Polymer Side Groups Research Articles

Molding blends of silicone polymer / polypropylene with durable resistant to extreme conditions based on migration and compatibility of molecular chains

Because of low surface energy, silicone polymers would easily peel off from polypropylene (PP) substrate as hydrophobic coatings and they are incompatible with PP in melt-blending process as well. Therefore, ethylene polymers modified with both silicone and alkane side-groups were prepared by nucleophilic substitution in this work. It was confirmed that these prepared polymers could migrate and aggregate to the surface of the blends at that melting temperature when blended with PP due to the low surface energy and high entropy of silicone side groups. Meanwhile, chain entanglement was achieved between alky side-groups of silicone polymers and polymer chain of PP by melt-blending process, so that the compatibility of the blends was improved and the bonding force of two polymers increased simultaneously. Accordingly, molding blends with stable and durable hydrophobility were successfully gained based on migration of silicone and entanglement of alkane and PP. It’s noticeable that the water contact angle of the blend remained to be about 106° from 113°, even soaking in acid (pH = 1) and alkali (pH = 14) solutions, deionized water and anhydrous ethanol, or under multiple strong frictions. This will provide a facile and effective strategy to endow general materials with durable antifouling properties directly by injection molding without additional coating.

Electrodeposition of Polymer Networks as Conformal and Uniform Ultrathin Coatings.

Natural systems, synthetic materials, and devices almost always feature interphases that control the flow of mass and energy or stabilize interfaces between incompatible materials. With technologies transitioning to non-planar and 3D mesoscale architectures, novel deposition methods for realizing ultrathin coatings and interphases are required. Polymer networks are of particular interest for their tunable chemical and physical properties combined with their structural integrity. Here, the electrodeposition of polymer networks (EPoN) is introduced as a general approach to uniformly coat non-planar conductive materials. Conceptually, EPoN utilizes electrochemically activated crosslinkers as polymer end groups to confine their network formation exclusively to the material surface upon charge transfer, yielding a passivating and self-limiting growth of conformal and uniform coatings with tunable submicron thickness on conductive materials. EPoN is found to result in thin functional films of various polymer backbones and side group chemistries as demonstrated for poly(ether) and poly(acrylamide) based polymers as solid electrolyte and thermally responsive interphases, respectively.

Stereoselective Crystallization of Chiral Pharmaceuticals Aided by Cellulose Derivatives through Helical Pattern Matching.

Stereoselective inhibition aided by "tailor-made" polymeric additives is an efficient approach to obtain enantiopure compounds through conglomerate crystallization. The chemical and configurational match between the side groups of polymers and the molecules of undesired enantiomer is considered to be a necessary condition for successful stereoseparation. Whereas in this contribution, we present an effective resolution of chiral pharmaceuticals by using cellulose acetates as the additives, which stereoselectively reside on the specific crystal faces of one enantiomer and inhibit its crystal nucleation and growth through helical pattern and supramolecular interaction complementarity. An investigation of nimodipine serves as a case study to highlight the novelty of this strategy wherein R-crystals exhibiting an impressive enantiomeric excess value of 97 % can be attained by employing a mere 0.01 wt % cellulose acetate. Guaifenesin and phenyl lactic acid are also well-resolved by utilizing this methodology. Our work not only brings about a brand-new design strategy for "tailor-made" additives, but will also promote the further exploration of the endless potential for utilizing natural biomolecules in chiral recognition and resolution.

Fluorine-Functionalized Polyphosphazene Immunoadjuvant: Synthesis, Solution Behavior and In Vivo Potency.

