Electron promotion by surface functional groups of single wall carbon nanotubes to overlying metal particles in a fuel-cell catalyst.

A remarkable promotion: Functional groups added onto single-wall carbon nanotubes (SWNTs) can significantly influence the activity of a noble metal for formic acid oxidation. Phenolate groups on SWNTs under alkaline conditions can double the activity of 20 % w/w Pd compared to unmodified SWNTs. This catalyst has 14 times higher activity than the commercial benchmark catalyst (10 % w/w Pd on Vulcan).

Filled and glycosylated carbon nanotubes for in vivo radioemitter localization and imaging.

Functionalization of nanomaterials for precise biomedical function is an emerging trend in nanotechnology. Carbon nanotubes are attractive as multifunctional carrier systems because payload can be encapsulated in internal space whilst outer surfaces can be chemically modified. Yet, despite potential as drug delivery systems and radiotracers, such filled-and-functionalized carbon nanotubes have not been previously investigated in vivo. Here we report covalent functionalization of radionuclide-filled single-walled carbon nanotubes and their use as radioprobes. Metal halides, including Na(125)I, were sealed inside single-walled carbon nanotubes to create high-density radioemitting crystals and then surfaces of these filled-sealed nanotubes were covalently modified with biantennary carbohydrates, improving dispersibility and biocompatibility. Intravenous administration of Na(125)I-filled glyco-single-walled carbon nanotubes in mice was tracked in vivo using single-photon emission computed tomography. Specific tissue accumulation (here lung) coupled with high in vivo stability prevented leakage of radionuclide to high-affinity organs (thyroid/stomach) or excretion, and resulted in ultrasensitive imaging and delivery of unprecedented radiodose density. Nanoencapsulation of iodide within single-walled carbon nanotubes enabled its biodistribution to be completely redirected from tissue with innate affinity (thyroid) to lung. Surface functionalization of (125)I-filled single-walled carbon nanotubes offers versatility towards modulation of biodistribution of these radioemitting crystals in a manner determined by the capsule that delivers them. We envisage that organ-specific therapeutics and diagnostics can be developed on the basis of the nanocapsule model described here.

Electron transport behavior of individual zinc oxide coated single-walled carbon nanotubes.

Uniform zinc oxide coated single-walled nanotubes (SWNTs) were fabricated by ultrasonic irradiation with acid-treated SWNTs, zinc acetate, and triethanolamine at low temperature in aqueous phase processing. The ZnO coating process did not decrease the dark current of the SWNTs, but a real decrease in the steady state negative photocurrent was observed after ZnO coating, suggesting a clear photosensitization effect. Transport measurements reveal that the negative photocurrent in s (semiconducting)-SWNTs@ZnO could be described by electron-hole compensation behavior attributed to the ZnO layer under ultraviolet excitation. This simple coating method for one-dimensional material can open up new possibilities for multifunctional nanodevices.

Enhanced sidewall functionalization of single-wall carbon nanotubes using nitric acid.

When a sample of as-made single-walled carbon nanotubes (SWNTs) is treated with nitric acid, oxidation debris are formed due to the functionalization (mainly carboxylation) of the amorphous carbon present in the sample and a continuous coating along the carbon nanotube walls is created preventing the sidewall functionalization of the SWNTs. This oxidation debris can be easily removed by an aqueous base wash leaving behind a sample with a low degree of functionality. After removal of the amorphous carbon (by steam purification) from a sample of as-made SWNTs, the resulting purified SWNTs are readily carboxylated on the walls by nitric acid treatment. The use of steam for the purification of SWNTs samples allows the removal of the amorphous carbon and graphitic layers coating the metal particles present in the sample without altering the tubular structure of the SWNTs. The exposed metal particles can then be easily removed by an acid wash. Comparison between the steam treatment and molten sodium hydroxide treatment is made.

Core-shell PbI2@WS2 inorganic nanotubes from capillary wetting.

Multiwall WS(2) nanotube templates were used as hosts to prepare core-shell PbI(2)@WS(2) nanotubes by a capillary-wetting method. Conformal growth of PbI(2) layers on the inner wall of the relatively wide WS(2) nanotubes (i.d. ca. 10 nm) leads to nanotubular structures which were not previously observed in narrow carbon nanotube templates. Image simulation after structural modeling (see picture) showed good agreement with the experimental HRTEM image.

