Magnetic Removal of Micro- and Nanoplastics from Water-from 100 nm to 100 µm Debris Size.

Clean water is one of the most important resources of the planet but human-made contamination with diverse pollutants increases continuously. Microplastics (<5 mm diameter) which can have severe impacts on the environment, are present worldwide. Degradation processes lead to nanoplastics (<1 µm), which are potentially even more dangerous due to their increased bioavailability. State-of-the-art wastewater treatment plants show a deficit in effectively eliminating micro- and nanoplastics (MNP) from water, particularly in the case of nanoplastics. In this work, the magnetic removal of three different MNP types across three orders of magnitude in size (100 nm-100 µm) is investigated systematically. Superparamagnetic iron oxide nanoparticles (SPIONs) tend to attract oppositely charged MNPs and form aggregates that can be easily collected by a magnet. It shows that especially the smallest fractions (100-300 nm) can be separated in ordinary high numbers (1013  mg-1 SPION) while the highest mass is removed for MNP between 2.5 and 5 µm. The universal trend for all three types of MNP can be fitted with a derived model, which can make predictions for optimizing SPIONs for specific size ranges in the future.

Direct-Patterning ZnO Deposition by Atomic-Layer Additive Manufacturing Using a Safe and Economical Precursor.

Area-selective atomic layer deposition (AS-ALD) is a bottom-up nanofabrication method delivering single atoms from a molecular precursor. AS-ALD enables self-aligned fabrication and outperforms lithography in terms of cost, resistance, and equipment prerequisites, but it requires pre-patterned substrates and is limited by insufficient selectivity and finite choice of substrates. These challenges are circumvented by direct patterning with atomic-layer additive manufacturing (ALAM) - a transfer of 3D-printing principles to atomic-layer manufacturing where a precursor supply nozzle enables direct patterning instead of blanket coating. The reduced precursor vapor consumption in ALAM as compared with ALD calls for the use of less volatile precursors by replacing diethylzinc used traditionally in ALD with bis(dimethylaminopropyl)zinc, Zn(DMP)2 . The behavior of this novel ZnO ALAM process follows that of the corresponding ALD in terms of deposit quality and growth characteristics. The temperature window for self-limiting growth of stoichiometric, crystalline material is 200-250 °C. The growth rates are 0.9 Å per cycle in ALD (determined by spectroscopic ellipsometry) and 1.1 Å per pass in ALAM (imaging ellipsometry). The preferential crystal orientation increases with temperature, while energy-dispersive X-ray spectroscopic and XPS show that only intermediate temperatures deliver stoichiometric ZnO. A functional thin-film transistor is created from an ALAM-deposited ZnO line and characterized.

Supraparticles with a Mechanically Triggerable Color-Change-Effect to Equip Coatings with the Ability to Report Damage.

Small scratches and abrasion cause damage to packaging coatings. Albeit often invisible to the human eye, such small defects in the coating may ultimately have a strong negative impact on the whole system. For instance, gases may penetrate the coating and consequently the package barrier, thus leading to the degradation of sensitive goods. Herein, the indicators of mechanical damage in the form of particles are reported, which can readily be integrated into coatings. Shear stress-induced damage is indicated by the particles via a color change. The particles are designed as core-shell supraparticles. The supraparticle core is based on rhodamine B dye-doped silica nanoparticles, whereas the shell is made of alumina nanoparticles. The alumina surface is functionalized with a monolayer of a perylene dye. The resulting core-shell supraparticle system thus contains two colors, one in the core and one in the shell part of the architecture. Mechanical damage of this structure exposes the core from the shell, resulting in a color change. With particles integrated into a coating lacquer, mechanical damage of a coating can be monitored via a color change and even be related to the degree of oxygen penetration in a damaged coating.

Host-Guest Systems on the Surface of Functionalized Superparamagnetic Iron Oxide Nanoparticles (SPIONs) Utilizing Hamilton Receptors and Cyanurate Derivative Molecules.

The study of hydrogen bonding interactions at the level of functionalized nanoparticles remains highly challenging and poorly explored area. In this work, superparamagnetic iron oxide nanoparticles (SPIONs) were orthogonally functionalized using receptors bearing multiple hydrogen bonding motifs. Pristine SPIONs were modified by wet chemical processes with Hamilton receptors (hosts), or cyanurate-guest molecules linked to phosphonic acid moieties for monolayer functionalization. The modified surfaces were fully characterized and the number of attached ligands on the surface were determined. The host-guest interactions on the interface of modified SPIONs were investigated by using UV-Vis spectroscopic titrations. Functionalized SPIONs demonstrated two to three magnitudes stronger binding affinities as compared to the related molecular interactions in solution due to synergistic effects on complex surface environment. Higher supramolecular binding ratios of host-guest interactions on the modified surface were emerged. These studies provide fundamental insights into supramolecular complexations on the surface at solid-liquid interface systems with applications in engineered nanomaterials, nano-sensing devices, and drug delivery systems.

