全文获取类型
收费全文 | 1616篇 |
免费 | 192篇 |
国内免费 | 104篇 |
专业分类
化学 | 1857篇 |
晶体学 | 14篇 |
综合类 | 7篇 |
数学 | 4篇 |
物理学 | 30篇 |
出版年
2024年 | 2篇 |
2023年 | 21篇 |
2022年 | 49篇 |
2021年 | 162篇 |
2020年 | 104篇 |
2019年 | 74篇 |
2018年 | 53篇 |
2017年 | 63篇 |
2016年 | 80篇 |
2015年 | 82篇 |
2014年 | 88篇 |
2013年 | 154篇 |
2012年 | 94篇 |
2011年 | 73篇 |
2010年 | 69篇 |
2009年 | 93篇 |
2008年 | 83篇 |
2007年 | 77篇 |
2006年 | 82篇 |
2005年 | 81篇 |
2004年 | 74篇 |
2003年 | 73篇 |
2002年 | 27篇 |
2001年 | 17篇 |
2000年 | 18篇 |
1999年 | 25篇 |
1998年 | 22篇 |
1997年 | 9篇 |
1996年 | 11篇 |
1995年 | 15篇 |
1994年 | 14篇 |
1993年 | 5篇 |
1992年 | 7篇 |
1991年 | 3篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1984年 | 1篇 |
1981年 | 1篇 |
排序方式: 共有1912条查询结果,搜索用时 31 毫秒
91.
An electrophoretically mediated microanalysis method with partial filling technique was developed for screening aromatase inhibitors in traditional Chinese medicine. The in‐capillary enzymatic reaction was performed in 20 mM sodium phosphate buffer (pH 7.4), and sodium phosphate buffer (20 mM, pH 8.0) was used as a background electrolyte. A long plug of coenzyme reduced β‐nicotinamide adenine dinucleotide 2′‐phosphate hydrate dissolved in the reaction buffer was hydrodynamically injected into a fused silica capillary followed by the injection of reaction buffer, enzyme, and substrate solution. The reaction was initiated with a voltage of 5 kV applied to the capillary for 40 s. The voltage was turned off for 20 min to increase the product amount and again turned on at a constant voltage of 20 kV to separate all the components. Direct detection was performed at 260 nm. The enzyme activity was directly assayed by measuring the peak area of the produced β‐nicotinamide adenine dinucleotide phosphate and the decreased peak area indicated the aromatase inhibition. Using the Lineweaver–Burk equation, the Michaelis–Menten constant was calculated to be 50 ± 4.5 nM. The method was applied to the screening of aromatase inhibitors from 15 natural products. Seven compounds were found to have potent AR inhibitory activity. 相似文献
92.
The adsorption and inhibition effect of xanthione (XION) on mild steel in 0.5 M H2SO4 at 303–333 K were studied using gravimetric and UV–visible spectrophotometric methods. The results obtained show that XION acts as an effective corrosion inhibitor for mild steel in sulphuric acid and inhibition efficiency reaches 98.0% at a very low inhibitor concentration of 10 μM. Inhibition efficiency was found to increase with increase in XION concentration but decreased with temperature suggesting physical adsorption mechanism. Arrhenius law and its transition equation lead to estimate the activation parameters of the corrosion process. XION inhibits the corrosion of mild steel effectively at moderate temperature and adsorbs according to the Langmuir isotherm. Thermodynamic parameters governing the adsorption process have been calculated and discussed. The UV–visible absorption spectra of the solution containing the inhibitor after the immersion of mild steel specimen indicate the formation of a XEN–Fe complex. Attempt to correlate the molecular structure to quantum chemical indices was made using density functional theory (DFT). 相似文献
93.
94.
95.
Dr. Matthieu Fonvielle Dénia Mellal Delphine Patin Maxime Lecerf Dr. Didier Blanot Dr. Ahmed Bouhss Dr. Marco Santarem Dr. Dominique Mengin‐Lecreulx Dr. Matthieu Sollogoub Dr. Michel Arthur Dr. Mélanie Ethève‐Quelquejeu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(4):1357-1363
Peptidyl–RNA conjugates have various applications in studying the ribosome and enzymes participating in tRNA‐dependent pathways such as Fem transferases in peptidoglycan synthesis. Herein a convergent synthesis of peptidyl–RNAs based on Huisgen–Sharpless cycloaddition for the final ligation step is developed. Azides and alkynes are introduced into tRNA and UDP‐MurNAc‐pentapeptide, respectively. Synthesis of 2′‐azido RNA helix starts from 2′‐azido‐2′‐deoxyadenosine that is coupled to deoxycytidine by phosphoramidite chemistry. The resulting dinucleotide is deprotected and ligated to a 22‐nt RNA helix mimicking the acceptor arm of Ala‐tRNAAla by T4 RNA ligase. For alkyne UDP‐MurNAc‐pentapeptide, meso‐cystine is enzymatically incorporated into the peptidoglycan precursor and reduced, and L ‐Cys is converted to dehydroalanine with O‐(mesitylenesulfonyl)hydroxylamine. Reaction of but‐3‐yne‐1‐thiol with dehydroalanine affords the alkyne‐containing UDP‐MurNAc‐pentapeptide. The CuI‐catalyzed azide alkyne cycloaddition reaction in the presence of tris[(1‐hydroxypropyl‐1H‐1,2,3‐triazol‐4‐yl)methyl]amine provided the peptidyl‐RNA conjugate, which was tested as an inhibitor of non‐ribosomal FemXWv aminoacyl transferase. The bi‐substrate analogue was found to inhibit FemXWv with an IC50 of (89±9) pM , as both moieties of the peptidyl–RNA conjugate contribute to high‐affinity binding. 相似文献
96.
