Counterion effects on the mesomorphic and electrochemical properties of guanidinium salts.

Ionic liquid crystals (ILCs) combine the ion mobility of ionic liquids with the order and self-assembly of thermotropic mesophases. To understand the role of the anion in ILCs, wedge-shaped arylguanidinium salts with tetradecyloxy side chains were chosen as benchmark systems and their liquid crystalline self-assembly in the bulk phase as well as their electrochemical behavior in solution were studied depending on the anion. Differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and X-ray diffraction (WAXS, SAXS) experiments revealed that for spherical anions, the phase width of the hexagonal columnar mesophase increased with the anion size, while for non-spherical anions, the trends were less clear cut. Depending on the anion, the ILCs showed different stability towards electrochemical oxidation and reduction with the most stable being the PF6 based compound. Cyclic voltammetry (CV) and density functional theory (DFT) calculations suggest a possible contribution of the guanidinium cation to the oxidation processes.

Identification of the First Sulfobetaine Hydrogel-Binding Peptides via Phage Display Assay.

Using the M13 phage display, a series of 7- and 12-mer peptides which interact with new sulfobetaine hydrogels are identified. Two peptides each from the 7- and 12-mer peptide libraries bind to the new sulfobetaine hydrogels with high affinity compared to the wild-type phage lacking a dedicated hydrogel binding peptide. This is the first report of peptides binding to zwitterionic sulfobetaine hydrogels and the study therefore opens up the pathway toward new phage or peptide/hydrogel hybrids with high application potential.

Modification of 3D-Printed PLA Structures Using Photo-Iniferter Polymerization: Toward On-Demand Antimicrobial Water Filters.

Water filtration is an important application to ensure the accessibility of clean drinking water. As requirements and contaminants vary on a local level, adjustable filter devices and their evaluation with contaminants are required. Within this work, modular filter devices are designed featuring an adjustable surface functionalization. For this purpose, 3D-printed structures are created consisting of bio-based poly(lactic acid) (PLA) that are manufactured by extrusion printing. The surface of PLA is activated with amino groups that are used to install xanthates as chain transfer agents. Subsequently, photo-iniferter (PI) polymerization is used to create cationic polymer brushes on the surface of PLA substrates. Multiple surface characterization techniques are employed to prove successful growth of polymer brushes on PLA. After initial optimization studies on flat surfaces, filter devices are printed, functionalized, and used to remove bacteria from contaminated water. Significant reduction of the number of microorganisms is detected after filtration (single filtration or cycling) and contaminating organism can also be removed from freshwater samples by simple incubation with a 3D-printed filter. The herein developed setup for producing functional filter devices and probing their performance in affinity filtration is a useful platform technology, enabling the rapid testing of polymer brushes for such applications.

Ligand Effect in 1-Octanethiol Passivation of InP/ZnSe/ZnS Quantum Dots-Evidence of Incomplete Surface Passivation during Synthesis.

The lack of anionic carboxylate ligands on the surface of InP/ZnSe/ZnS quantum dots (QDs), where zinc carboxylate ligands can be converted to carboxylic acid or carboxylate ligands via proton transfer by 1-octanethiol, is demonstrated. The as-synthesized QDs initially have an under-coordinated vacancy surface, which is passivated by solvent ligands such as ethanol and acetone. Upon exposure of 1-octanethiol to the QD surface, 1-octanethiol effectively induces the surface binding of anionic carboxylate ligands (derived from zinc carboxylate ligands) by proton transfer, which consequently exchanges ethanol and acetone ligands that bind on the incomplete QD surface. These systematic chemical analyses, such as thermogravimetric analysis-mass spectrometry and proton nuclear magnetic resonance spectroscopy, directly show the interplay of surface ligands, and it associates with QD light-emitting diodes (QD-LEDs). It is believed that this better understanding can lead to industrially feasible QD-LEDs.

Tetrahalidometallate(II) Ionic Liquids with More than One Metal: The Effect of Bromide versus Chloride.

