The influence of flexible spacer and the chirality of the core on the formation of chiral nematic phase of symmetric dimers containing trifluoromethyl terminal

Seven symmetric liquid crystal (LC) dimers containing different chiral cores and LC arms have been synthesised, termed EPDA-(R,S)PD, TFBDA-(R,S)PD, TFBA-(R,S)PD, TFBDA-(R)PD, TFBA-(R)PD, TFBDA-IB and TFBA-IB, respectively. TFBDA-(R,S)PD, TFBA-(R,S)PD, TFBDA-(R)PD and TFBDA-IB displayed chiral smectic A (SmA*) phase, while EPDA-(R,S)PD, TFBA-(R)PD and TFBA-IB exhibited chiral nematic (N*) phase. The effects of flexible spacer, structural type of LC arms and the chirality of the cores on the thermal properties of the dimers and the formation of N* phase have been studied. The results indicated that the chiral core was prone to induce the N* phase in LC dimer that contained nematic arms although the chirality of the core is very weak, while for the smectic LC arms containing CF3 terminal, the removal of the flexible spacer between chiral core and rigid LC units was conducive to the formation of N* phase. For example, TFBDA-(R)PD and TFBDA-IB displayed SmA* phase, while TFBA-(R)PD and TFBA-IB exhibited N* phase. However TFBA-(R,S)PD did not display N* phase, which reminded us that the chirality of the core and the conformation of the dimer also played an influence in the formation of the LC phase.     

Magnetite nanoparticles/chiral nematic liquid crystal composites with magnetically addressable and magnetically erasable characteristics

A magnetite (Fe₃O₄) nanoparticle/chiral nematic liquid crystal (N*-LC) composite was prepared and filled into a planar treated cell. The Fe₃O₄ nanoparticles had been modified by oleic acid so that they could be better dispersed in the composite. When a magnetic field was scanned on the outer surface of the cell locally, Fe₃O₄ nanoparticles moved towards the inner surface of the cell correspondingly, and the black expected information was displayed. When the magnet was applied to the opposite outer surface, the information was erased. After polymer network walls were prepared in the composite, the resolution of the information displayed increased. Then, through the formation of hydrogen bonds between the nanoparticles and chiral pyridine compound (CPC) doped in the composite, the pitch length of the N*-LC could be adjusted by altering the intensity of the applied magnetic field. The composite doped with CPC could potentially be used as a material for a type of reflective colour paper with magnetically controllable characteristics.     

Study on selective reflection properties of chiral nematic liquid crystalline composites with a non‐uniform pitch distribution

The preparation is reported of particles of photopolymerisable monomer/chiral dopant composites with a crystalline (Cr)‐chiral nematic (N*) phase transition. By mixing particles with different pitches of the N* phase in the Cr phase and crosslinking the liquid crystal (LC) monomer molecules by photopolymerisation in the planarly oriented N* phase, an N*‐LC composite film with a non‐uniform pitch distribution was obtained. Experimental results show that the bandwidth of the reflection spectrum and the location of reflection band of the composite films can be controlled accurately by controlling the pitch lengths of the N* phase of the particles. Effects of polymerisation temperature and UV intensity on the non‐uniform pitch distribution of N*‐LC composite films were investigated.     

磁性聚苯胺纳米微球的合成与表征

报道了具有核壳结构的Fe3O4-聚苯胺磁性纳米微球的合成方法和表征结果.微球同时具有导电性和磁性能.在优化的实验条件下,可得到饱和磁化强度Ms为55.4 emu/g,矫顽力Hc为62 Oe的磁性微球.微球的导电性随着微球中Fe含量的增加而下降.微球的磁性能则随着Fe含量的增加而增大.Fe3O4磁流体的粒径和磁性聚苯胺微球的粒径均在纳米量级.纳米Fe3O4粒子能够提高复合物的热性能.实验表明,磁流体和聚苯胺之间可能存在着一定的相互作用,但这种相互作用较为复杂,难于研究     

Three-layer composite magnetic nanoparticle probes for DNA

A method for synthesizing composite nanoparticles with a gold shell, an Fe3O4 inner shell, and a silica core has been developed. The approach utilizes positively charged amino-modified SiO2 particles as templates for the assembly of negatively charged 15 nm superparamagnetic water-soluble Fe3O4 nanoparticles. The SiO2-Fe3O4 particles electrostatically attract 1-3 nm Au nanoparticle seeds that act in a subsequent step as nucleation sites for the formation of a continuous gold shell around the SiO2-Fe3O4 particles upon HAuCl4 reduction. The three-layer magnetic nanoparticles, when functionalized with oligonucleotides, exhibit the surface chemistry, optical properties, and cooperative DNA binding properties of gold nanoparticle probes, but the magnetic properties of the Fe3O4 inner shell.     

