Synthesis, Structure, and Phosphatase-Like Activity of a New Trinuclear Gd Complex with the Unsymmetrical Ligand H(3)L As a Model for Nucleases

The new trinuclear gadolinium complex [Gd(3)L(2)(NO(3))(2)(H(2)O)(4)]NO(3)center dot 8H(2)O (1) with the unsymmetrical ligand 2-[N-bis-(2-pyridylmethyl)aminomethyl]-4-methyl-6-[N-bis(2-hydroxy-2-oxoethyl)aminomethyl] phenol (H(3)L) was synthesized and characterized. The new ligand H(3)L was obtained in good yield. Complex I crystallizes in an orthorhombic cell, space group Pcab. Kinetic studies show that complex 1 is highly active in the hydrolysis of the substrate 2,4-bis(dinitrophenyl)phosphate (K(m) = 4.09 mM, V(max) = 2.68 x 10(-2) mM s(-1), and k(cat) = V(max)/[1] = 0.67 s(-1)). Through a potentiometric study and determination of the kinetic behavior of 1 in acetonitrile/water solution, the species present in solution could be identified, and a trinuclear monohydroxo species appears to be the most prominent catalyst under mild conditions. Complex 1 displays high efficiency in DNA hydrolytic cleavage, and complete kinetic studies were carried out (K(m) = 4.57 x 10(-4) M, K(cat)` = 3.42 h(-1), and k(cat)`/K(m) = 7.48 x 10(3) M(-1) h(-1)). Studies with a radical scavenger (dimethyl sulfoxide, DMSO) showed that it did not inhibit the activity, indicating the hydrolytic action of 1 in the cleavage of DNA, and studies on the incubation of distamycin with plasmid DNA suggest that 1 is regio-specific, interacting with the minor groove of DNA.

Lu-Hf and U-Pb age determination of Capivarita Anorthosite in the Dom Feliciano Belt, Brazil

The Capivarita Anorthosite, formed in an intraplate environment and later metamorphosed under amphibolites fades conditions, is exposed in the Dom Feliciano Belt as part of the Brasiliano magmatic arc and occurs as a roof-pedant in, or is even intruded by, 0.6 Ga post-collisional granites. In this work, magmatic and metamorphic minerals were dated using the LA-MC-ICP-MS in situ method. U-Pb magmatic and metamorphic zircon dating yielded an age of 1573 +/- 21 Ma and of 606 +/- 6 Ma, respectively, whereas the igneous titanite dating yielded an age of 1530 +/- 33 Ma and the metamorphic ages were 651 +/- 9 Ma and 601 +/- 5 Ma. The Lu-Hf model ages showed two clusters from 1.81 to 2.03 Ga (calf from +2.21 to +6.42) and 2.55-2.62 Ga (epsilon epsilon Hf from -4.59 to -5.64). This intraplate magmatism can be connected to a very important episode of continental accretion in an extensional setting from the fragmentation of the supercontinent during the Early Mesoproterozoic. (C) 2011 Elsevier B.V. All rights reserved.

Effects of Micelles and Vesicles on the Oximolysis of p-Nitrophenyl Diphenyl Phosphate: A Model System for Surfactant-Based Skin-defensive Formulations against Organophosphates

The rates of oximolysis of p-nitrophenyl diphenyl phosphate (PNPDPP) by Acetophenoxime; 10-phenyl-10-hydi-oxyiminodecanoic acid; 4-(9-carboxynonanyl)-1-(9-carboxy-1-hydroyiminononanyl) benzene; 1-dodecyl-2-[(hydroxyimino)methyl]-pyridinium chloride (IV) and N-methylpyridinium-2-aldoxime chloride were determined in micelles of N-hexadecyl-N,N,N-trimethylammonium chloride (CTAC), N-hexadecyl-N,N-dimethylammonium propanesulfonate and dioctadecyldimethylammonium chloride (DODAC) vesicles. The effects of CTAC micelles and DODAC vesicles on the rates of oxymolysis of O,O-Diethyl O-(4-nitrophenyl) phosphate (paraoxon) by oxime IV were also determined. Analysis of micellar and vesicular effects on oximolysis of PNPDPP, using pseudophase or pseudophase with explicit consideration of ion exchange models, required the determination of the aggregate`s effects on the pK(a), of oximes and on the rates of PNPDPP hydrolysis. All aggregates increased the rate of oximolysis of PNPDPP and the results were analyzed quantitatively. In particular, DODAC vesicles catalyzed the reaction and increased the rate of oximolysis of PNPDPP by IV several million fold at pH`s compatible with pharmaceutical formulations. The rate increase produced by DODAC vesicles on the rate of oximolysis paraoxon by IV demonstrates the pharmaceutical potential of this system, since the substrate is used as an agricultural defensive agent and the surfactant is extensively employed in cosmetic formulations. (C) 2008 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 98:1040-1052, 2009

