Total synthesis of kendomycin: a macro-C-glycosidation approach

Kendomycin, also known as (-)-TAN 2162, is a novel polyketide-derived ansamycin isolated from Streptomyces sp., which exhibits potent antagonist and agonist activities at the endothelin and calcitonin receptors, respectively. This bacterial metabolite also possesses a strong antibiotic activity against a range of gram-positive and -negative bacteria and cytostatic effects on the growth of human cancer cell lines. When a novel macroglycosidation reaction is employed as the key step, the first enantioselective total synthesis of kendomycin has been accomplished. A Friedel-Crafts-type ring closure of the acyclic precursor containing tetrahydropyran and benzofuran moieties produces the macrocycle as a single stereoisomer in good yield, thus establishing the aryl C-glycosidic linkage of the ansa core. This reaction requires a phenolic glycosyl acceptor and appears to proceed through a rapid O-glycosidation followed by a slow rearrangement to an aryl C-glycoside. The requisite secomacrocycle is prepared by the Pd(0)-catalyzed B-alkyl Suzuki-Miyaura cross-coupling of two subunits, which in turn can be expeditiously assembled from readily available building blocks in a modular fashion.     

K对Mn—Co—O的结构及氧化活性的影响

利用XRD,TPD,TFD-MS及催化氧化反应等实验技术,研究了K对Mn-Co-O的结构及氧化活性的影响。XRD结果表明,Mn-Co-O系已形成反尖晶石型的MnCo_2O_4结构;K-Mn-Co-O系中除MnCo_2O_4型结构外,还有新相KMnO_2存在。根据O_2的TPD-MS及吡啶的TPD结果,Mn-Co-O中添加适量的K能提高供氧活性和增加供氧数目,但酸中心数目减少,强度降低。K对Mn-Co—O催化剂氧化活性的影响随反应物分子结构的不同而异,对乙酸乙脂、苯甲酰氯等极性有机物的完全氧化反应,K能提高氧化活性,但对苯、正己烷等非极性有机物的完全氧化反应,K使其活性降低。     

Semiclassical approach to collision-induced emission in the presence of intense laser radiation: An aspect in the study of cooperative chemical and optical pumping

Collion-induced emission in molecular systems in an intense laser field is studied using the semiclassical approach, with a view towards cooperative chemical and optical pumping in laser production. The formalism is developed with the electronic-field representation, which treats collision and radiative interaction on the same footing. Electronic-field surfaces can be regarded as forming spectra for spontaneous emission; and particular emission events can be accounted for by propagating classical trajectories on emission electronic-field surfaces. Pre-emission loss from the excited state is dealt with by propagating classical trajectories on a loss surface along a complex contour of emission branch points. This loss surface is derived on the basis of localized radiative couplings between electronic-field states and provides a framework to treat the general problem of discrete state-continuum interactions. The formalism is applied to a two-state, collinear exponential model to compute S-matrix elements and transition probabilities between asymptotic states.     

Fibrous crystalline hydrogels formed from polymers possessing a linear poly(ethyleneimine) backbone

Novel thermoreversible physical hydrogels formed from polymers with linear and star architectures possessing a linear poly(ethyleneimine) (PEI) backbone have been investigated. The hydrogelation occurred simply upon natural cooling of hot aqueous solutions of PEIs to room temperature. The X-ray diffraction and differential scanning calorimetry measurements for the resultant hydrogels unambiguously indicated that the hydrogelation originated from the formation of dihydrate crystalline structures of PEI. These crystalline hydrogels are structurally unique and hierarchical. Microscopic images revealed that the morphologies of the crystalline hydrogels depend on their molecular architectures. The linear PEI resulted in branched fibrous bundles organized by unit crystalline nanofibers with a width of ca. 5-7 nm. The six-armed star with benzene ring core produced fanlike fibrous bundles while the four-armed star with porphyrin core assembled into asterlike aggregates. The critical concentration of gelation (C(G)) was low (about 0.2 approximately 0.3%) and the thermoreversible gel-sol transition temperatures (T(G)) were controllable from approximately 43 to approximately 79 degrees C. The hydrogels formed in the presence of the various aqueous additives including organic solvents, hydrophilic polymers, physical cross-linker, chemical cross-linker, and base enabling modification and functionalization during synthesis. The mechanical properties of the hydrogels could be improved by chemical cross-linking of preformed hydrogels by glutaraldehyde. Physically and physical/chemical cross-linked hydrogels served as excellent template roles in biomimetic silicification, which produced silica-PEI hybrid powder or monolith constructed by nanofibers.     

