Lichtabsorption und Substituenteneffekte bei Stilben-4-diazoniumionen

Light Absorption and Substituent Effects of Stibene-4-diazonium Ions Substituent effects on ṽ_max-values of 31 stilbene-4-diazonium ions are studied. With increasing donor strength of a substituent in 4′-position the long wave absorption band of stibene-4-diazonium ions shifts from the ultraviolet to the red region of the spectrum. The particular deep colour of diazonium compounds may be described by the very high σ_p-Hammett-constant of the diazonium group. The substituent effects found characterize stilbene diazonium ions as typical donor-acceptor chromogenes.     

Änderung der Lichtabsorption von 4′-Diethylamino-α-cyanostilben-4-diazoniumionen durch Komplexbildung mit Ethylenglycolderivaten,Kronenethern und Valinomycin

Colour Change of 4-Diethylamino-α-cyano-stilbene-4-diazonium Ions by Complex Formation with Ethylenglycol Derivatives, Crownethers and Valinomycine The formation and light absorption of complexes consisting of coloured stilbene-4-diazonium ions and different ethylenglycoles, crownethers and valinomycine were investigated. On complex formation the longest wavelength absorption band of the diazonium compounds shifts hypsochromically. This hypsochromism is solvent dependent. The difference between the absorption maximum of a free and complexed diazonium ion increases with increasing polarity and decreasing n-donicity of the solvents. Other complex forming cations are able to replace the diazonium ions in the complexes, whereby the colours of the original diazonium ions are regenerated. These colour changes can be used to indicate the ability of n-donor compounds to act as an ionophore.     

Photoresponsive optically active polymers—a review

Photoresponsive macromolecules are of interest both as novel organic materials for applications in photodevices and as models for photomodulated biological processes. The presence in polymer chains of photosensitive groups and of chiral groups capable of inducing optical activity into the polymer is very useful for the analysis of photomodulated structural variations and allows storage of the light effect in the form of chiral information. Polypeptides bearing photochromic groups in the side chains are very convenient as the chiroptical properties of the peptide chromophore can be correlated to the backbone conformation. Thus polymers of L-aspartic acid, L-glutamic acid and L-lysine with azobenzene or stilbene groups attached covalently to the side chains are discussed in terms of photoinduced conformational changes and chiroptical information storage in the spectral region of the peptide and of the photoresponsive chromophore. Optically active photochromic macromolecules with hydrocarbon backbone, such as copolymers of (—)-menthyl acrylate with vinyl or acryloyl derivatives of azobenzene, stilbene and indolinospirobenzopyran, also show in some cases photodependence of chiroptical properties with evidence of at least local conformational changes as a consequence of light irradiation which can be used for chiral information.     

Optical switching behavior of polymer‐dispersed liquid crystal composite films with various novel azobenzene derivatives

Polymer‐dispersed liquid crystal (PDLC) composite films were fabricated by thermal polymerization with E7 liquid crystal, monomers, and novel azobenzene derivatives synthesized in this study. To investigate the effects of azocompounds on the optical switching of PDLC films, a series of novel azobenzene derivatives of 4‐alkyloxy‐4′‐methoxyazobenzene with carbon numbers of 3–6, chiral compounds of amyl‐4‐(4‐hexyloxyphenylazo)benzoate, and bornyl‐4‐(4‐hexyloxyphenylazo)benzoate were synthesized. The compounds synthesized in this investigation were identified using FTIR, NMR, and elemental analysis. The optical texture of the composite films was analyzed under crossed nicols with a polarizing microscope. The morphological observation of the solid polymer in the composite films was performed with a scanning electron microscope (SEM). The optical behavior of the composite films on UV irradiation and the effects of the curing time on the thermal stability of the composite films were investigated. Isomerization of the azobenzene derivatives due to UV irradiation was confirmed by a texture study and image recording method. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 789–799, 2004     

Azo disperse dyes for synthetic fibres. I: 2-Methyl- and 2-phenylquinazolone derivatives

Ten variously substituted derivatives ( IVa – j ) of 4′(quinazol-4-on-3-yl) azobenzene were prepared. The effects of the nature and orientation of the substituents on the colour and dyeing properties of these dyes on polyester and acrylic fibres were evaluated.     

