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41.
B. R. Harvey M. B. Lovett S. J. Boggis 《Journal of Radioanalytical and Nuclear Chemistry》1987,115(2):357-368
Selected experiences in the control of contamination and the threat it poses to the quality of analytical date are discussed in the context of the whole analytical process from collection of marine environmental samples, through handling and radiochemical separation, to the final interpretation of results. Examples include a demonstration of the contamination introduced during sediment core sectioning, contamination of sea water by a ship's pumping system, and the effect of filtration on the apparent partitioning of radionuclides between solid and liquid phases of sea water. 相似文献
42.
Kevin Doyle Maxine Roberts Jenna Harvey Richard Hewer Matthias Zebisch Victor Rangel Meigang Gu Yiming Wu Lichao Yang Mark Carlton Lee Dawson Roland Bürli 《Helvetica chimica acta》2023,106(9):e202300080
Brain concentrations of nicotinamide adenine dinucleotide (NAD+), an important cellular co-factor, tend to decrease with age and in neurodegeneration. As the NADase cluster of differentiation 38 (CD38) significantly contributes to NAD+ consumption, we reasoned that CD38 inhibition may be of therapeutic value for CNS disorders. The new pyrazole compound was designed based on a known CD38 inhibitor and showed good inhibitory potency. Several attempts to co-crystallise this pyrazole with CD38 and cyclic adenosine diphosphate ribose (cADPR) culminated in a high-resolution X-ray structure, in which the pyrazolyl group in the new compound formed a covalent bond with one of the ribosyl units of cADPR. This reaction proceeded under retention of configuration and resulted in a neutral ribosyl-pyrazole conjugate that is embedded within the active site of the enzyme. An analysis of this structural complex gave rise to design principles that enabled the preparation of more potent CD38 inhibitors with drug-like properties. 相似文献
43.
Dr. Stéphanie Essafi Dr. David P. Tew Prof. Jeremy N. Harvey 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(21):5884-5888
Extensive density functional theory (DFT) calculations using the B3LYP functional were used to explore the sextet and quartet energy potential energy surfaces (PESs) of the title reaction, and as a basis to fit global analytical reactive PESs. Surface-hopping dynamics on these PESs reproduce the experimentally observed reactivity and confirm that hydrogen activation rather than spin-state change is rate-limiting at low reaction energy, where the main products are Fe+ and H2O. A change in spin state is inefficient in the product region so that excited-state 4Fe+ is the dominant product. At higher energies, spin-allowed hydrogen atom abstraction to form FeOH+ predominates. At intermediate energy, a previously unexpected rebound mechanism contributes significantly to the reactivity. 相似文献
44.
45.
Zbyněk Brůža Dr. Jiří Kratochvíl Prof. Jeremy N. Harvey Dr. Lubomír Rulíšek Dr. Lucie Nováková Jana Maříková Dr. Jiří Kuneš Prof. Pavel Kočovský Prof. Milan Pour 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(34):8053-8060
Pyran-2-ones 3 undergo a novel Pd0-catalyzed 1,3-rearrangement to afford isomers 6 . The reaction proceeds via an η2-Pd complex, the pyramidalization of which (confirmed by quantum chemistry calculations) offers a favorable antiperiplanar alignment of the Pd−C and allylic C−O bonds ( C ), thus allowing the formation of an η3-Pd intermediate. Subsequent rotation and rate-limiting recombination with the carboxylate arm then gives isomeric pyran-2-ones 6 . The calculated free energies reproduce the observed kinetics semi-quantitatively. 相似文献
46.
We have introduced four alternative teaching strategies into our yearlong organic chemistry course and have assessed changes in student performance relative to the same course taught by the same instructors using a more traditional lecture format. These strategies, which include reading worksheets, dialogues, in-class worksheets, and role-playing, allow the professor to move through a learning cycle that may effectively accommodate the students needs and multiple learning styles. The reading worksheets guide students through the concept phase and dialogues help students identify the importance of the concepts as they articulate these ideas for themselves. Group worksheets and role-playing provide opportunities for peer-interaction, application of knowledge, creativity, and self-expression. Others have shown that active learning strategies neither enhance nor diminish a students ability to retain factual information, a finding that is supported by our study. Our data from this one study show, however, that students taught by a more traditional approach demonstrate a greater variation in final exam performance between first and second semesters than those taught using a combination of techniques. This result reflects a shift in emphasis from the professor as an information source to the actively engaged student taking responsibility for his or her own learning. This study suggests that these methods, when used in a consistent fashion in conjunction with interactive lecturing, provide a broad base to facilitate student learning and aid in the development of higher order thinking skills. 相似文献
47.
