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.

Wavelength Orthogonal Photodynamic Networks.

The ability of light to remotely control the properties of soft matter materials in a dynamic fashion has fascinated material scientists and photochemists for decades. However, only recently has our ability to map photochemical reactivity in a finely wavelength resolved fashion allowed for different colors of light to independently control the material properties of polymer networks with high precision, driven by monochromatic irradiation enabling orthogonal reaction control. The current concept article highlights the progress in visible light-induced photochemistry and explores how it has enabled the design of polymer networks with dynamically adjustable properties. We will explore current applications ranging from dynamic hydrogel design to the light-driven adaptation of 3D printed structures on the macro- and micro-scale. While the alternation of mechanical properties via remote control is largely reality for soft matter materials, we herein propose the next frontiers for adaptive properties, including remote switching between conductive and non-conductive properties, hydrophobic and hydrophilic surfaces, fluorescent or non-fluorescent, and cell adhesive vs. cell repellent properties.

Near Infrared Light Induced Radical Polymerization in Water.

We introduce a gold nanorod (AuNR) driven methodology to induce free radical polymerization in water with near infrared light (800 nm). The process exploits photothermal conversion in AuNR and subsequent heat transfer to a radical initiator (here azobisisobutyronitrile) for primary radical generation. A broad range of reaction conditions were investigated, demonstrating control over molecular weight and reaction conversion of dimethylacrylamide polymers, using nuclear magnetic resonance spectroscopy. We underpin our experimental data with finite element simulation of the spatio-temporal temperature profile surrounding the AuNR directly after femtosecond laser pulse excitation. Critically, we evidence that polymerization can be induced through biological tissues given the enhanced penetration depth of the near infrared light. We submit that the presented initiation mechanism in aqueous systems holds promise for radical polymerization in biological environments, including cells.

Multicomponent Reactions in Polymer Chemistry Utilizing Heavier Main Group Elements.

Herein, a concise overview of the use of heavier main group elements in multicomponent reactions and their use in polymer chemistry is provided. Incorporating heavier elements into macromolecular structures via multicomponent reactions allows for the rapid development of materials with unique properties that are not readily achieved using carbon, nitrogen, and/or oxygen. Elements in Group 13, Group 14, Group 15, and Group 16 are specifically covered examining both the familiar and unfamiliar properties of these elements and how they are used in multicomponent chemistry. Furthermore, elements that both take part in the reaction mechanism and remain in the macromolecular structure upon completion are only briefly explored. Some of the state-of-the-art work going into developing these heavier element multicomponent reactions are highlighted and it is hoped to inspire other polymer chemists to explore other parts of the periodic table.

Wavelength-Selective Folding of Single Polymer Chains with Different Colors of Visible Light.

Photochemistry allows chemists to exert control over chemical reactions with spatiotemporal precision. Furthermore, light holds the potential to not only gate when and where but also which reaction takes place. Herein, two photocycloaddition reactions-initiated by different colors of visible light-are utilized to control the intramolecular crosslinking of single polymer chains. Irradiation with blue light (λmax = 470 nm) triggers a [2 + 2] photocycloaddition inducing an initial intramolecular crosslinking reaction, whereas subsequent irradiation with violet light (λmax = 415 nm) induces a [4 + 4] photocycloaddition, fully compacting the dual photoreactive polymer into a single-chain nanoparticle. Importantly, both crosslinked states are accessible under ultra-mild conditions requiring nothing but two different colors of visible light. The reported strategy of wavelength-selective crosslinking degrees provides key potential to be translated into materials applications for the remote control of mechanical properties on the molecular level.

Facile Synthesis and In-Depth Characterization of Polymethacrylimides with Tunable Properties.

High-performance polymers such as polymethacrylimides have outstanding properties, for example, a unique strength-to-weight ratio and a high thermal stability, usually coupled to a high glass transition temperature. However, the requirement of high processing temperatures caused by these high glass-transition temperatures is often not desired for melt extrusion processes. Herein, a novel and straightforward imidization process of poly(methacrylic anhydrides) is presented with different ratios of ammonia and N-isopropylamine that is induced by thermal treatment. Therefore, polymethacrylimides with a varying degree of N-substitution, and thus a varying number of hydrogen-bond-donating moieties, are synthesized under facile reaction conditions. An in-depth investigation into the structures obtained with this new methodology is undertaken via a combination of nuclear magnetic resonance spectroscopy (NMR), Fourier-transform infrared spectroscopy (FT-IR), and high-resolution electrospray ionization mass spectrometry (ESI-MS). Additionally, thermal properties of the materials are investigated using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) analyses. These latter measurements highlight the key opportunity available with this novel synthesis to tailor the thermal properties of the polymer by providing a clear correlation between hydrogen bond formation, as observed by FT-IR, and the glass transition temperature.

