One-pot synthesis of supramolecular polymer containing quadruple hydrogen bonding units

A facile, efficient technique was built to synthesize a supramolecular material containing quadruple hydrogen bonding sites. The current approach presented here involves a single-step reaction between the amine of precursor, e.g. methyl isocytosine (MIC) and the epoxy group of polymer, e.g. poly(ethylene glycol diglycidyl ether) (PEG DGE, M_n = 526 g/mol, as verified using ¹H NMR and FT-IR spectroscopy. Wide angle X-ray scattering (WAXS), UV/visible spectroscopy and differential scanning calorimeter (DSC) clearly show that the product is not a simple mixture of two components, but the supramolecular polymer containing quadruple hydrogen bonding sites. Complex melt viscosities reveal that mechanical properties of the supramolecular polymer are enhanced by more than 10⁴ times compared to the pristine low molecular weight polymer, giving rise to the significant change of physical state from liquid to solid. Current approach also illustrates an advantageous route because it does not need the selective use of monofunctionalized precursor and not produce a dead, difunctionalized precursor.     

DNA-inspired hierarchical polymer design: electrostatics and hydrogen bonding in concert

Nucleic acids and proteins, two of nature's biopolymers, assemble into complex structures to achieve desired biological functions and inspire the design of synthetic macromolecules containing a wide variety of noncovalent interactions including electrostatics and hydrogen bonding. Researchers have incorporated DNA nucleobases into a wide variety of synthetic monomers/polymers achieving stimuli-responsive materials, supramolecular assemblies, and well-controlled macromolecules. Recently, scientists utilized both electrostatics and complementary hydrogen bonding to orthogonally functionalize a polymer backbone through supramolecular assembly. Diverse macromolecules with noncovalent interactions will create materials with properties necessary for biomedical applications.     

Supramolecular structures and properties models of macrocyclic polymer complexes

Two novel supramolecular complexes of types [Ru(L)(H₂L)Cl·OH₂] and [Ru(HL_n)Cl₃] (where H₂L is a potential tetradentate ligand derived from hydrazine hydrate and diethyl malonate, and HL_n is a potential bidentate ligand derived from coupling of allyl azo‐β‐diketone) have been synthesized and characterized by elemental analysis, conductance and magnetic measurements, followed by ¹H NMR, to determine the effect of substituents on the intramolecular hydrogen bond. The electronic properties and models of the bonding of ligands and complexes were investigated by UV–Vis and IR spectroscopies. The first type of complex contains terminal hydrazinic nitrogen atoms with an unshared electron pair and may take part in nucleophilic condensations. Therefore, the reactions of allyl‐β‐diketone complexes with malonic dihydrazide have also been studied, as these cause ring closure and formation of supramolecular macrocyclic ligand complexes. The wavelengths of the principal electronic absorption peaks have been accounted for quantitatively in terms of crystal field theory, and various parameters have been evaluated. On the basis of the electronic spectra, an octahedral geometry has been established for the polymer complexes C. The macrocyclic polymer complexes D are pentacoordinate, and a trigonal‐bipyramidal environment (D_3h) is suggested for the ruthenium(III) ion. The effect of the Hammett constant on the ligand field parameters is also discussed. Copyright © 2004 John Wiley & Sons, Ltd.     

Supramolecular architectures in metal(II) (Cd/Zn) halide/nitrate complexes of cytosine/5‐fluorocytosine

