Effect of Counterions on the Soft Ionization Mass Spectra of Analytes with Multiple Permanent Charges.

Multiply permanently charged analytes (MPCAs) are of great interest for various applications. MPCA soft ionization mass spectra (MS) strongly depend on the counterions of MPCA. We have studied thoroughly this effect to expand the use of MS in MPCA characterization. To this end, ß-cyclodextrin-based MPCAs with 7 (MIM7NBCD) and 14 (MIM14BCD) quaternary ammonium charges with a series of monovalent counterions were prepared and their MS were measured using two of the most popular soft ionization techniques, electrospray ionization (ESI) and matrix-assisted laser desorption ionization (MALDI). MALDI MS of both analytes were well resolved, with signals assignable to the analytes only with the two least basic tested counterions (ClO4- and TfO-). Similarly, analyte-assignable signals were observed in ESI MS of MIM14BCD only with ClO4- and TfO-. The situation was opposite with ESI MS of MIM7NBCD where assignable signals were observed with Cl- but not with TfO-. Thus, to get high-quality MS, binding between the MPCA permanent charges and the counterions must be of the optimal effective strength, given also by the number of analyte permanent charges as shown by the simple combinatorial model of binding. Of practical interest is the observation that unsuitable counterions can be replaced in situ by an excess of corresponding acid. The findings form a coherent framework for interpreting and improving MPCA mass spectra.

Acid-assisted polymerization: the novel synthetic route of sensing layers based on PANI films and chelating agents protected by non-biofouling layer for Fe2+ or Fe3+ potentiometric detection.

A new synthetic method for the fabrication of a sensing layer is presented. PANI films as an ion-to-electron transducer were prepared via acid-assisted polymerization in concentrated formic acid (HCOOH) in the presence of ethanol and ammonium persulfate (APS, as the initiator). The ratio of monomer to ammonium persulfate was 1 : 0.1. 2,2-Bipyridyl, 1,10-phenanthrolin-5-amine, and 8-hydroxyquinoline were used as chelating agents that can complex Fe2+ or Fe3+ ions. The proposed sensors demonstrated an appropriate reproducibility with a rapid response to the presence of Fe2+ or Fe3+ ions, even at T ∼ 37 °C. It was revealed that the method of deposition of a chelating molecule affects the response of sensors. The in situ deposition during acid-assisted polymerization leads to a fast response compared to the layer-by-layer deposition. PMeOx/X1-PANI@FTO and PMeOx/Z1-PANI@FTO sensors exhibit rapid response and are considered a promising detection layer for Fe2+ or Fe3+ ions respectively. We envision that this system can contribute to the next generation of advanced bio-sensors for the potentiometric detection of iron.

Low-Temperature Meltable Elastomers Based on Linear Polydimethylsiloxane Chains Alpha, Omega-Terminated with Mesogenic Groups as Physical Crosslinkers: A Passive Smart Material with Potential as Viscoelastic Coupling. Part I: Synthesis and Phase Behavior.

Physically crosslinked low-temperature elastomers were prepared based on linear polydimethylsiloxane (PDMS) elastic chains terminated on both ends with mesogenic building blocks (LC) of azobenzene type. They are generally (and also structurally) highly different from the well-studied LC polymer networks (light-sensitive actuators). The LC units also make up only a small volume fraction in our materials and they do not generate elastic energy upon irradiation, but they act as physical crosslinkers with thermotropic properties. Our elastomers lack permanent chemical crosslinks-their structure is fully linear. The aggregation of the relatively rare, small, and spatially separated terminal LC units nevertheless proved to be a considerably strong crosslinking mechanism. The most attractive product displays a rubber plateau extending over 100 °C, melts near 8 °C, and is soluble in organic solvents. The self-assembly (via LC aggregation) of the copolymer molecules leads to a distinctly lamellar structure indicated by X-ray diffraction (XRD). This structure persists also in melt (polarized light microscopy, XRD), where 1-2 thermotropic transitions occur. The interesting effects of the properties of this lamellar structure on viscoelastic and rheological properties in the rubbery and in the melt state are discussed in a follow-up paper ("Part II"). The copolymers might be of interest as passive smart materials, especially as temperature-controlled elastic/viscoelastic mechanical coupling. Our study focuses on the comparison of physical properties and structure-property relationships in three systems with elastic PDMS segments of different length (8.6, 16.3, and 64.4 repeat units).

