The electrochemical behavior of three differently charged drug molecules (zwitter-ionic acetylcarnitine, bi-cationic succinylcholine and tri-cationic gallamine) was studied at the interface between two immiscible electrolyte solutions. Tetramethylammonium was used as a model mono cationic molecule and internal reference. The charge and molecular structure were found to play an important role in the drug lipophilicity. The studied drugs gave a linear correlation between the water – octanol (logPoctanol) partition coefficients and the electrochemically measured water – 1,2-dichloroethane (logPDCE) partition coefficients. Comparison with tetraalkylammonium cations indicating that the correlation between logPoctanol and logPDCE is molecular structure dependent. The highest measured sensitivity and lowest limit of detection were found to be 0.543 mA·dm3·mol− 1 and 6.25 μM, respectively, for the tri-cationic gallamine. The sensitivity for all studied ions was found to be a linear function of molecular charge. The dissociation constant of the carboxylic group of zwiter-ionic acetylcarnitine was calculated based on voltammetric parameters and was found to be 4.3. This study demonstrates that electrochemistry at the liquid – liquid interface is powerful technique when it comes to electroanalytical or pharmacokinetic drug assessment.@en

Capacitors made of interdigitated electrodes (IDEs) as a transducer platform for the sensing of volatile organic compounds (VOCs) have advantages due to their lower power operation and fabrication using standard micro-fabrication techniques. Integrating a micro-electromechanical system (MEMS), such as a microhotplate with IDE capacitor, further allows study of the temperature- dependent sensing response of VOCs. In this paper, the design, fabrication, and characterization of a low-power MEMS microhotplate with IDE capacitor to study the temperature-dependent sensing response to methanol using Zeolitic imidazolate framework (ZIF-8), a class of metal-organic framework (MOF), is presented. A Titanium nitride (TiN) microhotplate with aluminum IDEs suspended on a silicon nitride membrane is fabricated and characterized. The power consumption of the ZIF-8 MOF-coated device at an operating temperature of 50 ∘ C is 4.5 mW and at 200 ∘ C it is 26 mW. A calibration methodology for the effects of temperature of the isolation layer between the microhotplate electrodes and the capacitor IDEs is developed. The device coated with ZIF-8 MOF shows a response to methanol in the concentration range of 500 ppm to 7000 ppm. The detection limit of the sensor for methanol vapor at 20 ∘ C is 100 ppm. In situ study of sensing properties of ZIF-8 MOF to methanol in the temperature range from 20 ∘ C to 50 ∘ C using the integrated microhotplate and IDE capacitor is presented. The kinetics of temperature-dependent adsorption and desorption of methanol by ZIF-8 MOF are fitted with double-exponential models. With the increase in temperature from 20 ∘ C to 50 ∘ C, the response time for sensing of methanol vapor concentration of 5000 ppm decreases by 28%, whereas the recovery time decreases by 70%.@en

Here, we report the covalent coupling of poly (styrene-co-maleic anhydride) onto γ-alumina to develop high-performance organic solvent nanofiltration (OSN) membranes. A high molecular weight (M w ) alternating copolymer of maleic anhydride (MA) and styrene (St) was synthesized and directly grafted to the γ-alumina membrane, while commercially available low M w random copolymers of St and MA were also investigated. We show that solute rejection and membrane permeability strongly depend on the nature of the applied copolymer. In particular, the M w of the copolymer applied is potentially the key for improving the membrane performance. When a high M w copolymer was applied, the grafted layer covered the surface of the membrane. This results in membranes with significantly improved rejection, while maintaining a high permeability. In contrast, we observed pore grafting by applying low M w copolymers, which resulted in membranes with slightly higher rejection and dramatically lower permeability compared to unmodified membrane. The best results were obtained by grafting γ-alumina with a high M w alternating copolymer. These membranes showed a solute rejection of 98% for Sudan Black B (457 g mol −1 ) in toluene, while the permeability remained high at 2.9 L m −2 h −1 bar −1 . @en

The development of controlled polymerization techniques in the last decade has enabled polymer brushes to be grown from inorganic substrates with precision. Less studied are brushes grown from concave geometries of high curvature, such as mesopores, despite their application potential in the separation sciences. The method used here, surface-initiated, activators-regenerated-by-electron-transfer, atom-transfer radical polymerization (SI-ARGET-ATRP), is used to grow a polystyrene brush grown from aluminum oxide pores of 5 nm diameter, to-date the most confined geometry in which ATRP has been conducted. The brush is characterized by TGA, AFM, and FTIR, the latter two methods applied specifically to the external brush. Additionally, permporometry as well as permeability and retention measurements are used to characterize the graft within the mesopores. We show that the brush length is tunable, that the brush length is solvent-dependent, and we also demonstrate the application potential of this hybrid material as an organic solvent nanofiltration membrane. This new class of membranes shows excellent performance: a toluene permeability of 2.0 L m−2 h−1 bar−1 accompanied by a 90% rejection of diphenylanthracene (MW 330 g mol−1).@en

