ABSTRACT
Charge detection mass spectrometry (CDMS) depends on the measurement of the charge induced on a cylinder by individual ions by means of a charge-sensitive amplifier. Electrical noise limits the accuracy of the charge measurement and the smallest charge that can be detected. Thermal noise in the feedback resistor is a major source of electrical noise. We describe the implementation of a charge-sensitive amplifier without a feedback resistor. The design has significantly reduced 1/f noise facilitating the detection of high m/z ions and substantially reducing the measurement time required to achieve almost perfect charge accuracy. With the new design we have been able to detect individual ions carrying a single charge. This is an important milestone in the development of CDMS.
ABSTRACT
Spontaneous mass and charge losses from individual multi-megadalton ions have been observed with charge detection mass spectrometry (CDMS) by trapping single hepatitis B virus (HBV) capsids for 3 s. Gradual increases in the oscillation frequency of single ions in the ion trap are attributed mainly to mass loss (probably solvent, water, and/or salt). The total mass lost during the 3 s trapping period peaks at around 20 kDa for 4 MDa HBV T = 4 capsids. Discrete frequency drops punctuate the gradual increases in the oscillation frequencies. The drops are attributed to a sudden loss of charge. In most cases a single positive charge is lost along with some mass (on average around 1000 Da). Charge loss occurs for over 40% of the trapped ions. It usually occurs near the beginning of the trapping event, and it occurs preferentially in regions of the trap with strong electric fields, indicating that external electric fields promote charge loss. This process may contribute to the decrease in m/z resolution that often occurs with megadalton ions. Graphical Abstract á .
ABSTRACT
Quadrupole mass filters (QMFs) are usually not used to analyze high m/z ions, due to the low frequency resonant circuit that is required to drive them. Here we describe a new approach to generating waveforms for QMFs. Instead of scanning the amplitude of a sine wave to measure the m/z spectrum, the frequency of a trapezoidal wave is digitally scanned. A synchronous, narrow-range (<0.2%) amplitude scan overlays the frequency scan to improve the sampling resolution. Because the frequency is the primary quantity that is scanned, there is, in principle, no upper m/z limit. The frequency signal is constructed from a stabilized base clock using a field programmable gate array. This signal drives integrating amplifiers which generate the trapezoidal waves. For a trapezoidal wave the harmonics can be minimized by selecting the appropriate rise and fall times. To achieve a high resolving power, the digital signal has low jitter, and the trapezoidal waveform is generated with high fidelity. The QMF was characterized with cesium iodide clusters. Singly and multiply charged clusters with z up to +5 were observed. A resolving power of â¼1200 (FWHM) was demonstrated over a broad m/z range. Resolution was lost above 20,000 Th, partly because of congestion due to overlapping multiply charged clusters. Ions were observed for m/z values well in excess of 150,000 Th.
ABSTRACT
A one-hundred-anode microchannel plate detector is constructed on a 10 cm × 15 cm printed circuit board and attached to a homebuilt matrix assisted laser desorption ionization (MALDI) time-of-flight mass spectrometer. Ringing and cross talk between anodes have been successfully eliminated and preliminary mass spectra of peptide ions recorded. With one hundred anodes on the printed circuit board, spatial information about the ion beam can also be readily determined with this detector. During operation, the detector anode assembly loses sensitivity after ions strike it for a considerable period of time due to charging of the non-conductive regions between anodes. However, this effect can be minimized by deflecting matrix ions away from the detector.
