全文获取类型
收费全文 | 32996篇 |
免费 | 5900篇 |
国内免费 | 2587篇 |
专业分类
化学 | 20242篇 |
晶体学 | 550篇 |
力学 | 912篇 |
综合类 | 199篇 |
数学 | 972篇 |
物理学 | 10432篇 |
无线电 | 8176篇 |
出版年
2024年 | 75篇 |
2023年 | 269篇 |
2022年 | 503篇 |
2021年 | 612篇 |
2020年 | 925篇 |
2019年 | 984篇 |
2018年 | 923篇 |
2017年 | 1160篇 |
2016年 | 1424篇 |
2015年 | 1764篇 |
2014年 | 1892篇 |
2013年 | 3183篇 |
2012年 | 2252篇 |
2011年 | 2285篇 |
2010年 | 1870篇 |
2009年 | 1915篇 |
2008年 | 2057篇 |
2007年 | 1991篇 |
2006年 | 1855篇 |
2005年 | 1697篇 |
2004年 | 1595篇 |
2003年 | 1440篇 |
2002年 | 1385篇 |
2001年 | 999篇 |
2000年 | 1010篇 |
1999年 | 795篇 |
1998年 | 706篇 |
1997年 | 566篇 |
1996年 | 484篇 |
1995年 | 500篇 |
1994年 | 376篇 |
1993年 | 324篇 |
1992年 | 281篇 |
1991年 | 213篇 |
1990年 | 172篇 |
1989年 | 130篇 |
1988年 | 132篇 |
1987年 | 116篇 |
1986年 | 108篇 |
1985年 | 88篇 |
1984年 | 92篇 |
1983年 | 45篇 |
1982年 | 64篇 |
1981年 | 48篇 |
1980年 | 43篇 |
1979年 | 45篇 |
1978年 | 20篇 |
1977年 | 14篇 |
1976年 | 9篇 |
1973年 | 19篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
901.
In the present study a multi-residue analytical method was developed for monitoring some polar pesticides such as acephate,
methamidophos, carbofuran, isoproturon, dimethoate in water with SPE (solid-phase extraction) and LC–MS–MS. Acetochlor was
taken as surrogate, and alachlor as internal standard. SPE with different types of columns was compared with LLE (liquid-liquid
extraction). Further, the breakthrough volume for different pesticides was determined. The results showed that the selected
pesticides can be determined very sensitively with LC–MS–MS. The minimum detectable quantity (MDQ) for each pesticide was
about 1.0 ng. To date, SPE cartridge studies showed that the Oasis HLB cartridges were suitable for further studies. However,
for Oasis HLB cartridge, different pesticide showed different breakthrough volume. The results showed that for acephate and
methamidophos, the breakthrough volume was about 30 mL of water sample, much less than the breakthrough volume of other pesticides
studied. Because of the higher vapor pressure and higher Henry's constant of methamidophos, dimethoate and carbofuran, much
attention should be paid on their losses in the evaporation step of the experiment. This analytical method can be applied
to determine pesticide contamination in environmental water samples.
Revised: 12 September 2005 and 21 October 2005 相似文献
902.
With the combination of the the stoichiometric displacement model for retention (SDM-R) in reversed phase liquid chromatography (RPLC) and the stoichiometric displacement model for adsorption (SDM-A) in physical chemistry,the total number of moles of the re-solvated methanol of stationary phase side.nr,and that of solute side in the mobile phase,q,corresponding the one mole of the desorbing solute,were separately determined and referred as the characterization parameters of the contributions of the adsorption mechanism and partition mechanism to the solute retention,respectively.A chromatographic system of insulin,using mobile phase consisting of the pseudo-homologue of alcohols(methanol,ethanol and 2-propanol)-water and trifluoroacetic acid was employed.The maximum number of the methanol layers on the stationary phase surface was found to be 10.6,only 3 of which being valid in usual RPLC,traditionally referred as a volume process in partition mechanism.However,it still follows the SDM-R.Both of q and nr of insulin were found not to be zero,indicating that the retention mechanism of insulin is a mixed mode of partition mechanism and adsorption mechanism.When methanol is used as the organic modifier,the ratio of q/nr was 1.13,indicating the contribution to insulin retention due to partition mechanism being a bit greater than that due to adsorption mechanism.A linear relationship between q,or nr and the carbon number of the pseudo-homologue in the mobile phase was also found.As a methodology for investigating the retention mechanism retention and behavior of biopolymers.a homologue of organic solvents as the organic modifier in mobile phase has also been explored. 相似文献
903.
New uniform algorithm to predict reversed phase retention values under different gradient conditions
Wang Longxing 《Analytica chimica acta》2003,476(1):123-129
A new numerical emulation algorithm was established to calculate retention parameters in RP-HPLC with several retention times under different linear or nonlinear binary gradient elution conditions and further predict the retention time under any other binary gradient conditions. A program was written according to this algorithm and nine solutes were used to test the program. The prediction results were excellent. The maximum relative error of predicted retention time was less than 0.45%. 相似文献
904.
Egorochkin A. N. Voronkov M. G. Skobeleva S. E. Zderenova O. V. 《Russian Chemical Bulletin》2001,50(1):35-42
The first vertical ionization potentials (I) of phosphorus compounds P(Xi)3, OP(Xi)3, SP(Xi)3, (4-XC6H4)3P, and PCX are related to the inductive, resonance, and polarizability parameters of inorganic, organic, and organometallic substituents X by dependences of the type I = I
H + aI + bR
+ + c, where I
H is the I value for X = H. The I values are also affected by hyperconjugation. The ratio of the contributions of the resonance (bR
+) and polarizability (c) effects to the I value is determined by the degree of delocalization of the unpaired electron and the positive charge in the radical cations formed upon ionization of neutral molecules. The R
+ resonance parameters of organosilicon, organogermanium, and organotin substituents bound to the P
·+ radical cation center were calculated for the first time. 相似文献
905.
