吡啶-2,6-二甲酸衍生物及其Tb(Ⅲ)和Eu(Ⅲ)配合物的合成与荧光性质

以吡啶-2,6-二甲酸(DPA)为起始物,合成了4-羟甲基吡啶-2,6-二甲酸(4-HMDPA)和4-(N,N-二羧甲基氨基)亚甲基吡啶-2,6-二甲酸(4-BMDPA)两种新型多功能配体,并制备了DPA,4-HMDPA及4-BMDPA的Tb(Ⅲ)和Eu(Ⅲ)配合物,对配合物的固体和溶液态的荧光性质进行了研究. 结果表明,在吡啶4位引入弱吸电子基团4-羟甲基会减弱稀土配合物的荧光强度; 在水溶液中稀土配合物与溶液的pH值有着密切的关联,中性水溶液中荧光强度较大; 分子偶极矩较小的溶剂中稀土配合物荧光强度较强. 表明4-BMDPA是较理想的稀土荧光敏化剂.     

吡啶-2,6-二甲酰胺衍生物Tb(Ⅲ)、Eu(Ⅲ)配合物的制备及荧光性能测试

从吡啶-2,6-二甲酸(L1)出发,合成了2种含有多个共轭体系和多齿的N2,N6-二(3-甲基吡啶)-2-取代吡啶-2,6-二甲酰胺(L2)配体和N2,N6-二对甲苯基吡啶-2,6-二甲酰胺 (L3) 配体;制备了化合物N2,N6-二(3-甲基吡啶)-2-取代吡啶-2,6-二甲酰胺(L2)与Tb(Ⅲ)和Eu(Ⅲ)的配合物,培养出了单晶.通过红外光谱、元素分析和X射线单晶衍射仪确定配合物的组成和结构.结果表明:在Tb(Ⅲ)配合物的稀溶液中,当溶液pH值为7时荧光强度最强,pH值大于或小于7荧光强度都逐渐减弱;当溶液pH为7时,N2,N6-二(3-甲基吡啶)-2-取代吡啶-2,6-二甲酰胺对Tb(Ⅲ)的荧光强度敏化远大于吡啶-2,6-二甲酸;N2,N6-二(3-甲基吡啶)-2-取代吡啶-2,6-二甲酰胺和吡啶-2,6-二甲酸与Eu(Ⅲ)形成稀的配合物溶液的荧光强度随pH值的增加而增大(pH 3～11).     

吡啶-2,6-二甲酰腙类化合物及其Tb(Ⅲ)和Eu(Ⅲ)配合物的合成与荧光性能

吡啶-2,6-二甲酸经酯化,肼解得吡啶-2,6-二甲酰肼(2),(2)与芳香醛缩合得到了3个新的酰腙配体:吡啶-2,6-二甲酰肼苯甲醛腙(3a)、吡啶-2,6-二甲酰肼水杨醛腙(3b)和吡啶-2,6-二甲酰肼呋喃甲醛腙(3c),其结构经元素分析、IR、1HNMR和MS进行了确认。制备了吡啶-2,6-二甲酰肼与这三种新型配体的Tb(III)和Eu(III)配合物,并对配合物的溶液态的荧光性质进行了研究。结果表明,吡啶-2,6-二甲酰肼苯甲醛腙(3a)和吡啶-2,6-二甲酰水杨醛腙(3b)作为荧光敏化剂,对Eu3+和Tb3+的荧光敏化性能比吡啶-2,6-二甲酰肼以及大多数吡啶-2,6-二甲酸衍生物要好,是较理想的稀土荧光敏化剂,它们的稀土配合物在分子偶极矩较小的溶剂中荧光强度较强。     

新型吡唑啉酮稀土配合物的合成及荧光性能

通过分子设计,以吡啶-2,6-二甲酸为起始原料,合成了一种新型双吡唑啉酮吡啶配体:2,6-二(1-苯基4-乙氧羰基-5-吡唑啉酮-3-基)吡啶(H2L)。配体与稀土Eu(Ⅲ)和Tb(Ⅲ)离子成功螯合形成配合物。配体和配合物经FT-IR,1H NMR和元素分析进行表征,并确定配合物组成为RE2L3.4H2O。对配合物的紫外吸收和光致发光性能进行了检测,结果显示Eu(Ⅲ)和Tb(Ⅲ)离子能够有效地被有机配体敏化,发射出高亮、半峰宽狭窄的单色光。研究表明目标配合物能够成为优秀的发光材料。     

一个新双氮杂冠醚及其稀土硝酸盐配合物的合成表征

合成了一个新的二十员大环双氮杂冠醚及其与稀土硝酸盐所形成的1∶2(M∶L)型配合物, 并经过红外光谱, 元素分析, 摩尔电导, 热分析及荧光光谱等方法表征. 结果表明, 配位是通过配体中的C-O-C进行的, 而Ar-O-C未参与配位, 同时含两分子配位水, 对Sm3+, Eu3+, Tb3+, Dy3+的配合物进行了荧光光谱测定, 均有较强的荧光强度, 其中Tb(Ⅲ)配合物荧光强度最高.     