Fifteen N-butylpyridinium salts - five monometallic [C4 Py]2 [MBr4 ] and ten bimetallic [C4 Py]2 [M0.5 a M0.5 b Br4 ] (M=Co, Cu, Mn, Ni, Zn) - were synthesized, and their structures and thermal and electrochemical properties were studied. All the compounds are ionic liquids (ILs) with melting points between 64 and 101 °C. Powder and single-crystal X-ray diffraction show that all ILs are isostructural. The electrochemical stability windows of the ILs are between 2 and 3 V. The conductivities at room temperature are between 10-5 and 10-6  S cm-1 . At elevated temperatures, the conductivities reach up to 10-4  S cm-1 at 70 °C. The structures and properties of the current bromide-based ILs were also compared with those of previous examples using chloride ligands, which illustrated differences and similarities between the two groups of ILs.

Ionic Liquids with More than One Metal: Optical and Electrochemical Properties versus d-Block Metal Combinations.

Thirteen N-butylpyridinium salts, including three monometallic [C4 Py]2 [MCl4 ], nine bimetallic [C4 Py]2 [M1-x a Mx b Cl4 ] and one trimetallic compound [C4 Py]2 [M1-y-z a My b Mz c Cl4 ] (M=Co, Cu, Mn; x=0.25, 0.50 or 0.75 and y=z=0.33), were synthesized and their structure and thermal and electrochemical properties were studied. All compounds are ionic liquids (ILs) with melting points between 69 and 93 °C. X-ray diffraction proves that all ILs are isostructural. The conductivity at room temperature is between 10-4 and 10-8  S cm-1 . Some Cu-based ILs reach conductivities of 10-2  S cm-1 , which is, however, probably due to IL dec. This correlates with the optical bandgap measurements indicating the formation of large bandgap semiconductors. At elevated temperatures approaching the melting points, the conductivities reach up to 1.47×10-1  S cm-1 at 70 °C. The electrochemical stability windows of the ILs are between 2.5 and 3.0 V.

Insights about the Absence of Rb Cation from the 3D Perovskite Lattice: Effect on the Structural, Morphological, and Photophysical Properties and Photovoltaic Performance.

Efficiencies >20% are obtained from the perovskite solar cells (PSCs) employing Cs+ and Rb+ based perovskite compositions; therefore, it is important to understand the effect of these inorganic cations specifically Rb+ on the properties of perovskite structures. Here the influence of Cs+ and Rb+ is elucidated on the structural, morphological, and photophysical properties of perovskite structures and the photovoltaic performances of resulting PSCs. Structural, photoluminescence (PL), and external quantum efficiency studies establish the incorporation of Cs+ (x < 10%) but amply rule out the possibility of Rb-incorporation into the MAPbI3 (MA = CH3 NH3+ ) lattice. Moreover, morphological studies and time-resolved PL show that both Cs+ and Rb+ detrimentally affect the surface coverage of MAPbI3 layers and charge-carrier dynamics, respectively, by influencing nucleation density and by inducing nonradiative recombination. In addition, differential scanning calorimetry shows that the transition from orthorhombic to tetragonal phase occurring around 160 K requires more thermal energy for the Cs-containing MAPbI3 systems compared to the pristine MAPbI3 . Investigation including mixed halide (I/Br) and mixed cation A-cation based compositions further confirms the absence of Rb+ from the 3D-perovskite lattice. The fundamental insights gained through this work will be of great significance to further understand highly promising perovskite compositions.

CuS nanoplates from ionic liquid precursors-Application in organic photovoltaic cells.

Hexagonal p-type semiconductor CuS nanoplates were synthesized via a hot injection method from bis(trimethylsilyl)sulfide and the ionic liquid precursor bis(N-dodecylpyridinium) tetrachloridocuprate(ii). The particles have a broad size distribution with diameters between 30 and 680 nm and well-developed crystal habits. The nanoplates were successfully incorporated into organic photovoltaic (OPV) cells as hole conduction materials. The power conversion efficiency of OPV cells fabricated with the nanoplates is 16% higher than that of a control device fabricated without the nanoplates.

