Polarized spectroscopy of hybrid materials of chiral Schiff base cobalt(II), nickel(II), copper(II), and zinc(II) complexes and photochromic azobenzenes in PMMA films

A chiral Schiff base complex, bis(N-R-1-phenylethyl-3,5-dichlorosalicydenaminato) cobalt(II) was prepared newly and characterized to be a distorted tetrahedral trans-[CoN₂O₂] coordination geometry. Organic/inorganic hybrid materials containing the related cobalt(II), nickel(II), copper(II), and zinc(II) complexes and photochromic azobenzene in polymethylmethacrylate (PMMA) cast films were assembled for comparison of their flexibility and molecular arrangement in the photofunctional medium. Characterization of each component and hybrid materials was carried out by means of absorption and CD spectra and thermal analysis (TG–DTA and DSC). Moreover, we have attempted to observe changes of conformation and/or molecular arrangement of the complexes or azobenzene induced by cis–trans photoisomerization of azobenzene after alternate irradiation of polarized UV and visible light. Gradual increase of optical anisotropy was observed for all the hybrid materials regardless of flexibility of Schiff base complexes, and the degree of dichroism and weak intermolecular interactions were discussed based on polarized absorption electronic spectra.     

含手性末端基偶氮聚合物膜的全息光栅研究

偶氮苯侧链型高分子由于其含有偶氮苯基团 ,在光作用下会发生可逆的顺反异构过程 ,具有光致取向特性 ,在光学处理、衍射光学、投影显示、光开关等许多方面具有潜在的应用性[1] .近 1 0多年来国内外学者对此类化合物进行了广泛的研究 ,已有文献报道可利用Ａｒ+激光束在偶氮苯聚合物薄膜上直接“写入”表面凸起光栅 ,并且通过原子力显微镜观测到光栅起伏 .这种光栅很稳定 ,并可以利用光学方法“擦去” .偶氮苯聚合物上述独有的性质引起了许多学者的兴趣[2 ,3] .另一方面 ,由于旋光性聚合物在光学物理性质上的优势 ,我们已将手性基团引入偶氮苯…     

Amorphous Porous Organic Polymers Based on Schiff‐Base Chemistry for Highly Efficient Iodine Capture

Porous organic polymers (POPs) have been considered as prominent adsorbents for volatile iodine. So far, both crystalline and amorphous POPs have accomplished excellent iodine capture capability. Considering the difficulty and challenges in preparing perfect crystalline POPs, more explorations into developing versatile amorphous POPs are needed. Herein, amorphous POPs based on the Schiff‐base reaction were designed and synthesized for volatile iodine removal. Four amorphous POPs products named as NDB‐H , NDB‐S , ADB‐HS , and ADB‐S obtained under different solvothermal conditions were investigated in terms of their morphologies, porosity, and their iodine enrichment performance in detail. It is noteworthy that excellent efficiency for removing iodine vapor was acquired for NDB‐S (≈425 wt %), ADB‐HS (≈345 wt %), and ADB‐S (≈342 wt %). Remarkably, NDB‐H exhibited an iodine capture capacity up to ≈443 wt %. Excellent reusability was obtained as well. Amorphous NDB‐H has accomplished an extremely high iodine capture performance, illustrating the great chance to exploit versatile amorphous POPs for iodine enrichment and removal based on Schiff‐base chemistry.     

Synthesis,Characterization, and Anticancer Potency of Branched Poly (p-Hydroxy Styrene) Schiff-Bases

A significant issue in cancer biology is finding anticancer therapies that effectively kill cancer cells. Through the use of several aldehydes, Schiff bases based on branched poly (p-hydroxy styrene) are created. The branched polymer is first chloroacetylated, then aminated with 1,4-phenylenediamine, and finally, aldehydes are reacted with the aminated polymer to produce the Schiff base compounds. Through the utilization of FTIR, TGA, XRD, NMR, and elemental analysis, all synthesized Schiff-bases are identified and characterized. Further, the antineoplastic potential of all Schiff bases is evaluated against different cancer cell lines. The results gained from this study indicate that the Schiff base polymers have cytotoxic power against cancer cells depending on cancer cell type and this antiproliferation potency is dose-concentration dependent. Importantly, the prepared S1 Schiff-base polymer shows potent cytotoxicity and is able to trigger the apoptosis and reactive oxygen species (ROS) in MCF-7 cells. Further, it downregulates VEGFR protein expression. The Schiff base polymers would have extensive applications in the biological disciplines.     

