Chiral separation of enantiomers of amino acid derivatives by high-performance liquid chromatography on a norvancomycin-bonded chiral stationary phase

A novel norvancomycin-bonded chiral stationary phase (NVC-CSP) was synthesized by using the chiral selector of norvancomycin. The chiral separation of enantiomers of several dansyl-amino acids by high-performance liquid chromatography (HPLC) in the reversed-phase mode is described. The effects of some parameters, such as organic modifier concentration, column temperature, pH and flow rate of the mobile phase, on the retention and enantioselectivity were investigated. The study showed that ionic, as well as hydrophobic interactions were engaged between the analyte and macrocycle in this chromatographic system. Increasing pH of buffers usually improved the chiral resolution for dansyl-alpha-amino-n-butyric acid (Dns-But), dansyl-methionine (Dns-Met) and dansyl-threonine (Dns-Thr), but not for dansyl-glutamic acid (Dns-Glu) which contains two carboxylic groups in its molecular structure. The natural logarithms of selectivity factors (In alpha) of all the investigated compounds depended linearly on the reciprocal of temperature (1/T), most processes of enantioseparation were controlled enthalpically. Interestingly, the process of enantioseparation for dansyl-threonine was enthalpy-controlled at pH of 3.5, while at pH of 7.0, it was entropy-controlled according to thermodynamic parameters Delta(R,S)DeltaHdegrees and Delta(R,S)DeltaSdegrees afforded by Van't Hoff plots. In order to get baseline separation for all the solutes researched, norvancomycin was also used as a chiral mobile phase additive. In combination with the NVC-CSP remarkable increases in enanselectivity were observed for all the compounds, as the result of a "synergistic" effect. (C) 2003 Elsevier B.V. All rights reserved.

A novel process for converting coalmine-drained methane gas to syngas over nickel-magnesia solid solution catalysts

A novel process is developed in this paper for utilizing the coalmine-drained methane gas that is usually vented straight into the atmosphere in most coalmines worldwide. It is expected that low-cost syngas can be produced by the combined air partial oxidation and CO2 reforming of methane, because this process utilizes directly the methane, air, and carbon dioxide in the coalmine-drained gas without going through the separation step. For this purpose, a nickel-magnesia solid solution catalyst was prepared and its catalytic performance for the proposed process was investigated. It was found that calcination temperature has significant influence on the catalytic performance due to the different extent of solid solution formation in the catalysts. A uniform nickel-magnesia solid solution catalyst exhibits higher stability than the catalysts in which NiO has not completely formed solid solution with MgO. Its catalytic activity and selectivity remain stable during 120 h of reaction. The product H-2/CO ratio is mainly dependent on the feed gas composition. By changing CO2/air ratio of the feed gases, syngas with a H-2/CO ratio between 1 and 1.9 can be obtained. The influences of reaction temperature and nickel loading on the catalytic performance were also investigated. (c) 2004 Elsevier B.V All rights reserved.

Electrochromatographic evaluation of a silica monolith capillary column for separation of basic pharmaceuticals

A silica-based monolithic capillary column was prepared via a sol-gel process. The continuous skeleton and large through-pore structure were characterized by scanning electron microscopy (SEM). The native silica monolith has been successfully employed in the electrochromatographic separation of beta-blockers and alkaloids extracted from traditional Chinese medicines (TCMs). Column efficiencies greater than 250000 plates/m for capillary electrochromatography (CEC) separation of basic compounds were obtained. It was observed that retention of basic pharmaceuticals on the silica monolith was mainly contributed by a cation-exchange mechanism. Other retention mechanisms including reversed-phase and normal-phase mechanisms and electrophoresis of basic compounds also played a role in separation. A comparison of the differences between CEC and capillary zone electrophoresis (CZE) separation was also discussed.

