全文获取类型
收费全文 | 1725篇 |
免费 | 135篇 |
国内免费 | 9篇 |
专业分类
化学 | 1392篇 |
晶体学 | 14篇 |
力学 | 36篇 |
数学 | 126篇 |
物理学 | 301篇 |
出版年
2023年 | 6篇 |
2022年 | 22篇 |
2021年 | 50篇 |
2020年 | 23篇 |
2019年 | 43篇 |
2018年 | 27篇 |
2017年 | 22篇 |
2016年 | 71篇 |
2015年 | 57篇 |
2014年 | 80篇 |
2013年 | 108篇 |
2012年 | 138篇 |
2011年 | 154篇 |
2010年 | 109篇 |
2009年 | 91篇 |
2008年 | 116篇 |
2007年 | 97篇 |
2006年 | 85篇 |
2005年 | 72篇 |
2004年 | 65篇 |
2003年 | 65篇 |
2002年 | 88篇 |
2001年 | 42篇 |
2000年 | 24篇 |
1999年 | 25篇 |
1998年 | 18篇 |
1997年 | 15篇 |
1996年 | 13篇 |
1995年 | 12篇 |
1994年 | 10篇 |
1993年 | 8篇 |
1992年 | 7篇 |
1991年 | 11篇 |
1990年 | 7篇 |
1989年 | 6篇 |
1988年 | 4篇 |
1987年 | 5篇 |
1986年 | 3篇 |
1985年 | 10篇 |
1984年 | 3篇 |
1983年 | 6篇 |
1982年 | 11篇 |
1981年 | 5篇 |
1980年 | 6篇 |
1979年 | 8篇 |
1978年 | 6篇 |
1977年 | 6篇 |
1968年 | 1篇 |
1967年 | 1篇 |
1934年 | 1篇 |
排序方式: 共有1869条查询结果,搜索用时 15 毫秒
21.
Using column-switching liquid chromatography/tandem mass spectrometry (LC-MS/MS), we developed an improved analytical method of urinary estriol glucuronides. This new method is derived predominantly from maternal and fetal precursors in pregnancy. We used in the following procedure: first, we filtered urine samples with a membrane filter. Next, we directly injected the 50 microL aliquot of urine samples onto a pre-column. Then, after activating the column-switching valve, we backflushed the loaded samples onto the C(18) analytical column. Urine samples can be assayed within 20 min without any sample preparation steps. We monitored separated estriol glucuronides by negative electrospray ionization (ESI) and selected-reaction monitoring (SRM). The calibration range of estriol-3-glucuronide (E3-3G) and estriol-16-glucuronide (E3-16G) was 0.1-20 microg/mL and the linearity of the method was 0.9984 for E3-3G and 0.9987 for E3-16G. The limits of detection at a signal-to-noise (S/N) ratio of 3 were 10 ng/mL (E3-3G) and 5 ng/mL (E3-16G). The analytical recovery was over 85% and, in general, inter-day and intra-day variability for precision and accuracy were less than 10%. When applied to a pregnancy urine sample to biomedical monitoring of the function of the maternal/fetal unit, the proposed method allowed rapid and sensitive screening for the detection of E3-3G and E3-16G. 相似文献
22.
[reaction: see text]. A novel synthetic methodology for 2,5-disubstituted tetrahydrofurans having an allenyl group at the 3-position via Prins-type cyclization was developed. The reaction led to excellent selectivity and moderate to high yields. 相似文献
23.
Imide-siloxane block copolymer/silica hybrid membranes: preparation, characterization and gas separation properties 总被引:1,自引:0,他引:1
Ho Bum Park Jang Ki Kim Sang Yong Nam Young Moo Lee 《Journal of membrane science》2003,220(1-2):59-73
Imide-siloxane block copolymer/silica hybrid membranes with covalent bonds were prepared via sol–gel reaction. The structural informations of these hybrid membranes were obtained by using Fourier transform-infrared spectrometry (FT-IR), 29Si nuclear magnetic resonance (29Si NMR), XPS and thermogravimetric analysis (TGA). The gas separation properties of the hybrid membranes were also investigated in terms of organosiloxane (PDMS) or silica content at various temperatures. In the hybrids, the addition of PDMS phase increased the permeabilities of gases such as He, CO2, O2, and N2, indicating that the gas transport occurred mainly through rubbery organic matrix. Meanwhile, the PDMS phase contributed the decreased gas selectivities to nitrogen but the reduction in selectivities was very small in comparison with other siloxane containing polymeric membranes. This might be due to the restriction of chain mobility by the existence of inorganic component such as silica network in the hybrids. Additionally, the increase of silica content in these hybrid membranes considerably retarded the falling-off of gas selectivity at elevated temperature. The increase of silica content in hybrid membranes resulted in well-formed silica networks and hence these inorganic components restricted the plasticization of organic matrix by the thermal segmental motion of organic components, leading to preventing the large decrease of the gas selectivity. 相似文献
24.
