Effect of Tacticity Sequence of the Poly(N-isopropylacrylamide) Oligomer on Phase Transition Behavior in Aqueous Solution.

The tacticity of poly(N-isopropylacrylamide) (PNIPAM) has a strong impact on the lower critical solution temperature (LCST) in aqueous solution. The sequence of meso diads (m) and racemo diads (r) further contributes to such an effect. In this work, the phase transition behaviors of poly(N-isopropylacrylamide) pentamers with four kinds of sequences, i.e., rrmm, rmmr, mrrm, and rmrm, in water were studied applying replica exchange molecular dynamics with a modified OPLS/AA force field. The difference in local component concentration in the system was used as an order parameter to quantitatively describe the phase separation extent. It was found that the phase separation degree of rrmm and rmmr is higher than that of mrrm and rmrm at the same temperature. The LCSTs of rrmm and rmmr are lower than those of mrrm and rmrm. The radial distribution function and hydrogen bond analysis revealed that the average values of hydrogen bonds between pentamers for rrmm and rmmr are greater than those of mrrm and rmrm, whereas the average values of hydrogen bonds between pentamers and water for rrmm and rmmr are less than those of mrrm and rmrm. It was demonstrated that the isotactic triad (mm) plays an important role in the thermosensitive behaviors of the PNIPAM pentamer. The increase of isotactic triad (mm) content in the PNIPAM chain promotes the formation of intermolecular hydrogen bonds between amide and amide and leads to a higher aggregation of the pentamer with the sequence of rrmm or rmmr. Finally, the effect of the isotactic triad was qualitatively explained with the mean-field theory.

Modeling and Off-Design Performance Analysis of a Screw Expander-Based Steam Pressure Energy Recovery System in a Combined Heat and Power Unit.

A screw expander-based heating system is proposed based on a 330 MW combined heat and power unit to recover the extraction steam pressure energy. EBSILON Professional software was applied to model the proposed system, and the thermal performance of the traditional system and the new system was compared under different operating conditions. The results show that under the designed heating condition, the standard coal consumption rate of the new system is reduced by 4.74 g/kWh, and the exergy efficiency of the heating process is increased by 17.29%. When the extraction steam pressure changes with the load within a range greater than 0.1 MPa, there is an optimal operating range for the new system, which is related to the built-in pressure ratio of the screw expander and the extraction steam pressure difference, and the distribution of the optimal operating range varies with the supply-water temperature. The heating process exergy efficiency of the two systems shows opposite trends under off-design conditions. Additionally, under the condition of meeting the extraction steam pressure, the method for increasing the output power of the screw expander by adjusting the butterfly valve to increase the extraction steam pressure only increases the standard coal consumption rate of the system. Furthermore, through an application case study, the annual economic benefit of the new system is expected to be ¥ 4.15 million, and the payback period is 5.02 years.

Tunable oligo-histidine self-assembled monolayer junction and charge transport by a pH modulated assembly.

Histidine works as an important mediator in the charge transport process through proteins via its conjugate side group. It can also stabilize a peptide's secondary structure through hydrogen bonding of the imidazole group. In this study, the conformation of the self-assembled monolayer (SAM) and the charge transport of the tailor-made oligopeptide hepta-histidine derivative (7-His) were modulated through the pH control of the assembly environment. Histidine is found to be an efficient tunneling mediator in monolayer junctions with an attenuation factor of ß = ∼0.5 Å-1. Successful theoretical model fitting indicates a linear increase in the number of tunneling sites as the 7-His SAM thickness increases, following the deprotonation of histidine. Combined with the ultraviolet photoelectron spectroscopy (UPS) measurements, a modulable charge transport pathway through 7-His with imidazole groups of histidine as tunneling foot stones is revealed. Histidine therefore possesses a large potential for modulable functional (bio)electronic devices.

Self-assembly of amphiphilic truncated cones to form hollow nanovesicles.

