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Responsive nanomaterials that can undergo reversible changes in morphology are interesting for the development of functional materials that interact with and respond to their environment. Amphiphilic block copolymers are well-known for their ability to create a wide range of supramolecular nanostructures in solution. Arylazopyrazoles (AAPs) are versatile molecular photoswitches, which change their configuration and hydrophobicity upon irradiation with UV light (365 nm, Z isomer, less hydrophobic) and green light (520 nm, E isomer, more hydrophobic). In this work, photoswitchable block copolymers containing arylazopyrazole tetraethylene glycol methacrylate (AAPMA) and oligo(ethylene glycol) methacrylate (OEGMA) forming amphiphilic POEGMA- b -PAAPMA with varying block lengths are prepared by RAFT polymerization. The photochemical properties of AAP persist in the polymers. Due to their amphiphilic structure, the polymers self-assemble into supramolecular morphologies in water. Remarkably, photoisomerization results in a reversible change in the self-assembly behavior. Specifically, spherical and cylindrical micelles are observed for POEGMA 33 - b -PAAPMA 47 when illuminated with green or UV light during assembly. Furthermore, the morphology of assembled structures can be reversibly switched by subsequent irradiation with UV and green light.

Azoarene isomerization lies at the heart of numerous applications from catalysis or energy storage to photopharmacology. While efficient switching between their E and Z isomers predominantly relies on UV light, a recent study by Klajn and co-workers introduced visible light sensitization of E azoarenes and subsequent isomerization as a tool coined disequilibration by sensitization under confinement (DESC) to obtain high yields of the Z isomer. This host-guest approach is, however, still constrained to minimally substituted azoarenes with limited applicability in advanced molecular systems. Herein, we expand DESC for the assembly of surfactants at the air-water interface. Leveraging our expertise with photoswitchable amphiphiles, we induce substantial alterations of water's surface tension through reversible arylazopyrazole isomerization. After studying the binding of charged surfactants to the host, we find that the surface activity differences upon visible light irradiation for both isomers are comparable to those obtained by UV light excitation. The method is demonstrated on a large concentration range and can be activated using green or red light, depending on the sensitizer chosen. The straightforward implementation of photoswitch sensitization in a complex molecular network showcases how DESC enables the improvement of existing systems and the development of novel applications driven by visible light., (© 2024 Wiley‐VCH GmbH.)

In order to design new nanomaterials with improved functionalities, magnetite nanoparticles (MNP) modified with arylazopyrazole (AAP) molecular photoswitches are presented. Water dispersibility is achieved by using poly(acrylic acid) (pAA) as a multidentate ligand, which is modified with AAP by amide coupling. The polymer ligand stabilizes the MNP, allows for E - Z isomerization of the photoswitch, and provides pH responsiveness. Three different AAP are synthesized and attached to pAA via amide coupling giving pAA-AAP with photoswitches substituted statistically along the hydrophilic polymer backbone. MNP are synthesized by coprecipitation and pAA-AAP is introduced as a stabilizing agent in situ. Photoisomerization of pAA-AAP and pAA-AAP@MNP is investigated showing good photostationary states and cyclability. The MNP can be assembled and dispersed reversibly in water either by applying a magnetic field or by a change in pH.

This study investigates unexpected competitive host-guest interactions of β-cyclodextrin (β-CD), which can occur with polymers in aqueous solution, using the examples of the two polymers poly(oligo(ethylene glycol) methyl ether methacrylate) and poly(glycerol mono methacrylate). Systematic structural modifications of the polymer provide insight into the host-guest interaction with β-CD and the competition between side chains and end groups such as hydrophobic end groups remaining from reversible addition fragmentation chain transfer polymerization or intentionally implemented molecular recognition units such as arylazopyrazole photoswitches., (© 2024 Wiley‐VCH GmbH.)

Inspired by nature, self-regulation can be introduced in synthetic hydrogels by incorporating chemo-mechanical signals or coupled chemical reactions to maintain or adapt the material's physico-chemical properties when exposed to external triggers. In this work, we present redox and light dual stimuli responsive hydrogels capable of rapidly adapting the polymer crosslinking network while maintaining hydrogel stability. Upon irradiation with UV light, polymer hydrogels containing redox responsive disulfide crosslinks and light responsive ortho-nitrobenzyl moieties show a release of payload accompanied by adaptation of the hydrogel network towards higher stiffness due to in situ crosslinking by S-nitrosylation. Whereas the hydrogel design allows the network to either become softer in presence of reducing agent glutathione or stiffer upon UV irradiation, simultaneous application of both stimuli induces network self-regulation resulting in a pulsatile form of payload release from the hydrogel. Finally, adaptive stiffness was used to make tunable hydrogels as substrates for different cell lines., (© 2024 Wiley-VCH GmbH.)

Molecular photoswitches are increasingly being implemented in bioactive compounds and responsive materials. For this purpose, photoswitches must be coupled to a wide variety of substrates and scaffolds. We present a library of "clickable" arylazopyrazoles (AAPs), which can be conjugated by Cu-catalyzed alkyne azide cycloaddition (CuAAC). All synthesized AAP alkynes show good photostationary states (at least 88%) and long half-life times of the Z -isomer (18 to 108 h). The AAP azides decompose upon exposure to ultraviolet (UV) irradiation, but after CuAAC, all AAPs exhibit good photophysical properties.

