Analysis of nucleotides directly from TLC plates using MALDI-MS detection

The natural pyrethrins, cinerin I, jasmolin I and pyrethrin I, have been hydrolyzed to chrysanthemic acid (CA) in subcritical water in the presence of basic alumina. The hydrolysis and extraction was performed in situ with subcritical water. The conversion to acid is reproducible at 200?°C and 30 min with an RSD of 19% (n = 16) at a concentration level of 1.2 × 10^–8 mol/L CA and 12% (n = 12) at concentration level of 1.2 × 10^–7 mol/L CA. An analytical method using Solid Phase Micro Extraction (SPME) combined with GC-FID or -MSD was developed and optimized. For SPME an equilibration time of 20 min at pH of 2 was required. Three fibers, 100 μm polydimethylsiloxane (PDMS), 85 μm polyacrylate (PA) and 65 μm carbowax/divinylbenzene (CW) were evaluated. The Carbowax/divinylbenzene fiber has the highest affinity for CA, but the capacity decreases significantly from experiment to experiment. The most reproducible and most stable one was the PDMS fiber. Two internal standards, octanoic acid and cis-chrysanthemic acid, were used because CA degrades slowly at 200?°C in water. This method was applied to analyze some products which contain pyrethrum as an active ingredient, such as insect spray, shampoo against lice, and dried chrysanthemum flowers. The results are comparable to SFC-FID data and correspond to the values given by the manufacturer.     

Collision induced dissociation study of ester-based polyurethane fragmentation reactions

A combination of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) collision induced dissociation (CID) and ion mobility separations (IMS) was used to study a complex mixture composed of unreacted polyester starting material (polybutylene adipate) and polyurethane (PUR) end products. Collision induced dissociation fragmentation identified two primary fragmentation mechanisms of PURs, which were used to generate a general fragmentation model. Predicted fragment ions were used to distinguish: (1) linear and cyclic PURs, (2) hard-block and soft-block PURS, (3) the degree of “blockiness” within hard- and soft-block PURs, (4) the location of the MDI linkages within each PUR chain, and (5) the relative intensities of various isobars intermingled within a precursor mass peak. These results were consistent with the observed IMS separations.     

Dielectric‐loaded plasmonic waveguide components: Going practical

Surface plasmon propagating modes supported by metal/dielectric interfaces in various configurations can be used for radiation guiding similarly to conventional dielectric waveguides. Plasmonic waveguides offer two attractive features: subdiffraction mode confinement and the presence of conducting elements at the mode‐field maximum. The first feature can be exploited to realize ultrahigh density of nanophotonics components, whereas the second feature enables the development of dynamic components controlling the plasmon propagation with ultralow signals, minimizing heat dissipation in switching elements. While the first feature is yet to be brought close to the domain of practical applications because of high propagation losses, the second one is already being investigated for bringing down power requirements in optical communication systems. In this review, the latest application‐oriented research on radiation modulation and routing using thermo‐optic dielectric‐loaded plasmonic waveguide components integrated with silicon‐based photonic waveguides is overviewed. Their employment under conditions of real telecommunications is addressed, highlighting challenges and perspectives.     

EXAFS characterization of Ti/Al2O3 supports and Co/Ti/Al2O3 catalysts

The structure of Ti/Al₂O₃ supports (0–14 wt% Ti) and Co/Ti/Al₂O₃ catalysts (3 wt% Co) was examined by EXAFS. The results indicated that the Ti was present primarily as a highly dispersed surface phase. The Ti EXAFS results indicated that the Ti species were octahedrally coordinated. Evidence of Ti—Ti interactions was found for all loadings (2–14 wt% Ti) suggesting that the Ti surface species are present as small clusters of TiO₂.The Co EXAFS results showed evidence for several structurally different Co surface phases as a function of Ti loading. Evidence of a Co species interacting with the Ti surface phase was observed for the 3% Co/2% Ti-3%Co/6%Ti catalysts. At the highest loadings studied, 3%Co/8%Ti and 3%Co/14%Ti, evidence was found for a CoTiO₃-like phase.     

