A new and rapid method for the determination of nicarbazin residues in poultry feed, eggs and muscle tissue using supercritical fluid extraction and high performance liquid chromatography

A simple and rapid method, using supercritical fluid extraction (SFE) with off-line high-performance liquid chromatography for the isolation and determination of nicarbazin, a popular broad-spectrum coccidiostatic drug used principally in poultry, is described. Results show good repeatability with a minimum quantification level of 0.4 microgram g-1 and mean 'spiked' recoveries of 98%, 100% and 99% using poultry feeds (n = 18), eggs (n = 28) and chicken tissue (n = 20), respectively. SFE using carbon dioxide is proposed as an alternative isolation method to the current Association of Official Analytical Chemists (AOAC) procedure which involves the use of large volumes of a harmful solvent (dimethylformamide) and requires a long tedious separation and clean-up regime (6 h) prior to its determination.     

Shift to Pseudomonic acid B production in P. fluorescens NCIMB10586 by mutation of mupirocin tailoring genes mupO, mupU, mupV, and macpE

Mupirocin, a polyketide-derived antibiotic from Pseudomonas fluorescens NCIMB10586, is a mixture of pseudomonic acids (PA) that target isoleucyl-tRNA synthase. The mup gene cluster encodes both type I polyketide synthases and monofunctional enzymes that should play a role during the conversion of the product of the polyketide synthase into the active antibiotic (tailoring). By in-frame deletion analysis of selected tailoring open-reading frames we show that mupQ, mupS, mupT, and mupW are essential for mupirocin production, whereas mupO, mupU, mupV, and macpE are essential for production of PA-A but not PA-B. Therefore, PA-B is not simply produced by hydroxylation of PA-A but is either a precursor of PA-A or a shunt product. In the mupW mutant, a new metabolite lacking the tetrahydropyran ring is produced, implicating mupW in oxidation of the 16-methyl group.     

Multiple state emission from rhodium(I) and iridium(I) complexes

The effect of temperature (2–100 K) on the emission spectra and lifetimes of [M(2 = phos)₂]ClO₄ (M = Rh(I), Ir(I): 2 = phos is cis-1,2-bis-(diphenylphosphino)ethylene) is interpreted with a two-level spin-orbit-split emitting manifold. For [Ir(2 = phos)₂]ClO₄, Δ? = 143cm^?1, τ(lower) = 999μs, and τ(higher) = 1.54 μs. For the rhodium species, Δ? = 35 cm^?1, τ(lower) = 5920 μs, and τ(higher) = 20.3 μs.     

First in vitro directed biosynthesis of new compounds by a minimal type II polyketide synthase: evidence for the mechanism of chain length determination

The minimal actinorhodin polyketide synthase bearing two point mutations (KSbeta Q161A, ACP C17S) was chemically modified to carry novel C4 to C8 starter units on the ACP: on incubation with an excess of malonyl CoA new 16-carbon polyketides are made, supporting a measuring mechanism.     

Wrinkle morphologies with two distinct wavelengths

Wrinkles with two distinct wavelengths formed sequentially on the same surface are investigated. A series of aligned wrinkles are formed through local strain application on a partially crosslinked elastomer. After the formation of these primary wrinkles, the elastomer is fully crosslinked, and a mechanical compressive strain is applied to the sample orthogonal to the primary wrinkles. This mechanical strain results in smaller secondary wrinkles superimposed on the larger primary aligned wrinkles. Resulting biaxial morphologies suggest that the primary pattern directs the formation of the smaller wrinkles. The modulus mismatch of the substrate on primary and secondary wrinkle formation dictates the ratio between the two resulting wavelengths, as well as the specific biaxial morphologies, ranging from zigzag ridges to ellipsoidal bumps or corn‐on‐the‐cob structures to the classic herringbone. The sequential strain wrinkling process has the potential to be used on an industrial scale for the facile formation of surface topography with two discrete, tunable lateral dimensions over large surface areas. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Controlled evaporative self-assembly of polymer nanoribbons using oscillating capillary bridges

