How to give away £100 million: information for senior decision makers

Every year the National Coal Board divides about £100 million capital for purchasing mining machinery between 12 mining regions. This paper discusses how the allocation should be made, and in particular what information should be provided to the senior management staff who take the final decision.     

Big and little Meccano

The emergence of the mechanical bond during the past 25 years is giving chemistry a fillip in more ways than one. While its arrival on the scene is already impacting materials science and molecular nanotechnology, it is providing a new lease of life to chemical synthesis where mechanical bond formation occurs as a consequence of the all-important templation orchestrated by molecular recognition and self-assembly. The way in which covalent bond formation activates noncovalent bonding interactions, switching on molecular recognition that leads to self-assembly, and the template-directed synthesis of mechanically interlocked molecules—of which the so-called catenanes and rotaxanes may be regarded as the prototypes—has introduced a level of integration into chemical synthesis that has not previously been attained jointly at the supramolecular and molecular levels. The challenge now is to carry this level of integration during molecular synthesis beyond relatively small molecules into the realms of precisely functionalized extended molecular structures and superstructures that perform functions in a collective manner as the key sources of instruction, activation, and performance in multi-component integrated circuits and devices. These forays into organic chemistry by a scientific nomad are traced through thick and thin from the Athens of the North to the Windy City by Lake Michigan with interludes on the edge of the Canadian Shield beside Lake Ontario, in the Socialist Republic of South Yorkshire, on the Plains of Cheshire beside the Wirral, in the Midlands in the Heartland of Albion, and in the City of Angels beside the Peaceful Sea.     

Cp(Pri2MeP)FeH2SiR3: nonclassical iron silyl dihydride

Reactions of a new borohydride complex 2 with hydrosilanes afford half-sandwich dihydride silyl complexes 3a-f. According to X-ray and DFT evidence complexes 3 have unprecedented double H...Si...H interligand interactions.     

Simple cubic super crystals containing PbTe nanocubes and their core-shell building blocks

We report a preparation of high-quality cubic PbTe nanocrystals and their assembly into both square-array, two-dimensional patterns and three-dimensional simple cubic super crystals. The influence of oleylamine in the nanocrystal synthesis and core-shell formation through an anion-exchange mechanism was also studied. The simple cubic super crystals together with two-dimensional assembly patterns containing PbTe nanocubes and their core-shell building blocks were examined using TEM, SEM, AFM, XRD, SAXS, and FTIR. Such super crystals consisting of cubic structural building blocks may allow engineering of more complex materials from which novel properties may emerge.     

Selective photochemical functionalization of surfactant-dispersed single wall carbon nanotubes in water

Ultraviolet (UV) irradiation of single wall carbon nanotubes (SWCNTs) individually dispersed in surfactants leads to diameter and type-selective photohydroxylation of the nanotubes. Photohydroxylation of first semiconductor and then small diameter metallic SWCNTs was confirmed after 254 nm UV irradiation in acidic, neutral, and basic aqueous solutions at ambient and elevated temperatures. The increased oxygen content of the SWCNTs after UV irradiation, as detected by X-ray photoelectron spectroscopy, suggests that SWCNTs were hydroxylated by reaction with water. Attenuated total reflectance Fourier transform infrared analysis provides evidence of hydroxyl functional groups on their surface. This photochemical reaction is impeded by molecular oxygen and appears to involve a reactive intermediate generated in the vicinity of semiconducting SWCNTs. This represents a noncontaminating selective reaction in the liquid phase that uses an intrinsic property of the tubes.     

Stable luminescence from individual carbon nanotubes in acidic, basic, and biological environments

Aqueous surfactant suspensions of single walled carbon nanotubes (SWNTs) are very sensitive to environmental conditions. For example, the photoluminescence of semiconducting SWNTs varies significantly with concentration, pH, or salinity. In most cases, these factors restrict the range of applicability of SWNT suspensions. Here, we report a simple strategy to obtain stable and highly luminescent individualized SWNTs at pH values ranging from 1 to 11, as well as in highly saline buffers. This strategy relies on combining SWNTs previously suspended in sodium dodecylbenzene sulfonate (SDBS) with biocompatible poly(vinyl pyrrolidone) (PVP), which can be polymerized in situ to entrap the SWNT-SDBS micelles. We present a model that accounts for the photoluminescence stability of these suspensions based on PVP morphological changes at different pH values. Moreover, we demonstrate the effectiveness of these highly stable suspensions by imaging individual luminescent SWNTs on the surface of live human embryonic kidney cells (HEK cells).     

Towards the automatic analysis of NMR spectra: part 7. Assignment of 1H by employing both 1H and 1H/13C correlation spectra

A reliable method of automatically assigning one-dimensional proton spectra is described. The method relies on the alignment of the proton spectrum with an associated heteronuclear single-quantum coherence (HSQC) spectrum, transferring the stoichiometry and couplings to the HSQC. The HSQC spectrum is then assigned using a linear assignment procedure in which a fitness function incorporating (1)H chemical shifts, (1)H couplings and (13)C shifts are employed. The method uniquely employs a sequential procedure in which only correlations of like stoichiometry are assigned at the same time.     

Hydrogen bonding to divalent sulfur

A combination of vapor phase infrared spectroscopy and ab initio calculations has been used to show that sulfur is weaker than, but nearly equivalent to, oxygen as a hydrogen bond acceptor. Enthalpies of hydrogen bond formation were obtained for the hydrogen bonded complexes formed between methanol and either dimethyl sulfide or dimethyl ether by temperature dependence studies of the infrared spectra.     

N-Phosphino-amidines and -guanidines: synthesis, structure and P,N-chelate chemistry

The syntheses of the cyclic N-phosphino-amidines and -guanidines Ph2PN(Pri)C(NPri2)N(Pri) ( 1) and Ph2PN(c-Hex)C(R)N(c-Hex) [R = piperazino ( 2), morpholino ( 3), Me ( 4), and Ph ( 5)] are reported. DFT studies have identified the preferred structures for compounds 1-5 with the E-configuration being the most stable form for the N-phosphino-amidines, while the Z-conformation is preferred for the N-phosphino-guanidines something that highlights the potential of such systems to act as kappa2-P,N-chelates. The differences in donor characteristics of 2-5 have been probed through the study of their corresponding P(V) selenide derivatives ( 6-9) and their complexes with the cis-RhCl(CO) (10-12) and cis-PdCl2 (13-17) fragments. In line with the DFT studies both the amidines and guanidines are found to coordinate as kappa2-P,N-chelates, with the latter being moderately weaker donor ligands. The molecular structures of compounds 3 and 4, together with those of the Rh and Pd complexes 10 and 15, respectively, have been determined in the solid state by X-ray crystallography, the latter confirming bidentate kappa2-P,N-chelation.     

Synthesis of morpholin-2-ones by chemoselective intramolecular rhodium-catalyzed reductive ring expansion of oxazolidines

The rhodium-catalyzed reductive intramolecular ring expansion of N-(ethoxycarboxymethyl)oxazolidines was carried out under an atmosphere of carbon monoxide and hydrogen to afford N-methylmorpholin-2-ones in good to excellent yields.