全文获取类型
收费全文 | 5077篇 |
免费 | 268篇 |
国内免费 | 134篇 |
专业分类
化学 | 3340篇 |
晶体学 | 58篇 |
力学 | 202篇 |
综合类 | 7篇 |
数学 | 923篇 |
物理学 | 949篇 |
出版年
2023年 | 65篇 |
2022年 | 89篇 |
2021年 | 133篇 |
2020年 | 164篇 |
2019年 | 158篇 |
2018年 | 148篇 |
2017年 | 101篇 |
2016年 | 197篇 |
2015年 | 173篇 |
2014年 | 214篇 |
2013年 | 378篇 |
2012年 | 336篇 |
2011年 | 382篇 |
2010年 | 234篇 |
2009年 | 210篇 |
2008年 | 325篇 |
2007年 | 282篇 |
2006年 | 265篇 |
2005年 | 248篇 |
2004年 | 190篇 |
2003年 | 175篇 |
2002年 | 148篇 |
2001年 | 103篇 |
2000年 | 60篇 |
1999年 | 65篇 |
1998年 | 58篇 |
1997年 | 49篇 |
1996年 | 36篇 |
1995年 | 42篇 |
1994年 | 37篇 |
1993年 | 32篇 |
1992年 | 17篇 |
1991年 | 23篇 |
1990年 | 22篇 |
1989年 | 19篇 |
1988年 | 15篇 |
1987年 | 16篇 |
1986年 | 18篇 |
1985年 | 28篇 |
1984年 | 23篇 |
1983年 | 25篇 |
1982年 | 24篇 |
1981年 | 23篇 |
1980年 | 19篇 |
1979年 | 12篇 |
1978年 | 11篇 |
1977年 | 12篇 |
1976年 | 6篇 |
1973年 | 7篇 |
1935年 | 6篇 |
排序方式: 共有5479条查询结果,搜索用时 546 毫秒
121.
V. Pichon H. Rogniaux N. Fischer-Durand S. Ben Rejeb F. Le Goffic M. -C. Hennion 《Chromatographia》1997,45(1):289-295
Summary The trace-level determination of organic pollutants in complex matrices is difficult and often not reliable because theccurrent
extraction procedures are non-selective. New extraction sorbents involving antigen-antibody interactions, called immunosorbents
(ISs), have been synthesised in order to trap a group of structurally related pollutants. The IS capacity is always high for
the analyte-antigen used to make the antibodies, but can be low for some related compounds. In this work, we show the relationship
that exists between capacity, break-through volume and recovery of analytes because of the competition between the structurally
related compounds for antibody sites. Breakthrough due to the overloading of the column should be avoided because calibration
curves are no longer linear. The capacity of two ISs, one made for trapping the triazine pesticide group and the second for
the phenylurea, group, have been optimised by selecting silica with 50 nm pore size. Calibration curves are linear for all
the compounds in a mixture of ten phenylureas up to a concentration of 5 to 10 μg L−1 for each compound when handling 50 mL water samples through a precolumn packed with 0.22 g of IS. Under these conditions,
reliable quantitative results are obtained because calibration curves are similar when compounds are alone or in a mixture.
Application to the clean-up of soil extracts illustrates the high selectivity and the high potential of these new sorbents
in environmental analysis.
Presented at the 21st ISC held in Stuttgart, Germany, 15th–20th September, 1996 相似文献
122.
Kim N Kim W Lee S Lee H Rhee H Choi Y Jung Y Cha S 《Experimental & molecular medicine》1999,31(4):185-190
Clinical cases of type-1 hypersensitive reaction to rice (Oryza sativa) have been reported in western countries as well as in Japan. Among rice proteins, 14-16 kD globulin proteins encoded by multiple gene family have been identified as major rice allergens. In this study, a rice cDNA library was constructed using lambda UniZap vector and screened with a rat anti-16 kD globulin protein polyclonal antibody in order to isolate Korean rice allergenic cDNA clones. Five independent cDNA clones, termed RAK1-5, were obtained after second rounds of plaque assay and immunoblot analysis. These clones encoded 13-19 kD recombinant proteins upon IPTG induction, which were identified by the polyclonal antibody in immunoblot analysis. DNA sequencing analysis showed that RAK1-4 have 99% sequence homology with RA5b, and RAK5 is closely related with RA14c. This result indicated that RA5b gene is widely distributed in our cDNA library among other possible rice allergenic genes, and more study is needed to isolate heterogeneous or novel rice allergen genes. 相似文献
123.
