Monomers In Chains Research Articles

On-surface stepwise dehalogenative homocoupling of 2,7-dibromotriphenylene on Au(111) surface

The dehalogenative homocoupling of DBTP molecules on Au(111) surface has been investigated at a single molecular level by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The length and morphology of the carbon-carbon coupling chain are adjusted by stepwise thermal excitation. Gradual annealing of the sample at 323 and 353 K promotes the dehalogenative homocoupling, resulting in the formation of oligomer and long straight chains that branch out or form combs. Such straight chains show an obvious zipper-like double-chain structure when annealed at 373 K. Our results show that Br-H bonds between straight chains play a stabilizing role in the zipper structure. During further annealing to a maximum of 453 K, both dehalogenative homocoupling and cross-coupling occur between the chains. The number of monomers in the molecular chains formed at 453 K is 16–20, accounting for the largest proportion.

Additivity and non-additivity of dissociation energies in intermolecular interactions. Theoretical studies on (H2)n, n = 2-8, (CO2)n, n = 2-6 and (HF)n, n = 2-8

CCSD(T) and MP2 results using the aug-cc-pV5Z basis set are reported for chain, cyclic and other structures of the clusters (H2)n, n = 2-8, (CO2)n, n = 2-6 and (HF)n, n = 2-8. In chain-like structures of (H2)n and (CO2)n, with the bonding type of the dimer maintained, the dissociation energy De of the dimer doubles for the trimer, triples for the tetramer, and so on. Due to these systems being dominated by short-range forces, interactions are essentially restricted to neighbouring monomers. For other types of (H2)n and (CO2)n structures, the multipliers relative to the dimerisation energy can be much higher. Dissociation energies for the hexamers in S6 symmetry of both H2 (379 cm−1) and CO2 (4925 cm−1) are over ten times the respective dimerisation energies. For the chain-like trimer of HF, however, De is in excess of double the dimer value. Mainly due to longer-range dipolar forces, the interactions reach beyond the neighbouring monomers. The interaction energy between HF monomers in chains follows an approximate R−2 (R being the F–F distance) relationship, The calculated dissociation energies of the HF octamer are 15,985 cm−1 (factor of 10.4) for the chain, and 21,003 cm−1 (factor of 13.7) for the C6h cyclic structure.

Templated Ring-Opening Metathesis (TROM) of Cyclic Olefins Tethered to Unimolecular Oligo(thiophene)s

We developed a fully abiotic approach to template the synthesis of discrete unimolecular polyolefins. Discrete, unimolecular oligo(thiophene)s with alternating sequence were obtained by iterative convergent/divergent couplings and then functionalized with pendant cyclic olefin monomers in the side chains. Upon treatment with the Grubbs third-generation catalyst in dilute solution (0.15 mM in DCM at 0 °C), the pendant monomers undergo templated ring-opening metathesis (TROM). Then, the daughter olefin is liberated from the parent thiophene by hydrolysis. Cyclooctenes undergo TROM to afford macrocyclic products that exactly replicate the chain length of the parent oligomer, as evidenced by MALDI MS/MS and NMR. Norbornene derivatives also undergo TROM and replicate unimolecular chain lengths, but in contrast, they exclusively form the linear oligomeric products with styrenic end groups. A template that was functionalized with one norbornene unit at the α chain end, followed by five cyclooctene units along th...

Comparison of two coarse-grained models of cis-polyisoprene with and without pressure correction

We investigate two coarse-grained models of a cis-polyisoprene melt. The bonded interactions which are used in both models are derived by Boltzmann inversion of the probability distributions of the bonded variables in a single chain simulation. The non-bonded interactions are derived by an iterative Boltzmann inversion method in the melt state with pressure correction in a model and without in the other model. In our mapping rule, two or three carbons are grouped into coarse-grained beads. The trade-off relationship between pressure and compressibility is observed in the coarse-grained models. Since the relaxation dynamics of the coarse-grained models are accelerated by the smoothed potentials, single numerical factors are introduced to rescale the time scale of the coarse-grained models, respectively. The factors of the two models are in the same order but the model with pressure correction displays larger acceleration than the other. It is found that the stress relaxation function near equilibrium and the nonlinear viscosity under steady shear are essentially the same between the two coarse-grained models in the rescaled time scales despite of their different equilibrium pressures. We also study the dependency of the rescaling factors on the chain length of the polymer. The rescaling factors increase with increasing the chain length and exponentially saturates to certain values around 100 monomers in chains.

