Self-assembly of a series of extended architectures based on polyoxometalate clusters and silver coordination complexes

Three unusual compounds based on polyoxometalate building blocks, [(H2O)5Na2(C6NO2H4)(C6NO2H5)3Ag2][Ag2IMo6O24(H2O)4] x 6.25H2O (1), [(H2O)4Na2(C6NO2H5)6Ag3][IMo6O24] x 6H2O (2), and (C6NO2H6)2[(C6NO2H5)2Ag][Cr(OH)6Mo6O18] x 4H2O (3), have been synthesized and characterized by elemental analysis; IR, XPS, and ESR spectroscopy; TG analysis; and single-crystal X-ray diffraction. Compound 1 is constructed from the cationic two-dimensional (2D) coordination polymer sheets which are constituted of [(H2O)5Na2(C6NO2H4)(C6NO2H5)3Ag2]3+ and anionic [Ag2IMo6O24(H2O)4]3- chains as pillars, forming a three-dimensional (3D) supramolecular framework via weak Ag-O interactions. Compound 2 is composed of the well-defined [IMo6O24]5- building blocks, which are linked through trinuclear Ag-pyridine-3-carboxylic acid, [(C6NO2H5)6Ag3]3+, fragments into a one-dimensional (1D) hybrid chain; adjacent chains are further connected by sodium cations to yield a novel 2D network. Compound 3 has a 1D chainlike structure constructed from [Cr(OH)6Mo6O18]3- building blocks and Ag-pyridine-4-carboxylic acid coordination units. The crystal data for these compounds are the following: 1, triclinic, P1, a = 13.280(3) A, b = 13.641(3) A, c = 16.356(3) A, alpha = 89.68(3) degrees, beta = 88.31(3) degrees, gamma = 75.87(3) degrees, Z = 2; 2, triclinic, P1, a = 11.978(2) A, b = 12.008(2) A, c = 13.607(3) A, alpha = 116.14(3) degrees, beta = 108.85(3) degrees, gamma = 93.86(3) degrees, Z = 1; 3, triclinic, P1, a = 10.458(2) A, b = 10.644(2) A, c = 12.295(3) A, alpha = 97.40(3) degrees, beta = 112.38(3) degrees, gamma = 113.59(3) degrees, Z = 1.     

Addition of grignard reagents to aryl acid chlorides: an efficient synthesis of aryl ketones

[chemical reaction: see text]. Direct addition of Grignard reagents to acid chlorides in the presence of bis[2-(N,N-dimethylamino)ethyl] ether proceeds selectively to provide aryl ketones in high yields. A possible tridentate interaction between Grignard reagents and bis[2-(N,N-dimethylamino)ethyl] ether moderates the reactivity of Grignard reagents, preventing the newly formed ketones from nucleophilic addition by Grignard reagents.     

Long‐range π‐type hydrogen bond in dimers CH2?HF,CH2O?H2O,and CH2O?NH3

Using four basis bets, (6‐311G(d,p), 6‐31+G(d,p), 6‐31++G(2d,2p), and 6‐311++G(3df,3pd), the optimized structures with all real frequencies were obtained at the MP2 level for the dimers CH₂O? HF, CH₂O? H₂O, CH₂O? NH₃, and CH₂O? CH₄. The structures of CH₂O? HF, CH₂O? H₂O, and CH₂O? NH₃ are cycle‐shaped, which result from the larger bend of σ‐type hydrogen bonds. The bend of σ‐type H‐bond O…H? Y (Y?F, O, N) is illustrated and interpreted by an attractive interaction of a chemically intuitive π‐type hydrogen bond. The π‐type hydrogen bond is the interaction between one of the H atoms of CH₂O and lone pair(s) on the F atom in HF, the O atom in H₂O, or the N atom in NH₃. In contrast with the above three dimers, for CH₂O? CH₄, because there is not a π‐type hydrogen bond to bend its linear hydrogen bond, the structure of CH₂O? CH₄ is noncyclic shaped. The interaction energy of hydrogen bonds and the π‐type H‐bond are calculated and discussed at the CCSD (T)/6‐311++G(3df,3pd) level. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Preparation of crosslinked polystyrene-supported ethylenediamine via a S-containing spacer and adsorption properties towards metal ions

