Carbon nanotube/gold nanoparticles/polyethylenimine-functionalized ionic liquid thin film composites for glucose biosensing

A novel glucose biosensor based on immobilization of glucose oxidase (GOD) in thin films of polyethylenimine-functionalized ionic liquid (PFIL), containing a mixture of carbon nanotubes (CNT) and gold nanoparticles (AuNPs) and deposited on glassy carbon electrodes, was developed. Direct electrochemistry of glucose oxidase in the film was observed, with linear glucose response up to 12 mM. The PFIL-stabilized gold nanoparticles had a diameter of 2.4 +/- 0.8 nm and exhibited favorable stability (stored even over one month with invisible change in UV-vis spectroscopic measurements).

MICROSTRUCTURE AND MECHANICAL PROPERTIES OF TI-BASED METALLIC GLASS MATRIX COMPOSITES

Ti40Cu40Ni10Zr10-xScx (x = 0.5 and 1, at%) alloys were prepared by copper mould casting method. Microstructures of the phi 3 mm rod alloys were investigated by XRD and SEM. The results showed that the phi 3 mm rods were glassy matrix with TiCu crystalline phase. Mechanical properties were studied by compressive test. Ti40Cu40Ni10Zr9Sc1 alloy exhibited good compressive strength over 2200 MPa and superior compressive deformation is about 7.9%.

Electrochemical characteristics of glucose oxidase adsorbed at carbon nanotubes modified electrode with ionic liquid as binder

Multiwall carbon nanotubes (CNTs)-modified electrode has been prepared by using ionic liquid (IL) as the binder. The as-prepared CNTs-IL composite modified electrode has good biocompatibility and is a suitable matrix to immobilize biomolecules. Glucose oxidase (GOx), containing flavin adenine dinucleotide as active site, stably adsorbed on modified electrode surface has resulted in the direct electron transfer. The electron transfer rate of 9.08 s(-1) obtained is much higher than that of GOx adsorbed on the CNTs papers (1.7 s(-1)), and the process is more reversible with small redox peak separation of 23 mV This may be due to the synergetic promotion of CNTs and IL to electron transfer of the protein, especially the IL as the binder, showing better electrochemical properties than that of chitosan and Nafion. Furthermore, GOx adsorbed at the modified electrode exhibits good stability and keeps good electrocatalytic activity to glucose with broad linear range up to 20 mM. Besides, the simple preparation procedure and easy renewability make the system a basis to investigate the electron transfer kinetics and biocatalytic performance of GOx and provide a promising platform for the development of biosensors.

Room temperature ionic liquid doped DNA network immobilized horseradish peroxidase biosensor for amperometric determination of hydrogen peroxide

A novel electrochemical H2O2 biosensor was constructed by embedding horseradish peroxide (HRP) in a 1-butyl-3-methylimidazolium tetrafluoroborate doped DNA network casting on a gold electrode. The HRP entrapped in the composite system displayed good electrocatalytic response to the reduction of H2O2. The composite system could provide both a biocompatible microenvironment for enzymes to keep their good bioactivity and an effective pathway of electron transfer between the redox center of enzymes, H2O2 and the electrode surface. Voltammetric and time-based amperometric techniques were applied to characterize the properties of the biosensor. The effects of pH and potential on the amperometric response to H2O2 were studied. The biosensor can achieve 95% of the steady-state current within 2 s response to H2O2. The detection limit of the biosensor was 3.5 mu M, and linear range was from 0.01 to 7.4 mM. Moreover, the biosensor exhibited good sensitivity and stability. The film can also be readily used as an immobilization matrix to entrap other enzymes to prepare other similar biosensors.

Shear-induced spiral-like morphology of a main-chain liquid crystalline poly(aryl ether ketone)

The shear-induced spiral-like morphology of a main-chain thermotropic liquid crystalline poly(aryl ether ketone) is observed and characterized by means of polarizing light microscopy, atomic force microscopy, transmission electron microscopy and electron diffraction techniques. The spiral-like texture is formed during shearing in the temperature range of liquid crystalline to isotropic transition (335-340 degreesC), and dispersed discontinuously in the mosaic matrix. Electron diffraction results indicate that the spiral exhibits orthorhombic lateral packing of the crystals and homeotropic alignment of the molecules. The spiral formation process and possible affecting factors are discussed.

Determination of p-toluene sulfonic acid in phenol matrix by capillary zone electrophoresis with ultraviolet detection

The p-toluene sulfonic acid (MA) in phenol matrix was separated and determined by capillary electrophoresis with ultraviolet detector. the effect of the concentration and pH of the buffer on separation was investigated. Cinnamic acid has been chosen as the internal standard from four compounds, the calibration curves of PTSA in 50 mg/L phenol matrix were obtained with and without the internal standard. The linear range was from 1.25 to 12.5 mg/L and the correlation coefficient was 0.9999 for both curves. The limit of detection of PISA was 0.75 mg/L at 3 times of SIN. Finally, the concentration of PTSA in four synthesized samples was determined with method of standard additions, and the effect of matrix was discussed. The values of MA in these samples were 1.01, 0.94, 1.56 and 0.00 mg/L respectively.

