Critical adsorption on nonspherical colloidal particles

We consider a nonspherical colloidal particle immersed in a fluid close to its critical point. The temperature dependence of the corresponding order parameter profile is calculated explicitly. We perform a systematic expansion of the order parameter profile in powers of the local curvatures of the surface of the colloidal particle. This curvature expansion reduces to the short distance expansion of the order parameter profile in the case that the solvent is at the critical composition.     

Cooperativity in the adsorption of magnetic colloidal particles

In this paper we investigate the adsorption of magnetic particles onto magnetically patterned substrates. We find that the adsorption process is cooperative, where the probability of adsorption decreases with increasing substrate occupancy (namely, density of adsorbed particles). The effect of cooperativity can be accounted for by a simple modification of the adsorption probability as manifested by the binomial distribution. The negative cooperativity found in the magnetic particle adsorption is not due to direct repulsion between particles, but to screening of the surface's magnetic field by previously adsorbed particles. Thus, the adsorption of magnetic colloids on magnetic substrates is a self-limiting process.     

Microcalorimetric studies of the structure of supported bimetallic catalyst particles

Microcalorimetric studies of oxygen and hydrogen chemisorption during the last decade improved the understanding of the structure and structural dynamics of supported bimetallic catalyst particles. For example, it was found that on graphitic supports two different reduced surface compositions/structures can be created for base metal/noble metal particles. Appropriate treatments switch the surface from almost pure reduced base metal to true alloy. Calorimetric studies also indicate support interactions play a major role in controlling bimetallic particle surface structure. In contrast to behaviour found on graphitic supports, iron/noble metal particles supported on refractory oxides apparently do not form alloy surfaces. The reduced surface is dominated by the noble metal. Several studies indicate the value of the models of surface composition/structure developed using microcalorimetry for predicting the activity/selectivity of bimetallic particles.     

Effect of charged colloidal particles on adsorption of surfactants at oil-water interface

A change of oil/water interfacial tension in the presence of cationic or anionic surfactants in an organic phase was observed due to the addition of charged fine solids in the aqueous phase. The charged fine solids in the aqueous phase adsorb surfactants diffused from the oil phase, thereby causing an increase in the bulk equilibrium surfactant concentration in the aqueous phase, governed by the Stern-Grahame equation. Consequently, surfactant adsorption at the oil-water interface increases, which was demonstrated from the measured reduction of the oil-water interfacial tension. The increased surfactant partition in the aqueous phase in the presence of the charged particles was confirmed by the measured decrease in the surface tension for the collected aqueous solution after solids removal, as compared with the cases without solids addition.     

菲咯啉铜切割DNA反应的微量热法研究

利用流动式和间歇式微量热法研究了菲咯啉铜(Ⅱ)-巯基乙醇-O~2体系切割小牛胸腺双链DNA(dsDNA)反应的热力学,确定该DNA断链的总反应为较快的放热反应和焓驱动的反应,但该反应的前期为快速吸热过程,310.15K和pH=7.0时该反应的总摩尔反应焓(Δ~rH~m~,~3)和前期摩尔反应焓(Δ~rH~m~,~1)分别为-35.1和7.29kJ·mol^-^1。同时采用琼脂糖凝胶电泳法观察到了菲咯啉铜(Ⅱ)-巯基乙醇-O~2体系对DNA链的断裂现象。     

Specific cation adsorption on protein-covered particles and its influence on colloidal stability

Protein coated particles present an anomalous colloidal stability at high ionic strength when the classical theory (DLVO) predicts aggregation. This observed deviation from DLVO behaviour appears for electrolyte concentrations above some critical bulk value. As we have suggested in previous publications the existence of an additional short-range repulsive 'hydration force' due to specific hydrated cation adsorption could explain this anomalous stability. The overlap of the hydration layers when two particles approach should provoke this repulsive force. New evidence of this mechanism has been observed when electrophoretic mobilities of protein-carrying latex particles were measured at various concentrations of sodium and calcium chloride. In the latter case a sign reversal of zeta-potential was found, probably due to the specific adsorption of Ca(2+) ions on protein molecules. The adsorption increases with the medium pH. These results have been analyzed following the treatment proposed by Ohshima and co-workers for large charged colloidal particles coated with a layer of protein. This study shows an increase in the positive fixed-charge density on the protein caused by the adsorption of cations.     

SERS studies of the adsorption of guanine derivatives on gold colloidal nanoparticles

Surface enhanced Raman scattering spectra of guanine, guanosine and 2'-deoxyguanosine adsorbed on gold colloidal nanoparticles were obtained. From the striking similarity of the SERS spectra of these compounds, it can be evidenced that guanosine and 2'-deoxyguanosine adsorb on gold nanoparticles through the guanine moiety. The molecular sites involved in the interaction with the gold surface are the same for the 3 compounds: the oxygen of the carbonilic group and the N(7) atom. Guanine, guanosine and 2'-deoxyguanosine adsorb on the gold substrates with a tilted orientation with respect to the metal surface. SERS data were interpreted taking into account density functional theoretical (DFT) calculations of guanine.     

