全文获取类型
收费全文 | 32398篇 |
免费 | 5959篇 |
国内免费 | 2759篇 |
专业分类
化学 | 11230篇 |
晶体学 | 259篇 |
力学 | 5366篇 |
综合类 | 344篇 |
数学 | 2441篇 |
物理学 | 10089篇 |
无线电 | 11387篇 |
出版年
2024年 | 145篇 |
2023年 | 471篇 |
2022年 | 842篇 |
2021年 | 1025篇 |
2020年 | 1290篇 |
2019年 | 1127篇 |
2018年 | 1090篇 |
2017年 | 1360篇 |
2016年 | 1555篇 |
2015年 | 1593篇 |
2014年 | 1957篇 |
2013年 | 2844篇 |
2012年 | 2235篇 |
2011年 | 2231篇 |
2010年 | 1725篇 |
2009年 | 1739篇 |
2008年 | 1806篇 |
2007年 | 1874篇 |
2006年 | 1796篇 |
2005年 | 1578篇 |
2004年 | 1407篇 |
2003年 | 1265篇 |
2002年 | 1075篇 |
2001年 | 979篇 |
2000年 | 891篇 |
1999年 | 749篇 |
1998年 | 663篇 |
1997年 | 585篇 |
1996年 | 547篇 |
1995年 | 477篇 |
1994年 | 390篇 |
1993年 | 328篇 |
1992年 | 281篇 |
1991年 | 200篇 |
1990年 | 161篇 |
1989年 | 139篇 |
1988年 | 140篇 |
1987年 | 91篇 |
1986年 | 73篇 |
1985年 | 69篇 |
1984年 | 68篇 |
1983年 | 19篇 |
1982年 | 62篇 |
1981年 | 45篇 |
1980年 | 13篇 |
1979年 | 25篇 |
1978年 | 16篇 |
1977年 | 17篇 |
1975年 | 8篇 |
1957年 | 16篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
1.
《Mendeleev Communications》2022,32(5):597-600
Calorimetric monitoring of the autoclave reaction N2O4 + C2H4 at –85 to +10 °C under argon pressure 10–30 bar revealed that the exothermic chemical reaction started at temperatures above –52 °C at 10 bar, whereas an intensive exothermic reaction started at –85 °C and pressure of 30 bar. IR study showed that oligo/polynitroethylene was formed at 30 bar, while carbonyl and hydroxy compound as well as nitrate R–ONO2 formation occurred upon processing at 10 bar. 相似文献
2.
Saqib Kamal Arif I. Inamdar Kuan-Ru Chiou Batjargal Sainbileg Muhammad Usman Jenq-Wei Chen Tzuoo-Tsair Luo Michitoshi Hayashi Chen-Hsiung Hung Wen-Feng Liaw Kuang-Lieh Lu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(30):e202103905
The dielectric properties of coordination polymers has been a topic of recent interest, but the role of different functional groups on the dielectric properties of these polymers has not yet been fully addressed. Herein, the effects of electron-donating (R=NH2) and electron-withdrawing (R=NO2) groups on the dielectric behavior of such materials were investigated for two thermally stable and guest-free Zn-based coordination polymers, [Zn(L1)(L2)]n ( 1 ) and [Zn(L1)(L3)]n ( 2 ) [L1=2-(2-pyridyl) benzimidazole (Pbim), L2=5-aminoisophthalate (Aip), and L3=5-nitroisophthalate (Nip)]. The results of dielectric studies of 1 revealed that it possesses a high dielectric constant (κ=65.5 at 1 kHz), while compound 2 displayed an even higher dielectric constant (κ=110.3 at 1 kHz). The electron donating and withdrawing effects of the NH2 and NO2 substituents induce changes in the polarity of the polymers, which is due to the inductive effect from the aryl ring for both NO2 and NH2. Theoretical results from density functional theory (DFT) calculations, which also support the experimental findings, show that both compounds have a distinct electronic behavior with diverse wide bandgaps. The significance of the current work is to provide information about the structure-dielectric property relationships. So, this study promises to pave the way for further research on the effects of different functional groups on coordination polymers on their dielectric properties. 相似文献
3.
Edward G. Sheetz Zhao Zhang Alyssa Marogil Minwei Che Dr. Maren Pink Dr. Veronica Carta Prof. Dr. Krishnan Raghavachari Prof. Dr. Amar H. Flood 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(60):e202201584
The recognition of boron compounds is well developed as boronic acids but untapped as organotrifluoroborate anions (R−BF3−). We are exploring the development of these and other designer anions as anion-recognition motifs by considering them as substituted versions of the parent inorganic ion. To this end, we demonstrate strong and reliable binding of organic trifluoroborates, R−BF3−, by cyanostar macrocycles that are size-complementary to the inorganic BF4− progenitors. We find that recognition is modulated by the substituent's sterics and that the affinities are retained using the common K+ salts of R−BF3− anions. 相似文献
4.
Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by 18O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts. 相似文献
5.
6.
Tetsuo Irifune Chiaki Ueda Shohei Ohshita Hiroaki Ohfuji Takehiro Kunimoto Toru Shinmei 《高压研究》2020,40(1):96-106
ABSTRACTNano-polycrystalline diamond (NPD) with various grain sizes has been synthesized from glassy carbon at pressures 15–25?GPa and temperatures 1700–2300°C using multianvil apparatus. The minimum temperature for the synthesis of pure NPD, below which a small amount of compressed graphite was formed, significantly increased with pressure from ~1700°C at 15?GPa to ~1900°C at 25?GPa. The NPD having grain sizes less than ~50?nm was synthesized at temperatures below ~2000°C at 15?GPa and ~2300°C at 25?GPa, above which significant grain growth was observed. The grain size of NPD decreases with increasing pressure and decreasing temperature, and the pure NPD with grain sizes less than 10?nm is obtained in a limited temperature range around 1800–2000°C, depending on pressure. The pure NPD from glassy carbon is highly transparent and exhibits a granular nano-texture, whose grain size is tunable by selecting adequate pressure and temperature conditions. 相似文献
7.
Bo Wang Edison Huixiang Ang Yang Yang Yufei Zhang Hongbo Geng Minghui Ye Cheng Chao Li 《Advanced functional materials》2020,30(28)
Orthorhombic molybdenum trioxide (MoO3) is one of the most promising anode materials for sodium‐ion batteries because of its rich chemistry associated with multiple valence states and intriguing layered structure. However, MoO3 still suffers from the low rate capability and poor cycle induced by pulverization during de/sodiation. An ingenious two‐step synthesis strategy to fine tune the layer structure of MoO3 targeting stable and fast sodium ionic diffusion channels is reported here. By integrating partially reduction and organic molecule intercalation methodologies, the interlayer spacing of MoO3 is remarkably enlarged to 10.40 Å and the layer structural integration are reinforced by dimercapto groups of bismuththiol molecules. Comprehensive characterizations and density functional theory calculations prove that the intercalated bismuththiol (DMcT) molecules substantially enhanced electronic conductivity and effectively shield the electrostatic interaction between Na+ and the MoO3 host by conjugated double bond, resulting in improved Na+ insertion/extraction kinetics. Benefiting from these features, the newly devised layered MoO3 electrode achieves excellent long‐term cycling stability and outstanding rate performance. These achievements are of vital significance for the preparation of sodium‐ion battery anode materials with high‐rate capability and long cycling life using intercalation chemistry. 相似文献
8.
Xiaofan Zhang 《中国物理 B》2022,31(11):114209-114209
We theoretically investigate the yield enhancement of elliptical high harmonics in the interaction of molecules with bicircular laser pulses by solving the time-dependent Schrödinger equation. It is shown that by adjusting the relative intensity ratio of the two bicircular field components in specific ranges the yield of the molecular high harmonics for the plateau and cutoff regions can be respectively enhanced. To analyze this enhancement phenomenon, we calculate the weights of the electron classical trajectories. Additionally, we also study the ellipticity distribution of harmonics for different intensity ratios. We find that these enhanced harmonics are elliptically polarized, which we mainly attribute to the recombination dipole moment of the major weighted trajectories. These enhanced elliptical extreme ultraviolet and soft x-ray radiations may serve as essential tools for exploring the ultrafast dynamics in magnetic materials and chiral media. 相似文献
9.
Mining high utility itemsets (HUIs) from transaction databases considers such factors as the unit profit and quantity of purchased items. Two-phase tree-based algorithms transform a database into compressed tree structures and generate candidate patterns through a recursive pattern-growth procedure. This procedure requires a lot of memory and time to construct conditional pattern trees. To address this issue, this study employs two compressed tree structures, namely, Utility Count Tree and String Utility Tree, to enumerate valid patterns and thus promote fast utility computation. Furthermore, the study presents an algorithm called single-phase utility computation (SPUC) that leverages these two tree structures to mine HUIs in a single phase by incorporating novel pruning strategies. Experiments conducted on both real and synthetic datasets demonstrate the superior performance of SPUC compared with IHUP, UP-Growth, and UP-Growth+ algorithms. 相似文献
10.
We generalize Nagel’s formula for the Szegö kernel and use it to compute the Szegö kernel on a class of non-compact CR manifolds whose tangent space decomposes into one complex direction and several totally real directions. We also discuss the control metric on these manifolds and relate it to the size of the Szegö kernel. 相似文献