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941.
942.
Rademacher C Guiard J Kitov PI Fiege B Dalton KP Parra F Bundle DR Peters T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(27):7442-7453
Noroviruses attach to their host cells through histo blood group antigens (HBGAs), and compounds that interfere with this interaction are likely to be of therapeutic or diagnostic interest. It is shown that NMR binding studies can simultaneously identify and differentiate the site for binding HBGA ligands and complementary ligands from a large compound library, thereby facilitating the design of potent heterobifunctional ligands. Saturation transfer difference (STD) NMR experiments, spin-lock filtered NMR experiments, and interligand NOE (ILOE) experiments in the presence of virus-like particles (VLPs), identified compounds that bind to the HBGA binding site of human norovirus. Based on these data two multivalent prototype entry-inhibitors against norovirus infection were synthesized. A surface plasmon resonance based inhibition assay showed avidity gains of 1000 and one million fold over a millimolar univalent ligand. This suggests that further rational design of multivalent inhibitors based on our strategy will identify potent entry-inhibitors against norovirus infections. 相似文献
943.
Numbers whose continued fraction expansion contains only small digits have been extensively studied. In the real case, the Hausdorff dimension ?? M of the reals with digits in their continued fraction expansion bounded by M was considered, and estimates of ?? M for M???? were provided by Hensley (J. Number Theory 40:336?C358, 1992). In the rational case, first studies by Cusick (Mathematika 24:166?C172, 1997), Hensley (In: Proc. Int. Conference on Number Theory, Quebec, pp. 371?C385, 1987) and Vallée (J. Number Theory 72:183?C235, 1998) considered the case of a fixed bound M when the denominator N tends to ??. Later, Hensley (Pac. J. Math. 151(2):237?C255, 1991) dealt with the case of a bound M which may depend on the denominator N, and obtained a precise estimate on the cardinality of rational numbers of denominator less than N whose digits (in the continued fraction expansion) are less than M(N), provided the bound M(N) is large enough with respect to N. This paper improves this last result of Hensley towards four directions. First, it considers various continued fraction expansions; second, it deals with various probability settings (and not only the uniform probability); third, it studies the case of all possible sequences M(N), with the only restriction that M(N) is at least equal to a given constant M 0; fourth, it refines the estimates due to Hensley, in the cases that are studied by Hensley. This paper also generalises previous estimates due to Hensley (J. Number Theory 40:336?C358, 1992) about the Hausdorff dimension ?? M to the case of other continued fraction expansions. The method used in the paper combines techniques from analytic combinatorics and dynamical systems and it is an instance of the Dynamical Analysis paradigm introduced by Vallée (J. Théor. Nr. Bordx. 12:531?C570, 2000), and refined by Baladi and Vallée (J. Number Theory 110:331?C386, 2005). 相似文献
944.
Steven Pauwels Leen Antonio Ivo Jans Anneleen Lintermans Patrick Neven Frank Claessens Brigitte Decallonne Jaak Billen Dirk Vanderschueren Pieter Vermeersch 《Analytical and bioanalytical chemistry》2013,405(26):8569-8577
The need for a routinely applicable assay to measure low estradiol levels in adult men, postmenopausal women, and young adolescents was recently discussed in an Endocrine Society position statement. Our aim was to develop a sensitive liquid chromatography–tandem mass spectrometry method for estradiol and estrone in human serum without the need for derivatization or extended extraction protocols. After protein precipitation of serum with a mixture of methanol/acetonitrile (85/15) (v/v) containing isotopic internal standards (17β-estradiol-16,16,17-d 3 and estrone-2,3,4-13C), we quantified estradiol and estrone by two-dimensional liquid chromatography–tandem mass spectrometry with electrospray ionization in the negative mode monitoring 5?×?271.20→145.00 (17β-estradiol) and 269.20→145.00 (estrone). Sensitivity was increased by using fluoride and summation of 5 identical transitions for estradiol. Our method was analytically validated, compared against direct immunoassays using serum of 25 adult men, and clinically tested by measuring samples of 3 men at baseline and after chemical castration, 30 postmenopausal women and 15 patients receiving aromatase inhibitors. Total imprecision was below 20 % for the low quality controls. Limit of quantification was 1.3 ng/L (4.8 pmol/L) for estradiol and 1.2 ng/L (4.4 pmol/L) for estrone. Estradiol in Certified Reference Material BCR-576 was within specified uncertainty limits. No significant ion suppression or interference was observed. Our method showed modest correlation with direct immunoassay for estradiol (r 2?=?0.64) but no correlation for estrone (r 2?=?0.12). Patient sample results were within expected ranges. In conclusion, we developed a routinely applicable liquid chromatography–tandem mass spectrometry method for estradiol and estrone measurement which is sensitive enough for use in men, postmenopausal women, and young adolescents. Figure
Chromatogram of E2 in serum with S/N for one MRM and for the summation of 5 identical MRMs 相似文献
945.
