Tubular Structures of Calcium Carbonate: Formation,Characterization, and Implications in Natural Mineral Environments

Chemical gardens are self-assembled tubular precipitates formed by a combination of osmosis, buoyancy, and chemical reaction, and thought to be capable of catalyzing prebiotic condensation reactions. In many cases, the tube wall is a bilayer structure with the properties of a diaphragm and/or a membrane. The interest in silica gardens as microreactors for materials science has increased over the past decade because of their ability to create long-lasting electrochemical potential. In this study, we have grown single macroscopic tubes based on calcium carbonate and monitored their time-dependent behavior by in situ measurements of pH, ionic concentrations inside and outside the tubular membranes, and electrochemical potential differences. Furthermore, we have characterized the composition and structure of the tubular membranes by using ex situ X-ray diffraction, infrared and Raman spectroscopy, as well as scanning electron microscopy. Based on the collected data, we propose a physicochemical mechanism for the formation and ripening of these peculiar CaCO₃ structures and compare the results to those of other chemical garden systems. We find that the wall of the macroscopic calcium carbonate tubes is a bilayer of texturally distinct but compositionally similar calcite showing high crystallinity. The resulting high density of the material prevents macroscopic calcium carbonate gardens from developing significant electrochemical potential differences. In the light of these observations, possible implications in materials science and prebiotic (geo)chemistry are discussed.     

Preliminary investigation of the simultaneous detection of sugars,ascorbic acid,citric acid,and sodium benzoate in non-alcoholic beverages by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used for the simultaneous detection of sugars, ascorbic acid, citric acid, sodium and/or potassium benzoate in non-alcoholic beverages, with meso-tetrakis(pentafluorophenyl)porphyrin (MW 974) as a matrix. Using potassium hydroxide as dopant, fructose/glucose was detected as the potassiated molecule at m/z 219, whereas potassiated sucrose, [Sucrose. K](+), was detected at m/z 381. Using sodium hydroxide as dopant, the fructose and sucrose ions were detected at m/z 203 and 365, respectively. Citric acid generated multiple ions at m/z 269, 307, and 345, which were assigned to [Citricbond;H+2K](+), [Citricbond;2H+3K](+), and [Citricbond;3H+4K](+), respectively. However, a stored methanolic solution of citric acid produced additional ions at m/z 283, 297, and 321, which were attributed to [Citricbond;2H+CH(3)+2K](+), [Citricbond;3H+2CH(3)+2K](+), and [Citricbond;3H+CH(3)+3K](+), respectively, due to esterification that took place during storage. The limits of detection in water were: ascorbic acid, 0.30 wt%; citric acid, 0.5 wt%; and sodium benzoate, 0.001 wt%. In the beverage formulations, the limits of detection were: ascorbic acid 0.3 wt%, citric acid 0.3 wt%, and sodium benzoate 0.02 wt%. Spiking a water or beverage solution that contained ascorbic and/or citric acid with less than 0.6 wt% of tartaric acid lowered the detection limits of ascorbic and citric acids to 0.2 wt%. This study demonstrates the potential for using MALDI-TOFMS in the quality control analyses of non-alcoholic beverages, particularly with regard to the detection of low molecular weight organic acids in commercial beverage formulations.     

Three Saponins, a Steroid, and a Flavanol Glycoside from Achyrantes aspera

Summary.  Three bisdesmosidic saponins, 20-hydroxyecdysone, and quercetin-3-O-β-D-galactoside were isolated from the methanol extract of the aerial parts of Achyranthes aspera L. (Amaranthaceae). Their structures were established on the basis of NMR spectroscopic analysis; the complete ¹H and ¹³C assignments of the compounds were achieved by means of 2D NMR studies. Received July 21, 1999. Accepted August 26, 1999     

Effects of A1 site occupation on dielectric and ferroelectric properties of Sr4CaRTi3Nb7O30（R=Ce,Eu） tungsten bronze ceramics

Sr4Ca RTi3Nb7O30（R = Ce, Eu） tungsten bronze ceramics are prepared by a standard solid state reaction method. The effects of A1 site occupation on the dielectric and ferroelectric properties of Sr4 Ca RTi3Nb7O30（R = Ce, Eu） tetragonal tungsten bronzes are investigated. The Sr4 Ca Ce Ti3Nb7O30 shows a normal transition behavior due to the closer size ion occupation in A1 sites, which could suppress the distortion of B2 octahedra effectively. Sr4 Ca Eu Ti3Nb7O30 ceramic exhibits two dielectric anomalies, which might be related to the fact that the large radius difference between Ca^2＋ and Eu^3＋ could lead to the uneven distribution of Ca^2＋ and Eu^3＋ in A1 sites and form two slightly different kinds of compositions with different transition temperatures in the structure. Our results indicate that the ionic radius difference in A1 sites plays an important role in determining the dielectric and ferroelectric natures of the filled tungsten bronze ceramics. Polarization–electric field（P–E） curves are evaluated at room temperature and both of them show hysteresis loops. Sr4 Ca Ce Ti3Nb7O30 shows a fat hysteresis loop, indicating the long-range ferroelectric order in the ceramic. The current density–electric field（J–E） curves are measured at room temperature with a largest leakage current density of ～ 10^-6A/cm^2, indicating that their leakage currents are rather low.     

Influence on friction behavior of micro-texturing under lubricated non-conformal contact

Laser surface texturing (LST) is a well-known surface engineering process used to create arranged dimples on surface using a material ablation process. In this process, a well arranged micro-dimple can produce significant improvements of engineering components in aspects such as load carrying capacity, wear resistance, wetting characteristics and reduction of friction coefficient. In the present work, we investigated the effect of multi-dimple LST steel surfaces on tribological properties under non-conforming contact. The multi-dimple textured surfaces with some specific formula arrays were fabricated by laser ablation process on steel disc by combining patterns of circles and triangles, and circles and squares, having different dimple densities to optimize the surface texturing effect on tribological performance. The tribological test of multi-dimple textured surface was performed by a ball-on-flat unidirectional tribometer in lubricated condition, and the results compared with that of a single-dimple and untextured (polished and ground) surfaces. The results indicate that the surface with multi-dimple textured patterns had better friction performance than the untextured and single-dimple textured surfaces. The beneficial effect of multi-dimple textured patterns was associated with transition of lubrication from boundary to mixed lubrication regime.