Improving peak shapes with counter gradients in two-dimensional high performance liquid chromatography

To achieve the greatest peak capacity in two-dimensional high performance liquid chromatography (2D-HPLC) a gradient should be operated in both separation dimensions. However, it is known that when an injection solvent that is stronger than the initial mobile phase composition is deleterious to peak performance, thus causing problems when cutting a portion from one gradient into another. This was overcome when coupling hydrophilic interaction with reversed phase chromatography by introducing a counter gradient that changed the solvent strength of the second dimension injection. It was found that an injection solvent composition of 20% acetonitrile in water gave acceptable results in one-dimensional simulations with an initial composition of 5% acetonitrile. When this was transferred to a 2D-HPLC separation of standards it was found that a marked improvement in peak shape was gained for the moderately retained analytes (phenol and dimethyl phthalate), some improvement for the weakly retained caffeine and very little change for the strongly retained n-propylbenzene and anthracene which already displayed good chromatographic profiles. This effect was transferred when applied to a 2D-HPLC separation of a coffee extract where the indecipherable retention profile was transformed to a successful application multidimensional chromatography with peaks occupying 71% of the separation space according to the geometric approach to factor analysis.

Counter-terrorism and (in)security : Fallout from the Bali bombing

In the wake of the Bali bombing the Australian government has proposed a number of national security measures that pose a real danger to human security in Australia and the region. These measures include renewed and increased military and intelligence exchanges with Indonesia, and laws that allow the Australian Security Intelligence Organization (ASIO) to detain people without charge or even suspicion in order to gather intelligence. In less emotional times these initiatives would be rejected as contrary to human rights concerns and Australia’s democratic traditions, which include the rule of law and due process protections. In the current climate, however, human rights and civil liberties are apt to be portrayed as unaffordable luxuries.

Effects of variation in modulator temperature during cryogenic modulation in comprehensive two-dimensional gas chromatography

Many modulation systems in comprehensive 2D GC (GC×GC) are based on cryogenic methods. High trapping temperatures in these systems can result in ineffective trapping of the more volatile compounds, whilst temperatures that are too low can prevent efficient remobilisation of some compounds. To better understand the trapping and release of compounds over a wide range of volatilities, we have investigated a number of different constant temperature modulator settings, and have also examined a constant temperature differential between the cryo-trap and the chromatographic oven. These investigations have led us to modify the temperature regulation capabilities of the longitudinally modulated cryogenic system (LMCS). In contrast to the current system, where the user sets a constant temperature for the cooling chamber, the user now sets the temperature difference between the cryo-trap and the chromatographic oven. In this configuration, the cooling chamber temperature increases during the chromatographic run, tracking the oven temperature ramp. This produces more efficient, volatility-dependent modulation, and increases the range of volatile compounds that can be analysed under optimal trap-and-release conditions within a single analytical run. This system also reduces cryogenic fluid consumption.

Phenyl-type and C1 stationary phases for environmentally friendlier chromatography

C1 and phenyl-type stationary phases were assessed in terms of their environmental impact on separations using as test solutes polycyclic aromatic hydrocarbons. Methanol (MeOH) and acetonitrile (ACN) mobile-phase gradients were employed. These stationary phases were examined to determine if different physical and chemical properties possessed by these surfaces decreased the organic solvent consumption, and yet maintained peak capacity. The cumulative energy demand (CED) was used to gauge the environmental impact of the separations. The separation of the polycyclic aromatic hydrocarbon test mixture using current methodologies (i.e. a C18/ACN combination) had a CED of 1.13 MJ-eq, and a peak capacity of 27 peaks (resolving 7 of 12 peak pairs with R_s>1). In comparison, a butyl phenyl stationary phase with a methanol mobile phase had a peak capacity of 26, but with a CED of 0.670 MJ-eq. Monolithic columns containing C18 and C1 phases were also tested. A monolithic C18 column with MeOH had the lowest CED at 0.675 MJ-eq, a peak capacity of 28 peaks and good resolving power (resolving ten peak pairs with R_s>1), suggesting that this is a viable option with respect to reducing environmental impact for these types of analyses.

Next generation robotic counter IED technology : A step change in capability

Improvised Explosive Devices (IEDs) are reported as the number one cause of injury and death for allied troops in the current theater of operation. Deakin University’s Centre for Intelligent Systems Research (CISR) is working on next-generation technology to combat the threat. In 2006 CISR was awarded funding through the Capability and Technology Demonstrator (CTD) Program managed by the Australian Defence Force. The objective was to investigate the use of haptics or force feedback technology for Counter-IED (CIED) tasks. Over the past six years, engineers from CISR have worked alongside Defence stakeholders to develop a series of robotic platforms designed to immerse a soldier in the remote environment. Utilising a natural user interface, haptic force feedback and stereovision, the technology has undergone initial trials in Sydney, Canberra, Woomera and at the CISR testing facility in Geelong, Australia. The technology has proved popular among operators allowing them increased fidelity and manipulation speed while significantly reducing required training. CISR has a history of rapidly delivering technology to meet the needs of police and law enforcement in Australia. The OzBot™ series of robots developed in conjunction with the Victorian Police is currently in service and used extensively for hostage negotiation and first responder roles. The CISR robotics group works on technologies that reduce operator fatigue, minimise training liability and maintenance. Over 55 engineers develop simulation environments for increased training availability and continuous improvement to the current range of mobile platforms, including communications range, payload, manipulator reach and capability. This paper describes a number of the technologies, methods and systems developed by CISR for IED neutralisation, with the aim to increasing military awareness of Australian capability.

Doing the counter-regulation shuffle: the importance of flexibility and hunger for predicting food consumption following a preload

Objectives
This study utilised the preload paradigm to evaluate whether trait-like dieting attitudes and behaviours (dietary restraint and flexibility in dieting rules) and context-specific factors (negative mood and hunger) predict food consumption among male and female participants.
Methods
Following a high calorie preload, 79 participants aged 18–40 completed a deceptive taste test in which they were encouraged to eat as much of the taste test foods as desired, and this ad libitum intake was measured.
Results
Although each predictor (except negative mood) predicted consumption when tested individually, regression analyses revealed that dieting flexibility and current hunger were the strongest unique predictors of intake. Mood failed to directly predict food consumption, nor did it moderate the relationship between restraint and food intake.ConclusionCollectively, findings suggest that emphasis on dietary restraint in preload studies may be misplaced, as other proximal and stable factors may better predict food consumption.