Atom transfer radical polymerization (ATRP) of oligo­(ethylene oxide) methyl ether methacrylate (OEOMA, M n = 950 or 2080; OEOMA is also termed poly­(ethylene glycol) methyl ether methacrylate, PEGMA) macromonomers was investigated as a function of initial monomer concentration, [OEOMA]0, ranging from 50 to 300 mM, and up to 4.5 kbar. Polymerizations were successfully carried out in organic solvents with [OEOMA]0 > 75 mM, whereas with [OEOMA]0 = 50 mM no monomer conversion was observed at ambient pressure, indicating that the macromonomer concentration was below its equilibrium monomer concentration ([M]e). High pressure reduced [M]e to a level lower than under ambient pressure, allowing polymerization at [OEOMA]0 = 50 mM up to high monomer conversion and yielding polymers with narrow molecular weight distribution. By varying the targeted degree of polymerization of OEOMA, brushlike or starlike poly­(OEOMA) were prepared under both ambient and high pressure.

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Due to their capacity to conduct complex organic transformations, enzymes find extensive use in medical and industrial settings. Unfortunately, enzymes are limited by their poor stability when exposed to harsh non-native conditions. While a host of methods have been developed to stabilize enzymes in non-native conditions, recent research into the synthesis of polymer−enzyme biohybrids using reversible deactivation radical polymerization approaches has demonstrated the potential of increased enzymatic activity in both native and non-native environments. In this manuscript, we utilize the enzyme lipase, as a model system, to explore the impact that modulation of grafted polymer molecular weight has on enzyme activity in both aqueous and organic media. We studied the properties of these hybrids using both solution-phase enzyme activity methods and coarse-grain modeling to assess the impact of polymer grafting density and grafted polymer molecular weight on enzyme activity to gain a deeper insight into this understudied property of the biohybrid system.

The effect of polyhedral oligomeric silsesquioxane (POSS) on the synthesis and properties of hybrid organic–inorganic ionogels was investigated using octakis(methacryloxypropyl) silsesquioxane (methacryl-POSS). Ionogels were prepared in situ by thiol-ene photopolymerization of triallyl isocyanurate with pentaerythritol tetrakis(3-mercaptopropionate) in a mixture of imidazolium ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMImNTf2) and propylene carbonate (PC). Investigations included the kinetics of hybrid materials formation and selected physical and mechanical properties. The disadvantage of ionogels without the methacryl-POSS modifier is leakage and insufficient mechanical properties. Modifying the thiol-ene matrix by the addition of methacryl-POSS made it possible to obtain non-leaking ionogels with improved mechanical and conductive properties. The steric hindrance of POSS cages and high-density network formation played important roles in ionogel synthesis: decrease of polymerization rate (with almost no effect on conversion), as well as dimensions of the formed polymer spheres during dispersion polymerization (highly cross-linked polymer has poorer solubility in polymerizing medium at a similar conversion, and nucleation begins at lower conversion), an increase of glass transition temperature and puncture strength. Hybrid ionogels with high ionic conductivity in the range of 4.0–5.1 mS∙cm−1 with the maximum parameter for 1.5 wt.% addition of the methacryl-POSS were obtained, which can be associated with ion-pair dissociations in ionic liquid clusters caused by methacryl-POSS.

Porphyromonas gingivalis is a keystone pathogen of the human dysbiotic oral microbiome that causes severe periodontitis. It employs a type-IX secretion system (T9SS) to shuttle proteins across the outer membrane (OM) for virulence. Uniquely, T9SS cargoes carry a C-terminal domain (CTD) as a secretion signal, which is cleaved and replaced with anionic lipopolysaccharide by transpeptidation for extracellular anchorage to the OM. Both reactions are carried out by PorU, the only known dual-function, C-terminal signal peptidase and sortase. PorU is itself secreted by the T9SS, but its CTD is not removed; instead, intact PorU combines with PorQ, PorV, and PorZ in the OM-inserted “attachment complex.” Herein, we revealed that PorU transits between active monomers and latent dimers and solved the crystal structure of the ∼260-kDa dimer. PorU has an elongated shape ∼130 Å in length and consists of seven domains. The first three form an intertwined N-terminal cluster likely engaged in substrate binding. They are followed by a gingipain-type catalytic domain (CD), two immunoglobulin-like domains (IGL), and the CTD. In the first IGL, a long “latency β-hairpin” protrudes ∼30 Å from the surface to form an intermolecular β-barrel with β-strands from the symmetric CD, which is in a latent conformation. Homology modeling of the competent CD followed by in vivo validation through a cohort of mutant strains revealed that PorU is transported and functions as a monomer through a C690/H657 catalytic dyad. Thus, dimerization is an intermolecular mechanism for PorU regulation to prevent untimely activity until joining the attachment complex.

