Monodisperse Polymer Research Articles

Study of Kinetics and Macroinitiator Efficiency in Surface-Initiated Atom-Transfer Radical Polymerization

Generation of surface-tethered block copolymer brushes with well-defined physicochemical characteristics requires achieving good control over the degree of polymerization of each block of the copolymer. In order to precisely form these block copolymer layers, one must (1) utilize a polymerization scheme that is capable of generating nearly monodisperse polymers, (2) fully characterize the kinetics of surface-initiated polymerization, and (3) produce macroinitiators with living characteristics capable of reinitiating the growth of each subsequent block. In this work, we describe technological steps leading to the controlled growth of surface-tethered homopolymers and multiblock copolymers via surface-initiated atom transfer radical polymerization (ATRP) from flat substrates. We first report on investigating the ability of a macroinitiator to reinitiate a homopolymer brush. We use computer simulations to illustrate the advantages of an “added deactivator” type ATRP over the traditional “sacrificial initiator” ATRP. In the section describing the formation of multiblock copolymer brushes we show that the growth of individual blocks in a multiblock copolymer brush depends on the type of macroinitiator and the type of monomer used to produce the subsequent block. We demonstrate that while poly(methyl methacrylate) and poly(2-hydroxyethyl methacrylate) form multiblock copolymer brushes readily (up to a hexablock reported herein), achieving good control over growth of surface-tethered multiblock copolymers comprising poly(methyl methacrylate) and poly(dimethylaminoethyl methacrylate) blocks with equal lengths of both blocks is challenging.

DNA Nanotechnology Technique for Monodisperse Synthesis

I consider the synthesis of high molecular weight, monodisperse polymers starting from small, monodisperse chains end-labeled with DNA ligands. When these ligands are appropriately designed, a two-stage mixing protocol results in a solution of chains of twice the original molecular weight. The process can be repeated to produce larger and larger chains, of essentially biologically precise molecular weights. The design of precision branched, di-, tri-, and multiblock copolymers is possible under a slight generalization of protocol.

Agitation requirement for synthesis of micron-sized monodisperse polymer particles in soap-free polymerization method

Single-stage polymerization recently proposed for producing micron-sized polymer particles in aqueous media by Gu, Inukai and Konno (2002) was carried out under the control of agitation with styrene monomer, an amphoteric initiator, 2,2′-azobis [N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate and a pH buffer NH3/NH4Cl at a monomer concentration of 1.1 kmol/m3 H2O, an initiator concentration of 10 mol/m3 H2O and a buffer concentration of [NH3] = [NH4Cl] = 10 mol/m3 H2O. In the polymerizations, impeller speed was ranged from 300 to 500 rpm to satisfy complete dispersion of the monomer phase and not to introduce the gas phase from the free surface. Polymerization experiments under steady agitation indicated that impeller speed was an important factor for size distribution of polymer particles. An increase in impeller speed promoted particle coagulation during the polymerization to enlarge the average size of polymer particles but widen the size distribution. To produce polymer particles with narrow size distribution, stepwise reduction in impeller speed was examined in the polymerization experiments. It was demonstrated that this method was more effective than the steady agitation. The impeller speed reduction could produce highly monodisperse particles with an average size of 2 μm and a coefficient of variation of size distributions of 2.2% that was much smaller than typical monodispersity criterion of 10%.

Coarse grained model of entangled polymer melts

A coarse graining procedure aimed at reproducing both the chain structure and dynamics in melts of linear monodisperse polymers is presented. The reference system is a bead-spring-type representation of the melt. The level of coarse graining is selected equal to the number of beads in the entanglement segment, Ne. The coarse model is still discrete and contains blobs each representing Ne consecutive beads in the fine scale model. The mapping is defined by the following conditions: the probability of given state of the coarse system is equal to that of all fine system states compatible with the respective coarse state, the dissipation per coarse grained object is similar in the two systems, constraints to the motion of a representative chain exist in the fine phase space, and the coarse phase space is adjusted such to represent them. Specifically, the chain inner blobs are constrained to move along the backbone of the coarse grained chain, while the end blobs move in the three-dimensional embedding space. The end blobs continuously redefine the diffusion path for the inner blobs. The input parameters governing the dynamics of the coarse grained system are calibrated based on the fine scale model behavior. Although the coarse model cannot reproduce the whole thermodynamics of the fine system, it ensures that the pair and end-to-end distribution functions, the rate of relaxation of segmental and end-to-end vectors, the Rouse modes, and the diffusion dynamics are properly represented.

