全文获取类型
收费全文 | 3736篇 |
免费 | 61篇 |
国内免费 | 17篇 |
专业分类
化学 | 2300篇 |
晶体学 | 26篇 |
力学 | 75篇 |
数学 | 599篇 |
物理学 | 814篇 |
出版年
2022年 | 30篇 |
2021年 | 37篇 |
2020年 | 58篇 |
2019年 | 41篇 |
2018年 | 25篇 |
2017年 | 22篇 |
2016年 | 45篇 |
2015年 | 51篇 |
2014年 | 47篇 |
2013年 | 164篇 |
2012年 | 162篇 |
2011年 | 178篇 |
2010年 | 99篇 |
2009年 | 87篇 |
2008年 | 153篇 |
2007年 | 189篇 |
2006年 | 177篇 |
2005年 | 173篇 |
2004年 | 168篇 |
2003年 | 139篇 |
2002年 | 124篇 |
2001年 | 84篇 |
2000年 | 96篇 |
1999年 | 51篇 |
1998年 | 65篇 |
1997年 | 53篇 |
1996年 | 62篇 |
1995年 | 62篇 |
1994年 | 50篇 |
1993年 | 70篇 |
1992年 | 43篇 |
1991年 | 40篇 |
1990年 | 44篇 |
1989年 | 45篇 |
1988年 | 37篇 |
1987年 | 42篇 |
1986年 | 41篇 |
1985年 | 58篇 |
1984年 | 47篇 |
1983年 | 38篇 |
1982年 | 34篇 |
1981年 | 37篇 |
1980年 | 36篇 |
1979年 | 26篇 |
1978年 | 30篇 |
1977年 | 39篇 |
1976年 | 45篇 |
1975年 | 49篇 |
1974年 | 41篇 |
1973年 | 45篇 |
排序方式: 共有3814条查询结果,搜索用时 15 毫秒
91.
Blake AJ Bencini A Caltagirone C De Filippo G Dolci LS Garau A Isaia F Lippolis V Mariani P Prodi L Montalti M Zaccheroni N Wilson C 《Dalton transactions (Cambridge, England : 2003)》2004,(17):2771-2779
The coordination chemistry of the new pyridine-based, N2S2-donating 12-membered macrocycle 2,8-dithia-5-aza-2,6-pyridinophane (L1) towards Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II) has been investigated both in aqueous solution and in the solid state. The protonation constants for L1 and stability constants with the aforementioned metal ions have been determined potentiometrically and compared with those of ligand L2, which contains a N-aminopropyl side arm. The measured values show that Hg(II) in water has the highest affinity for both ligands followed by Cu(II), Cd(II), Pb(II), and Zn(II). For each metal ion considered, 1:1 complexes with L1 have also been isolated in the solid state, those of Cu(II) and Zn(II) having also been characterised by X-ray crystallography. In both complexes L1 adopts a folded conformation and the coordination environments around the two metal centres are very similar: four positions of a distorted octahedral coordination sphere are occupied by the donor atoms of the macrocyclic ligand, and the two mutually cis-positions unoccupied by L1 accommodate monodentate NO3- ligands. The macrocycle L1 has then been functionalised with different fluorogenic subunits. In particular, the N-dansylamidopropyl (L3), N-(9-anthracenyl)methyl (L4), and N-(8-hydroxy-2-quinolinyl)methyl (L5) pendant arm derivatives of L1 have been synthesised and their optical response to the above mentioned metal ions investigated in MeCN/H2O (4:1 v/v) solutions. 相似文献
92.
A.A. Baker J.B. Headridge S.R. Keown G.D. Long P.A. Vergnano M.I. Wilson 《Analytica chimica acta》1979
The extraction method with hydrogen, hitherto used to determine mobile nitrogen in steels over the temperature range 350–450°C, has been employed at higher temperatures to determine nitrogen bound as aluminium nitride, or as titanium nitride or carbonitride. In steels containing only silicon and titanium as deoxidizers, the nitrogen remaining after passage of hydrogen at 600 or 750°C is present as titanium nitride or carbonitride and can be determined by difference. In steels containing only silicon and aluminium as deoxidizers, the nitrogen remaining after passage of hydrogen at 600°C is present as aluminium nitride and can also be determined by difference. This was verified by determining the aluminium nitride indirectly. The nitrogen released from both the aluminium and titanium steels in hydrogen at 600°C probably results from dissociation of submicroscopic particles of manganese silicon nitride. 相似文献
93.
A method for the direct gravimetric determination of osmium with 1:2:3-benzotriazole in acetic acid-sodium acetate buffer is presented. The method is accurate and reproducible, and the conditions used in the determination are not critical. The precipitate is a stoichiometric compound which is stable from room temperature up to 200°. It appears that 1:2:3-benzotriazole is probably the first organic reagent to be used successfully in the direct gravimetric determination of osmium. 相似文献
94.