Covalent 2D Patterning, Local Electronic Structure and Polarization Switching of Graphene at the Nanometer Level.

A very facile and efficient protocol for the covalent patterning and properties tuning of graphene is reported. Highly reactive fluorine radicals were added to confined regions of graphene directed by laser writing on graphene coated with 1-fluoro-3,3-dimethylbenziodoxole. This process allows for the realization of exquisite patterns on graphene with resolutions down to 200 nm. The degree of functionalization, ranging from the unfunctionalized graphene to extremely high functionalized graphene, can be precisely tuned by controlling the laser irradiation time. Subsequent substitution of the initially patterned fluorine atoms afforded an unprecedented graphene nanostructure bearing thiophene groups. This substitution led to a complete switch of both the electronic structure and the polarization within the patterned graphene regions. This approach paves the way towards the precise modulation of the structure and properties of nanostructured graphene.

Mixed Organic Ligand Shells: Controlling the Nanoparticle Surface Morphology toward Tuning the Optoelectronic Properties.

Precise control over the ratio of perylene bisimide (PBI) monomers and aggregates, immobilized on alumina nanoparticle (NP) surfaces, is demonstrated. Towards this goal, phosphonic acid functionalized PBI derivatives (PA-PBI) are shown to self-assemble into stoichiometrically mixed monolayers featuring aliphatic, glycolic, or fluorinated phosphonic acid ligands, serving as imbedding matrix (PA-M) to afford core-shell NPs. Different but, nevertheless, defined PBI monomer/aggregate composition is achieved by either the variation in the PA-PBI to PA-M ratios, or the utilization of different PA-Ms. Various steady-state as well as time-resolved spectroscopy techniques are applied to probe the core-shell NPs with respect to changes in their optical properties upon variations in the shell composition. To this end, the ratio between monomer and excimer-like emission assists in deriving information on the self-assembled monolayer composition, local ordering, and corresponding aggregate content. With the help of X-ray reflectivity measurements, accompanied by molecular dynamics simulations, the built-up of the particle shells, in general, and the PBI aggregation behavior, in particular, are explored in depth.

Spatially Resolved Bottom-Side Fluorination of Graphene by Two-Dimensional Substrate Patterning.

Patterned functionalization can, on the one hand, open the band gap of graphene and, on the other hand, program demanding designs on graphene. The functionalization technique is essential for graphene-based nanoarchitectures. A new and highly efficient method was applied to obtain patterned functionalization on graphene by mild fluorination with spatially arranged AgF arrays on the structured substrate. Scanning Raman spectroscopy (SRS) and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDS) were used to characterize the functionalized materials. For the first time, chemical patterning on the bottom side of graphene was realized. The chemical nature of the patterned functionalization was determined to be the ditopic scenario with fluorine atoms occupying the bottom side and moieties, such as oxygen-containing groups or hydrogen atoms, binding on the top side, which provides information about the mechanism of the fluorination process. Our strategy can be conceptually extended to pattern other functionalities by using other reactants. Bottom-side patterned functionalization enables utilization of the top side of a material, thereby opening up the possibilities for applications in graphene-based devices.

Enhanced In Vitro Biocompatibility and Water Dispersibility of Magnetite and Cobalt Ferrite Nanoparticles Employed as ROS Formation Enhancer in Radiation Cancer Therapy.

Efficient magnetic reactive oxygen species (ROS) formation enhancing agents after X-ray treatment are realized by functionalizing superparamagnetic magnetite (Fe3 O4 ) and Co-ferrite (CoFe2 O4 ) nanoparticles with self-assembled monolayers (SAMs). The Fe3 O4 and CoFe2 O4 nanoparticles are synthesized using Massart's coprecipitation technique. Successful surface modification with the SAM forming compounds 1-methyl-3-(dodecylphosphonic acid) imidazolium bromide, or (2-{2-[2-hydroxy-ethoxy]-ethoxy}-ethyl phosphonic acid provides biocompatibility and long-term stability of the Fe3 O4 and CoFe2 O4 nanoparticles in cell media. The SAM-stabilized ferrite nanoparticles are characterized with dynamic light scattering, X-ray powder diffraction, a superconducting quantum interference device, Fourier transform infrared attenuated total reflectance spectroscopy, zeta potential measurements, and thermogravimetric analysis. The impact of the SAM-stabilized nanoparticles on the viability of the MCF-7 cells and healthy human umbilical vein endothelial cells (HUVECs) is assessed using the neutral red assay. Under X-ray exposure with a single dosage of 1 Gy the intracellular SAM stabilized Fe3 O4 and CoFe2 O4 nanoparticles are observed to increase the level of ROS in MCF-7 breast cancer cells but not in healthy HUVECs. The drastic ROS enhancement is associated with very low dose modifying factors for a survival fraction of 50%. This significant ROS enhancement effect by SAM-stabilized Fe3 O4 and CoFe2 O4 nanoparticles constitutes their excellent applicability in radiation therapy.

