糠醛缩胺型高分子-稀土发光配合物的制备及发光特性

通过三步大分子反应法,制备了糠醛缩苯胺型席夫碱功能聚砜和糠醛缩环己胺型席夫碱功能化聚砜。首先,通过傅克烷基化反应在聚砜(PSF)侧链键合氯甲基,制备氯甲基化聚砜CMPSF;以制备的氯甲基化聚砜为亲电试剂,与糠醛(FF)发生傅克烷基化反应,制备侧链键合有糠醛基团的功能化聚砜PSF-FF;使糠醛的醛基分别与苯胺(AN)和环己胺(CA)的氨基发生席夫碱反应,制备糠醛缩苯胺型席夫碱功能聚砜PSF-FA和糠醛缩环己胺型席夫碱功能化聚砜PSF-FC。用红外光谱(FTIR)和核磁共振氢谱(IHNMR)表征功能化聚砜的结构。在此基础上,以这两种功能化聚砜为大分子配体,分别与Eu(Ⅲ)离子和Tb(Ⅲ)离子进行配位,制备了二元配合物PSF-(FA)3-Eu(Ⅲ)、PSF-(FA)3-Tb(Ⅲ)和PSF-(FC)3-Eu(Ⅲ)、PSF-(FC)3-Tb(Ⅲ),初步探索了配合物的光致发光性能。重点研究了制备糠醛缩胺型功能化聚砜PSF-FA和PSF-FC的反应,考察分析了主要因素对CMPSF与FF之间傅克烷基化反应(属亲电取代反应)的影响规律。结果表明,对于该傅克烷基化反应,N,N-二甲基乙酰胺因极性较强为适宜的溶剂,反应适宜的温度为70℃。二元配合物PSF-(FA)3-Eu(Ⅲ)发射Eu(Ⅲ)离子特征荧光(红光),即大分子配体PSF-FA可敏化Eu(Ⅲ)离子的荧光发射,而PSF-(FA)_3-Tb(Ⅲ)无明显的荧光效果,大分子配体PSF-FA的三重态能级与Eu(Ⅲ)离子共振能级比较匹配;配合物PSF-(FC)3-Tb(Ⅲ)发射Tb(Ⅲ)离子的特征荧光(绿光),即大分子配体PSF-FC可敏化Tb(Ⅲ)离子的荧光发射,而PSF-(FA)_3-Eu(Ⅲ)无明显的荧光效果,大分子配体PSF-FC的三重态能级与Tb(Ⅲ)离子共振能级比较匹配。     

在聚砜侧链合成与键合双齿席夫碱配基及功能化聚砜-Tb(Ⅲ)离子配合物荧光发射性能初探

使氯甲基化聚砜(CMPSF)的氯甲基与乙醛酸(GA)的羧基发生酯化反应,将乙醛(AL)基团键合在聚砜侧链,制得改性聚砜PSF-AL;接着,又使3-氨基吡啶(AP)的伯氨基与PSF-AL的醛基发生席夫碱反应,在聚砜侧链合成与键合了具有特定结构的双齿席夫碱配基AA,从而获得了双齿席夫碱配基功能化聚砜PSF-AA,采用红外光谱(FTIR)和核磁共振氢谱(¹H NMR)等技术手段对其结构进行了表征。 以功能化聚砜PSF-AA为大分子配体,与Tb(Ⅲ)离子及Eu(Ⅲ)离子分别配位,制得了二元高分子-稀土配合物PSF-(AA)₃-Tb(Ⅲ)和PSF-(AA)₃-Eu(Ⅲ),初步探索了两种配合物的光致发光性能。 重点研究了功能化聚砜PSF-AA的制备反应,考察与分析了主要因素对CMPSF与GA之间酯化反应的影响规律,优化了反应条件。 CMPSF与GA之间的酯化反应属氯烷的亲核取代反应,实验结果表明,适宜的溶剂为极性较强的N,N-二甲基乙酰胺,75 ℃为适宜的反应温度。 大分子配体PSF-AA对Eu(Ⅲ)离子不产生敏化作用,而对Tb(Ⅲ)离子的荧光发射则产生强烈的敏化作用,配合物PSF-(AA)₃-Tb(Ⅲ)发射出较强的Tb(Ⅲ)离子的特征荧光,即表现出发射绿光的光致发光性能。     

