Detection of Polymolecular Associations in Hydrophobized Chitosan Derivatives using Fluorescent Probes

The microenvironment formed by lauroyl and stearoyl derivatives of chitosan in solution has been studied using two fluorescent probes, pyrene and nabumetone. Existence or not of microdomains formed by polymolecular associations, the inherent hydrophobicity of them in aqueous solution, and the influence of degree of substitution (DS) of derivatives were investigated by emission properties of pyrene and strengthened by the photophysical behavior of nabumetone. Additionally, the ratio between the fluorescence intensities of first (~372 nm) to the third (~384 nm) bands of the emission spectrum of pyrene was used to determine the critical aggregation concentration (CAC). In a previous work, it was already reported the characterization of chitosan derivatives by three spectroscopic techniques (¹³C-NMR, ¹H-NMR and infrared), as well as data on the solubility and swelling-index of them. In addition of that, the new results show that the investigated lauroyl and stearoyl derivatives of chitosan are expected to be potential models for applications in the medical field.     

Synthesis and Optical Properties of Various Thienyl Derivatives of Pyrene

A series of various thienyl derivatives of pyrene were synthesized by Stille cross-coupling procedure. Their structures were characterized by ¹H NMR, ¹³C NMR and elemental analysis. The spectroscopic characteristics were investigated by UV–vis absorption and fluorescence spectra. Based on quantum chemical calculations, the energy levels of investigated molecules with respect to the pyrene molecule were also discussed.     

Thiophene-fluorene derivatives with high three-photon absorption activities and their application to optical power limiting

The three-photon absorption (3PA) properties of two thiophene-fluorene derivatives (abbreviated as MOTFTBr and {ATFTBr}) have been determined by using a Q-switched Nd:YAG laser pumped with 38ps pulses at 1064nm in DMF. The measured 3PA cross-sections are 152\times 10^-78cm⁶s² and 139\times 10^-78cm⁶s², respectively. The optimized structures were obtained by AM1 calculations and the results indicate that these two molecules show nonplanar structures, and attaching different donors has different effects on the molecular structure. The charge density distributions during the excitation were also systematically studied by using AM1 method. In addition, an obvious optical power limiting effect induced by 3PA has been demonstrated for both derivatives.     

Comparative DFT Computational Studies with Experimental Investigations for Novel Synthesized Fluorescent Pyrazoline Derivatives

A novel series of pyrazoline derivatives were synthesized and their spectral properties were characterized via FT-IR, ¹H, and ¹³C NMR. The electronic transitions and fluorescence properties were tracked via UV-Vis and emission spectrometry. The density functional theory (DFT) calculations have been also computed to get spot onto the geometry, electronic transitions and spectroscopic properties theoretically that has been compared with the encountered experimental ones. Moreover, the dipole moment, optimized energy, HOMO - LUMO energies and band gaps were calculated for novel candidates pyrazoline derivatives with highly fluorescence quantum yield.     

Novel Thiazole Based Styryl Dyes with Benzimidazole Unit - Synthesis,Photophysical and TD-DFT Studies

Three new Y-shaped styryl dyes were designed and synthesized from thiazole carbaldehyde with different active methylene compounds as acceptor moieties. All the dyes were characterized by IR, ¹HNMR, MS/LCMS/HRMS. Spectroscopic properties and non-linear optical properties styryl derivatives were analyzed and the effect of change in solvent polarity on their absorption and emissive properties has been investigated. The dye with (1-phenylethylidene) propanedinitrile unit shows red shift absorption/emission profile among all the dyes. Density Functional Theory and Time Dependent-Density Functional Theory computations have been used for comparative study with the experimental data and also to understand the structural, molecular, electronic and photophysical parameters of the styryl dyes. The computational method was also employed to investigate the nonlinear optical properties of the styryl dyes in different organic solvent. The unsubstituted benzimidazolyl thiazole styryl dyes possess good non-linear optical properties.     

