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51.
Lobana Tarlok S. Paul Seema Hundal Geeta Obrai Sangeeta 《Transition Metal Chemistry》1999,24(2):202-205
Reaction of 1-hydroxypyridine-2-thione (HpyOS) in CHCl3 with Ag2CO3 suspended in CHCl3 under magnetic stirring followed by addition of PPh3 yields a product of stoichiometry: Ag(pyOS)(PPh3). The compound adopts a dimeric structure [Ag(pyOS)(PPh3)]2 (1) where each Ag atom acquires a distorted tetrahedral geometry by co-ordinating to one oxygen, two sulphur and one phosphorus atoms. The Ag2S2 core forms a parallelogram [Ag—S 2.507(1), 2.822(1)Å] with Ag—S—Ag and S—Ag—S angles of 74.8(1) and 105.2(1)°, respectively. 相似文献
52.
Andrew J. Taylor Dr. Robert Hein Sophie C. Patrick Prof. Jason J. Davis Prof. Paul D. Beer 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2024,136(6):e202315959
Anion sensing via either optical or electrochemical readouts has separately received enormous attention, however, a judicious combination of the advantages of both modalities remains unexplored. Toward this goal, we herein disclose a series of novel, redox-active, fluorescent, halogen bonding (XB) and hydrogen bonding (HB) BODIPY-based anion sensors, wherein the introduction of a ferrocene motif induces remarkable changes in the fluorescence response. Extensive fluorescence anion titration, lifetime and electrochemical studies reveal anion binding-induced emission modulation through intramolecular photoinduced electron transfer (PET), the magnitude of which is dependent on the nature of both the XB/HB donor and anion. Impressively, the XB sensor outperformed its HB congener in terms of anion binding strength and fluorescence switching magnitude, displaying significant fluorescence turn-OFF upon anion binding. In contrast, redox-inactive control receptors display a turn-ON response, highlighting the pronounced impact of the introduction of the redox-active ferrocene on the optical sensing performance. Additionally, the redox-active ferrocene motif also serves as an electrochemical reporter group, enabling voltammetric anion sensing in competitive solvents. The combined advantages of both sensing modalities were further exploited in a novel, proof-of-principle, fluorescence spectroelectrochemical anion sensing approach, enabling simultaneous and sensitive read out of optical and electrochemical responses in multiple oxidation states and at very low receptor concentration. 相似文献
53.
H. Binder R. Kellner K. Vaas M. Hein F. Baumann M. Wanner R. Winter W. Kaim W. Hnle Y. Grin U. Wedig M. Schultheiss R. K. Kremer H. G. von Schnering O. Groeger G. Engelhardt 《无机化学与普通化学杂志》1999,625(7):1059-1072
Halogenation of nido-B10H14 with C2H2Cl4, C2Cl6, Br2, or I2, produces by cluster degradation the (2 n)-closo-clusters B9X9 (X = Cl, Br, I). The synthesis of salts of the perhalogenated radical anions of the type (2 n + 1)-closo-[B9X9]· – and of the corresponding dianions (2 n + 2)-closo-[B9X9]2– from neutral B9X9 is described [n is the number of cluster atoms; (2 n), (2 n + 1), and (2 n + 2) is the number of cluster electrons]. Molecular and crystal structures of B9Cl9, B9Br9, [(C6H5)4P][B9Br9] · CH2Cl2, and [(C4H9)4N]2[B9Br9] · CH2Cl2 have been determined via X-ray diffraction. All three oxidation states of the cluster retain the tricapped trigonal prism. The reduction of the clusters B9X9 was shown by cyclic voltammetry in CH2Cl2 to proceed via two successive one-electron reversible steps, separated by at least 0.4 V. The paramagnetic radical anions [B9X9]· – (X = Cl, Br) were further characterized by magnetic susceptibility measurements of [Cp2Fe][B9X9] and [Cp2Co][B9X9], respectively. The EPR spectra of [B9X9]· – (X = Cl, Br, I) in glassy frozen CH2Cl2 solutions showed increasing g anisotropy for the heavier halogen derivatives, illustrating significant halogen participation at the singly occupied MO. The 11B NMR spectra of CD2Cl2 solutions of the neutral clusters B9X9 exhibit only one sharp resonance, indicating that the boron atoms are highly fluxional in solution. In contrast, two different boron resonances as expected for a rigid tricapped trigonal prism are clearly observed for the [B9X9]2– dianions in solutions and for solid B9Br9 in the 11B MAS NMR spectra. Temperature dependent 11B MAS NMR experiments on B9Br9 and [B9Br9]2– in the solid state show a reversible coalescence of the two resonances at higher temperature. 11B MAS NMR spectra and DTA measurements of [B9Br9]2– showed a phase transition. 相似文献
54.
Boor Singh Lalia K. Yamada M. S. Hundal Jin-Soo Park Gu-Gon Park Won-Yong Lee Chang-Soo Kim S. S. Sekhon 《Applied Physics A: Materials Science & Processing》2009,96(3):661-670
Polymer–ionic liquid composite electrolytes based on poly (vinylidenefluoride-co-hexafluoropropylene) (PVdF–HFP) and room
temperature ionic liquid: 2,3-dimethyl-1-octylimidazolium hexafluorophosphate (DMOImPF6) have been synthesized and studied. The addition of dimethylacetamide (DMA) and propylene carbonate (PC), both with high
dielectric constant and low viscosity, to polymer electrolytes has been found to result in an enhancement of conductivity
by one order of magnitude. Composite polymer electrolytes containing ionic liquid have been found to be thermally stable upto
300°C. Motional narrowing observed in the variation of line width of 1H and 19F NMR peaks with temperature suggests that both cations and anions are mobile in these electrolytes. 相似文献
55.
