Reversible Trans-cis Research Articles

A novel azo-thiourea based visible light switchable anion receptor

A novel azo-thiourea based anion receptor can be synthesized by coupling a bis-azoaniline motif with butyl isothiocyanate with 45% yield under mild conditions. It was found that azo-thiourea was an excellent receptor to recognize various di-carboxylate anions. It can serve as a colorimetric sensor for azelate ion and led to a significant change in the absorption spectrum. Furthermore, a reversible trans–cis isomerization of azo-thiourea induced by visible lights was confirmed by 1H NMR spectroscopy.

Multimodal Stimuli-Responsive Poly(2-isopropyl-2-oxazoline) with Dual Molecular Logic Gate Operations

Azobenzene end-functionalized telechelic POx (Az-POx-Az) was designed for as multimodal stimuli-responsive polymer. Az-POx-Az (0.25 g/L) in physiological saline (150 mM NaCl) phosphate buffered solution (10 mM PBS, pH 7.4) exhibited fully reversible trans–cis photoisomerism upon alternate irradiation with 365 and 254 nm UV light. The photoisomerization of the azobenzene moieties influenced the lower critical solution temperature (LCST), and the cis form exhibited a slightly higher LCST than the trans form. Circular dichroism measurements of Az-POx-Az with cyclodextrins (CDs) exhibited induced circular dichroism at the absorption band of the azobenzene moiety, indicating the formation of host–guest complexes between the azobenzene moieties in Az-POx-Az and the CDs. After formation of host–guest complexes consisting of the azobenzene moieties and the CDs, Az-POx-Az exhibited increased LCSTs. Interestingly, the LCSTs of Az-POx-Az with α-CD and β-CD moved in opposite directions upon photoisomerization. By the...

Controlled Modulation of Lipid Bilayer State by a Photosensitive Membrane Effector

The lipid membrane matrix represents a 2-D liquid-crystal, the properties of which, at fixed other conditions, are locally modulated by the presence of effectors as e.g. cholesterol (passive) or proteins (passive and active). Not only does the incorporation of effectors into the host matrix locally or even globally modify the initial state of the host per se, most probably the state of the matrix in turn serves as a control tool for regulating the work of functional units (e.g. proteins).Results are presented on a membrane model system that was inoculated with a photosensitive and thus active variety of cholesterol. Azobenzene-cholesterol (azo-chol) exhibits a reversible trans-cis transition (365nm: trans- to cis-; 455nm: cis- to trans-). In a membrane, the azobenzene group, covalently connected to the cholesterol by an ester bond, is confined into the headgroup region. The system was explored by a combination of spectroscopic (UV-vis, NMR, mass spectroscopy), thermodynamic (Langmuir compression, calorimetry) and structural studies (X-ray/neutron reflectometry, grazing incidence X-ray diffraction). The conformational change of the guest upon illumination is coupled into the host system, inducing a transition of the whole membrane. The increased demand of headgroup area for the cis-azo-group pushes the membrane into a more compressed state, and vice versa for trans-azo-chol. The switching process between the two final states exhibits first-order kinetics. The state of the host bilayer is modulated as a response to the conformational switching of the guest effector via external light illumination. In a more general context, similar behavior may be found upon the conformational changes of membrane proteins during work.

Reversible Control of Radius and Morphology of Fluorene‐Azobenzene Copolymer Nanowires by Light Exposure

The preparation of photoresponsive polymer nanowires comprising photochromic azobenzene (Azo) and π‐conjugated fluorene (FO) units is reported. Well‐defined and uniform nanowires of the copolymer (PFOAzo) were successfully fabricated by the single particle nanofabrication technique after optimizing the FO:Azo ratio and the development conditions. Azo units in the PFOAzo nanowires underwent reversible trans–cis–trans isomerization upon exposure to ultraviolet or visible light, leading to changes in the radius (between ca. 6 and 8 nm) and morphology (straight or wavy) of the nanowires. The oligo(alkylfluorene) units in the backbone are found to profit the crosslinking efficiency upon high‐energy ion beam irradiation, and more importantly, provide sufficient flexibility to allow reversible photoswitching. This demonstration of the photoluminescence, semiconducting, and mechanical properties of the PFOAzo nanowires is an important advance in the evolution of electro‐mechanical nanomaterials.

