Enzymatic determination of sorbic acid

 An enzymatic method for the determination of sorbic acid based on the spectrophotometric measurement of sorbyl coenzyme A (sorbyl CoA) at 300 nm was developed. Sorbic acid is converted to sorbyl CoA with acyl CoA synthetase (EC 6.2.1.3) in the presence of coenzyme A and adenosine-5′-triphosphate. The reaction is made quantitative by irreversibly hydrolyzing pyrophosphate formed during the acylation reaction to phosphate in the presence of inorganic pyrophosphatase (EC 3.6.1.1). The absorbance measured at 300 nm is specific for sorbyl CoA and its value is proportional to the amount of sorbic acid in the sample solution. Accuracy, repeatability and recovery rates after standard addition to sample solutions were evaluated. All steps of the enzymatic analysis were carried out on an automatic centrifugal analyzer. The method is fast, precise and reliable, and therefore well suited for routine determinations, especially for high sample throughputs. Received: 7 June 1999 / Revised version: 12 August 1999     

Au dissolution during the anodic response of short-chain alkylthiols with polycrystalline Au electrodes

The electrochemical characteristics of polycrystalline Au in LiClO₄ electrolyte solutions containing 3-mercaptopropionic acid (MPA) or meso-2,3-dimercaptosuccinic acid (DMSA) were studied with linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) over a wide range of positive potentials vs. Ag/AgCl. The EIS data exhibited linear capacitive behaviour at 0.0 V with either MPA or DMSA added directly to the electrolyte suggesting the formation of an adsorbed layer of the alkylthiol on the electrode surface. Above this potential, a single well-defined impedance loop appeared for electrolyte solutions containing DMSA or MPA, an observation indicative of a charge transfer reaction that could be related to several processes including oxidative desorption, oxidation of the alkylthiol, or Au oxidation/dissolution. To test for Au dissolution, the electrode was held at 0.8 V vs. Ag/AgCl for 12 h in electrolytes containing MPA or DMSA followed by surface analysis with Atomic Force Microscopy and solution analysis with Atomic Absorption Spectroscopy. When the electrolyte contained MPA, the extended potential holding procedure resulted in significant roughening of the electrode with no detectable quantities of Au in the electrolyte. X-ray photoelectron spectroscopy (XPS) analysis of the Au surface revealed an additional species in the Au 4f_7/2 spectrum indicating the presence of an insoluble electrochemically generated Au(I)–MPA species. When the electrolyte contained DMSA, the Au electrode appeared smoother, 56.6 ± 9.6 ppb of Au was detected in the electrolyte and the XPS analysis displayed a single species in the Au 4f_7/2 spectrum indicative of metallic Au after the potential holding procedure. Both observations with MPA and DMSA support the charge transfer resistance to be at least partially related to the corrosion of Au, but also suggest that an electrochemically generated Au–DMSA species is soluble and of potential industrial relevance.     

Multifunctional fiberglass-reinforced PMMA-BaTiO3 structural/dielectric composites

Fiberglass-reinforced polymer composites were investigated for potential use as structural dielectrics in multifunctional capacitors that require simultaneous excellent mechanical properties and good energy storage characteristics. Composites were fabricated employing poly(methyl methacrylate), PMMA, as the structural matrix. While barium titanate (BaTiO₃) nanopowder was added to the composites for its high room temperature dielectric constant, fiberglass was employed to confer high stiffness. A conductive polymer blend of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonate (PEDOT:PSS) was used to coat the BaTiO₃ nanoparticles with the purpose of further elevating the dielectric constant of the resultant PMMA-composites. FTIR spectroscopy, TGA and SEM measurements were conducted to prove the successful coating of BaTiO₃ nanoparticles with the PEDOT:PSS blend. TEM measurements revealed a good dispersion of coated nanoparticles throughout the PMMA matrix. The fiberglass-reinforced-PMMA composites containing neat and coated BaTiO₃ were found to exhibit excellent stiffness. In addition, the use of PEDOT:PSS in conjunction with BaTiO₃ was observed to improve the dielectric constant of the composites. Finally, the dielectric constant of the structural composites was found to vary only slightly with temperature.     

Doping-induced broadening of the hole density-of-states in conducting polymers

The density-of-states distribution in conducting polymers reflects the energy disorder caused by electrostatic and steric interactions resulting from the different environment in which each molecule is placed. In case of p-doping (oxidation), the highest occupied molecular orbital (HOMO) manifold spreads in energy following a distribution as a result of long-range electrostatic (dipolar) interactions with the surrounding disordered host. In this paper the repercussion of the dipolar disorder on electrochemical signals of standard polypyrrole films is explored. The analysis is based on the chemical capacitance variation with the applied potential in experiments performed in quasi-equilibrium conditions. In addition to the Gaussian shape of cyclic voltammograms at low-doping levels, the model is able to qualitatively account for the current plateau usually observed at high oxidation potentials. This approach allows to estimating the dipolar moment associated to the polymer/dopant complex.     

