全文获取类型
收费全文 | 84719篇 |
免费 | 12197篇 |
国内免费 | 8545篇 |
专业分类
化学 | 58493篇 |
晶体学 | 901篇 |
力学 | 5453篇 |
综合类 | 697篇 |
数学 | 10110篇 |
物理学 | 29807篇 |
出版年
2024年 | 163篇 |
2023年 | 1548篇 |
2022年 | 2658篇 |
2021年 | 2715篇 |
2020年 | 2984篇 |
2019年 | 2907篇 |
2018年 | 2532篇 |
2017年 | 2296篇 |
2016年 | 3546篇 |
2015年 | 3599篇 |
2014年 | 4306篇 |
2013年 | 5839篇 |
2012年 | 7162篇 |
2011年 | 7440篇 |
2010年 | 5110篇 |
2009年 | 4898篇 |
2008年 | 5226篇 |
2007年 | 4655篇 |
2006年 | 4445篇 |
2005年 | 3929篇 |
2004年 | 3146篇 |
2003年 | 2494篇 |
2002年 | 2365篇 |
2001年 | 1977篇 |
2000年 | 1824篇 |
1999年 | 1906篇 |
1998年 | 1579篇 |
1997年 | 1405篇 |
1996年 | 1451篇 |
1995年 | 1286篇 |
1994年 | 1177篇 |
1993年 | 1027篇 |
1992年 | 914篇 |
1991年 | 793篇 |
1990年 | 666篇 |
1989年 | 568篇 |
1988年 | 443篇 |
1987年 | 399篇 |
1986年 | 349篇 |
1985年 | 359篇 |
1984年 | 231篇 |
1983年 | 201篇 |
1982年 | 162篇 |
1981年 | 130篇 |
1980年 | 90篇 |
1979年 | 54篇 |
1978年 | 57篇 |
1977年 | 52篇 |
1975年 | 58篇 |
1973年 | 58篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Two new mixed-ligands lanthanide coordination polymers, [Ln(Ac)(ip)(H2O)2]·0.5H2O (Ln=La (1); Ln=Eu (2); Ac=acetate; ip=isophthalate) have been synthesized under hydrothermal condition. Single-crystal X-ray analyses show that complexes 1 and 2 are three-dimensional structure in which lanthanide ions are bridged by monocarboxylate ligand, acetate or dicarboxylate ligand, isophthalate. And the central lanthanide ions, La3+ and Eu3+, are both nine-coordinate with oxygen atoms. The thermogravimetric analysis was carried out to examine the thermal stability of the title complexes. And the photoluminescence property of complex 2 was also investigated. 相似文献
992.
Synthetic erythropoietic proteins: tuning biological performance by site-specific polymer attachment
Chen SY Cressman S Mao F Shao H Low DW Beilan HS Cagle EN Carnevali M Gueriguian V Keogh PJ Porter H Stratton SM Wiedeke MC Savatski L Adamson JW Bozzini CE Kung A Kent SB Bradburne JA Kochendoerfer GG 《Chemistry & biology》2005,12(3):371-383
Chemical synthesis in combination with precision polymer modification allows the systematic exploration of the effect of protein properties, such as charge and hydrodynamic radius, on potency using defined, homogeneous conjugates. A series of polymer-modified synthetic erythropoiesis proteins were constructed that had a polypeptide chain similar to the amino acid sequence of human erythropoietin but differed significantly in the number and type of attached polymers. The analogs differed in charge from +5 to -26 at neutral pH and varied in molecular weight from 30 to 54 kDa. All were active in an in vitro cell proliferation assay. However, in vivo potency was found to be strongly dependent on overall charge and size. The trends observed in this study may serve as starting points for the construction of more potent synthetic EPO analogs in the future. 相似文献
993.
A novel indium silicate, Rb3In(H2O)Si5O13, has been synthesized using a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction. The structure consists of five-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to four adjacent five-membered rings to form a 3D silicate framework that belongs to the CdSO4 topological type. The InO6 octahedron shares five of its corners with five different SiO4 tetrahedra to form a 3D frame-work that delimits two types of channels to accommodate the rubidium cations. The sixth corner of InO6 is coordinated H2O. The structure is related to that of the titanium silicate ETS-10, and these are the only two metal silicates that have the CdSO4-topological-type structure. In addition, the crystal of Rb3In(H2O)Si5O13 shows an intense second harmonic generation signal. Crystal data: H2Rb3InSi5O14, monoclinic, space group Cc (No. 9), a = 9.0697(5) A, b = 11.5456(6) A, c = 13.9266(8) A, beta = 102.300(1) degrees, V = 1424.8(1) A3, and Z = 4. 相似文献
994.
The nitridation of Si(100) by ammonia and the subsequent oxidation of the nitrided surface by both gaseous atomic and molecular oxygen was investigated under ultrahigh vacuum (UHV) conditions using X-ray photoelectron spectroscopy (XPS). Nitridation of Si(100) by the thermal decomposition of NH3 results in the formation of a subsurface nitride and a decrease in the concentration of surface dangling bond sites. On the basis of changes in the N1s spectra obtained after NH3 adsorption and decomposition, we estimate that the nitride resides about four to five layers below the vacuum-solid interface and that the concentration of surface dangling bonds after nitridation is only 59% of its value on Si(100)-(2 x 1). Oxidation of the nitrided surface is found to produce an oxide phase that remains in the outer layers of the solid and interacts only weakly with the underlying nitride for oxygen coverages up to 2.5 ML. Slight changes in the N1s spectra observed after oxidizing at 300 K are suggested to arise primarily from the introduction of strain within the nitride, and by the formation of a small amount of Si2=N-O species near the nitride-oxide interface. The nitrogen bonding environment changes negligibly after oxidizing at 800 K, which is indicative of greater phase separation at elevated surface temperature. Nitridation is also found to significantly reduce the reactivity of the Si(100) surface toward both atomic and molecular oxygen. A comparison of the oxygen uptake on the clean and nitrided surfaces shows quantitatively that the decrease in dangling bond concentration is responsible for the reduced activity of the nitrided surface toward oxidation, and therefore that dangling bonds are the initial adsorption site for both gaseous oxygen atoms and molecules. Increasing the surface temperature is found to promote the uptake of oxygen when O2 is used as the oxidant, but brings about only a small enhancement in the uptake of gaseous O-atoms. The different effects of surface temperature on the uptake of O versus O2 are interpreted in terms of the efficiency at which dangling bond pairs are regenerated on the surface at elevated temperature and the different site requirements for the adsorption of O and O2. 相似文献
995.
