全文获取类型
收费全文 | 1323篇 |
免费 | 132篇 |
国内免费 | 115篇 |
专业分类
化学 | 831篇 |
晶体学 | 28篇 |
力学 | 65篇 |
综合类 | 6篇 |
数学 | 208篇 |
物理学 | 432篇 |
出版年
2023年 | 19篇 |
2022年 | 37篇 |
2021年 | 40篇 |
2020年 | 33篇 |
2019年 | 36篇 |
2018年 | 40篇 |
2017年 | 41篇 |
2016年 | 42篇 |
2015年 | 58篇 |
2014年 | 77篇 |
2013年 | 99篇 |
2012年 | 96篇 |
2011年 | 104篇 |
2010年 | 66篇 |
2009年 | 47篇 |
2008年 | 66篇 |
2007年 | 68篇 |
2006年 | 74篇 |
2005年 | 46篇 |
2004年 | 51篇 |
2003年 | 33篇 |
2002年 | 29篇 |
2001年 | 28篇 |
2000年 | 28篇 |
1999年 | 28篇 |
1998年 | 22篇 |
1997年 | 20篇 |
1996年 | 18篇 |
1995年 | 22篇 |
1994年 | 12篇 |
1993年 | 7篇 |
1992年 | 13篇 |
1991年 | 12篇 |
1990年 | 11篇 |
1989年 | 9篇 |
1988年 | 7篇 |
1987年 | 5篇 |
1986年 | 7篇 |
1985年 | 9篇 |
1984年 | 11篇 |
1982年 | 7篇 |
1981年 | 9篇 |
1980年 | 21篇 |
1979年 | 6篇 |
1977年 | 8篇 |
1976年 | 5篇 |
1974年 | 6篇 |
1973年 | 6篇 |
1972年 | 4篇 |
1969年 | 4篇 |
排序方式: 共有1570条查询结果,搜索用时 15 毫秒
21.
Martinez-Diaz MV Rodriguez-Morgade MS Feiters MC van Kan PJ Nolte RJ Stoddart JF Torres T 《Organic letters》2000,2(8):1057-1060
[formula: see text] New unsymmetrically substituted DB24C8-phthalocyanines, which are able to form complexes with suitable dialkylammonium cations, have been prepared. These complexes most probably have a pseudorotaxane geometry. 相似文献
22.
In an earlier study we showed that a blend of thermoresponsive and nonthermoresponsive hydroxyalkylcelluloses could be used to create a thermally tunable polymer network for double-stranded (ds) DNA separation. Here, we show the generality of this approach using a family of polymers suited to a wider range of DNA separations: a blended mixture of N,N-dialkylacrylamide copolymers with different thermoresponsive behaviors. A mixture of 47% w/w N,N-diethylacrylamide (DEA)/53% w/w N,N-dimethylacrylamide (DMA) (DEA47; thermoresponsive, transition temperature = 55 degrees C in water) and 30% w/w DEA/70% w/w DMA (DEA30; nonthermoresponsive, transition temperature > 85 degrees C in water) copolymers in the ratio of 1:5 w/w DEA47:DEA30 was used to separate a dsDNA restriction digest (PhiX174-HaeIII). We investigated the effects of changing mesh size on dsDNA separation, as controlled by temperature. We observed good DNA separation performance with the copolymer blend at temperatures ranging from 25 degrees C to 48 degrees C. The separation selectivity was evaluated quantitatively for certain DNA fragment pairs as a function of temperature. The results were compared with those obtained with a control matrix consisting only of the nonthermoresponsive DEA30. Different DNA fragment pairs of various sizes show distinct temperature-dependent selectivities. Over the same temperature range, no significant temperature dependence of selectivity is observed for these DNA fragment pairs in the nonthermoresponsive control matrix. Overall, the results show similar trends in the temperature dependency of separation selectivity to what was previously observed in hydroxyalkylcellulose blends, for the same DNA fragment pairs. Finally, we showed that a ramped temperature scheme enables improved separation in the blended copolymer matrix for both small and large DNA fragments, simultaneously in a single capillary electrophoresis (CE) run. 相似文献
23.
An atomic-absorption spectrophotometric method has been developed for the indirect determination of phosphorus. The calibration graph is linear over the range 0.025-0.2 mug of phosphorus. The relative standard deviation is 1.3% for 0.2 mug of phosphorus (6 replicates). The method has been applied to the determination of phosphate in natural water samples. The enhancement effect of acetone on the determination is discussed. 相似文献
24.
本文应用碱性气体吸附的红外光谱和TPD技术研究了FeZSM-5(F_4)的酸性,酸性顺序为:H-F_4>Fe_2O_3/F_4>F_4原粉>水热处理的K-F_4>Li-F_4>NaF_4>K-F_4>NaOH/F_4,比较了酸强度和积炭对乙苯氧化脱氢性能的影响,以及催化剂酸碱性质与积炭的关系.结果表明,乙苯氧化脱氢反应是在酸碱协同作用下进行的,积炭也参与了氧化脱氢反应,催化剂表面上L酸中心产生的具有一定C、H、O比的积炭具有高的氧化脱氢活性.碱金属阳离子改性的具有L酸中心的FeZSM-5是乙苯氧化脱氢的高活性催化剂。 相似文献
25.
