Foldable Polymer Research Articles

Supramolecular Organic Ferroelectric Materials from Donor-Acceptor Systems.

Organic ferroelectric (FE) materials, though known for more than a century, are yet to reach close to the benchmark of inorganic or hybrid materials in terms of the magnitude of polarization. Amongst the different classes of organic systems, donor (D)-acceptor (A) charge-transfer (CT) complexes are recognized as promising for ferroelectricity owing to their neutral-to-ionic phase transition at low temperature. This review presents an overview of different supramolecular D-A systems that have been explored for FE phase transitions. The discussion begins with a general introduction of ferroelectricity and its different associated parameters. Then it moves on to show early examples of CT cocrystals that have shown FE properties at sub-ambient temperature. Subsequently, recent developments in the field of room temperature (RT) ferroelectricity, exhibited by H-bond-stabilized lock-arm supramolecular-ordering (LASO) in D-A co-crystals or other FE CT-crystals devoid of neutral-ionic phase transition are discussed. Then the discussion moves on to emerging reports on other D-A soft materials such as gel and foldable polymers; finally it shows very recent developments in ferroelectricity in supramolecular assemblies of single-component dipolar or ambipolar π-systems, exhibiting intra-molecular charge transfer. The effects of structural nuances such as H-bonding, balanced charge transfer and chirality on the observed ferroelectricity is described with the available examples. Finally, piezoelectricity in recently reported ambipolar ADA-type systems are discussed to highlight the future potential of these soft materials in micropower energy harvesting.

Preparation and characterization of novel transparent and foldable polymers modified with Cr(III), Co(II), Ni(II), and Cu(II) complexes

The properties of films prepared from polystyrene (PS), poly(methyl methacrylate) (PMMA), and polystyrene (PS)/poly(methyl methacrylate) (PMMA) blends and composite films prepared with metal ion-centered complexes were compared. New complexes of Cr(III), Co(II), Ni(II), and Cu(II) prepared according to the template were synthesized from ligand L (4-hydroxy-N-[2-[(4-hydroxybenzoyl)amino]ethyl]benzamide) prepared by condensation of 4-hydroxybenzoic acid and ethylenediamine. Structural analysis of ligands and complexes were determined by LC-MS, 1H-NMR, FTIR, UV-Vis, and XRD. The conductivities and magnetic susceptibility of novel complexes were measured. Morphological properties of the transparent films by SEM and AFM, their thermal stabilities by TGA, and their optical properties by refractometry were characterized. Original composite films of PS, PMMA, and PS/PMMA blend modified with novel complexes were obtained as thermally stable, transparent, and foldable composite films with permanent colors.

Hierarchical assembly of foldable polymers and applications in organic optoelectronics and antibacterial or antiviral materials.

Aggregation of amphiphilic polymers in block-selective solvents produces different nanostructures, which have been studied extensively for wide-ranging applications. Nevertheless, such immiscibility-driven aggregation does not endow them with the desired structural precision, predictability or surface functional group exposure, which significantly impact their functional applications. More recently, biomimetic folded structures of synthetic macromolecules (mostly oligomers) have come to the fore, but such studies have been limited to probe the secondary structures. In this article, we have collated hierarchical structures of foldamers, especially highlighting our recent contribution to the field of chain-folding regulated assembly of segmented polyurethanes (PUs) and their functional applications. A series of such PUs have been discussed, which contain a segmented hydrocarbon backbone and alternately placed pendant solvophilic groups. In either water or highly non-polar solvents (TCE, MCH), depending on the nature of the pendant group, they exhibit folded structures stabilized by intra-chain H-bonding. Hierarchical assembly of such folded chains by inter-chain H-bonding and/or π-stacking leads to the formation of well-defined nanostructures with functional applications ranging from organic optoelectronics to biomaterials. For example, a segmented PU with appended naphthalene-diimide (NDI) chromophores showed a pleated structure in MCH, which helped in organization of the NDI chromophores within π-stacking distance. Such folded polymer chains eventually produced nanotubular structures with excellent electron mobility. They also showed efficient intercalation of the pyrene (Py) donor by NDI-Py charge-transfer interaction and in this case the mixed nanotubular structure exhibited prominent room-temperature ferroelectricity. On the other hand, having cationic functionalities as the pendant groups such chain-folding regulated assembly produced unilamellar polymersomes with excellent antibacterial activity with very low minimum inhibitory concentrations (<10 μg mL-1). Replacing the pendant amine functionality with sulphate groups made these polyurethanes highly potent antiviral materials. In the absence of the alternating connectivity of the solvophobic and solvophilic segments or rigid hydrocarbon backbone, such folding propensity is destroyed, leading to structural collapse. While significant efforts have been made in correlating primary structures of wide-ranging polymers with their functional applications, this article demonstrates the direct correlation between the secondary structures of polymers and their functional properties.