Two novel chelating resins were prepared by anchoring ethylenediamine to crosslinked polystyrene via a spacer containing sulfide. Their structures were characterized by Fourier transform-infrared spectra (FTIR) and scanning electron microscopy (SEM). Porous structure parameters of the resins were measured by ASAP 2020 using BET and BJH methods. Their adsorption capacities for several heavy metal ions especially Hg²⁺ were investigated. The results showed that for the two resins, the more N contents did not mean the better adsorption capacity and the saturated adsorption capacity of poly(2-ethylenediamidomercaptomethylstyrene) (PSM-EDA) for Hg²⁺ could reach to 3.0 mmol/g at room temperature. Isothermal adsorptions of the resins for Hg²⁺ could be described by Langmuir formula. The adsorption mechanism of the resins for Hg²⁺, Cu²⁺ and Ag⁺ was confirmed by X-ray photoelectron spectroscopy (XPS) and FTIR.     

Synthesis of [18,19,21,22‐13C4]‐Labeled Tautomycin as an NMR Probe of Protein Phosphatase Inhibitor

We have accomplished the synthesis of ¹³C‐labeled tautomycin at the C18, C19, C21, and C22 positions starting from 100 % [¹³C]triethylphosphonoacetate for the purpose of elucidating the dynamics and conformation of the C17–C26 moiety. NMR spectroscopy of ¹³C‐labeled tautomycin revealed strong binding with protein phosphatase type 1 and new features in the ¹³C NMR spectrum, such as the very small three‐bond coupling constants (²J).     

Structural Study of Alkaline 1-Phenyl-1H-1, 2, 3, 4-tetrazole-5-thiolate Salts: An Example of Periodicity in Alkaline Cations

The alkaline 1-phenyl-1H-1, 2, 3, 4-tetrazole-5-thiolate salts, M[C₆H₅N₄CS] (M = Li ( 1 ), Na ( 2 ), K ( 3 ), Rb ( 4 ) and Cs ( 5 )) were obtained and characterized by means of mass spectrometry (FAB⁺) and NMR (¹H; ¹³C) spectroscopy. The structures of Na ( 2 ), K ( 3 ), Rb ( 4 ) and Cs ( 5 ) compounds were determined by X-ray diffraction methods. The ligand shows a rich variety of coordination patterns with the alkaline cations. The formation of a four-membered ring MSCN in the compounds with heavier alkali cations (K, Rb and Cs) is shown. In all the cations the coordination number around it increases with the ionic radius. Compounds with Cs⁺ and Rb⁺ exhibited the formation of Cs-C and Rb-C interactions with the phenyl group.     

Studies on the Synthesis and Properties of Temperature Responsive and Biodegradable Hydrogels

Novel linear poly(NIPA‐co‐CL) copolymers have been synthesized by radical copolymerization of N‐isopropylacrylamide (NIPA) and 2‐methylene‐1,3‐dioxepane (MDO). The structure of copolymers was confirmed by ¹H NMR and IR spectroscopy. Cross‐linked poly(NIPA‐co‐CL) hydrogels have also been prepared in toluene using N,N′‐methylenebisacrylamide as cross‐linking agent. The hydrogels thus obtained exhibit good temperature response and are biodegradable in the presence of proteinase K.

Temperature influence on the enzymatic degradation by proteinase K of poly(NIPA‐co‐CL) hydrogel (G‐60).     

