Atom‐transfer radical grafting polymerization of 2‐methacryloyloxyethyl phosphorylcholine from silicon wafer surfaces

2‐Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was grafted from silicon wafer surfaces at room temperature by combining self‐assembly of initiator and surface‐initiated atom transfer radical polymerization. Two methods were used to control the grafting process. One was to add free initiator to the reaction system; the other was to add excess deactivator. The grafting densities up to 0.3 chains/nm² were obtained. The surface thickness increased linearly with MPC conversion. The thickness depended on catalyst and monomer concentrations, as well as activator/deactivator ratio. Poly(MPC) layers of >100 nm thick were obtained by optimizing the polymerization conditions. A second block of either poly(MPC) or poly[2‐(dimethylamino)ethyl methacrylate] was also grown from the grafted poly(MPC), demonstrating the system livingness. X‐ray photoelectron spectroscopy was used to examine the surface chemical compositions showed good agreement with the theoretical values. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2931–2942, 2004     

Ultrathin polydimethylsiloxane-coated carbonyl iron particles and their magnetorheological characteristics

An ultrathin polydimethylsiloxane (PDMS) layer with a mean thickness of 1 nm was coated on soft magnetic carbonyl iron (CI) particles by using a simple thermal evaporation process, and then their physical characteristics were examined using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), thermal gravimetry analysis (TGA), and vibrating sample magnetometry (VSM). Magnetorheological (MR) fluid was prepared by using PDMS-coated CI powder, and its rheological behavior was investigated under different external magnetic field strengths using a rotational rheometer. The CI particles coated by a thin PDMS layer showed higher oxidation temperature than pristine CI particles and MR fluid consisting of PDMS-coated CI particles demonstrated better dispersion stability in a nonmagnetic carrier fluid.     

Viscoelastic and thermal behaviour of ternary blends polystyrene/polycarbonate/tetramethylpolycarbonate

The thermal analysis characteristics of ternary blends polystyrene(PS)/polycarbonate(PC)/tetramethylpolycarbonate (MPC) show that the PS forms mostly a pure PS phase, whereas the PC and MPC go into a second phase very close to a binary blend of the same PC/MPC weight composition. However, an additional broad glass transition is observed for most blends within the same temperature range (129–133°). On the other hand, the viscoelastic properties of the ternary blends containing 75% PC/MPC weight fraction exhibit an additional low frequency (large relaxation times) relaxation domain. This relaxation domain might be attributed either to a PS/MPC interphase or to PS “trapped” at the PS-PC/MPC interphase.     

Optimization design of the road unit in a hydronic snow melting system with porous snow

Hydronic snow melting systems are renewable and reliable to eliminate the slippery conditions on the road. In this study, a hydronic snow melting system was implemented in Harbin, China. The characteristics of porous snow were applied to develop a transient two-dimensional model, according to the experimental results. It is the first time that the snow microstructure was considered in the model for the hydronic snow melting system. Three parameters (embedded pipe depth, embedded pipe spacing, and supplied fluid temperature) were compared and analyzed to optimize the design of the hydronic snow melting system in the cold regions. The results indicated that the snow can be cleared in 4.5 h regardless of the fluctuation of parameters. The rank of influence degree was embedded pipe depth?>?supplied fluid temperature?>?embedded pipe spacing when the target was the maximum melting rate. However, the rank of influence degree changed as supplied fluid temperature?>?embedded pipe depth?>?embedded pipe spacing when the target was the average road surface temperature at the heating time of 6 h. The embedded pipe design should be the embedded pipe depth of 80 mm and embedded pipe spacing of 140 mm at the effects of thermal stress and pipe cost. The control strategy was that the supplied fluid temperature should be 298.15 K in the heating period of 0–1 h, then gradually increased to 308.15 K in the heating period of 1–4 h, and eventually decreased to 298.15 K in the heating period of 4–6 h to save energy. This work can offer a good reference for the optimization and design of hydronic snow melting systems in cold regions.

