Design and Synthesis of Two Aromatic Amines with Dendritic Structure

The design and synthesis of two aromatic amines with dendritic structures, i.e. 3,4,5‐tribenzyloxyaniline (3,4,5‐G₁‐NH₂) and 2,5‐dibenzyloxyaniline (2,5‐G₁‐NH₂), were conducted. A coupling reaction of three or two equivalents of benzyl bromide to one equivalent of methyl hydroxybenzoate generated methyl 3,4,5‐tribenzyloxybenzoate (3,4,5‐G₁‐COOCH₃), methyl 2,5‐dibenzyloxybenzoate (2,5‐G₁‐COOCH₃) and 2,6‐dibenzyloxybenzoate (2,6‐G₁‐COOCH₃) in high yields. All G₁‐COOCH₃ derivatives were studied by X‐ray analysis. The results show that these dendrons have sufficient volume to be used as the fine ligands for certain catalysts. The amide intermediates (benzamide, G₁‐CONH₂) were obtained by reaction between ammonia and G₁‐COOCH₃. Interestingly, 2,6‐dibenzyloxybenzamide (2,6‐G₁‐CONH₂) can not be prepared in the same condition, which may be due to the overlarge steric block. Sodium hypochlorite was an effective oxidant to generate methyl carbamates G₁‐ NHCO₂CH₃.     

Chiral bifunctional squaramide catalyzed asymmetric tandem Michael-cyclization reaction: efficient synthesis of optically active 2-amino-4H-chromene-3-carbonitrile derivatives

We have developed an efficient bifunctional squaramide catalyst for the asymmetric tandem Michael addition–cyclization of malononitrile to functionalized nitroolefins. This organocatalytic asymmetric reaction provides convenient and valuable access to highly functionalized 2-amino-4H-chromene derivatives, which possess important biological activities, in good yields with moderate to high enantioselectivities (up to 95% ee).     

Organocatalyzed enantioselective michael addition of 2-hydroxy-1,4-naphthoquinone to β,γ-unsaturated α-ketophosphonatesθ

By employing a cinchonine-based thiourea as catalyst, highly enantioselective Michael addition reactions of 2-hydroxy-1,4-naphthoquinone to β,γ-unsaturated α-ketophosphonates were realized. The reaction afforded the corresponding β-substituted carboxylates in excellent yields with high levels of enantioselectivities (94->99% ee) upon quenching the generated parent structures with DBU and MeOH as a second nucleophile.     

Study of Phase Separation of Poly(N-isopropylacrylamide-co-styrene) Aqueous Solutions with Rayleigh Scattering Technique

A thermally sensitive copolymer, poly(N‐isopropylacrylamide‐co‐styrene) [P(NIPAM‐co‐St)] (M_n?9.5×10⁵ g/mol and M_w/M_n?1.51) was synthesized by soap‐free emulsion polymerization. The phase separation of the copolymer in water was investigated by Rayleigh scattering (RS) technique. The RS spectra revealed the transition of molecular conformation and the aggregation of molecular chains in the course of phase separation. The coil‐to‐globule and globule‐to‐coil transitions of P(NIPAM‐co‐St) chains were found in one heating‐and‐cooling cycle. By means of Avrami formula, apparent activation energy of phase separation of P(NIPAM‐co‐St) aqueous solutions was estimated. Moreover, a model was proposed to describe the phase separation process.     

基于PCE方法的翼型不确定性分析及稳健设计简

由于能够获得一个既经济又对参数变化不敏感的设计结果,稳健型设计在工程设计中备受关注. 不确定性分析是稳健型设计的关键. 因此研究了基于混沌多项式的不确定性分析方法,并将其与CFD 方法结合,对计算空气动力学设计中的不确定性影响进行了量化分析. 首先以RAE2822 翼型为算例,对其跨音速马赫数不确定影响进行了分析,研究了多项式阶次对计算的影响,分析了平均流场和方差. 接着结合超临界翼型的马赫数稳健型设计验证了混沌多项式方法在稳健型设计中的有效性. 优化结果表明,稳健型优化后的翼型阻力系数明显降低,同时对于马赫数的敏感性显著减小. 通过分析表明混沌多项式方法能够大幅提高稳健型优化设计效率,能很好地应用于气动稳定性设计.     

