全文获取类型
收费全文 | 1651篇 |
免费 | 76篇 |
国内免费 | 4篇 |
专业分类
化学 | 1355篇 |
晶体学 | 15篇 |
力学 | 31篇 |
数学 | 48篇 |
物理学 | 282篇 |
出版年
2023年 | 18篇 |
2022年 | 13篇 |
2021年 | 20篇 |
2020年 | 37篇 |
2019年 | 42篇 |
2018年 | 23篇 |
2017年 | 19篇 |
2016年 | 37篇 |
2015年 | 36篇 |
2014年 | 44篇 |
2013年 | 96篇 |
2012年 | 96篇 |
2011年 | 97篇 |
2010年 | 49篇 |
2009年 | 49篇 |
2008年 | 89篇 |
2007年 | 71篇 |
2006年 | 82篇 |
2005年 | 62篇 |
2004年 | 61篇 |
2003年 | 48篇 |
2002年 | 41篇 |
2001年 | 55篇 |
2000年 | 32篇 |
1999年 | 34篇 |
1998年 | 12篇 |
1997年 | 13篇 |
1996年 | 22篇 |
1995年 | 9篇 |
1994年 | 24篇 |
1993年 | 16篇 |
1992年 | 44篇 |
1991年 | 21篇 |
1990年 | 24篇 |
1989年 | 23篇 |
1988年 | 27篇 |
1987年 | 26篇 |
1986年 | 18篇 |
1985年 | 22篇 |
1984年 | 25篇 |
1983年 | 15篇 |
1982年 | 12篇 |
1979年 | 9篇 |
1977年 | 10篇 |
1975年 | 11篇 |
1974年 | 8篇 |
1973年 | 8篇 |
1964年 | 9篇 |
1962年 | 7篇 |
1960年 | 7篇 |
排序方式: 共有1731条查询结果,搜索用时 15 毫秒
161.
Shaohua Guo Dr. Pan Liu Dr. Yang Sun Kai Zhu Dr. Jin Yi Prof. Mingwei Chen Prof. Masayoshi Ishida Prof. Haoshen Zhou 《Angewandte Chemie (International ed. in English)》2015,54(40):11701-11705
Recently, there has been great interest in developing advanced sodium‐ion batteries for large‐scale application. Most efforts have concentrated on the search for high‐performance electrode materials only in sodium half‐cells. Research on sodium full cells for practical application has encountered many problems, such as insufficient cycles with rapid capacity decay, low safety, and low operating voltage. Herein, we present a layered P2‐Na0.66Ni0.17Co0.17Ti0.66O2, as both an anode (ca. 0.69 V versus Na+/Na) and as a high‐voltage cathode (ca. 3.74 V versus Na+/Na). The full cell based on this bipolar electrode exhibits well‐defined voltage plateaus near 3.10 V, which is the highest average voltage in the symmetric cells. It also shows the longest cycle life (75.9 % capacity retention after 1000 cycles) in all sodium full cells, a usable capacity of 92 mAh g?1, and superior rate capability (65 mAh g?1 at a high rate of 2C). 相似文献
162.
Dr. Shintaro Ishida Dr. Takashi Abe Dr. Fumiya Hirakawa Tomoyuki Kosai Katsuhiro Sato Prof. Dr. Mitsuo Kira Prof. Dr. Takeaki Iwamoto 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(43):15100-15103
A persistent dialkylsilanone was synthesized by the dehydrobromination of a dialkylbromosilanol with tris(trimethylsilyl)silyl potassium in solution at ?80 °C: It was characterized by NMR and IR spectroscopy, and was tested in several reactions. In 29Si NMR spectrum in [D8]toluene, the signal due to the unsaturated silicon nuclei was observed at 128.7 ppm. Reactions of the dialkylsilanone with water and mesitonitrile oxide gave a silanediol and a [2+3] cycloadduct, respectively. The silanone remains intact in [D8]toluene below ?80 °C for at least two days, while it undergoes unprecedented isomerization to give a siloxysilene by means of 1,3‐silyl migration at higher temperatures. 相似文献
163.
Dr. Masahito Yoshida Yoshitaka Ishida Kenta Adachi Hayato Murase Dr. Hiroshi Nakagawa Prof.Dr. Takayuki Doi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(50):18417-18430
The solid‐phase combinatorial synthesis of cyclodepsipeptide destruxin E has been demonstrated. The combinatorial synthesis of cyclization precursors 8 was achieved by using a split and pool method on SynPhase Lanterns. The products were successfully macrolactonized in parallel in the solution phase by using 2‐methyl‐6‐nitrobenzoic anhydride and 4‐(dimethylamino)pyridine N‐oxide to afford macrolactones 9 , and the subsequent formation of an epoxide in the side chain gave 18 member destruxin E analogues 6 . Biological evaluation of analogues 6 indicated that the N‐MeAla residue was crucial to the induction of morphological changes in osteoclast‐like multinuclear cells (OCLs). Based on structure–activity relationships, azido‐containing analogues 15 were then designed for use as a molecular probe. The synthesis and biological evaluation of analogues 15 revealed that 15 b , in which the Ile residue was replaced with a Lys(N3) residue, induced morphological changes in OCLs at a sufficient concentration, and modification around the Ile residue would be tolerated for attachment of a chemical tag toward the target identification of destruxin E ( 1 ). 相似文献
164.
