全文获取类型
收费全文 | 717篇 |
免费 | 23篇 |
国内免费 | 4篇 |
专业分类
化学 | 514篇 |
晶体学 | 9篇 |
力学 | 7篇 |
数学 | 83篇 |
物理学 | 131篇 |
出版年
2021年 | 10篇 |
2020年 | 14篇 |
2019年 | 10篇 |
2018年 | 11篇 |
2016年 | 12篇 |
2015年 | 11篇 |
2014年 | 12篇 |
2013年 | 44篇 |
2012年 | 34篇 |
2011年 | 35篇 |
2010年 | 27篇 |
2009年 | 25篇 |
2008年 | 38篇 |
2007年 | 27篇 |
2006年 | 33篇 |
2005年 | 28篇 |
2004年 | 35篇 |
2003年 | 29篇 |
2002年 | 33篇 |
2001年 | 15篇 |
2000年 | 11篇 |
1999年 | 7篇 |
1998年 | 7篇 |
1997年 | 8篇 |
1994年 | 6篇 |
1993年 | 4篇 |
1992年 | 10篇 |
1991年 | 10篇 |
1990年 | 11篇 |
1989年 | 17篇 |
1988年 | 7篇 |
1987年 | 6篇 |
1986年 | 6篇 |
1985年 | 15篇 |
1984年 | 12篇 |
1983年 | 12篇 |
1982年 | 8篇 |
1981年 | 8篇 |
1980年 | 9篇 |
1979年 | 9篇 |
1978年 | 7篇 |
1977年 | 4篇 |
1976年 | 6篇 |
1974年 | 6篇 |
1973年 | 7篇 |
1972年 | 5篇 |
1969年 | 5篇 |
1968年 | 7篇 |
1966年 | 4篇 |
1965年 | 4篇 |
排序方式: 共有744条查询结果,搜索用时 15 毫秒
31.
Summary Alumina may be considerably modified by impregnating at 100°C in the alkali metal phosphate solution. The available solution for modification was the KOH–K2HPO4–AlPO4 (11.51M) solution or the NaOH–Na2 HPO4 (0.81.1 M or 11.5M) solution. The appreciable improvement on chromatograms was obtained by preheating of the alumina, especially above 800°C prior to impregnating A further modification may be made by ignition of the alumina impregnated. The x-ray diffraction studies revealed the phase transformation of the alumina inducing the modification, and the essential factor of the present modification method being the thermal treatment of the alumina at temperatures forming -alumina. 相似文献
32.
Manabu Naito 《Annali di Matematica Pura ed Applicata》1984,136(1):1-13
Summary The equation to be considered is of the form (1) x(n)(t)+p(t)x(g(t))=0 (t>a), where =±1, p(t) > 0 for ta and g(t) as t. It is well- known that a nonoscillatory solution x(t) of (1) satisfies (2) x(t)x(i)(t)>0 (0il), (–1)i–lx(t)x(i)(t)>0 (lin) for some integer l, 0ln, (–1)n–l–1=1. In this paper, for a given l such that 0n–l–1=1, necessary conditions and sufficient conditions are found for (1) to have a solution x(t) which satisfies (2), and a necessary and sufficient condition is established in order that for every >0 the equation x(n)(t)+p(t)x(g(t))=0 (t>a) has a solution x(t) which satisfies (2). Related results are also contained. 相似文献
33.
Michael reaction of 1,7-pctadien-3-one with 2-methylcyclopentane-1,3-dione, followed by intramolecular aldol condensation promoted by L-amino acids produced the optically active (+)-4-(3-butenyl)-7a-methyl-5,6,7,7a-tetrahydroindane-1,5-dione in high chemical and optical yields. The PdCl2-catalyzed oxidation of the terminal double bond gave the methyl ketone, which had 76% optical purity and was made 100% optically pure by recrystallization. Then aldol condensation afforded the tricyclic ketone, which was alkylated with 3-butenyl iodide to afford (?)-3β-t-butoxy-2,3,3a,4,5,7,8,9,9aβ,9bα-decahydro-6-(3-butenyl)-3aβ-methyl-1H-benz[e]inden-7-one. The synthesis of this compound means the total synthesis of (+)-19-nortestosterone. 相似文献
34.
Shuichi Naito Shigeru Aida Toshiki Kasahara Toshihiro Miyao 《Research on Chemical Intermediates》2006,32(3-4):279-290
In situ infrared spectroscopy was applied to elucidate the reaction mechanism of CO hydrogenation over Pd/CeO2. Instead of direct dissociation of CO, a new reaction pathway is proposed for methane formation, involving geminal dicarbonyl intermediates and (HCO)2(a) intermediates, which may be located on the surface of Pd covered with thin layers of reduced ceria (SMSI effect). Transformation of methane formation sites into methanol formation ones by the oxidation with water vapor formed during the CO?H2 reaction is proposed, which may be located on the Pd (111) planes adjacent to ceria support. 相似文献
35.
