Enantio- and Regioselective Electrooxidative Cobalt-Catalyzed C-H/N-H Annulation with Alkenes.

In recent years, the merging of electrosynthesis with 3d metal catalyzed C-H activation has emerged as a sustainable and powerful technique in organic synthesis. Despite the impressive advantages, the development of an enantioselective version remains elusive and poses a daunting challenge. Herein, we report the first electrooxidative cobalt-catalyzed enantio- and regioselective C-H/N-H annulation with olefins using an undivided cell at room temperature (up to 99 % ee).

Analysis of Isotopically Depleted Proteins Derived from and Cell Lines by Liquid Chromatography 21 T Fourier Transform-Ion Cyclotron Resonance Mass Spectrometry.

Protein mass measurement by mass spectrometry is complicated by wide isotopic distributions that result from incorporation of heavy isotopes of C, H, N, O, and S, thereby limiting signal-to-noise ratio (SNR) and accurate intact mass determination, particularly for larger proteins [Fenselau et al. 1983, 55 (2), 353-356]. Observation of the monoisotopic mass-to-charge ratio (/) is the simplest and most accurate way to determine intact protein mass, but as mass increases, the relative abundance of the monoisotopic peak becomes so low that it is often undetectable.

Synthesis, characterization, solution chemistry and anticancer activity of [NiCl(PhP-N(R)-PPh)] (R = 2-CHPy, CHPh and p-tol) complexes.

In this work three Ni complexes with general formula [NiCl(PhP-N(R)-PPh)], R = 2-CHPy (Py = pyridine) - 1, CHPh (Ph = phenyl) - 2 and p-tol (p-tol = p-tolyl) - 3, were synthesized and characterized. These complexes were obtained in high yield by the reaction of NiCl.6HO and the corresponding diphenylphosphinoamine ligand (PhP-N(R)-PPh) in CHCl/MeOH (1:1) solution, at room temperature (∼25 °C), and characterized by H and P {H} NMR, vibrational spectroscopy in the infrared region, electronic spectroscopy in the UV-Vis regions, elemental analysis (%C, %H, %N) and single-crystal X-ray diffraction.

Assignment of aromatic side-chain spins and characterization of their distance restraints at fast MAS.

The assignment of aromatic side-chain spins has always been more challenging than assigning backbone and aliphatic spins. Selective labeling combined with mutagenesis has been the approach for assigning aromatic spins. This manuscript reports a method for assigning aromatic spins in a fully protonated protein by connecting them to the backbone atoms using a low-power TOBSY sequence.

A three-step pathway from (2-aminophenyl)chalcones to novel styrylquinoline-chalcone hybrids: synthesis and spectroscopic and structural characterization of three examples.

Three new styrylquinoline-chalcone hybrids have been synthesized using a three-step pathway starting with Friedländer cyclocondensation between (2-aminophenyl)chalcones and acetone to give 2-methyl-4-styrylquinolines, followed by selective oxidation to the 2-formyl analogues, and finally Claisen-Schmidt condensation between the formyl intermediates and 1-acetylnaphthalene. All intermediates and the final products have been fully characterized by IR and H/C NMR spectroscopy, and by high-resolution mass spectrometry, and the three products have been characterized by single-crystal X-ray diffraction. The molecular conformations of (E)-3-{4-[(E)-2-phenylethenyl]quinolin-2-yl}-1-(naphthalen-1-yl)prop-2-en-1-one, CHNO, (IVa), and (E)-3-{4-[(E)-2-(4-fluorophenyl)ethenyl]quinolin-2-yl}-1-(naphthalen-1-yl)prop-2-en-1-one, CHFNO, (IVb), are very similar.

Control of Fluorescence of Organic Dyes in the Solid-State by Supramolecular Interactions.

Fluorescent organic dyes play an essential role in the creation of new "smart" materials. Fragments and functional groups capable of free rotation around single bonds can significantly change the fluorescent organic dye's electronic structure under analyte effects, phase state transitions, or changes in temperature, pressure, and media polarity. Dependencies between steric and electronic structures become highly important in transition from a solution to a solid-state.

Selective Synthesis of Pyrazolonyl Spirodihydroquinolines or Pyrazolonyl Spiroindolines under Aerobic or Anaerobic Conditions.

Presented herein is a condition-controlled selective synthesis of pyrazolonyl spirodihydroquinolines or pyrazolonyl spiroindolines through formal [5 + 1] or [4 + 1] spiroannulation of 2-alkenylanilines with diazopyrazolones. Mechanistically, the formation of the title products involves initial generation of a pyrazolonyl spiro-fused seven-membered ruthenacycle species serving as a key intermediate through Ru(II)-catalyzed C-H/N-H bonds metalation, carbene formation, and its migratory insertion. When the reaction is carried out under air, the key intermediate undergoes reductive elimination to afford spirodihydroquinoline.

