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51.
Victoria A. Ternes Hannah A. Morgan Austin P. Lanquist Michael J. Murray Bradley M. Wile 《应用有机金属化学》2020,34(4):e5459
Herein we report the preparation of a series of Ru(II) complexes featuring α-iminopyridine ligands bearing thioether functionality (NNSR, where R = Me, CH2Ph, Ph). Metallation using [(p-cymene)RuCl]2 permits access to Ru complexes with a κ2-N,N donor set in which the thioether moiety remains uncoordinated. In the presence of a strong field ligand such as acetonitrile or triphenylphosphine, the p-cymene moiety is displaced, and the ligand adopts a κ3-N,N,S binding mode. These complexes are characterized using a combination of solution and solid state methods, including the crystal structure of [(NNSMe)Ru (NCMe)2Cl]Cl. The κ2-N,N-Ru(II) complexes are shown to serve as efficient precatalysts for the oxidation of sec-phenethyl alcohol at modest loadings (alcohol: Ru = 20:1), using a variety of external oxidants and solvents. The complex bearing an S-Ph donor was found to be the most active oxidation catalyst of those surveyed, suggesting that the thioether donor plays an active role in the catalytic cycle. 相似文献
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53.
Summary Polyamines and polyamine conjugates display a diverse range of important biological functions, ranging from antibiotics to immunosuppressants and glutamate receptor antagonists. For these reasons, polyamines provide an excellent template/scaffold for combinatorial chemistry. In this paper we present methods for the solid-phase immobilisation of polyamines for use in synthetic and combinatorial chemistry and describe how they have been employed in the preparation of a number of important polyamine conjugates and polyamine libraries. Thus, we have designed, synthesised and utilised a number of polyamine linkers for both solution and resin screening combinatorial application. 相似文献
54.
Duncan Farquharson Gregory (1813–1844) was a mathematician and founder of the Cambridge Mathematical Journal. His 1841 Examples of the Processes of the Differential and Integral Calculus was an extensive revision of Peacock's 1820 textbook of a similar title. Among the new material in Gregory's version is an exposition of symbolical algebra, prominently featuring the method of “separation of symbols.” We examine Gregory's career; the mathematicians he influenced; and Servois and Murphy, who influenced him. We consider Gregory's use of separation of symbols in the Examples and consider whether he believed these techniques to be capable of providing an adequate foundation for calculus. © 2002 Elsevier Science (USA).Le mathématicien Duncan Farquharson Gregory (1813–1844) fut également fondateur du Cambridge Mathematical Journal. Son ouvrage publié en 1841, Examples of the Processes of the Differential and Integral Calculus, constitue une révision substantielle du livre de Peacock au titre similaire. L'un des apports du livre de Gregory est un exposé de l'algèbre symbolique, et en particulier de la méthode de séparation des symboles. Dans cet article nous passons en revue la carrière de Gregory et nous parlons des mathématiciens qu'il a influencés, ainsi que de l'influence que Servois et Murphy ont eu sur ses travaux. Nous considérons son usage de la séparation des symboles dans ses Examples, et nous examinons si Gregory croyait que ses techniques pouvaient constituer un fondement pour le calcul différentiel. © 2002 Elsevier Science (USA).MSC 1991 subject classifications: 01A55, 01A70, 01A50, 26-03, 26A03, 34-03, 34A30. 相似文献
55.
A simple means is deduced for determining conditions for secondary particle formation in emulsion polymerization systems in systems where the amount of added surfactant is below the cmc. A new radical formed from initiator in the aqueous phase will undergo some polymerization with aqueous-phase monomer, but must have three possible eventual fates: aqueous-phase termination, entry into a preexisting particle, or creation of a new particle. The means for determining the onset and extent of secondary nucleation is to modify HUFT theory to take into account a successful model for entry [ Macromolecules, 24, 1629 (1991)] which states that entry occurs if and only if the aqueous-phase radical has achieved a critical degree of polymerization z. Particle formation below the cmc is by homogeneous/coagulative nucleation which (if coagulation is ignored) gives an upper bound to the rate of formation of precursor particles; these are of a degree of polymerization Jcrit > z. The resulting equations are readily solved, and require only a knowledge of the aqueous-phase propagation and termination rate coefficients (the latter is very high: ca. 109 dm3 mol−1 s−1 for termination between the very small radicals), z and jcrit. Easily applied means are given for estimating all these quantities. The treatment gives good accord with experimentally observed conditions for the onset of secondary nucleation in low-surfactant systems (including taking in situ micellization into account). 相似文献
56.
