Effect Of Molecular Architecture Research Articles

Effect of molecular architecture on the crystalline structure and stiffness of iPP homopolymers: Modeling based on annealing experiments

ABSTRACTFive polypropylene (PP) homopolymers were selected and their molecular structure was thoroughly characterized to determine the effect of molecular architecture on their annealing behavior and on the ultimate stiffness achieved by heat treatment. Molecular mass and its distribution were characterized by rheological measurements, while chain regularity was determined by differential scanning calorimetry (DSC) using stepwise isothermal segregation technique (SIST). The samples were annealed in two different ways. Tensile bars were treated in an oven at 165 °C for increasing times to determine changes in stiffness. Various defects (microcracks and voids) developed during the annealing of tensile specimens that did not allow the reliable determination of modulus by direct measurement. On the other hand, the second approach, the annealing of small samples in a DSC cell clearly showed the changes occurring in crystalline structure and also the effect of nucleation and molecular architecture on them. The large molecular weight fraction used to facilitate nucleation hinders crystal perfection, whereas the presence of a heterogeneous nucleating agent increases overall crystallinity, but does not influence recrystallization during annealing. Melting traces were transformed into lamella thickness distributions from which average lamella thickness was derived. Lamella thickness and crystallinity, the independent variables of the model equation used for the calculation of modulus, were extrapolated to infinite annealing time to predict maximum stiffness. The value obtained, 3.5 GPa, is very far from the theoretically predicted 40 GPa of oriented crystals, which cannot be achieved under practical conditions. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3365–3373, 2013

Positron annihilation lifetime spectroscopy for miscibility investigations of styrene–butadiene–styrene copolymer/polystyrene blends

The free volume parameters of styrene–butadiene–styrene copolymer/polystyrene (SBS/PS) blends were investigated with positron annihilation lifetime spectroscopy (PALS) in this study. The behaviors of free volume distribution, average free volume, and relative fractional free volume revealed the difference of interfacial miscibility. Based on different models, inter‐chain interaction parameter β, geometric factor γ, and hydrodynamic interaction parameter α obtained from free volume data were employed to further determine the effect of molecular architecture and styrene content on the miscibility. The results suggest the better miscibility in star‐shaped SBS/PS blends than that of corresponding linear SBS/PS systems, even than that of systems containing more styrene unit. In addition, differential scanning calorimetry, dynamic mechanical analysis, and scanning electron microscopy, which are sensitive to heterogeneities in larger domain size, give different results of miscibility from free volume data. It should be attributed the difference of characterization scale. The mechanical property corroborates the results of miscibility. POLYM. ENG. SCI., 54:785–793, 2014. © 2013 Society of Plastics Engineers

Dynamics in Anionic Micelles: Effect of Phenyl Ring

Micellar dynamics in sodium dodecyl benzene sulfonate (SDBS) is studied using quasi-elastic neutron scattering (QENS) technique. Results are compared with sodium dodecyl sulfate (SDS), a very similar surfactant except for the presence of a phenyl ring in SDBS. SDBS is a very important system for various industrial usages and variety of other applications. The aim here is to investigate the effect of molecular architecture of the surfactant molecule on micellar dynamics. Analysis of the QENS data showed that there exists two distinct motions in both of the micellar systems: whole micellar motion or global motion and the internal motion of the monomer within the micelles. The global diffusion associated with the whole micelle is found to be Fickian in nature. The diffusion coefficient corresponding to the global motion is found to be significantly lower for SDBS than SDS micelles. As far as internal motion is concerned, the structure factor indicates that the alkyl chains are more flexible in SDS compared with SDBS. Similar behavior is also reported in a recent molecular-dynamics simulation study. Detailed analysis showed that a localized translational diffusion model in which the hydrogen atoms undergo diffusion within a sphere could describe the internal motions in both the micelles. Diffusion coefficients corresponding to internal motions is found to be lower in the case of SDBS micelles compared with SDS micelles, implying that internal motions in SDBS micelles are relatively hindered vis-a-vis SDS micelles. This could be understood in terms of denser packing in SDBS micelles due to the presence of π-stacking.

