A Mechanisms and Kinetics Study of Polymeric Thin-Film Deposition in Glow Discharge

Polymeric thin-film deposition in a capacitively coupled rf glow discharge of styrene has been investigated. A kinetic scheme for the polymerization was proposed in which initiation of monomers by electron impact was followed by propagation and termination as in conventional polymerization, the initiation rate constant being a function of electron temperature alone. Four mechanism models were examined, depending on where each reaction step takes place: in the gas phase or on the substrate. Free-radical polymerization was assumed. Experiments were carried out at pressures ranging from 0.25 to 1.05 Torr and at voltages and currents that yielded cold and stable discharges. Substrate temperature was controlled. Deposition rate was determined by weighing. A regression program was used in addition to experimental tests in which substrate temperature was varied. The best approximation to the plasma polymer deposition process was found to be the following model: monomers are activated in the gas phase by electron bombardment and subsequently diffuse to the substrate where they propagate and terminate, adsorption of monomers on the substrate playing an important role. A rate expression relating polymer film deposition rate to the experimental variables is presented.     

STRUCTURE STERIQUE DES COMPOSES CYCLIQUES DU PHOSPHORE. XIII. ETUDE PAR MOMENT DIPOLAIRE DES OXO-2 ET THIO-2 PERHYDRO OXAZAPHOSPHORINES-1,3,2

Abstract

L'étude par moment dipolaire de la conformation de huit perhydro oxazaphosphorines-1,3,2 est décrite. The conformation of eight perhydro 1,3,2-oxazaphosphorines is studied by means of dipole moments.     

VICINAL DIBROMO-1-HYDROXYPHOSPHOLANE 1-OXIDES

Abstract

2,3-Dibromo-1-hydroxyphospholane 1-oxide and 3,4-dibromo-1-hydroxyphospholane 1-oxide were prepared in high yield by bromine addition to 1-hydroxyphosphol-2-ene 1-oxide or 1-hydroxyphosphol-3-ene 1-oxide, respectively. Both compounds were characterized by ¹H, ³¹P and ¹³C nmr, IR, Laser Raman and mass spectrometry.     

Synthesis and Application of Hydride Silica Composites for Rapid and Facile Removal of Aqueous Mercury

The adsorption of ionic mercury(II) from aqueous solution on functionalized hydride silicon materials was investigated. The adsorbents were prepared by modification of mesoporous silica C‐120 with triethoxysilane or by converting alkoxysilane into siloxanes by reaction with acetic acid. Mercury adsorption isotherms at 20 °C are reported, and maximum mercury loadings were determined by Langmuir fitting. Adsorbents exhibited efficient and rapid removal of ionic mercury from aqueous solution, with a maximum mercury loading of approximately 0.22 and 0.43 mmol of Hg g^?1 of silica C‐120 and polyhedral oligomeric silsesquioxane (POSS) xerogel, respectively. Adsorption efficiency remained almost constant from pH 2.7 to 7. These inexpensive adsorbents exhibiting rapid assembly, low pH sensitivity, and high reactivity and capacity, are potential candidates as effective materials for mercury decontamination in natural waters and industrial effluents.     

Synthesis and MRSA PK inhibitory activity of thiazole containing deoxytopsentin analogues

The public health care crisis caused by the emergence of drug resistant bacterial strains, e.g., methicillin resistant Staphylococcus aureus (MRSA) has underlined the urgent need to accelerate the discovery of new chemical entities active against antibiotic resistant bacteria. We report here the synthesis of a series thiazole containing deoxytopsentin analogues, which show moderate activity against a target MRSA pyruvate kinase enzyme: an evolutionary conserved hub protein critical for bacterial survival. A Hantzsch thiazole coupling between α-oxo-1H-indole-3-thioacetamides and 2-bromo-1-(1H-indol-3-yl)-ethanones provided facile access to the thiazole containing deoxytopsentin compounds.     

Fluorescent 2-(2′-hydroxybenzofuran)benzoxazole (HBBO) borate complexes: synthesis,optical properties,and theoretical calculations

The multi-step synthesis, structural and optical properties of original luminescent borate complexes derived from 2-(2′-hydroxybenzofuran)benzoxazole (HBBO) are reported. Functionalization at position 3 of the benzofuran ring was readily achieved through an electrophilic cyclization key step followed by a Sonogashira cross-coupling reaction. The optical properties of the resulting boron difluoride dyes highlight different photophysical behaviors depending on the nature of the substitution at position 3 of the benzofuran core (^tBu-phenylacetylene or NⁿBu₂-phenylacetylene). The NⁿBu₂-phenylacetylene moiety favors a sizeable intramolecular charge transfer as evidenced by a strong solvatochromism; a feature further confirmed by ab initio calculations.     