The inclusion of fluorine motifs in drugs and drug delivery systems is an established tool for modulating their biological potency. Fluorination can improve drug specificity or boost the vehicle's ability to cross cellular membranes. However, the approach has yet to be applied to vaccine adjuvants. Herein, the synthesis of fluorinated bioisostere of a clinical stage immunoadjuvant-poly[di(carboxylatophenoxy)phosphazene], PCPP-is reported. The structure of water-soluble fluoropolymer-PCPP-F, which contains two fluorine atoms per repeat unit-was confirmed using 1H, 31P and 19F NMR, and its molecular mass and molecular dimensions were determined using size-exclusion chromatography and dynamic light scattering. Insertion of fluorine atoms in the polymer side group resulted in an improved solubility in acidic solutions and faster hydrolytic degradation rate, while the ability to self-assemble with an antigenic protein, lysozyme-an important feature of polyphosphazene vaccine adjuvants-was preserved. In vivo assessment of PCPP-F demonstrated its greater ability to induce antibody responses to Hepatitis C virus antigen when compared to its non-fluorinated counterpart. Taken together, the superior immunoadjuvant activity of PCPP-F, along with its improved formulation characteristics, demonstrate advantages of the fluorination approach for the development of this family of macromolecular vaccine adjuvants.

A “metal ions-induced poisoning behavior of biomolecules” inspired polymeric probe for Cu2+ selective detection on basis of coil to helix conformation transition

The interaction between heavy metal ions (e.g. Cu2+, Pb2+, Cr6+) and bioactive biomolecules can severely cause the “poisoning behavior” due to the secondary structure transition. While in a bioinspiration strategy, functional polymers with the ability of selectively responding to metal ions can be used as effective probe candidate for metal ion detection. Herein, a series of functional substituted polyacetylenes with glycine pendants (P-Gly-NH2) are deliberately designed and synthesized as a fresh member of polymeric probe arsenal for selective ions recognition. According to chemical and structural characterization including FT-IR, NMR, GPC, UV–vis and so on, the synthesized P-Gly-NH2 polymers with glycine amide pendants possess random coil conformation on the conjugated main chains. Benefit from remarkable water-soluble ability and secondary structure, P-Gly-NH2 can simulate the biomolecules and apply for heavy metal ions detection in aqueous solution. Because of the complexing interaction with Cu2+, the particular “random coil to helical” conformation transition of P-Gly-NH2 backbone can be observed by UV–vis characterization in ion recognition experiments. Moreover, the relevant results of ions interfering and titration experiments also confirm that this selective detection towards Cu2+ exhibits an outstanding time-efficiency and reliability with the corresponding detection limitation around 0.128 mg/L. As revealed in UV–vis, Raman, FT-IR and XPS spectra characterization, this conformation transition of P-Gly-NH2 is owing to the complexing interaction between Cu2+ and nitrogen atoms in polymer side groups, resulting in an ordered cis-cisoidal helical structures in polymer backbones. In a word, this study not only paves a new way for design and synthesis of water-soluble amino acid-based substituted polyacetylenes, but also implements the functional polymeric probes for selective and sensitive detection of heave ions through a bioinspiration strategy.

Effect of Position and Structure of the Terminal Moieties in the Side Group on the Liquid Crystal Alignment Behavior of Polystyrene Derivatives.

We synthesized a series of polystyrene derivatives containing various side groups, such as the 4-(tert-butyl)-phenoxymethyl, 3-(tert-butyl)-phenoxymethyl, 2-(tert-butyl)-phenoxymethyl, 4-cumyl-phenoxymethyl, and 4-trityl-phenoxymethyl groups, through a polymer modification reaction to examine the liquid crystal (LC) alignment of these derivatives. In general, the vertical LC alignment on polymer films can be affected by the position and structure of the terminal moiety of the polymer side group. For example, the LC cells fabricated with 4-(tert-butyl)-phenoxymethyl-substituted polystyrene having a tert-butyl moiety as a para-type attachment to the phenoxy groups of the polystyrene derivatives exhibited vertical LC alignment, whereas the LC cells prepared from 3-(tert-butyl)- and 2-(tert-butyl)-phenoxymethyl-substituted polystyrene films exhibited planar LC alignment. In addition, the LC cells fabricated from 4-cumyl- and 4-trityl-phenoxymethyl-substituted polystyrene films with additional phenyl rings in the side groups exhibited planar LC alignment, in contrast to the LC alignment of the (tert-butyl)-phenoxymethyl-substituted polystyrene series. The vertical LC orientation was well correlated with the surface energy of these polymer films. For example, vertical LC orientation, which mainly originates due to the nonpolar tertiary carbon moiety having bulky groups, was observed when the surface energy of the polymer was lower than 36.6 mJ/m2.

