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Sulfonamides have many important biological applications, yet their synthesis often involves long reaction times under dry and non-ambient conditions. Here we report the synthesis of a large range of sulfonamides at room temperature using 4-nitrophenyl benzylsulfonate as a starting material. Sulfonamides were prepared from a wide range of aliphatic, linear, and cyclic amines, anilines, and N-methylanilines. The yields and reaction times observed here were comparable to or better than those reported previously, establishing sulfur-phenolate exchange as a viable alternative.

SuFEx chemistry has recently evolved as next-generation click chemistry. However, in most SuFEx syntheses, additional reagents/catalysts and carefully controlled conditions are still needed. Here, we aim to further generalize S(VI) exchange chemistry, using 4-nitrophenyl phenylmethanesulfonate as example, in which the nitrophenolate group is exchanged for a wide range of (substituted) phenols and alkyl alcohols. Quantitative yields were reached within 10 min under ambient conditions and required only filtering through silica as workup.

Ion channels, many expressed in insect neural and muscular systems, have drawn huge attention as primary targets of insecticides. With the recent technical breakthroughs in structural biology, especially in cryo-electron microscopy (cryo-EM), many new high-resolution structures of ion channel targets, apo or in complex with insecticides, have been solved, shedding light on the molecular mechanism of action of the insecticides and resistance mutations. These structures also provide accurate templates for structure-based insecticide screening and rational design. This review summarizes the recent progress in the structural studies of 5 ion channel families: the ryanodine receptor (RyR), the nicotinic acetylcholine receptor (nAChR), the voltage-gated sodium channel (VGSC), the transient receptor potential (TRP) channel, and the ligand-gated chloride channel (LGCC). We address the selectivity of the channel-targeting insecticides by examining the conservation of key coordinating residues revealed by the structures. The possible resistance mechanisms are proposed based on the locations of the identified resistance mutations on the 3D structures of the target channels and their impacts on the binding of insecticides. Finally, we discuss how to develop “green” insecticides with a novel mode of action based on these high-resolution structures to overcome the resistance.

With the ever-evolving cannabis industry, low-cost and high-throughput analytical methods for cannabinoids are urgently needed. Normally, (potentially) psychoactive cannabinoids, typically represented by Δ9-tetrahydrocannabinol (Δ9-THC), and nonpsychoactive cannabinoids with therapeutic benefits, typically represented by cannabidiol (CBD), are the target analytes. Structurally, the former (tetrahydrocannabinolic acid (THCA), cannabinol (CBN), and THC) have one olefinic double bond and the latter (cannabidiolic acid (CBDA), cannabigerol (CBG), and CBD) have two, which results in different affinities toward Ag(I) ions. Thus, a silica gel thin-layer chromatography (TLC) plate with the lower third impregnated with Ag(I) ions enabled within minutes a digital chromatographic separation of strongly retained CBD analogues and poorly retained THC analogues. The resolution (Rs) between the closest two spots from the two groups was 4.7, which is almost 8 times higher than the resolution on unmodified TLC. After applying Fast Blue BB as a chromogenic reagent, smartphone-based color analysis enabled semiquantification of the total percentage of THC analogues (with a limit of detection (LOD) of 11 ng for THC, 54 ng for CBN, and 50 ng for THCA when the loaded volume is 1.0 μL). The method was validated by analyzing mixed cannabis extracts and cannabis extracts. The results correlated with those of high-performance liquid chromatography with ultraviolet detection (HPLC-UV) (R2 = 0.97), but the TLC approach had the advantages of multi-minute analysis time, high throughput, low solvent consumption, portability, and ease of interpretation. In a desiccator, Ag(I)-TLC plates can be stored for at least 3 months. Therefore, this method would allow rapid distinction between high and low THC varieties of cannabis, with the potential for on-site applicability.

