Crystallization of calcium sulfate on polymeric surfaces

Surface crystallization of calcium sulfate dihydrate (gypsum) on a series of polymeric surfaces was studied using a quartz microbalance system. Polyelectrolyte multilayer films (positively and negatively charged surfaces) were formed on the quartz crystal microbalance (QCM) sensors utilizing a layer-by-layer spin-assembly method. The kinetics of gypsum surface crystallization was quantified in terms of the evolution of gypsum mineral scale on the different surfaces. For comparison mineral scaling was also evaluated on silica and polyamide surfaces. For surfaces of the same charge polarity (+/-), the mass density of gypsum scale was lower (PSS相似文献   

Charge, stereochemistry, or epitaxy? Toward controlled biomimetic nucleation at mixed monolayer templates

Floating monolayer mixtures of cationic dioctadecyldimethyldiammonium bromide and anionic lipids were used as variable templates for the biomimetic nucleation of calcium carbonate and studied using grazing incidence X-ray diffraction. Varying the ratio of constituents changes the monolayer charge, structure, and molecular tilt. The nucleating surface of calcite also changes as the mixture is varied, and at an 80:20 ratio the (012) face is seen under a floating monolayer template for the first time. Our results indicate that the average template lattice is the major controlling factor in the oriented nucleation of CaCO(3). This is in contrast to the current view that the orientation is controlled by the stereochemical matching of the terminal functional group and molecular tilt with respect to the carbonate groups in the crystal.     

牛血清白蛋白Langmuir膜控制方解石形成取向生长的球形微晶

本文以生物矿化模型系统为基础，利用LB技术，采用本体交换的方法，制备了牛血清白蛋白(BSA)Langmuir膜，以更加接近生物矿化的方法研究了BSA Langmuir膜对碳酸钙晶体生长的取向、形貌和晶型的控制作用。XRD分析表明晶体为碳酸钙的方解石晶型，且晶体仅沿(104)晶面有取向生长。SEM分析表明结晶初期碳酸钙以球状的晶体存在，随着时间的延长，BSA对晶体形貌的控制作用逐渐减弱，直到完全不起作用，在结晶后期形成菱方形晶体，但晶体生长取向和晶型始终没有发生变化。说明BSA Langmuir膜对碳酸钙的生长取向、晶型和形貌有较好的控制作用。     

Construction and molecular modeling of phospholipid surfaces

A protocol is given for the construction of phospholipid surfaces that possess variable head groups and thus variable net charge. Ab initio quantum mechanical calculations are performed to establish the necessary force field (AMBER) parameters. The charge distribution is defined by an electrostatic potential method consistent with the ab initio wave function. As a model calculation, a monolayer surface with head groups of phosphatidylserine and phosphatidylcholine derived from the crystal structure of 1,2-dilauroyl-DL-phosphatidylethanolamine (DLPE) is placed in a water bath with two Ca(II) ions present. The resultant surface is energy-optimized followed by 64 ps of molecular dynamics integration. Evaluation of calcium ion coordination environments, characterization of the P-N dipole inclination with respect ot the plane of the monolayer, and calculation of molecular surface area is performed and compared with experimental data.     

The Application of Ammonium Hydroxide and Sodium Hydroxide for Reagent Softening of Water

The calcium carbonate crystallization from aqueous solutions in the presence of alkali additives such as sodium hydroxide and ammonium hydroxide has been researched. It is found CaCO₃ crystallizes predominantly in the modification of aragonite in the presence of ammonium hydroxide. The calcium carbonate formation rate in an alkaline medium and the gaseous reaction products due to sorption of gas bubbles on crystal surfaces, affect the aragonite structure formation. It is shown use of ammonium hydroxide for water treatment can solve two urgent tasks such as water softening and exclusion sediment of deposits on the equipment surfaces by a calcium carbonate crystallization in the form of aragonite.     

