Design,synthesis, characterization,photophysical and pH chemosensor studies of novel 2,4,6-trisubstituted pyridines

For the application in organic electronics as well as pH meters, a series of novel 2,4,6-trisubstituted pyridines have been synthesized by the reaction of substituted aromatic aldehydes and substituted 3-acetylcoumarin with ammonium acetate. The structures of all the new compounds were characterized by IR, NMR, and GC–MS analysis. The important photo physical prerequisites for organoelectronic such as optical absorption and thermal stability were determined for the synthesized molecules. Optical properties were studied by UV–visible absorption and fluorescence spectroscopy. Optical band gaps of the 2,4,6-trisubstituted pyridines were found to be around 3.01–3.06?eV as calculated from their onset absorption edge. The pH-dependent changes in the fluorescence intensity suggest that 2,4,6-trisubstituted pyridines are useful applicants in intracellular pH meters.     

Synthesis,characterization, and photophysical properties of paraben substituted cyclotriphosphazenes with hydrophilic side groups

Abstract

In this study, five new paraben substituted cyclotriphosphazene compounds containing hydrophilic glycol groups were successfully synthesized. All synthesized cyclotriphosphazene compounds 1-10 were fully characterized via general spectroscopic techniques such as ¹H, ³¹P NMR and MALDI-TOF mass spectrometry. In addition, the investigations of the UV-vis absorption and fluorescence emission properties of the 1-10 carried out via absorption and fluorescence spectroscopies in different solvents. The absorbance bands of the all synthesized compounds 1-10 were observed at about 230–300?nm in all solvents studied. Furthermore, the highest fluorescence emission intensity of the compounds 1-10 was observed in tetrahydrofuran at about 312?nm and the lowest emission intensity was observed in chloroform. The synthesized molecules can be used as custom designed molecules to investigate the DNA binding properties in automatic biosensor device in our laboratories, since they carry hydrophilic glycol units for water solubility and paraben derivatives for DNA effecting properties.     

Synthesis of psoralens and analogues.

This review presents briefly the various classical syntheses of psoralens and angelicins which generally start from preformed suitably substituted coumarin or benzofuran derivatives. However, the discovery of the photocyclo-C-4 addition of psoralens to pyrimidine bases prompted new developments in this area. In particular, improved synthesis of psoralens and substituted angelicins, and synthesis of new analogues such as furochromenes, pyridopsoralens, pyrano benzopyrandiones, dioxinocoumarins and aza-psoralens were described recently. This review focuses on the chemical syntheses of these various compounds.     

Synthesis of Pyridine N‐Oxide–BF2CF3 Complexes and Their Fluorescence Properties

Pyridine N‐oxide–BF₂CF₃ and –BF₂C₂F₅ complexes and their derivatives were synthesized. Most of the complexes show fluorescence both in solution and in the solid state. By expanding the π‐conjugated skeleton, the color of the fluorescence could be changed dramatically. A fluorophore with a high solvent dependency could also be produced. Since such compounds can be synthesized on a gram scale in high yield, and are stable to oxygen, water, and heat, the complexes hold great potential as organic functional materials.     

Synthesis and spectral properties of polymethine-cyanine dye-nitroxide radical hybrid compounds for use as fluorescence probes to monitor reducing species and radicals

