全文获取类型
收费全文 | 17837篇 |
免费 | 2802篇 |
国内免费 | 2919篇 |
专业分类
化学 | 12934篇 |
晶体学 | 323篇 |
力学 | 1086篇 |
综合类 | 313篇 |
数学 | 2343篇 |
物理学 | 6559篇 |
出版年
2024年 | 53篇 |
2023年 | 228篇 |
2022年 | 527篇 |
2021年 | 579篇 |
2020年 | 597篇 |
2019年 | 621篇 |
2018年 | 558篇 |
2017年 | 559篇 |
2016年 | 724篇 |
2015年 | 787篇 |
2014年 | 1005篇 |
2013年 | 1297篇 |
2012年 | 1416篇 |
2011年 | 1588篇 |
2010年 | 1221篇 |
2009年 | 1243篇 |
2008年 | 1402篇 |
2007年 | 1241篇 |
2006年 | 1142篇 |
2005年 | 904篇 |
2004年 | 746篇 |
2003年 | 614篇 |
2002年 | 699篇 |
2001年 | 610篇 |
2000年 | 569篇 |
1999年 | 405篇 |
1998年 | 274篇 |
1997年 | 236篇 |
1996年 | 255篇 |
1995年 | 216篇 |
1994年 | 150篇 |
1993年 | 143篇 |
1992年 | 132篇 |
1991年 | 115篇 |
1990年 | 109篇 |
1989年 | 93篇 |
1988年 | 70篇 |
1987年 | 58篇 |
1986年 | 47篇 |
1985年 | 54篇 |
1984年 | 31篇 |
1983年 | 41篇 |
1982年 | 28篇 |
1981年 | 28篇 |
1980年 | 21篇 |
1979年 | 14篇 |
1978年 | 12篇 |
1977年 | 12篇 |
1976年 | 12篇 |
1974年 | 14篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
91.
92.
The complexes [Ru(salen)(NO)Cl] and [Ru(salen)(NO)(H(2)O)](+) were shown to release the nitrosyl ligand as nitric oxide upon exposure to visible light in organic and aqueous solutions respectively, by means of UV-visible, EPR, and FTIR spectroscopies. The former was prepared by a new synthetic route and had its structure determined by single-crystal X-ray diffraction. A crystal of the dichloromethane solvate is orthorhombic, space group Fdd2 (No. 43) and formula C(16)H(14)ClN(3)O(3)Ru.CH(2)Cl(2), with Z = 16 and cell parameters a = 25.489(4), b = 33.435(4), and c = 9.3716(9) A. The electronic absorption spectra of the complexes were calculated using the INDO/S method. The water-soluble complex is a potential drug for antitumoral phototreatment. 相似文献
93.
Robert R Hudgins Fang Huang Gabriela Gramlich Werner M Nau 《Journal of the American Chemical Society》2002,124(4):556-564
A fluorescent amino acid derivative (Fmoc-DBO) has been synthesized, which contains 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) as a small, hydrophilic fluorophore with an extremely long fluorescence lifetime (325 ns in H2O and 505 ns in D2O under air). Polypeptides containing both the DBO residue and an efficient fluorescence quencher allow the measurement of rate constants for intramolecular end-to-end contact formation. Bimolecular quenching experiments indicated that Trp, Cys, Met, and Tyr are efficient quenchers of DBO (k(q) = 20, 5.1, 4.5, and 3.6 x 10(8) M(-1) x s(-1) in D2O), while the other amino acids are inefficient. The quenching by Trp, which was selected as an intrinsic quencher, is presumed to involve exciplex-induced deactivation. Flexible, structureless polypeptides, Trp-(Gly-Ser)n-DBO-NH2, were prepared by standard solid-phase synthesis, and the rates of contact formation were measured through the intramolecular fluorescence quenching of DBO by Trp with time-correlated single-photon counting, laser flash photolysis, and steady-state fluorometry. Rate constants of 4.1, 6.8, 4.9, 3.1, 2.0, and 1.1 x 10(7) s(-1) for n = 0, 1, 2, 4, 6, and 10 were obtained. Noteworthy was the relatively slow quenching for the shortest peptide (n = 0). The kinetic data are in agreement with recent transient absorption studies of triplet probes for related peptides, but the rate constants are significantly larger. In contrast to the flexible structureless Gly-Ser polypeptides, the polyproline Trp-Pro4-DBO-NH2 showed insignificant fluorescence quenching, suggesting that a high polypeptide flexibility and the possibility of probe-quencher contact is essential to induce quenching. Advantages of the new fluorescence-based method for measuring contact formation rates in biopolymers include high accuracy, fast time range (100 ps-1 micros), and the possibility to perform measurements in water under air. 相似文献
94.