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.

Single-Chain Nanoparticles as Catalytic Nanoreactors.

The need for efficient, tailor-made catalysts has inspired chemists to fuse the design principles of natural enzymes with synthetic macromolecular architectures. A highly interesting pathway mimics a metallo-enzyme's tertiary structure via the target placement of metal-ions in a tailor-made polymeric framework, resulting in catalytically active single-chain nanoparticles. Initial studies reveal unusual and promising effects, regarding both new catalyst characteristics and a high impact on product formation. These multifunctional nanoreactors, constructed from simple folded polymer chains, will lead to advanced bioinspired catalytic systems. As found in enzymes, their impact lies specifically within the defined construction of a polymeric pocket around the catalytic active cores for substrate recognition.

Intrinsically Fluorescent, Stealth Polypyrazoline Nanoparticles with Large Stokes Shift for In Vivo Imaging.

Recent advances in super-resolution microscopy and fluorescence bioimaging allow exploring previously inaccessible biological processes. To this end, there is a need for novel fluorescent probes with specific features in size, photophysical properties, colloidal and optical stabilities, as well as biocompatibility and ability to evade the reticuloendothelial system. Herein, novel fluorescent nanoparticles are introduced based on an inherently fluorescent polypyrazoline (PPy) core and a polyethylene glycol (PEG) shell, which address all aforementioned challenges. Synthesis of the PPy-PEG amphiphilic block copolymer by phototriggered step-growth polymerization is investigated by NMR spectroscopy, size-exclusion chromatography, and mass spectrometry. The corresponding nanoparticles are characterized for their luminescent properties and hydrodynamic size in various aqueous environments (e.g., cell culture media). PPy nanoparticles particularly exhibit a large Stokes shift (Δλ = 160 nm or Δν > 7000 cm-1 ) with visible light excitation and strong colloidal stability. While clearance by macrophages and endothelial cells is minimal, PPy displays good biocompatibility. Finally, PPy nanoparticles prove to be long circulating when injected in zebrafish embryos, as observed by in vivo time-lapse fluorescence microscopy. In summary, PPy nanoparticles are highly promising to be further developed as fluorescent nanodelivery systems with low toxicity and exquisite retention in the blood stream.

Engineering Nitroxide Functional Surfaces Using Bioinspired Adhesion.

We pioneer a versatile surface modification strategy based on mussel-inspired oxidative catecholamine polymerization for the design of nitroxide-containing thin polymer films. A 3,4-dihydroxy-l-phenylalanine (l-DOPA) monomer equipped with a 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-derived oxidation-labile hydroxylamine functional group is employed as a universal coating agent to generate polymer scaffolds with persistent radical character. Various types of materials including silicon, titanium, ceramic alumina, and inert poly(tetrafluoroethylene) (PTFE) were successfully coated with poly(DOPA-TEMPO) thin films in a one-step dip-coating procedure under aerobic, slightly alkaline (pH 8.5) conditions. Steadily growing polymer films (∼1.1 nm h-1) were monitored by ellipsometry, and their thicknesses were critically compared with those obtained from atomic force microscopic cross-sectional profiles. The heterogeneous composition of surface-adherent nitroxide scaffolds examined by X-ray photoelectron spectroscopy was correlated to that examined by in-solution polymer analysis via high-resolution electrospray ionization mass spectrometry, revealing oligomeric structures with up to six repeating units, mainly composed of covalently linked dihydroxyindole along the polymer backbone. Critically, the reversible redox-active character of the nitroxide-containing polymer scaffolds was investigated by cyclic voltammetric measurements, revealing a convenient and facile access route to electrochemically active nitroxide polymer coatings with potential application in electronic devices such as organic radical batteries.

Delivery of Amonafide from Fructose-Coated Nanodiamonds by Oxime Ligation for the Treatment of Human Breast Cancer.

