全文获取类型
收费全文 | 6545篇 |
免费 | 1205篇 |
国内免费 | 887篇 |
专业分类
化学 | 4887篇 |
晶体学 | 76篇 |
力学 | 549篇 |
综合类 | 93篇 |
数学 | 711篇 |
物理学 | 2321篇 |
出版年
2024年 | 16篇 |
2023年 | 141篇 |
2022年 | 265篇 |
2021年 | 254篇 |
2020年 | 329篇 |
2019年 | 287篇 |
2018年 | 230篇 |
2017年 | 245篇 |
2016年 | 322篇 |
2015年 | 345篇 |
2014年 | 417篇 |
2013年 | 498篇 |
2012年 | 618篇 |
2011年 | 626篇 |
2010年 | 438篇 |
2009年 | 439篇 |
2008年 | 408篇 |
2007年 | 337篇 |
2006年 | 319篇 |
2005年 | 260篇 |
2004年 | 249篇 |
2003年 | 201篇 |
2002年 | 199篇 |
2001年 | 190篇 |
2000年 | 129篇 |
1999年 | 123篇 |
1998年 | 114篇 |
1997年 | 84篇 |
1996年 | 106篇 |
1995年 | 67篇 |
1994年 | 72篇 |
1993年 | 53篇 |
1992年 | 46篇 |
1991年 | 34篇 |
1990年 | 30篇 |
1989年 | 25篇 |
1988年 | 19篇 |
1987年 | 14篇 |
1986年 | 24篇 |
1985年 | 19篇 |
1984年 | 11篇 |
1983年 | 12篇 |
1982年 | 10篇 |
1981年 | 5篇 |
1980年 | 4篇 |
1979年 | 2篇 |
1975年 | 1篇 |
排序方式: 共有8637条查询结果,搜索用时 31 毫秒
171.
Oligomerization and Polymerization of Ethylene Initiated by a Novel Ni(Ⅱ)-Based Acetyliminopyridine Complexes as Single-Site Catalysts
下载免费PDF全文
![点击此处可从《天然气化学杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Baojun Zhang Yanji Wang Gang Wang Jun Cao Shukun Sun Lihua Xing Yongcheng Sun Yunguang Han Hebei University of Technology Tianjin China Research Institute of Daqing Petrochemical Company Daqing Heilongjiang China College of Chemical Science Engineering China University of Petroleum Beijing China 《天然气化学杂志》2007,16(1):64-69
Novel Ni(Ⅱ)-based acetyliminopyridine complexes 1b, 2b, 3b (1-3b), which are synthesized from ligands 1a, 2a, 3a (1-3a) and [NiCl2(DME)], are suitable precursors for the catalysts that are necessary for ethylene oligomerization and polymerization reactions, activated by methylaluminoxane (MAO). The MAO-treated 1-3b presents an active catalytic center, which may oligomerize and polymerize ethylene to produce linearα-olefins and polyethylene, respectively. The molecular weight distributions of oligomers that are obtained are in good agreement with the Schulz-Flory rules for oligomers>C4. The activity of 3b-MAO complex is 6.3×107 g/(molNi·h) at 50℃. The activities and molecular weight distributions of oligomers show significant reliance on the structures of catalyst precursors. 相似文献
172.
A sensitive catalytic method is developed for the spectrophotometric determination of oxalic acid. The procedure is based on the effect of oxalate on the oxidation of Victoria blue B by dichromate in dilute sulfuric acid medium. The reaction is quantitatively estimated by measuring the decrease in absorbance of Victoria blue B at the maximum wavelength of 610nm after quenching the reaction with tap water. The factors effecting the sensitivity and reproducibility of the reaction were studied. The method is not interfered with by foreign species generally associated with oxalate and oxalic acid. The described method is simple, specific, inexpensive and suitable for oxalic acid concentrations of between 0.06 and 9.0µgmL–1. It was validated with satisfactory results by determining oxalic acid content in water extracts from plant materials such as spinach and Lathyrus sativus. 相似文献
173.
利血平的光化学荧光特性及其应用 总被引:3,自引:1,他引:3
在10%HAc介质中,利血平经紫外光照射时,其光化学反应产物具有强烈荧光(λ_(ax)=385 nm,λ_(ax)=490 nm)。利血平浓度在0.01~0.30μg/ml范围内,荧光强度与浓度呈良好的线性关系,由此建立了利血平的光化学荧光测定法。方法的检出限为1.3 ng/ml,相对标准偏差为1.6%。本法简便快速且灵敏度高,可用于片剂及注射液中利血平含量的测定。 相似文献
174.
