Synthesis, structure and reactivity of novel CuI, CuII and CuIII complexes containing triaza and hexaaza macrocyclic ligands

El treball de tesi s'emmarca dins del camp de la bioinorgànica, disciplina que estudia les propietats estructurals i de reactivitat dels centres actius dels enzims, servint-se de models síntètics de baix pes molecular per tal d'intentar reproduïr la reactivitat presentada per l'enzim i conèixer els mecanismes de reacció a nivell molecular que tenen lloc en els processos biològics.1 Més concretament el treball posa especial èmfasi en els processos d'activació d'oxigen molecular que tenen lloc en les metaloproteïnes de Coure del Tipus 3, com són l'hemocianina i la tirosinasa, ambdues presentant un complex dinuclear de Cu(I)) en el centre actiu de la forma reduïda, capaç d'activar l'O2 cap a espècies de tipus peròxid.2 Un altre camp d'interès ha estat l'estudi dels processos d'activació d'enllaços C-H no activats en hidrocarburs, tant per la seva importàcia a nivell industrial com per comprendre els mecanismes intrínsecs d'aquesta activació a través de metalls de trancisió.3,4 Durant el treball de tesi presentat s'ha desenvolupat la síntesi de nous complexes de Coure(I), Coure(II) y Cu(III) utilitzant lligands macrocíclics de tipus triaza i hexaaza, i s'han estudiat la seves propietats estructurals així com la seva reactivitat. La reacció dels lligands triazacíclics H32m, H2Me33m i H33m amb sals de coure(II) dóna lloc a una reacció de desproporció de Cu(II) per obtenir-se en quantitats equimolars un complex organometàl·lic de Cu(III) i un complex de Cu(I). La caracterizació estructural exhaustiva dels complexes del tipus aryl-Cu(III) evidencia la formació d'un enllaç organometàl·lic entre l'àtom de Cu(III) i el carboni més próxim de l'anell aromàtic del lligand. Aquesta reacció, a més de representar una nova forma de desproporció en la química del Cu, suposa l'activació d'un enllaç C-H aromàtic a temperatura ambient que, mitjançant l'estudi cinètic d'aquesta desproporció per espectroscòpia UV-Vis, dels càlcul de l'efecte cinètic isotòpic utilitzant el lligand deuterat en el C-H de l'anell, juntament amb el recolzament teòrics dels càlculs DFT per a la optimització de geometries d'intermedis de reacció, ens permeten proposar un mecanisme de reacció pel nostre sistema, on l'activació de l'enllaç C-H aromàtic transcorre per la formació d'un enllaç de tipus agòstic C-H ? Cu(II),5 seguit de la desprotonació del C-H aromàtic per acció d'una base i posterior transferència electrònica per obtenir el complex organometàlic de Cu(III) i el complex de de Cu(I). En quant a la reactivitat d'aquests complexes organometàl·lics aryl-Cu(III) s'ha observat que una base en medi aquós causa la inestabilitat d'aquests compostos, evolucionant cap a la inserció d'un àtom d'oxigen sobre la posició activada de l'anell aromàtic, per a donar lloc a un complex dinuclear de Cu(II) amb dos grups fenoxo actuant de pont entre els àtoms metàl·lics. La reacció transcorre per un intermedi colorejat, caracteritzat com el complex ayl-Cu(III) monodesprotonat en una de les seves amines benzíliques, els quals s'observen igualment en la reacció dels correponents complexos de Cu(I) amb oxigen molecular (O2). És en els nostres sistemes en els quals es descriu per primera vegada la participació d'intermedis organometàl·lics Cu(III)-C en processos d'hidroxilació aromàtica, tals com el desenvolupat per l'enzim tirosinasa o per alguns dels seus models químics de síntesi.6,7,8 S'han estudiat les propietats magnètiques dels quatre bis(fenoxo)complexes de Cu(II) descrits, obtenint-se uns acoplaments de tipus antiferromagnètic o ferromagnètic de diversa magnitud, depenent del solapament orbitalari a l'enllaç Cu-O, a través del qual es produeix el superintercanvi. Nous complexos de Cu(I) sintetitzats amb lligands hexaazamacrocíclics han estat estudiats, i posant especial èmfasi a la seva reactivitat respecta a l'activació d'oxigen molecular (O2). S'ha observat una reactivitat diferenciada segons la concentració de complex de Cu(I) utilitzada, de manera que a altes concentracions s'obté un carbonato complex tetranuclear de Cu(II) per fixació de CO2 atmosfèric, mentre que a baixes concentracions s'observa la hidroxilació aromàtica intramolecular d'un dels anells benzílics del lligand, reacció que presumiblement transcorre per atac electrofílic d'un peroxo complex intermedi sobre el sistema ? de l'anell.6 Els resultats obtinguts en aquest treball ens mostren la facilitat per activar enllaços C-H aromàtics per metalls de transició de la primera sèrie (Cu, Ni) quan aquests estan suficientment pròxims a l'enllaç C-H, en unes condicions de reacció molt suaus (1atm., temperatura ambient). Els nous complexos organometàl·lics Aryl-Cu(III) són el producte d'una nova reacció de desproporció de Cu(II), així com un posició aromàtica activada que podria ser el punt de partida per l'estudi de funcionalització selectiva d'aquests grups aromàtics.

