排序方式: 共有30条查询结果,搜索用时 187 毫秒
1.
Kozikowski AP Tückmantel W Böttcher G Romanczyk LJ 《The Journal of organic chemistry》2003,68(5):1641-1658
We report an improved synthesis of bis(5,7,3',4'-tetra-O-benzyl)epicatechin 4beta,8-dimer (3) from 5,7,3',4'-tetra-O-benzylepicatechin (1) and 5,7,3',4'-tetra-O-benzyl-4-(2-hydroxyethoxy)epicatechin (2) by replacing the previously employed Lewis acid, titanium tetrachloride, with the clay mineral Bentonite K-10. Under the same conditions, the benzyl-protected all-4beta,8-trimer, -tetramer, and -pentamer were obtained regioselectively from their lower homologues, albeit in rapidly decreasing yields. Reaction of 2 with an organoaluminum thiolate generated from 2-mercaptobenzothiazole and trimethylaluminum followed by acetylation produced 3-O-acetyl-4-[(2-benzothiazolyl)thio]-5,7,3',4'-tetra-O-benzylepicatechin (12). Medium-sized protected oligomers with 4beta,8-interflavan linkages are obtained in improved yields by using this compound as the electrophile and silver tetrafluoroborate as activator and are isolated by reversed-phase HPLC. Their deprotection by ester saponification followed by hydrogenolysis yielded the free procyanidins, which were characterized as their peracetates. The synthetic procyanidins are identical by normal-phase HPLC with fractions isolated from cocoa. The principle of chain extension by two members was demonstrated using a dimeric electrophile obtained by self-condensation of compound 12. Both the synthetic and natural pentamer 32 inhibit the growth of several breast cancer cell lines. Using the MDA MB 231 line, it was established that this outcome is based on the induction of cell cycle arrest in the G0/G1 phase. Subsequent cell death is more likely necrotic rather than apoptotic. Control experiments demonstrate that the polyphenol itself, rather than hydrogen peroxide potentially formed by its autoxidation, is the causative agent. 相似文献
2.
Saher Helmy A Hutchings DC Kleckner TC Marsh JH Bryce AC Arnold JM Stanley CR Aitchison JS Brown CT Moutzouris K Ebrahimzadeh M 《Optics letters》2000,25(18):1370-1372
We report the observation of second-harmonic generation by type I quasi phase matching in a GaAs-AlAs superlattice waveguide. Quasi phase matching was achieved through modulation of the nonlinear coefficient chi((2))(zxy), which we realized by periodically tuning the superlattice bandgap. Second-harmonic generation was demonstrated for fundamental wavelengths from 1480 to 1520 nm, from the third-order gratings with periods from 10.5 to 12.4microm . The second-harmonic signal spectra demonstrated narrowing owing to the finite bandwidth of the quasi-phase-matching grating. An average power of ~110 nW was obtained for the second harmonic by use of an average launched pump power of ?2.3mW . 相似文献
3.
Stephen G. Davies Ai M. Fletcher Gesine J. Hermann Giovanna Poce Paul M. Roberts Andrew D. Smith Miles J. Sweet James E. Thomson 《Tetrahedron: Asymmetry》2010,21(13-14):1635-1648
The doubly diastereoselective conjugate addition of the antipodes of lithium N-benzyl-N-(α-methylbenzyl)amide to a range of enantiopure N-enoyl oxazolidin-2-ones has been used as a mechanistic probe to determine that the reactive conformation is the anti-s-cis form. The β-amino carbonyl products resulting from these conjugate addition reactions are useful templates for further elaboration into an α,β,α-pseudotripeptide. 相似文献
4.
5.
A new class of distributional transformations is introduced, characterized by equations relating function weighted expectations of test functions on a given distribution to expectations of the transformed distribution on the test functions higher order derivatives. The class includes the size and zero bias transformations, and when specializing to weighting by polynomial functions, relates distributional families closed under independent addition, and in particular the infinitely divisible distributions, to the family of transformations induced by their associated orthogonal polynomial systems. For these families, generalizing a well known property of size biasing, sums of independent variables are transformed by replacing summands chosen according to a multivariate distribution on its index set by independent variables whose distributions are transformed by members of that same family. A variety of the transformations associated with the classical orthogonal polynomial systems have as fixed points the original distribution, or a member of the same family with different parameter. 相似文献
6.
Let n be an integer and A0,..., Ak random subsets of {1,..., n} of fixed sizes a0,..., ak, respectively chosen independently and uniformly. We provide an explicit and easily computable total variation bound between
the distance from the random variable
, the size of the intersection of the random sets, to a Poisson random variable Z with intensity λ = EW. In particular, the bound tends to zero when λ converges and
for all j = 0,..., k, showing that W has an asymptotic Poisson distribution in this regime.
Received February 24, 2005 相似文献
7.
Thomas Bridge Saher A. Shaikh Paul Thomas Joaquin Botta Peter J. McCormick Amit Sachdeva 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(50):18154-18161
Antibodies have found applications in several fields, including, medicine, diagnostics, and nanotechnology, yet methods to modulate antibody–antigen binding using an external agent remain limited. Here, we have developed photoactive antibody fragments by genetic site‐specific replacement of single tyrosine residues with photocaged tyrosine, in an antibody fragment, 7D12. A simple and robust assay is adopted to evaluate the light‐mediated binding of 7D12 mutants to its target, epidermal growth factor receptor (EGFR), on the surface of cancer cells. Presence of photocaged tyrosine reduces 7D12‐EGFR binding affinity by over 20‐fold in two out of three 7D12 mutants studied, and binding is restored upon exposure to 365 nm light. Molecular dynamics simulations explain the difference in effect of photocaging on 7D12‐EGFR interaction among the mutants. Finally, we demonstrate the application of photoactive antibodies in delivering fluorophores to EGFR‐positive live cancer cells in a light‐dependent manner. 相似文献
8.
9.
Dr. Gesine Schmidt Dr. Christoph Timm Dr. Achim Grube Dr. Christian A. Volk Priv.‐Doz. Dr. Matthias Köck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(26):8180-8189
Four new 3‐alkyl pyridinium alkaloids, the viscosalines B1 ( 1 a ), B2 ( 1 b ), E1 ( 2 a ), and E2 ( 2 b ), were isolated from the Arctic sponge Haliclona viscosa. The structure elucidation of these isomeric compounds was challenging due to ambiguous fragments that derive during “standard” mass spectrometric fragmentation experiments. The final structure elucidation relied on the use of a combination of synthesis, liquid chromatography, and mass spectrometry. Three different mass spectrometers were used to differentiate between the synthetic structural isomers: a time‐of‐flight (TOF) mass spectrometer and two ion‐trap mass spectrometers with different ion‐transfer technologies (i.e., skimmer versus funnel optics). Although at first none of the spectrometers returned spectra that permitted structure elucidation, all three mass spectrometers provided analysis that successfully differentiated between the isomers after thorough method optimization. The use of in‐source collision‐induced dissociation (CID) with the ion trap and TOF instrument returned the most interesting results. The mode of fragmentation of the viscosalines under different experimental conditions is described herein. After successful optimization of the mass spectrometric method applied, the chromatographic method was improved to distinguish the previously inseparable isomers. Finally, both the liquid chromatography and mass spectrometric methods were applied to the natural products and the results compared to those from the synthetic compounds. 相似文献
10.
Friedrich-Rust M Romenski O Meyer G Dauth N Holzer K Grünwald F Kriener S Herrmann E Zeuzem S Bojunga J 《Ultrasonics》2012,52(1):69-74