全文获取类型
收费全文 | 1382篇 |
免费 | 143篇 |
国内免费 | 104篇 |
专业分类
化学 | 1033篇 |
晶体学 | 15篇 |
力学 | 48篇 |
综合类 | 3篇 |
数学 | 217篇 |
物理学 | 313篇 |
出版年
2023年 | 27篇 |
2022年 | 20篇 |
2021年 | 34篇 |
2020年 | 43篇 |
2019年 | 52篇 |
2018年 | 42篇 |
2017年 | 36篇 |
2016年 | 52篇 |
2015年 | 58篇 |
2014年 | 55篇 |
2013年 | 77篇 |
2012年 | 116篇 |
2011年 | 95篇 |
2010年 | 81篇 |
2009年 | 70篇 |
2008年 | 80篇 |
2007年 | 73篇 |
2006年 | 70篇 |
2005年 | 73篇 |
2004年 | 56篇 |
2003年 | 45篇 |
2002年 | 57篇 |
2001年 | 56篇 |
2000年 | 38篇 |
1999年 | 31篇 |
1998年 | 13篇 |
1997年 | 18篇 |
1996年 | 27篇 |
1995年 | 18篇 |
1994年 | 15篇 |
1993年 | 9篇 |
1992年 | 18篇 |
1991年 | 13篇 |
1990年 | 10篇 |
1989年 | 9篇 |
1988年 | 11篇 |
1987年 | 4篇 |
1986年 | 7篇 |
1985年 | 5篇 |
1984年 | 2篇 |
1983年 | 5篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1967年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有1629条查询结果,搜索用时 203 毫秒
11.
Cooperative Crystallization of Heterometallic Indium–Chromium Metal–Organic Polyhedra and Their Fast Proton Conductivity 下载免费PDF全文
Dr. Quan‐Guo Zhai Chengyu Mao Dr. Xiang Zhao Dr. Qipu Lin Fei Bu Xitong Chen Prof. Dr. Xianhui Bu Prof. Dr. Pingyun Feng 《Angewandte Chemie (International ed. in English)》2015,54(27):7886-7890
Metal–organic polyhedra (MOPs) or frameworks (MOFs) based on Cr3+ are notoriously difficult to synthesize, especially as crystals large enough to be suitable for characterization of the structure or properties. It is now shown that the co‐existence of In3+ and Cr3+ induces a rapid crystal growth of large single crystals of heterometallic In‐Cr‐MOPs with the [M8L12] (M=In/Cr, L=dinegative 4,5‐imidazole‐dicarboxylate) cubane‐like structure. With a high concentration of protons from 12 carboxyl groups decorating every edge of the cube and an extensive H‐bonded network between cubes and surrounding H2O molecules, the newly synthesized In‐Cr‐MOPs exhibit an exceptionally high proton conductivity (up to 5.8×10?2 S cm?1 at 22.5 °C and 98 % relative humidity, single crystal). 相似文献
12.
Andrea Schenkmayerová Anikó Bertóková Jana Šefčovičová Vladimír Štefuca Marek Bučko Alica Vikartovská Peter Gemeiner Ján Tkáč Jaroslav Katrlík 《Analytica chimica acta》2015
A microbial biosensor for 2-phenylethanol (2-PE) based on the bacteria Gluconobacter oxydans was developed and applied in monitoring of a biotechnological process. The cells of G. oxydans were immobilized within a disposable polyelectrolyte complex gel membrane consisting of sodium alginate, cellulose sulphate and poly(methylene-co-guanidine) attached onto a miniaturized Clark oxygen electrode, forming whole cell amperometric biosensor. Measured changes in oxygen concentration were proportional to changes in 2-PE concentration. The biosensor sensitivity was 864 nA mM−1 (RSD = 6%), a detection limit of 1 μM, and the biosensor response towards 2-PE was linear in the range 0.02–0.70 mM. The biosensor preserved 93% of its initial sensitivity after 7 h of continuous operation and exhibited excellent storage stability with loss of only 6% of initial sensitivity within two months, when stored at 4 °C. The developed system was designed and successfully used for an off-line monitoring of whole course of 2-PE biooxidation process producing phenylacetic acid (PA) as industrially valuable aromatic compound. The biosensor measurement did not require the use of hazardous organic solvent. The biosensor response to 2-PE was not affected by interferences from PA and phenylacetaldehyde at concentrations present in real samples during the biotransformation and the results were in a very good agreement with those obtained via gas chromatography. 相似文献
13.
