全文获取类型
收费全文 | 3294篇 |
免费 | 352篇 |
国内免费 | 662篇 |
专业分类
化学 | 3668篇 |
晶体学 | 37篇 |
力学 | 28篇 |
综合类 | 9篇 |
物理学 | 566篇 |
出版年
2024年 | 9篇 |
2023年 | 27篇 |
2022年 | 59篇 |
2021年 | 89篇 |
2020年 | 109篇 |
2019年 | 95篇 |
2018年 | 103篇 |
2017年 | 121篇 |
2016年 | 131篇 |
2015年 | 136篇 |
2014年 | 157篇 |
2013年 | 345篇 |
2012年 | 215篇 |
2011年 | 237篇 |
2010年 | 173篇 |
2009年 | 203篇 |
2008年 | 198篇 |
2007年 | 192篇 |
2006年 | 176篇 |
2005年 | 186篇 |
2004年 | 151篇 |
2003年 | 160篇 |
2002年 | 102篇 |
2001年 | 86篇 |
2000年 | 94篇 |
1999年 | 71篇 |
1998年 | 72篇 |
1997年 | 85篇 |
1996年 | 43篇 |
1995年 | 43篇 |
1994年 | 52篇 |
1993年 | 27篇 |
1992年 | 23篇 |
1991年 | 12篇 |
1990年 | 20篇 |
1989年 | 17篇 |
1988年 | 17篇 |
1987年 | 33篇 |
1986年 | 38篇 |
1985年 | 60篇 |
1984年 | 25篇 |
1983年 | 24篇 |
1982年 | 36篇 |
1981年 | 30篇 |
1980年 | 18篇 |
1979年 | 6篇 |
1978年 | 2篇 |
排序方式: 共有4308条查询结果,搜索用时 171 毫秒
11.
Whereas glucose oxidase and related proteins are encapsulated readily in silica sol–gels, α-hydroxy enzymes such as lactate
oxidase (LOx), are reported to be damaged by electrostatic interaction with these matrices. Based on a previous report, poly(ethyleneimine),
PEI, was evaluated as a protecting compound under conditions suited to analytical measurements. With LOx and PEI co-encapsulated
in a silica sol–gel, the enzyme retained 62% of its initial activity after 20 days. In the absence of PEI, activity was lost
during the processing. Batch analytical measurements with enzyme-doped sol–gel yielded a linear response over the range 0.5–2.0 mM
lactate and a detection limit of 0.03 mM lactate. Both simple incorporation of LOx in a silica sol–gel and an alternative
protection method, blocking the ion-exchange sites on silica with La(III), failed. These negative results supported the hypothesis
that the efficacy of PEI was related to its formation of a protective sheath around the enzyme.
Author for correspondence. E-mail: coxja@muohio.edu
Received July 29, 2002; accepted December 15, 2002
Published online May 19, 2003 相似文献
12.
掺Eu3+硅基材料的发光性质 总被引:9,自引:5,他引:4
通过溶胶-凝胶技术制备了掺Eu^3 的硅基材料并测试了其三维荧光光谱、激光谱和发射光谱,结果显示,最佳激发波波长为350nm,最强荧光波长为620nm;在350nm光激发下的发射光谱显示Eu^3 的特征发射光谱,产生4条谱带,分别是577nm(^5D0-^7F0),588nm(^5D0-^7F1),596nm(^5D0-^7F1)和610nm(^5D0-^7F2)。 相似文献
13.
When some parameters cannot be easily measured experimentally, mathematical models can often be used to deconvolute or interpret data collected on complex systems, such as those characteristic of many environmental problems. These models can help quantify the contributions of various physical or chemical phenomena that contribute to the overall behavior, thereby enabling the scientist to control and manipulate these phenomena, and thus to optimize the performance of the material or device. In the first case study presented here, a model is used to test the hypothesis that oxygen interactions with hydrogen on the catalyst particles of solid oxide fuel cell anodes can sometimes occur a finite distance away from the triple phase boundary (TPB), so that such reactions are not restricted to the TPB as normally assumed. The model may help explain a discrepancy between the observed structure of SOFCs and their performance. The second case study develops a simple physical model that allows engineers to design and control the sizes and shapes of mesopores in silica thin films. Such pore design can be useful for enhancing the selectivity and reactivity of environmental sensors and catalysts. This paper demonstrates the mutually beneficial interactions between experiment and modeling in the solution of a wide range of problems. 相似文献
14.
John Boyle Ica Manas‐Zloczower DonaldL. Feke 《Particle & Particle Systems Characterization》2004,21(3):205-212
The dispersion behavior of agglomerates of several grades of fumed silica in poly(dimethyl siloxane) liquids has been studied as a function of particle morphology and applied flow conditions. The effects of primary particle size and aggregate density and structure on cohesivity were probed through tensile and shear strength tests on particle compacts. These cohesivity tests indicated that the shear strength of particle compacts was two orders of magnitude higher than the tensile strength at the same overall packing density. Experiments carried out in both steady and time‐varying simple‐shear flows indicate that dispersion occurs through tensile failure. In the steady‐shear experiments,enhanced dispersion was obtained at higher levels of applied stress and, at comparable levels of applied stress, dispersion was found to proceed faster at higher shear rates. Experiments conducted in time‐varying flows further corroborated the results obtained in tensile cohesivity tests. Experiments in which the mean and maximum stresses in the time‐varying flows were matched to the stresses produced in steady shear flows highlight the influence of flow dynamics on dispersion behavior. 相似文献
15.
