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991.
Sven M. Papidocha Hendrik H. Bulthaupt Prof. Erick M. Carreira 《Angewandte Chemie (International ed. in English)》2023,62(48):e202310149
The first total synthesis of heavily oxidized cassane-type diterpenoid neocaesalpin A ( 1 ) is disclosed. At the heart of the synthesis lies an intermolecular Diels–Alder reaction that rapidly assembles the target framework from commercial materials. A carefully orchestrated sequence of oxidations secured the desired oxygenation pattern. Late-stage release of the characteristic butenolide occurred through a novel mercury(II)-mediated furan oxidation. Successful extension of the route allowed preparation of neocaesalpin AA ( 2 ) as well as nominal neocaesalpin K ( 3 ) and suggested structural revision of neocaesalpin K, leading to the hypothesis that the two are likely the same natural product with correct assignment as 2 . 相似文献
992.
Goenaga-Infante H Sturgeon R Turner J Hearn R Sargent M Maxwell P Yang L Barzev A Pedrero Z Cámara C Díaz Huerta V Fernández Sánchez ML Sanz-Medel A Emese K Fodor P Wolf W Goldschmidt R Vacchina V Szpunar J Valiente L Huertas R Labarraque G Davis C Zeisler R Turk G Rizzio E Mackay LG Myors RB Saxby DL Askew S Chao W Jun W 《Analytical and bioanalytical chemistry》2008,390(2):629-642
Results of an international intercomparison study (CCQM-P86) to assess the analytical capabilities of national metrology institutes
(NMIs) and selected expert laboratories worldwide to accurately quantitate the mass fraction of selenomethionine (SeMet) and
total Se in pharmaceutical tablets of selenised-yeast supplements (produced by Pharma Nord, Denmark) are presented. The study,
jointly coordinated by LGC Ltd., UK, and the Institute for National Measurement Standards, National Research Council of Canada
(NRCC), was conducted under the auspices of the Comité Consultatif pour la Quantité de Matière (CCQM) Inorganic Analysis Working
Group and involved 15 laboratories (from 12 countries), of which ten were NMIs. Apart from a protocol for determination of
moisture content and the provision of the certified reference material (CRM) SELM-1 to be used as the quality control sample,
no sample preparation/extraction method was prescribed. A variety of approaches was thus used, including single-step and multiple-step
enzymatic hydrolysis, enzymatic probe sonication and hydrolysis with methanesulfonic acid for SeMet, as well as microwave-assisted
acid digestion and enzymatic probe sonication for total Se. For total Se, detection techniques included inductively coupled
plasma (ICP) mass spectrometry (MS) with external calibration, standard additions or isotope dilution MS (IDMS), inductively
coupled plasma optical emission spectrometry , flame atomic absorption spectrometry and instrumental neutron activation analysis.
For determination of SeMet in the tablets, five NMIs and three academic/institute laboratories (of a total of five) relied
upon measurements using IDMS. For species-specific IDMS measurements, an isotopically enriched standard of SeMet (76Se-enriched SeMet) was made available. A novel aspect of this study relies on the approach used to distinguish any errors
which arise during analysis of a SeMet calibration solution from those which occur during analysis of the matrix. To help
those participants undertaking SeMet analysis to do this, a blind sample in the form of a standard solution of natural abundance
SeMet in 0.1 M HCl (with an expected value of 956 mg kg−1 SeMet) was provided. Both high-performance liquid chromatography (HPLC)–ICP-MS or gas chromatography (GC)–ICP-MS and GC-MS
techniques were used for quantitation of SeMet. Several advances in analytical methods for determination of SeMet were identified,
including the combined use of double IDMS with HPLC-ICP-MS following extraction with methanesulfonic acid and simplified two-step
enzymatic hydrolysis with protease/lipase/driselase followed by HPLC-ICP-IDMS, both using a species-specific IDMS approach.
