全文获取类型
收费全文 | 16543篇 |
免费 | 2182篇 |
国内免费 | 1450篇 |
专业分类
化学 | 11137篇 |
晶体学 | 137篇 |
力学 | 2570篇 |
综合类 | 208篇 |
数学 | 720篇 |
物理学 | 5403篇 |
出版年
2024年 | 37篇 |
2023年 | 161篇 |
2022年 | 445篇 |
2021年 | 493篇 |
2020年 | 621篇 |
2019年 | 543篇 |
2018年 | 508篇 |
2017年 | 567篇 |
2016年 | 773篇 |
2015年 | 759篇 |
2014年 | 797篇 |
2013年 | 2042篇 |
2012年 | 986篇 |
2011年 | 1012篇 |
2010年 | 733篇 |
2009年 | 834篇 |
2008年 | 774篇 |
2007年 | 925篇 |
2006年 | 797篇 |
2005年 | 771篇 |
2004年 | 719篇 |
2003年 | 596篇 |
2002年 | 552篇 |
2001年 | 426篇 |
2000年 | 410篇 |
1999年 | 337篇 |
1998年 | 357篇 |
1997年 | 313篇 |
1996年 | 250篇 |
1995年 | 255篇 |
1994年 | 184篇 |
1993年 | 207篇 |
1992年 | 179篇 |
1991年 | 130篇 |
1990年 | 99篇 |
1989年 | 79篇 |
1988年 | 91篇 |
1987年 | 63篇 |
1986年 | 55篇 |
1985年 | 53篇 |
1984年 | 46篇 |
1983年 | 13篇 |
1982年 | 29篇 |
1981年 | 30篇 |
1980年 | 21篇 |
1979年 | 31篇 |
1978年 | 13篇 |
1976年 | 13篇 |
1973年 | 13篇 |
1972年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
Zhihong Zhao Bin Wang Rui Tan Wenjing Liu Minghui Zhang 《Magnetic resonance in chemistry : MRC》2022,60(4):427-433
In this study, the transverse relaxation time (T2) of activated carbon (AC) in different relative environment humidity was detected firstly by low-field nuclear magnetic resonance (LFNMR). The pore size (diameter) of AC distributions was calculated by the relationship between T2 and surface relaxation rate (ρ), where ρ was obtained by the detection of nine porous materials with known pore size. The results showed that the pore size distributions of AC calculated by ρ < 0.19 nm/ms were in good agreement with that obtained by nitrogen adsorption method and proved that LFNMR as a new detection method was feasible for characterizing AC pore size distribution. 相似文献
2.
《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
3.
《Mendeleev Communications》2022,32(4):534-536
Correlation times and diffusion coefficients of water molecules were measured for the first time by 1H spin relaxation and pulsed field gradient NMR in Li+, Na+ and Cs+ ionic forms of Nafion 117 membrane. Hydration numbers of Li+, Na+ and Cs+ cations were calculated. It was shown that at high humidity macroscopic transfer is controlled by the local translational motion of water molecules. 相似文献
4.
当煤层上方为坚硬顶板时,在工作面回采期间容易出现大面积悬顶,导致巷旁充填体出现大变形破坏,极大威胁采煤安全.为解决这一问题,以某矿1205工作面沿空留巷为工程背景,分析了爆炸围岩裂隙范围和坚硬顶板破断特征,建立了切顶卸压围岩结构力学模型,研究表明,相邻炮孔爆炸后,炮孔间裂隙互相贯穿,降低了顶板强度,同时当切顶角为15°时,巷道稳定性较好.工程实践结果表明:采用爆破切顶技术后,顶板下沉量减小了62.3%,较好地保证了围岩稳定性. 相似文献
5.