A new, high performance liquid chromatography method has been developed for the separation of monovinyl- and divinyl-protochlorophyllides, using commercially available, C30 reverse phase column and isocratic elution. This method can be used both for analytical applications and preparative scale purification of monovinyl- and divinyl-protochlorophyllides using the same column where submilimolar concentrations of the crude protochlorophyllide extract can be separated in one run. The purity of the obtained protochlorophyllides was demonstrated by spectroscopic methods, as well by the formation of aggregates in toluene. 相似文献
16.
E.M. Rabinovich D.W. Johnson Jr. A. Mishkevich E.A. Chandross J. Thomson Jr. 《Journal of Sol-Gel Science and Technology》2003,28(1):19-29
Particulate sol-gel technology uses larger particles than that of alkoxide-derived gels and provides larger pore sizes in the gelled object. This allows relatively rapid drying and fabrication of large rods or tubular shapes. However, the formation of more complex or flat shapes, which require extensive surface contact with a mold, is more difficult. The shrinkage during drying, with the significantly greater stress of surface friction due to adhesion, frequently leads to cracking.We have demonstrated a solution to this problem by floating the gel on the surface of a dense liquid. Dry silica panels up to 28 × 40 × 0.7 cm3 were prepared in this way. The use of patterning molds allowed the fabrication of more sophisticated shapes. These bodies were sintered to transparent vitreous silica articles of near net dimensions. 相似文献
17.
Roxana S. Timofte 《Tetrahedron letters》2004,45(1):39-42
High surface area silica pellets are excellent supports for the preparation of silica supported reagents and solid-phase basal linkers through reaction with (RO)3Si(CH2)3FG (FG=NH2, NHMe, Cl, NHC(O)NH2, OC(O)CMe(CH2), NCO, NEt2). High loadings (0.66-2.15 mmol g−1) of grafted silane materials are realised at synthetically useful loadings per pellet (ca. 0.06 mmol). Preliminary trials show that trial linker chemistry and ligand synthesis can be carried out on these materials and that these reactions can be monitored by solid state 13C NMR studies on individual pellets. 相似文献
18.
Jin Sun Yihu Song Qiang Zheng Hong Tan Jie Yu Hong Li 《Journal of Polymer Science.Polymer Physics》2007,45(18):2594-2602
The reinforcement and nonlinear viscoelastic behavior have been investigated for silica (SiO2) filled solution‐polymerized styrene butadiene rubber (SSBR). Experimental results reveal that the nonlinear viscoelastic behavior of the filled rubber is similar to that of unfilled SSBR, which is inconsistent with the general concept that this characteristic comes from the breakdown and reformation of the filler network. It is interesting that the curves of either dynamic storage modulus (G′) or loss tangent (tan δ) versus strain amplitude (γ) for the filled rubber can be superposed, respectively, on those for the unfilled one, suggesting that the primary mechanism for the Payne effect is mainly involved in the nature of the entanglement network in rubbery matrix. It is believed there exists a cooperation between the breakdown and reformation of the filler network and the molecular disentanglement, resulting in enhancing the Payne effect and improving the mechanical hysteresis at high strain amplitudes. Moreover, the vertical and the horizontal shift factors for constructing the master curves could be well understood on the basis of the reinforcement factor f(φ) and the strain amplification factor A(φ), respectively. The surface modification of SiO2 causes a decrease in f(φ), which is ascribed to weakeness of the filler–filler interaction and improvement of the filler dispersion. However, the surface nature of SiO2 hardly affects A(φ). © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2594‐2602, 2007 相似文献
19.
E. Maria Claesson Nilesh C. Mehendale Robertus J.M. Klein Gebbink Gerard van Koten Albert P. Philipse 《Journal of magnetism and magnetic materials》2007
Monodisperse magnetizable colloidal silica particles in a stable dispersion have been functionalized with a homogeneous catalyst: a PCP–pincer Pd-complex. In a proof-of-principle experiment we demonstrate the catalytic activity of the colloids in a C–C bond formation reaction. Advantages of the magnetic silica carriers are the large surface-to-volume ratio and the easy recovery by magnetic separation. After magnetic separation, the catalyst-loaded particles are readily redispersed for further use. 相似文献
20.
H. Hommel A. Touhami A. Halli A. P. LeGrand 《Journal of Polymer Science.Polymer Physics》1995,33(16):2189-2198
EPR spectroscopy of labeled poly(ethylene oxide) (PEO) grafted on silica has been used to characterize the conformation and local dynamics of the chains. Grafted molecules of MW 2000 with grafting ratios of 0.045, 0.057, 0.126, and 0.42 molecules/nm2 were in contact with benzene. The mobility of the label was compared with that observed for solution of PEO from very diluted to highly concentrated and even bulk PEO. Thus, the concentration inside the grafted layer could be evaluated and also the thickness, which evolves rather linearly with the grafting ratio. © 1995 John Wiley & Sons, Inc. 相似文献