全文获取类型
收费全文 | 6095篇 |
免费 | 1124篇 |
国内免费 | 1629篇 |
专业分类
化学 | 4590篇 |
晶体学 | 204篇 |
力学 | 451篇 |
综合类 | 163篇 |
数学 | 830篇 |
物理学 | 2610篇 |
出版年
2024年 | 8篇 |
2023年 | 88篇 |
2022年 | 235篇 |
2021年 | 260篇 |
2020年 | 263篇 |
2019年 | 259篇 |
2018年 | 245篇 |
2017年 | 295篇 |
2016年 | 241篇 |
2015年 | 356篇 |
2014年 | 364篇 |
2013年 | 506篇 |
2012年 | 536篇 |
2011年 | 546篇 |
2010年 | 505篇 |
2009年 | 497篇 |
2008年 | 527篇 |
2007年 | 454篇 |
2006年 | 407篇 |
2005年 | 386篇 |
2004年 | 264篇 |
2003年 | 188篇 |
2002年 | 212篇 |
2001年 | 222篇 |
2000年 | 243篇 |
1999年 | 131篇 |
1998年 | 69篇 |
1997年 | 63篇 |
1996年 | 62篇 |
1995年 | 65篇 |
1994年 | 62篇 |
1993年 | 43篇 |
1992年 | 36篇 |
1991年 | 29篇 |
1990年 | 34篇 |
1989年 | 31篇 |
1988年 | 11篇 |
1987年 | 10篇 |
1986年 | 9篇 |
1985年 | 15篇 |
1984年 | 10篇 |
1983年 | 14篇 |
1982年 | 11篇 |
1981年 | 5篇 |
1980年 | 8篇 |
1979年 | 9篇 |
1978年 | 4篇 |
1965年 | 2篇 |
1957年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有8848条查询结果,搜索用时 31 毫秒
91.
高效液相色谱-电喷雾质谱(HPLC-ESI-MS/MS)测定新型抗癌铂配合物 总被引:2,自引:0,他引:2
采用高效液相色谱-电喷雾-多级质谱法(HPLC-ESI-MS/MS), 研究了cis-3,5-diisopropylsalylic cyclohexanodiaminoplatinum(Ⅱ)的电喷雾质谱行为, 鉴定了其杂质, 并测定了其纯度. 相似文献
92.
The title compound, {[Cu(2,2'-bipy)(C7H4O5S)(H2O)2](H2O}n (2,2'-bipy = 2,2'- bipyridine), was synthesized by the hydrothermal reaction of Cu(NO3)2(3H2O, 2,2'-bipyridine and 2-sulphobenzoic acid, and structurally characterized by single-crystal X-ray diffraction analysis. The crystal is of triclinic, space group P with a = 9.21(3), b = 10.17(3), c = 10.77(3) (A), α = 77.017(16), β = 89.80(8), γ = 68.46(7)°, V = 911(5) (A)3, Z = 2, (D/s)max = 0.001, Mr = 473.94, Dc = 1.728 g/cm3, μ(MoKα) = 1.365 mm-1, F(000) = 486, the final R = 0.0246 and wR = 0.0628 for 3809 observed reflections with I > 2σ(I). The mononuclear crystal structure extends into a two-dimensional net- work via hydrogen-bonding interactions and a three-dimensional framework is further formed by means of π-π stacking interactions. 相似文献
93.
94.
通过由Fe3(CO)12、RSH和Et3N所形成的[(μ-CO)(μ-RS)Fe2(CO)6]Et3NH于室温下分别与对或间苯二甲酰氯的原位反应,首次合成6个结构新颖的苯二甲酰基桥联铁硫配合物[(μ-RS)·Fe2(CO)6]2(μ-p-OCC6H4CO-p-μ)(R=Et,n-Bu,t-Bu)以及[(μ-RS)Fe2(CO)6]2(μ-m-OCC6H4CO-m-μ)(R=n-Pr,n-Bu,t-Bu)。经元素分析、IR光谱及1HNMR表征了它们的结构,并讨论了产物的生成过程。此外,还提出了合成对苯二甲酰氯的一种新方法。 相似文献
95.
With the assistance of HPLC-ESI-MS/MS, the self-assembly products of serine and histidine penta-coordinated phosphorus compound were separated and identified. The expectative product was seryl-histidine dipeptide, but it was found that there was almost equimolar amount of histidyl-histidine dipeptide as well as seryl-histidine dipeptide. The mechanism was speculated that there was iigand exchange between penta-coordinated phosphoryl serine and histidine in the reaction process. As a result,two types of dipeptide were produced. 相似文献
96.
