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It is well accepted that adding nanoparticles (NPs) to polymer melts can result in significant property improvements. Here we focus on the causes of mechanical reinforcement and present rheological measurements on favourably interacting mixtures of spherical silica NPs and poly(2-vinylpyridine), complemented by several dynamic and structural probes. While the system dynamics are polymer-like with increased friction for low silica loadings, they turn network-like when the mean face-to-face separation between NPs becomes smaller than the entanglement tube diameter. Gel-like dynamics with a Williams-Landel-Ferry temperature dependence then result. This dependence turns particle dominated, that is, Arrhenius-like, when the silica loading increases to ∼31 vol%, namely, when the average nearest distance between NP faces becomes comparable to the polymer's Kuhn length. Our results demonstrate that the flow properties of nanocomposites are complex and can be tuned via changes in filler loading, that is, the character of polymer bridges which 'tie' NPs together into a network.

Large-scale molecular dynamics simulations are used to study the internal relaxations of chains in nanoparticle (NP)/polymer composites. We examine the Rouse modes of the chains, a quantity that is closest in spirit to the self-intermediate scattering function, typically determined in an (incoherent) inelastic neutron scattering experiment. Our simulations show that for weakly interacting mixtures of NPs and polymers, the effective monomeric relaxation rates are faster than in a neat melt when the NPs are smaller than the entanglement mesh size. In this case, the NPs serve to reduce both the monomeric friction and the entanglements in the polymer melt, as in the case of a polymer-solvent system. However, for NPs larger than half the entanglement mesh size, the effective monomer relaxation is essentially unaffected for low NP concentrations. Even in this case, we observe a strong reduction in chain entanglements for larger NP loadings. Thus, the role of NPs is to always reduce the number of entanglements, with this effect only becoming pronounced for small NPs or for high concentrations of large NPs. Our studies of the relaxation of single chains resonate with recent neutron spin echo (NSE) experiments, which deduce a similar entanglement dilution effect.

The resemblance between colloidal and molecular polymerization reactions is very useful in fundamental studies of polymerization reactions, as well as in the development of new nanoscale systems with desired properties. Future applications of colloidal polymers will require nanoparticle ensembles with a high degree of complexity that can be realized by hetero-assembly of NPs with different dimensions, shapes, and compositions. A method has been developed to apply strategies from molecular copolymerization to the co-assembly of gold nanorods with different dimensions into random and block copolymer structures (plasmonic copolymers). The approach was extended to the co-assembly of random copolymers of gold and palladium nanorods. A kinetic model validated and further expanded the kinetic theories developed for molecular copolymerization reactions., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Mechanical activation of chemical bonds typically involves the application of external forces, which implies a broad distribution of bond tensions. We demonstrate that controlling the flow profile of a macromolecular fluid generates and delineates mechanical force concentration, enabling a hierarchical activation of chemical bonds on different length scales from the macroscopic to the molecular. Bond tension is spontaneously generated within brushlike macromolecules as they spread on a solid substrate. The molecular architecture creates an uneven distribution of tension in the covalent bonds, leading to spatially controlled bond scission. By controlling the flow rate and the gradient of the film pressure, one can sever the flowing macromolecules with high precision. Specific chemical bonds are activated within distinct macromolecules located in a defined area of a thin film. Furthermore, the flow-controlled loading rate enables quantitative analysis of the bond activation parameters.

