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排序方式: 共有1210条查询结果,搜索用时 432 毫秒
61.
Die in hochaufgelösten Protonenresonanzspektren von 15N-markierten Pyrimidinderivaten infolge der indirekten Spin-Spin-Kopplung zwischen 15N und dem um zwei Bindungen entfernten Proton auftretenden Aufspaltungen liefern Aussagen über den Ort der Markierung im Pyrimidinring. Quantitative Angaben über die relative Häufigkeiten von 15N in diesen Positionen werden unter Verwendung der Rechentechnik erhalten. Die Ergebnisse über die relative Häufigkeiten von 15N im gesamten Molekül stimmen gut mit den massenspektrometrischen Werten überein. 相似文献
62.
Using chemical separations and radiometric measurements medium-half-life irradiation products of molybdenum with 12.5 MeV deuterons were determined (90Nb, 92Nb, 95mNb, 95Nb, 96Nb, 99Mo, 95mTc, 96Tc, 99mTc) as well as thick target yields for some of them: 92Nb (0.22 μCi/μAh), 95Nb(0.05 μCi/μAh), 99Mo (64 μCi/μAh), 95mTc(0.76 μCi/μAh), 96Tc((62.5 μCi/μAh). Moreover isolation possibiities of radioactive preparations from removed worn-cut molybdenum parts of the U-120 cycletron are discussed. 相似文献
63.
Although terminal chalcogeno ligands are well known for the group 5 and 6 transition metals, they are highly unusual for the oxophilic group 4 metals and unknown so far for the lanthanides or actinides. Cs3UP2S8, is the first actinide compound containing a terminal M=S group. It was synthesized by reacting uranium metal, Cs2S, S, and P2S5 in a 4:1:8:3 ratio at 700 °C in an eutectic LiCl/CsCl mixture. The crystal structure was determined by single‐crystal X‐ray diffraction techniques. Cs3UP2S8 crystallizes in the rhombohedral space group R$\bar{3}$ [a = 15.5217(8) Å; c = 35.132(2) Å, V = 8305.0(8) Å3, Z = 18]. The crystal structure is based on a tetrahedral network type, wherein the uranium atoms are coordinated by a unusual sulfido moiety and thiophosphate groups in a pseudo‐tetrahedral fashion. The U=S distance of 2.635(3) Å observed in the sulfide moiety is approx. 0.2 Å shorter than the average U–S single bond length, indicating a double‐bond type character. 相似文献
64.
Jan Schwarzbauer Larissa Dsikowitzky Sabine Heim Ralf Littke 《International journal of environmental analytical chemistry》2013,93(6):349-364
This study describes the application of a common analytical procedure adapted for compound-specific stable carbon isotope analyses of riverine contaminants. To evaluate the sensitivity of the analytical method and the precision of the isotopic data obtained, a set of numerous substances at different concentration levels were measured. For most of the anthropogenic contaminants investigated (including chlorinated aliphatics and aromatics, musk fragrances, phthalate-based plasticizers and tetrabutyl tin) acceptable carbon isotope analyses could be obtained down to amounts of approximately 5?ng absolutely applied to the gas chromatograph. These amounts correspond to concentrations in water samples at a natural abundance level of approximately 50–200?ng?L?1 (low to medium contaminated river systems). However, it has to be considered that the precision and the sensitivity of the analytical method depend partially on the chemical properties of the substances measured. Five recovery experiments were conducted to assess changes in carbon isotope ratios during sample preparation and measurement. The compounds selected for these experiments are known riverine contaminants. Isotopic shifts or higher variations of the isotope ratios as a result of the analytical procedures applied were observed only for a couple of contaminants. Furthermore, compound-specific carbon isotope analyses were performed on eight water extracts of the Rhine river. By comparing the variation of the data of several individual compounds with the deviations obtained from the recovery experiments, it was possible to differentiate contaminants with unaffected isotope ratios and substances with significant alterations of the δ13C-values. 相似文献
65.
Sarata Kumar Sahoo Yuji Nakamura Kunio Shiraishi Akimasa Masuda 《International journal of environmental analytical chemistry》2013,93(12):919-926
A chemical and mass-spectrometric procedure for uranium isotopic analysis using a thermal ionisation mass spectrometer equipped with a Wide Aperture Retardation Potential energy filter has been developed and applied to uranium isotopic measurements for various soil samples. Soil samples were digested using a microwave digestor. Uranium was isolated from soil samples by the chemical separation procedure based on the use of anion-exchange resin and UTEVA extraction chromatography column. The isotope ratios were measured for two certified reference materials by using a VG Sector 54-30 thermal ionisation mass spectrometer in dynamic mode with Faraday cup and Daly ion counting system. Replicates of standard reference materials showed excellent analytical agreement with established values supporting the reliability and accuracy of the method. Precision of the 235U/238U ratio was achieved by a correction factor of 0.22% amu as a function of ion-beam intensity with sample loads of around 250?ng of U. The resulting reproducibility for standards and soil samples was better than 0.2% at two standard deviations (SD). Uranium isotopic compositions have been determined in several reference soil samples such as Buffalo river sediment, NIST 2704, river sediment SRM 4350b and ocean sediment NIST-4357 and a Chernobyl soil sample. There was a significant deviation from the natural uranium in comparison with Chernobyl soil samples. 相似文献
66.
