全文获取类型
收费全文 | 33126篇 |
免费 | 3840篇 |
国内免费 | 2954篇 |
专业分类
化学 | 16077篇 |
晶体学 | 276篇 |
力学 | 1354篇 |
综合类 | 187篇 |
数学 | 2296篇 |
物理学 | 8474篇 |
综合类 | 11256篇 |
出版年
2024年 | 109篇 |
2023年 | 534篇 |
2022年 | 902篇 |
2021年 | 1034篇 |
2020年 | 988篇 |
2019年 | 919篇 |
2018年 | 810篇 |
2017年 | 850篇 |
2016年 | 1146篇 |
2015年 | 1292篇 |
2014年 | 1520篇 |
2013年 | 1984篇 |
2012年 | 2229篇 |
2011年 | 2369篇 |
2010年 | 1638篇 |
2009年 | 1662篇 |
2008年 | 1915篇 |
2007年 | 1796篇 |
2006年 | 1608篇 |
2005年 | 1321篇 |
2004年 | 1074篇 |
2003年 | 938篇 |
2002年 | 919篇 |
2001年 | 750篇 |
2000年 | 719篇 |
1999年 | 1031篇 |
1998年 | 916篇 |
1997年 | 894篇 |
1996年 | 979篇 |
1995年 | 810篇 |
1994年 | 821篇 |
1993年 | 566篇 |
1992年 | 542篇 |
1991年 | 510篇 |
1990年 | 384篇 |
1989年 | 349篇 |
1988年 | 313篇 |
1987年 | 217篇 |
1986年 | 163篇 |
1985年 | 97篇 |
1984年 | 66篇 |
1983年 | 51篇 |
1982年 | 40篇 |
1981年 | 28篇 |
1980年 | 32篇 |
1979年 | 19篇 |
1978年 | 10篇 |
1977年 | 8篇 |
1975年 | 7篇 |
1973年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
271.
A Taylor dispersion tube has been used to measure mutual diffusion in aqueous solutions of glycine hydrochloride at 25°C and concentrations from 0.0005 to 0.5 M. Analysis of the dispersion profiles shows that the diffusion of glycine hydrochloride (GlyHCl) produces a subtantial additional flow of hydrochloric acid that is liberated by the dissociation: GlyH+ + Cl- Gly + H+ + Cl-. Diffusion in this system is, therefore, a ternary process described by the equations J
1(GlyHCl) = – D
11C
1 – D
12C
2 and J
2(HCl) = –D
21C
1 – D
22C
2 for the coupled fluxes of total glycine hydrochloride (1) and hydrochloric acid (2) components. The ratio D
21/D
11 of measured diffusion coefficients indicates that up to two moles of HCl are cotransported per mole of GlyHCl. Although protonated glycine diffuses with relatively mobile Cl– counterions, the main diffusion coefficient of glycine hydrochloride, D
11, is lower than or nearly identical to the diffusion coefficient of aqueous glycine. A model for the diffusion of protonated solutes is developed to interpret this result and the large coupled flows of HCl. Diffusion coefficients are also reported for the aqueous hydrochlorides of 3- and 4-aminobenzoic acids. 相似文献
272.
Jinzhang Gao Yongjun Liu Wu Yang Lumei Pu Jie Yu Quanfang Lu 《Central European Journal of Chemistry》2005,3(3):377-386
A plasma induced degradation process has been studied to treat 4-nitrotoluene (4-NT) present as an aqueous pollutant. The
plasma was locally generated from a glow discharge around a tip of a platinum anode in an electrolytic solution. The influence
of initial pH and Fe2+ on the degradation was examined. Major intermediates resulting from the degradation process were identified. Amongst the
aromatic intermediates, p-hydroxybenzoic acid was the predominant degradation product. The formation of oxalic acid, malic
acid was also observed. The final products of degradation were NH
4
+
, NO
3
−
and CO2. Based on the analysis of intermediates and the kinetic considerations, the degradation was shown to follow a pseudo-first
order reaction hence, a possible reaction pathway was proposed. 相似文献
273.
测定了Pt-Sn型催化剂浸渍状态下的Sn-119、Pt-195的多核核磁共振。当SnCl2/DCl溶液体系中加入H2PtCl6以后,出现了Sn(Ⅳ)和另外一种Sn(Ⅱ)的构型,Sn-119峰向高场位移,说明部分Sn(Ⅱ)被氧化成Sn(Ⅳ),H2PtCl6的量对这种氧化性影响较小。而H2PtCl6/D2O溶液体系中加入SnCl2以后部分Pt(Ⅳ)被还原成Pt(Ⅱ),随着SnCl2量的增加,Pt(Ⅱ) 相似文献
274.
Z. P. Lu L. Stachowicz P. Kong J. Heberlein E. Pfender 《Plasma Chemistry and Plasma Processing》1991,11(3):387-394
Diamond crystals and films have been success full y synthesized by DC thermal plasma jet CVD at a pressure of I atrn. A novel triple torch plasma reactor has been used to generate a convergent plasma volume to entrain the participating gases. Three coalescing plasma jets produces! by this reactor direct the dissociated and ionized gaseous species onto ( 100) silicon wafer substrates where the diamond grows. In a typical 10-min run, depending on the method of .substrate preparation, either microcrystals with sizes up to 8 m or continuous films with thicknesses of 1–2 m have been obtained. X-ray diffraction, scanning electron microscopy, and Raman spectroscopy have been used for the characterization of the crystals and of the films. 相似文献
275.
