大黄鱼肌肉中7种金属元素的原子吸收光谱分析

采用干法分解样品,应用火焰原子吸收光谱法测定了大黄鱼肌肉中、Ca、Cu、Zn、Fe、Mn、Cd、Pb的含量。研究了不同元素的仪器最佳工作条件、方法的准确度和精密度。在选定的实验条件下,大黄鱼中各元素间相互不干扰,可在同一份制备液中进行7种元素的分别测定。结果表明,大黄鱼肌肉中Ca、Cu、Zn、Fe和Mn含量分别为303.36、1.51、21.98、164.33、1.33μg/g,Cd、Pb未检出。方法加标回收率为93.9%—104.0%,相对标准偏差（n=8）为1.1%—2.5%,测定方法简单易行,方便快捷,结果可靠。     

季铵盐型双子表面活性剂C14-s-C14·2Br的聚集行为

用1H NMR弛豫、2D NOESY研究了双子表面活性剂14-s-14胶束在重水溶液中的聚集行为. 1H NMR自旋-晶格、自旋-自旋弛豫实验表明, 联结基团质子及其邻近的亚甲基质子的运动受到严重限制, 表明这些质子形成胶束疏水核的壳层；而远离极性头的疏水质子的运动则相对自由, 说明其位于胶束的内部. 14-s-14系列(s=2, 3, 4)的弛豫实验结果还表明, 联结基团越短, 分子的碳氢链在疏水核中的排列越紧密. 与14-4-14的对应单链表面活性剂TTAB相比, 它们的分子运动更受限制. 14-4-14的2D NOESY 谱给出了与16-4-16类似的交叉峰信息, 这表明14-4-14同16-4-16一样, 形成了表面不平滑的球形胶束. 因此, 烷烃链的长短对胶束中分子的排列方式没有影响.     

液态29Si NMR研究TEOS/DDS混合体系的氨催化水解动力学

原位引入有机组分对氧化硅体系改性是合成有机-无机杂化硅材料的重要方法.利用原位的29Si液体核磁,研究了甲醇为溶剂、氨水催化条件下的四乙氧基硅烷（TEOS）和二甲基二乙氧基硅烷（DDS）原位共水解的动力学过程.通过改变反应体系中氨和水的浓度,拟合出单体及中间产物浓度随时间的变化曲线,得到了TEOS和DDS各自的水解速率常数以及相应各反应物的反应级数.与单前驱体水解一致的是,在双前驱体系中TEOS和DDS自身的反应级数仍保持一级,但是氨和水的反应级数都有不同程度的增大.与单前驱体水解速率方程相比,混合体系中TEOS的水解速率常数增大.同时,DDS在双前驱体中比单前驱体中的水解速率常数有很大程度的减少.水解动力学表明,TEOS和DDS在双前驱体体系中显示出更平行的水解速率.利用固体29SiMAS NMR,XPS及小角X射线散射（SAXS）手段对双前驱体体系研究得到的信息显示,碱催化条件下原位的TEOS水解中间物与DDS中间产物的原位共缩聚程度很弱.     

Synthesis and characterization of novel heteronuclear complexes of Ln(Ⅲ)-Cu(Ⅱ) with non-cyclic polyether Schiff base

Nine novel heteronuclear complexes of Ln(Ⅲ)-Cu(Ⅱ) with salicylidene tetraethvlcne glycol diamine (SALTTA) have been synthesized and characterized.They have the general formulae [LnCu2(SALTTA)2(NO3)3](NO3)4 3H2O (Ln=La,Pr.Nd,Srn) and [LnCu3(SALTTA)3(NO3)5]-(NO3)4-4H2O (Ln=Gd,Tb,Er,Yb,Y).The IR spectra show that vc=N in the Ln(Ⅲ)-Cu(Ⅱ) het-eronuclear complexes are splitted up into two peaks with a far distance.It has been confirmed that oxygen atoms in oxyethylene of the ligand are not all coordinated to the central metal ions by both IR and NMR methods.     

三氟乙酸溶液中尼龙6链凝聚缠结的NMR弛豫研究

采用1D和2DNMR技术,归属了三氟乙酸(TFA)溶液中尼龙6链上的主要¹HNMR共振信号.不同温度下测定的自旋-自旋弛豫时间(t2)提供了大分子主链间凝聚缠结及TFA溶液中尼龙6链随温度变化的动力学信息.结果表明,尼龙6主链上亚甲基基团有不同程度的凝聚缠结,距离CO和NH基团越远,凝聚缠结越明显.与CO和NH基团相连的亚甲基基团的缠结不很明显,主要是因为尼龙6链间氢键的存在.升高温度,热运动加快,这些凝聚缠结逐渐减弱.NH质子的t2H值几乎不随温度变化,TFA质子的t2H值随温度升高而快速下降,表明尼龙6链间氢键随温度升高而破坏,TFA质子又与因温度升高而从尼龙6中释放出来的自由NH和CO基团形成新的氢键.     

