Single Atom Alloy Preparation and Applications in Heterogeneous Catalysis

There have been remarkable progresses in manipulating heterogeneous catalysts' nanostructures in the past decade. The concept of single atom alloy (SAA) was firstly proposed in 2012 when researchers successfully stabilized single Pd atoms on the Cu(111) surface. However, earlier work in 2009, which focused on replacing one Au atom with a Pd atom in thiolate protected Au₂₅ nanoclusters, could also be considered as the pioneer work of single atom alloy. Both kinds of single atom alloys exhibited the potential of maximum utilization of scarce elements and attractive catalytic performances. The well‐defined structures of SAA catalysts make accurate modeling possible, which further realizes the rational design of single atom alloy catalysts. In this review, we summarize the research trajectory of single atom alloys as well as recent achievements in this field. We also introduce several commonly adopted characterization methods for SAA catalysts such as scanning tunneling microscopy (STM), temperature programmed reaction (TPR), extended X‐ray absorption fine structure (EXAFS) spectra, matrix assisted laser desorption/ionization mass spectrum (MALDI‐MS) and differential pulse voltammetry (DPV). Through discussing recent progresses in SAA catalysts, we propose that future researches in this filed should be focused on exploring new kinds of metal nanocrystals and controlling the nanostructure of SAA even more precisely.     

Preparation of 2,4-diarylquinolines and substituted dihydrobenz-[c]acridines by the condensation of certain c(α),o-dilithiooximes with 2-aminobenzophenones

C(α),O-Dilithiooximes were prepared in an excess of lithium diisopropylamide and condensed with several 2-aminobenzophenones, followed by acid hydrolysis of the oximes to the ketones, which then underwent cyclodehydration and linear dehydration to give substituted quinolines or dihydrobenz[c]acridines.     

Anomalies in the asymmetric hydroboration of olefins with the 11 adduct of (+)-α-pinene and BH3 · THF

The hydroboration of cis-2-butene and cis-3-hexene with pure diisopinocampheylborane (IPC₂BH) and monoisopinocampheylborane (IPCBH₂), both prepared from (+)-α-pinene, were studied. In contrast to IPC₂BH, which yielded R-(?)-2-butanol and R-(?)-3-hexanol in 98.4 and 94.5% optical purities, IPCBH₂ yielded S-(+)-2-butanol and S-(+)-3-hexanol in 23.6 and 19.7% optical purifies respectively. PMR examination of the methanolyzed products were utilized to establish the species present in the freshly prepared and aged $\text{1}\text{1}$ adduct from (+)-α-pinene and BH₃ · THF. The results confirm the interpretation previously advanced for the major differences realized in asymmetric hydroboration with the fresh and aged $\text{1}\text{1}$ adducts.     

Molecular structure and pseudopolymorphism of squamtin A from Annona squamosa

The cyclopeptide, squamtin A (1, formula: C₃₉H₆₀O₁₁N₈S), was found to crystallized in two pseudopolymorphisms, i.e. 1·(H₂O)_3.5 and 1·(H₂O)_3.9. The composition of the amino acids and their linkage sequences are the same. The main differences between the two kinds of crystals lie in the positions and occupancies of the water molecules, the positions of the sulfur atoms and the conformation of the side chains. The absolute configuration of 1 is established by X-ray analysis in combination with the Marfey's analysis of its hydrolysates.     

Analysis of bufadienolides in the Chinese drug ChanSu by high-performance liquid chromatography with atmospheric pressure chemical ionization tandem mass spectrometry

The qualitative analysis of bufadienolides in the Chinese drug ChanSu was performed using high-performance liquid chromatography with atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS/MS). Bufadienolides are the major bioactive constituents of ChanSu, which is used to treat heart failure and cancer in traditional Chinese medicine. The APCI-MS fragmentation behavior of bufadienolides was studied. For bufadienolides with only hydroxyl substituents, the fragmentation was characterized by successive eliminations of H(2)O and CO molecules, and the profile of MS/MS product ions was correlated with the number of hydroxyl groups. If a C-16 acetoxyl group was present, the fragmentation of [M+H](+) ions was triggered by initial loss of 60 Da (HOAc). The elimination of CO was significant for bufadienolides with a 19-formyl group, and the 19-hydroxyl group could be characterized by the loss of 30 Da (HCHO). These fragmentation rules were applied to the identification of bufadienolides in a methanolic extract of ChanSu, which was separated on a C(18) column with gradient elution. A total of 35 bufadienolides were identified, including four new constituents. The method established here facilitated the convenient and rapid quality control of ChanSu crude drug and its pharmaceutical preparations.     

Ab initio studies of the allylic hydroxylation: DFT calculation on the reaction of 2-methyl-2-butene with selenium dioxide

The mechanism of the allylic oxidation of 2-methyl-2-butene with selenium dioxide has been investigated by ab initio quantum mechanics. Transition states for two major steps (an ene reaction and a [2,3]-sigmatropic rearrangement) of this reaction have been optimized by the B3LYP/6-311+G(d,p) method. A comparison of the energies of the transition states shows that the anti-endo and syn-endo approaches are the efficient routes in the ene reaction and the methyl (C4) group is sited in a pseudo-equatorial environment in cyclic transition states during the [2,3]-rearrangement. Calculations also show the kind of the terminal alkyl (C4) substituents may control (E)-selectivity in the formation of the allylic alcohols.     

含有陡峭势阱和凹凸非线性项的Kirchhoff型问题的多重正解*

在这篇文章中, 作者研究涉及凹凸非线性项的Kirchhoff型问题-(a + b ∫R3|▽u|²dx) Δu + λV (x)u = μf(x)|u|^q?2u + |u|^p?2u, x ∈ R³,u ∈ H¹(R³),其中a,b > 0 是常数, λ, μ > 0 是参数, 1 < q < 2, 4 < p < 6 且 V 是一个非负连续位势. 在f(x) 和 V 的合适条件下,此问题正解的存在性和集中性能够通过Nehari 流形和Ekeland 变分原理得到.