Oligo Ethylene Oxide Research Articles

Mechanical properties of co-continuous network polymers packed with thiol-ene thermosets in epoxy monolith

Co-continuous network polymers (CNPs) as the new polymer composites are fabricated by filling the continuous pores of an epoxy monolith with a high glass transition temperature (Tg) using another kind of network polymer with a low Tg. In this study, we prepared sheet-like and cylindrical CNPs using thiol–ene thermosets as the second component with a low Tg. A thiol–ene reaction is suitable for the preparation of thermosets with a controlled network structure. Here, various thiols and acrylates including the different numbers of functional groups and/or oligo(ethylene oxide) spacers with different lengths are used for the fabrication of the second thermosetting component. We investigated the tensile and compression mechanical properties of the produced CNPs. Dynamic mechanical analysis (DMA) of the thiol–ene bulk thermosets (BTs) as the second component was also carried out in order to clarify the influence of the Tg and the crosslinking density on the mechanical and physical properties of the CNPs. The results of the mechanical tests were discussed on the functionality of the used acrylate and thiol compounds. In conclusion, we have revealed that the properties of CNPs are not only dependent on the crosslinking density, but also significantly affected by the detailed network structure of the second component.

Hydrophilic Poly(meth)acrylates by Controlled Radical Branching Polymerization: Hyperbranching and Fragmentation.

Topology significantly impacts polymer properties and applications. Hyperbranched polymers (HBPs) synthesized via atom transfer radical polymerization (ATRP) using inimers typically exhibit broad molecular weight distributions and limited control over branching. Alternatively, copolymerization of inibramers (IB), such as α-chloro/bromo acrylates with vinyl monomers, yields HBPs with precise and uniform branching. Herein, we described the synthesis of hydrophilic HB polyacrylates in water by copolymerizing a water-soluble IB, oligo(ethylene oxide) methyl ether 2-bromoacrylate (OEOBA), with various hydrophilic acrylate comonomers. Visible-light-mediated controlled radical branching polymerization (CRBP) with dual catalysis using eosin Y (EY) and copper complexes resulted in HBPs with various molecular weights (M n = 38 000 to 170 000) and degrees of branching (2%-24%). Furthermore, the optimized conditions enabled the successful application of the OEOBA to synthesize linear-hyperbranched block copolymers and hyperbranched polymer protein hybrids (HB-PPH), demonstrating its potential to advance the synthesis of complex macromolecular architecture under environmentally benign conditions. Copolymerization of hydrophilic methacrylate monomer, oligo(ethylene oxide) methyl ether methacrylate (OEOMA500), and inibramer OEOBA was accompanied by fragmentation via β-carbon C-C bond scission and subsequent growth of polymer chains from the fragments. Furthermore, computational studies investigating the fragmentation depending on the IB and comonomer structure supported the experimental observations. This work expands the toolkit of water-soluble inibramers for CRBP and highlights the critical influence of the inibramer structure on reaction outcomes.

Study of absorption and emission spectra of substituted terthiophene compounds by methods of theoretical chemistry.

Terthiophene derivatives attract interest due to their prospective applications in optoelectronic or sensor devices. Due to their nontoxicity they can be considered as suitable candidates in biological applications. Supramolecular organization of the matter is one of the most interesting topics in contemporary materials science. Amphiphilic chromophores based on substituted terthiophenes are capable of self-assembly into supramolecular architectures. In this work, we aim at simulation of the spectral properties of terthiophene with oligo(ethylene oxide) substituents by the methods of quantum chemistry and molecular dynamics (MD). The potential energy surface (PES) of this molecule was determined by the methods of density functional theory (DFT) for the ground state and time-dependent density-functional theory (TD-DFT) for the excited state. MD simulations in water than revealed the most frequented molecular conformations in both these states. Absorption and fluorescence spectra were determined for all these conformations, including the surrounding water molecules, using TD-DFT and averaged over the conformation space to obtain the final absorption and fluorescence spectrum. The calculated spectra were compared with their experimental counterparts and the differences were discussed in context of the supramolecular structure revealed by confocal microscopy. In spite of its simplicity, this approach provides a satisfactory approximation of absorption and fluorescent spectra of these molecules obtained by computational methods.