The growth of crystals in solution

The crystallization of sparingly soluble salts from their aqueous supersaturated solutions is discussed from the standpoint of two important applications; scale formation and biological mineralization. Theories of crystal growth are outlined and the importance of kinetic factors in determining the nature of the growing phases is discussed. The kinetic factors can be studied by using a highly reproducible seeded growth technique and under certain conditions secondary nucleation can also be induced on the surface of the inoculating seed crystals. The kinetics of crystallization of the alkaline earth surfaces and the calcium phosphates is discussed. In the latter systems, temperature, supersaturation, surface concentration, pH, ionic strength and the presence of foreign ions are important in determining the nature of the phase which grows on the added seed crystals. The mechanism of the retardation of crystal growth by added crystallization inhibitors is illustrated by the influence of organic phosphonate molecules upon the precipitation of calcium carbonate.     

Ordered adsorption of coagulation factor XII on negatively charged polymer surfaces probed by sum frequency generation vibrational spectroscopy

Electrostatic interactions between negatively charged polymer surfaces and factor XII (FXII), a blood coagulation factor, were investigated by sum frequency generation (SFG) vibrational spectroscopy, supplemented by several analytical techniques including attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), quartz crystal microbalance (QCM), ζ-potential measurement, and chromogenic assay. A series of sulfonated polystyrenes (sPS) with different sulfonation levels were synthesized as model surfaces with different surface charge densities. SFG spectra collected from FXII adsorbed onto PS and sPS surfaces with different surface charge densities showed remarkable differences in spectral features and especially in spectral intensity. Chromogenic assay experiments showed that highly charged sPS surfaces induced FXII autoactivation. ATR-FTIR and QCM results indicated that adsorption amounts on the PS and sPS surfaces were similar even though the surface charge densities were different. No significant conformational change was observed from FXII adsorbed onto surfaces studied. Using theoretical calculations, the possible contribution from the third-order nonlinear optical effect induced by the surface electric field was evaluated, and it was found to be unable to yield the SFG signal enhancement observed. Therefore it was concluded that the adsorbed FXII orientation and ordering were the main reasons for the remarkable SFG amide I signal increase on sPS surfaces. These investigations indicate that negatively charged surfaces facilitate or induce FXII autoactivation on the molecular level by imposing specific orientation and ordering on the adsorbed protein molecules. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Differentiating calcium carbonate polymorphs by surface analysis techniques—an XPS and TOF‐SIMS study

Calcium carbonate has evoked interest owing to its use as a biomaterial, and for its potential in biomineralization. Three polymorphs of calcium carbonate, i.e. calcite, aragonite, and vaterite were synthesized. Three conventional bulk analysis techniques, Fourier transform infrared (FTIR), X‐ray diffraction (XRD), and SEM, were used to confirm the crystal phase of each polymorphic calcium carbonate. Two surface analysis techniques, X‐ray photoelectron spectroscopy (XPS) and time‐of‐flight secondary ion mass spectroscopy (TOF‐SIMS), were used to differentiate the surfaces of these three polymorphs of calcium carbonate. XPS results clearly demonstrate that the surfaces of these three polymorphs are different as seen in the Ca(2p) and O(1s) core‐level spectra. The different atomic arrangement in the crystal lattice, which provides for a different chemical environment, can explain this surface difference. Principal component analysis (PCA) was used to analyze the TOF‐SIMS data. Three polymorphs of calcium carbonate cluster into three different groups by PCA scores. This suggests that surface analysis techniques are as powerful as conventional bulk analysis to discriminate calcium carbonate polymorphs. Copyright © 2008 John Wiley & Sons, Ltd.     

Localized Crystallization of Enantiomeric Organic Compounds on Chiral Micro‐patterns from Various Organic Solutions

The controlled crystallization of enantiomers of an organic compound (a cyclic phosphoric acid derivative) on templated micro‐patterned functionalised surfaces is demonstrated. Areas where a complementary chiral thiol has been located were effective heterogeneous nucleation centres when a solution of the compound is evaporated slowly. Various organic solvents were employed, which present a challenge with respect to other examples when water is used. The solvent and the crystallization method have an important influence on the crystal growth of these compounds. When chloroform was employed, well‐defined crystals grow away from the surface, whereas crystals grow in the plane from solutions in isopropanol. In both cases, nucleation is confined to the polar patterned regions of the surface, and for isopropanol growth is largely limited within the pattern, which shows the importance of surface chemistry for nucleation and growth. The apparent dependence on the enantiomer used in the latter case could imply stereo‐differentiation as a result of short‐range interactions (the templating monolayer is disordered, even at the nanometre scale). The size of the pattern of chiral monolayer also determines the outcome of the crystallization; 5 μm dots are most effective. Despite the low surface tension of the samples (relative to the high surface tension of water), differential solvation of the polar and hydrophobic layers of the solvents allows crystallization in the polar regions of the monolayer, therefore the polarity of the regions in which heterogeneous nucleation takes place is indeed very important. Despite the complex nature of the crystallization process, these results are an important step towards to the use of patterned surfaces for heterogeneous selective nucleation of enantiomers.     

