PREPARATION AND PROPERTIES OF ETHYL-CYANOETHYL CELLULOSE/POLYACRYLIC ACID COMPOSITE FILMS WITH REFLECTION COLORS*

Ethyl-cyanoethyl cellulose [(E-CE)C]/acrylic acid (AA) becomes a cholesteric liquid crystalline solution withvivid colors when the (E-CE)C concentration is 42 wt%～52 wt%. (E-CE)C/polyacrylic acid (PAA) composites withcholesteric structure were prepared by polymerzing AA in (E-CE)C/AA liquid crystalline solutions. The layers of orderedpolymer chains in the cholesteric phase were inclined during polymerization and the degree of the inclination depended onthe polymerization temperature and the concentration of the solution before polymerization. The cholesteric structure in thecomposites could not be changed when temperature was lower than 100℃. Cross-linking of the PAA in compositesimproved their water-resistance. The cholesteric order of the composites without cross-linking was destroyed when theywhere immersed in water. The color derived from the selective reflection of the cholesteric phase of the cross-linkedcomposites turned from blue to red after the composites absorbed water. The color of the composites could be returned to theoriginal one when the absorbed water was removed from the swollen composites.     

Macromolecular cholesteric order observed by electron microscopy

The macromolecular cholesteric structure in the ethyl-cyanoethyl cellulose [(E-CE)C]/acrylic acid [AA] cholesteric liquid crystalline solutions is studied by directly observing the morphology and structure of the ethyl-cyanoethyl cellulose [(E-CE)C]/polyacrylic acid [PAA] using electron microscopy. A periodical lamellar structure is observed in ultrathin slices of the composites with cholesteric order by both transmission electron microscopy (TEM) and low-voltage scanning electron microscopy (LVSEM). It is suggested that the periodical lamellar structure is induced by the twist of the molecular orientation in the cholesteric phase and reflects the structural features of the macromolecular cholesteric phase. The macromolecular cholesteric phase exhibits the twisted ring morphology in the initial stage of the formation of the liquid crystalline phase. The swelling of the ultrathin slices with cholesteric order in water is heterogeneous, which suggests the tight packing of the (E-CE)C chains in the direction of the helix axis in the macromolecular cholesteric phase. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 439–445, 1998     

Textures and defects in lyotropic liquid crystals of ethyl-cyanoethyl cellulose

Textures and defects in ethyl-cyanoethyl cellulose [(E-CE)C]/dichloroacetic acid (DCA) cholesteric liquid crystalline solutions and in (E-CE)C/polyacrylic acid (PAA) composites were observed and studied by polarizing microscopy and electron microscopy. The existence of χ, λ and τ disclinations were observed in the mesophase with disk-like and band-like textures. Pairs of disclinations with different signs were also found in the mesophase with the band-like texture. Domain walls were observed in (E-CE)C/PAA composite films with cholesteric order by TEM. The orientation of polymer chains in the vicinity of the core of the disclinations is discussed.     

乙基氰乙基纤维素/交联聚丙烯酸复合物膜的溶胀行为

研究了乙基氰乙基纤维素 [(E CE)C] 交联聚丙烯酸 [PAA]胆甾相液晶复合物膜的厚度以及膜的组成对膜在水中的溶胀行为的影响 .复合物膜越厚则达到溶胀平衡所需要的时间越长 ,但是其最大溶胀率是相同的 .复合物膜的最大溶胀率先是随着 (E CE)C浓度的增加而增加 ,当 (E CE)C的浓度大于 5 1wt%的时候 ,复合物膜的最大溶胀率几乎不再发生变化 .复合物膜的交联密度越大 ,其最大溶胀率越小 ,溶胀速率也随着膜的交联 (点 )密度的增加而减小 .研究还发现复合物膜的交联 (点 )密度越大 ,其溶胀前后最大选择性反射光波长的位移也越小 .     

Alignment of liquid crystal molecules on oriented (E-CE)C/PAA films

A film of ethyl-cyanoethyl cellulose/polyacrylic acid, (E-CE)C/PAA, using an alignment layer of liquid crystal (5CB), was prepared by shearing and then photo-polymerization of an (E-CE)C/AA solution. The orientation of the (E-CE)C chains in the sheared film and the alignment of the 5CB molecules on the films were investigated by polarizing optical microscopy and FTIR. It was found that the (E-CE)C/PAA oriented film showed perfect alignment ability for the 5CB molecules. The director of the 5CB molecules on the oriented film does not lie along the orientation direction of the (E-CE)C main chains, but inclines to that of the (E-CE)C main chains. The direction of the 5CB molecular orientation on the (E-CE)C/PAA oriented film is influenced by the degree of orientation of the (E-CE)C chains in the oriented film.     

