全文获取类型
收费全文 | 8171篇 |
免费 | 1327篇 |
国内免费 | 981篇 |
专业分类
化学 | 5838篇 |
晶体学 | 120篇 |
力学 | 454篇 |
综合类 | 53篇 |
数学 | 1135篇 |
物理学 | 2879篇 |
出版年
2024年 | 25篇 |
2023年 | 175篇 |
2022年 | 324篇 |
2021年 | 295篇 |
2020年 | 305篇 |
2019年 | 303篇 |
2018年 | 259篇 |
2017年 | 266篇 |
2016年 | 428篇 |
2015年 | 421篇 |
2014年 | 552篇 |
2013年 | 606篇 |
2012年 | 769篇 |
2011年 | 778篇 |
2010年 | 512篇 |
2009年 | 457篇 |
2008年 | 512篇 |
2007年 | 403篇 |
2006年 | 415篇 |
2005年 | 375篇 |
2004年 | 325篇 |
2003年 | 243篇 |
2002年 | 226篇 |
2001年 | 188篇 |
2000年 | 128篇 |
1999年 | 189篇 |
1998年 | 125篇 |
1997年 | 96篇 |
1996年 | 117篇 |
1995年 | 112篇 |
1994年 | 94篇 |
1993年 | 57篇 |
1992年 | 60篇 |
1991年 | 60篇 |
1990年 | 71篇 |
1989年 | 45篇 |
1988年 | 29篇 |
1987年 | 22篇 |
1986年 | 29篇 |
1985年 | 15篇 |
1984年 | 14篇 |
1983年 | 14篇 |
1982年 | 8篇 |
1981年 | 10篇 |
1979年 | 3篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1928年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
Xue-qiang Yin 《Tetrahedron》2004,60(15):3451-3455
Prior to this work only two examples of carbanucleosides possessing a C-1′/C-6′ double bond had been reported and they were minor derivatized side products arising during other targeted syntheses. To develop this structural feature into a new class of potential antiviral agents, the 5′-nor derivative of aristeromycin with such an olefinic structure (6) represents the first example. In this regard, treatment of (1′S,2′S,3′S,4′R,5′S)-6-chloro-9-(2′,3′-isopropylidenedioxy-6′-oxabicyclo[3.1.0]hex-4′-yl)purine (7) with sodium methoxide yielded 6 via an E′2-like elimination pathway. A convenient way to the C-4′ epimer of 6 (that is, 17) also arose during these studies and is described. Antiviral analysis of 6 and 17 failed to produce any significant activity. 相似文献
102.
Yin J Aviles P Lee W Ly C Guillen MJ Munt S Cuevas C Faircloth G 《Rapid communications in mass spectrometry : RCM》2005,19(5):689-695
A rapid and sensitive liquid chromatography/tandem mass spectrometry (LC/MS/MS) assay was developed and validated to quantify a novel antineoplastic agent, PM00104, in mouse, rat, dog, and human plasma. The method was validated to demonstrate the specificity, limit of quantification (LOQ), accuracy, and precision of measurements. The calibration range for PM00104 was established using PM00104 standards from 0.01-5.0 ng/mL in blank plasma. The selected reaction monitoring (SRM), based on the m/z 692.2 --> 218.2 transition, was specific for PM00104, and that based on the m/z 697.2 --> 218.2 transition was specific for PM00104 ((13)C(2),(2)H(3)) (the internal standard, IS); no endogenous materials interfered with the analysis of PM00104 and IS from blank plasma. The assay was linear over the concentration range 0.01-5.0 ng/mL. The correlation coefficients for the calibration curves ranged from 0.9981-0.9999. The mean intra-day and inter-day accuracies for all calibration standards (n = 8) ranged from 97-105% (< or =5% bias) in human plasma, and the mean inter-day precision for all calibration standards was less than 8.5%. The mean intra- and inter-day assay accuracy for all quality control (QC) replicates in human plasma (n = 9), determined at each QC level throughout the validated runs, ranged from 96-112% (< or =12% bias) and from 102-105% (< or =5% bias), respectively. The mean intra- and inter-day assay precision was less than 15.0 and 11.8% for all QC levels, respectively. For the QC samples prepared in animal species plasma, the %CV values of the assays ranged from 1.8-8.8% in mouse plasma, from 3.7-13.8% in rat plasma, and from 3.0-7.2% in dog plasma. The assay accuracies ranged from 92-102% (< or =8% bias) for all QC levels prepared in mouse plasma; ranged from 93-106% (< or =7% bias) in rat plasma; and ranged from 95-114% (< or =14% bias) in dog plasma. The assay has been used to support preclinical pharmacokinetic and toxicokinetic studies and is currently used to measure PM00104 plasma concentrations to support clinical trials. 相似文献
103.
[formula: see text] The first general intermolecular C-N bond-forming reactions between aryl halides and amides were realized using a palladium catalyst with Xantphos as the ligand. Aryl triflates, carbamates, and sulfonamides are also viable substrates for the amidations, which proceed at 45-110 degrees C with 1-4 mol% of Pd catalyst in 66-99% yields and exhibit good functional group compatibility. 相似文献
104.