R. M. Cassidy S. Elchuk 《International journal of environmental analytical chemistry》2013,93(3-4):287-294
Abstract The potential of high-performance liquid chromatography (HPLC) for the determination of U(VI) in ground waters and urine has been examined under a variety of HPLC experimental conditions. Conventional cross-linked and bonded-phase ion exchangers, both cation and anion, were studied with aqueous mobile phases containing tartrate, citrate, or α-hydroxyisobutyrate. The best chromatography was obtained on bonded-phase cation exchangers with an α-hydroxyisobutyrate eluent. The metal ions were detected either by visible spectrophotometry after a post-column reaction with a complexing reagent, or with a polarographic detector. Dectection after post-column reaction gave the best sensitivity; the detection limit (2 × baseline noise was 6 ng or 60 ng.ml?1 for 100 μl samples. In-line trace enrichment was used to decrease detection limits and linear calibration curves were observed in the ranges studied; 0.5 to 50 ng.mL?1 for ground waters and 25 to 400 ng.mL?1 for artificial urine. 相似文献
67.
Neven Cukrov Nataša Tepić Dario Omanović Sonja Lojen Elvira Bura-Nakić Vjeročka Vojvodić 《International journal of environmental analytical chemistry》2013,93(10):1187-1199
Multivariate statistical analyses were applied on the measured physico-chemical (Cd, Pb, Cu, Zn, Mg, Ca, O2, alkalinity, temperature, pH, SAS, DOC and DIC) and isotopic parameters (δ13C and δ18O) to estimate and distinguish anthropogenic from natural influences to the water system of the Krka River. Analyses were conducted on the data collected during six years from twelve sampling sites. On the basis of orientation, positioning and grouping of parameters arranged by biplots, four main hypotheses were defined and finally statistically confirmed. Thereof, two main and distinct processes occurring in the Krka River could be highlighted: (i) upstream pollution, caused by the inflow of untreated waste-waters of city of Knin and (ii) downstream self-purification, caused by the sedimentation and/or co-precipitation of pollutants coupled by the inflow of clean subterranean water (groundwater recharge). Grouping of (i) hydrological and carbon cycle connected parameters, and (ii) anthropogenically influenced correlated parameters were proposed as a result of statistical analysis. Regarding the pH, it is shown that a stream section influenced by the subterranean inflow of Zrmanja River is statistically significantly different for all sampling campaigns during six years, being lower for about 0.5 pH unit. 相似文献
68.
CMPO-离子液体萃取分离铀(VI)体系的电化学性质 总被引:1,自引:0,他引:1
研究了辛基(苯基)-N,N-二异丁基胺甲酰基甲基氧化膦(CMPO)-离子液体(IL)从硝酸铀酰水溶液中萃取铀(VI)的电化学行为, 离子液体(IL)为1-丁基-3-甲基咪唑双三氟甲基磺酰亚胺盐(C4mimNTf2). 用等摩尔系列法测得萃取过程中CMPO与U(VI)形成摩尔比为3:1的配合物. 用循环伏安法研究了萃取液中U(VI)-CMPO配合物的电化学性质, 结果表明, 在C4mimNTf2中U(VI)-CMPO 配合物经过准可逆还原生成U(V)-CMPO 配合物, U(VI)/U(V)电对的表观氧化还原电势(EΘ, vs Fc/Fc+)为(?0.885±0.008) V. 对萃取液进行控制电位电解, 发现在铂片上有沉淀析出. X射线光电子能谱(XPS) 测试结果表明, 沉积物中只含有U(VI)、U(IV)和氧, 而CMPO和C4mimNTf2没有被夹带析出. 相似文献
69.
70.
Kinetics and Mechanism of Catalytic Reduction of U(VI) with Hydrazine on Platinum Catalysts in Nitric Acid Media 下载免费PDF全文
Xiao-teng Zhang Shuai Hao Fei-fei Tang Bin Li Xian-ming Zhou Li-sheng Liu Liang-shu Xia 《化学物理学报(中文版)》2022,35(5):813-822
The kinetics of U(IV) produced by hydrazine reduction of U(VI) with platinum as a catalyst in nitric acid media was studied to reveal the reaction mechanism and optimize the reaction process. Electron spin resonance (ESR) was used to determine the influence of nitric acid oxidation. The effects of nitric acid, hydrazine, U(VI) concentration, catalyst dosage and temperature on the reaction rate were also studied. In addition, the simulation of the reaction process was performed using density functional theory. The results show that the influence of oxidation on the main reaction is limited when the concentration of nitric acid is below 0.5 mol/L. The reaction kinetics equation below the concentration of 0.5 mol/L is found as: -dc(UO22+)/dt)=kc0.5323(UO22+)c0.2074(N2H5+)c-0.2009(H+). When the temperature is 50 ℃, and the solid/liquid ratio r is 0.0667 g/mL, the reaction kinetics constant is k=0.00199 (mol/L)0.4712/min. Between 20 ℃ and 80 ℃, the reaction rate gradually increases with the increase of temperature, and changes from chemically controlled to diffusion-controlled. The simulations of density functional theory give further insight into the influence of various factors on the reaction process, with which the reaction mechanisms are determined according to the reaction kinetics and the simulation results. 相似文献