Chemical differences between sapwood and heartwood of Chamaecyparis obtusa detected by ToF-SIMS

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to investigate the distribution of elements, Na, Mg, Al, K, and Ca, and lignin, in the contiguous growth rings including the sapwood/heartwood boundary in Hinoki cypress (Chamaecyparis obtusa). Lignin was distributed almost uniformly from sapwood to heartwood. The concentrations of most of the elements showed a drastic increase or decrease in the transition zone between sapwood and heartwood. The ToF-SIMS mapping analysis showed that most of the elements predominantly localized in the ray parenchyma cells in the inner transition zone and heartwood, while the elements showed no localization and distributed almost uniformly in the outer transition zone near sapwood. The result suggests that the ray parenchyma cells play a role in behaviors of elements during the transition from sapwood to heartwood.     

A new analysis of the depolymerized fragments of lignin polymer in the plant cell walls using ToF-SIMS

High mass resolution ToF-SIMS spectra by Au⁺ primary ion bombardment were used to investigate exact structures of characteristic ions of lignin in plant cell walls. Previous study using Ga primary ion bombardment showed the characteristic peaks of guaiacyl lignin at m/z 137 ([C₈H₉O₂]⁺) and 151 ([C₈H₇O₃]⁺ and [C₉H₁₁O₂]⁺), but it was unclear whether the peak at m/z 151 in the spectrum of lignin in situ in plant cell walls is actually a double-component, [C₈H₇O₃]⁺ (151.0394) and [C₉H₁₁O₂]⁺ (151.0758). This report achieved a higher mass resolution with lignin samples, showing that the peak at m/z 151 is dominated by the C₆-C₁ benzoyl ion, [C₈H₇O₃]⁺, not the C₆-C₂ ion, [C₉H₁₁O₂]⁺.     

Quantitative ToF-SIMS studies of protein drug release from biodegradable polymer drug delivery membranes

Biodegradable polymers are of interest in developing strategies to control protein drug delivery. The protein that was used in this study is Keratinocyte Growth Factor (KGF) which is a protein involved in the re-epithelialization process. The protein is stabilized in the biodegradable polymer matrix during formulation and over the course of polymer degradation with the use of an ionic surfactant Aerosol-OT (AOT) which will encapsulate the protein in an aqueous environment. The release kinetics of the protein from the surface of these materials requires precise timing which is a crucial factor in the efficacy of this drug delivery system.Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used in the same capacity to identify the molecular ion peak of the surfactant and polymer and use this to determine surface concentration. In the polymer matrix, the surfactant molecular ion peak was observed in the positive and negative mode at m/z 467 and 421, respectively. These peaks were determined to be [AOT + Na⁺] and [AOT − Na⁺]. These methods are used to identify the surfactant and protein from the polymer matrix and are used to measure the rate of surface accumulation. The second step was to compare this accumulation rate with the release rate of the protein into an aqueous solution during the degradation of the biodegradable film. This rate is compared to that from fluorescence spectroscopy measurements using the protein autofluorescence from that released into aqueous solution [C.M. Mahoney, J. Yu, A. Fahey, J.A.J. Gardella, SIMS depth profiling of polymer blends with protein based drugs, Appl. Surf. Sci. 252 (2006), 6609-6614.].     

ToF-SIMS studies of Bacillus using multivariate analysis with possible identification and taxonomic applications

In this paper we discuss the application of ToF-SIMS with an Au₃⁺ primary ion beam, combined with principal components analysis (PCA) and discriminant function analysis (DFA) for the identification of individual strains of two Bacillus species. The ToF-SIMS PC-DFA methodology is capable of distinguishing bacteria at the strain level based on analysis of surface chemical species. By classifying the data using hierarchical cluster analysis (HCA) we are able to show quantitative separation of species and of these strains. This has taxonomic implications in the areas of rapid identification of pathogenic microbes isolated from the clinic, food and environment.     

Hair dye distribution in human hair by ToF-SIMS

A single hair sample preparation protocol modified from reported method was developed and used to prepare longitudinally sectioned hair for ToF-SIMS analysis. Preliminary results demonstrate that ToF-SIMS is capable of providing molecular distribution of fragment ions from intrinsic constituents as well as external chemicals like the hair dye ingredients used in this study. The observation of pPDA and H₂PO₄⁻ penetrating into the internal region of hair might initiate a renewed interest in exposure study.     