Implementation and application of basis set superposition error-correction schemes to the theoretical modeling of weak intermolecular interactions

This thesis deals with the so-called Basis Set Superposition Error (BSSE) from both a methodological and a practical point of view. The purpose of the present thesis is twofold: (a) to contribute step ahead in the correct characterization of weakly bound complexes and, (b) to shed light the understanding of the actual implications of the basis set extension effects in the ab intio calculations and contribute to the BSSE debate. The existing BSSE-correction procedures are deeply analyzed, compared, validated and, if necessary, improved. A new interpretation of the counterpoise (CP) method is used in order to define counterpoise-corrected descriptions of the molecular complexes. This novel point of view allows for a study of the BSSE-effects not only in the interaction energy but also on the potential energy surface and, in general, in any property derived from the molecular energy and its derivatives A program has been developed for the calculation of CP-corrected geometry optimizations and vibrational frequencies, also using several counterpoise schemes for the case of molecular clusters. The method has also been implemented in Gaussian98 revA10 package. The Chemical Hamiltonian Approach (CHA) methodology has been also implemented at the RHF and UHF levels of theory for an arbitrary number interacting systems using an algorithm based on block-diagonal matrices. Along with the methodological development, the effects of the BSSE on the properties of molecular complexes have been discussed in detail. The CP and CHA methodologies are used for the determination of BSSE-corrected molecular complexes properties related to the Potential Energy Surfaces and molecular wavefunction, respectively. First, the behaviour of both BSSE-correction schemes are systematically compared at different levels of theory and basis sets for a number of hydrogen-bonded complexes. The Complete Basis Set (CBS) limit of both uncorrected and CP-corrected molecular properties like stabilization energies and intermolecular distances has also been determined, showing the capital importance of the BSSE correction. Several controversial topics of the BSSE correction are addressed as well. The application of the counterpoise method is applied to internal rotational barriers. The importance of the nuclear relaxation term is also pointed out. The viability of the CP method for dealing with charged complexes and the BSSE effects on the double-well PES blue-shifted hydrogen bonds is also studied in detail. In the case of the molecular clusters the effect of high-order BSSE effects introduced with the hierarchical counterpoise scheme is also determined. The effect of the BSSE on the electron density-related properties is also addressed. The first-order electron density obtained with the CHA/F and CHA/DFT methodologies was used to assess, both graphically and numerically, the redistribution of the charge density upon BSSE-correction. Several tools like the Atoms in Molecules topologycal analysis, density difference maps, Quantum Molecular Similarity, and Chemical Energy Component Analysis were used to deeply analyze, for the first time, the BSSE effects on the electron density of several hydrogen bonded complexes of increasing size. The indirect effect of the BSSE on intermolecular perturbation theory results is also pointed out It is shown that for a BSSE-free SAPT study of hydrogen fluoride clusters, the use of a counterpoise-corrected PES is essential in order to determine the proper molecular geometry to perform the SAPT analysis.

