全文获取类型
收费全文 | 1167篇 |
免费 | 44篇 |
国内免费 | 46篇 |
专业分类
化学 | 867篇 |
晶体学 | 10篇 |
力学 | 34篇 |
数学 | 83篇 |
物理学 | 263篇 |
出版年
2024年 | 5篇 |
2023年 | 9篇 |
2022年 | 28篇 |
2021年 | 27篇 |
2020年 | 17篇 |
2019年 | 26篇 |
2018年 | 8篇 |
2017年 | 7篇 |
2016年 | 24篇 |
2015年 | 29篇 |
2014年 | 51篇 |
2013年 | 53篇 |
2012年 | 74篇 |
2011年 | 101篇 |
2010年 | 59篇 |
2009年 | 77篇 |
2008年 | 94篇 |
2007年 | 75篇 |
2006年 | 80篇 |
2005年 | 51篇 |
2004年 | 34篇 |
2003年 | 27篇 |
2002年 | 28篇 |
2001年 | 19篇 |
2000年 | 18篇 |
1999年 | 14篇 |
1998年 | 12篇 |
1997年 | 19篇 |
1996年 | 14篇 |
1995年 | 12篇 |
1994年 | 16篇 |
1993年 | 11篇 |
1992年 | 13篇 |
1991年 | 7篇 |
1990年 | 8篇 |
1989年 | 5篇 |
1988年 | 6篇 |
1987年 | 4篇 |
1986年 | 8篇 |
1985年 | 8篇 |
1982年 | 4篇 |
1981年 | 6篇 |
1980年 | 8篇 |
1979年 | 4篇 |
1978年 | 5篇 |
1977年 | 3篇 |
1976年 | 8篇 |
1975年 | 5篇 |
1974年 | 12篇 |
1973年 | 12篇 |
排序方式: 共有1257条查询结果,搜索用时 15 毫秒
961.
Fei-Peng Hsieh & Shu-Rong Xu 《计算数学(英文版)》1990,8(3):212-222
It is showed that, for many commonly used difference models on hyperbolic initial boundary value problems, the necessary and sufficient condition for GKS-stability is a necessary condition for $l_2$-stability. 相似文献
962.
The crystalline structure of dried cotton fibers at varying development stages has been investigated using wide angle x-ray diffraction (WAXS) techniques. The cellulose I crystalline structure has been confirmed on dried SJ-2 Acala cotton fibers collected at varying developmental stages and at maturity. The cellulose I crystalline structure is clearly evident at the early developmental stage of 21 days postanthesis (dpa). The crystal system remains unchanged during the cotton fiber biosynthesis and at maturity. The degree of crystallinity and crystallite dimensions in the cotton fibers increase with cell development. The most significant increments are observed between 21 and 34 dpa (i.e., during the first half of the secondary wall thickening process). The unit cell sizes slightly decrease and thus the crystal density increases with fiber development. The alignment of the glucosidic rings in respect to the 002 planes improves with fiber cell development. © 1996 John Wiley & Sons, Inc. 相似文献
963.
Huang HC Chang TY Chang LZ Wang HF Yih KH Hsieh WY Chang TM 《Molecules (Basel, Switzerland)》2012,17(4):3902-3916
This study was aimed at investigating the antimelanogenic and antioxidative properties of the essential oil extracted from leaves of V. negundo Linn and the analysis of the chemical composition of this essential oil. The efficacy of the essential oil was evaluated spectrophotometrically, whereas the volatile chemical compounds in the essential oil were analyzed by gas chromatography-mass spectrometry (GC-MS). The results revealed that the essential oil effectively suppresses murine B16F10 tyrosinase activity and decreases the amount of melanin in a dose-dependent manner. Additionally, the essential oil significantly scavenged 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS) radicals, and showed potent reducing power versus metal-ion chelating properties in a dose-dependent pattern. The chemical constituents in the essential oil are sesquiterpenes (44.41%), monoterpenes (19.25%), esters (14.77%), alcohols (8.53%), aromatic compound (5.90%), ketone (4.96%), ethers (0.4%) that together account for 98.22% of its chemical composition. It is predicted that the aromatic compound in the essential oil may contribute to its antioxidant activities. The results indicated that essential oil extracted from V. negundo Linn leaves decreased melanin production in B16F10 melanoma cells and showed potent antioxidant activities. The essential oil can thereby serve as an inhibitor of melanin synthesis and could also act as a natural antioxidant. 相似文献
964.