Highly Efficient Encapsulation and Phase Separation of Apolar Molecules by Magnetic Shell-by-Shell-Coated Nanocarriers in Water.

We report on the development of a supramolecular nanocarrier concept that allows for the encapsulation and separation of small apolar molecules from water. The nanocarriers consist of shell-by-shell-coated nanoparticles such as TiO2 and ferromagnetic Fe3 O4 . The first ligand shell is provided by covalently bound hexadecyl phosphonic acid (PAC16 ) and the second shell by noncovalently assembled amphiphiles rendering the hybrid architecture soluble in water. Agitation of these constructs with water containing the hydrocarbons G1-G4, the fluorescent marker G5, the polychlorinated biphenyl PCB 77, or crude oil leads to a very efficient uptake (up to 411 %) of the apolar contaminant. In case of the hybrids containing a Fe3 O4 core, straightforward phase separation by the action of an external magnet is provided. The load can easily be released by a final treatment with an organic solvent.

Structural investigations of self-assembled monolayers for organic electronics: results from X-ray reflectivity.

Self-assembled monolayers (SAMs) have been established as crucial interlayers and electronically active layers in organic electronic devices, such as organic light emitting diodes (OLEDs), organic photovoltaics (OPVs), organic thin film transistors (OTFTs), and nonvolatile memories (NVMs). The use of self-assembling functionalized organic molecules is beneficial due to mainly three advantages compared with common thin film deposition approaches. (1) Molecular self-assembly occurs with surface selectivity, determined by the interaction between the functional anchor group of the organic molecules and the target surface. (2) The film thickness of the resulting layers is perfectly controllable on the angstrom scale, due to the self-terminating film formation to only a single molecular layer. And finally, (3) the wide variability in the chemical structure of such molecules enables different SAM functionalities for devices, ranging from electrical insulation to charge storage to charge transport. The SAM approach can be further expanded by employing several functionalized molecules to create mixed SAMs with consequently mixed properties. The function of SAMs in devices depends not only on the chemical structure of the molecules but also on their final arrangement and orientation on the surface. A reliable and nondestructive in-depth characterization of SAMs on nonconductive oxide surfaces is still challenging because of the very small thickness and the impracticality of methods such as scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). In this Account, we illustrate how X-ray reflectivity (XRR) provides analytical access to major questions of SAM composition, morphology, and even formation by means of investigations of pure and mixed SAMs based on phosphonic acids (PAs) of various chain structures on flat alumina (AlOx) surfaces. XRR is an analytical method that provides access to spatially averaged structural depth profiles over a relatively large area of several square micrometers. The key outcome of XRR, the surface-normal electron density profile of the SAMs, leads to precise information on the SAM thickness with subangstrom resolution and allows for the determination of molecular tilt angles and packing densities. We have systematically increased the chemical complexity of PA molecules and the resulting SAMs, utilizing XRR to provide insight into the SAM structures. In SAMs composed of functionalized molecules or complex chain structures, the distribution of electron rich and electron poor signatures is detected and thus the molecular order within the SAM is determined. In mixed SAMs of two different molecular species, electron density profiles reveal the morphology and how the surface-normal structure changes if one component of the mixed SAM is altered. Furthermore, XRR was applied to investigate in situ the self-assembly of functionalized PA molecules from solution by tracking the monolayer growth over time. Even though the results provided by XRR on in-plane molecular arrangement are limited, it presents excellent information on the molecular scale along the surface normal and in addition allows for drawing conclusions on the intermolecular interactions within the SAM.

Quantitative Determination and Comparison of the Surface Binding of Phosphonic Acid, Carboxylic Acid, and Catechol Ligands on TiO2 Nanoparticles.

