Atmospheric-pressure laser ionization: a novel ionization method for liquid chromatography/mass spectrometry.

Abstract

We report on the development of a new laser-ionization (LI) source operating at atmospheric pressure (AP) for liquid chromatography/mass spectrometry (LC/MS) applications. APLI is introduced as a powerful addition to existing AP ionization techniques, in particular atmospheric-pressure chemical ionization (APCI), electrospray ionization (ESI), and atmospheric pressure photoionization (APPI). Replacing the one-step VUV approach in APPI with step-wise two-photon ionization strongly enhances the selectivity of the ionization process. Furthermore, the photon flux during an ionization event is drastically increased over that of APPI, leading to very low detection limits. In addition, the APLI mechanism generally operates primarily directly on the analyte. This allows for very efficient ionization even of non-polar compounds such as polycyclic aromatic hydrocarbons (PAHs). The APLI source was characterized with a MicroMass Q-Tof Ultima II analyzer. Both the effluent of an HPLC column containing a number of PAHs (benzo[a]pyrene, fluoranthene, anthracene, fluorene) and samples from direct syringe injection were analyzed with respect to selectivity and sensitivity of the overall system. The liquid phase was vaporized by a conventional APCI inlet (AP probe) with the corona needle removed. Ionization was performed through selective resonance-enhanced multi-photon ionization schemes using a high-repetition-rate fixed-frequency excimer laser operating at 248 nm. Detection limits well within the low-fmol regime are readily obtained for various aromatic hydrocarbons that exhibit long-lived electronic states at the energy level of the first photon. Only molecular ions are generated at the low laser fluxes employed (∼1 MW/cm2). The design and performance of the laser-ionization source are presented along with results of the analysis of aromatic hydrocarbons. Copyright © 2005 John Wiley & Sons, Ltd.

The development of ionization methods operating directly at atmospheric pressure (API) has enormously increased the applicability and analytical power of mass spectrometry, in particular atmospheric-pressure chemical ionization (APCI) and electrospray ionization (ESI).1–4 Both techniques allow the direct determination of analytes present in either liquid or gaseous (APCI only) matrices. Coupling of API techniques with chromatographic pre-separation stages, e.g., liquid chromatography (LC), further increases the analytical power of these methods. Quadrupole, ion trap and time-of-flight (TOF) mass analyzers have all been successfully coupled to LC/API interfaces. Today, such instruments are widely applied in routine analysis. A fundamental difference between APCI and ESI is the ionization mechanism: APCI requires the complete evaporation of solvents and analytes prior to ionization in the gas phase. With ESI, ionization occurs in the liquid phase and is followed by evaporation of the solvent droplets generated in the spray source. Generally, ESI produces either protonated or deprotonated ions of most polar compounds with high efficiency, in the positive and negative ionization mode, respectively, with virtually no fragmentation of the molecular ions. Ionization of compounds of lower polarity is preferably performed with APCI through interaction of a corona discharge with the solvent/analyte gas mixture generated upstream in a heated nebulizer inlet stage. The ionization efficiency for analytes with little or no polarity is usually insufficient with both techniques. In this case, additional methods are required, such as coupling of an electrochemical stage with ESI,5–16 coordination ionspray,17–21 or dissociative and non-dissociative electron-capture ionization with APCI.22–26

An alternative approach to the ionization of non-polar analytes at atmospheric pressure was introduced recently by Syage et al.27, 28 as atmospheric pressure photoionization (APPI) and by Robb et al.29, 30 as dopant-assisted (DA) APPI. Both techniques are based on single-photon ionization (PI), which has long been known from applications in ion-mobility mass spectrometry31–34 and in photoionization detectors (PID).35–37 The ionization process in APPI is initiated by VUV radiation, which ionizes species with ionization potentials (IP) lower than the photon energy. Frequently, the VUV radiation used is obtained from rare-gas discharge lamps. The most widely applied photon source is the krypton lamp emitting at λ = 123.9 nm (10 eV) and 116.5 nm (10.6 eV). Other discharge lamps are commercially available, but are generally less stable than the Kr lamp in prolonged operation.

With APPI, as is generally true for all ionization techniques operating at atmospheric pressure, thermodynamically favored ion/molecule reactions control the distribution of ions entering the collision-free region of the mass analyzer. In some cases, particularly at lower collision rates such as in low-pressure photoionization (LPPI),38 kinetic control of the ion distribution is also observed.39 In positive ion mode, the ionization efficiency for a specific analyte is thus primarily dependent on the ionization potential (IP) and the proton affinity (PA) of all the compounds present in the high-pressure region. The initial step in the photoionization of a molecule M is photon absorption and subsequent electron ejection to form the molecular radical cation M.+. Provided that the IPs of all the other species present in the ionization region, in particular of the matrix molecules, are higher than the photon energy, then this step should be specific towards the analyte. However, in the presence of protic solvent molecules and/or other analytes present in large excess, [M]+. can undergo further transformations. This is of particular interest in dopant-assisted APPI (see below). Other ionization mechanisms for APPI have been invoked. As an example, APPI (10 eV photons) with acetonitrile (CH3CN) as solvent can lead to predominant formation of [M+H]+ ions, although the IP of CH3CN is more than 2.2 eV higher than the available photon energy.40 This result is rationalized by the following mechanism: First, matrix molecules present in large excess absorb a significant fraction of 10 eV photons to form electronically highly excited neutral species, which rapidly isomerize to products with IPs lower than the photon energy. Ionization of the isomers/clusters and subsequent reaction with further matrix molecules or cluster formation leads ultimately to relatively long-lived species that can transfer protons to the analytes present. Therefore, more polar drug compounds in CH3CN/H2O mixtures are usually observed as [M+H]+ in APPI, whereas non-polar compounds such as naphthalene usually form [M]+..41 A detailed mechanistic analysis of [M+H]+ formation is given by Syage.39