Interaction of cationic bilayer fragments with a model oligonucleotide

The interaction between cationic bilayer fragments and a model oligonucleotide was investigated by differential scanning calorimetry, turbidimetry, determination of excimer to monomer ratio of 2-(10-(1-pyrene)-decanoyl)-phosphatidyl-choline in bilayer fragment dispersions and dynamic light scattering for sizing and zeta-potential analysis. Salt (Na(2)HPO(4)), mononucleotide (2`-deoxyadenosine-5`-monophosphate) or poly (dA) oligonucleotide (3`-AAA AAA AAA A-5`) affected structure and stability of dioctadecyldimethylammonium bromide bilayer fragments. Oligonucleotide and salt increased bilayer packing due to bilayer fragment fusion. Mononucleotide did not reduce colloid stability or did not cause bilayer fragment fusion. Charge neutralization of bilayer fragments by poly (dA) at 1:10 poly (dA):dioctadecyldimethylammonium bromide molar ratio caused extensive aggregation, maximal size and zero of zeta-potential for the assemblies. Above charge neutralization, assemblies recovered colloid stability due to charge overcompensation. For bilayer fragments/poly (dA), the nonmonotonic behavior of colloid stability as a function of poly (dA) concentration was unique for the oligonucleotide and was not observed for Na(2)HPO(4) or 2`-deoxyadenosine-5`-monophosphate. For the first time, such interactions between cationic bilayer fragments and mono- or oligonucleotide were described in the literature. Bilayer fragments/oligonucleotide assemblies may find interesting applications in drug delivery. (c) 2010 Elsevier B.V. All rights reserved.

Determination of amino acids by capillary electrophoresis-electrospray ionization-mass spectrometry: An evaluation of different protein hydrolysis procedures

In this work, a CE equipment, online hyphenated to an IT MS analyzer by a linear sheath liquid interface promoting ESI, was used to develop a method for quantitative determination of amino acids. Under appropriate conditions (BGE composition, 0.8% HCOOH, 20% CH(3)OH; sheath liquid composition, 0.8% HCOOH, 60% methanol; V(ESI), +4.50 W), analytical curves of all amino acids from 3 to 80 mg/L were recorded presenting acceptable linearity (r > 0.99). LODs in the range of 16-172 mu mol/L were obtained. BSA, a model protein, was submitted to different hydrolysis procedures (classical acid and basic, and catalyzed by the H(+) form of a cation exchanger resin) and its amino acid profiles determined. In general, the resin-mediated hydrolysis yields were overall similar or better than those obtained by classical acid or basic hydrolysis. The resulting experimental-to-theoretical BSA concentration ratios served as correction factors for the quantitation of amino acids in Brazil nut resin generated hydrolysates.

Self-determination theory and needs satisfaction in marketing education : are we meeting the needs of students in large marketing classes?

