Studying the Symphonizing Effect of NLO Properties in Hydrated and Non-hydrated Donor Acceptor Complexes Formed Via Charge Transfer.

The present work intended to report the synthesis of newly designed donor-acceptor complexes of the pyrimidine-based system namely TAPHIA 1 and TAPHIA 2, which are symphonized to give the NLO properties. The methodologies adopted for both complexes were different and hence influenced their geometrical properties. The synthesized complexes were characterized using different techniques including SCXRD, FTIR, UV, PXRD, and TGA to confirm their formation. The SCXRD analysis revealed that TAPHIA 1 was crystallized in the Pca21 space group in an orthorhombic system while TAPHIA 2 was crystallized in the P21/c space group in a monoclinic system. The third-order NLO properties of both complexes were explored using the Z-Scan technique by employing a continuous wave (CW) diode laser of 520 nm. The third-order NLO parameters including nonlinear refractive index (n2), nonlinear absorption coefficient (ß) and nonlinear optical susceptibility (χ (3)) were calculated at different powers; 40, 50 and 60 mW at fixed solution concentration (10 mM) for both the complexes. Moreover, the experimental properties including NLO, FTIR, and UV were well corroborated with theoretical results obtained at the B3LYP-D3/6-31++G(d,p) level of theory. The analysis of the theoretical and experimental properties of both complexes suggests that TAPHIA 2 is a better applicant to be employed in optical devices than TAPHIA 1 due to the enhanced ability of internal charge transfer.

Impact of Internal Charge Transfer on the Photophysical Properties of Pyridine-Fused Phosphorus-Nitrogen Heterocycles.

The phosphaquinolinone scaffold has been previously studied as a modular core for a variety of fluorescent species where use of substituent effects has focused on increasing or decreasing electron density in the core rings. We now report the synthesis and analysis of several pyridine-containing phosphaquinolinone species exhibiting notable linear conjugation from the aryl-substituent to electron-withdrawing pyridyl nitrogen. Varying the nature of the aryl substituent from electron-withdrawing to electron-donating leads to the generation of an internal charge-transfer (ICT) band in the absorbance spectrum, which becomes the dominant absorbance in terms of intensity in the most electron-rich -NMe2 example. This heterocycle exhibits improved photophysical properties compared to others in the set including high quantum yield and considerably red-shifted emission. The enhanced ICT can be observed in the X-ray data where a rare example of molecule co-planarity is observed. Computational data show increased localization of negative charge on the pyridyl nitrogen as the electron-donating character of the aryl-substituent increases.

Fluorescent Molecular Logic Gates and Pourbaix Sensors in Polyacrylamide Hydrogels.

Polyacrylamide hydrogels formed by free radical polymerisation were formed by entrapping anthracene and 4-amino-1,8-naphthalimide fluorescent logic gates based on photoinduced electron transfer (PET) and/or internal charge transfer (ICT). The non-covalent immobilisation of the molecules in the hydrogels resulted in semi-solid YES, NOT, and AND logic gates. Two molecular AND gates, examples of Pourbaix sensors, were tested in acidic aqueous methanol with ammonium persulfate, a strong oxidant, and displayed greater fluorescence quantum yields than previously reported. The logic hydrogels were exposed to aqueous solutions with chemical inputs, and the fluorescence output response was viewed under 365 nm UV light. All of the molecular logic gates diffuse out of the hydrogels to some extent when placed in solution, particularly those with secondary basic amines. The study exemplifies an effort of taking molecular logic gates from homogeneous solutions into the realm of solid-solution environments. We demonstrate the use of Pourbaix sensors as pE-pH indicators for monitoring oxidative and acidic conditions, notably for excess ammonium persulfate, a reagent used in the polymerisation of SDS-polyacrylamide gels.

Effect of pH on Fluorescence Spectra of Coumarin Derivatives.

Colourless crystalline solid coumarin with a bitter taste and sweet vanilla-like odor mostly acts as chemical protection against predators in plants. Anticoagulants (blood thinners), anti-fungicidal, anti-tumor and anti-inflammatory properties of coumarin are all used to treat skin diseases. Because of internal charge transfer (ICT), coumarin molecules displayed a solvatochromic effect in various solvents of varying polarity. The emission wavelength dependent fluorescence intensity was also affected by pH.

