Microscale plasma-initiated patterning (muPIP)

A novel technique to create biomolecular micropatterns of varying complexity on several types of polymer substrates is presented. This method uses a patterned PDMS stamp to preferentially expose or protect areas of an underlying polymer substrate from oxygen plasma. Following plasma treatment, the substrate is immersed in a biomolecular ink, whereby molecules preferentially adsorb to either the plasma-exposed or plasma-protected substrate regions, depending on the particular substrate/ink combination. Using this method, polyethylene (PE), polystyrene (PS), poly(methyl methacrylate) (PMMA), poly(dimethylsiloxane) (PDMS), and poly(hydroxybutyrate/hydroxyvalerate) (PHBV) were micropatterned with different aqueous-based biomolecular inks (i.e., goat anti-rabbit immunoglobulin G, poly-l-lysine, and bovine serum albumin (BSA)). Water contact angle measurements performed on substrates after oxygen plasma exposure showed that the hydrophilicity of substrate areas exposed to plasma was significantly greater than that of areas protected from plasma by the PDMS stamp. In addition, scanning electron microscopy results demonstrated that substrate areas exposed to plasma were physically modified (e.g., roughened) compared to adjacent, protected areas. Areas in contact with a patterned PDMS stamp during plasma exposure were found to be physically unaffected by plasma treatment, and exhibited spatial features/dimensions consistent with the corresponding features of the patterned stamp. Last, protein patterns of BSA on the polymer substrates were stable and distinct after 4 weeks of incubation at 37 degrees C.     

三氟氯乙烯和六氟丙烯等离子体聚合物的ESR研究

用ESR分析了三氟氯乙烯(CTFE)和六氟丙烯(HFP)等离子体聚合的气体冷凝物和固体膜,其气体冷凝膜有70条超精细裂分线.并研究了它的ESR信号随温度的变化,把气体冷凝物和固体膜分别在室温中暴露在空气中三个月,十六个月或十五个月,ESR信号依然存在,这表明有十分稳定的游离基存在.     

Seeded dispersion polymerization of MMA using submicron PMMA particles as seed: a mechanistic study

Micron-size poly(methyl methacrylate) (PMMA) particles having a narrow particle size distribution were prepared by seeded dispersion polymerization of methyl methacrylate (MMA) using submicron PMMA particles as seed. The processes of particle aggregation and nucleation were controlled by the initial seed size, initial seed number, and initiator concentration, determining the formation of the mature particles and the number (N _(final)) and size of the final particles. It was found that N _(final) was equal to the number of particles produced in the absence of seed (N _{(ab initio)}) when the initial number of seed particles (N _(initial)) was less than N _{(ab initio)}. When N _(initial) was greater than N _{(ab initio)}, N _(final) was equal to k?×?N _(initial), where the value of k was a function of seed size and initiator concentration. k increased with seed size and was less than 1 at high initiator concentrations (0.52 and 1.00 %), while at low initiator concentrations (0.23 and 0.30 %), a maximum value of k was found for a 198 nm seed size. k could be greater than unity in some cases.     

Spectra analysis of Nd(DBM)3(TPPO)2 in MMA solution and PMMA matrix

The absorption spectra of Nd(DBM)3(TPPO)2 (DBM = dibenzoylmethane; TPPO = triphenylphosphine oxide) in methyl methacrylate (MMA) and polymethyl methacrylate (PMMA) were measured. Slater-Condon parameters (F2, F4, F6), Lander parameter (zeta4f), nephelauxetic effect parameters (beta, delta) and Judd-Ofelt parameters (Omega2, Omega4, Omega6) were calculated on the basis of the absorption spectra. Analysis of the relationship between the structure of rare-earth complexes and the nephelauxetic effect, Judd-Ofelt parameter Omega2 was carried out. The radiative properties of Nd(DBM)3(TPPO)2 in PMMA were also predicted according to the Judd-Ofelt theory. The values of the radiative lifetime and the emission cross-section of 4F3/2 --> 4I11/2 fluorescence transition are comparable with those shown by glasses used in the solid-state laser applications.     

