In this study, coenzyme Q(10) (CoQ(10)) has been investigated by in situ near-infrared Fourier transform surface-enhanced Raman scattering (NIR-FT-SERS) spectroelectrochemistry and angle-resolved X-ray photoelectron spectroscopy (AR-XPS) on silver surface. The surface adsorption behavior of the coenzyme Q(10) radical intermediate could be monitored by potential-dependent SERS technique. At the ...

Purpose of Review: Laparoscopic radical nephroureterectomy (LNU) is being increasingly performed at several centers across the world. This review analyzes the published perioperative and oncologic outcomes of this procedure. Recent Findings: Laparoscopic radical nephroureterectomy (LNU) for upper tract TCC is performed pure laparoscopically (LNU) or hand-assisted (HALNU). The most debated issue...

The kinetics of formation and breakdown of the putative active oxygenating intermediate in cytochrome P450, a ferryl-oxo-(pi) porphyrin cation radical (Compound I), have been analyzed in the reaction of a thermostable P450, CYP119, with meta-chloroperoxybenzoic acid (m-CPBA). Upon rapid mixing of m-CPBA with the ferric form of CYP119, an intermediate with spectral features characteristic of a f...

Unique bicyclic octosyl uronic acid nucleosides include ezomycin, malayamycin, and octosyl acid (OA). They are structurally characterized by OA, an unusual 8-carbon furanosyl nucleoside core proposed to be the precursor to polyoxin and nikkomycin. Despite the well-known bioactivity of these nucleoside antibiotics, the biosynthesis of OA has not been elucidated yet. Here we report the two pivota...

A comprehensive product study, performed via the turbulent flow chemical ionization mass spectrometry (TF-CIMS) technique, of the primary OH-initiated oxidation of many of the atmospherically abundant aromatic compounds was performed. The bicyclic peroxy radical intermediate, a key proposed intermediate species in the Master Chemical Mechanism (MCM) for the atmospheric oxidation of aromatics, w...

Cofactor-free oxidases and oxygenases promote and control the reactivity of O2 with limited chemical tools at their disposal. Their mechanism of action is not completely understood and structural information is not available for any of the reaction intermediates. Near-atomic resolution crystallography supported by in crystallo Raman spectroscopy and QM/MM calculations showed unambiguously that ...

Cfr-dependent methylation of C8 of A2503 in 23S ribosomal RNA confers bacterial resistance to an array of clinically important antibiotics that target the large subunit of the ribosome, including the synthetic oxazolidinone antibiotic linezolid. The key element of the proposed mechanism for Cfr, a radical S-adenosylmethionine enzyme, is the addition of a methylene radical, generated by hydrogen...

Fish sauces are fermented seasonings traditionally used throughout Asia, including Japan. Here, we report on the antioxidant activity of 30 fish sauces, among them a puffer fish sauce developed specifically for this study. To determine the antioxidant activity (i.e., the peroxyl radical elimination capacity) of the fish sauces, the oxygen radical absorbance capacity (ORAC) was measured. ORAC va...

We consider the Rosenfeld-Gröbner algorithm for computing a regular decomposition of a radical differential ideal generated by a set of ordinary differential polynomials in n indeterminates. For a set of ordinary differential polynomials F , let M(F ) be the sum of maximal orders of differential indeterminates occurring in F . We propose a modification of the Rosenfeld-Gröbner algorithm, in whi...

The 1,2,4-benzotriazine 1,4-dioxides are an important class of potential anticancer drugs that selectively kill the low-oxygen (hypoxic) cells found in solid tumors. These compounds undergo intracellular one-electron enzymatic reduction to yield an oxygen-sensitive drug radical intermediate that partitions forward, under hypoxic conditions, to generate a highly reactive secondary radical that c...