Arylazopyrazoles (AAPs) are an important class of molecular photoswitches with high photostationary states (PSS) and long thermal lifetimes. The ultrafast photoisomerization of four water-soluble arylazopyrazoles, all of them featuring an ortho -dimethylated pyrazole ring, is studied by narrowband femtosecond transient absorption spectroscopy and ab initio molecular dynamics simulations. Upon S 1 (nπ*) photoexcitation of the planar E -isomers ( E -AAPs), excited-state bi-exponential decays with time constants τ 1 in the 220-440 fs range and τ 2 in the 1.4-1.8 ps range are observed, comparable to those reported for azobenzene (AB). This is indicative of the same photoisomerization mechanism as has been reported for ABs. In contrast to the planar E -AAPs, a twisted E -AAP with two methyl groups in ortho -position of the phenyl ring displays faster initial photoswitching with τ 1 = 170 ± 10 fs and τ 2 = 1.6 ± 0.1 ps. Our static DFT calculations and ab initio molecular dynamics simulations of E -AAPs on the S 0 and S 1 potential energy surfaces suggest that twisted E -isomer azo photoswitches exhibit faster initial photoisomerization dynamics out of the Franck-Condon region due to a weaker π-coordination of the central CNNC unit to the aromatic ligands.

Invited for the cover of this issue are the groups of Kentaro Tanaka at Nagoya University and Bart Jan Ravoo at the University of Münster. The image depicts the photoisomerization of a mesogen upon irradiation with different wavelengths of light. Read the full text of the article at 10.1002/chem.202302958., (© 2024 Wiley-VCH GmbH.)

Azoheteroarenes are emerging as powerful alternatives to azobenzene molecular photoswitches. In this study, water-soluble arylazoisoxazole photoswitches are introduced. UV/vis and NMR spectroscopy revealed moderate to very good photostationary states and reversible photoisomerization between the E- and Z-isomers over multiple cycles with minimal photobleaching. Several arylazoisoxazoles form host-guest complexes with β- and γ-cyclodextrin with significant differences in binding constants for each photoisomer as shown by isothermal titration calorimetry and NMR experiments, indicating their potential for photoresponsive host-guest chemistry in water. One carboxylic acid functionalized arylazoisoxazole can act as a hydrogelator, allowing gel properties to be manipulated reversibly with light. The hydrogel was characterized by rheological experiments, atom force microscopy and transmission electron microscopy. These results demonstrate that arylazoisoxazoles can find applications as molecular photoswitches in aqueous media., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Light-responsive surfaces are attracting increasing interest, not least because their physicochemical properties can be selectively and temporally controlled by a non-invasive stimulus. Most existing immobilization strategies involve the chemical attachment of light-responsive moieties to the surface, although this approach often suffers from a low surface concentration of active species or a high inhomogeneity of applied coatings. Herein, electropolymerization of carbazoles as a facile and rapid approach for preparing light-responsive azo-based surface coatings is presented. The electrochemical oxidative polymerization of bis-carbazole containing azo-monomers yields stable films, in which the photochemical properties and specific pH sensitivity of azo molecular switches are retained. Moreover, the molecular design enables electrocatalytic control over Z→E azo double bond isomerization facilitated by the conductive polycarbazole backbone. Ultimately, the high degree of control over macromolecular properties yields conductive surface coatings responsive to a range of stimuli, showing great promise as a strategy for versatile application in organic electronics., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Aromatic units tethered with an azo (-N=N-) functionality comprise a unique class of compounds, known as molecular photoswitches, exhibiting a reversible transformation between their E- and Z-isomers in response to photo-irradiation. Photoswitches have been explored extensively in the recent past to prepare dynamic self-assembled materials, optoelectronic devices, responsive biomaterials, and more. Most of such materials involve azobenzenes as the molecular photoswitch and to date, SciFinder lists more than 7000 articles and 1000 patents. Subsequently, a great deal of effort has been invested to improve the photo-isomerization efficiency and related mesoscopic properties of azobenzenes. Recently, azoheteroarenes and cyclic azobenzenes, such as arylazopyrazoles, arylazoisoxazoles, arylazopyridines, and diazocines, have emerged as second generation molecular photoswitches beyond conventional azobenzenes. These photoswitches offer distinct photoswitching behavior and responsive properties which make them highly promising candidates for multifaceted applications ranging from photoresponsive materials to photopharmacophores. In this minireview, we introduce the structural refinement and photoresponsive properties of azoheteroarenes and diazocines and summarize the state-of-the-art on utilizing these photoswitches as responsive building blocks in supramolecular assembly, material science and photopharmacology, highlighting their versatile photochemical behavior, enhanced functionality, and latest applications., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Time-of-flight secondary ion mass spectrometry is one of the most promising techniques for label-free analysis of biomolecules with nanoscale spatial resolution. However, high-resolution imaging of larger biomolecules such as phospholipids and peptides is often hampered by low yields of molecular ions. Matrix-enhanced SIMS (ME-SIMS), in which an organic matrix is added to the sample, is one promising approach to enhancing the ion yield for biomolecules. Optimizing this approach has, however, been challenging because the processes involved in increasing the ion yield in ME-SIMS are not yet fully understood. In this work, the matrix α-cyano-4-hydroxycinnamic acid (HCCA) has been combined with cluster primary ion analysis to better understand the roles of proton donation and reduced fragmentation on lipid molecule ion yield. A model system consisting of 1:100 mol ratio dipalmitoylphosphatidylcholine (DPPC) in HCCA as well as an HCCA-coated mouse brain cryosection have been studied using a range of Bi and Ar cluster ions. Although the molecular ion yield increased with an increase in cluster ion size, the enhancement of the signals from intact lipid molecules decreased with an increase in cluster ion size for both the model system and the mouse brain. Additionally, in both systems, protonated molecular ions were significantly more enhanced than sodium and potassium cationized molecules for all of the primary ions utilized. For the model system, the DPPC molecular ion yield was increased by more than an order of magnitude for all of the primary ions studied, and fragmentation of DPPC was dramatically reduced. However, on the brain sample, even though the HCCA matrix reduced DPPC fragmentation for all of the primary ions studied, the matrix coating suppressed the ion yield for some lipids when the larger cluster primary ions were employed. This indicated insufficient migration of the lipids into the matrix coating, so that dilution by the matrix overpowered the enhancement effect. This study provides strong evidence that the HCCA matrix both enhances protonation and reduces fragmentation. For imaging applications, the ability of the analytes to migrate to the surface of the matrix coating is also a critical factor for useful signal enhancement. This work demonstrates that the HCCA matrix provides a softer desorption environment when using Bi cluster ions than that obtained using the large gas cluster ions studied alone, indicating the potential for improved high spatial resolution imaging with ME-SIMS.

