伯胺N_(1923)与其它试剂对金属离子(Zn~(2+).Cd~(2+).RE~(3+))的萃取及协同萃取

胺类萃取剂具有其独特优点，特别是伯胺，因含有活泼氢，既能作为“阴离子交换剂”，又能与被萃的含氧金属络阴离了形成氢键而溶剂化，同时伯胺为一路易斯碱，可作为配体与某些金属离子形成配位键等，因而已广泛地用于金属离子的提纯与分离工业中。然而，1）为了寻找新的、更有效的萃取及协同萃取体系，以适应分析分离各种金属离子，改善金属离子的分离工艺；2）研究萃取和协同萃取的一般规律，探寻其内在规律性，充实完善萃取化学原理的内容；3）研究多元配合物的组成、结构和机理；4）系统地研究和比较不同结构胺类萃取剂与其它萃取剂对金属离子的萃取及协同萃取的相互作用，探讨多元配合物的形成条件等，因此，研究伯胺N_(1923)与其它萃取剂在不同酸度、不同条件，不同体系中对Zn(II)、Cd(II)、Re(III)的萃取及协同萃取具有一定意义。本文分别研究了伯胺N_(1923)与中性磷试剂对ZnCl_2、CdCl_2、Zn(SCN)_2的协同萃取；伯胺N_(1923)与HPMBP对RE（III）的协同萃取以及伯胺N_(1923)在不同介质中对Sc(III)的萃取机理等，并用得到了一些有意义的结果与结论。一、伯胺N_(1923)与中性磷萃取剂(TBP, DBBP)对Zn(II)、Cd(II)的协同萃取1. 伯胺N_(1923)与TBP、DBBP对ZnCl_2的协萃取 研究了伯胺N_(1923)与TBP、DBBP的正庚烷溶液从盐酸介质中对ZnCl_2的萃取机理，用斜率法、等摩尔系列法确定了协萃配合物组成为：(RNH_3Cl)_3·ZnCl_2·B、(RNH_3Cl)_2·ZnCl_2·B (B = TBP·DBBP)协萃反应为：ZnCl_2 + (RNH_3Cl)_3_((o)) + TBP_((o)) →~(K_(12)(TBP) (RNH_3Cl)_3·ZnCl_3·ZnCl_2·TBP_((o)) ZnCl_2+Z/3(RNH_3Cl)_(3(o)) + DBBP_((o)) → (RNH_3Cl)_2 · ZnCl_2·DBBP_((o))协萃配合物生成反应为：(RNH_3Cl)_3·ZnCl_(2(o)) + TBP_((o))→~(B_(12)(TBP) (RNH_3Cl)_3·ZnCl_2·TBP_((o)) (RNH_3Cl)_3·ZnCl_(2(o)) + DBBP_((o)) →~(B_(12)(DBBP) (RNH_3Cl)_2·ZnCl_2·DBBP_((o)) + RNH_3Cl_((o))同时发现，中性磷试剂对Zn(II)的协萃效应大小影响有下列关系：DBBP>TBP。并求得了协萃反应平衡常数和协萃配合物生成反应平衡常数。在研究溶剂对协同效应影响时发现，对芳香烃及其衍生物，分配比（D）与溶剂介电常数（ε）的关系为D_∝1/ε，而对芳香烃及其衍生物，分配比（D）与介电常数（ε）的关系为D_∝ε。讨论了温度对协萃反应的影响，对协萃配合物的IR、NMR谱也进行了研究。2.伯胺N_(1923)与TBP对Zn_(SCN)_2的协同萃取研究了伯胺N_(1923)与TBP的庚烷溶液从硝酸底液中对Zn(SCN)_2的萃取机理，用等摩尔系列法、斜率法确定了TBP和Zn(SCN)_2以及伯胺N_(1923)与TBP对Zn(SCN)_2的协萃配合物组成分别为：Zn(SCN)_2·3TBP. (RNH_3)_2Zn(SCN)_4·TBP,协谇反应为：Zn(SCN)_4~(2-) + (RNH_3NO_3)_(2(o)) + TBP_((o)) → (RNH_3)_2Zn(SCN)_4·TBP_((o)) + 2NO_3~-协萃配合物三种可能生成反应为(RNH_3)_2Zn(SCN)_(4(o)) + TBP_((o)) → ~(B'12) (RNH_3)_2Zn(SCN)_4·TBP_((o)) (a) (RNH_3NO_3)_(2(o)) + Zn(SCN)_2·3TBP_((o)) + 