The total ion yield in APPI is rather low as a result of both the limited VUV photon flux and the above-mentioned series of reactions, which potentially occur in parallel. Consequently, Bruins and co-workers introduced dopant-assisted atmospheric-pressure photoionization (DA-APPI)29 as a new ionization method, in which the total number of ions produced by the discharge lamp is greatly increased by the addition of a large quantity of a directly ionizable compound (dopant) to the liquid stream. If the dopant is selected so that its photoions have a relatively high recombination energy, or a low proton affinity, then dopant ions may react with other compounds present in the ionization region by charge exchange or proton transfer. Besides acetone and toluene, anisole was recently introduced as an effective dopant for APPI.42 The dopant-induced subsequent ion/molecule reactions can improve the sensitivity, but may render the analysis of APPI mass spectra more difficult, e.g., because of adduct formation.29, 41, 42 Moriwaki et al.43 have demonstrated the ultra-sensitive detection of various aromatic hydrocarbons. The reported detection limits when using DA-APPI and single ion monitoring are well within the low-nmol/L range. The various AP ionization methods were described recently in reviews by Hayen and Karst44 and by Van Berkel.45

In this paper we present a novel ionization method, atmospheric-pressure laser ionization (APLI). APLI is based on resonant or near-resonant two-photon ionization of aromatic ring systems. To our knowledge this is the first report describing the analytical application of resonantly enhanced multi-photon ionization (REMPI) in conjunction with commercially available ion sources operating at atmospheric pressure. We note that the acronym APLI has been used in the literature before.46–48 In view of the presently described newly evolving laser ionization technique operating at ion source pressures around p = 1 atm, the acronym APLI becomes ambiguous. In order to describe the former technique more accurately, the term medium-pressure laser ionization (MPLI) has been introduced49 with the intention of better distinguishing the three pressure regimes in which currently applied laser ionization techniques operate. The commonly used inlet systems for laser ionization mass spectrometry are shown in Fig. 1. Figure 1(a) shows the traditional supersonic jet expansion method using a skimmed and collimated molecular beam. Ionization occurs far downstream of the high-pressure nozzle, usually at a distance of 5–20 cm, well behind the sudden-freeze surface50 of the gas jet. The ro-vibrational temperatures of the analytes present in the ionization volume are usually well below 10 K allowing for high-resolution spectroscopic investigations. However, since the molecular number density decreases roughly with 1/r2 from the nozzle,50 and the ionization volume is rather small, the method is not well suited for analytical applications. The jet-REMPI approach (Fig. 1(b)), as introduced by Oser et al.,51 with orthogonal beam geometry operates also in a low-pressure background but without using skimmers. The ionization region is located just downstream of the sudden-freeze surface of the gas jet. Ro-vibrational cooling is thus still efficient, but the ionization volume is greatly increased, leading to favorable detection limits. A comparable linear setup was introduced by Onoda et al.,52 as shown in Fig. 1(c). The ionization volume is further increased by application of a line focus setup. Using MPLI (Fig. 1(d)), the ionization region is located as close as 0.5 mm from the nozzle orifice and thus within the continuous region of the jet, approaching local pressures up to 10 mbar. Ro-vibrational cooling is limited, which favors ionization with broad-bandwidth laser sources. The high analyte density allows for selective ultra-sensitive measurements (see Refs. 46–49 for details). Employing APLI (Fig. 1(e)), as presented in this contribution, ionization occurs at atmospheric pressure, upstream of the mass spectrometer sampling orifice. Ro-vibrational cooling does not occur. The generated photoions are directed towards the sampling orifice of the mass spectrometer by an external electrical field and drawn into the differential pumping stage mainly through collisions with the bath gas.

Figure 1.

Overview of inlet systems commonly used for laser ionization mass spectrometry. (a) Traditional skimmed supersonic jet setup for general spectroscopic applications shown in collinear configuration. (b) DLR jet-REMPI approach.51 (c) Collinear ionization scheme as reported by Onoda et al.52 (d) MPLI approach as described in detail in Refs. 46–49. (e) APLI approach as introduced in this contribution. Ionization occurs at p = 1 atm. In each panel, the laser-irradiated area is represented by the bold circle or ellipse connected to the arrow labeled ‘ions’. PV = pulsed valve; DP = differential pumping stage; IS = ion source; IO = ion optics; A = analyzer; +/− = high voltage repeller/extraction electrode potentials. Dotted areas indicate regions at or above atmospheric pressure.

EXPERIMENTAL

Reagents

Dichloromethane, acetonitrile, methanol, benzo[a]pyrene, fluoranthene, anthracene and fluorene were obtained from Merck (Darmstadt, Germany) and were of chromatographic or analytical grade.

Halogenated aromatic oligomers and the aromatic iridium complexes were provided by the research group of Prof. U. Scherf, Center for Polymer Technology, University of Wuppertal, Germany.

All other chemicals were from Merck (Darmstadt, Germany) and of the highest purity available and were used without further treatment.

Instrumentation

All experiments were performed with a MicroMass Q-Tof Ultima II orthogonal time-of-flight mass spectrometer (Eschborn, Germany) equipped with an APLI interface made by the machine shop of the Chemistry Department at the University of Wuppertal, Germany. The interface was based on the design of the original MicroMass Z-Spray™ interface. The heated AP probe was used without modification at T = 250–350°C. For APLI operation, the corona needle was removed, and an additional repeller electrode was installed. Typical voltages in the range +150 to +200 V were applied to the repeller when the instrument was operating in the positive ion mode. The ion-block temperature was generally maintained at T = 250°C. High-purity nitrogen was used as nebulizer, cone and desolvation gas with flow rates of approximately 0.3, 0.16, and 2.5 L min−1, respectively. The REMPI light source employed was a compact Lamdba Physik (Göttingen, Germany) OPTex excimer laser running at 248 nm (KrF*). Typical operating conditions were 100 Hz repetition rate, 15 mJ pulse energy, and 8 ns pulse duration. The laser beam was delivered unfocused to the APLI interface through fused-silica windows. No attempts were made to synchronize the orthogonal TOF pusher sequence with the laser pulse train (see discussion). The samples were injected into the probe with either a syringe pump (Harvard Apparatur, Hugstetten, Germany) at a flow rate of 500 μL/min or with a 30-μL loop in a Waters (Eschborn, Germany) 2690 HPLC system at a flow rate of 800 μL min−1. Figure 2 shows a schematic diagram of the setup.