N-Heterocyclic carbene (NHC)-modified planar gold surfaces (NHC@Au) were found to be more susceptible toward wet chemical etching than undecorated surface areas. Site-selective decoration of NHCs on Au was achieved by microcontact printing (μCP) of the NHC precursors 1,3-bis(diisopropylphenyl)imidazol-3-ium hydrogen carbonate (IPr(H)[HCO 3 ]) or 1,3-dimethylbenzimidazol-3-ium hydrogen carbonate (BIMe(H)[HCO 3 ]). Strikingly, BIMe@Au showed concentration-dependent etching behavior, tunable from a positive resist to a negative resist. Surface patterning was verified by time-of-flight secondary-ion mass spectrometry and Kelvin probe force microscopy. Moreover, orthogonal μCP enabled the patterned functionalization of planar Au with both IPr and 1-eicosanethiol and the subsequent formation of three-dimensional structures with a single etching step. The selective removal of Au by functionalization with a surface ligand is unprecedented and enables novel applications of NHCs in materials chemistry and nanofabrication.

Cellular membrane area is a key parameter for any living cell that is tightly regulated to avoid membrane damage. Changes in area-to-volume ratio are known to be critical for cell shape, but are mostly investigated by changing the cell volume via osmotic shocks. In turn, many important questions relating to cellular shape, membrane tension homeostasis and local membrane area cannot be easily addressed because experimental tools for controlled modulation of cell membrane area are lacking. Here we show that photoswitching an amphiphilic azobenzene can trigger its intercalation into the plasma membrane of various mammalian cells ranging from erythrocytes to myoblasts and cancer cells. The photoisomerization leads to a rapid (250-500 ms) and highly reversible membrane area change (ca 2 % for erythrocytes) that triggers a dramatic shape modulation of living cells., (© 2023. The Author(s).)

Nanoparticles offer unique physical and chemical properties. Dip pen nanolithography of nanoparticles enables versatile patterning and nanofabrication with potential application in electronics and sensing, but is not well studied yet. Herein, the patterned deposition of various nanoparticles onto unmodified silicon substrates is presented. It is shown that aqueous solutions of hydrophilic citrate and cyclodextrin functionalized gold nanoparticles as well as poly(acrylic) acid decorated magnetite nanoparticles are feasible for writing nanostructures. Both smaller and larger nanoparticles can be patterned. Hydrophobic oleylamine or n-dodecylamine capped gold nanoparticles and oleic acid decorated magnetite nanoparticles are deposited from toluene. Tip loading is carried out by dip-coating, and writing succeeds fast within 0.1 s. Also, coating with longer tip dwell times, at different relative humidity and varying frequency are studied for deposition of nanoparticle clusters. The resulting feature size is between 300 and 1780 nm as determined by scanning electron microscopy. Atomic force microscopy confirms that the heights of the deposited structures correspond to a single or double layer of nanoparticles. Higher writing speeds lead to smaller line thicknesses, offering possibilities to more complex structures. Dip pen nanolithography can hence be used to pattern nanoparticles on silicon substrates independent of the surface chemistry., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

Photoswitches have long been employed in coatings for surfaces and substrates to harness light as a versatile stimulus to induce responsive behavior. We previously demonstrated the viability of arylazopyrazole (AAP) as a photoswitch in self-assembled monolayers (SAMs) on silicon and glass surfaces for photoresponsive wetting applications. We now aim to transfer the excellent photophysical properties of AAPs to polymer brush coatings. Compared to SAMs, polymer brushes offer enhanced stability and an increase of the thickness and density of the functional organic layer. In this work, we present thiolactone acrylate copolymer brushes which can be post-modified with AAP amines as well as hydrophobic acrylates, making use of the unique chemistry of the thiolactones. This strategy enables photoresponsive wetting with a tuneable range of contact angle change on glass substrates. We show the successful synthesis of thiolactone hydroxyethyl acrylate copolymer brushes by means of surface-initiated atom-transfer radical polymerization with the option to either prepare homogeneous brushes or to prepare micrometer-sized brush patterns by microcontact printing. The polymer brushes were analyzed by atomic force microscopy, time-of-flight secondary ion spectrometry, and X-ray photoelectron spectroscopy. Photoresponsive behavior imparted to the brushes by means of post-modification with AAP is monitored by UV/vis spectroscopy, and wetting behavior of homogeneous brushes is measured by static and dynamic contact angle measurements. The brushes show an average change in static contact angle of around 13° between E and Z isomer of the AAP photoswitch for at least five cycles, while the range of contact angle change can be fine-tuned between 53.5°/66.5° ( E / Z ) and 81.5°/94.8° ( E / Z ) by post-modification with hydrophobic acrylates.

