全文获取类型
收费全文 | 89995篇 |
免费 | 697篇 |
国内免费 | 552篇 |
专业分类
化学 | 25777篇 |
晶体学 | 809篇 |
力学 | 6824篇 |
综合类 | 2篇 |
数学 | 32142篇 |
物理学 | 15670篇 |
无线电 | 10020篇 |
出版年
2023年 | 155篇 |
2022年 | 206篇 |
2021年 | 218篇 |
2020年 | 196篇 |
2019年 | 216篇 |
2018年 | 11951篇 |
2017年 | 11537篇 |
2016年 | 7113篇 |
2015年 | 1097篇 |
2014年 | 584篇 |
2013年 | 607篇 |
2012年 | 4455篇 |
2011年 | 11897篇 |
2010年 | 6977篇 |
2009年 | 6899篇 |
2008年 | 7320篇 |
2007年 | 9740篇 |
2006年 | 309篇 |
2005年 | 1595篇 |
2004年 | 1757篇 |
2003年 | 2175篇 |
2002年 | 1081篇 |
2001年 | 251篇 |
2000年 | 296篇 |
1999年 | 153篇 |
1998年 | 197篇 |
1997年 | 143篇 |
1996年 | 196篇 |
1995年 | 116篇 |
1994年 | 74篇 |
1993年 | 94篇 |
1992年 | 52篇 |
1991年 | 64篇 |
1990年 | 55篇 |
1989年 | 58篇 |
1988年 | 58篇 |
1987年 | 57篇 |
1986年 | 58篇 |
1985年 | 48篇 |
1984年 | 42篇 |
1983年 | 36篇 |
1982年 | 41篇 |
1981年 | 38篇 |
1980年 | 46篇 |
1979年 | 44篇 |
1914年 | 45篇 |
1913年 | 40篇 |
1912年 | 40篇 |
1909年 | 41篇 |
1908年 | 40篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Jacopo Sgrignani Filomena De Luca Hayarpi Torosyan Jean-Denis Docquier Da Duan Beatrice Novati Fabio Prati Giorgio Colombo Giovanni Grazioso 《Journal of computer-aided molecular design》2016,30(10):851-861
β-Lactamases are bacterial enzymes conferring resistance to β-lactam antibiotics in clinically-relevant pathogens, and represent relevant drug targets. Recently, the identification of new boronic acids (i.e. RPX7009) paved the way to the clinical application of these molecules as potential drugs. Here, we screened in silico a library of ~1400 boronic acids as potential AmpC β-lactamase inhibitors. Six of the most promising candidates were evaluated in biochemical assays leading to the identification of potent inhibitors of clinically-relevant β-lactamases like AmpC, KPC-2 and CTX-M-15. One of the selected compounds showed nanomolar K i value with the clinically-relevant KPC-2 carbapenemase, while another one exhibited broad spectrum inhibition, being also active on Enterobacter AmpC and the OXA-48 class D carbapenemase. 相似文献
992.
Organic–inorganic hybrid compounds of transition metal mono-substituted molybdophosphates, (H2bipy)2[PNi(Hbipy)Mo11O39]·4H2O (1), (H2bipy)1.5[HPCu(Hbipy)Mo11O39]·4H2O (2) (bipy = 4,4′-bipyridine), were synthesized hydrothermally and characterized by elemental analysis, IR spectroscopy, TGA, fluorescent spectroscopy, powder and single crystal X-ray diffraction methods. In 1 and 2 the transition metal atom (Ni and Cu) occupies one site of twelve molybdenum atoms of Keggin anion and combines a monoprotonated bipyridine molecular cation, Hbipy+, forming a 4,4′-bipyridine–decorated M-substituted molybdophosphate anion (M = Ni and Cu). In 1 two anions form a dimer through hydrogen bonds, in 2 the anions form a chain through hydrogen bonds. The dimers or the chains, H2bipy2+ cations and lattice water molecules are connected by hydrogen bonds, giving supramolecular compounds. The two kinds of bipy molecules, coordinated and uncoordinated, in 1 and 2 give two emission peaks in their photoluminescent spectra. 相似文献
993.
Xiaoqing Liang Xue Wu Xiaoming Huang Yan Su Jun Hu Jijun Zhao 《Journal of Cluster Science》2016,27(3):935-946
We employ a noncollinear implementation of density functional theory (DFT) including spin–orbit coupling (SOC) interaction to calculate the magnetic properties of Irn (n = 2–5) clusters. The impact of the magnetic anisotropy on the geometric structures and magnetic properties has been analyzed. SOC leads to formation of large orbital moment and a mixing of different spin states, but does not affect the relative stability of different structural isomers for a given cluster. In order to measure the SOC effect, we further define the spin–orbit energy (Eso) and compute the exact values. Magnetic anisotropy energies (MAEs) obtained from DFT calculations are further supported by the results of torque approach. We find that MAEs of Ir2 and Ir3 in ground state configurations are 40.6 and 28.5 meV respectively, while the MAE decreases to 9 meV for Ir4. For Ir5, MAE for its ground state structure increases to 38.3 meV. 相似文献
994.