Overall, satisfactory agreement amongst participants was achieved; results averaged 337.6 mg kg−1 (n = 13, with a standard deviation of 9.7 mg kg−1) and 561.5 mg kg−1(n = 11, with a standard deviation of 44.3 mg kg−1) with median values of 337.6 and 575.0 mg kg−1 for total Se and SeMet, respectively. Recovery of SeMet from SELM-1 averaged 95.0% (n = 9). The ability of NMIs and expert laboratories worldwide to deliver accurate results for total Se and SeMet in such materials
(selensied-yeast tablets containing approximately 300 mg kg−1 Se) with 10% expanded uncertainty was demonstrated. The problems addressed in achieving accurate quantitation of SeMet in
this product are representative of those encountered with a wide range of organometallic species in a number of common matrices.
Figure Looking into the quantitative speciation of selenium in pharmaceutical supplements Photo courtesy of LGC. 相似文献
993.
Chuan-Min Lee 《Discrete Mathematics》2008,308(18):4185-4204
Let Y be a subset of real numbers. A Y-dominating function of a graph G=(V,E) is a function f:V→Y such that for all vertices v∈V, where NG[v]={v}∪{u|(u,v)∈E}. Let for any subset S of V and let f(V) be the weight of f. The Y-domination problem is to find a Y-dominating function of minimum weight for a graph G=(V,E). In this paper, we study the variations of Y-domination such as {k}-domination, k-tuple domination, signed domination, and minus domination for some classes of graphs. We give formulas to compute the {k}-domination, k-tuple domination, signed domination, and minus domination numbers of paths, cycles, n-fans, n-wheels, n-pans, and n-suns. Besides, we present a unified approach to these four problems on strongly chordal graphs. Notice that trees, block graphs, interval graphs, and directed path graphs are subclasses of strongly chordal graphs. This paper also gives complexity results for the problems on doubly chordal graphs, dually chordal graphs, bipartite planar graphs, chordal bipartite graphs, and planar graphs. 相似文献
994.
A dominating set of vertices S of a graph G is connected if the subgraph G[S] is connected. Let γc(G) denote the size of any smallest connected dominating set in G. A graph G is k-γ-connected-critical if γc(G)=k, but if any edge is added to G, then γc(G+e)?k-1. This is a variation on the earlier concept of criticality of edge addition with respect to ordinary domination where a graph G was defined to be k-critical if the domination number of G is k, but if any edge is added to G, the domination number falls to k-1.A graph G is factor-critical if G-v has a perfect matching for every vertex v∈V(G), bicritical if G-u-v has a perfect matching for every pair of distinct vertices u,v∈V(G) or, more generally, k-factor-critical if, for every set S⊆V(G) with |S|=k, the graph G-S contains a perfect matching. In two previous papers [N. Ananchuen, M.D. Plummer, Matching properties in domination critical graphs, Discrete Math. 277 (2004) 1-13; N. Ananchuen, M.D. Plummer, 3-factor-criticality in domination critical graphs, Discrete Math. 2007, to appear [3].] on ordinary (i.e., not necessarily connected) domination, the first and third authors showed that under certain assumptions regarding connectivity and minimum degree, a critical graph G with (ordinary) domination number 3 will be factor-critical (if |V(G)| is odd), bicritical (if |V(G)| is even) or 3-factor-critical (again if |V(G)| is odd). Analogous theorems for connected domination are presented here. Although domination and connected domination are similar in some ways, we will point out some interesting differences between our new results for the case of connected domination and the results in [N. Ananchuen, M.D. Plummer, Matching properties in domination critical graphs, Discrete Math. 277 (2004) 1-13; N. Ananchuen, M.D. Plummer, 3-factor-criticality in domination critical graphs, Discrete Math. 2007, to appear [3].]. 相似文献
995.