The ryanodine receptor (RyR) is one of the primary targets of commercial insecticides. The diamide insecticide family, including flubendiamide, chlorantraniliprole, cyantraniliprole, etc., targets insect RyRs and can be used to control a wide range of destructive agricultural pests. The diamide insecticides are highly selective against lepidopteran and coleopteran pests with relatively low toxicity for non-target species, such as mammals, fishes, and beneficial insects. However, recently mutations identified on insect RyRs have emerged and caused resistance in several major agricultural pests throughout different continents. This review paper summarizes the recent findings on the structure and function of insect RyRs as insecticide targets. Specifically, we examine the structures of RyRs from target and non-target species, which reveals the molecular basis for insecticide action and selectivity. We also examine the structural and functional changes of RyR caused by the resistance mutations. Finally, we examine the progress in RyR structure-based insecticide design and discuss how this might help the development of a new generation of green insecticides.

This work presents a novel route for creating metal-free antiviral coatings based on polymer brushes synthesized by surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer (SI-PET-RAFT) polymerization, applying eosin Y as a photocatalyst, water as a solvent, and visible light as a driving force. The polymer brushes were synthesized using N-[3-(decyldimethyl)-aminopropyl] methacrylamide bromide and carboxybetaine methacrylamide monomers. The chemical composition, thickness, roughness, and wettability of the resulting polymer brush coatings were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), water contact angle measurements, and ellipsometry. The antiviral properties of coatings were investigated by exposure to severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and avian influenza viruses, with further measurement of residual viable viral particles. The best performance was obtained with Cu surfaces, with a ca. 20-fold reduction of SARS-Cov-2 and a 50-fold reduction in avian influenza. On the polymer brush-modified surfaces, the number of viable virus particles decreased by about 5-6 times faster for avian flu and about 2-3 times faster for SARS-CoV-2, all compared to unmodified silicon surfaces. Interestingly, no significant differences were obtained between quaternary ammonium brushes and zwitterionic brushes.

Reaction rates of strained cycloalkynes and cycloalkenes with 1,2-quinones were quantified by stopped flow UV-Vis spectroscopy. Surprisingly, it was determined that 8-membered BCN-OH reacts substantially (16 times) faster than the more strained 7-membered THS. Thermodynamic activation parameters, obtained from the linearized Eyring equation and stopped-flow measurements, revealed that the reaction of both BCN-OH and THS with ortho-quinones is entropycontrolled, ruling out a relevant contribution of secondary orbital interactions (SOIs) as earlier proposed.

The efficient development of functional and sustainable polymers not only requires rapid formation under mild conditions but also a high degree of control over the polymer structure, as well as gentle degradation routes that do not diminish their function. A significant step forward was set by the groups of Wu and Sharpless, as outlined in ACS Central Science, in which they use sulfur exchange click chemistry to access polymers via a chain-growth mechanism and pave the way toward mild degradation and application as degradable gels.

The products of the SuFEx reaction between sulfonimidoyl fluorides and phenols, sulfonimidates, are shown to display dynamic covalent chemistry with other phenols. This reaction was shown to be enantiospecific, finished in minutes at room temperature in high yields, and useful for both asymmetric synthesis and sustainable polymer production. Its wide scope further extends the usefulness of SuFEx and related click chemistries.

We studied the mechanistic and biological origins of anti-inflammatory poly-unsaturated fatty acid-derived

Click chemistry has been established rapidly as one of the most valuable methods for the chemical transformation of complex molecules. Due to the rapid rates, clean conversions to the products, and compatibility of the reagents and reaction conditions even in complex settings, it has found applications in many molecule-oriented disciplines. From the vast landscape of click reactions, approaches have emerged in the past decade centered around oxidative processes to generate in situ highly reactive synthons from dormant functionalities. These approaches have led to some of the fastest click reactions know to date. Here, we review the various methods that can be used for such oxidation-induced “one-pot” click chemistry for the transformation of small molecules, materials, and biomolecules. A comprehensive overview is provided of oxidation conditions that induce a click reaction, and oxidation conditions are orthogonal to other click reactions so that sequential “click-oxidation-click” derivatization of molecules can be performed in one pot. Our review of the relevant literature shows that this strategy is emerging as a powerful approach for the preparation of high-performance materials and the generation of complex biomolecules. As such, we expect that oxidation-induced “one-pot” click chemistry will widen in scope substantially in the forthcoming years.