Various hybrid compounds comprised of two types of nitroxide radicals and either a pentamethine (Cy5) or trimethine cyanine (Cy3) were synthesized. The nitroxide radicals were linked either via an ester-bond to one or two N-alkyl carboxyl-terminated groups of Cy5, or via two amido-bonds (aminocarbonyl or carbonylamino group) to the 5-position of the indolenine moieties of Cy5 and Cy3. Changes in fluorescence and ESR intensities of the hybrid compounds were measured before and after addition of Na ascorbate in PBS (pH 7.0) to reduce the radicals. Among the hybrid compounds synthesized, those that linked the nitroxide radicals via an aminocarbonyl residue at the 5-position of the indolenine moieties on Cy5 and Cy3 exhibited a 1.8- and 5.1-fold increase in fluorescence intensity with the reduction of the nitroxide segment by the addition of Na ascorbate, respectively. In contrast, fluorescence intensity was not enhanced in the other hybrid compounds. Thus, the hybrid compounds which exhibited an increase in fluorescent intensity with radical reduction can be used in the quantitative measurement of reducing species such as Fe(2+) and ascorbic acid, and hydroxyl radicals. Because these hybrid compounds have the advantage of fluorescing at longer wavelengths-661 (Cy5) or 568 (Cy3)nm, respectively, they can be used to measure radical-reducing species or radicals either in solution or in vivo.     

含萘直链多胺化合物的荧光pH效应及核苷磷酸盐的分子识别

合成了三种含萘但链长不同的多胺类化合物.研究了它们在不同pH条件下的荧光光谱，发现所研究化合物的荧光强度与pH值间有着强烈的依赖关系，因此这类化合物可用作测定溶液pH值的荧光探针.在上述化合物溶液中分别引入不同的核苷磷酸盐（ATP、ADP、AMP），发现所研究的化合物如N-(2-氨乙基)-N’-（2-[(1-萘甲基)氨乙基]）乙二胺(化合物3)，其荧光可被不同的核苷磷酸盐所猝灭.以Stern-Volmer常数（KSV）或猝灭常数（Kq）作为评估猝灭能力大小的标准表明,不同核苷磷酸盐的猝灭能力是各不相同的.其中ATP有着对化合物3荧光最大的猝灭功能.实验结果表明,分子尺寸的匹配和化合物中基团的空间合理排布是化合物和核苷磷酸盐间能发生相互作用的重要根据,而猝灭则强烈地依赖于这类物种间的相互作用,因此可利用化合物荧光强度的改变来识别各种不同的核苷磷酸盐.     

Design and synthesis of anti-barnacle active fluorescence-labeled probe compounds and direct observation of the target region in barnacle cypris larvae for dimethyl-isocyanoalkyl compounds

Anti-barnacle active fluorescence-labeled probe compounds were synthesized, and the interaction between the synthesized probe compounds and the cypris larvae of barnacles was observed under a fluorescence microscope. The observation suggests that anti-fouling active isocyano substances would express activity by acting on the oil cell area in barnacle cypris larvae.     

SPECTROSCOPIC PROPERTIES AND PHOTOREACTIVITY WITH DNA OF NEW MONOFUNCTIONAL PYRIDOPSORALENS

Abstract— New psoralen derivatives have been synthesized in order to enhance their affinity towards DNA. The spectral properties (absorption, fluorescence emission, fluorescence quantum yield) and the photostability of pyrido[3,4-c]psoralen are first reported. The drastic changes observed in the solubility and in the fluorescence emission when these compounds are added to native DNA give evidence of the formation of non covalent dark complexes. Upon UV irradiation (365 nm) of the complexes, a photobinding occurs. Heat denaturation and renaturation experiments of modified DNA show that only monoadducts are formed. From the analysis of their fluorescence properties the involvement of the 4', 5' double bond is assumed. The monofunctional character has also been established for psoralens having a fused pyridine ring in the 4', 5' site. On the opposite, a fused tetrahydropyrido group in the 4', 5' site is inefficient to inactivate this reactive site.     