2SCN~-→~(β"12)→(RNH_3)Zn(SCN)_4βTBP_((o))+2TBP_((o))+2NO_3~- (b) (RNH_3NO_3)_(2(o)) + (RNH_3)_2Zn(SCN)_(4(o)) + 2SCN~- + Zn(SCN)_2.3TBP_((o)) →~(β"12)→R(RNH_3)_2Zn(SCN)_4.TBP_((o)) + 2NO_3~- + TBP_((o)) (c) 求得了协萃反应及生成反应的平衡常数，并由生成反应常数可知：β"'_(12) > β'_(12) > β"_(12)，即反应（c）对协萃配合物的生成贡献最大，其次反应（a），最小的是反应（b），同时还发现，不同阴离子对协萃效应影响有下列关系：SCN~- > Cl~_。并对协萃配合物的IR谱进行了研究，讨论了温度对协萃反应的影响。3. 伯胺N_(1923)与TBP、DBBP对Cd（II）的协同萃取研究了伯胺N_(1923)与TBP、DBBP的正庚烷溶液从盐酸介质中对Cd(II)的协同萃取，用等摩尔系列法、斜率法确定了协萃配合物组成为(RNH_3Cl)_2·CdCl_2·B，协萃反应及协萃配合物生成的反应分别为：CdCl_2 + 2/3 (RNH_3Cl)_(3(o)) + B_((o)) →~(K_(12)) → (RNH_3Cl)_2·CdCl_2·B_((o)) (RNH_3Cl_3)·CdCl_2_((o)) + B_((o)) →~(BR)(RNH_3Cl)_2·CdCl_2·B_((o)) + RNH_3Cl_((o))求得了协萃反应及生成反应平衡常数，计算了协萃反应的热力学函数值，结果还发现与Zn(II)协同萃取比较，协同效应大小有下列关系：Zn(II) > Cd(II)，由实验结果证实了“萃取效应大，则协萃效应小，反之，萃取效应小，则协同效应大”这一结论。并对协萃配合物的IR、NMR谱进行了研究。二. 伯胺N_(1923)与HPMBP对RE（III）的协同萃取研究了伯胺N_(1923)与HPMBP的二甲苯溶液在盐酸介质中对RE（III）的协萃机理（RE~(3+ = La~(3+), Pr~(3+), Eu~(3+), Gd~(3+), Tb~(3+), Er~(3+), Yb~(3+)和Y~(3+)）用斜率法及等摩尔系列法确定了协萃配合物组成为RNH_3Ln(PMBP)_4。求得了关于Pr(III)的协萃反应及生成反应的平衡常数值，协萃反应及生成反应分别为：Ln~(3+) + 4HPMBP_((o)) + RNH_3Cl_((o)) → RNH_3LN(PMBP)_(4(o)) + 4H~+ + Cl~- Ln(PMBP)_(3(o)) + RNH_3Cl_((o)) → RNH_3Ln(PMBP)_(4(o)) + H~+ + Cl~- 结果还发现协萃系数（R）随稀土元素的原子序数（Z）递变而出现“双峰效应”（未见文献报道），而且随RNH_3Cl浓度增加到某一一出现反协同效应。同时研究了关于Pr(III)协萃配合物的IR、NMR谱。三、伯胺N_(1923)在硝酸盐及硫氰酸盐混合介质中对Sc(III)的萃取研究了RNH_3NO_3在硝酸盐和硫氰酸盐混合介质中萃取Sc(III)的机理，结果发现，钪是以Sc(OH)_2~+形式萃入有机相的，且SCN~-, NO_3~-对RNH_3nO_3萃取Sc(III)具有协同效应，并且斜率法、连续变化法及PH值测定确定了萃取反应为：Sc(OH)_2~+ + SCN~- + 2(RNH_3NO_3)_(2((o)) → (RNH_3nO_3)_4.Sc(OH)_2SCN_((o)) Sc(OH)_2~+ + SCN~- + NO_3~- + (RNH_3NO_3)_(2(o)) → (RNH_3NO_3)_2.Sc(OH)(SCN)NO_3 + OH~-求得了反应的平衡常数及热力学函数值。

