Examining the interaction of growing crops with local climate using a coupled crop-climate model

This paper examines to what extent crops and their environment should be viewed as a coupled system. Crop impact assessments currently use climate model output offline to drive process-based crop models. However, in regions where local climate is sensitive to land surface conditions more consistent assessments may be produced with the crop model embedded within the land surface scheme of the climate model. Using a recently developed coupled crop–climate model, the sensitivity of local climate, in particular climate variability, to climatically forced variations in crop growth throughout the tropics is examined by comparing climates simulated with dynamic and prescribed seasonal growth of croplands. Interannual variations in land surface properties associated with variations in crop growth and development were found to have significant impacts on near-surface fluxes and climate; for example, growing season temperature variability was increased by up to 40% by the inclusion of dynamic crops. The impact was greatest in dry years where the response of crop growth to soil moisture deficits enhanced the associated warming via a reduction in evaporation. Parts of the Sahel, India, Brazil, and southern Africa were identified where local climate variability is sensitive to variations in crop growth, and where crop yield is sensitive to variations in surface temperature. Therefore, offline seasonal forecasting methodologies in these regions may underestimate crop yield variability. The inclusion of dynamic crops also altered the mean climate of the humid tropics, highlighting the importance of including dynamical vegetation within climate models.

Intercomparison of radiative forcing calculations of stratospheric water vapour and contrails

Seven groups have participated in an intercomparison study of calculations of radiative forcing (RF) due to stratospheric water vapour (SWV) and contrails. A combination of detailed radiative transfer schemes and codes for global-scale calculations have been used, as well as a combination of idealized simulations and more realistic global-scale changes in stratospheric water vapour and contrails. Detailed line-by-line codes agree within about 15 % for longwave (LW) and shortwave (SW) RF, except in one case where the difference is 30 %. Since the LW and SW RF due to contrails and SWV changes are of opposite sign, the differences between the models seen in the individual LW and SW components can be either compensated or strengthened in the net RF, and thus in relative terms uncertainties are much larger for the net RF. Some of the models used for global-scale simulations of changes in SWV and contrails differ substantially in RF from the more detailed radiative transfer schemes. For the global-scale calculations we use a method of weighting the results to calculate a best estimate based on their performance compared to the more detailed radiative transfer schemes in the idealized simulations.

Fourier transform, null variety, and Laplacian's eigenvalues

We consider a quantity κ(Ω)—the distance to the origin from the null variety of the Fourier transform of the characteristic function of Ω. We conjecture, firstly, that κ(Ω) is maximised, among all convex balanced domains of a fixed volume, by a ball, and also that κ(Ω) is bounded above by the square root of the second Dirichlet eigenvalue of Ω. We prove some weaker versions of these conjectures in dimension two, as well as their validity for domains asymptotically close to a disk, and also discuss further links between κ(Ω) and the eigenvalues of the Laplacians.

Efficiency and purity control in the preparation of pure and/or aluminum-doped barium ferrites by hydrothermal methods using ferrous ions as reactants

The synthesis of hexagonal barium ferrite (BaFe12O19) was studied under hydrothermal conditions by a method in which a significant amount of ferrous chloride was introduced along side ferric chloride among the starting materials. Though all of the Fe2+ ions in the starting material were converted to Fe3+ ions in the final product, Fe2+ was confirmed to participate differently from the Fe3+ used in the conventional method in the mechanism of forming barium ferrite. Indeed the efficiency of the synthesis and the quality of the product and the lack of impurities such as Fe2O3 and BaFe2O4 were improved when Fe2+ was included. However, the amount of ferrous ions that could be included to obtain the desired product was limited with an optimum ratio of 2:8 for FeCl2/FeCl3 when only 2h of reaction time were needed. It was also found that the role of trivalent Fe3+ could be successfully replaced by Al3+. Up to 50% of their on could be replaced by Al3+ in the reactants to produce Al- doped products. It was also found that the ratio of Fe2+/M3+ could be increased in the presence of Al3+ to produce high quality barium ferrite.

Peptidomimetic design of unusual turns by incorporating flexible and rigid omega-amino acids simultaneously

The tripeptides Boc-Gly-Aib-m-ABA-OMe (I), Boc-beta Ala-Aib-m-ABA-OMe (II) and Boc-gamma Abu-Aib-rn-ABA-OMe (III) (Aib: alpha-aminoisobutyric acid, beta Ala: beta-alanine, gamma Abu: gamma-aminobutyric acid, m-ABA: meta-aminobenzoic acid) with homologated amino acids at the N-terminus, the rigid gamma-amino acid m-ABA at the C-terminus and the helicogenic Aib at the central position have been chosen to create unusual turns. Single crystal X-ray diffraction studies, solvent dependent NMR titrations and 2D NMR analysis reveal that peptides II and III adopt unusual turns of 11- and 12-membered rings stabilized by modified 4 -> 1 type intramolecular hydrogen bonds. Solution phase studies indicate that peptide I exists in the beta-turn conformation stabilized by 10-membered intramolecular hydrogen bonding.

Nickel(II) and copper(II) complexes of unsymmetrical tetradentate reduced Schiff base ligands

Two new reduced Schiff base ligands, [HL1 = 4-(2-[(pyridin-2-ylmethyl)-amino]-ethylimino)-pentan-2-one and HL2 =4-[2-(1-pyridin-2-yl-ethylamino)-ethylimino]-pentan-2-one] have been prepared by reduction of the corresponding tetradentate unsymmetrical schiff bases derived from 1.1: 1 condensation of 1,2-ethanediamine, acetylacetone and pyridine-2-carboxaldehyde/2-acetyl pyridine. Four complexes, [Ni(L-1)]ClO4 (1), [Cu(L-1)]ClO4 (2). [Ni(L-2)]ClO4 (3). and [Cu(L-2)]ClO4 (4) with these two reduced Schiff base ligands have been synthesized and structurally characterized by X-ray crystallography. The mono-negative ligands L-1 and L-2 are chelated in all four complexes through the four donor atoms to form square planar nickel(II) and copper(II) complexes Structures of 3 and 4 reveal that enantiomeric pairs are crystallized together with opposite chirality in the nitrogen and carbon atoms. The two Cu-II complexes (2 and 4) exhibit both irreversible reductive (Cu-II/Cu-II, E-pc. -1.00 and -1.04 V) and oxidative (Cu-II/CUII, E-pa, + 1.22 and + 1.17 V, respectively) responses in cyclic voltammetry. The electrochemically generated Cu-1 species for both the complexes are unstable and undergo disproportionation.

Metal-directed assembly of large dinuclear copper(II) dithiocarbamate macrocyclic complexes

The synthesis of a range of dinuclear Cu(II) dithiocarbamate (dtc)-based macrocycles and their characterisation are described. By carefully tuning the size of the aromatic spacer, cavities of different dimensions can be designed. The length and flexibility of the chosen spacer group dictates the intermetallic distance and hence the degree of communication between the two metal centres as evidenced by electrochemical and EPR experiments. This is illustrated by crystallographic evidence that show the macrocycles can host guests (such as CH2Cl2) or can fold and form unexpected Cu(I) dtc clusters.