全文获取类型
收费全文 | 871篇 |
免费 | 6篇 |
国内免费 | 6篇 |
专业分类
化学 | 647篇 |
晶体学 | 4篇 |
力学 | 20篇 |
数学 | 40篇 |
物理学 | 172篇 |
出版年
2023年 | 4篇 |
2022年 | 5篇 |
2021年 | 4篇 |
2020年 | 4篇 |
2019年 | 11篇 |
2018年 | 11篇 |
2017年 | 5篇 |
2016年 | 10篇 |
2015年 | 13篇 |
2014年 | 13篇 |
2013年 | 25篇 |
2012年 | 36篇 |
2011年 | 52篇 |
2010年 | 28篇 |
2009年 | 37篇 |
2008年 | 57篇 |
2007年 | 60篇 |
2006年 | 62篇 |
2005年 | 67篇 |
2004年 | 51篇 |
2003年 | 34篇 |
2002年 | 42篇 |
2001年 | 11篇 |
2000年 | 14篇 |
1999年 | 9篇 |
1998年 | 9篇 |
1997年 | 3篇 |
1996年 | 17篇 |
1995年 | 10篇 |
1994年 | 4篇 |
1993年 | 10篇 |
1992年 | 11篇 |
1991年 | 4篇 |
1990年 | 9篇 |
1988年 | 4篇 |
1987年 | 7篇 |
1986年 | 9篇 |
1985年 | 19篇 |
1984年 | 17篇 |
1983年 | 6篇 |
1982年 | 9篇 |
1981年 | 9篇 |
1980年 | 6篇 |
1979年 | 7篇 |
1978年 | 11篇 |
1977年 | 3篇 |
1975年 | 6篇 |
1974年 | 4篇 |
1968年 | 6篇 |
1967年 | 3篇 |
排序方式: 共有883条查询结果,搜索用时 31 毫秒
191.
Ikeda A Sato T Kitamura K Nishiguchi K Sasaki Y Kikuchi J Ogawa T Yogo K Takeya T 《Organic & biomolecular chemistry》2005,3(16):2907-2909
Various types of lipid membrane-incorporated C60 with high C60 concentrations can be prepared easily in several hours using the C60 exchange method and the photocleaving activity of cationic lipid membrane-incorporated C60 was appreciably higher than that of the C60.gamma-CDx complex. 相似文献
192.
Ariga K Urakawa T Michiue A Kikuchi J 《Langmuir : the ACS journal of surfaces and colloids》2004,20(16):6762-6769
As a novel category of two-dimensional lipid clusters, dendrimers having an amphiphilic structure in every unit were synthesized and labeled "spider-web amphiphiles". Amphiphilic units based on a Lys-Lys-Glu tripeptide with hydrophobic tails at the C-terminal and a polar head at the N-terminal are dendrically connected through stepwise peptide coupling. This structural design allowed us to separately introduce the polar head and hydrophobic tails. Accordingly, we demonstrated the synthesis of the spider-web amphiphile series in three combinations: acetyl head/C16 chain, acetyl head/C18 chain, and ammonium head/C16 chain. All the spider-web amphiphiles were synthesized in satisfactory yields, and characterized by 1H NMR, MALDI-TOFMS, GPC, and elemental analyses. Surface pressure (pi)-molecular area (A) isotherms showed the formation of expanded monolayers except for the C18-chain amphiphile at 10 degrees C, for which the molecular area in the condensed phase is consistent with the cross-sectional area assigned for all the alkyl chains. In all the spider-web amphiphiles, the molecular areas at a given pressure in the expanded phase increased in proportion to the number of units, indicating that alkyl chains freely fill the inner space of the dendritic core. The mixing of octadecanoic acid with the spider-web amphiphiles at the air-water interface induced condensation of the molecular area. From the molecular area analysis, the inclusion of the octadecanoic acid bears a stoichiometric characteristic; i.e., the number of captured octadecanoic acids in the spider-web amphiphile roughly agrees with the number of branching points in the spider-web amphiphile. 相似文献
193.
A 60kDa spider toxin binding protein from bovine brain was solubilized with digitonin and purified up to 5800-folds over starting crude homogenate. The purification procedure entailed DEAE-cellulose, concanavalin-A affinity, 1-naphthylacetyl spermine affinity and high performance liquid chromatography. The purified protein owned a very high affinity for ligand 125I-JSTX-3 binding Kd 15.6nM and Bmax 6.5nM. The amino acid composition of the protein was determined. The N-terminal amino acid sequence analysis yielded a unique sequence: NH2-X-Pro-X-Val-Tyr-Phe-Lys-Glu-Gln-Phe-Leu-Asp-Gly-Asp-X. 相似文献
194.
Nagawa Y Suga J Hiratani K Koyama E Kanesato M 《Chemical communications (Cambridge, England)》2005,(6):749-751
A novel [3]rotaxane composed of two 25-membered crownophanes and one axle molecule having two anthryl end groups was successfully synthesized via covalent bond formation followed by aminolysis, and can incorporate caesium ion into the space between the two macrocycles as a 1 : 1 sandwich-type complex, whereas it makes a 1 : 2 complex with lithium ion. 相似文献
195.
