全文获取类型
收费全文 | 1983篇 |
免费 | 88篇 |
国内免费 | 10篇 |
专业分类
化学 | 1568篇 |
晶体学 | 25篇 |
力学 | 15篇 |
数学 | 114篇 |
物理学 | 359篇 |
出版年
2023年 | 19篇 |
2022年 | 23篇 |
2021年 | 28篇 |
2020年 | 40篇 |
2019年 | 42篇 |
2018年 | 21篇 |
2017年 | 17篇 |
2016年 | 52篇 |
2015年 | 37篇 |
2014年 | 60篇 |
2013年 | 96篇 |
2012年 | 137篇 |
2011年 | 132篇 |
2010年 | 82篇 |
2009年 | 55篇 |
2008年 | 138篇 |
2007年 | 111篇 |
2006年 | 125篇 |
2005年 | 126篇 |
2004年 | 115篇 |
2003年 | 94篇 |
2002年 | 72篇 |
2001年 | 25篇 |
2000年 | 26篇 |
1999年 | 15篇 |
1998年 | 17篇 |
1997年 | 22篇 |
1996年 | 19篇 |
1995年 | 19篇 |
1994年 | 13篇 |
1993年 | 18篇 |
1992年 | 12篇 |
1991年 | 11篇 |
1990年 | 11篇 |
1988年 | 10篇 |
1987年 | 10篇 |
1986年 | 9篇 |
1985年 | 19篇 |
1984年 | 21篇 |
1983年 | 12篇 |
1982年 | 15篇 |
1981年 | 21篇 |
1980年 | 20篇 |
1979年 | 17篇 |
1978年 | 13篇 |
1977年 | 17篇 |
1976年 | 11篇 |
1975年 | 9篇 |
1974年 | 8篇 |
1973年 | 9篇 |
排序方式: 共有2081条查询结果,搜索用时 15 毫秒
91.
The demand for more efficient methods of establishing the undetermined stereochemistries of peptidic natural products continues unabated. A new method for microscale stereochemical determination was devised by integrating solid-phase synthesis, split-and-mix randomization, 18O/16O-encoding of d /l -configurations, tandem mass spectrometry, and biological evaluation. Here we applied gramicidin A as the molecule for a blind test. Gramicidin A and its 31 diastereomers were randomly prepared in microgram scale with 18O/16O-stereochemical encoding and subjected to MS/MS-structural determination and cytotoxicity assay. Only the parent gramicidin A was selected from among the 32 stereoisomers, validating the high reliability of the present strategy. 相似文献
92.
93.
The decomposition of protein molecules from a mixed-protein solution on the surface of calcium hydroxyapatite (CaHap) and Ti(IV)-doped CaHap (TiHap) particles with a Ti/(Ca + Ti) atomic ratio (X Ti) of 0.10 and 0.20 under UV irradiation of 365 nm in wavelength was investigated. Acidic bovine serum albumin (BSA) and basic lysozyme (LSZ) were employed as a model of pathogenic proteins. The photocatalytic activities of TiHap particles were estimated from the decomposition of BSA and LSZ from the BSA (2.5 mg/cm3)–LSZ(1.0 mg/cm3) mixture under 1 mW/cm2 UV irradiation dispersed in a 10-mL quartz tube. No change in BSA concentration by UV irradiation was observed for all the unheated original CaHap and TiHap particles without and with low photocatalytic activities, respectively. Similar results were observed for the systems that employed heat-treated particles endowed a high photocatalytic activity by heat treatment at 650 °C for 1 h. On the other hand, a selective photocatalytic decomposition was observed for the LSZ, i.e., only LSZ molecules were decomposed completely from the BSA (2.5 mg/cm3)–LSZ(1.0 mg/cm3) mixture by using heat-treated TiHap particles with X Ti?=?0.10 and 0.20. This selective decomposition by TiHap particles was interpreted by higher adsorption affinity of positively charged LSZ to highly negatively charged TiHap together with low molecular weight and rigid structure of LSZ molecules. 相似文献
94.
Zihui Li Hiroaki Sai Kwan Wee Tan Tobias N. Hoheisel Sol M. Gruner Ulrich Wiesner 《Journal of Sol-Gel Science and Technology》2014,70(2):286-291
A novel strategy for fabrication of ordered ceramic–metal nanocomposites was demonstrated by multifunctional block copolymer/metal nanoparticle self-assembly. Hybrid organic–inorganic block copolymer poly(3-methacryloxypropyl-T8-heptaisobutyl-polyhedral oligomeric silsesquioxane-block-N,N-dimethylaminoethyl methacrylate) was synthesized and used as a bi-functional structure directing agent for ligand-stabilized platinum nanoparticles to form ordered organic–inorganic nanocomposites with dense loading of inorganic species in both microphase separated domains. Subsequently, thin films of the hybrid material were converted to ordered silica (ceramic)–platinum (metal) nanocomposites via UV-assisted ozonolysis. This is the first time ordered ceramic–metal nanocomposites were achieved through a bottom-up approach, opening up opportunities for the design and synthesis of a broad range of ordered inorganic–inorganic nanocomposites. 相似文献
95.