An integrated "rigid-flexible" strategy by side chain engineering towards high ion-conduction cationic covalent organic framework electrolytes.

In recent years, solid-state lithium metal batteries (SSLMBs) have become a new development trend, and it has become a top priority to design solid-state electrolytes (SSEs) that can rapidly and stably transport lithium ions in a variety of climatic environments. In this work, an integrated "rigid-flexible" dual-functional strategy is proposed to develop a cationic covalent organic framework (EO-BIm-iCOF) with well-defined flexible oligo(ethylene oxide) (EO) chains as an SSE for SSLMBs. As expected, the synergistic effects of the rigid cationic framework and flexible EO chains not only promote the dissociation of LiTFSI salts, but also greatly improve the transport of lithium ions, which endows LITFSI@EO-BIm-iCOF SSEs with a high Li+ conductivity of 1.08 × 10-4 S cm-1 and ionic transference number of 0.69 at room temperature. Besides, the molecular dynamics (MD) simulations have also elucidated the diffusion and transport mechanism of lithium ions in LITFSI@EO-BIm-iCOF SSEs. Interestingly, the assembled SSLMBs wherein LiFePO4 is paired with LITFSI@EO-BIm-iCOF SSEs display decent electrochemical properties at higher and lower temperatures. This work provides a great development prospect for the application of cationic COFs in solid-state batteries.

Photo-RDRP for everyone: Smartphone light-induced oxygen-tolerant reversible deactivation radical polymerization

Oxygen-tolerant reversible deactivation radical polymerization (RDRP) was carried out utilizing a smartphone flashlight. Well-controlled poly(oligo(ethylene oxide) monomethyl ether methacrylate) (POEOMA500) with relatively low dispersity (Đ = 1.16–1.35) was obtained employing dual catalysis atom transfer radical polymerization (ATRP) with CuBr2/tris(2-pyridylmethyl)amine (TPMA) and three different organic photocatalytic dyes (i.e. eosin Y (EY), fluorescein (FL), and riboflavin (RF)). The smartphone flashlight was also used for carrying out oxygen-tolerant photoinduced electron/energy transfer (PET) reversible addition–fragmentation chain transfer (RAFT) polymerization with EY and dithioesters RAFT agents , and photoiniferter (PI) RAFT polymerization with trithiocarbonate RAFT agent. The formation of crosslinked gels and facile measurement of gel points via recording the gelation process by in-built smartphone camera was also demonstrated.

Capturing Nano‐Scale Inhomogeneity of the Electrode Electrolyte Interface in Sodium‐Ion Batteries Through Tip‐Enhanced Raman Spectroscopy

AbstractA prime challenge in the development of new battery chemistries is the fundamental understanding of the generation of the electrode–electrolyte interface (EEI) and its evolution upon cycling. Tip‐enhanced Raman spectroscopy (TERS) under an inert gas atmosphere is employed to study the chemical components of the anode/cathode electrolyte interface in a sodium‐ion battery. After the first cycle, TERS reveals that the EEI mostly consists of organic carbonate/dicarbonate, oligoethylene oxides, α,β‐unsaturated vinyl ketones/acetates, and inorganic species ClO4−, ClO3−, and Na2CO3. Whereas after 5× cycling, the EEI composition has evolved to contain long chain monodentate or bridging/bidentate carboxylates and alkoxides. The TERS map reveals the nano‐scale heterogeneity present in the EEI layers and elucidates a multilayered nano‐mosaic coating structure. The sheer volume of Raman signature present in the TERS signal can completely unravel the mysteries regarding the chemical composition and may shed light to the physicochemical behavior of the EEI.

