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151.
The one-pot synthesis of tetrahydrofluorenones, the core 6-5-6 tricyclic structural motif found in norditerpenoid natural products, from alkylidene Meldrum's acids via thermal Diels-Alder/BF3.OEt2-catalyzed Friedel-Crafts acylation reactions is described. A series of tetrahydrofluorenones was assembled in good yields, and the Diels-Alder/Friedel-Crafts acylation protocol allowed modification of the substitution within the rings. 相似文献
152.
An off-set stack and a saddle-like distortion are revealed by the molecular structures of [Ru(bpy)2(N-HSB)].2PF6 and [Ru(bpy)2(N-(1/2)HSB)].2PF6. 相似文献
153.
The novel complexes [Zn(L)Cl] (1), [Cd(L)Cl] (2), [Hg(L)Cl] (3), {[Hg(L)Cl].NaOH.2H2O} (3.NaOH.2H2O), and {[Hg3(HL)2Cl6].2H2O} (4) (L = -SCH2CH2NH2) were prepared and investigated by means of IR spectroscopy and single-crystal X-ray diffraction. The crystal structures of 1, 2, and 3.NaOH.2H2O show chelating N,S-coordination of the cysteaminate ligand, bridging S, and terminally coordinating Cl. Apart from these common features, the coordination geometries and modes of intermolecular association are different. 1 forms a cyclic tetramer with a Zn4S4 ring, and 3.NaOH.2H2O contains one-dimensional [Hg(L)Cl]n chains with S-bridged Hg atoms. Zn and Hg atoms in 1 and 3.NaOH.2H2O are tetracoordinate with a distorted tetrahedral M(ClNS2) geometry (M = Zn, Hg). Each Cd atom of 2 binds to three S atoms and vice versa, such that layers of distorted Cd3S3 hexagons are formed. 2 is the first example for a compound exhibiting a group 12-group 16 layer structure, which can be described as an analogue of a graphite layer. Additionally, each Cd atom binds to a chlorine atom and a nitrogen atom from a cysteaminate ligand resulting in pentacoordination with a distorted trigonal bipyramidal Cd(ClNS3) geometry. 4 contains two differently coordinate Hg atoms. One displays a distorted trans-octahedral Hg(Cl4S2) geometry, while the other is coordinated by four Cl atoms and one S atom and additionally forms a long Hg...Cl contact. 相似文献
154.
Moschou EA Nicholson AD Jia G Zoval JV Madou MJ Bachas LG Daunert S 《Analytical and bioanalytical chemistry》2006,385(3):596-605
This work demonstrates the development of microfluidic compact discs (CDs) for protein purification and fractionation integrating a series of microfluidic features, such as microreservoirs, microchannels, and microfluidic fractionators. The CDs were fabricated with polydimethylsiloxane (PDMS), and each device contained multiple identical microfluidic patterns. Each pattern employed a microfluidic fractionation feature with operation that was based on the redirection of fluid into an isolation chamber as a result of an overflow. This feature offers the advantage of automated operation without the need for any external manipulation, which is independent of the size and the charge of the fractionated molecules. The performance of the microfluidic fractionator was evaluated by its integration into a protein purification microfluidic architecture. The microfluidic architecture employed a microchamber that accommodated a monolithic microcolumn, the fractionator, and an isolation chamber, which was also utilized for the optical detection of the purified protein. The monolithic microcolumn was polymerized “in situ” on the CD from a monolith precursor solution by microwave-initiated polymerization. This technique enabled the fast, efficient, and simultaneous polymerization of monoliths on disposable CD microfluidic platforms. The design of the CD employed allows the integration of various processes on a single microfluidic device, including protein purification, fractionation, isolation, and detection.
相似文献
155.
We show that a broad class of fully nonlinear, second‐order parabolic or elliptic PDEs can be realized as the Hamilton‐Jacobi‐Bellman equations of deterministic two‐person games. More precisely: given the PDE, we identify a deterministic, discrete‐time, two‐person game whose value function converges in the continuous‐time limit to the viscosity solution of the desired equation. Our game is, roughly speaking, a deterministic analogue of the stochastic representation recently introduced by Cheridito, Soner, Touzi, and Victoir. In the parabolic setting with no u‐dependence, it amounts to a semidiscrete numerical scheme whose timestep is a min‐max. Our result is interesting, because the usual control‐based interpretations of second‐order PDEs involve stochastic rather than deterministic control. © 2009 Wiley Periodicals, Inc. 相似文献
156.
157.
