NMR Chemical Shielding and Spin-Spin Coupling Constants of Liquid NH(3): A Systematic Investigation using the Sequential QM/MM Method

The NMR spin coupling parameters, (1)J(N,H) and (2)J(H,H), and the chemical shielding, sigma((15)N), of liquid ammonia are studied from a combined and sequential QM/MM methodology. Monte Carlo simulations are performed to generate statistically uncorrelated configurations that are submitted to density functional theory calculations. Two different Lennard-Jones potentials are used in the liquid simulations. Electronic polarization is included in these two potentials via an iterative procedure with and without geometry relaxation, and the influence on the calculated properties are analyzed. B3LYP/aug-cc-pVTZ-J calculations were used to compute the V(N,H) constants in the interval of -67.8 to -63.9 Hz, depending on the theoretical model used. These can be compared with the experimental results of -61.6 Hz. For the (2)J(H,H) coupling the theoretical results vary between -10.6 to -13.01 Hz. The indirect experimental result derived from partially deuterated liquid is -11.1 Hz. Inclusion of explicit hydrogen bonded molecules gives a small but important contribution. The vapor-to-liquid shifts are also considered. This shift is calculated to be negligible for (1)J(N,H) in agreement with experiment. This is rationalized as a cancellation of the geometry relaxation and pure solvent effects. For the chemical shielding, U(15 N) Calculations at the B3LYP/aug-pcS-3 show that the vapor-to-liquid chemical shift requires the explicit use of solvent molecules. Considering only one ammonia molecule in an electrostatic embedding gives a wrong sign for the chemical shift that is corrected only with the use of explicit additional molecules. The best result calculated for the vapor to liquid chemical shift Delta sigma((15)N) is -25.2 ppm, in good agreement with the experimental value of -22.6 ppm.

Sequential injection analysis (SIA) and response surface methodology: A versatile small volume approach for optimization of photo-Fenton processes

Optimization of photo-Fenton degradation of copper phthalocyanine blue was achieved by response surface methodology (RSM) constructed with the aid of a sequential injection analysis (SIA) system coupled to a homemade photo-reactor. Highest degradation percentage was obtained at the following conditions [H(2)O(2)]/[phthalocyanine] = 7, [H(2)O(2)]/[FeSO(4)] = 10, pH = 2.5, and stopped flow time in the photo reactor = 30 s. The SIA system was designed to prepare a monosegment containing the reagents and sample, to pump it toward the photo-reactor for the specified time and send the products to a flow-through spectrophotometer for monitoring the color reduction of the dye. Changes in parameters such as reagent molar ratios. residence time and pH were made by modifications in the software commanding the SI system, without the need for physical reconfiguration of reagents around the selection valve. The proposed procedure and system fed the statistical program with degradation data for fast construction of response surface plots. After optimization, 97% of the dye was degraded. (C) 2009 Elsevier B.V. All rights reserved.

Development of a sequential injection chromatography (SIC) method for determination of simazine, atrazine, and propazine

This paper describes the development of a sequential injection chromatography (SIC) procedure for separation and quantification of the herbicides simazine, atrazine, and propazine exploring the low backpressure of a 2.5 cm long monolithic C(18) column. The separation of the three compounds was achieved in less than 90 s with resolution > 1.5 using a mobile phase composed by ACN/1.25 mmol/L acetate buffer (pH 4.5) at the volumetric ratio of 35:65 and flow rate of 40 mu L/s. Detection was made at 223 nm using a flow cell with 40 mm of optical path length. The LOD was 10 mu g/L for the three triazines and the quantification limits were of 30 mu g/L for simazine and propazine and 40 mu g/L for atrazine. The sampling frequency is 27 samples per hour, consuming 1.1 mL of ACN per analysis. The proposed methodology was applied to spiked water samples and no statistically significant differences were observed in comparison to a conventional HPLC-UV method. The major metabolites of atrazine and other herbicides did not interfere in the analysis, being eluted from the column either together with the unretained peak, or at retention times well-resolved from the studied compounds.