Synthesis of organic–inorganic hybrid azobenzene materials for the preparation of nanofibers by electrospinning

The new photochromic hybrid materials containing different mole fractions of highly photoactive 4-[(E)-[4-[ethyl(2-hydroxyethyl)amino]phenyl]azo]-N-(4-methylpyrimidin-2-yl)benzenesulfonamide (SMERe) were prepared by a low temperature sol–gel process. The guest–host systems with triethoxyphenylsilane matrix were obtained. These materials were used to form thin transparent films by a spin-coating technique. Then the ability of thin hybrid films to reversible trans–cis photoisomerization under illumination was investigated using ellipsometry and UV–Vis spectroscopy. The reversible changes of refractive index of the films under illumination were in the range of 0.005–0.056. The maximum absorption of these materials was located at 462–486nm. Moreover, the organic–inorganic azobenzene materials were used to form nanofibers by electrospinning using various parameters of the process. The microstructure of electrospun fibers depended on sols properties (e.g. concentration and viscosity of the sols) and process conditions (e.g. the applied voltage, temperature or type of the collector) at ambient conditions. The morphology of obtained nanofibers was analyzed by an optical microscopy and scanning electron microscopy. In most instances, the beadless fibers were obtained. The wettability of the surface of electrospun fibers deposited on glass substrates was investigated.

Synthesis and characterization of azobenzene hydroxypropyl cellulose with photochromic and thermotropic liquid crystal properties

Two types of photochromic azobenzene hydroxypropyl celluloses (azo-HPCs) are prepared by homogeneous etherification of HPC with 4-(2,3-epoxypropoxy)-azobenzene and bromoethoxy-azobenzene in N,N-dimethylacetamide under mild conditions. The degree of substitution of azo moiety of azo-HPCs is tuned in the range of 0.6–1.8 by adjusting the mole ratio of azobenzene to HPC. Their chemical structures and properties are characterized by elemental analysis, infrared spectroscopy, nuclear magnetic resonance, thermogravimetric analysis, and differential scanning calorimetry. Compared to other cellulose ethers and esters with glass transition temperature (Tg) of normally larger than 100 °C, the azo-HPC derivatives display very low Tg of ca. 20–40 °C. The azobenzenoxy-ethoxy-HPC is a thermotropic liquid crystal which displays cholesteric texture at 165 °C while cooling from its isotropic melt. Their solutions show almost fully reversible trans–cis–trans transition upon alternating irradiation of UV and visible light.

Spectral and time-resolved properties of novel hetarylazo dyes containing hydrogenated quinolines and triazole moieties

The spectral characteristics of novel hetarylazo dyes containing triazole and hydrogenated quinoline moieties and the spectral and time-resolved parameters of photochemical processes occurring upon their photoexcitation were studied by stationary spectrophotometry and pulse photolysis. All compounds have an intense absorption maximum in the visible spectral range at 470–500 nm with ɛ = 17000–27000 L mol−1 cm−1. Upon excitation with the visible light, reversible trans-cis photoisomerization occurs, which is followed by thermal cis-trans isomerization. The temporal parameters of the isomerization depend on the azo dye structure. The introduction of bulky substituents in the triazole and hydroquinoline moieties results in the increase in characteristic times of the thermal transformation of the generated transient species from milliseconds to seconds and in the partial irreversibility of the process.

Triple stimuli-responsive amphiphilic glycopolymer

Triple stimuli (temperature/pH/photo)-responsive amphiphilic glycopolymer, poly(2-(dimethylamino)ethyl methacrylate-co-6-O-methacryloyl-1,2,3,4-di-O-isopropylidene-D-galactopyranose)-b-poly(4-(4-methoxyphenylazo)phenoxy methacrylate) [P(DMAEMA-co-MAIpGP)-b-PMAZO] was synthesized by atom transfer radical polymerization, followed by the hydrolysis of MAIpGP groups, resulting in the target product poly(2-(dimethylamino)ethyl methacrylate-co-6-O-methacryloyl-D-galactopyranose)-b-poly(4-(4-methoxyphenylazo)phenoxy methacrylate) [P(DMAEMA-co-MAGP)-b-PMAZO]. The composition, moleculer weight, and moleculer weight distribution of the resultant polymers were characterized by 1H NMR and gel permeation chromatography. The micelles formed in aqueous solutions were simulated by various chemical and physical stimuli and characterized by dynamic light scattering, transmission electron microscopy, and UV-vis spectroscopy. It was found that the glycopolymer is responsive to three different types of stimulus (light, temperature, and pH). The poly(2-(dimethylamino) ethyl methacrylate) segments give thermo- and pH-responsiveness. The presence of the azobenzene moiety endows the block copolymer to exhibit light-responsiveness due to its reversible trans-cis isomerization conversion. The triple stimuli-responsive glycopolymer micelles can simulate biomacromolecues in vivo/in vitro environment and can be expected to open up new applications in various fields. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2131–2138