Low temperature synthesis and characterization of rare earth orthoferrites LnFeO3 (Ln=La, Pr and Nd) from molten NaOH flux

Rare earth orthoferrites of the general formula LnFeO₃ (Ln=La, Pr and Nd) phases have been synthesized for the first time in molten NaOH flux at a temperature as low as 400 ^°C. The flux-grown oxides were characterized by XRD, SEM, EDX, FT-IR and temperature dependent electrical resistivity measurements. The crystal structures of these materials have been refined by the Rietveld profile analysis method using powder XRD data. All these oxides crystallize in the orthorhombic structure (space group Pbnm, no. 62) and exhibit insulating behavior. As-synthesized samples show three active IR absorption bands for Fe-O stretching vibration (ν₁ mode) and O-Fe-O deformation vibration (ν₂ mode). In the KOH flux on the other hand, no product formation is observed, thus providing evidence for the differences in the two alkali fluxes.     

ToF-SIMS characterisation of diterpenoic acids after chromatographic separation

Microcolumn liquid chromatography (μHPLC) coupled on-line with time of flight secondary ion mass spectrometry (ToF-SIMS) was applied for mixture of diterpenoic acids (abietic, gibberellic and kaurenoic) analysis. Chromatographic effluent, with analytes separated, was carried out directly onto different, ToF-SIMS compatible surface substrates, for further ToF-SIMS analysis. Silica gel Si₆₀, aluminium backplate modified Si₆₀, monolithic silica gel and Raman spectroscopy chromatographic thin layers were used as the deposition substrates in this experiment. By ToF-SIMS surface imaging the deposition trace picture has been obtained. Effluent deposition surface area was scanned for diterpenoic acid fragment mass values based on mass spectrometric library. Measured ToF-SIMS dataset of fragment abundance and intensities were used for preliminary fragmentation schemes construction. The lowest substrate background activity has been established for monolithic silica gel thin layer and aluminium backplate modified Si₆₀ thin layer. In the case of Raman spectroscopy pre-treated thin layer or conventional chromatographic thin layer Si₆₀, the both, high background signal intensity and impossibility to construct negative ions surface image, were observed. Diterpenoic acids studied serve the similar mass spectrum but ToF-SIMS coupled with liquid chromatographic separation brings new impact to the positive identification of analytes studied.     

Characterisation of human hair surfaces by means of static ToF-SIMS: A comparison between Ga and C60 primary ions

This study deals with the secondary ion yield improvement induced by using C₆₀⁺ primary ions instead of Ga⁺ ones to characterize human hair surfaces by ToF-SIMS. For that purpose, a bunch of hair fibres has been analysed with both ion sources. A high improvement is observed for the detection of amino acids with C₆₀⁺ primary ions as compared to Ga⁺ ions. As an example, a yield enhancement factor greater than 3000 is found for the CNO⁻ peak. A similar gain is observed for the positive secondary ions characteristic of the amino acids. Most of the atomic ions, such as Ca⁺, O⁻ and S⁻, constitute minor peaks with C₆₀⁺ ions while they often dominate the spectrum in the case of Ga⁺ ions. However, with the C₆₀⁺ source, a series of inorganic combination peaks with the elements Ca, S and O are observed in the positive spectra (i.e. HCaSO₄⁺), while they are marginal with the Ga⁺ source. For the mass range beyond 100 m/z and in both polarities, the hair fingerprints are similar with both sources. In average, for a comparable number of primary ions per spectrum, the C₆₀⁺ ion source gives intensities between two and three orders of magnitude higher than the Ga⁺ one.     

ToF-SIMS PCA analysis of Myrtus communis L.

Nowadays there is a growing interest of researchers for the application of sophisticated analytical techniques in conjunction with statistical data analysis methods to the characterization of natural products to assure their authenticity and quality, and for the possibility of direct analysis of food to obtain maximum information. In this work, time-of-flight secondary ion mass spectrometry (ToF-SIMS) in conjunction with principal components analysis (PCA) are applied to study the chemical composition and variability of Sardinian myrtle (Myrtus communis L.) through the analysis of both berries alcoholic extracts and berries epicarp. ToF-SIMS spectra of berries epicarp show that the epicuticular waxes consist mainly of carboxylic acids with chain length ranging from C20 to C30, or identical species formed from fragmentation of long-chain esters. PCA of ToF-SIMS data from myrtle berries epicarp distinguishes two groups characterized by a different surface concentration of triacontanoic acid. Variability in antocyanins, flavonols, α-tocopherol, and myrtucommulone contents is showed by ToF-SIMS PCA analysis of myrtle berries alcoholic extracts.     

