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211.
Jennifer Paola Hernández Mancera Francisco Núñez-Zarur Soledad Gutiérrez-Oliva Alejandro Toro-Labbé Ricardo Vivas-Reyes 《Journal of computational chemistry》2020,41(23):2022-2032
Quantum chemical calculations were used to study the mechanism of Diels-Alder reactions involving chiral anthracenes as dienes and a series of dienophiles. The reaction force analysis was employed to obtain a detailed scrutiny of the reaction mechanisms, it has been found that thermodynamics and kinetics of the reactions are quite consistent: the lower the activation energy, the lower the reaction energy, thus following the Bell-Evans-Polanyi principle. It has been found that activation energies are mostly due to structural rearrangements that in most cases represented more than 70% of the activation energy. Electronic activity mostly due to changes in σ and π bonding were revealed by the reaction electronic flux (REF), this property helps identify whether changes on σ or π bonding drive the reaction. Additionally, new global indexes describing the behavior of the electronic activity were introduced and then used to classify the reactions in terms of the spontaneity of their electronic activity. Local natural bond order electronic population analysis was used to check consistency with global REF through the characterization of specific changes in the electronic density that might be responsible for the activity already detected by the REF. Results show that reactions involving acetoxy lactones are driven by spontaneous electronic activity coming from bond forming/strengthening processes; in the case of maleic anhydrides and maleimides it appears that both spontaneous and non-spontaneous electronic activity are quite active in driving the reactions. 相似文献
212.
Ana Salomé Pires João Batista Dina Murtinho Célia Nogueira Anna Karamysheva M. Luísa Ramos Bruce F. Milne Nuno Tiago Tavares José Gonçalves Ana Cristina Gonçalves Ana Margarida Abrantes Rui Soares Teresa Gonçalves Maria Filomena Botelho M. Elisa Silva Serra 《应用有机金属化学》2020,34(5):e5569
Platinum metal complexes are the most common chemotherapeutics currently used in cancer treatment. However, the frequent adverse effects, as well as acquired resistance by tumor cells, urge the development of effective alternatives. In the recent past, copper complexes with Schiff base ligands have emerged as good alternatives, showing interesting results. Accordingly, and in continuation of previous studies in this area, three new camphoric acid-derived halogenated salen ligands and their corresponding Cu (II) complexes were synthesized and their antitumor activity was evaluated in order to determine the influence of the type and number of halogens present (Br, Cl). The in vitro cytotoxic activity was screened against colorectal WiDr and LS1034 and against breast MCF-7 and HCC1806 cancer cell lines. The results proved the halogenated complexes to be very efficient, the tetrachlorinated Cu (II) complex being the most promising, presenting IC50 of 0.63–1.09 μM for the cell lines studied. The complex also shows selectivity to colorectal cancer cells compared to non-tumor colon cells. It is worth highlighting that the tetrachlorinated Cu (II) complex, our most efficient complex, shows a significantly more powerful antitumor effect than the reference drugs currently used in conventional chemotherapy. The halogenated salen and corresponding complexes were also screened for their antimicrobial activity against four bacterial species-Staphylococcus aureus, Enterococcus faecalis, Escherichia coli and Pseudomonas aeruginosa-and four fungal species-Candida albicans, Candida glabrata, Aspergillus fumigatus and Alternaria alternata. The compounds were found to exhibit moderate to strong antibacterial activity against the bacterial strains studied. NMR studies and theoretical calculations provided some insight into the structure of the ligands and copper complexes. Considering the results presented herein, our work validates the potential use of copper-based chemotherapeutics as alternatives for cancer treatment. 相似文献
213.
