Single Polymer Chain Research Articles

Flow Photochemistry for Single-Chain Polymer Nanoparticle Synthesis.

Single chain polymer nanoparticles (SCNP) are an attractive polymer architecture that provides functions seen in folded biomacromolecules. The generation of SCNPs, however, is limited by the requirement of a high dilution chemical step, necessitating the use of large reactors to produce processable quantities of material. Herein, the chemical folding of macromolecules into SCNPs is achieved in both batch and flow photochemical processes by the previously described photodimerization of anthracene units in polymethylmethacrylate (100 kDa) under UV irradiation at 366 nm. When employing flow chemistry, the irradiation time is readily controlled by tuning the flow rates, allowing for the precise control over the intramolecular collapse process. The flow system provides a route at least four times more efficient for SCNP formation, reaching higher intramolecular cross-linking ratios five times faster than batch operation.

Emergence of low-symmetry foldamers from single monomers.

Self-assembly is a powerful method to obtain large discrete functional molecular architectures. When using a single building block, self-assembly generally yields symmetrical objects in which all the subunits relate similarly to their neighbours. Here we report the discovery of a family of self-constructing cyclic macromolecules with stable folded conformations of low symmetry, which include some with a prime number (13, 17 and 23) of units, despite being formed from a single component. The formation of these objects amounts to the production of polymers with a perfectly uniform length. Design rules for the spontaneous emergence of such macromolecules include endowing monomers with a strong potential for non-covalent interactions that remain frustrated in competing entropically favoured yet conformationally restrained smaller cycles. The process can also be templated by a guest molecule that itself has an asymmetrical structure, which paves the way to molecular imprinting techniques at the level of single polymer chains.

Development and Testing of an All-Atom Force Field for Diketopyrrolopyrrole Polymers with Conjugated Substituents.

We develop an all-atom force field for a series of diketopyrrolopyrrole polymers with two aromatic pyridine substituents and a variable number of π-conjugated thiophene units in the backbone (DPP2PymT), used as donor materials in organic photovoltaic devices. Available intrafragment parameterizations of the individual fragment building blocks are combined with interfragment bonded and nonbonded parameters explicitly derived from density functional theory calculations. To validate the force field, we perform classical molecular dynamics simulations of single polymer chains with m = 1, 2, 3 in good and bad solvents and of melts. We observe the expected dependence of the chain conformation on the solvent quality, with the chain collapsing in water, and swelling in chloroform. The glass-transition temperature for the polymer melts is found to be in the range of 340–370 K. Analysis of the mobility of the conjugated segments in the polymer backbone reveals two relaxation processes: a fast one with a characteristic time at room temperature on the order of 10 ps associated with nearly harmonic vibrations and a slow one on the order of 100 ns associated with temperature-activated cis–trans transitions.

Mean-field tricritical polymers

We provide an introductory account of a tricritical phase diagram, in the setting of a mean-field random walk model of a polymer density transition, and clarify the nature of the density transition in this context. We consider a continuous-time random walk model on the complete graph, in the limit as the number of vertices $N$ in the graph grows to infinity. The walk has a repulsive self-interaction, as well as a competing attractive self-interaction whose strength is controlled by a parameter $g$. A chemical potential $\nu$ controls the walk length. We determine the phase diagram in the $(g,\nu)$ plane, as a model of a density transition for a single linear polymer chain. A dilute phase (walk of bounded length) is separated from a dense phase (walk of length of order $N$) by a phase boundary curve. The phase boundary is divided into two parts, corresponding to first-order and second-order phase transitions, with the division occurring at a tricritical point. The proof uses a supersymmetric representation for the random walk model, followed by a single block-spin renormalisation group step to reduce the problem to a 1-dimensional integral, followed by application of the Laplace method for an integral with a large parameter.

Long-Range LMCT Coupling in EuIII Coordination Polymers for an Effective Molecular Luminescent Thermometer*.

