Optical and photoelectrical studies of gold nanoparticle-decorated C60 films

Optical and photoelectrical studies were performed on octane-1,8-dithiol cross-linked fullerene films, with supported gold nanoparticles (C₆₀-DT-Au). According to high-resolution transmission electron microscopy observations, the average size of obtained gold nanoparticles was about 5 nm, and the shape was spherical. The comparative investigation of optical properties of pristine and cross-linked with octane-1,8-dithiol C₆₀ films, decorated with gold nanoparticles, found the difference in the extinction coefficient spectra, which was observed also in the photocurrent spectra of barrier heterostructure Au/C₆₀/Si. The analysis of dark current-voltage characteristics for Au/C₆₀/Si heterostructures showed that the model for them includes the barrier at the C₆₀/Si interface and internal barriers in the C₆₀ layer, caused by the trapping centers. The hopping mechanism of the current transport in the C₆₀ layer was supplemented with the Poole-Frenkel emission process on these centers, with the barrier height greater for the fullerene C₆₀ film cross-linked with octane-1,8-dithiol.     

Synthesis and characterization of phospholipid-functionalized silver nanoparticles

Functionalizations of silver nanoparticles (AgNPs) by phospholipids (PLs) have been manifested well by means of covalent connection between AgNPs with PLs. After functionalization, the attached PLs can self-assemble into bilayer structures on the surfaces of AgNPs. TEM displays the images of pure AgNPs and functionalized AgNPs with certain thickness of the phospholipid bilayers, as a result of chemical connection existing in AgNPs-PL conjugates. UV-vis and IR spectra confirm the strong Ag-S interaction between silver and sulfur produced during the reactions. This new modification method for AgNPs offers a good opportunity to functionalize nanoparticles with biological activity.     

C60/PVK/CdS纳米粒子功能复合 LB 膜研究

目的 尝试用Ｌａｎｇｍｕｉｒ－Ｂｌｏｄｇｅｔｔ（ＬＢ）技术组装Ｃ６０技术组装Ｃ６０功能复合体系的新方法。方法 采用（ＬＢ）技术制备Ｃ６０／ＰＶＫ／ＣｄＳ花生酸混合ＬＢ膜并利用界面化学反应技术将混合膜与硫化氢气体反应制得Ｃ６０／ＰＶＫ／ＣｄＳ纳米粒子功能复合ＬＢ膜并进行紫外光谱表征。结果 含不同比例Ｃ６０的Ｃ６０ＰＶＫ／ＡＡ体系可以在辐亚相上形成稳定的单层膜并转移到固体基片上得到了ＬＢ多层膜,ＬＢ混     

天然石墨-纳米银/聚氨酯导电复合薄膜的制备及性能

采用热处理还原银盐原位引入银粒子的方法, 成功制备了天然石墨-纳米银/聚氨酯(C-Ag/PU)导电复合薄膜。并通过透射电镜(TEM)、 扫描电镜(SEM)观察了该复合薄膜的微观结构, 用X射线衍射仪(XRD)跟踪了银的还原和银粒子的生长过程, 探讨了加热温度和加热时间对银还原过程的影响, 研究了纳米银的生成和聚集对C/PU复合体系导电性能的影响。结果表明, 随着热处理的进行, 银粒子不断地生成和聚集, 最终以纳米尺寸(约10nm)均匀分散在聚合物基体中。纳米银粒子在天然石墨粒子之间起到了桥梁的作用, 改善了复合体系的导电通路, 显著提高了复合体系的导电性。      

Electronic charge transfer in cobalt doped fullerene thin films and effect of energetic ion impacts by x-ray absorption spectroscopy

We report on the electronic charge transfer in cobalt doped fullerene thin films by means of near-edge x-ray-absorption fine structure (NEXAFS) spectroscopy measurement. Co-doped fullerene films were prepared by co-deposition technique and subjected to energetic ion irradiation (120 MeV Au) for possibly alignment or interconnect of randomly distributed metal particles. Polarization dependent NEXAFS spectra revealed the alignment of Co and C atoms along the irradiated ionic path. The structural changes in Co-doped as-deposited and ion irradiated fullerene films were investigated by means of Raman spectroscopy measurements. Downshift of pentagonal pinch mode A_g(2) in Raman spectroscopy indicated the electronic charge transfer from Co atom to fullerene molecules, which is further confirmed by NEXAFS at C K-edge for Co-doped fullerene films.     

