Full-dimensional quantum calculations of ground-state tunneling splitting of malonaldehyde using an accurate ab initio potential energy surface

Quantum calculations of the ground vibrational state tunneling splitting of H-atom and D-atom transfer in malonaldehyde are performed on a full-dimensional ab initio potential energy surface (PES). The PES is a fit to 11 147 near basis-set-limit frozen-core CCSD(T) electronic energies. This surface properly describes the invariance of the potential with respect to all permutations of identical atoms. The saddle-point barrier for the H-atom transfer on the PES is 4.1 kcal/mol, in excellent agreement with the reported ab initio value. Model one-dimensional and "exact" full-dimensional calculations of the splitting for H- and D-atom transfer are done using this PES. The tunneling splittings in full dimensionality are calculated using the unbiased "fixed-node" diffusion Monte Carlo (DMC) method in Cartesian and saddle-point normal coordinates. The ground-state tunneling splitting is found to be 21.6 cm(-1) in Cartesian coordinates and 22.6 cm(-1) in normal coordinates, with an uncertainty of 2-3 cm(-1). This splitting is also calculated based on a model which makes use of the exact single-well zero-point energy (ZPE) obtained with the MULTIMODE code and DMC ZPE and this calculation gives a tunneling splitting of 21-22 cm(-1). The corresponding computed splittings for the D-atom transfer are 3.0, 3.1, and 2-3 cm(-1). These calculated tunneling splittings agree with each other to within less than the standard uncertainties obtained with the DMC method used, which are between 2 and 3 cm(-1), and agree well with the experimental values of 21.6 and 2.9 cm(-1) for the H and D transfer, respectively. (C) 2008 American Institute of Physics.

Land administration in a micro-state: the role of land use planning

Land policy in micro-states and the land administration that underpins it is often devised within a legacy framework inherited from a colonial past. Independence has allowed self-determination of the future political direction yet the range, legal framework, institutional structure and administration systems tend to mirror those of ex-colonial powers. Do land policies, administration systems and processes developed to serve large heavily populated countries scale down to serve the requirements of micro-states? The evidence suggests not: many land administration systems in the Caribbean face difficulties due to poor records, unclear title, exploitation of state lands, incomplete or ongoing land reform programmes, irregular or illegal settlement and non-enforced planning regulations. Land matters are typically the responsibility of several government departments and agencies responsible for land titling and registration, cadastral surveying of property interests, physical planning, taxation and financial regulation. Although planning is regarded as a land administration function, organisational responsibility usually rests with local rather than central government in large countries, but in microstates local government may be politically weak, under-resourced or even non-existent. Using a case study approach this paper explores how planning functions are organised in the Caribbean state of St Vincent & the Grenadines in relation to land administration as a whole and compares the arrangement with other independent micro-states in the region.

Management of elderly patients with breast cancer: updated recommendations of the International Society of Geriatric Oncology (SIOG) and European Society of Breast Cancer Specialists (EUSOMA)

As the mean age of the global population increases, breast cancer in older individuals will be increasingly encountered in clinical practice. Management decisions should not be based on age alone. Establishing recommendations for management of older individuals with breast cancer is challenging because of very limited level 1 evidence in this heterogeneous population. In 2007, the International Society of Geriatric Oncology (SIOG) created a task force to provide evidence-based recommendations for the management of breast cancer in elderly individuals. In 2010, a multidisciplinary SIOG and European Society of Breast Cancer Specialists (EUSOMA) task force gathered to expand and update the 2007 recommendations. The recommendations were expanded to include geriatric assessment, competing causes of mortality, ductal carcinoma in situ, drug safety and compliance, patient preferences, barriers to treatment, and male breast cancer. Recommendations were updated for screening, primary endocrine therapy, surgery, radiotherapy, neoadjuvant and adjuvant systemic therapy, and metastatic breast cancer.

