Cadmium O‐alkylxanthates as CVD precursors of CdS: a chemical characterization

Cadmium bis(O‐alkylxanthates) are potential single‐source molecular precursors for the chemical vapor deposition (CVD) of Cd(II) sulfide thin films. In this work, a multi‐technique characterization of Cd(O‐RXan)₂ compounds [where O‐RXan is CH₃CH₂OCS₂ (O‐EtXan) or (CH₃)₂CHOCS₂ (O‐ⁱPrXan)] is performed by means of several analytical methods (extended x‐ray absorption fine structure, Raman, Fourier transform infrared and optical absorption, spectroscopics ¹H and ¹³C NMR, thermal analysis and mass spectrometry) for a thorough investigation of their structure and chemical–physical properties. The most important results concerning the chemical behavior under different experimental conditions, with particular attention to relevant properties for CVD applications, are presented and discussed. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis and characterization of zinc bis(O‐isopropylxanthate) as a single‐source chemical vapor deposition precursor for ZnS

The utilization of single‐source molecular precursors in chemical vapor deposition (CVD) experiments requires a deep knowledge of their chemico‐physical properties, with particular regard to thermal stability and fragmentation pattern. This study describes the synthesis and characterization of zinc bis(O‐isopropylxanthate), Zn(O‐ⁱPrXan)₂, [O‐ⁱPrXan = (CH₃)₂CHOCS₂], a single‐source precursor for the CVD of zinc(II) sulfide thin films and nanorods. Several analytical methods yielding complementary information (extended X‐ray absorption fine structure, Raman, FT‐IR, UV–Vis optical absorption, ¹H and ¹³C NMR, thermogravimetric analysis, differential scanning calorimetry as well as mass spectrometry techniques, i.e. electrospray and electron ionization, mass‐analyzed ion kinetic energy) are adopted for a comprehensive investigation of purity, structure, thermal behavior and decomposition pathways of the molecule. The most significant results are discussed critically and the properties useful for CVD applications are highlighted. Copyright © 2005 John Wiley & Sons, Ltd.     

A new glucosidic phthalide from Helichrysum microphyllum subsp. tyrrhenicum from La Maddalena Island (Sardinia,Italy)

In this study, we reported the analysis of the medium polarity fraction obtained from an accession of Helichrysum microphyllum subsp. tyrrhenicum from La Maddalena Island. Besides several compounds already evidenced in this species and related genera, i.e. micropyrone (1), arzanol (2), helipyrone (3), acetyl-bitalin derivatives (4, 5), gnaphaliol (6), caffeic acid (7), ursolic acid (8), 7-O-β-(d-glucopyranosyl)-5-methoxy-1(3H)-isobenzofuranone (9), gnaphaliol-9-O-β-d-glucopyranoside (11) and gnaphaliol-3-O-β-d-glucopyranoside (12), the presence of a new glycosidic phthalide, 6-O-β-(d-glucopyranosyl)-4-methoxy-1(3H)-benzofuranone (10), was evidenced for the first time, which resulted in a structural isomer of compound (9). The occurrence of this new benzofuranone derivative is an additional evidence of the deep intraspecific variability expressed by this species, which was also stated for the non-volatile components, and may be a distinctive trait of the population growing on La Maddalena Island.     

Scoring Unusual Words with Varying Mismatch Errors

Patterns consisting of strings with a bounded number of mismatches are central to coding theory and find multiple applications in text processing and computational biology. In this latter field, the presence of over-represented patterns of this kind has been linked, for instance, to modeling regulatory regions in biosequences. The study and computation of expected number of occurrences and related scores for these patterns is made difficult by the sheer explosion of the roster of candidates that need to be evaluated. In recent work, properties of pattern saturation and score monotonicity have proved capable to mitigate this problem. In such a context, expectation and score monotonicity has been established within the i.i.d. model for all cases of interest except that of a fixed word length with a varying number of mismatches. The present paper completes this investigation by showing that the expected number of occurrences in a textstring for such a word is bi-tonic, that is, behaves as a unimodal function of the number of errors. This extends to this case the time and space savings brought about by discovery algorithms based on pattern saturation. Work Supported in part by the Italian Ministry of University and Research under the Bi-National Project FIRB RBIN04BYZ7, and by the Research Program of Georgia Tech. An extended abstract related to this work was presented at the Dagstuhl Seminar Dagstuhl on “Combinatorial and Algorithmic Foundations of Pattern and Association Discovery”, May 14-19, 2006 [3].     

In Situ Observation of C−C Coupling and Step Poisoning During the Growth of Hydrocarbon Chains on Ni(111)

The synthesis of high-value fuels and plastics starting from small hydrocarbon molecules plays a central role in the current transition towards renewable energy. However, the detailed mechanisms driving the growth of hydrocarbon chains remain to a large extent unknown. Here we investigated the formation of hydrocarbon chains resulting from acetylene polymerization on a Ni(111) model catalyst surface. Exploiting X-ray photoelectron spectroscopy up to near-ambient pressures, the intermediate species and reaction products have been identified. Complementary in situ scanning tunneling microscopy observations shed light onto the C−C coupling mechanism. While the step edges of the metal catalyst are commonly assumed to be the active sites for the C−C coupling, we showed that the polymerization occurs instead on the flat terraces of the metallic surface.     

