配位聚合物{[CoL][FeⅡFeⅢ(ox)3·1.5H2O]}∞的合成、波谱表征和磁学性质

A new Schiff base complex， CoL(ClO₄)·3H₂O (1) {L represents condensed from equal molar ratio of sali-cylaldehyde and diethylenetriamine} was synthesized and characterized. Further， a new coordination polymer， {[CoL][Fe^ⅡFe^Ⅲ(ox)₃·1.5H₂O]}_∞ (2)， was synthesized and characterized， where ox^2-=oxalate. The results of the IR and M?ssbauer spectra of 2 revealed that the coordination polymer exists 2-D layer structure in the solid state， and anions layer was formed by [^ⅡFe^Ⅲ(ox)₃]^- unit. The magnetic properties of 2 have been measured and the results indicate that there is magnetic ordering in the low temperature， which may arise from intermolecular ferromagnetic interactions or spin canted effects.     

配位聚合物{[MnL][FeⅡFeⅢ(ox)3·1.5H2O]}∞的合成及其磁学性质

合成和表征了一种新的Schiff碱配合物MnL(ClO4)*3H2O(1)(其中L为n(水杨醛)∶n(二乙撑三胺)=1∶1缩合而成的Schiff碱).1与FeSO4*7H2O和K3[Fe(ox)3]*3H2O(ox=oxalate)进一步反应,生成了双金属层状配位聚合物{[MnL][FeⅡFeⅢ(ox)3]*1.5H2O}∞(2).IR和Mssbauer谱测定结果表明,2具有二维层状结构,其阴离子层由[FeⅡFeⅢ(ox)3]-单元构成.变温磁化率(5K～100K)测试结果表明,2中的自旋载体之间存在反铁磁交换作用.5K时的磁滞现象表明2在低温时可能存在铁磁有序,这可能是亚铁磁或自旋倾斜造成的.     

Influence of target surface degradation on the properties of r.f. magnetron‐sputtered calcium phosphate coatings

This paper reports a detailed study of how repeated r.f. magnetron sputtering from a hydroxyapatite (HA) powder target affects the nature and reproducibility of a sequential series of thin‐film coatings deposited onto Ti6Al4V substrates. An evaluation of the effective lifespan of the HA sputter targets and the reproducibility of the calcium phosphate (CaP) coatings produced from them has been made from Fourier transform infrared spectroscopy, XPS and, as appropriate, atomic force microscopy and SEM/energy dispersive x‐ray analyses. The annulus region of the target surface, from which sputtering under r.f. magnetron conditions normally occurs, showed severe surface degradation after only one deposition run, as indicated by significant PO₄^3? and OH^? depletion. This deterioration continued after each subsequent deposition cycle but to a much lesser extent than that observed in the initial sputtering period. The layers produced from all of the sputter runs contained the expected Ca²⁺ and PO₄^3? species characteristic of a CaP system but were OH^? deficient in the as‐deposited state. However, the chemical and morphological properties of the coatings did not change significantly until after the third consecutive sputter cycle. Hence, these data indicate that, even though a significant level of degradation of the HA target occurs at the outset of the sputtering procedure, the general plasma conditions employed here have a dominant influence on the coating properties until a critical degradation condition is met. As such, the compacted HA powder targets of interest can have a life‐cycle greater than single usage without detriment to the chemistry and morphology of the coatings produced from them. Copyright © 2003 John Wiley & Sons, Ltd.     

荧光钙探针试剂及其在生物分析中的应用

本文评论了荧光钙探针试剂合成、性质、结构和生物分析应用方面的进展。各种典型的荧光钙探针试剂均已分别加以讨论。     

内蒙古牧区蒙、汉族人发铜、锌、铁、锶及钙的X-射线荧光光谱法测定

用X-射线荧光光谱法，测定了387例内蒙古牧区蒙古族、汉族成人和儿童的发中铜(Cu)、锌(Zn)、铁(Fe)、锶(St)及钙(Ca)的含量，对同一地区蒙、汉族成人间，成人及儿童间发中五种元素含量进行了比较分析。结果表明：蒙汉族成人发中Cu，Zn、Fe含量不受种族及饮食习惯的影响，其含量无显著性差异；蒙汉族成人发中Sr和Ca含量存在着相平行的显著差异；牧区儿童发Zn含量与牧区成人发Zn含量差异无显著性意义，提示牧区儿童不缺Zn，可能与多动物性食物有关；牧区儿童发中Cu、Fe、Sr、Ca均显著低于牧区成人、可能与儿童发育旺盛和Zn摄入量高对Cu、Fe吸收发生抑制有关。     

Tetramethylammonium-calcium-triazid. Darstellung und Kristallstruktur

[N(CH₃)₄]Ca(N₃)₃,M=240.29, was prepared from aqueous solutions of tetramethylammoniumazide with calciumazide at 298 K. The crystals are tetragonala=936.6(7) pm,c=694.7(5)pm, space group P4/nmm,Z=2, (x)=1.31Mgm^–3. The crystal structure was determined by single crystal x-ray diffraction (234 Mo-K-reflections, =0.469 mm^–1,R=0.064). Calcium is octahedrally coordinated to six azide groups. The octahedra are connected via azide groups to a threedimensional array with the complex ammonium ions between. The terminal nitrogen atoms of the azide groups and the methyl groups are considerably disordered.

