Steffen M. Weidner

Mass spectrometry in polymer chemistry: a state-of-the-art up-date

Two decades after the introduction of matrix assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI), soft ionization mass spectrometry represents a powerful toolset for the structural investigation of synthetic polymers. The present review highlights the current state-of-the-art, covering the latest developments of novel techniques, enabling instrumentation as well as the important applications of soft ionization MS from the beginning of 2008. Special attention is paid to the role that soft ionization MS has played in the mechanistic investigation of radical polymerization processes since 2005.

Mass Spectrometry of Synthetic Polymers

Scope 4349 New Techniques and Principles 4349 Matrix-Free Laser Methods 4349 Fundamentals of MALDI and ESI 4350 Solvent-Based MALDI Methods 4350 Solvent-Free MALDI Methods 4350 Solvent-Based Condensed-Phase Separation Methods 4350 Solvent-Free Gas-Phase Separation Methods 4351 Other Methods 4351 Polymer Synthesis 4351 Copolymers 4351 Dendrimers and Hyperbranched Polymers 4352 Other Polymers 4352 Copolymer Analysis 4353 Fragmentation Techniques 4354 Polymer Degradation 4355 Polymer Surface and Interface 4357 Conclusion 4358 Literature Cited 4359

Analytically monitored digestion of silver nanoparticles and their toxicity on human intestinal cells

Abstract Orally ingested nanoparticles may overcome the gastrointestinal barrier, reach the circulatory system, be distributed in the organism and cause adverse health effects. However, ingested nanoparticles have to pass through different physicochemical environments, which may alter their properties before they reach the intestinal cells. In this study, silver nanoparticles are characterised physicochemically during the course of artificial digestion to simulate the biochemical processes occurring during digestion. Their cytotoxicity on intestinal cells was investigated using the Caco-2 cell model. Using field-flow fractionation combined with dynamic light scattering and small-angle X-ray scattering, the authors found that particles only partially aggregate as a result of the digestive process. Cell viabilities were determined by means of CellTiter-Blue® assay, 4′,6-diamidino-2-phenylindole-staining and real-time impedance. These measurements reveal small differences between digested and undigested particles (1–100 µg/ml or 1–69 particles/cell). The findings suggest that silver nanoparticles may indeed overcome the gastrointestinal juices in their particulate form without forming large quantities of aggregates. Consequently, the authors presume that the particles can reach the intestinal epithelial cells after ingestion with only a slight reduction in their cytotoxic potential. The study indicates that it is important to determine the impact of body fluids on the nanoparticles of interest to provide a reliable interpretation of their nano-specific cytotoxicity testing in vivo and in vitro.

Determination of critical conditions of adsorption for chromatography of polymers.

Liquid chromatography (LC) at critical conditions of adsorption was used to separate various poly(ethylene oxides), poly(propylene oxides) and their copolymers. For the first time, the determination of the critical conditions by means of Ultra Performance Liquid Chromatography (UPLC) coupled to Electrospray Ionization Time-of-flight Mass Spectrometry (ESI-TOF MS) is reported. In contrast to established, mostly laborious routines to find suitable chromatographic separation conditions, this coupling enables a very fast adjustment of parameters. Similar to LC Matrix-assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (LC/MALDI MS) coupling, a two-dimensional analysis of homo- and copolymers regarding its functionality type and molecular weight distribution, as well as copolymer composition, can be performed simultaneously. Furthermore, there is no need for using polymer standards for the determination of critical conditions or Size Exclusion Chromatography calibration.

In Situ Analysis of a Bimodal Size Distribution of Superparamagnetic Nanoparticles

The dispersed iron oxide nanoparticles of ferrofluids in aqueous solution are difficult to characterize due to their protective polymer coatings. We report on the bimodal size distribution of superparamagnetic iron oxide nanoparticles found in the MRI contrast agent Resovist, which is a representative example of commercial nanoparticle-based pharmaceutical formulations. The radii of the majority of the nanoparticles (>99%) range from 4 to 13 nm (less than 1% of the particles display radii up to 21 nm). The maxima of the size distributions are at 5.0 and 9.9 nm. The analysis was performed with in situ characterization of Resovist via online coupling of asymmetrical flow field-flow fractionation (A4F) with small-angle X-ray scattering (SAXS) using a standard copper X-ray tube as a radiation source. The outlet of the A4F was directly coupled to a flow capillary on the SAXS instrument. SAXS curves of nanoparticle fractions were recorded at 1-min time intervals. We recommend using the A4F-SAXS coupling as a routine method for analysis of dispersed nanoparticles with sizes in the range of 1-100 nm. It allows a fast and quantitative comparison of different batches without the need for sample preparation.