Asymmetric Ring-Opening of Cyclohexene Oxide with Mercaptan (Thiophenols) Catalyzed by Chiral Schiff Base/Ti(OPr- i ) 4 or (−)-(S)-Binaphthol/Ti(OPr- i ) 4

New chiral Schiff base ligands 1-4 were synthesized starting from (+)-camphor and (+)-1-(4-nitrophenyl)-2-amino-1,3-propanediol, and their application in asymmetric ring-opening of cyclohexene oxide using mercaptan (thiophenols) as nucleophiles was investigated. The aymmetric ring-opening of cylohexene oxide catalyzed respectively by chiral Schiff bases 1-4 /Ti(OPr- i ) 4 and ( m )-(S)-1,1'-binaphthalene-2,2'-diol 5 /Ti(OPr- i ) 4 complex afforded the corresponding chiral g -hydroxysulfides 6-10 in lower to good yield with lower to moderate ee values. Moreover, the using of ( m )-(S)-1,1'-binaphthalene-2,2'-diol as ligand led to better chiral induction effect.     

基于多质点模型的准球形丝阵参数优化研究

基于多质点薄壳模型对准球形丝阵负载参数进行优化,使得终态等离子体具有预期的内爆特性。通过对丝阵初始位形优化,可以获得期望的终态等离子体壳纵横比,并且终态纵横比对负载初始质量变化不敏感。对于固定电流波形(峰值1.2 MA、上升时间80ns),优化计算了初始丝长度15.4mm的丝阵线质量。结果表明,当丝阵初始线质量约为150μg/cm时,赤道半径为2mm、纵横比为1的终态等离子体壳具有最大动能1.5kJ。同时,还针对不同幅度及上升时间的电流进行优化计算,计算结果表明终态等离子体壳的优化的最高动能与电流峰值平方成正比,与最高动能相应的线质量与电流上升时间平方成正比。     

三角翼大迎角流场结构和气动力特性的数值分析研究

采用数值计算方法对亚音速三角翼纵向及带有小侧滑情况下的流场结构和气动力特性进行了计算。文中给出了三角翼大迎角纵向情况下气动力、机翼前缘分离涡轴线位置和旋涡破裂位置随迎角的变化规律，以及带有横侧小扰动和小侧滑情况下流场结构的非对称性对气动力的影响。计算结果表明与实验结果符合较好。     

Asymmetric synthesis of the C1–C6 portion of the psymberin using an Evans chiral auxiliary

The C1–C6 region of the potent cytotoxic agent psymberin has been synthesized. The key transformations of the synthesis are an auxiliary-controlled addition of a Sn(II)-glycolate enolate to an aldehyde to yield the anti-aldol product and transforming the primary alcohol into a terminal olefin utilizing organoselenium chemistry.     

Fe2+ and Co2+ Improved the Affinities of 7-Hydroxyflavone, Chrysin and Quercetin for Human Serum Albumin In Vitro

Chrysin, 7-hydroxyflavone, and quercetin were studied for their affinities with human serum albumin (HSA) in the presence and absence of Fe²⁺ and Co²⁺. The fluorescence intensities of HSA decrease remarkably with increasing concentration of the tested flavonoids. Chrysin resulted in a blue-shift of the emission line λ _em of HSA from 336 to 330 nm whereas quercetin showed an obvious red-shift of λ _em from 336 to 347 nm. However, the extents of the λ _em shifts induced by flavonoids in the presence of mental ions are much bigger than those of the corresponding systems in the absence of mental ions. Fe²⁺ and Co²⁺ increased the quenching constants of the tested flavonoids for HSA by 12.4–48.1 and 15.0–66.7 %, respectively. The affinities of 7-hydroxyflavone, chrysin and quercetin for HSA increased by about 6.42, 7.38 and 0.62 %, respectively, in the presence of Fe²⁺. Co²⁺ increased the affinities of 7-hydroxyflavone, chrysin, and quercetin for HSA about 8.43, 7.86 and 11.73 %, respectively.