The aim of this study is to assess whether universities are meeting the needs of students in large marketing classes. In so doing the study investigates the application of self determination theory and psychological needs satisfaction. The basic needs scale, comprising of three constructs; Control, Competence and Caring was adapted and used to evaluate students’ perception of an introductory marketing subject. The study used a multi-method approach consisting of a literature review, a qualitative phase involving in-depth interviews with marketing teaching staff and focus groups with marketing students and a survey of students about introductory level marketing. An adapted version of the basic psychological needs scale was included in a questionnaire that was administered to a convenience sample of 366 students. MANOVA, ANOVA and descriptive statistics were used to analyse the data. The results show that the psychological needs satisfaction of many students are not being fully realised. It was also found that marketing degree students enjoyed the challenges and were more stimulated by the subject. The higher achieving students enjoyed the challenge of the subject more than the lower achieving students. As a result of this study, there are three suggestions for further research. Firstly, further study should compare subjects, with relatively small enrolments, to those with large enrolments to corroborate the value of this method of assessing student satisfaction. Secondly, the use of a larger sample across other universities would confirm whether these findings hold for other institutions. Finally, it is suggested that a structural model should be developed to extend this investigation of student satisfaction and the constructs used in the study.

A model of the Australia-US exchange rate

This paper develops a model of exchange rate determination within an error correction framework. The intention is to identify both long and short term determinants that can be used to forecast the AUD/US exchange rate. The paper identifies a set of significant variables associated with exchange rate movements over a twenty year period from 1984 to 2004. Specifically, the overnight interest rate differential, Australia's foreign trade-weighted exposure to commodity prices as well as exchange rate volatility are variables identified that are able explain movements in the AUDIUS dollar relationship. An error correction model is subsequently constructed that incorporates an equilibrium correction term, a short-term interest rate differential variable, a commodity price variable and a proxy for exchange rate volatility. The model is then used to forecast out of sample and is found to dominate a naIve random walk model based on three different metrics.

Instructional strategies integrating cognitive style construct : a meta-knowledge processing model

The overarching goal of this dissertation was to evaluate the contextual components of instructional strategies for the acquisition of complex programming concepts. A meta-knowledge processing model is proposed, on the basis of the research findings, thereby facilitating the selection of media treatment for electronic courseware. When implemented, this model extends the work of Smith (1998), as a front-end methodology, for his glass-box interpreter called Bradman, for teaching novice programmers. Technology now provides the means to produce individualized instructional packages with relative ease. Multimedia and Web courseware development accentuate a highly graphical (or visual) approach to instructional formats. Typically, little consideration is given to the effectiveness of screen-based visual stimuli, and curiously, students are expected to be visually literate, despite the complexity of human-computer interaction. Visual literacy is much harder for some people to acquire than for others! (see Chapter Four: Conditions-of-the-Learner) An innovative research programme was devised to investigate the interactive effect of instructional strategies, enhanced with text-plus-textual metaphors or text-plus-graphical metaphors, and cognitive style, on the acquisition of a special category of abstract (process) programming concept. This type of concept was chosen to focus on the role of analogic knowledge involved in computer programming. The results are discussed within the context of the internal/external exchange process, drawing on Ritchey's (1980) concepts of within-item and between-item encoding elaborations. The methodology developed for the doctoral project integrates earlier research knowledge in a novel, interdisciplinary, conceptual framework, including: from instructional science in the USA, for the concept learning models; British cognitive psychology and human memory research, for defining the cognitive style construct; and Australian educational research, to provide the measurement tools for instructional outcomes. The experimental design consisted of a screening test to determine cognitive style, a pretest to determine prior domain knowledge in abstract programming knowledge elements, the instruction period, and a post-test to measure improved performance. This research design provides a three-level discovery process to articulate: 1) the fusion of strategic knowledge required by the novice learner for dealing with contexts within instructional strategies 2) acquisition of knowledge using measurable instructional outcome and learner characteristics 3) knowledge of the innate environmental factors which influence the instructional outcomes This research has successfully identified the interactive effect of instructional strategy, within an individual's cognitive style construct, in their acquisition of complex programming concepts. However, the significance of the three-level discovery process lies in the scope of the methodology to inform the design of a meta-knowledge processing model for instructional science. Firstly, the British cognitive style testing procedure, is a low cost, user friendly, computer application that effectively measures an individual's position on the two cognitive style continua (Riding & Cheema,1991). Secondly, the QUEST Interactive Test Analysis System (Izard,1995), allows for a probabilistic determination of an individual's knowledge level, relative to other participants, and relative to test-item difficulties. Test-items can be related to skill levels, and consequently, can be used by instructional scientists to measure knowledge acquisition. Finally, an Effect Size Analysis (Cohen,1977) allows for a direct comparison between treatment groups, giving a statistical measurement of how large an effect the independent variables have on the dependent outcomes. Combined with QUEST's hierarchical positioning of participants, this tool can assist in identifying preferred learning conditions for the evaluation of treatment groups. By combining these three assessment analysis tools into instructional research, a computerized learning shell, customised for individuals' cognitive constructs can be created (McKay & Garner,1999). While this approach has widespread application, individual researchers/trainers would nonetheless, need to validate with an extensive pilot study programme (McKay,1999a; McKay,1999b), the interactive effects within their specific learning domain. Furthermore, the instructional material does not need to be limited to a textual/graphical comparison, but could be applied to any two or more instructional treatments of any kind. For instance: a structured versus exploratory strategy. The possibilities and combinations are believed to be endless, provided the focus is maintained on linking of the front-end identification of cognitive style with an improved performance outcome. My in-depth analysis provides a better understanding of the interactive effects of the cognitive style construct and instructional format on the acquisition of abstract concepts, involving spatial relations and logical reasoning. In providing the basis for a meta-knowledge processing model, this research is expected to be of interest to educators, cognitive psychologists, communications engineers and computer scientists specialising in computer-human interactions.