Surface-enhanced Raman scattering study of the adsorption of croconate violet on colloidal silver particles

Very stable silver particle suspension has been synthesized for use in surface-enhanced Raman scattering (SERS) spectroscopy with near-infrared exciting radiation. Such citrate-stabilized silver particles were obtained through a suitable control of the nucleation and growth process during the synthesis. The SERS spectra of the bis(dicyanomethylene) croconate dianion or croconate violet (CrocV) were obtained, with excitation in the near-infrared and in the visible region. The differences in the spectral patterns were correlated with a pre-resonance Raman effect of the adsorbate. The vibrational frequencies of CrocV isolated and interacting with silver surface were obtained through theoretical calculations using DFT method that together the surface selection rules allowed to perform the vibrational assignment of the SERS spectra and to infer the adsorption geometry.     

Microcalorimetric studies of the adsorption of N-ethylpyrrolidone,oligomeric and polymeric vinylpyrrolidone from CHCl3 on silica

Adsorption enthalpies of N-ethylpyrrolidone, oligomeric and polymeric vinylpyrrolidone from CHCl₃ solution on silica interfaces (Aerosil 200) have been measured at 25 °C by microcalorimetry. The dependence on surface coverage has been examined using measured adsorption isotherms. Binding enthalpies are calculated with fractions of adhered segments obtained by IR spectrometry and wetting enthalpies received from calorimetry. Fractions of adhered segments are derived from the adsorption enthalpies assuming equal binding enthalpies of monomers and polymer segments and considering desorption enthalpies of the solvent depending on the surface area of the polymer segments. The resulting enthalpies are compared with literature values from other solvents and the incongruity of the fraction of adhered segments obtained by IR, ESR, NMR and microcalorimetry is explained.Herrn Professor Dr. Robert Kerber zum 60. Geburtstag gewidmet.     

NMR studies of sorption and adsorption phenomena in colloidal systems

NMR methods provide chemically selective tools, particularly suitable to detect the molecular environment of molecular species in micro-heterogeneous materials. They are consequently applied to solve many questions in colloid science. The present review covers NMR studies of molecular adsorption onto particle surfaces as well as sorption into colloidal particles. Various methods ranging from liquid or solid state spectral analysis over spin relaxation to pulsed field gradient diffusion NMR have been employed in this field, monitoring either the chemical environment or the restricted dynamics of adsorbed or encapsulated guest molecules. Adsorption systems include surfactant layers, stabilizing ligands, small molecules, polymer layers or polyelectrolyte multilayers at the surface of various types of particles. Sorption into colloidal particles and detection of their position in specific compartments of the colloid are particularly relevant in systems employed as colloidal carriers, such as micelles, vesicles, or hollow polymeric capsules. With guest molecules considered as model compounds for drugs these studies have large relevance for the development of nanoparticle drug delivery systems.     

Microcalorimetric investigation of water vapor adsorption on silica gel

In this study, the activities of four ginsenosides Rc, Re, Rd, and Rf on splenic lymphocytes growth were studied by microcalorimetry. Some qualitative and quantitative information, such as the metabolic power–time curves, growth rate constant k, maximum heat-output power of the exponential phase P _max and the corresponding appearance peak time t _max, total heat output Q _t, and promotion rate R _p of splenic lymphocytes growth affected by the four ginsenosides were calculated. In accordance with thermo-kinetic model, the corresponding quantitative relationships of k, P _max, t _max, Q _t, R _p, and c were established, . Also, the median effective concentration (EC₅₀) was obtained by quantitative analysis. Based on both the quantitative quantity–activity relationships (QQAR) and EC₅₀, the sequence of promotion activity was Rc > Re > Rd > Rf. The analysis of structure–activity relationships showed that the number, type, and position of sugar moieties on the gonane steroid nucleus had important influences on the promotion activity of Rc, Re, Rd, and Rf on splenic lymphocytes growth. Microcalorimetry can be used as a useful tool for determining the activity and studying the quantity–activity relationship of drugs on cell.     