A design for an effective molecular luminescent thermometer based on long-range electronic coupling in lanthanide coordination polymers is proposed. The coordination polymers are composed of lanthanide ions EuIII and GdIII , three anionic ligands (hexafluoroacetylacetonate), and a chrysene-based phosphine oxide bridges (6,12-bis(diphenylphosphoryl)chrysene). The zig-zag orientation of the single polymer chains induces the formation of packed coordination structures containing multiple sites for CH-F intermolecular interactions, resulting in thermal stability above 350 °C. The electronic coupling is controlled by changing the concentration of the GdIII ion in the EuIII -GdIII polymer. The emission quantum yield and the maximum relative temperature sensitivity (Sm ) of emission lifetimes for the EuIII -GdIII polymer (Eu:Gd=1:1, Φtot =52 %, Sm =3.73 % K-1 ) were higher than those for the pure EuIII coordination polymer (Φtot =36 %, Sm =2.70 % K-1 ), respectively. Enhanced temperature sensing properties are caused by control of long-range electronic coupling based on phosphine oxide with chrysene framework.

Heat conduction in polymer chains with controlled end-to-end distance.

The low thermal conductance of polymers is one of the major drawbacks for many polymer-based products. However, a single polymer chain when stretched can have high thermal conductivities. We use non-equilibrium molecular dynamics simulations to study the steady-state thermal conductance along finite macromolecules under mechanical control of the end-to-end distance. We find that the nature of heat transport along such chains strongly depends on mechanical tuning, leading to significantly different heat conductions and temperature profiles along the chain in the compressed-chain and stretched-chain limits. This transition between modes of behaviors appears to be a threshold phenomenon: at relatively small end-to-end distances, the thermal conductance remains almost constant as one stretches the polymer chain. At given critical end-to-end distances, thermal conductances start to increase, reaching the fully extended chain values. Correlated with this behavior are two observations: first, the temperature bias falls mostly at contacts in the fully stretched chain, while part of it falls along the molecule in the compressed limit. Second, the heat conduction does not change significantly with the chain length in the stretched-chain limit but decreases dramatically when this length increases in the compressed molecule. This suggests that heat transfer along stretched chains is mostly ballistic, while in the compressed chain, heat is transferred by diffusive mechanisms. Significantly, these trends persist also for a large range of molecular structures and force fields, and the changing behavior correlates well with mode localization properties. Similar studies conducted with disordered chains and bundles of several chains show remnants of the same behavior.

Molecular motor-functionalized porphyrin macrocycles

Molecular motors and switches change conformation under the influence of an external stimulus, e.g. light. They can be incorporated into functional systems, allowing the construction of adaptive materials and switchable catalysts. Here, we present two molecular motor-functionalized porphyrin macrocycles for future photo-switchable catalysis. They display helical, planar and point chirality, and are diastereomers, which differ in the relative orientation of the motor and macrocyclic components. Fluorescence, UV-vis, and 1H NMR experiments reveal that the motor-functionalized macrocycles can bind and thread different variants of viologen guests, including a one-side blocked polymeric one of 30 repeat units. The latter feature indicates that the motor systems can find the open end of a polymer chain, thread on it, and move along the chain to eventually bind at the viologen trap, opening possibilities for catalytic writing on single polymer chains via chemical routes.

Controlling the Chain Folding for the Synthesis of Single-Chain Polymer Nanoparticles Using Thermoresponsive Polymers

Synthetic polymer single-chain nanoparticles (SCNPs) are an emerging new class of nanomaterials that possess similar folded structures as natural proteins. However, most SCNPs reported so far are p...

Stealth and Bright Monomolecular Fluorescent Organic Nanoparticles Based on Folded Amphiphilic Polymer.

Fluorescent nanoparticles (NPs), owing to their superior brightness, are an attractive alternative to organic dyes. However, their cellular applications remain limited because of their large size, poor homogeneity, and nonspecific interactions in biological media. Herein, we propose a concept of monomolecular fluorescent organic nanoparticles of high brightness and very small size (10-14 nm) built of a single amphiphilic polymer bearing specially designed fluorescent dyes. We found that high PEGylation of poly(maleic anhydride-alt-1-octadecene (PMAO) favors a single-chain polymer folding into monomolecular stealth NPs with highly reduced nonspecific interactions with proteins and live cells. To ensure high stability of our NPs, the fluorophores (BODIPYs) are covalently linked to the polymer through an optimized linker. Among tested linkers of different lengths and polarity, a short medium-polar linker favoring location of the dyes at NPs interface ensures good fluorescence quantum yield and small particle size. The fluorescence brightness of these NPs has been dramatically enhanced by increasing the bulkiness of the BODIPY dyes that prevents their H-aggregation, reaching 2500000 M-1 cm-1 (extinction coefficient × quantum yield). Fluorescence microscopy revealed that the single-particle brightness of these NPs is ∼5-fold higher than that of QDot-585 using the same excitation wavelength (532 nm). Finally, when microinjected inside cells, these small and stealth NPs (10 nm diameter) distribute more evenly than 20 nm QDots inside the cytosol, showing similar spreading as a fluorescent protein. Thus, the developed monomolecular NPs, owing to their small size and stealth properties, are artificial analogues of fluorescent proteins, surpassing the latter >50-fold in terms of brightness.