Three new metal(II)–cytosine (Cy)/5‐fluorocytosine (5FC) complexes, namely bis(4‐amino‐1,2‐dihydropyrimidin‐2‐one‐κN³)diiodidocadmium(II) or bis(cytosine)diiodidocadmium(II), [CdI₂(C₄H₅N₃O)₂], ( I ), bis(4‐amino‐1,2‐dihydropyrimidin‐2‐one‐κN³)bis(nitrato‐κ²O,O′)cadmium(II) or bis(cytosine)bis(nitrato)cadmium(II), [Cd(NO₃)₂(C₄H₅N₃O)₂], ( II ), and (6‐amino‐5‐fluoro‐1,2‐dihydropyrimidin‐2‐one‐κN³)aquadibromidozinc(II)–6‐amino‐5‐fluoro‐1,2‐dihydropyrimidin‐2‐one (1/1) or (6‐amino‐5‐fluorocytosine)aquadibromidozinc(II)–4‐amino‐5‐fluorocytosine (1/1), [ZnBr₂(C₄H₅FN₃O)(H₂O)]·C₄H₅FN₃O, ( III ), have been synthesized and characterized by single‐crystal X‐ray diffraction. In complex ( I ), the Cd^II ion is coordinated to two iodide ions and the endocyclic N atoms of the two cytosine molecules, leading to a distorted tetrahedral geometry. The structure is isotypic with [CdBr₂(C₄H₅N₃O)₂] [Muthiah et al. (2001). Acta Cryst. E 57 , m558–m560]. In compound ( II ), each of the two cytosine molecules coordinates to the Cd^II ion in a bidentate chelating mode via the endocyclic N atom and the O atom. Each of the two nitrate ions also coordinates in a bidentate chelating mode, forming a bicapped distorted octahedral geometry around cadmium. The typical interligand N—H…O hydrogen bond involving two cytosine molecules is also present. In compound ( III ), one zinc‐coordinated 5FC ligand is cocrystallized with another uncoordinated 5FC molecule. The Zn^II atom coordinates to the N(1) atom (systematic numbering) of 5FC, displacing the proton to the N(3) position. This N(3)—H tautomer of 5FC mimics N(3)‐protonated cytosine in forming a base pair (via three hydrogen bonds) with 5FC in the lattice, generating two fused R₂²(8) motifs. The distorted tetrahedral geometry around zinc is completed by two bromide ions and a water molecule. The coordinated and nonccordinated 5FCs are stacked over one another along the a‐axis direction, forming the rungs of a ladder motif, whereas Zn—Br bonds and N—H…Br hydrogen bonds form the rails of the ladder. The coordinated water molecules bridge the two types of 5FC molecules via O—H…O hydrogen bonds. The cytosine molecules are coordinated directly to the metal ion in each of the complexes and are hydrogen bonded to the bromide, iodide or nitrate ions. In compound ( III ), the uncoordinated 5FC molecule pairs with the coordinated 5FC ligand through three hydrogen bonds. The crystal structures are further stabilized by N—H…O, N—H…N, O—H…O, N—H…I and N—H…Br hydrogen bonds, and stacking interactions.     

Characterization of Defined Metal‐Containing Supramolecular Block Copolymers

The characterization of metal‐containing supramolecular polymers by gel permeation chromatography (GPC) or matrix‐assisted laser desorption ionisation time‐of‐flight mass spectrometry (MALDI‐TOF MS) is complicated because of the interaction of the charged materials with the GPC column material in the first case and fragmentation due to the applied laser energy in the latter case. In this contribution we report recent advances made for the characterization of supramolecular polymers based on terpyridine metal complexes utilizing GPC and MALDI‐TOF MS. In particular for GPC analysis, the choice of solvent and additive was found to be crucial for a successful characterization. Furthermore, MALDI‐TOF MS spectra of these compounds are not straightforward to interpret. Both aspects are discussed in detail with the result of a better understanding and improved analysis possibilities of the mentioned supramolecular polymers.

A GPC‐coupled in‐line diode array spectrum of one of the complexes investigated here.     

Supramolecular structures of metal complexes containing barbiturate and 1,2-bis(4-pyridyl)-ethane

