Stability testing in an integrated scheme

ISO Guide 35 deals with RM stability issues and scrutinizes the evaluation of stability testing results under the assumption that either there is no trend at all (a rather rare situation), or any observed deterministic change is insignificant and thus can be neglected. However, market demands for reliable reference materials are obviously not limited to stable or at least seemingly stable materials. In many analytical applications, analytes and measurands under consideration are known, or at least suspected, to be unstable on time scales that may vary widely from measurand to measurand. The Federal Institute for Materials Research and Testing (BAM) has developed (and successfully uses) an integrated approach in its certification practice. The approach is based on an initial stability study and subsequent post-certification monitoring. Data evaluation is model-based and takes advantage of all information collected in the stability testing scheme(s). It thus allows one to deal with any kind of instability observed, to assess limiting time intervals at any stress condition in the range tested, to estimate a final expiry date for materials with detected instabilities or the maximum admissible re-testing interval for seemingly stable materials, and to assess maximum admissible stress loads during delivery of the material to the customer. The article describes (and exemplifies) typical study layout, the model selection, and the integrated data assessment.     

Analytic calculation of scaling dimensions: Tricritical hard squares and critical hard hexagons

The finite-size corrections, central chargesc, and scaling dimensionsx of tricritical hard squares and critical hard hexagons are calculated analytically. This is achieved by solving the special functional equation or inversion identity satisfied by the commuting row transfer matrices of these lattice models at criticality. The results are expressed in terms of Rogers dilogarithms. For tricritical hard squares we obtainc=7/10,x=3/40, 1/5, 7/8, 6/5 and for hard hexagons we obtainc=4/5,x=2/15, 4/5, 17/15, 4/3, 9/5, in accord with the predictions of conformal and modular invariance.     

Chemical analysis of acidic silicon etch solutions: I. Titrimetric determination of HNO3, HF, and H2SiF6

The chemical etching of silicon using HF-HNO₃ mixtures is a widely used process in the processing of silicon wafers for microelectronic or photovoltaic applications. The control of the etch bath composition is the necessary condition for an effective bath utilization, for the replenishment of the consumed acids, and to maintain a certain etch rate. The present paper describes two methods for the total analysis of the individual etch bath constituents HF, HNO₃, and H₂SiF₆. Both methods start with an aqueous acid-base titration determining the total acid concentration and the concentration of H₂SiF₆. The first method is an acid-base titration using a 0.1 mol L⁻¹ methanolic solution of cyclohexylamine (CHA) as non-aqueous titrant to determine the content of nitric acid. Then, the amount of hydrofluoric acid is calculated from the difference between the total acid and nitric acid content. The second method is based on the determination of the total fluoride concentration using a fluoride ion-selective electrode (F-ISE). The content of hydrofluoric acid is obtained from the difference between the total fluoride content and the amount of fluoride bound as H₂SiF₆. The amount of nitric acid results finally calculated as difference to the total acid content.     

Intercalation of Dyes Containing SO3H Groups into Zn–Al Layered Double Hydroxide

The intercalates of Naphthol Yellow S, Tropaeolin 000, and Tropaeolin 00 were prepared by heating [Zn_0.67Al_0.33(OH)₂](CO₃)_0.165 · 0.5H₂O with acidic forms of the dye solutions in an open reaction vessel. The intercalates were characterized by chemical and thermal analysis, X-ray powder diffraction and UV–VIS spectroscopy. A possible arrangement of the dye molecules in the intercalates was suggested on the basis of their chemical compositions and interlayer distances, by taking into account van der Waals dimensions of the guest molecules and by assuming that the structure of the host layers is not changed during the intercalation process.     

Solution- and bound-state conformational study of N,N',N"-triacetyl chitotriose and other analogous potential inhibitors of hevamine: application of trNOESY and STD NMR spectroscopy

The solution-state conformations of N,N',N"-triacetyl chitotriose (1) and other potential chitinase inhibitors 2-4 were studied using a combination of NMR spectroscopy (NOESY) and molecular mechanics calculations. Determination solely of the global energy minimum conformation was found to be insufficient for an agreement with the NMR results. An appropriate consistency between the NMR experimental data and theoretical calculations was only reached by assessing the structures as population-weighted average conformers based on Boltzmann distributions derived from the calculated relative energies. Analogies, but also particular differences, between the synthetic compounds 2-4 and the naturally-occurring N,N',N"-triacetyl chitotriose were found. Furthermore, the conformation of compounds 1 and 2 when bound to hevamine was also studied using transferred NOESY experiments and the binding process was found to impart a level of conformational restriction on the ligands. The preferred conformation as determined for 1 in the bound state to hevamine belonged to one of the conformational families found for the compound when free in solution, although full characterisation of the bound-state conformations was impeded due to severe signal overlap. Saturation transfer difference NMR experiments were also employed to analyse the binding epitopes of the bound compounds. We thus determined that it is mainly the acetyl amido groups of the trisaccharide and the heterocyclic moiety which are in close contact with hevamine.     

Automated multiple-layer spotting for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry of synthetic polymers utilizing ink-jet printing technology

Recently, a new multiple-layer matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) sample spotting technique for poly(ethylene glycol), offering improved analysis possibilities, was described. In this contribution the application of ink-jet printing to automated, multiple-layer MALDI-TOFMS sample preparation of synthetic polymers is presented, allowing accurate deposition of matrix, additive and analyte solutions. The new sample preparation technique was evaluated for poly(ethylene glycol) as well as poly(methyl methacrylate) standards, and optimized settings for both synthetic polymers have been obtained.     

Intercalation of 1,2-Alkanediols into α-Zirconium Hydrogenphosphate

Intercalation compounds of α-Zr(HPO₄)₂ · H₂O with 1,2-alkanediols (from C3 to C16) have been prepared by replacing 1-propanol in α-Zr(HPO₄)₂ · 2C₃H₇OH with the desired 1,2-alkanediols by a treatment in a microwave field. It was found that the intercalates contain 1.5 molecules of diol per formula unit. The diol molecules are placed between the host layers in a bimolecular way with their aliphatic chains tilted at an angle of 51°. The diol molecules are anchored in the interlayer space by H-bonds. A mixed intercalate, containing 1,2-butanediol and 1,2-decanediol in a roughly equimolar ratio, is formed when the α-Zr(HPO₄)₂ · 2C₃H₇OH intercalate, suspended in a mixture of 1,2-butanediol and 1,2-decanediol, is exposed to microwave radiation. No new phase containing both types of the guest molecules was observed when the 1-propanol intercalate, suspended in a mixture of 1-propanol and 1,2-octanediol, is exposed to microwave radiation.