全文获取类型
收费全文 | 5244篇 |
免费 | 187篇 |
国内免费 | 32篇 |
专业分类
化学 | 4127篇 |
晶体学 | 48篇 |
力学 | 55篇 |
数学 | 310篇 |
物理学 | 923篇 |
出版年
2023年 | 29篇 |
2022年 | 38篇 |
2021年 | 48篇 |
2020年 | 67篇 |
2019年 | 96篇 |
2018年 | 59篇 |
2017年 | 45篇 |
2016年 | 103篇 |
2015年 | 102篇 |
2014年 | 114篇 |
2013年 | 236篇 |
2012年 | 279篇 |
2011年 | 343篇 |
2010年 | 187篇 |
2009年 | 191篇 |
2008年 | 333篇 |
2007年 | 320篇 |
2006年 | 288篇 |
2005年 | 294篇 |
2004年 | 267篇 |
2003年 | 207篇 |
2002年 | 208篇 |
2001年 | 97篇 |
2000年 | 94篇 |
1999年 | 76篇 |
1998年 | 61篇 |
1997年 | 57篇 |
1996年 | 74篇 |
1995年 | 66篇 |
1994年 | 48篇 |
1993年 | 59篇 |
1992年 | 65篇 |
1991年 | 49篇 |
1990年 | 46篇 |
1989年 | 53篇 |
1988年 | 55篇 |
1987年 | 45篇 |
1986年 | 52篇 |
1985年 | 89篇 |
1984年 | 60篇 |
1983年 | 38篇 |
1982年 | 44篇 |
1981年 | 41篇 |
1980年 | 36篇 |
1979年 | 46篇 |
1978年 | 38篇 |
1977年 | 29篇 |
1975年 | 30篇 |
1974年 | 30篇 |
1973年 | 28篇 |
排序方式: 共有5463条查询结果,搜索用时 328 毫秒
81.
A nondestructive photon activation procedure with 30 MeV bremsstrahlung followed by high-resolution gamma-spectrometry has
been applied to the multielement determination in tobacco leaves and commercial cigarettes. The elements determined by this
method included essential minor elements such as Ca, Cl, K and Mg, essential trace elements such as Fe, Mn and Zn, and possibly
toxic elements such As and Sb. The NBS Orchard Leaves could successfully be used as a comparative standard. The method is
quite simple and gives good reproducible results for at least 12 elements. 相似文献
82.
Shin-ichiro Shoda Yoshinori Misawa Yousuke Nishijima Yukiko Tawata Tomohiko Kotake Masato Noguchi Atsushi Kobayashi Takeshi Watanabe 《Cellulose (London, England)》2006,13(4):477-484
Chitinase-catalyzed hydrolytic and transglycosylating behavior of 1,2-oxazoline derivative of N-acetyllactosamine (LacNAc-oxa) 1 has been investigated. An extremely rapid hydrolysis (ring-opening of the oxazoline moiety) could be observed, suggesting that 1 behaves as a transition state analogue substrate for chitinase A1 (Bacillus circulans WL-12). This disaccharide monomer 1 was found to polymerize under basic conditions, giving rise to novel oligosaccharides having a β(1-4)–β(1-6) repeating unit in the main chain. The degree of polymerization of the resulting oligosaccharides was up to 5. This is the first example of enzymatic glycosylation reaction forming a β(1-6) bond catalyzed by chitinase. 相似文献
83.
[reaction: see text] A rhenium complex, [ReBr(CO)(3)(thf)](2), catalyzed the intermolecular reactions of 1,3-dicarbonyl compounds with terminal acetylenes and gave the corresponding alkenyl derivatives in excellent yields. These reactions could apply to an intramolecular version and gave the corresponding cyclic compounds quantitatively. 相似文献
84.
Tamura O Shiro T Ogasawara M Toyao A Ishibashi H 《The Journal of organic chemistry》2005,70(12):4569-4577
The 4-hydroxy 4-substituted glutamic acid moiety is a common substructure of biologically important natural products such as monatin [(2S,4S)-2], lycoperdic acid (3), and dysiherbaine (4). To develop methodology for syntheses of these natural products, cycloadditions of nitrone 5 with 2-substituted 2-propen-1-ols 6 and 2-substituted acrylates 8 were investigated. Reactions of nitrone 5 with alcohols 6 in the presence of MgBr2OEt2 gave cycloadducts 7 in a highly stereoselective manner, whereas noncatalyzed reactions of 5 with acrylates 8 afforded adducts 9. Using the former reaction, syntheses of monatin [(2S,4S)-2], monatin derivative 18, and lycoperdic acid (3) were accomplished. The C4-epimer of monatin [(2S,4R)-2)] was also synthesized by employing the latter cycloaddition. 相似文献
85.
Yoshihisa Kurasawa Yoshihisa Okamoto Atsushi Takada 《Journal of heterocyclic chemistry》1985,22(3):935-936
Novel compounds 8-(quinoxalin-2-yl)-1,2,4-triazolo[3,4-f][1,2,4]triazines 3a,b were obtained by a new annulation method in the 1,2,4-triazine synthesis. 相似文献
86.
The solvent extraction of copper(II) with trimethylacetic acid using benzene and 1-octanol as solvents was performed at 25 degrees C and 0.1 mole. dm(-3) ionic strength in the aqueous phase. In contrast to the extraction of copper(II) with a saturated straight-chain carboxylic acid in benzene, the dimeric copper(II) trimethylacetate was observed to dissociate into the monomer, even at a moderately high concentration of copper(II) in the benzene phase. In the system using 1-octanol as a solvent, both the monomeric and dimeric copper(II) species are suggested to be solvated by some 1-octanol molecules. It has been found that the dimerization and adduct formation of copper(II) species in benzene may more effectively enhance the extractability of copper(II) than the solvation by 1-octanol molecules. 相似文献
87.
