Systematic Study of the Interaction Between VIV Centres and LnIII Ions in Well Defined {V 2 IV LnIII}{AsIIIW9O33}2 Sandwich-Type Clusters: Part 2

The gadolinium (Gd) member of a new type of heteropolytungstates that contain one lanthanide and two transition metal ions in a triangular arrangement is reported. The compound NaK₆Gd_0.33 [((VO)₂Gd(H₂O)₄K₂(H₂O)₂(Na)(H₂O)₂)(α-B-AsW₉O₃₃)₂]·24H₂O (1) was prepared from acidified aqueous solutions of Na₂WO₄·2H₂O, As₂O₃ and VOSO₄·5H₂O to which Gd³⁺ ions were added. The single crystal X-ray structure analysis (monoclinic, space group P2₁/m) shows that the anion consists of two [α-B-As^IIIW₉O₃₃]^9? trilacunary Keggin-type units linked by two VO²⁺, one Gd³⁺ as well as weakly by two K⁺ and one Na⁺ ions, resulting in a sandwich-type structure with idealized C _2v symmetry. The problem of positioning crystal lattice and special polyoxometalate sites with different cations is discussed also in connection with supramolecular chemistry aspects and as an option for further research. A fit of the magnetic susceptibility yielded exchange coupling constants of J _VV = ?2.55 cm^?1 (anti-ferromagnetic) between the vanadium ions and J _GdV = 0.6 cm^?1 (ferromagnetic) between the Gd and each of the two vanadium ions. The complete magnetochemical analysis also revealed a partial occupancy of the Na⁺ sites in the counter-cation–water system by Gd³⁺ ions (0.33 Gd³⁺ ions in total).     

Combined QCM-D/GE as a tool to characterize stimuli-responsive swelling of and protein adsorption on polymer brushes grafted onto 3D-nanostructures

A combined setup of quartz crystal microbalance and generalized ellipsometry can be used to comprehensively investigate complex functional coatings comprising stimuli-responsive polymer brushes and 3D nanostructures in a dynamic, noninvasive in situ measurement. While the quartz crystal microbalance detects the overall change in areal mass, for instance, during a swelling or adsorption process, the generalized ellipsometry data can be evaluated in terms of a layered model to distinguish between processes occurring within the intercolumnar space or on top of the anisotropic nanocolumns. Silicon films with anisotropic nanocolumnar morphology were prepared by the glancing angle deposition technique and further functionalized by grafting of poly-(acrylic acid) or poly-(N- isopropylacrylamide) chains. Investigations of the thermoresponsive swelling of the poly-(N-isopropylacrylamide) brush on the Si nanocolumns proved the successful preparation of a stimuli-responsive coating. Furthermore, the potential of these novel coatings in the field of biotechnology was explored by investigation of the adsorption of the model protein bovine serum albumin. Adsorption, retention, and desorption triggered by a change in the pH value is observed using poly-(acrylic acid) functionalized nanostructures, although generalized ellipsometry data revealed that this process occurs only on top of the nanostructures. Poly-(N-isopropylacrylamide) is found to render the nanostructures non-fouling properties.     

From Light to Structure: Photo Initiators for Radical Two-Photon Polymerization

Two-photon polymerization (2PP) represents a powerful technique for the fabrication of precise three-dimensional structures on a micro- and nanometer scale for various applications. While many review articles are focusing on the used polymeric materials and their application in 2PP, in this review the class of two-photon photo initiators (2PI) used for radical polymerization is discussed in detail. Because the demand for highly efficient 2PI has increased in the last decades, different approaches in designing new efficient 2PIs occurred. This review summarizes the 2PIs known in literature and discusses their absorption behavior under one- and two-photon absorption (2PA) conditions, their two-photon cross sections (σ_TPA) as well as their efficiency under 2PP conditions. Here, the photo initiators are grouped depending on their chromophore system (D-π-A-π-D, D-π-D, etc.). Their polymerization efficiencies are evaluated by fabrication windows (FW) depending on different laser intensities and writing speeds.     

Tannin-Mordant Coloration with Matcha (camelia sinensis) and Iron(II)-Lactate on Human Hair Tresses

The aim of this work was to optimize our natural hair dyeing system which we described in our previous work and to compare with other dyeing systems. Therefore, we investigated concentration limits of matcha and mordant and compared this new dyeing method with commercial permanent systems on the market. Completely unpigmented hair tresses were dyed with matcha powder (camelia sinensis) and iron(II)-lactate. To investigate the wash fastness and concentration limits, the differently dyed hair tresses were spectrophotometrically measured. The comparison of the damage potential for which cysteic acid is an indicator was measured by NIR. The concentration of matcha and mordant are responsible for the intensity of the color results. The higher the matcha or the mordant concentration, the darker the color results of the dyed hair tresses. Hair damage of matcha mordant dyeing is comparable with results of commercial permanent hair coloration systems. Moreover, the results of wash fastness of matcha mordant dyed hair tresses is comparable and even better by tendency to permanent colored hair tresses.     

