Ionization of Acetylacetone in Me2SO—Water Mixtures. Reactivity—Selectivity Principle or Principle of Imperfect Synchronization?

Rate constants for the reversible deprotonation of acetylacetone were measured in carboxylate and amine buffers in water and in 50%, 90% and 95% Me₂SO at 20°C. The Brønsted plot for the carboxylate ions is curved in the Me₂SO—water mixtures, but straight in water. The curvature is in the direction predicted by the Reactivity—Selectivity Principle (RSP). However, the Brønsted plot for the reaction with primary amines is straight in all solvents. This suggests that the curvature observerd with the carboxylate ions is caused by loss of solvation of the base; this loss of solvation is ahead of bond formation in the transition state rather than being a manifestation of the RSP. (Note that all Brønsted plots are based on pK_a values measured in the respective solvents.) The intrinsic rate constant (k₀) for proton transfer increases with the addition of Me₂SO, and more so with the carboxylate buffers than with the amines. This increase in k₀ is attributed to delayed solvation of the developing enolate ion in the transition state; with the carboxylate buffers, an additional factor is the early loss of solvation of the base. The various solvation effects observed in this study can all be understood in the context of the Principle of Imperfect Synchronization (PIS).     

Glass fiber-filled thermoplastics. I. Wall and processing effects on rheological properties

A systematic study of wall effects on the shear viscosity of short glass fiber-filled polypropylene and polystyrene is presented. The dependence of these effects on capillary radius, shear rate, temperature, and polymer matrix is examined. The “true” viscosity curves of these materials (free from wall effects) can be obtained by an extrapolation procedure. Breakage of glass fibers in the high shear-rate processes of extrusion and injection molding lead to an appreciable reduction of the viscosity of these materials and is probably the more important effect to take into account in these processes.     

Pyramid collaborative filtering technique for an intelligent autonomous guide agent

This article presents an autonomous guide agent that can observe a community of learners on the web, interpret the learners' inputs, and then assess their sharing. The goal of this agent is to find a reliable helper (tutor or other learner) to assist a learner in solving his task. Despite the growing number of Internet users, the ability to find helpers is still a challenging and important problem. Although helpers could have much useful information about courses to be taught, many learners fail to understand their presentations. For that, the agent must be able to deal autonomously with the following challenges: Do helpers have information that the learners need? Will helpers present information that learners can understand? And can we guarantee that these helpers will collaborate effectively with learners? We have developed a new filtering framework, called a pyramid collaborative filtering model, to whittle the number of helpers down to just one. We have proposed four levels for the pyramid. Moving from one level to another depends on three filtering techniques: domain model filtering, user model filtering, and credibility model filtering. A new technique is filtering according to helpers' credibilities. Our experiments show that this method greatly improves filtering effectiveness. © 2007 Wiley Periodicals, Inc. Int J Int Syst 22: 1065–1082, 2007.     

Electrochemical behaviour of copper in neutral aerated chloride solution. I. Steady-state investigation

The electrochemical behaviour of a Cu rotating disc electrode in neutral aerated NaCl solution was investigated in the cathodic and anodic ranges and at the corrosion potential. In the cathodic range, where the reduction of oxygen takes place, reduction peaks allow the identification and quantitative evaluation of insoluble corrosion products (CuCl and Cu₂O). In the anodic range Cu is dissolved, most likely as CuCl ₂ ^– . A new mechanism for the anodic dissolution is proposed after comparing our data with previously published mechanisms. Corrosion currents were found to decrease with time and to be a function of the rotation rate of the electrode. Both the mixed kinetics of the anodic partial reaction and diffusion through a porous layer seem to be relevant in controllingl _corr.     

Plasma and lipoprotein fatty acid composition in glycogen storage disease type I

Nocturnal intragastric feeding has been shown to be an effective means to improve clinical and biochemical features in glycogen storage disease type I (GSD-I). In this study, we investigated the fatty acid patterns in a whole plasma and in circulating lipoproteins in patients on this therapy. The results demonstrated massive concentration of total fatty acids coupled with higher levels of triglycerides, free cholesterol, cholesterol ester and phospholipids. This hyperlipidemia involved all fatty acids without distinction of carbon or bond numbers. However, the increase was more pronounced for saturated than polyunsaturated fatty acids, as was demonstrated by the ratios of both oleic acid to linoleic acid (1.91±0.40 vs 0.80±0.09 in controls) and of ω3+ω6 to ω9 fatty acid families (0.92±0.11 vs 1.66±0.08 in controls). The fatty acid patterns in very low (VLDL), low (LDL) and high (HDL) density lipoprotein showed substantial differences in composition, reflecting an association between an abnormal lipoprotein pattern and essential fatty acid deficiency. Furthermore, GSD-I patients exhibited a significant increase in VLDL (17±2 vs 47±7 mg/dl) and LDL cholesterol (124±7 vs 206±24 mg/dl), coupled with a decrease in HDL cholesterol (49±4 vs 28±3 mg/dl). These data documenting high LDL cholesterol and low HDL cholesterol associated with an increased concentration and proportion of saturated fatty acids suggest that GSD-I patients on nocturnal intragastric feeding are at high risk for atherosclerosis and its complications.     