Administered activity and metastatic cure probability during radioimmunotherapy of ovarian cancer in nude mice with 211At-MX35 F(ab′)2

To elucidate the therapeutic efficacy of alpha-radioimmunotherapy of ovarian cancer in mice. This study: (i) estimated the minimum required activity (MRA), giving a reasonable high therapeutic efficacy; and (ii) calculated the specific energy to tumor cell nuclei and the metastatic cure probability (MCP) using various assumptions regarding monoclonal-antibody (mAb) distribution in measured tumors. The study was performed using the alpha-particle emitter Astatine-211 (211At) labeled to the mAb MX35 F(ab')2. Animals were inoculated intraperitoneally with approximately 1 x 10(7) cells of the cell line NIH:OVCAR-3. Four weeks later animals were treated with 25, 50, 100, or 200 kBq 211At-MX35 F(ab')2 (n = 74). Another group of animals was treated with a nonspecific mAb: 100 kBq 211At-Rituximab F(ab')2 (n = 18). Eight weeks after treatment the animals were sacrificed and presence of macro- and microscopic tumors and ascites was determined. An MCP model was developed and compared with the experimentally determined tumor-free fraction (TFF). When treatment was given 4 weeks after cell inoculation, the TFFs were 25%, 22%, 50%, and 61% after treatment with 25, 50, 100, or 200 kBq (211)At-MX35 F(ab')2, respectively, the specific energy to irradiated cell nuclei varying between approximately 2 and approximately 400 Gy. As a significant increase in the therapeutic efficacy was observed between the activity levels of 50 and 100 kBq (TFF increase from 22% to 50%), the conclusion was that the MRA is approximately 100 kBq (211)At-MX35 F(ab')2. MCP was most consistent with the TFF when assuming a diffusion depth of 30 mum of the mAbs in the tumors.

Preparation of narrow‐disperse or monodisperse poly{[poly(ethylene glycol) methyl ether acrylate]‐co‐(acrylic acid)} microspheres with ethyleneglycol dimethacrylate as crosslinker by distillation precipitation polymerization

AbstractNarrow‐disperse or monodisperse poly{[poly(ethylene glycol) methyl ether acrylate]‐co‐(acrylic acid)} (poly(PEGMA‐co‐AA)) microspheres were prepared by distillation precipitation polymerization with ethyleneglycol dimethacrylate (EGDMA) as crosslinker with 2,2′‐azobisisobutyronitrile as initiator in neat acetonitrile in the absence of any stabilizer, without stirring. The diameters of the resultant poly(PEGMA‐co‐AA‐co‐EGDMA) microspheres were in the range 200–700 nm with a polydispersity index of 1.01–1.14, which depended on the comonomer feed of the polymerization. The addition of the hydrogen bonding monomer acrylic acid played an essential role in the formation of narrow‐disperse or monodisperse polymer microspheres during the polymerization. Copyright © 2006 Society of Chemical Industry

Bifunctional monodisperse microspheres of copolymers of methyl methacrylate and N-vinylformamide

Emulsion copolymerization of methyl methacrylate and N-vinylformamide in the presence of azo initiators and dextran as a polymeric stabilizer was analyzed with the aim to prepare monodisperse polymer microspheres with a polyfunctional surface. Hydrolysis of comonomer units and cationic groups of the initiator residues in the surface layer of the particles to give amphoteric surfaces containing carboxy and amino groups was studied. The optimal conditions of formation of monodisperse microspheres with diameter varied in the 340–660 nm range and the conditions of their hydrolysis, which allow direct control of the amount and nature of functional groups on their surface, were found.

Design and Size Control of Uniform Zeolite Nanocrystals Synthesized in Adjustable Confined Voids Formed by Recyclable Monodisperse Polymer Spheres

Design and Size Control of Uniform Zeolite Nanocrystals Synthesized in Adjustable Confined Voids Formed by Recyclable Monodisperse Polymer Spheres

Emulsifier-free emulsion copolymerization of styrene with methacrylic acid as a method of preparing building blocks for photonic crystals

Monodisperse polymer particles with diameters from 230 to 420 nm have been synthesized by the emulsifier-free emulsion copolymerization of styrene with methacrylic acid. It has been shown that an initiator, chain regulators, comonomer ratio, and pH of a medium influence the dispersity of latexes, the distribution of carboxyl groups in polymer particles, as well as their swelling behavior and electrophoretic mobility. These characteristics of polymer particles are substantial for designing perfect lattices of three-dimensional photonic crystals on their basis.

Virial coefficients and osmotic pressure in polymer solutions in good-solvent conditions

We determine the second, third, and fourth virial coefficients appearing in the density expansion of the osmotic pressure Pi of a monodisperse polymer solution in good-solvent conditions. Using the expected large-concentration behavior, we extrapolate the low-density expansion outside the dilute regime, obtaining the osmotic pressure for any concentration in the semidilute region. Comparison with field-theoretical predictions and experimental data shows that the obtained expression is quite accurate. The error is approximately 1%-2% below the overlap concentration and rises at most to 5%-10% in the limit of very large polymer concentrations.