香豆素-铜离子(II)配合物硫醇荧光探针的合成及荧光性质的研究

以8-甲酰基-7-羟基香豆素-3-甲酸乙酯与2-氨基苯酚为原料合成了一种亚氨基香豆素类衍生物,其在与铜离子络合后制成了香豆素-铜离子配合物硫醇荧光探针。该探针在体积分数50%的乙醇水溶液中对含有巯基的氨基酸具有良好的选择性。通过荧光光谱,研究了探针的检测机理。在探针识别过程中荧光强度明显增加,在365 nm紫外光激发下荧光颜色由绿色变为蓝色,可以实现可视化检测。     

Synthesis,characterization, and photochemical properties of chromophores containing photoresponsive azobenzene and stilbene

In this article, we describe the synthesis of two azobenzene and two stilbene‐based diacetylene chromophores containing terminal electron‐donating (? OCH₃) and electron‐withdrawing (? NO₂) terminal groups with esterification reactions. The target compounds were characterized by NMR, X‐ray diffraction (XRD), absorption, and photoluminescence spectroscopies. We investigated the structural effects of these photochromic compounds on the E–Z photoisomerization and 1,4‐addition under UV irradiation. 4‐[(4‐Nitrophenyl)‐diazenyl]phenyl pentacosa‐10,12‐diynoate, incorporating the electron‐withdrawing nitro group (? NO₂), underwent the fastest rate of Z‐to‐E isomerization in darkness via a rotation mechanism. Our results demonstrate that self‐assembled azobenzene Z isomers exhibited enhanced fluorescence under UV irradiation. XRD spectroscopy identified bilayer packing by the polydiacetylene films after 1,4‐addition. Chromophores comprising the diacetylene group presented moderate photochromic stability upon 1,4‐addition, changing from their original yellowish color to form a blue phase. These synthesized compounds may be useful in the development of new and unique functional materials that exhibit bistable photochromism. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

芪类糖苷化合物合成研究

根据丹参水溶性成分中丹参酸B的苯并呋哺结构,合成了各种芪类化合物,而羟基芪类化合物理化性质上的缺陷限制了临床试用,设计对其进行糖苷化修饰。以丹酚酸类化合物为先导,设计合成了两个芪类化合物及其葡萄搪、半乳糖和乳糖搪苷类衍生物。     

Investigation on stilbene‐ and azobenzene‐based liquid crystalline organophosphorus polymers

Two series of combined liquid crystalline polyphosphates bearing dual photoreactive mesogenic units (stilbene and azobenzene/α‐methylstilbene and azobenzene) were synthesized by solution polycondensation method. The structures of the synthesized polymers were confirmed by various spectroscopic techniques. Thermogravimetric analysis reveals that they are stable between 230 and 320°C. Differential scanning calorimetry studies were done to study the liquid crystalline property, and glass‐transition, melting, and isotropization temperatures for all the polymers. Polarizing optical microscope shows the birefringent melt for all the polymers exhibiting liquid crystalline property. The photochemical response was studied by UV–visible and fluorescence spectroscopy for all the polymers. The photocrosslinking reaction of the stilbene containing polymers was ascertained by spectroscopic and photolysis studies. The rate of the switching time for the conversion of trans to cis form of azobenzene unit was investigated by UV spectroscopy. The terminal substituents in the side chain affects the texture of liquid crystalline phase for all the polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Bioactive Derivatives of Isopropylstilbene from Mutasynthesis and Chemical Synthesis

Isopropylstilbene is a natural product from Photorhabdus luminescens TT01, with multiple biological activities. A mutant deficient in the production of both anthraquinones and cinnamic acid was constructed, thus giving a clean background according to UV detection. This anthraquinone and stilbene deficient (ASD) mutant was used in mutasynthesis experiments to obtain new stilbene derivatives, which were detected by GC–MS. The structures of the new derivatives were confirmed by detailed MS analysis and then chemically synthesised; all of the natural and synthetic compounds were tested against protozoa that cause tropical diseases. Two compounds obtained by mutasynthesis showed the highest activity against Trypanosoma cruzi, the causative agent of Chagas disease, and Leishmania donovani, which causes leishmaniasis.     

