3D Printable Modular Soft Elastomers from Physically Cross-linked Homogeneous Associative Polymers.

Three-dimensional (3D) printing of elastomers enables the fabrication of many technologically important structures and devices. However, there remains a critical need for the development of reprocessable, solvent-free, soft elastomers that can be printed without the need for post-treatment. Herein, we report modular soft elastomers suitable for direct ink writing (DIW) printing by physically cross-linking associative polymers with a high fraction of reversible bonds. We designed and synthesized linear-associative-linear (LAL) triblock copolymers; the middle block is an associative polymer carrying amide groups that form double hydrogen bonding, and the end blocks aggregate to hard glassy domains that effectively act as physical cross-links. The amide groups do not aggregate to nanoscale clusters and only slow down polymer dynamics without changing the shape of the linear viscoelastic spectra; this enables molecular control over energy dissipation by varying the fraction of the associative groups. Increasing the volume fraction of the end linear blocks increases the network stiffness by more than 100 times without significantly compromising the extensibility. We created elastomers with Young's moduli ranging from 8 kPa to 8 MPa while maintaining the tensile breaking strain around 150%. Using a high-temperature DIW printing platform, we transformed our elastomers to complex, highly deformable 3D structures without involving any solvent or post-print processing. Our elastomers represent the softest melt reprocessable materials for DIW printing. The developed LAL polymers synergize emerging homogeneous associative polymers with a high fraction of reversible bonds and classical block copolymer self-assembly to form a dual-cross-linked network, providing a versatile platform for the modular design and development of soft melt reprocessable elastomeric materials for practical applications.

Dynamics of Associative Polymers with High Density of Reversible Bonds.

An associative polymer carries many stickers that can form reversible associations. For more than 30 years, the understanding has been that reversible associations change the shape of linear viscoelastic spectra by adding a rubbery plateau in the intermediate frequency range, at which associations have not yet relaxed and thus effectively act as crosslinks. Here, we design and synthesize new classes of unentangled associative polymers carrying unprecedentedly high fractions of stickers, up to eight per Kuhn segment, that can form strong pairwise hydrogen bonding of ∼20k_{B}T without microphase separation. We experimentally show that reversible bonds significantly slow down the polymer dynamics but nearly do not change the shape of linear viscoelastic spectra. This behavior can be explained by a renormalized Rouse model that highlights an unexpected influence of reversible bonds on the structural relaxation of associative polymers.

Role of Hydrogen Bonding in Green Fluorescent Protein-like Chromophore Emission.

The fluorescence emission from green fluorescent protein (GFP) is known to be heavily influenced by hydrogen bonding between the core fluorophore and the surrounding side chains or water molecules. Yet how to utilize this feature for modulating the fluorescence of GFP chromophore or GFP-like fluorophore still remains elusive. Here we present theoretical calculations to predict how hydrogen bonding could influence the excited states of the GFP-like fluorophores. These studies provide both a new perspective for understanding the photophysical properties of GFP as well as a solid basis for the rational design of GFP-based fluorophores.

Racemic Fluorescence Probe for Enantiomeric Excess Determination: Application of Cononsolvency of a Polymer in Sensing.

Both racemic and optically active 3,3'-diformyl-1,1'-BINOL-based diinitiators (BINOL = 1,1'-bi-2-naphthol) were used to carry out the atom transfer radical polymerization (ATRP) of N-isopropylacrylamide to make polymers rac-1, ( R)-1, and ( S)-1 which are soluble in water as well as organic solvents. These polymers are found to exhibit a unique cononsolvency property. Mixing an aqueous solution of a polymer and Zn2+ with a dichloromethane solution of ( S)- or ( R)-amino alcohols led to the formation of polymer films at the interface of the water and dichloromethane phases. The polymer films were separated and showed highly enantioselective fluorescence enhancement in DMSO solution. When the polymers were treated with a mixture of the enantiomers of an amino alcohol, no fluorescence enhancement was observed unless one of the enantiomers was in excess of the other. Such a large nonlinear effect allows the racemic polymer rac-1 to be used to determine the ee of the amino alcohol. This represents the first example to use a racemic fluorescent probe to determine the ee of a chiral molecule.

Molecular Architecture Directs Linear-Bottlebrush-Linear Triblock Copolymers to Self-Assemble to Soft Reprocessable Elastomers.

Linear-bottlebrush-linear (LBBL) triblock copolymers represent an emerging system for creating multifunctional nanostructures. Their self-assembly depends on molecular architecture but remains poorly explored. We synthesize polystyrene-block-bottlebrush polydimethylsiloxane-block-polystyrene triblock copolymers with controlled molecular architecture and use them as a model system to study the self-assembly of LBBL polymers. Unlike classical stiff rod-flexible linear block copolymers that are prone to form highly ordered nanostructures such as lamellae, at small weight fractions of the linear blocks, LBBL polymers self-assemble to a disordered sphere phase, regardless of the bottlebrush stiffness. Microscopically, characteristic lengths increase with the bottlebrush stiffness by a power of 2/3, which is captured by a scaling analysis. Macroscopically, the formed nanostructures are ultrasoft, reprocessable elastomers with shear moduli of about 1 kPa, two orders of magnitude lower than that of conventional polydimethylsiloxane elastomers. Our results provide insights on exploiting the self-assembly of LBBL polymers to create soft functional nanostructures.

Amphiphilic Polymer-Based Fluorescent Probe for Enantioselective Recognition of Amino Acids in Immiscible Water and Organic Phases.

Atom transfer radical polymerization (ATRP) of N-isopropylacrylamide was conducted in the presence of a 3,3'-diformyl-1,1'-BINOL-based diinitiator (BINOL=1,1'-bi-2-naphthol) to give polymer (S)-7, which was soluble in both water and common organic solvents. Polymer (S)-7 in combination with Zn2+ in aqueous solution (BICINE buffer at pH 8.80) showed highly enantioselective fluorescence enhancement in the presence of a number of amino acids. It was found that chloroform can be used to extract the aqueous polymer-Zn2+ -amino acid solution and the resulting chloroform extract maintained the highly enantioselective fluorescence response. Thus, the enantiomeric composition of a chiral amino acid can be determined in the two immiscible solvents of water and chloroform. The aqueous polymer-Zn2+ -amino acid solution showed a lower critical solution temperature (LCST) at 34 °C, above which the polymer-Zn2+ -amino acid adduct precipitated out. Measuring the fluorescence of the precipitate redissolved in the aqueous buffer solution showed the retention of the high enantioselectivity. Both the chloroform extraction and the thermo-induced precipitation have allowed the fluorescence response of the sensor toward amino acids to be measured away from the original substrate solution. These two strategies should minimize the interference by other reaction components on the fluorescence measurement when the sensor is applied to analyze the asymmetric reaction screening experiments.