螯形主体分子的设计、包结性能及其在细辛挥发油 有效成分选择分离中的应用

设计了两种新的具有螯形骨架的主体分子反式-1,2-二苯基-1,2-苊二醇(1)和顺式-1,2-二(1'-萘基)-1,2-苊二醇(2),主体(1),(2)可与许多有机小分子化合物形成配位包合物。用IR和粉末XRD表征了主体分子(1)和(2)的包结物,用^1NMR测定了包结物的主客体分子摩尔比：(1)·DMF(1:2),(1)·DMSO(1:2),(1)·THF(1:2),(1)·二氧六环(1:1),(1)·吡啶(1:1),(2)·DMF(1:1)和(2)·DMSO(1:1)。单晶X射线衍射分析了包结物的晶体结构,(1)·DMF：空间群Pnaa,a=0.9377(1)nm,b=1.4351(1)nm,c=4.0463(3)nm;(1)·DMSO：空间群Pbcn,a=1.6278(1)nm,b=1.0751(1)nm,c=1.4980(1)nm;(2)·DMF：P2~1/n,a=0.9796(1)nm,b=1.2377(1)nm,c=2.2344(3)nm,β=93.02(1)°;游离主体(1)：空间群P1,a=1.0461(1)nm,b=1.1213(1)nm,c=1.5496(1)nm,α=81.74(1)°,β=75.71(1)°,γ=89.00(1)°;分析了主体分子的刚性和柔韧性对包结性能的影响。并研究了主体分子(1)选择分离细辛挥发油,将顺甲基异丁香酚从挥发油中分离出来。     

螯形主体分子的设计、包结性能及其在细辛挥发油 有效成分选择分离中的应用

设计了两种新的具有螯形骨架的主体分子反式-1,2-二苯基-1,2-苊二醇(1)和顺式-1,2-二(1'-萘基)-1,2-苊二醇(2),主体(1),(2)可与许多有机小分子化合物形成配位包合物。用IR和粉末XRD表征了主体分子(1)和(2)的包结物,用^1NMR测定了包结物的主客体分子摩尔比：(1)·DMF(1:2),(1)·DMSO(1:2),(1)·THF(1:2),(1)·二氧六环(1:1),(1)·吡啶(1:1),(2)·DMF(1:1)和(2)·DMSO(1:1)。单晶X射线衍射分析了包结物的晶体结构,(1)·DMF：空间群Pnaa,a=0.9377(1)nm,b=1.4351(1)nm,c=4.0463(3)nm;(1)·DMSO：空间群Pbcn,a=1.6278(1)nm,b=1.0751(1)nm,c=1.4980(1)nm;(2)·DMF：P2~1/n,a=0.9796(1)nm,b=1.2377(1)nm,c=2.2344(3)nm,β=93.02(1)°;游离主体(1)：空间群P1,a=1.0461(1)nm,b=1.1213(1)nm,c=1.5496(1)nm,α=81.74(1)°,β=75.71(1)°,γ=89.00(1)°;分析了主体分子的刚性和柔韧性对包结性能的影响。并研究了主体分子(1)选择分离细辛挥发油,将顺甲基异丁香酚从挥发油中分离出来。     

高性能NiCoP基超级电容器电化学性能

采用水热和低温磷化反应两步法,在无添加沉淀剂条件下成功在泡沫镍上合成纳米花状镍钴磷化物(NiCoP/NF)。研究结果表明,镍/钴元素物质的量之比为1∶1时,在1 A·g~(-1)电流密度下,Ni_(1/2)Co_(1/2)P/NF的比容量高达1 276.36 F·g~(-1),在10 A·g~(-1)电流密度下充放电循环3 000次后,比容量保持率为78.23%。此外,以Ni_(1/2)Co_(1/2)P/NF为正极,活性炭(AC)为负极组装的非对称超级电容器(Ni_(1/2)Co_(1/2)P/NF//AC/NF)在725 W·kg~(-1)的功率密度下,能量密度高达36.25 Wh·kg~(-1)。     

