Determination of benzalkonium chloride in eye care products by high-performance liquid chromatography and solid-phase extraction or on-line column switching.

Benzalkonium chloride (BAK) is a mixture of alkylbenzyldimethylammonium chlorides, which is commonly used as a bacteriostat. In this work, the three major homologues of BAK are quantitated in the over-the-counter eye care products Murine and Murine Plus using high-performance liquid chromatography (HPLC). The analytes are separated from various product excipients and concentrated by either solid-phase extraction onto Sep-Pak C18 cartridges or by an on-line column-switching technique using 1-cm reversed-phase precolumns. Absolute recoveries of BAK homologues by the solid-phase extraction technique ranged from 97.2 to 98.7% for standards and from 98.0 to 98.4% for samples. Absolute recovery of the BAK homologues by the column-switching technique was 101.3% for standards and ranged from 99.9 to 103.7% for samples. Relative recoveries were quantitative by both techniques. Assay precision (R.S.D. values) were +/- 2.2% to +/- 2.6% and +/- 0.4% to +/- 0.8% by solid-phase extraction and column-switching techniques, respectively. The method provides advantages of high sample throughput, excellent column life and automation.     

Engineered protein cages for nanomaterial synthesis

Self-assembled particles of genetically engineered human L subunit ferritin expressing a silver-binding peptide were used as nanocontainers for the synthesis of silver nanoparticles. The inner cavity of the self-assembled protein cage displays a dodecapeptide that is capable of reducing silver ions to metallic silver. This chimeric protein cage when incubated in the presence of silver nitrate exhibits the growth of a silver nanocrystal within its cavity. Our studies indicate that it is possible to design chimeric cages, using specific peptide templates, for the growth of other inorganic nanoparticles.     

Synthesis and characterisation of advanced UHMWPE/silver nanocomposites for biomedical applications

A supercritical fluid (SCF) route for facile and homogeneous introduction of silver nanoparticles into polymer hosts is described. Our focus is on ultra-high molecular weight polyethylene (UHMWPE). We demonstrate that the metallic nanoparticles have a substantial effect upon the wear and tribochemical properties of the polymer substrate.     

COSMIC(90): An improved molecular mechanics treatment of hydrocarbons and conjugated systems

Summary Four modifications to the COSMIC molecular mechanics force field are described, which greatly increase both its versatility and the accuracy of calculated conformational energies. The Hill non-bonded van der Waals potential function has been replaced by a two-parameter Morse curve and a new H-H potential, similar to that in MM3, incorporated. Hydrocarbon energies in particular are much improved.A simple iterative Hückel pi-electron molecular orbital calculation allows modelling of conjugated systems. Calculated bond lengths and rotational barriers for a series of conjugated hydrocarbons and nitrogen heterocycles are shown to be as accurate as those determined by the MM2 SCF method.Explicit hydrogen-bonding potentials for H-bond acceptor-donor atom pairs have been included to give better hydrogen bond energies and lengths. The van der Waals radii of protonic hydrogens are reduced to 0.5 Å and the energy well depth is increased to 1.0 kcal mol^-1.Two new general atom types, N⁺ _sp ² and O^- _sp ³ , have been introduced which allow a wide variety of charged conjugated systems to be studied. A minimum of parameterisation is required, as the new types are easily included in the Hückel scheme which automatically adjusts bond and torsional parameters according to the defined bond-order relationships.     

Tailoring the optical and magnetic properties of La-BaM hexaferrites by Ni substitution

