scholarly journals Selective solvent conditions influence sequence development and supramolecular assembly in step-growth copolymerization

Author(s):  
Ryan Hamblin ◽  
Nhu Nguyen ◽  
Kateri DuBay

Sequence control in synthetic copolymers remains a tantalizing objective in polymer science due to the influence of sequence on material properties and self-organization. A greater understanding of sequence development throughout the polymerization process will aid the design of simple, generalizable methods to control sequence and tune supramolecular assembly. In previous simulations of solution-based step-growth copolymerizations, we have shown that weak, non-bonding attractions between monomers of the same type can produce a microphase separation among the lengthening nascent oligomers and thereby alter sequence. This work explores the phenomenon further, examining how effective attractive interactions, mediated by a solvent selective for one of the reacting species, impact the development of sequence and the supramolecular assembly in a simple A-B copolymerization. We find that as the effective attractions between monomers increase, an emergent self-organization of the reactants causes a shift in reaction kinetics and sequence development. When the solvent-mediated interactions are selective enough, the simple mixture of A and B monomers oligomerize and self-assemble into structures characteristic of amphiphilic copolymers. The composition and morphology of these structures and the sequences of their chains are sensitive to the relative balance of affinities between the comonomer species. Our results demonstrate the impact of differing A-B monomer-solvent affinities on sequence development in solution-based copolymerizations and are of consequence to the informed design of synthetic methods for sequence controlled amphiphilic copolymers and their aggregates.

Soft Matter ◽  
2021 ◽  
Author(s):  
Ryan L Hamblin ◽  
Nhu Q Nguyen ◽  
Kateri H DuBay

Sequence control in synthetic copolymers remains a tantalizing objective in polymer science due to the influence of sequence on material properties and self-organization. A greater understanding of sequence development throughout...


Processes ◽  
2021 ◽  
Vol 9 (2) ◽  
pp. 276
Author(s):  
Hang Jia ◽  
Haoxi Ben ◽  
Fengze Wu

Biochar is generally accepted and increasingly valued in scientific circles as solid products in the thermochemical conversion of biomass, mainly because of its rich carbon content. The purpose of this research is to investigate the impact of biochar from different sources on wheat growth. In particular, this work focused on the effect of different preparation methods and raw material of biochar on the growth of wheat and aim to find a potential soil substitute that can be used for crop cultivation. Two synthetic methods were evaluated: hydrothermal conversion and pyrolysis. The characterization of biochar was determined to explore the impact of its microstructure on wheat growth. The results show that the yield of biochar produced from high-pressure reactor is significantly higher than that obtained by using microwave reactor. For example, the biochar yield obtained through the former is about six times that of the latter when using steamed bread cooked as biomass raw material. In addition, the growth trend of wheat indicates that biochar has different promoting effects on the growth of wheat in its weight and height. The pyrolyzed carbon is more suitable for wheat growth and is even more effective than soil, indicating that pyrolyzed biochar has more potential to be an alternative soil in the future. Moreover, this research tries to explore the reasons that affect crop growth by characterizing biochar (including scanning electron microscopy (SEM), biofilm electrostatic test (BET) and Fourier transform infrared (FT-IR)). The results indicate that the biochar containing more pits and less hydroxyl functional are more suitable for storing moisture, which is one of the significant factors in the growth of crops. This study provides evidence of the effects of biochar on crop growth, both in terms of microstructure and macroscopic growth trends, which provides significant benefits for biochar to grow crops or plants.