The development of controlled polymerization techniques in the last decade has enabled polymer brushes to be grown from inorganic substrates with precision. Less studied are brushes grown from concave geometries of high curvature, such as mesopores, despite their application potential in the separation sciences. The method used here, surface-initiated, activators-regenerated-by-electron-transfer, atom-transfer radical polymerization (SI-ARGET-ATRP), is used to grow a polystyrene brush grown from aluminum oxide pores of 5 nm diameter, to-date the most confined geometry in which ATRP has been conducted. The brush is characterized by TGA, AFM, and FTIR, the latter two methods applied specifically to the external brush. Additionally, permporometry as well as permeability and retention measurements are used to characterize the graft within the mesopores. We show that the brush length is tunable, that the brush length is solvent-dependent, and we also demonstrate the application potential of this hybrid material as an organic solvent nanofiltration membrane. This new class of membranes shows excellent performance: a toluene permeability of 2.0 L m−2 h−1 bar−1 accompanied by a 90% rejection of diphenylanthracene (MW 330 g mol−1).@en

The development of controlled polymerization techniques in the last decade has enabled polymer brushes to be grown from inorganic substrates with precision. Less studied are brushes grown from concave geometries of high curvature, such as mesopores, despite their application potential in the separation sciences. The method used here, surface-initiated, activators-regenerated-by-electron-transfer, atom-transfer radical polymerization (SI-ARGET-ATRP), is used to grow a polystyrene brush grown from aluminum oxide pores of 5 nm diameter, to-date the most confined geometry in which ATRP has been conducted. The brush is characterized by TGA, AFM, and FTIR, the latter two methods applied specifically to the external brush. Additionally, permporometry as well as permeability and retention measurements are used to characterize the graft within the mesopores. We show that the brush length is tunable, that the brush length is solvent-dependent, and we also demonstrate the application potential of this hybrid material as an organic solvent nanofiltration membrane. This new class of membranes shows excellent performance: a toluene permeability of 2.0 L m−2 h−1 bar−1 accompanied by a 90% rejection of diphenylanthracene (MW 330 g mol−1).@en

Selective ion removal has been a point of focus in capacitive deionization because of its industrial applications such as water purification, water softening, heavy metal separation and resource recovery. Conventionally, carbon is used as electrode material for selectivity. However, recent developments focus on intercalation materials such as Prussian Blue Analogues, due to their size-based preference towards cations. Selectivity of nickel hexacyanoferrate electrodes from a mixture of Na+, Mg2+, and Ca2+ ions was studied in this work. Here, a CDI cell with two identical NiHCF electrodes was operated in two desalination modes: (a) cyclic, in which ions are removed from and released into the same water reservoir and thus, the ion concentration remains the same after one cycle, and (b) continuous, in which ions are removed from one water reservoir and released back in a different reservoir. An average separation factor of ≈15 and 25, reflecting the selectivity of the electrodes, was obtained for Na+ over Ca2+ and Mg2+ from an equimolar solution of Na+, Ca2+ and Mg2+ in both, cyclic and continuous desalination. It was concluded that NiHCF, used in a symmetric CDI cell, is a promising material for highly selective removal of Na+ from a multivalent ion mixture.@en

