全文获取类型
收费全文 | 9605篇 |
免费 | 873篇 |
国内免费 | 3162篇 |
专业分类
化学 | 10020篇 |
晶体学 | 167篇 |
力学 | 110篇 |
综合类 | 95篇 |
数学 | 1556篇 |
物理学 | 1692篇 |
出版年
2024年 | 22篇 |
2023年 | 151篇 |
2022年 | 174篇 |
2021年 | 288篇 |
2020年 | 344篇 |
2019年 | 346篇 |
2018年 | 298篇 |
2017年 | 313篇 |
2016年 | 378篇 |
2015年 | 343篇 |
2014年 | 416篇 |
2013年 | 803篇 |
2012年 | 499篇 |
2011年 | 549篇 |
2010年 | 483篇 |
2009年 | 588篇 |
2008年 | 610篇 |
2007年 | 682篇 |
2006年 | 548篇 |
2005年 | 558篇 |
2004年 | 519篇 |
2003年 | 477篇 |
2002年 | 382篇 |
2001年 | 375篇 |
2000年 | 303篇 |
1999年 | 289篇 |
1998年 | 261篇 |
1997年 | 236篇 |
1996年 | 228篇 |
1995年 | 181篇 |
1994年 | 179篇 |
1993年 | 195篇 |
1992年 | 189篇 |
1991年 | 136篇 |
1990年 | 128篇 |
1989年 | 147篇 |
1988年 | 151篇 |
1987年 | 162篇 |
1986年 | 156篇 |
1985年 | 146篇 |
1984年 | 134篇 |
1983年 | 87篇 |
1982年 | 35篇 |
1981年 | 32篇 |
1980年 | 22篇 |
1979年 | 23篇 |
1978年 | 14篇 |
1977年 | 13篇 |
1976年 | 10篇 |
1974年 | 15篇 |
排序方式: 共有10000条查询结果,搜索用时 140 毫秒
91.
Jana Beinhauer Liangqiao Bian Hui Fan Marek Šebela Maciej Kukula Jose A. Barrera Kevin A. Schug 《Analytica chimica acta》2015
Estrone (E1), estradiols (α/β-E2), and estriol (E3) are four major metabolically active estrogens exerting strong biological activities at very low circulating concentrations. This paper reports a sensitive and efficient method with automated, on-line clean-up and detection to determine trace estrogens in a small volume of serum samples using liquid chromatography–electrospray ionization–tandem mass spectrometry directly, without off-line liquid–liquid or solid-phase extraction pretreatments. Serum aliquots (charcoal stripped fetal bovine serum, 100 μL) were spiked with four estrogen standards and their corresponding isotope-labeled internal standards, then bulk derivatized with 2-fluoro-1-methyl-pyridium p-toluenesulfonate (2-FMP) to establish the calibration curves and perform method validation. Calibration was established in the concentration ranges of 5–1000 pg mL−1, and demonstrated good linearity of R2 from 0.9944 to 0.9997 for the four derivatized estrogens. The lower detection limits obtained were 3–7 pg mL−1. Good accuracy and precision in the range of 86–112% and 2.3–11.9%, respectively, were observed for the quality control (QC) samples at low, medium, and high concentration levels. The stability tests showed that the derivatized serum samples were stable 8 h after derivatization at room temperature and at least to 48 h if stored at −20 °C. The method was applied to measure trace estrogens in real human and bovine serum samples, and three of four estrogen compounds studied were observed and quantified. 相似文献
92.
