An automated microreactor for semi-continuous biosensor measurements.

Living bacteria or yeast cells are frequently used as bioreporters for the detection of specific chemical analytes or conditions of sample toxicity. In particular, bacteria or yeast equipped with synthetic gene circuitry that allows the production of a reliable non-cognate signal (e.g., fluorescent protein or bioluminescence) in response to a defined target make robust and flexible analytical platforms. We report here how bacterial cells expressing a fluorescence reporter ("bactosensors"), which are mostly used for batch sample analysis, can be deployed for automated semi-continuous target analysis in a single concise biochip. Escherichia coli-based bactosensor cells were continuously grown in a 13 or 50 nanoliter-volume reactor on a two-layered polydimethylsiloxane-on-glass microfluidic chip. Physiologically active cells were directed from the nl-reactor to a dedicated sample exposure area, where they were concentrated and reacted in 40 minutes with the target chemical by localized emission of the fluorescent reporter signal. We demonstrate the functioning of the bactosensor-chip by the automated detection of 50 μgarsenite-As l(-1) in water on consecutive days and after a one-week constant operation. Best induction of the bactosensors of 6-9-fold to 50 μg l(-1) was found at an apparent dilution rate of 0.12 h(-1) in the 50 nl microreactor. The bactosensor chip principle could be widely applicable to construct automated monitoring devices for a variety of targets in different environments.

Estudo químico-computacional da reatividade de aziridinona e diaziridinona através de cálculos semi-empíricos

The results of semiempirical molecular orbital calculations performed on aziridinone and diaziridinone employing the MNDO, AM1, and PM3 molecular models are presented. The AM1 method, which best reproduces ground-state molecular properties, is used to calculate electronic parameters and the use of these parameters for the evaluation of reactivity is discussed.

Pork Barrel politics in semi-democracies: the Spanish 'Parlamentary roads', 1874-1915

This paper analyzes the effects of parliamentary representation on road infrastructure expenditure during the Spanish Restoration. Using a panel dataset of Spanish provinces in 1880-1914 we find that the allocation of administrative resources among provinces depended both on the delegation characteristics (such as the share of MPs with party leadership positions, and their degree of electoral independence), and the regime"s global search for stability. These results point to the importance of electoral dynamics within semi-democratic political systems, and offer an example of the influence of government tactics on infrastructure allocation.

Pork Barrel politics in semi-democracies: the Spanish 'Parlamentary roads', 1874-1915

This paper analyzes the effects of parliamentary representation on road infrastructure expenditure during the Spanish Restoration. Using a panel dataset of Spanish provinces in 1880-1914 we find that the allocation of administrative resources among provinces depended both on the delegation characteristics (such as the share of MPs with party leadership positions, and their degree of electoral independence), and the regime"s global search for stability. These results point to the importance of electoral dynamics within semi-democratic political systems, and offer an example of the influence of government tactics on infrastructure allocation.

Nitração do fenol, um método em escala semi-micro para disciplina prática de 4 horas

A procedure for the nitration of phenol in a semi-micro scale, followed by separation of the formed orto- and para-nitrophenol isomers by column chromatography, is described. All the experiment, including determination of the melting point of the isolated products, require a period of 4 hours, and it is suitable for organic chemistry laboratory undergraduate courses.

Avaliação da salinização de açudes no semi-árido brasileiro por ICP-AES

The salt accumulation process in some reservoirs of regular and irregular use (from 10 to 50 years of constrution), located in the Southeast of Bahia State was evaluated. Inductively coupled plasma atomic emission spectrometry was used to evaluate the concentrations of Na, K, Ca and Mg in water samples from inside and upstream of the reservoirs. The results showed that for reservoirs of irregular use, the salt accumulation, indicated by the tracer Na, increases with the age of the reservoirs, however for the reservoirs of regular use the hydraulic retention time is the main parameter.

Estudo semi-empírico de ácidos hidroxâmicos: ácido formoidroxâmico e derivados do aleloquímico dimboa

Open chain hydroxamic acid (Hx) can exist as Z and E diastereomers of two tautomers, hydroxamic acid and hydroximic acid. The conformational stability of the formohydroxamic acid isomers evaluated by PM3 compared better to ab initio results from the literature than AM1 results. Structural data of the cyclic Hx 2,4-dihydroxy-7-metoxy-2H-1,4-benzoxazin-3(4 H)-one (DIMBOA) obtained by both semiempirical methods compared well to ab initio results. pKa data from the literature for derivatives of the aldolic isomer of DIMBOA were compared to the stability of the anions resulting from the loss of protons of their phenol and hydroxamic acid groups, determined as the difference in heat of formation between anionic and neutral forms, calculated by AM1 and PM3 methods. Good correlations between theoretical and experimental data were obtained for both semiempirical methods.

Síntese de sulfadiazina e sulfadiazina de prata em escala semi-micro: prática experimental em síntese de fármacos

The total synthesis of sulfadiazine and silver sulfadiazine from readily available starting materials was adapted to semi-micro laboratory scale and is proposed as an experiment in drug synthesis for undergraduate courses.