Shear effects on the properties and separation characteristics of whey protein precipitates

Selective isoelectric whey protein precipitation and aggregation is carried out at laboratory scale in a standard configuration batch agitation vessel. Geometric scale-up of this operation is implemented on the basis of constant impeller power input per unit volume and subsequent clarification is achieved by high speed disc-stack centrifugation. Particle size and fractal geometry are important in achieving efficient separation while aggregates need to be strong enough to resist the more extreme levels of shear that are encountered during processing, for example through pumps, valves and at the centrifuge inlet zone. This study investigates how impeller agitation intensity and ageing time affect aggregate size, strength, fractal dimension and hindered settling rate at laboratory scale in order to determine conditions conducive for improved separation. Particle strength is measured by observing the effects of subjecting aggregates to moderate and high levels of process shear in a capillary rig and through a partially open ball-valve respectively. The protein precipitate yield is also investigated with respect to ageing time and impeller agitation intensity. A pilot scale study is undertaken to investigate scale-up and how agitation vessel shear affects centrifugal separation efficiency. Laboratory scale studies show that precipitates subject to higher impeller shear-rates during the addition of the precipitation agent are smaller but more compact than those subject to lower impeller agitation and are better able to resist turbulent breakage. They are thus more likely to provide a better feed for more efficient centrifugal separation. Protein precipitation yield improves significantly with ageing, and 50 minutes of ageing is required to obtain a 70 - 80% yield of α-lactalbumin. Geometric scale-up of the agitation vessel at constant power per unit volume results in aggregates of broadly similar size exhibiting similar trends but with some differences due to the absence of dynamic similarity due to longer circulation time and higher tip speed in the larger vessel. Disc stack centrifuge clarification efficiency curves show aggregates formed at higher shear-rates separate more efficiently, in accordance with laboratory scale projections. Exposure of aggregates to highly turbulent conditions, even for short exposure times, can lead to a large reduction in particle size. Thus, improving separation efficiencies can be achieved by the identification of high shear zones in a centrifugal process and the subsequent elimination or amelioration of such.

Development of low-cost sensing and separation devices based on macro, micro and nano technology for health applications

The work presented in this thesis described the development of low-cost sensing and separation devices with electrochemical detections for health applications. This research employs macro, micro and nano technology. The first sensing device developed was a tonerbased micro-device. The initial development of microfluidic devices was based on glass or quartz devices that are often expensive to fabricate; however, the introduction of new types of materials, such as plastics, offered a new way for fast prototyping and the development of disposable devices. One such microfluidic device is based on the lamination of laser-printed polyester films using a computer, printer and laminator. The resulting toner-based microchips demonstrated a potential viability for chemical assays, coupled with several detection methods, particularly Chip-Electrophoresis-Chemiluminescence (CE-CL) detection which has never been reported in the literature. Following on from the toner-based microchip, a three-electrode micro-configuration was developed on acetate substrate. This is the first time that a micro-electrode configuration made from gold; silver and platinum have been fabricated onto acetate by means of patterning and deposition techniques using the central fabrication facilities in Tyndall National Institute. These electrodes have been designed to facilitate the integration of a 3- electrode configuration as part of the fabrication process. Since the electrodes are on acetate the dicing step can automatically be eliminated. The stability of these sensors has been investigated using electrochemical techniques with excellent outcomes. Following on from the generalised testing of the electrodes these sensors were then coupled with capillary electrophoresis. The final sensing devices were on a macro scale and involved the modifications of screenprinted electrodes. Screen-printed electrodes (SPE) are generally seen to be far less sensitive than the more expensive electrodes including the gold, boron-doped diamond and glassy carbon electrodes. To enhance the sensitivity of these electrodes they were treated with metal nano-particles, gold and palladium. Following on from this, another modification was introduced. The carbonaceous material carbon monolith was drop-cast onto the SPE and then the metal nano-particles were electrodeposited onto the monolith material

Practical solvent system selection for counter-current separation of pharmaceutical compounds

Counter-current chromatography (CCC) is a technique that shows a lot of potential for large scale purification. Its usefulness in a "research and development" pharmaceutical environment has been investigated, and the conclusions are shown in this article. The use of CCC requires the development of an appropriate solvent system (a parameter of critical importance), a process which can be tedious. This article presents a novel strategy, combining a statistical approach and fast HPLC to generate a three-dimensional partition coefficient map and rapidly predict an optimal solvent system. This screen is performed in half a day and involves 9 experiments per solvent mixture. Test separations were performed using that screen to ensure the validity of the method.