Fabrication and characterization of Zn1−xAlxO nanoparticles by DC arc plasma

In this paper we have introduced a simple method for the fabrication of aluminum doped zinc oxide (AZO) nanoparticles. The Zn_1−xAl_xO nanoparticles with different concentrations of Al (x=0.01, 0.03, 0.06, 0.09, 0.12) were fabricated successfully by this method. The samples were analyzed by the use of several techniques such as SEM, EDX, XRD, PL and UV-vis spectroscopy. The SEM images showed that the fabricated nanoparticles had spherical shapes. The XRD patterns of the samples indicated that the Al atoms substituted in the Zn positions in the crystal lattice of ZnO and there were some changes in the lattice parameters. A blue shift in the λ_max of the absorption and a red shift in the λ_max of the emission were observed. The results also indicated that the amount of shifts had a direct relationship with the changes in the lattice parameters.     

Multiplicities without KNO: Parton branching versus negative binomial

It is shown that parton branhing equations for the probability P_mn of m quarks and n gluons have exact solutions which violate KNO scaling. Only the approximate solution is exactly a KNO function. Corrections to this approximate solution approach KNO scaling from below in the high-z tail, in agreement with recent collider data and in contrast to the negative binomial distribution.     

Plasma enhanced CVD of SiOxCyHz thin film on different textile fabrics: Influence of exposure time on the abrasion resistance and mechanical properties

In order to improve textile fabric abrasion resistance, in this work a SiO_xC_yH_z thin film was realized by low pressure plasma chemical vapour deposition (PCVD) at room temperature, using hexamethyldisiloxane (HMDSO) as precursor compound. To test changes in the performance properties of the surface finished samples as a function of the type of the substrate, the deposition was carried out on different textile fabrics. The polymerization processes were followed by weight measurements of textile fabrics. It was found that, after PCVD, a significantly lower fabric weight loss was observed on treated samples after rubbing than on the untreated samples. The morphology, elemental composition and type of chemical bonding present in the film applied on textile fabrics were also investigated using electron scanning microscopy (SEM), energy dispersive X-ray (EDX) and infrared spectroscopy techniques (FT-IR (ATR)). The results showed a substantial enhancement of wear resistance for the surfaces modified with the presented process, while tensile and tearing strength were adversely affected.     

Localization of Na and K in rat cerebellum with imaging TOF-SIMS

High pressure-frozen (HPF), freeze-fractured and freeze-dried rat cerebellum was analyzed with imaging TOF-SIMS equipped with a Bi-cluster ion source. Data were collected separately as spectra of high mass resolution m/Δm > 8000 and images of high lateral resolution <700 nm. Images were made showing the localization of the peaks m/z = 22.99, and m/z = 39.1.Topographical effects were noted due to the freeze fracture method. This effect was compensated by normalizing images of specific secondary ions to the intensity of total secondary ions and by making PCA analysis of the image. The results showed that potassium ions were localized in blood vessels and cortex cells and sodium ions were localized in blood vessels and cerebellar interstitial tissue and in the nuclei of some cells. The sodium ion concentration was found to be higher in blood vessels than in the interstitium.     

Imaging subcellular features of a sectioned rat brain using time-of-flight secondary ion mass spectrometry and scanning probe microscopy

Coronal sections of unfixed rat brain samples were prepared on a flat substrate in order to reveal hippocampal formation (CA1-4 pyramidal neurons) and adjacent neocortical white matter. We demonstrate the feasibility of using surface sensitive techniques such as time-of-flight secondary ion mass spectrometry (ToF-SIMS) and scanning probe microscopy (SPM) to probe lipid distribution, as well as the subcellular features of neurons. In the same anatomical areas, the phase shift image in SPM is especially useful in revealing the cross-section of subcellular structures. We show that the phase shift images reveal distinctive subcellular features and ion images of CN⁻ and PO₂⁻ fragments from ToF-SIMS appear to define some of the subcellular features.     

Copper diffusion in Ti-Si-N layers formed by inductively coupled plasma implantation

Ternary Ti-Si-N refractory barrier films of 15 nm thick was prepared by low frequency, high density, inductively coupled plasma implantation of N into Ti_xSi_y substrate. This leads to the formation of Ti-N and Si-N compounds in the ternary film. Diffusion of copper in the barrier layer after annealing treatment at various temperatures was investigated using time-of-flight secondary ion mass spectrometer (ToF-SIMS) depth profiling, X-ray diffractometer (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) and sheet resistance measurement. The current study found that barrier failure did not occur until 650 °C annealing for 30 min. The failure occurs by the diffusion of copper into the Ti-Si-N film to form Cu-Ti and Cu-N compounds. FESEM surface morphology and EDX show that copper compounds were formed on the ridge areas of the Ti-Si-N film. The sheet resistance verifies the diffusion of Cu into the Ti-Si-N film; there is a sudden drop in the resistance with Cu compound formation. This finding provides a simple and effective method of monitoring Cu diffusion in TiN-based diffusion barriers.     