Responsive Polyesters with Alkene and Carboxylic Acid Side-Groups for Tissue Engineering Applications.

Main chain polyesters have been extensively used in the biomedical field. Despite their many advantages, including biocompatibility, biodegradability, and others, these materials are rather inert and lack specific functionalities which will endow them with additional biological and responsive properties. In this work, novel pH-responsive main chain polyesters have been prepared by a conventional condensation polymerization of a vinyl functionalized diol with a diacid chloride, followed by a photo-induced thiol-ene click reaction to attach functional carboxylic acid side-groups along the polymer chains. Two different mercaptocarboxylic acids were employed, allowing to vary the alkyl chain length of the polymer pendant groups. Moreover, the degree of modification, and as a result, the carboxylic acid content of the polymers, was easily tuned by varying the irradiation time during the click reaction. Both these parameters, were shown to strongly influence the responsive behavior of the polyesters, which presented adjustable pKα values and water solubilities. Finally, the difunctional polyesters bearing the alkene and carboxylic acid functionalities enabled the preparation of cross-linked polyester films by chemically linking the pendant vinyl bonds on the polymer side groups. The biocompatibility of the cross-linked polymers films was assessed in L929 fibroblast cultures and showed that the cell viability, proliferation, and attachment were greatly promoted on the polyester surface, bearing the shorter alkyl chain length side groups and the higher fraction of carboxylic acid functionalities.

Investigation of poly(phenylacetylene) derivatives for carbon precursor with high carbon yield and good solubility

This paper investigates a family of poly(phenylacetylene) derivatives with a p-electrons conjugated polymer backbone and side groups containing only sp2 and sp carbons. The objective is to identify the suitable carbon precursor that is processible and can be transformed to carbonaceous material with high carbon yield by a simple (one-step) thermal transformation process (without any external reagent). Poly(phenylacetylene) with para-substituted acetylene group poly(PA-A) shows an exceptionally high C-yield (~90%) in one-step heating from ambient temperature to 1000 °C under N2 atmosphere. Unfortunately, this poly(PA-A) polymer is quite sensitive to heat and light with very limited solubility. On the other hand, poly(phenylacetylene) with para-substituted phenylacetylene group, i.e. poly(PA-PA), offers a relatively high C-yield (~80%) and also good solubility in common organic solvents, such as toluene and tetrahydrofuran (THF). Several uniform dark-red poly(PA-PA) fibers with smooth surface and fiber diameter in the range of 3–6 μm were prepared from 30 wt% poly(PA-PA)/THF solution using electrospinning technique. The resulting precursor fibers were converted to the corresponding carbon structure in a one-step thermal heating process under N2 atmosphere. Both X-ray and Raman spectra show the polymorphous carbon morphology with the graphene crystalline domains.

Fluorinated Polymers via Para-Fluoro-Thiol and Thiol-Bromo Click Step Growth Polymerization.

Click reactions are utilized widely to modify chain ends and side groups of polymers while click polymerizations based on step-growth polymerization of bifunctional monomers have recently attracted increased attention of polymer chemists. Herein, the combination of two highly efficient click reactions, namely para-fluoro-thiol click and thiol-bromo substitution reactions, is demonstrated to form fluorinated polymers with tuned hydrophobicity owing to the nature of the dithiol linker compound. The key compound in this study is 2,3,4,5,6-pentafluoro benzyl bromide that provides the combination of thiol click reactions. The thiols used here are 4,4-thiobisbenzenthiol, 2,2'-(ethylenedioxy) diethanethiol, and 1,2-ethanedithiol that allow tuning of the properties of obtained polymers. The step-growth click reaction conditions are optimized by screening the effect of reaction temperature, base, solvent, and stochiometric ratio of the compounds. Thermal properties and hydrophobicity of synthesized polymers are determined via water contact angle, thermogravimetric analysis and differential scanning calorimetry measurements, showing thermal stability up to 300 °C, glass transition temperatures ranging from -25 to 82 °C and water contact angles ranging from 55 to 90 °C.