A study of Aconitum alkaloids from aconite roots in Aconitum carmichaeli Debx using matrix-assisted laser desorption ionization mass spectrometry

In the present paper a study of C-19-diterpene type of aconitum alkaloids, extracted from aconite roots in Aconitum carmichaeli Debx has been made using matrix-assisted laser desorption/ionization time of Eight mass spectrometry (MALDI-TOFMS), The results demonstrated that the aconitum alkaloids from aconite roots can be determined simultaneously by this method, which was found to be superior to other analytical methods with regard to speed and sensitivity. Fourteen known aconitum alkaloids, including aconitines, benzoylaconitines and lipoaconitines, were assigned in the methanol extract and three compounds not reported before have been targeted separation. The evaluation of the efficiency of different extractions has been studied. These results suggested that the differences of the polarity and basicity of aconitine, and benzoylaconitines and lipoaconitines result from the C-8 constituent groups that are easily lost under MALDI, (C) 1998 John Wiley & Sons, Ltd.

Liquid crystalline polymer as a processing agent in blends of poly(ether-ketone)/LCP70

Blends of a liquid crystalline thermotropic copolyester (LCP70) and an amorphous phenolphthalein based poly(ether-ketone)(PEK-C) with two viscosities were prepared by melt blending. The blends' morphology, rheological and mechanical properties were investigated by DSC, SEM, mechanical and rheological tests. It was observed that the optimum composition of the PEK-C/LCP70 blend was 10 wt% LCP for both mechanical and rheological properties. When the LCP content was less than 10%, the LCP phase existed as finely dispersed fibrous domains with a diameter of about 1 mu m in the matrix, and both tensile and flexural properties were improved. In contrast, when the LCP content reached 20% or more, the LCP domains coalesced to ellipsoidal particles with a diameter of about 5 mu m, and the mechanical properties decreased as a result. It is demonstrated that pure PEK-C with a high viscosity which was difficult to process by melt extrusion, could be extruded conveniently when 10% LCP70 was incorporated. It is emphasized that LCP not only can be used as a reinforcing phase but also an effective processing agent for engineering thermoplastics, especially for those with high viscosity and narrow processing window. (C) 1997 Elsevier Science Ltd.

IN-SITU COMPOSITE - PHENOLPHTHALEIN POLYETHERSULFONE-THERMOTROPIC LIQUID-CRYSTALLINE POLYMER BLENDS

Phase behavior, thermal, theological and mechanical properties plus morphology have been studied for a binary polymer blend. The blend is phenolphthalein polyethersulfone (PES-C) with a thermotropic liquid crystalline polymer (LCP), a condensation copolymer of p-hydroxybenzoic acid with ethylene terephthalate (PHB-PET). It was found that these two polymers form optically isotropic and homogeneous blends by means of a solvent casting method. The homogeneous blends undergo phase separation during heat treatment. However, melt mixed PES-C/PHB-PET blends were heterogeneous based upon DSC and DMA analysis and SEM examination. Addition of LCP in PES-C resulted in a marked reduction of melt viscosity and thus improved processability. Compared to pure PES-C, the charpy impact strength of the blend containing 2.5% LCP increased 2.5 times. Synergistic effects were also observed for the mechanical properties of blends containing < 10% LCP. Particulates, ribbons, and fibrils were found to be the typical morphological units of PHB-PET in the PES-C matrix, which depended upon the concentration of LCP and the processing conditions.

Application of liquid pre-column capillary electrophoresis technique to the study of interaction between drug enantiomers and human serum albumin

Based on the chiral separation of several basic drugs, dimetindene, tetryzoline, theodrenaline and verapamil, the liquid pre-column capillary electrophoresis (LPC-CE) technique was established. It was used to determine free concentrations of drug enantiomers in mixed solutions with human serum albumin (HSA). To prevent HSA entering the CE chiral separation zone, the mobility differences between HSA and drugs under a specific pH condition were employed in the LPC. Thus, the detection confusion caused by protein was totally avoided. Further study of binding constants determination and protein binding competitions was carried out. The study proves that the LPC technique could be used for complex media, particularly the matrix of protein coexisting with a variety of drugs.