J. Šesták D. Sedmidubsky G. Moiseev 《Journal of Thermal Analysis and Calorimetry》1997,48(5):1105-1122
Thermochemical and thermodynamical properties of HTSC phases are reviewed for the Y-Ba-Cu-O system and also presented for the newly calculated Bi-Sr-Cu-O system stressing out stoichiometric and phenomenological viewpoints. Simulated data are listed for (H
298
o
-H
o
o
, phase transformation temperatures, standard entropies, standard enthalpies of formation, heat capacities in crystalline phase, etc. Pseudobinary phase diagrams are treated showing the effect of oxygen partial pressure particularly illustrated on the (Sr, Bi, Ba)-Cu-O system.The work was carried out under the project No. A 2010532 supported by the Grant Agency of Academy of Sciences of the Czech Republic and the grant No. 104/97/0589 financed by the Grant Agency of the Czech Republic. 相似文献
906.
Efficient Separation of Hydrophobic Molecules by Molecularly Imprinted Cyclodextrin Polymers 总被引:2,自引:0,他引:2
Hiroyuki Asanuma Takayuki Hishiya Makoto Komiyama 《Journal of inclusion phenomena and macrocyclic chemistry》2004,50(1-2):51-55
Cyclodextrins were cross-linked with toluene 2,4-diisocyanate in dimethyl sufoxide in the presence of hydrophobic biomolecules as templates, and the imprinted polymers were applied to the stationary phases of high performance liquid chromatography. Molecular imprinting efficiently promoted the binding-affinity and substrate-selectivity towards the template molecule, compared with the control polymers prepared in their absence. When cholesterol (template molecule) was complexed with cyclodextrins prior to the polymerization, for example, the imprinted polymer retained cholesterol more strongly than other steroids. Upon the polymerization without a template molecule, the binding towards steroids was much weaker. Besides steroids, imprinting was effective for various hydrophobic and rigid template molecules. Since binding of the guest molecule was based on inclusion complex formation with cyclodextrins, separation could be achieved in the solvents containing water. These polymeric receptors are also applicable to selective recognition of biologically important molecules or removal of toxic molecules from aqueous media. Thus, imprinting of cyclodextrins is useful for the preparation of synthetic tailor-made receptors for various kinds of hydrophobic guest molecules. 相似文献
907.
Different physical chemical methods were used to study the thermochemical processes in a system involving a natural phosphate and complex acid salts of ammonium sulphate. The products of decomposition of the double ammonium salt and the products of their interactions with the phosphate were identified. The formation of ammonium and calcium polyphosphates and the disproportionation of P3O 10 5? and P2O 7 4? to PO 4 3? and PO 3 ? were found to depend on the circumstances of the thermal interactions. 相似文献
908.
茉莉醛相转移催化合成法的改良 总被引:4,自引:0,他引:4
茉莉醛又称2-戊基肉桂醛,具有优雅的茉莉花香,是一种深受调香师喜爱的合成香料。目前已广泛应用于各种日用化学品中。 相似文献
909.
The leaching of two estrogens, 17β-estradiol and estrone, and two degradation products of non-ionic surfactants, octylphenol and nonylphenol, through a soil column were studied to estimate their transport behavior. Different concentration methods (lyophilization, solid phase extraction, and liquid–liquid extraction) were evaluated for analyzing these compounds in small effluent fractions (30–50 mL) collected. Liquid chromatography-mass spectrometry (LC-MS-MS) and gas chromatography-mass spectrometry (GC-MS) were employed for quantitative analysis of these compounds. After comparison, the lyophilization-LC-MS-MS method was found to be best suited for the analysis of the two estrogen hormones and the liquid–liquid extraction-GC-MS method best for the analysis of the two phenols in small samples in the soil column study. Because of their high sorption capacity, these compounds were mostly sorbed in the upper part of the soil column and were difficult to detect in column effluent. 相似文献
910.
O. Slisenko E. Lebedev P. Pissis A. Spanoudaki E. Kontou O. Grigoryeva 《Journal of Thermal Analysis and Calorimetry》2006,84(1):15-19
The structure-property relationships of thermoplastic
polymer blends based on poly(ether-urethane) ionomer (PEUI) and ion-containing
styrene-acrylic acid copolymer (S-co-AA(K))
have been investigated by using DMTA, DSC and TGA, as well as tensile tests.
Convergence of the glass transition temperature (Tg)
values of the PEUI and the S-co-AA(K) components
in the blends studied, as compared to the individual polymers, was found and
explained by improving compatibility of the components due to increasing effective
density of physical networks formed by ion-dipole and ion-ion interactions
of ionic groups of the components. Character of E'=f(T) and E'=f(T) dependencies confirms the increase of the effective
density of physical networks in the compositions studied compared to individual
PEUI and S-co-AA(K). Improvement of end-use
properties, i.e. thermal stability and tensile properties has been found for
the PEUI/S-co-AA(K) compositions with lower
content of S-co-AA(K) (i.e. <10 mass%)
and explained by formation of additional network of intermolecular ionic bonds
between the functional groups of PEUI and S-co-AA(K). 相似文献