Lu Y Xiong H Jiang X Xia Y Prentiss M Whitesides GM 《Journal of the American Chemical Society》2003,125(42):12724-12725
Asymmetric dimers consisting of gold microcrystals and spherical silica colloids have been fabricated by depositing thin films of gold onto the spherical colloids to form half-shells, followed by annealing at elevated temperatures. The capability and feasibility of this procedure have been demonstrated with silica and titania beads of 0.2-2 mum in diameter and gamma-Fe2O3/polystyrene@SiO2 core-shell particles 0.5 mum in size. The dimensions of gold microcrystals could be conveniently varied in the range of 100-650 nm by controlling the thickness of gold films and/or the diameter of the spherical colloids. This method provides another route to asymmetric dimers made of colloidal particles that could be different in size, chemical composition, surface functionality, density or sign of surface charge, bulk property, or a combination of these properties. 相似文献
276.
Maximum spectrum of continuous wavelet transform and its application in resolving an overlapped signal 总被引:2,自引:0,他引:2
Xiaoquan L Hongde L Zhonghua X Qiang Z 《Journal of chemical information and computer sciences》2004,44(4):1228-1237
To estimate the number of peaks and to find the individual peak positions in an overlapped signal, a new method called maximum spectrum of continuous wavelet transform (MSCWT) was developed by extracting the maximum coefficients of continuous wavelet transform (CWT). The peak position in MSCWT was the same as that in its original signal. In this process, CWT was performed not on a single dilation but on an appreciation dilation range. To obtain such a range, a new criterion was introduced to choose a center dilation, which was used to form the dilation range. If Cdilation denoted the center dilation, the proper dilation range was [Cdilation -6 +/- 2, Cdilation +1 +/- 1]. The Mexican Hat function was an analytical wavelet. Utilizing the information of the peak number and the position detected by MSCWT, a fitting route was performed to recover the original signal. One simulated and four true overlapped signals, including high performance liquid chromatography (HPLC), ultraviolet-visible (UV) spectrum, and differential pulse voltammetric (DPV), were processed, and the results indicated that MSCWT could detect an overlapped peak number and position, and the curve fitting based on information of MSCWT had a higher accuracy. The proposed method was an efficient one in resolving different types of overlapped signals. 相似文献
277.
Liu H Hu Y Yang S Guo W Lu X Zhao L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(21):6392-6406
We report herein a comprehensive study of photoinduced reactions in complexes of Mg+ with primary (n-propyl- and isopropylamine) and secondary amines (dipropyl- and diisopropylamine) in the spectral range of 230-440 nm. Similar to the methyl- and ethylamine complexes studied previously, N-H bond activation of these complexes is very unfavorable. Instead, the C(alpha)-C, C-N, and C(alpha)-H bond-cleavage photoproducts are observed after photoexcitation of the Mg+ complexes (3(2)P<--3(2)S). For Mg+(primary amine) complexes, for example, Mg+-NH2CH2CH2CH3, and Mg+-NH2CH(CH3)2, the photoproducts resulting from C(alpha)--C rupture prevail after P(z) and charge-transfer excitations, whereas the Mg+ photofragment is predominant upon P(x,y) excitation. However, with further N-alkyl substitution, as in Mg+(secondary amine) complexes, for example, Mg+-NH(CH2CH2CH3)2 and Mg+-NH[CH(CH3)2]2, a novel intracomplex C-C coupling photoreaction dominates on P(x,y) excitation of Mg+, which is believed to arise from Mg+* insertion into the C-N bond. With P(z) and charge-transfer excitation, the Mg-R elimination photoproducts, arising from C(alpha)-C bond cleavage, predominate. The energetics and possible mechanisms of the intracomplex photoreactions are analyzed in detail with the help of extensive quantum mechanics calculations. 相似文献
278.
279.
An efficient and a quick microwave‐assisted synthesis of benzimidazoles and trisubstituted imidazoles was developed. Three benzimidazoles were obtained as a result of the condensation of 1,2‐phenylenediamine with carboxylic acids and acetoacetic ester without catalyst. A series of trisubstituted imidazoles were synthesized by condensation of benzil, aromatic aldehyde and ammonium acetate in the presence of glacial acetic acid. 相似文献
280.
Shen YH Li SH Li RT Han QB Zhao QS Liang L Sun HD Lu Y Cao P Zheng QT 《Organic letters》2004,6(10):1593-1595
Both coriatone (1). a novel highly oxygenated picrotoxane-type sesquiterpene, and corianlactone (2). with an unprecedented sesquiterpene basic skeleton, named coriane, were isolated from Coriaria nepalensis Wall. The structures of 1 and 2 were determined by analysis of their two-dimensional NMR data, and the structure of 2 was confirmed by X-ray analysis. Compounds 1 and 2 showed no remarkable inhibitory activity toward K(562) cells. They are cytotoxic with IC(50) > 50 microg/mL (cis-platinim: IC(50) = 0.49 microg/mL). 相似文献