Enzymatic Synthesis of Glucose- and Xylose Laurate Esters Using Different Acyl Donors,Higher Substrate Concentrations,and Membrane Assisted Solvent Recovery

Glucose- and xylose laurate esters are enzymatically synthesized using equimolar substrate concentrations in 2-methyl-2-butanol, comparing free lauric acid with methyl- and vinyl-laurate as acyl donors. All reactions result in ≥70% acyl donor conversions after 72 h but the activated donors are also partially hydrolyzed to lauric acid, highlighting the difficulty in controlling water presence in this particular reaction system. The esterification of xylose generates a complex product profile, with several regioisomers of monoesters and diesters. The esterification of glucose is quite selective, forming mainly the 6-O monoester (≥96%) with a small presence of two diester isomers (4%). Increasing substrate concentration up to 800 millimoles kg⁻¹ results in lower conversion values (down to 58%) but shows that the reaction proceeds successfully even in the presence of high amounts of insoluble glucose. However, the reaction is less selective and the proportion of diester increases, becoming up to 46% (molar fraction) of the final product. Solvent recovery after esterification can be achieved by organic solvent nanofiltration through a polymeric membrane able to retain ≥80% of all reaction substrates and products. Practical Applications: The use of high substrate concentrations during the enzymatic synthesis of sugar ester biosurfactants leads to product titers that are more industrially appealing, without the need to find a solvent that can solubilize all initial substrate. The sustainability of the enzymatic conversion at mild temperatures can be enhanced by recycling of the reaction solvent through organic solvent nanofiltration, an energy efficient alternative to other traditional methods like distillation.     

Towards an international tradable green certificate system—The challenging example of Belgium

In Europe, a common framework for renewable energy sources (RES) is aspired. Tradable green certificates (TGCs) are a market-based cost-efficient means to stimulate electricity production from RES. Since TGCs are the most widespread support scheme in Europe together with feed-in tariffs, chances are that a common European framework could well be based on TGCs. However, while integrating currently existing different national TGC systems, any remaining differences should be carefully considered. Just how difficult the creation of an international TGC market would be is illustrated in this paper by the case of Belgium, where no less than 4 different TGC systems exist nowadays. The example of Belgium illustrates that harmonizing different TGC systems is easier said than done and represents a serious challenge. This clearly illustrates that a single European support scheme for RES, however desirable, is still far in the future.     

Microdosimetric characterisation of 28 kVp Mo/Mo,Rh/Rh,Rh/Al,W/Rh and Mo/Rh mammography X ray spectra

Microdosimetric characteristics of 28 kVp mammography X ray spectra were studied for several target/added filtration combinations (Mo/Mo, Rh/Rh, Rh/Al, W/Rh, Mo/Rh). Monte Carlo techniques were used to model X ray production from mammography units and to calculate distributions of absorbed dose and energy imparted in breast tissue. The results show that the dose averaged lineal energy is about 5.0 keV.micron-1, about 25% higher than for general diagnostic imaging X ray spectra. Significant differences in lineal energy between the five X ray qualities were noted, with the highest value for the commonly used Mo/Mo combination. Spectral hardening with depth in the tissues causes a 5% decrease in lineal energy over 5 cm. No significant differences were found for the different tissue compositions.     

Residual models and stochastic realization in state-space identification

This paper presents theory and algorithms for validation in system identification of state-space models from finite input-output sequences in a subspace model identification framework. Our formulation includes the problem of rank-deficient residual covariance matrices, a case which is encountered in applications with mixed stochastic-deterministic input-output properties as well as for cases where outputs are linearly dependent. Similar to the case of prediction-error identification, it is shown that the resulting model can be decomposed into an input-output model and a stochastic innovations model. Using the Riccati equation, we have designed a procedure to provide a reduced-order stochastic model that is minimal with respect to system order as well as the number of stochastic inputs thereby avoiding several problems appearing in standard application of stochastic realization to the model validation problem.     

In-water calibration of PDR 192Ir brachytherapy sources with an NE2571 ionization chamber

An ionometric calibration procedure for 192Ir PDR brachytherapy sources in terms of dose rate to water is presented. The calibration of the source is performed directly in a water phantom at short distances (1.0, 2.5 and 5.0 cm) using an NE2571 Farmer type ion chamber. To convert the measured air-kerma rate in water to dose rate to water a conversion factor (CF) was calculated by adapting the medium-energy x-ray dosimetry protocol for a point source geometry (diverging beam). The obtained CF was verified using two different methods. Firstly, the CF was calculated by Monte Carlo simulations, where the source-ionization chamber geometry was modelled accurately. In a second method, a combination of Monte Carlo simulations and measurements of the air-kerma rate in water (at 1.0, 2.5 and 5.0 cm distance) and in air (1 m distance) was used to determine the CF. The obtained CFs were also compared with conversion factors calculated with the adapted dosimetry protocol for high-energy photons introduced by T?lli. All calculations were done for a Gammamed PDR 192Ir source-NE2571 chamber geometry. The conversion factors obtained with the four different methods agree to within 1% at the three distances of interest. We obtained the following values (medium-energy x-ray protocol): CF(1 cm) = 1.458; CF(2.5 cm) = 1.162; CF(5.0 cm) = 1.112 (1 sigma = 0.7% for the three distances of interest). The obtained results were checked with TLD measurements. The values of the specific dose rate constant and the radial dose function calculated in this work are in accordance with the literature data.     