Poly(phenylisopropenylketone (PPIK) and copolymers of PIK and methylmethacrylate (MMA) or styrene (St) were irradiated in benzene solution at 30° with 313 nm light (stationary irradiations) or with 347 nm light (flash photolysis experiments). Homo PPIK undergoes main chain degradation (β-scission) with ø(S) ≈ 0.05. The quantum yield for α-scission is ø(α) = 0.3. For copolymers of MMA and PIK (1 to 15 mol%), ø(S) is 0.04 independent of the copolymer composition. With copolymers of St and PIK, ø(S) was found to increase with decreasing PIK content and to approach 0.15 for very small PIK contents. The flash photolysis experiments showed: (a) the carbonyl triplet decay rate constant kT(6 × 106 sec?1) for CP-MMA-PIK samples is independent of copolymer composition but is lower than for homo PPIK (1 × 107 sec?1). In CP-St-PIK samples kT decreases with decreasing PIK content [from 8 × 106 sec?1 (12 mol% PIK) to 3 × 106 sec?1 (1 mol% PIK)]; (b) the transient spectra of triplet decay products indicate the formation of benzoyl radicals in the cases of PPIK and CP-MMA-PIK, and the formation of various different species in the case of CP-St-PIK.The results are consistent with the following concept. In homo PPIK and CP-MMA-PIK, α-scission (Norrish type I) is the dominant chemical route of triplet deactivation. In CP-St-PIK, however, type II processes become more and more important as the PIK content decreases. 相似文献
36.
Motokawa M Kobayashi H Ishizuka N Minakuchi H Nakanishi K Jinnai H Hosoya K Ikegami T Tanaka N 《Journal of chromatography. A》2002,961(1):53-63
Reduction of through-pore size and skeleton size of a monolithic silica column was attempted to provide high separation efficiency in a short time. Monolithic silica columns were prepared to have various sizes of skeletons (approximately 1-2 microm) and through-pores (approximately 2-8 microm) in a fused-silica capillary (50-200 microm I.D.). The columns were evaluated in HPLC after derivatization to C18 phase. It was possible to prepare monolithic silica structures in capillaries of up to 200 microm I.D. from a mixture of tetramethoxysilane and methyltrimethoxysilane. As expected, a monolithic silica column with smaller domain size showed higher column efficiency and higher pressure drop. High external porosity (> 80%) and large through-pores resulted in high permeability (K = 8 x 10(-14) -1.3 x 10(-12) m2) that was 2-30 times higher than that of a column packed with 5-mirom silica particles. The monolithic silica columns prepared in capillaries produced a plate height of about 8-12 microm with an 80% aqueous acetonitrile mobile phase at a linear velocity of 1 mm/s. Separation impedance, E, was found to be as low as 100 under optimum conditions, a value about an order of magnitude lower than reported for conventional columns packed with 5-microm particles. Although a column with smaller domain size generally resulted in higher separation impedance and the lower total performance, the monolithic silica columns showed performance beyond the limit of conventional particle-packed columns under pressure-driven conditions. 相似文献
37.
Here, we report a diversity-oriented synthetic approach toward skeletally diverse, cyclized peptidomimetics with diverse appendages. Starting from α-(N-acylamino)amides with various appendages, 12 to 16-membered lactams with defined olefin geometry were synthesized by a common synthetic sequence. We also synthesized the macrocycle in a liquid phase directed toward a construction of the peptidomimetics library. 相似文献
38.
Single nucleotide polymorphisms (SNPs) of cancer repression gene p53 were analyzed electrochemically with ferrocenyl naphthalene diimide (1) as a hybridization indicator. The SNPs studied were the transition to A from G in the codon for amino acid at positions 175, 248 or 273 and the transversion to C from G in the codon for the amino acid at position 72. Thus, 20-meric oligonucleotides carrying the SNP site were used both as a sample and a probe with the latter immobilized on an electrode. Even one base difference on the p53 gene resulted in a significant difference in the current response of 1 and the magnitude of the response correlated with the amount of the DNA hybrid on the electrode. Moreover, when PCR products of exon 4, on which the P72/R72 SNP resides, of the p53 gene were analyzed by this method, the heterozygote and homozygotes were discriminated with modest precision. 相似文献
39.
Minemura Y Ito S Miyao T Naito S Tomishige K Kunimori K 《Chemical communications (Cambridge, England)》2005,(11):1429-1431
In preferential CO oxidation in H2-rich gas, K-Pt/Al2O3(K/Pt = 10) was very effective in decreasing CO concentration below 10 ppm in the 375-410 K range, and the turnover frequency of the K-Pt/Al2O3 was 20 times as high as that of Pt/Al2O3 at 353 K; furthermore, the activity of CO oxidation was promoted drastically by the presence of H2. 相似文献
40.
Miyata O Nishiguchi A Ninomiya I Aoe K Okamura K Naito T 《The Journal of organic chemistry》2000,65(21):6922-6931
A combination of sulfanyl radical addition-cyclization of dienes connected with hydroximates and subsequent conversion of the resulting cyclic hydroximate to the lactones provides a novel method for the construction of alpha,beta-disubstituted gamma-lactones. Upon treatment with thiophenol in the presence of AIBN, dienes connected with hydroximates smoothly underwent sulfanyl radical addition-cyclization to give cyclic cis- and trans-hydroximates. Hydrolysis of cyclic hydroximates gave the desired cis- and trans-lactones in high yield. This method was successfully applied to the practical synthesis of (+/-)-oxo-parabenzlactone. 相似文献