全文获取类型
收费全文 | 1990篇 |
免费 | 261篇 |
国内免费 | 240篇 |
专业分类
化学 | 1391篇 |
晶体学 | 20篇 |
力学 | 88篇 |
综合类 | 4篇 |
数学 | 330篇 |
物理学 | 658篇 |
出版年
2024年 | 2篇 |
2023年 | 47篇 |
2022年 | 42篇 |
2021年 | 78篇 |
2020年 | 101篇 |
2019年 | 71篇 |
2018年 | 61篇 |
2017年 | 66篇 |
2016年 | 95篇 |
2015年 | 87篇 |
2014年 | 92篇 |
2013年 | 139篇 |
2012年 | 158篇 |
2011年 | 172篇 |
2010年 | 92篇 |
2009年 | 113篇 |
2008年 | 125篇 |
2007年 | 119篇 |
2006年 | 93篇 |
2005年 | 94篇 |
2004年 | 54篇 |
2003年 | 42篇 |
2002年 | 40篇 |
2001年 | 44篇 |
2000年 | 46篇 |
1999年 | 37篇 |
1998年 | 26篇 |
1997年 | 27篇 |
1996年 | 42篇 |
1995年 | 35篇 |
1994年 | 34篇 |
1993年 | 28篇 |
1992年 | 24篇 |
1991年 | 33篇 |
1990年 | 25篇 |
1989年 | 14篇 |
1988年 | 15篇 |
1987年 | 13篇 |
1986年 | 11篇 |
1985年 | 10篇 |
1984年 | 11篇 |
1983年 | 4篇 |
1982年 | 8篇 |
1981年 | 5篇 |
1980年 | 4篇 |
1979年 | 5篇 |
1977年 | 2篇 |
1975年 | 2篇 |
1968年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有2491条查询结果,搜索用时 15 毫秒
111.
Wen Zhou Xiao-Li Sun Lin Gu Fei-Fei Bao Xin-Xin Xu Chun-Yan Pang Zhi-Guo Gu Zaijun Li 《Journal of Radioanalytical and Nuclear Chemistry》2014,300(2):843-852
Three new mesoporous silica materials IL15SGs (HF15SG, TF15SG and DF15SG) doped with benzo-15-crown-5 and imidazolium based ionic liquids (C8mim+PF6 ?, C8mim+BF4 ? or C8mim+NTf 2 ? ) have been prepared by a simple approach to separating lithium isotopes. The formed mesoporous structures of silica gels have been confirmed by transmission electron microscopy image and N2 gas adsorption–desorption isotherm. Imidazolium ionic liquids acted as templates to prepare mesoporous materials, additives to stabilize extractant within silica gel, and synergetic agents to separate the lithium isotopes. Factors such as lithium salt concentration, initial pH, counter anion of lithium salt, extraction time, and temperature on the lithium isotopes separation were examined. Under optimized conditions, the extraction efficiency of HF15SG, TF15SG and DF15SG were found to be 11.43, 10.59 and 13.07 %, respectively. The heavier isotope 7Li was concentrated in the solution phase while the lighter isotope 6Li was enriched in the gel phase. The solid–liquid extraction maximum single-stage isotopes separation factor of 6Li–7Li in the solid–liquid extraction was up to 1.046 ± 0.002. X-ray crystal structure analysis indicated that the lithium salt was extracted into the solid phase with crown ether forming [(Li0.5)2(B15)2(H2O)]+ complexes. IL15SGs were also easily regenerated by stripping with 20 mmol L?1 HCl and reused in the consecutive removal of lithium ion in five cycles. 相似文献
112.
