Advancements and Challenges in the Synthesis of Oxymethylene Ethers (OMEs) as Sustainable Transportation Fuels.

The urgent need for sustainable alternatives to fossil fuels in the transportation sector is driving research into novel energy carriers that can meet the high energy density requirements of heavy-duty vehicles without exacerbating the climate change. This concept article examines the synthesis, mechanisms, and challenges associated with oxymethylene ethers (OMEs), a promising class of synthetic fuels potentially derived from carbon dioxide and hydrogen. We highlight the importance of OMEs in the transition towards non-fossil energy sources due to their compatibility with the existing Diesel infrastructure and their cleaner combustion profile. The synthesis mechanisms, including the Schulz-Flory distribution and its implications for OME chain length specificity, and the role of various catalysts and starting materials are discussed in depth. Despite advancements in the field, significant challenges remain, such as overcoming the Schulz-Flory distribution, efficiently managing water byproducts, and improving the overall energy efficiency of the OME synthesis. Addressing these challenges is crucial for OMEs to become a viable alternative fuel, contributing to the reduction of greenhouse gas emissions and the transition to a sustainable energy future in the transportation sector.

Oxymethylene Ether (OME) Fuel Catalyst Screening Using In Situ NMR Spectroscopy.

Online NMR measurements are introduced in the current study as a new analytical setup for investigation of the oxymethylene dimethyl ether (OME) synthesis. For the validation of the setup, the newly established method is compared with state-of-the-art gas chromatographic analysis. Afterwards, the influence of different parameters, such as temperature, catalyst concentration and catalyst type on the OME fuel formation based on trioxane and dimethoxymethane is investigated. As catalysts, AmberlystTM 15 (A15) and trifluoromethanesulfonic acid (TfOH) are utilized. A kinetic model is applied to describe the reaction in more detail. Based on these results, the activation energy (A15: 48.0 kJ mol-1 and TfOH: 72.3 kJ mol-1 ) and the order in catalyst (A15: 1.1 and TfOH: 1.3) are calculated and discussed.

Investigation of the cooperative-effects of Lewis- and Brønstedt acids in homogeneously catalyzed OME fuel synthesis by inline-NMR monitoring.

Via inline-nuclear magnetic resonance measurements, the homogeneously catalyzed poly(oxymethylene dimethyl ether) fuel synthesis using trioxane and dimethoxy methane is investigated. Besides the Brønsted acid (BA) catalyst triflic acid (TfOH) different metal halides are studied as Lewis-acidic (LA) catalysts. Among the used LAs, MgCl2, the weakest based on electronegativity, reveals the highest catalytical activity. Additionally, the influence of the concentration of BA and LA is investigated. An increase in BA concentration leads to an exponential increase of the reaction rate, while increasing the concentration of the LA leads to a volcano plot with its optimum at a LA : BA ratio of 1 : 3. The influence of the LA on the electron density of the intermediate formaldehyde is concluded as the main factor for this behavior.

Fully Automated Multi-Step Synthesis of Block Copolymers.

An automated synthesis protocol is developed for the synthesis of block copolymers in a multi-step approach in a fully automated manner. For this purpose, an automated dialysis setup is combined with robot-based synthesis protocols. Consequently, several block copolymerizations are executed completely automated and compared to the respective manual synthesis. As a result, this study opens up the field of autonomous multi-step reactions without any human interactions.

Miniemulsion polymerization at low temperature: A strategy for one-pot encapsulation of hydrophobic anti-inflammatory drugs into polyester-containing nanoparticles.

HYPOTHESIS: Conventional synthesis methods of polymeric nanoparticles as drug delivery systems are based on the use of large amounts of organic solvents, hence requiring several steps for the obtaining of waterborne dispersions. In view of the need for new environmentally friendly methods, emulsion polymerization and their related techniques are a good alternative for the production of monodispersed waterborne dispersions of biodegradable nanoparticles in a cleaner, reproducible and faster manner. EXPERIMENTS: Herein, the miniemulsion polymerization technique at low temperature using poly(2-ethyl-2-oxazoline) as surfactant has been developed for poly(hydroxyethyl methacrylate-lactic acid) and poly(hydroxyethyl methacrylate-lactic-co-glycolic acid) nanoparticles. Additionally, the anti-inflammatory drug BRP-187 was used to proof the potential of this technique in the encapsulation of hydrophobic drugs. The effect of the oligomer composition on the miniemulsion and the final dispersion stability, the final oligomer conversion, the polymer particle size and the drug encapsulation efficiency has been studied. FINDINGS: Monodisperse spherical particles ranging between 170 and 250 nm in diameter in long term non-toxic stable waterborne dispersions were obtained with drug encapsulation efficiencies up to 66%. In contrast with conventional synthesis techniques, residual organic solvents are completely removed and, thus, the potential of redox initiated miniemulsion polymerization to obtain stable drug loaded poly(hydroxyethyl methacrylate-lactic acid) and poly(hydroxyethyl methacrylate-lactic-co-glycolic acid) nanoparticles in an efficient and fast manner is shown.

Improvement of High-Throughput Experimentation Using Synthesis Robots by the Implementation of Tailor-Made Sensors.

A small, low-cost, self-produced photometer is implemented into a synthesis robot and combined with a modified UV chamber to enable automated sampling and online characterization. In order to show the usability of the new approach, two different reversible addition-fragmentation chain transfer (RAFT) polymers were irradiated with UV light. Automated sampling and subsequent characterization revealed different reaction kinetics depending on polymer type. Thus, a long initiation time (20 min) is required for the end-group degradation of poly(ethylene glycol) ether methyl methacrylate (poly(PEGMEMA)), whereas poly(methyl methacrylate) (PMMA) is immediately converted. Lastly, all photometric samples are characterized via size-exclusion chromatography using UV and RI detectors to prove the results of the self-produced sensor and to investigate the molar mass shift during the reaction.

Prediction of Nanoparticle Sizes for Arbitrary Methacrylates Using Artificial Neuronal Networks.

Particle sizes represent one of the key factors influencing the usability and specific targeting of nanoparticles in medical applications such as vectors for drug or gene therapy. A multi-layered graph convolutional network combined with a fully connected neuronal network is presented for the prediction of the size of nanoparticles based only on the polymer structure, the degree of polymerization, and the formulation parameters. The model is capable of predicting particle sizes obtained by nanoprecipitation of different poly(methacrylates). This includes polymers the network has not been trained with, indicating the high potential for generalizability of the model. By utilizing this model, a significant amount of time and resources can be saved in formulation optimization without extensive primary testing of material properties.

Automated Polymer Purification Using Dialysis.

The automated dialysis of polymers in synthetic robots is described as a first approach for the purification of polymers using an automated protocol. For this purpose, a dialysis apparatus was installed within a synthesis robot. Therein, the polymer solution could be transferred automatically into the dialysis tube. Afterwards, a permanent running dialysis could be started, enabling the removal of residual monomer. Purification efficiency was studied using chromatography and NMR spectroscopy, showing that the automated dialysis requires less solvent and is faster compared to the classical manual approach.