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61.
Martin Christlieb Hannah J. Claughton Andrew R. Cowley Julia M. Heslop Jonathan R. Dilworth 《Transition Metal Chemistry》2006,31(1):88-92
During the condensation of 4-methyl-4-phenyl-3-thiosemicarbazide (3) with 2,3-butanedione an unexpected by-product, 8a-methyl-6,8a-dihydro-8-methyl-2-[N-methyl-N-phenylamino]-5H-1,3,4-thiadiazolo[3,2-d][1,2,4]triazine-5-thione, (5) was obtained in addition to the desired bis(thiosemicarbazone) (4). An X-ray crystal structure was obtained and is presented together with a proposed mechanism for its formation. A brief investigation
of the coordination chemistry of bicycle (5) was carried out. The formation of cyclic compounds during the synthesis of analogues with extended backbones is also described. 相似文献
62.
Stable chlorins bearing few or no substituents have been subjected to a variety of reactions including demetalation, magnesium insertion, oxochlorin formation, and bromination followed by Suzuki coupling. The kinetics of deuteration also have been determined for two oxochlorins and a series of chlorins bearing 0, 1, 2, or 3 meso-aryl substituents. 相似文献
63.
64.
Sajal Sen Mark W. Perrin Adam C. Sedgwick Vincent M. Lynch Jonathan L. Sessler Jonathan F. Arambula 《Chemical science》2021,12(21):7547
Recent decades have witnessed the emergence of Au(i) bis-N-heterocyclic carbenes (NHCs) as potential anticancer agents. However, these systems exhibit little interaction with serum proteins (e.g., human serum albumin), which presumably impacts their pharmacokinetic profile and tumor exposure. Anticancer drugs bound to human serum albumin (HSA) often benefit from significant advantages, including longer circulatory half-lives, tumor targeted delivery, and easier administration relative to the drug alone. In this work, we present Au(i) bis-NHCs complexes, 7 and 9, capable of binding to HSA. Complex 7 contains a reactive maleimide moiety for covalent protein conjugation, whereas its congener 9 contains a naphthalimide fluorophore for non-covalent binding. A similar drug motif was used in both cases. Complexes 7 and 9 were prepared from a carboxylic acid functionalized Au(i) bis-NHC (complex 2) using a newly developed post-synthetic amide functionalization protocol that allows coupling to both aliphatic and aromatic amines. Analytical, and in vitro techniques were used to confirm protein binding, as well as cellular uptake and antiproliferative activity in A549 human lung cancer cells. The present findings highlight a hitherto unexplored approach to modifying Au(i) bis-NHC drug candidates for protein ligation and serve to showcase the relative benefits of covalent and non-covalent HSA binding.Au(i) bis-N-heterocyclic carbenes (NHCs) functionalized using an amide linker were found to bind to human serum albumin (HSA) in covalent and non-covalent fashion. The solubility and in vitro anti-cancer activity of these new conjugates were studied. 相似文献
65.
Hau Sun Sam Chan Amber L. Thompson Kirsten E. Christensen Jonathan W. Burton 《Chemical science》2020,11(42):11592
Laurefurenynes C–F are four natural products isolated from Laurencia species whose structures were originally determined on the basis of extensive nuclear magnetic resonance experiments. On the basis of a proposed biogenesis, involving a tricyclic oxonium ion as a key intermediate, we have reassigned the structures of these four natural products and synthesized the four reassigned structures using a biomimetic approach demonstrating that they are the actual structures of the natural products. In addition, we have developed a synthesis of the enantiomers of the natural products laurencin and deacetyllaurencin from the enantiomer of (E)-laurefucin using an unusual retrobiomimetic strategy. All of these syntheses have been enabled by the use of tricyclic oxonium ions as pivotal synthetic intermediates.The synthesis and structural reassignment of laurefurenynes C–F has been achieved, with the new structures fitting with a proposed biosynthesis. Also reported is the synthesis of ent-laurencin and ent-deacetyllaurencin via a retrobiomimetic approach. 相似文献
66.