     

Instabilité et décrochage tournant en grille d'aubes

Rotating stall is a fundamental hydrodynamic instability which is encountered in most hydraulic and aeraulic turbomachinery. It appears to exist only with cascades that considerably slow down the fluid flow and occurs in the form of rotating structures in which the flow rate may be negative. The paper analyses this instability and its transitions in a simple two-dimensional configuration using a multi-domain numerical scheme and solver. The space-time variation of the flow rates occurring for an angle of attack increasing by steps shows first standing waves, then intermittent and permanent travelling waves of limited amplitude, corresponding to blade stall. At higher angles of attack, a high amplitude wave propagates a single structure (cell) with a negative flow rate, corresponding to stalling of the cascade.     

Numerical Simulation of a PA66 Flow Behaviour in a Hot Runner Gate

Summary: In actual hot runner systems for the injection moulding process, the control of polymers in gate is passive, which means that the melt temperature distribution and associated flow conductance is governed by a balance of heat convection by the flowing melt with heat conduction from the hot melt to the cold mould. This paper examines the rheological and thermal behaviour of a PA66 during freeze-off and melt flow activation. Numerical simulations were carried out according to the Finite Volume Method as implemented in the Ansys CFX® code. Rheological and thermal data were obtained from a careful material characterization conducted on a capillary rheometer and a differential scanning calorimetry (DSC). The analyses indicated that relatively small changes in melt temperature and injection pressure can substantially increase the flow conductance and dynamically control both the gate freezing and the onset of melt flow in the subsequent cycle. Therefore, simple gate thermal actuators were designed and numerically implemented to active control the plastic melt flow. This numerical approach can be used to design and optimize the active control of hot runners gate when the use of mechanical actuation (i.e. valve gates) is not suitable due to excessive cost, critical maintenance or miniaturization of the entire system.     

CFD Simulation of a Hydrogen／Argon Plasma Jet Reactor for Coal Pyrolysis

A Computational Fluid Dynamics (CFD) model was formulated for DC arc hydrogen/argon plasma jet re-actors used in the process of the thermal H2/Ar plasma pyrolysis of coal to acetylene. In this model, fluid flow, convective heat transfer and conjugate heat conductivity are considered simultaneously. The error caused by estimating the inner-wall temperature of a reactor is avoided. The thermodynamic and transport properties of the hydrogen/argon mixture plasma system, which are usually expressed by a set of discrete da-ta, are fitted into expressions that can be easily implemented in the program. The effects of the turbulence are modeled by two standard k-ε equations. The temperature field and velocity field in the plasma jet reactor were calculated by employing SIMPLEST algorithm. The knowledge and insight obtained are useful for the design improvement and scale-up of plasma reactors.     

Control of anchoring of nematic fluids at polymer surfaces created by in situ photopolymerization

In situ photopolymerization of alkyl acrylate monomers in the presence of a nematic fluid provides a cellular matrix of liquid crystalline droplets in which the chemical structure of the encapsulating polymer exerts control over the alignment (anchoring) of the liquid crystalline molecules. Control is obtained by variation of the alkyl side chains and through copolymerization of two dissimilar monofunctional acrylates. For example, among a series of poly(methylheptyl acrylate)s, the 1-methylheptyl analogue prefers planar anchoring of a nematic (TL205) over the temperature range studied. However, the polymers of other methylheptyl side chains display a homeotropic-to-planar anchoring thermal transition temperature similar to that of the n-heptyl analogue. Copolymerization of two monofunctional acrylates with opposing tendencies of aligning liquid crystal leads to tunability of anchoring behavior over a wide temperature range. The broad anchoring transitions we observed provide a way of achieving highly tilted anchoring.     