Modelling, control and supervision for a class of hybrid systems

The aim of this thesis is to narrow the gap between two different control techniques: the continuous control and the discrete event control techniques DES. This gap can be reduced by the study of Hybrid systems, and by interpreting as Hybrid systems the majority of large-scale systems. In particular, when looking deeply into a process, it is often possible to identify interaction between discrete and continuous signals. Hybrid systems are systems that have both continuous, and discrete signals. Continuous signals are generally supposed continuous and differentiable in time, since discrete signals are neither continuous nor differentiable in time due to their abrupt changes in time. Continuous signals often represent the measure of natural physical magnitudes such as temperature, pressure etc. The discrete signals are normally artificial signals, operated by human artefacts as current, voltage, light etc. Typical processes modelled as Hybrid systems are production systems, chemical process, or continuos production when time and continuous measures interacts with the transport, and stock inventory system. Complex systems as manufacturing lines are hybrid in a global sense. They can be decomposed into several subsystems, and their links. Another motivation for the study of Hybrid systems is the tools developed by other research domains. These tools benefit from the use of temporal logic for the analysis of several properties of Hybrid systems model, and use it to design systems and controllers, which satisfies physical or imposed restrictions. This thesis is focused in particular types of systems with discrete and continuous signals in interaction. That can be modelled hard non-linealities, such as hysteresis, jumps in the state, limit cycles, etc. and their possible non-deterministic future behaviour expressed by an interpretable model description. The Hybrid systems treated in this work are systems with several discrete states, always less than thirty states (it can arrive to NP hard problem), and continuous dynamics evolving with expression: with Ki ¡ Rn constant vectors or matrices for X components vector. In several states the continuous evolution can be several of them Ki = 0. In this formulation, the mathematics can express Time invariant linear system. By the use of this expression for a local part, the combination of several local linear models is possible to represent non-linear systems. And with the interaction with discrete events of the system the model can compose non-linear Hybrid systems. Especially multistage processes with high continuous dynamics are well represented by the proposed methodology. Sate vectors with more than two components, as third order models or higher is well approximated by the proposed approximation. Flexible belt transmission, chemical reactions with initial start-up and mobile robots with important friction are several physical systems, which profits from the benefits of proposed methodology (accuracy). The motivation of this thesis is to obtain a solution that can control and drive the Hybrid systems from the origin or starting point to the goal. How to obtain this solution, and which is the best solution in terms of one cost function subject to the physical restrictions and control actions is analysed. Hybrid systems that have several possible states, different ways to drive the system to the goal and different continuous control signals are problems that motivate this research. The requirements of the system on which we work is: a model that can represent the behaviour of the non-linear systems, and that possibilities the prediction of possible future behaviour for the model, in order to apply an supervisor which decides the optimal and secure action to drive the system toward the goal. Specific problems can be determined by the use of this kind of hybrid models are: - The unity of order. - Control the system along a reachable path. - Control the system in a safe path. - Optimise the cost function. - Modularity of control The proposed model solves the specified problems in the switching models problem, the initial condition calculus and the unity of the order models. Continuous and discrete phenomena are represented in Linear hybrid models, defined with defined eighth-tuple parameters to model different types of hybrid phenomena. Applying a transformation over the state vector : for LTI system we obtain from a two-dimensional SS a single parameter, alpha, which still maintains the dynamical information. Combining this parameter with the system output, a complete description of the system is obtained in a form of a graph in polar representation. Using Tagaki-Sugeno type III is a fuzzy model which include linear time invariant LTI models for each local model, the fuzzyfication of different LTI local model gives as a result a non-linear time invariant model. In our case the output and the alpha measure govern the membership function. Hybrid systems control is a huge task, the processes need to be guided from the Starting point to the desired End point, passing a through of different specific states and points in the trajectory. The system can be structured in different levels of abstraction and the control in three layers for the Hybrid systems from planning the process to produce the actions, these are the planning, the process and control layer. In this case the algorithms will be applied to robotics ¡V a domain where improvements are well accepted ¡V it is expected to find a simple repetitive processes for which the extra effort in complexity can be compensated by some cost reductions. It may be also interesting to implement some control optimisation to processes such as fuel injection, DC-DC converters etc. In order to apply the RW theory of discrete event systems on a Hybrid system, we must abstract the continuous signals and to project the events generated for these signals, to obtain new sets of observable and controllable events. Ramadge & Wonham¡¦s theory along with the TCT software give a Controllable Sublanguage of the legal language generated for a Discrete Event System (DES). Continuous abstraction transforms predicates over continuous variables into controllable or uncontrollable events, and modifies the set of uncontrollable, controllable observable and unobservable events. Continuous signals produce into the system virtual events, when this crosses the bound limits. If this event is deterministic, they can be projected. It is necessary to determine the controllability of this event, in order to assign this to the corresponding set, , controllable, uncontrollable, observable and unobservable set of events. Find optimal trajectories in order to minimise some cost function is the goal of the modelling procedure. Mathematical model for the system allows the user to apply mathematical techniques over this expression. These possibilities are, to minimise a specific cost function, to obtain optimal controllers and to approximate a specific trajectory. The combination of the Dynamic Programming with Bellman Principle of optimality, give us the procedure to solve the minimum time trajectory for Hybrid systems. The problem is greater when there exists interaction between adjacent states. In Hybrid systems the problem is to determine the partial set points to be applied at the local models. Optimal controller can be implemented in each local model in order to assure the minimisation of the local costs. The solution of this problem needs to give us the trajectory to follow the system. Trajectory marked by a set of set points to force the system to passing over them. Several ways are possible to drive the system from the Starting point Xi to the End point Xf. Different ways are interesting in: dynamic sense, minimum states, approximation at set points, etc. These ways need to be safe and viable and RchW. And only one of them must to be applied, normally the best, which minimises the proposed cost function. A Reachable Way, this means the controllable way and safe, will be evaluated in order to obtain which one minimises the cost function. Contribution of this work is a complete framework to work with the majority Hybrid systems, the procedures to model, control and supervise are defined and explained and its use is demonstrated. Also explained is the procedure to model the systems to be analysed for automatic verification. Great improvements were obtained by using this methodology in comparison to using other piecewise linear approximations. It is demonstrated in particular cases this methodology can provide best approximation. The most important contribution of this work, is the Alpha approximation for non-linear systems with high dynamics While this kind of process is not typical, but in this case the Alpha approximation is the best linear approximation to use, and give a compact representation.