Abstract— The primary and secondary electron transfer reactions which occurred upon laser flash photolysis of electrically neutral and positively-charged lipid bilayer vesicles containing chlorophyll, benzoquinone and cytochrome c were determined by time-resolved difference spectral and kinetic measurements, and compared with previous results obtained with negatively-charged vesicles (Y. Fang and G. Tollin, Photochem. Photobiol. 1988). The extent to which oxidized cytochrome c could function as an electron acceptor from triplet state chlorophyll, and reduced cytochrome c could act as an electron donor to chlorophyll cation radical, decreased from negatively-charged to electrically neutral to positively-charged vesicles, in agreement with expectations based on changes in the ability of cytochrome c to bind to the bilayer. In all three types of vesicles, cytochrome c reduction by benzoquinone anion radical occurred in the aqueous phase. 相似文献
95.
96.
提出了一种利用解码技术对全息显微畸变图像进行校正的方法。把全息记录中的显微镜预放大过程作为物光波产生畸变的编码过程;在波前再现过程中,用全息记录中的预放大显微镜对再现的赝实像再次放大进行解码,从而获得清晰的全息显微图像。实验验证了该方法的有效性。 相似文献
97.
Wenyu Fang Yiyu Feng Jian Gao Hui Wang Jing Ge Qingbin Yang Wei Feng 《Molecules (Basel, Switzerland)》2022,27(10)
Molecular photoswitches are considered to be important candidates in the field of solar energy storage due to their sensitive and reversible bidirectional optical response. Nevertheless, it is still a daunting challenge to design a molecular photoswitch to improve the low solar spectrum utilization and quantum yields while achieving charging and discharging of heat without solvent assistance. Herein, a series of visible-light-driven ethylene-bridged azobenzene (b-Azo) chromophores with different alkyne substituents which can undergo isomerization reactions promoted in both directions by visible light are reported. Their visible light responsiveness improves their solar spectrum utilization while also having high quantum yields. In addition, as the compounds are liquids, there is no need to dissolve the compounds in order to exploit this switching. The photoisomerization of b-Azo can be adjusted by alkyne-related substituents, and hexyne-substituted b-Azo is able to store and release photothermal energy with a high density of 106.1 J·g−1, and can achieve a temperature increase of 1.8 °C at a low temperature of −1 °C. 相似文献
98.
Zhuwei Wang Zhicheng Liu Lihan Liu Chao Fang Meng Li Jingcheng Zhao 《Entropy (Basel, Switzerland)》2022,24(5)
With the rapid development of wireless sensor technology, recent progress in wireless sensor and actuator networks (WSANs) with energy harvesting provide the possibility for various real-time applications. Meanwhile, extensive research activities are carried out in the fields of efficient energy allocation and control strategy design. However, the joint design considering physical plant control, energy harvesting, and consumption is rarely concerned in existing works. In this paper, in order to enhance system control stability and promote quality of service for the WSAN energy efficiency, a novel three-step joint optimization algorithm is proposed through control strategy and energy management analysis. First, the optimal sampling interval can be obtained based on energy harvesting, consumption, and remaining conditions. Then, the control gain for each sampling interval is derived by using a backward iteration. Finally, the optimal control strategy is determined as a linear function of the current plant states and previous control strategies. The application of UAV formation flight system demonstrates that better system performance and control stability can be achieved by the proposed joint optimization design for all poor, sufficient, and general energy harvesting scenarios. 相似文献
99.
100.
Heterometallic cluster-based framework materials are of interest in terms of both their porous structures and multi-metallic reactivity. However, such materials have not yet been extensively investigated because of difficulties in their synthesis and structural characterization. Herein, we reported the designable synthesis of atomically precise heterometallic cluster-based framework compounds and their application as catalysts in aldol reactions. By using the synergistic coordination protocol, we successfully isolated a broad range of compounds with the general formula, [Al4M4O4(L)12(DABCO)2] (L = carboxylates; DABCO = 1,4-diazabicyclo[2.2.2]-octane; M2+ = Co2+, Mn2+, Zn2+, Fe2+, Cd2+). The basic heterometallic building blocks contain unprecedented main-group γ-alumina moieties and surrounding unsaturated transition metal centers. Interestingly, the porosity and interpenetration of these frameworks can be rationally regulated through the unprecedented strategy of increment of the metal radius in addition to general introduction of sterically bulky groups on the ligand. Furthermore, these porous materials are effective catalysts for aldol reactions. This work provides a catalytic molecular model platform with accurate molecular bonding between the supporters and catalytically active metal ions.Mesoporous heterometallic architectures are designed by the incorporation of the Al4O4 cubane and interpenetration regulation. 相似文献