Preparation and Characterisation of Nano-Structured WO<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> Layers for Photoelectrochromic Devices

Nano-structured WO₃-TiO₂ layers were prepared by the sol-gel route. To obtain transparent, porous and crack free layers up to 0.8 μ m with a single dipping cycle a templating strategy was used. As a template three-dimensionally network based on organically modified silane was introduced to the WO₃ and TiO₂ sols. The WO₃ layers were dip-coated onto the conductive glass substrate (TCO) and the TiO₂ layers on the top of the WO₃ layer. The morphology and the structure of the layers were determined by Scanning Electron Microscopy (SEM), High Resolution Transmission Electron Microscopy (HR-TEM), Energy Dispersive X-Ray Spectroscopy (EDXS), Auger and Infrared spectroscopy. SEM image of the WO₃-TiO₂ layer confirmed the nano-porosity of the layers and give the size of the particles of about 10 nm for TiO₂ and 30 nm for WO₃ layer. Further analysis indicated that the titanium sol penetrates the WO₃ layer. Particles in the WO₃ layer consist of a crystalline monoclinic WO₃ core surrounded by a 5–10 nm amorphous phase consisting of WO₃, TiO₂ and SiO₂. The WO₃-TiO₂ layers were used to assemble all solid state photoelectrochromic (PE) devices. Under 1 sun irradiation (1000 W/m²) the visible transmittance of the PE device changes from 62% to 1.6%. The colouring and bleaching processes last about 10 minutes.     

Low-temperature versus oxygen plasma treatment of water-based TiO2 paste for dye-sensitized solar cells

High-temperature treatment steps in fabrication process of dye sensitized solar cell (DSSC) significantly contribute to the manufacturing costs and limit the use of temperature sensitive substrates. Therefore our aim was to develop a simple method for the preparation of water-based TiO₂ paste. The paste is based on peroxotitanic acid (PTA) sol–gel matrix and commercial TiO₂ nanoparticles (P25). Two fabrication processes to decompose/transform the PTA matrix in the printed TiO₂ layer are explored and combined: annealing at temperatures up to 250 °C and/or oxygen plasma treatment. The results show that the PTA matrix in the paste converts to anatase phase and to some extent also attaches to the TiO₂ nanoparticles P25 acting as an interconnecting network within TiO₂ layer. The transformation of the PTA matrix occurs around 250 °C, but in the presence of TiO₂ nanoparticles P25 it starts already at 120 °C. In addition the results reveal that the crystallization is achievable also solely with the oxygen plasma treatment. The efficiency of the TiO₂ layers, exposed to different post-deposition treatments, is evaluated in DSSCs. The results show that oxygen plasma treatment of the TiO₂ layers could efficiently replace temperature curing at 250 °C. Within this study the DSSCs with the efficiency up to 4.2 % measured under standard test conditions (1,000 W/m², AM1.5, 25 °C) were realized.     

Size‐Selective Encapsulation of Hydrophobic Guests by Self‐Assembled M4L6 Cobalt and Nickel Cages

Subtle differences in metal–ligand bond lengths between a series of [M₄L₆]^4? tetrahedral cages, where M=Fe^II, Co^II, or Ni^II, were observed to result in substantial differences in affinity for hydrophobic guests in water. Changing the metal ion from iron(II) to cobalt(II) or nickel(II) increases the size of the interior cavity of the cage and allows encapsulation of larger guest molecules. NMR spectroscopy was used to study the recognition properties of the iron(II) and cobalt(II) cages towards small hydrophobic guests in water, and single‐crystal X‐ray diffraction was used to study the solid‐state complexes of the iron(II) and nickel(II) cages.     

ZnCl2-mediated stereoselective addition of terminal alkynes to D-(+)-mannofuranosyl nitrones

[reaction: see text] An optimized process for the addition of terminal alkynes to chiral nitrones using ZnCl2 and NEt3 in toluene is reported. The new reaction protocol is facile to perform and cost-effective. The resulting optically active propargyl N-hydroxylamines are isolated in good to excellent yield and high diastereoselectivity.     

Cocrystal Formation through Mechanochemistry: from Neat and Liquid‐Assisted Grinding to Polymer‐Assisted Grinding

Mechanochemistry is an effective method for the preparation of multicomponent crystal systems. In the present work, we propose an alternative to the established liquid‐assisted grinding (LAG) approach. Polymer‐assisted grinding (POLAG) is demonstrated to provide a new class of catalysts for improving reaction rate and increasing product diversity during mechanochemical cocrystallization reactions. We demonstrate that POLAG provides advantages comparable to the conventional liquid‐assisted process, whilst eliminating the risk of unwanted solvate formation as well as enabling control of resulting particle size. It represents a new approach for the development of functional materials through mechanochemistry, and possibly opens new routes toward the understanding of the mechanisms and pathways of mechanochemical cocrystal formation.     

