全文获取类型
收费全文 | 4335篇 |
免费 | 624篇 |
国内免费 | 164篇 |
专业分类
化学 | 4226篇 |
晶体学 | 3篇 |
力学 | 24篇 |
综合类 | 21篇 |
数学 | 609篇 |
物理学 | 240篇 |
出版年
2023年 | 52篇 |
2022年 | 99篇 |
2021年 | 180篇 |
2020年 | 208篇 |
2019年 | 153篇 |
2018年 | 170篇 |
2017年 | 132篇 |
2016年 | 214篇 |
2015年 | 241篇 |
2014年 | 277篇 |
2013年 | 389篇 |
2012年 | 244篇 |
2011年 | 309篇 |
2010年 | 234篇 |
2009年 | 281篇 |
2008年 | 255篇 |
2007年 | 266篇 |
2006年 | 228篇 |
2005年 | 205篇 |
2004年 | 162篇 |
2003年 | 154篇 |
2002年 | 203篇 |
2001年 | 59篇 |
2000年 | 50篇 |
1999年 | 41篇 |
1998年 | 33篇 |
1997年 | 45篇 |
1996年 | 35篇 |
1995年 | 27篇 |
1994年 | 29篇 |
1993年 | 23篇 |
1992年 | 9篇 |
1991年 | 12篇 |
1990年 | 8篇 |
1989年 | 7篇 |
1988年 | 9篇 |
1987年 | 12篇 |
1986年 | 5篇 |
1985年 | 8篇 |
1984年 | 5篇 |
1983年 | 7篇 |
1982年 | 8篇 |
1981年 | 5篇 |
1980年 | 8篇 |
1979年 | 6篇 |
1976年 | 2篇 |
1973年 | 2篇 |
1969年 | 2篇 |
1968年 | 2篇 |
1959年 | 1篇 |
排序方式: 共有5123条查询结果,搜索用时 15 毫秒
31.
Prof. Dr. Hiroyoshi Takamura Takayuki Fujiwara Yohei Kawakubo Prof. Dr. Isao Kadota Prof. Dr. Daisuke Uemura 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(6):1979-1983
Stereoselective and streamlined synthesis of the proposed C79–C104 fragment 2 of symbiodinolide ( 1 ), a polyol marine natural product with a molecular weight of 2860, was achieved. In the synthetic route, the proposed C79–C104 fragment 2 was synthesized by utilizing a Julia–Kocienski olefination and subsequent Sharpless asymmetric dihydroxylation as key transformations in a convergent manner. Detailed comparison of the 13C NMR chemical shifts between the natural product and the synthetic C79–C104 fragment 2 revealed that the stereostructure at the C91–C99 carbon chain moiety of symbiodinolide ( 1 ) should be reinvestigated. 相似文献
32.
Total Synthesis,Stereochemical Assignment,and Field‐Testing of the Sex Pheromone of the Strepsipteran Xenos peckii 下载免费PDF全文
Dr. Huimin Zhai Michael Hrabar Regine Gries Prof. Gerhard Gries Prof. Robert Britton 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(18):6190-6193
The sex pheromone of the endoparasitoid insect Xenos peckii (Strepsiptera: Xenidae) was recently identified as (7E,11E)‐3,5,9,11‐tetramethyl‐7,11‐tridecadienal. Herein we report the asymmetric synthesis of three candidate stereostructures for this pheromone using a synthetic strategy that relies on an sp3–sp2 Suzuki–Miyaura coupling to construct the correctly configured C7‐alkene function. Comparison of 1H NMR spectra derived from the candidate stereostructures to that of the natural sex pheromone indicated a relative configuration of (3R*,5S*,9R*). Chiral gas chromatographic (GC) analyses of these compounds supported an assignment of (3R,5S,9R) for the natural product. Furthermore, in a 16‐replicate field experiment, traps baited with the synthetic (3R,5S,9R)‐enantiomer alone or in combination with the (3S,5R,9S)‐enantiomer captured 23 and 18 X. peckii males, respectively (mean±SE: 1.4±0.33 and 1.1±0.39), whereas traps baited with the synthetic (3S,5R,9S)‐enantiomer or a solvent control yielded no captures of males. These strong field trapping data, in combination with spectroscopic and chiral GC data, unambiguously demonstrate that (3R,5S,9R,7E,11E)‐3,5,9,11‐tetramethyl‐7,11‐tridecadienal is the X. peckii sex pheromone. 相似文献
33.
利用TG-FTIR对松木屑、褐煤及其混合物的共气化过程及气化产物进行了分析,研究了掺混比例、升温速率以及反应气氛对共气化过程的影响。结果表明,松木屑加入后提高了试样的反应活性,随松木屑比例增加,气化失重速率逐渐降低,CO的开始析出温度及析出峰面积ACO呈降低趋势;较低的升温速率有利于CO和CH4的析出,随着升温速率的增加,DTG曲线向高温侧移动,最大失重速率显著增加,褐煤热解对应的峰逐渐消失;CO2气氛对挥发分析出阶段的失重行为影响不明显;空气气氛时挥发分析出阶段的两个失重峰分别对应挥发分的燃烧和固定碳燃烧,该气氛下没有明显的焦炭气化阶段。 相似文献
34.
35.
(+)-Boronolide and (+)-deacetylboronolide were synthesized using Pd-catalyzed CO insertion and lactonization as the key step. As to the 13C NMR data of (+)-deacetylboronolide, the assignment at C-6 position should be revised. 相似文献
36.
