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81.
82.
We report in situ high-resolution transmission electron microscopy observing the shrinkage of single-layer giant fullerenes (GF). At temperatures approximately 2000 degrees C, the GF volume reduces by greater than one 100-fold while the fullerene shell remains intact, evolving from a slightly polygonized to a nearly spherical shape with a smaller diameter. The number of carbon atoms in the GF decreases linearly with time until the small subbuckyball cage opens and rapidly disappears. Theoretical modeling indicates that carbon atoms are removed predominantly from the weakest binding energy sites, i.e., the pentagons, leading to the constant evaporation rate. The fullerene cage integrity is attributed to the collective behavior of interacting defects. These results constitute the first experimental evidence for the "shrink-wrapping" and "hot-giant" fullerene formation mechanisms. 相似文献
83.
An efficient approach for the synthesis of monosubstituted aromatic compounds relying on a ring-closing metathesis followed by spontaneous 1,2-elimination is presented. The efficiency for late-stage functionalization is highlighted in various solvents (up to 920 TON). This approach is compatible with strained cycles and other multiple bonds in the substrate. 相似文献
84.
85.
Boris Wilthan 《Journal of Thermal Analysis and Calorimetry》2014,118(2):603-611
This study addresses the lack of published information regarding uncertainty for high temperature heat flux differential scanning calorimeters. No data were found in the existing literature stating an uncertainty budget for temperatures above 1,000 °C. The presented results identify the main influencing factor for uncertainty with the instruments used—measurement repeatability—up to a temperature of 1,400 °C. Results show findings from analyzing a series of repeated baseline and sapphire measurements and the influence from different working equations. The uncertainty budget for temperature calibration of DSCs is crucial in cases where accuracy in temperature is significant. Data are also provided from repeated temperature calibrations on the melting point of pure metals from a supplied standard set that comes with the instrument. In addition, carbon eutectics have been used to address an issue resulting from the lack of available calibration materials for high temperatures up to 1,500 °C (above the melting point of gold). 相似文献
86.
Large Hexagonal Bi‐ and Trilayer Graphene Single Crystals with Varied Interlayer Rotations 下载免费PDF全文
Zheng Yan Yuanyue Liu Long Ju Zhiwei Peng Dr. Jian Lin Dr. Gunuk Wang Dr. Haiqing Zhou Changsheng Xiang E. L. G. Samuel Carter Kittrell Dr. Vasilii I. Artyukhov Prof. Feng Wang Prof. Boris I. Yakobson Prof. James M. Tour 《Angewandte Chemie (International ed. in English)》2014,53(6):1565-1569
Bi‐ and trilayer graphene have attracted intensive interest due to their rich electronic and optical properties, which are dependent on interlayer rotations. However, the synthesis of high‐quality large‐size bi‐ and trilayer graphene single crystals still remains a challenge. Here, the synthesis of 100 μm pyramid‐like hexagonal bi‐ and trilayer graphene single‐crystal domains on Cu foils using chemical vapor deposition is reported. The as‐produced graphene domains show almost exclusively either 0° or 30° interlayer rotations. Raman spectroscopy, transmission electron microscopy, and Fourier‐transformed infrared spectroscopy were used to demonstrate that bilayer graphene domains with 0° interlayer stacking angles were Bernal stacked. Based on first‐principle calculations, it is proposed that rotations originate from the graphene nucleation at the Cu step, which explains the origin of the interlayer rotations and agrees well with the experimental observations. 相似文献
87.
Ortal Haik Francis Susai Amalraj Daniel Hirshberg Luba Burlaka Michael Talianker Boris Markovsky Ella Zinigrad Doron Aurbach Jordan K. Lampert Ji-Yong Shin Martin Schulz-Dobrick Arnd Garsuch 《Journal of Solid State Electrochemistry》2014,18(8):2333-2342
Thermodynamic instability of positive electrodes (cathodes) in Li-ion batteries in humid air and battery solutions results in capacity fading and batteries degradation, especially at elevated temperatures. In this work, we studied thermal interactions between cathode materials Li2MnO3, xLi2MnO3 .(1???x)Li(MnNiCo)O2,LiNi0.33Mn0.33Co0.33O2, LiNi0.4Mn0.4Co0.2O2, LiNi0.8Co0.15Al0.05O2 LiMn1.5Ni0.5O4, LiMn(or Fe)PO4, and battery solutions containing ethylene carbonate (EC) or propylene carbonate (PC), dimethyl carbonate (DMC) or ethylmethyl carbonate (EMC) and LiPF6 salt in the temperature range of 40–400 °C. It was found that these materials are stable chemically and well performing in LiPF6-based solutions up to 60 °C. The thermal decomposition of the electrolyte solutions starts >180 °C. The macro-structural transformations of cathode materials upon exothermic reactions were studied by transmission electron microscopy (TEM), X-ray difraction (XRD) and Raman spectroscopy. Differential scanning calorimetry (DSC) studies have shown that the exothermic reactions in the temperature range of 60–140 °C lead to partial decomposition of both the cathode material and electrolyte solution. The systems thus formed consisted of partially decomposed solutions and partially chemically delithiated cathode materials covered by reactions products. Thermal reactions terminate and this system reaches equilibrium at about 120 °C. It remains stable up to the beginning of the solution decomposition at about 180 °C. The increased content of surface Li2CO3 is found to significantly affect the thermal processes at high temperature range due to extensive exothermic decomposition at low temperatures. 相似文献
88.
