Polyampholytic Graft Copolymers as Matrix for TiO2/Eosin Y/[Mo3S13]2− Hybrid Materials and Light-Driven Catalysis

An effective strategy to enhance the performance of inorganic semiconductors is moving towards organic-inorganic hybrid materials. Here, we report the design of core–shell hybrid materials based on a TiO₂ core functionalized with a polyampholytic (poly(dehydroalanine)-graft-(n-propyl phosphonic acid acrylamide) shell (PDha-g-PAA@TiO₂). The PDha-g-PAA shell facilitates the efficient immobilization of the photosensitizer Eosin Y (EY) and enables electronic interactions between EY and the TiO₂ core. This resulted in high visible-light-driven H₂ generation. The enhanced light-driven catalytic activity is attributed to the unique core–shell design with the graft copolymer acting as bridge and facilitating electron and proton transfer, thereby also preventing the degradation of EY. Further catalytic enhancement of PDha-g-PAA@TiO₂ was possible by introducing [Mo₃S₁₃]²⁻ cluster anions as hydrogen-evolution cocatalyst. This novel design approach is an example for a multi-component system in which reactivity can in future be independently tuned by selection of the desired molecular or polymeric species.     

Tunable phase‐separation behavior of thermoresponsive polyampholytes through molecular design

Here, we report that carboxylated poly‐l ‐lysine, a polyampholyte, shows lower critical solution temperature (LCST)‐type temperature‐responsive liquid–liquid phase separation and coacervate formation in aqueous solutions. The phase‐separation temperature of polyampholytes is strongly affected by the polymer concentration, balance between the carboxyl and amino groups, hydrophobicity of the side chain, and NaCl concentration in the solution. We concluded that the phase separation was caused by both electrostatic interactions between the carboxyl and amino groups and intermolecular hydrophobic interactions. The addition of NaCl weakened the electrostatic interactions, causing the two phases to remix. The introduction of the hydrophobic moiety decreased the phase‐separation temperature by making the molecular interactions stronger. Finally, temperature‐responsive hydrogels were prepared from the polyampholytes to explore their applicability as biomaterials and in drug delivery systems. The fine‐tuning of the phase‐separation temperature of poly‐l ‐lysine‐based polyampholytes through molecular design should open new avenues for their use in precisely controlled biomedical applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 876–884     

Synthesis of Cationic and Ampholytic Starch Graft Acrylamide and their Aqueous Salt Absorption

Acrylamide was grafted onto starch using ceric(IV) ion as initiator. Starch–graft-polyacrylamide was then modified through Mannich reaction using formaldehyde and diethylamine to give poly(N, N′-[(diethylamino) methyl]-acrylamide). The modified-graft copolymer was quaternized using different reagents; methyl iodide, n-butylbromide, sodium chloroacetate and propane sultone to give cationic and ampholytic graft materials. The absorbing properties of the produced materials toward deionized water and aqueous salt solutions were investigated. Studies of the absorbing properties of polyampholytes have revealed that these materials do not shrink upon increasing salt concentration. Kinetics of swelling in deionized water is also discussed.     

Ionic Mixed Interactions in Macromolecules

Purely ionic interactions in natural and synthetic macromolecules involve the mutual interaction of fixed charges and their interaction with mobile ions. Such charge‐dependent interactions lead to well‐documented effects, including chain expansion of polyelectrolytes, globularization of polyampholytes, distributions of mobile ions according to charge screening, or ion condensation models. A variety of structural features, functions, and applications of these systems is amplified by the superimposition of charge‐independent effects associated with the occurrence of less polar or hydrophobic groups, special salts, surfactants, or complementary protein assemblies. For instance, ionic and hydrophobic attractive interactions stabilize pearls (or rings)‐on‐a‐string conformations, possibly a model for the formation of the chromatin assembly. The attractive interactions due to hydrophobic fatty acid groups attached to polysaccharides promote the formation of vesicles that entrap and slowly release water‐soluble drugs. Intra‐ and intermolecular associations based on ion‐pairing mixed interactions also control the formation of host–guest compounds, protein conformation, and the assembly of layered polyelectrolytes. Metallo‐supramolecular polymers and networks are formed due to the coordination of multivalent cations with bi‐ and trifunctional organic ligands. The association of lithium salts to polymers in the absence of water allows the formation of highly efficient energy sources. It also allows the identification of the ionic species that control charge‐independent contributions to Hofmeister effects. This critical review presents a synthetic classification of systems displaying ionic mixed interactions, and a discussion of underlying molecular mechanisms.     

