Light Scattering Study of Turbid Heat-Set Globular Protein Gels Using Cross-Correlation Dynamic Light Scattering

The structure factor of aqueous solutions of the globular protein β-lactoglobulin was determined as a function of heating time at 76°C. We show how the effect of multiple scattering on the scattered light intensity can be effectively corrected using cross-correlation dynamic light scattering even if the transmission is only 1%. The structure factor of aggregated and gelled proteins can be described by the Ornstein–Zernike equation. The system is characterized by a correlation length that increases with heating time and stabilizes some time after the gel is formed. The correlation length of the protein gels decreases with decreasing concentration. Measurements after progressive dilution of a sample close to the gel point showed that the protein aggregates are initially interpenetrated and disinterpenetrate upon dilution.     

Characterization of Titania/Silica Gel by Means of Low-Pressure Nitrogen Adsorption

Adsorbents synthesized by grafting of titania onto mesoporous silica gel surfaces at different temperatures were studied by means of nitrogen adsorption–desorption and water desorption. The pore size distribution f(R_p) of titania/silica gel depends on the titania concentration (C_TiO2) and the temperature of titania synthesis. Nonuniformity of TiO₂ phase is maximal at a low C_TiO2 value (3.2 wt.% anatase deposited at 473 K), and two peaks of the fractal dimension distribution f(D) are observed at such a concentration of titania, but at larger C_TiO2 values, only one f(D) peak is seen. More ordered filling of pores and adsorption sites by nitrogen, reflecting in the shape of adsorption energy distributions f(E) at different pressures of adsorbate, is observed for adsorbent with titania (rutile+anatase) grafted on silica gel at a higher temperature (673 K).     

Thermodynamic quantities of surface formation of aqueous electrolyte solutions. V. Aqueous solutions of aliphatic amino acids

The surface tension of aqueous solutions of glycine, L-alanine, L-valine, and L-leucine has been observed using the drop volume method as a function of temperature and concentration. The L-leucine molecules form an adsorbed film, while glycine affects the water surface in accordance with simple salts which dissociate into cations and anions completely. The surface tension data have been analyzed in view of K. Motomura's thermodynamic treatment (J. Colloid Interface Sci.64, 348 (1978)), and the thermodynamic quantities relevant to the surface have been shown systematically.     

Adsorption of 1,4-Benzenedithiol on Gold and Silver Surfaces: Surface-Enhanced Raman Scattering Study

The adsorption behavior of 1,4-benzenedithiol (1,4-BDT) on colloidal gold and silver surfaces has been investigated by means of surface-enhanced Raman scattering (SERS). 1,4-BDT chemisorbed dissociatively on both gold and silver surfaces but as mono- and dithiolate, respectively. Regardless of the bulk concentration of 1,4-BDT, only a monolayer was assembled on the silver surface with a flat orientation by forming two Ag–S bonds. On the gold surface, the monothiolate species,1,4-BDT⁻¹, appeared to assume a rather flat orientation at a very low surface coverage, but as the surface coverage was increased, the adsorbate took a perpendicular orientation. Furthermore, when the bulk concentration of 1,4-BDT was close to that required for a full-monolayer coverage limit, a band assignable to the S–S stretching vibration appeared at 536 cm⁻¹ in the gold sol SERS spectra. A separate ellipsometry measurement performed with vacuum-evaporated gold substrates revealed that up to tetralayers could be assembled on gold in 1 mM n-hexane solution of 1,4-BDT while at best a bilayer formed in either methanol or ethanol solution. The different adsorbate structure of 1,4-BDT on gold and silver was overall quite comparable to that of p-xylene-α,α′-dithiol.     

Sol–gel processing of IrO<Subscript>2</Subscript>–TiO<Subscript>2</Subscript> mixed metal oxides based on a hexachloroiridate precursor

Mixed IrO₂–TiO₂ oxides were prepared by the sol–gel method upon acid-catalysed hydrolysis of an iridium solution in ethanol mixed with titanium tetraethoxide in ethanol. The iridium solution was obtained by reaction of the sodium hexachloroiridate(IV) precursor in the presence of sodium ethoxide in ethanol. Gels were formed in all but the high-Ir samples. Analysis of the dried gels showed minority-phase enrichment at the surface and the presence of Ir(III), while microscopy showed evidence for dispersed iridium-containing nanoparticles (1–20 nm in diameter). XRD powder patterns of the calcined material showed peaks due to a small amount of crystalline NaCl impurity which could be removed by washing. This left amorphous phases, except in the Ir:Ti 3:2 case, which showed evidence for the presence of separate crystalline oxide phases: anatase, IrO₂ and Ti _x Ir_1−x O₂.     

