Nitrate ion association with Nd3+

The overall stability constantsK ₁ andK ₂ of NdNO ₃ ²⁺ and Nd(NO₃) ₂ ⁺ complexes were determined (K ₁=1.77;K ₂=1.28) using an extraction method with tri-n-butyl phosphate as the extractant. The ratio ₁/₂ of the stepwise stability constants is discussed. It was established that the Nd(NO₃) ₂ ⁺ complex was an outer-sphere ion pair.

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Die Assoziation von Nitrat-Ion mit Nd³⁺

Zusammenfassung Mittels einer Extraktionsmethode wurden die StabilitätskonstantenK ₁ undK ₂ von NdNO ₃ ²⁺ - und Nd(NO₃)⁺-Komplexen bestimmt (K ₁=1.77;K ₂=1.28; Tri-n-butylphosphat als Extraktionsmittel). Das Verhältnis ₁/₂ der stufenweisen Stabilitätskonstanten wird diskutiert. Es stellte sich heraus, daß der Nd(NO₃)⁺-Komplex als ein Outer-Shere-Ionenpaar vorliegt.

     

Neue acetonylsubstituierte Azole II. 3-Acetonyl-1,2,4-oxadiazole, 2-Acetonyl-1,3,4-oxadiazole und 5-Acetonyl-1,2,4-thiadiazole

3-Acetonyl-1,2,4-oxadiazoles and 2-acetonyl-1,3,4-oxadiazoles are accessible starting with the ketal of acetoacetamide oxime and the ketal of acetoacetic acid hydrazide, respectively. 5-Acetonyl-1,2,4-thiadiazoles are obtained from 5-chloro-1,2,4-thiadiazoles andtert.-butyl acetoacetate. These Acetonyl-azoles are starting materials for three series of azolylvinyl phosphates and phosphonates.

Herrn Prof. Dr.Klaus Weissermel zu seinem 60. Geburtstag.     

用双氧水绿色氧化环己酮合成己二酸的研究

以30%的双氧水为氧化剂, 钨酸钠与含N或O的双齿有机配体(草酸)形成的络合物为催化剂, 在无有机溶剂、无相转移剂的条件下, 研究了环己酮氧化制己二酸的反应. 研究结果表明, 用廉价的草酸为配体, 最佳反应条件为钨酸钠∶草酸∶环己酮∶30%的双氧水的物质的量比为2.0∶3.3∶100∶350, 在92 ℃下反应12 h, 可制得80.6%的己二酸; 用GC-MS跟踪了氧化过程中三种主要物质环己酮、己内酯及己二酸含量随反应时间的变化关系, 提出了其主要氧化机理为环己酮首先经Beayer-Villiger氧化反应生成己内酯, 己内酯进一步氧化成己二酸.     

Excess molar enthalpies of binary mixtures for (tributyl phosphate+methanol/ethanol) at 298.15 K

Excess molar enthalpies of binary mixtures for tributyl phosphate (TBP)+methanol/ethanol were measured with a TAM air Isothermal calorimeter at 298.15 K and ambient. The results for xTBP+(1–x)CH₃OH are negative in the whole range of composition, while the values for xTBP+(1–x)C₂H₅OH change from positive values at low x to small negative values at high x. The experimental results have been correlated with the Redlich–Kister polynomial. IR spectra of the mixtures were measured to investigate the effect of hydrogen bonding in the mixture.     

一种新的磷酸根离子敏感电极研究

一种新的磷酸根离子敏感电极研究肖丹，俞汝勤，李军，袁孔铨（湖南大学化学化工系，长沙，４１００８２）关键词磷酸根，离子选择电极，磷酸二氢根磷酸根离子浓度的测定在化学化工、环境保护、生命科学和临床医学等领域有着重要的意义。对磷酸根离子敏感电极的研究和探索...     

Intercalation of Cyclic Amines into α-Titanium Phosphate

The intercalation of some amines (aniline, benzylamine, cyclohexylamine,piperidine, pyridine, pyrazine and piperazine) into -titaniumphosphate, Ti(HPO₄)_2×H₂O,has been investigated by the batch method and/or by exposing the host to thevapour of the amines. The changes in the interlayer distance of the solidduring the intercalation process was followed by X-ray powder diffraction.The new intercalates were characterised by chemical and thermal analysis.Materials with a monolaminar and/or bilaminar arrangement of amine moleculesin the phosphate interlayer region are obtained depending on the nature ofthe amine. Due to steric hindrance, saturated phases are not obtained forall amines studied. The thermal decomposition of the intercalates (nitrogenatmosphere), takes place in three stages: dehydration, removal of amines andcondensation of the hydrogenphosphate to pyrophosphate groups.     

