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Malcolm L H Green

Publications and source records attributed to Malcolm L H Green.

At least 19 recordsLinked to original sources
PubMed2006

Purification and opening of carbon nanotubes using steam.

Purification and opening of carbon nanotubes has been carried out by treatment of as-made single-wall carbon nanotubes (SWNTs) with pure steam at 1 atm pressure. Treated samples have been characterized by high-resolution transmission electron microscopy and IR and Raman spectroscopy. Comparison between the steam purification and the standard nitric acid purification treatment shows that steam is less aggressive toward damage to the tubular nanotube wall structure and forms fewer functional groups.

Journal Article↗
PubMed2006

Cobalt N-heterocyclic carbene alkyl and acyl compounds: synthesis, molecular structure and reactivity.

The N-heterocyclic-carbene containing cobalt carbonyl compound [Co(IMes)(CO)3(Me)] (IMes = 1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene), 1, has been synthesised by tertiary phosphine displacement from [Co(PPh3)(CO)3(Me)]. Subsequent carbonylation afforded the acyl derivative [Co(IMes)(CO)3(COMe)], 2. Similarly, the compound [Co(IMes)(CO)3(COEt)], 3, has been synthesised. The compounds 2 and 3 have been shown to react with dihydrogen to form the cobalt hydride compound [Co(IMes)(CO)3(H)], 4. The molecular structures of compounds 1 and 2 have been determined.

Journal Article↗
PubMed2006

Correlation of structural and electronic properties in a new low-dimensional form of mercury telluride.

Using high resolution electron microscopy and first principles quantum mechanical calculations we have explored the fundamental physics and chemistry of the semiconductor, HgTe grown inside single wall carbon nanotubes. This material forms a low-dimensional structure based on a repeating Hg2Te2 motif in which both atom species adopt new coordination geometries not seen in the bulk. Density-functional theory calculations confirm the stability of this structure and demonstrate conclusively that it arises solely as a consequence of constrained low dimensionality. This change is directly correlated with a modified electronic structure in which the low-dimensional form of HgTe is transformed from a bulk semimetal to a semiconductor.

Journal Article↗
PubMed2006

Migratory insertion in N-heterocyclic carbene-containing Fe carbonyl complexes: an experimental and theoretical study.

The compound [Fe(eta-C5H5)(CO)2(Me)] reacts thermally with N-heterocyclic carbenes (L) to give both alkyl, [Fe(eta-C5H5)(L)(CO)(Me)], and acyl, [Fe(eta-C5H5)(L)(CO)(COMe)], derivatives. The reaction temperature has been shown to affect the product distribution. The alkyl and acyl derivatives exist in an equilibrium that is more easily perturbed than in the tertiary phosphine analogues. DFT studies on the reactivity of [Fe(eta-C5H5)(CO)2(Me)] with PH3 and dihydroimidazole-2-ylidene (IH) have shown that CO exchange is energetically favoured for IH, and energetically disfavoured for PH3. The products of CO-induced migratory insertion, [Fe(eta-C5H5)(L)(CO)(COMe)], are more stable than the parent alkyl, [Fe(eta-C5H5)(L)(CO)(Me)], compounds. This stabilisation is larger when L = IH than when L = PH3. Stabilisation of the transition state by agostic interactions was seen in both instances, but this was significantly more pronounced for L = IH.

Journal Article↗
PubMed2006

B(C6F5)3 adducts of transition metal acyl compounds.

The transition metal acyl compounds [Co(L)(CO)3(COMe)] (L = PMe3, PPhMe2, P(4-Me-C6H4)3, PPh3 and P(4-F-C6H4)3), [Mn(CO)5(COMe)] and [Mo(PPh3)(eta(5)-C5H5)(CO)2(COMe)] react with B(C6F5)3 to form the adducts [Co(L)(CO)3(C{OB(C6F5)3}Me)] (L = PMe3, 1, PPhMe2, 2, P(4-Me-C6H4)3, 3, PPh3, 4, P(4-F-C6H4)3), 5, [Mn(CO)5(C{OB(C6F5)3}Me)] 6 and [Mo(eta(5)-C5H5)(PPh3)(CO)2(C{OB(C6F5)3}Me)], 7. Addition of B(C6F5)3 to a cooled solution of [Mo(eta(5)-C5H5)(CO)3(Me)], under an atmosphere of CO gave [Mo(eta(5)-C5H5)(CO)3(C{OB(C6F5)3}Me)] 8. In the presence of adventitious water, the compound [Co{HOB(C6F5)3}2{OP(4-F-C6H4)3}2] 9, was formed from [Co(P(4-F-C6H4)3)(CO)3(C{OB(C6F5)3}Me)]. The compounds 4 and 9 have been structurally characterised. The use of B(C6F5)3 as a catalyst for the CO-induced migratory-insertion reaction in the transition metal alkyl compounds [Co(PPh3)(CO)3(Me)], [Mn(CO)5(Me)], [Mo(eta(5)-C5H5)(CO)3(Me)] and [Fe(eta(5)-C5H5)(CO)2(Me)] has been investigated.