Interfacial Properties and Hopping Diffusion of Small Nanoparticle in Polymer/Nanoparticle Composite with Attractive Interaction on Side Group.

The diffusion dynamics of fullerene (C) in unentangled linear atactic polystyrene (PS) and polypropylene (PP) melts and the structure and dynamic properties of polymers in interface area are investigated by performing all-atom molecular dynamics simulations. The comparison of the results in two systems emphasises the influence of local interactions exerted by polymer side group on the diffusion dynamics of the nanoparticle. In the normal diffusive regime at long time scales, the displacement distribution function (DDF) follows a Gaussian distribution in PP system, indicating a normal diffusion of C. However, we observe multiple peaks in the DDF curve for C diffusing in PS melt, which indicates a diffusion mechanism of hopping of C. The attractive interaction between C and phenyl ring side groups are found to be responsible for the observed hopping diffusion. In addition, we find that the C is dynamically coupled with a subsection of a tetramer on PS chain, which has a similar size with C. The phenyl ring on PS chain backbone tends to have a parallel configuration in the vicinity of C surface, therefore neighbouring phenyl rings can form chelation effect on the C surface. Consequently, the rotational dynamics of phenyl ring and the translational diffusion of styrene monomers are found to be slowed down in this interface area. We hope our results can be helpful for understanding of the influence of the local interactions on the nanoparticle diffusion dynamics and interfacial properties in polymer/nanoparticle composites.

Effect of Chain Rigidity on the Decoupling of Ion Motion from Segmental Relaxation in Polymerized Ionic Liquids: Ambient and Elevated Pressure Studies

Conductivity in polymer electrolytes has been generally discussed with the assumption that the segmental motions control charge transport. However, much less attention has been paid to the mechanism of ion conductivity where the motions of ions are less dependent (decoupled) on segmental dynamics. This phenomenon is observed in ionic materials as they approach their glass transition temperature and becomes essential for design and development of highly conducting solid polymer electrolytes. In this paper, we study the effect of chain rigidity on the decoupling of ion transport from segmental motion in three polymerized ionic liquids (polyILs) containing the same cation–anion pair but differing in flexibility of the polymer backbones and side groups. Analysis of dielectric and rheology data reveals that decoupling is strong in vinyl-based rigid polymers while almost negligible in novel siloxane-based flexible polyILs. To explain this behavior, we investigated ion and chain dynamics at ambient and elevated ...

Intrinsically Hierarchical Nanoporous Polymers via Polymerization-Induced Microphase Separation

The synthesis of microporous polymers generally requires postpolymerization modification via hyper-cross-linking to trap the polymeric network in a state with high void volume. An alternative approach utilizes rigid, sterically demanding monomers to inhibit efficient packing, thus leading to a high degree of free volume between polymer side groups and main chains. Herein we combine polymers of intrinsic microporosity with polymerization-induced microphase separation (PIMS), a versatile methodology for the synthesis of nanostructured materials that can be rendered mesoporous. Copolymerization of various styrenic monomers with divinylbenzene in the presence of a poly(lactide) terminated with a chain-transfer agent (PLA-CTA) results in kinetic trapping of a microphase-separated state. Subsequent etching of PLA provides a bicontinuous mesoporous network. Using equilibrium and kinetic nitrogen sorption experiments as well as positron annihilation lifetime spectroscopy (PALS), we demonstrate that variations in ...

