Synthesis of organofunctional silanes with sterically hindered substituents at silicon atoms

Organofunctional silanes with more sterically hindered substituents at the silicon atom than the typical methoxy (ethoxy) group have lately been frequently used as silane coupling agents, in polymer coupling systems, sol‐gel processes and also as interpenetrating polymer network substrates. New and very efficient synthetic ways leading to organofunctional silanes of the above type with methacryl, amine, chloro and isocyanato functional groups are proposed here. Catalytic transesterification and/or alcoholysis of chloropropyltrialkoxysilanes followed by­nucleophilic substitution has been employed. Copyright © 2001 John Wiley & Sons, Ltd.     

Low-loss geodesic lens: Meridional profile and fabrication tolerances

The most recent formulation of the perfect geodesic lens problem is utilized to evaluate a novel solution. This solution describes a smooth geodesic depression profile with a finite value of its local curvature radius at the edge of the lens. This feature should minimize radiation and scattering losses by the guided modes that take place mainly at the lens boundary. The external rounded section of the proposed lens is described by a simple, explicit expression that considerably eases designing procedure. The presented lens is capable of perfect focusing once the theoretically prescribed ideal depression profile is accurately fabricated. For straightforward examination of the influence of technological grinding errors on the lens focal characteristics, a simple analytical method is proposed and investigated.     

Effect of crown-ether surfactants on flame atomic absorption and flame emission signals of some monovalent cations

Two surface-active and one surface-inactive 18-crown-6 derivatives were synthesized and evaluated for their abilities to enhance flame atomic absorption and flame emission signals of monovalent cations. Enhancement of potassium signals were noted for the surface-active compounds but not for the surface-inactive compound. The critical micelle concentration was determined and compared to the degree of enhancement. Surfactant-induced signal enhancements are not due to the slight or moderate decrease in the size of the aerosol first produced in the nebulizing chamber. Additional mechanistic considerations are discussed.     

The equipotential surfaces of cubic lattices

The areas of zero electrostatic potential within an array of electric charges in an ionic crystal can be represented as a zero equipotential surface (ZEPS), which separates space into domains of positive and negative potential. ZEPS are conventionally expressed in terms of nodal surfaces. We express the coordinates and charge distribution of several ZEPS in terms of the Jacobi theta functions, and provide their graphical visualisation.     

Preparation and characterization of 1,2,3‐triazole‐cured polymers from endcapped azides and alkynes

Fourteen commercial polyols have been characterized by GPC, NMR spectroscopy, and elemental analysis. From these, eight corresponding tosylates, six nitrate esters, seven mesylates, 13 alkynes, and 14 azides have been prepared and all these derivatives have been fully characterized. Five alkyne monomers and eight azide monomers were also prepared. Twelve alkynes and 13 azides (functionality 2–4) were combined in 1,3‐dipolar cycloaddition reactions under neat conditions to prepare triazole‐cured polymers, avoiding any heavy metal catalyst. Characterization by NMR spectroscopy, elemental analysis, and gel permeation chromatography indicated triazole polymers 14 , 22 , 23 , 28 , and 30 with degrees of polymerization of 17–28 to be the best candidates for future work. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 238–256, 2008     

Syntheses and reactions of terpene β-hydroxyselenides and β-hydroxydiselenides

A convenient method for the synthesis of optically active trans-hydroxyselenides and trans-hydroxydiselenides from the bicyclic terpene group based on the reactions of sodium selenide or sodium diselenide with cis- and trans-(+)-3-carane, trans-(+)-2-carane and (?)-β-pinane epoxides is described. The corresponding cis-hydroxy and cis-methoxydiselenides were obtained in the reaction of sodium diselenide with β-hydroxy- and β-methoxytosylates. The influence of a hydroxy group at the β-position on the diastereomeric ratio of the products of the asymmetric methoxyselenenylation of styrene has been established by composition of the products, crystal structure analyses, and theoretical calculations using a DFT method on the B3LYP level (6-311G(d)).     

Simultaneous confidence bands for the integrated hazard function

The construction of the simultaneous confidence bands for the integrated hazard function is considered. The Nelson–Aalen estimator is used. The simultaneous confidence bands based on bootstrap methods are presented. Four methods of construction of such confidence bands are proposed. The weird and conditional bootstrap methods are used for resampling. Simulations are made to compare the actual coverage probability of the bootstrap and the asymptotic simultaneous confidence bands. It is shown that the equal-tailed bootstrap confidence band has the coverage probability closest to the nominal one. We also present application of our confidence bands to the data regarding survival after heart transplant. This research was partly supported by AGH grant No. 10.420.03.     

Retention behaviour of some high-intensity sweeteners on different SPE sorbents

The objective of this paper is to provide information about application of solid-phase extraction (SPE) for isolation of nine high-intensity sweeteners (acesulfame-K, alitame, aspartame, cyclamate, dulcin, neotame, saccharin, sucralose and neohesperidin dihydrochalcone) from aqueous solutions. The influence of several types of LC-MS compatible buffers (different pH values and compositions) on their recovery has been studied and discussed. A number of commercially available SPE cartridges, such as Chromabond C18ec, Strata-X RP, Bakerbond Octadecyl, Bakerbond SDB-1, Bakerbond SPE Phenyl, Oasis HLB, LiChrolut RP-18, Supelclean LC-18, Discovery DSC-18 and Zorbax C18 were tested in order to evaluate their applicability for the isolation of analytes. Very high recoveries (better than 92%) of all studied compounds were obtained using formic acid-N,N-diisopropylethylamine buffer adjusted to pH 4.5 and C₁₈-bonded silica sorbents. Behaviour of polymeric sorbents strongly depends on their structure. Strata-X RP behaves much like a C₁₈-bonded silica sorbent. Recoveries obtained using Oasis HLB were comparable with those observed for silica-based sorbents. The only compound less efficiently (83%) retained by this sorbent was cyclamate. Bakerbond SDB-1 shows unusual selectivity towards aspartame and alitame. Recoveries of these two sweeteners were very low (26 and 42%, respectively). It was also found that aspartame and alitame can be selectively separated from the mixture of sweeteners using formic acid-triethylamine buffer at pH 3.5.     

Vibrational spectroscopy differentiates between multipotent and pluripotent stem cells

Over the last few years, there has been an increased interest in the study of stem cells in biomedicine for therapeutic use and as a source for healing diseased or injured organs/tissues. More recently, vibrational spectroscopy has been applied to study stem cell differentiation. In this study, we have used both synchrotron based FTIR and Raman microspectroscopies to assess possible differences between human pluripotent (embryonic) and multipotent (adult mesenchymal) stem cells, and how O(2) concentration in cell culture could affect the spectral signatures of these cells. Our work shows that infrared spectroscopy of embryonic (pluripotent) and adult mesenchymal (multipotent) stem cells have different spectral signatures based on the amount of lipids in their cytoplasm (confirmed with cytological staining). Furthermore, O(2) concentration in cell culture causes changes in both the FTIR and Raman spectra of embryonic stem cells. These results show that embryonic stem cells might be more sensitive to O(2) concentration when compared to mesenchymal stem cells. While vibrational spectroscopy could therefore be of potential use in identifying different populations of stem cells further work is required to better understand these differences.