二苯并18-冠-6配合物[NH4(DB18-C-6)]2[Pd(SCN)4]的合成与结构分析

研究了二苯并18-冠-6(DB18-C-6)与(NH4)2[Pd(SCN)4]的反应,通过元素分析、红外光谱、单晶X射线衍射对生成的配合物[NH4(DB18-C-6)]2[Pd(SCN)4](1)进行了结构分析.1为三斜晶系,空间群P-1,晶体学数据:a=0.8705(3)nm,b=1.1954(4)nm,c=1.3044(4)nm,α=73.216(5)°,β=78.897(5)°,γ=81.105(6)°,V=1.2682(7)nm3,Z=1,F(000)=568,R1=0.0301,wR2=0.0431.配合物由二个[NH4(DB18-C-6)]+配阳离子和一个[Pd(SCN)4]2-配阴离子组成,二者通过N-H…N氢键形成中性配合物,配合物中不存在阳离子-π相互作用.     

[Na(18-C-6)]2[Cu(i-mnt)2]的合成与结构分析

研究了18-冠-6与Na2[Cu(i-mnt)2][i-mnt=异丁二腈烯二硫醇阴离子,S2CC(CN)2-2]的反应,得到的配合物[Na(18-C-6)]2[Cu(i-mnt)2](1)通过元素分析、红外光谱、X射线单晶衍射进行了结构分析.配合物为单斜晶系,空间群P2(1)/c.晶体学结构数据a=1.2819(11),b=1.1793(10),c=1.4928(13)nm,β=99.121(16)°,V=2.228(3)nm3,Z=2,Dcaled.=1.369g/cm3,F(000)=958,R1=0.0521,wR2=0.1003.1中的[Cu(i-mnt)2]基团通过配体i-mnt的氮原子与两个[Na(18-C-6)]基团中的钠原子成键,形成稳定的中性配合物.     

苯并18-冠-6配合物[K(B18-C-6)]SCN的合成与结构分析

苯并 18 -冠 - 6 (B18- C- 6 )与 K2 [Cd(SCN) 4 ]反应 ,得到了 [K(B18- C- 6 ) ]SCN配合物。通过元素分析、红外光谱、单晶 X射线衍射进行了结构分析。该配合物为单斜晶系 ,空间群 P2 (1) / c,晶体学数据 :a=0 .996 0(3) nm,b=2 .5 0 97(7) nm,c=0 .8374 (2 ) nm,β=10 6 .5 19(5 )°,V=2 .0 0 6 7(10 ) nm3 ,Z=4 ,F(0 0 0 ) =86 4,R1=0 .0 4 2 9,w R2 =0 .0 5 75。结构分析表明 ,该配合物由一个 [K(B18- C- 6 ) ]配阳离子和一个 SCN阴离子组成 ,配合物的两个分子通过 K+ - π相互作用形成一维链状结构     

苯并15冠5钯配合物:[K(B15C5)_2]_2[Pd(SCN)_4]的合成与结构研究

合成了苯并 15冠 5与钯生成的配合物 :[K( B15C5) 2 ]2 [Pd( SCN) 4],并通过元素分析、红外光谱及 X射线单晶结构分析进行了表征。配合物为单斜晶系、空间群 P2 1/ n。晶体学数据 :a=1.2 0 4 30 ( 7) ,b=1.932 99( 10 ) ,c=1.56680 ( 9) nm,β=10 8.1190 ( 10 )°,V=3.4 665( 3) nm3,Z=2 ,F( 0 0 0 ) =142 4 ,R1=0 .0 50 0 ,w R2 =0 .1549。配合物由两个 [K( B15C5) ]+2 配阳离子和一个 [Pd( SCN) 4]2 -配阴离子组成。四个硫氰酸根的硫原子与钯原子配位 ,[Pd( SCN) 4]2 -为平面方形构型。 K+与 2个冠醚环的 10个氧原子成键而形成夹心型结构。两个苯并 15冠 5的苯环相对钾原子呈反式排列     

