Impact of oil type on nanoemulsion formation and Ostwald ripening stability

The formation of stable transparent nanoemulsions poses two challenges: the ability to initially create an emulsion where the entire droplet size distribution is below 80 nm, and the subsequent stabilization of this emulsion against Ostwald ripening. The physical properties of the oil phase and the nature of the surfactant layer were found to have a considerable impact on nanoemulsion formation and stabilization. Nanoemulsions made with high viscosity oils, such as long chain triglycerides (LCT), were considerably larger ( D = 120 nm) than nanoemulsions prepared with low viscosity oils such as hexadecane ( D = 80 nm). The optimization of surfactant architecture, and differential viscosity eta D/eta C, has led to the formation of remarkably small nanoemulsions. With average sizes below 40 nm they are some of the smallest homogenized emulsions ever reported. What is more remarkable is that LCT nanoemulsions do not undergo Ostwald ripening and are physically stable for over 3 months. Ostwald ripening is prevented by the large molar volume of long chain triglyceride oils, which makes them insoluble in water thus providing a kinetic barrier to Ostwald ripening. Examination of the Ostwald ripening of mixed oil nanoemulsions found that the entropy gain associated with oil demixing provided a thermodynamic barrier to Ostwald ripening. Not only are the nanoemulsions created in this work some of the smallest reported, but they are also thermodynamically stable to Ostwald ripening when at least 50% of the oil phase is an insoluble triglyceride.     

Mechanistic insights into NO3* induced self-terminating radical oxygenations, part 1: a computational study on NO3* and its addition to alkynes

The geometry of the nitrate radical, NO3*, for which unrestricted Hartree-Fock (HF) breaks spatial symmetry of the wave function, was optimized using hybrid density functionals that include varying fractions of Hartree-Fock exchange. Although symmetry breaking was not observed even when the functional with the highest HF exchange (BHandHLYP) was used, only B3LYP correctly describes the D(3h) symmetry of NO3* as ground-state structure with the lowest energy. Further, geometries and energies of the stationary points in the addition of NO3* to ethyne, propyne, and 2-butyne were calculated using ab initio and density functional methods. The reactions proceed through Z-configurated transition states leading to Z-configurated vinyl radicals with the activation barrier decreasing with increasing methyl substitution at the C[triple bond]C by ca. 11 kJ mol(-1) per methyl group. It was found that the results obtained at the BHandHLYP/cc-pVDZ level of theory are in good agreement with the data from single-point QCISD and CCSD(T) calculations.     

A Review of Surface Functionalized Amine Terminated Dendrimers for Application in Biological and Molecular Sensing

Dendrimers are three dimensional nanosized synthetic molecules that have internal cavities and numerous surface groups. In recent times they have received increased attention in sensing applications. For dendrimers to be used as sensors, they most commonly require functionalization at their surface. This is because the surface is generally the first point of contact between the dendrimer and the outside world, hence surface functionalization serves to selectively home in on the target analyte. Further, sensor signals may be transmitted through surface functionalities e.g. fluorochromic molecules. It is therefore important to document surface functionalization approaches. Dendrimers with amine surface groups have the advantage of being able to be conjugated to other molecules via an amide linkage, which is one of the most fundamental and widespread chemical bonds in nature. In this paper we demonstrate the properties of dendrimers that make them so applicable to sensing. We review several methods for functionalizing dendrimers via an amide linkage, as well as present a review of surface functionalized polyamidoamine, polyamine, and polypeptide dendrimers that have been employed for biological, chemical and molecular sensing.     

Zur Stereochemie der Vitamin D3-Epoxide Röntgenstrukturanalyse einer 5,6-7,8-Diepoxidverbindung

Epoxidation of vitamin D₃ with benzonitrile ¦H₂O₂¦ KHCO₃ (Payne's reagent) yields exclusively the 5,6-mono-oxirane2. Further epoxidation with the same reagent gives the 5,6-7,8-bisepoxide3 a. Its stereochemistry and therefore the stereochemistry of2 was established by single crystal X-ray analysis of thep-Brbenzoate3b. Thereby for the first time a directive effect of a homoallylic hydroxyl group during thePayne-epoxidation was established.

Herrn Prof.Mihailovic (Universität Belgrad) mit den besten Wünschen zum 60. Geburtstag gewidmet.     

161Dy Time‐Domain Synchrotron Mössbauer Spectroscopy for Investigating Single‐Molecule Magnets Incorporating Dy Ions

Time‐domain synchrotron Mössbauer spectroscopy (SMS) based on the Mössbauer effect of ¹⁶¹Dy has been used to investigate the magnetic properties of a Dy^III‐based single‐molecule magnet (SMM). The magnetic hyperfine field of [Dy(Cy₃PO)₂(H₂O)₅]Br₃?2 (Cy₃PO)?2 H₂O?2 EtOH is with B₀=582.3(5) T significantly larger than that of the free‐ion Dy^III with a ⁶H_15/2 ground state. This difference is attributed to the influence of the coordinating ligands on the Fermi contact interaction between the s and 4f electrons of the Dy^III ion. This study demonstrates that ¹⁶¹Dy SMS is an effective local probe of the influence of the coordinating ligands on the magnetic structure of Dy‐containing compounds.     

