Configurational enthalpy of polystyrene

Recent precision measurements of the heats of combustion of atactic and isotactic polystyrene permit an unequivocal calculation of the enthalpy difference in the bulk amorphous forms of the two isomers of this polymer. Contributions to this quantity arise mainly from the differences in nonbonded interactions in the two configurations but may also contain terms relating to higher energy conformations and to intermolecular interactions. The thermochemical and NMR data of specific polymers and of simple molecules are discussed in a comparison with model compound calculations. The thermochemical method has potentially important applications in studying molecular interactions in stereoregular polymers.     

Mesoscopic description of solvent effects on polymer dynamics

Solvent effects on polymer dynamics and structure are investigated using a mesoscopic solvent model that accounts for hydrodynamic interactions among the polymer beads. The simulation method combines molecular dynamics of the polymer chain, interacting with the solvent molecules through intermolecular forces, with mesoscopic multiparticle collision dynamics for the solvent molecules. Changes in the intermolecular forces between the polymer beads and mesoscopic solvent molecules are used to vary the solvent conditions from those for good to poor solvents. Polymer collapse and expansion dynamics following changes in solvent conditions are studied for homopolymer and block copolymer solutions. The frictional properties of polymers are also investigated.     

The enthalpy of dilution as a direct characteristic of the energy spectrum of intermolecular interaction in polymer solutions and gels

Calorimetric data on the concentration dependences of the enthalpy of dilution of polymer solutions are analyzed. The profiles of concentration dependences strongly depend on the nature of intermolecular interactions in polymer solutions and gels and on the specific features of their structure, including phase and relaxation states. Therefore, the concentration dependence of the enthalpy of dilution is treated as a spectral curve containing information on the energy state of the polymer solution and gel as a function of concentration. Theoretical models are considered that allow estimation of quantitative contributions from paired intermolecular and electrostatic interactions in solutions and contributions provided by the metastable state of a glassy polymer and by the presence of crystalline ordering.     

Epoxy resin/poly(ethylene oxide) (PEO) and poly(ε-caprolactone) (PCL) blends cured with 1,3,5-trihydroxybenzene: miscibility and intermolecular interactions

Epoxy resin (ER)/poly(ethylene oxide) (PEO) and/or poly(e-caprolactone) (PCL) blends cured with 1,3,5-trihydroxybenzene (THB) were prepared via the in situ curing reaction of epoxy monomers in the presence of PEO and/or PCL, which started from the initially homogeneous mixtures of DGEBA, THB and PEO and/or PCL. The miscibility and the intermolecular specific interactions in the thermosetting polymer blends were investigated by means of differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). The two systems displayed single and composition-dependant glass transition temperatures (T _gs), indicating the full miscibility of the thermosetting blends. The experimental T _gs of the blends can be well accounted for by Gordon-Taylor and Kwei equations, respectively. The T _g-composition behaviors were compared with those of poly(hydroxyether of bisphnol A) (Phenoxy) blends with PEO and PCL. It is noted that the formation of crosslinked structure has quite different effects on miscibility and intermolecular hydrogen bonding interactions for the thermosetting polymer blends. In ER/PEO blends, the strength of the intermolecular hydrogen bonding interactions is weaker than that of the self-association in the control epoxy resin, which is in marked contrast to the case of Phenoxy/PEO blends. This suggests that the crosslinking reduces the intermolecular hydrogen bonding interactions, whereas the intermolecular hydrogen bonding interactions were not significantly reduced by the formation of the crosslinking structure in ER/PCL blends.     

Physical organic chemistry of supramolecular polymers

Unlike the case of traditional covalent polymers, the entanglements that determine properties of supramolecular polymers are defined by very specific, intermolecular interactions. Recent work using modular molecular platforms to probe the mechanisms underlying mechanical response of supramolecular polymers is reviewed. The contributions of supramolecular kinetics, thermodynamics, and conformational flexibility to supramolecular polymer properties in solutions of discrete polymers, in networks, and at interfaces, are described. Molecule-to-material relationships are established through methods reminiscent of classic physical organic chemistry.     