NMR研究溶液中正十四烷基硫酸钠/正十四烷基聚氧乙烯醚(3)表面活性剂之间的相互作用

采用¹HNMR弛豫、自扩散系数和二维相敏(2DNOESY)实验研究了正十四烷基硫酸钠[n-CH₃(CH₂)₁₃OSO₃Na(STS)]和正十四烷基聚氧乙烯醚(3)[n-CH₃(CH₂)₁₃O(C₂H₄O)₃H(C₁₄E₃)]在溶液中的自聚集以及二者混合后的相互作用.结果表明,STS与C₁₄E₃混合后存在相互作用,并形成混合胶束;弛豫实验表明,混合胶束中STS疏水链质子运动更加受阻,C₁₄E₃的α-(4″)和β-CH₂(3″)处链堆积紧密.C₁₄E₃的亲水端(CH₂CH₂0)₃链卷曲紧贴在疏水壳表面外链堆积较紧密处.自扩散系数测量表明,混合胶束比单一阴离子表面活性剂形成的胶束大.单一非离子型胶束和混合胶束的亲水端(CH₂CH₂0)₃(5″)链构成相应较软和松散的外壳.单一C₁₄E₃在极性溶剂氯仿溶液中,质子运动比在水中自由度大,但2DNOESY谱中出现了少量分子间的交叉峰,也可能形成了一些小的聚集体.     

Synthesis and characterization of novel heteronuclear complexes of Ln(III)-Cu(II) with non-cyclic polyether Schiff base

Nine novel heteronuclear complexes of Ln(III)-Cu(II) with salicylidene tetraethylene glycol diamine (SALTTA) have been synthesized and characterized. They have the general formulae [L_nC_u2(SALTTA)₂(NO₃)₃](NO₃)₄·3H₂O (Ln=La, Pr, Nd, Sm) and [LnCu₃(SALTTA)₃(NO₃)₅]-(NO₃)₄·4H₂O (Ln=Gd, Tb, Er, Yb, Y). The IR spectra show that v_C=N in the Ln(III)-Cu(II) heteronuclear complexes are splitted up into two peaks with a far distance. It has been confirmed that oxygen atoms in oxyethylene of the ligand are not all coordinated to the central metal ions by both IR and NMR methods.     

表面活性剂在水溶液中自聚集的NMR研究

用质子化学移位 ,自扩散系数和核磁弛豫方法研究了正十二烷基磺酸钠(SDSN) ,正十六烷基三甲基溴化铵 (CTAB)和TritonX 1 0 0等 3种类型表面活性剂及其在溶液中生成的胶团的动态行为 .3种体系的化学移位 ,自扩散系数和自旋 晶格弛豫时间 (T₁) ,自旋 自旋弛豫时间 (T₂ )均在临界胶团浓度 (cmc)附近有明显的转折点 ,并在 5～ 1 0倍cmc左右时趋向平衡 .T₁和T₂值的测量表明TritonX 1 0 0分子在溶液中的浓度低于cmc时进行着快速的各向同性运动 .生成胶团后 ,胶团核中的疏水碳氢链紧密堆积使其CH₂ 和CH₃ 基团进行着偏离极限窄化条件的运动 .而胶团核外的亲水醚氧长链则进行着相对自由的运动 .但是由于胶团中的分子密集 ,亲水长链产生局部缠结引起T1和T2 值变短 .SDSN和CTAB生成的胶团核内的碳氢链的状态和TritonX 1 0 0的相同 .     

Studies on synthesis and magnetic resonance of lanthanide complexes with novel Schiff base derived from noncyclic polyether and β-diketone

Nine h( III) complexes with a novel Schiff base derived from diglycolamine and benzoylacetone (BZDA) have been synthesized and characterized. They can be formulated as [Ln₂(BZDA)₃(NO₃)₃](NO₃)₃-nH₂O (Ln? La, Pr, Nd, Sm, n = 4; Ln = Gd, Tb, Er, Yb, Y, n = 7). Enamic form mechanism in this β-diketone Schiff base and its Complexes were suggested and proved by IR, UV and NMR methods. The ¹³C spin-lattice relaxation time T₁ and the ratios of r(C_i-In)/ ^r (c_j-in) were measured by a 500 MHz NMR instrument for elucidating the formation of the stable six-membered chelate ring structure in these complexes. The EPR spectrum of the Gd( III) complex exhibits the “U” spectral feature and “zero field effect”. On the basis of them, the crystal field strength and the local symmetry around Gd ³⁺ in the complex have been discussed.     

Interaction of poly(vinylpyrrolidone) with cationic and nonionic surfactants in aqueous solution studied by <Superscript>1</Superscript>H NMR

Aqueous solutions of surfactant at various concentrations with 0.2% poly(vinylpyrrolidone) (PVP) were studied by ¹H NMR methods, including relaxation time and self-diffusion coefficient measurements and two-dimensional nuclear Overhauser enhancement spectroscopy. Two surfactants were concerned: cationic cetyltrimethylammonium bromide (CTAB) and nonionic Triton X-100 (TX-100). In the presence of 0.2% PVP, the variation of the T ₂ values of CTAB protons is similar to that in the absence of PVP. Relaxation times of PVP protons are not significantly affected by the increasing concentration of CTAB. This indicates that no interaction between PVP and CTAB could be detected. However, in the presence of 0.2% PVP, TX-100 micelles are formed at a concentration lower than its normal critical micellization concentration. According to the results of relaxation time measurement of water protons, the presence of 0.2% PVP also induces the contraction of the hydrophilic layer of the TX-100 micelle. This indicates some interaction between PVP and TX-100, but the mechanism of this interaction needs further investigation.