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61.
A simple, sensitive and rapid method for the determination of the pesticides ziram and zineb was described. This new method was based on the coupling of FIA methodology and direct chemiluminescent detection; this approach had not been used up to now with these pesticides. The additional use of an ‘on line’ photochemical reaction, which was performed by using a photoreactor consisting of a long piece of PTFE helically coiled around a 15 W low-pressure lamp, increased by a factor >20 the chemiluminometric response of the pesticides. An additional 3-fold improvement in the analytical signal was also achieved by using quinine as sensitizer. The obtained throughputs were very high (121 and 101 h−1 for ziram and zineb, respectively); this feature together with its low limit of detection (1 ng mL−1) makes this method particularly well suited to routine analyses of environmental samples. On the other hand, its applicability to two members of the dithiocarbamate family of pesticides, makes it promising for the determination of the rest of the members of this family. The method was demonstrated by application to spiked water samples from different origins (ground, river and irrigation). 相似文献
62.
Hector Castro-Abril Jónathan Heras Jesús del Barrio Laura Paz Clara Alcaine Marina Pérez Aliácar Diego Garzón-Alvarado Manuel Doblaré Ignacio Ochoa 《Macromolecular bioscience》2023,23(10):2300108
Mechanical interactions between cells and their microenvironment play an important role in determining cell fate, which is particularly relevant in metastasis, a process where cells invade tissue matrices with different mechanical properties. In vitro, type I collagen hydrogels have been commonly used for modeling the microenvironment due to its ubiquity in the human body. In this work, the combined influence of the stiffness of these hydrogels and their ultrastructure on the migration patterns of HCT-116 and HT-29 spheroids are analyzed. For this, six different types of pure type I collagen hydrogels by changing the collagen concentration and the gelation temperature are prepared. The stiffness of each sample is measured and its ultrastructure is characterized. Cell migration studies are then performed by seeding the spheroids in three different spatial conditions. It is shown that changes in the aforementioned parameters lead to differences in the mechanical stiffness of the matrices as well as the ultrastructure. These differences, in turn, lead to distinct cell migration patterns of HCT-116 and HT-29 spheroids in either of the spatial conditions tested. Based on these results, it is concluded that the stiffness and the ultrastructural organization of the matrix can actively modulate cell migration behavior in colorectal cancer spheroids. 相似文献
63.
Pereira CC Balula SS Paz FA Valente AA Pillinger M Klinowski J Gonçalves IS 《Inorganic chemistry》2007,46(21):8508-8510
The oxo-bridged dimer [Mo(2)O(4)(mu(2)-O)Cl(2)(pzH)(4)] (1; pzH = pyrazole) exhibits unusually high activity in the liquid-phase catalytic epoxidation of the cyclic olefins cyclooctene and (R)-(+)-limonene under mild conditions and in the absence of additional organic solvents, using tert-butyl hydroperoxide as the oxidant. The complex is stable under the reaction conditions and can be used in further catalytic runs without significant loss of performance. An X-ray crystallographic investigation reveals that 1 has an unprecedented and extremely rare all-cis configuration at each of the MoO(2)-(mu(2)-O)Cl(pzH)(2) cores, which can be understood by considering supramolecular contacts and geometric factors. 相似文献
64.
Carmen Paz Suárez Araujo Patricio García Báez Álvaro Sánchez Rodríguez José Juan Santana Rodríguez 《Analytical and bioanalytical chemistry》2009,394(4):1059-1072
In this paper, we approach, using neural computation and ensemble systems, a pattern classification problem in fluorescence
spectrometry, the resolution of difficult multi-fungicide mixtures (overlapping), specifically the benzimidazole fungicides,
benomyl, carbendazim, thiabendazole and fuberidazole. These fungicides are compounds of an important environmental interest.