纳米TiO2低温水解法的晶型控制合成及其表面织构的研究

分别以TiCl₄，Ti(NO₃)₄和Ti(SO₄)₂为前驱体，在低温和强酸性条件下，通过水解反应可控地合成了具有不同晶相组成，且比表面积较高的纳米TiO₂，并用XRD，TEM和N₂^-吸附脱附技术对其晶相、粒径大小、形貌及比表面积进行了表征。结果表明，钛离子在有Cl^-、NO₃^-存在的酸性溶液中水解，水解温度≤80 ℃，可以生成结晶良好的具有细小晶粒尺寸和较高比表面积的金红石型纳米TiO₂粉体，水解温度>80 ℃，反而有锐钛矿型TiO₂生成，而在有SO₄^2-存在的酸性溶液中，TiO₂样品的晶相组成不随水解温度的变化而改变，均为锐钛矿型，其比表面积可达300 m²·g^-1。     

Flow of Multicomponent Electrolyte Solutions through Narrow Pores of Nanofiltration Membranes

The slow flow of a multicomponent electrolyte solution in a narrow pore of a nanofiltration membrane is considered. The well-known semiempirical method of subdivision of electrical potential into quasi-equilibrium and streaming parts and the definition of streaming concentrations and pressure are discussed. The usefulness of this tool for solving the electrohydrodynamic equations is shown and justified: the use of a small parameter enables a system of electrohydrodynamic partial differential equations to be reduced to a system of ordinary differential equations for streaming functions. Boundary conditions for streaming functions at both the capillary inlet and outlet are derived. The proposed model is developed for the flow of a multicomponent electrolyte solution with an arbitrary number of ions. This is coupled with (i) the introduction of specific interactions between all ions and the pore wall and (ii) the inclusion of the dissociation of water in both conservation and transport equations. Effective distribution coefficients of ions are introduced that are functions of both the specific interaction potentials and the surface potential of the nanofiltration membrane material. The axial dependency of surface potential is expressed by the use of a charge regulation model from which the discontinuity in electric potential and ion pore concentrations at the pore inlet and outlet can be described.A relation between the frequently used capillary and homogeneous models of nanofiltration membranes is developed. An example of application of the homogeneous model for interpretation of experimental data on nanofiltration separation of electrolyte solutions is presented, which shows a reasonable predictive ability for the homogeneous model.     

Adsorption and direct probing of fibrinogen and sodium myristate at the air/water interface

Fibrinogen (FB), a serum protein, is considered a major inhibitor of lung surfactant function at the lining layer of the alveoli. In this study, the adsorption of aqueous bovine FB at the air/water interface was investigated with tensiometry and directly probed for the first time with ellipsometry and infrared reflection adsorption spectroscopy (IRRAS). The tension results show that FB has moderate surface activity. The surface densities of FB were calculated by using two different ellipsometry models to range from 3±0.2 to 17±2 mg/m², for 7.5 to 750 ppm of FB in water at 25°C. Although FB at concentrations from 75 to 750 ppm reached about the same steady surface tension value, the surface densities at 750 ppm FB were substantially larger. The same techniques were used for studying aqueous mixtures of 7.5 to 750 ppm FB with 2 mM of sodium myristate (SM) to investigate a possible interaction of the SM with the protein. The behavior of the FB/SM mixtures was found to be close to that of SM alone. The surface tension of the FB/SM mixtures reached values less than 10 mN/m under surface area oscillation at 20 or 80 rpm. These results and the ellipsometry and the IRRAS results indicate that at a concentration of 2 mM SM, FB, up to 750 ppm, does not inhibit the surfactant surface-tension-lowering function. In certain cases the results demonstrate that FB and SM may act cooperatively in lowering the surface tension.     

Simple sol–gel route to synthesis of mesoporous TiO<Subscript>2</Subscript>

Mesoporous TiO₂ with a high specific surface area was prepared from titanium sulfate solution in a simple sol–gel route, where formamide was used as pH adjusting agent. TiO₂ had a high resistance to phase transformation, and maintained monophasic anatase after calcinating at 600 °C. The highest specific surface area achieved on the prepared samples is 231.90 m² g⁻¹ after calcinating at 450 °C.     