Evaporative self-assembly (ESA), based on the “coffee-ring” effect, is a versatile technique for assembling particle solutions into mesoscale patterns and structures on different substrates. ESA works with a wide variety of organic and inorganic materials, where the solution is a combination of volatile solvent and nonvolatile solute. Modified ESA methods, such as “stop-and-go flow coating,” use a programmed meniscus “stick–slip” motion to create mesoscale assemblies with controlled shape, size, and architecture. However, current methods are not scalable for increased production volumes or patterning large surface areas. We demonstrate a new ESA method, where an oscillating blade controls the meniscus depinning and drives the evaporative assembly of solutes at the pinned meniscus. Results show that oscillation frequency and substrate speed control time/distance intervals between successive meniscus depinning, and the assembly dimensions depend on solution concentration, oscillation frequency, substrate speed, and meniscus height. We report the mechanism of the meniscus depinning and the control over assembly cross-sectional dimensions. This advance provides a scalable ESA method with faster processing times and maintained advantages. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1545–1551     

Micromechanical Properties of Microstructured Elastomeric Hydrogels

Local, micromechanical environment is known to influence cellular function in heterogeneous hydrogels, and knowledge gained in micromechanics will facilitate the improved design of biomaterials for tissue regeneration. In this study, a system comprising microstructured resilin‐like polypeptide (RLP)–poly(ethylene glycol) (PEG) hydrogels is utilized. The micromechanical properties of RLP‐PEG hydrogels are evaluated with oscillatory shear rheometry, compression dynamic mechanic analysis, small‐strain microindentation, and large‐strain indentation and puncture over a range of different deformation length scales. The measured elastic moduli are consistent with volume averaging models, indicating that volume fraction, not domain size, plays a dominant role in determining the low strain mechanical response. Large‐strain indentation under a confocal microscope enables the visualization of the microstructured hydrogel micromechanical deformation, emphasizing the translation, rotation, and deformation of RLP‐rich domains. The fracture initiation energy results demonstrate that failure of the composite hydrogels is controlled by the RLP‐rich phase, and their independence with domain size suggested that failure initiation is controlled by multiple domains within the strained volume. This approach and findings provide new quantitative insight into the micromechanical response of soft hydrogel composites and highlight the opportunities in employing these methods to understand the physical origins of mechanical properties of soft synthetic and biological materials.     

Water cavitation of hydrogels

Using the cavitation rheology (CR) technique developed in our labs, we show that fluids with negligible interfacial tensions with a surrounding material can be used to induce an elastic, cavitation instability in that material. We do this by changing the cavitation media from air, which was demonstrated to induce cavitation at the tip of a syringe needle in previous studies, to water, which has a negligible surface tension with the surrounding poly(vinyl alcohol) hydrogel material. In this case, the critical pressure in which this instability occurs can be directly related to the elastic modulus of the surrounding network and is shown to be nearly independent of length scale. This independence of size scale has important implications in the use of CR for the characterization of mechanical properties from molecular to macroscopic length scales. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1423–1427, 2010     

Adhesion of nonplanar wrinkled surfaces

Topological patterns on polymer surfaces can significantly alter and control adhesion. In this study, the effect of surface wrinkles on a spherical surface on adhesion has been studied. Surface wrinkling induced by swelling of a crosslinked polydimethylsiloxane elastomer constrained by a stiff, thin surface layer (silicate) is used to produce topographic features of various length scales over a large curved area. By controlling the properties of the stiff layer and the applied strain conditions, surface wrinkles of varying amplitude and wavelength are obtained. The effect of wrinkle morphology on adhesion is quantified, and the results display a transition from enhancement of adhesion to decrease depending upon wrinkle dimensions. A simple phenomenological model is proposed that describes the change of adhesion behavior as a function of wrinkle morphology. Our results provide a critical understanding toward tuning the adhesion behavior of nonplanar surfaces consisting of periodic topographic structures. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011