Synthesis,Crystal Structures,and Spectroscopic Properties of Novel Gadolinium and Erbium Triphenylsiloxide Coordination Entities

In alkali metal and lanthanide coordination chemistry, triphenylsiloxides seem to be unduly underappreciated ligands. This is as surprising as that such substituents play a crucial role, among others, in stabilizing rare oxidation states of lanthanide ions, taking a part of intramolecular and molecular interactions stabilizing metal-oxygen cores and many others. This paper reports the synthesis and characterization of new lithium [Li₄(OSiPh₃)₄(THF)₂] (1), and sodium [Na₄(OSiPh₃)₄] (2) species, which were later used in obtaining novel gadolinium [Gd(OSiPh₃)₃(THF)₃]·THF (3), and erbium [Er(OSiPh₃)₃(THF)₃]·THF (4) configuration, it can result in res were determined for all 1–4 compounds, and in addition, IR, Raman, absorption spectroscopy studies were conducted for 3 and 4 lanthanide compounds. Furthermore, direct current (dc) variable-temperature magnetic susceptibility measurements on polycrystalline samples of 3 and 4 were carried out in the temperature range 1.8–300 K. The 3 shows behavior characteristics for the paramagnetism of the Gd³⁺ ion. In contrast, the magnetic properties of 4 are dominated by the crystal field effect on the Er³⁺ ion, masking the magnetic interaction between magnetic centers of neighboring molecules.     

The properties of the interfacial antimony cell and its application in potentiometric titrations of alkaloids in non-conducting solutions

The behaviour of an interfacial antimony device in potentiometric titrations in non-conducting solutions is described. In tests of the device, various alkaloids were titrated with organic acids, p-toluenesulphonic acid being the most satisfactory. The non-conducting media examined were chloroform, ligroin, benzene and carbon tetrachloride. In all cases, solutions of the titrant and the sample were prepared in the same organic solvent. Alkaloids in the range 10^?3–10^?4 M could usually be titrated with a precision of about 2%.     

Two-dimensional miscibility studies--the analysis of interaction between long-chain alcohols and semifluorinated alkanes

This work presents the results of phase behavior studies of two-dimensional (2D) binary systems involving semifluorinated alkanes (SFAs) and fatty alcohols. Four different SFAs were selected for investigations: (i) with a short and branched perfluorinated moiety (iF3H20), (ii) with a short and normal perfluorinated chain (F4H20), (iii) with a long and branched perfluorinated fragment (iF9H20), and (iv) with a long and normal perfluorinated group (F10H20). Two alcohols were selected to mix with the above-mentioned SFAs: tetradecanol and docosanol. The measurements were based on surface pressure/area isotherms in addition to Brewster angle microscope (BAM) imaging. Dependencies of the collapse surface pressure and the compression modulus vs the monolayer composition together with the excess free energy of mixing values, complemented with BAM images, enabled us to draw some general conclusions regarding the phase behavior of the investigated mixed systems. Generally, it has been noticed that the addition of docosanol into an SFA monolayer exerts a condensing effect, contrary to tetradecanol. Moreover, SFAs with a long perfluorinated segment mix to a larger extent with alcohols as compared to their analogues having a short perfluorinated moiety. The resultant phase diagrams for all the investigated eight mixtures are presented and discussed.     

Miniaturized electronic tongue with an integrated reference microelectrode for the recognition of milk samples

This work presents the application of a new construction of an electronic tongue for the classification of milk originating from various producers. Integrated array of microelectrodes was fabricated from epoxy-glass laminate. PVC membranes with various additives were used as chemosensitive layers. The developed device is capable of recognition of milk samples with high correctness. Moreover, the application of miniaturized reference electrode, integrated on the same substrate, also provided satisfactory results, which can be helpful in future constructions of hand-held electronic tongue systems.     

Collective rotations of ferroelectric liquid crystals at the air/water interface

We study the Langmuir monolayers of four different ferroelectric liquid crystals on water surface. Two of them are attached to water surface by their polar groups, and the chiral groups, at the opposite ends of the elongated molecules, remain well above the interface. The other two ferroelectrics have both groups (polar and chiral) at close proximity, and therefore the chiral group is also attached to the surface or even submerged in water. We demonstrate that only when the chiral group of the ferroelectric liquid crystal in Langmuir monolayer is not attached to the interface and stays in the air does the system exhibit the collective rotations induced by evaporation of water (described for the first time by: Tabe, Y.; Yokoyama, H. Nat. Mater. 2003, 2, 806). The isotherms of surface pressure and surface potential versus molecular area of four compounds were measured with simultaneous observations using Brewster angle microscopy. Experimental data of the compression isotherms are described with a van der Waals model with very good accuracy, and the fitted parameters were used for calculations of compressibility coefficients for different phases found in the compounds under investigations. The ability of the two compounds for rotation and the disability of the two others is discussed in a context of thermodynamic properties of the monolayers.     

Algorithms generating images of attractors of generalized iterated function systems

The paper is devoted to searching algorithms which will allow to generate images of attractors of generalized iterated function systems (GIFS in short), which are certain generalization of classical iterated function systems, defined by Mihail and Miculescu in 2008, and then intensively investigated in the last years (the idea is that instead of selfmaps of a metric space X, we consider mappings form the Cartesian product X×...×X to X). Two presented algorithms are counterparts of classical deterministic algorithm and so-called chaos game. The third and fourth one is fitted to special kind of GIFSs - to affine GIFS, which are, in turn, also investigated.     

Surface activity of commercial food grade modified starches

An attempt to quantitative evaluation of the functionality of food grade chemically modified starches in the emulsion systems by estimation of their surface activity as well as the capability of thickening food products was the main purpose of this present work. It was stated that chemically modified starches reveal higher surface activity at air/water and toluene/water interfaces in comparison to the native starch. The increase of the degree of substitution of polar carboxyl groups as well as rather non-polar acetyl ones results in an enhance of surface activity. Starch sodium octenylsuccinate stands out from other investigated starches, in its excellent capability of lowering surface and interfacial tension. Cross-linked starches reveal excellent stabilisation activity at a pH range of 5.5–7.0 but their surface activity is lower than those of other modified starches. Acetylated starch as well as starch sodium octenylsuccinate reveal satisfactory thickening capability up to pH 4.5 and moreover their surface activity (especially of E 1450) allows us to recommend them as functional constituents of food emulsions. Low thickening capability of oxidised starches rather excluded these derivatives from the group of potential functional additives for food emulsions.     

Radical–anion coupling through reagent design: hydroxylation of aryl halides

The design and development of an oxime-based hydroxylation reagent, which can chemoselectively convert aryl halides (X = F, Cl, Br, I) into phenols under operationally simple, transition-metal-free conditions is described. Key to the success of this approach was the identification of a reducing oxime anion which can interact and couple with open-shell aryl radicals. Experimental and computational studies support the proposed radical-nucleophilic substitution chain mechanism.

The design and development of an oxime-based hydroxylation reagent, which can chemoselectively convert aryl halides (X = F, Cl, Br, I) into phenols under operationally simple, transition-metal-free conditions is described.     

NHC-Rhodium-Catalyzed Synthesis of Novel Silsesquioxanes Containing S-Si and S-Ge Bonds and Their Application in Hydrosilylation Process

The efficient and straightforward NHC-rhodium-catalyzed thiol-silane and thiol-germanane coupling reactions, leading to new classes of functionalized SQ-based materials, are presented for the first time. The proposed strategies use commercially available reagents and show a broad functional groups tolerance, which opens a possibility of effective synthetic procedures of biologically active compounds.