Molecular Dynamics Calculations for the Temperature Response of Poly(alkylated tri(ethylene oxide)isocyanate) Aqueous Solution

Aqueous solutions of conventional temperature-responsive amphiphilic polymers undergo a coil–globule conformational transition around the lower critical solution temperature (LCST) that causes the polymer surfaces to become hydrophobic and the polymers to aggregate together. Isocyanate polymers with alkylated oligo(ethylene oxide) side chains are expected to have rigid main chains and, thus, do not undergo the coil–globule structural transition, but they have recently been reported to exhibit temperature-responsive properties. In this study, molecular dynamics was used to calculate the agglomeration tendencies of two chains of poly(alkylated tri(ethylene oxide)isocyanate) (PRTEOIC, where R = methyl (Me) or ethyl (Et)) in aqueous solution to elucidate the LCST phenomenon in the absence of coil–globule conformational transition. Our MD simulations showed that aggregation also occurs in rod polymers. Furthermore, we found that both (PMeTEOIC)2 and (PEtTEOIC)2 showed parallel agglomeration of the two molecular chains with increasing temperature, but only (PMeTEOIC)2 showed a metastable T-shaped agglomeration in the middle temperature range. The crossing-point temperature (TCRP) at which the density of the first hydrophobic hydration shell around the sidechain alkyl group equals the bulk water density is a useful indicator for predicting the LCST of rod polymers with dense side chains terminated by alkyl groups.

Fine-tuning morphology via oligo(ethylene oxide) side chain engineering for squaraine-based organic solar cells

Two squaraine dyes (SQs), USQ-O bearing oligo(ethylene oxide) (OE) chain, and USQ-C bearing alkyl chain, were synthesized. The influence of OE side chain on photovoltaic performances was systematically investigated. USQ-C and USQ-O show similar absorption spectra in dilute solutions, energy levels, charge mobility and the molecular electrostatic potential (ESP) on the conjugated skeleton. However, USQ-O exhibits hypsochromic absorption band compared to that of USQ-C in the film, and the distribution of positive and negative alternating ESP on the OE side chain. Significantly different electrostatic interactions and multiple hydrogen bonds among OE side chains could greatly affect the behaviors of intermolecular interactions, and, in turn, influence the photophysical properties of pristine/blend films and the miscibility with PC71BM acceptor. USQ-O-based devices exhibit higher short circuit current than that of USQ-C-based (13.94 vs 12.36 mA cm−2), which could be principally put down to the effective improvement of the blending morphology. These results indicate that simply substituted alkyl chain by OE chain for SQ is an effective strategy for optimizing morphology.

Electronic and Structural Properties of Core-Shell Amino-Silica Nanoparticles: DFT And SCC-DFTB Calculation

Introduction: Silica nanoparticles (SNP) are extremely promising tools in nanotechnology and nano medicine. In most of applications such as capture and release of bacteriophage viruses the nano-structures of silica are coated by bio-compatible groups such as amine compounds. The presence of amino groups on the surface of the biosensors enables the installation of analyte receptors and antifouling agents such as oligo (ethylene oxide). Therefore, in this study, the electronic and structural properties of Core-Shell amino- Silica Nanoparticles are investigated.Material and Methods: In this investigation, we aim at obtaining the optimized structures and evaluate the geometries of the ground state for (SiO2) n (n=16, 20) nanoclusters. The electronic properties computed by density functional theory with GGA approximation and SCC-DFTB with hybrid Slater-Koster files are investigated and the effect of functionalization on such properties is discussed.Results: Solvolysis of studied structures is examined and it is shown that the highest occupied and lowest unoccupied molecular orbital states shift to obviously higher energy levels, which lead to more stable hydrogenated nanoclusters. The stability of nanoclusters rises by functionalization with amino and methylamine groups. Charge analysis of functionalized systems indicates the reactivity of nanoclusters. The results obtained in this paper are useful for chemical and biochemical applications of silica nanostructures.Conclusion: Results show that the length of amine hydrocarbon chain can control the electronic and magnetic properties of studied silica nanocluster (SNP) with different number of SiO2 unit. Pure ultra-small nanocluster shows the impressive spin splitting around the Fermi level, which is due to the spin splitting of outer silicon atoms. This feature of silica nanoclusters may be notable for applications in electronics.

