Dynamic behaviour of river colloidal and dissolved organic matter through cross-flow ultrafiltration system

Through cross-flow filtration (CFF) with a 1-kDa regenerated cellulose Pellicon 2 module, the ultrafiltration characteristics of river organic matter from Longford Stream, UK, were investigated. The concentration of organic carbon (OC) in the retentate in the Longford Stream samples increased substantially with the concentration factor (cf), reaching approximately 40 mg/L at cf 15. The results of dissolved organic carbon (DOC) and colloidal organic carbon (COC) analysis, tracking the isolation of colloids from river waters, show that 2 mg/L of COC was present in those samples and good OC mass balance (77-101%) was achieved. Fluorescence measurements were carried out for the investigation of retentate and permeate behaviour of coloured dissolved organic materials (CDOM). The concentrations of CDOM in both the retentate and permeate increased with increasing cf, although CDOM were significantly more concentrated in the retentate. The permeation model expressing the correlation between log[CDOM] in the permeate and logcf was able to describe the permeation behaviour of CDOM in the river water with regression coefficients (r(2)) of 0.94 and 0.98. Dry weight analysis indicated that the levels of organic colloidal particles were from 49 to 71%, and between 29 and 51% of colloidal particles present were inorganic. COC as a percentage of DOC was found to be 10-16% for Longford Stream samples.     

Study of the structure of poly(methyl methacrylate) obtained in the presence of potassium hydride

Electrospray ionization mass spectrometry (ESI-MS) in positive- and negative-ion mode and multi-step tandem mass spectrometry (ESI-MS ( n) ) were selected for the determination of the structure of poly(methyl methacrylate) obtained using potassium hydride as initiator. Macromolecules with methoxy and methyl starting groups, i. e. those situated at the beginning of the polymer backbone, were observed in this case. No other differences in the chain structure were found in the polymer.     

Numerical treatment discussion and ab initio computational reinvestigation of physisorption of molecular hydrogen on graphene

A numerical treatment suitable for the computational investigation of physisorption of molecular hydrogen on carbon nanostructures has not been sufficiently discussed. In this paper it is shown that results used as a reference are actually a product of poorly solved interactions and contaminated estimates with errors which would be of the order of 60%. Moreover, using ab initio molecular orbital theory, under the rigid monomer supermolecular approach, the physisorption energy of molecular hydrogen on graphene was reinvestigated. The graphene surface was modeled as a coronenelike (C(24)H(12)) graphene sheet. The basis set superposition error was corrected by means of the counterpoise method. The H(2)-H(2) and H(2)-benzene interactions were examined, under systematic combinations of basis sets and correlation methods, including the aug-cc-pVQZ basis set and the coupled cluster correlation method with single, double, and noniterative triple excitations, searching for a numerical treatment with a reasonable trade-off between efficiency and accuracy. Asymmetrical modeling strategies, using diffusion augmented basis sets with preference for the adsorbate, were found to be effective. Also local modeling strategies, using more complete basis sets for the nearest atoms to the adsorbate than for the rest of the substrate, were considered. The aug-cc-pVTZ basis set for the adsorbate and for the nearest atoms to the adsorbate and the cc-pVTZ basis set for the rest of the cluster-modeled graphene, at the second-order Moller-Plesset perturbation theory correlation level, was selected as reference treatment. It was found that the physisorption energy of molecular hydrogen on graphene would be of the order of 0.06 eV, which would be 25% less than what has been previously published, though it would be sufficient to permit the storage of hydrogen physisorbed on carbon. To our knowledge this would be the most realistic theoretical estimate of the mentioned energy to date.     

涂敷氧化铁电极的光电化学和介电性质的研究

本文利用涂敷Fe(C_8H_(15)O_2)_3[2-乙基己醇酸铁(Ⅲ)]于Fe,Ti,Pt金属基片上,热氧化分解制成多晶氧化铁电极。对其介电、光电化学行为的测定,表明它们与利用热氧化法以及阳极氧化法所制成的多晶氧化铁电极的性能相似,具有n型半导体的特性。借助于交流阻抗的快速测定,并且选择了一种等效电路,测定了空间电荷区电阻、电容的变化。这种方法可以用来监测光电极的相对光效率。     

