全文获取类型
收费全文 | 1436篇 |
免费 | 31篇 |
国内免费 | 7篇 |
专业分类
化学 | 1047篇 |
晶体学 | 16篇 |
力学 | 26篇 |
数学 | 56篇 |
物理学 | 329篇 |
出版年
2022年 | 9篇 |
2021年 | 14篇 |
2020年 | 14篇 |
2019年 | 19篇 |
2018年 | 8篇 |
2016年 | 25篇 |
2015年 | 24篇 |
2014年 | 24篇 |
2013年 | 64篇 |
2012年 | 53篇 |
2011年 | 79篇 |
2010年 | 40篇 |
2009年 | 43篇 |
2008年 | 72篇 |
2007年 | 83篇 |
2006年 | 68篇 |
2005年 | 71篇 |
2004年 | 61篇 |
2003年 | 64篇 |
2002年 | 74篇 |
2001年 | 41篇 |
2000年 | 34篇 |
1999年 | 30篇 |
1998年 | 21篇 |
1997年 | 12篇 |
1996年 | 11篇 |
1995年 | 11篇 |
1994年 | 13篇 |
1993年 | 17篇 |
1992年 | 38篇 |
1991年 | 21篇 |
1990年 | 20篇 |
1989年 | 21篇 |
1988年 | 21篇 |
1987年 | 15篇 |
1986年 | 7篇 |
1985年 | 22篇 |
1984年 | 15篇 |
1983年 | 17篇 |
1982年 | 14篇 |
1981年 | 15篇 |
1980年 | 10篇 |
1979年 | 10篇 |
1978年 | 10篇 |
1977年 | 14篇 |
1976年 | 11篇 |
1975年 | 10篇 |
1974年 | 13篇 |
1973年 | 15篇 |
1968年 | 9篇 |
排序方式: 共有1474条查询结果,搜索用时 0 毫秒
61.
Polychlorinated biphenyls (PCBs) and chlorobenzenes (CBzs) are two classes of dioxin precursors formed in municipal solid waste incinerators (MSWIs); they produce negative health effects similar to those of dioxins. Reducing the analytical time required for determining the concentrations of these compounds in MSWIs is important for quickly evaluating their importance and assessing associated health risks. In the present study, water is used as a safe and environmentally friendly solvent in microwave-assisted extraction (MAE) for PCB and CBz analyses. MAE is compared with traditional Soxhlet extraction (SE) to determine the extraction efficiencies. The evaluation of extraction efficiencies shows that MAE has a high extraction efficiency compared with that of SE when water content is lower than 60%. Furthermore, the extraction time and organic solvent consumption are reduced with MAE compared with SE. 相似文献
62.
Dr. Yoshiyuki Kageyama Tomonori Ikegami Yuta Kurokome Prof. Dr. Sadamu Takeda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(25):8669-8675
Macroscopic and spatially ordered motions of self‐assemblies composed of oleic acid and a small amount of an azobenzene derivative, induced by azobenzene photoisomerization, was previously reported. However, the mechanism of the generation of submillimeter‐scale motions by the nanosized structural transition of azobenzene was not clarified. Herein, an underlying mechanism of the motions is proposed in which deprotonation of carboxyl groups in cooperation with azobenzene photoisomerization causes a morphological transition of the self‐assembly, which in turn results in macroscopic forceful dynamics. The photoinduced deprotonation was investigated by potentiometric pH titration and FTIR spectroscopy. The concept of hierarchical molecular interaction generating macroscale function is expected to promote the next stage of supramolecular chemistry. 相似文献
63.
64.
