全文获取类型
收费全文 | 2330篇 |
免费 | 30篇 |
国内免费 | 16篇 |
专业分类
化学 | 1375篇 |
晶体学 | 15篇 |
力学 | 39篇 |
数学 | 484篇 |
物理学 | 463篇 |
出版年
2022年 | 20篇 |
2021年 | 23篇 |
2020年 | 27篇 |
2019年 | 18篇 |
2018年 | 19篇 |
2017年 | 19篇 |
2016年 | 40篇 |
2015年 | 31篇 |
2014年 | 39篇 |
2013年 | 104篇 |
2012年 | 82篇 |
2011年 | 90篇 |
2010年 | 55篇 |
2009年 | 46篇 |
2008年 | 85篇 |
2007年 | 91篇 |
2006年 | 99篇 |
2005年 | 93篇 |
2004年 | 94篇 |
2003年 | 72篇 |
2002年 | 56篇 |
2001年 | 33篇 |
2000年 | 26篇 |
1998年 | 19篇 |
1997年 | 20篇 |
1996年 | 44篇 |
1995年 | 34篇 |
1994年 | 24篇 |
1993年 | 27篇 |
1992年 | 33篇 |
1991年 | 24篇 |
1990年 | 18篇 |
1989年 | 19篇 |
1987年 | 18篇 |
1986年 | 22篇 |
1985年 | 30篇 |
1984年 | 33篇 |
1983年 | 17篇 |
1982年 | 38篇 |
1981年 | 28篇 |
1980年 | 42篇 |
1979年 | 37篇 |
1978年 | 32篇 |
1977年 | 41篇 |
1976年 | 47篇 |
1975年 | 42篇 |
1974年 | 35篇 |
1973年 | 26篇 |
1972年 | 17篇 |
1971年 | 21篇 |
排序方式: 共有2376条查询结果,搜索用时 15 毫秒
101.
Francis M. Wampler Arthur T. Blades Paul Kebarle 《Journal of the American Society for Mass Spectrometry》1993,4(4):289-295
The total current and selected ion currents from the electrospray ionization (ES1) of 10?5 M solutions of cocaine hydrochloride and deoxycytidine monophosphate (dCMP) monosodium salt in methanol and water solvents were compared in positive and negative ion modes, respectively, without and with SF6, gas as a discharge suppressant. The ESI onset voltages (Von), were the same for the positive and negative ion modes. The Von, for methanol was much lower than that for water and in agreement with the equation of D. P. H. Smith, who attributes the difference to the higher surface tension of water. The onset of electric discharge (Vdis) without SF6, occurred at lower capillary voltages for the negative relative to the positive ion mode for methanol; but Vdis is much higher than Von for methanol, and discharges do not interfere with ESI operation. For water, Von ≈ Vdis in the absence of SF6, in the negative ion mode, and ESI operation is impossible without SF6, discharge suppression. The discharge problem in the positive ion mode is less severe, but SF6, is still very useful. A dynamic range of 10 ?7–10?5 M was obtained by selected ion monitoring of [dCMP - H]? at 4.5 and 20 μL/min. flows. Subpicomole detection limits for the nucleotide salt were obtained under these conditions. 相似文献
102.
Michael G. Ikonomou Arthur T. Blades Paul Kebarle 《Journal of the American Society for Mass Spectrometry》1991,2(6):497-505
An equation by D. P. H. Smith predicts the capillary voltage required for the onset of electrospray (ES). For different solvents the voltage increases with the square root of the surface tension. Water requires a potential that is 1.8 times higher than that for methanol. This is verified experimentally. The higher potential required for water leads to ES in the presence of corona electric discharge. For low total ES plus corona currents, the electrosprayed analyte ion intensity is not adversely affected by the presence of discharge. At high total currents, there is a large decrease of analyte sensitivity. The sensitivity decrease is probably due to adverse space charge effect at high currents. The discharge can be suppressed by adding sulfur hexafluoride to the ambient gas. Both sensitivity and signal stability are improved. However, the sensitivity still remains lower by a factor of ≈ 4 relative to that observed with methanol. This is attributed to lower efficiency of gas-phase ion formation from charged water, relative to methanol, droplets. 相似文献
103.
Parthey CG Matveev A Alnis J Bernhardt B Beyer A Holzwarth R Maistrou A Pohl R Predehl K Udem T Wilken T Kolachevsky N Abgrall M Rovera D Salomon C Laurent P Hänsch TW 《Physical review letters》2011,107(20):203001
We have measured the 1S-2S transition frequency in atomic hydrogen via two-photon spectroscopy on a 5.8 K atomic beam. We obtain f(1S-2S) = 2,466,061,413,187,035 (10) Hz for the hyperfine centroid, in agreement with, but 3.3 times better than the previous result [M. Fischer et al., Phys. Rev. Lett. 92, 230802 (2004)]. The improvement to a fractional frequency uncertainty of 4.2 × 10(-15) arises mainly from an improved stability of the spectroscopy laser, and a better determination of the main systematic uncertainties, namely, the second order Doppler and ac and dc Stark shifts. The probe laser frequency was phase coherently linked to the mobile cesium fountain clock FOM via a frequency comb. 相似文献
104.