Rheology and Permeability of Crosslinked Polyacrylamide Gel

Gels produced by crosslinking polyacrylamide solutions with chromium (III) have been characterized by dynamic rheology studies. To vary the gel strength, different polymer concentrations were used, while keeping the temperature, salinity, and crosslinker concentration constant. Both the loss and storage moduli increased with the polymer concentration for this gel system. The storage modulus at the end of the gelation was used to characterize the gel strength. Steady-state water flow experiments through gel-filled capillary tubes were performed, with the aim of linking the gel strength and flow behavior. The permeability was found to be a function of the water flow rate (velocity) and polymer concentration. Two parameters were used to characterize the flow behavior, intrinsic gel permeability and elasticity index, which are each functions of the polymer concentration. However, only one parameter is needed to fully identify the flow and rheological gel properties, as the elasticity index and storage modulus are linked by a power-law relationship. The loss modulus and intrinsic permeability are correlated with the storage modulus and elasticity index, respectively. A theoretical model for this behavior linking both gel properties based on the dual domain structure was used to demonstrate that the flow and rheological behavior of the gel are indeed related and that the gel strength controls the water permeability. Implications for prediction of flow of water through gels emplaced in a porous medium are discussed.     

Removal of proteinaceous soils using hydroxyl radicals generated by the electrolysis of hydrogen peroxide

We have developed here for the first time a novel method to generate hydroxyl radicals, *OH, by applying slightly negative electric potentials (-0.2--0.8 V vs Ag/AgCl) to the surface of a metal (or metal oxide) that is in contact with hydrogen peroxide solution containing a supporting electrolyte. Namely, *OH radicals were generated at the surface by the electrolysis of hydrogen peroxide according to the equation, H2O2+e- --> *OH+OH-. This method was used to clean a stainless steel fouled with a model protein, beta-lactoglobulin. The *OHs generated at the surface were effective in removing beta-lactoglobulin that had been irreversibly adsorbed, by several minutes of treatment at room temperature (22+/-2 degrees C). The removal rates measured for various concentrations of H2O2 and supporting electrolyte and different potentials were determined exclusively by the electric current.     

Dynamic surface tension and its diffusional decay of dodecyl ethoxylates with different homologue distribution

Dynamic surface tension and its diffusional decay have been studied with four different polydisperse C12E7 at different temperatures and different concentrations. The CMC and the headgroup area from equilibrium surface tension were shown with polydispersity and temperature. The chain length of oxyethylene on the surface was derived from comparison between the headgroup area of monodisperse dodecyl ethoxylates and that of polydisperse C12E7. The values for (Deff/D) were deduced with a diffusion-controlled adsorption model using parameters obtained from equilibrium surface tension. It was shown at short adsorption time that molecules were really adsorbed onto the surface in a diffusion-controlled manner. At a comparably long adsorption time, the ratios (Deff/D) were calculated by assuming the selective adsorption onto the surface. The modified Arrhenius-type equation was proposed by putting a concentration term in front of the exponential terms. The modified Arrhenius-type equation gave Ea=30 kJ/mole for this system. Ea directly derived without an Arrhenius plot was between 9 to 11 kJ/mole. It was an indication that the activation energy alone was not enough to explain the decay of dynamic surface tensions.     

低密度薄水铝石晶体的水热生长过程

对Al2(SO4)3-CO(NH2)2-H2O体系在[Al3＋]=0.2 mol•L－1、[CO(NH2)2]:[Al3＋]=2∶1和反应2 h的水热条件下,不同反应温度的晶体生长过程进行了研究,得到呈多孔、针状团簇体状的微米级低密度薄水铝石晶体.采用ICP-AES、XRD、FT-IR、SEM、BET和粒径分布等手段对反应液和产物进行了分析和表征.结果表明,140 ℃时氢氧化铝凝胶或无定形粉体的析出已大部分完成,温度升高到180 ℃后,产物的结晶度变好,堆密度从117.2 kg•m－3相应增加到158.2 kg•m－3,比表面也从75.3 m2•g－1增加到88.3 m2•g－1,但平均粒径有所下降.晶体前驱体在550 ℃焙烧2 h后完全转化为形貌相似并且比表面增加的γ-Al2O3.     

Crystal phase evolution of TiO2 nanoparticles with reaction time in acidic solutions studied via freeze-drying method

The crystal phase evolution of TiO₂ nanoparticles, during hydrolysis and condensation of titanium tetraisopropoxide, was quenched at various reaction times by a freeze-drying method, followed by various characterizations. Three types of solutions with different acid input times were studied: (1) addition in infinite time (no addition), (2) addition at 24 h after the hydrolysis/condensation reaction started, and (3) addition from the beginning of the reaction. The acid-free solution yielded amorphous TiO₂, which transformed to anatase very slowly. The acid input in 24 h resulted in a fast transformation of amorphous to a metastable anatase having a highly distorted atomic arrangement: thereby its transformation to a more stable phase, rutile, was suitable. The acid addition from the beginning of the reaction yielded the formation of a relatively stable anatase from the hydrolysis seed, thereby the subsequent transformation to rutile was sluggish.     

