Gradient macroporous polymers were produced by polymerization of emulsion templates comprising a continuous monomer phase and an internal aqueous template phase. To produce macroporous polymers with gradient composition, pore size, and foam density, we varied the template formulation, droplet size, and internal phase ratio of emulsion templates continuously and stacked those prior to polymerization. Using the outlined approach, it is possible to vary one property along the resulting macroporous polymer while retaining the other properties. The elastic moduli and crush strengths change along the gradient of the macroporous polymers; their mechanical properties are dominated by those of the weakest layers in the gradient. Macroporous polymers with gradient chemical composition and thus stiffness provide both high impact load and energy adsorption, rendering the gradient foam suitable for impact protective applications. We show that dual-dispensing and simultaneous blending of two different emulsion formulations in various ratios results in a fine, bidirectional change of the template composition, enabling the production of true gradient macroporous polymers with a high degree of design freedom.
Single chain nanoparticles (SCNPs) are a highly versatile polymer architecture consisting of single polymer chains that are intramolecularly crosslinked. Currently, SCNPs are discussed as powerful macromolecular architectures for catalysis, delivery and sensors. Herein, we introduce a methodology based on Förster Resonance Energy Transfer (FRET) to evidence the folding of single polymer chains into SCNPs via fluorescence readout. We initially introduce a molecular FRET pair based on a bimane and nitrobenzoxadiazole (NBD) moiety and study its fluorescence properties in different solvents. We subsequently construct a low dispersity polymer chain carrying NBD units, while exploiting the bimane units for intramolecular chain collapse. Upon chain collapse and SCNP formation - thus bringing bimane and NBD units into close proximity - the SCNPs report their folded state by a strong and unambiguous FRET fluorescence signal. The herein introduced reporting of the folding state of SCNPs solely relies on an optical readout, opening avenues to monitoring SCNP folding without recourse to complex analytical methodologies.
We introduce a class of single-chain nanoparticles (SCNPs) that respond to visible light (λmax =415â nm) with complete unfolding from their compact structure into linear chain analogues. The initial folding is achieved by a simple esterification reaction of the polymer backbone constituted of acrylic acid and polyethylene glycol carrying monomer units, introducing bimane moieties, which allow for the photochemical unfolding, reversing the ester-bond formation. The compaction and the light driven unfolding proceed cleanly and are readily followed by size exclusion chromatography (SEC) and diffusion ordered NMR spectroscopy (DOSY), monitoring the change in the hydrodynamic radius (RH ). Importantly, the folding reaction and the light-induced unfolding are reversible, supported by the high conversion of the photo cleavage. As the unfolding reaction occurs in aqueous systems, the system holds promise for controlling the unfolding of SCNPs in biological environments.
Independently addressing photoreactive sites within one molecule with two colours of light is a formidable challenge. Here, we combine two sequence independent λ-orthogonal chromophores in one heterotelechelic dilinker molecule, to exploit their disparate reactivity utilizing the same reaction partner, a maleimide-containing polymer. We demonstrate that polymer network formation only proceeds if two colours of light are employed. Upon single colour irradiation, linker-decorated post-functionalized polymers are generated at either wavelength and in either sequence. Network formation, however, is only achieved by sequential or simultaneous two colour irradiation. The herein introduced photoreactive system demonstrates the power of wavelength orthogonal chemistry in macromolecular synthesis.
Wood, being renewable and highly abundant material, with excellent high specific strength and stiffness, has received increasing attention to be used in high performance applications such as the structural element of a battery case in an electric vehicle. For a successful implementation of wood in the automotive sector, it is, therefore, crucial to understand the behaviour of wood during and after temperature exposure and in the event of fire with the presence/absence of oxygen. In this study, the mechanical properties of thermally modified and unmodified European beech and birch in air and nitrogen environments at six different treatment intensities were characterised using compression tests, tensile tests, shear tests and Poisson's ratio tests. Further, the elastic properties of these wood species were quantified using the ultrasound measurements. The obtained strength and stiffness exhibited mild improvement upon moderate temperature treatment (200 °C), followed by a decrease at elevated temperature levels. This improvement was somewhat more pronounced under nitrogen treatment than under air treatment conditions. Nevertheless, a more noticeable decrease in the material performance was observed in beech compared to birch, occurring at earlier stages of modifications. This study confirms the tension-compression asymmetry of beech and birch where higher Young's moduli were obtained from tensile than from compression tests for reference and thermally treated beech and birch. The shear moduli obtained from ultrasound for birch were comparable to those obtained from quasi-static tests, whereas there was an overestimation of approximately 11-59% for the shear modulus of beech compared to quasi-static tests. Poisson's ratios from ultrasound tests corresponded well with those from quasi-static tests for untreated beech and birch, but not for thermally modified samples. The Saint-Venant model can satisfactorily predict the shear moduli of untreated and treated beech wood.
