Hydrogen Bonding

Methods enabling the broad diversification of C(sp3)-H bonds from a common intermediate are especially valuable in chemical synthesis. Herein, we report a site-selective (N-phenyltetrazole)thiolation of aliphatic and (hetero)benzylic C(sp3)-H bonds using a commercially available disulfide to access N-phenyltetrazole thioethers. The thioether products are readily elaborated in diverse fragment couplings for C-C, C-O, or C-N construction. The C-H functionalization proceeds via a radical-chain pathway involving hydrogen atom transfer by the electron-poor N-phenyltetrazolethiyl radical...

The poor bulk-phase and interphase stability, attributable to adverse internal stress, impede the cycling performance of silicon microparticles (μSi) anodes and its commercial application for high-energy-density lithium-ion batteries. In this work, we propose a groundbreaking gradient-hierarchically ordered conductive (GHOC) network structure, ingeniously engineered to enhance the stability of both bulk-phase and the solid electrolyte interphase (SEI) configurations of μSi. Within the GHOC network architecture, two-dimensional transition metal carbides (Ti3 C2 Tx ) acts as a conductive "brick", establishing a highly conductive inner layer on μSi, while the porous outer layer, composed of one-dimensional Tempo-oxidized cellulose nanofibers (TCNF) and polyacrylic acid (PAA) macromolecule, functions akin to structural "rebar" and "concrete", effectively preserves the tightly interconnected conductive framework though multiple bonding mechanisms, including covalent and hydrogen bonds...

The ternary germanide Mg5.57 Ni16 Ge7.43 (cubic, space group Fm\overline{3}m, cF116) belongs to the structural family based on the Th6 Mn23 -type. The Ge1 and Ge2 atoms fully occupy the 4a (m\overline{3}m symmetry) and 24d (m.mm) sites, respectively. The Ni1 and Ni2 atoms both fully occupy two 32f sites (.3m symmetry). The Mg/Ge statistical mixture occupies the 24e site with 4m.m symmetry. The structure of the title compound contains a three-core-shell cluster. At (0,0,0), there is a Ge1 atom which is surrounded by eight Ni atoms at the vertices of a cube and consequently six Mg atoms at the vertices of an octahedron...

CONTEXT: A complex supramolecular process involving electrostatic and dispersion interactions and asphaltene aggregation is associated with detrimental petroleum deposition and scaling that pose challenges to petroleum recovery, transportation, and upgrading. The homodimers of seven heterocyclic model compounds, representative of moieties commonly found in asphaltene structures, were studied: pyridine, thiophene, furan, isoquinoline, pyrazine, thiazole, and 1,3-oxazole. The contributions of hydrogen bonding involving water bridges spanning between dimers and π-π stacking to the total interaction energy were calculated and analyzed...

A novel class of crystalline porous materials has been developed utilizing multilevel dynamic linkages, including covalent B-O, dative B←N and hydrogen bonds. Typically, boronic acids undergo in situ condensation to afford B3O3-based units, which further extend to molecular complexes or chains via B←N bonds. The obtained superstructures are subsequently interconnected via hydrogen bonds and π-π interactions, producing crystalline porous organic frameworks (CPOFs). The CPOFs display excellent solution processability, allowing dissolution and subsequent crystallization to their original structures, independent of recrystallization conditions, possibly due to the diverse bond energies of the involved interactions...

Hydrogen production via the photocatalytic water splitting reaction on semiconductors presents a promising avenue to directly achieve solar energy conversion and storage. Bismuth-based semiconductors with layered structures, a hierarchical arrangement of components stacked in the form of two-dimensional extended layers where the atoms within each layer are typically strongly bonded, while the interactions between the layers are relatively weak, have emerged as an important series of photocatalyst candidates...