The global rise of antimicrobial resistance (AMR) that increasingly invalidates conventional antibiotics has become a huge threat to human health. Although nanosized antibacterial agents have been extensively explored, they cannot sufficiently discriminate between microbes and mammals, which necessitates the exploration of other antibiotic-like candidates for clinical uses. Herein, two-dimensional boron nitride (BN) nanosheets are reported to exhibit antibiotic-like activity to AMR bacteria. Interestingly, BN nanosheets had AMR-independent antibacterial activity without triggering secondary resistance in long-term use and displayed excellent biocompatibility in mammals. They could target key surface proteins (e.g., FtsP, EnvC, TolB) in cell division, resulting in impairment of Z-ring constriction for inhibition of bacteria growth. Notably, BN nanosheets had potent antibacterial effects in a lung infection model by P. aeruginosa (AMR), displaying a 2-fold increment of survival rate. Overall, these results suggested that BN nanosheets could be a promising nano-antibiotic to combat resistant bacteria and prevent AMR evolution.

Many biomedical fields rely on proteins that are selectively modified with novel chemical entities. These are often attached using reactive or catalytic moieties, but the position where these moieties are attached is often poorly controlled. In this work, we assess how catalyst position affects the efficiency and selectivity of protein modification. For this, we anchored a template DNA strand to the active site of three different proteins, which were subsequently hybridized to DNA strands that contained catalysts at different positions. We found that catalysts operating via a covalently bound reactant intermediate show a strong correlation between their distance to the protein surface and their efficiency and that the site-selectivity of the modification is affected by the position of the catalyst. Our results are rationalized using computational simulations, showing that one-point anchoring of the DNA construct leads to notable differences in the site of modification.

Herein, we describe the selective positioning of metal-organic framework (MOF) nanoparticles UiO-66 (Universitet i Oslo; Zr6O4(OH)4(bdc)6; bdc2- = benzene-1,4-dicarboxylate) and MIL-101 (Matérial Institut Lavoisier, Cr3O(OH) (H2O)2(bdc)3) at defined positions on a patterned substrate. For this purpose, patterned alkyne- and carboxylic acid-terminated self-assembled organic monolayer (SAM)-modified silicon surfaces were prepared by liquid immersion and microcontact printing (μCP). Preformed UiO-66 and MIL-101 nanometer-sized MOFs (NMOFs) were synthesized by solvothermal synthesis, and the nanocrystallite particles' exterior surface was functionalized in order to generate reactive sites (such as azides and amines) at the NMOFs. Copper-catalyzed alkyne azide cycloaddition and N-hydroxysuccinimide-mediated amide formation were used to selectively position the NMOFs at the surface of pre-patterned substrates. The resulting surfaces were thoroughly investigated by scanning electron microscopy, infrared spectroscopy, and X-ray photoelectron spectroscopy, confirming the validity of the presented approach. We hope that our research paves the way for microsystem integration of NMOFs, for example, in microfluidic devices/reactors, and further investigation of their enhanced catalytic activity.

In this work, we demonstrate that fine-grained, quantitative control over macroscopic dynamic material properties can be achieved using the Hammett equation in tuneable dynamic covalent polyimine materials. Via this established physical-organic principle, operating on the molecular level, one can fine-tune and control the dynamic material properties on the macroscopic level, by systematic variation of dynamic covalent bond dynamics through selection of the appropriate substituent of the aromatic imine building blocks. Five tuneable, crosslinked polyimine network materials, derived from dianiline monomers with varying Hammett parameter (σ) were studied by rheology, revealing a distinct correlation between the σ value and a range of corresponding dynamic material properties. Firstly, the linear correlation of the kinetic activation energy (Ea) for the imine exchange to the σ value, enabled us to tune the Ea from 16 to 85 kJ mol−1. Furthermore, the creep behaviour (γ), glass transition (Tg) and the topology freezing transition temperature (Tv), all showed a strong, often linear, dependence on the σ value of the dianiline monomer. These combined results demonstrate for the first time how dynamic material properties can be directly tuned and designed in a quantitative – and therefore predictable – manner through correlations based on the Hammett equation. Moreover, the polyimine materials were found to be strong elastic rubbers (G′ > 1 MPa at room temperature) that were stable up to 300 °C, as confirmed by TGA. Lastly, the dynamic nature of the imine bond enabled not only recycling, but also intrinsic self-healing of the materials over multiple cycles without the need for solvent, catalysts or addition of external chemicals., Controlling macroscopic material properties of dynamic covalent polyimines via the electronic effect of dianiline monomers based on the Hammett equation.

