Poly(ethylene imine)‐graft‐poly(ethylene oxide) brush‐like copolymers: Preparation,thermal properties,and selective supramolecular inclusion complexation with α‐cyclodextrin

Poly(ethylene imine)‐graft‐poly(ethylene oxide) (PEI‐g‐PEO) copolymers were synthesized via Michael addition reaction between acryl‐terminated poly(ethylene oxide) methyl ether (PEO) and poly(ethylene imine) (PEI). The brush‐like copolymers were characterized by means of Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. It is found that the crystallinity of the PEO side chains in the copolymers remained unaffected by the PEI backbone whereas the crystal structure of PEO side chains was altered to some extent by the PEI backbone. The crystallization behavior of PEO blocks in the copolymers suggests that the bush‐shaped copolymers are microphase‐separated in the molten state. The PEO side chains of the copolymers were selectively complexed with α‐cyclodextrin (α‐CD) to afford hydrophobic side chains (i.e., PEO/α‐CD inclusion complexes). The X‐ray diffraction (XRD) shows that the inclusion complexes (ICs) of the PEO side chains displayed a channel‐type crystalline structure. It is identified that the stoichiometry of the inclusion complexation of the PEI‐g‐PEO with α‐CD is close to that of the control PEO with α‐CD. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2296–2306, 2008     

Nanostructured thermoset epoxy resin templated by an amphiphilic poly(ethylene oxide)‐block‐poly(dimethylsiloxane) diblock copolymer

An amphiphilic poly(ethylene oxide)‐block‐poly(dimethylsiloxane) (PEO–PDMS) diblock copolymer was used to template a bisphenol A type epoxy resin (ER); nanostructured thermoset blends of ER and PEO–PDMS were prepared with 4,4′‐methylenedianiline (MDA) as the curing agent. The phase behavior, crystallization, hydrogen‐bonding interactions, and nanoscale structures were investigated with differential scanning calorimetry, Fourier transform infrared spectroscopy, transmission electron microscopy, and small‐angle X‐ray scattering. The uncured ER was miscible with the poly(ethylene oxide) block of PEO–PDMS, and the uncured blends were not macroscopically phase‐separated. Macroscopic phase separation took place in the MDA‐cured ER/PEO–PDMS blends containing 60–80 wt % PEO–PDMS diblock copolymer. However, the composition‐dependent nanostructures were formed in the cured blends with 10–50 wt % PEO–PDMS, which did not show macroscopic phase separation. The poly(dimethylsiloxane) microdomains with sizes of 10–20 nm were dispersed in a continuous ER‐rich phase; the average distance between the neighboring microdomains was in the range of 20–50 nm. The miscibility between the cured ER and the poly(ethylene oxide) block of PEO–PDMS was ascribed to the favorable hydrogen‐bonding interaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3042–3052, 2006     

Supramolecular polyseudorotaxanes formation between star‐block copolymer and α‐cyclodextrin: From outer block to diblock inclusion complexation

A series of star‐block poly(L ‐lactide)‐b‐poly(ethylene oxide) (SPLLA‐b‐PEO) copolymers were synthesized by ring‐opening polymerization (ROP) and DCC chemistry. The inclusion complexes of SPLLA‐b‐PEO copolymers and α‐cyclodextrin (α‐CD) were prepared with two different methods. FTIR, ¹H NMR, WAXD, DSC, and TGA indicate that α‐CD only can be threaded onto PEO blocks in inclusion complexes of α‐CD‐SPLLA‐b‐PEO1.1K‐a, α‐CD‐SPLLA‐b‐PEO2K‐a, and α‐CD‐SPLLA‐b‐PEO5K‐a formed without heating and ultrasonication, and can be threaded onto both PLLA and PEO blocks in inclusion complexes of α‐CD‐SPLLA‐b‐PEO1.1K‐b, α‐CD‐SPLLA‐b‐PEO2K‐b, and α‐CD‐SPLLA‐b‐PEO5K‐b formed with heating and ultrasonication. Namely, α‐CDs can be threaded onto PEO blocks and the flanking bulky PLLA blocks of star‐block copolymers to form stable polyseudorotaxanes with heating method and ultrasonication to conquer the activation energy barrier of the inclusion complexation between bulky PLLA and α‐CD and the effect of the steric hindrance of star‐block copolymers. With the alteration of preparing methods, the inclusion complexes of α‐CD with the outer PEO block or PEO and PLLA blocks were obtained successfully. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2754–2762, 2009     