A rare case of solution and solid state inter-conversion of two copper(II) dimers and a copper(II) chain

Three Cu(II)-azido complexes of formula [Cu2L2(N-3)(2)] (1), [Cu2L2(N-3)(2)]center dot H2O (2) and [CuL(N-3)](n) (3) have been synthesized using the same tridentate Schiff base ligand HL (2-[(3-methylaminopropylimino)-methyl]-phenol), the condensation product of N-methyl-1,3-propanediamine and salicyldehyde). Compounds 1 and 2 are basal-apical mu-1,1 double azido bridged dimers. The dimeric structure of 1 is centro-symmetric but that of 2 is non-centrommetric. Compound 3 is a mu-1,1 single azido bridged 1D chain. The three complexes interconvert in solution and can be obtained in pure form by carefully controlling the synthetic conditions. Compound 2 undergoes an irreversible transformation to 1 upon dehydration in the solid state. The magnetic properties of compounds 1 and 2 show the presence of weak antiferromagnetic exchange interactions mediated by the double 1,1-N-3 azido bridges (J = -2.59(4) and -0.10(1) cm-(1), respectively). The single 1,1-N-3 bridge in compound 3 mediates a negligible exchange interaction.

Targeting myocardial remodelling to develop novel therapies for heart failure: a position paper from the Working Group on Myocardial Function of the European Society of Cardiology

The failing heart is characterized by complex tissue remodelling involving increased cardiomyocyte death, and impairment of sarcomere function, metabolic activity, endothelial and vascular function, together with increased inflammation and interstitial fibrosis. For years, therapeutic approaches for heart failure (HF) relied on vasodilators and diuretics which relieve cardiac workload and HF symptoms. The introduction in the clinic of drugs interfering with beta-adrenergic and angiotensin signalling have ameliorated survival by interfering with the intimate mechanism of cardiac compensation. Current therapy, though, still has a limited capacity to restore muscle function fully, and the development of novel therapeutic targets is still an important medical need. Recent progress in understanding the molecular basis of myocardial dysfunction in HF is paving the way for development of new treatments capable of restoring muscle function and targeting specific pathological subsets of LV dysfunction. These include potentiating cardiomyocyte contractility, increasing cardiomyocyte survival and adaptive hypertrophy, increasing oxygen and nutrition supply by sustaining vessel formation, and reducing ventricular stiffness by favourable extracellular matrix remodelling. Here, we consider drugs such as omecamtiv mecarbil, nitroxyl donors, cyclosporin A, SERCA2a (sarcoplasmic/endoplasmic Ca(2 +) ATPase 2a), neuregulin, and bromocriptine, all of which are currently in clinical trials as potential HF therapies, and discuss novel molecular targets with potential therapeutic impact that are in the pre-clinical phases of investigation. Finally, we consider conceptual changes in basic science approaches to improve their translation into successful clinical applications.

Short report: Historical analysis of a near disaster: Anopheles gambiae in Brazil

Attributed to human-mediated dispersal, a species of the Anopheles gambiae complex invaded northeastern Brazil in 1930. This event is considered unique among the intercontinental introductions of disease vectors and the most serious one: ""Few threats to the future health of the Americas have equalled that inherent in the invasion of Brazil, in 1930, by Anopheles gambiae."" Because it was only in the 1960s that An. gambiae was recognized as a species complex now including seven species, the precise species identity of the Brazilian invader remains a mystery. Here we used historical DNA analysis of museum specimens, collected at the time of invasion from Brazil, and aimed at the identification of the Brazilian invader. Our results identify the arid-adapted Anopheles arabiensis as being the actual invading species. Establishing the identity of the species, in addition to being of intrinsic historical interest, can inform future threats of this sort especially in a changing environment. Furthermore, these results highlight the potential danger of human-mediated range expansions of insect disease vectors and the importance of museum collections in retrieving historical information.

Solid-state NMR characterization of a series of copolymers containing fluorene, phenylene and thiophene units

Fluorene and thiophene units are commonly used in polymeric materials for electro-optical applications. Due to differences in reactivity, the final composition of polymers containing these components often differs from that used in their preparation. This contribution describes the synthesis of PPV type terpolymers built by fluorene, phenylene and thiophene units and their quantification by CPMAS NMR. The similarity of the three aromatic co-monomers makes it difficult to separate the analytical responses that would allow quantification of each copolymer unit in the chain. In this sense, we show that the combination of dipolar dephased CPMAS with radiofrequency ramp and proper spectral treatment allows a good estimation and quantification of the copolymer constitution. (C) 2011 Elsevier Ltd. All rights reserved.