全文获取类型
收费全文 | 7385篇 |
免费 | 385篇 |
国内免费 | 44篇 |
专业分类
化学 | 5592篇 |
晶体学 | 68篇 |
力学 | 146篇 |
数学 | 511篇 |
物理学 | 1497篇 |
出版年
2023年 | 48篇 |
2022年 | 94篇 |
2021年 | 172篇 |
2020年 | 131篇 |
2019年 | 154篇 |
2018年 | 115篇 |
2017年 | 111篇 |
2016年 | 265篇 |
2015年 | 226篇 |
2014年 | 298篇 |
2013年 | 450篇 |
2012年 | 588篇 |
2011年 | 660篇 |
2010年 | 398篇 |
2009年 | 362篇 |
2008年 | 533篇 |
2007年 | 443篇 |
2006年 | 426篇 |
2005年 | 352篇 |
2004年 | 295篇 |
2003年 | 256篇 |
2002年 | 284篇 |
2001年 | 139篇 |
2000年 | 129篇 |
1999年 | 82篇 |
1998年 | 46篇 |
1997年 | 66篇 |
1996年 | 60篇 |
1995年 | 49篇 |
1994年 | 32篇 |
1993年 | 46篇 |
1992年 | 46篇 |
1991年 | 30篇 |
1990年 | 36篇 |
1989年 | 40篇 |
1988年 | 15篇 |
1987年 | 18篇 |
1986年 | 17篇 |
1985年 | 31篇 |
1984年 | 25篇 |
1983年 | 19篇 |
1982年 | 19篇 |
1981年 | 14篇 |
1980年 | 13篇 |
1979年 | 11篇 |
1978年 | 15篇 |
1977年 | 19篇 |
1976年 | 12篇 |
1975年 | 12篇 |
1970年 | 17篇 |
排序方式: 共有7814条查询结果,搜索用时 421 毫秒
71.
J. Jung H. S. Jeong H. H. Chung M. J. Lee J. H. Jin K. B. Park 《Journal of Radioanalytical and Nuclear Chemistry》2003,255(3):543-546
The radioactive concentrations of radionuclides were measured in the soil and groundwater below the 12 GeV proton beam-line tunnel at KEK. Various long-lived radionuclides, (7Be, 22Na, 46Sc, 54Mn, 60Co, 134Cs, 152Eu and 154Eu) were observed in the soil samples by -ray spectra measurements, and 3H was also detected by liquid scintillation counting. On the other hand, 3H, 22Na and 54Mn, which were leached from the soil were measured in the groundwater below the EP2 beam line. 3H and 22Na were also found in slight amounts in groundwater collected in a well dug beside the East Counter Hall. From a comparison with the radioactive concentration in soil and groundwater, the order of the leaching percentages were 3H>22Na>54Mn. This tendency was in agreement with an experimental result of the RI laboratory. 相似文献
72.
Four new heterometallic glutarate coordination polymers, [Eu2M(H2O)4][O2C(CH2)3CO2]4.2H2O (M = Mn (1), Fe (2), Co (3) and Ni (4)) have been obtained under hydrothermal synthesis. The single-crystal X-ray diffraction analyses showed that they have two-dimensional frameworks based on the linear polyhedral chains consisting of two nine-coordinated Eu(III)O9 and a six-coordinated M(II)O6. These 1-D MO6-Eu2O16 chains are cross-linked by glutarate ligands as an interchain pillared architecture, whose conformations vary depending upon the transition metals. The magnetic behavior of the compounds show a weak antiferromagnetic interaction, in which shielding of the 4f electrons by the outer shell electrons effectively precludes significant coupling interactions between the Eu-4f electrons and transition metal (M)-3d electrons. 相似文献
73.
This paper describes an efficient synthetic route for various types of novel carbocyclic nucleosides. The required stereochemistry of the targeted nucleosides was successfully obtained with use of Grubbs cyclization and Trost allylic alkylation from the carbohydrate chiral template "D-lactose". 相似文献
74.
The 13C-NMR spectra of the synthetic membrane modifying nonadecapeptide Boc-(Aib-l-Ala)5-Gly-Ala-Aib-Pro-Ala- Aib-Aib-Glu(OBz)-Gln-OMe (Aib = α-aminoisobutyric acid), and of synthetic intermediates were used for conformational analysis in solution. The assignments of the 13C-NMR signals of Aib are based on the magnetic nonequivalence (MNE) of the geminal Cβ-signals in asymmetric environment resulting in a shift difference of 0.2–0.5 ppm due to neighbouring chiral residues. More than 4 ppm MNE are observed due to α-helical conformation and about 2.5 ppm for Aib situated in the corners of a rigid β-turn. The Ala-Cα signal is also sensitive to different secondary structures. The Cα signal for C-terminal alanine is found at 49–50 ppm, and for alanine within unordered oligopeptides it absorbs at 50–51 ppm. α-Helical environment shifts the Ala-Cα signal to lower field down to 54 ppm. In methanolic solution the nonadecapeptide shows a α-helical N-terminal region. For the C-terminus beginning with proline-14 no periodically ordered conformation is observed, and we suggest a sequence of β-turns. Furthermore the typical E/Z isomerism of the prolyl-peptide bond can be observed on proline itself and on its neighbour alanine. 相似文献
75.