The introduction of a strategy toward polymer/nanodiamond hybrids with high polymer grafting density and accessible polymer structural characterization is of critical importance for nanodiamonds' surface modification and bioagent attachment for their biomedical application. Here, we report a glycopolymer/nanodiamond hybrid drug delivery system, which was prepared by grafting amonafide-conjugated glycopolymers onto the surface of nanodiamonds via oxime ligation. Poly(1-O-methacryloyl-2,3:4,5-di-O-isopropylidene-ß-d-fructopyranose)-b-poly(3-vinylbenzaldehyde-co-methyl methacrylate), featuring pendant aldehyde groups, is prepared via RAFT polymerization. The anticancer drug amonafide is conjugated to the polymer chains via imine chemistry, resulting in acid-degradable imine linkages. The obtained amonafide-conjugated glycopolymers are subsequently grafted onto the surface of aminooxy-functionalized nanodiamonds via oxime ligation. The molecular weight of the conjugated polymers is characterized by size-exclusion chromatography (SEC), while the successful conjugation and corresponding grafting density is assessed by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric aanalysis (TGA). Our results indicate that the mass percentage of amonafide in the polymer chains is around 17% and the surface density of polymer chains is 0.24 molecules/nm2. The prepared drug delivery system has a hydrodynamic size around 380 nm with low PDI (0.3) and can effectively deliver amonafide into breast cancer cell and significantly inhibit the cancer cell viability. In 2D cell culture models, the IC50 values of ND-Polymer-AMF delivery system (7.19 µM for MCF-7; 4.92 µM for MDA-MB-231) are lower than those of free amonafide (11.23 µM for MCF-7; 13.98 µM for MDA-MB-231). An inhibited cell viability of nanodiamonds/polymer delivery system is also observed in 3D spheroids' models, suggesting that polymer-diamonds hybrid materials can be promising platforms for breast cancer therapy.

Making and Breaking Chemical Bonds by Chemiluminescence.

Chemiluminescent (CL) reactions are powerful analytical tools and are present in commercially available everyday objects such as glow sticks. Herein, the photons generated by chemiluminescence are exploited to induce covalent bond breakage and formation, using a chemically generated photonic field at ambient temperature through space as energy transducer. Remarkably, the generated photons enable both the cleavage of species generating radicals as well as the execution of [2 + 2] cycloadditions, demonstrating that disparate types of reactions can be triggered. The herein-presented photochemical concept establishes the field of CL-induced photochemistry, which is poised to enable photochemical transformations in situations where physical light sources, such as lamps, LEDs, and lasers cannot be employed, including in biological environments.

Stepwise Light-Induced Dual Compaction of Single-Chain Nanoparticles.

A photochemical strategy for the sequential dual compaction of single polymer chains is introduced. Two photoreactive methacrylates, with side chains bearing either a phenacyl sulfide (PS) or an α-methylbenzaldehyde (photoenol, PE) moiety, are selectively incorporated by one-pot iterative reversible-addition fragmentation chain transfer copolymerization into the outer blocks of a well-defined poly(methyl methacrylate) based ABC triblock copolymer possessing a nonfunctional spacer block (Mn = 23 400 g mol-1 , D = 1.2; ≈15 units of each photoreactive moieties of each type) as well as in model statistical copolymers bearing only one type of photoreactive unit. Upon UVA irradiation, PS and PE lead to highly reactive thioaldehydes and o-quinodimethanes, which rapidly react with dithiol and diacrylate linkers, respectively. The monomerfunctional copolymers are employed to establish the conditions for controlled intramolecular photo-crosslinking, which are subsequently applied to the bifunctional triblock copolymer. All compaction/folding experiments are monitored by size-exclusion chromatography and dynamic light scattering. The dual compaction consists of two events of dissimilar amplitude: the first folding step reveals a large reduction in hydrodynamic diameters, while the second compaction lead to a far less pronounced reduction of the single-chain nanoparticles size, consistent with the reduced degrees of freedom available after the first covalent compaction step.

Dynamic Macromolecular Material Design-The Versatility of Cyclodextrin-Based Host-Guest Chemistry.

