全文获取类型
收费全文 | 3365篇 |
免费 | 316篇 |
国内免费 | 606篇 |
专业分类
化学 | 3670篇 |
晶体学 | 122篇 |
力学 | 30篇 |
综合类 | 24篇 |
数学 | 3篇 |
物理学 | 438篇 |
出版年
2024年 | 7篇 |
2023年 | 26篇 |
2022年 | 76篇 |
2021年 | 106篇 |
2020年 | 141篇 |
2019年 | 129篇 |
2018年 | 106篇 |
2017年 | 103篇 |
2016年 | 160篇 |
2015年 | 163篇 |
2014年 | 191篇 |
2013年 | 299篇 |
2012年 | 221篇 |
2011年 | 204篇 |
2010年 | 170篇 |
2009年 | 195篇 |
2008年 | 196篇 |
2007年 | 193篇 |
2006年 | 204篇 |
2005年 | 182篇 |
2004年 | 190篇 |
2003年 | 176篇 |
2002年 | 189篇 |
2001年 | 104篇 |
2000年 | 86篇 |
1999年 | 84篇 |
1998年 | 64篇 |
1997年 | 45篇 |
1996年 | 46篇 |
1995年 | 42篇 |
1994年 | 35篇 |
1993年 | 17篇 |
1992年 | 25篇 |
1991年 | 21篇 |
1990年 | 15篇 |
1989年 | 11篇 |
1988年 | 8篇 |
1987年 | 8篇 |
1986年 | 13篇 |
1985年 | 6篇 |
1984年 | 4篇 |
1983年 | 4篇 |
1981年 | 4篇 |
1980年 | 6篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1973年 | 1篇 |
排序方式: 共有4287条查询结果,搜索用时 15 毫秒
1.
Herein, we report an addition to the toolbox for the monitoring and quantification of the hydrolytic decay of pentose-1-phosphates, which are known to be elusive and difficult to quantify. This communication describes how apparent equilibrium shifts of a nucleoside phosphorolysis reaction can be employed to calculate hydrolytic loss of pentose-1-phosphates based on the measurement of post-hydrolysis equilibrium concentrations of a nucleoside and a nucleobase. To demonstrate this approach, we assessed the stability of the relatively stable ribose-1-phosphate at 98 °C and found half-lives of 1.8–11.7 h depending on the medium pH. This approach can be extended to other sugar phosphates and related reaction systems to quantify the stability of UV-inactive and hard-to-detect reaction products and intermediates. 相似文献
2.
Hideaki Murasugi Dr. Shohei Kumagai Dr. Hiroaki Iguchi Prof. Dr. Masahiro Yamashita Dr. Shinya Takaishi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(42):9885-9891
Crystal structures of a series of organic–inorganic hybrid gold iodide perovskites, formulated as A2[AuII2][AuIIII4] [A=methylammonium (MA) ( 1 ) and formamidinium (FA) ( 2 )], A′2[I3]1−x[AuII2]x[AuIIII4] [A′=imidazolium (IMD) ( 3 ), guanidinium (GUA) ( 4 ), dimethylammonium (DMA) ( 5 ), pyridinium (PY) ( 6 ), and piperizinium (PIP) ( 7 )], systematically changed depending on the cation size. In addition, triiodide (I3−) ions were partly incorporated into the AuI2− sites of 3 – 7 , whereas they were not incorporated into those of 1 and 2 . Such a difference comes from the size of the organic cation. Optical absorption spectra showed characteristic intervalence charge-transfer bands from AuI to AuIII species, and the optical band gap increased as the size of the cation became larger. 相似文献
3.
Phase modulation in dipolar-coupled A2 spin systems: effect of maximum state mixing in H NMR in vivo
Leif Schrder Christian Schmitz Peter Bachert 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,171(2):69
Coupling constants of nuclear spin systems can be determined from phase modulation of multiplet resonances. Strongly coupled systems such as citrate in prostatic tissue exhibit a more complex modulation than AX connectivities, because of substantial mixing of quantum states. An extreme limit is the coupling of n isochronous spins (An system). It is observable only for directly connected spins like the methylene protons of creatine and phosphocreatine which experience residual dipolar coupling in intact muscle tissue in vivo. We will demonstrate that phase modulation of this “pseudo-strong” system is quite simple compared to those of AB systems. Theory predicts that the spin-echo experiment yields conditions as in the case of weak interactions, in particular, the phase modulation depends linearly on the line splitting and the echo time. 相似文献
4.
The electronic structure and chemical bonding in a recently synthesized inorganic fullerene-like molecule, [CuCl]20[Cp*FeP5]12[Cu-(CH3CN) +
2Cl−]5 has been studied by a density functional approach. Geometrical optimization of the three basic structural units of the molecule
is performed with Amsterdam Density Functional Program. The results are in agreement with the experiment. Localized MO’s obtained
by Boys-Foster method give a clear picture of the chemical bonding in this molecule. The reason why CuCl can react with Cp*FeP5 in solvent CH3CN to form the fullerene-like molecule is explained in terms of the soft-hard Lewis acid base theory and a new concept of
covalence. 相似文献
5.
