全文获取类型
收费全文 | 7443篇 |
免费 | 1383篇 |
国内免费 | 1196篇 |
专业分类
化学 | 6079篇 |
晶体学 | 82篇 |
力学 | 398篇 |
综合类 | 83篇 |
数学 | 789篇 |
物理学 | 2591篇 |
出版年
2024年 | 30篇 |
2023年 | 151篇 |
2022年 | 328篇 |
2021年 | 310篇 |
2020年 | 360篇 |
2019年 | 412篇 |
2018年 | 309篇 |
2017年 | 289篇 |
2016年 | 404篇 |
2015年 | 418篇 |
2014年 | 465篇 |
2013年 | 589篇 |
2012年 | 708篇 |
2011年 | 669篇 |
2010年 | 417篇 |
2009年 | 426篇 |
2008年 | 459篇 |
2007年 | 369篇 |
2006年 | 360篇 |
2005年 | 321篇 |
2004年 | 276篇 |
2003年 | 243篇 |
2002年 | 325篇 |
2001年 | 268篇 |
2000年 | 167篇 |
1999年 | 153篇 |
1998年 | 130篇 |
1997年 | 74篇 |
1996年 | 86篇 |
1995年 | 65篇 |
1994年 | 65篇 |
1993年 | 51篇 |
1992年 | 77篇 |
1991年 | 49篇 |
1990年 | 51篇 |
1989年 | 30篇 |
1988年 | 22篇 |
1987年 | 24篇 |
1986年 | 24篇 |
1985年 | 13篇 |
1984年 | 8篇 |
1983年 | 11篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1971年 | 1篇 |
1959年 | 2篇 |
1957年 | 2篇 |
1936年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 76 毫秒
991.
A novel high performance liquid chromatography-chemiluminescence(HPLC-CL) method for investigation of in vitro metabolism of repaglinide in pig liver microsomes with microdialysis sampling technique was developed.The chromatographic separation was performed on a Hypersil BDS-C18 column with an isocratic mobile phase consisting of methanol and 0.01 mol/L KH2PO4(pH 3.0)(volume ratio 75:25) at a flow rate of 1.0 mL/min.The detection was based on the chemiluminescence reaction of repaglinide with acidic potassium permanganate(KMnO4) and tris(2,2’-bipyridyl)ruthenium(Ⅲ)(Ru(bpy)33+),which was immobilized on the cationic ion-exchange resin for obtaining high sensitivity and reducing consumption of expensive reagent. 相似文献
992.
993.
994.
U. Gianfranco Spizzirri Francesca Iemma Francesco Puoci Feng Xue Wei Gao Giuseppe Cirillo Manuela Curcio Ortensia I. Parisi Nevio Picci 《先进技术聚合物》2011,22(12):1705-1712
Novel stimuli‐responsive hydrophilic microspheres were prepared by free radical polymerization of hydroxyethyl methacrylate (HEMA) and methacrylic acid (MA), as hydrophilic monomers, and N‐isopropylacrylamide (NIPAAm) and N,N′‐ethylenebisacrylamide (EBA), as thermo‐sensitive monomer and crosslinker, respectively. Hydrophilic comonomers were introduced in the macromolecular network to synthesize materials with tunable thermal behavior. In addition, by introducing in the polymerization feed both a hydrophilic and a pH‐sensitive monomer, such as MA, dual stimuli‐responsive (pH and temperature) hydrogels were synthesized. The incorporation of monomers in the network was confirmed by infrared spectroscopy, while the network density and the shape of hydrogels was found to strictly depend on the concentration of monomers in the polymerization feed. Thermal analyses showed negative thermo‐responsive behavior with pronounced water affinity of microspheres at a temperature lower than lower critical solution temperature (LCST). In our experiment, the LCST values of the hydrogels were in the range 34.6–37.5°C, close to the body temperature, and the amount of hydrophilic moieties in the polymeric network allows to collect shrinking/swelling transition temperatures higher than the LCST of NIPAAm homopolymers. In order to test the preformed materials as drug carriers, diclofenac diethylammonium salt (DDA) was chosen and drug entrapment percent was determined. Drug release profiles, in media at different temperature and pH, depend on hydrogels crosslinking degree and drug–bead interactions. By using semi‐empirical equations, the release mechanism was extensively studied and the diffusional contribute was evaluated. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
995.
