全文获取类型
收费全文 | 14725篇 |
免费 | 2185篇 |
国内免费 | 3190篇 |
专业分类
化学 | 12300篇 |
晶体学 | 287篇 |
力学 | 640篇 |
综合类 | 239篇 |
数学 | 1541篇 |
物理学 | 5093篇 |
出版年
2024年 | 44篇 |
2023年 | 233篇 |
2022年 | 496篇 |
2021年 | 535篇 |
2020年 | 549篇 |
2019年 | 592篇 |
2018年 | 482篇 |
2017年 | 553篇 |
2016年 | 675篇 |
2015年 | 768篇 |
2014年 | 938篇 |
2013年 | 1254篇 |
2012年 | 1332篇 |
2011年 | 1412篇 |
2010年 | 1120篇 |
2009年 | 1026篇 |
2008年 | 1182篇 |
2007年 | 1077篇 |
2006年 | 982篇 |
2005年 | 792篇 |
2004年 | 660篇 |
2003年 | 517篇 |
2002年 | 509篇 |
2001年 | 464篇 |
2000年 | 383篇 |
1999年 | 293篇 |
1998年 | 197篇 |
1997年 | 140篇 |
1996年 | 137篇 |
1995年 | 129篇 |
1994年 | 117篇 |
1993年 | 90篇 |
1992年 | 66篇 |
1991年 | 62篇 |
1990年 | 67篇 |
1989年 | 30篇 |
1988年 | 43篇 |
1987年 | 19篇 |
1986年 | 29篇 |
1985年 | 27篇 |
1984年 | 20篇 |
1983年 | 16篇 |
1982年 | 8篇 |
1981年 | 6篇 |
1980年 | 5篇 |
1979年 | 6篇 |
1976年 | 3篇 |
1974年 | 2篇 |
1973年 | 3篇 |
1957年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
151.
A novel one-dimensional complex [Zn(NIT4py)2(DTB)2(H2O)2] (1), with mixed ligands [where NIT4py is 2-(4′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide and DTB is 3,5-dinitrobenzoate] has been synthesized and characterized by elemental analyses, i.r., u.v.–vis spectra, thermogravimetric analysis, X-ray single crystal diffraction and magnetic measurements. The complex crystallizes in the triclinic crystal system and space group Pî. The Zn II ion is in a distorted octahedral environment: two nitrogen atoms from two NIT4py entities, two oxygen atoms from two DTB units in the basal plane; and two oxygen atoms from the two water molecules in the axial position. The [Zn(NIT4py)2(DTB)2(H2O)2] units are connected as a one dimension chain by the intermolecular hydrogen bonds. The complex exhibits intramolecular antiferromagnetic interactions between the two radicals. 相似文献
152.
为将生物体内微观的蛋白行为可视化并以宏观信号呈现出来对蛋白进行实时、动态分析,借助SNAP-tag蛋白标签技术与有机小分子荧光染料,构建了一系列用于活细胞内实时监测目标蛋白的免洗荧光探针。标签蛋白SNAP-tag能够特异性识别探针中的苄基鸟嘌呤,从而使目标蛋白共价连接上荧光团(萘酰亚胺),携带上荧光信使。此外,由于萘酰亚胺从水环境中被牵引至SNAP-tag蛋白的疏水空腔,其荧光信号呈现出2~13倍的增强。通过SNAP-tag标签蛋白与目标蛋白的融合,该荧光探针实现了对活细胞内线粒体蛋白CoX8A及核内蛋白H2B特异性识别,在免洗条件下完成了对目标蛋白的实时追踪及原位分析。 相似文献
153.
Hydrous amorphous Al (HAO), Fe (HFO), and Mn (HMO) oxides are ubiquitous in the subsurface as both discrete particles and coatings and exhibit a high affinity for heavy metal contaminants. To assess risks associated with heavy metals, such as Pb, to the surrounding environment and manage remedial activities requires accurate mechanistic models with well-defined transport parameters that represent sorption processes. Experiments were conducted to evaluate Pb sorption to microporous Al, Fe, and Mn oxides, as well as to montmorillonite and HAO-coated montmorillonite. Intraparticle diffusion, a natural attenuating process, was observed to be the rate-limiting mechanism in the sorption process, where best-fit surface diffusivities ranged from 10(-18) to 10(-15) cm(2) s(-1). Specifically, diffusivities of Pb sorption to discrete aluminum oxide, aluminum oxide-coated montmorillonite, and montmorillonite indicated substrate surface characteristics influence metal mobility where diffusivity increased as affinity decreased. Furthermore, the diffusivity for aluminum oxide-coated montmorillonite was consistent with the concentrations of the individual minerals present and their associated particle size distributions. These results suggest that diffusivities for other coated systems can be predicted, and that oxide coatings and montmorillonite are effective sinks for heavy metal ions. 相似文献
154.
Mg-based hydrogen storage alloys Mg0.9Ti0.1-xZrxNi (x=0.02, 0.04, 0.06) were successfully prepared by means of mechanical alloying (MA). The effects of Zr addition on the discharge capacity and the cycle performance of the Mg-based electrodes were also studied. It was found that the discharge capacities were improved with addition of a small amount of Zr and the cycle performances of the alloy were stabilized with the addition of Ti. The effects of surface modification or coating on the properties of Mg0.9Ti0.06Zr0.04Ni were also studied. The results indicated that coating with graphite improved both the discharge capacity and cycle life of the amorphous Mg0.9Ti0.06Zr0.04Ni electrode. 相似文献
155.