Enhanced polymer mechanical degradation through mechanochemically unveiled lactonization

The mechanical degradation of polymers is typically limited to a single chain scission per triggering chain stretching event, and the loss of stress transfer that results from the scission limits the extent of degradation that can be achieved. Here, we report that the mechanically triggered ring-opening of a [4.2.0]bicyclooctene (BCOE) mechanophore sets up a delayed, force-free cascade lactonization that results in chain scission. Delayed chain scission allows many eventual scission events to be initiated within a single polymer chain. Ultrasonication of a 120 kDa BCOE copolymer mechanically remodels the polymer backbone, and subsequent lactonization slowly (~days) degrades the molecular weight to 4.4 kDa, > 10× smaller than control polymers in which lactonization is blocked. The force-coupled kinetics of ring-opening are probed by single molecule force spectroscopy, and mechanical degradation in the bulk is demonstrated. Delayed scission offers a strategy to enhanced mechanical degradation and programmed obsolescence in structural polymeric materials.

Characterization and preparation of green colored intramolecular novel ball type cobalt phthalocyanine complexes with single-chain polymer structure

The single-chain polymeric-ball type CoPcs (SCP-ball type CoPcs) were synthesized via the intramolecular macrocyclization reaction of cobalt phthalocyanines from poly(PNDEAMSt2%-co-St) (as named precursor copolymer1) and poly(PNDEAMSt6%-co-St), as named precursor copolymer2) as precursors under diluted solution conditions at 155 °C in presence of cyclohexanol. SCP-ball type CoPc1 and SCP-ball type CoPc2 were prepared from precursor copolymer1 and precursor copolymer2, respectively. The ball-type phthalocyanine moiety was incorporated into one side of the polymer chain. Both linear copolymer precursor and formation of ball-type cobalt phthalocyanine within a single-chain polymer were confirmed by FT-IR, 1H NMR, UV/Vis spectroscopy and MALDI-TOF-MS techniques. Particularly, the formation of SCP-ball type CoPc2 complex was characterized by almost disappearance of –CN band at 2230 cm−1 of the FT-IR and appearance of Q band between 601 and 673 nm. Average apparent activation energies of the thermal degradation of SCP-ball type CoPc2 calculated by three model-free methods in a period of α=0.07–0.90 have been estimated, and the activation energy for weight loss from 7% to 90% was increased from 33.16kj/mol to 36.73kj/mol, respectively. Optical and dielectrical measurements of linear copolymer precursor2 and SCP-ball type CoPc2 were carried out.

Formation of Supramolecular Polymer Network and Single-Chain Polymer Nanoparticles via Host–Guest Complexation from Pillar[5]arene Pendant Polymer

A pillar[5]arene pendant polymer was synthesized by ring-opening metathesis polymerization using the Grubbs first-generation catalyst and cross-linked using a bis(imidazolium) cross-linker via host...

Transient Multivalent Nanobody Targeting to CD206-Expressing Cells via PH-Degradable Nanogels.

To target nanomedicines to specific cells, especially of the immune system, nanobodies can be considered as an attractive tool, as they lack the Fc part as compared to traditional antibodies and, thus, prevent unfavorable Fc-receptor mediated mistargeting. For that purpose, we have site-specifically conjugated CD206/MMR-targeting nanobodies to three types of dye-labeled nanogel derivatives: non-degradable nanogels, acid-degradable nanogels (with ketal crosslinks), and single polymer chains (also obtained after nanogel degradation). All of them can be obtained from the same reactive ester precursor block copolymer. After incubation with naïve or MMR-expressing Chinese hamster ovary (CHO) cells, a nanobody mediated targeting and uptake could be confirmed for the nanobody-modified nanocarriers. Thereby, the intact nanogels that display nanobodies on their surface in a multivalent way showed a much stronger binding and uptake compared to the soluble polymers. Based on their acidic pH-responsive degradation potential, ketal crosslinked nanogels are capable of mediating a transient targeting that gets diminished upon unfolding into single polymer chains after endosomal acidification. Such control over particle integrity and targeting performance can be considered as highly attractive for safe and controllable immunodrug delivery purposes.

