Addition Fragmentation Research Articles

Synthesis of bio‐based modified amphoteric acrylate epoxy emulsion surface sizing agent via RAFT polymerization

AbstractThe synthesis of bio‐based modified amphoteric epoxy modified acrylate sizing emulsion based on reversible addition fragmentation chain transfer (RAFT) polymerization and its application in paper sizing were studied. A macromolecular chain transfer agent for RAFT polymerization was synthesized by the esterification of epoxy resin E‐51 with RAFT agent to eliminate the active groups on RAFT agent. Amphoteric polymer emulsifiers with good emulsification and dispersion effects in acidic and alkaline media were successfully prepared by RAFT polymerization. After neutralization, other monomers were polymerized to access cationic sizing emulsion (acid neutralization) and anionic sizing emulsion (alkali neutralization). The effects of bio‐based monomer content, hydrophilic monomer dimethylaminoethyl methacrylate (DM) content and degree of quaternization on the properties of sizing emulsion and sizing paper were further explored. In addition to the particle size and polymer dispersion index (PDI) of latex particles in different experimental groups, the water resistance, folding resistance, bursting strength, tensile strength and surface roughness of sized paper were analyzed and evaluated. Based on these results, a better sizing emulsion formulation was established. It was confirmed that the addition of bio‐based monomers can improve the sizing performance of paper.

Fiber Spinning of Polyacrylonitrile Terpolymers Containing Acrylic Acid and Alkyl Acrylates

Terpolymers of acrylonitrile with acrylic acid and alkyl acrylates, including methyl-, butyl-, 2-ethylhexyl-, and lauryl acrylates, were synthesized using the reversible addition–fragmentation chain transfer method. In this study, the focus was on the investigation of the impact of different monomer addition methods (continuous and batch) on both the rheological behavior of the spinning solutions and the mechanical properties of the resulting fibers. Our findings revealed that the method of monomer addition, leading either to non-uniform copolymers or to a uniform distribution, significantly influences the rheological properties of the concentrated solutions, surpassing the influence of the alkyl-acrylate nature alone. To determine the optimal spinning regime, we examined the morphology and mechanical properties at different stages of fiber spinning, considering spin-bond and orientation drawings. The fiber properties were found to be influenced by both the nature and introducing method of the alkyl-acrylate comonomer. Remarkably, the copolymer with methyl acrylate demonstrates the maximum drawing ratios and fiber tensile strength, reaching 1 GPa. Moreover, we discovered that continuous monomer addition allows for reaching the higher drawing ratios and superior fiber strength compared to the batch method.

Mechanism of sustainable photocatalysis based on doped-titanium dioxide nanoparticles for UV to visible light induced PET-RAFT photo-polymerization

Heterogeneous catalysis is an essential aspect for actual industrialization of chemical processes. Here a TiO2-based powder, typically used in photocatalysis, is exploited for the first time for visible-light-regulated Photoinduced Electron/Energy (PET)-reversible addition–fragmentation chain-transfer (RAFT). Titania is a non-toxic, low-cost, and heterogeneous catalyst that can offer several advantages in terms of sustainable polymerization and photocatalyst (PC) recovery. In this work, we aim not only at unraveling the mechanism of photopolymerization and the important interactions involved, but also at red-shifting the absorption region to achieve vis-light polymerization. The combination of the experimental investigation with Density Functional Theory (DFT) calculations provides new insights into the interactions between the chain transfer agents (CTAs) and the TiO2 surface, unveiling their pivotal role on the reaction rate and polymerization control. Moreover, to shift the polymerization under the less energetic blue light, high-surface area N-doped TiO2 nanoparticles are employed, avoiding the CTA degradation often observed with UV irradiation and increasing the overall sustainability of the process.

Synthesis and thermal behavior of RAFT-based copolymers of acrylonitrile and 1-vinylimidazole

The copolymers of acrylonitrile and 1-vinylimidazole with a narrow molecular weight distribution (MWD) were synthesized for the first time by the reversible addition–fragmentation chain transfer (RAFT) polymerization in a DMSO solution in the presence of acetic acid. Their thermal behavior difference upon heating in argon and in air along with ability to melt make them promising precursors for carbon fiber production.

