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1.
James H. Brewster 《Tetrahedron》1974,30(13):1807-1818
An expression for potential energy as a function of torsion angle about a saturated CC bond is developed analytically. This equation is used in the development of two methods for the conformational analysis of paraffins-one based on consideration only of exactly staggered conformers and one giving consideration to energy at 1° intervals of torsion angle. Two methods of assigning molecular rotations to hydrocarbon conformers are considered. Various combinations of results so obtained are compared as ways to calculate rotations for paraffins. 相似文献
2.
Examination of a large number of spectra indicates that bis-unsaturated compounds commonly undergo a skeletal rearrangement in which part or all or the bridging moiety is eliminated, often with concomitant loss of hydrogen atoms. The spectra of labeled azobenzene, diphenyl sulfide, and their p,p′-dimethyl derivatives show that scrambling of hydrogen atoms precedes or accompanies such rearrangements, in contrast to the loss of a p-methyl group from the latter derivatives. These results are rationalized in terms of the radical site formed on one unsaturated functional group attacking the polarizable π-electrons of the other unsaturated group. 相似文献
3.
Emil Pop Marcus E. Brewster J. J. Kaminski Nicholas Bodor 《International journal of quantum chemistry》1989,35(2):315-324
9-Amino-1,2,3,4-tetrahydroacridine (THA ), a potent cholinesterase inhibitor, was recently used in the treatment of Alzheimer's disease. On attempting to prepare a dihydropyridine ? pyridinium salt-based redox chemical delivery system (CDS ) to enhance brain delivery of THA , several of the practical synthetic challenges were examined by using a theoretical MO approach. The structures, reactivities and stability of THA , derivatives of THA and a model compound, 4-aminopyridine, a simple dibasic heterocyclic amine, were studied in the framework of the AM -1 approximation. The study included the possible protonated forms of THA and 4-aminopyridine. The calculated heats of formation showed that ring nitrogen protonated forms are more stable for both THA and 4-aminopyridine. The calculated heats of formation showed that ring nitrogen protonated forms are more stable for both THA and 4-aminopyridine, consistent with experimental results. Electron delocalization is responsible for the remarkable stability of these molecules and for the observed lack of reactivity of the amino group, both in the basic and protonated forms. The site of N-alkylation of the 9-nicotinamide derivative of THA (an intermediate in the synthesis of THA -CDS ) is controlled by electronic, thermodynamic, and steric factors. 相似文献
4.
Jef Peeters Peter Neeskens Marcus Eli Brewster 《Journal of inclusion phenomena and macrocyclic chemistry》2007,57(1-4):137-139
Pirodavir, 4-[2-[1-(6-Methyl-3-pyridazinyl)-4-piperidinyl]ethoxy]benzoic acid ethyl ester, is an antiviral compound which
has low aqueous solubility (<0.01 mg/ml). The compound is a weak base (pKa 5.8) with high lipophicity (logP 4.44). Ionization
of the compound increases the solubility in acidic medium to 2.3 mg/ml at pH 2.4. However, a low pH is not acceptable for
nasal application as this would induce irritation.
Extensive solubility studies were performed using different types of substituted cyclodextrins in order to select an appropriate
derivate capable of increasing solubility to an acceptable level for formulations for nasal application. Aqueous solubility
of pirodavir increased in a linear fashion with increasing concentration of most of the substituted cyclodextrins. However,
using 2-hydropropyl-β-cyclodextrin (HPBCD) the solubility increased in a non-linear fashion. Based on these studies HPBCD
was selected as the most appropriate excipient.
To support a clinical study on the treatment of rhinovirus cold by intranasal Pirodavir formulations were developed containing
up to 5 mg/ml of pirodavir and up to 10% of HPBCD. Stability of the formulations was studied and found to be acceptable. 相似文献
5.
6.
Using Goursat??s characterization of subgroups in a direct product, a characterization of subgroup containment in such a direct product is given. Applying this along with facts about p-groups we describe a process for obtaining the subgroup lattice of a direct product of p-groups. This process is implemented to portray the subgroup lattice of Q × Q, where Q is the quaternion group of order 8. 相似文献
7.
Richard C. Brewster Geňa Hahn Stacey Wynn Lamont Chester Lipka 《Discrete Mathematics》2012,312(10):1638-1645
The reconstruction number of a graph is the smallest number of vertex-deleted subgraphs needed to uniquely determine the graph up to isomorphism. Bollobás showed that almost all graphs have reconstruction number equal to three. McMullen and Radziszowski published a catalogue of all graphs on at most ten vertices with reconstruction number greater than three. We introduce constructions that generalize the examples identified in their work. In particular, we use lexicographic products of vertex transitive graphs with certain starter graphs from the work of Myrvold and from the work of Harary and Plantholt to generate new infinite families of graphs with high reconstruction numbers. In the process, we settle a question of McMullen and Radziszowski. 相似文献
8.
Emil Pop Stanislaw Rachwal Marcus E. Brewster 《International journal of quantum chemistry》1996,60(8):1829-1834
The allylic rearrangement of trans-pinocarveol esters ( I ) to myrtenol esters ( II ), a reaction of interest in the chemistry of terpenes and cannabinoids, has been theoretically investigated. The intramolecular, cyclization-induced rearrangement results in equilibrium mixtures of the starting compounds and the products with the ratio of I vs. II in the equilibrium mixture being determined by their thermodynamic stabilities. The relative thermodynamic stabilities as reflected by calculated AM1 heats of formations (ΔHf) were determined for various I-II ester pairs. The study, in agreement with available experimental evidence, indicates that generally I , which contain an endocyclic double bond, are more stable and thus predominantly form following rearrangements. In two cases (acetate and pivalate) the stability is reversed. Calculations performed for similar structures, esters of 2-methylene cyclohexane-1-ol ( IV ) and 1-cyclohexene-1-methanol ( V ) gave similar results. Structural and electronic factors which might influence the stability of these compounds were examined. Interestingly, a correlation between thermodynamic stability and dipole moments was observed. © 1996 John Wiley & Sons, Inc. 相似文献
9.
In this paper we extend the plane blow-up results of Grundy& McLaughlin (1997) to the three-dimensional Navier-Stokes equations.Using a solution structure originally due to Lin we first providenumerical evidence for the existence of blow-up solutions on- < x, z < , 0 y 1 with boundary conditions on y = 0and y = 1 involving derivatives of the velocity components.The formulation enables us to consider plane and radial flowas special cases. Various features of the computations are isolatedand are used to construct a formal asymptotic solution closeto blow-up. We show that the numerical and asymptotic analysesprovide a mutually consistent global picture which supportsthe conclusion that, for the family of problems we considerhere, blow-up in fact can take place in three dimensions butat an inverse linear rate rather than the faster inverse squareof the plane case. 相似文献
10.
Ice nucleating-active Pseudomonas fluorescens F264C was fed to Colorado potato beetles to determine bacterial retentioin in the beetle gut and its effect on the cold hardiness of this insect pest. The bacrterium was present in beetles recovered after overwintering in the field, seven months after their exposure to P. fluorescens. Retention was evident not only in the detection of the P. fluorescens ice nucleating gene, inaW, in bacterial cultures from beetle guts but also in the elevated supercooling points of some treated beetles. 相似文献