全文获取类型
收费全文 | 45571篇 |
免费 | 5551篇 |
国内免费 | 4460篇 |
专业分类
化学 | 21006篇 |
晶体学 | 318篇 |
力学 | 1560篇 |
综合类 | 271篇 |
数学 | 3332篇 |
物理学 | 11230篇 |
综合类 | 17865篇 |
出版年
2024年 | 150篇 |
2023年 | 658篇 |
2022年 | 1145篇 |
2021年 | 1228篇 |
2020年 | 1185篇 |
2019年 | 1234篇 |
2018年 | 1139篇 |
2017年 | 1065篇 |
2016年 | 1583篇 |
2015年 | 1745篇 |
2014年 | 2207篇 |
2013年 | 2802篇 |
2012年 | 3299篇 |
2011年 | 3467篇 |
2010年 | 2753篇 |
2009年 | 2792篇 |
2008年 | 3091篇 |
2007年 | 2957篇 |
2006年 | 2723篇 |
2005年 | 2198篇 |
2004年 | 1845篇 |
2003年 | 1493篇 |
2002年 | 1491篇 |
2001年 | 1289篇 |
2000年 | 1124篇 |
1999年 | 1295篇 |
1998年 | 1005篇 |
1997年 | 967篇 |
1996年 | 886篇 |
1995年 | 759篇 |
1994年 | 707篇 |
1993年 | 601篇 |
1992年 | 454篇 |
1991年 | 474篇 |
1990年 | 370篇 |
1989年 | 305篇 |
1988年 | 269篇 |
1987年 | 200篇 |
1986年 | 122篇 |
1985年 | 85篇 |
1984年 | 67篇 |
1983年 | 45篇 |
1982年 | 35篇 |
1981年 | 25篇 |
1980年 | 29篇 |
1978年 | 16篇 |
1977年 | 17篇 |
1976年 | 16篇 |
1975年 | 16篇 |
1973年 | 18篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Vinylic cyclopropanes were formed highly selectively via the Pd(PPh(3))(4)-catalyzed insertion-intramolecular nucleophilic substitution reaction of aryl or 1-alkenyl iodides with 2-(2', 3'-dienyl)malonates. The regioselectivity observed here is different from what was reported by Cazes et al. 相似文献
992.
Nanoporous TiO2 photocatalysts were prepared by use of controlled drying method with surfactants. The surface area and porous properties are dependent on the chain length of incorporated surfactant cation. The TiO2 materials prepared in the presence of surfactant molecules during the gel formation exhibit much higher photocatalytic activity than that prepared in the absence of surfactants. 相似文献
993.
Yajing Yin Ping Wu Yafen Lü Pan Du Yanmao Shi Chenxin Cai 《Journal of Solid State Electrochemistry》2007,11(3):390-397
A single-walled carbon nanotube (SWNT)-modified electrode was fabricated and characterized by SEM and ac impedance techniques.
The direct electrochemistry of cytochrome c (Cyt c), which was adsorbed on the surface of the SWNT, was studied by cyclic voltammetry. The results from cyclic voltammetry and
infrared spectroscopy indicated that Cyt c remained in its original structure and did not undergo structural change after its immobilization on the SWNT. Further results
demonstrated that the SWNT had promotional effects on the direct electron transfer of Cyt c and also indicated that the immobilized Cyt c retained its electrocatalytic activity to the reduction of H2O2. This modified electrode might be used in development of new biosensors and the biofuel cells. 相似文献
994.
外加盐作用形成的正负离子表面活性剂双水相 总被引:1,自引:0,他引:1
癸基三乙基溴化铵-癸基磺酸钠(C10NE-C10SO3)等摩尔混合均相体系(即使在表面活性剂总浓度高达0.2 mol•L-1时仍然可形成稳定的均相溶液)在外加盐NaF、Na2SO4和Na3PO4的作用下可自发分离成两个水相(双水相).研究了该类双水相体系的形成、相行为及其对牛血清蛋白(BSA)的分配,并与普通的正负离子表面活性剂混合双水相体系进行了比较.结果表明,该类双水相体系克服了普通的正负离子表面活性剂混合双水相体系的一些不足,具有一些独特的优点.该类双水相体系的相行为可以通过外加盐进行调控,通过外加盐的种类来调控和优化BSA的分配行为.图1表2参8 相似文献
995.