2001 ◽  
Vol 38 (2) ◽  
pp. 293-308 ◽  
Author(s):  
Andreas Prokoph ◽  
Anthony D Fowler ◽  
R Timothy Patterson

Wavelet transform and other signal analysis techniques suggest that the planktic foraminiferal (PF) long-term evolutionary record of the last 127 Ma can be attributed to complex periodic and nonlinear patterns. Correlation of the PF extinction pattern with other geological series favors an origin of the ~30 Ma periodicity and self-organization by quasi-periodic mantle-plume cycles that in turn drive episodic volcanism, CO2-degassing, oceanic anoxic conditions, and sea-level fluctuations. Stationary ~30 Ma periodicity and a weak secular trend of ~100 Ma period are evident in the PF record, even without consideration of the mass extinction at the K–T boundary. The 27–32 Ma periodicity in the impact crater record and lows in the global sea-level curve, respectively, are ~6.5 Ma and ~2.3 Ma out of phase with PF-extinction data, although major PF-extinction events correspond to the bolide impacts at the K–T boundary and in late Eocene. Another six extinction events correspond to abrupt global sea-level falls between the late Albian and early Oligocene. Self-organization in the PF record is characterized by increased radiation rates after major extinction events and a steady number of baseline species. Our computer model of long-term PF evolution replicates this SO pattern. The model consists of output from the logistic map, which is forced at 30 Ma and 100 Ma frequencies. The model has significant correlations with the relative PF-extinction data. In particular, it replicates singularities, such as the K–T event, nonstationary 2.5–10 Ma periodicities, and phase shifts in the ~30 Ma periodicity of the PF record.


Soft Matter ◽  
2015 ◽  
Vol 11 (45) ◽  
pp. 8801-8811 ◽  
Author(s):  
Bo Lin ◽  
Lan Liu ◽  
Shijie Zhang ◽  
Junzuo Huang ◽  
Fuan He ◽  
...  

The microphase separation of amphiphilic dendrimer copolymers in a selective solvent with different excluded volume effects (αS) is investigated using three-dimensional real space self-consistent field theory.


Author(s):  
Najib Aragrag ◽  
Dario C. Castiglione

This chapter is intended to provide a general introduction to the laboratory techniques used in polymer synthesis, by focusing on some relatively well-known polymerizations that occur by chain-growth processes. In this way some of the more commonly used procedures in polymer chemistry are described. Due to the nature of the intermediates produced, such as free radicals, carbanions, carbocations, together with a range of organometallic species, the techniques often involve handling compounds in the complete absence of oxygen and moisture. Because of this the best results may require quite sophisticated equipment and glassware; however, it is our intention to show that the general procedures are accessible to any reasonably equipped laboratory, and indeed some of the techniques are suitable for use in an undergraduate teaching laboratory. Chain-growth polymerization involves the sequential step-wise addition of monomer to a growing chain. Usually, the monomer is unsaturated, almost always a derivative of ethene, and most commonly vinylic, that is, a monosubstituted ethane, 1 particularly where the growing chain is a free radical. For such monomers, the polymerization process is classified by the way in which polymerization is initiated and thus the nature of the propagating chain, namely anionic, cationic, or free radical; polymerization by coordination catalyst is generally considered separately as the nature of the growing chain-end may be less clear and coordination may bring about a substantial level of control not possible with other methods. Ring-opening polymerizations exhibit many of the features of chain-growth polymerization, but may also show some of the features expected from stepgrowth polymerizations. However, it is probably fair to say that from a practical point of view the techniques involved are rather similar or the same as those used in chain-growth processes and consequently some examples of ring-opening processes are provided here. It is particularly instructive to consider the requirements of chain-growth compared to step-growth processes in terms of the demands for reagent purity and reaction conditions.


