Reaction Mechanism About Isomerization of Resin Acids and Synthesis of Acrylopimaric Acid Based on DFT Calculation

Acrylopimaric acid is considered one of the possible substitutes for petroleum-based polymeric monomers, which is an important industrial product. Resin acids were isomerized to form levopimaric acid(4), which reacted with acrylic acid to synthesize isomers of acrylopimaric acid. Density functional theory calculation was used to investigate the reaction mechanisms with seven reaction paths in five different solutions. The values of ΔG were sorted from highest to lowest by levopimaric acid(4), neoabietic acid(3), palustric acid(2), and bietic acid(1). From the perspective of dynamics, the energy barrier in the isomerization of palustric acid(2) to levopimaric acid(4) was the lowest, whereas the highest energy barrier was the isomerization of neoabietic acid(3) to levopimaric acid(4) in the same solution. The addition reaction of levopimaric acid(4) and acrylic acid(5) to acrylopimaric acid c(8) was the optimal reaction path dynamically. However, ΔG of acrylopimaric acid c(8) was higher than that of acrylopimaric acid d(9). In general, the rates of isomerization reactions for rosin resin acids and addition reaction for acrylopimaric acid in water were higher than those in other solvents. HOMO-LUMO and ESP were analyzed for 8 kinds of molecules. For acylpyimaric acid, the non-planar six-memed ring and the C-C double bonds were easily attacked by nucleophile, while the non-planar six-memed ring and the carboxyl group are easily reacted with electrophiles. The highest electrostatic potential of the eight molecules is located at H of the carboxyl group, while the highest electrostatic potential is located at C-O double bond of the carboxyl group.

The Regulation of O2 Spin State and Direct Oxidation of CO at Room Temperature Using Triboelectric Plasma by Harvesting Mechanical Energy

Oxidation reactions play a critical role in processes involving energy utilization, chemical conversion, and pollutant elimination. However, due to its spin-forbidden nature, the reaction of molecular dioxygen (O2) with a substrate is difficult under mild conditions. Herein, we describe a system that activates O2 via the direct modulation of its spin state by mechanical energy-induced triboelectric corona plasma, enabling the CO oxidation reaction under normal temperature and pressure. Under optimized reaction conditions, the activity was 7.2 μmol h−1, and the energy consumption per mole CO was 4.2 MJ. The results of kinetic isotope effect, colorimetry, and density functional theory calculation studies demonstrated that electrons generated in the triboelectric plasma were directly injected into the antibonding orbital of O2 to form highly reactive negative ions O2−, which effectively promoted the rate-limiting step of O2 dissociation. The barrier of the reaction of O2− ions and CO molecular was 3.4 eV lower than that of O2 and CO molecular. This work provides an effective strategy for using renewable and green mechanical energy to realize spin-forbidden reactions of small molecules.

Incorporation of Different Metal Ion for Tuning Color and Enhancing Antioxidant Activity of Curcumin/Palygorskite Hybrid Materials

Curcumin is one of the dietary dyes extracted from turmeric and used for prevention and treatment of various illnesses. However, the low bioavailability and poor stability of curcumin limits its relevant applications. Therefore, different metal ions including Cu2+, Zn2+, Mg2+, Al3+, or Fe3+ were incorporated to tune the color, enhance the environmental stability and antioxidant activity of curcumin in the presence of palygorskite in this study. The as-prepared samples were studied using X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, Zeta potential, and transmission electron microscopy. In addition, the density functional theory calculation was also performed to explore the possible interaction among metal ions, curcumin and palygorskite. It was found that the color changing and stability enhancing were ascribed to the curcumin-metal ions coordination as well as chemical interactions between curcumin-metal complex and palygorskite. Moreover, the as-prepared composites showed more excellent color, thermal stability, antioxidant activity, and fluorescence properties than that of the curcumin/palygorskite composites due to the presence of metal ions. The finding of this investigation may contribute to developing the multifunctional composites with different colors and good antioxidant activity for relevant applications based on curcumin and palygorskite.

