Laser ionization sources using

There are two common occasions when rapid measurement is preferable. The first is with ionization sources using laser desorption or radionuclides. A pulse of ions is produced in a very short interval of time, often of the order of a few nanoseconds. If the mass spectrometer takes 1 sec to attempt to scan the range of ions produced, then clearly there will be no ions left by the time the scan has completed more than a few nanoseconds (ion traps excluded). If a point ion detector were to be used for this type of pulsed ionization, then after the beginning of the scan no more ions would reach the collector because there would not be any left The array collector overcomes this difficulty by detecting the ions produced all at the same instant. 

A connnon feature of all mass spectrometers is the need to generate ions. Over the years a variety of ion sources have been developed. The physical chemistry and chemical physics communities have generally worked on gaseous and/or relatively volatile samples and thus have relied extensively on the two traditional ionization methods, electron ionization (El) and photoionization (PI). Other ionization sources, developed principally for analytical work, have recently started to be used in physical chemistry research. These include fast-atom bombardment (FAB), matrix-assisted laser desorption ionization (MALDI) and electrospray ionization (ES). 

A further important property of the two instruments concerns the nature of any ion sources used with them. Magnetic-sector instruments work best with a continuous ion beam produced with an electron ionization or chemical ionization source. Sources that produce pulses of ions, such as with laser desorption or radioactive (Californium) sources, are not compatible with the need for a continuous beam. However, these pulsed sources are ideal for the TOF analyzer because, in such a system, ions of all m/z values must begin their flight to the ion detector at the same instant in... 

When mass spectrometry was first used as a routine analytical tool, El was the only commercial ion source. As needs have increased, more ionization methods have appeared. Many different types of ionization source have been described, and several of these have been produced commercially. The present situation is such that there is now only a limited range of ion sources. For vacuum ion sources, El is still widely used, frequently in conjunction with Cl. For atmospheric pressure ion sources, the most frequently used are ES, APCI, MALDI (lasers), and plasma torches. 

The ablated vapors constitute an aerosol that can be examined using a secondary ionization source. Thus, passing the aerosol into a plasma torch provides an excellent means of ionization, and by such methods isotope patterns or ratios are readily measurable from otherwise intractable materials such as bone or ceramics. If the sample examined is dissolved as a solid solution in a matrix, the rapid expansion of the matrix, often an organic acid, covolatilizes the entrained sample. Proton transfer from the matrix occurs to give protonated molecular ions of the sample. Normally thermally unstable, polar biomolecules such as proteins give good yields of protonated ions. This is the basis of matrix-assisted laser desorption ionization (MALDI). 

In contrast to the other ion sources, the MALDI source may operate under high vacuum or under atmospheric pressure. In the latter case the acronym AP-MALDI (atmospheric pressure matrix assisted laser desorption ionization) is used. 

Mass spectrometric measurements of ions desorbed/ionized from a surface by a laser beam was first performed in 1963 by Honig and Woolston [151], who utilized a pulsed mby laser with 50 p,s pulse length. Hillenkamp et al. used microscope optics to focus the laser beam diameter to 0.5 p,m [152], allowing for surface analysis with high spatial resolution. In 1978 Posthumus et al. [153] demonstrated that laser desorption /ionization (LDI, also commonly referred to as laser ionization or laser ablation) could produce spectra of nonvolatile compounds with mass > 1 kDa. For a detailed review of the early development of LDI, see Reference 154. There is no principal difference between an LDI source and a MALDI source, which is described in detail in Section 2.1.22 In LDI no particular sample preparation is required (contrary to... 

There are three types of ion production using lasers as vaporization and ionization sources, laser ablation (LA), direct laser vaporization (DLV), and matrix assisted laser desorption ionization (MALDI). 

There have been fewer studies of the reactions of M ions with potential ligand molecules. Laser ablation, which has been the major ionization source for the production of bare metal ions, produces very few negative ions. Electron impact with low-energy electrons (12 eV) of metal carbonyls has been used to produce [Co(CO)4]- and Fc( CO)4 from Co2(CO)8 and Fe(CO)5. Collision-induced dissociation of these two anions produced Co- and Fc, which could be isolated. Both Co- and Fe were reacted with H2S, aliphatic thiols, aromatic thiols, CS2, and disulfides (153). Reactions with H2S gave the metal monosulfide anion [MS]-, which reacted with H2S by two pathways. 

Analytes must be liberated from their associated solvent molecules as well as be ionized to allow mass separation. Several ionization methods enable ion production from the condensed phase and have been used for the coupling of CE to MS. Among them, atmospheric pressure ionization (API) methods, matrix-assisted laser desorption/ionization (MALDI), and inductively coupled plasma (ICP) ionization are mainly used. API techniques are undoubtedly the most widespread ionization sources and cover different analyte polarity ranges. 

In summary, the use of mass spectrometric methods, combined with various approaches to vaporizing and ionizing the particles, is gaining increasing popularity and interest for the analysis of continuous sources of particles or single particles. The problem of quantification of the components seen by single-particle laser ionization techniques remains to be solved. On the other hand, the vaporization approaches can provide quantitative data on some volatile and semivolatile components but cannot measure the nonvolatile species and, at present, do not provide a full mass spectrum for a single particle. 

In contrast, the LA-ICP-MS (in comparison to laser ionization mass spectrometry (LIMS) where the ion source operates under high vacuum conditions) at present, in spite of the disadvantage of a higher polyatomic ion formation rate, uses an argon plasma ionization at normal pressure - a promising inorganic mass spectrometric technique for trace, isotope and surface analysis which will... 

In the past, for the analysis of thin sections of tissues or thin transparent foils a laser ionization ion source in the transmission or reflection mode of laser irradiation (using e.g., the LAMMA 500 or LAMMA 1000, respectively) was employed. The lateral resolution observed in the transmission mode was about 1 (im and in the reflection mode 5-20 gm. 

Figure 9.61 ToF mass spectrum of metal-carbon cluster ions (TiC2+ and ZrnCm+ cluster ions) using a titanium-zirconium (50 50) mixed alloy rod produced in a laser vaporization source (Nd YAG, = 532 nmj and ionization by a XeCI excimer laser (308 ). ( . M. Davis, S. J. Peppernick and A. W Castleman, J. Chem. Phys., 124, 164304(2006). Reproduced by permission of American Institute of Physics.)...

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