AFM单分子力谱在真实材料及生物体系中的应用——挑战与机遇并存

基于原子力显微镜技术（AFM）的单分子力谱是研究分子间分子内相互作用的有效手段．为了简化样品体系及数据的解析,真实的生物或材料体系通常被简化,其中的目标分子被提取并桥连于AFM的针尖与固体基片之间进行研究,这是认识真实体系的有效途径．随着技术的不断进步（包括样品固定方法的改进）,使得直接研究真实生物及材料体系中的各种弱相互作用成为可能,此种条件下获得的信息对相关生命过程的调控及高性能材料的设计更具指导意义．本文概述了近几年基于AFM力谱技术在活体细胞以及高分子材料领域的研究进展,分析了存在的主要问题,并对相关领域的未来进行了展望．     

Steric effects and competitive intra‐ and intermolecular host‐guest complexation between beta‐cyclodextrin and adamantyl substituted poly(acrylate)s in water: A 1H NMR,rheological and preparative study

A ¹H NMR and rheological study of host‐guest complexation interactions between three β‐cyclodextrin and three adamantyl substituted poly(acrylate)s, and also between them and adamantan‐1‐carboxylate and native β‐cyclodextrin, respectively, is reported. A close correllation between molecular level interactions and macroscopic characteristics of polymer networks in aqueous solution exists. It is found that intra‐ and intermolecular host‐guest complexation between the host β‐cyclodextrin and guest adamantyl substituents and the length of the aliphatic tether between them and the poly(acrylate) backbone have important roles. Dominantly, steric effects and competitive intra‐ and intermolecular host‐guest complexation are found to control poly(acrylate) isomeric interstrand linkage in polymer network formation. The preparations of five new 3% randomly substituted poly(acrylate)s are reported. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1818–1825, 2010     

Interactions underpinning the plasticization of a polymer matrix: a dynamic and structural analysis of DMP-plasticized cellulose acetate

This work establishes that the plasticization effect of a classical petrochemical plasticizer, dimethyl phthalate (DMP), on a polymer matrix, cellulose acetate (CA), is due to the development of intermolecular interactions of dipolar type. Plasticized cellulose acetate films are studied with regard to the interactions between the polymer and plasticizer at the macroscopic scale by thermogravimetric analysis and differential scanning calorimetry. At the molecular level, Fourier transform infrared spectroscopy and dielectric relaxation spectroscopy are used to elucidate the nature of interactions that are responsible for the plasticizing effects. These static and dynamic complementary analyses evidenced that DMP does not establish H-bonding interactions with the polymer chains of cellulose acetate but rather weaker interactions of dipolar type. These dipole–dipole interactions that develop between acetyl side groups of CA and the ester phthalate moieties of DMP increase the overall mobility of CA chains and also locally influence the molecular mobility and the water uptake tendency.     

Formation of a True Molecular Composite using Optimal Hydrogen Bonding

Guidelines for creating miscible blends containing a liquid crystalline polymer and an amorphous polymer by optimizing intermolecular interactions between the two polymers are presented. It is shown that by controlling the spacing between the functional groups that participate in hydrogen bonding along the amorphous polymer chain, the extent of intermolecular interactions between the two polymers is optimized, and this induces miscibility in the systems studied.     

First disyndiotactic polymer from a 1,4-disubstituted butadiene by alternate molecular stacking in the crystalline state

We report the first synthesis of a disyndiotactic polymer through topochemical polymerization using di(4-methoxybenzyl)muconate as the 1,3-diene dicarboxylate monomer. It provides a tritactic polymer under photoirradiation in the crystalline state, as a result of the alternate molecular stacking in a column formed in the crystals with aid of weak hydrogen bonds such as CH/pi and CH...O intermolecular interactions.     