Group Sequential Communication (GSC): Especificação e Análise de Desempenho de umMecanismo de Comunicação de Tempo Real Compatível ao Padrão IEEE 802.11/11e Aplicado à Automação Industrial

This thesis proposes the specification and performance analysis of a real-time communication mechanism for IEEE 802.11/11e standard. This approach is called Group Sequential Communication (GSC). The GSC has a better performance for dealing with small data packets when compared to the HCCA mechanism by adopting a decentralized medium access control using a publish/subscribe communication scheme. The main objective of the thesis is the HCCA overhead reduction of the Polling, ACK and QoS Null frames exchanged between the Hybrid Coordinator and the polled stations. The GSC eliminates the polling scheme used by HCCA scheduling algorithm by using a Virtual Token Passing procedure among members of the real-time group to whom a high-priority and sequential access to communication medium is granted. In order to improve the reliability of the mechanism proposed into a noisy channel, it is presented an error recovery scheme called second chance algorithm. This scheme is based on block acknowledgment strategy where there is a possibility of retransmitting when missing real-time messages. Thus, the GSC mechanism maintains the real-time traffic across many IEEE 802.11/11e devices, optimized bandwidth usage and minimal delay variation for data packets in the wireless network. For validation purpose of the communication scheme, the GSC and HCCA mechanisms have been implemented in network simulation software developed in C/C++ and their performance results were compared. The experiments show the efficiency of the GSC mechanism, especially in industrial communication scenarios.

Spot-test identification and rapid quantitative sequential analysis of dipyrone

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Sequential injection analysis system with spectrophotometric detection for determination of norfloxacin and ciprofloxacin in pharmaceutical formulations

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

A flow-injection-ICP system sequential multielemental analysis with simultaneously mercury(II) preconcentration step

A flow-injection system for multielemental analysis with a mercury(II) preconcentration step using a resin Chelite-S(R)(Serva Feinbiochemica Heidelberg, Part No. 41709) packed minicolumn by inductively coupled plasma atomic emission spectroscopy is described. A mercury reductive elution procedure with a mixture of SnCl2/HCl was used, which allows use of 6 mol/L HCl solution instead of concentrated hydrochoric acid. The main parameters related to ICP operation, such as radio frequency power (950-1750 W), auxiliary argon flow (0.0-1.5 L/min) and spray chamber nebulizer pressure (15-35 psi), were studied. Optimization of the FIA system was reached by defining the best eluent carrier stream (1.4-2.8 mL/min), Hgdegrees carrier stream (10-40 mL min(-1)), loading time (0.5-4.0 min), sample flow rate (1.25-10.0 mL/min), temperature of reactor gas liquid separator (GLS) (25-75 degreesC) and eluent volume (50-350 muL). Throughput is around 30 samples per hour for analytical solutions within the range 50-2500 ng Hg(II)/L. Results from certified material showed good precision (RSD < 3%, n = 12) and no statistical difference was observed for real samples analyzed by AAS and by the proposed system.

Simple orbit determination using GPS based on a least-squares algorithm employing sequential givens rotations

A low-cost computer procedure to determine the orbit of an artificial satellite by using short arc data from an onboard GPS receiver is proposed. Pseudoranges are used as measurements to estimate the orbit via recursive least squares method. The algorithm applies orthogonal Givens rotations for solving recursive and sequential orbit determination problems. To assess the procedure, it was applied to the TOPEX/POSEIDON satellite for data batches of one orbital period (approximately two hours), and force modelling, due to the full JGM-2 gravity field model, was considered. When compared with the reference Precision Orbit Ephemeris (POE) of JPL/NASA, the results have indicated that precision better than 9 m is easily obtained, even when short batches of data are used. Copyright (c) 2007.

Batch, sequential and hybrid approaches to spacecraft sensor alignment estimation

Two Kalman-filter formulations are presented for the estimation of spacecraft sensor misalignments from inflight data. In the first the sensor misalignments are part of the filter state variable; in the second, which we call HYLIGN, the state vector contains only dynamical variables, but the sensitivities of the filter innovations to the misalignments are calculated within the Kalman filter. This procedure permits the misalignments to be estimated in batch mode as well as a much smaller dimension for the Kalman filter state vector. This results not only in a significantly smaller computational burden but also in a smaller sensitivity of the misalignment estimates to outliers in the data. Numerical simulations of the filter performance are presented.

Sequential spectrophotometric determination of chromium(III) and chromium(VI) using flow injection analysis

A flow injection analysis (FIA) procedure for the speciation of Cr(III) and Cr(VI) using the 1,5-diphenylcarbazide (DPC) method is presented. As Cr(III) does not interfere in the Cr(VI) - DPC reaction, both Cr(VI) and total chromium [after the on-line oxidation of Cr(III) by Ce(IV)] are sequentially determined. Cr(III) is obtained by difference. Under the experimental conditions described, the calibration graphs are linear up to 2 μg mh1 of Cr(VI) and 4 μg ml-1 of Cr(III). The detection limits found were 18 ng ml -1 for Cr(VI) and 55 ng ml-1 for Cr(III), at a signal to noise ratio of 3. The common interfering elements in the Cr(VI) - DPC reaction were investigated under dynamic FIA conditions. The FIA method was also compared with the conventional spectrophotometric procedure.