Figure 2.

Bottom panel: Schematic diagram of the experimental setup. For most experiments the direct syringe pump driven inlet was used. AP = heated probe; IS = ion source (see upper panel); IO = ion transfer optics; HV = additional high-voltage power supply required for APLI operation; TO = UV transfer optics for laser beam delivery into the ion source. Solid arrows represent fluid flow, dotted arrows gas flow, respectively. Top panel: Schematic of the modified Z-spray™ ion source. The additional repeller is mounted opposite from the MS sampling nozzle. The laser beam is directed close to the nozzle without shining light on the metal surfaces.

RESULTS AND DISCUSSION

REMPI as analytical method

APLI utilizes resonantly enhanced multi-photon ionization (REMPI) as the primary ion production mechanism. The reactions listed below summarize well-described excitation pathways53–57 along with possible interfering processes, such as deactivation upon rapid intersystem crossing (ISC) and photodissociation at intermediate energy levels: Stepwise excitation

equation image(1a)
equation image(1b)

Precursor-ion fragmentation via ladder-switch mechanism

equation image(2a)
equation image(2b)

Photodissociation at intermediate levels

equation image(3)

Deactivation via ISC

equation image(4)

Reactions 1(a) and 1(b) represent a classical (m + n) REMPI process; for analytical applications in most cases m = 1, 2 and n = 1, 2. Although higher-order processes have been reported (e.g., (3 + 1) REMPI of CO58), they are very unlikely to occur with overall efficiencies sufficient for analytical applications. Even if m = 2, i.e., two photons are to be absorbed by the target molecule within a time frame of fs (or quasi simultaneously) for a resonant population of the intermediate level M*, the power density within the interaction volume has to be in the order of several GW/cm2. Under such conditions the ionization step 1(b) usually follows immediately, partly because the Franck-Condon (FC) overlap between a highly excited state (e.g., a Rydberg state) and low ionic states is often favorable.59 Although such power densities are easily achievable by tight focusing of a conventional ns laser beam with good beam quality, two effects have to be considered: First, the ionization volume (i.e., the region close to the laser beam focus) is significantly smaller compared to other ionization methods, severely limiting the detection limit. Second, when ns pulses are applied, further absorption of photons by the precursor ion is unavoidable, leading to fragmentation of the precursor ion via ladder-switch mechanisms53 (cf. reactions 2(a) and 2(b)).

Whereas rapid photodissociation (reaction 3) generally leads to unfavorable ion yields, deactivation of resonantly excited states through intersystem crossing processes (reaction 4) appears to be less critical for larger molecules. Upon the application of a second light source with higher energy photons, these states can be pumped above the ionization threshold provided that the FC factors are still favorable after ISC. One fundamental difference between APLI and APPI is the role of the mobile phase molecules (MP) of the HPLC stage or the solvent molecules (S) when using direct syringe injection. Since MP and S, e.g., H2O, CH3CN, CH3OH, are essentially transparent within the UV wavelength range used in APLI, significant absorption of the incident photons and thus any energy transfer steps from MP to the analyte M, isomerization of MP to yield reactive or ionizable species, as well as other processes involving highly excited MP or S molecules, as observed in APPI, can be excluded. It follows that the photon flux provided by the laser within the ionization volume is generally independent of the composition of the liquid phase entering the heated AP probe and fully available for analyte ionization.

In summary, for analytical applications of REMPI, overall resonant, low-order processes are the most favorable, in particular one-color (1 + 1) REMPI. Multi-color excitation significantly broadens the applicability of REMPI, but is not discussed here. In addition, ultra-fast excitation avoids a number of the interferences listed above, in particular photodissociation at intermediate levels,60–62 but the instrumentation currently available in the required energy range is not yet as user friendly as compact stand-alone ns laser sources.

REMPI of aromatic hydrocarbons

It is well known that numerous aromatic hydrocarbons are very efficiently ionized via (1 + 1) REMPI (see, e.g., Refs. 63 and 64, and references cited therein). The main reasons are high molecular absorption coefficients in the near UV, relatively large lifetimes of the intermediate S1 or S2 states, and favorable location of these states: Since the IP is often lower than the energy of the sum of two photons, ionization occurs readily from the resonantly pumped intermediate states. It follows that rather unfocused laser beams can be used, making this compound class ideally suited for REMPI analysis. A substantial body of reports on the analytical application of REMPI to the measurement of aromatics exists in the literature (see Ref. 64 for a recent review). The majority of these papers are concerned with the detection of toxic aromatic substances in exhaust gases such as from municipal waste incinerators,65–67 but also analysis of process gases,68–70 as well as vehicle exhaust measurements,71–73 besides many others, have been reported.

Generally REMPI is regarded as a highly selective ionization method: The target molecules are introduced into the ion source by means of a supersonic expansion stage, which drastically narrows the rotational population density in the ground state (cf. Fig. 1(a)). Tuneable narrow-bandwidth laser sources are required for efficient resonant excitation. At atmospheric pressure, however, the absorption features of aromatic hydrocarbons become broad and unresolved, and fixed-frequency lasers can be employed. Nevertheless, the ionization process remains selective towards the class of aromatic hydrocarbons with long-lived intermediate states: There are only a very limited number of non-aromatic analytes with molecular properties comparable to those described above. More importantly, the bulk gases N2 and O2, as well as virtually all traditional HPLC solvents (e.g., H2O, CH3OH, and CH3CN), exhibit only very small absorption cross sections in the near-UV region used for excitation. Furthermore, at least three photons would be required for their ionization; this is very unlikely to occur under the present experimental conditions, i.e., power densities in the order of 1 MW/cm2. As discussed above, this represents a major advantage of APLI over APPI, where the absorption cross sections of the bulk gases/solvents are comparably high in the energy range of the VUV lamp, leading to severe loss of photons available for direct ionization of analytes present.

