EXCITATION ENERGY TRANSFER IN THE CRYPTOPHYTES. FLUORESCENCE EXCITATION SPECTRA AND PICOSECOND TIME-RESOLVED EMISSION SPECTRA OF INTACT ALGAE AT 77 K

Excitation spectra of chlorophyll- a (Chl- a ) fluorescence in intact cells of Cryptomonas ovata, Chroomonas pauciplastida and Chroomonas salina were determined at 77 K. For all species the excitation spectra for emission from Chl- a associated with photosystem II (PSII) showed increased contributions by a carotenoid (493 nm) and phycobiliproteins, and decreased contributions by carotenoid (417 nm, 505 nm) and Chl- a (445 nm) as compared to excitation spectra for emission from Chl- a associated with photosystem I (PSI). Excitation spectra of C. salina and C. ovata showed an increased contribution by Chl- c ² to PSII Chl- a fluorescence emission. In all three species the absorbance band positions of Chl- a , as determined from the excitation spectra, were similar to those previously described in green plants. green algae and phycobilisome-containing organisms. Time-resolved 77 K fluorescence emission spectra of C. ovata and C. salina showed successive emission from both phycoerythrin and Chl- c ², PSII Chl- a , and PSI Chl- a. C. pauciplastida showed successive emission from phycocyanin, PSII Chl- a , and PSI Chl- a. Spectral red-shifts with time were observed for the phycobiliprotein peaks in all three species. The fluorescence decay of phycoerythrin in C. ovata and C. salina was faster than that of phycocyanin in C. pauciplastida. The results are discussed in relation to the organization of the antenna pigments of PSII and PSI in the cryptophyte algae.     

Studies on the substrate specificity of Escherichia coli galactokinase

In vitro glycorandomization (IVG) technology is dependent upon the ability to rapidly synthesize sugar phosphates. Compared with chemical synthesis, enzymatic (kinase) routes to sugar phosphates would be attractive for this application. This work focuses upon the development of a high-throughput colorimetric galactokinase (GalK) assay and its application toward probing the substrate specificity and kinetic parameters of Escherichia coli GalK. The demonstrated dinitrosalicylic assay should also be generally applicable to a variety of sugar-processing enzymes. [reaction: see text]     

Random Walk Conditioned to Stay Positive

A random walk that is certain to visit (0, ) has associatedwith it, via a suitable h-transform, a Markov chain called ‘randomwalk conditioned to stay positive’, which is defined properlybelow. In continuous time, if the random walk is replaced byBrownian motion then the analogous associated process is Bessel-3.Let (x) = log log x. The main result obtained in this paper,which is stated formally in Theorem 1, is that, when the randomwalk has zero mean and finite variance, the total time for whichthe random walk conditioned to stay positive is below x ultimatelylies between Lx²/(x) and Ux²(x), for suitable (non-random) positiveL and finite U, as x goes to infinity. For Bessel-3, the bestL and U are identified.     

Limiting point processes in the branching random walk

Summary Take the nth generation of a supercritical branching random walk (a spatially homogeneous branching process) as a process of cluster centres and take independent copies of some simple point process Y as the clusters. Let the resulting point process be Y _n . For a given sequence of real numbers {x _n } let Y _n be centred on x _n . Under certain conditions, when an appropriate scale change is made, the resulting point process converges in distribution to a non-trivial limit.     

Bio-inspired approaches to sensing for defence and security applications

Interdisciplinary research in biotechnology and related scientific areas has increased tremendously over the past decade. This rapid pace, in conjunction with advances in microfabricated systems, computer hardware, bioengineering and the availability of low-powered miniature components, has now made it feasible to design bio-inspired materials, sensors and systems with tremendous potential for defence and security applications. To realize the full potential of biotechnology and bio-inspiration, there is a need to define specific requirements to meet the challenges of the changing world and its threats. One approach to assisting the defence and security communities in defining their requirements is through the use of a conceptual model. The distributed or intelligent autonomous sensing (DIAS) system is one such model. The DIAS model is not necessarily aimed at a single component, for instance a sensor, but can include a system, or even a system of systems in the same way that a single organism, a multi-cellular organism or group of organisms is configured. This paper provides an overview of the challenges to and opportunities for bio-inspired sensors and systems together with examples of how they are being implemented. Examples focus on both learning new things from biological organisms that have application to the defence and security forces and adapting known discoveries in biology and biochemistry for practical use by these communities.     