3,3,6,6-四甲基-9-对氯苯基-1,8-二氧代-2,3,4,5,6,7-六氢氧杂蒽的合成和晶体结构

标题化合物C2 3H2 5O3Cl是由对氯苯甲醛与 5,5 二甲基 1 ,3环己二酮在乙二醇中反应而得。结构通过单晶X 射线衍射法测定 ,其晶体属于单斜晶系 ,空间群P2 1 /n ,a =6.0 4 8(1 ) ,b =1 9.543(3) ,c =1 7.42 0 (3) ,β =97.2 9(1 )° ,V =2 0 4 2 .2 (6) 3,Mr=384.90 ,Dc=1 2 52 g/cm3,Z =4,μ(MoKα) =2 .0 6cm- 1 ,F(0 0 0 ) =81 6。晶体结构用直接法解出 ,经用全矩阵最小二乘法对原子参数进行修正 ,最终的偏离因子为R =0 .0 39,Rw=0 .0 4 7。X 射线衍射分析表明 :平面 1 (C(8) -C(9) -C(1 9) )与平面 2 (C(1 0 ) -C(1 1 ) -C(1 2 ) )之间的两面角为1 6.2 4° ;平面 1与平面 3(C(7) -C(8) -C(9) )之间的两面角为 1 77.37° ;平面 1与平面 4(C(1 )-C(5) -C(6) )之间的两面角为 98.2 1°;平面 2与平面 3之间的两面角为 1 61 .1 2° ;平面 2与平面 4之间的两面角为 81 .98°;平面 3与平面 4之间的两面角为 79.1 5°     

合成抗孕酮新药RU-486中间体3,3-乙撑二氧-5α,10α及5β,10β-环氧-Δ~(9(11))-雌烯-17α(1-丙炔基)-17β醇的薄层分析

采用薄层色谱成功地分离了 3,3-乙撑二氧 - Δ5(1 0 ) ,9(1 1 ) -雌甾二烯 - 1 7α( 1 -丙炔基 ) - 1 7β醇的环氧化产物 3,3-乙撑二氧 - 5α,1 0α-环氧 -Δ9(1 1 ) -雌烯 - 1 7α( 1 -丙炔基 ) - 1 7β醇 (简称 Iα)和 3,3-乙撑二氧 - 5β,1 0β-环氧 -Δ9(1 1 ) -雌烯 - 1 7α( 1 -丙炔基 ) - 1 7β醇 (简称 Iβ) ,并对 Iα 和 Iβ进行了定性和定量分析 ,其结果在红外谱图、核磁实验中得到验证。     

{[Ag(ATO)~2]ClO~4}~n的制备和分子结构

通过4-氨基-1,2,4-三唑-5-酮(ATO)水溶液与高氯酸银溶液反应,制备了聚高氯酸二(4-氨基-1,2,4-三唑-5-酮)合银(I)。并用X射线衍射、红外光谱和TG-DTG对其进行了结构表征。晶体属三斜晶系,空间群为P1,a=0.7534(1)nm,b=0.8505(1)nm,c=1.0257(1)nm;α=69.47(1)ⅲ,β=72.69(1)ⅲ,γ=86.00(1)ⅲ;V=0.5872(1)nm^3,Z=2,D~c=2.305g/cm^3,F(000)=400;偏离因子R为0.0358。中心银离子表现为较为特殊的三配位。     

Li4Mn5O12包覆对三元正极材料结构和性能的影响

LiNi(1/3)Mn(1/3)Co(1/3)O2具有很高的理论比容量,但是三元正极材料在高电压下长循环时,其表面结构发生较大的衰退,导致电池的循环性能和倍率性能变差。本文采用耐高电压且结构稳定的富锂尖晶石Li4Mn5O(12)包覆LiNi(1/3)Mn(1/3)Co(1/3)O2可以有效改善材料的电化学性能。通过XRD、SEM、XPS和TEM等手段对包覆后的材料进行分析,证实了在LiNi(1/3)Mn(1/3)Co(1/3)O2的表面形成了10nm厚的均匀Li4Mn5O(12)的包覆层;在循环100圈后,包覆后的LiNi(1/3)Mn(1/3)Co(1/3)O2仍具有179.5m Ah/g的放电比容量和88.6%容量保持率,明显高于未包覆的LiNi(1/3)Mn(1/3)Co(1/3)O2的78.3%容量保持率。因此,利用富锂尖晶石Li4Mn5O(12)包覆LiNi(1/3)Mn(1/3)Co(1/3)O2为实现更高能量密度的锂离子电池提供了新的途径。     

