Synthesis of polypeptide based rod-coil block copolymers

A bifunctional initiator was synthesized and used for a sequence of a nickel initiated polymerization of gamma-benzyl-L-glutamate-N-carboxy anhydride and atom transfer radical polymerization of methyl methacrylate yielding a rod-coil block copolymer.     

Self-assembly of rod-coil block copolymers

We present a self-consistent field theory model for the self-assembly behavior of rod-coil block copolymers. The orientational interactions between the rods were modeled through a Maier-Saupe interaction, while the enthalpic interactions between rods and coils were modeled through a standard Flory-Huggins approach. We outline a "real-space" numerical approach to solve the self-consistent field equations for such rod-coil block copolymers. A major focus of our work is upon the nonlamellar phases observed in the experiments on such polymers. To develop a physical understanding of these phases and their regimes of occurrence, we compute the two-dimensional phase diagram for our model. The latter shows significant departures from the one-dimensional phase diagram, but matches qualitatively with the existing experimental results. We also present scaling arguments that rationalize the numerical results for the self-assembly behavior.     

Synthesis and characterization of luminescent rod-coil block copolymers by atom transfer radical polymerization: utilization of novel end-functionalized terfluorenes as macroinitiators

Two novel, rigid, photoluminescent, substituted terfluorene derivatives were synthesized by utilizing direct bromination and Suzuki coupling reactions. These oligomers were used as initiators for the atom transfer radical polymerization (ATRP) of styrene and tert-butyl acrylate. Thus, diblock and triblock rod-coil block copolymers were prepared with well-defined structure, as far as their size and shape is concerned. Molecular weights up to approximately 21 000 and polydispersity indices not exceeding 1.5 in most cases were obtained. The copolymers emit blue light in solution, and their luminescence properties remain practically invariable when passing from solution to the solid state. No ground-state aggregation or excimer formation were observed in the solid state, even after annealing at high temperatures.     

Synthesis and characterization of a poly(para-phenyleneethynylene)-block-poly(ethylene oxide) rod-coil block copolymer

The synthesis of the poly(para-phenyleneethynylene)-block-poly(ethylene oxide) block copolymer (PPE-b-PEO) ( 1 ) via condensation of endfunctionalized poly(para-phenyleneethynylene) (PPE) ( 5 ) and poly(ethylene oxide) monomethyl ether (PEO) is reported. This is achieved by the initial synthesis of a PPE homopolymer with quantitative terminal functionalization, as proven by ¹H NMR and field desorption mass spectrometry (FD-MS). Reaction of the latter with PEO affords the block copolymer 1 , which was characterized by ¹H NMR spectroscopy, FD-MS and gel permeation chromatography (GPC). Furthermore it is shown that matrix assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF-MS) is a suitable method to investigate PPE-b-PEO with respect to molecular weights and copolymer composition.     

Synthesis and endosomolytic properties of poly(amidoamine) block copolymers

The poly(amidoamine)s (PAAs) ISA 1 and ISA 23 display pH-dependent conformational change and pH-dependent membrane perturbation. These properties confer potential for use as endosomolytic polymers for intracytoplasmic delivery of toxins and genes. Both polymers are relatively non-toxic, and moreover ISA 23 has the beneficial property in vivo, of being non hepatotropic when administered intravenously. Although ISA 23 and ISA 1 demonstrate ability to transfect cells, ISA 1 is also able to promote intracellular delivery of non-permeant toxins. The aim of this study was to synthesise random and block copolymers of ISA 1 and ISA 23 and investigate whether these second generation hybrids would allow optimisation of PAA biological characteristics. Random and block copolymers of ISA 1 and ISA 23 were synthesised by hydrogen transfer polyaddition to generate a library of PAAs with an ISA 23:ISA 1 molar ratios of 2:1 to 4:1. The resultant polymers have a pI slightly below 7.4 and a M(w) of 19,900-49,000 g/mol and a M(n) of 13,100-24,100 g/mol. Whereas none of the random or block copolymers were haemolytic at pH 7.4 all demonstrated pH-dependent membrane activity. At pH 5.5 they caused 50-60% haemoglobin (Hb) release over 1 h. This was slightly less than that seen for ISA 23 (80% Hb release). None of the copolymers were cytotoxic against B16F10 cells during a 72 h incubation (IC(50) > 2 mg/ml; MTT assay). The ability of the random and block copolymer PAAs to deliver the toxin gelonin was also examined, but only ISA 1 and the block copolymer B2 (ISA 23:ISA 1 at a 2:1 molar ratio) were able to promote intracellular delivery, as measured by cytotoxic activity. It would be interesting to study the body distribution of B2 and determine whether this toxin-delivering PAA is able to escape liver capture.     

