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991.
在阴离子交换树脂催化剂上合成二丙酮醇的动力学研究 总被引:1,自引:0,他引:1
动力学研究表明,在碱性树脂催化剂上丙酮缩合制二丙酮醇是一个1-1级可逆反应,本文对此多相催化的反应机理进行了探讨。 相似文献
992.
两位置交换问题魔角旋转核磁共振时域信号的准确解 总被引:2,自引:0,他引:2
已知两位置交换分子运动速率对于静态13CNMR谱的影响是由一简单代数关系决定,它已成为分析固体中分子运动的常规方法.慢速的魔角旋转可以保留边带,所产生的边带型原则上也可用来分析分子运动,只是缺乏象静态谱那样的简单的关系,以至于在实际应用上是不可行的.本文给出作者所发现的存在分子运动时魔角旋转核磁共振自由诱导衰减信号的解析表达式的理论推导,提供分析固体分子运动的理论谱计算公式.我们选择二甲矾(dimethylsulfone)作为模型化合物,记录其不同温度下13CNMR谱,又计算了两个甲基做两位置交换运动的理论谱.理论谱与实验谱定性一致.定量上,边带强度存在一些差别,但边带宽度符合很好.通过理论谱与实验谱的比较,得到交换速率与温度的对应关系.虽然本文限于化学位移各向异性相互作用两位置交换问题,但容易推广到偶极作用多位置交换问题. 相似文献
993.
B. H. Robinson C. Mailer A. W. Reese 《Journal of magnetic resonance (San Diego, Calif. : 1997)》1999,138(2):210-219
This work demonstrates that homogeneous linewidths can be extracted from continuous wave electron paramagnetic resonance spectra and that they quantitatively agree with the predictions of existing relaxation theory. We suggest that relaxation theory can be used to predict experimental lineshapes provided that the simulations properly include sources of broadening. We have found that the rotational correlation times for spin labels in different percentages of glycerol/water mixtures are best modeled by a power law treatment for the viscosity, similar to that for translational diffusion. The translational diffusion coefficients themselves also have a power law dependence on the viscosity for glycerol/water mixtures. The linewidths were linearly dependent upon both the oxygen and the spin label concentration. The hyperfine splittings of all nuclei were observed to decrease linearly with increasing spin label concentration, completely at odds with existing theory which predicts a quadratic dependence upon concentration. The linear dependence was independent of hyperfine splitting until the magnitude of the hyperfine splitting was less than the homogeneous linewidth. 相似文献
994.
A. Krushelnitsky D. Reichert G. Hempel V. Fedotov H. Schneider L. Yagodina A. Schulga 《Journal of magnetic resonance (San Diego, Calif. : 1997)》1999,138(2):244-255
Superslow backbone dynamics of the protein barstar and the polypeptide polyglycine was studied by means of a solid-state MAS 1D exchange NMR method (time-reverse ODESSA) that can detect reorientation of nuclei carrying anisotropic chemical shift tensors. Experiments were performed on carbonyl 13C in polyglycine (natural abundance) and backbone 15N nuclei in uniformly 15N-enriched barstar within a wide range of temperatures in dry and wet powders for both samples. Two exchange processes were observed in the experiments: molecular reorientation and spin diffusion. Experimental conditions that are necessary to separate these two processes are discussed on a quantitative level. It was revealed that the wet protein undergoes molecular motion in the millisecond range of correlation times, whereas in dry protein and polyglycine molecular reorientations could not be detected. The correlation time of the motion in the wet barstar at room temperature is 50-100 ms; the activation energy is about 80 kJ/mol. Previously, protein motions with such a long correlation time could be observed only by methods detecting chemical exchange in solution (e.g., hydrogen exchange). The application of solid-state MAS exchange spectroscopy provides new opportunities in studying slow biomolecular dynamics that is important for the biological function of proteins. 相似文献
995.
The alkalization of carboxylated acrylic polymer latexes by sodium hydroxide gives rise to swelling of the particles. For
a poly(n-butyl acrylate) latex copolymerized with 15 wt % methacrylic acid (MAA) and 7 wt % acrylonitrile the particle volume increases
by a factor of 30. The alkali-swelling does not depend on the type of monovalent cation used in the base (LiOH, NaOH, KOH,
NH4OH). In contrast, when bivalent cation bases such as Ca(OH)2 are employed no latex swelling is observed during neutralization because of ionic crosslinking of the copolymer chains. Crosslinking
also takes place when the bivalent cations (Ca2+, Zn2+, Mg2+) are added as chlorides to dispersions with latexes previously swollen by sodium hydroxide. In these experiments the original
size of the latexes is reached again at a molar ratio MAA: bivalent metal ion of 2:1, i.e. at charge compensation of the carboxyl
groups. The shrinking behavior is almost independent of the type of bivalent metal ion used. On the other hand, it is more
pronounced when trivalent cations such as Fe3+ are added. In general, the experiments demonstrate that the alkali swelling of acrylic latexes is dominated by electrostatic
forces.
Received: 18 August 1998 Accepted in revised form: 26 October 1998 相似文献
996.
合成了一系列大取代二茂铁三碘化物,通式为(RC~5H~4)~2FeI~3。通过元素分析,红外光谱,质谱,顺磁共振谱,穆斯堡尔谱和电导率对这些化合物进行了表征。测定了化合物[CH~2(CH~2)~3C(2-CH~2C~5H~4N)C~5H~4]~2FeI~4.H~2O的晶体结构,该晶体属三斜晶系,P-1空间群,晶胞参数:a=0.9593(1),b=1.3999(2),c=1.4537(2)nm。α=109.64(1),β=97.25(1),γ=104.69(1)ⅲ。V=1.7299nm^3,Mr=1030.13,Dx=1.98g/cm^3,Z=2。结果表明,取代二茂铁被碘部分氧化,导致中心金属铁表现为混合价态;由于茂环上大取代基的影响,使得I~3^-与I~3^-之间未能形成碘链,因此这些化合物的电导率很低。 相似文献
997.
998.
999.
本文研究了高分子催化剂—Fe3+-阳离子交换树脂在苯的羟基化合成苯酚反应中的应用。本催化剂具有操作简便、无腐蚀性,催化剂易从反应混合物中分离,并能重复使用等优点。 相似文献
1000.
NH4^+改型钾丝光沸石及其离子交换性 总被引:1,自引:0,他引:1
用铵盐改型钾丝光沸石,通过X-射线衍射,红外分析,分配系数,离子交换等温线及交换容量等的测定,就其结构及交换性能进行了研究;并与铵改型钠丝光沸石和天然斜发沸石等进行比较,表明NH4^+改型后的钾丝光沸石对K^+具有较高的交换容量和较好的K^+/Na^+分离效果。 相似文献