Synthesis and Characterization of α,ω‐bi[2,4‐dinitrophenyl (DNP)] poly(2‐methoxystyrene) Functional Polymers. Initial Evaluation of the Interaction of the Functional Polymers with RBL Mast Cells

Two series of functional polymers, α,ω‐bi[2,4‐dinitrophenyl][poly(ethylene oxide)‐b‐poly(2‐methoxystyrene)‐b‐poly(ethylene oxide)] (DNP‐PEO‐P2MS‐PEO‐DNP) and α,ω‐bi[2,4‐dinitrophenyl caproic][poly(ethylene oxide)‐b‐poly(2‐methoxystyrene)‐b‐poly(ethylene oxide)] (CDNP‐PEO‐P2MS‐PEO‐CDNP), were synthesized by anionic living polymerization. The polymers were characterized by FT‐IR, ¹H‐NMR and Gel Permeation Chromatography (GPC). The molecular weight distributions for the lower molecular weight functional polymers were slightly broad (1.3–1.5). However, the molecular weight distributions for higher molecular weight polymers were narrower (1.1–1.2). Differential scanning calorimetry (DSC) studies showed thermal transitions indicative of the presence of microphases in the polymer solid state. The polymers were white powders and soluble in tetrahydrofuran. The binding affinity of DNP‐PEO‐P2MS‐PEO‐DNP ligands towards anti DNP IgE was determined by titrations with fluorescently labeled FITC‐IgE. A water soluble CDNP‐PEO‐P2MS‐PEO‐CDNP/DMEG (dimethoxyethylene glycol) complex binds and achieves steady state binding with solution IgE within a few seconds. This strongly suggests that CDNP functional polymers with improved water solubility have potential in therapeutics. Higher molecular weight (water insoluble) CDNP‐PEO‐P2MS‐PEO‐CDNP polymers were electrosprayed as fibers (500 nm) on silicon surface. Fluorescence spectroscopy clearly showed that RBL mast cells were interacting with the fibers suggesting that the cell‐surface receptors were clustered along the fiber surface. These observations suggest that the functional polymers hold promise for developing an antibody detection device.     

Water‐soluble poly(ethylene oxide)‐block‐poly(p‐phenylene vinylene) copolymer: Synthesis and characterization

Water‐soluble and photoluminescent block copolymers [poly(ethylene oxide)‐block‐poly(p‐phenylene vinylene) (PEO‐b‐PPV)] were synthesized, in two steps, by the addition of α‐halo‐α′‐alkylsulfinyl‐p‐xylene from activated poly(ethylene oxide) (PEO) chains in tetrahydrofuran at 25 °C. This copolymerization, which was derived from the Vanderzande poly(p‐phenylene vinylene) (PPV) synthesis, led to partly converted PEO‐b‐PPV block copolymers mixed with unreacted PEO chains. The yield, length, and composition of these added sequences depended on the experimental conditions, namely, the order of reagent addition, the nature of the monomers, and the addition of an extra base. The addition of lithium tert‐butoxide increased the length of the PPV precursor sequence and reduced spontaneous conversion. The conversion into PPV could be achieved in a second step by a thermal treatment. A spectral analysis of the reactive medium and the composition of the resulting polymers revealed new evidence for an anionic mechanism of the copolymerization process under our experimental conditions. Moreover, the photoluminescence yields were strongly dependant on the conjugation length and on the solvent, with a maximum (70%) in tetrahydrofuran and a minimum (<1%) in water. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4337–4350, 2005     

Effect of Shear Flow on the Polymeric Gels Formed by Macroscopic Phase Separation

Summary: Shear‐induced phase behavior of poly(ethylene oxide‐b‐(DL ‐lactic acid‐co‐glycolic acid)‐b‐ethylene oxide) (PEO‐PLGA‐PEO) triblock copolymers in water is investigated using rheology and small‐angle neutron scattering equipped with an in situ Couette shear cell. For gels formed by the macroscopic phase separation, the steady shear experiment reveals that the flow‐induced anisotropy on a nanometer length scale at a critical shear rate and the phase separation on a larger length scale are successively induced with a further increase in the shear rate. In particular, the hard gels show a memory effect inscribed by a pre‐high shear in contrast to the soft gels.