Beauty Das Pronobesh Chattopadhyay Manabendra Mandal Brigitte Voit Niranjan Karak 《Macromolecular bioscience》2013,13(1):126-139
Hyperbranched polyurethanes are synthesized using TDI, PCL diol, butanediol, and pentaerythritol (1–5 wt%) as the B4 reactant with and without the monoglyceride of sunflower oil. The biodegradation, physico‐mechanical, and thermal properties are found to be tailored by varying the percentage weight of the branching unit. An MTT/hemolytic assay and subcutaneous implantation in Wistar rats followed by cytokine/ALP assay and histopathology studies confirm a better biocompatibility of HBPU with MG than without MG. HBPU supports the proliferation of dermatocytes with no toxic effect in major organs, in addition the in vitro degraded products are non‐toxic. Cell adherence and proliferation endorse the bio‐based HBPU as a prospective scaffold material in the niche of tissue engineering.
946.
Brigitte Osterath 《Nachrichten aus der Chemie》2014,62(2):125-127
947.
Enantiomerization Pathway and Atropochiral Stability of the BINAP Ligand: A Density Functional Theory Study 下载免费PDF全文
Juan Sanz García Dr. Christine Lepetit Dr. Yves Canac Prof. Remi Chauvin Dr. Martial Boggio‐Pasqua 《化学:亚洲杂志》2014,9(2):462-465
A theoretical study of the enantiomerization pathway of BINAP, the paradigm of atropochiral ligands in asymmetric organometallic catalysis, is reported. Density functional theory was used with the B3PW91 functional and the 6‐31G(d,p) basis set. The calculation level was validated through the study of the syn and anti enantiomerization pathways of the 1,1′‐binaphthyl reference for which the enantiomerization barrier was calculated to be in good agreement with experimental data. Calculations were then performed on BINAP itself using the same level of theory, and showed that its enantiomerization mechanism follows the syn route through a concerted, yet highly asynchronous, all‐chiral process. The enantiomerization barrier was computed at 213 kJ mol?1 and proved little sensitive to the functional or to the basis set used, with values always larger than 200 kJ mol?1. The configurational stability of BINAP was finally characterized by a computed Oki’s racemization temperature of 491 °C. 相似文献
948.
The synthesis and characterization of new 1,10-phenanthroline-based chromophores LT1, LT2 and LD1 featuring fluorene unit(s) are reported. Their absorption and emission as well as their two-photon absorption properties in the 450-650 nm spectral range are discussed in comparison with the parent 1,10-phenanthroline and already described ligands L1 and L2. 相似文献
949.
950.
Nohra B Rodriguez-Sanz E Lescop C Réau R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(11):3391-3403
Bis(2-pyridyl)phosphole 1 reacted with Cu(I) sources giving rise to dicationic or neutral dimers 2,3. In these derivatives, 1 acts as a 1kappaN:1,2kappaP:2kappaN donor with a symmetrically bridging P centre. X-ray diffraction studies of these species revealed no constraint due to the unusual coordination mode of the P donor. A comparative study with a monometallic Cu(I) complex in which 1 acts as a P,N chelate is presented. The acetonitrile ligands of the dicationic complex 2 can be displaced by a variety of donors. Bipyridine (bipy) acts as a chelating donor, while 1,1'-bis(diphenylphosphino)methane (dppm) and bis(2-pyridyl)phosphole 1 behave as bridging ligands. By using dppm and 1, the complexes arising from the stepwise displacement of the acetonitrile ligands of complex 2 can be isolated. X-ray diffraction studies performed on these novel complexes revealed that the P centre can easily switch from a bridging to a semibridging coordination mode. Of particular interest, within the same unit cell, complexes with P centres exhibiting bridging and semibridging coordination modes are observed. This switching can be induced by weak effects such as a different conformation of the incoming ligand. Cu(I) dimers assembled by 1 are air-stable derivatives that are not water sensitive. Hydrolysis of the PF(6) (-) counterion occurs under drastic conditions and results in the formation of a PO(2)F(2) fragment coordinated to a Cu(I)-1 fragment. 相似文献