Publications

We present the use of an ultraporous permanently polarized hydroxyapatite (upp-HAp) catalyst for continuous and highly efficient production of formic acid (predominant) and acetic acid using wet CO2 (i.e. CO2 bubbled into liquid water) as a reagent. In all cases, reactions were conducted at temperatures ranging from 95 to 150 degrees C, using a CO2 constant flow of 100 mL s(-1), and without applying any external electric field and/or UV radiation. Herein, we study how to transfer such a catalytic system from batch to continuous reactions, focusing on the water supply (proton source): (1) wet CO2 or (2) liquid water in small amounts is introduced in the reactor. In general, the reduction of CO2 to formic acid predominates over the C-C bond formation reaction. On the other hand, when liquid water is added, two interesting outcomes are observed: (1) the yield of products is higher than in the first scenario (>2 mmol g(c)(-1)min(-1)) while the initial liquid water remains largely available due to the mild reaction temperature (95 degrees C); and (2) a high yield of ethanol (>0.5 mmol g(c)(-1)min(-1)) is observed at 120 degrees C, as a result of the increased efficiency of the C-C bond formation. Analysis of kinetic studies through temporal and temperature dependence shows that CO2 fixation is the rate limiting step, ruling out the competing effect of proton adsorption on the binding sites and confirming the crucial role of water. The activation energy for the CO2 fixation reaction has been determined to be 66 +/- 1 kJ mol(-1), which is within the range of conventional electro-assisted catalysts. Finally, mechanistic insights on the CO2 activation and role of the binding sites of upp-HAp are provided through isotopic-labeling ((CO2)-C-13) and near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) studies.

JTD Keywords: Butano, Challenges, Co2 reduction, Fuels, Hydrogenation, Mechanism, Nanomaterials, Noble-metal

We demonstrate that enzyme-catalyzed reactions can be observed in zero- and low-field NMR experiments by combining recent advances in parahydrogen-based hyperpolarization methods with state-of-the-art magnetometry. Specifically, we investigated two model biological processes: the conversion of fumarate into malate, which is used in vivo as a marker of cell necrosis, and the conversion of pyruvate into lactate, which is the most widely studied metabolic process in hyperpolarization-enhanced imaging. In addition to this, we constructed a microfluidic zero-field NMR setup to perform experiments on microliter-scale samples of [1-C-13]-fumarate in a lab-on-a-chip device. Zero- to ultralow-field (ZULF) NMR has two key advantages over high-field NMR: the signals can pass through conductive materials (e.g., metals), and line broadening from sample heterogeneity is negligible. To date, the use of ZULF NMR for process monitoring has been limited to studying hydrogenation reactions. In this work, we demonstrate this emerging analytical technique for more general reaction monitoring and compare zero- vs low-field detection.

JTD Keywords: Fumarates, Hydrogenation, Magnetic resonance imaging, Magnetic resonance spectroscopy, Nmr j-spectroscopy, Pyruvic acid

We present a versatile method for the preparation of hyperpolarized [1-13C]fumarate as a contrast agent for preclinical in vivo MRI, using parahydrogen-induced polarization (PHIP). To benchmark this process, we compared a prototype PHIP polarizer to a state-of-the-art dissolution dynamic nuclear polarization (d-DNP) system. We found comparable polarization, volume, and concentration levels of the prepared solutions, while the preparation effort is significantly lower for the PHIP process, which can provide a preclinical dose every 10 min, opposed to around 90 min for d-DNP systems. With our approach, a 100 mM [1-13C]-fumarate solution of volumes up to 3 mL with 13-20% 13C-hyperpolarization after purification can be produced. The purified solution has a physiological pH, while the catalyst, the reaction side products, and the precursor material concentrations are reduced to nontoxic levels, as confirmed in a panel of cytotoxicity studies. The in vivo usage of the hyperpolarized fumarate as a perfusion agent in healthy mice and the metabolic conversion of fumarate to malate in tumor-bearing mice developing regions with necrotic cell death is demonstrated. Furthermore, we present a one-step synthesis to produce the 13C-labeled precursor for the hydrogenation reaction with high yield, starting from 13CO2 as a cost-effective source for 13C-labeled compounds.

JTD Keywords: Animals, Contrast media, Fumarates, Hydrogenation, Magnetic resonance imaging, Magnetic resonance spectroscopy, Mice, Para-hydrogen

JTD Keywords: added value chemicals, amino-acids, catalytic-hydrogenation, climate, design, electrochemical reduction, electroreduction, green co2 conversion to ethanol, nitrogen, photocatalytic reduction, polarized hydroxyapatite, recycling co2, sea-level, Acetone, Added value chemicals, Added-value chemicals, C-c coupling, Calcium apatites, Carbon dioxide, Carbon-dioxide, Co 2 reduction, Co2 reduction, Ethanol, Green co2 conversion to ethanol, Hard tissues, Hydroxyapatite, Mixtures, Morphology, Morphology and composition, Naturally occurring, Organic carbon, Phosphate minerals, Polarized hydroxyapatite, Recycling co2