全文获取类型
收费全文 | 28300篇 |
免费 | 806篇 |
国内免费 | 230篇 |
专业分类
化学 | 19282篇 |
晶体学 | 128篇 |
力学 | 648篇 |
综合类 | 1篇 |
数学 | 5387篇 |
物理学 | 3890篇 |
出版年
2022年 | 183篇 |
2021年 | 276篇 |
2020年 | 347篇 |
2019年 | 313篇 |
2018年 | 276篇 |
2017年 | 292篇 |
2016年 | 600篇 |
2015年 | 621篇 |
2014年 | 659篇 |
2013年 | 1406篇 |
2012年 | 1407篇 |
2011年 | 1706篇 |
2010年 | 952篇 |
2009年 | 814篇 |
2008年 | 1464篇 |
2007年 | 1466篇 |
2006年 | 1553篇 |
2005年 | 1394篇 |
2004年 | 1327篇 |
2003年 | 1098篇 |
2002年 | 1046篇 |
2001年 | 453篇 |
2000年 | 407篇 |
1999年 | 395篇 |
1998年 | 386篇 |
1997年 | 432篇 |
1996年 | 398篇 |
1995年 | 360篇 |
1994年 | 391篇 |
1993年 | 345篇 |
1992年 | 320篇 |
1991年 | 320篇 |
1990年 | 278篇 |
1989年 | 280篇 |
1988年 | 260篇 |
1987年 | 218篇 |
1986年 | 245篇 |
1985年 | 361篇 |
1984年 | 370篇 |
1983年 | 315篇 |
1982年 | 348篇 |
1981年 | 316篇 |
1980年 | 338篇 |
1979年 | 271篇 |
1978年 | 300篇 |
1977年 | 279篇 |
1976年 | 223篇 |
1975年 | 190篇 |
1974年 | 195篇 |
1973年 | 165篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
951.
Comprehensive two-dimensional (2D) chromatographic techniques can be considered innovative methods, only quite recently developed. Since their introduction to the chromatographic community, these techniques have been used in several fields and have gained an excellent reputation as valuable and powerful analytical tools. The revolutionary aspect of comprehensive multidimensional (MD) techniques, in respect to classical MD chromatography, is that the entire sample is subjected to the 2D advantage. The resulting unprecedented separating capacity makes these approaches prime choices when analysts are challenged with highly complex mixtures. Furthermore, in the case of automated systems, instrumental analysis times are roughly the same as in monodimensional applications. The present review reports various comprehensive chromatographic applications on different food matrices. The GC x GC section highlights two fundamental aspects for component separation/identification: the exceptional peak capacity and the formation of group types on the 2D space plane. The LC x LC section reports the employment in food analysis of a recently developed multidimensional normal-phase (NP)-reversed-phase (RP) high performance liquid chromatography (HPLC) system. Also reported are comprehensive LC x GC and packed column supercritical fluid chromatography (pSFC x pSFC) applications in this field. 相似文献
952.
Chemical genetics is an emerging field that takes advantage of combinatorial chemical and small molecule libraries to dissect complex biological processes. Here we establish a fluorescence-based assay to screen for inhibitors of iron uptake by mammalian cells. Using this approach, we screened the National Cancer Institute's Diversity Set library for inhibitors of non-transferrin bound iron uptake. This screen identified 10 novel small molecule inhibitors of iron transport with IC(50) values that ranged from 5 to 30 microM. Of these ten compounds, only two blocked uptake of iron mediated by transferrin. Thus, this study characterizes the first small molecule inhibitors that distinguish between different pathways of iron transport. 相似文献
953.
William Doherty Peter Halley Les Edye David Rogers Francisco Cardona Yoosup Park Tim Woo 《先进技术聚合物》2007,18(8):673-678
Sugarcane fiber (i.e. bagasse) lignin has a larger fraction of aromatics unsubstitution in the ortho position than hardwood or softwood lignin and hence has the greater ability to be derivatized. Furthermore, organosolv lignin has a higher purity than sulfonated and kraft lignins. This work examines the purification of organosolv lignin derived from bagasse and the physico‐chemical properties of the lignin and lignin‐phenol formaldehyde (PF) resin coatings, and composites. The wetability tests have shown that lignin and lignin‐PF resin films are effective water barrier coatings, though the contact angles of lignin‐PF resin films were considerably less than the wax films. The overall mechanical properties (i.e. peak stress, peak strain and modulus) of the bagasse fiber composites were lower than the values obtained with the composites without the inclusion of bagasse fiber. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
954.
Novel enrofloxacin imprinted polymer applied to the solid-phase extraction of fluorinated quinolones from urine and tissue samples 总被引:1,自引:0,他引:1
A new molecularly imprinted polymer, prepared following a non-covalent approach, was synthesised using enrofloxacin as a template molecule. The imprinting effect of the polymer was verified by chromatographic evaluation and, interestingly, this evaluation also revealed that the imprinted polymer showed a high degree of cross-reactivity for ciprofloxacin, the major metabolite of enrofloxacin. The molecularly imprinted polymer was then applied as a selective sorbent in a two-step solid-phase extraction method focussing upon complex biological matrices, specifically human urine and pig liver. This two-step solid-phase extraction protocol, in which a commercial Oasis HLB cartridge and a molecularly imprinted solid-phase extraction cartridge were combined, allowed enrofloxacin and ciprofloxacin to be determined by liquid chromatography coupled to a UV detector at levels below the maximum residue limits established by the European Union. The quantification and detection limits in tissue samples of enrofloxacin and ciprofloxacin were established at 50 μg kg−1 and 30 μg kg−1, respectively. 相似文献
955.