Preparation of zwitterionic sulfobetaine end‐functionalized poly(ethylene glycol)‐b‐poly(caprolactone) diblock copolymers and examination of their thermogelling properties

To investigate thermogelling behavior, in this study, we prepared a methoxy poly(ethylene glycol)‐b‐poly(ε‐caprolactone) diblock copolymer (MPC) with varying hydrophobic poly(ε‐caprolactone) (PCL) lengths and an MPC featuring a zwitterionic sulfobetaine (MPC‐ZW) at the chain end of the PCL segment. The terminal zwitterionic sulfobetaine was stoichiometrically modified to the terminal MPC diblock copolymer. The introduction of the zwitterionic end group lowered the crystallization enthalpies of the PCL block segments and increased the solubility of the diblock copolymer. The MPC and MPC‐ZW copolymers thus obtained formed translucent emulsions at room temperature when prepared as 20 wt %. When the temperature was increased above room temperature, MPC and MPC‐ZW exhibited a sol‐to‐gel phase transition. The phase transition and the gelation time of MPC and MPC‐ZW were affected by the length of the hydrophobic segments and the zwitterionic end group. Furthermore, introducing a zwitterionic end group into the PCL segment altered the onset temperature of gelation. Thus, we conclude that zwitterionic end groups introduced into PCL segments of distinct lengths could serve as key determinants in the thermogelling behavior of copolymers. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2185–2191     

Portable single-sided NMR measurements at variable temperatures: Implementation of a thermo-controlled device and application to the heating of bread dough

A temperature control unit was implemented to vary the temperature of samples studied on a commercial Mobile Universal Surface Explorer nuclear magnetic resonance (MOUSE-NMR) apparatus. The device was miniaturized to fit the maximum MOUSE sampling depth (25 mm). It was constituted by a sample holder sandwiched between two heat exchangers placed below and above the sample. Air was chosen as the fluid to control the temperature at the bottom of the sample, at the interface between the NMR probe and the sample holder, in order to gain space. The upper surface of the sample was regulated by the circulation of water inside a second heat exchanger placed above the sample holder. The feasibility of using such a device was demonstrated first on pure water and then on several samples of bread dough with different water contents. For this, T1 relaxation times were measured at various temperatures and depths and were then compared with those acquired with a conventional compact closed-magnet spectrometer. Discussion of results was based on biochemical transformations in bread dough (starch gelatinization and gluten heat denaturation). It was demonstrated that, within a certain water level range, and because of the low magnetic field strength of the MOUSE, a linear relationship could be established between T1 relaxation times and the local temperature in the dough sample.     

Autonomously-triggered microfluidic cooling using thermo-responsive hydrogels

We present autonomously-triggered on-chip microfluidic cooling devices that utilize thermo-responsive hydrogels to adapt to local environmental temperatures. An external rotating magnetic stirrer couples with an in situ fabricated nickel impeller in these centrifugal-based microfluidic cooling devices to recirculate cooler water. Temperature-responsive hydrogels, which exhibit volumetric expansion and contraction, are integrated at the axle of the impeller. In this design, the hydrogels behave similar to an automotive clutch, to autonomously control the impeller's rotation as a function of the local environmental temperature. Therefore, the hydrogels act as both sensors and actuators and help take away the necessity for additional temperature sensing, feedback, and/or control units here. Cooling devices capable of on-chip thermal management at multiple predetermined onset operation points are realized by changes to the composition of hydrogel to alter its lowest critical solution temperature (LCST). Furthermore, the effect of magnetic stirrer frequency on the fluid cooling and flowrates for different two-blade nickel impeller designs are presented.     

Melting curve and fluid equation of state of carbon dioxide at high pressure and high temperature

The melting curve and fluid equation of state of carbon dioxide have been determined under high pressure in a resistively heated diamond anvil cell. The melting line was determined from room temperature up to 11.1+/-0.1 GPa and 800+/-5 K by visual observation of the solid-fluid equilibrium and in situ measurements of pressure and temperature. Raman spectroscopy was used to identify the solid phase in equilibrium with the melt, showing that solid I is the stable phase along the melting curve in the probed range. Interferometric and Brillouin scattering experiments were conducted to determine the refractive index and sound velocity of the fluid phase. A dispersion of the sound velocity between ultrasonic and Brillouin frequencies is evidenced and could be reproduced by postulating the presence of a thermal relaxation process. The Brillouin sound velocities were then transformed to thermodynamic values in order to calculate the equation of state of fluid CO2. An analytic formulation of the density with respect to pressure and temperature is proposed, suitable in the P-T range of 0.1-8 GPa and 300-700 K and accurate within 2%. Our results show that the fluid above 500 K is less compressible than predicted from various phenomenological models.     

