全文获取类型
收费全文 | 3832篇 |
免费 | 246篇 |
国内免费 | 17篇 |
专业分类
化学 | 2706篇 |
晶体学 | 16篇 |
力学 | 71篇 |
数学 | 530篇 |
物理学 | 772篇 |
出版年
2023年 | 57篇 |
2022年 | 79篇 |
2021年 | 123篇 |
2020年 | 176篇 |
2019年 | 197篇 |
2018年 | 91篇 |
2017年 | 77篇 |
2016年 | 216篇 |
2015年 | 168篇 |
2014年 | 178篇 |
2013年 | 237篇 |
2012年 | 309篇 |
2011年 | 311篇 |
2010年 | 187篇 |
2009年 | 152篇 |
2008年 | 233篇 |
2007年 | 186篇 |
2006年 | 181篇 |
2005年 | 129篇 |
2004年 | 79篇 |
2003年 | 63篇 |
2002年 | 57篇 |
2001年 | 47篇 |
2000年 | 39篇 |
1999年 | 26篇 |
1998年 | 20篇 |
1997年 | 21篇 |
1996年 | 25篇 |
1995年 | 24篇 |
1994年 | 20篇 |
1993年 | 19篇 |
1992年 | 26篇 |
1991年 | 22篇 |
1990年 | 27篇 |
1989年 | 15篇 |
1988年 | 14篇 |
1987年 | 16篇 |
1986年 | 18篇 |
1985年 | 10篇 |
1984年 | 15篇 |
1983年 | 15篇 |
1982年 | 18篇 |
1981年 | 17篇 |
1979年 | 17篇 |
1978年 | 24篇 |
1977年 | 12篇 |
1976年 | 17篇 |
1975年 | 8篇 |
1974年 | 9篇 |
1973年 | 10篇 |
排序方式: 共有4095条查询结果,搜索用时 15 毫秒
71.
Sebastian T. Le QuementMette Ishoey Mette T. PetersenPernille M. Simonsen Nanna S. HolckThomas E. Nielsen 《Tetrahedron letters》2011,52(52):7049-7053
An approach for the solid-phase synthesis of apoptosis-inducing Smac peptidomimetics is presented. Using a Rink linker strategy, tetrapeptides mimicking the N-4-terminal residue of the Smac protein [(N-Me)AVPF sequence] were synthesized on PEGA resin in excellent purities and yields. Following two synthetic routes, a known tetrapeptide, incorporating a substituted proline, previously shown to exhibit excellent biological activity in vitro as well as low toxicity, was synthesized effectively on a solid support. 相似文献
72.
Xie W Herrmann C Kömpe K Haase M Schlücker S 《Journal of the American Chemical Society》2011,133(48):19302-19305
The synthesis of bifunctional Au/Pt/Au nanoraspberries for use in quantitative in situ monitoring of platinum-catalyzed reactions by surface-enhanced Raman scattering (SERS) is presented. Highly convolved SERS spectra of reaction mixtures can be decomposed into the contributions of distinct molecular species by multivariate data analysis. 相似文献
73.
Thermophysical properties and material modelling of acrylic bone cements used in vertebroplasty 总被引:1,自引:0,他引:1
Sebastian Kolmeder Alexander Lion Ralf Landgraf Jörn Ihlemann 《Journal of Thermal Analysis and Calorimetry》2011,105(2):705-718
The stabilization of osteoporotic vertebrae with acrylic bone cement, called vertebroplasty, is a common procedure in modern
surgery. However, the thermomechanical-chemically coupled material behaviour of curing bone cements makes the application
even for experienced surgeons difficult and can lead to potential complications like heat necrosis, leaking bone cement, embolisms
and postoperative load shifting. In order to reduce these potential complications, to minimize the risks and to better understand
the occurring effects, the thermophysical properties of a commercial acrylic bone cement were investigated in detail using
differential scanning calorimetry, volumetric dilatometry and temperature controlled rheometry. More specifically, the reaction
kinetics, the specific heat, the thermal conductivity, the thermal expansion, the chemical shrinkage as well as the mechanical
behaviour was studied during the reaction process of the bone cement. Furthermore, the explored material behaviour is described
by a customized material model that takes into account all observed effects. With the aid of this model the inhomogeneous
chemical, thermal and mechanical states that appear during the application and curing of acrylic bone cements, can be studied
by finite element treatment. 相似文献
74.
Isomerism, conformations, and molecular structure of a model molecule of vitamin K1 with a truncated side chain have been studied by the density functional theory calculations using B3LYP method and double-
and triple-ζ correlation consistent basis sets. The conformations of two possible (E and Z) isomers, formed by the rotations around three single C–C bonds closest to the naphthoquinone ring, have been studied. The
lowest energy conformers are stabilized by additional hydrogen bonds between hydrogen atoms of the side chain and an oxygen
atom in the naphthoquinone subunit. It is interesting to note that the structure of the energetically preferred conformer
of the E-isomer (3c) has been found to be similar to the solid state structures of phylloquinones in the photosystem I of cyanobacterium
Synechococcus elongatus. The excited electronic states of two lowest energy conformers have also been investigated. 相似文献
75.
Abstract The phosphonium salts have been prepared by the reaction of triphenylphosphine with the corresponding halomethanes (eq. (1)) and bromine (eq.(2)), respectively. 相似文献
76.