Ionogels Based on Poly(methyl methacrylate) and Metal-Containing Ionic Liquids: Correlation between Structure and Mechanical and Electrical Properties.

Ionogels (IGs) based on poly(methyl methacrylate) (PMMA) and the metal-containing ionic liquids (ILs) bis-1-butyl-3-methlimidazolium tetrachloridocuprate(II), tetrachloride cobaltate(II), and tetrachlorido manganate(II) have been synthesized and their mechanical and electrical properties have been correlated with their microstructure. Unlike many previous examples, the current IGs show a decreasing stability in stress-strain experiments on increasing IL fractions. The conductivities of the current IGs are lower than those observed in similar examples in the literature. Both effects are caused by a two-phase structure with micrometer-sized IL-rich domains homogeneously dispersed an IL-deficient continuous PMMA phase. This study demonstrates that the IL-polymer miscibility and the morphology of the IGs are key parameters to control the (macroscopic) properties of IGs.

Modular thiol-ene chemistry approach towards mesoporous silica monoliths with organically modified pore walls.

The surface modification of mesoporous silica monoliths through thiol-ene chemistry is reported. First, mesoporous silica monoliths with vinyl, allyl, and thiol groups were synthesized through a sol-gel hydrolysis-polycondensation reaction from tetramethyl orthosilicate (TMOS) and vinyltriethoxysilane, allyltriethoxysilane, and (3-mercaptopropyl)trimethoxysilane, respectively. By variation of the molar ratio of the comonomers TMOS and functional silane, mesoporous silica objects containing different amounts of vinyl, allyl, and thiol groups were obtained. These intermediates can subsequently be derivatized through radical photoaddition reactions either with a thiol or an olefin, depending on the initial pore wall functionality, to yield silica monoliths with different pore-wall chemistries. Nitrogen sorption, small-angle X-ray scattering, solid-state NMR spectroscopy, elemental analysis, thermogravimetric analysis, and redox titration demonstrate that the synthetic pathway influences the morphology and pore characteristics of the resulting monoliths and also plays a significant role in the efficiency of functionalization. Moreover, the different reactivity of the vinyl and allyl groups on the pore wall affects the addition reaction, and hence, the degree of the pore-wall functionalization. This report demonstrates that thiol-ene photoaddition reactions are a versatile platform for the generation of a large variety of organically modified silica monoliths with different pore surfaces.

Poly(ethylene oxide)-b-poly(3-sulfopropyl methacrylate) block copolymers for calcium phosphate mineralization and biofilm inhibition.

Poly(ethylene oxide) (PEO) has long been used as an additive in toothpaste, partly because it reduces biofilm formation on teeth. It does not, however, reduce the formation of dental calculus or support the remineralization of dental enamel or dentine. The present article describes the synthesis of new block copolymers on the basis of PEO and poly(3-sulfopropyl methacrylate) blocks using atom transfer radical polymerization. The polymers have very large molecular weights (over 10(6) g/mol) and are highly water-soluble. They delay the precipitation of calcium phosphate from aqueous solution but, upon precipitation, lead to relatively monodisperse hydroxyapatite (HAP) spheres. Moreover, the polymers inhibit the bacterial colonization of human enamel by Streptococcus gordonii, a pioneer bacterium in oral biofilm formation, in vitro. The formation of well-defined HAP spheres suggests that a polymer-induced liquid precursor phase could be involved in the precipitation process. Moreover, the inhibition of bacterial adhesion suggests that the polymers could be utilized in caries prevention.

Synthesis and Characterization of Ultra-Small Gold Nanoparticles in the Ionic Liquid 1-Ethyl-3-methylimidazolium Dicyanamide, [Emim][DCA].

