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31.
Brown coals have a considerable number of acidic functional groups of which the main component is carboxyl groups, and the acidity has a wide distribution. In this paper, changes of the acidity distribution were examined by aqueous titration when brown coal was heat-treated to control its acidity distribution. For Loy Yang brown coal from Australia dried at 50 degrees C under vacuum (LY50), the acid dissociation constant, Ka, was distributed over a wide pKa range between 2 and 9. Then, using Gaussian functions, the acidity distribution was divided into four groups, which were characterized by average pKa values: average pKa value of 3.8 (hereafter referred to as Group A), 5.2 (Group B), 6.8 (Group C), and 8.3 (Group D). Among them, Groups A, B, and C were assigned to carboxyl groups. From the changes of the number of carboxyl groups when brown coal was heat-treated up to 400 degrees C, it was found that the way of decrease was different among these acidic groups. The decrease of the amount of carboxyl groups in Group C was significant, and at 325 degrees C most of them disappeared. On the other hand, the carboxyl groups in Group A remained even at a high temperature of 400 degrees C. We estimated approximately the structures around carboxyl groups for LY50 and their structural changes by heat treatment using the known pKa values for simple carboxylic acids and the pKa values calculated by the MOPAC program for complicated carboxylic acids. 相似文献
32.
Kondo T Kaneko Y Taguchi Y Nakamura A Okada T Shiotsuki M Ura Y Wada K Mitsudo TA 《Journal of the American Chemical Society》2002,124(24):6824-6825
Pyranopyrandiones were prepared by a novel ruthenium-catalyzed carbonylative dimerization of cyclopropenones via C-C bond cleavage. For example, treatment of dipropylcyclopropenone with a catalytic amount of Ru3(CO)12 and NEt3 in THF under 15 atm of carbon monoxide at 140 degrees C for 20 h gave a novel functional monomer, 3,4,7,8-tetrapropylpyrano[6,5-e]pyran-2,6-dione, in an isolated yield of 81%. Unsymmetrically substituted pyranopyrandiones were also obtained by ruthenium-catalyzed carbonylative coupling of cyclopropenones with alkynes under similar reaction conditions. 相似文献
33.
Summary A study is made of the mechanism of hemolysis by anionic surface-active agents. It is supposed that the primary site of the hemolytic attack by anionic agents is the protein moiety of the red cell membrane at physiological pH. The role of phospholipid release in hemolysis increases as the PH of the medium decreases.
Zusammenfassung Der Mechanismus der Hämolyse durch anionische oberflächenaktive Agentien wurde untersucht. Es ist anzunehmen, daß primär der hämolytische Angriff durch anionische Agentien beim physiologischen PH am Proteinteil der Erythrozyt-Membran zu suchen ist. Mit der Abnahme des PH des Mediums spielt die Phospholipid-Freistellung bei der Hämolyse eine immer größere Rolle.相似文献
34.
Sulfate ion in river water is determined by flow injection analysis at a rate of 30 samples per hour; the sulfate contents are typically less than 30 ppm. The reagent solution contains dimethylsulfonazo-III, barium chloride, potassium nitrate and chloroacetate buffer in 70% () ethanol, and is saturated with barium sulfate. The aqueous carrier stream is also saturated with barium sulfate. The sample is filtered and treated with Amberlite IR120-B cation-exchanger before injection into the carrier stream, and the decoloration of the barium—dimethylsulfonazo-III complex by sulfate is measured at 662 nm. The calibration graph is linear over the range 0–30 μg ml-1 for sulfate in water. 相似文献
35.
Tsutomu Kagiya Shizuo Narisawa Taizo Ichida Kenichi Fukui Hisao Yokota Masatsune Kondo 《Journal of polymer science. Part A, Polymer chemistry》1966,4(2):293-299
The copolymerization of carbon monoxide and aziridines such as ethylenimine and propylenimine was carried out by γ-ray irradiation. Aziridines and carbon monoxide were allowed to copolymerize under γ-ray irradiation from a Co60 source and gave a crystalline solid copolymer. The yield of the copolymer increased with reaction temperature. The composition of copolymers obtained did not depend on the feed ratio of monomers and was found to be almost equimolar. The copolymer of ethylenimine and carbon monoxide melted at about 322–335°C. with decomposition and has an infrared spectrum identical with that of poly-β-alanine obtained by the hydrogen-migration polymerization of acrylamide. The hydrolyzed product of the ethylenimine–carbon monoxide copolymer was confirmed to be β-alanine by paper chromatography. These results lead to the conclusion that the copolymerization of aziridines and carbon monoxide took place alternatively by γ-ray irradiation, and produced crystalline poly-β-alanines. 相似文献
36.