含羧基侧基聚芳醚酮-钐配位聚合物的制备及其荧光性能研究

分别采用自制的3种含羧基侧基的聚芳醚酮(PEK-1、PEK-2和PEK-3)作为高分子配体,1,10-邻菲罗啉(Phen)作为协同配体,钐(Sm3+)作为中心离子,制备了一系列新型的含羧基聚芳醚酮-钐配位聚合物(PEK-Sm3+-Phen).通过红外光谱和紫外-可见吸收光谱分析表明钐离子同时与高分子配体和小分子配体发生了配位,且由X-射线衍射分析证实钐离子通过配位的方式能够均匀地分布于配位聚合物体系中.采用荧光激发和发射光谱对制备的配位聚合物荧光性能进行了研究,结果表明这些配位聚合物在紫外光激发下均能够发射出较强的Sm3+的特征荧光,且因刚性PEK高分子链的引入配位体系的结构更加稳定,并使Sm3+配位环境的对称性降低,从而其荧光强度远高于相应的小分子配合物.同时讨论了不同高分子配体对配位聚合物荧光强度的影响,带有较多烷基取代基的PEK-1使PEK-1-Sm3+-Phen显示出最高的荧光强度.进一步研究了PEK-1-Sm3+-Phen的荧光发射强度与Sm3+含量之间的关系,其荧光强度随着Sm3+含量的增加而逐渐增大,当Sm3+的含量达到15.73wt%时,荧光强度出现最大值.     

Eu~(3+)-Dy~(3+)稀土配合物的合成及其发光性质

以2,4,6-吡啶三甲酸为配体,通过水热方法合成出含Eu3+和Dy3+两种稀土离子的一系列配合物;测定了配合物的发光性质.结果表明,通过掺杂不同比例的Dy3+可以得到荧光强度不同的配合物,其在紫外光照射下发出Eu3+的特征红色荧光;随着Dy3+含量的增加,Eu3+的特征荧光逐渐减弱.这说明该系列配合物中的Dy3+对Eu3+的荧光产生猝灭作用;其原因可能是配体吸收的激发能被Dy3+在近红外区的辐射跃迁所损耗.     

稀土烟酸与8-羟基喹啉三元配合物的合成、表征及荧光光谱

合成了 4种稀土烟酸 (HL)与 8 羟基喹啉 (Hhq)的三元固体配合物 ,对它们进行元素分析 ,确定其通式为REL2 ·hq·2H2 O (RE =La ,Eu ,Tb ,Dy) ,用摩尔电导、TG DTA分析、IR、UV和荧光光谱等研究了配合物的有关性质。结果表明 ,烟酸脱掉羧酸上的质子以酸根的形式与稀土离子呈双齿配位 ,而吡啶环上的氮原子未参加配位。hq- 的羟基氧和杂氮原子与RE3+ 离子配位。配体与稀土配位后 ,配合物中稠环数目增多 ,π键共轭程度增大。配合物中所含的水可能为配位水。荧光光谱研究发现 ,La和Dy的配合物的荧光表现为配体的荧光 ,Eu配合物中心离子的特征荧光峰表现不明显 ,而Tb配合物中配体能有效地将吸收的能量传递给Tb3+ ,敏化Tb3+ 的发光 ,发射较强荧光     

稀土-2,6-吡啶二甲酸-氧化三苯基膦配合物的合成及其荧光性质

稀土离子尤其是Sm,Eu,Tb,Dy因为其良好的荧光性能而得到了广泛的研究和应用[1,2]。吡啶二甲酸和氧化三苯基膦这两种配体有较大范围的共轭π键,在近紫外区又都有较宽的吸收带和较强的吸收峰,与稀土离子配位后可以构成有效的能量传递体系,将它们在近紫外区吸收的能量有效地传递给     

铕、铽2,6-二甲酸吡啶、α-甲酸吡啶络合物的研究

近年来,稀土络合物的发光引起了人们的重视。Yamazoe等报道了R-CH=CH-COO~-类及β-羧酸吡啶铕、铽络合物的发光性能。山添等报道了α-甲酸吡啶铕、铽络合物的摩擦发光。本文制备了铕和铽的2,6-二甲酸吡啶络合物Na_3[Ln(DPA)_3]·NaCl·_3H_2O和α-甲酸吡啶络合物Ln(DPA)(PA)·1.5NaCl·3H_2O(Ln=Eu、Tb;DPA=2,6-二甲酸吡啶酸根;PA=α-甲酸吡啶酸根),并测定了络合物的红外光谱和荧光光谱。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

解决能源问题的新途径——光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。