Chan Sik Cho Tae Kyung Kim Bok Tae Kim Tae-Jeong Kim Sang Chul Shim 《Journal of organometallic chemistry》2002,650(1-2):65-68
Nitroarenes react with trialkylamines in the presence of a catalytic amount of a ruthenium catalyst together with tin(II) chloride dihydrate at 180 °C in an aqueous medium (toluene–H2O) to afford the corresponding quinolines in moderate to good yields. The catalytic pathway seems to be proceeded via a sequence involving initial reduction of nitroarenes to anilines, alkyl group transfer from alkylamines to anilines to form an imine, dimerization of imine, and heterocyclization. 相似文献
25.
K. No Hyun J. Lee Ki M. Park Shim S. Lee Kwan H. Noh Sung K. Kim Ji Y. Lee Jong S. Kim 《Journal of heterocyclic chemistry》2004,41(2):211-219
A series of novel 1,3‐altemate calix[4]arene azacrowns having mono and bis crown ethers on the lower rim of the calix[4]arene framework were synthesized. Solid‐state structures confirmed the three dimensional conformation of compounds 1–3. 相似文献
26.
27.
A silica monomer-estrone complex (EstSi) having a thermally cleavable urethane bond and a cross-linkable triethoxysilane group was synthesized. From EstSi and TEOS, spherical silica particles with sizes of 1.5-3 mum were prepared. The template molecules were removed from the silica matrix by heating at 180 degrees C in DMSO in the presence of water, generating a cavity with an amino group. The control silica particles that had the same sizes and shapes were obtained with aminopropyl triethoxysilane and TEOS. When ethylene glycol was added in place of H2O, an ethyl alcoholic group was formed in the cavity. Their recognition ability and specific binding for estrone were characterized by uptake experiments. The estrone-imprinted silica particles showed a much higher recognition ability than the control silica particles and higher selectivity for estrone than testosterone propionate. 相似文献
28.
Abstract— The photoreaction of 8-methoxypsoralen (8-MOP) with thymidine in solid film state yielded two 4', 5'-monoadducts (a pair of diastereomers) and three 3,4-monoadducts. The stereochemistry of two 4', 5'-monoadducts was found to be cis-syn and trans-syn and one 3,4-monoadduct was cis-anti. In addition to these monoadducts, 3,4-, 4', 5'-biadducts were also formed during the reaction, but the isolation of each isomer of these adducts was not successful; however, the formation of these biadducts was confirmed by UV, IR, TLC and photosplitting experiments. 相似文献
29.
We study compact connected surfaces inm-dimensional Euclidean spaceE
m (3 m 5) with a point through which every geodesic is aW-curve regarded as a curve in Em. 相似文献
30.
The total synthesis of a new platelet aggregation-inhibiting gamma-lactam PI-091 (1) gave a 1:1 diastereomeric mixture at the gamma-ketal carbon. The high-yielding aldol reaction of an appropriately protected 1,3,4-trihydroxy-4-methyldecan-2-one 42, prepared from D-glucose, with the kinetically generated enolate of 3-methyl-2-butanone provided 43. The resulting diastereomeric mixture of the aldol adduct 43 was converted to a 2,4-alkylated furan 45 via an intramolecular ketalization followed by dehydration. The addition of a singlet oxygen to the alpha-trimethylsilylated furan 48derived from 45 under photochemical conditions efficiently provided an alpha,gamma-dialkylated gamma-hydroxy gamma-lactone 47. The transformation of methyl ketal 52 prepared from 47 into gamma-hydroxy gamma-lactam 53 was achieved by exposure to liquid ammonia in MeOH. The total synthesis of 1 was achieved from 52 through the Dess-Martin periodinane oxidation of the secondary hydroxy group in the side chain. The present total synthesis revealed that the stereogenic carbon center in the side chain in natural 1 is S. 相似文献