MATRIX ASSISTED LASER DESORPTION IONIZATION MASS

SPECTROMETRY MALDI-TOF MS

Polymer industrial applications depend on their mechanical properties, which are strongly

linked to the chemical structure and molecular mass of these big molecules. Thus, it is

important to determine polymer chain molecular weights and polymer constitution1,2. Typical

analytical techniques used are based on colligative properties determination to obtain

molecular weight averages. Nevertheless, chemical structure information is not possible to

acquire. Size exclusion chromatography (SEC) is commonly used to measure molecular

weight distribution and polydispersity, but has shown some drawbacks related with the

limitation of calibration standards and analyte adsorption.1-3. Moreover, mass spectrometry

MS may be a suitable technique to characterize polymers because the structure of the material

does not interfere in the mass molecular analysis. However, producing gas-phase ions from

polymers is a big limitation, for polymers are composed of big, entangled chains. A

modification of the conventional MS has been developed to successfully characterize

polymers, known as MALDI MS. This technique is based in the generation of polymer-matrix

vapour droplets, which are carried out to a time of flight TOF mass spectrum1,2,4.

Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF

MS) is a soft ionization method where the source of ions is the matrix, which is an organic

compound with the ability to absorb laser energy. The detector is a time-of-light analyzer 1,4,5.

First, the polymer sample is mixed with the matrix in a solvent. Metal ions are often added to

maximize cationization. Then, the solution is dispersed in a metal target and allowed to dry

under vacuum conditions. During drying, the solvent is separated and the sample co-crystalize

within the matrix, so that the polymer is homogeneously spread in the matrix. At that point,

the sample is exposed to U-V laser beam, and protonated ions are form. At each laser

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pulsation, the matrix absorbs the laser energy and small portions of the matrix are vaporized

together with polymer, as shown in figure 11,2,6.

Figure 1. Ionization process in MALDI MS7

When the ions are formed, they are accelerated at a set potential. At this stage, the

difference in the mass-to-charge ratio (m/z) of the ions enables to separate and detect them as

function of their different flight times. The TOF spectrometer measures the signal in terms of

time, which is proportional to the m/z ratio according to equation 12

m 2 U t2
= 2 Equation 1
z s

Where m is the ion mass, z the number of charges, t the flight time, U the accelerating

voltage and s the flight distance. Finally, a characteristic mass spectrum of the analysed

sample is obtained2.

The sample preparation is a really important and critical step in MALDI TOF analysis

because homogenous analyte-matrix mixture must be obtained to minimize mass

discrimination. The matrix must accomplish several parameters: it must show stability under

vacuum, have good solubility in organic solvents and with the polymer in solid state.

Furthermore, the matrix must absorb energy at the laser wavelength, usually at 337 nm,

convert this energy to discharge ions together with analyte molecules. The polymer has to

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effectively dissolve in the solvent, so that interactions between the polymer chains are

avoided. The matrix: polymer ratio depends on the sample preparation method, usually is

about 1000:11,2,8. Optimizing the matrix and solvent choice, sample preparation method and

matrix: polymer ratio, MALDI TOF provides useful information to characterize a great

variety of polymers.

Molecular weight averages Mn and Mw, polydispersity index, mass of the repeat unit and

end-group information can be obtained using MALDI TOF analysis. From the mass spectrum

obtained, the peak to peak distance gives information about the repeat unit mass. Moreover,

the end group mass can be obtained from each signal of the spectrum by the subtraction of the

repeat unit mass1,2. This technique gives accurate information when synthetic polymers with

polydispersity values less than 1.1 are evaluated. When MALDI analysis is combined with

SEC, high dispersity polymers are first fractionated in small portions and then analysed,

giving reliable information2,9. Furthermore, MALDI-TOF MS allows to determine oligomer

molecular weight, rate coefficients of chemical reactions, detection of impurities and isotropic

sequences. This system also gives information about branched polymers and copolymers,

when the technique is combined with SEC 1,4. MALDIT TOF technique allows the analysis of

high molecular weight polymers. It is a fast technique and allows the analysis of a great

variety of the synthetic polymers independently of their chemical structure. Nevertheless, the

technique shows some limitations in the analysis of polydispersity polymers and the analysis

of molecules with little stability in the ion gas-phase1.

MALDI-TOF MS is a useful technique to characterize a large variety of polymers, which

gives accurate information about polymer, repeated unit and end group structure. In

combination with other techniques, more complex systems can be analysed and the

limitations of this technique can be controlled.

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References

1
R. N. Jagtap and A. H. Ambre, Bull. Mater. Sci., 2005, 28, 515-528.

2
H. J. Rader and W. Schrepp, Acta Polymer, 1998, 49, 272-293.

3
H. Shion and N. Ellor,

https://www.waters.com/webassets/cms/library/docs/720002100en.pdf, (accessed November

2019).

4
D. Campbell, R. A. Pethrick and J. R. White, Polymer characterization: physical

techniques, CRC Press, Florida, 2000.

5
G. Montaudo, M. S. Montaudo, C. Puglisi and F. Samperi, Journal of Polymer Science,

1996, 34, 439-447.

6
N. Singhal, M. Kumar, P. K. Kanaujia and J. S Virdi, Frontiers in microbiology, 2015, 6,

DOI: 10.3389/fmicb.2015.00791.

7
Schimadzu corporation, https://www.shimadzu.com/an/lifescience/maldi/princpl1.html,

(accesed November 2019).

8
M. E. Payne and S. M. Grayson, Journal of visualized experiments, 2018, 136, DOI:

10.3791/57174.

9
A. Marie, F. Foumier and J. C. Tabet, Analytical Chemistry, 2000, 72, 5106-5114.

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