The thermally sensitive characteristics of a (smectic LCP/ nematic LC/chiral dopant) ternary composite system

A transition between the transparent smectic A (SmA) phase and the light scattering chiral nematic (N*) phase was realized based on the thermally induced SmA N* phase transition for the homeotropically aligned \[liquid crystalline polymer (LCP)/liquid crystal (LC)/chiral dopant] ternary composite system. The LCP played an important role in increasing the intensity of the light scattering of the heat-induced N* phase. Meanwhile the effects of the composition of the ternary composite system on the thermo-optical characteristics were also investigated.     

Mesomorphic Characteristics of Induced Chiral Nematic Phase of [Smectic LCP,PS(4BC/DM)/Nematic LC,E7/Chiral Dopant,CB-15]-Ternary Composite System

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Y2O3纳米粒子/碳纳米管复合体的制备及其催化高氯酸铵热分解

采用化学液相沉淀法制备Y2O3纳米粒子/碳纳米管复合体(Y2O3/CNTC),利用扫描电镜(SEM)和X 射线光电子能谱(XPS)对其结构和成分进行了表征. 结果表明, Y2O3纳米粒子能负载在碳纳米管上,且负载效果较好. 采用差热分析研究了Y2O3/CNTC 对高氯酸铵热分解的催化性能, 结果表明, Y2O3 /CNTC 可显著降低高氯酸铵(AP)的高温分解峰温,表现出对AP 高温分解良好的催化性能. 相同量的Y2O3/CNTC 和纯Y2O3纳米粒子进行对比, Y2O3 /CNTC表现出更强的催化性能.当Y2O3/CNTC的质量分数为4%时,使AP的高温分解峰温提前131.14C[deg].     

Temperature dependent light transmission-light scattering switching of (homeotropic liquid crystalline polymer network/liquid crystals/chiral dopant) composite film

A (photo-polymerizable liquid crystal (LC) monomer/LCs/chiral dopant/photoinitiator) mixture with a smectic A (SmA)-chiral nematic (N*) phase transition was sandwiched between two ITO glass substrates which were not subjected to any surface orientation treatment. When an electric field-induced homeotropically oriented SmA phase of the mixture was irradiated with UV light, an oriented liquid crystalline polymer (LCP) network was formed upon photo-polymerization of the LC monomer. Then, a (homeotropically oriented LCP network/LCs/chiral dopant) composite with a SmA-N* phase transition was prepared. A focal-conic texture appeared in the heat-induced N* phase of the composite upon heating from the transparent state of the homeotropically oriented SmA phase; the focal-conic texture exhibited strong light scattering. Upon cooling the composite to the SmA phase, this phase was again homeotropically oriented due to the strong intermolecular interaction between the LC molecules and the homeotropically oriented LCP network. Thus, the transparent state of the SmA phase and the light scattering state of the N* phase occurred reversibly upon cooling and heating, accompanied by the thermal SmA-N* phase transition.     

Temperature dependent light transmission-light scattering switching of (homeotropic liquid crystalline polymer network/liquid crystals/chiral dopant) composite film

A (photo-polymerizable liquid crystal (LC) monomer/LCs/chiral dopant/photoinitiator) mixture with a smectic A (SmA)-chiral nematic (N*) phase transition was sandwiched between two ITO glass substrates which were not subjected to any surface orientation treatment. When an electric field-induced homeotropically oriented SmA phase of the mixture was irradiated with UV light, an oriented liquid crystalline polymer (LCP) network was formed upon photo-polymerization of the LC monomer. Then, a (homeotropically oriented LCP network/LCs/chiral dopant) composite with a SmA-N* phase transition was prepared. A focal-conic texture appeared in the heat-induced N* phase of the composite upon heating from the transparent state of the homeotropically oriented SmA phase; the focal-conic texture exhibited strong light scattering. Upon cooling the composite to the SmA phase, this phase was again homeotropically oriented due to the strong intermolecular interaction between the LC molecules and the homeotropically oriented LCP network. Thus, the transparent state of the SmA phase and the light scattering state of the N* phase occurred reversibly upon cooling and heating, accompanied by the thermal SmA-N* phase transition.     