The design of responsive coatings has gained increasing attention recently, with light-responsive interfaces receiving particular appreciation, as their surface properties can be modulated with excellent spatiotemporal control. In this article, we present light-responsive conductive coatings acquired through a copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction between electropolymerized azide-functionalized poly(3,4-ethylenedioxythiophene) ( PEDOT-N 3 ) and arylazopyrazole ( AAP )-bearing alkynes. The UV/vis and X-ray photoelectron spectroscopy (XPS) data indicate a successful post-modification, supporting a covalent attachment of AAP moieties to PEDOT-N 3 . The thickness and degree of PEDOT-N 3 modification are accessible by varying the amount of passed charge during electropolymerization and time of reaction, respectively, providing a degree of synthetic control over the physicochemical material properties. The produced substrates demonstrate a reversible and stable light-driven switching of photochromic properties in both "dry" and swelled states, as well as efficient electrocatalytic Z → E switching. The AAP -modified polymer substrates exhibit a light-controlled wetting behavior, demonstrating a consistently reversible switching of the static water contact angle with a difference up to 10.0° for CF 3 -AAP @ PEDOT-N 3 . The results highlight the application of conducting PEDOT-N 3 for the covalent immobilization of molecular switches while preserving their stimuli-responsive features.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is one of the most important techniques for chemical imaging of nanomaterials and biological samples with high lateral resolution. However, low ionization efficiency limits the detection of many molecules at low concentrations or in very small volumes. One promising approach to increasing the sensitivity of the technique is by the addition of a matrix that promotes ionization and desorption of important analyte molecules. This approach is known as matrix-enhanced secondary-ion mass spectrometry (ME-SIMS). We have investigated the effect of matrix acidity on molecular ion formation in three different biomolecules. A series of cinnamic acid based matrixes that vary in acidity was employed to systematically investigate the influence of matrix acidity on analyte ion formation. The positive ion signal for all three biomolecules showed a strong increase for more acidic matrixes. The most acidic matrix was then vapor-deposited onto mouse brain sections. This led to significant enhancement of lipid signals from the brain. This work indicates that proton donation plays an important role in the formation of molecular ions in ME-SIMS.

Surface patterning of functional materials is a key technology in various fields such as microelectronics, optics, and photonics. In micro- and nanofabrication, polymers are frequently employed either as photoreactive or thermoresponsive resists that enable further fabrication steps, or as functional adlayers in electronic and optical devices. In this article, a method is presented for imprint lithography using low molecular weight arylazoisoxazoles photoswitches instead of polymer resists. These photoswitches exhibit a rapid and reversible solid-to-liquid phase transition upon photo-isomerization at room temperature, making them highly suitable for reversible surface functionalization at ambient conditions. Beyond photo-induced imprint lithography with multiple write-and-erase cycles, prospective applications as patterned matrix for nanoparticles and etch resist on gold surfaces are demonstrated., (© 2022 The Authors. Small published by Wiley-VCH GmbH.)

Azobenzenes are among the best-studied molecular photoswitches and play a key role in the search for red-shifted photoresponsive materials for extended applications. Currently, most approaches deal with aromatic substitution patterns to achieve visible light application, on occasion paired with protonation to yield red-shifted absorption of the azonium species. Appropriate substitution patterns are essential to stabilize the latter approach, as conventional acids are known to induce a fast Z - to E -conversion. Here, we show that steady-state protonation of the azo-bridge instead is possible in simple azobenzenes when the p K a of the acid is low enough, yielding both the Z - and E -azonium as supported by UV-vis- and 1 H NMR spectroscopy as well as density functional theory calculations. Moreover, the steady-state protonation of para -methoxyazobenzene, specifically, yields photoisomerizable azonium ions in which the direction of switching is essentially reversed, that is, visible light produces the out-of-equilibrium Z -azonium. Although the current conditions render the visible light photoswitch unsuitable for in vivo and material application, the demonstrated understanding of simple azobenzenes paves the way for a great range of further work on this already widely studied photoswitch.

The development of redox-triggerable peptide hydrogels poses fundamental challenges, since the highly specific peptide architectures required inevitably limit the versatility of such materials. A powerful, yet rarely applied approach to bypass those barriers is the application of a mediating redox reaction to gradually decrease the pH during hydrogel formation. We report a versatile strategy to trigger the formation of peptide hydrogels from readily accessible acid-triggerable gelators by generating protons by oxidation of thioethers with triiodide. Adding thiodiglycol as a readily available thioether auxiliary to the basic precursor solution of a peptide gelator efficiently yielded hydrogels after mixing with triiodide, as studied in detail for Nap-FF and demonstrated for other peptides. Furthermore, incorporation of the thioether moiety in the gelator backbone via the amino acid methionine, as shown for the tailormade Nap-FMDM peptide, reduces the number of required additives., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The high spatiotemporal resolution of light as an external stimulus allows the control of shape, mechanical properties, and even forces generated by photoresponsive soft materials. For this purpose, supramolecular systems that respond readily and reversibly to photoirradiation and convert microscopic changes into macroscopic effects are needed. This work demonstrates the reversible light-responsive modulation of the osmotic pressure of an aqueous solution of an azobenzene-containing polymer (azopolymer) and α-cyclodextrin. Osmometry shows that this multivalent and photoresponsive host-guest complex can be used to modulate the concentration of solutes in the solution. Upon alternating irradiation with UV and blue light, the osmolality is reversibly switched by 28 mOsm kg -1 . The switching amplitude increases linearly with the concentration of azopolymer and cyclodextrin. This drastic change in osmotic pressure is achieved by carefully designing an azopolymer that provides multivalent interactions as well as high water solubility. In this way, our study demonstrates a tunable control of colligative properties by photoinduced modulation of supramolecular interactions.

