Preparation of Core–Shell‐Type Poly(ethylene glycol)‐Grafted Polystyrene Resins and Their Characteristics in Solid‐Phase Peptide Synthesis

By suspension polymerization using styrene, divinylbenzene, and synthetic poly(ethylene glycol) (PEG) macromonomers, we have prepared core–shell‐type resins that have a highly crosslinked polystyrene core and a PEG shell. The PEG macromonomer, which has a vinyl group and an amino group at each terminal, plays a role as a stabilizer in the suspension polymerization system. All the resins were of the bead type with a diameter of 38–150 μm. The loading capacities of the amino groups were 0.1–0.2 mmol · (g resin)⁻¹ and the thickness of the PEG shell 2–4 μm, which was verified by cross‐sectioned views of the fluorescamine‐coupled beads. During coupling of amino acids in solid‐phase peptide synthesis, the resin showed better yields than TentaGel resin, especially during the first coupling step. In the enzymatic cleavage reaction, the resin‐bound peptides were shaved about 5–10 times more than TentaGel resin.

SEM micrograph of CutiCore resin (×200).     

Poly(N‐isopropylacrylamide) Brush Fabricated by Surface‐Initiated Photopolymerization and its Response to Temperature

A well‐defined, high‐density poly(N‐isopropylacrylamide) (PNIPAM) brush was fabricated through a novel and reliable strategy by the combination of the self‐assembly of a monolayer of dendritic photoinitiator and surface‐initiated photopolymerization. The whole fabrication process of the PNIPAM brush was followed by water contact angles, X‐ray photoelectron spectroscopy, and atomic force microscopy. Characterization of the PNIPAM brush, such as molecular weight and thickness determination, were measured by gel permeation chromatography, and ellipsometry, and the graft density was estimated. The temperature response of the PNIPAM brush was further investigated and the result verified the coil‐to‐globule transition of the PNIPAM chains in water from low to high temperature.

     

Coil‐to‐Globule Transition of Poly(N‐isopropylacrylamide) in Aqueous Solution: Kinetics in Bulk and Nanopores

Differential scanning calorimetry (DSC) is used to study the kinetics of the coil‐to‐globule transition in aqueous solutions of poly(N‐isopropoylacrylamide) (PNIPAM) prepared in the bulk (3 and 10 wt%) and nanoconfined (10 wt% inside 30 nm silica pores) forms. It is demonstrated that the kinetics can be described in terms of the classical nucleation model. The proposed treatment affords estimating the free‐energy barrier and pre‐exponential factor of the transition. The application of the nucleation model to the DSC data collected for the three systems studied provides physical insights into the effect of increasing the transition temperature due to dilution and nanoconfinement. Dilution appears to raise the free‐energy barrier, whereas nanoconfinement causes a decrease in the pre‐exponential factor.

     

Gamma‐Cyclodextrin‐Recognition‐Responsive Characteristics of Poly(N‐isopropylacrylamide)‐Based Hydrogels with Benzo‐12‐crown‐4 Units as Signal Receptors

Molecular‐recognition‐responsive characteristics of a novel poly(N‐isopropylacrylamide‐co‐benzo‐12‐crown‐4‐acrylamide) (PNB12C4) hydrogel have been investigated. In the prepared PNB12C4 hydrogel, benzo‐12‐crown‐4 (B12C4) groups act as guest molecules and γ‐cyclodextrin (γ‐CD)‐receptors, and poly(N‐isopropylacrylamide) (PNIPAM) networks act as phase‐transition actuators. The formation of stable γ‐CD/B12C4 complexes enhances the hydrophilicity of the PNB12C4 hydrogel networks, and induces positive shift of the volume phase transition temperature (VPTT) of PNB12C4 hydrogel. Moreover, the PNB12C4 hydrogel also shows thermoresponsive adsorption property selectively towards γ‐CD. The γ‐CD‐recognition sensitivity of PNB12C4 hydrogel can be dramatically improved by increasing γ‐CD concentration in solution or B12C4 content in PNB12C4 copolymer networks. The results in this study provide valuable information for developing crown ether‐based smart materials in various applications.