Cedric L. Hugelshofer Dr. Thomas Magauer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(42):15125-15136
We present a full account of the development of a strategy that culminated in the first total syntheses of the unique oxetane‐containing natural product (+)‐dictyoxetane and the macrocyclic diterpene (+)‐dolabellane V. Our retrosynthetic planning was guided by both classical and nonconventional strategies to construct the oxetane, which is embedded in an unprecedented 2,7‐dioxatricyclo[4.2.1.03,8]nonane ring system. Highlights of the successful approach include highly diastereoselective carbonyl addition reactions to assemble the full carbon skeleton, a Grob fragmentation to construct the 11‐membered macrocycle of (+)‐dolabellane V, and a bioinspired 4‐exo‐tet, 5‐exo‐trig cyclization sequence to form the complex dioxatricyclic framework of (+)‐dictyoxetane. Furthermore, an unprecedented strain‐releasing type I dyotropic rearrangement of an epoxide‐oxetane substrate was developed. 相似文献
37.
CH Oxidation of Ingenanes Enables Potent and Selective Protein Kinase C Isoform Activation 下载免费PDF全文
Dr. Yehua Jin Dr. Chien‐Hung Yeh Dr. Christian A. Kuttruff Dr. Lars Jørgensen Dr. Georg Dünstl Dr. Jakob Felding Dr. Swaminathan R. Natarajan Prof. Dr. Phil S. Baran 《Angewandte Chemie (International ed. in English)》2015,54(47):14044-14048
Ingenol derivatives with varying degrees of oxidation were prepared by two‐phase terpene synthesis. This strategy has allowed access to analogues that cannot be prepared by semisynthesis from natural ingenol. Complex ingenanes resulting from divergent C? H oxidation of a common intermediate were found to interact with protein kinase C in a manner that correlates well with the oxidation state of the ingenane core. Even though previous work on ingenanes has suggested a strong correlation between potential to activate PKCδ and induction of neutrophil oxidative burst, the current study shows that the potential to activate PKCβII is of key importance while interaction with PKCδ is dispensable. Thus, key modifications of the ingenane core allowed PKC isoform selectivity wherein PKCδ‐driven activation of keratinocytes is strongly reduced or even absent while PKCβII‐driven activation of neutrophils is retained. 相似文献
38.
Stereochemical Studies of the Karlotoxin Class Using NMR Spectroscopy and DP4 Chemical‐Shift Analysis: Insights into their Mechanism of Action 下载免费PDF全文
Dr. Amanda L. Waters Dr. Joonseok Oh Prof. Allen R. Place Prof. Mark T. Hamann 《Angewandte Chemie (International ed. in English)》2015,54(52):15705-15710
After publication of karlotoxin 2 (KmTx2; 1 ), the harmful algal bloom dinoflagellate Karlodinium sp. was collected and scrutinized to identify additional biologically active complex polyketides. The structure of 1 was validated and revised at C49 using computational NMR tools including J‐based configurational analysis and chemical‐shift calculations. The characterization of two new compounds [KmTx8 ( 2 ) and KmTx9 ( 3 )] was achieved through overlaid 2D HSQC NMR techniques, while the relative configurations were determined by comparison to 1 and computational chemical‐shift calculations. The detailed evaluation of 2 using the NCI‐60 cell lines, NMR binding studies, and an assessment of the literature supports a mode of action (MoA) for targeting cancer‐cell membranes, especially of cytostatic tumors. This MoA is uniquely different from that of current agents employed in the control of cancers for which 2 shows sensitivity. 相似文献
39.
Automated headspace solid‐phase microextraction and on‐fiber derivatization for the determination of clenbuterol in meat products by gas chromatography coupled to mass spectrometry 下载免费PDF全文
A method was developed for the determination of clenbuterol in meat using stable‐isotope‐dilution gas chromatography with mass spectrometry coupled with solid‐phase microextraction and on‐fiber derivatization. The samples were first homogenized with hydrochloric acid followed by protein deposition. After headspace solid‐phase microextraction and on‐fiber derivatization, the content of clenbuterol was measured with the aid of stable‐isotope dilution. The condition of solid‐phase microextraction was optimized by central composite design. The relative standard deviations, limit of detection, and recoveries for clenbuterol were 4.2–9.2%, 0.48 μg/kg, and 96–104%, respectively. The proposed method was satisfactory for analysis of real samples as compared with the Chinese standard method. 相似文献
40.
Tracing novel hemostatic compounds from heating products of total flavonoids in Flos Sophorae by spectrum–effect relationships and column chromatography 下载免费PDF全文
Hao Wu Yaozong Pan Kuilong Wang Liping Liu Yangping Jin Chenchao Zhang 《Journal of separation science》2015,38(10):1691-1699
Flos Sophorae and its processed product have been clinically used to treat hemorrhage. In this study, the total ion chromatographic fingerprints of the heating products of total flavonoids in Flos Sophorae were established by high‐performance liquid chromatography with tandem mass spectrometry and the hemostatic activities were studied by hemostatic screening tests in vivo. The spectrum–effect relationships between fingerprints and hemostatic activities were investigated using canonical correlation analysis to trace the peaks responsible for the hemostatic effects. The predicted active peaks in fingerprints were isolated by column chromatography and their structures were identified by NMR spectroscopy and mass spectrometry. The hemostatic activities of them were verified by platelet aggregation and procoagulation assays in vitro. Canonical correlation analysis results showed that peak 8 and peak 11 were correlated most closely, thus probably being the main hemostatic compounds. Through column chromatography separation, peak 8 (compound I) and peak 11 (compound II) were obtained with purities of 95.61 and 93.38%, respectively, and were discovered new hemostatic compounds named as huaicarbon A (I) and huaicarbon B (II), respectively. This study provides a universal model to trace the active compounds of other herbs which have bioactivity enhancement after processing by spectrum–effect relationships and column chromatography. 相似文献