Theranostic applications of fluorescent liquid crystalline nanoparticles

Lipid liquid crystalline nanoparticles can find application as nanocarriers in several fields of the daily life but, very likely, the pharmaceutical arena is the most relevant. Indeed, several problems encountered in drugs administration (e.g. critical sideeffects from antitumor drugs) require alternative, less invasive, but simultaneously efficient therapeutic routes to be explored. Novel fields of personalized nanomedicine are developing in this direction. One of the most interesting is theranostic, which calls for the design of platforms capable of combining therapeutic and diagnostic functionalities. In this optic, we explored the potential of monoolein-based cubosomes and hexosomes as nanocarriers for theranostic purposes. Our work focussed on the design of lipid nanoparticles able to deliver antineoplastic drugs and imaging probes for fluorescent optical in vitro and in vivo imaging. We developed cubosome formulations loaded with antineoplastic drugs and useful for the fluorescence imaging of cells. Such formulations were also actively targeted to cancer cells and coupled with a NIR-emitting fluorophore, which was the promise for in vivo applications. We also investigated hexosomes with encouraging results encapsulating in their lipid matrix a BODIPY derivative with solvatochromic properties, helpful for the understanding of the dye localization. Importantly, we reported (manuscript submitted) the first proof-of-principle for in vivo fluorescence optical imaging application using monoolein-based cubosomes in a healthy mouse animal model. Finally, since relatively little is known about the interaction of cubosomes with biological systems, their effects on lipid droplets, mitochondria and lipid profile of HeLa cells were deeply studied. This thesis is divided in two main parts. The introduction section reports on the essential background of the research field, and it is followed by the publications (published or submitted) resulting from these three years of work.

In vitro release of nonoxynol-9 from silicone matrix intravaginal rings

The controlled-release characteristics of matrix silicone intravaginal rings loaded with between 100 and 971 mg of nonoxynol-9 have been investigated with a view to developing a ring that may offer a new female-controlled method for the prevention of transmission of sexually transmitted diseases, particularly HIV. Intravaginal rings containing 253, 487 and 971 mg of nonoxynol-9 provided a daily release of 2 mg or more over the 8-day release period, the minimal amount of nonoxynol-9 considered to provide an effective vaginal concentration for the prevention of HIV. Furthermore, the maximum daily release of N9 was about 6 mg, an amount significantly smaller than that observed for other nonoxynol-9 products whose large daily doses may in fact increase the occurrence of HIV by causing epithelial damage to the vaginal tissue. The release mechanism of the liquid nonoxynol-9 from the intravaginal rings has also been investigated and compared to models describing the release of solid drugs from the rings. It has been demonstrated through release studies and surface microscopy that a drug depletion zone is not established in such liquid-loaded intravaginal ring systems, with implications for the release kinetics. (C) 2003 Elsevier B.V. All rights reserved.

The Co-Entrapment of a Homogeneous Catalyst and an Ionic Liquid by a Sol-gel Method: Recyclable Ionogel Hydrogenation Catalysts

Molecular hydrogenation catalysts have been co-entrapped with the ionic liquid [Bmim]NTf(2) inside a silica matrix by a sot-gel method. These catalytic ionogels have been compared to simple catalyst-doped glasses, the parent homogeneous catalysts, commercial heterogeneous catalysts, and Rh-doped mesoporous silica. The most active ionogel has been characterised by transmission electron microscopy, X-ray photoelectron spectroscopy, and solid state NMR before and after catalysis. The ionogel catalysts were found to be remarkably active, recyclable and resistant to chemical change.

Gelation of ionic liquids using a cross-linked poly(ethylene glycol) gel matrix

Conductive ionic liquid -poly(ethylene glycol) (IL-PEG) gels have been prepared by gelation of the hydrophobic ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [(C(6)mim] [NTf2]) by the cross-linking reaction of disuccinimidylpropyl PEG monomers with four-arm tetraamine PEG cross-linkers. This is the first time that a crosslinked PEG matrix, such as this, has been used to gel nonaqueous solvents. Initial studies screening other ionic liquids as solvents indicate that the gelation of the ionic liquid is both cation and anion dependent with smaller, coordinating cations disrupting or preventing gel formation.

Investigation on drop penetration and wetting characteristics of powder-liquid systems in relation to the mixing of acrylic bone cement

This study investigated methyl methacrylate – polymethyl methacrylate powder bed interactions through droplet analyses, using model fluids and commercially available bone cement. The effects of storage temperature of liquid monomer and powder packing configuration on drop penetration time were investigated. Methyl methacrylate showed much more rapid imbibition than caprolactone due to decrease in both contact angle and fluid viscosity. Drop penetration of caprolactone through polymethyl methacrylate increased with decrease in bed macro-voids and increase in bulk density as predicted by the modified constant drawing area penetration model and confirmed by drop penetration images. Linear relationships were found between droplet mass and drawing area with imbibition time. Further experiments showed gravimetric analysis of the polymerised methyl methacrylate – polymethyl methacrylate matrix under various storage temperatures correlated with Reynolds number and Washburn analyses. These observations have direct implications for the design of mixing and delivery systems for acrylic bone cements used in orthopaedic surgery.