Dynamic and adaptive materials are powerful constructs in macromolecular and polymer chemistry with a wide array of applications in drug delivery, bioactive systems, and self-healing materials. Very often, dynamic materials are based on carefully tailored cyclodextrin host-guest interactions. The precise incorporation of these host and guest moieties into macromolecular building blocks allows the formation of complex macromolecular structures with predefined functions. Thus, dynamic materials with extraordinary adaptive property profiles-responsive to thermal, chemical, and photonic fields-become accessible. This Review explores the hierarchical formation of dynamic materials and complex macromolecular structures from the molecular via the macromolecular to the colloidal and macroscopic level, with a specific emphasis on the functionality and responsiveness of the assemblies, specifically in biological contexts.

Cycloadditions in modern polymer chemistry.

Synthetic polymer chemistry has undergone two major developments in the last two decades. About 20 years ago, reversible-deactivation radical polymerization processes started to give access to a wide range of polymeric architectures made from an almost infinite reservoir of functional building blocks. A few years later, the concept of click chemistry revolutionized the way polymer chemists approached synthetic routes. Among the few reactions that could qualify as click, the copper-catalyzed azide-alkyne cycloaddition (CuAAC) initially stood out. Soon, many old and new reactions, including cycloadditions, would further enrich the synthetic macromolecular chemistry toolbox. Whether click or not, cycloadditions are in any case powerful tools for designing polymeric materials in a modular fashion, with a high level of functionality and, sometimes, responsiveness. Here, we wish to describe cycloaddition methodologies that have been reported in the last 10 years in the context of macromolecular engineering, with a focus on those developed in our laboratories. The overarching structure of this Account is based on the three most commonly encountered cycloaddition subclasses in organic and macromolecular chemistry: 1,3-dipolar cycloadditions, (hetero-)Diels-Alder cycloadditions ((H)DAC), and [2+2] cycloadditions. Our goal is to briefly describe the relevant reaction conditions, the advantages and disadvantages, and the realized polymer applications. Furthermore, the orthogonality of most of these reactions is highlighted because it has proven highly beneficial for generating unique, multifunctional polymers in a one-pot reaction. The overview on 1,3-dipolar cycloadditions is mostly centered on the application of CuAAC as the most travelled route, by far. Besides illustrating the capacity of CuAAC to generate complex polymeric architectures, alternative 1,3-dipolar cycloadditions operating without the need for a catalyst are described. In the area of (H)DA cycloadditions, beyond the popular maleimide/furan couple, we present chemistries based on more reactive species, such as cyclopentadienyl or thiocarbonylthio moieties, particularly stressing the reversibility of these systems. In these two greater families, as well as in the last section on [2+2] cycloadditions, we highlight phototriggered chemistries as a powerful tool for spatially and temporally controlled materials synthesis. Clearly, cycloaddition chemistry already has and will continue to transform the field of polymer chemistry in the years to come. Applying this chemistry enables better control over polymer composition, the development of more complicated polymer architectures, the simplification of polymer library production, and the discovery of novel applications for all of these new polymers.

Thermoresponsive Agarose Based Microparticles for Antibody Separation.

We report the development of thermoresponsive 4-mercaptoethylpyridine (MEP)-based chromatographic microsphere based resins for antibody separation that show switchable release abilities by adsorbing immunoglobulins at 40 °C and releasing the proteins at 5 °C. The thermoswitchable release properties were introduced to the porous resins by the grafting of linear poly(N-isopropylacrylamide) (PNIPAM) chains synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization, which were modified to possess MEP end functionalities. Adsorption of γ-globulins as a model antibody on the shortest PNIPAM-MEP (3 kDa) grafted microparticles display binding capacities of up to 20 g L(-1) at 40 °C and a significant decrease in binding capacity to less than 2.5 g L(-1) at 5 °C. By switching the temperature to 5 °C, the release of bound γ-globulins is shown to be as high as 90%. The effects of polymer chain length on the binding capacity are studied in detail and found to be critical as they influence the density of MEP functionalities on the particle surfaces.

Fructose-Coated Nanodiamonds: Promising Platforms for Treatment of Human Breast Cancer.

