全文获取类型
收费全文 | 2363篇 |
免费 | 91篇 |
国内免费 | 75篇 |
专业分类
化学 | 1508篇 |
晶体学 | 18篇 |
力学 | 109篇 |
综合类 | 1篇 |
数学 | 306篇 |
物理学 | 587篇 |
出版年
2023年 | 23篇 |
2022年 | 15篇 |
2021年 | 43篇 |
2020年 | 28篇 |
2019年 | 39篇 |
2018年 | 18篇 |
2017年 | 18篇 |
2016年 | 45篇 |
2015年 | 39篇 |
2014年 | 86篇 |
2013年 | 119篇 |
2012年 | 173篇 |
2011年 | 183篇 |
2010年 | 117篇 |
2009年 | 118篇 |
2008年 | 118篇 |
2007年 | 134篇 |
2006年 | 138篇 |
2005年 | 118篇 |
2004年 | 102篇 |
2003年 | 66篇 |
2002年 | 73篇 |
2001年 | 56篇 |
2000年 | 42篇 |
1999年 | 35篇 |
1998年 | 33篇 |
1997年 | 27篇 |
1996年 | 17篇 |
1995年 | 27篇 |
1994年 | 30篇 |
1993年 | 28篇 |
1992年 | 25篇 |
1991年 | 21篇 |
1990年 | 24篇 |
1989年 | 21篇 |
1988年 | 17篇 |
1987年 | 19篇 |
1985年 | 31篇 |
1984年 | 35篇 |
1983年 | 22篇 |
1982年 | 22篇 |
1981年 | 21篇 |
1980年 | 13篇 |
1979年 | 12篇 |
1978年 | 17篇 |
1977年 | 16篇 |
1976年 | 18篇 |
1975年 | 17篇 |
1974年 | 16篇 |
1973年 | 11篇 |
排序方式: 共有2529条查询结果,搜索用时 78 毫秒
41.
Metal (M) oxide (M: Ir, Os, Pd, Pt, Rh, Ru) together with MaO2 and MnO2 alone, were coated on SnO2 films and the anode behavior was examined in 1.0 N H2SO4, 1.0 N NaOH and 1.0, N NaCl aqueous solutions at 25°. The results are compared with those of DSA and of metallic Pt. 相似文献
42.
A square-wave voltammetric method together with Nafion®-coated carbon paste electrodes were used for the selective determination of uric acid in the presence of a high concentration of ascorbic acid. Since the oxidation potential of uric acid is about 200 mV more positive than that of ascorbic acid at the Nafion®-coated carbon paste electrode, the selectivity can be greatly improved simply by applying an electrolysis potential of +0.4 V vs. Ag/AgCl where only ascorbic acid is oxidised. The acceptable tolerance of ascorbic acid concentration for the determination of uric acid is as high as 1.5 mM. With 30 s of electrolysis time, a linear calibration curve is obtained over the 0–50 μM range in 0.05 M citrate buffer solution, pH 4.0, with slope (μA/μM) and correlation coefficient of 0.34 and 0.9984, respectively. The detection limit (3σ) is 0.25 μM. The practical analytical utility is illustrated by selective measurements of uric acid in human urine without any preliminary treatment. 相似文献
43.
A cumulative selection procedure for choosing configuration functions for inclusion in CI calculations is described. The objective of the method is to obtain equal energy loss, relative to unselected calculations, for different states and different regions of the potential surface. Results obtained from calculations on the BH molecule indicate an overall advantage in comparison to the threshold selection procedure, particularly with regard to molecular geometry changes. 相似文献
44.
Jo‐Nan Chen Fang‐Ming Hsu Hui‐Chun Wang Chung‐Wen Wu Pao‐Swu Cheng Wen‐Liang Tsai 《中国化学会会志》2006,53(4):931-938
Four series of compounds 11?50 containing terminal alicyclic rings such as cyclohexylmethyl, cyclopentylmethyl, cyclobutylmethyl, and cyclopropylmethyl rings were synthesized and their liquid crystal behavior studied. The ring size and the length of flexible alkoxy chain influence the phase formation in different ways. While the smaller ring and the shorter alkoxy chain tend to favor the formation of the N phase, the larger ring and the longer alkoxy chain tend to favor the formation of the SmC phase. All the compounds except 11 and 21 exhibit SmA phases. The widest temperature range of the N, SmA, and SmC phases are found in the compounds 41 , 46 , and 20 , respectively, which are 75 °C for 41 , 115 °C for 46 , and 100 °C for 20 . 相似文献
45.
