Poly-Phthalocyanine–Doped Graphene Oxide Nanosheet Conjugates for Electrocatalytic Oxidation of Drug Residues

Donor and acceptor phthalocyanine molecules were copolymerized and linked to graphene oxide nanosheets through amidation to yield electrocatalytic platforms on glassy carbon electrodes. The platforms were characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier-transform infrared (FTIR) spectroscopy, UV/Vis spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. The fabricated electrochemical catalytic surfaces were then evaluated toward electrocatalytic detection of ascorbic acid and tryptophan. These were characterized by a wide linear dynamic range and low limits of detection and quantification of 2.13 and 7.12 µM for ascorbic acid and 1.65 and 5.5 µM for tryptophan, respectively. The catalytic rate constant was 1.86 × 104 and 1.51 × 104 M−1s−1 for ascorbic acid and tryptophan, respectively. The Gibbs energy for catalytic reactions was −17.45 and −14.83 kJ mol−1 depicting a spontaneous reaction on the electrode surface. The sensor platform showed an impressive recovery when applied in real samples such as fresh cow milk, in the range 91.71–106.73% for both samples. The developed sensor therefore shows high potential for applicability for minute quantities of the analytes in real biological samples.

Common Kinetic Mechanism of Abasic Site Recognition by Structurally Different Apurinic/Apyrimidinic Endonucleases

Apurinic/apyrimidinic (AP) endonucleases Nfo (Escherichia coli) and APE1 (human) represent two conserved structural families of enzymes that cleave AP-site–containing DNA in base excision repair. Nfo and APE1 have completely different structures of the DNA-binding site, catalytically active amino acid residues and catalytic metal ions. Nonetheless, both enzymes induce DNA bending, AP-site backbone eversion into the active-site pocket and extrusion of the nucleotide located opposite the damage. All these stages may depend on local stability of the DNA duplex near the lesion. Here, we analysed effects of natural nucleotides located opposite a lesion on catalytic-complex formation stages and DNA cleavage efficacy. Several model DNA substrates that contain an AP-site analogue [F-site, i.e., (2R,3S)-2-(hydroxymethyl)-3-hydroxytetrahydrofuran] opposite G, A, T or C were used to monitor real-time conformational changes of the tested enzymes during interaction with DNA using changes in the enzymes’ intrinsic fluorescence intensity mainly caused by Trp fluorescence. The extrusion of the nucleotide located opposite F-site was recorded via fluorescence intensity changes of two base analogues. The catalytic rate constant slightly depended on the opposite-nucleotide nature. Thus, structurally different AP endonucleases Nfo and APE1 utilise a common strategy of damage recognition controlled by enzyme conformational transitions after initial DNA binding.

The Role of Redox Potential and Molecular Structure of Co(II)-Polypyridine Complexes on the Molecular Catalysis of CO2 Reduction

In this work, we report the electrochemical response of a family of Co(II) complexes, [CoII(L)3]2+ and [CoII(L’)2]2+ (L = 2,2’-bipyridine, 1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, and 4,7-diphenyl-1,10-phenanthroline; L’ = terpyridine and 4-chloro-terpyridine), in the presence and absence of CO2 in order to understand the role of the redox potential and molecular structure on the molecular catalysis of CO2 reduction. The tris chelate complexes exhibited three electron transfer processes [CoII(L)3]2+ ⇄ [CoIII(L)3]3+ + 1e−, [CoΙΙ(L)3]2++1e− ⇄ [CoΙ(L)3]+, and [CoΙ(L)3]+ + 2e- ⇄ [CoΙ(L)(L−)2]−. In the case of complexes with 1,10-phen and 2,2-bipy, the third redox process showed a coupled chemical reaction [CoΙ(L)(L−)2]− → [CoΙ(L−)2]− + L. For bis chelate complexes, three electron transfer processes associated with the redox couples [CoΙΙ(L)2]/[CoIII(L)2]3+, [CoΙΙ(L)2]2+/[CoΙ(L)2]+, and [CoΙ(L)2]+/[CoΙ(L)(L−)] were registered, including a coupled chemical reaction only for the complex containing the ligand 4-chloro-terpyridine. Foot to the wave analysis (FOWA) obtained from cyclic voltammetry experiments allowed us to calculate the catalytic rate constant (k) for the molecular catalysis of CO2 reduction. The complex [Co(3,4,7,8-tm-1,10-phen)3]2+ presented a high k value; moreover, the complex [Co(4-Cl-terpy)3]2+ did not show catalytic activity, indicating that the more negative redox potential and the absence of the coupled chemical reaction increased the molecular catalysis. Density functional theory (DFT) calculations for compounds and CO2 were obtained to rationalize the effect of electronic structure on the catalytic rate constant (k) of CO2 reduction.