Contrasting Seasonal Survivorship of Two Migratory Songbirds Wintering in Threatened Mangrove Forests

Long-distance migrants wintering in tropical regions face a number of critical conservation threats throughout their lives, but seasonal estimates of key demographic parameters such as winter survival are rare. Using mist-netting-based mark-recapture data collected in coastal Costa Rica over a six-year period, we examined variation in within- and between-winter survivorship of the Prothonotary Warbler (Protonotaria citrea; 753 young and 376 adults banded), a declining neotropical habitat specialist that depends on threatened mangrove forests during the nonbreeding season. We derived parallel seasonal survivorship estimates for the Northern Waterthrush (Seiurus noveboracensis; 564 young and 93 adults banded), a cohabitant mangrove specialist that has not shown the same population decline in North America, to assess whether contrasting survivorship might contribute to the observed differences in the species’ population trajectories. Although average annual survival probability was relatively similar between the two species for both young and adult birds, monthly estimates indicated that relative to Northern Waterthrush, Prothonotary Warblers exhibited: greater interannual variation in survivorship, especially within winters; greater variation in survivorship among the three study sites; lower average between-winter survivorship, particularly among females, and; a sharp decline in between-winter survivorship from 2003 to 2009 for both age groups and both sexes. Rather than identifying one seasonal vital rate as a causal factor of Prothonotary Warbler population declines, our species comparison suggests that the combination of variable within-winter survival with decreasing between-winter survival demands a multi-seasonal approach to the conservation of this and other tropical-wintering migrants.

Boundary value problems for third-order linear PDEs in time-dependent domains

We present the extension of a methodology to solve moving boundary value problems from the second-order case to the case of the third-order linear evolution PDE qt + qxxx = 0. This extension is the crucial step needed to generalize this methodology to PDEs of arbitrary order. The methodology is based on the derivation of inversion formulae for a class of integral transforms that generalize the Fourier transform and on the analysis of the global relation associated with the PDE. The study of this relation and its inversion using the appropriate generalized transform are the main elements of the proof of our results.

