Adsorption and Vibration of O on the Pt Stepped Surfaces

1 INTRODUCTION Atom adsorption on transition metal surfaces has attracted special attention as a basis for understand- ing the fundamental processes of oxidative cataly- sis. An oxygen-covered platinum surface for example, plays a central role in several important reactions, such as oxidation of carbon monoxide[1]. Moreover, the behavior of oxygen in the proximity of surface defects like kinks and steps is a central issue in understanding the chemisorption processes on ca- talytic surfaces…     

Adsorption and Vibration of CI Atoms on Ni Low-index Surfaces

The 5-parameter Morse potential（5-MP） of the interactions between Cl atoms and Ni surfaces was constructed. The adsorption and diffusion of Cl atoms on Ni low index-surfaces were investigated with 5-MP in detail. All the critical characteristics of the system, such as adsorption site, adsorption geometry, binding energy, eigenvalues for vibration, etc. were obtained. The calculated results show that chlorine atoms are likely to be adsorbed on the high symmetry- sites. Cl atoms locate on the four-fold hollow sites of the intact Ni（100） surface, while they tend to occupy threefold sites on the Ni（ 111 ） surface. The four-fold hollow sites are the most stable adsorption sites on the Ni （110） surface for Cl, although the three-fold sites and the long-bridge sites are stable adsorption sites on the Ni（110） surface for the atoms of the first and second periods. For the Cl-Ni surface adsorption system, the surface binding energy of a Cl atom is relevant to the coarse degree of the cluster surface, and the binding energies have an order of Ni （ 111 ） 〈 Ni（100） 〈Ni（100）.     

Surface-enhanced Raman Scattering from Molecules Adsorbed on Mixed Silver／Gold Nanoparticle Surfaces

Since the first discovery of Surface-Enhanced Raman Scattering(SERS) from pyridine molecules adsorbed at roughened silver electrodes in 1974 by Fleischmann et al.,the research of SERS has made tremendous progress in applications of it to various fields of science and technology. Experimentally, metal colloids show favorable properties for being used as substrates in SERS. And a-mong them,silver and gold colloids are largely em-     

Electrochemical Nanoparticle Sizing Via Nano-Impacts: How Large a Nanoparticle Can be Measured?

The field of nanoparticle (NP) sizing encompasses a wide array of techniques, with electron microscopy and dynamic light scattering (DLS) having become the established methods for NP quantification; however, these techniques are not always applicable. A new and rapidly developing method that addresses the limitations of these techniques is the electrochemical detection of NPs in solution. The ‘nano-impacts’ technique is an excellent and qualitative in situ method for nanoparticle characterization. Two complementary studies on silver and silver bromide nanoparticles (NPs) were used to assess the large radius limit of the nano-impact method for NP sizing. Noting that by definition a NP cannot be larger than 100 nm in diameter, we have shown that the method quantitatively sizes at the largest limit, the lower limit having been previously reported as ∼6 nm.¹     

A DFT Study of Thiophene Adsorption on the Rh（111） Surfaces

Thiophene adsorption on the Rh(111) surfaces has been investigated by density functional theory.The results show that the adsorption at the hollow and bridge sites is the most stable.The molecular plane of the thiophene ring is distorted,the C=C bond is stretched to 1.448  and the C-C bond is shortened to 1.390.The C-H bonds tilt 22～42oaway from the surface.The calculated adsorption geometries are in reasonable agreement with population analysis and density of states.The thiophene molecule obtains 0.74 electrons,reflecting the interaction between the lone pair of sulfur and the d-orbitals of metal.The reaction paths and transition states for desulfurization of the molecule have been investigated.The bridge adsorption structure of thiophene leads to a thiol via an activated reaction with an energetic barrier of 0.30 eV.This second step is slightly difficult,and dissociation into a C4H4 fragment and a sulfur atom is possible,with an energetic barrier of 0.40 eV.     

