Post Polymerization Research Articles

Light-matter interaction during and post polymerization in self-written polymer waveguide integrated with optical fibers

Self-written polymer waveguide is a polymer interconnection structure often integrated with optical fibers. The structure is fabricated by photopolymerization, through which a photon beam initiates a polymerization reaction to change liquid monomer into a solid polymer. During light-matter interaction photoinitiator molecules are excited to the singlet and then to the third state to form free radicals by attaching to the adjacent monomer molecules. The free radicals in turn form polymer chains and cross-linked structures. Photo-induced polymerization leads to a raised refractive index of the monomer and forms an optical waveguide. The change is permanent to allow the process of self-focusing and self-trapping of the propagation light beam and hence guide it to the aligned optical fiber. In this article, light matter interaction during polymer waveguide fabrication and post polymerization has been investigated. A photopolymer system of acrylate-based monomer, co-initiator amine and photo initiator is used to study the absorption of the monomer mixture at the spectral range of 450–550 nm. Then photobleaching was investigated after waveguide fabrication. The optical transmission efficiency of the polymer bridge increases as absorption ceases within the polymer structure such that optical loss reduces from 1.1 dB to about 0.65 dB.

Surface mannosylation of dispersion polymerisation derived nanoparticles by copper mediated click chemistry

Spherical polymer particles with alkyne functionalities were obtained by polymerisation induced self-assembly using Cu(0) mediated radical polymerisation. Mannosylation by click reaction produced cyto-compatible lectin binding nanoparticles.

Fabrication of GSH‐Responsive Poly(Tertiary Amine‐Oxide)‐Based Nanomedicines for Enhanced Anticancer Drug Release

AbstractPoly(tertiary amine‐oxide)‐based polymeric nanocarriers have showed more functionalities than stealthy PEG‐based analogs due to the structure of phospholipid affinitive N‐oxides groups, which has attracted considerable attention to the synthesis of various zwitterionic copolymers with tertiary amine‐oxide grafts for enhanced anticancer drug delivery. However, poly(tertiary amine‐oxide)‐based amphiphilic copolymers with tumor intracellular microenvironment sensitivities, to the knowledge, have been rarely reported likely due to the lack of a controlled synthetic strategy. Herein, a reducible zwitterionic copolymer, poly(ε‐caprolactone)25‐SS‐poly(2‐(N‐oxide‐N,N‐diethylamino)ethyl methacrylate)30 (PCL25‐SS‐OPDEA30) is designed and synthesized successfully via combination of controlled polymerization techniques and post polymerization modification. Specifically, postoxidation of poly(tertiary amine) is confirmed to be a better synthetic strategy toward a well‐defined polymer structure relative to direct polymerization of N,N‐diethylaminoethyl methacrylate (ODEA). The effect of disulfide bridges on the self‐assembly behaviors, in vitro drug loading and drug release properties is investigated in detail. Notablely, the resulting micelles self‐assembled from PCL25‐SS‐OPDEA30 show much greater colloidal stability, higher drug loading content (DLC), and better in vitro tumor cell inhibition than the reduction‐insensitive counterparts. Overall, this study reports a robust strategy toward zwitterionic nanomedicines for on‐demand anticancer drug delivery.

The Rapid Mechanochemical Synthesis of Microporous Covalent Triazine Networks: Elucidating the Role of Chlorinated Linkers by a Solvent‐Free Approach

AbstractThe mechanochemical synthesis of porous covalent triazine networks (CTNs), exhibiting theoretically ideal C/N ratios and high specific surface areas, is presented. Employing this solvent‐free approach allows to minimize the ecological impact of the synthesis by bypassing hazardous wastes, while simultaneously observing the reactions between the individual starting materials separately for the first time. Especially the role of dichloromethane needs to be reconsidered, functioning as a linker between the nitrogen‐containing node cyanuric chloride and the aromatic monomer 1,3,5‐triphenylbenzene, as proven by X‐ray photoelectron spectroscopy and 1H → 13C Cross‐Polarization magic‐angle‐spinning nuclear magnetic resonance spectroscopy. This results in a drastic enhancement of the reaction rate, reducing the synthesis time down to 1 minute. Additionally, this linkage over a C1 bridge enables the incorporation of nitrogen into already synthesized polymers by post polymerization functionalization. The variation of the synthesis building blocks, namely the linker, node, and monomer, results in a variety of nitrogen‐containing polymers with specific surface areas of up to 1500 m2 g−1. Therefore, the presented approach is capable to target the synthesis of various CTNs with a minimal use of chlorinated linker, rendering the concept as a sustainable alternative to the classical solution‐based synthesis.