The Aramid-Coating-on-Aramid Strategy toward Strong, Tough, and Foldable Polymer Aerogel Films.

Aerogel has been much highlighted as an emerging lightweight thermal insulation material, but problems such as fragility, low strength, liquid permeability, and lack of flexibility greatly limit further applications. In this work, a facile aramid-coating-on-aramid (ACoA) method is demonstrated to fabricate all-aramid aerogel composite films for thermal insulation. The method started from the bottom-up synthesis of polymerization-induced para-aramid nanofibers (PANF), which were easily transformed into aerogel films through the vacuum-assisted filtration followed by the freeze-drying techniques. Then, the heterocyclic aramid (HA) solution prepared through the low-temperature-solution polycondensation was used as the coating to be applied onto the PANF aerogel films, and composite films of HA/PANF aerogel were simply achieved with HA contributed to the dense and continuous surface layer. The bulk HA film is of superior mechanical and thermal properties to those of the PANF film. Moreover, reliable interfacial interlocking structures were developed beneath the outermost surface via the interpenetration of the infiltrated HA with PANF network. The comprehensive result was the 15 times enhanced tensile strength, 33 times enhanced fracture toughness, the high thermal decomposition temperature, and the additional flexibility for the foldable films of HA/PANF aerogel. The sealing of the surface macropores greatly suppressed the surface chalking and high water absorption. However, the survival of the tiny pores inside the composite maintained the low enough level of the thermal conductivity to provide effective protections against high temperature not only in air but also under wet or even liquid conditions, suggesting the broader applications for thermal insulation.

Designing ultratough, malleable and foldable biocomposites for robust green electronic devices

Nanoscale domains and entangled interfaces create ultratough, malleable and foldable polymer blends from common biodegradable plastics, which find applications in green flexible electronic devices.

Completely foldable electronics based on homojunction polymer transistors and logics.

An increase in the demand for completely foldable electronics has motivated efforts for the development of conducting polymer electrodes having extraordinary mechanical stability. However, weak physical adhesion at intrinsic heterojunctions has been a challenge in foldable electronics. This paper reports the completely foldable polymer thin-film transistors (PTFTs) and logic gate arrays. Homojunction-based PTFTs were fabricated by selectively doping p-type diketopyrrolopyrrole-based semiconducting polymer films with FeCl3 to form source/drain electrodes. The doping process caused a gradual work function change with depth, which promoted charge injection to semiconducting regions and provided a low contact resistance. In addition, the interfacial adhesion in the PTFTs was improved by interfacial cross-linking between adjacent component layers. The electrical performance of the resulting PTFTs was maintained without noticeable degradation even after extreme folding, suggesting that the proposed fabrication strategy can further be applied to various semiconducting polymers for the realization of foldable electronics.

