Nitrosylation of Nitric‐Oxide‐Sensing Regulatory Proteins Containing [4Fe‐4S] Clusters Gives Rise to Multiple Iron–Nitrosyl Complexes

The reaction of protein‐bound iron–sulfur (Fe‐S) clusters with nitric oxide (NO) plays key roles in NO‐mediated toxicity and signaling. Elucidation of the mechanism of the reaction of NO with DNA regulatory proteins that contain Fe‐S clusters has been hampered by a lack of information about the nature of the iron‐nitrosyl products formed. Herein, we report nuclear resonance vibrational spectroscopy (NRVS) and density functional theory (DFT) calculations that identify NO reaction products in WhiD and NsrR, regulatory proteins that use a [4Fe‐4S] cluster to sense NO. This work reveals that nitrosylation yields multiple products structurally related to Roussin's Red Ester (RRE, [Fe₂(NO)₄(Cys)₂]) and Roussin's Black Salt (RBS, [Fe₄(NO)₇S₃]. In the latter case, the absence of ³²S/³⁴S shifts in the Fe?S region of the NRVS spectra suggest that a new species, Roussin's Black Ester (RBE), may be formed, in which one or more of the sulfide ligands is replaced by Cys thiolates.     

Antibacterial activity of cyclo(L-Pro-L-Tyr) and cyclo(D-Pro-L-Tyr) from Streptomyces sp. strain 22-4 against phytopathogenic bacteria

Two bioactive cyclic dipeptides, cyclo(L-Pro-L-Tyr) and cyclo(D-Pro-L-Tyr), were isolated from the culture broth of Streptomyces sp. strain 22-4 and tested against three economically important plant pathogens, Xanthomonas axonopodis pv. citri, Ralstonia solanacearum and Clavibacter michiganensis. Both cyclic dipeptides were active against X. axonopodis pv. citri and R. Solanacearum with MIC of 31.25 μg/mL. No activity could be observed against C. michiganensis.     

The variety generated by {\mathbb {A}(\mathcal {T})}– two counterexamples

We show that \({\mathcal {V}(\mathbb {A}(\mathcal {T}))}\) does not have definable principal subcongruences or bounded Maltsev depth. When the Turing machine \({\mathcal {T}}\) halts, \({\mathcal {V}(\mathbb {A}(\mathcal {T}))}\) is an example of a finitely generated semilattice based (and hence congruence \({\wedge}\)-semidistributive) variety with only finitely many subdirectly irreducible members, all finite. This is the first known example of a variety with these properties that does not have definable principal subcongruences or bounded Maltsev depth.     

Stable carbon and nitrogen isotope discrimination and turnover in a small-bodied insectivorous lizard

Laboratory experiments are useful for estimating the carbon and nitrogen isotope discrimination factors and turnover rates that are critical for drawing field-based inferences on consumer diets using stable isotopes. Although the utility of these discrimination factors is widely recognized, work in terrestrial systems has largely been limited to studies involving mammals and birds. In contrast, scant attention has been paid to the application of isotopic techniques to reptiles, despite their broad diversity in terms of numbers of species as well as their trophic roles. Here we estimate carbon and nitrogen isotope discrimination factors and turnover for the tree lizard (Urosaurus ornatus) using a diet-switch experiment. Lizards were collected from a C₄-dominated grassland and then switched to C₃-based diet (crickets) in the laboratory. We estimated discrimination by lizard claw tissue as Δ¹³C?=?1.2?±?0.1?‰ for carbon and Δ¹⁵N?=?0.7?±?0.1?‰ (mean?±?1 SE) for nitrogen, with 95?% turnover occurring after ～15.5 days. These estimates should be appropriate for use in trophic studies of U. ornatus, and possibly other related small-bodied insectivorous lizards.     

Silver(I) mediated folding of a molecular basket

We have investigated Ag(I) mediated folding of a tridentate compound, containing three pyridine flaps tethered to a semirigid scaffold, into a molecular basket, using both experimental and theoretical methods. The basket formation has been shown to be highly favorable in organic media (Delta G degrees = -7.2 kcal/mol), with the assembly process allowing for another ligand to bind preferentially on the outer side.     

Simultaneous LC-MS/MS quantitation of a highly hydrophobic pharmaceutical compound and its metabolite in urine using online monolithic phase-based extraction

This article describes the use of monolithic material as extraction support in simultaneous LC-MS/MS quantitation of a highly hydrophobic pharmaceutical compound and its hydroxylated metabolite in urinary matrix. DMSO was added to urine samples to aid the solubilization of analytes during storage and transfer. Samples were then diluted and injected onto an online extraction system for high-throughput analysis in an automated fashion. A linear range of 1.03-103 ng/mL was validated for the parent compound and 7.02-1400 ng/mL for the metabolite. The accuracy (%bias) at the lower LOQ (LLOQ) for the parent compound was -2.9% and the precision (%CV) at the LLOQ was 5.4%, while the accuracy at LLOQ for the metabolite was 6.3% and the precision at LLOQ was 5.5%. The results show that quantitative LC-MS/MS analysis by online extraction using the monolithic support is reproducible, sensitive, and accurate enough to satisfy bioanalytical testing requirements in a good laboratory practice (GLP) regulated environment. Monolithic phase based online extraction provided efficient sample cleanup, which was evidenced in matrix effect testing against multiple lots of urinary matrix. The method described within can be a generic approach for quantitative analysis of analytes with poor solubility in aqueous matrix.