《Studies in Applied Mathematics》2018,141(3):399-417
We extend our previous results characterizing the loading properties of a diffusing passive scalar advected by a laminar shear flow in ducts and channels to more general cross‐sectional shapes, including regular polygons and smoothed corner ducts originating from deformations of ellipses. For the case of the triangle and localized, cross‐wise uniform initial distributions, short‐time skewness is calculated exactly to be positive, while long‐time asymptotics shows it to be negative. Monte Carlo simulations confirm these predictions, and document the timescale for sign change. The equilateral triangle appears to be the only regular polygon with this property—all others possess positive skewness at all times. Alternatively, closed‐form flow solutions can be constructed for smooth deformations of ellipses, and illustrate how both nonzero short‐time skewness and the possibility of multiple sign switching in time is unrelated to domain corners. Exact conditions relating the median and the skewness to the mean are developed which guarantee when the sign for the skewness implies front (more mass to the right of the mean) or back (more mass to the left of the mean) “loading” properties of the evolving tracer distribution along the pipe. Short‐ and long‐time asymptotics confirm this condition, and Monte Carlo simulations verify this at all times. The simulations are also used to examine the role of corners and boundaries on the distribution for short‐time evolution of point source , as opposed to cross‐wise uniform, initial data. 相似文献
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.
Erosion and sediments transport processes have a great impact on industrial structures and on water quality. Despite its limitations, the Saint‐Venant‐Exner system is still (and for sure for some years) widely used in industrial codes to model the bedload sediment transport. In practice, its numerical resolution is mostly handled by a splitting technique that allows a weak coupling between hydraulic and morphodynamic distinct softwares but may suffer from important stability issues. In recent works, many authors proposed alternative methods based on a strong coupling that cure this problem but are not so trivial to implement in an industrial context. In this work, we then pursue 2 objectives. First, we propose a very simple scheme based on an approximate Riemann solver, respecting the strong coupling framework, and we demonstrate its stability and accuracy through a number of numerical test cases. However, second, we reinterpret our scheme as a splitting technique and we extend the purpose to propose what should be the minimal coupling that ensures the stability of the global numerical process in industrial codes, at least, when dealing with collocated finite volume method. The resulting splitting method is, up to our knowledge, the only one for which stability properties are fully demonstrated. 相似文献
8.
Teobald Kupka Małgorzata A. Broda Piotr P. Wieczorek 《Magnetic resonance in chemistry : MRC》2020,58(6):584-593
The biologically active alkaloid muscimol is present in fly agaric mushroom (Amanita muscaria), and its structure and action is related to human neurotransmitter γ-aminobutyric acid (GABA). The current study reports on determination of muscimol form present in water solution using multinuclear 1H and 13C nuclear magnetic resonance (NMR) experiments supported by density functional theory molecular modeling. The structures of three forms of free muscimol molecule both in the gas phase and in the presence of water solvent, modeled by polarized continuous model, and nuclear magnetic isotropic shieldings, the corresponding chemical shifts, and indirect spin–spin coupling constants were calculated. Several J-couplings observed in proton and carbon NMR spectra, not available before, are reported. The obtained experimental spectra, supported by theoretical calculations, favor the zwitterion form of muscimol in water. This structure differs from NH isomer, previously determined in dimethyl sulfoxide (DMSO) solution. In addition, positions of signals C3 and C5 are reversed in both solvents. 相似文献
9.
András Gy. Németh Renáta Szabó Dr. Attila Domján Prof. György M. Keserű Dr. Péter Ábrányi-Balogh 《ChemistryOpen》2021,10(1):16-27
The development of a new three-component chromatography-free reaction of isocyanides, amines and elemental sulfur allowed us the straightforward synthesis of thioureas in water. Considering a large pool of organic and inorganic bases, we first optimized the preparation of aqueous polysulfide solution from elemental sulfur. Using polysulfide solution, we were able to omit the otherwise mandatory chromatography, and to isolate the crystalline products directly from the reaction mixture by a simple filtration, retaining the sulfur in the solution phase. A wide range of thioureas synthesized in this way confirmed the reasonable substrate and functional group tolerance of our protocol. 相似文献
10.
ABSTRACTQM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S4 state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)4–O(5) bond and the π*-LUMO of the Mn(V)1=O(6) bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn4O6 cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)1=O(6) bond to the σ*-LUMO of the Mn(IV)4–O(5) bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)4–O(5)]-? part is relaxed to the ?Mn(III)4?…?O(5)- structure and the cation radical [O(6)=Mn(V)1]+ ? part is relaxed to the +O(6)–Mn(IV)1? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)4->Mn(III)4 and Mn(V)1->Mn(IV)1. On the other hand, the O(5)- and O(6)+ sites generated undergo the O–O bond formation in the CaMn4O6 cluster. The Ca(II) ion in the cubane- skeleton of the CaMn4O6 cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)1=O(6) and σ*-LUMO of Mn(IV)4–O(5), indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism. 相似文献