2D SANS patterns clearly show the memory effect of the hard gels at a pre‐high shear.     

Mobility Tuning of Polyrotaxane Surfaces to Stimulate Myocyte Differentiation

Polyrotaxanes, consisting of poly(ethylene glycol) and α‐cyclodextrins, are mechanically interlocked supermolecules. The structure allows α‐cyclodextrins to move along the polymer, referred to as molecular mobility. Here, polyrotaxane‐based triblock copolymers, composed of polyrotaxanes with different degrees of methylation and poly(benzyl methacrylate) at both terminals, are coated on culture surfaces to fabricate dynamic biointerfaces for myocyte differentiation. The molecular mobility increases with the degree of methylation and the contact angle hysteresis of water droplets and air bubbles. When the mouse myoblast cell line C2C12 is cultured on methylated polyrotaxane surfaces, the expression levels of myogenesis‐related genes, myogenin (Myog) and myosin heavy chain (Myhc) are altered by the degree of methylation. Polyrotaxane surfaces with intermediate degrees of methylation promote the highest expression levels among all the surfaces. The polyrotaxane surface provides an appropriate environment for myocyte differentiation by accurately adjusting the degrees of methylation.     

Construction of different supramolecular polymer systems by combining the host–guest and hydrogen‐bonding interactions

Poly(ethylene glycol) (PEG) can form either the inclusion complex with α‐cyclodextrins (α‐CDs) through host–guest interactions or the interpolymer complex with poly(acrylic acid) (PAA) through hydrogen‐bonding interaction. Mixing α‐CD, PEG, and PAA ternary components in an aqueous solution, the competition between host–guest and hydrogen‐bonding interactions occurs. Increasing feed ratio of α‐CD:EG:AA from 0:1:1 to 0.2:1:1 (molar ratio), various interesting supramolecular polymer systems, such as hydrogen‐bonding complex, dynamic polyrotaxane, crystalline inclusion complex, and thermoresponsive hydrogel, are successively obtained. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1114–1120, 2008     

Supramolecular nanostructures from self‐assembly of T‐shaped rod building block oligomers

T‐shaped coil–rod–coil oligomers, consisting of a dibenzo[a,c]phenazine unit and phenyl groups linked together with acetylenyl bonds at the 2,7‐position of dibenzo[a,c]phenazine as a rigid segment have been synthesized. The coil segments of these new molecules composed of poly(ethylene oxide) (PEO)–poly(propylene oxide) (PPO) incorporating lateral methyl groups between the rod and coil segment and two flexible alkyl groups connecting with the rigid segment at the 4,6‐position of dibenzo[a,c]phenazine, respectively. The experimental results reveal that the length of the flexible PEO coil chain influence construction of various supra‐nanostructures from lamellar structure to rectangular columnar structure. It is also shown that introduction of different length of alkyl side chain groups in the backbone of the T‐shaped molecules affect the self‐organization behavior to form hexagonal perforate layer or oblique columnar structures. In addition, lateral methyl groups attached to the surface of rod and coil segments, dramatically influence the self‐assembling behavior in the crystalline phase. T‐shaped molecules containing a lateral methyl group at the surface of rod and PEO coil segments, self‐assemble into 3D body‐centered tetragonal structures in the crystalline phase, while molecules without a lateral methyl group based on PEO coil chain self‐organize into 2D oblique columnar crystalline structures. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5021–5028     

Synthesis and characterization of amphiphilic copolymer of linear poly(ethylene oxide) linked with [poly(styrene‐co‐2‐hydroxyethyl methacrylate)‐graft‐poly(ε‐caprolactone)] using sequential controlled polymerization