We introduce single-chain nanoparticles (SCNPs) exclusively folded by covalently bonded ferrocene units. Specifially, we demonstrate the ability of 2-ferrocenyl-1,10-phenanthroline to fuse single-chain collapse with the concomitant introduction of a donor functionality allowing the installation of a Pd-catalytic site, affording the first heterobimetallic ferrocene-functionalized SCNP.
Printed organic and inorganic electronics continue to be of large interest for sensors, bioelectronics, and security applications. Many printing techniques have been investigated, albeit often with typical minimum feature sizes in the tens of micrometer range and requiring post-processing procedures at elevated temperatures to enhance the performance of functional materials. Herein, we introduce laser printing with three different inks, for the semiconductor ZnO and the metals Pt and Ag, as a facile process for fabricating printed functional electronic devices with minimum feature sizes below 1 µm. The ZnO printing is based on laser-induced hydrothermal synthesis. Importantly, no sintering of any sort needs to be performed after laser printing for any of the three materials. To demonstrate the versatility of our approach, we show functional diodes, memristors, and a physically unclonable function based on a 6 × 6 memristor crossbar architecture. In addition, we realize functional transistors by combining laser printing and inkjet printing.
It is demonstrated that the postfunctionalization of solid polymeric microspheres can generate fully and throughout functionalized materials, contrary to the expectation that core-shell structures are generated. The full functionalization is illustrated on the example of photochemically generated microspheres, which are subsequently transformed into polyradical systems. Given the all-organic nature of the functionalized microspheres, characterization methods with high analytical sensitivity and spatial resolution are pioneered by directly visualizing the inner chemical distribution of the postfunctionalized microspheres based on characteristic electron energy loss signals in transmission electron microscopy (TEM). Specifically, ultrasonic ultramicrotomy is combined successfully with electron energy loss spectroscopy (EELS) and electron spectroscopic imaging (ESI) during TEM. These findings open a key avenue for analyzing all-organic low-contrast soft-matter material structures, while the specifically investigated system concomitantly holds promise as an all-radical solid-state functional material.
Driven by the demand for highly specialized polymeric materials via milder, safer, and sustainable processes, we herein introduce a powerful, purely light driven platform for microsphere synthesis - including facile synthesis by sunlight. Our light-induced step-growth precipitation polymerization produces monodisperse particles (0.4-2.4 µm) at ambient temperature without any initiator, surfactant, additive or heating, constituting an unconventional approach compared to the classically thermally driven synthesis of particles. The microspheres are formed via the Diels-Alder cycloaddition of a photoactive monomer (2-methylisophthaldialdehyde, MIA) and a suitable electron deficient dienophile (bismaleimide). The particles are stable in the dry state as well as in solution and their surface can be further functionalized to produce fluorescent particles or alter their hydrophilicity. The simplicity and versatility of our approach introduces a fresh opportunity for particle synthesis, opening access to a yet unknown material class.
We herein report the first light-driven selective monoderivatization (desymmetrization) of two chemically equivalent carbonyl groups in a single chromophore. By comparing of four symmetric regioisomers, featuring two equivalent ortho-methylbenzaldehyde units, we identify dimethyltherephtalaldehydes (DMTAs) which can be activated in a dual wavelength-selective fashion. Under visible light and UV-light irradiation, DMTAs undergo two consecutive Diels-Alder reactions exhibiting near-quantitative endo-selectivity (>99%) and provide excellent yields (96-98%). The influence of the regioisomerism of the dialdehydes on their photochemical behavior is profound, evidenced by an in-depth investigation of their photochemical performance. We exemplify the capability of the photosystems via the synthesis of complex Diels-Alder adducts with various dienophiles, including alkynes.
