Two new triterpenoid glycosides from the stems of Camellia oleifera Abel

Two new oleanane-type triterpenoid glycosides, 3-O-β-D-xylopyranosyl-(1→2)-α-L-arabinopyranosyl-(1→3)-[β-D-glucuronopyranosyl-(1→2)]-β-D-glucuronopyranosyl-22α-angeloyloxyolean-12-ene-15α,16α,28-triol(1) and 3-O-β-D-xylopyranosyl-(1→2)-α-L-arabinopyranosyl-(1→3)-[β-D-glucuronopyranosyl-(1→2)]-β-D-glucuronopyranosyl-21β-acetyl-22α-angeloyloxyolean-12-ene-16α,28-diol (2) were isolated from the stems of Camellia oleifera Abel. Their structures were elucidated by means of spectroscopic methods and chemical evidence. The cytotoxic activities of compounds 1–2 were evaluated against five human tumour cell lines (HCT-8, BGC-823, A5049, and A2780). Compounds 1–2 showed cytotoxic activity against five human cancer cell lines, with IC₅₀ values ranging from 3.15 to 7.32 μM.     

Hydrothermal synthesis, structures, and photoluminescent properties of benzenepentacarboxylate bridged networks incorporating zinc(II)-hydroxide clusters or zinc(II)-carboxylate layers

The first coordination compounds of partially or wholly deprotonated benzenepentacarboxylic acid (H5L) were synthesized in the presence or absence of auxiliary 2,2'-bipyridyl (2,2'-bpy) and 1,10-phenanthroline (phen) ligands, and their crystal structures and photoluminescent properties were characterized. Their formulas are [Zn6(mu3-OH)2(L)2(H2O)6]n (1), [Zn5(mu3-OH)2(HL)2(2,2'-bpy)2]n (2), [Zn2(HL)(phen)2(H2O)2]n (3), and [Zn5(L)2(phen)4(H2O)3]n.2nH2O (4). Both 1 and 2 are three-dimensional (3D) zinc(II)-hydroxide cluster based coordination frameworks. 1 contains distorted chairlike hexanuclear Zn6(mu3-OH)2 cluster units as secondary building blocks. Each Zn6(mu3-OH)2 unit connects six others through the three-connected nodes of L5- ligands into a 3D rigid and condensed coordination network, whereas in 2, each pentanuclear Zn5(mu3-OH)2 unit connects the other six ones through the three-connected [HL]4- nodes into a 3D network in the simple cubic packing mode. 3 has two-dimensional (2D) Zn(II)-carboxylate supramolecular layers constructed from a one-dimensional (1D) coordination chain structure by hydrogen bonds of the water and mu5-[HL]4- bridges, whereas 4 has 2D coordination layers composed of Zn(II) and mu8-L5- bridges. The adjacent coordination assemblies in 3 and 4 are further extended by hydrogen bonds and pi...pi interactions into 3D supramolecular architectures. 1-4 are photoluminescent active materials, and their photofluorescent properties are closely related to their intrinsic structure arrangements.     

黑磷各向异性拉曼光谱表征及电学特性

采用机械剥离法制备出层状黑磷,通过微纳加工制备0°—360°四对对称电极并以黑磷作为沟道材料的背栅型场效应晶体管,对层状黑磷的拉曼光谱及其场效晶体管的电学输运特性进行了研究.偏振拉曼图谱结果表明,黑磷的3个特征峰强度随偏振角改变呈现180°周期变化;不同角度电极源漏电流表明,黑磷在0°(180°)扶手椅方向附近呈现最大源漏电流,均表现出黑磷各向异性特性.另外,不同电极角度栅压-源漏电流转移特性曲线表明其在45°(225°)和90°(270°)方向呈现微弱双极性,在0°(180°)和135°(315°)方向呈现空穴型输运特性.     

Generation of multiparticle three-dimensional entanglement state via adiabatic passage

A scheme is proposed for generating a multiparticle three-dimensional entangled state by appropriately adiabatic evolutions, where atoms are respectively trapped in separated cavities so that individual addressing is needless. In the ideal case, losses due to the spontaneous transition of an atom and the excitation of photons are efficiently suppressed since atoms are all in ground states and the fields remain in a vacuum state. Compared with the previous proposals, the present scheme reduces its required operation time via simultaneously controlling four classical fields. This advantage would become even more obvious as the number of atoms increases. The experimental feasibility is also discussed. The successful preparation of a high-dimensional multiparticle entangled state among distant atoms provides better prospects for quantum communication and distributed quantum computation.     

CTMAB-Al复合改性蒙脱石的表征及应用

以钠基蒙脱石（Na-MMT）为原料,用十六烷基三甲基溴化铵（CTMAB）预先改性,再用羟基铝柱撑液改性,制备不同CTMAB用量的复合改性蒙脱石（CTMAB-Al-MMT）,用于同时吸附水中苯酚和镉离子.复合改性蒙脱石用X射线衍射（XRD）、傅里叶红外光谱（FTIR）表征.结果表明,CTMAB和羟基铝阳离子已有效进入蒙脱石层间,层间距随CTMAB加载量增大而增加,吸附率随CTMAB加载量增大有明显提高.当复合改性蒙脱石用量为0.1g/50mL,吸附时间2h,pH=10时,苯酚吸附率达92.1％,镉离子吸附率达98.8％.     