亚磺化脱卤研究 VII. 全氟碘代烷与SO~3^-的反应

全氟碘代烷R~FI[R~F=CF~3(CF~2)~5(1a);H(CF~2)~4(1b);H(CF~2)~8(1c);Cl(CF~2)~6(1d);Cl(CF~2)~8(1e)Cl(CF~2)~8(1f);;NaO~3S(CF~2)~20(CF~2)~2(1g);NaO~3S(CF~2)~2O(CF~2)~4(1h)]及α,ω-二碘化物I(CF~2)~nI[n=4(1i);n=6(1j)]与Ce^4^+-亚硫酸氢钠于70℃左右、pH3～4的溶液中反应,形成相应的全氟烷基亚磺酸盐,产率70～85%。全氟氯代烷和全氟溴代烷在同样条件下未能发生反应。     

两个具有相似{V10}狚阴离子骨架的化合物的合成和结构表征

本文描述了两个具有相似阴离子骨架的化合物,犤Na2(H2O)10(NH4)4犦犤V10O28犦(1)和犤Na2(H2O)10(NH4)4犦犤V9MoO28犦(2)。化合物1的阴离子是一个常见的钒十骨架,而化合物2与化合物1是同晶异质体,化合物2的阴离子是混有一个钼原子的钒十骨架。X-射线晶体结构测定表明,这两个化合物均属于三斜晶系,P1珔空间群。晶胞参数分别为化合物1:a=0.86024(4)nm,b=1.04561(5)nm,c=1.12828(4)nm,α=68.833(1)°,β=87.158(1)°,γ=67.065(1)°;化合物2:a=0.86511(3)nm,b=1.04549(5)nm,c=1.12446(5)nm,α=69.071(1)°,β=87.145(1)°,γ=66.982(1)°。     

用循环拆分法制备手性萘乙胺

研究了1-(1-萘基)乙胺[(RS)-1]和1-(2-萘基)乙胺[(RS)-2]的循环拆分方法。以D-酒石酸为拆分剂,分别拆分(RS)-1和(RS)-2得到了(R)-1-(1-萘基)乙胺(收率31%,98%ee)和(R)-1-(2-萘基)乙胺(收率30%,98%ee),并对母液中的非目标对映异构体成功的进行了消旋化,实现了循环拆分。     

Preparation and properties of polyurethane networks based on α,ω-difunctional poly(hexafluoropropylene oxide)

Poly(hexafluoropropylene oxide), poly(HFPO), networks were prepared from functional polymers by end linking via urethane groups. The prepolymers were characterized by NMR spectroscopy and GPC. The networks were characterized by determination of the number of network chains from the shear modulus, and were snown to contain both trifunctional crosslinks and difunctional links. The properties of the networks were investigated by a range of techniques. Compared with fully-fluorinated networks formed via triazine cross-links, investigated previously, the urethane-linked networks were more readily prepared but were poorer elastomers, were less thermally stable, and were less resistant to swelling by common polar solvents. © 1995 John Wiley & Sons, Inc.     

南瓜籽烘烤前后化学成分的分析

对烘烤前后南瓜籽中的化学成分进行分析并对比。采用同时蒸馏萃取装置萃取南瓜籽中的挥发性成分,采取超临界CO2萃取技术萃取南瓜籽油脂,并将其分为酸、碱、中性三个部分,用气相色谱-质谱联用方法分析其中化学成分并进行对比。结果表明,南瓜籽挥发性成分中含有多种醛类和酯类化合物,烘烤后产生了大量的烷基吡嗪,其在碱性部分中的相对含量比烘烤前提高14倍多,不饱和醛类化合物含量也有明显提高。南瓜籽油脂中的主要化学成分是油酸、亚油酸及其酯类。还含有生物活性功能成分如植物甾醇、角鲨烯和维生素E等。烘烤后除角鲨烯含量有所降低,维生素E、植物甾醇、亚麻酸等均有提高。     

云南菊科中草药中铅含量特征分析

论述了云南２７种菊科中草药及其水提取物中铅含量的特征。菊科植物及水提物中铅含量的频数分布为正偏态,两者的相关系数ｒ＝０．０９,未呈现显著的线性相关。提取率较高的山紫苑、佩兰、木香铅实际含量低;铅含量高的叶下花、狭叶兔耳风、臭灵丹提取率又较低,减少了人体对Ｐｂ的过量摄入。     

Synthesis,Luminescence and Intramolecular Energy Transfer of Binary and Ternary Rare Earth Complexes with Aromatic Carboxylic Acids and 1, 10-Phenanthroline

A series of binary and ternary rare earth complexes with para-substitued benzoic acids and 1,10-phenanthroline were synthesized. The phosphorescence spectra were measured and the lowest triplet state energies of ligands were determined, the phosphorescence lifetimes were obtained and intramolecular energy transfer mechanism between ligands was studied. The luminescence properties were also measured and were in agreement with the prediction. The energy match and intramolecular energy transfer process in these binary and ternary complexes were discussed in detail.     