Improving signal-to-noise and, thereby, image contrast is one of the key challenges needed to expand the useful applications of mass spectrometry imaging (MSI). Both instrumental and data analysis approaches are of importance. Univariate denoising techniques have been used to improve contrast in MSI images with varying levels of success. Additionally, various multivariate analysis (MVA) methods have proven to be effective for improving image contrast. However, the distribution of important but low intensity ions can be obscured in the MVA analysis, leading to a loss of chemically specific information. In this work we propose inverse maximum signal factors (MSF) denoising as an alternative approach to both denoising and multivariate analysis for MSI imaging. This approach differs from the standard MVA techniques in that the output is denoised images for each original mass peak rather than the frequently difficult to interpret scores and loadings. Five tests have been developed to optimize and validate the resulting denoised images. The algorithm has been tested on a range of simulated data with different levels of noise, correlated noise, varying numbers of underlying components, and nonlinear effects. In the simulations, an excellent correlation between the true images and the denoised images was observed for peaks with an original signal-to-noise ratio as low as 0.1, as long as there was sufficient intensity in the sum of the selected peaks. The power of the approach was then demonstrated on two time-of-flight secondary ion mass spectrometry (ToF-SIMS) images that contained largely uncorrelated noise and a laser post-ionization matrix-assisted laser desorption/ionization mass spectrometry (MALDI-2-MS) image that contained strongly correlated noise. The improvements in signal-to-noise increased with decreasing intensity of the original peaks. A signal-to-noise improvement of as much as two orders of magnitude was achieved for very low intensity peaks. MSF denoising is a powerful addition to the suite of image processing techniques available for studying mass spectrometry images.

Surface coatings that respond to external influences and change their physical properties upon application of external stimuli are of great interest, with light being a particularly desirable choice. Photoswitches such as azobenzenes have been employed in a range of photoresponsive coatings. One striking change in physical property of many photoresponsive coatings is their responsive wettability upon illumination. In this work, we present photoswitchable self-assembled monolayers based on arylazopyrazoles (AAPs). In solution, AAPs offer significant improvements in terms of the photostationary state, thermal stability, and fatigue resistance. The AAP photoswitch is coupled to triethoxysilanes for an easy, one-step functionalization of glass and silicon oxide surfaces. We show the synthesis of AAP-based silanes and the successful surface functionalization, and we confirm the excellent photoswitchability of the AAPs in a self-assembled monolayer upon alternating irradiation with UV (365 nm) and green (520 nm) light. The self-assembled monolayers are investigated by UV/vis spectroscopy, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and contact angle goniometry. We furthermore investigate the effect of substitution of the AAPs on the photoresponsive wetting behavior and compare this with density functional theory (DFT) calculations of the dipole moments of the AAPs.

Bidirectional photoswitching of arylazopyrazoles with visible light is enabled by substitution with pyrrolidine and piperidine in the ortho -position of the phenyl ring. The absorption maxima were red-shifted and the molar absorption coefficients in the visible range increased significantly, allowing the use of blue light (λ = 465 nm) for the E → Z isomerization and red light (λ = 600 nm) for the Z → E isomerization. N -Methylation of the pyrazole leads to an excellent thermal stability of the Z isomer.

Stimuli-responsive self-assembly of nanoparticles is a versatile approach for the bottom-up fabrication of adaptive and functional nanomaterials. For this purpose, anisotropic building blocks are of particular importance due to the unique shapes and structures that can be obtained upon self-assembly. Here, we demonstrate the photo-responsive self-assembly of plasmonic magnetic "dumbbell" Janus nanoparticles (Au-Fe 3 O 4 ) via the host-guest interaction of the supramolecular host cyclodextrin and the molecular photoswitch arylazopyrazole. We developed efficient ligand exchange procedures that enable the introduction of functional ligands, respectively, to the surface of the gold or magnetite core of the dumbbell. Our results indicate that distinct nanoparticle superstructures arise in aqueous solutions if nanoparticle aggregation is crosslinker-induced or self-induced and that the reversible formation and fragmentation of the superstructures can be modulated with light.

Cyclodextrin-based liquid crystals and their emerging applications are described in this tutorial review, which covers reports from the last decade with a focus on recent developments. Although cyclodextrins are among the best studied macrocyclic host molecules and liquid crystals have found widespread technological application, the integration of cyclodextrins in liquid crystals as versatile supramolecular materials has been barely explored. However, in the last few years promising innovations in molecular design as well as proof-of-concept applications such as ion-conductive and proton-conductive liquid crystals, nanoparticle additives for liquid crystal display technology, polyrotaxane-based liquid crystals and liquid crystal-based sensors have been reported. We discuss various examples of cyclodextrin-based liquid crystals that demonstrate the significant potential of these unique soft materials for future research and interdisciplinary applications.

Biodegradable supramolecular micelles were prepared exploiting the host-guest interaction of cyclodextrin and adamantane. Cyclodextrin-initiated polypeptides acted as the hydrophilic corona, whereas adamantane-terminated polycaprolactones served as the hydrophobic core.