Fusion-fission in the35Cl +12C reaction at Elab=180 MeV

The properties of the two-body channels populated in the³⁵Cl +¹²C reaction, at a bombarding energy of 180 KeV, have been studied by means of a kinematical coincidence technique. Binary reaction products show full energy equilibration and isotropic angular distributions in the center-of-mass frame. The asymmetrical elemental distribution of the fully-damped yields, similar to that observed previously in the³²S +²⁴Mg reaction, suggests the occurence of fusion-fission rather than orbiting.     

Hydrogen bonding,polarity and matrix effects on the spectroscopic and photophysical properties of some N- and 3-substituted derivatives of carbazoles

Fluorescence spectra and photophysical properties of N-cyano and N-carboethoxy carbazole derivatives have been compared to the equivalent 3-substituted compounds in fluid polar and unpolar solutions and in a low temperature rigid matrix at 77 K. The 3-carboethoxy derivatives have been shown to form an excited state complex (exciplex) with ethanol in fluid solutions. On the other hand the photophysical properties of the N-substituted derivatives are much affected by the solvent polarity in fluid solutions in that the radiationless decay rate constants show a marked increase in these media. A tentative explanation has been given in terms of the relative energy gap existing between the ¹L_b and the ¹L_a states of these molecules.     

A Study on the Permeability of the Triton X-100 Micelles by Fluorescence Decay Kinetics of Probe Molecules

Abstract

The third armonic (355 nm) of a pulsed Nd-YAG laser has been used to excite pyrene in micellar solutions of Triton X-100. Fluorescence quenching by nitromethane and triethylamine of the excited state of pyrene in Triton X-100 has been studied. Quenching rate constant values of 4.94 ± 0.13 × 10⁸M^?1s^?1 and 1.50 ± 0.04 × 10⁸M^?1s^?1 for deactivation by nitromethane and triethylamine, respectively, have been measured. The values obtained are discussed in terms of the interface permeability.     

Infrared Study (3700 - 3000 cm−1) of Hydrogen Bonds Involving Triphenyl Derivatives of Group V Elements

The hydrogen bonded complexes between hydroxylic derivatives and nitrogen bases have been extensively studied by infrared spectrometry but very few experimental results are available for bases involving other elements of group V. Some thermodynamic or spectroscopic data have however been reported for the interaction between alcohol derivatives or phenol and trialkyl- or triphenylphosphine derivatives^1–5 but the electron donor ability of the other compounds is not clearly established especially in the case of phenyl derivatives who have n-and π-electron-donor centers. In this case, the properties of the hydrogen bond can be investigated as a useful tool for the evaluation of the donor properties of the heteroatom and the nature of his interaction with the π ring system⁶. In this work, we have determined the thermodynamic constants and the frequency shifts of the ν_OH stretching vibration of hydrogen bonded complexes involving phenol derivatives and triphenylarsine. The influence of the acidity of the phenol molecules on the properties of the complexes is discussed. Some additional data are reported for complexes involving Ph₃X derivatives (X = N,P,Sb) and discussed as a function of the ionization potential of the heteroatom and the π-ring electrons.     

Photoinduced Intramolecular Electron Transfer and Electronic Coupling Interactions in π- Expanded Imidazole Derivatives

An intramolecular excited charge transfer (CT) analysis of imidazole derivatives has been made. The determined electronic transition dipole moments has been used to estimate the electronic coupling interactions between the excited charge transfer singlet state (¹CT) and the ground state (S₀) or the locally excited state (¹LE). The properties of excited ¹CT state imidazole derivatives have been exploited by the significant contribution of the electronic coupling interactions. The excited state intramolecular proton transfer (ESIPT) analysis has also been discussed.     

Solvent Dependence of Tautomeric Equilibria of 1‐(o‐Substituted Phenyl)Barbituric and ‐2‐Thiobarbituric Acid Derivatives

Abstract

The enolisation tendencies of 1‐(o‐substituted phenyl)barbituric and ‐2‐thiobarbituric acid derivatives have been studied by observing the behaviour of the compounds in different solvents by ¹H and ¹³C NMR. It has been found that the enolisation tendencies of the thiobarbituric acid derivatives observed in polar solvents are greater than those of the barbituric acid derivatives. The ratio of keto–enol tautomers of thiobarbituric acid derivatives in DMSO and in DMF has been calculated.     

