Headspace solid-phase microextraction with novel sol-gel permethylated-beta-cyclodextrin/hydroxyl-termination silicone oil fiber for determination of polybrominated diphenyl ethers by gas chromatography-mass spectrometry in soil

A simple, sensitive, and accurate method for determination of polybrominated diphenyl ethers (PBDEs) in soil has been developed based on headspace solid-phase microextraction (HS-SPME) followed by gas chromatography-mass spectrometry (GC-MS). Permethylated-beta-cyclodextrin/hydroxyl-termination silicone oil (PM-beta-CD/OH-TSO) fiber was first prepared by sol-gel technology and employed in SPME procedure. By exploiting the superiorities of sot-gel coating technique and the advantages of the high hydrophobic doughnut-shaped cavity of PM-beta-CD, the novel fiber showed desirable operational stability and extraction ability. After optimization on extraction conditions like water addition, extraction temperature, extraction time, salts effect, and solvents addition, the method was validated in soil samples, achieving good linearity (r>0.999), precision (R.S.D. < 10%), accuracy (recovery>78%), and detection limits (S/N =3) raging from 13.0 to 78.3 pg/g. (c) 2007 Published by Elsevier B.V.

Methanol synthesis from CO2 using a silicone rubber/ceramic composite membrane reactor

A one-dimensional isothermal pseudo-homogeneous parallel flow model was developed for the methanol synthesis from CO2 in a silicone rubber/ceramic composite membrane reactor. The fourth-order Runge-Kutta method was adopted to simulate the process behaviors in the membrane reactor. How those parameters affect the reaction behaviors in the membrane reactor, such as Damkohler number Da, pressure ratio p(r), reaction temperature T, membrane separation factor alpha, membrane permeation parameter phi , as well as the non-uniform parameter of membrane permeation L-1, were discussed in detail. Parts of the theoretical results were tested and verified; the experimental results showed that the conversion of the main reaction in the membrane reactor increased by 22% against traditional fixed bed reactor, and the optimal non-uniform parameter of membrane permeation rate, L-1.opt ,does exist. (C) 2003 Elsevier B.V All rights reserved.

Perfectly Hydrophobic Silicone Nanofiber Coatings: Preparation from Methyltrialkoxysilanes and Use as Water-Collecting Substrate

Perfectly hydrophobic (PHO) coatings consisting of silicone nanofibers have been obtained via a solution process using methyltrialkoxysilanes as precursors. On the basis of thermal gravimetry and differential thermal analysis (TG-DTA) and Fourier transform infrared spectroscopy (FTIR) results, the formula of the nanofibers was tentatively given and a possible growth mechanism of the nanofibers was proposed. Because of the low affinity between the coatings and the small water droplet, when using these coatings as substrate for collecting water vapor, the harvesting efficiency could be enhanced as compared with those from bare glass substrate for more than 50% under 25 degrees C and 60-90% relative humidity. By removing the surface methyl group by heat treatment or ultraviolet (UV) irradiation, the as-prepared perfectly hydrophobic surface can be converted into a superhydrophilic surface.

Design of silicone rubber according to requirements based on the multi-objective optimization of chemical reactions

The explicit expression between composition and mechanical properties of silicone rubber was derived from the physics of polymer elasticity, the implicit expression among material composition, reaction conditions and reaction efficiency was obtained from chemical thermodynamics and kinetics, and then an implicit multi-objective optimization model was constructed. Genetic algorithm was applied to optimize material composition and reaction conditions, and the finite element method of cross-linking reaction processes was used to solve multi-objective functions, on the basis of which a new optimization methodology of crosslinking reaction processes was established. Using this methodology, rubber materials can be designed according to pre-specified requirements.