Improving the Performance of ZnS Photocatalyst in Degrading Organic Pollutants by Constructing Composites with Ag2O

ZnS is a promising photocatalyst in water purification, whereas its low photon efficiency and poor visible-light response restrict its application. Constructing composites may help solve these problems. In this work, Ag2O was introduced to ZnS for the first time based on their energy band characteristics to form a novel ZnS/Ag2O composite photocatalyst. In the model reaction of degrading methylene blue, the as-designed catalyst exhibited high catalytic activity among a series of ZnS-based composite photocatalysts under similar conditions. The catalytic rate constant was up to 0.138 min−1, which is 27.4- and 15.6-times higher than those of ZnS and Ag2O. This composite degraded 92.4% methylene blue in 50 min, while the ratios were 31.9% and 68.8% for ZnS and Ag2O. Catalytic mechanism study based on photoluminescence and radical-scavenging experiments revealed that the enhanced photocatalytic activity was attributed to the composite structure of ZnS/Ag2O. The structure not only facilitated the separation and transmission of photogenerated carriers but also extended the light response range of the catalyst. The as-designed ZnS/Ag2O composite is promising in degrading organic pollutants in water.

Facile Use of Silver Nanoparticles-Loaded Alumina/Silica in Nanofluid Formulations for Enhanced Catalytic Performance toward 4-Nitrophenol Reduction

The introduction of toxic chemicals into the environment can result in water pollution leading to the degradation of biodiversity as well as human health. This study presents a new approach of using metal oxides (Al2O3 and SiO2) modified with a plasmonic metal (silver, Ag) nanoparticles (NPs)-based nanofluid (NF) formulation for environmental remediation purposes. Firstly, we prepared the Al2O3 and SiO2 NFs of different concentrations (0.2 to 2.0 weight %) by ultrasonic-assisted dispersion of Al2O3 and SiO2 NPs with water as the base fluid. The thermo-physical (viscosity, activation energy, and thermal conductivity), electrical (AC conductivity and dielectric constant) and physical (ultrasonic velocity, density, refractive index) and stability characteristics were comparatively evaluated. The Al2O3 and SiO2 NPs were then catalytically activated by loading silver NPs to obtain Al2O3/SiO2@Ag composite NPs. The catalytic reduction of 4-nitrophenol (4-NP) with Al2O3/SiO2@Ag based NFs was followed. The catalytic efficiency of Al2O3@Ag NF and SiO2@Ag NF, for the 4-NP catalysis, is compared. Based on the catalytic rate constant evaluation, the catalytic reduction efficiency for 4-NP is found to be superior for 2% weight Al2O3@Ag NF (92.9 × 10−3 s−1) as compared to the SiO2@Ag NF (29.3 × 10−3 s−1). Importantly, the enhanced catalytic efficiency of 2% weight Al2O3@Ag NF for 4-NP removal is much higher than other metal NPs based catalysts reported in the literature, signifying the importance of NF formulation-based catalysis.

Solely electrochemical synthesis of Prussian Blue based nanozymes ‘artificial peroxidase’

We report on fully electrochemical flow-through synthesis of Prussian Blue based nanozymes defeating peroxidase in terms of more than 200 times higher catalytic rate constant (kcat=6∙104 s-1). Being reagentless, reproducible,...

Selective Electrocatalytic CO2 Reduction to CO by an NHC-Based Organometallic Heme Analogue

Molecular first-row transition metal complexes for electrocatalytic CO₂ reduction mostly feature N-donor supporting ligands, iron porphyrins being among the most prominent catalysts. Introducing N-heterocyclic carbene (NHC) ligation has previously shown promising effects for some systems, yet the application of NHC iron complexes for electrochemical CO₂ reduction has so far remained unreported. Herein we show that the macrocyclic tetracarbene iron complex [LFe(NCMe)₂](OTf)₂ (<b>1</b>), which can be described as an organometallic heme analogue, mediates selective electrocatalytic CO₂-to-CO conversion with a faradaic efficiency of over 90% and a very high initial observed catalytic rate constant (<i>k</i>_obs) of 7,800 s⁻¹. Replacement of an axial MeCN ligand by CO significantly increases the catalyst stability and turnover number, while the rate of catalysis decreases only slightly (<i>k</i>_obs = 3,100 s⁻¹). Ferrous complexes with one or two axial CO ligands, [LFe(NCMe)(CO)](OTf)₂ (<b>1-CO</b>) and [LFe(CO)₂](OTf)₂ (<b>1-(CO)₂</b>), have been isolated and fully characterized. Based on linear sweep voltammogram (LSV) spectroelectro-IR (SEC-IR) studies for <b>1</b> and <b>1-CO</b>, both under N₂ and CO₂ atmosphere, a mechanistic scenario in anhydrous acetonitrile is proposed. It involves two molecules of CO₂ and results in CO and CO₃²⁻ formation, whereby the first CO₂ binds to the doubly reduced, pentacoordinated [LFe⁰(CO)] species. This work commences the exploration of the reductive chemistry by the widely tunable macrocyclic tetracarbene iron motif, which is topologically similar to hemes but electronically distinct as the strongly s-donating and redox inactive NHC scaffold leads to metal-centered reduction and population of the exposed d_z² orbital, in contrast to ligand-based orbitals in the analogous porphyrin systems.