Differences between water-soluble and water-insoluble melanin derived from mushroom.

Melanin is a natural pigment with a high content and a complex polymer structure. In this study, both water-soluble and water-insoluble melanin were obtained from the fruiting bodies of the mushroom , and scanning electron microscopy (SEM), ultraviolet (UV) absorption, Fourier transform infrared (FTIR) spectroscopy, elemental analysis, nuclear magnetic resonance (NMR) spectroscopy, pyrolysis gas chromatography mass spectroscopy (Py-GCMS), and matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF-MS/MS) were used to analyze the water-soluble and water-insoluble fungal melanin (IHFM). Differences in the chemical composition and structure of fungal melanin (IHFM) were found.

The First Noncovalent-Bonded Supramolecular Frameworks of (Benzylthio)Acetic Acid with Proline Compounds, Isonicotinamide and Tryptamine.

The co-crystallization of (benzylthio)acetic acid (HBTA) with L-proline (L-PRO), D-proline (D-PRO), DL-proline (DL-PRO), isonicotinamide (INA) and tryptamine (TPA) led to the formation of five novel crystalline compounds: L-PRO·HBTA (), D-PRO·HBTA (), DL-PRO·HBTA (), INA·HBTA () and TPA·BTA (). The prepared supramolecular assemblies were characterized by single crystal X-ray diffraction, an elemental analysis, FT-IR spectroscopy and a thermal analysis based on thermogravimetry (TG) combined with differential scanning calorimetry (DSC). Additionally, their melting points through TG/DSC measurements were established.

Coupled C, H, N, S and Fe biogeochemical cycles operating in the continental deep subsurface of the Iberian Pyrite Belt.

Microbial activity is a major contributor to the biogeochemical cycles that make up the life support system of planet Earth. A 613 m deep geomicrobiological perforation and a systematic multi-analytical characterization revealed an unexpected diversity associated with the rock matrix microbiome that operates in the subsurface of the Iberian Pyrite Belt (IPB). Members of 1 class and 16 genera were deemed the most representative microorganisms of the IPB deep subsurface and selected for a deeper analysis.

Cu(II)-Catalyzed, Site Selective Sulfoximination to Indole and Indolines via Dual C-H/N-H Activation.

A copper-catalyzed protocol furnishing -arylated sulfoximines has been developed via dual N-H/C-H activation. Arylalkyl- and less reactive diarylsulfoximines were efficiently coupled with privileged scaffolds like indolines, indoles, and -Ar-7-azaindoles. Sulfoximines based on medicinally relevant scaffolds (phenothiazine, dibenzothiophene, thioxanthenone) were also well tolerated.

Mutation patterns and evolutionary action score of TP53 enable identification of a patient population with poor prognosis in advanced non-small cell lung cancer.

Background: TP53 mutations are frequent in non-small cell lung cancer (NSCLC). Different categories of TP53 mutations may be associated with survival in advanced NSCLC, but their effect on prognosis is diverse. To date, a comprehensive comparison of the relationship between different classes of TP53 alterations and survival in advanced NSCLC has rarely been performed.

Comparative antibacterial activities of and extracts against and with studying on disc diffusion assay, material characterizations, and batch experiments.

Using extracted plants is an attractive option because they consist of good chemical properties against different types of bacteria, and the idea of a form modification in beads may conveniently apply to the disinfection of wastewater systems. and leaves were extracted for the synthesis of bead materials and studied material characterizations. A disc diffusion assay, batch experiments, adsorption isotherms, adsorption kinetics, and desorption experiments were studied for investigating the bacteria removal efficiencies of materials.

Contrast phase recognition in liver computer tomography using deep learning.

Hepatocellular carcinoma (HCC) has become the 4th leading cause of cancer-related deaths, with high social, economical and health implications. Imaging techniques such as multiphase computed tomography (CT) have been successfully used for diagnosis of liver tumors such as HCC in a feasible and accurate way and its interpretation relies mainly on comparing the appearance of the lesions in the different contrast phases of the exam. Recently, some researchers have been dedicated to the development of tools based on machine learning (ML) algorithms, especially by deep learning techniques, to improve the diagnosis of liver lesions in imaging exams.

Identification of nitrogen pollution sources and transport transformation processes in groundwater of different landforms using C, H, N, and O isotope techniques: an example from the lower Weihe River.

Nitrogen pollution in groundwater is an environmental issue of global concern. Identifying nitrogen pollution sources and determining migration and transformation processes are the major ways to prevent and control nitrogen pollution in the groundwater on a regional scale. In this study, groundwater in the lower Wei River was investigated by combining multi-isotope tracing techniques with the SIAR hybrid model (source resolution) to trace the nitrate sources and their contribution rate to nitrogen pollution in groundwater of different geomorphological units, considering types of geomorphology as the units.