Measurement of the surface density of states by field ionization

It is shown that recent measurements of field ion energy distributions from clean tungsten surfaces probe the density of metal states in the vicinity of the surface. We find j(ω) = (2π/kh)Σ_m| ∫ d³rψ_m(r)γ_z|²δ(ω??_m), where j(ω) is the ion current a ω, ψ_mand ?_m are electronic metal eigenfunctions and eigenvalues in the presence of the external electric field used in field ionization and γ(z) is a function which is large near the noble gas atom. An explicit expression for γ(z) is given in the text. It is estimated that tungsten metal states with values of k₆ at least as large as 0.5 Å^?1 make an appreciable contribution to j(ω) where k₆ is the electron momentum parallel to the surface.     

Thiolated cyclodextrin self-assembled monolayer-like characterized with secondary ion mass spectrometry

In the work the focus is on the preparation of self-assembled monolayer-like films consisting of thiolated cyclodextrin on gold substrate and a characterization by using secondary ion mass spectrometry. The short (1 min) and long (1 h) time preparations of self-assembled monolayer-like films, resulting in submonolayer and monolayer regimes, are investigated, respectively. The observed species of thiolated cyclodextrin (M as molecular ion) self-assembled monolayer-like films are assigned to three groups: Au_xH_yS_z clusters, fragments with origin in cyclodextrin molecule associated with Au, and molecular ions. The group of Au_xH_yS_z (x = 2-17, y = 0-2, z = 1-5) clusters have higher intensities than other species in the positive and even more in negative mass spectra. Interestingly, the dependence between the number of Au and S atoms shows that with the increasing size of Au_xH_yS_z clusters up to 11 Au atoms, the number of associated S atoms is also increasing and then decreasing. Molecular species as (M−S+H)Na⁺, (M+H)Na⁺, AuMNa⁺, (M₂−S)Na⁺, and M₂Na⁺ are determined, and also in cationized forms with K⁺. The intensities of thiolated cyclodextrin fragments at the long time preparation are approximately 10 times higher than the intensities of the same fragments observed at the short time. The largest observed ions in thiolated cyclodextrin self-assembled monolayer-like films are AuM₂ and Au₂M. The thiolated cyclodextrin molecular ions are compared with hexadecanethiol molecular ions in the form of Au_xM_w where the values of x and w are smaller for thiolated cyclodextrin than for hexadecanethiol. This result is supported with larger, more compact, and more stabile thiolated cyclodextrin molecule.     

ToF-SIMS study of chemical composition and formation of all-nanoparticle multilayer films

All-nanoparticle multilayer films were prepared by layer-by-layer deposition of SiO₂ and Al₂O₃ nanoparticles onto polyester (PE) substrate. The top-most SiO₂ (and Al₂O₃) layer was characterized using ToF-SIMS and SEM. An element-specific homogeneity index obtained by ToF-SIMS measurement provides clue to the formation mechanism. Experimental results from ToF-SIMS and SEM accord well with molecular dynamics simulation results, demonstrating the potential of using ToF-SIMS to study all-nanoparticle multilayer films.     

Enhanced peptide molecular imaging using aqueous droplets

A new method in time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging, the droplet-enhanced method, was developed for the molecular analysis of biomaterials. To facilitate the ionization of biomolecules, a small amount of aqueous solution containing a variety of protonation agents as ionization-enhancing agents was dropped onto peptide samples before ToF-SIMS measurement. Using trifluoroacetic acid (TFA) as an enhancing agent, protonated insulin (MW 5733) ions were detected as not only [M + H]⁺ but also [M + 2H]²⁺ and [M + 3H]³⁺ from its film sample, using a Ga⁺ primary beam. TFA promoted the ionization of the large molecules much more effectively than did the other acids, and this peculiarity is related to both Na⁺ and Au₃⁺ intensities. We also demonstrated the visualization of dot-patterned insulin drawn with our bubble jet (BJ) printing technology using insulin molecular ion signals.     

Experimental investigations on a toroidal screw pinch

High-β Deuterium plasmas in a temperature range of 0.1–1 keV were produced in the fast toroidal screw pinch experiment ISAR IV (B _max≈33 kG,I _{z max}≈100–150 kA, coil diameter 12 cm, aspect ratio 5). The experimentally determined growth rates of the appearing instabilities—especially them=1 mode—are compared with two simple models and a more exact numerical calculation. This comparison and direct measurements of the magnetic field distribution show that the constant pitch model of Bobeldijk¹ is a suitable first approximation for the normal screw pinch. Using a delay of thez and θ-bank as a first simple method of field programming this constant pitch profil could be varied in different directions. The results are discussed in more detail and confirm the theoretical picture of stability behaviour of the high-β screw pinch.