Effects of carbon nanotubes (CNTs) on the processing and in-vitro degradation of poly(dl-lactide-co-glycolide)/CNT films

Nanocomposite films based on single wall carbon nanotubes (SWNTs) and poly(dl-lactide-co-glycolide) copolymer (50:50 PLGA) were processed and analyzed. The purpose of this study was to investigate the effect of different functionalization systems on the physical stability and morphology of PLGA films. Both covalent and non covalent functionalization of carbon nanotubes were considered in order to control the interactions between PLGA and SWNTs and to understand the role of the filler in the biodegradation properties. Using a solvent casting process, different PLGA/SWNT nanocomposites were prepared and incubated using organic solution under physiological conditions. In-vitro degradation studies were conducted by measurements of weight loss, infrared spectroscopy, glass transition temperature and SEM observations as a function of the incubation time, over a 9-week period. All PLGA films were degraded by hydrolitical degradation. However, a different degradation mechanism was observed in the case of functionalized SWNTs with respect to pristine material. It has been observed that system composition and SWNT functionalization may play a crucial role on the autocatalytic effect of the degradation process. These studies suggest that the degradation kinetics of the films can be engineered by varying carbon nanotube (CNT) content and functionalization. The combination of biodegradable polymers and CNTs opens a new perspective in the self-assembly of nanomaterials and nanodevices.     

Controlled surface functionalization of silica nanospheres by covalent conjugation reactions and preparation of high density streptavidin nanoparticles

Silica nanoparticles with a diameter of 100 nm were covalently modified at their surface by adjustable amounts of amine and carboxyl functional groups. Bioconjugation studies of two proteins, streptavidin and streptactin, with the functional nanoparticles resulted in optimum binding of the proteins to a long-chain carboxyl-terminated linker. The surface functionalization of the nanoparticles was monitored by a variety of independent methods, including zeta-potential measurements, dynamic light scattering (DLS), scanning electron microscopy (SEM), particle charge detection titrations (PCD) and elemental analysis. At the surface of the nanoparticles, a functional surface group density of 1.8 amino groups per nm2 was realized. The amine functions were quantitatively transferred to carboxyl groups coupled with a linker elongation. Streptavidin was immobilized by covalent binding to the carboxyl linkers and resulted in a protein density at the surface of the nanoparticles that was three times higher than the highest binding densities at nanoparticles published to date. The binding capacity of the streptavidin-covered nanoparticles for ligand biotin was quantified by titration with biotin-4-fluorescein to 2.5 biotin binding sites per 100 nm2.     

Incorporation of liquid-like multiwalled carbon nanotubes into an epoxy matrix by solvent-free processing

Covalent attachment of 2,2'-(ethylenedioxy)-diethylamine to multiwalled carbon nanotubes (MWCNTs) produced amino-functionalized MWCNTs which behaved like liquids at ambient temperature. These liquid-like MWCNTs (l-MWCNTs) could be homogeneously dispersed and chemically embedded in an epoxy matrix by solvent-free processing. In contrast, solid MWCNTs (s-MWCNTs) functionalized by 1,8-diaminooctane were poorly dispersed in epoxy although they possess chemical structures and functionalization comparable to l-MWCNTs. An epoxy composite filled with pristine MWCNTs (p-MWCNTs) was also fabricated in the absence of a solvent at the same loading for comparison. The molecular level coupling of l-MWCNTs and epoxy provided significant improvements in overall mechanical properties relative to those composites containing p-MWCNTs and s-MWCNTs. The Young's modulus, storage modulus, tensile strength, failure strain and toughness of neat epoxy were increased by 28.4, 23.8, 22.9, 24.1 and 66.1%, respectively, by adding 0.5?wt% of l-MWCNTs. Thus, functionalized carbon nanotubes in liquid form contributed to better dispersion and superior interfacial bonding with the epoxy matrix, thereby facilitating greater mechanical reinforcement efficiency.     

Investigations of the Interaction of Nickel and Carbon Monoxide with Solid Films of C60 and C70 by UV and X-Ray Photoelectron Spectroscopy

Based on UV and X-ray photoelectron spectroscopy, it is shown that nickel metal clusters deposited on solid C₆₀ and C₇₀ films cause marked changes in the valence band spectra. In addition, the C 1s core-level of the fullerenes shift to lower binding energies while the Ni 2p_3/2 core level shifts towards higher binding energies, especially at small metal coverages. These observations signify the occurrence of charge-transfer from the nickel metal to the fullerene. We also show that CO adsorbs weakly on C₆₀ and C₇₀ surfaces.     