Christe KO Wilson WW Petrie MA Michels HH Bottaro JC Gilardi R 《Inorganic chemistry》1996,35(17):5068-5071
The infrared and Raman spectra of the NH(4)(+), K(+), and Cs(+) salts of N(NO(2))(2)(-) in the solid state and in solution have been measured and are assigned with the help of ab initio calculations at the HF/6-31G and MP2/6-31+G levels of theory. In agreement with the variations observed in the crystal structures, the vibrational spectra of the N(NO(2))(2)(-) anion are also strongly influenced by the counterions and the physical state. Whereas the ab initio calculations for the free N(NO(2))(2)(-) ion indicate a minimum energy structure of C(2) symmetry, Raman polarization measurements on solutions of the N(NO(2))(2)(-) anion suggest point group C(1) (i.e., no symmetry). This is attributed to the very small (<3 kcal/mol) N-NO(2) rotational barrier in N(NO(2))(2)(-) which allows for easy deformation. 相似文献
48.
Knots can occur in real and model biological macromolecules. We describe a program for determining whether or not any knots are present in model structures and for classifying those knots that do occur. The program computes the Alexander polynomial, Δ(t), for any model. This polynomial characterizes the knot in the sense that if two knots have different Alexander polynomials, then the knots are topologically distinct. The Alexander polynomial of the circle, or trivial knot, is Δ(t)≡1. If the computed Alexander polynomial is not identically equal to unity, then the structure is nontrivially knotted, and the program will then determine a lower bound on the minimum number of path crossings. The program is entirely general, and may be used to analyze any closed polygonal path. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 813–818, 1999 相似文献
49.
Fabrication of Defined Polydopamine Nanostructures by DNA Origami‐Templated Polymerization 下载免费PDF全文
Yu Tokura Sean Harvey Chaojian Chen Prof. Dr. Yuzhou Wu Dr. David Y. W. Ng Prof. Dr. Tanja Weil 《Angewandte Chemie (International ed. in English)》2018,57(6):1587-1591
A versatile, bottom‐up approach allows the controlled fabrication of polydopamine (PD) nanostructures on DNA origami. PD is a biosynthetic polymer that has been investigated as an adhesive and promising surface coating material. However, the control of dopamine polymerization is challenged by the multistage‐mediated reaction mechanism and diverse chemical structures in PD. DNA origami decorated with multiple horseradish peroxidase‐mimicking DNAzyme motifs was used to control the shape and size of PD formation with nanometer resolution. These fabricated PD nanostructures can serve as “supramolecular glue” for controlling DNA origami conformations. Facile liberation of the PD nanostructures from the DNA origami templates has been achieved in acidic medium. This presented DNA origami‐controlled polymerization of a highly crosslinked polymer provides a unique access towards anisotropic PD architectures with distinct shapes that were retained even in the absence of the DNA origami template. 相似文献
50.
Victoria Hunnam David J. Harvey David A. Priestman Robert H. Bateman Robert S. Bordoli Richard Tyldesley 《Journal of the American Society for Mass Spectrometry》2001,12(11):1220-1225
This paper reports the use of a quadrupole time-of-flight (Q-TOF) mass spectrometer fitted with a matrix-assisted laser desorption/ionization (MALDI) ion source for the analysis of neutral and acidic glycosphingolipids. All compounds gave strong [M + Na]+ ions with 2,5-dihydroxybenzoic acid as the matrix, with no loss of sensitivity with increasing mass as was observed from the corresponding ions produced by electrospray. Neutral glycosphingolipids showed negligible in-source fragmentation but sialylated compounds fragmented by loss of sialic acid. However, these losses were not accompanied by unfocused post-source-decay ions as observed with MALDI-reflectron-TOF instruments. The MS/MS spectra were almost identical to those obtained by electrospray. Fragmentation of all compounds was mainly by glycosidic cleavage to give ions, both with and without the ceramide moiety, which defined the carbohydrate chain sequence. Weak ions which defined the sphingosine chain length and abundant ions, produced by loss of the acyl chain, were present when this chain contained a 2-hydroxy group. The technique was applied to the identification of ceramide-trihexosides present in tissues from mice genetically modified to model one of the glycolipid storage diseases (Fabry disease). 相似文献