Preparation and Properties of Physical Gel on Medical Titanium Alloy Surface.

Medical titanium alloy Ti-6Al-4V (TC4) has been widely used in the medical field, especially in human tissue repair. However, TC4 has some shortcomings, which may cause problems with biocompatibility and mechanical compatibility in direct contact with the human body. To solve this problem, physical gels are formed on the surface of TC4, and the storage modulus of the formed physical gel matches that of the human soft tissue. 2-bromoisobutyryl bromide (BIBB) and dopamine (DA) were used to form initiators on the surface of hydroxylated medical titanium alloy. Different initiators were formed by changing the ratio of BIBB and DA, and the optimal one was selected for subsequent reactions. Under the action of the catalyst, L-lactide and D-lactide were ring-opened polymerized with hydroxyethyl methacrylate (HEMA), respectively, to form macromolecular monomers HEMA-PLLA29 and HEMA-PDLA29 with a polymerization degree of 29. The two macromolecular monomers were stereo-complexed by ultrasound to form HEMA-stereocomplex polylactic acid (HEMA-scPLA29). Based on two monomers, 2-(2-methoxyethoxy) ethyl methacrylate (MEO2MA) and oligo (ethylene oxide) methacrylate (OEGMA), and the physical crosslinking agent HEMA-scPLA29, physical gels are formed on the surface of TC4 attached to the initiator via Atom Transfer Radical Addition Reaction (ATRP) technology. The hydrogels on the surface of titanium alloy were characterized and analyzed by a series of instruments. The results showed that the storage modulus of physical glue was within the range of the energy storage modulus of human soft tissue, which was conducive to improving the mechanical compatibility of titanium alloy and human soft tissue.

RNA-Polymer Hybrids via Direct and Site-Selective Acylation with the ATRP Initiator and Photoinduced Polymerization.

Combining synthetic polymers with RNA paves the way for creating RNA-based materials with non-canonical functions. We have developed an acylation reagent that allows for direct incorporation of the atom transfer radical polymerization (ATRP) initiator into both short synthetic oligoribonucleotides and natural biomass RNA extracted from torula yeast. The acylation was performed in a quantitative yield. The resulting initiator-functionalized RNAs were used for grafting polymer chains from the RNA by photoinduced ATRP, resulting in RNA-polymer hybrids with narrow molecular weight distributions. The RNA initiator was used for the polymerization of oligo(ethylene oxide) methyl ether methacrylate, poly(ethylene glycol) dimethacrylate, and N-isopropylacrylamide monomers, resulting in RNA bottlebrushes, hydrogels, and stimuli-responsive materials. This approach, readily applicable to both post-synthetic and nature-derived RNA, can be used to engineer the properties of a variety of RNA-based macromolecular hybrids and assemblies providing access to a wide variety of RNA-polymer hybrids.

Insect-Inspired Strategy for Conferring Reversible, High Responsivity on Microgels to Dilute-Source CO2.

We described an insect-inspired strategy for conferring reversible, high responsivity on polymer microgels to dilute-source CO2 (≤5000 ppm in gas mixtures). This is demonstrated on oligo(ethylene oxide)-based microgels that contain tertiary amines on the polymer chains with proper organic small molecular carbonates in the polymer-solvent system. Similar to the synergistic contribution of the CO2 receptor subunits in mosquitoes for CO2 response, laser light scattering and related studies indicated that the CO2-response of the microgels in terms of the volume changes works through the coordination of different functional moieties in the system, making it different from the conventional CO2-response mechanism. While this pushes the lower response threshold of CO2 concentration down to ca. 1000 ppm, this unique strategy can also satisfy the urge to achieve both effective CO2 capture and facile CO2 release, making it possible to couple the detection with the capture and utilization of indoor excess CO2.

Unraveling the Role of Non-Fullerene Acceptor with High Dielectric Constant in Organic Solar Cells.

