Effect of temperature and mixing conditions on quality and consistency of poly(methyl methacrylate) bone cement

The mixing of poly(methyl methacrylate) (PMMA) bone cement has been studied to develop methods for preparing a consistently high quality cement. A novel droplet test experimental procedure was developed that characterised the wetting characteristics involved in bone cement mixing. Using this technique it was established that increased wetting occurred by mixing bone cement at a lower temperature (-28 degreesC) than normal mixing at room temperature.

Chromium, iron, ruthenium and gold complexes of 3,3-(biphenyl-2,2 '-diyl)-1-diphenylphosphino-1-phenylallene: A versatile ligand

Successive treatment of 9-(phenylethynyl)fluoren-9-ol (1a), with HBr, butyllithium and chlorodiphenylphosphine furnishes 3,3-(biphenyl-2,2'-diyl)-1-diphenylphosphino-1-phenylallene (5). Moreover, reaction of 1a directly with chlorodiphenylphosphine yields the corresponding allenylphosphine oxide (6). The allenylphosphine (5), and Fe-2(CO)(9) initially form the phosphine-Fe(CO)(4) complex, 11, which is very thermally sensitive and readily loses a carbonyl ligand. In the resulting phosphine-Fe(CO)(3) system, 12, the additional site at iron is coordinated by the allene double bond adjacent to phosphorus; the Fe(CO) 3 tripod in 12 exhibits restricted rotation on the NMR time-scale even at room temperature. The corresponding chromium complex, (5)-Cr(CO)5 (9), has also been prepared. The gold complexes (5)AuCl (13), and [(5)-Au(THT)](+) X-, where (THT) is tetrahydrothiophene, and X = PF6 (14a), or ClO4 (14b), are analogous to the known triphenylphosphine-gold complexes. In contrast, in the (arene)(allenylphosphine) RuCl2 system the allene double bond adjacent to phosphorus displaces a chloride, and the resulting cationic species undergoes nucleophilic attack by water yielding ultimately a five-membered Ru-P-C=C-O ruthenacycle (17). Thus, the allenylphosphine (5), reacts initially as a conventional mono-phosphine but, when the metal centre has a readily displaceable ligand such as a carbonyl or halide, the allene double bond adjacent to the phosphorus can also function as a donor. X- ray crystal structures are reported for 5, 6, 11, 12, 13, 14a, 14b and 17.

New families of enantiopure cyclohexenone cis-diol, o-quinol dimer and hydrate metabolites from dioxygenase-catalysed dihydroxylation of phenols

Toluene dioxygenase-catalysed cis-dihydroxylation of phenols has led to the discovery of new enantiopure cyclohexenone cis-diol, o-quinol dimer and phenol hydrate metabolites having synthetic potential.

The structural characterization and hydroformylation activity of the tri-rhodium complex [Rh-3(mu(2)-dppm)(2)(mu(2)-CO)(3)(K-1-CO)(3)]BF4

Rh-2(cod)(2)(mu(2)-dppm)(mu(2)-Cl)]BF4 (1) rearranges under carbon monoxide to give [Rh-3(mu(2)-dppm)(2)-(mu(2)-CO)(3)(K-1-CO)(3)]BF4 (2). Complex 2 has been structurally characterized by single crystal X-ray crystallography. The hydroformylation activities of 1 and 2 were compared for substrates styrene and 1-hexene and the activity of 2 found to be unexpectedly high.

New catanionic surfactants based on 1-alkyl-3-methylimidazolium alkylsulfonates, [C(n)H(2n+1)mim][CmH2m+1SO3]: mesomorphism and aggregation

Anionic and cationic alkyl-chain effects on the self-aggregation of both neat and aqueous solutions of 1-alkyl-3-methylimidazolium alkylsulfonate salts ([C(n)H(2n+ 1)mim][CmH2m+1SO3]; n = 8, 10 or 12; m = 1 and n = 4 or 8; m = 4 or 8) have been investigated. Some of these salts constitute a novel family of pure catanionic surfactants in aqueous solution. Examples of this class of materials are rare; they are distinct from both mixed cationic-anionic surfactants (obtained by mixing two salts) and gemini surfactants (with two or more amphiphilic groups bound by a covalent linker). Fluorescence spectroscopy and interfacial tension measurements have been used to determine critical micelle concentrations (CMCs), surface activity, and to compare the effects of the alkyl-substitution patterns in both the cation and anion on the surfactant properties of these salts. With relatively small methylsulfonate anions (n = 8, 10 and 12, m = 1), the salts behave as conventional single chain cationic surfactants, showing a decrease of the CMC upon increase of the alkyl chain length (n) in the cation. When the amphiphilic character is present in both the cation and anion (n = 4 and 8, m = 4 and 8), novel catanionic surfactants with CMC values lower than those of the corresponding cationic analogues, and which exhibited an unanticipated enhanced reduction of surface tension, were obtained. In addition, the thermotropic phase behaviour of [C(8)H(18)mim][C8H18SO3] (n = m = 8) was investigated using variable temperature X-ray scattering, polarising optical microscopy and differential scanning calorimetry; formation of a smectic liquid crystalline phase with a broad temperature range was observed.

