共查询到20条相似文献,搜索用时 0 毫秒
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Anton Kaufmann 《Journal of mass spectrometry : JMS》2020,55(9):ii-ii
Liquid chromatography coupled to quadrupole‐based tandem mass spectrometry (QqQ) is termed the “gold standard” for bioanalytical applications because of its unpreceded selectivity, sensitivity, and the ruggedness of the technology. More recently, however, high‐resolution mass spectrometry (HRMS) has become increasingly popular for bioanalytical applications. Nonetheless, this technique is still viewed, either as a screening technology or as a research tool. Although HRMS is actively discussed during scientific conferences, it is yet to be widely utilised in routine laboratory settings and there remains a reluctance to use HRMS for quantitative measurements in regulated environments. This paper does not aim to comprehensively describe the potential of the latest HRMS technology, but rather, it focuses on what results can be obtained and outlines the author's experiences over a period of many years of the routine application of various forms of HRMS instrumentation. Fifteen years ago, some nine different QqQ methods were used in the author's laboratory to analyse a variety of different veterinary drug resides. Today, many more analytes are quantified by seven HRMS methods and just three QqQ methods remain in use for the analysis of a small set of compounds yet to be upgraded to HRMS analysis. This continual upgrading and migration of analytical methods were accompanied by regularly participating in laboratory proficiency tests (PTs). The PT reports (covering a range of analytes and analytical methods) were used to compare the accuracy of HRMS‐ versus QqQ‐based measurements. In the second part of this paper, the particular strengths and limitations of HRMS for both method development and routine measurements are critically discussed. This also includes some anecdotal experiences encountered when replacing QqQ assays with HRMS methods. 相似文献
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Wei-Yang Kong Siew Ching Ngai Bey-Hing Goh Learn-Han Lee Thet-Thet Htar Lay-Hong Chuah 《Molecules (Basel, Switzerland)》2021,26(14)
The rise in cancer cases in recent years is an alarming situation worldwide. Despite the tremendous research and invention of new cancer therapies, the clinical outcomes are not always reassuring. Cancer cells could develop several evasive mechanisms for their survivability and render therapeutic failure. The continuous use of conventional cancer therapies leads to chemoresistance, and a higher dose of treatment results in even greater toxicities among cancer patients. Therefore, the search for an alternative treatment modality is crucial to break this viscous cycle. This paper explores the suitability of curcumin combination treatment with other cancer therapies to curb cancer growth. We provide a critical insight to the mechanisms of action of curcumin, its role in combination therapy in various cancers, along with the molecular targets involved. Curcumin combination treatments were found to enhance anticancer effects, mediated by the multitargeting of several signalling pathways by curcumin and the co-administered cancer therapies. The preclinical and clinical evidence in curcumin combination therapy is critically analysed, and the future research direction of curcumin combination therapy is discussed. 相似文献
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Shao HB Li-Ye C Gang W Jin-Heng Z Zhao-Hua L 《Colloids and surfaces. B, Biointerfaces》2007,55(2):251-255
The First International Conference on the Theory and Practices in Bio-water-saving (ICTPB) was held from May 21 to 25, 2006 in Beijing, China. This indicated that the work related to this hot topic on the globe has been paid more attention to. Most progress in this field has been presented from near 300 participating people worldwide, who were meeting together to discuss about the theory and practices of water-saving biology and how to serve global agricultural and ecological sustainable development. The work related to bio-water-saving has been involved in different scales and soil–plant root biointerfaces. On the basis of this background and in combination with the work from our laboratory and the center, we provided some ideas for global bio-water-saving in this paper, sharing the achievement in this field and advocating true bio-water-saving for the world and promoting the pace of global bio-water-saving. 相似文献
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Coombs ND Stasch A Cowley A Thompson AL Aldridge S 《Dalton transactions (Cambridge, England : 2003)》2008,(3):332-337
