Extracellular matrix of the human cyclic corpus luteum

Extracellular matrix regulates many cellular processes likely to be important for development and regression of corpora lutea. Therefore, we identified the types and components of the extracellular matrix of the human corpus luteum at different stages of the menstrual cycle. Two different types of extracellular matrix were identified by electron microscopy; subendothelial basal laminas and an interstitial matrix located as aggregates at irregular intervals between the non-vascular cells. No basal laminas were associated with luteal cells. At all stages, collagen type IV α1 and laminins α5, β2 and γ1 were localized by immunohistochemistry to subendothelial basal laminas, and collagen type IV α1 and laminins α2, α5, β1 and β2 localized in the interstitial matrix. Laminin α4 and β1 chains occurred in the subendothelial basal lamina from mid-luteal stage to regression; at earlier stages, a punctate pattern of staining was observed. Therefore, human luteal subendothelial basal laminas potentially contain laminin 11 during early luteal development and, additionally, laminins 8, 9 and 10 at the mid-luteal phase. Laminin α1 and α3 chains were not detected in corpora lutea. Versican localized to the connective tissue extremities of the corpus luteum. Thus, during the formation of the human corpus luteum, remodelling of extracellular matrix does not result in basal laminas as present in the adrenal cortex or ovarian follicle. Instead, novel aggregates of interstitial matrix of collagen and laminin are deposited within the luteal parenchyma, and it remains to be seen whether this matrix is important for maintaining the luteal cell phenotype.

Diels-Alder reactions as an efficient route to high purity cyclic polymers

A simple and efficient route for the synthesis of cyclic polymer systems is presented. Linear furan protected α-maleimide-ω-cyclopentadienyl functionalized precursors (poly(methyl methacrylate) and poly(tert-butyl acrylate)) were synthesized via atom transfer radical polymerization (ATRP) and subsequent substitution of the bromine end-group with cyclopentadiene. Upon heating at high dilution, deprotection of the dieneophile occurs followed by an intramolecular Diels–Alder reaction yielding a high purity cyclic product.

Simultaneous voltammetric determination of three herbicides in food and water samples with the aid of chemometrics

Differential pulse stripping voltammetry method(DPSV) was applied to the determination of three herbicides, ametryn, cyanatryn, and dimethametryn. It was found that their voltammograms overlapped strongly, and it is difficult to determine these compounds individually from their mixtures. With the aid of chemometrics, classical least squares(CLS), principal component regression(PCR) and partial least squares(PLS), voltammogram resolution and quantitative analysis of the synthetic mixtures of the three compounds were successfully performed. The proposed method was also applied to the analysis of some real samples with satisfactory results.

Response of partially grouted wider reinforced masonry walls to inplane cyclic shear

Partially grouted wider reinforced masonry wall, built predominantly using face shell bedded hollow concrete blocks, is an economical structural system and is popularly used in the cyclonic areas; its out-of-plane response to lateral loading is well understood, unfortunately its inplane shear behaviour is less well understood as to the effect of partial gouting in intervening the load paths within the wall. For rational analysis of the wall clarification is sought as to whether the wall acts as a composite of unreinforced panels and reinforced cores or as a continuum of masonry embedded with reinforced at wider spacing. This paper reports the results of four full scale walls tested under inplane cyclic shear loading to provide some insight into the effect of the grout cores in altering the load paths within the wall. The global lateral load - lateral deflection hysteric curves as well as local responses of some critical zones of the shear walls are presented.

Wider reinforced masonry shear walls subjected to cyclic lateral loading

Partially grouted wider reinforced masonry wall, built predominantly with the use of face shell bedded hollow concrete blocks, is adopted extensively in the cyclonic areas due to its economy. Its out-of-plane response to lateral pressure loading is well definied; however its in-plane shear behaviour is less well understood, in particular it is unclear how the grouted reinforced cores affect the load paths within the wall. For the rational design of the walls, clarification is sought as to whether the wall acts as a composite of unreinforced panels surrounded by the reinforced cores or simply as a continuum embedded with reinforcement at wider spacing. This paper reports four full scale walls tested under in-place cyclic shear loading to provide some insight into the effect of the grout cores in altering the load paths within the wall. The global lateral load - lateral deflection hysteretic curves as well as the local responses of some critical zones of the shear walls are presented. It is shown that the aspect ratio of the unreinforced masonry panels surrounded by the reinforced grouted cores within the shear walls have profound effect in ascertaining the behaviour of the shear walls.