Influence of plasma treatment on the molar mass of poly(ethylene terephthalate) investigated by different chromatographic and spectroscopic methods

The influence of different types of low and atmospheric pressure plasma on poly( ethylene terephthalate) (PET) has been studied in terms of changes in molar mass and molar mass distribution. Apart from a variation of plasma gases (oxygen, helium) different types of plasma ( microwave, radio frequency, corona discharge ) were used for the plasma surface modification. The changes in molar mass and types of functional end groups of lower molar mass products were investigated by means of matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOFMS), whereas the high-molar mass fraction was analyzed by means of size-exclusion chromatography (SEC). The formation of crosslinked products during exposure to a helium plasma, which emits preponderately energy-rich and intense ultraviolet radiation, was proved by means of thermal field-flow fractionation (ThFFF). This method combined with a multiangle laser light scattering (MALLS) detector allows detection of weakly crosslinked polymers and microgels.

Synthesis of terpene–poly(ethylene oxide)s by t-BuP4-promoted anionic ring-opening polymerization

Terpene alcohols (menthol, retinol, cholesterol, and betulin) together with the phosphazene base t-BuP4 were used as initiating systems for anionic ring-opening polymerization of ethylene oxide. The polymerizations were conducted in a controlled manner with the initial molar ratio of t-BuP4 to hydroxyl groups of 0.01–0.2, yielding a series of biohybrid polymers comprising terpene entities and poly(ethylene oxide) (PEO) chains with low polydispersities and tunable compositions (57–87 wt% of PEO). Samples were characterized by NMR and UV/visible spectroscopy, MALDI-TOF mass spectrometry, and size exclusion chromatography; thermal properties were studied by differential scanning calorimetry. The concept of this study opens a new toolbox of terpene-based biohybrid polymers with variable properties and functions.

Coding and decoding libraries of sequence-defined functional copolymers synthesized via photoligation

Designing artificial macromolecules with absolute sequence order represents a considerable challenge. Here we report an advanced light-induced avenue to monodisperse sequence-defined functional linear macromolecules up to decamers via a unique photochemical approach. The versatility of the synthetic strategy—combining sequential and modular concepts—enables the synthesis of perfect macromolecules varying in chemical constitution and topology. Specific functions are placed at arbitrary positions along the chain via the successive addition of monomer units and blocks, leading to a library of functional homopolymers, alternating copolymers and block copolymers. The in-depth characterization of each sequence-defined chain confirms the precision nature of the macromolecules. Decoding of the functional information contained in the molecular structure is achieved via tandem mass spectrometry without recourse to their synthetic history, showing that the sequence information can be read. We submit that the presented photochemical strategy is a viable and advanced concept for coding individual monomer units along a macromolecular chain.

MALDI-TOF imaging mass spectrometry of artifacts in dried droplet polymer samples

AbstractMatrix-assisted laser desorption/ionization-time-of-flight (MALDI-TOF) imaging of polystyrenes with various molecular masses was applied to study spatial molecular mass distribution of polymers in sample spots prepared by the “dried droplet” method. When different solvents and target surfaces were examined, a segregation of single homologous polymers was observed depending upon the evaporation rate of the solvent. For the observed patterns left by the evaporating droplet, a hypothesis is offered taking into account different hydrodynamic interactions and diffusion. The results illustrate that spot preparation using the conventionally “dried droplet” method is prone to artifacts and should be avoided for reliable and reproducible MALDI mass spectrometry experiments with regards to the determination of molecular masses and mass distributions. FigureThe homogeneity of MALDI spots strongly depends on several parameters. MALDI-TOF imaging was applied to investigate the local distribution of polymers in sample spots prepared by the ‘dried droplet’ method. A solvent depending segregation of single polymer homologs was found and a possible explanation based on diffusion effects while solvent evaporation was presented and discussed. The results clearly suggest avoiding spot preparation using the conventionally ‘dried droplet’ method for MS experiments with regard to the determination of molecular masses and mass distributions. Optical image (left) and ion intensity distribution of PS 45 (middle) and PS 55 silver adduct ions prepared using the ‘dried droplet’ sample preparation (DMAc, retinoic acid)

Characterization of alkyl polyglycosides by both reversed-phase and normal-phase modes of high-performance liquid chromatography

Alkyl polyglycosides today represent the most important sugar surfactant. Nonionic sugar surfactants produced via different synthetic routes are mixtures of alkyl homologues, oligomers, anomers and isomers. Alkyl homologues and oligomers of alkyl mono- and diglucosides were separated by reversed-phase high-performance liquid chromatography (HPLC) with methanol-water as the mobile phase using a gradient elution. The gradient was optimized in respect to a simultaneous separation of alkyl glycosides according to their alkyl chain length and alkyl polyoxyethylene glucosides with regard to their length of the polyoxyethylene spacer. The separation of alkyl glycosides into alpha- and beta-anomers was carried out by normal-phase HPLC with isooctane-ethyl acetate (60:40, v/v)-2-propanol in the gradient mode. Light scattering detection was used. Matrix-assisted laser desorption ionization time-of-flight mass spectra of alkyl glucosides and dodecyl glucosides with oxyethylene spacer groups are presented.