An efficient conversion of berberine into a rhoeadine via an indenobenzazepine

Treatment of ketoaziridine $\text{4}$ with aqueous formaldehyde gives the unusual bridged indenobenzazepine derivative $\text{6}$ whose reduction uith sodium cyanoborohydride produces trans ketol $\text{8}$. In the presence of hydrochloric acid, $\text{8}$ undergoes irreversible conversion to the more stable cis ketol $\text{10}$. Periodate oxidation of $\text{8}$ supplies γ-laotone $\text{11}$. NaBH₄ reduction of $\text{11}$ followed by acid treatment affords δ-lactone $\text{12}$ which upon reduction and O-methylation furnishes cis rhoeadine analog $\text{14}$.     

Konyanin: a new lignan from hapuophyllum vulcaniclm

Konyanin ($\text{1}$), obtained from $\text{Haplophyllum vulcanicum}$ (Rutaceae), is the first known 1,4-dihydroarylnaphthalene lignan in which the lactone carbonyl is bonded to C-3 rather than to C-2. Detailed NMR spectral data have been complied for the accompanying lignans (-)-kusunokinin ($\text{5}$) and diphyllin ($\text{7}$).     

酶促聚合和原子转移自由基聚合“一锅法”合成嵌段聚合物及其性能表征

用酶促聚合和原子转移自由基聚合相结合的"一锅法"合成了聚甲基丙烯酸正丁酯嵌段聚10-羟基癸酸[PBMA-b-P(10-HD)],通过核磁共振(1H NMR)、傅里叶红外光谱(FTIR)和凝胶渗透色谱(GPC)对其结构以及分子量与其分子量分布进行了表征,并通过动态光散射仪(DLS)和原子力显微镜(AFM)对聚合物在水溶液中的性质进行了研究.所得嵌段聚合物纳米粒子呈球形结构,平均直径为135 nm左右.     

The First Principles Investigations of the Thermoelectric Properties of GaN with p- and n-Type Doping

We investigate the thermoelectric properties of GaN with p-and n-type doping by the first principles calculation and the semi-classical Boltzmann theory. We find that the power factors (S2σof p-type GaN (-3500 W/mK2) is about twice that of the n-type (-1750 W/mK2), which indicates the thermoelectric properties of p-type GaN would be better. Thermal conductivity of GaN crystal decreases rapidly as the temperature increases, but it is still too large for thermoelectric applications. The figure of merit (ZT) estimated at 1500 K is 0.134 for p-type GaN crystal and 0.062 for the n-type.     

Theoretical Investigations of Nonlinear Optical Properties of Transition Metal Cluster Anions

In the framework of density functional theory （DFT）, the electronic excitations and nonlinear optical （NLO） properties of six binuclear transition metal cluster anions with the formula of [Ch2M-（μ-Ch）2-M＇CN]^2- （M = Mo, W; Ch = S, Se; M＇ = Cu, Ag） have been systemically investigated at both cases of gas phase and DMF solution. The obtained electronic absorption spectra reveal that the element replacements of metals M and ligands Ch have significant influence on the absorptions, especially on the low-lying ones. In addition, the transitions of μ-Ch→M are dominant for the low-lying excitations, whereas the transitions of M＇→M as well as Ch→M are mainly responsible for the higher excitations. The calculated molecular first and second hyperpolarizabilities present the remarkable element substitution and solvent effects. The analyses show that the transitions involving μ-Ch→M charge transfer make the critical contributions to the first hyperpolarizability t, and that the charge transfers from the moieties of MCh4 to M＇CN as well as those of μ-Ch→M and M＇→M are responsible for the second hyperpolarizability y. Moreover, the introduction of solvent leads to the results that the transitions within the moieties of MCh4 and M＇CN make larger contributions to the hyperpolarizability, especially to γ.     

TDDFT studies of electronic structure and first hyperpolarizability of terta-nuclear cubane-like transition metal clusters

The TDDFT method is first applied in a series of tetra-nuclear transition metal clusters studies for nonlinear optical properties. The results indicate that the charge transfer inside the metal core [MCu3X4] (M=W, Mo; X=S, O, Cl, Se, Br) makes contribution to the optical nonlinearity. It is possible to enhance the hyperpolarizability by substituting the ligands of the clusters.     

Revised structure for fumarofine,an indenobenzazepine type alkaloid

Fumarofine is not a spirobenzylisoquinoline. Rather, it is the first know reduced indenobensazepine alkaloid, and possesses the cis B/C fused structure $\text{7}$. Rearrangement of synthetic spirobensylisoquinoline $\text{12}$ using methanesulfonyl chloride furnished indenobensazepine $\text{14}$. Osmium tetroxide oxidation of $\text{14}$ gave cis-glysol $\text{15}$. O-Methylfumarofine ($\text{8}$) was then obtained through pyridinium chlorochromate oxidation of $\text{15}$.     

The photochemistry of proaporphines: a new route to the aporphines

Proaporphines undergo light catalyzed rearrangement. Pakistanamine ($\text{1}$) is thus converted into lumipakistanine ($\text{2}$), while pronuciferine ($\text{7}$) and N-acetylnorpronuciferine ($\text{8}$) afford the corresponding C-9 hydroxylated aporphines $\text{9}$ and $\text{10}$. Possible biogenetic schemes for the formation of C-8, C-9-, and C-8,9-substituted aporphines are presented.     

相对论性核与乳胶(Ag)碰撞中灰粒子的系统研究 *

用描写相对论性核 核碰撞的LUCIAE模型和相应的事件产生器系统地研究了 1 4.6 ,6 0和 2 0 0AGeV的O核、2 0 0AGeV的Si和S核以及 1 1 .6AGeV的Au核与乳胶 (Ag)碰撞中灰粒子产生的平均多重数、多重数分布以及角分布 3个物理量同入射能量、射弹质量及碰撞中心度间的关系 ,还研究了再散射在灰粒子产生机制中的作用 .LUCIAE的这些研究结果与相应的EMU0 1乳胶实验结果都相一致 .     

NUCLEAR CHARGE DISPERSION OF FRAGMENTS IN HIGH ENERGY PROTON-NUCLEUS COLLISION

The charge dispersion of fragments in high energy p+Cu,Kr and Xe reactions are calculated by statistical model and Monte Carlo technique.The corresponding data are reproduced quite well.It is shown that the charge dispersions are all nearly gaussian.The mass dependence of the most probable fragment charge reflects the rest target memory effect.