7-(对甲酰基苯偶氮)-8-羟基喹啉-5-磺酸的合成及其双波长分光光度法测定镓 总被引:1,自引:0,他引:1
7-(对甲酰基苯偶氮)-8-羟基喹啉-5-磺酸是一新显色剂。该试剂在微碱性介质中(pH=7.5)与镓形成黄色络合物。络合物λmax=392nm,摩尔吸光系数ε392=2.24×104L·mol-1·cm-1。同时在500nm呈现负峰,用双峰观波长法测定镓ε392~500=6.89×104L·mol-1·cm-1,灵敏度是单波长法的三倍多.线性范围0~2.0×10-5mol/L。用拟定的方法测定了掺硅的GaAS材料及岩石中的镓,加入回收率为106%~110%;方法的相对标准偏差小于1.6%。 相似文献
996.
多维核磁共振技术的飞速发展议得其在生物大分子结构测定方面的应用已经达到可以与【射线晶体学并驾齐驱的地步.蛋白质结构堆积紧密,较适合于用核磁共振方法给出确定的结构.与蛋白质不同的是多肽的柔性较大,在溶液中可能存在多种构象,核磁共振实验给出的只是平均信息*.利用核磁,(振数据构建分子结构模型常用的方法有距离几何、分子动力学等,在由核磁共振NOESZ得到的距离信息足够多时可以给出较好的结果问.由于多肽本身的特点:柔性较大,由核磁共振得到的距离信息较少等,利用距离几何、分子动力学方法进行构象搜索时容易陷入… 相似文献
997.
The distribution coefficients of oil and curing agent in PP/EPDM TPV were calculated by measuring the melting point of the PP phase using differential scanning calorimetry (DSC). The PP/EPDM TPV was prepared by using a twin screw extruder and a peroxide curing agent was used. The peroxide induces the degradation of PP, resulting in the decrease of Tm. The oil in PP phase also decreases the Tm. Based on the Tm difference among pure PP and PP/EPDM TPV before and after extraction by cylcohexane, the calculated oil distribution coefficient is 0.537. The addition sequence of PP, oil, and curing agent has a significant effect on the Tm and the calculated curing agent distribution coefficient is 0.52. Both of the coefficients are less than 1. Based on the calculation of the two coefficients, a rationale design of thermoplastic vulcanizate (TPV) can be made by proper control of raw materials, addition sequence, and processing parameters. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
998.
A reversed-phase LC–MS method with quadrupole-time of flight (QTOF) detection has been developed for the determination of four dinitro-toluenesulfonic acids and two amino-nitro-toluenesulfonic acids in groundwater. The analytes were separated by HPLC with 0.1% (v/v) formic acid as mobile phase modifier compatible with mass spectrometric detection. QTOF-MS analysis with negative ion electrospray ionization afforded good selectivity and sensitivity for analysis of the dinitro- and amino-nitro-toluenesulfonic acids. Structure elucidation and confirmation were accomplished by tandem mass spectrometry. Characteristic ions resulting from the loss of NO, NO2, and SO2 from the [M–H]– ions were detected. An intense fragment ion at m/z 80 representing the [SO3]– ion was detected for all dinitro- and amino-nitro-toluenesulfonic acids. Solid-phase extraction using a co-polymer cartridge was developed for preconcentration of the analytes from water. Good recovery (>85%) was achieved when 0.1% formic acid was added into the water samples before extraction. Method detection limits ranged from 10 to 76 ng L–1 for the targeted compounds when 10 mL water was analyzed. Groundwater samples collected from wells close to a former ammunition plant in Stadtallendorf, Germany, were analyzed for the dinitro- and amino-nitro-toluenesulfonic acids. 相似文献
999.
1000.
Sem DS Bertolaet B Baker B Chang E Costache AD Coutts S Dong Q Hansen M Hong V Huang X Jack RM Kho R Lang H Ma CT Meininger D Pellecchia M Pierre F Villar H Yu L 《Chemistry & biology》2004,11(2):185-194
Genomics-driven growth in the number of enzymes of unknown function has created a need for better strategies to characterize them. Since enzyme inhibitors have traditionally served this purpose, we present here an efficient systems-based inhibitor design strategy, enabled by bioinformatic and NMR structural developments. First, we parse the oxidoreductase gene family into structural subfamilies termed pharmacofamilies, which share pharmacophore features in their cofactor binding sites. Then we identify a ligand for this site and use NMR-based binding site mapping (NMR SOLVE) to determine where to extend a combinatorial library, such that diversity elements are directed into the adjacent substrate site. The cofactor mimic is reused in the library in a manner that parallels the reuse of cofactor domains in the oxidoreductase gene family. A library designed in this manner yielded specific inhibitors for multiple oxidoreductases. 相似文献