A Low‐Temperature Molecular Precursor Approach to Copper‐Based Nano‐Sized Digenite Mineral for Efficient Electrocatalytic Oxygen Evolution Reaction

In the urge of designing noble metal‐free and sustainable electrocatalysts for oxygen evolution reaction (OER), herein, a mineral Digenite Cu₉S₅ has been prepared from a molecular copper(I) precursor, [{(PyHS)₂Cu^I(PyHS)}₂](OTf)₂ ( 1 ), and utilized as an anode material in electrocatalytic OER for the first time. A hot injection of 1 yielded a pure phase and highly crystalline Cu₉S₅, which was then electrophoretically deposited (EPD) on a highly conducting nickel foam (NF) substrate. When assessed as an electrode for OER, the Cu₉S₅/NF displayed an overpotential of merely 298±3 mV at a current density of 10 mA cm^?2 in alkaline media. The overpotential recorded here supersedes the value obtained for the best reported Cu‐based as well as the benchmark precious‐metal‐based RuO₂ and IrO₂ electrocatalysts. In addition, the choronoamperometric OER indicated the superior stability of Cu₉S₅/NF, rendering its suitability as the sustainable anode material for practical feasibility. The excellent catalytic activity of Cu₉S₅ can be attributed to the formation of a crystalline CuO overlayer on the conductive Cu₉S₅ that behaves as active species to facilitate OER. This study delivers a distinct molecular precursor approach to produce highly active copper‐based catalysts that could be used as an efficient and durable OER electro(pre)catalysts relying on non‐precious metals.     

Stable cellulose nanospheres for cellular uptake

Pure, perfectly spherical cellulose nanoparticles with sizes of ≈80-260 nm can be prepared by dialysis starting from trimethylsilylcellulose (TMSC). The aqueous suspensions obtained are storable for several months. Subsequent covalent labeling of the cellulose nanoparticles with FITC has no influence on particle size, shape, and stability. The particles can be sterilized and suspended in biological media without structural changes. Incorporation of FITC-labeled cellulose nanoparticles into living human fibroblasts is studied using confocal LSM. In contrast to cellulose nanocrystals, fast cellular uptake is found for the nanospheres without transfection reagents or attachment of a receptor molecule. This suggests an influence of the geometry of biocompatible nanomaterials on endocytosis.     

Mixed electrolytes in hydrophobic interaction chromatography†

An essential part of the modulation of protein‐binding capacity in hydrophobic interaction chromatography is the buffer‐salt system. Besides using “single” electrolytes, multicomponent electrolyte mixtures may be used as an additional tool. Both the protein solubility and the binding capacity depend on the position of a salt in the so‐called Hofmeister series. Specific interactions are observed for an individual protein‐salt combination. For salt mixtures, selectivity, recovery, and binding capacity do not behave like for the single salts that are positioned in between the two mixed components in the Hofmeister series, as the continuous correlation would suggest. Thus, finding strategies for mixed salts could potentially lead to improved capacities in hydrophobic interaction chromatography. Mixtures of ammonium sulfate, sodium citrate, sodium sulfate, sodium chloride, sodium acetate, and glycine were used to investigate the binding capacities for lysozyme and a monoclonal antibody on various hydrophobic resins. Resin capacity for two investigated proteins increases when mixtures consisting of a chaotropic and a kosmotropic salt are applied. It seems to be related to the rather basic isoelectric points of the proteins.     

Identification of polyimide materials using quantitative CE with UV and QTOF‐MS detection

Polyimides (PIs) are a group of widely used synthetic materials that service a variety of different purposes including microelectronics, insulating films and aerospace applications. Depending on the requirements (defined by the particular final product), the actual composition of PIs may show substantial chemical variation. To study this variation in chemical structure, CE‐MS can be employed for the determination of PI composition following chemical degradation of the polymer sample. PI is chemically decomposed to corresponding aromatic diamine and carboxylic acid components using an alkali fusion reaction. Solid polymer samples are fused in a potassium hydroxide melt yielding reaction products that are diluted in acid and can be immediately analysed by CE coupled to a Q/TOF‐MS with quantification performed using conventional UV detection. This approach involves a simple and rapid sample preparation yielding both qualitative and quantitative information regarding the chemical composition of the polymer. Application of the CE‐MS approach is shown for a range of commercially available PI and poly(amide–imide) materials and the results are used to infer the respective chemical compositions.     

Inverse colloidal crystal membranes for hydrophobic interaction membrane chromatography

A collaborative study on the robustness and portability of a capillary electrophoresis‐mass spectrometry method for peptide mapping was performed by an international team, consisting of 13 independent laboratories from academia and industry. All participants used the same batch of samples, reagents and coated capillaries to run their assays, whereas they utilized the capillary electrophoresis‐mass spectrometry equipment available in their laboratories. The equipment used varied in model, type and instrument manufacturer. Furthermore, different types of sheath‐flow capillary electrophoresis–mass spectrometry interfaces were used. Migration time, peak height and peak area of ten representative target peptides of trypsin‐digested bovine serum albumin were determined by every laboratory on two consecutive days. The data were critically evaluated to identify outliers and final values for means, repeatability (precision within a laboratory) and reproducibility (precision between laboratories) were established. For relative migration time the repeatability was between 0.05 and 0.18% RSD and the reproducibility between 0.14 and 1.3% RSD. For relative peak area repeatability and reproducibility values obtained were 3–12 and 9–29% RSD, respectively. These results demonstrate that capillary electrophoresis‐mass spectrometry is robust enough to allow a method transfer across multiple laboratories and should promote a more widespread use of peptide mapping and other capillary electrophoresis‐mass spectrometry applications in biopharmaceutical analysis and related fields.