An efficient new method for extraction, separation and purification of psoralen and isopsoralen from Fructus Psoraleae by supercritical fluid extraction and high-speed counter-current chromatography

Psoralen and isopsoralen were extracted from Fructus Psoraleae (Psoralea corylitolia L.) by supercritical CO2. The effect of various parameters, i.e., pressure, temperature and sample particle size on yield was investigated with an analytical-scale supercritical fluid extraction (SFE) system to find the optimal conditions. The process was then scaled up by 50 times with a preparative SFE system under the optimized conditions of pressure (26 MPa), temperature (60 degrees C) and a sample particle size of 40-60 mesh. The yield of the preparative SFE was 9.1% and the combined yield of psoralen and isopsoralen was 2.5 mg/g of dry seeds. Psoralen and isopsoralen in the extract were separated and purified by high-speed counter-current chromatography with a two-phase solvent system composed of n-hexane-ethyl acetate-methanol-water (1:0.7:1:0.8, v/v), and the fractions were analyzed by HPLC, MS, 1HNMR and 13C NMR. The structures of the products were further confirmed by comparison with authentic samples (National Institute of the Control of Pharmaceutical and Biological Products, Beijing, China).     

超临界压力下国产航油RP-3导热系数的流动法测量

为了测量高温高压条件下航空燃料的导热系数,基于恒热流密度条件下,常物性不可压缩流体在圆管层流充分发展时的努塞尔数为常数原理,搭建了导热系数测量装置。通过牛顿冷却定律测量管内流体充分发展时的换热系数,可以在线测量流体的导热系数。经不确定度分析得到实验条件下最大相对不确定度为5.76%。使用乙苯和正十烷验对实验装置进行了标定,结果表明实验值与参考值比较的最大绝对偏差为5.36%。最后对2.5、3和3.5MPa下,不同温度范围的国产航油RP-3导热系数进行了测量。     

Stabilized liposomes with phospholipid polymers and their interactions with blood cells

To stabilize a phospholipid liposome, addition of various water-soluble polymers into a liposomal aqueous suspension was investigated. The water-soluble polymers were poly(ethylene oxide) (PEO), poly(N-vinyl pyrrolidone) (PVPy) and poly[2-methacryloyloxyethyl phosphorylcholine(MPC)], and poly[MPC-co-n-butyl methacrylate(BMA)]. The gel–liquid crystal transition temperature (T_c) of the diparmitoylphosphatidylcholine (DPPC) liposome was not changed by addition of these polymers significantly. However, membrane fluidity of DPPC liposome treated with water-soluble polymers, which was measured with fluorescence probe, depended on the chemical structure of the water-soluble polymers. In the case of PEO and PVPy, the temperature dependence of membrane fluidity was the same as that of the original DPPC liposome, on the other hand, poly(MPC) and poly(MPC-co-BMA) induced a rise in the temperature where an increase in the membrane fluidity was observed. The release of carboxy fluorescein from the DPPC liposome was suppressed by the addition of the MPC polymers. The liposomes in the MPC polymer solution were stable compared with those in water when plasma was added into the suspension. Interactions with stabilized liposome with blood cells such as platelets and erythrocytes were evaluated. Activation of platelets in contact with liposome covered with poly(MPC) or poly(MPC-co-BMA) was less than PEO-stabilized liposome. On the other hand, no hemolysis of erythrocytes was observed when every polymer-treated liposome was added in the suspension of erythrocytes. Based on these results, the MPC polymers could interact with the liposome surface, adsorb on the liposomes and stabilize them, and had no adverse effect to the blood cells even when they were in a physiological environment.     