Steam purification for the removal of graphitic shells coating catalytic particles and the shortening of single-walled carbon nanotubes.

Purification and shortening of single-walled carbon nanotubes (SWNTs) is carried out by treatment with steam. During the steam purification the graphitic shells coating the catalytic metal particles are removed. Consequently, the exposed catalytic particles can be easily dissolved by treatment with hydrochloric acid. No damage to the carbon nanotube tubular structure is observed, even after prolonged treatment with steam. Samples are characterized by HRTEM, TGA, magnetic measurements, Raman spectroscopy, AFM, and XPS.

A simple method for the containment and purification of filled open-ended single wall carbon nanotubes using C60 molecules.

Soluble materials placed inside opened SWNTs can be contained using fullerenes to block the ends, thereby providing a way to remove the excess of external soluble material present in the initial product formed by low temperature filling of open-ended single wall carbon nanotubes; the C60-blocked filled SWNTs can then be used in applications in which leakage is undesirable.

The role of photoinduced defects in TiO2 and its effects on hydrogen evolution from aqueous methanol solution.

The hydrogen evolution from aqueous methanol solutions was found to follow two stages of zero order kinetics during photoreactions using TiO 2 as the photocatalyst. Maximal hydrogen evolution was found at the 10% (v/v) methanol solution. X-ray photoelectron spectroscopy (XPS) shows that Ti(1566) defects are formed on the surface of TiO 2 and X-ray powder diffraction (XRD) indicates that Ti(1566) defects are also formed in the bulk after photoreaction. Formation of defects is also shown by broadening of Bragg peaks and blue shifts and peak broadening in Raman spectroscopy. The defect disorder results in the increase of hydrogen evolution. UV-vis diffuse reflection spectra confirm that new absorptions in the visible light region are related to the defect content. At high methanol concentration, XPS implies that the active sites of the surface are blocked by hydroxyl groups, which results in the decrease of hydrogen evolution. TEM images showed that the photoreaction occurred on the surface of the photocatalyst as the surface of the TiO 2 became rough after the photoreaction.

Effects of covalent functionalization on the biocompatibility characteristics of multi-walled carbon nanotubes.

We report the effect of chemical modification of multi-walled carbon nanotubes (MWNTs) on their activation of the human serum complement system, as well as the adsorption of human plasma proteins on MWNTs. Four different types of chemically-modified MWNTs were tested for complement activation via the classical and alternative pathways using haemolytic assays. Human plasma protein binding was also tested using an affinity chromatography technique based on carbon nanotube-Sepharose matrix. Covalent functionalization of MWNTs greatly altered the level of activation of the complement system via the classical pathway. For example, MWNTs functionalised with epsilon-caprolactam or L-alanine showed respectively >90% and >75% reduction in classical pathway activation compared with unmodified MWNTs. These results demonstrate for the first time that these types of chemical modification are able to alter considerably the levels of specific complement proteins bound by pristine MWNTs (used as a control experiment). The reduced levels of complement activation via the classical pathway, that are likely to increase biocompatibility, were directly correlated with the amount of C1q protein bound to chemically modified carbon nanotubes. An inverse correlation was also observed between the amount of complement factor H bound to chemically modified MWNTs and the level of complement consumption via the alternative pathway. Binding of human plasma and serum proteins to pristine and modified MWNTs was highly selective. The chemical modifications studied generally increased nanotube dispersibility in aqueous media, but diminished protein adsorption.

Comment on "Hydride, gold(i) and related derivatives of the unsaturated ditungsten anion [W2Cp2(µ-PCy2)(µ-CO)2]-" by M. A. Ruiz et al., Dalton Trans., 2014, 43, 16044.

Application of the covalent bond classification to the compounds [M2(η5-C5H5)2(µ-H)(µ-PCy2)(CO)2] (M = Mo, W) identifies the compounds as having two M-M bonds and a 2 electron 3 centre (2e-3c) bond incorporating the bridging hydrogen, in accord with density functional calculations, and assigns their class as ML4X4.