Christman KL Requa MV Enriquez-Rios VD Ward SC Bradley KA Turner KL Maynard HD 《Langmuir : the ACS journal of surfaces and colloids》2006,22(17):7444-7450
Micron and submicron-scale features of aldehyde functionality were fabricated in polymer films by photolithography to develop a platform for protein immobilization and assembly at a biologically relevant scale. Films containing the pH-reactive polymer poly(3,3'-diethoxypropyl methacrylate) and a photoacid generator (PAG) were patterned from 500 nm to 40 mum by exposure to 365 nm (i-line) light. Upon PAG activation and hydrolysis of acetals, aldehyde groups formed. After the films were incubated with a biotinylated aldehyde reactive probe, the X-ray photoelectron spectroscopy results were consistent with biotin being attached to the surface. The background was subsequently passivated by flood exposure and incubation with an aminooxy-terminated poly(ethylene glycol), resulting in a 98% reduction in nonspecific protein adsorption. Protein patterning and assembly was demonstrated using streptavidin, biotinylated anthrax toxin receptor-1, and the protective antigen moiety of anthrax toxin and confirmed by fluorescence microscopy and atomic force microscopy (AFM). AFM demonstrated that 500 nm protein features were achieved. Because of the abundance of biotinylated proteins, this methodology provides a platform for protein immobilization and assembly for various applications in biotechnology. 相似文献
57.
Kusari U Li Y Bradley MG Sneddon LG 《Journal of the American Chemical Society》2004,126(28):8662-8663
In contrast to reactions that have been observed in traditional organic solvents, decaborane olefin-hydroboration and alkyne-insertion reactions have been found to proceed in ionic liquid solvents without the need of a catalyst. These reactions now provide important new, high-yield synthetic pathways to functionalized decaborane and o-carborane clusters. 相似文献
58.
In this study we synthesized and characterized mirror image barnase (B. amyloliquefaciens ribonuclease). d-Barnase was identical to l-barnase, when analyzed by liquid chromatography and mass-spectrometry. Proteolysis of the mirror image enzyme revealed that in contrast to its native counterpart, d-barnase was completely stable to digestive proteases. In enzymatic assays, d-barnase had the reciprocal chiral specificity and was fully active towards mirror image substrates. Interestingly, d-barnase also hydrolyzed the substrate of the native chirality, albeit 4000 times less efficiently. This effect was further confirmed by digesting a native 112-mer RNA with the enzyme. Additional studies revealed that barnase accommodates a range of substrates with various chiralities, but the prime requirement for guanosine remains. These studies point toward using mirror image enzymes as modern agents in biotechnology. 相似文献
59.
Heterologous expression and mutagenesis of the enterocin type II polyketide synthase (PKS) system suggest for the first time that the association of an extended set of proteins and substrates is needed for the effective production of the enterocin-wailupemycin polyketides. In the absence of its endogenous ketoreductase (KR) EncD in either the enterocin producer "Streptomyces maritimus" or the engineered host S. lividans K4-114, the enterocin minimal PKS is unable to produce benzoate-primed polyketides, even when complemented with the homologous actinorhodin KR ActIII or with EncD active site mutants. These data suggest that the enterocin PKS requires EncD to serve a catalytic and not just a structural role in the functional PKS enzyme complex. This strongly implies that EncD reduces the polyketide chain during elongation rather than after its complete assembly, as suggested for most type II PKSs. 相似文献
60.
Top-down patterning of zeolitic imidazolate framework composite thin films by deep X-ray lithography
Dimitrakakis C Marmiroli B Amenitsch H Malfatti L Innocenzi P Grenci G Vaccari L Hill AJ Ladewig BP Hill MR Falcaro P 《Chemical communications (Cambridge, England)》2012,48(60):7483-7485
For the first time a top-down process was used to control the spatial location of Metal-Organic Frameworks on a surface. Deep X-ray lithography was utilised to micropattern a Zeolitic Imidazolate Framework layer on a sol-gel surface, with exposure hardening the sol-gel by inducing crosslinking while leaving the frameworks intact. 相似文献