Polymer 4D printing: Advanced shape-change and beyond

4D printing is an exciting branch of additive manufacturing. It relies on established 3D printing techniques to fabricate objects in much the same way. However, structures which fall into the 4D printed category have the ability to change with time, hence the “extra dimension.” The common perception of 4D printed objects is that of macroscopic single-material structures limited to point-to-point shape change only, in response to either heat or water. However, in the area of polymer 4D printing, recent advancements challenge this understanding. A host of new polymeric materials have been designed which display a variety of wonderful effects brought about by unconventional stimuli, and advanced additive manufacturing techniques have been developed to accommodate them. As a result, the horizons of polymer 4D printing have been broadened beyond what was initially thought possible. In this review, we showcase the many studies which evolve the very definition of polymer 4D printing, and reveal emerging areas of research integral to its advancement.     

Chiral phase transition and equation of state in chiral imbalance

The chiral phase transition and equation of state are studied within a novel self-consistent mean-field approximation of the two-flavor Nambu-Jona-Lasinio model. In this newly developed model, modifications to the chemical μ and chiral chemical \begin{document}$\mu_5$\end{document} potentials are naturally included by introducing vector and axial-vector channels from Fierz-transformed Lagrangian to the standard Lagrangian. In the proper-time scheme, the chiral phase transition is a crossover in the \begin{document}$T-\mu$\end{document} plane. However, when \begin{document}$\mu_5$\end{document} is incorporated, our study demonstrates that a first order phase transition may emerge. Furthermore, the chiral imbalance will soften the equation of state of quark matter. The mass-radius relationship and tidal deformability of quark stars are calculated. The maximum mass and radius decrease as \begin{document}$\mu_5$\end{document} increases. Our study also indicates that the vector and axial-vector channels exhibit an opposite influence on the equation of state.     

Synthesis of diisocyanides with phenolic groups and their polymerization to helically chiral poly(quinoxaline‐2,3‐diyl)s

The development of synthetic routes which lead to five new diisocyanide monomers with one or two phenolic groups is described. Their polymerization behavior is studied with Pd‐ and Ni‐based initiators, as well as under microwave irradiation. The polymerizability is mainly dominated by steric effects as is concluded from experiments using different protecting groups. Chiroptical properties of these new polymers are studied by CD‐spectroscopy. After deprotection, helically chiral poly(quinoxalin‐2,3‐diyl)s are obtained which display a Brønsted function attached to a stereolabile biaryl axis whose configuration should be influenced by the chiral polymer backbone. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1320–1329     

Effect of additive length and chemistry on the morphology of blends of conjugated thiophenes and fullerene derivative acceptor molecules

Small molecule additives have been shown to increase the device efficiency of conjugated polymer (donor) and fullerene derivative (acceptor) based organic solar cells by modifying the morphology of the device active layer. In this paper we conduct a systematic study of how additives affect the donor‐acceptor morphology using molecular dynamics simulations of blends of thiophene‐based oligomers, mimicking poly(3‐dodecylthiophene) (P3DDT) or poly(2,2′:5′,2”‐3,3”‐didocyl‐terthiophene) (PTTT), and fullerene derivatives with additives of varying length and chemical functionalization, mimicking experimentally used additives like methyl ester additives, diiodooctane, and alkanedithiols. We find that functionalization of additives with end groups that are attracted to acceptor molecules are necessary to induce increased donor‐acceptor macrophase separation. In blends where acceptors intercalate between oligomer alkyl side chains, functionalized additives decrease acceptor intercalation. Functionalized additives with shorter alkyl segments increase acceptor macrophase separation more than additives with same chemical functionalization but longer alkyl segments. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1046–1057     

Van't Hoff analysis in chiral chromatography

The present review discusses the theory and application of van't Hoff analysis in chiral chromatography, with main focus on liquid chromatography. The topics considered include the physical meaning of van't Hoff equation's parameters, interpretation of thermodynamic data in terms of retention and enantioseparation mechanisms, abnormal behavior of van't Hoff plots, and best practices to avoid biased results.     