Adsorption of Ions on Zirconium Oxide Surfaces from Aqueous Solutions at High Temperatures

Surface titrations were carried out on suspensions of monoclinic ZrO₂ from 25 to 290 °C slightly above saturation vapor pressure at ionic strengths of 0.03, 0.1 and 1.0 mol⋅kg⁻¹(NaCl). A typical increase in surface charge was observed with increasing temperature. There was no correlation between the radius of the cations, Li⁺, Na⁺, K⁺ and (CH₃)₄N⁺, and the magnitude of their association with the surface. The combined results were treated with a 1-pK_a MUSIC model, which yielded association constants for the cations (and chloride ion at low pH) at each temperature. The pH of zero-point-charge, pH_zpc, decreased with increasing temperature as found for other metal oxides, reaching an apparent minimum value of 4.1 by 250 °C. Batch experiments were performed to monitor the concentration of LiOH in solutions containing suspended ZrO₂ particles from 200 to 360 °C. At 350 and 360 °C, Li⁺ and OH⁻ ions were almost totally adsorbed when the pressure was lowered to near saturation vapor pressure. This reversible trend has implications not only to pressure-water reactor, PWR, operations, but is also of general scientific and other applied interest. Additional experiments probed the feasibility that boric acid/borate ions adsorb reversibly onto ZrO₂ surfaces at near-neutral pH conditions as indicated in earlier publications. Electronic Supplementary Material  The online version of this article () contains supplementary material, which is available to authorized users.     

Oxygen Atom Adsorption and Diffusion on Pd Low-index Surfaces and （311） Stepped Surface

Introduction Atom adsorption on transition metal surfaces has attracted special attention as a base for understanding the fundamental processes of oxidative catalysis. Particularly interesting is the adsorption and diffusion of oxygen on well-defined metal surfaces. An oxygen covered palladium surface, for example, plays a central role in several important reactions such as oxidation of carbon monoxide and ammonia. In particular, the (100), (111), (110) surfaces and the interactions with oxyge…     

When and How Do Diaminocarbenes Dimerize?

No example of a simple uncatalyzed dimerization of a diaminocarbene has been clearly established, so it is timely to ask what factors control the thermodynamics of this reaction, and what mechanisms are responsible for the observed dimerizations? In agreement with qualitative experimental observations, the dimerizations of simple five‐ and six‐membered‐ring diaminocarbenes are calculated to be 100 kJ mol^?1 less favorable than those of acyclic counterparts. This large difference is semiquantitatively accounted for by bond and torsional angle changes around the carbene centers. Carbenes such as (Et₂N)₂C are kinetically stable in THF at 25 °C in agreement with calculated energy barriers, but they rapidly dimerize in the presence of the corresponding formamidinium ion. This proton‐catalyzed process is probably the most common mechanism for dimer formation, and involves formation of C‐protonated dimers, which can be observed in suitable cases. The possibility of alkali‐metal‐promoted dimerization is raised, and circumstantial evidence for this is presented.     

How Do Charges Travel through DNA?-An Update on a Current Debate

The effects of oligonucleotide sequence, base pairing, stacking, and duplex microstructure as well as donor-acceptor distance, labeling site, and driving force on charge-transfer reactions in DNA are of interest, yet relatively few experiments have been performed to address many of these issues. This article summarizes recent results on DNA-mediated charge transfer and highlights experimental and theoretical issues that are still unanswered or unresolved.     

Adsorption and Vibration of O Atoms on Fe Low-index and Fe （211） High-index Surfaces

IntroductionThe interaction of oxygen with iron in lowcoverageregimes is considered to be an important step in the for-mation of oxides in corrosion science and in Fisher-Tro-psch process for the synthesis of ammonia over the het-erogeneous catalysts[1]. …     

DFT Study of Thiophene Adsorption on the Pd（111） and Pt（111） Surfaces

Thiophene adsorption on the(111) surfaces of Pd and Pt have been investigated by density functional theory.The results indicate that the adsorption at the hollow sites is the most stable.To our interest,the molecular plane of thiophene ring is distorted with C=C bond being elongated to 1.450  and C-C bond being shortened to 1.347 ,and the C-H bonds tilt 13.91～44.05o away from this plane.Furthermore,analysis on population and density of states verified the calculated adsorption geometries.Finally,charge analysis suggests that thiophene molecule is an electron acceptor,reflecting the interaction between the lone pair of sulfur and the d-orbitals of metal.     