Author(s):  
Ian L. Hosier ◽  
Alun S. Vaughan

Polymer science is, of course, driven by the desire to produce new materials for new applications. The success of materials such as polyethylene, polypropylene, and polystyrene is such that these materials are manufactured on a huge scale and are indeed ubiquitous. There is still a massive drive to understand these materials and improve their properties in order to meet material requirements; however, increasingly polymers are being applied to a wide range of problems, and certainly in terms of developing new materials there is much more emphasis on control. Such control can be control of molecular weight, for example, the production of polymers with a highly narrow molecular weight distribution by anionic polymerization. The control of polymer architecture extends from block copolymers to other novel architectures such as ladder polymers and dendrimers. Cyclic systems can also be prepared, usually these are lower molecular weight systems, although these also might be expected to be the natural consequence of step-growth polymerization at high conversion. Polymers are used in a wide range of applications, as coatings, as adhesives, as engineering and structural materials, for packaging, and for clothing to name a few. A key feature of the success and versatility of these materials is that it is possible to build in properties by careful design of the (largely) organic molecules from which the chains are built up. For example, rigid aromatic molecules can be used to make high-strength fibres, the most highprofile example of this being Kevlar®; rigid molecules of this type are often made by simple step-growth polymerization and offer particular synthetic challenges as outlined in Chapter 4. There is now an increasing demand for highly specialized materials for use in for example optical and electronic applications and polymers have been singled out as having particular potential in this regard. For example, there is considerable interest in the development of polymers with targeted optical properties such as second-order optical nonlinearity, and in conducting polymers as electrode materials, as a route towards supercapacitors and as electroluminescent materials. Polymeric materials can also be used as an electrolyte in the design of compact batteries.


Polymers ◽  
2019 ◽  
Vol 11 (9) ◽  
pp. 1522
Author(s):  
Ming Zhang ◽  
Mingqing Chen ◽  
Zhongbin Ni

We synthesized PPG-terminated tetra-carbamates as a new toughening additive for epoxy thermosets through facile addition reaction of hexamethylene diisocyanate (HDI) with poly(tetra-methylene glycols) (PTMG) and poly(propylene glycols) (PPG). The effects of prepared tetra-carbamates on the rheological behavior of neat epoxy resin were studied along with the various cured properties of their modified epoxy systems. Four carbamate groups (–NHCOO–) endow the prepared additives not only with good intramolecular interactions, but also with optimal intermolecular interactions with epoxy polymers. This results in the suitable miscibility of the additives with the epoxy matrix for the formation of the typical biphasic structure of microparticles dispersed in the epoxy matrix via polymerization-induced microphase separation. The impact strength and critical stress concentration factor (KIC) of cured modified epoxy systems with the additives are significantly higher than those of unmodified epoxy systems, without sacrificing the processability (Tg) and flexural strength. The toughening mechanism is understood as a synergism combination among the phase separation mechanism, the in situ homogeneous toughening mechanism, and the particle cavitation mechanism.


2020 ◽  
Vol 117 (24) ◽  
pp. 13227-13237 ◽  
Author(s):  
Rabiya Noori ◽  
Daniel Park ◽  
John D. Griffiths ◽  
Sonya Bells ◽  
Paul W. Frankland ◽  
...  

Communication and oscillatory synchrony between distributed neural populations are believed to play a key role in multiple cognitive and neural functions. These interactions are mediated by long-range myelinated axonal fiber bundles, collectively termed as white matter. While traditionally considered to be static after development, white matter properties have been shown to change in an activity-dependent way through learning and behavior—a phenomenon known as white matter plasticity. In the central nervous system, this plasticity stems from oligodendroglia, which form myelin sheaths to regulate the conduction of nerve impulses across the brain, hence critically impacting neural communication. We here shift the focus from neural to glial contribution to brain synchronization and examine the impact of adaptive, activity-dependent changes in conduction velocity on the large-scale phase synchronization of neural oscillators. Using a network model based on primate large-scale white matter neuroanatomy, our computational and mathematical results show that such plasticity endows white matter with self-organizing properties, where conduction delay statistics are autonomously adjusted to ensure efficient neural communication. Our analysis shows that this mechanism stabilizes oscillatory neural activity across a wide range of connectivity gain and frequency bands, making phase-locked states more resilient to damage as reflected by diffuse decreases in connectivity. Critically, our work suggests that adaptive myelination may be a mechanism that enables brain networks with a means of temporal self-organization, resilience, and homeostasis.


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