Split Hopkinson bars are used for the dynamic mechanical characterisation of materials under high strain rates. Many of these test benches are designed in such a way that they can either be used for compressive or tensile loading. The goal of the present work is to develop a release mechanism for an elastically pre-stressed Split Hopkinson bar that can be universally used for tensile or compressive loading. The paper describes the design and dimensioning of the release mechanism, including the brittle failing wear parts from ultra-high strength steel. Additionally, a numerical study on the effect of the time-to-full-release on the pulse-shape and pulse-rising time was conducted. The results of the analytical dimensioning approaches for the release mechanism, including the wear parts, were validated against experimental tests. It can be demonstrated that the designed release concept leads to sufficiently short and reproducible pulse rising times of roughly 0.11 ms to 0.21 ms, depending on the pre-loading level for both the tension and compression wave. According to literature, the usual pulse rising times can range from 0.01 ms to 0.35 ms, which leads to the conclusion that a good average pulse rising time was achieved with the present release system.
In order to use wood for structural and load-bearing purposes in mechanical engineering, basic information on the impact behaviour of the material over a wide temperature range is needed. Diffuse porous hardwoods such as solid birch wood (Betula pendula) and solid beech wood (Fagus sylvatica) are particularly suited for the production of engineered wood products (EWPs) such as laminated veneer lumber (LVL) or plywood due to their processability in a veneer peeling process. In the frame of this study, solid birch wood and solid beech wood samples (300 × 20 × 20 mm3) were characterised by means of an impact pendulum test setup (working capacity of 150 J) at five temperature levels, ranging from -30 °C to +90 °C. The pendulum hammer (mass = 15 kg) was equipped with an acceleration sensor in order to obtain the acceleration pulse and deceleration force besides the impact bending energy. In both solid birch wood and solid beech wood, the deceleration forces were highest at temperatures at and below zero. While the average impact bending energy for solid birch wood remained almost constant over the whole considered temperature range, it was far less stable and prone to higher scattering for solid beech wood.
High-voltage busbars are important electrical components in today's electric vehicle battery systems. Mechanical deformations in the event of a vehicle crash could lead to electrical busbar failure and hazardous situations that pose a threat to people and surroundings. In order to ensure a safe application of busbars, this study investigated their mechanical behavior under high strain rate loading using a split Hopkinson pressure bar. Two different types of high-voltage busbars, consisting of a polyamide 12 and a glass-fiber-reinforced (30%) polyamide 6 insulation layer, were tested. Additionally, the test setup included a 1000 V electrical short circuit measurement to link the electrical with the mechanical failure. It was found that the polyamide 12 insulated busbars' safety regarding insulation failure increases at high loading speed compared to quasi-static measurements. On the contrary, the fiber-reinforced polyamide 6 insulated busbar revealed highly brittle material behavior leading to reduced bearable loads and intrusions. Finally, the split Hopkinson pressure bar tests were simulated. Existing material models for the thermoplastics were complemented with an optimized generalized incremental stress state-dependent model (GISSMO) with strain rate dependency. A good agreement with the experimental behavior was achieved, although the absence of viscoelasticity in the underlying material models was notable.
We introduce a highly efficient ligation system based on a visible light-induced rearrangement affording a thiophenol which rapidly undergoes thiol-Michael additions. Unlike conventional light-triggered thiol-ene/yne systems, which rely on the use of photocaged bases/nucleophiles, (organo)-photo catalysts, or radical photoinitiators, our system provides a light-induced reaction in the absence of any additives. The ligation is self-catalyzed via the pyridine mediated deprotonation of the photochemically generated thiophenol. Subsequently, the thiol-Michael reaction between the thiophenol anion and electron deficient alkynes/alkenes proceeds additive-free. Hereby, the underlying photoinduced rearrangement of o-thiopyrinidylbenzaldehyde (oTPyB) generating the free thiol is described for the first time. We studied the influence of various reactions conditions as well as solvents and substrates. We exemplify our findings in a polymer end group modification and obtained macromolecules with excellent end group fidelity.
The control of chemical functionalization with orthogonal light stimuli paves the way toward manipulating materials with unprecedented spatiotemporal resolution. To reach this goal, we herein introduce a photochemical reaction system that enables two-color control of covalent ligation via an oxo-Diels-Alder cycloaddition between two separate light-responsive molecular entities: a UV-activated photocaged diene based on ortho-quinodimethanes and a carbonyl dienophile appended to a diarylethene photoswitch, whose reactivity can be modulated upon illumination with UV and visible light.