Studies on plasma-initiated polymerization of acrylamide in solid state and in solution

Plasma-initiated polymerization is applied to acrylamide both in solid state and in solution. The effect of the amount of water, in addition to certain operational parameters such as applied vacuum, post polymerization period, and temperature, are well verified. Characteristics of polymers are determined by IR spectroscopy and X-ray diffraction studies as well as by intrinsic viscosity determinations.     

Improved synthesis of 5(6)-vinylbenzimidazole: Some polymerization studies

A general one-step reduction ring closure of o-nitroacetanalides is applied to the synthesis of 5(6)-acetylbenzimidazole and 5(6)-acetyl-2-methylbenzimidazole in good yield. The former is readily converted to the vinyl monomer by reduction and dehydration. Polymerization of this monomer with free-radical initiation under a variety of conditions gives polymers with essentially identical nuclear magnetic resonance (NMR) spectra, implying no basic change in polymer structure.     

Synthesis and kinetic studies of PMMA nanoparticles by non-conventionally initiated emulsion polymerization

The aqueous emulsifier-free emulsion polymerization of methyl methacrylate (MMA) was studied under the catalytic effect of in situ developed bivalent transition metal-EDTA complex with ammonium persulfate (APS, (NH₄)₂S₂O₈) as initiator. Out of these, Cu(II)-EDTA system was selected for detailed kinetic and spectrometric study of polymerization. The apparent activation energy E_a, 34.5 kJ/mol, activation energy of initiator decomposition E_d, 26.9 kJ/mol, energy of propagation E_p, 29 kJ/mol and energy of termination E_t, 16 kJ/mol were reported. The emulsion polymer (PMMA) latex was characterized through the determination of the size and morphology by scanning electron microscopy, the average molecular weight by GPC and viscosity methods and the sound velocity by ultrasonic interferometer. From the kinetic results, the rate of polymerization, R_p at 50 °C was expressed by

     

Correlation between polymerization of cyclic butylene terephthalate (CBT) and crystallization of polymerized CBT

The correlation between ring-opening polymerization(ROP) of cyclic butylene terephthalate(CBT) and crystallization of polymerized CBT(p CBT) strongly affected the final properties of p CBT and its composites.The major objective of this contribution is to pinpoint the threshold temperature between them and the interrelation is successfully disclosed.That is,crystallization during polymerization occurs below 204 °C and the crystallization properties of p CBT are determined by this isothermal ROP stage; polymerization and crystallization are gradually separated with the increase of temperature of ROP(TP) from 204 °C,and the crystallization properties of p CBT are dominated by cooling stage; only polymerization is performed above 212 °C.Moreover,quantitative analysis suggests that uniform crystal size distributions and thicker lamellar crystals derive from the stage of crystallization during polymerization.On the contrary,the crystal size distributions become wider above 204 °C of TP and lead to obvious double melting peaks during heating scan.These efforts provide a very useful guide for the related investigation and application of CBT.     

Preparation and characterization of plasma polymerized (ethylene + oxygen) thin films

This report describes the preparation and characterization of plasma polymerized (ethylene + oxygen) (PPEO) thin films. The PPEO films described herein represent a unique class of materials from the standpoint of stoichiometry, chemical functionality, and crosslink density. It will be shown that PPEO deposition rate and structure, evidenced both at the surface and in the bulk, are strongly dependent upon the flow rate of O₂ in the ethylene/O₂ feed gas mixture. High O₂ flow rates produce films with relatively high oxygen concentrations. Furthermore, increasing O₂ flow rates lead to film structures which increasingly favor the incorporation of highly oxidized carbon functionalities. These effects (increasing film concentrations of oxygen and highly oxidized carbon functionalities) appear to show no further increase for O₂ flow rates greater than or equal to ca. 10% of the ethylene flow rate.     

Mechanistic studies of plasma polymerization of allylamine

Plasma polymerization of allylamine is performed both in continuous wave and pulsed mode. Chemical derivatization is applied to determine primary and secondary amine concentration. Primary amines are efficiently formed, but secondary amines are more abundant. A polymerization mechanism is proposed to account for the difference in amine content obtained from comparison between continuous wave and pulsed mode plasma polymerization. The AFM measurements performed on ultrathin (1-10 nm) plasma polymers confirm the continuity of films and that the film growth on silicon occurs via a layer-by-layer mechanism because no islandlike structures were detected.     

