Parametric characterizations in superparamagnetic latex

The effect of synthesis parameters on the production of superparamagnetic latex, which are magnetite nanoparticles covered with a poly(methyl methacrylate) layer, were studied. The synthesis method was based on the developed route of emulsifier-free emulsion polymerization. Under this study, effects of the monomer and initiator concentrations, the amount of magnetic sol, the stirring rate and the adding rate of the magnetic sol on the properties of synthesized latexes were investigated. The characterizations were performed by a high resolution transmission electron microscopy, a dynamic light scattering, a vibrating sample magnetometer and a gel permeation chromatography. The results showed that the monomer concentration was found to be the most effective parameter on latex stability. As the initiator amount and the stirring rate increased, saturation magnetization and average molecular weight decreased due to the reactions occurring between surfaces of magnetite nanoparticles and initiator fragments. On increasing amount of magnetic sol, the saturation magnetization and polymer molecular weight increased but the size of nanospheres was unchanged because of the ions in magnetic sol. It was seen that the desired size and magnetic properties of the latex could be obtained since the parameters were found to have substantial impact on their properties.     

Sputtering of ice films by the bombardment of Ar ions

The process of sputtering ice films covered on Au(1 1 1) surface at normal incidence by Ar ions with an initial energy of E₀ = 300 eV and 700 eV has been investigated by the molecular dynamic simulation. The mass spectrum and kinetic energy distributions have been calculated. Our simulations clearly show that the mass spectrum contains peaks of the water molecules, water clusters and Au atoms. These results are of interest for the study of mass spectrometry in films and surfaces.     

DMTA investigation of solvents effects on viscoelastic properties of porous CaCO3-SBR latex composites

The impact of water, linseed oil and mineral oil solvents on the viscoelastic properties of calcium carbonate-caboxylated styrene buradiene (CaCO₃-SBR) porous coatings has been investigated using a dynamic mechanical thermal analysis (DMTA) technique in single cantilever mode from −30 °C to 70 °C. Water and oils reduce the glass transition temperature (Tan Delta peak) of pure latex. Oils increase the rubbery storage modulus which may be due to oxidation leading to entangled chains that contribute to resistance to deformation. Scanning electron microscopy (SEM) was used to visualise the porous structure of these composites. Further analysis using Image J software showed that increasing the latex content results in the development of small circular (2D) pores. The effect of solvents on the elastic response of coating depends on the chemical nature of the solvent and its molecular size. Linseed oil and water decreased the composite’s storage modulus for 5, 10 and 15 pph coatings, in contrast to mineral oil which had a negative impact at relatively higher latex content (50 pph). The drop in the strength and storage modulus of solvent saturated latex coatings is proportional to the solvent surface tension to viscosity ratio. The low values of storage modulus were interpreted as low adhesion between CaCO₃ particles and the carboxylated styrene- butadiene matrix. For low latex content coatings, low storage modulus is due to porosity which forms suitable sites for cracks initiation and propagation through the coatings. At higher latex volume fraction coatings the composite behaviour approaches that of pure latex.     

Preparation of submicrometer-sized titania hollow spheres by templating sulfonated polystyrene latex particles

Submicrometer-sized titania hollow spheres with tunable shell thickness and smooth surfaces have been successfully synthesized by employing sulfonated polystyrene (PS) latex particles as a template in sol-gel method. The structure of the particles was characterized by scanning electron microscopy and transmission electron microscopy. The shell thickness was readily tuned by altering the concentration of titanium tetrabutoxide (TBOT) in ethanol solutions. The surface roughness as well as the shell thickness has the tendency to increase with the increase in the concentration of TBOT. The diameter of the hollow spheres was on the average of 20-26% smaller than the diameter of template PS latex particles. Some titania fragments were also observed for the sample with the highest TBOT concentration.     