分子印迹聚吡咯/Fe3O4复合材料的制备及其在识别色氨酸光学异构体中的应用

首先利用共沉淀法合成了磁性材料Fe3O4,再以吡咯为单体,L-色氨酸为模板分子,采用化学聚合法使吡咯在Fe3O4表面发生原位聚合,同时通过分子间的作用力以及氢键作用将模板分子掺杂到Fe3O4表面的聚吡咯中,从而制备了分子印迹聚吡咯/Fe3O4复合材料,并且利用该材料的磁性质实现固液分离。在1 mol/L的NaOH溶液中,通过施加1 V的电位使聚吡咯发生过氧化从而使L-色氨酸模板分子脱掺杂。根据分子印迹的原理,该分子印迹的复合材料可用于识别L-色氨酸光学异构体。将扫描电镜、X射线衍射及电化学法用于该分子印迹复合材料的表征。将该材料填入到多孔陶瓷管,将L-和D-色氨酸溶液分别流过该多孔陶瓷管,流出液用高效液相色谱检测,发现该复合材料对于L-色氨酸的富集能力接近D-色氨酸的两倍,说明该复合材料具有作为手性识别色谱固定相的潜力。     

Fluorinated chiral nematic liquid crystal dimers based on (S)-1-phenylethane-1,2-diol

ABSTRACT

A series of symmetric liquid crystal (LC) dimers with the same chiral core (S)-1-phenylethane-1,2-diol ((S)-PE) have been synthesised, termed TBDA-(S)-PE, 3F3B-(S)-PE, 3F2B-(S)-PE, 1F3B-(S)-PE, 1F2B-(S)-PE, respectively. Chemical structures and LC properties of the five symmetric LC dimers were characterised by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance hydrogen spectrometer (¹H NMR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and polarised optical microscopy (POM). TBDA-(S)-PE displayed enantiotropic chiral smectic A (S_mA*) phase while 3F3B-(S)-PE, 3F2B-(S)-PE, 1F2B-(S)-PE all displayed enantiotropic chiral nematic (N*) phase and 1F3B-(S)-PE displayed monotropic N* phase. The results indicated that the removal of the flexible spacers between the rigid mesogenic arm and the chiral core facilitated the formation of the N* phase. When the rigid mesogenic units are connected to the chiral core directly, the structure of the terminal fluorine group and the rigidity of the mesogenic unit played certain influence on the thermal properties of the LC dimers, but did not change the type of mesomorphic phase. Compared to 3F3B-(S)-PE and 1F3B-(S)-PE, 3F2B-(S)-PE and 1F2B-(S)-PE displayed wider LC ranges, respectively, suggesting molecular regularity had greater influence on LC-isotropic (I) transition temperature.     

Tunable backflow in chiral nematic liquid crystals via twist-bend nematogens and surface-localised in-situ polymer protrusions

Dynamic electro-optic response of the liquid crystal (LC) director shows a backflow effect that is manifested as an optical bounce in chiral nematic LCs (N*LC) during field-induced homeotropic-twisted transition. The bend elastic constant (K₃₃) strongly influences the dynamics of backflow at the N*LC in homeotropic-twisted transition. The cyanobiphenyl LC dimers – CB7CB, CB9CB and CB11CB – possess a unique characteristic of inherent bend molecular configuration that lowers K₃₃. With the modulation of the effective K₃₃ in dimer-doped N*LCs, we report the tunability of the optical bounce that decreases with the increase in the length of flexible spacers in LC dimers. The doped LC dimers with short spacer lengths not only generate a strong backflow with an enhanced twist degeneracy of the LC director across the cell, but also prolong the time of disappearance of the optical bounce. Furthermore, we demonstrate the suppression of the optical bounce with surface localised polymer protrusions having 50–100 nm diameters, which allow faster dynamic relaxation process and reduced backflow. We envision a novel design of a tunable microfluidic device for precise flow control of organic or inorganic matter in LC medium that exploits the tunable backflow in LC dimer-doped N*LCs.     

Polyelectrolyte/magnetite nanoparticle multilayers: preparation and structure characterization

Polyelectrolyte composite planar films containing a different number of iron oxide (Fe3O4) nanoparticle layers have been prepared using the layer-by-layer adsorption technique. The nanocomposite assemblies were characterized by ellipsometry, UV-vis spectroscopy, and AFM. Linear growth of the multilayer thickness with the increase of the layer number, N, up to 12 reflects an extensive character of this parameter in this range. A more complicated behavior of the refractive index is caused by changes in the multilayer structure, especially for the thicker nanocomposites. A quantitative analysis of the nanocomposite structure is provided comparing a classical and a modified effective medium approach taking into account the influence of light absorption by the Fe3O4 nanoparticles on the complex refractive index of the nanocomposite and contributions of all components to film thickness. Dominant influence of co-adsorbed water on their properties was found to be another interesting peculiarity of the nanocomposite film. This effect, as well as possible film property modulation by light, is discussed.     

