Effect of Water Addition during Preparation on the Early-Time Photodynamics of CH3 NH3 PbI3 Perovskite Layers.

The effect of water addition during preparation of a CH3 NH3 PbI3 layer on the photodynamics is studied by femtosecond transient absorption. Both the regular perovskite and the aqueous analogue show charge thermalisation on a timescale of about 500 fs. This process is, however, less pronounced in the latter layer. The spectral feature associated with hot charges does not fully decay on this timescale, but also shows a long-lived (sub-ns) component. As water molecules may interfere with the hydrogen bonding between the CH3 NH3+ cations and the inorganic cage, this effect is possibly caused by immobilisation of cation motion, suggesting a key role of CH3 NH3+ dipole reorientation in charge thermalisation. This effect shows the possibility of controlling hot charge carrier cooling to overcome the Shockley-Queisser limit.

Porous Layered Double Hydroxides Synthesized using Oxygen Generated by Decomposition of Hydrogen Peroxide.

Porous magnesium-aluminium layered double hydroxides (LDH) were prepared through intercalation and decomposition of hydrogen peroxide (H2O2). This process generates oxygen gas nano-bubbles that pierce holes in the layered structure of the material by local pressure build-up. The decomposition of the peroxide can be triggered by microwave radiation or chemically by reaction with iodide (I-) ions. The carbonate LDH version [Mg0.80Al0.20(OH)2](CO3)0.1∙mH2O was synthesized by microwave-assisted urea coprecipitation and further modified by iodide or H2O2 intercalation. High resolution Scanning Electron Microscopy (HR-SEM) and Brunauer-Emmet-Teller (BET) analysis were used to assess the morphology and surface area of the new porous materials. The presence of H2O2 in the interlayer region and later decomposition triggered by microwave radiation generated more pores on the surface of the LDH platelets, increasing their specific surface area from initially 9 m2/g to a maximum of 67 m2/g. X-Ray Diffraction showed that the formation of the pores did not affect the remaining crystal structure, allowing possible further functionalization of the material.

Surface micropatterning with zirconia and calcium phosphate ceramics by micromoulding in capillaries.

An increasing demand exists for biomaterials that are able to actively participate in the process of repair and regeneration of damaged or diseased organs and tissues. Patterning of surfaces of biomaterials with distinct chemical or physical cues is an attractive way to obtain spatial control over their interactions with the biological system. In the current study, micromoulding in capillaries method was used to pattern silicon substrates with bioinert yttria-stabilised zirconia or with bioactive calcium phosphate ceramics, both widely used biomaterials in orthopaedics and dentistry. Micrometer-scale patterns consisted of parallel lines with varying width and spacing. Both ceramics were successfully deposited on the substrate in a pattern defined by the mould. While the yttria-stabilised zirconia pattern was highly homogenous and smooth (Rq = 5.5 nm), the calcium phosphate pattern, consisting of dicalcium phosphate anhydrous before, and of ß-tricalcium phosphate after annealing, exhibited a less homogenous morphology and higher roughness (Rq = 893 nm). Both materials allowed attachment and proliferation of the MG-63 osteosarcoma cell line, independent of the pattern used. While a preferential orientation of cells in the direction of the pattern lines was observed for all patterns, this effect was more pronounced on the lines with a width of up to 20 µm on both yttria-stabilised zirconia and calcium phosphate ceramics, as compared to wider patterns. Furthermore, the cells retained an elongated morphology for a longer period of time on narrow patterns. Micromoulding in capillaries appeared to be a suitable method to pattern both types of ceramics, however further optimisation is needed to improve homogeneity and obtain better control over the chemical phase and crystalline structure of calcium phosphate patterns.

A new water absorbable mechanical Epidermal skin equivalent: the combination of hydrophobic PDMS and hydrophilic PVA hydrogel.

Research on human skin interactions with healthcare and lifestyle products is a topic continuously attracting scientific studies over the past years. It is possible to evaluate skin mechanical properties based on human or animal experimentation, yet in addition to possible ethical issues, these samples are hard to obtain, expensive and give rise to highly variable results. Therefore, the design of a skin equivalent is essential. This paper describes the design and characterization of a new Epidermal Skin Equivalent (ESE). The material resembles the properties of epidermis and is a first approach to mimic the mechanical properties of the human skin structure, variable with the length scale. The ESE is based on a mixture of Polydimethyl Siloxane (PDMS) and Polyvinyl Alcohol (PVA) hydrogel cross-linked with Glutaraldehyde (GA). It was chemically characterized by XPS and FTIR measurements and its cross section was observed by macroscopy and cryoSEM. Confocal Microscope analysis on the surface of the ESE showed an arithmetic roughness (Ra) between 14-16 µm and contact angle (CA) values between 50-60°, both of which are close to the values of in vivo human skins reported in the literature. The Equilibrium Water Content (ECW) was around 33.8% and Thermo Gravimetric Analysis (TGA) confirmed the composition of the ESE samples. Moreover, the mechanical performance was determined by indentation tests and Dynamo Thermo Mechanical Analysis (DTMA) shear measurements. The indentation results were in good agreement with that of the target epidermis reported in the literature with an elastic modulus between 0.1-1.5 MPa and it showed dependency on the water content. According to the DTMA measurements, the ESE exhibits a viscoelastic behavior, with a shear modulus between 1-2.5MPa variable with temperature, frequency and the hydration of the samples.

Dielectrophoretic alignment of metal and metal oxide nanowires and nanotubes: a universal set of parameters for bridging prepatterned microelectrodes.

Nanowires and nanotubes were synthesized from metals and metal oxides using templated cathodic electrodeposition. With templated electrodeposition, small structures are electrodeposited using a template that is the inverse of the final desired shape. Dielectrophoresis was used for the alignment of the as-formed nanowires and nanotubes between prepatterned electrodes. For reproducible nanowire alignment, a universal set of dielectrophoresis parameters to align any arbitrary nanowire material was determined. The parameters include peak-to-peak potential and frequency, thickness of the silicon oxide layer, grounding of the silicon substrate, and nature of the solvent medium used. It involves applying a field with a frequency >10(5) Hz, an insulating silicon oxide layer with a thickness of 2.5 µm or more, grounding of the underlying silicon substrate, and the use of a solvent medium with a low dielectric constant. In our experiments, we obtained good results by using a peak-to-peak potential of 2.1 V at a frequency of 1.2 × 10(5) Hz. Furthermore, an indirect alignment technique is proposed that prevents short circuiting of nanowires after contacting both electrodes. After alignment, a considerably lower resistivity was found for ZnO nanowires made by templated electrodeposition (2.2-3.4 × 10(-3) Ωm) compared to ZnO nanorods synthesized by electrodeposition (10 Ωm) or molecular beam epitaxy (MBE) (500 Ωm).