Exploring the potential of iron-based metal-organic frameworks as peroxidase nanozymes for glucose detection with various secondary building units.

Finding materials in biosensing that balance enzyme-like reactivity, stability, and affordability is essential for the future. Because of their unique peroxidase properties, including variable pore size, surface area, and Lewis acid active sites, iron-based metal-organic frameworks (MOFs) have evolved as viable possibilities. In this study, we constructed a Fe-MOF and tested its peroxidase-like activity and responsiveness toward H2O2 colorimetric techniques. Using encapsulation, we incorporated glucose oxidase into the ZIF-90 PVP MOF and conducted a sequential reaction with the Fe-MOF to detect glucose. The results showed better peroxidase catalytic activity of the MIL-88B(Fe) (1,4-NDC) MOF and similar secondary building unit (SBU) Fe-MOFs were studied in other peroxidase nanozyme studies. When combined with an enzyme-encapsulating ZIF-90 PVP MOF, they could be sequentially employed for glucose detection purposes. This study highlights the potential of nanozymes as an alternative to natural enzymes, with promising applications in biosensing and beyond.

Synergistic Functionality of Dopants and Defects in Co-Phthalocyanine/B-CN Z-Scheme Photocatalysts for Promoting Photocatalytic CO2 Reduction Reactions.

The realization of solar-light-driven CO2  reduction reactions (CO2 RR) is essential for the commercial development of renewable energy modules and the reduction of global CO2 emissions. Combining experimental measurements and theoretical calculations, to introduce boron dopants and nitrogen defects in graphitic carbon nitride (g-C3 N4 ), sodium borohydride is simply calcined with the mixture of g-C3 N4 (CN), followed by the introduction of ultrathin Co phthalocyanine through phosphate groups. By strengthening H-bonding interactions, the resultant CoPc/P-BNDCN nanocomposite showed excellent photocatalytic CO2 reduction activity, releasing 197.76 and 130.32 µmol h-1  g-1 CO and CH4 , respectively, and conveying an unprecedented 10-26-time improvement under visible-light irradiation. The substantial tuning is performed towards the conduction and valance band locations by B-dopants and N-defects to modulate the band structure for significantly accelerated CO2 RR. Through the use of ultrathin metal phthalocyanine assemblies that have a lot of single-atom sites, this work demonstrates a sustainable approach for achieving effective photocatalytic CO2 activation. More importantly, the excellent photoactivity is attributed to the fast charge separation via Z-scheme transfer mechanism formed by the universally facile strategy of dimension-matched ultrathin (≈4 nm) metal phthalocyanine-assisted nanocomposites.

Regulating the Coordination Environment of Single-Atom Catalysts Anchored on Thiophene Linked Porphyrin for an Efficient Nitrogen Reduction Reaction.

The electrochemical nitrogen reduction reaction (NRR) offers a promising strategy to resolve high energy consumption in the nitrogen industry. Recently, the regulation of the electronic structure of single-atom catalysts (SACs) by adjusting their coordination environment has emerged as a rather promising strategy to further enhance their electrocatalytic activity. Herein, we design novel SACs supported by thiophene-linked porphyrin (TM-N4/TP and TM-N4-xBx/TP, where TM = Sc to Au) as potential NRR catalysts using density functional theory calculations. Among these catalysts, TM-N4/TP (TM = Ti, Nb, Mo, Ta, W, and Re) and TM-N4/TP with a water bilayer (TM = Nb, Mo, W, and Re) show excellent activity (low limiting potential) but low selectivity. Encouragingly, we find that Mo-N3B/TP, Mo-N2B2-2/TP, W-N3B/TP, W-N2B2-2/TP, Re-N3B/TP, Re-N2B2-2/TP, and Re-N2B2-1/TP serve as the most efficient NRR electrocatalysts, as they present stability, superior activity, better selectivity with low limiting potentials (-0.18 ∼ -0.90 V), and high Faradaic efficiencies (>99.80%). Based on microkinetic modeling, kinetic analysis of the NRR is performed and shows that the Re-N2B2-1/TP catalyst is more efficient for NH3 formation. Additionally, multiple-level descriptors provide insight into the origin of NRR activity and enable fast prescreening among numerous candidates. This work provides a new perspective to design highly efficient catalysts for the NRR under ambient conditions.

Hydrogen-Bond-Donor-Directed Switching of Enantioselectivity in the Vinylogous Aldol-Cyclization Cascade Reaction of Prostereogenic 3-Alkylidene Oxindoles with Isatins and o-Quinones.