Syntheses and properties of photochromic polymers of the azobenzene and thiazine series

Photochromic polymers of the azobenzene and thiazine series were synthesized via two routes: (1) synthesis of vinyl photochromic monomers and subsequent polymerization and (2) chemical reactions of the substrate polymers with photochromic components. Polyvinylaminoazobenzenes, polyvinylhydroxyazobenzenes, polyacrylamidomethylaminoazobenzenes, and polyacrylamidomethylthionine were thus prepared and their photochromic behavior investigated. In the case of azobenzene polymers, irradiations from a 100-W projection lamp are enough to induced reversible changes in absorption spectra both in benzene solutions and film states, their absorption maxima being located around 400 mμ in the dark. Better results are obtained for some polymers as compared with the corresponding low molecular weight compounds; in the case of the thionine polymer (absorption maximum, ca. 600 mμ), the presence of ferrous ion remarkably enhances the photosensitivity in aqueous solutions, but incorporation of some polymers containing hydroxyl groups, such as poly(vinyl alcohol), are preferable for film states.     

Pulse injection analysis of the binding of serum proteins to porous polymer gels modified with formyl groups

Highly porous spherical polymer gels were modified with formyl groups by a modified Friedel-Crafts reaction and the interaction of serum proteins with the modified gels were examined by pulse injection analysis. The introduction of formyl groups into the polymer greatly increases its protein-binding capacity, and the protein bound to the gel is not eluted by washing with acid, alkali or urea solution. The effects of temperature and the percentage of formyl group substitution on the binding capacity indicate that the binding process can be interpreted as initial approach of the protein to the polymer surface, caused by the hydrophobic interaction, followed by formation of a stable Schiff base between the polymer gel and the protein. Theoretical treatment of the elution behaviour of the protein from the polymer-packed column is also examined, with the assumption that there are three kinds of binding site in the polymer gel: surface, macropore and micropore regions. These polymers are shown to be useful for the removal of proteins from biological samples in clinical assays using immobilized enzymes.     

Synthesis of iron-containing polymers with azo dyes in the backbones or side chains

The synthesis of cationic cyclopentadienyliron-containing polymers with pendent azobenzene chromophores was accomplished via metal-mediated nucleophilic aromatic substitution reactions. All of the desired polymers were isolated as vibrantly coloured materials and displayed excellent solubility in polar aprotic solvents. Cationic and neutral cyclopentadienyliron polymers incorporating azo dyes in the backbone were also prepared. Reactions of azo dyes with dichlorobenzene complexes allowed for the isolation of cationic cyclopentdienyliron (CpFe₊) complexes with azo dye chromophores. These complexes were then reacted with 1,1′-ferrocenedicarbonyl chloride to produce the trimetallic monomers with terminal chloro groups. These monomers contained two pendent CpFe₊ cations and a neutral iron moiety in the backbone. Nucleophilic substitution reactions of these monomers with oxygen and sulfur containing dinucleophiles gave rise to a new class of polymeric materials. The pendent CpFe₊ moieties could also be cleaved from the polymer backbones using photolysis to afford novel ferrocene based polymers. The UV-vis spectra of the organoiron monomers and polymers display similar wavelength maxima however incorporating azobenzene chromophores with electron-withdrawing substituent into the polymer chains resulted in bathochromic shifts of the λ_max values.     

Holographic grating recording in azobenzene functionalized polymers

A group of 22 polymers have been synthesized to test their suitability for recording holographic gratings. Polyamides, polyimides, polyesters and their combinations were functionalized with pendant azobenzene groups containing single or double N=N. The polymers were studied using a standard degenerate two-wave mixing technique, which enables measurement of light-induced periodic modification of polymer refractive index and absorption coefficient by analysis of the diffracted light. Two qualitatively different configurations of the holographic polarization recording were used, s-s and s-p. The relationship between structural properties of polymer matrix and azobenzene groups and the holographic grating recording kinetics and light diffraction efficiency was investigated.     