Molecular bottle-brushes are highly branched macromolecules with side chains densely grafted to a long polymer backbone. The brush-like architecture allows focusing of the side-chain tension to the backbone and its amplification from the pico-Newton to nano-Newton range. The backbone tension depends on the overall molecular conformation and the surrounding environment. Here we study the relation between the tension and conformation of the molecular brushes in solutions, melts, and on substrates. In solutions, we find that the backbone tension in dense brushes with side chains attached to every backbone monomer is on the order of f(0)N(3/8) in athermal solvents, f(0)N(1/3) in theta solvents, and f(0) in poor solvents and melts, where N is the degree of polymerization of side chains, f(0) approximately equal k(B)T/b is the maximum tension in side chains, b is the Kuhn length, k(B) is Boltzmann's constant, and T is the absolute temperature. Depending on the side chain length and solvent quality, molecular brushes develop tension on the order of 10-100 pN, which is sufficient to break hydrogen bonds. Significant amplification of tension occurs upon adsorption of brushes onto a substrate. On a strongly attractive substrate, maximum tension in the brush backbone is approximately f(0)N, reaching values on the order of several nano-Newtons, which exceeds the strength of a typical covalent bond. At low grafting density and high spreading parameter, the cross-sectional profile of an adsorbed molecular brush is approximately rectangular with a thickness approximately b (A/S)1/2, where A is the Hamaker constant, and S is the spreading parameter. At a very high spreading parameter (S > A), the brush thickness saturates at monolayer approximately b. At a low spreading parameter, the cross-sectional profile of adsorbed molecular brush has a triangular tent-like shape. In the cross-over between these two opposite cases, covering a wide range of parameter space, the adsorbed molecular brush consists of two layers. Side chains in the lower layer gain surface energy due to the direct interaction with the substrate, while the second layer spreads on the top of the first layer. Scaling theory predicts that this second layer has a triangular cross-section with width R approximately N(3/5) and height h approximately N(2/5). Using self-consistent field theory we calculate the cap profile y(x) = h(1 - x2/R2)2, where x is the transverse distance from the backbone. The predicted cap shape is in excellent agreement with both computer simulation and experiment.

We discovered pH-induced selective desorption and readsorption of weakly acidic polymers from polyacid or polybase layer-by-layer films. In situ attenuated total reflection Fourier transform infrared spectroscopy confirms the selectivity of polyacid release and shows that film response is caused by pH-induced charge imbalance. Experimentally the characteristic time of chain release tau scales with molar mass M as M(1.1+/-0.1). A new theoretical model of "sticky gel electrophoresis" of entangled polyacids agrees with experiments and predicts tau approximately MH, where H is film thickness. Neutron reflectivity shows that polyacid release results in disordering of the film structure.

The generalization of the Flory theorem for structurally asymmetric mixtures was derived and tested by direct visualization of conformational transformations of brushlike macromolecules embedded in a melt of linear chains. Swelling of a brush molecule was shown to be controlled not only by the degree of polymerization (DP) of the surrounding linear chains, N(B), but also by the DP of the brush's side chains, N, which determines the structural asymmetry of the mixed species. The boundaries of the swelling region were established by scaling analysis as N(2) < N (B) < N (A)/N, where N (A) is the degree of polymerization of the brush backbone. Experiment and theory demonstrated good agreement.

Organized arrays of anisotropic nanoparticles show electronic and optical properties that originate from the coupling of shape-dependent properties of the individual nanorods. The organization of nanorods in a controllable and predictable way provides a route to the fabrication of new materials and functional devices. So far, significant progress has been achieved in the self-assembly of nanorod arrays, yet the realization of a range of different structures requires changing the surface chemistry of the nanoparticles. We organized metal nanorods in structures with varying geometries by using a striking analogy between amphiphilic ABA triblock copolymers and the hydrophilic nanorods tethered with hydrophobic polymer chains at both ends. The self-assembly was tuneable and reversible and it was achieved solely by changing the solvent quality for the constituent blocks. This approach provides a new route to the organization of anisotropic nanoparticles by using the strategies that are established for the self-assembly of block copolymers.

Polymeric nanogel vectors were developed for cellular gene and antisense delivery. Inverse microemulsion polymerization was utilized to synthesize biocompatible nanogels with controlled size, morphology, and composition. The chemical composition, size, polydispersity, stability, and swelling behavior of the nanogels were investigated by NMR, light scattering, transmission electron microscopy, and atomic force microscopy. The cell viability, uptake, and physical stability of nanogel-DNA complexes were evaluated under physiological conditions. Monodisperse nonionic and cationic nanogels were produced with controllable sizes ranging from 40 to 200 nm in diameter. The nanogels demonstrated extended stability in aqueous media and exhibited low toxicity in cell culture. Cationic nanogels formed monodisperse complexes with oligonucleotides and showed enhanced oligonucleotide uptake in cell culture. The nanogels synthesized in this study demonstrate potential utility as carriers of oligonucleotides and DNA for antisense and gene delivery.