We report on gold clusters with around 62 gold atoms and a diameter of 1.15±0.10 nm. Dispersions of the clusters are long-term stable for two years at ambient conditions. The synthesis was performed by mixing tetrachloroauric acid (HAuCl4 ⋅ 3 H2 O) with the ionic liquid 1-ethyl-3-methylimidazolium dicyanamide ([Emim][DCA]) at temperatures of 20 to 80 °C. Characterization was performed with small-angle X-ray scattering (SAXS), UV-Vis spectroscopy, and MALDI-TOF mass spectrometry. A three-stage model is proposed for the formation of the clusters, in which cluster growth from gold nuclei takes place according to the Lifshitz-Slyozov-Wagner (LSW) model followed by oriented attachment to form colloidal stable clusters.

Boosting the photo-switchability of double-responsive water-soluble polymers by incorporating arylazopyrazole dyes.

Dual thermo- and light-responsive water-soluble copolymers that respond to exclusively non-invasive triggers are obtained by functionalising poly(N,N-dimethylacrylamide) with arylazopyrazole side chains. The light-induced E-Z (trans-Z) photo isomerisation of these dyes provides an exceptionally effective photo-switch, which can reversibly shift the LCST-type phase transition temperatures by almost 25 K.

Dynamics of Water Clusters Confined in Ionic Liquid at an Elevated Pressure.

Over the years, numerous experimental and theoretical efforts have been dedicated to investigating the mysteries of water and determining its new unexplored physical properties. Despite this, high-pressure studies of water and aqueous mixtures close to the glass transition still represent an unknown area of research. Herein, we address a fundamental issue: the validity of the density scaling concept for fast water dynamics. For this purpose, we performed ambient and high-pressure dielectric measurements of a supercooled equimolar aqueous mixture of an acidic ionic liquid. All isothermal and isobaric relaxation data describing the time scale of charge transport (τσ) and fast dynamics within the water clusters (τν) reveal visual evidence of a liquid-glass transition. Furthermore, both relaxation processes satisfy the ργ/T scaling concept with a single exponent γ = 0.58. Thus, the scaling exponent is a state-point-independent parameter for the dynamics of water clusters confined in ionic liquid investigated in the pressure range up to 300 MPa.

Advances in Biomimetics: Combination of Various Effects at Different Scales.

Biomimetics (bionics, bioinspired technology) refers to research on living systems and attempts to transfer their properties to engineering applications [...].

Efficient Removal of Tetracycline and Bisphenol A from Water with a New Hybrid Clay/TiO2 Composite.

New TiO2 hybrid composites were prepared from kaolin clay, predried and carbonized biomass, and titanium tetraisopropoxide and explored for tetracycline (TET) and bisphenol A (BPA) removal from water. Overall, the removal rate is 84% for TET and 51% for BPA. The maximum adsorption capacities (qm) are 30 and 23 mg/g for TET and BPA, respectively. These capacities are far greater than those obtained for unmodified TiO2. Increasing the ionic strength of the solution does not change the adsorption capacity of the adsorbent. pH changes only slightly change BPA adsorption, while a pH > 7 significantly reduces the adsorption of TET on the material. The Brouers-Sotolongo fractal model best describes the kinetic data for both TET and BPA adsorption, predicting that the adsorption process occurs via a complex mechanism involving various forces of attraction. Temkin and Freundlich isotherms, which best fit the equilibrium adsorption data for TET and BPA, respectively, suggest that adsorption sites are heterogeneous in nature. Overall, the composite materials are much more effective for TET removal from aqueous solution than for BPA. This phenomenon is assigned to a difference in the TET/adsorbent interactions vs the BPA/adsorbent interactions: the decisive factor appears to be favorable electrostatic interactions for TET yielding a more effective TET removal.

Cellulose-based adsorbents for solid phase extraction and recovery of pharmaceutical residues from water.