Chemical reaction networks (CRN) embedded in hydrogels can transform responsive materials into complex self-regulating materials that generate feedback to counter the effect of external stimuli. This study presents hydrogels containing the β-cyclodextrin (CD) and ferrocene (Fc) host-guest pair as supramolecular crosslinks where redox-responsive behavior is driven by the enzyme-fuel couples horse radish peroxidase (HRP)-H 2 O 2 and glucose oxidase (GOx)-d-glucose. The hydrogel can be tuned from a responsive to a self-regulating supramolecular system by varying the concentration of added reduction fuel d-glucose. The onset of self-regulating behavior is due to formation of oxidation fuel in the hydrogel by a cofactor intermediate GOx[FADH 2 ]. UV/Vis spectroscopy, rheology, and kinetic modeling were employed to understand the emergence of out-of-equilibrium behavior and reveal the programmable negative feedback response of the hydrogel, including the adaptation of its elastic modulus and its potential as a glucose sensor., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

A procedure for the solid-phase extraction of antibiotics (enoxacin, ofloxacin, norfloxacin, ciprofloxacin, and sparfloxacin) in water has been developed. The sorbent used is based on a poly(glycidyl-co-ethylene dimethacrylate) network, whose previously modified surface has been functionalized with γ-cyclodextrin through a click-chemistry reaction. The architecture of the material has been characterized by thermogravimetric analysis, N 2 adsorption-desorption, Raman spectroscopy, confocal microscopy, and scanning electron microscopy, showing good capability to be used as a filler for extraction cartridges. The optimization of the extraction methodology shows good intra-day and inter-day repeatability of the extraction procedure, with coefficients of variation between 2.5 and 5.1% and the possibility of reusing the material at least five times. The detection limits of the method have been established at the μg L -1 level, confirming the possibility of quantifying trace levels. To end, real groundwater samples have been analyzed and the results are comparable with those obtained with a reference method. The proposed material can be used for assessing the presence of antibiotics in aqueous environments through an extraction procedure taking advantage of the presence of γ-cyclodextrin on its structure., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The transport of membrane impermeable compounds into cells is a prerequisite for the efficient cellular delivery of hydrophilic and amphiphilic compounds and drugs. Transport into the cell's cytosolic compartment should ideally be controllable and it should involve biologically compatible and degradable vehicles. Addressing these challenges, nanocontainers based on cyclodextrin amphiphiles that are stabilized by a biodegradable peptide shell are developed and their potential to deliver fluorescently labeled cargo into human cells is analyzed. Host-guest mediated self-assembly of a thiol-containing short peptide or a cystamine-cross-linked polypeptide shell on cyclodextrin vesicles produce short peptide-shelled (SPSV ss ) or polypeptide-shelled vesicles (PPSV ss ), respectively, with redox-responsive and biodegradable features. Whereas SPSV ss are permeable and less stable, PPSV ss effectively encapsulate cargo and show a strictly regulated release of membrane impermeable cargo triggered by either reducing conditions or peptidase treatment. Live cell experiments reveal that the novel PPSV SS are readily internalized by primary human endothelial cells (human umbilical vein endothelial cells) and cervical cancer cells and that the reductive microenvironment of the cells' endosomes trigger release of the hydrophilic cargo into the cytosol. Thus, PPSV SS represent a highly efficient, biodegradable, and tunable system for overcoming the plasma membrane as a natural barrier for membrane-impermeable cargo., (© 2021 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Supramolecular nanogels are an emerging class of polymer nanocarriers for intracellular delivery, due to their straightforward preparation, biocompatibility, and capability to spontaneously encapsulate biologically active components such as DNA. A completely biodegradable three-component cationic supramolecular nanogel was designed exploiting the multivalent host-guest interaction of cyclodextrin and adamantane attached to a polypeptide backbone. While cyclodextrin was conjugated to linear poly-L-lysine, adamantane was grafted to linear as well as star shaped poly-L-lysine. Size control of nanogels was obtained with the increase in the length of the host and guest polymer. Moreover, smaller nanogels were obtained using the star shaped polymers because of the compact nature of star polymers compared to linear polymers. Nanogels were loaded with anionic model cargoes, pyranine and carboxyfluorescein, and their enzyme responsive release was studied using protease trypsin. Confocal microscopy revealed successful transfection of mammalian HeLa cells and intracellular release of pyranine and plasmid DNA, as quantified using a luciferase assay, showing that supramolecular polypeptide nanogels have significant potential in gene therapy applications., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Molecular photoswitches play a vital role in the development of responsive materials. These molecular building blocks are particularly attractive when multiple stimuli can be combined to bring about physical changes, sometimes leading to unexpected properties and functions. The arylazoisoxazole molecular switch was recently shown to be capable of efficient photoreversible solid-to-liquid phase transitions with application in photoswitchable surface adhesion. Here, we show that the arylazoisoxazole forms thermally stable and photoisomerisable protonated Z - and E -isomers in an apolar aprotic solvent when the p K a of the applied acid is sufficiently low. The tuning of isomerisation kinetics from days to seconds by the p K a of the acid not only opens up new reactivity in solution, but also the solid-state photoswitching of azoisoxazoles can be efficiently reversed with selected acid vapours, enabling acid-gated photoswitchable surface adhesion., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The spatial and temporal control of gene expression at the post-transcriptional level is essential in eukaryotic cells and developing multicellular organisms. In recent years optochemical and optogenetic tools have enabled the manipulation and investigation of many steps in the involved processes. However, examples for light-mediated control of eukaryotic mRNA processing and the responsible enzymes are still rare. In particular, methylation of the 5' cap of mRNA is required for ribosome assembly, and the responsible guanine-N7 methyltransferase (MTase) from E. cuniculi (Ecm1) proved suitable for activating translation. Here, we report on a photoswitchable MTase obtained by bridging the substrate-binding cleft of Ecm1 with a tetra- ortho -methoxy-azobenzene. This azobenzene derivative is characterized by efficient trans -to- cis isomerization using red light at 615 nm. Starting from a cysteine-free Ecm1 variant (ΔCys), we used a computational approach to identify suitable conjugation sites for the azobenzene moiety. We created and characterized the four best-ranked variants, each featuring two appropriately positioned cysteines close to the substrate-binding cleft. Conjugating and crosslinking the azobenzene between C149/C155 in a designed Ecm1 variant (VAR3-Az) enabled light-dependent modulation of the MTase activity and showed a 50% higher activity for the cis form than the trans -form of the azobenzene conjugated to VAR3-Az., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

