全文获取类型
收费全文 | 15323篇 |
免费 | 2686篇 |
国内免费 | 1903篇 |
专业分类
化学 | 11291篇 |
晶体学 | 227篇 |
力学 | 861篇 |
综合类 | 130篇 |
数学 | 1607篇 |
物理学 | 5796篇 |
出版年
2024年 | 62篇 |
2023年 | 317篇 |
2022年 | 563篇 |
2021年 | 549篇 |
2020年 | 586篇 |
2019年 | 650篇 |
2018年 | 526篇 |
2017年 | 509篇 |
2016年 | 719篇 |
2015年 | 734篇 |
2014年 | 934篇 |
2013年 | 1227篇 |
2012年 | 1430篇 |
2011年 | 1553篇 |
2010年 | 1034篇 |
2009年 | 1008篇 |
2008年 | 1014篇 |
2007年 | 991篇 |
2006年 | 796篇 |
2005年 | 687篇 |
2004年 | 582篇 |
2003年 | 444篇 |
2002年 | 415篇 |
2001年 | 350篇 |
2000年 | 329篇 |
1999年 | 251篇 |
1998年 | 212篇 |
1997年 | 168篇 |
1996年 | 186篇 |
1995年 | 147篇 |
1994年 | 154篇 |
1993年 | 118篇 |
1992年 | 115篇 |
1991年 | 93篇 |
1990年 | 87篇 |
1989年 | 77篇 |
1988年 | 44篇 |
1987年 | 41篇 |
1986年 | 42篇 |
1985年 | 40篇 |
1984年 | 29篇 |
1983年 | 16篇 |
1982年 | 6篇 |
1981年 | 11篇 |
1980年 | 6篇 |
1979年 | 11篇 |
1977年 | 6篇 |
1976年 | 8篇 |
1975年 | 6篇 |
1957年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
251.
Tetrahydrofurans (THFs) and tetrahydropyrans (THPs) are important core scaffolds frequently found in many molecules of medicinal importance. Herein, we report a novel copper-catalyzed hydroxycyclopropanol ring-opening cyclization methodology to synthesize di- or tri-substituted THFs and THPs. In this reaction, a strained C–C bond was cleaved and a new Csp3–O bond was formed to produce the aforementioned O-heterocycles. The new THF synthesis features a broad substrate scope, scalability, and good functional-group tolerability. It enabled us to complete the shortest enantioselective syntheses of hyperiones A and B (3 and 4 steps, respectively), which is significantly shorter than the previously reported two total syntheses (≥10 steps).A novel Cu-catalyzed hydroxycyclopropanol ring-opening cyclization was developed to synthesize substituted tetrahydrofuran/tetrahydropyran molecules including two norlignan natural products hyperiones A and B. 相似文献
252.
The precise location of C C bonds in bioactive molecules is critical for a deep understanding of the relationship between their structures and biological roles. However, the traditional ultraviolet light-based approaches exhibited great limitations. Here, we discovered a new type of visible-light activated [2 + 2] cycloaddition of carbonyl with C C bonds. We found that carbonyl in anthraquinone showed great reactivities towards C C bonds in lipids to form oxetanes under the irradiation of visible-light. Combined with tandem mass spectrometry, this site-specific dissociation of oxetane enabled precisely locating the C C bonds in various kinds of monounsaturated and polyunsaturated lipids. The proof-of-concept applicability of this new type of [2 + 2] photocycloaddition was validated in the global identification of unsaturated lipids in a complex human serum sample. 86 monounsaturated and polyunsaturated lipids were identified with definitive positions of C C bonds, including phospholipids and fatty acids even with up to 6 C C bonds. This study provides new insights into both the photocycloaddition reactions and the structural lipidomics.A new visible-light activated [2 + 2] cycloaddition reaction was discovered and enabled pinpointing carbon–carbon double bonds in lipids. 相似文献
253.