Margaret C. Gerthoffer Sikai Wu Bo Chen Tao Wang Steven Huss Shalisa M. Oburn Vincent H. Crespi John V. Badding Elizabeth Elacqua 《Chemical science》2020,11(42):11419
Limited supramolecular strategies have been utilized to synthesize sequence-defined polymers, despite the prominence of noncovalent interactions in materials design. Herein, we illustrate the utility of ‘sacrificial’ aryl-perfluoroaryl supramolecular synthons to synthesize sp3-hybridized nanothreads from sp2-enriched reactants. Our strategy features A–B reactant pairs in the form of a phenol:pentafluorophenol co-crystal that is preorganized for an electronically-biased and sequence-defined polymerization. The polymerization, initiated at 12 GPa, affords an alternating copolymer featuring exogenous –OH functionalities. The external substitution is confirmed through IR spectroscopy. Importantly, the inclusion of the functional unit provides the first experimental glimpse at reaction mechanism: keto–enol tautomerization that can only occur during cycloaddition is observed through IR spectroscopy. Our approach realizes the first example of a functionalized nanothread and attains sequence definition through sacrificial supramolecular preorganization and presents a further approach for de novo design of complex nanothreads.Supramolecular synthons are exploited to synthesize –OH functionalized sp3-rich sequence-defined nanothreads using pressure-induced polymerization of a phenol:pentafluorophenol co-crystal. 相似文献
996.
The development of highly active and stable reversible oxygen electrocatalysts is crucial for improving the efficiency of metal-air battery devices. Herein, an efficient liquid exfoliation strategy was designed for producing silk-like FeS2/NiS2 hybrid nanocrystals with enhanced reversible oxygen catalytic performance that displayed excellent properties for Zn-air batteries. Because of the unique silk-like morphology and interface nanocrystal structure, they can catalyze the oxygen evolution reaction (OER) efficiently with a low overpotential of 233 mV at j = 10 mA cm?2. This is an improvement from the recently reported catalysts in 1.0 M KOH. Meanwhile, the oxygen reduction reaction (ORR) activity of the silk-like FeS2/NiS2 hybrid nanocrystals showed an onset potential of 911 mV and a half-wave potential of 640 mV. In addition, the reversible oxygen electrode activity of the silk-like FeS2/NiS2 hybrid nanocrystals was calculated to be 0.823 V, based on the potential of the OER and ORR. Further, the homemade rechargeable Zn-air batteries using FeS2/NiS2 hybrid nanocrystals as the air-cathode displayed a high open-circuit voltage of 1.25 V for more than 17 h and an excellent rechargeable performance for 25 h. The solid Zn-air batteries exhibited an excellent rechargeable performance for 15 h. This study provided a new method for designing interface nanocrystals with a unique morphology for efficient multifunctional electrocatalysts in electrochemical reactions and renewable energy devices. 相似文献
997.
998.
The keto-enol tautomerization of p-hydroxyphenylpyruvic acid (pHPP) in aqueous solutions and the complexation reaction between enolic pHPP and boric acid have been studied by electrochemical techniques including linear sweep voltammetry (LSV), pulse voltammetry, and cyclic voltammetry (CV), combining with UV spectrometry. Electrochemical techniques reveal that in aqueous solution, there are two tautomers of pHPP: enolic form and ketonic form; the former exists mainly in freshly prepared pHPP solution, and the latter exists mainly in equilibrium solution. Both enolic and ketonic pHPP are electroactive. The electrochemical oxidation of enolic pHPP gives rise to two anodic waves, I(a) and II(a), while the electrochemical oxidation of ketonic pHPP only results in the observation of the second wave II(a). The oxidation process I(a) is revealed to be associated with the quasi-reversible, two-electron two-proton oxidation of "C=C"group at the side chain of enolic pHPP, and the oxidation process II(a) is proposed to result from the irreversible oxidation of phenolic hydroxyl group. It is observed that in aqueous solution, enolic pHPP can quickly complex with boric acid to yield enol-borate complex that can also oxidize at a glassy carbon electrode to yield an anodic wave. 相似文献
999.
Three new hetero‐bischelated rhodium (III) complexes of cis‐[Rh(PA)(L)Cl2]Cl (where PA = phenylpyridin‐2‐ylmethylene‐amine; L = 2,2′‐bipyridine, 2,2′‐dipyridylamine and 1,10‐phenanthroline) have been successfully prepared and characterized. Each complex shows high intensity bands in the UV region, and these are assigned to spin‐allowed π‐π* transitions. The medium‐intensity absorption band profile in the lower energy region can be explained by convolution of spin‐allowed CT and d‐d* transitions. The emission spectra at low temperature (77 K) of these complexes in EtOH/MeOH (4:1 v/v) are virtually identical. They all exhibit a broad, symmetric, and structureless red emission with a microsecond lifetime and hence are assigned as the d‐d* phosphorescence. 相似文献
1000.