全文获取类型
收费全文 | 28350篇 |
免费 | 5102篇 |
国内免费 | 4118篇 |
专业分类
化学 | 20836篇 |
晶体学 | 288篇 |
力学 | 1864篇 |
综合类 | 338篇 |
数学 | 3427篇 |
物理学 | 10817篇 |
出版年
2024年 | 25篇 |
2023年 | 531篇 |
2022年 | 575篇 |
2021年 | 858篇 |
2020年 | 1070篇 |
2019年 | 1063篇 |
2018年 | 859篇 |
2017年 | 827篇 |
2016年 | 1284篇 |
2015年 | 1256篇 |
2014年 | 1502篇 |
2013年 | 2084篇 |
2012年 | 2460篇 |
2011年 | 2697篇 |
2010年 | 1982篇 |
2009年 | 1924篇 |
2008年 | 2172篇 |
2007年 | 1929篇 |
2006年 | 1846篇 |
2005年 | 1469篇 |
2004年 | 1215篇 |
2003年 | 1065篇 |
2002年 | 977篇 |
2001年 | 792篇 |
2000年 | 670篇 |
1999年 | 650篇 |
1998年 | 549篇 |
1997年 | 469篇 |
1996年 | 457篇 |
1995年 | 391篇 |
1994年 | 330篇 |
1993年 | 294篇 |
1992年 | 247篇 |
1991年 | 192篇 |
1990年 | 198篇 |
1989年 | 138篇 |
1988年 | 115篇 |
1987年 | 102篇 |
1986年 | 80篇 |
1985年 | 65篇 |
1984年 | 37篇 |
1983年 | 36篇 |
1982年 | 31篇 |
1981年 | 13篇 |
1980年 | 14篇 |
1979年 | 4篇 |
1977年 | 5篇 |
1973年 | 3篇 |
1970年 | 3篇 |
1957年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 625 毫秒
961.
962.
Optimizing the quadruple-potential waveform for the pulsed amperometric detection of neomycin 总被引:3,自引:0,他引:3
Determination of neomycin is important for quality control of the pharmaceutical preparation. A quadruple-potential waveform used for pulsed amperometric detection of neomycin was investigated. The waveform cleans the electrode by application of a potential more negative than the potential limit to avoid the formation of gold oxide during applying positive potential to clean gold electrode, thus decreasing the dissolution resulting recession of the gold working electrode within gold oxide formation/reduction cycles in the triple-potential waveform. Waveform parameters were optimized to maximize the signal-to-noise ratio (S/N). The detection limit of neomycin B is lower than 0.01 microg/ml. The linearity of framycetin (plotted as peak area of neomycin B) ranges from 0.05 to 100 microg/ml with correlation coefficient 0.9998. R.S.D. (n = 60) of the peak area of neomycin B is lower than 2%. The quadruple-potential waveform shows low detection limits and long-term reproducibility. 相似文献
963.
合成了两种固态稀土丙氨酸配合物[Ho2(Ala)4(H2O)8]Cl6和[ErY(Ala)4(H2O)8](ClO4)6 (Ala为丙氨酸),用量热和热分析方法研究了这两种配合物的热力学性质.用全自动高精密绝热量热计测定了在78~377 K温区内的低温热容.对于[Ho2(Ala)4(H2O)8]Cl6,在214~255 K温区内发现一固-固相变,其相变温度为235.09 K.对于[ErY(Ala)4(H2O)8](ClO4)6,在99~121 K温区内也发现一固-固相变,其相变温度为115.78 K. [Ho2(Ala)4(H2O)8]Cl6固-固相变焓为3.02 kJ• mol-1,相变熵为12.83 J•K-1•mol-1; [ErY(Ala)4(H2O)8](ClO4)6 固-固相变焓为1.96 kJ•mol-1,相变熵为16.90 J•K-1•mol-1.同时,用TG技术在40~800 ℃温区研究了两配合物的热稳定性.由TG/DTG曲线分析可知, [Ho2(Ala)4(H2O)8]Cl6从80 ℃到479 ℃热分解分两步完成, [ErY(Ala)4(H2O)8](ClO4)6从120 ℃到430 ℃热分解分三步完成. 相似文献
964.
Mass-selected C60 beam produced by laser ablation was accelerated and bombarded the (0001) surface of highly oriented pyrolitic graphite and (111) surface of gold single crystal. The samples were characterized by STM. The STM images showed that, the deposited species collapsed and formed planar structure on the solid surface, but the collapsed species were not dissociated and well oriented on the surface. Both positive and negative C60 ions were observed in the desorption mass spectra, confirming that the species collapsed on the solid surface are still the C60 clusters. 相似文献
965.
Ohsedo Y Takashina R Gong JP Osada Y 《Langmuir : the ACS journal of surfaces and colloids》2004,20(16):6549-6555
Hydrogels of poly(2-hydroxyethyl methacrylate) (PHEMA) with well-defined polyelectrolyte brushes of poly(sodium 4-styrenesulfonate) (PNaSS) of various molecular weights were synthesized, keeping the distance between the polymer brushes constant at ca. 20 nm. The effect of polyelectrolyte brush length on the sliding friction against a glass plate, an electrorepulsive solid substrate, was investigated in water in a velocity range of 7.5 x 10(-5) to 7.5 x 10(-2) m/s. It is found that the presence of polymer brush can dramatically reduce the friction when the polymer brushes are short. With an increase in the length of the polymer brush, this drag reduction effect only works at a low sliding velocity, and the gel with long polymer brushes even shows a higher friction than that of a normal network gel at a high sliding velocity. The strong polymer length and sliding velocity dependence indicate a dynamic mechanism of the polymer brush effect. 相似文献
966.
