全文获取类型
收费全文 | 2416篇 |
免费 | 329篇 |
国内免费 | 258篇 |
专业分类
化学 | 1833篇 |
晶体学 | 29篇 |
力学 | 98篇 |
综合类 | 13篇 |
数学 | 236篇 |
物理学 | 794篇 |
出版年
2024年 | 3篇 |
2023年 | 40篇 |
2022年 | 74篇 |
2021年 | 77篇 |
2020年 | 82篇 |
2019年 | 101篇 |
2018年 | 74篇 |
2017年 | 60篇 |
2016年 | 99篇 |
2015年 | 95篇 |
2014年 | 131篇 |
2013年 | 171篇 |
2012年 | 191篇 |
2011年 | 230篇 |
2010年 | 148篇 |
2009年 | 126篇 |
2008年 | 168篇 |
2007年 | 160篇 |
2006年 | 141篇 |
2005年 | 128篇 |
2004年 | 74篇 |
2003年 | 65篇 |
2002年 | 79篇 |
2001年 | 49篇 |
2000年 | 38篇 |
1999年 | 37篇 |
1998年 | 32篇 |
1997年 | 31篇 |
1996年 | 32篇 |
1995年 | 32篇 |
1994年 | 23篇 |
1993年 | 18篇 |
1992年 | 30篇 |
1991年 | 13篇 |
1990年 | 23篇 |
1989年 | 17篇 |
1988年 | 15篇 |
1987年 | 15篇 |
1986年 | 8篇 |
1985年 | 13篇 |
1984年 | 14篇 |
1983年 | 9篇 |
1982年 | 6篇 |
1981年 | 7篇 |
1980年 | 4篇 |
1979年 | 5篇 |
1978年 | 4篇 |
1975年 | 3篇 |
1961年 | 1篇 |
1954年 | 1篇 |
排序方式: 共有3003条查询结果,搜索用时 0 毫秒
11.
相转移催化合成对甲氧基肉桂酸-2-乙基己酯的研究 总被引:5,自引:1,他引:5
对甲氧基肉桂酸 2 乙基己酯是一种有效的UVB防晒剂[1 ,2 ] ,一般采用Claisen Schmidt缩合反应制得[3] ,但由于催化剂KOH处于水相 ,对反应物不能充分起到催化作用导致产率较低[4] 。我们利用乙二醇 (PEG)为相转移催化剂合成立体专一的反式对甲氧基肉桂酸 2 乙基己酯 ,产率提高到 72 .5 %。合成路线如下 :1 实验部分1 .1 仪器与试剂BIO RAPFT45 0红外光谱仪 ,用液膜法测试 ;Brurer AM 30 0超导核磁共振仪 (溶剂DC Cl3) ;MAT/44S ,GC MS型色质联用谱仪 ;试剂均为分析纯 ,上海化学试剂… 相似文献
12.
As a natural diterpenoid, crotophorbolone possesses a challenging trans,trans-5/7/6 framework decorated with six contiguous stereogenic centers and is structurally and biogenetically related to tigliane-type diterpenoids with intriguing bioactivities such as phorbol and prostratin. Based on the convergent strategy, we completed an eighteen-step total synthesis of crotophorbolone starting from (−)-carvone and (+)-dimethyl-2,3-O-isopropylidene-l-tartrate. The key elements of the synthesis involve expedient installation of the six-membered ring and the five-membered ring with multiple functional groups at an early stage, cyclization of the seven-membered ring through alkenylation of the ketone between the five-membered ring and the six-membered ring, functional group-sensitive ring-closing metathesis and final selective introduction of hydroxyls at C20 and C4.Convergent total synthesis of crotophorbolone was accomplished in 18 longest linear steps. Observation of unexpected thermodynamic stability of a cis,trans-5/7/6 tricycle would benefit synthetic design of tigliane- and daphnane-related diterpenoids. 相似文献
13.
Adam Bange Jian Tu Xiaoshan Zhu Chong Ahn H. Brian Halsall William R. Heineman 《Electroanalysis》2007,19(21):2202-2207
A microbead based sandwich immunoassay for MS2 bacteriophage was developed using an interdigitated array (IDA) electrode with nanoscale dimensions (220 nm electrode width, 620 nm gap). The IDA was fabricated using an electron beam lithographic lift‐off technique. After an antibody‐assisted capture of MS2 using paramagnetic microbeads, a β‐galactosidase labeled secondary antibody was used to convert p‐aminophenyl‐β‐D ‐galactopyranoside (PAPG) into the redox active p‐aminophenol (PAP). Amperometric detection of PAP with IDA electrodes at +300 and ?200 mV vs. a Ag/AgCl reference electrode was used to measure the result, detecting MS2 concentrations as low as 10 ng/mL. 相似文献
14.
