pH-Dependent Photoinduced Interconversion of Furocoumaric and Furocoumarinic Acids

Photo-controlled or photo-regulated molecules, especially biologically active and operating in physiological conditions, are in steady demand. Herein, furocoumaric and furocoumarinic acids being (Z/E)-isomers relative to each other were obtained in two stages starting from psoralen: the alkaline solvolysis of psoralen led to furocoumaric acid, which was further Z → E photoisomerized (365 nm) to furocoumarinic acid. The kinetics of Z → E photoisomerization was monitored by HPLC and UV-vis spectrophotometry. Photophysical characteristics in the aqueous phase for both acids, as well as the reversibility of (Z/E) photoisomerization process, were also assessed. Furocoumarinic acid was found to be visibly fluorescent at pH 2.0–12.0, with the maxima of fluorescence emission spectra being pH-dependent. The reverse E → Z photoisomerization predicted by quantum chemistry calculations as energetically favorable for the monoanionic form of furocoumarinic acid was proved in the experiment while being complicated by pyrone ring closure back to psoralen in acidic and neutral conditions. The preparative synthesis of furocoumarinic acid outlined in this work is particularly valuable in view of a wide range of pharmacological effects previously predicted for this compound.     

Influence of photoinduced isomerization on the chiral separation of novel liquid crystalline materials with a diazene moiety

The influence of photoinduced isomerization on the enantiomeric separation of two newly synthesized liquid crystalline materials, liquid crystals 1 and 2, was studied by high‐performance liquid chromatography on a chiral stationary phase Chiralpack AD‐3. Both materials have one chiral center and one diazene moiety. The compounds were separated into their E and Z isomeric forms. The conditions and time scale of the ultraviolet‐induced E to Z transition were briefly evaluated. Under the optimized conditions, we were able to baseline separate the S and R enantiomers of both the studied materials in their E isomeric form. The chiral separation of liquid crystal 2 after ultraviolet irradiation was unsuccessful. In contrast, the chiral separation of liquid crystal 1 possessing a similar structure to liquid crystal 2 provided baseline separation in its Z isomeric form as well. Previously, we have shown the influence of photoinduced isomerization and its utilization in the enantioseparation on relatively simple molecules. Here, we demonstrate that (1) much more complex compounds can also be successfully separated despite the bulkiness of the achiral part of the structure and (2) photoinduced isomerization even for such complex molecules still strongly influences their chromatographic properties.     

Antimicrobial components of the red alga Laurencia hybrida (Rhodophyta,Rhodomelaceae)

Two unstable antimicrobial metabolites have been isolated from aqueous methanolic extracts of fresh samples of the red alga Laurencia hybrida. The molecules have been identified as 11-formyl-undeca-5(Z), 8(E), 10(E)-trienoic acid and 9-hydroxyeicosa-2(Z), 5(Z), 7(E), 11(Z), 14(Z)-pentaenoic acid.     

Thermo-physical properties of the binary mixture of benzaldehyde with bromobenzene at 303.15, 308.15, and 313.15?K

The values of density, viscosity, and ultrasonic velocity for the binary liquid mixture of benzaldehyde with bromobenzene have been measured over the entire range of composition at 303.15, 308.15, and 313.15?K. These values have been used to calculate the excess molar volume (V ^E), deviation in viscosity (????), deviation in velocity (?U), deviation in isentropic compressibility (??? _s), excess internal pressure (???), excess intermolecular free length (?L _f), and excess acoustic impedance (?Z). McAllister??s three-body-interaction model is used for correlating kinematic viscosity of binary mixtures. The excess values were correlated using the Redlich?CKister polynomial equation to obtain their coefficients and standard deviations. The thermo-physical properties (density, viscosity, and ultrasonic velocity) under the study were fitted to the Jouyban?CAcree model.     