Prediction of the formation and stabilities of energetic salts and ionic liquids based on ab initio electronic structure calculations

A computational approach to predict the thermodynamics for forming a variety of imidazolium-based salts and ionic liquids from typical starting materials is described. The gas-phase proton and methyl cation acidities of several protonating and methylating agents, as well as the proton and methyl cation affinities of many important methyl-, nitro-, and cyano- substituted imidazoles, have been calculated reliably by using the computationally feasible DFT (B3LYP) and MP2 (extrapolated to the complete basis set limit) methods. These accurately calculated proton and methyl cation affinities of neutrals and anions are used in conjunction with an empirical approach based on molecular volumes to estimate the lattice enthalpies and entropies of ionic liquids, organic solids, and organic liquids. These quantities were used to construct a thermodynamic cycle for salt formation to reliably predict the ability to synthesize a variety of salts including ones with potentially high energetic densities. An adjustment of the gas phase thermodynamic cycle to account for solid- and liquid-phase chemistries provides the best overall assessment of salt formation and stability. This has been applied to imidazoles (the cation to be formed) with alkyl, nitro, and cyano substituents. The proton and methyl cation donors studied were as follows: HCl, HBr, HI, (HO)(2)SO2, HSO3CF3 (TfOH), and HSO3(C6H4)CH3 (TsOH); CH3Cl, CH3Br, CH3I, (CH3O)(2)SO2, CH3SO3CF3 (TfOCH3) and CH3SO3(C6H4)CH3 (TsOCH3). As substitution of the cation with electron-withdrawing groups increases, the triflate reagents appear to be the best overall choice as protonating and methylating agents. Even stronger alkylating agents should be considered to enhance the chances of synthetic success. When using the enthalpies of reaction for the gas-phase reactants (eq 6) to form a salt, a cutoff value of - 13 kcal mol(-1) or lower (more negative) should be used as the minimum value for predicting whether a salt can be synthesized.

Multiply reconfigurable ‘plug and play’ molecular logic via self-assembly

A substantial set of ion-driven molecular logic gates are implemented in turn by arranging the association between easily available lumophores and receptors in detergent micelles.

Choline saccharinate and choline acesulfamate: Ionic liquids with low toxicities

Choline saccharinate and choline acesulfamate are two examples of hydrophilic ionic liquids, which can be prepared from easily available starting materials (choline chloride and a non-nutritive sweetener). The (eco)toxicity of these ionic liquids in aqueous solution is very low in comparison to other types of ionic liquids. A general method for the synthesis and purification of hydrophilic ionic liquids is presented. The method consists of a silver-free metathesis reaction, followed by purification of the ionic liquid by ion-exchange chromatography. The crystal structures show a marked difference in hydrogen bonding between the two ionic liquids, although the saccharinate and the acesulfamate anions show structural similarities. The optimized structures, the energetics, and the charge distribution of cation-anion pairs in the ionic liquids were studied by density functional theory (DFT) and second-order (Moller-Plesset) perturbation theory calculations. The occupation of the non-Lewis orbitals was considered to obtain a qualitative picture of the Lewis structures. The calculated interaction energies and the dipole moments for the ion pairs in the gas phase were discussed.

Reactivity of ammonium chloride/mercuric chloride mixtures with monel containers. The new compounds (NH4)(2)(NH3)(x)[Ni(NH3)(2)Cl-4] and (NH4)(5)Cl-2[CuCl2][CuCl4]

Ammonium chloride/mercuric chloride mixtures (molar ratio 2: 1) react at 350degreesC with Monel (Cu68Ni32) to yield (NH4)NiCl3 and mercury and copper amalgam, respectively. With larger amounts of (NH4)Cl in the reaction mixture, dark green (NH4)(2)(NH3)(x)[Ni(NH3)(2)Cl-4] (x approximate to 0.77) (1) is also formed as a main product. Light blue crystals of the mixed-valent copper(I,II) chloride (NH4)(5)Cl-5[CuCl2][CuCl4] (2) were obtained as a minor byproduct from a 4:1 reaction mixture. The crystal structures were determined from single crystal X-ray data; (1): tetragonal, I4/mmm, a = 770.9(1), e = 794.2(2) pm, 190 reflections, R-1 = 0.0263; (2): tetragonal, I4/mcm, a = 874.8(1), c = 2329.2(3) pm, 451 reflections, R-1 = 0.0736. In (1) Ni2+ resides in trans-[Ni(NH3)(2)Cl-4](2-) octahedra, and in (2) copper(l) is linearly two-coordinated in ECUC121- and copper(II) resides in a flattened tetrahedron [CuCl4](2-) with a tetrahedricity of 89%. (C) 2001 Elsevier Science.

