Synthesis of Silicone‐Methacrylate Copolymers by ATRP Using a Nickel‐Based Supported Catalyst

Summary: A nickel (II) bromide catalyst immobilized onto crosslinked diphenylphosphinopolystyrene (PS‐PPh₃/NiBr₂) was used for the synthesis of silicone‐methacrylate copolymers by atom transfer radical polymerization (ATRP) of various methacrylate monomers using ω‐bromide silicone chains as macroinitiator. The polymerization proved to be very well‐controlled when a sufficient amount of soluble ligand, i.e., triphenylphosphine (PPh₃), was added to the polymerization medium. Under these conditions, this technique efficiently led to the production of different copolymers with controlled compositions and molecular weights as well as narrow polydispersity indices ( < 1.5). The recovered copolymers proved to be almost free of catalyst residues. Indeed, inductively coupled plasma (ICP) analysis revealed a metal content lower than 100 ppm, representing only a few percent of the initial metal content in the polymerization medium.

Synthesis of PDMS block copolymer in toluene catalyzed by PS‐PPh₃/NiBr₂ in the presence of soluble PPh₃ at 90 °C.     

Low-Diffusion Fricke Gel Dosimeters with Core-Shell Structure Based on Spatial Confinement

The diffusion of ferric ions is an important challenge to limit the application of Fricke gel dosimeters in accurate three-dimensional dose verification of modern radiotherapy. In this work, low-diffusion Fricke gel dosimeters, with a core-shell structure based on spatial confinement, were constructed by utilizing microdroplet ultrarapid freezing and coating technology. Polydimethylsiloxane (PDMS), with its excellent hydrophobicity, was coated on the surface of the pellets. The concentration gradient of the ferric ion was realized through shielding half of a Co-60 photon beam field size, and ion diffusion was measured by both ultraviolet-visible spectrophotometry and magnetic resonance imaging. No diffusion occurred between the core-shell pellets, even at 96 h after irradiation, and the diffusion length at the irradiation boundary was limited to the diameter (2–3 mm) of the pellets. Furthermore, Monte Carlo calculations were conducted to study dosimetric properties of the core-shell dosimeter, which indicated that a PDMS shell hardly affected the performance of the dosimeter.     

<Emphasis Type="Italic">In vitro</Emphasis> blood flow in a rectangular PDMS microchannel: experimental observations using a confocal micro-PIV system

Progress in microfabricated technologies has attracted the attention of researchers in several areas, including microcirculation. Microfluidic devices are expected to provide powerful tools not only to better understand the biophysical behavior of blood flow in microvessels, but also for disease diagnosis. Such microfluidic devices for biomedical applications must be compatible with state-of-the-art flow measuring techniques, such as confocal microparticle image velocimetry (PIV). This confocal system has the ability to not only quantify flow patterns inside microchannels with high spatial and temporal resolution, but can also be used to obtain velocity measurements for several optically sectioned images along the depth of the microchannel. In this study, we investigated the ability to obtain velocity measurements using physiological saline (PS) and in vitro blood in a rectangular polydimethysiloxane (PDMS) microchannel (300 μm wide, 45 μm deep) using a confocal micro-PIV system. Applying this combination, measurements of trace particles seeded in the flow were performed for both fluids at a constant flow rate (Re = 0.02). Velocity profiles were acquired by successive measurements at different depth positions to obtain three-dimensional (3-D) information on the behavior of both fluid flows. Generally, the velocity profiles were found to be markedly blunt in the central region, mainly due to the low aspect ratio (h/w = 0.15) of the rectangular microchannel. Predictions using a theoretical model for the rectangular microchannel corresponded quite well with the experimental micro-PIV results for the PS fluid. However, for the in vitro blood with 20% hematocrit, small fluctuations were found in the velocity profiles. The present study clearly shows that confocal micro-PIV can be effectively integrated with a PDMS microchannel and used to obtain blood velocity profiles along the full depth of the microchannel because of its unique 3-D optical sectioning ability. Advantages and disadvantages of PDMS microchannels over glass capillaries are also discussed.     

