C∙∙∙O and Si∙∙∙O Tetrel Bonds: Substituent Effects and Transfer of the SiF3 Group.

The tetrel bond (TB) between 1,2-benzisothiazol-3-one-2-TF3-1,1-dioxide (T = C, Si) and the O atom of pyridine-1-oxide (PO) and its derivatives (PO-X, X = H, NO2, CN, F, CH3, OH, OCH3, NH2, and Li) is examined by quantum chemical means. The Si∙∙∙O TB is quite strong, with interaction energies approaching a maximum of nearly 70 kcal/mol, while the C∙∙∙O TB is an order of magnitude weaker, with interaction energies between 2.0 and 2.6 kcal/mol. An electron-withdrawing substituent on the Lewis base weakens this TB, while an electron-donating group has the opposite effect. The SiF3 group transfers roughly halfway between the N of the acid and the O of the base without the aid of cooperative effects from a third entity.

Experimental and Theoretical Evidence of a Pb⋠⋠⋠Pb Ditetrel Bond Without a σ-Hole.

The crystal structure of a newly synthesized compound, [PbL(Ac)]2 , (where L=2 (amino(pyrazin-2-yl) methylene) hydrazinecarbothioamide, Ac=acetate anion) exhibits a close contact between pairs of Pb atoms, suggesting a ditetrel bond, in addition to two Pb⋅⋅⋅O tetrel bonds, and two C-H⋅⋅⋅O H-bonds. The presence of this ditetrel bond as an attractive component is confirmed by various quantum chemical methods. This novelty of this particular bond is its existence even in the absence of a σ-hole on the Pb atom, which is typically considered a prerequisite for a bond of this type. From a wider perspective, a survey of the Cambridge Structural Database suggests this bond may be more common than was hitherto thought, with 44 examples of Pb⋅⋅⋅Pb contacts amongst a total number of 219 examples of T⋅⋅⋅T interactions in general (T=Si, Ge, Sn, Pb).

Donor-Acceptor Complexes of (5,10,15,20-Tetra(4-methylphenyl)porphyrinato)cobalt(II) with Fullerenes C60: Self-Assembly, Spectral, Electrochemical and Photophysical Properties.

The noncovalent interactions of (5,10,15,20-tetra(4-methylphenyl)porphinato)cobalt(II) (CoTTP) with C60 and 1-N-methyl-2-(pyridin-4-yl)-3,4-fullero[60]pyrrolidine (PyC60) were studied in toluene using absorption and fluorescence titration methods. The self-assembly in the 2:1 complexes (the triads) (C60)2CoTTP and (PyC60)2CoTTP was established. The bonding constants for (C60)2CoTTP and (PyC60)2CoTTP are defined to be (3.47 ± 0.69) × 109 and (1.47 ± 0.28) × 1010 M-2, respectively. 1H NMR, IR spectroscopy, thermogravimetric analysis and cyclic voltammetry data have provided very good support in favor of efficient complex formation in the ground state between fullerenes and CoTTP. PyC60/C60 fluorescence quenching in the PyC60/C60-CoTTP systems was studied and the fluorescence lifetime with various CoTTP additions was determined. The singlet oxygen quantum yield was determined for PyC60 and the intensity decrease in the 1O2 phosphorescence for C60 and PyC60 with the CoTTP addition leading to the low efficiency of intercombination conversion for the formation of the 3C60* triplet excited state was found. Using femtosecond transient absorption measurements in toluene, the photoinduced electron transfer from the CoTTP in the excited singlet state to fullerene moiety was established. Quantum chemical calculations were used for the determination of molecular structure, stability and the HOMO/LUMO energy levels of the triads as well as to predict the localization of frontier orbitals in the triads.

Effect of lipid on surimi gelation properties of the three major Chinese carp.