In this study, we reported a hydrogen-bond-donor-directed enantiodivergent vinylogous aldol-cyclization cascade reaction of 3-alkylidene oxindoles with isatins and o-quinones. Both enantiomers can be prepared by thiourea or squaramide cinchona alkaloid bifunctional organocatalysts with the same quinine scaffold. Kinetic study data provided the possible reaction mechanism for the vinylogous aldol-cyclization cascade reaction. The DFT calculation data showed the geometry of the generated dienolates from pronucleophiles dominated the observed switch of enantioselectivity.

Enantioselective Organocatalytic Three-Component Vinylogous Michael/Aldol Tandem Reaction among 3-Alkylidene oxindoles, Methyleneindolinones, and Aldehydes.

We reported a one-pot enantioselective three-component vinylogous Michael/aldol tandem reaction of prochiral 3-alkylidene oxindoles with methyleneindolinones and aldehydes using bifunctional organocatalysts. A variety of enantioenriched 3,3-disubstituted oxindoles 3 and spirolactones 4 were generated in moderate yields (up to 78%) with high stereoselectivities (up to >20:1 dr, >99% ee). Intriguingly, we observed that the aldol reaction with paraformaldehyde generates 3,3-disubstituted oxindoles 3 bearing a hydroxymethyl group, while the reaction with aliphatic aldehydes generates spirolactones 4.

Mechanistic Insight into the Synergetic Interaction of Ammonia Borane and Water on ZIF-67-Derived Co@Porous Carbon for Controlled Generation of Dihydrogen.

Regarding dihydrogen as a clean and renewable energy source, ammonia borane (NH3BH3, AB) was considered as a chemical H2-storage and H2-delivery material due to its high storage capacity of dihydrogen (19.6 wt %) and stability at room temperature. To advance the development of efficient and recyclable catalysts for hydrolytic dehydrogenation of AB with parallel insight into the reaction mechanism, herein, ZIF-67-derived fcc-Co@porous carbon nano/microparticles (cZIF-67_nm/cZIF-67_µm) were explored to promote catalytic dehydrogenation of AB and generation of H2(g). According to kinetic and computational studies, zero-order dependence on the concentration of AB, first-order dependence on the concentration of cZIF-67_nm (or cZIF-67_µm), and a kinetic isotope effect value of 2.45 (or 2.64) for H2O/D2O identify the Co-catalyzed cleavage of the H-OH bond, instead of the H-BH2NH3 bond, as the rate-determining step in the hydrolytic dehydrogenation of AB. Despite the absent evolution of H2(g) in the reaction of cZIF-67 and AB in the organic solvents (i.e., THF or CH3OH) or in the reaction of cZIF-67 and water, Co-mediated activation of AB and formation of a Co-H intermediate were evidenced by theoretical calculation, infrared spectroscopy in combination with an isotope-labeling experiment, and reactivity study toward CO2-to-formate/H2O-to-H2 conversion. Moreover, the computational study discovers a synergistic interaction between AB and the water cluster (H2O)9 on fcc-Co, which shifts the splitting of water into an exergonic process and lowers the thermodynamic barrier for the generation and desorption of H2(g) from the Co-H intermediates. With the kinetic and mechanistic study of ZIF-67-derived Co@porous carbon for catalytic hydrolysis of AB, the spatiotemporal control on the generation of H2(g) for the treatment of inflammatory diseases will be further investigated in the near future.

Unraveling Catalytic Mechanisms for CO Oxidation on Boron-Doped Fullerene: A Computational Study.

By means of spin-polarized density functional theory (DFT) computations, we unravel the reaction mechanisms of catalytic CO oxidation on B-doped fullerene. It is shown that O2 species favors to be chemically adsorbed via side-on configuration at the hex-C-B site with an adsorption energy of -1.07 eV. Two traditional pathways, Eley-Rideal (ER) and Langmuir-Hinshelwood (LH) mechanisms, are considered for the CO oxidation starting from O2 adsorption. CO species is able to bind at the B-top site of the B-doped fullerene with an adsorption energy of -0.78 eV. Therefore, CO oxidation that occurs starting from CO adsorption is also taken into account. Second reaction of CO oxidation occurs by the reaction of CO + O → CO2 with a very high energy barrier of 1.56 eV. A trimolecular Eley-Rideal (TER) pathway is proposed to avoid leaving the O atom on the B-doped fullerene after the first CO oxidation. These predictions manifest that boron-doped fullerene is a potential metal-free catalyst for CO oxidation.