Hydroxyapatite/hyperbranched polyitaconic acid/chitosan composite scaffold for bone tissue engineering

AbstractIn this study, a promising modified composite scaffold (hydroxyapatite/hyperbranched polyitaconic acid/chitosan) was synthesized for bone tissue engineering. Novel hyperbranched polyitaconic acid was prepared through the polymerization of itaconic acid using reversible addition fragmentation chain transfer using a macro‐RAFT agent. The chemical structure of the prepared hyperbranched polyitaconic acid was characterized by FTIR and 1HNMR and was subsequently embedded into hydroxyapatite/chitosan composite. The obtained modified composite scaffold was evaluated by characterizing its porosity, mechanical properties, bioactivity and cytotoxicity. The results showed that the modified composite scaffold had higher mechanical strength (i.e., 0.56 ± 0.03 MPa) in comparison to chitosan/hydroxyapatite scaffold only (i.e., 0.31 ± 0.01 MPa) and also showed higher bioactivity. In addition, the modified composite scaffold (HAP/HBP‐RAFT‐PI/CS) showed anticancer properties and enhanced human skin fibroblasts proliferation.

Polymeric Surfactants Bearing Divalent Carboxy Pendants for Stable Color Dispersions with High Redispersibility

Inkjet printing of ink requires dyes or pigments insoluble in water but uniformly dispersing as fine particles for a long period. In addition, redispersibility after solidification by solvent vaporization around the jetting heads is also important for performance. In this study, thus, a series of amphiphilic copolymers were prepared for a dispersant of inkjet using reversible addition fragmentation chain-transfer copolymerization of styrene (St), benzyl acrylate (BnA), and phenoxyethyl acrylate (PEA) as a hydrophobic monomer with acrylic acid (AA) and itaconic acid (IA) as a hydrophilic monomer. To understand the fundamental properties and potentials as a polymer dispersant, the surface parameters and rheology of the copolymers and their color dispersions in aqueous media were investigated. The aqueous solutions were typical Newtonian fluids, whereas the color dispersions were non-Newtonian fluids with shear-thinning properties and yield values ranging from 0.57 to 1.04 Pa. Although the surface parameters, such as surface tension (γ), molecular occupied area (Amin), and zeta potential (ζ), did not show clear correlation with polymer structures, their behaviors as a dispersant were significantly different. The color dispersants containing the copolymer of St or BnA as a hydrophobic monomer and IA and AMPS as hydrophilic monomers exhibited sufficient redispersion both for yellow and cyan inks, even after the aging test at 60 °C for 5 days, whereas other copolymers did not exhibit such superior performances. In addition, the color dispersions of the copolymer of St, IA, and AMPS (St-IA-AMPS) showed lower viscosity and yield value and became closer to Newtonian fluid compared with that of St, AA, and AMPS (St-AA-AMPS). Thus, St-IA-AMPS provided good redispersibility and avoided sedimentation. These results suggest that the most suitable dispersant for inkjet inks among the polymers investigated was the copolymer of St, IA, and AMPS.

Poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) Monoliths by Spinodal Decomposition for Hydrodynamic Chromatography

Porous materials with low tortuosities are needed when efficient liquid transport through a substrate is required. Thus, the development of materials with homogeneous interconnected pores can improve the performance of porous supports for flow-through applications. In this paper, the synthesis of a poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) monolith by spinodal decomposition is reported. The obtainment of experimental conditions for phase separation by spinodal decomposition was achieved by using a reversible addition–fragmentation chain transfer (RAFT) polymerization mechanism for the synthesis of porous monoliths. Moreover, the chemical nature and composition of the porogen mixture were found to be key factors in the porous structure of the resulting materials. Mixtures of poly(tert-butyl methacrylate) and dioxane were used as porogens for the obtainment of monoliths by spinodal decomposition, and the composition of the porogen mixture allowed control over their pore size. The obtained methacrylate monoliths were used as stationary phases for hydrodynamic chromatography and allowed size-based separations of high-molar-mass polymer standards.

The Parallel Structure-Activity Relationship Screening of Three Compounds Identifies the Common Agonist Pharmacophore of Pyrrolidine Bis-Cyclic Guanidine Melanocortin-3 Receptor (MC3R) Small-Molecule Ligands.