Poly(azobenzene acrylate-co-fluorinated acrylate) Spin-Coated Films: Influence of the Composition on the Photo-Controlled Wettability

The wetting properties of spin-coated films of copolymers based on azobenzene and fluorinated units have been investigated. The copolymers, denoted as poly(Azo-co-AcRf6), have been synthesized by free-radical polymerization of different proportions of acrylate monomers bearing either an azobenzene group or a semifluorinated side chain. The UV-visible spectroscopy analysis of the different spin-coating films through a cycle of UV and visible light irradiation indicates the reversible trans-cis isomerization of azobenzene groups. Simultaneously, atomic force microscopy shows that surface roughness does not exceed 1 nm. Advancing and receding contact angles of water and diiodomethane have been measured before and after UV photoirradiation of the different surfaces. In particular, a decrease in the advancing contact angles has been observed upon trans-cis isomerization of azobenzene groups. Switching variations up to 50° have been evidenced without any introduction of surface nanoroughness. Surface free-energy evaluations have been deduced from these measurements, including dispersive and polar components. The results show that, through surface composition and UV photoirradiation, a large range of surface free-energies can be obtained, from 7 to 46 mN·m(-1).

Preparation, photoisomerization, and microfabrication with two‐photon polymerization of crosslinked azo‐polymers

ABSTRACTWe report the preparation, photoisomerization properties, and three‐dimensional (3D) microstructure fabrication with two‐photon polymerization of crosslinked azo‐polymers. A series of bi‐acrylate‐substituted azobenzene derivatives were designed and synthesized as the monomers and/or crosslinkers of the crosslinked azo‐polymers. The doping concentration of the derivatives in pre‐polymer resins was significantly increased due to the introduction of bulky tert‐butyl and flexible alkyl chains. The double‐exponential dynamics of trans‐to‐cis photoisomerization of the azo‐polymers indicated the coexistence of different processes for the azobenzene moieties in the polymeric crosslinked networks. The crosslinked azo‐polymers exhibited ideal “on–off” switching performance in the highly reversible trans–cis–trans isomerization cycles. Furthermore, we prepared a photoresist containing the azobenzene derivative for 3D microstructure fabrication based on two‐photon polymerization. A woodpile photonic crystal with a photonic bandgap at telecommunication wavelength region was successfully fabricated with the azobenzene‐containing photoresist, which would open the way for the design and manufacturing of miniature optical communication devices. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2947–2956, 2013

Reversible photoisomerization of azobenzene-containing polymeric systems driven by visible light

A novel class of azobenzene-containing polymeric systems with reversible trans–cis photoisomerization behavior driven by visible light (ca. 450 nm) has been successfully prepared and this opens up a pathway for azobenzene-based systems in biomedical applications.

Different formation kinetics and photoisomerization behavior of self-assembled monolayers of thiols and dithiolanes bearing azobenzene moieties

Self-assembled monolayers (SAMs) containing azobenzene moieties are very attractive for a wide range of applications, including molecular electronics and photonics, bio-interface engineering and sensoring. However, very little is known about the aggregation and photoswitching behavior that azobenzene units undergo during the SAM formation process. Here, we demonstrate that the formation of thiol-based SAMs containing azobenzenes (denoted as AzoSH) on gold surfaces is characterised by a two-step adsorption kinetics, while a three-step assembly process has been identified for dithiolane-based SAMs containing azobenzenes (denoted AzoSS). The H-aggregation on the AzoSS SAMs was found to be remarkably dependent on the time of self-assembly, with less aggregation as a function of time. While photoisomerization of the AzoSH was suppressed for all different assembly times, the reversible trans-cis photoisomerization of AzoSS SAMs formed over 24 hours was clearly observed upon alternating UV and Vis light irradiation. We contend that detailed information on formation kinetics and related optical properties is of crucial importance for elucidating the photoswitching capabilities of azobenzene-based SAMs.

