A comparative STM study of Ru nanoparticles deposited on HOPG by mass-selected gas aggregation versus thermal evaporation

Scanning tunneling microscopy was used to compare the morphologies of Ru nanoparticles deposited onto highly-oriented graphite surfaces using two different physical vapour deposition methods; (1) pre-formed mass-selected Ru nanoparticles with diameters between 2 nm and 15 nm were soft-landed onto HOPG surfaces using a gas-aggregation source and (2) nanoparticles were formed by e-beam evaporation of Ru films onto HOPG. The particles generated by the gas-aggregation source are round in shape with evidence of facets resolved on the larger particles. Annealing these nanoparticles when they are supported on unsputtered HOPG resulted in the sintering of smaller nanoparticles, while larger particles remained immobile. Nanoparticles deposited onto sputtered HOPG surfaces were found to be stable against sintering when annealed. The size and shape of nanoparticles deposited by e-beam evaporation depend to a large extent on the state of the graphite support and the temperature. Ru deposition onto unsputtered HOPG is characterised by bimodal growth with large flat particles formed on the substrate terraces and smaller diameter particles aligned along the substrate steps. Evaporation onto sputtered HOPG results in the formation of 2 nm round particles with a narrow size distribution. Finally, thermal deposition onto both sputtered and unsputtered HOPG at 660 °C results in larger particles showing a flat Ru(0 0 0 1) top facet.     

纳米ZnO的表面化学修饰及其分析表征

采用水溶性羟丙基甲基纤维素HPMC对无机纳米ZnO粒子进行物理吸附处理 ,获得了核为无机纳米ZnO ,外壳为水溶性高分子HPMC的粒子。然后在其上进行了甲基丙烯酸甲酯的接枝聚合。采用红外光谱、差热分析的方法对复合粒子进行了表征 ,并采用透射电镜观察了粒子的形貌。红外光谱表明在纳米ZnO的表面吸附了HPMC并接枝了PMMA ,差热分析表明HPMC ,HPMC g PMMA和ZnO/HPMC g PMMA的热稳定性逐渐提高 ,透射电镜观察表明 ,在纳米ZnO的表面粘附了一层聚合物 ,成功地实现了纳米粒子的表面修饰。     

Radical grafting from carbon fiber surface: graft polymerization of vinyl monomers initiated by azo groups introduced onto the surface

This paper describes the radical graft polymerizations of vinyl monomers from carbon fiber surface initiated by azo groups introduced onto the fiber surface. The carbon fiber used in this experiment was the polyacrylonitrile type. The introduction of azo groups onto the carbon fiber surface was achieved by the reaction of 4,4'-azobis (4-cyanopentanoic acid) with isocyanate groups which were previously attached onto the surface by the treatment of the fiber with tolylene 2,4-diisocyanate. The amount of surface azo groups introduced onto nitric acid-treated carbon fiber was determined to be 0.60 x 10^-5 mol 9^-1 by nitrogen analysis. The radical graft polymerization of methyl methacrylate (MMA) was tried. Though the thermal polymerization of MMA proceeded slightly in the absence or in the presence of untreated carbon fiber, the rate of the polymerization was considerably low. In contrast, the graft polymerization of MMA was initiated in the presence of the carbon fiber having surface azo groups, and part of resultant poly(MMA) grafted onto the surface. The percentage of grafting increased with an increase in polymerization time and reached 42.8% after 24 h. The graft polymerizations of other monomers, such as styrene, vinyl acetate, and acrylic acid, were also initiated by the surface azo groups attached onto the carbon fiber, and the corresponding polymer effectively grafted onto the surface.     