Sterically encumbered amido ligands based on a 1,8-diarylcarbazol-9-yl backbone have been investigated as electronically distinct alternatives to the widely-used terphenyl ligand class in the stabilization of low-coordinate metal complexes, and structurally characterized for the first time. While 1,8-diphenylcarbazol-9-yl derivatives are readily available, facile rotation about the Cipso-Cipso bonds leads to structurally characterized main group derivatives {e.g., [(1,8-Ph,-3,6-Me2C12H4N)K]2} in which the coordination geometry at the metal centre is augmented by secondary metal arene interactions. By contrast, the extra bulk inherent in the corresponding 1,8-dimesityl ligand results in essentially perpendicular alignments of the arene and carbazole planes, and a substituent-enforced sterically protected pocket. Comparative structural studies of complexes containing the GaCl2 fragment imply that the 1,8-dimesitylcarbazol-9-yl framework offers greater steric protection at the metal centre than does the corresponding 2,6-dimesitylphenyl ligand. 相似文献
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[structure: see text] The conventional interpretation of proton NMR chemical shifts is supported by large basis set ab initio quantum mechanical calculations. The benzene protons are predicted to lie within the deshielding zone defined in terms of the out-of-plane magnetic shielding domain. However, ring currents by themselves are not sufficient to account quantitatively for the observed benzene proton downfield chemical shift. sigma-Electron contributions must also be taken into account. The conventional explanation for the ethyne proton chemical shift is valid. 相似文献
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2,3-Di-O-benzyl-4,6-O-benzylidene-thiohexopyranosides, on activation with 1-benzenesulfinyl piperidine and triflic anhydride, react with allyl silanes and stannanes, and with silyl enolethers to give C-glycosides. In the mannose series the beta-isomers are formed selectively whereas the glucose series provides the alpha-anomers. This selectivity pattern parallels that of O-glycoside formation and eliminates the need to consider donor-acceptor hydrogen bonding in the formation of the O-glycosides. 相似文献
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Sergey Vyazovkin 《Macromolecular rapid communications》2002,23(13):771-775
The activation energy, E, of nonisothermal crystallization of polymer melts has been frequently evaluated by the Kissinger equation with positive rates of temperature variation, β. It is demonstrated that dropping the negative sign for β is a mathematically invalid procedure that generally makes the Kissinger equation inapplicable to the processes that occur on cooling. Simulations and an experimental example demonstrate that the use of this invalid procedure may result in erroneous values of E. Alternative methods of estimating the correct E values are suggested. 相似文献
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《Chemical physics letters》2002,350(1-2):134-140
We investigate the feasibility of using nuclear magnetic resonance (NMR) chemical shift calculations as a tool to provide structural information for C20 fullerene type molecules. NMR chemical shifts are extremely sensitive to the local chemical environment of an atom, reflecting unambiguously its bond lengths and angles as well as its hybridization. Thus, they can distinguish between the different isomers that are candidates for the ground state of this molecule. We calculate the NMR shifts for several C20 isomers and show that NMR constitutes a potential tool to discriminate and identify experimentally a particular C20 molecular conformation, and also the level of theory which best describes the experimental structure. 相似文献
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Nafisah Al‐Rifai Hannelore Rücker Dr. Sabine Amslinger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(45):15384-15395
Thiol‐mediated processes play a key role to induce or inhibit inflammation proteins. Tailoring the reactivity of electrophiles can enhance the selectivity to address only certain surface cysteines. Fourteen 2′,3,4,4′‐tetramethoxychalcones with different α‐X substituents (X=H, F, Cl, Br, I, CN, Me, p‐NO2‐C6H4, Ph, p‐OMe‐C6H4, NO2, CF3, COOEt, COOH) were synthesized, containing the potentially electrophilic α,β‐unsaturated carbonyl unit. The assessment of their reactivity as electrophiles in thia‐Michael additions with cysteamine shows a change in the reactivity of more than six orders of magnitude. Moreover, a clear correlation between their reactivity and an influence on the inflammation proteins heme oxygenase‐1 (HO‐1) and the inducible NO synthase (iNOS) is demonstrated. As the biologically most active compound, the α‐CF3‐chalcone is shown to inhibit the NO production in RAW264.7 mouse macrophages in the nanomolar range. 相似文献
