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71.
Sarah J.P. Yoon-Miller 《Tetrahedron letters》2007,48(5):827-830
A three step, convergent synthesis of 4-aryl-3-pyrrolin-2-ones from a tetramic acid has been developed. The key transformation utilized a Suzuki-Miyaura cross-coupling reaction between a 4-tosyloxy-3-pyrrolin-2-one and an arylboronic acid. This work also provides access to 4-arylpyrrolidin-2-ones, cyclic analogs of γ-aminobutyric acid (GABA). Hydrogenation of 4-(4′-chlorophenyl)-3-pyrrolin-2-one proceeded smoothly to give baclofen lactam. 相似文献
72.
Frdric Tronc Warner Chen Mitchell A. Winnik Sarah T. Eckersley Gene D. Rose J. M. Weishuhn D. M. Meunier 《Journal of polymer science. Part A, Polymer chemistry》2002,40(22):4098-4116
This article describes the results of experiments examining the competition between the polymer diffusion rate and the crosslinking rate in low‐glass‐transition‐temperature, epoxy‐containing latex films in the presence of a diamine. We examined films formed from donor‐ and acceptor‐labeled poly(butyl acrylate‐co‐methyl methacrylate‐co‐glycidyl methacrylate) copolymer latex and studied the influence of several parameters on the growth rate of gel content and the rate of polymer diffusion. These factors include the molecular weight of the latex polymer, the presence or absence of a diamine crosslinking agent, and the cure protocol. The results were compared to the predictions of a recent theory of the competition between crosslinking and polymer diffusion across interfaces. In the initially formed films, polymer diffusion occurs more rapidly than the chemical reaction rate. Therefore, these films fall into the fast‐diffusion category of this model. In our system (unlike in the model), the latex polymer has a broad distribution of molecular weights and a distribution of diffusivities. The shortest chains contribute to the early time diffusion that we measure. At later stages of our experiment, slower diffusing species contribute to the signal that we measure. The diffusion time decreases substantially, and we observe a crossover to a regime in which the chemical reaction dominates. The increases in chain branching and gel formation bring polymer diffusion to a halt. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4098–4116, 2002 相似文献
73.
Düggeli M Goujon-Ginglinger C Ducotterd SR Mauron D Bonte C von Zelewsky A Stoeckli-Evans H Neels A 《Organic & biomolecular chemistry》2003,1(11):1894-1899
A series of new tetradentate ligands containing two bipyridine groups or two pyridine moieties carrying amine substituents has been synthesised either from 5'- and 6'-substituted chiral bipyridines, or from chiral pyridine derivatives. These precursors have been prepared from (-)-alpha-pinene or (-)-myrtenal, respectively. The structures of three tetradentate-, and of five chiral bipyridine ligands have been determined by X-ray diffraction. 相似文献
74.
Tandem mass spectrometry is used to monitor the contamination of banknotes by cocaine. By introducing a series of banknotes into an instrument a distribution of contamination can be obtained. The distribution of samples arising from defendants where the banknotes have been in close proximity to cocaine should differ from the distribution from the general background population. Peak picking and integration is used to produce a series of intensity readings for a batch of banknotes. By visually inspecting these distribution, and applying a variety of chemometric methods (principal components analysis, cluster analysis and class modelling via Mahalanobis distance) it is possible to discriminate effectively between the two classes of distribution (7157 background notes and 4826 case notes alleged to be from drug dealers). By calculating the Mahalonobis distance over 100 bootstrap iterations, background samples were correctly classified 96.48% of the time, while case samples were correctly classified 89.37% of the time. 相似文献
75.
It is difficult to quantify NH4+ by ion chromatography in the presence of high concentrations of Na+ due to peak overlap. The Dionex IonPac CS15 column, which contains phosphonate, carboxylate, and 18-crown-6 functional groups, was originally developed to overcome this problem. We have found that the addition of 18-crown-6 to the eluent promotes improved peak resolution between Na+ and NH4+ even at concentrations as high as 60,000 to 1 using this column. Its use also improves the separation of alkali and alkaline earth metal and amine cations. Mobile phase 18-crown-6 increased the retention times of CH3NH3+, NH4+, and K+, and decreased the retention time of Sr2+. The retention times of Li+, Na+, Mg2+, Ca2+, (CH3)2NH2+, and (CH3)3NH+ were not affected. This method makes possible the direct analysis of ammonia from nitrogenase, the enzyme responsible for biological nitrogen fixation. The resolution of the NH4+ peak from the Na+ and Mg2+ peaks improved from zero resolution to values of 6.19 and 5.65, respectively. This technique considerably reduces the analysis time of NH4+ in the presence of high concentrations of Mg2+ and Na+ over traditional indophenol measurements. 相似文献
76.