Gerald D Fong Robert L Kuczkowski Arthur J Ashe 《Journal of Molecular Spectroscopy》1978,70(2):197-208
The microwave spectrum of 121-SbC5H5, 123-SbC5H5, β-dideutero 121-SbC5H3D2 and 123-SbC5H3D2 has been assigned in the region 26.5–40.0 GHz. The respective rotational constants and uncertainties are: A = 4512.69 ± 0.42, B = 1738.00 ± 0.01, C = 1254.51 ± 0.01; A = 4512.84 ± 0.30, B = 1729.80 ± 0.01, C = 1250.22 ± 0.01; A = 4176.18 ± 0.33, B = 1660.94 ± 0.01, C = 1188.15 ± 0.01; A = 4176.60 ± 0.61, B = 1652.94 ± 0.03, C = 1184.03 ± 0.03 (in MHz units). The structure is found to be planar, C2v in symmetry. The and ∠CSbC = 92.9° ± 1.0°. The nuclear quadrupole coupling constants for the 121 and 123 antimony isotopes are χaa = 456.4 ± 4.1 MHz, η = 0.396 ± 0.008, and χaa = 583.00 ± 5.3 MHz, η = 0.399 ± 0.008, respectively. Several alternate techniques using the coupling constants as data support a σ-donating property for antimony. 相似文献
105.
An isomorphism is established between eertain compact and noncompact formulations of Abelian gauge theory on a lattice. For weak coupling, the mass gap predicted by the Higgs mechanism is then established. 相似文献
106.
We prove that for any of a wide class of elliptic surfaces X defined over a number field k, if there is an algebraic point on X that lies on only finitely many rational curves, then there is an algebraic point on X that lies on no rational curves. In particular, our theorem applies to a large class of elliptic K3 surfaces, which relates to a question posed by Bogomolov in 1981. 相似文献
107.
The effects of an externally applied magnetic field on the Anderson localization of electromagnetic waves in an alternating layered system of vacuum and semiconducting slabs are studied. Specifically, a waveguide formed from perfectly conducting parallel plates which contain between them an array of vacuum and n-type semiconductor slabs is examined in the presence of an external static magnetic field applied parallel to both the plates and the slab surfaces. The widths of the slabs in the array are random but with a randomness such that the array of slabs is almost periodic, and we study only electromagnetic modes which propagate perpendicular to the slab surfaces. The localization length is obtained by studying the reflection and transmission properties of a finite array of slabs in the limit that it becomes semi-infinite. Two types of system are treated: (i) a reciprocal system which exhibits a localization length that does not depend on the sign of the applied magnetic field, and (ii) a non-reciprocal system which exhibits a localization length that depends on the sign of the applied magnetic field. 相似文献
108.
Intensification of oxidation capacity using chloroalkanes as additives in hydrodynamic and acoustic cavitation reactors 总被引:1,自引:0,他引:1
Chakinala AG Gogate PR Chand R Bremner DH Molina R Burgess AE 《Ultrasonics sonochemistry》2008,15(3):164-170
The effect of the presence and absence of the chloroalkanes, dichloromethane (CH(2)Cl(2)), chloroform (CHCl(3)) and carbon tetrachloride (CCl(4)) on the extent of oxidation of aqueous I(-) to I(3)(-) has been investigated in (a) a liquid whistle reactor (LWR) generating hydrodynamic cavitation and (b) an ultrasonic probe, which produces acoustic cavitation. The aim has been to examine the intensification achieved in the extent of oxidation due to the generation of additional free radicals/oxidants in the reactor as a result of the presence of chloroalkanes. It has been observed that the extent of increase in the oxidation reaction is strongly dependent on the applied pressure in the case of the LWR. Also, higher volumes of the chloroalkanes favour the intensification and the order of effectiveness is CCl(4)>CHCl(3)>CH(2)Cl(2). However, the results with the ultrasonic probe suggest that an optimum concentration of CH(2)Cl(2) or CHCl(3) exists beyond which there is little increase in the extent of observed intensification. For CCl(4), however, no such optimum concentration was observed and the extent of increase in the rates of oxidation reaction rose with the amount of CCl(4) added. Stage wise addition of the chloroalkanes was found to give marginally better results in the case of the ultrasonic probe as compared to bulk addition at the start of the run. Although CCl(4) is the most effective, its toxicity and carcinogenicity may mean that CH(2)Cl(2) and CHCl(3) offer a safer viable alternative and the present work should be useful in establishing the amount of chloroalkanes required for obtaining a suitable degree of intensification. 相似文献
109.
Arthur H. G. David Pablo García-Cerezo Dr. Araceli G. Campaña Prof. Francisco Santoyo-González Dr. Victor Blanco 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(24):6170-6179
We report the application of the click Michael-type addition reaction to vinyl sulfone or vinyl sulfonate groups in the synthesis of rotaxanes through the threading-and-capping method. This methodology has proven to be efficient and versatile as it allowed the preparation of rotaxanes using template approaches based on different noncovalent interactions (i.e., donor-acceptor π–π interactions or hydrogen bonding) in yields of generally 60–80 % and up to 91 % aided by the mild conditions required (room temperature or 0 °C and a mild base such as Et3N or 4-(N,N-dimethylamino)pyridine (DMAP)). Furthermore, the use of vinyl sulfonate moieties, which are suitable motifs for coupling-and-decoupling (CAD) chemistry, implies another advantage because it allows the controlled chemical disassembly of the rotaxanes into their components through nucleophilic substitution of the sulfonates resulting from the capping step with a thiol under mild conditions (Cs2CO3 and room temperature). 相似文献
110.
Grigor’ev Arthur A. Kayukov Yakov S. Nikiforova Anastasiya L. Karpov Sergey V. Shchegravina Ekaterina S. Kayukova Olga V. Tafeenko Victor A. 《Chemistry of Heterocyclic Compounds》2019,55(2):167-171
Chemistry of Heterocyclic Compounds - 4-Acyl-2-amino-6-chloropyridine-3,5-dicarbonitriles underwent heterocyclization in the presence of ammonia in aqueous dioxane medium, involving the... 相似文献