Mori Y Hirokawa T Aoki K Satomi H Takeda S Aburada M Miyamoto K 《Chemical & pharmaceutical bulletin》2008,56(5):682-687
We previously reported a quinoxalin-2-one compound (Compound 1) that had inhibitory activity equivalent to existing platelet-derived growth factor-beta receptor (PDGFbeta R) inhibitors. Lead optimization of Compound 1 to increase its activity and selectivity, using structural information regarding PDGFbeta R-ligand interactions, is urgently needed. Here we present models of the PDGFbeta R kinase domain complexed with quinoxalin-2-one derivatives. The models were constructed using comparative modeling, molecular dynamics (MD) and ligand docking. In particular, conformations derived from MD, and ligand binding site information presented by alpha-spheres in the pre-docking processing, allowed us to identify optimal protein structures for docking of target ligands. By carrying out molecular modeling and MD of PDGFbeta R in its inactive state, we obtained two structural models having good Compound 1 binding potentials. In order to distinguish the optimal candidate, we evaluated the structural activity relationships (SAR) between the ligand-binding free energies and inhibitory activity values (IC50 values) for available quinoxalin-2-one derivatives. Consequently, a final model with a high SAR was identified. This model included a molecular interaction between the hydrophobic pocket behind the ATP binding site and the substitution region of the quinoxalin-2-one derivatives. These findings should prove useful in lead optimization of quinoxalin-2-one derivatives as PDGFb R inhibitors. 相似文献
65.
Kawasaki T Suzuki K Hatase K Otsuka M Koshima H Soai K 《Chemical communications (Cambridge, England)》2006,(17):1869-1871
Enantiomorphous crystals composed of achiral hippuric acid, i.e., naturally occurring N-benzoylglycine, have been used successfully as chiral inducers in enantioselective synthesis in combination with asymmetric autocatalysis to afford the product with extremely high enantiomeric excess. 相似文献
66.
Aoki S Sakurama K Matsuo N Yamada Y Takasawa R Tanuma S Shiro M Takeda K Kimura E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(35):9066-9080
A new fluorescent probe for Zn2+, namely, 8-hydroxy-5-N,N-dimethylaminosulfonylquinolin-2-ylmethyl-pendant cyclen (L8), was designed and synthesized (cyclen=1,4,7,10-tetraazacyclododecane). By potentiometric pH, 1H NMR, and UV spectroscopic titrations, the deprotonation constants pKa1-pKa6 of L(8)4 HCl were determined to be <2, <2, <2 (for amino groups of the cyclen and quinoline moieties), 7.19+/-0.05 (for 8-OH of the quinoline moiety), 10.10+/-0.05, and 11.49+/-0.05, respectively, at 25 degrees C with I=0.1 (NaNO3). The results of 1H NMR, potentiometric pH, and UV titrations, as well as single-crystal X-ray diffraction analysis, showed that L8 and Zn2+ form a 1:1 complex [Zn(H-1L8)], in which the 8-OH group of the quinoline ring of L8 is deprotonated and coordinates to Zn2+, in aqueous solution at neutral pH. On addition of one equivalent of Zn2+ and Cd2+, the fluorescence emission of L8 (5 microM) at 512 nm in aqueous solution at pH 7.4 [10 mM HEPES with I=0.1 (NaNO3)] and 25 degrees C increased by factors of 17 and 43, respectively. We found that the cyclen moiety has the unique property of quenching the fluorescence emission of the quinolinol moiety when not complexed with metal cations, but enhancing emission when complexed with Zn2+ or Cd2+. In addition, the Zn2+-L8 complex [Zn(H-1L8)] is much more thermodynamically and kinetically stable (Kd{Zn(H-1L8)}=[Zn2+]free[L8]free/[Zn(H-1L8)]=8 fM at pH 7.4) than the Zn2+ complexes of our previous Zn2+ fluorophores ([Zn(H-1L2)] and [Zn(L3)]). Furthermore, formation of [Zn(H-1L8)] is much faster than those of [Zn(H-1L2)] and [Zn(L3)]. The staining of early-stage apoptotic cells with L8 is also described. 相似文献
67.
Takeda A Yokoyama Y Ito S Miyazaki T Shimotani H Yakigaya K Kakiuchi T Sawa H Takagi H Kitazawa K Dragoe N 《Chemical communications (Cambridge, England)》2006,(8):912-914
The synthesis of a mg amount of pure argon containing fullerene allowed the synthesis of the first endohedral superconductors with critical temperatures lower than expected, an indication of the strong influence of the argon atom on the C60 cage. 相似文献
68.