The novel Schiff's base (CS6) was synthesized and confirmed by various studies. The B3LYP/cc-pVDZ basis set was used for theoretical study and the results indicated that both the theoretical and experimental studies correlated well. The interaction energy of CS6-water complex calculated by using the local energy decomposition analysis was found to be -7.28 kcal/mol. The TD-TFT method was used for the calculation of electronic absorption spectrum. This study confirmed that the observed wavelength and the simulated wavelength in the electronic spectra were almost similar...

It is of great importance to understand the intrinsic relationship between phototautomerization and photoelectric properties for the exploration of novel organic materials. Here, in order to chemically control the protonation process, the aminated isoxazole derivative (2,2'-(isoxazolo[5,4- d ]isoxazole-3,6-diyl)dibenzenaminium, DP-DA-DPIxz) with -N═ as the proton acceptor was designed to achieve the twisted intramolecular charge transfer (TICT) state which was triggered by an excited-state intramolecular proton transfer (ESIPT) process...

There is growing acknowledgment that the properties of the electrochemical interfaces play an increasingly pivotal role in improving the performance of the hydrogen evolution reaction (HER). Here, we present, for the first time, direct dynamic spectral evidence illustrating the impact of the interaction between interfacial water molecules and adsorbed hydroxyl species (OHad ) on the HER properties of Ni(OH)2 using Au/core-Ni(OH)2 /shell nanoparticle-enhanced Raman spectroscopy. Notably, our findings highlight that the interaction between OHad and interfacial water molecules promotes the formation of weakly hydrogen-bonded water, fostering an environment conducive to improving the HER performance...

In this paper, a carbon dot hydrogel composite (CDs-Hy) capable of efficiently removing Pb(II) was prepared by hydrogen bonding self-assembly in combination with carbon dots and a hydrogel. CDs-Hy was characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS), and the effect of the adsorption conditions on the adsorption efficiency of CDs-Hy was studied. The results of the study showed that the incorporation of carbon dots, on the one hand, significantly increased the adsorption capacity of the material...

Carbon dots (CDs) are novel nanomaterials with dimensions less than 10 nm that have attracted much attention due to their outstanding optical properties. However, the development of solid-state fluorescence and afterglow methods has been relatively slow, although the properties of these materials under liquid conditions have been extensively studied. In recent years, embedding CDs in a matrix has been shown to prevent aggregation quenching and inhibit nonradiative transitions, thus realizing solid-state fluorescence and afterglow, which has greatly broadened the research and application areas of CDs...

A trinuclear linear mixed-valence centrosymmetric cobalt(iii)-cobalt(ii)-cobalt(iii) complex, [CoII {(μ-L)(μ-Hglu)CoIII (OH2 )}2 ](ClO4 )2 ·6H2 O has been synthesized during tetradentate N2 O2 donor 'Schiff base' ligand, H2 L { N , N '-bis(salicylidene)-1,3-diaminopropane} and glutaric acid (H2 glu) as anionic co-ligand. The complex has been characterized by spectroscopic measurements and its solid state structure has been determined by single crystal X-ray diffraction analysis. The supra-molecular assembly formed by the hydrogen bonding interactions in the solid state of the complex has been analysed using DFT calculations...

New amide conjugates 1-6 of hydroxycinnamic acids (HCA) and 5'-deoxy-5-fluorocytidine (5-dFCR), the prodrug of 5-fluorouracil (5-FU), were synthesized and tested in vitro against pancreatic cancer lines (PDAC). The compounds showed slightly higher efficacy against primary BxPC-3 cells (IC50 values of 14-45 μM) than against metastatic AsPC-1 (IC50 values of 37-133 μM), and similar to that of 5-FU for both PDAC lines. Compound 1, which has a para -(acetyloxy)coumaroyl substituent, was found to be the most potent (IC50 = 14 μM) with a selectivity index of approximately 7 to normal dermal fibroblasts (IC50 = 96 μM)...

