Piperazine-containing polymer brush layer as supported base catalyst in a glass microreactor

The covalent attachment of piperazine onto the inner walls of a microreactor using glycidyl methacrylate polymer brushes has been demonstrated. The piperazine-containing polymer brushes were first grown on a flat silicon oxide surface and were characterized by contact angle, Fourier transform infrared (FT-IR), ellipsometry, and X-ray photoelectron spectroscopy (XPS). The applicability of the catalytic polymer brushes in a microreactor was demonstrated for the Knoevenagel and nitroaldol condensation reactions, and the synthesis of coumarin derivatives. The catalytic activity of the microreactor was still intact even after 2 months

Assessment of Cooperativity in Ternary Peptide-Cucurbit[8]uril Complexes

Evaluating cooperativity for cucurbit[8]uril (CB[8])-mediated ternary complexation is required for understanding and advancing designs of such ternary self-assembled systems. A key issue is to dissect the contributions of the binding steps of the first and second guest molecules to the overall ternary complex formation energy. This is addressed by performing concentration-dependent titrations between CB[8] and guests by means of concentration-dependent calorimetric and 1H-NMR titrations. The sensitivity of the fitting of the cumulative heat of complexation of the calorimetric titrations is evaluated in terms of fitting error and enthalpy–entropy compensation and, together with the NMR spectroscopic analysis of the separate species, non-cooperative binding is conceived to be the most probable binding scenario. The binding behavior of CB[8] homoternary complexes is similar to CB[8] heteroternary complexes, with an enthalpy-driven tight fit of the guests in the CB[8] cavity overcoming the entropic penalty. Also for these types of complexes, a non-cooperative binding is the most probable

Chemical strategies for the presentation and delivery of growth factors

Since the first demonstration of employing growth factors (GFs) to control cell behaviour in vitro, the spatiotemporal availability of GFs in vivo has received continuous attention. In particular, the ability to physically confine the mobility of GFs has been used in various tissue engineering applications e.g. stents, orthopaedic implants, sutures and contact lenses. The lack of control over the mobility of GFs in scaffolds jeopardizes their performance in vivo. In this feature article, an overview is given on how to effectively present GFs on scaffolds. In the first part, non-covalent strategies are described covering interaction motifs that are generic to direct GF immobilization. In the second part, covalent strategies are described emphasizing the introduction of reactive groups in existing biomaterials. The feature article ends with a description of strategies based on the physical entrapment of growth factors

Utilizing the Oxygen Reduction Reaction in Particle Impact Electrochemistry:A Step toward Mediator-Free Digital Electrochemical Sensors

The current blockade particle impact method opens a route toward highly parallelized single-entity electrochemical assays. An important limitation is, however, that a redox mediator must be present in the sample, which can detrimentally interfere with molecular recognition processes. Dissolved O2 that is naturally present in aqueous solutions under ambient conditions can in principle serve as a suitable mediator via the oxygen reduction reaction (ORR). Here, we demonstrate the validity of this concept by performing current blockade experiments to capture and detect individual microparticles at Pt microelectrodes using solely the ORR. The readout modality is independent of the absolute O2 concentration, allowing operation under varying conditions. We further determine how the trajectories of individual microparticles are influenced by the combination of electrophoresis and electroosmotic flows and how these can be utilized to provide continuous detection of cationic particles in water for environmental monitoring.</p

Attachment of streptavidin to β-cyclodextrin molecular printboards via orthogonal host-guest and protein-ligand interactions

Streptavidin (SAv) is attached to β-cyclodextrin (β-CD) self-assembled monolayers (SAMs) via orthogonal host-guest and SAv-biotin interactions. The orthogonal linkers consist of a biotin functionality for binding to SAv and adamantyl functionalities for host-guest interactions at β-CD SAMs. SAv complexed to excess monovalent linker in solution and then attached to a β-CD SAM could be removed by rinsing with a 10 mM β-CD solution. When SAv was attached to the β-CD SAM via the divalent linker, it was impossible to remove SAv from the surface by the same rinsing procedure. This is interpreted by assuming that two SAv binding pockets are oriented towards the β-CD SAM resulting in (labile) divalent and (stable) tetravalent β-CD-adamantyl interactions for the mono- and divalent linkers, respectively. This was confirmed by experiments at varying β-CD concentrations. When the [linker]/[SAv] ratio is reduced, a clear trend in the divalent-linker case is seen: the less linker the more protein could be removed from the surface. It is proven that the orthogonality of the binding motifs and the stability of the divalent linker at the -CD SAM allows the stepwise assembly of the complex at the β-CD SAM by first adsorbing the linker, followed by SAv. This stepwise assembly allows the controlled heterofunctionalization of surface-immobilized SAv

Regioselectivity Control of the Ring Opening of Epoxides With Sodium Azide in a Microreactor

The reaction of different types of aromatic and aliphatic epoxides with sodium azide to give vicinal azido alcohols was studied in a microreactor with and without pillars in the channels. Dependent on the substrate, the regioselectivity of the ring opening is affected by the used solvent system, viz. acetonitrile–water (sometimes with 10% acetic acid to promote the reactivity of substrates) or t-butyl acetate–water containing Tween80 as a surfactant. For styrene oxide and α-methylstyrene oxide, the α/ß regioselectivity changes from 4 to 10 and 1.7 to 6.2, respectively, going from acetonitrile–water to Tween80-containing t-butyl acetate–water. The addition of a surfactant (Tween80) stabilizes the interface in the biphasic t-butyl acetate–water. Pillar-containing microreactors gave better conversions than microreactors without pillars and lab scale reactions, probably due to better mixing

High-Resolution Contact Printing with Chemically Patterned Flat Stamps Fabricated by Nanoimprint Lithography

Chemically patterned flat stamps provide an effective solution to avoid mechanical stamp-stability problems currently encountered in microcontact printing. A new method is developed to fabricate chemical patterns on a flat PDMS stamp using nanoimprint lithography. Sub-100 nm gold patterns are successfully replicated by these chemically patterned flat PDMS stamps. \ud \u

Erratum:Influenza as a molecular walker (Chemical Science (2020) 11 (27–36) DOI: 10.1039/c9sc05149j)

The authors regret that incorrect details were given for ref. 70 in the original article. The correct version of ref. 70 is given below as ref. 1. The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.</p