The second virial coefficient, A[SUB2], is evaluated between pairs of short chain molecules by direct simulations using a parallel tempering Monte Carlo method where the centers of mass of the two molecules are coupled by a harmonic spring. Three off-lattice polymer models are considered, one with rigid bonds and two with flexible bonds, represented by the finitely extensible nonlinear elastic potential with different stiffness. All the models considered account for excluded volume interactions via the Lennard-Jones potential. In order to obtain the second virial coefficient we calculate the effective intermolecular interaction between the two polymer chains. As expected this intermolecular interaction is found to be strongly dependent upon chain length and temperature. For all three models the θ temperature (θ[SUBn]), defined as the temperature at which the second virial coefficient vanishes for chains of finite length, varies as θ[SUBn]-θ[SUB∞]&vprop;n[SUP-1/2], where n is the number of bonds in the polymer chains and θ[SUB∞] is the θ point for an infinitely long chain. Introducing flexibility into the model has two effects upon θ[SUBn]; the θ temperature is reduced with increasing flexibility, and the n dependence of θ[SUBn] is suppressed. For a particular choice of spring constant an n-independent θ temperature is found. We also compare our results with those obtained from experimental studies of polystyrene in decalin and cyclohexane, and for poly(methyl methacrylate) in a water and tert-butyl alcohol mixture, and show that all the data can be collapsed onto a single universal curve without any adjustable parameters. We are thus able to relate both A[SUB2] and the excluded volume parameter v, to the chain interaction parameter z, in a way relating not only the data for different molecular weights and temperatures, but also for different polymers in different solvents. [ABSTRACT FROM AUTHOR]

Chiral packing of ligands on the surface of nanoparticles (NPs) is of fundamental and practical importance, as it determines how NPs interact with each other and with the molecular world. Herein, for gold nanorods (NRs) capped with end‐grafted nonchiral polymer ligands, we show a new mechanism of chiral surface patterning. Under poor solvency conditions, a smooth polymer layer segregates into helicoidally organized surface‐pinned micelles (patches). The helicoidal morphology is dictated by the polymer grafting density and the ratio of the polymer ligand length to nanorod radius. Outside this specific parameter space, a range of polymer surface structures was observed, including random, shish‐kebab, and hybrid patches, as well as a smooth polymer layer. We characterize polymer surface morphology by theoretical and experimental state diagrams. The helicoidally organized polymer patches on the NR surface can be used as a template for the helicoidal organization of other NPs, masked synthesis on the NR surface, as well as the exploration of new NP self‐assembly modes. Gold nanorods, end‐grafted with achiral polymer ligands, show a new mechanism of chiral surface patterning giving a helicoidal morphology. This morphology is dictated by the relationship between the polymer grafting density and the ratio of the polymer length to the nanorod radius. [ABSTRACT FROM AUTHOR]

The effects of polydispersity on the linear viscoelastic properties of concentrated polymer solutions and melts are analyzed. Existing theories for the dynamics of linear polymers, based on the idea of each polymer confined in a fixed tube, are shown to be incapable of describing observed rheological response of polydisperse polymers. A model is proposed which, in a self-consistent manner, solves the many chain problem given the solution to the single chain problem. Two types of polymer relaxation are incorporated in the model. The first type is escape of a polymer from its tube by motion of the polymer itself. It includes all dynamic modes available to the single chain in a tube—those due to its reptation—as well as other modes, such as fluctuations in tube length. The second type is relaxation of a polymer chain by the motions of the surrounding polymers forming its tube (constraint release). The relaxation modulus is then the product of two functions μ(t) and R(t). μ(t) is the fraction of tube occupied at time t=0 that has not been evacuated at time t, thereby representing escape of the polymer from its tube (solution to the single chain problem). R(t) represents relaxation by the constraint release process, which is modeled by a Rouse chain with random bead mobilities. The probability distribution of these mobilities is determined, in a self-consistent way, from the disentanglement rates due to the tube evacuation processes of the surrounding chains. Thus R(t) is calculated from the spectrum of relaxation rates of the μ(t) processes for the surrounding chains. The predictions of the model with some single chain solutions μ(t) from the literature are compared with oscillatory shear data for binary blends of nearly monodisperse polybutadiene, in which both components are well entangled. [ABSTRACT FROM AUTHOR]