Evaluation of a rapid semi-quantitative analysis approach using inductively coupled plasma optical emission spectrometry with axial viewing

This work describes a rapid screening procedure for simultaneous determination of multiple elements by inductively coupled plasma optical emission spectrometry with axial viewing. The process requires no calibration reference solutions, and therefore requires a shorter analysis time per sample. The “Rapid Quant for Axial” worksheet contains stored calibration functions that are not adjusted between analyses. These functions were applied to the analysis of standard reference materials to demonstrate the effectiveness of the screening tool. Quantitative recoveries were obtained for most elements in a variety of biological materials. Aluminum, Cu, Mn, P, and Zn were determined in spinach leaves, for example, with errors ranging from − 45% (Al) to + 23% (Cu). A simulation of the worksheet procedure was also tested. With this technique, a single user-specific, multi-element reference solution was used to prepare a new set of calibration parameters to replace those stored in the worksheet. This procedure proved to be useful for sample screening when the analytes of interest were not present in the original calibration file, or when their concentrations differed significantly from those previously stored.     

Validation of an MPC Polymer Coating to Attenuate Surface‐Induced Crosstalk between the Complement and Coagulation Systems in Whole Blood in In Vitro and In Vivo Models

Artificial surfaces that come into contact with blood induce an immediate activation of the cascade systems of the blood, leading to a thrombotic and/or inflammatory response that can eventually cause damage to the biomaterial or the patient, or to both. Heparin coating has been used to improve hemocompatibility, and another approach is 2‐methacryloyloxyethyl phosphorylcholine (MPC)‐based polymer coatings. Here, the aim is to evaluate the hemocompatibility of MPC polymer coating by studying the interactions with coagulation and complement systems using human blood in vitro model and pig in vivo model. The stability of the coatings is investigated in vitro and MPC polymer‐coated catheters are tested in vivo by insertion into the external jugular vein of pigs to monitor the catheters' antithrombotic properties. There is no significant activation of platelets or of the coagulation and complement systems in the MPC polymer‐coated one, which was superior in hemocompatibility to non‐coated matrix surfaces. The protective effect of the MPC polymer coat does not decline after incubation in human plasma for up to 2 weeks. With MPC polymer‐coated catheters, it is possible to easily draw blood from pig for 4 days in contrast to the case for non‐coated catheters, in which substantial clotting is seen.     

An extrusion fluidic driving method for continuous-flow polymerase chain reaction on a microfluidic chip

A novel extrusion driving protocol was developed based on micro-fabricated polydimethylsiloxane (PDMS) pneumatic valves. High efficiency liquid transfer was performed by using entirely overlapping control channels and fluid channels. A 0.5-s time is sufficient for the transfer of 9 μL sample solution between two chambers in the microchip with a nitrogen pressure of 70 kPa. The driving method was used in a microfluidic polymerase chain reaction (PCR) system, and rapid cycling of the PCR mixture in a closed loop was achieved. The amplification of DNA was demonstrated via both three-stage and two-stage PCR thermal cycling on the microchips resulting in significant reduction of the PCR time. The amplifications of 144-bp and 200-bp DNA fragments were achieved within 24 min using a three-stage protocol with 30 thermal cycles, and 130-bp DNA fragments within 12 min by using 20 thermal cycles in the two-stage system, compared to about 2 h in benchtop PCR with the same number of thermal cycles.     

Sub-second thermal desorption of a micro-sorbent trap for the analysis of ambient volatile organic compounds

This study investigates a novel approach of fast thermal desorption on a micro-sorbent trap for analyzing ambient volatile organic compounds (VOCs) by gas chromatography with flame ionization detection. Unlike conventional approaches, the temperature feedback mechanism for temperature control was abandoned, which often poses a limit to the heating speed due to slow response of the sensor and the control algorithm. Instead, a series of programmed a.c. pulses was given to the Ni-Cr wire coiled around the micro-trap to perform instant heating from room temperature to 250 degrees C within a fraction of a second, maintained at 250 degrees C during injection, and subsequently to 300 degrees C for trap cleaning. Temperature fluctuation around a high temperature set point could be maintained within +/- 10 degrees C. Significant improvement in resolution and peak height was obtained compared to a trap with temperature feedback and control algorithm. While keeping resolution at a satisfactory level, the sub-second desorption approach allows faster chromatography and at the same time increases the sensitivity of VOC analysis.