The effect of the anchoring group on the detailed polymerization kinetics was investigated using monomethacryloxy-heptaisobutyl POSS (1M-POSS). This compound was copolymerized with lauryl methacrylate (LM) as the base monomer, at various molar ratios. The process was initiated photochemically. The polymerization kinetics were followed by photo-DSC and photorheology while the polymers were characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). For comparison, a methacrylate containing the branched siloxy-silane group (TSM) was also studied. It was found that the modifiers with a bulky substituent have a dual effect on the termination process: (i) At low concentrations, they increase the molecular mobility by increasing the free volume fraction, which leads to an acceleration of the termination and slows the polymerization; while (ii) at higher concentrations, they retard molecular motions due to the “anchor effect” that suppresses the termination, leading to acceleration of the polymerization. The anchor effect can also be considered from a different point of view: The possibility of anchoring a monomer with a long substituent (LM) around the POSS cage, which can further enhance propagation. These conclusions were derived based on kinetic results, determination of polymerization rate coefficients, and copolymer analysis.

The influence of ene and thiol monomer structure on the mechanical and electrochemical properties of thiol–ene polymeric ionogels were investigated. Ionogels were obtained in situ by thiol–ene photopolymerization of 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TATT), 2,4,6-triallyloxy-1,3,5-triazine (TAT), diallyl phthalate (DAP), and glyoxal bis(diallyl acetal) (GBDA) used as enes and trimethylolpropane tris(3-mercaptopropionate) (TMPTP), pentaerythritol tetrakis(3-mercaptopropionate) (PETMP), and pentaerythritol tetrakis(3-mercaptobutyrate) (PETMB) used as thiols in 70 wt.% of ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMImNTf2). The mechanical strength of ionogels was studied by puncture resistance and ionic conductivity by electrochemical impedance spectroscopy. The course of photopolymerization by photo-DSC method (differential scanning calorimetry) as well as characterization of compositions and its components (by IR and UV spectroscopy-Kamlet–Taft parameters) were also studied. The resulting ionogels were opaque, with phase separation, which resulted from the dispersion mechanism of polymerization. The mechanical and conductive properties of the obtained materials were found to be largely dependent on the monomer structure. Ionogels based on triazine monomers TAT and TATT were characterized by higher mechanical strength, while those based on aliphatic GBDA had the highest conductivity. These parameters are strongly related to the structure of the polymer matrix, which is in the form of connected spheres. The conductivity of ionogels was high, in the range of 3.5–5.1 mS∙cm−1.

Flexible ionogels with good mechanical properties were obtained in situ by thiol-ene photopolymerization of trimethylolpropane tris(3-mercaptopropionate) (TMPTP) and 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TATT) (with C=C: SH ratio 1:1) in four imidazolium ionic liquids (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide—EMImNTf2, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate-EMImOTf, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide-BMImNTf2, and 1-butyl-3-methylimidazolium trifluoromethanesulfonate—BMImOTf) used in the range 50 to 70 wt.%. The mechanical and electrochemical properties of obtained ionogels were examined. Ionogels with ionic liquids (ILs) with NTf2− anion are more puncture resistant than with OTf− anion. Moreover, ionogels with the NTF2− anion have better electrochemical properties than those with the OTf− anion. Although it should be noted that ionogels with the EMIm+ cation have a higher conductivity than the BMIm+. This is connected with intermolecular interactions between polymer matrix and IL related to the polarity of IL described by the Kamlet-Taft parameters. These parameters influence the morphology of the polymer matrix (as shown by the SEM micrograph), which is formed by interconnected polymer spheres.