Because of this, from an analytical point of view, it is interesting to develop sensitive, selective and simple methods for
their determination. Fluorescence spectrometry has proven to be a sensitive and selective technique for determination of many
compounds of environmental interest, but in some cases it is not enough. HUMANN is a hierarchical, unsupervised, modular,
adaptive neural net with high biological plausibility, which has shown to be suitable for identification of these fungicides
and organochlorinated compounds of environmental interest. We propose two modular artificial intelligent systems, with a structure
of pre-processing and processing stage, a multi-input HUMANN-based system, using multi-fluorescence spectra as input to the
system, and a HUMANN-ensemble system. We analyze the optimal configuration of inputs and the ensemble in order to obtain better
results. We study such figures as precision and sensitivity of the method. Our proposal is a smart, flexible and effective
complementary method, which allows reducing the analytical and/or computational complexity of the analysis.
Figure Stages in identification of benzimidazole fungicides
Based on a contribution presented at the XIII International Symposium on Luminescence Spectrometry held in Bologna, Italy
from Sept. 7–11, 2008. 相似文献
65.
66.
Nieto-Oberhuber C López S Muñoz MP Jiménez-Núñez E Buñuel E Cárdenas DJ Echavarren AM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(6):1694-1702
Gold(I) complexes are the most active catalysts for the biscyclopropanation of dienynes to form tetracyclic compounds. PtII and ZnII are also able to promote the biscyclopropanation, although less efficiently. The configurations obtained in all cases with the use of gold(I) catalysts can be explained by the pathway proceeding through anti cyclopropyl gold carbenes. Similar intermediates are most probably involved in reactions catalyzed by RuII and PtII. Two different cyclopropanation pathways have been found; they depend on the structures of the cyclopropyl gold carbenes (anti or syn) and the relative arrangements of the metal carbenes and the alkenes. 相似文献
67.
Bray KL Lloyd-Jones GC Muñoz MP Slatford PA Tan EH Tyler-Mahon AR Worthington PA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(34):8650-8663
The mechanism of the highly regioselective cycloisomerisation of dimethyl hept-1,6-dienyl-4,4-dicarboxylate (1) by a neutral pre-catalyst, [(tBuCN)(2)PdCl(2)] (8), to generate dimethyl 3,4-dimethylcyclopent-2-ene-1,1-dicarboxylate (3) has been investigated by isotopic labelling (reactions involving single and mixed samples of 1,1,2,6,7,7-[(2)H(6)]-1; 3,3,5,5-[(2)H(4)]-1; 1,7-(Z,Z)-[(2)H(2)]-1; [1,3-(13)C(1),5,7-(13)C(1)]-1 and [1,3-(13)C(1),6-(2)H(1)]-1) and by study of the reactions of dimethyl 1-aryl-hept-1,6-dienyl-4,4-dicarboxylates (9 a-e, where aryl is p-C(6)H(4)-X; X=H, OMe, Me, Cl, CF(3)) and dimethyl hept-1,5-dienyl-4,4-dicarboxylate (14), a 1,5-diene isomer of 1. The mechanism proposed involves the generation of a monochloro-bearing palladium hydride which undergoes a simple hydropalladation, carbopalladation, Pd/H dyotropy, beta-H elimination sequence to generate 3. A key point that emerges is that chelation of the 1,6-diene 1 at various stages in the mechanism plays an important role in determining the regioselectivity of the reaction. The selective generation of 3 with pre-catalysts of the form L(2)PdCl(2), as compared to the generation of dimethyl 3-methylene-4-methyl-cyclopentane-1,1-dicarboxylate (2) with pre-catalysts of the form [(MeCN)(2)Pd(allyl)]OTf (5) is ascribed to the absence of chloride ion in the latter, which makes an additional coordination site available throughout turnover. Liberation of the product 3 when [(tBuCN)(2)PdCl(2)] (8) is employed as pre-catalyst, is proposed to proceed via a mono- to bidentate switch in the pi-coordination of diene 1 (eta(2) to bis-eta(2)) displacing pi-coordinated 3 from Pd. When 1-aryl-1,6-dienes 9 are employed as substrates, the electron-donor property of the aryl group is found to influence the regioselectivity of cyclisation. Electron-withdrawing groups favour dimethyl 3-arylmethyl-4-methylcyclopent-2-ene-1,1-dicarboxylates (10), whilst electron-donating aryl groups favour 3-arylidene-4-methyl-cyclopentane-1,1-dicarboxylates (11). The regioselectivity (10/11) correlates with the Hammett sigma(+) values (rho(+)=1.3, r (2)=0.975) indicative of a strong pi-resonance contribution from the aryl ring rather than a simple sigma-inductive effect. Intermolecular modulation of regioselectivity is observed and the net effect proposed to arise through the (pi-->d) donation ability of the vinyl arene in the diene displacing product (10/11) via a mono- to bidentate switch in coordination. The isomerisation process increasingly sequesters Pd as turnover proceeds leading to a powerful inhibition mechanism and ultimately a limitation in turnover number to about 80. 相似文献
68.