Ariane Wohlfarth Adarsh S. Gandhi Shaokun Pang Mingshe Zhu Karl B. Scheidweiler Marilyn A. Huestis 《Analytical and bioanalytical chemistry》2014,406(6):1763-1780
Background
PB-22 (1-pentyl-8-quinolinyl ester-1H-indole-3-carboxylic acid) and 5F-PB-22 (1-(5-fluoropentyl)-8-quinolinyl ester-1H-indole-3-carboxylic acid) are new synthetic cannabinoids with a quinoline substructure and the first marketed substances with an ester bond linkage. No human metabolism data are currently available, making it difficult to document PB-22 and 5F-PB-22 intake from urine analysis, and complicating assessment of the drugs’ pharmacodynamic and toxicological properties.Methods
We incubated 10 μmol/l PB-22 and 5F-PB-22 with pooled cryopreserved human hepatocytes up to 3 h and analyzed samples on a TripleTOF 5600+ high-resolution mass spectrometer. Data were acquired via TOF scan, followed by information-dependent acquisition triggered product ion scans with mass defect filtering (MDF). The accurate mass full scan MS and MS/MS metabolite datasets were analyzed with multiple data processing techniques, including MDF, neutral loss and product ion filtering.Results
The predominant metabolic pathway for PB-22 and 5F-PB-22 was ester hydrolysis yielding a wide variety of (5-fluoro)pentylindole-3-carboxylic acid metabolites. Twenty metabolites for PB-22 and 22 metabolites for 5F-PB-22 were identified, with the majority generated by oxidation with or without glucuronidation. For 5F-PB-22, oxidative defluorination occurred forming PB-22 metabolites. Both compounds underwent epoxide formation followed by internal hydrolysis and also produced a cysteine conjugate.Conclusion
Human hepatic metabolic profiles were generated for PB-22 and 5F-PB-22. Pentylindole-3-carboxylic acid, hydroxypentyl-PB-22 and PB-22 pentanoic acid for PB-22, and 5′-fluoropentylindole-3-carboxylic acid, PB-22 pentanoic acid and the hydroxy-5F-PB-22 metabolite with oxidation at the quinoline system for 5F-PB-22 are likely the best targets to incorporate into analytical methods for urine to document PB-22 and 5F-PB-22 intake.Metabolism of synthetic cannabinoids PB-22 and 5F-PB-22 by human hepatocyte incubation and high-resolution mass spectrometry 相似文献
113.
Lihong Lin Wei Yu Yanan Pang Changsong Sun Qinghe Meng Xiaolei Li Xingjie Guo 《Analytical and bioanalytical chemistry》2014,406(22):5521-5526
A simple, sensitive, and reliable liquid chromatography tandem mass spectrometry (LC-MS/MS) method has been developed for determination of pyraoxystrobin in rat plasma and applied to a toxicokinetics study. The separation was performed by gradient elution on a Luna 5 μ C18 (2) 100 Å column (50?×?4.6 mm I.D., 5 μm) with mobile phase: water (0.1 % formic acid, v/v)/acetonitrile (0.1 % formic acid, v/v), followed by quantification with a mass detector in multiple reaction monitoring (MRM) mode using ESI as an interface. The calibration curve was linear over a concentration range of 1.00–200 ng/mL. The recovery for pyraoxystrobin ranged from 101.4 to 108.2 %. The intraday bias and precision ranged from ?9.3 to 8.1 % and from 0.7 to 8.4 %, respectively, and the interday bias and precision ranged from ?0.3 to 4.0 % and from 4.4 to 7.2 %, respectively. The toxicokinetics of pyraoxystrobin after single 100 and 1,000 mg/kg oral doses were studied in rats. Figure
The chromatogram of pyraoxystrobin highest calibration standard (ULOQ) extract. 相似文献
114.
运用分子动力学模拟,研究了腺苷酸(激动剂)与A2AAR腺苷受体蛋白的相互作用和配体结合诱导的蛋白动力学变化.识别了与腺苷酸结合力强于0.5kcal/mol的关键基团:A63^2.61,I66^2.64,V84^3.32,L85^3.33,T88^3.36,F168^5.29,M177^5.38,L249^6.51,H250^6.52和N253^6.55,观察到腺苷酸没有与L167^5.28相互作用,这一结果支持了L167^5.28是抑制剂特异性结合位点,不与激动剂结合.未结合配体(激动剂或抑制剂)的单体A2AAR和腺苷酸结合后的A2AAR在构象上有三个不同功能性开关.腺苷酸结合可以诱导A2AAR腺苷受体蛋白的构象调整,使得三个功能性开关器件的构象与单体A2AAR不同. 相似文献
115.
