Properties and applications of precision oligomer materials; where organic and polymer chemistry join forces

Precise oligomeric materials constitute a growing area of research with implications for various applications as well as fundamental studies. Notably, this field of science which can be termed macro-organic chemistry, draws inspiration from both traditional polymer chemistry and organic synthesis, combining the molecular precision of organic chemistry with the materials properties of macromolecules. Discrete oligomers enable access to unprecedented materials properties, for example, in self-assembled structures, crystallization, or optical properties. The degree of control over oligomer structures resembles many biological systems and enables the design of materials with tailored properties and the development of fundamental structure–property relationships. This Review highlights recent developments in macro-organic chemistry from synthetic concepts to materials properties, with a focus on self-assembly and molecular recognition. Finally, an outlook for future research directions is provided.     

Influence of Amide Connectivity on the Hydrogen-Bond-Directed Self-Assembly of [n.n]Paracyclophanes

Reported here is the synthesis and self-assembly characterization of [n.n]paracyclophanes ( [n.n]pCps , n=2, 3) equipped with anilide hydrogen bonding units. These molecules differ from previous self-assembling [n.n]paracyclophanes ( [n.n]pCps ) in the connectivity of their amide hydrogen bonding units (C-centered/carboxamide vs. N-centered/anilide). This subtle change results in a ≈30-fold increase in the elongation constant for the [2.2]pCp -4,7,12,15-tetraanilide ( [2.2]pCpNTA ) compared to previously reported [2.2]pCp -4,7,12,15-tetracarboxamide ( [2.2]pCpTA ), and a ≈300-fold increase in the elongation constant for the [3.3]pCp -5,8,14,17-tetraanilide ( [3.3]pCpNTA ) compared to previously reported [3.3]pCp -5,8,14,17-tetracarboxamide ( [3.3]pCpTA ). The [n.n]pCpNTA monomers also represent the reversal of a previously reported trend in solution-phase assembly strength when comparing [2.2]pCpTA and [3.3]pCpTA monomers. The origins of the assembly differences are geometric changes in the association between [n.n]pCpNTA monomers—revealed by computations and X-ray crystallography—resulting in a more favorable slipped stacking of the intermolecular π-surfaces ( [n.n]pCpNTA vs. [n.n]pCpTA ), and a more complementary H-bonding geometry ( [3.3]pCpNTA vs. [2.2]pCpNTA ).     

A Districtwide Study of Automaticity When Included in Concept‐Based Elementary School Mathematics Instruction

While conceptual understanding of properties, operations, and the base‐ten number system is certainly associated with the ability to access math facts fluently, the role of math fact memorization to promote conceptual understanding remains contested. In order to gain insight into this question, this study looks at the results when one of three elementary schools in a school district implements mandatory automaticity drills for 10 minutes each day while the remaining two elementary schools, with the same curriculum and very similar demographics, do not. This study looks at (a) the impact that schoolwide implementation of automaticity drills has on schoolwide computational math skills as measured by the ITBS and (b) the relationship between automaticity and conceptual understanding as measured by statewide standardized testing. The results suggest that while there may be an association between automaticity and higher performance on standardized tests, caution should be taken before assuming there are benefits to promoting automaticity drills. These results are consistent with those that support a process‐driven approach to automaticity based on familiarity with properties and strategies associated with the base‐ten number system; they are not consistent with those that support an answer‐driven approach to automaticity based on memorization of answers.     

Random k‐SAT and the power of two choices

We study an Achlioptas‐process version of the random k‐SAT process: a bounded number of k‐clauses are drawn uniformly at random at each step, and exactly one added to the growing formula according to a particular rule. We prove the existence of a rule that shifts the satisfiability threshold. This extends a well‐studied area of probabilistic combinatorics (Achlioptas processes) to random CSP's. In particular, while a rule to delay the 2‐SAT threshold was known previously, this is the first proof of a rule to shift the threshold of k‐SAT for . We then propose a gap decision problem based upon this semi‐random model. The aim of the problem is to investigate the hardness of the random k‐SAT decision problem, as opposed to the problem of finding an assignment or certificate of unsatisfiability. Finally, we discuss connections to the study of Achlioptas random graph processes. © 2014 Wiley Periodicals, Inc. Random Struct. Alg., 47, 163–173, 2015     

Fluorogel Elastomers with Tunable Transparency,Elasticity, Shape‐Memory,and Antifouling Properties

Omniphobic fluorogel elastomers were prepared by photocuring perfluorinated acrylates and a perfluoropolyether crosslinker. By tuning either the chemical composition or the temperature that control the crystallinity of the resulting polymer chains, a broad range of optical and mechanical properties of the fluorogel can be achieved. After infusing with fluorinated lubricants, the fluorogels showed excellent resistance to wetting by various liquids and anti‐biofouling behavior, while maintaining cytocompatiblity.     

Electroactive Polymers: Developments of and Perspectives for Dielectric Elastomers

We present the development and applications of dielectric elastomers. For the last 10 years the significance of this class of polymers has risen as more applications seem possible and first products have been commercialized.     

Intrinsic chirality of multipartite graphs

We classify which complete multipartite graphs are intrinsically chiral.     

Established and emerging strategies for polymer chain-end modification

The development of “controlled” and “living” polymerization processes with high end-group fidelity has enabled an unprecedented range of polymeric materials with specific chain-end functionality to be prepared. This highlight provides an overview of available strategies and evaluation of recent approaches for the chain-end functionalization of polymers prepared through controlled chain-growth polymerizations. As a tribute to Professor Robert B. Grubbs on the occasion of his 75th birthday, we also take this opportunity to highlight methods for the chain-end modification of polymers prepared by ring-opening metathesis polymerization within the broader context of functional group tolerant, living polymerizations. Finally, we focus attention toward new directions in polymer chain-end modifications, describing existing gaps in current strategies, and detailing recently reported protocols that show significant improvements over traditional methods. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2903–2914     

Three-dimensional manganese dioxide-functionalized carbon nanotube electrodes for electrochemical supercapacitors

Three-dimensional manganese dioxide (MnO₂)-functionalized multiwalled carbon nanotube (MWCNT) electrodes have been produced by a simple and scalable thermal decomposition process. The electrodes are prepared by treating planar MWCNT sheets with manganese(II) nitrate (Mn(NO₃)₂) solution and annealing at low temperature (200–300 °C) and ambient pressure. The morphology, chemical composition, and structure of the resulting matrices have been investigated with scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and X-ray diffraction. Supercapacitors assembled with three-dimensional electrodes exhibit a 14-fold increase in specific capacitance (C _sp) in comparison to those containing pristine, two-dimensional MWCNT electrodes. C _sp varies linearly with Mn(NO₃)₂ thermal decomposition temperature (from 100 to 61 F/g at 0.2 A/g), a trend that is discussed in the context of nitrate reaction chemistry and MWCNT structure. This efficient and promising approach allows for simultaneous enhancement of electrode–electrolyte contact area and incorporation of redox-based charge storage within electrochemical capacitors.