Increasing the relative dielectric constant is a constant pursuit of organic semiconductors, but it often leads to multiple changes in device characteristics, hindering the establishment of a reliable relationship between dielectric constant and photovoltaic performance. Herein, a new non-fullerene acceptor named BTP-OE is reported by replacing the branched alkyl chains on Y6-BO with branched oligoethylene oxide chains. This replacement successfully increases the relative dielectric constant from 3.28 to 4.62. To surprise, BTP-OE offers consistently lower device performance relative to Y6-BO in organic solar cells (16.27% vs 17.44%) due to the losses in open-circuit voltage and fill factor. Further investigations unravel that BTP-OE has resulted in reduced electron mobility, increased trap density, enhanced first order recombination, and enlarged energetic disorder. These results demonstrate the complex relationship between dielectric constant and device performance, which provide valuable implications for the development of organic semiconductors with high dielectric constant for photovoltaic application.

Protic ion-crosslinked polymer ionic liquid (PIL) based on linear oligomers

A method for the synthesis of a protic ion-crosslinked polymeric ionic liquid (PIL) which turns into a liquid state at a temperature below 50 °C using a reaction of basic and acidic linear oligomers was developed. The product of interaction of α,ω-diglycidyl ester of oligoethylene oxide MM 1000 with an excess of 1-(3-aminopropyl)imidazole (PEO–2Im) was used as the basic oligomer. It contains two types of basic centers with a significant difference in basicity (aliphatic secondary amino groups and imidazole heterocycles), as well as secondary hydroxyl groups at the ends of oligoether chain. A linear oligomer with terminal sulfonic acid groups (PEO–2SO3H) was obtained by the interaction of of oligoethylene oxide MM 1000 with 2-sulfobenzoic acid cyclic anhydride. Protic ion-crosslinked PIL was synthesized by completely neutralization of basic centers of oligomer PEO–2Im by acidic oligomer PEO–2SO3H at their molar ratio 1:2 respectively. The structure of the obtained PIL was characterized by FTIR and 1Н NMR- spectroscopy methods. According to DSC, the synthesized ion-crosslinked PIL contains two types of crystalline formations with melting temperatures of 36,3 °C and 45,8 °C formed by fragments of oligoethylene oxide during the transfer of protons between different types of ion centers. Determined by the TGA method the temperature of the onset of decomposition, which corresponds to 5% mass loss, is 265 °C. The proton conductivity of the ion-crosslinked PIL was studied by the DRS method in anhydrous conditions in the temperature range from 40 to 100 °C. At a temperature of 100 °C, the proton conductivity is 3,1·10-4 S/cm. The achieved values of proton conductivity and thermal stability make the obtained compound promising as a proton-conducting medium for various electrochemical devices.

Ultrasmall, elementary and highly translational nanoparticle X-ray contrast media from amphiphilic iodinated statistical copolymers.

To expand the single-dose duration over which noninvasive clinical and preclinical cancer imaging can be conducted with high sensitivity, and well-defined spatial and temporal resolutions, a facile strategy to prepare ultrasmall nanoparticulate X-ray contrast media (nano-XRCM) as dual-modality imaging agents for positron emission tomography (PET) and computed tomography (CT) has been established. Synthesized from controlled copolymerization of triiodobenzoyl ethyl acrylate and oligo(ethylene oxide) acrylate monomers, the amphiphilic statistical iodocopolymers (ICPs) could directly dissolve in water to afford thermodynamically stable solutions with high aqueous iodine concentrations (>140mg iodine/mL water) and comparable viscosities to conventional small molecule XRCM. The formation of ultrasmall iodinated nanoparticles with hydrodynamic diameters of ca. 10nm in water was confirmed by dynamic and static light scattering techniques. In a breast cancer mouse model, invivo biodistribution studies revealed that the 64Cu-chelator-functionalized iodinated nano-XRCM exhibited extended blood residency and higher tumor accumulation compared to typical small molecule imaging agents. PET/CT imaging of tumor over 3 days showed good correlation between PET and CT signals, while CT imaging allowed continuous observation of tumor retention even after 10 days post-injection, enabling longitudinal monitoring of tumor retention for imaging or potentially therapeutic effect after a single administration of nano-XRCM.