Well-defined carboxyl end-functionalized glycopolymer Poly(1-O-methacryloyl-2,3:4,5-di-O-isopropylidene-ß-d-fructopyranose) (Poly(1-O-MAipFru)62) has been prepared via reversible addition-fragmentation chain transfer polymerization and grafted onto the surface of amine-functionalized nanodiamonds via a simple conjugation reaction. The properties of the nanodiamond-polymer hybrid materials ND-Poly(1-O-MAFru)62 are investigated using infrared spectroscopy, thermogravimetric analysis, dynamic light scattering, and transmission electron microscopy. The dispersibility of the nanodiamonds in aqueous solutions is significantly improved after the grafting of the glycopolymer. More interestingly, the cytotoxicity of amine-functionalized nanodiamonds is significantly decreased after decoration with the glycopolymer even at a high concentration (125 µg/mL). The nanodiamonds were loaded with doxorubicin to create a bioactive drug delivery carrier. The release of doxorubicin was faster in media of pH 5 than media of pH 7.4. The nanodiamond drug delivery systems with doxorubicin are used to treat breast cancer cells in 2D and 3D models. Although the 2D cell culture results indicate that all nanodiamonds-doxorubicin complexes are significantly less toxic than free doxorubicin, the glycopolymer-coated nanodiamonds-doxorubicin show higher cytotoxicity than free doxorubicin in the 3D spheroids after treatment for 8 days. The enhanced cytotoxicity of Poly(1-O-MAFru)62-ND-Dox in 3D spheroids may result from the sustained drug release and deep penetration of these nanocarriers, which play a role as a "Trojan Horse". The massive cell death after 8-day incubation with Poly(1-O-MAFru)62-ND-Dox demonstrates that glycopolymer-coated nanodiamonds can be promising platforms for breast cancer therapy.

Polymer-Fullerene Network Formation via Light-Induced Crosslinking.

A facile and efficient methodology for the formation of polymer-fullerene networks via a light-induced reaction is reported. The photochemical crosslinking is based on a nitrile imine-mediated tetrazole-ene cycloaddition reaction, which proceeds catalyst-free under UV-light irradiation (λmax = 320 nm) at ambient temperature. A tetrazole-functionalized polymer (Mn = 6500 g mol(-1) , Ð = 1.3) and fullerene C60 are employed for the formation of the hybrid networks. The tetrazole-functionalized polymer as well as the fullerene-containing networks are carefully characterized by NMR spectrometry, size exclusion chromatography, infrared spectroscopy, and elemental analysis. Furthermore, thermal analysis of the fullerene networks and their precursors is carried out. The current contribution thus induces an efficient platform technology for fullerene-based network formation.

Determining Free-Radical Propagation Rate Coefficients with High-Frequency Lasers: Current Status and Future Perspectives.

Detailed knowledge of the polymerization mechanisms and kinetics of academically and industrially relevant monomers is mandatory for the precision synthesis of tailor-made polymers. The IUPAC-recommended pulsed-laser polymerization-size exclusion chromatography (PLP-SEC) approach is the method of choice for the determination of propagation rate coefficients and the associated Arrhenius parameters for free radical polymerization processes. With regard to specific monomer classes-such as acrylate-type monomers, which are very important from a materials point of view-high laser frequencies of up to 500 Hz are mandatory to prevent the formation of mid-chain radicals and the occurrence of chain-breaking events by chain transfer, if industrially relevant temperatures are to be reached and wide temperature ranges are to be explored (up to 70 °C). Herein the progress and state-of-the-art of high-frequency PLP-SEC with pulse repetition rates of 500 Hz is reported, with a critical collection of to-date investigated 500 Hz data as well as future perspectives for the field.

Just Add Salt: A Mass Spectrometric Analysis Method for Imaging Anion-Exchanged Poly(Ionic Liquid)s.

We report the first mass spectrometric analysis of poly(ionic liquid)s (PILs) containing weakly coordinating anions introduced by a fast, simple, and quantitative postmodification method on the example of the hydrophilic, well-defined poly(vinylbenzylpyridinium chloride) p([VBPy]Cl) species, analyzed with an in-source collision induced dissociation-Orbitrap mass spectrometry (MS) protocol. Using the MS approach allows for the precise structural elucidation of ion-exchanged p([VBPy]Cl) utilizing AgX (X = NO3- , CF3 CO2- , BF4- ) salts. The anion exchange is shown to be quantitative - without observing residual chlorinated PIL - on rapid time scales, using only filtration as a standard procedure during sample preparation. In addition, the influence of weakly coordinating anions on the ionization behavior of PILs is studied in detail.