Secondary Structure in Nonpeptidic Supramolecular Block Copolymers

Proteins contain a level of complexity-secondary and tertiary structures-that polymer chemists aim to imitate. The bottom-up synthesis of protein-mimicking polymers mastering sequence variability and dispersity remains challenging. Incorporating polymers with predefined secondary structures, such as helices and π-π stacking sheets, into block copolymers circumvents the issue of designing and predicting one facet of their 3D architecture. Block copolymers with well-defined secondary-structure elements formed by covalent chain extension or supramolecular self-assembly may be considered for localized tertiary structures.In this Account, we describe a strategy toward block copolymers composed of units bearing well-defined secondary structures mixed in a "plug-and-play" manner that approaches a modicum of the versatility seen in nature. Our early efforts focused on the concept of single-chain collapse to achieve folded secondary structures through either hydrogen bonding or quadrupole attractive forces. These cases, however, required high dilution. Therefore, we turned to the ring-opening metathesis polymerization (ROMP) of [2.2]paracyclophane-1,9-dienes (pCpd), which forms conjugated, fluorescent poly(p-phenylenevinylene)s (PPVs) evocative of β-sheets. Helical building blocks arise from polymers such as poly(isocyanide)s (PICs) or poly(methacrylamide)s (PMAcs) containing bulky, chiral side groups while the coil motif can be represented by any flexible chain; we frequently chose poly(styrene) (PS) or poly(norbornene) (PNB). We installed moieties for supramolecular assembly at the chain ends of our "sheets" to combine them with complementary helical or coil-shaped polymeric building blocks.Assembling hierarchical materials tantamount to the complexity of proteins requires directional interactions with high specificity, covalent chain extension, or a combination of both chemistries. Our design is based on functionalized reversible addition-fragmentation chain-transfer (RAFT) agents that allowed for the introduction of recognition motifs at the terminus of building blocks and chain-terminating agents (CTAs) that enabled the macroinitiation of helical polymers from the chain end of ROMP-generated sheets and/or coils. To achieve triblock copolymers with a heterotelechelic helix, we relied on supramolecular assembly with helix and coil-shaped building blocks. Our most diverse structures to date comprised a middle block of PPV sheets, parallel or antiparallel, and supramolecularly or covalently linked, respectively, end-functionalized with molecular recognition units (MRUs) for orthogonal supramolecular assembly. We explored PPV sheets with multiple folds achieved by chain extension using alternating pCpd and phenyl-pentafluorophenyl β-hairpin turns. Using single-molecule polarization spectroscopy, we showed that folding occurs preferentially in multistranded over double-stranded PPV sheets. Our strategy toward protein-mimicking and foldable polymers demonstrates an efficient route toward higher ordered, well-characterized materials by taking advantage of polymers that naturally manifest secondary structures. Our studies demonstrate the retention of distinct architectures after complex assembly, a paradigm that we believe may extend to other polymeric folding systems.

Highly transparent, writable and photoluminescent foldable polymer film: When fluorescent dyes or pigments join cellulose-based microgel

We prepared a self-dispersed cellulose-based microgel via chemically bonding hydrophilic gelatin peptide chain onto cellulose glucose chain. Following, a variety of highly transparent, foldable, and writable photoluminescent polymer films was obtained through loading organic dyes and inorganic pigments onto cellulose-based microgel matrix, respectively. Benefiting from the coupling sites and network effect of microgel as well as the abundant hydroxyl, amino, and imino groups in its structure, the microgel containing organic dyes and inorganic pigments exhibit good dispersion and stability, and the resultant photoluminescent films emit bright yellow, orange, yellow-green, and blue-green fluorescence under UV light, respectively, especially the cellulose-based microgel stabilized inorganic alkaline earth aluminate hybrids exhibit continuous luminescence for a long time in the dark. Compared with the existing regenerated cellulose or CNCs-based fluorescent films, the cellulose-based microgel fluorescent films present higher transmittance and good biodegradability. This study can bring new ideas for the development of flexible luminescent devices.

Realization of Foldable Polymer Solar Cells Using Ultrathin Cellophane Substrates and ZnO/Ag/ZnO Transparent Electrodes (Solar RRL 10∕2018)

In article no. 1800123, Weiyan Wang, Weijie Song, and co-workers demonstrate foldable polymer solar cells using ultrathin paper substrates to relieve strain, combined with foldable ZnO/ultrathin Ag/ZnO electrodes. The solar cells maintain 92% of the initial efficiency after 35 folding cycles.