In0.2 Ga0.8 As-GaAs复合应力缓冲层上的1.3 μmInAs/GaAs自组织量子点

用光荧光谱和原子力显微镜测试技术系统研究了在2 nm In0.2Ga0.8As和x ML GaAs的复合应力缓冲层上生长的InAs/GaAs自组织量子点的发光特性和表面形貌.采用In0.2Ga0.8As与薄层GaAs复合的应力缓冲层,由于减少了晶格失配度致使量子点密度从约1.7×109 cm-2显著增加到约3.8×109cm-2.同时,复合层也有利于提高量子点中In的组份,使量子点的高宽比增加,促进量子点发光峰红移.对于x=10 ML的样品室温下基态发光峰达到1350 nm.

2-D and 3-D processing and interpretation of multi-fold ground penetrating radar data:a case history from an archaeological site

A 2.5-D and 3-D multi-fold GPR survey was carried out in the Archaeological Park of Aquileia (northern Italy). The primary objective of the study was the identification of targets of potential archaeological interest in an area designated by local archaeological authorities. The second geophysical objective was to test 2-D and 3-D multi-fold methods and to study localised targets of unknown shape and dimensions in hostile soil conditions. Several portions of the acquisition grid were processed in common offset (CO), common shot (CSG) and common mid point (CMP) geometry. An 8×8 m area was studied with orthogonal CMPs thus achieving a 3-D subsurface coverage with azimuthal range limited to two normal components. Coherent noise components were identified in the pre-stack domain and removed by means of FK filtering of CMP records. Stack velocities were obtained from conventional velocity analysis and azimuthal velocity analysis of 3-D pre-stack gathers. Two major discontinuities were identified in the area of study. The deeper one most probably coincides with the paleosol at the base of the layer associated with activities of man in the area in the last 2500 years. This interpretation is in agreement with the results obtained from nearby cores and excavations. The shallow discontinuity is observed in a part of the investigated area and it shows local interruptions with a linear distribution on the grid. Such interruptions may correspond to buried targets of archaeological interest. The prominent enhancement of the subsurface images obtained by means of multi-fold techniques, compared with the relatively poor quality of the conventional single-fold georadar sections, indicates that multi-fold methods are well suited for the application to high resolution studies in archaeology.

齐聚[3,2-b]并二噻吩的合成、表征及其在有机薄膜晶体管中的应用

通过Stille偶联反应合成了5,5″-二辛基-2,2′∶5′2″-三联[3,2-b]并二噻吩,并对该化合物的物理化学性质以及真空蒸镀薄膜的结构和形貌进行了详细表征.以这一化合物作为半导体层、采用顶电极结构制备了有机薄膜晶体管,并对薄膜生长基底温度做了优化,发现基底温度为100℃时器件性能最好,迁移率达到0.13 cm2/V.s,开关比为7×103,阈值电压为-19V.

Fabrication and luminescent properties of rare earths-doped Gd-2(WO4)(3) thin film phosphors by Pechini sol-gel process

Rare earth ions (Eu3+ and Dy3+)-doped Gd-2(WO4)(3) phosphor films were prepared by a Pechini sol-gel process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), atomic force microscopy (AFM) and photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting powders and films. The results of XRD indicate that the films begin to crystallize at 600degreesC and the crystallinity increases with the elevation of annealing temperatures. The film is uniform and crack-free, WO(4)(2-)mainly consists of closely packed fine particles with an average grain size of 80 nm. Owing to an energy transfer from 4 groups, the rare earth ions show their characteristic emissions in crystalline Gd-2(WO4)(3) phosphor films, i.e., D-5(J) -F-7(J), (J = 0, 1, 2, 3; J' = 0 1, 2, 3, 4, not in all cases) transitions for Eu3+ and F-4(9/2)-H-6(J) (J = 13/2, 15/2) transitions for D Y3+, with the hypersensitive transitions D-5(0)-F-7(2) (Eu3+) and F-4(9/2) - H-6(13/2) (Dy3+) being the most prominent groups, respectively.

Electrogenerated chemiluminescence sensing platform using Ru(bpy)(3)(2+) doped silica nanoparticles and carbon nanotubes

An effective electrogenerated chemiluminescence (ECL) sensor was developed by coimmobilization of the Ru(bpy)(2)(3+)-doped silica (RuDS) nanoparticles and carbon nanotubes (CNTs) on glassy carbon electrode through hydrophobic interaction. The uniform RuDS nanoparticles were prepared by a water-in-oil (W/O) microemulsion method and Ru(bpy)(3)(2+) doped inside could still maintain its high ECL efficiency. With such unique immobilization method, a great deal of Ru(bpy)(3)(2+) was immobilized three-dimensionally on the electrode , which could greatly enhance the ECL response and result in the increased sensitivity. On the other hand, CNTs played dual roles as matrix to immobilize RuDS nanoparticles and promoter to accelerate the electron transfer between Ru(bpy)(3)(2+) and the electrode. The as-prepared ECL sensor displayed good sensitivity and stability.

Dinuclear half-sandwich complexes containing bridging 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolato ligands. Molecular structures of Cp2Fe2(CO)(3)[mu-Se2C2(B10H10)], Cp2Ru2[mu-S2C2(B10H10)](2), and CP*Ru-2(2)(mu-Se)[mu-Se2C2(B10H10)].