The modeling of coalition for environmental protection within co-utility framework

The game theoretic modelling of coalition for environmental protection within the framework of a new concept of co-utility is discussed. The co-utility concept contains mainly two elements. Firstly, agents can increase their payoffs by collaborating with each-other. Secondly, the outcome of collaboration is robust towards internal and external disturbances. The advantages of using of co-utility are two-fold. Primarily, the co-utility concept is broad and can serve as an umbrella concept in all applications where agents have a space for simultaneous improvement of payoffs. Secondly the co-utility concept can be associated with different stability concept such as myopic or farsighted stability. The myopic and farsighted co-utile sets are defined and their element-co-utile outcomes are found.     

Crystallographic analysis of metal-ion binding to human ubiquitin

The metal-binding ability of human ubiquitin (hUb) towards a selection of biologically relevant metal ions and complexes has been probed. Different techniques have been used to obtain crystals suitable for crystallographic analysis. In the first type of experiments, crystals of hUb have been soaked in solutions containing copper(II) acetate and two metallodrugs, Zeise salt (K[PtCl(3)(η(2)-C(2)H(4))]·H(2)O) and cisplatin (cis-[PtCl(2)(NH(3))(2)]). The Zeise salt is used in a test for hepatitis, whereas cisplatin is one of the most powerful anticancer drugs in clinical use. The Zeise salt readily reacts with hUb crystals to afford an adduct with three platinum residues per protein molecule, Pt(3)-hUb. In contrast, copper(II) acetate and cisplatin were found to be unreactive for contact times up to one hour and to cause degradation of the hUb crystals for longer times. In the second type of experiments, hUb was cocrystallized with a solution of copper(II) or zinc(II) acetate or cisplatin. Zinc(II) acetate gives, at low metal-to-protein molar ratios (8:1), crystals containing one metal ion per three molecules of protein, Zn-hUb(3) (already reported in previous work), whereas at high metal-to-protein ratios (70:1) gives crystals containing three Zn(II) ions per protein molecule, Zn(3)-hUb. In contrast, once again, copper(II) acetate and cisplatin, even at low metal-to-protein ratios, do not give crystalline material. In the soaking experiment, the Zeise anion leads to simultaneous platination of His68, Met1, and Lys6. Present and previous results of cocrystallization experiments performed with Zn(II) and other Group 12 metal ions allow a comprehensive understanding of the metal-ion binding properties of hUb with His68 as the main anchoring site, followed by Met1 and carboxylic groups of Glu16, Glu18, Glu64, Asp21, and Asp32, to be reached. In the case of platinum, Lys6 can also be a binding site. The amount of bound metal ion, with respect to that of the protein, appears to be a relevant parameter influencing crystal packing.     

Sodium dithorium trisphosphate — A new ferroelectric substance

Some analyses of polycrystalline samples with the formula MTh₂(PO₄)₃ (M = Li, Na, K, Rb and Cs) have shown that only NaTh₂(PO₄)₃ has piezoelectric properties as well as the ability to retain polarization after the action of an electric field.In the following experiments the hysteresis loops in single crystals of NaTh₂(PO₄)₃ were recorded and ferroelectric parameters at room temperature were determined.     

AgTh2(PO4)3 — A new case of the non-hydrogen bonded phosphate ferroelectric

The basic crystallographic data of AgTh₂(PO₄)₃ single crystals have been determined for the first time by means of X-ray diffraction methods. The crystals are monoclinic, space group isCc with four formula units per unit cell. The dimensions of the unit cell are:a=17·385 Å,b=6·815 Å,c=8·148 Å,β=101·10°. Using the Sawyer and Tower method it has been proved that the crystals possess ferroelectric properties. Performing the measurements at room temperature the values of spontaneous polarization and coercive field in the direction normal to (100) face have been determined.     

Thermally stimulated depolarization current of novolac resin

A novolac phenol-formaldehyde resin was investigated via the thermally stimulated depolarization current, using integral and partial measurements in the temperature range from 137 to 270 K. Tow broadened peaks, assigned as Β₁, and Β₂, appeared at about 160 and 190 K. The influence of water and ¯M_n was investigated. The activation energy E_a vs. T relationship was analysed, and a search was made for compensation phenomena. The distribution of the relaxing dipolesN vs. E_a was approximated. Three different relaxation ranges were distinguished. All the motions were attributed to the rotation of the phenyl rings. The differences found are due to the heterogeneity in the resin. Contamination with water increases the polarizability, decreases the structure differences and relieves the motions in the resin. A resin with a smaller ¯M_n exhibits a higher polarizability and a decreases in structure variety.