Wilson Cunico Claudia R. B. Gomes Solange M. S. V. Wardell John N. Low Christopher Glidewell 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(7):o411-o414
rac‐2‐Isopropyl‐3‐(2‐nitrobenzyl)‐1,3‐thiadiazolin‐4‐one, C13H16N2O3S, is a rare example of a racemate crystallizing in the space group P212121, with one molecule each of S and R configurations, whose conformations are almost mirror images, within the asymmetric unit. The molecules of S configuration are linked by two C—H...O hydrogen bonds into a three‐dimensional framework, and the molecules of R configuration are linked by two further C—H...O hydrogen bonds into a different type of three‐dimensional framework; the two frameworks are linked by a fifth C—H...O hydrogen bond. 相似文献
95.
Sources of systematic errors in analytical results are discussed, and suggestions are made for the investigation and reporting of such errors when characterizing the performances of analytical methods. The four types of error considered arise from: (1) blank determinations, (2) calibration, (3) differences in the efficiencies with which different forms of the determinand are measured, and (4) interferences. The comparison of results with accepted values of standard samples or with the results obtained by standard methods is also discussed. 相似文献
96.
Michels JJ O'Connell MJ Taylor PN Wilson JS Cacialli F Anderson HL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(24):6167-6176
A series of conjugated polyrotaxane insulated molecular wires are synthesised by aqueous Suzuki polymerisation, using hydrophobic binding to promote threading of the cyclodextrin units. These polyrotaxanes have conjugated polymer cores based on poly(para-phenylene), polyfluorene, and poly(diphenylene-vinylene), threaded through 0.9-1.6 cyclodextrins per repeat unit. Bulky naphthalene-3,6-disulfonate endgroups prevent the macrocycles from slipping off the conjugated polymer chains. Dialysis experiments show that the cyclodextrins become unthreaded only if smaller stoppers are used. MALDI TOF mass spectra detect oligomers with up to ten threaded cyclodextrins, and reveal the presence of some defects that result for oxidative homo-coupling of boronic acids. Weight-average molecular weights were determined by analytical ultracentrifugation, demonstrating that step-growth polymerisation is efficient enough to achieve degrees of polymerisation up to approximately 20 repeat units (84 para-phenylenes). The fluorescence spectra of these polyrotaxanes indicate that the presence of the threaded cyclodextrin macrocycles reduces the flexibility of the conjugated polymer pi-systems. Both the solution and the solid-state photoluminescence quantum yields are enhanced upon threading of the conjugated polyaromatic cores through alpha- or beta-cyclodextrins, and the emission spectra of the polyrotaxanes are blue-shifted compared to the corresponding unthreaded polymers. The greater weight of the 0-0 transition in the emission spectra, as well as the smaller Stokes shift, indicate that the polyrotaxanes are more rigid than the unthreaded polymers. 相似文献
97.
The design and operation of an automatic controlled-potential coulometer is described. It was primarily designed for use with mg quantities of uranium, neptunium and plutonium but can in principle be used on any element possessing more than one valency state in solution. It is capable of an accuracy and precision of ±0.25% and can analyse up to 20 samples on a set programme without operator attention. 相似文献
98.
Roland A. Bougon Karl O. Christe William W. Wilson 《Journal of fluorine chemistry》1985,30(2):237-239
Evidence is presented for the existence of (O2+)2MF62?(M=Ni,Mn) salts. These salts are marginally stable up to about 10°C and are characterized by an OO stretching frequency of about 1805 cm?1. 相似文献
99.
Molecular mechanics calculations indicate that the deformed chair and twisted-boat conformations are similar in energy for a 4,4-dimethyl-3-keto steroid. Earlier dipole moment work on such compounds is discussed. The crystal structure of 4,4-dimethylandrostan-3-on-17β-yl benzoate has been determined. The crystals are orthorhombic, P212121, a = 17.096 (2), b = 22.136 (e), c = 6.217 (1) A. The structure was solved by direct methods and refined by least squares to R ? 0.039, RXXX = 0.038, based on 2168 observed reflections. Ring A is shown to exist in a chair form, deformed as indicated by the calculations. 相似文献
100.
Milligan DB Freeman CG Maclagan RG McEwan MJ Wilson PF Anicich VG 《Journal of the American Society for Mass Spectrometry》2001,12(5):557-564
The ion-molecule reactivity of the products formed in the association reactions of HCNH+ with C2H2 (C3H4N+) and C2H4 (C3H6N+) has been investigated to provide information on the structures of the adducts thus formed. The C3H4N+ and C3H6N+ adducts were formed in the reaction flow tube of a flowing afterglow sourced-selected ion flow tube (FA-SIFT) and their reactivity with a neutral molecular "probe" examined. The reactivity of possible known structural isomers for the C3H4N+ and C3H6N+ ions was investigated in both the FA-SIFT and an ion cyclotron resonance spectrometer (ICR). Ab initio investigations of the potential energy surfaces for both structures at the G2(MP2) level have also been performed and structures corresponding to local minima on both surfaces have been identified and evaluated. The results of these experimental and theoretical studies show that at room temperature, the C3H4N+ adduct ion contains two isomers; a less reactive one that is likely to be a four-membered cyclic covalent isomer (approximately 70%) and a faster reacting component that is probably an electrostatic complex (approximately 30%). The C3H6N+ adduct ion formed from HCNH+ + C2H4 at room temperature is a single isomer that is likely to be the four-membered covalently bound cyclic CH2CH2CHNH+ species. 相似文献