锂离子蓄电池正极材料LiFePO4研究进展

锂离子电池正极材料正在向着高比能量、长寿命、低成本、环境友好的方向发展,而具有橄榄石结构的LiFePO_4正极材料以其结构稳定、成本低、无污染等优点成为21世纪最理想的绿色电源,但自身也存在缺点。综述了锂离子电池正极材料LiFePO_4的研究进展。系统地阐述了LiFePO_4的晶体结构特征及性能、多种合成方法以及掺杂多种导电材料和控制晶体生长制备纳米粉体对材料性能的影响。对该材料的应用前景进行了展望,并提出了下一步可能的研究趋势。     

ESR Studies on a Friedel‐Crafts Alkylation Reaction in [bmim]Cl‐AlCl3 Ionic Liquid

The paramagnetic complexes formed in Friedel‐Crafts alkylation reaction systems are invistigated by electron spin resonance (ESR) spectroscopy, in room temperature ionic liquids system 1‐butyl‐3‐methyl‐limidazolium chloride‐aluminium chloride ([bmim]Cl‐AlCl₃). The results indicate that ESR spectra observed are due to polycyclic aromatic radical cations formed from their parent hydrocarbons. ESR spectrum of spin adduct is obtained in an ionic liquid system composed of [bmim]Cl‐AlCl₃. In acidic solution the ¹⁴N hyperfine coupling constant of 4‐oxo‐TEMPO, 2.15 mT, is appreciably larger due to an adduct formed with AlCl₃.     

Prototype of immunochromatographic assay strips using colloidal CdTe nanocrystals as biological luminescent label

Colloidal semiconductor nanocrystals have attracted considerable attention as a novel biological luminescent label. The bioinorganic conjugates of luminescent CdTe nanocrystals and protein, including CdTe/BSA (bovine serum albumin) and CdTe/MAB (mouse monoclonal antibody against hepatities B surface antigen), were formed via electrostatic/coordination self-assembly. Pure CdTe nanocrystals, CdTe/BSA and CdTe/MAB were used in the immunochromatographic assay experiments, respectively. And the results indicated that CdTe nanocrystals could be used and developed as a novel label with good stability, high sensitivity and facile determination of several analytes in immunochromatographic assay strips.     

Two organometallic fragments inclusioned in a 1,3-alternate calix[4]arene tetraphosphane: evidence for transition metal-arene interaction through the cavity

The preparation of an 1,3-alternate calix[4]arene tetraphosphane ligand, 25,26,27,28-tetrakis{2-(diphenylphosphino)ethoxy}calix[4]arene (4), is described. Ligand 4 is obtained in four steps in 17% overall yield. Reaction of 4 with AgBF4 produced the encapsulated two silver complex [Ag2{(P,P,P,P)-tetraphencalix[4]arene}](BF4)2. The solid-state structure shows that the encapsulated silver undergoes a substantial pi-interaction by two opposite arene rings. Rhodation of 4 employing [Rh(cot)2]BF4 yielded the encapsulated complex with a bent coordination mode. Two organometallic fragments inclusioned inside a 1,3-alternate calix[4]arene tetraphosphane was also achieved by the reaction of 4 with [PtH(PPh3)2 (thf)]+. Full characterization includes X-ray structural studies of compounds 4-6.     

New Dammarane Monodesmosides from the Acidic Deglycosylation of Notoginseng‐Leaf Saponins

Three new dammarane monodesmosides, named notoginsenosides Ft₁ ( 1 ), Ft₂ ( 2 ), and Ft₃ ( 3 ), together with three known ginsenosides, were obtained from a mild acidic hydrolysis of the saponins from notoginseng (Panax notoginseng (Burk .) F. H. Chen ) leaves. Their structures were elucidated to be (3β,12β,20R)‐12,20‐dihydroxydammar‐24‐en‐3‐yl O‐β‐D ‐xylopyranosyl‐(1 → 2)‐O‐β‐D ‐glucopyranosyl‐(1 → 2)‐β‐D ‐glucopyranoside ( 1 ), (3β,12β)‐12,20,25‐trihydroxydammaran‐3‐yl O‐β‐D ‐xylopyranosyl‐(1 → 2)‐O‐β‐D ‐glucopyranosyl‐(1 → 2)‐β‐D ‐glucopyranoside ( 2 ), and (3β,12β,24ξ)‐12,20,24‐trihydroxydammar‐25‐en‐3‐yl O‐β‐D ‐xylopyranosyl‐(1 → 2)‐O‐β‐D ‐glucopyranosyl‐(1 → 2)‐β‐D ‐glucopyranoside ( 3 ), by means of spectroscopic evidences. The known ginsenosides Rh₂ and Rg₃ 4 – 6 were obtained as the major products from this acidic deglycosylation.     