Improved Spectral Coverage and Fluorescence Quenching in Donor–acceptor Systems Involving Indolo[3‐2‐b]carbazole and Boron‐dipyrromethene or Diketopyrrolopyrrole

A novel π‐conjugated triad and a polymer incorporating indolo[3,2‐b]‐carbazole (ICZ) and 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) were synthesized via a Sonogashira coupling. Compared to the parent BODIPY the absorption and fluorescence spectrum were for both compounds broader and redshifted. The redshift of the fluorescence and the decrease of the fluorescence quantum yield and decay time upon increasing solvent polarity were attributed to the formation of a partial charge‐transfer state. Upon excitation in the ICZ absorption band the ICZ fluorescence was quenched in both compounds mainly due to energy transfer to the BODIPY moiety. In a similar ICZ–π–DPP polymer (where DPP is diketopyrrolopyrrole), a smaller redshift of the absorption and fluorescence spectra compared to the parent DPP was observed. A less efficient quenching of the ICZ fluorescence in the ICZ–π–DPP polymer could be related to the unfavorable orientation of the transition dipoles of ICZ and DPP. The rate constant for energy transfer was for all compounds an order of magnitude smaller than predicted by Förster theory. While in a solid film of the triad a further redshift of the absorption maximum of nearly 100 nm was observed, no such shift was observed for the ICZ–π–BODIPY polymer.     

Synthesis,Photophysical Properties,and Antimicrobial Activity of Novel Styryl Colorants Derived from 7‐Methoxy‐1,4‐diphenethyl‐1,2,3,4‐tetrahydroquinoxaline‐6‐carbaldehyde

The novel 1,4‐diphenethyl‐1,2,3,4‐tetrahydro‐7‐methoxyquinoxalin‐6‐carbaldehyde was synthesized by reductive alkylation of 6‐methoxy quinoxaline with phenyl acetic acid and was further subjected to Knoevenagel condensation with various active methylene compounds to synthesize novel styryl colorants. Photophysical properties of styryl colorants were studied using UV–visible and fluorescence spectroscopy. These colorants displayed orange to violet hue and showed fluorescence emission maxima in the region of 560–640 nm, and displayed a large Stokes shift (85–104 nm). Compounds were subjected to thermogravimetric analysis which showed excellent stability up to 310°C. These styryl compounds were evaluated for their antimicrobial study as antifungal against Candida albicans C. albicans and Aspergillus niger and antibacterial against Escherichia coli and Staphylococcus aureus. The results revealed good antimicrobial activity against tested organisms. The synthesized chromophores were characterized using elemental analysis, FTIR, ¹³C‐NMR and ¹H‐NMR spectroscopy and mass spectrometry.     

Synthesis,characterization, and antioxidant and anticholinesterase activities of pyrazolo derivatives

Twenty-four pyrazolo derivatives (1–4)(a-f) were synthesized and characterized by FTIR, ¹H, and ¹³C NMR (Nuclear Magnetic Resonance), and elemental analysis. The synthesized compounds were also investigated for their antioxidant and anticholinesterase activities. The compounds (3–4)(a-f) carrying morpholine ring were more active than the piperidinyl containing compounds (1–2)(a-f) in both activities. The compound 4f showed higher activity in both assays as compared with the others. Additionally, the anticholinesterase activity test provided higher values than the galantamine in the BChE assay. Therefore, compound 4f can be used as anticholinesterase agent and/or anticholinesterase assay standard.     

Synthesis of optically active 2,7-disubstituted naphthalene derivatives and evaluation of their enantioselective recognition ability

The palladium-catalyzed amination was used to synthesize 2,7-diamino derivatives of naphthalene containing two chiral substituents and fluorophore groups (dansyl, 7-methoxycoumarin, 6,7-dimethoxycoumarin, 6-aminoquinoline). The synthesized compounds were studied by UV absorption and fluorescence spectroscopy in the presence of individual enantiomers of amino alcohols and salts of 21 metals. The possibility of using these compounds as fluorescent detectors for optically active compounds and metals was examined. In the presence of (S)-leucinol, the diquinoline derivative showed enhanced emission with a maximum at shorter wavelengths, which is not typical of its (R) isomer. This fact can be used for the recognition of these enantiomers. A number of naphthalene derivatives can be considered as potential fluorescent chemosensors for Cu^II cations due to the total fluorescence quenching in the presence of this metal.