To mimic the unique properties of capsid (protein shell of a virus), we performed Brownian dynamics simulations of the self-assembly of amphiphilic truncated cone particles with anisotropic interactions. The particle shape of a truncated cone in our simulations depended on the cone angle θ, truncated height h c and particle type (A x B y and B x A y B z ). The hydrophobic A moieties and hydrophilic B moieties are responsible for attractive and repulsive interactions, respectively. By varying the particle shape, truncated cones can assemble into hollow and vesicle-like clusters with a specific cluster size N. To assemble into hollow vesicles, the truncated height h c must be below a critical value. When h c exceeds this critical value, malformation will occur. The dynamics shows that the vesicle formation occurs in three stages: initially the growth is slow, then rapid, and finally it slows down. The truncated height h c has a stronger impact on the growth kinetics than the cone angle θ or the particle type. We explored how the cluster packing depended on the cooling rate and particle number as well as discussing the relationship between the cluster geometry and the interparticle interactions. Further, we also discuss possible methods to experimentally prepare the truncated cones. The results of our work deepen our understanding of the self-assembly behavior of truncated cones and our results will aid the effective design of particle building blocks for novel nanostructures.

Molecular dynamics simulation of electric-field-induced self-assembly of diblock copolymers.

The self-assembly of block copolymers under an external electric field was studied with a coarse-grained polarizable model that hybridizes the conventional polymeric coarse-grained model and Drude oscillator. The polarizability of the coarse-grained polymeric segment was reflected by the Drude oscillator. Applying this model, the alignment of the lamellar phase of the block copolymer melt under an external electric field was observed and the dynamic coupling information between chain polarization and interface orientation induced by the external electric field was obtained. It is demonstrated that the alignment of the lamellar structure along the electric field direction results from the polarizability difference of the polymer components. Finally, the transitions of phase structures of the block copolymer under an external electric field, from spherical phase to cylindrical phase, from gyroid structure to cylindrical phase, and from gyroid structure to lamellae phase were simulated. The specific evolution pathways were shown.

Tuning phase structures of a symmetrical diblock copolymer with a patterned electric field.

Electric fields can induce the orientation of the phase interfaces of block copolymers and provide a potential method to tune polymer phase structures for nanomaterial manufacture. In this work, we applied self-consistent field theory to study the self-assembly of a diblock copolymer confined between two parallel neutral substrates on which a set of electrodes was imposed to form a patterned electric field. The results showed that an alternatively distributed electric field can induce the formation of a parallel lamellar phase structure, which exists stably only in the system with selective substrates. The phase structure was proved to be sensitive to the characteristics of the electric field distribution, such as the strength of the electric field, the size and position of the electrodes, and the corresponding phase diagram was calculated in detail. The transition pathway of the phase structure from the perpendicular layered phase to the parallel layered phase was further analysed using the minimum energy path method. It is shown that the path and the active energy barrier of the phase transition depend on the electric field strength. Compound electric field patterns that can be designed to control the formation of novel and complex microphase structures were also examined.

Kinetics of a Multilamellar Lipid Vesicle Ripening: Simulation and Theory.

Lipid vesicle ripening via unimolecular diffusion and exchange greatly influences the evolution of complex vesicle structure. However, this behavior is difficult to capture using conventional experimental technology and molecular simulation. In the present work, the ripening of a multilamellar lipid vesicle (MLV) is effectively explored using a mesoscale coarse-grained molecular model. The simulation reveals that a small MLV evolves into a unilamellar vesicle over a very long time period. In this process, only the outermost bilayer inflates, and the inner bilayers shrink. With increasing MLV size, the ripening process becomes complex and depends on competition between a series of adjacent bilayers in the MLV. To understand the diffusion behavior of the unimolecule, the potentials of mean force (PMFs) of a single lipid molecule across unilamellar vesicles with different sizes are calculated. It is found that the PMF of lipid dissociation from the inner layer is different than that of the outer layer, and the dissociation energy barrier sensitively depends on the curvature of the bilayer. A kinetics theoretical model of MLV ripening that considers the lipid dissociation energy for curved bilayers is proposed. The model successfully interprets the MLV ripening process with various numbers of bilayers and shows potential to predict the ripening kinetics of complex lipid vesicles.

Self-assembly of Janus ellipsoids: a Brownian dynamics simulation with a quantitative nonspherical-particle model.

