Theory and use of the pseudophase model in gas-liquid chromatographic enantiomeric separations

The theory and use of the "three-phase" model in enantioselective gas-liquid chromatography utilizing a methylated cyclodextrin/polysiloxane stationary phase is presented for the first time. Equations are derived that account for all three partition equilibria in the system, including partitioning between the gas mobile phase and both stationary-phase components and the analyte equilibrium between the polysiloxane and cyclodextrin pseudophase. The separation of the retention contributions from the achiral and chiral parts of the stationary phase can be easily accomplished. Also, it allows the direct examination of the two contributions to enantioselctivity, i.e., that which occurs completely in the liquid stationary phase versus the direct transfer of the chiral analyte in the gas phase to the dissolved chiral selector. Six compounds were studied to verify the model: 1-phenylethanol, alpha-ionone, 3-methyl-1-indanone, o-(chloromethyl)phenyl sulfoxide, o-(bromomethyl)phenyl sulfoxide, and ethyl p-tolylsulfonate. Generally, the cyclodextrin component of the stationary phase contributes to retention more than the bulk liquid polysiloxane. This may be an important requirement for effective GC chiral stationary phases. In addition, the roles of enthalpy and entropy toward enantiorecognition by this stationary phase were examined. While enantiomeric differences in both enthalpy and entropy provide chiral discrimination, the contribution of entropy appears to be more significant in this regard. The three-phase model may be applied to any gas-liquid chromatography stationary phase involving a pseudophase.     

Identification of ritual blood in African artifacts using TOF-SIMS and synchrotron radiation microspectroscopies

A new protocol is implemented to demonstrate the presence of blood in the patina of African art objects from Mali. Divided into three steps, the protocol first consists in demonstrating the presence of proteins and localizing them in the sample's cross sections using time-of-flight secondary ion mass spectrometry (TOF-SIMS) and synchrotron-based infrared microspectrometry (microFT-IR). In a second time, TOF-SIMS is used to investigate heme, which is a blood marker. If heme is missing, which could mean that it is too degraded to be detected, X-ray microfluorescence (microXRF) and X-ray absorption near-edge microspectroscopy (microXANES) are used to prove the presence of iron in the protein area and to get a fingerprint of its chemical environment. This permits us thus to demonstrate that iron is indeed linked with proteins and not with mineral phases of the sample. Coupled with the ritual context of the objects, this constitutes a proof of the use of blood. Thanks to this protocol, which has the major advantage of avoiding false positive results, the presence of blood has been demonstrated in seven out of the eight studied samples.     

Seeing is believing? When scanning electron microscopy (SEM) meets clinical dentistry: The replica technique.

In restorative dentistry, the in situ replication of intra‐oral situations, is based on a non‐invasive and non‐destructive scanning electron microscopy (SEM) evaluation method. The technique is suitable for investigation restorative materials and dental hard‐ and soft‐tissues, and its interfaces. Surface characteristics, integrity of interfaces (margins), or fracture analysis (chipping, cracks, etc.) with reliable resolution and under high magnification (from ×50 to ×5,000). Overall the current study aims to share detailed and reproducible information about the replica technique. Specific goals are: (a) to describe detailed each step involved in producing a replica of an intra‐oral situation, (b) to validate an integrated workflow based on a rational sequence from visual examination, to macrophotography and SEM analysis using the replica technique; (c) to present three clinical cases documented using the technique. A compilation of three clinical situations/cases were analyzed here by means the replica technique showing a wide range of possibilities that can be reached and explored with the described technique. This guidance document will contribute to a more accurate use of the replica technique and help researchers and clinicians to understand and identify issues related to restorative procedures under high magnification.     

New insights into the morphological stability of eutectic and peritectic coupled growth

Both eutectic and peritectic alloys exhibit three-phase equilibria and are used in diverse practical applications ranging from casting and welding to growing superconducting crystals. In-situ composites formed by the diffusively coupled growth of two solid phases are ubiquitous in eutectic solidification. This growth, however, is generally only stable over a finite range of eutectic spacing. The addition of a dilute ternary impurity can destabilize the interface and produce coarse two-phase cellular structures. Whether coupled growth is theoretically possible in peritectic alloys has been a question for over 40 years. This article reviews the current status of phase-field modeling of polyphase solidification in eutectic and peritectic alloys. Also discussed are new findings from both simulations and experiments that shed new light on the similarities and differences between the morphological stability of eutectic and peritectic coupled growth. For more information, contact Alain Karma, Northeastern University, Physics Department and Center for Interdisciplinary Research on Complex Systems, Boston, MA 02115; e-mail a.karma@neu.edu.     

Use of artificial intelligence in analytical systems for the clinical laboratory

The incorporation of information-processing technology into analytical systems in the form of standard computing software has recently been advanced by the introduction of artificial intelligence (AI), both as expert systems and as neural networks.This paper considers the role of software in system operation, control and automation, and attempts to define intelligence. AI is characterized by its ability to deal with incomplete and imprecise information and to accumulate knowledge. Expert systems, building on standard computing techniques, depend heavily on the domain experts and knowledge engineers that have programmed them to represent the real world. Neural networks are intended to emulate the pattern-recognition and parallel processing capabilities of the human brain and are taught rather than programmed. The future may lie in a combination of the recognition ability of the neural network and the rationalization capability of the expert system.In the second part of the paper, examples are given of applications of AI in stand-alone systems for knowledge engineering and medical diagnosis and in embedded systems for failure detection, image analysis, user interfacing, natural language processing, robotics and machine learning, as related to clinical laboratories.It is concluded that AI constitutes a collective form of intellectual propery, and that there is a need for better documentation, evaluation and regulation of the systems already being used in clinical laboratories.     

