全文获取类型
收费全文 | 6811篇 |
免费 | 976篇 |
国内免费 | 551篇 |
专业分类
化学 | 4783篇 |
晶体学 | 32篇 |
力学 | 364篇 |
综合类 | 16篇 |
数学 | 789篇 |
物理学 | 2354篇 |
出版年
2024年 | 22篇 |
2023年 | 151篇 |
2022年 | 214篇 |
2021年 | 283篇 |
2020年 | 281篇 |
2019年 | 239篇 |
2018年 | 219篇 |
2017年 | 177篇 |
2016年 | 290篇 |
2015年 | 280篇 |
2014年 | 371篇 |
2013年 | 454篇 |
2012年 | 602篇 |
2011年 | 619篇 |
2010年 | 412篇 |
2009年 | 348篇 |
2008年 | 423篇 |
2007年 | 373篇 |
2006年 | 348篇 |
2005年 | 265篇 |
2004年 | 201篇 |
2003年 | 158篇 |
2002年 | 129篇 |
2001年 | 131篇 |
2000年 | 124篇 |
1999年 | 134篇 |
1998年 | 107篇 |
1997年 | 92篇 |
1996年 | 122篇 |
1995年 | 103篇 |
1994年 | 70篇 |
1993年 | 63篇 |
1992年 | 69篇 |
1991年 | 57篇 |
1990年 | 74篇 |
1989年 | 53篇 |
1988年 | 34篇 |
1987年 | 29篇 |
1986年 | 24篇 |
1985年 | 18篇 |
1984年 | 16篇 |
1983年 | 16篇 |
1982年 | 15篇 |
1981年 | 10篇 |
1979年 | 20篇 |
1978年 | 15篇 |
1977年 | 14篇 |
1976年 | 10篇 |
1975年 | 13篇 |
1973年 | 13篇 |
排序方式: 共有8338条查询结果,搜索用时 15 毫秒
961.
Facile Access to cis‐2,6‐Disubstituted Tetrahydropyrans by Palladium‐Catalyzed Decarboxylative Allylation: Total Syntheses of (±)‐Centrolobine and (+)‐Decytospolides A and B 下载免费PDF全文
Jing Zeng Yu Jia Tan Dr. Jimei Ma Min Li Leow Davin Tirtorahardjo Prof. Dr. Xue‐Wei Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(2):405-409
cis‐2,6‐Tetrahydropyran is an important structural skeleton of bioactive natural products. A facile synthesis of cis‐2,6‐disubstituted‐3,6‐dihydropyrans as cis‐2,6‐tetrahydropyran precursors has been achieved in high regio‐ and stereoselectivity with high yields. This reaction involves a palladium‐catalyzed decarboxylative allylation of various 3,4‐dihydro‐2H‐pyran substrates. Extending this reaction to 1,2‐unsaturated carbohydrates allowed the achievement of challenging β‐C‐glycosylation. Based on this methodology, the total syntheses of (±)‐centrolobine and (+)‐decytospolides A and B were achieved in concise steps and overall high yields. 相似文献
962.
Efficient Copper‐Catalyzed Direct Intramolecular Aminotrifluoromethylation of Unactivated Alkenes with Diverse Nitrogen‐Based Nucleophiles 下载免费PDF全文
Dr. Jin‐Shun Lin Ya‐Ping Xiong Can‐Liang Ma Li‐Jiao Zhao Prof. Dr. Bin Tan Prof. Dr. Xin‐Yuan Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(5):1332-1340
A mild, convenient, and step‐economical intramolecular aminotrifluoromethylation of unactivated alkenes with a variety of electronically distinct, nitrogen‐based nucleophiles in the presence of a simple copper salt catalyst, in the absence of extra ligands, is described. Many different nitrogen‐based nucleophiles (e.g., basic primary aliphatic and aromatic amines, sulfonamides, carbamates, and ureas) can be employed in this new aminotrifluoromethylation reaction. The aminotrifluoromethylation process allows straightforward access to diversely substituted CF3‐containing pyrrolidines or indolines, in good to excellent yields, through a direct difunctionalization strategy from the respective acyclic starting materials. Mechanistic studies were conducted and a plausible mechanism was proposed. 相似文献
963.