3,4‐Dihydroxy‐L ‐phenylalanine (dopa) and 2‐(3,4‐dihydroxyphenyl)ethylamine (dopamine) were investigated as reducing agent and stabilizer for synthesis of gold nanoparticles (AuNPs) by one‐pot heating of a solution of HAuCl4/dopa or dopamine. AuNPs with different sizes were obtained by controlling the mass ratios of HAuCl4/dopa or dopamine. The formation mechanism for AuNPs was also proposed. Immobilization of horseradish peroxidase (HRP) and promotion of its electron transfer by polydopa film were investigated for preparation of H2O2 biosensor. Alkaline dopa solution was dropped onto a gold electrode for the formation of polydopa film. HRP was immobilized on the polydopa film through interactions between heme centre of HRP and the amine and carboxyl groups in polydopa. The AuNPs embedded in the polydopa film improved the electron transfer efficiency. These two factors allowed successful development of a H2O2 sensor with HRP@polydopa‐AuNPs electrode. Due to its biocompatibility, the polydopa‐AuNPs film provided good retention of enzyme activity and long‐term stability of the sensor. A rapid catalytic response (3 s) and a linear range from 0.006 to 5.0 mmol L?1 were obtained for H2O2. This facile preparation strategy can be extended to other enzyme‐based biosensors. 相似文献
996.
Sundberg TB Darricarrere N Cirone P Li X McDonald L Mei X Westlake CJ Slusarski DC Beynon RJ Crews CM 《Chemistry & biology》2011,18(10):1300-1311
Identification of methionine aminopeptidase-2 (MetAP-2) as the molecular target of the antiangiogenic compound TNP-470 has sparked interest in N-terminal Met excision's (NME) role in endothelial cell biology. In this regard, we recently demonstrated that MetAP-2 inhibition suppresses Wnt planar cell polarity (PCP) signaling and that endothelial cells depend on this pathway for normal function. Despite this advance, the substrate(s) whose activity is altered upon MetAP-2 inhibition, resulting in loss of Wnt PCP signaling, is not known. Here we identify the small G protein Rab37 as a MetAP-2-specific substrate that accumulates in the presence of TNP-470. A functional role for aberrant Rab37 accumulation in TNP-470's mode of action is demonstrated using a Rab37 point mutant that is resistant to NME, because expression of this mutant phenocopies the effects of MetAP-2 inhibition on Wnt PCP signaling-dependent processes. 相似文献
997.
A new dendritic gelator with carbazole as the building block (HBCD) was synthesized. It was found that H-bonding between the amide groups and π-π interaction between the aromatic rings played predominant roles in the gel formation. Meanwhile, significant aggregation-induced emission enhancement was observed in the gel state due to the formation of J-aggregates and the restricted molecular motion. Notably, the gel state of HBCD can be destroyed upon addition of F(-), accompanied by fluorescence enhancement on account of the formation of N-HF(-), which could further lead to the increased coplanarity of HBCD. The sensory capability of HBCD exhibited a high selectivity towards F(-) instead of the Cl(-), Br(-), I(-) and AcO(-) anions, which could be explained by the fact that the steric hindrance of the dendrimer would go against the interactions between the larger anions and HBCD. 相似文献
998.
A chemical investigation reveals that the resistance to acylation of an anti-tuberculosis drug, isoniazid is a consequent result of the inclusion or exclusion of cucurbit[n]urils (n = 6 or 7). The (1)H NMR spectra analysis shows that the different interaction models of the isoniazid with the two cucurbiturils are dependent on the cavity size of the hosts. Quantum chemistry calculations with density functional theory method indicate that the interaction of the isoniazid with both cucurbiturils is through thermodynamic stabilization in both the gas phase and aqueous solution through hydrogen bonding on the portal carbonyls of the cucurbiturils. Electronic absorption titration spectra suggest the hosts and guest interact in a ratio of 1 : 1 with moderate binding constants. Acylation kinetics of isoniazid with various acylating agents in the presence of the cucurbiturils revealed that resistance is only dependent on the host-isoniazid ratio, and independent on the size of the cucurbiturils and the species of acylating agents. 相似文献
999.
Catalytic asymmetric 1,3-dipolar cycloaddition of various azomethine ylides with diethyl 2-(3,3-diphenylpropa-1,2-dienylidene)malonate has been developed successfully with good to excellent enantioselectivity for the effcient construction of 3-vinylidene-pyrrolidine derivatives containing a unique allene moiety. 相似文献
1000.
Xue L Shi L Han Y Xia C Huynh HV Li F 《Dalton transactions (Cambridge, England : 2003)》2011,40(29):7632-7638
A series of carbene complexes [PdBr(2)((i)Pr(2)-bimy)L] (C2-C13) with different types of co-ligands (L) have been tested for their catalytic activities in the carbonylative annulation of 2-iodophenol with phenylacetylene in DMF to afford the respective flavone 2a. Complex C12 with an N-phenylimidazole co-ligand showed the best activity and also afforded high yields when the substrate scope was extended to other aryl or pyridyl acetylenes. In addition, catalyst C12 was also efficient in the carbonylative annulation of 2-iodoaniline with acid chlorides giving the desirable 2-substituted 4H-3,1-benzoxazin-4-ones (4) in good yields. Additionally, this Pd-NHC complex also proved to be a very efficient catalyst for the hydroxycarbonylation of iodobenzene derivatives at low catalyst loading and under low CO pressure. These results demonstrate the versatility and efficiency of this phosphine-free Pd(II)-NHC complex in different types of carbonylations of aryl iodides under mild conditions. 相似文献