Non-contact handling in microassembly: Acoustical levitation

Microassembly is currently of the utmost importance in industry. Nevertheless, the classical assembly processes are no longer usable for very small components, typically ranging from 10  m to 10 mm, since usually neglected surface forces disturb the handling task by inducing adhesion between the component and the gripper. A promising alternative to tackle surface forces consists in levitating the handled component. The various advantages of this contactless handling method are reviewed here and justify the choice of this approach. Consequently, the numerous physical principles suitable for contactless handling are briefly described together with their limitations. The evaluation shows that acoustic levitation is best fitted in the case of microassembly. A classification of literature applications is presented hereafter with special focus on acoustic levitation. Finally, the most common models of acoustical levitation are inspected in a general way. The described models come within the scope of non-linear acoustics.     

Les glissements de terrain du quartier Bélouizdad, Constantine, Algérie

In Constantine, Belouizdad district landslides are extensive (Fig. 1). They occur along a hillside largely urbanized, and cover over 30 hectares. Dozens of houses were destroyed. The formations raised by these movements correspond to the alternating of thick Miocene clays and conglomerates. These contain several aquifers. The study of these landslides is conducted on the basis of recognition by deep boreholes equipped with piezometers and inclinometers. The inclinometric measurements have revealed failure surfaces sometimes deep (20 to 30 m) and north displacement, towards the Rhumel wadi. The use of a stability calculation software “Talren” shows on the one hand, the high sensitivity of unstable Miocene formations in the presence of water and on the other hand, a significant revival of the safety factor by reducing the pore pressure. The recommended solutions are therefore a lowering of underground water levels. Two techniques are recommended : deep drainage trench or galleries combined with radiating drainage holes.     

Reactive and non-reactive transport modelling in partially water saturated argillaceous porous media around the ventilation experiment, Mont Terri

At Mont Terri Underground Research Laboratory (URL) Switzerland, a specific experiment has been performed in a tunnel, in order to investigate the hydro-mechano-chemical (HMC) perturbations induced in the argillaceous formation by forced ventilation. This experiment has been selected in the international project DECOVALEX to be used for process model development and validation. The numerical simulation of the geochemical response to the ventilation experiment (VE) is the object of the present paper, focusing on the transport of chloride as a conservative species and sulphate as a reactive species. Utilising the validated hydro-mechanical (HM) results from earlier steps of the DECOVALEX task, reactive and non-reactive transport models, incorporating the current understanding of the geochemistry at the site, were successfully constructed for the whole experimental period. The associated parametric and process uncertainty analyses clearly demonstrate that the basic HM understanding must be sound. However, to demonstrate this degree of robustness, the explicit inclusion of process representations of water desaturation, liquid vaporisation, species exclusion porosity, and redox processes, is required.     

Beurteilung bestehender Stahltragwerke: Empfehlungen zur Abschätzung der Restnutzungsdauer

Assessment of existing steel structures: recommendations for estimation of remaining fatigue life. The growing importance of sustainability affects new markets for the construction industry; the rehabilitation and refurbishment of existing buildings and civil engineering works is getting more and more into the focus of construction activities. This also applies to bridges as well where the quality management comprising the full life of a bridge has a long tradition. For bridges in particular the enormous increase of freight‐volume on roads and rails and the growing age of the bridges cause the question, whether the existing structures are still fit for use and whether or not they can be retrofitted and if so how that could be done. For decision making concerning measures for maintenance and refurbishment of a bridge or its substitution by a new bridge the value of the residual service life is very important. Therefore the bridge authorities have been cooperating for a long time to develop appropriate methods for determining the residual safety and service life of existing bridges. Also the International Technical‐Scientific Organisations as the ECCS and fip as well as Standard Organisations as ISO and CEN have cared for an international exchange of views and the harmonisation of methods. For steel bridges in particular the Technical Committee 6 – Fatigue – of the ECCS has taken over the task to develop a technical guidance for the assessment of existing steel bridges on the grounds of national experiences and the present state of the art [1]. This guidance has been prepared to serve as a basis for CEN/TC 250 – the CEN‐Technical Committee responsible for the structural Eurocodes – for future further development of these Eurocodes to include the assessment and retrofitting of existing structures. The result of the development of ECCS‐TC 6 is a technical‐scientific report which has been published by the Commission of the EU (DG‐Research – Joint Research Centre – JRC) in the frame of a cooperation agreement between the JRC and the ECCS. This report may be used as a technical recommendation as long as the revision of the Eurocodes has not been carried out. This contribution gives the main information from the JRC‐ECCS‐report [1], that can be downloaded free of charge from the e‐bookshop of the Commission.