This paper describes the photochemical surface modification of polystyrene (PS) substrates using vacuum ultraviolet (VUV) light 172 nm in wavelength. We have particularly focused on the effects of atmospheric pressure during VUV irradiation on the obtained surface's wettability and the stability of the wettability, in addition to its chemical structure, morphology, and photooxidation rate. Samples were photoirradiated with VUV light under pressures of 10, 10(3), or 10(5) Pa. Although, in each case, the originally hydrophobic PS surface became highly hydrophilic, the final water-contact angle and photooxidation rate depended on the atmospheric pressure. The samples treated at 10 Pa were less wettable than those prepared at 10(3) and 10(5) Pa due to the shortage of oxygen molecules in the atmosphere. The minimum water-contact angles of the samples treated at 10, 10(3), and 10(5) Pa were about 8 degrees, 0 degrees, and 0 degrees, respectively. With the samples prepared at 10 and 10(3) Pa, photooxidation reactions proceeded in the topmost region closest to the surface, while at 10(5) Pa photooxidation was found to be greatly enhanced in the deeper regions, as evidenced by angle-resolved X-ray photoelectron spectroscopy. Photoetching rates were determined through atomic force microscope observation of microstructured PS samples prepared by a simple mesh-contact method. As estimated from AFM images of the latticed microstructures obtained, the rates of samples prepared at 10(3) and 10(5) Pa were about 1.5 and 1.3 nm/min, respectively. However, no photoetched features were observable on the sample surface prepared at 10 Pa. Hydrophilic stability also varied greatly depending on atmospheric pressure. The hydrophilicity of samples treated at 10 and 10(3) Pa gradually decreased as they were exposed to air. On the other hand, the sample surface prepared at 10(5) Pa showed excellent hydrophilicity even after being left in air for 30 days. 相似文献
88.
A method for the enantiomeric determination of 2,7,8-trimethyl-2-(beta-carboxyethyl)-6-hydroxy chroman (LLU-alpha, gamma-CEHC) in rat plasma was developed using high-performance liquid chromatography (HPLC) with a fluorimetric derivatization with 4-N, N-dimethylaminosulfonyl-7-piperazino-2,1,3-benzoxadiazole (DBD-PZ) followed by O-acetylation with acetyl chloride. The proposed HPLC system used two non-chiral columns (phenyl and octadecylsilica) and a chiral column (a modified cellulose type), which were connected via two column-switching valves. A derivatized sample prepared from rat plasma was first separated on the phenyl column, and the fraction including LLU-alpha derivative was introduced to the octadecylsilica column to quantify the concentration of the mixture of S- and R-LLU-alpha. Finally, the LLU-alpha derivative was directly injected into the chiral column to obtain the ratio of the enantiomers. The proposed HPLC system was applied to the enantiomeric determination of LLU-alpha in plasma after intravenous administration of racemic LLU-alpha. S-LLU-alpha was eliminated faster than R-LLU-alpha, and its concentration in plasma decreased to one-third at 2 min after dosing. 相似文献
89.
E Makino N Iwasaki N Yagi T Ohashi H Kato Y Ito H Azuma 《Chemical & pharmaceutical bulletin》1990,38(1):201-207
Various pyrazine derivatives were synthesized and their antiallergic activity was examined. The inhibitory activity on allergic histamine release of the compounds bearing a 5-tetrazolyl group was more potent than that of the corresponding carboxyl derivatives. The introduction of -CONH- or -NHCO- between the pyrazine ring and the 5-tetrazolyl group as a spacer greatly enhanced the activity. N-(1H-Tetrazol-5-yl)-2-pyrazinecarboxamide (I-3) was estimated to exhibit nearly the same potency as disodium cromoglycate (DSCG). The structure-activity relationship among various derivatives modified by introducing some substituents onto the 3-, 5- or 6-position of the pyrazine ring of I-3 was investigated. The activity remained unchanged or was reduced when such substituents as methyl, chloro, methoxy, methylamino and dimethylamino were introduced at the 3- or 5-position. In contrast, 6-substitution with various alkylamino groups more or less increased the activity. Among them, the 6-dimethylamino (I-17c) and 6-(1-pyrrolidinyl) (I-34) derivative were proved to be most potent. The IC50 values (concentration which produces 50% inhibition of the allergic histamine release) of I-17c and I-34 were determined to be 4.7 x 10(-10) and 4.6 x 10(-10) M, respectively. These two compounds produced a potent inhibitory activity on passive cutaneous anaphylaxis (PCA) in rat, not only by the intravenous route (ED50 = 0.0096 mg/kg for both compounds) but also by the oral route (ED50 = 0.19 and 0.18 mg/kg, respectively). On the other hand, when the pyrazine ring of some representative compounds was replaced with a pyridine ring, the inhibitory activity on histamine release was significantly reduced. 相似文献
90.
Yutaka Sawada Junji Yamaguchi Osamu Sakurai Keizo Uematsu Nobuyasu Mizutani Masanori Kato 《Thermochimica Acta》1979,34(2):233-237
An exothermic phenomenon and a simultaneous rapid evolution of a small amount of carbon dioxide at ?500°C during thermal decomposition of hydromagnesite 4 MgCO3 · Mg(OH)2 · 4 H2O was studied by isothermal DSCTG in a carbon dioxide atmosphere. It was quantitatively confirmed that the exothermic phenomenon was due to crystallization of MgCO3 from the amorphous phase and that the evolution of carbon dioxide was due to decomposition of the MgCO3 by the heat of crystallization (?3.4 kcal mole?1. 相似文献