Reaction of 1,6-enynes with a hydrosilane in the presence of immobilized cobalt/rhodium bimetallic nanoparticles gives 2-methyl-1-silylmethylidene-2-cyclopentanes in the absence of carbon monoxide and 2-formylmethyl-1-silylmethylidene-2-cyclopentanes under 1 atm of carbon monoxide, respectively. [reaction: see text] 相似文献
76.
A high-performance liquid chromatographic (HPLC) procedure has been evaluated to establish a routine test in the clinical laboratory for measuring the profiles of estrogen and progestin receptor isoforms in human breast and endometrial tumors. This procedure will be used to determine if there is a relationship between particular isoform profiles and response to various endocrine therapies. Evaluation of various HPLC modes has shown that high-performance ion-exchange chromatography (HPIEC) with silica-based anion exchangers offers a promising approach. In this paper, we have compared HPIEC columns of different lengths (10 and 25 cm) and pore sizes (300, 500 and 1,000 A) in order to obtain an optimal separation procedure. Because of receptor lability, all investigations were performed at 4 degrees C. The mobile phase consisted of 10-500 mM phosphate buffer, supplemented with the stabilizing agent, sodium molybdate at pH 7.4. Recoveries from each of the columns were between 70-100%. The length of the column did not influence significantly the retention time and salt concentration required for elution of receptor proteins. However, pore sizes appeared to alter these parameters. With a larger pore size (1,000 A), the retention of proteins was lower (elution with 50 mM phosphate) than that observed with the 500-A pore size column (elution with 100 mM phosphate) or of the 300-A pore size column (elution with 150 mM phosphate). Based solely on recovery patterns and peak shape, we conclude that separation of receptor isoforms on a 1,000-A, 25-cm column is best suited for clinical analysis. 相似文献
77.
Using reaction rate data collected in aprotic solvents, we have determined that the Baylis-Hillman rate-determining step is second order in aldehyde and first order in DABCO and acrylate. On the basis of these data, we have proposed a new mechanism involving a hemiacetal intermediate. The proposed mechanism was then supported using two different kinetic isotope experiments. 相似文献
78.
In this paper, adsorption characteristics of methyl mercaptan on virgin activated carbon and copper chloride impregnated activated carbons were studied by using a dynamic adsorption method in a fixed bed. The activated carbons were characterized by nitrogen adsorption, XRD, TGA and solubility tests. The impregnation of copper chloride on the activated carbon significantly enhanced the adsorption capacity of methyl mercaptan, despite a notable decrease in microporosity. It is likely that copper chloride may act as adsorption site for methyl mercaptan. Copper chloride on the activated carbon in a range of 3-20 wt% Cu content was present mostly in the amorphous form of CuCl(2), according to the results of the solubility, XRD and TGA tests. Starting at 10 wt% in Cu loading, the adsorption capacity for methyl mercaptan decreases gradually. It is likely that a decrease in the degree of copper chloride dispersion and an accessibility of small pores may lead to the decrease in the adsorption capacity of the activated carbon for methyl mercaptan. 相似文献
79.
Moonhor Ree Jong-Seong KimJae Jung Kim Byeang Hyean KimJuyoung Yoon Heesoo Kim 《Tetrahedron letters》2003,44(45):8211-8215
The synthesis of novel cavitands containing four fluorophores [tert-butoxycarbonyl protected 2,2′-bis(furyl)benzidine (t-BOC FurylBz) or 5,5′-bis(4-aminophenyl)-2,2′-bifuryl (t-BOC PFDA)] and ionophoric functional groups on the upper rim is reported. The cavitands bearing the four fluorophores emit blue light photoluminescence. In particular, the cavitand containing PFDA moieties exhibits a high photoluminescence quantum yield. 相似文献
80.
[Rb2(H2O)2][Re3(μ-Cl)3Br7(H2O)2]2 · H2O, a Mixed Halide-Hydrate with the Anionic Dimer {[Re3(μ-Cl)3Br7(H2O)2]2 · H2O}2? [Rb2(H2O)2][Re3(μ-Cl)3Br7(H2O)2]2 · H2O crystallizes as dark redbrown single crystals from an hydrobromic-acid solution of ReCl3 and RbBr at 0°C. An important feature of the crystal structure (monoclinic, C2/c; a = 1494.61(8); b = 835.71(4); c = 3079.96(19) pm; β = 97.801(4)°; Vm = 573.9(4) cm3mol?1; R = 0.060; Rw = 0.038) is the connection of two anions [Re3(μ-Cl)3Br7(H2O)2]? via a water molecule to dimers, {[Re3(μ-Cl)3Br7(H2O)2]2 · H2O}2?. These dimeric units are contained in slabs that are stacked in the [001] direction and held together by Rb+ cations and crystal water. 相似文献