To investigate the dynamic stereochemical inversion behavior of pillar[5]arenes (P[5]s) in more detail, we synthesized a series of novel rim-differentiated P[5]s with various substituents and examined their rapid rotations by variable-temperature NMR (203–298 K). These studies revealed for the first time the barrier of “methyl-through-the-annulus” rotation (ΔG‡ = 47.4 kJ·mol–1 in acetone) and indicated that for rim-differentiated P[5]s with two types of alkyl substituents, the smaller rim typically determines the rate of rotation. However, substituents with terminal C=C or C≡C bonds give rise to lower inversion barriers, presumably as a result of attractive π–π interactions in the transition state. Finally, data on a rim-differentiated penta-methyl-penta-propargyl P[5] exhibited the complexity of the overall inversion dynamics.

This work presents a new method for the synthesis of antifouling polymer brushes using surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain-transfer polymerization with eosin Y and triethanolamine as catalysts. This method proceeds in an aqueous environment under atmospheric conditions without any prior degassing and without the use of heavy metal catalysts. The versatility of the method is shown by using three chemically different monomers: oligo(ethylene glycol) methacrylate, N-(2-hydroxypropyl)methacrylamide, and carboxybetaine methacrylamide. In addition, the light-triggered nature of the polymerization allows the creation of complex three-dimensional structures. The composition and topological structuring of the brushes are confirmed by X-ray photoelectron spectroscopy and atomic force microscopy. The kinetics of the polymerizations are followed by measuring the layer thickness with ellipsometry. The polymer brushes demonstrate excellent antifouling properties when exposed to single-protein solutions and complex biological matrices such as diluted bovine serum. This method thus presents a new simple approach for the manufacturing of antifouling coatings for biomedical and biotechnological applications.

The realization of covalent adaptable networks with excellent mechanical and dynamic properties remains a major challenge. Herein, the acylsemicarbazide (ASC) moieties with dynamic reversibility and multiple hydrogen bonding were disclosed and used to prepare transparent, high modulus, and malleable polymer networks. It was found that the ASC moiety can reversibly generate isocyanate and hydrazide at elevated temperatures, that is, exhibiting dynamic reversibility. ASC can also produce the disordered multiple hydrogen bonds that contribute to superior mechanical strength for dynamic polymers. The hydrogen bonding in ASC moieties can diminish the energy barrier for the cleavage of dynamic covalent bonds, and the dissociation of ASC moieties further promotes the disruption of hydrogen bonds, showing the synergistic dynamic effects. ASC moieties provide a valuable molecular engineering opportunity toward high-performance dynamic polymer materials. The polymer containing ASC moieties possesses excellent optical transparency, superb mechanical performance (Young's modulus up to 1.7 GPa), together with malleable and healing properties.

Silicon nanoparticles (Si NPs) are a good alternative to conventional heavy metal-containing quantum dots in many applications, due to their low toxicity, low cost, and the high natural abundance of the starting material. Recently, much synthetic progress has been made, and crystalline Si NPs can now be prepared in a matter of hours. However, the passivation of these particles is still a time-consuming and difficult process, usually requiring high temperatures and/or harsh reaction conditions. In this paper, we report an easy method for the room-temperature functionalization of hydrogen-terminated Si NPs. Using silanol compounds, a range of functionalized Si NPs could be produced in only 1 h reaction time at room temperature. The coated NPs were fully characterized to determine the efficiency of binding and the effects of coating on the optical properties of the NPs. It was found that Si NPs were effectively functionalized, and that coated NPs could be extracted from the reaction mixture in a straightforward manner. The silanol coating increases the quantum yield of fluorescence, decreases the spectral width and causes a small (∼50 nm) blue-shift in both the excitation and emission spectra of the Si NPs, compared to unfunctionalized particles.