The vapor‐phase reaction of citronellal (CTN) at 220 °C and atmospheric pressure has been studied using mesoporous molecular sieves and zeolites in a fixed‐bed reactor. The primary products included isopulegol (IPG), menthone, and pulegol with subsequent reactions to form cyclic hydrocarbons. The CTN conversion and the product selectivity depend on the acidity and the textural property of catalysts. Lewis and/or Brönsted acid sites are essential for catalyzing this reaction. An increase of SiO2/Al2O3 mol ratio diminishes the acid amount of all catalysts and enhances both the surface area and the structural order of MCM‐41. The catalytic activity follows the order of MCM‐41 > HZSM‐5 > Hβ > USY, in accordance with the relative total acid amount except that of MCM‐41. Despite its low acidity, Si‐MCM‐41 exhibits the best catalytic performance due to its uniform mesopores, large surface area and good stability; the CTN conversion and the IPG yield attain 91.9% and 58.6%, respectively, after at least 25 h time‐on‐stream. 相似文献
97.
鹿角短指软珊瑚Sinularia Cervicornis Tix-Dur 中的一个新糖甙-Cervicoside 总被引:1,自引:0,他引:1
珊瑚属腔肠动物门 ( Clelenterata) ,海鸡冠目 ( Alcyonacea) ,是一种热带与亚热带海洋中广泛分布Scheme 1 Structure of cervicoside(1 )的低等海洋生物 .软珊瑚的次生代谢物中含有萜类和甾体类等各类生理活性物质[1~ 5] .我们在对鹿角短指软珊瑚的次生代谢产物研究中 ,分离到一个新三糖甙 ,命名为 Cervicoside( 1 ) ,结构见 Scheme 1 .该化合物具有较强的体外抗癌活性 .1 实验部分1 .1 样品 鹿角短指软珊瑚采自海南岛三亚海域 .样品储藏于中山大学化学与化学工程学院天然有机化学研究室 ,编号为 98- SY- 3.种属由中国科学院南海… 相似文献
98.
The adsorptive and electrochemical behaviors of medecamycin were investigated on a glassy carbon electrode (GCE) pretreated by anodic oxidation at +1.8 V for 5 min in 0.025 mol l–1 NH3-NH4Cl (pH 8.6) solution. An adsorptive stripping voltammetric method for the determination of medecamycin at the pretreated glassy carbon electrode has been developed. Medecamycin was accumulated in NH3-NH4Cl buffer (pH 9.0) at a potential of –0.7 V (vs. saturated calomel electrode (SCE)) for a certain time, and then determined by second-order differential anodic stripping voltammetry. The second-order differential anodic stripping peak current at +0.72 V was proportional to the concentration of medecamycin in the range 2.0 g ml–1 to 50.0 g ml–1. The detection limit (three times the signal-to-noise) was 1.0 g ml–1 and the relative standard deviation of the results was 3.28% for eight successive determinations of 10.0 g ml–1 medecamycin. This method has been applied to the direct determination of medecamycin in commercial tablets and spiked urine samples with satisfactory results. 相似文献
99.
100.
Using renewable green hydrogen and carbon dioxide (CO2) to produce methanol is one of the fundamental ways to reduce CO2 emissions in the future, and research and development related to catalysts for efficient and stable methanol synthesis is one of the key factors in determining the entire synthesis process. Metal nanoparticles stabilized on a support are frequently employed to catalyze the methanol synthesis reaction. Metal-support interactions (MSIs) in these supported catalysts can play a significant role in catalysis. Tuning the MSI is an effective strategy to modulate the activity, selectivity, and stability of heterogeneous catalysts. Numerous studies have been conducted on this topic; however, a systematic understanding of the role of various strengths of MSI is lacking. Herein, three Cu/ZnO-SiO2 catalysts with different strengths of MSI, namely, normal precipitation Cu/ZnO-SiO2 (Nor-CZS), co-precipitation Cu/ZnO-SiO2 (Co-CZS), and reverse precipitation Cu/ZnO-SiO2 (Re-CZS), were successfully prepared to determine the role of such interactions in the hydrogenation of CO2 to methanol. The results of temperature-programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS) characterization illustrated that the MSI of the catalysts was considerably affected by the precipitation sequence. Fourier transform infrared reflection spectroscopy (FT-IR) results indicated that the Cu species existed as CuO in all cases and that copper phyllosilicate was absent (except for strong Cu-SiO2 interaction). Transmission electron microscopy (TEM), X-ray diffraction (XRD), and N2O chemical titration results revealed that strong interactions between the Cu and Zn species would promote the dispersion of Cu species, thereby leading to a higher CO2 conversion rate and improved catalytic stability. As expected, the Re-CZS catalyst exhibited the highest activity with 12.4% CO2 conversion, followed by the Co-CZS catalyst (12.1%), and the Nor-CZS catalyst (9.8%). After the same reaction time, the normalized CO2 conversion of the three catalysts decreased in the following order: Re-CZS (75%) > Co-CZS (70%) > Nor-CZS (65%). Notably, the methanol selectivity of the Re-CZS catalyst was found to level off after a prolonged period, in contrast to that of Co-CZS and Nor-CZS. Investigation of the structural evolution of the catalyst with time on stream revealed that the high methanol selectivity of the catalyst was caused by the reconstruction of the catalyst, which was induced by the strong MSI between the Cu and Zn species, and the migration of ZnO onto Cu species, which caused an enlargement of the Cu/ZnO interface. This work offers an alternative strategy for the rational and optimized design of efficient catalysts. 相似文献