Spiropyran-containing water-soluble and photoreversible copolymers

Photoreversibility in polymer design enables the control of physical properties using light, and in concert with water-solubility permits applications in aqueous environments. Inspired by environmental application, the primary goal of this paper is to develop a new synthesis pathway and to characterize the structure and functional behavior of spiropyran-containing photoreversible and water-soluble polymers. A one-step facile acylation reaction yielded the spiropyran-containing acrylate (SPA) monomer. Free radical copolymerization afforded a series of copolymers of SPA and oligo(ethylene oxide) monoacrylate monomer (OEOA) (Mn = 480 g/mol). Thermal analysis, including thermogravimetric analysis and differential scanning calorimetry, revealed the influence of SPA content on copolymer weight loss profile and OEOA side chain crystallization/melting. Copolymers exhibited good water solubility owing to the hydrophilic OEOA side chain. Solution rheology unveiled a shear-thickening effect related to the SPA pendent group and revealed the solution viscosity dependence on polymer concentration in aqueous solutions. In water, the designed spiropyran-containing polymers displayed photoreversibility and exhibited high photo-fatigue resistance with >90% of UV–vis absorbance preserved after five cycles. Preliminary Cu2+ complexation studies with SPA-co-OEOA copolymers indicated 88% removal of Cu2+ after UV irradiation, which suggests opportunities as light-responsive polymers for Cu2+ removal.

Fully Oxygen-Tolerant Visible-Light-Induced ATRP of Acrylates in Water: Toward Synthesis of Protein-Polymer Hybrids.

Over the last decade, photoinduced ATRP techniques have been developed to harness the energy of light to generate radicals. Most of these methods require the use of UV light to initiate polymerization. However, UV light has several disadvantages: it can degrade proteins, damage DNA, cause undesirable side reactions, and has low penetration depth in reaction media. Recently, we demonstrated green-light-induced ATRP with dual catalysis, where eosin Y (EYH2) was used as an organic photoredox catalyst in conjunction with a copper complex. This dual catalysis proved to be highly efficient, allowing rapid and well-controlled aqueous polymerization of oligo(ethylene oxide) methyl ether methacrylate without the need for deoxygenation. Herein, we expanded this system to synthesize polyacrylates under biologically relevant conditions using CuII/Me6TREN (Me6TREN = tris[2-(dimethylamino)ethyl]amine) and EYH2 at ppm levels. Water-soluble oligo(ethylene oxide) methyl ether acrylate (average M n = 480, OEOA480) was polymerized in open reaction vessels under green light irradiation (520 nm). Despite continuous oxygen diffusion, high monomer conversions were achieved within 40 min, yielding polymers with narrow molecular weight distributions (1.17 ≤ D̵ ≤ 1.23) for a wide targeted DP range (50-800). In situ chain extension and block copolymerization confirmed the preserved chain end functionality. In addition, polymerization was triggered/halted by turning on/off a green light, showing temporal control. The optimized conditions also enabled controlled polymerization of various hydrophilic acrylate monomers, such as 2-hydroxyethyl acrylate, 2-(methylsulfinyl)ethyl acrylate), and zwitterionic carboxy betaine acrylate. Notably, the method allowed the synthesis of well-defined acrylate-based protein-polymer hybrids using a straightforward reaction setup without rigorous deoxygenation.

Convenient and industrially viable internal plasticization of poly(vinyl chloride): copolymerization of vinyl chloride and commercial monomers

A new strategy involving the internal plasticization of poly(vinyl chloride) (PVC) is successfully achieved by copolymerization of vinyl chloride (VC) and commercial available monomers such as n-butyl acrylate (n-BA) and oligo(ethylene oxide) methyl ether acrylate (OEOA). To evaluate the effect on glass transition temperatures (Tg) of the resulting PVC-co-POEOA, PVC-co-PBA and PVC-co-PBA-co-POEOA copolymers, solvent, initiator, polymerization temperature and VC/n-BA/OEOA monomers ratios were systematically investigated. These internally plasticized PVC-based copolymers were fully characterized by 1H NMR, FTIR, SEC, DMTA, TGA and DSC to determine the composition, molecular weight, dispersity, and thermal properties. The experimental Tg values of the PVC-co-PBA-co-POEOA copolymers were even lower than those predicted by the Fox equation (TgFOX) indicating effective plasticization of PVC and reached values as low as −57 °C. Under optimized conditions, it was possible to afford different degrees of internal plasticization just by varying the initial VC/n-BA/OEOA monomer ratio. Most significantly, the plasticizing moieties of internally plasticized PVC copolymers are truly covalently bonded to the polymer, resulting in the absence of any migration upon extraction under conditions where commonly used plasticizers are readily extractable.