载铅(Ⅱ)高硅质大气矿物细颗粒对大肠杆菌的毒性作用研究

以大气颗粒物中的高硅质矿物细颗粒--石英粉尘和重金属离子附载污染物Pb(Ⅱ)为实验材料,人工制备载铅石英粉尘。以1.6 g·L-1的载铅(Ⅱ)石英粉尘及不同浓度的PbCl₂染毒大肠杆菌细胞,观察染毒2 h后对机体的联合氧化损伤效应,并探讨其对大肠杆菌表面基团及蛋白酰胺I带二级结构的影响。结果表明,与Pb(Ⅱ)、载铅石英粉尘作用后,大肠杆菌细胞活力降低,胞内活性氧(ROS)及丙二醛(MDA)产生增多、谷胱甘肽(GSH)含量下降,引起细菌氧化应激水平的提高;皮尔逊(Pearson)相关性分析显示载铅石英粉尘的细菌毒性与粉尘中Pb(Ⅱ)可交换态含量成正相关,载带高浓度Pb(Ⅱ)的石英粉尘组胞内ROS/MDA水平与其单纯石英粉尘组和Pb(Ⅱ)组比较显著增加(p<0.05);重金属Pb(Ⅱ)、载铅石英粉尘对大肠杆菌菌体表面基团的影响主要集中于磷酸二酯基团和表面多糖分子,采用二阶导、去卷积和谱线拟合技术对酰胺Ⅰ带特征峰(1 600～1 700 cm-1)进行分峰拟合后发现,与Pb(Ⅱ)、载铅石英粉尘(Q-Pb-0,Q-Pb-3)作用后,β-sheets/α-helices的比值由对照组的1.41分别降低到1.33,1.27和1.22,表明细菌表面蛋白质结构发生了变化,从而可能影响了细菌的生理活动。研究表明自由基所产生的氧化损伤可能是载Pb(Ⅱ)石英粉尘的一种重要毒性作用机制,载带Pb(Ⅱ)的复合石英粉尘在致大肠杆菌机体氧化损伤效应方面二者存在一定的协同作用。     

Nanoparticle Probes for Quantifying Supramolecular Determinants of Biosurface Affinity

Interactions between macromolecular systems and biosurfaces are complicated by the complexity of these multivalent interactions and challenges in quantifying affinities. In this study, a library of gold nanoparticles (AuNPs) with different functional head groups as multivalent probes to quantify biosurface affinity, using hair as a model targeted substrate, is used. The adhesion of the AuNPs is quantified by inductively coupled plasma mass spectrometry. Using this method it is demonstrated that multiple supramolecular forces affect affinity. As expected, electrostatic interaction is a strong driving force for adhesion of the nanoparticle tags onto hair in aqueous solution, evidenced by a much higher level of gold adsorption for cationic AuNPs compared to anionic or neutral AuNPs. Functionalized cationic AuNPs are synthesized with systematically varied terminal groups and are screened for deposition onto hair. AuNP adhesion onto hair in water generally decreases as a function of increasing hydrophobicity; however, electron‐rich aromatic rings provide significantly enhanced attachment. Although the intact, healthy hair cuticle is considered negatively charged and hydrophobic, the findings indicate that hydrophobic interactions are not as critical to deposition of AuNPs onto hair as the electrostatic component from the presence and accessibility of the cationic moieties, which are the greatest drivers for deposition onto hair.     

Charged black holes in phantom cosmology

In the classical relativistic regime, the accretion of phantom-like dark energy onto a stationary black hole reduces the mass of the black hole. We have investigated the accretion of phantom energy onto a stationary charged black hole and have determined the condition under which this accretion is possible. This condition restricts the mass-to-charge ratio in a narrow range. This condition also challenges the validity of the cosmic-censorship conjecture since a naked singularity is eventually produced due to accretion of phantom energy onto black hole.     

Colour superconductivity in finite systems

We have studied the effects of finite size on the two flavor colour superconducting state. Since the baryon number in the BCS state is only fixed on average, we have projected the state onto a fixed baryon number. The resulting state has been then projected onto a colour-singlet state, by integrating onto the colour group manifold. The effects of both projections have been evaluated numerically.     