GaPO4 high temperature crystal microbalance demonstration up to 720°C

Quartz-homeotypic gallium (ortho-) phosphate, GaPO₄, is of special interest for resonator applications asking for temperature compensated cuts with higher electro-mechanical coupling than quartz and operational temperatures up to 970°C. The crystal microbalance technique, well known for quartz (QCM) which can be used only at moderate temperatures, can now be extended to much higher temperatures using GaPO₄ crystals, benefiting from all three advantages mentioned above. Two different experiments were done to demonstrate the advantages of a crystal microbalance based on GaPO₄. First, the GaPO₄ resonator was used for film thickness determination and compared with a commercial QCM. This experiment demonstrated that the measuring range can be extended by using GaPO₄ resonators instead of quartz. The second experiment demonstrates the possibility for thermogravimetric analysis up to 720°C by using a new concept for resonator mounting.This revised version was published online in November 2005 with corrections to the Cover Date.     

Precise Conductance Measurements on Dilute Aqueous Solutions of Sodium and Potassium Hydrogenphosphate and Dihydrogenphosphate

Precise conductance measurements are reported on dilute aqueous solutions of the sodium and potassium salts of orthophosphoric acid at 25 ^∘C. Conductance measurements on solutions of electrolytes such as these phosphate salts that exist in solution as complicated mixtures of ions have previously proved difficult to interpret. To overcome this, a mathematical method has been developed to calculate the concentrations of all the species in the aqueous system M₃PO₄/M₂HPO₄/M₂HPO₄/H₃PO₄ (M = Na or K) over a continuous range of stoichiometries. The Lee–Wheaton conductance equation has been used to interpret the conductance of these multicomponent solutions in terms of the limiting ionic conductances and concentrations of all the ions in the solution. The limiting molar conductances of the ions H₂PO₄ ⁻ and HPO₄ ²⁻ and the ion-pair formation constants of these ions with sodium and potassium ions were determine This work has enabled the accurate determination of solution parameters for the important hydrogenphosphate ions in water and provides an excellent example of the use of an advanced conductance theory in the analysis of the conductance of multicomponent electrolyte systems.     

四苯基卟啉在改性磷酸锆层间的插入及荧光增强

近年来,出于节约一次性能源的考虑,人们已经加大对太阳能等天然资源的利用,致力于模拟天然光合作用的研究[1￣3],而光合作用中的捕光复合物又称为光子天线。光子天线中往往存在一种或几种猝灭剂,猝灭剂吸收光子后产生激发态的能量可以在不同分子或者同一分子的不同生色团之间转移,转移出能量的一方为能量给体,另一方为能量受体。     

The role of radicals in enzymatic processes

Research on the mechanism of action of coenzyme B12, adenosylcobalamin, as a graduate student introduced the author to the field of organic free radicals in enzymology. Twenty years later, related work on S-adenosylmethionine (SAM) as a "poor man's coenzyme B12" was initiated in a detailed analysis of the mechanism of action of lysine 2,3-aminomutase (LAM). The interconversion of L-lysine and L-beta-lysine is catalyzed by LAM, which requires SAM, pyridoxal-5'-phosphate (PLP), and a [4Fe-4S] cluster as coenzymes. The mechanism of this reaction has been delineated as a radical isomerization, in which radical formation is initiated by the [4Fe-4S]-dependent cleavage of the SAM into methionine and the 5'-deoxyadenosyl radical. The mechanism of this process is discussed, together with the role of this radical in hydrogen abstraction from lysine to initiate the substrate radical isomerization. The chemistry underlying the functions of SAM, PLP, and [4Fe-4S] in the action of LAM is novel in all respects, except for the formation of a lysine-PLP aldimine at the active site. Of the four free radicals in the mechanism, three have been characterized by EPR spectroscopy. In the suicide inactivation of adenosylcobalamin-dependent dioldehydrase (DDH) by glycolaldehyde, the formation of cob(II)alamin and 5'-deoxyadenosine is accompanied by the conversion of glycolaldehyde to cis-ethanesemidione radical at the active site. The cis-ethanesemidione radical has been characterized by EPR spectroscopy. Its exceptional stability at the active site is the basis for the inactivation of DDH by glycolaldehyde.