Application and comparison of derivative-free optimization algorithms to control and optimize free radical polymerization simulated using the kinetic Monte Carlo method

The diversity of the potential arrangements of multiple monomers along the length of polymer chains and their impact on polymer properties spark interest in the design of polymer sequence characteristics for particular applications. Kinetic Monte Carlo (KMC) is a technique that can track the explicit arrangement of monomers in the polymer chains, yet it is difficult to integrate with conventional gradient-based optimization algorithms that are typically invoked to design polymer properties. In this work, we applied and compared derivative-free optimization algorithms to incorporate KMC simulations and find synthesis conditions for achieving property targets and minimizing reaction time, advancing our ability to carry out the design of polymer microstructures and control polymerization processes.

NMR characterization of methylcellulose: Chemical shift assignment and mole fraction of monomers in the polymer chains

Methylcellulose samples with different degrees of substitution were prepared by a heterogeneous reaction of cellulose. Two-dimensional NMR spectroscopy provided complete assignment of the 1H and 13C chemical shifts of the un-, 2-mono-, 3-mono-, 6-mono-, 2,3-di-, 2,6-di-, 3,6-di-, and 2,3,6-tri-substituted anhydroglucose units (AGUs). Comparative analysis of the chemical shift data revealed the relationship between the methyl substituents at the 2-, 3-, and 6-positions and the 1H and 13C chemical shifts of the AGUs; additivity could be applied to the 1H and 13C chemical shifts of methylcellulose. Quantitative 13C NMR spectra of the samples determined the composition of the eight AGUs and the substituent distribution at the 2-, 3-, and 6-positions of cellulose. This provided estimations of the hydroxyl group reactivity toward methylation and the interactions between the substituent groups within the same AGU.

Ordered Toroid Structures of Nanoparticles in Self-attractive Semiflexible Polymer/Nanoparticle Composites

By employing dynamic Monte Carlo simulations, we investigate a coil-to-toroid transition of self-attractive semiflexible polymers and the spatial distributions of nanoparticles in self-attractive semiflexible polymer/nanoparticle composites. The conformation of self-attractive semiflexible polymers depends on bending energy and self-attractive interactions between monomers in polymer chains. A three-stage process of toroid formation for self-attractive semiflexible chains is shown: several isolated toroids, a loose toroid structure, and a compact toroid structure. Utilizing the compact toroid conformations of self-attractive semiflexible chains, we can control effectively the spatial distributions of nanoparticles in self-attractive semiflexible polymer nanocomposites, and an unconventional toroid structure of nanoparticles is observed.

Polystyrene comb architectures as model systems for the optimized solution electrospinning of branched polymers

The bead to bead-free fibers transition for electrospun filaments was investigated for well-defined linear and comb homopolymers. A series of monodisperse model comb structures with well-defined backbone and side chains was synthesized using anionic polymerization of polystyrene (PS). All model combs had the same backbone and a similar total molecular weight. The length and number of branches was varied, but the total number of monomers in the side chains was nearly constant. Solutions of these polystyrenes in N,N-dimethylformamide (DMF) were electrospun under identical conditions to determine the effect of molecular topology on the morphology of the fibers. The morphology and fiber diameter for all PS model polymers depended on the zero shear viscosity, η0. The comb solutions generally formed fibers at lower η0 and the fibers had larger diameters compared with linear polystyrene. The bead to fiber transition occurred at substantially lower polymer concentrations for combs with fewer, but longer branches.

NMR characterization of sodium carboxymethyl cellulose: Substituent distribution and mole fraction of monomers in the polymer chains

A series of sodium carboxymethyl cellulose (CMC) samples with degrees of substitution (DS) from 0.68 to 2.84 were prepared from cellulose by multistep carboxymethylation. Two-dimensional NMR spectroscopic analyses allowed complete assignment of the 1H and 13C chemical shifts of the eight anhydroglucose units (AGUs) found in CMC: 2,3,6-tri-, 2,3-di-, 2,6-di-, 3,6-di-, 2-mono-, 3-mono-, 6-mono-, and unsubstituted AGUs. A comparative analysis of the chemical shift data revealed the substituent effects of the carboxymethyl groups at the 2-, 3-, and 6-positions on the 1H and 13C chemical shifts of the AGUs and that additivity could be applied to the 1H and 13C chemical shifts of CMC. Quantitative 13C NMR spectra of the CMC samples allowed determination of the AGU composition, as well as the substituent distribution at the 2-, 3-, and 6-positions of cellulose, which allowed estimation of the reactivity of the hydroxyl groups toward the carboxymethylation.