APLI source operation

As mentioned above, for APLI operation the heated AP probe was used without modification. Since the corona needle is removed or disconnected from the high-voltage supply, an additional electrical-field gradient directing the laser-generated ions towards the sampling cone of the ion block is required. This gradient was introduced by installation of an additional repeller electrode, as shown in the inset in Fig. 2. Optimizing the repeller voltage and the distance to the sampling nozzle increased the total ion-signal intensity by a factor of 50–100 over operation of the source without this electrode present. A typical value of +180 V resulted in maximum sensitivity (the sampling cone was always held at a constant potential of +88 V). The positioning of the laser-beam axis relative to the sampling cone was less critical; however, the maximum sensitivity was achieved when the beam was positioned directly in front of the nozzle, as expected.

The TOF pusher pulse frequency, adjustable approximately from 4 to 30 kHz depending on the recorded mass range, was not synchronized with the laser-pulse train. The ion-signal intensity depended almost linearly on the laser-pulse repetition rate in the range 10–100 Hz and leveled off at higher frequencies. This observation is in accord with the assumption that below 100 Hz molecules in the ionization volume of approximately 1 cm3 are irradiated only once. This estimate is based on the assumption that the entire gas flow of approximately 3 L min−1 from the AP probe passes through the irradiated region. At higher laser-pulse frequencies, the gas in the ionization volume is only partly replaced.

It is pointed out that the performance of the arrangement described is far from optimum; however, in this contribution, we focus on the description of the efficiency of the APLI processes rather than the optimization of the APLI source geometry.

APLI of selected aromatic hydrocarbons

In the section below, we report APLI mass spectra of several aromatic hydrocarbons, which include polycyclic and polymeric structures, heterocycles, and coordination complexes. The polarity of the analytes was generally low. For selected PAHs, APCI measurements were also performed for comparison; in all other cases the quality of APCI mass spectra was not sufficient for a meaningful interpretation of the data.

Figure 3 shows a typical mass spectrum obtained for a representative non-polar PAH, benzo[a]pyrene. Only the precursor ion is produced with very high efficiency. The sample, dissolved in CH2Cl2, was directly injected with a syringe pump into the source via the heated AP probe. Current detection limits for benzo[a]pyrene are in the fmol range; however, as already discussed, the ion source is operating far from optimal performance. Similar results were obtained for anthracene, fluorene, and fluoranthene. APLI is thus extremely sensitive towards the determination of non-polar PAHs and could prove to be a powerful alternative to APCI and APPI. Recently reported detection limits for DA-APPI of the above PAHs among others are about an order of magnitude higher.43

Figure 3.

APLI raw mass spectrum obtained for benzo[a]pyrene, which is representative for most unsubstituted polycyclic aromatic hydrocarbons. Only the precursor ion is detected as major signal. The inset shows a close-up of the mass region of the molecular ion. Direct syringe pump injection with a flow rate of 200 μL/min was used. Sample concentration: 200 ng/L. Solvent: CH2Cl2.

More complex systems, with aromatic rings in oligo– or polymeric structures, were also investigated. In particular, the influence of heteroatoms, e.g., halogens, was of interest, since such molecules are often used as building blocks in advanced materials synthesis. An APLI mass spectrum of C50H45Cl is shown in Fig. 4 with the calculated isotopic pattern of the precursor ion in the inset for comparison. As in the case of the PAHs, the precursor ion signal is dominating the spectrum. Excellent agreement is found between the calculated and experimentally recorded spectrum. Minor signals are due to the presence of compounds which are either by-products of the synthesis or impurities resulting from thermal degradation within the AP probe. The synthetic procedure suggests that products with structures as shown in Fig. 4 may still be present after purification of the raw material. Since the AP probe temperature was relatively low (250°C) along with a rather high total gas flow present, we expect thermal degradation to be of minor importance. Another example is given in Fig. 5. The building block C36H22Br4 was introduced as 1 μM solution (in CH2Cl2) via the heated AP probe. Again, virtually no fragmentation occurred. The agreement between calculated isotopic pattern and experimental results is demonstrated in the inset.

Figure 4.

APLI raw mass spectrum of C50H45Cl. The molecular structure of the compound is shown on the right-hand side of the panel. Direct syringe injection of the sample dissolved in CH2Cl2 was used. Most abundant signals correspond to the molecular ion. The inset shows a close-up of the precursor ion mass region (top trace) and a calculated centroid spectrum74 of C50H45Cl. The patterns of the signals in the labeled regions correspond well to the molecular ions of compounds shown on the left-hand side of the panel. The synthetic procedure suggests that these signals are most likely due to remaining impurities after purification of the raw synthesis product. Ionic fragmentation is considered to be negligible under the present soft ionization conditions with a laser power density of 2 MW cm−2.

Figure 5.

APLI raw mass spectrum of C36H22Br4 using direct syringe injection of the sample dissolved in CH2Cl2. The inset shows a close-up of the precursor ion region (upper trace) and a calculated centroid spectrum74 (see also caption to Fig. 4).

The compound shown in the left panel of Fig. 6 was the target of a recent synthesis effort at the University of Wuppertal. We have employed APLI to investigate the synthesis products. The right panel in Fig. 6 shows an APLI spectrum obtained at an intermediate stage of the work. The signals in the two individual regions of the mass spectrum are fully compatible with the proposed structures shown in both lower panels of Fig. 6, as judged by the isotopic pattern of the signals recorded. The synthetic procedure has not yet been fully achieved, but, as shown, the approach is very promising. State-of-the-art analysis of such building blocks and reaction products includes field desorption (FD) MS. However, the sample preparation time for FD-MS is significantly longer than for APLI-MS. The latter method requires only a dilution step and loading of the syringe pump.

