Nonlinear Enzyme Kinetics Can Lead to High Metabolic Flux Control Coefficients: Implications for the Evolution of Dominance

In a classic study, Kacser & Burns (1981, Genetics 97, 639-666) demonstrated that given certain plausible assumptions, the flux in a metabolic pathway was more or less indifferent to the activity of any of the enzymes in the pathway taken singly. It was inferred from this that the observed dominance of most wild-type alleles with respect to loss-of-function mutations did not require an adaptive, meaning selectionist, explanation. Cornish-Bowden (1987, J. theor. Biol. 125, 333-338) showed that the Kacser-Burns inference was not valid when substrate concentrations were large relative to the relevant Michaelis constants. We find that in a randomly constructed functional pathway, even when substrate levels are small, one can expect high values of control coefficients for metabolic flux in the presence of significant nonlinearities as exemplified by enzymes with Hill coefficients ranging from two to six, or by the existence of oscillatory loops. Under these conditions the flux can be quite sensitive to changes in enzyme activity as might be caused by inactivating one of the two alleles in a diploid. Therefore, the phenomenon of dominance cannot be a trivial ''default'' consequence of physiology but must be intimately linked to the manner in which metabolic networks have been moulded by natural selection.

An asymmetric homodinuclear complex containing the mu-x-oxobis(mu-x-carboxylato)diruthenium(III) core: X-ray structure of [Ru20(o2ec6H4-p-OMe)3(en) (PPh3)2] (C104)" 3CHC13

Asymmetric tri-bridged diruthenium(III) complexes, [Ru2O(O(2)CR)(3)(en) (PPh(3))(2)](ClO4) (R = C6H4-p-X: X = OMe (1a), Me (1b); en=1,2-diaminoethane), were prepared and structurally characterized. Complex 1a 3CHCl(3), crystallizes in the triclinic space group P (1) over bar with a = 14.029(5), b = 14.205(5), c = 20.610(6) Angstrom, alpha= 107.26(3), beta = 101.84(3), gamma= 97.57(3)degrees, V= 3756(2) Angstrom(3) and Z = 2. The complex has an {Ru-2(mu-O)(mu-O(2)CR)(2)(2+)} core and exhibits [O4PRu(mu-O)RuPO2N2](+) coordination environments for the metal centers. The novel structural feature is the asymmetric arrangement of ligands at the terminal sites of the core which shows an Ru... Ru separation of 3.226(3) Angstrom and an Ru-O-Ru angle of 119.2(5)degrees. An intense visible band observed near 570 nm is assigned to a charge transfer transition involving the d pi-Ru(III) and p pi-mu-O Orbitals. Cyclic voltammetry of the complexes displays a reversible Ru-2(III,III) reversible arrow Ru-2(III,IV) couple near 0.8 V (versus SCE) in MeCN-0.1 M TBAP.

Axial binding of 2-methylimidazole to the tetraarylcarboxylatodiruthenium (II, III) core: X-ray crystal structure of [Ru-2(O2CC6H4-p-OMe)(4)(2-mimH)(2)](ClO4). 1.75CH(2)Cl(2).H2O

