Strong electron-phonon coupling in Be<Subscript>1−x</Subscript>B<Subscript>2</Subscript>C<Subscript>2</Subscript>: ab initio studies

Several structures for off-stoichiometric beryllium diboride dicarbide Be_1−xB₂C₂ have been designed, and their properties studied from first-principles density functional methods. Among the most stable phases examined, the layered hexagonal structures are shown to exhibit various features in the electronic properties and in the lattice dynamics reminiscent of the superconducting magnesium diboride and alkaline earth-intercalated graphites. For substoichiometric composition x ∼ 1/3, the system is found metallic with a moderately strong electron-phonon coupling through a predominant contribution arising from high frequency streching modes modulating the σ-bonding of the B-C network, and a weaker contribution at medium frequency range of the phonon spectra, arising from the intercalent motion coupled to the π-bonding states. Further, anharmonicities emerging from the proximity of the Fermi level to the σ-band edge, contributes to reduce the phonon softening hence stabilizing the structure. All these effects appear to combine favourably to produce a high temperature phonon-superconductivity.     

Heterocyclization of amino alcohols into saturated cyclic quaternary ammonium salts

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Silver(I)‐Catalyzed Enantioselective [3+2]‐Cycloaddition Reaction of α‐Silylimines: A Facile Route to Quaternary‐Carbon‐Rich Scaffolds

A silver‐catalyzed highly enantioselective 1,3‐dipolar cycloaddition reaction of α‐silylimines with pyrone‐based trisubstituted olefins was developed affording bi‐ and tricyclic α‐quaternary‐carbon‐rich pyrano‐pyrrolidines in excellent yields. The tricyclic benzopyrone adducts thus obtained were efficiently transformed into highly complex tetracyclic scaffolds supporting four consecutive stereogenic centers with three quaternary carbons.     

Synthesis and Spectroscopic Characterisation of 2,3‐Epoxy/ 3‐Chloro‐2‐hydroxy Propyl Derivatives of Quaternary Ammonium Salts:Useful Cationic Fixing Agents

Eight mono-reactive and four bis-reactive 2,3-epoxy/3-chloro-2-hydroxy propyl derivatives of quaternary ammonium salts have been synthesised by reacting epichlorohydrin with suitable tertiary amines and diamines. Mono-reactive derivatives also contain cyano and carboxylic groups in addition to 2,3-epoxy/3-chloro-2-hydroxy propyl groups. The structures of these quaternary ammonium salts have been characterised using IR and ¹H NMR spectroscopic techniques. These quaternary ammonium chlorides have been applied to the cotton fabrics as pretreatments and aftertreatments and promising results have been obtained.     

Enantioselective Synthesis of [b]-Annulated Azepane Scaffolds

Cyclopenta-, benzo-, and cyclohepta[b]-annulated azepane scaffolds were prepared in two steps from optically active cyclic α-allyl-β-oxoesters. The first step was ruthenium-catalyzed olefin cross metathesis with acrylonitrile. The second step was palladium-catalyzed dihydrogenation which consists of three consecutive processes: The hydrogenation of the C−C double and C−N triple bonds was followed by the reductive amination via the iminium ion formed in situ from the primary amino function and the endocyclic carbonyl group. This last step gave, stereoselectively, the annulated azepanes with relative trans-configuration. The amino function and the ester group define two points for further diversification of the scaffolds. The trifluoroacetyl derivatives allowed to establish the enantiopurity of the products to be 97–98 % ee by GLC on a chiral phase. The relative trans-configurations and in one case also the absolute (R,R)-configuration was established by X-ray crystallography.     

Asymmetric Synthesis of a Quaternary Carbon Stereogenic Center by Organocatalysis Using a Primary Amino Acid and Its Salt

In this personal account, our recent developments on the asymmetric synthesis of a quaternary carbon stereogenic center by organocatalysis using a primary amino acid and its salt as a catalyst are described in three chapters: (1) conjugate addition to nitroalkenes and vinyl ketones, (2) nucleophilic addition to π-allyl palladium complexes, and (3) nucleophilic substitution reactions with allyl and propargyl halides. By these methods, asymmetric α-allylation of α-branched aldehydes and ketones smoothly proceeded to give γ-nitroaldehydes, ketoaldehydes, α-allylated aldehydes, and α-allylated β-ketoesters possessing a quaternary carbon stereogenic center in good yields with high enantioselectivities.     

The Total Synthesis of Inostamycin A

The first total synthesis of inostamycin A is described. With efficient and stereoselective synthetic routes to aldehyde 3 and ketone 4 developed through asymmetric aldol reactions, addition reactions and reduction, and with chiral building blocks, the two large fragments were coupled with remarkable anti stereoselectivity and efficiency by aldol condensation. The coupling reaction provided the complete carbon skeleton with all the requisite functional groups and stereogenic centers for inostamycin A. The two quaternary carbons at C20 and C16 of ketone 4 were elaborated in a highly stereocontrolled manner by addition reactions of the transmetallated 5 to ethyl ketone 6 and the transmetallated 7 to methyl ketone 8 , respectively, in which the use of LaCl₃ for transmetallation was critical for high coupling efficiency.     

薄膜梯度扩散-分光光度法富集测量水中痕量Mo (VI)

建立了薄膜梯度扩散(DGT)- 硫氰酸钾(PT)分光光度法(DGT-PT法)富集测量水中痕量Mo (VI) 的分析方法。本研究先以聚季铵盐(PQAS)溶液为结合相的DGT技术 (PQAS DGT) 原位分离富集水中Mo (VI),再以PT分光光度法测定DGT结合相中Mo (VI)的含量,最后依据DGT方程计算水中Mo (VI)的浓度。DGT-PT法测得配制水中Mo ( VI) 的回收率为96.3% ~ 101.3%,相对标准偏差(RSD)为1.3% ~4.0%;测得工业废水中Mo (VI) 的浓度为27.13 ~ 121.79mg/L,加标回收率为96.0% ~ 101.6%。当采样时间为48h,PQAS DGT对水中Mo (VI) 富集近18倍,可显著降低分析方法的检测限,实现水中痕量Mo (VI) 的定量检测。