156.
Nam W Oh SY Sun YJ Kim J Kim WK Woo SK Shin W 《The Journal of organic chemistry》2003,68(20):7903-7906
The catalytic epoxidation of cyclohexene by iron(III) porphyrin complexes and H2O2 has been investigated in alcohol solvents to understand factors affecting the catalyst activity in protic solvents. The yields of cyclohexene oxide and the Fe(III/II) reduction potentials of iron porphyrin complexes were significantly affected by the protic solvents, and there was a close correlation between the product yields and the reduction potentials of the iron porphyrin catalysts. The role of alcohol solvents was proposed to control the electronic nature of iron porphyrin complexes that determines the catalyst activity in the epoxidation of olefins by H2O2. We have also demonstrated that an electron-deficient iron porphyrin complex can catalyze the epoxidation of olefins by H2O2 under conditions of limiting substrate with high conversion efficiency in a solvent mixture of CH3OH and CH2Cl2. 相似文献
157.
Multilayer vesicles and vesicle clusters formed by the fullerene-based surfactant C60(CH3)5K 总被引:3,自引:0,他引:3
Burger C Hao J Ying Q Isobe H Sawamura M Nakamura E Chu B 《Journal of colloid and interface science》2004,275(2):632-641
The self-assembly behavior of a fullerene-based surfactant, C60(CH3)5K, in water was studied using a combination of static and dynamic light scattering, as well as transmission electron microscopy, and compared to that of the compound C60(C6H5)5K. Both fullerene surfactant systems spontaneously assemble into large vesicles consisting of closed spherical shells formed by bilayers, with critical aggregation concentrations (CAC) lower than 10(-6) g ml(-1). At low concentrations, the aggregate sizes of C60(CH3)5K (radius R approximately 26.8 nm) and C60(C6H5)5K (R approximately 17.0 nm) were found to be substantially different from each other, showing that the change of the substituents surrounding the polar cyclopentadienide head group makes it possible to control the size of the resulting aggregates. Furthermore, the C60(CH3)5K vesicles were found to exist in two qualitatively different types of aggregation with a critical reaggregation concentration (CRC) located at 3.30 x 10(-6) g ml(-1). Above the CRC, larger aggregates were observed (R approximately 37.6 nm), showing a more complex form of supramolecular aggregation, e.g., in terms of multi-bilayer vesicles and/or of clusters of bilayer vesicles. 相似文献
158.
DNA works as hereditary material and plays vital role in life science. The study of the binding of small molecules complex to DNA has been the focus of intense investigation, owning to their stereo and sequence specific interaction with the double helix1-… 相似文献
159.
A novel norvancomycin-bonded chiral stationary phase (NVC-CSP) was synthesized by using the chiral selector of norvancomycin. The chiral separation of enantiomers of several dansyl-amino acids by high-performance liquid chromatography (HPLC) in the reversed-phase mode is described. The effects of some parameters, such as organic modifier concentration, column temperature, pH and flow rate of the mobile phase, on the retention and enantioselectivity were investigated. The study showed that ionic, as well as hydrophobic interactions were engaged between the analyte and macrocycle in this chromatographic system. Increasing pH of buffers usually improved the chiral resolution for dansyl--amino-n-butyric acid (Dns-But), dansyl-methionine (Dns-Met) and dansyl-threonine (Dns-Thr), but not for dansyl-glutamic acid (Dns-Glu) which contains two carboxylic groups in its molecular structure. The natural logarithms of selectivity factors (ln ) of all the investigated compounds depended linearly on the reciprocal of temperature (1/T), most processes of enantioseparation were controlled enthalpically. Interestingly, the process of enantioseparaton for dansyl-threonine was enthalpy-controlled at pH of 3.5, while at pH of 7.0, it was entropy-controlled according to thermodynamic parameters ΔR,SΔH° and ΔR,SΔS° afforded by Van’t Hoff plots. In order to get baseline separation for all the solutes researched, norvancomycin was also used as a chiral mobile phase additive. In combination with the NVC-CSP, remarkable increases in enanselectivity were observed for all the compounds, as the result of a “synergistic” effect. 相似文献
160.
An improved method has been developed for the determination of acrylamide in infant powdered milk and baby foods in jars, a particular class of foodstuffs which represent an important source of nutrition for young infants and babies. This method uses isotope dilution liquid chromatography coupled to a tandem mass spectrometer with electrospray ionization and is significantly more sensitive than previous published methods with a limit of quantification estimated at 1 microg kg(-1). The new method offers effective sample preparation procedures including defatting with petroleum ether, extraction with aqueous solution of sodium chloride, further liquid-liquid extraction with ethyl acetate and clean-up by solid-phase extraction (SPE) with HLB 200 mg cartridges. The analytical method was well validated and good results were obtained with respect to repeatability (RSD < 5%) and recovery (86-97%) which fulfilled the requirements defined by European Union (EU) legislation. The acrylamide level in infant powdered milk and baby foods in jars were 3.01-9.06 microg kg(-1) and 6.80-124.93 microg kg(-1), respectively. Especially, this new method is successfully applied to the trace quantification of acrylamide in infant/baby foods, the content of which is less than 10 microg kg(-1). 相似文献