A Novel Pyrene Fluorescent Sensor Based on the π–π Interaction Between Pyrene and Graphene of Graphene–Cadmium Telluride Quantum Dot Nanocomposites

In this article, water-soluble graphene–cadmium telluride quantum dot nanocomposites were fabricated through the synthesis of cadmium telluride quantum dots in the presence of graphene aqueous dispersion. It was found that pyrene could remarkably quench fluorescence of graphene–cadmium telluride quantum dot nanocomposites. On this basis, a novel method for the determination of pyrene was developed. Factors affecting the pyrene detection were investigated, and the optimum conditions were determined. Under the optimum conditions, a linear relationship could be established between the quenching of fluorescence intensity of graphene–cadmium telluride quantum dot nanocomposites and the pyrene concentration in the range of 6.00 × 10^?8–2.00 × 10^?6 mol L^?1 with a correlation coefficient of 0.9959. The detection limit was 4.02 × 10^?8 mol L^?1. Furthermore, the nanocomposites were applied to practical determination of pyrene in different water samples with satisfactory results.     

Schiff Base Functionalized 1,2,4-Triazole and Pyrene Derivative for Selective and Sensitive Detection of Cu2+ ion in the Mixed Organic- Aqueous Media

We have prepared Schiff base functionalized 1,2,4-triazole and pyrene derivative for selective, sensitive, and naked eye colorimetric detection of Cu²⁺ in the mixed organic- aqueous media. Amongst the 18 different metal ions studied for absorption and fluorescence titration, only Cu²⁺ ion encourages the modification in spectral properties of Schiff base functionalized 1,2,4-Triazole and Pyrene Probe. The stoichiometric ratio of the TP-Cu²⁺ complex was determined to be 2:1 according to Job’s plot. The lower detection limit estimated for Cu²⁺ is 0.234 nM which shows excellent sensitivity and selectivity of the present analytical method towards detection of Cu²⁺ ion in the mixed organic-aqueous media. The present approach has been successfully utilized for the quantitative determination of Cu²⁺ ion from environmental aqueous solution.

     

AIE Based Coumarin Chromophore - Evaluation and Correlation Between Solvatochromism and Solvent Polarity Parameters

A new class of red emitting extensively conjugated donor-π-acceptor type dyes bearing coumarin units have been synthesized by condensation of 7-(diethylamino)-2-oxo-2 H-chromene-3-carbaldehyde with different active methylenes. All the dyes are characterized by ¹H NMR, ¹³C NMR and HRMS spectroscopy. The photophysical behaviour and the relation between structure and properties of the coumarin “push–pull” derivatives were investigated experimentally. The dyes exhibited positive solvatochromism and solvatofluorism in solution of varying polarity. These coumarin dyes show aggregation induced emission properties with red emitting fluorescence. They show absorption in the range of 501–528 and emission in the range of 547–630 nm. We evaluated photophysical properties of coumarin dyes using solvotochromism and solvent dependent shift in the emission wavelength. All the synthesized coumarin dyes COS1-COS4 are showing very good solvatochromic properties.     

Highly efficient greenish blue-emitting organic diodes based on pyrene derivatives

We report the synthesis of pyrene derivatives as the light emissive layer for highly efficient organic electroluminescence (EL) diodes. Multilayer devices were fabricated with pyrene derivatives (ITO/NPB (50 nm)/blue material (30 nm)/BCP (10 nm)/Alq₃ (30 nm)/LiF (1 nm)/Al). By using 1,1′-dipyrene (DP) and 1,4-dipyrenyl benzene (DPB), the devices produced the blue EL emissions with 1931 Commission International de L’Eclairage coordinates of (x=0.21, y=0.35) and (x=0.19, y=0.25), respectively. The device with DPB shows a maximum brightness of 42,445 cd/m² at 400 mA/cm² and the luminance efficiency of 8.57 cd/A and 5.18 lm/W at 20 mA/cm².     