苯并15冠5钯配合物：［K(B15C5)2］2［Pd(SCN)4］的合成与结构研究

合成了苯并15冠5与钯生成 的配合物：[K(B15C5)2]2[Pd(SCN)4],并通过元素分析,红外光谱及X射线单晶结构分析进行了表征,配合物为单斜晶系,空间群p21/n,晶体学数据：a=1.20430(7),b=1.93299(10),c=1.56680(9)nm,β=108.1190*10),V=3.4665(3)nm3,Z=2,F(000)=1424,R1=0.05000,wR2=0.1549.配合物由两个[K(B15C5)]2^ 配阳离子和一个[Pd(SCN)4]^2-配阴离子组成,四个硫氰酸根的硫原子与钯原子配位,[Pd(SCN)2]^2-为平面方形构型,K＋与2个冠醚环的10个氧原子成键而形成夹心型结构,两个苯并15冠5的苯环相对钾原子呈反式排列。     

{[K(18-C-6)][K(H2O)2]}[Cd(CN)4]的合成与结构分析

合成了配合物 { [K(18- C- 6 ) ][K(H2 O) 2 ]} [Cd(CN) 4 ](1) ,并通过元素分析、红外光谱、单晶 X-射线衍射进行了结构分析。配合物属单斜晶系 ,空间群 P2 (1) / n。晶体学数据 :a=0 .936 5 3(18) nm,b=1.6 178(3) nm,c=1.74 81(3) nm,β=91.332 (3)°,V=2 .6 479(9) nm3 ,Z=4 ,Dcalcd=1.4 5 3g/ cm3 ,F(0 0 0 ) =12 0 8,R1=0 .0 317,w R2 =0 .0 5 6 7。配合物中 [K(18- C- 6 ) ],[K(H2 O) 2 ]和 [Cd(CN) 4 ]基团通过 K N键和 K —π相互作用形成三维网状结构     

[K(15-C-5)2]2[Ni(i-mnt)2]·2H2O的合成与结构分析

研究了15-冠-5与K2[Ni(i-mnt)2]{i-mnt=异丁二腈烯二硫醇阴离子,[S2C2(CN)2]2-}的反应,得到的配合物[K(15-C-5)2]2[Ni(i-mnt)2]·2H2O(1)通过元素分析、红外光谱、X射线单晶衍射进行了结构分析。配合物为三斜晶系,空间群P-1。晶体学结构数据:a=1.2674(5)nm,b=1.6317(7)nm,c=1.7771(7)nm,α=102.397(7)°,β=104.828(8)°,γ=93.659(7)°,V=3.442(2)nm3Z=2,F(000)=1412,R1=0.0727,wR2=0.1283。(1)中的[Ni(i-mnt)2]基团通过配体i-mnt的氮原子与两个[K(15-C-5)2]基团之中的钾原子成键,形成稳定的中性配合物。     

[{Na(18-C-6)}2(H2O)][Ni(i-mnt)2]的合成与结构分析

研究了18-冠-6与Na2[Ni(i-mnt)2]{i-mnt=异丁二腈烯二硫醇阴离子,[S2C2(CN)2]2-}的反应,得到的配合物[{Na(18-C-6)}2(H2O)][Ni(i-mnt)2](1),通过元素分析、红外光谱、X射线单晶衍射进行了结构分析。配合物为三斜晶系,空间群P-1。晶体学结构数据:a=1.0991(12)nm,b=1.1011(12)nm,c=1.1305(12)nm,α=70.44(2)°,β=87.44(2)°,γ=62.552(19)°,V=1.134(2)nm3,Z=1,F(000)=488,R1=0.3771,wR2=0.1497。(1)中的[Ni(i-mnt)2]基团通过配体i-mnt的氮原子与两个[Na(18-C-6)]基团之中的钠原子成键,形成稳定的中性配合物。     