Sarah Eichenberger Moritz Hnig Matthieu J. R. Richter Renana Gershoni-Poranne Erick M. Carreira 《Chemical science》2020,11(20):5294
A novel Lewis acid-catalyzed cycloisomerization of alkylidenecyclopropane acylsilanes is disclosed. The readily available starting materials participate in tandem Prins addition/ring expansion/1,2-silyl shift to grant access to bicyclo[4.2.0]octanes and bicyclo[3.2.0]heptanes, which are common motifs in terpenoid natural products. Notably, the transformation relies on the ability of acylsilanes to act sequentially as acceptors and donors on the same carbon atom.A novel Lewis acid-catalyzed cycloisomerization of alkylidenecyclopropane acylsilanes is disclosed that involves tandem Prins addition/ring expansion/1,2-silyl shift to grant access to bicyclo[4.2.0]octanes and bicyclo[3.2.0]heptanes. 相似文献
77.
A number of rhenium complexes with binaphthyridine and biquinoline ligands have been synthesized and studied. These are [Re(L)(CO)3Cl] where L = 3,3'-dimethylene-2,2'-bi-1,8-naphthyridine (dbn), 2,2'-bi-1,8-naphthyridine (bn), 3,3'-dimethylene-2,2'-biquinoline (dbq), and 3,3'-dimethyl-2,2'-biquinoline (diq). This series represents ligands in which the electronic properties and steric preferences are tuned. These complexes are modeled using density functional theory (DFT). An analysis of the resonance Raman spectra for these complexes, in concert with the vibrational assignments, reveals that the accepting molecular orbital (MO) in the metal-to-ligand charge transfer (MLCT) transition is the LUMO and causes bonding changes at the inter-ring section of the ligand. The electronic absorption spectroelectrochemistry for the reduced complexes of [Re(dbn)(CO)3Cl], [Re(dbq)(CO)3Cl], and [Re(diq)(CO)3Cl] suggest that the singly occupied MO is delocalized over the entire ligand structure despite the nonplanar nature of the diq ligand in [Re(diq)(CO)3Cl]. The IR spectroelectrochemistry for [Re(dbn)(CO)3Cl], [Re(dbq)(CO)3Cl], and [Re(bn)(CO)3Cl] reveal that reduction lowers the CO ligand vibrational frequencies to a similar extent in all three complexes. The substitution of naphthyridine for quinoline has little effect on the nature of the singly occupied MO. These data are supported by DFT calculations on the reduced complexes, which reveal that the ligands are flattened out by reduction: This may explain the similarity in the properties of the reduced complexes. 相似文献
78.
Xu Zhao Sarah E. Cleary Ceren Zor Nicole Grobert Holly A. Reeve Kylie A. Vincent 《Chemical science》2021,12(23):8105
Heterogeneous biocatalytic hydrogenation is an attractive strategy for clean, enantioselective C X reduction. This approach relies on enzymes powered by H2-driven NADH recycling. Commercially available carbon-supported metal (metal/C) catalysts are investigated here for direct H2-driven NAD+ reduction. Selected metal/C catalysts are then used for H2 oxidation with electrons transferred via the conductive carbon support material to an adsorbed enzyme for NAD+ reduction. These chemo-bio catalysts show improved activity and selectivity for generating bioactive NADH under ambient reaction conditions compared to metal/C catalysts. The metal/C catalysts and carbon support materials (all activated carbon or carbon black) are characterised to probe which properties potentially influence catalyst activity. The optimised chemo-bio catalysts are then used to supply NADH to an alcohol dehydrogenase for enantioselective (>99% ee) ketone reductions, leading to high cofactor turnover numbers and Pd and NAD+ reductase activities of 441 h−1 and 2347 h−1, respectively. This method demonstrates a new way of combining chemo- and biocatalysis on carbon supports, highlighted here for selective hydrogenation reactions.Heterogeneous chemo-bio catalytic hydrogenation is an attractive strategy for clean, enantioselective C X reduction. 相似文献
79.
Inteins are self-cleavable proteins that under reducing conditions can be cleaved from a recombinant target protein. Industrially, an intein-based system could potentially reduce production costs of recombinant proteins by facilitating a highly selective affinity purification using an inexpensive substrate such as chitin. In this study, SuperPro Designer was used to simulate the large-scale recovery of a soluble recombinant protein expressed in Escherichia coli using an intein-mediated purification process based on the commercially available IMPACT system. The intein process was also compared with a conventional process simulated by SuperPro. The intein purification process initially simulated was significantly more expensive than the conventional process, primarily owing to the properties of the chitin resin and high reducing-agent (dithiothreitol [DTT]) raw material cost. The intein process was sensitive to the chitin resin binding capacity, cleavage efficiency of the intein fusion protein, the size of the target protein relative to the intein tag, and DTT costs. An optimized intein purification process considerably reduced costs by simulating an improved chitin resin and alternative reducing agents. Thus, to realize the full potential of intein purification processes, research is needed to improve the properties of chitin resin and to find alternative, inexpensive raw materials. 相似文献
80.