Molecular dynamics study on thermal conductance between a nanotip and a substrate under vertical forces and horizontal sliding.

The heat transfer between a nanotip and its substrate is extremely complex but is a key factor in determining the measurement accuracy in tip-assisted nanomanufacturing and thermometry. In this work, the heat transfer from the nanotip to the substrate during sliding is investigated using molecular dynamics simulations. Interfacial interaction and bond formation are analyzed during the sliding process. The results show that the increase of vertical force would greatly improve the interface thermal conductance between the nanotip and the substrate. It is found that more bonds are formed and there are larger contact areas at the interface. In addition, we found that the thermal conductivity of the nanotip is another obstacle for heat transfer between the tip and substrate and it is greatly limited by the nanotip diameter near contact which is close to or even smaller than the phonon mean free path. Meanwhile, the dynamic formation and breakage of the covalent bonds during the sliding could gradually smoothen the tip apex and enhance the thermal transport at the interface. This work provides guidance for the thermal design of a nanotip-substrate system for nanoscale thermal transport measurements.

Bioinspired Manganese and Iron Complexes for Enantioselective Oxidation Reactions: Ligand Design, Catalytic Activity, and Beyond.

The development of efficient methods for the enantioselective oxidation of organic molecules continues to be an important goal in organic synthesis; in particular, the use of earth-abundant metal catalysts and environmentally friendly oxidants in catalytic asymmetric oxidation reactions has attracted significant interest over the last several decades. In nature, metalloenzymes catalyze a wide range of oxidation reactions by activating dioxygen under mild conditions. Inspired by selective and efficient oxidation reactions catalyzed by metalloenzymes, researchers have developed a number of synthetic model compounds that mimic the functionality of metalloenzymes. Among the reported biomimetic model compounds, tetradentate aminopyridine (N4) ligands have emerged as appealing frameworks because of their easy synthesis and facile diversification, and their complexes with metals such as Fe and Mn have proven to be versatile and powerful catalysts for a variety of (enantioselective) oxidation reactions. In this Account, we describe our efforts on the design of chiral N4 ligands and the use of their manganese and iron complexes in asymmetric oxidation reactions with H2O2 as the terminal oxidant, aiming to show general strategies for asymmetric oxidation reactions that can guide the rational design of ligands and relevant metal catalysts. In studies of manganese catalysts, the aryl-substituted (R,R)-mcp [mcp = N,N'-dimethyl-N,N'-bis(pyridine-2-ylmethyl)cyclohexane-1,2-diamine] manganese complexes exhibited high enantioselectivity in the asymmetric epoxidation (AE) of various olefins with H2O2 while requiring stoichiometric acetic acid as an additive for the activation of H2O2. To address this issue, we established bulkier N4 ligands for this catalytic system in which a catalytic amount of sulfuric acid enables the manganese-complex-catalyzed AE with improved stereocontrol and efficiency. In addition, this system was found to be active for the oxidative kinetic resolution of secondary alcohols. Further exploration of the structure-reactivity relationships has shown that aminobenzimidazole N4 ligands derived from l-proline, in which the conventional pyridine donors are replaced by benzimidazoles, act as promising ligands. These novel C1-symmetric manganese catalysts showed dramatically improved activities with unprecedented turnover numbers in the AE reactions. Notably, this class of manganese complexes can catalyze the oxidation of the C-H bonds of spirocyclic hydrocarbons and spiroazacyclic compounds in a highly enantioselective manner, providing ready access to chiral spirocyclic ß,ß'-diketones and spirocyclic alcohols. Remarkably, iron catalysts with these chiral N4 ligands are effective for AE of olefins, enabling rare examples of highly enantioselective syntheses of epoxides by the iron catalysts. Finally, mechanistic studies provide valuable insights into the roles of the carboxylic acid and sulfuric acid in the catalytic oxidation reactions. Thus, the results described in this Account have demonstrated the importance of tunability and compatibility of the ligands for the development of efficient oxidation catalysts with earth-abundant transition metals and environmentally benign oxidants, and we hope that our study will pave the way for the discovery of efficient oxidation catalysis.