Sample size determination for kernel regression estimation using sequential fixed-width confidence bands

We consider a random design model based on independent and identically distributed pairs of observations (Xi, Yi), where the regression function m(x) is given by m(x) = E(Yi|Xi = x) with one independent variable. In a nonparametric setting the aim is to produce a reasonable approximation to the unknown function m(x) when we have no precise information about the form of the true density, f(x) of X. We describe an estimation procedure of non-parametric regression model at a given point by some appropriately constructed fixed-width (2d) confidence interval with the confidence coefficient of at least 1−. Here, d(> 0) and 2 (0, 1) are two preassigned values. Fixed-width confidence intervals are developed using both Nadaraya-Watson and local linear kernel estimators of nonparametric regression with data-driven bandwidths. The sample size was optimized using the purely and two-stage sequential procedures together with asymptotic properties of the Nadaraya-Watson and local linear estimators. A large scale simulation study was performed to compare their coverage accuracy. The numerical results indicate that the confi dence bands based on the local linear estimator have the better performance than those constructed by using Nadaraya-Watson estimator. However both estimators are shown to have asymptotically correct coverage properties.

On the stress function-based OWA determination method with optimization criteria

The ordered weighted averaging (OWA) determination method with stress function was proposed by Yager, and it makes the OWA operator elements scatter in the shape of the stress function. In this paper, we extend the OWA determination with the stress function method using an optimization model. The proposed method transforms the OWA optimal solution elements into the interpolation points of the stress function. The proposed method extends the basic form of the stress function method with both scale and vertical shift transformations.We also explore a number of properties of this optimization-based stress function method. The OWA operator optimal solution elements can distribute as the shape of the given stress function in a parameterized way, in which case, the solution always possesses the arithmetic average operator as a special case.

Online audio background determination for complex audio environments

We present a method for foreground/background separation of audio using a background modelling technique. The technique models the background in an online, unsupervised, and adaptive fashion, and is designed for application to long term surveillance and monitoring problems. The background is determined using a statistical method to model the states of the audio over time. In addition, three methods are used to increase the accuracy of background modelling in complex audio environments. Such environments can cause the failure of the statistical model to accurately capture the background states. An entropy-based approach is used to unify background representations fragmented over multiple states of the statistical model. The approach successfully unifies such background states, resulting in a more robust background model. We adaptively adjust the number of states considered background according to background complexity, resulting in the more accurate classification of background models. Finally, we use an auxiliary model cache to retain potential background states in the system. This prevents the deletion of such states due to a rapid influx of observed states that can occur for highly dynamic sections of the audio signal. The separation algorithm was successfully applied to a number of audio environments representing monitoring applications.