New terpenoid dyes, 3-arylazocamphor derivatives: Dyeing performance and fastness properties

The 3-arylazocamphor (I–VI) and 3-arylazocamphor-2-oxime (VII–XI) dyes were prepared, for use as azodisperse dyes by coupling camphor or camphoroxime respectively with the appropriate diazonium salt in cold ethanol containing sodium acetate solution (10%). The structure of these compounds (I–XI) was established by studying their elemental analysis, i.r. and u.v. spectra. The effect of the nature and position of substituent in the arylazo moiety on the colour, dyeing behaviour, rate of exhaustion and fastness properties when applied to protein and man-made fibres were discussed. The effect of after-treatment with different metal salts on the dyed woollen fibre was also investigated.     

Synthesis and some reactions of 1-(4.6-dimethoxybenzo-furanyl)- and 1-(4.6.7-trimethoxybenzofuranyl)butane-1.2.3-trione-2-arylhydrazones

Both 4.6-dimethoxy-( 1c ) and 4.6.7-trimethoxy-5-acetoacetylbenzofuran 1d are obtained from visnaginone ( 1a ) and khellinone methyl ethers 1b , respectively, by a CLAISEN condensation. The β-diketones 1c and 1d couple with aromatic diazonium compounds to form the hydrazones 2a – i . 1-(4.6-Dimethoxybenzofuranyl)- and 1-(4.6.7-trimethoxybenzofuranyl)butane-1.2.3-trione-2-arylhydrazones 2 a–i react with hydrazine hydrate in acetic acid to yield the corresponding pyrazole derivatives 3a–i or 4a–i . The monohydrazones 5a–b are isolated when 2e or 2i are treated with hydrazine hydrate in ethanol. The hydrazones are converted to the respective pyrazoles by the action of glacial acetic acid. Hydroxylamine hydrochloride reacts with 1.2.3-trione-2-arylhydrazones 2a, c, e, f and i to yield the corresponding isoxazole derivatives 6a–e or 7a–e . The 2-arylhydrazones 2a, c, d, e, h and i form the corresponding pyrazole derivatives 8a–f when treated with semicarbazide hydrochloride.     

Structures and Anti-Inflammatory Evaluation of Phenylpropanoid Derivatives from the Aerial Parts of Dioscorea polystachya

Seven undescribed phenylpropanoid constituents, including three new bibenzyl derivatives (1–3) along with four new benzofuran stilbene derivatives (4–7), were isolated from the aerial parts of Dioscorea polystachya. The structures of these compounds were elucidated using a combination of spectroscopic analyses, including UV, IR, HRESIMS, 1D, and 2D NMR. Further, all the compounds were evaluated on the anti-inflammatory activity for their inhibition of nitric oxide (NO) production by RAW 264.7 macrophages cells, and some of them (1–3 and 6) displayed inhibitory activity with IC₅₀ values in the range of 9.3–32.3 μM. Moreover, compound 3 decreased the expression of iNOS in Western blot analysis, suggesting compound 3 is mediated via the suppression of an LPS-induced NF-κB inflammasome pathway.     

Extraction of Pb2+ with p-tert-butylcalix [4]-, [5]-, [6]Arene Carboxylic Acid Ligands and their Monomeric Counterpart: A Thermodynamic Approach

Studies on extraction equilibrium constants at different temperatures and thermodynamic parameters of solvent extraction of Pb²⁺ ion with carboxylic acid derivatives of different ring size calixarenes and structure related monomeric compound have been carried out. The extraction equilibrium constants corresponding to calix[n]arene (n?=?4, 5, 6) derivatives decrease in the order [5]arene > [6]arene > [4]arene. In all cases, the complexation process is primarily enthalpy driven. The favorable enthalpic contribution for extraction of Pb²⁺ is in the order hexamer ≈ monomer > tetramer > pentamer. However, the unfavorable entropic loss follows the order: monomer > hexamer > tetramer > pentamer. Overall stability of the host-guest complex is the function of entropy-enthalpy compensation and the free energy of complexation is minimum for the pentamer, followed by tetramer ≈ hexamer and monomer. Although the carboxylic acid derivative of calix[4]arene is more preorganized than the calix[5]arene derivative, extraction of Pb²⁺ ion with the tetramer passes through greater entropic loss than that with the pentamer and the degree of preorganization of calix[4]arene derivative is far from perfect for the complexation and extraction of Pb²⁺ ion. As compared to tetrameric and hexameric counterparts, the structural features of the carboxylic acid derivative of calix[5]arene prior to complexation contribute much to interact with the Pb²⁺ ion and form a thermodynamically stable complex. Supplementary materials are available for this article. Go to the publisher's online edition of Solvent Extraction and Ion Exchange to view the supplemental file.     