A cell culturing system that integrates the cell loading function on a single platform and evaluation of the pulsatile pumping effect on cells

In this paper, we present a novel microfluidic system with pulsatile cell storing, cell-delivering and cell culturing functions on a single PDMS platform. For this purpose, we have integrated two reservoirs, a pulsatile pumping system containing two soft check valves, which were fabricated by in situ photopolymerization, six switch valves, and three cell culture chambers all developed through a simple and rapid fabrication process. The sample volume delivered per stroke was 120 nl and the transported volume was linearly related to the pumping frequency. We have investigated the effect of the pulsatile pneumatic micropumping on the cells during transport. For this purpose, we pumped two types of cell suspensions, one containing human breast adenocarcinoma cells (MCF-7) and the other mesenchymal stem cells (hMSCs) derived from bone marrow. The effect of pulsatile pumping on both cell types was examined by short and long-term culture experiments. Our results showed that the characteristics of both cells were maintained; they were not damaged by the pumping system. Evaluations were carried out by morphological inspection, viability assay and immunophenotyping analysis. The delivered MCF-7 cells and hMSCs spread and proliferated onto the gelatin coated cell culture chamber. This total micro cell culture system can be applied to cell-based high throughput screening and for co-culture of different cells with different volume.     

基于玻璃基底微流控芯片的制备

介绍一种基于玻璃基底微流控芯片的制作方法,通过光刻工艺在玻璃基底表面刻蚀出微通道。利用氧等离子体对聚二甲基硅氧烷（Polydimethylsiloxane,PDMs）和微通道所在的基底表面进行处理,使PDMS与基底表面性质由疏水性变为亲水性,完成PDMS与玻璃基底的共价键结合。通过实验表明,经氧等离子体处理之后的PDMS与玻璃基底的密封效果较好。鉴于PDMS具有良好的热稳定性,无毒性,以及较好的光学特性等,此微流控芯片可用于生物医学以及化学领域中的化学发光及荧光检测。     

Characterization of Polydimethylsiloxane (PDMS) Properties for Biomedical Micro/Nanosystems

Polydimethylsiloxane (PDMS Sylgard 184, Dow Corning Corporation) pre-polymer was combined with increasing amounts of cross-linker (5.7, 10.0, 14.3, 21.4, and 42.9 wt.%) and designated PDMS1, PDMS2, PDMS3, PDMS4, and PDMS5, respectively. These materials were processed by spin coating and subjected to common micro-fabrication, micro-machining, and biomedical processes: chemical immersion, oxygen plasma treatment, sterilization, and exposure to tissue culture media. The PDMS formulations were analyzed by gravimetry, goniometry, tensile testing, nano-indentation, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). Spin coating of PDMS was formulation dependent with film thickness ranging from 308 microm on PDMS1 to 171 microm on PDMS5 at 200 revolutions per minute (rpm). Ultimate tensile stress (UTS) increased from 3.9 MPa (PDMS1) to 10.8 MPa (PDMS3), and then decreased down to 4.0 MPa (PDMS5). Autoclave sterilization (AS) increased the storage modulus (sigma) and UTS in all formulations, with the highest increase in UTS exhibited by PDMS5 (218%). PDMS surface hydrophilicity and micro-textures were generally unaffected when exposed to the different chemicals, except for micro-texture changes after immersion in potassium hydroxide and buffered hydrofluoric, nitric, sulfuric, and hydrofluoric acids; and minimal changes in contact angle after immersion in hexane, hydrochloric acid, photoresist developer, and toluene. Oxygen plasma treatment decreased the contact angle of PDMS2 from 109 degrees to 60 degrees. Exposure to tissue culture media resulted in increased PDMS surface element concentrations of nitrogen and oxygen.     