Cellulose has attracted interest from researchers both in academic and industrial sectors due to its unique structural and physicochemical properties. The ease of surface modification of cellulose by the integration of nanomaterials, magnetic components, metal organic frameworks and polymers has made them a promising adsorbent for solid phase extraction of emerging contaminants, including pharmaceutical residues. This review summarizes, compares, and contrasts different types of cellulose-based adsorbents along with their applications in adsorption, extraction and pre-concentration of pharmaceutical residues in water for subsequent analysis. In addition, a comparison in efficiency of cellulose-based adsorbents and other types of adsorbents that have been used for the extraction of pharmaceuticals in water is presented. From our observation, cellulose-based materials have principally been investigated for the adsorption of pharmaceuticals in water. However, this review aims to shift the focus of researchers to the application of these adsorbents in the effective pre-concentration of pharmaceutical pollutants from water at trace concentrations, for quantification. At the end of the review, the challenges and future perspectives regarding cellulose-based adsorbents are discussed, thus providing an in-depth overview of the current state of the art in cellulose hybrid adsorbents for extraction of pharmaceuticals from water. This is expected to inspire the development of solid phase exraction materials that are efficient, relatively cheap, and prepared in a sustainable way.

Carbon-based ionogels: tuning the properties of the ionic liquid via carbon-ionic liquid interaction.

The behavior of two ionic liquids (ILs), 1-ethyl-3-methylimidazolium dicyanamide [Emim][DCA] and 1-ethyl-3-methylimidazolium triflate [Emim][TfO], in (meso)porous carbonaceous hosts was investigated. Prior to IL incorporation into the host, the carbon matrix was thermally annealed between 180 and 900 °C to control carbon condensation and surface chemistry. The resulting materials have an increasing "graphitic" carbon character with increasing treatment temperature, reflected in a modified behavior of the ILs when impregnated into the carbon host. The two ILs show significant changes in the thermal behavior as measured from differential scanning calorimetry; these changes can be assigned to anion-π interaction between the IL anions and the pore wall surfaces of these flexible carbonaceous support materials.

Template synthesis of dual-functional porous MoS2 nanoparticles with photothermal conversion and catalytic properties.

Advanced catalysis triggered by photothermal conversion effects has aroused increasing interest due to its huge potential in environmental purification. In this work, we developed a novel approach to the fast degradation of 4-nitrophenol (4-Nip) using porous MoS2 nanoparticles as catalysts, which integrate the intrinsic catalytic property of MoS2 with its photothermal conversion capability. Using assembled polystyrene-b-poly(2-vinylpyridine) block copolymers as soft templates, various MoS2 particles were prepared, which exhibited tailored morphologies (e.g., pomegranate-like, hollow, and open porous structures). The photothermal conversion performance of these featured particles was compared under near-infrared (NIR) light irradiation. Intriguingly, when these porous MoS2 particles were further employed as catalysts for the reduction of 4-Nip, the reaction rate constant was increased by a factor of 1.5 under NIR illumination. We attribute this catalytic enhancement to the open porous architecture and light-to-heat conversion performance of the MoS2 particles. This contribution offers new opportunities for efficient photothermal-assisted catalysis.

Effect of the Post-Harvest Processing on Protein Modification in Green Coffee Beans by Phenolic Compounds.

The protein fraction, important for coffee cup quality, is modified during post-harvest treatment prior to roasting. Proteins may interact with phenolic compounds, which constitute the major metabolites of coffee, where the processing affects these interactions. This allows the hypothesis that the proteins are denatured and modified via enzymatic and/or redox activation steps. The present study was initiated to encompass changes in the protein fraction. The investigations were limited to major storage protein of green coffee beans. Fourteen Coffea arabica samples from various processing methods and countries were used. Different extraction protocols were compared to maintain the status quo of the protein modification. The extracts contained about 4-8 µg of chlorogenic acid derivatives per mg of extracted protein. High-resolution chromatography with multiple reaction monitoring was used to detect lysine modifications in the coffee protein. Marker peptides were allocated for the storage protein of the coffee beans. Among these, the modified peptides K.FFLANGPQQGGK.E and R.LGGK.T of the α-chain and R.ITTVNSQK.I and K.VFDDEVK.Q of ß-chain were detected. Results showed a significant increase (p < 0.05) of modified peptides from wet processed green beans as compared to the dry ones. The present study contributes to a better understanding of the influence of the different processing methods on protein quality and its role in the scope of coffee cup quality and aroma.