Richardsonpanduro3047

The trichophycin family of compounds are chlorinated polyketides first discovered from environmental collections of a bloom-forming Trichodesmium sp. cyanobacterium. In an effort to fully capture the chemical space of this group of metabolites, the utilization of MS/MS-based molecular networking of a Trichodesmium thiebautii extract revealed a metabolome replete with halogenated compounds. Subsequent MS-guided isolation resulted in the characterization of isotrichophycin C and trichophycins G-I (1-4). These new metabolites had intriguing structural variations from those trichophycins previously characterized, which allowed for a comparative study to examine structural features that are associated with toxicity to murine neuroblastoma cells. Additionally, we propose the absolute configuration of the previously characterized trichophycin A (5). Overall, the metabolome of the Trichodesmium bloom is hallmarked by an unprecedented amount of chlorinated molecules, many of which remain to be structurally characterized.Enantioselective diverse synthesis of a small-molecule collection with structural and functional similarities or differences in an efficient manner is an appealing but formidable challenge. Asymmetric preparation and branching transformations of tetrahydroindolizines in succession present a useful approach to the construction of N-heterocycle-containing scaffolds with functional group, and stereochemical diversity. Herein, we report a breakthrough toward this end via an initial diastereo- and enantioselective [3 + 2] cycloaddition between pyridinium ylides and enones, following diversified sequential transformations. Chiral N,N'-dioxide-earth metal complexes enable the generation of optically active tetrahydroindolizines in situ, across the strong background reaction for racemate-formation. In connection with deliberate sequential transformations, involving convenient rearomatic oxidation, and light-active aza-Norrish II rearrangement, the tetrahydroindolizine intermediates were converted into the final library including 3-arylindolizine derivatives and dicarbofunctionalized 1,5-dicarbonyl compounds. More importantly, the stereochemistry of four-stereogenic centered tetrahydroindolizine intermediates could be efficiently transferred into axial chirality in 3-arylindolizines and vicinal pyridyl and aryl substituted 1,5-diketones. In addition, densely functionalized cyclopropanes and bridged cyclic compounds were also discovered depending on the nature of the pyridinium ylides. Mechanism studies were involved to explain the stereochemistry during the reaction processes.We show that by working in a basis similar to that of the natural transition orbitals and using a modified zeroth-order Hamiltonian, the cost of a recently introduced perturbative correction to excited-state mean field theory can be reduced from seventh to fifth order in the system size. The (occupied)2(virtual)3 asymptotic scaling matches that of ground-state second-order Møller-Plesset theory but with a significantly higher prefactor because the bottleneck is iterative it appears in the Krylov-subspace-based solution of the linear equation that yields the first-order wave function. Here, we discuss the details of the modified zeroth-order Hamiltonian we use to reduce the cost and the automatic code generation process we used to derive and verify the cost scaling of the different terms. Overall, we find that our modifications have little impact on the method's accuracy, which remains competitive with singles and doubles equation-of-motion coupled cluster.Eight new dioxopiperazine alkaloids, penispirozines A-H (1-8), were discovered from the mangrove-derived fungus Penicillium janthinellum HDN13-309. Their structures were elucidated by spectroscopic analysis, TDDFT-ECD calculations, and X-ray diffraction. Compound 1 had an unusual pyrazino[1,2]oxazadecaline coupled with a thiophane ring system, and compound 2 possessed a 6/5/6/5/6 pentacyclic ring system with two rare spirocyclic centers. Interestingly, compounds 3-8 were distinguished by not only the existence of a spiro-thiophane or spiro-furan ring system but also the chirality of the pentacyclic moiety. Compounds 3 and 4 increased the expression of the two relevant phase II detoxifying enzymes SOD2 and HO-1 at 10 μM.Electronically excited states characterized by intramolecular charge transfer play an essential role in many biological processes and optical devices. The ability to make quantitative ab initio predictions of the relative energetics involved is a challenging yet desirable goal, especially for large molecules in solution. In this work, we present a data set of 61 experimental measurements of absorption and emission processes, both in the gas phase and in solvents representing a broad range of polarities, which involve intramolecular charge transfer mediated by a nonzero, "twisted" dihedral angle between one or more donor and acceptor subunits. Among a variety of density functionals investigated within the framework of linear-response theory, the "optimally tuned" LRC-ωPBE functional, which utilizes a system-specific yet nonempirical procedure to specify the range-separation parameter, emerges as the preferred choice. For the entire set of excitation energies, involving changes in dipole moment ranging from 4 t we demonstrate the utility of the optimally tuned density functional approach by targeting the charge-transfer states of a large biomimetic model system for light-harvesting structures in Photosystem II.Surface plasmon resonance imaging (SPRi) has been increasingly used in the label-free detections of various biospecies, such as organic toxins, proteins, and bacteria. In combination with the well-developed microarray immunoassay, SPRi has the advantages of rapid detection in tens of minutes and multiplex detection of different targets with the same biochip. Both prism-based and prism-free configurations of SPRi have been developed for highly integrated portable immunosensors, which have shown great potential on pathogen detection and living cell imaging. This review summarizes the recent advances in immunoassay biosensing with SPRi, with special emphasis on the multiplex detections of foodborne pathogens. selleck chemical Additionally, various spotting techniques, surface modification protocols, and signal amplification methods have been developed to improve the specificity and sensitivity of the SPRi biochip. The challenges in multiplex detections of foodborne pathogens in real-world samples are addressed, and future perspectives of miniaturizing SPRi immunosensors with nanotechnologies are discussed.