The influence of pH and anions on the adsorption mechanism of rifampicin on silver colloids

The influence of pH and anions on the adsorption mechanism of rifampicin on colloidal silver nanoparticles has been analysed by electronic absorption, resonance Raman (RR) and surface‐enhanced resonance Raman spectroscopy (SERRS). Rifampicin is a widely used antibiotic with a zwitterionic nature. SERRS spectra of rifampicin adsorbed on silver sols, prepared using hydroxylamine hydrochloride as reducing agent, undergo dramatic changes upon lowering the pH. The spectral form changes progressively from that characteristic of chemisorbed rifampicin (at pH > 7) to one very similar to the rifampicin RR spectrum (at lower pH), indicative of a modification of the adsorption mechanism on the surface of the Ag nanoparticles. The RR‐type SERRS spectrum is proposed to result from formation of an ion pair between rifampicin and Cl⁻ anions, which, deriving from the colloid preparation, are adsorbed on the Ag surface. The addition of anions to the hydroxylamine hydrochloride sol facilitates conversion from the chemisorbed to ion pair form and leads to an order of magnitude increase in the SERRS signal. Copyright © 2007 John Wiley & Sons, Ltd.     

Exciton energy transfer between adsorbates

The electron excitation energy transfer between adsorbed molecules on a solid surface via virtual and real surface excitons is considered. The rate of energy transfer via virtual excitons is calculated analytically. The nonradiative energy transfer to surface impurity centers is considered in the case of rapid migration of virtual or real excitons leading to repeatedly changed distances between centers of excitation localization. A theoretical model of the kinetics of “surface exciton-T-center” cross annihilation is constructed as a mirror image of the theory of cross annihilation of oxygen-containing objects adapted to a system of quasiparticles.     

CO adsorption on Rh, Pd and Ag atoms deposited on the MgO surface: a comparative ab initio study

The adsorption properties of CO molecules adsorbed on Rh, Pd, and Ag atoms supported on various sites of the MgO surface have been studied by means of a density functional cluster model approach. The metal atoms are stabilized with different binding energies on the regular and morphological defect sites of the surface. Among others we considered oxide anions, neutral and charged anion vacancies (F centers) located at terraces, steps, edges, and corners. CO is used as a probe molecule to characterize where the metal atoms are located. This is done by analyzing how the metal-CO binding energy and the C-O stretching frequency change as function of the substrate site where the metal atom is bound.     

Adsorption and deposition of anthraquinone-2-carboxylic acid on alumina studied by inelastic electron tunneling spectroscopy, infrared reflection absorption spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy

The adsorption state of anthraquinone-2-carboxylic acid (AQ-2-COOH) deposited from acetone solutions (0.01-1.00 mg/ml) on native oxide surfaces of Al films was characterized by inelastic electron tunneling spectroscopy, infrared reflection absorption spectroscopy, and X-ray photoelectron spectroscopy. The oxide was prepared on evaporated Al films at room temperature in an oxygen-dc glow discharge. The morphology of the deposited AQ-2-COOH on the oxide surfaces was observed and analyzed by atomic force microscopy. These surface analyses showed that AQ-2-COOH is adsorbed predominantly as a uniform nanometer-scale film of carboxylate anions on the oxide surfaces deposited from solutions with concentrations lower than or equal to 0.02 mg/ml. It was found that AQ-2-COOH is adsorbed as both a uniform film of anions and as micron-sized particles of neutral molecules with heights of a few tens of nanometers when AQ-2-COOH is deposited from solutions with concentrations higher than 0.02 mg/ml. A comparison of the results obtained by these surface analytical techniques clearly shows the features and advantages of these analytical techniques.     

