Dynamic Covalent Bonds of Si-OR and Si-OSi Enabled A Stiff Polymer to Heal and Recycle at Room Temperature

As stiff polymers are difficult to self-heal, the balance between polymers’ self-healing ability and mechanical properties is always a big challenge. Herein, we have developed a novel healable stiff polymer based on the Si-OR and Si-OSi dynamic covalent bonds. The self-healing mechanism was tested and proved by the small molecule model experiments and the contrast experiments of polymers. This polymer possesses excellent tensile, bending properties as well as room temperature self-healing abilities. Moreover, due to the sticky and shapeable properties under wetting conditions, the polymer could be used as an adhesive. Besides, even after four cycles of recycling, the polymer maintains its original properties, which meets the requirements of recyclable materials. It was demonstrated that the polymer exhibits potential application in some fields, such as recyclable materials and healable adhesives.

Point perturbations

This chapter discusses the energetics of point perturbations arising from intrinsic and extrinsic defects, and intentional and unintentional impurities. Point perturbations can be short range or long range. This requires the inclusion of core potential, exchange correlation and Hartree or Hartree-Fock potential. Hubbard energy, which is useful for Hartree calculations in a localized state, is introduced. An approach to calculating the behavior arising in shallow dopants (long range) and deep centers (short range) is presented. The tight binding defect-molecule model is used to explore the appearance of bonding and antibonding states in vacancies, interstitials and substitutional deep centers and some common complexes, such as the DX center, using configuration coordinates to understand the electronic and lattice energy contributions in the defect behavior. Finally, the chapter summarizes other important centers, such as the Pb center and the F center, before reviewing the implications of centers in light interaction and Poole-Frenkel conduction.

A fast and versatile cross-linking strategy via o-phthalaldehyde condensation for mechanically strengthened and functional hydrogels

Fast and catalyst-free cross-linking strategy is of great significance for construction of covalently cross-linked hydrogels. Here, we report the condensation reaction between o-phthalaldehyde (OPA) and N-nucleophiles (primary amine, hydrazide and aminooxy) for hydrogel formation for the first time. When four-arm poly(ethylene glycol) (4aPEG) capped with OPA was mixed with various N-nucleophile-terminated 4aPEG as building blocks, hydrogels were formed with superfast gelation rate, higher mechanical strength and markedly lower critical gelation concentrations, compared to benzaldehyde-based counterparts. Small molecule model reactions indicate the key to these cross-links is the fast formation of heterocycle phthalimidine product or isoindole (bis)hemiaminal intermediates, depending on the N-nucleophiles. The second-order rate constant for the formation of phthalimidine linkage (4.3 M−1 s−1) is over 3000 times and 200 times higher than those for acylhydrazone and oxime formation from benzaldehyde, respectively, and comparable to many cycloaddition click reactions. Based on the versatile OPA chemistry, various hydrogels can be readily prepared from naturally derived polysaccharides, proteins or synthetic polymers without complicated chemical modification. Moreover, biofunctionality is facilely imparted to the hydrogels by introducing amine-bearing peptides via the reaction between OPA and amino group.