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Cycloidal sector mass analyzers have, in principle, perfect focusing due to perpendicularly oriented uniform electric and magnetic fields, making them ideal candidates for incorporation of spatially coded apertures. We have previously demonstrated a proof-of-concept cycloidal-coded aperture miniature mass spectrometer (C-CAMMS) instrument and achieved a greater than 10-fold increase in throughput without sacrificing resolution, compared with a single slit instrument. However, artifacts were observed in the reconstructed mass spectrum due to nonuniformity in the electric field and misalignment of the detector and the ion source with the mass analyzer focal plane. In this work, we modified the mass analyzer design of the previous C-CAMMS instrument to improve electric field uniformity, improve the alignment of the ion source and the mass analyzer with the detector, and increase the depth-of-focus to further facilitate alignment. A comparison of reconstructed spectra of a mixture of dry air and toluene at different electric fields was performed using the improved C-CAMMS prototype. A reduction in reconstruction artifacts compared to our proof-of-concept C-CAMMS instrument highlights the improved performance enabled by the design changes.We report a protocol for the synthesis of 3-organyl-4-(organylchalcogenyl)isoquinoline-2-oxides via electrophilic cyclization between alkynylbenzaldoximes and diorganyl dichalcogenides promoted by Oxone. A total of 21 3-organyl-4-(organylchalcogenyl)isoquinoline-2-oxides were selectively obtained in yields of up 93% under an ultrasound irradiation condition in short reaction times (10-70 min). Additionally, the synthetic usefulness of the 3-phenyl-4-(phenylselanyl)isoquinoline-2-oxide was demonstrated in the annulation reaction with 1-(2-bromophenyl)-3-phenylprop-2-yn-1-one and in the deoxygenation reaction with phenylboronic acid.This initial study evaluates vacuum matrix-assisted ionization (vMAI) mass spectrometry (MS) for identification and determination of tryptic peptides from the biomarker protein progastrin releasing peptide (ProGRP). Similar peptides and charge states were observed as in liquid chromatography (LC) electrospray ionization (ESI) MS. The prolonged ion duration in vMAI with similar charge states as in ESI was advantageous for determining the MS/MS fragmentation conditions compared to MAI. It is assumed that the vacuum ionization conditions lower the detection limits of the experiment. This may be the reason vMAI combined with high resolution MS enabled detection of tryptic peptides from more digested proteins than MAI selected reaction monitoring MS. Additionally, MAI ion mobility spectrometry MS (MAI-IMS-MS) was evaluated for differentiation of intact protein isoforms, successfully enabling differentiation of the isoforms by drift time selection. Examples are both shown for model proteins bovine serum albumin, cytochrome C, and lysozyme and the clinically relevant small cell lung cancer protein biomarker ProGRP, which exists in three isoforms. Coupling with the vacuum ionization conditions using a dedicated vacuum-probe source MAI enables information to be extracted readily as with conventional approaches, just faster.Pt(II) diynes and polyynes incorporating 5,5'- and 6,6'-disubstituted 2,2'-bipyridines were prepared following conventional Sonogashira and Hagihara dehydrohalogenation reaction protocols. Using Pt(II) dimers and polymers as a rigid-rod backbone, four new heterobimetallic compounds incorporating Re(CO)3Cl as a pendant functionality in the 2,2'-bipyridine core were obtained. The new heterobimetallic Pt-Re compounds were characterized by analytical and spectroscopic techniques. The solid-state structures of a Re(I)-coordinated diterminal alkynyl ligand and a representative model compound were determined by single-crystal X-ray diffraction. Detailed photophysical characterization of the heterobimetallic Pt(II) diynes and polyynes was carried out. We find that the incorporation of the Re(CO)3Cl pendant functionality in the 2,2'-bipyridine-containing main-chain Pt(II) diynes and polyynes has a synergistic effect on the optical properties, red shifting the absorption profile and introducing strong long-wavelength absorptions. The Re(I) moiety also introduces strong emission into the monomeric Pt(II) diyne compounds, whereas this is suppressed in the polyynes. The extent of the synergy depends on the topology of the ligands. Computational modeling was performed to compare the energetic stabilities of the positional isomers and to understand the microscopic nature of the major optical transitions. We find that 5,5'-disubstituted 2,2'-bipyridine systems are better candidates in terms of yield, photophysical properties, and stability than their 6,6'-substituted counterparts. Overall, this work provides an additional synthetic route to control the photophysical properties of metallaynes for a variety of optoelectronic applications.Fungal infections could cause tremendous decreases in crop yield and quality. Natural products, including flavonoids and (iso)quinolines, have always been an important source for lead discovery in medicinal and agricultural chemistry. To promote the discovery and development of new fungicides, a series of 3-(iso)quinolinyl-4-chromenone derivatives was designed and synthesized by the active substructure splicing principle and evaluated for their antifungal activities. The lead optimization was guided by bioactivity. The bioassay data revealed that the 3-quinolinyl-4-chromenone 13 showed significant in vitro activities against S. sclerotiorum, V. mali, and B. cinerea with EC50 values of 3.65, 2.61, and 2.32 mg/L, respectively. The 3-isoquinolinyl-4-chromenone 25 exhibited excellent in vitro activity against S. sclerotiorum with an EC50 value of 1.94 mg/L, close to that of commercial fungicide chlorothalonil (EC50 = 1.57 mg/L) but lower than that of boscalid (EC50 = 0.67 mg/L). For V. Pifithrin-μ inhibitor mali and B. cinerea, 3-isoquinolinyl-4-chromenone 25 (EC50 = 1.56, 1.54 mg/L) showed significantly higher activities than chlorothalonil (EC50 = 11.24, 2.92 mg/L). In addition, in vivo experiments proved that compounds 13 and 25 have excellent protective fungicidal activities with inhibitory rates of 88.24 and 94.12%, respectively, against B. cinerea at 50 mg/L, while the positive controls chlorothalonil and boscalid showed inhibitory rates of 76.47 and 97.06%, respectively. Physiological and biochemical studies showed that the primary action of mechanism of compounds 13 and 25 on S. sclerotiorum and B. cinerea may involve changing mycelial morphology and increasing cell membrane permeability. In addition, compound 13 may also affect the respiratory metabolism of B. cinerea. This study revealed that compounds 13 and 25 could be promising candidates for the development of novel fungicides in crop protection.
Website: https://www.selleckchem.com/products/pifithrin-u.html
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