Inhomogeneous character of the initial stage of ion beam deposition of ultrathin gold films

Gold films with thicknesses ranging from below 1 nm to 3 nm have been simultaneously deposited by the ion beam sputter technique onto the surface of glass substrates smooth on a subnanometer level and onto Si(001) substrates with nanodimensional inhomogeneities in the form of germanium atomic islands. Irrespective of the substrate surface nature, gold deposition initially leads to the formation of a stable layer with a thickness of several atomic monolayers. The gold films with thicknesses above 2 nm are continuous and homogeneous. Terminated in an intermediate stage, the sputter deposition of gold may result in the formation of an inhomogeneous layer of the island type. The results are interpreted taking into account the well-known fact that a high-energy component is present in the flux of the ion beam sputtered target material.     

Inlet ionization: a new highly sensitive approach for liquid chromatography/mass spectrometry of small and large molecules

Inlet ionization is a new approach for ionizing both small and large molecules in solids or liquid solvents with high sensitivity. The utility of solvent based inlet ionization mass spectrometry (MS) as a method for analysis of volatile and nonvolatile compounds eluting from a liquid chromatography (LC) column is demonstrated. This new LC/MS approach uses reverse phase solvent systems common to electrospray ionization MS. The first LC/MS analyses using this novel approach produced sharp chromatographic peaks and good quality full mass range mass spectra for over 25 peptides from injection of only 1 pmol of a tryptic digest of bovine serum albumin using an eluent flow rate of 55 μL min(-1). Similarly, full acquisition LC/MS/MS of the MH(+) ion of the drug clozapine, using the same solvent flow rate, produced a signal-to-noise ratio of 54 for the major fragment ion with injection of only 1 μL of a 2 ppb solution. LC/MS results were acquired on two different manufacturer's mass spectrometers using a Waters Corporation NanoAcquity liquid chromatograph.     

Surface-Enhanced Raman Scattering Detection of pH with Silica-Encapsulated 4-Mercaptobenzoic Acid-Functionalized Silver Nanoparticles

Sensors based upon surface-enhanced Raman spectroscopy (SERS) are attractive because they have narrow, vibrationally specific spectral peaks that can be excited using red and near-infrared light which avoids photobleaching, penetrates tissue, and reduces autofluorescence. Several groups have fabricated pH nanosensors by functionalizing silver or gold nanoparticle surfaces with an acidic molecule and measuring the ratio of protonated to deprotonated Raman bands. However, a limitation of these sensors is that macromolecules in biological systems can adsorb onto the nanoparticle surface and interfere with measurements. To overcome this interference, we encapsulated pH SERS sensors in a 30 nm thick silica layer with small pores which prevented bovine serum albumin (BSA) molecules from interacting with the pH-indicating 4-mercaptobenzoic acid (4-MBA) on the silver surfaces but preserved the pH-sensitivity. Encapsulation also improved colloidal stability and sensor reliability. The noise level corresponded to less than 0.1 pH units from pH 3 to 6. The silica-encapsulated functionalized silver nanoparticles (Ag-MBA@SiO(2)) were taken up by J774A.1 macrophage cells and measured a decrease in local pH during endocytosis. This strategy could be extended for detecting other small molecules in situ.     

Using volatile solvents for ion formation in liquid molecular beam expansion mass spectrometry

Cocrystallization between analyte and matrix is required by matrix-assisted laser desorption/ionization and can represent a significant limitation of the technique. A molecular beam expansion, mass spectrometric method has been developed to explore the possibility of using pure solvents as matrix to avoid cocrystallization. Two kinds of solvent, liquid CS2 and liquid or supercritical CO2, have been studied with 266-nm UV laser irradiation. We successfully ionized a number of compounds, including caffeine, guanine, cholesterol, and mixed fullerenes. Under some conditions, the mass spectra reflect parent radical cations formed by photoionization. Under other conditions, protonated, sodiated (and with CS2 even sulfated) ions are seen reflecting a nonunimolecular ionization process. When UV-transparent CO2 is used as a solvent, only analyte molecules with a UV chromophore are detected. However, with UV-absorbing CS2, we demonstrate ionization of molecules lacking a UV chromophore. This work provides strong evidence that one can form solvent clusters containing analyte, that laser photoionization of the solvent precedes ionization of the analyte, and that solvent evaporation along with the indirect ionization leads to reduced parent ion fragmentation. The exploration of this now demonstrated concept with other solvents would appear fruitful for future work.     