     

Formation of CaF and AlF in the arc plasma and spectrochemical determination of Ca and Al

Summary The influence of chemical reactions in d.c. arc plasma on the atomic emission determination of traces has been investigated. The effect of added NH₄F on the intensity of spectral lines of Ca and Al was examined. A decrease of the spectral line intensities of Ca and Al in the presence of NH₄F occurred, if the sample had not been mixed in the electrode with NH₄F. The AlF band spectrum, transition A ¹ X ¹ , was observed in absorption of the arc radiation. Further, the axial intensity distribution of Ca, Al, Ga and Ag spectral lines and of the head of the green system of CaF band, has been measured. The depressive effect of fluorine on spectral line intensities of Ca, Al, Ga and Ag has to be connected with the processes in plasma. It is suggested that the formation of fluoride radicals could take part in this effect.

---

Bildung von CaF und AlF im Bogenplasma und spektrochemische Bestimmung von Ca und Al

Zusammenfassung Der Einfluß von chemischen Reaktionen im Lichtbogenplasma auf die spektrochemische Spurenanalyse wurde erörtert. Die Wirkung einer Zugabe von Ammoniumfluorid auf die Intensitäten der Spektrallinien des Calciums und Aluminiums wurde untersucht. Wenn die Probe nicht in der Elektrode mit NH₄F gemischt war, wurde eine Intensitätserniedrigung von Ca- und Al-Spektrallinien in Anwesenheit von NH₄F beobachtet. Das AlF-Bandenspektrum, Übergang A ¹ X ¹ , wurde in Absorption der Bogenstrahlung beobachtet. Die Axialverteilung der Linienintensitäten von Ca, Al, Ga und Ag wie auch der Intensität der Kante des grünen Systems der CaF-Banden wurde untersucht. Die depressive Wirkung des Fluors auf die Linienintensitäten von Ca, Al, Ga und Ag sollte mit den Vorgängen im Plasma in Zusammenhang gebracht werden. Es kann vorausgesetzt werden, daß die Bildung der Fluoridradikale bei diesem Effekt eine Rolle spielt.

     

A mild and practical method for the regioselective synthesis of N-acylated 3,4-dihydropyrimidin-2-ones. New acyl transfer reagents

The treatment of 3,4-dihydropyrimidin-2-ones with n-BuLi at −78 °C, followed by quenching with various electrophiles furnished N3-substituted derivatives, regioselectively. Further, N1,N3-diacyl derivatives were found to transfer N1-acyl groups to nucleophilic sites.     

Small angle neutron scattering studies on nonaqueous dispersions of calcium carbonate Part 2. Determination of the form factor for concentric spheres

Colloidal dispersions of calcium carbonate, stabilised primarily by a surface active agent, in both toluene and dodecane have been examined by small angle neutron scattering. A model has been developed to simulate the scattering behaviour of the particles and is based on the idea of a concentric sphere with a homogeneous layer of adsorbed material surrounding a core particle. Computations based on the model show a wide variation of scattering behaviour with variation of the coherent scattering length of the dispersion medium. These predictions were confirmed by experiment. A method is described for analysis of the experimental data which leads to a determination of the thickness of the adsorbed layer, the radius of the core particle and the standard deviation of core particle radius.     

Conductivity Studies of Dilute Aqueous Solutions of Oxalic Acid and Neutral Oxalates of Sodium, Potassium, Cesium, and Ammonium from 5 to 35°C

Conductivity measurements of oxalic acid and neutral oxalates (disodium oxalate, dipotassium oxalate, dicesium, and diammonium oxalate) were performed on dilute aqueous solutions, c < 3 × 10^–3 mol-dm^–3, from 5 to 35°C. These data and those available from the literature were analyzed in terms of dissociation steps of oxalic acid, the Onsager conductivity equation for neutral oxalates, the Quint–Viallard conductivity equation for the acid, and the Debye–Hückel equation for activity coefficients, to give the limiting equivalent conductances of bioxalate anion ;(HC₂O₄ ^–) and oxalate anion (1/2C₂O₄ ^2–) and the corresponding dissociation constants K ₁ and K ₂.