全文获取类型
收费全文 | 50213篇 |
免费 | 9405篇 |
国内免费 | 7460篇 |
专业分类
化学 | 37321篇 |
晶体学 | 743篇 |
力学 | 3070篇 |
综合类 | 487篇 |
数学 | 5327篇 |
物理学 | 20130篇 |
出版年
2024年 | 152篇 |
2023年 | 903篇 |
2022年 | 1773篇 |
2021年 | 1865篇 |
2020年 | 2055篇 |
2019年 | 2103篇 |
2018年 | 1848篇 |
2017年 | 1798篇 |
2016年 | 2485篇 |
2015年 | 2630篇 |
2014年 | 3182篇 |
2013年 | 4101篇 |
2012年 | 4764篇 |
2011年 | 4761篇 |
2010年 | 3454篇 |
2009年 | 3525篇 |
2008年 | 3848篇 |
2007年 | 3266篇 |
2006年 | 3009篇 |
2005年 | 2502篇 |
2004年 | 1916篇 |
2003年 | 1602篇 |
2002年 | 1670篇 |
2001年 | 1285篇 |
2000年 | 1023篇 |
1999年 | 895篇 |
1998年 | 683篇 |
1997年 | 611篇 |
1996年 | 546篇 |
1995年 | 446篇 |
1994年 | 425篇 |
1993年 | 329篇 |
1992年 | 279篇 |
1991年 | 241篇 |
1990年 | 207篇 |
1989年 | 144篇 |
1988年 | 118篇 |
1987年 | 91篇 |
1986年 | 104篇 |
1985年 | 80篇 |
1984年 | 44篇 |
1983年 | 44篇 |
1982年 | 27篇 |
1981年 | 31篇 |
1980年 | 18篇 |
1979年 | 21篇 |
1977年 | 11篇 |
1975年 | 12篇 |
1974年 | 11篇 |
1925年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 12 毫秒
991.
天然水体底质中腐植酸的光谱表征 总被引:3,自引:0,他引:3
分别用紫外-可见光谱、傅立叶变换红外光谱(FTIR)、三维荧光光谱和荧光等高线谱对提取的腐植酸和商品腐植酸进行了表征,并将分析结果与Aldrich和上海试剂二厂生产的腐植酸进行了比较。结果表明:3种底质腐植酸之间以及同商品腐植酸的紫外-可见光谱、傅立叶变换红外光谱(FTIR)相似,含有相同类型的官能团。对不同腐植酸的三维荧光光谱和荧光等高线谱的分析表明其在结构上存在一定的差异;腐植酸有较明显的荧光光谱特性,可以尝试使用三维荧光光谱技术来揭示其在结构上的差异。 相似文献
992.
乙烯基硅烷-丙烯酸酯乳液共聚动力学研究 总被引:7,自引:0,他引:7
以乙烯基三乙氧基硅烷(VTES)、丙烯酸酯为单体,乙氧基醇磺基琥珀酸二钠(A—102)为乳化剂,合成了有机硅改性丙烯酸酯共聚乳液。研究了乳化剂、引发剂、VTES、反应温度以及功能性单体甲基丙烯酸羟乙酯(HEMA)对乳液共聚反应速率的影响。结果表明:聚合速率随乳化剂浓度、引发剂浓度、HEMA浓度的增大及反应温度的升高而增大,但随VTES浓度增大而逐渐减小。由实验得出恒速阶段聚合反应速率R_p与乳化剂浓度C_E、引发剂浓度C_1及有机硅单体浓度C_(VTES)的关系为R_p∝C_E~(0.35)C_I~(0.48)C_(VTES)~(-0.64),表观活化能E_a为81.1kJ·mol~(-1)。 相似文献
993.
994.
2,6—二甲基吡啶在Y型分子筛的Bronsted和Lewis酸中心上的吸附动力学董玉林,杨孔章(山东大学胶体与界面化学研究所,济南250100)关键词Y型分子筛,酸中心,Lewis酸中心,2,6—二甲基吡啶,吸附动力学沸石分子筛是一类固体酸催化剂,在... 相似文献
995.
Lu C Wei F Wu N Huang L Zhao X Jiao X Luo C Cao W 《Langmuir : the ACS journal of surfaces and colloids》2004,20(3):974-977
A kind of hybrid multilayer film based on mercaptobenzoic acid-capped Au nanoparticles (MBA-Au-NPs) and photoreactive nitrodiazoresin (NDR) has been fabricated via electrostatic self-assembly. Upon exposure to UV light, the initial ionic bonds between the layers of the film convert into covalent bonds and the film stability toward polar solvents, salt, or surfactant solutions increases significantly. The micropatterned NDR/MBA-Au-NP film with the covalently linked architecture was formed by selecting exposure of the film through a photomask and later developed in sodium dodecyl sulfate (SDS) aqueous solution. The metallic Au-NP micropatterns, furthermore, are produced by sintering the micropatterned NDR/MBA-Au-NP film at 550 degrees C, at which the organic components are removed completely. The well-defined micropatterns were characterized with atomic force microscopy (AFM), field emission scanning electron microscopy (FE-SEM), microscope with a charge-coupled device (CCD) camera, and X-ray photoelectron spectroscopy (XPS). 相似文献
996.
