Spectro-electrochemical and DFT studies of a planar Cu(II)–phenolate complex active in the aerobic oxidation of primary alcohols

A square-planar compound [Cu(pyrimol)Cl] (pyrimol = 4-methyl-2-N-(2-pyridylmethylene)aminophenolate) abbreviated as CuL–Cl) is described as a biomimetic model of the enzyme galactose oxidase (GOase). This copper(II) compound is capable of stoichiometric aerobic oxidation of activated primary alcohols in acetonitrile/water to the corresponding aldehydes. It can be obtained either from Hpyrimol (HL) or its reduced/hydrogenated form Hpyramol (4-methyl-2-N-(2-pyridylmethyl)aminophenol; H2L) readily converting to pyrimol (L-) on coordination to the copper(II) ion. Crystalline CuL–Cl and its bromide derivative exhibit a perfect square-planar geometry with Cu–O(phenolate) bond lengths of 1.944(2) and 1.938(2) Å. The cyclic voltammogram of CuL–Cl exhibits an irreversible anodic wave at +0.50 and +0.57 V versus ferrocene/ferrocenium (Fc/Fc+) in dry dichloromethane and acetonitrile, respectively, corresponding to oxidation of the phenolate ligand to the corresponding phenoxyl radical. In the strongly donating acetonitrile the oxidation path involves reversible solvent coordination at the Cu(II) centre. The presence of the dominant CuII–L. chromophore in the electrochemically and chemically oxidised species is evident from a new fairly intense electronic absorption at 400–480 nm ascribed to a several electronic transitions having a mixed pi-pi(L.) intraligand and Cu–Cl -> L. charge transfer character. The EPR signal of CuL–Cl disappears on oxidation due to strong intramolecular antiferromagnetic exchange coupling between the phenoxyl radical ligand (L.) and the copper(II) centre, giving rise to a singlet ground state (S = 0). The key step in the mechanism of the primary alcohol oxidation by CuL–Cl is probably the alpha-hydrogen abstraction from the equatorially bound alcoholate by the phenoxyl moiety in the oxidised pyrimol ligand, Cu–L., through a five-membered cyclic transition state.

Understanding stakeholder requirements on an NHS hospital project: application of semiotics-rooted theories.

Hospitals represent complex and difficult contexts for AEC (architecture, engineering and construction) professionals to engage with due to their functional complexity and diversity of stakeholder interests (i.e. patient, visitor, medical specialist). Hospital designers need to take note of changing NHS policy contexts (e.g. the possible empowerment of general practitioners to shape services), technological advances in medical equipment design and the potential health needs of future generations. It is imperative for hospital designers and architects to align their processes and methodologies (e.g. briefing and requirements capture) to the needs and desires of their clients so that a medical facility design is produced which is truly aligned to the requirements of the hospital stakeholders. Semiotics, the “study” or “discipline” of signs aims to investigate the nature of signs (their inception, representation and meaning), whilst semiotics-rooted theories are concerned with investigating how meaning and understanding is mobilized between persons and between organisations. This paper details a semiotics-rooted research approach for investigating the interactions between hospital designers and stakeholders on a forthcoming NHS hospital project in the UK. A semiotics grounded study will potentially provide a deeper understanding of how meaning and understanding is established between hospital project stakeholders and construction professionals.

Anisotropic films of polypyrrole formed electrochemically using a non-planar dopant

We report the electrochemical preparation of electrically conducting films based on polypyrrole, using 10-camphorsulfonate as the dopant, which exhibit a highly anisotropic molecular organisation. This contrasts with earlier reports, in which anisotropy appeared to be restricted to films prepared using aromatic-based planar dopants. Possible growth mechanisms for these materials to account for the molecular anisotropy are discussed.

Tree species diversity interacts with elevated CO2 to induce a greater root system response

As a consequence of land use change and the burning of fossil fuels, atmospheric concentrations of CO2 are increasing and altering the dynamics of the carbon cycle in forest ecosystems. In a number of studies using single tree species, fine root biomass has been shown to be strongly increased by elevated CO2. However, natural forests are often intimate mixtures of a number of co-occurring species. To investigate the interaction between tree mixture and elevated CO2, Alnus glutinosa, Betula pendula and Fagus sylvatica were planted in areas of single species and a three species polyculture in a free-air CO2 enrichment study (BangorFACE). The trees were exposed to ambient or elevated CO2 (580 µmol mol-1) for four years. Fine and coarse root biomass, together with fine root turnover and fine root morphological characteristics were measured. Fine root biomass, and morphology responded differentially to elevated CO2 at different soil depths in the three species when grown in monocultures. In polyculture, a greater response to elevated CO2 was observed in coarse roots to a depth of 20 cm, and fine root area index to a depth of 30 cm. Total fine root biomass was positively affected by elevated CO2 at the end of the experiment, but not by species diversity. Our data suggest that existing biogeochemical cycling models parameterised with data from species grown in monoculture may be underestimating the belowground response to global change.