Yosselin Huentupil Patricio Chung Néstor Novoa A. Hugo Klahn Manuela E. Medina Jonathan Cisterna Iván Brito Andrés Rivera Rodrigo López-Muñoz Rodrigo Arancibia 《应用有机金属化学》2020,34(9):e5788
In the research of new compounds with multifunctional applications, heterobinuclear palladium (II) complexes based on organometallic dithiocarbazates (DTCZs) have been isolated. The organometallic DTCZ ligands of the general formula [{(η5-C5H4)-CH=NNHC(S)SCH3}]MLn [MLn = Re (CO)3 ( 2a ); Mn (CO)3 ( 2b ); FeCp ( 2c )] were prepared by the reaction between formyl organometallic precursors ( 1a−c ) with S-methyldithiocarbazate. Subsequently, a two-step reaction of 2a−c with: (i) K2[PdCl4] and (ii) PPh3 yielded heterobinuclear complexes [Pd{MLn(η5-C5H4)-CH=NNHC(S)SCH3}–(Cl)(PPh3)] [MLn = Re (CO)3 ( 3a ); Mn (CO)3 ( 3b ); FeCp ( 3c )]. All compounds were characterized by conventional spectroscopic techniques (infrared spectroscopy, nuclear magnetic resonance spectroscopy, mass spectrometry and elemental analysis). In addition, the molecular structures of 2a , 2c and 3c were determined by single-crystal X-ray diffraction. The new palladium (II) complexes ( 3a−c ) were evaluated as antiproliferative agents against non-small cell lung cancer cells (H1299 cells). Complexes 3a and 3b containing cyrhetrenyl- and cymantrenyl-DTCZ ligands, respectively, were more active than their ferrocenyl analogue 3c . The activity was associated with the electron-withdrawing properties of the (η5-C5H4)M (CO)3 moieties and their better lipophilicity than that of the ferrocenyl analogue. In addition, we studied the capacity of metalloligands ( 2a−c ) and palladium (II) complexes ( 3a−c ) to remove methylene blue in water under UV–visible light irradiation. The results established that the complexes showed moderate efficiency and were less active than their corresponding free ligands. 相似文献
214.
Gustavo D. Mendes Thais da Silva Pereira Júlio César Rodrigues Elaine Marcílio Santos Mariani Rafaela Souza Rodrigo Alvaro Brandão Lopes-Martins Natalícia de Jesus Antunes Ronilson Agnaldo Moreno Gilberto De Nucci 《Biomedical chromatography : BMC》2020,34(4):e4731
To assess the bioequivalence of two zolpidem hemitartrate formulations in 30 healthy volunteers. Plasma samples were obtained over a 24 h period. Plasma concentrations of zolpidem were analyzed by liquid chromatography coupled to tandem mass spectrometry with positive ion electrospray ionization using multiple reaction monitoring. Values of peak concentration (Cmax), area under curve (AUC), half-life, elimination constant, volume of distribution and clearance showed statistically significant differences when comparing women (604.34 ng h/ml, 127.36 ng/ml, 4.4 h, 0.18 1/h, 50.56 L and 8.55 L/h, respectively) and men (276.1 ng h/ml, 70.9 ng/ml, 3.3 h, 0.26 1/h, 91.42 L and 24.34 L/h, respectively), receiving the same dose (5 mg), respectively. The geometric means with corresponding 90% confidence interval for Test/Reference percentage ratios were 99.73% (CI 93.69–106.16) for Cmax, 97.44% (90% CI = 91.85–103.37%) for area under curve of plasma concentration until the last concentration observed (AUClast) and 98.30% (90% CI = 92.48–104.49) for the area under curve between the first sample (pre-dosage) and infinity (AUC0–inf). Since the 90% CI for AUClast, AUC0–inf and Cmax ratios were within the 80–125% interval proposed by the US Food and Drug Administration, it was concluded that zolpidem hemitartrate formulation (5 mg orodispersible tablet) is bioequivalent to the zolpidem hemitartrate formulation (Patz SL 5 mg sublingual tablet) with regard to both the rate and the extent of absorption. A new formulation of zolpidem 2.5 mg may be useful in women for the same clinical benefits as the 5 mg formulation in men. 相似文献
215.
João Marcos G. Barbosa Milenna K. Fernandes Rodrigues Lurian C. David Taynara C. e Silva Danielly A. Fortuna Lima Naiara Z. Pereira Emmanuel B. D'Alessandro Anselmo E. de Oliveira Paulo H. Jorge da Cunha Maria Clorinda S. Fioravanti Nelson R. Antoniosi Filho 《Biomedical chromatography : BMC》2020,34(11):e4935
An innovative volatolomic approach employs the detection of biomarkers present in cerumen (earwax) to identify cattle intoxication by Stryphnodendron rotundifolium Mart., Fabaceae (popularly known as barbatimão). S. rotundifolium is a poisonous plant with the toxic compound undefined and widely distributed throughout the Brazilian territory. Cerumen samples from cattle of two local Brazilian breeds (‘Curraleiro Pé-Duro’ and ‘Pantaneiro’) were collected during an experimental intoxication protocol and analyzed using headspace (HS)/GC–MS followed by multivariate analysis (genetic algorithm for a partial least squares, cluster analysis, and classification and regression trees). A total of 106 volatile organic metabolites were identified in the cerumen samples of bovines. The intoxication by S. rotundifolium influenced the cerumen volatolomic profile of the bovines throughout the intoxication protocol. In this way, it was possible to detect biomarkers for cattle intoxication. Among the biomarkers, 2-octyldecanol and 9-tetradecen-1-ol were able to discriminate all samples between intoxicated and nonintoxicated bovines. The cattle intoxication diagnosis by S. rotundifolium was accomplished by applying the cerumen analysis using HS/GC–MS, in an easy, accurate, and noninvasive way. Thus, the proposed bioanalytical chromatography protocol is a useful tool in veterinary applications to determine this kind of intoxication. 相似文献
216.