Prof. Yukishige Ito Prof. Yasuhiro Kajihara Prof. Yoichi Takeda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(67):15461-15470
The introduction of Asn-linked glycans to nascent polypeptides occurs in the lumen of the endoplasmic reticulum of eukaryotic cells. After the removal of specific sugar residues, glycoproteins acquire signals in the glycoprotein quality control (GPQC) system and enter the folding cycle composed of lectin-chaperones calnexin (CNX) and calreticulin (CRT), glucosidase II (G-II), and UDP-Glc:glycoprotein glucosyltransferase (UGGT). G-II initiates glycoproteins’ entry and exit from the cycle, and UGGT serves as the “folding sensor”. This account summarizes our effort to analyze the properties of enzymes and lectins that play important roles in GPQC, especially those involved in the CNX/CRT cycle. To commence our study, general methods for the synthesis of high-mannose-type glycans and glycoproteins were established. Based on these, various substrates to analyze components of the GPQC were created, and properties of CRT, G-II, and UGGT have been clarified. 相似文献
69.
K. Yanagisawa H. Takeda K. Miyamoto S. Fuma N. Ishii 《Journal of Radioanalytical and Nuclear Chemistry》2002,251(2):277-280
Tracer experiments on the transfer of carbon from culture solution to Daphnia magna through phytoplankton have been carried out using 13C and infrared absorption method. The purpose of this experiment is to investigate the experimental systems for the use of 13C in aquatic system. Daphnia magna was cultured in a 100 ml of solution containing phytoplankton and 20 mg of NaH13CO3 for 24 hours in the light and dark conditions (2000 lux, 14 hour light and 10 hours dark at 25 C). The concentration of 13C in Daphnia magna under light condition was about 2.0% (atom% excess), while in the dark condition 13C tracer was not detected. The concentration of 13C in phytoplankton under light condition was around 20%. It was suggested that 13C added as carbonate in the culture solution was photosynthetically assimilated by phytoplankton and then transferred to Daphnia magna. Using this system, the effect of UV-B exposure on the 13C uptake of Daphnia magna has been examined. The UV-B intensity was 95 mW/cm2 and exposure time was 15, 30, and 60 minutes. The concentration of 13C in Daphnia magna decreased with increasing exposure time. The Daphnia magna exposed to UV-B for 15 minutes intakes phytoplankton as much as control, while 30 minutes and 60 minutes exposures were lower than control. The lower concentrations of 13C observed in Daphnia magna were due to less intake of phytoplankton caused by the UV-B exposure. 相似文献
70.
Kojima Kunihiko Miyazaki Mitsuharu Mizukami Fujio Maeda Kazuyuki 《Journal of Sol-Gel Science and Technology》1997,8(1-3):77-81
The structure of iron oxide was controlled by regulating the hydrolytic polymerization of aquo iron complexes with organic
polydentate ligands such as diols. Iron oxides were prepared by calcining the precursor polymers obtained from iron nitrate
nonahydrate and diols. When the diols were 1,2-pentanediol, 1,2-hexanediol and 1,2-octanediol, α-Fe2O3 with corundum structure appeared exclusively or as the main crystalline phase, in spite of the amount of diol used and the
calcination temperature. In the case of 1,2-decanediol and 1,2-dodecanediol, when five moles of the diols were used to one
mole of iron nitrate and the calcination temperatures were below 400°C, ψ-Fe2O3 with spinel structure appeared as the main phase and, when less than five moles of the diols were used, α-Fe2O3 appeared exclusively or as the main phase, irrespective of the calcination temperature. This tendency was also observed in
thin films. Thus, a transparent magnetic film composed of γ-Fe2O3 could be prepared by applying a benzene solution of the iron polymer, obtained with 5 equivalents of 1,2-decanediol, on quartz
and calcining the gel film at 350°C. 相似文献