Preparation of a novel polysulfone/polyethylene oxide/silicone rubber multilayer composite membrane for hydrogen-nitrogen separation

A novel poly sulfone/polyethylene oxide/silicone rubber (PSOPEO/SR) multilayer composite membrane was fabricated by double coating polysulfone substrate membrane with polyethylene oxide and silicone rubber. Gas permeation experiments were performed at 30 degrees C for hydrogen and nitrogen. PSf(PEO/SR membrane displayed high and steady performance for H-2/N-2: permeances of H-2 and N-2 of 49.51 and 0.601 GPU, respectively, and H-2/N-2 ideal separation factor of 82.3. It was explained that layer interfaces due to the introduction of PEO layer act as the permselective media and are responsible for the higher H-2/N-2 ideal separation factor which has exceeded the intrinsic permselectivities of the three polymers used in this study. (c) 2005 Elsevier B.V. All rights reserved.

Oscillatory instability of Rayleigh-Marangoni-Bénard convection in two-layer liquid systems

The oscillatory behaviour of the Rayleigh-Marangoni-Bénard convective instability (R-M-B instability) regarding two combinations of two-layer fluid systems has been investigated theoretically and numerically. For the two-layer system of Silicone oil (10cSt) over Fluorinert (FC70), both linear instability analysis and 2D numerical simulation show that the instability of the system depends strongly on the depth ratio Hr = H1/H2 of the two-layer liquid. The oscillatory regime at the onset of R-M-B convection enlarges with reducing Γ = Ra/Ma values. In the two-layer system of Silicone oil (2cSt) over water, it loses its stability and onsets to steady convection at first, then the steady convection bifurcates to oscillatory convection with increasing Rayleigh number Ra. This behaviour was found through numerical simulation above the onset of steady convection in the case of r = 2.9, ε=(Ra-Ruc)/Rac = 1.0, and Hr = 0.5. Our findings are different from the previous study of the Rayleigh-Benard instability and show the strong effects of the thermocapillary force at the interface on the time-dependent oscillations at or after the onset of convection. We propose a secondary oscillatory instability mechanism to explain the experimental observation of Degen et al. [Phys. Rev. E, 57 (1998), 6647-6659].

Oscillatory Instabilities of Two-Layer Rayleigh-Marangoni-Benard Convection

The Rayleigh–Marangoni–Bénard convective instability (R–M–B instability) in the two-layer systems such as Silicone oil (10cSt)/Fluorinert (FC70) and Silicone oil (2cSt)/water liquids are studied. Both linear instability analysis and nonlinear instability analysis (2D numerical simulation) were performed to study the influence of thermocapillary force on the convective instability of the two-layer system. The results show the strong effects of thermocapillary force at the interface on the time-dependent oscillations at the onset of instability convection. The secondary instability phenomenon found in the real two-layer system of Silicone oil over water could explain the difference in the comparison of the Degen’s experimental observation with the previous linear stability analysis results of Renardy et al.

On-Board Experimental Study Of Bubble Thermocapillary Migration In A Recoverable Satellite

An on-board space experiment of bubble thermocapillary migration was performed in the Chinese 22nd recoverable satellite in 2005. Silicone oil of nominal viscosity 5cSt was used as the continuous phase in the experiment. Air bubbles were injected into the liquid in the same direction as the constant temperature gradient in the liquid. The velocities of bubbles were obtained by recording the paths of the bubbles. The results indicate that the scaled velocity of bubbles decreases with an increase of the Marangoni number extended to 9288, which agrees with the results of previous space experiments and numerical simulation. In addition, the interaction between two bubbles was also observed in the space experiment. The trajectories and the velocities of the bubbles were obtained. The two-bubble experiment results are also consistent with the theoretical analysis.

Oscillatory Instability of Rayleigh-Marangoni-Benard Convection in Two-Layer System