     

Temperature and pH Dual‐Responsive Behavior of Dendritic Poly(N‐isopropylacrylamide) with a Polyoligomeric Silsesquioxane Core and Poly(2‐hydroxyethyl methacrylate) Shell

Novel temperature and pH dual‐responsive dendritic polyoligomeric silsesquioxane (POSS)–poly(N‐isopropylacrylamide) (PNIPAm)–poly(2‐hydroxyethyl methacrylate) (PHEMA) copolymers are prepared via atom transfer radical polymerization and click reactions. The cloud points (T_c) decrease with decreasing pH from 10.0 to 5.0 due to the weakened inter‐molecular interactions and enhanced intra‐molecular hydrogen bonding, whereas the T_c exhibits a small increase from pH 5.0 to 4.0 because of the better solvation of PHEMA at highly acidic conditions. The above findings are corroborated by the different sizes of aggregates observed by dynamic light scattering. The encapsulation of a fluorescent dye and stimulated release by temperature and pH changes are also demonstrated.     

Triggering the Thermosensitive Properties of Hydrophobically Modified Poly(N‐isopropylacrylamide) by Complexation with Cyclodextrin Polymers

Summary: Hydrophobically modified poly(N‐isopropylacrylamide) (PNIPAM) containing either an adamantyl or a dodecyl group were prepared and characterized. Self‐association in aqueous solutions was evidenced by fluorescence measurements using pyrene as a probe. The lower critical solution temperatures (LCST) were determined from cloud point measurements. They strongly depended on the hydrophobic group and the substitution level. The association between hydrophobically modified PNIPAM and β‐cyclodextrin (monomers and polymers) was investigated by cloud point and viscosity measurements. The presence of β‐cyclodextrin monomers generally shifted the LCST to a higher temperature, the complexation increasing the solubility of PNIPAM chains. β‐Cyclodextrin polymers mixed with hydrophobically modified PNIPAM generated supramolecular assemblies. This was evidenced by viscosity measurements of the mixtures at temperatures lower than the LCST. Moreover, depending on the substitution level of the PNIPAM, the LCST was increased (1% hydrophobic groups) or decreased (4% hydrophobic groups) by more than 10 °C upon β‐cyclodextrin polymer addition.

Transmission variations of different mixtures of PNIPAM‐C12 with cyclodextrin compounds vs temperature.     

Synthesis of Poly(N‐isopropylacrylamide)‐Block‐Poly(tert‐Butyl Methacrylate) Block Copolymer by Visible Light–Induced Metal‐Free Atom Transfer Polymerization

Atom transfer radical polymerization (ATRP) is one of the most powerful methodologies for polymerization. Well‐controlled ATRP of N‐isopropylacrylamide (NIPAAm) could be obtained in organic‐water mixture solvent with conventional metal catalyst/ligand catalyst system. However, the mixture solvent is not suitable for copolymerization of NIPAAm with hydrophobic monomers. Moreover, further purification of metal was required for biomedical polymerization. Here, poly(N‐isopropylacrylamide) (PNIPAAm) is synthesized by visible light–induced metal‐free ATRP using a photoredox catalyst. PNIPAAm is obtained with high conversion and controlled molecular weight with low dispersity. Moreover, poly(N‐isopropylacrylamide)‐block‐poly(tert‐butyl methacrylate) (PNIPAAm‐b‐PMAA) block copolymer can be synthesized by such metal‐free ATRP. PNIPAAm‐b‐PMAA can be obtained by following hydrolysis.     

Polymers Diffusivity Encoded by Stimuli‐Induced Phase Transition: Theory and Application to Poly(N‐Isopropylacrylamide) with Hydrophilic and Hydrophobic End Groups

