二苯并-18-冠-6-甲醛聚合物柱色谱分离富集化学发光法测定痕量金

研究了用一种新的高分子冠醚聚合物(二苯并-18-冠-6-甲醛聚合物)作为色谱柱的固定相，分离富集痕量金，再用化学发光法进行测定；在盐酸介质中，高分子冠醚对金的吸附率可达100％，吸附的金可被硫脲完全解吸，吸附容量为19.40mg/g；化学发光法测定操作简便，效果令人满意；研究结果表明：把高分子冠醚聚合物作为分离富集手段与具有高灵敏度的化学发光法结合进行痕量分析是一种很有前途的方法。     

Lipophilicity determination of some new crown ethers by reversed-phase thin-layer chromatography

Summary The lipophilicity of 28 modified crown ether derivatives was determined by reversed-phase thin-layer chromatography (RPTLC) using various organic phases and supports. The lipophilicity values determined in different RPTLC systems showed good correlations, however the quality of the organic phase (methanol, acetone, acetonitrile) and the support characteristics influenced to a small extent the determination.     

表面活性剂与金属离子的相互作用

烷基硫酸盐(CnS)的抗盐能力很差,在其中引进氧乙烯基(Eo)以后,形成的烷基聚氧乙烯基醚硫酸盐(CnEnS)的抗盐能力明显增强。把CnEnS加到CnS中,形成混合表面活性剂的低温抗盐能力也将明显改善。Doscher、Schott等人认为,CnEnS中的Eo与高价金属阳离子形成了一种“复合物”,这使得CnEnS具有很强的抗盐能力。Chiu则没有发现这种“复合物”。显然,了解CnEmS的抗盐机理,对于该类表面活性剂的理论研究和实际应用,都有重要的意义。     

Synthesis and Adsorption Property of Two Polymeric Adsorbents with Pendent Ether Bonds

Two polymeric adsorbents, poly(methyl p-vinylbenzvl ether) and oolv(ohenvl p-vinylbenzyl ether), were synthesized from chloromethylated polystyrene, Their adsorptionproperty for phenol in hexane solution was investigated. The results showed that the twoadsorbents adsorb phenol from hexane solution through hydrogen-bonding and π-π stacking interaction.     

三苯甲基醚直接转化成丙酮化合物的反应

介绍了一种新的高效的由三苯甲基醚直接生成丙酮化合物的方法, 也就是使三氟乙酸条件下脱三苯甲基的反应和生成丙酮化合物的反应在一个反应瓶中同时进行, 使脱三苯甲基作用后生成的醇继续反应得到高产率的丙酮化合物. 这种方法对于分子中同时含有对酸敏感的其他官能团的三苯甲基醚分子的脱保护非常有用.     

[Co（H2o）4（NCS）2]（18—C—6）的薄层光谱电化学研究

利用光谱电化学方法来研究冠醚类化合物的文章尚未见报导.本文在测定用凝胶法合成的[Co(H_2O)(NCS)_2](18-C-6)的核磁共振谱和红外光谱的基础上,使用循环伏安法和薄层光谱电化学技术,在金微栅电极上测定了此配合物在乙腈溶剂中的第一步克式量电势(E~0′)和电子转移数(n),并推测了电还原反应机理.     

一类新的毛细管气相色谱固定液—侧链液晶冠醚聚硅氧烷的研究

合成了一种新的毛细管气相色谱用固定液——侧链含冠醚液晶的聚硅氧烷,这种固定液易于涂渍在弹性石英毛细管柱上,柱效高,热稳定性好,极性中等,它具有高分子液晶和高分子冠醚固定液的双重保留性能,适于分离多种异构体。     

Synthesis of poly[arylene ether sulfone-b-vinylidene fluoride] block copolymers

A series of α,ω-dihydroxy polyarylene sulfones (PAES) were synthesized comprising bisphenol A (PAES1, M_n=1800, 4900, and 9500 daltons), 4,4^′-biphenol (PAES2, M_n=4100 daltons), and hexafluorobisphenol A (PAES3, M_n=3300 daltons). These were reacted with α,ω-dibromo poly(vinylidene fluoride) (PVDF, M_n=1200 daltons) prepared by telomerization, to yield block copolymers possessing rigid and flexible segments. Block copolymers were characterized by FTIR, NMR, GPC, DSC, TGA and TEM. In several cases the block copolymers exhibited distinct thermal transitions, i.e. T_m and T_g for PVDF and PAES segments, respectively. Where observable, T_g of PAES domains in the block copolymers occurred at a temperature lower than the corresponding PAES homopolymer due to the flexible nature of the surrounding PVDF domains. Block copolymers exhibited a similar thermal stability to the corresponding PAES homopolymers but higher stability than the PVDF homopolymer, and much higher still than α,ω-dibromo PVDF. TEM analyses indicate that phase separation of PAES and PVDF domains occurs on the nanometer scale.     

Aqueous solubilities and octanol-water partition coefficients of binary liquid mixtures of organic compounds at 25°C

From thermodynamics and certain assumptions it is shown that, under the usual experimental conditions, the octanol-water partition coefficient (K_o/w) of a given organic liquid should be the same whether the substance is partitioned neat or as part of a mixture. Measurements of several mixtures of n-propylbenzene (log K_o/w=3.71±0.04)+ethylbenzene (log K_o/w=3.16±0.01) clearly confirm this. It is also shown that the aqueous solubility (S_w) of a neat organic liquid can be related to its aqueous solubility (S _w ), when it is present at volume fraction in an organic liquid mixture, by S _w =S_w, where is its activity coefficient in the organic mixture. The measured S _w values for n-propylbenzene + ethylbenzene (1), n-hexane + nitrobenzene (>1) and di-isopropyl ether + chloroform (<1) are found to be in good agreement with the predicted values (average differences of, respectively, <2%, 8% and 6%). In general, the bounds on S _w are expected to be 0w w.     

Alkali Cation Ligating Chains and Sheets of the Macrocycle 1, 7‐Dithia‐18‐Crown‐6 with Bridging Iodo‐ and Thiocyanatocuprate(I) Units

Treatment of an acetonitrile solution of CuI with 1, 7‐dithia‐18‐crown‐6 (1, 7‐DT18C6) at 100°C affords the coordination polymer ¹[(CuI)₂(1, 7‐DT18C6)₂] ( 1 ) in which 1, 7‐DT18C6 ligands bridge (CuI)₂ rings into double chains. 1D polymers of the type ¹[M{(Cu₃I₄)(1, 7‐DT18C6)}] (M = K, 2 ; M = Cs, 3 ) can be isolated under similar conditions in the presence of respectively KI and CsI. Both contain bridging heptacyclic [Cu₆I₈]^2— units but crystallise in different space groups, namely P1 and C2/m. The cesium cation of 3 is markedly displaced from the best plane through the thiacrown ether donor atoms. Reaction of 1, 7‐DT18C6 with CuSCN in the presence of NaSCN yields ²[{Na(CH₃CN)₂} {(CuSCN)₂(1, 7‐DT18C6)}][Cu(SCN)₂] ( 4 ), in which ¹[(CuSCN)₂] double chains are linked through macrocycles into sheets. Infinite ¹[{Cu(SCN)₂}^—] chains compensate the charge of the Na⁺ cations. Complex 1 can imbibe 0.90 mol CsNO₃ per mol of 1, 7‐DT18C6 pairs.