The melanocortin receptors are involved in numerous physiological pathways, including appetite, skin and hair pigmentation, and steroidogenesis. In particular, the melanocortin-3 receptor (MC3R) is involved in fat storage, food intake, and energy homeostasis. Small-molecule ligands developed for the MC3R may serve as therapeutic lead compounds for treating disease states of energy disequilibrium. Herein, three previously reported pyrrolidine bis-cyclic guanidine compounds with five sites for molecular diversity (R1-R5) were subjected to parallel structure-activity relationship studies to identify the common pharmacophore of this scaffold series required for full agonism at the MC3R. The R2, R3, and R5 positions were required for full MC3R efficacy, while truncation of either the R1 or R4 positions in all three compounds resulted in full MC3R agonists. Two additional fragments, featuring molecular weights below 300 Da, were also identified that possessed full agonist efficacy and micromolar potencies at the mMC5R. These SAR experiments may be useful in generating new small-molecule ligands and chemical probes for the melanocortin receptors to help elucidate their roles in vivo and as therapeutic lead compounds.

A smart material: Multi-stimulus-responsive composite microspheres prepared via RAFT polymerization as recyclable pickering emulsifiers and their application in stabilizing real oil phases

The development of smart composites to sustainably separate and recover oil from oily water had attracted much attention. In this study, tri-block (P(LMA-b-NIPAM-b-AA)) polymer brushes were controllably “grown on” the Fe3O4 surface by three-step surface-initiated reversible addition fragmentation chain transfer (SI-RAFT) polymerization to prepare Fe3O4-P(LMA-b-NIPAM-b-AA) (MNPLNA) magnetic nanospheres with interfacial activity. The MNPLNA nanospheres were characterized to demonstrate the triple response of pH, temperature and magnetism. Meanwhile, the comparison experiments showed that the MNPLNA nanospheres with tri-block structure had excellent interfacial activity. Then, the O/W type of Pickering emulsion was prepared by using MNPLNA nanospheres as the particle emulsifier. The size variation pattern of Pickering emulsion was comprehensively investigated by adjusting the concentration of nanospheres, oil-water ratio, electrolyte concentration and polarity of oil phase. Pickering emulsions were controllably separated by the action of an external magnetic field, and could be reversibly switched at least 10 cycles between emulsified and broken states under the trigger of pH and temperature. In addition, MNPLNA nanospheres exhibited excellent emulsification properties for stabilizing variety of real oil phases (e.g., canola oil, kerosene, diesel and crude oil). Based on this, MNPLNA nanospheres were applied as smart multifunctional materials in simulated kerosene-containing wastewater separation. MNPLNA nanospheres could be used to recover kerosene with high recovery rate after 10 separation cycles under the stepwise action of pH, temperature and magnetic field.

An In Vitro Comparison of Elastoplastic and Viscoelastic Behavior of Dental Composites with Reversible Addition–Fragmentation Chain Transfer-Mediated Polymerization

Reversible addition–fragmentation chain transfer (RAFT)-mediated polymerization has been implemented in commercially available bulk-fill dental composites, with the idea of either optimizing polymerization at depth, while providing sufficient opacity, or reducing exposure time. The elastoplastic and viscoelastic behavior of the materials pursuing both ideas are described comparatively in connection with the microstructure of the materials and artificial aging. A 3-point bending test was followed by reliability and fractographical analyses. The elastoplastic and viscoelastic behavior was monitored with an instrumented indentation test equipped with a DMA-module at various frequencies (0.5–5 Hz). Data reveal that the similarity in filler loading is reflected in similar elastic moduli. Increased strength was offset by higher plasticity and creep and was related to microstructure. Aging showed a significantly stronger influence on material behavior than differences in composition. The elastoplastic parameters of both materials deteriorate as a result of aging, but to a material-specific extent. Aging has a strong influence on elastic material behavior, but very little on viscous material behavior. The parameter that is most sensitive to aging is damping behavior. Detailed laboratory characterization indicates comparable in vitro behavior with clinically successful materials.

Crystal Structure of Poly(7-heptalactone)

The crystal structure of poly(7-heptalactone) (PHL) is presented. PHL has been synthesized by a combination of ring-opening polymerization of η-heptalactone and reversible addition–fragmentation chain transfer polymerization using diphenyl phosphate as catalyst. The noncommercial available η-heptalactone monomer has been prepared by oxidation of cycloheptanone. The crystal structure of PHL has been determined by analysis of the X-ray powder diffraction profiles and of the electron diffraction patterns of single crystals and calculations of lattice energy. The structure has been refined with the Rietveld full-profile refinement. Chains in trans planar conformation are packed in an orthorhombic unit cell with axes a = 7.37 Å, b = 5.05 Å, and c = 10.07 Å according to the space group symmetry P21.