The self‐diffusion of various nano‐objects investigated by high‐resolution nuclear magnetic resonance diffusometry proves to be an efficient method for the characterization of dynamics, aggregation kinetic, and matrix morphology. This study investigates how the two‐state model and Boltzmann function approach can be used for the evaluation of the thermodynamic parameters of temperature‐induced phase transition encoded in polymer diffusivity. The characteristics of the phase transition given by the transition temperature, change of entropy, and width of transition are obtained for poly(N‐isopropylacrylamide) (PNIPAm) linear polymers with hydrophilic and hydrophobic end‐group functionalization. The effect of end groups upon the polymer diffusivity is investigated as a function of molecular weight (M _n), from which fractal dimensions and hydrodynamic drag coefficients are obtained. The PNIPAm diffusivity is affected strongly by the end groups, and it is reflected in the hydrodynamic radius dependence upon molecular weight that obeys different power‐law relations. In this study, the synthesis of α‐ω‐heterotelechelic PNIPAm of different molecular weights with a thiol end group and a hydrophilic NIPAm‐like as well as a hydrophobic benzyl end group are described by reversible addition–fragmentation chain‐transfer polymerization.     

Synthesis and Hole‐Transporting Property of a Novel Poly(N‐vinylcarbazole) Copolymer with Metal‐Coordination Sites

Summary: Hole transporting poly(N‐vinylcarbazole) copolymers with phenylazomethine dendron units acting as metal ligation sites were synthesized. These polymers possess both hole‐transport and metal‐collecting units with simple σ‐bond linkages. Complexation in the phenylazomethine dendron unit within these copolymers by SnCl₂ has been successfully observed by the change in the UV‐vis spectra. The complexation changes the HOMO/LUMO energy gap that results in a spectral red‐shift. Using copolymers as a hole‐transport layer, only complexation with metal ions leads to an enhanced maximum luminescence. Such a complexation results in a high electroluminescence efficiency because the p‐type‐doped structure acts as the hole‐transport layer.

Copolymerization for the preparation of DPAGn(x)‐Cbz(y).     

The Dependence of the Cloud Point,Clearing Point,and Hysteresis of Poly(N‐isopropylacrylamide) on Experimental Conditions: The Need for Standardization of Thermoresponsive Transition Determinations

Inappropriately, the critical solution temperature (CST) of lower CST(LCST)‐ or upper CST(UCST)‐type thermoresponsive polymers, measured by one, individual set of conditions, is considered almost exclusively as the LCST or UCST, respectively. These are correctly the minimum or maximum, respectively, of the full phase diagrams. Because the dynamic phase transition depends on the conditions, and no standardized or widely accepted process exists for CST determination, systematic investigations are carried out with the most widely investigated poly(N‐isopropylacrylamide) (PNIPAAm) to unveil the effect of data evaluation, measurement conditions on the transmittance–temperature curves, cloud point (T _CP), clearing point (T _CL), and heating–cooling hysteresis. The unusual dependence of the fundamental hysteresis parameters, i.e., width of hysteresis (X _H) and extent of transmittance recovery (Y _H), on a broad range of conditions is revealed for the first time. On the basis of the findings, the inflection point of transmittance(absorbance)–temperature curves as T _CP and T _CL, 0.1 wt% solution, 0.2 °C min⁻¹ heating/cooling steps with 5 min equilibration between the gradual change of temperature, 488 nm wavelength to obtain data comparable to light scattering at this wavelength, and determination of X _H and Y _H are proposed as standard set of conditions.

     

Structure and Properties of Poly(ε‐caprolactone) Networks with Modulated Water Uptake

Summary: A PCL macromonomer was obtained by the reaction of PCL diol with methacrylic anhydride. The effective incorporation of the polymerizable end groups was assessed by FT‐IR and ¹H NMR spectroscopy. PCL networks were then prepared by photopolymerization of the PCL macromonomer. Furthermore, the macromonomer was copolymerized with HEA, with the aim of tailoring the hydrophilicity of the system. A set of hydrophilic semicrystalline copolymer networks were obtained. The phase microstructure of the new system and the network architecture was investigated by DSC, IR, DMS, TG, dielectric spectroscopy and water sorption studies. The presence of the hydrophilic units in the system prevented PCL crystallization on cooling; yet there was no effect on the glass transition process. The copolymer networks showed microphase separation and the α relaxation of the HEA units moved to lower temperatures as the amount of PCL in the system increased.

Ideal structure, compatible with the experimental results, for the hydrophilized poly(ε‐caprolactone) networks with modulated water uptake.