Antibacterial surfaces through dopamine functionalization and silver nanoparticle immobilization

Immobilization of silver nanoparticles on the dopamine functionalized polyimide (PI) films was carried out by photo-induced silver ion-reduction under atmosphere conditions. The dopamine has been successfully deposited on the PI surface in mild aqueous environments. The effects of pH, dopamine concentration and reaction time on the dopamine polymerization were investigated. The water contact angles of the poly(dopamine) functionalized PI films reduced remarkably in comparison with that of the pristine PI film. The chemical composition and structure of the UV-induced deposited-silver on the modified PI films were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The topography of the modified PI films was investigated by scanning electron microscope (SEM). The deposited poly(dopamine) layer acted as binding sites for the silver ions. The silver-plated PI films showed good antibacterial activity due to that biofilm formation was inhibited on the polymeric surfaces in contact with bacteria.     

Fullerene films deposited by evaporation in vacuum using spot-focused annular electron beam

A rapidly focused annular electron beam can provide for the effective evaporation of a fullerene mixture in a vacuum of ～10^?2 Pa. A 1-kW beam focused into a spot within 0.1–1 s produces explosive evaporation of a fullerene target at an extremely high efficiency of heating. A comparison of the Raman and electronic absorption spectra of the initial fullerene powder and a film deposited upon its evaporation shows that C₆₀ and C₇₀ fullerenes are evaporated without rupture of C-C covalent bonds. The electron beam evaporation in vacuum has been successfully used to obtain fullerene films on substrates with an area of ～0.1 m².     

Electron structure of thin fullerene films deposited by various methods

The valence-band photoelectron spectra and the photoelectron energy loss spectra behind the C1s peak in the X-ray photoelectron spectra were studied in thin fullerene films deposited by various methods. The fine structure in the density of states near the valence band bottom observed for the fullerene films deposited by the method of pulsed supersonic molecular beam (SMB) with a helium carrier may be indicative of the presence of a long-range order. The spectra of π-plasmon losses in the films obtained by methods of thermal and SMB deposition exhibit a significant difference that can be related to a closer packing of C₆₀ molecules in the latter case.     

Composite inks of poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate)/silver nanoparticles and electric/optical properties of inkjet-printed thin films

Poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate)/silver nanoparticles composite inks have been prepared through in situ synthesis and ultrasonic dispersion. The developed inks were proved to be suitable for various inkjet printing trials to deposit the thin films which were subsequently characterized to assess their electric and optical properties. The results have indicated that the dedoping of PSS from PEDOT during the in situ synthesis can be detrimental to the conductivity of the deposited composite films. However, the addition of silver nanoparticles to pristine PEDOT:PSS has significantly enhanced the conductivity of the thin films, with an inevitable loss in transparency. The various factors that can influence the properties of the thin films have also been analyzed and discussed. This study provides an insight into the effect of silver nanoparticles on PEDOT:PSS thin films deposited using inkjet printing process, and their properties due to the methods of ink formulation.     

Estimation of thermo-mechanical and fire resistance profile of epoxy coated polyurethane/fullerene composite films

Novel polyurethane (PU) was prepared and reinforced with fullerene C-60 (1–10 wt.%). An epoxy, diglycidyl 1,2-cyclohexanedicarboxylate, was coated on PU/Full-C60 films using dip coating technique. Epoxy coated PU/Full-C60 revealed dense and consistent network morphology of epoxy-polyurethane with embedded fullerene nanoparticles. Epoxy coated PU/Full-C60 1–10 films showed higher values of tensile strength 86.9–90.3 MPa (79% increase relative to PU) and tensile modulus 33.3–47.6 GPa. In Epoxy coated PU/Full-C60 1–10, T_max was increased to 521°C and char yield to 45%. Moreover increasing fullerene content decreased PHRR from 302 to 138 kW/m², i.e., 55% reduction in flammability than PU.     

Glucose/Fe-doped C70 fullerene hybrid biosensor: theoretical study

Abstract

The interaction between glucose molecule and C70 fullerene (pristine and Fe-doped) was investigated with the aid of density functional theory. Our results provide useful information that uncover the chemical and biological activities of C70 when interact with glucose molecule. To mimic real situations, all possible configurations of glucose with respect to fullerene were investigated under both vacuum and distilled water mediums. As expected, no significant change in the calculated energy gaps for all pristine configurations regardless the simulated medium, which indicates that the interaction between glucose molecule and pristine Fullerene is weak physisorption. However, doping fullerene with Fe atom significantly reduced the energy gap for all configurations of the complex which in turn offers an advantage over pristine fullerene for measuring glucose in real situations such as blood.     

