全文获取类型
收费全文 | 3979篇 |
免费 | 196篇 |
国内免费 | 49篇 |
专业分类
化学 | 2707篇 |
晶体学 | 54篇 |
力学 | 93篇 |
数学 | 527篇 |
物理学 | 843篇 |
出版年
2023年 | 23篇 |
2022年 | 43篇 |
2021年 | 73篇 |
2020年 | 66篇 |
2019年 | 75篇 |
2018年 | 48篇 |
2017年 | 51篇 |
2016年 | 131篇 |
2015年 | 103篇 |
2014年 | 121篇 |
2013年 | 251篇 |
2012年 | 287篇 |
2011年 | 328篇 |
2010年 | 210篇 |
2009年 | 160篇 |
2008年 | 257篇 |
2007年 | 219篇 |
2006年 | 236篇 |
2005年 | 195篇 |
2004年 | 168篇 |
2003年 | 160篇 |
2002年 | 134篇 |
2001年 | 73篇 |
2000年 | 79篇 |
1999年 | 68篇 |
1998年 | 27篇 |
1997年 | 53篇 |
1996年 | 42篇 |
1995年 | 40篇 |
1994年 | 31篇 |
1993年 | 45篇 |
1992年 | 51篇 |
1991年 | 41篇 |
1990年 | 36篇 |
1989年 | 32篇 |
1988年 | 17篇 |
1987年 | 19篇 |
1986年 | 18篇 |
1985年 | 33篇 |
1984年 | 25篇 |
1983年 | 6篇 |
1982年 | 17篇 |
1981年 | 15篇 |
1980年 | 11篇 |
1979年 | 20篇 |
1978年 | 14篇 |
1977年 | 9篇 |
1976年 | 6篇 |
1974年 | 13篇 |
1973年 | 10篇 |
排序方式: 共有4224条查询结果,搜索用时 15 毫秒
121.
This paper describes the design, fabrication, and test of a PDMS/PMMA-laminated microfluidic device for an immunosensing biochip. A poly(dimethyl siloxane)(PDMS) top substrate molded by polymer casting and a poly(methyl methacrylate)(PMMA) bottom substrate fabricated by hot embossing are bonded with pressure and hermetically sealed. Two inlet ports and an air vent are opened through the PDMS top substrate, while gold electrodes for electrochemical biosensing are patterned onto the PMMA bottom substrate. The analyte sample is loaded from the sample inlet port to the detection chamber by capillary force, without any external intervening forces. For this and to control the time duration of sample fluid in each compartment of the device, including the inlet port, diffusion barrier, reaction chamber, flow-delay neck, and detection chamber, the fluid conduit has been designed with various geometries of channel width, depth, and shape. Especially, the fluid path has been designed so that the sample flow naturally stops after filling the detection chamber to allow sufficient time for biochemical reaction and subsequent washing steps. As model immunosensing tests for the microfluidic device, functionalizations of ferritin and biotin to the sensing surfaces on gold electrodes and their biospecific interactions with antiferritin antiserum and streptavidin have been investigated. An electrochemical detection method for immunosensing by biocatalyzed precipitation has been developed and applied for signal registration. With the biochip, the whole immunosensing processes could be completed within 30 min. 相似文献
122.
123.
Trace metal ions in highly saline samples such as urine were determined with capillary electrophoresis (CE) without desalting or off-line preconcentration. By mixing with a dye, 4-(2-pyridylazo) resorcinol (PAR), the metal ions were converted into anionic complexes having strong absorbance near 500 nm. A large volume of the metal-PAR complex sample solution injected into a coated capillary was stacked isotachophoretically and separated under a reverse potential. The salt anion (chloride) and PAR in the sample matrix acted as the leading and terminating electrolytes, respectively. In a sample containing a 250 mM NaCl matrix, more than 400-fold enhancement in the absorbance detector response was realized compared to the normal CE injection mode. Combination of the dye complexation and isotachophoretic stacking provided excellent detection limits (S/N = 3) for three trace metal ions in the low ppb range (Fe(2+), 0.7 ppb, Ni(2+), 0.4 ppb; Zn(2+), 1.2 ppb) with absorbance detection. The migration time reproducibility was excellent (relative standard deviations: standard samples < 1%, urine samples approximately 1%). The proposed method is convenient and fast, and the sample analysis can be completed within 20 min. 相似文献
124.
We synthesized a novel colorimetric anion chemosensor bearing benzimidazole motifs as recognition sites in the pods of the receptor. The addition of tetrabutylammonium salts of F− or AcO− to the solution of receptor caused dramatic color changes from colorless to yellow, which was clearly visible to the naked eye. The receptor showed no significant changes on addition of other anions such as Cl−, Br−, I−, NO3−, and H2PO4−. 相似文献
125.
Molecular diodes based on conjugated diblock co-oligomers 总被引:2,自引:0,他引:2
This report describes synthesis and characterization of a molecular diode based upon a diblock conjugated oligomer system. This system consists of two conjugated blocks with opposite electronic demand. The molecular structure exhibits a built-in electronic asymmetry, much like a semiconductor p-n junction. Electrical measurements by scanning tunneling spectroscopy (STS) clearly revealed a pronounced rectifying effect. Definitive proof for the molecular nature of the rectifying effect in this conjugated diblock molecule is provided by control experiments with a structurally similar reference compound. 相似文献
126.