Research on the suitability of organosolv semi-chemical triticale fibers as reinforcement for recycled hdpe composites

The main objective of this research was to study the feasibility of incorporating organosolv semi-chemical triticale fibers as the reinforcing element in recycled high density polyethylene (HDPE). In the first step, triticale fibers were characterized in terms of chemical composition and compared with other biomass species (wheat, rye, softwood, and hardwood). Then, organosolv semi-chemical triticale fibers were prepared by the ethanolamine process. These fibers were characterized in terms of its yield, kappa number, fiber length/diameter ratio, fines, and viscosity; the obtained results were compared with those of eucalypt kraft pulp. In the second step, the prepared fibers were examined as a reinforcing element for recycled HDPE composites. Coupled and non-coupled HDPE composites were prepared and tested for tensile properties. Results showed that with the addition of the coupling agent maleated polyethylene (MAPE), the tensile properties of composites were significantly improved, as compared to non-coupled samples and the plain matrix. Furthermore, the influence of MAPE on the interfacial shear strength (IFSS) was studied. The contributions of both fibers and matrix to the composite strength were also studied. This was possible by the use of a numerical iterative method based on the Bowyer-Bader and Kelly-Tyson equations

Determinação de hidrocarbonetos voláteis e semi-voláteis na atmosfera

This paper focuses: (i) the development of a measurement technique for the determination of atmospheric C2-C6 hydrocarbons with sampling in canisters and analysis by gas chromatography/flame ionisation detector (GC/FID), (ii) the improvement of an existent adsorption-sampling technique with Tenax TA tubes for the determination of C6-C11 hydrocarbons and analysis by GC/FID after thermal desorption and cryogenic concentration, (iii) the identification of compounds present in ambient air by gas chromatography/mass spectrometry (GC/MS) for both canister and Tenax samples, (iv) a program of interlaboratorial comparison for quality control of C2-C11 analyses, and (v) the seasonal characterisation of ambient air C2-C11 hydrocarbons.

A Practical Micro Mechanical Model Based Local Approach Methodology for the Analysis of Ductile Fracture of Welded T-Joints

This thesis concentrates on developing a practical local approach methodology based on micro mechanical models for the analysis of ductile fracture of welded joints. Two major problems involved in the local approach, namely the dilational constitutive relation reflecting the softening behaviour of material, and the failure criterion associated with the constitutive equation, have been studied in detail. Firstly, considerable efforts were made on the numerical integration and computer implementation for the non trivial dilational Gurson Tvergaard model. Considering the weaknesses of the widely used Euler forward integration algorithms, a family of generalized mid point algorithms is proposed for the Gurson Tvergaard model. Correspondingly, based on the decomposition of stresses into hydrostatic and deviatoric parts, an explicit seven parameter expression for the consistent tangent moduli of the algorithms is presented. This explicit formula avoids any matrix inversion during numerical iteration and thus greatly facilitates the computer implementation of the algorithms and increase the efficiency of the code. The accuracy of the proposed algorithms and other conventional algorithms has been assessed in a systematic manner in order to highlight the best algorithm for this study. The accurate and efficient performance of present finite element implementation of the proposed algorithms has been demonstrated by various numerical examples. It has been found that the true mid point algorithm (a = 0.5) is the most accurate one when the deviatoric strain increment is radial to the yield surface and it is very important to use the consistent tangent moduli in the Newton iteration procedure. Secondly, an assessment of the consistency of current local failure criteria for ductile fracture, the critical void growth criterion, the constant critical void volume fraction criterion and Thomason's plastic limit load failure criterion, has been made. Significant differences in the predictions of ductility by the three criteria were found. By assuming the void grows spherically and using the void volume fraction from the Gurson Tvergaard model to calculate the current void matrix geometry, Thomason's failure criterion has been modified and a new failure criterion for the Gurson Tvergaard model is presented. Comparison with Koplik and Needleman's finite element results shows that the new failure criterion is fairly accurate indeed. A novel feature of the new failure criterion is that a mechanism for void coalescence is incorporated into the constitutive model. Hence the material failure is a natural result of the development of macroscopic plastic flow and the microscopic internal necking mechanism. By the new failure criterion, the critical void volume fraction is not a material constant and the initial void volume fraction and/or void nucleation parameters essentially control the material failure. This feature is very desirable and makes the numerical calibration of void nucleation parameters(s) possible and physically sound. Thirdly, a local approach methodology based on the above two major contributions has been built up in ABAQUS via the user material subroutine UMAT and applied to welded T joints. By using the void nucleation parameters calibrated from simple smooth and notched specimens, it was found that the fracture behaviour of the welded T joints can be well predicted using present methodology. This application has shown how the damage parameters of both base material and heat affected zone (HAZ) material can be obtained in a step by step manner and how useful and capable the local approach methodology is in the analysis of fracture behaviour and crack development as well as structural integrity assessment of practical problems where non homogeneous materials are involved. Finally, a procedure for the possible engineering application of the present methodology is suggested and discussed.

Real-Time Simulation of Mobile and Industrial Machines Using the Multibody Simulation Approach

This thesis introduces a real-time simulation environment based on the multibody simulation approach. The environment consists of components that are used in conventional product development, including computer aided drawing, visualization, dynamic simulation and finite element software architecture, data transfer and haptics. These components are combined to perform as a coupled system on one platform. The environment is used to simulate mobile and industrial machines at different stages of a product life time. Consequently, the demands of the simulated scenarios vary. In this thesis, a real-time simulation environment based on the multibody approach is used to study a reel mechanism of a paper machine and a gantry crane. These case systems are used to demonstrate the usability of the real-time simulation environment for fault detection purposes and in the context of a training simulator. In order to describe the dynamical performance of a mobile or industrial machine, the nonlinear equations of motion must be defined. In this thesis, the dynamical behaviour of machines is modelled using the multibody simulation approach. A multibody system may consist of rigid and flexible bodies which are joined using kinematic joint constraints while force components are used to describe the actuators. The strength of multibody dynamics relies upon its ability to describe nonlinearities arising from wearing of the components, friction, large rotations or contact forces in a systematic manner. For this reason, the interfaces between subsystems such as mechanics, hydraulics and control systems of the mechatronic machine can be defined and analyzed in a straightforward manner.