Artificial intelligence (AI) is accelerating the development of unconventional computing paradigms inspired by the abilities and energy efficiency of the brain. The human brain excels especially in computationally intensive cognitive tasks, such as pattern recognition and classification. A long-term goal is de-centralized neuromorphic computing, relying on a network of distributed cores to mimic the massive parallelism of the brain, thus rigorously following a nature-inspired approach for information processing. Through the gradual transformation of interconnected computing blocks into continuous computing tissue, the development of advanced forms of matter exhibiting basic features of intelligence can be envisioned, able to learn and process information in a delocalized manner. Such intelligent matter would interact with the environment by receiving and responding to external stimuli, while internally adapting its structure to enable the distribution and storage (as memory) of information. We review progress towards implementations of intelligent matter using molecular systems, soft materials or solid-state materials, with respect to applications in soft robotics, the development of adaptive artificial skins and distributed neuromorphic computing.

The surface chemistry of colloidal silica has tremendous effects on its properties and applications. Commonly the design of silica particles is based on their de novo synthesis followed by surface functionalization leading to tailormade properties for a specific purpose. Here, the design of robust "precursor" polymer-decorated silica nano- and microparticles is demonstrated, which allows for easy post-modification by polymer embedded thiolactone chemistry. To obtain this organic-inorganic hybrid material, silica particles (SiO 2 P) were functionalized via surface-initiated atom transfer radical polymerization (SI-ATRP) with poly(2-hydroxyethyl acrylate) (PHEA)-poly(thiolactone acrylamide (PThlAm) co-polymer brushes. Exploiting the versatility of thiolactone post-modification, a system was developed that could be used in three exemplary applications: 1) the straightforward molecular post-functionalization to tune the surface polarity, and therefore the dispersibility in various solvents; 2) the immobilization of metal nanoparticles into the polymer brushes via the in situ formation of free thiols that preserved catalytic activity in a model reaction; 3) the formation of redox-responsive, permeable polymer capsules by crosslinking the thiolactone moieties with cystamine dihydrochloride (CDH) followed by dissolution of the silica core., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Hydroarylation is an effective strategy to rapidly increase the complexity of organic structures by transforming flat alkene moieties into three-dimensional frameworks. Many strategies have already been developed to achieve the hydroarylation of styrenes, however most of these reports examine the hydroarylation of unpolar, β-mono- or β-unsubstituted styrenes, while exploring mainly electron-rich benzene nucleophiles. Herein, we report a mild and general catalytic system for the selective hydroheteroarylation of multiply substituted styrenes and heteroaromatic styrenes. Mechanistic analysis of the reaction led to the discovery of commercially available 2,2':5',2''-terthiophene as a key reagent., (© 2021 Wiley-VCH GmbH.)

Inspired by the way templates have been used to drive dynamic combinatorial libraries by molecular recognition, we exploited the photo-responsive host-guest interaction of an azo-based photoswitch with permethylated cyclodextrin to reversibly manipulate the dynamic covalent interaction of a phenyl boronic acid and d-fructose by irradiation with light.

Hydrogels that respond to non-invasive, external stimuli such as a magnetic field are of exceptional interest for the development of adaptive soft materials. To date magneto tuneable gels are predominantly based on macromolecular building blocks, while comparable low molecular weight systems are rarely found in the literature. Herein, we report a highly efficient peptide-based gelator (Nap GFYE), which can form hydrogels and incorporate Fe3O4 superparamagnetic nanoparticles in the gel matrix. The magnetic nanoparticles act as a physical crosslinker for the self-assembled peptide nanostructures and thus give rise to a fortified hybrid gel with distinctively improved mechanical properties. Furthermore, the particles provide the material with magnetic susceptibility and a gel to sol transition is observed upon application of a weak magnetic field. Magnetization of the inorganic-organic hybrid nanomaterial leads to on-demand release of an incorporated fluorescent dye into the supernatant.

Light-responsive modulation of the longitudinal (T1) and transversal relaxation times of a fluorinated cyclodextrin has been achieved by host-guest complexation with arylazopyrazole-modified metal complexes in aqueous solution. This supramolecular concept can potentially be applied to the development of contrast agents for 19F magnetic resonance imaging (MRI).

Correction for 'Cyclodextrin-based superparamagnetic host vesicles as ultrasensitive nanobiocarriers for electrosensing' by Jose Muñoz et al., Nanoscale, 2020, 12, 9884-9889, DOI: .