Juan M. Aceves-Hernández Esther Agacino-Valdés Manuel Paz 《Journal of Molecular Structure》2006,786(1):1-8
Hydrochlorothiazide was characterized in order to determine the possible structural modifications at different temperatures due to its importance as a drug to control heart diseases and a diuretic. This compound could present conformers due to the rotation of the NH2 group, which was studied by using different techniques such as Thermal Analysis, IR spectroscopy, X-Ray Diffraction and complemented by theoretical calculations. The theoretical and experimental results point to the conclusion that no polymorphic forms are present in the compound under study. The calculations confirm the apparent difference in values between theory and experiment for the vibration frequencies explained by the hydrogen bonds between near molecules. 相似文献
69.
A new PCR-CGE (size and color) method for simultaneous detection of genetically modified maize events 总被引:1,自引:0,他引:1
We present a novel multiplex PCR assay for simultaneous detection of multiple transgenic events in maize. Initially, five PCR primers pairs specific to events Bt11, GA21, MON810, and NK603, and Zea mays L. (alcohol dehydrogenase) were included. The event specificity was based on amplification of transgene/plant genome flanking regions, i.e., the same targets as for validated real-time PCR assays. These short and similarly sized amplicons were selected to achieve high and similar amplification efficiency for all targets; however, its unambiguous identification was a technical challenge. We achieved a clear distinction by a novel CGE approach that combined the identification by size and color (CGE-SC). In one single step, all five targets were amplified and specifically labeled with three different fluorescent dyes. The assay was specific and displayed an LOD of 0.1% of each genetically modified organism (GMO). Therefore, it was adequate to fulfill legal thresholds established, e.g., in the European Union. Our CGE-SC based strategy in combination with an adequate labeling design has the potential to simultaneously detect higher numbers of targets. As an example, we present the detection of up to eight targets in a single run. Multiplex PCR-CGE-SC only requires a conventional sequencer device and enables automation and high throughput. In addition, it proved to be transferable to a different laboratory. The number of authorized GMO events is rapidly growing; and the acreage of genetically modified (GM) varieties cultivated and commercialized worldwide is rapidly increasing. In this context, our multiplex PCR-CGE-SC can be suitable for screening GM contents in food. 相似文献
70.
M. Fernandes F. A. Almeida Paz J. F. Mano V. de Zea Bermudez 《Crystal Research and Technology》2014,49(6):418-430
The influence of myristyl alcohol (CH3(CH2)13OH), cetyl alcohol (CH3(CH2)15OH) and behenyl alcohol (CH3(CH2)21OH) on the structure, morphology, size and surface properties of calcium carbonate (CaCO3) has been investigated. Changes in the nature of the washing solvent, in the CnOH/Ca2+ and CO32−/Ca2+ molar ratios and in temperature have been also evaluated. The sole polymorph produced was rhombohedral calcite. At room temperature, while microspheres composed of submicrocubes were produced at a high molar ratio CO32−/Ca2+ and low CH3(CH2)15OH concentration, a stoichiometric molar ratio CO32−/Ca2+ and high CH3(CH2)15OH concentration induced the formation of microcubes and microboxes. In the presence of this alkanol (12 % molar) a significant enhancement of the water contact angle (ca. 40 °) resulted in a sample obtained with a stoichiometric CO32−/Ca2+ ratio. These results emphasize the key role played by the three non‐ionic surfactants in the formation of materials with variable crystal shape and wettability and thus technological interest for a range of applications. 相似文献