Robotic multiwell planar patch-clamp for native and primary mammalian cells

Robotic multiwell planar patch-clamp has become common in drug development and safety programs because it enables efficient and systematic testing of compounds against ion channels during voltage-clamp. It has not, however, been adopted significantly in other important areas of ion channel research, where conventional patch-clamp remains the favored method. Here, we show the wider potential of the multiwell approach with the ability for efficient intracellular solution exchange, describing protocols and success rates for recording from a range of native and primary mammalian cells derived from blood vessels, arthritic joints and the immune and central nervous systems. The protocol involves preparing a suspension of single cells to be dispensed robotically into 4-8 microfluidic chambers each containing a glass chip with a small aperture. Under automated control, giga-seals and whole-cell access are achieved followed by preprogrammed routines of voltage paradigms and fast extracellular or intracellular solution exchange. Recording from 48 chambers usually takes 1-6 h depending on the experimental design and yields 16-33 cell recordings.

The influence of biostimulants on growth and vitality of three urban tree species following transplanting

Four commercially available, biostimulants sold under the trade names ‘Generate’, ‘Crop Set’, ‘Fulcrum’ and ‘Redicrop 2000’ were applied either as a root drench or foliar spray to three transplant-sensitive tree species, red oak(Quercus rubra), birch(Betula pendula) and beech (Fagus sylvatica) post transplanting. The short and long-term efficacy of the biostimulants on growth was quantified by recording root and shoot vigour at week 8 and 20. In addition, improvements in tree vitality were assessed by measurement of a chlorophyll a performance index based on leaf chlorophyll fluorescence emissions. Irrespective of species, no significant effect of mode of application (foliar spray versus root drench) was recorded on growth and vitality. The biostimulants Generate and Fulcrum increased growth of all three tree species. No significant effects on growth and chlorophyll fluorescence of birch and beech were recorded following applications of the biostimulants Crop Set and Redicrop 2000, however, significant increase in growth of red oak was recorded. Only the biostimulant Generate increased chlorophyll fluorescence values of all test species. Results show use of biostimulants can improve root and shoot vigour following transplanting. However, selection of an appropriate biostimulant is critical as effects on growth and vitality can vary widely between tree species possibly as a result of the differing active ingredient used in the formulation of the product.

Interface dynamics in planar neural field models

Neural field models describe the coarse-grained activity of populations of interacting neurons. Because of the laminar structure of real cortical tissue they are often studied in two spatial dimensions, where they are well known to generate rich patterns of spatiotemporal activity. Such patterns have been interpreted in a variety of contexts ranging from the understanding of visual hallucinations to the generation of electroencephalographic signals. Typical patterns include localized solutions in the form of traveling spots, as well as intricate labyrinthine structures. These patterns are naturally defined by the interface between low and high states of neural activity. Here we derive the equations of motion for such interfaces and show, for a Heaviside firing rate, that the normal velocity of an interface is given in terms of a non-local Biot-Savart type interaction over the boundaries of the high activity regions. This exact, but dimensionally reduced, system of equations is solved numerically and shown to be in excellent agreement with the full nonlinear integral equation defining the neural field. We develop a linear stability analysis for the interface dynamics that allows us to understand the mechanisms of pattern formation that arise from instabilities of spots, rings, stripes and fronts. We further show how to analyze neural field models with linear adaptation currents, and determine the conditions for the dynamic instability of spots that can give rise to breathers and traveling waves.

Seal Formation in Silicon Planar Patch-Clamp Microstructures

This paper presents a microfabricated planar patch-clamp electrode design and looks at the impact of several physical characteristics on seal formation. The device consists of a patch aperture, 1.5-2.5 mum in diameter and 7-12 mum in depth, with a reverse-side deep-etched 80-mum well. The patch aperture was coated with either thermal oxide or plasma-enhanced chemical vapor deposited (PECVD) SiO2. Some of the thermal oxide devices were converted into protruding nozzle structures, and some were boron-doped. Seal formation was tested with cultured N2a neuroblastoma cells. The PECVD oxide devices produced an average seal resistance of 34 MOmega(n = 24), and the thermal oxide devices produced an average seal resistance of 96 MOmega(n = 59). Seal resistance was found to positively correlate with patch aperture depth. Whole-cell recordings were obtained from 14% of cells tested with the thermal oxide devices, including a single recording where a gigaohm seal was obtained.