Enantioselective synthesis of spirooxindole benzoquinolizines via organo-catalyzed cascade reactions.

A Michael-Mannich-hemiaminalization-dehydration cascade reaction was developed for the construction of spirooxindole benzoquinolizine derivatives. Additionally, spirooxindole benzoindolizidine was prepared conveniently through a ring-contracted rearrangement reaction from spirooxindole benzoquinolizine.

Squaramide-Catalyzed Synthesis of Enantioenriched Spirocyclic Oxindoles via Ketimine Intermediates with Multiple Active Sites.

A new method for the construction of five-membered spirocyclic oxindoles is based on a Michael-Mannich cascade reaction of a ketimine intermediated catalyzed by a bifunctional quinine-derived squaramide. The desired products were obtained in excellent yields (up to 94%) and stereoselectivities (up to >20:1 d.r., >99% ee). A scaled-up variant also proceeded smoothly showing that the one-pot reaction might find application in the synthesis of bioactive-compound libraries.

Design of Unconventional Polymers with Thermal Contraction Units for High-Performance Dental Adhesives.

The coefficient of thermal expansion (CTE) of adhesives is considered to be a vital parameter for dental restoration due to the oral temperature fluctuation induced by hot and cold drinks in daily life. Even more challenging, the adhesives need to bond various materials with different CTE values, and mismatched thermal expansion at the interface of two materials will produce thermal stress and cause cracking, leading to bond failure. In this study, we designed and synthesized a divinyl monomer containing a dibenzocyclooctadiene (DBCOD) unit, which was incorporated into a commercial adhesive, Single Bond Universal (SBU) to prepare low CTE adhesives. The CTE value of the adhesives can be adjusted low to 6.5 ppm/K, which is much lower than that of pure SBU. Mimicking the real applying conditions, the composite resin columns were bonded to the zirconia ceramics as a dental crown with our designed adhesives, and the shear bond strength test was carried out before and after 10 000 thermal cycles between 5 and 55 °C. The shear bond strength of pure SBU retains 44.7% of its original value after 10 000 thermal cycles, while those low CTE adhesives retain 74.6% and 61.9% of shear bond strength due to less deformation and interfacial stress during thermocycling. The newly designed adhesives provide a persistent way to enhance the shear bond strength and achieve a long lifetime in tooth restoration.

Ballistic Thermal Transport at Sub-10 nm Laser-Induced Hot Spots in GaN Crystal.

Ballistic thermal transport at nanoscale hotspots will greatly reduce the performance of a Gallium nitride (GaN) device when its characteristic length reaches the nanometer scale. In this work, the authors develop a tip-enhanced Raman thermometry approach to study ballistic thermal transport within the range of 10 nm in GaN, simultaneously achieving laser heating and measuring the local temperature. The Raman results show that the temperature increase from an Au-coated tip-focused hotspot up to two times higher (40 K) than that in a bare tip-focused region (20 K). To further investigate the possible mechanisms behind this temperature difference, the authors perform electromagnetic simulations to generate a highly focused heating field, and observe a highly localized optical penetration, within a range of 10 nm. The phonon mean free path (MFP) of the GaN substrate can thus be determined by comparing the numerical simulation results with the experimentally measured temperature increase which is in good agreement with the average MFP weighted by the mode-specific thermal conductivity, as calculated from first-principles simulations. The results demonstrate that the phonon MFP of a material can be rapidly predicted through a combination of experiments and simulations, which can find wide application in the thermal management of GaN-based electronics.

A DFT study on the C-H oxidation reactivity of Fe(iv)-oxo species with N4/N5 ligands derived from l-proline.