Tobias Becherer Christian Grunewald Vivienne Engelschalt Gerhard Multhaup Thomas Risse Rainer Haag 《Analytica chimica acta》2015
Coatings based on dendritic polyglycerol (dPG) were investigated for their use to control nonspecific protein adsorption in an assay targeted to analyze concentrations of a specific protein. We demonstrate that coating of the sample vial with dPG can significantly increase the recovery of an antibody after incubation. First, we determine the concentration dependent loss of an antibody due to nonspecific adsorption to glass via quartz crystal microbalance (QCM). Complementary to the QCM measurements, we applied the same antibody as analyte in an surface plasmon resonance (SPR) assay to determine the loss of analyte due to nonspecific adsorption to the sample vial. For this purpose, we used two different coatings based on dPG. For the first coating, which served as a matrix for the SPR sensor, carboxyl groups were incorporated into dPG as well as a dithiolane moiety enabling covalent immobilization to the gold sensor surface. This SPR-matrix exhibited excellent protein resistant properties and allowed the immobilization of amyloid peptides via amide bond formation. The second coating which was intended to prevent nonspecific adsorption to glass vials comprised a silyl moiety that allowed covalent grafting to glass. For demonstrating the impact of the vial coating on the accuracy of an SPR assay, we immobilized amyloid beta (Aβ) 1-40 and used an anti-Aβ 1-40 antibody as analyte. Alternate injection of analyte into the flow cell of the SPR device from uncoated and coated vials, respectively gave us the relative signal loss (1 − RUuncoated/RUcoated) caused by the nonspecific adsorption. We found that the relative signal loss increases with decreasing analyte concentration. The SPR data correlate well with concentration dependent non-specific adsorption experiments of the analyte to glass surfaces performed with QCM. Our measurements show that rendering both the sample vial and the sensor surface is crucial for accurate results in protein assays. 相似文献
93.
Rücktitelbild: Cofactor‐Free Light‐Driven Whole‐Cell Cytochrome P450 Catalysis (Angew. Chem. 3/2015)
94.
Theoretical insight of nitric oxide adsorption on neutral and charged Pdn (n = 1–5) clusters 下载免费PDF全文
Pakiza Begum Pranjal Gogoi Bhupesh Kumar Mishra Ramesh Chandra Deka 《International journal of quantum chemistry》2015,115(13):837-845
Density functional theory (DFT) calculations within the framework of generalized gradient approximation have been used to systematically investigate the adsorption of nitric oxide (NO) molecule on neutral, cationic, and anionic Pdn (n = 1–5) clusters. NO coordinate to one Pd atom of the cluster by the end‐on mode, where the tilted end‐on structure is more favorable due to the additional electron in the π* orbital. On the contrary, in the neutral and cationic Pd2 system, NO coordinates to the bridge site of cluster preferably by the side‐on mode. Charge transfer between Pd clusters and NO molecule and the corresponding weakening of N? O bond is an essential factor for the adsorption. The N? O stretching frequency follow the order of cationic > neutral > anionic. Binding energy of NO on anionic clusters is found to be greater than those of neutral and cationic clusters. © 2015 Wiley Periodicals, Inc. 相似文献
95.
QM/MM modeling of the hydroxylation of the androstenedione substrate catalyzed by cytochrome P450 aromatase (CYP19A1) 下载免费PDF全文
Ignacio Viciano Raquel Castillo Sergio Martí 《Journal of computational chemistry》2015,36(23):1736-1747
CYP19A1 aromatase is a member of the Cytochrome P450 family of hemeproteins, and is the enzyme responsible for the final step of the androgens conversion into the corresponding estrogens, via a three‐step oxidative process. For this reason, the inhibition of this enzyme plays an important role in the treatment of hormone‐dependent breast cancer. The first catalytic subcycle, corresponding to the hydroxilation of androstenedione, has been proposed to occur through a first hydrogen abstraction and a subsequent oxygen rebound step. In present work, we have studied the mechanism of the first catalytic subcycle by means of hybrid quantum mechanics/molecular mechanics methods. The inclusion of the protein flexibility has been achieved by means of Free Energy Perturbation techniques, giving rise to a free energy of activation for the hydrogen abstraction step of 13.5 kcal/mol. The subsequent oxygen rebound step, characterized by a small free energy barrier (1.5 kcal/mol), leads to the hydroxylated products through a highly exergonic reaction. In addition, an analysis of the primary deuterium kinetic isotopic effects, calculated for the hydrogen abstraction step, reveals values (~10) overpassing the semiclassical limit for the C? H, indicating the presence of a substantial tunnel effect. Finally, a decomposition analysis of the interaction energy for the substrate and cofactor in the active site is also discussed. According to our results, the role of the enzymatic environment consists of a transition state stabilization by means of dispersive and polarization effects. © 2015 Wiley Periodicals, Inc. 相似文献
96.