Ginting Suka IrwanShin-ichi Kuroda Hitoshi Kubota Takashi Kondo 《European Polymer Journal》2002,38(6):1145-1150
The effect of monomer concentration on photografting of methacrylic acid (MAA) onto linear low-density polyethylene (PE) film (thickness=30 μm) was investigated at 60 °C in water solvent together with the location of MAA-grafted chains. Xanthone was used as a photoinitiator which was coated on the film sample earlier. The higher percentage of grafting and graft efficiency were afforded for the system with the higher monomer concentration. The resultant MAA-grafted films were subjected to measurements of pH-responsive character and ability to adsorb cupric ion in order to understand the characteristics of function introduced. The grafted samples exhibited the pH-responsive character, where they shrank and swelled in acidic and alkaline media, respectively. The pH-responsive character of the grafted films was higher for the samples prepared in the system with a higher monomer concentration. Moreover, the grafted samples exhibited the ability to adsorb cupric ion, and the ability was reduced when the sample was prepared in the system with a higher monomer concentration. The different extents of the pH-responsive character and ability to adsorb cupric ion of the resulting grafted PE films were discussed in terms of location of grafted chains in the film substrate, which was determined by a scanning electron microscope and an attenuated total reflection infrared spectroscopy. 相似文献
37.
Dosimetry of fast neutrons in 1W nuclear reactor with plastic nuclear-track detectors 总被引:1,自引:0,他引:1
A nuclear reactor at Kinki University is operated at the maximum of 1W. It produces fission neutrons as much as gamma-rays. To facilitate its use for neutron radiobiology, fast neutrons inside the reactor were measured with nuclear-track detectors TS 16 N and a pair of ion chambers. The angular dependence of TS 16 N response, an anisotropy of fast neutron fluxes in the reactor and misuse of the kerma factor assumed for radiation protection business are the major causes of discrepancy is measured doses by the two methods. Correction factors for the three causes are proposed. After correction, neutron doses estimated with TS 16 N and chambers agree within 5%. The dose-rate at the reactor's center is about 20 tissue-cGy/h. This is the first in situ dosimetry of fast neutrons in a reactor with track detectors attached to biologic samples. Our routine usage has demonstrated that, if used with caution, TS 16 N elements are handy, reliable monitors for fast neutron dosimetry as they are insensitive to contaminated gamma-rays and small enough to be attached to biologic samples. 相似文献
38.
The relationship between the chemical structure of nematic liquid crystals and their pretilt angles 总被引:1,自引:0,他引:1
About 50 different additives in one or more of three different nematic mixtures have been investigated to clarify the relationship between the chemical structure of the liquid crystal and the pretilt angle on a polyimide surface. The pretilts found for cells have been explained within our recently proposed population distribution model. For compounds with cyano-groups at one end, we find that the in-plane order is governed both by the surface-mesogen interaction and by the relative strength of the intermolecular interactions in the nematic phase. This strength is nearly linear in alkyl chain length for the compounds investigated. Changes in the strength due to variations in the core of the molecules can be calculated easily by using group contributions from the known Parachors. The in-plane order can be treated as a simple product of the contributions from the liquid crystal and from the polyimide. Different polar end groups will give different angles between the surface and the optical axis of the individual mesogens in the first monolayer. The cyano-group gives the highest angle and alkyl groups the lowest. For nitro-compounds the dimers formed are so strongly bound that they do not break up at the surface. Nitro-compounds will thus act as dialkyl compounds. For dialkyl compounds the pretilt angles are dominated by the difference between the chain lengths at the two ends of the molecule. 相似文献
39.
40.
Hamada Fumio Kondo Yoshihiko Ito Riko Suzuki Iwao Osa Tetsuo Ueno Akihiko 《Journal of inclusion phenomena and macrocyclic chemistry》1993,16(3):273-281
The crystal structure of thiamine iodide sesquihydrate has been determined by X-ray diffraction methods as a host-guest model for coenzyme-substrate interactions. The asymmetric unit contains two chemical units. Both the thiamine molecules A and B, which are crystallographically independent, assume the usualF conformation and have a disordered hydroxyethyl side chain. An iodide anion (or a water molecule) bridges the pyrimidine and thiazolium rings of molecule A (or B) by forming a hydrogen bond with the amino group and an electrostatic contact with the thiazolium ring to stabilize the molecular conformation. In the crystal the thiamine molecules self-associate to form a pipe-like polymeric structure, in which four thiamine hosts surround an iodide guest and hold it through C(2)-H...I hydrogen bonds and thiazolium...I electrostatic interactions. Crystal data: C12H17N4OS+·I– · 1.5 H2O, monoclinic,P21/c, a=12.585(2), b=25.303(5), c=12.030(2) Å, =115.15(1)°,V=3468(1) Å3,Z=8,D
c=1.606 g cm–3,R=0.045 for 3328 observed reflections.
Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP. 82156 (13 pages). 相似文献