Semiquantitative Approach for Polyester Characterization Using Matrix-Assisted Laser Desorption Ionization/Time-of-Flight Mass Spectrometry Approved by 1H NMR.

Matrix-assisted laser desorption ionization/time-of-flight (MALDI/ToF) mass spectrometry and 1H NMR were used for the structural investigation of isophthalic and maleic acid copolyesters with neopentyl glycol. Since both methods provided information on the ratio of incorporated acid components and terminating groups, results were compared and linear correlations (R2 = 0.96-0.98) could be found. This suggests that MALDI/ToF MS is a suitable tool for the semiquantitative characterization of polyester systems. For the isophthalic/maleic acid ratio, MALDI results yielded constantly lower values than 1H NMR, which was attributed to varying ionization efficiencies of homo- and copolyesters. Ratios of carboxylic and hydroxylic terminating groups, which are conventionally still measured by time consuming complex titrations, were measured with MALDI and 1H NMR and were in good agreement. Both methods either excluded or distinguished unreacted monomers in the polyester bulk in contrast to acid-base titrations where those monomers severely distort the results. Additional structural information could be gained including the observation of cyclic structures (MALDI), E/Z isomerism from maleic to fumaric acid, and the statistical distribution of the acid components within the polyester chain (1H NMR). While 1H NMR peak assignments have to be verified by 13C NMR and multidimensional techniques, MALDI/ToF MS provides a straightforward technique that can be applied to other polyester systems without major alterations.

Grinding of nano-graphite inkjet inks for application in organic solar cells.

The production of printable graphene flakes is not easy to scale up when produced by ultrasonication and purified by centrifugation. In this work, natural graphite flakes were exfoliated by wet ball milling in water supported by the addition of sodium deoxycholate as a surfactant and the dispersion was formulated for inkjet printing. By subsequent dilution and filtration of the milling paste, more than 45 l of a stable dispersion of nano-graphite particles in one batch process was obtained. The dispersion was characterized by thermogravimetric analysis and UV-vis spectroscopy to determine concentration, and experiments to measure long-term stability were conducted. The nano-graphite particles were analyzed by optical microscopy, scanning electron microscopy and Raman spectroscopy, revealing 300-400 nm sized particles. The dispersion was formulated into an inkjet ink and tested as interfacial hole transport layer between the anode and the photo-active bulk-heterojunction layer of an organic solar cell with inverted structure. The nano-graphite flakes are inkjet printable and conductive and therefore show potential as a low-cost alternative to polymer poly(3,4-ethylenedioxythiophene) polystyrene sulfonate.

Phosphoramide Hydrogels as Biodegradable Matrices for Inkjet Printing and Their Nano-Hydroxyapatite Composites.

Inkjet printing is a leading technology in the biofabrication of three-dimensional biomaterials, offering digital, noncontact deposition with micron-level precision. Among these materials, hydroxyapatite is widely recognized for its use in bone tissue engineering. However, most hydroxyapatite-laden inks are unsuitable for inkjet printing. To address this, we developed photocurable and biodegradable phosphoramide-based hydrogels containing thiol-functionalized polyethylene glycol via click chemistry. These hydrogels degrade into phosphates, the natural component of bone. The rheological properties of the inks are finely tuned through chemical design to meet the requirements of nanohydroxyapatite composite inks for piezoelectric inkjet printing. We demonstrated their printability using simple geometric patterns, showcasing a versatile and efficient solution for the precise inkjet printing of biomaterial composites.