Charging and stabilization of Pd atoms and clusters on an electron-rich MgO surface

We report density functional theory calculations on the interaction of Pd atoms and small Pd clusters with an electron-rich MgO surface. This surface can be generated by forming a specific kind of defects, named (H⁺)(e⁻) centers, using well known chemical recipes. By deposition of gas-phase Pd atoms on the properly functionalized MgO surface, one can generate collections of small Pd cluster anions with peculiar chemical properties. The (H⁺)(e⁻) centers act as nucleation sites for diffusing Pd atoms and favor the formation of small, thermally stable clusters. The presence of an extra charge on the metal cluster results in a large vibrational red-shift of adsorbed CO molecules. The present results intend to stimulate experimental work to produce stable metal cluster anions on the surface of an ionic oxide.     

New surface ionization processes

The results of analysis of processes including surface ionization are presented. It is found that these processes do not fit into the classical theory of surface ionization. This concerns the processes with diffusion exchange of particles between the adsorbed layer and the bulk of the emitter, catalytic processes on the emitter surface involving individual centers, as well as processes occurring in the adsorbed layers under illumination, electron bombardment, and in electric fields. We consider the results of analysis of surface ionization of alkali metal atoms and organic molecules on the surface of gold intermetallide (Na _x Au _y ), considerably extending information about this phenomenon.     

Stability of negative ions near the surface of a solid

Stationary states of molecular negative ions (anions) near the surface of a solid are investigated. The lone electron is assumed to interact with a diatomic molecule and the surface of the solid. The energies of electron levels are determined by solving the 2D Schrödinger equation. It is shown that its stable solutions exist at distances from the surface greater than some critical distance, otherwise the electron is detached from the anion. In the case of attraction between the electron and the solid, the interaction potential between the anion and the solid appears to have the Lennard-Jones form and the ion is separated from the surface by some equilibrium distance.     

The formation of new adsorption centers on platinized SiO2 surfaces

Kinetic and spectral characteristics of luminescence and excitation of luminescence of magnesium phthalocyanine (MgPc) molecules adsorbed on silicon dioxide (SiO₂) are studied. They are found to be affected by finely divided platinum (Pt) present at the surface and hydration. The deposition of a Pt catalyst on SiO₂ leads to the formation of new centers. Adsorption of MgPc molecules at these centers increases the lifetime of excited states of the former. Luminescence of charge transfer complexes and the protonized form of phthalocyanine is detected at the platinized surface of silicon dioxide.     

Influence of the substrate structure on the bonding of chemisorbed acetylene to transition metal surfaces

The electronic spectrum of acetylene adsorbed on various transition metals has been measured by ultraviolet photoemission spectroscopy in various laboratories. At low temperatures (T < 150 K), all measurements concur in finding an electron spectrum that differs only moderately from the gas phase spectrum of acetylene. At room temperature, the electron spectrum of acetylene is reported to be similar to the low-temperature form on Ir(100) and Pt(100), but acetylene is reported to form an olefinic surface complex on Pd(111) and Pt(111) surfaces. In order to examine whether the surface structure of the substrate is responsible for the difference, we have measured the electronic spectrum of acetylene adsorbed on the Pd(100) and Ru(0001) surfaces. At 120 K, the spectrum of adsorbed acetylene is again a distorted gas phase spectrum on both surfaces. At 330 K, we find the acetylenic form (with a splitting of 2.5 eV of the σ-orbitals) on Pd(100) and an olefinic form on the basal plane of Ru. We conclude that the olefinic complex is proper to the threefold symmetry of the (111) and (0001) surfaces and the gas-like form is favored on the (100) surfaces of the fcc crystals.     

The adsorption of oxygen on a stepped platinum single crystal surface

The adsorption of oxygen on the Pt(S)-[12(111) × (111) surface has been studied by Auger electron spectroscopy, low energy electron diffraction and thermal desorption spectroscopy. Two types of adsorbed oxygen have been identified by thermal desorption spectroscopy and low energy electron diffraction: (a) atoms adsorbed on step sites; (b) atoms adsorbed on terrace sites. The kinetics of adsorption into these two states can be modeled by considering sequential filling of the two adsorbed atomic states from a mobile adsorbed molecular precursor state. Adsorption on the step sites occurs more rapidly than adsorption onto the terraces. The sticking coefficient for oxygen adsorption is initially 0.4 on the step sites and drops when the step sites are saturated. The heat of desorption from the step site (45 ± 4 kcal/mole) is about 15% larger than the heat of desorption from the terraces.     

