Extension of a combined analytical/numerical initial value problem solver for unsteady periodic flow

Here we describe analytical and numerical modifications that extend the Differential Reduced Ejector/ mixer Analysis (DREA), a combined analytical/numerical, multiple species ejector/mixing code developed for preliminary design applications, to apply to periodic unsteady flow. An unsteady periodic flow modelling capability opens a range of pertinent simulation problems including pulse detonation engines (PDE), internal combustion engine ICE applications, mixing enhancement and more fundamental fluid dynamic unsteadiness, e.g. fan instability/vortex shedding problems. Although mapping between steady and periodic forms for a scalar equation is a classical problem in applied mathematics, we will show that extension to systems of equations and, moreover, problems with complex initial conditions are more challenging. Additionally, the inherent large gradient initial condition singularities that are characteristic of mixing flows and that have greatly influenced the DREA code formulation, place considerable limitations on the use of numerical solution methods. Fortunately, using the combined analytical–numerical form of the DREA formulation, a successful formulation is developed and described. Comparison of this method with experimental measurements for jet flows with excitation shows reasonable agreement with the simulation. Other flow fields are presented to demonstrate the capabilities of the model. As such, we demonstrate that unsteady periodic effects can be included within the simple, efficient, coarse grid DREA implementation that has been the original intent of the DREA development effort, namely, to provide a viable tool where more complex and expensive models are inappropriate. Copyright © 2002 John Wiley & Sons, Ltd.     

Influence of heat treatment conditions on the porosity changes of sulfonated styrene/divinylbenzene copolymers

Sulfonic cation exchangers with two ion exchange group concentrations (0.5 and 2.4 mmol/g, samples A and B, respectively) were obtained by sulfonation of a porous styrene (S) and divinylbenzene (DVB) copolymer with chlorosulfonic acid. Strong thermal decomposition of the sulfonated copolymer A, accompanied by significant changes in its porous structure, starts at ca. 400°C. The char has no sulfonic groups. After heat treatment at 400°C in steam, a sorbent was obtained (yield 65%) that shows higher phenol sorption than the untreated sample when related to the bed volume. The chlorosulfonic derivatives of the initial copolymer were less thermally resistant than the sulfonic ones obtained by hydrolysis. Pyrolysis of the cation exchanger B, in its H+ and Ca²⁺ forms, was carried out at 900°C (yield of both chars close to 30%). By subsequent steam activation at 800°C to a 50% burn-off of the char, sorbents with well-developed, but distinctly different, porous structures were obtained. The activated char from the sulfonated copolymer in its hydrogen form was highly microporous and indicated an effective surface area of 1180 m²/g. However, because of a low contribution of mesopores, its ability to adsorb phenol from the liquid phase was not very high. The activated char from the calcium-doped copolymer, indicating a smaller surface area (580 m²/g) but characterized by a well-developed mesoporosity, was a better sorbent for phenol. © 1994 John Wiley & Sons, Inc.     

Crystalline structure of polyamide 12 as revealed by solid‐state 13C NMR and synchrotron WAXS and SAXS

The crystalline structure of polyamide‐12 (PA12) was studied by solid‐state ¹³C nuclear magnetic resonance (NMR) as well as by synchrotron wide‐ and small‐angle X‐ray scattering (WAXS and SAXS). Isotropic and oriented PA12 showed different NMR spectra ascribed to γ‐ and γ′‐crystalline modifications, respectively. On the basis of the position of the first diffraction peak, the isotropic γ‐form and the oriented γ′‐form were shown to be with hexagonal crystalline lattice at room temperature. When heated, the two PA12 polymorphs demonstrated different behaviors. Above 140 °C, the isotropic γ‐PA12 partially transformed into α‐modification. No such transition was observed with the oriented γ′‐PA12 phase even after annealing at temperatures close to melting. A γ′–γ transition was observed here only after isotropization by melting point. Various structural parameters were extracted from the WAXS and SAXS patterns and analyzed as a function of temperature and orientation: the degree of crystallinity, the d‐spacings, the Bragg's long spacings, the average thicknesses of the crystalline (l_c) and amorphous (l_a) phases, and the linear crystallinity x_cl within the lamellar stacks. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3720–3733, 2005     

Magydardiendiol,diterpenoid with a new skeleton from magydaris panacifolia (umbelliferae).

Three new diterpenoids with a substituted α-cyclogeraniol skeleton have been isolated from the umbelliferae $\text{Magydaris panacifolia}$ (Vahl) Lange, for which the names of magydar-2,13-dien-11,17-diol, $\text{1}$, magydar-2,10 (20), 13-trien-17-ol, $\text{2}$, and magydar-2,10(20), 13-trien-17-yl acetate, $\text{3}$, are proposed. The structures of these substances have been deduced from spectroscopic and chemical data.     

