Stripping voltammetry for the determination of trace metal speciation and in-situ measurements of trace metal distributions in marine waters

Progress in marine chemistry has been driven by improved sampling and sample handling techniques, and developments in analytical chemistry. Consequently, during the last 20 years our understanding of marine trace metal biogeochemistry has improved a great deal. Stripping voltammetric techniques (anodic stripping voltammetry and adsorptive cathodic stripping voltammetry) have made an important contribution to this understanding. The selectivity and extremely low detection limits have made stripping voltammetry a widely used technique for trace metal speciation and trace metal distribution measurements in seawater. Stripping voltammetry is very suitable for ship-board and in-situ applications because of the portability, low cost and capability for automation of the voltammetric instrumentation. Future developments in stripping voltammetry can be expected in the field of stand-alone submersible voltammetric analysers, capable of continuous trace metal measurements. Future applications of stripping voltammetry can be found in the interactions between trace metal speciation and growth and the functioning of organisms in pristine and metal polluted marine waters.     

Phase field simulation of thermomechanical fracture

In Francfort and Marigo's variational free-discontinuity formulation of brittle fracture [1] cracking is regarded as an energy minimization process, where the total energy is minimized with respect to any admissible crack set and displacement field. No additional criterion is needed to determine crack paths, branching of cracks and crack initiations. However, a direct discretization of the model is faced with significant technical problems, as it involves minimizations in a set of possibly discontinuous functions. A regularized version of the model has been introduced by Bourdin [2] and based on this, we use the concept of a continuum phase field model to simulate cracking processes. Cracks are indicated by the order parameter of the phase field model and cracking can be regarded as a phase transition problem. Additionally, introducing the heat equation into the model, it is capable to also take account of crack propagation due to thermal stresses. In the numerical implementation, crack parameter as well as temperature are treated as additional degrees of freedom and the coupled field equations are solved using the finite element method together with an implicit time integration scheme. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Polyphosphinoborane Block Copolymer Synthesis Using Catalytic Reversible Chain-Transfer Dehydropolymerization

An amphiphilic block copolymer of polyphosphinoborane has been prepared by a mechanism-led strategy of the sequential catalytic dehydropolymerization of precursor monomers, H₃B ⋅ PRH₂ (R=Ph, n-hexyl), using the simple pre-catalyst [Rh(Ph₂PCH₂CH₂PPh₂)₂]Cl. Speciation, mechanism and polymer chain growth studies support a step-growth process where reversible chain transfer occurs, i.e. H₃B ⋅ PRH₂/oligomer/polymer can all coordinate with, and be activated by, the catalyst. Block copolymer [H₂BPPhH]₁₁₀-b-[H₂BP(n-hexyl)H]₁₁ can be synthesized and self-assembles in solution to form either rod-like micelles or vesicles depending on solvent polarity.     

Olefin Dihydroxylation Using Nitroarenes as Photoresponsive Oxidants

Vicinal diols are abundant among natural and synthetic molecules, and also represent valuable intermediates throughout organic synthesis. Olefin dihydroxylation is an effective strategy to access these derivatives owing to the broad range and availability of alkene feedstocks. OsO₄ is among the most used reagents to achieve this transformation, yet its high toxicity and cost remain concerning. Herein, we present a mechanistically distinct strategy for olefin dihydroxylation using nitroarenes as photoresponsive oxidants. Upon purple LEDs irradiation, these species undergo a [3+2]-photocycloaddition with a wide range of olefins to give stable 1,3,2-dioxazolidine intermediates. These species can be accumulated in solution and then reduced in situ to the desired diols, utilising readily accessible and easy to handle solid reagents as H₂ surrogates.     

Photodegradation of CuBi2O4 Films Evidenced by Fast Formation of Metallic Bi using Operando Surface-sensitive X-ray Scattering**

CuBi₂O₄ has recently emerged as a promising photocathode for photo-electrochemical (PEC) water splitting. However, its fast degradation under operation currently poses a limit to its application. Here, we report a novel method to study operando the semiconductor-electrolyte interface during PEC operation by surface-sensitive high-energy X-ray scattering. We find that a fast decrease in the generated photocurrents correlates directly with the formation of a metallic Bi phase. We further show that the slower formation of metallic Cu, as well as the dissolution of the electrode in contact with the electrolyte, further affect the CuBi₂O₄ activity and morphology. Our study provides a comprehensive picture of the degradation mechanisms affecting CuBi₂O₄ electrodes under operation and poses the methodological basis to investigate the photocorrosion processes affecting a wide range of PEC materials.     

Rapid Phase Transitions of Thermotropic Glycolipid Quasicrystal and Frank-Kasper Mesophases: A Mechanistic Rosetta Stone

Experimental results are presented that serve to lower the barrier for developing the science and technology of non-classical thermotropic glycolipid mesophases, which now include dodecagonal quasicrystal (DDQC) and Frank–Kasper (FK) A15 and σ mesophases that can be produced under mild conditions from a versatile class of sugar-polyolefin conjugates. By employing “alloys” comprised of mono- and disaccharide-polyolefin conjugates, and optionally with vitamin E as a small molecule phase modulator, we report the spontaneous formation of stable A15 mesophases at ambient temperature. We further document a rich thermotropic phase map that includes DDQC, A15, and σ mesophases of tunable periodicity that are connected through rapid thermotropic phase transitions as a function of increasing temperature in the order: liquid-like packing (LLP)→DDQC → A15→σ→ disorder. This first direct observation of a rapid thermotropic A15→σ phase transition provides support for a diffusionless martensitic process proceeding through strain-induced introduction of planar defects into the A15 lattice.