Alexeev OS Chin SY Engelhard MH Ortiz-Soto L Amiridis MD 《The journal of physical chemistry. B》2005,109(49):23430-23443
TiO2- and gamma-Al2O3-supported Pt catalysts were characterized by HRTEM, XPS, EXAFS, and in situ FTIR spectroscopy after activation at various conditions, and their catalytic properties were examined for the oxidation of CO in the absence and presence of H2 (PROX). When gamma-Al2O3 was used as the support, the catalytic, electronic, and structural properties of the Pt particles formed were not affected substantially by the pretreatment conditions. In contrast, the surface properties and catalytic activity of Pt/TiO2 were strongly influenced by the pretreatment conditions. In this case, an increase in the reduction temperature led to higher electron density on Pt, altering its chemisorptive properties, weakening the Pt-CO bonds, and increasing its activity for the oxidation of CO. The in situ FTIR data suggest that both the terminal and bridging CO species adsorbed on fully reduced Pt are active for this reaction. The high activity of Pt/TiO2 for the oxidation of CO can also be attributed to the ability of TiO2 to provide or stabilize highly reactive oxygen species at the metal-support interface. However, such species appear to be more reactive toward H2 than CO. Consequently, Pt/TiO2 shows substantially lower selectivities toward CO oxidation under PROX conditions than Pt/gamma-Al2O3. 相似文献
127.
Jeong Hyun Yeum Byung Chul Ji Chul Joo Lee Ji Youl Lee Sang‐Seob Lee Sam Soo Kim Joon Ho Kim Won Seok Lyoo 《Journal of polymer science. Part A, Polymer chemistry》2002,40(8):1103-1111
To prepare water‐soluble, syndiotacticity‐rich poly(vinyl alcohol) (PVA) microfibrils for various industrial applications, we synthesized syndiotacticity‐rich, low molecular weight PVA by the solution polymerization of vinyl pivalate (VPi) in tetrahydrofuran (THF) at low temperatures with 2,2′‐azobis(2,4‐dimethylvaleronitrile) (ADMVN) as an initiator and successive saponification of poly(vinyl pivalate) (PVPi). Effects of the initiator and monomer concentrations and the polymerization temperature were investigated in terms of the polymerization behaviors and molecular structures of PVPi and the corresponding syndiotacticity‐rich PVA. The polymerization rate of VPi in THF was proportional to the 0.91 power of the ADMVN concentration, indicating the heterogeneous nature of THF polymerization. The low‐temperature solution polymerization of VPi in THF with ADMVN proved to be successful in obtaining water‐soluble PVA with a number‐average degree of polymerization (Pn) of 300–900, a syndiotactic dyad content of 60–63%, and an ultimate conversion of VPi into PVPi of over 75%. Despite the low molecular weight of PVA with Pn = 800, water‐soluble PVA microfibrillar fibers were prepared because of the high level of syndiotacticity. In contrast, for PVA with Pn = 330, shapeless and globular morphologies were observed, indicating that molecular weight has an important role in the in situ fibrillation of syndiotacticity‐rich PVA. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1103–1111, 2002 相似文献
128.
In this paper,we are interested in HSS preconditioners for saddle point lin- ear systems with a nonzero(2,2)-th block.We study an approximation of the spectra of HSS preconditioned matrices and use these results to illustrate and explain the spectra obtained from numerical examples,where the previous spectral analysis of HSS precon- ditioned matrices does not cover. 相似文献
129.
Laser cladding of copper with molybdenum for wear resistance enhancement in electrical contacts 总被引:1,自引:0,他引:1
Laser cladding of Mo on Cu has been attempted with the aim of enhancing the wear resistance and hence increasing the service life of electrical contacts made of Cu. In order to overcome the difficulties arising from the large difference in thermal properties and the low mutual solubility between Cu and Mo, Ni was introduced as an intermediate layer between Mo and Cu. The Ni and Mo layers were laser clad one after the other to form a sandwich layer of Mo/Ni/Cu. Excellent bonding between the clad layer and the Cu substrate was ensured by strong metallurgical bonding. The hardness of the surface of the clad layer is seven times higher than that of the Cu substrate. Pin-on-disc wear tests consistently showed that the abrasive wear resistance of the clad layer was also improved by a factor of seven as compared with untreated Cu substrate. The specific electrical contact resistance of the clad surface was about 5.6 × 10−7 Ω cm2. 相似文献
130.
本文主要描述小分子在真空紫外波段(VUV,6-20 eV)光解离动力学的最新实验和理论研究进展.得益于基于商业化激光器的真空紫外光源技术,以及离子速度成像、高分辨氢原子-里德堡态标记-飞行时间测量和VUV-VUV泵浦-探测等方法的发展,研究人员现在可以对很多小分子在真空紫外波段的光解离动力学进行量子态到量子态层面的测量和研究,本文重点综述H_2(D_2,HD),CO,N_2,NO,O_2,H_2O(D_2O,HOD),CO_2,N_2O以及一些多原子分子在真空紫外波段光解离动力学的最新研究进展.这些小分子在真空紫外波段的光解离在天体化学以及大气化学中有着非常重要的应用.分子吸收一个VUV光子以后,通常会被直接激发到比较高的电子激发态,解离过程会涉及到多个电子态势能面之间的复杂非绝热相互作用.在实验上对解离截面等参数进行从量子态到量子态层面的精细测量对于深入了解这些复杂的势能面之间的相互作用有非常重要的意义.最近建成的大连相干光源是目前世界上唯一一台在真空紫外波段工作的自由电子激光,具有脉冲能量高、扫描范围宽(50~150 nm)等优越的性能,它的建成必将会大大促进小分子真空紫外光解离研究的发展. 相似文献