Two new silver(I) trans‐cinnamates, namely [Ag(2‐cca)(H2O)]2 ( 1 ) and [Ag(4‐cca)]n ( 2 ) (2‐ccaH = 2‐chlorocinnamic acid and 4‐ccaH = 4‐chlorocinnamic acid), were synthesized and structurally characterized. Single crystal X‐ray studies reveal that each silver(I) atom in 1 is two‐coordinate by a 2‐chlorocinnamate ligand and one water molecule to afford a discrete centrosymmetric dimer with the ligand‐unsupported Ag···Ag interactions (3.218(4) Å), while a pair of symmetry‐related silver(I) atoms in 2 are clamped by two μ2‐η1:η1 4‐chlorocinnamate ligands to yield a binuclear silver(I) moiety incorporating a ligand‐supported Ag···Ag interaction (2.819(5) Å). Both complexes 1 and 2 show potent urease inhibitory activities with the respective IC50 values of 0.66 and 1.10 μM. 相似文献
97.
Three new micropeptins, micropeptin KR1030, KR1002 and KR998 and the known microcyclamide GL546A were isolated from the extract of Microcystis sp. bloom material collected in Kabul Reservoir, Israel. The planar structures of the compounds were determined by homonuclear and inverse-heteronuclear 2D-NMR techniques as well as high-resolution mass spectrometry. The absolute configuration of the asymmetric centres of the amino acids was studied using Marfey's method for HPLC. The inhibitory activity of the compounds was determined for the serine proteases: trypsin, chymotrypsin and elastase. 相似文献
98.
Jian-Jun Tang Li Zhang Li-Ping Jiang Lei Di Yong-Ming Yan Zheng-Chao Tu Cui-Ping Yang Zhi-Li Zuo Bo Hou Hou-Lin Xia Yong-Bin Chen Yong-Xian Cheng 《Tetrahedron》2014
Polyrhachis dives is consumed as an insect food in some regions of China. In this study, new dopamine derivatives, (+)-polyrhadopamine A (1a) and (−)-polyrhadopamine A (1b), (+)-polyrhadopamine B (2a) and (−)-polyrhadopamine B (2b), and polyrhadopamines C–E (3–5), were isolated from this species. The structures and stereochemistry of these substances were assigned by using spectroscopic and computational methods. Compounds 1a, 1b, 2a, and 2b are dimeric N-acetyldopamine derivatives, 3 is a dopamine analog containing an unusual sulfone group, and 4 and 5 possess a rare benzo[d]thiazole moiety. The functions of these substances as ROCK1/2 inhibitors, neural stem cell (NSCs) proliferation stimulators, immunosuppressive, and anti-inflammatory agents were determined. 相似文献
99.
《Tetrahedron letters》2014,55(51):7015-7018
Recently, we have identified the first inhibitors of Rad6B, an E2 enzyme essential for post-replication DNA repair and a potential new drug target for the treatment of breast cancer. We report two newly optimised synthetic routes to our [4-amino-6-(phenylamino)-1,3,5-triazin-2-yl]methyl 4-nitrobenzoate target compounds TZ8 and TZ9 with general applicability for further structure–activity relationship studies around this pharmacophore. The key step involved the condensation/cyclisation between phenylbiguanide and either ethyl bromoacetate or dimethyloxalate in good yield. 相似文献
100.
The spectroscopic properties of Nω-nitro-l-arginine were investigated by FT-IR, UV-VIS, and 1H NMR spectra. Geometrical parameters and energies were calculated using the density functional theory (DFT) B3LYP method with the 6-311G basis set. Geometrical optimization of the molecule has been performed, vibrational spectra have been calculated, and fundamental vibrations have been determined from the total energy distribution (TED) of the vibrational modes. The HOMO-LUMO analysis is carried out for various electric fields (0.0–0.025 A?1). The HOMO-LUMO gap is decreased while increasing the electric field. The calculated quantum chemical parameters are calculated and correlated to the inhibition efficiency, A Mullliken population was also important for determining local reactivity by indicating reactive centers and identifying potential nucleophilic and electrophilic attack sites. Charge transfer occurs inside the compound based on the HOMO LUMO gap. Calculations of DFT were evaluated in their ability to predict inhibition efficiency. 相似文献