Building the niche through time: using 13,000 years of data to predict the effects of climate change on three tree species in Europe

Aim  Species distribution models (SDMs) based on current species ranges underestimate the potential distribution when projected in time and/or space. A multi-temporal model calibration approach has been suggested as an alternative, and we evaluate this using 13,000 years of data. Location  Europe. Methods  We used fossil-based records of presence for Picea abies, Abies alba and Fagus sylvatica and six climatic variables for the period 13,000 to 1000 yr bp. To measure the contribution of each 1000-year time step to the total niche of each species (the niche measured by pooling all the data), we employed a principal components analysis (PCA) calibrated with data over the entire range of possible climates. Then we projected both the total niche and the partial niches from single time frames into the PCA space, and tested if the partial niches were more similar to the total niche than random. Using an ensemble forecasting approach, we calibrated SDMs for each time frame and for the pooled database. We projected each model to current climate and evaluated the results against current pollen data. We also projected all models into the future. Results  Niche similarity between the partial and the total-SDMs was almost always statistically significant and increased through time. SDMs calibrated from single time frames gave different results when projected to current climate, providing evidence of a change in the species realized niches through time. Moreover, they predicted limited climate suitability when compared with the total-SDMs. The same results were obtained when projected to future climates. Main conclusions  The realized climatic niche of species differed for current and future climates when SDMs were calibrated considering different past climates. Building the niche as an ensemble through time represents a way forward to a better understanding of a species' range and its ecology in a changing climate.

Effective LAI and CHP of a single tree from small-footprint full-waveform LiDAR

This letter has tested the canopy height profile (CHP) methodology as a way of effective leaf area index (LAIe) and vertical vegetation profile retrieval at a single-tree level. Waveform and discrete airborne LiDAR data from six swaths, as well as from the combined data of six swaths, were used to extract the LAIe of a single live Callitris glaucophylla tree. LAIe was extracted from raw waveform as an intermediate step in the CHP methodology, with two different vegetation-ground reflectance ratios. Discrete point LAIe estimates were derived from the gap probability using the following: 1) single ground returns and 2) all ground returns. LiDAR LAIe retrievals were subsequently compared to hemispherical photography estimates, yielding mean values within ±7% of the latter, depending on the method used. The CHP of a single dead Callitris glaucophylla tree, representing the distribution of vegetation material, was verified with a field profile manually reconstructed from convergent photographs taken with a fixed-focal-length camera. A binwise comparison of the two profiles showed very high correlation between the data reaching R2 of 0.86 for the CHP from combined swaths. Using a study-area-adjusted reflectance ratio improved the correlation between the profiles, but only marginally in comparison to using an arbitrary ratio of 0.5 for the laser wavelength of 1550 nm.

Classification of seed storage behaviour of 67 Amazonian tree species

Information was collated on the seed storage behaviour of 67 tree species native to the Amazon rainforest of Brazil; 38 appeared to show orthodox, 23 recalcitrant and six intermediate seed storage behaviour. A double-criteria key based on thousand-seed weight and seed moisture content at shedding to estimate likely seed storage behaviour, developed previously, showed good agreement with the above classifications. The key can aid seed storage behaviour identification considerably.

Simulation of tree-ring widths with a model for primary production, carbon allocation, and growth

We present a simple, generic model of annual tree growth, called "T". This model accepts input from a first-principles light-use efficiency model (the "P" model). The P model provides values for gross primary production (GPP) per unit of absorbed photosynthetically active radiation (PAR). Absorbed PAR is estimated from the current leaf area. GPP is allocated to foliage, transport tissue, and fine-root production and respiration in such a way as to satisfy well-understood dimensional and functional relationships. Our approach thereby integrates two modelling approaches separately developed in the global carbon-cycle and forest-science literature. The T model can represent both ontogenetic effects (the impact of ageing) and the effects of environmental variations and trends (climate and CO2) on growth. Driven by local climate records, the model was applied to simulate ring widths during the period 1958–2006 for multiple trees of Pinus koraiensis from the Changbai Mountains in northeastern China. Each tree was initialised at its actual diameter at the time when local climate records started. The model produces realistic simulations of the interannual variability in ring width for different age cohorts (young, mature, and old). Both the simulations and observations show a significant positive response of tree-ring width to growing-season total photosynthetically active radiation (PAR0) and the ratio of actual to potential evapotranspiration (α), and a significant negative response to mean annual temperature (MAT). The slopes of the simulated and observed relationships with PAR0 and α are similar; the negative response to MAT is underestimated by the model. Comparison of simulations with fixed and changing atmospheric CO2 concentration shows that CO2 fertilisation over the past 50 years is too small to be distinguished in the ring-width data, given ontogenetic trends and interannual variability in climate.