Pd-CuO/TiO2的还原和再氧化行为的研究

用TPR和TPO方法考察了载体TiO_2和金属Pd对CuO还原和再氧化行为的影响。发现TiO_2可显著降低CuO的还原和再氧化温度,担载Pd后,TiO_2上CuO甚至在十分温和条件下就能与H_2很快反应。文中就TiO_2和Pd的作用机理进行了讨论。     

CATALYTIC BEHAVIOR OF DOPED MTiO_3 CATALYSTS FOR OXIDATIVE DEHYDROGENATION OF ETHANE

用Ｌｉ＋部分替代ＭＴｉＯ３（Ｍ＝Ｃａ、Ｓｒ）催化剂中的Ｔｉ４＋，明显地提高了乙烷氧化脱氢（ＯＤＨＥ）反应中乙烯的选择性。在ＣａＴｉ０．９Ｌｉ０．１Ｏ３－δ催化剂上，反应温度为８５０℃时，乙烯选择性为７７．４％，乙烷转化率为８１．７％。Ｌｉ掺杂的作用是增加了催化剂的Ｐ型半导性和未充分还原的氧物种数目。     

Study on analysis of153Sm-EDTMP stability in vitro and vivo by HPLC

The behavior of¹⁵³Sm-EDTMP in vitro and vivo is analyzed by the size exclusion HPLC. The experimental results show that EDTMP amounts have an obvious effect on the stability in vitro and uptake of¹⁵³Sm-EDTMP in the liver. HPLC analysis of urine sample indicates that¹⁵³Sm-EDTMP es excreted in the original form. The behavior in vivo of¹⁵³Sm-EDTMP containing 4 μg is similar to that of¹⁵³Sm-EDTMP containing 50 μg EDTMP at 1 h post-injection.     

Geometry,stability and aromaticity of β-diketiminate-coordinated alkaline-earth compounds

Alkaline-earth (Ae) metals have attracted a wealth of interdependent research from synthetic chemists. In Ae-catalyzed organometallic reactions, β-diketiminate is a typical ligand used to stabilize Ae catalysts by forming six-membered rings comprising Ae metals. Herein, studies focusing on the configuration of β-diketiminate-coordinated Ae compounds observed that the CC and CN bonds are homogeneous and unchanged. Furthermore, energetic studies observed that the formation of the Ae-incorporated six-membered rings results in enhanced stability of >20 kcal/mol. The nucleus-independent chemical shifts, anisotropy of the induced current density, and molecular orbital analyses demonstrated the non-aromaticity of the β-diketiminate-coordinated Ae compounds. The improved stability of these compounds can be explained by the delocalization of the π electrons derived from the β-diketiminate moiety.     

Hydroxylation of nigranoic acid to 6β-hydroxynigranoic acid by Caryospora carllicarpa YMF1.01026

Microbial transformation of nigranoic acid by Caryospora carllicarpa YMF1.01026 afforded the new derivative 6β-hydro-xynigranoic acid. Its structure was elucidated by spectroscopic methods.     

A resonance light scattering method for determination of DNA using Ru(bpy)2PIP(V)2+

A novel method for DNA detection is proposed that is based on the enhancement of resonance light scattering (RLS) of Ru(bpy)₂PIP(V)²⁺ at pH 2.7. Under optimum conditions, good linear relationships were obtained in the wide concentration range of 16–5120 ng mL⁻¹. The linear equation is I _RLS = 13.15 + 171.4 c (μg mL⁻¹), the correlation coefficient (r) is 0.9999. The detection limit of calf thymus DNA is 5.02 ng mL⁻¹. Plasmid DNA extracted from bacillus subtilis was determined by the method with satisfactory results.     