Unraveling the Crystal Structure of Lanthanide–Murexide Complexes: Use of an Ancient Complexometry Indicator as a Near‐Infrared‐Emitting Single‐Ion Magnet 下载免费PDF全文
Xiaohui Yi Dr. Kevin Bernot Vincent Le Corre Dr. Guillaume Calvez Dr. Fabrice Pointillart Dr. Olivier Cador Dr. Boris Le Guennic Julie Jung Dr. Olivier Maury Dr. Virginie Placide Dr. Yannick Guyot Dr. Thierry Roisnel Dr. Carole Daiguebonne Prof. Olivier Guillou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(6):1569-1576
Herein, we provide some structural evidence of the complexation color‐change of murexide solutions in presence of lanthanide, which has been used for decades in complexometric studies. For Ln=Sm to Lu and Y, the compounds crystallize as monomeric [Ln(Murex)3] ? 11 H2O with an N3O6 tricapped square‐antiprism environment, which are stable up to 250 °C. Single‐ion magnet (SIM) behavior is then observed on the YbIII derivative in an original nine‐coordinated environment. In‐field slow relaxation (Δ=(15.6±1) K; τ0=2.73×10?6 s) is observed with a very narrow distribution of the relaxation time (αmax=0.09). Magnetic and photophysical properties can be correlated. On one hand the analysis of NIR emission spectrum permits to have access to crystal field parameters and to compare them with those extracted from dc measurements. On the other hand, magnetic measurements permit to identify the nature of the M J states involved in the 2F5/2→2F7/2 luminescence spectrum. The gap between the low‐lying states is in agreement with the energy barrier obtained from magnetic slow‐relaxation measurement. 相似文献
89.
Andrea Kunfermann Matthias Witschel Boris Illarionov Ren Martin Matthias Rottmann H. Wolfgang Hffken Michael Seet Wolfgang Eisenreich Hans‐Joachim Knlker Markus Fischer Adelbert Bacher Michael Groll Franois Diederich 《Angewandte Chemie (International ed. in English)》2014,53(8):2235-2239
The enzymes of the non‐mevalonate pathway for isoprenoid biosynthesis have been identified as attractive targets with novel modes of action for the development of herbicides for crop protection and agents against infectious diseases. This pathway is present in many pathogenic organisms and plants, but absent in mammals. By using high‐throughput screening, we identified highly halogenated marine natural products, the pseudilins, to be inhibitors of the third enzyme, IspD, in the pathway. Their activity against the IspD enzymes from Arabidopsis thaliana and Plasmodium vivax was determined in photometric and NMR‐based assays. Cocrystal structures revealed that pseudilins bind to an allosteric pocket by using both divalent metal ion coordination and halogen bonding. The allosteric mode of action for preventing cosubstrate (CTP) binding at the active site was elucidated. Pseudilins show herbicidal activity in plant assays and antiplasmodial activity in cell‐based assays. 相似文献
90.
Maksym S. Kazunin Oleksii Yu. Voskoboynik Inna S. Nosulenko Galina G. Berest Sergiy V. Kholodniak Boris O. Pryymenko Sergiy I. Kovalenko 《Journal of heterocyclic chemistry》2020,57(1):268-280
The synthesis of 6-(2-hydroxy-2-aryl (heteryl)ethyl)-1-methylpteridine-2,4,7(1H,3H,8H)-triones by the reduction of the corresponding ketones and the peculiarities of conversion of the synthesized alcohols to (E)-1-methyl-6-(2-aryl (heteryl)ethenyl)pteridine-2,4,7(1H,3H,8H)-triones was reported. The mechanism of monomolecular elimination that occurred in the presence of hydrogen halides was discussed, namely, the competitive formation of an energy-efficient conjugated system by deprotonation of a stable benzyl-type carbocation. Alternative synthesis methods of pteridine-2,4,7(1H,3H,8H)-triones were developed. Abovementioned approach involved [4+2]-cyclocondensation of 1-methyl-5,6-diaminouracil to 2-oxo-4-R-but-3-enoic acids and Knoevenagel condensation of 1,6-dimethylpteridine-2,4,7(1H,3H,8H)-trione with aromatic aldehydes. The antiradical, antimicrobial, and antifungal activities were studied for the synthesized compounds. 相似文献