Polymer size in dilute solutions in the good-solvent regime

We determine the density expansion of the radius of gyration, of the hydrodynamic radius, and of the end-to-end distance for a monodisperse polymer solution in good-solvent conditions. We consider the scaling limit (large degree of polymerization), including the leading scaling corrections. Using the expected large-concentration behavior, we extrapolate these low-density expansions outside the dilute regime, obtaining a prediction for the radii for any concentration in the semidilute region. For the radius of gyration, comparison with field-theoretical predictions shows that the relative error should be at most 5% in the limit of very large polymer concentrations.

Design and Size Control of Uniform Zeolite Nanocrystals Synthesized in Adjustable Confined Voids Formed by Recyclable Monodisperse Polymer Spheres

Design and Size Control of Uniform Zeolite Nanocrystals Synthesized in Adjustable Confined Voids Formed by Recyclable Monodisperse Polymer Spheres

Nonlinear Stress Relaxation of Molten Polymers: Experimental Verification of a New Theoretical Approach

Measurements of damping function for step shear up to strain γ = 5 are here reported for two monodisperse well-entangled polymer melts (polystyrene and polyisoprene). At variance with the classical prediction by Doi and Edwards, which gives an universal damping function for the class entangled polymers, the two measured damping functions are different from each other, and both are less strain thinning than the universal D−E prediction. We compare then our data to a recently proposed theory [Greco, F. Macromolecules 2004, 37, 10079−10088], explicitly accounting for the equilibrium average number n0 of Kuhn segments in a subchain. In the new theory, different n0 values lead to different damping functions. It is shown that the independently calculated n0 values for polystyrene (n0 = 25) and for polyisoprene (n0 = 51) lead to damping function predictions quite close to experiments. The number of Kuhn segments between entanglements is then a key parameter to give a consistent picture of polymer dynamics, as far as the nonlinear stress relaxation behavior is concerned.

Influence of the reaction mechanism on the time course of the entropy production during reversible polymerization

The paper shows the influence of the reaction mechanism on the time course of the entropy production sigma in a closed system during reversible polymerization. We consider two different reaction mechanisms with (a) being a polycondensation and (b) a chain growth mechanism. For both mechanisms explicit expressions for the entropy production sigma as a function of time t are derived. To demonstrate the application of these general expressions we consider two different polymerization experiments where the reaction starts (i) from monomer molecules polymerizing to a defined number average chain length x(n,eq) and (ii) from monodisperse polymer molecules reacting with each other under the constraint that x(n) is the same at the beginning and the end of the reaction. In both cases we treat the system to be ideal and describe the kinetics of the reversible polymerization reactions using two kinetic constants for the forward and backward reactions, respectively. Under these assumptions the difference in the curvature of the entropy production sigma between a polycondensation and a chain growth mechanism is only marginal if the reaction starts from monomer molecules polymerizing to a defined number average chain length x(n,eq).

Monodisperse hydrophilic polymer microspheres having carboxylic acid groups prepared by distillation precipitation polymerization

Monodisperse hydrophilic polymer microspheres having carboxyl acid group with spherical shape in the range of 160 nm and 1.52 μm were prepared by distillation copolymerizations of (meth)acrylic acid with either ethyleneglycol dimethacrylate (EGDMA) or divinylbenzene (DVB) as crosslinker. Polymerization was carried out with 2,2′-azobisisobutyronitrile (AIBN) as initiator in neat acetonitrile without stirring. The polymer microspheres were formed and precipitated out from the reaction medium during the distillation of the solvent from the reaction system through an entropic precipitation polymerization manner. The effects of the crosslinker degree on the morphology and the loading capacity of the carboxylic acid group of the resultant polymer microspheres were investigated. The growth procedures of poly(DVB- co -AA) microspheres were traced by SEM characterization. The steric stabilization through the pendent chains and surface gel and the electrostatic repulsion from the carboxyl acid groups contribute to the formation of monodisperse polymer microspheres.

Crystallization of colloidal crystal on hydrogel surface

A dip-coating method to fabricate wet and dry type of colloidal crystal films was developed. The wet type of colloidal crystal film was fabricated by lifting an agarose-hydrogel-coated substrate out of an aqueous suspension containing monodisperse polymer spheres and the dry type of colloidal crystal film was derived by following desiccation of the wet film. Monodisperse spheres formed ordered structures in the both type of the films, which contributed sharp reflection peaks. Brilliant colors were observed when the reflection peaks fell in the visible region. Formation mechanism of the colloidal crystal and their optical properties were discussed.

