Dynamic covalent chemistry in polymer networks : a mechanistic perspective

The incorporation of dynamic covalent linkages within and between polymer chains brings new properties to classical thermosetting polymer formulations, in particular in terms of thermal responses, processing options and intrinsic recycling abilities. Thus, in recent years, there has been a rapidly growing interest in the design and synthesis of monomers and cross-linkers that can be used as robust but at the same time reactive organic building blocks for dynamic polymer networks. In this perspective, a selection of such chemistries is highlighted, with a particular focus on the reaction mechanisms of molecular network rearrangements, and on how various mechanistic profiles can be related to the mechanical and physicochemical properties of polymer materials, in particular in relation with vitrimers, the recently defined third category of polymer materials. The recent advances in this area are not only expected to help direct promising emerging polymer applications, but also point towards the need for a better fundamental understanding of chemical reactivity within a macromolecular context

Injectable polypeptide hydrogels via methionine modification for neural stem cell delivery.

Injectable hydrogels with tunable physiochemical and biological properties are potential tools for improving neural stem/progenitor cell (NSPC) transplantation to treat central nervous system (CNS) injury and disease. Here, we developed injectable diblock copolypeptide hydrogels (DCH) for NSPC transplantation that contain hydrophilic segments of modified l-methionine (Met). Multiple Met-based DCH were fabricated by post-polymerization modification of Met to various functional derivatives, and incorporation of different amino acid comonomers into hydrophilic segments. Met-based DCH assembled into self-healing hydrogels with concentration and composition dependent mechanical properties. Mechanical properties of non-ionic Met-sulfoxide formulations (DCHMO) were stable across diverse aqueous media while cationic formulations showed salt ion dependent stiffness reduction. Murine NSPC survival in DCHMO was equivalent to that of standard culture conditions, and sulfoxide functionality imparted cell non-fouling character. Within serum rich environments in vitro, DCHMO was superior at preserving NSPC stemness and multipotency compared to cell adhesive materials. NSPC in DCHMO injected into uninjured forebrain remained local and, after 4 weeks, exhibited an immature astroglial phenotype that integrated with host neural tissue and acted as cellular substrates that supported growth of host-derived axons. These findings demonstrate that Met-based DCH are suitable vehicles for further study of NSPC transplantation in CNS injury and disease models

Synthesizing a Lego Forklift Controller in GR(1): A Case Study

Reactive synthesis is an automated procedure to obtain a correct-by-construction reactive system from a given specification. GR(1) is a well-known fragment of linear temporal logic (LTL) where synthesis is possible using a polynomial symbolic algorithm. We conducted a case study to learn about the challenges that software engineers may face when using GR(1) synthesis for the development of a reactive robotic system. In the case study we developed two variants of a forklift controller, deployed on a Lego robot. The case study employs LTL specification patterns as an extension of the GR(1) specification language, an examination of two specification variants for execution scheduling, traceability from the synthesized controller to constraints in the specification, and generated counter strategies to support understanding reasons for unrealizability. We present the specifications we developed, our observations, and challenges faced during the case study.Comment: In Proceedings SYNT 2015, arXiv:1602.0078

Learning Task Specifications from Demonstrations

Real world applications often naturally decompose into several sub-tasks. In many settings (e.g., robotics) demonstrations provide a natural way to specify the sub-tasks. However, most methods for learning from demonstrations either do not provide guarantees that the artifacts learned for the sub-tasks can be safely recombined or limit the types of composition available. Motivated by this deficit, we consider the problem of inferring Boolean non-Markovian rewards (also known as logical trace properties or specifications) from demonstrations provided by an agent operating in an uncertain, stochastic environment. Crucially, specifications admit well-defined composition rules that are typically easy to interpret. In this paper, we formulate the specification inference task as a maximum a posteriori (MAP) probability inference problem, apply the principle of maximum entropy to derive an analytic demonstration likelihood model and give an efficient approach to search for the most likely specification in a large candidate pool of specifications. In our experiments, we demonstrate how learning specifications can help avoid common problems that often arise due to ad-hoc reward composition.Comment: NIPS 201

Hierarchical Self-Assembly of Halogen-Bonded Block Copolymer Complexes into Upright Cylindrical Domains

Self-assembly of block copolymers into well-defined, ordered arrangements of chemically distinct domains is a reliable strategy for preparing tailored nanostructures. Microphase separation results from the system, minimizing repulsive interactions between dissimilar blocks and maximizing attractive interactions between similar blocks. Supramolecular methods have also achieved this separation by introducing small-molecule additives binding specifically to one block by noncovalent interactions. Here, we use halogen bonding as a supramolecular tool that directs the hierarchical self-assembly of low-molecular-weight perfluorinated molecules and diblock copolymers. Microphase separation results in a lamellar-within-cylindrical arrangement and promotes upright cylindrical alignment in films upon rapid casting and without further annealing. Such cylindrical domains with internal lamellar self-assemblies can be cleaved by solvent treatment of bulk films, resulting in separated and segmented cylindrical micelles stabilized by halogen-bond-based supramolecular crosslinks. These features, alongside the reversible nature of halogen bonding, provide a robust modular approach for nanofabricatio