Kinetics of phase transformations in a model with metastable fluid-fluid separation: A molecular dynamics study

By molecular dynamics (MD) simulations we study the crystallization process in a model system whose particles interact by a spherical pair potential with a narrow and deep attractive well adjacent to a hard repulsive core. The phase diagram of the model displays a solid-fluid equilibrium, with a metastable fluid-fluid separation. Our computations are restricted to fairly small systems (from 2592 to 10368 particles) and cover long simulation times, with constant energy trajectories extending up to 76x10(6) MD steps. By progressively reducing the system temperature below the solid-fluid line, we first observe the metastable fluid-fluid separation, occurring readily and almost reversibly upon crossing the corresponding line in the phase diagram. The nucleation of the crystal phase takes place when the system is in the two-fluid metastable region. Analysis of the temperature dependence of the nucleation time allows us to estimate directly the nucleation free energy barrier. The results are compared with the predictions of classical nucleation theory. The critical nucleus is identified, and its structure is found to be predominantly fcc. Following nucleation, the solid phase grows steadily across the system, incorporating a large number of localized and extended defects. We discuss the relaxation processes taking place both during and after the crystallization stage. The relevance of our simulation for the kinetics of protein crystallization under normal experimental conditions is discussed. (C) 2002 American Institute of Physics.

Critical stages of the brewing process for changes in antioxidant activity and levels of phenolic compounds in ale

Samples were taken at each stage of brewing (malt, milling, mashing, wort separation, hop addition, boiling, whirlpool, dilution, fermentation, warm rest, chill-lagering, beer filtration, carbonation and bottling, pasteurization, and storage). The level of antioxidant activity of unfractionated, low-molecular-mass (LMM) and high-molecular-mass (HMM) fractions was measured by the 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfortic acid) radical cation (ABTS(.+)) and ferric-reducing antioxidant power (FRAP) procedures. Polyphenol levels were assessed by HPLC. The LMM fraction ( 0.001) in catechin and ferulic acid levels. Increases in antioxidant activity levels were observed after mashing, boiling, fermentation, chill-lagering, and pasteurization, in line with previous studies on lager. Additionally, increases in the level of antioxidant activity occurred after wort separation and carbonation and bottling and were accompanied by increases in levels of most monitored polyphenols. Data from the ABTS(.-) and FRAP assays indicated that the compounds contributing to the levels of antioxidant activity responded differently in the two procedures. Levels of ferulic, vanillic, and chlorogenic acids and catechin accounted for 45-61% of the variation in antioxidant activity levels.

Friedel-Crafts Benzoylation of Anisole in Ionic Liquids: Catalysis, Separation, and Recycle Studies

The comparison of three ionic liquid-mediated catalytic processes for the benzoylation of anisole with benzoic anhydride is presented. A detailed understanding of the mechanism by which the zeolite and metal triflate reactions in bis{trifluoromethanesulfonyl}imide-based ionic liquids has been reported previously, and these routes are considered together with an indium chloride-based ionic liquid system. Solvent extraction and vacuum/steam distillation have been assessed as possible workup procedures, and an overall preliminary economic evaluation of each overall process is reported. Although the predominant activity is associated with the in situ formation of a homogeneous acid catalyst, the low cost and facile separation of the zeolite-catalysed process leads to this route being the most economically viable overall option. The results of a continuous flow miniplant based on the zeolite catalyst are also presented and compared with the reaction using a small plug How reactor.