Establishment of One-Pot Disulfide-Driven Cyclic Peptide Synthesis with a 3-Nitro-2-pyridinesulfenate.

We have developed a new one-pot disulfide-driven cyclic peptide synthesis. The entire process is carried out in the solid phase, thus eliminating complicated work up procedures to remove by-products and unreacted reagents and enabling production of high-purity cyclic disulfide peptides by simple cleavage of a peptidyl resin. The one-pot synthesis of oxytocin was accomplished in this way with an isolated yield of 28% over 13 steps. These include peptide chain elongation from an initial resin, sulfenylation of the protected side chain of a cysteine (Cys) residue, disulfide ligation between thiols in an additional peptide fragment and a 3-nitro-2-pyridinesulfenyl-protected cysteine (Cys(Npys))-containing peptide resin, subsequent intramolecular amide bond formation of the disulfide-connected fragments by an Ag+-promoted thioester method, followed by deprotection and HPLC purification.

A record of Late Jurassic vertebrates from Texas

ABSTRACT We present the first description of Jurassic vertebrate fossils from Texas. The vertebrate specimens were collected from the Upper Jurassic Malone Formation in the Malone Mountains of western Texas. The specimens are fragmentary and not particularly diagnostic, but probably represent elements of plesiosaurians. One specimen is similar to the caudal vertebra of a pliosaurid plesiosaurian, whereas another may be a partial propodial of a small plesiosaurian. Additional bone fragments are not identifiable at this time. These vertebrates were discovered along with abundant plant and invertebrate fossils. Previous studies of the invertebrate fossils indicate a Kimmeridgian to Tithonian age for the Malone Formation, which is consistent with a single grain age of 151±2 Ma from detrital zircon U–Pb geochronology obtained in this study. The Malone Formation was deposited in shallow marine to marginal marine environments along the northern edge of the Chihuahua trough. It is correlative with the La Casita and La Caja Formations of northern Mexico, where similar marine vertebrates have been reported. The Malone Formation is also correlative with the Morrison Formation to the north.

Development of analytical methods fort he quantitative analysis of the enzyme abundance and activity in the arachidonic acid cascade

The arachidonic acid (ARA) cascade is a key regulatory pathway where eicosanoids and other oxylipins are formed via the oxidation of polyunsaturated fatty acids. These oxylipins are involved in controlling physiological functions such as vascular tone, blood clotting and immune regulation. Changes in the oxylipin pattern can be caused by direct enzyme inhibition or modulated gene expression. In order to understand the effect mechanisms modulating the ARA cascade it is essential to not only investigate the metabolite, i.e. oxylipin, concentrations but also the abundances of the enzymes involved in their formation. For this reason, a quantitative targeted proteomics method for the ARA cascade was developed within this thesis.A detailed workflow for method development was established where enzyme/protein levels are measured via sequence‐specific, representative peptides chosen on the basis of several criteria. With liquid chromatography‐tandem mass spectrometry‐based analysis, the cyclooxygenase (COX) pathway of the ARA cascade was investigated in human colon carcinoma cell lines and primary macrophages where strong correlations were found between the oxylipins formed via the COX pathway and the COX‐2 abundance.The modulating effects of polyphenols on the 5‐lipoxygenase (LOX) pathway of the ARA cascade were investigated in cell‐free enzyme assays and human neutrophils. Resveratrol, its dimer ɛ‐viniferin and a resveratrol imine analogue directly inhibited the 5‐LOX with micromolar potencies and modulated the total oxylipin pattern in the neutrophils with remarkably different effects. Genistein did not act as a 5‐LOX inhibitor in the cell‐free assay but the modulated oxylipin pattern in the cells suggests a global cellular interference.The enzymes of the LOX pathway were included in the targeted proteomics method which together with an extended targeted oxylipin metabolomics platform enables a sensitive multi‐ omics analysis of the ARA cascade in a single sample. The comparison of the multiple reaction monitoring (MRM) detection and the MRM^‐based approach with an additional fragmentation step demonstrated that MRM is more favorable in targeted proteomics due to its higher sensitivity, greater linear range and higher multiplexing capacities. The analysis with the multi‐ omics approach showed that the 5 LOX protein is induced together with its product formation during the differentiation of human monocytic THP 1 cells to macrophages. M1‐like human primary macrophages were also characterized by the abundance of 5‐LOX and its activating protein (FLAP), while 15‐LOX and 15‐LOX‐2 dominated the protein pattern of the M2 like macrophages accompanied by high levels of the oxylipins formed via these enzymes. The developed methodology allows mechanistic investigation of a modulation of the ARA cascade as demonstrated by lipo‐poly‐saccharide stimulation as well as pharmaceutical treatment of the cells.Overall, with this thesis, a new quantitative proteomics strategy for the enzymes of the ARA cascade is established which can be easily extended to further proteins. The use of this technique in combination with targeted oxylipin metabolomics has provided new insights into the mechanisms involved in the modulation of the ARA cascade in human immune cells.