This work describes the synthesis, thermal, spectroscopic properties (Raman and infrared), and crystal structures of five new supramolecular compounds [Mn(bpa)(H₂O)₄]B₂?·?4H₂O (1), [Fe(bpa)(H₂O)₄]B₂?·?4H₂O (2), [Co(bpa)(H₂O)₄]B₂?·?4H₂O (3), [Zn(bpa)(H₂O)₄]B₂?·?4H₂O (4), and Co₂mal₂bpa?·?2H₂O (5), where B is the anion of barbituric acid, bpa is 1,2-bis(4-pyridyl)-ethane, and mal is malonate ion. Compounds 1–4 are isostructural, showing covalent linear 1-D [M(bpa)(H₂O)₄]²⁺ chains, which interact by hydrogen-bonding and π-stacking interactions with barbiturate and crystallization water molecules resulting in a 3-D arrangement, belonging to Pbcn space group. Compound 5 has been obtained from the opening of the barbituric acid ring, with the formation of malonate, coordinated simultaneously to three cobalts in a 1-D chain along the c-axis, whereas bpa ligand gives rise to another 1-D chain along the a- and b-axes, resulting in a 3-D coordination polymer containing cavities. The vibrational spectra of 1–4 are also very similar; Raman spectra display two intense bands related to bpa at 1616 and 1020?cm^?1, assigned to the (ν _CC/ν _CN) and ring stretching modes, respectively. The barbiturate is also confirmed by a band at 684?cm^?1; the interesting point to be emphasized is this vibrational mode is not observed for 5, corroborating the absence of this building block in the structure.     

Design of temperature sensitive imprinted polymer hydrogels based on multiple-point hydrogen bonding

Weakly cross-linked temperature sensitive imprinted polymer hydrogels that recognize L-pyroglutamic acid (Pga) molecules via multiple-point hydrogen bonding were designed and synthesized. The amount of adsorption for Pga in imprinted hydrogels is 3-4 times higher than that in non-imprinted hydrogels. The selectivity test of imprinted polymer gels was carried out by using a series of structurally related compounds Pga, pyrrolidine, 2-pyrrolidone, L-proline as substrates. The results show that imprinted polymer gels exhibit high selectivity for Pga as compared to all the other tested substrates. The imprinted polymer hydrogels show good temperature sensitivity, special selectivity and reusability, suggesting that the polymer hydrogels would have an enormous potential for application in controlled drug release and separation field.     

Particle and breath figure formation of triblock copolymers having self‐complementary hydrogen‐bonding units

Novel triblock copolymers having self‐complementary hydrogen‐bonding units were synthesized by using reversible addition–fragmentation transfer polymerization. As characterized by dynamic light scattering and atomic force microscopy, these polymers formed noncovalently crosslinked polymer particles and showed an aggregation behavior by intermolecular and intramolecular interactions. At low concentration, polymers formed nanoparticles, and the particle diameter increased with increasing polymer concentration. Well‐ordered hexagonal microstructures were prepared by “Breath Figure” technique with the triblock copolymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

The structures of the isomorphous potassium and rubidium salts of 4‐nitrobenzoic acid and an overview of the metal complex stereochemistries of the alkali metal salt series with this ligand

4‐Nitrobenzoic acid (PNBA) has proved to be a useful ligand for the preparation of metal complexes but the known structures of the alkali metal salts of PNBA do not include the rubidium salt. The structures of the isomorphous potassium and rubidium polymeric coordination complexes with PNBA, namely poly[μ₂‐aqua‐aqua‐μ₃‐(4‐nitrobenzoato)‐potassium], [K(C₇H₄N₂O₂)(H₂O)₂]_n, (I), and poly[μ₃‐aqua‐aqua‐μ₅‐(4‐nitrobenzoato)‐rubidium], [Rb(C₇H₄N₂O₂)(H₂O)₂]_n, (II), have been determined. In (I), the very distorted KO₆ coordination sphere about the K⁺ centres in the repeat unit comprise two bridging nitro O‐atom donors, a single bridging carboxylate O‐atom donor and two water molecules, one of which is bridging. In Rb complex (II), the same basic MO₆ coordination is found in the repeat unit, but it is expanded to RbO₉ through a slight increase in the accepted Rb—O bond‐length range and includes an additional Rb—O_carboxylate bond, completing a bidentate O,O′‐chelate interaction, and additional bridging Rb—O_nitro and Rb—O_water bonds. The comparative K—O and Rb—O bond‐length ranges are 2.7352 (14)–3.0051 (14) and 2.884 (2)–3.182 (2) Å, respectively. The structure of (II) is also isomorphous, as well as isostructural, with the known structure of the nine‐coordinate caesium 4‐nitrobenzoate analogue, (III), in which the Cs—O bond‐length range is 3.047 (4)–3.338 (4) Å. In all three complexes, common basic polymeric extensions are found, including two different centrosymmetric bridging interactions through both water and nitro groups, as well as extensions along c through the para‐related carboxylate group, giving a two‐dimensional structure in (I). In (II) and (III), three‐dimensional structures are generated through additional bridges involving the nitro and water O atoms. In all three structures, the two water molecules are involved in similar intra‐polymer O—H...O hydrogen‐bonding interactions to both carboxylate and water O‐atom acceptors. A comparison of the varied coordination behaviour of the full set of Li–Cs salts with 4‐nitrobenzoic acid is also made.     

