Diporphyrin tweezer for multichannel spectroscopic analysis of enantiomeric excess

Chiral 1,1’-binaphthyl-linked diporphyrin ‘tweezers’ (R)-1/(S)-1 and the corresponding zinc(II) complexes (R)-2/(S)-2 were prepared as chiral host molecules, and their utility for chiral analyses (especially enantiomeric excess (ee) determinations) were evaluated. Tris(1-n-dodecyl)porphyrins were used for the first time as the interacting units. Host capabilities of the diporphyrin tweezers were investigated by titrations with (R,R)- and (S,S)-cyclohexane-1,2-diamine (CHDA). The host molecules could be used as multichannel probes of ee by using UV-vis, circular dichroism (CD), fluorescence emission and ¹H nuclear magnetic resonance (¹H-NMR) methods. Chiral configurations could also be differentiated using CD or ¹H-NMR spectroscopy. All three optical techniques give good resolution of ee with reasonable sensitivity considering the low concentrations used (ca. 10⁻⁶ mol·L⁻¹). The ee determination of CHDA enantiomers using NMR spectroscopy is also possible because of the reasonably well separated resonances in the case of (R,R)- and (S,S)-CHDA. Non-metallated (R)-1/(S)-1 hosts could not be used to detect chiral information in a strongly acidic chiral guest. This work demonstrates the utility of 1,1’-binapthyl-linked chiral hosts for chiral analysis of ditopically interacting enantiomers.     

Hydration Kinetics and Phase Stability of Dicalcium Silicate Synthesized by the Pechini Process

Reactive dicalcium silicate (Ca₂SiO₄) has been synthesized by the Pechini process, and hydration kinetics studied. With increasing calcination temperature, the amorphous product first crystallizes to α'_L-phase and subsequently to the ß- and γ-phases. The specific surface area, ranging from 40 to 1 m²/g, strongly depends on the calcination temperature of 700°-1200°C for 1 h. Samples with a high surface area have a high water demand; a water/cement ratio >2.0 is required to produce formable pastes in some instances. Hydration kinetics are determined by XRD, ²⁹Si magic-angle spinning nuclear magnetic resonance (MAS NMR), and differential scanning calorimetry/thermogravimetry (DSG/TG). The hydration rate depends only on the surface area, not on the polymorph. Complete hydration occurs in as early as 7 d. Very little calcium hydroxide (Ca(OH)₂) is formed in the most reactive specimens (calcined at 700° and 800°C), which indicates the Ca/Si ratio in C-S-H gels is ∼2.0, but more Ca(OH)₂ forms from samples calcined at higher temperature. The silicate structure of the hydrated Ca₂SiO₄ pastes is investigated using ²⁹Si MAS NMR spectroscopy and trimethylsilylation analysis.     

Analysis of subcellular phosphatidyl choline in developing rabbit lung

Phosphatidyl choline is a major lung surfactant. Insufficient development of the surfactant in neonates is often associated with the Respiratory Distress Syndrome. The concentration and fatty acid composition of phosphatidyl choline have not been studied in the subcellular organelles of the developing lung. This study has investigated the development of the concentration and fatty acid composition of phosphatidyl choline in subcellular fractions of 28-day and 30-day fetal and maternal New Zealand rabbit lungs. The concentration of total phospholipids in lamellar bodies increased four to five fold from 28-day fetus to 30-day fetus which, in turn, was similar to the maternal level. Total phospholipid content increased only about 50% in mitochondria and microsomes. The percentage of phosphatidyl choline among total phospholipids in lamellar bodies increased successively from 60% at 28 days gestation to 84% at 30 days gestation and leveled at 84% in maternal lamellar bodies. Microsomal PC increased steadily from 52% in the 28-day fetus to 65% in the adult. Analysis of the fatty acid composition of phosphatidyl choline in lamellar bodies confirmed 16∶0 as the major fatty acid, and its content remained constant from 28 days gestation to adult. In contrast, the content of 16∶0 of the microsomal phosphatidyl choline decreased with increasing gestation. Changes of several unsaturated fatty acid components were observed in both lamellar bodies and microsomes in the developing lungs. Maturational development of phosphatidyl choline is reflected in an increase in the concentration of this surfactant, particularly in lamellar bodies, and possibly in remodeling of fatty acid composition in both lamellar bodies and microsomes.     