The hydroxylation of hexane by two FeIVO complexes bearing a pentadentate ligand (N5, Pro3Py) and a tetradentate ligand (N4, Pro2PyBn) derived from l-proline was studied by DFT calculations. Theoretical results predict that both FeIVO complexes hold triplet ground states. The hydrogen atom abstraction (HAA) processes by both FeIVO species proceed through a two-state reactivity, thus indicating that HAA occurs via a low-barrier quintet surface. Beyond the conventional rebound step, the dissociation path is also calculated and is found to potentially occur after HAA.

Catalytic Enantioselective Methylene C(sp3)-H Hydroxylation Using a Chiral Manganese Complex/Carboxylic Acid System.

Achieving direct C-H hydroxylation in a highly diastereo- and enantioselective manner is still a challenging goal. This reaction is mainly hindered by the potential for overoxidation of the generated alcohols as well as low stereoselectivity. Herein, we present an enantioselective benzylic C-H hydroxylation catalyzed by a manganese complex, H2O2, and a carboxylic acid in 2,2,2-trifluoroethanol. The benzylic alcohols were successfully furnished in excellent diastereoselectivities (up to >95:5) and enantioselectivities (up to 95% ee). As a highlight of this work, high diastereoselectivity of C-H hydroxylation could be achieved by tuning the amount of carboxylic acid additive.

Ligand regulation for manganese-catalyzed enantioselective epoxidation of olefins without acid.

A novel manganese catalyst bearing an l-proline-derived N4 ligand has been developed for enabling acid-free asymmetric epoxidation of olefins with tert-butyl hydroperoxide as the oxidant. A variety of olefins that are well-matched in size with the ligand pocket can be transformed to epoxides with excellent enantioselectivities. The smaller ligand pocket is also beneficial to the enantioselective epoxidation of simple olefins. Cryospray ionization mass spectrometry experiments reveal that a MnIV[double bond, length as m-dash]O species serves as an active epoxidizing species.

Manganese-Catalyzed Asymmetric Oxidation of Methylene C-H of Spirocyclic Oxindoles and Dihydroquinolinones with Hydrogen Peroxide.

A highly efficient strategy for the enantioselective oxidation of methylene C-H of spirocyclic oxindoles and dihydroquinolinones has been established, in which an earth-abundant manganese catalyst and hydrogen peroxide are used. Noteworthy, the manganese catalyst can be applied to the asymmetric hydroxylation of spirocyclic 2,3-dihydroquinolin-4-ones with 94-99% ee.

Efficient Aliphatic C-H Bond Oxidation Catalyzed by Manganese Complexes with Hydrogen Peroxide.

A tetradentate nitrogen ligand containing a benzimidazole ring and an electron-rich pyridine ring was developed, the resulting manganese complex exhibited good activity in the C-H oxidation of simple alkanes. In particular, cyclic aliphatic alkanes were transformed into ketones in very good yields (up to 89 %) by using environmentally benign H2 O2 as the terminal oxidant. This protocol was also applied successfully in benzylic C-H oxidation, giving the corresponding ketones with very good selectivities. In addition, tertiary C-H bond oxidation of complex molecules by the manganese complex showed potential utility for assembling alcohols with good selectivity in late-stage chemical synthesis.

CO2 as a C1 Source: B(C6F5)3-Catalyzed Cyclization of o-Phenylene-diamines To Construct Benzimidazoles in the Presence of Hydrosilane.

The catalytic construction of benzimidazoles using CO2 as a carbon source represents a facile and sustainable approach to obtaining these valuable compounds. Herein, we describe the B(C6F5)3-catalyzed synthesis of benzimidazoles via cyclization of o-phenylenediamines with CO2 and PhSiH3. This metal-free catalytic route achieves the desired products in high yield under convenient reaction conditions and is applicable to a broad substrate scope. A plausible mechanism for the reaction involving a frustrated Lewis pair pathway is proposed based on spectroscopic characterization (e.g., 13C NMR) of the reaction intermediates.