Qinghao Wu

Minimization of Fragmentation and Aggregation by Laser Desorption Laser Ionization Mass Spectrometry

AbstractMeasuring average quantities in complex mixtures can be challenging for mass spectrometry, as it requires ionization and detection with nearly equivalent cross-section for all components, minimal matrix effect, and suppressed signal from fragments and aggregates. Fragments and aggregates are particularly troublesome for complex mixtures, where they can be incorrectly assigned as parent ions. Here we study fragmentation and aggregation in six aromatic model compounds as well as petroleum asphaltenes (a naturally occurring complex mixture) using two laser-based ionization techniques: surface assisted laser desorption ionization (SALDI), in which a single laser desorbs and ionizes solid analytes; and laser ionization laser desorption mass spectrometry (L2MS), in which desorption and ionization are separated spatially and temporally with independent lasers. Model compounds studied include molecules commonly used as matrices in single laser ionization techniques such as matrix assisted laser desorption ionization (MALDI). We find significant fragmentation and aggregation in SALDI, such that individual fragment and aggregate peaks are typically more intense than the parent peak. These fragment and aggregate peaks are expected in MALDI experiments employing these compounds as matrices. On the other hand, we observe no aggregation and only minimal fragmentation in L2MS. These results highlight some advantages of L2MS for analysis of complex mixtures such as asphaltenes. Figureᅟ

Miniaturized Linear Wire Ion Trap Mass Analyzer.

We report a linear ion trap (LIT) in which the electric field is formed by fine wires held under tension and accurately positioned using holes drilled in two end plates made of plastic. The coordinates of the hole positions were optimized in simulation. The stability diagram and mass spectra using boundary ejection were compared between simulation and experiment and good agreement was found. The mass spectra from experiments show peak widths (fwhm) in units of mass-to-charge of around 0.38 Th using a scan rate of 3830 Th/s. The limits of detection are 137 ppbv and 401 ppbv for benzene and toluene, respectively. Different sizes of the wire ion trap can be easily fabricated by drilling holes in scaled positions. Other distinguishing features, such as high ion and photon transmission, low capacitance, high tolerance to mechanical and assembly error, and low weight, are discussed.

A compact tandem two-step laser time-of-flight mass spectrometer for in situ analysis of non-volatile organics on planetary surfaces

Two-step laser desorption mass spectrometry is a well suited technique to the analysis of high priority classes of organics, such as polycyclic aromatic hydrocarbons, present in complex samples. The use of decoupled desorption and ionization laser pulses allows for sensitive and selective detection of structurally intact organic species. We have recently demonstrated the implementation of this advancement in laser mass spectrometry in a compact, flight-compatible instrument that could feasibly be the centerpiece of an analytical science payload as part of a future spaceflight mission to a small body or icy moon.

Laser desorption lamp ionization source for ion trap mass spectrometry

A two-step laser desorption lamp ionization source coupled to an ion trap mass spectrometer (LDLI-ITMS) has been constructed and characterized. The pulsed infrared (IR) output of an Nd:YAG laser (1064 nm) is directed to a target inside a chamber evacuated to ~15 Pa causing desorption of molecules from the targets surface. The desorbed molecules are ionized by a vacuum ultraviolet (VUV) lamp (filled with xenon, major wavelength at 148 nm). The resulting ions are stored and detected in a three-dimensional quadrupole ion trap modified from a Finnigan Mat LCQ mass spectrometer operated at a pressure of ≥ 0.004 Pa. The limit of detection for desorbed coronene molecules is 1.5 pmol, which is about two orders of magnitude more sensitive than laser desorption laser ionization mass spectrometry using a fluorine excimer laser (157 nm) as the ionization source. The mass spectrum of four standard aromatic compounds (pyrene, coronene, rubrene and 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine (OPC)) shows that parent ions dominate. By increasing the infrared laser power, this instrument is capable of detecting inorganic compounds.

Experimental Observation of the Effects of Translational and Rotational Electrode Misalignment on a Planar Linear Ion Trap Mass Spectrometer

AbstractThe performance of miniaturized ion trap mass analyzers is limited, in part, by the accuracy with which electrodes can be fabricated and positioned relative to each other. Alignment of plates in a two-plate planar LIT is ideal to characterize misalignment effects, as it represents the simplest possible case, having only six degrees of freedom (DOF) (three translational and three rotational). High-precision motorized actuators were used to vary the alignment between the two ion trap plates in five DOFs—x, y, z, pitch, and yaw. A comparison between the experiment and previous simulations shows reasonable agreement. Pitch, or the degree to which the plates are parallel along the axial direction, has the largest and sharpest impact to resolving power, with resolving power dropping noticeably with pitch misalignment of a fraction of a degree. Lateral displacement (x) and yaw (rotation of one plate, but plates remain parallel) both have a strong impact on ion ejection efficiency, but little effect on resolving power. The effects of plate spacing (y-displacement) on both resolving power and ion ejection efficiency are attributable to higher-order terms in the trapping field. Varying the DC (axial) trapping potential can elucidate the effects where more misalignments in more than one DOF affect performance. Implications of these results for miniaturized ion traps are discussed. Graphical Abstractᅟ