Synthesis, density functional theory (DFT) studies and urease inhibition activity of chiral benzimidazoles.

A variety of benzimidazole by the heterocyclization of orthophenylenediamine were synthesized in 69-86% yields. The synthesized compounds 3a-f and 6a-f were characterized and further investigated as jack bean urease inhibitors. Density functional theory (DFT) studies were performed utilizing the basis set B3LYP/6-31G (d, p) to acquire perception into their structural properties. Frontier molecular orbital (FMO) analysis of all compounds 3a-f and 6a-f was computed at the same level of theory to get a notion about their chemical reactivity and stability. The mapping of the molecular electrostatic potential (MEP) over the entire stabilized molecular geometry indicated the reactive centers. They exhibited urease inhibition activity with IC50 between 22 and 99 µM. Compounds containing withdrawing groups on the benzene ring (3d, 6d) were not showing significant urease inhibition. The value obtained for 3a, 3b, 3f had shown their significant urease inhibition for both theoretical and experimental. Notably, the compound having S-configuration (3a) (22.26 ± 6.2 µM) was good as compared to its R enantiomer 3f (31.42 ± 23.3 µM). Despite this, we elaborated the computational studies of the corresponding compounds, to highlight electronic effect which include HOMO, LUMO, Molecular electrostatic potential (MEP) and molecular docking.

Computational Study on the Mechanisms and Rate Constants for the O(3P,1D) + OCS Reactions.

The mechanisms and kinetics of O(3P,1D) + OCS(X1Σ+) reactions have been studied by the high-level G2M(CC2) and CCSD(T)/6-311+G(3df)//B3LYP/6-311+G(3df) methods in conjunction with the transition-state theory and variational Rice-Ramsperger-Kassel-Marcus theory calculations. The result shows that the triplet surface proceeds directly by abstraction and substitution channels to produce SO(3P) + CO(X1Σ+) and S(3P) + CO2(X1 Σg+) by passing the barriers of 7.6 and 9.1 kcal·mol-1 at the G2M(CC2)//B3LYP/6-311+G(3df) level, respectively, while two stable intermediates, LM1 (OSCO1) and LM2 (SC(O)O1), are formed barrierlessly from O(1D) + OCS(X1Σ+) in the singlet surface, which lie at -40.5 and -50.1 kcal·mol-1 relative to O(3P) + OCS(X1Σ+) reactants and decompose to CO(X1Σ+) + SO(a1Δ) and S(1D) + CO2(X1Σg+). LM1 and LM2 may also be produced by singlet-triplet surface crossings via MSX1 and MSX2; the predicted total rate constant for the O(3P) + OCS(X1Σ+) reaction including the crossings, 9.2 × 10-11 exp(-5.18 kcal·mol-1/RT) cm3 molecule-1 s-1, is in good agreement with available experimental data. The branching ratio of the CO2 product channel, 0.22-0.32, between 1200 and 1600 K, is also in excellent agreement with the value of 0.2-0.3 measured by Isshiki et al. (J. Phys. Chem. A. 2003, 107, 2464).

Single Pt atom supported on penta-graphene as an efficient catalyst for CO oxidation.

Single-atom catalysts (SACs) have gained special attention due to their unique performances in CO oxidation. Herein, a single Pt atom supported on penta-graphene (Pt/PG) was explored as a SAC towards CO oxidation by applying spin-polarized first-principles calculations. The possible mechanisms for CO oxidation by O2 on Pt/PG, including two traditional mechanisms, Eley-Rideal (ER) and Langmuir-Hinshelwood (LH), and a new tri-molecular Eley-Rideal (TER) mechanism, are illustrated. Our computations revealed that the direct ER pathway (O2 + CO → O + CO2) and TER pathway (2CO + O2→ OCO-OCO → 2CO2) with activation energies of 0.11-0.20 eV and 0.35 eV for the rate-limiting step, respectively, were more preferable than the LH pathway (0.45 eV). The TER pathway was proposed as the most favored pathway since the adsorption of CO was much stronger than the adsorption of O2, allowing for the ER pathway to be restrained. This finding demonstrated that Pt/PG as a single-atom catalyst exhibited an excellent catalytic activity toward CO oxidation and provided a new strategy for the design of single-atom catalysts based on penta-graphene.

A simple approach to achieve a metastable metal oxide derived from carbonized metal-organic gels.