Thermally responsive complex polymer networks containing Fe3O4 nanoparticles: Composition/morphology/property relationship

In this research, the synthesis and properties of thermally responsive complex polymer networks containing Fe₃O₄ nanoparticles were studied. First, a stable ferrofluid containing Fe₃O₄ nanoparticles was synthesized via a coprecipitation method in the presence of a poly(acrylic acid) oligomer. This stable ferrofluid could mix well with water‐soluble monomers by the adjustment of its pH value. Second, a thermally responsive copolymer was synthesized in the presence of the ferrofluid containing Fe₃O₄ nanoparticles to obtain the complex polymer networks. By the adjustment of the pH value, the ferrofluid could remain stable in the polymerization system, in which N‐isopropylacrylamide (NIPAAm) and methacrylic acid (MAA) were used as comonomers to provide thermoresponsive properties and acid groups and ammonium persulfate and sodium metabisulfite were used as the redox initiator system. Several variables, such as the molar ratio of MAA to NIPAAm, the concentrations of the monomers and crosslinking agent, the addition of an ammonium solution, and the content of the ferrofluid, were studied in this polymerization. Their effects on the morphology, structure, polymerization rate, and thermal properties of the complex polymer networks were discussed. The swelling and thermoresponsive behaviors of the complex polymer networks containing Fe₃O₄ nanoparticles were also studied, and the composition–morphology–property relationship was established. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5923–5934, 2005     

Ultrasound in polymer chemistry: Revival of an established technique

The history of ultrasound in polymer chemistry goes back a long way. Initially, its uses were limited to being an alternative method of initiating radical polymerizations through the decomposition of solvents to form radicals or through the breakage of polymers leading to macroradicals. Recently, the raw power of ultrasound has been focused through the use of weak linkages in polymer chains, which enables the production of well‐defined macroradicals and coordinatively unsaturated metal complexes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5445–5453, 2006     

Diblock copolymer–azobenzene complexes through hydrogen bonding: Self‐assembly and stable photoinduced optical anisotropy

We have demonstrated the preparation of a series of photoaddressable supramolecular block copolymers by mixing a carboxy‐terminated azobenzene derivative, 6‐[4‐(4′‐cyanophenylazo)phenyloxy]hexanoic acid (AZO), and two polystyrene‐b‐poly(4‐vinylpiridine) (PS‐b‐P4VP) block copolymers. AZO can be selectively attached to the P4VP block of PS‐b‐P4VP through hydrogen bonding interactions. The assembly of AZO with vinylpyridine group‐containing polymers was initially investigated on a model system composed of P4VP homopolymer and AZO. Homogeneous liquid crystalline materials were obtained for ratios of AZO to vinylpyridine repeating unit, x, lower or equal to 0.50. Mixtures with higher x resulted in heterogeneous materials showing clear macrophase separation. Accordingly, a series of hydrogen‐bonded complexes of PS‐b‐P4VP and AZO, PS‐b‐P4VP(AZO)_x, with x = 0.25 and x = 0.50 were prepared. Lamellar and spherical morphologies were observed for the complexes based on PS24‐b‐P4VP9.5 (M_n,PS = 24,000, M_n,P4VP = 9500) and PS24‐b‐P4VP1.9 (M_n,PS = 24,000, M_n,P4VP = 1900), respectively. Photoinduced orientation of the azobenzene units was obtained in films of P4VP(AZO)_x and PS‐b‐P4VP(AZO)_x with x = 0.25 and 0.50 by using 488 nm linearly polarized light and characterized through birefringence and dichroism measurements. This investigation shows a versatile and less laborious approach to azobenzene‐containing polymer materials with low chromophore content, of interest in optical application. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Rigid chain ribbon‐like metallopolymers