Hydrophilic core-shell microspheres: a suitable support for controlled attachment of proteins and biomedical diagnostics

Functional hydrophilic microspheres (latex particles) have found various applications in life sciences and in medicine - particularly in latex diagnostic tests. This paper presents a comprehensive review of studies on latex particles with a hydrophilic interfacial layer composed of various hydrophilic polymers with reactive groups at the ends of macromolecules or at each monomeric unit along the chain. Typical examples of these hydrophilic polymers are poly(2-hydroxyethyl methyl methacrylate), poly(acrylic acid), poly(N,N-dimethylacrylamide), polysaccharides, poly(ethylene oxide) and polyglycidol. Hydrophilic microspheres with different morphologies (uniform or core-shell, see Figure) have been synthesized by emulsion and dispersion polymerizations. The chemical structure of polymers which constitute the interfacial layer of microspheres has been investigated using a variety of instrumental techniques (such as XPS, SSIMS and NMR) and analytical methods based on specific chemical reactions suitable for the determination of particular functional groups. Microspheres are exposed to contact with proteins in the majority of medical applications. This paper presents examples of studies on the attachment of these biomacromolecules to microspheres. The relation between the structure of the interfacial layer of microspheres and the ability of these particles for the covalent binding of proteins is discussed. Several examples of diagnostic tests, in which hydrophilic microspheres with adsorbed or covalently immobilized proteins were used as reagents, are presented. The paper also contains a short review of the application of magnetic hydrophilic particles for protein separation. Examples of hydrophilic latex particles used for hemoperfusion or heavy metal ion separation are presented. Hydrophilic microspheres with uniform or core-shell morphologies.     

Detection of phosphoproteins on electroblot membranes using a small-molecule organic fluorophore

A new formulation of the small-molecule organic fluorophore, Pro-Q Diamond dye, has been developed that permits rapid and simple detection of phosphoproteins directly on polyvinylidene difluoride (PVDF) or nitrocellulose membranes (electroblots). Protein samples are first separated by electrophoresis and then electroblotted to membranes, stained and destained, in an analogous manner as typically performed with Amido Black or Ponceau S dye staining of total protein profiles. After staining, blots are imaged using any of a variety of laser-based gel scanners, xenon-arc lamp-based gel scanners or charge-coupled device (CCD) camera-based imaging devices equipped with UV trans- or epi-illumination. The uncomplicated and reliable staining protocol delivers results in as little as 1 h and the limit of detection for the stain is typically 2-4 ng of phosphoprotein with a linear dynamic range of approximately 15-fold. Compared with traditional radiolabeling and antibody-based approaches, the new method offers significant advantages, including avoidance of radioactivity, no need for expensive antibodies, no requirement for blocking unoccupied sites on the membrane with protein or detergent solutions, no sequence context-specific binding to phosphorylated amino acid residues and the ability to analyze the native, steady-state phosphorylation of proteins obtained directly from tissue specimens or body fluids. Pro-Q Diamond dye binds directly and exclusively to the phosphate moiety, allowing it to detect the broadest spectrum of phosphorylated proteins possible. The stain binds noncovalently to phosphoproteins and is thus fully compatible with matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS) or Edman sequencing. The blot stain is also compatible with standard colorimetric, fluorogenic, and chemiluminescent detection techniques employed in immunoblotting.     

Spontaneous generation of chirality and chiroptical spectra of N-nitroso-2,4-diaryl-3-azabicyclo[3.3.1]nonanes

The crystal structures of several bicyclic N-nitrosamines indicate that they crystallize in the chiral (Sohncke) space group P2₁2₁2₁ as conglomerates. This allows the resolution of these compounds by manual picking of the enantiomorphous crystals. The optical activity of the single crystals was confirmed by their CD spectra taken in KBr disks. The absolute configurations of the title nitrosamines were assigned by crystallographic measurements and by a comparison of their CD spectra with those of a reference compound resolved by classical methods. The observed Cotton effect signs, corresponding to the n–π¹ transition, were correlated with the helicity of the inherently chiral nitrosamine chromophore.     

Design of polyglycidol-containing microspheres for biomedical applications

The paper presents a short review on the synthesis, characterisation and selected medical applications of poly(styrene/α-tert-butoxy-ω-vinylbenzyl-polyglycidol) (P(S/PGL)) microspheres. The soap-free emulsion-polymerisation of styrene and α-tert-butoxy-ω-vinylbenzyl-polyglycidol macromonomer (PGL) in water yielded core-shell microspheres with a low particle-diameter dispersity (ratio of the weight average particle diameter and the number average particle diameter). The interfacial fraction of PGL units, estimated by XPS, was in the range of 0–42 mole % depending on the concentration of the macromonomer in the polymerisation feed. The studies of adsorption of model proteins showed that the surface fraction of adsorbed protein was significantly reduced when the PGL interfacial fraction was higher than 40 mole %. The P(S/PGL) particles with covalently immobilised proteins were used for the preparation of photonic crystal assemblies suitable for applications in optical biosensors and the medical diagnostic test for the detection of Helicobacter pylori antibodies in the blood serum.     

[1,3‐Bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene]chloridogold(I)

The molecule of the title compound, [AuCl(C₂₇H₃₆N₂)], which belongs to a class of potentially catalytically active N‐heterocyclic carbene complexes, has crystallographic C₂ symmetry and approximate C_2v symmetry. The structure is isostructural with the Cu^I and Ag^I analogues. A previous report of the structure of the title compound as its toluene solvate [Fructos et al. (2005). Angew. Chem. Int. Ed. 44 , 5284–5288] has inaccurate geometry for the complex molecule as a consequence of probable incorrect refinement in the space group Cc, instead of C2/c [Marsh (2009). Acta Cryst. B 65 , 782–783]. The Au—C bond length of 1.998 (4) Å in the title compound is more consistent with the mean distance of 1.979 (14) Å found in 52 other reported [AuCl(carbene)] complexes than with the shorter distance of 1.942 (3) Å given for the refinement in the space group Cc for the toluene solvate and the value of 1.939 Å obtained from the recalculation of that structure in C2/c.