A well‐defined amphiphilic copolymer of ‐poly(ethylene oxide) (PEO) linked with comb‐shaped [poly(styrene‐co‐2‐hydeoxyethyl methacrylate)‐graft‐poly(ε‐caprolactone)] (PEO‐b‐P(St‐co‐HEMA)‐g‐PCL) was successfully synthesized by combination of reversible addition‐fragmentation chain transfer polymerization (RAFT) with ring‐opening anionic polymerization and coordination–insertion ring‐opening polymerization (ROP). The α‐methoxy poly(ethylene oxide) (mPEO) with ω,3‐benzylsulfanylthiocarbonylsufanylpropionic acid (BSPA) end group (mPEO‐BSPA) was prepared by the reaction of mPEO with 3‐benzylsulfanylthiocarbonylsufanyl propionic acid chloride (BSPAC), and the reaction efficiency was close to 100%; then the mPEO‐BSPA was used as a macro‐RAFT agent for the copolymerization of styrene (St) and 2‐hydroxyethyl methacrylate (HEMA) using 2,2‐azobisisobutyronitrile as initiator. The molecular weight of copolymer PEO‐b‐P(St‐co‐HEMA) increased with the monomer conversion, but the molecular weight distribution was a little wide. The influence of molecular weight of macro‐RAFT agent on the polymerization procedure was discussed. The ROP of ε‐caprolactone was then completed by initiation of hydroxyl groups of the PEO‐b‐P(St‐co‐HEMA) precursors in the presence of stannous octoate (Sn(Oct)₂). Thus, the amphiphilic copolymer of linear PEO linked with comb‐like P(St‐co‐HEMA)‐g‐PCL was obtained. The final and intermediate products were characterized in detail by NMR, GPC, and UV. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 467–476, 2006     

High conversion synthesis of pyrene end functionalized polyrotaxane based on poly(ethylene oxide) and alpha-cyclodextrins

We describe the quantitative synthesis of new pyrene labeled cyclodextrin-based polyrotaxane starting from pseudopolyrotaxane of alpha,omega-dimethacrylate poly(ethylene oxide) (PEO) and alpha-cyclodextrins (alpha-CDs). Using a solvent mixture (H2O/dimethyl sulfoxide (DMSO)), an almost quantitative conversion in polyrotaxane can be achieved using the coupling reaction between methacrylic functions and 1-pyrene butyric acid N-hydroxysuccinimide ester. This result is due to the fast blocking reaction of the pseudopolyrotaxane telechelic functions. The polyrotaxanes are characterized by NMR, size exclusion chromatography (SEC), and small-angle neutron scattering (SANS). A rodlike structure of the polyrotaxane is evidenced by SANS, and a persistence length of 70 A is determined. This result corresponds to an almost completely stretched PEO chain of 1000 g.mol(-1) molecular weight. We furthermore studied the opposite case of low packing density polyrotaxanes that were also silylated to suppress interactions between cyclodextrins. We observed a random coil structure only for silylated low packed polyrotaxane. This result demonstrates that both hydrogen bonding and packing density can explain the rodlike structure of cyclodextrin-based polyrotaxane.     

Preparation of poly(ethylene oxide)‐block‐poly(isoprene) by nitroxide‐mediated free radical polymerization from PEO macroinitiators

Amphiphilic poly(ethylene oxide)‐block‐poly(isoprene) (PEO‐b‐PI) diblock copolymers were prepared by nitroxide‐mediated polymerization of isoprene from alkoxyamine‐terminal poly(ethylene oxide) (PEO). PEO monomethyl ether (M_n ≈ 5200 g/mol) was functionalized by esterification with 2‐bromopropionyl bromide with subsequent copper‐mediated replacement of the terminal bromine with 2,2,5‐trimethyl‐4‐phenyl‐3‐azahexane‐3‐nitroxide. The resulting PEO‐alkoxyamine macroinitiator was used to initiate polymerization of isoprene in bulk and in solution at 125 °C to yield PEO‐b‐PI block copolymers with narrow molecular weight distributions (M_w/M_n ≤ 1.1). Polymerizations were first order in isoprene through 35% conversion. Micellar aggregates of PEO‐b‐PI in aqueous solution were crosslinked by treatment with a water‐soluble redox initiating system, and persistent micellar structures were observed in the dry state by AFM. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2977–2984, 2005     

Easy and effective method to produce functionalized particles for cellular uptake

