Photo-induced chemistry for the design of oligonucleotide conjugates and surfaces

A photocaged diene is introduced at the 5′-end of oligonucleotides using the H-phosphonate approach. The photoenol-functionalized DNA is subsequently employed for the conjugation to a protein and the spatially controlled immobilization onto surfaces using a light-induced Diels–Alder cycloaddition. Fully functional protein–DNA conjugates and patterned DNA surfaces are obtained under mild irradiation conditions

Heterobimetallic Eu(III)/Pt(II) single-chain nanoparticles: a path to enlighten catalytic reactions

We introduce the formation and characterization of heterometallic single-chain nanoparticles entailing both catalytic and luminescent properties. A terpolymer containing two divergent ligand moieties, phosphines and phosphine oxides, is synthesized and intramolecularly folded into nanoparticles via a selective metal complexation of Pt(II) and Eu(III). The formation of heterometallic Eu(III)/Pt(II) nanoparticles is evidenced by size exclusion chromatography, multinuclear NMR ($^{1}$H, $^{31}$P{$^{1}$H}, $^{19}$F, $^{195}$Pt) as well as diffusion-ordered NMR and IR spectroscopy. Critically, we demonstrate the activity of the SCNPs as a homogeneous and luminescent catalytic system in the amination reaction of allyl alcohol

Flexible Ink‐Jet Printed Polymer Light‐Emitting Diodes using a Self‐Hosted Non‐Conjugated TADF Polymer

Thermally activated delayed fluorescent (TADF) emitters have become the leading emissive materials for highly efficient organic light-emitting diodes (OLEDs). The deposition of these materials in scalable and cost-effective ways is paramount when looking toward the future of OLED applications. Herein, a simple OLED with fully solution-processed organic layers is introduced, where the TADF emissive layer is ink-jet printed. The TADF polymer has electron and hole conductive side chains, simplifying the fabrication process by removing the need for additional host materials. The OLED has a peak emission of 502 nm and a maximum luminance of close to 9600 cd m$_{−2}$. The self-hosted TADF polymer is also demonstrated in a flexible OLED, reaching a maximum luminance of over 2000 cd m$_{−2}$. These results demonstrate the potential applications of this self-hosted TADF polymer in flexible ink-jet printed OLEDs and, therefore, for a more scalable fabrication process

Hetero-Diels–Alder Cycloaddition with RAFT Polymers as Bioconjugation Platform

We introduce the bioconjugation of polymers synthesized by RAFT polymerization, bearing no specific functional end group, by means of hetero‐Diels–Alder cycloaddition through their inherent terminal thiocarbonylthio moiety with a diene‐modified model protein. Quantitative conjugation occurs over the course of a few hours, at ambient temperature and neutral pH, and in the absence of any catalyst. Our technology platform affords thermoresponsive bioconjugates, whose aggregation is solely controlled by the polymer chains

Hetero-Diels-Alder-Cycloaddition mit RAFT-Polymeren als Biokonjugationsplattform

Wir stellen die Biokonjugation von Polymeren vor, die durch RAFT‐Polymerisation mittels Hetero‐Diels‐Alder‐Cycloaddition durch ihren inhärenten terminalen Thiocarbonylthiorest mit einem dienmodifizierten Modellprotein synthetisiert wurden und keine spezifische funktionelle Endgruppe tragen. Die quantitative Konjugation erfolgt im Verlauf einiger Stunden bei Raumtemperatur und nahezu neutralem pH‐Wert und in Abwesenheit jeglichen Katalysators. Unsere Technologieplattform liefert thermoresponsive Biokonjugate, deren Aggregation allein durch die Polymerketten gesteuert wird

Visible light-induced switching of soft matter materials properties based on thioindigo photoswitches

Thioindigos are visible light responsive photoswitches with excellent spatial control over the conformational change between their trans- and cis- isomers. However, they possess limited solubility in all conventional organic solvents and polymers, hindering their application in soft matter materials. Herein, we introduce a strategy for the covalent insertion of thioindigo units into polymer main chains, enabling thioindigos to function within crosslinked polymeric hydrogels. We overcome their solubility issue by developing a thioindigo bismethacrylate linker able to undergo radical initiated thiol-ene reaction for step-growth polymerization, generating indigo-containing polymers. The optimal wavelength for the reversible trans-/cis- isomerisation of thioindigo was elucidated by constructing a detailed photochemical action plot of their switching efficiencies at a wide range of monochromatic wavelengths. Critically, indigo-containing polymers display significant photoswitching of the materials’ optical and physical properties in organic solvents and water. Furthermore, the photoswitching of thioindigo within crosslinked structures enables visible light induced modulation of the hydrogel stiffness. Both the thioindigo-containing hydrogels and photoswitching processes are non-toxic to cells, thus offering opportunities for advanced applications in soft matter materials and biology-related research

Inkjet‐Printed Self‐Hosted TADF Polymer Light‐Emitting Diodes

Thermally activated delayed fluorescent (TADF) materials are extensively investigated as organic light-emitting diodes (OLEDs) with TADF emitting layers demonstrating high efficiency without the use of heavy metal complexes. Therefore, solution-processable and printable TADF emitters are highly desirable, moving away from expensive vacuum deposition techniques. In addition, using emissive materials not requiring an external host simplifies the fabrication process significantly. Herein, OLEDs using a solution-processable TADF polymer that do not need an external host are introduced. The non-conjugated TADF polymer features a TADF emitter (4-(9H-carbazol-9-yl)-2-(3′-hydroxy-[1,1′-biphenyl]-3-yl)-isoindoline-1,3-dione) as a side chain, as well as a hole-transporting side chain and an electron-transporting side chain on an inactive polymer backbone. All organic layers of the OLEDs are fabricated using solution processing methods. The OLEDs with inkjet-printed emissive layers have comparable maximum current and external quantum efficiency as their spin-coated counterparts, exceeding luminance of 2000 cd m$^{-2}$. The herein-explored strategy is a viable route toward self-hosted printable TADF OLEDs