Mechanism of plasma-initiated polymerization: Concerning the nature of solvent effects on the lifelike polymerization of water-soluble vinyl monomers

To provide a satisfactory basic understanding of the solvent effect of plasma-initiated polymerization, we have carried out several kinds of polymerizations of various water-soluble vinyl monomers. It has been shown that aqueous solution of such vinyl monomers underwent the polymerizations induced by methyl isobutyrate (MIB) plasma-exposed glass surface. The invisible ultrathin polymer film trapping an active radical species deposited on the plasma-exposed glass surface apparently induced the polymerizations. The efficiency, however, was largely dependent on the solvent used: the solvent can be considered to act as “an initiation-activator” for the lifelike postpolymerization. The nature of the solvent effect was ascribed to the physicomechanical property such as swelling ability and/or solubility toward the ultrathin film formed on the glass surface. Thus it has been suggested that the choice of good-balanced combination between the structural feature of the plasma-induced ultrathin polymer film and the solvent as an initiation-activator is important to achieve activity of a desired solution polymerization.     

Preparation of Al(OH)3/PMMA nanocomposites by emulsion polymerization

Al(OH)₃/PMMA nanocomposites were prepared by the emulsion polymerization of methyl methacrylate (MMA) in the presence of surface‐functionalized Al(OH)₃ particles. Nanosized Al(OH)₃ particles were previously functionalized with a silane coupling agent, 3‐(trimethoxysilyl) propyl methacrylate (γ‐MPS), which was confirmed by FT‐IR and XRF analysis. The average size of seed particles was around 70 nm, and the density of the coupling agent on the particles was calculated to be 8.9 µmol m^?2. The emulsion polymerization was attempted at relatively high solid content of 40–46 wt%. The ratio of the seed particles to MMA had a strong influence on the stability of latex as well as the morphology of composites. Nanocomposites where several PMMA nodules were attached on the surface of Al(OH)₃ core were produced with stable latex emulsion when the weight percents of Al(OH)₃ to MMA were below 20. In the case of higher ratio of 30%, however, the latexes became unstable with an aggregation, and the product morphology was in the shape of large composite. Thermogravimetric analysis showed an improved thermal stability of PMMA composites with the incorporation of Al(OH)₃ nanoparticles. Copyright © 2008 John Wiley & Sons, Ltd.     

Hydrophilic modification of poly(vinylidene fluoride) (PVDF) by in situ polymerization of methyl methacrylate (MMA) monomer

The hydrophilicity of poly(vinylidene fluoride) (PVDF) was first improved by in situ polymerization of polar monomer in PVDF solution. Methyl methacrylate was adopted as the reaction monomer, and the polymerization occurred in a solution of PVDF in N,N-dimethylformamide. PVDF/poly(methyl methacrylate) (PMMA) blend was obtained after in situ polymerization. The relative hydrophilicity of the in situ blend was characterized by contact angle measurement. At the same time, the hydrophilicity of the PVDF/PMMA blends prepared by solution blending was compared with that of the in situ blend. The contact angle measurements indicated that in situ polymerization has a stronger modifying effect on the hydrophilicity of PVDF than solution blending.     

Mass spectrometry of poly(methyl methacrylate) (PMMA) prepared by atom transfer radical polymerization (ATRP)

Poly(methyl methacrylate) (PMMA) was synthesized via atom transfer radical polymerization (ATRP). As a catalyst copper(I)thiocyanate (CuSCN) was used with N-n-pentyl-2-pyridylmethanimine as a ligand. Infrared spectroscopy and matrix assisted laser desorption ionization time-of-flight mass spectrometry were used to characterize the synthesized polymers. From this it was clear that at least to some extent thiocyanate was present as end groups of the PMMA chains. This observation is discussed in view of a phenomenon called halogen exchange, which has been reported before for bromine/chlorine exchange in ATRP.     