Construction of ternary mixture of long-chain acrylates for lower-temperature and higher-effect rotator phase photopolymerization

Low-temperature rotator phase photopolymerization is meeting great challenges due to the polymerization can’t occur after the rotator phase transform into crystalline phase, thus lower transition temperature between these two phases (TC-R) is needed. In this work, ternary mixture of hexadecyl acrylate (HDA), tetradecyl acrylate (TDA) and dodecyl acrylate (DDA) was constructed by drawing on the experiences of previous binary mixtures. Since the advantages of each component were combined, the mixture was proved possessing stable rotator phase, and the TC-R of the mixture achieved −38.11℃, which was 9.14℃ lower than the previous binary mixtures of octadecyl acrylate (ODA) and TDA. The photopolymerization kinetic of ternary mixture was investigated, which showed efficient photopolymerization at −30℃, moreover, the conversions between −25℃∼-15℃ were 6 %∼12 % higher than those of the binary mixture of ODA/TDA. In addition, it was found that the rotator phase photopolymerization of ternary mixture showed the properties similar to living polymerization, which performed post polymerization to realize complete conversion of monomers. Meanwhile, the feature of post polymerization demonstrated that besides TC-R, the spatial distance between adjacent monomers also significantly affect the conversion in rotator phase.

Electro-stimulated drug release by methacrylated hyaluronic acid-based conductive hydrogel with enhanced mechanical properties

Recently, the design of stimuli-responsive hydrogels for controlled drug delivery systems has been extensively investigated to meet therapeutic needs and optimize the release pattern of the drug. Being a natural polyelectrolyte, hyaluronic acid (HA) is excellent potential to generate new opportunities for electro-responsive drug carrier applications. In the current study, HA-based electroconductive hydrogel was developed as a novel smart drug carrier for anti-inflammatory drug release by the combination of in-situ and post polymerization mechanisms. HA was modified through methacrylation reaction to introduce photocrosslinkable groups into its structure and then reduced graphene oxide (rGO) was encapsulated into methacrylated HA (HA/MA) hydrogel by using the photopolymerization technique. In the post polymerization process, polyaniline (PANI) was incorporated/loaded into HA/MA-rGO polymeric network produced in previous step. The produced HA/MA-rGO-PANI hydrogel exhibited sufficient electrical conductivity providing the desirable electro-responsive ability for Ibuprofen (IBU) release. Furthermore, it has superior mechanical performance compared to pure (HA/MA) and rGO containing (HA/MA-rGO) hydrogels. IBU release from the hydrogel was successfully triggered by electrical stimulation and the cumulative drug release also enhanced by increasing of the applied voltage. These results highlighted that the novel HA/MA-rGO-PANI hydrogel could be a promising candidate for electrical-stimulated anti-inflammatory release systems in neural implant applications.

Poly(carboxyethyl acrylate-co-ethylene glycol dimethacrylate) precursor monolith with bonded (S)-(-)-1-(2-naphthyl) ethylamine ligands for use in chiral and achiral separations by capillary electrochromatography

In this research report, the previously developed poly(carboxyethyl acrylate-co-ethylene glycol dimethacrylate) precursor monolith (referred to as carboxy monolith) is further exploited in the preparation of a chiral stationary phase for enantiomeric separations. The carboxy monolith precursor was subjected to post polymerization functionalization (PPF) with the chiral selector (S)-(-)-1-(2-naphthyl) ethylamine (NAS) at room temperature in the presence of N, N´-dicyclohexylcarbodiimide (DCC) in chloroform. The DCC, which is an organic soluble carbodiimide, permits the linkage for the amine functionality of the chiral ligand NAS to the carboxy group of the monolithic surface forming a stable amide linkage. The NAS column thus obtained allowed not only enantiomeric separations in the RP mode via its chiral site but also the separation of nonpolar species via its achiral functionality offering both hydrophobic and π-π interactions for aromatic compounds such toluene derivatives and polyaromatic hydrocarbons. The dual interaction sites (e.g., chiral, and achiral) of the NAS present a convenient column for the separations of slightly polar and nonpolar chiral and achiral solutes in the RP mode.