玻璃微珠/Ag/TiO2可见光催化剂的制备与表征

通过离子交换法将Ag纳米颗粒负载于玻璃微珠的表面及浅表层,并以钛酸四丁酯的乙醇溶液为前驱体,将TiO₂负载于包含银的玻璃微珠表面,制得一种玻璃微珠/Ag/TiO₂复合光催化剂。由于纳米银的表面等离子体吸收效应,该复合光催化剂具有一定的可见光响应特性。利用XRD、SEM对样品进行表征,可发现玻璃微珠表面形成一层均匀多孔的锐钛矿TiO₂,其粒径均在50 nm左右。由漫反射光谱可得出该催化剂具有较强的可见光吸收,并在降解甲基橙溶液的试验中表现出较好的可见光催化活性。     

H(2)O Outgassing Properties of Fumed and Precipitated Silica Particles by Temperature-Programmed Desorption

Temperature-programmed desorption was performed at temperatures up to 850 K on as-received fumed and precipitated silica particles. Physisorbed water molecules on both types of silica had activation energies in the range of 38–61 kJ/mol. However, the activation energies of desorption for chemisorbed water varied from 80 to >247 kJ/mol for fumed silica, Cab-O-Sil-M-7D, and 96 to 155 kJ/mol for precipitated silica, Hi-Sil-233. Our results suggest that physisorbed water can be effectively pumped away at room temperature (or preferably at 320 K) in a matter of hours. Chemisorbed water with high activation energies of desorption (>126 kJ/mol) will not escape silica surfaces in 100 years even at 320 K, while a significant amount of the chemisorbed water with medium activation energies (80–109 kJ/mol) will leave the silica surfaces in that time span. Most of the chemisorbed water with activation energies <126 kJ/mol can be pumped away in a matter of days in a good vacuum environment at 500 K. We had previously measured about 0.1–0.4 wt% of water in silica-reinforced polysiloxane formulations containing 21% Cab-O-Sil-M-7D and 4% Hi-Sil-233. Comparing present results with these formulations, we conclude that the adsorbed H₂O and the Si–OH bonds on the silica surfaces are the major contributors to water outgassing from these types of silica-filled polymers.     

二氧化钛纳米微粒的制备与光催化活性

本文采用溶液－凝胶法制备了粒径为１０－２０ｎｍ左右的二氧化钛纳米微粒。用ＸＲＤ研究了二氧化钛溶胶的热处理过程,研究表明温度在４７３Ｋ－６７３Ｋ左右ＴｉＯ２向量 粒呈不规整锐钛矿结构,粒径约为１０－２０ｎｍ。在８７３Ｋ左右ＴｉＯ２微粒出现锐钛矿与金红石型混晶结构。     

Contribution to the Determination of Kinetic Parameters of the Sol-Gel Transformation by Rheological Measurements

The system tetraethoxysilane(TEOS)–water–ethanol has been studied by rheological measurements. Different molar ratios of TEOS : water (1 : 4, 1 : 10, and 1 : 20) are studied at different temperatures (30, 40, and 50°C). The dynamic viscosity (rotating mode) at a constant shear rate (100 s⁻¹) and the elastic and viscous moduli (oscillating mode) at a constant frequency (1 Hz) are determined. The viscosity–time curves are evaluated by application of a nucleation and particle growth model. Good agreement between experiments and theory is observed. The model allows the determination of the complex rate constant of silica precipitation. The temperature-dependent measurements gave the possibility to determine the apparent energy of activation by common methods. The results are in agreement with data from the literature. The gel time defined as intersection point of elastic and plastic moduli and its dependence on temperature are evaluated by the Smoluchowski model. The energy of activation for the coagulation was determined and found to be in the correct order of magnitude.     

Preparation and characterization of hollow spheres of rutile

Hollow spherical particles of rutile were obtained by coating colloidal polystyrene beads with a titanium oxide hydrate layer and subsequently calcining at elevated temperatures under an oxygen atmosphere. In order to investigate the optimum conditions for the preparation of these hollow beads the maximum temperature and heating rate were systematically varied. The dimensions of the voids and the shell thickness of the hollow beads can be tailored by the size of the polystyrene beads and the thickness of the inorganic layer, respectively.     

Analysis of the Silica Surface Free Energy by the Imbibition Technique

The surface free energy of silica and its components have been evaluated from imbibition experiments performed with liquids of differing surface properties by the distance–time method. Data were analyzed by a parabolic fit to Washburn's equation, because of the uncertainty in the exact position and time at which penetration begins in these kinds of experiments. In addition to the mathematical treatment of the experimental results, the influence of the components and parameters of the surface tension of the liquids used on the values of the solid surface free-energy components has been analyzed.