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排序方式: 共有299条查询结果,搜索用时 15 毫秒
291.
Takao Fujimori Kousuke KurisakiTadashi Okobira Kazuya UezuKazuhisa Yoshimura 《Polymer Degradation and Stability》2011,96(8):1516-1521
This paper deals with the desulfonation properties of some strong acid cation-exchange resins. The sulfate concentration in solution is continuously increased when a strong acid cation-exchange resin is mixed with water. The leaching of sulfate results from the desulfonation of the fixed group, and the amount of leached sulfate depends on the counter ion charge, the crosslinking degree and the exchanger matrix. The effects of the counter ion charge on the desulfonation rate suggested that the counter ion induces the nucleophilic attack of a water molecule on the sulfo group. This interpretation was supported by semiempirical molecular orbital calculations for the C6H5SO3−Mm+ (Mm+ = Na+, Mg2+ and Al3+) systems, and the transition state of the Na+ system was successfully predicted by DFT calculations. The crosslinking degree influenced the desulfonation rate, which can be related to the decreasing hydration number of each counter ion in the resin phase with the increasing crosslinking degree. Furthermore, different exchanger matrices produced the differences in the rates, which may be derived from the electron-density donation from the exchanger matrix to the sulfo group. The desulfonation is governed by the electron-density of the sulfur atom and the water activity in the solid phase. 相似文献
292.
Shimoyama A Saeki A Tanimura N Tsutsui H Miyake K Suda Y Fujimoto Y Fukase K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(51):14464-14474
Helicobacter pylori is a common cause of gastroduodenal inflammatory diseases such as chronic gastritis and peptic ulcers and also an important factor in gastric carcinogenesis. Recent reports have demonstrated that bacterial inflammatory processes, such as stimulation with H. pylori lipopolysaccharide (LPS), initiate atherosclerosis. To establish the structures responsible for the inflammatory response of H. pylori LPS, we synthesized various kinds of lipid A structures (i.e., triacylated lipid A and Kdo‐lipid A compounds), with or without the ethanolamine group at the 1‐phosphate moiety, by a new divergent synthetic route. Stereoselective α‐glycosylation of Kdo N‐phenyltrifluoroacetimidate was achieved by use of microfluidic methods. None of the lipid A and Kdo‐lipid A compounds were a strong inducer of IL‐1β, IL‐6, or IL‐8, suggesting that H. pylori LPS is unable to induce acute inflammation. In fact, the lipid A and Kdo‐lipid A compounds showed antagonistic activity against cytokine induction by E. coli LPS, except for the lipid A compound with the ethanolamine group, which showed very weak agonistic activity. On the other hand, these H. pylori LPS partial structures showed potent IL‐18‐ and IL‐12‐inducing activities. IL‐18 has been shown to correlate with chronic inflammation, so H. pylori LPS might be implicated in the chronic inflammatory responses induced by H. pylori. These results also indicated that H. pylori LPS can modulate the immune response: NF‐κB activation through hTLR4/MD‐2 was suppressed, whereas production of IL‐18 and IL‐12 was promoted. 相似文献
293.
Behenna DC Mohr JT Sherden NH Marinescu SC Harned AM Tani K Seto M Ma S Novák Z Krout MR McFadden RM Roizen JL Enquist JA White DE Levine SR Petrova KV Iwashita A Virgil SC Stoltz BM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(50):14199-14223
α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursor: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center. 相似文献
294.
Alfred Q.R. Baron John P. Sutter Satoshi Tsutsui Takahiko Masui Rolf Heid 《Journal of Physics and Chemistry of Solids》2008,69(12):3100-3102
We have measured the buckling, B1g, phonon mode of optimally doped, de-twinned, YBa2Cu3O7−δ using inelastic X-ray scattering (IXS) at BL35XU of SPring-8. Measurements of this mode, which has atomic motion transverse to the Cu-O planes, serve to demonstrate some of the advantages of the unique two-dimensional (2-D) analyzer array at BL35. Analysis based on fitting the entire spectra simultaneously at 10 and 100 K shows that the buckling mode is rather broad in the middle of the zone (near (0.3 0 0)). We see a consistent softening of the mode at 10 K as compared to 100 K for all measured wave-vectors (h 0 0), and a q-dependent softening as zone center is approached. 相似文献
295.
Nishio T An T Nomura A Miyachi K Eguchi T Sakata H Lin S Hayashi N Nakai N Machida M Hasegawa Y 《Physical review letters》2008,101(16):167001
Superconductivity of nanosized Pb-island structures whose radius is 0.8 to 2.5 times their coherence length was studied under magnetic fields using low-temperature scanning tunneling microscopy and spectroscopy. Spatial profiles of superconductivity were obtained by conductance measurements at zero-bias voltage. Critical magnetic fields for vortex penetration and expulsion and for superconductivity breaking were measured for each island. The critical fields depending on the lateral size of the islands and existence of the minimum lateral size for vortex formation were observed. 相似文献
296.
297.
298.
Dr. Daichi Kato Dr. Peng Song Dr. Hiroki Ubukata Haruki Taguro Dr. Cédric Tassel Dr. Kohei Miyazaki Prof. Takeshi Abe Dr. Kousuke Nakano Prof. Kenta Hongo Prof. Ryo Maezono Prof. Hiroshi Kageyama 《Angewandte Chemie (International ed. in English)》2023,62(30):e202301416
Mixed-anion compounds have attracted growing attentions, but their synthesis is challenging, making a rational search desirable. Here, we explored LaF3-LaX3 (X=Cl, Br, I) system using ab initio structure searches based on evolutionary algorithms, and predicted LaF2X and LaFX2 (X=Br, I), which are respectively isostructural with LaHBr2 and YH2I, consisting of layered La-F blocks with single and double ordered honeycomb lattices, separated by van der Waals gaps. We successfully synthesized these compounds: LaF2Br and LaFI2 crystallize in the predicted structure, while LaF2I is similar to the predicted one but with different layer stacking. LaF2I exhibits fluoride ion conductivity comparable to that of non-doped LaF3, and has the potential to show better ionic conductivity upon appropriate doping, given the theoretically lower diffusion energy barrier and the presence of soft iodine anions. This study shows the structure prediction using evolutionary algorithms will accelerate the discovery of mixed-anion compounds in future, in particular those with an ordered anion arrangement. 相似文献
299.