Deposits of clastic carbonate-dominated (calciclastic) sedimentary slope systems in the rock record have been identified mostly as linearly-consistent carbonate apron deposits, even though most ancient clastic carbonate slope deposits fit the submarine fan systems better. Calciclastic submarine fans are consequently rarely described and are poorly understood. Subsequently, very little is known especially in mud-dominated calciclastic submarine fan systems. Presented in this study are a sedimentological core and petrographic characterisation of samples from eleven boreholes from the Lower Carboniferous of Bowland Basin (Northwest England) that reveals a >250 m thick calciturbidite complex deposited in a calciclastic submarine fan setting. Seven facies are recognised from core and thin section characterisation and are grouped into three carbonate turbidite sequences. They include: 1) Calciturbidites, comprising mostly of highto low-density, wavy-laminated bioclast-rich facies; 2) low-density densite mudstones which are characterised by planar laminated and unlaminated muddominated facies; and 3) Calcidebrites which are muddy or hyper-concentrated debrisflow deposits occurring as poorly-sorted, chaotic, mud-supported floatstones. These

Phd by thesis

Electrografting refers to the electrochemical reaction that permits organic layers to be attached to solid conducting substrates. This definition can be extended to reactions involving an electron transfer between the substrate to be modified and the reagent, but also to examples where a reducing or oxidizing reagent is added to produce the reactive species. These methods are interesting as they provide a real bond between the surface and the organic layer. Electrografting applies to a variety of substrates including carbon, metals and their oxides, but also dielectrics such as polymers. Since the 1980s several methods have been developed, either by reduction or oxidation, and some of them have reached an industrial stage. This critical review describes the methods that are used for electrografting, their mechanism, the formation and growth of the layers as well as their applications (742 references).

Electrografting: a powerful method for surface modification

Quantum-dot-based photoelectrochemical sensors are powerful alternatives for the detection of chemicals and biochemical molecules compared to other sensor types, which is the primary reason as to why they have become a hot topic in nanotechnology-related analytical methods. These sensors basically consist of QDs immobilized by a linking molecule (linker) to an electrode, so that upon their illumination, a photocurrent is generated which depends on the type and concentration of the respective analyte in the immediate environment of the electrode. The present review provides an overview of recent developments in the fabrication methods and sensing concepts concerning direct and indirect interactions of the analyte with quantum dot modified electrodes. Furthermore, it describes in detail the broad range of different sensing applications of such quantum-dot-based photoelectrochemical sensors for inorganic and organic (small and macro-) molecules that have arisen in recent years. Finally, a number of aspects concerning current challenges on the way to achieving real-life applications of QD-based photochemical sensing are addressed.

Quantum-dot-based photoelectrochemical sensors for chemical and biological detection.

The understanding of protein adsorption at charged surfaces is important for a wide range of scientific disciplines including surface engineering, separation sciences and pharmaceutical sciences. Compared to chemical entities having a permanent charge, the adsorption of small ampholytes and proteins is more complicated as the pH near a charged surface can be significantly different from the value in bulk solution. In this work, we have developed a phenomenological adsorption model which takes into account the combined role of interfacial ion distribution, interfacial charge regulation of amino acids in the proximity of the surface, electroneutrality, and mass balance. The model is straightforward to apply to a given set of experimental conditions as most model parameters are obtained from bulk properties and therefore easy to estimate or are directly measurable. The model provides a detailed understanding of the importance of surface charge on adsorption and in particular of how changes in surface charge, concentration, and surface area may affect adsorption behavior. The model is successfully used to explain the experimental adsorption behavior of the two model proteins lysozyme and α-lactalbumin. It is demonstrated that it is possible to predict the pH and surface charge dependent adsorption behavior from experimental or theoretical estimates of a preferred orientation of a protein at a solid charged interface.

Protein adsorption at charged surfaces: the role of electrostatic interactions and interfacial charge regulation.

Thin mesoporous films of α-Fe(2)O(3) have been prepared on conducting glass substrates using layer-by-layer self-assembly of ca. 4 nm hydrous oxide nanoparticles followed by calcining. The electrodes were used to study the oxygen evolution reaction (OER) in the dark and under illumination using in situ potential-modulated absorption spectroscopy (PMAS) and light-modulated absorption spectroscopy (LMAS) combined with impedance spectroscopy. Formation of surface-bound higher-valent iron species (or "surface trapped holes") was deduced from the PMAS spectra measured in the OER onset region. Similar LMAS spectra were obtained at more negative potentials in the onset region of photoelectrochemical OER, indicating involvement of the same intermediates. The impedance response of the mesoporous α-Fe(2)O(3) electrodes exhibits characteristic transmission line behavior that is attributed to slow hopping of holes, probably between surface iron species. Frequency-resolved PMAS and LMAS measurements revealed slow relaxation behavior that can be related to the impedance response and that indicates that the lifetime of the intermediates (or trapped holes) involved in the OER is remarkably long.

https://purehost.bath.ac.uk/ws/files/213267/Peter_JACS_2012_134_1228.pdf

New insights into water splitting at mesoporous α-Fe2O3 films: a study by modulated transmittance and impedance spectroscopies.

Reference LEPA-ARTICLE-2002-021doi:10.1021/jp015533oView record in Web of Science Record created on 2005-11-07, modified on 2017-05-12

Photoinduced Electron Transfer at Liquid/Liquid Interfaces. Part VI. On the Thermodynamic Driving Force Dependence of the Phenomenological Electron-Transfer Rate Constant

The initial stages of the heterogeneous photoreduction of quinone species by self-assembled porphyrin ion pairs at the water|1,2-dichloroethane (DCE) interface have been studied by ultrafast time-resolved spectroscopy and dynamic photoelectrochemical measurements. Photoexcitation of the water-soluble ion pair formed by zinc meso-tetrakis(p-sulfonatophenyl)porphyrin (ZnTPPS4-) and zinc meso-tetrakis(N-methylpyridyl)porphyrin (ZnTMPyP4+) leads to a charge-separated state of the form ZnTPPS3-−ZnTMPyP3+ within 40 ps. This charge-separated state is involved in the heterogeneous electron injection to acceptors in the organic phase in the microsecond time scale. The heterogeneous electron transfer manifests itself as photocurrent responses under potentiostatic conditions. In the case of electron acceptors such as 1,4-benzoquinone (BQ), 2,6-dichloro-1,4-benzoquinone (DCBQ), and tetrachloro-1,4-benzoquinone (TCBQ), the photocurrent responses exhibit a strong decay due to back electron transfer to the oxidized porp...

Photoinduced Electron Transfer at Liquid|Liquid Interfaces: Dynamics of the Heterogeneous Photoreduction of Quinones by Self-Assembled Porphyrin Ion Pairs

Nicolas Eugster

Papers

Photoinduced Electron Transfer at Liquid/Liquid Interfaces. Part VI. On the Thermodynamic Driving Force Dependence of the Phenomenological Electron-Transfer Rate Constant

Photoinduced Electron Transfer at Liquid|Liquid Interfaces: Dynamics of the Heterogeneous Photoreduction of Quinones by Self-Assembled Porphyrin Ion Pairs

Adsorption and photoreactivity of CdSe nanoparticles at liquid|liquid interfaces

Simulations of the adsorption of ionic species at polarisable liquid∣liquid interfaces

A generalised model for dynamic photocurrent responses at dye-sensitised liquid|liquid interfaces