Environmental and food analysis by desorption atmospheric pressure photoionization‐mass spectrometry

Desorption atmospheric pressure photoionization‐mass spectrometry (DAPPI‐MS) is a versatile surface analysis technique for a wide range of analytes, especially for neutral and non‐polar analytes. Here, a set of analytes typically found in environmental or food samples was analyzed by DAPPI‐MS. The set included five polyaromatic hydrocarbons (PAHs), one N‐PAH, one brominated flame retardant, and nine pesticides, which were studied with three different spray solvents: acetone and toluene in positive ion mode, and anisole in negative ion mode. The analytes showed [M + H]⁺, M^+?, and [M–H]^? ions as well as fragmentation and substitution products. Detection limits for the studied compounds ranged from 30 pg to 1 ng (from 0.14 to 5.6 pmol). To demonstrate the feasibility of the use of DAPPI‐MS two authentic samples – a circuit board and orange peel – and a spiked soil sample were analyzed. Tetrabromobisphenol A, imazalil, and PAHs were observed from the three above‐mentioned samples, respectively. The method is best suited for rapid screening analysis of environmental or food samples. Copyright © 2010 John Wiley & Sons, Ltd.     

Polymer translocation under time-dependent driving forces: resonant activation induced by attractive polymer-pore interactions

We study the driven translocation of polymers under time-dependent driving forces using N-particle Langevin dynamics simulations. We consider the force to be either sinusoidally oscillating in time or dichotomic noise with exponential correlation time, to mimic both plausible experimental setups and naturally occurring biological conditions. In addition, we consider both the case of purely repulsive polymer-pore interactions and the case with additional attractive polymer-pore interactions, typically occurring inside biological pores. We find that the nature of the interaction fundamentally affects the translocation dynamics. For the non-attractive pore, the translocation time crosses over to a fast translocation regime as the frequency of the driving force decreases. In the attractive pore case, because of a free energy well induced inside the pore, the translocation time can be a minimum at the optimal frequency of the force, the so-called resonant activation. In the latter case, we examine the effect of various physical parameters on the resonant activation, and explain our observations using simple theoretical arguments.     

Desorption atmospheric pressure photoionization with polydimethylsiloxane as extraction phase and sample plate material

Desorption atmospheric pressure photoionization (DAPPI) is an ambient ionization technique for mass spectrometry (MS) that can be used to ionize polar as well as neutral and completely non-polar analytes. In this study polydimethylsiloxane (PDMS) was used as a solid phase extraction sorbent for DAPPI-MS analysis. Pieces of PDMS polymer were soaked in an aqueous sample, where the analytes were sorbed from the sample solution to PDMS. After this, the extracted analytes were desorbed directly from the polymer by the hot DAPPI spray solvent plume, without an elution step. Swelling and extracting the PDMS with a cleaning solvent prior to extraction diminished the high background in the DAPPI mass spectrum caused by PDMS oligomers. Acetone, hexane, pentane, toluene, diisopropylamine and triethylamine were tested for this purpose. The amines were most efficient in reducing the PDMS background, but they also suppressed the signals of low proton affinity analytes. Toluene was chosen as the optimum cleaning solvent, since it reduced the PDMS background efficiently and gave intensive signals of most of the studied analytes. The effects of DAPPI spray solvents toluene, acetone and anisole on the PDMS background and the ionization of analytes were also compared and extraction conditions were optimized. Anisole gave a low background for native PDMS, but toluene ionized the widest range of analytes. Analysis of verapamil, testosterone and anthracene from purified, spiked wastewater was performed to demonstrate that the method is suited for in-situ analysis of water streams. In addition, urine spiked with several analytes was analyzed by the PDMS method and compared to the conventional DAPPI procedure, where sample droplets are applied on PMMA surface. With the PDMS method the background ion signals caused by the urine matrix were lower, the S/N ratios of analytes were 2-10 times higher, and testosterone, anthracene and benzo[a]pyrene that were not detected from PMMA in urine, were observed in the MS spectrum.     

A new exact discrete linear reformulation of the quadratic assignment problem

The quadratic assignment problem (QAP) is a challenging combinatorial problem. The problem is NP-hard and in addition, it is considered practically intractable to solve large QAP instances, to proven optimality, within reasonable time limits. In this paper we present an attractive mixed integer linear programming (MILP) formulation of the QAP. We first introduce a useful non-linear formulation of the problem and then a method of how to reformulate it to a new exact, compact discrete linear model. This reformulation is efficient for QAP instances with few unique elements in the flow or distance matrices. Finally, we present optimal results, obtained with the discrete linear reformulation, for some previously unsolved instances (with the size n = 32 and 64), from the quadratic assignment problem library, QAPLIB.     

Modeling incoherent reflections from rough room surfaces with image sources

Reflections at rough surfaces change the temporal structure of the reflected signal. This paper shows how to incorporate this temporal behavior in geometric room acoustics modeling. Specifically, a beam tracer is used for calculating the image sources and reflection paths. The roughness of the surfaces is taken into account in post-processing. A single reflection is assumed to distribute the energy according to an exponential function in time based on Biot's rough surface modeling theory. Multiple reflections are modeled with convolutions of exponential functions which are approximated as gamma functions.     

Analysis of lipids with desorption atmospheric pressure photoionization-mass spectrometry (DAPPI-MS) and desorption electrospray ionization-mass spectrometry (DESI-MS)

In this article, the effect of spray solvent on the analysis of selected lipids including fatty acids, fat-soluble vitamins, triacylglycerols, steroids, phospholipids, and sphingolipids has been studied by two different ambient mass spectrometry (MS) methods, desorption electrospray ionization-MS (DESI-MS) and desorption atmospheric pressure photoionization-MS (DAPPI-MS). The ionization of the lipids with DESI and DAPPI was strongly dependent on the spray solvent. In most cases, the lipids were detected as protonated or deprotonated molecules; however, other ions were also formed, such as adduct ions (in DESI), [M-H](+) ions (in DESI and DAPPI), radical ions (in DAPPI), and abundant oxidation products (in DESI and DAPPI). DAPPI provided efficient desorption and ionization for neutral and less polar as well as for ionic lipids but caused extensive fragmentation for larger and more labile compounds because of a thermal desorption process. DESI was more suitable for the analysis of the large and labile lipids, but the ionization efficiency for less polar lipids was poor. Both methods were successfully applied to the direct analysis of lipids from pharmaceutical and food products. Although DESI and DAPPI provide efficient analysis of lipids, the multiple and largely unpredictable ionization reactions may set challenges for routine lipid analysis with these methods.     

Hybrid waveguide-surface plasmon polariton modes in a guided-mode resonance grating

We analyze the coupling between surface plasmon polaritons in a metal grating and the guided modes of a dielectric waveguide. Our model structure is a gold wire grating on a slab waveguide made of silicon nitride on silica wafer. The excitation of guided-mode resonances, surface plasmon polariton modes and hybrid waveguide-plasmon modes are observed in numerical simulations. Our experiments verify the existence of the predicted modes. These hybrid modes add significant degrees of freedom in designing structures for plasmonic applications.     

Picosecond pulse laser ablation of yttria-stabilized zirconia from kilohertz to megahertz repetition rates

Thin films of yttria stabilized zirconia were deposited onto silicon substrates using high repetition rate picosecond pulse lasers. The applied lasers covered the repetition rate range from 10 kHz to 4 MHz. We found that the laser pulse overlapping which results from increased repetition rates led to considerable changes in the ablation process. Defect formation and local heating lead to lower ablation thresholds and, with sufficiently high repetition rates, to melting of the target and even to thermal evaporation. We found that yttria-stabilized zirconia (YSZ) films deposited with picosecond pulses at 1064 nm wavelength below repetition rates of 2 MHz have rough, nanostructured morphology and the same atomic ratio of yttrium and zirconium as the target. Films deposited with 2 MHz and higher repetition rates with high number of overlapping pulses are very smooth, but are yttrium deficient, providing evidence of the importance of the thermal processes.     

Oxidation of Cyclic Hemiacetals into Diketones: Final Steps in the Conversion of a Triterpenoid Ring a into a Steroidal Enone by a New Short Route

As a part of our studies in the conversion of triterpenoids into steroids we have reported¹ that the Jones oxidation of some triterpenoid hemiacetals (1) gives acyloxy acids (2) instead of the desired 1,5-diketones (3). We now report² the shortest route yet for the reconstruction of a triterpenoid ring A ketone (4) into a steroidal enone (7) involving as key steps the exhaustive Baeyer-Villiger oxidation³ of triterpenoid ketones (4) into δ-lactones (5) and mild chromium(VI) oxidation of cyclic hemiacetals (1) into diketones (3).     

Effect of cationic polymethacrylates on the rheology and flocculation of microfibrillated cellulose

Using two cationic methacrylate polymers: poly([2-(methacryloyloxy)ethyl] trimethyl ammonium iodide) (PDMQ) and poly[(stearyl methacrylate)-stat-([2-(methacryloyloxy)ethyl] trimethyl ammonium iodide)] (PSMA13Q), we modified microfibrillated cellulose (MFC) water suspensions. The aim was to affect the flocculation and rheological behavior of the MFC suspension. PDMQ is a strongly cationic polymer while PSMA13Q, also a cationic polymer, contains hydrophobic segments. We studied the MFC/polymer suspension rheological properties with a rotational rheometer in oscillatory and flow measurements. To observe structural changes in suspensions at different shear rates, we measured flow curves with transparent outer geometry and photographed the sample with a digital camera. The oscillatory measurements showed that a small amount of the cationic PDMQ in the MFC suspension strengthened the gel, whereas a small amount of amphiphilic PSMA13Q weakened it. Increased amounts of either polymer increased the gel strength. PSMA13Q also changed the rheological character of the MFC suspension turning it more fluid-like. When we photographed the flow curve measurement, we saw a clear change in the floc structure. This floc structure rupture coincided with a transient region in the flow curve.