Fourier transform mechanical spectroscopy technique (FTMS) is utilized as a powerful tool to study the sol-gel transition
of covalent bonded polymeric network. Winter and Chambon criteria resulting from the fractal-geometry characteristic of the
gel networks allow the determination of the gel point with only single experiment using this technique. The gelation behaviors
of low melt viscosity ternary systems of benzoxazine, epoxy, and phenolic resins are investigated and analyzed by the technique
in order to study the effect of epoxy diluent on the rheological property development before and after the gel points. The
gel time at 140 °C ranges from 5 min to 30 min and less than 5 min at 180 °C for all tested ternary system compositions. The
gelation of the ternary mixture shows an Arrhenius-type behavior and the gel time can be well-predicted by the Arrhenius equation.
Received: 23 November 1999 Accepted: 2 January 2001 相似文献
165.
166.
This study describes the framework of the quantum mechanical (QM)/Monte Carlo (MC)/free‐energy perturbation (FEP) method, a FEP method based on MC simulations using quantum chemical calculations. Because a series of structures generated by interpolating internal coordinates between transition state and reactant did not produce smooth free‐energy profiles, we used structures from the intrinsic reaction coordinate calculations. This method was first applied to the Diels–Alder reaction between methyl vinyl ketone and cyclopentadiene and produced ΔG values of 20.1 and 21.4 kcal mol?1 in aqueous and methanol solutions, respectively. They are very consistent with the experimentally observed values. The other two applications were the free‐energy surfaces for the Cope elimination of N,N‐dimethyl‐3‐phenylbutan‐2‐amine oxide in aqueous, dimethyl sulfoxide, and tetrahydrofuran solutions, and the Kemp decarboxylation of 6‐hydroxybenzo‐isoxazole‐3‐carboxylic acid in aqueous, dimethyl sulfoxide, and CH3CN solutions. The calculated activation free energies differed by less than 1.8 kcal mol?1 from the experimental values for these reactions. Although we used droplet models for the QM/MC/FEP simulations, the calculated results for three reactions are very close to the experimental data. It was confirmed that most of the interactions between the solute and solvents can be described using small numbers of solvent molecules. This is because a few solvent molecules can produce large portions of the solute–solvent interaction energies at the reaction centers. When we confirmed the dependency on the droplet sizes of solvents, the QM/MC/FEP for a large droplet with 106 water molecules produced a ΔG value similar to the experimental values, as well as that for a small droplet with 34 molecules. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011 相似文献
167.
Determination methods of halide ions (X(-) = F(-), Cl(-), Br(-) and I(-)) by electrospray ionization mass spectrometry (ESIMS) were developed, where negative ions of the ternary complexes of group-13 elements, nitrilotriacetic acid (NTA), and halides were measured. In particular, these halides were simultaneously determined by measuring [InX(nta)](-), and the limits of detection (LODs) were 1.1 μmol dm(-3) for F(-), 0.32 μmol dm(-3) for Cl(-), 3.8 nmol dm(-3) for Br(-), and 1.6 nmol dm(-3) for I(-), respectively. This approach was extended to the determination of CN(-), where the ternary complex of Cu(II), CN(-) and 4-(2-pyridylazo)resorcinol (PAR), i.e., [(63)Cu(II)(CN)(par)](-) (m/z 302) was measured. The LOD for CN(-) was 20 nmol dm(-3). 相似文献
168.
169.
170.
Kato S Tani K Ishida M Nonogaki J Ebihara M Hayashi S Nakanishi W Niyomura O Ando F Koketsu J 《Dalton transactions (Cambridge, England : 2003)》2011,40(32):8156-8169
A series of selenium and tellurium bis(carbodithioates and carbothioates) were synthesized. X-Ray structure analysis revealed that Se(SSCC(6)H(4)OMe-2)(2), Te(SSCC(6)H(4)OMe-2)(2) and Te(SSCC(6)H(4)Me-4)(2) have trapezoidal-planar configuration of ES(4) (E = Se, Te) and despite the larger atomic radii, the C=S···Te distances in Te(SSCC(6)H(4)OMe-2)(2) are comparable to those in the corresponding selenium derivatives Se(SSCC(6)H(4)OMe-2)(2). Molecular-orbital calculations performed on compounds E(E'SCR)(2) (E = S, Se, Te; E' = O, S; R = Me, Ph, C(6)H(4)OMe-2) showed that the syn-conformers of Se(SSCR)(2) and Te(SSCR)(2) are more stable than the corresponding anti-ones, while, in the case of carbothioic acid derivatives, E(SOCR)(2) showed that their anti-conformers are all more stable than the corresponding syn-ones. Natural bond orbital (NBO) analyses of these dithio-compounds revealed that two types of orbital interactions, n(S(1))→σ*(E-S(2)) and n(O)→σ*(E-S(2)), play a role in the bonding of E[S(2)S(1)CC(6)H(4)OMe-2](2) (E = Se, Te) and the former play a particularly predominant role. 相似文献