二甲基亚砜中E-Ni-Co合金膜的电化学制备 总被引:3,自引:0,他引:3
利用循环伏安法和恒电位电解法研究了室温条件下在LiClO4-二甲基亚砜(DMSO)体系中Er-Ni-Co功能合金膜的电化学制备.实验结果表明, 在0.1 mol•L-1 ErCl3-0.1 mol•L-1 NiCl2-0.1 mol•L-1 CoCl2-0.1 mol•L-1 LiClO4-DMSO体系中,控制电位在-2.20~-2.50 V范围内进行恒电位电解,得到表面均匀、附着力强、有金属光泽的黑色非晶态Er-Ni-Co合金膜, 其中Er的质量分数可达9.21%~18.90%. 相似文献
965.
Cheng‐Hsien Hsieh 《中国化学会会志》2007,54(1):31-34
The liquid precipitation method using zinc acetate dihydrate was applied for the synthesis of uniform and spherical ZnO nanoparticles. The ultrafine zinc oxid was prepared in a water‐ethanol mixture solution. The solution containing zinc cation was soluble in water. The surface‐active agent triethanolamine (TEA) was soluble in ethanol. Then alkali precipitated by adding n‐propylamine. The spherical zinc oxide particle morphology was found to be highly dependent on the zinc salt concentration, ethanol‐water ratio, and the surface‐active agent additive. The process can produce white ZnO powder of 50–90 nm in size. The morphology of zinc oxide showed a powder shape by transmission electron microscopy (TEM), the crystallization phase structure of zinc oxide by X‐ray diffraction (XRD), and the zinc oxide remaining by using an organic analysis by infrared spectroscopy (IR). 相似文献
966.
Improving the Ring‐opening Polymerization of l‐Lactide Using n‐Butyl Lithium with Various Bidentate Ligands
下载免费PDF全文

Hsuan‐Ying Chen Yen‐Tzu Huang Jaya Kishore Vandavasi Yu‐Hsieh Chen Chia‐Hao Kuei 《中国化学会会志》2016,63(10):859-863
A series of bidentate ligands were examined to improve the catalytic activity of l ‐lactide (LA) polymerization by using n‐butyl lithium and BnOH. For LA polymerization, n‐butyl lithium with tetraisopropyl methylenebis(phosphonate) (L8 ) showed the greatest catalytic activity but with poor controllability of the polymer molecular weight. The polydispersity indices (PDIs) could be improved without BnOH addition, but Mn GPC was much different from the Mn Cal . 1H NMR spectra confirmed that the cyclized PLA was obtained, thus implying that active chain‐end mechanisms were operative in LA polymerization. 相似文献
967.
This paper describes a newly developed high performance liquid chromatography/electrospray/mass spectrometry (HPLC/ES/MS) method for the determination of flunarizine (FZ) in artificial cerebrospinal fluid. The optimization for the detection of FZ in biological fluid by LC/ES/MS was investigated. The effects of solvent composition, the addition of modifier and flow rate on the detection of FZ by ES/MS were examined. The detection limit of this method (0.8 nM) proved to be much better than previously reported methods. Satisfactory accuracy (98.2–106.0%) of this newly developed method was obtained. The application of this method was demonstrated by analyzing FZ in rat microdialysis samples. 相似文献
968.
