Nucleophilicity at copper(-I) in a compound with a Cu-Mg bond.

Copper is ubiquitous as a structural material, and as a reagent in (bio)chemical transformations. A vast number of chemical reactions rely on the near-inevitable preference of copper for positive oxidation states to make useful compounds. Here we show this electronic paradigm can be subverted in a stable compound with a copper-magnesium bond, which conforms to the formal oxidation state of Cu(-I).

A simply accessible organometallic system to gauge electronic properties of N-heterocyclic carbenes.

The intricate σ and π-bonding of N-heterocyclic carbenes (NHCs) to metals and the need to quantify their electronic properties to rationalize reactivity of complexes have resulted in the creation of numerous methodologies to understand the NHC-metal interaction which are, as we now show, flawed. Our search for a unified, easily accessible system to gauge these fundamental properties has resulted in the discovery of two systems that highlight the flaws present in existing systems and provide a more accurate measure of the NHC ligand electronic properties.

Copper(I) Catalysed Diboron(4) Reduction of Nitrous Oxide.

A process for the catalytic reduction of nitrous oxide using NHC-ligated copper(I) tert-butoxide precatalysts and Bpin as the reductant is reported. These reactions proceed under mild conditions via copper(I)-boryl intermediates which react with NO by facile O-atom insertion into the Cu-B bond and liberate N. Turnover numbers >800 can be achieved at 80 °C under 1 bar NO.

Dial-a-base mechanochemical synthesis of N-heterocyclic carbene copper complexes.

Liquid assisted ball milling of [NHC]HBr (NHC = N-heterocyclic carbene) salts with copper(I) chloride, and a range of alkali metal complexes was shown to efficiently produce (NHC)CuX (NHC = normal or RE-NHC, X = halide, alkoxide, amide, alkyl, aryl; RE-NHC = ring-expanded NHC).

The structures and reactivity of NHC-supported copper(i) triphenylgermyls.

Deprotonation of triphenyl germane with NHC-supported copper alkoxides afforded four novel (NHC)CuGePh complexes. Of these, (IPr)CuGePh (IPr = :C{N(2,6-iPrCH)CH}) was selected for further investigation. Analysis by EDA-NOCV indicates it to be a germyl nucleophile and its σ-bond metathesis reaction with a range of p-block halides confirmed it to be a convenient source of [PhGe].

Acyclic Boryl Complexes of Copper(I).

Reaction of (6-Dipp)CuOtBu (6-Dipp=C{NDippCH } CH , Dipp=2,6-iPr C H ) with B (OMe) provided access to (6-Dipp)CuB(OMe) via σ-bond metathesis. (6-Dipp)CuB(OMe) was characterised by NMR spectroscopy and X-ray crystallography and shown to be a monomeric acyclic boryl of copper. (6-Dipp)CuB(OMe) reacted with ethylene and diphenylacetylene to provide insertion compounds into the Cu-B bond which were characterised by NMR spectroscopy in both cases and X-ray crystallography in the latter.

DNA-Protein Interactions Studied Directly Using iSCAT Imaging of GNP-Tagged Proteins.

Many protein interactions with DNA are reliant on the presence of specific DNA sequences, adducts, or structures. In bulk-phase experiments such DNA features are facile to include in a study. For single-molecule imaging this can be more difficult, because the constraints of the assay limit the variety of adducts that can be used.

Single molecule iSCAT imaging reveals a fast, energy efficient search mode for the DNA repair protein UvrA.

Exposure to UV radiation results in numerous DNA lesions, which threaten genome integrity. The nucleotide excision DNA repair pathway detects and repairs a range of such UV-induced DNA lesions. In bacteria, initial damage detection and verification is carried out by two proteins: UvrA and UvrB.

The structures of ring-expanded NHC supported copper(I) triphenylstannyls and their phenyl transfer reactivity towards heterocumulenes.

Three ring-expanded N-heterocyclic carbene-supported copper(I) triphenylstannyls have been synthesised by the reaction of (RE-NHC)CuOBu with triphenylstannane (RE-NHC = 6-Mes, 6-Dipp, 7-Dipp). The compounds were characterised by NMR spectroscopy and X-ray crystallography. Reaction of (6-Mes)CuSnPh with di--tolyl carbodiimide, phenyl isocyanate and phenylisothiocyanate gives access to a copper(I) benzamidinate, benzamide and benzothiamide respectively phenyl transfer from the triphenylstannyl anion with concomitant formation of (PhSn).

A stable ring-expanded NHC-supported copper boryl and its reactivity towards heterocumulenes.

Reaction of bis(pinacolato)diboron with (6-Dipp)CuOBu generates a ring-expanded N-heterocyclic carbene supported copper(I) boryl, (6-Dipp)CuBpin. This compound showed remarkable stability and was characterised by NMR spectroscopy and X-ray crystallography. (6-Dipp)CuBpin readily dechalcogenated a range of heterocumulenes such as CO, isocyanates and isothiocyanates to yield (6-Dipp)CuXBpin (X = O, S).

Rib osteomyelitis in three foals.

Three foals aged between 21 and 44 days were presented for evaluation of pyrexia and lameness. Each had subcutaneous abscessation associated with osteomyelitis of a rib at the costochondral junction and pathological fracture of the affected rib; one foal had more than one rib affected. Other localised sites of infection included other sites of osteomyelitis, omphalophlebitis, uveitis, enterocolitis, and calcaneal bursitis.

Surgical treatment of carpal flexural deformity in 72 horses.

Unlabelled: Carpal flexural deformities (CFD) are frequently encountered in the horse, with both congenital and acquired forms described. The success of surgical correction of CFD, both in terms of the ability to achieve a straight palmar carpal angle and the impact on future athletic performance, requires further investigation.

Objective: To report the surgical management and outcome of treatment of flexural deformity of the carpus in 72 horses up to 12 months of age.

Repair of sinocutaneous fistulae in two horses.

Chronic facial defects extending into the sinuses of two mares were repaired using periosteal flaps. Partial osseous bridging was established over the defects following repair. Previous attempts to close the defects with skin alone had failed.

Placing healers, healees, and healing into a wider research context.

Healers claim that they can relieve, and often heal, injury and illness against the odds of medical prognosis. Skeptics say that such claims can be accounted for by possible misdiagnosis, uncritical reportage, placebo response, and coincident natural improvement. Their a priori objection is that subjective intention in one person cannot, of itself, affect the physiology and/or mental processes of another person.

Report of the New England Task Force on Reducing Heart Disease and Stroke Risk.

Five years ago, a task force on reducing risk for heart disease and stroke was established by the six New England States. The task force included representatives from State public health departments, academia, the corporate sector, and voluntary organizations. This article is the final report of the task force.

Industrial hypertension program in a rural state. Efficacy and cost effectiveness.

A program was designed to evaluate the efficacy and cost of detecting and treating hypertension in an industrial population of a rural state. Original screening and evaluation was initiated by a trained blood-pressure technician team, but initiation of therapy was the responsibility of the private physician. Follow-up data were obtained at one year by rescreening in 83% and by telephone contact in 91% of the original hypertensive patients.

Industrial hypertension control program in a rural state.

Many problems remain in attempting to improve the detection and management of hypertension in the United States. This study applied a previously established model community hypertension program to a wide geographic area in a rural state. In 47 industries in 18 communities, 15,689 subjects were screened for the presence of hypertension.