全文获取类型
收费全文 | 4291篇 |
免费 | 106篇 |
国内免费 | 13篇 |
专业分类
化学 | 3147篇 |
晶体学 | 13篇 |
力学 | 97篇 |
数学 | 576篇 |
物理学 | 577篇 |
出版年
2023年 | 25篇 |
2022年 | 30篇 |
2021年 | 31篇 |
2020年 | 50篇 |
2019年 | 40篇 |
2018年 | 31篇 |
2017年 | 26篇 |
2016年 | 110篇 |
2015年 | 90篇 |
2014年 | 77篇 |
2013年 | 173篇 |
2012年 | 183篇 |
2011年 | 275篇 |
2010年 | 135篇 |
2009年 | 139篇 |
2008年 | 260篇 |
2007年 | 217篇 |
2006年 | 220篇 |
2005年 | 204篇 |
2004年 | 199篇 |
2003年 | 136篇 |
2002年 | 125篇 |
2001年 | 79篇 |
2000年 | 78篇 |
1999年 | 55篇 |
1998年 | 52篇 |
1997年 | 68篇 |
1996年 | 64篇 |
1995年 | 66篇 |
1994年 | 80篇 |
1993年 | 75篇 |
1992年 | 49篇 |
1991年 | 57篇 |
1990年 | 51篇 |
1989年 | 50篇 |
1988年 | 62篇 |
1987年 | 43篇 |
1986年 | 45篇 |
1985年 | 64篇 |
1984年 | 46篇 |
1983年 | 47篇 |
1982年 | 48篇 |
1981年 | 54篇 |
1980年 | 33篇 |
1979年 | 33篇 |
1978年 | 23篇 |
1977年 | 32篇 |
1976年 | 35篇 |
1975年 | 33篇 |
1973年 | 22篇 |
排序方式: 共有4410条查询结果,搜索用时 15 毫秒
61.
19F nuclear magnetic resonance studies on imidosulphuroxide difluorides Non equivalent fluorine atoms bounded to hexavalent sulphur of the NSOF2 group in thionyl compounds give extreme AB-spectra. 相似文献
62.
Binding of bis-picolylamine-naphthalene diimide-peptide nucleic acid conjugates to complementary DNA is strongly dependent upon Zn2+; ultimately, hybridization is switched ON in the presence muM Zn2+. 相似文献
63.
Marzouki SM Limam F Smaali MI Ulber R Marzouki MN 《Applied biochemistry and biotechnology》2005,127(3):201-214
Analysis of peroxidase activity by native polyacrylamide gel electrophoresis (PAGE) from a garlic bulb (Allium sativum L) extract showed two major activities (designated POX1 and POX2). The POX2 isoenzyme was purified to homogeneity by ammonium sulfate precipitation, gel filtration, and cation-exchange chromatography. The purified enzyme was found to be monomeric with a molecular mass of 36.5 kDa, as determined by sodium dodecyl sulfate-PAGE. The optimum temperature ranged from 25 to 40 degrees C and optimum pH was about 5.0. The apparent Km values for guaiacol and H2O2 were 9.5 and 2 mM, respectively. POX2 appeared highly stable since 50% of its activity was conserved at 50 degrees C for 5 h. Moreover POX2 was stable over a pH range of 3.5-11.0. Immobilization of POX2 was achieved by covalent binding of the enzyme to an epoxy-Sepharose matrix. The immobilized enzyme showed great stability toward heat and storage when compared with soluble enzyme. These properties permit the use of this enzyme as a biosensor to detect H2O2 in some food components such as milk or its derivatives. 相似文献
64.
Organophosphorus pesticides are commonly used in both agricultural and residential settings. The widespread use of these chemicals makes it almost impossible for humans to avoid exposure. In order to determine background human exposure, there is a need for fast, reliable, and sensitive analytical methods. We have developed a sensitive method to quantify specific biomarkers of the organophosphorus pesticides acephate, azinphos, chlorpyrifos, coumaphos, diazinon, isazofos, malathion, methamidophos, parathion and pirimiphos or their O,O-dimethyl analogues in human urine, as their selective metabolites or as the intact pesticide. Isotopically labeled internal standards were used for eight of the analytes. The use of labeled internal standards in combination with high-performance liquid chromatography electrospray ionization–tandem mass spectrometry provided a high degree of specificity. Repeated analysis of urine samples fortified with high and low concentrations of the analytes gave relative standard deviations (RSD) of less than 10% for the analytes with an isotopically labeled standard. Analytes without isotopically labeled standards had higher RSD. For all compounds except methamidophos and acephate, the recoveries were greater than 70%. The limits of quantification for most of the analytes were in the range of 0.1 to 1 ng/mL. We detected concentrations of most of these pesticides and/or their metabolites in urine samples from non-occupationally exposed persons using our method. Our frequencies of detection for the analytes measured ranged from 1% to 98%. 相似文献
65.