Nocturnal road traffic noise assessment and sleep research: The usefulness of different timeframes and in- and outdoor noise measurements

In this paper, we investigated the procedure of noise assessment in the study of nocturnal noise exposure during sleep in the home situation. The use of two different timeframes (fixed from 11 PM to 07 AM versus personal “Time in Bed” period) was explored as well as the relation between indoor and outdoor noise levels and between the actual and estimated noise levels. Noise recordings were performed inside and outside the bedroom of 24 subjects living in high density road traffic noise areas in the Brussels’ Capital Region during seven consecutive days. Indoor and outdoor noise indicators L_Aeq, L_Amax and individual noise events were analysed. Subjects completed a daily sleep log in which the Time in Bed period was assessed. The results indicate that, for outdoor noise assessment, the use of an average L_Aeq might not be sufficient to reflect well the noise levels during the sleep period. For indoor measurements, significant differences were found in the comparison between both timeframes (L_Aeq: T = 16; p < .001). Considering the relation between indoor and outdoor measurements, low correlations (r = .49; p < .001) were found even when the location of the bedroom as a mediating factor was accounted for (street side; r = .52; p < .001). Therefore, from our study, caution is needed when relying on outdoor noise measurements for the evaluation of sleep disturbances. Furthermore, one needs to be aware of the weak correspondence between indoor and outdoor noise levels in the discussion of what a harmonized noise indicator for the evaluation of noise exposure and sleep disturbances should consist of.     

Contrast enhanced maximum intensity projection ultrasound imaging for assessing angiogenesis in murine glioma and breast tumor models: A comparative study

The purpose of this study was to prospectively compare noninvasive, quantitative measures of vascularity obtained from four contrast enhanced ultrasound (US) techniques to four invasive immunohistochemical markers of tumor angiogenesis in a large group of murine xenografts. Glioma (C6) or breast cancer (NMU) cells were implanted in 144 rats. The contrast agent Optison (GE Healthcare, Princeton, NJ) was injected in a tail vein (dose: 0.4 ml/kg). Power Doppler imaging (PDI), pulse-subtraction harmonic imaging (PSHI), flash-echo imaging (FEI), and Microflow imaging (MFI; a technique creating maximum intensity projection images over time) was performed with an Aplio scanner (Toshiba America Medical Systems, Tustin, CA) and a 7.5 MHz linear array. Fractional tumor neovascularity was calculated from digital clips of contrast US, while the relative area stained was calculated from specimens. Results were compared using a factorial, repeated measures ANOVA, linear regression and z-tests. The tortuous morphology of tumor neovessels was visualized better with MFI than with the other US modes. Cell line, implantation method and contrast US imaging technique were significant parameters in the ANOVA model (p < 0.05). The strongest correlation determined by linear regression in the C6 model was between PSHI and percent area stained with CD31 (r = 0.37, p < 0.0001). In the NMU model the strongest correlation was between FEI and COX-2 (r = 0.46, p < 0.0001). There were no statistically significant differences between correlations obtained with the various US methods (p > 0.05). In conclusion, the largest study of contrast US of murine xenografts to date has been conducted and quantitative contrast enhanced US measures of tumor neovascularity in glioma and breast cancer xenograft models appear to provide a noninvasive marker for angiogenesis; although the best method for monitoring angiogenesis was not conclusively established.     

Phase-contrast volume holographic imaging system

A phase-contrast volume holographic imaging system for three-dimensional contrast enhancement is presented. The system utilizes a spatial filter placed on a conjugate plane to the volume holographic pupil to simultaneously enhance weak phase information at different depths within an object. The proposed system was validated with experimental image data obtained in mouse colon samples and quantitative measurements of modulation transfer function as well.     

Incompletely condensed fluoroalkyl silsesquioxanes and derivatives: precursors for low surface energy materials

A novel synthetic method was developed for the controlled functionalization of fluorinated polyhedral oligomeric silsesquioxanes (F-POSS), which are useful as low surface energy materials for superhydrophobic and superoleophobic materials. Utilizing triflic acid, open-cage compounds were created and then reacted with a variety of dichlorosilanes to produce functional F-POSS structures possessing alkyl-, aryl-, and acrylate-based moieties. The crystal structure for an endo,endo-disilanol F-POSS compound was determined by single-crystal X-ray diffraction. The chemical structures were confirmed using multinuclear NMR spectroscopy ((1)H, (13)C, (19)F, and (29)Si), FT-IR, and combustion analysis. Dynamic contact angle measurements of these compounds were taken with water and hexadecane. These novel structures were found to possess excellent wetting-resistant behavior, similar to that of the parent F-POSS compound. They are the first well-defined fluorinated nano-building blocks with a controlled level of reactive functionality for the development of new superhydrophobic and superoleophobic materials.