Side-group size effects on interfaces and glass formation in supported polymer thin films

Recent studies on glass-forming polymers near interfaces have emphasized the importance of molecular features such as chain stiffness, side-groups, molecular packing, and associated changes in fragility as key factors that govern the magnitude of Tg changes with respect to the bulk in polymer thin films. However, how such molecular features are coupled with substrate and free surface effects on Tg in thin films remains to be fully understood. Here, we employ a chemically specific coarse-grained polymer model for methacrylates to investigate the role of side-group volume on glass formation in bulk polymers and supported thin films. Our results show that bulkier side-groups lead to higher bulk Tg and fragility and are associated with a pronounced free surface effect on overall Tg depression. By probing local Tg within the films, however, we find that the polymers with bulkier side-groups experience a reduced confinement-induced increase in local Tg near a strongly interacting substrate. Further analyses indicate that this is due to the packing frustration of chains near the substrate interface, which lowers the attractive interactions with the substrate and thus lessens the surface-induced reduction in segmental mobility. Our results reveal that the size of the polymer side-group may be a design element that controls the confinement effects induced by the free surface and substrates in supported polymer thin films. Our analyses provide new insights into the factors governing polymer dynamics in bulk and confined environments.

Photoresponsive liquid crystalline polymer single-chain nanoparticles

Single-chain nanoparticles prepared from a side-chain liquid crystalline polymer bearing azobenzene moieties can be multifunctional.

P-Doping of polystyrene polymers with attached functional side-groups from solution

Study on the electrical properties of side-group polymers, p-doped with strong acceptors and deposited from solution.

The role of macromolecules in the formation of kidney stones.

The formation of crystal aggregates, one of the critical processes in kidney stone pathogenesis, involves interactions between crystals (predominantly calcium oxalate monohydrate, COM) and urinary constituents (e.g., proteins), which serve as an adhesive "glue" between crystals in stones. To develop a better understanding of the protein-crystal interactions that lead to crystal aggregation, we have measured the effect of model proteins on bulk COM crystal properties as well as their adsorption on crystal surfaces using three synthetic polyanions: poly(aspartic acid) (polyD), poly(glutamic acid) (polyE), and poly(acrylic acid) (polyAA). These anionic macromolecules reduced the amount of COM crystal aggregation in bulk solution to an extent similar to that observed for mixture of proteins from normal urine, with little difference between the polymers. In contrast, the polymers exhibited differences in measures of COM crystal growth. Polycations such as poly(arginine) (polyR) and poly(lysine) (polyK) reduced aggregation weakly and exerted negligible effects on crystal growth. All polyions were found to associate with COM crystal surfaces, as evidenced by changes in the zeta potential of COM crystals in electrophoretic mobility measurements. On the other hand, COM aggregation and possibly growth can be promoted by many binary mixtures of polycations and polyanions, which appeared to be mediated by polymer aggregate formation rather than loss of crystal charge stabilization. Similarly, crystal aggregation promotion behavior can be driven by forming aggregates of weakly charged polyanions, like Tamm-Horsfall protein, suggesting that polymer (protein) aggregation may play a critical role in stone formation. Sensitivity of polyanion-COM crystal surface interactions to the chemical composition of polymer side groups were demonstrated by large differences in crystal aggregation behavior between polyD and polyE, which correlated with atomic force microscopy (AFM) measurements of growth inhibition on various COM surfaces and chemical force microscopy (CFM) measurements of unbinding forces between COM crystal surfaces and AFM tips decorated with either carboxylate or amidinium moieties (mimicking polyanion and polyR side chains, respectively). The lack of strong interaction for polyE at the COM (100) surface compared to polyD appeared to be the critical difference. Finally, the simultaneous presence of polyanions and polycations appeared to alter the ability of polycations to mediate unbinding forces in CFM and promote crystal growth. In summary, polyanions strongly associated with COM surfaces and influenced crystallization, while polycations did not, though important differences were observed based on the physicochemical properties of polyanions. Observations suggest that COM aggregation with both polyanion-polycation mixtures and weakly charged polyanions is promoted by polymer aggregate formation, which plays a critical role in bridging crystal surfaces.