Olsson M Joabsson F Piculell L 《Langmuir : the ACS journal of surfaces and colloids》2005,21(4):1560-1567
The influence of added colloidal particles on the phase separation of mixed aqueous polymer solutions is investigated. Two types of particles (polystyrene latex or silica) and different combinations of segregating polymers (dextran of varying molar mass combined with poly(ethylene oxide) (PEO) of varying molar mass, or Ucon, a copolymer of ethylene oxide and propylene oxide) were used. All systems displayed particle-induced instability effects, but the extent of the effect varied strongly between the various combinations and with the amount of added salt. Very large instability effects were seen in certain mixtures. Two mechanisms, both relying on the adsorption of at least one of the polymers to the particle surface, seem to operate. Close to the cloud-point curve of the particle-free polymer1/polymer2/water mixture, adsorption of PEO or Ucon to the particles gives rise to a capillary-induced phase separation. Close to the dextran/water axis of the phase diagram, the adsorbing polymer gives rise to a surface modification of the particles, which then interacts repulsively with the surrounding dextran solution. 相似文献
66.
The N,N-diisopropylaminomethyl aluminium compound [tBu2AlCH2NiPr2 x LiCl]2(1) and the gallium compounds Li[tBu2Ga(CH2NiPr2)2](2) and [tBu2GaCH2N(H)iPr2]Cl x tBu3Ga (3) were prepared by transmetallation of N,N-diisopropylaminomethyllithium LiCH2NiPr2 with di-tert-butylaluminium or -gallium chloride, and characterised by elemental analyses, multinuclear NMR spectroscopy (1H, 13C, 27Al, 7Li) and IR spectroscopy. The crystal structures have been determined by single crystal X-ray diffraction. Compound aggregates as a centrosymmetric dimer, with two Al-C-N units connected by a frame of two LiCl molecules [Al-Cl 2.367(1), Cl-Li 2.339(4) and 2.374(4), Li-N 1.977(4)A]. Compound 2 is a lithium organogallate with two weak LiN bonds [1.965(7) and 1.937(7)A]. Compound 3 contains two different moieties: tBu3Ga and a [tBu2GaCH2N(H)iPr2]+ cation, which are bridged by a Cl- anion [Ga-Cl 2.445(1) and 2.579(1), HCl 2.362(3)A]. 相似文献
67.
Detlef Schrder Jessica Loos Helmut Schwarz Roland Thissen Jana Roithova Zdenek Herman 《International journal of mass spectrometry》2003,230(2-3):113
Singly and doubly charged C4H3+/2+ ions generated upon electron ionization (EI) of the neutral precursors 1,3-butadiene, benzene, and exo-methylene cyclopropane, respectively, are examined by sector-field mass-spectrometry. Charge stripping of the mass-selected monocations affords the corresponding dications and charge exchange of the C4H32+ dications allows for the reverse redox process. Refined analysis and additional MS/MS studies suggest that the monocations are mixtures of isomeric ions formed upon ionization, whereas only a single type of dication seems to be formed. As an average of energy-resolved measurements, a vertical ionization energy of IEv(C4H3+)=16.5±0.4 eV is derived. In addition to the experimental work, density functional theory is used for a computational exploration of the mono- and dicationic species. The best theoretical estimates are IEa(C4H3+)=16.33 eV and IEv(C4H3+)=16.49 eV for the most stable isomer H2C=C---CCH+. Combination of the experimental and theoretical findings leads to the conclusion that the diacetylene cation C4H2+ has indeed a positive proton affinity of PA(C4H2+)=1.50±0.42 eV. 相似文献
68.
The In-flame detector earlier applied to the specific chlorine (359.9 nm) and bromine (372.7 nm) analysis has now been employed for the iodine determination at 409.9 nm. It is shown that the resolution power of a GC column can be improved by such a specific detector. After calibration quantitative measurements of the iodine contents of the GC fractions are possible. The detection limits are 0.01–1.4 μg of iodine. 相似文献
69.
Hydrogen peroxide is determined by a chemiluminescence method with a reagent containing 100 μM luminol and 3 μM microperoxidase at pH 10 (carbonate buffer). Microperoxidase is superior to hematin as a catalyst. The method uses an automated flow injection system with a throughput of 2 samples per minute. The log—log calibration plot is linear (slope 1.3) from the detection limit, 3 × 10-9 M up to 10-5 M H2O2. The background emission is low. Impurities in the carrier stream and from some plastics may cause elevated background unless precautions are taken. 相似文献
70.
Roland Sandn 《Journal of polymer science. Part A, Polymer chemistry》1985,23(8):2279-2281
Mixing and curing experiments with suspensions of boron in hydroxyl-terminated polybutadiene (HTPB) have been performed. In kneading experiments on a plastograph very high viscous masses with bad curing properties were obtained. The experiments indicated that HTPB is attached with its OH groups to acidic impurities on the surface of the boron powder. By adding a basic substance, such as octadecyl amine, mixing and curing were undertaken with much less difficulty. 相似文献