侧链键合双齿席夫碱配基聚砜的制备及大分子-Eu(Ⅲ)配合物荧光发射特性

在制备氯甲基化聚砜(CMPSF)的基础上,以对羟基苯甲醛(HBA)为试剂,通过亲核取代反应,将苯甲醛(BA)键合在聚砜侧链,制得改性聚砜PSF-BA;接着,又使3-氨基吡啶(AP)与PSF-BA的醛基发生席夫碱反应,在聚砜侧链合成与键合了双齿席夫碱(SB)配基,形成了侧链键合有双齿席夫碱配基的功能化聚砜PSFSB。采用红外光谱(FTIR)和核磁共振氢谱(1H-NMR)对其结构进行了表征。以大分子PSF-SB为第一配体,以邻菲罗啉(Phen)为第二配体,与Eu(Ⅲ)离子配位,分别制得了二元和三元高分子-稀土配合物PSF-(SB)3-Eu(Ⅲ)和PSF-(SB)3-Eu(Ⅲ)-(Phen)1,初步探索了配合物的荧光发射性能。本文重点研究了功能化聚砜PSF-SB的制备反应及表征,考察了主要因素对CMPSF与HBA之间亲核取代反应的影响规律,分析了反应机理,优化了反应条件。实验结果表明,对于CMPSF与HBA之间的亲核取代反应,极性较强的N,N-二甲基乙酰胺为适宜的溶剂,90℃为适宜的反应温度。大分子配体PSF-SB对Eu(Ⅲ)离子的荧光发射可产生明显的敏化作用,二元和三元高分子-稀土配合物都发射出较强的Eu(Ⅲ)离子特征荧光。     

萘甲酸功能化聚砜的制备及其与Eu(Ⅲ)稀土离子配合物的荧光发射特性

以1,4-二氯甲氧基丁烷(BCMB)为氯甲基化试剂,使聚砜(PSF)氯甲基化(CM),形成氯甲基化聚砜(CMPSF),然后用6-羟基-2-萘甲酸(HNA)使CMPSF的氯甲基与HNA的酚羟基之间发生亲核取代反应,将萘甲酸(NA)配基键合在聚砜侧链,制得了功能化改性的聚砜NAPSF。采用红外光谱和核磁共振氢谱对其结构进行了表征。考察了主要因素对CMPSF与HNA之间亲核取代反应的影响规律,分析了反应机理,优化了反应条件。结果表明,CMPSF与HNA之间取代反应的速率与亲核试剂HNA的浓度无关,遵循SN1的反应机理;使用极性较强的溶剂二甲亚砜,有利于亲核取代反应的进行;在适宜条件下,CMPSF的氯甲基转化率可达96%,NA的键合量为1.68 mmol/g。将NAPSF与Eu(Ⅲ)离子配位,制得了聚合物-稀土配合物NAPSF-Eu(Ⅲ),它不仅发射出Eu3+离子的特征荧光,而且对Eu3+离子的荧光发射显示出很强的敏化作用。萘甲酸功能化的大分子配基NAPSF对Eu3+离子的敏化作用,远强于苯甲酸(BA)功能化的大分子配基BAPSF对Eu3+离子的敏化作用。     

双齿席夫碱配基功能化的聚砜与Eu(Ⅲ)离子所形成的高分子-稀土配合物的制备及其荧光发射特性

通过分子设计,经过几步大分子反应,在聚砜(PSF)侧链键合了双齿席夫碱(SB)配基,制得了双齿席夫碱配基功能化的聚砜(PSF-SB)。在此基础上,以PSF-SB为大分子配体,以邻菲咯啉(Phen)为小分子配体,与Eu(Ⅲ)离子螯合配位,分别制备了二元高分子-稀土发光配合物PSF-(SB)3-Eu(Ⅲ)与三元高分子-稀土发光配合物PSF-(SB)3-Eu(Ⅲ)-(Phen)1,采用红外光谱和紫外吸收光谱对配合物进行了表征。研究了配合物的荧光发射性能与发光机理。制备了配合物的固体薄膜,考察了固体薄膜的荧光发射性能。结果表明,大分子配基PSF-SB本身具有强的荧光发射,但与Eu(Ⅲ)离子配位后,其自身的荧光发射大为减弱,其与Eu(Ⅲ)离子所形成的二元或三元高分子-稀土配合物均能发射出很强的Eu(Ⅲ)离子的特征荧光,即键合在PSF侧链的双齿席夫碱配基能有效地产生分子内能量转移,强烈地敏化Eu(Ⅲ)离子的荧光发射。第二配体的协同配位效应与对配位水分子的置换作用使得三元配合物的荧光发射强度高于二元配合物。     