Novel methods to make synthetic chiral polymers are highly desirable given their potential in a rapidly increasing number of bio-inspired applications. The enantiospecific sulfur–fluorine exchange (SuFEx) reaction of chiral di-sulfonimidoyl fluorides (di-SFs) with diphenols, was used to produce high-molecular-weight chiral polymers with configurational backbone chirality. The resulting new class of polymers, polysulfonimidates, can be efficiently produced via this step-growth mechanism for a wide range of di-SFs and diphenols, yielding MnPS up to 283 kDa with a typical dispersity Đ around 1.6. The optical activity of the resulting chiral polymers is largely due to the intrinsic asymmetry of the S atoms (configurational chirality). Finally, the enantiospecificity (ee>98 %) of the polymerization reaction was demonstrated by the degradation of a disulfide-containing polysulfonimidate. This novel route towards configurational main-chain chirality opens up new approaches towards tailor-made chiral polymers with precisely defined properties.

Vektorielle Katalyse – die Steuerung von mehrstufigen Reaktionen in einer programmierten Abfolge und durch definierte räumliche Lokalisierung in einem mikroskaligen Reaktor – ist ein grundlegendes Ziel in der bioinspirierten Katalyseforschung. Die Übertragung von Konzepten aus der natürlichen Kaskaden-Biokatalyse zu künstlichen hierarchischen chemischen Systeme bleibt jedoch eine Herausforderung. Hier zeigen wir die Integration von zwei verschiedenen oberflächenverankerten, nanometergroßen metallorganischen Gerüsten (MOFs) in einem mikrofluidischen Reaktor zur Modellierung der vektoriellen Katalyse. Die Katalysatoren wurden an definierten Abschnitten entlang des Mikrokanals immobilisiert, dies ermöglichte eine zweistufige Kaskadenreaktion mit vollständiger Umsetzung nach 30 Sekunden und hohen Umsatzfrequenzen (TOF≈105 h−1).

A “rim-differentiated” pillar[6]arene (RD-P[6]) was obtained successfully, with the assistance of a dimeric silver trifluoroacetate template, among eight different constitutional isomers in a direct and regioselective manner. The solid-state conformation of this macrocycle could switch from the 1,3,5-alternate to a truly rim-differentiated one upon guest inclusion. This highly symmetric RD-P[6] not only hosts metal-containing molecules inside its cavity, but also can form a pillar[6]arene-C60 adduct through co-crystallization on account of donor-acceptor interactions. The development of synthetic strategies to desymmetrize pillararenes offers new opportunities for engineering complex molecular architectures and organic electronic materials.

Linear-bottlebrush-linear (LBBL) triblock copolymers are emerging systems for topologically-tunable elastic materials. In this paper, a new synthetic methodology is presented to synthesize LBBL polystyrene-block-bottlebrushpolydimethylsiloxane-block-polystyrene (PS-b-bbPDMS-b-PS) triblock copolymer via the “grafting onto” approach where the precursors are individually synthesized through living anionic polymerization and selective coupling reaction. In this two-step approach, polystyrene-block-polymethylvinylsiloxane (PS-b-PMVS) diblock copolymer with a low dispersity couples with another living PS block to form PS-b-PMVS-b-PS triblock copolymer. Secondly, this is followed by grafting of separately prepared monohydride-terminated PDMS chains with controllable grafting density through a hydrosilylation reaction. In addition to fully tunable architectural parameters, this approach permits a quantitative determination of the ratio of diblock and triblock bottlebrush copolymers and consistency between batches, highlighting the feasibility for scaled-up production. These LBBL triblock copolymers self-assemble into soft, low-modulus thermoplastic elastomers, and the precise knowledge of the composition is crucial for correlating microstructure to mechanical properties.