Geoff Cloke at 65: a pioneer in organometallic chemistry.

Professor Geoff Cloke FRS celebrates his 65th birthday in 2018. In a career spanning four decades, his research endeavours have accounted for some of the most innovative synthetic chemistry of the modern era, with his many publications describing truly exceptional compounds and experimental methods that portray a unique chemical imagination. In addition to his scientific accomplishments, Cloke can be particularly proud of his successful mentoring, a level of dedication that propelled many students and post-docs on to become research leaders in their own right. In compiling this collection of some of his research articles, a small cross-section of his friends, colleagues and collaborators, wish to pay tribute to his modesty, compassion and generous personality.

Removal of amorphous carbon for the efficient sidewall functionalisation of single-walled carbon nanotubes.

The sidewall functionalisation of carbon nanotubes using the standard nitric acid treatment can be greatly enhanced by first removing the amorphous carbon present in the sample.

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.

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.

Opening and reversible filling of single-walled carbon nanotubes with various materials.

Single-walled carbon nanotubes have been advocated as perfect candidates for the sustainable miniaturisation of electronic and mechanical nanoscale devices. The encapsulation of selected compounds within the inner hollow cavity of SWNTs allows controlled preparation of nano-meter size "nanowires" and "nanocables" with purpose-tailored physical properties. Therefore is crucial to have control of opening and closing their tips. In a previous study we showed that molten metal hydroxide [MOH (M==Cs, Na)] is filled into the carbon nanotubes and can be easily washed out with water leaving opened nanotubes. Following this approach we have explored the use of milder ways to open SWNTs that can be easily scalable for the production of large amount of opened SWNTs. The opened tubes have then successfully been filled in solution with various inorganic and organic materials.

The classification and representation of main group element compounds that feature three-center four-electron interactions.

This article provides a means to classify and represent compounds that feature 3-center 4-electron (3c-4e) interactions in terms of the number of electrons that each atom contributes to the interaction. Specifically, Class I 3c-4e interactions are classified as those in which two atoms provide one electron each and the third atom provides a pair of electrons (i.e. LX2), while Class II 3c-4e interactions are classified as those in which two atoms each provide a pair of electrons and the third atom contributes none (i.e. L2Z). These classes can be subcategorized according to the nature of the central atom. Thus, Class I interactions can be categorized according to whether the central atom provides one (i.e.µ-X) or two (i.e.µ-L) electrons, while Class II interactions can be categorized according to whether the central atom provides none (i.e.µ-Z) or two (i.e.µ-L) electrons. The use of appropriate structure-bonding representations for these various interactions provides a means to determine the covalent bond classification of the element of interest.

Direct imaging of o-carborane molecules within single walled carbon nanotubes.

Ortho-carborane molecules have been inserted into single walled carbon nanotubes (SWNTs) and imaged directly by high resolution transmission electron microscopy (HRTEM); both discrete molecules and 'zig-zag' 1D chains of o-carborane 'petit pois' were observed to pack into the tubule capillaries.

Directly observed covalent coupling of quantum dots to single-wall carbon nanotubes.

Carboxylate chemistry is used to covalently couple metal nanoparticles to defect sites in controllably oxidized single-walled carbon nanotube termini and side-walls, and this process monitored by atomic force microscopy.

Bimetallic nanoparticles aligned at the tips of carbon nanotubes.

Cluster-derived bimetallic nanoparticles have been deposited onto multi-wall carbon nanotubes and shown to be generally homogeneously dispersed, of uniform small sizes, of the same composition as the starting mixed-metal clusters, and to have a tendency to align at the tips of the tubules.

Encapsulation of quaternary 1D pentlandite-type alloy crystals within conical multi-layer carbon nanotubes.

Ordered 1D crystals of a complex pentlandite-type alloy with the general composition (Fe,Ni,Co)9S8 have been synthesised inside conical Multi Walled Carbon Nanotubes (MWNTs); the crystals are observed as a by-product of an arc-evaporation synthesis of Double Walled Carbon Nanotubes (DWNTs).