The hydrological response of heavy clay grassland soils to rainfall in south‐west England using δ2H

Stable isotopes of water have been previously used in catchment studies to separate rain‐event water from pre‐event groundwater. However, there are a lack of studies at the smaller scale looking at the separation of event water from pre‐event water. This is particularly relevant for heavy clay soil systems through which the movement of water is uncertain but is thought to be rainwater‐dominated. The data presented here were collected at a rural site in the south‐west of England. The historic rainfall at the site was isotopically varied but similar to the global meteoric water line, with annual weighted means of ?37‰ for δ²H and ?5.7‰ for δ¹⁸O and with no seasonal variation. Drainage was sampled from the inter‐flow (surface runoff + lateral through‐flow) and drain‐flow (55 cm deep mole drains) pathways of two 1 ha lysimeters during two rainfall events, which had δ²H values of ?68‰ and ?92‰, respectively. The δ²H values of the lysimeter drainage water suggest that there was no contribution of event water during the first, small discharge (Q) event; however, the second larger event did show isotopic variation in δ²H values negatively related to Q indicating that rainwater was contributing to Q. A hydrograph separation indicated that only 49–58% of the inter‐flow and 18–25% of the drain‐flow consisted of event water. This was surprising given that these soil types are considered retentive of soil water. More work is needed on heavy clay soils to understand better the nature of water movement from these systems. Copyright © 2010 John Wiley & Sons, Ltd.     

Calculating the low temperature vapour line by Monte Carlo

A combination of canonical and grand-canonical ensemble Monte Carlo calculations, together with the virial expansion, have been used to calculate the thermodynamic properties of the liquid/vapour co-existence curve of the (6 : 12) Lennard-Jones fluid for reduced temperatures, [Ttilde] ? 1·1. The results for the liquid density and energy and the latent heat of vaporization are believed to be precise, with the exception of the point at [Ttilde]=1·1 which may lie outside the range of the function fitting the liquid phase Monte Carlo data. The liquid density and the saturated vapour pressure are in very good agreement with the results of perturbation theory. The latent heat of vaporization does not agree well with the experimental data for argon though the fit to liquid density and internal energy is good.     

Concise preparation of novel tricyclic chemotypes: fused hydantoin-benzodiazepines

The following article describes a concise synthesis of a collection of 4,5-dihydro-1H-benzo[e][1,4]diazepines fused to a hydantoin ring. Molecular complexity and biological relevance are high and structures are generated in a mere three steps, employing the Ugi reaction to assemble diversity reagents. The protocol represents a novel UDC (Ugi-deprotect-cyclize) strategy employed in the Ugi-5-component CO₂-mediated condensation, followed by further cyclization under basic conditions, to afford the fused hydantoin. Mechanistic caveats, dependent on the aldehydes of choice will be revealed and a facile oxidation of the final products to imidazolidenetriones is briefly discussed.     

Phase transitions in the litharge and antilitharge structures

Abstract

The compounds PbO and LiOD possess the layered, tetragonal B10 structure and the corresponding antistructure respectively at 1 bar. They undergo very different phase transitions at moderate pressure. At 5 kbar, PbO undergoes a slight, reversible distortion to an orthorhombic phase. The structure is probably an expanded NaCl derivative.

The high-P LiOD phase begins to grow slowly above 17 kbar. Infrared and Raman data indicate that hydrogen bonding is present in the new phase. Neutron powder data indexed on a monoclinic cell. The structure is likely to be similar to that of T1I and NaOH, distorted by the H-bonding.     

Sequential monitoring of a Bernoulli sequence when the pre-change parameter is unknown

The task of monitoring for a change in the mean of a sequence of Bernoulli random variables has been widely studied. However most existing approaches make at least one of the following assumptions, which may be violated in many real-world situations: (1) the pre-change value of the Bernoulli parameter is known in advance, (2) computational efficiency is not paramount, and (3) enough observations occur between change points to allow asymptotic approximations to be used. We develop a novel change detection method based on Fisher’s exact test which does not make any of these assumptions. We show that our method can be implemented in a computationally efficient manner, and is hence suited to sequential monitoring where new observations are constantly being received over time. We assess our method’s performance empirically via using simulated data, and find that it is comparable to the optimal CUSUM scheme which assumes both pre- and post-change values of the parameter to be known.     

Metal segregation in bimetallic clusters and its possible role in synergism and bifunctional catalysis

Aspects of the reactivity of segregated bimetallic compounds and their unusual catalytic properties are reviewed with an emphasis on the author's own studies of platinum—ruthenium mixed-metal cluster complexes and their ability to produce hydrogenation and hydrosilylation of alkynes, catalytically.     

Directed evolution of cyclic peptides for inhibition of autophagy

In recent decades it has become increasingly clear that induction of autophagy plays an important role in the development of treatment resistance and dormancy in many cancer types. Unfortunately, chloroquine (CQ) and hydroxychloroquine (HCQ), two autophagy inhibitors in clinical trials, suffer from poor pharmacokinetics and high toxicity at therapeutic dosages. This has prompted intense interest in the development of targeted autophagy inhibitors to re-sensitize disease to treatment with minimal impact on normal tissue. We utilized Scanning Unnatural Protease Resistant (SUPR) mRNA display to develop macrocyclic peptides targeting the autophagy protein LC3. The resulting peptides bound LC3A and LC3B—two essential components of the autophagosome maturation machinery—with mid-nanomolar affinities and disrupted protein–protein interactions (PPIs) between LC3 and its binding partners in vitro. The most promising LC3-binding SUPR peptide accessed the cytosol at low micromolar concentrations as measured by chloroalkane penetration assay (CAPA) and inhibited starvation-mediated GFP-LC3 puncta formation in a concentration-dependent manner. LC3-binding SUPR peptides re-sensitized platinum-resistant ovarian cancer cells to cisplatin treatment and triggered accumulation of the adapter protein p62 suggesting decreased autophagic flux through successful disruption of LC3 PPIs in cell culture. In mouse models of metastatic ovarian cancer, treatment with LC3-binding SUPR peptides and carboplatin resulted in almost complete inhibition of tumor growth after four weeks of treatment. These results indicate that SUPR peptide mRNA display can be used to develop cell-penetrating macrocyclic peptides that target and disrupt the autophagic machinery in vitro and in vivo.

SUPR peptide mRNA display was used to evolve a cell-permeable, macrocyclic peptide for autophagy inhibition.     

Qualitative Identification of an Unknown Pesticide Using GC-MS and Online Resources

A senior-level instrumental analysis experiment is described in which students examine fruit for pesticide residues. This experiment involves fundamental instruction in sample preparation, the use of gas chromatography (GC) to resolve and deduce important components of a commercial pesticide preparation by matching against a certified standard, and unambiguous identification of the active pesticide by using mass spectrometry in conjunction with public data available on the Internet.