Derivatization of surface-bound peptides for mass spectrometric detection via threshold single photon ionization

Chemical derivatization of peptides allows efficient F2 laser single photon ionization (SPI) of Fmoc-derivatized peptides covalently bound to surfaces. Laser desorption photoionization mass spectrometry using 337-nm pulses for desorption and 157.6-nm pulses for threshold SPI forms large ions identified as common peptide fragments bound to either Fmoc or the surface linker. Electronic structure calculations indicate the Fmoc label is behaving as an ionization tag for the entire peptide, lowering the ionization potential of the complex below the 7.87-eV photon energy. This method should allow detection of many molecular species covalently or electrostatically bound to surfaces.     

Molecular formula analysis by an MS/MS/MS technique to expedite dereplication of natural products

A facile and sensitive mass spectrometric method has been developed for the dereplication of natural products. The method provides information about the molecular formula and substructure of a precursor molecule and its fragments, which are invaluable aids in dereplication of natural products at their early stages of purification and characterization. Collision-induced MS/MS technique is used to fragment a precursor ion into several product ions, and individual product ions are selected and subjected to collision-induced MS/MS/MS analysis. This method enables the identification of the fragmentation pathway of a precursor molecule from its first-generation fragments (MS/MS), through to the nth generation product ions (MSn). It also allows for the identification of the corresponding neutral products released (neutral losses). Elements used in the molecular formula analysis include C, H, N, O, and S, as most natural products are constituted by these five elements. High-resolution mass separation and accurate mass measurements afforded the unique identification of molecular formula of small neutral products. Through sequential add-up of the molecular formulas of the small neutral products, the molecular formula of the precursor ion and its productions were uniquely determined. The molecular formula of the precursor molecule was then reversely used to identify or confirm the molecular formula of the neutral products and that of the productions. The molecular formula of the neutral fragments allowed for the identification of substructures, leading to a rapid and efficient characterization of precursor natural product. The method was applied to paclitaxel (C47H51NO14; 853 amu) to identify its molecular formula and its substructures, and to characterize its potential fragmentation pathways. The method was further validated by correctly identifying the molecular formula of minocycline (C23H27N3O7; 457 amu) and piperacillin (C23H27N5O7S; 517 amu).     

Carbohydrate structural isomers analyzed by sequential mass spectrometry

Consistent with the goals of a comprehensive carbohydrate sequencing strategy, we extend earlier reports to include the characterization of structural (constitutional) isomers. Protocols were developed around ion trap instrumentation providing sequential mass spectrometry (MSn) and supported with automation and related computational tools. These strategies have been built on the principle that for a single structure all product spectra upon sequential fragmentation are reproducible and each stage represents a rational spectrum of its precursor; i.e., all major fragments should be accounted for. Anomalous ions at any stage are clues indicating the presence of structural isomers. Gas-phase isolation and subsequent fragmentation of such ions provide an opportunity to specifically resolve selected structures for their detailed characterization. Importantly, some isomers were not detected following MS2 and required multiple (MSn>2) stages for their characterization. Derivatization remains critical to position substructures in a glycan array since product ions carry fragmentation "scars" throughout the MSn tree. Equally as important are the pathway relationships between each stage and the greater yield of fragments with the smaller number of oscillators. Applications were directed to the structural isomers in ovalbumin and IgG, where, in the latter case, several previously unreported glycans were detected. Procedures were supported with bioinformatics tools for assimilating structure from the MSn data sets.     

Effect of reducing disulfide-containing proteins on electrospray ionization mass spectra

Electrospray ionization produces multiply charged molecular ions for biomolecules with molecular weights in excess of 100,000. This allows mass spectrometers with limited mass-to-charge range to extend their molecular weight range by a factor equal to the number of charges. The maximum number of observed charges for peptides and smaller proteins correlates well with the number of basic amino acid residues (Arg, Lys, His), except for disulfide-containing molecules, such as lysozyme and bovine albumin. However, reduction of disulfide linkages with 1,4-dithiothreitol (Cleland's reagent) may allow the protein to be in an extended conformation and make "buried" basic residues available for protonation to yield higher charged molecular ions by the electrospray ionization process. For larger proteins reduction of disulfide bridges greatly increases the maximum charge state, but charging of basic amino acid residues remains less efficient than for smaller proteins.     