Photooxidized products of recombinant alpha A-crystallin and W9F mutant

Human lenses contain many photosensitizers that absorb light at wavelengths above 300 nm, most notably UVA light (320-400 nm). Kynurenine (Kyn) and 3-hydroxykynurenine (HK), two of the best-known photosensitizers in the human lens, may play a significant role in photooxidation-related changes in lens proteins, such as conformational change and aggregation. In vitro irradiation experiments with proteins indicate that the Trp residue (with maximal absorption at 295 nm) is more susceptible to photooxidation by UVB light (280-320 nm) than by UVA light, but most UVB light below 300 nm is screened by the cornea and little reaches the lens, especially the nuclear region where nuclear color develops. Therefore, if photooxidation is an important contributor to nuclear color or nuclear cataract, it must arise from a photosensitized reaction. In the present study, we use recombinant alpha A- and its Trp-deficient mutant W9F as models to study the effects of UVA irradiation in the presence of HK or Kyn and of UVB (300 nm) irradiation on alpha-crystallins. alpha A-crystallin showed a large decrease in Trp fluorescence and a large increase in non-Trp (blue) fluorescence after the HK-sensitized or 300 nm photooxidation. For the W9F mutant, a smaller decrease in protein fluorescence (lambda ex at 280 nm) and a smaller increase in blue fluorescence than for the wild-type alpha A-crystallin were observed. A decrease in the near-UV CD was also observed for both photooxidized alpha A and the W9F mutant. The effect of Kyn sensitization is smaller than that of HK sensitization. A study of chaperone-like activity indicated that only 300 nm photooxidized alpha A and the W9F mutant increased the ability to protect insulin from dithiothreitol-induced aggregation. Thus, sensitized photooxidation can occur in amino acids other than Trp by UVA in the presence of HK or Kyn with effects similar to, albeit smaller than, those of direct UVB (300 nm) photooxidation.     

Determination of trace selenium in human plasma and hair with ternary inclusion compound-fluorescent spectrophotometry

A method for determination of selenium in plasma and hair with ternary inclusion compound-fluorescent spectrophotometry has been developed. The determination of selenium in plasma and hair can be performed directly in aqueous solution. Blood and hair samples were destroyed by oxygen flask combustion. The linear range was 10-500 ng mL-1 for plasma and 10-100 ng mL-1 for hair. Within-day and day-to-day precisions for plasma ranged from 5.4% to 9.3% (n = 7) and from 3.5% to 14.5% (n = 7), respectively. Within-day precisions for hair ranged from 0.6% to 6.2% (n = 7). Recoveries ranged from 91.0% to 97.8% for plasma and from 95.0% to 102.0% for hair. The blood samples from 15 Hans and 20 Uygurs in Xinjiang Uygur automatic region and 23 Hans in Liaoning province were collected and determined. It was indicated that no statistically significant difference in plasma selenium concentration of the Hans between Xinjiang and Liaoning was found (F = 1.36, P > 0.05). However, there were statistically significant differences between the Hans and the Uygurs in Xinjiang (F = 1.01, P < 0.01) and between males and females in the two areas (P < 0.01). There was a low correlation between plasma selenium concentration and hair selenium concentration. The ratio of hair selenium concentration to plasma selenium concentration was 2.17, with a range of 1.63-2.88.     

Die Ringinversions-Barriere in [2.2]Metacyclophan

From racemization studies on optically active [2.2]metacyclophanes substituted in position 4, the parameters of activation for the inversion of the tenmembered ring were found to be: G ₄₂₃ =31.5 kcal/mole, H =27.5 kcal/mole and S =–10 Cl/mole.Racemization does not occurvia bond forming or breaking; the value for the inversion barrier is not affected by substituents in position 4 and therefore corresponds to the value of unsubstituted [2.2]metacyclophane, whereas substituents in the bridge exert a distinct influence. These results can easily be explained on the basis of the isoconformational concept.

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Herrn Prof. Dr.O. Hoffmann-Ostenhof mit besten Wünschen zum 60. Geburtstag gewidmet.