New chiral liquid crystal monomers and cholesteric polyacrylates: synthesis and characterisation

The synthesis of new chiral monomers (M₁ ?M₃ ) based on menthol and the corresponding polyacrylates (P₁ ?P₃ ) is described. The chemical structures, formula and phase behaviour of the obtained monomers and polymers were characterised with FT-IR, ¹H-NMR, elemental analyses, differential scanning calorimetry (DSC), polarising optical microscopy (POM) and X-ray diffraction (XRD). The effect of the mesogenic core rigidity, spacer length and menthyl steric effect on the phase behaviour of M₁ ?M₃ and P₁ ?P₃ is discussed. The expected mesophase of the compounds based on menthol can be obtained by inserting a flexible spacer between the mesogenic core and the terminal groups. For the chiral monomers and polyacrylates, their corresponding melting temperature (T _m), glass transition temperature (T _g) and clearing temperature (T _i) increased with an increase of the mesogenic core rigidity; while the T _m, T _g and T _i decreased with increasing the spacer length. M₁ and P₁ showed no mesophase, while M₂ and M₃ all revealed a SmC* and cholesteric phases. P₂ and P₃ only showed a cholesteric phase.     

Effect of the twisted alignment on the liquid crystal wave‐front corrector

The effect of twisted alignment on the phase modulation of a liquid crystal wave‐front corrector was investigated. First, the effect of twisted alignment is discussed in terms of the modulation principle of the liquid crystal molecule. Only partial incident light can be modulated because of the effect of the twisted alignment. Other unmodulated light will affect the correction accuracy and the resolution of the image. The blazed grating method is proposed to solve this problem. Adaptive correction was performed without the blazed grating method and the correction results are poor. A similar adaptive correction experiment was performed with the blazed grating method and a better correction result is obtained. The residual averaged wave‐front errors are PV = 0.101λ and RMS = 0.015λ and a resolvable image is obtained.     

The optimal cell gap determination of a liquid crystal wavefront corrector from a single photoelectric measurement

It has been a crucial technique to improve the dynamic response characteristics of a liquid crystal wavefront corrector (LCWFC) with optimal cell gap since the LCWFC needs at least 2π (or π) phase modulation in adaptive optics systems (AOSs). We have given a complete process for obtaining the optimal cell gap accurately from a single photoelectric measurement, which can be conducted with a liquid crystal (LC) cell of any known thickness. This method has been analysed theoretically and confirmed experimentally by using a wedge-shaped cell; the experimental results match very well with the theoretical analysis. The response time of an optimal gap cell can be a novel evaluation method of response performance of LC materials.     

The effect of mesogenic and non-mesogenic crosslinking units on the phase behaviour of side-chain smectic and cholesteric elastomers

Chiral monomer (M₁ ), mesogenic and non-mesogenic crosslinking agents (C₁ and C₂ ), and the corresponding liquid crystalline elastomers (P₁ and P₂ series), have been synthesised. Their chemical structures have been characterised by Fourier transform infrared or ¹H nuclear magnetic resonance and their phase behaviour investigated by differential scanning calorimetry, polarising optical miscoscopy, thermo-gravimetric analysis (TGA) and X-ray diffraction. The effect of the crosslinking unit on the phase behaviour of the elastomers has been studied. M₁ showed a cholesteric oily streak and focal conic texture. C₂ exhibited a nematic enantiotropic thread-like and schlieren texture, and a monotropic fan-shaped texture in the S_A phase. Due to the introduction of the mesogenic crosslinking unit, elastomers, P_2-1 ?P_2-5 , exhibited a cholesteric phase, while elastomers, P_1-1 ?P_1-4 , derived from a non-mesogenic crosslinking unit, exhibit a S_A phase. As the content of the crosslinking unit increased, the T _g of the P₁ series initially decreased and then increased, and the T _i of the series decreased. In the P₂ series the T _g increased, but the T _i initially increased and then decreased. TGA confirmed that all the elastomers had improved thermal stability.     

Synthesis and characterization of side chain cholesteric liquid crystalline elastomers derived from chiral bisolefinic crosslinking units

In this work we prepared a nematic monomer (4′‐allyloxybiphenyl 4′‐ethoxybenzoate, M₁ ), a chiral crosslinking agent (isosorbide 4‐allyloxybenzoyl bisate, M₂ ) and a series of new side chain cholesteric liquid crystalline elastomers derived from M₁ and M₂ . The chemical structures of the monomers and polymers were confirmed by FTIR and ¹H NMR spectroscopy. The mesomorphic properties were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy and X‐ray diffraction. The effect of the content of the crosslinking unit on phase behaviour of the elastomers is discussed. Polymer P₁ showed a nematic phase, P₂ –P₇ showed a cholesteric phase; P₆ formed a blue Grandjean texture over a broad temperature range 145–209.6°C, with no changed on the cooling. Polymers P₄ –P₇ , with more than 6?mol?% of chiral crosslinking agent, gave rise to selective reflection. Elastomers containing less than 15?mol?% of the crosslinking units displayed elasticity, reversible phase transition with wide mesophase temperature ranges, and high thermal stability. Experimental results demonstrated that, with increasing content of crosslinking agent, the glass transition temperatures first fell and then increased; the isotropization temperatures and mesophase temperature ranges decreased.     