Journal Article↗
PubMed2005

Complement activation and protein adsorption by carbon nanotubes.

As a first step to validate the use of carbon nanotubes as novel vaccine or drug delivery devices, their interaction with a part of the human immune system, complement, has been explored. Haemolytic assays were conducted to investigate the activation of the human serum complement system via the classical and alternative pathways. Western blot and sodium dodecyl sulphate-polyacrylamide gel electrophoresis (SDS-PAGE) techniques were used to elucidate the mechanism of activation of complement via the classical pathway, and to analyse the interaction of complement and other plasma proteins with carbon nanotubes. We report for the first time that carbon nanotubes activate human complement via both classical and alternative pathways. We conclude that complement activation by nanotubes is consistent with reported adjuvant effects, and might also in various circumstances promote damaging effects of excessive complement activation, such as inflammation and granuloma formation. C1q binds directly to carbon nanotubes. Protein binding to carbon nanotubes is highly selective, since out of the many different proteins in plasma, very few bind to the carbon nanotubes. Fibrinogen and apolipoproteins (AI, AIV and CIII) were the proteins that bound to carbon nanotubes in greatest quantity.

Adsorption↗
PubMed2005

Phase separation of Lal3 inside single-walled carbon nanotubes.

Simple binary solids can be found to adopt unprecedented structures when confined into nanometre-sized cavities, such as the inner cylindrical bore of single-walled carbon nanotubes (SWNT). In the case of the discussed Lal(x)@SWNT encapsulation composite, the Lal2 "crystal" fragment adopts the structure of bulk Lal3, with one third of the iodine positions unoccupied. A complete characterisation of the encapsulation composite was achieved using an enhanced digital restoration approach of high-resolution transmission electron microscopy (HRTEM) images. The resulting complex exit surface wave provides information about the precise structural data of both filling material and host SWNT, establishing the SWNT's chirality and thus enabling a prediction of the composite's overall electron-transport properties.

Journal Article↗
PubMed2004

Single-walled carbon nanotubes filled with M OH (M = K, Cs) and then washed and refilled with clusters and molecules.

Heating single-walled carbon nanotubes (SWNTs) with molten hydroxides MOH (M = K, Cs) gave MOH@SWNT in good yield; high resolution transmission electron microscopy (HRTEM) indicated that CsOH in CsOH@SWNT often adopts twisted 1D crystal structures inside SWNTs; treating MOH@SWNT with water at room temperature removes the soluble hydroxide filling and the resulting SWNTs may then be filled using aqueous solutions of uranyl acetate or uranyl nitrate at rt giving SWNTs filled with UO(2) clusters and uranyl acetate molecules.

Journal Article↗
PubMed2004

Structure and dynamics of a dihydrogen/hydride ansa molybdenocene complex.

