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Two-dimensional (2D)-structured photocatalysts with atomically thin layers not only have the potential to enhance hydrogen generation efficiency but also allow more direct investigations of the effects of surface terminations on photocatalytic activity. Taking 2D Bi2WO6 as a model, we found that the configuration of bilayer Bi2O2 sandwiched by alternating WO4 layers enabled the thermodynamic driving potential for photocatalytic hydrogen evolution. Without Pt deposition, the H2 generation efficiency can reach to 56.9 μmol/g/h by 2D Bi2WO6 as compared with no activity of Bi2WO6 nanocrystals under simulated solar light. This configuration is easily functionalized by adsorption of Cl-/Br- to form Bi-Cl/Bi-Br bonds, which leads to the decrease of recombination in photogenerated charge carriers and narrower band gaps. This work highlights an effective way to design photocatalysts with efficient hydrogen evolution by tuning the surface terminations.ConspectusArtificial metalloenzymes (ArMs) are obtained by inserting homogeneous catalysts into biological scaffolds and are among the most promising strategies in the quest for new-to-nature biocatalysts. The quality of their design strongly depends on how three partners interact the biological host, the "artificial cofactor," and the substrate. However, structural characterization of functional artificial metalloenzymes by X-ray or NMR is often partial, elusive, or absent. How the cofactor binds to the protein, how the receptor reorganizes upon the binding of the cofactor and the substrate, and which are the binding mode(s) of the substrate for the reaction to proceed are key questions that are frequently unresolved yet crucial for ArM design. Such questions may eventually be solved by molecular modeling but require a step change beyond the current state-of-the-art methodologies.Here, we summarize our efforts in the study of ArMs, presenting both the development of computational strategies and their applicaigns of ArMs to guide experiments toward chemical and mutational changes that improve their activity and/or enantioselective profiles and expand toward future directions.It is well known that the upconversion luminescence from lanthanide metal-organic frameworks (Ln-MOFs) is difficult to achieve, and thus, there are few reports on dual luminescence-based MOFs. Here, dual-mode light-emitting Ln-MOFs are synthesized using a low-cost hydrothermal method. Our results show that the obtained Ln-MOFs not only have high thermal stability (up to 420°) but also are stable in deionized water. The dual-mode up- and downconversion luminescence is simultaneously observed from Er-Eu-MOFs. The temperature-dependent fluorescence decay time is calculated to be ranging from 0.46 to 0.36 ms for temperatures from 100 to 300 K. We suggested that this phenomenon was because the number of phonons participating in the MOF matrix increases with temperature during the luminescence process, and the phonons interact with the electrons in the material. The values of the J-O parameters calculated from the emission spectra indicated that the symmetry around Eu3+ ions in Eu-MOF is the highest, which was also higher than that of Er-Eu-MOF. To explore the potential applications of Eu-MOFs in white light-emitting diodes (LEDs), red emission from Eu-MOFs was combined with blue, green, and yellow emissions from metal halide perovskites to achieve white light emission. White light with excellent color quality and vision performance was obtained. These findings demonstrate that Ln-MOFs are potentially successful materials for applications in white LEDs.Through an "isoreticular expansion" strategy, a large number of highly porous zirconium-based metal-organic frameworks (Zr-MOFs) have been achieved using extended organic linkers in the past few years. However, interpenetrated Zr-MOFs with ftw topology have scarcely been reported, mainly owing to the used bulky tetratopic linkers that effectively prevent the network interpenetration. Here, we report a new family of zirconium and lanthanide (Ln) MOFs with ftw topology, constructed by hexanuclear Zr or Ln (Ln = Eu, Tb, Gd, Dy, Tm, Yb, Nd, and Er) clusters and a spirobifluorene-center tetracarboxylate linker. Our studies reveal that the isostructural Zr and Ln MOFs are all doubly interpenetrated with ultrahigh thermal and chemical stability. The observed unusual interpenetration can be attributed to the specific geometry of the spirobifluorene-center tetratopic linker. Gas adsorption studies show that the interpenetrated Zr-MOF is still highly porous and exhibits high performance for CO2 storage, which can be attributed to the strong CO2 binding environment contributed by the reduced pore size. In addition, the presented MOFs display strong characteristic luminescence in the UV-vis-NIR region. Moreover, the incorporation of the spiro-center linker into the framework can efficiently produce two-photon-excited photoluminescence with a large action cross-section value, which also benefited from the high packing density of the nonlinear optical chromophore linker in the interpenetrated structure.A suitable insulating polymer material that is compatible with the fabrication process of organic transistors and has excellent electrical properties is critically required for the next-generation flexible organic electronics. In this study, using a one-step polymerization method, we synthesized two different solution-processable polyimides (PIs) incorporated with abundant trifluoromethyl groups. Not only were the two resulting PIs-termed 6FDA-6FDAM-PI and 6FDA-TFMB-PI-well soluble in organic solvents, but also they showed transparent and colorless optical properties. The fluorinated PI films showed smooth surface topographies and surface energy values that were appropriate for their use in bottom-gate organic transistors. Organic transistors separately fabricated with 6FDA-6FDAM-PI and 6FDA-TFMB-PI as the gate insulators showed excellent device performance and electrical stability under various testing conditions, especially