全文获取类型
收费全文 | 1420篇 |
免费 | 45篇 |
国内免费 | 6篇 |
专业分类
化学 | 764篇 |
晶体学 | 8篇 |
力学 | 77篇 |
数学 | 296篇 |
物理学 | 326篇 |
出版年
2023年 | 9篇 |
2022年 | 20篇 |
2021年 | 35篇 |
2020年 | 29篇 |
2019年 | 40篇 |
2018年 | 33篇 |
2017年 | 34篇 |
2016年 | 58篇 |
2015年 | 34篇 |
2014年 | 52篇 |
2013年 | 92篇 |
2012年 | 96篇 |
2011年 | 114篇 |
2010年 | 75篇 |
2009年 | 61篇 |
2008年 | 89篇 |
2007年 | 69篇 |
2006年 | 74篇 |
2005年 | 72篇 |
2004年 | 54篇 |
2003年 | 54篇 |
2002年 | 39篇 |
2001年 | 11篇 |
2000年 | 17篇 |
1999年 | 22篇 |
1998年 | 19篇 |
1997年 | 18篇 |
1996年 | 17篇 |
1995年 | 16篇 |
1994年 | 14篇 |
1993年 | 5篇 |
1992年 | 5篇 |
1991年 | 12篇 |
1990年 | 8篇 |
1989年 | 6篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1984年 | 8篇 |
1982年 | 3篇 |
1980年 | 4篇 |
1979年 | 5篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1973年 | 2篇 |
1972年 | 2篇 |
1969年 | 2篇 |
1966年 | 2篇 |
1938年 | 7篇 |
排序方式: 共有1471条查询结果,搜索用时 46 毫秒
41.
We apply a recent result of Borichev–Golinskii–Kupin on the Blaschke-type conditions for zeros of analytic functions on the complex plane with a cut along the positive semi-axis to the problem of the eigenvalues distribution of the Fredholm-type analytic operator-valued functions. 相似文献
42.
Dr. Alexander A. Larin Alexander V. Shaferov Dr. Alexander S. Kulikov Prof. Dr. Alla N. Pivkina Konstantin A. Monogarov Dr. Artem O. Dmitrienko Dr. Ivan V. Ananyev Dr. Dmitry V. Khakimov Prof. Dr. Leonid L. Fershtat Prof. Dr. Nina N. Makhova 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(59):14628-14637
A series of novel energetic materials comprising of azo-bridged furoxanylazoles enriched with energetic functionalities was designed and synthesized. These high-energy materials were thoroughly characterized by IR and multinuclear NMR (1H, 13C, 14N) spectroscopy, high-resolution mass spectrometry, elemental analysis, and differential scanning calorimetry (DSC). The molecular structures of representative amino and azo oxadiazole assemblies were additionally confirmed by single-crystal X-ray diffraction and X-ray powder diffraction. A comparison of contributions of explosophoric moieties into the density of energetic materials revealed that furoxan and 1,2,4-oxadiazole rings are the densest motifs while the substitution of the azide and amino fragments on the nitro and azo ones leads to an increase of the density. Azo bridged energetic materials have high nitrogen-oxygen contents (68.8–76.9 %) and high thermal stability. The synthesized compounds exhibit good experimental densities (1.62–1.88 g cm−3), very high enthalpies of formation (846–1720 kJ mol−1), and, as a result, excellent detonation performance (detonation velocities 7.66–9.09 km s−1 and detonation pressures 25.0–37.7 GPa). From the application perspective, the detonation parameters of azo oxadiazole assemblies exceed those of the benchmark explosive RDX, while a combination of high detonation performance and acceptable friction sensitivity of azo(1,2,4-triazolylfuroxan) make it a promising potential alternative to PETN. 相似文献
43.
44.
On the long‐range relativistic effects in the 15N NMR chemical shifts of halogenated azines
下载免费PDF全文
![点击此处可从《Magnetic resonance in chemistry : MRC》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dmitry O. Samultsev Yury Yu. Rusakov Leonid B. Krivdin 《Magnetic resonance in chemistry : MRC》2017,55(11):990-995
Long‐range β‐ and γ‐relativistic effects of halogens in 15N NMR chemical shifts of 20 halogenated azines (pyridines, pyrimidines, pyrazines, and 1,3,5‐triazines) are shown to be unessential for fluoro‐, chloro‐, and bromo‐derivatives (1–2 ppm in average). However, for iodocontaining compounds, β‐ and γ‐relativistic effects are important contributors to the accuracy of the 15N calculation. Taking into account long‐range relativistic effects slightly improves the agreement of calculation with experiment. Thus, mean average errors (MAE) of 15N NMR chemical shifts of the title compounds calculated at the non‐relativistic and full 4‐component relativistic levels in gas phase are accordingly 7.8 and 5.5 ppm for the range of about 150 ppm. Taking into account solvent effects within the polarizable continuum model scheme marginally improves agreement of computational results with experiment decreasing MAEs from 7.8 to 7.4 ppm and from 5.5 to 5.3 ppm at the non‐relativistic and relativistic levels, respectively. The best result (MAE: 5.3 ppm) is achieved at the 4‐component relativistic level using Keal and Tozer's KT3 functional used in combination with Dyall's relativistic basis set dyall.av3z with taking into account solvent effects within the polarizable continuum solvation model. The long‐range relativistic effects play a major role (of up to dozen of parts per million) in 15N NMR chemical shifts of halogenated nitrogen‐containing heterocycles, which is especially crucial for iodine derivatives. This effect should apparently be taken into account for practical purposes. 相似文献
45.
