In the last decades, surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) has attracted increasing interest due to its unique capabilities, achievable through the nanostructured substrates used to promote the analyte desorption/ionization. While the most widely recognized asset of SALDI-MS is the untargeted analysis of small molecules, this technique also offers the possibility of targeted approaches. In particular, the implementation of SALDI-MS imaging (SALDI-MSI), which is the focus of this review, opens up new opportunities. After a brief discussion of the nomenclature and the fundamental mechanisms associated with this technique, which are still highly controversial, the
Surface-enhanced
Raman scattering (SERS) is a powerful and sensitive
technique for the detection of fingerprint signals of molecules and
for the investigation of a series of surface chemical reactions. Many
studies introduced quantitative applications of SERS in various fields,
and several SERS methods have been implemented for each specific application,
ranging in performance characteristics, analytes used, instruments,
and analytical matrices. In general, very few methods have been validated
according to international guidelines. As a consequence, the application
of SERS in highly regulated environments is still considered risky,
and the perception of a poorly reproducible and insufficiently robust
analytical technique has persistently retarded its routine implementation.
Collaborative trials are a type of interlaboratory study (ILS) frequently
performed to ascertain the quality of a single analytical method.
The idea of an ILS of quantification with SERS arose within the framework
of Working Group 1 (WG1) of the EU COST Action BM1401 Raman4Clinics
in an effort to overcome the problematic perception of quantitative
SERS methods. Here, we report the first interlaboratory SERS study
ever conducted, involving 15 laboratories and 44 researchers. In this
study, we tried to define a methodology to assess the reproducibility
and trueness of a quantitative SERS method and to compare different
methods. In our opinion, this is a first important step toward a “standardization”
process of SERS protocols, not proposed by a single laboratory but
by a larger community.
Photochemically cross-linked shape-memory polymer (SMP) materials have been achieved by functionalizing chain-ends of star-shaped poly(ε-caprolactone) (PCL) with 7-hydroxypropoxy-4-methylcoumarin followed by photodimerization of these end-groups. The kinetics of the network formation in function of the photosensitizer concentration has been studied by swelling experiments and rheology. Thanks to the design of a dedicated homemade mold, highly reproducible irradiation conditions have been achieved allowing to study the network formation and properties, especially the shapememory properties, in relation to the coumarin dimerization degree as determined by Raman spectroscopy. In optimized conditions, PCL-based SMP materials exhibiting high fixity and recovery have been achieved in remarkably short irradiation time, typically 5 min. In addition, the precise control of the network cross-link density with the irradiation time, so as the high stability of the formed networks toward temperature variations was also demonstrated allowing the fine-tuning of the network properties by the irradiation process. Finally, the reversible character of the coumarin dimerization under light irradiation of appropriate wavelength has been quantified by Raman spectroscopy. The dimer photocleavage allows the photoreconfiguration of the networks offering the ability to modify the "permanent" shape of the SMP material, while preserving the excellent shape-memory properties.
The variable configuration of Raman spectroscopic platforms is one of the major obstacles in establishing Raman spectroscopy as a valuable physicochemical method within real-world scenarios such as clinical diagnostics. For such real world applications like diagnostic classification, the models should ideally be usable to predict data from different setups. Whether it is done by training a rugged model with data from many setups or by a primary-replica strategy where models are developed on a 'primary' setup and the test data are generated on 'replicate' setups, this is only possible if the Raman spectra from different setups are consistent, reproducible, and comparable. However, Raman spectra can be highly sensitive to the measurement conditions, and they change from setup to setup even if the same samples are measured. Although increasingly recognized as an issue, the dependence of the Raman spectra on the instrumental configuration is far from being fully understood and great effort is needed to address the resulting spectral variations and to correct for them. To make the severity of the situation clear, we present a round robin experiment investigating the comparability of 35 Raman spectroscopic devices with different configurations in 15 institutes within seven European countries from the COST (European Cooperation in Science and Technology) action Raman4clinics. The experiment was developed in a fashion that allows various instrumental configurations ranging from highly confocal setups to fibre-optic based systems with different excitation wavelengths. We illustrate the spectral variations caused by the instrumental configurations from the perspectives of peak shifts, intensity variations, peak widths, and noise levels. We conclude this contribution with recommendations that may help to improve the inter-laboratory studies.
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