Effect of molecular architecture on micellization, drug loading and releasing of multi-armed poly(ethylene glycol)-b-poly(ε-caprolactone) star polymers

This study investigated the effect of molecular architecture of amphiphilic star polymers on micelle formation and drug loading and releasing. For this, multi-armed star block copolymers having poly(ethylene glycol) as a hydrophilic block and poly(e-caprolactone) as a hydrophobic block were synthesized by using a divergent synthetic method consisting of a coupling reaction and a ring opening polymerization. The molecular weight and molecular weight distribution of the block copolymers were characterized by 1H NMR and GPC measurements. Dynamic light scattering and fluorescence spectroscopic analysis were employed to observe micellization, drug loading, and drug release behaviors. We have figured out that the number of arms is a critical factor that changes critical micelle concentration as well as drug loading and releasing behaviors; increase in the number of arms not only led to lowering the critical micelle concentration and drug release rate but also increased the micelle size and drug loading efficiency.

Dissipative particle dynamics simulation of onion phase in star-block copolymer

A dissipative particle dynamics simulation technique was used to investigate the effect of molecular architecture of star-block copolymer on the patterned structure in a nanodroplet. With increasing the ratio of solvophilic to block length to solvophobic block length(RH/T), solvophobic sphere, ordered hexagonal phase, onion phase, perforated onion phase and flocculent phase are formed, respectively. Since onion phase has potential application in controlled drug release, it has received wide attention experimentally and theoretically. Our simulation indicates onion phase forms at a certain RH/T(close to but less than 1). A star-block copolymer molecule has two conformations in onion phase: either fully located in a shell or shared by two neighboring shells. Central structure affects onion’s final shape. The molecular number of the copolymer in each shell is a quadratic function of the shell’s radius. The arm number of star-block copolymer has little influence on onion’s structure, but slightly affects the solvent content. Additionally, we studied the influence of arm length on onion’s structure.

Reconfiguring the architectures of cationic helical polypeptides to control non-viral gene delivery

Poly(γ-4-((2-(piperidin-1-yl)ethyl)aminomethyl)benzyl-l-glutamate) (PPABLG), a cationic helical polypeptide, has been recently developed by us as an effective non-viral gene delivery vector. In attempts to elucidate the effect of molecular architecture on the gene delivery efficiencies and thereby identify a potential addition to PPABLG with improved transfection efficiency and reduced cytotoxicity, we synthesized PEG-PPABLG copolymers with diblock, triblock, graft, and star-shaped architectures via a controlled ring-opening polymerization. The PPABLG segment in all copolymers adopted helical structure; all copolymers displayed structure-related cell penetration properties and gene transfection efficiencies. In HeLa and HepG-2 cells, diblock and triblock copolymers exhibited reduced membrane activities and cytotoxicities but uncompromised gene transfection efficiencies compared to the non-PEGylated homo-PPABLG. The graft copolymer revealed lower DNA binding affinity and membrane activity presumably due to the intramolecular entanglement between the grafted PEG segments and charged side chains that led to reduced transfection efficiency. The star copolymer, adopting a spherical architecture with high density of PPABLG, afforded the highest membrane activity and relatively low cytotoxicity, which contributed to its potent gene transfection efficiency that outperformed the non-PEGylated PPABLG and Lipofectamine™ 2000 by 3–5 and 3–134 folds, respectively. These findings provide insights into the molecular design of cationic polymers, especially helical polypeptides towards gene delivery.

Ionic Aggregate Structure in Ionomer Melts: Effect of Molecular Architecture on Aggregates and the Ionomer Peak

We perform a comprehensive set of coarse-grained molecular dynamics simulations of ionomer melts with varying polymer architectures and compare the results to experiments in order to understand ionic aggregation on a molecular level. The model ionomers contain periodically or randomly spaced charged beads, placed either within or pendant to the polymer backbone, with the counterions treated explicitly. The ionic aggregate structure was determined as a function of the spacing of charged beads and also depends on whether the charged beads are in the polymer backbone or pendant to the backbone. The low wavevector ionomer peak in the counterion scattering is observed for all systems, and it is sharpest for ionomers with periodically spaced pendant charged beads with a large spacing between charged beads. Changing to a random or a shorter spacing moves the peak to lower wavevector. We present new experimental X-ray scattering data on Na(+)-neutralized poly(ethylene-co-acrylic acid) ionomers that show the same two trends in the ionomer peak, for similarly structured ionomers. The order within and between aggregates, and how this relates to various models used to fit the ionomer peak, is quantified and discussed.

Molecular Architecture Influences the Thermally Induced Aggregation Behavior of Elastin-like Polypeptides

Elastin-like polypeptides are thermally responsive polymers that exhibit phase separation above a transition temperature. The effect of molecular architecture on the temperature responsive behavior of elastin-like polypeptide solutions was investigated by characterization of solutions of three-armed star polypeptides, linear polypeptides, and their mixtures. These biosynthesized polypeptides have precise lengths and amino acid sequences. Transition temperatures were measured as a function of molecular weight and solution concentration and compared to their linear counterparts. Like their linear counterparts, the transition temperature is linearly related to log concentration. A mathematical relationship was used to fit the transition temperature data of different polypeptide lengths to a volume-based concentration using the polymer coil volume. The results of this model suggest that the linear ELP is in a random coil conformation at the transition temperature while the three-armed ELP is in a compact extended coil conformation, consistent with different pathways for aggregation. Solutions containing both trimer and linear constructs have two transition temperatures, further supporting differing aggregation behaviors.

Self-assembly of non-linear polymers at the air/water interface: the effect of molecular architecture

In comparison with conventional linear polymers, due to the presence of joints, branches, end groups, etc, non-linear polymers possess more variables that allow for the tailoring of steric constraints, stacking interactions, and hydrogen bonding of these polymers at the air/water interface to precisely control the self-assembly process to yield functional Langmuir–Blodgett (LB) films for various applications. This Review summarizes recent developments in the field of self-assembly of non-linear polymers at the air/water interface, focusing on the influence of molecular architecture. Four classes of non-linear systems (polymer brushes, star-like polymers, dendritic polymers, and linear–dendritic polymers) with representative examples are highlighted to elaborate their interfacial behaviors originating from different molecular architectures.

Microphase separation in thin films of supramolecular assemblies composed of a triblock copolymer and low‐molecular‐weight additive

AbstractThe phase behavior of supramolecular assemblies (SMAs) formed by poly(4‐vinylpyridine)‐block‐polystyrene‐block‐poly(4‐vinylpyridine) (P4VP‐b‐PS‐b‐P4VP) triblock copolymer with 2‐(4′‐hydroxybenzeneazo)benzoic acid (HABA) was investigated with respect to the molar ratio (X) between HABA and 4VP monomer unit in bulk as well as in thin films. The results were compared with SMAs formed by a PS‐b‐P4VP diblock copolymer of similar composition as the triblock but half the molecular weight to ascertain the effect of molecular architecture on microphase separation. In bulk, both the di‐ and triblock SMAs showed composition‐dependent morphological transitions, which could be tuned by HABA/4VP molar ratio. The domain spacing of the SMA was not significantly affected by the molecular architecture of the constituting block copolymers. In thin films also, both the di‐ and triblock SMAs showed more or less similar morphological transitions depending on X. Interestingly, the domain orientation of the cylindrical or lamellar microdomains in the SMAs was influenced by the molecular architecture of the block copolymer. After chloroform annealing, although the diblock SMAs showed in‐plane orientation of the domains, triblock SMAs showed perpendicular domain orientation. The perpendicular orientation of the microdomains in triblock was favored because it allowed the mid‐PS blocks to acquire normal distribution of loop and bridged conformations. Furthermore, the orientation of the lamellar and cylindrical microdomains of the diblock SMAs was found to switch to perpendicular orientation after annealing in 1,4‐dioxane vapors. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1594–1605, 2010

Effect of molecular architecture on the self-diffusion of polymers in aqueous systems: A comparison of linear, star, and dendritic poly(ethylene glycol)s

Star polymers with a hydrophobic cholane core and four poly(ethylene glycol) (PEG) arms, CA(EG n) 4, have been synthesized by anionic polymerization. Pulsed-gradient spin-echo NMR spectroscopy was used to study the diffusion behavior of the star polymers, ranging from 1000 to 10,000 g/mol, in aqueous solutions and gels of poly(vinyl alcohol) (PVA) at 23 °C. The star polymers have a lower self-diffusion coefficient than linear PEGs at equivalent hydrodynamic radius. In water alone, the star polymers and their linear homologues have a similar diffusion behavior in the dilute regime, as demonstrated by the similar concentration dependence of the self-diffusion coefficients. In the semidilute regime, the star polymers tend to aggregate due to their amphiphilic properties, resulting in lower self-diffusion coefficients than those of linear PEGs. 1H NMR T 1 measurements at 10–70 °C revealed that the PEG arms of the star polymers are more mobile than the core, suggesting the star polymers in solution have a conformation similar to that of poly(propylene imine) dendrimers.

Evolution of interphase in styrene-butadiene block copolymers as revealed by 1H solid-state NMR: Effect of temperature and molecular architecture

1H spin-diffusion solid-state NMR, in combination with other techniques, was utilized to investigate the effect of molecular architecture and temperature on the interphase thickness and domain size in poly(styrene)-block-poly(butadiene) and poly(styrene)-block-poly(butadiene)-block-poly(styrene) copolymers (SB and SBS) over the temperature range from 25 to 80°C. These two block copolymers contain equal PS weight fraction of 32wt%, and especially, polystyrene (PS) and polybutadiene (PB) blocks are in glass and melt state, respectively, within the experimental temperature range. It was found that the domain sizes of the dispersed phase and interphase thicknesses in these two block copolymers increased with increasing temperature. Surprisingly we found that the interphase thicknesses in these two block copolymers were obviously different, which was inconsistent with the theoretical predictions about the evolution of interphase in block copolymer melts by self-consistent mean-field theory (SCFT). This implies that the interphase thickness not only depends strongly on the binary thermodynamic interaction (χ) between the PS and PB blocks, but also is influenced by their molecular architectures in the experimental temperature range.

Synthesis and Property of Y-Shaped Thermoresponsive Block Copolymers

Novel Y-shaped amphiphilic block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide), PEG-b-(PNIPAM)2, were successfully synthesized through atom transfer radical polymerization (ATRP). A difunctional macroinitiator was prepared by esterification of 2,2-dichloroacetyl chloride with poly(ethylene glycol) monomethyl ether (PEG). The copolymers were obtained via the ATRP of N-isopropylacrylamide (NIPAM) with CuCl/Me6TREN as catalyst and DMF/H2O (v/v = 3:1) mixture as solvent. The resulting polymers were characterized by gel permeation chromatography (GPC) and 1H NMR. These block copolymers show controllable molecular weights and narrow molecular weight distributions (PDI <1.15). Their phase transition temperatures and enthalpy changes in aqueous solution were measured by differential scanning calorimetry (DSC). The results indicate a significant influence of the macromolecular architecture on the phase transition. This is the first study into the effect of molecular architecture on the phase transition using Y-shaped amphiphilic block copolymer composed of PEG and PNIPAM.

Infrared spectroscopy studies of mixtures prepared with synthetic ceramides varying in head group architecture: Coexistence of liquid and crystalline phases

The barrier function of the skin is provided by the stratum corneum (SC), the outermost layer of the skin. Ceramides (CERs), cholesterol (CHOL) and free fatty acids (FFAs) are present in SC and form highly ordered crystalline lipid lamellae. These lamellae are crucial for a proper skin barrier function. In the present study, Fourier transform infrared spectroscopy was used to examine the lipid organization of mixtures prepared from synthetic CERs with CHOL and FFAs. The conformational ordering and lateral packing of these mixtures showed great similarities to the lipid organization in SC and lipid mixtures prepared with native CERs. Therefore, mixtures with synthetic CERs serve as an excellent tool for studying the effect of molecular architecture of CER subclasses on the lipid phase behavior. In SC the number of OH-groups in the head groups of CER subclasses varies. Furthermore, acylCERs with a linoleic acid chemically bound to a long acyl chain are also identified. The present study revealed that CER head group architecture affects the lateral packing and conformational ordering of the CER:CHOL:FFA mixtures. Furthermore, while the majority of the lipids form a crystalline packing, the linoleate moiety of the acylCERs participates in a “pseudo fluid” phase.

Effect of Porogen Molecular Architecture and Loading on Structure of Porous Thin Films

The effects of molecular architecture and loading of a porogen material on the structural characteristics of methylsilsesquioxane (MSQ)-based porous films are examined using X-ray porosimetry (XRP) and small-angle neutron scattering (SANS). Either linear (NG) or star-shaped (TP) polymers are used as the porogen here and blended with the MSQ material at loadings from 20 to 50% by mass, resulting in porosities between 30 and 60% by volume, regardless of porogen architecture. This indicates that the MSQ matrix material contains approximately 10% by volume inherent microporosity. The average pore size increases with increased porogen loadings in a way that depends on the porogen architecture. The NG porogen tends to aggregate, more than tripling the average pore size as the porogen loading increases from 20 to 50% by mass (22 to 76 Å in diameter). By contrast, the TP porogen has less propensity to aggregate, leading to a smaller increase in terms of percent change in the average pore size for the same porogen loading range (76 to 132 Å in diameter). Changes in the porogen type or loading do not influence the wall density (1.47 ± 0.01) g/cm3 of the material between the pores, whereas the coefficient of thermal expansion (CTE) is approximately 1.5 times greater for the NG samples than for the TP samples at all porogen loadings.

Molecular Architecture Effect on the Self-Assembly Behavior of Comb-Coil Block Copolymers Displaying Lamellae-within-Lamellae Morphology

Supramolecular comb-coil block copolymers formed by the stoichiometric complexation of two amphiphilic surfactants, dodecylbenzenesulfonic acid (DBSA) and 3-pentadecylphenol (PDP), with the poly(4-vinylpyridine) (P4VP) blocks in a linear PS-b-P4VP and a nonlinear AnBn-type heteroarm star PS-P4VP copolymer have been investigated. All linear and heteroarm star systems under study exhibited lamellae-within-lamellae morphology even at high PS volume fraction, at which the previously studied systems showed lamellae-within-cylinder or lamellae-within-sphere morphology. The interlamellar distances of the larger-scale copolymer microdomains were found to be much larger in all heteroarm complexes than those in their linear counterparts. This was attributed to the chain crowding effect coupled with the different types of arrangement of comb blocks forming the smaller-scale lamellar mesophase. Moreover, the order−disorder transition temperatures of both the larger- and smaller-scale structures in the heteroarm star ...

Effect of molecular architecture on the morphology diversity of the multicompartment micelles: A dissipative particle dynamics simulation study

Dissipative particle dynamics simulation is performed to study the sensitive influence of the molecular architecture and/or segment sequence on the morphology diversity of the multicompartment micelles. The multicompartment micelle morphologies formed by ABC triblock copolymers with various molecular architectures, such as the linear, the pentalinear, the cyclic, the star-like, the tetra-arm, and the π-shape are investigated, and different morphologies of the multicompartment micelles, for example, worm-like, “hamburger”, sheet-like with pores, “sweet potato” with alternating layers, sheet-like with cylinder-inclusion, and three-dimensional network are observed in this work. The density profiles and the radial distribution functions are calculated to characterize the structures of the multicompartment micelles. The preparation of complex multicompartment micelles can be fulfilled by simply changing the segment sequence and molecular architecture such as adding new bonds and grafting points.

Surface segregation of highly branched polymer additives in linear hosts

Entropy-driven segregation of various branched and hyperbranched polymeric additives in chemically similar linear polymer hosts is studied using self-consistent (SCF) mean-field lattice simulations. The simulations account for the effect of molecular architecture on local configurational entropy in the blends, but ignores the effect of architecture on local density and blend compressibility. Star, dendrimer, and comb-like additives are all found to be enriched at the surface of chemically identical linear host polymers. The magnitude of their surface excess increases with increased number of chain ends and decreases with increased segmental crowding near the branch point. Provided the number of arms and molecular weight of the branched additives are maintained constant, we find that the simplest branched architecture, the symmetric star, exhibits the strongest preference for the surface of binary polymer blends. We show that a single variable, here termed the “entropic driving force density,” controls the relative surface affinities of branched additives possessing a wide range of architectures. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1788–1801, 2008

Effect of Molecular Architecture on Phase Behavior of Graft Copolymers

Influence of molecular architecture on phase behavior of graft copolymer melts was studied by using a reciprocal-space self-consistent filed theory (SCFT). The phase diagrams were examined as functions of the architectural parameters describing the graft copolymers (i.e., the number of grafts and the position of first junction). In comparison with the well-known phase diagram of diblock copolymers, the phase diagrams of the graft copolymers are asymmetric. When the number of grafts or the position of first junction varies, the boundaries of order-order transitions have shifts due to the variation in the chain stretching energy. The change in molecular architecture also significantly alters the domain spacing of ordered structures but has weak impact on the density distributions of graft copolymers. For comparison of the theoretical predictions with the existing experimental results, the phase diagrams of graft copolymers were also calculated at strong segregation. The SCFT calculations can accurately capture the characteristics of the phase behavior of graft copolymer melts.

Effects of Molecular Architecture on the Dynamics of Photoinduced Electron Transfer Processes in Porphyrin-[60]Fullerene Hybrid Systems

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