In this contribution, a versatile approach for the synthesis of functionalized particles for drug delivery is presented, using two nonaggressive standardized procedures. The first procedure considered is the functionalization of an azido‐terminated α‐norbornenyl poly(ethylene oxide) (PEO) macromonomer with an alkyne‐containing active molecule via the copper catalyzed azide alkyne cycloaddition, click type reaction. The functionalized macromonomer is then polymerized by Ring‐Opening Metathesis Polymerization (ROMP) in dispersion to form functionalized particles. The second procedure consists in synthesizing particles by ROMP in dispersed media of norbornene with azido‐terminated α‐norbornenyl PEO macromonomer. The ROMP was initiated by the first generation Grubbs catalyst. Such functionalized core‐shell particles have stealthy properties due to their PEO shell and can be viewed as universal nanocarriers on which any alkyne‐modified active molecule can be grafted by click chemistry. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis and characterization of side‐chain liquid crystalline ABC triblock copolymers with p‐methoxyazobenzene moieties by atom transfer radical polymerization

A series of novel side‐chain liquid crystalline ABC triblock copolymers composed of poly(ethylene oxide) (PEO), polystyrene (PS), and poly[6‐(4‐methoxy‐4′‐oxy‐azobenzene) hexyl methacrylate] (PMMAZO) were synthesized by atom transfer radical polymerization (ATRP) using CuBr/1,1,4,7,7‐pentamethyldiethylenetriamine (PMDETA) as a catalyst system. First, the bromine‐terminated diblock copolymer poly(ethylene oxide)‐block‐polystyrene (PEO‐PS‐Br) was prepared by the ATRP of styrene initiated with the macro‐initiator PEO‐Br, which was obtained from the esterification of PEO and 2‐bromo‐2‐methylpropionyl bromide. An azobenzene‐containing block of PMMAZO with different molecular weights was then introduced into the diblock copolymer by a second ATRP to synthesize the novel side‐chain liquid crystalline ABC triblock copolymer poly(ethylene oxide)‐block‐polystyrene‐block‐poly[6‐(4‐methoxy‐4′‐oxy‐azobenzene) hexyl methacrylate] (PEO‐PS‐PMMAZO). These block copolymers were characterized using proton nuclear magnetic resonance (¹H NMR) and gel permeation chromatograph (GPC). Their thermotropic phase behaviors were investigated using differential scanning calorimetry (DSC) and polarized optical microscope (POM). These triblock copolymers exhibited a smectic phase and a nematic phase over a relatively wide temperature range. At the same time, the photoresponsive properties of these triblock copolymers in chloroform solution were preliminarily studied. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4442–4450, 2008     

New solvent for polyrotaxane. II. Dissolution behavior of polyrotaxane in ionic liquids and preparation of ionic liquid‐containing slide‐ring gels

The dissolution behavior of polyrotaxanes, consisting of α‐cyclodextrin and poly(ethylene glycol), with different molecular weights (2000 and 35,000) was investigated. Halogen‐containing ionic liquids, such as chlorides or bromides, were found to be good solvents for polyrotaxanes, regardless of their cations. Dissolution required a high temperature (above 90 °C), while intensive heating over 105 °C seemed to cause decomposition of the polyrotaxane. The discovery of new solvents for polyrotaxane was applied in the preparation of ionic liquid‐containing slide‐ring gels (SR gels), that is supramolecular networks of polyrotaxane swollen with ionic liquids, using a devised “non‐drying” technique accompanied by solvent exchange. Significant swelling of the SR gels with the ionic liquids was confirmed by dynamic mechanical measurements. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1985–1994, 2006     

Heterograft copolymers of poly(ε‐caprolactone) prepared by combination of ATRA “grafting onto” and ATRP “grafting from” processes

This paper aims at reporting on the synthesis of a heterograft copolymer by combining the “grafting onto” process based on atom transfer radical addition (ATRA) and the “grafting from” process by atom transfer radical polymerization (ATRP). The statistical copolymerization of ε‐caprolactone (εCL) and α‐chloro‐ε‐caprolactone (αClεCL) was initiated by 2,2‐dibutyl‐2‐stanna‐1,3‐dioxepane (DSDOP), followed by ATRA of parts of the chlorinated units of poly(αClεCL‐co‐εCL) on the terminal double bond of α‐MeO,ω‐CH₂?CH? CH₂? CO₂‐poly(ethylene oxide) (PEO). The amphiphilic poly(εCL‐g‐EO) graft copolymer collected at this stage forms micelles as supported by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The unreacted pendant chloro groups of poly(εCL‐g‐EO) were used to initiate the ATRP of styrene with formation of copolymer with two populations of randomly distributed grafts, that is PEO and polystyrene. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6015–6024, 2006     

