Electrically tunable polarisation-independent blue-phase liquid crystal binary phase grating via phase-separated composite films

A simple method for fabricating polarisation-independent blue-phase liquid crystal phase grating is demonstrated by implementing photopolymerisation-induced phase separation through a binary photomask. The dynamic focusing property of the proposed liquid crystal grating is independent of the polarisation state of incident light. The efficiency of various diffraction orders for the phase grating was measured as a function of the applied voltage. Experimental results show that the maximum diffraction efficiency reaches 36% for the ±1 order, which approaches the theoretical limit ~41%. The measured rise time is 1.4 ms and fall time is 2.2 ms. Such a tunable grating has great potential for photonic applications.     

Synthesis of the first mixed ligand Mn (II) and Cd (II) complexes of 4-methoxy-pyridine-2-carboxylic acid,molecular docking studies and investigation of their anti-tumor effects in vitro

The first mixed ligand Mn (II) and Cd (II) complexes containing 4-methoxy-pyridine-2-carboxylic acid (4-mpic) and 4,4′-dimethyl-2,2′-bipyridine (dmbpy) were synthesized in this study. The geometric structures of [Mn(4-mpic)₂(dmbpy)] (complex 1 ) and [Cd(4-mpic)₂(dmbpy)] (complex 2 ) were determined by single crystal X-Ray diffraction method. FT-IR and UV–Vis spectra were also recorded to investigate vibrational and electronic properties of complexes 1 and 2 . Density functional theory (DFT) calculations were also carried out to provide a deep understanding in geometric, spectroscopic, electronic and nonlinear optical (NLO) properties of complexes 1 and 2 . The first-order hyperpolarizibility (β) parameter calculated as 332.9736 × 10⁻³⁰ esu demonstrated that complex 1 is an extremely promising candidate to NLO materials. Natural bond orbital (NBO) analysis not only verified the distorted octahedral geometries of central metal ions, but also found out the high-energy interactions responsible for biological activities for complexes 1 and 2 . Anti-cancer activities of complexes 1 and 2 were tested on human breast carcinoma cell line MCF-7 (ER and PR positive, HER2 negative) and the triple negative breast carcinoma cell line MDA-MB 231 (ER, PR and HER2 negative). Dose–response relationship derived from MTT assays indicates that complexes 1 and 2 are showing concentration-dependent effects, which could suggest a potential use for these drug combinations in cancer cell lines.     

Synthesis and polymerizations of phosphonated‐bis(methacrylamide)s for dental applications

Novel phosphonate and phosphonic acid‐containing bis(methacrylamide)s were synthesized. The phosphonate‐containing monomers ( 1a and 1b ) were synthesized by amidation of 2‐(2‐chlorocarbonyl‐allyloxymethyl)‐acryloylchloride with diethyl 2‐aminoethylphosphonate and diethyl 1‐aminomethylphosphonate. The phosphonic acid‐containing monomers ( 2a and 2b ) were synthesized by hydrolysis of 1a and 1b with trimethylsilyl bromide (TMSBr). All monomers were liquids and dissolved in water and ethanol. Thermal homopolymerization of 1a and 1b in bulk and solution using 2,2′‐azobis(isobutyronitrile) (AIBN) at 80 °C gave crosslinked polymers indicating low cyclization tendencies of these monomers. They were also homopolymerized using photo‐DSC with 2,2′‐dimethoxy‐2‐phenyl acetophenone (DMPA) as photoinitator, and their maximum rates of polymerization were found to be higher than commercial monomers 2,2‐bis[4‐(2‐hydroxy‐3‐methacryloyloxy propyloxy) phenyl] propane (Bis‐GMA) and 2‐hydroxyethyl methacrylate (HEMA), indicating their potential as reactive diluents or crosslinkers in dental materials. In fact, copolymerization with monomer 1a resulted in improvements in photopolymerization kinetics of both Bis‐GMA and HEMA. The acidic nature of the aqueous solutions (pH of 2a : 1.42, 2b : 1.53), stability under aqueous conditions after 1 month of study at 37 °C, interaction of 2a with hydroxyapatite (HAP) as representative of both monomers, and copolymerizability of the same with HEMA make these monomers suitable as adhesive monomers in dental adhesives, although their low observed reactivities may present a drawback. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Tuning the Electrochemical Properties of Novel Asymmetric Integral Sulfonated Polysulfone Cation Exchange Membranes

In this study, novel asymmetric integral cation exchange membranes were prepared by the wet phase inversion of sulfonated polysulfone (SPSf) solutions. SPSf with different degrees of sulfonation (DS) was synthesized by variation in the amount of chlorosulfonic acid utilized as a sulfonating agent. The characterization of SPSf samples was performed using FTIR and ¹H-NMR techniques. SPSf with a DS of 0.31 (0.67 meq/g corresponding ion exchange capacity) was chosen to prepare the membranes, as polymers with a higher DS resulted in poor mechanical properties and excessive swelling in water. By a systematic study, the opportunity to tune the properties of SPSf membranes by acting on the composition of the polymeric solution was demonstrated. The effect of two different phase inversion parameters, solvent type and co-solvent ratio, were investigated by morphological and electrochemical characterization. The best properties (permselectivity of 0.86 and electrical resistance of 6.3 Ω∙cm²) were obtained for the membrane prepared with 2-propanol (IPA):1-Methyl-2-pyrrolidinone (NMP) in a 20:80 ratio. This membrane was further characterized in different solution concentrations to estimate its performance in a Reverse Electrodialysis (RED) operation. Although the estimated generated power was less than that of the commercial CMX (Neosepta) membrane, used as a benchmark, the tailor-made membrane can be considered as a cost-effective alternative, as one of the main limitations to the commercialization of RED is the high membrane price.     