Molecular orientation and photoswitching kinetics on single-walled carbon nanotubes by optical second harmonic generation

Electrical conduction through chromophore-functionalized nanotubes can be modulated by light with wavelengths expected to isomerize the chromophores. Here, we use second harmonic generation to directly measure the orientation and photoisomerization kinetics of azo-benzene chromophores on single-walled carbon nanotubes. We find a net chromophore orientation with an average chromophore tilt angle of 40° ± 3°. We show that this angle can be reduced effectively to zero with an applied corona field. Periodic illumination with unpolarized 495 nm light induces reversible trans-cis switching, enabling the extraction of switching time scales both with and without an applied electric field.

Producing Cost Savings through an Employer Sponsored Medication Therapy Management (MTM) Program for Patients with Diabetes

A series of well-defined ABA-triblock copolymers P(NB-PtBA)x-b-P(NB-PFP)y-b-P(NB-PtBA)x were synthesized by living ring-opening metathesis polymerization (ROMP) of norbornenyl-poly(tert-butyl acrylate) (NB-PtBA), norbornenyl-pentafluorophenyl (NB-PFP) and NB-PtBA in a sequential manner by the use of Grubbs’ third generation catalyst (G3). The corresponding amphiphilic ABA-triblock azobenzene copolymers P(NB-PAA)x-b-P(NB-Azo)y-b-P(NB-PAA)x were obtained in high yields after subsequent post-polymerization modifications, including the reaction of active esters with amine-functionalized azobenzene to introduce the azobenzene unit, and the hydrolysis reaction to remove the tert-butyl groups. Under alternating UV and visible light illumination, the light response behaviors of the polymers were demonstrated by UV–Vis spectroscopy, and the reversible changes were observed as a result of the reversible trans-cis photoisomerization of azobenzene mesogens. These amphiphilic copolymers can also spontaneously self-assemble into spherical nanoparticles in an aqueous medium, and the hydrodynamic diameter increases as the hydrophobic NB-Azo content increases.

Synthesis and Characterization of Azobenzene-Functionalized Hyperbranched Polymers

Azobenzene functionalized hyperbranched polymers (HBAzPs) have been synthesized by polycondensation of 4,4′-di((2-hydroxyethoxy)azobenzene and 1,3,5-benzenetricarboxylic acid chloride in presence of triethylamine at room temperature through A2 + B3 polymerization approach. The structure and properties of HBAzPs were characterized by 1H NMR, IR, GPC, DSC and UV-Visible spectrometry. Molecular weights as well as properties of HBAzPs were found to be greatly influenced by molar ratio of monomers, amount of triethylamine and monomer concentration. HBAzP solutions in THF showed absorbances at 356 nm and 450 nm corresponding to π-π* and n-π* electronic transitions of azobenzene chromophores, respectively. A reversible trans-cis photoisomerization of HBAzPs was observed upon irradiation of UV and visible light.

A Light‐Controlled Molecular Brake with Complete ON–OFF Rotation

A light-controlled molecular machine based on cyclic azobenzenophanes consisting of a dioxynaphthalene rotating unit and a photoisomerizable dioxyazobenzene unit bridged by methylene spacers is reported. In compounds 1 and 2, 1,5- and 2,6-dioxynaphthalene moieties, respectively, are linked to p-dioxyazobenzene by different methylene spacers (n=2 in 1a and 2; n=3 in 1b), whereas a 1,5-dioxynaphthalene moiety is bonded to m-dioxyazobenzene by bismethylene spacers in 3. In 1b and 2, the naphthalene ring can rotate freely in both the trans and cis states at room temperature. The rotation speed can be controlled either by photoinduced reversible trans-cis (E-Z) isomerization of the azobenzene or by keeping the system at low temperature, as is evident from its NMR spectra. Furthermore, for the first time, we demonstrate a light-controlled molecular brake, wherein the rotation of the naphthalene moiety through the cyclophane is completely OFF in the trans isomer of compound 3 due to its smaller cavity size. Such restricted rotation imparts planar chirality to the molecule, and the corresponding enantiomers could be resolved by chiral HPLC. However, the rotation of the naphthalene moiety is rendered ON in the cis isomer due to its increased cavity size, and it is manifested experimentally by the racemization of the separated enantiomers by photoinduced E-Z isomerization.