A strategy for fabricating zirconium oxide doped nanoporous carbons derived from metal-organic gels (MOGs) is reported. For the first time, the achievement of metastable ZrO2-NPCs is demonstrated. The direct pyrolysis of MOGs provided new perspective in developing metal oxide-doped NPCs and circumvented the shortcomings of existing methods in synthesizing metastable ZrO2 doped NPCs.

Catalytic CO oxidation on B-doped and BN co-doped penta-graphene: a computational study.

The catalytic reaction of carbon monoxide oxidation on boron-doped and boron-nitrogen co-doped penta-graphene materials has been systematically studied by utilizing spin-polarized density functional theory (DFT) calculations. Various pathways including the Eley-Rideal (ER), Langmuir-Hinshelwood (LH), and tri-molecular Eley-Rideal (TER) mechanisms were considered in which the TER mechanism is a newly proposed reaction mechanism for CO oxidation. According to the calculation results, the ER, LH and TER mechanisms of CO oxidation can occur and compete with each other because of the related small overall reaction energy barriers (0.11-0.35 eV for the ER mechanism, 0.16-0.17 eV for the LH mechanism, and no activation energy for the TER mechanism). Our study helps to understand the various pathways for the CO oxidation process and suggests that both B-doped and BN co-doped penta-graphene sheets may serve as effective metal-free catalysts for low-temperature CO oxidation.

Monitoring the Effect of Different Metal Centers in Metal-Organic Frameworks and Their Adsorption of Aromatic Molecules using Experimental and Simulation Studies.

In this study, the adsorption behavior of different metal centers in analogous M-1,4-NDC frameworks (1,4-NDC=1,4-naphthalenedicarboxylate) towards guest molecules through simulation studies and experimental studies is reported. Simulation studies showed that the adsorption behavior of analogous M-1,4-NDC is affected by the atomic radius of the metal center, which was found to be in agreement with the experimental studies.

Nitrogen-doped C60 as a robust catalyst for CO oxidation.

The O2 activation and CO oxidation on nitrogen-doped C59 N fullerene are investigated using first-principles calculations. The calculations indicate that the C59 N fullerene is able to activate O2 molecules resulting in the formation of superoxide species ( O2-) both kinetically and thermodynamically. The active superoxide can further react with CO to form CO2 via the Eley-Rideal mechanism by passing a stepwise reaction barrier of only 0.20 eV. Ab initio molecular dynamics (AIMD) simulation is carried out to evidence the feasibility of the Eley-Rideal mechanism. In addition, the second CO oxidation takes place with the remaining atomic O without any activation energy barrier. The full catalytic reaction cycles can occur energetically favorable and suggest a two-step Eley-Rideal mechanism for CO oxidation with O2 catalyzed by the C59 N fullerene. The catalytic properties of high percentage nitrogen-doped fullerene (C48 N12 ) is also examined. This work contributes to designing higher effective carbon-based materials catalysts by a dependable theoretical insight into the catalytic properties of the nitrogen-doped fullerene. © 2017 Wiley Periodicals, Inc.

Nitrogen-doped porous carbon material derived from metal-organic gel for small biomolecular sensing.

A simple preparation method of N-doped PCM via direct carbonization of nitrogen containing metal-organic gel was demonstrated. The resultant N-PCM, with high surface area, mesoporosity, and high UV absorption ability, was used as a matrix to assist small-biomolecule sensing in laser desorption/ionization mass spectrometry.

Investigation of the self-assembly of CS and PCL copolymers with different molecular weights in water solution by coarse-grained molecular dynamics simulation.

Coarse-grained molecular dynamics (CGMD) simulation was employed to investigate how stable chondroitin sulfate-graft-polycaprolactone (CS-PCL, CP) copolymers self-assemble into micelles in an aqueous environment. Three types of CP containing low (2.4%), medium (6.3%), and high (18.7%) PCL contents (denoted L-CP, M-CP, and H-CP, respectively) in which PCL molecules consisting of 63 monomers were grafted onto each CS molecule consisting of 120 monomers were considered. L-CP and M-CP were found to display spheroidal micellar structures, while H-CP presented a rod-like structure, in agreement with previous experimental observations. In addition, the entanglement of the PCL segment increased as its molecular weight was increased. The number density distribution profiles of PCL, CS, and water molecules indicated that there were a few water molecules between the PCL core of the micelle and the water solution surrounding the micelle (in the micelle layer immediately above the core), and the number density of water in the CP micelle increased as the PCL content decreased. Using the radius of gyration, the three-dimensional conformations of the micelles were explored. When the number of CP chains was 3, H-CP adopted a long nanorod form, whereas L-CP and M-CP were roughly nanospherical. When the number of CP chains was increased beyond 3, however, the structure of L-CP changed from a nanosphere to a nanodisk. Finally, the slope of the mean square displacement profile was greatest when the molecular weight of the PCL segment was lowest, indicating that the mobilities of the CS and PCL segments are highest in L-CP. The self-diffusion coefficients of the CS and PCL segments decreased as the number of PCL segments grafted increased. Graphical abstract Morphologies of H-CP micelle.