A major challenge in nanotechnology is that of determining how to introduce green and sustainable principles when assembling individual nanoscale elements to create working devices. For instance, textile nanofinishing is restricted by the many constraints of traditional pad-dry-cure processes, such as the use of costly chemical precursors to produce nanoparticles (NPs), the high liquid and energy consumption, the production of harmful liquid wastes, and multistep batch operations. By integrating low-cost, scalable, and environmentally benign aerosol processes of the type proposed here into textile nanofinishing, these constraints can be circumvented while leading to a new class of fabrics. The proposed one-step textile nanofinishing process relies on the diffusional deposition of aerosol NPs onto textile fibers. As proof of this concept, we deposit Ag NPs onto a range of textiles and assess their antimicrobial properties for two strains of bacteria (i.e., Staphylococcus aureus and Klebsiella pneumoniae). The measurements show that the logarithmic reduction in bacterial count can get as high as ca. 5.5 (corresponding to a reduction efficiency of 99.96%) when the Ag loading is 1 order of magnitude less (10 ppm; i.e., 10 mg Ag NPs per kg of textile) than that of textiles treated by traditional wet-routes. The antimicrobial activity does not increase in proportion to the Ag content above 10 ppm as a consequence of a "saturation" effect. Such low NP loadings on antimicrobial textiles minimizes the risk to human health (during textile use) and to the ecosystem (after textile disposal), as well as it reduces potential changes in color and texture of the resulting textile products. After three washes, the release of Ag is in the order of 1 wt %, which is comparable to textiles nanofinished with wet routes using binders. Interestingly, the washed textiles exhibit almost no reduction in antimicrobial activity, much as those of as-deposited samples. Considering that a realm of functional textiles can be nanofinished by aerosol NP deposition, our results demonstrate that the proposed approach, which is universal and sustainable, can potentially lead to a wide number of applications.@en

This study demonstrates the effective separation of alkali metal cations using a Supported Liquid Membrane (SLM) containing lipophilic, negatively charged borate moieties, operating under electro dialysis conditions. The selectivity of the membrane is essentially based on differences in dehydration energy and mobility between ion species. The system favors the ion species with the largest crystal radius, despite its lower mobility. In mixtures of K+ and Na+, the SLM separates K+ from Na+ with a separation efficiency ranging from ~20% to 90%, depending on the feed solution composition. With solutions containing either K+ or Na+ and Li+, the K+/Na+ over Li+ separation efficiency is nearly 100%. Addition of 15-crown-5 derivative does not improve SLM behavior, but slows down the K+ current by approximately 30% whereas the Na+ current remains unaffected. As supported by simulations, the free K+ and Na+ ratio in the membrane (and with that the current ratio) is entirely defined by partitioning and the feed concentration ratio, regardless the presence of 15-crown-5. As a result, the current ratio of two ion species can be described exclusively in terms of their feed concentrations and crystal radii because the latter parameter defines both partitioning and mobility.@en

Microporous polymer frameworks have attracted considerable attention to make novel separation layers owing to their highly porous structure, high permeability, and excellent molecular separation. This study concerns the fabrication and properties of thin melamine-based microporous polymer networks with a layer thickness of around 400 nm, supported on an α-alumina support and their potential use in organic solvent nanofiltration. The modified membranes show excellent solvent purification performances, such as n-heptane permeability as high as 9.2 L m−2 h−1 bar −1 in combination with a very high rejection of approximately 99 % for organic dyes with molecular weight of ≥457 Da. These values are higher than for the majority of the state-of-the-art membranes. The membranes further exhibit outstanding long-term operation stability. This work significantly expands the possibilities of using ceramic membranes in organic solvent nanofiltration.@en

A model is presented for the Na+ and K+ levels in the irrigation water of greenhouses, specifically those for the cultivation of tomato. The model, essentially based on mass balances, not only describes the accumulation of Na+ but includes a membrane unit for the selective removal of Na+ as well. As determined by the membrane properties, some of the K+ is removed as well. Based on real-life process parameters, the model calculates the Na+ and K+ concentration at three reference points. These process parameters include the evapotranspiration rate, the K+ uptake by the plants, the Na+ and K+ content of the fertilizer, the Na+ leaching out from the hydroponic substrate material, and the Na+ and K+ removal efficiency of the membrane unit. Using these parameters and given a constant K+ concentration of the irrigation water entering the greenhouse of 6.6 mM (resulting in the optimal K+ concentration for tomato cultivation), the composition of the solution is completely defined at all three reference points per irrigation cycle. Prime aim of this investigation is to explore the requirements for the selective membrane that currently is developed in our lab. It is found that even for a limited Na+ over K+ selectivity of 6, after a number of cycles the Na+ level reaches steady state at a level below the upper (toxic) threshold for tomato cultivation (20 mM). Economic aspects and ways of implementation of such a system are briefly discussed.@en

