全文获取类型
收费全文 | 2285篇 |
免费 | 92篇 |
国内免费 | 320篇 |
专业分类
化学 | 2142篇 |
晶体学 | 17篇 |
力学 | 5篇 |
综合类 | 16篇 |
数学 | 242篇 |
物理学 | 275篇 |
出版年
2024年 | 9篇 |
2023年 | 68篇 |
2022年 | 50篇 |
2021年 | 75篇 |
2020年 | 151篇 |
2019年 | 105篇 |
2018年 | 94篇 |
2017年 | 114篇 |
2016年 | 106篇 |
2015年 | 67篇 |
2014年 | 132篇 |
2013年 | 508篇 |
2012年 | 167篇 |
2011年 | 137篇 |
2010年 | 99篇 |
2009年 | 114篇 |
2008年 | 111篇 |
2007年 | 121篇 |
2006年 | 115篇 |
2005年 | 86篇 |
2004年 | 87篇 |
2003年 | 56篇 |
2002年 | 11篇 |
2001年 | 12篇 |
2000年 | 12篇 |
1999年 | 8篇 |
1998年 | 10篇 |
1997年 | 12篇 |
1996年 | 7篇 |
1995年 | 10篇 |
1994年 | 5篇 |
1993年 | 9篇 |
1992年 | 3篇 |
1991年 | 6篇 |
1990年 | 4篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有2697条查询结果,搜索用时 0 毫秒
41.
《Mendeleev Communications》2021,31(5):673-676
New pathways of reaction between 1-methylthiourea or 1-methylurea and benzil bring about new derivatives of (2S*,3aR*,6aS*)-perhydro-3aH-[1,3]dioxolo[4,5-d]imidazole and racemic (4S*,5R*)-4-alkoxy-5-hydroxy-1-methyl-4,5-diphenylimidazolidine-2-thiones. Some of the obtained urea-and thiourea derivatives were characterized by X-ray diffraction, which showed their supramolecular organization governed by the directionality of hydrogen bonds at the acceptor side C=O or C=S groups. 相似文献
42.
《Mendeleev Communications》2021,31(6):824-826
The study of oxidation step in the preparation of benzocamalexin by the α-amidoalkylation–oxidation sequence revealed the formation of perchloro-1,2-phenylene dibenzoate as the product of transformation of tetrachloro- 1,2-benzoquinone applied as the oxidant. The structures of benzocamalexin and perchloro-1,2-phenylene dibenzoate were confirmed by X-ray diffraction analysis. The extraction step in the final isolation of benzocamalexin is supposed to be crucial for the complete transformation of mono- and di- acylated perchloropyrocatechol. 相似文献
43.
在纤维素三(3,5-二甲基苯基氨基甲酸酯)(Chiralcel OD-H)和Pirkle型(R, R)-Whelk-O1手性柱上对手性氨基酚1-(α-氨基苄基)-2-萘酚(Betti 碱)及其衍生物1-(α-苄氨基苄基)-2-萘酚和1-(α-哌啶基苄基)-2-萘酚对映体分离进行了研究,分别考察了在正己烷流动相中,碱性添加剂、醇类添加剂的种类和浓度对手性拆分的影响。结果表明:溶质在Chiralcel OD-H柱上的分离效果好,而在(R, R)-Whelk-O1手性柱上只有1-(α-苄氨基苄基)-2-萘酚部分分离。研究了空间立体结构因素对手性分离的影响,初步探讨和比较了溶质在这2种手性柱上的手性识别机理。发现对(R, R)-Whelk-O1柱,溶质与固定相之间的吸引作用很小,而对于Chiralcel OD-H柱,溶质在手性空腔中的空间适应性很可能是手性识别的关键。 相似文献
44.
We reported in this paper FTIR linear diehroic spectroscopy and anisotropic properties of the nanoparticulate α-Fe_2O_3-stearate alternating Langmuir-Blodgett films (Fe_2O_3-St LB films) a new inorganic-organic quantum superlattice system. A new method fitted to inorganic-organic alternating films is used to study the molecular orientation and discuss the order arrangement of the nanopartieles in the films. The the results show that a configuration of stearate ions bound to the surface of the nano-particles: COO~- group are spherically bound to the surface of the nanoparticles; the hydrocarbon chains are almost perpendicular (31°±5°) to the substrate (7 nm-Fe_2O_3-St LB films). The orientation of hydrocarbon chains and CH_2 scissors vibration show the existence of trans-zigzag planar structure for C—C broken bone of the hy7drocarbon chains, which is related to high-order structure of the alternate films. 相似文献
45.
