Factors affecting biomass production and nutritive value of Calliandra calothyrsus leaf as fodder for ruminants

Calliandra calothyrsus is a tree legume native to Mexico and Central America. The species has attracted considerable attention for its capacity to produce both fuelwood and foliage for either green manure or fodder. Its high content of proanthocyanidins (condensed tannins) and associated low digestibility has, however, limited its use as a feed for ruminants, and there is also a widespread perception that wilting the leaves further reduces their nutritive value. Nevertheless, there has been increasing uptake of calliandra as fodder in certain regions, notably the Central Highlands of Kenya. The present study, conducted in Embu, Kenya, investigated effects of provenance, wilting, cutting frequency and seasonal variation both in the laboratory (in vitro digestibility, crude protein, neutral detergent fibre, extractable and bound proanthocyanidins) and in on-station animal production trials with growing lambs and lactating goats. The local Kenyan landrace of calliandra (Embu) and a closely-related Guatemalan provenance (Patulul) were found to be significantly different, and superior, to a provenance from Nicaragua (San Ramon) in most of the laboratory traits measured, as well as in animal production and feed efficiency. Cutting frequency had no important effect on quality; and although all quality traits displayed seasonal variation there was little discernible pattern to this variation. Wilting had a much less negative effect than expected, and for lambs fed calliandra as a supplement to a low quality basal feed (maize stover), wilting was actually found to give higher live-weight gain and feed efficiency. Conversely, with a high quality basal diet (Napier grass) wilting enhanced intake but not live-weight gain, so feed efficiency was greater for fresh material. The difference between fresh and wilted leaves was not great enough to justify the current widespread recommendation that calliandra should always be fed fresh.

Extracellular disulfide exchange and the regulation of cellular function

An emerging concept is that disulfide bonds can act as a dynamic scaffold to present mature proteins in different conformational and functional states on the cell surface. Two examples are the conversion of the receptor, integrin a alpha(IIb)beta(3), from a low affinity to a high affinity state, and the interaction of CD4 receptor with the HIV-1 envelope glycoprotein gp120 to promote virus-cell fusion. In both of these cases there is a remodeling of the protein disulfide bonding pattern. The formation and rearrangement of disulfide bonds is modulated by a family of enzymes known as the thiol isomerases, which include protein disulfide isomerase (PDI), ERp5, ERp57, and ERp72. While these enzymes were reported originally to be restricted in location to the endoplasmic reticulum, in some cells thiol isomerases are found on the cell surface. This may indicate a wider role for these enzymes in cell function. In platelets it has been shown that reagents that react with cell surface sulfhydryl groups are capable of blocking a number of functional responses, including integrin-mediated aggregation, adhesion, and granule secretion. Furthermore, the use of function blocking antibodies to either PDI or ERp5 causes inhibition of these functional responses. This review summarizes current knowledge of the extracellular regulation of disulfide exchange and the implications of this in the regulation of cell function.

Quantum mechanics studies of the tautomers of diacetylformoin, an important maillard product and odorant

Diacetylformoin (3,4-dihydroxy-3-hexene-2,5-dione) has 16 tautomers, many with several possible conformations and all have been geometry optimised using quantum mechanics at the HF/6-31+G* level. Eleven structures have been identified with energies within 10 kcal mol(-1) of the minimum energy structure. Of these eight are acyclic and three cyclic. Calculations of NMR spectra have clarified the identity of the acyclic and cyclic structures found experimentally. The mechanism for cyclisation has been investigated and transition states obtained. The lowest energy reaction path requires the loss and gain of a proton during cyclisation. (c) 2006 Elsevier B.V. All rights reserved.