Lee SH Chin CH Chen WK Huang WJ Hsieh CC 《Physical chemistry chemical physics : PCCP》2011,13(18):8515-8525
We conducted the title reaction using a crossed molecular-beam apparatus, quantum-chemical calculations, and RRKM calculations. Synchrotron radiation from an undulator served to ionize selectively reaction products by advantage of negligibly small dissociative ionization. We observed two products with gross formula C(2)H(3)N and C(2)H(2)N associated with loss of one and two hydrogen atoms, respectively. Measurements of kinetic-energy distributions, angular distributions, low-resolution photoionization spectra, and branching ratios of the two products were carried out. Furthermore, we evaluated total branching ratios of various exit channels using RRKM calculations based on the potential-energy surface of reaction N((2)D)+C(2)H(4) established with the method CCSD(T)/6-311+G(3df,2p)//B3LYP/6-311G(d,p)+ZPE[B3LYP/6-311G(d,p)]. The combination of experimental and computational results allows us to reveal the reaction dynamics. The N((2)D) atom adds to the C=C π-bond of ethene (C(2)H(4)) to form a cyclic complex c-CH(2)(N)CH(2) that directly ejects a hydrogen atom or rearranges to other intermediates followed by elimination of a hydrogen atom to produce C(2)H(3)N; c-CH(2)(N)CH+H is the dominant product channel. Subsequently, most C(2)H(3)N radicals, notably c-CH(2)(N)CH, further decompose to CH(2)CN+H. This work provides results and explanations different from the previous work of Balucani et al. [J. Phys. Chem. A, 2000, 104, 5655], indicating that selective photoionization with synchrotron radiation as an ionization source is a good choice in chemical dynamics research. 相似文献
969.
Chi‐Fong Lin Wen‐Der Lu Pei‐Chen Hsieh Yao‐Haur Kuo Huey‐Fen Chiu Chyi‐Jia Wang Ming‐Jung Wu 《Helvetica chimica acta》2002,85(8):2564-2575
The activities of a series of acyclic enediynes, 2‐(6‐substituted hex‐3‐ene‐1,5‐diynyl)benzonitriles ( 1 – 5 ) and their derivatives 7 – 23 were evaluated against several solid tumor cell lines and topoisomerase I. Compounds 1 – 5 show selective cytotoxicity with Hepa cells, and 2‐[6‐phenylhex‐3‐ene‐1,5‐diynyl]benzonitrile ( 5 ) reveals the most‐potent activity. Analogues 8 – 10 and 13 – 22 also have the same effect with DLD cells; 1‐[(Z)‐dec‐3‐ene‐1,5‐diynyl)‐4‐nitrobenzene 21 shows the highest activity among them. Moreover, 1‐[(Z)‐dec‐3‐ene‐1,5‐diynyl]‐2‐(trifluoromethyl)benzene ( 20 ) exhibits the strongest inhibitory activity with the Hela cell line. Derivatives 9, 10, 18 , and 23 display inhibitory activities with topoisomerase I at 87 μM . The cell‐cycle analysis of compound 5 , which induces a significant blockage in S phase, indicates that these novel enediynes probably undergo other biological pathways leading to the cytotoxicity, except the inhibitory activity toward topoisomerase I. 相似文献
970.
This report describes the synthesis, characterization, and X-ray crystal structures of two Mn(III) complexes, Mn(DMHP)3 x 12H2O and Mn(DMHP)2Cl x 0.5H2O (DMHP = 1,2-dimethyl-3-hydroxy-4-pyridinone). Mn(DMHP)2Cl was prepared from the reaction of Mn(II) chloride with 2 equiv of DMHP under reflux in the presence of triethylamine. Mn(DMHP)3 was obtained by reacting Mn(II) acetate with 3 equiv of DMHP in the presence of sodium acetate. Mn(DMHP)3 could also be prepared by reacting Mn(OAc)3 x 2H2O with 3 equiv of DMHP in the presence of triethylamine. Both Mn(III) complexes have been characterized by elemental analysis, infrared spectroscopy, electronic paramagnetic resonance, electrospray ionization spectroscopy, electrochemical method, and X-ray crystallography. The X-ray crystal structure of Mn(DMHP)2Cl x 0.5H2O revealed a rare example of five-coordinated Mn(III) complexes with two bidentate ligands and a square pyramidal coordination geometry. Surprisingly, the average Mn-O (hydroxy) bond distance in Mn(DMHP)2Cl x 0.5H2O is approximately 0.025 A longer than that of the average Mn-O (carbonyl) bond, suggesting an extensive delocalization of electrons in the two pyridinone rings. The structure of Mn(DMHP)3 x 12H2O, a rare example of six-coordinate high-spin Mn(III) complexes without Jahn-Teller distortion, is isostructural to M(DMHP)3 x 12H2O (M = Al, Ga, Fe, and In). The electrochemical data for Mn(DMHP)3 suggests that the Mn(III) oxidation state is highly stabilized by three DMHP ligands. DMHP has the potential as a chelator for the removal of excess intracellular Mn and the treatment of chronic Mn toxicity. 相似文献