Development and validation of an HPLC-UV detection assay for the determination of rufinamide in human plasma and saliva

The development of a simple and rapid high-performance liquid chromatography (HPLC) method for the determination of the new antiepileptic drug rufinamide (RFN) in human plasma and saliva is reported. Samples (250 μl) are alkalinized with ammonium hydroxide (pH 9.25) and extracted with dichloromethane using metoclopramide as internal standard. Separation is achieved with a Spherisorb silica column (250 × 4.6 mm i.d., 5 μm) at 30 °C using as mobile phase a solution of methanol/dichloromethane/n-hexane 10/25/65 (vol/vol/vol) mixed with 6 ml ammonium hydroxide. The instrument used was a Shimadzu LC-10Av chromatograph and flow rate was 1.5 ml min^-1, with a LaChrom L-7400 UV detector set at 230 nm. Calibration curves are linear [r ² = 0.998 ± 0.002 for plasma (n = 10) and r ² = 0.999 ± 0.001 for saliva (n = 9)] over the range of 0.25–20.0 μg ml^-1, with a limit of quantification at 0.25 μg ml^-1. Precision and accuracy are within current acceptability standards. The assay is suitable for pharmacokinetic studies in humans and for therapeutic drug monitoring.     

Gadolinium-doped LipoCEST agents: a potential novel class of dual 1H-MRI probes

A novel class of paramagnetic liposome-based systems acting as dual T(1) and CEST (1)H-MRI contrast agents is described. The vesicles contain a shift reagent in the aqueous core and a Gd-complex on the external surface conjugated through a biodegradable linker. As such, the probe can generate T(1) contrast only, but after the cleavage and removal of the Gd-coating, the CEST contrast is switched on.     

Gold nanoparticles incarcerated in nanoporous syndiotactic polystyrene matrices as new and efficient catalysts for alcohol oxidations

The controlled synthesis of gold nanoparticles (AuNPs), incarcerated in a semicrystalline nanoporous polymer matrix that consisted of a syndiotactic polystyrene-co-cis-1,4-polybutadiene multi-block copolymer is described. This catalyst was successfully tested in the oxidation of primary and secondary alcohols, in which we used dioxygen as the oxidant under mild conditions. Accordingly, (±)-1-phenylethanol was oxidised to acetophenone in high yields (96%) in 1 h, at 35 °C, whereas benzyl alcohol was quantitatively oxidised to benzaldehyde with a selectivity of 96% in 6 h. The specific rate constants calculated from the corresponding kinetic plots were among the highest found for polymer-incarcerated AuNPs. Similar values in terms of reactivity and selectivity were found in the oxidation of primary alcohols, such as cinnamyl alcohol and 2-thiophenemethanol, and secondary alcohols, such as indanol and α-tetralol. The remarkable catalytic properties of this system were attributed to the formation, under these reaction conditions, of the nanoporous ε crystalline form of syndiotactic polystyrene, which ensures facile and selective accessibility for the substrates to the gold catalyst incarcerated in the polymer matrix. Moreover, the polymeric crystalline domains produced reversible physical cross-links that resulted in reduced gold leaching and also allowed the recovery and reuse of the catalyst. A comparison of catalytic performance between AuNPs and annealed AuNPs suggested that multiple twinned defective nanoparticles of about 9 nm in diameter constituted the active catalyst in these oxidation reactions.     

Is the Reduction in Tracer Diffusivity under Nanoscopic Confinement Related to a Frustrated Segmental Mobility?

We developed an experimental method for the determination of the tracer diffusivity D_tr in ultrathin polymer films, and the changes in the segmental mobility of tracer molecules while they diffuse through matrices of different thickness and get adsorbed onto a target substrate. D_tr starts decreasing already at 120–150 nm and drops to 1% of its bulk value in films as thin as 7.5 nm. We discuss the results highlighting a strong decoupling between the reduction in mass transport at the nanoscale and the increase in the glass transition temperature determined via capacitive dilatometry together with a breakdown of the Stokes–Einstein relation between orientational and translational degrees of freedom.

     

Wooden windows: Sound insulation evaluation by means of artificial neural networks

Windows are the weakest part of a façade in terms of acoustic performance: the weighted sound insulation index (R_w), measured according to ISO 140-3, is the fundamental parameter to evaluate the façade acoustic insulation.The paper aims at developing an artificial neural network (ANN) model to estimate the R_w value of wooden windows based on a limited number of windows parameters; this is a new approach because acoustic phenomena are non-linear and affected by a plurality of factors and, therefore, usually investigated through experimentation.Data set is taken from experimental campaigns carried out at the Laboratory of Acoustics, University of Perugia. A multilayer feed-forward approach was chosen and the model was implemented in MATLAB. On the basis of the results obtained by means of a preliminary training and test campaign of several ANN architectures, five main parameters were selected as network inputs: window typology, frame and shutters thickness, number of gaskets, R_w of glazing; R_w value of the window is the network output. Different ANN configurations were trained and a root mean-square error less than 3% was obtained, comparable to measurement uncertainty.This approach allows to develop a model which, with input parameters varying within appropriate ranges, can easily estimate the acoustic performance of wooden windows without experimental campaign on prototypes, saving both money and time. If the training data set is large enough, the presented approach could be very useful for design and optimization of acoustic performance of new products.