Figure 6.

Application example of APLI for synthesis control. Top left: Structure of the target molecule to be synthesized. Top right: Survey spectrum using APLI recorded during an intermediate state of the optimization of the synthetic procedure for the target compound. The raw product was dissolved in CH2Cl2 and directly injected. The labeled mass regions correspond to the panels below. Panel equation image: Close-up of the corresponding mass region in the survey spectrum along with a calculated centroid spectrum74 for the molecular ion of the compound shown in the bottom panel. Panel equation image: Close-up of the corresponding mass region in the survey spectrum along with a calculated centroid spectrum74 for the molecular ion of the compound shown in the bottom panel.

In conclusion, APLI represents a powerful new technique for mass spectrometric investigations of polymeric and polycyclic aromatic molecules. The quality of the spectra provides a basis for a critical evaluation of the progress of the synthesis and the purity of the products. The simplicity of the setup, which is comparable to APCI, allows for swift, and sensitive analysis of polymeric compounds with respect to their elemental composition and support of proposed structures, which are otherwise difficult to analyze.

APLI vs. APCI

A comparison of the performance of APLI and APCI is presented in Figs. 7 and 8. First, a solution containing benzo[a]pyrene in CH3CN was injected directly through the heated AP probe by syringe. For APCI operation, the corona needle was installed, and the source parameters were then optimized. For APLI, the source geometry was identical, but the needle was removed and the repeller electrode (see above) installed. In Figs. 7(a) and 7(b) the mass spectra obtained with APLI and APCI, respectively, are shown. The former method generates only parent radical ions [M]+. (along with background noise), whereas the latter generates [M+H]+ ions, as expected. However, the signal intensity [M]+. vs. [M+H]+ is at least a factor of 100 higher in APLI with simultaneously greatly reduced noise. The two effects result in a limit of detection (LOD) for benzo[a]pyrene that is about three orders of magnitude lower than with APLI (see above). It is pointed out that photoions generated in only 100 laser shots were co-added within the accumulation time of 1 s, since the laser pulse frequency was set to 100 Hz. In contrast hereto, using APCI with continuous ion generation, signals from more than 10 000 spectra are co-added in the same time period, because the TOF pusher frequency in both cases was about 30 kHz. These results suggest the possible further improvement of APLI upon phase locking the laser and TOF pusher pulse frequencies.

Figure 7.

Comparison of two raw mass spectra of benzo[a]pyrene dissolved in CH3CN using APLI (top trace) and APCI (bottom trace). For APLI the concentration was a factor of 500 lower. Direct syringe injection was used. The background signals originate from contamination from earlier experiments.

Figure 8.

Comparison of mass selectively recorded HPLC chromatograms of a PAH mixture containing benzo[a]pyrene (a), fluoranthene (b), anthracene (c), and fluorene (d), using APCI (left panel) and APLI (right panel). Note that normalized abundances are plotted for each chromatogram, i.e., the maximum observed value at the precursor ion mass intensity is set to 100%. Absolute ion signals are at least two orders of magnitude higher for APLI. Additionally, the signal from the UV diode-array detector mounted at the end of the HPLC column is shown [(e) in both panels]. Injection volume: 30 μL. UV detection wavelength: 254 nm. See Table 1 and text for further details.

In a second set of experiments, an HPLC stage was coupled to the AP probe. Four PAHs (benzo[a]pyrene, fluoranthene, anthracene and fluorene) were dissolved in CH3CN and then separated chromatographically (cf. Table 1 for details) for mass-selective detection. For comparison, the same mixture was analyzed using APLI and APCI-MS, respectively, under otherwise identical chromatographic conditions. For APLI, the precursor ion [M]+ was monitored, for APCI [M+H]+. The signals from the HPLC UV-diode-array detector were monitored simultaneously. The results are summarized in Figs. 8(a) (APLI) and 8(b) (APCI).

Table 1. Gradient program for the HPLC analysis. Column used: RP18e (LiChrosphere 100; 250 × 4 mm; 5 μm) from Merck (Darmstadt, Germany). The PAH mixture: benzo[a]pyrene, fluoranthene, anthracene, and fluorene (20 mg/L of each PAH)
Time [min] Eluent A methanol/water (4:1) [%] Eluent B methanol [%]
0 60 40
3 50 50
5 45 55
5.5 0 100
14 0 100
15 60 40

The results clearly show the advantages of APLI for PAH analysis. First, the spectra obtained with APLI are distinguished by a reduced base-line noise. Second, the ionization efficiency for the various PAHs is generally orders of magnitude higher for APLI. Using APCI, only in the case of benzo[a]pyrene were relatively high signal intensities obtained, while, for anthracene, significantly lower signal intensities were recorded and fluoranthene und fluorene were even below the APCI detection limit in this concentration range. Both effects, base-line noise reduction and much larger ionization efficiency, lead to detection limits which are at least two orders of magnitude lower for APLI as compared to APCI.

CONCLUSIONS

APLI is a very promising addition to the existing ionization sources operating at atmospheric pressure, in particular APCI, ESI, and APPI. Currently, the method is selective towards the analysis of simple, polymeric or polycyclic aromatic hydrocarbons, which may also contain heteroatoms. For these compound classes, APLI is extremely sensitive, with current detection limits in the fmol range. It is expected that this limit will significantly improve upon optimization of the source geometry and synchronization of the laser and mass spectrometer. In contrast to past applications of REMPI as an analytical technique, APLI is simple to operate. Most AP mass spectrometers can easily be retro-fitted with an APLI stage.