An electron induced two-dimensional switch made of azobenzene derivatives anchored in supramolecular assemblies

Supramolecular assemblies of 4-anilino-4'-nitroazobenzene are investigated on the Au(111) surface by low temperature scanning tunneling microscopy and spectroscopy with submolecular resolution. Adsorption at 250 K leads to three different structures that are formed via hydrogen bonds: a star structure and two types of line structures: a meandering and a zigzag line. The formation of these supramolecular assemblies is affected by the available space on the fcc domains of the reconstructed Au(111) substrate as well as by the two-dimensional chirality of the molecules on the surface. The star structure is enantiomerically pure, while both types of lines consist of a racemic mixture. Bonding between homochiral pairs differ from the one between heterochiral pairs in the position of the hydrogen bonds. Inside these supramolecular assemblies two configurations of the molecules are identified: An almost straight trans-configuration and a slightly bent cis*-configuration. The trans-configuration largely reflects the structure of this isomer in gas phase, while the cis*-configuration is two-dimensional on the surface in contrast to the three-dimensional gas phase cis-configuration. The reversible trans-cis* isomerization is induced by electron tunneling through the LUMO+1 state of the molecule, which is located at +2.9 V.

Photo-induced control of bubble domains in chiral–nematic liquid crystal by a violet laser beam

The stable bubble domains generated by mixing 10% of chiral molecules into an azobenzene liquid crystal (LC)-doped nematic host can be optically controlled by a violet laser beam (415 nm). The photon-induced reversible trans–cis photo-isomerisation of azobenzene changes the helical twisting power (HTP) of LC mixtures in which the HTP of cis-azobenzene LC is lower than trans-azobenzene LC. Under the irradiation of an optical field (>20 mW cm − 2), the helical pitch distance, which is inverted proportional to the HTP, increases and the bubble domains disappear. Immediate obstruction of laser light irradiation initiates cholesteric nucleation, merging of domains and the subsequent generation of stably dispersed bubble domains.

Synthesis of azobenzene‐functionalized two‐arm, three‐arm and four‐arm telomers using polyfunctional chain transfer agents

AbstractBACKGROUND: Star‐shaped polymers are very attractive because of their interesting properties such as reduced viscosity, good solubility, low glass transition temperature and fast response to external stimuli. The incorporation of azobenzene moieties in star‐shaped polymers could significantly widen their potential applications in various optical devices. One of the most important properties of the azobenzene chromophore is its reversible trans–cis photoisomerization induced by UV or visible light. Photoisomerization induces conformational changes in azopolymer chains, which in turn lead to macroscopic variations in chemical and physical properties of the surroundings and media.RESULTS: This study reports the synthesis of azobenzene‐functionalized two‐, three‐ and four‐arm telomers via free radical telomerization using the di‐, tri‐ and tetrafunctional chain transfer agents 1,2‐ and 1,4‐benzenedimethanethiol, trimethylolpropane‐tris(2‐mercaptoacetate) and pentaerythritol‐tetrakis(3‐mercaptopropionate), respectively, in the presence of azobisisobutyronitrile. Azotelomers were characterized using gel permeation chromatography and 1H NMR and Fourier transform infrared spectroscopy. Thermal phase transition behaviors were investigated using differential scanning calorimetry and polarized optical microscopy. Azotelomers synthesized in this study showed reversible photoisomerization and a fast generation of birefringence.CONCLUSION: Considering the photoisomerization behavior and birefringence of the two‐, three‐ and four‐arm azotelomers, it can be concluded that they could be potential candidates for use in various optical devices. Copyright © 2009 Society of Chemical Industry

AB INITIO STUDY OF THE MOLECULAR STRUCTURE AND THERMAL CIS–TRANS ISOMERIZATION OF 3,3′-DIAMINO-4,4′-AZOFURAZAN AND 3,3′-DIAMINO-4,4′-AZOXYFURAZAN

In this work, we carried out the density functional theory (DFT) calculations in order to understand the molecular structures and thermal trans–cis isomerization of 3,3′-diamino-4,4′-azofurazan (DAAzF) and 3,3′-diamino-4,4′-azoxyfurazan (DAAF). We found that the azo group oxidation of DAAzF leading to the formation of DAAF induced evidently the twist of azofurazan molecule and weakened one of CN bonds connecting the furazan rings and azo group. This means that DAAzF is more stable than DAAF. In addition, the oxidation of azo group has a significant influence on the energy difference between trans- and cis-isomer of azofurazan. The energy difference between the isomers of DAAF is only about half of that of DAAzF. Furthermore, the thermal trans–cis isomerization of DAAzF and DAAF was found to follow a different mechanism: an inversion mechanism for DAAzF and a rotation mechanism for DAAF. By analyzing the reversible trans–cis isomerization process, we firstly proposed that a self-desensitization effect could be responsible for the low sensitivity of azofurazan. This new desensitization mechanism may be useful in the design of novel high energetic density material.