Thermal and Structural Characterization of Two Crystalline Polymorphs of Tafamidis Free Acid.

Tafamidis, chemical formula CHClNO, is a drug used to delay disease progression in adults suffering from transthyretin amyloidosis, and is marketed worldwide under different tradenames as a free acid or in the form of its meglumine salt. The free acid (CAS no. 594839-88-0) is reported to crystallize as distinct (polymorphic) crystal forms, the thermal stability and structural features of which remained thus far undisclosed.

Characterization of Self-Growing Biomaterials Made of Fungal Mycelium and Various Lignocellulose-Containing Ingredients.

In this study, novel blends of mycelium biocomposites (MB) were developed. Various combinations of birch sawdust and hemp shives with birch bark (BB) and wheat bran (WB) additives were inoculated with basidiomycete to produce self-growing biomaterials. MB were characterized according to mycelial biomass increment in final samples, changes in chemical composition, elemental (C, H, N) analyses, granulometry of substrates, water-related and mechanical properties, as well as mold resistance and biodegradability.

Exploration of Molecular Structure, DFT Calculations, and Antioxidant Activity of a Hydrazone Derivative.

The hydrazine derivatives are known to possess several biological activities including anticancer, antibacterial and anti-fungal, anticonvulsant, and antioxidant. This communication presents the synthesis, X-ray crystal structure analysis, DFT calculations, cell cytotoxicity, and antioxidant activity of the Schiff base 4,4'-((1E,1'E)-hydrazine-1,2-diylidenebis(ethan-1-yl-1-ylidene))bis(benzene-1,3-diol) (compound ). We have also isolated the side product compound and characterized it using single X-ray crystallography.

Copper-Catalyzed C7-Selective C-H/N-H Cross-Dehydrogenative Coupling of Indolines with Sulfoximines.

Cu-catalyzed cross-dehydrogenative coupling of the C7 C-H bond of indolines with sulfoximines has been accomplished. The reaction can be extended to the cross-dehydrogenative coupling of -aryl 7-azaindoles with monoselectivity. The use of first-row copper catalysis, substrate scope, and late-stage synthetic applications are the important practical features.

Antibacterial activities against and of extracted leaf materials by disc diffusion assay and batch experiments.

The use of contaminated water by bacteria may cause many diseases, and thus clean water is needed. Chlorine is normally used for the disinfection of wastewater treatment; however, it produces unwanted odors. Using extracted () is an interesting choice because it is a good chemical compound for bacterial inhibitions.

Global Impact of the COVID-19 Pandemic on Stroke Volumes and Cerebrovascular Events: A 1-Year Follow-up.

Background And Objectives: Declines in stroke admission, IV thrombolysis (IVT), and mechanical thrombectomy volumes were reported during the first wave of the COVID-19 pandemic. There is a paucity of data on the longer-term effect of the pandemic on stroke volumes over the course of a year and through the second wave of the pandemic. We sought to measure the effect of the COVID-19 pandemic on the volumes of stroke admissions, intracranial hemorrhage (ICH), IVT, and mechanical thrombectomy over a 1-year period at the onset of the pandemic (March 1, 2020, to February 28, 2021) compared with the immediately preceding year (March 1, 2019, to February 29, 2020).

Proteomics-Compatible Fourier Transform Isotopic Ratio Mass Spectrometry of Polypeptides.

Measuring the relative abundances of heavy stable isotopes of the elements C, H, N, and O in proteins is of interest in environmental science, archeology, zoology, medicine, and other fields. The isotopic abundance measurements of the fine structure of immonium ions with ultrahigh resolution mass spectrometry obtained in gas-phase fragmentation of polypeptides have previously uncovered anomalous deuterium enrichment in (hydroxy)proline of bone collagen in marine mammals. Here, we provide a detailed description and validation of this approach and demonstrate per mil-range precision of isotopic ratio measurements in aliphatic residues from proteins and cell lysates.

Rh(III)-Catalyzed Oxidative Domino C-H/N-H Annulation: Diarylureas as Arylamine Donors for the Assembly of Indolo[2,1-]isoquinolines.

An efficient and convenient Rh(III)-catalyzed double aryl C(sp2)-H bond and N-H activation and annulation reaction is reported for the synthesis of indolo[2,1-]isoquinolines in the presence of the Cu(OAc) oxidant under heating conditions. Distinct from previous works with other arylamine donors, one molecule of 1,3-diarylurea can serve as a precursor of two molecules of arylamine in the reaction with diaryl-substituted alkynes.