金负载量对低温水煤气变换Au/α-Fe2O3催化剂结构和性能的影响 总被引:5,自引:3,他引:5
采用共沉淀法制备了低温水煤气变换Au/α-Fe2O3催化剂。通过正交实验优化催化剂的还原活化条件,考察了金负载量对催化剂性能的影响。采用BET、XRD、UV-VIS、XRF、H2-TPR和O2-TPO等表征手段对催化剂的结构进行分析,并与其催化性能进行关联。结果表明,(1)采用10%-H2/N2还原气将催化剂在150 ℃原位还原9 h,其催化活性最高;(2)金的最佳负载量为8.00%,此时在催化剂制备过程中金的流失量较少,金粒子较小,也有利于抑制催化剂在反应过程中烧结;(3)TPR-TPO结果表明,金的负载量为8.00%时,Au/α-Fe2O3催化剂具有较易被还原、不易被氧化的性质,从而显示出最高催化活性。(4)Au/α-Fe2O3催化剂中的金以单质金(Au0)形式存在;其高活性与Au0-Fe3O4间的协同作用有关。 相似文献
46.
We reported the environmental benign synthesis of chalcones,2-pyrazolines and cyclohexanones under microwave irradiation.Chalcones were obtained by the condensation of each of 2-hydroxyacetophenone derivatives with a-naphthaldehyde under microwave irradiation.The condensation reactions of each of synthesized chalcones with phenyl hydrazine under microwave irradiation in the presence of dry acetic acid as a cyclizing agent gave 2-pyrazolines.Also,the new cyclohexenone derivatives,valuable intermediates to synthesize fused heterocycles,have been prepared by the cyclocondensation of each of hydroxychalcones with ethyl acetoacetate.The structures of the synthesized compounds were elucidated by infrared(IR) spectrometry,nuclear magnetic resonance(NMR),mass spectrometry(MS) and elmental analysis.The results indicate that unlike classical heating,microwave irradiation results in higher yields with shorter and cleaner reactions.The synthesized compounds were screened for antimicrobial activity against Staphylococcus aureus,Escherichia coli,Candida Albicans and Aspergillus niger.We clarified the effects of different substituents in the tested compounds on the obtaind antibacterial activities and antifungal activities. 相似文献
47.
Shang Wu Hongheng Yu Qinzheng Hu Quanlu Yang Shouwang Xu Tian Liu 《Tetrahedron letters》2017,58(51):4763-4765
A silver-catalyzed decarboxylative cross-coupling of α-keto acids with alkenes is reported. The method, with a wide range of substrate tolerance and mild operational conditions, can produce various chalcone derivatives in moderate to high yields from easily available starting materials. 相似文献
48.
Aleksandra Minić Jovana P. Bugarinović Anka Pejović Danijela Ilić Komatina Goran A. Bogdanović Ivan Damljanović Dragana Stevanović 《Tetrahedron letters》2018,59(38):3499-3502
A simple one-pot synthesis of new ferrocene-containing 1,3-thiazinan-2-imines from 3-arylamino-1-ferrocenylpropan-1-ols and phenyl isothiocyanate has been developed. The key intermediate β-hydroxy thioureas were generated in situ using ultrasound irradiation and subsequent cyclization was achieved by the addition of acetic acid. The scope of the reaction towards various 3-arylamino-1-ferrocenylpropan-1-ols has been explored and the corresponding 3-aryl-6-ferrocenyl-N-phenyl-1,3-thiazinan-2-imines were obtained in moderate to high yields (52–90%). 相似文献
49.
Murali Krishna Kolli Palani Elamathi Vishweshwar Rao Katta Gajendrasinh Balvantsinh Raolji 《合成通讯》2018,48(6):638-649
One-pot synthesis of α-aminophosphonates directly from aryl nitro compounds, aldehydes/ketones, and diethyl phosphite using sodium dithionite through reduction and followed by Kabachnik–Fields reaction under metal-free conditions is reported. The major advantages are excellent yield, high chemoselectivity, neutral reaction medium, and simple experimental procedure. This methodology consists of the following steps: 1) amine formation from nitro compound, 2) imine formation from amine and aldehyde/ketone, 3) phosphate addition to imine. 相似文献
50.
Kukhtin-Ramirez反应是有机化学中一类重要的极性反转反应.利用三价磷的还原性对α-羰基酮化合物进行极性反转,所生成的Kukhtin-Ramirez活性中间体在诸多转化中都展现出了其作为1,1-偶极子的化学性质.近年来关于该活性中间体的反应研究主要包括:极性X—H键插入反应、还原性加成反应、形式[2+1]环加成反应、形式[4+1]环加成反应、形式[4+2]环加成反应.这些转化为一些重要的多官能团化合成中间体及结构复杂的环状化合物提供了高效简洁的合成方法,凸显了Kukhtin-Ramirez极性反转反应在有机合成中的重要性. 相似文献