Central concepts of the reptation model of polymer relaxation by disentanglement are the confining tube, the primitive path, and the entanglement net. These are given more precise definitions and are expounded upon here. The entanglement net is regarded as the set of primitive paths of the molecules. The scaling relation connecting distance between entanglements and concentration is derived by a self-consistency argument. Explicit results on probability distributions characterizing unentangled loops and primitive path lengths are derived. The polymers are modeled as random walks in a regular entanglement net. Results are presented as a function of the spacing between entanglements. [ABSTRACT FROM AUTHOR]

Organized arrays of anisotropic nanoparticles show electronic and optical properties that originate from the coupling of shape-dependent properties of the individual nanorods. The organization of nanorods in a controllable and predictable way provides a route to the fabrication of new materials and functional devices. So far, significant progress has been achieved in the self-assembly of nanorod arrays, yet the realization of a range of different structures requires changing the surface chemistry of the nanoparticles. We organized metal nanorods in structures with varying geometries by using a striking analogy between amphiphilic ABA triblock copolymers and the hydrophilic nanorods tethered with hydrophobic polymer chains at both ends. The self-assembly was tuneable and reversible and it was achieved solely by changing the solvent quality for the constituent blocks. This approach provides a new route to the organization of anisotropic nanoparticles by using the strategies that are established for the self-assembly of block copolymers. [ABSTRACT FROM AUTHOR]

Abstract: Polyelectrolytes are polymers carrying either positively or negatively charged ionizable groups. The properties of these polymers in solutions and at charged surfaces depend on the fraction of dissociated ionic groups, solvent quality for polymer backbone, solution dielectric constant, salt concentration, and polymer–substrate interactions. In this review, we summarize the current development of theoretical models describing properties of polyelectrolyte solutions and adsorption of charged polymers at surfaces and interfaces. We discuss in detail the conformational properties of polyelectrolyte chains in dilute and semidilute solutions, the phenomenon of counterion condensation, the necklace structure of polyelectrolytes in poor solvent conditions for polymer backbone, the dynamics of polyelectrolyte solutions, the surface overcharging by adsorbed polyelectrolytes and its implication for assembled polyelectrolyte multilayers. [Copyright &y& Elsevier]

The mechanical properties of covalent polymer networks often arise from the permanent end-linking or cross-linking of polymer strands, and molecular linkers that break more easily would likely produce materials that require less energy to tear. We report that cyclobutane-based mechanophore cross-linkers that break through force-triggered cycloreversion lead to networks that are up to nine times as tough as conventional analogs. The response is attributed to a combination of long, strong primary polymer strands and cross-linker scission forces that are approximately fivefold smaller than control cross-linkers at the same timescales. The enhanced toughness comes without the hysteresis associated with noncovalent cross-linking, and it is observed in two different acrylate elastomers, in fatigue as well as constant displacement rate tension, and in a gel as well as elastomers. [ABSTRACT FROM AUTHOR]

The details of how a mucus hydrogel forms from its primary structural component, mucin polymers, remain incompletely resolved. To explore this, we use a combination of macrorheology and single-particle tracking to investigate the bulk and microscopic mechanical properties of reconstituted MUC5AC mucin gels. We find that analyses of thermal fluctuations on the length scale of the micrometer-sized particles are not predictive of the linear viscoelastic response of the mucin gels, and that taken together, the results from both techniques help to provide complementary insight into the structure of the network. In particular, we show that macroscopic stiffening of MUC5AC gels can be brought about in different ways by targeting specific associations within the network using environmental triggers such as modifications to the pH, surfactant, and salt concentration. Our work may be important for understanding how environmental factors, including pathogens and therapeutic agents, alter the mechanical properties of fully constituted mucus. [ABSTRACT FROM AUTHOR]