Preparation of monodisperse polymer particles and capsules by ink-jet printing

Micron-sized particles with a narrow size distribution are prepared by ink-jet printing technology. Droplets of a polymer solution are printed with the nozzle submerged into an aqueous phase. The particles are formed upon removal of the solvent for the polymer. The particle size can be accurately predicted from the initial drop size and the polymer concentration. The method is also suitable for the preparation of monodisperse capsules with a well-defined core and shell using an additional non-solvent for the polymer. Hollow capsules are prepared by removal of the non-solvent from core of the capsules using freeze-drying. This leads to gas-filled capsules with a well-defined polymeric shell and a diameter in the range of 5 μm, which may be applied as an ultrasound contrast agent.

Synthesis of monodisperse nickel‐coated polymer particles by electroless plating method utilizing functional polymeric ligands

AbstractIn the electroless plating process, to omit a sensitizing process with SnCl2, we utilized amino‐functional groups on polymer particles. At first, highly monodisperse functional polymer particles could be prepared by a two‐step seeded polymerization of styrene, divinylbenzene, and glycidyl methacrylate. Then, surface epoxy‐functional groups were converted to amino‐functional groups by treating the particles with a diamine. By using these surface amino functionalities, we tried to prepare uniformly metal‐coated monodisperse polymer particles by electroless plating method. The constituents of an electroless nickel solution bath are nickel salt, a reducing agent, suitable complexing agents, and stabilizers. And the metal thickness was simply controlled by changing the loading amount of substrate polymer particles. Morphological observation of nickel‐plated polymer particles was conducted by using optical microscopy, scanning electron microscopy, and transmission electron microscopy. The structural composition of plated nickel was also investigated. Most of all, the function and the efficiency of the amino‐functional group of polymer particles as a polymeric ligand for metal binding was elucidated. From all observations, it was evident that in the electroless metal plating process without any sensitization step, the deposition of metal clusters on substrate particles is largely dependent upon the particle surface functionality. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3801–3808, 2006

Critical Elements of Oligosaccharide Acceptor Substrates for the Pasteurella multocida Hyaluronan Synthase

Three-dimensional structures are not available for polysaccharide synthases and only minimal information on the molecular basis for catalysis is known. The Pasteurella multocida hyaluronan synthase (PmHAS) catalyzes the polymerization of the alternating beta1,3-N-acetylglucosamine-beta1,4-glucuronic acid sugar chain by the sequential addition of single monosaccharides to the non-reducing terminus. Therefore, PmHAS possesses both GlcNAc-transferase and glucuronic acid (GlcUA)-transferase activities. The recombinant Escherichia coli-derived PmHAS enzyme will elongate exogenously supplied hyaluronan chains in vitro with either a single monosaccharide or a long chain depending on the UDP-sugar availability. Competition studies using pairs of acceptors with distinct termini (where one oligosaccharide is a substrate that may be elongated, whereas the other cannot) were performed here; the lack of competition suggests that PmHAS contains at least two distinct acceptor sites. We hypothesize that the size of the acceptor binding pockets of the enzyme corresponds to the size of the smallest high efficiency substrates; thus we tested the relative activity of a series of authentic hyaluronan oligosaccharides and related structural analogs. The GlcUA-transferase site readily elongates (GlcNAc-GlcUA)(2), whereas the GlcNAc-transferase elongates GlcUA-Glc-NAc-GlcUA. The minimally sized oligosaccharides, elongated with high efficiency, both contain a trisaccharide with two glucuronic acid residues that enabled the identification of a synthetic, artificial acceptor for the synthase. PmHAS behaves as a fusion of two complete glycosyltransferases, each containing a donor site and an acceptor site, in one polypeptide. Overall, this information advances the knowledge of glycosaminoglycan biosynthesis as well as assists the creation of various therapeutic sugars for medical applications in the future.

Effect of PVA in dispersion polymerization of MMA

Monodisperse poly(methylmethacrylate) microspheres having a diameter of 2.6 μm and a molecular weight of 102,277 g/mol with 5.3% of the C v (the coefficient of variation) were synthesized by the dispersion polymerization using hydrophilic polyvinylalcohol (PVA) in methanol/water mixture media. Then, the structural verification of the synthesized materials is confirmed by using 1H NMR and FT-IR spectroscopy. The effects of PVA and the polymerization parameters such as the initiator, monomer and stabilizer concentrations, and the reaction time on the characteristics of the final particles were studied. Thus, the role of PVA in the dispersion polymerization of MMA is not only a steric stabilizer by physically adsorbed in methanol phase, but also a colloid protective to give relatively monodisperse polymer particles in water phase, simultaneously.