Production and Application of the Langmuir Aggregates of Eosine with Cetyl Trimethyl Ammonium Bromide

The procedure of microphase adsorption–spectral correction is applied to the interaction of eosine Y (EO) to the micelles of cetyl trimethyl ammonium bromide (CTAB). The Langmuir aggregation of EO on CTAB occurs owing to microelectrostatic attraction. The results have shown that at pH 3.8, monomeric and micellar aggregates have the structure EO₅·CTAB₂ and (EO₅·CTAB₂)₃₉. The adsorption constant of an aggregate is 7.01·10⁵, its molar absorption coefficient is = 8.8·10⁴ liters·mole^–1·cm^–1 at 550 nm. Application of the aggregation of EO on CTAB gives satisfactory results for quantitative determination of cation surfaceactive agents (surfactants).     

用有限解析差分格式数值求解化学输运方程

本文用有限解析差分格式研究在多孔介质中化学输运问题的数值模型,系统地计算结果表明:1.有限解析差分格式能够消除数值弥散和伪振荡; 2.随着弥散数(Peclct数)的减小(增加),浓度突破曲线将延迟到达和形状变陡,最终趋近浓度对流曲线;3.当流速数增加后,非稳态吸附对浓度分布的影响趋近稳态吸附的影响。     

Random and cooperative sequential adsorption on infinite ladders and strips

We analyze various processes where particles are added irreversibly and sequentially at the sites of infinite ladders or broader strips (i.e., on terraces) of adsorption sites. For sufficiently narrow strips or ladders, exact solution in closed form is possible for a variety of processes. Often this is most naturally achieved by mapping the process onto an equivalent one-dimensional process typically involvingcompetitive adsorption. We demonstrate this procedure for sequential adsorption with nearest-neighbor exclusion on a 2× square ladder. For other select processes on strips slightly too broad for exact solution, almost exact analysis is possible exploiting an empty-site shielding property. In this way, we determine a jamming coverage of 0.91556671 for random sequential adsorption of dimers on a 2× square ladder. For broader strips, we note that the complexity of these problems quickly approaches that for × lattices.     

Hydrogen adsorption on Pt-decorated closed-end armchair (3,3), (4,4) and (5,5) single-walled carbon nanotubes

ABSTRACT

Structures of small lengths of capped (3,3), (4,4) and (5,5) single-walled carbon nanotubes (SWCNTs) and their structures decorated by Pt atom and Pt_n clusters (n = 2–4) were obtained using density functional theory calculations. Binding abilities of Pt atom and Pt_n clusters on the outer surface of SWCNTs at various adsorption sites were explored. Adsorptions of H₂ onto Pt atom of the Pt-decorated (3,3), (4,4) and (5,5) SWCNTs were studied and their adsorption energies are reported. The thermodynamic properties and equilibrium constants for H₂ adsorptions on the Pt₄-decorated (3,3), (4,4) and (5,5) SWCNTs were obtained. The adsorption of H₂ on the Pt atom of the Pt₄/(3,3) SWCNT was found to be the most preferred reaction of which enthalpy and free energy changes at room temperature are ?46.61 and ?23.99 kcal/mol, respectively.     

H2S在Fe(100)面吸附的第一性原理研究

基于密度泛函理论第一性原理, 在广义梯度近似下, 研究了表面覆盖度为0.25 ML (monolayer)时硫化氢分子在Fe(100)面吸附的结构和电子性质, 并与单个硫原子吸附结果进行了对比. 结果表明: 硫化氢分子吸附在B2位吸附能最小为-1.23 eV, 最稳定, B1位吸附能最大为-0.01 eV, 最不稳定; 并对硫化氢分子在B1位和B2位吸附后的电子态密度进行了分析, 也表明了吸附在B2位稳定, 且吸附在B2位后硫化氢分子几何结构变化不大; 将硫化氢中硫原子吸附与单个硫原子吸附的电子性质进行了比较, 发现前者吸附作用非常微弱; 同时对吸附后的Fe(100)面进行了对比, 单个硫原子吸附的Fe(100)面电子态密度出现了一系列峰值且离散分布, 生成了硫化亚铁, 表明在硫化氢环境下, 主要是硫化氢析出的硫原子发生了吸附. 关键词： 第一性原理 Fe(100)表面 吸附能 硫化氢     

Detection of tobacco smoke deposition by hyperpolarized krypton-83 MRI

Despite the importance of the tobacco smoke particulate matter in the lungs to the etiology of pulmonary disease in cigarette smokers, little is currently known about the spatial distribution of particle deposition or the persistence of the resulting deposits in humans, and no satisfactory technique currently exists to directly observe tobacco smoke condensate in airways. In this proof-of-principle work, hyperpolarized (hp) 83Kr MRI and NMR spectroscopy are introduced as probes for tobacco smoke deposition in porous media. A reduction in the hp-83Kr longitudinal (T1) relaxation of up to 95% under near-ambient humidity, pressure and temperature conditions was observed when the krypton gas was brought into contact with surfaces that had been exposed to cigarette smoke. This smoke-induced acceleration of the 83Kr self-relaxation was observed for model glass surfaces that, in some experiments, were coated with bovine lung surfactant extract. However, a similar effect was not observed with hp-(129)Xe indicating that the 83Kr sensitivity to smoke deposition was not caused by paramagnetic species but rather by quadrupolar relaxation due to high adsorption affinity for the smoke deposits. The 83Kr T1 differences between smoke-treated and untreated surfaces were sufficient to produce a strong contrast in variable flip angle FLASH hp-83Kr MRI, suggesting that hp-83Kr may be a promising contrast agent for in vivo pulmonary MRI.     

