全文获取类型
收费全文 | 332888篇 |
免费 | 8853篇 |
国内免费 | 3892篇 |
专业分类
化学 | 183281篇 |
晶体学 | 3713篇 |
力学 | 14681篇 |
综合类 | 224篇 |
数学 | 39426篇 |
物理学 | 104308篇 |
出版年
2021年 | 2422篇 |
2020年 | 3052篇 |
2019年 | 2937篇 |
2018年 | 2868篇 |
2017年 | 2743篇 |
2016年 | 5110篇 |
2015年 | 4421篇 |
2014年 | 5849篇 |
2013年 | 15883篇 |
2012年 | 13006篇 |
2011年 | 15681篇 |
2010年 | 9841篇 |
2009年 | 9759篇 |
2008年 | 13987篇 |
2007年 | 13988篇 |
2006年 | 13481篇 |
2005年 | 12238篇 |
2004年 | 10842篇 |
2003年 | 9494篇 |
2002年 | 9233篇 |
2001年 | 10102篇 |
2000年 | 7571篇 |
1999年 | 6102篇 |
1998年 | 4778篇 |
1997年 | 4788篇 |
1996年 | 4743篇 |
1995年 | 4678篇 |
1994年 | 4366篇 |
1993年 | 4158篇 |
1992年 | 4575篇 |
1991年 | 4417篇 |
1990年 | 4104篇 |
1989年 | 3899篇 |
1988年 | 4160篇 |
1987年 | 3794篇 |
1986年 | 3679篇 |
1985年 | 5336篇 |
1984年 | 5387篇 |
1983年 | 4349篇 |
1982年 | 4724篇 |
1981年 | 4751篇 |
1980年 | 4477篇 |
1979年 | 4612篇 |
1978年 | 4612篇 |
1977年 | 4588篇 |
1976年 | 4560篇 |
1975年 | 4451篇 |
1974年 | 4317篇 |
1973年 | 4486篇 |
1972年 | 2532篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
991.
Frontispiece: Gd‐DTPA‐Dopamine‐Bisphytanyl Amphiphile: Synthesis,Characterisation and Relaxation Parameters of the Nanoassemblies and Their Potential as MRI Contrast Agents 下载免费PDF全文
992.
Selective Permeability of Uranyl Peroxide Nanocages to Different Alkali Ions: Influences from Surface Pores and Hydration Shells 下载免费PDF全文
Yunyi Gao Fadi Haso Jennifer E. S. Szymanowski Jing Zhou Lang Hu Prof. Dr. Peter C. Burns Prof. Dr. Tianbo Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(51):18785-18790
The precise guidance to different ions across the biological channels is essential for many biological processes. An artificial nanopore system will facilitate the study of the ion‐transport mechanism through nanosized channels and offer new views for designing nanodevices. Herein we reveal that a 2.5 nm‐sized, fullerene‐shaped molecular cluster Li48+mK12(OH)m[UO2(O2)(OH)]60?(H2O)n (m≈20 and n≈310) ( U60 ) shows selective permeability to different alkali ions. The subnanometer pores on the water–ligand‐rich surface of U60 are able to block Rb+ and Cs+ ions from passing through, while allowing Na+ and K+ ions, which possess larger hydrated sizes, to enter the interior space of U60 . An interestingly high entropy gain during the binding process between U60 and alkali ions suggests that the hydration shells of Na+/K+ and U60 are damaged during the interaction. The ion selectivity of U60 is greatly influenced by both the morphologies of the surface nanopores and the dynamics of the hydration shells. 相似文献
993.
Frontispiece: Surface Segregated AgAu Tadpole‐Shaped Nanoparticles Synthesized Via a Single Step Combined Galvanic and Citrate Reduction Reaction 下载免费PDF全文
994.
为了探讨2,3-二氢黄酮类化合物在发光材料方面的应用,首先合成了2,3-二氢黄酮类衍生物[3-(2-萘甲酰基)-2-苯基苯并二氢吡喃-4-酮(L)]配体,然后利用Eu(III)与此配体和水/邻菲罗啉(Phen)反应得到两种新型的红色荧光配合物。运用元素分析、红外光谱与荧光光谱等手段对相关物质进行了系统的表征。表征结果表明:两个新配合物的组成分别为Eu(L)3·2H2O和Eu(L)3·Phen;荧光光谱研究显示,两种配合物的配体能将吸收的能量有效地传递给铕离子,从而使配合物发射出强的铕离子的特征荧光,且两个配合物Eu(L)3·2H2O和Eu(L)3·Phen均以5D0→7F2跃迁的荧光发射最强。得到了两种新的高效的红色荧光材料。 相似文献
995.
Deniz Aydemir Alper Kiziltas Douglas J. Gardner Yousoo Han Gokhan Gunduz 《International Journal of Polymer Analysis and Characterization》2015,20(3):231-239
The aim of this study was to measure the thermal properties of foamed nano/macro filler–reinforced styrene maleic anhydride (SMA) composites. SMA (66%) as a polymer matrix (10% maleic anhydride content) and various fillers including wood flour, starch, α-cellulose, microcrystalline cellulose and cellulose nanofibrils as reinforcing agents (30%) and lubricant (4%) were used to manufacture the composites in a twin-screw extruder. According to the thermogravimetric analysis (TGA) results, thermal degradation of all the foamed composites was found to be lower than that of SMA composites. The storage modulus values were negatively affected with a second time foaming (reprocessing [recycling] the initially processed composites a second time), as were loss modulus and Tg. As a result, second-time-foamed composite modulus values were lower than those of the foamed composites. According to the melt flow index (MFI) results, viscosity of the SMA was found to increase with the addition of fillers. 相似文献
996.