离子束溅射法制备碳氮薄膜及其结构表征

采用离子束溅射沉积技术,对不同氮离子束能量情况下制备的氮化碳薄膜,进行了拉曼(Raman)和红外光谱(FT-IR)分析,并采用透射电子显微镜(TEM)分析其表面形貌,研究所制备薄膜的化学组成和键合结构。结果显示:随着氮离子束能量增大,氮碳薄膜的沉积速率减小,薄膜结构中sp2含量增大,薄膜有序度增加,另外薄膜结构的团簇尺寸大幅下降,团簇趋于均匀分布。     

Ion Beam Modification of Powders in the Rotating Wing Drum

Most of the properties of powders are determined by their surface characteristics. Therefore, surface modification techniques are a promising tool for powder modification. Among these are ion beam methods such as ion implantation, ion beam sputtering and ion beam assisted deposition. These techniques are typical line-of-sight processes. Only those parts of a workpiece, or for the present case a powder particle, which are directly turned towards the source of ion or atom beam and are not shaded off, are treated properly. This renders uniform treatment of powders difficult. In the present study, facilities for ion beam treatment of powders are described. The features of a rotating wing drum for agitating the powder while under bombardment by an ion beam are discussed in detail. As an example, results of ion beam sputter deposition of alumina powder with gold are presented. Trace analytical methods were used to determine the amount of de posited gold in dependence on the process parameters. The powder grain surfaces were investigated with electron microscopy.     

New developments in ionized-cluster beam and reactive ionized-cluster beam deposition techniques

Ionized-cluster beam (ICB) and reactive ionized-cluster beam (R-ICB) deposition techniques are described from the standpoint of the ion-based technique, as applied to the production of thin film devices. In ICB deposition, clusters (macroparticles consisting of approximately 10³ atoms loosely coupled together) instead of atomic or molecular particles are used after ionization, resulting in a remarkable improvement of epitaxial film growth and of the quality of deposited films with strong adhesion. This paper describes in detail the influences of the ion content and the acceleration voltage on nucleation and film properties. MnBi films as magneto-optical memories and ZnO epitaxial films as optical devices are discussed as practical applications of the ICB and R-ICB deposition techniques.     

Clustering effects on discontinuous gold film NanoCells

Reproducible negative differential resistance (NDR)-like switching behavior is observed in NanoCells. This behavior is attributed to the formation of filaments and clusters between the discontinuous gold films. Control experiments are performed by self-assembly of insulating molecules between the gold islands and conducting molecules on these islands. Additional control experiments are performed by removing the filaments and clusters between islands using a piranha bath. The results are consistent with theoretical predictions and extend the domain of molecular electronics based in organic molecules to include nanosized clusters as active units. This facilitates a scenario where synthetically accessible organic molecules, with defined characteristics, can be adjusted by metallic nanoclusters as an in situ fine-tuning element, able to compensate for the lack of addressing in the nanosize regime.     

Carbon nanotubes induce secondary structure changes of bovine albumin in aqueous phase

Interaction of nanomaterials to protein molecules is one of the most important issues to deeply understand the influences of the nanomaterials upon physiological processes and protein functions. So far most of investigations focused on the protein molecules adsorbed on the nanomaterials surface, less is known about those in the aqueous phase (not absorbed). In this work, luminescent spectroscopy analysis, circular dichroism measurement, atomic force microscopy, matrix-assisted laser desorption/ionization time of flight mass spectrometry, isoelectric focusing and sulfate polyacrylamide gel electrophoresis were used to investigate the influence of oxidized water-soluble multiwalled carbon nanotubes (CNT) dispersing in aqueous solution upon the structures of bovine serum albumin (BSA) through co-incubation. We focused on BSA molecules that stayed in the aqueous phase instead of those adsorbed by CNT. Experimental results show that the fractions of beta-sheet decreased from 33.3% to 29.8% and beta-turn increased from 2% to 5% in reference with native BSA. There was a slight increase of alpha-helix and a slight reduction of random coil. BSA molecules that had been encountered with CNT and were left in the solution formed a loose and flatten morphology on graphite substrates instead of their native tight and round morphology observed by AFM. The value of isoelectric point for BSA after exposed to CNT moved towards to a higher pH position compared with native BSA. All together, it was concluded that the oxidized water-soluble multiwalled carbon nanotubes not only adsorb bovine serum albumin molecules to their surface, but also induces albumin molecules in the aqueous solution undergo secondary structure changes, which lead to a conformation change.     