Synthesis of poly(thiocarbonate)s from the copolymerization of epoxides and carbon disulfide (CS2) remains a tough challenge, due to inevitable oxygen‐sulfur atom scrambling process. In this work, we utilized the oxygen‐sulfur exchange reaction (O‐S ER) to synthesize a random copolymer with monothiocarbonate and trithiocarbonate units from CS2 and phenyl glycidyl ether (PGE) via metal‐free Lewis pairs. The copolymers contained monothiocarbonate and trithiocarbonate units of which the molar fraction could be tuned by varying either the types of Lewis pairs or the reaction temperature. Keeping track on the intermediate provided an insight in the process of O‐S ER and thus gave a hint to control the product structure. Production and consumption of phenyl thioglycidyl ether was the key process to regulate the chain structure. Remarkably, the oxygen atoms of PGE could be excluded out of the chain, resulting in the nearly complete production of poly(trithiocarbonate)s. Correspondingly, the refractive index of this kind of copolymer could be regulated in a wide range of 1.73—1.79 (at 590 nm). 相似文献
175.
176.
H. Zhang Z. F. Chai H. B. Sun J. L. Zhang H. Ouyang L. Xin Y. D. Chuai 《Journal of Radioanalytical and Nuclear Chemistry》2007,271(1):31-35
The concentrations and distributions of total halogen (TX), extractable organohalogen (EOX) and extractable persistent organohalogen
(EPOX) were determined in 20 kinds of yogurt specimens collected from Chinese supermarkets using neutron activation analysis
(NAA) and gas chromatography equipped with a 63Ni electron capture detector (GC-ECD). The results indicated that the halogens in yogurt mainly existed as non-extractable
organohalogen compounds. About 25–30% of EOX was EPOX. EOCl and EPOCl were the main organohalogen species in yogurt. The average
concentration of the identified organochlorine, such as organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs),
was below 4% of EPOCl. 相似文献
177.
Improvement of cyclosporin A determination in whole blood by reversed-phase high-performance liquid chromatography 总被引:1,自引:0,他引:1
A chromatographic method was developed for the determination of cyclosporin A in human whole blood using reversed-phase HPLC at room temperature. Most previous reports carried out this liquid chromatographic separation at temperatures above 70 degrees C. The present procedure greatly improves the detection limit by controlling peak broadening effects, as well as the lifetime of the column at room temperature. Under optimal conditions and using ketoconazole as an internal standard, the calibration graph was linear in the range of 16-1000 microg/L with a relative standard deviation of 3.72% at 150 microg/L and 2.45% at 300 microg/L (n = 11) of cyclosporin A. The detection limit was of 5.0 microg/L cyclosporin A. By this procedure, cyclosporin A pharmacokinetic parameters in healthy Chinese subjects were studied. The developed method could be applied to the quantification of cyclosporin A in human blood samples and allows the study of its pharmacokinetics in routine laboratories. 相似文献
178.
Xian Rong Cai Hao Chen Tao Zhang Xing Xu Ying Li Qing Jiang 《中国化学快报》2007,18(11):1342-1346
A novel oxadiazole-based copolymer has been successfully synthesized through the palladium-catalyzed cross-coupling polycondensation method.The copolymer P is soluble in common organic solvents.Its structure has characterized by ~1H NMR,~(13)C NMR,gel permeation chromatagraphy (GPC),UV-vis absorbance (Abs) and photoluniminescence (PL) spectroscopy,and cyclic voltammetry (CV).Investigation of its optical properties revealed that it is yellow emitting material,and the electrochemical analysis showed that P was well suited poly (2,5-dioctyloxy-p-phenylenevinylene) (PDOCPV) for photovoltaic devices,so the copolymer P is able to act as an electron acceptor in combination with PDOCPV as the electron donor to quench photoluminescence of the copolymer in the blend,indicative of the efficient photoinduced electron transfer from the PDOCPV to the P. 相似文献
179.
A novel protocol for assembling polycyclic ethers was developed and successfully applied to the synthesis of the EFGH ring system of ciguatoxin CTX3C. A key transformation involves construction of an O,S-acetal through coupling of alpha-chlorosulfide and a secondary alcohol under mild conditions. The method is highly applicable to use with sensitive substrates and will enable the synthesis of various natural and artificial polycyclic ethers. [reaction: see text] 相似文献
180.
The electronic structure of adenosylcobalamin (B12 coenzyme, AdoCbl) has been calculated by a density functional method, using the orthogonalized linear combination of the atomic orbital method (OLCAO). Since a fixed accurately determined geometry was needed in such calculations, the crystal structure of adenosylcobalamin has been redone and refined to R = 0.065, using synchrotron diffraction data. Comparison with the recently reported electronic structures of cyano- (CNCbl) and methylcobalamin (MeCbl) shows that the net charges and bond orders vary only on the axial donors. The values in the three cobalamins suggest that the Co-C bond in MeCbl has a strength similar to that in AdoCbl, but it is significantly weaker that that in CNCbl. Present results are compared with those previously reported for the analogous corrin derivatives; i.e., simplified cobalamins with the side chains a-f replaced by H atoms. Despite a qualitative agreement, a discrepancy in the calculated HOMO-LUMO gap is found. 相似文献