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The formation of CuCl nanoplatelets from the ionic liquid precursor (ILP) butylpyridinium tetrachlorocuprate [C4Py](2)[CuCl4] using ascorbic acid as a reducing agent was investigated. In particular, electron paramagnetic resonance (EPR) spectroscopy was used to evaluate the interaction between ascorbic acid and the Cu(II) ion before reduction to Cu(I). EPR spectroscopy suggests that the [CuCl4](2-) ion in the neat IL is a distorted tetrahedron, consistent with DFT calculations. Addition of ascorbic acid leads to the removal of one chloride from the [CuCl4](2-) anion, as shown by DFT and the loss of symmetry by EPR. DFT furthermore suggests that the most stable adduct is formed when only one hydroxyl group of the ascorbic acid coordinates to the Cu(II) ion.
Industrialized food production is in urgent search for alternative packaging materials, which can serve the requirements of a globalized world in terms of longer product shelf lives, reduced freight weight to decrease transport costs, and better barrier functionality to preserve its freshness. Polymer materials containing organically modified nano clay particles as additives are one example for a new generation of packaging materials with specific barrier functionality to actually hit the market. Clay types used for these applications are aluminosilicates, which belong to the mineral group of phyllosilicates. These consist of nano-scaled thin platelets, which are organically modified with quaternary ammonium compounds acting as spacers between the different clay layers, thereby increasing the hydrophobicity of the mineral additive. A variety of different organically modified clays are already available, and the use as additive for food packaging materials is one important application. To ensure valid risk assessments of emerging nano composite polymers used in the food packaging industry, exact analytical characterization of the organically modified clay within the polymer matrix is of paramount importance. Time-of-flight SIMS in combination with multivariate statistical analysis was used to differentiate modified clay reference materials from another. Time-of-flight SIMS spectra of a reference polymer plate, which contained one specific nano clay composite, were acquired. For each modified clay additive, a set of characteristic diagnostic ions could be identified, which then was used to successfully assign unknown clay additives to the corresponding reference material. Thus, the described methodology could be used to define and characterize nano clay within polymer matrices. Copyright (c) 2014 John Wiley & Sons, Ltd.
Silver nanoparticles (SNP) are among the most commercialized nanoparticles. Here, we show that peptide-coated SNP cause functional impairment of human macrophages. A dose-dependent inhibition of phagocytosis is observed after nanoparticle treatment, and pretreatment of cells with N-acetyl cysteine (NAC) can counteract the phagocytosis disturbances caused by SNP.
Using the surface-sensitive mode of time-of-flight secondary ion mass spectrometry, in combination with multivariate statistical methods, we studied the composition of cell membranes in human macrophages upon exposure to SNP with and without NAC preconditioning. This method revealed characteristic changes in the lipid pattern of the cellular membrane outer leaflet in those cells challenged by SNP. Statistical analyses resulted in 19 characteristic ions, which can be used to distinguish between NAC pretreated and untreated macrophages. The present study discusses the assignments of surface cell membrane phospholipids for the identified ions and the resulting changes in the phospholipid pattern of treated cells. We conclude that the adverse effects in human macrophages caused by SNP can be partially reversed through NAC administration. Some alterations, however, remained.
The sensing potential of CuO nanoparticles synthesized via. precipitation from a water/ionic liquid precursor (ILP) mixture was investigated. The particles have a moderate surface area of 66 m(2)/g after synthesis, which decreases upon thermal treatment to below 5 m(2)/g. Transmission electron microscopy confirms crystal growth upon annealing, likely due to sintering effects. The as-synthesized particles can be used for ethanol sensing. The respective sensors show fast response and recovery times of below 10 s and responses greater than 2.3 at 100 ppm of ethanol at 200 degrees C, which is higher than any CuO-based ethanol sensor described so far.
The article describes the synthesis and properties of new ionogels for ion transport. A new preparation process using an organic linker, bis(3-(trimethoxysilyl) propyl) amine (BTMSPA), yields stable organosilica matrix materials. The second ionogel component, the ionic liquid 1-methyl-3-(4-sulfobutyl) imidazolium 4-methylbenzenesulfonate, [BmimSO(3)H][PTS], can easily be prepared with near-quantitative yields. [BmimSO(3)H][PTS] is the proton conducting species in the ionogel. By combining the stable organosilica matrix with the sulfonated ionic liquid, mechanically stable, and highly conductive ionogels with application potential in sensors or fuel cells can be prepared.