Three prototypes of dinuclear complexes were obtained from the reactions of dilithium 1,2-dicarbacloso-dodecaborane-1,2-dichalcogenolates, (B10H10)C-2-(ELi)(2) (E = S, Se), with CpFe(CO)(2)Cl (1), CpRu(PPh3)(2)Cl (2), or [Cp*RuCl2](2) (3), respectively, and their structures have been determined by X-ray crystallography.

The AFM characterization of Ni(phen)(3)(2+) fixing effects on DNA

In this paper, the fixing and stretching effect of Ni(phen)(2+)(3) with different concentrations on DNA had been studied by Tapping mode AFM. Under an ambient condition, the high-resolution DNA images were obtained, the average height, width and length of well spread DNA molecules were measured. The results showed that because of the variations of ionic concentration, the density and topography of DNA molecules on substrate had a great difference. The AFM and gel electrophoresis results also showed that, under our experimental condition, DNA molecules kept intact, Ni(phen)(2+)(3) did not catalyze the cleavage activity of EcoRI, therefore, Ni (phen)(2+)(3) would be used to make high-resolution physical mapping of DNA by AFM.

THE CLEAVAGE REACTION OF THE MO-MO TRIPLE BOND - THE CRYSTAL-STRUCTURES OF MOLYBDENUM COMPLEXES [CPMO(CO)(2)(C(5)H(4)NS)], [CPMO(CO)(2)(C(9)H(6)NS)]O=PPH(3) AND [CPMO(CO)(2)(S(2)CNME(2)]

The reactions of [Cp2Mo2(CO)4] (1) with 2,2'-dipyridyl disulphide (C5H4NS-)2, 8,8'-diquinolyl disulphide (C9H6NS-)2 and tetramethyl thiuram disulphide (Me2NC(S)S-)2 in toluene solution resulted in the cleavage of the Mo-Mo triple bond to yield molybdenum complexes [CpMo(CO)2(C5H4NS)] (2), [CpMo(CO)2(C9H6NS)] (3) and [CpMo(CO)2(S2CNMe2)] (4), respectively. The molecular structures of 2, 3 . O=PPh3 and 4 were determined by X-ray diffraction studies. Crystals of 2 are monoclinic, space group P2(1)/n, with Z = 4, in a unit cell of dimensions a = 6.448(1), b = 12.616(2), c = 14.772(2) angstrom, beta = 92.85(1)-degrees. The structure was refined to R = 0.028 and R(w) = 0.039 for 1357 observed reflections. Crystals of 3 . O=PPh3 are triclinic, space group P1BAR, with Z = 2, in a unit cell of dimensions a = 11.351(3), b = 13.409(3), c = 9.895(2) angstrom, alpha = 94.59(2), beta = 90.35(2), gamma = 78.07(2)-degrees. The structure was refined to R = 0.033 and R(w) = 0.037 for 3260 observed reflections. Crystals of 4 are monoclinic, space group P2(1)/a and Z = 4 with a = 12.468(5), b = 7.637(2), c = 13.135(4) angstrom, beta = 96.62(3). The structure was refined to R = 0.032 and R(w) = 0.042 for 1698 observed reflections. Each of complexes 2-4 contains a cyclopentadienyl ligand, a cis pair of carbonyls and a chelate ligand (S,N donor or S,S donor). All the compounds have distorted square-pyramid structures.

Structure and biological activities of 2-(1,3-dithiolan-2-ylidene)-1-phenyl-2-(1,2,4-triazol-1-yl) ethanone

In order to find leading compounds with an excellent fungicidal activity, the tide compound 2-(1,3-dithiolan-2-yl-idene) -1-phenyl-2-(1,2,4-triazol-1-yl) ethanone was synthesized according to the biological isosterism and its structure was confirmed by means of IR, MS, H-1 NMR and elemental analysis. The single crystal structure of the tide compound was determined by X-ray diffraction. The preliminary biological test shows that the synthesized compound exhibits some biological activities.