Quantitative Auger electron spectroscopy; A comparison of techniques for adsorbed tin on iron

Three independent approaches are discussed for the quantitative calibration of tin adsorbed on the surface of iron monitored by Auger electron spectroscopy. Two of the approaches involved measurement of the substrate and condensate Auger electron intensities at stages during the condensation of tin or stannic oxide on pure iron. The condensate quantity was directly monitored by a quartz crystal oscillator and the growth form by measurements of the elastic scattering. Allowances were made for changes in the tin Auger electron peak structure due to its combination with the oxygen in the oxide condensate. These two calibrations compare very closely with a calibration obtained from the cleavage face of a single crystal of α-iron containing 7.9 wt % of tin in solid solution. A calibration in terms of relative peak intensities is obtained for tin on iron and it is concluded that the quantifica- tion procedures are applicable, even for strongly bonded compounds.     

Electron paramagnetic resonance of radiation-induced paramagnetic centers in an aerogel

Silicon oxide aerogel samples irradiated with x rays at room temperature have been analyzed using the electron paramagnetic resonance method. It has been found that three types of paramagnetic centers appear: paramagnetic centers with a g factor of 2.0035, centers associated with the presence of protons in SiO₂ globules, and centers in the adsorbed film on the aerogel surface. The fast (T _fast = 30 h) and slow (T _slow = 70 d) processes have been revealed in the recombination of these centers.     

F−, Cl−, Li+ and Na+ adsorption on AlN nanotube surface: A DFT study

Adsorption of two anions (F⁻ and Cl⁻) and two cations (Li⁺ and Na⁺) on the surface of aluminum nitride nanotubes (AlNNTs) is investigated by density functional theory. The reactions are site-selective, so that the cations and anions prefer to be adsorbed atop the N and Al atoms of the tube surface, respectively. The adsorption energies of anions (−4.46 eV for F⁻ and −1.12 eV for Cl⁻) are much higher than those of cations (about −0.17 eV for Li⁺ and −0.12 eV for Na⁺) which can be explained using frontier molecular orbital theory. It was found that the adsorption of anions may facilitate the electron emission from the AlNNT surface by reducing the work function due to the charge transfer occurs from the anions to the tube. It has been predicted that in contrast to the cations the adsorption of anions also obviously increases the electrical conductivity of AlNNT.     

Specific adsorption of halide and pseudohalide ions at electrochemically roughened versus smooth silver-aqueous interfaces

The differential capacitance of electrochemically roughened silver surfaces in mixed perchlorate electrolytes containing chloride, bromide, iodide, thiocyanate, or azide anions has been measured as a function of electrode potential and anion concentration. These results are compared with corresponding data for electropolished silver in order to ascertain the influence of surface roughening on the double-layer structure and composition of polycrystalline silver-aqueous interfaces. The surface concentrations of specifically adsorbed anions were obtained from these capacitance-potential data using a “Hurwitz-Parsons” type of analysis. Although electrochemical roughening by means of a conventional oxidation-reduction cycle in chloride media is a prerequisite to the appearance of Surface-Enhanced Raman Scattering (SERS) for these adsorbates, it yields only moderate (ca. 1.5- to 2-fold) increases in the actual surface area and has a relatively minor effect on their average surface concentration. However, roughening does induce noticeable changes in the morphology of the capacitance-potential curves which are traced to alterations in the surface-crystallite structure. Comparisons between the potential dependence of SERS with corresponding capacitance-potential data indicate that anion coverages close to a monolayer are necessary for stable SERS. This is attributed to the stabilization of Raman-active silver clusters by surrounding adsorbed anions.     

