EDTA-甘氨酸联合法制备LaAlO3基电解质材料及其电性能

采用EDTA-甘氨酸联合法(EGCP)合成具有钙钛矿结构的La0.90Sr0.10Al0.97Mg0.03O3-δ(LSAM)粉体。采用TG-DSC,XRD,ICP-OES和TEM对粉体进行表征。在750℃下,无定形结构的粉末直接转化为钙钛矿结构的LSAM粉体。经1000℃煅烧3 h后的粉体,团聚程度低,粒径分布均匀,平均粒径约为77 nm,具有良好的烧结性能。通过SEM对材料的显微结构进行观察并分析其对电性能的影响。采用直流四电极法在空气中测定材料的总电导率,在800℃时,EGCP合成的LSAM电解质的总电导率为1.50×10-2S.cm-1,比固相法的高47.1%。     

A tridentate CNO‐donor palladium(II) complex as efficient catalyst for direct C―H arylation: Application in preparation of imidazole‐based push–pull chromophores

A series of imidazolium chlorides for the formation of tridentate CNO‐donor palladium(II) complexes featuring N‐heterocyclic carbene moieties have been developed from cheap and readily available starting materials with high yields. Their palladium complexes were prepared by reactions between the ligand precursors and PdCl₂ using K₂CO₃ as base in pyridine with reasonable yields. These air‐stable metal complexes were characterized using ¹H NMR and ¹³C{¹H} NMR spectroscopy and elemental analyses. Heteronuclear multiple bond correlation experiments were performed to identify key NMR signals of these compounds. The structures of two of the complexes were also established by single‐crystal X‐ray diffraction analysis. One of these complexes was successfully applied in the direct C―H functionalization reactions between heterocyclic compounds and aryl bromides, producing excellent yields of coupled products. The coupling reactions were scalable, allowing grams of coupled products to be obtained with a mere 2 mol% of Pd loading. The catalyst system developed allowed the large‐scale preparation of several push–pull chromophores straightforwardly. Photophysical properties based on UV–visible and fluorescence spectroscopy for these chromophores were investigated. Deep blue photoluminescence with moderate quantum efficiency and twisted intramolecular charge transfer excited state were observed for these chromophores. Density functional theory (DFT) and time‐dependent DFT calculations were performed to support the experimental results.     

The importance of protonation and tautomerization in relative binding affinity prediction: a comparison of AMBER TI and Schrödinger FEP

In drug discovery, protonation states and tautomerization are easily overlooked. Through a Merck–Rutgers collaboration, this paper re-examined the initial settings and preparations for the Thermodynamic Integration (TI) calculation in AMBER Free-Energy Workflows, demonstrating the value of careful consideration of ligand protonation and tautomer state. Finally, promising results comparing AMBER TI and Schrödinger FEP+ are shown that should encourage others to explore the value of TI in routine Structure-based Drug Design.     

Hydrostatic Pressure Studies Distinguish Global from Local Protein Motions in C−H Activation by Soybean Lipoxygenase‐1

The proposed contributions of distinct classes of local versus global protein motions during enzymatic bond making/breaking processes has been difficult to verify. We employed soybean lipoxygenase‐1 as a model system to investigate the impact of high pressure at variable temperatures on the hydrogen‐tunneling properties of the wild‐type protein and three single‐site mutants. For all variants, pressure dramatically elevates the enthalpies of activation for the C−H activation. In contrast, the primary kinetic isotope effects (KIEs) for C−H activation and their corresponding temperature dependencies remain unchanged up to ca. 700 bar. The differential impact of elevated hydrostatic pressure on the temperature dependencies of rate constants versus substrate KIEs provides direct evidence for two distinct classes of protein motions: local, isotope‐dependent donor–acceptor distance‐sampling modes, and a more global, isotope‐independent search for productive protein conformational sub‐states.     

Enantioselective Total Synthesis of (+)‐Steenkrotin A and Determination of Its Absolute Configuration

The first enantioselective total synthesis of (+)‐steenkrotin A has been achieved in 18 steps and 4.2 % overall yield. The key features of the strategy entail a Rh‐catalyzed O?H bond insertion followed by an intramolecular carbonyl‐ene reaction, two sequential SmI₂‐mediated Ueno–Stork and ketyl–olefin cyclizations, and a cascade intramolecular aldol condensation/vinylogous retro‐aldol/aldol process with inversion of the relative configuration at the C7 position. The absolute configuration of (+)‐steenkrotin A was determined based on the stepwise construction of the stereocenters during the total synthesis.     

A conjectural formula for genus one Gromov-Witten invariants of some local Calabi-Yau <Emphasis Type="Italic">n</Emphasis>-folds

We conjecture a formula for the generating function of genus one Gromov-Witten invariants of the local Calabi-Yau manifolds which are the total spaces of splitting bundles over projective spaces. We prove this conjecture in several special cases, and assuming the validity of our conjecture we check the integrality of genus one Bogomol’nyi-Prasad-Sommerfield (BPS) numbers of local Calabi-Yau 5-folds defined by Klemm and Pandharipande.