Background and line interference corrections in quantitative GD-OES – New approaches to an old problem

The origin of radiative background in GD-OES is discussed, in connection with the problem of multi-matrix measurements in depth profile analysis. Backed by some experimental evidence in the form of line scans, it is argued that line emission from sample material and the plasma gas (Ar) make up the dominating contributions to the radiative background. The contribution from Ar, in this work termed Matrix-independent Background (MIB), is investigated in more detail. It is shown that, at constant voltage and current, the Ar emission intensity is nearly constant and independent of the pressure, but somewhat matrix-dependent. It is suggested that the MIB can be expressed as a linear function of the intensity of an Ar reference line. This idea is tested experimentally by making intensity measurements on a large set of calibration standards of varying composition. The results are fitted to a calibration function which allows optional definitions of the MIB. It is shown that with a MIB defined as a linear function of the Ar intensity, the different contributions to the spectral background can be more accurately determined than with the MIB defined as a constant.     

Quantitative depth profiling in glow discharge spectroscopies – A new deconvolution technique to separate effects of an uneven erosion crater shape

An algorithm is presented as a concept for the quantification in direct current and radiofrequency glow discharge (GD) modes for GD optical emission spectroscopy. The algorithm is divided into excitation and sputtering part and thus it is possible to distinguish between the different excitation processes and to consider equivalent sputtering crater formations in both modes. Intensity-time profiles are affected corresponding to the method by several effects. One important effect is that sputtering occurs at a single time in different depths because of curved crater bottoms, this is usually called crater effect. The main purpose is to introduce an iterative deconvolution technique which for the quantification numerically takes into account the curved sputtering crater bottom. Input data for the deconvolution technique are the calibrated mass-time profile, the partial densities of the sample constituents and the measured final shape of the sputtering crater. Using a relatively simple model for ion sputtering the deconvolution technique improves iteratively the calculated layer structure by means of information on crater formation. The mathematical handling is illustrated for the quantification of a depth profile of a multilayer sample of ten 100 nm layers. The resulting concentration-depth profile reflects excellently the real elemental distribution of the multilayer system.     

Photocontrolled Release of Chemicals from Nano‐ and Microparticle Containers

A benzoin‐derived diol linker was synthesized and used to generate biocompatible polyesters that can be fully decomposed on demand upon UV irradiation. Extensive structural optimization of the linker unit was performed to enable the defined encapsulation of diverse organic compounds in the polymeric structures and allow for a well‐controllable polymer cleavage process. Selective tracking of the release kinetics of encapsulated model compounds from the polymeric nano‐ and microparticle containers was performed by confocal laser scanning microscopy in a proof‐of‐principle study. The physicochemical properties of the incorporated and released model compounds ranged from fully hydrophilic to fully hydrophobic. The demonstrated biocompatibility of the utilized polyesters and degradation products enables their use in advanced applications, for example, for the smart packaging of UV‐sensitive pharmaceuticals, nutritional components, or even in the area of spatially selective self‐healing processes.     

Catenation and Aggregation of Multi‐Cavity Coordination Cages

A series of metal‐mediated cages, having multiple cavities, was synthesized from Pd^II cations and tris‐ or tetrakis‐monodentate bridging ligands and characterized by NMR spectroscopy, mass spectrometry, and X‐ray methods. The peanut‐shaped [Pd₃L¹₄] cage deriving from the tris‐monodentate ligand L¹ could be quantitatively converted into its interpenetrated [5Cl@Pd₆L¹₈] dimer featuring a linear {[Pd‐Cl‐]₅Pd} stack as an unprecedented structural motif upon addition of chloride anions. Small‐angle neutron scattering (SANS) experiments showed that the cigar‐shaped assembly with a length of 3.7 nm aggregates into mono‐layered discs of 14 nm diameter via solvophobic interactions between the hexyl sidechains. The hepta‐cationic [5Cl@Pd₆L¹₈] cage was found to interact with polyanionic oligonucleotide double‐strands under dissolution of the aggregates in water, rendering the compound class interesting for applications based on non‐covalent DNA binding.     

Degradation of azithromycin using Ti/RuO<Subscript>2</Subscript> anode as catalyst followed by DPV,HPLC–UV and MS analysis

The electrodegradation of azithromycin was studied by its indirect oxidation using dimensionally stable Ti/RuO₂ anode as catalyst in the electrolyte containing methanol, 0.05 M NaHCO₃, sodium chloride and deionized water. The optimal conditions for galvanostatic electrodegradation for the azithromycin concentration of 0.472 mg cm^?3 were found to be NaCl concentration of 7 mg cm^?3 and the applied current of 300 mA. The differential pulse voltammetry using glassy carbon electrode was performed for the first time in the above-mentioned content of electrolyte for the nine concentration of azithromycin (0.075–0.675 mg cm^?3) giving the limits of azithromycin detection and of quantification as: LOD 0.044 mg cm^?3 and LOQ 0.145 mg cm^?3. The calibration curve was constructed enabling the electrolyte analysis during its electrodegradation process. The electrolyte was analyzed by high-performance liquid chromatography and electrospray ionization time-of-flight mass spectrometry. The electrooxidation products were identified and after 180 min there was no azithromycin in the electrolyte while TOC analysis showed that 79% of azithromycin was mineralized. The proposed degradation scheme is presented.     