The effect of the monomer feed ratio and applied potential on copolymerization: investigation of the copolymer formation of ferrocene-functionalized metallopolymer and EDOT

In this study, we reported synthesis of ferrocene functioned conducting metallopolymer to enhance the understanding of properties of polymers. One of the crucial ways in the electrochromic polymer materials research was tuning color by means of copolymerization and change of polymer backbones and side groups. For this purpose, we synthesized copolymer of 4-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl)amido ferrocenyl dithiophosphonate with EDOT via potentiodynamic electrolysis. Spectral and electrochemical characterizations of the copolymer were investigated. In addition, the spectral properties of the copolymers prepared by different applied potentials and different monomer feed ratio were studied. For the first time, copolymer composition and the monomer reactivity ratios were approximately calculated by using the spectral data.

Structural Characterizations of Palladium Clusters Prepared by Polyol Reduction of [PdCl 4 ] (2-) Ions.

Palladium nanoparticles are of great interest in many industrial fields, ranging from catalysis and hydrogen technology to microelectronics, thanks to their unique physical and chemical properties. In this work, palladium clusters have been prepared by reduction of [PdCl4]2− ions with ethylene glycol, in the presence of poly(N-vinyl-2-pyrrolidone) (PVP) as stabilizer. The stabilizer performs the important role of nucleating agent for the Pd atoms with a fast phase separation, since palladium atoms coordinated to the polymer side-groups are forced at short distances during nucleation. Quasispherical palladium clusters with a diameter of ca. 2.6 nm were obtained by reaction in air at 90°C for 2 hours. An extensive materials characterization by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and other characterizations (TGA, SEM, EDS-SEM, and UV-Vis) has been performed in order to evaluate the structure and oxidation state of nanopalladium.

Deciphering Physical versus Chemical Contributions to the Ionic Conductivity of Functionalized Poly(methacrylate)-Based Ionogel Electrolytes.

Polymer-supported ionic liquids (ionogels) are emergent, nonvolatile electrolytes for electrochemical energy storage applications. Here, chemical and physical interactions between the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI TFSI) and three different cross-linked polymer scaffolds with varying chemical functional groups have been investigated in ionogels fabricated via in situ UV-initiated radical polymerization of methyl methacrylate (MMA), 2,2,2-trifluoroethyl methacrylate (TFEMA), or 2-(dimethylamino)ethyl methacrylate (DMAEMA) and a small amount of the cross-linker pentaerythritol tetraacrylate. Experimental findings demonstrate that the chemical functionality of the polymer side groups can significantly affect the degree of ion dissociation within the ionic liquid component of the ionogel and that the fraction of dissociated ions is the dominant factor in determining relative ionic conductivity in these materials, rather than any large differences in ion diffusivity. The MMA-based polymer scaffold exhibits a stronger attractive interaction with EMI TFSI (as evidenced by a higher activation energy of ionic conductivity) compared to the TFEMA- and DMAEMA-based scaffolds, resulting in consistently lower ionic conductivity values for MMA-based ionogels. These results may offer guidance toward the rational selection of future polymer-ionic liquid pairings in order to maximize the fraction of dissociated ions, thereby yielding highly conductive ionogel electrolytes.

Molecular Engineering of Ion-Conducting Polymers for Fuel Cell Membrane Applications

Aromatic polymers functionalized with various sulfonate groups and ammonium cations were synthesized for use in proton exchange membranes (PEMs) and anion exchange membranes (AEMs), respectively. The effect of these different ionic side groups of polymers on membrane transport properties will be discussed. On second part, high-molecular-weight quaternary ammonium (QA)-tethered aromatic polymers that are void of alkaline labile C–O bonds were prepared to achieve improved stability of AEM fuel cells. This new class of hydrocarbon polymers showed high hydroxide ion conductivity and excellent alkaline stability at 80 °C. Overall, this work provides a new synthetic strategy for preparation of AEMs with good fuel cell performance and excellent stability.