Supply, demand and a failure of understanding: addressing the culture clash between archaeologists' expectations for training and employment in 'academia' versus 'practice

A university degree is effectively a prerequisite for entering the archaeological workforce in the UK. Archaeological employers consider that new entrants to the profession are insufficiently skilled, and hold university training to blame. But university archaeology departments do not consider it their responsibility to deliver fully formed archaeological professionals, but rather to provide an education that can then be applied in different workplaces, within and outside archaeology. The number of individuals studying archaeology at university exceeds the total number working in professional practice, with many more new graduates emerging than archaeological jobs advertised annually. Over-supply of practitioners is also a contributing factor to low pay in archaeology. Steps are being made to provide opportunities for vocational training, both within and outside the university system, but archaeological training and education within the universities and subsequently the archaeological labour market may be adversely impacted upon by the introduction of variable top-up student fees.

Problem structuring methods: theorizing the benefits of deconstructing sustainable development projects

Problem structuring methods or PSMs are widely applied across a range of variable but generally small-scale organizational contexts. However, it has been argued that they are seen and experienced less often in areas of wide ranging and highly complex human activity-specifically those relating to sustainability, environment, democracy and conflict (or SEDC). In an attempt to plan, track and influence human activity in SEDC contexts, the authors in this paper make the theoretical case for a PSM, derived from various existing approaches. They show how it could make a contribution in a specific practical context-within sustainable coastal development projects around the Mediterranean which have utilized systemic and prospective sustainability analysis or, as it is now known, Imagine. The latter is itself a PSM but one which is 'bounded' within the limits of the project to help deliver the required 'deliverables' set out in the project blueprint. The authors argue that sustainable development projects would benefit from a deconstruction of process by those engaged in the project and suggest one approach that could be taken-a breakout from a project-bounded PSM to an analysis that embraces the project itself. The paper begins with an introduction to the sustainable development context and literature and then goes on to illustrate the issues by grounding the debate within a set of projects facilitated by Blue Plan for Mediterranean coastal zones. The paper goes on to show how the analytical framework could be applied and what insights might be generated.

The acoustic signature of fluid flow in complex porous media

Effective medium approximations for the frequency-dependent and complex-valued effective stiffness tensors of cracked/ porous rocks with multiple solid constituents are developed on the basis of the T-matrix approach (based on integral equation methods for quasi-static composites), the elastic - viscoelastic correspondence principle, and a unified treatment of the local and global flow mechanisms, which is consistent with the principle of fluid mass conservation. The main advantage of using the T-matrix approach, rather than the first-order approach of Eshelby or the second-order approach of Hudson, is that it produces physically plausible results even when the volume concentrations of inclusions or cavities are no longer small. The new formulae, which operates with an arbitrary homogeneous (anisotropic) reference medium and contains terms of all order in the volume concentrations of solid particles and communicating cavities, take explicitly account of inclusion shape and spatial distribution independently. We show analytically that an expansion of the T-matrix formulae to first order in the volume concentration of cavities (in agreement with the dilute estimate of Eshelby) has the correct dependence on the properties of the saturating fluid, in the sense that it is consistent with the Brown-Korringa relation, when the frequency is sufficiently low. We present numerical results for the (anisotropic) effective viscoelastic properties of a cracked permeable medium with finite storage porosity, indicating that the complete T-matrix formulae (including the higher-order terms) are generally consistent with the Brown-Korringa relation, at least if we assume the spatial distribution of cavities to be the same for all cavity pairs. We have found an efficient way to treat statistical correlations in the shapes and orientations of the communicating cavities, and also obtained a reasonable match between theoretical predictions (based on a dual porosity model for quartz-clay mixtures, involving relatively flat clay-related pores and more rounded quartz-related pores) and laboratory results for the ultrasonic velocity and attenuation spectra of a suite of typical reservoir rocks. (C) 2003 Elsevier B.V. All rights reserved.