The effect of 3D weaving and consolidation on carbon fiber tows, fabrics, and composites

This article investigates the damage imparted on load-bearing carbon fibers during the 3D weaving process and the subsequent compaction behavior of 3D woven textile preforms. The 3D multi-layer reinforcements were manufactured on a textile loom with few mechanical modifications to produce preforms with fibers orientated in the warp, weft, and through-the-thickness directions. Tensile tests were conducted on three types of commercially available carbon fibers, 12k HTA, 6k HTS, and 3k HTS in an attempt to quantify the effect of fiber damage induced during the 3D weaving process on the mechanical and physical performance of the fiber tows in the woven composite. The tests were conducted on fiber tows sampled from different locations in the manufacturing process from the bobbin, through the creel and loom mechanism, to the final woven fabric. Mechanical and physical testing were then conducted to quantify the tow geometry, orientation and the effect of compaction during manufacture of two styles of 3D woven composite by vacuumassisted resin transfer molding (VaRTM).

A stereocontrolled method for the synthesis of D- and L-2-deoxy-C-nucleosides using an intramolecular Sakurai-type cyclisation reaction

A novel synthetic procedure has been developed that provides access to D/L-2-deoxy-C-nucleosides from 3,4-epoxytetrahydrofuran in seven steps and in moderate to good yields. The key chemical transformation was the Lewis acid catalysed intramolecular cyclisation reaction of an acetal for which the stereochemical outcome was dependent of the reagents' ratio.

From PASS 1 to YES to AND logic: building parallel processing into molecular logic gates by sequential addition of receptors

The synthesis and photophysical characterization of a novel molecular logic gate 4, operating in water, is demonstrated based on the competition between. fluorescence and photoinduced electron transfer (PET). It is constructed according to a 'fluorophore-spacer-receptor(1)-spacer-receptor(2)' format where anthracene is the. fluorophore, receptor(1) is a tertiary amine and receptor(2) is a phenyliminodiacetate ligand. Using only protons and zinc cations as the chemical inputs and. fluorescence as the output, 4 is demonstrated to be both a two-input AND and INH logic gate. When 4 is examined in context to the YES logic gates 1 and 2, and the two-input AND logic gate 3 and three-input AND logic gate 5, each with one or more of the following receptors including a tertiary amine, phenyliminodiacetate or benzo-15-crown-5 ether, logic gate 4 is the missing link in the homologous series. Collectively, the molecular logic gates 1-5 corroborate the PET 'fluorophore-spacer-receptor' model using chemical inputs and a light-signal output and provide insight into controlling the. fluorescence quantum yield of future PET-based molecular logic gates.

Small angle neutron scattering from 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids ([C(n)mim][PF6], n=4, 6, and 8)

The presence of local anisotropy in the bulk, isotropic, and ionic liquid phases-leading to local mesoscopic inhomogeneity-with nanoscale segregation and expanding nonpolar domains on increasing the length of the cation alkyl-substituents has been proposed on the basis of molecular dynamics (MD) simulations. However, there has been little conclusive experimental evidence for the existence of intermediate mesoscopic structure between the first/second shell correlations shown by neutron scattering on short chain length based materials and the mesophase structure of the long chain length ionic liquid crystals. Herein, small angle neutron scattering measurements have been performed on selectively H/D-isotopically substituted 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids with butyl, hexyl, and octyl substituents. The data show the unambiguous existence of a diffraction peak in the low-Q region for all three liquids which moves to longer distances (lower Q), sharpens, and increases in intensity with increasing length of the alkyl substituent. It is notable, however, that this peak occurs at lower values of Q (longer length scale) than predicted in any of the previously published MD simulations of ionic liquids, and that the magnitude of the scattering from this peak is comparable with that from the remainder of the amorphous ionic liquid. This strongly suggests that the peak arises from the second coordination shells of the ions along the vector of alkyl-chain substituents as a consequence of increasing the anisotropy of the cation, and that there is little or no long-range correlated nanostructure in these ionic liquids.