Enantioselective Fluorescent Sensors for Amino Acid Derivatives Based on BINOL Bearing S-tryptophan Unit: Synthesis and Chiral Recognition

Four novel derivatives of BINOL bearing S-tryptophan unit have been prepared and the structures of these compounds characterized by IR, MS, ¹H and ¹³C NMR spectroscopy and elemental analysis. The enantioselective recognition of these receptors has been studied by fluorescence titration and ¹H NMR spectroscopy. The receptors exhibited different chiral recognition abilities towards N-Boc-protected amino acid anions and formed 1:1 complexes between host and guest. Receptors exhibit excellent enantioselective fluorescent recognition ability towards the amino acid derivatives.     

UV Spectra of Some Derivatives of 1–3 Benzodioxole with Weakly Perturbating Substituents (-CH2X). Study of a Constant Component of Intensity

In a preceding work⁽¹⁾ we have studied the UV-Visible spectrum of pterocarpin, a natural product which is known, with many of its derivatives, for its antifungal properties.^(2–6) The molecule of pterocarpin contains the benzodioxole moiety (figure I) whose presence could be a factor favourable to such properties. Furthermore, some of the benzodioxole derivatives are known as popular drug of abuse (ecstasy).^(7–10) Among our studies on the benzodioxole derivatives substituted in para to one of the oxygen atoms, we present in that paper the results of our UV spectroscopic investigations. This work concerns molecules with substitutents weakly interacting with the π system (i.e. substituents whose type is-CH₂X), since the spectra of these molecules display a basic phenomenon which has never been observed.     

Facile synthesis, optical properties and theoretical calculation of two novel two-photon absorption chromophores

Two heterocycle-based derivatives that can be used as two-photon absorption chromophore, 9-butyl-3-(2, 6-diphenylpyridin-4-yl)-9H-carbazole (BDPYC) and 9-butyl-3-(4-(2, 6-diphenylpyridin-4-yl)styryl)-9H-carbazole (BDPSC) have been successfully synthesized and fully characterized by elemental analysis, IR, ¹H NMR, ¹³C NMR and MS. The molecules possess D-π-A structures, but have different π bridge. The 9-butylcarbazole is used as a donor (D), and the pyridine ring is used as an acceptor (A). One- and two-photon absorption and excited fluorescence properties in various solvents were experimentally investigated. Two-photon initiated optical data recording experiments have been carried out under 740 nm laser radiation, and the possible mechanism of optical data storage is discussed based on theoretical calculations.     

Photophysical Behaviour of Novel Quaternary Pyrenoyl Salts and Their Sensitivity Towards Bile Salt Micellization

The present work describes the synthesis and characterization of pyrene derivatives, N-(1-Pyrenoylmethyl) pyridinium bromide (PM-PB) and N-(1-Pyrenoylmethyl)-N,N,N-triethylammonium bromide (PM-TAB). The photophysical behavior of these molecules has been studied in various protic and aprotic solvents. Using steady state fluorescence intensity, fluorescence anisotropy and dynamic fluorescence lifetime studies, the sensitivity of these molecules towards the micellization process of bile salts has been monitored. These derivatives have been effectively used in estimating critical micellar concentration (CMC) of bile salt, sodium deoxycholate (NaDC).

     

Comparison of Responsive Behaviors of Two Cinnamic Acid Derivatives Containing Carbazolyl Triphenylethylene

Two cinnamic acid derivatives (CPA and CPC) containing carbazolyl triphenylethylene moiety have been synthesized and characterized. The two derivatives possessed aggregation-induced emission property. They exhibited different and interesting responsive behaviors to solvents, water and metal ions. Considering the structural differences between the two derivatives resulting in different interactions between their molecules and the various media was proposed as a possible explanation for these observations. The intermolecular interactions of CPC were much stronger than those of CPA, which promoted molecular association through intermolecular hydrogen bonding to form multimers. It was found that CPC and CPA exhibited high sensitivity to K⁺ and Mn²⁺, respectively. It is suggested that the derivatives have potential technological applications in chemosensor fields.