Nitrogen-doped carbon nanotube as a potential metal-free catalyst for CO oxidation.

We elucidate the possibility of nitrogen-doped carbon nanotube as a robust catalyst for CO oxidation. We have performed first-principles calculations considering the spin-polarization effect to demonstrate the reaction of CO oxidation catalyzed by the nitrogen-doped carbon nanotube. The calculations show that O2 species can be partially reduced with charge transfer from the nitrogen-doped carbon nanotube and directly chemisorbed on the C-N sites of the nitrogen-doped carbon nanotube. The partially reduced O2 species at the C-N sites can further directly react with a CO molecule via the Eley-Rideal mechanism with the barriers of 0.45-0.58 eV for the different diameter of nanotube. Ab initio molecular dynamics (AIMD) simulations were performed and showed that the oxidation of CO occurs by the Eley-Rideal mechanism. The relationship between the curvature and reactivity of the nitrogen doped carbon nanotube was also unraveled. It appears that the barrier height of the rate-limiting step depends on the curvature of the nitrogen-doped carbon nanotube in the trend of (3,3)-NCNT < (4,4)-NCNT < (5,5)-NCNT (decreases with increased curvature). Using this relationship, we can predict the barriers for other N-doped carbon nanotubes with different tube diameters. Our results reveal that the nitrogen doped carbon nanomaterials can be a good, low-cost, and metal-free catalyst for CO oxidation.

The CO oxidation mechanism on the W(111) surface and the W helical nanowire investigated by the density functional theory calculation.

Two CO oxidation reactions (CO + O2 → CO2 + O and CO + O → CO2) were considered in the Eley-Rideal (ER) reaction mechanism. These oxidation processes on the W(111) surface and the W helical nanowire were investigated by the density functional theory (DFT) calculation. The stable adsorption sites of O2 and O as well as their adsorption energies were obtained first. In order to understand the catalytic properties of the W helical nanowire, the Fukui function and local density of state (LDOS) profiles were determined. The nudged elastic band (NEB) method was applied to locate transition states and minimum energy pathways (MEPs) of CO oxidation processes on the W helical nanowire and on the W(111) surface. In this study, we have demonstrated that the catalytic ability of the W helical nanowire is superior to that of the W(111) surface for CO oxidation.

To Transfer or Not to Transfer? Development of a Dinitrosyl Iron Complex as a Nitroxyl Donor for the Nitroxylation of an Fe(III) -Porphyrin Center.

A positive myocardial inotropic effect achieved using HNO/NO(-) , compared with NO⋅, triggered attempts to explore novel nitroxyl donors for use in clinical applications in vascular and myocardial pharmacology. To develop M-NO complexes for nitroxyl chemistry and biology, modulation of direct nitroxyl-transfer reactivity of dinitrosyl iron complexes (DNICs) is investigated in this study using a Fe(III) -porphyrin complex and proteins as a specific probe. Stable dinuclear {Fe(NO)2 }(9) DNIC [Fe(µ-(Me) Pyr)(NO)2 ]2 was discovered as a potent nitroxyl donor for nitroxylation of Fe(III) -heme centers through an associative mechanism. Beyond the efficient nitroxyl transfer, transformation of DNICs into a chemical biology probe for nitroxyl and for pharmaceutical applications demands further efforts using in vitro/in vivo studies.

Promoting ethylene epoxidation on gold nanoclusters: self and CO induced O2 activation.

We have investigated the epoxidation of ethylene heterogeneously catalyzed by small gold nanoclusters based on density functional theory calculations. A promising trimolecular Langmuir-Hinshelwood mechanism via co-adsorbed ethylene- and CO-assisted reaction is addressed which provides significant insights into the fundamental catalytic mechanism for ethylene oxidation on small Au nanoclusters. O2 activation is found to be a key step for accelerating ethylene oxidation. Especially, the coadsorbed neighboring CO is found to be more robust for promoting the activation of the O-O bond, resulting in the formation of epoxide and CO2 due to the barrierless process. The new CO-promoted oxidation mechanism has also been clarified by the ab initio MD simulations.