Rhamnosylation of lignans by a Streptomyces strain

Screening of 400 Streptomyces strains for biotransformation of the natural lignan matairesinol led to the identification of Streptomyces sp. LS136, capable of producing a single metabolite in moderate yields. Isolation and purification by preparative HPLC, followed by structural analyses by LC-MS and NMR, established the structure as matairesinol-4-O-rhamnoside. This bacterial strain was also used for rhamnosylation of the abundant natural lignans, hydroxymatairesinol and secoisolariciresinol.     

Normative KGP agents

We extend the logical model of agency known as the KGP model, to support agents with normative concepts, based on the roles an agent plays and the obligations and prohibitions that result from playing these roles. The proposed framework illustrates how the resulting normative concepts, including the roles, can evolve dynamically during the lifetime of the agent. Furthermore, we illustrate how these concepts can be combined with the existing capabilities of KGP agents in order to plan for their goals, react to changes in the environment, and interact with other agents. Our approach gives an executable specification of normative concepts that can be used directly for prototyping applications. Fariba Sadri is a senior lecturer at Imperial College London, from where she received her PhD. Her earlier work concentrated on integrity of deductive databases and temporal reasoning, in particular using the event calculus. In more recent years her work has been on agent technologies and multi-agent systems. She has worked on logic-based agent models, reasoning, dynamic belief revision, and inter-agent communication and negotiation for resources. She was co-awarded an EPSRC grant for research into logic-based multi-agents and was co-investigator in the EU SOCS project. Kostas Stathis is a senior lecturer at Royal Holloway, University of London and he holds a PhD from Imperial College London. His research interests are in the area of computational intelligence in general and in the intersection of computational logic and cognitive systems for social computing applications in particular. His research interests include: representation of human-computer (or computer-computer) interaction as a game; cognitive & autonomous agents; artificial agent societies; agent communication; programmable agents and agent platforms. He is a co-investigator of the EU ArguGRID project and was a co-investigator of the EU SOCS project. Francesca Toni is a senior lecturer at Imperial College London, from where she received her PhD. Her earlier work focused on abductive reasoning. In more recent years, she focused on argumentation, agent models and multi-agent systems. She has worked on computational logic-based agent models, agent reasoning, dynamic belief revision, and inter-agent communication and negotiation for resources. She has been co-ordinator of the EU SOCS project, which developed the KGP model of agency, and is coordinator of the EU ArguGRID project, on the application of argumentative agents within grid systems.     

A mathematical model of the ring-spinning process

This paper develops a mathematical model of the ring-spinning process that takes into account its non-stationary nature. A complex system of differential equations is obtained, which from a mathematical point of view constitutes a ‘free-boundary’ problem. Its solution involves definition of suitable boundary conditions related to the mechanical characteristics of the process and of the spinning machine itself. The boundary conditions which determine the solution are pointed out. A numerical solution of the system of differential equations can be obtained by the Finite-Segments method, as shown in an example.     

Cationic poly(methacryl oxyethyl trimethylammonium) and its poly(ethylene glycol)‐grafted analogue as capillary coating materials in electrophoresis

Cationic polyelectrolytes were synthesized and used as semipermanent coating materials for capillaries in electrophoresis. The polyelectrolytes used were a homopolymer of poly(methacryl oxyethyl trimethylammonium chloride) (PMOTAC) and its poly(ethylene glycol) (PEG)‐grafted analogue. Two PMOTAC polyelectrolytes, with molar masses of 85,000 and 300,000 g/mol, and PEG‐grafted PMOTAC with a molar mass of 280,000 g/mol were synthesized and then characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. Attachment of the polyelectrolytes to the wall of the fused silica capillary for electrophoresis caused the electroosmotic flow (EOF) to reverse. The polyelectrolyte coatings were tested over the pH range 2–11 at different buffer ionic strengths, and the most stable and strongest anodic EOFs were obtained at acidic pH values with low ionic strength buffers. Between runs the capillary is merely rinsed for 2 or 3 min with the background electrolyte solution. With the PMOTAC coatings at pH values ≤5, the RSDs of the EOFs were less than 2.9% after 60 injections. The effects of the molar mass of the polycation and of PEGylation of PMOTAC on the interactions between the polycations and basic proteins were studied at acidic pH values. The differences in the effective electrophoretic mobilities, resolution values, and plate numbers of the proteins with the different coatings were due to the EOF, as demonstrated through calculations of reduced mobilities, relative resolution values, and relative plate numbers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2655–2663, 2007     

From model compounds to extended pi-conjugated systems: synthesis and properties of dithieno[3,2-b:2',3'-d]phospholes