5-Aryl-6-arylthio-2,2'-bipyridine and 6-Arylthio-2,5-diarylpyridine Fluorophores: Pot, Atom, Step Economic (PASE) Synthesis and Photophysical Studies.

A PASE (pot, step, atom, economic) synthetic approach to 5-aryl-6-arylthio-2,2'-bipyridine and 6-arylthio-2,5-diarylpyridine ligands/fluorophores has been reported via SNH in 6-aryl-5H-1,2,4-triazines/aza-Diels-Alder reaction sequence. In this article, the "1,2,4-triazine" methodology was successfully used for the synthesis of C6-thiophenol-substituted (2,2'-bi)pyridines as it is well known that thio-substituted (bi)pyridines and their aza-analogs are of wide practical interest. The photophysical properties of the obtained compounds are studied and compared with those reported earlier for 6-substituted 2,2'-bipyridines. The influence of the nature of substituents in the 6-arylthio(bi)pyridine core on the photophysical properties is discussed. It was observed that the new compounds exhibited promising photophysical properties and could be considered as potential push-pull fluorophores. In addition, they demonstrated greater Stokes shift values compared to the previously described 6-H, 6-arylamino and 6-pentafluoro-2,2'-bipyridines and higher fluorescence quantum yields values compare to pentafluorophenyl-substituted 2,2'-bipyridines. Depending on a nature of (bi)pyridine fluorophore LE (locally excited) and/or ICT (intramolecular charge transfer) state were prevailing in emission spectra.

Aminoantipyrine based efficient chemosensor for Zn(II) ions and its effectiveness in live cell imaging.

A simple imine based receptor NA-1 has been synthesized for detection of Zinc ions. Probe NA-1 showed the selective colorimetric changes with Zinc (II) ions whereas other metal ions didn't showed any observable colorimetric changes. The probe showed the very selective turn-on fluorescence response with Zn(II) ions among other rival metal ions like Cd(II) and Hg(II). The mode of binding was studied by 1H-nmr titrations and fluorescence spectroscopy. Jobs plot analysis confirming that the probe NA-1 forms 1:1 complex with Zn(II). The observed fluorescence and absorption change further supported by theoretical calculations. The turn-on fluorescence of the probe NA-1 is probably attributable to the interruption of intramolecular charge transfer as well as ESIPT. The limit of detection of the probe for Zn(II) sensing is in the range of 14 nano molar. Cytotoxicity (MTT) assay of the probe in live HeLa cells is showing that the probe is least toxic to cells. The probe NA-1 is effectively applied to detect Zn(II) ions in HeLa cells and suggesting the probe is NA-l permeable to cell wall and viable for Zinc(II) ions imaging in live cells.

Theoretical and experimental study on the effects of pH and surfactant on the internal charge transfer process in distyrylnaphthalene-based conjugated oligoelectrolytes.

In this study we have investigated the effects of pH and surfactant on the internal charge transfer (ICT) process in the DSNN derivative, DSNN-NMe+3 (4,4'-bis(4'-(N,N-bis(6″-(N,N,N-trimethylammonium)hexyl)amino)-styryl) naphthalene tetraiodide) with the aim to show that environmentally-induced changes in the degree of ICT process determine the spectral response of the DSNN chromophore. Obtained results showed that DSNN chromophore exhibits evident changes in linear optical properties (absorption/emission wavelengths, quantum yield) upon protonation. These changes are a manifestation of the attenuation of the internal charge transfer processes, which accompanies binding of proton to the nitrogen atoms of the dialkylamino groups at the termini of DSNN chromophore. The results obtained in this study clearly demonstrated the sensitivity of the ICT process in DSNN upon protonation, which, together with the affinity of DSNN towards biological and artificial membranes, may open new perspectives for its utility in fluorescence-based sensing. Moreover, the studied compound showed substantial surfactochromic effects in the ionic and non-ionic surfactant solutions, which indicate the formation of various self-organized DSNN-surfactant aggregates. The structure of these aggregates is determined by the type of specific intermolecular interactions between the chromophore and surfactant molecules. The knowledge of the nature of these interactions may be substantial in the future development of DSNN-based sensing platforms with suitable optical properties.