Yury Yu. Rusakov Irina L. Rusakova Leonid B. Krivdin 《Magnetic resonance in chemistry : MRC》2014,52(5):214-221
Four‐component relativistic calculations of 77Se–13C spin–spin coupling constants have been performed in the series of selenium heterocycles and their parent open‐chain selenides. It has been found that relativistic effects play an essential role in the selenium–carbon coupling mechanism and could result in a contribution of as much as 15–25% of the total values of the one‐bond selenium–carbon spin‐spin coupling constants. In the overall contribution of the relativistic effects to the total values of 1J(Se,C), the scalar relativistic corrections (negative in sign) by far dominate over the spin‐orbit ones (positive in sign), the latter being of less than 5%, as compared to the former (ca 20%). A combination of nonrelativistic second‐order polarization propagator approach (CC2) with the four‐component relativistic density functional theory scheme is recommended as a versatile tool for the calculation of 1J(Se,C). Solvent effects in the values of 1J(Se,C) calculated within the polarizable continuum model for the solvents with different dielectric constants (ε 2.2–78.4) are next to negligible decreasing negative 1J(Se,C) in absolute value by only about 1 Hz. The use of the locally dense basis set approach applied herewith for the calculation of 77Se–13C spin‐spin coupling constants is fully justified resulting in a dramatic decrease in computational cost with only 0.1–0.2‐Hz loss of accuracy. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
46.
47.
Alexander A. Larin Dr. Nikita V. Muravyev Prof. Dr. Alla N. Pivkina Dr. Kyrill Yu. Suponitsky Dr. Ivan V. Ananyev Dr. Dmitry V. Khakimov Dr. Leonid L. Fershtat Prof. Dr. Nina N. Makhova 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(16):4225-4233
A series of highly energetic organic salts comprising a tetrazolylfuroxan anion, explosophoric azido or azo functionalities, and nitrogen-rich cations were synthesized by simple, efficient, and scalable chemical routes. These energetic materials were fully characterized by IR and multinuclear NMR (1H, 13C, 14N, 15N) spectroscopy, elemental analysis, and differential scanning calorimetry (DSC). Additionally, the structure of an energetic salt consisting of an azidotetrazolylfuroxan anion and a 3,6,7-triamino-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazolium cation was confirmed by single-crystal X-ray diffraction. The synthesized compounds exhibit good experimental densities (1.57–1.71 g cm−3), very high enthalpies of formation (818–1363 kJ mol−1), and, as a result, excellent detonation performance (detonation velocities 7.54–8.26 kms−1 and detonation pressures 23.4–29.3 GPa). Most of the synthesized energetic salts have moderate sensitivity toward impact and friction, which makes them promising candidates for a variety of energetic applications. At the same time, three compounds have impact sensitivity on the primary explosives level (1.5–2.7 J). These results along with high detonation parameters and high nitrogen contents (66.0–70.2 %) indicate that these three compounds may serve as potential environmentally friendly alternatives to lead-based primary explosives. 相似文献
48.
49.
Amit M. Jabgunde Rahul S. Patil Swarup De Eveline Lescrinier Steven De Jonghe Leonid Beigelman Piet Herdewijn 《Tetrahedron》2019,75(8):1107-1114
The synthesis of 3′-fluoro-4′-amino-hexitol nucleosides with a uracil and cytosine nucleobase was performed. The synthesis started from 1,5:2,3-dianhydro-4,6-benzylidene-allitol and afforded the target compounds in 15 steps. These protected hexitol nucleosides are valuable building blocks for the preparation of a new class of oligonucleotides. 相似文献
50.
Bushmeleva A. S. Tafeenko V. A. Zakharov V. N. Lobova A. A. Aslanov Leonid A. 《Structural chemistry》2019,30(2):425-434
Structural Chemistry - Contradictory literature on the alkali-assisted exfoliation of the melon and searching for the best precursors for different heptazine derivative synthesis led us to the... 相似文献