Theta Point Calculation of a Polymer Chain with Electric Dipole Moments: Monte Carlo Simulation

Monte Carlo simulations are used to simulate a single polymer chain in a more generalized model. The more generalized model differs from the simpler models by including dipole-dipole interactions. The polymer chain is modeled as a freely rotating chain where the neighboring beads are connected by harmonic spring. Excluded volume effects are included employing modified Lennard-Jones potential. As the extension in this work, each monomer unit carries permanently a freely-rotating electric dipole moment. After getting the system equilibrated the average values are measured and Θ-temperature of the system is determined. The effects of the presence of the dipole moments to the Θ-temperature of the system are investigated. The results are analyzed in comparison with a bare model.

Shear-Induced Adhesion of Alternating Peptides Prepared by Ugi Four-Center Three-Component Reaction.

The development of new peptide-based glues has been strongly urged from the viewpoints of industrial applications and biomedical engineering. However, the large-scale synthesis of polypeptides with an ordered sequence is highly challenging, which strictly restricts materials resources for the research and development of polypeptides. In this work, the framework of adhesive alternating peptides has been designed to be glycine (Gly)-N-substituted valine (Val) as the dipeptide repeating sequence, considering the peptapeptide repeating sequence of viscoelastic natural elastin as a motif. The alternating peptides are prepared via three-component polymerization exploiting Ugi four-center three-component reaction as the elemental polymerization reaction. The adhesive strength (SAdh ) values of the polymers are evaluated by a shear adhesive test method using two glass plates. Alternating peptides with Gly-N-benzylated Val dipeptide repeating units exhibit the optimal adhesive properties such as much higher SAdh than that of conventional fibrin glue and a unique readhesion capability. It is indicated that the remarkably high SAdh would be attributed to the shear-induced structural change of single polymer chain, the slow relaxation of extended structure, and the weak interchain interactions. Due to the favorable adhesive properties of alternating peptides, these adhesives may be highly suitable for real-world applications.

Janus-Like Single-Chain Polymer Nanoparticles as Two-in-One Emulsifiers for Aqueous and Nonaqueous Pickering Emulsions

The exploration of Pickering emulsions is very significant owing to their versatile and important applications in many scopes. In this study, synthesis of a novel kind of single-chain polymer nanoparticle (SCPN) and its stabilized Pickering emulsions were demonstrated. To this end, linear-dendritic diblock copolymers consisting of poly((2-dimethylamino) ethyl methacrylate) (PDMAEMA) blocks and four-generation dendritic aliphatic polyester blocks (G4) have been first synthesized by the combination of click chemistry and reversible addition-fragmentation chain transfer (RAFT) polymerization reaction. The subsequent intramolecular cross-linking of the PDMAEMA block of PDMAEMA-b-G4 copolymers in DMF using 1,4-diiodobutane as cross-linkers afforded Janus-like SCPNs that exhibited a cross-linked PDMAEMA head tethered by a short dendritic tail. The molecular weight and distribution together with the structure of polymers were carefully characterized by GPC and NMR spectroscopy. By the employment of the as-synthesized Janus-like SCPNs as Pickering emulsifiers, aqueous and nonaqueous Pickering emulsions including water-in-oil and oil-in-oil as well as ionic liquid-in-oil were generated. Under the same conditions, it was found that the long-term stabilities of Pickering emulsions stabilized by Janus-like SCPNs were superior to those of Pickering emulsions stabilized by their linear quaternized PDMAEMA-b-G4 by CH3I analogous.

An extended eight-chain model for hyperelastic and finite viscoelastic response of rubberlike materials: Theory, experiments and numerical aspects