Silicon semiconductors with a thin surface layer of silica were first modified with polyelectrolytes (polyethyleneimine, polystyrene sulfonate and poly(allylamine)) via a facile layer-by-layer deposition approach. Subsequently, lipid vesicles were added to the preformed polymeric cushion, resulting in the adsorption of intact vesicles or fusion and lipid bilayer formation. To study involved interactions we employed optical reflectometry, electrochemical impedance spectroscopy and fluorescent recovery after photobleaching. Three phospholipids with different charge of polar head groups, i.e. 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), 1,2-dioleoyl-sn-glycero-3-phospho-L-serine (DOPS) and 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) were used to prepare vesicles with varying surface charge. We observed that only lipid vesicles composed from 1:1 (mole:mole) mixture of DOPC/DOPS have the ability to fuse onto an oppositely charged terminal layer of polyelectrolyte giving a lipid bilayer with a resistance of >100 kΩ. With optical reflectometry we found that the vesicle surface charge is directly related to the amount of mass adsorbed onto the surface. An interesting observation was that zwitterionic polar head groups of DOPC allow the adsorption on both positively and negatively charged surfaces. As found with fluorescent recovery after photobleaching, positively charged surface governed by the presence of poly(allylamine) as the terminal layer resulted in intact DOPC lipid vesicles adsorption whereas in the case of a negatively charged silica surface formation of lipid bilayers was observed, as expected from literature.@en

Affinity layers play a crucial role in chemical sensors for the selective and sensitive detection of analytes. Here, we report the use of composite affinity layers containing Metal Organic Frameworks (MOFs) in a polymeric matrix for sensing purposes. Nanoparticles of NH2-MIL-53(Al) were dispersed in a Matrimid polymer matrix with different weight ratios (0-100 wt %) and drop-casted on planar capacitive transducer devices. These coated devices were electrically analyzed using impedance spectroscopy and investigated for their sensing properties toward the detection of a series of alcohols and water in the gas phase. The measurements indicated a reversible and reproducible response in all devices. Sensor devices containing 40 wt % NH2-MIL-53(Al) in Matrimid showed a maximum response for methanol and water. The sensor response time slowed down with increasing MOF concentration until 40 wt %. The half time of saturation response (τ0.5) increased by ∼1.75 times for the 40 wt % composition compared to devices coated with Matrimid only. This is attributed to polymer rigidification near the MOF/polymer interface. Higher MOF loadings (≥50 wt %) resulted in brittle coatings with a response similar to the 100 wt % MOF coating. Cross-sensitivity studies showed the ability to kinetically distinguish between the different alcohols with a faster response for methanol and water compared to ethanol and 2-propanol. The observed higher affinity of the pure Matrimid polymer toward methanol compared to water allows also for a higher uptake of methanol in the composite matrices. Also, as indicated by the sensing studies with a mixture of water and methanol, the methanol uptake is independent of the presence of water up to 6000 ppm of water. The NH2-MIL-53(Al) MOFs dispersed in the Matrimid matrix show a sensitive and reversible capacitive response, even in the presence of water. By tuning the precise compositions, the affinity kinetics and overall affinity can be tuned, showing the promise of this type of chemical sensors.@en

Surface-modified silicon nanowire-based field-effect transistors (SiNW-FETs) have proven to be a promising platform for molecular recognition in miniature sensors. In this work, we present a novel nanoFET device for the sensitive and selective detection of explosives based on affinity layers of metal−organic polyhedra (MOPs). The judicious selection of the geometric and electronic characteristics of the assembly units (organic ligands and unsaturated metal site) embedded within the MOP cage allowed for the formation of multiple charge-transfer (CT) interactions to facilitate the selective explosive inclusion. Meanwhile, the host-stabilized CT complex inside the cage acted as an effective molecular gating element to strongly modulate the electrical conductance of the silicon nanowires. By grafting the MOP cages onto a SiNWFET device, the resulting sensor showed a good electrical sensing capability to various explosives, especially 2,4,6-trinitrotoluene (TNT), with a detection limit below the nanomolar level. Importantly, coupling MOPswhich have tunable structures and propertiesto SiNW-based devices may open up new avenues for a wide range of sensing applications, addressing various target analytes.@en

Surface-modified silicon nanowire-based field-effect transistors (SiNW-FETs) have proven to be a promising platform for molecular recognition in miniature sensors. In this work, we present a novel nanoFET device for the sensitive and selective detection of explosives based on affinity layers of metal−organic polyhedra (MOPs). The judicious selection of the geometric and electronic characteristics of the assembly units (organic ligands and unsaturated metal site) embedded within the MOP cage allowed for the formation of multiple charge-transfer (CT) interactions to facilitate the selective explosive inclusion. Meanwhile, the host-stabilized CT complex inside the cage acted as an effective molecular gating element to strongly modulate the electrical conductance of the silicon nanowires. By grafting the MOP cages onto a SiNWFET device, the resulting sensor showed a good electrical sensing capability to various explosives, especially 2,4,6-trinitrotoluene (TNT), with a detection limit below the nanomolar level. Importantly, coupling MOPswhich have tunable structures and propertiesto SiNW-based devices may open up new avenues for a wide range of sensing applications, addressing various target analytes.@en