The adsorption, desorption, co-adsorption, and exchange behavior of phosphonic acid, carboxylic acid, and catechol derivatives on the surface of titanium oxide (anatase) nanoparticles are investigated. Thermogravimetric analysis provides a facile and fast-track quantitative determination of the wet-chemical monolayer adsorption constants and grafting densities of ten adsorbates, all under neutral pH conditions. This characterization protocol allows straightforward quantification of the relevant thermodynamic data of ligand adsorption and a comparison of ligand adsorption strengths. The reported procedure is proposed as a universal tool and it should be applicable to many other colloidal metal oxide materials. Moreover, the determined values for the adsorption constants and the monolayer grafting densities provide a toolbox for the assessment of the adsorbates' behavior in desorption, exchange, and co-adsorption equilibria. This versatile evaluation procedure will help to identify optimal monolayer-surface combinations and to evaluate critical parameters, such as monolayer robustness, ligand exchange rates, or targeted mixed assembly of functionalities.

Enhancing the Dispersibility of TiO2 Nanorods and Gaining Control over Region-Selective Layer Formation.

We demonstrate that the dispersibility and reactivity of core-shell TiO2 nanorods (NRs) can be controlled significantly through functionalization with a combination of ligands based on phosphonic acid derivatives (PAs). Specifically, a glycol based PA allows dispersion of the NRs in methanol (MeOH). On the other hand, incorporating an alkyne terminated PA in the ligand shell of the NRs allows for a copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction with an azide-patterned aluminum oxide (AlOx) substrate and forms a region-selectively deposited film of NRs. We clearly demonstrate that the quality of the NR films correlates strongly with the stability of the NR dispersions in the reaction medium. In particular, tuning the concentration of alkyne PA in the ligand shell inhibits aggregation of the NRs on the substrate, while reactivity for the CuAAC reaction is maintained. The surface coverage with NRs fits the Langmuir model. This study illustrates that surface functionalization of AlOx substrates can be effectively and conveniently controlled through enhancing the dispersibility of the NRs using mixed ligand shells.

Wide Band-Gap Bismuth-based p-Dopants for Opto-Electronic Applications.

Ten new efficient p-dopants for conductivity doping of organic semiconductors for OLEDs are identified. The key advantage of the electrophilic tris(carboxylato) bismuth(III) compounds is the unique low absorption of the resulting doped layers which promotes the efficiency of OLED devices. The combination of these features with their low fabrication cost, volatility, and stability, make these materials very attractive as dopants in organic electronics.

Very Facile Polarity Umpolung and Noncovalent Functionalization of Inorganic Nanoparticles: A Tool Kit for Supramolecular Materials Chemistry.

The facile assembly of shell-by-shell (SbS)-coated nanoparticles [TiO2-PAC16]@shell 1-7 (PAC16 = hexadecylphosphonic acid), which are soluble in water and can be isolated as stable solids, is reported. In these functional architectures, an umpolung of dispersibility (organic apolar versus water) was accomplished by the noncovalent binding of ligands 1-7 to titania nanoparticles [TiO2-PAC16] containing a first covalent coating with PAC16. Ligands 1-7 are amphiphilic and form the outer second shell of [TiO2-PAC16]@shell 1-7. The tailor-designed dendritic building blocks 3-5 contain negative and positive charges in the same molecule, and ligands 6 and 7 contain a perylenetetracarboxylic acid dimide (PDI) core (6/7) as a photoactive reporter component. In the redox and photoactive system [TiO2-PAC16]@shell 7, electronic communication between the inorganic core to the PDI ligands was observed.

Region-Selective Deposition of Core-Shell Nanoparticles for 3D Hierarchical Assemblies by the Huisgen 1,3-Dipolar Cycloaddition.

A method for the region-selective deposition of nanoparticles (NPs) by the Huisgen 1,3-dipolar cycloaddition is presented. The approach enables defined stacking of various oxide NPs in any order with control over layer thickness. Thereby the reaction is performed between a substrate, functionalized with a self-assembled monolayer of an azide-bearing phosphonic acid (PA) and aluminum oxide (AlO(x)) NPs functionalized with an alkyne bearing PA. The layer of alkyne functionalized AlO(x) NPs is then used as substrate for the deposition of azide-functionalized indium tin oxide (ITO) NPs to provide a binary stack. This progression is then conducted with alkyne-functionalized CeO2 NPs, yielding a ternary stack of NPs with three different NP cores. The stacks are characterized by AFM and SEM, defining the region-selectivity of the deposition technique. Finally, these assemblies have been tested in devices as a dielectric to form a capacitor resulting in a dramatic increase in the measured capacitance.

Fullerene van der Waals oligomers as electron traps.

