全文获取类型
收费全文 | 8207篇 |
免费 | 1715篇 |
国内免费 | 2091篇 |
专业分类
化学 | 6206篇 |
晶体学 | 256篇 |
力学 | 584篇 |
综合类 | 144篇 |
数学 | 920篇 |
物理学 | 3903篇 |
出版年
2024年 | 21篇 |
2023年 | 133篇 |
2022年 | 284篇 |
2021年 | 318篇 |
2020年 | 342篇 |
2019年 | 354篇 |
2018年 | 302篇 |
2017年 | 361篇 |
2016年 | 472篇 |
2015年 | 464篇 |
2014年 | 542篇 |
2013年 | 734篇 |
2012年 | 763篇 |
2011年 | 756篇 |
2010年 | 642篇 |
2009年 | 687篇 |
2008年 | 714篇 |
2007年 | 618篇 |
2006年 | 613篇 |
2005年 | 499篇 |
2004年 | 386篇 |
2003年 | 275篇 |
2002年 | 286篇 |
2001年 | 281篇 |
2000年 | 263篇 |
1999年 | 178篇 |
1998年 | 111篇 |
1997年 | 78篇 |
1996年 | 90篇 |
1995年 | 54篇 |
1994年 | 57篇 |
1993年 | 45篇 |
1992年 | 54篇 |
1991年 | 34篇 |
1990年 | 48篇 |
1989年 | 34篇 |
1988年 | 26篇 |
1987年 | 16篇 |
1986年 | 17篇 |
1985年 | 8篇 |
1984年 | 12篇 |
1983年 | 12篇 |
1982年 | 6篇 |
1981年 | 4篇 |
1980年 | 2篇 |
1979年 | 4篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1974年 | 2篇 |
1971年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
102.
In the present paper, we describe a microfluidics-based sensing system for nonelectroactive anions under negative separation electric field by mounting a single carbon fiber disk working electrode (WE) in the end part of a poly(dimethylsiloxane) microchannel. In contrast to work in a positive separation electric field described in our previous paper (Anal. Chem. 2004, 76, 6902-6907), here the electrochemical reduction reaction at the WE is not coupled with the separation high-voltage (HV) system, whereas the electrochemical oxidation reaction at the WE is coupled with the separation HV system. The electroactive indicator is the carbon fiber WE itself but not dissolved oxygen. This provides a convenient and sensitive means for the determination of nonelectroactive anions by amperometry. The influences of separation voltage, detection potential, and the distance between the WE and the separation channel outlet on the response of the detector have been investigated. The present detection mode is successfully used to electrochemically detect F-, Cl-, SO4(2-), CH3COO-, H2PO4-. Based on the preliminary results, a detection limit of 2 microM and a dynamic range up to three orders of magnitude for Cl- could be achieved. 相似文献
103.
Protein tyrosine phosphatase 1B (PTP1B) functions by removing the phosphoryl group from tyrosinephosphorylated proteins in
insulin signaling and metabolism. The regeneration of the active site involves a sulphenylamide intermediate derived from
the intrastrand cross-linking between the catalytic serine and the neighboring backbone nitrogen. Two mechanisms have been
proposed for the formation of the sulphenylamide intermediate and the subsequent reactivation of the catalytic site. In the
current work, the proposed mechanisms have been investigated by the use of density functional theory calculations. Our results
suggest that these two mechanisms have similar overall energy barriers and that the preferred route will be determined by
the availability of hydrogen peroxide or other oxidizing reagents. 相似文献
104.
PAMAM树形分子对CaCO3结晶影响的研究 总被引:6,自引:0,他引:6
研究了不同端基的聚酰胺胺(PAMAM)树形分子对CaCO3在水溶液中结晶的影响。分别利用傅立叶变换红外光谱(FTIR)、X-射线衍射(XRD)、扫描电镜(SEM)等测试手段对样品进行了分析。结果表明:没有树形分子存在时CaCO3是粒径为10μm的菱形方解石晶体;端基为-COONa的树形分子存在时CaCO3则是粒径为1~2μm的球形球霰石晶体;-COOCH3端基PAMAM树形分子存在时得到的CaCO3相似文献
105.