We investigate the impact of Ni insertion on the structural,optical,and magnetic properties of Ba_0.8La_0.2Fe_12-xNi_xO₁₉hexaferrites(Ni substituted La-BaM hexaferrites).Samples were prepared using the conventional co-precipitation method and sintered at 1000℃for 4 hours to assist the crystallization process.An analysis of the structure of the samples was carried out using an x-ray diffraction(XRD)spectrometer.The M-type hexagonal structure of all the samples was confirmed using XRD spectra.The lattice parameters a and c were found to be in the ranges of 5.8925±0.001 nm–5.8952±0.001 nm and 23.2123±0.001 nm–23.2219±0.001 nm,respectively.The M-type hexagonal nature of the prepared samples was also indicated by the presence of corresponding FT-IR bands and Raman modes in the FT-IR and Raman spectra,respectively.EDX results confirmed the successful synthesis of the samples according to the required stoichiometric ratio.A UV-vis spectrometer was used to record the absorption spectra of the prepared samples in the wavelength range of 200 nm–1100 nm.The optical energy bandgap of the samples was found to be in the range of 1.21 eV–3.39 eV.The M–H loops of the samples were measured at room temperature at an applied magnetic field range of 0 kOe–60 kOe.A high saturation magnetization of 99.92 emu/g was recorded in the sample with x=0 at a microwave operating frequency of 22.2 GHz.This high value of saturation magnetization is due to the substitution of La3+ions at the spin-up(12k,2a,and 2b)sites.The Ni substitution is proven to be a potential candidate for the tuning of the optical and magnetic parameters of M-type hexaferrites.Therefore,we suggest that the prepared samples are suitable for use in magneto-optic applications.     

Identification of peptides that promote the rapid precipitation of germania nanoparticle networks via use of a peptide display library

Peptides that promote the rapid, room-temperature precipitation of amorphous germania nanoparticle networks from solution have been identified via use of a combinatorial peptide display library.     

Metal-assisted in situ formation of a tridentate acetylacetone ligand for complexation of fac-Re(CO)3+ for radiopharmaceutical applications

Reaction of [NEt4]2[ReBr3(CO)3] with 2,4-pentanedione (acac) yields a complex of the type fac-Re(acac)(OH2)(CO)3 (1) under aqueous conditions. 1 was further reacted with a monodentate ligand (pyridine) to yield a fac-Re(acac)(pyridine)(CO)3 complex (2). Complex 1 was found to react with primary amines to generate a Schiff base (imine) in aqueous solutions. When a mixed-nitrogen donor bidentate ligand, 2-(2-aminoethyl)pyridine, that has different coordination affinities for fac-Re(acac)(OH2)(CO)3 was utilized, a unique tridentate ligand was formed in situ utilizing a metal-assisted Schiff base formation to yield a complex fac-Re(CO)3(3[(2-phenylethyl)imino]-2-pentanone) (3). Tridentate ligand formation was found to occur only with the Re-coordinated acac ligand. Reactions of acac with fac-Re(CO)3Br(2-(2-aminoethyl)pyridine) (4) or a mixture of [NEt4]2[ReBr3(CO)3], acac, and 2-(2-aminoethyl)pyridine did not yield the formation of complex 3 in water.     

Effects of digestion,chemical separation,and deposition on Po-210 quantitative analysis

The purpose of this work was to determine polonium losses from a variety of sample types (soil, cotton fiber, and air filter) due to digestion technique, chemical separation, and deposition method for alpha energy analysis. Results demonstrated that yields from a perchloric acid wet-ash (87 ± 5 %) were similar to that from a microwave digestion (100 ± 7 %), but both were greater than the dry-ash procedure (38 ± 5 %). The polonium was separated from an SRM soil using an AG1X8 ion exchange column and deposited on a Ag disk with a recovery of 83 ± 7 % of polonium-209 (Po-209). Deposition yields without chemical separation averaged 90 ± 5 % of Po-209. The polonium-210 content was successfully measured in the three matrix types and quantitated using alpha spectroscopy.     

Tetramethylcyclopentadienylselenium derivatives

Bis(1,2,3,4-tetramethylcyclopentadienyl)selane (1) has been prepared by the reaction of tetramethylcyclopentadienyllithium (Cp(t)Li) with selenium bis(diethyldithiocarbamate). Treatment of Cp(t)Li with elemental selenium, followed by air oxidation, led to loss of the allylic hydrogen atom, and formation of the novel tricyclic compound 1,4,5,6,7,10,11,12-octamethyltricyclo[7.3.0.0]-2,8-diselenadodeca-3,5,9,11-tetraene (2). The sulfur analogue of 2 has been obtained by a similar procedure. The X-ray crystal structures of compounds 1 and 2 have been determined, and the molecular geometry observed for has been probed using DFT calculations.