天文斑点成像技术中的噪声影响分析

为进一步说明天文像复原新方法-迭代位移叠加法的性质，对探测器的附加噪声在斑点干涉术、斑点掩模法和迭代位移叠加法中的影响分别进行了分析。结果表明：在斑点掩模法中，复杂的噪声高阶矩统计被引入了重谱的噪声偏差，因此对噪声极为敏感，使数据处理更加复杂化；与斑点掩模法相比，迭代位移叠加法仅涉及对噪声的一阶矩统计平均，所以此新方法的特点是对噪声不敏感，具有图像复原处理过程简单快捷的优越性。     

Conformational analysis of dipeptide‐derived polyisocyanides

The conformational properties of polymers derived from isocyanodipeptides have been investigated with a combination of model calculations, X‐ray diffraction, and circular dichroism spectroscopy. Depending on the configuration of the side chains, defined arrays of hydrogen bonds along the polymeric backbone are formed. This leads to a well‐defined conformation as, for example, expressed in the formation of lyotropic liquid‐crystalline phases and increased helical stability. Upon the disruption of the hydrogen bonds by a strong acid, a less well‐defined macromolecular conformation is observed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1725–1736, 2003     

Ergodic properties and thermodynamic behavior of elementary reversible cellular automata. I. Basic properties

This is the first part of a series devoted to the study of thermodynamic behavior of large dynamical systems with the use of a family of fully-discrete and conservative models named elementary reversible cellular automata (ERCAs). In this paper, basic properties such as conservation laws and phase space structure are investigated in preparation for the later studies. ERCAs are a family of one-dimensional reversible cellular automata having two Boolean variables on each site. Reflection and Boolean conjugation symmetries divide them into 88 equivalence classes. For each rule, additive conserved quantities written in a certain form are regarded as a kind of energy, if they exist. By the aid of the discreteness of the variables, every ERCA satisfies the Liouville theorem or the preservation of phase space volume. Thus, if an energy exists in the above sense, statistical mechanics of the model can formally be constructed. If a locally defined quantity is conserved, however, it prevents the realization of statistical mechanics. The existence of such a quantity is examined for each class and a number of rules which have at least one energy but no local conservation laws are selected as hopeful candidates for the realization of thermodynamic behavior. In addition, the phase space structure of ERCAs is analyzed by enumerating cycles exactly in the phase space for systems of comparatively small sizes. As a result, it is revealed that a finite ERCA is not ergodic, that is, a large number of orbits coexist on an energy surface. It is argued that this fact does not necessarily mean the failure of thermodynamic behavior on the basis of an analogy with the ergodic nature of infinite systems.     

Tribute to Endre Csáki and Pál Révész

Summary This article provides a glimpse of some of the highlights of the joint work of Endre Csáki and Pál Révész since 1979. The topics of this short exploration of the rich stochastic milieu of this inspiring collaboration revolve around Brownian motion, random walks and their long excursions, local times and additive functionals, iterated processes, almost sure local and global central limit theorems, integral functionals of geometric stochastic processes, favourite sites--favourite values and jump sizes for random walk and Brownian motion, random walking in a random scenery, and large void zones and occupation times for coalescing random walks.     

Polymerization behaviors of racemic and chiral amphiphilic monomers in organized bilayer membranes of lamellar liquid crystalline phase

A racemic amphiphilic monomer, n‐dodecyl glyceryl itaconate (DGI), forms bilayer membranes in water in the presence of small amount of ionic cosurfactant and shows iridescent color. A chiral DGI, S‐DGI, also shows an iridescent property, but with a rather red shift in the color, which can be ascribed to the increased packing density of the monomer in the bilayer membranes. Chrial DGI has a more compact packing density than racemic one owing to closer distance between the monomer molecules; the conversion rate, however, is slower than that of racemic one when H₂O₂ is used as an initiator. When the initiator is changed to an amphiphilic one, 4‐(2‐hydroxyethoxy) phenyl‐(2‐hydroxy‐2‐propyl) ketone (Irgacure 2959), the chiral DGI shows even a little faster conversion rate than that of racemic one. The NMR chemical shift results of protons in benzene ring show that the molecules of Irgacure 2959 insert into the bilayer membranes. The molecular weights of the corresponding polymers prove that the initiation by H₂O₂ is restricted compared to that by Irgacure 2959. It is concluded that the decelerated polymerization behavior of chiral DGI initiated by H₂O₂ is a result of limited diffusion of the initiator into the lamellar bilayer structures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4891–4900, 2007