Interpretation of mass spectra from organic compounds in aerosol time-of-flight mass spectrometry

Organic compounds containing a variety of functional groups have been analyzed using aerosol time-of-flight mass spectrometry. Both positive and negative laser desorption/ionization mass spectra have been acquired for compounds of relevance to ambient air particulate matter, including polycyclic aromatic hydrocarbons, heterocyclic analogues, aromatic oxygenated compounds such as phenols and acids, aliphatic dicarboxylic acids, and reduced nitrogen species such as amines. In many cases, positive ion mass spectra are similar to those found in libraries for 70-eV electron impact mass spectrometry. However, formation of even-electron molecular ions due to adduct formation also plays a major role in ion formation. Negative ion mass spectra suggest that organic compounds largely disintegrate into carbon cluster fragments (C(n)- and C(n)H-). However, information about the heteroatoms present in organic molecules, especially nitrogen and oxygen, is carried dominantly by negative ion spectra, emphasizing the importance of simultaneous analysis of positive and negative ions in atmospheric samples.     

Tandem mass spectrometry characteristics of silver-cationized polystyrenes: backbone degradation via free radical chemistry

The [M + Ag](+) ions of polystyrene (PS) oligomers are formed by matrix-assisted laser desorption/ionization, and their fragmentation characteristics are determined by tandem mass spectrometry experiments in a quadrupole/time-of-flight mass spectrometer. Collisionally activated dissociation (CAD) of [M + Ag](+) starts with random homolytic C-C bond cleavages in the PS chain, which generate radical ions carrying either the initiating (a(n*), b(n*)) or the terminating (y(n*), z(n*)) chain end and primary (a(n*), y(n*)) or benzylic (b(n*), z(n*)) radical centers. The fragments ultimately observed arise by consecutive, radical-induced dissociations. The primary radical ions mainly decompose by monomer evaporation and, to a lesser extent, by beta-H(*) loss. The benzylic radical ions primarily decompose by 1,5-H rearrangement (backbiting) followed by beta C-C bond scissions; this pathway leads to either closed-shell fragments with CH(2) end groups, internal fragments with 2-3 repeat units, or truncated benzylic b(n*)/z(n*) radical ions that can undergo anew backbiting. The same internal fragments are produced in all backbiting steps; hence, these fragments and small benzylic radical ions (which cannot undergo backbiting) dominate the low-mass region of the CAD spectra, while the less abundant closed-shell fragments with CH(2) end groups (a(n)/y(n)) dominate the medium- and high-mass regions. The latter fragments are suitable for determining the individual initiating and terminating end groups, whereas the internal ions could be valuable in sequence analyses of styrene copolymers.     

Debris cloud distributions at oblique impacts

The purpose of this study is to obtain mass, spray angle and velocity distributions of fragments in debris cloud generated by oblique impacts on an aluminum alloy plate. Hypervelocity impact tests were performed with a two-stage light gas gun at Kyushu Institute of Technology. The impact angles were changed to 0°, 15°, 30°, 45° and 60°. The projectile impacted on the targets at 2 km/s. After the impact, the debris cloud was taken with flash X-rays and an ultra high-speed video camera. The fragments were then captured in a stack of polystyrene sheets. As a result, the projectile was broken up into smaller fragments by oblique impacts with the larger impact angles. Lower velocity fragments dispersed in wider spray angles according to the increase of the impact angles.     

Tandem fourier transform mass spectrometry studies of surface-induced dissociation of benzene monomer and dimer ions on a self-assembled fluorinated alkanethiolate monolayer surface

A new instrument configuration based on a Finnigan FTMS-2000 platform has been applied to the study of surface-induced dissociation (SID) in this research. Benzene monomer ions C(6)H(6)(+) and dimer ions (C(6)H(6))(2)(+) were impacted on a fluorinated self-assembled monolayer surface at collision energies ranging from 1 to 70 eV. Benzene cations were chosen for this study because the fragmentation characteristics of the molecular cation are well known and its SID has been thoroughly investigated. SID spectra obtained by FTMS-SID are very similar to those reported in the literature for the same surface but exhibit much higher mass resolution. A comparison study of collision-induced dissociation (CID) and SID of benzene molecular cations was performed utilizing the same ICR cell and ion detection protocol. It is demonstrated that SID provides both much higher energy deposition and a narrower internal energy distribution than CID. The present instrument geometry and experimental protocol demonstrate much higher efficiencies than previous SID studies by FTMS and much higher mass resolution than previous SID studies using other types of mass analyzers.     