Diruthenium (II. III) complexes of the type [Ru-2(O2CAr)(4) (2-mimH)(2)](ClO4) (Ar = C6H4-p-X : X=OMe,1, X=Me, 2, 2-mimH=2-methylimidazole) have been isolated from the reaction of Ru2Cl(O2CAr)(4) with 2-mimH in CH2Cl2 followed by the addition of NaClO4. The crystal structure of 1.1.75CH(2)Cl(2).H2O has been determined. The crystal belongs to the monoclinic space group p2(1)/c with the following unit cell dimensions for the C40H40N4O16ClRu2.1.75CH(2)Cl(2).H2O (M = 1237.0) : a = 12.347(3)Angstrom, b = 17.615(5)Angstrom, c = 26.148(2)Angstrom,beta = 92.88(1)degrees. v = 5679(2)Angstrom(3). Z=4, D-c = 1.45 g cm(-3). lambda(Mo-K-alpha) = 0.7107 Angstrom, mu(Mo-K-alpha) = 8.1 cm(-1), T = 293 K, R = 0.0815 (wR(2) = 0.2118) for 5834 reflections with 1 > 2 sigma(I). The complex has a tetracarboxylatodiruthenium (II, III) core and two axially bound 2-methylimidazole ligands. The Ru-Ru bond length is 2.290(1)Angstrom. The Ru-Ru bond order is 2.5 and the complex is three-electron paramagnetic. The complex shows an irreversible Ru-2(II,III)-->Ru-2(Il,II) reduction near -0.2 V vs SCE in CH2Cl2-0. 1 MTBAP. The complexes exemplify the first adduct of the tetracarboxylatodiruthenium (II,III) core having N-donor ligands

Structural and optical investigation of semiconductor CdSe/CdS core-shell quantum dot thin films

Highly luminescent CdSe/CdS core-shell nanocrystals have been assembled on indium tin oxide (ITO) coated glass substrates using a wet synthesis route. The physical properties of the quantum dots (QD) have been investigated using X-ray diffraction, transmission electron microscopy and optical absorption spectroscopy techniques. These quantum dots showed a strong enhancement in the near band edge absorption. The in situ luminescence behavior has been interpreted in the light of the quantum confinement effect and induced strain in the core-shell structure.

Enantiospecific approach to the tricyclic core structure of tricycloillicinone, ialibinones, and takaneones via ring-closing metathesis reaction

Enantiospecific synthesis of the tricyclic core structure present in the biologically active natural products tricycloillicinone, ialibinones, and takaneones, starting from the readily available campholenaldehyde employing a transannular RCM reaction as the key step, has been accomplished.

The sputtering temperature of a cooling cylindrical rod with an insulated core

By a standard application of Jones's method associated with the Wiener-Hopf technique an explicit solution is obtained for the temperature distribution inside a cylindrical rod with an insulated inner core when the rod is allowed to enter into a fluid of large extent with a uniform speed, and a simple integral expression is derived for the value of the sputtering temperature of the rod at the points of entry. Numerical results under certain special circumstances are also obtained and presented in the form of a table.

Risk management strategies using seasonal climate forecasting in irrigated cotton production: a tale of stochastic dominance.

Decision-making in agriculture is carried out in an uncertain environment with farmers often seeking information to reduce risk. As a result of the extreme variability of rainfall and stream-flows in north-eastern Australia, water supplies for irrigated agriculture are a limiting factor and a source of risk. The present study examined the use of seasonal climate forecasting (SCF) when calculating planting areas for irrigated cotton in the northern Murray Darling Basin. Results show that minimising risk by adjusting plant areas in response to SCF can lead to significant gains in gross margin returns. However, how farmers respond to SCF is dependent on several other factors including irrigators’ attitude towards risk.

Effect of exposure period on degree of dominance of phosphine resistance in adults of Rhyzopertha dominica (Coleoptera: Bostrychidae) and Sitophilus oryzae (Coleoptera: Curculionidae)

Degree of dominance of phosphine resistance was investigated in adults of Rhyzopertha dominica F and Sitophilus oryzae L. Efficacy of the grain fumigant phosphine depends on both concentration and exposure period, which raises the possibility that dominance levels vary with exposure period. New and published data were used to test this possibility in adults of R dominica and S oryzae fumigated for periods of up to 144 h. The concentrations required for control of homozygous resistant and susceptible strains and their F1 hybrids decreased with increasing exposure period. For both species the response lines for the homozygous resistant and susceptible strains and their F1 hybrids were parallel. Therefore, neither dominance level nor resistance factor was affected by exposure period. Resistance was incompletely recessive and the level of dominance, calculated at 50% mortality level, was -0.59 for R dominica and -0.65 for S oryzae. The resistant R dominica strain was 30.9 times more resistant than the susceptible strain, compared with 8.9 times for the resistant S oryzae strain. The results suggest that developing discriminating doses for detecting heterozygote adults of either species will be difficult.

