The Study of Electroactive Block Copolymer Containing Aniline Pentamer Isolated from Different Solvents

For the films and powder of polymers containing conductive oligomer are usually obtained from solution, the choice of better solvents for the regular arrangement of oligomers is very important for the higher conductivity. Because of the poor solubility of the oligomers, it is difficult to study the arrangement directly in most common solvents, so, we synthesized a triblock copolymer, mPEG2k-aniline pentamer-mPEG2k, as the model to investigate the arrangement-solvent relationship. For the poor solubility of the AP block in common solvents, the copolymer self-assembled into spheric micelles in toluene and into lamellar crystals in water and THF. The crystallinity (X-c) and crystallization temperature (T-c) values of mPEG blocks in powders prepared from different solvents differed obviously, which may be the effect of different self-assembled structures. From the two-phase model of one-dimensional electron density correlation function of SAXS, the long period of copolymer prepared from THF was presumably equal to the long period of pure mPEG plus the chain length of AP, which demonstrates that the AP blocks arrange regularly in the noncrystalline regions.

Effect of block sequence and block length on the stimuli-responsive behavior of polyampholyte brushes: hydrogen bonding and electrostatic interaction as the driving force for surface rearrangement

Diblock polyampholyte brushes with different block sequences (Si/SiO2/poly(acrylic acid)-b-poly (2-vinylpyridine) (PAA-b-P2VP) brushes and Si/SiO2/P2VP-b-PAA brushes) and different block lengths were synthesized by sequent surface-initiated atom transfer radical polymerization (ATRP). The PAA block was obtained through hydrolysis from the corresponding poly(tert-butyl acrylate). The polyampholyte brushes demonstrated unique pH-responsive behavior. In the intermediate pH region, the brushes exhibited a less hydrophilic wetting behavior and a rougher surface morphology due to the formation of polyelectrolyte complex through electrostatic interaction between oppositely charged blocks. In the low pH and high pH regions, the rearrangement of polyampholyte brushes showed great dependence on the block sequence and block length. The polyampholyte brushes with P2VP-b-PAA sequence underwent rearrangement during alternative treatment by acidic aqueous solution (low pH value) and basic aqueous solution (high pH value).

Solvent-induced Morphology of the Binary Mixture of Diblock Copolymer in Thin Film: The Block Length and Composition Dependence of Morphology

A series of binary SB blend samples with various overall volume fraction of PS (Phi(PS)) and different discrete distribution of the block length (denoted as d(PS) or d(PB)) were prepared by mixing various asymmetric poly(styrene)-block-poly(butadiene) (SB) block copolymers with a symmetric SB block copolymer. The influences of the external solvent field, composition, and the block length distribution on the morphologies of the blends in the thin films were investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The experimental results revealed that after solvent annealing, the interface of the blend thin films depended mainly on the cooperative effects of the annealing solvent and the inherently interfacial curvature of the blends. Upon exposure to the saturated vapor of cyclohexane, which has preferential affinity for the PB block, a "threshold" of Phi(PS) (approximate 0.635-0.707) was found. Below such threshold, the influence of the annealing solvent played an important role on the interfacial curvature of the blend thin film.

A self-consistent field theory study on the morphologies of linear ABCBA and H-shaped (AB)(2)C(BA)(2) block copolymers

By using a combinatorial screening method based on the self-consistent field theory, we investigate the equilibrium morphologies of linear ABCBA and H-shaped (AB)(2)C(BA)(2) block copolymers in two dimensions. The triangle phase diagrams of both block copolymers are constructed by systematically varying the volume fractions of blocks A, B, and C. In this study, the interaction energies between species A, B, and C are set to be equal. Four different equilibrium morphologies are identified, i.e., the lamellar phase (LAM), the hexagonal lattice phase (HEX), the core-shell hexagonal lattice phase (CSH), and the two interpenetrating tetragonal lattice phase (TET2). For the linear ABCBA block copolymer, the reflection symmetry is observed in the phase diagram except for some special grid points, and most of grid points are occupied by LAM morphology. However, for the H-shaped (AB)(2)C(BA)(2) block copolymer, most of the grid points in the triangle phase diagram are occupied by CSH morphology, which is ascribed to the different chain architectures of the two block copolymers. These results may help in the design of block copolymers with different microstructures.

Nonisothermal crystallization behavior of the poly(ethylene glycol) block in poly(L-lactide)-poly(ethylene glycol) diblock copolymers: Effect of the poly(L-lactide) block length

The confined crystallization behavior, melting behavior, and nonisothermal crystallization kinetics of the poly(ethylene glycol) block (PEG) in poly(L-lactide)poly(ethylene glycol) (PLLA-PEG) diblock copolymers were investigated with wideangle X-ray diffraction and differential scanning calorimetry. The analysis showed that the nonisothermal crystallization behavior changed from fitting the Ozawa equation and the Avrami equation modified by Jeziorny to deviating from them with the molecular weight of the poly(L-lactide) (PLLA) block increasing. This resulted from the gradual strengthening of the confined effect, which was imposed by the crystallization of the PLLA block. The nucleation mechanism of the PEG block of PLLA15000-PEG5000 at a larger degree of supercooling was different from that of PLLA2500-PEG5000, PLLA5000-PEG5000, and PEG5000 (the numbers after PEG and PLLA denote the molecular weights of the PEG and PLLA blocks, respectively). They were homogeneous nucleation and heterogeneous nucleation, respectively.

