首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   1294篇
  免费   42篇
  国内免费   317篇
化学   1545篇
晶体学   4篇
力学   4篇
综合类   11篇
数学   9篇
物理学   80篇
  2024年   3篇
  2023年   30篇
  2022年   159篇
  2021年   107篇
  2020年   76篇
  2019年   64篇
  2018年   42篇
  2017年   53篇
  2016年   58篇
  2015年   47篇
  2014年   58篇
  2013年   95篇
  2012年   69篇
  2011年   79篇
  2010年   67篇
  2009年   68篇
  2008年   76篇
  2007年   80篇
  2006年   80篇
  2005年   52篇
  2004年   58篇
  2003年   50篇
  2002年   28篇
  2001年   25篇
  2000年   21篇
  1999年   17篇
  1998年   16篇
  1997年   17篇
  1996年   14篇
  1995年   7篇
  1994年   8篇
  1993年   5篇
  1992年   4篇
  1991年   4篇
  1990年   6篇
  1989年   2篇
  1988年   4篇
  1987年   1篇
  1986年   1篇
  1984年   1篇
  1980年   1篇
排序方式: 共有1653条查询结果,搜索用时 15 毫秒
11.
全光亮镀铁工艺的研究   总被引:2,自引:0,他引:2  
介绍了一种新型的电镀光亮镀的工艺,使用了“抑氢剂”,并用小槽电镀,Hull Cell实验研究了镀液的性能,还运用线性电位扫描法,旋转圆盘电极法测试了镀液的阴极极化性能和整平性能,采用SEM法观察镀层的形貌,实验结果表明:光亮剂的加入可增大铁沉积时的阴极极化,并伴有整作用,而抑氢剂可增大氢在铁上析出的过电位,从而可提高铁沉积的电流效率并降低镀层的应力。  相似文献   
12.
We report a Raman technique applicable for the in situ analysis of the development of hydrogen bonds in the liquid water‐rich phase just before the onset of gas hydrate formation. Herewith, the phase transition as well as the working principle of hydrate formation inhibitors and promoters can be analyzed. © 2015 The Authors. Journal of Raman Spectroscopy published by John Wiley & Sons Ltd.  相似文献   
13.
14.
Pharyngoesophageal gastric acid reflux is thought to initiate chronic posterior laryngitis. The gold standard for measuring gastric reflux is dual-channel 24-hour pH monitoring. This is a time-consuming, inconvenient, expensive method that is not available in all areas. New therapeutic regimes that make use of proton pump inhibitors (PPIs) have proven to be therapeutically efficient for control of acid reflux. Twenty-four consecutive patients with chronic voice disorders and signs of posterior laryngitis were selected for therapy. Twenty-four hour pH monitoring was performed independently before the therapy. The trial therapy consisted of all patients receiving pantoprazole, 40 mg once daily for 6 weeks. Immediately following the therapy a statistically significant (p < 0.05) improvement was observed in all patients. This improvement was analyzed retrospectively by comparison with the results of 24-hour pH monitoring. In 71% of the patients the 24-hour pH-monitoring gave a positive result showing a high number of patients with extraesophageal reflux in our study group. Patients with positive results of pH-monitoring responded in a statistically significant manner (p < 0.05) to the pantoprazole therapy, whereas those patients without detected reflux did not. A 3-month follow-up of the patients with a positive result of the pH-monitoring confirmed the improvement. No patients reported adverse effects. A 6-week treatment with pantoprazole can be clinically justified. It helps to save time and reduce costs, allows for selection of reflux-negative patients for alternative therapy, and may prevent inadequate treatment of patients with false-negative pH monitoring. Twenty-four hour pH monitoring is still recommended for patients unresponsive to this trial therapy.  相似文献   
15.
The inhibitory activities, sulfhydryl bonds and far-UV circular dichroism (CD) spectra of Kunitz and Bowman–Birk soybean trypsin inhibitors (KTI and BBTI) were measured before and after ultrasound treatments. The differences between KTI and BBTI in conformation changes and resistance to ultrasound were observed. The secondary structures of KTI were found to be composed of β-sheet (22.5%), β-turn (16.2%) and random coils (61.4%) while that of BBTI composed of only β-sheet (52.6%) and random coils (47.4%). KTI lost its inhibitory activity more quickly than BBTI, proportionally to the ultrasound amplitudes and sonication durations used. Relevant synchronous phenomena observed included the inactivation of KTI, significant rise in sulfhydryl content and corresponding conformation changes, in which there were dramatic decreases in both β-turn and random coil contents and increase in the β-sheet structure over the entire sonication duration and ultrasonic amplitude scale used by the study. Ultrasound affected the activities and conformations of KTI and BBTI by exerting an influence on their disulfide bonds. For KTI, up to 55% of inhibitory activity could be inactivated, at which about 71.5% of disulfide bonds were altered and the [θ]200nm value was changed from native −2545 deg cm2 dmol−1 to −1827 deg cm2 dmol−1. Whereas for BBTI, far-UV CD spectra, β-sheet and random structures were barely affected, only about 5.29% of disulfide bonds were found altered and the [θ]200nm value was changed only from native −797 deg cm2 dmol−1 to −700 deg cm2 dmol−1. It is concluded that ultrasound inactivates KTI by inducing a reduction in the disulfide bonds and then changes the conformations.  相似文献   
16.