Studies of monolayer/substrate adhesion as function of the monolayer headgroup charge: DMPE and DMPA

The variation of the work of adhesion between lipid monolayers and a plane silicon oxide surface in a typical LB-configuration is measured as function of the subphase pH. The adhesion energy is deduced via fluorescence microscopy from the equilibrium meniscus height. With increasing pH the negative headgroup charge of both, dimyristoylphosphatidylethanolamine (DMPE) and dimyristoylphosphatidic acid (DMPA) monolayers increases. The increasing charge of DMPE is reflected in a measured decrease of the work of adhesion at higher pH. The DMPA/SiO₂ interaction is not affected by increasing headgroup charges. These results are qualitatively understood in terms of an electrostatic double layer interaction between charged surfaces. It predicts decreasing adhesion for increasing, but low surface charge densities (DMPE). whereas the adhesion is constant for high surface charge densities (DMPA).     

Sensitivity of cationic surfactant templates to specific anions in liquid interface crystallization

We investigated the specific effects of potassium salts of various anions upon the interfacially templated crystal nucleation of K(2)SO(4). Previously, we have shown that the presence of several salts at low concentrations could induce changes in important crystallization characteristics templated by 1-octadecylamine at the liquid-liquid interface, and that these changes depended greatly on the specific identity of the salt. In this work we extend our surfactant monolayers to include dimethyldioctadecylammonium bromide (DODAB) and hexadecyltrimethylammonium bromide (CTAB). Addition of 10 mM of various potassium salts results in a diminution in efficiency of the templating capability of CTAB monolayer, as evidenced by higher C(onset) values and polycrystalline habit. The ability of the anions to perturb these values varied in a manner consistent with a Hofmeister series. However, DODAB maintained its templating effectiveness regardless of the nature of the salt or concentration. DODAB and CTAB are likely to be undergoing different reordering effects in the monolayer upon binding with chaotropic anions: a combined reduction in surface charge with different monolayer ordering results in a differing template ability. These studies have provided significant insights into the understanding of the interaction of ordered surfactant arrays with salts, and provide exciting possibilities for crystal engineering and materials design.     

Calcium carbonate particle growth depending on coupling among adjacent layers in hybrid LB/LbL films

There are practical and academic situations that justify the study of calcium carbonate crystallization and especially of systems that are associated with organic matrices and a confined medium. Despite the fact that many different matrices have been studied, the use of well-behaved, thin organic films may provide new knowledge about this system. In this work, we have studied the growth of calcium carbonate particles on well-defined organic matrices that were formed by layer-by-layer (LbL) polyelectrolyte films deposited on phospholipid Langmuir-Blodgett films (LB). We were able to change the surface electrical charge density of the LB films by changing the proportions of a negatively charged lipid, the sodium salt of dimyristoyl-sn-glycero-phosphatidyl acid (DMPA), and a zwitterionic lipid, dimyristoyl-sn-glycero-phosphatidylethanolamine (DMPE). This affects the subsequent polyelectrolyte LbL film deposition, which also changes the the nature of the bonding (electrostatic interaction or hydrogen bonding). This approach allowed for the formation of calcium carbonate particles of different final shapes, roughnesses, and sizes. The masses of deposited lipids, polyelectrolytes, and calcium cabonate were quantified by the quartz crystal microbalance technique. The structures of obtained particles were analyzed by scanning electron microscopy.     