Proteomic analysis of the site specificity of glycation and carboxymethylation of ribonuclease

Proteomic analysis using electrospray liquid chromatography-mass spectrometry (ESI-LC-MS) has been used to compare the sites of glycation (Amadori adduct formation) and carboxymethylation of RNase and to assess the role of the Amadori adduct in the formation of the advanced glycation end-product (AGE), N-is an element of-(carboxymethyl)lysine (CIVIL). RNase (13.7 mg/mL, 1 mM) was incubated with glucose (0.4 M) at 37 degreesC for 14 days in phosphate buffer (0.2 M, pH 7.4) under air. On the basis of ESI-LC-MS of tryptic peptides, the major sites of glycation of RNase were, in order, K41, K7, K1, and K37. Three of these, in order, K41, K7, and K37 were also the major sites of CIVIL formation. In other experiments, RNase was incubated under anaerobic conditions (1 mM DTPA, N-2 purged) to form Amadori-modified protein, which was then incubated under aerobic conditions to allow AGE formation. Again, the major sites of glycation were, in order, K41, K7, K1, and K37 and the major sites of carboxymethylation were K41, K7, and K37. RNase was also incubated with 1-5 mM glyoxal, substantially more than is formed by autoxidation of glucose under experimental conditions, but there was only trace modification of lysine residues, primarily at K41. We conclude the following: (1) that the primary route to formation of CIVIL is by autoxidation of Amadori adducts on protein, rather than by glyoxal generated on autoxidation of glucose; and (2) that carboxymethylation, like glycation, is a site-specific modification of protein affected by neighboring amino acids and bound ligands, such as phosphate or phosphorylated compounds. Even when the overall extent of protein modification is low, localization of a high proportion of the modifications at a few reactive sites might have important implications for understanding losses in protein functionality in aging and diabetes and also for the design of AGE inhibitors.

Tracking and mean structure of easterly waves over the Intra-Americas Sea

Easterly waves (EWs) are prominent features of the intertropical convergence zone (ITCZ), found in both the Atlantic and Pacific during the Northern Hemisphere summer and fall, where they commonly serve as precursors to hurricanes over both basins.Alarge proportion of Atlantic EWs are known to form over Africa, but the origin of EWs over the Caribbean and east Pacific in particular has not been established in detail. In this study reanalyses are used to examine the coherence of the large-scale wave signatures and to obtain track statistics and energy conversion terms for EWs across this region. Regression analysis demonstrates that some EW kinematic structures readily propagate between the Atlantic and east Pacific, with the highest correlations observed across Costa Rica and Panama. Track statistics are consistent with this analysis and suggest that some individual waves are maintained as they pass from the Atlantic into the east Pacific, whereas others are generated locally in the Caribbean and east Pacific. Vortex anomalies associated with the waves are observed on the leeward side of the Sierra Madre, propagating northwestward along the coast, consistent with previous modeling studies of the interactions between zonal flow and EWs with model topography similar to the Sierra Madre. An energetics analysis additionally indicates that the Caribbean low-level jet and its extension into the east Pacific—known as the Papagayo jet—are a source of energy for EWs in the region. Two case studies support these statistics, as well as demonstrate the modulation of EW track and storm development location by the MJO.

Mono- and heterodimetallic FeII and RuII complexes based on a novel heteroditopic 4′-{bis(phosphanyl)aryl}-2,2′:6′,2″-terpyridine ligand

In the search for a versatile building block that allows the preparation of heteroditopic tpy-pincer bridging ligands, the synthon 14'-[C6H3(CH2Br)(2)-3,5]-2,2':6',2 ''-terpyridine was synthesized. Facile introduction of diphenylphosphanyl groups in this synthon gave the ligand 14'-[C6H3(CH2PPh2)2-3,5]-2,2':6',2"-terpyridine) ([tpyPC(H)Pj). The asymmetric mononuclear complex [Fe(tpy){tpyPC(H)P}](PF6)(2), prepared by selective coordination of [Fe(tpy)Cl-3] to the tpy moiety of [tpyPC(H)P], was used for the synthesis of the heterodimetallic complex [Fe(tpy)(tpyPCP)Ru(tpy)](PFC,)3, which applies the "complex as ligand" approach. Coordination of the ruthenium centre at the PC(H)P-pincer moiety of [Fe(tpy){tpyPC(H)P}](PF6)(2) has been achieved by applying a transcyclometallation procedure. The ground-state electronic properties of both complexes, investigated by cyclic and square-wave voltammetries and UV/Vis spectroscopy, are discussed and compared with those of [Fe(tPY)(2)](PF6)(2) and [Ru(PCP)(tpy)]Cl, which represent the mononuclear components of the heterodinuclear species. An in situ UV/Vis spectroelectrochemical study was performed in order to localize the oxidation and reduction steps and to gain information about the Fe-II-Ru-II communication in the heterodimetallic system [Fe(tpy)(tpyPCP)Ru(tpy)](PF6)(3) mediated by the bridging ligand [tpyPCP]. Both the voltammetric and spectroelectrochemical results point to only very limited electronic interaction between the metal centres in the ground state.

