全文获取类型
收费全文 | 70463篇 |
免费 | 9878篇 |
国内免费 | 6661篇 |
专业分类
化学 | 47060篇 |
晶体学 | 662篇 |
力学 | 4663篇 |
综合类 | 516篇 |
数学 | 8456篇 |
物理学 | 25645篇 |
出版年
2024年 | 228篇 |
2023年 | 1399篇 |
2022年 | 2285篇 |
2021年 | 2469篇 |
2020年 | 2524篇 |
2019年 | 2432篇 |
2018年 | 2195篇 |
2017年 | 1942篇 |
2016年 | 2967篇 |
2015年 | 3084篇 |
2014年 | 3652篇 |
2013年 | 4850篇 |
2012年 | 5891篇 |
2011年 | 6019篇 |
2010年 | 4083篇 |
2009年 | 4024篇 |
2008年 | 4191篇 |
2007年 | 3792篇 |
2006年 | 3573篇 |
2005年 | 3099篇 |
2004年 | 2480篇 |
2003年 | 1895篇 |
2002年 | 1684篇 |
2001年 | 1525篇 |
2000年 | 1420篇 |
1999年 | 1567篇 |
1998年 | 1334篇 |
1997年 | 1172篇 |
1996年 | 1232篇 |
1995年 | 1075篇 |
1994年 | 1010篇 |
1993年 | 866篇 |
1992年 | 768篇 |
1991年 | 665篇 |
1990年 | 555篇 |
1989年 | 482篇 |
1988年 | 367篇 |
1987年 | 349篇 |
1986年 | 297篇 |
1985年 | 303篇 |
1984年 | 202篇 |
1983年 | 176篇 |
1982年 | 145篇 |
1981年 | 112篇 |
1980年 | 82篇 |
1978年 | 56篇 |
1977年 | 52篇 |
1976年 | 50篇 |
1975年 | 57篇 |
1973年 | 57篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
931.
A number of experimental parameters have been optimized for the separation of 26 metal ions, including alkali, alkaline earth, transition and lanthanide metal ions. Experimental parameters that were evaluated included nature of indirect-detection reagent, pH of electrolyte, concentration of complexing agent and nature of the surface of the capillary; unbonded and C1 and C18 bonded phases were studied. In addition the effect of internal diameter on linearity and signal-to-noise ratio was examined, and separation efficiency was determined for a variety of experimental conditions. Detection limits (signal-to-noise RATIO = 3) were ca. 1 μg/ml for the lanthanides, ca. 0.6 μg/ml for transition and alkaline earth ions and ca. 0.1–0.8 μg/ml for alkali metal ions. The average relative standard deviations of were 3.7, 5.1 and 2.5% on unbonded, C1 and C18 capillaries, respectively. Whereas conventional regression analysis suggested that the calibration curves were linear over the range of 1·10−5 to 4·10−4 mol/l, sensitivity plots showed that the results were actually linear to within 6% only over the range of 2.5·10−5 to 4·10−4 mol/l. 相似文献
932.
Two-dimensional capillary electrophoresis was used for the separation of proteins and biogenic amines from the mouse AtT-20 cell line. The first-dimension capillary contained a TRIS–CHES–SDS–dextran buffer to perform capillary sieving electrophoresis, which is based on molecular weight of proteins. The second-dimension capillary contained a TRIS–CHES–SDS buffer for micellar electrokinetic capillary chromatography. After a 61-s preliminary separation, fractions from the first-dimension capillary were successively transferred to the second-dimension capillary, where they further separated by MECC. The two-dimensional separation required 60 min. 相似文献
933.
Xiu-Lin Zeng Wang-Hua Chen Jia-Cong Liu Jin-Lin Kan 《Journal of Molecular Structure》2007,810(1-3):47-51
Three density-functional methods (B3P86, B3PW91, and B3LYP) are employed to investigate the O–NO2 bond lengths, frontier orbital energies, and O–NO2 bond dissociation energies (BDEs) of n-propyl nitrate (NPN), isopropyl nitrate (IPN), 2-ethylhexyl nitrate (EHN), triethylene glycol dinitrate (Tri-EGDN), and tetraethylene glycol dinitrate (Tetra-EGDN). It is found that the O–NO2 bond lengthens (destabilizes) in the order of IPN, NPN, EHN, Tetra-EGDN, and Tri-EGDN. From the data of frontier orbital energies (EHOMO, ELUMO), and energy gaps (ΔE), we estimate the relative thermal stability ordering of five nitrates and their corresponding radicals. The predicted BDEs of O–NO2 bond in NPN, IPN, EHN, Tri-EGDN, and Tetra-EGDN, are 176.6, 174.5, 168.1, 156.1, and 159.3 kJ mol−1, respectively. Based on the finding that the present results of BDEs are well coincident with the experimental results of apparent activation energies from the literature, we can draw a conclusion that the experimental thermolysis of five nitrates is only unimolecular homolytical cleavage of the O–NO2 bonds. 相似文献
934.