Chromatographic identification of (E)- and (Z)-isomers of unsaturated organic compounds using their physicochemical characteristics

The values of physicochemical properties determine completely the sequence of chromatographic elution of (Z)- and (E)-isomers of 1,2-disubstituted unsaturated compounds and can therefore be used as reference data for their GC-identification. The isomer with the minimum boiling point, relative density, and refractive index has the least retention parameters. By the ratio of the values of these properties the (Z)- and (E)-isomers form two groups: (Z) > (E) and (Z) < (E). This feature is due to the larger polarity of the (Z)-isomers of asymmetrically substituted compounds containing polar substituents at the double bond C=C. The discovered regularities may be extended to the cis- and trans-isomers of 1,2-disubstituted cycloalkanes and even to the position isomers of substituted arenes.     

Insight into the pathway for biosynthesis of sesquarterpenes in nonpathogenic Mycobacterium species: identification of heptaprenylcycli-14E,18E-diene

A new sesquarterpene, heptaprenylcycli-14E,18E-diene, was isolated from Mycobacterium chlorophenolicum cells grown up to the stationary phase. The absence of heptaprenylcycli-14Z,18E-diene indicates that only (E,E,E)-geranylgeranyl diphosphate may be utilized as an intermediate of sesquarterpene biosynthesis in the stationary phase, in contrast with the logarithmic growth phase in which both (E,E)-farnesyl diphosphate and (E,E,E)-geranylgeranyl diphosphate are used. Further, our findings suggest that the stepwise reduction of the polyprenyl group in sesquarterpene biosynthesis might proceed in a different order from that in chlorophyll biosynthesis.     

Separation and Identification of Carotenoids in Flowers of Chelidonium majus L. and Inflorescences of Solidago canadensis L.

The current research project aimed at the carotenoid analysis of total extracts of the inflorescences of Canadian goldenrod (Solidago canadensis L.), and the flowers of greater celandine (Chelidonium majus L.). The plant extracts were separated and analyzed by column liquid chromatography (CLC) and LC. Carotenoids were identified on the basis of their UV–Vis spectroscopic properties in different solvents, chemical reactions [5,6-epoxide → 5,8-epoxide (furanoid oxide rearrangement), (E/Z)-isomerization] and by co-chromatography with authentic reference samples. The parallel use of CLC and LC allowed the identification of numerous minor carotenoids in all extracts and fractions.     

Photochemistry of 3,6-bis(styryl)pyridazines in solution and in neat liquid crystalline phase—optical switching and imaging techniques

3,6-Bis(styryl)pyridazines 1a-f with 2-6 alkoxy groups show on irradiation in solution a stereoisomerization which leads to a photostationary state of (E,E)- and (E,Z)-isomer. Sensitizing and quenching experiments reveal that the (E,E)→(E,Z) route is a pure triplet process, whereas the (E,Z)→(E,E) route can have a minor singlet by-reaction.Hexyloxy or dodecyloxy chains on the terminal benzene rings convey the (E,E)-isomers of compounds 1a,b,d-f thermotropic liquid crystalline properties. In particular S_A, S_C, and S_F/I phases were studied with regard to their photochemical behavior. Depending on the system, photodegradation of the smectic phase to the isotropic melt (S→I) or photoinduction of the smectic phase (I→S) can be achieved by alteration of the (E,E)/(E,Z) ratio. These processes represent the basis for imaging techniques (writing and erasing of information).     

Synthesis and optical properties of a poly(2′,5′-dioctyloxy-4,4′,4″- terphenylenevinylene) with high content of (Z) vinylene units

Poly(2′,5′-dioctyloxy-4,4′,4″-terphenylenevinylene) with (E) configuration of the vinylene double bonds was prepared by Suzuki-Miyaura polymerization of (E)-4,4′-dibromostilbene and 2,5-dioctyloxy-1,4-benzenediboronic acid. Attempts to extend this simple procedure to the synthesis of the polymer with (Z) configuration, starting from (Z)-4,4′-dibromostilbene, were unsuccessful. However, the use of (Z)-4,4′-diiodostilbene and a careful choice of Pd catalyst and experimental conditions, lead to a material with a >95/<5 (Z)/(E) ratio of vinylene units. The investigation of optical properties of both the (E) and (Z) polymers evidenced that (Z) linkages act as defects which reduce the effective conjugation length in the polymer backbone.     