Synthesis of block copolymers containing poly(ferrocenylmethyl methacrylate) units

Ferrocenylmethyl methacrylate (FMMA) has been polymerized by using LiAlH₄–tetramethyl-ethylenediamine initiation to form living polymers in high vacuum systems. The addition of methyl methacrylate or acrylonitrile to these living systems gave the block copolymers FMMA-block MMA and FMMA-block AN. The anions were not nucleophilic enough to initiate styrene polymerization. Therefore, living polystyrene was prepared (sodium naphthalide initiation in THF at ?78°C) and upon FMMA addition, styrene-block FMMA copolymers were formed. Extraction, precipitation, and gel-permeation chromatography studies were performed to examine the purity of the block copolymers.     

Square grains in asymmetric rod-coil block copolymers

Unlike the rounded grains that are well known to form in most soft materials, square grains of microphase-separated lamellae are observed in thin films of a rod-coil block copolymer because of hierarchical structuring originating from the molecular packing of the rods. The square grains are oriented with lamellar layers parallel to the film interface and result from growth along orthogonal low-surface-energy directions as a result of the effects of the tetragonal crystalline lattice that forms within the rod-rich lamellar nanodomains of poly(2,5-di(2'-ethylhexyloxy)-1,4-phenylene vinylene)-b-polyisoprene (PPV-b-PI). These grain shapes form only for a narrow range of coil volume fractions around 72% as a result of kinetic barriers at lower coil fractions and disordering of the lattice at higher coil fractions, and the polydisperse grain size suggests that growth is nucleation-limited. The grains form in both weakly and moderately segregated polymers at all annealing temperatures below the order-disorder transition, and they are observed for all thicknesses at which parallel-oriented grains are grown.     

Synthesis of poly(tert-butoxycarbonyl-p-phenylene): precursor to poly(p-phenylene)

Poly[2-(tert-butoxycarbonyl)-1,4-phenylene] ( 2 ) was prepared by the Ni-catalyzed polymerization of tert-butyl 2,5-dichlorobenzoate ( 1 ). The microstructure of polymer 2 was probably alternating head-to-head and tail-to-tail. This polymer was soluble in dipolar aprotic solvents, chloroform, tetrahydrofuran, and dichloromethane. Polymer 2 was saponified easily by thermal or acid treatment to yield poly[2-carboxy-1,4-phenylene] ( 3 ). Decarboxylation of polymer 3 in quinoline in the presence of copper(II) oxide produced poly(p-phenylene) (PPP) ( 4 ).     

Synthesis and micellar behavior of poly(acrylic acid-b-styrene) block copolymers

Poly(acrylic acid-b-styrene) (PAA-b-PS) amphiphilic block copolymers were synthesized by consecutive telomerization of tert-butyl acrylate, atom transfer radical polymerization (ATRP) of styrene, and hydrolysis. The resulting block copolymers were characterized by ¹H NMR and GPC. These amphiphilic block copolymeric micelles were prepared by dialysis against water. Transmission electron micrograph (TEM) and laser particle sizer measurements were used to determine the morphology and size of these micelles. The results showed that these amphiphilic block copolymers formed spherical micelles with average size of 140–190?nm. The critical micelle concentration (CMC) and the kinetic stability of these micelles were investigated by fluorescence technique, using pyrene as a fluorescence probe. The observed CMC value was in the range of 0.075–0.351?mg/L. Kinetic stability studies showed that the stability of micelles increased with the decrease of the pH value of the solution.     