Investigations of secondary nucleation by initial breeding in clear solution zeolite NaA systems

An investigation of the effects of adding seed crystals to a clear synthesis solution, which produced molecular sieve zeolite NaA, was carried out. The initial breeding secondary nucleation mechanism, whereby microcrystalline fragments are washed off seed crystal surfaces to catalyze zeolite crystal nucleation, was studied using SEM, powder X-ray diffraction, and quasi-electric light scattering spectroscopy (QELSS). It was determined that small seed crystals (about 1–3 μm) did not promote nucleation of a new population of zeolite crystals when added to a clear solution synthesis batch. However, much larger zeolite NaA crystals (about 40 μm) were demonstrated to promote zeolite crystal nucleation by an initial breeding mechanism. Small particulates were demonstrated to exist only on the larger crystal surfaces, could be washed off, and were observed in a filtrate solution by QELSS. Lastly, it has been shown that the source of these particulates is residual aluminosilicate material in the bulk solution phase which was not incorporated into the crystal mass at the time the seed crystals were synthesized. As such, stopping the syntheses of smaller seed crystals prematurely was sufficient to cause the formation of initial-bred nuclei in those samples.     

Analysis of native biological surfaces using a 100 kV massive gold cluster source

In the present work, the advantages of a new, 100 kV platform equipped with a massive gold cluster source for the analysis of native biological surfaces are shown. Inspection of the molecular ion emission as a function of projectile size demonstrates a secondary ion yield increase of ~100× for 520 keV Au(400)(4+) as compared to 130 keV Au(3)(1+) and 43 keV C(60). In particular, yields of tens of percent of molecular ions per projectile impact for the most abundant components can be observed with the 520 keV Au(400)(4+) probe. A comparison between 520 keV Au(400)(4+) time-of-flight-secondary ion mass spectrometry (TOF-SIMS) and matrix assisted laser desorption ionization-mass spectrometry (MALDI-MS) data showed a similar pattern and similar relative intensities of lipid components across a rat brain sagittal section. The abundant secondary ion yield of analyte-specific ions makes 520 keV Au(400)(4+) projectiles an attractive probe for submicrometer molecular mapping of native surfaces.     

Limitations of electrospray ionization of fulvic and humic acids as visible from size exclusion chromatography with organic carbon and mass spectrometric detection

A method was developed to link size exclusion chromatography electrospray ionization mass spectrometry (SEC-ESI-MS) analyses of fulvic and humic acids with SEC and organic carbon detection (SEC-OCD), the latter providing an absolute measure of the amount of organic matter eluting from the SEC column. This approach allows us to determine which molecular weight fraction of the complex polydisperse mixtures is detectable by ESI-MS. It could be shown that the cone voltage setting for the ESI interface has strong impact on ESI-MS detection. Using conventional settings for low molecular weight compounds, the high molecular weight (HMW) compounds are hardly amenable to ESI-MS. With increasing cone voltage, an increasing signal intensity is obtained for the HMW fraction that elutes at shorter retention times. However, mostly fragment ions are obtained under these conditions. Thus, the range of compounds amenable to ESI-MS analysis is restricted by the limited stability of the fulvic and humic acid molecules of higher molecular weight in the electrospray process rather than by the mass spectrometer used. Compounds above 1000 amu are hardly visible as intact ions. However, insight into structural characteristics of these compounds can be gained by investigating their fragment ions by SEC-ESI-MS. The use of SEC-OCD parallel to SEC-MS helps to assess and optimize the detection potential of ESI-MS for polydisperse mixtures.     

