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101.
The potential energy surfaces of the Li(n)Si(4)(-) (n = 0-5) clusters were explored using the Kick Coalescence method. We found that, for those systems with n ≤ 2, the butterfly and parallelogram Si(4)(2-) kernels prevail as building blocks; however, when n ≥ 3, the Si(4)(4-) tetrahedral kernel, which is commonly found in heavier alkali monosilicides, MSi (M = Na, K, Rb, Cs), arises as the prevailing building block. In addition, by a natural population analysis (NPA) we found that the maximum charge transfer -4 from Li atoms to Si atoms is attained when n = 3. The addition of more Li atoms to the Si(4)(4-) system does not increase the charge transfer, but keeps it almost constant at the maximum value. We also calculated theoretical vertical electron detachment energies (VDEs) for low-lying isomers of the Li(n)Si(4)(-) (n = 0-4) clusters in order to facilitate their experimental identification. 相似文献
102.
Perez-Peralta N Contreras M Tiznado W Stewart J Donald KJ Merino G 《Physical chemistry chemical physics : PCCP》2011,13(28):12975-12980
We have explored in silico the potential energy surfaces of the C(5)Li(n)(n-6) (n = 5, 6, and 7) clusters using the Gradient Embedded Genetic Algorithm (GEGA) and other computational strategies. The most stable forms of C(5)Li(5)(-) and C(5)Li(6) are two carbon chains linked by two lithium atoms in a persistent seven membered ring capped by two Li atoms. The other Li atoms are arrayed on the edge of the seven membered ring. In contrast, the global minimum structure for C(5)Li(7)(+) is a bicapped star of D(5h) symmetry. The molecular orbital analysis and computed magnetic field data suggest that electron delocalization, as well as the saturation of the apical positions of the five-membered carbon ring with lithium atoms in C(5)Li(7)(+) plays a key role in the stabilization of the carbon-lithium star. In fact, the planar star sub-structure for the carbon ring are unstable without the apical caps. This is also what has been found for the Si analogues. The split of the B(ind)(z) in its σ- and π-contribution indicates that C(5)Li(7)(+) is a π-aromatic and σ-nonaromatic system. 相似文献
103.
Cortez-Espinosa N Aviña-Verduzco JA Ramírez-Chávez E Molina-Torres J Ríos-Chávez P 《Natural product communications》2011,6(6):857-861
Acmella radicans (Asteraceae) produces at least seven alkamides, most with either an isobutyl- or phenylethyl group as the amine moiety. These moieties suggest that the amino acids valine and phenylalanine are the biosynthetic precursors of these alkamides. On the basis of labeled feeding experiments using either L-[2H8]valine or L-[2H8]phenylalanine we present evidence for the involvement of these two amino acids in the biosynthesis of (2E,6Z,8E)-N-isobutyl-2,6,8-decatrienamide (affinin) (1), (2Z,4E)-N-(2-phenylethyl)-2,4-octadienamide (2), (2E)-N-(2-phenylethyl)-nona-2-en-6,8-diynamide (3), and 3-phenyl-N-(2-phenylethyl)-2-propenamide (4). Alkamides were isolated from young A. radicans plants and analyzed by gas chromatography-mass spectrometry (GC-MS). Additionally, in cell free in vitro experiments based on isobutyl and phenylethylamide biosynthesis, using a colorimetric assay and GC-MS, valine and phenylalanine decarboxylase activities were assayed in the soluble extract of A. radicans leaves. 相似文献
104.
John S. Caughman Charles L. Dunn Nancy Ann Neudauer Colin L. Starr 《Discrete Mathematics》2011,(16):1803
Lattice chains and Delannoy paths represent two different ways to progress through a lattice. We use elementary combinatorial arguments to derive new expressions for the number of chains and the number of Delannoy paths in a lattice of arbitrary finite dimension. Specifically, fix nonnegative integers n1,…,nd, and let L denote the lattice of points (a1,…,ad)∈Zd that satisfy 0≤ai≤ni for 1≤i≤d. We prove that the number of chains in L is given by where . We also show that the number of Delannoy paths in L equals Setting ni=n (for all i) in these expressions yields a new proof of a recent result of Duchi and Sulanke [9] relating the total number of chains to the central Delannoy numbers. We also give a novel derivation of the generating functions for these numbers in arbitrary dimension. 相似文献
105.
Abstract A fiber optic probe was interfaced to a photon counting system for the determination of nicotinamide adenine dinucleotide reduced [NAD(P)H] by a bioluminescence method. The reagents employed in a bacterial luciferase/flavin mononucleotide /decanal system were optimized. Attempts were made to increase the quantum yield of the system. Dodecanal, tridecanal, and tetradecanal were evaluated as alternative aldehyde reagents for decanal, and hydrogen peroxide was added to the system. Neither attempt increased the quantum yield of the system. However, a relatively low detection limit of 1.6 × 10?9 M for NAD(P)H was obtained with a linear dynamic range of 3.8 orders of magnitude. These results demonstrate the sensitivity of this instrumentation and assay. 相似文献
106.