ChuanChunZOU ShuJieHOU PingShengLEI XiaoTianLIANG 《中国化学快报》2003,14(4):361-364
Two spirostanol saponins(gracillin and dioscin)which have the typical sugar moieties were synthesized facilely by a general approach. 相似文献
967.
968.
Zhan‐Xin Zhang Wei‐Dong Xie Ping‐Lin Li Yan‐Ping Shi Zhong‐Jian Jia 《Helvetica chimica acta》2006,89(12):2927-2933
Six new compounds were isolated from the whole plant of Sonchus uliginosus, including three eudesmane‐type sesquiterpenoids (1β,6α)‐1,6,14‐trihydroxyeudesm‐3‐en‐12‐oic acid γ‐lactone ( 1 ), (1β,6α)‐1,6,14‐trihydroxyeudesma‐3,11(13)‐dien‐12‐oic acid γ‐lactone ( 2 ), and (1β,6α)‐1,6‐dihydroxy‐14‐O‐[(4‐hydroxyphenyl)acetyl]eudesma‐3,11(13)‐dien‐12‐oic acid γ‐lactone ( 3 ), and three phenylpropane derivatives, 4‐hydroxy‐γ,3,5‐trimethoxybenzenepropanol ( 6 ), γ,3,4,5‐tetramethoxybenzenepropanol ( 7 ), and γ,3,4,5‐tetramethoxybenzenepropanol acetate ( 8 ), together with the two known compounds 4 and 5 . The new structures were elucidated by means of spectroscopic methods, such as IR, EI‐MS, HR‐ESI‐MS, 1D‐ and 2D‐NMR, and by comparison of the spectroscopic data with those reported for structurally related compounds. 相似文献
969.
Yixuan Xie Siyu Chen Qiongyu Li Ying Sheng Michael Russelle Alvarez Joeriggo Reyes Gege Xu Kemal Solakyildirim Carlito B. Lebrilla 《Chemical science》2021,12(25):8767
A cross-linking method is developed to elucidate glycan-mediated interactions between membrane proteins through sialic acids. The method provides information on previously unknown extensive glycomic interactions on cell membranes. The vast majority of membrane proteins are glycosylated with complicated glycan structures attached to the polypeptide backbone. Glycan–protein interactions are fundamental elements in many cellular events. Although significant advances have been made to identify protein–protein interactions in living cells, only modest advances have been made on glycan–protein interactions. Mechanistic elucidation of glycan–protein interactions has thus far remained elusive. Therefore, we developed a cross-linking mass spectrometry (XL-MS) workflow to directly identify glycan–protein interactions on the cell membrane using liquid chromatography-mass spectrometry (LC-MS). This method involved incorporating azido groups on cell surface glycans through biosynthetic pathways, followed by treatment of cell cultures with a synthesized reagent, N-hydroxysuccinimide (NHS)–cyclooctyne, which allowed the cross-linking of the sialic acid azides on glycans with primary amines on polypeptide backbones. The coupled peptide–glycan–peptide pairs after cross-linking were identified using the latest techniques in glycoproteomic and glycomic analyses and bioinformatics software. With this approach, information on the site of glycosylation, the glycoform, the source protein, and the target protein of the cross-linked pair were obtained. Glycoprotein–protein interactions involving unique glycoforms on the PNT2 cell surface were identified using the optimized and validated method. We built the GPX network of the PNT2 cell line and further investigated the biological roles of different glycan structures within protein complexes. Furthermore, we were able to build glycoprotein–protein complex models for previously unexplored interactions. The method will advance our future understanding of the roles of glycans in protein complexes on the cell surface.The cell surface glycocalyx is highly interactive defined by extensive covalent and non-covalent interactions. A method for cross-linking and characterizing glycan–peptide interactions in situ is developed. 相似文献
970.
Lin Jia Hui Yang Jun Deng Junmei Chen Yuan Zhou Pan Ding Leigang Li Na Han Yanguang Li 《中国化学》2019,37(5):497-500
Electrocatalytic carbon dioxide reduction holds great promise for reducing the atmospheric CO2 level and alleviating the energy crisis. High‐performance electrocatalysts are often required in order to lower the high overpotential and expedite the sluggish reaction kinetics of CO2 electroreduction. Copper is a promising candidate metal. However, it usually suffers from the issues of poor stability and low product selectivity. In this work, bimetallic Cu‐Bi is obtained by reducing the microspherical copper bismuthate (CuBi2O4) for selectively catalyzing the CO2 reduction to formate (HCOO–). The bimetallic Cu‐Bi electrocatalyst exhibits high activity and selectivity with the Faradic efficiency over 90% in a wide potential window. A maximum Faradaic efficiency of ~95% is obtained at –0.93 V versus reversible hydrogen electrode. Furthermore, the catalyst shows high stability over 6 h with Faradaic efficiency of ~95%. This study provides an important clue in designing new functional materials for CO2 electroreduction with high activity and selectivity. 相似文献