PH-responsive nanoparticles based on POEOMA-b-PDPA block copolymers for RNA encapsulation, protection and cell delivery

The use of gene-based products, such as DNA or RNA, is increasingly being explored for various innovative therapies. However, the success of these strategies is highly dependent on the effective delivery of these biomolecules to target cells. Therefore, the development of pH-responsive nanoparticles comprises the creation of intelligent delivery systems with high therapeutic efficiency. In this work, the pH-responsiveness of the poly(2-(diisopropylamino)ethyl methacrylate)) (PDPA) block was investigated for the encapsulation and delivery of small RNAs (sRNA) to cancer cells. The pH responsiveness was dependent on the protonation profile of the tertiary amines of PDPA, which directly affected the electrostatic interactions established with RNA. Thus, block copolymers based on poly(oligo(ethylene oxide) methyl ether methacrylate) (POEOMA) and PDPA, POEOMA-b-PDPA, were synthesized by supplemental activator and reducing agent atom transfer radical polymerization (SARA ATRP). The structure of the block copolymers was characterized by size exclusion chromatography and 1H NMR spectroscopy. The copolymers allowed effective complexation of model sRNAs and a pre-miRNA with efficiencies of about 89 % and 91 %, respectively. The characterization by dynamic light scattering revealed that these systems had sizes between 76 and 1375 nm. It was also found that the morphology of the polyplexes depended on the pH, since the preparation at a pH lower than the pKa of the copolymers resulted in spherical but polydisperse particles, while higher pH values resulted in nanoparticles with more homogeneous size, but altered morphology. Moreover, due to pH-responsiveness, it was achieved the release of RNA at pH higher than the pKa of the copolymers, while maintaining its integrity. The polyplexes also showed a high potential to protect RNA from RNases. The transfection of a lung cancer model (A549) and fibroblast cell lines showed that these polyplexes did not cause cell toxicity. In addition, the polyplexes enabled the effective transfection of the A549 cell line with pre-miRNA-29b and miRNA-29b, resulting in a decrease of expression levels of the target DNMT3B gene by approximately 51 % and 47 %, respectively. Overall, the POEOMA-b-PDPA copolymers proved to be a promising strategy for developing responsive delivery systems, that can play a critical role in some diseases, such as cancer, where pH varies between the intra and extracellular environments.

Blue‐light‐induced atom transfer radical polymerization enabled by iron/copper dual catalysis

AbstractPhotoinduced initiators for continuous activator regeneration atom transfer radical polymerization (PICAR ATRP) using sodium pyruvate and blue light (λmax = 456 nm) is reported. Water‐soluble oligo(ethylene oxide) methyl ether methacrylate (OEOMA500) was polymerized under biologically relevant conditions. Polymerizations were conducted with 1000 ppm (with respect to the monomer) concentrations of CuBr2, tris(2‐pyridylmethyl)amine, and 1000 ppm or less FeCl3 as a cocatalyst in water. Well‐defined polymers with up to 90% monomer conversion, high molecular weights (Mn > 190,000), and low dispersity (1.14 < Ð < 1.19) were synthesized in less than 60 min. The polymerization rate and dispersity were tuned by varying the concentration of sodium pyruvate (SP), iron, and supporting halide, as well as light intensity. The Cu/Fe dual catalysis provided oxygen tolerance enabling rapid, well‐controlled, aqueous PICAR ATRP of OEOMA500 without deoxygenation.