Nonequilibrium 2-hydroxyoctadecanoic acid monolayers: effect of electrolytes

2-Hydroxyacids display complex monolayer phase behavior due to the additional hydrogen bonding afforded by the presence of the second hydroxy group. The placement of this group at the position α to the carboxylic acid functionality also introduces the possibility of chelation, a utility important in crystallization including biomineralization. Biomineralization, like many biological processes, is inherently a nonequilibrium process. The nonequilibrium monolayer phase behavior of 2-hydroxyoctadecanoic acid was investigated on each of pure water, calcium chloride, sodium bicarbonate and calcium carbonate crystallizing subphases as a precursor study to a model calcium carbonate biomineralizing system, each at a pH of ～6. The role of the bicarbonate co-ion in manipulating the monolayer structure was determined by comparison with monolayer phase behavior on a sodium chloride subphase. Monolayer phase behavior was probed using surface pressure/area isotherms, surface potential, Brewster angle microscopy, and synchrotron-based grazing incidence X-ray diffraction and X-ray reflectivity. Complex phase behavior was observed for all but the sodium chloride subphase with hydrogen bonding, electrostatic and steric effects defining the symmetry of the monolayer. On a pure water subphase hydrogen bonding dominates with three phases coexisting at low pressures. Introduction of calcium ions into the aqueous subphase ensures strong cation binding to the surfactant head groups through chelation. The monolayer becomes very unstable in the presence of bicarbonate ions within the subphase due to short-range hydrogen bonding interactions between the monolayer and bicarbonate ions facilitated by the sodium cation enhancing surfactant solubility. The combined effects of electrostatics and hydrogen bonding are observed on the calcium carbonate crystallizing subphase.     

蔗糖/精氨酸体系中碳酸钙结晶的仿生合成

该文以更加接近生物矿化的方法研究了蔗糖/精氨酸体系对碳酸钙晶体取向、形貌和晶型的控制作用.XRD 分析表明,在蔗糖/L-精氨酸混合体系中合成的晶体主要为碳酸钙的球霰石晶型及少量的方解石型,在单独的蔗糖或L-精氨酸溶液中基本是球霰石晶型.SEM分析表明,蔗糖和L-精氨酸均可诱导形成特殊形貌的碳酸钙.实验结果表明,蔗糖/精...     

DPPC Langmuir monolayer at the air-water interface: probing the tail and head groups by vibrational sum frequency generation spectroscopy

Dipalmitoylphosphatidylcholine (DPPC) is the predominant lipid component in lung surfactant. In this study, the Langmuir monolayer of deuterated dipalmitoylphosphatidylcholine (DPPC-d62) in the liquid-expanded (LE) phase and the liquid-condensed (LC) phase has been investigated at the air-water interface with broad bandwidth sum frequency generation (BBSFG) spectroscopy combined with a Langmuir film balance. Four moieties of the DPPC molecule are probed by BBSFG: the terminal methyl (CD3) groups of the tails, the methylene (CD2) groups of the tails, the choline methyls (CH3) in the headgroup, and the phosphate in the headgroup. BBSFG spectra of the four DPPC moieties provide information about chain conformation, chain orientation, headgroup orientation, and headgroup hydration. These results provide a comprehensive picture of the DPPC phase behavior at the air-water interface. In the LE phase, the DPPC hydrocarbon chains are conformationally disordered with a significant number of gauche configurations. In the LC phase, the hydrocarbon chains are in an all-trans conformation and are tilted from the surface normal by 25 degrees. In addition, the orientations of the tail terminal methyl groups are found to remain nearly unchanged with the variation of surface area. Qualitative analysis of the BBSFG spectra of the choline methyl groups suggests that these methyl groups are tilted but lie somewhat parallel to the surface plane in both the LE and LC phases. The dehydration of the phosphate headgroup due to the LE-LC phase transition is observed through the frequency blue shift of the phosphate symmetric stretch in the fingerprint region. In addition, implications for lung surfactant function from this work are discussed.     

Lead adsorption on silver single crystal surfaces

Twin-electrode thin layer experiments have been carried out in the system Ag(hkl)/Pb²⁺, ClO₄^? in order to determine independently the charge and Pb²⁺ coverage fluxes of the lead underpotential adsorption. The electrosorption valency was found to be equal to the charge number of the lead ion. Therefore, the sorption behaviour of the system can be described by the metal monolayer model. The peak potentials of the cyclic voltammograms as well as the saturation coverages are only slightly dependent on the orientation of the silver single crystal surfaces used. Hypothetical superlattice structures for the monolayer formation are discussed. The Kolb-Gerischer linearity rule is considered critically.     