Origin of electronic absorption spectra of MLCT-excited and one-electron reduced 2,2′-bipyridine and 1,10-phenanthroline complexes

UV–Vis absorption spectra of one-electron reduction products and 3MLCT excited states of [ReICl(CO)3- (N,N)] (N,N = 2,20-bipyridine, bpy; 1,10-phenanthroline, phen) have been measured by low-temperature spectroelectrochemistry and UV–Vis transient absorption spectroscopy, respectively, and assigned by open-shell TD-DFT calculations. The characters of the electronic transitions are visualized and analyzed using electron density redistribution maps. It follows that reduced and excited states can be approximately formulated as [ReICl(CO)3(N,Nÿ)]ÿ and ⁄[ReIICl(CO)3(N,Nÿ)], respectively. UV–Vis spectra of the reduced complexes are dominated by IL transitions, plus weaker MLCT contributions. Excited-state spectra show an intense band in the UV region of 50% IL origin mixed with LMCT (bpy, 373 nm) or MLCT (phen, 307 nm) excitations. Because of the significant IL contribution, this spectral feature is akin to the principal IL band of the anions. In contrast, the excited-state visible spectral pattern arises from predominantly LMCT transitions, any resemblance with the reduced-state visible spectra being coincidental. The Re complexes studied herein are representatives of a broad class of metal a-diimines, for which similar spectroscopic behavior can be expected.

Nickel(II) and copper(II) complexes of Schiff base ligands containing N4O2 and N4S2 donors with pyrrole terminal binding groups: synthesis, characterization, X-ray structures, DFT and electrochemical studies

A series of hexadentate ligands, H2Lm (m = 1−4), [1H-pyrrol-2-ylmethylene]{2-[2-(2-{[1H-pyrrol-2-ylmethylene]amino}phenoxy)ethoxy]phenyl}amine (H2L1), [1H-pyrrol-2-ylmethylene]{2-[4-(2-{[1H-pyrrol-2-ylmethylene]amino}phenoxy)butoxy]phenyl}amine (H2L2), [1H-pyrrol-2-ylmethylene][2-({2-[(2-{[1H-pyrrol-2-ylmethylene]amino}phenyl)thio]ethyl}thio)phenyl]amine (H2L3) and [1H-pyrrol-2-ylmethylene][2-({4-[(2-{[1H-pyrrol-2-lmethylene]amino}phenyl)thio]butyl}thio) phenyl]amine (H2L4) were prepared by condensation reaction of pyrrol-2-carboxaldehyde with {2-[2-(2-aminophenoxy)ethoxy]phenyl}amine, {2-[4-(2-aminophenoxy)butoxy]phenyl}amine, [2-({2-[(2-aminophenyl)thio]ethyl}thio)phenyl]amine and [2-({4-[(2-aminophenyl)thio]butyl}thio)phenyl]amine respectively. Reaction of these ligands with nickel(II) and copper(II) acetate gave complexes of the form MLm (m = 1−4), and the synthesized ligands and their complexes have been characterized by a variety of physico-chemical techniques. The solid and solution states investigations show that the complexes are neutral. The molecular structures of NiL3 and CuL2, which have been determined by single crystal X-ray diffraction, indicate that the NiL3 complex has a distorted octahedral coordination environment around the metal while the CuL2 complex has a seesaw coordination geometry. DFT calculations were used to analyse the electronic structure and simulation of the electronic absorption spectrum of the CuL2 complex using TDDFT gives results that are consistent with the measured spectroscopic behavior of the complex. Cyclic voltammetry indicates that all copper complexes are electrochemically inactive but the nickel complexes with softer thioethers are more easily oxidized than their oxygen analogs.