Highly Transparent, Deformable, and Multifunctional AgPdCu/ITO/PTFE Hybrid Films for Self‐Cleaning, Flexible, and Energy‐Saving Smart Windows

AbstractRollable, bendable, twistable, and foldable polymer–oxide–metal multistacked hybrid films are demonstrated, which simultaneously act as multifunctional electrodes in flexible polymer‐dispersed liquid crystal (PDLC) windows and flexible and transparent thin‐film heaters (TFHs) for self‐cleanable and flexible smart windows. By continuous sputtering of a thin polytetrafluoroethylene (PTFE)–indium tin oxide (ITO)–AgPdCu (APC) multilayer on a colorless polyimide substrate, transparent and multifunctional films are fabricated with a low sheet resistance of 7 Ω □−1, high optical transmittance of 83% at a wavelength of 550 nm, low transmittance in the infrared region, and a high contact angle of 109°. Based on inner/outer bending, rolling, twisting, and folding tests, the outstanding flexibility of these PTFE/ITO/APC multistacked films is demonstrated. The flexible PDLC and flexible TFHs with PTFE/ITO/APC multistacked electrodes show a controllable transmittance range between the on and off states that is nearly 40%, and a high saturation temperature of 111 °C is observed at a low applied voltage of 4 V. The multifunctional properties of the flexible PDLC and TFHs fabricated on PTFE/ITO/APC hybrid films indicate that the polymer–oxide–metal hybrid film is a versatile transparent electrode that can be used for flexible, smart, and energy‐saving windows.

Water-borne foldable polymer solar cells: one-step transferring free-standing polymer films onto woven fabric electrodes

“Water-borne polymer solar cells (PSCs)” are demonstrated for the first time and a PCE of 2.90% was achieved using P3HT:PCBM.

Control of optical and electrical properties of nanosheets by the chemical structure of the turning point in a foldable polymer.

Oligomers of tetra(ethylene glycol)-disubstituted phenyl-capped bithiophene (Ph2TPh) linked by catechol and resorcinol were prepared. Catechol and resorcinol link the monomers via the ortho- and meta-positions of the benzene ring, respectively, and function as turning points in the folding process of the polymer. It was confirmed that the ortho-linked 8mer (o-8mer) and meta-linked 8mer (m-8mer) could form nanosheets through the self-assembly of folded polymers in o-dichlorobenzene. We confirmed that the arrangement of thiophene units inside the nanosheets was controllable by changing the chemical structure of the turning point. The different arrangements of the Ph2TPh units led to changes in other physical properties such as UV-Vis absorption, nanosheet thickness and charge carrier transport. The absorption spectrum of the o-8mer nanosheets suggested that the Ph2TPh units are arranged vertical to the lateral direction of the nanosheets. On the other hand, the Ph2TPh units in the m-8mer nanosheets were considered to have a tilted orientation. The change in the Ph2TPh tilt angle inside the nanosheets was supported by the different thicknesses of the o-8mer and m-8mer nanosheets. The relationship between the absorption spectrum and Ph2TPh unit arrangement was discussed based on the DFT calculation. Intrinsic charge carrier transport properties were evaluated by a noncontact microwave-based method. The o-8mer nanosheets showed higher conductivity than the m-8mer and triazole-linked-8mer nanosheets. The lifetime of charge carriers in the nanosheet was longer than that in the lamellar structure of the drop-cast film.

Selectively modulated inkjet printing of highly conductive and transparent foldable polymer electrodes for flexible polymer light-emitting diode applications

High efficient flexible polymer light-emitting devices which composed with highly conductive and transparent foldable polymer electrodes were fabricated. New doping materials, n-methyl-2-pyrrolidone (NMP) and n-methylformamide (NMF), have much improved the conductivity of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). The selectively modulated inkjet-printing method facilitated the PEDOT:PSS’s application to both transparent anodes and highly conductive bus line electrodes. Multiple-time printed PEDOT:PSS electrodes showed a similar performance to Ag bus lines while one-time printed anode showed a much better figure of merit than that of ITO on plastic. Due to the flexible property, high transparency and high work function of the polymeric anode, ITO-free PLEDs showed a high performance with foldable characteristics.

Foldable polymer patches with implemented pressure sensors

Foldable polymer patches with implemented pressure sensors

High performance foldable polymer thin film transistors with a side gate architecture

Foldable polymer thin film transistors gated by an ion gel dielectric were fabricated on a polymer substrate. Side gate structure was employed to simplify the fabrication process, which is a unique advantage of the transistors based on the ion gel dielectric. Utilizing the diffusion of crosslinkable oligomers in the P3HT thin films followed by UV gelation through a patterned mask, the ion gel made a strong bonding to the P3HT layer. Due to the deformable nature of the ion gel dielectric, the transistor arrays were electrically and mechanically stable at repeated folding events.