重氮偶合反应合成超支化偶氮聚合物的光响应性能研究

利用重氮偶合反应和后重氮偶合反应制备了主链和端基含有不同假芪型偶氮苯生色团的超支化偶氮聚合物.利用氢核磁共振、紫外光谱、红外光谱等分析手段确定了合成聚合物的结构、玻璃化转变温度和光谱特性等.研究了聚合物光致二向色性的性能,此聚合物的取向有序度为0.063.用两束相干的P偏振Ar+激光对聚合物膜进行光加工,得到形状规则的正弦波形表面起伏光栅,末端偶氮苯基团的引入极大地增加了超支化偶氮聚合物的光响应速度.     

偶氮共轭聚合物光电特性研究进展

芳香环或杂环通过NN双键连接形成的化合物如偶氮苯、偶氮吡咯等具有π共轭结构,此类分子有顺反两种构型,他们可以在光照条件下相互转换。分子构型转变会影响电子的共轭程度及其离域特性,因此含环结构的偶氮共轭分子具有光调制特性。反式偶氮苯分子为平面结构,顺式构型分子两个苯环有一定角度的扭转分子不在同一平面,实验和理论计算结果表明偶氮苯分子的键长、键角等受溶剂和取代基影响;光照可以实现偶氮苯分子的导电性改变,目前认为其导电性改变的原因主要是光致顺反异构而改变分子尺寸而引起。通过氮氮双键连接的杂环共轭分子能显著地降低分子的能隙,并使共轭化合物在更宽的波长范围内有强吸收,能提高太阳能光伏电池的转换效率,是理想的有机光伏材料。文章还对偶氮共轭聚合物的合成方法做了介绍,分析了含偶氮结构的共轭聚合物的光相应研究现状及其未来发展趋势。     

Synthesis and Properties of Novel Aromatic Azo Compounds from Hydroxyazobenzene and Cyanuric Chloride

A new series of aromatic azo compounds with one, two, three and five azobenzene units were facilely constructed by dehydrochlorination reaction between p‐hydroxyazobenzene, 4,4′‐dihydroxyazobenzene and cyanuric chloride under very mild conditions. Their solubility, crystallinity, thermostability, UV‐vis absorption properties and photoisomerization behaviors were carefully examined. When the number of azobenzene unit grew, the solubility of the synthesized compounds basically decreased, the crystallinity of the synthesized compounds firstly rose then dropped, while the thermostability and UV‐vis absorption ability of the synthesized compounds greatly improved. All the aromatic azo compounds exhibited typical reversible photoisomerization behaviors and were expected to be applied in photosensitive material areas.     

Surface organization, light-driven surface changes, and stability of semifluorinated azobenzene polymers

A series of polymers with 4-perfluoroalkyl-modified azobenzene side groups was investigated for its light-induced changes in surface properties. The ultraviolet (UV) light activated trans to cis isomerization of the azobenzene group, and the influence of molecular order and orientation on this process were studied using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and water contact angle measurements. Light-induced molecular reorganization in the near-surface region was studied by NEXAFS using in situ UV irradiation of polymer thin films. Differential scanning calorimetry and wide-angle X-ray scattering studies showed that sufficiently long fluoroalkyl groups formed well-ordered smectic mesophases in the bulk, as well as on the surface, which was evidenced by NEXAFS. The disruption of mesogen packing by photoisomerization was found to be influenced by the fluoroalkyl segment length. Surfaces with perfluorohexyl and perfluorooctyl groups that showed high orientational order were also highly resistant to light-induced changes. In such cases, the trans-cis isomerization resulted in greater lowering of the azobenzene phenyl ring order parameters than the perfluoroalkyl order parameters. UV exposure caused reorientation of the phenyl rings of the azobenzene group, but the terminal perfluoroalkyl segments remained more or less ordered.     