Concentration dependence of magnetic field effects on the ethyl-cyanoethyl cellulose/dichoroacetic acid cholesteric phase

The effects of an external magnetic field with intensity 9.4 T on the cholesteric phase in ethylcyanoethyl cellulose (E-CE)C]/dichloroacetic acid liquid crystalline solutions were investigated for different concentrations. It was found that the diamagnetic anisotropy of (E-CE)C is negative and the effect of the magnetic field on the orientation of the cholesteric phase is influenced by the concentration of the solution, because the liquid crystalline properties of the solutions vary with the concentration.     

Concentration dependence of magnetic field effects on the ethyl-cyanoethyl cellulose/dichoroacetic acid cholesteric phase

The effects of an external magnetic field with intensity 9.4 T on the cholesteric phase in ethylcyanoethyl cellulose (E-CE)C]/dichloroacetic acid liquid crystalline solutions were investigated for different concentrations. It was found that the diamagnetic anisotropy of (E-CE)C is negative and the effect of the magnetic field on the orientation of the cholesteric phase is influenced by the concentration of the solution, because the liquid crystalline properties of the solutions vary with the concentration.     

Effects of external fields on macromolecular cholesteric phase

Effects of external fields such as magnetic field and boundary conditions on supramolecular structure, molecular arrangement and the texture of the ethyl-cyanoethyl cellulose cholesteric liquid crystalline solutions were investigated. It was found that the molecules of (E-CE)C are oriented to perpendicular to the magnetic field and the diamagnetic anisotropy of (E-CE)C is negative. With homeotropic anchoring boundary condition, the molecules are aggregated with focal-conics arrangement the molecules are aggregated with planar arrangement with homogeneous anchoring boundary condition. The effects of the external field on the orientation of the cholesteric phase were influenced by the concentration of the solution because the twist power of the cholesteric was varied with the concentration. And the effects are also restrains by the surface tension of the interphase.     

Relaxation Processes in sheared films of ethyl-cyanoethyl cellulose cholesteric liquid crystalline solutions

The relaxation processes in sheared films of ethyl-cyanoethyl cellulose [(E-CE)C]/acrylic acid (AA) cholesteric liquid crystalline (LC) solutions were studied by polarizing optical microscopy (POM) and UV-Vis spectrophotometry. Under shearing normal to the helix axis and above the critical shear rate, the planar texture arrangement of the (E-CE)C/AA cholesteric LC solution was destroyed and transformed to the nematic phase. Observed by POM, the banded texture formed quickly following the cessation of the shear, but it was unstable and disappeared after several minutes. The reflection spectrum of the sheared (E-CE)C/AA cholesteric LC solution film was recorded as a function of relaxation time. It was found that the selective reflection property was lost under the shear, but the shape of the reflection spectrum recovered quickly with cessation of the shear, and the reflection peak in the spectrum became sharper with time, returning to the original form before shearing. A proposed model of the structural transformation during the relaxation was confirmed by additional optical measurement and transmission electron microscopy.     

UV irradiation gradient induced banded texture in photo-polymerized ethyl-cyanoethyl cellulose/poly(acrylic acid) cholesteric liquid crystalline films and patterns fabrication thereof

The photo-polymerization-induced banded texture of ethyl-cyanoethyl cellulose/acrylic acid/copper acrylate ((E-CE)C/AA/CuAA₂) cholesteric liquid crystalline (CLC) solutions were investigated. The results indicate that the CLC phase can be fixed by the photo-polymerization. Banded texture was obtained in the photo-polymerized CLC films. The orientation of the banded texture induced by the photo-polymerization depends on the gradient of UV irradiations on the surface of the (E-CE)C/AA/CuAA₂ CLC solutions. CLC films with different patterns can be obtained by introducing the UV irradiation gradient on the (E-CE)C/AA/CuAA₂ CLC solutions surface by using masks with different patterns. The simple approach for the fabrication of CLC films with different patterns may have the potential application in the fields of holographic image storage.     

