全文获取类型
收费全文 | 863篇 |
免费 | 36篇 |
国内免费 | 281篇 |
专业分类
化学 | 1081篇 |
晶体学 | 8篇 |
综合类 | 8篇 |
物理学 | 83篇 |
出版年
2024年 | 1篇 |
2023年 | 2篇 |
2022年 | 10篇 |
2021年 | 9篇 |
2020年 | 9篇 |
2019年 | 15篇 |
2018年 | 31篇 |
2017年 | 21篇 |
2016年 | 25篇 |
2015年 | 22篇 |
2014年 | 27篇 |
2013年 | 126篇 |
2012年 | 50篇 |
2011年 | 35篇 |
2010年 | 25篇 |
2009年 | 47篇 |
2008年 | 52篇 |
2007年 | 70篇 |
2006年 | 46篇 |
2005年 | 50篇 |
2004年 | 57篇 |
2003年 | 57篇 |
2002年 | 48篇 |
2001年 | 39篇 |
2000年 | 40篇 |
1999年 | 39篇 |
1998年 | 35篇 |
1997年 | 25篇 |
1996年 | 27篇 |
1995年 | 21篇 |
1994年 | 22篇 |
1993年 | 31篇 |
1992年 | 16篇 |
1991年 | 11篇 |
1990年 | 9篇 |
1989年 | 5篇 |
1988年 | 3篇 |
1987年 | 1篇 |
1986年 | 5篇 |
1985年 | 3篇 |
1984年 | 4篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1976年 | 3篇 |
排序方式: 共有1180条查询结果,搜索用时 0 毫秒
11.
Jochen Münchenberg Jens R. Goerlich Axel K. Fischer Peter G. Jones Reinhard Schmutzler 《无机化学与普通化学杂志》1996,622(2):348-354
Synthesis, Structure, and some Reactions of N-(N′,N′,N″,N″-tetramethyl)guanidinyl-substituted Phosphoryl Compounds The tetramethylguanidinyl-substituted phosphoryl compounds 1 – 10 were prepared in the reaction of the appropriate chlorophosphoryl compounds with either N′,N′,N″,N″-tetramethylguanidine (HTMG) or N-trimethylsilyl-(N′,N′,N″,N″-tetramethyl)guanidine (TMSTMG). With methyl iodide 1 reacted with N-alkylation to give the ammonium salt 11. 1 reacted with BF3 · Et2O at both imino nitrogen atoms with formation of the bis-BF3-adduct 12 . The X-ray structure determination of phenylphosphonic acid-bis(N′,N′,N″,N″-tetramethylguanidinide) 3 shows shortened PN-bonds and widened PNC-angles, consistent with the partial double bond character of the PN-bond. 相似文献
12.
合成了3个钛开环夹心羰基化合物.用1HNMR方法对3个钛开环夹心羰基化合物进行了研究实验结果表明,钛开环夹心羰基化合物的分子构象与开环配体的取代状况有关.由对称取代戊稀基配体形成的化合物只有1种构象,由非对称取代戊二稀基[2CH3C5H6]-形成的化合物具有2种构象(cis和trans). 相似文献
13.
Axially substituted tin phthalocyanines, namely dichloride-tetra-(pentyloxy) tin (IV) phthalocyanine 3 and its dimmer di-cyanine 4 were synthesized. The catalytic effect of H2O-free CaCl2 in quinoline was used for condensation of dihydroxy tin phthalocyanine 3 to the cofacially array dimmer 4. Their structures were characterized by UV-vis, IR, elemental analysis, MS, as well as 1HNMR spectroscopy. 相似文献
14.
N. N. Tonkikh A. Strakovs K. V. Rizhanova M. V. Petrova 《Chemistry of Heterocyclic Compounds》2004,40(7):949-955
In reactions of 3-(5- and 5,6-substituted 2-aminophenylamino)-5,5-dimethylcyclohex-2-en-ones with carbaldehydes of pyridine, thiophene, and furan and substituted benzaldehydes, we have obtained 21 novel 7H-7-methoxycarbonyl-, 7-benzoyl-, 7-trifluoromethyl-, 7-nitro- and 7,8-dichloro-11-aryl-3,3-dimethyl-1,2,3,4,10,11-hexahydro-5H-dibenzo[b,e]-1,4-diazepin-1-one. 相似文献
15.