Determination of Immunosuppressive Pharmaceuticals in Whole Blood Following Kidney Transplantation by High-performance Liquid Chromatography–Tandem Mass Spectrometry

Cyclosporine, tacrolimus, sirolimus, and everolimus are commonly used immunosuppressants following organ transplantation. Their monitoring is used to determine the optimal dose for therapeutic effectiveness and minimize toxicity. High-performance liquid chromatographic–tandem mass spectrometry with positive electrospray ionization and multiple reaction monitoring mode was validated for the determination of cyclosporine A, tacrolimus, sirolimus, and everolimus in whole blood. A C18 analytical column was employed with a gradient elution of pH 4.0 aqueous 10?mmol/L ammonium acetate and acetonitrile. For the pretreatment of whole blood, simple protein precipitation was used with methanol:zinc sulfate. The calibration curves were linear from 20.0 to 1000?ng/mL for cyclosporine A, 1.0 to 50?ng/mL for tacrolimus and sirolimus, and 1.0 to 30?ng/mL for everolimus. The intra-assay precision and inter-assay precision were less than 15%. The method provides reliable and reproducible results according to the linearity, precision, accuracy, recovery, and matrix effects. The method has been introduced to routine clinical practice in Slovakia for the determination of immunosuppressants in patients after kidney transplantation.     

Thickness difference induced pore structure variations in cellulosic separators for lithium-ion batteries

The pore structure of the separator is crucial to the performance of a lithium-battery as it affects the cell resistance. Herein, a straightforward approach to vary the pore structure of Cladophora cellulose (CC) separators is presented. It is demonstrated that the pore size and porosity of the CC separator can be increased merely by decreasing the thickness of the CC separator by using less CC in the manufacturing of the separator. As the pore size and porosity of the CC separator are increased, the mass transport through the separator is increased which decreases the electrolyte resistance in the pores of the separator. This enhances the battery performance, particularly at higher cycling rates, as is demonstrated for LiFePO₄/Li half-cells. A specific capacity of around 100 mAh g^?1 was hence obtained at a cycling rate of 2 C with a 10 µm thick CC separator while specific capacities of 40 and close to 0 mAh g^?1 were obtained for separators with thicknesses of 20 and 40 µm, respectively. As the results also showed that a higher ionic conductivity was obtained for the 10 µm thick CC separator than for the 20 and 40 µm thick CC separators, it is clear that the different pore structure of the separators was an important factor affecting the battery performance in addition to the separator thickness. The present straightforward, yet efficient, strategy for altering the pore structure hence holds significant promise for the manufacturing of separators with improved performance, as well as for fundamental studies of the influence of the properties of the separator on the performance of lithium-ion cells.     

A High‐Quality Professional Development for Teachers of Grades 3–6 for Implementing Engineering into Classrooms

With the increasing emphasis on integrating engineering into K‐12 classrooms to help meet the needs of our complex and multidisciplinary society, there is an urgent need to investigate teachers' engineering‐focused professional development experiences as they relate to teacher learning, implementation, and student achievement. This study addresses this need by examining the effects of a professional development program focused on engineering integration, and how teachers chose to implement engineering in their classrooms as a result of the professional development. 198 teachers in grades 3–6 from 43 schools in 17 districts participated in a yearlong professional development program designed to help integrate the new state science standards, with a focus on engineering, into their teaching. Posters including lesson plans and student artifacts were used to assess teachers' engineering practices and the implementation in their classrooms. Results indicated that the majority of the teachers who participated in the professional development were able to effectively implement engineering design lessons in their classrooms suggesting that the teachers' success in implementing engineering lessons in their classroom was closely related to the structure of the professional development program.     

Clique-cutsets beyond chordal graphs

Truemper configurations (thetas, pyramids, prisms, and wheels) have played an important role in the study of complex hereditary graph classes (eg, the class of perfect graphs and the class of even-hole-free graphs), appearing both as excluded configurations, and as configurations around which graphs can be decomposed. In this paper, we study the structure of graphs that contain (as induced subgraphs) no Truemper configurations other than (possibly) universal wheels and twin wheels. We also study several subclasses of this class. We use our structural results to analyze the complexity of the recognition, maximum weight clique, maximum weight stable set, and optimal vertex coloring problems for these classes. Furthermore, we obtain polynomial -bounding functions for these classes.