全文获取类型
收费全文 | 33076篇 |
免费 | 2765篇 |
国内免费 | 2403篇 |
专业分类
化学 | 32924篇 |
晶体学 | 518篇 |
力学 | 847篇 |
综合类 | 87篇 |
数学 | 184篇 |
物理学 | 3684篇 |
出版年
2024年 | 43篇 |
2023年 | 271篇 |
2022年 | 568篇 |
2021年 | 583篇 |
2020年 | 1033篇 |
2019年 | 1009篇 |
2018年 | 988篇 |
2017年 | 1409篇 |
2016年 | 1778篇 |
2015年 | 1405篇 |
2014年 | 1443篇 |
2013年 | 3171篇 |
2012年 | 2151篇 |
2011年 | 1905篇 |
2010年 | 1748篇 |
2009年 | 2073篇 |
2008年 | 1855篇 |
2007年 | 1963篇 |
2006年 | 1668篇 |
2005年 | 1462篇 |
2004年 | 1383篇 |
2003年 | 1108篇 |
2002年 | 904篇 |
2001年 | 678篇 |
2000年 | 646篇 |
1999年 | 609篇 |
1998年 | 541篇 |
1997年 | 503篇 |
1996年 | 466篇 |
1995年 | 466篇 |
1994年 | 394篇 |
1993年 | 320篇 |
1992年 | 295篇 |
1991年 | 203篇 |
1990年 | 173篇 |
1989年 | 157篇 |
1988年 | 179篇 |
1987年 | 183篇 |
1986年 | 116篇 |
1985年 | 87篇 |
1984年 | 103篇 |
1983年 | 26篇 |
1982年 | 68篇 |
1981年 | 34篇 |
1980年 | 20篇 |
1979年 | 21篇 |
1978年 | 7篇 |
1977年 | 6篇 |
1975年 | 4篇 |
1973年 | 7篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
R. Castanet 《Journal of Thermal Analysis and Calorimetry》1994,42(2-3):361-381
Due to improvements of high temperature calorimetry, the quantity of liquid alloys showing large negative departures from ideality increased strongly during the last decades. Such a behaviour is now explained by the occurence of chemical short-range order (CSRO), the stoichiometry of which is often elucidated from direct structural determinations as well as from modelization of the thermodynamic functions. In some extreme cases, the destruction of CSRO by increasing temperature lead to a genuine second order transition. The short rewiev of experimental results concerning the variation of physical properties of some liquid alloysvs. temperature and concentration agrees well with CSRO. Some examples of structural determination of CSRO in metallic melts are given. Finally, links between CSRO and phase diagrams and between CSRO and glass-forming ability are also examined. 相似文献
992.
A novel class of the liquid crystal polymers with mesogens laterally attached to flexible main chain backbones has been synthesized recently by us. While the flexible backbones tend to take configuration of maximum entropy the mesogenic side groups tend to orientate because of the anisotropie soft dispersion forces. A mean field theory is presented to describe the competition between these two trends which makes it possible for this class of polymers to show anisotropic (liquid crystal) phase within certain temperature range where the polymer main chains and the side chain mesogens will take approximately parallel arrangement, which is different from the normal side chain liquid crystal polymers. The temperature range of the liquid crystal phase, its ordering and phase transition all depend on the flexibility of the backbone, the strengthof the anisotropic forces of the side groups and the hinge elasticity. The results show that the liquid crystalisotropic phase transition is of the first order. The phase diagram, i. e. the dependence of the transition temperature on the structure of the polymers is also given. 相似文献
993.
Harald Greger Otmar Hofer Andreas Werner 《Monatshefte für Chemie / Chemical Monthly》1985,116(2):273-277
In addition to the well known affinin [=spilanthol, (2E,6Z,8E)-deca-2,6,8-trienoic acid isobutylamide (1)], the corresponding 2-methyl-butylamide (2), and two new acetylenic alkamides were isolated fromSpilanthes oleracea L. by reversed phase medium pressure chromatography: (Z)-non-2-en-6,8-diynoic acid isobutylamide (3) and (Z)-dec-2-en-6,8-diynoic acid isobutylamide (4). The structures and their stereochemistries were elucidated by1H-NMR,13C-NMR (2 and3), MS, UV, IR, and CD (2). The chemotaxonomic significance of the distribution of alkamides within theCompositae tribeHeliantheae is briefly discussed.
Neue Amide ausSpilanthes oleracea (Kurze Mitteilung)
Zusammenfassung AusSpilanthes oleracea wurden neben dem seit langem bekannten Affinin [=Spilanthol, (2E,6Z,8E)-Deca-2,6,8-triensäureisobutylamid (1)] durch Umkehrphasen-Mitteldruckchromatographie das entsprechende 2-Methylbutylamid (2) und zwei neue acetylenische Alkamide isoliert: (Z)-Non-2-en-6,8-diinsäure-isobutylamid (3) und (Z)-Dec-2-en-6,8-diinsäure-isobutylamid (4). Die Strukturen und deren Stereochemie wurden mittels1H-NMR,13C-NMR (2 und3), MS, UV, IR und CD (2) aufgeklärt. Die chemotaxonomische Bedeutung der Verbreitung von Alkamiden innerhalb der Compositen-TribusHeliantheae wird kurz diskutiert.相似文献
994.
