Notes

The particular Tunable Photophysical Properties of Enamine Intermediates Involved in Light-Driven Aminocatalysis.
Singlet vinylidenes (R2C═C) are proposed as intermediates in a series of organic reactions, and very few have been studied by matrix isolation or gas-phase spectroscopy. Triplet vinylidenes, however, featuring two unpaired electrons at a monosubstituted carbon atom are thus far only predicted as electronically excited-state species and represent an unexplored class of carbon-centered diradicals. We report the photochemical generation and low-temperature EPR/ENDOR characterization of the first ground-state high-spin (triplet) vinylidene. The zero-field splitting parameters (D = 0.377 cm-1 and |E|/D = 0.028) were determined, and the 13C hyperfine coupling tensor was obtained by 13C-ENDOR measurements. Most strikingly, the isotropic 13C hyperfine coupling constant (50 MHz) is far smaller than the characteristic values of triplet carbenes, demonstrating a unique electronic structure which is supported by quantum chemical calculations.Self-immolative polymers are an emerging class of macromolecules with distinct disassembly profiles that set them apart from other general degradable materials. These polymers are programmed to disassemble spontaneously from head to tail, through a domino-like fragmentation, upon response to extremal stimuli. In the time since we first reported this unique type of molecule, several groups around the world have developed new, creative molecular structures that perform analogously to our pioneering polymers. Self-immolative polymers are now widely recognized as an important class of stimuli-responsive materials for a wide range of applications such as signal amplification, biosensing, drug delivery, and materials science. The quinone-methide elimination was shown to be an effective tool to achieve rapid domino-like fragmentation of polymeric molecules. Thus, numerous applications of self-immolative polymers are based on this disassembly chemistry. Although several other fragmentation reactions achieved the function requested for sequential disassembly, we predominantly focused in this Perspective on examples of self-immolative polymers that disassemble through the quinone-methide elimination. Selected examples of self-immolative polymers that disassembled through other chemistries are briefly described. The growing demand for stimuli-responsive degradable materials with novel molecular backbones and enhanced properties guarantees the future interest of the scientific community in this unique class of polymers.Metal-organic frameworks (MOFs) are materials in which metals and organic compounds form crystalline and porous structures. Previous studies have investigated the relationships between the structure properties and physical properties of MOFs through molecular simulations, but the overall relationships in MOFs, including the relationships between the metals and organic components and the experimentally measured physical properties, have not been clarified. In this study, we developed two regression models between three elements in MOFs the components, structure properties, and gas-adsorption capacities as physical properties. Using a nonlinear regression analysis method, we succeeded in predicting the structure properties from the components and the physical properties from the structure properties.Methods for efficient simulations of multidimensional quantum dynamics are essential for theoretical studies of chemical systems where quantum effects are important, such as those involving rearrangements of protons or electronic configurations. Here, we introduce the functional tensor-train Chebyshev (FTTC) method for rigorous nuclear quantum dynamics simulations. click here FTTC is essentially the Chebyshev propagation scheme applied to the initial state represented in a continuous analogue tensor-train format. We demonstrate the capabilities of FTTC as applied to simulations of proton quantum dynamics in a 50-dimensional model of hydrogen-bonded DNA base pairs.Herein, we demonstrated an efficient protocol for reductive alkylation of azides/nitro compounds via a borrowing hydrogen (BH) method. By following this protocol, selective mono- and dialkylated amines were obtained under mild and solvent-free conditions. A series of control experiments and deuterium-labeling experiments were performed to understand this catalytic process. Mechanistic studies suggested that the Ir(III)-H was the active intermediate in this reaction. KIE study revealed that the breaking of the C-H bond of alcohol might be the rate-limiting step. Notably, this solvent-free strategy disclosed a high TON of around 5600. Based on kinetic studies and control experiments, a metal-ligand cooperative mechanism was proposed.BesC catalyzes the iron- and O2-dependent cleavage of 4-chloro-l-lysine to form 4-chloro-l-allylglycine, formaldehyde, and ammonia. This process is a critical step for a biosynthetic pathway that generates a terminal alkyne amino acid which can be leveraged as a useful bio-orthogonal handle for protein labeling. As a member of an emerging family of diiron enzymes that are typified by their heme oxygenase-like fold and a very similar set of coordinating ligands, recently termed HDOs, BesC performs an unusual type of carbon-carbon cleavage reaction that is a significant departure from reactions catalyzed by canonical dinuclear-iron enzymes. Here, we show that BesC activates O2 in a substrate-gated manner to generate a diferric-peroxo intermediate. Examination of the reactivity of the peroxo intermediate with a series of lysine derivatives demonstrates that BesC initiates this unique reaction trajectory via cleavage of the C4-H bond; this process represents the rate-limiting step in a single turnover reaction. The observed reactivity