Keita?Suzuki Jun-ichi?Oku Kenichi?Izawa Hiro-Fumi?OkabayashiEmail author Isao?Noda Charmian?J.?O’Connor 《Colloid and polymer science》2004,283(3):306-316
The two-step polymerization process of two well-defined polymeric silane coupling agents, triethoxysilyl-terminated polystyrene with molecular weights equal to 2400 [TESi-PS (2400)] and 8000 [TESi-PS (8000)], catalyzed by 0.1 mol/kg CH3SO3H, was traced as a function of reaction time using gel-permeation chromatography (GPC). Two sets of GPC traces, collected during the condensation, were then converted to two-dimensional (2D) correlation spectra by using generalized 2D correlation theory. The 2D correlation spectra elucidated details of the aggregate–aggregate correlations [in particular, the difference between the correlations of TESi-PS (2400) and TESi-PS (8000)], thus demonstrating the effect of aggregation on the polymerization. 相似文献
196.
Ariga K Yuki H Kikuchi J Dannemuller O Albrecht-Gary AM Nakatani Y Ourisson G 《Langmuir : the ACS journal of surfaces and colloids》2005,21(10):4578-4583
The monolayer properties of some single-chain polyprenyl phosphates (phytanyl, phytyl, and geranylgeranyl phosphates), which we regard as hypothetical primitive membrane lipids, were investigated at the air-water interface by surface pressure-area (pi-A) isotherm measurements. The molecular area/ pressure at various pH conditions dependence revealed the acid dissociation constants (pKa values) of the phosphate. The pKa values thus obtained at the air-water interface (pKa1 = 7.1 and pKa2 = 9.4 for phytanyl phosphate) were significantly shifted to higher pH than those observed in the bilayer state in water (pKa1 = 2.9 and pKa2 = 7.8). The difference in pKa values leads to a stability of the phosphate as both monolayer and bilayer states in a pH range of 2-6. In addition, the presence of ions such as sodium, magnesium, calcium, and lanthanum in the subphase significantly altered the stability of the polyprenyl phosphate monolayers, as shown by the determination of monolayer collapse and compression/expansion hysteresis. Although sodium ions in the subphase showed only a weak effect on the stabilization of the monolayer, addition of magnesium ions or of a small amount of calcium ions significantly suppressed the dissolution of the monolayer into the subphase and increased its mechanical stability against collapse. In contrast, the presence of larger amounts of calcium or of lanthanum ions induced collapse of the monolayers. Based on these experimental facts, a plausible scenario for the formation of primitive cell membrane by transformation of a monolayer to vesicle structures is proposed. 相似文献
197.
Yamada Ji Satoki S Mishima S Akashi N Takahashi K Masuda N Nishimoto Y Takasaki S Anzai H 《The Journal of organic chemistry》1996,61(12):3987-3995
Efficient synthetic methods for the construction of a wide variety of unsymmetrical tetrathiafulvalenes (TTFs) via the Me(3)Al-promoted reactions of organotin thiolates or selenolates with esters are described. Reaction of tin thiolates (3a-c and 10) and selenolates (3d, 5, and 7) with esters (11a,b) in the presence of Me(3)Al as a Lewis acid gave dihydrotetrathiafulvalene derivatives (12, 14, 15, and 17-20) and 1,3-dithiane derivatives (13 and 16). In addition, the synthesis of diselenadithiafulvalene derivatives (25-28) could be accomplished by Me(3)Al-mediated reaction of tin thiolate (2a) or selenolates (3d and 5) with esters (22a, 22d, and 24). Furthermore, the application of the Me(3)Al-promoted reaction of tin thiolate (34) with esters (11a-b, 22a-d, and 35a-b) for the synthesis of unsymmetrical TTFs-fused donors enabled us to obtain various TTFs-fused systems (29-33) in short steps. 相似文献
198.
Jun-ichi Hibino Seijiro Matsubara Yoshitomi Morizawa Koichiro Oshima Hitosi Nozaki 《Tetrahedron letters》1984,25(20):2151-2154
The reaction of terminal acetylenes with Bu3SnMgMe, Bu3SnA1Et2, or (Bu3Sn)2Zn in the presence of various transition-metal catalysts provides vinylstannanes in good yields. Whereas copper catalysed stannylmagnesation of 4-benzyloxy-1-butyne gives (E)-4-benzyloxy-1-tributylstannyl-1-butene exclusively, palladium catalysed stannylzincation affords 4-benzyloxy-2-tributylstannyl-1-butene preferentially. 相似文献
199.
Sueo Machi Takashi Tamura Miyuki Hagiwara Masao Gotoda Tsutomu Kagiya 《Journal of polymer science. Part A, Polymer chemistry》1966,4(2):283-291
In an attempt to elucidate the mechanism of chain-branch formation in the polymerization of ethylene, the effect of reaction conditions on short-chain branching in γ-radiationinduced polymerization of ethylene was investigated by using infrared spectroscopy. The concentration of methyl groups, i.e., the frequency of short-chain branching, increases with temperature and pressure and is independent of ethylene conversion to polymer and radiation intensity. The number of methyl groups per polymer molecule increases almost proportionally with the degree of polymerization. These facts indicate that short-chain branching occurs mainly by the mechanism of intramolecular hydrogen transfer. The effect of pressure on the rate of chain branching can be postulated by considering the transition state to be six-membered rings in hydrogen transfer reactions. The activation energy of chain branching is found to exceed that of propagation by 6 kcal./mole. 相似文献
200.
A new catalytic regioselective one-pot synthesis of hydroxyl-capped polyolefins is reported. This synthesis employs a new stereorigid bridged metallocene having an indenyl and a fluorenyl ligand named IF catalyst 1, exhibiting high catalytic performances. Here, we report on (1) the first example of allyl alcohol incorporation into the nonpolar polymer backbone using IF catalyst 1 and methylaluminoxane with high activity, high molecular weight, and high polar monomer uptake at high temperature, and (2) the first example of predominant end-site-selective introduction of an alcohol group into the polyolefins. Moreover, we observed the mixed regioselectivity by the type of alkylaluminum. 相似文献