Tautomerism and Geometric Isomerism in Arylazo-Phenols and Naphthols. Part III. Orthohydroxy Derivatives and their Reversible Photochemical Reactions

Solutions of o-hydroxy or o-methoxy azobenzene and phenylazonaphthalenes were studied spectroscopically and photochemically in a wide range of temperatures and solvents. All the hydroxy derivatives exist in solution in the azo form, except for (I) and (IV) which show an equilibrium between the azo and hydrazone forms. The latter predominates in (IV), and in (I) and (IV) is responsible for the so-called luminescence of o-hydroxy azo compounds. Luminescence was absent in the other compounds. All compounds except (IV) undergo distinct spectral changes when irradiated with ultraviolet or visible light at temperatures sufficiently low to prevent thermal reversion. In the methoxy derivatives the changes are due to cis-trans isomerization, as shown also by the activation energy of 23 kcal/mole for the thermal reversion. The same explanation is assumed for the hydroxy compounds. The detailed involvement of the hydrazonic form of (I) in these spectral changes is not clear. In rigid media at ?187°C, irradiation of (I) with visible light causes a different spectral change, tentatively ascribed to a “hydrazone” → “azo” conversion. Heating the solutions reverts the changes caused by irradiation. The kinetics of this reversion in the hydroxy compounds are complex, showing that the reactions are either catalyzed or else pass through a hydrazonic form, thereby proceeding with much smaller activation energies and frequency factors. It is suggested that several of the eight possible configurations of the “hydroxy” compounds serve as intermediates in the photochemical and thermal conversions, while others coexist in thermal equilibrium.     

Electroreduction of oxygen on glassy carbon electrodes modified with in situ generated anthraquinone diazonium cations

The electrochemical reduction of oxygen on glassy carbon (GC) electrodes modified with in situ generated diazonium cations of anthraquinone (AQ) has been studied using the rotating disk electrode (RDE) technique. The electrografting of the GC electrodes was carried out in two different media: in acetonitrile and in an aqueous acidic solution (0.5 M HCl). 1- and 2-Aminoanthraquinone were used as starting compounds for the formation of the corresponding diazonium derivatives. The anthraquinone diazonium cations were generated by reaction of the aminoanthraquinones with tert-butyl nitrite and sodium nitrite in acetonitrile and in 0.5 M HCl, respectively. For comparison purposes, the previously synthesised and crystallised diazonium tetrafluoroborates of anthraquinone were used for the GC surface modification. Cyclic voltammetry was employed to determine the surface concentration of AQ in O₂ free 0.1 M KOH. The electrocatalytic behaviour towards O₂ reduction was similar for all the AQ-modified electrodes studied. The kinetic parameters of oxygen reduction were determined using a surface redox catalytic cycle model. The rate constant of the reaction between the semiquinone radical anion of AQ and molecular oxygen was virtually independent of the point of attachment of the quinone to the electrode surface.     

Mediator and catalytic effects of porphyrin modified electrodes on redox LB films

In this work, the mediator and/or catalytic properties of modified ITO electrodes by oxidative electrodeposition of Ni-porphyrins have been analyzed. Thus, monolayers containing viologen or azobenzene derivatives, have been transferred onto the porphyrin modified electrodes by using the Langmuir-Blodgett (LB) technique. Following, the redox processes of these compounds forming the LB films and deposited on the modified electrode and the bare ITO have been investigated.The obtained results reveal not only the excellent mediator character of the porphyrinic electrodeposit throughout the viologen redox processes, but also its the catalytic action over the azobenzene kinetics. Specifically, for the last case, the NiTMPyP films accelerate the azobenzene kinetics up to 100 times with respect to those results obtained in absence of porphyrin.     