BACKGROUND: Gel properties are important in determining the quality of surimi. In addition to myofibrillar proteins, lipids play an important role in the formation of surimi gel. Phospholipids (PL) are amphoteric lipids that cannot be removed through rinsing. Paradoxically, the addition of PL increases or decreases gel strength. This research aimed to investigate the effects of specific lipids on the gelation properties of surimi from three different carp. RESULTS: The hardness, chewiness, and gel strength of bighead carp (Aristichthys nobilis: BC) surimi were higher, and the total lipid content was lower when compared with grass carp (Ctenopharyngodon idellus: GC) and silver carp (Hypophthalmichthys molitrix: SC) surimi. Bighead carp surimi had lower levels of phosphatidylethanolamine (PE), phosphatidylinositols (PI), and phosphatidylcholine (PC), and higher phosphatidylserine (PS) and sphingomyelin (SM) content. The gelation properties of surimi increased with increasing concentrations of SM and PS. Furthermore, increased levels of saturated fatty acids (SFAs) and decreased levels of polyunsaturated fatty acids (PUFAs) increased gelation properties. Finally, higher hydrophobic interactions and more disulfide bonds were shown to increase gel network structure stability, resulting in improving gel strength in BC surimi. CONCLUSION: The textural characteristics and gel strength of surimi were dependent on the PL content, including total lipid levels and the types of fatty acids. This may account for previous conflicting reports on PL effects on gel strength. This study provides insight into how the texture of surimi can be improved and provides a starting point for further research. © 2020 Society of Chemical Industry.

Proving and Probing the Presence of the Elusive C-H⋠⋠⋠O Hydrogen Bond in Liquid Solutions at Room Temperature.

Hydrogen bonds (H bonds) play a major role in defining the structure and properties of many substances, as well as phenomena and processes. Traditional H bonds are ubiquitous in nature, yet the demonstration of weak H bonds that occur between a highly polarized C-H group and an electron-rich oxygen atom, has proven elusive. Detailed here are linear and nonlinear IR spectroscopy experiments that reveal the presence of H bonds between the chloroform C-H group and an amide carbonyl oxygen atom in solution at room temperature. Evidence is provided for an amide solvation shell featuring two clearly distinguishable chloroform arrangements that undergo chemical exchange with a time scale of about 2 ps. Furthermore, the enthalpy of breaking the hydrogen bond is found to be 6-20 kJ mol-1 . Ab-initio computations support the findings of two distinct solvation shells formed by three chloroform molecules, where one thermally undergoes hydrogen-bond making and breaking.

Catalysis Based on C-I⋠⋠⋠π Halogen Bonds: Electrophilic Activation of 2-Alkenylindoles by Cationic Halogen-Bond Donors for [4+2] Cycloadditions.

Homo- and cross-[4+2] cycloadditions of 2-alkenylindoles, catalyzed by cationic halogen-bond donors, were developed. Under mild reaction conditions, 3-indolyl-substituted tetrahydrocarbazole derivatives were obtained in good to excellent yields. Experimental and quantum calculation studies revealed that the electrophilic activation of 2-alkenylindoles was achieved by C-I⋅⋅⋅π halogen bonds.

Nucleophilicities of Lewis Bases B and Electrophilicities of Lewis Acids A Determined from the Dissociation Energies of Complexes B⋯A Involving Hydrogen Bonds, Tetrel Bonds, Pnictogen Bonds, Chalcogen Bonds and Halogen Bonds.

It is shown that the dissociation energy D e for the process B⋯A = B + A for 250 complexes B⋯A composed of 11 Lewis bases B (N2, CO, HC≡CH, CH2=CH2, C3H6, PH3, H2S, HCN, H2O, H2CO and NH3) and 23 Lewis acids (HF, HCl, HBr, HC≡CH, HCN, H2O, F2, Cl2, Br2, ClF, BrCl, H3SiF, H3GeF, F2CO, CO2, N2O, NO2F, PH2F, AsH2F, SO2, SeO2, SF2, and SeF2) can be represented to good approximation by means of the equation D e = c ' N B E A , in which N B is a numerical nucleophilicity assigned to B, E A is a numerical electrophilicity assigned to A, and c ' is a constant, conveniently chosen to have the value 1.00 kJ mol-1 here. The 250 complexes were chosen to cover a wide range of non-covalent interaction types, namely: (1) the hydrogen bond; (2) the halogen bond; (3) the tetrel bond; (4) the pnictogen bond; and (5) the chalcogen bond. Since there is no evidence that one group of non-covalent interaction was fitted any better than the others, it appears the equation is equally valid for all the interactions considered and that the values of N B and E A so determined define properties of the individual molecules. The values of N B and E A can be used to predict the dissociation energies of a wide range of binary complexes B⋯A with reasonable accuracy.