A Precision Polyanion for High Performance Lithium-Ion Transport in Polymer Blend Electrolytes

A novel precision single ion conductor with an N-((trifluoromethyl)sulfonyl)phenylsulfonimide lithium salt covalently bound to every fifth carbon of a polyethylene backbone, p5PhTFSI-Li, was synthesized via post polymerization modification. The conversion to a trifluoromethanesulfonimide (TFSI) anion from the parent polymer bearing a phenylsulfonate anion was highly efficient (~90%) as determined by 19F-NMR analysis and corroborated through other spectroscopic methods. The bulky and flexible TFSI anion led to a reduced and observable glass transition temperature of ~199 °C and an improved thermal stability up to ~375 °C. Blending of p5PhTFSI-Li with poly(ethylene oxide) at various compositions was performed to investigate electrochemical performance and transference numbers with respect to the lithium electrode using a combination of impedance and polarization methods. At 90 °C, this system displayed high conductivity up to 2.00 X 10-4 S cm-1 and transference numbers were near unity independent of temperature, making this system highly competitive with other polyanion/polyether blend electrolytes. Investigations into the complex miscibility and phase behavior of these blends at various compositions was also probed by a combination of microscopy and differential scanning calorimetry.

Poly(carboxyethyl acrylate-co-ethylene glycol dimethacrylate) precursor monolith with bonded anthracenyl ligands for use in reversed-phase capillary electrochromatography based on hydrophobic and π-π interactions

In this research report, the post polymerization functionalization (PPF) of a carboxyethyl acrylate (CEA)-co-ethylene glycol dimethacrylate (EDMA) [poly-CEA-co-EDMA)] precursor monolith with 2-aminoanthracene was carried out in the presence of an organic solvent soluble carbodiimide, namely N,N´-dicyclohexylcarbodiimide (DCC), yielding the so-called anthracenyl-poly-CEA-co-EDMA monolith. This novel monolith proved to be an excellent monolithic stationary for reversed-phase capillary electrochromatography (RP-CEC) with hydrophobic and π-π interactions of a wide range of nonpolar solutes including those bearing aryl functional groups in their structures such as polycyclic aromatic hydrocarbons (PAHs), toluene derivatives and aniline derivatives as well as solutes carrying in their structures electron withdrawing substituents such as dinitrophenyl-amino acids (DNP-AAs) and di-DNP-AAs. The retention behaviors of the just mentioned solutes obtained on the anthracenyl-poly-CEA-co-EDMA monolithic column were compared to those obtained on octadecyl-poly-CEA-co-EDMA monolithic column prepared from the same carboxy-precursor monolith. The results demonstrated the superiority of anthracenyl column over the octadecyl column for the separation and enhanced selectivity for aromatic solutes since it provides not only hydrophobic interactions but also π-π interactions with aromatic nonpolar solutes.

PLA‐b‐SMA as an Amphiphilic Diblock Copolymer for Encapsulation of Lipophilic Cargo

AbstractThe encapsulation of active pharmaceutical ingredients (APIs) within drug delivery systems such as polymeric nanoparticles (PNPs) vastly improves the therapeutic efficiency of the incorporated APIs. PNPs synthesized using amphiphilic block copolymers are efficient drug delivery systems as the hydrophobic block facilitates the encapsulation of lipophilic components and the hydrophilic block constitutes the hairy corona of the PNP that stabilizes the nanocarriers against aggregation in solution. Poly(styrene‐alt‐maleic acid) (SMA) is an attractive polymer for the hydrophilic corona of PLA‐based nanoparticles as it allows for post polymerization functionalization and aids in the prevention of NP aggregation. The synthesis of a novel PLA‐b‐SMA block copolymer, via sequential ring opening polymerization (ROP) and reversible addition–fragmentation chain transfer (RAFT) polymerization, is presented. PLA macro‐CTAs, synthesized via ROP, can be chain extended via RAFT copolymerization of styrene and maleic anhydride to yield PLA‐b‐SMAnh and via RAFT polymerization of N‐vinylpyrrolidone to yield PLA‐b‐PVP block copolymers. Controlled hydrolysis of the anhydride moieties converts PLA‐b‐SMAnh into PLA‐b‐SMA. Monodisperse PLA‐b‐SMA and PLA‐b‐PVP nanoparticles (NPs) ranging in diameter between 60 and 220 nm are prepared. The lipophilic fluorescent dye DiI is encapsulated within the NPs successfully and these fluorescent NPs are used in a preliminary cell uptake study.