Alicia Henry Marie-France Vallat Gauthier Schrodj Philippe Fioux Vincent Roucoules Gregory Francius Jalal Bacharouche 《Plasma Chemistry and Plasma Processing》2016,36(2):627-650
Surface modification studies of non-vulcanized BR elastomers (butadiene rubber) by low-pressure air plasma treatment and the effect on ageing and adhesion performances are presented in this paper. In particular, the influence of discharge power and distance from the glow discharge, and impact of antioxidant molecules in the BR formulation were examined. To characterize the changes to the BR surface, XPS spectroscopy, contact angle measurements, AFM nanoindentation experiments and tack measurements were utilized. Oxidation and crosslinking were the main mechanisms observed on the polymer chains regardless of the plasma conditions used. Beyond a certain threshold of plasma energy (in our case, discharge power of ~60 W and exposure time of ~30 s), a steady state was reached irrespective of the distance from the glow discharge. The presence of antioxidant molecules considerably reduced crosslinking phenomena while maintaining oxidation processes on polymer chains and increasing the nitrogen content in the near surface region. The mechanisms responsible for these differences have been identified. Interestingly, the COOH/C=O ratio changed according to the balance between oxidation and crosslinking. The hydrophobic recovery rate was mainly driven by temperature-dependent dynamics and varied according to the degree of crosslinking in the surface region. It was found to be lower in air atmosphere in the presence of antioxidant molecules. Finally, the presence of antioxidant molecules in the BR formulation allowed the adhesion performances after plasma exposure to significantly increase. 相似文献
995.
Ladislav Androvič Jan Bartáček Miloš Sedlák 《Research on Chemical Intermediates》2016,42(6):5133-5145
This mini-review describes recent developments and trends in the area of syntheses and applications of azo compounds, which are planned to act as initiators of radical reactions, particularly polymerizations. The paper reports chemical modifications of well-known initiators (AIBN, etc.) or variants of syntheses of new types of these compounds. The chemical modifications of basic skeletons of azo initiators are discussed in the context with their properties and applications. Also discussed are the contemporary trends in the development of these initiators, particularly in preparation of microparticles and nanoparticles of polymers or hybrid inorganic–organic microparticles and nanoparticles prepared for intentional studies and applications. 相似文献
996.
Donguk Kim Seulah Lee Jihye Lee Yeseul Choi Jaeuk Shin Jung Kyoo Lee 《Research on Chemical Intermediates》2016,42(1):249-267
An in situ bimolecular reaction, in which syngas is fed with toluene as a secondary reactant (hereafter Tol in situ methylation), was studied over bifunctional catalysts comprised of methanol synthesis catalyst and H-ZSM-5 in a fixed-bed down-flow reactor at 460 psig. When physically mixed with H-ZSM-5 to form bifunctional catalysts, CrZ_HZ (Cr2O3/ZnO + HZSM-5) catalyst showed much higher activity than CZA_HZ (CuO/ZnO/Al2O3 + H-ZSM-5) in the Tol in situ methylation, while CrZ catalyst exhibited substantially lower activity than CZA in methanol synthesis. CO conversion to methanol in the Tol in situ methylation was estimated by Bz in situ methylation. The CO conversion to methanol was calculated to be in the range of 11–27 %, while that in methanol synthesis over CrZ was about 5 % at most due to chemical equilibrium limitation. By employing a silicalite-coated H-ZSM-5 (Sil/HZ) in bifunctional catalyst, xylene selectivity and para-xylene yield were much improved in the Tol in situ methylation. 相似文献
997.
Mi-Hyun Lee Bhari Mallanna Nagaraja Prakash Natarajan Ngoc Thanh Truong Kwan Young Lee Sungho Yoon Kwang-Deog Jung 《Research on Chemical Intermediates》2016,42(1):123-140
PtSn/θ-Al2O3 catalysts with different amounts of K (0.14, 0.22, 0.49, 0.72, and 0.96 wt%) are prepared to investigate the K effects on the PtSn catalyst in propane dehydrogenation (PDH). KPtSn catalyst with 0.xx wt% K, 0.5 wt% Pt and 0.75 wt% Sn is designated as xx-KPtSn. PDH was performed at 873 K and a gas hourly space velocity (GHSV) of 53,000 mL/gcat h. The temperature-programmed desorption (NH3-TPD), temperature-programmed reduction (TPR) and CO chemisorption of the KPtSn catalysts with K added revealed the potassium addition blocked the acid sites, promoted the reduction of Sn oxide and decreased the Pt dispersion. The formations of cracking products and higher hydrocarbons on acid sites were suppressed by the K effect of blocking the acid sites. In contrast, K addition at more than 0.72 wt% rather increased cracking products and the amount of coke, resulting in the severe deactivation of catalysts. The high cracking products on the KPtSn catalysts with the high amount of K should not be related to the acid sites, because the acid sites were monotonously decreased with an increase in the amount of K. Instead, the potassium affected the characteristics of PtSn. The interaction between Pt and Sn could be weakened by enriching the reduced Sn, because the K component promoted the reduction of Sn oxide in the TPR experiments. Therefore, the 14-KPtSn catalyst with the low amount of K exhibits the highest stability and selectivity among the prepared KPtSn catalysts due to the compromise of the advantageous (blocking the acid sites) and bad (weakening the interaction between Pt and Sn) effects of the K addition in PDH. 相似文献
998.