Pinkment: a synthetic platform for the development of fluorescent probes for diagnostic and theranostic applications

Reaction-based fluorescent-probes have proven successful for the visualisation of biological species in various cellular processes. Unfortunately, in order to tailor the design of a fluorescent probe to a specific application (i.e. organelle targeting, material and theranostic applications) often requires extensive synthetic efforts and the synthetic screening of a range of fluorophores to match the required synthetic needs. In this work, we have identified Pinkment-OH as a unique “plug-and-play” synthetic platform that can be used to develop a range of ONOO⁻ responsive fluorescent probes for a variety of applications. These include theranostic-based applications and potential material-based/bioconjugation applications. The as prepared probes displayed an excellent sensitivity and selectivity for ONOO⁻ over other ROS. In vitro studies using HeLa cells and RAW 264.7 macrophages demonstrated their ability to detect exogenously and endogenously produced ONOO⁻. Evaluation in an LPS-induced inflammation mouse model illustrated the ability to monitor ONOO⁻ production in acute inflammation. Lastly, theranostic-based probes enabled the simultaneous evaluation of indomethacin-based therapeutic effects combined with the visualisation of an inflammation biomarker in RAW 264.7 cells.

Pinkment, a resorufin based ONOO⁻ selective and sensitive ‘plug and play’ fluorescence-based platform for in vitro and in vivo use, enables facile functionalisation for various imaging and theranostic applications.     

Stereodivergent and regioselective synthesis of 3,4-cis- and 3,4-trans-pyrrolidinediols from alpha-amino acids

[reaction: see text] Highly stereodivergent Woodward-Prevost reaction applied to iodoacetates derived from homochiral alpha-amino acids afforded enantiopure 3,4-cis- and 3,4-trans-pyrrolidinediol derivatives, with control over the protecting group, allowing for differential protection.     

熔融LiCL中的Voronoi多面体

分子动力学计算表明,在熔融LiCl中存在与组分离子尺寸相当的微观空孔。微观空孔的分布规律对理解系统的扩散系数、电导系数、粘度、压缩率和热膨胀系数等都有重要意义,它们与自由体积模型中的自由体积也有密切的关系。     

Synthesis and Crystal Structure of Organocobalt(III) Complexes with Secondary Alkyls or Bulky Schiff Base Equatorial Ligands

Alkylcobalt(III) Schiff base B(12) model complexes with secondary alkyls or a bulky diamine in the equatorial position were synthesized and characterized. Structures have been first determined by X-ray diffraction analysis for i-C(4)H(9)Co(salen)(gamma-pic) (I), n-C(3)H(7)Co(salen)(gamma-pic) (II) and C(2)H(5)Co(SB) (III), where salen = N,N'-ethylenebis(salicylideneamine) dianion; SB = 1,1,2,2-tetramethyl-N,N'-ethylenebis(salicylideneamine) dianion, gamma-pic = gamma-picoline. Crystal data for I (CoC(26)N(3)O(2)H(30)): space group P2(1)/c with a = 6.661(5) ?, b = 18.612(2) ?, c = 19.533(3) ?, beta = 98.93(1) degrees, V = 2392.10 ?(3), D(calcd) = 1.320 g.cm(-3), Z = 4, and R = 0.048 for 4469 measured reflections. Crystal data for II (CoC(25)N(3)O(2)H(28)): space group P2(1)/c, a = 9.609(6) ?, b = 19.169(8) ?, c = 12.995(9) ?, beta = 106.9(7) degrees, V = 2290.4 ?(3), D(calcd) = 1.332 g.cm(-1), Z = 4, and R = 0.048 for 4358 measured reflections. Crystal data for III (CoC(22)N(2)O(2)H(27)): space group P2(1)/c, a = 8.318(3) ?, b = 21.579(2) ?, c = 11.572(2) ?, beta = 93.35(1) degrees, V = 2073.7 ?(3), D(calcd) = 1.314 g.cm(-1), Z = 4, and R = 0.060 for 3954 measured reflections. The crystal structure data reveal that complexes I and II display six-coordinate octahedral geometry; their Co-C, Co-N bond lengths, as well as the Co-C-C angles, are very close to those in 5'-deoxyadenosylcobalamin. Complex III is one of the very few compounds having five-coordinate square pyramidal geometry and observed instability of the Co-C bond.     

Fast determination of the tin content in cassiterite ores by photon activation method

Photon activation analysis has been success-fully applied to the fast and non-destructive analysis of tin in cassiterite ores based on the 159.7 keV gamma line of^123mSn produced in the¹²⁴Sn/γ, n/^123mSn reaction. In order to improve the accuracy of analytical results, corrections for self-absorption and pile-up effects were performed. Under typical conditions /15 μA electron beam current, 15 MeV bremsstrahlung energy, 5 min irradiation time and 10 min measurement/ the sensitivity of the analysis is 10 ppm. The proposed method can be used for routine analysis of tin in geological samples.