Diblock polyampholytes at the silicon–water interface: Adsorption as a function of block ratio and molecular weight

Polyampholytes are highly charged macromolecules carrying oppositely charged functional groups. This article reports on the adsorption of a weak diblock polyampholyte, poly(methacrylic acid)‐block‐poly[(dimethylamino)ethyl methacrylate], as a function of the copolymer composition and molecular weight. The adsorption experiments were performed on silicon substrates from aqueous polymer solutions at different pHs. The amount of adsorbed polyampholyte chains to the surface was determined by ellipsometry, whereas lateral structures were investigated by scanning force microscopy. A strong influence of pH on the adsorbed amount and the lateral structure formation at the surface was observed. Especially at the isoelectric point, drastic changes in adsorption behavior were detected. At low molecular weights, an increased adsorbed amount was detected, a behavior in contrast to common theoretical predictions. This phenomenon is explained by the high stability of absorbed micelles, which cover the silicon surface as a dense layer. We conclude that micelle formation is an important process for polyampholyte adsorption, which needs to be taken into account more explicitly. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 709–718, 2001     

Preparation and characterization of narrow compositional distribution polyampholytes as potential biomaterials: Copolymers of N-(3-aminopropyl)methacrylamide hydrochloride (APM) and methacrylic acid (MAA)

This article describes the preparation and solution properties of a series of polyampholytes composed of N-(3-aminopropyl)methacrylamide hydrochloride (APM) and methacrylic acid (MAA). In particular, conditions were found where the copolymers could be formed with little or no drift in composition over the course of polymerization to quite high conversions. The compositional drift, common to many copolymerizations, was limited by adjusting the reactivity of MAA through control of its degree of ionization (i.e., pH). As revealed by potentiometric measurements and changes in ¹H NMR spectra, the solution pH drifted over the course of some polymerizations. This was ascribed to changes in the pK_a values of the ammonium and carboxylate groups upon incorporation in the copolymer. The pH drift led to a change in degree of MAA ionization, and hence the relative reactivities of APM and MAA, but this effect could be minimized by using a buffer. Precipitation, which occurred during some polymerizations, could be prevented, in some cases, by the addition of salt or an organic cosolvent. Even in cases where precipitation could not be prevented, it was found that the copolymer was still formed with minimal compositional drift. The solubility of the resulting polyampholytes in aqueous solution was found to depend on their composition, as well as pH, ionic strength and temperature. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 353–365     

One‐Step Preparation and pH‐Tunable Self‐Aggregation of Amphoteric Aliphatic Polycarbonates Bearing Plenty of Amine and Carboxyl Groups

This paper reports a novel amphoteric aliphatic polycarbonate bearing both amine and carboxyl groups. In the absence of protection‐deprotection chemistry, the multi‐functionalized copolymer is synthesized by one‐step enzymatic copolymerization. The influences of the reaction conditions including monomer feed ratio and polymerization time are explored. The simultaneous incorporation of amine and carboxyl functionalities provides the copolymer with a pH‐tunable self‐aggregation feature, leading to various aggregation states including precipitated agglomerate, well‐dispersed positively or negatively charged nanoparticles in a controlled manner. The copolymer displays minimal cytotoxicity to 293T and HeLa cells.

     

Polyampholyte Nanoparticles Prepared by Self‐Complexation of Cationized Poly(γ‐glutamic acid) for Protein Carriers

A novel amphoteric poly(amino acid) is synthesized by grafting a cationic amino acid (L ‐Arg) to γ‐PGA to prepare charged NPs. γ‐PGA‐Arg NPs can be prepared by the self‐complexation of a single polymer by intra‐/inter‐molecular electrostatic interactions when the polymer is dispersed in water. The size and surface charge of the NPs can be regulated by the grafting degree of Arg (41, 56, and 83%). The smallest NPs are obtained at 56% grafting degree of the γ‐PGA‐Arg copolymer. The 56 and 83% grafting degree NPs are stable for at least 1 week. Depending on their surface charge, these NPs can selectively adsorb anionically or cationically charged proteins.

     

Kinetically controlled growth of gold nanotriangles in a vesicular template phase by adding a strongly alternating polyampholyte

This paper is focused on the temperature-dependent synthesis of gold nanotriangles in a vesicular template phase, containing phosphatidylcholine and AOT, by adding the strongly alternating polyampholyte PalPhBisCarb.

UV-vis absorption spectra in combination with TEM micrographs show that flat gold nanoplatelets are formed predominantly in the presence of the polyampholyte at 45°C. The formation of triangular and hexagonal nanoplatelets can be directly influenced by the kinetic approach, i.e., by varying the polyampholyte dosage rate at 45°C. Corresponding zeta potential measurements indicate that a temperature-dependent adsorption of the polyampholyte on the {111} faces will induce the symmetry breaking effect, which is responsible for the kinetically controlled hindered vertical and preferred lateral growth of the nanoplatelets.