Seven 3-methylidene-1H-indol-2(3H)-ones related to the multiple-receptor tyrosine kinase inhibitor sunitinib

The solid-state structures of a series of seven substituted 3-methylidene-1H-indol-2(3H)-one derivatives have been determined by single-crystal X-ray diffraction and are compared in detail. Six of the structures {(3Z)-3-(1H-pyrrol-2- ylmethylidene)-1H-indol-2(3H)-one, C13H10N2O, (2a); (3Z)-3-( 2-thienylmethylidene)-1H-indol-2(3H)-one, C13H9NOS, (2b); (3E)-3-(2-furylmethylidene)-1H-indol-2(3H)-one monohydrate, C13H9NO2 center dot H2O, (3a); 3-(1-methylethylidene)-1H-indol- 2(3H)-one, C11H11NO, (4a); 3-cyclohexylidene-1H-indol- 2(3H)-one, C14H15NO, (4c); and spiro[1,3-dioxane-2,3'-indolin]- 2'-one, C11H11NO3, (5)} display, as expected, intermolecular hydrogen bonding (N-H center dot center dot center dot O=C) between the 1H-indol-2(3H)-one units. However, methyl 3-(1-methylethylidene)- 2-oxo-2,3-dihydro-1H-indole-1-carboxylate, C13H13NO3, (4b), a carbamate analogue of (4a) lacking an N-H bond, displays no intermolecular hydrogen bonding. The structure of (4a) contains three molecules in the asymmetric unit, while (4b) and (4c) both contain two independent molecules.

Chironomid-based reconstructions of summer air temperature from lake deposits in Lyndon Stream, New Zealand spanning the MIS 3/2 transition

We present chironomid-based temperature reconstructions from lake sediments deposited between ca 26,600 cal yr BP and 24,500 cal yr BP from Lyndon Stream, South Island, New Zealand. Summer (February mean) temperatures averaged 1 1C cooler, with a maximum inferred cooling of 3.7 1C. These estimates corroborate macrofossil and beetle-based temperature inferences from the same site and suggest climate amelioration (an interstadial) at this time. Other records from the New Zealand region also show a large degree of variability during the late Otiran glacial sequence (34,000–18,000 cal yr BP) including a phase of warming at the MIS 2/3 transition and a maximum cooling that did not occur until the global LGM (ca 20,000 cal yr BP). The very moderate cooling identified here at the MIS 2/3 transition confirms and enhances the long-standing discrepancy in New Zealand records between pollen and other proxies. Low abundances (o20%) of canopy tree pollen in records from late MIS 3 to the end of MIS 2 cannot be explained by the minor (o5 1C) cooling inferred from this and other studies unless other environmental parameters are considered. Further work is required to address this critical issue.

Utilisation of ionic liquid solvents for the synthesis of Lily-of-the-Valley fragrance {beta-Lilial (R); 3-(4-t-butylphenyl)-2-methylpropanal}

The Heck arylation of 2-methylprop-2-en- I -ol in ionic liquids and organic solvents is reported using a range of homogeneous and heterogeneous palladium catalysts. Higher activity is observed in the ionic liquid media compared with N-methyl pyrrolidinone and under solventless conditions. The ionic liquid-catalyst system may be recycled easily with little loss in activity, although significant palladium leaching from the heterogeneous catalyst was observed. In the case of Trans-bis(2,3-dihydro-3-methylbenzothiazole-2-ylidene)diiodopalladium (11) reported to be highly active for this transformation, significant induction petiods were observed indicating that nanoparticles may be responsible for the catalysis. Using the ionic liquid Heck reaction, a recyclable synthesis for the fragrance beta-Lilial((R)) has been developed. (c) 2004 Elsevier B.V. All rights reserved.

3,5-dimethyl-4-amino-1,2,4-triazole (Dat) as a tridentate ligand in the polymeric cations of [Ag-3(Dat)(2)](NO3)(3)

Colourless single crystals of [Ag-3(Dat)(2)](NO3)(3) were obtained from a reaction of silver(l) nitrate and 3,5-dimethyl-4-amino-1,2,4-triazole (Dat). In the crystal structure (orthorhombic, Fdd2, Z = 8, a = 1100.1(2), b = 3500.3(2), c = 1015.4(3) pm, R, = 0.0434) there are two crystallographically non-equivalent silver sites in a one (Ag1) to two ratio (Ag2). Both resemble linear N-Ag-N coordination although angles are 163 degrees and 144 degrees, respectively Each Dat ligand coordinates with the two ring nitrogen atoms at 216 to 219 pm and with one amino-nitrogen atom at 229 pro. According to the composition [Ag-3(Dat)(2)](3+) = [(Dat)Ag-3/2](3+), a polymeric structure is built with all Ag+ ions bridging.

Anion-templated formation of a unique inorganic 'super-adamantoid' cage [Ag-6(triphos)(4)(O3SCF3)(4)](2+) [triphos = (PPh2CH2)(3)CMe]

In the presence of templating anions, 2:3 molar mixtures of triphos and silver(I) cations unexpectedly give novel hexanuclear cages, which result from an unusual 'endo-methyl' geometry of the triphos ligands.