Computational Insights into the Charge Relaying Properties of β‐Turn Peptides in Protein Charge Transfers 下载免费PDF全文
Ru Zhang Dr. Jinxiang Liu Dr. Hongfang Yang Shoushan Wang Meng Zhang Prof. Dr. Yuxiang Bu 《Chemphyschem》2015,16(2):436-446
Density functional theory calculations suggest that β‐turn peptide segments can act as a novel dual‐relay elements to facilitate long‐range charge hopping transport in proteins, with the N terminus relaying electron hopping transfer and the C terminus relaying hole hopping migration. The electron‐ or hole‐binding ability of such a β‐turn is subject to the conformations of oligopeptides and lengths of its linking strands. On the one hand, strand extension at the C‐terminal end of a β‐turn considerably enhances the electron‐binding of the β‐turn N terminus, due to its unique electropositivity in the macro‐dipole, but does not enhance hole‐forming of the β‐turn C terminus because of competition from other sites within the β‐strand. On the other hand, strand extension at the N terminal end of the β‐turn greatly enhances hole‐binding of the β‐turn C terminus, due to its distinct electronegativity in the macro‐dipole, but does not considerably enhance electron‐binding ability of the N terminus because of the shared responsibility of other sites in the β‐strand. Thus, in the β‐hairpin structures, electron‐ or hole‐binding abilities of both termini of the β‐turn motif degenerate compared with those of the two hook structures, due to the decreased macro‐dipole polarity caused by the extending the two terminal strands. In general, the high polarity of a macro‐dipole always plays a principal role in determining charge‐relay properties through modifying the components and energies of the highest occupied and lowest unoccupied molecular orbitals of the β‐turn motif, whereas local dipoles with low polarity only play a cooperative assisting role. Further exploration is needed to identify other factors that influence relay properties in these protein motifs. 相似文献
14.
Nanostructured copper‐coated solid‐phase microextraction fiber for gas chromatographic analysis of dibutyl phthalate and diethylhexyl phthalate environmental estrogens 下载免费PDF全文
A novel nanostructured copper‐based solid‐phase microextraction fiber was developed and applied for determining the two most common types of phthalate environmental estrogens (dibutyl phthalate and diethylhexyl phthalate) in aqueous samples, coupled to gas chromatography with flame ionization detection. The copper film was coated onto a stainless‐steel wire via an electroless plating process, which involved a surface activation process to improve the surface properties of the fiber. Several parameters affecting extraction efficiency such as extraction time, extraction temperature, ionic strength, desorption temperature, and desorption time were optimized by a factor‐by‐factor procedure to obtain the highest extraction efficiency. The as‐established method showed wide linear ranges (0.05–250 μg/L). Precision of single fiber repeatability was <7.0%, and fiber‐to‐fiber repeatability was <10%. Limits of detection were 0.01 μg/L. The proposed method exhibited better or comparable extraction performance compared with commercial and other lab‐made fibers, and excellent thermal stability and durability. The proposed method was applied successfully for the determination of model analytes in plastic soaking water. 相似文献
15.
PEG-related adhesives are limited in clinical use because they are easy to swell and cannot support the cell growth.In this study,we produced a series of POSS-modified PEG adhesives with high adhesive strength.Introduction of inorganic hydrophobic POSS units decreased the swelling of the adhesives and enhanced cell adhesion and growth.The in vitro cytotoxicity and in vivo inflammatory response experiments clearly demonstrated that the adhesives were nontoxic and possessed excellent biocompatibility.Compared with the sutured wounds,the adhesive-treated wounds showed an accelerated healing process in wounded skin model of the Bama miniature pig,demonstrating that the POSS-modified PEG adhesive is a promising candidate for wound closure. 相似文献
16.
