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841.
A. P. Gulea S. N. Spynu V. I. Tsapkov D. Poirier J. Roy 《Russian Journal of General Chemistry》2006,76(9):1458-1463
Isatin (L1) and N-methylisatin (L2) β-thiosemicarbazones react in ethanol with Cu(II) chloride and bromide in the presence of sulfanilamide (Streptocid, Sf1), N-acetylsulfanilamide (Sulfacyl, Sf2), Norsulfazole (Sf3), Aethazolum (Sf4), and Sulfadimesine (Sf5) to form coordination compounds Cu(Sf1–5)L1–2X2 · nH2O (X = Cl, Br; n = 2–5). All the complexes have a monomeric structure. Thiosemicarbazones L1 and L2 in these complexes are tridentate O,N,S ligands, and sulfanilamides Sf1–5 are monodentate ligands. Thermolysis of the substances involves the steps of dehydration (70–95°C) and complete decomposition (410–530°C). 相似文献
842.
Summary Chemiluminescent reactions of ozone with several classes of compounds at different temperatures are described. In a reaction chamber in front of a photomultiplier ozone is mixed with the compounds studied such as alkanes, olefins, alcohols, aromatics, C2H2, NO, vinyl chloride or H2S. The chemiluminescent emission is proportional to the concentration of the compound involved. At room temperature only olefinic hydrocarbons respond but at temperatures above 150°C also a response for alkanes, alcohols, CO etc. is obtained. It is suggested that next to the ozonide-excited formaldehyde mechanism the CO-CO
2
*
mechanism is responsible for the chemiluminescent emission at high temperature. A detection limit of a few ppb is achieved. Possible applications are a selective gas-chromatographic detector, an air pollution monitor for instance for CO, and a photochemical reactivity monitor.
Bestimmung reaktiver Kohlenwasserstoffe durch Chemiluminescenz
Zusammenfassung Chemiluminescenzreaktionen von Ozon mit verschiedenen Verbindungsgruppen (hauptsächlich Kohlenwasserstoffe) bei unterschiedlichen Temperaturen werden beschrieben. In einer Reaktionskammer werden die Verbindungen vor einem Photomultiplier mit Ozon vermischt. Es handelt sich u. a. um folgende Verbindungstypen: Alkane, Olefine, Alkohole, Aromaten, C2H2, NO, Vinylchlorid, H2S. Die Emissionsintensität ist proportional der Konzentration. Bei Raumtemperatur sprechen nur Olefine an, die übrigen Verbindungen erst über 150°C. Die Emission bei höherer Temperatur wird neben der Bildung von Formaldehyd auf die Reaktion CO-CO 2 * zurückgeführt. Die Nachweisgrenze beträgt wenige ppb. Als mögliche Anwendungsgebiete werden ein selektiver GC-Detektor, ein Monitor für Luftverunreinigungen (z.B. für CO) sowie ein Monitor zur Messung photochemischer Reaktivität der Luft genannt.
Presented at the 6th Annual Symposium on Recent Advances in the Analytical Chemistry of Pollutants, April 21–23, 1976; Vienna, Austria. 相似文献
843.
A good agreement has been observed between the proton longitudinal relaxation rate in the two and one layer hydrate of the Na-Llano vermiculite, the location of the Fe3+ paramagnetic centers within the octahedral and tetrahedral layers of the lattice and the electronic longitudinal relaxation rate using the dipolar electronic—proton spin interaction. The water content influences noticeably the electronic longitudinal relaxation time. 相似文献
844.
Closed-shell and DODS CNDO/2 calculations have been performed for neutral and charged TCNQ and TTF monomers and different dimers. For the sake of comparison the calculation have also performed for the corresponding TCNE molecules.The most important result obtained indicates a large splitting of the lowest unfilled level of TCNQ in going from the monomer to the stacked (TCNQ)2 dimer. The same holds true for the HOMO level of the (TTF)2 dimer. This indicates that one should expect a broad conduction band for the neutral poly (TCNQ) chain and a broad valence band for the neutral poly (TTF) chain. In order to test the quality of the CNDO/2 approximation scheme a comparison is attempted with existing experimental findings as well as with some MINDO results and available theoretical predictions within different approximation schemes. 相似文献
845.
Different transformations of the functions fixed on a heterocyclic molecule were made. It is thus possible to quickly determine the number of functions of each type present in the molecule: e.g. (i) all the functions are silylated and (ii) the alcohols are acetylated whilst the sulfates and acids are silylated. Mass spectra of atractylate, apoatractylate and gummiferine have been studied and the substituents are counted and enumerated. 相似文献
846.