Rapid determination of protein contents in microencapsulated fish oil supplements by ATR-FTIR spectroscopy and partial least square regression (PLSR) analysis

Following the recent success in quantitative analysis of essential fatty acid compositions in a commercial microencapsulated fish oil (?EFO) supplement, we extended the application of portable attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopic technique and partial least square regression (PLSR) analysis for rapid determination of total protein contents-the other major component in most commercial ?EFO powders. In contrast to the traditional chromatographic methodology used in a routine amino acid analysis (AAA), the ATR-FTIR spectra of the ?EFO powder can be acquired directly from its original powder form with no requirement of any sample preparation, making the technique exceptionally fast, noninvasive, and environmentally friendly as well as being cost effective and hence eminently suitable for routine use by industry. By optimizing the spectral region of interest and number of latent factors through the developed PLSR strategy, a good linear calibration model was produced as indicated by an excellent value of coefficient of determination R2 = 0.9975, using standard ?EFO powders with total protein contents in the range of 140-450 mg/g. The prediction of the protein contents acquired from an independent validation set through the optimized PLSR model was highly accurate as evidenced through (1) a good linear fitting (R2 = 0.9759) in the plot of predicted versus reference values, which were obtained from a standard AAA method, (2) lowest root mean square error of prediction (11.64 mg/g), and (3) high residual predictive deviation (6.83) ranked in very good level of predictive quality indicating high robustness and good predictive performance of the achieved PLSR calibration model. The study therefore demonstrated the potential application of the portable ATR-FTIR technique when used together with PLSR analysis for rapid online monitoring of the two major components (i.e., oil and protein contents) in finished ?EFO powders in the actual manufacturing setting.

A constitutive model of the deformation behaviour of twinning induced plasticity (TWIP) steel at different temperatures

The mechanical behaviour of Fe-18Mn-0.6C-1Al (wt%) TWIP steel was modelled in the temperature range from room temperature to 400°C. The proposed constitutive model was based on the Kocks-Mecking-Estrin (KME) model. The model parameters were determined using extensive experimental measurements of the physical parameters such as the dislocation mean free path and the volume fraction of twinned grains. More than 100 grains with a total area of ~300μm2 were examined at different strain levels over the entire stress-strain curve. Uniaxial tensile deformation of the TWIP steel was modelled for different deformation temperatures using a modelling approach which considers two distinct populations of grains: twinned and twin-free ones. A key point of the work was a meticulous experimental determination of the evolution of the volume fraction of twinned grains during uniaxial tensile deformation. This information was implemented in a phase-mixture model that yielded a very good agreement with the experimental tensile behaviour for the tested range of deformation temperatures. © 2014 Elsevier B.V.

Enhancing permanganate chemiluminescence detection for the determination of glutathione and glutathione disulfide in biological matrices

Acidic potassium permanganate chemiluminescence enables direct post-column detection of glutathione, but its application to assess the redox state of a wider range of biological fluids and tissues is limited by its sensitivity. Herein we show that the simple on-line addition of an aqueous formaldehyde solution not only enhances the sensitivity of the procedure by two orders of magnitude, but also provides a remarkable improvement in the selectivity of the reagent towards thiols such as glutathione (compared to phenols and amino acids that do not possess a thiol group). This enhanced mode of detection was applied to the determination of glutathione and its corresponding disulfide species in homogenised striatum samples taken from both wild type mice and the R6/1 transgenic mouse model of Huntington's disease, at both 8 and 12 weeks of age. No significant difference was observed between the GSH/GSSG ratios of wild type mice and R6/1 mice at either age group, suggesting that the early disease progression had not significantly altered the intracellular redox environment.

On the determination of the number of factors using information criteria with data-driven penalty

As is well known, when using an information criterion to select the number of common factors in factor models the appropriate penalty is generally indetermine in the sense that it can be scaled by an arbitrary constant, c say, without affecting consistency. In an influential paper, Hallin and Liška (J Am Stat Assoc102:603–617, 2007) proposes a data-driven procedure for selecting the appropriate value of c. However, by removing one source of indeterminacy, the new procedure simultaneously creates several new ones, which make for rather complicated implementation, a problem that has been largely overlooked in the literature. By providing an extensive analysis using both simulated and real data, the current paper fills this gap.