Janus ellipsoids as mesoscale building blocks can aggregate into various micelle-like structures in solution that have potential applications in many fields such as novel surfactants, photonic crystals, drug delivery and biochemical sensors. In this work, we present a novel nonspherical-particle model to investigate the self-assembly of Janus ellipsoids, which quantitatively reflects interaction dependence on the particle shape. The phase diagrams of Janus ellipsoids depending on the aspect ratio and the component ratio are achieved and various aggregates are observed such as a sandwich-type structure, columnar aggregates, vesicles, liquid crystals, random aggregation structures, spherical micelles and wormlike micelles. The specific heat capacity curves and temperature evolutions illustrate the formation processes of assembled superstructures detailedly. We analyze the potential energy surfaces (PESs) of interaction between two Janus ellipsoids and the minimum energy paths (MEPs) between saddle points on the PESs. It is found that the number of metastable conformation and the activation energy along MEPs rely not only on the ellipsoidal shape but also on the component ratio. This work provides rich and valuable information for a deep understanding of the self-assembly mechanism of Janus ellipsoids and design of new mesoscale building blocks.

Anion-dipole interactions make the homopolymers self-assemble into multiple nanostructures.

Anion-dipole interactions can make homopolymers self-assemble like an amphiphilic block copolymer. Generally, common homopolymers cannot self-assemble into multiple nanostructures. Here, it is reported that anion-dipole interactions can enable a number of homopolymers to achieve a variety of self-assembly behaviors in aqueous solution. Such interactions and self-assembly features have been exclusively reserved for amphiphilic (block) polymers until now.

Self-assembly of diblock copolymer confined in an array-structure space.

The combination of top-down and bottom-up technologies is an effective method to create the novel nanostructures with long range order in the field of advanced materials manufacture. In this work, we employed a polymeric self-consistent field theory to investigate the pattern formation of diblock copolymer in a 2D confinement system designed by filling pillar arrays with various 2D shapes such as squares, rectangles, and triangles. Our simulation shows that in such confinement system, the microphase structure of diblock copolymer strongly depends on the pitch, shape, size, and rotation of the pillar as well as the surface field of confinement. The array structures can not only induce the formation of new phase patterns but also control the location and orientation of pattern structures. Finally, several methods to tune the commensuration and frustration of array-structure confinement are proposed and examined.

Denaturation and renaturation behaviors of short DNA in a confined space.

A deep understanding to the denaturation and renaturation behaviors of DNA in a confined state is fundamentally important to control the self-assembly of DNA in a chamber or channel for various applications. In this report, we study the denaturation and renaturation behaviors of short DNA confined in cylindrical and spherical spaces with the 3-Site-Per-Nucleotide coarse-grained DNA model applying the replica exchange molecular dynamics technology. It is found that as the confinement size decreases, the melting temperature Tm increases and the transition becomes broad. The analysis of the potential of mean force shows that the confinement increases the relative free energy of the denatured state of DNA and decreases the renaturation energy barrier. Besides the denatured and native states, the metastable parallel-stranded structure is also found. The simulation results show that the shapes of the confinement spaces and the short DNA sequences remarkably affect the renaturation behavior. In the cylindrical space, the DNA renaturation changes from random-binding to slithering-binding with the size of the confinement space decreasing. In contrast, the DNA renaturation in the spherical and symmetrical confinement space proceeds through strand binding and rolling. The relationship between the melting temperature and the confinement size, ΔTm/Tm ∼ Rc (-υ), is estimated and the exponential index υ equals about 1.32 and 1.75 in the cylindrical and spherical confinements, respectively. It is further compared with the theoretical result of the rigid rod model and a qualitative agreement with the simulation is achieved.

Phase transition behaviours of a single dendritic polymer.