Modular and stereoselective synthesis of tetrasubstituted vinyl sulfides leading to a library of AIEgens

Tetraarylethylenes exhibit intriguing photophysical properties and sulfur atom frequently play a vital role in organic photoelectric materials and biologically active compounds. Tetrasubstituted vinyl sulfides, which include both sulfur atom and tetrasubstituted alkenes motifs, might be a suitable skeleton for the discovery of the new material molecules and drug with unique functions and properties. However, how to modular synthesis these kinds of compounds is still challenging. Herein, a chemo- and stereo-selective Rh(II)-catalyzed [1,4]-acyl rearrangements of α-diazo carbonyl compounds and thioesters has been developed, providing a modular strategy to a library of 63 tetrasubstituted vinyl sulfides. In this transformation, the yield is up to 95% and the turnover number is up to 3650. The mechanism of this reaction is investigated by combining experiments and density functional theory calculation. Moreover, the “aggregation-induced emission” effect of tetrasubstituted vinyl sulfides were also investigated, which might useful in functional material, biological imaging and chemicalnsing via structural modification.

Addition Coupled Electron Transfer (ACET) and Addition Coupled Electron Coupled Proton Transfer (ACPCET)

The new types of elementary reaction in which a nucleophilic addition (A) to quinones is coupled with electron transfer (ET) and even further proton transfer (PT) are suggested herein by density functional theory calculation, which are called Addition Coupled Electron Transfer (ACET) or Addition Coupled Electron Coupled Proton Transfer (ACPCET). With a [2.2]paracyclophane-derived biquinone (1) as the substrate, the nature of nucleophilic addition onto its sp2 carbons exhibits a change from stepwise A-ET-PT to ACET-PT and further to ACPCET, in parallel with the decreased nucleophilicity of the attacking reagent. In addition, we further proposed six possible potential energy surfaces and the coupling modes between A, ET and PT, in which three have been found in this work. Quasi-classical trajectory shows that the ACET and PT event can also be dynamically concerted even for an ACET-PT mechanism.

Addition Coupled Electron Transfer (ACET) and Addition Coupled Electron Coupled Proton Transfer (ACPCET)

The new types of elementary reaction in which a nucleophilic addition (A) to quinones is coupled with electron transfer (ET) and even further proton transfer (PT) are suggested herein by density functional theory calculation, which are called Addition Coupled Electron Transfer (ACET) or Addition Coupled Electron Coupled Proton Transfer (ACPCET). With a [2.2]paracyclophane-derived biquinone (1) as the substrate, the nature of nucleophilic addition onto its sp2 carbons exhibits a change from stepwise A-ET-PT to ACET-PT and further to ACPCET, in parallel with the decreased nucleophilicity of the attacking reagent. In addition, we further proposed six possible potential energy surfaces and the coupling modes between A, ET and PT, in which three have been found in this work. Quasi-classical trajectory shows that the ACET and PT event can also be dynamically concerted even for an ACET-PT mechanism.

Structure of PtRu/Ru(0001) and AgPd/Pd(111) surface alloys: A kinetic Monte Carlo study

Bimetallic surfaces allow tailoring their catalytic activity by modifying their composition and/or structure. However, under operating conditions, catalytically active bimetallic structures are often not stable and change their morphology which might reduce their functionality. Still, catalytically active structures do not necessarily need to be thermodynamically stable and might also be kinetically stabilized. Here we report kinetic Monte Carlo simulations based on density functional theory calculation to address the meta-stability of surface alloy systems. As structural changes can typically only occur via vacancy diffusion in the surface, we first determine the vacancy diffusion barrier as a function of their bimetallic environment. By determining the temporal evolution of the bimetallic surface alloys as a function of temperature, we analyze the factors underlying the stability and structure of the bimetallic surface alloys.

A First-Principles Study on Titanium-Decorated Adsorbent for Hydrogen Storage

Based on density functional theory calculation, we screened suitable Ti-decorated carbon-based hydrogen adsorbent structures. The adsorption characteristics and adsorption mechanism of hydrogen molecules on the adsorbent were also discussed. The results indicated that Ti-decorated double vacancy (2 × 2) graphene cells seem to be an efficient material for hydrogen storage. Ti atoms are stably embedded on the double vacancy sites above and below the graphene plane, with binding energy higher than the cohesive energy of Ti. For both sides of Ti-decorated double vacancy graphene, up to six H2 molecules can be adsorbed around each Ti atom when the adsorption energy per molecule is −0.25 eV/H2, and the gravimetric hydrogen storage capacity is 6.67 wt.%. Partial density of states (PDOS) analysis showed that orbital hybridization occurs between the d orbital of the adsorbed Ti atom and p orbital of C atom in the graphene layer, while the bonding process is not obvious during hydrogen adsorption. We expect that Ti-decorated double vacancy graphene can be considered as a potential hydrogen storage medium under ambient conditions.