Microcalorimetric studies on the dismutation of superoxide anion catalyzed by superoxide dismutase

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Pulsed field gradient NMR studies of polymer adsorption on colloidal CdSe quantum dots

Pulsed field gradient nuclear magnetic resonance (PFG NMR) experiments have been used to examine ligand exchange between poly(2-(N,N-dimethylamino)ethyl methacrylate) (PDMA) (Mn = 12,000, Mw/Mn = 1.20, Nn = 78) and trioctylphosphine oxide (TOPO) bound to the surface of CdSe/TOPO quantum dots (QDs). We show that PFG 1H NMR can quantify the displacement of TOPO by PDMA through its ability to differentiate signals due to TOPO bound to the QDs versus those from TOPO molecules free in solution. For CdSe QDs with a band edge absorption maximum at 558 nm (diameter 2.7 nm by transmission electron microscopy), we determined that, at saturation, 8 polymer chains on average displace greater than 90% of the surface TOPO groups. At partial saturation, with an average of 6 polymer chains/QD, each TOPO displaced requires 28 DMA repeat units. Assuming that one Me2N- group binds to a surface Cd2+ for each TOPO displaced, we infer that only about 3% of the DMA units are directly bound to the surface. The remaining groups are present as loops or tails that protrude into the solvent and increase the hydrodynamic diameter of the particles.     

Microcalorimetric study of adsorption of glycomacropeptide on anion-exchange chromatography adsorbent

The adsorption of glycomacropeptide (GMP) from cheese whey on an anion-exchange adsorbent was investigated using isothermal titration microcalorimetry to measure thermodynamic information regarding such processes. Isotherms data were measured at temperatures of 25 and 45 °C, pH 8.2 and various ionic strengths (0–0.08 mol L⁻¹ NaCl). The equilibrium data were fit using the Langmuir model and the process was observed to be reversible. Temperature was observed to positively affect the interaction of the protein and adsorbent. Microcalorimetric studies indicated endothermic adsorption enthalpy in all cases, except at 45 °C and 0.0 mol L⁻¹ NaCl. The adsorption process was observed to be entropically driven at all conditions studied. It was concluded that the increase in entropy, attributed to the release of hydration waters as well as bounded ions from the adsorbent and protein surface due to interactions of the protein and adsorbent, was a major driving force for the adsorption of GMP on the anion-exchange adsorbent. These results could allow for design of more effective ion-exchange separation processes for proteins.     

微量热法研究过氧化氢酶底物抑制动力学

过氧化氢酶是需氧生物体内抗氧化酶系的重要组分。过氧化氢酶催化过氧化氢分解是一个两底物酶促反应,依照Chance提出的机理,反应速率方程具有一级反应方程的形式。此反应在高浓度底物存在的情况下,表现出明显的不可逆底物抑制。本研究用热动力学方法研究了这一反应,提出了一种不可逆底物抑制机理,并应用该机理求出了相关动力学参数。在310.15K,pH=7.0时k0=9.6×10^5L·mol^-1^·s^-1,k1/k2=2.9×10^6。实验结果证明此机理正确有效。     

Microcalorimetric studies on the antimicrobial actions of different cephalosporins

Microcalorimetry was applied to study the effect of cephalosporins (cefazolin sodium and cefonicid sodium) on the E. coli growth. The microbial activity was recorded as power-time curves through an ampoule method with a TAM Air Isothermal Microcalorimeter at 37°C. The parameters such as the growth rate constant (k), inhibitory ratio (I), the maximum power output (P _m) and the time corresponding to the maximum power output (t _m) were calculated. The change tendencies of k, with the increasing of concentration (C) of the two cephalosporins, are similar which show that cefazolin sodium and cefonicid sodium have the same inhibitory mechanism. The experimental results reveal that cefonicid sodium has a stronger antibacterial activity towards E. coli than that of cefazolin sodium and this was coincide with the clinical manifestations.     

Microcalorimetric and infrared studies of ethanol and acetaldehyde adsorption to investigate the ethanol steam reforming on supported cobalt catalysts

Microcalorimetric and infrared studies of ethanol and acetaldehyde adsorption were carried out on fresh and deactivated ZnO-supported cobalt catalysts (Co/ZnO and Co/ZnO(d), respectively) as well as on ZnO support alone. The results were used to analyze the catalytic behavior of these materials for ethanol and acetaldehyde steam-reforming reactions. The Co/ZnO(d) sample contained extensive carbon deposition as shown by Raman spectroscopy and transmission electron microscopy. On fresh Co/ZnO, the adsorption energetics of ethanol and acetaldehyde (an intermediate in the ethanol reforming reaction) were similar. Under steam-reforming conditions at low conversion values of ethanol, acetaldehyde was selectively yielded. The presence of surface acetate species was shown from IR spectra following acetaldehyde adsorption. Besides that, the Co/ZnO catalyst was active and showed a high selectivity toward the reforming products, H2 and CO2, when the steam reforming of acetaldehyde was carried out at low conversion values. In contrast, on the deactivated sample, the strongest adsorption sites of ethanol have disappeared, and acetaldehyde was adsorbed with higher energy with respect to ethanol, resulting in the blockage of the active sites; a poorer catalytic performance in both ethanol and acetaldehyde steam-reforming reactions is observed. The presence of acetate species after adsorption of acetaldehyde on Co/ZnO(d) was not shown. The polymerization of acetaldehyde over Co/ZnO(d) was related to the decomposition of acetaldehyde under reforming conditions to give CO and CH4.