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- Absolute electron total ionization cross-sections: molecular analogues of DNA and RNA nucleobase and sugar constituents
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Accurate ionization cross-sections for DNA and RNA constituents in the condensed or aqueous phase are important parameters for models simulating radiation damage to genetic material in living cells. In this work, absolute gas-phase electron total ionization cross-sections (TICSs) have been measured for a series of six aromatic and eight non-aromatic cyclic species that can be considered as prototype functional group analogues for the nucleobases and sugar backbone constituents of DNA and RNA. TICSs for water, hexane, and ethylacetamide (a peptide bond analogue) are also reported. The experimental apparatus utilizes a cylindrical ion collector that surrounds the ionization region, providing essentially unit detection efficiency. Two theoretical models, the polarizability–correlation method and binary-encounter Bethe theory, are able to reproduce the measured maximum TICS well for all species studied. An empirical energy-dependent correction is found to yield improvement in the agreement between experimental energy-dependent cross sections and the predictions of the BEB model. Having characterised and optimised the performance of both models, they are then used to predict TICSs for gas-phase DNA and RNA nucleobases and sugars. Direct experimental determinations of TICSs for these species are difficult because of their low volatility, which makes it difficult to prepare suitable gas-phase samples for measurement.
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- The dissociative ionization dynamics of N2 and O2 molecules by electron impact: Velocity-map imaging
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This paper reports a crossed-beam velocity-map imaging study into the electron ionization dynamics of jet-cooled N2 and O2 molecules at electron collision energies from 35 to 100 eV. The use of velocity-map imaging detection provides insight into the detailed ionization dynamics through the dimension of the product ion kinetic energy associated with impulsive dissociation. In particular, “mesoscopic” cross sections corresponding to ionization from manifolds of energetically close states converging to the same dissociation asymptote are reported for a number of single-ionization channels. In addition, a range of double-ionization cross sections have been characterized, including those yielding X22+ dications. These are found to be in excellent agreement with other cross sections determined in coincidence measurements. This agreement supports a meaningful and accurate determination of the single-ionization channels.
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- Account: An introduction to velocity-map imaging mass spectrometry (VMImMS)
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This account introduces a new variant of time-of-flight (ToF) mass spectrometry (MS), termed Velocity-Map Imaging Mass Spectrometry (VMImMS). While the ion abundances recorded in conventional ToF-MS measurements are highly useful for molecular quantification and structure determination, the final parent and fragment ion yields are largely blind to the dynamics of the processes in which the ions were formed inside the mass spectrometer. By recording the velocity distribution of each ion in tandem with the mass spectrum, not only can the details of the dissociative ionization dynamics be unravelled, but the extra dimensions of information can be used for enhanced molecular fingerprinting, separating contributions from ions with identical mass-to-charge ratio, and resolving components within mixtures, to name but a few examples. Measuring ion velocity distributions within a mass spectrometry measurement is not new, but incorporating imaging techniques developed within the reaction dynamics community provides vastly improved velocity resolution for all ions simultaneously in a single-stage instrument. This account provides an introduction to VMImMS outlines the fundamental instrumentation and detector requirements and the challenges associated with developing the method further, and details proof-of-concept work from our laboratory on a number of potential applications of the technique.
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- Multimass Velocity-Map Imaging with the Pixel Imaging Mass Spectrometry (PImMS) Sensor: An Ultra-Fast Event-Triggered Camera for Particle Imaging
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We present the first multimass velocity-map imaging data acquired using a new ultrafast camera designed for time-resolved particle imaging. The PImMS (Pixel Imaging Mass Spectrometry) sensor allows particle events to be imaged with time resolution as high as 25 ns over data acquisition times of more than 100 μs. In photofragment imaging studies, this allows velocity-map images to be acquired for multiple fragment masses on each time-of-flight cycle. We describe the sensor architecture and present bench-testing data and multimass velocity-map images for photofragments formed in the UV photolysis of two test molecules: Br2 and N,N-dimethylformamide.
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- Exploring surface photoreaction dynamics using pixel imaging mass spectrometry (PImMS)
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A new technique for studying surface photochemistry has been developed using an ion imaging time-of-flight mass spectrometer in conjunction with a fast camera capable of multimass imaging. This technique, called pixel imaging mass spectrometry (PImMS), has been applied to the study of butanone photooxidation on TiO2(110). In agreement with previous studies of this system, it was observed that the main photooxidation pathway for butanone involves ejection of an ethyl radical into vacuum which, as confirmed by our imaging experiment, undergoes fragmentation after ionization in the mass spectrometer. This proof-of-principle experiment illustrates the usefulness and applicability of PImMS technology to problems of interest within the surface science community.
