Analysis of sensitivity enhancement by dynamic nuclear polarization in solid-state NMR: a case study of functionalized mesoporous materials.

We systematically studied the enhancement factor (per scan) and the sensitivity enhancement (per unit time) in (13)C and (29)Si cross-polarization magic angle spinning (CP-MAS) NMR boosted by dynamic nuclear polarization (DNP) of functionalized mesoporous silica nanoparticles (MSNs). Specifically, we separated contributions due to: (i) microwave irradiation, (ii) quenching by paramagnetic effects, (iii) the presence of frozen solvent, (iv) the temperature, as well as changes in (v) relaxation and (vi) cross-polarization behaviour. No line-broadening effects were observed for MSNs when lowering the temperature from 300 to 100 K. Notwithstanding a significant signal reduction due to quenching by TOTAPOL radicals, DNP-CP-MAS at 100 K provided global sensitivity enhancements of 23 and 45 for (13)C and (29)Si, respectively, relative to standard CP-MAS measurements at room temperature. The effects of DNP were also ascertained by comparing with state-of-the-art two-dimensional heteronuclear (1)H{(13)C} and (29)Si{(1)H} correlation spectra, using, respectively, indirect detection or Carr-Purcell-Meiboom-Gill (CPMG) refocusing to boost signal acquisition. This study highlights opportunities for further improvements through the development of high-field DNP, better polarizing agents, and improved capabilities for low-temperature MAS.

High-throughput analysis of algal crude oils using high resolution mass spectrometry.

Lipid analysis often needs to be specifically optimized for each class of compounds due to its wide variety of chemical and physical properties. It becomes a serious bottleneck in the development of algae-based next generation biofuels when high-throughput analysis becomes essential for the optimization of various process conditions. We propose a high-resolution mass spectrometry-based high-throughput assay as a 'quick-and-dirty' protocol to monitor various lipid classes in algal crude oils. Atmospheric pressure chemical ionization was determined to be most effective for this purpose to cover a wide range of lipid classes. With an autosampler-LC pump set-up, we could analyze algal crude samples every one and half minutes, monitoring several lipid species such as TAG, DAG, squalene, sterols, and chlorophyll a. High-mass resolution and high-mass accuracy of the orbitrap mass analyzer provides confidence in the identification of these lipid compounds. MS/MS and MS3 analysis could be performed in parallel for further structural information, as demonstrated for TAG and DAG. This high-throughput method was successfully demonstrated for semi-quantitative analysis of algal oils after treatment with various nanoparticles.

Functional mesoporous silica nanoparticles for the selective sequestration of free fatty acids from microalgal oil.

A series of 2d-hexagonally packed mesoporous silica nanoparticle material with 10 nm pore diameter (MSN-10) covalently functionalized with organic surface modifiers have been synthesized via a post-synthesis grafting method. The material structure has been characterized by powder X-ray diffraction, electron microscopy, and nitrogen sorption analyses, and the free fatty acid (FFA) sequestration capacity and selectivity was investigated and quantified by thermogravimetric and GC/MS analysis. We discovered that aminopropyl functionalized 10 nm pore mesoporous silica nanoparticle material (AP-MSN-10) sequestered all available FFAs and left nearly all other molecules in solution from a simulated microalgal extract containing FFAs, sterols, terpenes, and triacylglycerides. We also demonstrated selective FFA sequestration from commercially available microalgal oil.