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排序方式: 共有177条查询结果,搜索用时 359 毫秒
1.
Aidan Mooney John G. Keating Daniel M. Heffernan 《Chaos, solitons, and fractals》2006,30(5):1088-1097
A digital watermark is a visible, or preferably invisible, identification code that is permanently embedded in digital media, to prove owner authentication and provide protection for documents. Given the interest in watermark generation using chaotic functions a detailed study of one chaotic function for this purpose is performed. In this paper, we present an approach for the generation of watermarks using the logistic map. Using this function, in conjunction with seed management, it is possible to generate chaotic sequences that may be used to create highpass or lowpass digital watermarks. In this paper we provide a detailed study on the generation of optically detectable watermarks and we provide some guidelines on successful chaotic watermark generation using the logistic map, and show using a recently published scheme, how care must be taken in the selection of the function seed. 相似文献
2.
G L Grunewald M A Pleiss C L Gatchell R Pazhenchevsky M F Rafferty 《Journal of chromatography. A》1984,292(2):319-331
The elution behaviour of a selection of sequence variant and modified insulins has been compared on a C18 reversed-phase column. Observed elution times were compared with those expected from the nature of the differences from bovine insulin. In some cases prediction rules established for peptides are adequate to explain the observed elution and in others detailed knowledge of the structure of the protein is of considerable importance in understanding elution behaviour. 相似文献
3.
4.
Smith JC Siu KW Rafferty SP 《Journal of the American Society for Mass Spectrometry》2004,15(5):629-638
The investigation of protein quaternary structure, protein-cofactor, and protein-ligand interactions by mass spectrometry is often limited by the fragility of such interactions under experimental conditions. To develop more gentle conditions of perhaps general use, we used as a model for study the oxygenase domain of murine inducible nitric oxide synthase (iNOS), which is homodimeric, binds heme and tetrahydrobiopterin H(4)B cofactors, and the substrate L-arginine. The energetics of the collisions in q2 and in the lens region of the mass spectrometer were manipulated for varying the degree of solvation around the non-covalently bound ions. Furthermore, the number of low-energy collisions in the collision cell of the instrument was varied, focusing and dampening the ion beam. Under gentle source collision conditions, and using multiple low-energy collisions in the collision cell of the mass spectrometer, dimers of the iNOS oxygenase domain containing heme, H(4)B, and arginine were observed intact after electrospraying at pH values near neutrality; a mutant of this protein (Trp188 --> Phe) was monomeric and did not bind cofactors. The pH dependence of the iNOS oxygenase domain under acidic conditions was also studied; while heme remained bound to the protein between pH 2.5 and 4.0, the dimeric structure was disrupted. Our findings confirm that non-covalently bound macromolecular complexes are retained and observable using electrospray mass spectrometry under the appropriate experimental conditions. 相似文献
5.
Salt cluster ions of alkali metal chlorides ACl (A = Li(+), Na(+), K(+), Rb(+) and Cs(+)) and sodium salts NaB (B = I(-), HCOO(-), CH(3)COO(-), NO(2)(-), and NO(3)(-)), formed by electrospray ionization, were studied systematically by mass spectrometry. The influences on the total positive ion and negative ion currents of variation of solvent, solution concentration, desolvation temperature, solution flow-rate, capillary voltage and cone voltage were investigated. Only cone voltage was found to influence dramatically the distribution of salt cluster ions in the mass spectra observed. Under conditions of normal cone voltage of approximately 70 V, cluster ions having magic numbers of molecules are detected with high relative signal intensity. Under conditions of low cone voltage of approximately 10 V, the distribution of cluster ions detected is characterized by a relatively low average mass/charge ratio due to the presence of multiply charged cluster ions; in addition, there is a marked reduction in cluster ions having a magic number of molecules. Product ion mass spectra obtained by tandem mass spectrometry of cluster ions are characterized by a base peak having a magic number of molecules that is less than and closest to the number of molecules in the precursor ion. Structures have been proposed for some dications and some quadruply charged ions. At pH 3 and 11, the mass spectra of NaCl clusters show the presence of mixed clusters of NaCl with HCl and NaOH, respectively. The effects of ionic radius on 20 distributions of cluster ions for 10 salts were investigated; however, the fine structure of these effects is not readily discerned. 相似文献
6.