CO(2)-expanded solvents: unique and versatile media for performing homogeneous catalytic oxidations 总被引:2,自引:0,他引:2
Wei M Musie GT Busch DH Subramaniam B 《Journal of the American Chemical Society》2002,124(11):2513-2517
The work summarized here demonstrates a new concept for exploiting dense phase CO(2), media considered to be "green" solvents, for homogeneous catalytic oxidation reactions. According to this concept, the conventional organic solvent medium used in catalytic chemical reactions is replaced substantially (up to 80 vol %) by CO(2), at moderate pressures (tens of bars), to create a continuum of CO(2)-expanded solvent media. A particular benefit is found for oxidation catalysis; the presence of CO(2) in the mixed medium increases the O(2) solubility by ca. 100 times compared to that in the neat organic solvent while the retained organic solvent serves an essential role by solubilizing the transition metal catalyst. We show that CO(2)-expanded solvents provide optimal properties for maximizing oxidation rates that are typically 1-2 orders of magnitude greater than those obtained with either the neat organic solvent or supercritical CO(2) as the reaction medium. These advantages are demonstrated with examples of homogeneous oxidations of a substituted phenol and of cyclohexene by molecular O(2) using transition metal catalysts, cobalt Schiff-base and iron porphyrin complexes, respectively, in CO(2)-expanded CH(3)CN. 相似文献
997.
A flow injection method combined with Resonance light scattering detection was developed for the determination of protein
concentration in human serum samples. This method is based on the enhanced RLS signals of protein binding with the dye acid
chrome blue K. The enhanced RLS intensities at 264 nm, in an acidic aqueous solution, were proportional to the protein concentration
over the range of 2.0–40.0 μg·mL−1 for human serum albumin (HSA) and the limit of detection (3σ) is 85 ng·mL−1. This method was successfully applied to the quantification of total proteins in human serum samples. The maximum relative
standard deviation is less than 2% and the recovery is between 97 and 103% for the standard addition method. The sample throughput
was 60 h−1. 相似文献
998.
The paramagnetic complexes formed in Friedel‐Crafts alkylation reaction systems are invistigated by electron spin resonance (ESR) spectroscopy, in room temperature ionic liquids system 1‐butyl‐3‐methyl‐limidazolium chloride‐aluminium chloride ([bmim]Cl‐AlCl3). The results indicate that ESR spectra observed are due to polycyclic aromatic radical cations formed from their parent hydrocarbons. ESR spectrum of spin adduct is obtained in an ionic liquid system composed of [bmim]Cl‐AlCl3. In acidic solution the 14N hyperfine coupling constant of 4‐oxo‐TEMPO, 2.15 mT, is appreciably larger due to an adduct formed with AlCl3. 相似文献
999.
Carina Hey Pui Cheung Jianchao Xu Chi Lung Lee Yanfeng Zhang Ruohan Wei Donald Bierer Xuhui Huang Xuechen Li 《Chemical science》2021,12(20):7091
Herein, we report the development of a facile synthetic strategy for constructing diverse peptide structural architectures via chemoselective peptide ligation. The key advancement involved is to utilize the benzofuran moiety as the peptide salicylaldehyde ester surrogate, and Dap–Ser/Lys–Ser dipeptide as the hydroxyl amino functionality, which could be successfully introduced at the side chain of peptides enabling peptide ligation. With this method, the side chain-to-side chain cyclic peptide, branched/bridged peptides, tailed cyclic peptides and multi-cyclic peptides have been designed and successfully synthesized with native peptidic linkages at the ligation sites. This strategy has provided an alternative strategic opportunity for synthetic peptide development. It also serves as an inspiration for the structural design of PPI inhibitors with new modalities.Methods of introducing peptide salicylaldehyde esters and hydroxyl amine functionality into the peptide side chain have been developed. Diverse peptide structural motifs were constructed via ligation with native amide linkages at the ligation sites. 相似文献
1000.
Zeng W Wang AQ Fisher AL Musson DG 《Rapid communications in mass spectrometry : RCM》2003,17(22):2475-2482
A generic high-throughput liquid chromatography (HTLC) tandem mass spectrometry (MS/MS) assay for the determination of compound I in human urine and dialysate (hemodialysis) was developed and validated. By using the HTLC on-line extraction technique, sample pretreatment was not necessary. The sample was directly injected onto a narrow bore large particle size extraction column (50 x 1.0 mm, 60 microm) where the sample matrix was rapidly washed away using a high flow rate (5 mL/min) aqueous mobile phase while analytes were retained. The analytes were subsequently eluted from the extraction column onto an analytical column using an organic-enriched mobile phase prior to mass spectrometric detection. The analytes were then eluted from the analytical column to the mass spectrometer for the determination. The linear dynamic range was 2.0-6000 ng/mL for the urine assay and 0.1-300 ng/mL for the dialysate assay. Intraday accuracy and precision were evaluated by analyzing five replicates of calibration standards at all concentrations used to construct the standard curve. For the urine assay, the precision (RSD%, n=5) ranged from 1.9 to 8.0% and the accuracy ranged from 87.8 to 105.2% of nominal value. For the dialysate assay, the precision (RSD%, n=5) ranged from 1.1 to 10.0% and the accuracy from 94.5 to 105.2% of nominal value. In-source fragmentation of the acyl glucuronide metabolite (compound III) did not interfere with the determination of parent compound I. The developed HTLC/MS/MS methodology was specific for compound I in the presence of compound III. Column life-time is increased and sample analysis time is decreased over traditional reversed-phase methods when direct injection assays for urine and dialysate are coupled with the technology of HTLC. 相似文献