Plastics have become indispensable in modern life and the material of choice in packaging applications, but they have also caused increasing plastic waste accumulation in oceans and landfills. Although there have been continuous efforts to develop biodegradable plastics, the mechanical and/or transport properties of these materials still need to be significantly improved to be suitable for replacing conventional plastic packaging materials. Here we report a class of biorenewable and degradable plastics, based on copolymers of γ-butyrolactone and its ring-fused derivative, with competitive permeability and elongation at break compared to commodity polymers and superior mechanical and transport properties to those of most promising biobased plastics. Importantly, these materials are designed with full chemical recyclability built into their performance with desired mechanical and barrier properties, thus representing a circular economy approach to plastic packaging materials.

Plastics, used in countless consumer products that our daily lives depend on, have become indispensable materials essential for modern life and the global economy. At the same time, currently unsustainable practices in the production and disposal of plastics continue to deplete our finite natural resources and create severe worldwide environmental consequences. In the search for feasible solutions to these issues, significant recent advances have been made in developing chemically recyclable plastics, which allow for recovery of the buildingblock chemicals via depolymerization, for repolymerization to virgin-quality plastics, or for creative repurposing into value-added materials. Among such recyclable plastics, polyesters derived from renewable cyclic esters possess real potential to meet these challenges. Hence, this review highlights the plastics derived from common four-, five-, six-, seven-, and eight-membered cyclic esters by covering synthetic strategies, material properties, and, particularly, chemical recyclability. Such studies have culminated a recent discovery of infinitely recyclable plastics with properties of common plastics.

α-Methylene-γ-butyrolactone (MBL), a naturally occurring and biomass-sourced bifunctional monomer, contains both a highly reactive exocyclic C═C bond and a highly stable five-membered γ-butyrolactone ring. Thus, all previous work led to exclusive vinyl-addition polymerization (VAP) product P(MBL). Now, this work reverses this conventional chemoselectivity to enable the first ring-opening polymerization (ROP) of MBL, thereby producing exclusively unsaturated polyester P(MBL) with M up to 21.0 kg/mol. This elusive goal was achieved through uncovering the thermodynamic, catalytic, and processing conditions. A third reaction pathway has also been discovered, which is a crossover propagation between VAP and ROP processes, thus affording cross-linked polymer P(MBL). The formation of the three types of polymers, P(MBL), P(MBL), and P(MBL), can be readily controlled by adjusting the catalyst (La)/initiator (ROH) ratio, which is determined by the unique chemoselectivity of the La-X (X = OR, NR, R) group. The resulting P(MBL) is degradable and can be readily postfunctionalized into cross-linked or thiolated materials but, more remarkably, can also be fully recycled back to its monomer thermochemically. Computational studies provided the theoretical basis for, and a mechanistic understanding of, the three different polymerization processes and the origin of the chemoselectivity.

Stereoselective polymerization of chiral or prochiral monomers is a powerful method to produce high-performance stereoregular crystalline polymeric materials. However, for monomers with two stereogenic centers, it is generally necessary to separate diastereomers before polymerization, resulting in substantial material loss and added energy cost associated with the separation and purification process. Here we report a diastereoselective polymerization methodology enabled by catalysts that directly polymerize mixtures of eight-membered diolide (8DL) monomers with varying starting ratios of chiral racemic (rac) and achiral meso diastereomers into stereosequenced crystalline polyhydroxyalkanoates with isotactic and syndiotactic stereodiblock or stereotapered block microstructures. These polymers show enhanced ductility and toughness relative to polymers of pure rac-8DL, subject to tuning by variation of the diastereomeric ratio and structure of the 8DL monomers.

Bacterial poly(3-hydroxybutyrate) (P3HB) is a perfectly isotactic, crystalline material possessing properties suitable for substituting petroleum plastics, but high costs and low volumes of its production are impractical for commodity applications. The chemical synthesis of P3HB via ring-opening polymerization (ROP) of racemic β-butyrolactone has attracted intensive efforts since the 1960s, but not yet produced P3HB with high isotacticity and molecular weight. Here, we report a route utilizing racemic cyclic diolide (rac-DL) derived from bio-sourced succinate. With stereoselective racemic catalysts, the ROP of rac-DL under ambient conditions produces rapidly P3HB with perfect isotacticity ([mm] > 99%), high melting temperature (Tm = 171 °C), and high molecular weight (Mn = 1.54 × 105 g mol−1, Đ = 1.01). With enantiomeric catalysts, kinetic resolution polymerizations of rac-DL automatically stops at 50% conversion and yields enantiopure (R,R)-DL and (S,S)-DL with >99% e.e. and the corresponding poly[(S)-3HB] and poly[(R)-3HB] with high Tm = 175 °C.

A direct comparison of the self-assembly on Au and Ag of thiol and disulfide derivatives of viologens bearing long n-alkyl chains was made in order to ascertain the relative efficiency of monolayer formation for each type of functionality. The structures of the two derivatives that were studied can be written as CH3V2+(CH2)12SH and [CH3V2+(CH2)12S]2 for the thiol and disulfide, respectively, where V2+ represents the viologen (i.e. N,N‘-dialkyl-4,4‘-bipyridinium) redox group. In contrast to the behavior of n-alkane thiols and di-n-alkyl disulfides, which adsorb to give very nearly the same surface coverage and interfacial properties, these two viologen derivatives exhibit different saturation surface coverages of 1.8 × 10-10 mol cm-2 for the disulfide and 4.5 × 10-10 mol cm-2 for the thiol, as determined from the charge for exhaustive reduction and reoxidation of the viologen redox groups. In addition, monolayers of the thiol derivative that had very high surface coverages exhibited very sharply peaked cyclic voltammetric responses that are attributed to very strong interactions between the one-electron-reduced cation radicals in the monolayer, a phenomenon that does not occur in monolayers prepared from pure samples of the disulfide derivative. Vibrational spectroscopic examination of these monolayers under conditions in which this unique voltammetric response is observed revealed the presence of vibrational spectroscopic signatures of viologen dimer formation. Specifically, surface Raman spectroscopy (including surface-enhanced Raman, surface resonance Raman, and surface-enhanced resonance Raman) was used to demonstrate that the lateral interaction of the cation radical viologen redox groups in these monolayers results in the formation of π complex dimers. The presence of these dimers is correlated with the very sharply peaked cyclic voltammetric responses. The Raman bands due exclusively to the dimer are assigned to the out-of-phase coupling combination of the totally symmetric ring modes of the component cation radicals in the dimer.

No abstract

We herein report a water-stable three-dimensional Cu-based metal-organic framework (MOF) 1 supported by a tritopic quaternized carboxylate and 4,4'-dipyridyl sulfide as an ancillary ligand. This MOF exhibits unique pore shapes with aromatic rings, positively charged pyridinium and unsaturated Cu(II) cation centers, free carboxylates, tessellating H2O, and coordinating SO4(2-) on the pore surface. Compound 1 can interact with two carboxyfluorescein (FAM)-labeled single-stranded DNA sequences (probe ss-DNA, delineated as P-DNA) through electrostatic, π-stacking, and/or hydrogen-bonding interactions to form two P-DNA@1 systems, and thus quench the fluorescence of FAM via a photoinduced electron-transfer process. These P-DNA@1 systems can be used as effective fluorescent sensors for human immunodeficiency virus 1 double-stranded DNA and Sudan virus RNA sequences, respectively, with detection limits of 196 and 73 pM, respectively.