Design and characterization of a multisource hand-held tandem mass spectrometer

A wireless-controlled miniature rectilinear ion trap mass spectrometer system, total weight with batteries 5.0 kg, consuming less than 35 W of power, and having dimensions of 22 cm in length by 12 cm in width by 18 cm in height, is characterized. The design and construction of the mass spectrometer including mass analyzer, vacuum system, electronics system, and data acquisition and processing systems, is detailed. The mass spectrometer is compatible with various types of ionization sources including a glow discharge electron impact ionization source used in the internal ionization mode, and various atmospheric pressure ionization sources, including electrospray ionization, atmospheric pressure chemical ionization, and desorption electrospray ionization, which are employed for external, atmospheric pressure ionization. These external sources are coupled to the miniature mass spectrometer via a capillary interface that is operated in a discontinuous fashion (discontinuous atmospheric pressure interface) to maximize ion transport. The performance of the mass spectrometer for large and small molecules is characterized. Limits of detection in the parts-per-billion range were obtained for selected compounds examined using both the internal ionization and external ionization modes. Tandem mass spectrometry and fast in situ analysis capabilities are also demonstrated using a variety of compounds and ionization sources. Protein molecules are analyzed as the multiply protonated molecules with mass/charge ratios up to 1500 Da/charge.     

Design and performance of an instrument for soft landing of biomolecular ions on surfaces

A new ion deposition apparatus was designed and constructed in our laboratory. Our research objectives were to investigate interactions of biomolecules with hydrophilic and hydrophobic surfaces and to carry out exploratory experiments aimed at highly selective deposition of spatially defined and uniquely selected biological molecules on surfaces. The apparatus includes a high-transmission electrospray ion source, a quadrupole mass filter, a bending quadrupole that deflects the ion beam and prevents neutral molecules originating in the ion source from impacting the surface, an ultrahigh vacuum (UHV) chamber for ion deposition by soft landing, and a vacuum lock system for introducing surfaces into the UHV chamber without breaking vacuum. Ex situ analysis of surfaces following soft landing of mass-selected peptide ions was performed using 15 keV Ga+ time-of-flight secondary ion mass spectrometry and grazing incidence infrared reflection-absorption spectroscopy. It is shown that these two techniques are highly complementary methods for characterization of surfaces prepared with a range of doses of mass-selected biomolecular ions. We also demonstrated that soft landing of peptide ions on surfaces can be utilized for controlled preparation of peptide films of known coverage for fundamental studies of matrix effects in SIMS.     

The influence of beam defocus on volume growth rates for electron beam induced platinum deposition

Electron beam induced deposition (EBID) is a versatile method for the controlled fabrication of conducting, semi-conducting and non-conducting structures down to the nanometer scale. In contrast to ion beam induced deposition, EBID processes are free of sputter effects, ion implantation and massive heat generation; however, they have much lower deposition rates. To push the deposition efficiency further towards its intrinsic limits, the individual influences of the process parameters have to be explored. In this work a platinum pre-cursor is used for the deposition of conducting nanorods on highly oriented pyrolytic graphite. The study shows the influence of a beam defocus during deposition on the volume growth rates. The temporal evolution of volume growth rates reveals a distinct maximum which is dependent on the defocus introduced, leading to an increase of deposited volumes by a factor 2.5 after the same deposition times. The observed maximum is explained by an increasing and saturating electron yield contributing to the final deposition process and constantly decreasing diffusion abilities of the pre-cursor molecules toward the tip of the nanorods, which is further supported by dwell time experiments.     