Adsorption of 4,4′‐thiobisbenzenethiol on silver surfaces: surface‐enhanced Raman scattering study

Adsorption of 4,4′‐thiobisbenzenethiol (4,4′‐TBBT) on a colloidal silver surface and a roughened silver electrode surface was investigated by means of surface‐enhanced Raman scattering (SERS) for the first time, which indicates that 4,4′‐TBBT is chemisorbed on the colloidal silver surface as dithiolates by losing two H‐atoms of the S H bond, while as monothiolates on the roughened silver electrode. The different orientations of the molecules on both silver surfaces indicate the different adsorption behaviors of 4,4′‐TBBT in the two systems. It is inferred from the SERS signal that the two aromatic rings in 4,4′‐TBBT molecule are parallel to the colloidal silver surface as seen from the disappearance of ν_{C H} band (3054 cm⁻¹), which is a vibrational mode to be used to determine the orientation of a molecule on metals according to the surface selection rule, while on the roughened silver electrode surface they are tilted to the surface as seen from the enhanced signal of ν_{C H}. The orientation of the C‐S bond is tilted with respect to the silver surface in both cases as inferred from the strong enhancement of the ν_{C S}. SERS spectra of 4,4′‐TBBT on the roughened silver electrode with different applied potentials reveal that the enhancement of 4,4′‐TBBT on the roughened silver electrode surface may be related to the chemical mechanism (CM). More importantly, the adsorption of 4,4′‐TBBT on the silver electrode is expected to be useful to covalently adsorb metal nanoparticles through the free S H bond to form two‐ or three‐ dimensional nanostructures. Copyright © 2007 John Wiley & Sons, Ltd.     

Cs/GaN(0001)吸附体系电子结构和光学性质研究

采用基于第一性原理的密度泛函理论平面波超软赝势方法计算了 1/4ML Cs原子吸附 (2 × 2) GaN(0001) 表面的吸附能、能带结构、电子态密度、电荷布居数、功函数和光学性质. 计算发现, 1/4ML Cs 原子在 GaN(0001) 表面最稳定吸附位为 N 桥位, 吸附后表面仍呈现为金属导电特性, Cs原子吸附GaN(0001)表面后主要与表面 Ga 原子发生作用, Cs6s 态电子向最表面 Ga 原子转移, 引起表面功函数下降. 研究光学性质发现, Cs 原子吸附 GaN(0001) 表面后, 介电函数虚部、吸收谱、反射谱向低能方向移动.     

Surface chemistry of alkyl and perfluoro ethers: a FTIR and ab initio study of adsorption and decomposition of CF3OCF3 on an Al2O3 surface

The adsorption and thermal decomposition of perfluorodimethyl ether, (CF₃)₂O, on a high-surface-area Al₂O₃ surface was investigated by FTIR under both vacuum and pressure conditions. IR spectra in the 4000-1050 cm⁻¹ range were collected and the spectral assignments were assisted by quantum chemical ab initio calculations. The spectral evidence indicated that (CF₃)₂O decomposed to form adsorbed fluoroformate, FCOO (ads). Increases of temperature (up to 525 K) caused the FCOO (ads) to convert to hydrogen formate, HCOO (ads). Surface hydroxyl groups participated in the decomposition of (CF₃)₂O and the conversion of FCOO (ads) to HCOO (ads). A decomposition mechanism is proposed.     

Photochemistry in ordered physisorbed monolayers of dinitrogen tetroxide

The effects of physisorption and two-dimensional ordering on the photochemistry of N₂O₄ were investigated. Ordered monolayers were prepared by adsorption of NO₂ at 100 K on a water-ice surface. Irradiation with a continuous light source in the wavelength region 300–400 nm or with pulsed laser radiation at 355 nm resulted in exclusive desorption of NO₂. This desorption was induced by electronic absorption directly in the adsorbate via a transition corresponding to the ( )¹B_2u←( )¹A_g transition in N₂O₄, as in the gas phase. However, the subsequent dynamics in the excited state were markedly different from the gas-phase counterpart. Time-of-flight mass spectrometry of NO₂ photodesorbed at 355 nm revealed a most probable fragment translational energy of ca. 17 meV; and the angular distribution of the nascent NO₂ was peaked sharply in a direction around 10° from the normal. It is apparent that, despite the weak interaction with the substrate, significant energy transfer occurs in the ordered physisorbed monolayer to yield nascent NO₂ with very low translational energy and a constrained angle of escape which is consistent with a high degree of adsorbate order and alignment.