Polyethene with pendant fullerene moieties

Polyethene with fullerene moieties pendant on short-chain branches was prepared by the catalytic copolymerization of ethene and a fullerene-containing vinylic comonomer, yielding polyethene copolymers containing up to 25 wt% of C60.     

Enhancing calibration models for non-invasive near-infrared spectroscopical blood glucose determination

Partial least-squares regression (PLS) and radial basis function (RBF) networks are used to compute calibration models for non-invasive blood glucose determination by NIR diffuse reflectance spectroscopy. A model computation shows that even extremely small deviations of the spectra induce increased prediction errors. Since the spectral contribution of blood glucose is much smaller than deviations resulting from the non-invasive measuring process a method based on Pearson’s correlation coefficient can be used for evaluating the quality of the recorded spectra during the prediction step. Another method is based on the leverage values from the hat matrix of the RBF network. Both methods lead to a significant decrease in prediction error.     

Development and critical comparison of greener flow procedures for nitrite determination in natural waters

Two greener procedures for flow-injection spectrophotometric determination of nitrite in natural waters were developed and critically compared. Replacement of toxic reagents, waste minimization and treatment were exploited to attend the standards of clean chemistry. The flow system was designed with solenoid micro-pumps in order to minimize reagent consumption and waste generation. The first procedure is based on the Griess diazo-coupling reaction with sulfanilamide and N-(1-naphthyl)ethylenediamine (NED) yielding an azo dye, followed by photodegradation of the low amount of waste generated based on the photo-Fenton reaction. The second procedure is based on the formation of iodine from nitrite and iodide in acid medium in order to avoid the use of toxic reagents. For Griess method, linear response was achieved up to 1.0 mg L^− 1, described by the equation A = − 0.007 + 0.460C (mg L^− 1), r = 0.999. The detection limit was estimated as 8 μg L^− 1 at the 99.7% confidence level and the coefficient of variation was 0.8% (n = 20). The sampling rate was estimated as 108 determinations per hour. The consumption of the most toxic reagent (NED) is reduced 55-fold and 20-fold in comparison to batch method and flow injection with continuous reagent addition, respectively. A colorless residue was obtained by in-line photodegradation with reduction of 87% of the total organic carbon content. The results obtained for natural water samples were in agreement with those achieved by the reference method at the 95% confidence level. For the nitrite–iodide method, linear response was observed up to 2.0 mg L^− 1, described by the equation A = − 0.024 + 0.148C (mg L^− 1), r = 0.999. The detection limit was estimated as 25 μg L^− 1 at the 99.7% confidence level and the coefficient of variation was 0.6% (n = 20). The sampling rate was estimated as 44 determinations per hour. Despite avoiding the use of toxic reagents, the nitrite–iodide method presented worst performance in terms of selectivity and sensitivity.     

Diels-Alder chemistry on alkene functionalized films

A substrate-independent method has been devised for ring formation at solid surfaces. This entails the aminolysis reaction of allylamine with maleic anhydride pulsed plasma polymer films to yield terminal alkene groups at the surface. Subsequent exposure to 1,3-cyclohexadiene leads to a Diels-Alder type (4 + 2) cycloaddition reaction to give a mixture of endo- and exo-bicyclo[2.2.2]oct-2-ene rings.     

Stimulating effect of graphite admixture on hydrogen sorption-desorption properties of mechanically activated titanium powder

The effect of graphite admixture on hydrogen sorption-desorption properties of mechanically activated electron microscopy, temperature-programmed reaction, and temperature-programmed desorption techniques. The major effect of graphite addition was found to be the formation of microporous carbon matrix particles containing randomly distributed titanium particles only several nanometers in diameter. This powder architecture enhances hydrogen transport to the titanium surface without hindrances and promotes titanium-hydrogen interaction by modifying the titanium surface and subsurface layers with interstitial carbon atoms.     

OVERVIEW ON SURFACE MICROSTRUCTURING BY PHOTODESORPTION ETCHING OF CHLORINATED SILICON

Developing a mechanistic interpretation of complex dynamical chemical systems such as halogen photoetching requires correlated microscopic data on the kinetics, dynamics, surface composition and microstructure of prototypical and real surfaces. This overview is concerned especially with two important variables which significantly influence the microetching mechanisms and structures; (I) the role of electronic point defects induced by substitutional doping in producing site-specific reactions and, (II) the quantum mechanical enhancement of chemical reaction induced by uv-radiation at low fluences and temperatures.

From uv-photoetching and photodesorption studies of heavily doped Si(100) and Si(111) with chlorine beams at low laser fluences, the mechanisms of photostimulated desorption is analyzed based primarily on the kinetics of chemisorption and surface layer microanalysis obtained from core-level photoemission. These results are coupled with time-of-flight dynamical measurements on the energetics of the photodesorption process to provide a more unified understanding of anisotropic photon-stimulated microetching.

Substantial alterations of the etching mechanisms occur when selective surface molecular processes are driven quantum mechanically by low level photon radiation rather than thermally. This is clearly reflected in the dynamical mechanisms for photodesorption which become strongly site- and atomic process-selective illustrated by the energetics of the processes. Creation and transport of charged carriers, especially at high doping levels by photoionization coupled with field-induced charge transport, introduces new reaction channels into the surface chemistry leading to resultant changes in the microstructure on an atomic scale. The results from the kinetics, velocity dynamics and film composition measurements are combined in terms of the dependency of chlorine adsorption on doping at high carrier levels and low laser fluences, to provide an improved interpretation of the anisotropic microetching in terms of field-promoted electron-hole activation.     

Graphitized carbon black in quartz tubes for the sampling of indoor air nicotine and analysis by microwave thermal desorption-capillary gas chromatography

Nicotine in a smoky indoor air environment can be determined using graphitized carbon black as a solid sorbent in quartz tubes. The temperature stability, high purity, and heat absorption characteristics of the sorbent, as well as the permeability of the quartz tubes to microwaves, enable the thermal desorption by means of microwaves after active sampling. Permeation and dynamic dilution procedures for the generation of nicotine in the vapor phase at low and high concentrations are used to evaluate the performances of the sampler. Tube preparation is described and the microwave desorption temperature is measured. Breakthrough volume is determined to allow sampling at 0.1-1 L/min for definite periods of time. The procedure is tested for the determination of gas and paticulate phase nicotine in sidestream smoke produced in an experimental chamber.     

Catalytic conversion of 2-propanol on La2MnZnO6

The perovskite La₂MnZnO₆ has been synthesized by a ceramic technique and its catalytic activity has been tested for 2-propanol decomposition. The catalyst is totally selective to dehydrogenation of the alcohol. A possible mechanism for the reaction is proposed.

---

La₂MnZnO₆ 2-. . .