Solar signal propagation: the role of gravity waves and stratospheric sudden warmings

We use a troposphere‐stratosphere model of intermediate complexity to study the atmospheric response to an idealized solar forcing in the subtropical upper stratosphere during Northern Hemisphere (NH) early winter. We investigate two conditions that could influence poleward and downward propagation of the response: (1) the representation of gravity wave effects and (2) the presence/absence of stratospheric sudden warmings (SSWs). We also investigate how the perturbation influences the timing and frequency of SSWs. Differences in the poleward and downward propagation of the response within the stratosphere are found depending on whether Rayleigh friction (RF) or a gravity wave scheme (GWS) is used to represent gravity wave effects. These differences are likely related to differences in planetary wave activity in the GWS and RF versions, as planetary wave redistribution plays an important role in the downward and poleward propagation of stratospheric signals. There is also remarkable sensitivity in the tropospheric response to the representation of the gravity wave effects. It is most realistic for GWS. Further, tropospheric responses are systematically different dependent on the absence/presence of SSWs. When only years with SSWs are examined, the tropospheric signal appears to have descended from the stratosphere, while the signal in the troposphere appears disconnected from the stratosphere when years with SSWs are excluded. Different troposphere‐stratosphere coupling mechanisms therefore appear to be dominant for years with and without SSWs. The forcing does not affect the timing of SSWs, but does result in a higher occurrence frequency throughout NH winter. Quasi‐Biennial Oscillation effects were not included.

Three dimensional picture of the local structure of 1,4-Polybutadiene from a complete atomistic model and neutron scattering data

An efficient method of combining neutron diffraction data over an extended Q range with detailed atomistic models is presented. A quantitative and qualitative mapping of the organization of the chain conformation in both glass and liquid phase has been performed. The proposed structural refinement method is based on the exploitation of the intrachain features of the diffraction pattern by the use of internal coordinates for bond lengths, valence angles and torsion rotations. Models are built stochastically by assignment of these internal coordinates from probability distributions with limited variable parameters. Variation of these parameters is used in the construction of models that minimize the differences between the observed and calculated structure factors. A series of neutron scattering data of 1,4-polybutadiene at the region 20320 K is presented. Analysis of the experimental data yield bond lengths for C-C and C=C of 1.54 and 1.35 Å respectively. Valence angles of the backbone were found to be at 112 and 122.8 for the CCC and CC=C respectively. Three torsion angles corresponding to the double bond and the adjacent R and β bonds were found to occupy cis and trans, s(, trans and g( and trans states, respectively. We compare our results with theoretical predictions, computer simulations, RIS models, and previously reported experimental results.

A proposal for a new scenario framework to support research and assessment in different climate research communities

In this paper, we propose a scenario framework that could provide a scenario “thread” through the different climate research communities (climate change – vulnerability, impact, and adaptation (VIA) and mitigation) in order to provide assessment of mitigation and adaptation strategies and other VIA challenges. The scenario framework is organised around a matrix with two main axes: radiative forcing levels and socio-economic conditions. The radiative forcing levels (and the associated climate signal) are described by the new Representative Concentration Pathways. The second axis, socio-economic developments, comprises elements that affect the capacity for mitigation and adaptation, as well as the exposure to climate impacts. The proposed scenarios derived from this framework are limited in number, allow for comparison across various mitigation and adaptation levels, address a range of vulnerability characteristics, provide information across climate forcing and vulnerability states and span a full century time scale. Assessments based on the proposed scenario framework would strengthen cooperation between integrated-assessment modelers, climate modelers and vulnerability, impact and adaptation researchers, and most importantly, facilitate the development of more consistent and comparable research within and across communities.