The imbalance of amyloid-β (Aβ) production and clearance causes aggregation of Aβ 1-42 monomers to form fibrils and amyloid plaques, which is an indispensable process in the pathogenesis of Alzheimer's disease (AD), and eventually leads to pathological changes and cognitive impairment. Consequently, Aβ 1-42 is the most important target for the treatment of AD. However, developing a single treatment method that can recognize Aβ 1-42 , inhibit Aβ 1-42 fibrillation, eliminate amyloid plaques, improve cognitive impairments, and alleviate AD-like pathology is challenging. Here, a coassembly composed of cyclodextrin (CD) and calixarene (CA) is designed, and it is used as an anti-Aβ therapy agent. The CD-CA coassembly is based on the previously reported heteromultivalent recognition strategy and is able to successfully eliminate amyloid plaques and degrade Aβ 1-42 monomers in 5xFAD mice. More importantly, the coassembly improves recognition and spatial cognition deficits, and synaptic plasticity impairment in the 5xFAD mice. In addition, the coassembly ameliorates AD-like pathology including prevention of neuronal apoptosis and oxidant stress, and alteration of M1/M2 microglial polarization states. This supramolecular approach makes full use of both molecular recognition and self-assembly of macrocyclic amphiphiles, and is a promising novel strategy for AD treatment., (© 2020 Wiley-VCH GmbH.)

Although cyclodextrins (CDs) have been used as additives to small molecule surfactants, there are only a few examples of this cyclic oligosaccharide being used as a surfactant template. Herein, we present a novel ionic β-CD derivative that shows significant surface activity and stabilizes oil-in-water emulsions prepared with hexadecane as a model oil. The macrocyclic surfactant strongly reduces the oil-water surface tension with increasing concentration and shows a critical micelle concentration (CMC) around 5 mM. We demonstrate the stability of the oil-in-water emulsions and verify the possibility to address the emulsion droplet surface using molecular recognition of the β-CD cavity at the oil-water interface.

One of the central aims of synthetic biology and metabolic engineering is to mimic the integrality of eukaryotic cells to construct a multifunctional compartment system to perform multistep incompatible cascade reactions in a one-pot, controlled, and selective fashion. The key challenge is how to address the coexistence of antagonistic reagents and to incorporate these functionalities into an integrated system in a smart and efficient way. A novel strategy called "iterative etching-grafting" is proposed here based on monodispersed photonic spheres (PSs) prepared by microfluidics, which constructs a universal platform for incompatible cascade reactions. As a proof of concept, we spatiotemporally regulated the degree of etching of PSs, then grafted precursory groups of acid and base onto PSs, and incorporated a photocleavage method, which were capable of compartmentalizing the acid and base inside PSs. Utilizing the band-gap offsets of PSs could track the progress of cascade reactions in situ, and grafting various charged polymers on the surface of the pores by surface-initiated atom transfer radical polymerization (SI-ATRP) achieved the selectivity of the substrates, which flexibly constructed a multifunctional and integrated acid-base photonic multicompartment system (PMCS). The created PMCS shows excellent catalytic performance, convenient monitoring, and efficient substrate selectivity in the deacetalization-Knoevenagel cascade reaction. Furthermore, two types of electrophile/nucleophile PMCSs have also been accessibly constructed, demonstrating the facile generation of other incompatible systems with the versatility as well as the advancement and extensibility of the developed strategy.

The synthesis of adamantane-terminated polypeptides by N-carboxyanhydride (NCA) polymerization and their use in the template-based self-assembly of redox-responsive nanocontainers is described. Cyclodextrin vesicles (CDV) serve as a supramolecular template to anchor adamantane terminated polypeptides on to the surface of CDV and to form polypeptide shelled vesicles (PPSVss) which are stabilized by crosslinking with cystamin. Polypeptides are characterized by nuclear magnetic resonance, matrix-assisted laser desorption/ionization (MALDI), and gel permeation chromatography, and nanocontainer formation at each step is confirmed by dynamic light scattering (DLS) and zeta potential measurements. MALDI confirms the presence of the adamantane at the end of the polymers, and isothermal titration calomatry (ITC) of the adamantane-terminated polypeptides with β-cyclodextrin proves the capability of adamantane on the polypeptides to form host-guest inclusion complexes even with the longest polypeptides. Encapsulation of a model dye carboxyfluorescein in PPSVss and its redox-responsive release demonstrates the potential use of this novel type of completely biodegradable and biocompatible nanocontainer for the purpose of intracellullar delivery., (© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Responsive hybrid hydrogels composed of a self-assembling low molecular weight gelator and a polymeric network are of particular interest for the development of smart nanomaterials. Key advantages of such hybrid hydrogels are their ease in preparation as well as their unique mechanical properties. Herein we describe a photoresponsive peptide AAP-FGDS, which exhibits excellent photochemical properties and highly reversible changes in the rheological properties. Addition of AAP-FGDS to a covalent, non-responsive agarose network gives rise to a robust hybrid hydrogel with phototunable mechanical properties and shape memory. Upon irradiation with UV light the self-assembled three dimensional structure disaggregates to yield a softer yet self-supporting hydrogel. Irradiation with visible light followed by the reassembly of the peptide allows the fixation of a different shape programmed by mechanical deformation. Upon repeated deactivation of the peptide network the original shape is recovered.

Herein, we demonstrate the key impact of synergistic repulsive interactions on pathway complexity in aqueous media. To this end, we have examined the aqueous self-assembly of four new amphiphilic BODIPY dyes where the extent of repulsive interactions has been systematically varied.