全文获取类型
收费全文 | 4146篇 |
免费 | 150篇 |
国内免费 | 18篇 |
专业分类
化学 | 2906篇 |
晶体学 | 40篇 |
力学 | 95篇 |
数学 | 335篇 |
物理学 | 938篇 |
出版年
2024年 | 5篇 |
2023年 | 21篇 |
2022年 | 73篇 |
2021年 | 96篇 |
2020年 | 85篇 |
2019年 | 72篇 |
2018年 | 59篇 |
2017年 | 46篇 |
2016年 | 122篇 |
2015年 | 116篇 |
2014年 | 145篇 |
2013年 | 235篇 |
2012年 | 326篇 |
2011年 | 359篇 |
2010年 | 185篇 |
2009年 | 175篇 |
2008年 | 275篇 |
2007年 | 252篇 |
2006年 | 235篇 |
2005年 | 226篇 |
2004年 | 171篇 |
2003年 | 156篇 |
2002年 | 140篇 |
2001年 | 88篇 |
2000年 | 90篇 |
1999年 | 74篇 |
1998年 | 59篇 |
1997年 | 33篇 |
1996年 | 49篇 |
1995年 | 45篇 |
1994年 | 48篇 |
1993年 | 44篇 |
1992年 | 30篇 |
1991年 | 21篇 |
1990年 | 29篇 |
1989年 | 21篇 |
1988年 | 6篇 |
1987年 | 9篇 |
1986年 | 12篇 |
1985年 | 12篇 |
1984年 | 6篇 |
1983年 | 6篇 |
1982年 | 8篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1977年 | 4篇 |
1976年 | 5篇 |
1975年 | 4篇 |
1974年 | 7篇 |
1973年 | 4篇 |
排序方式: 共有4314条查询结果,搜索用时 15 毫秒
141.
Dr. Ying Wang Ara Cho Dr. Guangri Jia Prof. Xiaoqiang Cui Junhyeop Shin Prof. Inho Nam Kyung-Jong Noh Byoung Joon Park Rui Huang Prof. Jeong Woo Han 《Angewandte Chemie (International ed. in English)》2023,62(15):e202300119
Single-atom nanozymes (SAzymes) are promising in next-generation nanozymes, nevertheless, how to rationally modulate the microenvironment of SAzymes with controllable multi-enzyme properties is still challenging. Herein, we systematically investigate the relationship between atomic configuration and multi-enzymatic performances. The constructed MnSA−N3-coordinated SAzymes (MnSA−N3−C) exhibits much more remarkable oxidase-, peroxidase-, and glutathione oxidase-like activities than that of MnSA−N4−C. Based on experimental and theoretical results, these multi-enzyme-like behaviors are highly dependent on the coordination number of single atomic Mn sites by local charge polarization. As a consequence, a series of colorimetric biosensing platforms based on MnSA−N3−C SAzymes is successfully built for specific recognition of biological molecules. These findings provide atomic-level insight into the microenvironment of nanozymes, promoting rational design of other demanding biocatalysts. 相似文献
142.
In Paper I, we studied vibrational properties of normal bases, base derivatives, Watson-Crick base pairs, and multiple layer base pair stacks in the frequency range of 1400-1800 cm(-1). However, typical IR absorption spectra of single- and double-stranded DNA have been measured in D(2)O solution. Consequently, the more relevant bases and base pairs are those with deuterium atoms in replacement with labile amino hydrogen atoms. Thus, we have carried out density functional theory vibrational analyses of properly deuterated bases, base pairs, and stacked base pair systems. In the frequency range of interest, both aromatic ring deformation modes and carbonyl stretching modes appear to be strongly IR active. Basis mode frequencies and vibrational coupling constants are newly determined and used to numerically simulate IR absorption spectra. It turns out that the hydration effects on vibrational spectra are important. The numerically simulated vibrational spectra are directly compared with experiments. Also, the (18)O-isotope exchange effect on the poly(dG):poly(dC) spectrum is quantitatively described. The present calculation results will be used to further simulate two-dimensional IR photon echo spectra of DNA oligomers in the companion Paper III. 相似文献
143.
Activation of elemental sulfur by the monovalent nickel complex [PhTt (tBu)]Ni(CO) [PhTt(tBu)=phenyl{tris[(tert-butylmethyl)thio]methyl}borate] generates the disulfidodinickel(II) complex 2. This species is alternatively accessible via thermal decomposition of [PhTt (tBu)]Ni(SCPh3). Spectroscopic, magnetic, and X-ray diffraction studies establish that 2 contains a mu-eta(2):eta(2)-S2 ligand that fosters antiferromagnetic exchange coupling between the Ni (II) ions. This observation is in contrast to the lighter congener, oxygen, which strongly favors the bis(mu-oxo)dinickel(III) structure. 2 oxidizes PPh 3 to SPPh3 and reacts with O2, generating several products, one of which has been identified as [(PhTt (tBu))Ni]2(mu-S) (3). 相似文献
144.