Gelation characteristics and applications of poly(ethylene glycol) end capped with hydrophobic biodegradable dipeptides

Poly(ethylene glycol) (PEG) end capped with biodegradable hydrophobic dipeptides shows versatile gelation behavior in a wide range of aqueous and organic solvents. This gelation characteristic is attributed to the aggregation of polymer chains induced by dipeptide end groups. Both PEG molecular weight and molecular structure of end groups control this aggregation by striking a balance between two opposing molecular interactions: solubility of the PEG segment which tends to dissolve the polymer while hydrophobic and intermolecular noncovalent interactions between the end groups induce aggregation. Morphologically, this aggregated structure forms interpenetrating nano sheets with characteristic microstructural features. These gels are biodegradable and possess physicomechanical characteristics suitable for biomedical applications. Furthermore, proteins and hydrophobic model drugs can be encapsulated within the gels from aqueous and organic solvents, respectively, and can be released in a controlled fashion which indicates the applicability of the gels as drug delivery vehicles. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1917–1928     

Self-assembly of polypeptide-based block copolymer amphiphiles

The past decade has seen growing interest in the investigation of self-assembling nanostructures, particularly in aqueous solution. In this context, polypeptide-based copolymers show considerable promise as building blocks that allow enhanced control over intra- and intermolecular interactions, in concert with stable, yet modifiable, secondary and tertiary structures. We will focus here on the most recent advances in the formation of micelles and vesicles from peptide–polymer conjugates or from copolypeptide systems, and on the capacity of these structures to manifest stimuli-driven variation in size and shape. We will also discuss a new generation of materials based on protein-like copolymers that offer precise control over molecular composition and structure along with predetermined biological functionality.     

Molecular trapping on two-dimensional binary supramolecular networks

Molecular preferential adsorption on molecular patterned surfaces via specific intermolecular interactions provides an efficient route to construct ordered organic nanostructures for future nanodevices. Here, we demonstrate the preferential trapping of second-layer molecules atop two-dimensional binary supramolecular networks, F(16)CuPc on DIP:F(16)CuPc and 6P:F(16)CuPc systems, respectively, through intermolecular π-π interactions. The formation of the second-layer supramolecular nanostructures, individual molecular dots or linear molecular chains, can be controlled by the underlying molecular networks.     

Dielectric relaxation in polymeric solids Part 1. A new model for the interpretation of the shape of the dielectric relaxation function

A model is proposed which explains the shape of the dielectric relaxation function at the glass transition of polymers. The model is based on the idea that the molecular mobility at the glass transition is controlled by intra- and intermolecular interaction. In addition, a specific model for the local chain dynamics in amorphous polymer systems is used. According to the scaling hypothesis of molecular dynamics the model relates the high frequency dependence of the dielectric loss curve to the local chain dynamics and the low frequency dependence to the intermolecular correlation.     

Molecular determinants of protein-based coacervates

Protein–polyelectrolyte coacervates have gained interest for their potential to stabilize proteins or function as adhesives and their biological implications in the formation of membraneless organelles. To effectively design these materials or predict their biological formation, knowledge of the macromolecular properties that dictate phase separation is required. This review highlights recent advances in the understanding of molecular determinants of protein–polyelectrolyte phase behavior. Properties that promote the phase separation of protein–polyelectrolyte pairs are covered from the perspective of synthetic systems and simplified biological condensates. Prominent factors that determine coacervate formation and material properties include nonspecific intermolecular interactions, as well as specific biological interactions and structures. Here, we summarize the essential roles of electrostatics, including charge magnitude and distribution, (bio)polymer chemistry and structure, and post-translational modifications to protein phase separation in both a synthetic and cellular context.     