Combination of radon and stable isotope analysis as a tool for decision support concerning the remediation of NAPL-contaminated sites

The non-aqueous phase-liquid (NAPL)-contaminated aquifer at a major refinery site in Mexico was investigated. Owing to the depth of the contaminated aquifer section (NAPL source zone) of over 100 m below the surface, the actual aquifer material was not accessible for sampling. Information on the residual NAPL contamination of the aquifer could only be obtained indirectly by analysing groundwater samples from a few wells available at the site. To tackle the problem, an approach alternative to conventional groundwater analysis for dissolved NAPL was chosen. For evaluating the recent contamination and estimating its probable future development, the radioisotope radon-222 and the stable isotopes 13C, 34S and 18O were used as naturally occurring contamination tracers and process indicators. Radon was used as partitioning tracer for the approximate localization and semi-quantitative assessment of the NAPL source zone. The stable isotopes were used as indicators for naturally occurring biodegradation processes, which might potentially be implemented into future remediation schemes.     

Adaptation of electrodes and printable gel polymer electrolytes for optimized fully organic batteries

Despite intensive scientific efforts on the development of organic batteries, their full potential is still not being realized. The individual components, such as electrode materials and electrolytes, are in most cases developed independently and are not adjusted to each other. In this context, we report on the performance optimization of a full-organic solid-state battery system by the mutual adaptation of the electrode materials and an ionic liquid (IL)-based gel polymer electrolyte (GPE). The formulation of the latter was designed for a one-step manufacturing approach and can be applied directly to the electrode surface, where it is UV-cured to yield the GPE without further post-treatment steps. Herein, a special focus was placed on the applicability in industrial processes. A first significant capacity increase was achieved by the incorporation of the IL into the electrode composite. Furthermore, the GPE composition was adapted applying acrylate- and methacrylate-based monomers and combinations thereof with the premise of a fast curing step. Furthermore, the amount of IL was varied, and all combinations were evaluated for their final performance in cells. The latter variation revealed that a high ionic conductivity is not the only determining factor for a good cell performance. Next to a sufficient conductivity, the interaction between electrode and electrolyte plays a key role for the cell performance as it enhances the accessibility of the counter ions to the redox-active sites.     

Germaborenes: Borylene Transfer Agents for the Synthesis of Iminoboranes

Halide and phenyl substituted germaborenes were shown to react with azides at room temperature and transfer a borylene moiety to give iminoboranes. This iminoborane synthesis based on a borylene transfer route was investigated computationally in the case of the phenyl substituted germaborene.     

Phosphine-Stabilized Pnictinidenes

The reaction of the intramolecular germylene-phosphine Lewis pair (o-PPh₂)C₆H₄GeAr* ( 1 ) with Group 15 element trichlorides ECl₃ (E=P, As, Sb) was investigated. After oxidative addition, the resulting compounds (o-PPh₂)C₆H₄(Ar*)Ge(Cl)ECl₂ ( 2 : E=P, 3 : E=As, 4 : E=Sb) were reduced by using sodium metal or LiHBEt₃. The molecular structures of the phosphine-stabilized phosphinidene (o-PPh₂)C₆H₄(Ar*)Ge(Cl)P ( 5 ), arsinidene (o-PPh₂)C₆H₄(Ar*)Ge(Cl)As ( 6 ) and stibinidene (o-PPh₂)C₆H₄(Ar*)Ge(Cl)Sb ( 7 ) are presented; they feature a two-coordinate low-valent Group 15 element. After chloride abstraction, a cyclic germaphosphene [(o-PPh₂)C₆H₄(Ar*)GeP] [B(C₆H₃(CF₃)₂)₄] ( 8 ) was isolated. The ³¹P NMR data of the germaphosphene were compared with literature examples and analyzed by quantum chemical calculations. The phosphinidene was treated with [iBu₂AlH]₂, and the product of an Al−H addition to the low-valent phosphorus atom (o-PPh₂)C₆H₄(Ar*)Ge(H)P(H)Al(C₄H₉)₂ ( 9 ) was characterized.     

Composition of oxygen precipitates in Czochralski silicon wafers investigated by STEM with EDX/EELS and FTIR spectroscopy

In this work, we investigated the stoichiometry of oxygen precipitates in Czochralski silicon wafers. The thickness dependence of the Cliff–Lorimer sensitivity factor for the silicon/oxygen system was determined and applied for the investigation of the stoichiometry of oxygen precipitates by EDX. The results show that both plate‐like oxygen precipitates and a transitional form between plate‐like and octahedral precipi‐ tates consist of SiO₂. This was confirmed by EELS low loss spectra where the typical spectrum for amorphous SiO₂ was observed. Moreover, the absorption band of plate‐like precipitates at 1227 cm^–1 was found in the low temperature FTIR spectrum. It was demonstrated that this band can only be simulated by the dielectric constants of amorphous SiO₂. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)