Effect of chain microstructure on self-assembly and emulsification of amphiphilic poly(acrylic acid)-polystyrene copolymers.

In this study, a series of random copolymer poly(acrylic acid-co-styrene) (P(AA-co-St)) and block copolymer poly(acrylic acid)-b-polystyrene (PAA-b-PSt) with similar chemical composition but different chain microstructure were synthesized. The self-assembly behavior of random and block copolymers in selective solvent was investigated, and the structural evaluation of random and block copolymers micelles was carried out by transmission electron microscopy (TEM), dynamic light scattering (DLS) measurement, and X-ray photoelectron spectroscopy (XPS). Moreover, together with experimental characterization, the theoretical method dissipative particle dynamics (DPD) approach was applied to investigate the morphological structures of micelles composed from random and block copolymers. Results revealed that the structure of polymeric micelles is significantly affected by the distribution sequence of hydrophilic and hydrophobic monomers in copolymer chains. Furthermore, polymeric micelles based on P(AA-co-St) and PAA-b-PSt with about 50 mol% hydrophilic composition were chosen as the model to investigate the influence of micellar structure on emulsifying performance. For PAA-b-PSt micelles (B48), stable water-in-oil (w/o) emulsions could only obtained when the pH values were lower than 5. As a comparison, the P(AA-co-St) micelles (R49) had an excellent emulsification performance at 4-10 pH, and the pH-induced phase inversion derived from obtained emulsions observed at pH higher than 6. Preliminary results confirm that the micellar structure controlled by chain microstructure plays an important role in the interface behavior of polymer micelles. Compared with PAA-b-PSt micelles, P(AA-co-St) micelles have better interfacial performance and are more tailorable and controllable; thus they can be used as a model for further study of polymeric particulate emulsifiers. This paper provides new insight into the principles governing extremely high emulsifying efficiency of polymeric particulate emulsifiers and pH-responsive properties of the formed emulsions.

Intrachain exciton dynamics in conjugated polymer chains in solution.

We investigate exciton dynamics on a polymer chain in solution induced by the Brownian rotational motion of the monomers. Poly(para-phenylene) is chosen as the model system and excitons are modeled via the Frenkel exciton Hamiltonian. The Brownian fluctuations of the torsional modes were modeled via the Langevin equation. The rotation of monomers in polymer chains in solution has a number of important consequences for the excited state properties. First, the dihedral angles assume a thermal equilibrium which causes off-diagonal disorder in the Frenkel Hamiltonian. This disorder Anderson localizes the Frenkel exciton center-of-mass wavefunctions into super-localized local exciton ground states (LEGSs) and higher-energy more delocalized quasi-extended exciton states (QEESs). LEGSs correspond to chromophores on polymer chains. The second consequence of rotations-that are low-frequency-is that their coupling to the exciton wavefunction causes local planarization and the formation of an exciton-polaron. This torsional relaxation causes additional self-localization. Finally, and crucially, the torsional dynamics cause the Frenkel Hamiltonian to be time-dependent, leading to exciton dynamics. We identify two distinct types of dynamics. At low temperatures, the torsional fluctuations act as a perturbation on the polaronic nature of the exciton state. Thus, the exciton dynamics at low temperatures is a small-displacement diffusive adiabatic motion of the exciton-polaron as a whole. The temperature dependence of the diffusion constant has a linear dependence, indicating an activationless process. As the temperature increases, however, the diffusion constant increases at a faster than linear rate, indicating a second non-adiabatic dynamics mechanism begins to dominate. Excitons are thermally activated into higher energy more delocalized exciton states (i.e., LEGSs and QEESs). These states are not self-localized by local torsional planarization. During the exciton's temporary occupation of a LEGS-and particularly a quasi-band QEES-its motion is semi-ballistic with a large group velocity. After a short period of rapid transport, the exciton wavefunction collapses again into an exciton-polaron state. We present a simple model for the activated dynamics which is in agreement with the data.