In contrast to [Cp(2)MoH(3)](+), which is a thermally stable trihydride complex, the ansa-bridged analogue [(eta-C(5)H(4))(2)CMe(2)MoH(H(2))](+) (1) is a thermally labile dihydrogen/hydride complex. Partial deuteration of the hydride ligands allows observation of J(H)(-)(D) = 11.9 Hz in 1-d(1) and 9.9 Hz in 1-d(2) (245 K), indicative of a dihydrogen/hydride structure. There is a slight preference for deuterium to concentrate in the dihydrogen ligand. A rapid dynamic process interchanges the hydride and dihydrogen moieties in complex 1. Low temperature (1)H NMR spectra of 1 give a single hydride resonance, which broadens at very low temperature due to rapid dipole-dipole relaxation (T(1) = 23 ms (750 MHz, 175 K) for the hydride resonance in 1). Low temperature (1)H NMR spectra of 1-d(2) allow the observation of decoalescence at 180 K into two resonances. The bound dihydrogen ligand exhibits hindered rotation with DeltaG(150) = 7.4 kcal/mol, but H atom exchange is still rapid at all accessible temperatures (down to 130 K). Density functional calculations confirm the dihydrogen/hydride structure as the ground state for the molecule and give estimates for the energy of two hydrogen exchange processes in good agreement with experiment. The presence of the C ansa bridge is shown to decrease the ability of the metallocene fragment to donate to the hydrogens, thus stabilizing the (eta(2)-H(2)) unit and modulating the barrier to H(2) rotation.

Journal Article↗
PubMed2004

Growing and characterizing one-dimensional crystals within single-walled carbon nanotubes.

Single-walled carbon nanotubes (SWNTs) have been used as growth templates for spatially confined crystal growth. The comparative crystallization and high-resolution transmission electron microscopy imaging properties of simple binary halides formed by the alkali iodides MI (M = Li, K, Na, Rb and Cs) within SWNTs are described. The most common structure type observed within SWNTs was the rocksalt archetype, although CsI was observed to form both body-centred cubic (bcc) and rocksalt structure types. ThCl4 was found to form a chain structure of Th[Cl]8 polyhedra. HgI2 crystallized within nanotubes with ultra-narrow (i.e. 0.8 nm) capillaries was observed to form helical 2 x 1 layer crystals.

Journal Article↗
PubMed2003

An encapsulated helical one-dimensional cobalt iodide nanostructure.

Single-walled carbon nanotubes (SWNTs) can be used as templates for the growth of low-dimensional inorganic materials whose structures and properties often differ greatly from those of the bulk. Here we describe the detailed crystallography of an entire helical one-dimensional cobalt diiodide nanostructure encapsulated within a SWNT. This material has an unprecedented twisted double tetrahedral chain structure arising from a rotation of Co(2)I(4) units along its length. The complete nanostructure comprises two distinct regions with oppositely handed helices separated by a short disordered region. The encapsulating SWNT shows a commensurate ovoid distortion reflecting an unexpectedly strong interaction between the nanostructure and the SWNT.

Cobalt↗
PubMed2003

Chemical and biochemical sensing with modified single walled carbon nanotubes.

The nano dimensions, graphitic surface chemistry and electronic properties of single walled carbon nanotubes make such a material an ideal candidate for chemical or biochemical sensing. Carbon nanotubes can be nondestructively oxidized along their sidewalls or ends and subsequently covalently functionalized with colloidal particles or polyamine dendrimers via carboxylate chemistry. Proteins adsorb individually, strongly and noncovalently along nanotube lengths. These nanotube-protein conjugates are readily characterized at the molecular level by atomic force microscopy. Several metalloproteins and enzymes have been bound on both the sidewalls and termini of single walled carbon nanotubes. Though coupling can be controlled, to a degree, through variation of tube oxidative pre-activation chemistry, careful control experiments and observations made by atomic force microscopy suggest that immobilization is strong, physical and does not require covalent bonding. Importantly, in terms of possible device applications, protein attachment appears to occur with retention of native biological structure. Nanotube electrodes exhibit useful voltammetric properties with direct electrical communication possible between a redox-active biomolecule and the delocalized pi system of its carbon nanotube support.

Biosensing Techniques↗
PubMed2002

Bioelectrochemical single-walled carbon nanotubes.

Metalloproteins and enzymes can be immobilized on SWNTs of different surface chemistry. The combination of high surface area, robust immobilization and inherent nanotube electrochemical properties is of promising application in bioelectrochemistry.

Cytochrome c Group↗
PubMed2002

The formation of ReS(2) inorganic fullerene-like structures containing Re(4) parallelogram units and metal-metal bonds.

The encapsulation of ReO(x) within ReS(2) inorganic fullerene-like cages is described for the first time. The encapsulate was prepared by the sulfidization of both hand-milled and ball-milled samples of ReO(2); partial conversion of the oxide to the sulfide was achieved with the degree of sulfidization depending on the exposure to the sulfidizing agent, H(2)S.

Journal Article↗