全文获取类型
收费全文 | 5063篇 |
免费 | 837篇 |
国内免费 | 586篇 |
专业分类
化学 | 3555篇 |
晶体学 | 61篇 |
力学 | 307篇 |
综合类 | 35篇 |
数学 | 582篇 |
物理学 | 1946篇 |
出版年
2024年 | 12篇 |
2023年 | 107篇 |
2022年 | 91篇 |
2021年 | 144篇 |
2020年 | 196篇 |
2019年 | 144篇 |
2018年 | 155篇 |
2017年 | 140篇 |
2016年 | 222篇 |
2015年 | 223篇 |
2014年 | 295篇 |
2013年 | 336篇 |
2012年 | 429篇 |
2011年 | 466篇 |
2010年 | 354篇 |
2009年 | 321篇 |
2008年 | 324篇 |
2007年 | 321篇 |
2006年 | 288篇 |
2005年 | 249篇 |
2004年 | 195篇 |
2003年 | 136篇 |
2002年 | 156篇 |
2001年 | 122篇 |
2000年 | 106篇 |
1999年 | 119篇 |
1998年 | 108篇 |
1997年 | 97篇 |
1996年 | 94篇 |
1995年 | 67篇 |
1994年 | 82篇 |
1993年 | 55篇 |
1992年 | 56篇 |
1991年 | 57篇 |
1990年 | 35篇 |
1989年 | 52篇 |
1988年 | 36篇 |
1987年 | 34篇 |
1986年 | 14篇 |
1985年 | 14篇 |
1984年 | 9篇 |
1983年 | 8篇 |
1982年 | 4篇 |
1981年 | 8篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1957年 | 2篇 |
排序方式: 共有6486条查询结果,搜索用时 31 毫秒
151.
以D-核糖为原料,合成了1,4-脱水一双(氧特丁基二甲基甲硅烷基)-α-D-吡喃核糖(ADSR)和1,4-脱水-2,3-氧-亚异丙基-α-D-吡喃核糖(AIRP),研究了它们在SbCl5催化下的开环共聚合反应,并测定了共聚产物的比旋光度、分子量及1H、13CNMR谱。结果表明,尽管AIRP在均聚中总是得到单一的1-4β结构产物,而在共聚产物中,AIRP结构单元则为1—4β和1-5α的混合结构。同时发现,聚合温度对共聚物的产率和立体结构均有较大的影响。 相似文献
152.
ZnS胶体溶液中某些无机盐光化学过程中产生的阴离子自由基的ESR研究 总被引:4,自引:0,他引:4
本文用自旋捕捉与ESR技术相结合的方法研究了ZnS胶体溶液中某些无机盐光化学过程中产生的无机阴离子自由基,并对自由基产生的机理进行了讨论 相似文献
153.
Three new serratane triterpenoids, (3α,14α,15α,21α)‐3,14,15,21,29‐pentahydroxyserratan‐24‐oic acid ( 1 ), (3α,21β)‐serrat‐14‐ene‐3,21,24,30‐tetraol ( 2 ), and (3α,21α)‐serrat‐14‐ene‐3,21,24,29‐tetraol ( 3 ), were isolated from Phlegmariurus squarrosus, together with eight known compounds. Their chemical structures were elucidated on the basis of in‐depth spectroscopic analyses. 相似文献
154.
Influences of permeation of vanadium ions through PVDF-g-PSSA membranes on performances of vanadium redox flow batteries 总被引:6,自引:0,他引:6
Luo X Lu Z Xi J Wu Z Zhu W Chen L Qiu X 《The journal of physical chemistry. B》2005,109(43):20310-20314
The preparation and physical characterization of a poly(vinylidene fluoride)-graft-poly(styrene sulfonic acid) (PVDF-g-PSSA) membrane prepared by a solution-grafting method were described. These membranes exhibited high conductivity with a value 3.22 x 10(-2) S/cm at 30 degrees C. ICP studies revealed that the PVDF-g-PSSA membrane showed dramatically lower vanadium ion permeability compared to Nafion 117. Trivalent vanadium ions had the highest permeability through all these membranes in contrast to pentavalent vanadium ions with the lowest. The VRB with the low-cost PVDF-g-PSSA membrane exhibited a higher performance than that with Nafion 117 under the same operating conditions, and its energy efficiency reached 75.8% at 30 mA/cm(2). The performance of VRB with the PVDF-g-PSSA membrane can be maintained after more than 200 cycles at a current density of 60 mA/cm(2). 相似文献
155.
156.
A new triterpenoid, fornicatin C (= (3β)‐3‐hydroxy‐18(13 → 12β)‐abeo‐lanosta‐13(17),24‐dien‐18‐oic acid; 1 ), was isolated from the fruiting bodies of Ganoderma fornicatum, together with the known compounds fornicatin A ( 2 ) and fornicatin B ( 3 ), among other constituents. The structure of 1 was elucidated by means of spectroscopic techniques, and those of 2 and 3 were identified by comparing their spectroscopic data with those reported in the literature. 相似文献
157.