Ben Ghoulam M Moatadid N Graciaa A Lachaise J 《Langmuir : the ACS journal of surfaces and colloids》2004,20(7):2584-2589
Phase behaviors of water/nonionic surfactants/isooctane systems are determined experimentally in temperature-global surfactant concentration diagrams. The surfactants are monodistributed polyoxyethylene glycol n-dodecyl ether. They are used as model mixtures of two, three, or five compounds or as constituents of a commercial surfactant. It is found that the phase diagrams of these systems are bent gradually toward the highest temperatures as the global surfactant concentration decreases. Each phase diagram is well-characterized by the curve of the HLB (hydrophile-lipophile balance) temperature versus the global surfactant concentration. For any fixed global surfactant concentration, this temperature is the middle temperature of the three-phase region; it can be calculated from an additive rule of the HLB temperatures of the surfactants weighted by their mole fractions at the water/oil interface. These mole fractions are determined through the pseudophase model using surfactant partitioning. Calculations require the knowledge of the critical micelle concentration, the partition coefficient between water and oil, and the HLB temperature of each surfactant of the mixture. This treatment can be used to correctly predict the variation of the HLB temperatures of the surfactant mixtures studied versus the global surfactant concentration. Furthermore, these calculations show that the observed curvature of the phase diagrams at the lowest global concentrations is due to the most favorable partitioning toward the oil of the lowest ethoxylated surfactant molecules. 相似文献
124.
Wenxuan Jiang Wei Wei Tinglian Yuan Shasha Liu Ben Niu Hui Wang Wei Wang 《Chemical science》2021,12(24):8556
The inevitable microstructural defects, including cracks, grain boundaries and cavities, make a portion of the material inaccessible to electrons and ions, becoming the incentives for electrochemically inactive zones in single entity. Herein, we introduced dark field microscopy to study the variation of scattering spectrum and optical mass centroid (OMC) of single Prussian blue nanoparticles during electrochemical reaction. The “dark zone” embedded in a single electroactive nanoparticle resulted in the incomplete reaction, and consequently led to the misalignment of OMC for different electrochemical intermediate states. We further revealed the dark zones such as lattice defects in the same entity, which were externally manifested as the fixed pathway for OMC for the migration of potassium ions. This method opens up enormous potentiality to optically access the heterogeneous intraparticle dark zones, with implications for evaluating the crystallinity and electrochemical recyclability of single electroactive nano-objects.The schematic of single cubic-shaped Prussian blue (PB) mesocrystals formed by the oriented aggregation of small nanocrystals. The dark-field images of single PB nanoparticle at PB and Prussian white (PW) states, respectively. 相似文献
125.
Ben‐Yong Lou Yan‐Bin Huang 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(4):o246-o248
4,4′‐Bipyridyl N,N′‐dioxide crystallizes with 3‐hydroxy‐2‐naphthoic acid to give a centrosymmetric three‐component adduct, C10H8N2O2·2C11H8O3, which is engineered into a two‐dimensional layer structure by two kinds of π–π interactions. Weak C—H⋯O interactions further link the two‐dimensional structure into a three‐dimensional structure. 相似文献
126.
D. Axente M. Abrudean A. Bâldea 《Journal of Radioanalytical and Nuclear Chemistry》1996,207(1):163-170
The rate of nitrogen isotope exchange between NO and HNO3 has been measured as a function of nitric acid concentration of 1.5–4M·1–1. The exchange rate law is shown to beR=k[HNO3]2[N2O3] and the measured activation energy isE=67.78kJ ·M–1 (16.2 kcal·M–1). It is concluded that N2O3 participates in15N/14N exchange between NO and HNO3 at nitric acid concentrations higher than 1.5M·1–1. 相似文献
127.