Applications of laser microprobe mass spectrometry in organic analysis

The ability to focus the laser accurately onto the sample with a small beam diameter (2.0–3.0 μm) enables laser mass spectrometry to be used as a microprobe. Results from a fully automated ion-mapping system for laser mass spectrometry are described. These results show that the spatial resolution of the laser microprobe is primarily limited by the diameter of the laser beam. Factors such as laser power density, laser focus, sample preparation, and chemical environment influence the reproducibility of laser mass spectra significantly. Calibration curves obtained in the analysis of mixtures of phenanthrolines demonstrate that laser mass spectrometry can be used to quantify organic components. Preliminary results on the detection of neutral molecules resulting from metastable decomposition in the flight tube are also presented.     

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) of polyisoprenes

Polyisoprenes (PIPs) with average molecular weights from 650 to 800,000 Da have been studied by time-of-flight secondary ion mass Spectrometry (TOF-SIMS) in the static mode. Polymer samples were bombarded by argon primary ions, and positive SIMS spectra were collected. Effects of branching and unsaturation in the polymer structure on ion formation were studied. The pendant methyl group showed little tendency to fracture as a cation. In the low mass region, C_nH _2n–1 ⁺ appeared to be more intense than C_nH _2n+1 ⁺ , attributed to the double bond structure of polyisoprene. Additionally, ion formation varied as a function of polymer molecular weight. Cationized intact oligomers and fragments dominate the high mass region. Oligomer distributions were used to calculate average molecular weights for polyisoprenes. A statistical chain scission mechanism was used to qualitatively explain the formation of five clusters within a unique fragmentation pattern. Detailed studies of the cluster structure pointed out that each cluster contained several species having varied degrees of unsaturation. It is believed that double bond rearrangements occur.     

LC-MS/MS signal suppression effects in the analysis of pesticides in complex environmental matrices

The application of LC separation and mobile phase additives in addressing LC-MS/MS matrix signal suppression effects for the analysis of pesticides in a complex environmental matrix was investigated. It was shown that signal suppression is most significant for analytes eluting early in the LC-MS analysis. Introduction of different buffers (e.g. ammonium formate, ammonium hydroxide, formic acid) into the LC mobile phase was effective in improving signal correlation between the matrix and standard samples. The signal improvement is dependent on buffer concentration as well as LC separation of the matrix components. The application of LC separation alone was not effective in addressing suppression effects when characterizing complex matrix samples. Overloading of the LC column by matrix components was found to significantly contribute to analyte-matrix co-elution and suppression of signal. This signal suppression effect can be efficiently compensated by 2D LC (LC-LC) separation techniques. The effectiveness of buffers and LC separation in improving signal correlation between standard and matrix samples is discussed.     

Supramacromolecular self‐assembly: Chain extension,star and block polymers via pseudorotaxane formation from well‐defined end‐functionalized polymers

Dibenzo‐24‐crown‐8‐terminated polystyrene ( 5 ) was chain extended to “dimeric” 8 by pseudorotaxane formation with a ditopic guest, α,ω‐bis[p‐(N‐benzylammoniomethyl)phenoxy]heptane bis(hexafluorophosphate) ( 7 ). The three‐armed star polymer 11 was similarly formed by complexation of the dibenzo‐24‐crown‐8‐terminated polystyrene ( 5 ) with a tritopic secondary ammonium salt, 1,3,5‐tris[p‐(benzylammoniomethyl)phenyl]benzene tris(hexafluorophosphate) ( 10 ). Another three‐armed star polymer 13 was self‐assembled from dibenzo‐24‐crown‐8‐terminated polystyrene ( 5 ) and a tetratopic paraquat compound, 1,2,4,5‐tetrakis{p‐N‐[(N′‐methyl‐4,4′‐bipyridinium)methylphenyl]}benzene octakis(hexafluorophosphate) ( 12 ). The above chain extension and star polymer formation processes seemed to be cooperative; that is, the second and third complexation steps proceed with stepwise higher efficiencies than statistically expected. Dibenzo‐24‐crown‐8‐terminated polystyrene ( 5 ) was chain extended with secondary ammonium terminated polystyrene 14 , forming 16 , and also self‐assembled with a secondary ammonium ion terminated polyisoprene 15 to form supramolecular block copolymer 17 . These processes were examined by NMR, mass spectrometry and viscometery. Thus, although binding in these systems is not particularly strong (association constants <10⁴ M^?1), these examples provide proof‐of‐principle that pseudorotaxane formation is a viable concept for chain extension and self‐assembly of novel types of block copolymers and star polymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3518–3543, 2009