Sequential Determination of Cd, Cu and Pb in Tea Leaves by Slurry Introduction to Thermospray Flame Furnace Atomic Absorption Spectrometry

A simple procedure for the sequential determination of Cd, Cu and Pb in tea leaves by slurry introduction to thermospray flame furnace atomic absorption spectrometry was developed. Detection limits were 0.05 mg kg-1 for Cd, 2.1 mg kg-1 for Cu and 0.68 mg kg-1 for Pb using 0.67 % (m/v) slurries (100 mg/15 mL). © 2013 Springer Science+Business Media New York.

Evaluation of Bone Heating, Drill Deformation, and Drill Roughness After Implant Osteotomy: Guided Surgery and Classic Drilling Procedure

Purpose: This study evaluated and compared bone heating, drill deformation, and drill roughness after several implant osteotomies in the guided surgery technique and the classic drilling procedure. Materials and Methods: The tibias of 20 rabbits were used. The animals were divided into a guided surgery group (GG) and a control group (CG); subgroups were then designated (G0, G1, G2, G3, and G4, corresponding to drills used 0, 10, 20, 30 and 40 times, respectively). Each animal received 10 sequential osteotomies (5 in each tibia) with each technique. Thermal changes were quantified, drill roughness was measured, and the drills were subjected to scanning electron microscopy. Results: Bone temperature generated by drilling was significantly higher in the GG than in the CG. Drill deformation in the GG and CG increased with drill use, and in the CG a significant difference between GO and groups G3 and G4 was observed. In the GG, a significant difference between GO and all other groups was found. For GG versus CG, a significant difference was found in the 40th osteotomy. Drill roughness in both groups was progressive in accordance with increased use, but there was no statistically significant difference between subgroups or between GG and CG overall. Conclusion: During preparation of implant osteotomies, the guided surgery technique generated a higher bone temperature and deformed drills more than the classic drilling procedure. The increase in tissue temperature was directly proportional to the number of times drills were used, but neither technique generated critical necrosis-inducing temperatures. Drill deformation was directly proportional to the number of times the drills were used. The roughness of the drills was directly proportional to the number of reuses in both groups but tended to be higher in the GG group.

Post-processing of sequential indicator simulation realizations for modeling geologic bodies

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Rapid sample preparation procedure for As speciation in food samples by LC-ICP-MS

This paper describes a rapid method for arsenic (As) speciation by LC-ICP-MS in several types of food samples. Prior to analysis, samples were milled and the As species extracted from biological tissues by sonication in only 2 min with a solution containing MeOH (10%, v/v) plus HNO3 (2%, v/v). As species were separated by LC using an anion exchange column. Method detection limits for AsB, As3+,DMA, MMA and As5+ were 1.3, 0.9, 0.6, 0.7 and 0.8 ng g(-1), respectively. Method accuracy and precision were traceable to Certified Reference Materials SRM1577 bovine liver from the National Institute of Standards and Technology, CE278 mussel tissue from the Institute of Reference Materials and Measurements and DOLT-3 dogfish liver tissue and DORM-3 fish protein from the National Research Council of Canada. Finally, the method was applied to speciate As in food samples (egg, fish muscle, beef and chicken) purchased in Brazilian markets.

Electronic Properties of Water in Liquid Environment. A Sequential QM/MM Study Using the Free Energy Gradient Method

There is a continuous search for theoretical methods that are able to describe the effects of the liquid environment on molecular systems. Different methods emphasize different aspects, and the treatment of both the local and bulk properties is still a great challenge. In this work, the electronic properties of a water molecule in liquid environment is studied by performing a relaxation of the geometry and electronic distribution using the free energy gradient method. This is made using a series of steps in each of which we run a purely molecular mechanical (MM) Monte Carlo Metropolis simulation of liquid water and subsequently perform a quantum mechanical/molecular mechanical (QM/MM) calculation of the ensemble averages of the charge distribution, atomic forces, and second derivatives. The MP2/aug-cc-pV5Z level is used to describe the electronic properties of the QM water. B3LYP with specially designed basis functions are used for the magnetic properties. Very good agreement is found for the local properties of water, such as geometry, vibrational frequencies, dipole moment, dipole polarizability, chemical shift, and spin-spin coupling constants. The very good performance of the free energy method combined with a QM/MM approach along with the possible limitations are briefly discussed.