Synthesis and modeling of new phosphorus‐containing acrylates

New methacrylate monomers containing phosphonic acid or both phosphonic and carboxylic acids were synthesized through the reaction of t‐butyl α‐bromomethyl acrylate with triethyl phosphite followed by the selective hydrolysis of the phosphonate or t‐butyl ester groups with trimethylsilyl bromide and trifluoroacetic acid. The copolymerization of these monomers with 2‐hydroxyethylmethacrylate was investigated with photodifferential scanning calorimetry at 40 °C with 2,2′‐dimethoxy‐2‐phenyl acetophenone as a photoinitiator. Quantum mechanical tools were also used to understand the mechanistic behavior of the polymerization reactions of these synthesized monomers. The propagation and chain‐transfer reactions were considered and rationalized. A strong effect of the monomer structure on the rate of polymerization was observed. The polymerization reactivities of the monomers increased with decreasing steric hindrance and/or increasing hydrogen‐bonding capacity because of the hydrolysis of the phosphonate and the t‐butyl ester groups. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2574–2583, 2005     

Efficient immobilization and patterning of live bacterial cells

A monolayer of live bacterial cells has been patterned onto substrates through the interaction between CFA/I fimbriae and the corresponding antibody. Patterns of live bacteria have been prepared with cellular resolution on silicon and gold substrates for Salmonella enterica serovar Typhimurium as a model with high specificity and efficiency. The immobilized cells are capable of dividing in growth medium to form a self-sustaining bacterial monolayer on the patterned areas. Interestingly, the immobilized cells can alter their orientation on the substrate, from lying-down to standing-up, as a response to the cell density increase during incubation. This method was successfully used to sort a targeted bacterial species from a mixed culture within 2 h.     

Theoretical studies of molecular structure and vibrational spectra of melaminium citrate

The molecular geometry and vibrational frequencies of melaminium citrate in the ground state have been calculated using the Hartree-Fock (HF) and density functional method (B3LYP) with 6-31G(d) basis set. The optimized geometric bond lengths and bond angles obtained by using HF and density functional theory (DFT, B3LYP) show the best agreement with the experimental data. Comparison of the observed fundamental vibrational frequencies of melaminium citrate and calculated results by density functional B3LYP and Hartree-Fock methods indicate that B3LYP is superior to the scaled Hartree-Fock approach for molecular vibrational problems.     

Optical and structural properties of aluminium oxide thin films prepared by a non-aqueous sol–gel technique

Clear aluminium oxide sols without precipitation were synthesized via a non-aqueous sol–gel technique using three different alcohols (ethanol, isopropanol and n-butyl alcohol) as solvent, aluminium sec-butoxide as a precursor and acetyl acetone as a chelating agent. Although all sols could be successfully used to prepare thin films, the most stable one was prepared with n-butyl alcohol. Highly transparent, homogenous and amorphous aluminium oxide thin films were obtained on Si substrates after a heat treatment at 500 °C. X-Ray photoelectron spectroscopy (XPS) and Fourier transform infrared absorption (FT-IR) spectroscopy revealed all films were hydroxide free. The optical and structural properties of the films were particularly investigated. Any significant difference except from thickness on the film properties was not observed by changing the alcohol. Refractive index was used as an indication of the porosity of the films and ranged from 1.54 to 1.60.     

Synthesis and evaluation of new dental monomers with both phosphonic and carboxylic acid functional groups

Novel dental monomers containing both phosphonic and carboxylic acid functional groups were prepared. The monomers were based on t‐butyl α‐bromomethacrylate (t‐BuBMA) and synthesized in three steps: The reaction of o‐hydroxyaryl phosphonates [diethyl (2‐hydroxyphenyl) phosphonate, tetraethyl (2,5‐dihydroxy‐1,4‐phenylene) diphosphonate and tetraethyl 5,5′‐(propane‐2,2‐diyl)bis(2‐hydroxy‐5,1‐ phenylene) diphosphonate] with t‐BuBMA, the hydrolysis of phosphonate groups to phosphonic acid using trimethyl silylbromide, and the hydrolysis of the t‐butyl groups to carboxylic acid with trifluoroacetic acid. The monomers were solids and soluble in water and ethanol. The structures of the monomers were determined by Fourier transform infrared (FTIR), ¹H, ¹³C, and ³¹P nuclear magnetic resonance (NMR) spectroscopy. The copolymerization behaviors of the synthesized monomers with glycerol dimethacrylate were first investigated in bulk using photodifferential scanning calorimetry at 40 °C with 2,2′‐dimethoxy‐2‐phenyl acetophenone as photoinitiator. Then, the solution copolymerization of the monomers with acrylamide in ethanol and water was studied, indicating that the synthesized monomers are incorporated into the copolymers. The acidic nature of the aqueous solutions of these monomers (pH values 1.72–1.87) is expected to give them etching properties important for dental applications. The interaction of the monomers with hydroxyapatite was investigated using ¹³C NMR and FTIR techniques. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1953–1965, 2009