Yongzheng Cong Khatereh Motamedchaboki Santosh A. Misal Yiran Liang Amanda J. Guise Thy Truong Romain Huguet Edward D. Plowey Ying Zhu Daniel Lopez-Ferrer Ryan T. Kelly 《Chemical science》2021,12(3):1001
We report on the combination of nanodroplet sample preparation, ultra-low-flow nanoLC, high-field asymmetric ion mobility spectrometry (FAIMS), and the latest-generation Orbitrap Eclipse Tribrid mass spectrometer for greatly improved single-cell proteome profiling. FAIMS effectively filtered out singly charged ions for more effective MS analysis of multiply charged peptides, resulting in an average of 1056 protein groups identified from single HeLa cells without MS1-level feature matching. This is 2.3 times more identifications than without FAIMS and a far greater level of proteome coverage for single mammalian cells than has been previously reported for a label-free study. Differential analysis of single microdissected motor neurons and interneurons from human spinal tissue indicated a similar level of proteome coverage, and the two subpopulations of cells were readily differentiated based on single-cell label-free quantification.The combination of nanodroplet sample preparation, ultra-low-flow nanoLC, high-field asymmetric ion mobility spectrometry (FAIMS) and latest-generation mass spectrometry instrumentation provides dramatically improved single-cell proteome profiling. 相似文献
254.
The existence of solutions to a fourth-order p-Laplacian equation with boundary degeneracy is studied. For the purpose of solving the corresponding non-degenerate (with respect to the coefficient of fourth-order term) regularized problem, a fourth-order semi-discrete elliptic problem with homogeneous boundary conditions is established and its existence and uniqueness are obtained by the functional minimization method. It follows that the approximate solutions of the non-degenerate parabolic problem are constructed and the corresponding existence and uniqueness are discovered by a limit procedure from the energy estimation method and a compactness argument. Finally, the existence and regularity of solutions for the problem with boundary degeneracy is obtained by using a regularization parameter vanishing limit. 相似文献
255.
该文讨论了一类带扰动的随机脉冲泛函微分方程解的渐近性.通过比较扰动方程的解和原方程的解,得到了两者逼近的充分条件.首先,两者在有限的时间区间上相互逼近;其次,当扰动趋于零时,区间长度趋于无穷大,在这个区间上两个解仍然是相互逼近的.最后,举例说明了结果的有效性. 相似文献
256.
X. Y. Zhang S. Jin Y. C. Liang Y. F. Ming L. H. Yu M. G. Fan W. F. Wang S. D. Yao 《Research on Chemical Intermediates》1995,21(1):17-24
Photochromic reactions of four indolinospirooxazine derivatives have been studied using nanosecond laser flash photolysis
techniques. Photolysis of the four compounds in acetonitrile and in cyclohexane all leads to the formation of the short-lived
CT intermediates as the predominant photoproducts. In certain circumstances few photomerocyanines (PMC) can be observed. From
the absorption bands and the lifetimes of CT intermediates, it has been speculated that the substituents at the nitrogen atom
of the indole ring influence the structural characteristics of CT intermediates mainly through steric hindrance effects, whereas
the substituents at the 5 position of the indoline ring influence mainly through electron effects. A potential energy surface
model is established to explain the results. 相似文献
257.
LaSrBO4(B=Cu、Ni、 Co、 Fe、 Mn、 Cr ) was studied with respect to their preparation, characteristics and catalytic oxidation activity by means of XRD, XPS, electric conductivity and activity evaluation. Results showed that the calcination temperature has great influence on the formation of the phases of such samples, and was associated with the radius of B ion. The greater the B ion radius, the higher the calcination temperature required for the formation of the phases. It was also found that the activity and the relative content of adsorptive oxygen and lattice oxygen on the sample surf are, the activation energy of electron conduction and the CO oxidation activity may vary with different B ions, and demonstrate a dual-peak pattern with the increase in the number of 3d electrons of the B ion. 相似文献
258.
ONBAHADURASYMPTOTICEFFICIENCYINASEMIPARAMETRICREGRESSIONMODELLIANGHUA(梁华);CHENGPING(成平)(InstituteofSystemsScience,theChineseA... 相似文献
259.
Liang Chen 《Communications in Mathematical Physics》1995,167(2):431-469
A class of differential operator Lie algebras on the unit circle is introduced and discussed. They are the natural generalizations of the Witt algebra and the Virasoro algebra. Among them are the higher-spin algebrasW
1+ andW
which occur in the physics literature. 相似文献
260.