100th Anniversary of Macromolecular Science Viewpoint: Opportunities in the Physics of Sequence-Defined Polymers

Polymer science has been driven by ever-increasing molecular complexity, as polymer synthesis expands an already-vast palette of chemical and architectural parameter space. Copolymers represent a key example, where simple homopolymers have given rise to random, alternating, gradient, and block copolymers. Polymer physics has provided the insight needed to explore this monomer sequence parameter space. The future of polymer science, however, must contend with further increases in monomer precision, as this class of macromolecules moves ever closer to the sequence-monodisperse polymers that are the workhorses of biology. The advent of sequence-defined polymers gives rise to opportunities for material design, with increasing levels of chemical information being incorporated into long-chain molecules; however, this also raises questions that polymer physics must address. What properties uniquely emerge from sequence-definition? Is this circumstance-dependent? How do we define and think about sequence dispersity? How do we think about a hierarchy of sequence effects? Are more sophisticated characterization methods, as well as theoretical and computational tools, needed to understand this class of macromolecules? The answers to these questions touch on many difficult scientific challenges, setting the stage for a rich future for sequence-defined polymers in polymer physics

Recent progress in the science of complex coacervation

Complex coacervation is an associative, liquid–liquid phase separation that can occur in solutions of oppositely-charged macromolecular species, such as proteins, polymers, and colloids. This process results in a coacervate phase, which is a dense mix of the oppositely-charged components, and a supernatant phase, which is primarily devoid of these same species. First observed almost a century ago, coacervates have since found relevance in a wide range of applications; they are used in personal care and food products, cutting edge biotechnology, and as a motif for materials design and self-assembly. There has recently been a renaissance in our understanding of this important class of material phenomena, bringing the science of coacervation to the forefront of polymer and colloid science, biophysics, and industrial materials design. In this review, we describe the emergence of a number of these new research directions, specifically in the context of polymer–polymer complex coacervates, which are inspired by a number of key physical and chemical insights and driven by a diverse range of experimental, theoretical, and computational approaches

Experimental studies on treated sub-base soil with fly ash and cement for sustainable design recommendations

The pavement constructions on soft and expansive soils are not durable and unable to sustain heavy traffic loading. As a result, pavement failures and settlement problems will occur very often even under light traffic loading due to cyclic and rolling effects. Geotechnical engineers have dwelled deeply into this matter, and adopt various methods to improve the engineering characteristics of soft fine-grained soils and expansive soils. The problematic soils are either replaced by good and better quality material or treated by using chemical stabilization with various binding materials. Increased the strength and durability are also the part of the sustainability drive to reduce the environment footprint of the built environment by the efficient use of resources and waste recycle materials. This paper presents a series of laboratory tests and evaluates the effect of cement and fly ash on the strength and drainage characteristics of soil in Miri. The tests were performed at different percentages of cement and fly ash by dry weight of soil. Additional tests were also performed on soils treated with the combinations of fly ash with cement and lime. The results of this study indicate an increase in unconfined compression strength and a decrease in hydraulic conductivity of the treated soil

Left main bronchus compression due to main pulmonary artery dilatation in pulmonary hypertension: two case reports

Abstract. Pulmonary arterial dilatation associated with pulmonary hypertension may result in significant compression of local structures. Left main coronary artery and left recurrent laryngeal nerve compression have been described. Tracheobronchial compression from pulmonary arterial dilatation is rare in adults, and there are no reports in the literature of its occurrence in idiopathic pulmonary arterial hypertension. Compression in infants with congenital heart disease has been well described. We report 2 cases of tracheobronchial compression: first, an adult patient with idiopathic pulmonary arterial hypertension who presents with symptomatic left main bronchus compression, and second, an adult patient with Eisenmenger ventricular septal defect and right-sided aortic arch, with progressive intermedius and right middle lobe bronchi compression in association with enlarged pulmonary arteries

The automorphism group of separable states in quantum information theory

We show that the linear group of automorphism of Hermitian matrices which preserves the set of separable states is generated by \emph{natural} automorphisms: change of an orthonormal basis in each tensor factor, partial transpose in each tensor factor, and interchanging two tensor factors of the same dimension. We apply our results to preservers of the product numerical range.Comment: 15 page

Pressure dependence of the Verwey transition in magnetite: an infrared spectroscopic point of view

We investigated the electronic and vibrational properties of magnetite at temperatures from 300 K down to 10 K and for pressures up to 10 GPa by far-infrared reflectivity measurements. The Verwey transition is manifested by a drastic decrease of the overall reflectance and the splitting of the phonon modes as well as the activation of additional phonon modes. In the whole studied pressure range the down-shift of the overall reflectance spectrum saturates and the maximum number of phonon modes is reached at a critical temperature, which sets a lower bound for the Verwey transition temperature T$_{\mathrm{v}}$. Based on these optical results a pressure-temperature phase diagram for magnetite is proposed.Comment: 5 pages, 4 figures; accepted for publication in J. Appl. Phy

PRISM-Based Theory of Complex Coacervation: Excluded Volume versus Chain Correlation

Aqueous solutions of oppositely charged polyelectrolytes can undergo liquid–liquid phase separation into materials known as complex coacervates. These coacervates have been a subject of intense experimental and theoretical interest. Efforts to provide a physical description of complex coacervates have led to a number of theories that qualitatively (and sometimes quantitatively) agree with experimental data. However, this agreement often occurs in a degeneracy of models with profoundly different starting assumptions and different levels of sophistication. Theoretical difficulties in these systems are similar to those in most polyelectrolyte systems where charged species are highly correlated. These highly correlated systems can be described using liquid state (LS) integral equation theories, which surpass mean-field theories by providing information on local charge ordering. We extend these ideas to complex coacervate systems using PRISM-type theories and are able to capture effects not observable in traditional coacervate models, particularly connectivity and excluded volume effects. We can thus bridge two traditional but incommensurate theories meant to describe complex coacervates: the Voorn–Overbeek theory and counterion release. Importantly, we hypothesize that a cancellation of connectivity and excluded volume effects provides an explanation for the ability of Voorn–Overbeek theory to fit experimental data despite its well-known approximations

Higher rank numerical ranges of normal matrices

The higher rank numerical range is closely connected to the construction of quantum error correction code for a noisy quantum channel. It is known that if a normal matrix $A \in M_n$ has eigenvalues $a_1, \..., a_n$, then its higher rank numerical range $\Lambda_k(A)$ is the intersection of convex polygons with vertices $a_{j_1}, \..., a_{j_{n-k+1}}$, where $1 \le j_1 < \... < j_{n-k+1} \le n$. In this paper, it is shown that the higher rank numerical range of a normal matrix with $m$ distinct eigenvalues can be written as the intersection of no more than $\max\{m,4\}$ closed half planes. In addition, given a convex polygon ${\mathcal P}$ a construction is given for a normal matrix $A \in M_n$ with minimum $n$ such that $\Lambda_k(A) = {\mathcal P}$. In particular, if ${\mathcal P}$ has $p$ vertices, with $p \ge 3$, there is a normal matrix $A \in M_n$ with $n \le \max\left\{p+k-1, 2k+2 \right\}$ such that $\Lambda_k(A) = {\mathcal P}$.Comment: 12 pages, 9 figures, to appear in SIAM Journal on Matrix Analysis and Application

Numerical simulation of a supercritical inlet flow

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/76033/1/AIAA-1985-1214-300.pd