Experimental analysis and numerical modelling of the forming process of polypropylene replicas of micro-cavities using hot embossing

Numerical modelling of the deformation of a polymer using the finite elements method in axisymetrical mode was performed using the LsDyna^® software to describe the filling of micro-cavities during the forming process of the material using the hot embossing. These simulations firstly allow verifying whether the chosen forming process conditions promote or not an optimized filling of the superficial cavities in order to achieve precise replicas which best reproduce the superficial topography of the mould. The simulations were carried out to evaluate the filling of the cavities taking into account the mechanical behaviour of the selected polymer into the model. Moreover, these models were developed to verify the effect of the distribution of the mould cavities on their filling. The influence of the mobility of non deformable rigid plates on the filling of the cavities represents an auxiliary variable. In the approach presented, the compression plates are assumed to be parallel and non deformable, whereas the polymer disk follows a rubbery behaviour around a temperature equal to 140°C. Globally the modelling results are satisfactory for they are rather close to the experimental observations conducted. In summary, the effect of the normal stress as also the distribution of micro-cavities at the mould surface seem to prevail in the case of the forming process by hot embossing.     

Détermination du facteur de multiplication M pour un fonctionnement optimal des photodétecteurs à avalanche

The purpose of this paper is relative to the determination of the multiplication factor Mfor an optimum behaviour of the avalanche photodetector. Two types of avalanche photodetector s are compared: a silicon structure n ⁺ πpπp ⁺ Read diode and a GaAlAs heterostructure. Calculating the Noise Equivalent Power (nep)of the whole system, the law S_i(f) =2q I_phoM_x is used, where the parameter x is determined experimentally in both avalanche photodetectors. The exponent x (between 2 and 4) dominates in the nep expression and the ideal nep for the avalanche photodetector system is obtained when x equals 2.     

Optical properties of γ-irradiated synthetic sapphire and yttria-stabilized zirconia spectroscopic windows

Synthetic sapphire and yttria-stabilized zirconia single-crystals were irradiated by increasing doses of γ-radiation to study the changes of their optical properties. The optical transparency of -Al₂O₃ was nearly constant up to the γ-radiation dose of 150 kGy for the spectral range of 400–1000 nm, while yellowish-brown coloration of (Zr_0.89Y_0.11)O_1.94 appeared for irradiation above 1 kGy. However, after a short-term heating in the temperature of 210^oC stable discoloration of zirconia can be achieved.     

High‐dose cefazolin on consecutive hemodialysis in anuric patients with Staphylococcal bacteremia

Methicillin‐sensitive Staphylococcus aureus (MSSA) bacteremia is a leading cause of infection in hemodialysis (HD) patients. Cloxacillin, cefazolin, and vancomycin are the mainstay antimicrobials. Cloxacillin administration leads to frequent drug dosing, longer length of stay (LOS), and higher cost, while resistance and poorer outcomes are associated with vancomycin use. Dosing cefazolin during HD allows for prolonged blood therapeutic levels. We assessed the outcomes and safety of a strategy of treating MSSA bacteremia with 2–3 g cefazolin on HD only. All HD patients with MSSA bacteremia admitted in June–December 2009 at our center and receiving this regime were compared with historical controls who received cloxacillin. Demographic characteristics and outcome measures like mortality, LOS, cost, recrudescence, and adverse drug reactions were assessed. Of 27 consecutive episodes reviewed, 14 and 13 patients received cefazolin and cloxacillin, respectively. Baseline demographics were comparable between the 2 treatment groups. More than one‐third of the bacteremia was related to tunneled catheter infection. The 30‐day mortality of cloxacillin‐ and cefazolin‐treated patients was 15% and 7%, respectively (P=0.14). Two of the 11 survivors treated with cloxacillin (18%) had recrudescent bacteremia while none was observed in cefazolin‐treated survivors. Cefazolin was associated with shorter LOS (10 vs. 20 days, P<0.05) and lower cost (US$8262.00 vs. US$15,367.00, P<0.05). Cefazolin use resulted in 3 idiosyncratic adverse drug reactions. Cefazolin dosed on each HD in MSSA bacteremia leads to earlier discharge and less cost. Larger prospective studies are, however, warranted to fully assess its safety and efficacy.