Synthesis of Hydrophobic Block Copolymer Nanoparticles in Alcohol/Water Stabilized by Poly(methyl methacrylate) via RAFT Dispersion Polymerization-Induced Self-Assembly

Poly(methyl methacrylate) (PMMA) is an important common polymer widely used in industry. While PMMA has been used as a core-forming block for polymerization-induced self-assembly (PISA), a powerful approach for the synthesis of block copolymer nanoparticles, it has not been utilized as a corona block due to PMMA being insoluble in common solvents for PISA formulations (e.g., water and alcohols). Exploiting the solubility of PMMA-dithiobenzoate (DTB) in ethanol/water mixtures, such macroRAFT agents have in the present work been successfully employed for reversible addition–fragmentation chain transfer (RAFT) PISA in ethanol/water (80/20 by volume). RAFT dispersion polymerization of benzyl methacrylate mediated by PMMA-DTB macroRAFT agents with various degrees of polymerization has been investigated. Transmission electron microscopy analyses revealed well-defined block copolymer nano-objects, including spheres, worms, as well as vesicles. Nanoparticles comprising a PMMA outer layer would have superior compatibility with various hydrophobic polymer matrices, thereby enabling various new applications such as, e.g., use as nanofillers.

Novel Multi-Responsive Hyperbranched Polyelectrolyte Polyplexes as Potential Gene Delivery Vectors.

In this work, we investigate the complexation behavior of poly(oligo(ethylene glycol)methyl methacrylate)-co-poly(2-(diisopropylamino)ethyl methacrylate), P(OEGMA-co-DIPAEMA), hyperbranched polyelectrolyte copolymers, synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization, with short-linear DNA molecules. The synthesized hyperbranched copolymers (HBC), having a different chemical composition, are prepared in order to study their ability to bind with a linear nucleic acid at various N/P ratios (amine over phosphate groups). Specifically, the three pH and thermo-responsive P(OEGMA-co-DIPAEMA) hyperbranched copolymers were able to form polyplexes with DNA, with dimensions in the nanoscale. Using several physicochemical methods, such as dynamic and electrophoretic light scattering (DLS, ELS), as well as fluorescence spectroscopy (FS), the complexation process and the properties of formed polyplexes were explored in response to physical and chemical stimuli such as temperature, pH, and ionic strength. The mass and the size of polyplexes are shown to be affected by the hydrophobicity of the copolymer utilized each time, as well as the N/P ratio. Additionally, the stability of polyplexes in the presence of serum proteins is found to be excellent. Finally, the multi-responsive hyperbranched copolymers were evaluated regarding their cytotoxicity via in vitro experiments on HEK 293 non-cancerous cell lines and found to be sufficiently non-toxic. Based on our results, these polyplexes could be useful candidates for gene delivery and related biomedical applications.