Synthesis of conjugated polymers with azobenzene moieties in the main chain

Poly(phenylenevinylene)‐based conjugated polymers with azobenzene groups in the main chains were prepared by the Pd‐catalyzed coupling polymerization of divinylarenes with dihaloarenes. The Pd‐catalyzed coupling polymerization of 4,4′‐divinylazobenzene with dihaloarenes such as 1,3‐dibromobenzene, 1,4‐dibromo‐2,5‐dihexylbenzene, 4,4′‐dibromoazobenzene, and 4,4′‐diiodoazobenzene resulted in polymers with poor solubility. In contrast, soluble polymers containing azobenzene moieties in the main chains were attainable from divinylbenzenes with 4,4′‐dihaloazobenzenes if either or both of the monomers possessed hexyl groups on the aromatic rings. The number‐average molecular weight of the polymer exceeded 10,000 under optimized conditions, and the polymer showed a remarkably redshifted absorption in the visible region (456 nm). ¹H NMR and IR spectra supported that the polymers having only trans‐geometry for the double bonds. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1057–1063, 2000     

Synthesis and photoresponsive behavior of azobenzene-functionalized polythiophene films

In this paper, two kinds of azobenzene-functionalized polythiophene liquid-crystalline (LC) polymers with different spacer lengths (n = 6 and 11) were synthesized. The photochromic behaviors and photoresponsive property of these polymer films were investigated by means of spectrofluorophotometer, polarized optical microscope and ARC UV lamp. The results have shown that these liquid-crystalline polythiophene films exhibit a quite fast photochemical phase transition speed and a better opticalswitching property. Furthermore, the existence of the azobenzene moiety in the side chain has also rendered the polythiophene some interesting optical properties that can be modulated by UV light irradiation, e.g., the intensity of photoluminescent emission associated with the conjugated polythiophene main chain was found to decrease upon UV irradiation and the effect becomes more prominent when shorter spacers are used in between the azobenzene group and the main chain.     

Tailoring the liquid crystalline property via controlling the generation of dendronized polymers containing azobenzene mesogen

The first‐ and second‐generation dendronized polymers containing azobenzene mesogen were designed and successfully synthesized via free radical polymerization. The chemical structures of the monomers were confirmed by elemental analysis, ¹H NMR, and ¹³C NMR. The molecular characterizations of the polymers were performed with ¹H NMR and gel permeation chromatography. The phase structures and transition behaviors were studied using differential scanning calorimetry, polarized light microscopy, and small‐angle X‐ray scatter experiments. The experiment results revealed that the first‐generation dendronized polymer exhibited liquid crystalline behavior of the conventional side‐chain liquid crystalline polymer with azobenzene mesogen, that is, the polymer exhibited smectic phase structure at lower temperature and nematic phase structure at higher temperature. However, the second‐generation dendronized polymers exhibited more versatile intriguing liquid crystalline structures, namely smectic phase structure at lower temperature and columnar nematic phase structure at higher temperature, and moreover, the phase structure still remained before the decomposition temperature. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1149–1159, 2010     

Influence of linkage chemistry on folding,self-assembly,and photoresponse of amphiphilic azobenzene main chain polymers

Two types of amphiphilic polymers composed of azobenzene repeat units in the main chain connected either via ethynylene (acetylene) or butadiynylene (diacetylene) linkages and carrying oligo(ethylene glycol) side chains were reported. Synthesis was accomplished by polycondensation involving Sonogashira–Hagihara cross coupling and Glaser coupling, respectively. Solvent titration experiments revealed that both polymers fold into stable helices in a polar environment. While the ethynylene-bridged polymer resembled the behavior of its oligomeric counterparts, introduction of the extended diacetylene unit strengthened π,π-stacking interactions in case of the butadiynylene-bridged polymer leading to a pronounced aggregation tendency and suppressing photoisomerization in the folded state. Our study demonstrates the importance of backbone connectivity to balance intra- and intermolecular forces for the successful design of photoresponsive polymers. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 313–318     

Synthesis and characterization of a dye-functionalized polythiophene with different chromic properties

As a preliminary study aiming to possible applications, a polythiophene derivative with an azobenzene moiety (polyazothiophene) was synthesized and characterized by FTIR, ¹H NMR, DSC and HPSEC. Some aspects on the thermo- and solvatochromic properties of polyazothiophene, such as the influence of different solvents and solution concentration on the thermochromic effect, and the use of a large polarity range of solvents as well as an acid media in the solvatochromic effect were explored. Reversible thermochromic properties of dimethylformamide and toluene solutions were analyzed in the temperature range of 10-70 °C showing a blue-shift spectrum variation with temperature increase. Solvatochromic properties were observed for pure solvents and THF/hexane mixtures. Another chromic effect was achieved upon the addition of a protonic acid to the azothiophene polymer solution as result of the side- and main-chain protonation.     

