全文获取类型
收费全文 | 3102篇 |
免费 | 331篇 |
国内免费 | 518篇 |
专业分类
化学 | 3497篇 |
晶体学 | 13篇 |
力学 | 12篇 |
综合类 | 38篇 |
数学 | 92篇 |
物理学 | 299篇 |
出版年
2024年 | 16篇 |
2023年 | 89篇 |
2022年 | 359篇 |
2021年 | 282篇 |
2020年 | 223篇 |
2019年 | 178篇 |
2018年 | 164篇 |
2017年 | 150篇 |
2016年 | 182篇 |
2015年 | 120篇 |
2014年 | 169篇 |
2013年 | 316篇 |
2012年 | 164篇 |
2011年 | 138篇 |
2010年 | 143篇 |
2009年 | 133篇 |
2008年 | 158篇 |
2007年 | 152篇 |
2006年 | 150篇 |
2005年 | 117篇 |
2004年 | 109篇 |
2003年 | 105篇 |
2002年 | 61篇 |
2001年 | 49篇 |
2000年 | 34篇 |
1999年 | 29篇 |
1998年 | 30篇 |
1997年 | 22篇 |
1996年 | 23篇 |
1995年 | 14篇 |
1994年 | 14篇 |
1993年 | 15篇 |
1992年 | 9篇 |
1991年 | 10篇 |
1990年 | 11篇 |
1989年 | 4篇 |
1988年 | 4篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1984年 | 1篇 |
1981年 | 1篇 |
1980年 | 1篇 |
排序方式: 共有3951条查询结果,搜索用时 31 毫秒
101.
Dimethylcarbonate (DMC) is a valuable methylating reagent that can replace methyl halides and dimethylsulfate in the methylation of a variety of nucleophiles. It couples tunable reactivity and unprecedented selectivity towards mono-C- and mono-N-methylation. In addition, it is a prototype example of a green reagent, because it is nontoxic, is made by a clean process, is biodegradable, and reacts in the presence of a catalytic amount of base, thereby avoiding the formation of undesirable inorganic salts as by-products. Depending on the reaction conditions, DMC can be reacted under plug-flow, CSTR, or batch conditions. Other remarkable reactions are those where DMC behaves as an oxidant. The reactivity of other carbonates is reported as well. 相似文献
102.
Ding-Guo Liu Xiang-Zhu Wang Yang Gao Bihua Li Dajun Yang Terrence R. Burke Jr. 《Tetrahedron》2002,58(52):10423-10428
Phosphonomethylphenylalanine (Pmp, 2) has shown wide utility as a hydrolytically stable phosphtyrosyl (pTyr, 1) mimetic, particularly in Src homology 2 (SH2) domain-binding peptides. (2S,3R)-3-(4-(phosphonomethyl)phenyl)pipecolic acid (3) represents a variant of Pmp having φ and χ1 torsion angles constrained through incorporation into the piperidinyl ring structure contained within pipecolic acid. Reported herein is the enantioselective preparation of 3, in an orthogonally protected form (4) suitable for use in peptide synthesis. Stereochemistries at both the 2- and 3-positions are derived inductively from a single chiral center provided by the commercially available Evans chiral auxiliary, (4S)-4-benzyl-1,3-oxazolidin-2-one. Incorporation of 4 into a Grb2 SH2 domain-directed tripeptide (18) showed that Grb2 SH2 domain-binding affinity was reduced relative to the parent Pmp-containing tripeptide (19). Although conformational constraint did not enhance affinity in this case, novel amino acid analogue 4 may serve as a useful tool for the induction of defined phosphotyrosyl geometry in peptides directed at other signal transduction targets. 相似文献
103.