NiP和MoS催化剂在二苯并噻吩加氢脱硫反应中的氢溢流效应 《燃料化学学报》2015,43(6):708-713
对分层装填的Ni2P//MoS2催化剂上的二苯并噻吩加氢脱硫反应进行了研究。结果表明,分层装填的Ni2P/Al2O3和MoS2/Al2O3催化剂在二苯并噻吩加氢脱硫反应中存在氢溢流效应,氢溢流有助于提高MoS2催化剂的活性位密度和加氢脱硫反应速率。由于Ni2P比NiSx具有更强的氢分子解离能力,Ni2P//MoS2催化体系的氢溢流因子略高于NiSx//MoS2;相对于NiSx,Ni2P对MoS2催化剂是更好的助剂。 相似文献
97.
BImCl/CuCl离子液体脱除MTBE中硫醇机制及性能研究 《燃料化学学报》2015,43(9):1113-1119
以N-丁基咪唑、HCl和CuCl为原料两步法合成了离子液体[BIm]Cl/CuCl,并用傅里叶变换红外光谱FT-IR和傅里叶变换离子回旋共振质谱FT-ICR MS对其结构进行表征。采用差热扫描量热仪DSC、FT-IR以及紫外可见光谱UV-vis对吸附硫醇的[BIm]Cl/CuCl进行分析,讨论了[BIm]Cl/CuCl吸附硫醇的作用机制。以[BIm]Cl/CuCl为吸附剂,采用吸附蒸馏工艺脱除MTBE中的硫化物,MTBE硫含量可降低至5 μg/g以下,吸附剂进行多次循环使用且脱硫效果无明显降低。 相似文献
98.
溶剂极性控制下的煤抽余物吸附甲烷能力研究 《燃料化学学报》2015,43(10):1153-1157
基于原煤和有机溶剂抽余物的等温吸附实验结果,对比分析溶剂极性与其煤抽余物吸附甲烷能力变化关系,探讨抽提溶剂极性差异对煤抽余物吸附甲烷能力控制的地球化学机理。结果表明,煤溶剂抽余物等温吸附甲烷曲线都遵循Langmuir方程,且二硫化碳(CS2)和苯(C6H6)溶剂抽提作用增大了煤吸附甲烷量,四氢呋喃(THF)和丙酮溶剂抽提作用减小了煤吸附甲烷量。实验发现,煤抽余物吸附甲烷能力变化与抽提溶剂极性成负相关关系,该现象可用相似相容原理解释:CS2和C6H6溶剂极性较弱,抽提出较多具有非极性结构(-CH3和-CH2-)的烷烃和芳烃,为甲烷在煤表面吸附增多了吸附位而增强了抽余物吸附甲烷能力,THF和丙酮溶剂极性较强,抽提出较多具有极性结构(-CHO、-OH、和-COOH)的非烃和沥青质,减少了吸附位而降低煤抽余物的甲烷吸附能力。 相似文献
99.
100.
Ru添加对Co/SiO费托合成催化剂性能的影响 《燃料化学学报》2015,43(10):1230-1238
用初湿含浸法制备了不同Ru添加量的Co/SiO2模型催化剂,然后进行N2物理吸附、XRD、H2-TPD、DRIFTS等表征和微分固定床费托(F-T)反应评价。F-T反应结果表明,催化剂中添加Ru后,CO转化率显著提高,TOF值增大,CO2和CH4选择性降低,烯/烷比(O/P)降低。FT-IR表征说明,催化剂添加Ru后Co-O键的强度减弱,相对应的H2-TPR也表明,催化剂的还原度得到显著提高。还原后的催化剂XRD结果进一步证实,加入Ru后,催化剂无钴氧化物被检出,并且当Ru添加量为0.5%(质量分数)时催化剂中金属钴主要以六方密堆(hcp)形式存在。CO-DRIFTS结果显示,Ru的加入使CO的吸收峰发生红移,即Ru促进了CO的解离。H2-TPD结果则表明,随着Ru添加量的增加,催化剂表面COads/Cos和CO*/Cos增大,这是CH4选择性降低的主要原因。 相似文献