Wen-xun Guo Zong-li Shi Kui Liang Yan-li Liu Xian-hong Chen Wei Li 《Polymer Degradation and Stability》2007,92(3):407-413
New unsaturated polyesters of poly(fumaric acid-glycol-sebacic acid) copolymers and poly(maleic anhydride-glycol-sebacic acid) copolymers were prepared by melt polycondensation of the corresponding mixed monomers: sebacic anhydride, fumaric acid or maleic anhydride and glycol. Methyl-methacrylate (MMA) was used as crosslinker and dimer acid was used as thinner.In vitro studies showed that those copolymers are degradable in phosphate buffer at 37 °C and poly(fumaric acid-glycol-sebacic acid) has proper drug release rate as drug carriers. The biocompatibility of poly(fumaric acid-glycol-sebacic acid) copolymers under mice skin was also evaluated; macroscopic observation and microscopic analysis demonstrated that the copolymer is biocompatible and well tolerated in vivo. The injected poly(fumaric acid-glycol-sebacic acid) [molar ratio Mfumaric acid:Mglycol:Msebacic acid = 1.75:2.20:0.25] containing 5% adriamycin hydrochloride (ADM) in the mice bearing Sarcoma-180 tumor exhibited a good antitumor efficacy. The volume doubling time (VDT) (18 ± 2.5 days) of the tumor growth by this treatment was longer than that (7 ± 0.9 days) by the subcutaneous injection of ADM. 相似文献
935.
XRD and XPS are used to study the dispersion state of CuO on ceria surface. The dispersion capacity values of CuO measured
by the two methods are consistent, which are of 1.20 mmol CuO/100 m2 CeO2. In addition, the results reveal that highly dispersed Cu2+ ions are formed at low CuO loadings and that increasing the CuO content to a value higher than its dispersion capacity produces
crystalline CuO after the surface vacant sites on CeO2 are filled. The atomic composition of the outermost layer of the CuO/CeO2 samples has been probed by using static secondary ion mass spectroscopy (SSIMS), and the ratim of Cu/Ce are found to be 0.93
and 0.46 for the 1.22 and 0.61 mmol CuO/CeO2 samples respectively. Temperature-programmed reduction (TPR) profile with two reduction peaks at 156 and 165°C suggests that
the reduction of highly dispersed Cu2+ ions consists of two steps and is easier than that of CuO crystallites, in which the TPR profile has only one reduction peak
at about 249°C. The above experimental results are in good agreement with the prediction of the incorporation model.
Project supported by the National Natural Science Foundation of China. 相似文献
936.
Two 60-residue snake toxins with four disulfide bridges, cardiotoxin II and IV, of Taiwan cobra (Naja naja atra) have been rapidly prepared in overall yields of 3.9% (cardiotoxin II) and 3.7% (cardiotoxin IV) within three weeks using the chemical method. Physicochemical characterization of these synthetic cardiotoxins was carried out by amino acid analysis, mass spectroscopy, capillary electrophoresis, peptide mapping, circular dichroism spectroscopy, and lethal toxicity. As compared with natural cardiotoxins, the results indicated that the synthetic cardiotoxins possessed the same physicochemical properties as those of natural ones. Therefore, in addition to preparation of various important toxins with satisfactory quantities for biochemical and pharmacological studies within a short lime, this rapid method also provides an important route to obtain many interesting toxins and designed toxin analogues for structure/function relationship studies in the near further. 相似文献
937.
938.
The adsorption of α1-acid glycoprotein into bilirubin/cholesterol mixed monolayers with various component molar ratios is investigated using surface
pressure-area (π-A) isotherms and (dπ/dA)-A curves. The results showed that the surface area per molecule increased after the adsorption/insertion of glycoprotein molecules
into the monolayers. The compressibility of mixed monolayers increased as a result of hydrogen bonding between bilirubin and
glycoprotein molecules, while the interactions between bilirubin and cholesterol are weakened. The adsorption of glycoprotein
into a monolayer induced changes in molecular surface area depending on the surface pressure and molar fraction of bilirubin.
The transmission electron microscopy of mixed monolayers confirmed the insertion of glycoprotein particles of spherical shape
with an average diameter of about 80 nm into the monolayer.
The text was submitted by the authors in English. 相似文献
939.
Microwave irradiation of alkynyl allenes affords an intramolecular [2 + 2] cycloaddition reaction. This cycloaddition provides an efficient route to bicyclomethylenecyclobutenes. The reaction occurs with complete regioselectivity for the distal double bond of the allene for the selective formation of a variety of hetero- and carbocyclic substrates. Bicyclo[4.2.0]octadienes and bicyclo[5.2.0]nonadienes have been prepared in high yield. [reaction: see text] 相似文献
940.
Chen SH Su AC Chang CS Chen HL Ho DL Tsao CS Peng KY Chen SA 《Langmuir : the ACS journal of surfaces and colloids》2004,20(20):8909-8915
Morphological effects in luminescence properties of a representative semiconducting polymer, poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV), has recently attracted much attention. Previous studies indicated that short-term heat treatment of solution-cast MEH-PPV films may result in the formation of mesomorphic order that is responsible for the "red" emission around 640 nm, in contrast to the single-chromophore "yellow" emission near 590 nm from the disordered matrix. On the basis of microscopic and spectroscopic evidence for films cast from freshly prepared and aged solutions, here we show that prolonged storage of MEHyellowPPV solutions at room temperature or lower may result in retardation of the thermally induced mesophase formation in the subsequently cast films. According to small-angle neutron scattering and differential scanning calorimetric observations over aged MEH-PPV/toluene solutions, we propose that the suppressed transformation into mesomorphic order is due to further development of nanocrystalline aggregates that serve as physical cross-links among MEH-PPV chains in the solution state upon long-term storage. These solvent-induced nanocrystalline aggregates, however, do not exhibit new spectroscopic features beyond the suppression of "red" emission at 640 nm from the mesomorphic phase. 相似文献