全文获取类型
收费全文 | 562篇 |
免费 | 36篇 |
国内免费 | 2篇 |
专业分类
化学 | 452篇 |
晶体学 | 1篇 |
力学 | 14篇 |
数学 | 46篇 |
物理学 | 87篇 |
出版年
2024年 | 2篇 |
2023年 | 8篇 |
2022年 | 32篇 |
2021年 | 30篇 |
2020年 | 27篇 |
2019年 | 18篇 |
2018年 | 12篇 |
2017年 | 6篇 |
2016年 | 27篇 |
2015年 | 29篇 |
2014年 | 23篇 |
2013年 | 42篇 |
2012年 | 45篇 |
2011年 | 50篇 |
2010年 | 17篇 |
2009年 | 17篇 |
2008年 | 35篇 |
2007年 | 31篇 |
2006年 | 29篇 |
2005年 | 33篇 |
2004年 | 16篇 |
2003年 | 10篇 |
2002年 | 20篇 |
2000年 | 4篇 |
1999年 | 3篇 |
1998年 | 3篇 |
1997年 | 5篇 |
1996年 | 3篇 |
1995年 | 3篇 |
1994年 | 1篇 |
1992年 | 4篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 4篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1978年 | 1篇 |
1955年 | 1篇 |
排序方式: 共有600条查询结果,搜索用时 15 毫秒
581.
Solvation structure and ion complexation of La3+ in a 1 molal aqueous solution of lanthanum chloride
H/D isotopic substitution neutron scattering and X-ray scattering have been used to investigate the short and intermediate range solution structure in a 1 m aqueous solution of lanthanum chloride. To improve the reliability of the local structural information on the cation environment, information has been incorporated from Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy data into the applied analytical framework. The markedly different structural sensitivities of the experimental probes allow the construction of a detailed three-dimensional atomistic model using the Empirical Potential Structure Refinement (EPSR) technique. The results show that at the investigated concentration La(3+) is hydrated by eight water molecules and one chloride ion, forming an inner-sphere ion complex in which the water molecules maintain angular configurations consistent with a tricapped trigonal prism configuration. This local geometry considerably disrupts the bulk solvent structure. 相似文献
582.
Kouras-Hadef S de Sainte-Claire P ter Halle A Amine-Khodja A Richard C 《The journal of physical chemistry. A》2011,115(50):14397-14406
Substituted 4-amino-1,2,4-triazin-5-ones undergo photodeamination through cleavage of the N-NH(2) bond in the presence of oxygen and water. To elucidate the mechanism of this reaction, we investigated the photolysis of metamitron (4-amino-6-phenyl-3-methyl-1,2,4-triazin-5-one) by nanosecond laser flash photolysis, steady-state irradiation, and ab initio calculations. Upon pulsed laser excitation of deoxygenated aqueous metamitron, two transient species are clearly detected. The predictions of ab initio results are consistent with experimental results: (i) it is proposed here that the transient species are, respectively, the keto and diradical forms of the metamitron keto-enol tautomerism in the triplet state, and (ii) in water, the activation free energy barrier of enolization is drastically decreased. Thus, the formation of the diradical triplet is enabled in aqueous solvent. A detailed analysis of the intermediate structures that lead to the final products (HNO(2) and deaminometamitron) is provided. 相似文献
583.
584.
Sofia C.V. Latas Mário F.S. Ferreira 《The European physical journal. Special topics》2014,223(1):79-89
We investigate numerically, both in time and frequency domains, the influence of some higher-order effects, namely the third-order dispersion, intrapulse Raman scattering, and self-steepening, on the dynamics of different pulsating and chaotic solitons in dissipative systems, which are described by a generalized complex Ginzburg-Landau equation. We show that the higher-order effects can have a dramatic impact on the dynamics of such pulses and that, for some ranges of the parameter values, they can be transformed into fixed-shape solitons. This paper is dedicated to Prof. Helmut Brand on the occasion of his 60th birthday. 相似文献
585.
Vladimir Zaichick Sofia Zaichick 《Journal of Radioanalytical and Nuclear Chemistry》2013,298(3):1559-1566
The effect of age on trace element contents in intact prostate of 50 apparently healthy 0–30 year old males was investigated by neutron activation analysis with high resolution spectrometry of long-lived radionuclides. Mean values (M ± SΕΜ) for mass fraction (milligram per kilogram, on dry-weight basis) of trace elements were: Ag 0.0708 ± 0.0096, Co 0.0348 ± 0.0040, Cr 0.466 ± 0.069, Fe 100 ± 10, Hg 0.0258 ± 0.0025, Rb 12.6 ± 0.8, Sb 0.0576 ± 0.0066, Sc 0.0125 ± 0.0016, Se 0.478 ± 0.031, and Zn 273 ± 31, respectively. A strongly pronounced tendency of age-related increase in Se and Zn mass fraction and of age-related decrease in Co, Cr, Fe, and Sc mass fraction was observed in period of life from 0 to 30 years. 相似文献
586.