Multidimensional nano-HPLC coupled with tandem mass spectrometry for analyzing biotinylated proteins
Jens Sproß Sebastian Brauch Friedrich Mandel Moritz Wagner Stephan Buckenmaier Bernhard Westermann Andrea Sinz 《Analytical and bioanalytical chemistry》2013,405(7):2163-2173
Multidimensional high-performance liquid chromatography (HPLC) is a key method in shotgun proteomics approaches for analyzing highly complex protein mixtures by complementary chromatographic separation principles. Here, we describe an integrated 3D-nano-HPLC/nano-electrospray ionization quadrupole time-of-flight mass spectrometry system that allows an enzymatic digestion of proteins followed by an enrichment and subsequent separation of the created peptide mixtures. The online 3D-nano-HPLC system is composed of a monolithic trypsin reactor in the first dimension, a monolithic affinity column with immobilized monomeric avidin in the second dimension, and a reversed phase C18 HPLC-Chip in the third dimension that is coupled to a nano-ESI-Q-TOF mass spectrometer. The 3D-LC/MS setup is exemplified for the identification of biotinylated proteins from a simple protein mixture. Additionally, we describe an online 2D-nano-HPLC/nano-ESI-LTQ-Orbitrap-MS/MS setup for the enrichment, separation, and identification of cross-linked, biotinylated species from chemical cross-linking of cytochrome c and a calmodulin/peptide complex using a novel trifunctional cross-linker with two amine-reactive groups and a biotin label. Figure
Schematic representations of the online 3D-nano-HPLC/nano-ESI-Q-TOF-MS/MS setup; LP loading pump, NP nano-pump 相似文献
77.
Lena Scherthan Sebastian F. M. Schmidt Hendrik Auerbach Tim Hochdrffer Juliusz A. Wolny Wenli Bi Jiyong Zhao Michael Y. Hu Tom Toellner E. Ercan Alp Dennis E. Brown Christopher E. Anson Annie K. Powell Volker Schünemann 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(11):3482-3487
Time‐domain synchrotron Mössbauer spectroscopy (SMS) based on the Mössbauer effect of 161Dy has been used to investigate the magnetic properties of a DyIII‐based single‐molecule magnet (SMM). The magnetic hyperfine field of [Dy(Cy3PO)2(H2O)5]Br3?2 (Cy3PO)?2 H2O?2 EtOH is with B0=582.3(5) T significantly larger than that of the free‐ion DyIII with a 6H15/2 ground state. This difference is attributed to the influence of the coordinating ligands on the Fermi contact interaction between the s and 4f electrons of the DyIII ion. This study demonstrates that 161Dy SMS is an effective local probe of the influence of the coordinating ligands on the magnetic structure of Dy‐containing compounds. 相似文献
78.
Selda Kabatas Paola Agüi‐Gonzalez Kim‐Ann Saal Sebastian Jhne Felipe Opazo Silvio O. Rizzoli Nhu T. N. Phan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(11):3476-3481
Boron has been employed in materials science as a marker for imaging specific structures by electron energy loss spectroscopy (EELS) or secondary ion mass spectrometry (SIMS). It has a strong potential in biological analyses as well; however, the specific coupling of a sufficient number of boron atoms to a biological structure has proven challenging. Herein, we synthesize tags containing closo‐1,2‐dicarbadodecaborane, coupled to soluble peptides, which were integrated in specific proteins by click chemistry in mammalian cells and were also coupled to nanobodies for use in immunocytochemistry experiments. The tags were fully functional in biological samples, as demonstrated by nanoSIMS imaging of cell cultures. The boron signal revealed the protein of interest, while other SIMS channels were used for imaging different positive ions, such as the cellular metal ions. This allows, for the first time, the simultaneous imaging of such ions with a protein of interest and will enable new biological applications in the SIMS field. 相似文献
79.
Sebastian Grieger Beata M. Szydowska Vaishnavi J. Rao Eva Steinmann Marcus Dodds Zahra Gholamvand Georg S. Duesberg Jana Zaumseil Claudia Backes 《Angewandte Chemie (International ed. in English)》2020,59(33):13785-13792
In recent years, various functionalization strategies for transition‐metal dichalcogenides have been explored to tailor the properties of materials and to provide anchor points for the fabrication of hybrid structures. Herein, new insights into the role of the surfactant in functionalization reactions are described. Using the spontaneous reaction of WS2 with chloroauric acid as a model reaction, the regioselective formation of gold nanoparticles on WS2 is shown to be heavily dependent on the surfactant employed. A simple model is developed to explain the role of the chosen surfactant in this heterogeneous functionalization reaction. The surfactant coverage is identified as the crucial element that governs the dominant reaction pathway and therefore can severely alter the reaction outcome. This study shows the general importance of the surfactant choice and how detrimental or beneficial a certain surfactant can be to the desired functionalization. 相似文献
80.
Mathias Mallmann Sebastian Wendl Dr. Philipp Strobel Dr. Peter J. Schmidt Prof. Dr. Wolfgang Schnick 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(28):6257-6263
Nitridophosphates exhibit an intriguing structural diversity with different structural motifs, for example, chains, layers or frameworks. In this contribution the novel nitridophosphate Sr3P3N7 with unprecedented dreier double chains is presented. Crystalline powders were synthesized using the ammonothermal method, while single crystals were obtained by a high-pressure multianvil technique. The crystal structure of Sr3P3N7 was solved and refined from single-crystal X-ray diffraction and confirmed by powder X-ray methods. Sr3P3N7 crystallizes in monoclinic space group P2/c. Energy-dispersive X-ray and Fourier-transformed infrared spectroscopy were conducted to confirm the chemical composition, as well as the absence of NHx functionality. The optical band gap was estimated to be 4.4 eV using diffuse reflectance UV/Vis spectroscopy. Upon doping with Eu2+, Sr3P3N7 shows a broad deep-red to infrared emission (λem=681 nm, fwhm≈3402 cm−1) with an internal quantum efficiency of 42 %. 相似文献