全文获取类型
收费全文 | 4482篇 |
免费 | 132篇 |
国内免费 | 10篇 |
专业分类
化学 | 3628篇 |
晶体学 | 33篇 |
力学 | 47篇 |
数学 | 196篇 |
物理学 | 720篇 |
出版年
2023年 | 25篇 |
2021年 | 33篇 |
2020年 | 48篇 |
2019年 | 68篇 |
2018年 | 38篇 |
2017年 | 22篇 |
2016年 | 67篇 |
2015年 | 60篇 |
2014年 | 97篇 |
2013年 | 207篇 |
2012年 | 206篇 |
2011年 | 263篇 |
2010年 | 104篇 |
2009年 | 119篇 |
2008年 | 237篇 |
2007年 | 247篇 |
2006年 | 240篇 |
2005年 | 285篇 |
2004年 | 218篇 |
2003年 | 186篇 |
2002年 | 200篇 |
2001年 | 128篇 |
2000年 | 155篇 |
1999年 | 54篇 |
1998年 | 54篇 |
1997年 | 46篇 |
1996年 | 68篇 |
1995年 | 37篇 |
1994年 | 57篇 |
1993年 | 40篇 |
1992年 | 58篇 |
1991年 | 52篇 |
1990年 | 44篇 |
1989年 | 46篇 |
1988年 | 56篇 |
1987年 | 48篇 |
1986年 | 67篇 |
1985年 | 61篇 |
1984年 | 72篇 |
1983年 | 38篇 |
1982年 | 41篇 |
1981年 | 42篇 |
1980年 | 36篇 |
1979年 | 42篇 |
1978年 | 32篇 |
1977年 | 31篇 |
1976年 | 24篇 |
1975年 | 35篇 |
1974年 | 32篇 |
1973年 | 23篇 |
排序方式: 共有4624条查询结果,搜索用时 31 毫秒
81.
The photo-induction of free radicals in synthetic L-dihydroxyphenylalanine (L-DOPA) melanin in the presence of bovine serum albumin (BSA) was studied by electron paramagnetic resonance (EPR) spectroscopy. By monitoring the signal intensities and progressive microwave power saturation it was shown that L-DOPA melanin in solution behaves as a single macromolecule, interacting with BSA and molecular oxygen. In the absence of oxygen, the EPR signal of L-DOPA melanin was homogeneously broadened; the magnetic interaction with oxygen induced inhomogeneous broadening. In aqueous solution, the presence of BSA decreased the accessibility of oxygen to paramagnetic centres in the melanin. On UV-visible illumination, the presence of BSA modified the rates of formation and decay of photoinduced free radicals, resulting in a net enhancement of the EPR signal compared with that observed in pure L-DOPA melanin. 相似文献
82.
Seiji Miyano Osamu Yamashita Kunihiro Sumoto Keiyu Shima Mariko Hayashimatsu Fumio Satoh 《Journal of heterocyclic chemistry》1987,24(1):271-274
The method for preparing 7a-substituted hexahydro-1H-pyrrolizines 2 from 1,2,3,5,6,7-hexahydropyrrol-izinium Perchlorate (3) was investigated, by which introduction of a wide variety of functionalities on C(7a) could be achieved easily. 相似文献
83.
Seiji Shinkai Youichiro Hara Osamu Manabe 《Journal of polymer science. Part A, Polymer chemistry》1982,20(4):1097-1105
Three thiazolium-containing polymers, Th-7, Th-33, and Th-18-Py [where Th-x and Py mean x mol % thiazolium unit and pyridinium unit (54 mol %), respectively], were synthesized from partially p-chloromethylated polystyrene. The catalytic activities of these polymer catalysts in acyloin condensation of aldehydes and decarboxylation of α-keto acids were estimated kinetically by oxidative trapping of the key intermediate by flavin (flavin-trapping technique). In aqueous solution at 30°C, the catalytic activity of Th-18-Py and Th-33 in condensation of p-chlorobenzaldehyde was comparable with that of the cationic-micelle-bound thiazolium ion, whereas Th-7 and a monomeric thiazolium compound (N-benzylthiazolium bromide) scarcely exhibited any catalytic activity. The catalysis of the polymer-bound thiazolium ions was sensitively suppressed by increased ionic strength. These results suggest that the pendent thiazolium ion is activated by the relatively high charge density along the polymer chain: the cationic environment is able to facilitate dissociation of the thiazolium ion to the ylid form and deprotonation of the thiazolium-aldehyde adduct to the key intermediate. 相似文献
84.
Ammoniacal copper quat (ACQ) compound wood preservative is comprised of copper and quaternary ammonium compounds with benzalkonium chloride (BAC) as the active ingredient. Solid-phase extraction (SPE) followed by liquid chromatography with ultraviolet detection (LC-UV) was developed for quantitative determination of BAC in treated wood. Five species of wood were used, Japanese cedar (Cryptomeria japonica), Japanese larch (Larix leptolepis), Yezo spruce (Picea jezoensis), Sakhalin fir (Abies sachalinensis), and western hemlock (Tsuga heterophylla). BAC used in the present study was composed of 66% C12, 33% C14 and less than 1% C16. BAC was added to each wood species (500 mg) then extracted with HCl-ethanol (20 ml) and quantitatively determined with LC-UV (262 nm). Wood extractives from the heartwood of each species, except western hemlock, interfered with quantitative determination of BAC, but SPE with an Oasis MCX cartridge was effective in preventing this. Using the present methods, BAC homologue peaks were clearly confirmed without interference. Recoveries from wood ranged from 92 to 101% and the limit of quantitation was approximately 240 microg/g wood for the C12 and C14 homologues. 相似文献
85.