有机改性蒙脱石的表征及去除污水COD的应用

以钠基蒙脱石(Na-MMT)为原料,十六烷基三甲基溴化铵(CTAB)为改性剂,水相合成法制备了有机改性蒙脱石(OMMT),用于吸附污水中有机污染物,降低污水化学需氧量(COD)值。所制备的有机改性蒙脱石经XRD、FTIR表征,结果显示CTAB已经插入蒙脱石层间,层间距有明显增大,d(001)从未改性前的1.53nm增大到2.53nm。水样COD测定结果表明,将其用于COD=503.8mg/L的污水,pH=7,有机改性蒙脱石用量1.0g/100mL,吸附时间1h时,可使COD降至46.3mg/L,COD去除率达90.8%。     

Intramolecular ipso-halocyclization of 4-(p-unsubstituted-aryl)-1-alkynes leading to spiro[4,5]trienones: scope, application, and mechanistic investigations

A new, general method for the synthesis of spiro[4,5]trienones is described by the intramolecular ipso-halocyclization of 4-(p-unsubstituted-aryl)-1-alkynes. In the presence of halide electrophiles, a variety of 4-(p-unsubstituted-aryl)-1-alkynes underwent the intramolecular ipso-halocyclization with water smoothly, affording the corresponding halo-substituted spiro[4,5]trienones in moderate to good yields. The obtained spiro[4,5]trienones can be applied in constructing the azaquaternary tricyclic skeleton via Pd-catalyzed Heck reaction. Notably, the prepared spiro[4,5]trienones and azaquaternary tricycles are of importance in the areas of pharmaceuticals and agrochemicals. The mechanism of the intramolecular ipso-halocyclization reaction is also discussed according to the (18)O-labeling experiments and DFT calculations.     

阻变存储器复合材料界面及电极性质研究

采用基于密度泛函理论的第一性原理对比研究了Cu（111）/HfO₂（001）,Cu（111）/HfO₂（010）,Cu（111）/HfO₂（100）三种复合材料界面模型的失配率、界面束缚能、电荷密度、电子局域函数以及差分电荷密度. 计算结果表明：Cu（111）/HfO₂（010）失配率最小,界面束缚能最大,界面体系相对最稳定;对比电荷密度及电子局域函数图显示,只有HfO₂（010）方向形成的复合材料体系出现了垂直Cu电极方向完整连通的电子通道,表明电子在此方向上具有局域性、连通性,与阻变存储器（RRAM）器件导通方向一致;差分电荷密度图显示,Cu（111）/HfO₂（010）复合材料体系界面处存在电荷密度分布重叠的现象,界面处有电子的相互转移、成键的存在;进一步计算了Cu（111）/HfO₂（010）体系距离界面不同位置的间隙Cu原子形成能,表明越靠近界面Cu原子越容易进入HfO₂ 体内,在外加电压下易发生电化学反应,从而导致Cu导电细丝的形成与断裂. 研究结果可为RRAM存储器的制备及性能的提高提供理论指导和设计工具. 关键词： 阻变存储器 复合材料 界面 电子通道     

一类具有偏差变元的Liénard型方程的周期解

利用重合度理论研究了一类具偏差变元的Liénard型方程x″+f1(x)|x′|2n+f2(t,x(t),x(t-0τ(t)))x′+g(t,x(t-1τ(t)))=p(t).获得了该方程存在ω-周期解的若干新结论,改进推广了有关文献中的已有结果.     

Theoretical study on the mechanism of cycloaddition reaction between dimethyl germylidene and formaldehyde

The cycloaddition mechanism of the reaction between singlet dimethyl germylidene and formaldehyde has been investigated with MP2/6-31G* method, including geometry optimization and vibrational analysis for the involved stationary points on the potential energy surface. The energies of the different conformations are calculated with CCSD (T)//MP2/6-31G* method. From the potential energy profile, we predict that the cycloaddition reaction between singlet dimethyl germylidene and formaldehyde has two dominant reaction pathways. First dominant reaction pathway consists of three steps: (1) the two reactants (R1, R2) firstly form an intermediate INT1a through a barrier-free exothermic reaction of 43.0 kJ/mol; (2) INT1a then isomerizes to a four-membered ring compound P1 via a transition state TS1a with an energy barrier of 24.5 kJ/mol; (3) P1 further reacts with formaldehyde(R2) to form a germanic heterocyclic compound INT3, which is also a barrier-free exothermic reaction of 52.7 kJ/mol; Second dominant reaction pathway is as following: (1) the two reactants (R1, R2) firstly form a planar four-membered ring intermediate INT1b through a barrier-free exothermic reaction of 50.8 kJ/mol; (2) INT1b then isomerizes to a twist four-membered ring intermediate INT1.1b via a transition state TS1b with an energy barrier of 4.3 kJ/mol; (3) INT1.1b further reacts with formaldehyde(R2) to form an intermediate INT4, which is also a barrier-free exothermic reaction of 46.9 kJ/mol; (4) INT4 isomerizes to a germanic bis-heterocyclic product P4 via a transition state TS4 with an energy barrier of 54.1 kJ/mol.