Synthesis and characterization of fluorinated poly(imide siloxane) block copolymers

Five new block copoly(imide siloxane)s have been prepared by reacting two different diamines, 4,4″-bis(p-aminophenoxy)-3,3″-trifluoromethyl terphenyl (APTTFT) and amino-propyl terminated polydimethylsiloxane (APPS), separately with 4,4′-(4,4′-isopropylidenediphenoxy)bis(phthalic anhydride); BPADA. The reactions were conducted by a two pot solution imidization technique. The diamine APTTFT and the dianhydride BPADA composed the hard block segment while APPS and BPADA composed the soft block segment. The soft and hard blocks of different block lengths were generated by different stoichiometric imbalance in two different flasks and the final polymers were obtained by reacting both the blocks together. Different block copoly(imide siloxane)s were prepared on increasing the hard block lengths (DP) from 7 to 12, 18, 23 and 28 and the soft block lengths (DP) from 4 to 6, 8, 10 and 12, respectively. The resulting polymers have been well characterized by NMR, DSC and DMA techniques. The properties of the block copolymers were compared with the analogous random copolymers and homopolyimide prepared without APPS.     

Photophysical properties of hydroxylated amphiphilic poly(p-phenylene)s

A homologous series of polyhydroxylated poly(p-phenylene)s with different alkoxy groups (C6PPPOH, C12PPPOH, and C18PPPOH) were synthesized with use of the Suzuki polycondensation reaction. Comparative studies of the structure correlation between their photophysical properties and film morphology is described. The absorption and emission spectra of polymers in solution and thin films showed similar features indicating that the electronic properties in solution were retained in the film state. Compared to the polymer with the short alkoxy chains (C6PPPOH), the polymers with long alkoxy groups (C12PPPOH and C18PPPOH) showed improved film forming properties with continuous and smooth film morphology. The absorption properties of the C12PPPOH showed an enhanced effective conjugation length and high quantum yield implying planarization of the backbone through alkoxy chain packing (C12H25O-) and potential hydrogen bonds. No overlap in the absorption and emission spectra was observed, which indicated minimized excimer formation or excitation energy transfer in the films. Time-resolved fluorescence measurements showed that the decay times increased from 43 ps (C6PPPOH) to 78 ps (C12PPPOH) and 99 ps (C18PPPOH). Electrochemical studies were performed for all polymers and the observed oxidation potential for C6PPPOH was higher than that of C12PPPOH and C18PPPOH. In addition, the C12PPPOH has the lowest band gap of DeltaE = 2.59 eV when compared to the 3.1 (C6PPPOH) and 2.61 eV (C18PPPOH) gaps. The optical band gaps estimated from the absorption onset of the polymers are significantly higher than those obtained from electrochemical data. C12PPPOH was chosen for investigating the charge carrier mobility by the time-of-flight (TOF) technique. The observed results also showed negative field dependent values of the drift mobility for the polymer C12PPPOH.     

Synthesis and aggregation of poly(valine)‐poly (ethylene glycol) block copolymers

The solubility nature of many medicines presents a challenge for successful delivery of these drugs to the body. Polymeric carriers are potentially viable as vessels for both the protection and transport of these medicinal substances. In an effort to generate polymeric materials for this desired application, A‐B‐A triblock copolymers have been synthesized with a central block composed of hydrophilic poly (ethylene glycol) (PEG) and flanking hydrophobic sequences composed of five valine units terminated with end groups of varying hydrophobicity. These copolymers were constructed by adding amino acids stepwise to the hydrophilic block using solution phase chemistry. The self‐assembly behavior of all polymers was investigated using fluorimetry with a pyrene probe. In general, copolymers with more hydrophobic end groups exhibited lower critical aggregation concentrations (CACs). Fmoc‐terminated copolymers displayed the lowest CAC of 0.032 mg/mL and demonstrated little cytotoxicity when exposed to SW620 colorectal cancer cells. Transmission electron micrographs show the presence of multiple compartments within these spherical assemblies, which may prove useful in encapsulating medicinal substances. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5381–5389, 2008     

Synthesis of poly(p-dioxanone)-based block copolymers in supercritical carbon dioxide