Synthesis and biological activities of the tris-oxazole macrolactone analogs of mycalolides

Mycalolides are tris-oxazole macrolides isolated from the marine sponge Mycale sp., which shows cytotoxic, antifungal, and actin-depolymerizing activities. To develop an efficient synthetic route of mycalolides and to evaluate its functional mechanism of biological activities, tris-oxazole macrolactone analogs of mycalolides were synthesized through the use of ring-closing metathesis (RCM). The presence/absence of protecting groups at C3, solvent polarity, and reaction temperature significantly affected the stereoselectivity of RCM (E/Z=2.5/1.0–1.0/2.5). The 19E- and 19Z-stereoisomers both exhibited moderate cytotoxicity against tumor cells, but neither showed significant actin-depolymerizing properties or antimycotic activity against pathogenic fungi. Thus, both the side-chain (actin-binding) moiety and the macrolactone moiety were suggested to be essential for the potent biological activities of the parent molecules.     

Molecular rotors: synthesis and evaluation as viscosity sensors

It has been shown that compounds containing the p-N,N-dialkylaminobenzylidene cyanoacetate motif can serve as fluorescent non-mechanical viscosity sensors. These compounds, referred to as molecular rotors, belong to a class of fluorescent probes that are known to form twisted intramolecular charge-transfer complexes in the excited state. In this study we present the synthesis and spectroscopic characterization of these compounds as viscosity sensors. The effects of the molecular structure and electronic density of these rotors to the emission wavelength, fluorescence intensity, and viscosity sensitivity are discussed.     

Photochemistry of dienones—X: Photochemistry of (e)-β-ionone oxime ethyl ether

(E)-β-ionone oximc ethyl ether [(E, E)-4] upon direct irradiation with λ either254or 313 nm yields the geometrical isomer (E, Z)-4 and (Z)-retro-γ-ionone oxime ethyl ether (Z,E)-5 as the sole primary products, illustrating (E)-(Z) isomerization (φ₃₁₃ =0.49) and a 1, 5-hydrogen shift (φ313 =0.15) respectively. From studies with triplet photosensitizers and with ethyl iodide (to enhance the singlet-triplet intersystem crossing) it is concluded that these two products in the direct irradiation result only from the singlet excited state, and that the inter-system crossing quantum yield is relatively low. Upon prolonged irradiation of (E,E)-4 with λ 313 nm the eventual products are (Z,E)-5 and (Z,Z)-5, whereas with λ 254 nm they are (E,E)-5 and [(Z,E)-5 and/or (E,Z)-5]. Upon triplet photosensitization (E,E)-4 undergoes only (E)-(Z) isomerization, leading to a mixture of all the four geometrical isomers of4. From the dependence of the geometrical isomer distribution in the photostationary state on the triplet energy of the sensitizer the triplet energies of (E,E)-4, (E, Z)-4, (Z, E)-4, and (Z, Z)-4 have been determined to be ca 55, < 55,57, and 57 $\text{kcal}\text{mol}$ respectively.     

Photoconversion of o-hydroxycinnamates to coumarins and its application to fluorescence imaging

(E)-o-Hydroxycinnamates were synthesized and their photochemical behavior was investigated in liquid and solid states. It was confirmed by ¹H NMR spectroscopy that the (E)-o-hydroxycinnamates converted into the corresponding coumarins via (Z)-o-hydroxycinnamate intermediates. The photoconversion was greatly accelerated in the presence of p-toluenesulfonic acid. The optical properties of the cinnamates were compared with those of the corresponding coumarins. Fluorescence imaging was successfully accomplished by photoirradiation of PMMA films containing the cinnamates.     