Thermal activation of molecularly-wired gold nanoparticles on a substrate as catalyst 总被引:5,自引:0,他引:5
Luo J Jones VW Maye MM Han L Kariuki NN Zhong CJ 《Journal of the American Chemical Society》2002,124(47):13988-13989
The ability to prepare nanostructured metal catalysts requires the ability to control size and interparticle spatial and surface access properties. In this work, we report novel findings of an atomic force microscopic investigation of a controlled thermal activation strategy of gold catalysts nanostructured via molecular wiring or linking on a substrate surface. Gold nanocrystals of approximately 2 nm diameter capped by decanethiolate and wired by 1,9-nonanedithiolate on mica substrates were studied as a model system. By manipulating the activation temperature (200-250 degrees C), the capping/wiring molecules can be removed to produce controllable particle size and interparticle spatial morphology. The electrocatalytic activity of the activated nanostructures toward methanol oxidation, which is of fundamental importance to fuel cell catalysis, has been demonstrated. The novelty of the findings is the viability of a thermal activation strategy of core-shell nanostructured catalysts based on molecularly predefined interparticle spatial properties on a substrate, which upon further investigation may form the basis for spatially controllable nanostructured catalysts. 相似文献
107.
NEW PHTHALOCYANINE PHOTOSENSITIZERS FOR PHOTODYNAMIC THERAPY 总被引:2,自引:1,他引:2
Nancy L. Oleinick Antonio R. Antunez Marian E. Clay Boris D. Rihter Malcolm E. Kenney 《Photochemistry and photobiology》1993,57(2):242-247
Six new aluminum and silicon phthalocyanines have been synthesized and their photocytotoxicity toward V79 cells has been studied. The compounds that have been prepared are: AIPcOSi(CH3)2(CH2),N(CH3)2, I; AIPcOSi(CH3)2(CH2)3N(CH3)3+I?, II; CH3SiPcOSi(CH3)2(CH2)3N(CH3)2, III; HOSiPcOSi(CH3)2(CH2)3N(CH3)2, IV; HOSiPcOSi(CH3)2(CH2)3)3(CH3)3+I?, V; and SiPc[OSi(CH3)2(CH2)3N(CH3)3+I?]2, VI. Relative growth delay values for compounds I-VI and relative cytotoxicity values for compounds I, II, IV, V and VI have been determined. Compounds I and II have been shown to be comparable in photocytotoxicity to what is presumed to be AIPcOH.xH2O, and compound IV has been shown to have greater activity. The classes of compounds to which these six compounds belong appear to have potential for photodynamic therapy. 相似文献
108.
Pablo Fuentealba Lorenzo Serón Camila Sánchez Jorge Manzur Verónica Paredes-Garcia Nancy Pizarro 《Journal of Coordination Chemistry》2014,67(23-24):3894-3908
A family of macrocyclic complexes [M2LnCl2] have been synthesized and characterized (M: CuII or ZnII; Ln: macrocyclic ligand derived from 2-hydroxy-5-methyl-1,3-benzenedicarbaldehyde and different aliphatic diamines and o-phenylenediamine). The influence of the aromaticity of the ligand and the metal center on the spectroscopic properties of the complexes (absorption and emission) has been studied. Making use of the weak interactions between hydrated potassium ions and the layers of the K0.4Mn0.8PS3 precursor, the obtained macrocyclic complexes have been intercalated in the interlamellar space by a microwave assisted cationic exchange reaction. The optical properties of the obtained hybrid materials are reported. The absorption edge, recorded by solid state reflectance spectroscopy for CuII and the ZnII macrocycle-based composites, is 1.67–1.76 eV, both shifted to lower energy compared with that of the pristine MnPS3. 相似文献
109.
We report a case study that explored how three college students mentally represented the knowledge they held of inferential statistics, how this knowledge was connected, and how it was applied in two problem solving situations. A concept map task and two problem categorization tasks were used along with interviews to gather the data. We found that the students’ representations were based on incomplete statistical understanding. Although they grasped various concepts and inferential tests, the students rarely linked key concepts together or to tests nor did they accurately apply that knowledge to categorize word problems. We suggest that one reason the students had difficulty applying their knowledge is that it was not sufficiently integrated. In addition, we found that varying the instruction for the categorization task elicited different mental representations. One instruction was particularly effective in revealing students’ partial understandings. This finding suggests that modifying the task format as we have done could be a useful diagnostic tool. 相似文献
110.