Imaging of femtosecond bond breaking and charge dynamics in ultracharged peptides

We study bond breaking and charge dynamics of ionized peptides in both real and reciprocal space.

Beyond strain release: Delocalisation-enabled organic reactivity

Strain energy has long been recognised as a fundamental driving force for organic reactions. However, the release of strain alone is an insufficient predictor of reactivity, as seen in the equivalent strain energies but disparate reactivity of cyclopropane and cyclobutane. Here we show that electronic delocalisation is a key factor that operates alongside strain release to boost reactivity, significantly lowering the energy required for bond-breaking in cyclopropanes, cycloalkynes and cycloalkenes. Consideration of thermodynamic and delocalisation parameters explains the relative rates of reaction of molecules containing these functional groups, leading to a ‘hierarchy of delocalisation’ and a rule-of-thumb model that accurately predicts activation barriers. The implications of these principles are demonstrated in the context of the reactions of strained building blocks commonly encountered in total synthesis, medicinal chemistry, polymer science and bioconjugation.

Heterogeneous Photocatalysis of Metronidazole in Aquatic Samples

Metronidazole (MET) is a commonly detected contaminant in the environment. The compound is classified as poorly biodegradable and highly soluble in water. Heterogeneous photocatalysis is the most promoted water purification method due to the possibility of using sunlight and small amounts of a catalyst needed for the process. The aim of this study was to select conditions for photocatalytic removal of metronidazole from aquatic samples. The effect of catalyst type, mass, and irradiance intensity on the efficiency of metronidazole removal was determined. For this purpose, TiO2, ZnO, ZrO2, WO3, PbS, and their mixtures in a mass ratio of 1:1 were used. In this study, the transformation products formed were identified, and the mineralization degree of compound was determined. The efficiency of metronidazole removal depending on the type of catalyst was in the range of 50–95%. The highest MET conversion (95%) combined with a high degree of mineralization (70.3%) was obtained by using a mixture of 12.5 g TiO2–P25 + PbS (1:1; v/v) and running the process for 60 min at an irradiance of 1000 W m−2. Four MET degradation products were identified by untargeted analysis, formed by the rearrangement of the metronidazole and the C-C bond breaking.

Low-Temperature Mechano-Chemical Rubber Reclamation Using Terpinene as a Swelling Agent to Enhance Bond-Breaking Selectivity

Common swelling agents used in the mechano-chemical rubber devulcanization process usually require high temperatures to achieve satisfactory swelling effects, which results in severe production of pollutants and reduces the selectivity of bond scissions. This work presents an environmentally friendly swelling agent, terpinene, which can swell the rubber crosslink structures at low temperatures. Both a rubber swelling experiment and a rubber reclaiming experiment with a mechano-chemical devulcanization method are conducted to explore the swelling effects of terpinene. After soaking in terpinene at 60 °C for 90 min, the length elongation of the rubber sample reaches 1.55, which is much higher than that in naphthenic oil and is comparable to that in toluene. When adding 3 phr of terpinene for every 100 phr of waste rubber during the reclaiming process, the bond scissions exhibit high selectivity. After revulcanization, the reclaimed rubbers have a tensile strength of 17 MPa and a breaking elongation of 400%. Consequently, the application of terpinene as the swelling agent in the LTMD method can greatly improve the properties of reclaimed rubbers, thereby enhancing the dual value for the economy and environment.

Breaking a dative bond with mechanical forces

Bond breaking and forming are essential components of chemical reactions. Recently, the structure and formation of covalent bonds in single molecules have been studied by non-contact atomic force microscopy (AFM). Here, we report the details of a single dative bond breaking process using non-contact AFM. The dative bond between carbon monoxide and ferrous phthalocyanine was ruptured via mechanical forces applied by atomic force microscope tips; the process was quantitatively measured and characterized both experimentally and via quantum-based simulations. Our results show that the bond can be ruptured either by applying an attractive force of ~150 pN or by a repulsive force of ~220 pN with a significant contribution of shear forces, accompanied by changes of the spin state of the system. Our combined experimental and computational studies provide a deeper understanding of the chemical bond breaking process.

Estimating the activation energy of bond hydrolysis by time-resolved weighing of dissolving crystals

Bond-breaking activation energy EB is nowadays a key parameter for understanding and modeling crystal dissolution processes. However, a methodology to estimate EB based on classical dissolution experiments still does not exist. We developed a new method based on the calibration of a Kossel type dissolution model on measured dissolution rates obtained by mass (or volume) variations over time. The dissolution model does not depend on the geometry of the crystal surface but only on the density of the different types of sites (kink, step, terrace, bulk). The calibration method was applied to different experimental setups (flow through and batch) with different ways of estimating the dissolution rates (solute concentration in the fluid, surface topography) for calcite crystals. Despite the variety of experimental conditions, the estimated bond-breaking activation energies were very close to each other (between 31 and 35 kJ/mol) and in good agreement with ab initio calculations.

Tetrabutylammonium Iodide Mediated Sulfenylation of Poly­substituted 1H-Pyrazol-5-amines with Arylsulfonyl Hydrazides

A TBAI-mediated sulfenylation of N,3-diaryl-1-arylsulfonyl-1H-pyrazol-5-amines with arylsulfonyl hydrazides has been established, and an expanded inventory of N,5-diaryl-4-(arylthio)-1H-pyrazol-3-amines was constructed through C–S bond formation and N–S bond breaking. Mechanistic investigations suggest thiosulfonate as a key intermediate in the sulfenylation, and the detosylation is promoted by the generated arylsulfinic acid. The method is characterized by simple operating conditions, broad substrate range as well as gram-scale reaction.

Assessment of the Mechanism of Adhesive Destruction Coatings

Information on deformation of coatings at different loading levels during peeling is given. It is shown that the deformations of the organosilicon coating appear already at the initial stages of loading, and the obtained data correlate with the data on acoustic emission. For a polyvinyl acetate coating at low loading levels, equal to 0.3-0.4 R, the release of acoustic signal energy is not observed. The absence of signals with a large amplitude at loading levels up to 0.7-0.8 R indicates the development of plastic deformations in the contact zone of the coating with the substrate. It was found that early localization of bond breaking in the contact zone, leading to the formation of a fracture focus, occurs in organosilicon coatings KO-168. For PVAC coatings, an abrupt growth of cracks is characteristic, which is preceded by its slow growth. The pseudoplastic mechanism of destruction of PVAC coatings has been established. The influence of the nature of the substrate on the change in the nature of the peeling of the coatings is considered.