Chemical characterization of individual, airborne sub-10-nm particles and molecules

A nanoaerosol mass spectrometer (NAMS) is described for real-time characterization of individual airborne nanoparticles. The NAMS includes an aerodynamic inlet, quadrupole ion guide, quadrupole ion trap, and time-of-flight mass analyzer. Charged particles in the aerosol are drawn through the aerodynamic inlet, focused through the ion guide, and captured in the ion trap. Trapped particles are irradiated with a high-energy laser pulse to reach the "complete ionization limit" where each particle is thought to be completely disintegrated into atomic ions. In this limit, the relative signal intensities of the atomic ions give the atomic composition. The method is first demonstrated with sucrose particles produced with an electrospray generator. Under the conditions used, the particle detection efficiency (fraction of charged particles entering the inlet that are subsequently analyzed) reaches a maximum of 10(-4) at 9.5 nm in diameter and the size distribution of trapped particles has a geometric standard deviation of 1.1 based on a log-normal distribution. A method to deconvolute overlapping multiply charged ions (e.g. C3+ and O4+) is presented. When applied to sucrose spectra, the measured C/O atomic ratio is 1.1, which matches the expected ratio from the molecular formula. The spectra of singly charged bovine serum albumin (BSA) molecules are also presented, and the measured and expected C/N/O atomic ratios are within 15% of the each other. Also observed in the BSA spectra are signals from 13C and 32S which arise from 40 and approximately 34 atoms per molecule (particle), respectively. Potential applications of NAMS to atmospheric chemistry and biotechnology are briefly discussed.     

Electrochemical synthesis of gold nanoparticles onto indium tin oxide glass and application in biosensors

A simple one-step method for the electrochemical deposition of gold nanoparticles (GNPs) onto bare indium tin oxide film coated glass substrate without any template or surfactant was investigated. The effect of electrolysis conditions such as potential range, temperature, concentration and deposition cycles were examined. The connectivity of GNPs was analyzed by UV-Vis absorption spectroscopy and scanning electron microscopy. The nanoparticles were found to connect in pairs or to coalesce in larger numbers. The twin GNPs display a transverse and a longitudinal localized surface plasmon resonance (LSPR) band, which is similar to that of gold nanorods. The presence of longitudinal LSPR band correlates with high refractive index sensitivity. Conjugation of the twin-linked GNPs with albumin bovine serum-biotin was employed for the detection of streptavidin as a model based on the specific binding affinity in biotin/streptavidin pairs. The spectrophotometric sensor showed concentration-dependent binding for streptavidin.     

Immobilization of angiotensin II and bovine serum albumin on strip-patterned ZnO nanorod arrays

For an effective protein immobilization for highly sensitive biosensors, we determined the binding properties and characteristics of angiotensin II and bovine serum albumin on the surface of patterned ZnO nanorod arrays (NRAs) which were selectively grown on desired areas of Si substrates. The surfaces of ZnO NRAs were modified by 3-aminopropyltriethoxysilane and gluteraldehyde, and the activated NRAs were then conjugated with angiotensin II protein and bovine serum albumin. The silanization process and conjugation of protein were verified by secondary ion mass spectroscopy (SIMS) and X-ray photoelectron spectroscopy (XPS) techniques. The immobilizing densities of proteins determined by Coomassie protein assay were 4.5 microg/cm2 for angiotensin II and 5.3 microg/cm2 for bovine serum albumin.     

Laser desorption combined with hyperthermal surface ionization time-of-flight mass spectrometry

A setup combining laser desorption of nonvolatile molecules and their aerodynamic acceleration in a supersonic molecular beam followed by hyperthermal surface ionization in a reflectron time-of-flight mass spectrometer is described. While laser desorption performs the intact transfer of the analyte molecules into the gas phase, hyperthermal surface ionization opens up the possibility to efficiently ionize even larger molecules with a small and potentially controlled degree of fragmentation. Being an ionization technique, which is particularly effective for aromatic and heterocyclic compounds, the selectivity can further be increased by tuning the kinetic energy to which the molecules are accelerated in the supersonic beam. The results obtained for several polycyclic aromatic hydrocarbons and biochemical substances show that sufficient acceleration can be achieved even for molecules with a molecular weight above 5000 amu and that HSI preserves its advantageous features even for thermally labile large molecules such as insulin.     