Selective Electrocatalytic CO2 Reduction to CO by an NHC-Based Organometallic Heme Analogue

Molecular first-row transition metal complexes for electrocatalytic CO₂ reduction mostly feature N-donor supporting ligands, iron porphyrins being among the most prominent catalysts. Introducing N-heterocyclic carbene (NHC) ligation has previously shown promising effects for some systems, yet the application of NHC iron complexes for electrochemical CO₂ reduction has so far remained unreported. Herein we show that the macrocyclic tetracarbene iron complex [LFe(NCMe)₂](OTf)₂ (<b>1</b>), which can be described as an organometallic heme analogue, mediates selective electrocatalytic CO₂-to-CO conversion with a faradaic efficiency of over 90% and a very high initial observed catalytic rate constant (<i>k</i>_obs) of 7,800 s⁻¹. Replacement of an axial MeCN ligand by CO significantly increases the catalyst stability and turnover number, while the rate of catalysis decreases only slightly (<i>k</i>_obs = 3,100 s⁻¹). Ferrous complexes with one or two axial CO ligands, [LFe(NCMe)(CO)](OTf)₂ (<b>1-CO</b>) and [LFe(CO)₂](OTf)₂ (<b>1-(CO)₂</b>), have been isolated and fully characterized. Based on linear sweep voltammogram (LSV) spectroelectro-IR (SEC-IR) studies for <b>1</b> and <b>1-CO</b>, both under N₂ and CO₂ atmosphere, a mechanistic scenario in anhydrous acetonitrile is proposed. It involves two molecules of CO₂ and results in CO and CO₃²⁻ formation, whereby the first CO₂ binds to the doubly reduced, pentacoordinated [LFe⁰(CO)] species. This work commences the exploration of the reductive chemistry by the widely tunable macrocyclic tetracarbene iron motif, which is topologically similar to hemes but electronically distinct as the strongly s-donating and redox inactive NHC scaffold leads to metal-centered reduction and population of the exposed d_z² orbital, in contrast to ligand-based orbitals in the analogous porphyrin systems.

Modulation of conformational equilibrium by phosphorylation underlies the activation of deubiquitinase A

Deubiquitinases deconjugate ubiquitin modifications from target proteins and are involved in many cellular processes in eukaryotes. The functions of deubiquitinases are regulated by post-translational modifications, mainly phosphorylation and ubiquitination. Post-translational modifications can result in subtle changes in structural and dynamic properties, which are difficult to identify but functionally important. In this work, we used NMR spectroscopy to characterize the conformational properties of the human deubiquitinase A (DUBA), a negative regulator of type I interferon. DUBA activity is regulated by phosphorylation at a single serine residue, Ser-177. We found that the catalytic rate constant of DUBA is enhanced by phosphorylation. By comparing NMR and enzyme kinetics data among different forms of DUBA with low and high activities, we concluded that a two-state equilibrium that was present only in phosphorylated DUBA is important for DUBA activity. Our results highlight the importance of defining conformational dynamics in understanding the mechanism of DUBA activation.

Simultaneous Electrochemical Detection of Nitrite and Hydrogen Peroxide Based on 3D Au-rGO/FTO Obtained Through a One-Step Synthesis

In this paper, Au and reduced graphene oxide (rGO) were successively deposited on fluorine-doped SnO2 transparent conductive glass (FTO, 1 × 2 cm) via a facile and one-step electrodeposition method to form a clean interface and construct a three-dimensional network structure for the simultaneous detection of nitrite and hydrogen peroxide (H2O2). For nitrite detection, 3D Au-rGO/FTO displayed a sensitivity of 419 μA mM−1 cm−2 and a linear range from 0.0299 to 5.74 mM, while for the detection of H2O2, the sensitivity was 236 μA mM−1 cm−2 and a range from 0.179 to 10.5 mM. The combined results from scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, X-ray diffraction measurements (XRD) and electrochemical tests demonstrated that the properties of 3D Au-rGO/FTO were attributabled to the conductive network consisting of rGO and the good dispersion of Au nanoparticles (AuNPs) which can provide better electrochemical properties than other metal compounds, such as a larger electroactive surface area, more active sites, and a bigger catalytic rate constant.