Relaxing the Tropics to an ‘observed’ state: analysis using a simple baroclinic model

The technique of relaxation of the tropical atmosphere towards an analysis in a month-season forecast model has previously been successfully exploited in a number of contexts. Here it is shown that when tropical relaxation is used to investigate the possible origin of the observed anomalies in June–July 2007, a simple dynamical model is able to reproduce the observed component of the pattern of anomalies given by an ensemble of ECMWF forecast runs. Following this result, the simple model is used for a range of experiments on time-scales of relaxation, variables and regions relaxed based on a control model run with equatorial heating in a zonal flow. A theory based on scale analysis for the large-scale tropics is used to interpret the results. Typical relationships between scales are determined from the basic equations, and for a specified diabatic heating a chain of deductions for determining the dependent variables is derived. Different critical time-scales are found for tropical relaxation of different dependent variables to be effective. Vorticity has the longest critical time-scale, typically 1.2 days. For temperature and divergence, the time-scales are 10 hours and 3 hours, respectively. However not all the tropical fields, in particular the vertical motion, are reproduced correctly by the model unless divergence is heavily damped. To obtain the correct extra-tropical fields, it is crucial to have the correct rotational flow in the subtropics to initiate the Rossby wave propagation from there. It is sufficient to relax vorticity or temperature on a time-scale comparable or less than their critical time-scales to obtain this. However if the divergent advection of vorticity is important in the Rossby Wave Source then strong relaxation of divergence is required to accurately represent the tropical forcing of Rossby waves.

On the Convergence of Two-Stage Iterative Processes for Solving Linear Equations

This paper considers two-stage iterative processes for solving the linear system $Af = b$. The outer iteration is defined by $Mf^{k + 1} = Nf^k + b$, where $M$ is a nonsingular matrix such that $M - N = A$. At each stage $f^{k + 1} $ is computed approximately using an inner iteration process to solve $Mv = Nf^k + b$ for $v$. At the $k$th outer iteration, $p_k $ inner iterations are performed. It is shown that this procedure converges if $p_k \geqq P$ for some $P$ provided that the inner iteration is convergent and that the outer process would converge if $f^{k + 1} $ were determined exactly at every step. Convergence is also proved under more specialized conditions, and for the procedure where $p_k = p$ for all $k$, an estimate for $p$ is obtained which optimizes the convergence rate. Examples are given for systems arising from the numerical solution of elliptic partial differential equations and numerical results are presented.

Thermogravimetric analysis of water release from wheat flour and wheat bran suspensions

Bran is hygroscopic and competes actively for water with other key components in baked cereal products like starch and gluten. Thermogravimetric analysis (TGA) of flour–water mixtures enriched with bran at different incorporation levels was performed to characterise the release of compartmentalised water. TGA investigations showed that the presence of bran increased compartmentalised water, with the measurement of an increase of total water loss from 58.30 ± 1.93% for flour only systems to 71.80 ± 0.37% in formulations comprising 25% w/w bran. Deconvolution of TGA profiles showed an alteration of the distribution of free and bound water, and its interaction with starch and gluten, within the formulations. TGA profiles showed that water release from bran-enriched flour is a prolonged event with respect to the release from non-enriched flour, which suggests the possibility that bran may interrupt the normal characteristic processes of texture formation that occur in non-enriched products.

Separating the dynamical effects of climate change and ozone depletion. Part II: Southern Hemisphere troposphere

The separate effects of ozone depleting substances (ODSs) and greenhouse gases (GHGs) on forcing circulation changes in the Southern Hemisphere extratropical troposphere are investigated using a version of the Canadian Middle Atmosphere Model (CMAM) that is coupled to an ocean. Circulation-related diagnostics include zonal wind, tropopause pressure, Hadley cell width, jet location, annular mode index, precipitation, wave drag, and eddy fluxes of momentum and heat. As expected, the tropospheric response to the ODS forcing occurs primarily in austral summer, with past (1960-99) and future (2000-99) trends of opposite sign, while the GHG forcing produces more seasonally uniform trends with the same sign in the past and future. In summer the ODS forcing dominates past trends in all diagnostics, while the two forcings contribute nearly equally but oppositely to future trends. The ODS forcing produces a past surface temperature response consisting of cooling over eastern Antarctica, and is the dominant driver of past summertime surface temperature changes when the model is constrained by observed sea surface temperatures. For all diagnostics, the response to the ODS and GHG forcings is additive: that is, the linear trend computed from the simulations using the combined forcings equals (within statistical uncertainty) the sum of the linear trends from the simulations using the two separate forcings. Space time spectra of eddy fluxes and the spatial distribution of transient wave drag are examined to assess the viability of several recently proposed mechanisms for the observed poleward shift in the tropospheric jet.