全文获取类型
收费全文 | 8238篇 |
免费 | 1401篇 |
国内免费 | 1007篇 |
专业分类
化学 | 5945篇 |
晶体学 | 126篇 |
力学 | 458篇 |
综合类 | 56篇 |
数学 | 1172篇 |
物理学 | 2889篇 |
出版年
2024年 | 34篇 |
2023年 | 195篇 |
2022年 | 358篇 |
2021年 | 305篇 |
2020年 | 336篇 |
2019年 | 330篇 |
2018年 | 268篇 |
2017年 | 269篇 |
2016年 | 430篇 |
2015年 | 418篇 |
2014年 | 557篇 |
2013年 | 607篇 |
2012年 | 767篇 |
2011年 | 781篇 |
2010年 | 504篇 |
2009年 | 454篇 |
2008年 | 514篇 |
2007年 | 406篇 |
2006年 | 409篇 |
2005年 | 376篇 |
2004年 | 327篇 |
2003年 | 248篇 |
2002年 | 231篇 |
2001年 | 193篇 |
2000年 | 129篇 |
1999年 | 191篇 |
1998年 | 125篇 |
1997年 | 102篇 |
1996年 | 114篇 |
1995年 | 115篇 |
1994年 | 96篇 |
1993年 | 58篇 |
1992年 | 58篇 |
1991年 | 59篇 |
1990年 | 68篇 |
1989年 | 45篇 |
1988年 | 29篇 |
1987年 | 23篇 |
1986年 | 30篇 |
1985年 | 15篇 |
1984年 | 14篇 |
1983年 | 16篇 |
1982年 | 9篇 |
1981年 | 11篇 |
1979年 | 3篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1928年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
担载液相催化剂的研究——Ⅳ.催化剂的原位红外光谱表征 总被引:1,自引:0,他引:1
本文利用原位红外光谱方法对铑基担载液相催化剂(SLPC)在接近于实际反应条件下进行了表征。结果表明,新鲜催化剂上,铑膦络合物主要以二聚物的形式存在,如Rh_2(CO)_2(PPh_3)_4而在合成气或反应气氛中,催化剂铑膦络合物以单核络合物HRh(CO)_2(PPh_3)_2的形式存在。文中还对SLPC在CO,H_2,C_2-H_4,空气和HCl中处理时铑络合物种的变化进行了原位观察。实验结果表明,SLPC上活性铑络合物与对应的均相过程完全一致,进一步证实了SLPC催化在微观上就是一个均相催化过程。 相似文献
102.
The development of highly active and stable reversible oxygen electrocatalysts is crucial for improving the efficiency of metal-air battery devices. Herein, an efficient liquid exfoliation strategy was designed for producing silk-like FeS2/NiS2 hybrid nanocrystals with enhanced reversible oxygen catalytic performance that displayed excellent properties for Zn-air batteries. Because of the unique silk-like morphology and interface nanocrystal structure, they can catalyze the oxygen evolution reaction (OER) efficiently with a low overpotential of 233 mV at j = 10 mA cm?2. This is an improvement from the recently reported catalysts in 1.0 M KOH. Meanwhile, the oxygen reduction reaction (ORR) activity of the silk-like FeS2/NiS2 hybrid nanocrystals showed an onset potential of 911 mV and a half-wave potential of 640 mV. In addition, the reversible oxygen electrode activity of the silk-like FeS2/NiS2 hybrid nanocrystals was calculated to be 0.823 V, based on the potential of the OER and ORR. Further, the homemade rechargeable Zn-air batteries using FeS2/NiS2 hybrid nanocrystals as the air-cathode displayed a high open-circuit voltage of 1.25 V for more than 17 h and an excellent rechargeable performance for 25 h. The solid Zn-air batteries exhibited an excellent rechargeable performance for 15 h. This study provided a new method for designing interface nanocrystals with a unique morphology for efficient multifunctional electrocatalysts in electrochemical reactions and renewable energy devices. 相似文献
103.
A general method for the intermolecular coupling of aryl halides and amides using a Xantphos/Pd catalyst is described. This system displays good functional group compatibility, and the desired C-N bond forming process proceeds in good to excellent yields with 1-4 mol % of the Pd catalyst. Additionally, the arylation of sulfonamides, oxazolidinones, and ureas is reported. The efficiency of these transformations was found to be highly dependent on reaction concentrations and catalyst loadings. A Pd complex resulting from oxidative addition of 4-bromobenzonitrile, (Xantphos)Pd(4-cyanophenyl)(Br) (II), was prepared in one step from Xantphos, Pd(2)(dba)(3), and the aryl bromide. Complex II proved to be an active catalyst for the coupling between 4-bromobenzonitrile and benzamide. X-ray crystallographic analysis of II revealed a rare trans-chelating bisphosphine-Pd(II) structure with a large bite angle of 150.7 degrees. 相似文献
104.
