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Self-healing polymer materials have drawn rapidly increasing interest over the last decade, and have been studied and used in an ever-increasing range of applications. Herein, we successfully make the covalent urea bond – a pinnacle of stability due to strong resonance effects – dynamic in nature through mediation of zinc salts. The dynamic covalent character of urea in the presence of zinc ions is confirmed through dissociation reaction experiments and quantum chemical calculations of small-molecule model urea compounds. In line with our experiments, the modelling results suggest that the presence of zinc ions speeds up the reaction of urea dissociation by two orders of magnitude via the formation of O-bound Zn complexes. Based on such dynamic covalent urea bonds, we then develop a novel class of self-healing polymer materials with excellent healing efficiencies. Different kinds of self-healing and reprocessable polyurea materials were prepared, with polymer properties that can be easily tuned by varying the degree of crosslinking and the molecular weight of the siloxane precursor. Since different kinds of self-healing polyurea materials could easily be prepared due to the commercial availability of a very wide range of amine and isocyanate monomers, this introduction of self-healing properties is expected to have significant potential in a range of applications, such as coatings, paints, and 3D printing. In addition, this introduces polyureas and other urea-containing polymers as a class of highly stable, yet easily reprocessable plastics, which is highly relevant given the globally desired more sustainable use of plastics.

Molecular simulations were used to compute the equilibrium concentrations of the different species in CO2/monoethanolamine solutions for different CO2 loadings. Simulations were performed in the Reaction Ensemble using the continuous fractional component Monte Carlo method at temperatures of 293, 333, and 353 K. The resulting computed equilibrium concentrations are in excellent agreement with experimental data. The effect of different reaction pathways was investigated. For a complete understanding of the equilibrium speciation, it is essential to take all elementary reactions into account because considering only the overall reaction of CO2 with MEA is insufficient. The effects of electrostatics and intermolecular van der Waals interactions were also studied, clearly showing that solvation of reactants and products is essential for the reaction. The Reaction Ensemble Monte Carlo using the continuous fractional component method opens the possibility of investigating the effects of the solvent on CO2 chemisorption by eliminating the need to study different reaction pathways and concentrate only on the thermodynamics of the system.

Poster presented at CHAINS 2016 Symposium, The Netherlands

A series of novel discotic liquid crystal compounds containing three pendent triphenylenes connected to a triazine core via spacers of different length that were linked via a triazole group as obtained from an azide–alkyne click reaction was investigated. All compounds of the series exhibit wide-range columnar phases from room temperature to more than 100°C. X-ray reflection measurements indicate an ordering with separate columns of the triazine and triphenylene cores. Quantum chemical calculations confirmed the significant contributions of the triazine and triazole groups to the p–p stacking in the columns. This type of organisation reveals an additional feature of triazole-forming click chemistry and indicates interesting properties for optoelectronic applications.

Piperazine is a widely studied solvent for post-combustion carbon dioxide capture. To investigate the possibilities of further improving this process, the electronic and steric effects of -CH(3), -CH(2)F, -CH(2)OH, -CH(2)NH(2), -COCH3 , and -CN groups of 2,5-disubstituted piperazines on the pKa and carbamate stability towards hydrolysis are investigated by quantum chemical methods. For the calculations, B3LYP, M11L, and spin-component-scaled MP2 (SCS-MP2) methods are used and coupled with the SMD solvation model. The experimental pK(a) values of piperazine, 2-methylpiperazine, and 2,5-dimethylpiperazine agree well with the calculated values. The present study indicates that substitution of -CH(3), -CH(2) NH(2), and -CH(2) OH groups on the 2- and 5-positions of piperazine has a positive impact on the CO(2) absorption capacity by reducing the carbamate stability towards hydrolysis. Furthermore, their higher boiling points, relative to piperazine itself, will lead to a reduction of volatility-related losses.