Lan Luo Ziyi Zhang Yanhua Chen Lixia Zhang Xiangfeng Bu Hanqi Zhang 《International journal of environmental analytical chemistry》2017,97(12):1178-1191
A simple and sensitive surface-enhanced Raman spectroscopy (SERS) method for the detection of safranine T (ST) and Hg2+ using silver nanoparticles (AgNPs) as substrate was developed. ST can absorb on the surface of AgNPs through electrostatic interaction, the electromagnetic effect combined with chemical adsorption effect give a notable Raman enhancement for ST. The presence of Hg2+ well decreased the absorbed ST molecules on AgNPs, leading to a significant decrease of SERS signals thus enabling to detect Hg2+. The determination conditions for SERS, including the amount of AgNPs, the concentration of NaCl, the concentration of HCl, the concentration of ST and the reaction time, were optimised. Under the optimised experimental conditions, good linear responses were obtained for ST and Hg2+ in the concentration ranges of 0.01–4.0 μmol L?1 (3.5–1403.4 ng mL?1) and 0.01–2.0 μmol L?1 (2.0–401.2 ng mL?1), the limit of detection were 3.0 nmol L?1 (1.1 ng mL?1) and 2.0 nmol L?1 (0.4 ng mL?1), respectively. The present method was subsequently applied to the determination of ST in tomato sauces and Hg2+ in environmental waters, the recoveries of ST and Hg2+ in spiked samples are 95.5–107.8% and 91.4–110.8 %, respectively. 相似文献
17.
18.
Wenting Bu Qiuju Guo Jian Zheng Shigeo Uchida 《Journal of Radioanalytical and Nuclear Chemistry》2017,311(2):999-1005
Surface soil samples collected in the Jiuquan region in the downwind area of the Chinese nuclear test site (CNTs) were analyzed for Pu isotopes. The 239+240Pu activities ranged from 0.025 ± 0.009 to 0.89 ± 0.16 mBq g?1, varying significantly with different sampling sites. The Dunhuang city that is located in the southwestern part of the Jiuquan region received the heaviest Pu deposition (239+240Pu activities, 0.23–0.89 mBq g?1). Most of the 240Pu/239Pu isotopic ratios were similar with that of the global fallout. However, the low values (0.080–0.147) observed in three sampling sites further supported the finding of Pu originated from CNTs in that region. 相似文献
19.
A weighted (unweighted) graph is called equiarboreal if the sum of weights (the number) of spanning trees containing a given edge in is independent of the choice of edge. In this paper, we give some resistance characterizations of equiarboreal weighted and unweighted graphs, and obtain the necessary and sufficient conditions for -subdivision graphs, iterated double graphs, line graphs of regular graphs and duals of planar graphs to be equiarboreal. Applying these results, we obtain new infinite families of equiarboreal graphs, including iterated double graphs of 1-walk-regular graphs, line graphs of triangle-free 2-walk-regular graphs, and duals of equiarboreal planar graphs. 相似文献
20.
Let \(\mathcal {U}=\{U(t,s)\}_{t\ge s\ge 0}\) be a strongly continuous and exponentially bounded evolution family acting on a complex Banach space X and let \(\mathcal {X}\) be a certain Banach function space of X-valued functions. We prove that the growth bound of the family \(\mathcal {U}\) is less than or equal to \(-\frac{1}{c(\mathcal {U}, \mathcal {X})}\) provided that the convolution operator \(f\mapsto \mathcal {U}*f\) acts on \(\mathcal {X}.\) It is well known that under the latter assumption, the convolution operator is bounded and then \(c(\mathcal {U}, \mathcal {X})\) denotes (ad-hoc) its norm in \(\mathcal {L}(\mathcal {X}).\) As a consequence, we prove that if \(\sup \nolimits _{s\ge 0}\int \nolimits _{s}^\infty \Vert U(t,s)\Vert dt=u_1(\mathcal {U})<\infty ,\) then \(\omega _0(\mathcal {U})u_1(\mathcal {U})\le -1.\) Finally, we give an example showing that the accuracy of the estimates may be quite accurate. 相似文献