A set of new copolymers is here reported in which the repeating units are connected each other through Cu(II) metal centers. The coordination link is based on the bis‐chelating properties of salicylaldiminate groups of two different monomers. Due to their chemical structure, the two monomers afford, respectively, flexible and rigid repeating units in the metallocopolymers constitution upon coordination to copper centers. All the copolymers were soluble and easily processable. As shown by XRD analysis, rigid units' rich copolymers adopt a ribbon‐like structure in solid state in which highly planar strands of polymer stack thanks to π?π interactions, similarly to the polymer composed exclusively by rigid units. This behavior can be justified assuming the existence of a partial block character in copolymer constitution where long sequences of rigid units are alternated to sequences of flexible units. This assumption is supported also by DSC and UV–Vis analysis. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2412–2421     

Quadruple hydrogen bonding containing supramolecular thermoplastic elastomers: Mechanical and morphological correlations

We report the design of bioinspired, reversible supramolecular thermoplastic elastomers (TPEs) functionalized with ureido‐cytosine (UCyt) complementary quadruple hydrogen bonding (QHB) sites. The polymer contained a soft poly(n‐butyl acrylate) central block that imparted flexibility and two external, hard nucleobase‐containing blocks that contributed to structural integrity. In addition, the hard block with pendant QHB motifs served as efficient physical crosslinks to further enhance the thermomechanical performance, where the polymer service window extended up to 30 °C higher compared to the controls that bear dimeric hydrogen bonding units. The resulting UCyt copolymers also exhibited improved surface and bulk morphology, which self‐assembled into well‐ordered lamellar microstructures. Moreover, the polymer displayed an unexpected moisture‐resistant property with less than 1 wt % equilibrium moisture uptake even at 95% relatively humidity, which presumably correlated with its well‐ordered and densely‐packed morphology facilitated by strong hydrogen bonding. Variable temperature Fourier‐transform infrared spectroscopy experiments further confirmed the thermoreversibility of hydrogen bonding, indicating melt‐processablility and recyclability of the polymer. These physical properties verified quadruple bonding dominated behavior, and structure–property–morphology relationships suggest key design parameters for future TPEs. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 13–23     

End‐functionalization of semiconducting species with dendronized terpyridine–Ru(II)–terpyridine complexes

Semiconducting oligomers and polymers decorated with two or one dendronized tpy‐Ru(II)‐tpy metallocomplexes are presented. Initially, free terpyridine end‐functionalized semiconducting oligomers (distyrylanthracene, quinquephenylene, mono‐ and trifluorenes) were prepared while in a second approach, atom transfer radical polymerization was employed for the preparation of side‐chain oligomeric and polymeric (oxadiazole)s using a terpyridine initiator. These terpyridine‐bearing oligomers and polymers were complexated with a Percec‐type first‐generation (G1) dendronized terpyridine–Ru(III)Cl₃ monocomplex, having two dodecyloxy groups. All oligomeric and polymeric metallocomplexes were characterized via NMR spectroscopies for their structural perfection and via UV‐Vis and PL spectroscopies for their optical properties. The existence of the organic semiconducting blocks in combination with the terpyridine–Ru(II)–terpyridine groups afforded hybrid metallo‐semiconducting species presenting the optical features of both their components. Moreover, their thin‐film morphologies were investigated through atomic force microscopy, revealing, in some cases, an organization tendency in the nanometer scale. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1939–1952, 2009     

Metallo‐Supramolecular Diethylene Glycol: Water‐Soluble Reversible Polymers

Bis(2,2′:6′,2″‐terpyrid‐4′‐yl) diethylene glycol was synthesized as a monomer unit and further utilized for polymerization with FeCl₂ in order to form water‐soluble coordination polymers. Viscosity measurements and film‐forming properties indicate the formation of linear coordination polymers or larger ring structures. The terpyridine/iron(II) complexes are stable up to temperatures of 210 °C, but can be uncomplexed by the addition of an excess of a strong competitive ligand (HEDTA) under mild conditions.