Reaction between 2-vinyl pyridine and azodicarboxylates 2 or 5 gives N,N'-disubstituted tetrahydropyrido[3,2-c]pyridazines 3 and 6, and dihydro-3H-pyrido[1,2-c]triazines 4 and 7; 2-(prop-1-en-1-yl)-pyridine 8 gives hydropyridopyridazines 10 and 11 but 2-(prop-1-en-2-yl)pyridine 9 gives mainly the ‘ene’ addition product 12. From 4-vinyl-pyridine and esters 2 or 5 diesters of tetrahydropyrido[3,4-c]pyridazine-1,2-dicarboxylic acid, 25 and 26 are obtained, and from 2-methyl-5-vinylpyridine both possible cyclisation products, the tetrahydro-pyrido[2,3-c]pyridazines 33 and 36, and -pyrido[4,3-c]pyridazines 34 and 37. The di-t-butyl esters 6, 11, 26, and 37 are quantitatively decarbalkoxylated in TFA, giving tetrahydropyridopyridazines 16, 18, 27, and 41; of these, the first three were oxidized to give pyrido[2,3-c]-pyridazine 15, its 3-methyl derivative 19, and pyrido[3,4-c]pyridazine 28 respectively. A dihydropyrido[4,3-c]-pyridazine 42 was obtained from compound 41. Thieno[2,3-c]-pyridazine 48 has been similarly prepared from 2-vinylthiophen, but 2-(prop-1-en-2-yl)thiophen gave an ene addition compound 51 and a dihydrothienopyridazine 50. Reactions with other vinylpyridines, and with vinylfurans, were unsuccessful. 相似文献
7.
Xin Chen Aleksandra M. Krajewska Dr. Cormac McGuinness Amy Lynes David McAteer Nina Berner Prof. Georg Duesberg Prof. Jonathan N. Coleman Prof. Aidan R. McDonald 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(3):984-992
Covalently tethering photosensitizers to catalytically active 1T-MoS2 surfaces holds great promise for the solar-driven hydrogen evolution reaction (HER). Herein, we report the preparation of two new RuII-complex-functionalized MoS2 hybrids [RuII(bpy)2(phen)]-MoS2 and [RuII(bpy)2(py)Cl]-MoS2. The influence of covalent functionalization of chemically exfoliated 1T-MoS2 with coordinating ligands and RuII complexes on the HER activity and photo-electrochemical performance of this dye-sensitized system was studied systematically. We find that the photo-electrochemical performance of this RuII-complex-sensitized MoS2 system is highly dependent on the surface extent of photosensitizers and the catalytic activity of functionalized MoS2. The latter was strongly affected by the number and the kind of functional groups. Our results underline the tunability of the photovoltage generation in this dye-sensitized MoS2 system by manipulation of the surface functionalities, which provides a practical guidance for smart design of future dye-sensitized MoS2 hydrogen production devices towards improved the photofuel conversion efficiency. 相似文献
8.
Giuseppe Spedalotto Dr. Robert Gericke Marta Lovisari Dr. Erik R. Farquhar Dr. Brendan Twamley Dr. Aidan R. McDonald 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(51):11983-11990
Hydroxide-bridged high-valent oxidants have been implicated as the active oxidants in methane monooxygenases and other oxidases that employ bimetallic clusters in their active site. To understand the properties of such species, bis-μ-hydroxo-NiII2 complex ( 1 ) supported by a new dicarboxamidate ligand (N,N′-bis(2,6-dimethyl-phenyl)-2,2-dimethylmalonamide) was prepared. Complex 1 contained a diamond core made up of two NiII ions and two bridging hydroxide ligands. Titration of the 1 e− oxidant (NH4)2[CeIV(NO3)6] with 1 at −45 °C showed the formation of the high-valent species 2 and 3 , containing NiIINiIII and NiIII2 diamond cores, respectively, maintaining the bis-μ-hydroxide core. Both complexes were characterised using electron paramagnetic resonance, X-ray absorption, and electronic absorption spectroscopies. Density functional theory computations supported the spectroscopic assignments. Oxidation reactivity studies showed that bis-μ-hydroxide-NiIII2 3 was capable of oxidizing substrates at −45 °C at rates greater than that of the most reactive bis-μ-oxo-NiIII complexes reported to date. 相似文献
9.
We prove that every Kirchberg algebra in the UCT class has nuclear dimension 1. We first show that Kirchberg 2-graph algebras with trivial K0 and finite K1 have nuclear dimension 1 by adapting a technique developed by Winter and Zacharias for Cuntz algebras. We then prove that every Kirchberg algebra in the UCT class is a direct limit of 2-graph algebras to obtain our main theorem. 相似文献
10.
Paolo Pirovano Adriana M. Magherusan Ciara McGlynn Andrew Ure Amy Lynes Dr. Aidan R. McDonald 《Angewandte Chemie (International ed. in English)》2014,53(23):5946-5950
Metal‐bound superoxide intermediates are often implicated as electrophilic oxidants in dioxygen‐activating metalloenzymes. In the nonheme iron α‐ketoglutarate dependent oxygenases and pterin‐dependent hydroxylases, however, FeIII–superoxide intermediates are postulated to react by nucleophilic attack on electrophilic carbon atoms. By reacting a CuII–superoxide complex ( 1 ) with acyl chloride substrates, we have found that a metal–superoxide complex can be a very reactive nucleophile. Furthermore, 1 was found to be an efficient nucleophilic deformylating reagent, capable of Baeyer–Villiger oxidation of a number of aldehyde substrates. The observed nucleophilic chemistry represents a new domain for metal–superoxide reactivity. Our observations provide support for the postulated role of metal–superoxide intermediates in nonheme iron α‐ketoglutarate dependent and pterin‐dependent enzymes. 相似文献