The effect of cellulose-based polyelectrolytes on biomimetic calcium phosphate mineralization is described. Three cellulose derivatives, a polyanion, a polycation, and a polyzwitterion were used as additives. Scanning electron microscopy, X-ray diffraction, IR and Raman spectroscopy show that, depending on the composition of the starting solution, hydroxyapatite or brushite precipitates form. Infrared and Raman spectroscopy also show that significant amounts of nitrate ions are incorporated in the precipitates. Energy dispersive X-ray spectroscopy shows that the Ca/P ratio varies throughout the samples and resembles that of other bioinspired calcium phosphate hybrid materials. Elemental analysis shows that the carbon (i.e., polymer) contents reach 10% in some samples, clearly illustrating the formation of a true hybrid material. Overall, the data indicate that a higher polymer concentration in the reaction mixture favors the formation of polymer-enriched materials, while lower polymer concentrations or high precursor concentrations favor the formation of products that are closely related to the control samples precipitated in the absence of polymer. The results thus highlight the potential of (water-soluble) cellulose derivatives for the synthesis and design of bioinspired and bio-based hybrid materials.
Klassischerweise haben Salze, beispielsweise Kochsalz, Schmelzpunkte von einigen hundert Grad Celsius und mehr. Ionische Flüssigkeiten sind dagegen Salze, deren Schmelzpunkt zum Teil weit unter der Raumtemperatur liegt. Sie sind daher bei Raumtemperatur flüssig. Obwohl ionische Flüssigkeiten seit 1914 bekannt sind, hatten sie bis vor 15 Jahren keinerlei Bedeutung. Heute jedoch werden ionische Flüssigkeiten aufgrund ihrer vorteilhaften Eigenschaften, wie hohe Leitfähigkeit oder hohe Temperaturstabilität, unter anderem zur Papierverarbeitung oder in flexiblen Solarzellen eingesetzt. Die Antrittsvorlesung wird sich insbesondere mit der Herstellung anorganischer Partikel befassen und zeigen, wie ionische Flüssigkeiten zur Herstellung neuer Materialien für verschiedene Anwendungen genutzt werden können.
Ionogels (IGs), also termed ion gels, are functional hybrid materials based on an ionic liquid (IL) and a polymeric, hybrid, or inorganic matrix. IGs combine the properties of the matrix such as mechanical strength with IL properties like high ionic conductivity, high thermal stability, or catalytic activity. IGs are thus attractive for many applications, but the vast majority of IGs made and published so far are bulk materials or dense films. Applications like sensing or catalysis, however, would benefit from IGs with high surface areas or defined surface morphologies or architectures. In spite of this, only relatively few examples of high-surface-area IGs have been made so far; this has mostly been achieved by electrospinning, which has proven to be a promising strategy towards advanced IGs. The current review discusses first developments and outlines the future potential of electrospun ionogels, predominantly from a materials and inorganic chemistry perspective.
Luminescent Ionogels with Excellent Transparency, High Mechanical Strength, and High Conductivity
(2020)
The paper describes a new kind of ionogel with both good mechanical strength and high conductivity synthesized by confining the ionic liquid (IL) 1-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide ([Bmim][NTf₂]) within an organic–inorganic hybrid host. The organic–inorganic host network was synthesized by the reaction of methyltrimethoxysilane (MTMS), tetraethoxysilane (TEOS), and methyl methacrylate (MMA) in the presence of a coupling agent, offering the good mechanical strength and rapid shape recovery of the final products. The silane coupling agent 3-methacryloxypropyltrimethoxysilane (KH-570) plays an important role in improving the mechanical strength of the inorganic–organic hybrid, because it covalently connected the organic component MMA and the inorganic component SiO₂. Both the thermal stability and mechanical strength of the ionogel significantly increased by the addition of IL. The immobilization of [Bmim][NTf₂] within the ionogel provided the final ionogel with an ionic conductivity as high as ca. 0.04 S cm⁻¹ at 50 °C. Moreover, the hybrid ionogel can be modified with organosilica-modified carbon dots within the network to yield a transparent and flexible ionogel with strong excitation-dependent emission between 400 and 800 nm. The approach is, therefore, a blueprint for the construction of next-generation multifunctional ionogels.