本文基于密度泛函理论(DFT)的第一性原理研究了苯并三氮唑(BTA)分子吸附于铜表面的反应活性特征及其吸附在三种不同取向晶面时的电荷转移以及成键情况,结果表明:BTA分子的亲电和亲核活性中心为N(1)、N(2)和C(5),在铜表面垂直吸附时为化学吸附,Cu原子的最外层价电子转移到N(2)原子上,两者形成配位键;BTA分子在三种不同取向的铜表面吸附时的吸附能大小为:Cu(110)x>Cu(100)x>Cu(111)x(x=T、B、H),T表示顶位,B表示桥位,H表示空位;BTA吸附在Cu(111)面的转移电荷量:T(顶位)>B(桥位)>H(空位).  相似文献   
17.
Herein we report a facile synthesis of esters of bis‐α‐aminoalkylphosphinic acids obtained by an addition of Cbz‐protected phosphinic analogues of amino acid methyl esters to an appropriate imine in refluxing benzene. Complete deprotection of the esters could be achieved in one step by the action of 30% HBr in acetic acid.  相似文献   
18.
The aggregation coupled sedimentation of asphaltene particles in toluene and heptanes mixture are investigated in the presence of two asphaltene inhibitors including, dodecyle resorcinol (DR) and hazelnut oil. An image processing technique is adopted in the three sections in a settling column setup. The aggregation and sedimentation phenomena are evaluated through a time-driven Monte Carlo (MC) model. The results are in good agreement with the obtained experimental results. The results indicate that in controlling asphaltene sedimentation DR is more effective. The results also revealed that the hazelnut oil has a capacity to inhibit asphaltene sedimentation at high concentration.  相似文献   
19.
A new type of berberine derivatives was obtained by the reaction of berberrubine with aliphatic sulfonyl chlorides. The new polycyclic compounds have a sultone ring condensed to C and D rings of a protoberberine core. The reaction conditions were developed to facilitate the formation of sultones with high yields without by-product formation. Thus, it was shown that the order of addition of reagents affects the composition of the reaction products: when sulfochlorides are added to berberrubine, their corresponding 9-O-sulfonates are predominantly formed; when berberrubine is added to pre-generated sulfenes, sultones are the only products. The reaction was shown to proceed stereo-selectively and the cycle configuration was confirmed by 2D NMR spectroscopy. The inhibitory activity of the synthesized sultones and their 12-brominated analogs against the DNA-repair enzyme tyrosyl-DNA phosphodiesterase 1 (Tdp1), an important target for a potential antitumor therapy, was studied. All derivatives were active in the micromolar and submicromolar range, in contrast to the acyclic analogs and 9-O-sulfonates, which were inactive. The significance of the sultone cycle and bromine substituent in binding with the enzyme was confirmed using molecular modeling. The active inhibitors are mostly non-toxic to the HeLa cancer cell line, and several ligands show synergy with topotecan, a topoisomerase 1 poison in clinical use. Thus, novel berberine derivatives can be considered as candidates for adjuvant therapy against cancer.  相似文献   
20.
Solvothermal synthesis of multiple dihydropyrimidinones at a time has been developed in inexpensive and green bio-based solvent lactic acid without any additional catalysts or additives. By this method, thirty new dihydropyrimidinone derivatives were synthesized in two batches and characterized. All of the compounds were screened by Eg5 motor protein ATPase assay, and the positive compounds were tested against the Caco-2 cell line, HeLa cell line, L929 cell line and T24 cell line in vitro. Among them, compound C9 exhibited the best inhibitory activity against motor protein ATPase with an IC50 value of 30.25 μM and significant cytotoxic activity in the micromolar range against the cells above. The Lineweaver–Burk plot revealed that compound C9 was a mixed-type Eg5 inhibitor. A molecular modeling study using the Discovery Studio program was performed, where compound C9 exhibited good binding interaction with Eg5 motor protein ATPase, and this was consistent with the attained experimental results.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号