Accurate Quantification of Sulfonamide Metabolites in Goat Meat: A New Strategy for Minimizing Interaction between Sheep Serum Albumin and Sulfonamide Metabolites.

To date, the determination of sulfonamide metabolites in animal-derived food has universal disadvantages of low throughput and no integrated metabolites involved. In this study, a powerful and reliable strategy for high-throughput screening of sulfonamide metabolites in goat meat was proposed based on an aqueous two-phase separation procedure (ATPS) combined with ultrahigh-performance liquid chromatography quadrupole-Orbitrap high-resolution mass spectrometry (UHPLC-Q-Orbitrap). Noncovalent interactions including van der Waals force, hydrogen bonding, and hydrophobic effect were determined to be staple interactions between the sulfonamide metabolites and sheep serum albumin by fluorescence spectroscopy and molecular docking technology, and an 80% acetonitrile-water solution/(NH4)2SO4 was used as ATPS in order to release combined sulfonamide metabolites and minimize the influence of sheep serum albumin. Sulfonamide metabolites in the matrix were screened based on a mechanism of mass natural loss and core structure followed by identification combined with the pharmacokinetic. The developed strategy was validated according to EU standard 2002/657/EC with CCα ranging from 0.07 to 0.98 µg kg-1, accuracy recovery with 84-107%, and RSDs lower than 8.9%. Eighty seven goat meat samples were used for determination of 26 sulfonamides and 8 potential metabolites. On the basis of the established innovative process, this study has successfully implemented the comprehensive detection of sulfonamide metabolites, including N4-acetylated substitution, N4-hydroxylation, 4-nitroso, azo dimers, oxidized nitro, N4 monoglucose conjugation, ß-d-glucuronide, and N-4-aminobenzenesulfonyl metabolites, which were shown to undergo oxidation, hydrogenation, sulfation, glucuronidation, glucosylation, and O-aminomethylation.

Enhanced Molecular Recognition between Nucleobases and Guanine-5'-monophosphate-disodium (GMP) by Surfactant Aggregates in Aqueous Solution.

Only specific base pairs on DNA can bind with each other through hydrogen bonds, which is called the Watson-Crick (W/C) pairing rule. However, without the constraint of DNA chains, the nucleobases in bulk aqueous solution usually do not follow the W/C pairing rule anymore because of the strong competitive effect of water and the multi-interaction edges of nucleobases. The present work applied surfactant aggregates noncovalently functionalized by nucleotide to enhance the recognition between nucleobases without DNA chains in aqueous solution, and it revealed the effects of their self-assembling ability and morphologies on the recognition. The cationic ammonium monomeric, dimeric, and trimeric surfactants DTAB, 12-3-12, and 12-3-12-3-12 were chosen. The surfactants with guanine-5'-monophosphate-disodium (GMP) form micelles, vesicles, and fingerprint-like and plate-like aggregates bearing the hydrogen-bonding sites of GMP, respectively. The binding parameters of these aggregates with adenine (A), uracil (U), guanine (G), and cytosine(C) indicate that the surfactants can promote W/C recognitions in aqueous solution when they form vesicles (GMP/DTAB) or plate-like aggregates (GMP/12-3-12) with proper molecular packing compactness, which not only provide hydrophobic environments but also shield non-W/C recognition edges. However, the GMP/12-3-12 micelles with loose molecular packing, the GMP/12-3-12 fingerprint-like aggregates where the hydrogen bond sites of GMP are occupied by itself, and the GMP/12-3-12-3-12 vesicles with too strong self-assembling ability cannot promote W/C recognition. This work provides insight into how to design self-assemblies with the performance of enhanced molecule recognition.