Wet air oxidation in a catalytic membrane reactor: Model and industrial wastewaters in single tubes and multichannel contactors

Recent results on catalytic wet air oxidation applied to a membrane contactor are presented that give new insight following a series of previous publications. Model and industrial effluents are treated in both single tube and multichannel catalytic systems. Characterisation of the catalytic material (solid analyses, electron microscopy, EDS and EPMA) is carried out, in order to determine the catalyst distribution. Catalytic results show performances heavily dependent on the nature of the effluent and the operating conditions, and to a lesser extent on the catalytic membrane characteristics. At 80 °C, an industrial effluent is oxidised at a membrane surface related rate of 3.8 mmol/s/m². This result is achieved using a membrane containing about 0.1 wt.% Pt. This allows a revised and improved technico-economical evaluation of the Watercatox process.     

Low-noise operation modes of a passively mode-locked fiber laser

Optimum low-noise operation modes of a passively mode-locked fiber laser are described and characterized. The laser produces 60 fs bandwidth limited pulses with root mean square amplitude fluctuations of 0.4% in a frequency-band from 30 Hz to 100 kHz. It is shown that low-noise operation up to 5 dB below the amplitude noise of the pump laser is possible with overall negative cavity group-velocity dispersion and a large difference between the intracavity loss under free-running and mode-locked laser operation. Additional frequency stabilization reduces the timing jitter to 4 fs in a frequency band from 1 kHz to 100 kHz and 110 fs in the 30 Hz to 100 kHz band     

Estimated benefits of glycemic control in microvascular complications in type 2 diabetes

BACKGROUND: The benefits of intensive glycemic control in patients with type 2 diabetes are not well quantified. It is therefore not clear which patients will benefit most from aggressive glycemic control. OBJECTIVE: To evaluate the efficacy of glycemic control in type 2 diabetes. DESIGN: Markov decision model. PATIENTS: Diabetic patients at a health maintenance organization. MAIN OUTCOME MEASURES: Risks for developing blindness and end-stage renal disease; number of patients and patient-years needed to treat to prevent complications. RESULTS: For a patient in whom diabetes developed before 50 years of age, reducing hemoglobin A1c levels from 9% to 7% results in an estimated 2.3-percentage point decrease (from 2.6% to 0.3%) in lifetime risk for blindness due to retinopathy. The same change in a patient with diabetes onset at 65 years of age would be expected to decrease the risk for blindness by 0.5 percentage points (from 0.5% to < 0.1%). However, the Markov model predicts substantially greater benefit when moving from poor to moderate glycemic control than when moving from moderate to almost-normal glycemic control. Targeting less than 20% of the patients at one health maintenance organization for intensified therapy may prevent more than 80% of the preventable patient-time spent blind. The risks for end-stage renal disease and the risk reduction provided by improved glycemic control are lower than those for blindness. CONCLUSIONS: This probability model, based on extrapolation from the experience with type 1 diabetes, suggests that patients with early onset of type 2 diabetes will accrue substantial benefit from almost-normal glycemic control. In patients with later onset, moderate glycemic control prevents most end-stage complications caused by microvascular disease. These results have important implications for informing patients and allocating health care resources.     

Programmable 2D linear filter for video applications

A fully integrated 2-D linear filter including a line buffer for a 7×7 kernel is presented. To run the filter in real time at video clock frequencies, an array of pipelined carry-save adders was used as a very fast arithmetic unit. The filter chip contains 292451 transistors on a silicon area of 135 mm². The maximum clock frequency under worst-case conditions for technology and temperature was simulated to be 20 MHz. The main blocks are designed as independent parameterizable modules. The line buffer and the arithmetic unit are available as macros in a standard cell library for semicustom design. With these macros a semicustom chip for image enhancement in a X-ray system was produced. This chip works with a system frequency of 13 MHz. The line buffer module is used in another full-custom image processing chip-a two-dimensional rank order filter with a kernel size of also 7×7. This chip contains more than 300000 transistors on a silicon area of 103 mm². In this case the module containing the 1-D FIR (finite impulse response) filters is replaced by additional pixel delays and a sorter module. Simulations have shown that the chip could work with clock frequencies up to 20 MHz     

Real time X-ray scattering study of the formation of ZnS nanoparticles using synchrotron radiation

We investigate the growth of ZnS nanoparticles by a real-time simultaneous small and wide angle X-ray scattering (SAXS, WAXS) study using synchrotron radiation. Zinc chloride and elemental sulfur were dissolved in oleylamine. The formation of nanoparticles was induced by heating to 170 °C and 215 °C. The influence of temperature, reaction time, and sulfur concentration was investigated. After a short phase of rapid growth, saturation in size and a slower growth is observed depending on the temperature. The final size of the nanoparticles ranges between 2 and 6 nm for the investigated growth conditions and increases with the reaction temperature and sulfur concentration. SAXS analysis allows for determination of the size of the nanoparticles and proves also the existence of an organized layer of oleylamine molecules covering the nanoparticles' surfaces, which, however, appears only for diameters of the nanoparticles larger than approximately 2.8 nm. The investigation of the measured structure factor of the nanoparticle assemblies showed that the distance of an attractive interaction is 2.5 nm, which was interpreted as a consequence of the ordered oleylamine surface layer.