Thiol-yne click (TYC) chemistry was utilized as a copper-free click reaction for the modification of alkyne-terminated monolayers on oxide-free Si(111) surfaces, and the results were compared with the analogous thiol–ene click (TEC) chemistry. A wide range of thiols such as 9-fluorenylmethoxy-carbonyl cysteine, thio-ß-d-glucose tetraacetate, thioacetic acid, thioglycerol, thioglycolic acid, and 1H,1H,2H,2H-perfluorodecanethiol was immobilized using TYC under photochemical conditions, and all modified surfaces were characterized by static water contact angle measurements, X-ray photoelectron spectroscopy (including a simulation thereof by density functional calculations), and infrared absorption reflection spectroscopy. Surface-bound TYC proceeds with an efficiency of up to 1.5 thiols per alkyne group. This high surface coverage proceeds without oxidizing the Si surface. TYC yielded consistently higher surface coverages than TEC, due to double addition of thiols to alkyne-terminated monolayers. This also allows for the sequential and highly efficient attachment of two different thiols onto an alkyne-terminated monolayer.

H-Si(111)-terminated surfaces were alkenylated via two routes: Through a novel one-step gas-phase hydrosilylation reaction with short alkynes (C3 to C6) and for comparison via a two-step chlorination and Grignard alkenylation process. All modified surfaces were characterized by static water contact angles and X-ray photoelectron spectroscopy (XPS). Propenyl- A nd butenyl-coated Si(111) surfaces display a significantly higher packing density than conventional C10-C18 alkynederived monolayers, showing the potential of this approach. In addition, propyne chemisorption proceeds via either of two approaches: The standard hydrosilylation at the terminal carbon (lin) at temperatures above 90°C and an unprecedented reaction at the second carbon (iso) at temperatures below 90°C. Molecular modeling revealed that the packing energy of a monolayer bonded at the second carbon is significantly more favorable, which drives iso-attachment, with a dense packing of surface-bound iso-propenyl chains at 40% surface coverage, in line with the experiments at

The pKa of the conjugate acids of alkanolamines, neurotransmitters, alkaloid drugs and nucleotide bases are calculated with density functional methods (B3LYP, M08-HX and M11-L) and ab initio methods (SCS-MP2, G3). Implicit solvent effects are included with a conductor-like polarizable continuum model (CPCM) and universal solvation models (SMD, SM8). G3, SCS-MP2 and M11-L methods coupled with SMD and SM8 solvation models perform well for alkanolamines with mean unsigned errors below 0.20 pKa units, in all cases. Extending this method to the pKa calculation of 35 nitrogen-containing compounds spanning 12 pKa units showed an excellent correlation between experimental and computational pKa values of these 35 amines with the computationally low-cost SM8/M11-L density functional approach.

The influence of electronic and steric effects on the stabilities of carbamates formed from the reaction of CO2 with a wide range of alkanolamines was investigated by quantum chemical methods. For the calculations, B3LYP, M11-L, MP2, and spin-component-scaled MP2 (SCS-MP2) methods were used, coupled with SMD and SM8 solvation models. A reduction in carbamate stability leads to an increased CO2 absorption capacity of the amine and a reduction of the energy required for solvent regeneration. Important factors for the reduction of the carbamate stability were an increase in steric hindrance around the nitrogen atom, charge on the N atom and intramolecular hydrogen bond strength. The present study indicates that secondary ethanolamines with sterically hindering groups near the N atom show significant potential as candidates for industrial CO2-capture solvents.

Quantum chemical studies are used to understand the electronic and steric effects on the mechanisms of the reaction of substituted ethanolamines with CO2. SCS-MP2/6-311+G(2d,2p) calculations are used to obtain the activation energy barriers and reaction energies for both the carbamate and bicarbonate formation. Implicit solvent effects are included with the universal solvation model SMD. Carbamate formation is more favorable than bicarbonate formation for monoethanolamine (MEA) both kinetically and thermodynamically. Increase of the steric hindrance on the C atoms around the N atom in substituted ethanolamines favors bicarbonate formation over carbamate formation with lower activation barriers and thereby higher reaction rates. In contrast, substitution by an N-methyl or N-ethyl group on MEA leads to a lower activation barrier for both carbamate formation and bicarbonate formation. As a result, higher reaction rates are expected as compared to MEA, and therefore these compounds have significant potential as industrial CO2 capturing solvents.