Sofia M. Eriksson Elizabeth A. Mackey Richard M. Lindstrom George P. Lamaze Kelly P. Grogan Dennis E. Brady 《Journal of Radioanalytical and Nuclear Chemistry》2013,298(3):1819-1822
An automated delayed-neutron activation analysis system has been installed at the NIST research reactor. This work involved characterization of the transfer time of the system, evaluation of blanks, and tests of the system’s analytical capabilities through quantitative analysis for uranium in several natural matrix standard reference materials (SRMs). The calibration curve was shown to be linear up to at least 20 μg of uranium, and the well-thermalized reactor irradiation position makes the system insensitive to thorium and oxygen. For SRMs 1646a Estuarine Sediment and 2710a Montana Soil the values determined for this work agree with the reference and certified values, respectively. The mass fraction of uranium in SRM 695 Multi-Nutrient Fertilizer is the first reported for this material. For this system and the irradiation, transfer, and counting times used, the limit of detection for natural uranium is 20 ng, which corresponds to approximately 200 pg of 235U. 相似文献
587.
Alaa S. Abd-El-Aziz Sofia Tesfalidet Christine R. de Denus Krystyna Lezynska 《合成通讯》2013,43(10):1415-1426
A novel route to the synthesis of some 2-aryl alkanoic acid esters has been achieved. Aromatic nucleophilic substitution of various arene cyclopenta-dienyliron complexes with ethyl ethylacetoacetate and ethyl methylacetoacetate produced the complexed alkanoic acid esters. Photolysis of these complexes resulted in the liberation of the free esters in good yields. 相似文献
588.
Sofia Popescu Mircea Stefanescu Elisabeth Popovici Ioana Perhaita 《Journal of Thermal Analysis and Calorimetry》2013,114(2):765-775
Thermal analysis and infrared (IR) spectroscopy are modern physical–chemical methods suitable for the investigation of the kidney stones composition. The applications of these methods in our work were anticipated by performing the standard thermal analysis and standard infrared spectra on pure compounds: oxalates, phosphate, carbonate, and uric acid. This work reveals a logical algorithm for correlating the experimental data regarding urolithiasis types and compositions by thermal analysis methods, Fourier Transform Infrared (FT-IR) spectroscopy, and second derivative FT-IR spectra. The limits and performance of each analysis method have been highlighted, and by correlating the results of both methods we have obtained comprehensive information for the identification and/or determination of the main components as well as of organic and/or inert impurities in calculi composition. The data regarding the urinary calculi composition are important for the clinical guideline in the prophilaxy and methaphylaxy of urolithiasis. 相似文献
589.
Ana Sofia Freitas Marta Costa Olívia Pontes Veronique Seidel Fernanda Proena Susana M. Cardoso Rui Oliveira Ftima Baltazar Cristina Almeida-Aguiar 《Molecules (Basel, Switzerland)》2022,27(13)
Renal cell carcinoma is the most lethal cancer of the urological system due to late diagnosis and treatment resistance. Propolis, a beehive product, is a valuable natural source of compounds with bioactivities and may be a beneficial addition to current anticancer treatments. A Portuguese propolis sample, its fractions (n-hexane, ethyl acetate, n-butanol and water) and three subfractions (P1–P3), were tested for their toxicity on A498, 786-O and Caki-2 renal cell carcinoma cell lines and the non-neoplastic HK2 kidney cells. The ethyl acetate fraction showed the strongest toxicity against A498 (IC50 = 0.162 µg mL−1) and 786-O (IC50 = 0.271 µg mL−1) cells. With similar toxicity against 786-O, P1 (IC50 = 3.8 µg mL−1) and P3 (IC50 = 3.1 µg mL−1) exhibited greater effect when combined (IC50 = 2.5 µg mL−1). Results support the potential of propolis and its constituents as promising coadjuvants in renal cell carcinoma treatment. 相似文献
590.
Davide Mendes Sofia Branco Maria Rosa Paiva Stefan Schütz Eduardo P. Mateus Marco Gomes da Silva 《Molecules (Basel, Switzerland)》2022,27(13)
Multidimensional gas chromatography is, presently, an established and powerful analytical tool, due to higher resolving power than the classical 1D chromatographic approaches. Applied to multiple areas, it allows to isolate, detect and identify a larger number of compounds present in complex matrices, even in trace amounts. Research was conducted to determine which compounds, emitted by host plants of the eucalyptus weevil, Gonipterus platensis, might mediate host selection behavior. The identification of a pheromone blend of G. platensis is presented, revealing to be more attractive to weevils of both sexes, than the individual compounds. The volatile organic compounds (VOCs) were collected by headspace solid phase microextraction (HS-SPME), MonoTrapTM disks, and simultaneous distillation-extraction (SDE). Combining one dimensional (1D) and two-dimensional (2D) chromatographic systems—comprehensive and heart-cut two-dimensional gas chromatography (GC×GC and H/C-MD-GC, respectively) with mass spectrometry (MS) and electroantennographic (EAD) detection, enabled the selection and identification of pertinent semiochemicals which were detected by the insect antennal olfactory system. The behavioral effect of a selected blend of compounds was assessed in a two-arm olfactometer with ten parallel walking chambers, coupled to video tracking and data analysis software. An active blend, composed by cis and trans-verbenol, verbenene, myrtenol and trans-pinocarveol was achieved. 相似文献