全文获取类型
收费全文 | 2129篇 |
免费 | 142篇 |
国内免费 | 28篇 |
专业分类
化学 | 1509篇 |
晶体学 | 41篇 |
力学 | 89篇 |
数学 | 175篇 |
物理学 | 485篇 |
出版年
2024年 | 17篇 |
2023年 | 23篇 |
2022年 | 105篇 |
2021年 | 140篇 |
2020年 | 98篇 |
2019年 | 88篇 |
2018年 | 82篇 |
2017年 | 63篇 |
2016年 | 103篇 |
2015年 | 86篇 |
2014年 | 102篇 |
2013年 | 153篇 |
2012年 | 164篇 |
2011年 | 173篇 |
2010年 | 106篇 |
2009年 | 78篇 |
2008年 | 89篇 |
2007年 | 83篇 |
2006年 | 69篇 |
2005年 | 67篇 |
2004年 | 51篇 |
2003年 | 36篇 |
2002年 | 28篇 |
2001年 | 14篇 |
2000年 | 11篇 |
1999年 | 8篇 |
1998年 | 6篇 |
1997年 | 15篇 |
1996年 | 21篇 |
1995年 | 9篇 |
1994年 | 13篇 |
1993年 | 14篇 |
1992年 | 8篇 |
1991年 | 14篇 |
1990年 | 11篇 |
1989年 | 5篇 |
1988年 | 9篇 |
1987年 | 14篇 |
1986年 | 14篇 |
1985年 | 14篇 |
1984年 | 12篇 |
1982年 | 14篇 |
1981年 | 5篇 |
1980年 | 7篇 |
1978年 | 7篇 |
1977年 | 6篇 |
1976年 | 7篇 |
1975年 | 5篇 |
1973年 | 8篇 |
1972年 | 7篇 |
排序方式: 共有2299条查询结果,搜索用时 15 毫秒
31.
The complexation of triprolidine hydrochloride (TRP) and β-cyclodextrin (β-CD) in deuterium oxide was investigated by 400 MHz 1^H NMR spectroscopy. The 800 MHz 2D ROESY data revealed that two 1 :1 and one 2 : 1 β-CD-TRP inclusion complexes were formed. Both aromatic moieties (p-tolyl and pyridyl ring) has entered into the β-CD cavity, confirming the existence of two different equilibria for 1 : 1 inclusion complexes in which p-tolyl ring of the guest is more tightly held by the host cavity. The ROE intermolecular interactions provided the plausible structures of these 1 : 1 and 2 : 1 stoichiometric inclusion complexes of β-CD-triprolidine hydrochloride in solu- tion. 相似文献
32.
Summary
Sensitive and Selective Spectrophotometric Method for the Determination of Trace Amounts of Osmium with 1,2,3-Indanetrione Monothiosemicarbazone
A simple, sensitive and selective spectrophotometric method has been developed for the determination of osmium using 1,2,3-indane-trione monothiosemicarbazone (ITMT). The method is based on the colour reaction between ITMT and osmium(VIII) in hydrochloric acid (0.32–0.60 M) medium. The calibration graph for measurement at 440 nm is linear in the range 1.4–33.6g of osmium per 25ml, with a molar absorptivity of 6.43×104l·mole–1·cm–1. The effect of interferences has been studied and the method applied to the determination of osmium in synthetic samples whose composition correspond to osmiridium or syserkite, with good results. 相似文献
33.
A radiochemical displacement method for the determination of micro amounts of Hg(II) has been developed. 65Zn was displaced from the Zn-1-(2-pyridylazo-2-naphthol) complex at pH 5 in borate buffers by Hg (II). 10-80 micrograms of mercury could be determined. Interference of various metal ions and methods for suppression have also been carried out. 相似文献
34.
Christian C. Van de Sande Syed Zahoor Ahmad Friedrich Borchers Karsten Levsen 《Journal of mass spectrometry : JMS》1978,13(11):666-670
Gaseous protonated aziridine ions are produced at the threshold from β-phenoxyethylamine molecular ions. The evidence for this is collisional activation spectra, using various precursors (including labelled analogues) under electron impact and field ionization conditions. Partial conversion to the acyclic \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CH}_{\rm 3} {\rm CH = }\mathop {\rm N}\limits^ + {\rm H}_{\rm 2} $\end{document} isomer occurs at higher electron energies and is rationalized by means of a potential energy surface constructed from energetic data. 相似文献
35.
Syed Laik Ali 《Analytical and bioanalytical chemistry》1972,262(4):278-282
The different aspects of Vitamin D3 determination and the data reported in the literature are discussed. The spectrophotometric determination of Vitamin D3 in cod-liver oil is carried out after the alkaline saponification, extraction of unsaponified parts, precipitation of accompanying sterols and the column- and thin-layer chromatographic purification and separation of vitamin D3 on 40 cm plates from other vitamins. The dyestuff α-naphtholbenzein is suited well as standard substance for the better location and identification of vitamin D3 zone on the thin-layer plate. The results obtained from the chemical method were checked through the simultaneous biological determination. 相似文献
36.
