全文获取类型
收费全文 | 14676篇 |
免费 | 666篇 |
国内免费 | 98篇 |
专业分类
化学 | 10411篇 |
晶体学 | 81篇 |
力学 | 237篇 |
数学 | 2157篇 |
物理学 | 2554篇 |
出版年
2023年 | 106篇 |
2022年 | 104篇 |
2021年 | 209篇 |
2020年 | 349篇 |
2019年 | 307篇 |
2018年 | 192篇 |
2017年 | 157篇 |
2016年 | 490篇 |
2015年 | 377篇 |
2014年 | 447篇 |
2013年 | 748篇 |
2012年 | 909篇 |
2011年 | 1081篇 |
2010年 | 592篇 |
2009年 | 465篇 |
2008年 | 858篇 |
2007年 | 857篇 |
2006年 | 837篇 |
2005年 | 783篇 |
2004年 | 611篇 |
2003年 | 443篇 |
2002年 | 490篇 |
2001年 | 224篇 |
2000年 | 217篇 |
1999年 | 189篇 |
1998年 | 190篇 |
1997年 | 169篇 |
1996年 | 197篇 |
1995年 | 167篇 |
1994年 | 185篇 |
1993年 | 164篇 |
1992年 | 142篇 |
1991年 | 121篇 |
1990年 | 101篇 |
1989年 | 87篇 |
1988年 | 68篇 |
1987年 | 74篇 |
1985年 | 122篇 |
1984年 | 103篇 |
1983年 | 75篇 |
1982年 | 118篇 |
1981年 | 96篇 |
1980年 | 83篇 |
1979年 | 109篇 |
1978年 | 95篇 |
1977年 | 88篇 |
1976年 | 97篇 |
1975年 | 67篇 |
1974年 | 63篇 |
1973年 | 89篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
171.
Osterloh FE Hiramatsu H Dumas RK Liu K 《Langmuir : the ACS journal of surfaces and colloids》2005,21(21):9709-9713
A scaleable chemical approach to functional nanoscale analogues of the magnetic compasses in magnetotactic bacteria is described. LiMo(3)Se(3)-Fe(3)O(4) nanowire-nanoparticle composites were synthesized by a reaction of 3-iodopropionic acid treated LiMo(3)Se(3) nanowire bundles with oleic acid-stabilized Fe(3)O(4) nanoparticles of 2.8, 5.3, and 12.5 nm size in tetrahydrofuran. Transmission electron micrographs show that the composite consists of Fe(3)O(4) nanoparticles attached to the surfaces of the 4-6 nm thick nanowire bundles. UV/vis spectra reveal absorptions from the nanowire (506 nm) and magnetite components (280-450 nm), and IR spectra show characteristic bands for the propionic acid linkers and for the residual oleic acid ligands on the magnetite particles. In the presence of excess oleic acid, the nanocomposites undergo rapid disassembly, suggesting that Fe(3)O(4) nanoparticles are bonded to nanowires via carboxylate groups from the linkers. Ultrasonication of a dispersion of the composite in THF produces individual LiMo(3)Se(3)-Fe(3)O(4) clusters, which are 340 +/- 107 nm long and 20 +/- 5 nm thick, depending on the sonication time and Fe(3)O(4) nanoparticle size. Field cooled and zero-field cooled magnetization measurements reveal that the blocking temperature (T(B) = 100 K) of the clusters with 5.3 nm Fe(3)O(4) is increased as compared to the free nanoparticles (T(B) = 30 K). Directional dipolar interactions in the clusters lead to magnetic anisotropy, which makes it possible to align the clusters in a magnetic field (900 Oe). 相似文献
172.
M. Harangozó V. Frank J. Tölgyessy M. Ondráček 《Journal of Radioanalytical and Nuclear Chemistry》1994,182(1):57-62
Radionuclide X-ray fluorescence method with a Si/Li semiconductor detector and238Pn exciting source was used in the study of Mn, Fe, Cu, Zn, and Pb content of solid emissions, raw and final materials of a brick factory. From the point of view of metal content, the working environment of the brick factory is safe for workers. 相似文献
173.
Alfred Deege Heribert Husmann Eduard Hübinger Frank Kobor Gerhard Schomburg 《Journal of separation science》1993,16(10):587-593
Complex mixtures of partially alkylated cyclodextrins can be analyzed by both HPLC and high temperature capillary GC. Because of the limited efficiency of LC, suitable analytical and preparative separations can be achieved only with systems of carefully optimized selectivity. Using LC it has been possible to isolate and purify single cyclodextrin species from very complex mixtures of components which contain unreacted hydroxyl groups in addition to the alkoxy groups. Analysis of the reaction mixtures and of fractions taken from LC separations can be performed with advantage by high resolution capillary GC at high temperatures between 300 and 400 °C. The thermal stability of partially alkylated cyclodextrins in high temperature GC is considerably increased by trimethylsilylation of the free hydroxyl groups. Fast atom bombardment mass spectrometry and proton NMR were used to identify species isolated from the preparative LC separations. 相似文献
174.