Dr. Wei Liu Dr. Qiu‐Han Lin Dr. Yu‐Zhang Yang Dr. Xue‐Jiao Zhang Prof. Yu‐Chuan Li Dr. Zhi‐Hui Lin Prof. Si‐Ping Pang 《化学:亚洲杂志》2014,9(2):479-486
A family of energetic salts with high thermal stability and low impact sensitivity based on an oxygen‐containing cation, 2,4‐diamino‐1,3,5‐triazine‐6‐one, were synthesized and fully characterized by IR and multinuclear (1H, 13C) NMR spectroscopy, elemental analysis, and differential scanning calorimetry. Insights into their sensitivities towards impact, friction, and electrostatics were gained by submitting the materials to standard tests. The structures of 2,4‐diamino‐1,3,5‐triazine‐6‐one nitrate, 2,4‐diamino‐1,3,5‐triazine‐6‐one sulfate, 2,4‐diamino‐1,3,5‐triazine‐6‐one perchlorate, 2,4‐diamino‐1,3,5‐triazine‐6‐one 5‐nitrotetrazolate were determined by single‐crystal X‐ray diffraction; their densities are 1.691, 1.776, 1.854, and 1.636 g cm?3, respectively. Most of the salts decompose at temperatures over 180 °C; in particular, the salts 2,4‐diamino‐1,3,5‐triazine‐6‐one nitrate and 2,4‐diamino‐1,3,5‐triazine‐6‐one perchlorate, which decompose at 303.3 and 336.4 °C, respectively, are fairly stable. Furthermore, most of the salts exhibit excellent impact sensitivities (>40 J), friction sensitivities (>360 N), and are insensitive to electrostatics. The measured densities of these energetic salts range from 1.64 to 2.01 g cm?3. The detonation pressure values calculated for these salts range from 14.6 to 29.2 GPa, and the detonation velocities range from 6536 to 8275 m s?1; these values make the salts potential candidates for thermally stable and insensitive energetic materials. 相似文献
116.
Shupeng Liu Jing Huang Zhenyi Chen Na Chen Fufei Pang Tingyun Wang Linshui Hu 《Journal of Raman spectroscopy : JRS》2015,46(2):197-201
Liquid chromatography and mass spectrometry were time‐consuming and expensive as the main methods for the drug analysis at present, and the samples must be pretreated. The Raman spectroscopy measurement methods were fast and simple, so the Raman spectroscopy methods for the drug analysis were explored in this paper. An optical fiber nano‐probe coated with gold nanoparticles was fabricated and used with surface‐enhanced Raman spectroscopy (SERS) to measure levofloxacin lactate. The resulting SERS spectra of levofloxacin lactate in mouse blood that was detected by the optical fiber nano‐probe clearly showed the characteristic wave numbers of levofloxacin lactate, indicating that optical fiber nano‐probes can be used with spectral techniques to analyze drugs in vitro or potentially even in vivo. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
117.
Qin Kaiwei Guo Lei Ming Shujun Zhang Shoute Guo Yanbin Pang Lei Li Tao 《Catalysis Surveys from Asia》2022,26(2):115-128
Catalysis Surveys from Asia - The catalytic performances and mechanism differences of model catalysts Cu–SSZ-13 and Fe–SSZ-13 with similar metal content and Si/Al ratio were compared.... 相似文献
118.
Jun-Jie Shi Qi-Hui Jiang Tian-Ning Zhang Hao Sun Wen-Wen Shi Hendra Gunosewoyo Fan Yang Jie Tang Tao Pang Li-Fang Yu 《Molecules (Basel, Switzerland)》2021,26(5)
Sigma-1 (σ-1) receptor agonists are considered as potential treatment for stroke. TS-157 is an alkoxyisoxazole-based σ-1 receptor agonist previously discovered in our group. The present study describes TS-157 profile in a battery of tests for cerebral ischemia. Initial evaluation demonstrated the compound’s safety profile and blood–brain barrier permeability, as well as its ability to induce neurite outgrowth in vitro. The neurite outgrowth was shown to be mediated via σ-1 receptor agonism and involves upregulation of ERK phosphorylation (pERK). In particular, TS-157 also significantly accelerated the recovery of motor function in rats with transient middle cerebral artery occlusion (tMCAO). Overall, the results herein support the notion that σ-1 receptor agonists are potential therapeutics for stroke and further animal efficacy studies are warranted. 相似文献
119.