Preparation and optical performance of chiral polymers having azobenzene segments

A series of monomeric azobenzene derivatives of 6‐(4‐nitro‐4′‐oxy‐azobenzene acrylate with carbon numbers of 6 and 11, and the chiral monomer of bornyl 4‐(6‐acryloyloxyhexyloxy)‐phenyl‐4′‐benzoate were synthesized. Chiral polymers having bornyl group end‐capped pendants with azobenzene‐derived segments were prepared. Molecular structures and polymer compositions were confirmed by using ¹H‐NMR, elemental analysis, FTIR, and UV–vis analyzers. Thermodynamic properties of both monomers and polymers were investigated. Specific rotations of chiral monomers and polymers were estimated by using an automatic digital polarimeter. Liquid crystalline textures of monomers and polymers were analyzed by using a polarizing optical microscope and confirmed by a small‐angle X‐ray analyzer. The optical reflection characteristics of composite cells with chiral nematic liquid crystal and various amounts of azobenzene derivatives were evaluated by using a UV–vis spectrophotometer. The reliability and stability of the composite cells with E48/S811 and azobenzene derivatives were studied. The photoisomerization of the chiral polymer film was investigated by using SEM and AFM analyzers. It was found that the UV irradiation of a laser spot caused the shrinkage of polymer film due to the photoisomerization of azobenzene segments. The contraction of the polymer film can be recovered by heat treatment. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3693–3704, 2004     

Controllable preparation and near infrared optical limiting properties of fluorene‐containing polyacetylenes

Two novel fluorene functionalized polyacetylenes with different conjugation bridge architectures (stilbene and azobenzene), poly[2‐[4‐vinyl‐4′‐(N‐methyl, N‐ethyl‐yl propargyloxy) phenyl azo]‐9,9‐dioctylfluorene] ( PC1 ), poly[2‐[4‐vinyl‐4′‐(N‐methyl, N‐ethyl‐yl propargyl group) stilbene ethenyl]‐9,9‐dioctylfluorene] ( PC2 ), were designed and prepared through using [Rh(nbd)Cl]₂‐Et₃N as the catalysts, respectively. These polymers are soluble in common organic solvents, such as toluene, chloroform, 1,2‐dichloromethane, and tetrahydrofuran, which their structures and properties were systematically characterized by means of Fourier transform infrared spectroscopy, nuclear magnetic resonance, elemental analyses, UV–vis, photoluminescence, thermogravimetric analysis, gel permeation chromatography, and Z‐scan technique. The optical limiting properties were investigated at 780 nm with 450 fs laser pulses. Remarkably, it is expected that, by incorporation of fluorene into functional polyacetylene has endowed the resultant polymers with well optical limiting properties and thermal stability. Additionally, the nonlinear optical properties of functionalized polyacetylenes were significantly affected by different molecular structure of conjugated bridge of substituted group. The polyacetylenes with azobenzene ( PC2 ) conjugated bridge displaying well two‐photon absorption cross‐sections of 3950 cm/GM (2010 cm/GM for PC1 containing stilbene), owning to stronger π‐conjugated chromophores of objective polymer and intramolecular charge transfer effect. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46100.     

Reactions of α-Arylhydrazono-β-oxo-β-phenyl-propionitriles

ω-Cyanoacetophenone was coupled with a variety of aromatic diazonium chlorides to give the corresponding arylazo derivatives 1 a – g . Analysis of the IR and UV spectra of these compounds indicated that they exist mainly as the corresponding arylhydrazones. Compounds 1 a – d, f, g reacted with diazomethane to yield the N-methyl-arylhydrazones 2 a – f . 3-Amino-4-arylazo-5-phenylpyrazoles 5 a – g and 4-arylazo-5-imino-1,3-diphenyl-2-pyrazolines 6 a – g were obtained by the interaction of 1 a – g with hydrazine hydrate and with phenylhydrazine, respectively.