The effect of a series of novel Schiff base compounds on Staphylococcus aureus was studied by microcalorimetric method at 37 °C The results showed that all of the organic compounds had the capacity to inhibit the growth of S. aureus in different extent. And the extent and duration of the inhibitory effect on the growth of S. aureus, judged from the rate constant (k), varied with the different structure of the Schiff base compounds. According to the power-time curves, the multiplication rate constant and inhibition ratio were calculated. The growth rate constant of S. aureus (in log phase) in the presence of Schiff base compounds decreased with the increasing of the concentrations of these compounds regularly. The experimental results revealed that the hydrophilicity of Schiff bases had a great influence on their antibacterial activity. Of these Schiff bases, the greater their hydrophilicity, the higher their antibacterial activity. The antibacterial structure-activity relationship (SAR) of Schiff base derivatives was also briefly discussed. 相似文献
105.
本文利用高压法制备HFe2Co(CO)9(μ3-S),作为原料,经脱质子化作用,再分别与(PPh3)2Cu(NO3)和PPh3AuCl反应,将Ph3Cu-或Ph3Au-联接到原始簇合物的中心骨架上,使簇核扩大,得到了组成为(PPh3)2CuFe2Co(CO)8(μ3-S)和(PPh3)3AuFe2Co(CO)7(μ3-S)的化合物.文中对此两个新化合物进行了IR,UV,1H和31P NMR.元素分析、熔点测定等性质表征,并对(PPh3)2CuFe2Co(CO)7(μ3-S)进行了单晶X-射线衍射分析.两个化合物具有类似的中心骨架,在Fe2和Co原子三角形的上面和下面分别键联着Cu和S,或Au和S原子,构成了三角双锥结构.其中一个簇合物由二个三苯基膦和八个羰基配位,另一个则由三个三苯基膦和七个羰基配位. 相似文献
106.
地锦草总黄酮最佳提取分离工艺的研究 总被引:2,自引:0,他引:2
采用四因素三水平的正交实验方法,对地锦草总黄酮的最佳提取工艺进行了探索.采用乙酸乙酯萃取、酸碱沉淀、铅盐沉淀3种方法,对其最佳分离工艺进行了探索.正交实验结果表明:温浸法中四因素对地锦草黄酮的影响顺序为乙醇浓度>样液比>提取温度>提取时间.通过实验得到了地锦草总黄酮的最佳提取工艺:以10倍体积的50%的乙醇水溶液在80℃浸提1 h.地锦草总黄酮的最佳分离方法为酸碱沉淀法.这些数据为中药地锦草的开发和应用提供了科学依据. 相似文献
107.
本文采用XE-60交联弹性石英性细管柱及407有机体埴充柱气色谱法可分分析丙烯腈中有机杂质。通过对柱长、担体粒度、液膜厚度、柱温和载气流量的选择。确定出最佳色 谱条件。 相似文献
108.
109.
High-level expression of soluble human β-defensin-2 fused with green fluorescent protein in Escherichia coli cell-free system 总被引:2,自引:0,他引:2
Human β-defensin-2 (hBD2), a small cationic peptide, exhibits a broad range of antimicrobial activity and does not acquire
any microbial resistance. To produce this uneasily detectable, degradable, and toxic polypeptide efficiently, an alternative
approach based on the Escherichia coli cell-free biosynthesis system was proposed. The approach implies that a polypeptide of interest is synthesized as a fusion
protein linked to a green fluorescent protein (GFP) through a cleavable spacer. With batch-mode operation, a significant amount
of hBD2 fused with GFP (0.25 mg/mL) can be expressed in this cell-free system. The productivity of the fusion protein can
be improved up to 1.2 mg/mL by employing a continuous-exchange cell-free system. Furthermore, the GFP moiety provides directly
visible and quantitative monitoring of the polypeptide synthesis, and the product is soluble and stable. This work will be
helpful in allowing the rapid and visible expression of other similar defensins using an in vitro cell-free system. 相似文献
110.