New avenue for mid-UV-range detection of underivatized carbohydrates and amino acids in capillary electrophoresis

Capillary electrophoresis (CE) appeared as an interesting alternative to chromatographic methods for carbohydrate analysis, but it can be difficult to implement, because of the lack of easily ionizable functions and chromophore groups. Recently, a promising method was proposed by Rovio et al. for the CE separation under extremely high alkaline conditions of neutral carbohydrates under their alcoholate form and their direct UV detection [Rovio et al. Electrophoresis 2007, 28, 3129-3135; and Rovio et al. J. Chromatogr. A 2008, 1185, 139-144], which is claimed to be due to the absorption of enediolate at 270 nm. Even so, most of the detected compounds in Rovio's paper (for example, sucrose) cannot give such enediolate, lacking a carbonyl group. In this work, a deeper insight was paid to the understanding of detection mechanism. In effect, unusual detection phenomena were observed in comparing reducing and nonreducing carbohydrate behaviors, which pointed to the existence of photochemical reactions in the detection window. A more systematic study of the influence of many parameters (carbohydrate nature, electrolyte pH, residence time in the detection window, and capillary diameter) was undertaken. In addition to this, most of this work was performed under cathodic (reversed) electro-osmotic flow conditions (using Polybrene-modified capillaries), to obtain much faster separations than under Rovio's conditions. This study also opens up new avenues for the detection in mid-UV range of non-UV-absorbing compounds bearing reducing moieties, such as amino acids.     

Compound-specific chlorine isotope analysis: a comparison of gas chromatography/isotope ratio mass spectrometry and gas chromatography/quadrupole mass spectrometry methods in an interlaboratory study

Chlorine isotope analysis of chlorinated hydrocarbons like trichloroethylene (TCE) is of emerging demand because these species are important environmental pollutants. Continuous flow analysis of noncombusted TCE molecules, either by gas chromatography/isotope ratio mass spectrometry (GC/IRMS) or by GC/quadrupole mass spectrometry (GC/qMS), was recently brought forward as innovative analytical solution. Despite early implementations, a benchmark for routine applications has been missing. This study systematically compared the performance of GC/qMS versus GC/IRMS in six laboratories involving eight different instruments (GC/IRMS, Isoprime and Thermo MAT-253; GC/qMS, Agilent 5973N, two Agilent 5975C, two Thermo DSQII, and one Thermo DSQI). Calibrations of (37)Cl/(35)Cl instrument data against the international SMOC scale (Standard Mean Ocean Chloride) deviated between instruments and over time. Therefore, at least two calibration standards are required to obtain true differences between samples. Amount dependency of δ(37)Cl was pronounced for some instruments, but could be eliminated by corrections, or by adjusting amplitudes of standards and samples. Precision decreased in the order GC/IRMS (1σ ≈ 0.1‰), to GC/qMS (1σ ≈ 0.2-0.5‰ for Agilent GC/qMS and 1σ ≈ 0.2-0.9‰ for Thermo GC/qMS). Nonetheless, δ(37)Cl values between laboratories showed good agreement when the same external standards were used. These results lend confidence to the methods and may serve as a benchmark for future applications.     

Zirconium oxide nanotube surface prompts increased osteoblast functionality and mineralization

Electrochemical formation of tunable nanoscale oxide layers on biomedical metallic surfaces has recently drawn much attention in biomaterials research. In this study, we report on the cellular response to a unique vertically aligned, laterally spaced nanotube nanostructure made of zirconium oxide (ZrO₂) fabricated by anodization. The growth, morphology, and functionality of osteoblasts cultured on ZrO₂ nanotubes have been investigated. The initial adhesion and spreading was considerably improved on the nanotube surface as compared to a flat zirconium (Zr) surface without a nanostructure. The morphology of the adhered cells on the nanotube surface elicited a highly organized cytoskeleton with crisscross patterned actin, which was lacking on the flat Zr. Increased alkaline phosphatase activity levels and the formation of calcified extracellular matrix implied improved osteoblast functionality and mineralization on the nanotube substrate. This in vitro study suggests that the ZrO₂ nanotubes provided an enhanced osteoblast response and demonstrated their apparent role in providing a platform for bone growth.     