Max separation clustering for feature extraction from Optical Emission Spectroscopy Data

This paper proposes max separation clustering (MSC), a new non-hierarchical clustering method used for feature extraction from optical emission spectroscopy (OES) data for plasma etch process control applications. OES data is high dimensional and inherently highly redundant with the result that it is difficult if not impossible to recognize useful features and key variables by direct visualization. MSC is developed for clustering variables with distinctive patterns and providing effective pattern representation by a small number of representative variables. The relationship between signal-to-noise ratio (SNR) and clustering performance is highlighted, leading to a requirement that low SNR signals be removed before applying MSC. Experimental results on industrial OES data show that MSC with low SNR signal removal produces effective summarization of the dominant patterns in the data.

Developing an integrated hydrograph separation and lumped modelling approach to quantifying hydrological pathways in Irish river catchments

An appreciation of the quantity of streamflow derived from the main hydrological pathways involved in transporting diffuse contaminants is critical when addressing a wide range of water resource management issues. In order to assess hydrological pathway contributions to streams, it is necessary to provide feasible upper and lower bounds for flows in each pathway. An important first step in this process is to provide reliable estimates of the slower responding groundwater pathways and subsequently the quicker overland and interflow pathways. This paper investigates the effectiveness of a multi-faceted approach applying different hydrograph separation techniques, supplemented by lumped hydrological modelling, for calculating the Baseflow Index (BFI), for the development of an integrated approach to hydrograph separation. A semi-distributed, lumped and deterministic rainfall runoff model known as NAM has been applied to ten catchments (ranging from 5 to 699 km2). While this modelling approach is useful as a validation method, NAM itself is also an important tool for investigation. These separation techniques provide a large variation in BFI, a difference of 0.741 predicted for BFI in a catchment with the less reliable fixed and sliding interval methods and local minima turning point methods included. This variation is reduced to 0.167 with these methods omitted. The Boughton and Eckhardt algorithms, while quite subjective in their use, provide quick and easily implemented approaches for obtaining physically realistic hydrograph separations. It is observed that while the different separation techniques give varying BFI values for each of the catchments, a recharge coefficient approach developed in Ireland, when applied in conjunction with the Master recession Curve Tabulation method, predict estimates in agreement with those obtained using the NAM model, and these estimates are also consistent with the study catchments’ geology. These two separation methods, in conjunction with the NAM model, were selected to form an integrated approach to assessing BFI in catchments.

A new and less destructive laboratory procedure for the physical separation of distal glass tephra shards from sediments

Tephrochronology, a key tool in the correlation of Quaternary sequences, relies on the extraction of tephra shards from sediments for visual identification and high-precision geochemical comparison. A prerequisite for the reliable correlation of tephra layers is that the geochemical composition of glass shards remains unaltered by natural processes (e.g. chemical exchange in the sedimentary environment) and/or by laboratory analytical procedures. However, natural glasses, particularly when in the form of small shards with a high surface to volume ratio, are prone to chemical alteration in both acidic and basic environments. Current techniques for the extraction of distal tephra from sediments involve the ‘cleaning’ of samples in precisely such environments and at elevated temperatures. The acid phase of the ‘cleaning’ process risks alteration of the geochemical signature of the shards, while the basic phase leads to considerable sample loss through dissolution of the silica network. Here, we illustrate the degree of alteration and loss to which distal tephras may be prone, and introduce a less destructive procedure for their extraction. This method is based on stepped heavy liquid flotation and which results in samples of sufficient quality for analysis while preserving their geochemical integrity. In trials, this method out-performed chemical extraction procedures in terms of the number of shards recovered and has resulted in the detection of new tephra layers with low shard concentrations. The implications of this study are highly significant because (i) the current database of distal tephra records and their corresponding geochemical signatures may require refinement and (ii) the record of distal tephras may be incomplete due to sample loss induced by corrosive laboratory procedures. It is therefore vital that less corrosive laboratory procedures are developed to make the detection and classification of distal glass tephra more secure.