Structure determination and relative properties of novel cubic borates MM'4(BO3)3 (M = Li, M' = Sr; M = Na, M' = Sr, Ba)

A series of novel borates, MM'4(BO3)3 (M = Li, M' = Sr; M = Na, M' = Sr, Ba), have been successfully synthesized by standard solid-state reaction. The crystal structures have been determined from powder X-ray diffraction data. They crystallize in the cubic space group Iad with large lattice parameters: a = 14.95066(5) A for LiSr4(BO3)3, a = 15.14629(6) A for NaSr4(BO3)3, and a = 15.80719(8) A for NaBa4(BO3)3. The structure was built up from 64 small cubic grids, in which the M' atoms took up the corner angle and the BO3 triangles or MO6 cubic octahedra filled in the interspaces. The isolated [BO3]3- anionic groups are perpendicular to each other, distributed along three 100 directions. The anisotropic polarizations were counteracting, forming an isotropic crystal. Sr and Ba atoms were found to be completely soluble in the solid solution NaSr(4-)xBax(BO3)3 (0 < or = x < or = 4). The photoluminescence of samples doped with the ions Eu2+ and Eu3+ was studied, and effective yellow and red emission was detected, respectively. The results are consistent with the crystallographic study. The DTA and TGA curves of them show that they are chemically stable and congruent melting compounds.     

硝酸肼的量热研究

用精密自动绝热量热计测定了在220 K—370 K温度范围内硝酸肼的热容、熔化热、熔化温度和熔化熵。所得热容数据的精密度以百分偏差的均方根值表示为±0.2％。三次熔化热测定的相对偏差为±0.1％。为验证结果的可靠性, 用该装置测定了冰的熔化热和熔化温度, 其结果与文献值一致; 又用法国SETARAM公司的高温量热计测定了硝酸肼的熔化热和熔化温度, 其结果与我们用量热法测定的结果一致; 从量热结果计算出了该试样的纯度, 该结果亦与化学分析的结果一致。这些均可说明我们所测得的数据是可靠的。     

Formate--the analogue of azide: structural and magnetic properties of M(HCOO)2(4,4'-bpy).nH2O (M = Mn, Co, Ni; n = 0, 5)

Reaction of transition metal formate M(HCOO)(2).2H2O (M = Mn, Co, Ni) with 4,4'-bpy (4,4-bipyridine) has led to four new compounds with the formula M(HCOO)2(4,4'-bpy).nH2O (M = Mn, Co (1.Mn, 2.Co), n = 0; M = Co, Ni (3.Co, 4.Ni), n = 5). Compounds 1.Mn and 2.Co are isomorphous and crystallized in the tetragonal crystal system with the chiral space group P4(1)2(1)2. They are of three-dimensional diamondoid structure connected by anti-anti formate with 4,4'-bpy in the cavities of the framework reinforcing the intermetallic connections; the diamond-like net was observed also in their azide analogue (Mn(N3)2(4,4'-bpy)). Compounds 3.Co and 4.Ni are isomorphous also but crystallized in the monoclinic crystal system with the space group Cc. Both structures are uninterpenetrated 3D "CdSO4" type with big channels, constructed by anti-anti formate and 4,4'-bpy. This type of net was not observed in their azide analogue. Residing in the channels, water molecules form a new type of 1D tape constructed by vertex-sharing cyclic pentamers. Magnetic measurements were performed on all of these four compounds. 1.Mn and 2.Co are weak ferromagnets with the critical temperature Tc = 5.3 and 7.4 K, respectively. 3.Co is an antiferromagnet with Neel temperature TN = 3.0 K, and 4.Ni is a weak ferromagnet below 20 K. Hysteresis loop can be observed for 2.Co and 4.Ni at 1.8 K. As an analogue of azide, formate can be used to construct molecular architectures, which structurally and magnetically have great similarities to and also differences from those of azide. This offers a promising method for the design of new molecular architectures with formate.     

用钐和四氯化钛体系一锅法合成咪唑烷衍生物

在四氢呋喃溶液中,用Sm/TiCl4体系还原亚胺合成了咪唑烷衍生物.发现当没有促进剂1,2-二溴乙烷时,咪唑烷衍生物的产率小于20%,加入1,2-二溴乙烷后,产率大大提高.产物的结构通过IR,1HNMR和MS光谱确证.根据实验结果提出了一个可能的反应机理.