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61.
[reaction: see text] Halogen-metal exchange reaction of 9-benzyl-6-iodopurine with iPrMgCl in toluene at -80 degrees C proceeds almost quantitatively. Such a purine-derived Grignard reagent reacts selectively with aldehydes in toluene, giving the corresponding alcohols in 25-62% yield, while other functional groups such as ketones, esters, and nitriles do not react under these conditions. The reaction can be extended to protected 6-iodopurine ribonucleoside. 相似文献
62.
Far-infrared laser magnetic resonance spectra of NHD (X 2A′') (0,0,0) have been observed. Data are presented for the rotational transitions 313 ← 202 and 413 ← 322 observed at wavelengths of 211.3 and 374.1 μm respectively. Theoretical values of the transition magnetic field strengths have been calculated using the best available molecular constants. The agreement between theory and experiment confirms our spectroscopic assignments, but indicates that with further experimental data, considerable refinement of the molecular constants will be obtained. 相似文献
63.
Complexes of aromatic or α,β-unsaturated nitriles YCN of the type (YCN)2(PR3)2Mo(CO)2 and (YCN)(PR3)3Mo(CO)2 are new chromophores. Their intense electronic absorption band in the visible spectrum is strongly influenced by substituents and solvent polarity. Acceptor properties of nitriles are discussed on the basis of CNDO-calculations. CT-character and solvato-chromism can be interpreted in terms of the back-bonding ability of the nitriles in electron-rich metal complexes. 相似文献
64.
This work describes the use of a dual-standard analysis approach termed the time-average ratio (TAR) in affinity capillary electrophoresis (ACE) to estimate binding constants of receptors to ligands. In this form of analysis the TAR is the migration time of the receptor divided by the average of the sum of the migration times of two non-interacting standards. This change in TAR as a function of the concentration of ligand yields a value for the binding constant. This concept is demonstrated using three model systems: carbonic anhydrase B (CAB, EC 4.2.1.1) and arylsulfonamides, vancomycin (Van) and ristocetin (Rist) from Streptomyces orientalis and Nocardia lurida, respectively, and d-Ala- d-Ala terminus peptides. Three ACE techniques are used to examine the three systems: standard ACE, flow-through partial-filling ACE (FTPFACE), and on-column derivatization coupled to ACE. The findings described here demonstrate that ACE data analyzed using the TAR form of analysis yield binding constants between receptors and ligands comparable to those estimated using other ACE forms of analysis. A comparison to three other forms of analysis is described. 相似文献
65.
An improved version of the disposable multichannel immunochemical biosensor for the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) based on a screen-printed amperometric transducer and monoclonal antibodies (MAb) against 2,4-D is reported. Entrapment within a thin Nafion film was used for the direct immobilization of MAb at the electrode surface. The amount of the tracer (2,4-D conjugated to acetylcholinesterase) bound in a competitive immunochemical reaction was determined amperometrically using acetylthiocholine iodide as substrate. The measuring procedure (times of incubation with tracer and substrate, pH, tracer concentration) was optimized. The sensor was able to detect less than 0.01 μg/L of free 2,4-D in water. One analysis (8 samples) was completed in 30 min (20 min for immunochemical reaction, 5 min incubation with substrate, 5 min measurement). The performance of the immunosensor (two configurations) was evaluated on real samples (tap water) with added 2,4-D. The determined amounts (mean values 0.097 to 0.105 and 0.89 to 1.13) corresponded well with the added contents of 2,4-D (0.100 and 1.00 μg/L, respectively). 相似文献
66.
Tsutsumi T Amakura Y Nakamura M Brown DJ Clark GC Sasaki K Toyoda M Maitani T 《The Analyst》2003,128(5):486-492
The chemical-activated luciferase expression (CALUX) assay is a reporter gene assay that detects dioxin-like compounds based on their ability to activate the aryl hydrocarbon receptor (AhR) and thus expression of the reporter gene. In this paper, the CALUX assay was examined for its application in the screening of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) in retail fish. The sample extracts were cleaned up on a sulfuric acid-silica gel column followed by an activated carbon column, and the AhR activity of the separated PCDD/F and dioxin-like PCB fractions was determined using the assay. The quantitative limit for 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) was 0.98 pg ml(-1) (0.19 pg assay(-1) in the standard curve, corresponding to 0.16 pg g(-1) of CALUX-based toxic equivalency (2,3,7,8-TCDD equivalents) in the tested sample. Recovery tests in which dioxins were added to fish samples resulted in acceptable recoveries (77-117%). The CALUX assay performed well in the analysis of dioxins in fish samples and a comparative study revealed a strong correlation between the CALUX assay and high-resolution gas chromatography-high-resolution mass spectrometry analysis for the determination of PCDD/Fs (r = 0.89) and dioxin-like PCBs (r = 0.91) in retail fish (n = 22). These data revealed that the CALUX assay would be a useful screening method for PCDD/Fs and dioxin-like PCBs in retail fish. 相似文献
67.
S. Kohn J. A. Brown R. H. Heffner C. Y. Huang T. A. Kitchens Jr. M. Leon C. E. Olsen M. E. Schillaci W. B. Gauster 《Hyperfine Interactions》1979,6(1-4):283-287
The + depolarization rate in diluteAlGd alloys containing 50 and 450 atomic ppm Gd was measured in a transverse field of 80 Oe over the temperature range 6–300 K. For both alloys, A increased dramatically above 200 K, reaching values of 0.69 and 0.93 s–1, respectively, near room temperature. The results are interpreted as providing evidence for a thermally-activated trapping mechanism.This work was supported by the U.S. Department of Energy. 相似文献
68.
R. H. Heffner J. A. Brown R. L. Hutson M. Leon D. M. Parkin M. E. Schillaci W. B. Gauster O. N. Carlson D. K. Rehbein A. T. Fiory 《Hyperfine Interactions》1979,6(1-4):237-240
We present the first results of a study of the effects of varying impurity concentration on the temperature dependence of the depolarization rate of positive muons implanted into vanadium. Data are reported for the most highly purified polycrystalline sample yet measured, and the same sample subsequently doped with about 500 ppm oxygen by weight. The data for the pure sample shows a low depolarization rate (<.15 sec–1) at all temperatures measured, showing a broad minimum centered at 35 K, followed by a sharp peak near 90 K and a rapid drop to negligible values at 200 K. The data is contrasted with previously published data [2] on less pure samples, and calls into question previous interpretations of the behavior of the + at low temperatures in impure vanadium [1] as one-phonon-assisted tunneling.This work was supported by the U. S. Department of Energy 相似文献
69.
Roberto Fernndez-Acosta Claudia Iriarte-Mesa Daniel Alvarez-Alminaque Behrouz Hassannia Bartosz Wiernicki Alicia M. Díaz-García Peter Vandenabeele Tom Vanden Berghe Gilberto L. Pardo Andreu 《Molecules (Basel, Switzerland)》2022,27(13)
The use of nanomaterials rationally engineered to treat cancer is a burgeoning field that has reported great medical achievements. Iron-based polymeric nano-formulations with precisely tuned physicochemical properties are an expanding and versatile therapeutic strategy for tumor treatment. Recently, a peculiar type of regulated necrosis named ferroptosis has gained increased attention as a target for cancer therapy. Here, we show for the first time that novel iron oxide nanoparticles coated with gallic acid and polyacrylic acid (IONP–GA/PAA) possess intrinsic cytotoxic activity on various cancer cell lines. Indeed, IONP–GA/PAA treatment efficiently induces ferroptosis in glioblastoma, neuroblastoma, and fibrosarcoma cells. IONP–GA/PAA-induced ferroptosis was blocked by the canonical ferroptosis inhibitors, including deferoxamine and ciclopirox olamine (iron chelators), and ferrostatin-1, the lipophilic radical trap. These ferroptosis inhibitors also prevented the lipid hydroperoxide generation promoted by the nanoparticles. Altogether, we report on novel ferroptosis-inducing iron encapsulated nanoparticles with potent anti-cancer properties, which has promising potential for further in vivo validation. 相似文献
70.
Nitrogen-containing heterocycles represent the majority of FDA-approved small-molecule pharmaceuticals. Herein, we describe a synthetic method to produce saturated N-heterocyclic drug scaffolds with an internal alkyne for elaboration. The treatment of N,N-dimethylhydrazinoalkenes with Et2Zn, followed by a Cu(I)-catalyzed cross-coupling with 1-bromoalkynes, results in piperidines and pyrrolidines with a good yield. Five examples are reported and a proposed mechanism for the Cu(I)-catalyzed cross-coupling is presented. 相似文献