The convective instabilities in two or more superposed layers heated from below were studied extensively by many scientists due to several interfacial phenomena in nature and crystal growth application. Most works of them were performed mainly on the instability behaviors induced only by buoyancy force, especially on the oscillatory behavior at onset of convection (see Gershuni et. Al.(1982), Renardy et. Al. (1985,2000), Rasenat et. Al. (1989), and Colinet et. Al.(1994)) . But the unstable situations of multi-layer liquid convection will become more complicated and interesting while considering at the same time the buoyancy effect combined with thermocapillary effect. This is the case in the gravity reduced field or thin liquid layer where the thermocapillary effect is as important as buoyancy effect. The objective of this study was to investigate theoretically the interaction between Rayleigh-Bénard instability and pure Marangoni instability in a two-layer system, and more attention focus on the oscillatory instability both at the onset of convection and with increasing supercriticality. Oscillatory behavious of Rayleigh-Marangoni-Bénard convective instability (R-M-B instability) and flow patterns are presented in the two-layer system of Silicon Oil (10cSt) over Fluorinert (FC70) for a larger various range of two-layer depth ratios (Hr=Hupper/Hdown) from 0.2 to 5.0. Both linear instability analysis and 2D numerical simulation (A=L/H=10) show that the instability of the system depends strongly on the depth ratio of two-layer liquids. The oscillatory instability regime at the onset of R-M-B convection are found theoretically in different regions of layer thickness ratio for different two-layer depth H=12,6,4,3mm. The neutral stability curve of the system displaces to right while we consider the Marangoni effect at the interface in comparison with the Rayleigh-Bénard instability of the system without the Marangoni effect (Ma=0). The numerical results show different regimes of the developing of convection in the two-layer system for different thickness ratios and some differences at the onset of pure Marangoni convection and the onset of Rayleigh-Bénard convections in two-layer liquids. Both traveling wave and standing wave were detected in the oscillatory instability regime due to the competition between Rayleigh-Bénard instability and Marangoni effect. The mechanism of the standing wave formation in the system is presented numerically in this paper. The oscillating standing wave results in the competition of the intermediate Marangoni cell and the Rayleigh convective rolls. In the two-layer system of 47v2 silicone oil over water, a transition form the steady instability to the oscillatory instability of the Rayleigh-Marangoni-Bénard Convection was found numerically above the onset of convection for ε=0.9 and Hr=0.5. We propose that this oscillatory mechanism is possible to explain the experimental observation of Degen et. Al.(1998). Experimental work in comparison with our theoretical findings on the two-layer Rayleigh-Marangoni-Bénard convection with thinner depth for H<6mm will be carried out in the near future, and more attention will be paid to new oscillatory instability regimes possible in the influence of thermocapillary effects on the competition of two-layer liquids

Substrate Strain and Proliferation & Differentiation of Bone Marrow Mesenchymal Stem Cells

New methods of surface modification of transparent silicone substrate were developed, and a new set of cell culture devices that provide homogeneous substrate strain was designed. Using the new device, effects of cyclic substrate strain on bone marrow mesenchymal stem cells(MSCs) were studied. It was found that cyclic strain influenced proliferation and differentiation of bone marrow MSCs in different ways.

Oscillatory Instabilities of Two-Layer Rayleigh-Marangoni-Benard Convection

The Rayleigh-Marangoni-Benard convective instability (R-M-B instability) in the two-layer systems such as Silicone oil (10cSt)/Fluorinert (FC70) and Silicone oil (2cSt)/water liquids are studied. Both linear instability analysis and nonlinear instability analysis (2D numerical simulation) were performed to study the influence of thermocapillary force on the convective instability of the two-layer system. The results show the strong effects of thermocapillary force at the interface on the time-dependent oscillations at the onset of instability convection. The secondary instability phenomenon found in the real two-layer system of Silicone oil over water could explain the difference in the comparison of the Degen's experimental observation with the previous linear stability analysis results of Renardy et al.

A solid-phase microextraction fiber coated with diglycidyloxycalix[4]arene yields very high extraction selectivity and sensitivity during the analysis of chlorobenzenes in soil