Theory for the solvation of alkali metal atoms in clusters of polar molecules. Many-body polarization interactions

We present a theory for the binding energy of clusters of polar molecules (ammonia or water) and an alkali metal atom (Na, Cs). The metal atom dissociates into a positive ion and a separate valence electron, which has the role of an excess electron. The positive ion and the electron have strong electromagnetic interactions with the molecules of the cluster. It is shown that the resulting polarization energy contains important many-body terms and that it is not possible to use a pair-potential approximation for the electronic potential. We propose a model for the ionization potential, including both-initial and final state effects. Our results for the ionization potential of metal-ammonia clusters agree well with recent experiments, indicating that a size-dependent transition from a single-center structure of small clusters to a fully solvated two-center structure for large clusters occurs. Spherically symmetric model structures do not yield a good agreement with experimental results for Na(H₂O)_n clusters. Thus these clusters either have a distinct asymmetric shape because of strong hydrogen bridge bonding or an autoionizing resonance might have been observed in the experiment instead of the true ionization threshold.     

Quantification of proteins on gold nanoparticles by combining MALDI-TOF MS and proteolysis

Protein-coated nanoparticles have been used in many studies, including those related to drug delivery, disease diagnosis, therapeutics, and bioassays. The number and density of proteins on the particles' surface are important parameters that need to be calculable in most applications. While quantification methods for two-dimensional surface-bound proteins are commonly found, only a few methods for the quantification of proteins on three-dimensional surfaces such as nanoparticles have been reported. In this paper, we report on a new method of quantifying proteins on nanoparticles using matrix assisted laser desorption/ionization time of flight (MALDI-TOF) mass spectrometry (MS). In this method, the nanoparticle-bound proteins are digested by trypsin and the resulting peptide fragments are analyzed by MALDI-TOF MS after the addition of an isotope-labeled internal standard (IS) which has the same sequence as a reference peptide of the surface-bound protein. Comparing the mass intensities between the reference peptide and the IS allows the absolute quantification of proteins on nanoparticles, because they have the same molecular milieu. As a model system, gold nanoparticles were examined using bovine serum albumin (BSA) as a coating protein. We believe that our strategy will be a useful tool that can provide researchers with quantitative information about the proteins on surfaces of three-dimensional materials.     

Copper quantum clusters in protein matrix: potential sensor of Pb2+ ion

A one-pot synthesis of extremely stable, water-soluble Cu quantum clusters (QCs) capped with a model protein, bovine serum albumin (BSA), is reported. From matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, we assign the clusters to be composed of Cu(5) and Cu(13) cores. The QCs also show luminescence properties having excitation and emission maxima at 325 and 410 nm, respectively, with a quantum yield of 0.15, which are found to be different from that of protein alone in similar experimental conditions. The quenching of luminescence of the protein-capped Cu QCs in the presence of very low hydrogen peroxide concentration (approximately nanomolar, or less than part-per-billion) reflects the efficacy of the QCs as a potential sensing material in biological environments. Moreover, as-prepared Cu QCs can detect highly toxic Pb(2+) ions in water, even at the part-per-million level, without suffering any interference from other metal ions.     

Direct fabrication of nanoscale bio-adhesive patterns by electron beam surface modification of plasma polymerized poly ethylene oxide-like coatings

In this study we present a method to produce nanostructured surfaces containing bio-adhesive features inside a non bio-adhesive matrix. The strategy is based on the combination of low pressure plasma polymerization and electron beam lithography processes and allows the fabrication of the structured materials in just two steps without using any solvents. In a first step, a thin protein-and-cell-repelling coating (～10?nm) is obtained by plasma polymerization of Di-glyme. Then, in a second step, the bio-adhesive properties of the layer are tuned by monitoring the concentration of ether bonds of the film by irradiating it locally by different irradiation doses with an electron beam. Time-of-flight secondary ion mass spectroscopy and atomic force microscopy analysis have been used to characterize the produced surfaces. Experiments with a model protein (bovine serum albumin) on the patterned surfaces show preferential adhesion to the irradiated regions, indicating the potential of this simple technique for the development of highly compacted sensitive bio-sensing devices.