Poly(p-dioxanone)–poly(ethylene glycol)–poly(p-dioxanone) triblock copolymers (PPDO–PEG–PPDO) were first synthesized by suspension ring-opening polymerization (ROP) of p-dioxanone (PDO) in supercritical carbon dioxide (scCO₂) using different molecular weights (2–10 K) of poly(ethylene glycol) (PEG) as macroinitiators. White and fine flow powders were successfully obtained when the molecular weight of PEG was below 6 K and its feed content below 20 wt.%. The ¹H nuclear magnetic resonance (NMR) result indicated the formation of PPDO–PEG–PPDO block structure even in a confined polymerized environment of particles. All the powderous samples contained irregular shaped particles that were observed by scanning electron microscope (SEM). Except for the copolymer with 10 wt.% PEG10K feed content, the mean particle sizes of other powderous samples showed identical values close to 15 μm. This fact was in agreement with the crystallinity of PPDO in the copolymers measured by differential scanning calorimetry (DSC). The water absorption of these copolymers was also measured, and as compared with PPDO homopolymer, the introduction of PEG increased the water absorption of the copolymers. The green and environmentally friendly method disclosed in this work is attractive to directly synthesize biodegradable polymeric particles with potential biomedical applications.     

Perforated layer structures in liquid crystalline rod-coil block copolymers

We report a novel observation of the tetragonal perforated layer structures in a series of rod-coil liquid crystalline block copolymers (BCPs), poly(styrene-block-(2,5-bis[4-methoxyphenyl]oxycarbonyl)styrene) (PS-b-PMPCS). PMPCS forms rigid rods while PS forms the coil block. Differential scanning calorimetry (DSC), polarized light microscopy (PLM), small-angle X-ray scattering (SAXS), wide-angle X-ray diffraction (WAXD), and transmission electron microscopy (TEM) techniques were used to investigate these rod-coil molecules, and a perforated layer structure was observed at f(PMPCS) approximately 0.37 in relatively low molecular weight (M(w)) samples and approximately 0.5 in high M(w) PS-b-PMPCS. This substantial phase boundary shift was attributed to the rod-coil nature of the BCP. The perforation obeys a tetragonal instead of hexagonal symmetry. The "onset" of perforation was also observed in real space in sample PS(272)-b-PMPCS(93) (f(PMPCS) approximately 0.52), in which few PS chains punctuate PMPCS layers. A slight increase in f(PS), by blending with PS homopolymer, led to a dramatic change in the BCP morphology, and uniform tetragonal perforations were observed at f(PMPCS) approximately 0.48.     

Swelling studies of crosslinked poly(p-phenylene terephthalamide) copolymers in sulfuric acid

In an attempt to improve the mechanical properties of extended chain polymers such as poly(p-phenylene terephthalamide) (PPTA), a crosslinkable terephthalic acid derivative (XTA) has been developed which can be incorporated into copolymers in various concentrations and activated after polymerization. The crosslinking of PPTA-co-XTA copolymer particles was investigated through a series of swelling experiments in concentrated H₂SO₄. The data show a systematic decrease in equilibrium swelling with increasing XTA content, indicating the XTA units are in fact acting as crosslink sites. Values for crosslink density were calculated from the Flory-Rehner theory of polymer swelling and compared with previous findings on crosslinked rigid polymer network systems. The effective number of crosslinks per XTA unit (efficiency) predicted by the Flory-Rehner theory increases and then decreases with % XTA. The decrease in crosslinking efficiency at high XTA concentrations is consistent with differential scanning calorimetry data which show the enthalpy of XTA reaction decreasing slightly with % XTA. The deviations at low % XTA may represent a failure of the Flory-Rehner theory to properly describe the rubbery elasticity of extended chain polymers. © 1994 John Wiley & Sons, Inc.     

Synthesis and characterization of poly(p-phenylene pyromellitamic acid)

Poly(p-phenylene pyromellitamic acid)s were synthesized over the weight-average molecular weight range 8,000 to 22,000. The polymers were recovered as amorphous powders composed of 3–4 × 1–2 μ platelets 0.1–0.2 μ thick containing 20–30% associated solvent. Consumption of reactants and attainment of the ultimate molecular weight of the polymer were found to occur within the first few minutes of reaction. The polymers were characterized by scanning electron microscopy; ultraviolet, visible, near-infrared, and infrared spectroscopy; x-ray analysis; viscometry; and light-scattering photometry. The intrinsic viscosity–molecular weight relation for the polymer in DMF was \documentclass{article}\pagestyle{empty}\begin{document}$ [\eta ] = 25.2 \times 10^{ - 4} \bar M_w^{0.56} $\end{document}.