Blind Test of Physics-Based Prediction of Protein Structures

We report here a multiprotein blind test of a computer method to predict native protein structures based solely on an all-atom physics-based force field. We use the AMBER 96 potential function with an implicit (GB/SA) model of solvation, combined with replica-exchange molecular-dynamics simulations. Coarse conformational sampling is performed using the zipping and assembly method (ZAM), an approach that is designed to mimic the putative physical routes of protein folding. ZAM was applied to the folding of six proteins, from 76 to 112 monomers in length, in CASP7, a community-wide blind test of protein structure prediction. Because these predictions have about the same level of accuracy as typical bioinformatics methods, and do not utilize information from databases of known native structures, this work opens up the possibility of predicting the structures of membrane proteins, synthetic peptides, or other foldable polymers, for which there is little prior knowledge of native structures. This approach may also be useful for predicting physical protein folding routes, non-native conformations, and other physical properties from amino acid sequences.

Statistical Mechanics of Helix Bundles Using a Dynamic Programming Approach

Despite much study, biomolecule folding cooperativity is not well understood. There are quantitative models for helix-coil transitions and for coil-to-globule transitions, but no accurate models yet treat both chain collapse and secondary structure formation together. We develop here a dynamic programming approach to statistical mechanical partition functions of foldamer chain molecules. We call it the ascending levels model. We apply it to helix-coil and helix-bundle folding and cooperativity. For 14- to 50-mer Baldwin peptides, the model gives good predictions for the heat capacity and helicity versus temperature and urea. The model also gives good fits for the denaturation of Oas's three-helix bundle B domain of protein A (F13W*) and synthetic protein alpha3C by temperature and guanidine. The model predicts the conformational distributions. It shows that these proteins fold with transitions that are two-state, although the transitions in the Baldwin helices are nearly higher order. The model shows that the recently developed three-helix bundle polypeptoids of Lee et al. fold anti-cooperatively, with a predicted value of DeltaHvH/DeltaHcal = 0.72. The model also predicts that two-helix bundles are unstable in proteins but stable in peptoids. Our dynamic programming approach provides a general way to explore cooperativity in complex foldable polymers.

Foldamers with Hybrid Biological and Synthetic Sequences as Selective DNA Fluorescent Probes

Foldable polymers with alternating single-strand deoxyribonucleic acid (ssDNA) and planar fluorescent organic chromophores can self-organize into folded nanostructures and hence are hybrid foldamers with biological sequences and synthetic properties. The biological sequence provides highly specific molecular recognition properties, while the physical properties of synthetic chromophores offer sensitive fluorescence detection. In this paper, we describe that rational designed hybrid foldamers exhibit potential in the detection of polynucleotides. Under strictly controlled laboratory conditions, fluorescence measurements indicate that configuration change due to binding of polynucleotides with one or two mismatched bases can be readily distinguished. These results shed light on the design and construction of nanostructured foldamers with actuator and sensory properties, which may find important applications as biological probes.

Folding versus Self‐Assembling.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Folding versus Self‐Assembling

Model foldable polymers with sequences of rigid hydrophobic chromophores and flexible hydrophilic tetra(ethylene glycol) were synthesized and used as a paradigm for studying molecular-folding and self-assembly phenomena. Our results demonstrate that intramolecular association or folding prevails over intermolecular interaction or self-assembling in the concentration region from 1 microM to 0.1 M. Importantly, folded polymeric nanostructures have absorption and fluorescence properties that are distinct from those of unfolded polymers or free monomers. We hypothesize that the origins of folding and self-assembly come from interactions between molecular units, and that the key parameter that regulates the on-and-off of such interactions is the distance R separating the two molecular units. Each molecular unit produces a characteristic force field, and when another molecular unit enters this field, the probability that the two units will interact increases significantly. A preliminary estimate of the radius of such a force field for the perylene tetracarboxylic diimide chromophore is about 90-120 A. As a result, phenomena associated with folding or self-assembly of molecular species are observed when these conditions are met in solution.