Contemporary Photoligation Chemistry: The Visible Light Challenge.

Catalyst-free and bond-forming light-induced reactions have seen an unprecedented renaissance in the realm of soft matter materials science due to their efficiency, spatio-temporal controllability and, sometimes, photoreversible nature. However, many of these reactions rely on the application of high energy UV light that can cause photo-degradation and is inapplicable in biological environments. If up-conversion systems or two-photon processes are to be avoided, strategies for red-shifting catalyst-free ligation technology are critically required. This Concept article introduces the reader to recent methods that lead to efficient, catalyst-free visible-light-induced ligation chemistry based on polyaromatic substituted photoreactive compounds-pyrene and anthracene-and, furthermore, emphasizes the broad and facile applicability of these molecules in polymeric material design. Concomitantly, we highlight that a careful action plot analysis of photochemical reactivity can provide deep insights into reactivity patterns, far beyond those suggested by the absorption spectrum. Indeed, we suggest that an action plot analysis is necessary for the evaluation of any photochemical system and its response to structural chemical changes.

Photochemically Induced Folding of Single Chain Polymer Nanoparticles in Water.

We pioneer the synthesis of fluorescent single chain nanoparticles (SCNPs) via UV-light induced folding based on tetrazole chemistry directly in pure water. Water-soluble photoreactive precursor polymers based on poly(acrylic acid) (PAA) bearing tetrazole, alkene and tetraethylene glycol monomethyl ether moieties, (PAAn(Tet/p-Mal/TEG)), or simply tetrazoles moieties, PAAn(Tet), were generated via RAFT polymerization. While tetrazole, ene, and acrylic acid containing polymers fold via dual nitrile imine-mediated tetrazole-ene cycloaddition (NITEC) as well as nitrile imine-carboxylic acid ligation (NICAL), tetrazole and acrylic acid only functional prepolymers fold exclusively via NICAL. A detailed study of the underpinning photochemistry of NITEC and NICAL is also included. The resulting water-soluble SCNPs were carefully characterized via analytical techniques such as NMR, UV-vis, and fluorescence spectroscopy, as well as SEC and DLS.

Degradable fluorescent single-chain nanoparticles based on metathesis polymers.

We introduce the facile synthesis of fluorescent single-chain nanoparticles (SCNPs) based on chain-shattering acyclic diene metathesis (ADMET) polymers featuring self-immolative azobenzene motifs. An electrophilic alkoxyetherification is utilized to introduce the photoreactive moieties required for the subsequent chain collapse via UV-induced nitrile imine-mediated tetrazole-ene cycloaddition (NITEC).

A novel facility for reduced-gravity testing: A setup for studying low-velocity collisions into granular surfaces.

This work presents an experimental design for studying low-velocity collisions into granular surfaces in low-gravity. In the experiment apparatus, reduced-gravity is simulated by releasing a free-falling projectile into a surface container with a downward acceleration less than that of Earth's gravity. The acceleration of the surface is controlled through the use of an Atwood machine, or a system of pulleys and counterweights. The starting height of the surface container and the initial separation distance between the projectile and surface are variable and chosen to accommodate collision velocities up to 20 cm/s and effective accelerations of ∼0.1 to 1.0 m/s(2). Accelerometers, placed on the surface container and inside the projectile, provide acceleration data, while high-speed cameras capture the collision and act as secondary data sources. The experiment is built into an existing 5.5 m drop tower frame and requires the custom design of all components, including the projectile, surface sample container, release mechanism, and deceleration system. Data from calibration tests verify the efficiency of the experiment's deceleration system and provide a quantitative understanding of the performance of the Atwood system.

Polybutadiene Functionalization via an Efficient Avenue.

We introduce a facile and quantitative postpolymerization functionalization methodology for 1,4-polybutadienes, allowing us to decorate their pendent alkene functionalities with bromine and alkoxyether motifs carrying an array of functional groups ranging from tetrazoles to pyrenes. Specifically, the approach makes use of a mild, metal-free, electrophilic cascade reaction employing N-bromosuccinimide (NBS), a cyclic ether (i.e., THF), and a functional carboxylic acid. Detailed NMR, SEC, and ATR-IR studies confirm the successful modification.