Merging organometallic chemistry with polyoxometalate chemistry

A series of polyoxomolybdate-incorporated organometallic complexes has been obtained by reaction of [MBr(CO)5] or solvated M(CO)3+ ions (M = Mn or Br) with (nBu4N)2[Mo2O7] in methanol, sometimes in the presence of triols of the type RC(CH2OH)3 (R = Me or CH2OH). Their molecular structures are related to those of previously described polyoxoalkoxomolybdates through the formal replacement of fac-MoO2(OR)+ units by topologically equivalent fac-M(CO)3+ units. Representative pairs of structurally related clusters include [Mo2O6(OMe)4-Re(CO)32]2- and [Mo4O10(OMe)6]2-, [Mo2O4MeC(CH2O)32Mn(CO)3]- and [Mo3O6(OMe)MeC(CH2O)32]-, [Mo2O4HOCH2C(CH2O)32Mn(CO)32] and [Mo4O8(OEt)2MeC(CH2O)32], [Mo6O16(OMe)2MeC(CH2O)32-Mn(CO)32]2- and [Mo8O20(OMe)4-MeC(CH2O)32]2-. Although the frameworks of the majority of derivatives are based on tetranuclear units which display the common rhomb-like structure, the alternative cubane-type arrangement is observed in [Mo2O5(OMe)5M(CO)32]-.     

A fluorimetric study of pindolol and its complexes with cyclodextrins

Spectrofluorimetric characteristics of pindolol have been investigated with the aim of using this technique for analytical determinations. Other monosubstituted indole derivatives, 4-methoxy and 5-methoxyindole, have been also studied for comparative purposes. Corrected excitation and emission wavelengths in different solvents are reported and the effect of solvent on the Stokes shifts of these compounds has been analysed using the Lippert equation. In addition, the Stokes shift of pindolol has been determined in dioxan-water solvent mixtures and the presence of specific solvent effects is discussed. The fluorescence of pindolol is pH dependent, the quantum yields determined in water are lower than those in other solvents. With respect to the sensitivity, it has been found that the detection limits in aqueous solutions are improved in the presence of beta and methyl-beta-cyclodextrin. Finally, a fluorimetric analysis of the interaction between pindolol and different cyclodextrins has been carried out in order to determine the apparent stability constants of the complexes and the thermodynamic parameters associated to complexation.     

Cover Picture

The cover picture shows a model of the "progenitor-TADDOLs" in front of a panorama of the Fünffingersstocks and the Wenden Glacier in the Titlisgebiet (Switzerland). The model is flanked by a stylized view of the general mechanistic model for the preferred stereochemical pathway of the Ti-TADDOLate-catalyzed reaction of chelating substrates (left) and a blackboard (right) showing formulae of compounds that can be prepared with high enantioselectivity by nucleophilic addition in the presence of titanium TADDOLates. From TADDOL, introduced in 1982, a genuine auxiliary system for the "introduction of chirality" (not only by reaction) has been developed, which, in the final sprint against the competition has a good chance of securing a place on the winning podium. The photograph of the mountain landscape was taken by Dr. J. Frackenpohl, the cover picture was generated by one of the authors (A.H.) of the comprehensive review of TADDOLs in this issue (p. 92 ff.) with the help of the program Povray. Supporting information for this article is available on the WWW under http://www.angewandte.com or from the author.     

Aggregation and reactivity of the cesium enolate of 6-phenyl-alpha-tetralone: comparison with the lithium enolate

The cesium enolate of 6-phenyl-alpha-tetralone (CsPAT) has a lambda(max) in THF at about 387 nm, but the variation with concentration is too small for application of singular value decomposition. Proton-transfer studies with several indicators show that CsPAT forms monomer-tetramer mixtures with a tetramerization equilibrium constant, K(1,4) = 2.3 x 10(11) M(-3). The pK of the monomer is 23.39 on a scale where fluorene is assigned 22.9 (per hydrogen). For comparison, the lithium enolate, LiPAT, is also a monomer-tetramer with K(1,4) = 4.7 x 10(10) M(-3) and a monomer pK = 14.22. HMPA in large amounts promotes dissociation to monomer with both enolates. Ion-pair S(N)2 initial rates were measured for CsPAT with several alkyl halides and with methyl tosylate and compared with other rates with LiPAT. In all cases, the enolate monomers are much more reactive than the aggregates. Reaction of CsPAT with alkyl halides is generally C-alkylation but HMPA promotes increasing amounts of O-alkylation. A new indicator, 11-methyl-11H-benzo[b]fluorene, has a pK on the cesium scale of 23.39.     

Total synthesis of (+)-belactosin A

A concise first total synthesis of the antitumour antibiotic belactosin A is reported, involving coupling of beta-lactone carboxylic acid 3 with N-Ala-aminocyclopropyl alanine 11.