氨基吡嗪型双齿席夫碱配基功能化聚砜的制备及其与Tb(Ⅲ)离子配合物的荧光发射特性

首先,通过苯甲醛(BA)改性的聚砜(BA-PSF)与氨基吡嗪(AP)发生席夫碱反应,制得了侧链含氨基吡嗪型双齿席夫碱配基(APSB)的功能化聚砜APSB-PSF。使用核磁共振氢谱(~1HNMR)、红外光谱(FT-IR)表征其化学结构。然后,以APSB-PSF为大分子配体,邻菲罗啉(Phen)为第二配体,使它们与Tb(Ⅲ)离子进行配位螯合反应,分别制备了二元高分子-稀土配合物Tb(Ⅲ)-(APSB)_3-PSF与三元配合物(Phen)_1-Tb(Ⅲ)-(APSB)_3-PSF,研究了配合物Tb(Ⅲ)-(APSB)_3-PSF和(Phen)_1-Tb(Ⅲ)-(APSB)_3-PSF的荧光发射特性与发光机理。实验结果表明,大分子配体APSB-PSF不但能够强烈地吸收紫外光,且其本身荧光强度很高;当APSB-PSF与Tb(Ⅲ)离子配位生成新的二元配合物后,其自身的吸光强度基本不变,但荧光强度却大为削弱,即能量发生了转移,该配合物同时发射出Tb(Ⅲ)离子的特征荧光,且由于接受了APSB-PSF转移的能量使其发光强度大大增强,即APSB-PSF对Tb(Ⅲ)离子发生了敏化作用。而配体APSB-PSF的三线态与Eu(Ⅲ)离子的共振能级不匹配,使APSB-PSF与Eu(Ⅲ)离子的配合物几乎不发射荧光。三元配合物不仅发射出Tb(Ⅲ)离子的特征荧光,且其发光强度高于二元配合物。     

芳羧酸功能化的聚砜与Tb(III)形成的高分子-稀土配合物的结构与荧光发射性能

通过大分子反应将苯甲酸(BA)键合在聚砜(PSF)侧链,制得芳羧酸功能化的聚砜(PSFBA).以PSFBA为大分子配基,以邻菲啰啉(Phen)为小分子配体,与Tb(Ⅲ)配位,分别制备了二元配合物PSFBA-Tb(Ⅲ)与三元配合物PSFBA-Tb(Ⅲ)-Phen,采用傅里叶变换红外(FTIR)光谱和紫外(UV)吸收光谱对配合物进行了表征,深入研究了配合物(溶液与薄膜)的荧光发射性能及热稳定性与结构的关系.研究结果表明,以PSFBA为大分子配基所形成的高分子-稀土配合物,均能发射出很强的Tb(Ⅲ)特征荧光,即键合在PSFBA侧链的配基BA能有效地敏化Tb(Ⅲ)的荧光发射.二元配合物PSFBA-Tb(Ⅲ)的表观饱和配位数为10,即当二元配合物具有PSF-(BA)5-Tb(Ⅲ)的结构时,BA对Tb(Ⅲ)的配位表观上达到饱和,此时二元配合物具有最强的荧光发射.按n(Phen):n(Tb(Ⅲ))=1的比例将Phen加入二元配合物PSF-(BA)5-Tb(Ⅲ)溶液中进行补充配位,所制备的三元配合物PSF-(BA)5-Tb(Ⅲ)-(Phen)1与惯用比例的三元配合物PSF-(BA)1-Tb(Ⅲ)-(Phen)3或PSF-(BA)1-Tb(Ⅲ)-(Phen)2相比,不仅荧光发射强度高,而且热稳定性能好,是一种高性能的场致发光材料.     