MC8 Peptide-Mediated Her-2 Receptor Targeting Based on PEI-β-CyD as Gene Delivery Vector

A novel vector with high gene delivery efficiency and special cell targeting ability was developed using a good strategy that utilized low molecular weight polyethylenimine (PEI; molecular weight, 600 KDa [PEI600]) cross-linked to β-cyclodextrin (β-CyD) via a facile synthetic route. Human epidermal growth factor receptor 2 (Her-2) are highly expressed in a variety of human cancer cells and are potential targets for cancer therapy. MC8 peptides, which have been proven to combine especially with Her-2 on cell membranes were coupled to PEI-β-CyD using N-succinimidyl-3-(2-pyridyldithio) propionate as a linker. The ratios of PEI600, β-CyD, and peptide were calculated based on proton integral values obtained from the ¹H-NMR spectra of the resulting products. Electron microscope observations showed that MC8-PEI-β-CyD can efficiently condense plasmid DNA (pDNA) into nanoparticles of about 200 nm, and MTT assays suggested the decreased toxicity of the polymer. Experiments on gene delivery efficiency in vitro showed that MC8-PEI-β-CyD/pDNA polyplexes had significantly greater transgene activities than PEI-β-CyD/pDNA in the Skov3 and A549 cells, which positively expressed Her-2, whereas, no such effect was observed in the MCF-7 cells, which negatively expressed Her-2. Our current research indicated that the synthesized nonviral vector shows improved gene delivery efficiency and targeting specificity in Her-2 positive cells.     

Exon Array Analysis of Alternative Splicing of Genes in SOD1G93A Transgenic Mice

Alternative splicing is a common strategy for creating functional diversities of proteins. While conventional identification of splice variants generally targets individual genes in amyotrophic lateral sclerosis, we present a novel exon-centric array that allows genome-wide identification of splice variants and concurrently provides analysis of gene expression. Compare 1 was asymptomatic SOD1G93A transgenic mice with nontransgenic littermates; compare 2 was symptomatic with asymptomatic transgenic mice. RT-PCR was performed to validate. Pathway and GO analysis were performed on abnormal genes. These findings could guide us to demonstrated the potential influence of mutant human CuZn-SOD1 and of splicing regulation in pathological processes.     

Curcumin Inhibits the Sortase A Activity of the Streptococcus mutans UA159

Streptococcus mutans (S. mutans) forms part of the commensal microflora and is deemed to be the major pathogen responsible for the generation of dental caries. The enzyme, sortase A enzyme, modulates the surface properties and cariogenicity of S. mutans. Curcumin has been reported to be an inhibitor of Staphylococcus aureus sortase A. In this study, inhibition of a purified S. mutans UA159 sortase A by curcumin was evaluated. Curcumin exerted strong inhibitory activity with a half maximal inhibitory concentration (IC₅₀) of 10.2?±?0.7 μM which was lower than the minimum inhibitory concentration of 175 μM and the minimum bactericidal concentration of 350 μM. These results indicated that curcumin is a S. mutans UA159 sortase A inhibitor and therefore represents as a promising anticaries agent.     

PMAA microgel surface-supported phase transfer catalyst as reusable microreactors for ultra-deep desulfurization

The reusable microreactors, poly(methacrylic acid) (PMAA) microgels surfacely covered with 3-(trimethoxysilyl)-propyldimethyloctadecyl ammonium chloride (AEM) and K₂{W(=O)(O₂)₂(H₂O)}₂ (W2) complexes, have been synthesized by using an ion exchange reaction between AEM located on PMAA microgels and W2 in aqueous solution. The final composite microspheres and intermediate products are characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, energy dispersive X-ray spectrophotometer, and thermogravimetric analysis, respectively. The results indicated the PMAA/AEM/W2 composite microspheres with surface-wrinkling morphology and core-shell structure. The feasibility of the composite microspheres used as reusable microreactors in catalytic oxidation of dibenzothiophene (DBT) was investigated. Additionally, the effects of some factors, including the amount of the microreactors, temperature, H₂O₂/DBT molar ratio, the loaded amount of AEM, DBT concentration, and recycling times, on the catalytic oxidation were examined. The results demonstrated that the prepared composite microspheres possess high catalytic performance and reusability in the catalytic oxidation of DBT.     

Cloud point extraction combined with graphite furnace atomic absorption spectrometry for the determination of chromium species and their distribution in cigarette and cigarette ash

In this article, the contents and distribution of total chromium, Cr(III) and Cr(VI) in various cigarettes and cigarette ashes were determined by using a cloud point extraction (CPE) separation/preconcentration combined with graphite furnace atomic absorption spectrometric (GFAAS) detection. Different extraction reagents, such as tetramethylammonium hydroxide (TMAH), Na₂HPO₄, Na₂CO₃/NaOH, NaOH and H₂O, were tested for the extraction of Cr species, and the extraction efficiency was estimated. The experimental results showed that TMAH was the most efficient extraction reagent for the analyte in cigarette samples. By using the established method, the total chromium, Cr(III) and Cr(VI) in various cigarettes and cigarette ashes were determined and their distribution was studied. It was found that Cr(III) is a main species in cigarettes, but that it can be partly oxidized to Cr(VI) during smoking.