Analysis of the interaction between human plasma fibronectin and gelatin by affinity electrophoresis
The interaction between human plasma fibronectin and gelatin was analyzed by affinity electrophoresis, in which the fibronectin was subjected to electrophoresis in a 4% polyacrylamide gel in the presence and absence of gelatin, as an affinity ligand, and the fibronectin band was stained by an immunoblotting method. The apparent dissociation constants (Kd) of fibronectin for gelatin were calculated from affinity plots based on the original affinity equation at different pHs, urea concentrations, and temperatures. The fibronectin exhibited much lower affinity in the presence of urea. The Kds at 37 degrees C were 1.49 X 10(-7) M, 2.50 X 10(-6) M, and 3.58 X 10(-6) M with 2 M, 3 M, and 4 M urea, respectively. The van't Hoff plots of Kd values against absolute temperature (T) showed that the value of log Kd decreased in proportion to the increase in the value of 1/T within the range of 15-50 degrees C. The standard enthalpy, the standard free energy change at 37 degrees C, and the entropy change at 37 degrees C for association were calculated to be -124.7 kJ/mol, -33.23 kJ/mol, and -295.1 J/mol/deg, respectively. These results suggest that a hydrophilic interaction, such as hydrogen bond or van der Waals interaction, plays an important role in the binding of plasma fibronectin to gelatin. 相似文献
86.
Cross-axis synchronous flow-through coil planet centrifuge (type XLL). I. Design of the apparatus and studies on retention of stationary phase 总被引:1,自引:0,他引:1
The fourth prototype holds a pair of column holders in the lateral position at 15 cm from the center of the rotary shaft horizontally mounted on the rotary frame at 7.6 cm from the central axis of the apparatus. Using short coils of 2.6 mm I.D. PTFE (polytetrafluoroethylene) tubing with 7.6 cm and 24 cm helical diameters, retention of the stationary phase was measured in ten pairs of two-phase solvent systems under various experimental conditions. Satisfactory retention was obtained by choosing proper combinations of three factors, i.e., the direction of planetary motion, head-tail elution mode, and inward-outward elution mode. The polar butanol solvent systems showed excellent retention from 65 to 80% in the 7.6 cm helical diameter left-handed coil. 相似文献
87.
The negative ion mass spectra of chlorine-containing molecules have been measured using a double focusing mass spectrometer with a photographic plate detector. The formulae of the negative ions not previously assigned using an electron multiplier detector have now been assigned. 相似文献
88.
Takaya Y Kikuchi H Terui Y Komiya J Furukawa KI Seya K Motomura S Ito A Oshima Y 《The Journal of organic chemistry》2000,65(4):985-989
For the elucidation of the diversity of secondary metabolites of Dictyostelium cellular slime molds, we investigate the constituent of three species of slime molds. From the methanol extract of their fruit bodies, we obtained three novel compounds, dictyopyrone A (1) and B (2) from D. discoideum and D. rhizoposium and dictyopyrone C (3) from D. longosporum. They possess a unique alpha-pyrone moiety with a side chain at the C-3 position. Their relative structures were elucidated by spectral means, and the absolute configuration was confirmed by asymmetric synthesis of 1. Since these compounds were obtained from different species of Dictyostelium slime molds, they may be a type of compound common to this genus. 相似文献
89.
Shin-ichi Hirano Toshinobu Yogo Wataru Sakamoto Seiji Yamada Tomoyuki Nakamura Tomoe Yamammto Hiroyuki Ukai Kouichi Banno Tomoko Nakafuku Yukari Ando 《Journal of Sol-Gel Science and Technology》2003,26(1-3):35-41
Nano sized crystalline particles/polymer hybrids were synthesized form designed metal-organic precursors. The newly developed method is composed of the synthesis of organic matrix by polymerization and the in situ nucleation and growth of crystalline oxide particles in the organic matrix below 100°C. The design of metal-organic precursor modified with polymerizable ligand and the selection of reaction conditions does influence the size and crystallinity of ceramic particles in organic matrix. The nano-sized magnetic particle/polymer hybrid exhibits the interesting feature of superparamagnetism and quantum size effect. The crystalline particles of BaTiO3/, PbTiO3/, and KNbO3/polymer hybrids behave to be dielectric and show the typical electro-rheological behavior. 相似文献
90.
Makoto Minato Takefumi Kaneko Shogo Masauji Takashi Ito 《Journal of organometallic chemistry》2006,691(11):2483-2488
We describe the synthesis of a new asymmetric P,N,N′-tridentate ligand (bis(pyrid-2-ylethyl) menthylphosphine, BPEMP), containing two pyridyl rings and (1S,2R,5S)-menthylphosphino group. The ligand is obtained in five steps from natural abundant l-menthol. The coordination behavior of the ligand toward cationic (allylic)Pd(II) moiety and its first application in palladium-catalyzed asymmetric allylic alkylation are presented. Crystallographic and spectroscopic analyses reveal that [(η3-allylic)Pd(BPEMP)]+ complex forms only one isomer in the solid state as well as in solution. 相似文献