Chromatographic separation simulation of metal‐chelating peptides from surface plasmon resonance binding parameters

Some metal‐chelating peptides have antioxidant properties, with potential nutrition, health, and cosmetics applications. This study aimed to simulate their separation on immobilized metal ion affinity chromatography from their affinity constant for immobilized metal ion determined in surface plasmon resonance, both technics are based on peptide‐metal ion interactions. In our approach, first, the affinity constant of synthetic peptides was determined by surface plasmon resonance and used as input data to numerically simulate the chromatographic separation with a transport‐dispersive model based on Langmuir adsorption isotherm. Then, chromatographic separation was applied on the same peptides to determine their retention time and compare this experimental t_R with the simulated t_R obtained from simulation from surface plasmon resonance data. For the investigated peptides, the relative values of t_R were comparable. Hence, our study demonstrated the pertinence of such numerical simulation correlating immobilized metal ion affinity chromatography and surface plasmon resonance.     

Selenium speciation in soil extracts using LC-ICP-MS

Selenium (Se) speciation in soil affects its bioavailability to crops. An analytical procedure for the determination of inorganic Se species (selenite and selenate) in soil extracts by anion-exchange liquid chromatography (LC) with ICP-MS detection has been developed, with 10-fold higher sensitivity than existing HGAAS-based soil Se measurements. A comparison of phosphate extraction solutions on agricultural soils amended with 20?µg?kg^–1 selenate or selenite was carried out, and a 0.016?M?KH₂PO₄ extraction solution is recommended. Recovery of selenate was >91%; however, selenite recovery ranged between 18.5% and 46.1%, due to rapid binding to the soil. Soil preparation did not have a significant (p?>?0.05) effect on the extractability of the selenate or selenite amendments. The stability of Se species in the phosphate extracts was variable, depending on temperature and storage time. Therefore, immediate (<1?h) analysis of the soil extracts is preferable. The method developed was applied to the determination of extractable Se from six arable soils in the UK. Extractable Se levels in these soils ranged between 6 and 13?µg?kg^–1 consisting of selenite and some soluble organic Se.     

Filling Length in Finitely Presentable Groups

We study the filling length function for a finite presentation of a group , and interpret this function as an optimal bound on the length of the boundary loop as a van Kampen diagram is collapsed to the basepoint using a combinatorial notion of a null-homotopy. We prove that filling length is well behaved under change of presentation of . We look at 'AD-pairs' (f,g) for a finite presentation : that is, an isoperimetric function f and an isodiametric function g that can be realised simultaneously. We prove that the filling length admits a bound of the form [g+1][log (f+1)+1] whenever (f,g) is an AD-pair for . Further we show that (up to multiplicative constants) if is an isoperimetric function ( ) for a finite presentation then ( ) is an AD-pair. Also we prove that for all finite presentations filling length is bounded by an exponential of an isodiametric function.Partially supported by NSF grant DMS-9800158Supported by EPSRC Award No. 98001683 and Corpus Christi College, Oxford.     

Use of labelled nitrogen to measure gross and net rates of mineralization and microbial activity in permanent pastures following fertilizer applications at different time intervals

Measurements of some of the main internal N-cycling processes in soil were obtained by labelling the inorganic N pool with the stable isotope of nitrogen ((15)N). The (15)N mean pool dilution technique, combined with other field measurements, enabled gross and net N-mineralization rates to be resolved in grassland soils, which had previously either received fertilizer N (F), or had remained unfertilized (U) for many years. The two soils were subdivided into plots that received N at different time intervals (over 3 weeks), prior to (15)N measurements being made. By this novel approach, possible 'priming' effects over time were investigated to try to overcome some of the temporal problems of isotopic labelling of soil N (native plus fertilizer) and to identify possible changes in a range of primary N-transformation processes. The results suggested that an overall stimulation of microbially mediated processes occurred with all N treatments, but there were inconsistencies associated with the release of N, both in the timing and the degree to which different processes responded to the application of fertilizer N. The rates of these processes were, however, within the range of previously reported data and the (15)N measurements were not adversely affected by the differences in N pools created by the treatments. Thus, the mean pool dilution technique was shown to be applicable to agricultural soils, under conditions relevant to grass swards receiving fertilizer. For example, between the U and F treatments, the size of inorganic N pools increased by five-fold and gross rates of mineralization reached 3.5 and 4.8 microg N g(-1) (dry soil) d(-1), respectively, but did not vary greatly with the timing of N applications. A correlation (r(2) = 0.57) was found between soil respiration (which is relatively simple to measure) and net mineralization (which is more time consuming), suggesting that the former might be used as an indicator of the latter. Although this relationship was stronger in previously unfertilized soils, the similarities found with fertilized soils suggest that this approach could be used to obtain information of wider agronomic value and would, therefore, warrant further work under a range of soil conditions.     