Surface modification of calcium carbonate: radical graft polymerization of vinyl monomers onto calcium carbonate surface initiated by azo groups introduced onto the surface

—The preparation of calcium carbonate modified by 12-hydroxystearate groups and the grafting of polymers onto the surface by the polymerization of vinyl monomers initiated by azo groups introduced onto the surface were investigated. The preparation of calcium carbonate modified by 12-hydroxystearate was achieved by the reaction of calcium chloride with sodium carbonate containing a small amount of sodium 12-hydroxystearate. The introduction of azo groups onto calcium carbonate was successfully achieved by the direct condensation of the carboxyl group of 4,4'-azobis(4-cyanopentanoic acid) with 12-hydroxystearate groups on the modified calcium carbonate using N,N'-dicyclohexylcarbodiimide as a condensing agent. It was found that the radical polymerization of vinyl monomers, such as methyl methacrylate (MMA), styrene, and N-vinylcarbazole (NVC), was initiated by azo groups introduced onto the surface, and the corresponding polymers were grafted onto the surface based on the propagation of polymer from the surface: the percentage of grafting of polyMMA, polystyrene, and polyNVC reached 5.7, 9.5 and 3.5%, respectively, at 70°C. The percentage of grafting was found to decrease with decreasing monomer concentration. The wettability of calcium carbonate surface was found to turn from hydrophilic to hydrophobic by the grafting of polymers.     

Composite of synthetic mica with polymers: grafting of polymers with controlled molecular weight onto synthetic mica by use of living polymer cation

The grafting of polymers onto synthetic mica surface and formation of an interlayer by the termination of living polymer cation with amino groups introduced onto the synthetic mica was investigated. The introduction of amino groups onto the synthetic mica was achieved by the reaction of silanol groups with γ-aminopropyltriethoxysilane. It was found that living poly(isobutyl vinyl ether) (polyIBVE) and living poly(2-methyl-2-oxazoline) (polyMeOZO) cations with controlled molecular weight and narrow molecular weight distribution were successfully terminated by amino groups of synthetic mica, and the corresponding polymers were grafted onto the surface and interlayer of the mica. The grafting of polyIBVE and polyMeOZO on the synthetic mica decreased with increasing molecular weight of the living polymer cations. The effect of reaction temperature on the grafting of polyMeOZO onto the synthetic mica was examined. The X-ray diffraction curves of polyMeOZO-grafted synthetic mica have a peak at 2 = 4.5° assigned 001 lattice spacing: the lattice spacing was expanded by the grafting of polyMeOZO in the interlayer of the synthetic mica.     

Structural, optical and electrochemical properties of TiO2 thin films grown by APCVD method

Atmospheric pressure chemical vapor deposition (APCVD) of TiO₂ thin films has been achieved onto glass and onto ITO-coated glass substrates, from the reaction of TiCl₄ with ethyl acetate (EtOAc). The effect of the synthesis temperature on the optical, structural and electrochemical properties was studied through spectral transmittance, X-ray diffraction (XRD) and electrochemical impedance spectroscopy (EIS) measurements. It was established that the TiO₂ films deposited onto glass substrate, at temperatures greater than 400 °C grown with rutile type tetragonal structure, whereas the TiO₂ films deposited onto ITO-coated glass substrate grown with anatase type structure. EIS was applied as suitable method to determine the charge transfer resistance in the electrolyte/TiO₂ interface, typically found in dye-sensitized solar cells.     

Peroxomonosulphate initiated graft copolymerization of aniline onto poly(propylene) fibre - A kinetic approach

Graft copolymerization of poly(aniline) (PANI) onto poly(propylene) (PP) fibre was carried out in aqueous acidic medium under nitrogen atmosphere by using peroxomonosulphate (PMS) as a lone initiator. The non-conducting fibre was now made into a conducting one through the chemical grafting of PANI units onto the PP fibre backbone. The content of PANI in the backbone was found to vary while varying the [ANI], [PMS] and amount of PP fibre. Various graft parameters were evaluated. The chemical grafting of PANI onto PP fibre was confirmed by conductivity measurements.     

XPS and bioactivity study of the bisphosphonate pamidronate adsorbed onto plasma sprayed hydroxyapatite coatings