The development and contribution of surface charge by crop residues in two Malawian acid soils

The effects of maize and soya bean residues on the pH and charge of a loamy sand (Kawalazi) and a sandy clay loam (Naming'omba) from Malawi were measured to determine both the indirect effect of the residues on soil charge through the changes in pH, and the direct contribution of charge carried on the residue surfaces. The soils had pH values (10 mM CaCl2) of 4.3 and 5.0 and organic matter contents were 1.4% and 2.7%, respectively. The clay fractions were dominated by kaolinite and goethite, and mica was present in both samples. The soils were incubated for 28 days with maize (Zea mays) and soya bean (Glycine max) residues. The maximum addition of residue (12.0%) in the Kawalazi and Naming'omba soils increased the pH from 4.3 and 5.0 to 4.8 and 5.3 (maize) and to 9.0 and 8.8 (soya bean), respectively. Negative charge increased from 2.1 and 4.7 cmol(c) kg(-1) to 3.8 and 7.5 (maize) and to 5.3 and 9.3 cmol(c) kg(-1) (soya bean). Positive charge increased from 0.72 and 0.62 to 0.87 and 0.85 cmol(c) kg(-1) (maize) and to 0.75 and 0.68 (soya bean). The charge contribution by the residues was calculated by difference between the charge on a sample incubated with residue and the charge on a soil without residue limed to the same pH value. Up to 100 cmolc negative charge and 10 cmol(c) of positive charge per kg of residue were directly contributed to the soil-residue mixture, the amounts depending on the type of residue, the extent to which the residue was decomposed in the soil and the pH of the mixture. The Anderson and Sposito method [Soil Sci. Soc. Am. J. 55 (1991) 1569] was used to partition the permanent negative charge (holding Cs+) from variable negative charge (holding Li+). In the pH range 3.7-6.5 the maize residue contributed between 3 and 26 cmol(c) of variable charge per kg of residue in the Kawalazi soil and between 6 and 25 cmol(c) per kg of residue in the Naming'omba soil. For soya bean the values were between I and 28 and between 4 and 68 cmolc per kg of residue, respectively. At a given pH value, the charge tended to increase with time of incubation and for a given addition of residue, pH decreased during incubation. Addition of residues contributed no permanent negative charge and the charge on the soil measured by Cs adsorption was independent of pH change caused by the residue showing that the method is valid for soil-residue mixtures. With time there was a decrease in the amount of permanent charge probably due to masking as humic material become adsorbed on mineral surfaces. (C) 2003 Elsevier Science B.V. All rights reserved.

Force constants and dipole‐moment derivatives of molecules from perturbed Hartree–Fock calculations

General expressions for the force constants and dipole‐moment derivatives of molecules are derived, and the problems arising in their practical application are reviewed. Great emphasis is placed on the use of the Hartree–Fock function as an approximate wavefunction, and a number of its properties are discussed and re‐emphasised. The main content of this paper is the development of a perturbed Hartree–Fock theory that makes possible the direct calculation of force constants and dipole‐moment derivatives from SCF–MO wavefunctions. Essentially the theory yields ∂ϕi / ∂RJα, the derivative of an MO with respect to a nuclear coordinate.

Integrable evolution equations in time-dependent domains

We discuss the implementation of a method of solving initial boundary value problems in the case of integrable evolution equations in a time-dependent domain. This method is applied to a dispersive linear evolution equation with spatial derivatives of arbitrary order and to the defocusing nonlinear Schrödinger equation, in the domain l(t)derivative is monotonic, and T is a fixed positive constant.

Phylogeny, function, and evolution of the cupins, a structurally conserved, functionally diverse superfamily of proteins