     

Synthesis and characterization of chiral polymer complexes incorporating polybinaphthyls,bipyridine, and Eu(III)

Chiral conjugated polymers P‐1 and P‐2 were synthesized by the polymerization of (S)‐3,3′‐diiodo‐2,2′‐bisbutoxy‐1,1′‐binaphthyl and (S)‐6,6′‐dibromo‐2,2′‐bisbutoxy‐1,1′‐binaphthyl, respectively, with 5,5′‐divinyl‐2,2′‐bipyridine through a Heck cross‐coupling reaction. Chiral polymer complexes P‐C‐1 and P‐C‐2 were obtained by the bipyridine chelating coordination of P‐1 and P‐2 with Eu(TTA)₃·2H₂O (where TTA is 2‐thenoyltrifluoroacetonate). Polymers P‐1 and P‐2 and polymer complexes P‐C‐1 and P‐C‐2 exhibited intense circular dichroism signals, with negative and positive Cotton effects in their circular dichroism spectra. The chiral polymers showed strong green‐blue fluorescence because of the efficient energy migration from the extended π‐electronic structure of the conjugated polymer main to the chiral binaphthyl core. The chiral polymer complexes could have not only polymer fluorescence but also the characteristic fluorescence of Eu(III) (⁵D₀→⁷F₂) at a different excited wavelength. These kinds of chiral polymer complexes incorporating polybinaphthyls, bipyridine, and Eu(III) moieties are expected to provide an understanding of the relationship between the structure and properties of chiral polymer complexes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 650–660, 2007     

Side‐chain terpyridine polymers through atom transfer radical polymerization and their ruthenium complexes

Polymers containing side‐chain terpyridine ligands of well‐defined architectures and controllable molecular weights and molecular weight distributions are reported. These polymers were synthesized by the atom transfer radical polymerization (ATRP) of a newly synthesized terpyridine monomer with three functional initiators. The obtained polymers were characterized with ¹H NMR and gel permeation chromatography techniques. The efficiency of the ATRP technique and the overall control of the molecular characteristics of the polymers were demonstrated by a kinetic study of the polymerization reaction. Subsequently, the ruthenium(III)/ruthenium(II) complexation chemistry was employed for the attachment of bis(dodecyloxy)‐functionalized terpyridine moieties onto each side 2,2′:6′,2″‐terpyridine unit of the main polymeric backbone. Thus, the grafting approach was successfully combined with the metal–ligand coordination chemistry for the preparation of highly soluble polymeric complexes. The resulting complexes were fully characterized by means of ¹H NMR, gel permeation chromatography, and ultraviolet–visible spectroscopy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4838–4848, 2005     

Interactions in a blend of two polymers greatly differing in glass transition temperature

Blends of poly(N‐methyldodecano‐12‐lactam) PMDL with poly(4‐vinyphenol) PVPh have been studied by the DSC and ATR FTIR methods. The difference in glass transition temperature T_g between the components is 206 °C. A single composition‐dependent T_g suggests miscibility of the system, that is, homogeneity on the scale of about 10 nm. Fitting of the equation of Brostow et al. to the T_g data indicates relatively strong specific interactions and high complexity of the system. The Schneider's equation applied separately to low‐ and high‐PVPh regions provides good agreement with experiment; the calculated curves cross at the point of PVPh weight fraction 0.27. In the low‐PVPh region, the analysis indicates weak interactions with predominance of segment homocontacts and strong involvement of conformational entropy. In the high‐PVPh region, strong specific interactions predominate and entropic effects are suppressed. Composition dependences of the heat capacity difference at T_g and the width of glass transition indicate strong interactions in the system and existence of certain heterogeneities on segmental level, respectively. According to ATR FTIR, hydrogen bonds between PVPh as proton donor and PMDL as proton acceptor induce miscibility in blends of higher PVPh content (above about 0.28 weight fraction). In low‐PVPh blends, it is conformational entropy that enables intimate intermolecular mixing. Hydrogen bonds adopt several (distorted) geometries and are on average stronger than average hydrogen bonds formed in self‐associating PVPh. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011