Synthesis of azobenzene‐containing polythiophenes and photoinduced anisotropy

Three new polythiophenes containing an azobenzene moiety in the side‐chain were synthesized and characterized. Two of them, which are slightly soluble in tetrahydrofuran to allow the preparation of thin films from solution casting, were used to investigate the photoinduced anisotropy arising from the photoisomerization of azobenzene in this type of polymer. The results show that, unlike other amorphous azobenzene polymers, only an extremely small anisotropy can be induced on excitation with an Ar⁺ laser at 488 nm in these azobenzene‐containing polythiophenes, and that this photoinduced anisotropy is observable only by heating the polymer to some temperatures below glass transition temperature. It is suggested that the inability for azobenzene polythiophenes to display a significant photoinduced anisotropy may be caused by some structural constraints and/or a severe interference from conjugated thiophene chains that absorb strongly in the visible region. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3445–3455, 2004     

Synthesis of novel side‐chain triphenylamine polymers with azobenzene moieties via RAFT polymerization and investigation on their photoelectric properties

Two novel and well‐defined polymers, poly[6‐(5‐(diphenylamino)‐2‐((4‐methoxyphenyl)diazenyl)phenoxy)hexyl methacrylate] (PDMMA) and poly[6‐(4‐((3‐ethynylphenyl)diazenyl) phenoxy)hexyl methacrylate] (PDPMMA), which bear triphenylamine (TPA) incorporated to azobenzene either directly (PDMMA) or with an interval (PDPMMA) as pendant groups were successfully prepared via reversible addition‐fragmentation chain transfer polymerization technique. The electrochemical behaviors of PDPMMA and PDMMA were investigated by cyclic voltammograms (CV) measurement. The hole mobilities of the polymer films were determined by fitting the J‐V (current‐voltage) curve into the space‐charge‐limited current method. The influence of photoisomerization of the azobenzene moiety on the behaviors of fluorescence emission, CV and hole mobilities of these two polymers were studied. The fluorescent emission intensities of these two polymers in CH₂Cl₂ were increased by about 100 times after UV irradiation. The oxidation peak currents (I_OX) of the PDMMA and PDPMMA in CH₂Cl₂ were increased after UV irradiation. The photoisomerization of the azobenzene moiety in PDMMA had significant effect on the electrochemical behavior, compared with that in PDPMMA. The changes of the hole mobility before and after UV irradiation were very small for both polymers. The HOMO energies (E_HOMO, HOMO: the highest occupied molecular orbital) of side chain moieties of TPA incorporated with cis‐isomer and trans‐isomer of azobenzene in PDMMA and PDPMMA were obtained by theoretical calculation, which are basically consistent with the experimental results. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Copper Adsorption on Chitosan-Derived Schiff Bases

The adsorption of Cu(II) ions onto the chitosan derived Schiff bases obtained from the condensation of chitosan with salicyaldehyde (polymer I), 2,4-dihydroxybenzaldehyde (polymer II) and with 4-(diethylamino) salicyaldehyde (polymer III) in aqueous solutions was investigated. Batch adsorption experiments were carried out as a function of contact time, pH, and polymer mass. The amount of metal-ion uptake of the polymers was determined by using atomic absorption spectrometry (AAS) and the highest Cu(II) ions uptake was achieved at pH 7.0 and by using sodium perchlorate as an ionic strength adjuster for polymers I, II, and III. The isothermal behavior and the kinetics of adsorption of Cu(II) ions on these polymers with respect to the initial mass of the polymer and temperature were also investigated; adsorption isothermal equilibrium data could be clearly explained by the Langmuir equation. The experimental data of the adsorption equilibrium from Cu(II) solution correlates well with the Langmuir isotherm equation.