BAND-LIKE TEXTURE OF ETHYLCYANOETHYL CELLULOSE MESOPHASE

In the ethyl-cyanoethylcellulose ((E-CE)C)/dichloroacetic acid (DCA) cholesteric liquid crystalline solution, the hand-like texture is formed when the mesophase aggregates with the disk-like texture grow to big enough and merge with each other with increasing concentration. The band-like texture is composed of parallel equidistant bright and dark alternative strips which are about 0.2-2.0 μm in width. In the band-like texture, the layers of ordered polymer chains are perpendicular to the solution film and the axes of helicoids are parallel to it. The width of the strips is different in different zones. Under the effect of an external magnetic field, the strips in the band-like texture first become wider and then narrower gradually.Moreover, the axes of helicoids in the (E-CE) C/DCA mesomorphic solution change from the direction normal to the magnetic field to the agreement with the magnetic field direction.     

PVA/PAA thermo-crosslinking hydrogel fiber: preparation and pH-sensitive properties in electrolyte solution

The preparation of thermo-crosslinking hydrogel fibers composed of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) was presented. The hydrogel fiber was prepared by extruding the spinning dope from in situ polymerization of acrylic acid in the presence of PVA into coagulating bath of saturated ammonium sulfate aqueous solution. The network was formed by thermally heating the dried fibers under vacuum. The final hydrogel fibers exhibit pH-sensitive behavior and show hysteresis loop in the pH range from 2.5 to 12.5. The pH value at which the swelling ratio of the fiber had a jump shifted to lower value with increasing the PAA content within the network. Increasing the heating temperature and time for the fibers, the swelling ratio decreased and the jump point pH shifted to higher pH value. The oscillatory swelling/contracting behavior of the hydrogel fiber exhibited a well reversible pH-responsive property.     

THE MORPHOLOGY AND STRUCTURE OF ETHYLCYANOETHYL CELLULOSE IN STYRENE AND POLYSTYRENE

Ethyl-cyanoethyl cellulose ((E-CE)C)/styrene solution could form anisotropic system when the concentration was high enough. The (E-CE)C/polystyrene(PS)multiphase polymer could be obtained by radical polymerization of the styrene in the solution. The (E-CE)C/PS multiphase polymer maintained both the crystalline structure of the (E-CE)C and the amorphous structure of the PS. In the multiphase polymer produced from the isotropic solution, however, the (E-CE)C formed spherulites and spread in the PS amorphous phase. While, in the multiphase polymer produced from the anisotropic solution, the (E-CE)formed cylinderic crystalline aggregates. Moreover, the ordered lamellar texture was also observed in the multiphase polymer produced from the anisotropic solution.     

活性炭复合改善聚丙烯酸凝胶耐盐性及其溶胀机理

在活性炭(Ac)存在的情况下通过自由基溶液聚合,以过硫酸铵为引发剂,N,N′-亚甲基双丙烯酰胺为交联剂,制备了活性炭复合聚丙烯酸凝胶(PAA/AC)。 考察了凝胶在蒸馏水、生理盐水和不同pH值缓冲溶液中的平衡溶胀比以及溶胀动力学,结果表明,活性炭能有效提高凝胶的平衡溶胀比,在实验设计的pH值范围内复合凝胶具有比PAA凝胶更高的平衡溶胀比,蒸馏水和生理盐水中PAA/AC凝胶的平衡溶胀比分别可达到303和60 g/g,约为PAA凝胶的2.4倍。 讨论了凝胶的溶胀机理,结果表明,活性炭成分的介入破坏了聚合物链段之间的聚集态结构,减弱了聚合物链段之间的相互作用,提高了凝胶的溶胀能力。 示差扫描量热仪测定复合前后凝胶的玻璃化转变温度,扫描电子显微镜观察了复合前后凝胶的断面网络结构,结果进一步表明活性炭复合后聚合物链段之间的作用力减弱。     

Effect of thermal annealing on a bilayer polyvinyl alcohol/polyacrylic acid electrospun hydrogel nanofibres loaded with doxorubicin and clarithromycin for a synergism effect against osteosarcoma cells