Clickable Periodic Mesoporous Organosilicas: Synthesis,Click Reactions,and Adsorption of Antibiotics 下载免费PDF全文
Dr. Jinsuo Gao Xueying Zhang Dr. Shutao Xu Prof. Feng Tan Prof. Xinyong Li Prof. Yaobin Zhang Prof. Zhenping Qu Prof. Xie Quan Dr. Jian Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(7):1957-1963
Pharmaceutical antibiotics are not easily removed from water by conventional water‐treatment technologies and have been recognized as new emerging pollutants. Herein, we report the synthesis of clickable azido periodic mesoporous organosilicas (PMOs) and their use as adsorbents for the adsorption of antibiotics. Ethane‐bridged PMOs, functionalized with azido groups at different densities, were synthesized by the co‐condensation of 1,2‐bis(trimethoxysilyl)ethane (BTME) and 3‐azidopropyltrimethoxysilane (AzPTMS), in the presence of nonionic‐surfactant triblock‐copolymer P123, in an acidic medium. Four different alkynes were conjugated to azide‐terminated PMOs by means of an efficient click reaction. The clicked PMOs showed improved adsorption capacity (241 μg g?1) for antibiotics (ciprofloxacin hydrochloride) compared with azido‐functionalized PMOs because of the enhanced π–π stacking interactions. These results indicate that click reactions can introduce multifunctional groups onto PMOs, thus demonstrating the great potential of PMOs for environmental applications. 相似文献
964.
Picomole‐level Formaldehyde Determination in Gaseous and Beer Samples Using Flow Injection Chemiluminescence Analysis 下载免费PDF全文
Based on the linear enhancement of formaldehyde (FA) within 7.0 ~ 1000 pmol l?1 on luminol—bovine serum albumin (BSA) chemiluminescence (CL) system, FA determination in air and beer samples using CL with flow injection (FI) was proposed. The detection limit was 2.5 pmol l?1 (3σ) and the relative standard deviations were less than 4.5% (n = 7). At a flow rate of 2.0 mL min?1, a whole analysis from sampling to washing only needed 32 s, offering a sample throughput of 112 h?1. This proposed method was successfully utilized to determine FA vapor pressure in liquid (121.8 ± 3.8 Pa), FA content in real air sample (8.93 ± 0.03 mg m?3), and FA levels in beer (199.5 ± 5.6 ~ 225.2 ± 3.5 mg l?1), giving determination recoveries from 90.7% to 109.3%. The mechanism of BSA—FA interaction was also investigated, showing FA binding to BSA was a spontaneous process mainly through hydrogen bonding and van der Waals force by FI‐CL, with binding constant K of 1.89 × 106 l mol?1 and the number of binding sites n of 0.86. Molecular docking analysis further revealed FA could enter into the pocket at subdomain IIA of BSA, with K of 1.71 × 105 l mol?1 and ΔG of ‐29.68 kJ mol?1. 相似文献
965.
Screening and analysis of metabolites in rat urine after oral administration of Apocynum venetum L. extracts using HPLC–TOF‐MS 下载免费PDF全文
Liang Zhao Lei Lv Hai Zhang Guang guo‐Tan Yifeng Chai Guoqing Zhang 《Journal of separation science》2014,37(5):515-526
HPLC with diode array detection and ESI‐TOF‐MS was used for the study of the constituents in Apocynum venetum L. extracts and the metabolites in rat urine after oral administration of A. venetum L. extracts. A formula database of the known constituents in A. venetum L. was established, and 21 constituents were rapidly identified by accurately matching their molecular masses with the formulae of the compounds in the database. Furthermore, 34 metabolites were detected and elucidated in the rat urine. The scientific and plausible biotransformation pathways of the flavonoid components in A. venetum L. were also proposed together with the presentation of clues for potential mechanisms of bioactivity. This specific and sensitive HPLC–ESI‐TOF‐MS method can be used to identify the chemical components in the extracts of A. venetum L. and their metabolites in rat urine. This method can also be used to reveal the possible metabolic mechanisms of action of the extract components in vivo. 相似文献
966.