This paper reports the use of X-ray photoelectron spectroscopy (XPS) to investigate bisphosphonate (BP) adsorption onto plasma sprayed hydroxyapatite (HA) coatings commonly used for orthopaedic implants. BPs exhibit high binding affinity for the calcium present in HA and hence can be adsorbed onto HA-coated implants to exploit their beneficial properties for improved bone growth at the implant interface. A rigorous XPS analysis of pamidronate, a commonly used nitrogenous BP, adsorbed onto plasma sprayed HA-coated cobalt-chromium substrates has been carried out, aimed at: (a) confirming the adsorption of this BP onto HA; (b) studying the BP diffusion profile in the HA coating by employing the technique of XPS depth profiling; (c) confirming the bioactivity of the adsorbed BP. XPS spectra of plasma sprayed HA-coated discs exposed to a 10 mM aqueous BP solution (pamidronate) for periods of 1, 2 and 24 h showed nitrogen and phosphorous photoelectron signals corresponding to the BP, confirming its adsorption onto the HA substrate. XPS depth profiling of the 2 h BP-exposed HA discs showed penetration of the BP into the HA matrix to depths of at least 260 nm. The bioactivity of the adsorbed BP was confirmed by the observed inhibition of osteoclast (bone resorbing) cell activity. In comparison to the HA sample, the HA sample with adsorbed BP exhibited a 25-fold decrease in primary osteoclast cells.     

Mutual information theory for biomedical applications: Estimation of three protein-adsorbed dialysis membranes

Protein-adsorbed dialysis membranes are evaluated with time-of-flight secondary ion mass spectrometry (TOF-SIMS) chemical imaging technique. Protein adsorption causing permeability change is one of big issues in the development of dialysis membranes. Bovine serum albumin adsorption onto three kinds of dialysis membranes has been evaluated with TOF-SIMS. In the present study three kinds of proteins, bovine serum albumin, α-chymotripsinogen A, and cytochrome C adsorbed onto hollow-fiber dialysis membranes, were measured by means of TOF-SIMS and then TOF-SIMS spectra were analyzed using mutual information. Then specific peaks of fragment ions related to α-chymotripsinogen A and bovine serum albumin were found, respectively. In this condition, however, specific peaks to cytochrome C were not able to find compared with other samples. Finally, chemical images of α-chymotripsinogen A and bovine serum albumin, respectively, adsorbed onto the membranes with co-existing proteins were obtained. The results of TOF-SIMS images of the proteins on the membranes show different tendency of adsorption depending on co-existing proteins. Further study is needed to study more detailed protein adsorption onto the membranes with co-existing proteins.     

The conductance of monoatomic As and Ag chains deposited onto silicon steps evaluated using a simplified scattering approach

The purpose of this study is the assessment of the properties of the conductance of deposited atomic chains. Therefore, linear chains of covalent and metallic atoms, i.e. As and Ag, deposited onto monolayer steps of the Si(1 0 0) surface have been considered. The study is based on the extended Hückel theory, used for the evaluation of both the electronic structure and the conductance, and the calculations analyze the binding and adsorption energies of chains of variable length deposited onto SA steps in the light of the similar properties of free standing chains and of chains deposited onto the flat Si(1 0 0) surface. This comparison shows that the stability of the chain depends on its composition, rather than on its length, and increases in the order: free standing, deposited onto SA, deposited onto Si(1 0 0). The central result of the calculations of the conductance is that the dependence of this quantity on the chain length and composition and on the type of substrate parallels the one of the characteristic energies.     

电化学汞齐法处理金表面的增强拉曼散射研究

采用汞盐的电化学还原法可通过控制电解的时间及速度来控制在金表面还原生成的金属汞的量,从而使金表面获得可控制的刻蚀,形成适当的粗糙度。以２,２ 联吡啶作为探针化合物吸附于在不同条件下汞齐化处理的金表面,收集其拉曼信号以确定最佳的刻蚀条件。经电化学汞齐化刻蚀活化的金表面比用通常的氧化还原循环处理的金表面具有更好的增强效果。将聚噻吩沉积在以上述刻蚀法粗糙化的金电极表面可获得信噪比高的亚单分子层的聚噻吩的ＳＥＲＳ谱,并表明在三氟化硼乙醚中沉积的聚噻吩较之在通常的有机溶剂中沉积的聚噻吩具有更有序的排列结构。     

DFT calculations for Au adsorption onto a reduced TiO2 (110) surface with the coexistence of Cl