PET导电纤维的制取及研究

以过氧化二苯甲酰为引发剂,使丙烯睛在涤沦(PET)纤维上接枝共聚。接枝纤维在含铜化合物,含硫还原剂溶液中反应,制备PET导电纤维。讨论了影响接枝共聚的各种因素,选择出最佳聚合条件。对该纤维的导电成份和结构以及性能进行了研究。     

Effect of Alkyl Chain Length of N-Alkyl-N′-(2-benzylphenyl)ureas on Gelation

Urea derivatives that were substituted with a 2-benzylphenyl group and an alkyl group functioned as low molecular weight gelators for various organic solvents and ionic liquids. Urea derivatives with long alkyl chains were effective for the gelation of polar solvents. However, they were not suitable for the gelation of non-polar solvents, whereas urea derivatives with short alkyl chains were effective. Ionic liquids were similar to polar solvents in that urea derivatives with long alkyl chains were the most effective gelators. The physical properties of the formed supramolecular gels were analyzed by dynamic viscoelasticity measurements using a rheometer.     

碳苷研究 V: 用Grignard试剂合成取代苯酚中酚羟基的保护及脱保护

本文报道了一些取代苯酚的合成, 并探讨了用Grignard试剂合成取代苯酚中酚羟基的保护及脱保护的问题. 利用苄基和甲基作为酚羟基的保护基, 对文献报道的切断醚键脱保护方法进行了评价. 找到了两种新体系能在更温和条件下切断醚键的方法, 指出了它们的适用条件. 实验结果符合硬软酸碱理论.     

膜催化研究II. 多孔无要膜的制备与表征及其反应器对甲醇脱氢反应的促进作用

采用溶胶-凝胶法制备了多孔氧化铝膜, 并通过DSC、TGA、SEM、N~2吸附和气体透过率测定等手段, 对膜的性能进行了表征。结果表明, 用这种方法制备的多孔氧化铝膜是一种均匀无裂痕和具有较窄孔径分布(约4nm)的膜材料。将此多孔氧化铝膜制成膜反应器后, 用于甲醇催化脱氢制甲醛的反应, 发现甲醇转化率比常规反应器有较大幅度的提高。同时首次尝试采用溶胶-凝胶法将催化活性组分直接负载到多孔氧化铝膜上, 从而得到了一种具有催化活性的多孔膜, 并考察了它的反应活性。文中对由这两种多孔膜及钯/陶瓷复合膜制成的反应器的特点进行了比较。     

幼儿身高、体重和头发、血液锌铅含量关系的研究

同步检测了151例3-4岁健康幼儿的身高、体重以及头和全血中的锌、铅含量。研究了身高、体重和锌、铅含量的关系,指出无论是发锌或血锌含量与身高、体重多数呈正相关,但发铅与身高、体重主要呈负相关,血铅与身高、体重的关系较为复杂,多为非线性的二次函数关系。     

FT-IR, FT-Raman spectra, density functional computations of the vibrational spectra and molecular geometry of biomolecule 5-aminouracil

FT-IR and FT-Raman spectra of the biomolecule 5-aminouracil were recorded in the regions 400–4000 cm⁻¹ and 10–3500 cm⁻¹, respectively. The observed vibrational wavenumbers were analyzed and assigned to different normal modes of vibration of the molecule. Density functional calculations were performed to support wavenumber assignments of the observed bands. A comparison with the molecule of uracil was made, and specific scale factors were employed in the predicted wavenumbers of 5-aminouracil. With the purpose of study the important molecule 5-aminouracil, its equilibrium geometry and harmonic wavenumbers were calculated for the first time by the B3LYP DFT method. The vibrational wavenumbers were compared with IR and Raman experimental data. Also good reproduction of the experimental wavenumbers is obtained and the % error is very small. All the tautomeric forms of 5-aminouracil were determined and optimized. The dimer forms were also simulated. The energy, atomic charges and dipole moments were discussed and several general conclusions were underlined.