the doubly charged quinine cation by Fe⁺⁺, Ag⁺, and Br^? was studied in the presence and absence of polyvinylsulfonate (PVS). The quenching by cationic species was greatly enhanced by PVS at low polyion concentrations; at higher concentrations of PVS, the fluorescence intensity increased owing to displacement of the quinine cations from the polyion domain. Quenching of quinine fluorescence by Br^? was repressed by PVS. Interpretation of the data with the use of Fe⁺⁺ as the quenching agent led to “effective concentrations” of counterions in the polyion domain similar to those calculated from the catalysis of the redox reaction of Co(NH₃)₅Cl⁺⁺ with Fe⁺⁺. This may indicate that the reagent ions are not rigidly bound to the polyion chain, since such binding would affect differently processes with high and low activation energies. The Stern-Volmer constant for self-quenching of the quinine fluorescence can also be obtained from fluorescence intensity data in PVS solution.     

Luminescent properties of tris(2,2'-bipyridine)ruthenium(II) in sol-gel-processed dip-coated thin films

The luminescence decay and spectral behavior of ruthenium(II)-tris-1,2-bipyridine dichloride dissolved in different organically modified silicate gel matrixes were investigated. Dip-coated thin films were synthesized from tetraethoxysilane (TEOS), methyltriethoxysilane (MTEOS), ethyltriethoxysilane (ETEOS), and methyl- trimethoxysilane (MTMOS). A blue shift in the ruthenium complex emission spectrum with respect to the aqueous solution was observed for all the films on the sol to gel conversion. This spectral shift was slightly dependent on the precursor used to obtain the films and independent of the reaction pH to prepare the "sol". In the data treatment of the time-resolved luminescence measurements, it was assumed that the distribution of the luminophore in the films was nonhomogeneous. The analysis of the luminescence decay profiles was based on a multisite model. All decay curves are best described by a double-exponential model. The parameters of the decay components depended principally on the thermal treatment used in the processing of the films. The lifetimes decreased and the emission espectra showed a red shift with the increase in the drying temperature. A luminescence quenching of the ruthenium complex in the films by dissolved oxygen in aqueous solution was also observed. The quenching rate constant obtained from the preexponential amplitude-weighted mean lifetimes (tau(M)) was in the order of 10(9) M(-1) s(-1). When a phenolic derivative was used as quencher the process rate was greatly reduced compared to the quenching in water. It would seem that the metallic complex sequestered within the film is placed either into a higher microviscosity microenvironment or in a location which the phenolic quencher cannot access. In both cases, the quenching plot based on tau(o)(M)/tau(M) could be fitted satisfactorily by a sum of two terms of Stern-Volmer. This fact is indicative of the matrix microheterogeneity for the films and is fully consistent with the biexponential nature of the luminescence intensity decay profiles.     

The impact of solvent polarity on intramolecular proton and electron transfer in 2-alkylamino-4-nitro-5-methyl pyridine N-oxides

The crystal structure of 2-butylamino-4-nitro-5-methyl pyridine N-oxide (2B5M) and solution studies of both 2B5M and 2-methylamino-4-nitro-5-methyl pyridine (2M5M) N-oxide are presented. Steady-state absorption and emission measurements were employed for both molecules while a picosecond fluorescence up-conversion technique was used to follow the dynamic behavior of the 2M5M system. The experimental methods were complemented by DFT and TD DFT B3LYP/6-31G(d,p) calculations involving ground and excited-state optimization which in the case of the smaller 2M5M molecule were extended to the CAM-B3LYP/6-31G(d,p) method. The solvent effect is incorporated by applying the polarizable continuum (PCM) model. The data reveal that the 2B5M molecule crystallizes in the monoclinic space group P2(1)/c and its crystal lattice is composed of monomers with intramolecular N-H···O [2.572(3) ?] hydrogen bonds, connected into a polymer network by weak intermolecular C-H…O [3.2-3.4 ?]-type interactions. Quantum-chemical calculations show that the aminoalkyl substitutent in aminoalkyl-pyridine N-oxides is a specific determinant of the CT nature of the lowest-lying excited electronic ππ* state, distinguishing them from other nitroaromatic compounds. The results of both picosecond fluorescence up-conversion experiments in different solvents and quantum-chemical calculations suggest that in nonpolar media the ESIPT process in 2M5M is favored, while in polar acetonitrile, the N* → PT* transition demands barrier-crossing and thus unfavorable thermodynamic conditions do not allow the ESIPT to occur. The signals of picosecond fluorescence up-conversion of 2M5M are solvent- and emission-wavelength dependent. The three time components found in a weakly polar isooctane-dioxane mixture have been attributed to solvation dynamics (～500 fs), and to relaxation of N* and PT* forms while in acetonitrile, a very rapid fluorescence decay with a time constant (2.3-4.0 ps) indicative of the presence of the normal (N*) form was observed. Much shorter fluorescence lifetimes in alcohols (a few picoseconds) and in D(2)O (less than 200 fs) than in aprotic solvents suggest that in protic media, the solvent molecules participate in the ESIPT, bridging between the methylamine group and the N-oxide group of 2M5M.     

Solid-phase rhodium carbenoid N-H insertion reactions: the synthesis of a diverse array of indoles

A solid-phase synthesis of an array of indoles is reported. The key step in our approach involves a N-H insertion reaction of N-alkylanilines into a highly reactive polymer-bound rhodium carbenoid intermediate to yield the corresponding alpha-arylamino-beta-ketoester. These insertion products were then treated under acid-catalyzed cyclodehydration conditions to yield a series of polymer-bound indole esters, which were subsequently cleaved from the resin under Lewis acid-promoted amidation conditions to yield the desired indoles in good yields and with excellent purities.