Rubberlike materials exhibit strong rate-dependent mechanical response which manifests itself in creep and relaxation tests as well as in the hysteresis curves under cyclic loading. Unlike linear viscoelasticity, creep and relaxation response of rubber is nonlinear and amplitude-dependent. Within this context, the contribution of this work is three fold. (i) On the experimental side, the characterization of equilibrium and non-equilibrium responses are carried out by means of uniaxial and equibiaxial extension tests. Also performed are the creep and relaxation experiments at various stress and strain levels. (ii) On the theoretical side, we extend the well-known eight-chain model via incorporating a simple yet instrumental tube-constraint term composed of the second invariant into the non-affine network contribution reflecting the ground state equilibrium response. For the non-equilibrium response, we propose a new evolution equation for the creep/relaxation behavior of rubberlike materials based on a relaxation kinetics of a single polymer chain. The geometric non-linearity is incorporated via the finite deformation kinematics based on the multiplicative split of the deformation gradient into elastic and viscous parts, whereas the volumetric and isochoric split of the deformation gradient is entirely discarded. The rheology uses a nonlinear spring responsible for equilibrium elastic response in parallel to n number of Maxwell elements, leading to a generalized Maxwell-Wiechert viscoelastic solid. (iii) The algorithmic implementation of the model features the spectral decomposition of the respective terms and is demonstrated within the context of the finite element method. The developed model is validated by fitting both the elastic and viscoelastic model responses with respect to the experimental data in the sense of uniaxial, (equi)biaxial extensions, and pure shear tests. Relaxation and creep behavior of the model are thoroughly assessed. Also presented in the manuscript is the capability and the performance of the model in the face of a relevant non-homogeneous boundary value problem. The quality of the findings earns the model vast utilization areas from an engineering perspective.

Recent Advances in the Synthesis and Application of Polymer Compartments for Catalysis.

Catalysis is one of the most important processes in nature, science, and technology, that enables the energy efficient synthesis of essential organic compounds, pharmaceutically active substances, and molecular energy sources. In nature, catalytic reactions typically occur in aqueous environments involving multiple catalytic sites. To prevent the deactivation of catalysts in water or avoid unwanted cross-reactions, catalysts are often site-isolated in nanopockets or separately stored in compartments. These concepts have inspired the design of a range of synthetic nanoreactors that allow otherwise unfeasible catalytic reactions in aqueous environments. Since the field of nanoreactors is evolving rapidly, we here summarize—from a personal perspective—prominent and recent examples for polymer nanoreactors with emphasis on their synthesis and their ability to catalyze reactions in dispersion. Examples comprise the incorporation of catalytic sites into hydrophobic nanodomains of single chain polymer nanoparticles, molecular polymer nanoparticles, and block copolymer micelles and vesicles. We focus on catalytic reactions mediated by transition metal and organocatalysts, and the separate storage of multiple catalysts for one-pot cascade reactions. Efforts devoted to the field of nanoreactors are relevant for catalytic chemistry and nanotechnology, as well as the synthesis of pharmaceutical and natural compounds. Optimized nanoreactors will aid in the development of more potent catalytic systems for green and fast reaction sequences contributing to sustainable chemistry by reducing waste of solvents, reagents, and energy.

Platinum Atoms Dispersed in Single-chain Polymer Nanoparticles

The intramolecular cross-linking of single polymer chains can form single-chain nanoparticles (SCNPs), which have many applications. In this study, styrenic copolymers with pendent triphenylphosphine as the coordination site for platinum ions (Pt(II)) and benzocyclobutene as the latent reactive groups are synthesized. Triphenylphosphine groups in the chains can coordinate Pt(II) and aid slight single-chain folding in dilute solution. The intramolecular cross-linking caused by the ring-open reaction of benzocyclobutene completes the single-chain collapse and forms stable SCNPs in dilute solution. Pt(II) embedded in SCNPs can be further reduced to platinum atoms (Pt(0)). Pt(0) steadily and atomically dispersed in SCNPs exhibits better catalytic properties than normal polymer carried platinum particles do for the reduction of p-nitrophenol to p-aminophenol.

Machine-learning-driven discovery of polymers molecular structures with high thermal conductivity

The ability to efficiently design new and advanced polymers with functional thermal properties is hampered by the high-cost and time-consuming experiments. Machine learning is an effective approach that can accelerate materials development by combining material science and big data techniques. Here, machine learning methods were used to predict the thermal conductivity of various single-chain polymers, and the relationship between molecular structures of polymer repeating units and thermal conductivity was also been investigated. The predict model starts from a benchmark dataset generated by large-scale molecular dynamics computations. In predict models, the polymers were ‘fingerprinted’ as simple, easily attainable numerical representations, which helps to develop an on-demand property prediction model. Further, potential quantitative relationship between molecular structures of polymer and thermal conductivity property was analyzed, and hypothetical polymers with ideal thermal conductivity were identified. The methods are shown to be general, and can hence guide the screening and systematic identification of high thermal conductivity.