Active site modification of the β-ketoacyl-ACP synthase FabF3 of Streptomyces coelicolor affects the fatty acid chain length of the CDA lipopeptides

Using site directed mutagenesis we altered an active site residue (Phe107) of the enzyme encoded by fabF3 (SCO3248) in the Streptomyces coelicolor gene cluster required for biosynthesis of the calcium dependent antibiotics (CDAs), successfully generating two novel CDA derivatives comprising truncated (C4) lipid side chains and confirming that fabF3 encodes a KAS-II homologue that is involved in determining CDA fatty acid chain length.     

Fabrication of 3D metal dot arrays by geometrically structured dynamic shadowing lithography

Sphere lithography (SL), sometimes erroneously generalized as nanosphere lithography (NSL), stands out as a versatile technique capable of producing 2D periodic micro- and nanostructures with general materials applicability, flexible size and shape control, high throughput, and elegance of simplicity. Many of the fundamental aspects of the features produced by SL have been investigated in a systematic manner, including the optical, magnetic, electronic, and catalytic behaviors with emphasis toward applications in biosensing, ultrasensitive spectroscopy, and nanodevice fabrication. Previous work has primarily focused on two-dimensional patterning, however, with little attention paid to vertical growth of the SL features. In this work, the 3D structural evolution of metal dot arrays at two different length scales was demonstrated by SL-based geometrically structured dynamic shadowing lithography (GSDSL). An empirically derived model of structural growth is also developed to predict the shape and size of the features in this system.     

Nonperturbative chemical modification of graphene for protein micropatterning

Graphene's extraordinary physical properties and its planar geometry make it an ideal candidate for a wide array of applications, many of which require controlled chemical modification and the spatial organization of molecules on its surface. In particular, the ability to functionalize and micropattern graphene with proteins is relevant to bioscience applications such as biomolecular sensors, single-cell sensors, and tissue engineering. We report a general strategy for the noncovalent chemical modification of epitaxial graphene for protein immobilization and micropatterning. We show that bifunctional molecule pyrenebutanoic acid-succinimidyl ester (PYR-NHS), composed of the hydrophobic pyrene and the reactive succinimide ester group, binds to graphene noncovalently but irreversibly. We investigate whether the chemical treatment perturbs the electronic band structure of graphene using X-ray photoemission (XPS) and Raman spectroscopy. Our results show that the sp(2) hybridization remains intact and that the π band maintains its characteristic Lorentzian shape in the Raman spectra. The modified graphene surfaces, which bind specifically to amines in proteins, are micropatterned with arrays of fluorescently labeled proteins that are relevant to glucose sensors (glucose oxidase) and cell sensor and tissue engineering applications (laminin).     

Detecting variation in chaotic attractors

If the output of an experiment is a chaotic signal, it may be useful to detect small changes in the signal, but there are a limited number of ways to compare signals from chaotic systems, and most known methods are not robust in the presence of noise. One may calculate dimension or Lyapunov exponents from the signal, or construct a synchronizing model, but all of these are only useful in low noise situations. I introduce a method for detecting small variations in a chaotic attractor based on directly calculating the difference between vector fields in phase space. The differences are found by comparing close strands in phase space, rather than close neighbors. The use of strands makes the method more robust to noise and more sensitive to small attractor differences.     

Thermal decomposition of CF3Br using Br-atom absorption

Br-atom atomic resonance absorption spectrometry (ARAS) has been developed and applied to measure thermal decomposition rate constants for CF₃Br (+ Kr)→CF₃+Br (+ Kr) over the temperature range, 1222–1624 K. The Br-atom curve-of-growth (145<λ<163 nm) was determined using this reaction. For [Br]≤1×10¹² molecules cm⁻³, absorbance, (ABS)=1.410×10⁻¹³ [Br], yielding σ=1.419×10⁻¹⁴ cm². The curve-of-growth was then used to convert (ABS) to Br-atom profiles which were then analyzed to give measured rate constants. These can be expressed in second-order by k₁=8.147×10⁻⁹ exp(−24488 K/T) cm³ molecule⁻¹ s⁻¹ (±33%, 1222≤T≤1624 K). A unimolecular theoretical approach was used to rationalize the data. Theory indicates that the dissociation rates are closer to second- than to first-order, i.e., the magnitudes are 30–53% of the low-pressure-limit rate constants over 1222–1624 K and 123–757 torr. With the known, E₀=ΔH₀⁰=70.1 kcal mole⁻¹, the optimized theoretical fit to the ARAS data requires 〈ΔE〉_down=550 cm⁻¹. These conclusions are consistent with recently published data and theory from Kiefer and Sathyanarayana. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 859–867, 1998     

Bioelectrocatalytic Synthesis: Concepts and Applications

Bioelectrocatalytic synthesis is the conversion of electrical energy into value-added products using biocatalysts. These methods merge the specificity and selectivity of biocatalysis and energy-related electrocatalysis to address challenges in the sustainable synthesis of pharmaceuticals, commodity chemicals, fuels, feedstocks and fertilizers. However, the specialized experimental setups and domain knowledge for bioelectrocatalysis pose a significant barrier to adoption. This review introduces key concepts of bioelectrosynthetic systems. We provide a tutorial on the methods of biocatalyst utilization, the setup of bioelectrosynthetic cells, and the analytical methods for assessing bioelectrocatalysts. Key applications of bioelectrosynthesis in ammonia production and small-molecule synthesis are outlined for both enzymatic and microbial systems. This review serves as a necessary introduction and resource for the non-specialist interested in bioelectrosynthetic research.