Microchannel plate for surface-induced dissociation in mass spectrometry

A new method for surface-induced dissociation of molecular ions, applied to tandem mass spectrometry, is achieved by collisions at a grazing angle on the inside channel surfaces of a microchannel plate. This technique, termed microchannel SID, is demonstrated by using both positive and negative parent ions in the energy range of 500-2000 eV. Fragmentation spectra of the pentapeptide leucine-enkephalin (555 daltons) at 500 eV show good sequence information with a net fragmentation efficiency of 14%. High mass fragmentation is demonstrated on (CsI)23Cs+ (6113 daltons), with the resultant spectrum showing all cluster fragments from n = 0 to 23.     

Micro-scale energy dissipation mechanisms during dynamic fracture in natural polyphase ceramic blocks

The dynamic fracture of natural polyphase ceramic (granite) blocks by high-speed impact at 207 m/s, 420 m/s and 537 m/s has been investigated. An electromagnetic railgun was used as the launch system. Results reveal that the number of fragments increases substantially, and the dominant length scale in their probability distributions decreases, as the impact energy is increased. Micro-scale studies of the fracture surfaces reveals evidence of localized temperatures in excess of 2000 K brought on by frictional melting via fracturing and slip along grain boundaries in orthoclase and plagioclase, and via transgranular fracture (micro-cracking) in quartz. The formation of SiO₂- and TiO₂-rich spheroids on fracture surfaces indicates that temperatures in excess of 3500 K are reached during fracture.     

Molecular depth profiling of histamine in ice using a buckminsterfullerene probe

We employ a buckminsterfullerene ion source to probe the distribution of histamine molecules at the water-ice/vacuum interface. The experiments utilize secondary ion mass spectrometry to detect molecular ions that are desorbed from a frozen aqueous histamine solution. The results show that this cluster ion probe induces an extraordinarily high sputter yield of 2400 ice molecules per impact event as determined by a quartz crystal microbalance. As a consequence of this high yield, we show that it is possible to produce molecular depth profiles of the top several hundred nanometers below the ice surface without destruction of the molecular ion signal by accumulation of beam-induced chemical damage. Similar profiles are reported for desorbed neutral molecular fragments by utilizing a high-power femtosecond-pulsed laser for photoionization. While this type of information could not be achieved using atomic projectiles, it is possible to remove the damage induced by such projectiles by subsequent cluster bombardment. These experiments are particularly important for organic surface analysis since they suggest that cluster ion probes may successfully be employed to remove overlayers that may mask the desired molecular information in static secondary ion mass spectral analysis.     

Influence of Calcium on the Physical Properties of Gelatin Solutions and on Symplex Formation with Macromolecular Polyanions

Complex-bound calcium ions strongly decrease the electric potential carried by gelatin. This applies to all UEP-gelatins and does not depend on their molecular mass. The influence of calcium ions on physical characteristics such as viscosity, is not significant.

Macromolecular polyanions such as polystyrene sulphonate (PSS) and i-carraghenan form symplex structures with gelatin on the basis of the Coulomb interactions. These symplexes coagulate on lowering the pH.

Calcium ions shift the range of coagulation depending on the molecular ratios of polyanions to cations (gelatin). Adding calcium ions to calciumfree gelatin gives a completely similar behaviour.

In the case of high molecular mass polyanions (PSS 300000 D) the effect of calcium ions on the viscosity is dramatic, with a loss of viscosity by a factor of 4 to 5.

The modifications of physical properties caused by calcium ions are explained in terms of interactions with free sulphonate or sulphate groups in the symplex structure.     

Impact behavior of hydroxyapatite reinforced polyethylene composites

Hydroxyapatite particulate reinforced high density polyethylene composite (HA-HDPE) has been developed as a bone replacement material. The impact behavior of the composites at 37 °C has been investigated using an instrumented falling weight impact testing machine. The fracture surfaces were examined using SEM and the fracture mechanisms are discussed. It was found that the fracture toughness of HA-HDPE composites increased with HDPE molecular weight, but decreased with increasing HA volume fraction. Examination of fracture surfaces revealed weak filler/matrix interfaces which can debond easily to enable crack initiation and propagation. Increasing HA volume fraction increases the interface area, and more cracks can form and develop, thus decreasing the impact resistance of the composites. Another important factor for the impact behavior of the composites is the matrix. At higher molecular weight, HDPE is able to sustain more plastic deformation and dissipates more impact energy, hence improving the impact property.