for pentacene-based devices. The excellent performance of the devices with fluorinated PIs was attributed to the enhanced microstructure of the organic semiconductor and the fluorine-rich characteristic of the underlying gate insulator. Furthermore, organic complementary circuits including the basic logic gates of NOT, NOR, and NAND were demonstrated using these devices.The metal-organic framework (MOF)-type MFM-300(Sc) exhibits a combined physisorption and chemisorption capture of H2S, leading to a high uptake (16.55 mmol g-1) associated with high structural stability. The irreversible chemisorbed sulfur species were identified as low-order polysulfide (n = 2) species. The isostructural MFM-300(In) was demonstrated to promote the formation of different polysulfide species, paving the way toward a new methodology to incorporate polysulfides within MOFs for the generation of novel MOF-lithium/sulfur batteries.In contrast to classical ion mobility spectrometers (IMS) operating at ambient pressure, the high kinetic energy ion mobility spectrometer (HiKE-IMS) is operated at reduced pressures between 10-40 mbar. In HiKE-IMS, ions are generated in a reaction region before they are separated in a drift region. Due to the operation at reduced pressure, it is possible to reach high reduced electric field strengths up to 120 Td in both the reaction as well as drift region, resulting in a pronounced decrease in chemical cross sensitivities and a significant enhancement of the dynamic range. Until now though, only limited knowledge about the ionization pathways in HiKE-IMS is available. Typically, proton bound water clusters, H+(H2O)n, are the most abundant positive reactant ion species in classical IMS with atmospheric chemical ionization sources. However, at reduced pressure and increased effective ion temperature, the reactant ion population significantly changes. As the ionization efficiency of analyte molecules in HiKE-IMS strongly depends on the reactant ion population, a detailed knowledge of the reactant ion population generated in HiKE-IMS is essential. Here, we present a coupling stage of the HiKE-IMS to a mass spectrometer enabling the identification of ion species and the investigation of ion molecule reactions prevailing in HiKE-IMS. https://www.selleckchem.com/products/danicopan.html In the present study, the HiKE-IMS-MS is used to identify positive reactant ion populations in both, purified air and nitrogen, respectively. The experimental data suggest the generation of systems of clustered primary ions (H+(H2O)n, NO+(H2O)m, and O2+(H2O)p), which most probably serve as reactant ions. Their relative abundances highly depend on the reduced electric field strength in the reaction region. Furthermore, their effective mobilities are studied as a function of the reduced electric field strength in the drift region.The electrification of crystalline deposits of organic compounds under high vacuum was measured and quantified. A group of compounds that produce multiply charged ions by matrix-assisted ionization were deposited on a metal plate, and the current was amplified and recorded; the total charge was obtained by integration of the current. Signals of several hundred picoamperes were obtained within 10 s of the application of high vacuum and persisted for several minutes as the compounds sublimed. The magnitude and sign of the charge were matrix dependent and were affected by the presence of organic or mineral acid in the crystalline deposit, as well as by the application of an electric field. The observations are interpreted as surface electrification caused by the emission of small charged matrix particles during sublimation, with ionic charge carriers comprising protons and hydroxide ions.The monofunctional primary complexes cis-[PtCl(NH3)2(L)]+, formed by the reaction of cisplatin, a major chemotherapeutic agent, with four nucleobases L, i.e., uracil (U), 2-thiouracil (2SU), 4-thiouracil (4SU), and 2,4-dithiouracil (24dSU), have been studied by a combination of infrared multiple photon dissociation (IRMPD) action spectroscopy in both the fingerprint (900-1900 cm-1) and the N-H/O-H stretching (3000-3800 cm-1) ranges, energy-resolved collision-induced dissociation (CID) mass spectrometry, and density functional calculations at the B3LYP/LACVP/6-311G** level. On the basis of the comparison across the experimental features and the linear IR spectra of conceivable structures, the cisplatin residue is found to promote a monodentate interaction preferentially with the O4(S4) atoms of the canonical forms of U, 4SU, and 24dSU and to the S2 atom of 2SU, yielding the most stable structures. Additional absorptions reveal the presence of minor, alternative tautomers in the sampled ion populations of 2SU and 24dSU, underlying the ability of cisplatin to increase the prospect of (therapeutically beneficial) nucleic acid strand disorder. Implication of these evidence may provide insights into drug mechanism and design.Shotgun lipidomics provides sensitive and fast lipid identification without the need for chromatographic separation. Challenges faced by shotgun analysis of glycerophospholipids (GPs) include the lack of signal uniformity across GP classes and the inability to determine the carbon-carbon double bond (C═C) location within the fatty acyl chains of an unsaturated species. Two distinct derivatization strategies were employed to both enhance the ionization of GPs, via trimethylation enhancement using 13C-diazomethane (13C-TrEnDi), as well as determine location of double bonds within fatty acyl chains, employing an in-solution photochemical reaction with acetone (via the Paternò-Büchi reaction). The modified GPs were then subjected to positive ion mode ionization via electrospray ionization, producing uniform ionization efficiencies for different classes of GP species. The GPs were charge inverted via gas-phase ion/ion reactions and sequentially fragmented using ion trap collision-induced dissociation (CID). The CID of the species led to fragmentation producing diagnostic ions indicative of C═C bond location.
