Intermetallic communication through a 1,3,5-triethynylbenzene connector

The electrochemical behavior of two series of homo- and heterometallic 1,3,5-triethynylbenzene-based transition metal complexes containing [(η²-dppf)(η⁵-C₅H₅)Ru], [(PPh₃)₂(η⁵-C₅H₅)Os], [(^tBu₂bpy)(CO)₃Re], and [(bpy)(CO)₃ClRe] (dppf = 1,1′-bis(diphenylphosphino)ferrocene; ^tBu₂bpy = 4,4′-di-tert-butyl-2,2′-bipyridyl; bpy = 2,2′-bipyridyl-5-yl) building blocks have been studied, showing that there is electronic interaction between the appropriate metal atoms. The electronic absorption spectra reveal high energy bands corresponding to intraligand π → π∗ transitions (bpy, alkynyl) and low energy absorptions which are attributed to MLCT transitions; replacement of ruthenium by osmium results in a blue-shift of the MLCT bands. The associated radical cations of three complexes were in situ generated by chemical oxidation and characterized by continuous wave electron paramagnetic resonance (EPR) investigations in X-band performed at low temperatures.     

Optimisation of aqueous synthesis of iron oxide nanoparticles for biomedical applications

Iron oxide nanoparticles (IONPs) were prepared via aqueous synthesis which combines alkaline co-precipitation (CP) of ferric and ferrous precursors with mild hydrothermal (HT) treatment without cupping agents (CA). In this novel synthesis route, CP + HT, we found the optimal synthesis conditions to obtain IONPs without a second phase and with the size larger than in standard CP: the equal number of Fe(II) and Fe(III) ions are co-precipitated with 6 M ammonia and further HT treated in mild conditions (120 °C for 24 h) without CA. The IONPs obtained by novel CP + HT route had faceted rectangular morphology, a mean TEM diameter of 21.5 ± 6.3 nm, a hydrodynamic diameter of 30.2 ± 9.1 nm and a zeta potential at pH 4 of 48.2 ± 0.6 mV. After the subsequent oxidation step, the final product (IONPs) was studied by XRD, FTIR and XPS, which confirmed the desired structure of γ-Fe₂O₃. Importantly, this synthesis was especially planned for the preparation of IONPs for biomedical applications. Thus, our novel synthesis was designed to be compliant with the regulations of nano-safety: no special atmosphere, no complex multistep size separation, no organic solvents or solvent exchange, no CA and their washing and the use of low temperature in the final optimised conditions. In addition, this simple synthesis route combines the CP and HT methods, which are both proven to be scalable. Moreover, repeatability and reproducibility of the optimal CP + HT synthesis were confirmed on the lab-scale; more than 100 repetitions with different dishes, different operators and different batches of chemicals were performed.     

Commodity and resource ETF trading patterns during the financial crisis

This study estimates the parameters of a power law fit of the distribution of log returns of exchange traded funds (ETFs) before, during, and after the recent financial crisis. It is found, that there is considerable variation both between ETFs and between calm and turbulent phases. Exponents of the daily log return distribution are estimated to lie mostly between 3.0 and 5.0 depending on the ETF. In minute‐by‐minute, trading data much lower power law exponents have been found concentrating between 3.0 and 4.0 and sometimes dropping to values close to or below 3.0. Further, there is evidence for changes in the distribution during times of turbulence (value of the exponent, improvement in the goodness of fit measures of the distribution). It can be hypothesized that effects such as, infinite variance (for α < 3) or changes in the form of the distribution can occur, in turn affecting the predictability of the system which has implications for the possibility to control or regulate financial markets under such conditions. © 2014 Wiley Periodicals, Inc. Complexity 21: 73–83, 2016     

Calix[4]pyrroles bearing quinolinium moiety for halide sensing in aqueous solution

Sensing of chloride in aqueous solution with high selectivity is a challenging task and has a great potential for cellular imaging and analytical applications in food chemistry. Supramolecular binding motif calix[4]pyrrole has been conjugated with a known fluorescent probe for chloride – a quinolinium dye - through conformationally flexible and rigid linkers. Effects of the supramolecular host on the properties of the fluorescent dye and vice versa have been investigated by NMR, X-ray crystallographic and spectroscopic methods. New fluorescent probes have demonstrated better binding and quenching properties towards chloride, bromide and iodide in a 1:1 water-methanol mixture as compared to free calix[4]pyrrole and the quinolinium dye.     