Proteins with molecular mass (M(r)) <20 kDa are often poorly separated in 2-D sodium dodecyl sulfate polyacrylamide gel electrophoresis. In addition, low-M(r) proteins may not be readily identified using peptide mass fingerprinting (PMF) owing to the small number of peptides generated in tryptic digestion. In this work, we used a 2-D liquid separation method based on chromatofocusing and non-porous silica reversed-phase high-performance liquid chromatography to purify proteins for matrix-assisted laser desorption/ionization time-of-flight mass spectrometric (MALDI-TOFMS) analysis and protein identification. Several proteins were identified using the PMF method where the result was supported using an accurate M(r) value obtained from electrospray ionization TOFMS. However, many proteins were not identified owing to an insufficient number of peptides observed in the MALDI-TOF experiments. The small number of peptides detected in MALDI-TOFMS can result from internal fragmentation, the few arginines in its sequence and incomplete tryptic digestion. MALDI-QTOFMS/MS can be used to identify many of these proteins. The accurate experimental M(r) and pI confirm identification and aid in identifying post-translational modifications such as truncations and acetylations. In some cases, high-quality MS/MS data obtained from the MALDI-QTOF spectrometer overcome preferential cleavages and result in protein identification. 相似文献
26.
Zhao J Zhang Y Kan Y Zhu L 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(3):679-688
The vibrational spectra of Group IIB elements halides MX2 and their dimers M2X4 (M=Zn(II), Cd(II) and Hg(II); X=F, Cl, Br and I) have been systematically investigated by ab initio RHF and B3LYP methods with LanL2MB, LanL2DZ and SDD basis sets. The optimized geometries, calculated vibrational frequencies are evaluated via comparison with the experimental data. The vibrational frequencies, calculated by these methods with different basis sets, are compared to each other too. The best results can be obtained by RHF/SDD method, with this method, the deviations for MX2 and Hg2X4 are <7%. Some vibrational frequencies of M2X4 that have not been experimentally reported are also predicted. 相似文献
27.
Hong‐Ze Gao Zhong‐Min Su Chun‐Sheng Qin Ri‐Gen Mo Yu‐He Kan 《International journal of quantum chemistry》2004,97(6):992-1001
Bis(2‐methyl‐8‐quinolinolato)aluminum(III) hydroxide complex (AlMq2OH) is used in organic light‐emitting diodes (OLEDs) as an electron transport material and emitting layer. By means of ab initio Hartree–Fock (HF) and density functional theory (DFT) B3LYP methods, the structure of AlMq2OH was optimized. The frontier molecular orbital characteristics and energy levels of AlMq2OH have been analyzed systematically to study the electronic transition mechanism in AlMq2OH. For comparison and calibration, bis(8‐quinolinolato)aluminum(III) hydroxide complex (Alq2OH) has also been examined with these methods using the same basis sets. The lowest singlet excited state (S1) of AlMq2OH has been studied by the singles configuration interaction (CIS) method and time‐dependent DFT (TD‐DFT) using a hybrid functional, B3‐LYP, and the 6‐31G* basis set. The lowest singlet electronic transition (S0 → S1) of AlMq2OH is π → π* electronic transitions and primarily localized on the different quinolate ligands. The emission of AlMq2OH is due to the electron transitions from a phenoxide donor to a pyridyl acceptor from another quinolate ligand including C → C and O → N transference. Two possible electron transfer pathways are presented, one by carbon, oxygen, and nitrogen atoms and the other via metal cation Al3+. The comparison between the CIS‐optimized excited‐state structure with the HF ground‐state structure indicates that the geometric shift is mainly confined to the one quinolate and these changes can be easily understood in terms of the nodal patterns of the highest occupied and lowest unoccupied molecular orbitals. On the basis of the CIS‐optimized structure of the excited state, TD‐B3‐LYP calculations predict an emission wavelength of 499.78 nm. An absorption wavelength at 380.79 nm on the optimized structure of B3LYP/6‐31G* was predicted. They are comparable to AlMq2OH 485 and 390 nm observed experimentally for photoluminescence and UV‐vis absorption spectra of AlMq2OH solid thin film on quartz, respectively. Lending theoretical corroboration to recent experimental observations and supposition, the reasons for the blue‐shift of AlMq2OH were revealed. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004 相似文献
28.
随着杂原子分子筛研究领域的开拓与发展,近年来,对钛硅沸石的研究逐渐增多.Ti-ZSM-11(TS-2)型分子筛是由Reddy,Ratanasarny等[1]首先合成的.钛硅沸石的表征与其它杂原子分子筛相比较为复杂,对杂原子Ti是否进入了骨架还没有一个直接的证据,且争议较多.在红外光谱的研究中,对960cm-1-980cm-1区间的特征吸收的归属也存在着很大的分歧[2-4].钛硅沸石在H2O2对有机化合物的选择氧化领域有极其优良的催化性能[1],因此,对它的开发有广泛的应用前景.本文以动态和静态相结合的水热晶化法合成了Ti-ZSM-11型分子筛.IR光… 相似文献
29.
Jinghe Zhang Yinan Wang Changhong Wang Kan Li Weifang Tang Jing Sun Xikui Wang 《Molecules (Basel, Switzerland)》2022,27(23)
When Aristolochia plants wilt and decay, aristolochic acids (AAs) are released into the soil, causing soil contamination. It has been demonstrated that aristolochic acid can be accumulated and enriched in crops through plant uptake. However, there is a lack of systematic studies on the migration and accumulation of AAs in a realistic simulated soil environment. In this study, Aristolochia herbal extracts were mixed with soil for growing three typical vegetables: lettuce, celery, and tomato. The contents of AAs in the above-mentioned plants were determined by an established highly sensitive LC-MS/MS method to study the migration and accumulation of AAs. We found that AAs in the soil can be transferred and accumulated in plants. AAs first entered the roots, which were more likely to accumulate AAs, and partially entered the above-ground parts. This further confirms that AAs can enter the food chain through plants and can have serious effects on human health. It was also shown that plants with vigorous growth and a large size absorbed AAs from the soil at a faster rate. The more AAs present in the soil, the more they accumulated in the plant. 相似文献
30.