Houfu Lv Dr. Tianfu Liu Dr. Xiaomin Zhang Dr. Yuefeng Song Hiroaki Matsumoto Prof. Dr. Na Ta Chaobin Zeng Prof. Dr. Guoxiong Wang Prof. Dr. Xinhe Bao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16102-16107
In situ exsolution of metal nanoparticles in perovskite under reducing atmosphere is employed to generate a highly active metal–oxide interface for CO2 electrolysis in a solid oxide electrolysis cell. Atomic-scale insight is provided into the exsolution of CoFe alloy nanoparticles in La0.4Sr0.6Co0.2Fe0.7Mo0.1O3−δ (LSCFM) by in situ scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy and DFT calculations. The doped Mo atoms occupy B sites of LSCFM, which increases the segregation energy of Co and Fe ions at B sites and improves the structural stability of LSCFM under a reducing atmosphere. In situ STEM measurements visualized sequential exsolution of Co and Fe ions, formation of CoFe alloy nanoparticles, and reversible exsolution and dissolution of CoFe alloy nanoparticles in LSCFM. The metal–oxide interface improves CO2 adsorption and activation, showing a higher CO2 electrolysis performance than the LSCFM counterparts. 相似文献
96.
Dr. Tomoya Oshikiri Haruki Jo Dr. Xu Shi Prof. Hiroaki Misawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(24):e202200288
Hot-hole injection from plasmonic metal nanoparticles to the valence band of p-type semiconductors and reduction by hot electrons should be improved for efficient and tuneable reduction to obtain beneficial chemical compounds. We employed the concept of modal strong coupling between plasmons and a Fabry-Pérot (FP) nanocavity to enhance the hot-hole injection efficiency. We fabricated a photocathode composed of gold nanoparticles (Au−NPs), p-type nickel oxide (NiO), and a platinum film (Pt film) (ANP). The ANP structure absorbs visible light over a broad wavelength range from 500 nm to 850 nm via hybrid modes based on the modal strong coupling between the plasmons of Au−NPs and the FP nanocavity of NiO on a Pt film. All wavelength regions of the hybrid modes of the modal strong coupling system promoted hot-hole injection from the Au−NPs to NiO and proton/water reduction by hot electrons. The incident photon-to-current efficiency based on H2 evolution through water/proton reduction by hot electrons reached 0.2 % at 650 nm and 0.04 % at 800 nm. 相似文献
97.
Deguchi K Keira T Yamada K Ito H Takegawa Y Nakagawa H Nishimura S 《Journal of chromatography. A》2008,1189(1-2):169-174
A novel chromatographic approach coupling anion-exchange (diethylaminoethylene) and hydrophilic-interaction (amide or zwitterionic type) columns was developed for the separating of 2-pyridylamino derivatives of N-glycans (PA-N-glycans). This is a kind of on-line, two-dimensional (2D) separation approach in hydrophilic-interaction chromatography (called the 2D-HILIC method), analogous to that of coupling cation- (or anion-, or mixed ion-) exchange and reversed-phase columns in hydrophobic interaction (reversed-phase) chromatography. The efficiency of the 2D-HILIC method was tested with biantennary neutral and sialylated PA-N-glycan standards by properly combining linear gradient elutions of water-acetonitrile and spiked-salt (ammonium acetate) elutions. The retention time RSDs of all the peaks in three sequential runs of a 100 min cycle are less than 0.52%, which indicates a reasonably good repeatability of the 2D-HILIC method. Then, the method was applied to a complex mixture of PA-N-glycans from human serum proteins. It was demonstrated that the neutral PA-N-glycans and mono-, di-, tri-, and tetrasialylated PA-N-glycans are able to be eluted in turn according to the number of sialic acids in an automated (programmed) single run. 相似文献
98.
Mengxing Cui Ryuichi Murase Yongbing Shen Tetsu Sato Shohei Koyama Kaiji Uchida Tappei Tanabe Shinya Takaishi Masahiro Yamashita Hiroaki Iguchi 《Chemical science》2022,13(17):4902
Electrical conduction among metallocycles has been unexplored because of the difficulty in creating electronic transport pathways. In this work, we present an electrocrystallization strategy for synthesizing an intrinsically electron-conductive metallocycle, [Ni6(NDI-Hpz)6(dma)12(NO3)6]·5DMA·nH2O (PMC-hexagon) (NDI-Hpz = N,N′-di(1H-pyrazol-4-yl)-1,4,5,8-naphthalenetetracarboxdiimide). The hexagonal metallocycle units are assembled into a densely packed ABCABC… sequence (like the fcc geometry) to construct one-dimensional (1D) helical π-stacked columns and 1D pore channels, which were maintained under the liberation of H2O molecules. The NDI cores were partially reduced to form radicals as charge carriers, resulting in a room-temperature conductivity of (1.2–2.1) × 10−4 S cm−1 (pressed pellet), which is superior to that of most NDI-based conductors including metal–organic frameworks and organic crystals. These findings open up the use of metallocycles as building blocks for fabricating conductive porous molecular materials.Intrinsically electron-conductive metallocycle was synthesized. π-Radicals play a key role in constructing π-stacked columns among molecular hexagons and achieving high electrical conductivity over 10−4 S cm−1 in polycrystalline pellet. 相似文献
99.
100.
In this paper, we describe a statistical method of quantification of the number of functional groups at the contact area of a probe tip for atomic force microscopy from the result of repetitive pull-off force measurements. We have investigated laboratory-made carbon nanotube (CNT) probe tips to apply them for chemical force microscopy because limited number of functional groups at the tip-end is expected. Using a CNT tip, we conducted repetitive pull-off force measurements against a self-assembled monolayer terminated with carboxyl group and analyzed them in terms of the number of hydrogen bond groups at the CNT tip. The elementary hydrogen bond rupture force quantum in n-decane medium was estimated to be 84.2 ± 0.5 pN in the present system. Thus it was revealed that only a couple of hydrogen bond groups of the CNT tip were participating in hydrogen bonding with the sample on an average in this experimental system. 相似文献