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61.
利用原位红外技术研究了CH3OH、CO、O2等在Pd/γAl2O3上的吸附情况及CH3OH和O2共吸附时表面物种的变化,结果表明:表面纯净的Pd/γAl2O3催化剂对甲醇具有很好的解离吸附性能,在无氧条件下,CH3OH可在其上脱氢产生HCHO及CO。Pd对O2的吸附力强,氧均以解离方式吸附于Pd/γAl2O3上。当吸附的[CH3O]与[O]在Pd/γAl2O3上相互作用时,可产生HCHO、CO、甲二氧基、甲酸根等中间物种 相似文献
62.
K对Mn—Co—O的结构及氧化活性的影响 总被引:1,自引:0,他引:1
利用XRD,TPD,TFD-MS及催化氧化反应等实验技术,研究了K对Mn-Co-O的结构及氧化活性的影响。XRD结果表明,Mn-Co-O系已形成反尖晶石型的MnCo_2O_4结构;K-Mn-Co-O系中除MnCo_2O_4型结构外,还有新相KMnO_2存在。根据O_2的TPD-MS及吡啶的TPD结果,Mn-Co-O中添加适量的K能提高供氧活性和增加供氧数目,但酸中心数目减少,强度降低。K对Mn-Co—O催化剂氧化活性的影响随反应物分子结构的不同而异,对乙酸乙脂、苯甲酰氯等极性有机物的完全氧化反应,K能提高氧化活性,但对苯、正己烷等非极性有机物的完全氧化反应,K使其活性降低。 相似文献
63.
稀土金属离子与人血清白蛋白的相互作用 总被引:3,自引:0,他引:3
本文用荧光光谱、紫外-可见吸收光谱法和循环伏安法研究了稀土金属离子Eu(Ⅲ)、Pr(Ⅲ)与人血清白蛋白(HSA)的相互作用。实验发现:Eu(Ⅲ)和Pr(Ⅲ)对HSA有较强的荧光猝灭作用。用Stern-Volmer方程分别对实验数据进行处理,结果发现:HSA与Eu(Ⅲ)、Pr(Ⅲ)发生反应生成了新的复合物,发生了分子内的非辐射能量转移。Eu(Ⅲ)、Pr(Ⅲ)对HAS的荧光猝灭作用,属于静态荧光猝灭。荧光猝灭图表明:Eu3+和Pr3+在HSA分子中至少有两类结合位点,Eu3+与HSA形成2.76∶1的复合物,结合常数lgK分别为12.03和9.05;Pr3+与HSA形成2.2∶1的复合物,结合常数lgK分别为9.89和6.97。同时用圆二色谱及同步荧光光谱法探讨了 Eu(Ⅲ)和Pr(Ⅲ)对HSA构象的影响。 相似文献
64.
Gerhard BringmannStefan Busemann 《Tetrahedron》2003,59(8):1245-1253
The first quantum chemical calculation of the circular dichroism (CD) spectra of michellamines has been achieved, based on a complete quantum chemical conformational analysis. Michellamines are dimeric naphthylisoquinoline alkaloids and thus naturally occurring quateraryls, with a large molecular size and flexibility and equipped with stereogenic centers and axes. 相似文献
65.
Linda Fluyt Kris Driesen Christiane Görller-Walrand 《Journal of solid state chemistry》2005,178(2):429-434
A new approach to unravel the site symmetry of lanthanides in solutions is presented. The magnetic circular dichroism spectra of Eu3+ in the symmetries D3h, C4v and D2d are simulated. In these simulations, the main idea is to introduce the magnetic field along a 3-fold axis, being the resultant of the three equivalent X-, Y- and Z-direction of a cube. This implies that the parallel and perpendicular Zeeman effects are taken into account simultaneously. 相似文献
66.
Marlin Opałło Nagao Kobayashi Tetsuo Osa 《Journal of inclusion phenomena and macrocyclic chemistry》1989,7(4):413-422
The complexation of 2,3-anthracenedicarboxylate (ADC) by- and-cyclodextrins in water containing an organic solvent has been studied by induced circular dichroism. It has been shown that an increase of organic solvent ratio causes the degradation of the 1:1 ADC:-CD complex and the liberation of one guest molecule from the 2:1 ADC:-CD complex in water. The higher the hydrophobicity of the cosolvent, the weaker the complexation of ADC by-CD. 相似文献
67.
Herein, we report the first use of chiral alkaloid brucine to synthesize novel porphyrin-brucine conjugate capable of acting as a gelator of methanol and acetonitrile at extremely low level of concentration. The synthesis, characterization and spectral properties of gelator based on a novel structural motif, quaternized alkaloid conjugates, are described. Different spectroscopic methods (1H NMR spectroscopy, Raman and infrared spectroscopy, and spectroscopy of electronic and vibrational circular dichroism) were used for characterization of the prepared organogel. The aggregation of the gelator studied by UV-vis spectroscopy and electronic circular dichroism showed the formation of chiral J-aggregates in water and water-methanol (1:1) mixture. A new methodology for the determination of functional groups involved in gel formation based on vibrational circular dichroism is presented. 相似文献
68.
Atsuya Muranaka Yoshiaki Asano Akihiko Tsuda Atsuhiro Osuka Nagao Kobayashi 《Chemphyschem》2006,7(6):1235-1240
The electronic excited states of a meso-meso beta-beta doubly linked bis-porphyrin are comprehensively investigated by measuring its circular dichroism (CD) and magnetic circular dichroism (MCD) spectra. The observed spectroscopic properties are rationalized by DFT calculations. The frontier molecular orbitals (MOs) are constructed by the linear combinations of the constituent monomers' four MOs. Comparison of a theoretical CD spectrum based on time-dependent DFT (TDDFT) with the experimental spectra resulted in the assignment of the helical conformation of the dimer. This assignment is contrary to the previous assignment based on the point-dipole approximation (exciton coupling theory). 相似文献
69.
Petrovic AG Polavarapu PL Drabowicz J Zhang Y McConnell OJ Duddeck H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(14):4257-4262
The enantiomers of 3,3,3',3'-tetramethyl-1,1'-spirobi[3 H,2,1]benzoxaselenole have been separated on a chiral preparative chromatographic column. The experimental vibrational circular dichroism (VCD) spectra have been obtained for both enantiomers in CH(2)Cl(2). The theoretical VCD spectra have been obtained by means of density functional theoretical calculations with the B3 LYP density functional. From a comparison of experimental and theoretical VCD spectra, the absolute configuration of an enantiomer with positive specific rotation in CH(2)Cl(2) at 589 nm is determined to be R. This conclusion has been verified by comparing results of experimental optical rotatory dispersion (ORD) and electronic circular dichroism (ECD) to predictions of the same properties using the B3 LYP functional for the title compound. 相似文献
70.
Garth J Simpson 《Chemphyschem》2004,5(9):1301-1310
Recent observations of remarkably large chiroptical effects in second-harmonic generation (SHG) and sum-frequency generation (SFG) measurements suggest exciting possibilities for the development of new chiral-specific spectroscopies and novel chiral materials for nonlinear optics. Several fundamental studies designed to elucidate the molecular and macromolecular origins of the chiral responses are reviewed to provide a framework for development of this emerging field. In general, the chiral activity in SHG and SFG has the potential to arise from complex interactions between hosts of different competing effects. Fortunately, relatively simple electric dipole-allowed mechanisms routinely dominate the nonlinear optical chiral activities of most practical systemsexpressions can often be generated to link the. This substantial reduction in complexity allows for the development of simple models connecting the macroscopic nonlinear optical response to intuitive molecular and supramolecular properties. 相似文献