Levamisole treatment of a child with severe aphthous stomatitis and neutropenia

The treatment of a 12-year-old girl with a lifelone history of recurrent infections and aphthous stomatitis is reported. A profound neutropenis, first noted at the age of 2 years, occurring at least every month was observed together with multiple mouth ulcers a sore throat and swelling of the jugular glands. Levamisole, originally described as an anthelmintic, has a beneficial effect on the symptoms of recurrent aphthous stomatitis. After levamisole treatment aphthous stomatitis was milder and in the 1-year follow-up period the patient was asymptomatic several times during a phase of obvious neutrophil depression. The child no longer complained of a sore throat with swelling of the jugular glands and the recurrent staphylococcal infections of the skin disappeared. After therapy a marked increase in monocytes at the moment of neutropenia was observed.     

Proprietes nucleophiles de surfaces de silicate tricalcique

It has been experimentaly established that surface centres of tricalcium silicate, which play a fundamental role in the hydration mechanism, present a highly nucleophilic character. Use of tetracyanoaethylen (TCNE) has shown the electron transfer from the surface centres towards adsorbed molecules with TCNE ions formation.Study of these ions' formation has been performed by thermoluminescence, electron spin resonance and microfluorescence measurements.Moreover, the effect of natural ageing and thermal treatment of tricalcium silicate on the nucleophilic character of the surface centres has also been studied.     

Corticotropin-dependent Cushing's syndrome in older people: presentation of five cases and therapeutical use of ketoconazole

BACKGROUND: Cushing's syndrome is a rare disorder. The corticotropin (ACTH)-dependent form of this syndrome generally results either from excessive ACTH secretion by a pituitary adenoma or ectopic secretion by a malignant tumor. Theoretically, the latter type can be assumed to occur more frequently in old age as the incidence of malignancy increases. METHODS: Diagnostic procedures for these five cases of Cushing's syndrome consisted of 24-hour urinary cortisol excretion, plasma ACTH and serum cortisol levels, oCRH stimulatory test, low-dose and high-dose dexamethasone suppression tests, CT scan or MR imaging of the pituitary region, and bilateral inferior petrosal sinus sampling. Patients were treated with ketoconazole, if possible, and evaluated according to clinical response and 24-hour urinary cortisol excretion. PATIENTS: The five cases presented were selected on the basis of age--75 years or older--from a total of about 100 patients presenting with Cushing's syndrome. In only three cases were signs of hypercorticism found on clinical examination. The other two patients were evaluated for adrenocortical excess because of severe hypokalemia and the fortuitous finding of enlarged adrenal glands on CT scan, respectively. RESULTS: As a result of endocrine testing, pituitary-dependent Cushing's disease was suspected in three patients and ectopic Cushing's syndrome in two patients. Imaging techniques demonstrated only one pituitary adenoma in the first three patients and a lung tumor in one of the latter two patients. Inferior petrosal sinus sampling confirmed the suspected origin of the Cushing's syndrome in the three patients in which this procedure was performed. All three patients with pituitary-dependent Cushing's disease underwent successful clinical and biochemical treatment with ketoconazole. CONCLUSION: Pituitary-dependent Cushing's disease may occur more frequently in patients older than 75 years of age than has previously been assumed. Because surgical treatment is not always easily tolerated by older patients, the steroidogenesis inhibitor, ketoconazole, can be a valuable alternative for the control of hypercorticism.     

Monte Carlo study of fluence perturbation effects on cavity dose response in clinical proton beams

Current protocols for clinical proton beam dosimetry have not implemented any chamber-dependent correction factors for absorbed dose determination. The present work initiates a Monte Carlo study of these factors with emphasis on proton fluence perturbation effects and preliminary calculations of perturbation effects from secondary electrons. The proton Monte Carlo code PTRAN was modified to allow simulation of proton transport in non-homogeneous geometries of both unmodulated and modulated beams. The dose to water derived from the dose calculated in an air cavity agrees well with results from analytical calculations assuming a displacement of the point of measurement. For unmodulated beams small differences, limited to 0.8%, could be partially attributed to proton multiple scattering. Effects of replacing water around the cavity with wall material are explained by the introduction of a water-equivalent wall thickness. For modulated beams no significant perturbation effects arise. Secondary electron spectra are calculated analytically. Preliminary electron transport calculations with EGS4 show that wall perturbations of the order of 1% could result. Perturbation effects caused by the energy transport of secondary particles from inelastic nuclear interactions have not been studied here. Inclusion of inelastic nuclear energy transfers in the cavity dose, assuming total local absorption, indicate that separate scaling of this contribution with the ratio of total inelastic nuclear cross sections could be important.