A New Quantum Cascade IR-Laser Online Detector: Chemical-Sensitive Size-Exclusion Chromatography Measurement at Unprecedented Low Levels.

Online chemically sensitive detectors for size exclusion chromatography (SEC) through coupled setups based on infrared (IR) (or NMR) spectrometers present new possibilities through unprecedented levels of polymer detail with respect to molecular weight and chemical composition. Herein, a new external cavity quantum cascade laser (EC-QCL) mid-IR spectrometer as a chemically sensitive online detector for SEC is custom-designed, built, and tested. This unique spectrometer features multiple broadly tunable EC-QCL sources, which can be operated in continuous wave and pulsed mode, accompanied with balanced liquid nitrogen cooled mercury cadmium telluride (MCT) detectors and a new custom-built transmission flow cell. Automated data analysis is done with a self-written MATLAB code. The limit of detection (LOD) is measured online, coupled with SEC chromatography, where on average, one carbonyl functionality in 530 000 g mol-1 at chromatographic conditions for SEC could be detected. It is possible to detect 0.46 µg (LOD) PMMA, which is approximately a factor of 30 lower than that reported for SEC-Fourier transform infrared.

Medium Resolution 1 H-NMR at 62 MHz as a New Chemically Sensitive Online Detector for Size-Exclusion Chromatography (SEC-NMR).

A state-of-the-art, medium-resolution 1 H-NMR spectrometer (62 MHz) is used as a chemically sensitive online detector for size-exclusion chromatography of polymers such as polymethylmethacrylate (PMMA) and polystyrene (PS). The method uses protonated eluents and works at typical chromatographic conditions with trace amounts of analytes (<0.5 g L-1 after separation). Strong solvent suppression, e.g., by a factor of 500, is achieved by means of T1 -filtering and mathematical subtraction methods. Substantial improvements are made with respect to previous work in terms of the sensitivity (signal-to-noise ratio up to 130:1, PMMA OCH3 ) and selectivity (peak width, full width half maximum (FWHM) 4 Hz on-flow). Typical homopolymers and a blend are investigated to deformulate their composition along the dimensions of molecular weight and NMR chemical shift. These results validate this new hyphenated chromatography method, which can greatly facilitate analysis and is much more effective than previously published results.

A Novel Approach for the Desalination of Seawater by Means of Reusable Poly(acrylic acid) Hydrogels and Mechanical Force.

Desalination of a sodium chloride solution is achieved by the incorporation of salt depleted water into an acrylic acid based hydrogel and the subsequent deswelling of the gel by mechanical force to gain water with a lower salt content. This is a new approach towards the problem of desalination of seawater that has, to the best of our knowledge, not been presented before. In a proof-of-principle experiment the salt content of a 10 g/L NaCl solution could be reduced by 35% in one cycle. The influence of main chemical parameters, e.g. degree of crosslinking, degree of neutralization and experimental parameters like particle size and salt concentration on the desalination process are examined. Possible optimum conditions for the desalination using a poly(acrylic acid) network are discussed and the construction of a simple apparatus for deswelling by mechanical force is described.