The sputtering temperature of a cooling cylindrical rod with an insulated core

By a standard application of Jones's method associated with the Wiener-Hopf technique an explicit solution is obtained for the temperature distribution inside a cylindrical rod with an insulated inner core when the rod is allowed to enter into a fluid of large extent with a uniform speed, and a simple integral expression is derived for the value of the sputtering temperature of the rod at the points of entry. Numerical results under certain special circumstances are also obtained and presented in the form of a table.

Ce CORE level X-ray photo electron spectroscopy of CeX2Si2 (X = Fe, Co, Ni and Cu)

Ce(3d) and (4d) core level XPS spectra of CeX = Fe, Co, Ni and Cu) suggest that the mean valence of Ce was as well as 4f hybridization strength decrease systematically from Fe to Cu. This observation is in agreement with the results of Bremstrahlung Isochromat Spectroscopy (BIS), but in disagreement with LIII-edge data reported earlier.

Rapid isolation and detection of erythropoietin in blood plasma by magnetic core gold nanoparticles and portable Raman spectroscopy

Isolating, purifying, and identifying proteins in complex biological matrices is often difficult, time consuming, and unreliable. Herein we describe a rapid screening technique for proteins in biological matrices that combines selective protein isolation with direct surface enhanced Raman spectroscopy (SERS) detection. Magnetic core gold nanoparticles were synthesised, characterised, and subsequently functionalized with recombinant human erythropoietin (rHuEPO)-specific antibody. The functionalized nanoparticles were used to capture rHuEPO from horse blood plasma within 15 minutes. The selective binding between the protein and the functionalized nanoparticles was monitored by SERS. The purified protein was then released from the nanoparticles’ surface and directly spectroscopically identified on a commercial nanopillar SERS substrate. ELISA independently confirmed the SERS identification and quantified the released rHuEPO. Finally, the direct SERS detection of the extracted protein was successfully demonstrated for in-field screening by a handheld Raman spectrometer within 1 minute sample measurement time.

Expert Identity in Development of Core-Task-Oriented Working Practices for Mastering Demanding Situations

The point of departure in this dissertation was the practical safety problem of unanticipated, unfamiliar events and unexpected changes in the environment, the demanding situations which the operators should take care of in the complex socio-technical systems. The aim of this thesis was to increase the understanding of demanding situations and of the resources for coping with these situations by presenting a new construct, a conceptual model called Expert Identity (ExId) as a way to open up new solutions to the problem of demanding situations and by testing the model in empirical studies on operator work. The premises of the Core-Task Analysis (CTA) framework were adopted as a starting point: core-task oriented working practices promote the system efficiency (incl. safety, productivity and well-being targets) and that should be supported. The negative effects of stress were summarised and the possible countermeasures related to the operators' personal resources such as experience, expertise, sense of control, conceptions of work and self etc. were considered. ExId was proposed as a way to bring emotional-energetic depth into the work analysis and to supplement CTA-based practical methods to discover development challenges and to contribute to the development of complex socio-technical systems. The potential of ExId to promote understanding of operator work was demonstrated in the context of the six empirical studies on operator work. Each of these studies had its own practical objectives within the corresponding quite broad focuses of the studies. The concluding research questions were: 1) Are the assumptions made in ExId on the basis of the different theories and previous studies supported by the empirical findings? 2) Does the ExId construct promote understanding of the operator work in empirical studies? 3) What are the strengths and weaknesses of the ExId construct? The layers and the assumptions of the development of expert identity appeared to gain evidence. The new conceptual model worked as a part of an analysis of different kinds of data, as a part of different methods used for different purposes, in different work contexts. The results showed that the operators had problems in taking care of the core task resulting from the discrepancy between the demands and resources (either personal or external). The changes of work, the difficulties in reaching the real content of work in the organisation and the limits of the practical means of support had complicated the problem and limited the possibilities of the development actions within the case organisations. Personal resources seemed to be sensitive to the changes, adaptation is taking place, but not deeply or quickly enough. Furthermore, the results showed several characteristics of the studied contexts that complicated the operators' possibilities to grow into or with the demands and to develop practices, expertise and expert identity matching the core task. They were: discontinuation of the work demands, discrepancy between conceptions of work held in the other parts of organisation, visions and the reality faced by the operators, emphasis on the individual efforts and situational solutions. The potential of ExId to open up new paths to solving the problem of the demanding situations and its ability to enable studies on practices in the field was considered in the discussion. The results were interpreted as promising enough to encourage the conduction of further studies on ExId. This dissertation proposes especially contribution to supporting the workers in recognising the changing demands and their possibilities for growing with them when aiming to support human performance in complex socio-technical systems, both in designing the systems and solving the existing problems.