Cytotoxicity of printed resin-based splint materials

ObjectivesPrinted splints may be an alternative as a treatment of functional disorders in addition to physical, manual and physiological therapeutics. The objective is to investigate whether different 3D printed splint materials, which are fabricated with different fabrication orientation and post-processing (washing and post polymerisation) exhibit different in vitro cytotoxicity. Material and Methods600 discs (n = 25 per group, 5mmx1mm) were printed (P30+ DLP-printer, Straumann, CH; 100 µm layer) from splint materials (M1: Luxaprint OrthoPlus, DMG, G; M2: V-Print Splint, Voco, G). Printing was performed under 90° (A1), 45° (A2) or 0° (A3) alignment to the building platform. Specimens were either automatically washed (W1) (Straumann P Wash, Straumann, CH) or manually cleaned (W2) (Voco Pre-/Main-Clean protocol, Voco, G), and post polymerization was performed (P1: Cure, Straumann, CH; P2: Otoflash N171, Ernst Hinrichs Dental, G). RAW264.7 mouse macrophages were exposed to extracts of the specimens and cytotoxicity was determined as cell survival using a crystal violet assay. Optical density values obtained from exposed cell cultures were normalized to untreated controls (100%), summarized as means and statistically analyzed (ANOVA, α=0.05). ResultsCell survival varied between 9.1+/-1.3% (alignment A2/post cure P2/material M2/wash system W2) and 58.5+/-5.9% (alignment A1/post cure P1/material M1/wash system W1). Univariate analysis of variance revealed significant differences between mean values for post cure (p = 0.000), wash system (p = 0.002) and materials (p = 0.000), but not for the alignment (p = 0.406). With standardised washing and adapted post cure, both tested materials provided lowest cytotoxicity even in all three printing alignments. ConclusionsThe selection of the material as well as the post-processing (post-polymerization, washing procedure) show influence on the in vitro cytotoxicity. Alignment during manufacturing does not affect toxicity. Clinical RelevanceMaterials, washing and post-polymerization should be matched to reduce cytotoxic effects during additive manufacturing.

The mechanochemical Friedel‐Crafts polymerization as a solvent‐free cross‐linking approach toward microporous polymers

AbstractHerein we report the mechanochemical Friedel‐Crafts alkylation of 1,3,5‐triphenylbenzene (TPB) with two organochloride cross‐linking agents, dichloromethane (DCM) and chloroform (CHCl3), respectively. During a thorough milling parameter evaluation, the DCM‐linked polymers were found to be flexible and extremely sensitive toward parameter changes, which even enables the synthesis of a polymer with a SSABET of 1670 m2/g, on par with the solution‐based reference. Contrary, CHCl3‐linked polymers are exhibiting a rigid structure, with a high porosity that is widely unaffected by parameter changes. As a result, a polymer with a SSABET of 1280 m2/g could be generated in as little as 30 minutes, outperforming the reported literature analogue in terms of synthesis time and SSABET. To underline the environmental benefits of our fast and solvent‐free synthesis approach, the green metrics are discussed, revealing an enhancement of the mass intensity, mass productivity and the E‐factor, as well as of synthesis time and the work‐up in comparison to the classical synthesis. Therefore, the mechanochemical polymerization is presented as a versatile tool, enabling the generation of highly porous polymers within short reaction times, with a minimal use of chlorinated cross‐linker and with the possibility of a post polymerization modification.