Acidic persulfate oxidation is one of the most common procedures used to digest dissolved organic phosphorus compounds in water samples for total dissolved phosphorus determination. It has been reported that the rates of phosphoantimonylmolybdenum blue complex formation were significantly reduced in the digested sample matrix. This study revealed that the intermediate products of persulfate oxidation, not the slight change in pH, cause the slowdown of color formation. This effect can be remedied by adjusting digested samples pH to a near neural to decompose the intermediate products. No disturbing effects of chlorine on the phosphoantimonylmolybdenum blue formation in seawater were observed. It is noted that the modification of mixed reagent recipe cannot provide near neutral pH for the decomposition of the intermediate products of persulfate oxidation. This study provides experimental evidence not only to support the recommendation made in APHA standard methods that the pH of the digested sample must be adjusted to within a narrow range of sample, but also to improve the understanding of role of residue from persulfate decomposition on the subsequent phosphoantimonylmolybdenum blue formation. 相似文献
996.
Starting from 4-bromo-Uhle's ketone (2), an alkylation step using ethyl 3-methylamino-propionate followed by intramolecular aldol condensation in two steps, transformation of the ester group into a methyl group, and finally cyclopropanation of the 8,9 double bond, resulted in a six-step total synthesis of (±)-cycloclavine (1). 相似文献
997.
Efficient total halogen-free photochemical bleaching of kraft pulps using alkaline hydrogen peroxide
Total halogen-free bleaching of kraft pulps was conducted by an oxidative photochemical process at room temperature using alkaline hydrogen peroxide. Selection of an appropriate wavelength of light was crucial for effective bleaching and avoiding degradation of cellulose. The wavelength of the light has to be selected so that the light is absorbed only by the colored compounds in the pulps and not by the bleaching reagents or the pulp itself. When a long-wavelength black-light fluorescent lamp was used in combination with aqueous hydrogen peroxide solution at pH 11, the bleaching efficiency for hardwood and softwood kraft pulps reached the same level as that obtained by conventional two-stage elemental chlorine-free processes. 相似文献
998.
Elminir HK Own HS Azzam YA Riad AM 《Journal of photochemistry and photobiology. B, Biology》2008,90(3):198-206
The problem we address here describes the on-going research effort that takes place to shed light on the applicability of using artificial intelligence techniques to predict the local noon erythemal UV irradiance in the plain areas of Egypt. In light of this fact, we use the bootstrap aggregating (bagging) algorithm to improve the prediction accuracy reported by a multi-layer perceptron (MLP) network. The results showed that, the overall prediction accuracy for the MLP network was only 80.9%. When bagging algorithm is used, the accuracy reached 94.8%; an improvement of about 13.9% was achieved. These improvements demonstrate the efficiency of the bagging procedure, and may be used as a promising tool at least for the plain areas of Egypt. 相似文献
999.
Dieter Spreen 《Archive for Mathematical Logic》2005,44(2):209-217
A strong reducibility relation between partial numberings is introduced which is such that the reduction function transfers exactly the numbers which are indices under the numbering to be reduced into corresponding indices of the other numbering. The degrees of partial numberings of a given set with respect to this relation form an upper semilattice.In addition, Ershovs completion construction for total numberings is extended to the partial case: every partially numbered set can be embedded in a set which results from the given set by adding one point and which is enumerated by a total and complete numbering. As is shown, the degrees of complete numberings of the extended set also form an upper semilattice. Moreover, both semilattices are isomorphic.This is not so in the case of the usual, weaker reducibility relation for partial numberings which allows the reduction function to transfer arbitrary numbers into indices.This research has partially been supported by INTAS under grant 00-499 Computability in Hierarchies and Topological Spaces.Mathematics Subject Classification (2000): 03D45 相似文献
1000.
This paper discusses the interfacing of continuous membrane extraction, pervaporation and on-line HPLC-UV detection into a total analytical system (TAS). Organics from a water sample were extracted into an organic solvent, and then concentrated via pervaporation prior to HPLC-UV detection. Factors affecting the system performance were studied. With optimized experimental parameters enrichment factors as high as 192 were obtained, the method detection limits were at low ng/mL levels, and the precisions were better than 5%. 相似文献