Investigation into modification of mass transfer kinetics by acrolein in a renal biochip

In this study we present a method for investigating the effect of acrolein, a nephrotoxic and urotoxic metabolite of the anticancerous prodrugs ifosfamide and cyclophosphamide, in a blood-renal barrier biochip. The real time monitoring of mass transfers of caffeine, vitamin B12 and albumin in the biochip was performed thanks to an in vitro dialysis method. The diffusion coefficients of the solutes and their dialysance from the apical to the basolateral compartments were found to be molecular weight and cell-membrane dependent, thus demonstrating the cell-barrier functionality. The toxicity induced by the acrolein led to modifications to mass transfer properties which appeared to be acrolein dose, time and solute molecular weight dependent. Solute mass transfer across the cell layer increased with acrolein concentrations. The sensitivity of this analysis method contributes to identify the mass transfer properties and to monitor the modification to the renal parameter when submitted to toxic cell compounds. The results provide the foundation for exploring kidney behavior in response to drugs thanks to a blood-tissue barrier model using a technique based on in vitro dialysis and real time analysis.     

Polymer-Based Packaging Platform for Hybrid Microfluidic Systems

A polymer-based packaging platform for creating hybrid microfluidic systems is presented. Polydimethylsiloxane (PDMS) is cast into an acrylic mold frame with suspended elements that are removed after curing to form chip cavities, inlet and outlet ports, microchannels, and reservoirs. The packaging approach enables the integration of off-the-shelf components such as pumps and valves with glass microfluidic devices, electronic chips, sample reservoirs, and flow channels. A particle pre-concentration module with a glass capture chip and integrated micropump is shown as an example. A pneumatically driven microfluidic pumping module is also shown. Custom microfluidic interconnects for interfacing to micro-scale fluidic systems are presented. The connectors are capable of withstanding more than 1000 psi and allow microdevices to be rapidly connected to macroscopic devices and systems, without the use of tools.     

Novel Surfactant-Induced MWCNTs/PDMS-Based Nanocomposites for Tactile Sensing Applications

The paper presents the use of surfactant-induced MWCNTs/PDMS-based nanocomposites for tactile sensing applications. The significance of nanocomposites-based sensors has constantly been growing due to their enhanced electromechanical characteristics. As a result of the simplified customization for their target applications, research is ongoing to determine the quality and quantity of the precursor materials that are involved in the fabrication of nanocomposites. Although a significant amount of work has been done to develop a wide range of nanocomposite-based prototypes, they still require optimization when mixed with polydimethylsiloxane (PDMS) matrices. Multi-Walled Carbon Nanotubes (MWCNTs) are one of the pioneering materials used in multifunctional sensing applications due to their high yield, excellent electrical conductivity and mechanical properties, and high structural integrity. Among the other carbon allotropes used to form nanocomposites, MWCNTs have been widely studied due to their enhanced bonding with the polymer matrix, highly densified sampling, and even surfacing throughout the composites. This paper highlights the development, characterization and implementation of surfactant-added MWCNTs/PDMS-based nanocomposites. The prototypes consisted of an optimized amount of sodium dodecyl sulfonate (SDS) and MWCNTs mixed as nanofillers in the PDMS matrix. The results have been promising in terms of their mechanical behaviour as they responded well to a maximum strain of 40%. Stable and repeatable output was obtained with a response time of 1 millisecond. The Young’s Modulus of the sensors was 2.06 MPa. The utilization of the prototypes for low-pressure tactile sensing applications is also shown here.     

Pharmaceutical applications of vibrational chemical imaging and chemometrics: a review

The emergence of chemical imaging (CI) has gifted spectroscopy an additional dimension. Chemical imaging systems complement chemical identification by acquiring spatially located spectra that enable visualization of chemical compound distributions. Such techniques are highly relevant to pharmaceutics in that the distribution of excipients and active pharmaceutical ingredient informs not only a product's behavior during manufacture but also its physical attributes (dissolution properties, stability, etc.). The rapid image acquisition made possible by the emergence of focal plane array detectors, combined with publication of the Food and Drug Administration guidelines for process analytical technology in 2001, has heightened interest in the pharmaceutical applications of CI, notably as a tool for enhancing drug quality and understanding process. Papers on the pharmaceutical applications of CI have been appearing in steadily increasing numbers since 2000. The aim of the present paper is to give an overview of infrared, near-infrared and Raman imaging in pharmaceutics. Sections 2 and 3 deal with the theory, device set-ups, mode of acquisition and processing techniques used to extract information of interest. Section 4 addresses the pharmaceutical applications.