Are the Interactions between Recombinant Prion Proteins and Polymeric Surfaces Related to the Hydrophilic/Hydrophobic Balance?

New non‐fouling tubes are developed and their influence on the adhesion of neuroproteins is studied. Recombinant prion proteins are considered as a single component representative of hydrophobic proteins. Samples are stored for 24 h at 4 °C in tubes coated with two different coatings: poly(N‐isopropylacrylamide) as a hydrophilic surface and a plasma‐fluorinated coating as a hydrophobic one. The protein adhesion is monitored by ELISA tests, XPS and confocal microscopy. It appears that the highest recovery of recombinant prion protein in the liquid phase is obtained with the hydrophilic surface while the hydrophobic character of the storage tube induces an important amount of biological loss. However, the recovery is not complete even for tubes coated with poly(N‐isopropylacrylamide).

     

Construction of CdS Nanoparticle Chain on DNA Template

Salmon sperm DNA was used as template to assembly and nucleate CdS nanoparticles.Transmission electron microscopy(TEM)images showed that the CdS nanoparticles fromed unique nanostructure which present regular and parallel chains along DNA molecular chaing.The width of every chain was about 3 nm.Raman and Xray photoelectron energy spectroscopy(XPS) confirmed that the nucleation sites of CdS nanoparticles were phosphate acid groups of DNA.     

Real-Time NMR. How Fast Can We Do It?

Network structure development during cross-linking photopolymerization of polyethylene glycol di-acrylate and its mixture with a mono-functional 2-ethylhexyl acrylate was studied using real-time proton NMR T₂ relaxation analysis. The time resolution of the method is typically in the order of seconds. The results reveal largely heterogeneous origin of network build up at the intermediate stages of photocuring. Domains of nano-gel are already formed on initial stages of UV-curing where hardly any change in viscosity is observed. Upon increasing curing time the fraction of gel increases at the expence of sol, the molar mass of network chains decreases and the molar mass of sol increases. The presence of mono-acrylate slows down the curing rate. The curing continues after UV-illumination causing a significant increase in the amount of gel and cross-link density in the gel. Thus, the NMR method is a valuable tool for characterization of the kinetics of photopolymerization, the development of molecular structure and the resultant molecular scale heterogeneity during photocuring.     

Do Intrinsically Disordered Proteins Possess High Specificity in Protein–Protein Interactions?

Specific protein–protein interactions are critical to cellular function. Structural flexibility and disorder‐to‐order transitions upon binding enable intrinsically disordered proteins (IDPs) to overcome steric restrictions and form complementary binding interfaces, and thus, IDPs are widely considered to have high specificity and low affinity for molecular recognition. However, flexibility may also enable IDPs to form complementary binding interfaces with misbinding partners, resulting in a great number of nonspecific interactions. Consequently, it is questionable whether IDPs really possess high specificity. In this work, we investigated this question from a thermodynamic viewpoint. We collected mutant thermodynamic data for 35 ordered protein complexes and 43 disordered protein complexes. We found that the enthalpy–entropy compensation for disordered protein complexes was more complete than that for ordered protein complexes. We further simulated the binding processes of ordered and disordered protein complexes under mutations. Simulation data confirmed the observation of experimental data analyses and further revealed that disordered protein complexes possessed smaller changes in binding free energy than ordered protein complexes under the same mutation perturbations. Therefore, interactions of IDPs are more malleable than those of ordered proteins due to their structural flexibility in the complex. Our results provide new clues for exploring the relationship between protein flexibility, adaptability, and specificity.     

How Many Molecules are Required to Obtain a Steady Faradaic Current from Mediated Electron Transfer at a Single Nanoparticle on a Supporting Surface?

We investigate the chronoamperometric noise characteristics of electron‐transfer reactions occurring on single nanoparticles (NPs) and assemblies of well‐separated NPs on a supporting surface. To this end, we combine a formerly described expression for the steady‐state current of a single particle with the shot‐noise model and derive an expression for the signal‐to‐noise ratio as a function of bulk concentration and particle radius. Our findings are supported by random‐walk simulations, which closely match the analytical results.