A new thermo- and photo-driven [2]rotaxane

A new rotaxane with functional chromophores porphyrin and fluorene as stoppers has been synthesized. It displays dual fluorescent character. The macrocycle ring can shuttle between the fumaramide part and the succinimide part on the dumbbell. Heating and UV light irradiating on the rotaxane lead to the reversible E/Z conversion, driving the ring to shuttle between the two stations. The optical properties of porphyrin and fluorene stoppers of the thread do not change so much while the ring shuttles because the macrocycle does not interact with the two stoppers. However, the active group, propargyloxyl, is introduced onto the two sides of the ring so that the rotaxane has the potential to be functionalized by further decoration.     

Influence of a Change in Helical Twisting Power of Photoresponsive Chiral Dopants on Rotational Manipulation of Micro‐Objects on the Surface of Chiral Nematic Liquid Crystalline Films

Herein we report a group of five planar chiral molecules as photon‐mode chiral switches for the reversible control of the self‐assembled superstructures of doped chiral nematic liquid crystals. The chiral switches are composed of an asymmetrically substituted aromatic moiety and a photoisomerizing azobenzene unit connected in a cyclic manner through methylene spacers of varying lengths. All the molecules show conformational restriction in the rotation of the asymmetrically substituted aromatic moiety in both the E and Z states of the azobenzene units resulting in planar chirality with separable enantiomers. Our newly synthesized compounds in pure enantiomeric form show high helical twisting power (HTP) in addition to an improved change in HTP between the E and Z states. The molecule with a diphenylnaphthalene unit shows the highest ever known initial helical twisting power among chiral dopants with planar chirality. In addition to the reversible tuning of reflection colors, we employed the enantiomers of these five compounds in combination with four nematic liquid crystalline hosts to study their properties as molecular machines; the change in HTP of the chiral dopant upon photoisomerization induces rotation of the texture of the liquid crystal surfaces. Importantly, this study has revealed a linear dependence of the ratio of the difference between HTPs before and after irradiation against the absolute value of the initial HTP, not the absolute value of the change in helical twisting power between two states, on the angle of rotation of micro‐objects on chiral nematic liquid crystalline films. This study has also revealed that a change in irradiation intensity does not affect the maximum angle of rotation, but it does affect the speed of rotational reorganization of the cholesteric helix.     

π-Extended conjugate phenylacetylenes. Synthesis of 4-[(E) and (Z)-2-(4-ethenylphenyl)ethenyl]pyridine. Dimerization, quaternation and formation of charge-transfer complexes

The conjugate (E)- and (Z)-(4′-pyridylethenyl)-4-phenylethyne (E-4 and Z-4) has been satisfactorily prepared by two different routes: (a) by dehydrohalogenation of 4′-pyridylethenyl-4-phenyl-β-chloroethene; (b) by the Wittig reaction between p-(iodobenzyl)(triphenyl)phosphine ylide and 4-pyridinecarboxaldehyde, E/Z isomer separation, and cross-coupling with 2-methyl-but-3-yn-2-ol followed the propanone elimination. The Glaser oxidative dimerization of (Z)-4 yields (Z,Z)-1,4-di[(4′-pyridylethenyl)-4-phenyl]-buta-1,3-diyne in good yield, (Z,Z)-5. (E,E)-5 was obtained by phase transfer oxidative dimerisation of (E)-4 in presence of their N-methyl salt (E)-10. Mono- and di-N-methylated salts of conjugate (E,E)-5 and (Z,Z)-5, were obtained by quaternation with iodomethane. The (Z,Z)-5 di-N-methylated salt forms charge-transfer complexes with TCNE, TCNQ and TMPD.     