Polyvinyl alcohol/polyacrylic acid (PVA/PAA) bilayer hydrogel nanofibres were successfully fabricated by electrospinning and physically crosslinked via heat treatment. The effects of the thermal annealing process on the structure, morphology, swelling, thermal properties and hydrophilicity of electrospun nanofibres were investigated. In addition, these membranes were also used to incorporate doxorubicin and clarithromycin for osteosarcoma treatment, one in each layer. These drugs were used because it is hypothesized in this work that a synergism occurs between both drugs. So, these membranes were analyzed towards their dual-drug release and potential cytotoxicity towards the U2OS human osteosarcoma cell line. Moreover, the water contact angle, disintegration, swelling and weight loss studies confirmed the rapid swelling and improved water stability of the annealed PVA/PAA bilayer nanofibres. The annealed bilayer nanofibres exhibited an increase in the average diameter and degree of crystallinity. In addition, the results revealed that a variation occurred in the degree of hydrophilicity of annealed PVA/PAA bilayer nanofibres. The PAA nanofibres surface exhibited higher hydrophilicity than the PVA nanofibres surface. Drug delivery presented to be as fast rate release for clarithromycin and slow-rate release for doxorubicin, which may be advantageous because both drugs exhibited to be synergetic for certain dosages presenting the combination of the drugs higher than 50% of cell inhibition, while these membranes had higher inhibition values (up to 90%), which was attributed to the PAA but also the drugs. These unique properties are of potential interest in drug delivery applications for dual drug delivery where the tunability of surfaces is desirable.     

Hydrostatic pressure effects on polymer cholesteric liquid-crystalline structure. I. Equilibrium structure of hydroxypropyl cellulose aqueous solution

The effect of pressure on the polymer cholesteric liquid-crystalline structure of hydroxypropyl cellulose aqueous solutions was studied using reflection spectra measurements. Pressures applied to the polymer liquid crystals ranged from 1 to 2000 bar. The equilibrium reflection spectrum of the cholesteric structure shifted to longer wavelengths, showing that the cholesteric pitch of the liquid-crystalline structure increases as the applied pressure increases. At pressures higher than 200 bar the maximum wavelength of reflection shifted linearly with the increase in applied pressure. At lower pressures, the cholesteric structure was influenced by the surface plane of the quartz window.     

Neutral and Charged Brushes Covalently Grafted from OH-Functionalized Mica Surfaces using Surface-Initiated ATRP – Swelling Investigation by AFM

Poly(acrylic acid) (PAA) and poly(tert-butyl acrylate) (PBA) brushes of various grafting densities were prepared via surface-initiated polymerization of tert-butyl acrylate on mica. PAA was prepared by hydrolyzing the PBA brushes. The swelling behavior of PBA and PAA brushes was studied as a function of grafting density by AFM. The swelling of the polymer layer was found to be higher for PAA in water than for the PBA sample swollen with DFM.     

pH敏感的聚(L-谷氨酸)-交联聚丙烯酸水凝胶的合成与性能研究

通过在聚L-谷氨酸侧链部分接枝甲基丙烯酸2-羟乙酯得到含有双键的聚(L-谷氨酸),将其与丙烯酸共聚得到由聚(L-谷氨酸)侧链接枝并交联聚丙烯酸的pH敏感水凝胶.研究水凝胶在不同pH的缓冲溶液中的溶胀性、溶胀动力学,并通过SEM观察水凝胶的微观结构.结果表明,水凝胶在低pH环境下的溶胀率明显低于高pH环境中的溶胀率,不同...     

A study on the swelling behavior of poly(acrylic acid) hydrogels obtained by electron beam crosslinking

Poly(acrylic acid) (PAA) hydrogels were prepared by using electron beam (EB) crosslinking of PAA homopolymer from its aqueous solutions. The swelling behavior of the hydrogels was studied as a function of the concentration of PAA solution, radiation dose, pH of the swelling medium and swelling time. Also the environmental pH effect on the water diffusion mode into hydrogels was investigated. These hydrogels clearly showed pH-sensitive swelling behavior with Fickian type of diffusion in the stomach-like pH medium (pH 1.3) and non-Fickian type in the intestine-like pH medium (pH 6.8).     

Hydrostatic pressure effects on polymer cholesteric liquid-crystalline structure. I. Equilibrium structure of hydroxypropyl cellulose aqueous solution

Abstract

The effect of pressure on the polymer cholesteric liquid-crystalline structure of hydroxypropyl cellulose aqueous solutions was studied using reflection spectra measurements. Pressures applied to the polymer liquid crystals ranged from 1 to 2000 bar. The equilibrium reflection spectrum of the cholesteric structure shifted to longer wavelengths, showing that the cholesteric pitch of the liquid-crystalline structure increases as the applied pressure increases. At pressures higher than 200 bar the maximum wavelength of reflection shifted linearly with the increase in applied pressure. At lower pressures, the cholesteric structure was influenced by the surface plane of the quartz window.