Die Selbstorganisation kolloidaler Analoga von molekularen Copolymeren kann grundlegende Erkenntnisse für die Gebiete der molekularen Copolymerisation und der Nanotechnologie liefern. In ihrer Zuschrift auf S. 2686 ff. präsentieren K. Liu, E. Kumacheva et al. eine mikroskopische und spektroskopische Analyse, mit deren Hilfe sie Design ‐ Regeln und ein kinetisches Modell für das Wachstum kolloidaler Zufalls ‐ und Blockcopolymere aus plasmonischen Nanostäben unterschiedlicher Länge und Zusammensetzung formulieren. [ABSTRACT FROM AUTHOR]

We report a predefined self-organization of gold nanorods (NRs) end-terminated with multiple polymer arms ("pom-poms") in higher-order structures. The assembly of polymer-tethered NRs was controlled by changing the structure of the polymer pom-poms. We show that the variation in the molecular weight of the polymer molecules and their relative location with respect to the long side of the NRs resulted in two competing association modes of the nanorods, that is, their side-by-side and end-to-end assembly, and produced bundles, chains, rings, and bundled chains of the NRs. The superposition of the two variables controlling the organization of NRs allowed us to create a map showing the variation in the longitudinal plasmonic bands of the NAs achieved by their self-assembly. [ABSTRACT FROM AUTHOR]

Molecular dynamics simulations confirm recent extensional flow experiments showing ring polymer melts exhibit strong extension-rate thickening of the viscosity at Weissenberg numbers Wi≪1. Thickening coincides with the extreme elongation of a minority population of rings that grows with Wi. The large susceptibility of some rings to extend is due to a flow-driven formation of topological links that connect multiple rings into supramolecular chains. Links form spontaneously with a longer delay at lower Wi and are pulled tight and stabilized by the flow. Once linked, these composite objects experience larger drag forces than individual rings, driving their strong elongation. The fraction of linked rings depends nonmonotonically on Wi, increasing to a maximum when Wi∼1 before rapidly decreasing when the strain rate approaches 1/τe. [ABSTRACT FROM AUTHOR]

We present a systematic investigation of well-characterized, experimentally pure polystyrene (PS) rings with molar mass of 161 000 g/mol in dilute solutions. We measure the ring form factor at θ- and good-solvent conditions as well as in a polymeric solvent (linear PS of roughly comparable molar mass) by means of small-angle neutron scattering (SANS). Additional dynamic light scattering (DLS) measurements support the SANS data and help elucidate the role of solvent quality and solution preparation. The results indicate the increase of ring dimensions as the solvent quality improves. Furthermore, the experimental form factors in both θ-solvent and linear matrix behave as ideal rings and are fully superimposable. The nearly Gaussian conformations of rings in a melt of linear chains provide evidence of threading of linear chains through rings. The latter result has implications for the dynamics of ring–linear polymer mixtures. [ABSTRACT FROM AUTHOR]

Abstract: We report a fully general technique addressing a long standing challenge of calculating conformational free energy differences between various states of a polymer chain from simulations using explicit solvent force fields. The main feature of our method is a special mapping variable, a path coordinate, which continuously connects two conformations. The path variable has been designed to preserve locality in the phase space near the path endpoints. We avoid the problem of sampling the unfolded states by creating an artificial confinement “tube” in the phase space that prevents the molecule from unfolding without affecting the calculation of the desired free energy difference. We applied our technique to compute the free energy difference between two native-like conformations of the small protein Trp-cage using the CHARMM force field with explicit solvent. We verified this result by comparing it with an independent, significantly more expensive calculation. Overall, the present study suggests that the new method of computing free energy differences between polymer chain conformations is accurate and highly computationally efficient. [Copyright &y& Elsevier]