Dendritic polymers with highly branching structures exhibit many unique properties. In this paper, a computational study using the Wang-Landau sampling technique is carried out to reveal the phase transition behaviours of dendritic homopolymers with various branching structures. Two types of dendritic homopolymers, dendrimers/dendrigrafts (D/D) and hyperbranched (HB) polymers are studied. It is found that with increasing degree of branching in the dendritic polymer, the liquid-solid (LS) transition temperature increases and the coil-globule (CG) transition becomes weak. Additionally, under similar degrees of branching and polymerization, D/D polymers have a higher LS transition temperature than HB polymers. The reason is that the D/D polymers have greater regularity in the radial distribution of the branching units, which facilitates monomer packing during the LS transition. The distinctive internal unit distribution at various temperatures is quantitatively analysed. Our results show the importance of dendritic polymer structure regularity in phase transition behaviours and are valuable in guiding the structural design of dendritic macromolecules for functionalization applications.

Melting processes of oligomeric α and ß isotactic polypropylene crystals at ultrafast heating rates.

The melting behaviors of α (stable) and ß (metastable) isotactic polypropylene (iPP) crystals at ultrafast heating rates are simulated with atomistic molecular dynamics method. Quantitative information about the melting processes of α- and ß-iPP crystals at atomistic level is achieved. The result shows that the melting process starts from the interfaces of lamellar crystal through random dislocation of iPP chains along the perpendicular direction of lamellar crystal structure. In the melting process, the lamellar crystal gradually expands but the corresponding thickness decreases. The analysis shows that the system expansion lags behind the crystallinity decreasing and the lagging extents for α- and ß-iPP are significantly different. The apparent melting points of α- and ß-iPP crystals rise with the increase of the heating rate and lamellar crystal thickness. The apparent melting point of α-iPP crystal is always higher than that of ß-iPP at differently heating rates. Applying the Gibbs-Thomson rule and the scaling property of the melting kinetics, the equilibrium melting points of perfect α- and ß-iPP crystals are finally predicted and it shows a good agreement with experimental result.

A DFT study of the regeneration process of zinc porphyrin analogues in dye-sensitized solar cells.

The regeneration reaction of sensitizers in dye-sensitized solar cells is one of the critical steps in photonic chemical circuits. In this report, the two-step regeneration reaction of a series of zinc porphyrin sensitizers with a variety of substituent groups, i.e., CN-, F-, Cl-, H-, PhCH3-, OH- and NH2- groups, has been studied using density functional theory (DFT). The effects of the substituent groups on the structures of zinc porphyrin sensitizers, the regeneration intermediates and the reaction thermodynamics and kinetics have been explored. It is found that substituent groups at meso-position of zinc porphyrins strongly influenced the mode of two-step regeneration. For Por-CN, Por-F and Por-Cl, the formation of DyeI(Zn) and DyeI(Zn)-I intermediates are dominant, whereas for Por-H, Por-PhCH3 and Por-OH, the formation of DyeI(Py) and DyeI(Py)-I intermediates predominate. Due to the stronger electron-withdrawing effect of CN- and F-, the corresponding Por-CN and Por-F have no energy barrier in reaction. This suggests that their regeneration should be faster than the others. Besides two-step regeneration, alternative regenerations including one-step regeneration and reductive quenching reaction of excited dye and the influences of substituent groups on the electron injection efficiency are also estimated. These results provide valuable information for the design of novel zinc porphyrin analogues for DSCs.

Phase segregation of a symmetric diblock copolymer in constrained space with a square-pillar array.

In this study, we apply a self-consistent field theory of polymers to study the structures of a symmetric diblock copolymer in parallel substrates filled with square-pillar arrays in which the substrates and pillars exhibit a weak preference for one block of the copolymer. Three classes of structures, i.e., lamellae, perpendicular cylinders, and bicontinuous structures, are achieved by varying the polymer film thickness, the pillar pitch (the distance between two centers of the nearest neighboring pillars), the gap and rotation of the pillars. Because of the confinement along horizontal directions imposed by the pillar array, eight novel types of perpendicular lamellar structures and eight novel types of cylindrical structures with various shapes and distributions occur. In the hybridization states of the parallel and perpendicular lamellar structures, several novel bicontinuous structures such as the double-cylinder network, pseudo-lamellae, and perforated lamellar structure are also found. By comparing the free energies of the various possible structures, the antisymmetric parallel lamellae are observed to be stable with the larger pillar gap at a certain film thickness. The structural transformations between the alternating cylindrical structures (alternating cross-shaped, square-shaped, and octagonal perpendicular cylinders) and parallel lamellae with increasing film thickness or pillar gap are well explained by the modified strong separation theory. Our results indicate that array confinement can be an effective method to prepare novel polymeric nanopattern structures.