Dimension Engineering of Stimuli-Responsive 1D Molecular Crystals into Unusual 2D and 3D Zigzag Waveguides

We demonstrate an innovative technique to achieve organic 2D and 3D waveguides with peculiar shapes from an acicular, stimuli-responsive molecular crystal, (2Z,2′Z)-3,3′-(anthracene-9,10-diyl)bis(2-(3,5-bis(trifluoromethyl)phenylacrylonitrile), Ant-CF₃. The greenish-yellow fluorescent (FL) Ant-CF₃ molecular crystals exhibit laser power-dependent permanent mechanical bending in 2D and 3D. Investigation of a single-crystal using spatially-resolved Raman/FL/electron microscopy, and theoretical calculations revealed photothermal (Z,E)/(E,E) isomerization-assisted transition from crystalline to amorphous phase at the laser-exposed regions. This phenomenon facilitates the dimension engineering of a 1D crystal waveguide into 2D waveguide on a substrate or a 3D waveguide in free space. The bends can be used as interconnection points to couple different optical elements. The presented technique has broader implications in organic photonics and other crystal-related photonic technologies.     

Rheological,morphological, thermal,and mechanical properties of blends of vectra A950 and poly(trimethylene terephthalate): A study on a high-viscosity-ratio system

Poly(trimethylene terephthalate) (PTT) and a liquid crystalline polymer, Vectra A950 (VA), were melt-blended and subjected to capillary rheometry. Effects of VA content, shear rate and temperature on viscosity and flow activation energy (E_a) were investigated. Partial fibrillation was found even though the viscosity ratio was greater than one, leading to the formation of in-situ composites. Thermal and thermogravimetric analysis of the blends suggested that they were immiscible and their thermal stabilities were enhanced. From tensile tests, the incorporation of VA improved tensile modulus, slightly decreased tensile strength, and drastically lowered elongation at break, compared to neat PTT. It was found that the blend with the best VA dispersion can be achieved at the minimum VA content (10 wt%) and lowest processing temperature (250 °C). Not only did this blend exhibit improved mechanical properties comparable to those of blends processed at temperatures closer to the crystalline-to-nematic transition of VA (～280 °C), it also shows enhanced processibility through the reduction of both melt viscosity and E_a.     

Regioselective biocatalytic hydrolysis of (E,Z)-2-methyl-2-butenenitrile for production of (E)-2-methyl-2-butenoic acid

Acidovorax facilis 72W nitrilase catalyzed the regioselective hydrolysis of (E,Z)-2-methyl-2-butenenitrile, producing only (E)-2-methyl-2-butenoic acid with no detectable conversion of (Z)-2-methyl-2-butenenitrile. (E)-2-Methyl-2-butenoic acid, produced in aqueous solution as the ammonium salt, was readily separated from (Z)-2-methyl-2-butenenitrile, and isolated in high yield and purity. The combination of nitrile hydratase and amidase activities of several Comamonas testosteroni strains were also highly regioselective for the production of (E)-2-methyl-2-butenoic acid from (E,Z)-2-methyl-2-butenenitrile.     

The geometric isomers of methyl-2,4,6-decatrienoate, including pheromones of at least two species of stink bugs

All eight geometric isomers of methyl 2,4,6-decatrienoate were synthesized from readily accessible starting materials by fully exploiting Wittig-type olefinations, and taking advantage of an easy separation of 2E and 2Z unsaturated esters. The aggregation pheromone of the brown-winged green bug, Plautia stali, methyl (E,E,Z)-2,4,6-decatrienoate (also a cross-attractant for the brown marmorated stink bug, Halyomorpha halys), was expediently produced in two easy steps from (E)-4,4-dimethoxy-2-butenal in 55% yield. The sex pheromone of the red-shouldered stink bug, Thyanta pallidovirens, methyl (E,Z,Z)-2,4,6-decatrienoate, was conveniently synthesized from 2,4-octadiyn-1-ol in 32% yield using in situ manganese dioxide oxidation-Wittig condensation in a key step.