BTA在铜表面吸附的密度泛函理论研究

本文基于密度泛函理论(DFT)的第一性原理研究了苯并三氮唑(BTA)分子吸附于铜表面的反应活性特征及其吸附在三种不同取向晶面时的电荷转移以及成键情况,结果表明：BTA分子的亲电和亲核活性中心为N(1)、N(2)和C(5),在铜表面垂直吸附时为化学吸附,Cu原子的最外层价电子转移到N(2)原子上,两者形成配位键;BTA分子在三种不同取向的铜表面吸附时的吸附能大小为：Cu(110)_x>Cu(100)_x>Cu(111)_x(x=T、B、H),T表示顶位,B表示桥位,H表示空位;BTA吸附在Cu(111)面的转移电荷量：T(顶位)>B(桥位)>H(空位).     

Angular-resolved photoemission from GaAs(110) surfaces with adsorbed Al

GaAs(110) surfaces with adsorbed Al were studied by a combination of angular-resolved valence band photoemission, Ga 3d core level photoemission, low energy electron loss spectroscopy and Auger electron spectroscopy. At room temperature Al is adsorbed on top of GaAs. After heat treatment the compound AlAs is formed at the surface, which is used as a substrate for Ga adsorption to form the inverted structure of the system GaAs + Al.     

Ion specificity and the theory of stability of colloidal suspensions

A theory is presented which allows us to accurately calculate the critical coagulation concentration of hydrophobic colloidal suspensions. For positively charged particles, the critical coagulation concentrations follow the Hofmeister (lyotropic) series. For negatively charged particles, the series is reversed. We find that strongly polarizable chaotropic anions are driven towards the colloidal surface by electrostatic and hydrophobic forces. Within approximately one ionic radius from the surface, the chaotropic anions lose part of their hydration sheath and become strongly adsorbed. The kosmotropic anions, on the other hand, are repelled from the hydrophobic surface. The theory is quantitatively accurate without any adjustable parameters. We speculate that the same mechanism is responsible for the Hofmeister series that governs stability of protein solutions.     

The growth of ice clusters on the Si(100)(2 × 1)-H(D) surface: Electron energy loss spectroscopy and thermal desorption studies

The growth of ice clusters on the Si(100)(2 × 1)-H surface has been investigated mainly by the use of high-resolution electron energy loss spectroscopy and thermal desorption spectroscopy. At 90 K, H₂O molecules are adsorbed on the (2 × 1)-H surface to form ice clusters by the hydrogen-bonding interaction. Four H₂O peaks are observed at 165, 185, 215 and 270 K in the thermal desorption spectra for the ice-covered surface. The peaks at 165 and 185 K correspond to the ice clusters and the peaks at 215 and 270 K to the strongly-bound H₂O species which play a role as the nucleation centers of the ice clusters desorbing as H₂O at 185 and 165 K, respectively.     

Reactions of weak organic acids with oxygen atoms on Ag(100): Facile and selective conversion of cyclohexene to benzene

The reactions of cyclohexene with atomically adsorbed oxygen on Ag(100) have been examined by both temperature programmed reaction mass spectrometry and electron energy loss vibrational spectroscopy. Cyclohexene reacts with adsorbed oxygen atoms to form benzene and surface hydroxyl groups, with benzene formation complete by 200 K, as evidenced by the vibrational spectra. Benzene formed from cyclohexene dehydrogenation remains chemisorbed on the silver surface until 275 K, when it desorbs. Surface hydroxyls undergo disproportionation at 300 K to form gaseous water and chemisorbed oxygen atoms. Competing with benzene formation is another reaction pathway which leads to cyclohexene combustion. Vibrational spectroscopy indicates that a key intermediate on the pathway to cyclohexene contains an intact C-O bond.     

载体钒氧化物中钒—吸附物分子相互作用的ESR研究

电子自旋共振技术已经用来研究还原态V_2O_5/SiO_2催化剂和各种吸附分子的相互作用。实验指出:具有四面体配位结构的V~(4+)离子是活性中心,V~(4+)和CH_2OH,HCl,CH_3CN分子的相互作用导致形成八面体配位结构的表面VO~(2+)络合物,它们的ESR和成键参数计算指出不成对电子主要定位在钒离子的d轨道上。77 K下吸附O_2分子已经观察到氧自由基的ESR信号,但吸附乙烯和丙烯不能改变V~(4+)离子的配位结构。