A bi-functional polymeric coating for the co-immobilization of proteins and peptides on microarray substrates

The analytical performance of the microarray technique in screening the affinity and reactivity of molecules towards a specific target, is highly affected by the coupling chemistry adopted to bind probes to the surface. However, the surface functionality limits the biomolecules that can be attached to the surface to a single type of molecule, thus forcing the execution of separate analyses to compare the performance of different species in recognizing their targets. Here we introduce a new N, N-dimethylacrylamide-based polymeric coating, bearing simultaneously different functionalities (N-acryloyloxysuccinimide and azide groups) to allow an easy and straightforward method to co-immobilize proteins and oriented peptides on the same substrate. The bi-functional copolymer has been obtained by partial post polymerization modification of the functional groups of a common precursor. A NMR characterization of the copolymer was conducted to quantify the percentage of NAS that has been transformed into azido groups. The polymer was used to coat surfaces onto which both native antibodies and alkyne modified peptides were immobilized, to perform the phenotype characterization of extracellular vesicles (EVs). This strategy represents a convenient method to reduce the number of analysis, thus possible systematic or random errors, besides offering a drastic shortage in time, reagents and costs.

Facile Synthesis of Novel Polyethyleneimine Functionalized Polymeric Protic Ionic Liquids (PolyE‐ILs) with Protagonist Properties for Acid Catalysis

AbstractPolyethyleneimine (PEI), a potent architecture backbone was explored for the synthesis of novel polymeric ionic liquids (PolyE‐ILs) with protagonist properties. The simple quaternization of PEI dendrimer with Bronsted acids (H2SO4, H3PO4, CH3SO3H, CF3COOH and TsOH) leads to formation of series of protic PolyE‐ILs with corresponding counter anions [HSO4]−, [H2PO4]−, [CH3SO3]−, [CF3COO]− and [TsO]−. The physicochemical properties of synthesized PolyE‐ILs were studied by using TGA, Hammett acidity, hydrodynamic radii, solubility, and elemental analysis. PolyE‐ILs showed characteristic Hammett acidity (0.94–1.78), good thermal stability (<250 °C) and enhanced hydrodynamic radii. However, use of PolyE‐IL can be promoted for their wide applications as an acid catalysts. The reported PolyE‐IL‐1 with sulfonic acid counter ion was explored as catalyst for esterification of (E)‐cinnamic acids and it showed good catalytic activity. The enhanced hydrodynamic radii due to the branched architecture of PEI dendrimers facilities the separation process via Nanofiltration (NF) membrane with no membrane fouling. Thus, PolyE‐ILs can be highly active, easily recoverable, and reusable catalyst for esterification reactions with superior sustainability and economics. In addition to this the present one pot PolyE‐IL synthesis process is non‐complex and simple as compared to conventional post polymerization, ion exchange, and nucleophilic addition etc., strategies for synthesis of PILs.

Shear Bond Strength of a Multi-Mode Universal Adhesive Containing Hydroxy-Apatite Nanoparticles to Dentin (In vitro study)

Aim: To evaluate the effect of addition of Hydroxyl-Apatite nanoparticles to a commercial universal adhesive on sheer-bond-strength to dentin using two application modes, immediately and after thermocycling. Methods: A-commercial UA was used for bonding composite-resin to dentin and considered as control. 10% of HAp were prepared and added to the commercial UA and considered as experimental. 88-freshly extracted sound human premolar teeth were sectioned to expose mid-coronal-dentin. Samples were y divided into: control and experimental group. Each group was further divided based on the application protocol. Half of the samples were stored in distilled water for 24h at 37°C for immediate SBS testing whereas the other half was subjected to thermocycling for 20,000 cycles. SBS was measured one-day post polymerization and after thermocycling using universal testing machine. SBS values and failure modes were recorded and statistically analyzed. Results: the experimental group presented significantly lower resin-dentin SBS than the control group. Thermocycling significantly lowered SBS values for both groups. When using SE mode, the experimental group reported lower resin-dentin SBS than the control group before and after thermocyclying. When using ER mode before thermocycling, no significant difference was found between the two groups, while after thermocycling, the experimental group reported significantly higher resin-dentin SBS than the control group. For both adhesive groups, mixed failure dominated with ER mode while adhesive failure dominated with SE mode. Conclusions:Addition of HA may provide resistance to degradation and offer a potential to improve resin-dentin bond stability against thermal changes when ER protocol is applied.