Etude de phosphates condenses diagramme d’equilibre du systeme AgPO3−Pr(PO3)3 Données sur AgPr(PO3)4
D. Ben Hassen-Chehimi M. Trabelsi-Ayedi 《Journal of Thermal Analysis and Calorimetry》1995,44(4):961-967
The AgPO3?Pr(PO3)3 system has been studied for the first time by differential thermal analysis, X-ray diffraction and IR spectroscopy. The system shows one compound AgPr(PO3)4 which melts in a peritectic decomposition at 1069 K. An eutectic appears at 761 K. AgPr(PO3)4 belongs to the monoclinic system with space group P2t/c,Z=4. The parameters of the unit cell are:a=12.000(9),b=13.177(4),c=7.046(5) Å and β=123o,81(6),Z=4. Its IR absorption spectrum is typical of chain phosphates. 相似文献
128.
Hui Chen Yujiao Fan Nian Zhang Sylvain Trpout Bergam Ptissam Annie Brûlet Ben Zhong Tang Min-Hui Li 《Chemical science》2021,12(15):5495
Fluorescent polymer cubosomes and hexosomes with aggregation-induced emission (AIE) were prepared from amphiphilic block copolymers PEG-b-PTPEMA where the hydrophobic block PTPEMA was a polymethacrylate with tetraphenylethene (TPE) as the AIE side group. Four highly asymmetric block copolymers with hydrophilic block weight ratio fPEG ≤ 20% were synthesized. Cubosomes and hexosomes with strong fluorescence emission were obtained by nanoprecipitation of polymers with fPEG < 9% in dioxane/water and THF/water systems. Their ordered internal structures were studied by electron microscopy (cryo-EM, SEM and TEM) and the X-ray scattering technique (SAXS). To elucidate the formation mechanisms of these inverted colloids, other parameters influencing the morphologies, like the water content during self-assembly and the organic solvent composition, were also investigated. This study not only inspires people to design novel building blocks for the preparation of functional cubosomes and hexosomes, but also presents the first AIE fluorescent polymer cubosome and hexosome with potential applications in bio-related fields.Fluorescent Imm cubosome and P6mm hexosome with aggregation-induced emission (AIE) were reported, which were formed by amphiphilic block copolymers PEG-b-PTPEMA. The length of hydrophobic block PTPEMA was adjusted to control morphology formation. 相似文献
129.
Cyrański MK Howard ST Chodkiewicz ML 《Chemical communications (Cambridge, England)》2004,(21):2458-2459
Various models applied to DFT structures and energies of 2-D and 3-D aromatic molecules shed new light on the effects of strain and aromaticity in these systems. The cyclic pi electron delocalisation does not stabilize the fullerene C60 formation; and 5-6 and 6-6 CC bonds have near-identical bond stretch potentials. 相似文献
130.
Monserrat García Gerhard van Vliet Mattijs G. J. ten Cate Francisco Chvez Ben Norder Bart Kooi Werner E. van Zyl Henk Verweij Dave H. A. Blank 《先进技术聚合物》2004,15(4):164-172
Solution impregnations, pulltrusion and film stacking are widely used methods to prepare thermoplastic composite materials. Extruders are used to melt the polymer and to incorporate fibers into the polymer in order to modify physical properties. In this article, the compounding of colloidal silica nanoparticles filled polyamide‐6 (PA‐6) is achieved using a twin‐screw extruder, which has a significant market share due to its low cost and easy maintenance. The experiments were performed at 250 rpm and the bulk throughput was 6 kg h?1 with a pump pressure of 30 bars. The composites were characterized with nuclear magnetic resonance (NMR), wide angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC) and transmission electron microscopy (TEM). As determined by WAXD, the PA‐6 showed higher amounts of γ‐phase when compared to other synthesis methods such as in situ polymerization. TEM pictures showed that the silica particles aggregated nevertheless, upon addition of 14% (w/w) silica the E‐modulus increased from 2.7 to 3.9 GPa indicating that an effective mechanical coupling with the polymer was achieved. The behavior, illustrated with dynamic mechanical analysis (DMA) curves, indicated that in general when a filled system is compared to unfilled material, the values of the moduli (E′ and E″) increased and tan δ decreased. Determination of molecular mass distribution of the samples by means of size exclusion chromatography (SEC) coupled to a refractive index (RI), viscosity (DV) and light scattering (LS) detector revealed that the addition of silica did not decrease the average molecular weight of the polymer matrix, which is of importance for composite applications. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献