Polymer‐regulated pattern formation in pseudo‐2D arrays of a fullerene derivative at the solution—Air interface

Self‐assembly of nanoparticles (NPs) into nonclose‐packed (ncp), semi‐two‐dimensional (2D) arrays is of interest in a variety of applications. Of special interest are photochemically active surfactant‐like fullerene derivatives [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM). The study presented here characterizes the morphology and structure of patterns formed by a mixture of PCBM NP and an amphiphilic block‐copolymer tethered at the water–air interface (a surface brush) as a function of the concentration of poly(ethylene oxide) (PEO) dissolved in the liquid subphase. Theoretical modeling of the system shows that the concentration of PEO in the subphase mediates the dimensions of the surface brush and at high PEO concentrations induces a collapse of the brush at the solution–air interface. The state of the surface brush is suggested to tune the semi‐2D patterns observed in the experiments via lateral depletion interactions and, in particular, induce lateral phase separation of the PCBM‐block copolymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Modification of the lyotropic liquid crystalline microstructure of amphiphilic block copolymers in the presence of cosolvents

This article reviews the results of recent investigations on the macroscopic (phase behavior) and microscopic (microstructure) aspects of the role of cosolvents on the self-assembly of amphiphilic copolymers. A comprehensive account of the systematic studies performed in ternary isothermal systems consisting of a representative poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) block copolymer (Pluronic P105, EO₃₇PO₅₈EO₃₇), water and a polar cosolvent (such as glycerol, propylene glycol or ethanol) is presented. The effect of cosolvents on the copolymer phase behavior is quantified in terms of the highest cosolvent/water ratio able to maintain the liquid crystalline structures. The effect of cosolvents on the microstructure of the lyotropic liquid crystals is quantified in terms of the degree of relative swelling per cosolvent content per copolymer content, a parameter that characterizes the given cosolvent and copolymer. The set of correlations on the cosolvent effects on the phase behavior or microstructure to the cosolvent physicochemical characteristics (such as octanol/water partition coefficient or solubility parameter) have led to the development of a hypothesis that accounts for the cosolvent effects on the self-assembly of PEO–PPO–PEO block copolymers and can be used to predict them. The rich structural diversity and the potential for a precise and convenient modification of the lyotropic liquid crystalline microstructure of the PEO–PPO–PEO block copolymers is discussed in comparison to the phase behavior of the low-molecular nonionic surfactants.     

Effect of incorporated CdS nanoparticles on the crystallinity and morphology of poly(styrene‐b‐ethylene oxide) diblock copolymers

Surface‐modified CdS nanoparticles selectively dispersed in hexagonally packed poly(ethylene oxide) (PEO) cylinders of poly(styrene‐b‐ethylene oxide) (PSEO) block copolymers were prepared. The photoluminescence and ultraviolet–visible characteristics of the presynthesized CdS nanoparticles in N,N‐dimethylformamide and in PEO domains of the PSEO block copolymers were determined. Because of strong interactions between the CdS nanoparticles and PEO chains, as shown by Fourier transform infrared spectroscopy, the incorporation of the CdS nanoparticles prevented the PEO cylinders from properly crystallizing; this was confirmed by differential scanning calorimetry and wide‐angle X‐ray diffraction measurements. The intercylinder distance between the swollen and reduced‐crystallinity CdS/PEO cylinders in turn increased, as confirmed by small‐angle X‐ray scattering and transmission electron microscopy. At a high CdS concentration (43 wt % or 8.3 vol % with respect to PEO), however, the hexagonally packed cylindrical nanostructure of the PSEO diblock copolymers was destroyed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1220–1229, 2005     

Cloud Point Phenomena of Mixed Block Copolymers

Cloud points data on solutions of a poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) abbreviated as EPE or Pluronics, such as P–65, P–84, P–85, P-105, L-64, and their mixtures at different salt (NaCl) concentrations in water are reported. The addition of NaCl to these mixed copolymers decreases cloud point, increases surface activity, and shifts micellization to lower concentration. In presence of NaCl, more surfactant is needed for demicellization of P105 micelles.