The cupin superfamily is a group of functionally diverse proteins that are found in all three kingdoms of life, Archaea, Eubacteria, and Eukaryota. These proteins have a characteristic signature domain comprising two histidine- containing motifs separated by an intermotif region of variable length. This domain consists of six beta strands within a conserved beta barrel structure. Most cupins, such as microbial phosphomannose isomerases (PMIs), AraC- type transcriptional regulators, and cereal oxalate oxidases (OXOs), contain only a single domain, whereas others, such as seed storage proteins and oxalate decarboxylases (OXDCs), are bi-cupins with two pairs of motifs. Although some cupins have known functions and have been characterized at the biochemical level, the majority are known only from gene cloning or sequencing projects. In this study, phylogenetic analyses were conducted on the conserved domain to investigate the evolution and structure/function relationships of cupins, with an emphasis on single- domain plant germin-like proteins (GLPs). An unrooted phylogeny of cupins from a wide spectrum of evolutionary lineages identified three main clusters, microbial PMIs, OXDCs, and plant GLPs. The sister group to the plant GLPs in the global analysis was then used to root a phylogeny of all available plant GLPs. The resulting phylogeny contained three main clades, classifying the GLPs into distinct subfamilies. It is suggested that these subfamilies correlate with functional categories, one of which contains the bifunctional barley germin that has both OXO and superoxide dismutase (SOD) activity. It is proposed that GLPs function primarily as SODs, enzymes that protect plants from the effects of oxidative stress. Closer inspection of the DNA sequence encoding the intermotif region in plant GLPs showed global conservation of thymine in the second codon position, a character associated with hydrophobic residues. Since many of these proteins are multimeric and enzymatically inactive in their monomeric state, this conservation of hydrophobicity is thought to be associated with the need to maintain the various monomer- monomer interactions. The type of structure-based predictive analysis presented in this paper is an important approach for understanding gene function and evolution in an era when genomes from a wide range of organisms are being sequenced at a rapid rate.

Effect of breed, gender, housing system and dietary crude protein content on performance of finishing beef cattle fed maize-silage-based diets

Maize silage-based diets with three dietary crude protein (CP) supplements were offered to 96 finishing cattle of contrasting breed (Holstein Friesian (HF) v. Simmental x HF (SHF)) and gender (bull v. steer) housed in two types of feeding system (group fed v. individually fed). The three protein supplements differed either in CP or protein degradability (degradable (LUDP) v. rumen undegradable (HUDP)) and provided CP concentrations of 142 (Con), 175 (LUDP) and 179 (HUDP) g/kg dry matter (DM) respectively, with ratios of degradable to undegradable of 3.0, 1.4 and 0.9:1 for diets Con, LOP and HUDP respectively. DM intakes were marginally higher (P = 0. 102) for LOP when compared with Con and HOP Rates of daily live-weight gain (DLWG) were higher (P = 0.005) in LUDP and HOP when compared with Con. HF had higher DM intakes than SHF although this did not result in any improvement in HF DLWG. Bulls had significantly better DM intakes, DLWG and feed conversion efficiency than steers. Conformation scores were better in SHF than HF (P < 0.001) and fat scores lower in bulls than steers (p < 0.001). There was a number of first order interactions established between dietary treatment, breed, gender and housing system with respect to rates of gain and carcass fat scores.

Alternatives to linear analysis of energy balance data from lactating dairy cows

The current energy requirements system used in the United Kingdom for lactating dairy cows utilizes key parameters such as metabolizable energy intake (MEI) at maintenance (MEm), the efficiency of utilization of MEI for 1) maintenance, 2) milk production (k(l)), 3) growth (k(g)), and the efficiency of utilization of body stores for milk production (k(t)). Traditionally, these have been determined using linear regression methods to analyze energy balance data from calorimetry experiments. Many studies have highlighted a number of concerns over current energy feeding systems particularly in relation to these key parameters, and the linear models used for analyzing. Therefore, a database containing 652 dairy cow observations was assembled from calorimetry studies in the United Kingdom. Five functions for analyzing energy balance data were considered: straight line, two diminishing returns functions, (the Mitscherlich and the rectangular hyperbola), and two sigmoidal functions (the logistic and the Gompertz). Meta-analysis of the data was conducted to estimate k(g) and k(t). Values of 0.83 to 0.86 and 0.66 to 0.69 were obtained for k(g) and k(t) using all the functions (with standard errors of 0.028 and 0.027), respectively, which were considerably different from previous reports of 0.60 to 0.75 for k(g) and 0.82 to 0.84 for k(t). Using the estimated values of k(g) and k(t), the data were corrected to allow for body tissue changes. Based on the definition of k(l) as the derivative of the ratio of milk energy derived from MEI to MEI directed towards milk production, MEm and k(l) were determined. Meta-analysis of the pooled data showed that the average k(l) ranged from 0.50 to 0.58 and MEm ranged between 0.34 and 0.64 MJ/kg of BW0.75 per day. Although the constrained Mitscherlich fitted the data as good as the straight line, more observations at high energy intakes (above 2.4 MJ/kg of BW0.75 per day) are required to determine conclusively whether milk energy is related to MEI linearly or not.