In heterogeneous catalysis, surface defects are widely regarded as an effective means to enhance the catalytic performance of catalysts. In this study, the oxygen vacancy-rich Mg(1- X ) Zn X O solid solution support was successfully prepared by doping a small amount of Zn into MgO nanocrystals. Based on this support, Ru/Ba-Mg(1- X ) Zn X O catalyst for ammonia synthesis was prepared. Characterization using TEM, EPR, XPS, and DFT calculations confirmed the successful substitution of Zn atoms for Mg atoms leading to the formation of more oxygen vacancies (OVs)...

In this study, a novel series of pyridine-based thiadiazole derivatives ( NTD1-NTD5 ) were synthesized as prospective anti-inflammatory agents by combining substituted carboxylic acid derivatives of 5-substituted-2-amino-1,3,4-thiadiazole with nicotinoyl isothiocyanate in the presence of acetone. The newly synthesized compounds were characterized by FTIR, 1 H NMR, 13 C NMR, and mass spectrometry. First, the compounds underwent rigorous in vivo testing for acute toxicity and anti-inflammatory activity and the results revealed that three compounds- NTD1 , NTD2 , and NTD3 , displayed no acute toxicity and significant anti-inflammatory activity, surpassing the efficacy of the standard drug, diclofenac...

Chitin is a polysaccharide similar to cellulose that contains abundant hydrogen bonds. Expansin-like proteins disrupt hydrogen bond networks, causing cellulose to swell and accelerating its degradation. We examined the effects of pretreatment with two expansin-like proteins, CxEXL22 ( Arthrobotrys sp. CX1) and HcEXL (Hahella chejuensis ), on chitin depolymerisation and enzymatic degradation. The efficiency of chitin degradation increased more than two-fold after pretreatment with expansin-like proteins. Following pretreatment with expansin-like proteins, chitin had a lower crystallinity index, greater d-spacing and crystallite size, and weaker hydrogen bonds, and the loosened porous microfibrils were more exposed than in untreated chitin...

Autocatalysis has been well recognized to implicate in the emergence of life and is intrinsic to the biomolecular replication. Recently, an efficient template autocatalysis driven by solvent-free crystallization has been reported. Herein, we unveil the role of intermolecular hydrogen (H) bonds formed by amides in crystallization-driven template autocatalysis (CDTA), which involves the autocatalytic activity, template selectivity, and thermal responsiveness. We found that the thermal-induced cis-trans isomerization of amides possibly affects the H-bonding-mediated template ability of products for autocatalytic transformation...

ConspectusBuckminsterfullerene, C60 , was discovered through a prominent mass peak containing 60 atoms produced from laser vaporization of graphite, driven by Kroto's interest in understanding the formation mechanisms of carbon-containing molecules in space. Inspired by the geodesic dome-shaped architecture designed by Richard Buckminster Fuller, after whom the particle was named, C60 was found to have a football-shaped structure comprising 20 hexagons and 12 pentagons. It sparked worldwide interest in understanding this new carbon allotrope, resulting in the awarding of the Noble Prize in Chemistry to Smalley, Kroto, and Curl in 1996...

Wound healing is an obvious clinical concern that can be hindered by inadequate angiogenesis, inflammation, and chronic hypoxia. While exosomes derived from adipose tissue-derived stem cells have shown promise in accelerating healing by carrying therapeutic growth factors and microRNAs, intracellular cargo delivery is compromised in hypoxic tissues due to activated hypoxia-induced endocytic recycling. To address this challenge, we have developed a strategy to coat oxygen nanobubbles with exosomes and incorporate them into a polyvinyl alcohol/gelatin hybrid hydrogel...

More than 70% of the potash fertilizer globally is produced by the froth flotation process, in which 4-dodecylmorpholine (DMP) serves as a reverse flotation agent. As the potash fertilizer production rapidly rises, the increased DMP levels in discharged brine pose a threat to the production of high-value chemicals. In this paper, composite particles of basic magnesium sulfate@TiO2 (BMS@TiO2 ) were prepared using a simple and mild loading method. These particles were utilized for the adsorption and photocatalytic degradation of DMP in brine...