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Very Discerning Procede C-C Connect Development via Palladium- Catalyzed Oxidative Carbonylation-Carbocyclization-Carbonylation-Alkynylation of Enallenes.
For validation of ab initio results, the fundamental vibration frequencies and absorption cross sections of the principal sulfur hexafluoride isotopologue are calculated, giving good agreement with cold (180 K) and room temperature (296 K) experimental spectra. Absorption cross sections calculated from our preliminary line list agree much better with these observations than the simulations using SF6 line-by-line lists constructed from effective models included in currently available spectroscopic databases.Considering that a molecular-level understanding of the azeotropic ethanol-water system can contribute to the search of new methodologies and/or modifications of industrial separation methods, this study tries to provide some clues to understand why azeotropes should be expected for ethanol, but not for methanol. Our exploration of the potential energy surface of (ethanol)6-water heteroheptamers, carried out at the B3LYP-D3/6-311++G(d,p) level, shows these heteroclusters to exhibit a cyclic structure where the cooperativity effects between the OH···O HBs is a fundamental ingredient. An analysis of this cooperativity clearly indicates that ethanol-water systems will exhibit a similarly high stability as the heterocluster size approaches the azeotrope. However, a similar behavior should not be expected for the methanol-containing analogues. A comparison between (ethanol)7, (ethanol)6-water, (methanol)7, and (methanol)6-water shows the ethanol-containing systems to be significantly more stable than the methanol-containing analogues. SD-208 manufacturer This result is probably due to the fact that the OH···O HBs are weaker than those found between ethanol molecules. However, our atoms in molecule (AIM) and noncovalent interaction (NCI) analyses unambiguously show that important contributors to the enhanced stability of the ethanol-containing clusters are the secondary van der Waals interactions between ethyl groups, which are not observed between methyl groups. Hence, while the formation of stable azeotropes is expected for the case of ethanol, for the methanol-containing analogues, the relative stability of the clusters is significantly smaller, and its formation is accompanied by an increase of the free energy.Perfluorodicarbonyl (PFDC) compounds may be emitted directly into the atmosphere or formed in the atmospheric degradation of trace fluorinated gases, such as unsaturated perfluoro cyclic compounds. A potential atmospheric removal process for PFDCs is UV photolysis, which is presently not well-characterized. In this work, UV and infrared absorption spectra of FC(O)C(O)F, FC(O)CF2C(O)F, and FC(O)CF2CF2C(O)F (three of the simplest PFDCs) and their 248 nm photolysis products are reported. UV spectra were measured at 296 K between 190 and 320 nm using single wavelength and broadband diode array spectroscopic measurement techniques. Infrared absorption spectra were measured at 296 K using Fourier transform infrared spectroscopy between 500 and 4000 cm-1. The PFDCs are shown to be potent greenhouse gases with radiative efficiencies (well-mixed) of 0.142, 0.218, and 0.293 W m-2 ppb-1 for FC(O)C(O)F, FC(O)CF2C(O)F, and FC(O)CF2CF2C(O)F, respectively. Photolysis product yields (248 nm) were measured using pulsed laser photolysis combined with infrared absorption detection of radical products scavenged to stable bromides by reaction with Br2. BrC(O)F was identified as a major stable end product in all systems with a yield greater than ∼90%. The infrared spectrum of BrC(O)F is reported as part of this study. FC(O)CBrF2 and FC(O)CF2CBrF2 were also identified as products in the photolysis of FC(O)CF2C(O)F and FC(O)CF2CF2C(O)F, respectively, by comparison with theoretically calculated infrared absorption spectra. A carbonyl difluoride (CF2O) primary photolysis yield of ∼10% was measured in the photolysis of FC(O)C(O)F.2',3',5'-Tri-O-acetyl-6,8-dithioguanosine (taDTGuo) is an analogue of nucleosides and currently under investigation as a potential agent for photodynamic therapy (PDT). Excitation by simultaneous two-photon absorption of visible or near-infrared light would provide an efficient PDT for deep-seated tumors. The two-photon absorption spectrum of taDTGuo was obtained by optical-probing photoacoustic spectroscopy (OPPAS). A two-photon absorption band corresponding to the S5 ← S0 transition was observed at 556 nm, and the two-photon absorption cross-section σ(2) was determined to be 26 ± 3 GM, which was much larger than that of other nucleobases and nucleosides. Quantum chemical calculations suggested that the large σ(2) value of taDTGuo was responsible for large transition dipole moments and small detuning energy resulting from the thiocarbonyl group at 6- and 8-positions. This is the first report on two-photon absorption spectra and cross-sections of thionucleoside analogues, which could be used to develop a more specific PDT for cancers in deep regions.Dielectric microstructures coupled with a conventional optical microscope have been proven to be a successful way to achieve super-resolution imaging. However, a limitation of such super-resolution imaging is the microstructure fabrication ability, which generally provides natural structures (such as spherical, hemispherical, superhemispherical microlenses, and so on). Meanwhile, the influences of microstructures with complex shapes on the super-resolved imaging still remain unknown. In this paper, direct laser writing (DLW) lithography is used to produce a series of complex microstructures, which are capable of achieving super-resolution imaging in the optical far-field region. Cylinder, truncated cone, hemisphere, and protruding hemisphere microstructures are successfully fabricated by this 3D printing technology, allowing us to resolve features as small as 100 nm under classical microscopy. Moreover, different microstructures lead to different photonic nanojet (PNJ) illuminations and collection efficiencies, resulting in a critical role in super-resolved imaging. The microstructures with spherical surfaces can easily collect the light scattered by the object and convert the high-spatial-frequency evanescent waves into propagating waves.
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