Density functional theory calculations indicate that van der Waals fullerene dimers and larger oligomers can form interstitial electron traps in which the electrons are even more strongly bound than in isolated fullerene radical anions. The fullerenes behave like "super atoms", and the interstitial electron traps represent one-electron intermolecular σ-bonds. Spectroelectrochemical measurements on a bis-fullerene-substituted peptide provide experimental support. The proposed deep electron traps are relevant for all organic electronics applications in which non-covalently linked fullerenes in van der Waals contact with one another serve as n-type semiconductors.

Broad-Spectrum Supramolecularly Reloadable Antimicrobial Coatings.

Antimicrobial surfaces limit the spread of infectious diseases. To date, there is no antimicrobial coating that has widespread use because of short-lived and limited spectrum efficacy, poor resistance to organic material, and/or cost. Here, we present a paint based on waterborne latex particles that is supramolecularly associated with quaternary ammonium compounds (QACs). The optimal supramolecular pairing was first determined by immobilizing selected ions on self-assembled monolayers exposing different groups. The QAC surface loading density was then increased by using polymer brushes. These concepts were adopted to develop inexpensive paints to be applied on many different surfaces. The paint could be employed for healthcare and food production applications. Its slow release of QAC allows for long-lasting antimicrobial action, even in the presence of organic material. Its efficacy lasts for more than 90 washes, and importantly, once lost, it can readily be restored by spraying an aqueous solution of the QAC. We mainly tested cetyltrimethylammonium as QAC as it is already used in consumer care products. Our antimicrobial paint is broad spectrum as it showed excellent antimicrobial efficiency against four bacteria and four viruses.

Improving the charge transport in self-assembled monolayer field-effect transistors: from theory to devices.

A three-pronged approach has been used to design rational improvements in self-assembled monolayer field-effect transistors: classical molecular dynamics (MD) simulations to investigate atomistic structure, large-scale quantum mechanical (QM) calculations for electronic properties, and device fabrication and characterization as the ultimate goal. The MD simulations reveal the effect of using two-component monolayers to achieve intact dielectric insulating layers and a well-defined semiconductor channel. The QM calculations identify improved conduction paths in the monolayers that consist of an optimum mixing ratio of the components. These results have been used both to confirm the predictions of the calculations and to optimize real devices. Monolayers were characterized with X-ray reflectivity measurements and by electronic characterization of complete devices.

Ultralow-power organic complementary circuits.

The prospect of using low-temperature processable organic semiconductors to implement transistors, circuits, displays and sensors on arbitrary substrates, such as glass or plastics, offers enormous potential for a wide range of electronic products. Of particular interest are portable devices that can be powered by small batteries or by near-field radio-frequency coupling. The main problem with existing approaches is the large power consumption of conventional organic circuits, which makes battery-powered applications problematic, if not impossible. Here we demonstrate an organic circuit with very low power consumption that uses a self-assembled monolayer gate dielectric and two different air-stable molecular semiconductors (pentacene and hexadecafluorocopperphthalocyanine, F16CuPc). The monolayer dielectric is grown on patterned metal gates at room temperature and is optimized to provide a large gate capacitance and low gate leakage currents. By combining low-voltage p-channel and n-channel organic thin-film transistors in a complementary circuit design, the static currents are reduced to below 100 pA per logic gate. We have fabricated complementary inverters, NAND gates, and ring oscillators that operate with supply voltages between 1.5 and 3 V and have a static power consumption of less than 1 nW per logic gate. These organic circuits are thus well suited for battery-powered systems such as portable display devices and large-surface sensor networks as well as for radio-frequency identification tags with extended operating range.

A Sustainable Method for Removal of the Full Range of Liquid and Solid Hydrocarbons from Water Including Up- and Recycling.

Beyond their CO2 emittance when burned as fuels, hydrocarbons (HCs) serve as omnipresent raw materials and commodities. No matter if as liquid oil spills or the endless amounts of plastic roaming the oceans, HCs behave as persistent pollutants with water as main carrier to distribute. Even if their general chemical structure [-(CH2 )n -] is quite simple, the endless range of n leads to contaminations of different appearances and properties. A water remediation method based on superparamagnetic iron oxide nanoparticles (SPIONs) modified with self-assembled monolayers of alkyl phosphonic acid derivatives is presented. These molecules enable the SPIONs to non-covalently bind HCs, independently from the molecular weight, size and morphology. The attractive interaction is mainly based on hydrophobic and Coulomb interaction, which allows recycling of the SPIONs. The superparamagnetic core allows a simple magnetic collection and separation from the water phase which makes it a promising addition to wastewater treatment. Agglomerates of collected plastic "waste" even exhibit superior adsorption properties for crude oil, another hydrocarbon waste which gives these collected wastes a second life. This upcycling approach combined with presented recycling methods enables a complete recycling loop.