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The oxygen-insensitive nitroreductase from Enterobacter cloacae (NR) catalyzes two-electron reduction of nitroaromatics to the corresponding nitroso compounds and, subsequently, to hydroxylamine products. NR has an unusually broad substrate repertoire, which may be related to protein dynamics (flexibility) and/or a simple non-selective kinetic mechanism. To investigate the possible role of mechanism in the broad substrate repertoire of NR, the kinetics of oxidation of NR by para-nitrobenzoic acid (p-NBA) were investigated using stopped-flow techniques at 4 °C. The results revealed a hyperbolic dependence on the p-NBA concentration with a limiting rate of 1.90 ± 0.09 s(-1), indicating one-step binding before the flavin oxidation step. There is no evidence for a distinct binding step in which specificity might be enforced. The reduction of p-NBA is rate-limiting in steady-state turnover (1.7 ± 0.3 s(-1)). The pre-steady-state reduction kinetics of NR by NADH indicate that NADH reduces the enzyme with a rate constant of 700 ± 20 s(-1) and a dissociation constant of 0.51 ± 0.04 mM. Thus, we demonstrate simple transient kinetics in both the reductive and oxidative half-reactions that help to explain the broad substrate repertoire of NR. Finally, we tested the ability of NR to reduce para-hydroxylaminobenzoic acid, demonstrating that the corresponding amine does not accumulate to significant levels even under anaerobic conditions. Thus E. cloacae NR is not a good candidate for enzymatic production of aromatic amines.
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http://dx.doi.org/10.1074/jbc.M113.547117 | DOI Listing |
J Org Chem
December 2024
Jiangsu Key Laboratory for Chemistry of Low Dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huaian 223300, China.
An unprecedented Pd-catalyzed cascade alkyne insertion/Heck/C-H activation reaction of -iodophenyl alkenyl ethers and diarylacetylenes has been developed. Diversified tetracyclic-fused dihydroindeno[2,1-]chromenes bearing a quaternary center were constructed in an efficient, straightforward, and atom-economic way with good to excellent yields. The protocol features high bonding efficiency, operational simplicity, broad substrate scope, and easy scale-up.
View Article and Find Full Text PDFLangmuir
December 2024
Key Laboratory of Biomedical Information Engineering of Ministry of Education, School of Life Science and Technology, Xi'an Jiaotong University, Xi'an, Shaanxi 710049, China.
Magnetic fluorescent nanomaterials have broad application prospects as taggants in fields such as anticounterfeiting identification, suspicious object tracking, and potential fingerprint recognition in forensic medicine. It is a common method to synthesize magnetic fluorescent composite nanoparticles by preparing a shell on the surface of magnetic particles to load fluorescent materials. In this work, a magnetic fluorescence nanohybrid was synthesized by in situ encapsulation of carbon quantum dots (CQDs) during the preparation of a SiO shell on the surface of FeO nanoparticles.
View Article and Find Full Text PDFAm J Hum Genet
December 2024
Department of Genetics, CHU Sainte-Justine, Montréal, QC, Canada. Electronic address:
E3 ubiquitin ligases have been linked to developmental diseases including autism, Angelman syndrome (UBE3A), and Johanson-Blizzard syndrome (JBS) (UBR1). Here, we report variants in the E3 ligase UBR5 in 29 individuals presenting with a neurodevelopmental syndrome that includes developmental delay, autism, intellectual disability, epilepsy, movement disorders, and/or genital anomalies. Their phenotype is distinct from JBS due to the absence of exocrine pancreatic insufficiency and the presence of autism, epilepsy, and, in some probands, a movement disorder.
View Article and Find Full Text PDFColloids Surf B Biointerfaces
December 2024
The Affiliated Guangdong Second Provincial General Hospital of Jinan University, PR China. Electronic address:
Alpha-fetoprotein (AFP), serves as a reliable and vital biomarker for precise diagnosis and effective monitoring of hepatocellular carcinoma, requires precise detection. Herein, a sandwich-structured electrochemical immunosensor was crafted, employing three-dimensional layered porous carbon modified with gold nanoparticles (Au NPs) as the substrate and Au NPs/CuS as the labeling compound for accurate and sensitive detection of AFP. Due to the effective coordination between the 3D carbon network, Au NPs, and hollow CuS nanocubes, the sandwich-structured electrochemical immunosensor was able to produce three distinct response signals via various detection techniques, demonstrating a broad linear range (0.
View Article and Find Full Text PDFACS Appl Mater Interfaces
December 2024
School of Material Science and Engineering, Shanghai University of Engineering Science, Shanghai 201620, P.R. China.
Soft actuators are limited by single-mode driving technology, which poses challenges in dealing with complex and multidimensional movements. In this study, a multiresponsive soft actuator was fabricated by integrating a microwrinkling structure into an MXene-based film, enabling programmable motions. To achieve this, we introduced -hexane into the film preparation process and utilized its rapid volatilization to accelerate the shrinkage difference between the film and the substrate.
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