The competitive ablation and polymerization (CAP) principle and the plasma sensitivity of elements in plasma polymerization and treatment

The competitive ablation and polymerization (CAP) principle relates the ablation of materials in plasma to the deposition of materials in plasma. Plasma polymerization and plasma treatment cannot be elucidated without consideration of the fragmentation of molecules in both the gas and solid phases. The general fragmentation tendency follows a plasma sensitivity series of the elements involved that is based on element electronegativity. When consecutive plasma treatments, sequential plasma polymerization, or a combination of plasma treatment and plasma polymerization are carried out in the same reactor, factors that are often not considered in an ordinary individual process become crucial. The CAP principle and the concept of a plasma sensitivity series of the elements explain the rather complicated and interrelated influences of fragmented elements in the plasma deposition of materials. Plasma polymers should be considered a mixture of oligomers and polymeric networks. The oligomer content in a plasma‐polymerized layer is vitally important to the adhesion of the plasma polymer to the substrate as well as to any subsequent coating applied to the layer of the plasma polymer. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 943–953, 2000     

Some aspects of plasma polymerization of fluorine-containing organic compounds

The polymerization of perfluorocarbons and fluorohydrocarbons was investigated by using both continuous and pulsed rf discharge (100 μsec on and 900 μsec off). Plasma polymerization of perfluorocarbons is generally slower than that of hydrocarbons, which seems to be due to the absence of contribution of fluorine detachment to the plasma polymerization. Presence of multiple bond(s) or cyclic structure in a monomer is necessary to obtain high enough polymerization; however, the plasma polymerization mechanism postulated to plasma polymerization of hydrocarbons is still valid to these monomers. Cyclic structure is very effective to enhance the plasma polymerization capability of perfluorocarbons. Saturated straight-chain perfluorocarbons do not polymerize well in plasma, but the grafting of fluorine-containing functions on the surface of polymeric substrate can be achieved by the plasma of these compounds. The effect of pulse on the plasma polymerization was found to be similar to that found for hydrocarbons.     

Preparation and properties of plasma-initiated graft copolymerized membranes for blood plasma separation

A hydrophilic composite membrane for blood plasma separation has been prepared by surface graft copolymerization initiated by low-temperature plasma (LTP). After short LTP pre-irradiation onto a microporous polypropylene (PP) membrane, N-N-dimethylacrylamide (DMAA) vapor was introduced for grafting. The PP membrane had a 0.45 μm effective pore size and a 130 μm thickness. The rate of DMAA grafting onto PP was very high, even in vapor-solid phase reaction under reduced pressure; DMAA 1 mm Hg (133Pa). The percentage of grafted poly-DMAA (PDMAA) reached 15% within 5 min post graft polymerization, and the membrane surface, including the interior surface of pores, became completely hydrophilic. There was no apparent change observed in the membrane morphology in the dry state after the PDMAA-grafted layer was formed. However, water flux significantly decreased, probably due to swelling of the PDMAA-grafted layer. With a grafting yield below 17%, the PDMAA-grafted PP (PP-g-PDMAA) membrane showed a good separation capability of plasma from whole blood. The PP-g-PDMAA membrane exhibited low complement activating potential, high sieving coefficient for plasma proteins and high blood compatibility. Decreases in adsorption of blood cells, plasma proteins, and other biomolecules may be the reason for the membrane performance.     

Atom transfer radical polymerized PMMA/magnetite nanocomposites and their magnetorheology

We synthesized core/shell-typed magnetic nanoparticle composites using poly(methyl methacrylate) (PMMA) as a shell and magnetite nanoparticle (MN) as a core, in which the PMMA shell was prepared via atomic transfer radical polymerization (ATRP) method. Chemical structure and morphology of the synthesized MN–PMMA nanocomposite were investigated using FT-IR and TEM, respectively. Magnetorheological (MR) fluid was prepared by dispersing synthesized MN–PMMA in non-magnetic medium. Both shear stress and shear viscosity of the MR fluids as a function of shear rate were measured using a rotational rheometer with a magnetic field generator, exhibiting that a yield stress increased with an external magnetic field strength.