Residual chlorines, which originate from HAuCl₄, enhance the aggregation of gold (Au) nanoparticles and clusters, preventing the generation of highly active supported Au catalysts. However, the detailed mechanism of residual-chlorine-promoted aggregation of Au is unknown. Herein to investigate this mechanism, density functional theory (DFT) calculations of Au and Cl adsorption onto a reduced rutile TiO₂ (110) surface were performed using a generalised gradient approximation Perdew, Burke, and Ernzerhof formula (GGA–PBE) functional and plane-wave basis. Although both Au and Cl atoms prefer to mono-absorb onto oxygen defect sites, Cl atoms have a stronger absorption onto a reduced TiO₂ (110) surface, abbreviated as rTiO₂ (110) in the following, than Au atoms. Additionally, co-adsorption of a Cl atom and a Au atom or Au nanorod onto a rTiO₂ surface was investigated; Cl adsorption onto an oxygen defect site weakens the interaction between a Au atom or Au nanorod and rTiO₂ (110) surface. The calculation results suggest that the depletion of interaction between Au and rTiO₂ surface is due to strong interaction between Cl atoms at oxygen defect sites and neighbouring bridging oxygen (O^B) atoms.     

Adsorption of naphthalene onto sonicated talc from aqueous solutions

The adsorption behavior of naphthalene onto naturally hydrophobic talc from aqueous solution was investigated in this study. The natural talc was first pretreated by sonication to improve the surface characteristics and enhance the uptake capacity by increasing the specific surface area (SSA) of talc. The naphthalene uptake of talc was found as 276 mg g^?1 and increased to 359 mg g^?1 after the sonication. Adsorption studies also showed that the adsorption of naphthalene onto the sonicated talc was not affected by changes in pH suggesting that the main driving forces for naphthalene adsorption onto talc was hydrophobic bonding rather than electrostatic force. The pseudo-first and pseudo-second orders and intraparticle diffusion equation were used to evaluate the kinetic data and the constants were determined. Adsorption process of naphthalene onto talc followed the pseudo-second-order rate expression for different initial naphthalene concentrations. The Langmuir and Freundlich isotherm models were used to model the isotherm data for their applicability. The Freundlich isotherm best fitted for the adsorption of naphthalene onto talc.     

Brownian gyrator: a minimal heat engine on the nanoscale

A Brownian particle moving in the vicinity of a generic potential minimum under the influence of dissipation and thermal noise from two different heat baths is shown to act as a minimal heat engine, generating a systematic torque onto the physical object at the origin of the potential and an opposite torque onto the medium generating the dissipation.     

有机高性能Kevlar纤维表面改性研究

试图通过化学处理方法在Kevlar纤维表面引入活性基团 ,从而达到对Kevlar纤维进行表面接枝改性的目的。通过红外光谱分析方法研究了甲苯 2 ,4 二异氰酸酯 (TDI)接枝Kevlar纤维的反应 ,探讨了水解时间对其产物中—O—H基含量的影响 ;纤维水解对接枝反应 ,及其己内酰胺的封端处理对接枝产物的影响。结果表明 ,纤维水解后含有较多的—O—H基 ,且有利于接枝反应的进行 ;而己内酰胺的封端处理可以得到稳定化的接枝产物。证明了只要在纤维表面引入少数活性基团就会有效地改善纤维 /树脂界面的结合。     

Ultrasound enhanced the binding ability of chitinase onto chitin: From an AFM insight

In order to evaluate the effect of ultrasound to chitinase from a molecular level, atomic force microscopy (AFM) was employed to investigate the interaction force of chitinase binding onto chitin surface. In the measurement of force-distance curve, a series of pull-off events were discovered using the immobilized AFM tips with chitinase either treated by ultrasound or not, whereas no interaction peak was observed by the AFM tips without chitinase, indicating that the obtained adhesion forces were coming from the binding functions between chitinase and chitin. Through the analysis of these force curves, at the loading velocity of 0.3 μm/s, the maximum binding force of the chitinase treated by ultrasound for 20 min onto chitin was measured to be 105.33 ± 23.51 pN, while the untreated onto chitin was 71.05 ± 12.73 pN, suggesting the stronger binding force between ultrasonic treated chitinase and chitin substrate. Therefore, AFM has provided a useful method to directly and quantitatively characterize the interactions between chitinase and chitin, and successfully proved that ultrasound could activate chitinase by enhancing the binding ability of chitinase onto chitin.