WANG Bingwu XU Guangxian & CHEN Zhida State Key Laboratory of Rare Earth Materials Chemistry Applications College of Chemistry Molecular Engineering Peking University Beijing China 《中国科学B辑(英文版)》2004,47(2)
The titled inorganic fullerene-like molecule (hereafter abbreviated as IFM) was recently synthe-sized by Bai et al.[1], which attracts a lot of interests from inorganic and organometallic chemists, and questions are raised for this smart molecule: (ⅰ) Why CuCl can react with Cp*FeP5 in solvent CH3CN to form IFM? (ⅱ) What is the nature of chemical bond-ing? (ⅲ) What is the covalence of Cu in this mole-cule? In this paper we intend to answer these questions in terms of the soft-hard … 相似文献
6.
The prepared amorphous
γ-ZrP\SiO2 composite had a complicated composition,
since a part of γ-ZrP is converted to α-form during the exfoliation
of it. The γ-ZrP\SiO2 composite have specific surface
area of 421 m2g–1.
The acidic P–OH groups of the lamellae species placed on the surface
(it is ≈1.0 meq g–1), do not destroy until
the temperature of 1030 K. During the thermal treatment the total mass loss
of 7.79% was found. This value corresponds to 0.42 mole of H2O
per molecule unit. The water loss process was found very slow, because of
the placing of bilamellar species in the composite. 相似文献
7.
A new method based on anion exchange resin separation and graphite furnace atomic absorption spectrometry (GFAAS) detection
is proposed for the determination of inorganic tin species. The result showed that Sn(IV) was quantitatively retained on the
resin when [HCl] = 9.0 mol · L−1, but Sn(II) could not be adsorbed on the resin under the same condition. Thus, a separation of Sn(II) and Sn(IV) has been
realized. When the concentration of NaOH solution was between 2.0–7.0 mol · L−1, Sn(IV) that adsorbed on the resin could be eluated from the resin completely. Meanwhile, under the atmosphere and the nitrogen
states, the translation between Sn(II) and Sn(IV) was investigated. Under the optimal conditions, the detection limit of Sn(IV)
is 0.40 μg · L−1 with RSD of 2.3% (n = 5, c = 2.0 μg · L−1). The proposed method was applied to the speciation analysis of tin in different water samples and the recovery of total
Sn was in the range of 98.7–101.7%. In order to verify the accuracy of the method, a certified reference water sample was
analyzed and the results obtained were in good agreement with the certified value. 相似文献
8.
9.
无机纳米粒子作为生物探针在生物分析中的研究进展 总被引:3,自引:0,他引:3
介绍了无机纳米粒子在生物分析领域的研究进展分别从生物分子与纳米粒子的耦联方式、检测生物分子的纳米金探针、核酸或蛋白质修饰的其它纳米探针以及生物纳米技术的应用前景4个方面对该领域的发展进行了概述。 相似文献
10.
本文对所合成的具有 [(PO4 ) 2 Mo5O1 5]簇骼的 3种新颖的有机 磷钼酸盐簇合物(NH3CH2 CH2 NH3) 2 5[(PO4 ) (HPO4 )Mo5O1 5]·7 5H2 O (Ⅰ ) ,(H3NCH2 CH2 NH3) 3·[(PO4 ) 2 Mo5O1 5]·3H2 O (Ⅱ )和(H3NCH2 CH2 NH3) 2 ·[Cu(en) ][(PO4 ) 2 Mo5O1 5]·5H2 O (Ⅲ )用FTIR ,NIR Raman ,紫外 可见漫反射光谱 (UV VisDRS)和荧光光谱等研究手段 ,对其进行光谱研究 ,探讨其结构和性能的关系。在这些化合物中 ,化合物Ⅰ和Ⅱ具有孤立的 [(PO4 ) 2 Mo5O1 5]簇骼基元 ,而化合物Ⅲ的 [(PO4 ) 2 Mo5O1 5]簇骼基元是由 [Cuen]基团桥联成链 ;磷钼酸盐的特征振动频率和这些化合物的结构相关 ;UV VisDRS显示 ,在 2 0 0和 2 6 0nm左右有两个杂多化合物的特征吸收谱带 ;化合物的稳态荧光光谱中 ,观察到以 2 4 0nm激发 ,在大约 4 0 0nm附近出现的由金属氧簇Oμ→Mo跃迁激发所引起的较强的发射峰 ,在化合物 (Ⅲ )中 ,还观察到通过 [Cuen]的荷移跃迁的以 5 70nm激发所产生的 6 0 4nm的发射峰。 相似文献