A Fluorescent Turn-On Carbazole-Rhodanine Based Sensor for Detection of Ag+ Ions and Application in Ag+ Ions Imaging in Cancer Cells.

Carbazole - Rhodanine conjugate is an effective fluorescent host for silver ions through fluorometric transformation from green to red color with a hyperchromic emission. An intramolecular charge transfer process derived from carbazole towards rhodanine favors interaction of thiocarbonyl S and carboxylic acid O of the rhodanine moiety towards Ag+ ion. Carbazole - rhodanine dyad accomplishes the lowest detection limit of 12.8 × 10-9 M and high quantum efficiency. A fluorescence reversibility of the probe with I- ion surges reutilization of sensor molecule as an Ag+ ion probe with minimal loss in the fluorescent efficiency. This fluorescent ligand is a biocompatible probe and is also a proficient candidate for fluorescent imaging of Ag+ ion in live cells.

A highly selective colorimetric and long-wavelength fluorescent probe for the detection of Hg2.

Currently, the fluorescent probe is an important method for detecting heavy metal ions, especially mercury ion (Hg2+ ), which is harmful to the health of humans and the environment due to its toxicity and extensive use. In this paper, we designed and synthesized a colorimetric and long-wavelength fluorescent probe Hg-P with high sensitivity and excellent selectivity, which could detect Hg2+ by the changes of visual color, fluorescence and absorption spectroscopy. With the addition of Hg2+ to probe Hg-P solution, its color changed from yellow to pink, and showed a 171 nm red-shifted absorption spectrum. Probe Hg-P was used in real water and soil solution samples to detect Hg2+ , and the result is satisfactory. Therefore, this new probe shows great value and application in detecting Hg2+ in the environment.

A Colorimetric and Fluorescent Probe for the Detection of Cu2+ in a Complete Aqueous Solution.

The fluorescent probe has become an important method for the detection of heavy metal ions. In the present work, a new and simple fluorescent probe, Cu-P, for detecting copper ion (Cu2+) was designed and synthesized. The probe has shown high sensitivity and selectivity toward Cu2+. The detection limit was 13 nM (based on the 3σ/slope). A significant color change from yellow to pink was observed; thus, the probe Cu-P could serve as a "naked-eye" indicator for Cu2+. Furthermore, the proposed probe was used to detect Cu2+ in real water and soil extract samples, with the result being satisfactory. Therefore, our proposed probe would provide a promising method for the detection of Cu2+ in the environment.

Synthesis of a single 1,8-naphthalimide fluorophore as a molecular logic lab for simultaneously detecting of Fe3+, Hg2+ and Cu2.

A novel fluorescence sensing 1,8-naphthalimide fluorophore is synthesized and investigated. The novel probe comprising two different binding moieties is capable to detect selectively Fe3+ over the other representative metal ions as well as a combination of biologically important cations such as Fe3+, Cu2+ and Hg2+ in the physiological range without an interfering effect of the pHs. Due to the remarkable fluorescence changes in the presence of Fe3+, Hg2+ and Cu2+ ions, INH and AND logic gates are executed and the system is able to act as a single output combinatorial logic circuit with three chemical inputs.

Synthesis, fluorescence-sensing and molecular logic of two water-soluble 1,8-naphthalimides.

Two novel highly water-soluble fluorescence sensing 1,8-naphthalimides are synthesized and investigated. The novel compounds are designed on the "fluorophore-receptor1-spacer-receptor2" model as a molecular fluorescence probe for determination of cations and anions in 100% aqueous media. The novel probes comprising N-imide and N-phenylpiperazine or morpholine substituents are capable to operate simultaneously via ICT and PET signaling mechanism as a function of pH and to recognize selectively Cu2+ and Hg2+ over the other representative metal ions. Due to the remarkable fluorescence changes in the presence of protons, hydroxyl anions, Hg2+ and Cu2+, INH and doubly disabled INH logic gates are executed and the systems are able to act as a single output combinatorial logic circuit with four chemical inputs.