Atsushi Narumi Sylvia Zeidler Haitham Barqawi Claudia Enders Wolfgang H. Binder 《Journal of polymer science. Part A, Polymer chemistry》2010,48(15):3402-3416
A cyclic initiator for the nitroxide‐mediated controlled radical polymerization (NMP) is a powerful tool for the preparation of macrocyclic polymers via a ring‐expansion vinyl polymerization mechanism. For this purpose, we prepared a Hawker‐type NMP‐initiator that includes an azide and a terminal alkyne as an acyclic precursor, which is subsequently tethered via an intramolecular azide/alkyne‐“click”‐reaction, producing the final cyclic NMP‐initiator. The polymerization reactions of styrene with cyclic initiator were demonstrated and the resultant polymers were characterized by the gel permeation chromatography (GPC) and the matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS). These results prove that the ring‐expansion polymerization of styrene occurred together with the radical ring‐crossover reactions originating from the exchange of the inherent nitroxides generating macrocyclic polystyrenes with higher expanded rings. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3402–3416, 2010 相似文献
158.
The present work describes an analytical procedure for the determination of the total iodine content in biological materials (serum, milk, plants, tissues etc.). Liquid samples can be directly analyzed after dilution, if necessary, by ICP-MS. Milk powder, plants and tissues were dissolved by using a modified simple Schöninger combustion, subsequently the residue was taken up in 0.1 mol/l NaOH and this solution was analyzed by ICP-MS. The detection limit is in the range of 0.01 g/l. The method was tested using different CRMs certified for the iodine content. 相似文献
159.
Determination and on-line clean-up of (fluoro)quinolones in bovine milk using column-switching liquid chromatography fluorescence detection 总被引:1,自引:0,他引:1
A simple, cost-effective, and high throughput method using on-line column-switching liquid chromatography fluorescence detection was developed and validated for analysing five (fluoro)quinolones (FQs)--enrofloxacin (ENRO), ciprofloxacin (CIPR), sarafloxacin (SARA), oxolinic acid (OXOL), and flumequine (FLUM) in bovine milk. Norfloxacin (NORF) and nalixidic acid (NALI) were used as internal standards. After simple deproteination of milk sample with 5% (w/v) metaphosphoric acid, the supernatant was subject to on-line column clean-up and direct analysis by LC-FLD. The extraction cartridge was prepared in-house by slurry packing with hydrophilic-lipophilic polymer sorbent. The accuracy of measurement for each (fluoro)quinolone at different maximum residue limits (MRL) was 101-103% (ENRO), 92.8-97.4% (CIPR), 89.8-92.8% (SARA), 116-121% (OXOL), and 81.3-85.5% (FLUM), whilst the precision was 2.9-6.1% (ENRO), 2.5-5.1% (CIPR), 2.3-5.0% (SARA), 3.1-5.9% (OXOL), and 5.6-6.5% (FLUM). The decision limits, detection capabilities, specificity and analytes stability during storage were also investigated. 相似文献
160.
Kinzie SD Thevis M Ngo K Whitelegge J Loo JA Abu-Omar MM 《Journal of the American Chemical Society》2003,125(16):4710-4711
Phenylalanine hydroxylase, a mononuclear non-heme iron enzyme, catalyzes the hydroxylation of phenylalanine to tyrosine in the presence of oxygen and reduced pterin cofactor. X-ray structural studies have established the coordination around the iron metal center and point to significant interactions within the second coordination sphere. One such interaction involves Tyr325 in human phenylalanine hydroxylase (hPAH), which forms a hydrogen-bonding network with an aqua ligand on iron and the pterin cofactor. The full-length tetramer (1-452) and truncated dimer (117-424) Tyr325Phe hPAH mutant enzymes showed similar kinetics, thermal stabilities, and oligomerization profiles as their corresponding wild-type proteins. The possibility of in vivo posttranslational hydroxylation that would restore the activity of hPAH was examined by mass spectrometry on the trypsin digested full-length (1-452) hPAH Tyr325Phe point mutant. The amino acid tags obtained by ESI-MS/MS confirmed the presence of a Phe325 in the peptide corresponding to the doubly charged precursor ion at m/z 916.4 (L A T I F W F T V E F G L C K), and its hydroxylated counterpart in the peptide corresponding to the m/z 924.4 (L A T I F-OH W F T V E F G L C K) byproduct ion series comprising the fragments y(5)-y(12). Furthermore, the point mutation Tyr325Ala resulted in an enzyme that was totally inactive and did not display any evidence of hydroxylation. These results demonstrate the importance of Tyr325 for proper conformation of the active site, substrate binding, and catalysis. The rescue of the Tyr325Phe mutant in hPAH via self-hydroxylation presents a novel example of oxidative repair on the molecular level. 相似文献