表面活性剂碳化法合成Fe3O4/C复合物及其电化学性能

以水热法合成的包覆油酸的α-Fe₂O₃粒子为前驱体, 在氩气下500 °C煅烧1 h, 得到Fe₃O₄/C纳米复合物. 用傅里叶变换红外(FTIR)光谱, X射线衍射(XRD), 扫描电镜(SEM), X射线能量散射(EDX)谱, 高分辨透射电镜(HRTEM), 元素分析, 循环伏安(CV)和恒流充放电测试等方法对材料的结构、形貌、成分及电化学性能进行了表征. 结果表明: 所制备的Fe₃O₄/C复合物呈长约200 nm, 粗约100 nm的纺锤形, 表面碳层厚约1-2 nm, 碳含量为1.956%(质量分数); 这种复合物作为锂离子电池负极材料具有很好的循环稳定性(在0.2C (1C=928 mA·g^-1)循环80次后具有691.7 mAh·g^-1比容量)和倍率性能(在2C循环20次后依然有520 mAh·g^-1比容量). 相对于未包覆的商业Fe₃O₄粒子, 复合物显著提高的电化学性能是由于碳包覆能防止粒子聚集, 提高导电性以及稳定固体电解质界面(SEI)膜.     

Fe_3O_4/Au composite nano-particles and their optical properties

The colloid gold and magnetic particle modified with various chemical groups have been widely used in the areas of biomedical and molecular biology[1―6]. Therefore, a great deal of attention has been given to the preparation and application of colloid go…     

有机盐制备的Fe3O4-葡聚糖纳米粒子的磁性能及表征

By means of chemical co-deposition method in which added Ferric citrate and Ferrous Gluconate, Fe3O4-Dextran composite nano-particles having average diameter 26 nm, was obtained. The particles had a core of diameter 4.1 nm Fe3O4 with a shell of thickness 11 nm Dextran. In the experiment the critical structure of Fe3O4 inorganic particles abstained without N2 protection had no changes. From the result, it can be proven that organic salt has anti oxidation properties and the composite particles have superparamagnetic whose good magnetization is 52 emu/g at 300 K, and 63 emu/g at 5 K. The structure, pattern diameter and magnetic properties of the Fe3O4-Dextran composite particles were examined by means of TEM, XRD, DLS and VSM.     

CuTAPc-Fe3O4纳米复合粒子及其漆酶固定化研究

漆酶的固定化研究对基于漆酶催化的光纤生物传感器具有十分重要的意义，制备了四氨基酞菁铜(CuTAPc)-Fe3O4纳米复合粒子，并用红外(IR)、场发射扫描电镜(FEG—SEM)、X射线衍射(XRD)、能谱、粒径仪等对其进行了表征．结果表明形成了以CuTAPc包覆在Fe3O4纳米粒子表面的纳米复合粒子，粒子呈现不规则球形，且分布均匀，粒子平均粒径在50nm左右，用此纳米复合粒子通过戊二醛交联法固定了漆酶，固定后的酶比游离酶具有更好的贮存稳定性及操作稳定性，这为研制高性能的光纤生物传感器打下了较好的基础。     

Dynamic Switching of the Circularly Polarized Luminescence of Disubstituted Polyacetylene by Selective Transmission through a Thermotropic Chiral Nematic Liquid Crystal

The circularly polarized luminescence (CPL) of chiral disubstituted liquid‐crystalline polyacetylene (di‐LCPA) can be dynamically switched and amplified from left‐ to right‐handed CPL and vice versa through the selective transmission of CPL across a thermotropic chiral nematic liquid crystal (N*‐LC) phase. By combining a chiral di‐LCPA CPL‐emitting film with an N*‐LC cell and tuning the selective reflection band of the N*‐LC phase to coincide with the CPL emission band, a CPL‐switchable cell was constructed. The phase change induced by the thermotropic N*‐LC cell by varying the temperature leads to a change in the selective transmission of CPL, which enables the dynamic switching and amplification of CPL. It is anticipated that CPL‐switchable devices might find applications in switchable low‐threshold lasers and optical memory devices.     

Size-controlled synthesis of magnetite nanoparticles

Monodisperse magnetite nanoparticles have been synthesized by high-temperature solution-phase reaction of Fe(acac)3 in phenyl ether with alcohol, oleic acid, and oleylamine. Seed-mediated growth is used to control Fe3O4 nanoparticle size, and variously sized nanoparticles from 3 to 20 nm have been produced. The as-synthesized Fe3O4 nanoparticles have inverse spinel structure, and their assemblies can be transformed into gamma-Fe2O3 or alpha-Fe nanoparticle assemblies, depending on the annealing conditions. The reported procedure can be used as a general approach to various ferrite nanoparticles and nanoparticle superlattices.