The cholesterol-lowering effect of guar gum is not the result of a simple diversion of bile acids toward fecal excretion

The effects of partially hydrolyzed, nonviscous, guar gum (PHGG) on cholesterol metabolism and digestive balance have been compared with those of native guar gum (GUAR) in rats adapted to 0.4% cholesterol diets. Both types of guar gum elicited acidic fermentations in the large intestine, but only GUAR effectively lowered plasma cholesterol (P<0.001), chiefly in the triglyceride-rich lipoprotein fraction. The biliary bile acid excretion was significantly enhanced in rats fed GUAR (P<0.05), as well as the intestinal and cecal bile acid pool (P<0.001). In rats fed GUAR and to a lesser extent in those fed PHGG, the fecal excretion of bile acids and neutral sterol was higher than in controls (P<0.01). The digestive balance (cholesterol intake-steroid excretion) was positive in control rats (+47 μmol/d), whereas it was negative in rats fed GUAR (−20 μmol/d), which could involve a higher rate of endogenous cholesterol synthesis. In rats fed PHGG, the steroid balance remained slightly positive. Liver 3-hydroxy-3-methylglutaryl-CoA (HMG-CoA) reductase activity was very low (22 pmol/min/mg protein), owing to cholesterol supplementation, in control rats or in rats fed PHGG, whereas it was markedly higher (+463%) in rats fed GUAR. In conclusion, even if PHGG does alter some parameters of the enterohepatic cycle of cholesterol and bile acids, its effects are not sufficient to elicit a significant cholesterol-lowering effect. The intestinal (ileal or cecal) reabsorption of bile acids was not reduced, but rather increased, by GUAR; nevertheless the intestinal capacities of reabsorption were overwhelmed by the enlargement of the digestive pool of bile acids. In the present model, induction of HMG-CoA reductase probably takes place in the presence of elevated portal bile acid concentrations.     

CFD in der chemischen Verfahrenstechnik aus industrieller Sicht

Computational fluid dynamics (CFD) is increasingly becoming established as a tool for analysis and design in the chemical industry. Several projects from various areas are introduced as examples of CFD projects from the perspective of the CFD user in chemical industry. The areas chosen are based on those in a process chain: transportation, mixing, reaction, and separation of materials. The most important steps and decisions in the use of CFD are presented from the perspective of the process engineer. This paper attempts to convey an appreciation for the possibilities and opportunities, but also for the limits of computational fluid dynamics.     

Infrared study of nitrogen monoxide adsorption on palladium ion-exchanged ZSM-5 catalysts

The adsorption of NO at room temperature on a H-ZSM-5 catalyst exchanged with Pd(NH₃) ₄ ²⁺ complex and activated in oxygen at 773 K has been examined by FTIR spectroscopy. After the oxidizing treatment, the Pd tetrammine complex decomposed into Pd(II) ions and/or Pd(II) hydroxyl complexes dispersed in the zeolite channels. The subsequent adsorption of NO at room temperature led to the reduction of Pd(II) to Pd(I) entities, resulting in the formation and adsorption of NO₂ on H-ZSM-5. The Pd(I) entities were shown to adsorb NO and form mononitrosyl complexes dispersed in the zeolite porosity and characterized by a single infrared absorption band at 1881 cm^–1. The Pd(I) mononitrosyl complex was shown to reversibly coordinate water and NO₂ molecules. The resulting nitrosyl complex was characterized by a single NO vibration band at 1836 cm^–1.     

Benefit evaluation for off‐site production in construction

Evaluating to what extent a component or building system should be produced off‐site is inadequate within the industry. The potential benefits of off‐site production (OSP) are commonly cited when justifying an OSP approach, yet holistic and methodical assessments of the applicability and overall benefit of these solutions, to a particular project, have been found to be deficient. Common methods of evaluation simply take material, labour and transportation costs into account when comparing various options, often disregarding other cost‐related items such as site facilities, crane use and rectification of works. These cost factors are usually buried within the nebulous preliminaries figure, with little reference to the building approach taken. Further, softer issues such as health and safety, effects on management and process benefits are either implicit or disregarded within these comparison exercises. Yet it is demonstrated that these issues are some of the most significant benefits of OSP. A series of case studies demonstrated that evaluation focus is almost solely on direct material and labour costs of components, without explicit regard for the wider cost or soft issue implications of OSP on a project. The paper argues that until evaluation is more holistic and value‐based rather than cost‐based, OSP uptake in construction will be slow.     

A triple spin-labeling strategy coupled with DEER analysis to detect DNA modifications and enzymatic repair

In a spin: Spin-labeled oligonucleotides produced by click chemistry can be studied by EPR, by using a DEER sequence. This was used to test a complex triple-labeling strategy with damaged DNA. Extensive and accurate analysis of DNA structure and enzymatic repair processes were performed after digestion by EndoIV. Modified DNA structures and DNA-protein interactions can now be readily studied.