There is a need to develop broadly applicable, highly sensitive detection methods for microchip CE that do not require analyte derivatization. LIF is highly sensitive but typically requires analyte derivatization. Electrochemistry provides an alternative method for direct analyte detection; however, in its most common form, direct current (DC) amperometry, it is limited to a small number of easily oxidizable or reducible analytes. Pulsed amperometric detection (PAD) is an alternative waveform that can increase the number of electrochemically detectable analytes. Increasing sensitivity for electrochemical detection (EC) and PAD requires the isolation of detection current (nA) from the separation current (muA) in a process generally referred to as current decoupling. Here, we present the development of a simple integrated decoupler to improve sensitivity and its coupling with PAD. A Pd microwire is used as the cathode for decoupling and a second Au or Pt wire is used as the working electrode for either EC or PAD. The electrode system is easy to make, requiring no clean-room facilities or specialized metallization systems. Sensitive detection of a wide range of analytes is shown to be possible using this system. Using this system we were able to achieve detection limits as low as 5 nM for dopamine, 74 nM for glutathione, and 100 nM for glucose. 相似文献
67.
In this article we give an existence theorem for localized travelling wave solutions on one-dimensional lattices with Hamiltonian $$H = \sum\limits_{n \in \mathbb{Z}} {\left( {\tfrac{1}{2}p_n^2 + V(q_{n + 1} - q_n )} \right)} ,$$ whereV(·) is the potential energy due to nearest-neighbour interactions. Until now, apart from rare integrable lattices like the Toda latticeV(φ)=ab ?1(e ?bφ+bφ?1), the only evidence for existence of such solutions has been numerical. Our result in particular recovers existence of solitary waves in the Toda lattice, establishes for the first time existence of solitary waves in the (nonintegrable) cubic and quartic latticesV(φ)= 1/2φ 2 + 1/3aφ 3,V(φ) = 1/2φ 2 + 1/4bφ 4, thereby confirming the numerical findings in [1] and shedding new light on the recurrence phenomena in these systems observed first by Fermi, Pasta and Ulam [2], and shows that contrary to widespread belief, the presence of exact solitary waves is not a peculiarity of integrable systems, but “generic” in this class of nonlinear lattices. The approach presented here is new and quite general, and should also be applicable to other forms of lattice equations: the travelling waves are sought as minimisers of a naturally associated variational problem (obtained via Hamilton's principle), and existence of minimisers is then established using modern methods in the calculus of variations (the concentration-compactness principle of P.-L. Lions [3]). 相似文献
68.
69.
Clayden J Turnbull R Helliwell M Pinto I 《Chemical communications (Cambridge, England)》2004,(21):2430-2431
Thiophene-3-carboxamides bearing allyl or benzyl substituents at nitrogen undergo dearomatising cyclisation on treatment with LDA. Rearrangements transform the dearomatised products into pyrrolinones, azepinones or partially saturated azepinothiophenes. 相似文献
70.
Reacting (−)-menthyl sulfinate with an atropisomeric but racemic aryllithium gives two atropdiastereoisomeric sulfoxides. Separation (by chromatography or crystallisation) and sulfoxide-lithium exchange of each diastereoisomer regenerates the aryllithium in enantiomerically pure form which can be quenched with a range of electrophiles with retention of stereochemical integrity. Overall the reaction sequence is a resolution but without the need for an acidic or basic substituent—a ‘traceless’ method. In certain instances, for example when the nucleophile is an ortholithiated peri-substituted 1-naphthamide, the diastereoisomeric sulfoxides may be interconverted thermally. This allows a dynamic resolution, under thermodynamic control, and hence in principle can give yields of the final products of greater than 50%. The utility of the method is demonstrated by the synthesis of a known atropisomeric phosphine ligand. 相似文献