E. J. Baran 《Monatshefte für Chemie / Chemical Monthly》1973,104(6):1653-1659
The mean amplitudes of vibration of ICl2
–, IBr2
–, BrCl2
– and ClF2
– have been calculated, from known spectroscopic data, in the temperature range between O° and 1000°K. Also generalized mean-square amplitudes and values for theBastiansen—Morino shrinkage effect are reported. The results are briefly discussed.
Mit 1 Abbildung 相似文献
Mit 1 Abbildung 相似文献
847.
A new method is proposed for routine determinations of oxidizable and reducible substances. A mathematical development and criticism of the method of Schierjott has led to a fundamental modification of the earlier experimental conditions (ratio of the oxidized/reduced forms of the reagent at the start and end of the redox reaction). This improvement allows a considerable increase in the sensitivity of the method and is particularly advantageous for the determination of substances of low reactivity, e.g. carbohydrates. Other advantages are a reduction in the quantity and thus cost of the necessary reagent, and a decreased risk of precipitation of the substances involved. The mathematical treatment of the proposed version allows a rigorous theoretical comparison of the two methods. An evaluation of the quality of the approximations introduced into both methods is also proposed, based on the calculation of the deviation (absolute and relative differences) of approximated values from theoretical values. The final part of the work deals with optimization of the different principal parameters, i.e. concentration of the reagent, temperature and reaction time. 相似文献
848.
Two C-lactosyl lipids and the related C-galactosyl lipids have been synthesised and their binding to RCA120 plant lectin was compared with a second series of thiolactosylethoxyalkanes. The interactions were measured quantitatively in real time by surface plasmon resonance (BIAcore) at a range of concentrations and temperatures from 5 to 30 degrees C. The C-galactosyl lipid (1,3-dimethyl-5-[beta-D-galactopyranosyl]-5-(4-octadecyloxybenzyl)pyrimidine-2,4,6-trione) bound much more weakly with a K(A) = 8.86 x 10(5) than the corresponding C-lactosyl lipid (1,3-dimethyl-5-[beta-D-galactopyranosyl-(1 --> 4)-beta-D-glucopyranosyl]-5-(4-octadecyloxybenzyl)pyrimidine-2,4,6-trione) (K(A) = 2.31 x 10(7)). The influence of the linker region of the two different series of lactosyl lipids was clearly demonstrated by the differences in the binding to RCA120 lectin. The changes in kinetic values and in the enthalpic and entropic contribution to the free energy of binding reflected the importance of the linker and the hydrocarbon anchor holding the synthetic glycolipids in the neomembrane. 相似文献
849.
A Diels-Alder reaction of novel inner-outer-ring 1,3-silyloxydienes 5-8 with a variety of dienophiles to afford highly functionalized polycyclic structures is reported. The inner-outer-ring 1,3-silyloxydienes 5-8 containing five- to seven-membered carbocyclic and heterocyclic rings were prepared in a single reaction vessel from 2-acetylcyclocarbonyls in quantitative yields. The Diels-Alder reaction with 1,4-benzoquinone (BQ), dimethyl acetylenedicarboxylate (DMAD), and methyl vinyl ketone (MVK) proceeded smoothly at room temperature, affording functionalized polycyclic naphthols, phenols, and enones with high regioselectivity and good yields (39-75%). Moreover, dienes 5-8 also reacted in a hetero-Diels-Alder reaction with benzaldehyde (BA) and N-benzylideneaniline (NBA) in the presence of catalytic amounts of ZnCl2, affording substituted polycyclic pyranones and pyridinones in good yields (40-93%). Overall, our synthetic strategy provides straightforward access to an interesting set of polycyclic structures useful for natural and nonnatural product synthesis. 相似文献
850.
M S Patterson S J Madsen B C Wilson 《Journal of photochemistry and photobiology. B, Biology》1990,5(1):69-84
Singlet oxygen (1O2) is thought to be the cytotoxic agent in photodynamic therapy (PDT) with current photosensitizers. Direct monitoring of 1O2 concentration in vivo would be a valuable tool in studying biological response. Attempts were made to measure 1O2 IR luminescence during PDT of cell suspensions and two murine tumour models using the photosensitizers Photofrin II and aluminium chlorosulphonated phthalocyanine. Instrumentation was virtually identical to that devised by Parker in the one positive report of in vivo luminescence detection in the literature. Despite the fact that our treatments caused cell killing and tissue necrosis, we were unable to observe 1O2 emission under any conditions. We attribute this negative result to a reduction in 1O2 lifetime in the cellular environment. Quantitative calibration of our system allowed us to estimate that the singlet oxygen lifetime in tissue is less than 0.5 microsecond. Some technical improvements are suggested which would improve detector performance and perhaps make such measurements feasible. 相似文献