离子对电荷转移配合物[NO2Py]x[Co（mnt）2]的合成、光谱和磁性表征

合成了两种新的离子对电荷转移配合物[NO2Py]x[Co(mnt)2],(NO2Py=1-(4-ritrobenzyl)pyridinium;mnt=maleonitriledithiolate;x=1or2时分别对应配合物2和1),并用元素分析和红外光谱、电喷雾质谱和固体反射电子光谱等谱学方法对两种配合物进行了表征.两种配合物在77K到300K范围内的变温磁化率结果表明,配合物2是抗磁性物质,经Pascal′s常数校正后的配合物1的磁化率遵循改进的Bleaney-Bowers方程,实验值和理论计算值能很好的吻合,非线性最小平方二乘法拟合所得的最佳拟合参数为g=2.392,2J/k=5.9K和θ=-4.9K,一致性因子R=7.20×10-9(R=∑(χobsi-χcalcdi)2/∑(χobsi     

水杨醛缩二乙基三胺铜配合物的合成与结构分析

合成了水杨醛缩二乙基三胺 (配体 L,2 - [(N- Salicylideneamino) ethyl]amine)与 Cu( )形成的配合物[Cu L(H2 O) ]Cl,通过元素分析、红外光谱、X射线单晶衍射进行了结构分析。配合物为单斜晶系 ,空间群P2 (1) / c,晶体学结构数据 ,a=0 .912 3(5 ) nm,b=1.382 1(7) nm,c=1.0 82 9(5 ) nm,β=10 1.712 (7)°,V=1.336 9(11) nm3 ,Z=4 ,Dcalcd=1.6 0 6 mg/ m3 ,F(0 0 0 ) =6 6 8,R1=0 .0 377,w R2 =0 .10 18。结构分析表明 ,配合物通过氢键形成二聚结构     

Surface Reconstruction with a Fractional Hole: (sqrt[5] x sqrt[5])R26.6 degrees LaAlO3 (001)

The structure of the (sqrt[5] x sqrt[5])R26.6 degrees reconstruction of LaAlO3 (001) has been determined using transmission electron diffraction combined with direct methods. It has a lanthanum oxide termination with one lanthanum vacancy per surface unit cell. Density functional calculations indicate that charge compensation occurs by a fractional number of highly delocalized holes, and that the surface contains no oxygen vacancies and the holes are not filled with hydrogen. The reconstruction can be understood in terms of expulsion of the more electropositive cation from the surface and increased covalency.     

Leberfunktionsuntersuchungen mit dem [15N]Ammoniumtest

In laboratory tests a method was developed for a non-contacting moisture gauging on conveyor belts of different materials like coal, clay, industrial slay and stones of inflating clay. The moisture was measured with an ²⁴¹ Am-Be-neutron source, the absolute necessary determination of the changing flow of material was made with the gamma rays of ¹³⁷Cs or ²⁴¹Am. The analysis of the records shows, that to all measuring values mathematical defined curves could be found, so that methods of calculation for the moisture content could be deduced. The maximal obtainable accuracy is about ±0.5 percentage by weight. With the industrial slay and the stones of inflating clay supplementary tests were made direct on the conveyor bell. They shows, that also in the practice good results can be obtained.     

The Fate of [15N]Ammonium and [15N]Nitrate in the Soil of a 140-Year-Old Spruce Stand (Picea Abies) in the Fichtelgebirge (NE-Bavaria)

Abstract

A ¹⁵N tracer-experiment was carried out in a 140-year-old spruce stand (Picea abies (L.) Karst.) in the Fichtelgebirge (NE-Bavaria, Germany). Highly enriched (98 at%) [¹⁵N]ammonium and [¹⁵N]nitrate were applied as tracers by simulation of a deposition of 41.3 mol N ha^?1 with 11 water m^?2. To examine seasonal variations of uptake by spruce and understorey vegetation, different plots were labelled in spring, summer and autumn 1994.

One aim of the present study was to perfect a method of preparation of soil extracts for isotope ratio mass spectrometry (IRMS) measurements. Ammonium and nitrate from soil extracts were prepared for IRMS measurements by steam distillation and subsequent freeze drying. Additionally, tracer distribution and transformations in the soil nitrogen pools were examined. Ammonium, nitrate and total nitrogen were examined in the organic layer and the upper 10 cm of the mineral soil during 3 months after the first tracer application in spring 1994.

In July 1994, three months after tracer application, 40% of the [¹⁵N]ammonium label and 29% of the [¹⁵N]nitrate label, respectively, were recovered in the total N pool of the investigated soil horizons. In the organic layer the L/Of horizon retained most of the recovered tracers. Nitrification, immobilisation and mineralisation occurred even under the conditions of high soil acidity at the study site.     

