Effect of charge of quaternary ammonium cations on lipophilicity and electroanalytical parameters: Task for ion transfer voltammetry

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.OLD ChemE/Organic Materials and Interface

Modelling the selective removal of sodium ions from greenhouse irrigation water using membrane technology

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.Accepted Author ManuscriptOLD ChemE/Organic Materials and Interface

Proteomics as a new tool to study fingermark ageing in forensics

Fingermarks are trace evidence of great forensic importance, and their omnipresence makes them pivotal in crime investigation. Police and law enforcement authorities have exploited fingermarks primarily for personal identification, but crucial knowledge on when fingermarks were deposited is often lacking, thereby hindering crime reconstruction. Biomolecular constituents of fingermark residue, such as amino acids, lipids and proteins, may provide excellent means for fingermark age determination, however robust methodologies or detailed knowledge on molecular mechanisms in time are currently not available. Here, we address fingermark age assessment by: (i) drafting a first protein map of fingermark residue, (ii) differential studies of fresh and aged fingermarks and (iii), to mimic real-world scenarios, estimating the effects of donor contact with bodily fluids on the identification of potential age biomarkers. Using a high-resolution mass spectrometry-based proteomics approach, we drafted a characteristic fingermark proteome, of which five proteins were identified as promising candidates for fingermark age estimation. This study additionally demonstrates successful identification of both endogenous and contaminant proteins from donors that have been in contact with various bodily fluids. In summary, we introduce state-of-the-art proteomics as a sensitive tool to monitor fingermark aging on the protein level with sufficient selectivity to differentiate potential age markers from body fluid contaminants.OLD ChemE/Organic Materials and InterfacesOLD BT/Cell Systems Engineerin

Controlled amino-functionalization by electrochemical reduction of bromo and nitro azobenzene layers bound to Si(111) surfaces

4-Nitrobenzenediazonium (4-NBD) and 4-bromobenzenediazonium (4-BBD) salts were grafted electrochemically onto H-terminated, p-doped silicon (Si) surfaces. Atomic force microscopy (AFM) and ellipsometry experiments clearly showed layer thicknesses of 2–7 nm, which indicate multilayer formation. Decreasing the diazonium salt concentration and the reaction time resulted in a smaller layer thickness, but did not prevent the formation of multilayers. It was demonstrated, mainly by X-ray photoelectron spectroscopy (XPS), that the diazonium salts not only react with the H-terminated Si surface, but also with electrografted phenyl groups via azo-bond formation. These azo bonds can be electrochemically reduced at Ered = ?1.5 V, leading to the corresponding amino groups. This reduction resulted in a modest decrease in layer thickness, and did not yield monolayers. This indicates that other coupling reactions, notably a biphenyl coupling, induced by electrochemically produced phenyl radicals, take place as well. In addition to the azo functionalities, the nitro functionalities in electrografted layers of 4-NBD were independently reduced to amino functionalities at a lower potential (Ered = ?2.1 V). The presence of amino functionalities on fully reduced layers, both from 4-NBD- and 4-BBD-modified Si, was shown by the presence of fluorine after reaction with trifluoroacetic anhydride (TFAA). This study shows that the electrochemical reduction of azo bonds generates amino functionalities on layers produced by electrografting of aryldiazonium derivatives. In this way multifunctional layers can be formed by employing functional aryldiazonium salts, which is believed to be very practical in the fabrication of sensor platforms, including those made of multi-array silicon nanowires.Chemical EngineeringApplied Science

Modified cation-exchange membrane for phosphate recovery in an electrochemically assisted adsorption-desorption process

A novel ion separation methodology using a cation-exchange membrane modified with iron oxide nanoparticles (Fe3O4 NPs) coated with polyhexamethylene guanidine (PHMG) is proposed. The separation is performed in an electrodialysis cell, where firstly phosphate is electro-adsorbed to the PHMG@Fe3O4 NP coating, followed by a desorption step by applying an electric current.Accepted Author ManuscriptChemE/Transport PhenomenaOLD ChemE/Organic Materials and InterfacesChemE/Advanced Soft Matte

Separation of alkali metal cations by a supported liquid membrane (SLM) operating under electro dialysis (ED) conditions

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.ChemE/Advanced Soft Matte

Influence of Conductivity and Dielectric Constant of Water–Dioxane Mixtures on the Electrical Response of SiNW-Based FETs

In this study, we report on the electrical response of top-down, p-type silicon nanowire field-effect transistors exposed to water and mixtures of water and dioxane. First, the capacitive coupling of the back gate and the liquid gate via an Ag/AgCl electrode were compared in water. It was found that for liquid gating smaller potentials are needed to obtain similar responses of the nanowire compared to back gating. In the case of back gating, the applied potential couples through the buried oxide layer, indicating that the associated capacitance dominates all other capacitances involved during this mode of operation. Next, the devices were exposed to mixtures of water and dioxane to study the effect of these mixtures on the device characteristics, including the threshold voltage (VT). The VT dependency on the mixture composition was found to be related to the decreased dissociation of the surface silanol groups and the conductivity of the mixture used. This latter was confirmed by experiments with constant conductivity and varying water–dioxane mixtures.ChemE/Chemical EngineeringApplied Science

Reaction-diffusion analysis for one-step plasma etching and bonding of microfluidic devices

A self-similar reaction front develops in reactive ion etching when the ions penetrate channels of shallow height h. This relates to the patterning of microchannels using a single-step etching and bonding, as described by Rhee et al. [Lab Chip 5, 102 (2005)] . Experimentally, we report that the front location scales as xf ? ht1/2 and the width is time-invariant and scales as ? ? h. Mean-field reaction-diffusion theory and Knudsen diffusion give a semiquantitative understanding of these observations and allow optimization of etching times in relation to bonding requirements.ChemE/Chemical EngineeringApplied Science

Nickel hexacyanoferrate electrodes for high mono/divalent ion-selectivity in capacitive deionization

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.OLD ChemE/Organic Materials and Interface

Fe₃O₄nanoparticles coated with a guanidinium-functionalized polyelectrolyte extend the pH range for phosphate binding

In this work commercially available Fe3O4 NPs were coated with polyallylamine hydrochloride (PAH) and PAH functionalized with guanidinium groups (PAH–Gu) for investigating the phosphate adsorption properties under alkaline conditions. The coating can be prepared easily and rapidly and results in Fe3O4 NPs with improved properties related to phosphate binding and colloidal stability. At a low initial phosphate concentration (2 mg L−1), the novel Fe3O4@PAH–Gu material was able to remove phosphate rather independently of the pH condition (4.0, 3.6 and 3.7 mg g−1 at pH = 5, 8 and 10, respectively), whereas for the uncoated Fe3O4 NPs the amount of adsorbed phosphate drops by >75% upon changing from acidic to alkaline conditions (0.84 mg g−1 at pH = 10). Under alkaline conditions, the fastest adsorption was observed for Fe3O4@PAH–Gu followed by Fe3O4@PAH and Fe3O4. This can be related to the additional interaction forces due to the presence of primary amine groups (in PAH and PAH–Gu) and Gu groups (in PAH–Gu only) in coatings. Over 80% of the phosphate adsorbed on the novel Fe3O4@PAH–Gu material was successfully desorbed and the coated NPs were re-used over three adsorption/desorption cycles. This work will stimulate the design and preparation of functionalized polyelectrolytes for an extended area of applications, especially for the selective removal of target compounds from wastewater.ChemE/Organic Materials and InterfacesChemE/Delft Ingenious Desig