Future directions of APLI include: (i) Multicolor excitation. This approach allows for selective, efficient excitation of analytes exhibiting more complex absorption features or strong ISC processes. (ii) Dopant-assisted APLI. Since aromatic hydrocarbons are efficiently ionized, as described, addition of an aromatic dopant to the HPLC effluent widens the applicability of the technique significantly. In particular, non-aromatic compounds will be ionizable. All mechanisms and processes as described in the literature for DA-APPI also hold for DA-APLI. (iii) Electron attachment ionization mass spectrometry at atmospheric pressure. Thermal electrons are generated by the interaction of the laser beam with metal surfaces. Resonance and/or dissociative electron capture then leads to ionization of the analyte. The work described above is in progress, and results will be described in upcoming contributions.

Acknowledgements

The authors thank Prof. Dr. U. Scherf, Center of Polymer Technology, University of Wuppertal, Germany, for providing samples. This work was funded in part by the State of NRW, Germany, through the ‘Innovations Fond’ program.

Share This:

CDC admits 98 million Americans were given cancer virus via the polio shot.

The CDC has admitted that between 1955–1963 over 98 million Americans received one or more doses of a polio shot which was contaminated with a cancer-causing virus called Simian vacuolating virus 40 (SV40). The CDC quickly took down the page, along with Google, but the site was luckily cached and saved to symbolize this grand admission.

CDC_Polio

To further confirm this unbelievable admission, Assistant Professor of Pathology at Loyola University in Chicago Dr. Michele Carbone has been able to independently verify the presence of the SV40 virus in tissue and bone samples from patients who died during that era. He found that 33% of the samples with osteosarcoma bone cancers, 40% of other bone cancers, and 60% of the mesothelioma’s lung cancers all contained this obscure virus. This leaves the postulation that upwards of 10–30 million actually contracted and were adversely affected by this virus, to be deadly accurate.

Source:

InvestmentWatchBlog.com

Share This:

Catastrophic Failure: Democrats Long-Held Strategy Of ‘Divide And Conquer’ Has Blown Up In Their Faces.

‘If, God Forbid, The Fragmented Mob Of Girlies, Girly Men, And Cowardly Thugs Start Major Violence, I Predict That We Will Finish It’  

hateful_dems.jpg

Submitted to All News Pipeline by William B Stoecker

It is no secret to most of us conservative patriots that, in addition to incrementalism, the left’s favorite tactic is divide and conquer. In one sense they have succeeded, setting Blacks against Whites, Demoncraps against Republicans, women against men, perverts against straights, and so on.

But I am reminded of the admonition: “Be careful what you wish for. You might just get it.” For the leftists have splintered their own movement into warring factions who, while denouncing “hate” actually hate one another as much as they hate us. Identity politics is doomed to catastrophic failure. Consider the groups who still support the Demoncrap, or Communist Party.

First, there are the traditional leftists, including the loveable “liberals.” Living as I do in the People’s Republic of California, ruled by Jerry Moonbeam, I know them all too well; they virtually surround me. They tend to be symbol oriented, meaning that they are not into deeds (like working at truly productive occupations) and believe in words…and the left is very, very good at rhetoric. Leftist elites say the prettiest things, and their UI (Useful Idiot) followers believe them.

wacky_fems.jpg

Women tend to be more verbal than men on the average…and are more prone to be leftists. Lawyers and college English teachers deal with words, and tend to be leftists. (By contrast, engineers, farmers, and ranchers deal with real things and do real deeds and tend to be more conservative). Leftists often live in a bubble or echo chamber and deal only with others of their own kind and hear only their own opinions (given to them by government, academia, and the slimestream media) bouncing back at them. They never have to defend their opinions in open and honest debate.

They are the ultimate conformists (although they see themselves as intellectual freethinkers). And they are incredibly egotistical…vanity, remember, is Satan’s favorite sin. Like eighteenth century European aristocrats, they simply assume that they are superior to us “deplorables” and “bitter clingers.” Their masters seduce them by telling them that if they accept an ideological package deal without question it will prove that they are bold, daring, sexy, intellectual, and compassionate.

Many of us patriots began as young “liberals,” including myself and even such famous figures as Joseph Farah of wnd.com, and Bill Jasper, Senior Editor of the Birch Society’s New American magazine. Gradually, we realized the error of our ways and possessed sufficient humility to admit that we were wrong, that, in fact, we had been played for fools. As more and more of the truth is exposed many leftists will convert. But most are too proud, too arrogant to admit that not only are they not superior to the rest of us, but that they have been self-deluded fools. They will double down and move further into the darkness. Their choice.

Then there are the radical feminists. They are leftist as well, of course, and many of them are lesbians. Supposedly they stand for women’s “rights,” but they all adored Slick Willy Clinton, who abused and even raped women, and probably had former WH intern Mary Mahoney and her co-workers murdered. And feminists just love Muslims, who murder their own wives and daughters, practice female circumcision, and force their women to wear black sacks over their heads.

In fact, feminists are what I call “againsters,” people who pretend to be for something, but are really nihilistic haters who are against almost everything. Aside from their desire to butcher unborn babies, feminists are united in their hatred and contempt for men. We can thank Adam Weishaupt himself for inspiring modern feminism. So already we can see a split in the left, between the men and the women.

let_him_in.jpg

The ranks of sexual perverts now include not only homosexuals and lesbians, but an ever-growing variety of trans-genders, sexually mutilated, or hormone-injected creatures. For a time their preferred abbreviated title was LGBT, but we can call them “Glibetts,” for GLBT. Of course, they have expanded their title, adding more and more letters, and demand that they be addressed by their preferred imaginary pronouns and want people who fail to guess their preference to be jailed for using the wrong pronoun. And they demand access to all bathrooms and shower facilities of both sexes, and are agressively pushing their agenda in the indoc centers formerly known as “public schools,” seeking to twist our children into little versions of themselves.

They claim to be a large minority of the population, but Gallup polls show that all of them together, homosexuals (I will not give them “gay”), lesbians, and the mutilated, make up only 3.8% of the US population…a shrill, strident minority. They have, however, contributed far more than their share of serial killers. Their relationship with heterosexual leftists is sketchy at best, and Muslims profess to hate them (but then Muslims hate everyone and everything on Earth, including each other). It is sobering to reflect that even Hitler, Stalin, and Mao never tried to force the pervert agenda on their people…but it’s happening here in the land of the “free.”