NMR-STUDY ON THE RELATIONSHIP BETWEEN MISCIBILITY AND ANTIAGING PERFORMANCE OF BLENDS CONTAINING BLOCK-COPOLYMERS

The anti-aging performance of blends of polystyrene (PS), styrene-butadiene triblock copolymers (SBS), and PS/styrene-butadiene (SB)-4A (Carm star SE block copolymer) has been studied by means of C-13 NMR techniques. It is found that the anti-aging performance of these kinds of blends largely depends on their miscibility with PS of different molecular weight M(PS). The larger the quantities of PS solubilized in polybutadiene (PBD) domains, the better the anti-aging performance of the blends. It is also found that the anti-aging performance of these blends has dependence on molecular architectures of the SE block copolymers. For the aged blends, the double bonds of PBD were broken, meanwhile serious cross-linking networks formed in the blends. The proposed anti-aging mechanism is that the PS solubilized in PBD domains can efficiently prevent oxygen molecules from diffusing into PBD domains, therefore, successfully stop the oxidative process of PBD.

"It is Quietly Chaotic. It Confuses Time"*: Final Report of Excavations at the Bordley-Randall Site in Annapolis, Maryland, 1993-1995 (18AP50)

*This extract is from Gay P. Crowther's description of the Randall Court pathway (Cowther 1985).

An introduction to China's rail transport Part 2: Urban rail transit systems, highway transport and the reform of China's railways

In this paper, an introduction is provided to some of the components of China's transport system. The authors include the urban rail transit systems, the highway transport systems and its competition for China's railways and the reform of China's railway industry. This is the second of two papers on the situation of rail transport in China.

Zone based systems design framework for the realisation of efficient block cipher based message authentication code algorithms

A zone based systems design framework is described and utilised in the implementation of a message authentication code (MAC) algorithm based on symmetric key block ciphers. The resulting block cipher based MAC algorithm may be used to provide assurance of the authenticity and, hence, the integrity of binary data. Using software simulation to benchmark against the de facto cipher block chaining MAC (CBC-MAC) variant used in the TinySec security protocol for wireless sensor networks and the NIST cipher block chaining MAC standard, CMAC; we show that our zone based systems design framework can lead to block cipher based MAC constructs that point to improvements in message processing efficiency, processing throughput and processing latency.

The Plasmodium falciparum Malaria M1 Alanyl Aminopeptidase (PfA-M1): Insights of Catalytic Mechanism and Function from MD Simulations

Malaria caused by several species of Plasmodium is major parasitic disease of humans, causing 1-3 million deaths worldwide annually. The widespread resistance of the human parasite to current drug therapies is of major concern making the identification of new drug targets urgent. While the parasite grows and multiplies inside the host erythrocyte it degrades the host cell hemoglobin and utilizes the released amino acids to synthesize its own proteins. The P. falciparum malarial M1 alanyl-aminopeptidase (PfA-M1) is an enzyme involved in the terminal stages of hemoglobin digestion and the generation of an amino acid pool within the parasite. The enzyme has been validated as a potential drug target since inhibitors of the enzyme block parasite growth in vitro and in vivo. In order to gain further understanding of this enzyme, molecular dynamics simulations using data from a recent crystal structure of PfA-M1 were performed. The results elucidate the pentahedral coordination of the catalytic Zn in these metallo-proteases and provide new insights into the roles of this cation and important active site residues in ligand binding and in the hydrolysis of the peptide bond. Based on the data, we propose a two-step catalytic mechanism, in which the conformation of the active site is altered between the Michaelis complex and the transition state. In addition, the simulations identify global changes in the protein in which conformational transitions in the catalytic domain are transmitted at the opening of the N-terminal 8 angstrom-long channel and at the opening of the 30 angstrom-long C-terminal internal chamber that facilitates entry of peptides to the active site and exit of released amino acids. The possible implications of these global changes with regard to enzyme function are discussed.

The Contemporary Urban Condition: Understanding the Globalizing City as Informal, Contested, and Anchored.

In attempting to expand the vocabulary of urban description and understanding, and to offer a new composite conceptual framework for a more integrated urban planning and policy, this essay addresses the informal, contested, and anchored dimensions of the urban in turn; second, it seeks to increasingly link the three within the new global context; and finally, it attempts to draw these strands together in a proposed reconceptualization of the contemporary city within a world where the global is urbanizing and the urban is globalizing.

The social consequences of broken urban structures: a case study of Belfast

This article explores how the design and layout of the urban environment can have significant social impacts on working class communities whose access to employment and other necessary services depends largely on public transport and safe walk-able streets. It does so by considering a case study of Belfast. Although Belfast has a distinctive recent history as the site of political violence and territorial division, it also has a spatial configuration that emerged out of a modernising roads and redevelopment programme in the 1960s and 1970s. However, an understanding of contemporary Belfast, particularly its urban structure and form, requires n analysis of how the social impacts of such ubiquitous regional and urban planning practices were not addressed. The article argues that a culture of ‘politically safe’ bureaucratic inaction developed during the ‘war years’ has been sustained in the ‘new democracy’. In turn, this has had significant consequences for the functioning of the city. Major areas of derelict land around the city core together with the impediments created by regional road infrastructure have combined to create a doughnut city that, on the one hand, facilitates a commuting middle class, while on the other, discriminates against the poorest inner city communities. The article goes on to examine how an activist urban design group, known as the Forum for Alternative Belfast, has responded to these challenges. It focuses particularly on action-research undertaken during its 2010 Summer School which aimed to address issues of disconnection in inner North Belfast that affect some of the most territorialised and deprived communities in the city.

In search of common grounds: Stitching the divided landscape of urban parks in Belfast's interface zones

Political and spatial contestation in divided cities contributes to strategies of self-defense that utilize physical and spatial settings to enable the constitution of social boundaries, borders and territories.
Urban parks that are designed to ease division through an open transitional landscape can instead facilitate further segregation through their spatial order and facility layout. This paper investigates the role of the spatial design and material landscape of integrated parks in Belfast interface areas as instruments of engagement or division. It does so by analyzing the spatial organization of the parks’ facilities and the resultant ‘social voids.’ Space, time and distance were found to be effective tools for the negotiation of privacy, the manifestation of power, and the interplay of dominance and self-confidence. In the context of a divided city, strong community-culture tends to reproduce new boundaries and territories within the shared landscape. Through user interviews and spatial analysis, this paper outlines the design principles that influence spatial behavior in the urban parks of contested urban landscapes. It argues that despite granting equal access to shared public facilities, social voids and physical gaps can instill practices of division that deepen territorial barriers, both psychologically and spatially.

The impact of interventions to promote physical activity in urban green space: A systematic review and recommendations for future research

Evidence is mounting on the association between the built environment and physical activity (PA) with a call for intervention research. A broader approach which recognizes the role of supportive environments that can make healthy choices easier is required. A systematic review was undertaken to assess the effectiveness of interventions to encourage PA in urban green space. Five databases were searched independently by two reviewers using search terms relating to 'physical activity', 'urban green space' and 'intervention' in July 2014. Eligibility criteria included: (i) intervention to encourage PA in urban green space which involved either a physical change to the urban green space or a PA intervention to promote use of urban green space or a combination of both; and (ii) primary outcome of PA. Of the 2405 studies identified, 12 were included. There was some evidence (4/9 studies showed positive effect) to support built environment only interventions for encouraging use and increasing PA in urban green space. There was more promising evidence (3/3 studies showed positive effect) to support PAprograms or PA programs combined with a physical change to the built environment, for increasing urban green space use and PAof users. Recommendations for future research include the need for longer term follow-up post-intervention, adequate control groups, sufficiently powered studies, and consideration of the social environment, which was identified as a significantly under-utilized resource in this area. Interventions that involve the use of PA programs combined with a physical change to the built environment are likely to have a positive effect on PA. Robust evaluations of such interventions are urgently required. The findings provide a platform to inform the design, implementation and evaluation of future urban green space and PAintervention research.

Chase over the Nile: The Social Evolution of Riverine Landscape in Urban Egypt

Throughout its history, Cairo evolved as a regional metropolis that sprawls along the banks of the Nile accumulating narratives of evolving social landscape. Overlooking the Nile reflected a privileged social position and place for the urban elite. In spatial terms, the urban bourgeoisie tend to develop living havens in enclaves that are distant from the populace’s everyday life. Ironically, exclusive settlements only attract urban growth further in their direction. This chapter offers an analytical reading of the socio-spatial structure of Cairo following the emergence and decline of a series bourgeoisie quarters along the shores of the Nile. It reports urban narratives based on archival records, documents and investigation of historical texts and travelers’ accounts. This essay argues that cities are essentially social constructs in which hierarchy and connectivity are fundamental aspects of its economic and spatial logic. Through social ambition and desire for upgrade, middle class infiltrate into bourgeoisie havens and sometimes encircle it, seeking better living condition inscribed by social mobility and connectivity to centres of wealth and power. Being both natural barrier and cohesive spine, the Nile helped Cairo to develop successive nucleuses of highly crafted urban experiences that have left their imprints on the contemporary urban scene.