Solid-phase microextraction (SPME) with a disposable ionic liquid (IL) coating was developed for headspace extraction of benzene, toluene, ethylbenzene, and xylenes (BTEX) in paints. The SPME fiber was coated with IL prior to every extraction, then the analytes were extracted and desorbed on the injection port of gas chromatography, and finally the IL coating on the fiber was washed out with solvents. The coating and washing out of IL from the fiber can be finished in a few minutes. This disposable IL-coated fiber was applied to determine BTEX in water-soluble paints with results in good agreement with that obtained by using commercially available SPME fibers. For all the four studied paints samples, the benzene contents were under the detection limits, but relatively high contents of toluene, ethylbenzene and xylenes (56-271 microg g(-1)) were detected with spiked recoveries in the range of 70-114%. Compared to the widely used commercially available SPME fibers, this proposed disposable IL-coated fiber has much lower cost per determination, comparable reproducibility (RSD < 11%), and no carryover between each determination. Considering that IL possess good extractability for various organic compounds and metals ions, and that task-specific IL can be designed and synthesized for selective extraction of target analytes, this disposable IL coating SPME might has great potential in sample preparation. 相似文献
106.
杯芳烃的分子设计(Ⅵ)--一种新的杯[4]磺胺衍生物的合成及晶体结构 总被引:2,自引:0,他引:2
杯芳烃是由酚单体通过亚甲基在羟基邻位桥连而成的环状低聚物, 它具有可调的杯状疏水空腔, 结构柔性较大, 构象可变, 并对中性分子和有机、无机离子具有选择性配位能力. 因此, 在其上下缘进行化学修饰所得到的杯芳烃衍生物可广泛应用于萃取分离、离子选择性电极、色谱分析、功能材料、催化及模拟酶等研究领域[1~4]. 相似文献
107.
An experimental investigation on shortening of travelling-wave ASE employing a transversal pumping is presented. A N2 laser with =337.1 nm, pulsewidth: 700 ps is used as a pump source. An ASE pulse with duration of 45, 55 and 45 ps from dye solution of Rh 6G, Rh B and C311, respectively, is obtained. Pulse shapes of output signals generated from these solutions in three different pumping schemes are compared. 相似文献
108.
CUI Wei HUANG Lei LI Wei WANG Li-ping 《高等学校化学研究》2006,22(2):236-238
Introduction S Adenosylmethionine(SAM)isabiologicallyac tivecompoundwidelydistributedinthebodytissues andfluids.Itisinvolvedinanumberofbiochemical reactions.Asamethylgroupdonor,itisimportantin transmethylationreactions,whichcontributestothe synthesesofsuc… 相似文献
109.
固体磷酸催化剂的活性相 总被引:8,自引:0,他引:8
研究了固体磷酸催化剂活性与其自由磷酸聚合态及磷酸硅晶型的关系,指出高活性磷酸催化剂应具备的条件,即自由磷酸中应为正磷酸和焦磷酸的混合物,结合态磷应具有“C”晶型。 相似文献
110.
Jian Wang Xing‐You Xu Lu‐De Lu Xu‐Jie Yang Wei‐Xing Ma Xiang‐Ning Cui 《Surface and interface analysis : SIA》2007,39(6):482-486
The streaming potential of supersaturated solution of binary carboxylic acids, which have even carbon atoms, was determined to characterize crystallization under different temperatures. The value of the streaming potential was related to the type and solubility of the acids and the starting temperature of crystallization, and was easily influenced by the pressure difference of the liquid or the rate of temperature decline. When the temperature was declined to the point where a crystal nucleus appeared, the streaming potential reached the minimum. Thereafter, as the temperature was sequentially lowered, some minicrystals grew, and the streaming potential presented an ascendant tendency. The higher the starting temperature of the acids saturated solution, the higher is the temperature corresponding to the streaming potential minimum. The less the carbon atoms in the acids and the greater the solubility of the acids are, the higher is the temperature of the streaming potential minimum. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献