High sensitivity analysis of nanogram quantities of glycosaminoglycans using ToF-SIMS

Glycosaminoglycans (GAGs) are important biopolymers that differ in the sequence of saccharide units and in post polymerisation alterations at various positions, making these complex molecules challenging to analyse. Here we describe an approach that enables small quantities (<200 ng) of over 400 different GAGs to be analysed within a short time frame (3–4 h). Time of flight secondary ion mass spectrometry (ToF-SIMS) together with multivariate analysis is used to analyse the entire set of GAG samples. Resultant spectra are derived from the whole molecules and do not require pre-digestion. All 6 possible GAG types are successfully discriminated, both alone and in the presence of fibronectin. We also distinguish between pharmaceutical grade heparin, derived from different animal species and from different suppliers, to a sensitivity as low as 0.001 wt%. This approach is likely to be highly beneficial in the quality control of GAGs produced for therapeutic applications and for characterising GAGs within biomaterials or from in vitro cell culture.

Poly(2-ethyl-2-oxazoline) Featuring a Central Amino Moiety.

The incorporation of an amino group into a bifunctional initiator for the cationic ring-opening polymerization (CROP) is achieved in a two-step reaction. Detailed kinetic studies using 2-ethyl-2-oxazoline demonstrate the initiators' eligibility for the CROP yielding well-defined polymers featuring molar masses of about 2000g mol-1 . Deprotection of the phthalimide moiety subsequent to polymerization enables the introduction of a cyclooctyne group in central position of the polymer which is further exploited in a strain-promoted alkyne-azide click reaction (SpAAC) with a Fmoc-protected azido lysine representing a commonly used binding motif for site specific polymer-protein/peptide conjugation. In-depth characterization via electrospray ionization mass spectrometry (ESI) confirms the success of all post polymerization modification steps.

Modelling Sorption Thermodynamics and Mass Transport of n-Hexane in a Propylene-Ethylene Elastomer.

Optimization of post polymerization processes of polyolefin elastomers (POE) involving solvents is of considerable industrial interest. To this aim, experimental determination and theoretical interpretation of the thermodynamics and mass transport properties of POE-solvent mixtures is relevant. Sorption behavior of n-hexane vapor in a commercial propylene-ethylene elastomer (V8880 VistamaxxTM from ExxonMobil, Machelen, Belgium) is addressed here, determining experimentally the sorption isotherms at temperatures ranging from 115 to 140 °C and pressure values of n-hexane vapor up to 1 atm. Sorption isotherms have been interpreted using a Non Random Lattice Fluid (NRLF) Equation of State model retrieving, from data fitting, the value of the binary interaction parameter for the n-hexane/V8880 system. Both the cases of temperature-independent and of temperature-dependent binary interaction parameter have been considered. Sorption kinetics was also investigated at different pressures and has been interpreted using a Fick’s model determining values of the mutual diffusivity as a function of temperature and of n-hexane/V8880 mixture composition. From these values, n-hexane intra-diffusion coefficient has been calculated interpreting its dependence on mixture concentration and temperature by a semi-empiric model based on free volume arguments.

Dynamic covalent chemistry for architecture changing interpenetrated and single networks

Dynamic single and interpenetrated materials were developed, with post polymerization network exchange enhancing the material properties.

Controlling the biodegradation rates of poly(globalide-co-ε-caprolactone) copolymers by post polymerization modification

Controlling the degradation rates of polymers is crucial for their application in tissue engineering or to achieve degradation of the polymers in the wastewater purification. As hydrophobic polyesters often exhibit very slow degradation rates, we report here increased biodegradation rates of poly(globalide-co-ε-caprolactone) copolymers (PGlCL) produced by enzymatic ring-opening copolymerization and post-functionalized with N-acetylcysteine by thiol-ene reaction. The degradation rates of the PGlCL and post-modified PGlCL-NAC films were determined by weight-loss experiments. The polymer films were immersed in phosphate-buffered saline (PBS) solution, and PBS containing lipase from Pseudomonas cepacia. The degree of functionalization affected the degradation behavior, and samples with a higher degree of functionalization presented higher weight loss. Finally, a degradation assay was performed in activated sludge, and PGlCL-NAC presented high degradability, having a degradation behavior similar to starch. Density Functional Theory (DFT) calculations were used to assess the changes in chemical properties and electronic charge distribution of PGlCL after its functionalization with NAC, helping to understand its influence in their degradability. The results obtained confirm the possibility to increase the degradation rates of copolyesters based on caprolactone and globalide by thiol-ene post-functionalization, being a promising alternative for applications in biomedicine or the packaging sector.