     

Solution proprieties of dendritic triazine/poly(ethylene glycol)/dendritic triazine block copolymers

Dendritic–linear–dendritic triblock copolymers based on poly(ethylene glycol) (PEG) as the core and dendritic triazine blocks were synthesized. The micellar and aggregation characteristics of the compounds were investigated with NMR and fluorescence spectroscopy. The NMR investigations were carried out in a variety of solvents. In those solvents in which both moieties of the linear–dendritic compounds were completely soluble, the NMR spectra of the linear–dendritic compounds were in the normal form, and all of the signals were as expected. However, in other solvents in which one of the moieties of the compounds was not very soluble, the NMR spectra of the compounds were not in the normal form, and some of the signals were broad or disappeared. The results could be related to the aggregation behavior of the block copolymers with extended or packed conformations of PEG in the solvents, as previously observed in similar systems. Also, fluorescence investigations of some of the isolated compounds in aqueous solutions displayed micellar behavior. The critical micelle concentrations of the copolymers were determined with a fluorescence technique. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 28–41, 2005     

Aggregation-induced multicolor luminescent nanoparticles with adaptive and fixed cores derived from brominated tetraphenylethene-containing block copolymer

Aggregation-induced emission (AIE)-active nanoparticles (NPs) exhibiting multicolor fluorescence and high-quantum yields independent of the environment are important for the further development of next-generation smart fluorescent materials. In this work, AIE-active amphiphilic block copolymers were designed and synthesized by RAFT polymerization of a brominated tetraphenylethene (TPE)-containing acrylate (A-TPE-Br). The block copolymer exhibited typical AIE effects in selective solvents, which can be explained by hydrophobic TPE aggregated in the core during micelle formation. Luminescent core–shell NPs with a crosslinked AIE core (fixed structure) were synthesized by the Suzuki coupling reaction of the bromine groups of the assembled block copolymer and boronic acid compounds. The NPs composed of TPE/thiophene crosslinked core showed green emission in both diluted state and solid state, implying the ability to fluoresce regardless of environmental changes and molecular dispersion. Multicolor luminescent NPs capable of changing color from blue to red were synthesized by changing the coupling compounds, such as anthracene for electron-rich units and benzothiadiazole for electron-deficient units. The effects of the nature of the donor and acceptor, as well as their combination (TPE/donor/acceptor sequence), on the color and fluorescent intensity of the core crosslinked NPs in the nonpolar and polar solvents, and solid state, were investigated.     

Design of novel substituted phthalocyanines; synthesis and fluorescence,DFT, photovoltaic properties

The 4-(2-[3,4-dimethoxyphenoxy] phenoxy) phthalonitrile was synthesized as the starting material of new syntheses. Zinc, copper, and cobalt phthalocyanines were achieved by reaction of starting compound with Zn(CH3COO)2, CuCl2, and CoCl2 metal salts. Basic spectroscopic methods such as nuclear magnetic resonance electronic absorption, mass and infrared spectrometry were used in the structural characterization of the compounds. Absorption, excitation, and emission measurements of the fluorescence zinc phthalocyanine compound were also investigated in THF. Then, structural, energy, and electronic properties for synthesized metallophthalocyanines were determined by quantum chemical calculations, including the DFT method. The bandgap of HOMO and LUMO was determined to be chemically active. Global reactivity (I, A, η, s, μ, χ, ω) and nonlinear properties were studied. In addition, molecular electrostatic potential (MEP) maps were drawn to identify potential reactive regions of metallophthalocyanine (M-Pc) compounds. Photovoltaic performances of phthalocyanine compounds for dye sensitive solar cells were investigated. The solar conversion efficiency of DSSC based on copper, zinc, and cobalt phthalocyanine compounds was 1.69%, 1.35%, and 1.54%, respectively. The compounds have good solubility and show nonlinear optical properties. Zinc phthalocyanine gave fluorescence emission.     