A non-aqueous reversed phase HPLC was developed for determining alpha-tocopherol in Sea buckthorn oil capsule without the need for saponification. A reversed phase column (Alltima C(18), 4.6 x 250 mm, 5 microm) was used with a mobile phase of methanol-acetonitrile (95 : 5, v/v) and flow rate of 1 ml/min. The contents in capsule were extracted with n-hexane. Detection wavelength was set at 292 nm. Each analysis requires no longer than 20 min. The linearity range for alpha-tocopherol was 9.4-47.0 microg/ml. The detection limit was 0.94 microg/ml. The mean recovery was 95.82 (RSD 2.3%). This method is suitable for quantitative analysis of alpha-tocopherol in Sea buckthorn oil or its Traditional Chinese Medicinal preparation. 相似文献
15.
A very simple, selective and sensitive method was developed for the spectrophotometric determination of Mo in the presence of W. The method was based on the formation of color charge transfer complex, molybdotungstophosphate-3,3',5,5'-tetramethylbezidine anion, which was solubilized and stabilized in PVA medium. Following the recommended procedure, molybdenum could be determined in the linear range of 0.04-2.5 mug ml(-1) and the molar absorptivity was 1.47x10(4) l mol(-1) cm(-1) at 660 nm. The proposed method had been applied to the determination of trace molybdenum in tungsten ore with satisfactory results. 相似文献
16.
本文用差热分析和X射线衍射方法测定了BaB_2O_4-CdO和BaB_2O_4-ZnO二元系相图。在BaB_2O_4-CdO体系中存在着一新化合物BaCdB_2O_5,在785±3℃同成份熔化。在BaB_2O_4-ZnO体系中,由包晶反应形成一新化合物BaZn_3B_2O_7,反应温度为903±3℃。在富BaB_2O_4区形成一个宽的低温相BaB_2O_4固溶区。研究结果表明,用Zn~(2 )替代BaB_2O_4中Ba~(2 )形成固溶体,不能将高温相BaB_2O_4稳定到室温,证实了“经验函数关系式”的预测结果。 相似文献
17.
Phosphoric acid at levels above 10-3 M depresses the S2 emission from sulphate, but concentrations up to 0.1 M may be necessary to eliminate cationic interferences. 相似文献
18.
The bimolecular single collision reaction potential energy surface of an isocyanate NCO radical with a ketene CH2CO molecule was investigated by means of B3LYP and QCISD(T) methods. The computed results indicate that two possible reaction channels exist on the surface. One is an addition-elimination reaction process, in which the CH2CO molecule is attacked by the nitrogen atom at its methylene carbon atom to lead to the formation of the intermediate OCNCH2CO followed by a C-C rupture channel to the products CH2NCO+CO. The other is a direct hydrogen abstraction channel from CHzCO by the NCO radical to afford the products HCCO+HNCO. Because of a higher barrier in the hydrogen abstraction reaction than in the addition-elimination reaction, the direct hydrogen abstraction pathway can only be considered as a secondary reaction channel in the reaction kinetics of NCO+ CH2CO. The predicted results are in good agreement with previous experimental and theoretical investigations. 相似文献
19.
Weizhen Lin Tiecheng Tu Jirong Dong Jiashang Zhang Nianyun Lin 《Radiation Physics and Chemistry》1998,53(6):651-655
ESR spectrum of neat histone H3 γ-irradiated and observed at 77 K with low microwave power and modulation amplitude showed multiple resolved structure depicting nonequivalent interaction of the unpaired electron located at amido-carbonyl radical anion [–
)NH–] of the peptide backbone with adjacent –NH– group and the β-proton of –CH group. The predominance of amido-carbonyl radical anion is in good accord with the expected partition of secondary electrons amongst the various electrophilic groups including peptide carbonyl and aromatic acid residues. Following a gradual rise of annealing temperature to room temperature, a double splitting spectrum from the well known -carbon amido radical was evolved. 相似文献
20.