Fluorescent Photoinduced Electron Transfer (PET) Logic Gates for Acidity (pH) and Redox Potential (pE).

This mini-review highlights the photophysical properties of fluorescent molecular logic gates responsive to acids and oxidants, particularly those developed in our laboratory the past few years. The review pays tribute to earlier developments that lay the foundation for this emerging class of molecules. The logic gates incorporate design concepts based on photoinduced electron transfer from the cross-fertilization of the fluorophore-spacer-receptor and fluorophore-spacer-electron-donor formats. The molecular logic gates explored in detail consist of anthracene and/or naphthalimide fluorophores, while the receptor and electron-donor are typically alkyl amines and ferrocene, respectively. This emerging class of molecule has numerous probable uses, most notably, in corrosion science, geochemistry, molecular cell biology and biomedical diagnostics.

Synthesis and Optoelectronic Properties of Thiophene Donor and Thiazole Acceptor Based Blue Fluorescent Conjugated Oligomers.

We report on the synthesis and characterization of low band gap, blue light emitting and thermal stable conjugated oligomer by Wittig condensation. Thiophene and thiazole type of donor-acceptor based series of conjugated oligomers, Oligo-4,5-bis-[2-[5-[2-thiophene-2-yl-vinyl]thiophene-2-yl]-vinyl]-thiazole (OBTV-TZ) and Oligo-2,4,5-Tris-[2-[5-[2-thiophene-2-yl-vinyl]thiophene-2-yl]-vinyl]-thiazole (OTTV-TZ) were synthesized. These oligomers were confirmed by FT-IR and (1)H-NMR and LC/MS analysis. The effect of the number of thiophene rings on the optical, electrochemical, thermal and morphological properties of the oligomers were systematically investigated. Both oligomers were exhibited almost same absorption wavelength in methanol solution (λmax = 365 nm and 369 nm) which indicates both oligomers illustrate similar intra molecular charge transfer (ICT). In solid state, the oligomers were exhibited broadening peaks with higher onset absorptions (λmax = 600 nm and 580 nm). The photoluminescence absorption spectrum of the oligomers was observed at 433 nm and 434 nm respectively in methanol solution with blue emission. The electrochemical band gap ([Formula: see text]) of the OBTV-TZ was 1.55 eV (low band gap) and OTTV-TZ was exhibited greater highest occupied molecular orbital (HOMO) value (E HOMO = -6.6 eV). Moreover morphological parameters of both oligomer film of 2D and 3D diagrams were observed by using AFM studies.

Novel PAMAM Dendron as a Bichromophoric Probe Based on Rhodamine 6G and 1,8-Naphthalimide.

A novel PAMAM dendron designed as a wavelength-shifting bichromophore with 1,8-naphthalimide energy "donor" capable of absorbing light and efficiently transferring the energy to a focal Rhodamine 6G "acceptor" was synthesized and investigated. Moreover, the system was configured on the "fluorophore-spacer-receptor" format. Thus, the distinguishing features of FRET systems were successfully combined with the properties of photoinduced electron transfer and classical ring-opening sensor systems. The synthesized compound shows excellent signaling properties towards protons, Hg(2+) and Fe(3+) ions, therefore, the system is able to act as an one-output combinatorial logic circuit with four chemical inputs.

Investigation of the S1/ICT equilibrium in fucoxanthin by ultrafast pump-dump-probe and femtosecond stimulated Raman scattering spectroscopy.

Time-resolved multi-pulse spectroscopic methods-pump-dump-probe (PDP) and femtosecond stimulated Raman spectroscopy-were used to investigate the excited state photodynamics of the carbonyl group containing carotenoid fucoxanthin (FX). PDP experiments show that S1 and ICT states in FX are strongly coupled and that the interstate equilibrium is rapidly (<5 ps) reestablished after one of the interacting states is deliberately depopulated. Femtosecond stimulated Raman scattering experiments indicate that S1 and ICT are vibrationally distinct species. Identification of the FSRS modes on the S1 and ICT potential energy surfaces allows us to predict a possible coupling channel for the state interaction.