Bao‐Shiang Lee Sangeeth Krishnanchettiar Syed Salman Lateef Nabila Salman Lateef Shalini Gupta 《中国化学会会志》2006,53(3):745-750
Avidin functional affinity electrophoresis (AFAEP) is substituted for an avidin affinity column (AAC) to capture biotinylated peptides in the Isotope‐Coded Affinity Tagging (ICAT) technique which is a valuable tool in quantitative proteomics. In this new technique, the AFAEP‐captured ICAT‐labeled biotinylated peptides are extracted with the biotin tag intact from the polyacrylamide gel piece with aqueous 95% formamide (pH 8.2) at 65 °C for 20 min, and then detected by a matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometer. Bovine serum albumin (BSA) and the 12C‐ and 13C‐ICAT reagents are used to test this AFAEP‐ICAT technique. The results show that both AFAEP and AAC methods provide quantitative information of the relative amounts of 12C‐ and 13C‐ICAT‐labeled biotinylated tryptic peptides of BSA in a sample. Compared with AAC, the AFAEP is cheaper to perform, more stringent in capturing the biotinylated peptides, and capable of simultaneously processing multiple samples. 相似文献
37.
The bis-phenyltin-substituted, lone-pair-containing tungstoarsenate [(C(6)H(5)Sn)(2)As(2)W(19)O(67)(H(2)O)](8)(-) (1) has been synthesized and characterized by multinuclear NMR, IR, and elemental analysis. Single-crystal X-ray analysis was carried out on (NH(4))(7)Na[(C(6)H(5)Sn)(2)As(2)W(19)O(67)(H(2)O)].17.5H(2)O (NH(4)(-1), which crystallizes in the monoclinic system, space group P2(1)/c, with a = 18.3127(17) A, b = 24.403(2) A, c = 22.965(2) A, beta = 106.223(2) degrees, and Z = 4. Polyanion 1 consists of two B-alpha-(As(III)W(9)O(33)) Keggin moieties linked via a WO(H(2)O) fragment and two SnC(6)H(5) groups leading to a sandwich-type structure with nominal C(2)(v) symmetry. Polyanion 1 is stable in solution as indicated by the expected 6-line pattern (4:4:4:4:2:1) in (183)W NMR and the expected (119)Sn, (13)C, and (1)H NMR spectra. Synthesis of 1 was accomplished by reaction of C(6)H(5)SnCl(3) and K(14)[As(2)W(19)O(67)(H(2)O)] in a 2:1 molar ratio in aqueous acidic medium (pH 2). In the solid-state structure of NH(4)(-1, neighboring polyanions are weakly bound via W-O-Na bonds leading to chains which interact with each other via the phenyl rings resulting in a 2-D assembly. 相似文献
38.
The importance of adsorption induced convection in the macropores of a bidisperse adsorbent particle is studied for a step change in mole fraction or total pressure at the surface of the particle. Material balance equations for a binary gas mixture are written for both the macropores and the macropores with allowance for convection in the macropores, which is described by Darcy's law. The coupled set o1' partial differential equations is solved by orthogonal collocation. The enhancement in mass transfer as a result of convection is assessed by comparing the fractional uptake curves obtained with and without allowance for convection. Both equilibrium-based and kinetic-based separation processes are considered. The effect of the presence of convection in determining the controlling diffusional resistance (macropore or micropore) is also examined. Due to inclusion of convection no single non-dimensional group alone can determine the relative importance of macropore and micropore resistances. Results show that convection can significantly affect the performance of an equilibrium-based macropore diffusion controlled process and that the enhancement in mass transfer is more for a particle with a high value of Darcy permeability. 相似文献
39.
Hashem EY Abu-Bakr MS Hussain SM 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2003,59(4):761-769
The solution properties of nickel complex with 4-(2'-benzo-thiazolylazo) salicylic acid (BTAS) have been studied by zero-order absorption spectrophotometry in 40% (v/v) ethanol at 20 degrees C and an ionic strength of 0.1 mol dm(-3) (KNO(3)). The equilibria that exist in solution were established and the basic characteristics of complexes formed were determined. A new direct spectrophotometric method for the determination of trace amounts of the nickel is proposed based on the formation of the Ni (BTAS) complex at pH 7.0. The absorption maximum, molar absorbtivity, and Sandell's sensitivity of 1:1 (M:L) complex are 525 nm, 0.6 x 10(4) l mol(-1) cm(-1) and 2.824 x 10(-9) microg cm(-2), respectively. The use of first-derivative spectrophotometry eliminates the interference of iron and enables the simultaneous determination of nickel and iron using BTAS. Quantitative determination of Ni(II) and Fe(III) is possible in the range (0.59-7.08) and (2.1-8.4) microg ml(-1), respectively with a relative standard deviation of 0.5%. The proposed method has been successfully applied to the simultaneous spectrophotometric determination of nickel and iron in steel alloys and aluminum alloys. 相似文献
40.
In this work 3-chloro-2-chlorocarbonylbenzo[b]thiophene (1) was prepared from cinnamic acid and then converted into the acid hydrazide 2. The azomethines 3a-e were prepared from the corresponding aryl aldehydes and the acid hydrazide 2. Treatment of compound 2 with formic acid gave the N-formyl acid hydrazide 4, which upon refluxing with phosphorous pentoxide or phosphorous pentasulphide in xylene yielded the corresponding 2- (3-chloro-1-benzothien-2-yl)-1,3,4-oxadiazole (5) and 2-(3-chloro-1-benzo-thien-2-yl)-1,3,4- thiadiazole (6). Reaction of 1-thiosemicarbazide 7 with NaOH leads to ring closure giving 5- (3-chloro-1-benzothien-2- yl)-4H-triazole-3-thiol (8) which is converted into a number of derivatives 9-12 Reaction of 2 with phenyl isothiocyanate and NaOH afforded 5-(3-chloro- 1-benzothien-2-yl)-4-(phenyl)-4H-1,2,4-triazole-3-thiol (14). 相似文献