Molecular dynamics study of the polymer clay nanocomposites (PCNs): Elastic constants and basal spacing predictions

Micromechanical approaches seem to be limited in the prediction of polymer nanocomposite properties, since the active molecular interactions between nanofillers and polymer matrix as well as those between nanofillers themselves, are far from being explicitly taken into consideration. The molecular interactions between nanofillers and polymer matrix lead to the so-called interphase region, where polymer chains mobility is reduced in the vicinity of nanofillers interface. Many assumptions are made on this interphase region to incorporate implicitly nanofillers/polymer interactions in micromechanical models. Experimental characterizations of this interphase and the confined interlayer polymer in the intercalated structure are not available to date. In this work, we have used isothermal–isostress (NσT) molecular dynamics simulation to predict the isothermal elastic constants of nylon-6 clay nanocomposites in the case of intercalated structure. The effect of the number of monomers in the nylon-6 chains on the basal spacing is evaluated. Isothermal bulk modulus is determined via isothermal–isobaric (NPT) molecular dynamics simulation. We also provide through this work an insight into molecular interactions in intercalated nylon-6 clay nanocomposites.

Functional Thin Films Resulting from Parylene–Vinyl Copolymerization

Quantum and kinetic studies of novel materials based on parylene polymers and variously substituted vinyl molecules are presented and discussed. It is demonstrated that the thin films which are the products of the copolymerization reactions can be prepared (i) within the parylene CVD process on active vinyl substrates or (ii) employing the same process but involving an additional source of vinyl molecules transported to the reaction chamber. Both methods lead to differently functionalized microstructures, primarily dominated by the parylene units, while the vinyl molecules appear relatively seldom (depending on the nature of the substituents used). The copolymerization is shown to be independent of penultimate monomers in linear chains and to undergo composition drift within certain scope. Namely, it is found that even a small amount of p-xylylene monomers in feed leads to the formation of long blocks of pure parylene while the substituted vinyl molecules are expected to appear occasionally in chains. Fin...

Molecular dynamics simulations of end‐grafted polymers with charged side chains

AbstractWe report molecular dynamics simulations on bottle‐brush polyelectrolytes end‐grafted to a planar surface. For each bottle‐brush polyelectrolyte, flexible charged side chains are anchored to one neutral main chain. The effects of the counterion valence and the grafting density on the density profiles and the structural characteristics of the brush were studied in this work. It is found that the electrostatic repulsion between charged monomers in the side chains leads an extended conformation of the brush in a solution containing monovalent counterions, while strong electrostatic binding of multivalent counterions to the side chains has a significant contribution to the collapse of the brush. For the trivalent case, the distribution of end monomers in the main chains becomes broader upon decreasing the grafting density, as compared with the monovalent case. However, the position of the distribution for the monovalent case is relatively insensitive to the change of the grafting density. Additionally, with increased counterion valence, enhanced electrostatic correlation between counterions and charged side chains also weakens the diffusive ability of counterions. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011

Interactions of polyelectrolyte brushes with oppositely charged surfactants

Using Brownian dynamics simulations, we study the effect of the charge ratio, the surfactant length, and the grafting density on the conformational behavior of the complex formed by the polyelectrolyte brush with oppositely charged surfactants. In our simulations, the polyelectrolyte chains and surfactants are represented by a coarse-grained bead-spring model, and the solvent is treated implicitly. It is found that varying the charge ratio induces different morphologies of surfactant aggregates adsorbed onto the brush. At high charge ratios, the density profiles of surfactant monomers indicate that surfactant aggregates exhibit a layer-by-layer arrangement. The surfactant length has a strong effect on the adsorption behavior of surfactants. The lengthening of surfactant leads to a collapsed brush configuration, but a reswelling of the brush with further increasing the surfactant length is observed. The collapse of the brush is attributed to the enhancement of surfactants binding to polyelectrolyte chains. The reswelling is due to an increase in the volume of adsorbed surfactant aggregates. At the largest grafting density investigated, enhanced excluded volume interactions limit the adsorption of surfactant within the polyelectrolyte brush. We also find that end monomers in polyelectrolyte chains exhibit a bimodal distribution in cases of large surfactant lengths and high charge ratios.