Electronic structure and spectra of [Cr(C6H6)2]+ and [Fe(C5H5)2]+

The high-resolution N.M.R. spectra of a series of bicyclo [2.2.1] heptanols are discussed. Three unusual features are observed: (a) relatively large ⁴ J's; (b) unequal J _endo-endo's and J _exo-exo's; and (c) unusual magnetic shieldings.

These are presented as empirical phenomena and only little attempt is made to discuss their implications.     

Chiral Fluorescence Recognition by Anthracene Fluorescent Dyes ⊂ Water-Soluble Pillar[5] arene containing Phosphonic Acid Group (PWP[5])

Chirality plays a pivotal role in drugs, agrochemicals and food additives et al. The enantiomers of a chiral molecule often show huge difference in bioactivity, metabolism, and toxicity et al. thereby, the recognition of chiral molecules shows an increasingly important priority. In this paper, a novel method for chiral fluorescence recognition based on anthracene fluorescent dyes (AD)???water-soluble pillar[5] arene containing phosphonic acid group (PWP[5]) is developed. The AD as guest molecule can complex with PWP [5] to form 1:1 AD???PWP[5] assembly, and this assembly can be further used as a fluorescent probe to identify D/L-phenylalanine and D/L-phenylalaninol by fluorescent titration. The fluorescence intensity of the assembly was significantly reduced for D-phenylalanine and D-phenylalaninol, while L-phenylalanine or L-phenylalaninol was added to AD???PWP[5] assembly, the fluorescence intensity of the assembly almost unchanged. Hence, the chiral recognition based on assembly between the achiral fused ring fluorescent dye and achiral PWP[5] was developed.

     

溴化5-[4-(3-吡啶丙氧基苯基)]-10，15，20-三苯基卟啉对铜离子显色反应的研究

本文研究了溴化 5- [4 - (3-吡啶丙氧基苯基 ) ]- 10 ,15,2 0 -三苯基卟啉 ,在 p H=4 .0时与 Cu2 + 的显色反应条件 ,其络合物最大吸收波长为 4 13nm。在相同条件下 ,试剂最大吸收波长为 4 4 4nm,对比度大约30 nm。试剂与铜络合比为 1∶ 1,表观摩尔吸光系数为 2 .9× 10 5L· mol-1·cm-1,铜含量在 0— 6 0 μg/ L范围内符合比耳定律 ,可用于痕量铜的测定。     

Phase portrait ofSU(5) model. II intermediate phasesSU(3)×[U(1)]2 and [SU(2)]2×[U(1)]2

The effective potential of the scalar field in theSU(5) model has extrema with symmetry:SU(5),SU(4)×U(1),SU(3)×SU(2)×U(1),SU(3)×[U(1)]², [SU(2)]²×[U(1)]². In our recent paper it was shown that theSU(4)×U(1) phase as well asSU(3)×SU(2)×U(1) phase were stable at the nonzero temperature in a vast region of parameters. In the present paper it is found that the [SU(2)]²×[U(1)]² symmetric vacuum is unstable and theSU(3)×[U(1)]² symmetric vacuum can be metastable in the certain interval of the temperature. Domains of the three phases:SU(4)×U(1),SU(3)×SU(2)×U(1),SU(3)×[U(1)]²-could co-exist in the early. Universe.     

九个苯并冠醚的13C-NMR谱研究

本文测定了九个苯并冠醚的¹³C-NMR和¹H-NMR谱,结合元素分析、红外、紫外、质谱等数据,确定了这些冠酸的分子结构。根据NMR谱的谱线位置、裂分情况及取代基诱导效应,归属了全部¹³C-NMR谱线。并讨论了苯环上不同取代基对冠醚环上各碳化学位移的影响。     

Free radicals in X-irradiated 15N-labelled 5-nitrouracil

An analysis of a simple model for the interaction region of the potential energy surface of a collinear atom-diatomic molecule reaction is used to interpret recent observations of periodic trajectories on accurate energy surfaces.