全文获取类型
收费全文 | 3775篇 |
免费 | 115篇 |
国内免费 | 35篇 |
专业分类
化学 | 2405篇 |
晶体学 | 26篇 |
力学 | 81篇 |
数学 | 702篇 |
物理学 | 711篇 |
出版年
2023年 | 22篇 |
2022年 | 65篇 |
2021年 | 109篇 |
2020年 | 56篇 |
2019年 | 85篇 |
2018年 | 91篇 |
2017年 | 78篇 |
2016年 | 171篇 |
2015年 | 116篇 |
2014年 | 169篇 |
2013年 | 284篇 |
2012年 | 232篇 |
2011年 | 244篇 |
2010年 | 173篇 |
2009年 | 166篇 |
2008年 | 195篇 |
2007年 | 222篇 |
2006年 | 192篇 |
2005年 | 177篇 |
2004年 | 155篇 |
2003年 | 128篇 |
2002年 | 85篇 |
2001年 | 50篇 |
2000年 | 40篇 |
1999年 | 47篇 |
1998年 | 42篇 |
1997年 | 39篇 |
1996年 | 41篇 |
1995年 | 55篇 |
1994年 | 28篇 |
1993年 | 31篇 |
1992年 | 25篇 |
1991年 | 26篇 |
1990年 | 22篇 |
1989年 | 16篇 |
1988年 | 16篇 |
1987年 | 15篇 |
1986年 | 12篇 |
1985年 | 28篇 |
1984年 | 22篇 |
1983年 | 21篇 |
1982年 | 17篇 |
1981年 | 11篇 |
1980年 | 10篇 |
1979年 | 8篇 |
1978年 | 9篇 |
1977年 | 7篇 |
1975年 | 5篇 |
1974年 | 6篇 |
1973年 | 5篇 |
排序方式: 共有3925条查询结果,搜索用时 15 毫秒
81.
To develop solid-phase synthesis of phosphinic peptides, different FmocXaaPsi{PO(OAd)CH(2)}XaaOH building blocks have been prepared, where Fmoc is (fluorenylmethoxy)carbonyl. In this respect, the protection of the hydroxyphosphinyl function in these phosphinic dipeptides by the adamantyl group turns out to be convenient. The phosphinic adamantyl esters are completely stable in basic conditions and can be removed under relatively mild acidic conditions. Using these building blocks, despite the bulkiness of the adamantyl group, no particular problem of coupling was observed during the solid-phase synthesis of phosphinic peptides by the Fmoc strategy. The developed methodology is of particular interest to facilitate the development of potent inhibitors of zinc-metalloproteases. 相似文献
82.
83.
We use an idea of countable separability of points and sets in topological spaces to prove results on intersection of measurable
multifunctions and an implicit function theorem. We generalize or extend in part some well known Himmelberg's theorems. 相似文献
84.
Estimating the pore size distribution of activated carbons from adsorption data of different adsorbates by various methods 总被引:1,自引:0,他引:1
Gauden PA Terzyk AP Rychlicki G Kowalczyk P Cwiertnia MS Garbacz JK 《Journal of colloid and interface science》2004,273(1):39-63
Experimental adsorption isotherms of four adsorbates (N2, Ar, C6H6, and CCl4) as well as adsorption enthalpy (C6H6 and CCl4) measured on two strictly microporous carbons are used to evaluate the porosity of adsorbents (i.e., pore size distributions (PSDs) and average pore diameter ( Lav )). The influence of the diameter of adsorbates ( dA) as well as of the temperature ( T ) is analyzed in order to explain the differences or similarities between the above-mentioned quantities for all systems. Proposed previously, the general relationships between the parameters of the Dubinin-Astakhov (DA) isotherm equation (the characteristic energy of adsorption ( E0 ) and the exponent of this equation ( n )) and the average slit-width of carbon micropores are investigated. Moreover, the thermodynamic verification of the Horvath-Kawazoe (HK) theory and the ND model is presented based on data of the adsorption and enthalpy of adsorption of benzene and carbon tetrachloride on two carbons. Finally, the pore diameters calculated from calorimetry data using the Everett and Powl method and those calculated applying the recently developed equations are compared. In our opinion the change of apparent PSD should be monitored by performing a series of isotherm measurements from high (equal and higher than room temperature) to low temperatures (ca. 77.5 K) as was presented in the current study. Moreover, the analysis of the experimental data leads to the conclusion that the entropy of C6H6 and CCl4 can approach to the values characteristic of quasi-solid (a partially ordered structure). Therefore, this behavior of the adsorbate should be taken into consideration in the theoretical assumptions of model and its thermodynamic verification. 相似文献
85.
M. B. Bogacki M. Wiśniewski J. Szymanowski 《Journal of Radioanalytical and Nuclear Chemistry》1998,228(1-2):57-61
Extraction of arsenic(V) from sulfuric acid solutions with various extractants in multistage counter-current extraction-stripping systems was compared. The extraction ability of the extractants studied showed the following order: ENIM 100>TBP=CYANEX 923>2-methylhexanol. The extraction depends significantly on the number of extraction stages and the phase ratios in extraction. The effects of the number of stripping stages and the phase ratio in stripping are less important. 相似文献
86.