A novel fiber coated with novel sol-gel (5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26,28-diglycidyloxycalix[4]arene/hydroxy-terminated silicone oil; diglycidyloxy-C[4]/OH-TSO) was prepared for use with headspace solid-phase microextraction (HS-SPME) combined with gas chromatography (GC) and electron capture detection (ECD), which was applied in order to determine nine chlorobenzenes in soil matrices. Due to the improved fiber preparation, which increases the percentage of calixarene in the coating, the new calixarene fiber exhibits very high extraction selectivity and sensitivity to chlorine-substituted compounds. Various parameters affecting the extraction efficiency were optimized in order to maximize the sensitivity during the chlorobenzene analysis. Interferences from different soil matrices with different characteristics were investigated, and the amount extracted was strongly influenced by the matrix. Therefore, a standard addition protocol was performed on the real soil samples. The linear ranges of detection for the chlorobenzenes tested covered three orders of magnitude, and correlation coefficients > 0.9976 and relative standard deviations (RSD) < 8% were observed. The detection limits were found at sub-ng/g of soil levels, which were about an order of magnitude lower than those given by the commercial poly(dimethylsiloxane) (PDMS) coating for most of the compounds. The recoveries ranged from 64 to 109.6% for each analyte in the real kaleyard soil matrix when different concentration levels were determined over the linear range, which confirmed the reliability and feasibility of the HS-SPME/GC-ECD approach using the fiber coated with diglycidyloxy-C[4]/OH-TSO for the ultratrace analysis of chlorobenzenes in complex matrices.

Determination of phthalate acid esters plasticizers in plastic by ultrasonic solvent extraction combined with solid-phase microextraction using calix[4]arene fiber

Ultrasonic solvent extraction combined with solid-phase microextraction (SPME) with calix[4]arene/hydroxy-terminated silicone (C[4]/OHTSO) oil coated fiber was used to extract phthalate acid esters (PAEs) plasticizers in plastic, such as blood bags, transfusion tubing, food packaging bag, and mineral water bottle for analysis by gas chromatography (GC). Both extraction parameters (i.e. extraction time, extraction temperature, ionic strength) and conditions of the thermal desorption in a GC injector were optimized by analysis of eight phthalates. The fiber shows wonderful sensitivity and selectivity to the tested compounds. Owing to its high thermal stability (380 degreesC), the carryover effect that often encountered when using conventional fibers can be reduced by appropriately enhancing the injector temperature. The method showed linear response over two to four orders of magnitude with correlation coefficients (r) better than 0.996, and limits of detection (LOD) ranged between 0.006 and 0.084 mug l(-1). The relative standard deviation values obtained were less than or equal to 10%. bis-2-Ethylhexyl phthalate (DEHP) was the sole analyte detected in these plastics and recoveries were in the ranges 95.5-101.4% in all the samples. (C) 2004 Elsevier B.V. All rights reserved.

Period-doubling bifurcations of the thermocapillary convection in a floating half zone

This study experimentally explored the fine structures of the successive period-doubling bifurcations of the time-dependent thermocapillary convection in a floating half zone of 10 cSt silicone oil with the diameter d (0)=3.00 mm and the aspect ratio A=l/d (0)=0.72 in terrestrial conditions. The onset of time-dependent thermocapillary convection predominated in this experimental configuration and its subsequent evolution were experimentally detected through the local temperature measurements. The experimental results revealed a sequence of period-doubling bifurcations of the time-dependent thermocapillary convection, similar in some way to one of the routes to chaos for buoyant natural convection. The critical frequencies and the corresponding fractal frequencies were extracted through the real-time analysis of the frequency spectra by Fast-Fourier-Transformation (FFT). The projections of the trajectory onto the reconstructed phase-space were also provided. Furthermore, the experimentally predicted Feigenbaum constants were quite close to the theoretical asymptotic value of 4.669 [Feigenbaum M J. Phys Lett A, 1979, 74: 375-378].

Preparation of nanoparticles of bipyridineruthenium and silicotungstate and application as electrochemiluminescence sensor

The novel nanoparticles, [Ru(bPY)(3)](2)SiW12O40 center dot 2H(2)O(2) were firstly synthesized and characterized by elemental analysis, IR, and TEM. The nanoparticles were used to fabricate a chemically modified carbon paste electrode (CPE) by dispersing nanoparticles and graphite powder in silicone grease. Thus-prepared CPE shows bifunctional electrocatalytic activities towards the reduction of nitrite and the oxidation of oxalate, and exhibits sensitive electrochemiluminescence (ECL).