Synthesis and properties of new tetrazines substituted by heteroatoms: towards the world's smallest organic fluorophores

New tetrazines substituted by heteroatoms have been synthesized and their electrochemical and photochemical properties investigated. All compounds are reversibly electroactive with standard potentials shifting cathodically according to the donor character of the substituent. The tetrazine derivatives are also fluorescent with maximum emission wavelengths in the range 550-575 nm. Some of them show very long fluorescence lifetimes (several tens of ns) and remain fluorescent in the solid state without major changes in the spectral features. The fluorescence of one of the derivatives can be efficiently quenched by the presence of electron-rich compounds such as triphenylamines, phenol or anisole, which make them very promising compounds for sensor applications.     

Preparation of core/shell/shell CoFe2O4/OCMC/Cu (BDC) nanostructure as a magnetically heterogeneous catalyst for the synthesis of substituted xanthenes,quinazolines and acridines under ultrasonic irradiation

Highly efficient synthesized magnetic cobalt ferrite nanoparticles supported on OCMC@Cu (BDC) was utilized in the preparation of biologically active heterocyclic compounds through one-pot three-component reactions between of aldehydes, dimedone, aryl amines/2-naphthol/urea under ultrasonic irradiation. This method has various advantages including excellent yields, little catalyst loading, simple procedure, facile catalyst separation, short reaction times, eco-friendly approach and simple purification. The catalyst was characterized by various spectroscopy methods such as fourier-transform infrared (FT-IR), energy-dispersive X-ray (EDX), scanning electron microscope (SEM), X-ray diffraction (XRD) and N₂ adsorption–desorption isotherm (BET). Furthermore, the heterocyclic compounds were characterized by spectral techniques. The nanocomposite was simply separated byusing an external magnet, and it can be recycled several times without significant loss of activity.     

Experimental and theoretical study of three new benzothiazole-fused carbazole derivatives

Three new D-π-A type compounds, each containing one benzothiazole ring as an electron acceptor and one N-ethylcarbazole group as electron donor, were synthesized and characterized by elemental analysis, NMR, MS and thermogravimetric analysis. The absorption and emission spectra of three compounds were experimentally determined in several solvents and were simultaneously computed using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The calculated reorganization energy for hole and electron indicates that three compounds are in favor of hole transport than electron transport. The calculated absorption and emission wavelengths are well coincident with the measured data. The calculated lowest-lying absorption spectra can be mainly attributed to intramolecular charge transfer (ICT). And the calculated fluorescence spectra can be mainly described as originating from an excited state with intramolecular charge transfer (ICT) character. The results show that three compounds exhibited excellent thermal stability and high fluorescence quantum yields, indicating their potential applications as excellent optoelectronic material in optical field.     

Synthesis and biological evaluation of novel sulfonamide derivatives of tricyclic thieno[2,3-<Emphasis Type="Italic">d</Emphasis>]pyrimidin-4(3<Emphasis Type="Italic">H</Emphasis>)-ones on melanin synthesis in murine B16 cells

Phototherapy with psoralens as photosensitizers is the commonly used method for the treatment of vitiligo. Considering the structure similarity between psoralens and thieno[2,3-d]pyrimidinones, a series of novel sulfonamide derivatives containing tricyclic thieno[2,3-d]pyrimidinone were synthesized and evaluated for melanin synthesis in murine B16 cells. All new compounds were characterized by ¹H NMR, ¹³C NMR, IR and HRMS (ESI). Among them, 6 compounds demonstrated excellent activity than positive control (8-methoxylpsoralen, 8-MOP) with more than 1.5-fold potency. Compound 11w with dichloro substitution at meta-positions in the benzenesulfonyl moiety was the most potent one (658.3 ± 8.7%), exhibiting 5.0-fold stronger activity than 8-MOP (130.9 ± 8.6%). The difluoro analog compound 11o increased melanin synthesis in murine B16 cells with a 4.35-fold potency as compared to 8-MOP. These compounds may serve as lead compounds for further drug discoveries for the treatment of vitiligo.