We investigate herein whether the reactivity and surface coverage of 1-alkenes toward hydrogen-terminated Si(111) surfaces [H-Si(111)] can be improved by introducing heteroatoms such as oxygen and sulfur at the α-position next to the alkene functional group. To this end, the reactivity of 1-pentene, 1-pentyne, vinyl ethyl ether, and vinyl ethyl sulfide toward H-Si(111) and the surface coverage of the resulting monolayers were studied and compared. All modified surfaces were characterized by static water contact angle measurements, ellipsometry, X-ray photoelectron spectroscopy (XPS), and infrared absorption reflection spectroscopy (IRRAS). Quantum chemical calculations were performed to calculate the activation barriers and driving forces for monolayer formation at the M11-L/6-311G(d,p) level of theory. Both experiments and theory indicate that the presence of α-heteroatoms next to the alkene function improved both the reactivity and surface coverage on H-terminated Si(111) surfaces.

The influence of electronic and steric effects on the reaction between CO(2) and monoethanolamine (MEA) absorbents is investigated using computational methods. The pK(a) of the alkanolamine, the reaction enthalpy for carbamate formation, and the hydrolytic carbamate stability are important factors for the efficiency of CO(2) capture. The steric and electronic effects of CH(3), CH(2)F, CHF(2), CF(3), F, dimethyl, difluoro, and bis(2-trifluoromethyl) substituents at the α carbon of MEA on this reaction are investigated. Density functional theory (DFT) (B3LYP, M06-2X, M08-HX and M11-L) and ab initio methods [spin component-scaled second-order Møller-Plesset theory (SCS-MP2), G3], each coupled with solvent models [conductor-like polarizable continuum model (CPCM) and universal solvation models (SM8 and SMD)], are shown to yield accurately calculated pK(a) values of the substituted MEAs. Specifically, G3, SCS-MP2, and M11-L methods coupled with the SMD and SM8 solvation models perform well with a mean unsigned error (MUE) of only 0.15, 0.24 and 0.25 pK(a) units, respectively. SCS-MP2 is used to calculate the reaction enthalpy for carbamate formation and the carbamate stability towards hydrolysis. With the introduction of β-fluoro substituents (especially the CH(2) F moiety) the reaction enthalpy for the formation of carbamates can be fine-tuned to be less exothermic than that using the unsubstituted MEA. This implies a reduced energy requirement for the solvent-regeneration step in the post-combustion carbon-capture method, which is currently the energy-limiting step in efficient CO(2) capture. β-Fluoro-substituted MEAs are also shown to form less stable carbamates than MEA. Thus, β-fluoro-substituted MEAs display a great potential for the use in the post-combustion carbon-capture process. Finally, a clear correlation is observed between the gas-phase basicity and the tendency to form carbamates. This allows for the rapid prediction of which species will be formed experimentally, and thus the CO(2)-absorbing capacities of alkanolamines can be estimated.

In this review, possible process steps for the production of bio-based industrial chemicals from glutamic acid are described, including a techno-economic assessment of all processes. The products under investigation were those that were shown to be synthesized from glutamic acid on lab-scale, namely N-methylpyrrolidone (NMP), N-vinylpyrrolidone (NVP), succinonitrile, and acrylonitrile. The goal was not only to assess the economic feasibility at this stage, but mainly to discover where is the most potential for improvements in these processes, in order to direct future research. The techno-economic assessment leads to the conclusion that the production of NMP and NVP is the most feasible both in terms of technology and economy. Bio-based acrylonitrile and succinonitrile do not seem very profitable under the current process configurations. Especially the acrylonitrile process shows very high costs in relation to the possible gains. Further optimization is necessary, but a clear direction where the optimization should be aimed could be derived from the assessment, and was provided in the discussion of the processes. The main point to optimize was the reaction of glutamic acid with sodium hypochlorite, a bottleneck in both the acrylonitrile and the succinonitrile process.