Dzygiel A Rzeszotarska B Masiukiewicz E Cmoch P Kamieński B 《Chemical & pharmaceutical bulletin》2004,52(2):192-198
Methyl 5-amino-1H-[1,2,4]triazole-3-carboxylate hydrochloride (1). and free ester (2). were obtained and 2 was reacted with Ac(2)O to give the acetylated products 3-6. Compounds 1-6 were studied using HPLC, GC-MS, FTIR and multinuclear NMR spectroscopy, including the cross-polarisation magic angle spinning (CPMAS) technique. The results of the acetylation of 2 were compared to those of the acetylation of 5-amino-1H-[1,2,4]triazole, and for 2 a significant decrease in the susceptibility to acetylation was found. The reaction of 2 with Ac(2)O at 20 degrees C, regardless of the amount and the concentration of the latter, including neat Ac(2)O, proceeds fully regioselectively and leads to one product: methyl 1-acetyl-5-amino-1H-[1,2,4]triazole-3-carboxylate (3). In sharp contrast to 5-amino-1H-[1,2,4]triazole, neither an additional monoacetylated isomer, whether annular or exocyclic, nor any diacetylated derivative could be detected. The diacetylation of 2 requires the process to be carried out in neat boiling Ac(2)O and, as in the case of 5-amino-1H-[1,2,4]triazole, gives two diacetylated isomers. These are methyl 1-acetyl-3-(acetylamino)-1H-[1,2,4]triazole-5-carboxylate (4) and 1-acetyl-5-(acetylamino)-1H-[1,2,4]triazole-3-carboxylate (5). Hypothetical pathways of their formation have been suggested. A mixture of 4 and 5 upon hydrolysis of the ring acetyl group gives the monoacetylated derivative methyl 5-(acetylamino)-1H-[1,2,4]triazole-3-carboxylate (6). The spectroscopic, structural and conformational characteristics of compounds 1-6 have been given and methods for their preparation have been provided. 相似文献
87.
Krzysztof Maruszewski Marek Jasiorski Witold Wacławek Wiesław Stręk Marek Lisowski 《Journal of Sol-Gel Science and Technology》1998,13(1-3):585-586
A series of silicate xerogels with entrapped chiral amino acids have been obtained via sol-gel technology. The transparent, glassy samples obtained exhibit chirality in the bulk due to the presence of the entrapped asymmetric molecules. Measurements of the optical activity of the doped xerogel samples revealed that the entrapment did not significantly influence the optical activity observed for liquid solutions of the amino acids. Thus, the sol-gel method enables the preparation of amorphous optical materials exhibiting properties of strictly spatially defined molecular systems. Apart from the obvious optical applications, such porous materials with asymmetric centers might find interesting applications in chiral chemical syntheses and separations. 相似文献
88.
5'-O-DMT-deoxyribonucleoside-3'-O-(2-selena-4,4-pentamethylene-1,3,2-oxathiaphospholane) monomers, derivatives of dA, dC, dG, and T, can be resolved into pure P-diastereomers by silica gel column chromatography. They have been used for DBU-promoted, either solution- or solid-phase synthesis of P-stereodefined phosphoroselenoate analogues of oligodeoxyribonucleotides. Fast- and slow-eluting monomers are precursors of phosphoroselenoate internucleotide linkage of R(P) and S(P) absolute configuration, respectively. [reaction: see text] 相似文献
89.
Serdar Karabcek Ismail Degirmencioglu Nevin Karabcek Mustafa Er Kerim Serbest 《Journal of heterocyclic chemistry》2003,40(4):639-643
The synthesis and structural properties of three novel imidates, 11,13‐bis‐(2‐amino‐ethylimino)‐1,10‐dioxa‐4,7‐dithiacyclotridecane ( 2 ), 11,13‐bis‐(3‐aminopropylimino)‐1,10‐dioxa‐4,7‐dithiacyclotridecane, ( 3 ) and 2,11‐dioxa‐5,8‐dithia‐13,16,19,22‐tetraazabicyclo[10.10.1]tricosa‐1(22),12‐diene, ( 4 ) have been described. These compounds were synthesized by treating 1,10‐dioxa‐4,7‐dithiacyclotridecane‐11,13‐diester ( 1 ) with the appropriate diamine under N2 and their structures have been characterised by elemental analyses, 1H‐ and 13C‐nmr, ir, and mass spectral studies. Elemental analyses and spectroscopic data support the proposed imidate structures. In addition, total energy and heat of formation (Figure 2) calculated for imidates 2a‐4a and 2b‐4b by the semiempirical AM1 calculations have shown that imidates 2b‐4b having intramolecular hydrogen bonds are more stable (5‐10 kcal/mol) than compounds 2a‐4a . 相似文献
90.
The described radiochromatographic method permits fast and high-sensitivity monitoring of soil biodegradation products of an insect growth regulator for its environmental risk assessment. We analyzed and compared two diastereoisomers of ethyl N-(2-(4-[(2-hydroxycyclohexyl) methyl]phenoxy)ethyl)carbamate, namely its cis-(1S,2S) isomer JN-W330 and a trans-(1R,2S) isomer JN-W331. Microbial conversion of the cis-isomer to the trans-isomer was proved by mass spectrometry analyzer. Among the chromatographic columns tested, the best separation was found with a 125 mm x 4 mm i.d. column packed with Supersphere 100 RP-C18, 5 microm and an acetonitrile-water gradient. The detection limit for the both isomers was in the range of 120-250 Bq (0.3-0.8 ng) at a concentration of 2 ng/ml with radiometric detection. The calibration curves for standard solutions were linear in the range of 150Bq-150kBq (r = 0.996). The method enabled us to compare the analyzed juvenoids with biologically active oostatic peptides in terms of their environmental safety. 相似文献