Graham Smith Urs D. Wermuth Peter C. Healy Jonathan M. White 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(4):o203-o207
The structures of two pseudopolymorphic hydrates of brucine, C23H26N2O4·4H2O, (I), and C23H26N2O4·5.25H2O, (II), have been determined at 130 K. In both (I) and (II) (which has two independent brucine molecules together with 10.5 water molecules of solvation in the asymmetric unit), the brucine molecules form head‐to‐tail sheet substructures, which associate with the water molecules in the interstitial cavities through hydrogen‐bonding associations and, together with water–water associations, give three‐dimensional framework structures. 相似文献
956.
Small-angle neutron scattering study of structural changes in temperature sensitive microgel colloids 总被引:3,自引:0,他引:3
Stieger M Richtering W Pedersen JS Lindner P 《The Journal of chemical physics》2004,120(13):6197-6206
The structure of temperature-sensitive poly(N-isopropylacrylamide) microgels in dilute suspension was investigated by means of small-angle neutron scattering. A direct modeling expression for the scattering intensity distribution was derived which describes very well the experimental data at all temperatures over an extensive q range. The overall particle form as well as the internal structure of the microgel network is described by the model. The influence of temperature, cross-linking density, and particle size on the structure was revealed by radial density profiles and clearly showed that the segment density in the swollen state is not homogeneous, but gradually decays at the surface. The density profile reveals a box profile only when the particles are collapsed at elevated temperatures. An increase of the cross-linking density resulted in both an increase of the polymer volume fraction in the inner region of the particle and a reduction of the smearing of the surface. The polymer volume fraction inside the colloid decreased with increasing particle size. The structural changes are in good agreement with the kinetics of the emulsion copolymerization used to prepare the microgel colloids. 相似文献
957.
Stefan Furegati Walter Ganci Fabrizio Gorla Urs Ringeisen Peter Rüedi 《Helvetica chimica acta》2004,87(10):2629-2661
Phosphorylation of suitable piperidine precursors yielded a series of novel decalin‐type O,N,P‐heterocycles. The title compounds, P(3)‐axially and P(3)‐equatorially X‐substituted, cis‐ and trans‐configurated 2,4‐dioxa‐7‐aza‐, 2,4‐dioxa‐8‐aza‐, and 2,4‐dioxa‐9‐aza‐3‐phosphabicyclo[4.4.0]decane 3‐oxides (X=Cl, F, 4‐nitrophenoxy, and 2,4‐dinitrophenoxy), are configuratively fixed and conformationally constrained P‐analogues of acetylcholine and as such represent acetylcholine (7‐aza and 9‐aza isomers) or γ‐homo‐acetylcholine mimetics (8‐aza isomers). Being irreversible inhibitors of acetylcholinesterase (AChE), the compounds are considered to be suitable probes for the investigation of the stereochemical course of the inhibition reaction by 31P‐NMR spectroscopy. Moreover, the design of these mimetics will enable studies of molecular interactions with AChE, in particular, the recognition conformation of acetylcholine. 相似文献
958.
Fractionation of a steam distilled residue of Commiphora confusa resin has yielded four novel dammarane triterpenes characterised as (20S)-3beta-acetoxy-12beta,16beta-trihydroxydammar-24-ene, (20S)-12beta,16beta-trihydroxydammar-24-ene-3beta-O-beta-glucopyranoside, (20S)-3beta-acetoxy-12beta,16beta,25-tetrahydroxydammar-23-ene, and (20S)-3beta,12beta,16beta,25-pentahydroxydammar-23-ene. The known compounds beta-amyrin, 3beta-amyrinacetate, 2-methoxyfuranodienone, 2-acetoxyfuranodienone, (20R)-3beta-acetoxy-16beta-dihydroxydammar-24-ene, (20R)-3beta,16beta-trihydroxydammar-24-ene, 3beta-acetoxy-16beta-hydroxydammar-24-ene, 3beta-hydroxydammar-24-ene, 3beta-acetoxydammar-24-ene, and beta-sistosterol were also isolated from the same extract. The structures of the compounds were determined using spectroscopic, physical, and chemical methods. 相似文献
959.
A Variety of potential–time waveforms are useful in pulsed electrochemical detection (PED) when applied for the amperometric detection of numerous polar organic compounds following their separation by liquid chromatography (LC). Here, we compare the waveforms for pulsed amperometric detection (PAD) and integrated voltammetric detection (IVD) applied for detection of organosulfur compounds at Au electrodes in acidic media. In PAD waveforms, electrodes response is measured at a constant detection potentials. In IVD waveforms, electrodes current is integrated throughout a fast cyclic scan of the detection potential. As a consequence of this difference in detection strategy, the background signal for IVD is significantly smaller for PAD in the detection of organosulfur compounds whose response mechanisms require the concomitant formation of surface oxides on Au electrodes. Furthermore, in comparison to Pad, IVD has a larger sensitivity and a diminished system peak from 02 dissolved in the sample. Use of a preadsorption step increases detection sensitivity in both PAD and IVD. The limit of detection (S/N=3)for cysteine in LC-IVD is ca. 6 nM for a 50-μl injection (i.e., 300 fmol) using a detection waveform that includes a 1000-ms preadsorption period. 相似文献
960.
Kristian Syberg Maria Bille Nielsen Lauge Peter Westergaard Clausen Geert van Calster Annemarie van Wezel Chelsea Rochman Albert A. Koelmans Richard Cronin Sabine Pahl Steffen Foss Hansen 《Current Opinion in Green and Sustainable Chemistry》2021
- Download : Download high-res image (101KB)
- Download : Download full-size image