The analysis of catecholamines, such as dopamine, epinephrine and norepinephrine in urine can be used in the diagnosis of certain pathologies, such as hormone-producing tumors. Here, a fast and simple quantitative boronate affinity paper spray tandem mass spectrometric (PS-MS/MS) method is established, which can improve selectivity and reduce ion suppression without needing any instrumental chromatography. We use here the property of boronic acids, which can selectively bind ortho-diol-containing compounds under alkaline conditions. Paper tip modification and catechol enrichment protocols were developed to selectively bind, clean up and subsequently desorb such catecholamines. Standard catecholamine solutions, as well as human urine samples were analyzed with the PS-MS(/MS) method, which is fast, cheap and easy-to-operate compared to HPLC-MS/MS. Despite its high simplicity, boronate affinity PS-MS/MS exhibits good performance compared to HPLC-MS/MS in human urine analysis in terms of precision (2.1%–7.2% vs. 1.1%–2.9%) and accuracy (−10.2%–9.3% vs. −4.8%–5.1%), and a physiologically relevant limit of detection (0.027–0.12 μg mL−1). The boronate affinity PS-MS/MS clearly achieved the detection limits that would allow the fast analysis of urine samples for clinical purposes, such as screening for pheochromocytoma (exceeding 0.5 μg mL−1).

A common method to study protein complexes is immunoprecipitation (IP), followed by mass spectrometry (thus labeled: IP-MS). IP-MS has been shown to be a powerful tool to identify protein-protein interactions. It is, however, often challenging to discriminate true protein interactors from contaminating ones. Here, we describe the preparation of antifouling azide-functionalized polymer-coated beads that can be equipped with an antibody of choice via click chemistry. We show the preparation of generic immunoprecipitation beads that target the green fluorescent protein (GFP) and show how they can be used in IP-MS experiments targeting two different GFP-fusion proteins. Our antifouling beads were able to efficiently identify relevant protein-protein interactions but with a strong reduction in unwanted nonspecific protein binding compared to commercial anti-GFP beads.

The structures of hierarchically assembled supramolecular architectures are dictated characteristically by the encoded symmetries and geometries of the corresponding building blocks. In literature, assorted Platonic molecular polyhedra have been built out of highly symmetric macrocycles. Nonetheless, the synthesis of pillararene-based molecular cages remains challenging owing to the underlying shape and limited derivatization strategies of this macrocyclic scaffold. Herein, we report the assembly of AgnL2 metal-organic pillars from rim-differentiated pillar[5]arene-derived ligands, Lm and Lp, through [N···Ag+···N] coordinative bonds. These stereolabile macrocycles undergo chiral self-sorting during complexation. Although the meta-substituted Lm forms diastereoisomeric Ag5Lm2 complexes without stereocontrol in solution, only a meso-Ag4Lm2 complex with a Ag4 kernel was observed in the solid state. In contrast, the narcissistic coassembly of the para-substituted Lp with AgPF6 results in enantiomeric Ag5Lp2 complexes resembling twisted pentagonal prisms. This research paves the way for the construction of deep-cavity metallocavitands and nanochannels with unique molecular recognition and transportation properties.

We studied the mechanistic and biological origins of anti-inflammatory poly-unsaturated fatty acid-derived N-acylethanolamines using synthetic bifunctional chemical probes of docosahexaenoyl ethanolamide (DHEA) and arachidonoyl ethanolamide (AEA) in RAW264.7 macrophages stimulated with 1.0 μg mL-1lipopolysaccharide. Using a photoreactive diazirine, probes were covalently attached to their target proteins, which were further studied by introducing a fluorescent probe or biotin-based affinity purification. Fluorescence confocal microscopy showed DHEA and AEA probes localized in cytosol, specifically in structures that point toward the endoplasmic reticulum and in membrane vesicles. Affinity purification followed by proteomic analysis revealed peroxiredoxin-1 (Prdx1) as the most significant binding interactor of both DHEA and AEA probes. In addition, Prdx4, endosomal related proteins, small GTPase signaling proteins, and prostaglandin synthase 2 (Ptgs2, also known as cyclooxygenase 2 or COX-2) were identified. Lastly, confocal fluorescence microscopy revealed the colocalization of Ptgs2 and Rac1 with DHEA and AEA probes. These data identified new molecular targets suggesting that DHEA and AEA may be involved in reactive oxidation species regulation, cell migration, cytoskeletal remodeling, and endosomal trafficking and support endocytosis as an uptake mechanism.