A novel colorimetric probe derived from isonicotic acid hydrazide for copper (II) determination based on internal charge transfer (ICT).

A novel isonicotic acid hydrazide Schiff base derivative N'-(3,5-di-tert-butyl-2-hydroxy-benzylidene) isonicotinohydrazide (DHIH) has been synthesized and developed as a high selective and sensitive colorimetric probe for Cu(2+) determination. Addition of Cu(2+) to the solution of DHIH resulted in a rapid color change from colorless to yellow together with an obvious new absorption band appeared at the range of 400-440 nm by forming a 1:1 complex. Experimental results indicated that the DHIH could provide absorption response to Cu(2+) with a linear dynamic range from 1.0×10(-5) to 1.0×10(-4)mol/L. The detection limit of Cu(2+) was 5.24×10(-7)mol/L with good tolerance of other metal ions.

5-Arylvinyl-2,2'-bipyridyls: Bright "push-pull" dyes as components in fluorescent indicators for zinc ions.

This article reviews the zinc(II)-dependent photophysical properties of arylvinylbipyridines (AVBs), a class of fluoroionophores in which 2,2'-bipyridyl and an aryl moiety are electronically conjugated. Zinc(II) binding of an AVB may lead to an emission bathochromic shift of the fluoroionophore without diminishing its fluorescence quantum yield. This observation can be explained using the excited state model of electron donor-π bridge-electron acceptor "push-pull" fluorophores, in which the bipy moiety acts as an electron acceptor, and zinc(II)-coordination strengthens its electron affinity. The spectral sensitivity of bipy-containing fluoroionophores, such as AVBs, to zinc(II) can be exploited to prepare fluorescent indicators for this ion. In several cases, AVB moieties are incorporated in fluorescent heteroditopic ligands, so that the variation of zinc(II) concentration over a relatively large range can be correlated to fluorescence changes in either intensity or color. AVB fluoroionophores are also used to introduce an intramolecular Förster resonance energy transfer (FRET) strategy for creating zinc(II) indicators with high photostability and a narrow emission band, two desired characteristics of dyes used in fluorescence microscopy.

Synthesis and photophysical characterization of quasi push-pull dicyanodibenzodioxins and their anti-tumor activity against glioma cell line C6.

Dibenzodioxins bearing multiple electron withdrawing groups were synthesized using a simple one-step methodology including examples of molecules possessing electron acceptor groups in both ends. As a consequence internal charge delocalization occurs and the optical spectra are found to be bathochromically shifted compared to similar examples known thus far. A theoretical analysis of the molecular orbitals reveals the origin of the peaks in the dibenzodioxin optical spectra. Select examples exhibit in vitro neuro-cytotoxicity against glioma cell line C6, a finding which enhances existing knowledge about the pharmacologically relevant structural motifs in dibenzodioxins.

A highly selective ratiometric fluorescent pH probe based on a PAMAM wavelength-shifting bichromophoric system.

A novel PAMAM wavelength-shifting bichromophoric system has been successfully developed. Novel compound was configured as a light harvesting antenna where the system surface is labeled with yellow-green emitting 4-(N,N-dimethylamino)ethylamino-1,8-naphthalimide "donor" units capable of absorbing light and efficiently transferring the energy to a focal Rhodamine 6G "acceptor". The periphery of the system was designed on the "fluorophore-spacer-receptor" format, capable of acting as a molecular fluorescence photoinduced electron transfer based probe. Due to the both effects, photoinduced electron transfer in the periphery of the system and pH dependent rhodamine core absorption, novel antenna is able to act as a selective ratiometric pH fluorescence probe in aqueous medium. Thus, the distinguishing features of the fluorescence resonance energy transfer systems were successfully combined with the properties of classical ring-opening charge transfer systems, which may be beneficially for monitoring pH variations in complex samples.