Surface ionization state and nanoscale chemical composition of UV-irradiated poly(dimethylsiloxane) probed by chemical force microscopy, force titration, and electrokinetic measurements

The surface chemistry and ionization state of cross-linked poly(dimethylsiloxane) (PDMS) exposed to UV/ozone were studied as a function of treatment time. Various complementary and independent experimental techniques were utilized, which yielded information on the macroscopic as well as the nanometric scale. The average chemical composition of the PDMS surface was quantitatively investigated by time-of-flight secondary ion mass spectrometry (ToF-SIMS). It was found that the top 1-2 nm surface layer was dominated by silanol groups (-SiOH) for which the concentration increased with increasing treatment dose. The lateral distributions of the silanol groups were analyzed on the nanometer scale by means of atomic force microscopy (AFM) with chemically functionalized tip probes in aqueous buffer solutions at varying pHs. Spatially dependent pull-off force curves (also called "force volume" imaging) indicated the presence of strong chemical heterogeneity of the probed surface. This heterogeneity took the form of patches of silanol functionalities with high local concentration surrounded by a matrix of predominantly hydrophobic domains at low pH. The average pull-off forces for the entire surface scanned were significantly reduced for pH values larger than a characteristic pK(a) constant (in the range between 4.5 and 5.5). The extent of the decrease in the pull-off force and the particular value of pK(a) were found to be a function of treatment time and to differ from the commonly reported values for silanol functional groups on a homogeneous silica surface. These dependences were ascribed to the evoking of a protonation/deprotonation process of the surface silanol groups which was sensitive to the hydrophobic/hydrophilic balance of their close molecular environment. Intermolecular hydrogen bonding may also account for the shifts in the surface pK(a). Furthermore, depending on the nature of the electrolyte, a third effect related to double layer composition, as determined by specific ion adsorption, was quantitatively analyzed by streaming potential measurements in the presence of sodium chloride and phosphate electrolytes.     

Polymers in an external periodic field: the effect of the excluded volume interactions

By developing and making use of the "transfer operator" formalism, we calculate the number density and average Flory end-to-end distance of the polymers placed in an external periodic field. The considered mathematical problem is of immediate relevance for such realistic physical systems as the homopolymers immersed in the host structure of alternating layers that have different affinities for homopolymers (e.g., lamellar microphases of copolymers, ripple morphology of the mixed brush, and lipidwater systems). In contrast to the conventional ground state dominance approximation, the developed method makes it possible to calculate the characteristic size (Flory radius R(F)) of the polymers in the direction of applied external periodic field, with the effect of the excluded volume taken into account. The excluded volume interactions are shown to qualitatively change the behavior of R(F) as a function of the reduced field strength theta relative to the case of ideal Gaussian polymers. In particular, in the limit of strong fields theta>1 the average Flory radius R(F) is found to saturate to its minimal value, which is calculated as a function of the excluded volume parameter u. This finding is in distinct contrast to the result for the Flory radius R(F) in the case of ideal polymers where R(F) approaches zero as the interaction parameter theta increases.     

Oxidative and reductive carbodiazenylation of nonactivated olefins

Procedures for the carbodiazenylation of nonactivated olefins with a wide range of aryldiazonium salts have been developed. The azo compounds obtained can serve as valuable precursors for beta-arylamines (carboamination products), beta-amino acids, ketones, and various heterocyclic structures.     

Nitro-substituted stilbeneboronate pinacol esters and their fluoro-adducts. Fluoride ion induced polarity enhancement of arylboronate esters

A series of stilbeneboronate pinacol cyclic esters, containing none to three nitro groups, have been synthesized by various olefination reactions and characterized by X-ray single-crystal structure analysis. A stilbeneboronate ester bearing electron-acceptor groups experiences transition to a push-pull pi-electron system upon complexation with one fluoride ion at the boron atom. The UV-vis absorption maxima of the presented nitro-substituted stilbeneboronate esters are red-shifted upon addition of fluoride ions, indicating this binding event. The enhancement of the polarity of the investigated compounds and the changes in the electronic system were investigated by UV-vis absorption spectroscopy and solvatochromism. Additionally, studies were performed by natural bond orbital (NBO) analysis and RI-CC2 calculations of the vertical excitation energies. The synergism of fluoride ion complexation and solvation upon the UV-vis band shift is interpreted in terms of linear solvation energy relationships (LSERs) using the Kamlet-Taft solvent parameter set. It is found that the UV-vis absorption of the fluoro-boronates is strongly dependent on the solvents hydrogen-bond donating ability.     

Allylation and vinylation of aryl radicals generated from diazonium salts

Allylation and vinylation of aryl radicals generated from aryl diazonium salts provides rapid and efficient access to chlorinated and brominated derivatives of styrene and allylbenzene. Allyl chlorides were found to be better substrates than bromides due to decreased halogen transfer. Donor- and acceptor-substituted diazonium salts are well tolerated. The products represent important precursors for numerous further transformations.