Selectivity in multicomponent analysis

Figures of merit for judging the selectivity of procedures for multicomponent analysis are compared with respect to their performance under different experimental conditions. The condition number of the calibration matrix is evaluated as being the most general selectivity measure. Practical selectivities based on the condition number are given for atomic and molecular spectroscopy and for electroanalytical methods. The most promising data reduction schemes, such as factor analysis or partial least squares in latent variables are discussed for systems with unselective sensors.     

Thermodynamics of lattice heteropolymers

We calculate thermodynamic quantities of hydrophobic-polar (HP) lattice proteins by means of a multicanonical chain-growth algorithm that connects the new variants of the Pruned-Enriched Rosenbluth Method and flat histogram sampling of the entire energy space. Since our method directly simulates the density of states, we obtain results for thermodynamic quantities of the system for all temperatures. In particular, this algorithm enables us to accurately simulate the usually difficult accessible low-temperature region. Therefore, it becomes possible to perform detailed analyses of the low-temperature transition between ground states and compact globules.     

Conformational transitions of nongrafted polymers near an absorbing substrate

We have performed multi-canonical chain-growth simulations of a polymer interacting with an adsorbing surface. The polymer, which is not explicitly anchored at the surface, experiences a hierarchy of phase transitions between conformations binding and nonbinding with the substrate. We discuss the phase diagram in the temperature-solubility plane and highlight the transition path through the free-energy landscape.     

GaAs/AlGaAs quantum wire lasers fabricated by cleaved edge overgrowth

We have used the molecular beam growth technique which we call "cleaved edge overgrowth" to fabricate quantum wire lasers, in which 1D quantum confinement is entirely defined by the growth process. The active region of our lasers consists of atomically precise quantum wires that form at the T-shaped intersections of 7 nm wide GaAs quantum wells grown along the [001] crystal axis and after an in situ cleave along the [110] crystal axis. The origin of the quantum mechanical bound state is the relaxation of quantum well confinement at this intersection. The high degree of structural perfection achievable in this way allows the observation of stimulated optical emission from the lowest exciton state in optically as well as in electrically pumped devices. The formation of a linear p-n junction in which the quantum wires are embedded is achieved by doping with Be and Si in the two orthogonal growth directions. Efficient current injection into the wires is demonstrated by the almost complete suppression of optical emission from the quantum well states as well as by threshold currents as low as 0.4 mA for uncoated devices at 1.7 K.     

An uncertainty budget for trace analysis by isotope-dilution ICP-MS with proper consideration of correlation

Isotope-dilution mass spectrometry (IDMS) is considered to be a method without significant correction factors. It is also believed that this method is well understood. But unfortunately a large number of different uncertainty budgets have been published that consider different correction factors. These differences lead to conflicting combined uncertainties especially in trace analysis. It is described how the known correction factors must be considered in the uncertainty budget of values determined by IDMS combined with ICP-MS (ICP-IDMS). The corrections applied are dead time, background, interference, mass discrimination, blank correction and air buoyancy.IDMS measurements consist always of a series of isotope abundance ratio measurements and can be done according to different measurement protocols. Because the measurement protocols of IDMS are often rather sophisticated, correlations of influence quantities are difficult to identify. Therefore the measurement protocol has to be carefully considered in the specification of the measurand and a strategy is presented to properly account for these correlations. This will be exemplified for the estimation of mass fractions of platinum group elements (PGEs) and Re in the geological reference material UB-N (from CRPG-CNRS, Nancy in France) with ICP-IDMS. The PGEs with more than one isotope and the element Re are measured with on-line cation-exchange chromatography coupled to a quadrupole ICP-MS. All contents are below 10 µg kg^–1. Only osmium is separated from the matrix by direct sparging of OsO₄ into the plasma. This leads to transient signals for all PGEs and Re. It is possible to estimate the combined uncertainties and keep them favourably small despite the low contents, the transient signals and the sophisticated correction model.     

Über Lösungs- und Verdünnungswärmen

Zusammenfassung Es werden Formeln für die Beziehungen zwischen den verschiedenen Lösungs- und Verdünnungswärmen gegeben, welche gestatten, sie aus den als Funktion der Wassermenge dargestellten totalen Lösungswärmen zu berechnen. Diese Funktionen können auch aus Lösungswärmen in Lösung und unter Mitbenützung von Verdünnungswärmen abgeleitet werden.Die Art der Berechnung und die erzielbare Genauigkeit (insbesondere für die infinitesimalen Lösungswärmen) werden an der Hand spezieller Interpolationsformeln und an einigen Zahlenbeispielen (Na₂CO₃, KClO₃, NaNO₃) erläutert.     

Speciation analysis of inorganic antimony in soil using HPLC-ID-ICP-MS

Speciation analysis of Sb(III) and Sb(V) in a soil sample was performed through extraction and on-line isotope dilution concentration determination after a chromatographic separation. The total Sb concentration found in a through traffic contaminated soil sample was (4.17 μg g⁻¹, 0.3 μg g⁻¹ SD, n=6). It was determined using ICP-MS after soil digestion using the sodium peroxide sintering method. The optimized extraction procedure for speciation analysis was carried out using 100 mmol L⁻¹ citric acid at pH 2.08 by applying an ultrasonic bath for 45 min at room temperature. The effects of citric acid concentration (0–500 mmol L⁻¹), pH (1–6), and temperature (30–60°C) on inorganic antimony species distribution in the examined sample were studied and optimized. The separation of Sb(III) and Sb(V) was achieved using an anion exchange column (PRP-X100) and 10 mmol L⁻¹ EDTA and 1 mmol L⁻¹ phthalic acid at pH 4.5 as a mobile phase. The eluent from the HPLC was mixed with an enriched (94.2%) ¹²³Sb spike solution that was pumped by a peristaltic pump with a constant flow rate (0.5 mL min⁻¹) in a three-way valve. The blend passed directly to the Conikal nebulizer of the ICP-MS. By using the above extraction procedure and methodology, 43.2% Sb(V) (2.9% RSD, n=3) and 6.0% Sb(III) (1.3% RSD, n=3) of total Sb found in the sample could be detected. The detection limits achieved by the proposed method were 20 ng L⁻¹ and 65 ng L⁻¹ for Sb(V) and Sb(III), respectively. The precision, evaluated by using RSD with 100 ng L⁻¹ calibration solutions, was 2.7% and 3.2% (n=6) for Sb(V) and Sb(III), respectively, in aqueous solutions.