Studyofthegrowthprocessofcolloidalparticlesofnonequilibriumandirreversibilityisanactiveareaofresearch.Therecognitionofcolloidalaggregatesasfractalobjectshasinspiredalargenumberofexperimentalandtheoreticalstudiesonthestructuralandkineticaspectsofaggregationprocesses"'.Morerecently,kineticsofhematiteaggregationbypolyacrylicacidhavebeenstudiedbyzhangandBume3.Theprimaryhematiteparticleswerequiteuniformandfairlyspherical.Inthispaper,wewillreportthesizeevolutionoffractalaggregatesofinitiallypolydis… 相似文献
105.
Yin M Wu CK Lou Y Burda C Koberstein JT Zhu Y O'Brien S 《Journal of the American Chemical Society》2005,127(26):9506-9511
It is well-known that inorganic nanocrystals are a benchmark model for nanotechnology, given that the tunability of optical properties and the stabilization of specific phases are uniquely possible at the nanoscale. Copper (I) oxide (Cu(2)O) is a metal oxide semiconductor with promising applications in solar energy conversion and catalysis. To understand the Cu/Cu(2)O/CuO system at the nanoscale, we have developed a method for preparing highly uniform monodisperse nanocrystals of Cu(2)O. The procedure also serves to demonstrate our development of a generalized method for the synthesis of transition metal oxide nanocrystals. Cu nanocrystals are initially formed and subsequently oxidized to form highly crystalline Cu(2)O. The volume change during phase transformation can induce crystal twinning. Absorption in the visible region of the spectrum gave evidence for the presence of a thin, epitaxial layer of CuO, which is blue-shifted, and appears to increase in energy as a function of decreasing particle size. XPS confirmed the thin layer of CuO, calculated to have a thickness of approximately 5 A. We note that the copper (I) oxide phase is surprisingly well-stabilized at this length scale. 相似文献
106.
Chen X Zhou L Zhang X Yin X Xu C Shan X Wei Z Xu K 《The Journal of chemical physics》2004,120(17):7933-7938
Electron momentum distributions for outer valence orbitals of CF2Cl2 have been obtained by (e,2e) electron momentum spectroscopy at an incident energy of 1200 eV + binding energy. The experimental electron momentum profiles are compared with Hartree-Fock and density functional theory (DFT) calculations using B3LYP hybrid functional with the 6-31G and 6-311+G* basis sets. Generally, the shapes of the experimental momentum profiles are well reproduced by DFT calculations using larger basis sets 6-311 + G*. An attempt has been made to clarify the ordering of the outer valence orbitals, which have been in controversy, by comparing experimental results with B3LYP/6-311 + G* calculations. 相似文献
107.
气溶胶前向散射大气能见度测量系统传递系数的标定及校准方法 总被引:4,自引:0,他引:4
分析了气溶胶的前向角散射特性,利用标准的大气透射仪标定前向散射大气能见度测量系统的传递系数。当系统结构发生变化时,传递系数也随之改变,为保证系统测量的准确性和简化系统传递系数的标定过程,提出了一种利用标准漫透射板校准系统传递系数的方法。该方法使用了两块具有相同透射系数的漫透射板,使气溶胶粒子团在前向半球上产生漫散射,此时探测器的测量值即为包含了仪器常数的定值。当系统结构改变时,这个测量值相对于原测量值的变化率作为比例系数代入系统传递系数的计算,实现校准。 相似文献
108.
Xue Luan Zhongcheng Cong Tassos P. Anastassiades Yin Gao 《Molecules (Basel, Switzerland)》2022,27(10)
Previously synthesized N-butyrylated hyaluronic acid (BHA) provides anti-inflammatory effects in rat models of acute gouty arthritis and hyperuricemia. However, the mechanism of action remains to be elucidated. Herein, the anti-inflammatory and antioxidative activities of BHA and the targeted signaling pathways were explored with LPS-induced RAW264.7 and an adjuvant-induced inflammation in a rat model. Results indicated that BHA inhibited the generation of pro-inflammatory cytokines TNFα, IL-1β and IL-6, reduced ROS production and down-regulated JAK1-STAT1/3 signaling pathways in LPS-induced RAW264.7. In vivo, BHA alleviated paw and joint swelling, decreased inflammatory cell infiltration in paw tissues, suppressed gene expressions of p38 and p65, down-regulated the NF-κB and MAPK signaling pathways and reduced protein levels of TNFα, IL-1β and IL-6 in joint tissues of arthritis rats. This study demonstrated the pivotal role of BHA in anti-inflammation and anti-oxidation, suggesting the potential clinical value of BHA in the prevention of inflammatory arthritis and is worthy for development as a new pharmacological treatment. 相似文献
109.
Yunrui Wei Xixi Zhang Zonghua Wang Jiangmei Yin Jinzhao Huang Gang Zhao Xijin Xu 《中国化学快报》2021,32(1):119-124
Hollow nanostructures have attracted increasing research interest in hydrogen evolution reaction owing to their unique structural features.Herein,Ni-Co mixed metal phosphide hollow and porous polyhedrons was successfully composited(expressed as NiCoP).Benefiting from the synergistic effects of ZIF-67 by doping Ni elements and the well-defined hollow and porous structure,the as-synthesized NiCoP hollow and porous polyhedrons exhibit better electrochemical properties and mechanical stability for hydrogen evolution reaction over a pH-universal range,with a small Tafel slopes of 72,101,176 mV/dec,and a low overpotential of 82,102,261 mV at a current density of 10 mA/cm2 in 0.5 mol/L H2SO4,1 mol/L KOH and1 mol/L phosphate buffer solution(PBS).This general strategy can also be applied to fabricate other hollow cobalt-based phosphides and MOFs-derived materials for HER. 相似文献