Neonatal exposure to synthetic estrogen endocrine disruptors or estrogen-receptor inhibitors induces developmental abnormalities in the male reproductive system. To investigate whether neonatal exposure affects spermatogenesis in juvenile and pubertal testis, Sprague-Dawley rat pups were given synthetic estrogen endocrine disruptors or estrogen-receptor inhibitors by a single injection on the day of birth at concentrations ranging between 2 to 40 mm, and sacrificed on day 21 (juvenile), 35 (prepuberty) or 50 (puberty). The testes were weighed and examined histologically at each stage. Further, the metabolites of steroidogenesis were analyzed using normal-phase high performance liquid chromatography. Neonatal exposure significantly reduced testis weights and steroidogenesis to one- fifth to one-half of that of the juvenile control, and further suppressed irreversible steroidogenesis and spermatogenesis during puberty. 相似文献
104.
105.
Protein kinases are an important class of enzymes controlling virtually all cellular signaling pathways. Consequently, selective inhibitors of protein kinases have attracted significant interest as potential new drugs for many diseases. Computational methods, including molecular docking, have increasingly been used in the inhibitor design process [1]. We have considered several docking packages in order to strengthen our kinase inhibitor work with computational capabilities. In our experience, AutoDock offered a reasonable combination of accuracy and speed, as opposed to methods that specialize either in fast database searches or detailed and computationally intensive calculations.However, AutoDock did not perform well in cases where extensive hydrophobic contacts were involved, such as docking of SB203580 to its target protein kinase p38. Another shortcoming was a hydrogen bonding energy function, which underestimated the attraction component and, thus, did not allow for sufficiently accurate modeling of the key hydrogen bonds in the kinase-inhibitor complexes.We have modified the parameter set used to model hydrogen bonds, which increased the accuracy of AutoDock and appeared to be generally applicable to many kinase-inhibitor pairs without customization. Binding to largely hydrophobic sites, such as the active site of p38, was significantly improved by introducing a correction factor selectively affecting only carbon and hydrogen energy grids, thus, providing an effective, although approximate, treatment of solvation. 相似文献
106.
Srinivasa Rao Dasari Subbaiah Tondepu Lakshmana Rao Vadali Nareshvarma Seelam 《合成通讯》2020,50(19):2950-2961
Abstract Polyethylene glycol-400 (PEG-400) has been developed as an efficient and eco-friendly reaction medium for the synthesis of new isoxazolyl pyrido[2,3-d]pyrimidine derivatives 11 from isoxazolyl cyanoacetamide synthon 7. Compound 7 was employed with various aromatic aldehydes 8 and malononitrile 9 in the presence of triethylamine (Et3N) to afford the corresponding (E)-6-amino-1-(3-methyl-5-styrylisoxazol-4-yl)-2-oxo-4-phenyl-1,2-dihydro- pyridine-3,5-dicarbonitrile 10 at room temperature by using PEG-400 as a solvent medium as well as catalyst. The intermediate 10 on treatment with thiourea in the presence of PEG-400 at 90?°C to give the target compounds isoxazolyl pyrido[2,3-d]pyrimidines 11 in good to excellent yields. The newly synthesized compounds 10 and 11 were characterized by IR, 1H NMR, 13C NMR, and HRMS analysis. The target compounds 11a-x was screened for their anti-inflammatory and analgesic activities. Among the tested compounds, the compounds 11s, 11t, 11u, 11v, 11w, and 11x showed significant anti-inflammatory and potent analgesic activities as that of reference drugs. The advantages of this protocol are operational simplicity, catalyst free, environmental safety, wide substrate scope, good yields, and PEG-400 can be recovered and reused. Most significant of all, this protocol is green. 相似文献
107.
A three dimensional pharmacophore model has been generated for glycogen synthase kinase-3 (GSK-3) inhibitots. A dataset consisting of 89 compounds was selected on the basis of the information content of the structures and activity data as required by the CATALYST system. The optimum model with four features (one hydrogen-bond acceptor unit, one ring aromatic unit, and two hydrophobic aromatic units) was selected with a good correlation coefficient (0.95). This model is able to predict the activity of other known GSK-3 inhibitors not included in the model generation, and can be further used to identify structurally diverse compounds with desired biological activity by virtual screening. 相似文献
108.