Reactions of equimolar solutions of copper(I) halides with 1-methyl-1,3-imidazoline-2-thione (SC4H6N2) in acetonitrile have yielded a trinuclear complex, {Cu3(η1-Br)3(μ-SC4H6N2)3} · CH3CN 1, and 1D polymer, {Cu2(μ-I)2(μ-SC4H6N2)2}n2. The thio-ligands/halogens adopt μ-S, η1-X or μ-X modes. There is weak interaction between trinuclear units {Cu···Br, 3.025 Å} and Cu···Cu contacts lie in the range, 2.974(2)–3.650(2) Å. Polymer 2 has alternating Cu2I2 and Cu2S2 cores involving sulfur/iodine bridging in a twisted ribbon type arrangement with short Cu···Cu distances {2.6912(9) and 2.785(9) Å}, respectively. The polynuclear complexes in dimethyl sulfoxide exhibit intense fluorescent bands {λem = 319 (1) and 322 (2)}. 相似文献
56.
57.
Nils Helge Schebb David Falck Helene Faber Eva-Maria Hein Uwe Karst Heiko Hayen 《Journal of chromatography. A》2009,1216(27):5249-5255
A new liquid chromatography–electrospray ionization mass spectrometry (LC–ESI-MS) method for the fast determination of phospholipase A2 (PLA2) activity has been developed. For the first time, the method allows the parallel detection of glycerophosphatidylcholine (GroPCho) as PLA2 substrate as well as of its products fatty acid (FA) and lyso-GroPCho. ESI-MS was carried out in negative ion mode, detecting the FA as [M − H]− ions and the lyso-GroPCho and GroPCho as acetate adducts [M + Ac]−. Utilizing a fast gradient on a short C5-modified silica gel column with 3 μm particles, five GroPChos, five FAs and six lyso-GroPChos could be separated according to their chain length in less than 3 min. A very high average chromatographic efficiency of 41,200 theoretical plates (plate height 0.5 μm) was achieved for the separation of the GroPChos. The method was applied for monitoring the release of arachidonic acid (20:4 FA) and 1-stearoyl-lyso-sn-GroPCho (18:0 GroPCho) from unilamellar vesicles of 1-stearoyl-2-arachidonoyl-sn-GroPCho (18:0/20:4 GroPCho). With a limit of detection of 0.5 pmol (total amount injected on column) for the FAs and lyso-GroPChos and 1.5 pmol for the GroPChos as well as a linear range of 1.5 decades, the method has proven to be suitable for the monitoring of different secretory PLA2 (sPLA2) conversions. Furthermore, it was applied to screen a small library of PLA2 inhibitors for their activity towards sPLA2 type V and snake venom of Bothrops moojeni. In both cases, active samples could be directly identified. With its short analysis time, its high chromatographic efficiency and the parallel detection of substrate and all products, the developed LC–ESI-MS method is well suited for the analysis of PLA2 activity. 相似文献
58.
A proficient etiquette for the stereoselective synthesis of novel 3-methylthio-β-lactams and their Lewis acid mediated functionalization is described. Treatment of 2-methylthioethanoic acid and appropriate imines in the Staudinger reaction leads to the stereocontrolled synthesis of novel trans-3-methylthio-β-lactams in excellent yields. cis-3-Chloro-3-methylthio-β-lactams, obtained from stereoselective chlorination of trans-3-methylthio-β-lactams using N-chlorosuccinimide (NCS) and AIBN, were subjected to Lewis acid (TiCl4 or SnCl4) mediated functionalization using various active aromatic, heterocyclic and aliphatic compounds (nucleophiles). This reaction provides an easy access to novel, stereoselective cis-3-monosubstituted-3-methylthio-β-lactams, which further undergo smooth desulfurization with Raney-nickel to afford C-3 cis- and trans-monosubstituted-β-lactams. The cis or trans configuration of the hydrogen/chloro/nucleophile substituent at C-3 was assigned with respect to C4–H. 相似文献
59.
Anno Hein Ioannis Karatasios Dionysis Mourelatos 《Analytical and bioanalytical chemistry》2009,395(7):2061-2071
The present case study concerns the technology of Byzantine wall paintings from the Mani Peninsula, Greece. An assemblage
of 12 Byzantine churches, constructed in the tenth to fifteenth century, was included in an initial analytical survey. Two
random samples of wall paintings were taken in each monument in order to study their micro stratigraphy and the composition
of pigment and plaster layers. Polished sections were fabricated for examination with optical microscopy and scanning electron
microscopy (SEM). Furthermore, selected samples were powdered and analysed with Fourier-transformed infrared spectroscopy
(FTIR) and X-ray diffraction (XRD). The analytical results achieved in this case study provided general conclusions concerning
painting techniques for wall paintings in a rather provincial area of the Byzantine Empire. The palette comprised mainly earthen
pigments like ochres and carbon black but occasionally also other pigments like cinnabar, minium and ultramarine. In view
of future studies, a portable X-ray fluorescence analysis (XRF) set-up was tested. 相似文献
60.
We introduce a topological graph parameter σ(G), defined for any graph G. This parameter characterizes subgraphs of paths, outerplanar graphs, planar graphs, and graphs that have a flat embedding
as those graphs G with σ(G)≤1,2,3, and 4, respectively. Among several other theorems, we show that if H is a minor of G, then σ(H)≤σ(G), that σ(K
n
)=n−1, and that if H is the suspension of G, then σ(H)=σ(G)+1. Furthermore, we show that μ(G)≤σ(G) + 2 for each graph G. Here μ(G) is the graph parameter introduced by Colin de Verdière in [2]. 相似文献