Properties of Super-Hydrophobic Copper and Stainless Steel Meshes: Applications in Controllable Water Permeation and Organic Solvents/Water Separation

The wettability and hydrophobicity of super-hydrophobic (SH) meshes is greatly influenced by their topographic structures, chemical composition and coating process. In this study, the properties of copper and stainless steel meshes, coated with super-hydrophobic electrolessly deposited silver were investigated. A new method to test the pressure resistance of super-hydrophobic mesh was applied to avoid any deformation of mesh. Results showed that SH copper mesh and SH stainless steel meshes with the same pore size have almost the same contact angle and the same hydrophobicity. SH copper mesh with a pore size of 122 μm can resist water pressure of 4900 Pa and a decrease of pore size of mesh can increase the pressure resistance of SH copper mesh. The SH copper mesh modified with 0.1 M HS(CH2)10COOH solution in ethanol has a controllable water permeation property by simply adjusting the pH of water solution. SH copper mesh shows super-oleophilicity with organic solvents and so with a water contact angle of 0° and it can be an effective tool for organic solvents/water separation. The separation efficiency of SH copper mesh for separating mixtures of organic solvent and water can be as high as 99.8%.

Deep separation of benzene from cyclohexane by liquid extraction using ionic liquids as the solvent

Separation of benzene and cyclohexane is one of the most important and difficult processes in the petrochemical industry, especially for low benzene concentration. In this work, three ionic liquids (ILs), [Bmim][BF ₄], [Bpy][BF ₄], and [Bmim][SCN], were investigated as the solvent in the extraction of benzene from cyclohexane. The corresponding ternary liquid-liquid equilibria (LLE) were experimentally determined at T = 298.15 K and atmospheric pressure. The LLE data were correlated with the nonrandom two-liquid model, and the parameters were fitted. The separation capabilities of the ILs were evaluated in terms of the benzene distribution coefficient and solvent selectivity. The effect of the IL structure on the separation was explained based on a well-founded physical model, COSMO-RS. Finally, the extraction processes were defined, and the operation parameters were analyzed. It shows that the ILs studied are suitable solvents for the extractive separation of benzene and cyclohexane, and their separation efficiency can be generally ranked as [Bmim][BF ₄] > [Bpy][BF ₄] > [Bmim][SCN]. The extraction process for a feed with 15 mol % benzene was optimized. High product purity (cyclohexane 0.997) and high recovery efficiency (cyclohexane 96.9% and benzene 98.1%) can be reached. © 2012 American Chemical Society.

Laterality as an indicator of emotional stress in ewes and lambs during a separation test

We assessed motor laterality in sheep to explore species-specific brain hemi-field dominance and how this could be affected by genetic or developmental factors. Further, we investigated whether directionality and strength of laterality could be linked to emotional stress in ewes and their lambs during partial separation. Forty-three ewes and their singleton lambs were scored on the (left/right) direction of turn in a y-maze to rejoin a conspecific (laterality test). Further, their behavioural response (i.e. time spent near the fence, vocalisations, and activity level) during forced separation by an open-mesh fence was assessed (separation test). Individual laterality was recorded for 44.2 % ewes (significant right bias) and 81.4 % lambs (equally biased to the left and the right). There was no significant association in side bias between dams and offspring. The Chi-squared test revealed a significant population bias for both groups (p < 0.05). Evolutionary adaptive strategies or stimuli-related visual laterality may provide explanation for this decision-making process. Absolute strength of laterality (irrespective of side) was high (Kolmogorov–Smirnov test, dams: D = 0.2; p < 0.001; lambs: D = 0.36, p < 0.0001). The Wilcoxon test showed that lateralised lambs and dams spent significantly more time near each other during separation than non-lateralised animals (p < 0.05), and that lateralised dams were also more active than non-lateralised ones. Arguably, the lateralised animals showed a greater attraction to their pair because they were more disturbed and thus required greater reassurance. The data show that measures of laterality offer a potential novel non-invasive indicator of separation stress.