Yuan-Yuan Zhou Shuang Guo Ying Wang Hong-Juan Song Hui-Rui Gao Xiao-Juan Zhang 《Natural product research》2020,34(13):1805-1813
AbstractFive new α-tetralone glycosides, juglanbiosides A-E (1–5), together with an α-tetralone derivative (15) and nine known 1,4-naphthoquinones (6–14) were isolated from the 95% EtOH extract of green walnut husks of Juglans mandshurica Maxim. Their structures were elucidated by comprehensive spectroscopic methods (1H, 13C NMR, DEPT, HSQC, HMBC, CD, HR-ESI-MS). In vitro cytotoxicities of all the isolated compounds were evaluated against BGC-823, HCT-15 and K562 cancer cell lines. 相似文献
109.
《Arabian Journal of Chemistry》2022,15(12):104330
The present study was carried out to design and synthesize a number of novel aromatic carboxamide derivatives of dehydroabietylamine. The preliminary antifungal assay indicated that most of title compounds displayed moderate to good antifungal activity toward the six fungal strains in vitro. Compounds 3i, 3q, 4b and 4d showed significant antifungal activity against Sclerotinia sclerotiorum, with EC50 values ranging from 0.067 ~ 0.393 mg/L. Compounds 3i, 4b and 4d also showed pronounced mycelial growth inhibition activities against B. cinerea and A. solani. Furthermore, in the in vivo assay, compound 4b exhibited brilliant protective activity against S. sclerotiorum-infected rape leaves. Meanwhile, the in vivo bioassay on tomato plants infected by B. cinerea showed that compound 3i and 4d displayed excellent protective activity at 200 mg/L, which were near to boscalid. Primary mechanistic study revealed that 4b could inhibit sclerotia formation as well as reduce the exopolysaccharide level. SEM and TEM analysis indicated that 4b possessed a strong ability to destroy the surface morphology of mycelia, cell structure and seriously interfere with the growth of the fungal pathogen. In addition, 4b exhibited good inhibitory activity (IC50 = 23.3 ± 1.6 μM) toward succinate dehydrogenase (SDH). Molecular modeling study confirmed the binding modes between compound 4b and SDH. The above antifungal results and fungicidal mechanism study revealed that this class of dehydroabietylamine derivatives could be potential SDH inhibitors and lead compounds for novel fungicides development. 相似文献
110.
Dendrimer‐encapsulated Cu(Π) nanoparticles immobilized on superparamagnetic Fe3O4@SiO2 nanoparticles as a novel recyclable catalyst for N‐arylation of nitrogen heterocycles and green synthesis of 5‐substituted 1H‐tetrazoles
下载免费PDF全文
![点击此处可从《应用有机金属化学》网站下载免费的PDF全文](/ch/ext_images/free.gif)
In this study, dendrimer‐encapsulated Cu(Π) nanoparticles immobilized on superparamagnetic Fe3O4@SiO2 nanoparticles were prepared via a multistep‐synthesis. Then, the synthesized composite was fully characterized by various techniques such as fourier transform infrared (FT‐IR) spectroscopy, X‐ray diffraction (XRD), dynamic light scattering (DLS), UV‐vis spectroscopy, energy dispersive X‐ray analysis (EDX), thermogravimetric analysis (TGA) and vibration sample magnetometer (VSM). From the information gained by FE‐SEM and TEM studies it can be inferred that the particles are mostly spherical in shape and have an average size of 50 nm. Also, the amount of Cu is determined to be 0.51 mmol/g in the catalyst by inductively coupled plasma (ICP) analyzer. This magnetic nano‐compound has been successfully applied as a highly efficient, magnetically recoverable and stable catalyst for N‐arylation of nitrogen heterocycles with aryl halides (I, Br) and arylboronic acids without using external ligands or additives. The catalyst was also employed in a one‐pot, three‐component reaction for the efficient and green synthesis of 5‐substituted 1H‐tetrazoles using various aldehydes, hydroxylamine hydrochloride and sodium azide in water. The magnetic catalyst can be easily separated by an external magnet bar and is recycled seven times without significant loss of its activity. 相似文献