The binding energy of molecules in thin fullerene films

Thin fullerene films formed using the methods of pulsed supersonic molecular beam (SMB) deposition and thermal deposition (TD) in vacuum were studied by thermodesorption (TDS) mass spectroscopy. The TDS spectra of SMB films show a significantly higher temperature of desorption (827.8 K) of fullerene molecules as compared to the value (583 K) observed in the spectra of TD films. It is suggested that the higher binding energies of fullerene molecules in the former films are explained by the formation of polymer structures due to heating in the course of TDS measurements.     

Thin fullerene-containing films synthesized by ion beam sputtering of fullerene mixtures with doping additives in vacuum

A new approach to the synthesis of films containing fullerenes and doping elements is described. It is suggested that a cluster mechanism of the target sputtering by accelerated ions makes possible the deposition of fullerenes on a substrate with a certain probability for dopant atoms being introduced into the cavities of fullerene molecules and a higher probability of their occurrence between fullerene molecules. The proposed method has been experimentally implemented by using an Ar⁺ ion beam to sputter C₆₀/C₇₀ fullerene mixtures (synthesized in a plasmachemical reactor at a pressure of 10⁵ Pa) pressed into disk targets with a doping element (Fe, Na, B, Gd, or Se). The ion beam sputtering of dopant-containing fullerene mixtures in a vacuum of ～10^?2 Pa allowed micron-thick films containing C₆₀ and C₇₀ fullerenes and the corresponding dopant element (Fe, Na, B, Gd, or Se) to be grown on quartz substrates.     

Thermal-Decomposition Spectra of Submicrometer Films of Polybutylmethacrylate–C<Subscript>60</Subscript> Fullerene Composite: Effects of Filler Concentration and UV Irradiation

Thermal-desorption mass spectra of optically thin films of polybutylmethacrylate–C₆₀ fullerene composite with various fullerene concentrations have been analyzed. The effects of UV radiation on the films under atmospheric conditions have been examined.     

Interaction between fullerenes and single-wall carbon nanotubes: the influence of fullerene size and electronic structure

A series of fullerenes and endohedral metallofullerenes peapods have been synthesized by supercritical method in high filling rate. The interaction between SWNTs and various kinds of fullerenes (C60, C70, C78, C84) and metallofullerenes (Gd@C82, Er@C82, Ho@C82, Y@C82) has been further investigated. The slight blue shift of G-band in Raman spectra with respect to pristine SWNTs was attributed to the charge transfer from SWNTs to fullerenes cage. The obvious RBM shift strongly depended on the distance between the inner wall of the SWNTs and the fullerene cage and also partly associated with the electronic structure of the fullerene. These results indicated that the interaction between fullerenes and SWNTs, which was considered to be the van de walls interaction, can be influenced by the cage size and the kind of fullerenes.     

Bare plasmonic metal nanoparticles: synthesis,characterisation and in vitro toxicity assessment on a liver carcinoma cell line

Metal nanoparticles have generated great interest due to their excellent optical and chemical properties. The widely used chemical method for synthesising nanoparticles involves capping agents for colloidal stability. However, there are scarce reports on the application of metal nanoparticles synthesised without using capping agents. Hence, there is a need to develop pristine nanoparticles devoid of capping that can be used for translational research. Here, the authors developed a facile and rapid method for synthesising bare metal nanoparticles (platinum/silver/gold) that are chemically reactive and stable for a month upon storage. They synthesised bare metal nanoparticles of sub‐15 nm and characterised using standard techniques (UV–VIS‐NIR/DLS/zeta//TEM/XRD). They assessed the safety of the synthesised nanoparticles on the liver carcinoma cell line (HepG2). Bare gold and platinum nanoparticles were non‐toxic in comparison to bare silver nanoparticles. Bare metal nanoparticles were also checked for metal detection wherein antimony, mercury and chromium were detected using bare gold and silver nanoparticles. The spectroscopic shifts of the nanoparticles when bound to metals resulted in blue and red shifting of the plasmon band, indicating the sensing of metals. These results show that bare metal nanoparticles have the potential to emerge as a promising candidate for biomedical and sensing applications.Inspec keywords: ultraviolet spectra, electrokinetic effects, liver, cellular biophysics, nanoparticles, cancer, toxicology, gold, platinum, X‐ray diffraction, silver, colloids, transmission electron microscopy, plasmonics, visible spectra, nanomedicineOther keywords: bare plasmonic metal nanoparticles, liver carcinoma cell line, capping agents, pristine nanoparticles, bare metal nanoparticles, synthesised nanoparticles, platinum nanoparticles, silver nanoparticles, XRD, TEM