Shaohua Guo Dr. Pan Liu Dr. Yang Sun Kai Zhu Dr. Jin Yi Prof. Mingwei Chen Prof. Masayoshi Ishida Prof. Haoshen Zhou 《Angewandte Chemie (International ed. in English)》2015,54(40):11701-11705
Recently, there has been great interest in developing advanced sodium‐ion batteries for large‐scale application. Most efforts have concentrated on the search for high‐performance electrode materials only in sodium half‐cells. Research on sodium full cells for practical application has encountered many problems, such as insufficient cycles with rapid capacity decay, low safety, and low operating voltage. Herein, we present a layered P2‐Na0.66Ni0.17Co0.17Ti0.66O2, as both an anode (ca. 0.69 V versus Na+/Na) and as a high‐voltage cathode (ca. 3.74 V versus Na+/Na). The full cell based on this bipolar electrode exhibits well‐defined voltage plateaus near 3.10 V, which is the highest average voltage in the symmetric cells. It also shows the longest cycle life (75.9 % capacity retention after 1000 cycles) in all sodium full cells, a usable capacity of 92 mAh g?1, and superior rate capability (65 mAh g?1 at a high rate of 2C). 相似文献
997.
Diferrocenophosphaborin: A Planar‐Chiral,Redox‐Active and Anion‐Responsive Ambiphilic Ligand 下载免费PDF全文
Dr. Jiawei Chen Didier A. Murillo Parra Prof. Dr. Roger A. Lalancette Prof. Dr. Frieder Jäkle 《Angewandte Chemie (International ed. in English)》2015,54(35):10202-10205
A new class of Janus‐like ambiphilic ligands is introduced. The rigid diferrocene backbone in heterocycles 4‐SnP and 4‐BP creates an unprecedented chiral environment as demonstrated by multinuclear NMR and single‐crystal X‐ray studies. In addition, the ligands are redox‐responsive and the Lewis acidic borane moiety in 4‐BP can be exploited to further tune the properties: a clear decrease in the CO stretching frequency of a Vaska‐type RhI complex 5‐BP is observed upon addition of fluoride ions. Thus, the Lewis acid and Lewis base sites influence each other and their strength can be modulated by redox chemistry and anion binding. 相似文献
998.
Dr. Hans‐Georg Stammler M. Sc. Sebastian Blomeyer Priv.‐Doz. Dr. Raphael J. F. Berger Prof. Dr. Norbert W. Mitzel 《Angewandte Chemie (International ed. in English)》2015,54(46):13816-13820
The charge density distribution of the trimethylaluminum dimer was determined by high‐angle X‐ray diffraction of a single crystal and quantum‐chemical methods and analyzed using the quantum theory of atoms in molecules. The data can be interpreted as Al2Me6 being predominantly ionically bonded, with clear indications of topological asymmetry for the bridging Al? C bonds owing to delocalized multicenter bonding. This interpretation is supported by the calculated magnetic response currents. The data shed new light on the bonding situation in this basic organometallic molecule, which was previously described by contradicting interpretations of bonding. 相似文献
999.
Dr. Yongjun Zhou Prof. Patrícia Prediger Prof. Luiz Carlos Dias Dr. Annabel C. Murphy Prof. Peter F. Leadlay 《Angewandte Chemie (International ed. in English)》2015,54(17):5232-5235
Elaiophylin is an unusual C2‐symmetric antibiotic macrodiolide produced on a bacterial modular polyketide synthase assembly line. To probe the mechanism and selectivity of diolide formation, we sought to reconstitute ring formation in vitro by using a non‐natural substrate. Incubation of recombinant elaiophylin thioesterase/cyclase with a synthetic pentaketide analogue of the presumed monomeric polyketide precursor of elaiophylin, specifically its N‐acetylcysteamine thioester, produced a novel 16‐membered C2‐symmetric macrodiolide. A linear dimeric thioester is an intermediate in ring formation, which indicates iterative use of the thioesterase active site in ligation and subsequent cyclization. Furthermore, the elaiophylin thioesterase acts on a mixture of pentaketide and tetraketide thioesters to give both the symmetric decaketide diolide and the novel asymmetric hybrid nonaketide diolide. Such thioesterases have potential as tools for the in vitro construction of novel diolides. 相似文献
1000.
Ammonia Activation by a Nickel NCN‐Pincer Complex featuring a Non‐Innocent N‐Heterocyclic Carbene: Ammine and Amido Complexes in Equilibrium 下载免费PDF全文
Rudy M. Brown Dr. Javier Borau Garcia Juuso Valjus Christopher J. Roberts Dr. Heikki M. Tuononen Dr. Masood Parvez Prof. Roland Roesler 《Angewandte Chemie (International ed. in English)》2015,54(21):6274-6277
A Ni0‐NCN pincer complex featuring a six‐membered N‐heterocyclic carbene (NHC) central platform and amidine pendant arms was synthesized by deprotonation of its NiII precursor. It retained chloride in the square‐planar coordination sphere of nickel and was expected to be highly susceptible to oxidative addition reactions. The Ni0 complex rapidly activated ammonia at room temperature, in a ligand‐assisted process where the carbene carbon atom played the unprecedented role of proton acceptor. For the first time, the coordinated (ammine) and activated (amido) species were observed together in solution, in a solvent‐dependent equilibrium. A structural analysis of the Ni complexes provided insight into the highly unusual, non‐innocent behavior of the NHC ligand. 相似文献