采用溶胶凝胶法以及静电纺丝法, 利用热处理工艺, 成功制备出了多晶锐钛矿型TiO2纳米线, 通过两线法在室温下测试单根TiO2纳米线的V-I曲线来研究其电输运性能及磁阻效应. 结果表明: 在无光照环境下其V-I曲线为不过零点的直线, 零场电阻较大, 在磁场作用下电阻下降, 表现出负磁阻效应; 紫外光辐照环境下TiO2纳米线载流子浓度增加使得电阻变小, 然而在磁场作用下电阻增大, 表现为正磁阻效应. 紫外光辐照导致的载流子浓度变化, 使得负磁阻转变为正磁阻, 我们将磁阻变化归结为d电子局域导致的负磁阻与能带劈裂导致的正磁阻两种机理相互竞争的结果. 相似文献
120.
乙炔氢氯化反应中的负载金-离子液体催化剂:离子态金物种的稳定机制 总被引:1,自引:0,他引:1
聚氯乙烯(PVC)作为世界通用工程塑料之一,具有优异的物理、化学和机械性能,在工业、农业、建筑、包装、电力等行业中应用广泛.氯乙烯是生产聚氯乙烯的重要单体.氯乙烯的生产主要有电石法和乙烯法两种工艺路线,由于我国“贫油、富煤、少气”的资源现状,电石法产能占全部产能的83%以上.电石法生产氯乙烯的原理是在氯化汞催化剂存在下,将电石水解精制后的乙炔气与氯化氢加成直接合成氯乙烯.随着节能减排及环保要求的逐渐提高和国际涉汞公约的实施,开发新一代绿色无汞催化剂具有重要的战略意义.近年来,金基催化剂是无汞催化剂基础研究和技术开发中最重要的方向.在之前的工作中,我们课题组首先报道了负载离子液体-金催化剂体系(Au-SILP)在电石法生产氯乙烯工艺中的应用,并发现离子液体的存在可以显著提高金活性物种在载体表面的分散度和稳定其化学价态.在后续研究中,我们在负载离子液体-金催化体系中引入金属铜离子(Cu^2+),利用反应过程中Au-Cu之间的氧化还原循环,设计并制备了金属铜基配位离子液体,构建了负载离子液体-金-铜催化剂体系.铜离子的引入形成了一个催化剂自身维持氧化态的微环境,实现了被还原金物种的原位氧化再生.本文在上述研究基础上,利用配位离子液体[Bmim][N(CN)2]中[N(CN)2^–]阴离子和阳离子金之间的强配位作用,构建出比Au-Cl键更稳定的Au–N键,并通过X射线光电子能谱(XPS)、球差校正-扫描透射电镜(AC-STEM)和扩展X射线吸收精细结构(EXAFS)表征证明了Au以单原子状态存在于载体表面.制备的Au-N(CN)2/AC催化剂在乙炔氢氯化反应中表现出比Au-Cl/AC和Au/AC催化剂更高的稳定性和催化活性以及更短的诱导期.进一步表征分析发现,[N(CN)2^–]配体促进了阳离子金和配体之间的电子转移,提高了阳离子金的电子云密度,削弱了乙炔在阳离子金上的吸附强度,抑制了其还原,提高了催化剂的稳定性.更重要的是,与阳离子金配位的[N(CN)2^–]配体使得反应过程中的氯化氢在氮位点发生化学解离,促进了氯化氢活化,同时降低了反应能垒.对负载配位离子液体-金催化体系反应诱导期的分析结果表明,反应诱导期与反应物(乙炔、氯化氢)分子在离子液体层中的溶解度无关,而主要取决于催化剂中Au(Ⅲ)物种的含量和反应物分子在离子液体中的扩散速率.上述研究结果进一步深化了离子液体和活性金物种之间电子的作用机理,建立了负载离子液体-金催化剂体系对反应物的活化机制和反应机理,为进一步开发具有工业应用价值的乙炔氢氯化反应无汞催化剂提供了科学基础和参考. 相似文献