Methane activation by group 5 transition-metal atoms in excess argon and the matrix infrared spectra of reaction products have been investigated. Vanadium forms only the monohydrido methyl complex (CH3-VH) in reaction with CH4 and upon irradiation. On the other hand, the heavier metals form methyl hydride and methylidene dihydride complexes (CH3-MH and CH2=MH2) along with the methylidyne trihydride anion complexes (CHMH3-). The neutral products, particularly the methylidene complex, increase markedly on irradiation whereas the anionic product depletes upon UV irradiation or addition of a trace of CCl4 or CBr4 to trap electrons. Other absorptions that emerge on irradiation and annealing increase markedly at higher precursor concentration and are attributed to a higher-order product ((CH3)2MH2)). Spectroscopic evidence suggests that the agostic Nb and Ta methylidene dihydride complexes have two identical metal-hydrogen bonds. 相似文献
145.
The interaction of the nitric oxide ions NO+ and NO- with benzene (C6H6) and the aromatic R-groups of the amino acids phenylalanine (Phe), tyrosine (Tyr), histidine (His), and tryptophan (Trp) have been examined using the DFT method B3LYP and the conventional electron correlation method MP2. In particular, the structures and complexation energies of the resulting half-sandwich Ar...NO+/- and sandwich [Ar...NO...Ar]+/- complexes have been considered. For the Ar...NO+ complexes, the presence of an electron rich heteroatom within or attached to the ring is found to not preclude the cation...pi bound complex from being the most stable. Furthermore, unlike the anionic complexes, the pi...cation...pi ([Ar...NO...Ar]+) complexes do not correspond to a "doubling" of the parent half-sandwich. 相似文献
146.
Kim HM Yang PR Seo MS Yi JS Hong JH Jeon SJ Ko YG Lee KJ Cho BR 《The Journal of organic chemistry》2007,72(6):2088-2096
A novel, two-photon probe for the detection of free Mg2+ ions in living cells and live tissues has been developed. The probe can be excited by 880 nm laser photons, emits strong two-photon excited fluorescence in response to Mg2+ ions, can be easily loaded into the cell and tissue, shows high photostability, and can measure the Mg2+ ion concentration without interference by Ca2+ ions in living cells. The intracellular dissociation constant (Kdi) for Mg2+ determined by the two-photon process is 2.5 mM, which is suitable for dynamic Mg2+ concentration measurement. In addition, the probe is capable of imaging endogenous stores of free Mg2+ at a few hundred micrometers depth in live tissues using two-photon microscopy (TPM). 相似文献
147.
148.
Sang-Bok Ma Kyung-Wan Nam Won-Sub Yoon Seong-Min Bak Xiao-Qing Yang Byung-Won Cho Kwang-Bum Kim 《Electrochemistry communications》2009,11(8):1575-1578
Nano-sized lithium manganese oxide (LMO) dispersed on carbon nanotubes (CNT) has been synthesized successfully via a microwave-assisted hydrothermal reaction at 200 °C for 30 min using MnO2-coated CNT and an aqueous LiOH solution. The initial specific capacity is 99.4 mAh/g at a 1.6 C-rate, and is maintained at 99.1 mAh/g even at a 16 C-rate. The initial specific capacity is also maintained up to the 50th cycle to give 97% capacity retention. The LMO/CNT nanocomposite shows excellent power performance and good structural reversibility as an electrode material in energy storage systems, such as lithium-ion batteries and electrochemical capacitors. This synthetic strategy opens a new avenue for the effective and facile synthesis of lithium transition metal oxide/CNT nanocomposite. 相似文献
149.
Cho KB Kim EJ Seo MS Shaik S Nam W 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(33):10444-10453
The experimentally measured bimolecular reaction rate constant, k(2) , should in principle correlate with the theoretically calculated rate-limiting free energy barrier, ΔG(≠) , through the Eyring equation, but it fails quite often to do so due to the inability of current computational methods to account in a precise manner for all the factors contributing to ΔG(≠) . This is further aggravated by the exponential sensitivity of the Eyring equation to these factors. We have taken herein a pragmatic approach for C?H activation reactions of 1,4-cyclohexadiene with a variety of octahedral nonheme Fe(IV) O complexes. The approach consists of empirically determining two constants that would aid in predicting experimental k(2) values uniformly from theoretically calculated electronic energy (ΔE(≠) ) values. Shown in this study is the predictive power as well as insights into energy relationships in Fe(IV) O C?H activation reactions. We also find that the difference between ΔG(≠) and ΔE(≠) converges at slow reactions, in a manner suggestive of changes in the importance of the triplet spin state weight in the overall reaction. 相似文献
150.
Giseop Kwak Hong‐Qing Wang Kyu‐Han Choi Kyu‐Ho Song Soon‐Hak Kim Hyeok‐Soo Kim Sam‐Jong Lee Ho‐Young Cho Eon‐Ju Yu Hyo‐Jeong Lee Eun‐Jung Park Lee‐Soon Park 《Macromolecular rapid communications》2007,28(12):1317-1324
New poly(diphenylacetylene)s with alkoxy and fluoroalkyl groups as electron‐donating and electron‐withdrawing groups, respectively, were synthesized by using a WCl6‐n‐Ph4Sn catalyst. The polymer solutions emitted strong, bluish‐green lights when photo‐excited. The polymers that contained the electron‐donating alkoxy groups showed longer fluorescence‐maximum peaks when compared to the polymers that contained the electron‐withdrawing fluoroalkyl groups. However, such an effect of the substituent on the absorption property was not clearly seen. The emission bands of the solid films did not show any significant red shift, relative to that of the dilute solution.