Synthetic studies towards the phloroglucin natural product hyperforin: construction of the fully prenylated bicyclic core

An approach towards the highly functionalized bicyclo[3.3.1]nonan-9-one core of the complex PPAP-based natural product hyperforin, with the full complement of prenyl substituents in required stereo-disposition, is delineated.

Comparison of Elasticity, Shell Core, and Sandwich Shell Theories

The problem of an infinite circular sandwich shell subjected to an a\isymmetric radial line load is investigated using three-dimensional elasticity theory, shell core method, and sandwich shell theory due to Fulton and Schmidt. A comparison of the stresses and displacements with an exact elasticity solution is carried out for various shell parameters in order to clearly bring out the limitations of sandwich shell theories of Fulton and Schmidt as well as the shell core solution.

Tacit Pedagogical Knowing: At the Core of Teacher's Professionality

The purpose of this research was to examine class teachers' interactive pedagogical thinking and action, in other words their tacit pedagogical knowing. Tacit pedagogical knowing was defined as a process in interactive teaching situation, through which a teacher finds solutions to surprising and challenging situations, pedagogical moments, so that the lesson continues. Teachers are able to describe their tacit pedagogical knowing afterwards and also find some reasons for it as well. More specifically, the aim was to study, 1) how does a class teacher's tacit pedagogical knowing appear in teacher's actions, and 2) what kinds of contents include in class teacher's tacit pedagogical knowing. The research material was gathered from four class teachers by videotaping their lessons and by stimulated recall interviews. In addition to this, the researcher spent a relatively long time in the research participants' classrooms. She conducted initial interviews and orientating observations by means of participant observation in order to get to know the participants and their contexts better. A phenomenologically oriented approach, which proceeded by following abductive logic, was used in the analysis procedures of the videotaped and stimulated recall data. In addition to this, correlation examinations were used in the validation of stimulated recall data analyses. The appearance of the tacit pedagogical knowing was observed in the videotaped data. The contents of tacit pedagogical knowing were defined by the analyses of stimulated recall data. According to the research results, a class teacher's tacit pedagogical knowing appears in the maintenance of the pedagogical relation, the teacher's relation to content, and the didactical relation. The contents of class teacher's tacit pedagogical knowing were many sided. The maintenance of the pedagogical relation, the teacher's relation to content, and the didactical relation were elements of the contents as well. In addition to these, the maintenance of teacher's pedagogical authority, the maintenance of the student's role or pedagogical authority, and the awareness of the nature of the content of instruction are included in the contents of teacher's tacit pedagogical knowing. The phenomenon of tacit pedagogical knowing was observed to be clearly a process-like and relational phenomenon. Based on the research results, a model of teacher's tacit pedagogical knowing was developed. Using the model, it is possible to illustrate the factors that are at the core of teacher's professionality. This model could be used in the context of teacher education, supervision, or in-service training.