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《Tetrahedron letters》1986,27(13):1501-1504
The enantioselectivity shown by the title reaction is explained by an intramolecular hydrogen bond in an enamine intermediate resulting from nucleophilic catalysis by one molecule of proline and by a proton transfer mediated by a second molecule of proline. 相似文献
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Carbon nanotubes (CNTs) show exceptional properties that render them attractive for incorporation in a new generation of high‐performance engineering composites with tailored properties. While a great deal of work has been done toward using CNTs as a reinforcing agent in polymer composites, the full potential of CNTs has yet to be reached. In this work, two case studies were proposed in order to analyze the effectiveness of CNTs and carbon fibers (CFs) as reinforcing agents. Micromechanics models for the stiffness and strength of hybrid composites, comprising CNTs and CFs are derived by considering the concept of effective fiber. In addition, the 2009 prices of commercially available CNTs are reviewed. The strongest, the stiffest, and the cheapest CFs commercially available are compared with single walled CNTs (SWCNTs) and multiwalled CNTs (MWCNTs). The simulated results from the micromechanics models show that the use of CFs makes the acquisition of composites with maximum tensile strengths of 4.18 GPa possible. Analysis of the cost versus property relation showed that CNTs are the most viable strengthening option for achieving composites with strengths of up to 11.61 GPa. It is also shown that CFs are the most viable stiffening option, making composites with Young's moduli of up to 383 GPa possible at the expense of the material's toughness. Moreover, it is shown that, in order to achieve CNT's true potential, several challenges have to be faced. CNTs have to be produced with higher purity, longer lengths, better integrity, in larger amounts, and at lower cost. Moreover, issues such as orientation of the CNTs, their concentration, interfacial adhesion, distribution, and dispersion have to be overcome.
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Yuri M. Boiko 《Colloid and polymer science》2013,291(9):2259-2262
Two bulk samples of one and the same or of different amorphous polymers were brought into contact and held for a chosen period of time at a constant healing temperature (T) over the interval of T from below the bulk glass transition temperature (T g bulk) by ~50 °C to above T g bulk by ~10 °C. As formed adhesive joints were shear-fractured in tension at room temperature, and lap-shear strength (σ) was measured as a function of T. It has been found that σ develops with T as logσ?~?1/T both at symmetric and asymmetric interfaces of polystyrene, poly (methyl methacrylate) and poly (2,6-dimethyl-1,4-phenylene oxide). This behaviour implies that there is no discontinuity in the evolution of σ when going through T g bulk, and that this process is controlled by one and the same diffusion mechanism both below and above T g bulk. The results obtained indicate that the contact layer of the polymers investigated is in the viscoelastic state at T well below T g bulk and support the concept of a decrease in the T g of a near-surface layer with respect to T g bulk. 相似文献
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Eli M. Espinoza Duoduo Bao Maciej Krzeszewski Daniel T. Gryko Valentine I. Vullev 《国际化学动力学杂志》2019,51(9):657-668
Attaining long-lived charge-transfer (CT) states is of the utmost importance for energy science, photocatalysis, and materials engineering. When charge separation (CS) is slower than consequent charge recombination (CR), formation of a CT state is not apparent, yet the CT process provides parallel pathways for deactivation of electronically excited systems. The nuclear, or Franck-Condon (FC), contributions to the CT kinetics, as implemented by various formalisms based on the Marcus transition-state theory, provide an excellent platform for designing systems that produce long-lived CT states. Such approaches, however, tend to underestimate the complexity of alternative parameters that govern CT kinetics. Here we show a comparative analysis of two systems that have quite similar FC CT characteristics but manifest distinctly different CT kinetics. A decrease in the donor-acceptor electronic coupling during the charge-separation step provides an alternative route for slowing down undesired charge recombination. These examples suggest that, while infrequently reported and discussed, cases where CR is faster than CS are not necessarily rare occurrences. 相似文献