Charge transport in nanoscale vertical organic semiconductor pillar devices

We report charge transport measurements in nanoscale vertical pillar structures incorporating ultrathin layers of the organic semiconductor poly(3-hexylthiophene)(P3HT). P3HT layers with thickness down to 5 nm are gently top-contacted using wedging transfer, yielding highly reproducible, robust nanoscale junctions carrying high current densities (up to $10^6$ A/m$^2$). Current-voltage data modeling demonstrates excellent hole injection. This work opens up the pathway towards nanoscale, ultrashort-channel organic transistors for high-frequency and high-current-density operation.Comment: 30 pages, 8 figures, 1 tabl

Quantitative reactive modeling and verification

Formal verification aims to improve the quality of software by detecting errors before they do harm. At the basis of formal verification is the logical notion of correctness, which purports to capture whether or not a program behaves as desired. We suggest that the boolean partition of software into correct and incorrect programs falls short of the practical need to assess the behavior of software in a more nuanced fashion against multiple criteria. We therefore propose to introduce quantitative fitness measures for programs, specifically for measuring the function, performance, and robustness of reactive programs such as concurrent processes. This article describes the goals of the ERC Advanced Investigator Project QUAREM. The project aims to build and evaluate a theory of quantitative fitness measures for reactive models. Such a theory must strive to obtain quantitative generalizations of the paradigms that have been success stories in qualitative reactive modeling, such as compositionality, property-preserving abstraction and abstraction refinement, model checking, and synthesis. The theory will be evaluated not only in the context of software and hardware engineering, but also in the context of systems biology. In particular, we will use the quantitative reactive models and fitness measures developed in this project for testing hypotheses about the mechanisms behind data from biological experiments

High compression strength single network hydrogels with pillar[5]arene junction points

The present study highlights a straightforward and versatile strategy for the synthesis of strong poly(2-isopropenyl-2-oxazoline) hydrogels with tunable properties by using a bifunctional macrocyclic pillar[5]arene host having two carboxylic acid groups as cross-linker. This new strategy provides access to materials with tailored properties from soft and flexible to rigid and strong. The mechanical properties and water uptake of the hydrogels could be effortlessly controlled during the synthesis step through variation of the cross-linker content and after cross-linking by guest-host interactions. The hydrogels displayed strongly enhanced mechanical properties (i.e., compression and tensile modulus, energy dissipation, stress at break and storage modulus) compared to their counterparts cross-linked with linear dicarboxylic acids. The remarkable properties of the pillar[5]arene cross-linked hydrogels were assigned to the transfer of the external stress to the rigid and bulky pillar[5]arene residues that contribute to the overall dimensional stability of the hydrogels and allow energy dissipation. Moreover, we demonstrate the applicability of these materials for water purification. The hydrogels showed high adsorption performance for phenols and dyes such as methylene blue and methyl red and they could be easily regenerated, by washing with an organic solvent for reuse

Functional poly(2-oxazoline)s by direct amidation of methyl ester side chains

Poly(2-alkyl/aryl-2-oxazoline)s (PAOx) are biocompatible pseudopolypeptides that have received significant interest for biomedical applications in recent years. The growing popularity of PAOx in recent years is driven by its much higher chemical versatility compared with the gold standard in this field, poly(ethylene glycol) (PEG), while having similar beneficial properties, such as stealth behavior and biocompatibility. We further expand the PAOx chemical toolbox by demonstrating a novel straightforward and highly versatile postpolymerization modification platform for the introduction of side-chain functionalities. PAOx having side chain methyl ester functionalities is demonstrated to undergo facile uncatalyzed amidation reactions with a wide range of amines, yielding the corresponding PAOx with side-chain secondary amide groups containing short aliphatic linkers as well as a range of side-chain functionalities including acid, amine, alcohol, hydrazide, and propargyl groups. The PAOx with side-chain methyl ester groups can be prepared by either partial hydrolysis of a PAOx followed by the introduction of the methyl ester via modification of the secondary amine groups with methyl succinyl chloride or by the direct copolymerization of a nonfunctional 2-oxazoline monomer with a 2-methoxycarbonylethyl-2-oxazoline. Thus, this novel synthetic platform enables direct access to a wide range of side-chain functionalities from the same methyl-ester-functionalized poly(2-oxazoline) scaffold