L-半胱氨酸自组装膜诱导草酸钙结晶研究

在CaCl2.H2O和Na2C2O4配制的过饱和溶液中,利用L-半胱氨酸(L-Cys)在金片上形成的自组装膜为模板,研究了草酸钙(CaOxa)在自组装膜上的结晶行为,并探讨了溶液pH对CaOxa晶体组成、晶型及其形貌的影响。采用X射线衍射(XRD)和扫描电子显微镜(SEM)等技术对CaOxa晶体的结构和形貌进行了表征。实验结果表明:当溶液pH=3.0时,溶液中可以形成一水草酸钙(CaC2O4.H2O,COM)和二水草酸钙(CaC2O4.2H2O,COD)晶体,而在同样pH条件下,在L-Cys自组装膜上只形成COD晶体,表明自组装单层对CaOxa晶体的成核和生长有重要影响。通过改变溶液的pH,在自组装单层上可以得到不同晶型和不同形状的CaOxa晶体。当pH=3.0时得到四方块状的COD晶体,而pH=5.0和pH=7.0时分别得到六边形和拉长六边形的COM晶体。     

Preparation of hemispherical hollow silica microcapsules with different affinity surface by using spherical vaterite calcium carbonate as template

We developed a method to prepare hemispherical hollow silica microcapsules (HHSM) with different affinity surfaces using spherical vaterite calcium carbonate (SVCC) as a template. The preparation process composed of the adhesion of calcium carbonate onto the surface of methyl methacrylate (MMA) droplets followed by suspension polymerization, the partial etching of calcium carbonate on the polymethyl methacrylate (PMMA) mother particle, the formation of silicon dioxide powder by sol–gel reaction and their deposition onto the etched flat surface of calcium carbonate, the surface modification of deposited silicon dioxide with silane coupling agent, the removal of the mother particle with acetone, the formation of silicon dioxide powder by sol–gel reaction and deposition onto the exposed hemispherical surface of calcium carbonate, and the surface modification of deposited silicon dioxide with silane coupling agent. The synthesized microcapsules had a complete hemispherical structure and both hydrophilic and hydrophobic surfaces. Copyright © 2007 John Wiley & Sons, Ltd.     

牛血清白蛋白LB膜诱导方解石的生长

采用模拟生物矿化的方法,研究了牛血清白蛋白(BSA) LB膜对碳酸钙晶体成核和生长的诱导控制作用。XRD、SEM结果表明：在BSA单层LB膜诱导下,形成形状规则、边缘清晰的多层盘状方解石晶体,且沿(104)晶面取向生长。说明牛血清白蛋白(BSA) LB膜对碳酸钙的形貌、生长取向性有很好的调控作用。     

Chemical and thermal stability of alkanethiol and sulfur passivated InP(100)

InP(100) surfaces treated with Na2Sx9H20 and CnH(2n+1)SH are examined by contact angle measurement, X-ray photoelectron spectroscopy, and atomic force microscopy to determine the chemical and thermal behavior of these passivated surfaces. The surfaces coated by octadecanethiol (n = 18) self-assembled monolayers (SAMs) are found to be more stable toward oxidation than the S-passivated surface. The chemical stability of octadecanethiol SAMs in various environments is examined. The thiol monolayer is found to be stable in 0.1 M HCl but degrades in 0.1 M NaOH, boiling chloroform, and water. The behavior of these surfaces at elevated temperatures under a vacuum is also investigated. The octadecanethiol-coated InP(100) is stable up to 473 K, above which the films begin to degrade. Unlike other substrates on which the entire molecule including the sulfur headgroup desorbs together, on InP, the sulfur headgroup remains on the surface even after annealing to 673 K. These observations suggest that the desorption occurs by S-C bond cleavage as well as In-S bond cleavage. The sulfur of S-passivated InP is found to be more thermally stable than that of the octadecanethiol monolayer, perhaps due to their different bonding geometries and hence energies.