To explore their suitability for applications in molecular optoelectronics and as sensory materials, novel dithieno[3,2-b:2',3'-d]phospholes have been synthesized and their reactivity and properties investigated. An efficient two-step synthesis allowed for a modular assembly of differently functionalized compounds. The dithieno[3,2-b:2',3'-d]phosphole system exhibits extraordinary optoelectronic properties with respect to wavelength, intensity, and tunability. Owing to the nucleophilic nature of the central phosphorus atom, its significant electronic influence on the conjugated pi system can be altered selectively by chemically facile modifications such as oxidation or complexation with Lewis acids or transition metals. All the dithienophosphole species presented show very strong blue photoluminescence with excellent quantum yield efficiencies supporting their potential utility as blue-light emitting components in organic light emitting diodes (OLEDs). Furthermore, depending on the electronic nature of the phosphorus center, the materials exhibit distinctive optoelectronic properties suggesting that the dithieno[3,2-b:2',3'-d]phosphole system may be useful as sensory material. Theoretical calculations, including time-dependent DFT methods, revealed the excellent predictability of the structures and optoelectronic properties of the functionalized dithienophospholes allowing the design of future dithieno[3,2-b:2',3'-d]phosphole-based materials to be "stream-lined". By using tin-functionalized dithienophosphole monomers, a strategy, which involves Stille coupling, towards extended pi-conjugated materials with significantly redshifted optoelectronic properties is also presented.     

The magnetic behaviour of [NnBu4]4[Ni16Pd16(CO)40]: an even-electron homoleptic carbonyl-metal cluster anion displaying a J = 2 ground state

The magnetic behaviour of the even-electron [Ni16Pd16(CO)40]4- cluster, in its [NnBu4]+ salt, has been investigated by magnetometry and muon spin rotation/relaxation (muSR) spectroscopy. The susceptibility measurements show an exceptionally high magnetic moment corresponding to a total spin value J=2. This suggests a Hund filling of a quadruplet ground state, quite unique in carbonyl-metal clusters. SQUID magnetometry shows a departure from the Curie-Weiss law, for T>150 K, and strong deviation from a Brillouin behaviour of the magnetisation curves. muSR spectroscopy in zero applied field shows a temperature independent decay of the muon spin polarisation, similar to that of a purely paramagnetic system. The observed muon spin repolarisation in a moderate external longitudinal field, however, invalidates this simple picture and suggests the presence of a local anisotropy field acting on the cluster's magnetic moment. A consistent interpretation of magnetometry and muSR results implies the occurrence of an additional interaction of the cluster spin with an effective crystalline field. The inclusion of this interaction in a model Hamiltonian allows us to successfully reproduce both the susceptibility and magnetisation data.     

Geranylgeraniol formation in Croton stellatopilosus proceeds via successive monodephosphorylations of geranylgeranyl diphosphate

The process of catalytic dephosphorylation of geranylgeranyl diphosphate (GGPP) to give geranylgeraniol (GGOH) in Croton stellatopilosus leaves was examined by in vivo chloroplast feedings with [1-³H]GGPP and [1-³H]GGMP and in vitro enzyme-catalyzed reactions. The results strongly suggest that the formation of GGOH from GGPP proceeds in the chloroplasts via two successive monodephosphorylation reactions. Hence, we name the enzyme geranylgeranyl diphosphate phosphatase rather than geranylgeranyl diphosphatase based on its catalytic mechanism.     

Induced Production,Synthesis, and Immunomodulatory Action of Clostrisulfone,a Diarylsulfone from Clostridium acetobutylicum

The anaerobe Clostridium acetobutylicum belongs to the most important industrially used bacteria. Whereas genome mining points to a high potential for secondary metabolism in C. acetobutylicum, the functions of most biosynthetic gene clusters are cryptic. We report that the addition of supra-physiological concentrations of cysteine triggered the formation of a novel natural product, clostrisulfone ( 1 ). Its structure was fully elucidated by NMR, MS and the chemical synthesis of a reference compound. Clostrisulfone is the first reported natural product with a diphenylsulfone scaffold. A biomimetic synthesis suggests that pentamethylchromanol-derived radicals capture sulfur dioxide to form 1 . In a cell-based assay using murine macrophages a biphasic and dose-dependent regulation of the LPS-induced release of nitric oxide was observed in the presence of 1 .     

2‐Hydroxy‐1,2,3,6‐tetrahydro‐azulen‐6‐carboxylic Acid Ethyl Ester—A Novel Precursor for a New Class of Liquid Crystalline Materials

A novel approach for the syntheses of carbene adduct 4 is reported. A ring-enlargement strategy was employed for the synthesis of precursors 5 and 6 and established the mechanism of the formation of azulene derivative 6. Synthesis of target precursor 13, a novel precursor for the synthesis of new mesogenic materials, and its various halogenated derivatives (14–16) was carried out.