Inline monitoring of high ammonia concentrations in methanol with a customized 3D printed flow cell

A novel system for inline monitoring of ammonia (NH3) suitable for methanol is presented. An optical ammonia sensor with a response time t90 of 33 s was combined with a tailor-made, 3D printed flow cell and allowed efficient measurements under continuous flow. The optical sensor includes a fluorescent indicator dye that is physically immobilized into a polyurethane hydrogel. A protective layer made of hydrophobic polyether sulfone (PES) shields the ammonia sensitive material against interfering substances and guarantees long-term stability in methanol. The sensor can be read out via a compact phase fluorimeter. Measurements in continuous flow are enabled by a flow cell manufactured via selective laser melting (SLM) of stainless steel. Stainless steel was chosen for the flow cell due to its good heat transfer properties and relatively good chemical resistance of NH3 in methanol. The measurements were successfully carried out with ammonia concentrations between 0.3 and 5.6 mol L− 1 NH3 in methanol at 25 °C up to 80 °C. Additionally, different flow-rates (0.5–2.0 mL min− 1), varying internal pressure (0.5–2.0 bar) as well as reversibility of the measurements at 25 and 60 °C were studied in detail. The sensor did not degrade indicated by sufficient signal and low drift over a period of two weeks, thus indicating the high potential of the novel set-up for real-time measurements in continuous flow applications. Graphical abstract

Optical ammonia sensors based on fluorescent aza-BODIPY dyes— a flexible toolbox

We present three types of optical ammonia sensors suitable for environmental, bioprocess, and reaction monitoring. A respective fluorescent BF2-chelated tetraarylazadipyrromethene dye (aza-BODIPYs) is physically entrapped in a polyurethane hydrogel (HydroMed D4) forming an emulsion system with vinyl-terminated polydimethylsiloxane (PDMS). The analyte-sensitive layer is covered by a hydrophobic membrane which excludes hydrophilic substances. Three different protection layers are tested, whereby the Teflon and the hydrophobic PES layers outperform a PDMS/TiO2 layer. Response times within their dynamic range of 15 s can be achieved, whereas the PDMS/TiO2-covered sensor requires at least 390 s. The three sensors entail the following concentration areas: first sensor 3 μg L−1–3 mg L−1 (LOD 0.23 μg L−1), second sensor 0.1–30 mg L−1 (LOD 28 μg L−1), and third sensor 3 mg L−1–1 g L−1 (LOD 0.51 mg L−1). Readout is performed with a commercially available phase fluorimeter combined with optical fibers. Dual-lifetime referencing (DLR) is used as referencing method and Egyptian blue acts as an inert reference material. No cross-sensitivity to pH changes can be detected.

Facile design of a dextran derived polyurethane hydrogel and metallopolymer: a sustainable approach for elimination of organic dyes and reduction of nitrophenols

This work reports a sustainable approach for fabrication of a highly cost-effective and operation-convenient adsorbent derived from dextran and its valorization to a metallopolymer photocatalyst.

Injectable Thermosensitive Formulation Based on Polyurethane Hydrogel/Mesoporous Glasses for Sustained Co-Delivery of Functional Ions and Drugs

Mini-invasively injectable hydrogels are widely attracting interest as smart tools for the co-delivery of therapeutic agents targeting different aspects of tissue/organ healing (e.g., neo-angiogenesis, inflammation). In this work, copper-substituted bioactive mesoporous glasses (Cu-MBGs) were prepared as nano- and micro-particles and successfully loaded with ibuprofen through an incipient wetness method (loaded ibuprofen approx. 10% w/w). Injectable hybrid formulations were then developed by dispersing ibuprofen-loaded Cu-MBGs within thermosensitive hydrogels based on a custom-made amphiphilic polyurethane. This procedure showed almost no effects on the gelation potential (gelation at 37 °C within 3–5 min). Cu2+ and ibuprofen were co-released over time in a sustained manner with a significantly lower burst release compared to MBG particles alone (burst release reduction approx. 85% and 65% for ibuprofen and Cu2+, respectively). Additionally, released Cu2+ species triggered polyurethane chemical degradation, thus enabling a possible tuning of gel residence time at the pathological site. The overall results suggest that hybrid injectable thermosensitive gels could be successfully designed for the simultaneous localized co-delivery of multiple therapeutics.