Commonly, modification of surfaces with thermoresponsive polymers is performed using poly(N-isopropylacrylamide) (poly(NIPAM)). However, integration of poly(NIPAM) with a second polymer to obtain more complex copolymer structures has proven challenging due to inherently poorly controllable polymerization characteristics of acrylamides. In this study, (N-(2-methacryloyloxyethyl)pyrrolidone (NMEP) is synthesized and polymerized under controlled conditions from silicon oxide substrates via surface-initiated atom transfer radical polymerization (SI-ATRP) to produce thermoresponsive poly(NMEP) brushes. The livingness of the brushes is demonstrated by reinitiation of poly(NMEP) brushes using oligo(ethylene glycol) methyl ether methacrylate to obtain diblock copolymer brushes. Following extensive characterization, the reversible thermoresponsive behavior of these poly(NMEP) brushes is demonstrated using phase-controlled AFM topography measurements in an aqueous liquid environment. These measurements indicate that at 27 °C the poly(NMEP) brushes are solvated and extend away from the surface, whereas at 60 °C the polymers are insoluble and reside in a collapsed conformation. Finally, to investigate the potential applicability of poly(NMEP) brushes in biomedical devices, the antifouling properties of the coating are tested in aqueous media containing BSA, fibrinogen, or 10% diluted human serum using quartz crystal microbalance with dissipation monitoring (QCM-D). These measurements reveal very good antifouling properties, even when exposed to 10% diluted human serum.

In this work, we tuned the ion selectivity of a polyelectrolyte multilayer (PEM)-coated, cation-exchange membrane (CMX) in a membrane capacitive deionization (MCDI) process by carefully studying different operational modes, namely constant voltage (CV) and constant current (CC). The monovalent cation selectivity and its time-dependent behavior were monitored at different voltage and current values. Upon optimizing the current density (10 A/m2) and the number of polyelectrolyte bilayers (5.5) on the CMX membranes, a time-independent and nearly full monovalent cation selectivity was obtained for various feed solutions, provided a polycation-terminated PEM was applied. Furthermore, the selectivity values of several commercially available cation-exchange membranes were tested under the optimized conditions and compared with CMX and PEM-CMX, yielding the best performance for PEM-CMX, regardless the composition of feed solution. Before this optimization, this MCDI system showed a time-dependent selectivity, with a maximum of ρMgNa ≈3. The results were rationalized by applying an MCDI model based on the dynamic potential profile, describing the potential drops across the membrane and demonstrating a threshold for the current density.

Vectorial Catalysis - controlling multi-step reactions in a programmed sequence and by defined spatial localization in a microscale device - is an enticing goal in bio-inspired catalysis research. However, translating concepts from natural cascade biocatalysis into artificial hierarchical chemical systems remains a challenge. Herein, we demonstrate integration of two different surface-anchored nanometer-sized metal-organic frameworks (MOFs) in a microfluidic device for modelling vectorial catalysis. Catalysts immobilization at defined sections along the microchannel and a two-step cascade reaction was conducted with full conversion after 30 seconds and high turnover frequencies (TOF = ~10 5 h -1 ).

The increased use of both pillar[5]arenes and pillar[6]arenes, stimulated by increasingly efficient syntheses of both, has brought forward the question as to what drives the intermediates in this Friedel–Crafts ring formation to form a pillar[5]arene, a pillar[6]arene, or any other sized macrocycle. This study sets out to answer this question by studying both the thermodynamics and kinetics involved in the absence and presence of templating solvents using high-end wB97XD/6-311G(2p,2d) DFT calculations.