Investigation into the transport, behaviour and deposition of combustion aerosols from transport sources

The deterioration of air quality is a significant issue in large and growing cities. This work investigates particulate emissions from transport, the largest source of air pollution in cities today. Emitters such as busy roads and diesel trains are investigated, with specific reference to the evolution of particles over time and distance. Diesel trains are investigated as an alternative to road traffic in investigating evolutionary processes. Higher emissions and solitary sources mean that the emitted plume can be observed over time in a single location. These results represent the first investigation of the evolution of fine and ultrafine aerosol particles from this type of source. Aerosols near a busy road are investigated, with the result that a dependence of total number concentration on distance from the road is shown to be related to the fragmentation of nanoparticle clusters. Local meteorological conditions are also monitored and humidity is shown to vary with distance from the road in a nonmonotonic way. Particles from a busy road were also examined using a scanning electron microscope, with the intention of understanding the make up of the emitted aerosol plume. It was determined that due to significant surface behaviour post-deposition, this method of analysis could not directly classify airborne pollutants. Some interesting results were obtained however, particularly in terms of composite particles and the analysis of deposited patterns. This thesis introduces new work in terms of the analysis of diesel train particulate emissions, as well as adding further evidence towards the fragmentation process of aerosol evolution in both background concentrations and emitted aerosol plumes.

Computational design of cyclic nitroxides as efficient redox mediators for dye-sensitized solar cells

Cyclic nitroxide radicals represent promising alternatives to the iodine-based redox mediator commonly used in dye-sensitized solar cells (DSSCs). To date DSSCs with nitroxide-based redox mediators have achieved energy conversion efficiencies of just over 5 % but efficiencies of over 15 % might be achievable, given an appropriate mediator. The efficacy of the mediator depends upon two main factors: it must reversibly undergo one-electron oxidation and it must possess an oxidation potential in a range of 0.600-0.850 V (vs. a standard hydrogen electrode (SHE) in acetonitrile at 25 °C). Herein, we have examined the effect that structural modifications have on the value of the oxidation potential of cyclic nitroxides as well as the reversibility of the oxidation process. These included alterations to the N-containing skeleton (pyrrolidine, piperidine, isoindoline, azaphenalene, etc.), as well as the introduction of different substituents (alkyl-, methoxy-, amino-, carboxy-, etc.) to the ring. Standard oxidation potentials were calculated using high-level ab initio methodology that was demonstrated to be very accurate (with a mean absolute deviation from experimental values of only 16 mV). An optimal value of 1.45 for the electrostatic scaling factor for UAKS radii in acetonitrile solution was obtained. Established trends in the values of oxidation potentials were used to guide molecular design of stable nitroxides with desired E° ox and a number of compounds were suggested for potential use as enhanced redox mediators in DSSCs. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cyclic imides and an open-chain amide carboxylic acid from the facile reaction of cis-cyclohexane-1,2-dicarboxylic anhydride with the isomeric monofluoroanilines

The structures of the cyclic imides cis-2-(2-fluorophenyl)-3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione, C14H14FNO2, (I), and cis-2-(4-fluorophenyl)-3a,4,5,6,7,7a-hexahydroisoindoline-1,3-dione, C14H14FNO2, (III), and the open-chain amide acid rac-cis-2-[(3-fluorophenyl)carbamoyl]cyclohexane-1-carboxylic acid, C14H16FNO3, (II), are reported. Cyclic imides (I) and (III) are conformationally similar, with comparable ring rotations about the imide N-Car bond [the dihedral angles between the benzene ring and the five-membered isoindole ring are 55.40 (8)° for (I) and 51.83 (7)° for (III)]. There are no formal intermolecular hydrogen bonds involved in the crystal packing of either (I) or (III). With the acid (II), in which the meta-related F-atom substituent is rotationally disordered (0.784:0.216), the amide group lies slightly out of the benzene plane [the interplanar dihedral angle is 39.7 (1)°]. Intermolecular amide-carboxyl N-HO hydrogen-bonding interactions between centrosymmetrically related molecules form stacks extending down b, and these are linked across c by carboxyl-amide O-HO hydrogen bonds, giving two-dimensional layered structures which lie in the (011) plane. The structures reported here represent examples of compounds analogous to the phthalimides or phthalanilic acids and have little precedence in the crystallographic literature.