Synthesis and evaluation of novel boron-containing complexes of potential use for the selective treatment of malignant melanoma

Boron-containing complexes that have the potential to irreversibly accumulate in melanoma cells have been prepared by reaction of amino acids with 9-methoxy-9-borabicyclo[3.3.1]nonane. The ability of each complex to act as a substrate for tyrosinase has been probed by oximetry. Increased uptake of the lead candidate in a tyrosinase-rich cell line, compared with a tyrosinase-absent cell line, is reported, with results correlating well with that for a drug currently approved for BNCT.

Self-assembled columns of fullerene

Columnar mesophases based on alternating triphenylene and hexaphenyltriphenylene moieties are exceptionally stable and able to accommodate bulky side-chain substituents within the alkyl chain continuum between the columns. This paper presents a system in which the triphenylene bears a fullerene on its side-chain and the hexaphenyltriphenylene equivalent is the aza-derivative hexakis(4-nonylphenyl)dipyrazino[2,3-f : 2'3'-h] quinoxalene, PDQ9. The mesophase formed was identified as hexagonal columnar (Col(h)) by X-ray diffraction (a = 25.2 angstrom and c = 3.5 angstrom) but, in addition to the expected peaks, there is indication of a two-dimensional hexagonal superlattice with d-spacing 59 angstrom. This superlattice is believed to arise from ordering of the fullerenes within the liquid crystal matrix. It can be explained on the assumption that, to maximise fullerene-fullerene contact, the fullerenes form chains which wrap around the central column in every group of seven columns of the triphenylene : PDQ9 Col(h) array.

The synthesis of dicobalt and dinickel complexes of trimethylsilylethynyl-1, 2-dihydrofullerene; characterisation by n.m.r. and structure of the first acyclic metal fullerene derivative: molecular structure of [η2-{2-H-1-(Me3SiC ≡ C)-C60}Ni2(η-C5H5)2]

The synthesis and characterisation of the complexes [η2-{2-H-1-(Me3SiC ≡ C)-C60}Co2(CO)6] (2)} and [η-2-{2-H-1-(Me3SiC ≡ C)-C60}Ni2η-C5H5)2] (3)} is reported, together with a single-crystal molecular structure for (3). This provides the first structural data for an acyclic metal derivative of [60]-fullerene.

Fullerene-like models for microporous carbon: a review

Microporous carbons are important in a wide variety of applications, ranging from pollution control to supercapacitors, yet their structure at the molecular level is poorly understood. Over the years, many structural models have been put forward, but none have been entirely satisfactory in explaining the properties of the carbons. The discovery of fullerenes and fullerene-related structures such as carbon nanotubes gave us a new perspective on the structure of solid carbon, and in 1997 it was suggested that microporous carbon may have a structure related to that of the fullerenes. Recently, evidence in support of such a structure has been obtained using aberration-corrected transmission electron microscopy, electron energy loss spectroscopy and other techniques. This article describes the development of ideas about the structure of microporous carbon, and reviews the experimental evidence for a fullerene-related structure. Theoretical models of the structural evolution of microporous carbon are summarised, and the use of fullerene-like models to predict the adsorptive properties of microporous carbons are reviewed.

Diviser, choisir et condenser: rubriques et illustrations du règne d'Uter et Pandragon dans le Merlin de Robert de Boron

La sélection opérée par les rubriques et les enluminures, formes contraintes qui échappent dans une certaine mesure à la linéarité du développement textuel, détermine la réception de l'œuvre. Les manuscrits comprenant des miniatures synthétiques (comme celles qui représentent l'enfance de Merlin) ou des séries iconographiques (comme celles qui rendent compte des amours d'Uterpandragon et Ygerne et de leurs conséquences) présentent donc un caractère exceptionnel, orientant la lecture du texte et son interprétation.

Construction impossible et défense improbable : la tour du roi Vertigier dans l'Historia Brittonum de Nennius, l'Historia Regum Britanniae de Geoffroy de Monmouth, le Brut de Wace et le Merlin de Robert de Boron

La question architecturale de l'impossibilité de l'usurpateur Vertigier à construire sa tour se double d'une réflexion politique et morale déterminante. La tour branlante est en effet à l'image du royaume déchiré de Grande Bretagne : elle emblématise l'instabilité politique et les affrontements militaires qui déterminent l'ascension illégitime puis la chute de ce mauvais roi.