D–A Conjugated Organic Polymers as Nonhomogeneous Photocatalysts for PET-RAFT Polymerization

D–A conjugated organic polymer (COP) photocatalysts are a very promising photocatalytic material because of their tunable structure at the molecular level and diverse species. D–A conjugated organic polymers composed of relatively weak donor units and strong acceptor units are more favorable for photogenerated charge migration and thus exhibit better photocatalytic activity. Herein, a series of D–A conjugated organic polymers were constructed by introducing CN-absorbing groups to the benzene ring using 1,3,5-triethynylbenzene as the donor unit and the benzene ring as the acceptor unit to catalyze the reversible addition–fragmentation chain transfer (RAFT) polymerization of methyl methacrylate under white light irradiation, and the resulting polymers had controlled molecular weight and narrow molecular weight distribution. The effect of increasing the number of CN groups on the photogenerated charge migration ability of the catalyst and the RAFT polymerization rate was investigated by both experiments and theoretical calculation to reveal the conformational relationship between the polymer structure and the photocatalytic RAFT polymerization rate. It is proved that D–A conjugated organic polymers composed of relatively weak donor units and strong acceptor units are more favorable for photogenerated charge migration and thus exhibit better photocatalytic activity.

Intertextuality and Its Different Facets in the Narrative Analysis of the Book of Esther and 3 Maccabees

While the interpretation of the book of Esther has posed many challenges in the past, a key and well-recognized aspect of this text is that it presents a narrative behind one of the most important Jewish holidays, namely, Purim. As such, it also strongly influenced Jewish culture, including similar texts written to cultivate Jewish traditions in the diaspora. In this article, an analysis of possible intertextual connections between Esther and the apocryphal book of 3 Maccabees is presented. The latter was likely written for Jews living in Alexandria. While this topic has been studied in the past by several authors, in this article emphasis is laid on narrative similarity between both books. In particular, five key elements of this similarity have been identified, and additional parallel fragments have been presented. Their distribution and their likely origin from different versions of the book of Esther support claims about the possible origin of 3 Maccabees from a mature version of Esther.

Character evolution of modern eupolypods supports the assignment of the fossil fern Cretacifilix fungiformis to Dryopteridaceae

The fossil fern species Cretacifilix fungiformis from mid-Cretaceous Kachin amber from Myanmar was previously assigned to eupolypod ferns for having sporangia with a vertical annulus and sporangial stalks 2–3 cells thick, along with monolete spores with a distinct perine. However, due to the insufficient documentation of character states and the unavailability of the holotype, the proposed affiliation of this fossil to derived families of eupolypods required further study. The recent discovery of additional leaf fragments of C. fungiformis from the same amber deposit enabled us to re-evaluate the relationships of this fossil taxon. Newly documented morphological evidence corroborated its placement within the eupolypod ferns. This was achieved by evaluating identifiable features present in the fossil species through an ancestral character state reconstruction utilizing a comprehensive, time-calibrated phylogeny of eupolypod ferns. Our character state reconstruction of extant eupolypod families and genera recovered morphological similarity of Cretacifilix to the closely related genera Arachniodes and Dryopteris, supporting an assignment of this fossil genus to the species-rich family Dryopteridaceae within the Polypodiineae.

RAFT Polymerisation and Hypercrosslinking Improve Crosslink Homogeneity and Surface Area of Styrene Based PolyHIPEs.

The influence of a polymerisation mechanism (reversible addition-fragmentation chain transfer; RAFT vs. free radical polymerisation; FRP) on the porous structure of highly porous poly(styrene-co-divinylbenzene) polymers was investigated. The highly porous polymers were synthesised via high internal phase emulsion templating (polymerizing the continuous phase of a high internal phase emulsion), utilising either FRP or RAFT processes. Furthermore, residual vinyl groups in the polymer chains were used for the subsequent crosslinking (hypercrosslinking) applying di-tert-butyl peroxide as the source of radicals. A significant difference in the specific surface area of polymers prepared by FRP (between 20 and 35 m2/g) and samples prepared by RAFT polymerisation (between 60 and 150 m2/g) was found. Based on the results from gas adsorption and solid state NMR, it could be concluded that the RAFT polymerisation affects the homogeneous distribution of the crosslinks in the highly crosslinked styrene-co-divinylbenzene polymer network. During the initial crosslinking, RAFT polymerisation leads to the increase in mesopores with diameters between 2 and 20 nm, resulting in good accessibility of polymer chains during the hypercrosslinking reaction, which is reflected in increased microporosity. The fraction of micropores created during the hypercrosslinking of polymers prepared via RAFT is around 10% of the total pore volume, which is up to 10 times more than for polymers prepared by FRP. Specific surface area, mesopore surface area, and total pore volume after hypercrosslinking reach almost the same values, regardless of the initial crosslinking. The degree of hypercrosslinking was confirmed by determination of the remaining double bonds by solid-state NMR analysis.