Thermal decomposition of dimethyl azo(bisisobutyrate) in a solution containing C(60) produced 1,4- and 1, 16-di(2-carbomethoxy-2-propyl)-1,x-dihydro[60]fullerenes in yields of 21% and 27%, respectively, based on reacted C(60). The structure of this first 1,16-dialkyl-1,16-dihydro[60]fullerene was assigned from (13)C 2D INADEQUATE NMR spectra. The 1,16-isomer has first and second electrochemical reduction potentials shifted positively by 0. 18 V relative to those of the 1,4-isomer. From the close similarity of all spectral, chromatographic, and electrochemical data, the previously unassigned isomer of 1,x-di(2-cyano-2-propyl)-1, x-dihydro[60]fullerene, which was obtained from azo(bisisobutyronitrile) and C(60), is also a 1,16-isomer. 相似文献
158.
The geometric and electronic structures of FeS(2) (100) surface have been studied by a quantum-mechanical calculation using a total-energy pseudopotential code, CASTEP. The (100) surface is very stable and does not give any significant geometric relaxation. The electronic structure of FeS(2) (100) surface is characterized by the appearance of new native surface states in the bulk band gap, which correspond to antibonding mixed Fea-Ssp(3) states. These surface states play an important role as mediators of electron transfer on both anodic and cathodic sites in the incipient oxidation of pyrite. Moreover, the (100) surface has small band gaps and shows some metallic character. It is predicted that the rate of cathodic reductive reaction of O(2) in the incipient oxidation of pyrite is much faster than previously considered. The transport of electrons from the anodic sites to the cathodic sites on the (100) surface is faster and hole injection of anodic sites is not the rate-determining step. So we can deduce that the rate-determining step of incipient oxidation for pyrite consists of both electron transfer of pyrite/aqueous O(2) interface and the splitting of H(2)O. 相似文献
159.
Zeng W Wang AQ Fisher AL Musson DG 《Rapid communications in mass spectrometry : RCM》2003,17(22):2475-2482
A generic high-throughput liquid chromatography (HTLC) tandem mass spectrometry (MS/MS) assay for the determination of compound I in human urine and dialysate (hemodialysis) was developed and validated. By using the HTLC on-line extraction technique, sample pretreatment was not necessary. The sample was directly injected onto a narrow bore large particle size extraction column (50 x 1.0 mm, 60 microm) where the sample matrix was rapidly washed away using a high flow rate (5 mL/min) aqueous mobile phase while analytes were retained. The analytes were subsequently eluted from the extraction column onto an analytical column using an organic-enriched mobile phase prior to mass spectrometric detection. The analytes were then eluted from the analytical column to the mass spectrometer for the determination. The linear dynamic range was 2.0-6000 ng/mL for the urine assay and 0.1-300 ng/mL for the dialysate assay. Intraday accuracy and precision were evaluated by analyzing five replicates of calibration standards at all concentrations used to construct the standard curve. For the urine assay, the precision (RSD%, n=5) ranged from 1.9 to 8.0% and the accuracy ranged from 87.8 to 105.2% of nominal value. For the dialysate assay, the precision (RSD%, n=5) ranged from 1.1 to 10.0% and the accuracy from 94.5 to 105.2% of nominal value. In-source fragmentation of the acyl glucuronide metabolite (compound III) did not interfere with the determination of parent compound I. The developed HTLC/MS/MS methodology was specific for compound I in the presence of compound III. Column life-time is increased and sample analysis time is decreased over traditional reversed-phase methods when direct injection assays for urine and dialysate are coupled with the technology of HTLC. 相似文献
160.
Jian Yan Xiang‐Ming Zhang Zhong‐Rong Li Lin Zhou Jian‐Chao Chen Li‐Rong Sun Ming‐Hua Qiu 《Helvetica chimica acta》2005,88(2):240-244
Three new triterpenoids, (3β,8β,14α,21α)‐26,27‐dinoronocerane‐3,8,14,21‐tetrol ( 1 ), (3β,8β,14α,21β)‐26,27‐dinoronocerane‐3,8,14,21‐tetrol ( 2 ), and lycopodiin A ( 3 ), together with four known compounds, lycoclavanol ( 4 ), lycoclaninol ( 5 ), α‐onocerin ( 6 ), and 3‐epilycoclavanol ( 7 ), were isolated from Lycopodium japonicum Thunb (Lycopodiaceae). Their structures were established by means of spectroscopic analyses. Compounds 3 and 7 showed moderate antitumor activity. Compounds 4 and 6 exhibited acetylcholinesterase inhibition activity. 相似文献