侧链键合双齿席夫碱配基的聚苯乙烯的制备与表征及其Eu(Ⅲ)配合物荧光发射性能之初探

以1,4-二氯甲氧基丁烷为氯甲基化试剂,制备了氯甲基化聚苯乙烯(CMPS),使CMPS的氯甲基与对羟基苯甲醛(HBA)发生亲核取代反应,将苯甲醛(BA)键合在聚苯乙烯侧链,制得改性聚苯乙烯PS-BA;使PS-BA的醛基与3-氨基吡啶(AP)的伯氨基发生席夫碱反应,在聚苯乙烯侧链合成与键合了双齿席夫碱(SB)配基,制得了侧链键合有双齿席夫碱配基的功能化聚苯乙烯PS-SB。 采用红外光谱(FTIR)和核磁共振氢谱(¹H NMR)对其结构进行了表征。 以大分子PS-SB为第一配体,以邻菲罗啉(Phen)为第二配体,与Eu(Ⅲ)离子配位,分别制得了二元和三元高分子-稀土配合物PS-(SB)₃-Eu(Ⅲ)和PS-(SB)₃-Eu(Ⅲ)-(Phen),初步探索了配合物的荧光发射性能。 实验结果表明,对于CMPS与HBA之间的亲核取代反应,使用极性较强的N,N-二甲基乙酰胺为溶剂比较适宜,80 ℃为适宜的反应温度。 大分子配体PS-SB对Eu(Ⅲ)离子的荧光发射可产生明显的敏化作用,二元和三元高分子-稀土配合物均发射出较强的Eu(Ⅲ)离子的特征荧光。     

氨基酚型双齿席夫碱配基功能化聚砜的制备及其与Eu(Ⅲ)离子所形成的配合物的光致发光性能

以对氯甲基苯甲醛(CMBA)为试剂,使聚砜(PSF)发生Friedel-Crafts烷基化反应,将苯甲醛(BA)键合在PSF侧链,制得改性聚砜PSF-BA,并考察了主要因素对Friedel-Crafts烷基化反应的影响规律;然后,使PSF-BA的醛基分别与邻氨基苯酚(OAP)及间氨基苯酚(MAP)的氨基发生缩合反应,从而在PSF侧链实现了氨基酚型双齿席夫碱配基的同步合成与键合,获得了2种功能化聚砜PSF-BAOA和PSF-BAMA。采用红外光谱(FT-IR)和核磁氢谱(1 H-NMR)对功能化聚砜的化学结构进行了表征。最后,使大分子配体PSF-BAOA和PSF-BAMA分别与Eu(Ⅲ)离子发生配位反应,制备了光致发光二元高分子-稀土配合物PSF-(BAOA)3-Eu(Ⅲ)与PSF-(BAMA)3-Eu(Ⅲ)。结果表明:溶剂的极性有利于聚砜与CMBA之间的Friedel-Crafts烷基化反应,适宜的溶剂为N,N-二甲基乙酰胺;适宜的温度为70℃。大分子配体PSF-BAOA和PSFBAMA对Eu(Ⅲ)离子的荧光发射均会产生强烈的敏化作用,2种二元高分子-稀土配合物均发射出强烈的Eu(Ⅲ)离子特征荧光。     

键合苯甲酸衍生物聚苯乙烯配体的合成及其Eu(Ⅲ)配合物的光致发光性能

使3-硝基-4-羟基苯甲酸(NHBA)的羟基与氯甲基化聚苯乙烯(CMPS)的氯甲基进行亲核取代反应,在聚苯乙烯侧链上引入硝基苯甲酸(NBA),制得了功能化的聚苯乙烯PS-NBA,考察了亲核取代反应的优化反应条件。 并使之与Eu(Ⅲ)配位,制得了高分子-稀土配合物PS-(NBA)3-Eu(Ⅲ)。 采用红外光谱(FTIR)和核磁共振氢谱(1H NMR)对PS-NBA的结构进行了表征,测试了配合物的荧光发射特性。 结果表明,NHBA苯环上的硝基可降低CMPS与NHBA之间取代反应的速率,使用极性较强的溶剂N,N-二甲基甲酰胺及在较高的反应温度(70 ℃)下,有利于亲核取代反应的进行。 大分子链上的配基NBA对Eu3+离子的荧光发射显示出很强的敏化作用,其敏化作用远强于苯甲酸(BA)配基,高分子-稀土配合物PS-(NBA)3-Eu(Ⅲ)具有比PS-(BA)3-Eu(Ⅲ)更强的荧光发射。     

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.     

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.     

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^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

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。