Black people have traditionally voted for the party of slavery, segregation, Jim Crow laws, and eugenics…the Demoncraps. Blacks make up only 13.3% of our population, but commit roughly half of all the crimes, and a disproportionate number of them are on welfare. Despite being the beneficiaries of the welfare, and affirmative action and quotas, they still pretend to be “oppressed.” Not a day goes by without Whites and others being robbed, raped, and murdered by Blacks, who have murdered White infants and tortured Whites to death, but the poor babies still pretend that they are the victims of racism.

In addition to Black Muslims and Black Panthers they have now formed yet another group of violent militants…Black Lives Matter, or BM. There are a small number of truly great Black patriots, but the majority of even otherwise decent and intelligent Blacks have drunk the koolaid. The BM types generally hate their fellow leftists who are White and Hispanic.

Hispanics make up 17.8% of the US population, and many of them, especially those whose families were already here when the Anglos arrived, are productive citizens and do not support the leftist agenda. But many do, especially the immigrants (both legal and illegal), many of whom escaped from Mexico and came here to wave the Mexican flag. They include such groups as La Raza, Spanish for “The Race.” Imagine the hue and cry if a group of Whites formed an organization called The Race.

Counting all immigrants, not just those from Latin America, the US as of 2016 had 42.4 million of them, some 13.3% of the population, including at least 12.5 million illegal aliens. Their net cost to taxpayers is some $116 billion per year. As of 2014 some 42% of immigrant households received some form of welfare and/or food stamps. Many of the Hispanic immigrants are in violent gangs like MS-13, and many of them are racists who hate Whites, Blacks, Jews, and Asians. Yet White leftists think they can make common cause with them.

religion_of_peace_NOT.jpg

And, finally, we come to the Muslims, those charming people who mutilate their little girls, make their wives wear black sacks, and murder their daughters in the name of “honor.” Not a day passes without news of some mass murder or bombing committed in the name of the “religion of peace.” When they have no Christians or Jews handy, they kill other Muslims, as in the recent terrorist attack in Egypt. Particularly in Europe, but also in Minnesota, where large numbers of Somali twofers (Black and Muslim) have been imported, Muslims commit most of the street crime in between major terrorist attacks.

Islam is now the third largest religion in America after Christianity and Judaism; there are now some 3.3 million Muslims here, and 72% are immigrants or the sons and daughters of immigrants. Many of them hate Blacks, and they hate all their fellow leftists who are not Muslim, especially the Jews. Yet leftists cannot bear to hear any criticism of Muslims, accusing critics of “racism,” despite the fact that Islam is not a race. But then leftists are not into truth, or logic, and “racism” is their designated conversation stopper.

This fragmentation is reflected in the leadership of the Demoncrap Party…you might think that this would doom them to electoral failure, but never underestimate the Republicans’ talent for (as the saying goes) snatching defeat from the jaws of victory.

By contrast, we patriots, a large and growing minority of the population, are relatively united. We may disagree on minor points, but we do not hate one another. Many of us have military training and experience, and many of us are armed. The leftist thugs who call themselves “Antifa,” meaning anti-fascist, are actually violent fascists; their logo is colored black, white, and red…the colors of the Nazi flag and (according to Plato) the stones of Atlantis. They, like the inner city Black “flash mobs” and the BM thugs, are very good at ganging up on women who are patriots, on children, and on the elderly and disabled. They are not accustomed to armed men fighting back.

If civil war erupts, the military and police will likely be split between those who will obey orders, any orders, and those who actually want to obey the law and protect and serve their fellow citizens. And the gulf between us and the left has grown, and, I believe, is now unbridgeable. What I have said about Muslims is also true of leftists: you cannot make agreements with people who always lie and always violate every agreement; you cannot compromise with people whose goal is your enslavement and death; and you cannot reason with the criminally insane. If, God forbid, the fragmented mob of girlies, girly men, and cowardly thugs start major violence, I predict that we will finish it.

William B Stoecker

The views expressed by story contributors to All News Pipeline are their own and do not always align completely with those of ANP.

By: allnewspipeline

Share This:

Trump administration allegedly considering plan to privatize CIA operations.

Trump CIAThe United States Central Intelligence Agency and the White House are considering several proposals to hire private companies to carry out covert operations abroad, according to a report. BuzzFeed News said on Thursday that the proposals were communicated to the White House in the summer. The news site, which described the proposed plans as “highly unusual”, quoted “three sources who have been briefed on or have direct knowledge of the proposals”. The sources told BuzzFeed that, if approved, the plans would include the establishment of large intelligence networks in so-called “denied areas” —namely foreign environments deemed hostile. The networks would recruit and handle local agents, carry out psychological operations, capture terrorism suspects and rendition them to the US or third countries. “Islamic extremism” is mentioned as the primary target of the proposals.

According to BuzzFeed, one of the proposals involves Amyntor Group, a private company headquartered in the remote town of Whitefish, in northwestern Montana. The company is staffed by former members of the US Intelligence Community who have security clearances. It specializes in intelligence training and risk assessment. But it also collects and analyzes intelligence and provides counterintelligence services for government agencies in America and what it calls “friendly foreign governments” abroad. The company has reportedly been holding discussions with senior officials in the administration of President Donald Trump in recent weeks, according to two of BuzzFeed’s sources. The same sources say that the move toward privatization of some intelligence operations is being led by a feeling in the Trump administration that the CIA has a negative view of the White House. They claim that the CIA is not prepared to go along with the Trump administration’s efforts to make the agency’s operations more aggressive and, in the words of its new director, Mike Pompeo, “much more vicious”. They therefore see privatization as a way to bypass the resistance and skepticism of the CIA’s upper management.