of BesC represents the first example of a dinuclear-iron enzyme that utilizes a diferric-peroxo intermediate to capably cleave a C-H bond as part of its native function, thus circumventing the formation of a high-valent intermediate more commonly associated with substrate monooxygenations."Hongmeiren" bananas are popular because of their red peel. Two extraction methods solvent-assisted flavor evaporation and headspace solid-phase microextraction, combined with gas chromatography-olfactometry and gas chromatography-mass spectrometry (GC-MS), were used to analyze the volatile components of "Hongmeiren" bananas. A total of 86 aroma compounds were identified by GC-MS, 62 of which were identified as the major aroma-active compounds with an odor activity value ≥ 1 or modified frequency ≥ 30%. Ethyl (E)-2-butenoate, 4-undecanone, and α-phellandrene were found in bananas for the first time. Sensory experiments showed that eight sweet-associated odorants could significantly achieve the sweetness enhancement effect at 30 g/L sucrose solution by odor-induced changes in taste perception. These experiments suggest that selected odorants can achieve sugar reduction, but with consideration of the sugar concentration. The study of the sweetness enhancement effect of individual compounds provides a more direct theoretical support for sugar reduction in the food industry.We have described a sulfonamide-selective ambient ion source coupled with electrospray ionization mass spectrometry (ESI-MS) for selective extraction and determination of trace sulfonamide antibiotics. It is obtained by modifying an iron sheet with a sulfadiazine-templated hydrophilic molecularly imprinted polymer (SF-HMIP). It behaves as both an online extractor and a MS ion source. Five sulfonamide antibiotics, including sulfamethoxazole (SMZ), sulfamerazine (SMR), sulfisoxazole (SIZ), sulfathiazole (ST), and sulfameter (SMD), were chosen to evaluate SF-HMIP coupled with ESI-MS, which showed good linearity in the range of 0.2-1000 ng/mL with correlation coefficient values (R2) over 0.9946. The limits of detection (LODs) for analysis of pure water and honey were in the range of 0.1-0.2 and 0.2-1.5 ng/mL, respectively. Limits of quantitation (LOQs) for analysis of pure water and honey were in the range of 0.3-0.5 and 1.0-5.0 ng/mL, respectively. The results demonstrated that SF-HMIP combined with ESI-MS could be applied for the direct analysis of five trace sulfonamide compounds in honey and pure water with recoveries ranging from 76 to 129%.Negative chemical ionization (NCI) and electron-capture negative ionization (ECNI) are gas chromatography-mass spectrometry (GC-MS) techniques that generate negative ions in the gas phase for compounds containing electronegative atoms or functional groups. In ECNI, gas-phase thermal electrons can be transferred to electrophilic substances to produce M-• ions and scarce fragmentation. As a result of the electrophilicity requirements, ECNI is characterized by high-specificity and low background noise, generally lower than EI, offering lower detection limits. The aim of this work is to explore the possibility of extending typical advantages of ECNI to liquid chromatography-mass spectrometry (LC-MS). The LC is combined with the novel liquid-EI (LEI) LC-EIMS interface, the eluent is vaporized and transferred inside a CI source, where it is mixed with methane as a buffer gas. As proof of concept, dicamba and tefluthrin, agrochemicals with herbicidal and insecticidal activity, respectively, were chosen as model compounds and detected together in a commercial formulation. The pesticides have different chemical properties, but both are suitable analytes for ECNI due to the presence of electronegative atoms in the molecules. The influence of the mobile phase and other LC- and MS-operative parameters were methodically evaluated. Part-per-trillion (ppt) detection limits were obtained. Ion abundances were found to be stable with quantitative linear detection, reliable, and reproducible, with no influence from coeluting interfering compounds from the sample matrix.Amidoboronic acid-containing peptidomimetics are an important class of scaffolds in chemistry and drug discovery. Despite increasing interest in boron-based enzyme inhibitors, constrained amidoboronic acids have received little attention due to the limited options available for their synthesis. We describe a new methodology to prepare both α- and β-amidoboronic acids that impose restrictions on backbone angles. Lewis acid-promoted Boyer-Schmidt-Aube lactam ring expansions using an azidoalkylboronate enabled generation of constrained α-amidoboronic acid derivatives, whereas assembly of the homologous β-amidoboronic acids was achieved through a novel boronic acid-mediated lactamization process stemming from an α-boryl aldehyde. The results of quantum chemical calculations suggest carboxylate-boron coordination to be rate-limiting for small ring sizes, whereas the tetrahedral intermediate formation is rate limiting in the case of larger rings. As part of this study, an application of β-amidoboronic acid derivatives as novel VIM-2 metallo-β-lactamase inhibitors has been demonstrated.The ability to manipulate C-C bonds for selective chemical transformations is challenging and represents a growing area of research. Here, we report a formal insertion of diazo compounds into the "unactivated" C-C bond of benzyl bromide derivatives catalyzed by a simple Lewis acid. The homologation reaction proceeds via the intermediacy of a phenonium ion, and the products contain benzylic quaternary centers and an alkyl bromide amenable to further derivatization. Computational analysis provides critical insight into the reaction mechanism, in particular the key selectivity-determining step.
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