固相萃取柱上衍生气相色谱-质谱法测定水中烷基酚 总被引:7,自引:0,他引:7
以烷基酚(APs)主要降解产物辛基酚(4-t-OP)、壬基酚(4-n-NP)为研究对象,建立了固相萃取(SPE)柱上衍生化、气相色谱-质谱(GC-MS)法测定水中APs的分析方法。以C18柱为固相萃取柱、N,O-(三甲基硅)三氟乙酰胺(BSTFA)为硅烷化试剂,设计五因素四水平正交实验L16(45),对衍生化影响因素、衍生化溶剂、衍生化时间以及SPE主要影响因素pH值、盐度和洗脱剂进行优化;在优化条件下,方法的回收率(高于80%)和重现性(RSD低于10%)结果令人满意,4-t-OP和4-n-NP的仪器检出限分别为3.35ng/L和6.38ng/L。采用建立的方法,回收率略高于传统的SPE萃取衍生法,具有有机溶剂用量少,方法简单快速、灵敏度高的特点,适用于河水和海水中痕量烷基酚的快速测定。 相似文献
175.
Rahimipour S Litichever-Coslovsky N Alaluf M Freeman D Ehrenberg B Weiner L Mazur Y Fridkin M Koch Y 《Photochemistry and photobiology》2005,81(2):250-258
A combination of light, oxygen and a photosensitizer is used to induce death of cancer cells by photodynamic therapy. In this study, we have synthesized several new methyl helianthrone derivatives and compared their phototoxicity with that of hypericin. In contrast to hypericin, methyl helianthrones are soluble in aqueous solutions and have a broad range of light absorbance, which allows the use of polychromatic light. Structural modifications of methyl helianthrone demonstrated that substitution of hydrogen atoms of methyl helianthrone at Positions 2 and 5 with Br atoms or methylation of its phenolic hydroxyls, significantly increases the corresponding singlet oxygen quantum yield and their phototoxicity toward alphaT3-1, M2R and LNCaP cells. The phototoxicity of some of these compounds was similar to that of hypericin. Methyl helianthrones, like hypericin, accumulated mainly in the perinuclear region as evident by confocal microscopy. Irradiation of cells pretreated with methyl helianthrone derivatives generates intracellular reactive oxygen species and lipid free radicals, as shown by a fluorescentic probe and electron paramagnetic resonance methods, respectively. The phototoxicity of these methyl helianthrones as well as their ability to oxidize membrane lipids were significantly decreased on addition of specific Type-II inhibitors, suggesting the involvement of singlet oxygen as the main oxidant. 相似文献
176.
The apparent molal volume and adiabatic compressibilities of some transition metal (Mn2+, Co2+ Ni2+, Cu2+, Zn2+, and Cd2+) sulfates have been determined at 25°C. Values of
to 11.4 cm3-mole–1 and
to 31.3 × 10–4cm3-mole–1-bar–1 at 1 atm were found for the formation of the transition metal sulfate ion pairs. These results are in good agreement with the values obtained from the high-pressure conductance measurements of Fisher et al., Shimizu et al., and Taniguchi et al. The volume and compressibility data indicate that 3.1±0.7 water molecules are lost when transition metals form ion pairs with SO
4
2–
. The fractions of inner-sphere ion pairs (20%) estimated in this study are in good agreement with the values obtained from ultrasonic measurements. 相似文献
177.
Abstract— Photofrin II (PF-II) is the commercial name of the active photosensitizer which is used in photodynamic therapy of cancer. The effect of the composition of lipid membranes on the binding of PF-II was studied and compared to hematoporphyrin derivative (Hpd), which is a complex mixture of porphyrins and from which PF-II is separated. We find that increasing the content of cholesterol in the bilayer decreases the partitioning of PF-II into the bilayer, similar to what we have found earlier with Hpd. However, inserting DMPC or DPPC into the membrane, which was shown to decrease the binding of Hpd, causes the opposite trend with PF-H. A membrane fluidizer such as benzyl alcohol also has different effects on the membrane binding of Hpd and PF-II. The rate of binding of PF-II to a lipid membrane is about 10 times lower than that of Hpd. These results as well as I- quenching of the fluorescence of the two porphyrins indicate that PF-II is immersed less homogeneously and deeper in the bilayer than Hpd. The unique additive-dependent binding of PF-II to lipid membranes calls for care in using Hpd as a model photosensitizer. 相似文献
178.
Electron micrographs of parallel arrays of negatively stained ramie cellulose protofibrils were analyzed using the two-dimensional digital autocorrelation function (ACF). The method is based upon the statistical analysis of images in real space. The ACF shows strong parallel streaks of high correlation, and the lateral distance between adjacent streaks allows the mean interfibrillar distance to be estimated as 3.7 nm. The intensity profile along the streaks shows a weak modulation with peaks occurring at integral multiples of 3 or 6 nm. These results provide direct evidence that there is a regular axial texture in the protofibrils, and corroborate the conclusions previously drawn from optical diffraction analysis. Using the difference vectors found in the ACF it has been possible to reduce the picture noise level by linear integration, thereby obtaining an enhanced image. A preliminary result obtained in this way suggests that the projected protofibril morphology associated with the observed axial periodicity is a ribbon-like zigzag structure. Possible applications of the method for future work are discussed. 相似文献
179.
Robin L. Garrell John C. Smyth Frank R. Fronczek Richard D. Gandour 《Journal of inclusion phenomena and macrocyclic chemistry》1988,6(1):73-78
Single crystal X-ray analysis of the 2:1 acetonitrile complex of 18-crown-6 is reported. Crystals of the complex are monoclinic,P21/n, witha=9.123(3),b=8.524(3),c=13.676(4) Å, =104.68(3)°, andD
c
=1.118 g cm–3 forZ=2. The complex lies on a center of symmetry, with the crown in theD
3d conformation. Methyl groups of the acetonitrile molecules have weak interactions with the crown oxygen atoms, and are tilted 31.7° from the host's threefold axis. Methyl hydrogen atoms are rotationally disordered about the acetonitrile axis.
Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82057 (12 pages). 相似文献
180.