BuzzFeed said it contacted the CIA about the Amyntor Group proposal, but the agency preferred not to comment. A press officer for the National Security Council, which is chaired by President Trump, said that its members were not aware of the privatization proposals. Amyntor Group commented through one of its lawyers, who told BuzzFeed that any contract signed between the company and the US government would be directed and controlled “by the proper government authority”.

By: Joseph Fitsanakis

Share This:

How A Dubious BBC Report Gave Israel The “Green Light” For Last Night’s Attack On Syria.

Syrian state television has confirmed that Israel attacked a military base outside of Damascus overnight on Friday, which Israeli media reports involved both surface-to-surface missiles and airstrikes, while Syria says its air defense systems were engaged and intercepted two missiles. Like other recent strikes inside Syria, the Israeli jets reportedly fired from over Lebanese airspace, in order to avoid both Syrian anti-aircraft missile systems and provoking a Russian response. Though the extent of the damage or casualties is not yet known, Syrian media has confirmed material damage to the base, and other reports indicate mass power outages in some of parts of Damascus occurred immediately after the attack, which SANA says happened at 12:30am local time. 

It appears the base is likely the same one featured in a November BBC report which showed satellite images detailing the purported construction and renovation of an “Iranian military base” near El-Kiswah, which lies 14 km (8 miles) south of Damascus. As we’ve noted before, the BBC report was dubiously sourced to “a Western intelligence source” and the story was quickly utilized by Israeli leaders to ratchet up rhetoric in preparing its case before the international community for further attacks on the supposed Iranian targets. Israel has long justified its attacks inside Syria by claiming to be acting against Hezbollah and Iranian facilities and arms depots. 


Image source: SANA

Indeed, BBC itself used ambiguous language in saying the satellite images “seem to show” construction activity at the site referenced by the intelligence source between January and October this year. However, the images don’t actually show much at all related to an Iranian military presence, but merely a series of two dozen large low-rise buildings – likely for housing soldiers and vehicles, which would be expected of any state army or sovereign nation.

Furthermore, the very title of the November piece – “Iran building permanent military base in Syria – claim” – underscores the complete lack of evidence for such a claim, which the BBC notes in the article is “impossible to independently verify.”

Yet in reporting last night’s Israeli strike on Syria, the BBC uncritically referenced its own prior unconfirmed “claim” to paint a picture that Israel is actually taking action against Iran and Hezbollah: “Israel has hit weapons sites before, in a bid to prevent arms being transferred to Syria’s Lebanese ally Hezbollah. Arms convoys in particular have been singled out by the Israeli air force.” 

And the BBC followed this with:

 
 

Last month the BBC revealed a claim that Iran was building a permanent military base near the town. A series of satellite images showed construction at the location of the alleged base, which was made known to the BBC by a western intelligence source.

 

Israeli Prime Minister Benjamin Netanyahu has previously warned that Israel would not allow Iran to establish any military presence in Syria.

So it appears the BBC is playing war propagandist for Israel, instead of including any level of critical inquiry regarding Israel’s unprovoked act of aggression against its neighbor. In short, the BBC spread what it acknowledged to be a mere “claim” based solely on an unnamed “Western intelligence source”. Then Israel used that claim to attack Syria, after which the BBC in circular fashion justified the attack based on its own original dubious “claim”.

Israeli media and politicians are currently using BBC published satellite images as “proof” that Israel attacked an “Iranian base” in Syria last night. Image source: BBC

Meanwhile, just about every major Israeli newspaper in today’s reporting is prominently featuring the prior BBC report as justification for the latest attack on Syria. The Times of Israel provides one such example among many when it says:

 
 

The alleged Israeli attack came three weeks after the BBC reported that Iran was building a permanent military base in Syria just south of Damascus. The British broadcaster commissioned a series of satellite pictures that showed widespread construction at the site.

Or see this op-ed in the Jerusalem Post today which references the BBC report as a watershed moment:

 
 

The attack raises several questions. Why wait so long to strike the Iranian base? What did “western intelligence sources” hope to accomplish by publishing information on the Iranian base? Why were the Iranians at the site given time to leave by their base becoming so public? The month’s activity appear to be part of a complex game being waged by Iran to entrench itself in Syria and Israel’s attempts to warn the Iranians off. Whatever was taking place at El-Kiswah had plenty of time to be wrapped up and moved if the Iranians were concerned about it being struck. If the reports about Israel’s threats to target sites between 40-60km from the Golan are accurate then it would indicate that the warnings have been manifested.

And nearly every major Israeli media source is also republishing the BBC satellite images as part of their reporting on the overnight strikes.

As we’ve long pointed out, anytime that Israel carries out acts of aggression against Syria, it can just blame Iran or Hezbollah and escape international criticism or condemnation. International media and Western governments have already demonstrated a penchant for towing the Israeli line whenever Iran can be conceivably blamed as a culprit – evidence or no evidence – this as Prime Minister Benjamin Netanyahu has made it official Israeli policy to oppose Iranian presence in Syria. 

Yet what key facts do the BBC and others leave out?

On Tuesday Israel’s own Defense Minister Avigdor Lieberman said that there are no Iranian military forces in Syria, but instead merely stuck to acknowledging “Iranian experts and advisers”. In comments to Israel’s Ynet news, Lieberman admitted, “It is true that there are a number of Iranian experts and advisers, but there is no Iranian military force on Syrian land.”

Clearly, Defense Minister Lieberman’s statement flies in the face of claims made by Netanyahu in his speech before the UN General Assembly this year when Netanyahu said, “We will act to prevent Iran from establishing permanent military bases in Syria for its air, sea and ground forces. We will act to prevent Iran from producing deadly weapons in Syria… And we will act to prevent Iran from opening new terror fronts against Israel along our northern border.”

In other words, Israel’s top military chief very publicly contradicted both Netanyahu’s and the BBC’s claims of Iranian military bases on Syrian soil, yet the BBC neglected to mention such essential information. Thus, it appears that the mainstream media is preparing us for war… but sadly, this is nothing new.

By: Tyler Durden

Share This: