Abstract β-Ketonitrosamines have been established as anionic synthons of the type (RCO+?CHNHR′). The enhanced acidity of protons at the α-carbon, as well as the ease of fragmentation of the title compounds, established them as synthetic equivalents of α-methylenealkylamino anions (?CH2NHR). We now report the equivalency of β-ketonitrosamines to α-methinyl methylamino (R?CHNHCH3) and α-methinyl alkylamino (R ?CHNHR′) anions. 相似文献
We have developed a multimodal ion source design that can be configured on the fly for various analysis modes, designed for more efficient and reproducible sampling at the mass spectrometer atmospheric pressure (AP) interface in a number of different applications. This vacuum-assisted plasma ionization (VaPI) source features interchangeable transmission mode and laser ablation sampling geometries. Operating in both AC and DC power regimes with similar results, the ion source was optimized for parameters including helium flow rate and gas temperature using transmission mode to analyze volatile standards and drug tablets. Using laser ablation, matrix effects were studied, and the source was used to monitor the products of model prebiotic synthetic reactions.
The fundamental ideas of Minkowski geometries are presented. Learning about Minkowski geometries can sharpen our students’ understanding of concepts such as distance measurement. Many of its ideas are important and accessible to undergraduate students. Following a brief overview, distance and orthogonality in Minkowski geometries are thoroughly discussed and many illustrative examples and applications are supplied. Suggestions for further study of these geometries are given. Indeed, Minkowski geometries are an excellent source of topics for undergraduate research and independent study. 相似文献
Osteoporosis is a major age-related source of morbidity and mortality. Increased bone resorption mediated by osteoclasts is central to its pathogenesis. Cytokines, particularly RANKL and TNFalpha, are often increased under pathologic conditions, leading to enhanced osteoclastogenesis. Black cohosh (Actaea/Cimicifuga racemosa L), a popular herbal supplement for the treatment of menopausal symptoms, was recently shown to have the beneficial effect of preventing bone loss. Here, we demonstrate that 25-acetylcimigenol xylopyranoside (ACCX), a triterpenoid glycoside isolated from black cohosh, potently blocks in vitro osteoclastogenesis induced by either RANKL or TNFalpha. This blockage of osteoclastogenesis elicited by ACCX results from abrogation of the NF-kappaB and ERK pathways induced by either RANKL or TNFalpha, respectively. Importantly, this compound attenuates TNFalpha-induced bone loss in vivo. Therefore, ACCX represents a potential lead for the development of a new class of antiosteoporosis agents. 相似文献
The effect of charge transfer reactions on analyte excitation and ionization in the inductively coupled plasma was studied by two independent techniques. In one technique, pulsed lasers were used to either deplete the ground state of neutral analyte atoms or enhance the population of selected states of the singly charged ion. In both cases the perturbed species were collision partners with argon in potential charge transfer reactions. The effects of charge transfer collisions could be detected in the form of changes in emission from product species. In the second technique, a simple correlation method was used to detect the link via charge transfer of neutral atom ground states and highly excited ionic levels. In the presence of charge transfer collisions, the populations of such linked levels show strong positive correlations. The two techniques were used to study the effects of charge transfer reactions on the third row elements Ca–Cu. With the exception of Cr and Mn, all of the elements studied showed positive evidence of excitation and ionization by charge transfer collision with argon. 相似文献
Planar laser-induced fluorescence was used to examine the effect of the sampling cone on analyte atom and ion distributions in the inductively coupled plasma used as an ion source for elemental mass spectrometry. Comparisons of planar laser-induced fluorescence images in the presence and absence of the sampling interface reveal that the insertion of the sampling cone into the plasma dramatically lowers singly-charged ion densities in the 1–2 mm region immediately upstream from the sampling cone, but increases densities in the region between 2 mm and 10 mm upstream from the sampling cone. Some of the drops in densities near the sampling cone can be attributed to acceleration of the plasma through the pumped sampling orifice. A shift in equilibrium between doubly and singly charged barium ions caused by cooling of the plasma is proposed to account for the increases in densities of Ba+ in the upstream region. 相似文献
Electric field gradient focusing (EFGF) is a technique used to simultaneously separate and concentrate biomacromolecules, such as proteins, based on the opposing forces of an electric field gradient and a hydrodynamic flow. Recently, we reported EFGF devices fabricated completely from copolymers functionalized with poly(ethylene glycol), which display excellent resistance to protein adsorption. However, the previous devices did not provide the predicted linear electric field gradient and stable current. To improve performance, Tris–HCl buffer that was previously doped in the hydrogel was replaced with a phosphate buffer containing a salt (i.e., potassium chloride, KCl) with high mobility ions. The new devices exhibited stable current, good reproducibility, and a linear electric field distribution in agreement with the shaped gradient region design due to improved ion transport in the hydrogel. The field gradient was calculated based on theory to be approximately 5.76 V/cm2 for R-phycoerythrin when the applied voltage was 500 V. The effect of EFGF separation channel dimensions was also investigated; a narrower focused band was achieved in a smaller diameter channel. The relationship between the bandwidth and channel diameter is consistent with theory. Three model proteins were resolved in an EFGF channel of this design. The improved device demonstrated 14,000-fold concentration of a protein sample (from 2 ng/mL to 27 μg/mL). 相似文献