Marine natural products

This review covers the literature published in 2003 for marine natural products, with 619 citations (413 for the period January to December 2003) referring to compounds isolated from marine microorganisms and phytoplankton, green algae, brown algae, red algae, sponges, coelenterates, bryozoans, molluscs, tunicates and echinoderms. The emphasis is on new compounds (656 for 2003), together with their relevant biological activities, source organisms and country or origin. Biosynthetic studies or syntheses that lead to the revision of structures or stereochemistries have been included (78), including any first total syntheses of a marine natural product.     

Modelling two-phase flow in porous media at the pore scale using the volume-of-fluid method

We present a stable numerical scheme for modelling multiphase flow in porous media, where the characteristic size of the flow domain is of the order of microns to millimetres. The numerical method is developed for efficient modelling of multiphase flow in porous media with complex interface motion and irregular solid boundaries. The Navier–Stokes equations are discretised using a finite volume approach, while the volume-of-fluid method is used to capture the location of interfaces. Capillary forces are computed using a semi-sharp surface force model, in which the transition area for capillary pressure is effectively limited to one grid block. This new formulation along with two new filtering methods, developed for correcting capillary forces, permits simulations at very low capillary numbers and avoids non-physical velocities. Capillary forces are implemented using a semi-implicit formulation, which allows larger time step sizes at low capillary numbers. We verify the accuracy and stability of the numerical method on several test cases, which indicate the potential of the method to predict multiphase flow processes.     

Biosynthesis of spiro-mamakone A, a structurally unprecedented fungal metabolite

Biosynthetic studies on spiro-mamakone A (1), a potently cytotoxic and antimicrobial compound from an endophytic fungus isolated from the New Zealand native tree Knightia excelsa (rewarewa), confirm the polyketide origins of this unique compound belonging to the spirobisnaphthalene class of compounds. The biosynthesis proceeds via an unprecedented symmetric enedione with the two halves of the molecule being formed from two separate pentaketide units connected by oxidative coupling.     

Evolving trends in the dereplication of natural product extracts. 3: further lasiodiplodins from Lasiodiplodia theobromae, an endophyte from Mapania kurzii

Two further lasiodiplodins, (3R,4R)-4-hydroxy-de-O-methyl-lasiodiplodin and (E)-9-etheno-de-O-methyl-lasiodiplodin, together with three known lasiodiplodins from a cytotoxic extract obtained from a culture of Lasiodiplodia theobromae, an endophyte from the root tissues of Mapania kurzii (Cyperaceae) from the Malaysian rain forest, were characterized on microgram scale.     

Dichlorocarbene Addition to

In contrast to the terminal phosphinidene complex PhPW(CO)(5) (2), which adds to [5]metacyclophane (1) in a 1,4-fashion, dichlorocarbene preferentially adds in a 1,2-fashion to the formal "anti-Bredt" type double bond of the aromatic ring of 1 to afford the norcaradiene 11b, which immediately rearranges to the bridged cycloheptatriene 12b and further by a [1,5] sigmatropic chlorine migration to the isomeric 13b as the first observable product. More slowly, the latter isomerizes via a dissociative mechanism to give 15b. A computational study supports the notion that the [1,5] chlorine migration in the rearrangement 12b --> 13b, for which an activation barrier of 70.2 kJ mol(-)(1) was calculated, is essentially concerted with minor charge separation. In contrast, the analogous [1,5] chlorine migration in the flat model compound 7,7-dichlorocycloheptatriene (12a) displays features of a dissociative pathway.     

Comparison of residual oil cluster size distribution, morphology and saturation in oil-wet and water-wet sandstone

We imaged an oil-wet sandstone at residual oil saturation (S(or)) conditions using X-ray micro-tomography with a nominal voxel size of (9 μm)(3) and monochromatic light from a synchrotron source. The sandstone was rendered oil-wet by ageing with a North Sea crude oil to represent a typical wettability encountered in hydrocarbon reservoirs. We measured a significantly lower S(or) for the oil-wet core (18.8%) than for an analogue water-wet core (35%). We analysed the residual oil cluster size distribution and find consistency with percolation theory that predicts a power-law cluster size distribution. We measure a power-law exponent τ=2.12 for the oil-wet core which is higher than τ for the water-wet system (τ=2.05), indicating fewer large clusters in the oil-wet case. The clusters are rough and sheet-like consistent with connectivity established through layers in the pore space and occupancy of the smaller pores; in contrast the clusters for water-wet media occupy the centres of the larger pores. These results imply less trapping of oil, but with a greater surface area for dissolution. In carbon storage applications, this suggests that in CO(2)-wet systems, capillary trapping is less significant, but that there is a large surface area for dissolution and reaction.     

Marine natural products

This review covers the literature published in 2006 for marine natural products, with 758 citations (534 for the period January to December 2006) referring to compounds isolated from marine microorganisms and phytoplankton, green algae, brown algae, red algae, sponges, cnidaria, bryozoans, molluscs, tunicates and echinoderms. The emphasis is on new compounds (779 for 2006), together with their relevant biological activities, source organisms and country of origin. Biosynthetic studies, first syntheses, and syntheses that lead to the revision of structures or stereochemistries, have been included.     

A Physically Based Model of Dissolution of Nonaqueous Phase Liquids in the Saturated Zone

The design of remediation strategies for nonaqueous phase liquid (NAPL) contaminants involves predicting the rate of NAPL dissolution. A physically based model of an idealized pore geometry was developed to predict nonaqueous phase liquid dissolution rate coefficients. A bundle of parallel pores in series model is used to represent NAPL dissolution as a function of three processes: pore diffusion, corner diffusion, and mixing and multiple contact. The dissolution rate coefficient is expressed in terms of the modified Sherwood number (Sh) and is a function of Peclet (Pe) number. The model captures the complex behavior of Sh versus Pe data for both water-wet (Powers, 1992) and NAPL-wet (Parker et al., 1991) media. For water-wet media, the observed behavior can be broken down into four distinct regions. Each region represents a different physical process controlling NAPL dissolution: the low-Pe region is controlled by pore diffusion; the low- to moderate-Pe region is a transition zone; the moderate-Pe region is controlled by mixing and multiple contact; and the high-Pe region is controlled by corner diffusion. For the high-Pe conditions typical of most column experiments, the model involves only one fitting parameter. For NAPL-wet media, NAPL dissolution is governed exclusively by corner diffusion, and the model again involves only one fitting parameter.     

Micromodel Observation of the Role of Oil Layers in Three-Phase Flow

We have studied the flow of a non-aqueous phase liquid (NAPL, or oil), water and air at the pore scale using a micromodel. The pore space pattern from a photomicrograph of a two-dimensional section through a Berea sandstone was etched onto a silicon wafer. The sizes of the pores in the micromodel are in the range 3–30,m and are the same as observed in the rock from which the image was taken. We conducted three-phase displacement experiments at low capillary numbers (in the order of 10^-7) to observe the presence of predicted displacement mechanisms at the pore scale. We observed stable oil layers between the wetting phase (water) and the non-wetting phase (gas) for the water–decane–air system, which has a negative equilibrium spreading coefficient, as well as four different types of double displacements where one fluid displaces another that displaces a third. Double imbibition and double drainage are readily observed, but the existence of an oil layer surrounding the gas phase makes the other double displacement combinations very unlikely.