Synthesis of 2‐Dihydrooxadiazolinyl Chromones

Reactions of the substituted 2‐formyl chromones with aroylhydrazines gave corresponding 2‐(aroylhydrazonomethylidyne) chromones. Then 2‐(3′‐acetyl‐5′‐aryl‐2′,3′‐dihydro‐1′,3′,4′‐oxadiazol‐2′‐yl) chromones were prepared by these 2‐(aroylhydrazonomethylidyne) chromones under refluxing with Ac₂O. All target compounds were characterized through elemental analysis and IR, ¹H NMR, MS.     

Synthesis and VUV-UV spectroscopic properties of rare earth borosilicate oxyapatite: RE5Si2BO13:Ln (RE=La, Gd, Y; Ln=Eu, Tb)

Three rare earth borosilicate oxyapatites, RE₅Si₂BO₁₃ (RE=La, Gd, Y), were synthesized via wet chemical method, of which RE₅Si₂BO₁₃ (RE=Gd, Y) were first reported in this work. In the three oxyapatites, [BO₄] and [SiO₄] share the [TO₄] tetrahedral oxyanion site, and RE³⁺ ions occupy all metal sites. The differential scanning calorimetry-thermo gravimetry measurements and high temperature powder X-ray diffraction pattern revealed a vitrification process within 300-1200 °C, which was due to the glass-forming nature of borosilicates. From the VUV excitation spectra of Eu³⁺ and Tb³⁺ in RE₅Si₂BO₁₃, the optical band gaps were found to be 6.31, 6.54 and 6.72 eV for RE₅Si₂BO₁₃ (RE=La, Gd, Y), respectively. The emission and excitation bands of Eu³⁺ and Tb³⁺ are discussed relating with their coordination environments. Among the three hosts, Y₅Si₂BO₁₃ would be the best for Eu³⁺ and Tb³⁺-doped phosphors.     

能动抛光磨盘的变形实验研究

 能动抛光磨盘实时产生不同的表面变形，在对大口径非球面光学元件进行精磨和抛光时实现与工件表面良好的大尺寸吻合，可以消除传统光学加工采用小尺寸磨头时带来的高频残余误差并提高加工效率。以加工直径1.3m左右，F/2的抛物面光学元件为例，对能动磨盘在不同离轴度时能够产生的变形进行了计算和实验。结果表明，能动磨盘能够以较高精度产生旋转对称或非对称的抛物面形状。对能动磨盘产生变形后的残余误差进行了分析。     

粉末压片-X荧光光谱法测定过磷酸钙中硫含量

硫是过磷酸钙中重要营养指标之一,为准确快速测定过磷酸钙中硫的含量,试验采用粉末压片-X荧光光谱法,将过磷酸钙试样充分干燥后研磨至粒度小于74 μm,采用硼酸镶边,在压力18 Mpa条件下保压30 s,制成样片。通过在过磷酸钙样品中添加不同质量的纯物质硫酸钙（质量分数范围1.52 %～17.21 %）,经过专用混匀设备混合均匀后,与试样压片相同条件下压制标准样片,作为过磷酸钙中硫的标准样品,建立硫标准曲线,曲线线性相关系数R2为0.9995,采用经验系数法校正干扰,建立了粉末压片-波长色散X射线荧光光谱法测定过磷酸钙中硫含量的方法, 方法检出限为0.002 %。对3个不同硫含量的过磷酸钙样品采用本实验方法重复测量7次,RSD在1.4 %~3.1 %,方法精密度性好,同时用高温燃烧红外光谱法和电感耦合等离子发射光谱法对比,三者测量结果相对极差小于2.0 %,测量结果无显著性差异。此方法不需要对样品进行熔融或溶解,样品制备简单,数据准确度和稳定性好,分析效率高,适合大批量样品中硫的测定。