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- Quantification of ions with identical mass-to-charge (m/z) ratios by velocity-map imaging mass spectrometry
- Description:
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Quantification of ions with identical mass-to-charge (m/z) ratios by velocity-map imaging mass spectrometry. By integrating a velocity-map imaging lens and position sensitive detector into an electron-impact time-of-flight mass spectrometer, it becomes possible to record ion kinetic energy release (KER) distributions for each fragment ion alongside the time-of-flight mass spectrum. The KER distributions allow ions of identical mass-to-charge ratio to be distinguished and quantified.
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- PImMS, a fast event-triggered monolithic pixel detector with storage of multiple timestamps
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PImMS, or Pixel Imaging Mass Spectrometry, is a novel high-speed monolithic CMOS imaging sensor tailored to mass spectrometry requirements, also suitable for other dark-field applications. In its application to time-of-flight mass spectrometry, the sensor permits ion arrival time distributions to be combined with 2D imaging, providing additional information about the initial position or velocity of ions under study. PImMS1, the first generation sensor in this family, comprises an array of 72 by 72 pixels on a 70 μm by 70 μm pitch. Pixels independently record digital timestamps when events occur over an adjustable threshold. Each pixel contains 4 memories to record timestamps at a resolution of 25 ns. The sensor was designed and manufactured in the INMAPS 0.18 μm process. This allows the inclusion of significant amounts of circuitry (over 600 transistors) within each pixel while maintaining good detection efficiency. We present an overview of the pixel and sensor architecture, explain its functioning and present test results, ranging from characterisation of the analogue front end of the pixel, to verification of its digital functions, to some first images captured on mass spectrometers. We conclude with an overview of the upcoming second generation of PImMS sensors.
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- The application of the fast, multi-hit, pixel imaging mass spectrometry sensor to spatial imaging mass spectrometry
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Imaging mass spectrometry is a powerful technique that allows chemical information to be correlated to a spatial coordinate on a sample. By using stigmatic ion microscopy, in conjunction with fast cameras, multiple ion masses can be imaged within a single experimental cycle. This means that fewer laser shots and acquisition cycles are required to obtain a full data set, and samples suffer less degradation as overall collection time is reduced. We present the first spatial imaging mass spectrometry results obtained with a new time-stamping detector, named the pixel imaging mass spectrometry (PImMS) sensor. The sensor is capable of storing multiple time stamps in each pixel for each time-of-flight cycle, which gives it multi-mass imaging capabilities within each pixel. A standard velocity-map ion imaging apparatus was modified to allow for microscope mode spatial imaging of a large sample area (approximately 5 × 5 mm2). A variety of samples were imaged using PImMS and a conventional camera to determine the specifications and possible applications of the spectrometer and the PImMS camera.
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- Fast sensors for time-of-flight imaging applications
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The development of sensors capable of detecting particles and radiation with both high time and high positional resolution is key to improving our understanding in many areas of science. Example applications of such sensors range from fundamental scattering studies of chemical reaction mechanisms through to imaging mass spectrometry of surfaces, neutron scattering studies aimed at probing the structure of materials, and time-resolved fluorescence measurements to elucidate the structure and function of biomolecules. In addition to improved throughput resulting from parallelisation of data collection – imaging of multiple different fragments in velocity-map imaging studies, for example – fast image sensors also offer a number of fundamentally new capabilities in areas such as coincidence detection. In this Perspective, we review recent developments in fast image sensor technology, provide examples of their implementation in a range of different experimental contexts, and discuss potential future developments and applications.
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- PImMS: A self-triggered, 25ns resolution monolithic CMOS sensor for Time-of-Flight and Imaging Mass Spectrometry
- Description:
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In this paper, we present the Pixel Imaging Mass Spectrometry (PImMS) sensor, a pixelated Time-of-Flight (TOF) sensor for use in mass spectrometry. The device detects any event which produces a signal above a programmable threshold with a timing resolution of 25ns. Both analogue and digital readout modes are available and all pixels can be individually trimmed to improve noise performance. The pixels themselves contain analogue signal conditioning circuitry as well as complex logic totalling more than 600 transistors. This large number can be achieved without any loss of quantum efficiency thanks to the use of the patented Isolated N-well Monolithic Active Pixels (INMAPS) process. In this paper, we examine the design of the PImMS 1.0 device and its successor PImMS 2.0, a significantly enlarged sensor with several added features. We will also present some initial results from mass spectrometry experiments performed with PImMS 1.0.