Phase transition of a single star polymer: a Wang-Landau sampling study.

Star polymers, as an important class of nonlinear macromolecules, process special thermodynamic properties for the existence of a common connecting point. The thermodynamic transitions of a single star polymer are systematically studied with the bond fluctuation model using Wang-Landau sampling techniques. A new analysis method employing the shape factor is proposed to locate the coil-globule (CG) and liquid-crystal (LC) transitions, which shows a higher efficiency and accuracy than the canonical specific heat function. The LC transition temperature is found to obey the identical scaling law as the linear polymers. However, the CG transition temperature shifts towards the LC transition with the increasing of the arm number. The reason is that for the star polymer a lower temperature is needed for the attractive force to overcome the excluded volume effect of the polymer chain because of its high arm density. This work clearly proves the structural distinction of the linear and star polymers can only affect the CG transition while has no influence on the LC transition.

Diffusion-limited hyperbranched polymers with substitution effect.

Highly branched structure has the essential influence on macromolecular property and functionality in physics and chemistry. In this work, we proposed a diffusion-limited reaction model with the consideration of macromolecular unit relaxations and substitution effect of monomers to study the structure of hyperbranched polymers prepared by slow monomer addition to a core molecule. The exponential relationship (R(g) ∼ N(λ)) between the radius of gyration R(g) and the degree of polymerization N, was systematically analyzed at various branching degrees. It is shown that the effective exponent λ(eff) decreases at lower N and but increases toward that of diffusion-limited aggregation (DLA) clusters (λ(DLA) = 0.4) with the degree of polymerization increasing. The substitution effect of monomers in reaction strongly influences the evolution pathway of λ(eff). With the static light scattering technique, the fractal property of internal chains was further calculated. A general law about the radial distribution of the units of diffusion-limited hyperbranched polymers was found that, at smaller reactivity ratio k(12), the radial density of all monomer units D(A) declines from the center region to the peripheral layer revealing the dense core structure; however, at larger k(12), the density distribution shows a loose-dense-loose structure. These structural characteristics are helpful to deeply understand the property of hyperbranched polymers.

Dynamics of vesicle formation from lipid droplets: mechanism and controllability.

A coarse-grained model developed by Marrink et al. [J. Phys. Chem. B 111, 7812 (2007)] is applied to investigate vesiculation of lipid [dipalmitoylphosphatidylcholine (DPPC)] droplets in water. Three kinds of morphologies of micelles are found with increasing lipid droplet size. When the initial lipid droplet is smaller, the equilibrium structure of the droplet is a spherical micelle. When the initial lipid droplet is larger, the lipid ball starts to transform into a disk micelle or vesicle. The mechanism of vesicle formation from a lipid ball is analyzed from the self-assembly of DPPC on the molecular level, and the morphological transition from disk to vesicle with increasing droplet size is demonstrated. Importantly, we discover that the transition point is not very sharp, and for a fixed-size lipid ball, the disk and vesicle appear with certain probabilities. The splitting phenomenon, i.e., the formation of a disk/vesicle structure from a lipid droplet, is explained by applying a hybrid model of the Helfrich membrane theory. The elastic module of the DPPC bilayer and the smallest size of a lipid droplet for certain formation of a vesicle are successfully predicted.

Spontaneous formation of complex micelles from a homogeneous solution.

We present an extensive computer simulation study of structure formation in amphiphilic block copolymer solutions after a quench from a homogeneous state. By using a mesoscopic field-based simulation method, we are able to access time scales in the range of a second. A "phase diagram" of final structures is mapped out as a function of the concentration and solvent philicity of the copolymers. A rich spectrum of structures is observed, ranging from spherical and rodlike micelles and vesicles to toroidal and net-cage micelles. The dynamical pathways leading to these structures are analyzed in detail, and possible ways to control the structures are discussed briefly.