Najim A. Al-Masoudi Nazik M. Aziz Abdulalah T. Mohammed 《Phosphorus, sulfur, and silicon and the related elements》2013,188(11):2891-2901
New Schiff base ligands (6–9) derived from 5-amino-4-phenyl-4H-1,2,4-triazole-3-thiol 1 and substituted benzaldehydes (2–5) as well as their metal complexes with Cu(II), Fe(II), Au(III), and Mn(II) (12–17) have been synthesized. A new benzothiazole derivative (11) was prepared from coupling of 7 with N-(benzothiazol-2-yl)-2-chloroacetamide 10. Their spectral properties were investigated. The newly designed and synthesized Schiff base ligands and the metal complexes were assayed for anti-HIV-1 and HIV-2 activity by examination of their inhibition of HIV-induced cytopathogenicity in MT-4 cells. Compounds 11 and 16 were found to be the most active inhibitors in cell culture (EC50 = 12.2 μg/mL (SI = 4) and > 2.11 μg/mL (SI = > 1), respectively) against HIV-1, whereas 11 showed inhibition against HIV-2 of EC50 > 10.2 μg/mL with SI = 9, which provided a good lead for further optimization. 相似文献
16.
《Analytical letters》2012,45(7):1055-1068
Abstract Tyrosinase-modified carbon paste electrodes were prepared using lyophilised powder of the enzyme purchased from different companies. The selectivity of these electrodes for nine phenolic compounds, including six substituted catechols, has been studied. The signals obtained for catechol were always higher than those found for other phenolic compounds. Cyclic voltammetry and flow injection measurements indicated that the response of the tyrosinase-modified carbon paste electrodes was limited by the rate of the enzymatic oxidation of catechols. Different approaches of paste electrode preparation have been studied and compared. Direct mixing of enzyme into the graphite powder doped with the osmium based mediator, resulted in the highest sensitivity for the studied substrates. However, substrate selectivity was found to be dependent on the source of enzyme used for electrode preparation. 相似文献
17.
取代四苯基卟啉锌配合物与咪唑类和吡啶类等含氮化合物轴向配位反应的研究在模拟生物体中锌酶的作用机理方面具有重要意义。在现有的文献中 ,人们的研究主要集中在四苯基卟啉的苯环上连有如卤素、甲氧基、甲基等较小取代基的卟啉锌上[1~3] ,对于结构不对称且苯环上连有氨基酸的四苯基卟啉锌与含氮化合物轴向配位反应的研究尚不多见。有关尾式氨基酸四苯基卟啉锌配合物的合成和性质我们进行过较系统的研究[4~6] 。本文以 5 ( 4 甘氨酸丁氧苯基 ) 1 0 ,1 5 ,2 0 三苯基卟啉锌 (ZnP)为锌酶的模型化合物 ,用热力学方法研究了它与吡啶 (… 相似文献
18.
单N-乙酸取代O2N2大环配体及其稀土配合物的合成与表征 总被引:2,自引:0,他引:2
Aseries of new rare earth complexes LnL(NO3)2·2H2O(Ln=La,Pr,Nd,Sm,Eu,Gd,Dy,Yb;L=1,2-diaza-3,4: 9,10-dibenzo-5,8-dioxyacyclopentadecane-N-acetic ion) were prepared. The complexes were characterized by elemental analysis, ICPmethod, IRspectra, 1H NMRand Molar conductance. It was found that the ether oxygen, carboxy oxygen and nitrogen atoms of the ligand are coordinated to the metal ion, as well as a free nitrate and coordianted nitrate ion in the complex. 相似文献
19.
In this study, Ag, Ni2+, and Fe2+ immobilized on hydroxyapatite‐core‐shell γ‐Fe2O3 nanoparticles (γ‐Fe2O3@HAp‐Ag, γ‐Fe2O3@HAp‐Ni2+, and γ‐Fe2O3@HAp‐Fe2+) as a new and reusable Lewis acid magnetic nanocatalyst was successfully synthesized and reported for an atom economic, extremely facile, and environmentally benign procedure for the synthesis of highly functionalized tetrahydropyridines derivatives 4a‐t is described by one‐pot five‐component reaction of 2 equiv of aldehydes 1 , 2 equiv of amines 2 , and 1 equiv of methyl acetoacetate 3 in EtOH at room temperature in good to high yields and short reaction time. The presented methodology offers several advantages such as easy work‐up procedure, reusability of the magnetic nanocatalyst, operational simplicity, green synthesis avoiding toxic reagents and solvent, mild reaction conditions, and no tedious column chromatographic separation. 相似文献
20.
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