Electrochromic and electrofluorochromic properties of a new boron dipyrromethene–ferrocene conjugate

A new boron dipyrromethene–ferrocene (BODIPY–Fc) conjugate with pentafluorophenyl as the meso substituent and two Fc termini was synthesized and its spectroscopic and electrochemical features were analyzed. An intramolecular charge transfer from the donor Fc to the acceptor BODIPY has been predicted by theory and confirmed experimentally, leading to efficient fluorescence quenching when the dyad is in the neutral state. Fluorescence can be triggered by oxidizing both ferrocenyl units either chemically or electrochemically. Eventually, a fully reversible fluorescence switch is evidenced by coupling TIRF microscopy with electrolysis in an electrochemical cell.

Engineering the electronic bandgaps and band edge positions in carbon-substituted 2D boron nitride: a first-principles investigation

Modification of graphene to open a robust gap in its electronic spectrum is essential for its use in field effect transistors and photochemistry applications. Inspired by recent experimental success in the preparation of homogeneous alloys of graphene and boron nitride (BN), we consider here engineering the electronic structure and bandgap of C2xB1−xN1−x alloys via both compositional and configurational modification. We start from the BN end-member, which already has a large bandgap, and then show that (a) the bandgap can in principle be reduced to about 2 eV with moderate substitution of C (x < 0.25); and (b) the electronic structure of C2xB1−xN1−x can be further tuned not only with composition x, but also with the configuration adopted by C substituents in the BN matrix. Our analysis, based on accurate screened hybrid functional calculations, provides a clear understanding of the correlation found between the bandgap and the level of aggregation of C atoms: the bandgap decreases most when the C atoms are maximally isolated, and increases with aggregation of C atoms due to the formation of bonding and anti-bonding bands associated with hybridization of occupied and empty defect states. We determine the location of valence and conduction band edges relative to vacuum and discuss the implications on the potential use of 2D C2xB1−xN1−x alloys in photocatalytic applications. Finally, we assess the thermodynamic limitations on the formation of these alloys using a cluster expansion model derived from first-principles.

Plasmodiophora brassicae in its Environment

Plasmodiophora brassicae Wor. is viewed in this article from the standpoint of a highly evolved and successful organism, well fitted for the ecological niche that it occupies. Physical, chemical, and biological components of the soil environment are discussed in relation to their effects on the survival, growth, and reproduction of this microbe. It is evident that P. brassicae is well equipped by virtue of its robust resting spores for survival through many seasonal cycles. Germination is probably triggered as a result of signals initiated by root exudates. The resultant motile zoospore moves rapidly to the root hair surface and penetration and colonization follow. The short period between germination and penetration is one of greatest vulnerability for P. brassicae. In this phase survival is affected at the very least by soil texture and structure; its moisture; pH; calcium, boron, and nitrogen content; and the presence of active microbial antagonists. These factors influence the inoculum potential (sensu Garrett, 1956) and its viability and invasive capacity. There is evidence that these effects may also influence differentially the survival of some physiologic races of P. brassicae. Considering the interaction of P. brassicae with the soil environment from the perspective of its biological fitness is an unusual approach; most authors consider only the opportunities to destroy this organism. The approach adopted here is borne of several decades spent studying P. brassicae and the respect that has been engendered for it as a biological entity. This review stops at the point of penetration, although some of the implications of the environment for successful colonization are included because they form a continuum. Interactions with the molecular and biochemical cellular environment are considered in other sections in this special edition.

Carbon-decorated FePt nanoparticles

FePt magnetic nanoparticles are an important candidate material for many future magnetic applications. FePt exists as two main phases, that is, a disordered face-centered cubic (fcc) structure, which is generally prepared by chemical methods at low temperatures, and the high-temperature chemically ordered face-centered tetragonal (fct) structure. The fee FePt, with low coercivity but associated with superparamagnetic properties, may find applications as a magnetic fluid or as a nanoscale carrier for chemical or biochemical species in biomedical areas, while fct FePt is proposed for use in ultrahigh-density magnetic recording applications. However, for both of these applications an enhancement of the intrinsically weak magnetic properties, the avoidance of magnetic interferences from neighbor particles, and the improved stability of the small magnetic body remain key practical issues. We report a simple synthetic method for producing FePt nanoparticles that involves hydrothermal treatment of Fe and Pt precursors in glucose followed by calcination at 900 degrees C. This new method produces thermally stable spheroidal graphite nanoparticles (large and fullerene-like) that encapsulate or decorate FePt particles of ca. 5 nm with no severe macroscopic particle coalescence. Also, a low coercivity of the material is recorded; indicative of small magnetic interference from neighboring carbon-coated particles. Thus, this simple synthetic method involves the use of a more environmentally acceptable glucose/aqueous phase to offer a protective coating for FePt nanoparticles. It is also believed that such a synthetic protocol can be readily extended to the preparation of other graphite-coated magnetic iron alloys of controlled size, stoichiometry, and physical properties.