Main‐Chain Linear Polyrotaxanes: Synthesis,Characterization, and Conformational Modulation

Two functional main‐chain linear polyrotaxanes, one a covalent polymeric chain that threads through many macrocycles ( P1 ) and the other a poly[n]rotaxane chain that is composed of many repeating rotaxane units ( P2 ), were synthesized by employing strong crown‐ether/ammonium‐based ( DB24C8 / DBA ) host–guest interactions and click chemistry. Energy transfer between the wheel and axle units in both polyrotaxanes was used to provide insight into the conformational information of their resulting polyrotaxanes. Steady‐state and time‐resolved spectroscopy were performed to understand the conformation differences between polymers P1 and P2 in solution. Additional investigations by using dynamic/static light scattering and atomic force microscopy illustrated that polymer P1 was unbending and had a rigid rod‐like structure, whilst polymer P2 was curved and flexible. This flexible topology facilitated the self‐assembly of polymer P2 into relatively large ball‐shaped particles. In addition, the energy transfer between the wheel and axle units was controlled by the addition of specific anions or base. The anion‐induced energy enhancement was attributed to a change in electrostatic interactions between the polymer chains. The base‐driven molecular shuttle broke the DB24C8 / DBA host–guest interactions. These results confirm that both intra‐ and intermolecular electrostatic interactions are crucial for modulating conformational topology, which determines the assembly of polyrotaxanes in solution.     

如何理解混合溶剂的良、劣性

对于高聚物,混合溶剂的性能往往不能直接从相应的两种组分溶剂的性能来推演。本文从溶度参数理论、高分子对溶剂的择优吸附以及体系的分子特征,尤其是基于分子间相互作用对混合溶剂的良劣性作了较为详细的讨论。     

Structural and thermodynamic characteristics of amide solvents

The structural and thermodynamic characteristics of amide solvents are calculated with different types of molecular self-assembly through hydrogen bonding. Under a model-based approach, the specific and nonspecific components of the total energy of intermolecular interactions are identified for primary, secondary, and tertiary amides of carboxylic acids. It is found that similarly to water, primary amides have a network of hydrogen bonds and belong to the class of liquids characterized by an increase in nonspecific interactions with temperature. In secondary amides with the chain self-assembly, the contribution of these interactions is practically independent of temperature, and in tertiary amides it decreases with an increase in temperature. The molar values of the specific and nonspecific components are used to analyze the intermolecular interactions and the structural properties of amides with different degrees of N-substitution.     

Supramolecular Chemistry in Microflow Fields: Toward a New Material World of Precise Kinetic Control

Constructing new and versatile self‐assembling systems in supramolecular chemistry is much like the development of new reactions or new catalysts in synthetic organic chemistry. As one such new technology, conventional supramolecular assembly systems have been combined with microflow techniques to control intermolecular or interpolymer interactions through precise regulation of a flowing self‐assembly field. The potential of the microflow system has been explored by using various simple model compounds. Uniform solvent diffusion in the microflow leads to rapid activation of molecules in a nonequilibrium state and, thereby, enhanced interactions. All of these self‐assembly processes begin from a temporally activated state and proceed in a uniform chemical environment, forming a synchronized cluster and resulting in effective conversion to supramolecules, with precise tuning of molecular (or polymer) interactions. This approach allows the synthesis of a variety of discrete microstructures (e.g., fibers, sheets) and unique supramolecules (e.g., hierarchical assemblies, capped fibers, polymer networks, supramolecules with time‐delayed action) that have previously been inaccessible.     

Selective generation of organic aggregates included within metal-organic micropores through vapor adsorption

The ethanol vapor adsorption behavior and the inclusion crystal structure of a 1D-transformable coordination polymer host were characterized. The adsorption jump was observed during phase transition or two-phase equilibrium with abnormal adsorption enthalpy caused by the nature of "mass induced phase transition." The included ethanol guests selectively form O-H...O hydrogen bonded pairs inside channels, suggesting selective construction of a specific cluster/aggregate in pores under control of thermodynamic factors and cooperative intermolecular interactions among the guest and channel surface.