Malleilactone, a Polyketide Synthase-Derived Virulence Factor Encoded by the Cryptic Secondary Metabolome of Burkholderia pseudomallei Group Pathogens

Sequenced bacterial genomes are routinely found to contain gene clusters that are predicted to encode metabolites not seen in fermentation-based studies. Pseudomallei group Burkholderia are emerging pathogens whose genomes are particularly rich in cryptic natural product biosynthetic gene clusters. We systematically probed the influence of the cryptic secondary metabolome on the virulence of these bacteria and found that disruption of the MAL gene cluster, which is natively silent in laboratory fermentation experiments and conserved across this group of pathogens, attenuates virulence in animal models. Using a promoter exchange strategy to activate the MAL cluster, we identified malleilactone, a polyketide synthase-derived cytotoxic siderophore encoded by this gene cluster. Small molecules targeting malleilactone biosynthesis either alone or in conjunction with antibiotics could prove useful as therapeutics to combat melioidosis and glanders.     

Crystallographic characterization of the metal–organic framework Fe2(bdp)3 upon reductive cation insertion

Precisely locating extra-framework cations in anionic metal–organic framework compounds remains a long-standing, yet crucial, challenge for elucidating structure–performance relationships in functional materials. Single-crystal X-ray diffraction is one of the most powerful approaches for this task, but single crystals of frameworks often degrade when subjected to post-synthetic metalation or reduction. Here, we demonstrate the growth of sizable single crystals of the robust metal–organic framework Fe₂(bdp)₃ (bdp²⁻ = benzene-1,4-dipyrazolate) and employ single-crystal-to-single-crystal chemical reductions to access the solvated framework materials A₂Fe₂(bdp)₃·yTHF (A = Li⁺, Na⁺, K⁺). X-ray diffraction analysis of the sodium and potassium congeners reveals that the cations are located near the center of the triangular framework channels and are stabilized by weak cation–π interactions with the framework ligands. Freeze-drying with benzene enables isolation of activated single crystals of Na_0.5Fe₂(bdp)₃ and Li₂Fe₂(bdp)₃ and the first structural characterization of activated metal–organic frameworks wherein extra-framework alkali metal cations are also structurally located. Comparison of the solvated and activated sodium-containing structures reveals that the cation positions differ in the two materials, likely due to cation migration that occurs upon solvent removal to maximize stabilizing cation–π interactions. Hydrogen adsorption data indicate that these cation–framework interactions are sufficient to diminish the effective cationic charge, leading to little or no enhancement in gas uptake relative to Fe₂(bdp)₃. In contrast, Mg_0.85Fe₂(bdp)₃ exhibits enhanced H₂ affinity and capacity over the non-reduced parent material. This observation shows that increasing the charge density of the pore-residing cation serves to compensate for charge dampening effects resulting from cation–framework interactions and thereby promotes stronger cation–H₂ interactions.

Single-crystal X-ray diffraction reveals structural influences on gas adsorption properties in anionic metal–organic frameworks.     

The growth of iterates of multivariate generating functions

The vector-valued function of a -vector has components . For each , is the (multivariate) Laplace transform of a discrete measure concentrated on with only a finite number of atoms. The main objective is to give conditions for the functional iterates of to grow like for a suitable . The initial stimulus was provided by results of Miller and O'Sullivan (1992) on enumeration issues in `context free languages', results which can be improved using the theory developed here. The theory also allows certain results in Jones (2004) on multitype branching to be proved under significantly weaker conditions.

     

Expected population size in the generation-dependent branching process

"A Malthusian parameter for the generation-dependent general branching process is introduced and some asymptotics of the expected population size, counted by a general non-negative characteristic, are discussed. Processes both with and without immigration are considered."