Synthesis and characterization of new polyurethanes: influence of monomer composition

Different polyurethanes (PU) were synthesized from polycaprolactone diol, 1.6-hexamethylene diisocyanate and bis(2-hydroxyethyl)terephthalate, using a two- and one-step methods providing regular and random distributions of starting monomers in the polyurethane chains. Even with an identical molar monomer composition, the properties of obtained PU are different depending on the method of synthesis. The chemical structure of PU was characterized by 1H and 13C NMR spectroscopy, as well as by FTIR and UV–Visible spectroscopy. The thermo-mechanical and hydrophilic properties of synthesized PU were also studied demonstrating the influence of aromatic ring in the macromolecular chain.

Synthesis and characterization of new polyurethane based on polycaprolactone

AbstractDifferent polyurethane (PU) were synthesized from ε‐polycaprolactone diol, 4,4′‐diphenyl methane diisocyanate (MDI) and bis(2‐hydroxyethyl)terephthalate (BHET), using a two‐step method and a one‐step method providing regular and random distributions of starting monomers in the PU chains. Even with an identical molar monomer composition, the properties of obtained PU are different depending on the method of synthesis. The structure of PU was characterized by 1H and 13C‐NMR and Fourier transform infrared spectroscopy (FTIR). The thermomechanical properties of synthesized PU were also studied demonstrating the influence of aromatic ring in the macromolecular chain. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Influence of the copolymer architecture and composition on the response and mechanical properties of pH-sensitive fibers

A series of copolymers based on acrylonitrile (AN) and acrylic acid (AA) with varying architecture and composition were synthesized using free radical polymerization. The distribution of monomers in the copolymer chains could be successfully controlled by regulating the addition of more reactive monomer (AA). Copolymers having nearly random distribution of comonomer moieties to block type distribution with different composition (10–50 mol % AA) were synthesized to investigate the effect of polymer architecture and composition on pH response and mechanical properties of resultant structures. These copolymers were solution spun from dimethylformamide-water system, drawn in coagulation bath, and annealed at 120°C for 2 h to make pH-sensitive fibers which were structurally stable without the need of chemical crosslinking. The fibers from block copolymers showed significantly better tensile strength (34.3 MPa), higher retractive forces (0.26 MPa), and enhanced pH response (swelling 3890%) in comparison with fibers from random copolymer (13.55 MPa, 0.058 MPa, and 1723%, respectively). The tensile strength and retractive forces could be further improved to a value of 72 MPa and 0.36 MPa, respectively, by changing the composition of the block copolymer while retaining the swelling percentage similar to the random copolymer mentioned above. It is proposed that on processing to fibers, the block copolymers could form a segregated domain structure with separate domains of AA and AN, where AN domains were responsible for high structural integrity by providing connectivity among polymer chains, while AA domains showed improved response to changing pH of the environment. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007

Hydrogen bonding in infinite hydrogen fluoride and hydrogen chloride chains

Hydrogen bonding in infinite HF and HCl bent (zigzag) chains is studied using the ab initio coupled-cluster singles and doubles (CCSD) correlation method. The correlation contribution to the binding energy is decomposed in terms of nonadditive many-body interactions between the monomers in the chains, the so-called energy increments. Van der Waals constants for the two-body dispersion interaction between distant monomers in the infinite chains are extracted from this decomposition. They allow a partitioning of the correlation contribution to the binding energy into short- and long-range terms. This finding affords a significant reduction in the computational effort of ab initio calculations for solids as only the short-range part requires a sophisticated treatment whereas the long-range part can be summed immediately to infinite distances.

Fractionation of Methyl Cellulose According to Polarity – a Tool to Differentiate First and Second Order Heterogeneity of the Substituent Distribution

AbstractSummary: A set of four MCs (DS 1.80–1.95) has been analyzed with regard to their substituent pattern in the glucosyl units and along the polymer chain. The average heterogeneity of methylation observed for the entire material was analyzed in more detail after fractionation according to polarity. All fractions obtained were analyzed with respect to their DS, monomer composition and deviation from a random distribution of these monomers in the polymer chains. By this approach, heterogeneity of first and second order could be differentiated. While for three of the MCs only a minor DS‐gradient over the material was observed, a more pronounced heterogeneity of first order was obtained for MC 4.ESI mass spectrum of the undissolved residue of MC 2 after deuteromethylation and partial hydrolysis; DP 2 and 3 are shown in detail. Signals are assigned according to the number of CH3‐groups.magnified imageESI mass spectrum of the undissolved residue of MC 2 after deuteromethylation and partial hydrolysis; DP 2 and 3 are shown in detail. Signals are assigned according to the number of CH3‐groups.