Summary Mercury(II) in the presence of a large excess of thiocyanate forms a violet colour with Rhodamine B. The complex formed can be stabilized by addition of poly(vinyl alcohol), and forms the basis for a spectrophotometric method for determination of trace amounts of mercury. The calibration graph for measurement at 610 nm is linear in the range 1–15g of mercury per 25 ml, with a molar absorptivity of 1.1×105l· mole–1·cm·. The effect of foreign ions has been studied and the method can be applied to the determination of mercury in air with reliable analytical results.
Spektrophotometrische Bestimmung von Quecksilber mit Rhodanid und Rhodamin B
Zusammenfassung In Gegenwart eines großen Überschusses von Rhodanid bildet Hg(II) mit Rhodamin B eine violette Färbung. Durch Zusatz von Polyvinylalkohol kann dieser Komplex stabilisiert werden und bietet somit die Grundlage für die spektrophotometrische Bestimmung von Hg-Spuren. Die Eichkurve für die Messung bei 610 nm verläuft für 1–15g Hg/25 ml linear. Die molare Absorptivität beträgt 1,1×105 l·mol–1·cm–1. Die Fremdionenwirkung wurde untersucht. Das Verfahren kann zur Hg-Bestimmung in Luft verwendet werden.相似文献
217.
A. F. Ibaez G. B. Yaculiano G. Y. Moltrasio Iglesias 《Journal of heterocyclic chemistry》1989,26(4):907-911
Synthesis and 1H-, 13C-nmr analysis of some substituted 3-phenyl-1,2,3,4-tetrahydroisoquinolines are reported. Spectroscopy assignments of hydrogen and carbon resonances were made on the basis of standard chemical shift theory, comparison with reference compounds, attached proton test and fully coupled 13C-nmr spectra. Data showed that at room temperature two conformers predominated for the 1,3-disubstituted and 1,2,3-trisubstituted isoquinolines. 相似文献
218.
Marlin Opałło Nagao Kobayashi Tetsuo Osa 《Journal of inclusion phenomena and macrocyclic chemistry》1989,7(4):413-422
The complexation of 2,3-anthracenedicarboxylate (ADC) by- and-cyclodextrins in water containing an organic solvent has been studied by induced circular dichroism. It has been shown that an increase of organic solvent ratio causes the degradation of the 1:1 ADC:-CD complex and the liberation of one guest molecule from the 2:1 ADC:-CD complex in water. The higher the hydrophobicity of the cosolvent, the weaker the complexation of ADC by-CD. 相似文献
219.
A convenient route to the daunomycinone precursor 18via a succession of Diels-Alder reactions from 2,7-dichloronaphthazarin (9) is described. In a similar manner, starting from 2,6-dichloronaphthazarin (19) compound 20, a regioisomer of 18,is synthesized. This methodology constitutes a regiospecific approach to (±)-daunomycinone and related anthracyclinones. 相似文献
220.
J. J. LaBrecque Z. A. De Benzo E. Marcano C. A. Peña 《Journal of Radioanalytical and Nuclear Chemistry》1984,84(2):407-413
The comparison of an ambient temperature mercuric iodide spectrometer (HgI2) with a conventional cooled Si(Li) spectrometer is presented for the determination of niobium in Venezuelan laterites in the laboratory. The energy resolution of the HgI2 spectrometer was only about 590 eV (FWHM) at 5.9 keV compared to about 150 eV for the conventional Si(Li) spectrometer. The efficiency was about 5 times lower in the region of the NbK
peak as compared to the Si(Li) detector. Even though its energy resolution and efficiency is much poorer than the conventional Si(Li), the results it produced for the determination of niobium were acceptable for use in the exploration and exploitation of a niobium-rich deposit such as Cerro Impacto, Estado Bolívar, Venezuela. 相似文献