Chien-Hui Li Keh-Ying Hsu Teh-Chou Chang 《Journal of polymer science. Part A, Polymer chemistry》1993,31(5):1119-1124
Three series of polymers containing p-phenylene diacrylic group were prepared by direct polycondensation in the presence of diphenylchlorophosphate and pyridine. Series I was prepared from p-phenylene bis(acrylic acid) with various hydroquinones. Series II was prepared from p-phenylene bis (β-cyano acrylic acid) with methylhydroquinone. Series III was prepared from 3-methyl-4-aminophenol with p-phenylene bis(acrylic acid) or p-phenylene bis(β-cyano acrylic acid), respectively. The phase behavior of these polymers was studied by differential scanning calorimetry (DSC), optical polarizing microscopy equipped with a heating stage, and wide-angle x-ray diffraction (WAXD). It was found that these polymers, except IIIb , exhibit thermotropic liquid-crystalline properties and show threaded or Schlieren texture under the optical polarizing microscopic observation. Furthermore, the melting temperatures of these polymers were decreased in the range of 254–354°C by incorporating with p-phenylene diacrylic group into the main chain. © 1993 John Wiley & Sons, Inc. 相似文献
46.
The retention properties of calcitonins on a reversed-phase column are examined using salmon calcitonin as the model compound. The effect of the concentration of organic modifier, buffer strength, pH of the mobile phase, and ion-pair reagent are studied. In the absence of an ionic modifier in the eluent the calcitonin peak shapes are not symmetrical. The addition of 0.1% trifluoroacetic acid (TFA), however, results in good peak characteristics without the need to add nonvolatile salts. The retention of the calcitonins was found to be very sensitive to the concentration of the organic modifier (acetonitrile) present in the mobile phase. A change of pH between 2 and 5 has only a slight effect of the k' of salmon calcitonin, but the k' increases significantly at higher pH values. The addition of a phosphate buffer to the mobile phase and an increase in the buffer concentration (0-0.2 M) causes a decrease in the retention of salmon calcitonin. Evidence shows that reproducible, quantitatively measurable data can be obtained using reversed-phase chromatography if the ion-pairing reagent and organic modifier concentrations are carefully controlled. The system also shows a good selectivity for the calcitonin series. Therefore, both highly selective methods (qualitative) as well as quantitative methods for analytical, pharmaceutical, and manufacturing use can be developed by adjusting the high-performance liquid chromatography (HPLC) conditions as discussed. 相似文献
47.
The fragmentation patterns of 3-methyl-2-butyl trifluoroacetate and 2-methyl-2-butyl trifluoroacetate were investigated by GC/MS/MS, with electron impact and collision-induced dissociation, on regular and isotope-labeled (deuterium and 18O) esters. The atoms found in various fragments could be traced back to specific positions in the parent molecules. In this way, molecular rearrangements potentially occurring during the formation of esters by trifluoroacetolysis of 3-methyl-2-butyl p-toluenesulfonate or trifluoroacetic acid addition to various 2-methylbutenes could be shown. Rearrangements also occurred during the fragmentation, particularly during the expulsion of the small fragments CO, C2H4 and F2CO. For the decompositions of oxygen-containing ions these rearrangements were highly specific. By contrast, alkyl cations lead to fragments that are fully scrambled (statistical label distribution). Alkene radical cations ([CnH2n]+ ˙) fragment to daughter ions that are extensively, but less than statistically scrambled. Hydrogen scrambling may also occur in fluoroalkyl cation fragments. 相似文献
48.
The boundary effect on the sedimentation of a colloidal particle is investigated theoretically by considering a composite sphere, which comprises a rigid core and an ion-penetrable membrane layer, in a spherical cavity. A pseudo-spectral method is adopted to solve the governing electrokinetic equations, and the influences of the key parameters on the sedimentation behavior of a particle are discussed. We show that both the qualitative and quantitative behaviors of a particle are influenced significantly by the presence of the membrane layer. For example, if the membrane layer is either free of fixed charge or positively charged and the surface potential of the rigid core is sufficiently high, the sedimentation velocity has a local minimum and the sedimentation potential has a local maximum as the thickness of the double layer varies. These local extrema are not observed when the membrane layer is negatively charged. If the double layer is thin, the influence of the fixed charge in the membrane layer on the sedimentation potential is inappreciable. 相似文献
49.
3-(2-羟基苯基)-5-苯基-6-乙氧羰基-2-环己烯酮的合成与晶体结构 总被引:3,自引:0,他引:3
合成了3-(2-羟基苯基)-5-苯基-6-乙氧羰基-2-环己烯酮.通过元素分析、红外光谱、紫外光谱、核磁共振氢谱和质谱对其组成和结构进行了表征.利用X射线衍射分析方法测定了它的晶体结构.该化合物的晶体属单斜晶系,空间群P21/c,a=1.41946(17)nm,b=0.58445(7)nm,c=2.1756(3)nm,β=104.795(2)°,V=1.7450(4)nm3,Z=4,Dc=1.280 g·cm-3,F(000)=712,μ=0.088mm-1,R1[I>2σ(I)]=0.0627,wR2[I>2σ(I)]=0.1484.晶体结构测定结果表明化合物分子中的环己烯部分为半椅式构象,分子间通过氢键形成具有16元环的二聚体. 相似文献
50.
(Z, E)-9, 11-Tetradecadienyl-l-acetate (1), a major component of the sex pheromone of Spodoptera litura (F.), and (Z, E}-9, 11-pentadecadienyl-1-acetate (2) were synthesized by the Wittig reaction between (E)-2-alkenal (3) and the ylid derived from 9-hydroxynonyltriphenylphosphonium bromide (4). 相似文献