Placement and characterization of pairs of luminescent molecules in spatially separated regions of nanostructured thin films

Methods of making mesostructured sol-gel silicate thin films containing two different molecules deliberately placed in two different spatially separated regions in a one-step, one-pot preparation are developed and demonstrated. When the structure-directing agent is the surfactant cetyltrimethylammonium bromide, the structure is 2-D hexagonal with lattice spacings between 31.6 and 42.1 angstroms depending on the dopant molecules and their concentrations. The three general strategies that are used to place the molecules are philicity (like dissolves like), bonding, and bifunctionality. These strategies take advantage of the different chemical and physical properties of the regions of the films. These regions are the inorganic silicate framework, the hydrophobic organic interior of the micelles, and the ionic interface between them. Luminescent molecules that possess the physical and chemical properties appropriate for the desired strategies are chosen. Lanthanide and ruthenium complexes with condensable trialkoxysilane groups are incorporated into the silicate framework. 1,4-Naphthoquinone, pyrene, rhodamine 6G and coumarin 540A, and lanthanides with no condensable trialkoxysilanes occupy the hydrophobic core of micelles by virtue of their hydrophobicity. The locations of the molecules are determined by luminescence spectroscopy and by luminescence lifetime measurements. In all cases, the long-range order templated into the thin film is verified by X-ray diffraction. The simultaneous placement of two molecules in the structured film and the maintenance of long-range order require a delicate balance among film preparation methodology, design of the molecules to be incorporated in specific regions, and concentrations of all of the species.     

Electrophoresis in the presence of gradients: I. Viscosity gradients

In many cases, the resolution provided by capillary electrophoresis systems approaches that predicted for diffusion-limited separations. Once all device-related sources of band broadening have been eliminated or minimized, only thermal diffusion remains. In principle, peaks can be sharpened using gradients of various system characteristics such as gel concentration, buffer viscosity and electric field. However, it is not clear whether this can actually increase the resolution of the system. In this article, we focus our attention on viscosity gradients and we examine both continuous and step-like variations. Our results indicate that the performance of electrophoretic systems cannot be improved by viscosity gradients. They may provide extra stacking, and thus improve the resolution, when the injection width is non-negligible. However, for the systems considered here, the best resolution is obtained when the viscosity is uniform and the stacking is entirely performed at injection. We conclude by discussing the link between these results, the fundamental laws of thermodynamics, the nature of the detection process and the importance of having nonlinear effects in nonuniform systems.     

Total synthesis of the mycolactones

[structure: see text] The first total synthesis of the mycolactones is reported. This work unambiguously confirms our earlier relative and absolute stereochemical assignment of the mycolactones.     

Materials science of the gel to fluid phase transition in a supported phospholipid bilayer

We report the results of in situ AFM measurements examining the phase transition of bilayers formed from the zwitterionic phospholipid, DMPC, 1,2-dimyristoyl-sn-glycero-3-phosphocholine, supported on mica. The images show that the fluid to gel phase transition process features substantial tearing of the bilayer due to the density change between the two phases. The gel to fluid transition is strongly affected by the resultant stress introduced into the gel phase, which changes the degree of cooperativity, the shape of developing fluid phase regions, and the course of the transition.