Xu-Feng Tan Li-Yong Yuan Chang-Ming Nie Kui Lui Zhi-Fang Chai Wei-Qun Shi 《Journal of Radioanalytical and Nuclear Chemistry》2014,302(1):281-288
Electrochemical behaviors of U(VI) in 1-butyl-3-methylimidazolium chloride (C4MimCl) with various water contents investigated by chronopotentiometry and cyclic voltammetry. The electrochemical reduction of U(VI) was identified to follow two processes: a lower valence intermediate U(V) was initially formed at the potential of ca. ?0.2 V(vs. Ag wire). Then, further deposition of UO2 was followed at around ?0.8 V. Little amount of water (1–4 wt%) in C4MimCl, however, has an effect on the U(VI) reduction by changing the current density of the redox reaction and the diffusion coefficient of U(VI) in C4MimCl. The deposited product by potentiostatic electrolysis on the surface of stainless steel electrode was characterized by the scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and X-ray diffraction (XRD) methods. Although the electrodeposited black film was amorphous, the electrochemical reduced product of U(VI) can be still confirmed to be UO2 by XRD after the crystallization of the amorphous deposits at 1,073 K in nitrogen atmosphere. 相似文献
967.
968.
Small peptides in serum are potential biomarkers for the diagnosis of cancer and other diseases. The identification of peptide biomarkers in human plasma/serum has become an area of high interest in medical research. However, the direct analysis of peptides in serum samples using mass spectrometry is challenging due to the low concentration of peptides and the high abundance of high-molecular-weight proteins in serum, the latter of which causes severe signal suppression. Herein, we reported that porous semiconductor-noble metal hybrid nanostructures can both eliminate the interference from large proteins in serum samples and significantly enhance the matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) yields of peptides captured on the nanostructure. Serum peptide fingerprints with high fidelity can be acquired rapidly, and successful discrimination of colorectal cancer patients based on peptide fingerprints is demonstrated. 相似文献
969.
Despite the common use of quadratic regression in LC–MS bioanalysis, how calibrator concentrations should be determined is still vague. Both the number and concentrations of calibrators are usually selected arbitrarily to each one's preference. The purposes of this research were to evaluate the impact of calibrator concentrations and to find new approaches with improved accuracy and reduced cost for LC–MS bioanalysis. It was found for the first time that the lower and upper limits of quantitation plus their geometric mean are the three critical concentrations for quadratic regression. When different concentration ranges, different response precisions, and various degrees of downward quadratic responses were simulated, the best accuracy was obtained by including these critical concentrations and using fewer calibrator concentrations with more replicates per concentration, instead of using more calibrator concentrations in duplicate. In many cases, when the aforementioned three concentrations are used, as few as two replicates per concentration are enough for routine use and up to 20% of time and cost can be saved. Furthermore, downward quadratic response should be eliminated or reduced as much as possible and upper limit quality control must be included in each batch to monitor the accuracy at the high concentration end. The retrospective data analysis of published experimental results corroborates the aforementioned findings. Finally, the typical “concerns” and potential applications of the new quadratic regression approaches are discussed. 相似文献
970.
Dr. Jinsuo Gao Xueying Zhang Dr. Shutao Xu Dr. Jian Liu Prof. Feng Tan Prof. Xinyong Li Prof. Zhenping Qu Prof. Yaobin Zhang Prof. Xie Quan 《化学:亚洲杂志》2014,9(3):908-914
Pharmaceutical antibiotics, as emerging contaminants, are usually composed of several functional groups that endow them with the ability to interact with adsorbents through different interactions. This makes the preparation of adsorbents tedious and time‐consuming to screen appropriate functionalized materials. Herein, we describe the synthesis of clickable SBA‐15 and demonstrate its feasibility as a screening material for the adsorption of antibiotics based on similar adsorption trends on materials with similar functional groups obtained by a click reaction and cocondensation/grafting methods. 相似文献