MALDI-ToF mass spectrometry detection of intramolecular composition gradient in copolymers.

Since their addition to the polymer-architecture portfolio, gradient copolymers have attracted significant attention. Up to now, however, the existence of the intramolecular composition gradient must have been ascertained by sampling during living copolymerization because a reliable method for the detection of the composition gradient in the finalized copolymer had not been established yet. Here we show that MALDI-ToF mass spectrometry not only identifies imperfect, i.e. prematurely terminated copolymers but these copolymers can be used as "time capsules" which provide information on composition evolution and the intramolecular composition gradient.

Hydrolysis of wheat B-starch and characterisation of acetylated maltodextrin.

Wheat B-starch was hydrolysed by α-amylase "Liquozyme supra" from Bacillus licheniformis at 90 °C and pH 7. After 2 h, the dextrose equivalent was 18; according to size exclusion chromatography, however, the hydrolysate contained not only dominant malto-oligosaccharides with the degree of polymerisation (DP)<10 but also more than 20% of components with DP higher than 40. The product was acetylated to a high degree as verified by FTIR and (1)H NMR (degree of substitution DS=3.1); nevertheless, detailed analysis of the MALDI-TOF mass spectra of the product showed that most of the malto-oligosaccharides molecules contained one or two residual hydroxyls. Size exclusion chromatography confirmed that the acetylated maltodextrin still contained a significant part with DP>40. This non-uniformity of acetylated maltodextrin, both with respect to DP and to DS, must be taken into account in the development of acetylated-maltodextrin applications such as use as plasticisers or compatibilisers in biodegradable composites.

Quantification in MALDI-TOF mass spectrometry of modified polymers.

MALDI-TOF mass spectrometry quantification is hampered by the poor reproducibility of the signal intensity and by molecular-mass and compositional discrimination. The addition of a suitable compound as an internal standard increases reproducibility and allows a calibration curve to be constructed. The concept was also verified with synthetic polymers but no instructions for practical implementation were given [H. Chen, M. He, J. Pei, H. He, Anal. Chem. 75 (2003) 6531-6535.], even though synthetic polymers are generally non-uniform with respect to molecular mass and composition and access to the polymer of the same molecular mass distribution and composition as that of the quantified one is thus the exception rather than rule. On the other hand, relative quantification of polymers e.g., the content of the precursor polymer in a batch of a modified polymer, is usually sought. In this particular case, the pure precursor is usually available and the modified polymer can serve as an internal standard. However, the calibration curve still cannot be constructed and the use of the internal standard has to be combined with the method of standard addition in which the precursor polymer is added directly to the analyzed sample. The experiments with simulated modified polymers, mixtures of poly(ethylene glycol) (PEG) and poly(ethylene glycol) monomethyl ether (MPEG) of similar molecular-mass distribution, revealed a power dependence of the PEG/MPEG signal-intensity ratio (MS ratio) on the PEG/MPEG concentrations ratio in the mixture (gravimetric ratio). The result was obtained using standard procedures and instrumentation, which means that the basic assumption of the standard-addition method, i.e., the proportionality of the MS and gravimetric ratios, generally cannot be taken for granted. Therefore, the multi-point combined internal-standard standard-addition method was developed and experimentally verified for the quantification of the precursor in modified polymers. In this method, the two parameters of the power-type calibration curve - the proportionality constant and the exponent-are assumed. If the exponent strongly deviates from unity the minority component can be significantly underrepresented in the spectrum. Therefore, the absence of the precursor polymer signals in the MALDI-TOF mass spectrum of a modified polymer sample does not prove the absence of the precursor in the sample. Such a conclusion has to be corroborated by the standard-addition method.

Quantitative interpretation of MALDI-TOF mass spectra of imperfect carbosilane dendrimers.

A general relationship is derived for the abundance of an imperfect dendrimer with a given number of missing constitutional repeating units in the two outmost layers. The relationship is used in the interpretation of the MALDI TOF mass spectrum of the second-generation carbosilane dendrimer prepared by the iterative divergent method. The model quantitatively describes the spectrum of the dendrimer and correctly predicts the MALDI TOF mass spectrum of its first-generation precursor. Thus, the use of well-resolved MALDI TOF mass spectra for assessing the purity of low-generation dendrimers with uniform end groups is substantiated for carbosilane dendrimers and to lesser extent for dendrimers in general.