Herein, we pioneer a wavelength-gated synthesis route to phenalene diimides. Consecutive Diels-Alder reactions of methylisophthalaldehydes and maleimides afford hexahydro-phenalene-1,6-diol diimides via 5-formyl-hexahydro-benzo[f]isoindoles as the intermediate. Both photoreactions are efficient (82-99 % yield) and exhibit excellent diastereoselectivity (62-98 %â d.r.). The wavelength-gated nature of the stepwise reaction enables the modular construction of phenalene diimide scaffolds by choice of substrate and wavelength. Importantly, this synthetic methodology opens a facile avenue to a new class of persistent phenalenyl diimide neutral radicals, constituting a versatile route to spin-active molecules.
The project WoodC.A.R. investigates the capabilities of wood and engineered wood-products (EWPs) for their application as a load-bearing material in automotive applications. For crash-relevant components, materials have to provide a high impact bending energy over a wide range of climatic conditions. This study investigates the effect of temperature on the bending behavior of solid birch wood beams (800 × 90 × 43 mm3) under quasi-static and dynamic loading. Specimens were exposed to a three-point bending test with lateral confinement, replicating the hypothetical installation environment in a car, at five temperature levels: -30 °C, 0 °C, +30 °C, +60 °C, and +90 °C. A cylindrical impactor (D = 254 mm, m = 91 kg) was propelled against the center of the beam with an initial velocity of 8.89 m/s (dynamic) and at a constant velocity of 10 mm/min (quasi-static), respectively. Specimens were conditioned in a freezer and a climate chamber, respectively. Temperature was monitored prior and during testing. Bulk density and global fiber deviation were determined afterwards. In both, the dynamic and the quasi-static load case maximum force slightly decreased with increasing temperature, but remained almost constant at temperatures exceeding +30 °C. On average, the maximum dynamic peak force level was twice as high as in quasi-static tests. In the quasi-static tests, the energy absorption remained constant at elevated temperatures (+30 °C to +90 °C) but decreased by about 50% at lower temperatures -30 °C and 0 °C. In the dynamic tests, the energy absorption remained almost constant throughout the entire temperature range.
We report a photochemical reaction system which requires activation by two colors of light. Specifically, a dual wavelength gated system is established by fusing the visible light mediated deprotection of a dithioacetal with the UV light activated Diels-Alder reaction of an o-methylbenzaldehyde with N-ethylmaleimide. Critically, both light sources are required to achieve the Diels-Alder adduct, irradiation with visible or UV light alone does not lead to the target product. The introduced dual gated photochemical system is particularly interesting for application in light driven 3D printing, where two color wavelength activated photoresists may become reality.
We introduce a highly efficient photoligation system, affording a pro-fluorescent Diels-Alder product that, on demand, converts into an intensively fluorescent naphthalene via E1 elimination in the presence of catalytic amounts of acid. The Diels-Alder reaction of the photocaged diene (o-quinodimethane ether or thioether) with electron-deficient alkynes is induced by UV or visible light. In contrast to previously reported ligation techniques directly leading to fluorescent products, the fluorescence is turned on after the photoligation. Thus, the light absorption of the fluorophore does not undermine the photoligation via competitive absorption, and as a result, photobleaching or side reactions of the fluorophore are not observed. Critically, the gated generation of a fluorescent product allows for fluorometric determination of the conversion. We employ a simple synthesis strategy for heterobifunctional electron-deficient alkynes allowing for facile functionalization of payload molecules.
Herein, we introduce a fast, additive-free, ambient temperature photochemical approach - utilising the novel Diels-Alder cycloaddition of a photo-active ortho-methylbenzaldehyde (oMBA) with a terminal alkyne - for preparing functional acid-sensitive profluorescent nano-/microspheres in one step. Not previously reported, the possibility of applying such a reaction in the context of particle synthesis provides new possibilities for particle design, where multi-step reactivity can be gated into distinct steps. First, a photochemically-gated particle formation step yields a material possessing a reactive, spring-loaded intermediate at every cross-linking point. A second, on-demand step to initiate fluorescence generation subsequently imparts the properties of the chemical transformation to the material itself. The synthesised particles are narrow-disperse with an average diameter ranging from 170-380 nm.