We have investigated in detail properties of hybrid polyelectrolyte-anion exchange membranes (AEMs) having different amounts of a guanidinium-modified poly(allylamine hydrochloride) (PAH-Gu) derivative (2, 5, and 8 wt%). The presence of guanidinium groups at the membrane surface was confirmed by XPS. For 2 and 5 wt% the blended membranes are homogeneous, while at 8 wt% segregation is observed by AFM. The membrane permselectivity and ionic electrical resistance for phosphate reduce upon incorporation of the PAH-Gu in the membrane, reflecting an increased co-ion (H+ and Na+) permeation. We conclude that PAH-Gu loaded in the AEM favors an interaction with phosphate. In electrodialysis, using sodium sulfate and sodium dihydrogen phosphate at equal concentrations in the source phase a slight preference for phosphate was observed. Our work shows that this facile membrane fabrication procedure shows great potential in terms of tuning the membrane properties. One way to boost selective ion transport could be by increasing the number of functional groups in the membrane.@en

We report an advanced treatment method for phosphoric acid recovery from leached sewage sludge ash. Layer-by-layer (LbL) polyelectrolyte deposition has been used as a tool to modify and convert a hollow ultrafiltration membrane into a nanofiltration (NF) LbL membrane for H3PO4 recovery. To build the LbL membrane, poly(styrenesulfonate) PSS was chosen as polyanion, while three different polycations were used: a permanently charged polyelectrolyte, poly(diallyldimethylammonium chloride), PDADMAC; a pH-dependent charged polyelectrolyte poly(allylamine hydrochloride), PAH; and a PAH modified with guanidinium groups (PAH-Gu). Based on detailed surface characterizations (AFM, XPS and Zeta-potential) it was concluded that both charge density and pH-responsiveness of the polycations are key parameters to control the final membrane surface structure and transport properties. The surface properties of LbL-coated membranes were correlated with the membrane filtration performance, when exposed to the real leached sewage sludge ash solution. The highest permeability was recorded for (PDADMAC/PSS)6, a result that was rationalized on its loose, and possibly less interpenetrated, structure, followed by (PAH-Gu/PSS)6 characterized by a more dense, compact layer. H3PO4 recovery was the highest in the case of (PDADMAC/PSS)6, but the retention of multivalent metals (Fe3+ and Mg2+) was low, leading to a more contaminated permeate. The opposite trend was observed for (PAH-Gu/PSS)6, resulting in a less metal-contaminated, but also a less H3PO4-concentrated permeate. Our LbL-modified membranes were found to improve the permeability and H3PO4 recovery compared to a commercially available acid-resistant NF membrane.@en

We report an advanced treatment method for phosphoric acid recovery from leached sewage sludge ash. Layer-by-layer (LbL) polyelectrolyte deposition has been used as a tool to modify and convert a hollow ultrafiltration membrane into a nanofiltration (NF) LbL membrane for H3PO4 recovery. To build the LbL membrane, poly(styrenesulfonate) PSS was chosen as polyanion, while three different polycations were used: a permanently charged polyelectrolyte, poly(diallyldimethylammonium chloride), PDADMAC; a pH-dependent charged polyelectrolyte poly(allylamine hydrochloride), PAH; and a PAH modified with guanidinium groups (PAH-Gu). Based on detailed surface characterizations (AFM, XPS and Zeta-potential) it was concluded that both charge density and pH-responsiveness of the polycations are key parameters to control the final membrane surface structure and transport properties. The surface properties of LbL-coated membranes were correlated with the membrane filtration performance, when exposed to the real leached sewage sludge ash solution. The highest permeability was recorded for (PDADMAC/PSS)6, a result that was rationalized on its loose, and possibly less interpenetrated, structure, followed by (PAH-Gu/PSS)6 characterized by a more dense, compact layer. H3PO4 recovery was the highest in the case of (PDADMAC/PSS)6, but the retention of multivalent metals (Fe3+ and Mg2+) was low, leading to a more contaminated permeate. The opposite trend was observed for (PAH-Gu/PSS)6, resulting in a less metal-contaminated, but also a less H3PO4-concentrated permeate. Our LbL-modified membranes were found to improve the permeability and H3PO4 recovery compared to a commercially available acid-resistant NF membrane.@en