Xianhao Lv Mizhen Sun Lei Xu Runzhe Wang Huayi Zhou Yuyu Pan Shitong Zhang Qikun Sun Shanfeng Xue Wenjun Yang 《Chemical science》2020,11(19):5058
Designing a donor–acceptor (D–A) molecule with a hybridized local and charge transfer (HLCT) excited state is a very effective strategy for producing an organic light-emitting diode (OLED) with a high exciton utilization efficiency and external quantum efficiency. Herein, a novel twisting D–π–A fluorescent molecule (triphenylamine–anthracene–phenanthroimidazole; TPAAnPI) is designed and synthesized. The excited state properties of the TPAAnPI investigated through photophysical experiments and density functional theory (DFT) analysis reveal that its fluorescence is due to the HLCT excited state. The optimized non-doped blue OLED using TPAAnPI as a light-emitting layer exhibits a novel blue emission with an electroluminescence (EL) peak at 470 nm, corresponding to the Commission International de L''Eclairage (CIE) coordinates of (0.15, 0.22). A fabricated device termed Device II exhibits a maximum current efficiency of 18.09 cd A−1, power efficiency of 12.35 lm W−1, luminescence of ≈29 900 cd cm−2, and external quantum efficiency (EQE) of 11.47%, corresponding to a high exciton utilization efficiency of 91%. Its EQE remains as high as 9.70% at a luminescence of 1000 cd m−2 with a low efficiency roll-off of 15%. These results are among the best for HLCT blue-emitting materials involved in non-doped blue fluorescent OLEDs. The performance of Device II highlights a great industrial application potential for the TPAAnPI molecule.A new pure fluorescent blue HLCT-emitter was designed and synthesized. Highly efficient non-doped blue OLEDs with low efficiency roll-off were achieved. 相似文献
999.
Deng B Wang Z Song J Xiao Y Chen D Huang J 《Analytical and bioanalytical chemistry》2011,401(7):2143-2152
The doxorubicin (DOX) uptake in single human leukemia K562 cells with changes in both drug dosage and exposure period was
studied using capillary electrophoresis (CE) coupled with laser-induced fluorescence (LIF) detection. The cells were treated
with DOX at different concentrations (1, 3, 10, 20, 30, and 50 μM) and for different exposure times (1, 3, 5, 24, and 48 h).
At least 20 cells were analyzed for each DOX-treated cell population. A marked heterogeneity in DOX uptake among single cells
was observed, because the relative standard deviation of the uptake of DOX by single cells ranged from 24.0% to 61.1% within
each cell population. The cell-to-cell heterogeneity in DOX uptake first decreased and then became constant with increasing
drug concentration, but it did not exhibit regular variation with increasing exposure time. The mean DOX uptake was a linear
function of drug concentration (r ≥ 0.9667). In terms of the correlation with exposure time, the mean DOX uptake reached its maximum at 3 h for the cell populations
treated with 1–10 μM DOX, while it kept increasing during 48 h exposure of cell populations to 20–50 μM DOX. Because it eliminates
DOX fluorescence quenching and sample loss, the CE-LIF method directly detects the true DOX uptake by single cells, and thus
presents accurate information on both the cell-to-cell heterogeneity in DOX uptake and the patterns of DOX uptake in K562
cells as functions of drug concentration and exposure time. 相似文献
1000.
Mesoporous carbons containing silver nanoparticles have been successfully synthesized under acidic conditions by employing
resorcinol and formaldehyde as carbon precursors and triblock copolymer EO101PO56EO101 (Lutrol F127) as a soft template. Silver nanoparticles of ∼90 nm were added to the synthesis mixture to achieve 10 wt% and
20 wt% of Ag loading in the carbon. Also, tetraethyl orthosilicate (TEOS) was introduced to the system in order to improve
adsorption properties of the silver-carbon composites and to reinforce its structure. The resulting carbons with incorporated
silver nanoparticles featured high surface areas, large total pore volumes and primary mesopores in the range between ∼6–7 nm. 相似文献