Acoustics impact on steam dryer induced by main steam line break in a boiling water reactor

In boiling water reactor (BWR) design, significant acoustic pressure loads impact the steam dryer hood as a result of the main steam line break outside containment (MSLB) event. When a main steam line breaks, it is assumed that the pipe instantaneously breaks completely open to the ambient environment (double-ended guillotine break). Due to the huge pressure difference between the inside of the reactor pressure vessel (RPV) and surrounding ambient environment, a shock wave will form at the break point and burst into the surrounding environment. At the same time, an expansion wave will travel upstream through the main steam line to the RPV, which results in a pressure reduction on the outside of the steam dryer hood. This expansion wave will create a substantial pressure difference between the two sides of the steam dryer hood with a resultant high stress on the hood. This differential pressure load is the acoustic load used in the structure design evaluations for this event. A key design basis requirement for the steam dryer is to maintain structural integrity during transient, and accident conditions. Demonstration that the steam dryers meet this design basis requires a calculation of the magnitude of the acoustic load on the steam dryer during a MSLB. In this study, computational fluid dynamics (CFD) is used as an alternate calculation method to investigate the phenomenon of MSLB. Transient simulations with fine time steps were carried out. The results show that CFD is a useful tool to provide additional information on the acoustic load as compared to the traditional methods. From the CFD results, the minimum pressure value and its distribution area at different flow times was identified. Through the modeling, an understanding of the detailed transient flow field, particularly the acoustic pressure field near the dryer hood during the MSLB was achieved.     

The Epidermal Growth Factor Receptor and Its Ligands in Cardiovascular Disease

The epidermal growth factor receptor (EGFR) family and its ligands serve as a switchboard for the regulation of multiple cellular processes. While it is clear that EGFR activity is essential for normal cardiac development, its function in the vasculature and its role in cardiovascular disease are only beginning to be elucidated. In the blood vessel, endothelial cells and smooth muscle cells are both a source and a target of EGF-like ligands. Activation of EGFR has been implicated in blood pressure regulation, endothelial dysfunction, neointimal hyperplasia, atherogenesis, and cardiac remodeling. Furthermore, increased circulating EGF-like ligands may mediate accelerated vascular disease associated with chronic inflammation. Although EGFR inhibitors are currently being used clinically for the treatment of cancer, additional studies are necessary to determine whether abrogation of EGFR signaling is a potential strategy for the treatment of cardiovascular disease.     

Static and dynamic heterogeneities in water

The thermodynamic behaviour of water seems to be related to static heterogeneities. These static heterogeneities are related to the local structure of water molecules and, when properly characterized, may offer an economical explanation of thermodynamic data. 'What matters' most in determining some of the unusual properties of liquid water may be the fact that the local geometry of the liquid molecules is not spherical or oblong, but rather tetrahedral. In respect to static heterogeneities, this local geometry is critical. The dynamic behaviour of water seems to be related to dynamic heterogeneities, which seem to explain the dynamics of supercooled liquid water well.     

Corrigendum of ‘A deterministic model for a repairable item inventory system with a finite repair rate’

The main purpose of this corrigendum is to indicate and rectify the same mistakes made by Schrady (1967 Schrady, D. A. 1967. “A Deterministic Inventory Model for Repairable Items.” Naval Research Logistics Quarterly 14: 391–398.[Crossref] , [Google Scholar]), Nahmias and Rivera (1979 Nahmias, S., and H. Rivera. 1979. “A Deterministic Model for a Repairable Item Inventory System with a Finite Repair Rate.” International Journal of Production Research 17: 215–221.[Taylor &; Francis Online], [Web of Science ®] , [Google Scholar]), and Teunter (2004 Teunter, R. H. 2004. “Lot-Sizing for Inventory Systems with Product Recovery.” Computers and Industrial Engineering 46: 431–441.[Crossref], [Web of Science ®] , [Google Scholar]) in the course of solving their respective models in order that subsequent researchers will not follow the same. To this end, we derive the corresponding correct global-optimal formulae for the substitution-policy model (1,?n), with infinite or finite recovery (or called repair) rate, using differential calculus, as well as providing a closed-form expression to identify the optimal positive integral value of n recovery set-ups. In addition, we also rectify the formulae and solution procedure for numerically solving the constrained non-linear programme.     

Temperature-insensitive polarimetric vibration sensor based on HiBi microstructured optical fiber

A new type of highly birefringent microstructured optical fiber has been tested for vibration measurements using a polarimetric technique. This technique takes advantage of the stress-induced phase shift between the two orthogonally polarized fiber eigenmodes. Comparison of three different fiber types shows that standard single-mode fibers do not provide stable measurements and that conventional polarization-maintaining fibers lead to a significant cross-sensitivity to temperature. However, for highly birefringent microstructured fibers specifically designed to provide a temperature-independent birefringence, our experiments show repeatable vibration measurements over a frequency range extending from 50?Hz to 1?kHz that are unaffected by temperature variations (up to 120?°C).     

Adaptive filtering of evoked potentials with radial-basis-function neural network prefilter

Evoked potentials (EPs) are time-varying signals typically buried in relatively large background noise. To extract the EP more effectively from noise, we had previously developed an approach using an adaptive signal enhancer (ASE) (Chen et al., 1995). ASE requires a proper reference input signal for its optimal performance. Ensemble- and moving window-averages were formerly used with good results. In this paper, we present a new method to provide even more effective reference inputs for the ASE. Specifically, a Gaussian radial basis function neural network (RBFNN) was used to preprocess raw EP signals before serving as the reference input. Since the RBFNN has built-in nonlinear activation functions that enable it to closely fit any function mapping, the output of RBFNN can effectively track the signal variations of EP. Results confirmed the superior performance of ASE with RBFNN over the previous method.