G. Theodoridis I. Papadoyannis A. Hermans-Lokkerbol R. Verpoorte 《Chromatographia》1995,41(3-4):153-160
Summary A major problem in the HPLC analysis of alkaloids is the poor peak shape and consequently low resolution, due to the interactions of the basic alkaloids with the residual acidic silanol groups of most reversed phase materials. The performance of new packing materials specially designed for the separation of basic compounds has been studied using mobile phases without the special additives commonly applied in the analysis of alkaloids. Strongly basic Cinchona alkaloids were used as test compounds. Retention characteristics and selectivities of each material were studied, after mobile phase optimisation for the column. The influence of the major factors (nature and content of the organic modifier, pH value, salt concentration) affecting resolution was studied. The mobile phases were chosen so that they could be used in thermospray LC-MS. The addition of salts to the mobile phase improves separation but in general the modification of the mobile phase gave little change in selectivity. The performance of silicabased C18 material proved superior to the polymer materials tested. 相似文献
995.
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
996.
Double Pore Silica Gel Monolith Applied to Liquid Chromatography 总被引:2,自引:0,他引:2
K. Nakanishi H. Minakuchi N. Soga N. Tanaka 《Journal of Sol-Gel Science and Technology》1997,8(1-3):547-552
Silica gels retaining double pore structure in the size ranges of micrometer and nanometer have been applied to the rod-shaped
monolithic column for liquid chromatography. The macropore structure was designed by controlling the phase separation process
induced by the hydrolysis and polycondensation of alkoxysilane, whereas the mesopore structure was tailored by the solvent
exchange treatments on wet gels. The size exclusion chromatograms on polystyrene standards exhibited almost similar features
for octadecyl-modified rod and conventional packed beads columns. The dependence of plate height on the velocity of mobile
phase determined for amylbenzene was by far weaker in the rod column than in the packed beads column, suggesting that additional
geometrical factors should be considered in describing the separation mechanism in the rod column. 相似文献
997.
Summary A method has been developed for the determination of trace levels of 32 pesticides, 19 explosives and 16 polycyclic aromatic
hydrocarbons (PAH) in water in three individual steps. Solid-phase enrichment (SPE) is coupled to high-performance liquid
chromatography (HPLC) with a fully automated system. The organic pollutants are enriched on reusable cartridges packed with
adsorbent materials: pesticides and explosives on a mixed bed of divinylbenzene-ethylvinylbenzene copolymers (LiChrolut EN?) and perfluorinated polyethylene (PolyF?), and polycyclic aromatic hydrocarbons on C18-modified silica (Zorbax? ODS1). Thermally assisted desorption (TAD) has been shown to increase the recovery of analytes significantly. As all enriched
analytes are transferred to the detector, only fifty millilitres of sample is needed for each single on-line analysis, compared
with at least a litre for conventional methods. The separation of the enriched organic analytes is performed on specialized
HPLC columns based on reversed-phase materials. The limits of detection of the system employed were found to be below 100
ng L−1. Use of fluorescence detection for the polycyclic aromatic hydrocarbons resulted in limits of detection in the upper pg L−1 range. Thek values, number of theoretical plates, the recovery rates and the limits of detection of this method for fast screening of
organic pollutants from three fifty-millilitre aqueous samples are described.
Presented at the 21st ISC held in Stuttgart, Germany, 15th–20th September, 1996 相似文献
998.
Cadmium colloids have been prepared by Chemical Liquid Deposition (CLD). The metal is evaporated to yield atoms which are solvated at liquid nitrogen temperature, and upon warming, stable liquid colloids are formed with particle size ranging between 25–100 Å. Zeta potentials were calculated according to the conversion of Hunter and the Hückel equation, for ethanol and dimethyl sulphoxide. UV/VIS measurement of most of the black colloids showed absorption band around 280 nm. For comparison, we prepared CdS colloid with size 400–625 Å. The colloids are stable to oxidation in air and/or oxygen bubbling. The synthesis of colloids and films from Cd with acetone, 2-butanone, ethanol, 2-propanol, 2-methoxyethanol, DMF and DMSO is reported. Transmission Electron Microscopy (TEM) allows us to determine particle size. 相似文献
999.
Summary A direct method for the simultaneous determination of tartaric, malic, lactic, acetic, citric, shikimic, fumaric and succinic acids in fruit juices and wines by isocratic reversed phase HPLC is reported.The variables (pH, ionic strength, flow and temperature) have been optimized by a modification of the original simplex method. The separation factor (s) and calibrated resolution product (r*) have been used as criteria for selectivity optimization. After validation, the method has been applied to the determination of carboxylic acids in apple, orange and lemon juices, white and red wines and musts during the fermenation process. 相似文献
1000.
Summary The chromatographic mobility of 21H, 23H-porphine and its Ni(II), Cu(II), Zn(II) and Pd(II) complexes were investigated by high-performance thin-layer chromatography on an octadecyl-bonded, silica gel plate with various polar organic solvents including alcohols, acetonitrile, dimethylsulfoxide and propylenecarbonate. The mobility generally decreases according to the central metal ion of the complex as follows: Zn(II)>(free porphine)>Ni(II)>Pd(II)>Cu(II). Methanol is a good choice of solvent for the separation of these metal porphine complexes. Successful separation of porphine and the four metal complexes is accomplished within 13 min on a LiChrosorb RP-18 column with methanol eluent. 相似文献