Carbon-encapsulated radioactive Tc-99m nanoparticles

A macroscopic quantity of quasi-spherical fullerene-like shells (see Figure) that encapsulate iron nanoparticles containing radioisotope Tc-99m are prepared for the first time. The nanocomposite is acid-non-leachable, retaining radioactivity at an extremely high level. This method will enable rigorous studies of what are currently theoretical descriptions of nanometer-scale medicinal delivery vehicles for diagnostic and therapeutic purposes.

Extended-chain, multinuclear transition metal complexes bridged by cyanodiazenido(1-), [N=N-C=N](-), ligands

Extended-chain complexes containing multiple transition metal centres linked by conjugated mu-cyanodiazenido(1-) ligands [N= N-C N]-have been obtained by reaction of trans-[BrW(dppe)(2)(N2CN)], 1, [dppe = 1,2-bis(diphenylphosphino) ethane] with dirhodium(II) tetra-acetate, bis(benzonitrile) palladium(II) dichloride, and bis(aqua) M(II) bis(hexa. uoroacetylacetonate) (M = Mn, Ni, Cu, Zn): stronger Lewis acids such as tetrakis(acetonitrile) palladium(II) tetra. uoroborate and boron trifl. uoride promote hydrolysis of complex 1, leading to the isolation of a novel carbamoylhydrazido(2-) complex, trans-[BrW(dppe) 2(N2HC=ONH2)](+)[BF4](-).

Nanosized polymetallic resorcinarene-based host assemblies that strongly bind fullerenes

Polymetallic nanodimensional assemblies have been prepared via metal directed assembly of dithiocarbamate functionalized cavitand structural frameworks with late transition metals (Ni, Pd, Cu, Au, Zn, and Cd). The coordination geometry about the metal centers is shown to dictate the architecture adopted. X-ray crystallographic studies confirm that square planar coordination geometries result in "cagelike" octanuclear complexes, whereas square-based pyramidal metal geometries favor hexanuclear "molecular loop" structures. Both classes of complex are sterically and electronically complementary to the fullerenes (C-60 and C-70). The strong binding of these guests occurred via favorable interactions with the sulfur atoms of multiple dithiocarbamate moieties of the hosts. In the case of the tetrameric copper(II) complexes, the lability of the copper(II)-dithiocarbamate bond enabled the fullerene guests to be encapsulated in the electron-rich cavity of the host, over time. The examination of the binding of fullerenes has been undertaken using spectroscopic and electrochemical methods, electrospray mass spectrometry, and molecular modeling.

Imaging the structure of activated carbon using aberration corrected TEM

The precise atomic structure of activated carbon is unknown, despite its commercial importance. Here we show that the structure of a commercial activated carbon can be imaged directly using aberration corrected transmission electron microscopy. Images are presented both of the as-produced carbon and of the carbon following heat- treatment at 2000°C. In the 2000°C carbon clear evidence is found for the presence of pentagonal rings, suggesting that the carbons have a fullerene-related structure.

Structural transformation of graphite by arc-discharge

The formation of novel structures by the passage of an electric current through graphite is described. These structures apparently consist of hollow three-dimensional graphitic shells bounded by curved and faceted planes, typically made up of two graphene layers. The curved structures were frequently decorated with nano-scale carbon particles, or short nanotubes. In some cases, nanotubes were found to be seamlessly connected to the thin shells, indicating that the formation of the shells and the nanotubes is intimately connected. Small nanotubes or nanoparticles were also sometimes found encapsulated inside the hollow structures, while fullerene-like particles were often seen attached to the outside surfaces. With their high surface areas and structural perfection, the new carbon structures may have applications as anodes of lithium ion batteries or as components of composite materials.